THERMODYNAMICS, KINETICS,

AND MICROPHYSICS OF CLOUDS

Climate change has provided a new impetus for research on clouds and precipitation. One of the greatest
uncertainties in current global climate models is cloud feedback, arising from uncertainties in the param-
eterization of cloud processes and their impact on the global radiation balance. In the past two decades,
substantial progress has been made in the simulation of clouds using cloud resolving models. However,
most of the parameterizations employed in these models have been empirically based. New theoretical
descriptions of cloud processes are now being incorporated into cloud models, using spectral microphysics
based on the kinetic equations for the drop and crystal size spectra along with the supersaturation equation,
and newer parameterizations of drop activation and ice nucleation based on the further development of the
classical nucleation theory. From these models, cloud microphysics parameterizations are being developed
for use in global weather and climate models.
Thermodynamics, Kinetics, and Microphysics of Clouds reflects this shift to an increasingly theoretical
basis for the simulation and parameterization of cloud processes. The book presents a unified theoretical
foundation that provides the basis for incorporating cloud microphysical processes in cloud and climate
models in a manner that represents interactions and feedback processes over the relevant range of environ-
mental and parametric conditions. In particular, this book provides:

• the closed system of equations of spectral cloud microphysics that includes kinetic equations for the
drop and crystal size spectra for regular and stochastic condensation/deposition and coagulation/accretion
along with the supersaturation equations;
• the latest theories and theoretical parameterizations of aerosol hygroscopic growth, drop activation, and
ice homogeneous and heterogeneous nucleation, derived from the general principles of thermodynamics
and kinetics and suitable for cloud and climate models;
• a theoretical basis for understanding the processes of cloud particle formation, evolution, and precipitation,
based on numerical cloud simulations and analytical solutions to the kinetic equations and supersaturation
equation;
• a platform for advanced parameterizations of clouds in weather prediction and climate models using
these solutions; and
• the scientific foundation for weather and climate modification by cloud seeding.

This book will be invaluable for researchers and advanced students engaged in cloud and aerosol physics,
and air pollution and climate research.

Vitaly I. Khvorostyanov is Professor of Physics of the Atmosphere and Hydrosphere, Central Aerological
Observatory (CAO), Russian Federation. His research interests are in cloud physics, cloud numerical model-
ing, atmospheric radiation, and cloud-aerosol and cloud-radiation interactions, with applications for climate
studies and weather modification. He has served as Head of the Laboratory of Numerical Modeling of
Cloud Seeding at CAO, Coordinator of the Cloud Modeling Programs on Weather Modification by Cloud
Seeding in the USSR and Russia, Member of the International GEWEX Radiation Panel of the World Climate
Research Program, and Member of the International Working Group on Cloud-Aerosol Interactions.
Dr. Khvorostyanov has worked as a visiting scientist and Research Professor in the United States, United
Kingdom, France, Germany, and Israel. He has co-authored nearly 200 journal articles and four books:
Numerical Simulation of Clouds (1984), Clouds and Climate (1986), Energy-Active Zones: Conceptual
Foundations (1989), and Cirrus (2002). Dr. Khvorostyanov is a member of the American Geophysical
Union and the American Meteorological Society.

Judith A. Curry is Professor and Chair of the School of Earth and Atmospheric Sciences at the Georgia
Institute of Technology. She previously held faculty positions at the University of Colorado, Penn State
University, and Purdue University. Dr. Curry’s research interests span a variety of topics in the atmospheric
and climate sciences. Current interests include cloud microphysics, air and sea interactions, and climate
feedback processes associated with clouds and sea ice. Dr. Curry is co-author of Thermodynamics of
Atmospheres and Oceans (1999) and editor of the Encyclopedia of Atmospheric Sciences (2003). She has
published more than 190 refereed journal articles. Dr. Curry is a Fellow of the American Meteorological
Society, the American Association for the Advancement of Science, and the American Geophysical Union.
In 1992, she received the Henry Houghton Award from the American Meteorological Society.
The Cloud
Percy Bysshe Shelley (1820)

I bring fresh showers for the thirsting flowers,

From the seas and the streams;
I bear light shade for the leaves when laid
In their noonday dreams.
From my wings are shaken the dews that waken
The sweet buds every one,
When rocked to rest on their mother’s breast,
As she dances about the sun.
I wield the flail of the lashing hail,
And whiten the green plains under,
And then again I dissolve it in rain,
And laugh as I pass in thunder.

I am the daughter of Earth and Water,

And the nursling of the Sky;
I pass through the pores of the oceans and shores;
I change, but I cannot die.
For after the rain, when with never a stain
The pavilion of Heaven is bare
And the winds and sunbeams with their convex gleams
Build up the blue dome of air,
I silently laugh at my own cenotaph
And out of the caverns of rain,
Like a child from the womb, like a ghost from the tomb,
I arise and unbuild it again.

(Poetical Works of Shelley (Cambridge Editions),

by Percy Bysshe Shelley (Author), Newell F. Ford (Introduction).
Publisher: Houghton Mifflin; Revised edition,
January 1975, 704 pages, ISBN-10: 0395184614)
THERMODYNAMICS,
KINETICS, AND
MICROPHYSICS OF CLOUDS

VITALY I. KHVOROSTYANOV
Central Aerological Observatory, Russia

JUDITH A. CURRY
Georgia Institute of Technology, USA
32 Avenue of the Americas, New York, NY 10013-2473, USA

Cambridge University Press is part of the University of Cambridge.

It furthers the University’s mission by disseminating knowledge in the pursuit of
education, learning, and research at the highest international levels of excellence.

www.cambridge.org
Information on this title: www.cambridge.org/9781107016033
© Vitaly I. Khvorostyanov and Judith A. Curry 2014

This publication is in copyright. Subject to statutory exception

and to the provisions of relevant collective licensing agreements,
no reproduction of any part may take place without the written
permission of Cambridge University Press.
First published 2014
Printed in the United States of America
A catalog record for this publication is available from the British Library.
Library of Congress Cataloging in Publication Data
Khvorostyanov, Vitaly I.
Thermodynamics, kinetics, and microphysics of clouds / Vitaly I. Khvorostyanov,
Judith A. Curry. — First edition.
pages cm
Includes bibliographical references and index.
ISBN 978-1-107-01603-3
1. Precipitation (Meteorology)—Measurement. 2. Cloud forecasting.
3. Precipitation forecasting. 4. Atmospheric thermodynamics. I. Curry, Judith A. II. Title.
QC925.K47 2014
551.57’6—dc23 2014001806
ISBN 978-1-107-01603-3 Hardback

Cambridge University Press has no responsibility for the persistence or accuracy of

URLs for external or third-party Internet Web sites referred to in this publication and does not
guarantee that any content on such Web sites is, or will remain, accurate or appropriate.
Contents

Preface page xv
1. Introduction 1
1.1. Relations among Thermodynamics, Kinetics, and Cloud Microphysics 1
1.2. The Correspondence Principle 2
1.3. Structure of the Book 3
2. Clouds and Their Properties 9
2.1. Cloud Classification 9
2.2. Cloud Regimes and Global Cloud Distribution 13
2.2.1. Large-Scale Condensation in Fronts and Cyclones 16
2.2.2. Sc-St Clouds and Types of Cloud-Topped Boundary Layer 18
2.2.3. Convective Cloudiness in the Intertropical Convergence Zone 19
2.2.4. Orographic Cloudiness 19
2.3. Cloud Microphysical Properties 20
2.4. Size Spectra and Moments 23
2.4.1. Inverse Power Laws 23
2.4.2. Lognormal Distributions 24
2.4.3. Algebraic Distributions 25
2.4.4. Gamma Distributions 26
2.5. Cloud Optical Properties 32
Appendix A.2. Evaluation of the Integrals
with Lognormal Distribution 44
3. Thermodynamic Relations 45
3.1. Thermodynamic Potentials 45
3.2. Statistical Energy Distributions 49
3.2.1. The Gibbs Distribution 49
3.2.2. The Maxwell Distribution 51
3.2.3. The Boltzmann Distribution 52
3.2.4. Bose–Einstein Statistics 54
3.2.5. Fermi–Dirac Statistics 55

v
vi Contents

3.3. Phase Rules 56

3.3.1. Bulk Phases 57
3.3.2. Systems with Curved Interfaces 57
3.4. Free Energy and Equations of State 59
3.4.1. An Ideal Gas 59
3.4.2. Free Energy and the van der Waals Equation of State
for a Non-Ideal Gas 62
3.5. Thermodynamics of Solutions 67
3.6. General Phase Equilibrium Equation for Solutions 70
3.6.1. General Equilibrium Equation 70
3.6.2. The Gibbs–Duhem Relation 72
3.7. The Clausius–Clapeyron Equation 73
3.7.1. Equilibrium between Liquid and Ice Bulk Phases 73
3.7.2. Equilibrium of a Pure Water Drop with Saturated Vapor 74
3.7.3. Equilibrium of an Ice Crystal with Saturated Vapor 75
3.7.4. Humidity Variables 78
3.8. Phase Equilibrium for a Curved Interface—The Kelvin Equation 80
3.9. Solution Effects and the Köhler Equation 81
3.10. Thermodynamic Properties of Gas Mixtures and Solutions 82
3.10.1. Partial Gas Pressures in a Mixture of Gases 82
3.10.2. Equilibrium of Two Bulk Phases around a Phase
Transition Point 83
3.10.3. Raoult’s Law for Solutions 84
3.10.4. Freezing Point Depression and Boiling Point Elevation 84
3.10.5. Relation of Water Activity and Freezing Point Depression 86
3.11. Adiabatic Processes 88
3.11.1. Dry Adiabatic Processes 88
3.11.2. Wet Adiabatic Processes 90
Appendix A.3. Calculation of Integrals with the Maxwell Distribution 95
4. Properties of Water and Aqueous Solutions 99
4.1. Properties of Water at Low Temperatures and High Pressures 99
4.1.1. Forms of Water at Low Temperatures 99
4.1.2. Forms of Water at High Pressures 101
4.2. Theories of Water 103
4.3. Temperature Ranges in Clouds and Equivalence of Pressure
and Solution Effects 107
4.4. Parameterizations of Water and Ice Thermodynamic Properties 108
4.4.1. Saturated Vapor Pressures 108
4.4.2. Heat Capacity of Water and Ice 109
4.4.3. Latent Heats of Phase Transitions 110
4.4.4. Surface Tension between Water and Air or Vapor 111
4.4.5. Surface Tension between Ice and Water or Solutions 112
Contents vii

4.4.6. Surface Tension between Ice and Air or Vapor 113

4.4.7. Density of Water 113
4.4.8. Density of Ice 113
4.5. Heat Capacity and Einstein-Debye Thermodynamic
Equations of State for Ice 114
4.6. Equations of State for Ice in Terms of Gibbs Free Energy 116
4.7. Generalized Equations of State for Fluid Water 120
4.7.1. Equations of the van der Waals Type and in
Terms of Helmholtz Free Energy 120
4.7.2. Equations of State Based on the Concept of the
Second Critical Point 122
Appendix A.4. Relations among Various Pressure Units 125
5. Diffusion and Coagulation Growth of Drops and Crystals 127
5.1. Diffusional Growth of Individual Drops 127
5.1.1. Diffusional Growth Regime 127
5.1.2. The Kinetic Regime and Kinetic Corrections to the Growth Rate 129
5.1.3. Psychrometric Correction Due to Latent Heat Release 132
5.1.4. Radius Growth Rate 135
5.1.5. Ventilation Corrections 137
5.2. Diffusional Growth of Crystals 138
5.2.1. Mass Growth Rates 138
5.2.2. Axial Growth Rates 141
5.2.3. Ventilation Corrections 143
5.3. Equations for Water and Ice Supersaturations 144
5.3.1. General Form of Equations for Fractional Water Supersaturation 144
5.3.2. Supersaturation Relaxation Times and Their Limits 147
5.3.3. Equation for Water Supersaturation in Terms
of Relaxation Times 149
5.3.4. Equivalence of Various Forms of Supersaturation Equations 151
5.3.5. Equation for Fractional Ice Supersaturation 152
5.3.6. Equilibrium Supersaturations over Water and Ice 154
Liquid Clouds 154
Ice Clouds 154
Mixed Phase Clouds 156
5.3.7. Adiabatic Lapse Rates with Non zero Supersaturations 157
5.4. The Wegener–Bergeron–Findeisen Process and Cloud Crystallization 158
5.5. Kinetic Equations of Condensation and Deposition in the Adiabatic Process 161
5.5.1. Derivation of the Kinetic Equations 161
5.5.2. Some Properties of Regular Condensation 163
5.5.3. Analytical Solution of the Kinetic Equations of
Regular Condensation 165
5.5.4. Equation for the Integral Supersaturation 167
viii Contents

5.6. Kinetic Equations of Coagulation 168

5.6.1. Various Forms of the Coagulation Equation 168
5.6.2. Collection Kernels for Various Coagulation Processes 170
Brownian Coagulation 170
Gravitational Coagulation 171
5.7. Thermodynamic and Kinetic Equations for Multidimensional Models 171
5.8. Fast Algorithms for Microphysics Modules in Multidimensional Models 173
6. Wet Aerosol Processes 181
6.1. Introduction 181
6.1.1. Empirical Parameterizations of Hygroscopic Growth 182
6.1.2. Empirical Parameterizations of Droplet Activation 183
6.2. Equilibrium Radii 186
6.2.1. Equilibrium Radii at Subsaturation 187
6.2.2. Equilibrium Radii of Interstitial Aerosol in a Cloud 193
6.3. Critical Radius and Supersaturation 197
6.4. Aerosol Size Spectra 203
6.4.1. Lognormal and Inverse Power Law Size Spectra 203
6.4.2. Approximation of the Lognormal Size Spectra
by the Inverse Power Law 203
6.4.3. Examples of the Lognormal Size Spectra,
Inverse Power Law, and Power Indices 204
6.4.4. Algebraic Approximation of the Lognormal Distribution 206
6.5. Transformation of the Size Spectra of Wet Aerosol at Varying Humidity 211
6.5.1. Arbitrary Initial Spectrum of Dry Aerosol 211
6.5.2. Lognormal Initial Spectrum of Dry Aerosol 212
6.5.3. Inverse Power Law Spectrum 216
6.5.4. Algebraic Size Spectra 218
6.6. CCN Differential Supersaturation Activity Spectrum 219
6.6.1. Arbitrary Dry Aerosol Size Spectrum 219
6.6.2. Lognormal Activity Spectrum 221
6.6.3. Algebraic Activity Spectrum 226
6.7. Droplet Concentration and the Modified Power Law for Drops Activation 230
6.7.1. Lognormal and Algebraic CCN Spectra 230
6.7.2. Modified Power Law for the Drop Concentration 231
6.7.3. Supersaturation Dependence of Power Law Parameters 233
Appendix A.6. Solutions of Cubic Equations for Equilibrium
and Critical Radii 237
7. Activation of Cloud Condensation Nuclei into Cloud Drops 241
7.1. Introduction 241
7.2. Integral Supersaturation in Liquid Clouds with Drop Activation 243
7.3. Analytical Solutions to the Supersaturation Equation 246
7.4. Analytical Solutions for the Activation Time, Maximum
Supersaturation, and Drop Concentration 250
Contents ix

7.5. Calculations of CCN Activation Kinetics 254

7.6. Four Analytical Limits of Solution 263
7.7. Limit #1: Small Vertical Velocity, Diffusional Growth Regime 265
7.7.1. Lower Bound 265
7.7.2. Upper Bound 268
7.7.3. Comparison with Twomey’s Power Law 270
7.8. Limit #2: Small Vertical Velocity, Kinetic Growth Regime 273
7.8.1. Lower Bound 273
7.8.2. Upper Bound 275
7.9. Limit #3: Large Vertical Velocity, Diffusional Growth Regime 277
7.9.1. Lower Bound 277
7.9.2. Upper Bound 277
7.10. Limit #4: Large Vertical Velocity, Kinetic Growth Regime 278
7.10.1. Lower Bound 278
7.10.2. Upper Bound 280
7.11. Interpolation Equations and Comparison with Exact Solutions 282
Appendix A.7. Evaluation of the Integrals J2 and J3 for Four Limiting Cases 284
8. Homogeneous Nucleation 289
8.1. Metastable States and Nucleation of a New Phase 290
8.2. Nucleation Rates for Condensation and Deposition 293
8.2.1. Application of Boltzmann Statistics 293
8.2.2. The Fokker–Planck, and the Frenkel–Zeldovich
Kinetic Equations and the Zeldovich Factor 295
8.2.3. Application of Bose–Einstein Statistics for Condensation
and Deposition 299
8.3. Nucleation Rates for Homogeneous Ice Nucleation 300
8.3.1. Nucleation Rates with the Boltzmann Distribution 300
8.3.2. Application of Bose–Einstein Statistics for Freezing 303
8.3.3. Parameterizations of Activation Energy 303
8.4. Semi-empirical Parameterizations of Homogeneous Ice Nucleation 305
8.5. Equations for Water and Ice Supersaturations with Homogeneous
Ice Nucleation 311
8.6. Critical Germ Size, Energy, and Homogeneous Freezing Rate 313
8.6.1. Derivation of the Critical Germ Size, Energy, and Nucleation Rate 313
8.6.2. Analysis and Properties of the Solution 319
8.6.3. Comparison with Other Models and Observations 322
8.6.4. The Freezing of Cloud Drops 325
8.7. Critical Freezing and Melting Temperatures of Homogeneous Freezing 328
8.7.1. General Expressions Based on Classical Theory 328
8.7.2. Liquidus Curves 331
8.7.3. Relation of the Freezing and Melting Point Depressions 332
8.7.4. Comparison with Observations 333
8.7.5. Equivalence of Solution and Pressure Effects 339
x Contents

8.8. Threshold or Critical Saturation Ratios for Homogeneous Freezing 345

8.8.1. General Equations 346
8.8.2. Parameterization of Effective Melting Heat 347
8.8.3. Derivation from Classical Theory of the Water Activity
Shift Method 350
8.8.4. Effects of Various Factors on the Critical Humidity Swhom
,cr 353
8.8.5. Calculations of Critical Relative Humidities over Water and Ice 354
8.9. Parcel Model Simulations of the Kinetics of Homogeneous Ice Nucleation 357
8.9.1. Parcel Model Description 357
8.9.2. Simulation Results 359
8.10. Analytical Parameterization of Homogeneous Ice Nucleation
Kinetics Based on Classical Nucleation Theory 368
8.10.1. General Features of Homogeneous Ice Nucleation Kinetics 368
8.10.2. The Freezing Rate and Its Simplification 369
8.10.3. Separation of Temperature and Supersaturation Dependencies 370
8.10.4. The Evolution of the Nucleation Rate and Crystal Concentration 373
8.10.5. Evaluation of the Deposition Integral Idep 377
8.10.6. Solution of Equations for the Supersaturation
and for Crystal Concentration 379
8.10.7. Particular Limiting Cases 381
Diffusion Growth Limit 381
Kinetic Growth and Large Particle Limits 381
8.10.8. Physical Interpretation 383
8.11. Temperature Effects and the Homogeneous Freezing of Cloud Drops 387
t

Appendix A.8. Evaluation of the Integrals J 0(ki ) = ∫ rc(,kef) (t , t0 ) exp(β t0 )dt0 391
0

9. Heterogeneous Nucleation of Drops and Ice Crystals 395

9.1. Introduction 395
9.2. Nucleation of Drops by Vapor Deposition on Water-Insoluble Particles 395
9.3. Modes of Ice Nucleation and Properties of Ice Nuclei 400
9.3.1. Modes of Ice Nucleation 400
9.3.2. Properties of Ice Nuclei 401
9.4. Empirical Parameterizations of Heterogeneous Ice Nucleation 404
9.5. Nucleation of Crystals in the Deposition Mode
on Water-Insoluble Particles 408
9.6. Ice Nucleation by Deliquescence-Freezing and Immersion 411
9.7. Critical Radius and Energy of Heterogeneous Freezing 412
9.7.1. Basic Dependencies of Heterogeneous Freezing 412
9.7.2. Volume Heterogeneous Freezing 414
9.7.3. Particular Cases of Critical Radius 419
9.7.4. Critical Energy of Volume Freezing 421
9.7.5. Modification of Critical Energy with Active Sites 423
Contents xi

9.8. Properties of the Deliquescence-Freezing Mode 426

9.8.1. Critical Radius, Energy, and the Nucleation Rate 426
9.8.2. Separation of Temperature, Supersaturation, and Aerosol
Dependences of the Critical Energy and Nucleation Rate 429
9.8.3. Separation of Insoluble Fractions between Activated Drops
and Unactivated CCN 434
9.8.4. Characteristic Relaxation Times of CCN Size
and Solution Concentration 435
9.9. Surface Freezing and Melting 436
9.9.1. Surface Freezing 436
9.9.2. Surface Melting 438
9.10. Nucleation in a Polydisperse Aerosol 440
9.10.1. Freezing of Haze Particles at Water Subsaturation in the DF Mode 440
9.10.2. Simultaneous Freezing in the DF and Immersion Modes
at Water Supersaturation 444
9.11. Critical Freezing and Melting Temperatures 446
9.11.1. General Equations 446
Volume Heterogeneous Freezing 446
Surface Quasi-Heterogeneous Freezing 450
Surface Quasi-Heterogeneous Melting 451
Liquidus Curves 452
9.12. Critical Saturation Ratios or Water Activities of Heterogeneous Freezing 452
9.12.1. General Equations 453
9.12.2. Simplifications of Equations for the Heterogeneous
Critical Saturation Ratio 454
9.12.3. Derivation from Classical Theory of the Water Activity Shift Method 456
9.12.4. Calculations of Critical Relative Humidities for
Heterogeneous Nucleation 458
9.12.5. Comparison of Critical Humidities for Heterogeneous
and Homogeneous Nucleation 463
9.13. Parcel Model for a Mixed-Phase Cloud 465
9.13.1. Supersaturation Equation with Nucleation of Drops and Crystals 466
9.13.2. Kinetic Equations for Droplet and Crystal Size Spectra with Particle
Nucleation 470
9.14. Parcel Model Simulations of Ice Nucleation Kinetics in Deliquescence-Freezing
Mode 470
9.14.1. Introduction 470
9.14.2. Simulation Characteristics 471
9.14.3. Kinetics of Ice Nucleation in the Mixed and Crystalline
Clouds with Weak Updrafts 473
9.14.4. Ice Nucleation Effects with Stronger Updrafts 482
9.14.5. Comparison with Homogeneous Nucleation Theory 485
xii Contents

9.15. Comparison of Simulated Crystal Concentrations with Experimental

Data and Parameterizations 491
9.16. Thermodynamic Constraints on Heterogeneous Ice Nucleation Schemes 497
9.17. Evaluation of Ice Nucleation and Cloud Phase State Parameterizations 501
10. Parameterizations of Heterogeneous Ice Nucleation 507
10.1. Analytical Parameterization of Heterogeneous Freezing Kinetics
Based on Classical Nucleation Theory (CNT) 507
10.1.1. Nucleation Rates in a Polydisperse Aerosol 507
10.1.2. Temporal Evolution of Supersaturation 508
10.1.3. Heterogeneous Nucleation Rate Derived from CNT
and Comparison with the Previous Parameterizations 510
10.1.4. Temporal Evolution of the Crystal Concentration 514
10.1.5. Comparison of Crystal Concentrations with Empirical
Parameterizations 515
10.1.6. Parameterization for the Large-Scale Models. Case 1:
Large Na and Crystal Concentrations Limited by Kinetics 516
10.1.7. Diffusion Growth Limit 520
10.1.8. The Kinetic Growth Limit, and Small and Large Particle Limits 522
10.1.9. Parameterization for the Large-Scale Models. Case 2:
Small IN Concentration Na and Crystal Concentration
Limited by Na 524
10.2. Temperature Effects and Heterogeneous Freezing of Cloud Drops 525
10.3. Parameterization of Deposition Ice Nucleation Based on
Classical Nucleation Theory 529
10.4. General Properties and Empirical Parameterizations of Contact Nucleation 533
10.4.1. General Properties 533
10.4.2. Empirical Parameterizations 535
10.5. Aerosol Scavenging by Drops 536
10.5.1. Brownian Diffusion 536
10.5.2. Thermophoresis 537
10.5.3. Diffusiophoresis 539
10.6. Freezing and Scavenging Rates 541
11. Deliquescence and Efflorescence in Atmospheric Aerosols 547
11.1. Phenomena of Deliquescence and Efflorescence 547
11.2. Theories and Models of Deliquescence and Efflorescence 549
11.3. A Model for Deliquescence of Salt Crystals Based
on the Entropy Equation 553
11.4. Applications of the Deliquescence Model 558
11.4.1. The Temperature Dependence of Dissolution Heat 559
11.4.2. The Temperature Dependence of Solubility 559
11.4.3. The Temperature Dependence of the Deliquescence
Relative Humidity 562
11.5. Phase Diagram of the Solution and Evaluation of the Eutectic Point 563
11.6. A Model for Efflorescence of Salt Crystals Based on the Entropy Equation 566
Contents xiii

11.7. Applications of the Efflorescence Model 570

11.7.1. The Temperature Dependence of Efflorescence 570
11.7.2. The Solute Activity and Mole Fraction Dependence of Efflorescence 571
11.7.3. The Joint Phase Diagram 573
12. Terminal Velocities of Drops and Crystals 577
12.1. Review of Previous Theories and Parameterizations 577
12.2. Basic Equations for Fall Velocities 582
12.3. Turbulent Corrections 587
12.4. Asymptotic Values and Applications for Spherical
and Nonspherical Particles 588
12.5. Corrections for Temperature and Pressure 591
12.6. Results of Calculations 593
12.6.1. Re-X Relation 593
12.6.2. The Drag Coefficient and “Crisis of Drag” 594
12.6.3. Application to Drops 596
12.6.4. Turbulent Corrections and Their Application to Aggregates 598
12.6.5. Other Crystal Habits 603
12.6.6. Application to Hail 605
12.6.7. Altitude Correction Calculations 606
12.7. Parameterizations for Large-Scale Models 608
12.8. Applications for Remote Sensing, Other Objects and Other Planets 610
13. Broad Size Spectra in Clouds and the Theory of Stochastic Condensation 613
13.1. Introduction 613
13.1.1. Mechanisms and Theories of the Formation of Broad Size
Spectra in Clouds 614
13.1.2. Kinetic Equations of Stochastic Condensation 618
13.2. Condensation in a Turbulent Cloud 623
13.2.1. Basic Equations 623
13.2.2. Stochastic Equations 624
13.2.3. Supersaturation Fluctuations 625
13.3. Evaluation of Correlation Functions 628
13.3.1. Expansions of Random Characteristics over the Turbulent Frequencies 628
13.3.2. Supersaturation as a Nonconservative Variable 629
13.3.3. Covariances with Supersaturation 630
13.3.4. Covariances with the Drop Size Distribution Function 631
13.4. General Kinetic Equations of Stochastic Condensation 633
13.5. Assumptions and Simplifications for Analytical Solutions 636
13.6. Approximation Neglecting the Diffusional Growth of Larger Particles 639
13.6.1. Small Particle Solution 640
13.6.2. Large Particle Solution 640
13.6.3. Merged Solution 641
13.6.4. Asymptotic Solutions 643
13.7. Solution Including the Diffusional Growth of Large Particles,
Sedimentation, and Coagulation 645
xiv Contents

13.8. Physical Interpretation of the Parameters 647

13.8.1. Various Forms of Solution Parameters 647
13.8.2. Solutions in the Form of Gamma Distributions 649
13.8.3. Solutions in the Form of Inverse Power Laws 654
13.9. Applications of the Solution for Liquid Clouds 656
13.10. Comparison with Previous Theories and Observations 661
13.11. Calculation of Size Spectra for a Crystalline Cloud 665
13.12. Derivation of the Generalized Stochastic Kinetic Equations
from the Fokker–Plank Equation 669
13.12.1. Chapman–Kolmogorov and Fokker–Planck Equations 669
13.12.2. Spatially Homogeneous Cloud 673
13.12.3. Spatially Inhomogeneous Cloud 676
Appendix A.13. Derivation and Solution of the Kummer Equation in Section 13.6.3 679
Appendix B.13. Solutions of Kinetic Equation of Section 13.7, Taking
into Account Diffusional Growth in the Tail 684
14. Analytical Solutions to the Stochastic Kinetic Equation for Precipitating Clouds 685
14.1. Introduction 685
14.2. Derivation of Kinetic Equations in Continuous Collection Approximations 688
14.3. Basic Equations and Assumptions for the Large-Size Fraction 692
14.4. Solutions for the Large-Size Fraction Taking into Account Diffusion
Growth and Coagulation 696
14.4.1. General Solution 696
14.4.2. Particular Case: Fall Speed as a Linear Function of Particle Size 698
14.4.3. Particular Case: Coagulation Growth Rate Much Greater
than Diffusion Growth Rate 699
14.4.4. Particular Case: Aerodynamic Regime for the Fall Speed
of Large Particles 700
14.4.5. Solutions for Subcloud Layers 702
14.5. Interpretation of Solutions 703
14.5.1. General Analysis of the Parameters 703
14.5.2. Example Calculations for a Crystalline Cloud 705
14.5.3. General Interpretation of the Solutions 709
14.6. Autoconversion and Corrections to the Analytical Solutions 712
14.7. The Coagulation Equation as the Integral Chapman–Kolmogorov
and Differential Fokker–Planck Equations 716
Appendix A.14. Evaluation of the Integrals in Section 14.4.2 for v(r) = Avr 722
Appendix B.14. Evaluation of the Integrals in Section 14.4.4 for v(r) = Avr1/2
(Aerodynamic Regime of Fall Velocities) 724
References 727
Notations 767
Index 777
Preface

Cloud microphysics is a branch of cloud physics that studies initiation, growth, and dissipation of
cloud and precipitation particles. Cloud microphysics is governed by the thermodynamic and kinetic
processes in clouds. The field of cloud microphysics has been intensively developed since the
1940s when the first successful experiments on cloud seeding were performed. The field has received
additional impetus in recent years from the challenges associated with forecasting precipitation and
understanding aerosol-cloud interactions in the context of climate change and feedback processes.
Several books on cloud microphysics are available, including Mason (1957), Fletcher (1962, 1970a),
Dufour and Defay (1963), Sedunov (1974), Voloshchuk and Sedunov (1975), Voloshchuk (1984),
Matveev (1984), Young (1993), Pruppacher and Klett (1997), and Cotton et al. (2011).
Thermodynamics, Kinetics, and Microphysics of Clouds extends the subject of cloud microphysics
beyond these previous treatments. The goals and contents of this book are formulated to:

• Present in compact form the major thermodynamic relations and kinetic equations required for
theoretical consideration of cloud microphysics;
• Review the currently known states of water in liquid, crystalline, and amorphous forms, and the
conceptual modern theories of water and equations of state for water in various states;
• Formulate a closed system of equations that describe the kinetics of cloud microphysical processes
and is suitable both for analytical studies and for inclusion in numerical models;
• Derive from theory generalized analytical parameterizations for aerosol deliquescence, hygroscopic
growth, efflorescence, and drop activation and ice nucleation in various modes;
• Demonstrate that these theoretical parameterizations generalize and unify previous parameteriza-
tions and include them as particular cases; express previous empirical parameters via atmospheric
and aerosol parameters and theoretical quantities;
• Derive the kinetic equations of stochastic condensation and coagulation and obtain their analytical
solutions that reproduce the observed drop and crystal size spectra; express parameters of empirical
distributions from theory; and
• Outline a path for future generalizations of the kinetic equations of cloud microphysics based on
the Chapman–Kolmogorov and Fokker–Planck equations.

Using the general principles of thermodynamics and kinetics, a closed system of equations is formu-
lated that includes kinetic equations for the drop and crystal size spectra along with the supersatura-
tion equations. Using these equations and further developing classical nucleation theory, theories are

xv

18:18:48
xvi Preface

developed of aerosol hygroscopic growth, drop activation, and ice homogeneous and heterogeneous
nucleation. Analytical expressions are obtained for the particle concentration, critical radii and ener-
gies of nucleation, nucleation rates that are expressed as functions of temperature, saturation ratio,
pressure, and aerosol concentration simultaneously and in factorized form. It is shown that the new
theoretical expressions generalize previous empirical parameterizations, can reduce to them in some
particular cases, and their empirical parameters are expressed via the aerosol parameters and physical
constants. The validity of these new theoretical expressions is verified in comparison with experi-
mental data, previous empirical and semi-empirical parameterizations, and parcel model simulations.
A similar theory is developed for the aerosol deliquescence and efflorescence. This allows for the
first time calculation from the theory of a unified phase diagram for solutions that are in agreement
with experimental phase diagrams.
Various analytical solutions to the kinetic equations and supersaturation equations are obtained
for adiabatic and non-adiabatic processes. These solutions are suitable both for analytical studies of
condensation and for inclusion in the numerical models. This system of equations, including kinetic
equations for drops and crystals and integral supersaturation equations, is generalized for the turbu-
lent atmosphere and multidimensional models. A fast algorithm for a numerical solution based on
the splitting method is described. Spectral bin microphysical method was applied for many years in
various 1D, 2D, and 3D models for various cloud types, and its applicability in the models of various
scales and dimensions is discussed.
The kinetic equations of stochastic condensation in a turbulent atmosphere are derived and gen-
eralized taking into account the coagulation and accretion processes. Various analytical solutions to
these stochastic equations are obtained, whose functional forms are similar to the gamma distribu-
tions and to exponential and inverse power laws that have been observed in clouds and precipitation.
The solution parameters are expressed via the atmospheric characteristics and physical constants, and
the solutions are verified through comparison with experimentally observed size spectra. These solu-
tions provide explanations of various empirical parameterizations and a platform for their refinement.
In addition to advancing our basic understanding of cloud microphysical processes, the theoretical
approach employed in this book supports the explanation and interpretation of laboratory and field
measurements in the context of instrument capabilities and limitations and motivates the design of
future laboratory and field experiments. In the context of models that include cloud processes, rang-
ing from small-scale models of clouds and atmospheric chemistry to global weather and climate
models, the unified theoretical foundations presented here provide the basis for incorporating cloud
microphysical processes in these models in a manner that represents the process interactions and
feedback processes over the relevant range of environmental and parametric conditions. Further, the
analytical solutions presented here provide the basis for computationally efficient parameterizations
that include the relevant parametric dependencies. The methods of cloud simulation using spectral
bin microphysics described here are especially suitable for modeling of weather modification by
cloud seeding since these methods are almost always based on modification of cloud microstructure
and phase state. These methods are also convenient for studies of inadvertent cloud modification by
anthropogenic and natural pollutions and for studies of cloud-radiation interactions.
This book incorporates the heritage of Russian cloud physics that introduced and developed
the kinetic equations for drop and crystal diffusion growth, the fast numerical algorithms for their

18:18:48
Preface xvii

solutions, and the stochastic approach to cloud microphysical processes. This Russian heritage is
combined with the best knowledge of cloud microphysics acquired and described in the Western
literature over the past several decades. A large amount of the material presented in this book is based
on original work conducted jointly by the authors over almost two decades. Some of this research has
been published previously in journal articles, but a large portion of this material is being published
here in this book for the first time, notably the parameterization of heterogeneous ice nucleation and
the theory of aerosol deliquescence and efflorescence.
Integration of Russian and Western perspectives on cloud physics was facilitated by the 1972 bilateral
treaty between the U.S. and USSR on Agreement and Cooperation in the Field of Environmental
Protection, specifically under Working Group VIII – The Influence of Environmental Change on
Climate. Its regular meetings and exchanges of delegations and information promoted interna-
tional collaboration, provided the foundation for long-term cooperation, and outlined proposals for
joint research. With the advent of the World Climate Research Programme (WCRP) in 1980, both
Khvorostyanov and Curry subsequently became members of the WCRP Working Group on Radiative
Fluxes, which later became the Radiation Panel of the Global Water and Energy Exchange Experiment
(GEWEX). The GEWEX Radiation Panel had regular annual meetings (where the authors participated
and met), which initiated the collaboration that has lasted for almost two decades, resulted in more
than 30 joint publications, and culminated in this book.
This book bridges Russian and Western perspectives of cloud physics. Khvorostyanov’s involve-
ment in the evolution of the Russian school of cloud physics includes development of cloud models
with spectral bin microphysics and applications to cloud seeding and cloud-radiation interactions.
Curry’s early cloud microphysics research focused on aircraft observations of cloud microphysics
and the development of parameterizations for cloud and climate models. Over the past 18 years,
Khvorostyanov and Curry have collaborated on a range of cloud microphysical topics of relevance
to understanding and parameterizing cloud processes for cloud and climate models, that integrate the
Russian perspectives on cloud microphysics into the broader community, and that combine Eastern
and Western approaches to cloud microphysics. In addition to summarizing and integrating these
perspectives and the broad body of recent research in cloud microphysics, throughout the book a
number of new results are included, as well as extensions and generalizations of existing ones.
This monograph is intended to provide a source of information for scientists engaged in teaching
and research in cloud physics and dynamics, aerosol physics, air pollution, and weather modification.
The book can be used as a textbook to provide graduate-level students with the theoretical founda-
tions of cloud microphysics. Researchers and students should have a basic background in physics and
thermodynamics and mathematical physics before using this book. Beyond this basic background,
the authors have made every effort to make the book as self-inclusive as possible. Formal derivations
and analytical solutions are emphasized, with every effort made to make the mathematical steps easy
to follow, including additional details in the appendices. A comprehensive bibliography is provided
that references seminal material in the primary literature and previous textbooks and monographs.
The authors gratefully acknowledge support from the DOE Atmospheric Radiation Measurement
Program and numerous NASA projects. Many basic concepts and views described in this book were
accumulated in multiyear fruitful collaboration with Prof. Mikhail Buikov, Prof. Kirill Kondratyev,
and Prof. Kenneth Sassen, to whom the authors are thankful. The authors also greatly appreciate the

18:18:48
xviii Preface

numerous useful discussions over many years on multiple aspects of cloud and climate studies with
Drs. Al Arking, Stefan Bakan, Neville Fletcher, Steve Ghan, Hartmut Grassl, Olaf Hellmuth, Peter
Hobbs, Paul Mason, Hugh Morrison, Leonid Matveev, Anna Pirnach, Bill Rossow, Yuri Sedunov,
Robert Schiffer, Victor Smirnov, Alexander Stepanov, Graeme Stephens, Vladimir Voloshchuk, and
many of our colleagues and co-authors who helped clarify various aspects of cloud microphysics.
In addition, the authors would like to thank Dr. Vladimir Chukin, Dr. Paul DeMott, and Dr. Hitoshi
Kanno for their useful discussions on ice nucleation and for providing experimental data. Dr. Osamu
Mishima and Dr. Thomas Koop are also thanked for their permission to adapt and use their conceptual
current schemes of the water states and phase diagrams. The authors are also grateful to Mrs. Sylvaine
Ferrachat from the group of Prof. Ulrike Lohmann at the Institute for Atmospheric and Climate Science,
Zurich, Switzerland, for preparing and providing the figure of the observed climatic global cloud
field based on the ISCCP data. They would also like to thank Dr. Yuxin Yun from the group of
Prof. Joyce Penner at the University of Michigan for providing the figure of the global cloud field
simulated with the climate model. Useful discussions with, and help from, Prof. Stephen Warren and
Dr. Ryan Eastman in preparing the figures of the global cloud field are greatly appreciated. Thanks
also to Drs. Vladimir Chukin, Olaf Hellmuth, and Vladimir Nikulin for their help in preparing some
of the figures.
This book was greatly facilitated and supported by the editors at Cambridge University Press:
Dr. Matt Lloyd, Ms. Sarika Narula, and Mrs. Shari Chappell; Ms. Saradha Chandrahasan (Project
Manager at S4Carlisle); and Mr. Michael McGee (Copy Editor). The authors greatly appreciate their
excellent organizational and editorial work. The authors are grateful to the Art Team of the S4Carlisle
Publishing Services who carefully and skillfully created the artwork, preparing the figures for
publication. Lastly, the authors gratefully acknowledge the permission granted them for reproducing
figures from published articles by the American Meteorological Society, the American Geophysical
Union, John Wiley & Sons, and the American Chemical Society.

Vitaly I. Khvorostyanov, Moscow, Russia

Judith A. Curry, Atlanta, Georgia, USA

18:18:48
1
Introduction

1.1. Relations among Thermodynamics, Kinetics,

and Cloud Microphysics

The most distinctive feature of the Earth when viewed from space is the presence of clouds covering
approximately 60% of its surface area. Clouds are a major factor in determining the Earth’s radiation
budget, by reflecting shortwave radiation and emitting longwave radiation. Through their ability to
precipitate, clouds provide virtually all of the fresh water on Earth. Clouds are associated with some
of the most damaging weather in the world: torrential rains, severe winds and tornadoes, hail, thunder
and lightning, and snowstorms. The latent heat released in clouds is an important source of energy
for scales of motion ranging from the global atmospheric circulation, to hurricanes and mid-latitude
cyclones, to individual storms. Clouds are also important in atmospheric chemistry because they play
an active role in many chemical reactions and transport chemicals through updrafts and scavenging
associated with precipitation.
A major challenge in understanding and modeling clouds is the broad range of spatial scales
involved. The scales range from the micron scale of individual cloud drops, to the scale of an indi-
vidual cloud (kilometers), up to the scale of the largest cloud systems (1000 km). Our present com-
putational capability allows only a small range of spatial scales to be simulated explicitly in a single
model; processes on the other scales are either specified or parameterized.
Cloud microphysics addresses processes at the smallest of these scales associated with the initia-
tion, growth, and dissipation of cloud and precipitation particles. Some of the most challenging issues
in cloud microphysics are associated with interactions between aerosol particles and cloud particles.
These interactions include heterogeneous nucleation of liquid and ice particles, homogeneous ice
nucleation, rates of water adsorption onto growing particles, the number concentration and size distri-
bution of a population of cloud particles, and the likelihood that the cloud will form precipitation-sized
particles. The influence of aerosols on cloud processes moulds cloud optical properties directly through
determination of the size and phase of cloud particles, and they indirectly influence radiative transfer
through determination of whether or not the cloud precipitates, and thereby determines cloud lifetime.
Cloud microphysical processes are intimately connected with cloud dynamical processes associated
with air motions on a range of scales, and through latent heat release and precipitation-induced down-
drafts, cloud microphysical processes influence cloud dynamics. An understanding of cloud–aerosol
interactions and ice nucleation has a direct application to weather modification through cloud seeding.
This book focuses on cloud microphysics processes in the context of providing a systematic and uni-
fied theoretical treatment of the thermodynamics and kinetics of cloud microphysical processes. Ther-
modynamics is a branch of theoretical physics that studies the properties of thermodynamic systems
in states of thermodynamic equilibrium and during transitions from one equilibrium state to the other.

1
2 Introduction

Physical kinetics is a branch of theoretical physics that considers the processes in systems that
are brought to a non-equilibrium state by external forces. One of the major premises of physical
kinetics is an assumption that local thermodynamic equilibrium is reached sufficiently fast in small
subdomains of the system (even though they contain a large number of particles), while the overall
system is in a non-equilibrium state. The microscopic method in physical kinetics describes the pro-
cesses in non-equilibrium states using distribution functions for various variables and solving kinetic
equations for them. The first kinetic equation was formulated by Ludwig Boltzmann in 1872 for the
kinetic theory of gases, which has served as a prototype for other numerous kinetic equations for
various processes, including the kinetic equations of coagulation and diffusion particles growth that
are considered in this book.
A cloud consisting of many drops and/or crystals surrounded by water vapor and other gases
comprises a thermodynamic system. Some microphysical processes in this system have small relax-
ation times for adjustment to an equilibrium state, and these subsystems can be considered in
thermodynamic equilibrium. For example, the vapor and temperature fields around a growing or
evaporating particle adjust almost instantaneously to the equilibrium state; nucleation of drops and
crystals usually occurs at conditions close to thermodynamic equilibrium. Thus, the properties of
nucleating particles can be evaluated from thermodynamic equilibrium equations.
Other microphysical processes (e.g., the diffusion and coagulation growth of drops and crystals)
have longer durations, the systems remain in non-equilibrium, and the evolution of their microphysical
properties can be considered using kinetic equations for drops and crystals distribution functions. Thus,
microphysical processes in clouds can be considered to be a combination of thermodynamic equilibrium
processes and kinetic non-equilibrium processes, depending on the system state.

1.2. The Correspondence Principle

There are many different parameterizations of various cloud microphysical processes and properties
used in atmospheric models: deliquescence of cloud condensation nuclei (CCN) and hygroscopic
growth; the activation of CCN into drops; homogeneous and heterogeneous ice nucleation; critical
humidities for ice nucleation; terminal velocities; the size spectra of drops and crystals (e.g., gamma
or exponential distributions) and their moments; and so on. Most of these parameterizations are based
on fits to experimental data, and their parameters may depend on specific observations, air mass, or
aerosol samples. Some of these empirical parameterizations extend and develop previous empirical
parameterizations, but many suggest newer expressions or newer parameter values. The correspon-
dence between the new and old parameterizations is often unclear. This creates uncertainty in the
choice of the optimum parameterizations for atmospheric models, which may lead to uncertainty in
the model simulation results. These uncertainties could be diminished if these parameterizations could
be derived from the theory and their parameters expressed via the atmospheric and aerosol properties.
A framework for pursuing this strategy is the correspondence principle, which is one of the major
principles in physics. The correspondence principle was formulated by Niels Bohr between 1913
and 1920 while developing his model of the atom and was later generalized in order to explain the
correspondence to, and remove the contradictions between, the new quantum mechanics and the
old classical physics. Subsequently, the correspondence principle has been generalized over sev-
eral decades and extended to other phenomena in physics and other sciences. The correspondence
1.3. Structure of the Book 3

principle states that a new theory or parameterization should not reject the previous correct theory
or parameterization but rather generalize them, so that the old (previous) theory becomes a particu-
lar case of the new theory. The new theory or parameterization contains a new parameter absent in
the previous theory; when its value tends to some limiting value, the new theory transforms into
the old theory. While the formulation of the correspondence principle is simple, it is nevertheless
a very powerful methodological tool in understanding natural phenomena and developing correct
generalizations of the existing theories and parameterizations. An important consequence of the
correspondence principle is that a newer theory should be able to express the empirical parameters
of the previous theories or parameterizations via the physical constants. The historical applications
of the correspondence principle are beyond the scope of this book. Here, we emphasize that: When
developing a new theory or parameterization, one should attempt to generalize previous theories and
express the empirical parameters via physical quantities. One of the major goals of this book is to
describe and develop further the theories that derive and generalize the known parameterizations of
cloud microphysics, and to express the empirical parameters via the parameters of the theory and
fundamental atmospheric constants. The correspondence principle provides an integrating frame-
work for this book, and many examples of correspondence between the older and newer theories and
parameterizations are described.

1.3. Structure of the Book

Chapter 2 is devoted to the general description of the global cloudiness and its major properties.
Cloud microphysical properties are defined and their characteristics are given. Mathematical formu-
lations are reviewed for various size spectra and their moments used for parameterization of cloud and
aerosol microphysical and optical properties: inverse power laws, generalized and ordinary gamma
distributions, lognormal distributions and their equivalent—algebraic distributions. Analytical methods
for evaluation of the moments of the distributions are described. A brief review is given of cloud
optical properties, as well as various parameterizations of their dependence on cloud microstructure.
Methods for evaluation of the extinction, scattering, and absorption coefficients are described for
polydisperse ensembles of drops and crystals.
Chapter 3 is devoted to the general description of the thermodynamic potentials and relations that
are used in the subsequent chapters. Five statistical energy distributions are described: the Gibbs dis-
tribution, and its four particular cases—the Maxwell, Boltzmann, Bose–Einstein, and Fermi–Dirac
distributions. Phase rules are formulated for bulk phases including systems with curved interfaces.
The equations of state for ideal and non-ideal gases are derived. Basic thermodynamic characteristics
of solutions are introduced, and their thermodynamic relations are described. A general equilibrium
equation (entropy equation) is derived, which serves as a basis for derivation of the following equa-
tions: the Clausius–Clapeyron equation for various interface systems (liquid and ice in bulk, water
drop and vapor, ice crystal and vapor), the Kelvin equation, and the Köhler equation.
The following thermodynamic properties of gas mixtures and solutions are derived: partial gas
pressures in a mixture of gases; equilibrium of two bulk phases around a phase transition point;
Raoult’s law; freezing point depression and boiling point elevation, and the relation of water activity
and freezing point depression. Equations are developed for dry and wet adiabatic processes that serve
as a platform for constructing Lagrangian parcel and Eulerian multidimensional cloud models.
4 Introduction

The properties of water and aqueous solutions, and their parameterizations, are considered in
Chapter 4. Various forms of water are described, including those that form at very low temperatures
and high pressures (liquid water, crystalline ices, and amorphous forms of water and ice), along with
possible transitions among them. Modern theories of water are reviewed, including stability limit
conjecture, singularity free theory, and the theories based on a hypothesis of the second critical point.
The temperature and pressure ranges in the clouds of Earth and on other planets of our solar system
are described. The equivalence of pressure and solution effects in aqueous solutions is also discussed.
A compact review is given of existing parameterizations of some basic water and ice thermodynamic
properties (saturated vapor pressures, surface tensions, heat capacities, heats of phase transitions, etc.).
Various equations of state for ice and liquid water are reviewed, including the Einstein-Debye
thermodynamic equations of state for ice, modern equations of van der Waals type, equations of state
for ice based on the Gibbs function and for fluid water based on the Helmholtz function and based on
the concept of the second critical point.
In Chapter 5, the diffusion and coagulation growth of drops and crystals is examined. The equa-
tions for the growth rates of individual drops and of crystals are derived. The equations account for
the effective diffusion coefficients, kinetic corrections, psychrometric corrections due to latent heat
release, and ventilation corrections, and are formulated in a convenient factorized form as a product
of the terms describing these factors and are valid in a wide range of diffusion growth rates from
diffusion to kinetic limits.
Calculations of drop and crystal diffusion growth require supersaturation equations. A detailed
derivation of the general equations for the fractional water and ice supersaturations is given from
the heat and vapor balance equations. The supersaturation absorption or relaxation times for drops
and crystals are introduced, which are the major scaling times of supersaturation absorption at con-
densation in clouds or the supersaturation release at evaporation. General mathematical expressions
are derived for the relaxation times, including their diffusion and kinetic limits. The supersaturation
equations are presented in various forms that can be convenient for various models or parameter-
izations. In particular, the quasi-equilibrium supersaturations over water and ice are obtained for
mixed-phase, liquid, and crystalline clouds that can be used in many cases in the models of all scales
instead of the saturation adjustment method. Kinetic equations of condensation and deposition in the
adiabatic process are derived, their analytical solutions in terms of the integral supersaturation are
obtained for arbitrary values of the condensation coefficients in the wide range of particle growth
rates, and the diffusion and kinetic limits of the solutions are found.
Chapter 6 examines aerosol hygroscopic growth and drop activation from cloud condensation
nuclei (CCN). Reviews are given of the existing empirical and semi-empirical parameterizations of
these processes and of the Köhler theory and its subsequent modifications. Hygroscopic growth of
mixed aerosol particles and activation of CCN are considered based on a modification of the Köhler
theory without the assumption of a dilute solution in CCN and using a newer parameterization of
a soluble CCN fraction that can be proportional to the volume or surface of CCN. New analytical
expressions are derived for the equilibrium radius of the wet aerosol in a cloudless atmosphere,
and in clouds, and for the critical radii and supersaturations for CCN activation. These expressions
generalize the known equations of the Köhler theory and are valid not only for diluted solutions but
for arbitrary insoluble fractions and for both volume-distributed soluble fractions and soluble shells
1.3. Structure of the Book 5

on the surface of an insoluble core (e.g., mineral dust particle). The accuracy and the regions of ap-
plicability of the classical expressions are clarified by the new solutions. Based on these new expres-
sions for the wet radii, a general but simple method is derived for calculation of the wet aerosol size
spectrum from the dry aerosol size spectrum. A general method is developed for transformation of the
CCN size spectra into differential CCN activity spectra by supersaturations using the equations for the
critical radii. Droplet concentrations are calculated by integration over supersaturations of the differ-
ential CCN activity spectra. A generalized power law for droplet concentration is derived that includes
Twomey’s power law as a limiting case, provides physically based expressions for Twomey’s parame-
ters, and ensures finite drop concentrations limited by CCN concentration at any large supersaturation.
The kinetics of drop formation in clouds is considered in Chapter 7. To study the kinetics of drop
nucleation in clouds, the integro-differential equation for integral water supersaturation in a cloud
is derived and analyzed. Solving the supersaturation equation using the algebraic form of the cloud
condensation nuclei (CCN) activity spectrum yields analytical expressions for the time of the CCN
activation process, the maximum supersaturation, and droplet concentration. All three quantities are
expressed as functions of the vertical velocity and characteristics of the CCN size spectra (mean
geometric radius, dispersion, and parameters of solubility). Analytical expressions for droplet con-
centration are found as algebraic functions of maximum supersaturation and as a generalized quasi-
power law, and are limited by the total CCN concentration at high supersaturations.
The kinetics of drop activation and the effects of aerosol properties and dynamics on drop concen-
tration are studied using two new methods based on numerical and analytical solutions. In the numer-
ical method, a simple and fast numerical algorithm and solution were developed that allow users to
obtain all these characteristics rapidly without running of extensive simulations using parcel models.
Analytical expressions are obtained for the time of CCN activation, maximum supersaturation, and
the concentration of activated droplets. Solutions are found for these parameters that are the products
of power laws by 6 variables: CCN concentration, mean radius, soluble fraction, vertical velocities,
surface tension, and condensation coefficient. The solution includes 4 limits: one is a generalization
of Twomey’s power law, and the other 3 limits are new.
In Chapter 8, the homogeneous nucleation of drops and crystals is considered. Using the concept
of metastable states, the Fokker–Planck and Frenkel–Zeldovich kinetic equations are derived for
the size distribution function of the germs of a new phase. Based on thermodynamic principles and
extending further classical nucleation theory, general equations for the critical germ radius, free
energy, and the nucleation rates are derived for homogeneous ice nucleation that express these
properties as functions of temperature, water saturation ratio, pressure, and the finite size of freezing
particles simultaneously. It is shown that the new expressions generalize and unify previously derived
equations and empirical parameterizations, and include them as particular cases.
Using these equations of extended classical nucleation theory, critical freezing and melting tem-
peratures of homogeneous freezing are derived as functions of saturation ratio, and critical saturation
ratios over water and ice are derived as a function of temperature. These equations explain, gener-
alize and unify existing empirical parameterizations, express their parameters via the atmospheric
and aerosol properties, and outline the limits of their applicability. A simple nonlinear equation is
obtained for the liquidus curves, and an analytical relation is found between the freezing and melting
point depressions. A simple quantitative expression is derived that establishes equivalence of the
6 Introduction

solution and pressure effects on freezing, that is in good agreement with observed relations. The
empirical water activity shift method is derived from the classical theory and its limitations are studied.
The kinetics of homogeneous ice nucleation is evaluated at various temperatures, aerosol concentra-
tions, and vertical velocities using parcel model simulations and the new equations for the critical
energies and nucleation rates. Simultaneous account for the temperature and supersaturation effects
on the nucleation rates produces very strong negative feedback that allows nucleation into crystals of
only a very small fraction of deliquescent haze particles.
A new parameterization of homogeneous ice nucleation for the models is developed based on
extended classical nucleation theory, whereby the critical energies and nucleation rates are presented
in a separable form as a product of the functions of temperature, supersaturation, and vertical velocities.
Limits of these equations are found for the diffusion and kinetic regimes of crystal growth, which
allows its application for pure and polluted clouds.
Chapter 9 is devoted to heterogeneous nucleation of drops and ice crystals. Nucleation of drops
by vapor deposition on water-insoluble particles is considered; the critical radii, energies, and nucle-
ation rates are derived; and the shape factor is introduced. The four basic modes of heterogeneous ice
nucleation on ice nuclei (deposition, deliquescence-freezing, immersion, and contact) are described,
along with the properties of ice nuclei (IN). A review is given of existing empirical and semi-empirical
parameterizations of heterogeneous ice nucleation. Nucleation of crystals in the deposition mode
on water-insoluble particles is considered in detail. The major focus of this chapter is on the
deliquescence-freezing and immersion-freezing modes. Through further developing classical nucle-
ation theory, equations are derived for the ice germ critical radius, energy and nucleation rate of ice
crystals as functions of temperature, water saturation ratio, droplet radius, external pressure, and mis-
fit strain between ice and insoluble substrate crystalline lattices. These equations generalize and unify
the previous expressions found for the critical germ radius and energy. The expressions for the critical
energy and nucleation rate are presented in the separable form as a product of the function depending
on temperature and supersaturation. This unification and separable representation of the temperature
and supersaturation dependencies provide a physical basis for existing empirical parameterizations of
crystal concentrations as functions of temperature or supersaturation or combined parameterizations
and allow further a rigorous theoretical derivation of the combined parameterization.
The equations are derived from classical nucleation theory for the critical freezing and melting
temperature as a function of saturation ratio, drops size, pressure, misfit strain, and active sites. Deri-
vation is given for the cases of volume heterogeneous freezing, surface quasi-heterogeneous freezing,
and surface quasi-heterogeneous melting. It is found that a simple nonlinear equation for liquidus
curves, which describes the freezing and melting point depressions, is a particular limiting case of
these equations for the infinitesimally small nucleation rates. Critical saturation ratios or water activi-
ties of heterogeneous freezing are derived as functions of temperature, drops size, pressure, misfit
strain, and active sites, and the empirical water activity shift method for heterogeneous nucleation
is derived from classical nucleation theory. The derived critical energies and nucleation rates of het-
erogeneous nucleation are applied and verified in parcel model simulation of a mixed-phase cloud
in a wide range of temperatures, aerosol concentrations, and vertical velocities. The kinetics of ice
nucleation and cloud glaciation are studied in detail. A semi-empirical parameterization of the final
concentrations of nucleated crystals is found as a function of temperature and vertical velocities. The
1.3. Structure of the Book 7

simulation results are compared with analogous simulations of homogeneous freezing described in
Chapter 8, which reveal the similarities and differences between heterogeneous and homogeneous
nucleation. The thermodynamic constrains on the empirical parameterizations are considered.
In Chapter 10, parameterizations of heterogeneous ice nucleation suitable for use in cloud and
climate models with large time and space steps are derived from extended classical nucleation theory.
Considering heterogeneous freezing of haze particles and drops, the critical energies and nucleation
rates are presented in a separable form as a product of the functions of temperature, supersaturation,
active site parameter, and vertical velocity. Integrating this nucleation rate over time and solving the
integral supersaturation equation yields a new equation for the crystal concentrations as the function
of temperature, critical or maximum supersaturation, vertical velocity, and a few fundamental con-
stants. It is shown that the new equations generalize and unify several previous empirical and semi-
empirical parameterizations, reduce them in some particular cases, and express their empirically
determined parameters via the atmospheric and aerosol properties and fundamental constants. The
limits of these equations are found for the diffusion and kinetic regimes of crystal growth, which allows
its application for pure and polluted clouds. These parameterizations of heterogeneous freezing are
compared with the analogous parameterizations of homogeneous freezing, and the differences are
described quantitatively. Similar parameterizations are developed for deposition ice nucleation and
for immersion drop freezing near water saturation. Contact ice nucleation is described: its general
properties, the three major mechanisms of aerosol scavenging by drops that may lead to contact
nucleation (Brownian diffusion, thermophoresis, and diffusiophoresis), the collection rates, probabili-
ties of freezing, and scavenging in polydisperse ensembles of drops and aerosols.
Chapter 11 considers the phenomena of deliquescence and efflorescence in atmospheric aero-
sols. The general properties of these processes are described, and previous theories and models of
deliquescence and efflorescence are reviewed. New models of deliquescence and efflorescence are
developed based on extensions of classical nucleation theory that are applied to salt crystallization
in solutions. Using the general equilibrium equation, expressions are derived for the critical radii,
energies, and nucleation rates of liquid germs on the surface of a particle at deliquescence, and
the critical radii, energies, and nucleation rates of the salt crystallization germs in supersaturated
solutions. These models are applied to analytical derivations and calculations of the temperature
dependencies of the dissolution heat and solubility, and to the temperature dependence of the deli-
quescence relative humidity. The results are compared with experimental data and good agreement
is found. Application of the efflorescence model to salt crystallization, along with the ice nucleation
model, allows calculation of the location of the eutectic point in solution and the right branch with
salt crystallization on the phase diagram of solutions. These calculations are combined with calcu-
lations of the freezing temperatures and a unified phase diagram of solutions is plotted, where all
four branches (deliquescence, efflorescence, freezing, and melting curves) are calculated based on a
unified basis using extended classical nucleation theory.
Chapter 12 presents a unified treatment of cloud particle fall velocities for both liquid and crys-
talline cloud particles over the wide size range observed in the atmosphere. A review is given of
previous theories and parameterizations of particle fall velocities. The representation in this book
is formulated in terms of the Best (or Davies) number, X, and the Reynolds number, Re. The fall
velocities are represented as generalized power laws. The coefficients of the power laws for the
8 Introduction

Re-X relation and for the fall velocities are found as the continuous analytical functions of X or
particle diameter over the entire hydrometeor size range, which makes this method convenient in
applications. The turbulent corrections for the drag coefficients and terminal velocities are derived.
Analytical asymptotic solutions are obtained for the coefficients of generalized power laws for the
two regimes that represent large and small particles and correspond to potential and aerodynamic
flows, respectively. The analytical temperature and pressure corrections for the wide size ranges are
derived and compared with previous parameterizations. The expressions for Re-X relation and drag
coefficients are applied to spherical and non-spherical drops, as well as several crystal habits, with
special attention paid to the turbulent corrections.
Chapter 13 considers stochastic condensation in clouds and formation of the broad size spectra of
drops and crystals. An extended review is given of various mechanisms that were suggested to explain
existence of the broad size spectra in clouds at all stages of their development. A new version of the
kinetic equation for stochastic condensation for the small-size fraction of drops and crystals spectra
is derived that is valid for arbitrary relative values of Lagrangian turbulent time and supersaturation
relaxation time. Analytical solutions are obtained under a number of assumptions. For this purpose,
a model of the condensation process in a turbulent cloud (stochastic condensation) is developed and
the Reynolds procedure is applied to the regular and fluctuation parts of all the quantities yielding
an equation in terms of covariances, which are incorporated into a kinetic equation to yield the final
kinetic equation of stochastic condensation. Particular cases of low-frequency and high-frequency
approximations are examined.
Using a few basic assumptions and simplifications, various analytical solutions are obtained for
the small-size fraction. Neglecting the diffusional growth of larger particles, solutions have the form
similar to the gamma distributions. Their indices that determine the breadth of the spectra and the rates
of coagulation and precipitation formation are expressed via atmospheric properties and fundamental
constants. Other solutions are obtained in the form of the generalized gamma distributions for the
cases, including the diffusional growth of large particles, sedimentation, and coagulation with the large
fraction when these processes are important. Finally, based on the integral Chapman–Kolmogorov
equation for stochastic processes, a general integral stochastic kinetic equation is formulated. Using
this equation, the differential Fokker–Planck equation for stochastic condensation is derived, and vari-
ous versions of the kinetic equations considered in this chapter are shown to be particular cases of this
Fokker–Planck equation.
Chapter 14 is devoted to analytical solutions to the stochastic kinetic equation of coagulation and
formation of the large-size fractions of the drop and crystal size spectra for precipitating clouds. The
kinetic equation of coagulation in approximation of continuous collection is derived from the general
coagulation equation, and the corresponding assumptions are discussed. Then, the basic stochastic
integral kinetic equation is simplified and reduced to a differential equation. The analytical solutions
to this equation are obtained for various cases in various forms that are similar to the gamma distribu-
tions, exponential Marshal–Palmer and inverse power law size spectra that have been determined
empirically. Finally, it is shown that the coagulation equation represents a particular case of the
integral Chapman–Kolmogorov equation and can be presented also as the differential Fokker–Planck
equation. Possible ways of generalization of the kinetic equations are outlined.
2
Clouds and Their Properties

2.1. Cloud Classification

Clouds represent the large visible ensembles of drops or crystals suspended in the gaseous atmo-
sphere. Clouds in the Earth’s atmosphere result from the condensation or deposition of water vapor.
Clouds on other planets may result from the condensation of the other gases. For example, clouds
on Venus may consist of sulfuric acid drops, some clouds on Mars may consist of CO2 ice crystals,
and the clouds on Jupiter may consist of H2O–NH3 drops and CH3 ice crystals (e.g., Curry and
Webster, 1999). Hereafter, we consider the Earth’s water clouds, although most of the equations in
this book can be applied with appropriate modifications to the clouds of other substances on other
planets.
Numerous studies of the condensation process have shown that condensation occurs when the water
vapor pressure slightly exceeds the saturated vapor pressure, or is supersaturatedated—i.e., the relative
humidity slightly exceeds 100%. At the same time, it is known that the relative humidity near the
ground is most often 40–80%, decreases upward, and is 2–3 times smaller at the level of the tro-
popause. Therefore, cloud formation requires a mechanism that increases the relative humidity to
≈100%. Cloud formation mechanisms include cooling due to vertical uplift (convection) or radiative
cooling, horizontal transport (advection) of heat and moisture, or the mixing of air masses. There is a
great variety of conditions and motions in the atmosphere that lead to cloud formation, which results
in a diversity of cloud properties and appearances.
Various classifications of clouds are used in meteorological literature. Classification by levels is
based on sorting clouds by the heights of their locations in the troposphere, and clouds are classified
as upper-, middle-, and low-layer clouds, and clouds of vertical development that have significant
vertical extension. Classification by temperature defines a cloud as warm if the entire cloud is warmer
than 0 °C; otherwise, the cloud is classified as cold. The similar classification by phase state charac-
terizes clouds as liquid, mixed-phase, or ice clouds.
The most commonly used cloud classification is based on the morphology of the cloud as defined by
its appearance as seen by a ground-based observer. This classification is adopted in the International
Atlas of Clouds developed and published by the World Meteorological Organization (WMO, 1975,
1987). This classification is tree-like (branched), similar to biological classifications of animals and
plants, and classifies the clouds using Latin names. The classification defines ten main groups called
genera, which are subdivided into species determined by the cloud shapes or internal structure, and
in turn, are subdivided into varieties determined by some specific features within a species—e.g., the
transparency or shapes of the boundaries.

9
10 Clouds and Their Properties

Upper-level clouds are often called cirriform clouds. These clouds form at very low temperatures,
generally below −40 °C, are mostly pure crystalline, and contain ice crystals of numerous forms.
Cirriform clouds often form in the front upper parts of atmospheric fronts just below the tropopause
when a warm air mass lifts above the cold air mass. Therefore, cirriform clouds often serve as indica-
tors of changing weather or approaching storms. Three of the 10 genera defined in the International
Atlas of Clouds as cirriform clouds are:

Cirrus (Ci)—Detached clouds in the form of white, delicate filaments, or white or mostly white
patches or narrow bands. These clouds have a fibrous (hairlike) appearance, or a silky sheen,
or both. The height of cirrus cloud bases is typically 7–10 km in the midlatitudes, and reaches
18 km in the tropics. Precipitation from these clouds forms bands of small crystals but they do
not reach the ground.
Cirrocumulus (Cc)—Thin white patches, sheets, or layers of cloud without shading, composed
of very small elements in the form of grains or ripples, merged or separate, and more or less
regularly arranged. The cloud base is 6–8 km in the midlatitudes, and the cloud thickness is
typically 0.2–0.4 km.
Cirrostratus (Cs)—Transparent whitish cloud veils with a fibrous (hair-like) or smooth appear-
ance that totally or partially cover the sky, and generally produce a halo phenomena. The
cloud base is 6–8 km in the midlatitudes, and can be much lower in the polar regions; the
cloud thickness ranges from 0.1 to 3 km. Their precipitation usually does not reach the ground.

A detailed description of various properties of cirriform clouds is given in Cirrus (2002).

The two genera classified as middle-level clouds are:

Altocumulus (Ac)—White or grey, or both white and grey, patches, sheets, or layers of cloud, gen-
erally with shading, and composed of laminae, rounded masses, or rolls, which are sometimes
partially fibrous or diffuse and which may or may not be merged. The cloud base is 2–6 km in
the midlatitudes, and the cloud thickness ranges from 0.2–0.7 km. Its precipitation may reach
the ground as raindrops or snow crystals. There are 2 species of Ac: wave-likee (Ac undulatus,
Ac und) and convective-likee (Ac cumuliformis, Ac cu).
Altostratus (As)—Greyish or bluish cloud sheet or layer with a striated, fibrous, or uniform
appearance, totally or partially covering the sky, and having parts thin enough to reveal the
sun at least dimly, as if through ground glass. The slightly fibrous structure may be caused
by the bands of precipitation. Altostratus does not produce halos. The cloud base is 3–5 km
in the midlatitudes, and the cloud thickness is about 1 km. Its precipitation often may reach
the ground. Types of As include the fog-likee cloud As nebulosus, As neb, and the wave-like
As undulatus, As und.

A recent review of the properties of mid-level clouds is given by Sassen and Wang (2012).
Low-level clouds include the following genera:

Stratocumulus (Sc)—Grey or whitish, or both grey and whitish, patches, sheets, or layers of
cloud which almost always have dark parts, composed of crenellations, rounded masses, or
rolls, which are nonfibrous (except when virga-inclined trails of precipitation are present)
2.1. Cloud Classification 11

and which may or may not be merged. The cloud base height is 0.5–1.5 km, and the cloud
thickness is about 0.2–0.8 km. Weak short-lived precipitation may reach the ground as rain or
snow. The species of this cloud genus include wave-like Sc (Stratocumulus undulatus, Sc und)
and convective-like Sc (Stratocumulus
atocumulus cumuliformis, Sc cuf).
Stratus (St)—Generally grey clouds with a fairly uniform base, which may produce drizzle, ice
prisms, or snow grains. If the sun is visible through the cloud, its outline is clearly discernible.
Stratus clouds do not produce halo phenomena except, possibly, at very low temperatures. The
height of the cloud base is 0.1–0.7 km, the cloud thickness is about 0.2–0.8 km. Sometimes
precipitation may reach the ground as drizzle or small snow. The species of this cloud genus
include fog-like clouds (Stratus nebulosus, St neb), wave-like clouds (St undulatus, St und),
and broken St (St fractus, St fr).

The other 3 of the main 10 genera may fill thick layers in the troposphere and spread among
several levels. They are the following.

Nimbostratus (Ns)—Grey cloud layer, often dark, sometimes with yellowish or bluish color, the
appearance of which is rendered diffuse by more or less continuously falling rain or snow,
which in most cases reaches the ground. The cloud layer is thick enough to completely obscure
the sun. Low, ragged clouds Frnb frequently occur below the nimbostratus layer and may
obscure the Ns layer above. The cloud base height is 0.1–1 km, cloud depth is 2–5 km and
greater.
Cumulus (Cu)—Detached clouds, generally dense and with sharp outlines developing verti-
cally in the form of rising mounds, domes, or towers, of which the bulging upper part often
resembles a cauliflower. The sunlit parts of these clouds are mostly brilliant white. Their base
is relatively dark, often grayish or bluish, and nearly horizontal. Sometimes cumulus clouds
are ragged. The cloud base is usually at 0.8–1.5 km in the midlatitudes, but can vary over a
wide range, depending on the relative humidity near the ground. Cloud depth may vary from
a few hundred meters to several km. Precipitation is usually absent. This cloud genus includes
three species. (a) Cumulus humilis (Cu hum)—cumulus clouds of only a slight vertical extent,
usually not greater than 1 km. They generally appear flattened because their vertical extent is
smaller than the horizontal sizes. (b) Cumulus mediocris (Cu med)—cumulus clouds of mod-
erate vertical extent, the tops of which show fairly small protuberances. (c) Cumulus congestus
(Cu cong)—cumulus clouds that exhibit marked vertical development; their bulging upper part
frequently resembles a cauliflower.
Cumulonimbus (Cb)—Heavy, dense clouds, with a considerable vertical extent. At least part
of their upper portion is usually smooth, fibrous, or striated and is nearly always flattened.
This part often spreads out in the shape of an anvil or vast plume. Under the base of these
clouds, which is generally very dark, there are frequently low ragged clouds and precipita-
tion, sometimes in the form of virga, which is trails of precipitation (fall streaks) falling
from the base but not reaching the earth’s surface). Cb clouds produce heavy rain and hail in
summer and heavy snowfall and graupel in winter. They are also the source of thunderstorms
and lightning.
12 Clouds and Their Properties

Fog is not considered in the Atlas of Clouds as a separate genus, but is defined as follows: ws: Fog—
Composed of very small water droplets (sometimes ice crystals) in suspension in the atmosphere.
It reduces the visibility at the earth’s surface generally to less than 1,000 m. The vertical extent of fog
ranges between a few meters and several hundred meters.
There are several types of fog, classifiedied by the mechanism of formation. Radiative fog forms
usually during calm nights due to radiative cooling of the underlying surface and the lower bound-
ary layer of the atmosphere. Advective fog forms due to advection and cooling of a warmer air mass
over a colder surface. Steam fog forms when water vapor evaporates from a warm surface into the
cold air. Steam fogs frequently form above cold ocean currents, over non-frozen rivers and lakes
in winter, and in polar regions over cracks in the sea ice and polynyas. In the cold polar regions
or midlatitudes at low w temperatures, so called “diamond dust” may occur, where ice crystals form
in the clear sky, sparkling in the sunlight. These clouds may spread down to the ground forming
ice fog.
A condensation trail or contrail forms behind the exhaust of an aircraft engine at high altitude
as a visible white plume. Contrails are similar to cirrus clouds and may have a noticeable effect on
weather and climate in regions with intensive air traffic (Liou et al., 1991; Schumann, 1994; Sassen,
1997). Another similar phenomenon is ship tracks that often form due to the warm moist air of ship
exhausts and that appear on satellite images as linear features of enhanced albedo (brighter white
bands) in the field of Sc clouds expelled by ship exhausts (Coakley et al., 1987). The effects of ship
tracks on weather and climate have also been studied (e.g., Ackerman, et al., 2003, and references
therein).
Orographic clouds and cloud systems formed above the mountains due to orographic uplift and
waves are sometimes included into the above 10 genera, but are often considered a separate cloud
genus.
Some typical cloud properties are given in Table 2.1, although the values can vary in the wide
ranges. A major factor determining cloud properties is the characteristic value of vertical velocity w
in updrafts, which influences their genesis. Low-level clouds are also strongly affected by the radia-
tive heat exchange and surface-atmosphere, heat-moisture exchange.

Table 2.1. The typical characteristics of various cloud types: depth H, vertical
velocity w, life time tlt (hours or minutes), liquid water content LWC or ice water
content IWC, the wet adiabatic cooling rate (∂T/∂t)wa = w(ga − gwa) and the infrared
cooling rate (∂T/∂t)ir . The data are compiled from Borovikov et al. (1963), Mason (1971),
Young (1993), Pruppacher and Klett (1997), and Cotton et al. (2011).

Fog Ns, As, Cu hu Cu Ci, Cs

Cloud type St, Sc Ac Cu med cong Cb Orographic Cc

Depth H, km 0.05−0.6 0.5−3 1.5 5 km 6−12 1.5−6 0.5−3

w, m s−1 ±0.010 0.01−1 1−3 3−10 5−30 0.5−2.0 0.01−1.5
Life time tlt 2−6 h 6−12 h 10−40 min 20−45 min 45 min 3−10 h 0.2−12 h
LWC, IWC, g/m3 0.05−0.3 0.05−0.4 0.3−1.0 0.5−2.5 1.5−5.0 0.2−2.0 0.001−0.2
(∂T/∂t)wa °C/h 0.2 0.2−20 20−60 60−200 100−600 10−40 0.2−20
(∂T/∂t)ir °C/h 1−4 1−6 1−4 1−4 1−4 1−4 0.1−3
2.2. Cloud Regimes and Global Cloud Distribution 13

2.2. Cloud Regimes and Global Cloud Distribution

A close correlation of cloudiness with vertical motions and areas of thermal contrasts, baroclinicity
and cyclogenesis, seen in Table 2.1, is supported by a comparison shown in Fig. 2.1 of observed
climatological global pressure fields with climatic fronts and cyclones from Blüthgen (1966), shown
in Fig. 2.2 observed global cloud amounts, and shown in Fig. 2.3 global cloud amounts simulated
with a modern general circulation model (GCM). The methods of construction of observed cloud

January

Figure 2.1. Global pressure field and dynamic structure of the atmosphere in January. 1) Regions
of high pressure; 2) low-pressure troughs; 3) Arctic; and 4) Polar climatological fronts in the
Northern and Southern Hemispheres; 5) Intertropical Convergence Zone (ITCZ); and 6) its North
and South branches (NITCZ and SITCZ). The other notations mean the following. The Northern
Hemisphere: NAmA is the North-American Anticyclone; NAC is the North-Atlantic Cyclone
(Iceland Depression), NAsA is the North Asian Anticyclone (Siberian High), NPC is the North
Pacific Cyclone (Aleutian Depression), NPA is the North Pacific Anticyclone (Honolulu High), and
NAA is the North Atlantic Anticyclone (Azores High). The Southern Hemisphere: SPA is the South
Pacific Anticyclone, SAA is the South Atlantic Anticyclone (Saint Helene Island High), SIA is the
South Indian Anticyclone, SPC and SAC are the South Pacific and South Atlantic Cyclones over
Antarctica. Adapted from Blüthgen (1966), with changes.
Total cloud cover
T
Annual (1983–2005) Average Cloud Amount (percent) Land & Ocean Areas
14

Figure 2.2. The observed cloud amount, annual average in percent over the years 1983–2005 from the International Satellite Cloud Climatology
Project (ISCCP), (Schiffer and Rossow, 1983; Han, et al., 1988; Rossow and Schiffer, 1999) (http://isccp.giss.nasa.gov/products/browsed2.html). The
figure was prepared using the D2 products of ISCCP and kindly provided by Mrs. Sylvaine Ferrachat from the group of Prof. Ulrike Lohmann at the
Institute for Atmospheric and Climate Science, Zurich, Switzerland.
2.2. Cloud Regimes and Global Cloud Distribution 15

Figure 2.3. Five-years’ averaged global cloud distribution for January simulated with the coupled
GCM CAM-IMPACT model described in Yun and Penner (2012). The figure was prepared and
kindly provided by Dr. Yuxin Yun from the group of Prof. Joyce Penner, University of Michigan.

climatologies are described by Warren et al. (2013). The observed cloud climatologies have been
developed mostly from two kinds of data: surface-based and satellite data. (1) The surface-based data
sets use visual observations of clouds from the Earth’s surface, as coded in weather reports from sta-
tions on land and ships in the ocean (e.g., London, 1957; Berlyand and Strokina, 1980; Hahn et al.,
1988; Hahn and Warren, 2007; Warren et al., 1985, 2013) (www.atmos.washington.edu/CloudMap).
(2) The satellite data sets use radiances measured by satellites in polar and geostationary orbits. Satel-
lites detect clouds principally at visible and thermal infrared wavelengths. The most comprehensive
satellite data set was collected in the framework of the International Satellite Cloud Climatology
Project (ISCCP). It originated in 1983 as the first project of the World Climate Research Program
(WCRP) and has continued for more than 30 years (Schiffer and Rossow, 1983; Han et al., 1988;
Rossow and Schiffer, 1999) (http://isccp.giss.nasa.gov/products/browsed2.html).
The observed cloud field is from ISCCP data during the years 1983–2005, prepared using the D2
products of ISCCP and kindly provided by Mrs. Sylvaine Ferrachat from the group of Prof. Ulrike
Lohmann at the Institute for Atmospheric and Climate Science, Zurich, Switzerland. Fig. 2.3 (kindly
provided by Yuxing Yun) shows global cloud distribution simulated with the use of the coupled
CAM-IMPACT climate model described in Yun and Penner (2012). The model consists of two com-
ponents: the NCAR Community Atmospheric Model (CAM3) (Collins et al., 2006), and the Univer-
sity of Michigan IMPACT aerosol model derived from the Lawrence Livermore National Laboratory
(LLNL) chemical transport model (Rotman et al., 2004; Penner et al., 1998). A comparison of
Figs. 2.1–2.3 shows that the features of global fields of pressure, winds, and climatic fronts (Fig. 2.1),
and cloudiness (Fig. 2.2) at present are sufficiently well reproduced by the general circulation model
(GCM) (Fig. 2.3).
16 Clouds and Their Properties

Since maxima of ascending velocities and advection rates are located in the climatic cyclones and
fronts (Fig. 2.1), these figures show a good correlation of clouds and dynamics—i.e., of maxima of
the monthly cloud amount and the areas of maximum vertical velocity. In this section, the global
distribution of cloudiness is analyzed with regard to cloud genesis.

2.2.1. Large-Scale Condensation in Fronts and Cyclones

The term “large scale condensation” is used in the general circulation model (GCM) to denote the
extended areas of stratiform cloudiness that form in atmospheric fronts and cyclones. Its global dis-
tribution and genesis are illustrated in Figs. 2.1, 2.2, and 2.3. The midlatitudes exhibit three maxima
of the cloud amount in Figs. 2.2 and 2.3, which appear due to the frontal and cyclonic activity shown
in Fig. 2.1.

1. In the Atlantic region, there is a pressure trough (the Iceland minimum) and two climatic fronts,
Arctic and Polar, in the northern part (Fig. 2.1). In winter, the Arctic front begins near the eastern
Canadian coast (about 40°N), runs south of Newfoundland to the northeast, passes the Iceland
depression and extends to the Novaya Zemlya islands, and sometimes further eastward, along
the entire Siberian coast. This front runs parallel and north of the Gulf Stream, continuing as the
warm North Atlantic Current and further as the Norwegian Current (Fig. 2.4).
The front is formed by the temperature contrast between Arctic snow and ice fields in
the north and the warm Gulf Stream in the south. The winter Polar front begins near the

180 180
80

60

40

23.5
0
23.5
40

60

Figure 2.4. Warm and cold ocean currents, open and closed convective cells and global distribution
of low cloudiness over the oceans (adapted from Agee, 1985, with changes). Horizontal axis is
longitude; vertical axis is latitude (degrees).
2.2. Cloud Regimes and Global Cloud Distribution 17

coast of Florida and runs south of the Gulf Stream and along both it and the Arctic front
(Figs. 2.1, 2.4).
Therefore, temperature contrasts between the warm ocean currents—the Gulf Stream and
the North Atlantic Current—and colder areas to the northwest (the cold Labrador Current and
the cold continents) and the south are sources of baroclinicity, which is responsible for the
formation of climatological fronts. The western sections of these fronts, where baroclinicity is
increased due to the temperature contrasts between the cold American continent and the warmer
ocean, are the scene of the maximum cyclogenesis. Developing cyclones move to the northeast
along both fronts (stormtracks) toward Europe. The cyclones are areas of permanent updrafts,
which generate persistent cloudiness in this area.
Thus, the dynamic structure of the pressure field and fronts determine the cloud distribution.
Figs. 2.2 and 2.3 show that a long band of the maximum cloud amount (up to 80–90%) is formed
in January, stretching from Cape Hatteras to Greenland and further northeastward to the Novaya
Zemlya Islands. This band coincides with the maximum of the large-scale updrafts along the
climatic fronts and the Iceland pressure trough (Fig. 2.1). That is why satellite images exhibit
persistent broad cloud bands along all of the Gulf Stream and North Atlantic Current. The cloud
amount here can be higher in winter than the annual average due to increasing horizontal tem-
perature gradients and baroclinicity in winter, which leads to the increase in cyclogenesis.
2. There is a kind of “translation symmetry” between the Atlantic and Pacific Oceans—that is,
a “parallel transfer” of the pressure and cloud patterns from one ocean to another that gives a
similar picture. In the Northern Pacific, similar to the Northern Atlantic, the maximum of the
monthly cloud amount (up to 80–90%, Figs. 2.2 and 2.3) is present at the Arctic and Polar fronts
and the Aleutian pressure minimum (Fig. 2.1), along the warm Kuroshio ocean current continu-
ing as the North Pacific Current (Fig. 2.4). This cloudiness can be seen in satellite pictures as a
broad band, stretching from Japan to the northeast, up to Alaska.
3. There is a kind of “mirror symmetry” between the Southern and Northern Hemispheres in the
Atlantic and Pacific oceans—that is, a mirror reflection of the Northern ocean relative to the equa-
tor that gives a similar but mirror picture in the Southern ocean. This is caused by the change of
the sign of the Coriolis force and the direction of cyclonic rotation between the hemispheres. In the
Southern Hemisphere clouds, a maxima in amount up to 70–90% are observed in the three oceans
at the Southern Polar fronts and in the pressure trough along the Antarctic Circumpolar Current
(Figs. 2.1 and 2.4).

Satellite images usually show these cloud areas in the form of “white spirals or commas,” which
begin to the west of the southern parts of South America, Africa, and Australia, and then run to the
southeast and merge with the cloud band formed in the pressure trough around the Antarctic Circum-
polar Current. The counterclockwise cyclonic rotation in the Northern Hemisphere is changed to the
opposite direction in the Southern Hemisphere due to the change of sign in the Coriolis force, which
determines the shape of these cloud spirals and commas and “the mirror symmetry” between the
Northern and Southern Hemispheres.
The clouds, linked to fronts and cyclones in these low-pressure patterns, often form three-level
systems of the Ns-As-Cs type and deep convective Cb clouds, especially at the cold fronts, so that
almost all 10 genera from the classifications described in Section 2.1 are met in these systems.
18 Clouds and Their Properties

2.2.2. Sc-St Clouds and Types of Cloud-Topped Boundary Layer

An increase of cloud amount in the eastern and western parts of the oceans (Figs. 2.2, 2.3) is caused
by the extended fields of Sc-St above the warm and cold ocean currents. The same western parts
of climatological fronts above the warm currents are the areas of widespread Sc fields within the
atmospheric cloud-topped boundary layer (CTBL), which consists mostly of open convective cells
(Fig. 2.4).
The five extended bands of low stratus clouds St-Sc exist within ABL over the cold ocean currents
near the western coasts of the continents (Figs. 2.2, 2.3, 2.4): near North America (cold California
Current), South America (cold Peru Current), North Africa (cold Azores or Canary Current), South
Africa (cold Benguala Current), West Australia (cold South Indian Current). The CTBL in eastern
parts of the oceans consists usually of closed convective cells that form above cold ocean currents.
Sc clouds in the ABL are formed under the influence of heat and moisture exchange with the surface
and by the CTBL dynamic structure.
Six major types of cloud-topped boundary layer (CTBL), important for cloud-resolving models
and climate modeling with GCMs, may be identified (CTBL, 1985; Agee, 1985, 1987; Brown, 1974;
Brümmer et al., 1985, 1992; Bakan, 1984; Chlond, 1992; Cotton et al., 2011; Curry and Herman,
1985; Curry et al., 1986, 1988, 1996, 2000; Herman and Goody, 1976; Herman and Curry, 1984;
Khvorostyanov, 1982; Klein et al., 2009; Lilly, 1968; Mason, 1985, 1989; Matveev, 1984; Moeng and
Arakawa, 1980; Morrison et al., 2005a,b; Randall, 1980; Randall et al., 2003).

1. Cold air outbreaks. Clouds form when cold air moves from the east of continents or from the
ice edge over warm ocean currents. The initial cloud formation is rather quick and is domi-
nated by strong heating and moisture transport from below. The clouds are initially cumuliform
(sometimes marine fog forms) and are organized in cloud streets along the wind, but eventually
develop into stratocumulus in the form of closed or open convective cells.
2. Marine stratocumulus boundary layers. This type of CTBL forms over cold ocean currents
generally to the west of continents. The dominant energy source for vertical mixing is radiative
cooling of the cloud tops. Clouds are usually organized in the closed convective cells.
3. Continental cloud-topped boundary layer. Under the influence of high-pressure patterns, low
cloud layers may form at night and persist for several days. These cloud layers are relatively thin
and are dominated by radiative processes.
4. Polar St-Sc clouds. Stratus clouds cover about 70% of the central Arctic basin during summer.
Radiative or advective cooling of relatively warm, moist air that is advected over the Arctic
Ocean is the dominant formation mechanism.
5. Stratocumuli associated with large-scale weather systems. The dominant feature of these
clouds is the strong large-scale vertical motions that are upward ahead of the low-pressure center
and downward behind. These cloud patterns move with the weather systems.
6. Trade-wind cloud-topped boundary layer. Trade-wind clouds form due to the buoyancy
caused by evaporation at the ocean surface. They usually form in the eastern parts of the oceans,
where the surface water temperature is relatively low and mostly cold air advection and a rather
low inversion (< 1,000 m) are observed. The inversion height increases and the stratiform struc-
ture breaks up toward the equator and toward the west.
2.2. Cloud Regimes and Global Cloud Distribution 19

The climatic distribution of the well-mixed cloud-topped boundary layers with convective cells
is given in Fig. 2.4 according to Agee (1985). Cellular cloud patterns are often exhibited on satellite
images of these areas, which correspond to the CTBL of types 1, 2, and 6 of the earlier classification.
The figure shows that the open convective cells with ascending motion and clouds at their boundaries
are formed over warm currents, and closed cells with upward motion and clouds at the cell centers
emerge over the cold currents.
Several types of models have been developed to explain the formation of the CTBL with clouds.
These are the bulk models, conceptual models, and models based on primitive equations. The
last type, in turn, contains two large classes: large eddy simulation (LES) models and turbulence
closure models. Some models are described and reviewed in Lilly (1968), Brown (1974), Moeng
and Arakawa (1980), Randall (1980), CTBL (1985), Curry et al. (1988, 1996), Chlond (1992),
Khvorostyanov (1995), Bretherton et al. (1999a,b), Randall et al. (2003), Khvorostyanov et al.
(2003), and Cotton et al. (2011).

2.2.3. Convective Cloudiness in the Intertropical Convergence Zone

In the tropics, there are clearly pronounced maxima of cloud amounts (mostly due to convective
clouds) which are linked to the intertropical convergence zone (ITCZ) consisting of one or two
branches (Fig. 2.1) and moving seasonally around the equator after the sun. The cloud amount max-
ima are especially large (up to 70–90%) in the regions where the ITCZ intersects the coastlines of
South America, South and Central Africa, Malaysia, and North Australia. Here, diurnal deep convec-
tion also makes considerable contribution to the total cloud amount and precipitation.

2.2.4. Orographic Cloudiness

In the mountains, orographic clouds make considerable contributions to the total cloud and precipitation
amounts. The orographic clouds are most frequent in the zones of updrafts on the upwind slopes of the
mountains, especially on the western slopes of the Cordillera, in the Rocky Mountains, in Scandinavia
due to prevailing western zonal winds, on the southwestern slopes of the Himalayas, and on the Hida
crest in Japan during the monsoon season (Figs. 2.1, 2.2). After passing a mountain crest in the westerly
winds, the descending and heating air becomes dry and clouds dissipate on the eastern (downwind)
slopes of the mountains, causing a lack of precipitation. If climatic westerly winds prevail, a sharp
asymmetry in precipitation often occurs between the western and eastern slopes of the mountain ridges.
For example, the annual precipitation sum may be 6000 mm on the western slopes of Cordillera and
only 200 mm on the eastern slopes and downwind in Patagonia, causing droughts. This lack of rainwater
or snow is a typical feature of many areas located to the east of the mountain crests. Under appropriate
conditions, the situation may be improved and the amount of precipitation falling out on the eastern
downwind slopes can be increased by artificial cloud seeding with ground-based aerosol generators or
from aircraft located near the upwind slopes of the mountain ridge (e.g., Young, 1974a, 1993; Kachurin,
1978; Dennis, 1980; Cotton et al., 1986; Berjulev et al., 1989; Khvorostyanov and Khairoutdinov, 1990).
The preceding brief review shows that all major, global, monthly, and annual cloud maxima are
closely linked to large-scale or mesoscale ascents due either to frontal and cyclonic circulations or to
20 Clouds and Their Properties

convective and orographic forcing. The exception are St-Sc clouds in CTBL that may exist for a long
time in the areas of large-scale descent, such as the Azores, Hawaii and the Arctic, St. Helene, and other
high-pressure centers. Mechanisms of their formation are more complicated and depend on surface
fluxes and on the entrainment rate in CTBL from above (e.g., Lilly, 1968; Randall, 1980; Moeng
and Arakawa, 1980; Agee, 1985, 1987). Cirrus clouds occur frequently as parts of the other cloud
systems—frontal, convective, or orographic cloudiness—but sometimes they can appear separately in
the areas of pressure troughs, wave disturbances, or jet streams in the upper troposphere (Cirrus, 2002).

2.3. Cloud Microphysical Properties

The microstructure of clouds is characterized by the phase, shape, and size spectra of their particles.
The size spectra of cloud drops and ice crystals are described by the size distribution ution functions f(r)
of the particles by radii r, or by diameters D or by other characteristic dimensions like the crystal
axes or maximum length. The size distributionution function by radii f(r) is the number of particles in the
range from a radius r to r + dr in some specified volume. The integral gral of f(r) over all radii is equal to
the number of particles N in this volume. If it is a unit volume (1 cm3 or 1 L or 1 m3), then N is equal
to the particle concentration and it is said that f(r) is normalized to the concentration N. Sometimes
the size spectrum can be normalized to unity—i.e., the integral gral of f(r) over r is equal to 1, then f(r)
represents a probability to find a particle in the range (r, r + dr). Evaluation of all moments with such
normalization requires multiplication by the particle concentration N. The size distribution function
by masses f(m) is the number of particles in the range of masses (m, m + dm) in a unit volume.
The most important and commonly used characteristics of cloud microstructure are concentra-
tions, mean radii, modal radii, effective radii, supersaturation absorption (relaxation) times, liquid
or ice water contents, visibility, precipitation rate, lidar and radar reflectivities, and the extinction,
scattering, and absorption coefficients.
Droplet and crystal concentrations or number densities, Nd and Nc, are the numbers of particles in
a unit volume of a cloud; they are the zero moments of the size spectra; for drops we have
∞
Nd = ∫ 0
fd (rd )drd = M d(0) . (2.3.1)

Hereafter, M(n) denotes the n-th moment of the size spectrum. The same definitions are valid for ice
crystals with a change of the subscript from “d” to “c”; for common definitions, we omit the sub-
scripts here. The mean radius rd of the droplets or the effective (mean) radius of the crystals rc is a
radius of the particles averaged over their ensemble. It is proportional to the first moment of the size
spectrum
∞
1 M (1)
rd = ∫
Nd 0
drrd = d .
rd fd (rd )d
Nd
(2.3.2)

The modal radius, rdm or rcm, of a size spectrum is the radius where the size spectrum has the maxi-
mum, it is determined from the condition

df
= 0. (2.3.3)
dr r = rm
2.3. Cloud Microphysical Properties 21

The effective radius, rd,eff or rc,eff , is the ratio of the 3rd to the 2nd moments of the spectrum. It is used
in calculations of radiative transfer in clouds:
< 3>
reff = . (2.3.4)
< 2>
The supersaturation absorption (relaxation) times, tfd and tfc, are the characteristic times of
supersaturation absorption by the droplets and crystals. As will be shown in Chapters 5, 6, and 7,
they are inversely proportional to the first moment of the size spectra in the diffusion regime of
particle growth:

τ fd (4π Dv N d rd )−1 , τ fc ~ (4π Dv N c rc ) −1 . (2.3.5)

The liquid water content ql (LWC), or ice water content qi (IWC), is the mass of drops or crystals
in a unit cloud volume:
∞
4π 4π 4π
ql = ρ d ∫ rd3 fd (rd ) drd = ρ w N d < rd3 > = ρ w N d M d( 3) , (2.3.6)
3 0
3 3
∞
4π 4π 4π
qi = ρi ∫ rc3 fc (rc ) drc = ρi N c < rc3 > = ρi N c M c( 3) . (2.3.7)
3 0
3 3

The liquid water path (LWP) and the ice water path (IWP) are defined as the integrals of LWC and
IWC overer the cloud layer from the cloud bottom zb to the cloud top zt:
zt zt

LWP = ∫ q
LW , = ∫ qi ( zz)dz . (2.3.7a)
zb zb

They characterize the amount of condensate contained in a cloud and are used for parameterizing
cloud optical properties.
The volume extinction, σɶ ext , k , scattering, σɶ sc , k , and absorption, αɶ abs , k , coefficients of the k-th
substance that characterize attenuation of radiation per unit length and are measured in cm−1 or in
km−1 are defined as
∞  2π rk 
σɶ ext , k π ∫ rk2 K ext , mk fk (rk ) dr
drk , (2.3.8a)
0  λ 
∞  2π rk 
σɶ sc , k π ∫ rk2 K sc , mk fk (rk ) dr
drk , (2.3.8b)
0  λ 
∞  2π rk 
αɶ abs , k π ∫ rk2 K abs , mk fk (rk ) dr
drk , (2.3.8c)
0  λ 
σɶ sc ,k σɶ sc ,k
σɶ sc ,k = σ
σ σɶ ext ,k − αɶ abs ,k , ω λ ,k = = , (2.3.8d)
σ ext ,k σ sc ,k + αɶ abs ,k
ɶ ɶ

where fk(rk) is the size spectrum of the k-th substance, and l is the wavelength of the radiation,
wl, k is the single-scattering albedo, Kext, Ksc, and Kabs are the factors of extinction, scattering, and
absorption, respectively. These factors can be calculated using Mie theory or various analytical
approximations (e.g., van de Hulst, 1957; Liou, 1980, 1992). If a drop or crystal is much greater
than the wavelength and the condition 2π k /λ >> 1 is satisfied and absorption is absent, then
22 Clouds and Their Properties

K ext (2π rk /λ ) ≈ 2, K sc (2π rk /λ ) ≈ 2 .. The corresponding mass coefficients that characterize scattering
or absorption of radiation per unit mass and are measured in cm2g−1 or m2g−1 are defined as

σ ext , k = σ
σ σɶ ext , k / qlk , σ sc , k = σ
σ σɶ sc , k / qlk , α abs , k αɶ abs , k / qlk , (2.3.8e)

where qlk is the LWC, IWC, or mass content of the other substance. These coefficients will be con-
sidered in more detail in Section 2.5. The optical thickness text,k
xt,k of the k-th substance in a cloud is

zt

τ ext ,k ∫σ
zb
ext ,k ( z )d
dz . (2.3.8f)

It characterizes the total (integral) extinction of radiation by a k-th substance in the cloud (by drops,
crystals, vapor, or aerosol). Similar optical thicknesses tsc,k , tabs,k are considered sometimes with
respect to the scattering and absorption coefficients.
The visibility or visual range in a fog or cloud, Lvis, is inversely proportional to the second moments
of the size spectra. It is usually defined in meteorology as a distance from which an object is seen
under the angle of the minimum threshold of 1/50. In liquid clouds, visibility is inversely proportional
to the extinction coefficient:
−1
3.91  ∞  2π rd  
Lvis = = 3.91 π ∫ rd2 K ext fd (rd )drd  . (2.3.9)
σ ext  0  λ  
Ohtake and Huffman (1969) modified this equation for the visibility in a mixed-phase or crystalline
fog or cloud by introducing corrections due to the presence of the ice phase. Assuming Kext ≈ 2, which
is a reasonable approximation for the visible wavelength l ∼ 0.5 μm and drops or crystals of a few
microns and larger, the expression of Ohtake and Huffman (1969) can be written as

−1 −1
∞ ∞   2.5  6qi 
1/ 3
 
3.91   .
2π  ∫0
Lvis = rd + ∫ r f (rc ) d
2
drrc     − 3 (2.3.10)
d
0
c c
  c  πρi N i   
 
With
ith fc = 0, this converts into the previous (Eqn. 2.3.9). This expression can be used for evaluation of
the visibility range in mixed and crystalline clouds and fogs.
The precipitation rate, P, is the intensity or mass flux of precipitation per unit area per unit time in
various forms: liquid (rain), mixed (rain with snow), or ice (snow):
∞
4π 4π
P=
3
∑ ∫v =
3
∑ρa k vk M k(3+ bk ) , (2.3.11)
k =1,2 0 k =1,2

where k = 1 and k = 2 mean droplets and crystals, M(3+b) is the (3+b)-th moment, and it is assumed that
the terminal velocity is described by the power law vk = avk rkbk . The more complicated dependencies
of v(r) are discussed in Chapter 12.
eflectivity factor ZR in terms of particle radii is proportional to the sixth moment of
The radar reflectivity
the size spectrum:
∞

Z R = < r 6 > = ∫ r 6 f (r ) d
dr = M (6) . (2.3.12)
0
2.4. Size Spectra and Moments 23

The radar reflectivity factor in terms of particle diameters ZD can be related to ZR using the relation
fr(r)dr = fD(D)dD, where subscripts “r” and “D” denote corresponding distributions. It then follows
from (Eqn. 2.3.12) that
∞

ZD D 6 > = ∫ D 6 f D ( D)ddD
D = M D(6) = 64 Z R . (2.3.13)
0

The corresponding backscatter cross-sections for spherical particles at radar wavelengths, l >> rm, in
the Rayleigh scattering limit are
2
π 5 nk2λ − 1
Ak = 64α rad Z R α rad = , (2.3.14)
λ 4 nk2λ + 2

where nkl = mkll − ikkl is the complex refractive index for water (k = 1) and ice (k = 2), mkll and kkl
are its real and imaginary parts. In the typical temperature range for not very cold clouds and the
wavelengths of meteorological radars, | (nk2λ− 1) /(nk2λ+ 2) |2 ≈ 0.93 for water and ≈ 0.21 for ice. That is,
1)/(
the contribution of ice into reflectivity is almost five times smaller for the same size spectra of drops
and crystals.

2.4. Size Spectra and Moments

Various parameterizations of the drop and crystal size distribution
ution functions f(r) have been developed
in cloud physics, including gamma distributions, generalized or modified gamma distributions, log-
normal distributions, exponential distributions, and inverse power laws. They are usually constructed
as empirical fits to measured size spectra. Size spectra can also be obtained as solutions of the cor-
responding kinetic equations that describe evolution of the size distribution functions and are consid-
ered in Chapters 5, 13, and 14. In this section, we present the major empirical parameterizations used
in cloud physics for the aerosol, droplet, and crystal size spectra and the analytical evaluation of their
moments used in various applications. The theoretical foundations for some of these expressions are
given in Chapters 13 and 14. Aerosol size spectra play a key role in the formation of drops on aerosol
particles (Chapters 6 and 7) and ice nucleation (Chapters 8, 9, and 10) and are considered here along
with the drop and crystal size spectra.

2.4.1. Inverse Power Laws

The inverse power law is frequently used for parameterization of the aerosol size spectra or the size
spectrum of large drops and crystals in the form

fa (ra ) = cNa ra−ν . (2.4.1)

The inverse power law was suggested by Junge in the 1950s (see Junge, 1963) as an empirical fit
to the observed aerosol size spectra. Junge obtained the slope v ª 4 as the most frequent value in
many measurements and in a significant radii range. This empirical inverse power law fit for aerosols
was later justified. It was derived from the solution of the coagulation equation, but the values of
24 Clouds and Their Properties

the slopes n appeared to be different in various ranges of the aerosol size spectrum. For example,
v ≈ −5/2 at radii ra ∼ 0.1 μm and v ≈ −9/2, at radii ra ∼ 5 μm. That is, the slopes increase with increasing
radius, and this power law was actually a “quasi power law” with variable slope (e.g., Junge, 1963;
Lushnikov and Smirnov, 1975; Smirnov, 1978; Pruppacher and Klett, 1997; Seinfeld and Pandis,
1998). The inverse power law explains some aerosol properties, in particular the inverse power law for
the aerosol extinction coefficient, ext − a (see Ångström, 1929, 1964, and Chapter 6 here), which
is convenient in evaluating those moments over limited ranges of the spectrum. Deficiencies of the
inverse power law are that the integrals over the entire spectrum diverge at small sizes, and it is neces-
sary to use several different slopes at various radii to approximate a measured spectrum. Therefore,
other distributions have been used to avoid these problems.
The inverse power law (Eqn. 2.4.1) with a negative index can approximate the spectrum of larger
cloud drops over the radius range from 100 to between 300 and 800 μm with v = −2 to −12 (Okita,
1961; Borovikov et al., 1965; Nevzorov, 1967; Ludwig and Robinson, 1970). The inverse power law
(Eqn. 2.4.1) has also been used to represent the ice crystal size spectra in cirrus and frontal clouds in
the intermediate size region from ∼ 20 to between 100 and 800 μm, with values of v in the range −2
to −8 (Heymsfield and Platt, 1984; Platt, 1997; Poellot et al., 1999; Ryan, 2000).

2.4.2. Lognormal Distributions

Lognormal distributions are used for parameterization of the aerosol size spectra (e.g., Whitby, 1978;
Jaenicke, 1988; Vignati et al., 2004) and for the drop and crystal size spectra in analyses of measured
cloud size spectra and some cloud models (e.g., Levin, 1954; Clark, 1976; Feingold and Levin,
1986). The lognormal size spectrum of aerosol or cloud drops and crystals fa(ra) can be presented in
the form:

Na  ln 2 (ra / ra 0 ) 
fa (ra ) = exp  − , (2.4.2)
2π (ln σ a )ra  2 ln 2 σ a 

where Na is the particle number concentration, sa is the dispersion of the spectrum and ra0 is the mean
geometric radius that is related to the modal radius ram as

ram = ra 0 exp(− ln 2 σ a ). (2.4.3)

The general n-th moment of the lognormal distribution is calculated in Appendix A.2 of
Chapter 2 and is
∞ ∞
Na  ln 2 (ra / ra 0 ) 
M ( n ) = ∫ ran fa (ra ) dra = ∫ ran−1 exp  −  dra
0
2π (ln σ a ) 0  2 ln 2 σ a 
 n 2 ln 2 σ a 
= N a ran0 exp   . (2.4.4)
 2
2.4. Size Spectra and Moments 25

In particular, the concentration, mean radius r , mean squared radius r2, and mean cubic radius r3 with
lognormal distributions follow from (Eqn. 2.4.4) for n = 0, 1, 2, and 3:

N a = M (0) , (2.4.5)
∞
1 M (1)  ln 2 σ a 
r1 =
Na ∫r
0
f (ra ) ddrra =
a a
Na
= ra 0 exp 
 2 
, (2.4.6a)

1/ 2 1/ 2
 1 ∞
  M (2) 
r2 = 
 Na
∫0 r f (ra ) ddrra  =  N a  = ra 0 exp ln σ a ,
2
a a ( ) (2.4.6b)

1/ 3 1/ 3
 1 ∞
  M (3)   3 ln 2 σ a 
r3 =  ∫0 ra fa (ra ) ddrra  =  N a  = ra 0 exp  2  .
3
(2.4.6c)
 Na

The aerosol mass content, liquid water content (LWC), or ice water content (IWC) in a unit volume
of the air is
∞
4 4 4  9 ln 2 σ a 
ql = πρa ∫ ra3 fa (ra ) dra = πρ a M (3) = πρa N a ra30 exp  , (2.4.7)
3 0
3 3  2 

where ra is the density of the aerosol material, water, or ice.

Several models of aerosol size spectra have been suggested as a superposition of several lognormal
modes as an approximation for more complex aerosols of various types: marine, continental, rural,
and urban (e.g., Whitby, 1978; Jaenicke, 1988; Vignati et al., 2004; Ghan et al., 2011)
m
N ai  ln 2 (rai /rai 0 ) 
fa (ra ) = ∑ exp  − , (2.4.8)
i =1 2π (ln σ ai )rai  2 ln 2 σ ai 

where the subscript i means the i-th mode, summation is performed by i over m modes; m = 4 in the
Jaenicke’s (1988) model, but can be smaller or greater in the other models. The value m = 3 is usually
chosen in parameterizations for polymodal aerosols, which describe a superposition of the three aerosol
modes: the smallest Aitken particles (ra < 0.01 μm), the larger submicron fraction (0.1 ≤ ra ≤ 1 μm),
and a coarse fraction (ra ≥ 1 μm, up to a few tens of microns) (e.g., Abdul-Razzak et al., 2000). A more
detailed model with m = 7 and the superposition of seven lognormal distributions was developed in the
aerosol module M7 by Vignatti et al. (2004), which consisted of four internally mixed aerosols contain-
ing both soluble and insoluble fractions, and three insoluble modes. This model M7 was also used in
mesoscale weather forecast and regional climate models (Zubler et al., 2011).

2.4.3. Algebraic Distributions

A lognormal size spectrum can be approximated by the superposition of the power laws with
positive indices at ra < ra0 and negative indices at ra > ra0 (see Section 6.4.2). Another convenient
26 Clouds and Their Properties

approximation of the lognormal distribution was found by Khvorostyanov and Curry (2006, 2007)
who introduced the algebraic size spectra

k a 0 N a (ra /ra 0 ) ka 0 −1
fa (ra ) = , (2.4.9)
ra 0 [1 + (ra /ra 0 ) k ]2

where the index ka 0 is defined as that introduced by Ghan et al. (1993):

4
ka 0 = . (2.4.10)
2π l σ a

Derivation of (Eqn. 2.4.9) from the lognormal spectrum (Eqn. 2.4.2) is given in Section 6.4.4. The
distribution (Eqn. 2.4.9) well approximates the lognormal spectrum, tends to zero at small and large
radii, and it allows easy analytical evaluation of the moments and various algebraic functions that
cannot be evaluated analytically with the lognormal spectrum, as will be illustrated in Chapter 6.

2.4.4. Gamma Distributions

The size spectra f(r) of cloud and fog drops and crystals can be conditionally separated into two major
fractions: particles with radii smaller than 25–50 μm, called small-size fraction; and larger particles,
called large-size fraction. The droplets and crystals of the small-size fraction with a modal radii of
a few microns have been reasonably approximated by generalized or modified gamma distributions
(Levin, 1954; Borovikov et al., 1963; Deirmendjan, 1969; Clark, 1974):

f (r ) = cN r p exp(− β r λ ) . (2.4.11)

We omit in this section the subscripts “d” for drops and “c” for crystals; these subscripts will appear
later when necessary.. Here, p > 0 is the spectral indexx or the shape parameter of the spectrum, b and l
determine its exponential tail, and cN is a normalization constant. This size spectrum is usually normal-
ized to the droplet or crystal concentration N, relating cN to N.
Calculation of the n-th moment of the generalized gamma distribution (Eqn. 2.4.11) gives
(Gradshteyn and Ryzhik, 1994)
∞ ∞

M (n) = ∫ r n =c ∫r
p+ n
exp(− β r λ ) dr
0 0

( p + n +1) / λ  p + n + 1
= cN λ 1 β Γ , (2.4.12)
 λ 

where Γ((x) is Euler’s gamma function. The concentration N is the 0-th moment and it follows from
this equation that
∞

N = M (0 ) = cN ∫ r p exp(− β r λ ) dr
0

( p +1) / λ  p + 1
= cN λ β 1
Γ . (2.4.13)
 λ 
2.4. Size Spectra and Moments 27

The constant cN can be expressed

xpressed via N using this relation
−1
  p + 1 
cN = Nλβ ( p +1) / λ  Γ  , (2.4.14a)
  λ 
and the normalized size spectrum can be written as
−1
  p + 1  p
f (r ) = Nλβ ( p +1) / λ  Γ λ
 r exp(− β r ) . (2.4.14b)
  λ 

The first moment determines the mean radius r . Using (Eqns. 2.4.13 and 2.4.14a), we obtain
∞ −1
 p + 2    p + 1 
M (1)= N r = ∫ rf (r )dr = N β (1/ λ )
Γ Γ . (2.4.15)
0
 λ    λ  

The mean radius r of the distribution follows from this relation:

−1
M (1)  p + 2    p + 1 
r = = β − (1/ λ ) Γ Γ . (2.4.16)
N  λ    λ  

The liquid (or ice) water content (LWC or IWC) is defined following equations from Section 2.3:
∞
4π 4π 4π
ql = ρ w < Nr 3 > = ρ w ∫ r 3 f (r ) dr = ρ w M (3)
3 3 0
3
−1
4π 3/ λ  p + 4    p + 1 
= ρw β Γ Γ . (2.4.17)
3  λ    λ  

The radar reflectivity in terms of radii ZR is defined as a sixth moment of the spectrum. It is obtained
from (Eqn. 2.4.12) and by substituting cN from (Eqn. 2.4.14a):
∞
+ 7) / λ ]
Γ[( p +
Γ
Z R = < r 6 > = ∫ r 6 f (r ) ddr = = Nβ −6 / λ
= M (6 ) = . (2.4.18)
0
Γ + 1) / λ ]
Γ[( p +

The radar reflectivity

vity in terms of particle diameters ZD can be related to ZR using a relation
fr(r)dr = fD(D)dD, where subscripts “r” and “D” denote the distributions by radius and diameter.
Thus, it follows from (Eqn. 2.4.18) that
∞

=<
ZD= < D 6 > = ∫ D 6 f D ( D)ddD =
= M D(6 ) =
= 26 Z R
0
−1
6/ λ  p + 7    p + 1 
= 26 N β
= Γ
Γ Γ . (2.4.18a)
 λ    λ  

The absolute spectral dispersion by radii is evaluated as

1 ∞
(r − r )2 f (r )dr
N ∫0
σ ra2 =
1
= ( M (2 ) − 2rM
rM (1) r 2 M ( 0) ). (2.4.19a)
N
28 Clouds and Their Properties

Substituting here the moments from (Eqns. 2.4.12 and 2.4.13) yields

2/λ  p + 1   p 3   p + 2  1  p 1 
σ ra2 = β 2/
Γ 1
Γ − Γ2 Γ .
 λ    λ   λ   λ   (2.4.19b)

The relative dispersion from (Eqns. 2.4.19b to 2.4.16) is

1/ 2
σ ra  Γ[( p + 1) / λ ) ( p 3) / λ ] 
σ rr = =  − 1 . (2.4.19c)
r  Γ 2
[( p + 2) / λ ] 
A particular case of the generalized gamma distribution (Eqn. 2.4.11) with p = l − 1 is called the
Weibull distribution:

f (r ) = cN r λ exp(− β r λ ) . (2.4.20a)

The relative spectral dispersion for the Weibull distribution follows from (Eqn. 2.4.19c):
1/2
σ ra  (1 λ) 
σ rr= = 2 − 1 . (2.4.20b)
r  Γ (1 + 1 / λ ) 
A particular case that occurs as an analytical solution to some kinetic equations is the Weibull dis-
tribution with l = 2, p = 1—i.e., f (r ) = cN r exp(− r 2 ) (see Chapter 13). The relative dispersion for
this spectrum is
1/2 1/2
 Γ (2)  4 
σ rr =  2 − 1 = − 1 = 0.523, (2.4.20c)
 Γ (3/2)  π 

that is, it does not depend on the spectral indices p and l. We used here the recurrent property of the
gamma function and its value
alue at x = ½:

Γ ( p + 1) = pΓ ( p), Γ (1) = 1, Γ (1/ 2) = π. (2.4.20d)

Another important particular case of (Eqn. 2.4.11) with p = 0 is the exponential distribution suggested
by Marshall and Palmer (1948) for raindrops, and by Gann and Marshall (1958) for snowflakes:

f (r ) = N 0 exp(− β r ) , (2.4.21)

b and N0 are often called the slope and the intercept of the spectrum.
A particular case of the generalized gamma distributions (Eqn. 2.4.11) with l = 1,

f (r ) = cN r p exp(− β r ) , (2.4.22)

is referred to as the simple gamma distribution or simply as the gamma distribution. Note that
the inverse power law (Eqn. 2.4.1) is a particular case of the gamma distribution (Eqn. 2.4.22) with
b = 0 and p < 0. All the moments of (Eqn. 2.4.22) can be obtained from the previous equations setting
l = 1, but these size spectra are often used without reference to the generalized gamma distributions
and the relations of the moments is simplified due to the recurrent relation (Eqn. 2.4.20d) for the
Euler gamma functions. Therefore, it is useful to provide a brief outline of evaluating moments of the
2.4. Size Spectra and Moments 29

gamma distribution. The general moment can be calculated using the definition of Γ((x) (Gradshteyn
and Ryzhik, 1994):
∞ ∞

M (n) = ∫ r n =c ∫r
p+ n
exp(− β r )dr
0 0
∞
cN cN
∫x
p+ n
= + +1
exp(− x )dx = Γ ( p + n + 1) . (2.4.23)
β 0
β p+ n+1

We assume that the size spectrum (Eqn. 2.4.22) is normalized to the concentration N:
∞
cN
N= ∫ f (r )dr = M = Γ ( p + 1) .
(0)
(2.4.23a)
0
β p+1

The normalization constant cN can be expressed

xpressed via N as

β p +1
cN = N . (2.4.24)
Γ ( p + 1)

Substitution of cN into (Eqn. 2.4.23) gives for n-th moment:

N Γ ( p + n + 1) N
M (n) = = n ( p + n)( p + n − 1)...( p + 1) , (2.4.25)
βn β

where we used the recurrent relation (Eqn. 2.4.20d), and where the gamma functions vanish. The first
three moments are
N N
M (0 ) = N , M (1) = ( p + 1) , M (2 ) = ( p + 2)( p + 1) ,
β β2
N
M (3) = ( p + 3)( p + 2)( p + 1) . (2.4.25a)
β3

The mean radius is determined from the first moment:

∞
1 M (1) ( p + 1)
N ∫0
r= rf (r ) dr = = . (2.4.26)
N β

The modal radius rm is determined from the condition df(rm)/dr = 0, which yields from (Eqn. 2.4.22)
p p
rm = =r . (2.4.27)
β p+1

The second equality relates the modal and mean radii. Using these definitions of cN and the mean
radius, the normalized size spectrum can be rewritten in the two forms convenient for calculations,
via b, and via the mean radius expressing from (Eqn. 2.4.26) β = ( p + 1) / r :

β p +1
f (r ) = N r p exp(− β r)
r (2.4.28a)
Γ ( p + 1)
( p + 1) p +1 1  r  − ( p +1) r / r
p

= N e . (2.4.28b)
Γ ( p + 1) r  r 
30 Clouds and Their Properties

The mean squared radius <rr2> needed in optical calculations is

1 ( 2) ( p + 2)( p + 1) p+2 2
<rr2 2> = M = = r . (2.4.29)
N β2 p+1

The effective radius reff is the ratio of the 3rd to the 2nd moment of the spectrum:

< 3> M (3) p + 3 p+3

reff = = (2 ) = r= rm . (2.4.30)
< > M p+2 p

The liquid water content qL is evaluated via the 3rd moment:

4 4 ( p + 3)( p + 2) 3
qL = πρ w M (3) = πρ w N r . (2.4.31)
3 3 ( p + 1)2

The ice water content qI is calculated with the same formula, replacing rw with ri, and keeping in
mind that N is then the crystal concentration. The absolute dispersion of the spectrum is expressed
via the 0th, 1st, and 2nd moments as
1 ∞ 1 ∞
)
2
= ∫ ( r 2 − 2rr
N ∫0
σ ra2 = − r +r2 f (r)
r dr
N 0
1 r2
= ( M (2 ) −
= M (1) +
− 2rrM + r 2 M ( 0) ) =
= . (2.4.32)
N p +1

The indexx p of the gamma distribution determines the relative spectral dispersion srr of the gamma
distribution (Eqn. 2.4.28a,b):
1/2
σ ra 1  1 ∞ 
σ rr =
r
=
rN ∫ (
0
)2 f (r )dr

= ( p + 1)−1/ 2 . (2.4.33)

Typical values for local volumes in liquid clouds of the indexx p = 6 − 15 were measured by Levin
(1954) and confirmed in many subsequent experiments (e.g., Noonkester, 1984; Austin et al., 1985;
Curry, 1986; see the review in Chapter 13). These values
alues of p correspond to the relative dispersion
sr = 0.38 − 0.25. Vice versa, the index
x p can be expressed from (Eqn. 2.4.33) via srr:

p = 1 / σ rr2 − 1. (2.4.33a)

If the relative dispersion of the spectrum is known from measurements (see Chapter 13), and assum-
ing that the spectrum is the gamma distribution, the index x p can be evaluated along with the other
moments, including cloud optical properties using the equations given earlier. The index x p and spec-
tral dispersions determine the rate of coagulation and accretion processes and therefore play an
important role in precipitation formation. The smaller the p and the larger the spectral dispersions in
a cloud, the faster this cloud may produce precipitation.
2.4. Size Spectra and Moments 31

In calculations of the droplets and crystal growth rates and the evolution of the size spectrum, the
minus first moment may be required (Chapter 5). It follows from the previous equations:

Γ ( p) N N p+1
M ( −1) = N β = = . (2.4.34)
Γ ( p + 1) rm r p

The radar reflectivity defined in Section 2.1 is evaluated via the 6-th moment (Eqn. 2.4.18) with
l = 1:
∞
Γ ( p + 7)
Z R = < r 6 > = ∫ r 6 f (r )ddr = M (6 ) = N β −6 . (2.4.35)
0
Γ ( p + 1)

Using the recurrent relation Γ((p + 1) = pΓ((p) and the relation for β = ( p + 1)/r , yields

( p + 6)( p + 5)( p + 4)( p + 3)( p + 2)

ZR= < r 6 > = N r 6 . (2.4.36)
( p + 1)5

An example of the typical size spectra observed in liquid clouds is shown in Fig. 2.5.

600
550
500 SW = 0.1%
Total size spectra (cm–3µm–1)

450 SW = 0.01%
400
350
300
250
200
150
100
50
0
0 1 2 3 4 5 6 7 8 9 10
Radius (µm)

Figure 2.5. An example of the typical size spectra observed in liquid clouds consisting of the aerosol
and droplet size spectra. The left branch with radii smaller than 1−2 μm is the size spectrum of
the wet interstitial aerosol described by the inverse power law or lognormal spectrum and limited
by the boundary radius rb ∼ 0.5−1 μm decreasing with increasing water supersaturation sw. The
right branch with modal radius near 3.5 μm is a droplet size spectrum with larger radii calculated
as a gamma distribution with mean radius r = 4 μm, indexx p = 6, and normalized to the droplet
concentration N = 500 cm−3. The minimum near 1−2 μm is caused by the superposition of these two
spectra.
32 Clouds and Their Properties

These size spectra consist of the superposition of the aerosol and droplet size spectra. The left branch
with r < 1–2 μm is the size spectrum of the wet interstitial aerosol described by the inverse power
law or lognormal spectrum and limited by the boundary radius, r < rb ∼ 0.5–1 μm, decreasing with
increasing water supersaturation sw as described in Chapter 6. The right branch with a modal radius
near 3.5 μm is a droplet size spectrum with larger radii. It is calculated here as a gamma distribution
with mean radius r = 4 μm, index x p = 6, and is normalized to the droplet concentration N = 500 cm−3.
The minimum near 1–2 μm is caused by the superposition of these two spectra; its position moves to
smaller radii with increasing sw.

2.5. Cloud Optical Properties

As described in Section 2.3, the mass absorption coefficients and scattering coefficients of droplets
and crystals in a polydisperse cloud can be calculated as integrals of the absorption and scattering
efficiencies with the size distribution function. The precise calculations of the absorption and scat-
tering efficiencies for spherical particles are based on Mie theory, with expansions into power series
by Legendre polynomials (e.g., van de Hulst, 1971; Liou, 1980), but they are too time-consuming
for cloud or climate models. The nonsphericity of drops and crystals and the mixture of various
crystal habits and shapes in clouds further complicate calculations. Therefore, various approximate
methods have been developed for parameterizations of cloud optical properties. A detailed descrip-
tion of the subject is beyond the scope of this book, and in the following text we give only a brief
introductory overview of some methods for calculation of optical parameters that are related to cloud
microphysics.
One method of parameterization of the absorption and scattering coefficients aLi, s SlLi
l , a lLi, optical
S

thickness ti , asymmetry parameter <cos q > and single-scattering albedo wl represents them as linear
functions of powers of effective radius re (Eqn. 2.3.4). Slingo and Schecker (1982) developed such
parameterizations of shortwave (l = 0.25–4 μm) optical properties for water clouds with 24-band
spectral resolution. Slingo (1989) showed that this scheme can be averaged over as few as 4 bands
and showed that this resolution allows reproduction with good accuracy the characteristics of solar
radiation measured by Herman and Curry (1984) in arctic St clouds. Ebert and Curry (1992), using
the results of calculations in Takano and Liou (1989) based on the ray-tracing technique, generalized
such parameterizations for crystalline clouds and non-spherical crystals with 5-band spectral resolu-
tion. The optical parameters in such schemes are parameterized as

τ i = IWP (ai + bi / re ), 1 − ω i = ci + di re , (2.5.1)

< cos θ i > ei fi re , α Li = aLi + bLi / re , (2.5.2)

where re is the effective crystal radius, i is the number of spectral interval or the transmission band,
IWP denotes here the ice water path for crystalline clouds and the liquid water path for liquid clouds.
The values of the parameters were fitted in Ebert and Curry (1992) for five intervals in the solar spec-
trum from 0.25 μm to 3.5 μm, and for five intervals in the infrared (longwave) spectrum from 4.0 to
200 μm. Liou (1992) and Fu and Liou (1993) described a parameterization for crystalline clouds with
expansion terms up to the third order by the effective crystal size. Such parameterizations are suitable
for both cloud and climate models.
2.5. Cloud Optical Properties 33

Another method is based on approximations of the exact numerical Mie calculations performed
for the particles with the size parameter x = 2pr pr/l, where l is the wavelength, and the complex refrac-
tive index nl = mill − ikill, where mill and kill are its real and imaginary parts. Shifrin (1955) calculated
the absorption efficiency Kabs from Mie theory for spherical particles and found a good analytical
approximation for a particle with radius r:
Sh
K abs (2π r /λ ) = 1 − exp(−ψ ), ψ = 8π κ λ /λ . (2.5.3)

This formula is an interpolation between the small and large particle limits, is valid both for weak
and strong absorption, and ensures good accuracy in calculations of Kabs. This expression should be
slightly corrected in order to give the correct Rayleigh–Gans limit (van de Hulst, 1971) at small y as
cor
K abs (2π rr/λ ) = 1 − exp[− (2 / 3)ψ ] . (2.5.4)
In the bands with weak absorption or for small particles, y << 1, and in bands with strong absorption,
y ≥ 1, the limits of (Eqn. 2.5.4) are

cor 2ψ 16π
πκ λ r cor
K abs ≈ = , at ψ << 1 d K abs ≈ 1at ψ >>1. (2.5.5)
3 3λ
The absorption cross-section is calculated as

σ abs = π r 2 K abs
co
cor
= π 2 {1 exp[ (2 /3)ψ ]} . (2.5.6)

Using (Eqns. 2.5.6 with 2.5.5) yields the limits at weak and strong absorption:

4πκ λ
σabs ≈
≈ << 1
V , at ψ <
<< nd σabs ≈ A at ψ ≥ 1, (2.5.7)
λ
pr3 and A = pr
where V = (4/3)pr pr2 are the volume and the projected surface area of a particle with radius r.
cor
These equations show that the efficiency factor K abs in (Eqn. 2.5.4) satisfies the requirement that the
weak absorption is volume-dependent (the first equation in (Eqn. 2.5.7)) and the strong absorption
is surface-dependent (second equation in (Eqn. 2.5.7)), as follows from the rigorous radiation theory
(van de Hulst, 1957; Kondratyev, 1969; Paltridge and Platt, 1976; Liou, 1980, 1992; Goody, 1995).
Van de Hulst (1957) developed an approximate but sufficiently accurate method, called the anoma-
lous diffraction theory (ADT), which considers the rays passing through and around the particle, and
therefore have different phases behind the particle. The extinction Kext and absorption Kabs factors
in ADT result from the interference of the rays with different phases that pass through the particle
with those that do not. Based on ADT, van de Hulst (1957) derived expressions for the scattering and
absorption factors for spherical particles:

 2π r 
2
cos z − y  cos z 
K ext ,n = 2 − 4 e sin (δ − z)
z +4 os 2 z − e − y cos (δ − 2z )] ,
[cos
[c (2.5.8a)
 λ  δ  δ 

 2π r  exp(−ψ ) exp(−ψ ) − 1
H
K abs ,n = 1 + 2 +2 , (2.5.8b)
 λ  ψ (ψ )2
34 Clouds and Their Properties

where n = mill − ikli is the complex refractive index, and

4π ri κ λi
δ= (mλi − 1), z = arctan ,
λ mλ i − 1
κ λiδ 4π riκ λi 8π riκ λi
y= = , ψ= . (2.5.9)
mλ i − 1 λ λ

The extinction and absorption factors (Eqn. 2.5.8a,b) were derived in the ADT by van de Hulst (1957)
under the following two assumptions:

| n − 1| <<
<< 1, and x = 2π /λ >> 1. (2.5.10)
The first condition, referred to as the soft-particle approximation, means that the refraction index of
the particle substance should be close to 1, |n| ∼ 1. The second requirement, x >> 1, is typical for the
geometric optics approximation. However, subsequent tests and comparisons with exact Mie calcula-
tions showed that these equations still describe the efficiency factors with reasonable accuracy up
to ml ∼ 1.3–1.5, and for x = 2pr pr/l ≤ 1 (e.g., van de Hulst, 1957; Stephens, 1984; Chylek and Klett,
1991a,b; Chylek and Videen, 1994) and can be applied for drops, many types of aerosol particles, and
for crystals with some modifications, taking into account their shapes. ADT has been a useful tool in
remote sensing of clouds with radars for evaluation of the optical properties of clouds consisting of
various crystal habits and shapes (Matrosov, 1997). By expanding into the power series, it is easily
H
shown that the asymptotics of K abs in (Eqn. 2.5.8b) at weak and strong absorptions are the same as
that of the interpolation equation (Eqn. 2.5.5), and the limits of sabs for these cases also reduce to
(Eqn. 2.5.7) with volume and surface absorption, respectively.
It is possible to integrate analytically formulae (Eqns. 2.5.3) – (2.5.9) for some types of the size
spectra—e.g., gamma distributions, and hence obtain analytical representations of the mass absorp-
tion and scattering coefficients (e.g., van de Hulst, 1957; Khvorostyanov, 1982, 1995; Stephens,
1984; Ackerman and Stephens, 1987; Kondratyev and Khvorostyanov, 1989; Kondratyev et al.,
1990; Stephens et al., 1990; Chylek and Klett, 1991a,b; Chylek and Videen, 1994; Mitchell and
Arnott, 1994; Khvorostyanov and Sassen, 1998a,b). ADT is also convenient for numerical integration
with the measured size spectra (Matrosov, 1997). The analytical approach for polydisperse clouds is
described in the following text.
Size spectra fi(ri) of drops and crystal are parameterized by the gamma distribution:

fi (ri ) = cN N i ri p exp[ − (p i +1)ri / ri ], (2.5.11)

where pi is the index of gamma-distribution, ri is the mean radius, Ni is the number concentration,
cN is the normalizing factor, and the subscript i denotes drops or crystals. Substitution of Kext from
(Eqn. 2.5.8a) and fi(ri) from (Eqn. 2.5.11) into expression (Eqn. 2.3.8a) for the extinction volume
coefficient ɶ ext ,i and integration yields an analytical expression for ɶ ext ,i :

∞  2π ri 
σɶ ext ,i π ∫ ri2 K ext , ni fi (ri d
drri
0  λ 
= Ag (1 − D2,ext + D3,ext − D4,ext ), (2.5.12a)
pi + 2
Ag = 2π ri 2 N i ,
pi + 1
2.5. Cloud Optical Properties 35

pr2 integrated over the size spectrum of the particles

where Ag is the geometric cross-section p
ensemble related to a unit volume, and

2( pi + 2) cos z  δ 
D2,ext = ( pi + 2 ) / 2 sin ( pi + 2) arctan − z , (2.5.12b)
ϕ δ  pi + y + 1 
pi + 1 (2 coss 2 z cos 2 z )
D3,ext = , (2.5.12c)
pi + 2 δ2

pi + 1 2 cos 2 z  δ 
D4,ext = 2 ϕ ( pi +1)/2
cos ( pi + 1)arctan − 2z  , (2.5.12d)
pi + 2 δ  pi + y + 1 
4π ri (mλ i − 1) κ λi
δ = , z = arctan , (2.5.13a)
λ mλ i − 1
1/2
δκ λi 4π riκ λi  y δ 
y= = , ϕ = 1 + + 2 
, (2.5.13b)
mλ i − 1 λ  ( pi + 1) 2
( pi + 1) 

and all the parameters with overbar are calculated with the mean radius ri . The last three terms in
(Eqn. 2.5.12a) are the corrections due to diffraction wave effects. After integration over the size spec-
trum, the accuracy of ADT approximation may increase relative to its accuracy for a single particle
since the phase shift between the rays passing through the particle and outside is smoothed due to
differences in the particle sizes. Thus, (Eqn. 2.5.12a–d) can be applicable for many particle types
including drops, crystals, and aerosols.
Equation (2.5.12a) is simplified for the case of solar radiation at l = 0.4 – 4 μm and for character-
istic sizes of drops and crystals of a few microns and greater. The expression (Eqn. 2.5.12a) for ɶ ext ,i
contains four terms in parentheses. The first term is 1 and the contribution of the other three terms
have maxima at the minimum values of δ and ϕ , which are in the denominators here. If ri is fixed,
δ and ϕ are minimum at maximum l. An estimate for l = 3.8 μm for the droplet size spectrum with
pi = 6 and ri = 4.7mm yields δ ≈ 4.6 and ϕ ≈ 1.6, and the contribution ution of the third term D3, ext into
(Eqn. 2.5.12a) is ∼10%. The coefficients before sin(. . .) in the second term D2, ext and before cos(. . .)
in the fourth term D4, ext are respectively 0.9 and 1.5%, and so these terms can be neglected. At smaller
wavelengths, δ and ϕ are greater, and the contribution ution of the terms D2, ext and D4, ext is even smaller.
Thus, only the first
irst and third terms, 1 and D3, ext, are retained for the SW (shortwave or solar) radiation
and for cloud particles of a few microns and greater. Note, however, that the contribution into ɶ ext ,i
in (Eqn. 2.5.12a) of the terms D2, ext and D4, ext can be comparable to the others for greater l—e.g., for
LW (longwave or infrared) or microwave radiation or for smaller particles sizes ∼1–2 μm or submi-
cron particles, when the contribution
ution of these terms may be comparable to D3, ext and all four terms
should be retained in (Eqn. 2.5.12a). Retaining in (Eqn. 2.5.12a) only the first and third terms (1 and
D3, ext) for cloud drops and spherically equivalent crystals in the SW spectrum, and expressing z , cos z ,
and cos(2 2 z ) via mli
l and kli from (Eqn. 2.5.13a), we have

pi + 2  pi + 1  λ 2  (mλ i − 1)2 − κ λ2i 

σɶ ext ,i 2π N i ri 2 1 + . (2.5.14)
pi + 1  pi + 2  8π 2 ri 2  [(mλ i − 1)2 + κ λ2i ]2 
36 Clouds and Their Properties

This expression predicts an anomalous dispersion—i.e., an increase in the extinction coefficient

with increasing wavelength, ∼l l2, of a few percent in the SW region, in agreement with observa-
tions. A more universal quantity that does not depend on particle concentration and is used in the
radiative transfer equations is the mass extinction coefficient λexti , which can be obtained by dividing
(Eqn. 2.5.14) by the LWC or IWC. For the gamma distribution:

4 ( p + 3)( pi + 2) 3
qLi = πρ w N i i ri , (2.5.15)
3 ( pi + 1)2

where rw denotes the density of water or ice, thus λexti ɶ ext ,i /qqLi and the mass coefficient is

3 pi + 1  p + 1 λ2 (mλ i − 1)2 − κ λ2i 

σ λexti =  1 + i . (2.5.16)
2 ρi ri pi + 3  pi + 2 8π ri [(mλ i − 1)2 + κ λ2i ]2 
2 2

The volume absorption coefficient αɶ abs ,i can be evaluated using either the interpolation formula
(Eqn. 2.5.4) or van de Hulst’s (1957) Equation (2.5.8b). Integrating (Eqn. 2.5.4) with the gamma
distribution (Eqn. 2.5.11), we obtain for any l and ri
∞
 2π r 
αɶ abs ,i ∫ πr
2 cor
K abs f (r ) dr
0
 λ  i i
− ( pi + 3 )
pi + 2   (16π / 3)κ λ i ri  
= π N i ri 2
1 − 1 +  . (2.5.17)
pi + 1   ( pi + 1)λ  


The volume scattering coefficient can be evaluated as ɶ sc ,i = ɶ ext ,i − ɶ abs ,i . Using (Eqns. 2.5.14 and
2.5.17), we obtain
− ( pi + 3 )
p +2  p + 1 λ 2 (mλi − 1)2 − κ λ2i  (16π / 3)κ λi ri  
σɶ sc ,i π N i ri 2 i  1+ i
+ 1 + . (2.5.18)
pi + 1 π 2 ri 2 [(mλi − 1)2 + κ λ2i ]2 
pi + 2 8π ( pi + 1)λ 
 
The mass scattering and absorption coefficients of drops and crystals in [cm2 g−1] or [m2 g−1] are
obtained by dividing by qLi. They can be expressed via the mean radius ri or via the effective
radii re often used in radiation calculations (given in (Eqn. 2.4.30)), re = r 3/r 2 = ( pi + 3) /( pi + 2 ) r i ,

σɶ sc ,i 3 pi + 1  pi + 1 λ 2 (mλ i − 1)2 − κ λ2i

σ λsci = = 1 +
qLi 4 ρi ri pi + 3  pi + 2 8π 2 ri 2 [(mλ i − 1)2 + κ λ2i ]2
− ( pi + 3 )
 (16π / 3)κ λ i ri  
+ 1+ , (2.5.19a)
 ( pi + 1)λ  

3 pi + 1  ( pi + 1)( pi + 3) λ 2 (mλ i − 1)2 − κ λ2i

σ λsci = 1 +
4 ρi re pi + 2  ( pi + 2) 3
8π re [(mλ i − 1)2 + κ λ2i ]2
2 2

− ( pi + 3 )
 ( pi + 2) 16πκ λ i re  
+ 1+ , (2.5.19b)
 ( pi + 1)( pi + 3) 3λ 

2.5. Cloud Optical Properties 37

− ( pi + 3 )
αɶ ext ,i 3 pi + 1   (16π / 3)κ λ i ri  
α Li = = 1 − 1 +  , (2.5.20a)
qLi 4 ρi ri pi + 3   ( pi + 1)λ  

− ( pi + 3 )
3 pi + 1   ( pi + 2) 16πκ λ i re  
α Li = 1 − 1 +  . (2.5.20b)
4 ρi re pi + 2   ( pi + 1)( pi + 3) 3λ  

The single scattering albedo now can be calculated as wl = ssc /s/sext , or 1 − wl = sabs /s
/sext .
Shown in Fig. 2.6 is the wavelength dependence of the mass absorption coefficient aLi calculated
using (Eqn. 2.5.20a), kli from Liou (1992), the index of gamma distribution ution pi = 6, and four mean
radii of 5, 10, 20, and 50 μm. One can see that for the small particles of 5 μm, the difference between
the maxima in the absorption bands near 4.5 μm, 6 μm, and 12–20 μm, and the minima in the trans-
parency windows near 5.5 m m and 8–12 m m reaches a factor of 2–3. With increasing size, this dif-
ference becomes smaller—i.e., the spectral dependence weakens and almost vanishes for r = 50 µm µ .
sc
Comparison of these mass scattering and absorption coefficients λ i and aLi obtained using ADT
with the corresponding coefficients calculated with Mie theory and the values of nl, kl tabulated
in Warren (1984) and Liou (1992) shows that the errors of the expressions (Eqns. 2.5.19a,b and
2.5.20a,b) for the SW spectrum mostly do not exceed 9–13%, and the errors at l < 2.4 m m do not
exceed 5%. These errors are much smaller than the errors that may occur in calculations of the cloud
radiative properties with some prescribed scattering and absorption coefficients that are independent
of temporal and spatial variations and cloud microstructure.
Some particular cases are useful for developing broadband parameterizations. For weak absorp-
tion, X λ = (16π / r λι /λ << 1 (i.e., kl < 1.5 × 10−2 in the SW region at l < 2.5 μm for drops or

0.14 rd = 5 µm
rd = 10 µm
LW absorption coefficient (m2 g–1)

0.12
rd = 20 µm
0.1 rd = 50 µm

0.08

0.06

0.04

0.02

0
4 6 8 10 12 14 16 18 20
Wavelength (µm)

Figure 2.6. Spectral dependence on the wavelength l of the LW absorption coefficient calculated
with anomalous diffraction theory; the droplet size spectra are gamma distributions with the mean
radii rd = 5, 10, 20 , and 50 m m and index
x p = 6.
38 Clouds and Their Properties

crystals with a radius of 5–10 μm), the expansion of (Eqns. 2.5.19a and 2.5.20a) by this parameter
up to second order yields
2
4πκ λ 2r ( p + 4)  4πκ λ i 
α Li = − , (2.5.21)
λρi 3 ρi ( pi + 1)  λ 
−2
3 pi + 1  1 pi + 1  2π ri (mλ i − 1)   λ
σ λsci = 1 +  
2 ρi ri pi + 3  2 pi + 2  λ  
2
λ 4πκ λ i 2r ( pi + 4)  4πκ λ i 
− + i . (2.5.22)
λρi 3 ρi ( pi + 1)  λ 

In bands with weak absorption and with small particles, when X λ = (16π / r λi /λ << 1, the major
contribution to the mass absorption coefficient aLi comes from the first term in (Eqn. 2.5.21), which
does not depend on the mean radius. For example, in the infrared window at l = 10 μm with kli ≈
5.1 × 10−2 (Warren, 1984; Liou, 1992), and ri = 10 μm, pi = 6, using (Eqn. 2.5.20a) for water drops
or small crystals with rw = 1 g cm−3 gives aLi ∼ 380 cm2 g−1, and an estimate with the approximate
(Eqn. 2.5.21) gives aLi ≈ 430 cm2 g−1—i.e., the error of (Eqn. 2.5.21) is ∼12%. In the bands with
strong absorption, (16π /3) i κ λ /λ ≥ 1, it follows from (Eqns. 2.5.19a and 2.5.20a) that

3 pi + 1 3 3
α Li ≈ σ λsc ≈ = = ω λ ≈ 0.5. (2.5.23)
4 ρi i pi + 3 4 ρi re 2 ρi De

This simple analytical limit corresponds to (Eqn. 2.5.2) or to a parameterization aLi(re) = aLi(re =
11 μm) × (11 μm /re) suggested in Stephens et al. (1990) for crystals in cirrus clouds, and its radius
dependence is similar to the parameterizations (Eqn. 2.5.2) by Slingo (1989) and Ebert and Curry
(1992).
These two limiting cases show that there are two different dependencies of the absorption coef-
ficient on the mean or effective radius in the bands with weak absorption or with sufficiently small
particles, Xl << 1, and in strong absorption bands or with large ge particles, Xl ≥ 1. In the first case,
aLi can be parameterized as a polynomial by ri or re, such as the linear function (Eqn. 2.5.21). In
the second case, aLi becomes a function of the inverse radius, 1/ ri or 1/re, as shown in (Eqn. 2.5.23)
and used in the parameterizations similar to (Eqn. 2.5.2). A rapid transition from one regime to
another can occur even at small changes of wavelengths due to increase in kli. In the example
considered earlier at l = 10 μm, we had Xl = 0.85 < 1, while a small shift to l = 11 μm with
arren, 1984) yields Xl = 3.77 >> 1 and (Eqn. 2.5.23) shows that α Li ∼ 1/r i
kli = 0.248 for ice (Warren,
in agreement with (Eqn. 2.5.2). An estimate with (Eqn. 2.5.23) gives aLi ∼ 540 cm2 g−1 for small
crystals with ri = 10 μm.
It is seen that (Eqns. 2.5.19a,b)–(2.5.23) predict dependence on the mean or effective radius similar
to the broad-band parameterizations (Eqns. 2.5.1 and 2.5.2) by Slingo (1989), Stephens et al. (1990),
Ebert and Curry (1992), Fu and Liou (1993), and others. Expressions (Eqns. 2.5.19a,b)–(2.5.21) in
various spectral regions or their expansions of by ri or re of the form (Eqn. 2.5.21)–(2.5.23) for vari-
ous wavelengths and models of the size spectra provide the functional form and coefficients for such
parameterizations. Note that due to the different functional dependencies of aLi on re or on 1/re, aLi
may change even at small changes of l or ref.
2.5. Cloud Optical Properties 39

Cloud emissivity ei can be written as

 zt 
εi 1 e  ∫ α Li [ri ( z)]
z qli ( z ) dz  (2.5.23a)
 zb 
≈ 1 − exp[−α Li (ri ) (L
Lwp)i ], (2.5.23b)

where z is the height in the cloud, zb and zt are the cloud boundaries (and the second equation is
valid if aLi weakly depends on height), (Lwp)i is the liquid or ice water path, and aLi is described by
(Eqn. 2.5.20a,b). The formulae for emissivities are used in cloud and climate models and in remote
sensing techniques for parameterization of longwave radiation. This equation with (Eqn. 2.5.20a,b)
allows determination of the effects on ei of the cloud microstructure and phase state. It also enables
determination of the different emissivities in the different channels of remote sensing devices. The dif-
ferent dependence of aLi on re at various wavelengths or bands may substantially influence the values
of ei. As seen from (Eqn. 2.5.23b), emissivity decreases with increasing ri and constant water path.
Another form of the volume absorption coefficient αɶ abs ,i is obtained by integration of the van de
Hulst absorption factor (Eqn. 2.5.8b) with the gamma distribution (Eqn. 2.5.11), which yields
∞
 2π r 
αɶ abs ,i ∫ πr K
2 H
f (r )dr
0
abs
 λ  i i

pi + 2  pi + 1  2   ψ 
− ( pi + 2 )
pi + 1  2   ψ 
− ( pi +1)
 
= π N i ri 2 1 +    1 +  +  
2 
1 +   − 1 ,
pi + 1  pi + 2  ψ   pi + 1  pi + 2  ψ   pi + 1   
  
(2.5.24)

where ψ = 8πκ
πκ λ i r / pi + 1)λ ]. The corresponding mass absorption coefficient is
− ( pi + 2 )
αɶ abs ,i 3 pi + 1  pi + 1  2   ψ 
α (H )
= = 1 + 1+
4 ρw r i + 3  pi + 2  ψ   pi + 1 
Li
qLi

p + 1  2   ψ 
− ( pi +1)
 

+ i  
2  
1 +   − 1 . (2.5.25)
pi + 2  ψ   pi + 1  
  

Its value at small kl or small r—i.e., at ψ <<1—is obtained by expanding ψ . Keeping the terms up to
the 3rd order by ψ , we obtain

4πκ λ i
α Li( H ) ≈ , (2.5.26)
λρi

which coincides with the major first term in the expansion (Eqn. 2.5.21) of the absorption coefficient
(Eqn. 2.5.20a) obtained with the interpolation absorption efficiency (Eqn. 2.5.4). The analogous ana-
lytical expressions for the extinction and absorption coefficients of polydisperse ensembles of the
volume equivalent spheres were obtained by Ackerman and Stephens (1987) and Stephens et al.
(1990) in a somewhat different form, as a real part of the two complex-conjugated expressions.
There have been many refinements to anomalous diffraction theory and its combinations with the
other methods for calculation of the optical coefficients. Stephens (1984) applied ADT for calculation
of the optical properties of circular cylinders that may approximate columnar crystals. Ackerman and
40 Clouds and Their Properties

Stephens (1987) incorporated into ADT a correction due to refraction and found that this modified
anomalous diffraction theory (MADT) does not appreciably increase the accuracy of the extinction
factor Kext over ADT but improves the accuracy of the absorption factor Kabs. Van de Hulst’s (1957) and
Bryant and Latimer (1969) generalized the anomalous diffraction theory for a variety of nonspherical
particles. The extinction and absorption cross-sections for this case can be written as integrals over the
projected area, A, of a particle on the plane perpendicular to the direction of the incoming radiation,

  2πκ λ i di   2π 
σ ext = 2 ∫ 1 − exp − cos  di (mλ i − 1)   dA , (2.5.27)
A
 λ   λ 
σ abs ∫ [1
A
exp( 4πκ
πκ λ i di /λ )] dA . (2.5.28)

Here di is the geometrical path of an individual ray through the particle. Chylek and Klett (1991a,b)
applied this version of ADT to hexagonal columns and plates that can approximate ice crystals in
clouds, integrated over the angles that determine di, and derived the extinction and absorption cross-
sections for these crystal types. Chylek and Videen (1994) integrated these cross-sections with the
gamma distributions and derived expressions for the extinction and absorption coefficients for the
polydisperse ensembles of crystals. These solutions considered only horizontal orientation of the col-
umns and plates and with the beam of incoming radiation perpendicular to the long axes of a column
or hexagonal side of a plate.
Mitchell and Arnott (1994, hereafter MA94) have chosen a somewhat different method following
Bryant and Latimer (1969). They suggested that for randomly oriented crystals tumbling through
space, the dependence on the angles between incident radiation and crystal axes is smoothed, and the
absorption efficiency is simplified and is reduced to the integrand in (Eqn. 2.5.28), then

K abs = (1 / A)σ abs = 1 πκ λ i i /λ ) ,

exp( 4πκ
= 1 − exp[−4πκ λ i (Vi / Ai ) /λ ] , (2.5.29)

where the geometrical path di is expressed via the crystal volume Vi and the projected area Ai as
di = Vi/Ai. The corresponding absorption cross-section is

σ abs Ai {1 exp[ 4πκ λi (Vi / i ) /λ ]]}.

πκ (2.5.30)

It is seen that (Eqn. 2.5.29 and Eqn. 2.5.30) generalize (Eqn. 2.5.4 and Eqn. 2.5.6) for non-spherical
particles and revert to the spherical particular case when di = Vi/Ai = (4/3)ri. The two limits of
(Eqn. 2.5.30) for weak and strong absorption or for small and large particles (4pklidi /l << 1 and >> 1,
respectively) reduce to the same two expressions in (Eqn. 2.5.7) as in the spherical case that deter-
mine the volume-dominated and surface-dominated absorption. For evaluation of the absorption
coefficient, MA94 parameterized the volume and projected area for various crystal habits and various
size regions based on the experimental data, and using some equations from Takano and Liou (1989),
approximated crystal size spectra with gamma distributions and derived analytical expressions for
the crystal absorption coefficient in terms of the incomplete gamma functions. For the extinction
coefficient, MA94 assumed the volume equivalent spheres, integrated with gamma distributions,
and obtained expressions similar to those in Stephens et al. (1990). An assumption in Mitchell and
Arnott (1994) on the chaotic crystal orientation is not always justified. It is known that ice crystals are
generally not randomly oriented in space. Large ice crystals fall preferentially with their major axis
2.5. Cloud Optical Properties 41

oriented horizontal, whereas smaller crystals may fall randomly oriented, or also exhibit preferred
orientations depending on their Reynolds number (Landau and Lifshitz, v. 6, 1959; Sassen, 1980;
Pruppacher and Klett, 1997; Cotton et al., 2011).
Several methods have been developed for calculation of the optical properties of nonspherical
crystals. Mischenko et al. (1991, 1996) performed detailed calculations based on the T-matrix of light
scattering and the exact solutions of electrodynamics equations. Fu (1996) calculated the SW single
scattering properties of hexagonal ice crystals using an improved geometric ray-tracing program
that can produce accurate results for size parameters larger than 15. Then, the crystal extinction and
absorption coefficients σ ext , σ abs , and the asymmetry factor g were averaged over the selected 28
crystal size spectra observed in tropical and midlatitude cirrus clouds and were parameterized as the
linear and cubic polynomials of the generalized effectivee size De:

σ ext = IWC (a0 + a1 /De ) , (2.5.31a)

2 3
1 − ωɶ = (σ abs /σ ext ) = b0 + b1 De + b D + b3 D ,
e e (2.5.31b)
2 3
g = c0 + c1 De + c D + c3 D ,
e e (2.5.31c)

where the overbar denotes averaging over the size spectra. The coefficients of this parameterization
were given in Fu (1996) for 25 and 6 bands. Fu et al. (1998) developed a similar parameterization for
the infrared radiative properties of cirrus clouds, using for randomly oriented hexagonal ice crystals
a composite scheme. This scheme employed a linear combination of single-scattering properties
from four methods: the Mie theory, the anomalous diffraction theory, the geometric optics method
(GOM), and the finite-difference time domain technique, which is accurate for a wide range of size
parameters. Similar refinements in calculations of the optical parameters of nonspherical crystals
were done by Yang et al. (2001) using the improved geometric optics approximation, and in a number
of subsequent works that are continuing at present.
Mitchell et al. (2006, hereafter M06) calculated extinction efficiencies Kext for nonspherical crys-
tals using the anomalous diffraction approximation (ADA) corrected for tunneling effects. Photon
tunneling accounts for radiation beyond the physical cross-section of a particle that is either absorbed
or scattered outside the forward diffraction peak. This correction results in multiplication of the
efficiencies or optical coefficients by the tunneling efficiency factor Te. Tunneling factors Te can
range from 0 to 1.0, with zero indicating no tunneling and 1.0 corresponding to spheres and the
maximum tunneling contribution. This new analytical form of ADA was referred to as modified ADA
or MADA. M06 compared MADA for a laboratory-grown ice cloud with measurements of Kext and
Kabs over the wavelength range 2–14 μm, and compared MADA with three popular schemes used
for predicting the radiative properties of cirrus clouds, Ebert and Curry (1992), Fu et al. (1998), and
Yang et al. (2001).
Fig. 2.7 shows a comparison of the MADA predictions from M06 (the data taken from M06) with
the scheme by Ebert and Curry (1992, EC92) and some its modification for the atmospheric window
region 8.0–12.5 μm. The whole curve from M06 (spheres) lies lower than the EC92 curve (triangles).
It is not surprising because a tunneling efficiency Te = 0.6 was used in M06 corresponding to hex-
agonal columns, while parameterization in Ebert and Curry was fitted for volume-equivalent spheres
with Te = 1. The curve “EC92, hex. col.” was calculated by multiplication of the equation from Ebert
and Curry ([Eqn. 2.5.2] here) by Te = 0.6, which corresponds to the same crystal shape of hexagonal
42 Clouds and Their Properties

M06, MADT, hex. col.

LW absorption coefficient, crystals (m2 g–1)

0.1
EC92, equiv. sph.
EC92, hex. col.
Eq. (2.5.23)

0.01

1E-3
0 50 100 150 200 250 300 350
Crystal equivalent diameter De(µm)

Figure 2.7. Longwave absorption coefficient aLi for crystals in the wavelength band 8−12 μm
calculated with various methods. Modified anomalous diffraction theory (MADT), Mitchell et al.
(2006), hexagonal columns (M06); Ebert and Curry (1992), equivalent spheres (triangles, EC92);
Ebert and Curry (1992) corrected for hexagonal columns, multiplied by Te = 0.6 (EC92, hex. col.,
crosses); calculation with Equation (2.5.23) of this section, aLi = (3/2riDe) with ri = 0.916 g cm−3.

columns as in M06. It is seen that EC92, hex. col., and M06 almost coincide, except for the region of
the smallest crystals. Also plotted in Fig. 2.7 is the absorption coefficient calculated with the simple
asymptotic limit (Eqn. 2.5.23) of the usual ADT described earlier. This parameterization also almost
coincides with both M06 and EC92, hex. col., because it accounts for the sufficiently strong absorp-
tion averaged over the window, being closer to EC92, hex. col., for small sizes and to M06 for larger
sizes. This example illustrates that various parameterizations may provide comparable accuracy.
These fine features of the optical coefficients can be masked in natural clouds by the tremendous
spatial and temporal variability of cloud microphysical properties. The absorption and scattering
coefficients measured in cirrus clouds varied by more than one order of magnitude and the reason for
this was not quite clear until recently (e.g., Stephens et al., 1990; CIRRUS-2002). Fig. 2.8 depicts
vertical profiles of the mass and volume scattering coefficient at l = 0.5 μm and LW absorption coef-
ficient calculated with ADT using equations of the type (Eqns. 2.5.17)–(2.5.20a) for a typical mid-
latitude cirrus cloud in the layer 6–9.5 km simulated in Khvorostyanov and Sassen (1998a,b, 2002)
with a 2D cloud model with spectral bin microphysics.
The properties of this cloud were similar to those observed in cirrus clouds described in Sassen
et al. (1989). Both mass coefficients decrease from cloud top to bottom by an order of magnitude
due to the inverse size dependence and increasing downward crystal size. Further, they exhibit a sig-
nificant horizontal variability due to variations in crystal sizes caused by the cellular convection and
horizontal variability of vertical velocity as simulated in Khvorostyanov and Sassen (1998a,b, 2002).
2.5. Cloud Optical Properties 43

10 10

9 9

Height (km)
Height (km)

8 x = 9 km 8
x = 33 km
7 x = 69 km 7
x = 84 km

6 6
0 500 1000 1500 2000 2500 0.0 0.2 0.4 0.6 0.8
Mass SW scattering coefficient, Volume SW scattering coefficient,
λ=0.5 µm (cm2 g–1) λ=0.5 µm (km–1)
(a) (b)

10 10

9 9
Height (km)

Height (km)

8 8

7 7

6 6
0 200 400 600 800 0.0 0.1 0.2 0.3
Mass LW absorption coefficient (cm2 g–1) Volume LW absorption coefficient (km–1)
(c) (d)

Figure 2.8. Vertical profiles of the mass and volume scattering coefficients in the SW region
(l = 0.5 μm) and LW absorption coefficients (l = 10.75 μm) in a midlatitude cirrus cloud with
boundaries of 6 and 9.5 km at 4 horizontal locations, x = 9, 33, 64, and 84 km. Modeling results
from Khvorostyanov and Sassen (1998b, 2002), with changes.

The maxima of volume coefficients are located closer to the middle cloud layer with a maximum of
IWC, and exhibit even greater horizontal variability. This example explains the wide variability of the
measured optical coefficients and shows a necessity of fine vertical and horizontal resolution in the
modeling of microphysical and radiative cloud properties.
The equations for the cloud extinction, scattering, and absorption coefficients described in this
section can be used in the radiative codes of cloud and climate models of various complexity, both
with bulk parameterization of cloud microphysics (e.g., Fowler et al., 1996; Lohmann et al., 1999;
Mokhov et al., 2002; Morrison et al., 2005a,b; Sud et al., 2007, 2009; Gettelman et al., 2008;
Morrison and Gettelman, 2008; Klein et al., 2009; Yun and Penner, 2012) and with spectral bin
microphysics (e.g., Kondratyev et al., 1990a,b; Khvorostyanov, 1982, 1995; Jensen et al., 1994, 2005;
Feingold et al., 1994; Khvorostyanov and Sassen, 1998b, 2002; Khvorostyanov et al., 2003, 2006;
Fridlind et al., 2004; Krakovskaia and Pirnach, 2004; Monier et al., 2006). Such an approach allows
us to account for the interactions of evolving cloud microstructure and cloud radiative properties.
44 Clouds and Their Properties

Appendix A.2 for Chapter 2. Evaluation of the Integrals

with Lognormal Distribution

The lognormal size spectrum of aerosol fa(ra) by the radii ra can be presented as

Na  ln 2 (ra /ra 0 ) 
fa (ra ) = exp  − , (A.2.1)
2π (ln σ a )ra  2 ln 2 σ a 

where Na is the aerosol number concentration, ra0 is the mean geometric radius and sa is the disper-
sion of the spectrum. The moment M(n) is
∞ ∞
N  ln 2 (ra /ra 0 ) 
M (n) = ∫ r n
2π ( σ a ) ∫0
n −1
= r exp − dr
dr. (A.2.2)
0  2 ln 2 σ a 

Introducing a new variable

ariable x = r/r0, (Eqn. A.2.2) can be rewritten as
∞
N a ran0  ln 2 x 
M ( n )= ∫
2π (ln σ a ) 0
x n −1 exp  −
 2 ln σ a
2 xdx.

(A.2.3)

After introducing a new variable z = (ln x ) /( 2 ln a ) and transformations, this becomes

N a ran0 ∞

=
M (n) =
π ∫ exp(n
−∞
σ a )z −
2 (ln σ − z2 ) d
dz . (A.2.4)

This integral is simplified with the new variable t = n ln σ a / 2 , and then

N a ran0  n 2 ln 2 σ a  ∞
M (n) =  ∫ exp[− ( z − t ) dz .
2
exp  (A.2.5)
π  2 −∞

The last integral

gral after substitution z − t = z' is reduced to the Gaussian integral
∞

∫ exp(−− z ' ) dz ' == π.

2
π (A.2.6)
−∞

(Gradshteyn and Ryzhik, 1994) and we obtain the n-th moment of the lognormal distribution

 n 2 ln 2 σ a 
M ( n ) = N a ran0 exp   . (A.2.7)
 2

All the particular moments are obtained by prescribing n the corresponding values, e.g., n = 1, 2, 3.
3
Thermodynamic Relations

This chapter describes the major thermodynamic functions and relations that provide the foundation
for the following chapters.

3.1. Thermodynamic Potentials

The state of a thermodynamic system is characterized by the three thermodynamic variables, pres-
sure p, temperature T, and volume V. For a homogeneous system of constant composition, these three
variables are related by an equation of state, so that only two of variables are independent. Entropy
Sh , internal energy E, enthalpy H, and the Gibbs function G are also state variables, and depend only
on the current state of the system and not on the process by which the system acquired that state.
Thermodynamic variables and functions are called extensive if they depend on mass (e.g., volume),
and intensive if they do not depend on mass and can be defined for every point of the system (e.g.,
temperature, density). The intensive variables are related to a unit mass or to a mole. The thermody-
namic system is further characterized by its chemical composition and phase state. If the composition
and phase state of a system is variable, there is an additional characteristic, the chemical potential m.
The processes occurring in a thermodynamic system can be described using scalar functions of the
thermodynamic variables called the thermodynamic potentials. We will use the following extensive
potentials, denoted by capital letters: internal energy E, enthalpy H, Helmholtz free energy F, the
Gibbs free energy G, and the Landau potential W. The corresponding intensive variables are obtained
by reducing to the corresponding mass. The corresponding intensive quantities are denoted here by
lowercase letters; the molar quantities are obtained by dividing extensive quantities by the number
of moles n (e.g., ĕ = E/n, h = H/n, f = F/n, g = G/n, v = W /n), and specific quantities are related to
a unit mass. For the molar potentials, it is convenient to use the molar entropy sh = Sh /n and molar
volume v = V/n.
The internal energy E is a measure of energy stored in a system and characterizes its internal
state—e.g., speed of the molecules, internal motion in the molecules (rotation and vibration), etc. The
first law of thermodynamics can be written for a reversible process as
c
dE = dQ + dW + ∑ µ dn , k k (3.1.1)
k =1

where Q is the heat and W is the expansion work done on the system that can be expressed for quasi-
static changes via the temperature T, entropy Sh, pressure p, and volume V as:

dQ = TdSη , dW = − pdV . (3.1.2)

45
46 Thermodynamic Relations

mk and nk are the chemical potential and the number of moles of the k-th chemical component.
Equation (3.1.1) shows that the chemical potential mk characterizes a change dE when the number of
moles changes by dnk. Now E can be specified as
c
dE = TdSη − pdV + ∑ µ dn k k . (3.1.3)
k =1

Integration at the constant intensive variables T, p, and mk yields

c
E = TSη − pV + ∑µ n k k . (3.1.3a)
k =1

The other thermodynamics potentials to be used—the heat function or enthalpy H, the Helmholtz
free energy F, the Gibbs free energy G, and the Landau potential W —are related to E, p, V, T, and Sh :
H = E + pV , (3.1.4)
F = E - TSh , (3.1.5)
G = E + pV − TSη = H − TSη , (3.1.6)

Ω = E − TSη − µ N = F − µ N ,
W (3.1.7)

where N is the total number of particles in the system. The differential of the enthalpy H in a system
with a variable number of moles is:
c
(3.1.8)
dH = TdSη + Vdp + ∑ µ dn k k .
k =1

This equation allows calculation of the natural variables of E: T, V, and mk

 ∂H   ∂H   ∂H 
T =  , V = , µk =   , (3.1.9)
 ∂ Sη  p ,nk  ∂ p  S η , nk
 ∂ nk  S , p , µi
h

where the subscripts denote constant corresponding values and mi ≠ mk. The differential of the Helm-
holtz free energy is
c
(3.1.10)
dF = − Sη dT − pdV + ∑ µ dn k k .
k =1

This allows calculations of Sh, p, and mk using F:

 ∂F   ∂F   ∂F 
Sη = −  , p = − , µk =  . (3.1.11)
 ∂T  V ,nk  ∂V  T ,nk 
 ∂nk  T ,V ,ni

The relation for p is used in Section 3.4 for derivation of the equation of state, and the equations for
mk are used in Section 3.10 and in subsequent chapters for evaluation of the chemical potentials of the
systems with variable numbers of particles.
The differential of the Gibbs free energy is
c
dG = − Sη dT + Vdp + ∑ µ dn k k . (3.1.12)
k =1
3.1. Thermodynamic Potentials 47

This gives the relations for Sh, V, and mk

 ∂G   ∂G   ∂G 
Sη = −  , V = , µk =  . (3.1.13)
 ∂T  p ,nk  ∂ p  T ,nk 
 ∂nk  T , p ,ni

The differential of W includes mk as a variable and is

c
dΩ = − Sη dT − pdV −
dW ∑ n dµ k k . (3.1.14)
k =1

This gives the relations

 ∂Ω   ∂Ω   ∂Ω 
Sη = −  , p = − , nk = −   . (3.1.15)
 ∂T  V ,nk  ∂V  T ,nk  ∂ µ k  T ,V

This allows a particular calculation of nk, therefore W is especially useful for calculations of the sta-
tistical distributions in systems with a variable number of particles, as shown in Section 3.2.
The molar Gibbs free energy is related to the chemical potential mk

 ∂G 
gk =   = µk . (3.1.16)
 ∂ nk  T , p , n

That is, the chemical potential is equal to the molar Gibbs free energy. Similar relations can be writ-
ten for the other potentials. Using (Eqn. 3.1.16), the Gibbs energy G can be rewritten as the sum over
the components
c c
G = ∑n µ = ∑n g
k k k k . (3.1.17)
k =1 k =1

Now, using these definitions and relations, we can introduce several useful quantities and equations.
Equation (3.1.8) shows that H characterizes the heat content in the system if p = const, and all
nk = const, and h characterizes the heat content per one mole at p = const. At constant pressure,
dp = 0, and a constant number of moles, dnk = 0, it follows from (Eqn. 3.1.8) that

 ∂ Sη   ∂ Sη 
dH = dQ = T  dT = C p dT , Cp = T  , (3.1.18a)
 ∂T  p ,nk  ∂T  v ,nk

where Cp is the heat capacity at constant pressure. It characterizes an increase in enthalpy or the heat
of a system with an increase of the temperature by one degree at constant pressure. A similar relation
is valid also for the molar or specific quantities at p = const,

 ∂sη   ∂sη 
dh = dq = T  dT = c p dT , cp = T  , (3.1.18b)
 ∂T  p  ∂T  p

For the process with constant volume, dV = 0, and nk = const, dnk = 0, (Eqn. 3.1.3) for dE reduces to

 ∂ Sη   ∂ Sη 
dE = dQ = T  dT = Cv dT , Cv = T  . (3.1.19a)
 ∂T  v ,nk  ∂T  v ,nk
48 Thermodynamic Relations

where CV is the heat capacity at constant volume. Equation (3.1.19a) shows that it characterizes
increase in the internal energy or heat of the body if the temperature increases by one degree at con-
stant volume. For a system of one mole or unit mass with just one substance, (Eqn. 3.1.3) becomes
deɶ = dq + dw = Tdsη − pdv , (3.1.19b)

where sh and v are the entropy and volume per unit mole or mass. A relation similar to (Eqn. 3.1.19a)
is valid also for the molar or specific quantities with v = const,

 ∂sη   ∂sη 
deɶ = dq = T  dT = cv dT , cv = T  , (3.1.19c)
 ∂T  v  ∂T  v

where cv is the heat capacity at constant volume per unit mole or mass. It was shown experimentally
that for an ideal gas, (∂eɶ / ∂ v )T = 0 (i.e., eɶ = eɶ (T )) and (∂h/∂p)T = 0 (i.e., h = h(T)). These equations
are used in Section 3.11 for consideration of adiabatic processes.
Two additional useful relations can be obtained for the molar entropy sh and molar volume vk. It
follows from (Eqns. 3.1.13 and 3.1.12) that

 ∂µk  ∂  ∂G 
 ∂T  =
∂T  ∂nk  p ,n
p , nk ≠ i k ≠i

∂  ∂G   ∂ Sη 
=   = −  = − sη k . (3.1.20)
∂ n k ∂T p , nk ≠ i  ∂ n k  T , p , nk ≠ i

Thus, the derivative ∂mk /∂T gives the molar entropy sη k . Similarly, the derivative ∂mk /∂p gives the
molar volume vk:

 ∂µk  ∂  ∂G 
 ∂p  p  ∂nk  T ,n
=
T , nk ≠ i
∂
k ≠i

∂  ∂G   ∂V 
=  = vk . (3.1.21)
∂nk  ∂p  T ,n
=
k ≠i
 ∂ n k  T , nk ≠ i

The molar Gibbs free energy gk, chemical potential mk, and enthalpy hk are related similarly to
(Eqn. 3.1.6) for G:
µ k = gk = hk − Tsη k , hk = µ k + Tsη k . (3.1.22)

This expression allows us to obtain a relation between mk and hk using (Eqn. 3.1.20), ∂ µ k / ∂T = − sη k ,

∂  µk  1 µ  ∂µ  
  = −  k −  k 
∂T  T  p ,ni ≠ k TT  ∂T   p , n
i≠k

1  µk  1  µ k + Tsηk  h
=−  + sηk  = −   = − k2 . (3.1.23)
T T  T  T  T

A similar relation follows from (Eqn. 3.1.21) for mk / T and vk

 ∂( µ k / T )  1  ∂µ  v (3.1.24)
 =  k = k.
∂ p  T ,n T  ∂ p  p,n T
i≠k i≠k
3.2. Statistical Energy Distributions 49

Equations (3.1.23 and 3.1.24) will be used in derivations of the conditions of equilibrium and several
fundamental laws in the following sections.
A useful relation can be derived from the expressions (Eqns. 3.1.3 and 3.1.3a) for the energy E.
Taking the total differential of (Eqn. 3.1.3a)
c c
dE = TdSη + Sη dT − pdV − Vdp + ∑ µ dn + ∑ n dµ
k k k k , (3.1.25)
k =1 k =1

and subtracting (Eqn. 3.1.3) from this expression yields

c

∑ n dµ k k = − Sη dT + Vdp . (3.1.26)
k =1

This is the Gibbs–Duhem relation. It can be written in another form introducing the mole fractions
for the k-th substance
c
x k = nk / ∑ nk . (3.1.27)
k =1

Dividing (Eqn. 3.1.26) by Snk, we obtain this relation in terms of mole fractions
c

∑ x dµ k k = − sη dT + vdp , (3.1.28)
k =1

where sh and v are the molar entropy and volume. This relation is simplified for an isothermic (T = const)
and isobaric (p = const) process,
c

∑ x dµ k k = 0. (3.1.29)
k =1

The Gibbs–Duhem relation can be a particularly useful tool in calculations and analyses of the labo-
ratory experiments when it is necessary to relate the properties of various substances—e.g., solute
and solvent as will be illustrated in Section 3.6 and in Chapter 11 on aerosol phase transitions.

3.2. Statistical Energy Distributions

There are five basic statistical distributions that play fundamental roles in statistical physics. The
Gibbs distribution was derived by Gibbs in 1901 for classical statistics, which assumes a continuous
energy spectrum. The Gibbs distribution was subsequently generalized for the quantum case with a
discrete energy spectrum and for the combined mixed continuous and discrete energy. The Gibbs dis-
tribution is the most general of the statistical distributions; the other four distributions can be derived
from the Gibbs distribution, as shown next.

3.2.1. The Gibbs Distribution

The Gibbs energy distribution for a thermodynamic system can be obtained from the micro-canonic
distribution. For a system having a constant number of particles at a quantum energy level n with
energy En, the micro-canonic distribution is

 F − En 
wnN = exp  , (3.2.1)
 kT 
50 Thermodynamic Relations

where k is the Boltzmann’s constant, F is the Helmholtz free energy, and wnN is the probability of
this state. The sum of all these probabilities should equal unity, thus the normalization condition is

 F   − En 
∑w nN
 kT  ∑
= exp  exp 
 kT 
= 1. (3.2.2)
n n

This yields

∑ exp 
− En   −F 
Z =  = exp  . (3.2.3)
n kT  kT 

The ensemble described by the distribution (Eqn. 3.2.1) is called the canonical ensemble, and the
quantity Z is called the statistical sum or the canonical partition function. The free energy F now can
be expressed via the statistical sum Z

F = − kT ln Z . (3.2.4)
This form for F is used in thermodynamical applications of the Gibbs formula (Eqn. 3.2.1), in par-
ticular, for derivation of the equation of state, as will be illustrated further on.
In classical physics with a continuous energy spectrum, the Gibbs distribution is

 F − E ( p, q) 
dρ ( p, q) = ρ ( p, q)dp dq = exp   d Γ , (3.2.5)
 kT
where p and q are generalized coordinates, their number is s, dpdq is the differential element of the
phase space—i.e., dpdq = (dp1dp2 . . . dps)(dq1dq2 . . . dqs), dΓ = dpdq /(h)s is the number of states in
this differential element of the phase space, h is the Planck constant, and it plays the role of an elemen-
tary cell in the phase space.
The differential form of the Gibbs distribution in the quasi-classical case is

 F − En ( p, q) 
dwn ( p, q) = exp 
  d Γ. (3.2.6)
kT

The form (Eqn. 3.2.6) is written for the quasi-classical case and implies that the energy En(p, q) has
two components: the continuous quasi-classical (e.g., the kinetic and potential energy of the motion
of gas molecules) and the internal energy that may have quantum levels (e.g., vibrational and rota-
tional) indicated by the subscript “n”.
From the normalization condition

∑ ∫ dw ( p, q) = 1,
n (3.2.7)
n Γ

we obtain F in the quasi-classical case

 − En ( p, q) 
F = − kT ln ∫ exp   d Γ. (3.2.8)
 kT

The system with a variable number of particles N is called the grand canonical ensemble. The Gibbs
distribution for the grand canonical ensemble is

 Ω + µ N − EnN 
wnN = exp   (3.2.9)
 kT
3.2. Statistical Energy Distributions 51

where wnN is the differential probability of the energy EnN at quantum level n with the number of par-
ticles N, and W is the Landau thermodynamic potential (Eqn. 3.1.7). The normalization condition is

 Ω + µ N − EnN 
∑∑w nN = ∑ ∑ exp  kT
 = 1. (3.2.10)
N n N n

Equation (3.2.10) gives for W

  µN   E 
Ω = − kT ln ∑  exp 
 kT  ∑
exp  − nN   . (3.2.11)
N  n
 kT  

This equation defines W as a function of T, m, N. The number of particles N in each state n can be
calculated as ∂W/∂m.

3.2.2. The Maxwell Distribution

In classical statistical mechanics, the energy E(p, q) can be presented as a sum of two terms, kinetic
energy Ekin(pm) that depends only on momentum pm, and potential energy Upot(q) depending only on
coordinate q. We can choose pm and q as generalized coordinates and write

E ( pm , q) = K kin ( pm ) + Upot (q) . (3.2.12)

Then, the energy distribution is factorized

Ekin ( pm ) U pot ( q )
− −
dw( pm , q) = AG e kT
e kT
= dw p ( pm )dwq (q). (3.2.13)

where AG is the normalization constant, and dwp and dwq are the corresponding energy distributions
by momentum and coordinates
Ekin ( pm )
−
dw p ( pm ) = a p e kT
dpm , (3.2.14)
U pot ( q )
−
dwq (q) = aq e KT
dq . (3.2.15)

The constants ap and aq are determined from the conditions that each of these probabilities should be
normalized to unity.
The kinetic energy of an atom or molecule with mass m is Ekin = ( px2 + py2 + pz2 ) /2m , where px,
py, and pz, are the Cartesian components of the momentum, then

 px2 + py2 + pz2 

dw p ( pm ) = a p exp  −  dpx dpy dpz . (3.2.16)
 2mkT 

The normalizing constant is calculated in Appendix A.3. It is a p = (2π mkT )−3/2, and the momentum
distribution is

 px2 + py2 + pz2 

dw p ( pm ) = (2π mkT )−3/ 2 exp  −  dpx dpy dpz . (3.2.17)
 2mkT 
52 Thermodynamic Relations

It is convenient sometimes to use instead of (Eqn. 3.2.16) the momentum distribution dwɶ p ( pm ) with
another normalization, aɶ p = 1:

 px2 + py2 + pz2 

dwɶ p ( pm ) = exp  −  dpx dpy dpz . (3.2.17a)
 2mkT 

It is clear that the integral of this distribution is equal to a −p1 = (2π mkT )3/2 .
Transformation to the velocity distribution can be done using the relations dpx,y,z = mdvx,y,z. Then,
we obtain from (Eqn. 3.2.17) in the Cartesian coordinate system in the velocities space

 m 
3/ 2
 m( v x2 + v y2 + vz2 ) 
dwv ( v x , v y vz ) =  exp  −  dv x dv y dvz , (3.2.18)
 2π kT   2 kT 
This is the Maxwell distribution derived by Maxwell in 1860. In the polar coordinate system of the
velocities space with the polar angles q, j, and velocity v it converts into
3/ 2
 m   mv 2  2
dwv ( v ,θ ,ϕ ) =  exp  − v sinθ dθ dϕ dv . (3.2.19)
 2π kT   2 kT 

The normalization constant av = (m/2pkT)3/2 for (Eqns. 3.2.18 and 3.2.19) is calculated in Appendix A.3.
The Maxwell distribution for water vapor normalized to the molecular concentration cv = rv /mw in this
polar coordinate system can be derived in a similar way or is obtained just by multiplication by cv:
3/ 2
 mw   m v2 
fv ( v )dv = cv  exp  − w  v 2 sinθ dθ dϕ , (3.2.20)
 2π kT   2 kT 

where mw is the mass of a water molecule and rv is the vapor density. The Maxwell distribution is
used in Chapter 5 to evaluate the kinetic molecular flux to the drops and crystals.

3.2.3. The Boltzmann Distribution

The Boltzmann distribution is applied to the ideal gas, whereby interaction among molecules can be
neglected. This implies that the interaction is really small at any distances, or the density of the gas
is small. A further requirement is that the quantum mechanical interactions caused by the particles’
identity can be also neglected. All of these requirements are fulfilled if the average number of par-
ticles nk in each energy state e k is small, nk << 1. If particle interactions can be neglected, then the
Gibbs distribution can be applied to individual molecules:

nk = aB exp(− ε k /kT ) . (3.2.21)

The normalizing coefficient aB can be expressed through the thermodynamic parameters of the gas.
The condition nk << 1 is equivalent to ek >> kT (i.e., this distribution becomes invalid at sufficiently
low temperatures).
This equation can be also directly derived from the Gibbs distribution (Eqn. 3.2.9) for a given
quantum state k. Since interaction among the molecules can be neglected, their total energy is a sum
of the molecular energies, E = nk ε k . Assuming also N = nk, and W = Wk for the given k-state, we can
write from (Eqn. 3.2.9)

 Ω k + n k ( µ − ε nk ) 
wnk = exp  . (3.2.22)
 kT 
3.2. Statistical Energy Distributions 53

When particles are absent at any state k, then nk = 0, and the condition wnk = exp(Ω k /kT ) = 1 is the
probability of such a state. Since nk << 1, this means that exp(Ω k /kT ) ≈ 1, that is, Wk ≈ 0. Then, the
Boltzmann distribution to find one particle in k-th state (nk = 1) can be simplified as

 µ − εk 
w1 = exp  . (3.2.23)
 kT 

The mean number of particles in this state is

 µ − εk 
nk = ∑w nk nk = w1 = exp 
 kT  , (3.2.24)
nk

since the probability for one particle coincides with w1. This expression is the Boltzmann distribution
(derived by Boltzmann in 1877).
For the classical case, the Boltzmann distribution can be written for the phase space of the general-
ized coordinates p, q as

 µ − ε ( p, q) 
dn( p, q) = exp   dpdq . (3.2.25)
 kT

If the energy of a molecule can be presented as a sum of the potential and kinetic energies as in
(Eqn. 3.2.12), then the probability is factorized into two dependencies by momentum pm or velocity
and by coordinates q as in (Eqn. 3.2.13):
Ekin ( pm ) U pot ( q )
− −
dN( pm , q) = AG e kT
e kT
= dNp ( pm ) dN q (q). (3.2.26)

If the gas is not located in an external field or if this field depends only on coordinates, then the
kinetic part dNp(pm) is described by the Maxwell distribution discussed earlier. If the generalized
coordinates q are Cartesian (x, y, z), the distribution dNq(q) = dNq(x,y,z) is
U pot ( x , y , z )
−
dN q ( x , y, z ) = n0 e kT
dV , (3.2.27)

where n0 is a normalization parameter. Since dNq(x,y,z) = n(x,y,z)dV with n(x,y,z) being the density of
the molecules, this gives for the spatial distribution n(x,y,z)
U pot ( x , y , z )
−
n ( x , y , z ) = n0 e kT
. (3.2.28)

This equation determines the concentration of the molecules in the point (x,y,z). Equations (3.2.27)
and (3.2.28) are called the Boltzmann distribution.
In particular, in the gravitational field directed along the z-axis, the potential energy is U = mgz, and
the Boltzmann distribution describes the known barometric formula for the density of the molecules
mgz
−
n ( z ) = n0 e kT
, (3.2.29)

where n0 is the density at the surface level. This equation can be rewritten for the gas density r = mn.
By multiplying the numerator and denominator in the exponent by Avogadro’s number, NAv, and
using the relations mNAv = M and kNAv = R, where M is the gas molecular weight and R is the universal
gas constant, this becomes
Mgz
−
ρ (z ) = ρ0 e RT
. (3.2.30)
54 Thermodynamic Relations

This equation shows that the density of a gas with greater molecular weight decreases with height
faster than the density of a lighter gas. Note that convection and turbulence in the atmosphere may
redistribute and mix the gases, so that their vertical distribution may not obey this relation.

3.2.4. Bose–Einstein Statistics

If the temperature of an ideal gas becomes sufficiently low or the density is high, then the criterion
for Boltzmann statistics nk << 1 is not satisfied. Bose–Einstein statistics apply when quantum effects
are important, the particles are indistinguishable, and they have an integer spin (internal momentum
of rotation); that is, counted in integer numbers of Planck constant h. Bose–Einstein statistics was
introduced for photons and then later generalized to atoms. Important applications of Bose–Einstein
statistics include the following: black-body radiation, which can be considered as an ideal gas of pho-
tons; evaluation of the heat capacities of the solids and gases; and ice nucleation at low temperatures.
Bose–Einstein statistics can be derived from the thermodynamic potential W in (Eqn. 3.2.11) for
an ideal gas. The energy EnN of gas particles in the k-th quantum state can be presented as a sum of
the energies ek of individual particles, the number of particles is N = nk, that is EnN = nkek. Substitution
of these relations into (Eqn. 3.2.11) yields for the thermodynamics potential Wk of this state
n
 µ−ε k
Ω k = − kT ln Z , Z = ∑  exp  kT k   . (3.2.31)
nk  
The statistical sum Z here represents a geometric progression by the powers nk and can be different
depending on the particles’ rotation moment, or spin. The spins of the particles can be either “integer”
(equal to Planck’s constant h—an example are photons—then the particles wave functions are sym-
metric) or “half-integer” (equal to h/2, then their wave functions are anti-symmetric—examples are
electrons, and the constituents of atomic nuclei, protons and neutrons). In this section, we consider
a system that has a symmetric function and the integer spin, as is the case with photons. Then, the
number of particles in each state can be unlimited. The geometric progression in (Eqn. 3.2.31) has an
infinite number of terms from nk = 0 to ∝ and converges for all terms if (m − ek) < 0. Summing up, we
{ }
−1
obtain Z k = 1 − exp ( µ − ε k ) / kT  , and

  µ − εk 
Ω k = kT ln 1 − exp    . (3.2.32)
  kT 
The number of particles in each k-state is

∂Ω k 1
nk = − = . (3.2.33)
∂µ exp[(ε k − µ ) / kT − 1 ]

This distribution is called Bose–Einstein statistics. It was derived by Bose in 1924 for photons and
generalized later by Einstein for atoms.
The particles that obey this statistics are called bosons (e.g., photons are bosons, and the recently
discovered Higgs particle that gives inertia to all the bodies is also a boson). If (ek − m) >> kT, then 1
in the denominator of (Eqn. 3.2.33) can be neglected, and we obtain

nk = exp[− (ε k − µ )/kT ] , (3.2.34)

3.2. Statistical Energy Distributions 55

which is the Boltzmann distribution. Therefore, Bose–Einstein statistics is a generalization of the

Boltzmann statistics for arbitrary relations of (ek − m) and kT, which is in agreement with the correspon-
dence principle. Boltzmann statistics has been used in classical derivations of the ice nucleation rates
(see Chapters 8 and 9). At very low temperatures or other conditions, when a relation (ek − m) ≤ kT is
satisfied, the Boltzmann distribution can become inapplicable and the Bose–Einstein distribution should
be used.
A well-known application of the Bose–Einstein distribution (Eqn. 3.2.33) is black-body radiation,
which represents the ideal gas of photons with a variable number of particles. The condition of energy
minimum gives m = 0 for this system, the energy of a photon is e = hv, where v is the frequency
of radiation, and the density of oscillators with the frequency n is dNn = (8p/c3)n 2dn (Landau and
Lifshitz, 1958b, v.5; Born, 1963). Multiplying this dNv by nν from (Eqn. 3.2.33), we obtain the
energy density of radiation:

8π h ν 3 dν
dρε (ν , T ) = ρε (ν , T )dν = 3
. (3.2.35)
c exp(hν /kT ) − 1

This is the Planck function for the black-body radiation, which follows from the Bose–Einstein dis-
tribution of the photon gas. Another application of the Bose–Einstein distribution for ice nucleation
will be considered in Chapters 8 and 9.

3.2.5. Fermi–Dirac Statistics

For completeness, we briefly outline the last of the major statistics. If the spin of the particles is
half-integer, h/2, like the electron spin, the wave function of the system is antisymmetric, changing
its sign at the interchange of any 2 particles. Then, the Pauli’s exclusion principle acts, which states
that not more than one particle can be in any quantum state. Thus, the number of particles nk in each
quantum energy level can only be 0 and 1. The statistical sum Z in (Eqn. 3.2.31) has only two terms
and this yields the W-potential

  µ − εk  
Ω k = − kT ln 1 + exp  . (3.2.36)
  kT  

Thus, the average number of particles in this k-state is

∂Ω k 1
nk = − = . (3.2.37)
∂µ exp[(ε k − µ ) /kT + 1 ]

This is called Fermi–Dirac statistics. The particles obeying Fermi–Dirac statistics are called fermions.
A gas or any system with this distribution is called a Fermi-gas or Fermi-system. An important
example of such Fermi-gas is the electron cloud in an atom or free electrons in metals; the pro-
tons and neutrons in atomic nuclei represent Fermi-liquid. The atoms with electrons fulfilling one
atomic electron shell constitute one period in the periodic table of the elements discovered by Dmitry
Mendeleev in 1869 (Landau and Lifshitz, v. 3, 1958a; Born, 1963). Due to Fermi–Dirac statistics, the
number of electrons in each quantum state is limited (0 or 1), quantum mechanics predicts that the
number of electrons in each atomic shell is limited and equal to ne = 2Np2, where Np is the principal
quantum number of the shell that determines the period in the periodic table. For example, for the
56 Thermodynamic Relations

2.0
Bose–Einstein

Statistical distributions
1.5

1.0 Fermi–Dirac

0.5
Boltzmann

0.0
Relative energy x = (ε−µ)/kT (arbitrary units)

Figure 3.1. Three major statistical distributions by Bose–Einstein, Fermi–Dirac, and Boltzmann.
At sufficiently high energies x = (e − m)/kT, all three statistics become close—that is, the Bose–
Einstein and Fermi–Dirac statistics convert into the Boltzmann distribution at the high energy limit
(e − m) >> kT.

periods with Np = 1, 2, and 3 in the table, these are: ne = 2 (hydrogen and helium in the 1st period),
8 and 18 in the 2nd and 3rd periods respectively, which explains the periodic table (when the number
of electrons in a shell becomes large, their mutual interactions, spin-orbital and other interactions
make the picture more complicated and influence the filling of the shell, the number of electrons in
each shell and the number of the elements in one period of the periodic table). The number of elec-
trons in each shell determines the chemical properties of the elements. Thus, all chemical properties
of all chemical elements follow from the Fermi–Dirac statistics and Pauli’s principle. Additional
important applications of this statistics are the theories of superconductivity and superfluidity. In
cloud physics, application of this statistics may be desirable—e.g., for consideration of cloud elec-
trification with strong ionization of ice molecules at low temperatures, when a large number of free
electrons may form, then their behavior may diverge from the Boltzmann distribution and obey the
Fermi–Dirac distribution.
As in the case with Bose–Einstein statistics, if (ek − m) >> kT, then 1 in the denominator of
(Eqn. 3.2.37) can be neglected, and we obtain again the Boltzmann distribution. Thus, Fermi–Dirac
statistics is another generalization of the Boltzmann distribution in agreement with the correspon-
dence principle, and the predictions of all three statistics coincide for the case (ek − m) >> kT. These
three distributions are shown in Fig. 3.1. It shows that at sufficiently low T or small e, Boltzmann
statistics becomes invalid and Bose–Einstein or Fermi–Dirac statistics should be used.

3.3. Phase Rules

The state of a thermodynamic system can be described using several intensive variables like tem-
perature T, pressure p, chemical potentials mk, etc. Not all of these variables are independent. The
number of independent variables is called the number of thermodynamic degrees of freedom and
obeys phase rules. These rules are different for systems consisting of bulk phases with and without
boundary surfaces.
3.3. Phase Rules 57

3.3.1. Bulk Phases

Consider a system of c components and j bulk phases that do not have the boundary surfaces among
the phases or components. The system can be described with the following variables:

T ; p1 ,..., pϕ ; x11, ,..., xcϕ , (3.3.1)

where T is the temperature, common for the entire system, pa is the pressure inside the a-th phase
(where a = 1,…, j—i.e., total j variables), and xga is the weight fraction of component g in phase a
(a = 1,…, j, and g = 1,…, c, which gives the total cj variables). Thus, (Eqn. 3.3.1) contains 1 + j + cj
variables, but not all of them are independent.
The weight fractions are constrained by j relations of mass conservation

∑x α
γ = 1, (3.3.2)
γ

where a = 1,…, j, that is, (Eqn. 3.3.2) forms j relations. Thus, (Eqns. 3.3.1 and 3.3.2) show that the
system is defined by
NNvv = 1 + ϕ + cϕ − ϕ = 1 + cϕ (3.3.3)

variables. There are two additional constraints: equality of pressures among the phases
p1 = .. = pα = ... = pϕ , (3.3.4)

which gives np = j − 1 relations, and equality of the j chemical potentials for c components,

µγ1 = .. = µγα = ... = µγϕ , (3.3.5)

which gives nm = c(j − 1) relations. So, we obtain the number of independent variables, or thermody-
namic degrees of freedoms or variance
Nww = N v − n p − nµ = 1 + cϕ − (ϕ − 1) − c(ϕ − 1) = c + 2 − ϕ .
N (3.3.6)

This is the Gibbs’ phase rule for bulk phases without curved interfaces.
If we have a homogeneous liquid or gas (e.g., air or water vapor), there is one component, c = 1,
and one phase, j = 1. Thus, Nw = 2, and there are two independent variables. This agrees with the fact
that the three variables describing the liquid, the density r, pressure p, and temperature T, are related
by one equation of state; that is, only two variables are independent, so the system is bivariant.
Consider liquid water in equilibrium with its vapor. Then, c = 1, j = 2, thus, Nw = 1 and there is
one independent variable, the system is monovariant. We can therefore consider vapor pressure as a
function of temperature. The same is valid for ice in equilibrium with vapor, c = 1, j = 2, thus, Nw = 1.
If liquid water is in equilibrium with its vapor and ice, c = 1, j = 3, thus, Nw = 0. In this case, there
are no independent variables, and equilibrium is possible at only one pressure and temperature, which
defines the triple point temperature.

3.3.2. Systems with Curved Interfaces

A more complicated case is a system of c components and j bulk phases separated by y curved inter-
faces, each comprising only a single surface phase, and having the radius of mean curvature rb . There
are no chemical reactions in the system. The system is characterized by the temperature T, pressures
58 Thermodynamic Relations

pa in the bulk phase a (a = 1, . . . , j), and the mass fractions dissolved in the bulk and adsorbed on
the surfaces. The components in the bulk phase are characterized by xga, the weight fractions of com-
ponent g in phase a, which gives a total of cj variables. The components adsorbed on the interfaces
can be characterized by the adsorbed mole fraction ngb (b = 1,…, y), or by their density, Ggb = ngb/Ab ,
called adsorption, where Ab is the surface area of the b-th surface. So, the variables describing the
system include the following:

T ; p1 ,..., pϕ ; x11, ,..., xcϕ ; Γ11 ,..., Γψc ; r1 ,..., rψ , (3.3.7)

that is, j pressures, cj volume fractions xga, cy adsorptions, and y radii of curvature. The total
number in this list is 1 + j + cj + cy + y. The same mass conservation (Eqn. 3.3.2) for the weight
fractions yields j constraints. Thus, the number of variables is
N v = 1 + ϕ + cϕ + cψ + ψ − ϕ = 1 + cϕ + ψ (c + 1). (3.3.8)

There are also another two types of constraints. The Laplace’s relations at each surface are

2σ β
pα − pα′ = , (3.3.9),
rβ

where pa and pα′ are pressures on the two sides of the surface, and sb is the surface tension on the
surface. This yields np = y relations. The chemical potentials are related now as

µγ1 = ... = µγα = ... = µγϕ = µγα 1 = ... = µγαβ = ... = µγαψ , (3.3.10)

where µγα is the chemical potential of component g in the bulk phase a (g = 1, …, c; and a = 1, …, j)
and µγαβ is the chemical potential of component g in the phase a adsorbed in the surface phase b
(b = 1, …, y).
Equations (3.3.9) and (3.3.10) express the conditions of equilibrium for this system. The condi-
tions for µγα give c(j − 1) relations, and the conditions for µγαβ give cy relations. Thus, (Eqn. 3.3.10)
gives total nm = c(j + y − 1) relations. So, we obtain the number of degrees of freedom to be

N w = N v − n p − nµ = 1 + cϕ + ψ (c + 1) − ψ − c(ϕ + ψ − 1). (3.3.11)

The summation on the right-hand side yields a simple result:

Nw = 1 + c . (3.3.12)

This is the phase rule for a system with the interfaces. It expresses an important property of the sys-
tem: the number of degrees of freedom is independent of the number of both bulk and surface phases.
When a component is absent in some phase (e.g., is insoluble), then one of the relations (Eqn. 3.3.10)
vanishes. However, since a condition of insolubility appears, the fraction xga = 0; thus the number of
constraints remains the same and the phase rule (Eqn. 3.3.12) holds.
Consider a few practically important applications of the phase rule (Eqn. 3.3.12).

1. A system comprised by a pure water drop of radius r surrounded by pure water vapor of pressure
er at a temperature T. The number of components is c = 1 (water), and Nw = 2. We may choose
T = const and study the dependence of er on r. This will give us Kelvin’s law for the dependence
er on r for the drop (Section 3.8). The same consideration of a crystal in water vapor will bring
us the dependence er on r for the crystal.
3.4. Free Energy and Equations of State 59

2. A system consisting of a pure water drop of radius r surrounded by humid air at total pressure p.
Now, c = 2 (water and air), and Nw = 3 from (Eqn. 3.3.12). To study the dependence er on r for a
drop or crystal, we have to take both T = const and p = const. This will also give us Kelvin’s law.
3. A system of an aqueous solution drop in humid air at pressure p and temperature T. The num-
ber of components c = 3 (salt, water, air), thus Nw = 4. However, the mass of salt in the drop
is constant despite possible changes of its radius due to growth or evaporation. This adds one
more constraint, and the actual number of thermodynamic degrees of freedom is Nw = 3 as in the
previous case.
4. A system of pure water drop with radius rw in humid air at pressure p and temperature T with
a spherical crystal of radius rc embedded in the drop. Then, c = 2 (water and air) and Nw = 3.
This system is considered in Chapters 8, 9, and 10 in connection with immersion freezing, along
with the other examples, and the phase rule helps to determine the degrees of freedom in such
systems.

3.4. Free Energy and Equations of State

3.4.1. An Ideal Gas

The ideal gas equation of state is usually given in books on atmospheric physics either without deri-
vation, or sometimes with simple physical derivations from molecular-kinetic theory. A more general
derivation can be done from the thermodynamic potentials (Landau and Lifshitz, 1958b), which
allows further generalizations for non-ideal gases and for the liquids.
The Helmholtz free energy F of the gas with the Boltzmann distribution by the energies ek is given
by Equations (3.2.3) and (3.2.4). The energy En in (Eqn. 3.2.3) can be written as a sum of the energies
ek of all N particles in the gas, and summing up independently over all the combinations of quantum
energies and over all particles, we obtain from the statistical sum Z in (Eqn. 3.2.3)
N
1  −E  1   −ε 
Z = ∏ ∑ exp  kTn  = N ! ∑ exp  kTk
N! N n
  , (3.4.1)
 n 
where the sign “N!” means the factorial, product of the natural numbers from 1 to N. The factor 1/N!
arises here because in this summation, each quantum state with the same energy distributions over
the N particles is counted N! times. This arises because the particles are identical; an interchange of
any two particles does not produce a new quantum state, but all such identical states are accounted
for in the sum independently. The number of such interchanges in a system of N particles is N!. Thus,
each state is counted in the sum N! times but should be counted just one time. Therefore, a correct
statistical sum is obtained by dividing by N!
Substituting this Z into (Eqn. 3.2.4), we obtain the free energy for a Boltzmann gas:

F = − kTN ln ∑ exp(− ε k / kT ) + kT ln N ! . (3.4.2)

i

Since N is a very large number, it is possible to use an approximate Stirling formula

ln N ! ≈ N ln( N / e) , (3.4.3)
60 Thermodynamic Relations

where e ≈ 2.718 is the base of the natural logarithm. Then, (Eqn. 3.4.2) can be rewritten as

F = − kTN ln  / kT )  .
e
∑ exp(−ε i (3.4.4)
N i 
In classical statistics, this equation becomes
ε ( pm , q )
e − dpm dq 
F = − kTN ln  ∫ e kT , (3.4.5)
N h3 

where pm and q are the momentum and coordinate that form the phase space of the generalized coor-
dinates, dpmdq is the differential volume of the phase space, h is the Planck constant, and dpmdq/(h)3
is the number of states in the phase space.
The energy of the gas molecules can be written as

px2 + py2 + pz2

ε ( px , py , pz ) = + eεk′, (3.4.6)
2m
where px, py, pz are the 3 components of momentum, and ek′ is the internal energy independent on
the speed of the molecules. In this case, the phase space [pm − q] consists of the three-dimensional
momentum space and three-dimensional Cartesian space with an element [dpmdq] = dpxdpydpzdV.
Accounting for this fact and substituting (Eqn. 3.4.6) into the integral (Eqn. 3.4.5) gives

e 
F = − kTN ln  Z1  , (3.4.7)
N 
where the statistical sum Z1 is

−
ε i′ ∞ ∞ ∞
 px2 + py2 + pz2  dpx dpy dpz
Z1 = ∑ e ∫ dV ∫ ∫ ∫ exp  −
kT
2mkT

h3
, (3.4.8)
i −∞ −∞ −∞

and the expression in exp represents the kinetic energy of the molecules.
The internal integral over the momentum is calculated in Appendix A.3, and gives

∞ ∞ ∞
 px2 + py2 + pz2  dpx dpy dpz  2π mkT 
3/ 2

∫ ∫ ∫ 
−∞ −∞ −∞
exp −
2mkT 
 h3
= 
h2 
 . (3.4.9)

Substitution of this into (Eqn. 3.4.8) and integration also over dV yields
3/ 2 ε i′
 2π mkT  −
Z1 = V 
 h 2  ∑e kT
. (3.4.10)
i

The factor V arises from the integration because molecular energy ei′ and dwp are independent on
coordinates. The integral over momentum space is calculated in Appendix A.3. Then, we obtain for
the free energy F:
3/ 2 ε i′
 eV  2π mkT  − 
F = − kTN ln  
h2 
 ∑e kT
. (3.4.11)
N i 
Its general evaluation can be rather complicated, as it requires knowledge of the internal energies ei′.
3.4. Free Energy and Equations of State 61

However, calculation of the gas pressure is simple. Separating now the term with V, the free energy
of an ideal gas can be rewritten
3/ 2
 eV   2π mkT  
Fid = − kTN ln     + Nf (T ), (3.4.12)
 N   h
2

where f(T) is some function of T—its exact form is unimportant because it is independent on V. (If the
internal energy of molecules is much smaller than the kinetic energy and can be neglected, ei′ ≈ 0,
then the sum in (Eqn. 3.4.11) is equal to 1, and f(T) is simply evaluated). The pressure is now obtained
from the relation (Eqn. 3.1.6):

∂ Fid kTN
p=− = , (3.4.13)
∂V V
or in another form
pV = kNT . (3.4.14)

This is the equation of state for an ideal gas.

Several other forms of this equation are useful in applications. For air, the mass is ma = naMa,
where Ma is the molecular weight and na is the number of moles, and the density ra = ma/V. If the
mass is one gram-molecule, na = 1 mole, then the number of molecules N is equal to Avogadro’s
number NAv = 6.023 × 1023 (molecules mole−1), the molar volume vam is related to the molecular mass
Ma as vam = Ma /ra, and the equation of state for one gram-molecule of the air at pressure pa can be
written as

pa va = kNAvT = RT, or pa = ra Ra T, (3.4.15)

where R = kNAv = 8.3144 × 107 erg mole−1 K−1 = 1.9858 cal mole−1 K−1 is the universal gas constant,
Ra = R/Ma = 2.8706 × 106 erg g−1 K−1 = 287 J K−1 kg−1 is the gas constant for the air.
If a gas consists of a mixture of gases that occupy a common volume V and have partial pressures
pk with a number of moles nk, then this equation becomes

pk V = nk RT . (3.4.15a)

For water vapor, the density is rv = mv /V, and the pressure is ev. For the mass of one gram-molecule,
the molar volume is vm = Mw /rv, and the equation of state for water vapor considered as an ideal gas
can be written as
ev vm = kNAv T = RT , ev = ρ v Rv T (3.4.16)

where Rv = R/Mw = 4.6150 × 106 erg g−1 K−1 is the gas constant for the vapor. The same equations of
state are valid for the saturated over water and ice vapor pressures ews, eis, and the densities rws, ris:

ews = ρ ws Rv T , (3.4.17)
eis = ρis Rv T . (3.4.18)

The Clausius–Clapeyron equation for ews, eis describing their temperature dependence, and other
atmospheric humidity variables will be described in Section 3.7.
62 Thermodynamic Relations

3.4.2. Free Energy and the van der Waals Equation of State for a Non-ideal Gas

The atmospheric gases at normal conditions in Earth’s atmosphere are close to ideal. The error of
the ideal gas equation for atmospheric vapor is about 1% under atmospheric conditions; therefore
the equations of state for the non-ideal gases usually are not used in most applications to Earth
atmospheric physics under moderate conditions. However, non-ideality of the gases increases as the
pressure increases or temperature decreases, and as a gas approaches the phase transition point into
a liquid (e.g., Curry and Webster, 1999). The non-ideal gases and liquids can be described with the
van der Waals equation of state and its modifications.
Since the 1990s, various modifications of the van der Waals equation of state have begun to play an
increasingly important role in studies of liquid water, its equilibrium with the vapor especially at low
temperatures, and the processes of ice nucleation (see Chapter 4). Therefore, a derivation is provided
in this subsection of the free energy F and of the van der Waals equation of state that describes the
non-ideal gases and liquids. This derivation provides a platform for understanding the modifications
of the van der Waals equation described in Chapter 4 and their applications for supercooled liquids.
The van der Waals equation can also be used for studies of the atmospheres and clouds of other
planets where gases behave as non-ideal because of the great variety of pressures and temperatures.
For example, the temperature and pressure in the atmosphere of Venus vary from ∼740 K and 88 atm
at the surface to less than 200 K and very low pressure at altitudes more that 100 km. The major con-
stituent of the Venusian atmosphere, CO2, has a critical point at Tcr = 304.2 K and pcr = 72.9 atm. The
critical point of CO2 is within the parameter range of the Venusian atmosphere, where its behavior is
different from the ideal gas—in particular, the lapse rate may substantially exceed the value for the
ideal gas (e.g., Callen, 1960; Curry and Webster, 1999, Chapter 14 therein). The atmospheres of the
Jovian planets (Jupiter, Saturn, Uranus, and Neptune) also have high pressures, and the gases may
behave as non-ideal. This may influence cloud formation on these planets.
For derivation of the van der Waals equation, consider a monatomic gas—a generalization for the
polyatomic gases can be derived in a similar way (Landau and Lifshitz, v. 5, 1958b). The motion of
its molecules can be considered as classical and its energy can be written as a sum of the kinetic ener-
gies pm2 /2m and the potential energy U of the molecular interactions:
N 2
pmi
E ( p, q) = ∑ +U, (3.4.19)
i =1 2m

where pm and q denote the momentum and coordinates of a molecule, and N is the number of mol-
ecules. For a monatomic gas, U is a function of only the distances between the atoms.
The statistical integral ∫ e − E ( pM ,q )/kT dpm dq in the Equation (3.4.5) for the free energy F becomes
a product of the integral over the atomic momentum pm and the integral over the coordinates, which
has the form
−U/KT
∫ ... ∫ e dv1 ...dv N , (3.4.20)

where integration over each volume dV = dxadyadza is performed over all the volume occupied by the
gas. For an ideal gas, U = 0, and this integral would be equal to VN. It is clear then that evaluation of
the free energy F from Equation (3.2.8) would give an expression

 1 
∫ ... ∫ e
−UkT
/
F = Fid − kT ln  N dV1 ...dVN  . (3.4.21)
V 
3.4. Free Energy and Equations of State 63

Adding and subtracting 1 in the integrand and using the relation ∫ ... ∫ dV ... dV
1 N = V N , we can rewrite
(Eqn. 3.4.21) as

 1 
∫ ... ∫ (e
−U/kT
F = Fid − kT ln  N − 1) dV1 ... dVN + 1  . (3.4.22)
V 
We assume further that the density of the gas is sufficiently small, so that only the collisions between
the two molecules are possible, while the collisions among the three and greater number of molecules
can be neglected. Interactions between the atoms become substantially strong and the integrand in
(Eqn. 3.4.22) is nonzero only when the two atoms are sufficiently close to each other. The number of
such couples of the atoms is CN2 = N(N − 1)/2. They give the non-zero contribution into the integral
in (Eqn. 3.4.22), which therefore can be written as

∫ ... ∫ (e
−U12 /kT
− 1) dV1 ... dVN , (3.4.23)

where U12 is the energy of interaction of the two atoms. U12 depends on the coordinates of any two
atoms, and we can integrate over the coordinates of all the other (N – 2) atoms, which yields V(N − 2).
Since N is very large, we can assume that N(N − 1) ≈ N2.
Then, we can write (Eqn. 3.4.22) as

 N2 
F = Fid − kT ln  2 ∫ ... ∫ (e −U12/kT − 1) dV1 dV2 + 1  , (3.4.23a)
 2V 
where dV1dV2 is a product of volume differentials of the first two atoms. We assumed that the gas
density is small, N/V <<1, and the first term under the logarithm sign is much smaller than 1 due to
the factor (N/V)2. Using the relation ln(1 + x) ≈ x at x << 1, we can write (Eqn. 3.4.23a) as

N2
... ( e −U12/kT − 1 ) dV1 dV2 .
2V 2 ∫ ∫
F = Fid − kT (3.4.24)

The potential energy U12 is a function only of the distance between the atoms—i.e., of the dif-
ference of their coordinates. We can perform a transformation of the coordinates, and instead of
the coordinates of each atom we introduce the coordinate of their center of inertia R12 and mutual
distance r12. Thus, U12 will depend only on r12, and we denote its differential as dV. We can integrate
over R12, which again gives V, and we finally obtain from (Eqn. 3.4.24)

N 2 kT
F = Fid + BW (T ) , (3.4.25)
V
1
2∫
BW (T ) = (1 − e −U12 /kT ) dV . (3.4.26)

The second term in (Eqn. 3.4.25) is a correction for non-ideal gas behavior, and these expressions
represent a platform for derivation of the van der Waals equation.
A schematic picture of the potential energy U12(r) versus distance r between the atoms for a
monatomic gas is given in Fig. 3.2. It shows that U12(r) is positive and very large at r < 2r0 (where
the repulsive forces dominate), passes zero at r = 2r0, and becomes negative at r > 2r0 (where attrac-
tive forces dominate), and so reaches a minimum -U0 at a larger r and tends to zero at a very large r.
U12(r) increases rapidly, with decreasing r at r < 2r0 and forms almost a potential wall, thereby
prohibiting mutual penetration of the atoms. Therefore, r0 can be interpreted as the atomic radius.
Equations (3.4.25) and (3.4.26) make sense if the integral BW converges—that is, if U12(r) decreases
64 Thermodynamic Relations

Potential energy U12(r)

U12>0

0
2r0 Distance r
U12 <0

U12,min = −U0

Figure 3.2. Potential energy U12(r) of interaction of two atoms of a non-ideal gas as a function of the
distance r between the atoms. U12(r) is positive and large at r < 2r0, U12(r) = 0 at the point r = 2r0
(denoted by the ellipse) becomes negative and reaches a minimum U0 at a larger r and tends to zero
at a very large r.

fast enough with r. If U12(r) decreases asymptotically as U12(r) ∼ 1/rn, then BW converges for n >3.
This occurs since the electrical forces between the electrically neutral atoms and the potential energy
of their interaction are often approximated as U12(r) = au/rn − bu/r6, where the first term describes
repulsion due to interaction of the two atomic electronic shells at small distances that grows with
decreasing radius as 1/rn, and the second term describes attraction at large distances, which arises
due to interaction of the electrical dipole moments and decrease at large r as U12(r) ∼ 1/r6 (Landau
and Lifshitz, v. 3, 1958a; Born, 1963).
Further derivation is based on the transformation of the integral BW(T). We assume that U0/kT << 1,
and since U12(r) depends only on r and does not depend on the angles, we can integrate over the
angles, write in spherical coordinates dV = 4pr2dr and present BW(T) as a sum of the two integrals:

1
2∫
BW (T ) = (1 − e −U12 ( r )/kT ) dV = I B1 + I B 2 (3.4.27)
2 r0 ∞

∫ (1 − e ∫ (1 − e
−U12 ( r ) / kT
I B1 = 2π ) r 2 dr , I B 2 = 2π −U12 ( r ) / kT
)r 2 dr (3.4.28)
0 2 r0

In the integral IB1, U12(r) is very large (see Fig. 3.2), thus we can assume U12(r)/kT >> 1 and neglect
exp(−U12(r)/kT). Then, IB1 is simply evaluated as

16π 3
I B1 = r0 = 4 v0 = b. (3.4.29)
3
Thus, IB1 = b is four times greater than the volume of an atom v0 = (4/3)pr03. In the second inte-
gral, IB2, the value U12(r) does not exceed U0, and, as we assumed U0/kT << 1, we have a condition
|U12(r)|/kT << 1. Then, we can expand into the power series exp(−U12(r)/kT), and keeping only the
first two terms, we have exp(−U12(r)/kT) ≈ 1 − U12(r)/kT), so substitution into IB2 yields
∞ ∞
2π a
I B2 ≈
kT ∫U
2 r0
12 (r )r 2 dr = −
kT
, a = −2π ∫U
2 r0
12 (r )r 2 dr . (3.4.30)
3.4. Free Energy and Equations of State 65

The minus sign is chosen because U12(r) < 0 in the integrand and the integral IB2 is negative. Sub-
stituting Equations 3.4.27–3.4.30 for BW(T) into (Eqn. 3.4.25) for F, we obtain

N2
F = Fid + ( kTb − a) . (3.4.31)
V
Substitution of Equation (3.4.12) for the free energy of the ideal gas Fid yields

e    2π mkT  3/ 2  Nb  N 2 a
F = Nf (T ) − kTN ln − kTN ln V    − − . (3.4.32)
   h
2
N  V  V

This equation still does not account for the limited compressibility of the gas; it allows V → 0
instead of some minimum Vmin determined by the volume of all molecules. This equation can be
modified as follows. In the preceding derivation, we assumed that although the gas is non-ideal,
its density is so small that the triple, quadruple, and higher order collisions can be neglected. This
is equivalent to the statement that the total volume occupied by the molecules Nv0 is much smaller
than the gas volume V (i.e., Nv0 << V). Since b = 4v0, this condition is equivalent to the condition
x = Nb/V << 1. For small x, an approximate relation can be used x ≈ ln(1 + x), and we can transform
the expression in (Eqn. 3.4.32) as

  2π mkT  3/ 2  Nb   2π mkT  3/ 2   Nb 
ln V    − ≈ ln V    + ln  1 − 
  h 2
  V  h 2
 V 
3/ 2
 2π mkT  
= ln   (V − Nb)  . (3.4.33)
 h
2


Substituting this relation into (Eqn. 3.4.32), we obtain F as

 eV  2π mkT  3/ 2  Nb   N 2 a
F = Nf (T ) − kTN ln     1 −  −
N h 2
V  V
  eV  2π mkT  3/ 2    Nb  N 2 a
= − kTN ln     + Nf (T )  − kTN ln  1 − − . (3.4.34)
 N h 2
  V  V

The first two terms here in the figure parentheses represent Fid according to (Eqn. 3.4.12), and finally

 Nb  N 2 a
F = Fid − kTN ln  1 − − . (3.4.35)
 V  V

This equation already has the property of final compressibility, the term under the logarithm sign
should be positive, thus V > Nb. Equation (3.4.35) is also used in terms of the number of moles n.
Using the relations n = N/NAv, k = R/Nav, and the notations am = aNAv2, bm = bNAv, we obtain

 nb  n 2 am
F = Fid − RTn ln  1 − m  − . (3.4.36)
 V  V

This gives for one mole

 b  a
Fm = Fid − RT ln  1 − m  − m . (3.4.37)
 V  V
66 Thermodynamic Relations

Equations like (Eqns. 3.4.35) and (3.4.37) are used in modifications of the free energy and van der
Waals equation for liquids (see Chapter 4). The gas pressure can now be evaluated from (Eqn. 3.4.35):

∂F ∂F kTN Nb N 2a
p=− = − id + − 2 . (3.4.38)
∂V ∂V V V − Nb V
Substituting here Equation (3.4.13) for the ideal gas, pid = −∂Fid / ∂V = kTN/V, and rearranging the
terms, we obtain

kTN  Nb  N 2 a kTN N 2a
p=  1 +  − 2 = − 2 . (3.4.39)
V V − Nb V V − Nb V
Or, finally,

 N 2a 
 p + (V − Nb) = kTN . (3.4.40)
V 2 

This is the van der Waals equation of state for the real gas. This equation is also used in terms of the
number of moles n,

 n 2 am 
 p + (V − nbm ) = RTn , (3.4.41a)
V 2 

where am and bm are the same as defined after (Eqn. 3.4.35). For one mole, we have

 am 
 p + 2  (V − bm ) = RT . (3.4.41b)
V

The van der Waals equation of state generalizes the equation of state for an ideal gas (Eqn. 3.4.15)
and converts into it for am = 0, bm = 0. These are two corrections to the equation of state for the ideal
gas. The pressure correction accounts for the pressure reduction dp = am /V2 due to interaction of the
gas molecules (the van der Waals forces); the volume correction accounts for the available volume
decrease d V = −bm due to the finite volume occupied by all gas molecules, called the excluded volume.
Both pressure and volume corrections were expressed in (Eqns. 3.4.29) and (3.4.30) via the parameters
of potential energy of intermolecular interactions.
In practice, the parameters am and bm are determined from measurements in order to reach the best
agreement of predictions of the van der Waals equation with experimental quantities. For water,
am = 5.26 cm3 atm mole−2, and bm = 30.5 cm3 mole−1. The corresponding values of bm for the major
air components, oxygen and nitrogen, are comparable, ≈32.6 and ≈38.5 cm3 mole−1, but the values of
am are almost 4 times smaller: 1.36 and 1.34 cm3 atm mole−2. This indicates that the excluded volume
only slightly varies among different gases. Calculations show that the molecular volumes of many
gases vary between v0 ∼ 1.7 and 4.9 (Å)3. Variation of the intermolecular forces characterized by am
is much greater.
Many modifications and generalizations of the van der Waals equation are used for studies of liq-
uids and solids, in particular for liquid water and ice. Some applications for water will be considered
in Chapter 4.
3.5. Thermodynamics of Solutions 67

3.5. Thermodynamics of Solutions

All these processes of drop and crystal nucleation substantially depend on the particles’ chemical
composition and concentrations of the solutions. The concentrations are characterized by the mole
fractions and molalities. In general, there can be several solutes in a solution, and the mole fraction
xkl of the substance k in solution is
nkl
x kl = , (3.5.1)
nsolv + nkl

where nsolv and nkl are the number of moles of solvent and the k-th solute in solution. The mole frac-
tions of solute xs and water xw in aqueous solution are defined via the corresponding number of moles
ns and nw in solution:
nw ns
xw = , xs = . (3.5.2)
nw + ns n w + ns

The molality M̂ is defined as the number of moles of salt dissolved in 1000 g of water. Then,
nw = 1000/Mw, with Mw being the molecular weight of water, ns = Mˆ , and

ns Mˆ
xs = = . (3.5.3)
ns + nw ˆ
M + 1000 / M w

The mole fraction xk of the k-th gas in the mixture of gases with the total pressure p is determined
from Dalton’s law as
pk = px k . (3.5.4)

In an “ideal” solution without interaction between the molecules of solvent and solute, Raoult’s
law acts, which states that the equilibrium vapor pressure pk is proportional to the mole fraction xkl of
this substance in solution (its derivation is given in Section 3.10),
pk = x kl pk 0 , (3.5.4a)

where pk0 is the partial vapor pressure of component k over a pure liquid of k-th component. Obvi-
ously, if only this pure component exists in the system, xkl = 1 and pk = pk0.
Now we can proceed to the derivation of the chemical potentials in solutions. From Equation (3.1.21)
of Section 3.1, we have for the molar chemical potential mvk and volume vk of an ideal gas k (vapor
phase, subscript “v”):

 ∂ µ kv 
 ∂ p  = vk . (3.5.5)
T , nk ≠ i

Substituting here vk = RT/pk from the equation of state (Eqn. 3.4.15a), we obtain

 ∂ µ kv  RT
 ∂ p  = .
T , nk ≠ i
pk
(3.5.6)

Integration of this equation for mkv yields

µ kv ( pk , T ) = µ kv 0 (T ) + RT ln pk . (3.5.7)
68 Thermodynamic Relations

Substituting here Raoult’s law (Eqn. 3.5.4a) for pk, we obtain for the vapor phase

µ kv ( pk , T ) = µ kv 0 (T ) + RT ln pk 0 + RT ln x k . (3.5.8)

When a gas and liquid are in equilibrium, the chemical potentials of the k-th component should
be equal in both phases, otherwise this component will be redistributed between the phases until
equilibrium is reached. Therefore, the chemical potential of the k-th substance in the liquid (subscript
“l”) with the partial pressure pk will be

µ kl ( pk , T ) = µ kl 0 (T ) + RT ln pk . (3.5.9)

The value of pk in a solution is determined by Raoult’s law. Substituting (Eqn. 3.5.4a) for Raoult’s
law into (Eqn. 3.5.9), we obtain
µ kl ( pk , T , x kl ) = µ k 0 ( p, T ) + RT ln x kl , (3.5.10)

where mk0(p, T) corresponds to zero xkl—that is, it depends on p and T, but not on xkl. The solutions
described by (Eqn. 3.5.10) are called ideal solutions. The chemical potential of water in an aqueous
solution can be written according to (Eqn. 3.5.10) as
µ w ( p, T , x w ) = µ w 0 ( p, T ) + RT ln x w . (3.5.11)

Most dilute non-electrolyte solutions are satisfactorily described by Equation (3.5.11).

However, solute present in deliquescent aerosol or in the drops may be salts or acids that dissoci-
ate into several ions. There are several methods to account for the degree of ionic dissociation of the
solutions. One way is introduction of the van’t Hoff factor i as
nkl
x kl = . (3.5.12)
nsolv + inkl

The van’t Hoff factor i should account for the effective increase or decrease of the number of ions in
a dissociated solution and was applied in earlier studies on cloud physics. This factor was introduced
in van’t Hoff’s equation for osmotic pressure. The disadvantages of this factor are that the values of i
are known for very few substances, and its effective values increase or vary non-monotonically with
decreasing solution molality (see Table 1 in Low, 1969). For example, for NaCl, a component of the
marine aerosol and cloud condensation nuclei, the number of ions is n = 2, while i ≠ 2, but i = 1.867
at molality Mˆ = 5 , and i = 2.659 at molality Mˆ = 0.1.
A more accurate modern approach is based on application of the concept of the activity of water aw
and the molal or practical osmotic potential Fs, which are related as

 mM   n 
aw = exp  −ν Φ s s w  = exp  −ν Φs s  , (3.5.13)
 mw M s   nw 

where n is the number of potential ions in a salt or acid, ms and Ms are the mass and molecular weight
of the soluble fraction, and mw is the mass of water in the solution. The water activity aw is also
expressed as aw = kwxw, where kw is the rational activity coefficient. The values of aw, Fs, and kw can be
determined from the measurements and the tabulated data are available (e.g., Low, 1969; Robinson
and Stokes, 1970; Pruppacher and Klett, 1997). In general, calculation of aw in an aqueous solution
drop is not a simple process and is often accompanied by calculations of physico-chemical properties
of solutions and particles growth.
3.5. Thermodynamics of Solutions 69

After deliquescence and hygroscopic or diffusion growth, the aerosol particle becomes a solution
drop with the mass maw, volume Vaw, and radius raw. The drop gains a mass of water mw with the
volume Vw. Evaluation of water activity and many other related aerosol properties (e.g., hygroscopic
growth, activation into cloud drops) is based on (Eqn. 3.5.13) and is often performed using two
approximations.
One approximation is based on the simplifying assumptions on the constancy of the water molar
volume in solution and additivity of the volume Vw of solvent (water) and the original volume Vd of
the dry particle, including solute (e.g., salt or acid) and insoluble core. These are good approxima-
tions for many common ionic solutes (Dufour and Defay, 1963; Pruppacher and Klett, 1997; Brechtel
and Kreidenweis, 2000a,b). Using the additivity property, the volume of the solution droplet Vaw can
be written as Vaw = Vw + Vd. Then, the volume Vw and mass mw of water are
Vw = Vaw − Vd , (3.5.14)
3
mw = ρ w (Vaw − Vd ) = (4/3)πρ w (raw − rd3 ). (3.5.15)

Substituting this mw into (Eqn. 3.5.13), we obtain

 3ν Φs M w ms   B 
aw = exp  − 3 3 
= exp  − 3 3
, (3.5.16)
 4π M s ρ w (raw − rd )   raw − rd 

where B is a parameter that describes the physico-chemical properties of the aerosol

3ν Φs M w ms
B= . (3.5.17)
4π M s ρ w

The parameter B is called the activity of a nucleus. It describes the effects of the soluble fraction of
an aerosol particle or cloud condensation nucleus (CCN) and determines the activity of this CCN for
activation of a cloud droplet (see Chapters 6 and 7).
In the other approximation, used for fully soluble particles with dry radius rs, the mass of
water mw is calculated as the difference between the total mass of solution mmaw = (4/3)prs′′″ ra3w,
where rs″ is the solution density, and the mass of the soluble fraction ms = (4/3)p rsrs3—i.e.,
mw = (4/3)p (rs′′″ ra3w − ρ s rs3 )—and water activity is
m

 ν Φ s M w ms 
aw = exp  − 3 . (3.5.18)
 M s [(4/3)π rs″raw − ms ] 

For sufficiently diluted solutions, mw >> ms, and rs″ ≈ rw, this expression is simplified as

 3ν Φ s M w ms   B
aw = exp  − 3 
= exp  − 3  , (3.5.19)
 4π M s ρ wraw   raw 

which is a particular case of (Eqn. 3.5.16) with rd = 0.

After introducing ak, the dependence of mk on the chemical composition can be rewritten with ak
instead of xkl

µ k ( p, T , ak ) = µ k 0 ( p, T ) + RT ln ak . (3.5.20)

In particular, for water,

µ w ( p, T , ak ) = µ w 0 ( p, T ) + RT ln aw . (3.5.21)
70 Thermodynamic Relations

Another characteristic of solutions used in calculations of their chemical and thermodynamic proper-
ties is the weight concentration or weight percent w of solute defined as
ms
w= ⋅ 100%, (3.5.22)
ms + m w

where ms and mw are the masses of solute and water in solution. Molality M̂ can be related to the
weight concentration w, the water saturation ratio Sw, molecular weights of solute Ms and water Mw,
and the number of ions ns and osmotic potential Fs of solvent as described earlier, and can be
expressed in the forms (e.g., Atkins, 1982; Martin, 2000)

10 3 ms 10 w 10 3 (1 − Sw )
Mˆ = , Mˆ = , Mˆ = . (3.5.23)
M s mw M s (1 − w/100) ν Φs M w

Using these relations, w can be expressed in terms of Sw:

ˆ
MM M s (1 − Sw )
w= s
100 % = 100 %. (3.5.24)
ˆ 3
M s (1 − Sw ) + ν s Φ s M w
MM s + 10

Another useful representation of w via mole fraction xs is

M s xs
w= 100%. (3.5.25)
M w + xs ( M s − M w )

3.6. General Phase Equilibrium Equation for Solutions

3.6.1. General Equilibrium Equation

It is convenient to study phase equilibrium in a thermodynamic system using the quantity mk/T. An
equation for phase equilibrium can be obtained from Equation (3.5.20) for chemical potential divid-
ing by T and taking the differential

 µ ( p, T , ak )   µ k 0 ( p, T ) 
d k
  = d   + Rd ln ak
T T
∂( µ k 0 /T ) ∂( µ k 0 /T )
= dT + dp + Rd ln ak . (3.6.1)
∂T ∂p

It was shown in Section 3.1 that the first derivative here is ∂/∂T(mk0 /T) = −hk0 /T 2, and the second
derivative is ∂/∂p(mk0 /T) = vk0 /T, where hk0 and vk0 are the enthalpy and molar volume of the pure
component k. Using these relations, we obtain

µ  h v
d  k  = − k20 dT + k 0 dp + Rd ln ak . (3.6.2)
 T  T T
Note that the subscript “0” here relates to the pure component k.
Now we consider an equilibrium thermodynamic system consisting of a spherical germ of the
bulk phase (2) of k-th component with the chemical potential mk,2 and radius r2 embedded within a
k-th component of spherical bulk phase (1) with chemical potential mk,1 and radius r1, with phase (1)
3.6. General Phase Equilibrium Equation for Solutions 71

itself being in equilibrium with the environment. An example is formation of an ice germ with radius
r2 (phase 2) within a supercooled liquid drop (phase 1) with radius r1, which is in equilibrium with
the environmental air.
If phase 2 is a solid (e.g., ice or salt crystal) that nucleates heterogeneously on the surface of a
foreign substrate, an additional term should be added to mk,2, which arises from the elastic strain e
caused by the misfit between ice and substrate lattices (Turnbull and Vonnegut, 1952; Young, 1993).
This strain increases the density of activation energy by Ce e 2 [erg cm−3] where Ce = 1.7 × 1011 erg cm−3
is the Turnbull-Vonnegut constant (Turnbull and Vonnegut, 1952), and e is measured in percent. The
term in mk,2/T associated with the elastic strain can be formulated as MkCe e 2/(Trk2) (Khvorostyanov
and Curry, 2004a,b) with Mk and rk2 being the molecular weight and the density of phase 2.
Both phases are assumed to be in equilibrium, thus their temperatures and chemical potentials are
equal, T1 = T2, mk,1 = mk,2, and

 µ k ,1   µ k ,2 
d  = d . (3.6.3)
 T1   T2 

Substituting here (Eqn. 3.6.2) for both phases, we can write

(hk 0,1 − hk 0,2 ) vk 0,1 vk 0,2 M k  Cε ε 2   ak 0,1 

− 2
dT + dp1 − dp2 − d  + Rd ln   = 0. (3.6.4)
T T T T  ρ k ,2   ak 0,2 

This is the general equilibrium or entropy equation that determines the equilibrium in the system. The
pressures p1 and p2 in these bulk phases are not equal, but obey Laplace’s equation or the conditions
of mechanical equilibrium:

2σ 1e 2σ 12
p1 = p + , p2 = p1 + , (3.6.5)
r1 r2

where s1e is the surface tension at the boundary between phase 1 and the environment (e.g., between
the drop and the air) and s12 is the surface tension at the boundary between phases 1 and 2 (e.g., the
liquid-ice interface), and p is the pressure in the environment (e.g., air).
The difference of molar enthalpies can be expressed via the latent heat of phase transition between
phases 1 and 2 as

hk 0,1 − hk 0,2 = Lˆ12 = L12 M k , (3.6.6)

where Lˆ12 and L12 are the molar and specific latent heats and Mk is the molecular weight of component k.
Substituting this relation and the Laplace’s relations (Eqn. 3.6.5) for pressure into (Eqn. 3.6.4), we
obtain

Lˆ12 ( vk 0,1 − vk 0,2 )  2σ 1e  vk 0,2  2σ 12 

− dT + d p + − d −
T 2
T  r1  T  r2 

 M k  Cε ε 2   ak ,1 
 − T d  ρ  + Rd ln  a  = 0 . (3.6.7)
 k ,2   k ,2 

This equation of the general equilibrium slightly generalizes the previous equation given in Dufour
and Defay (1963) and Pruppacher and Klett (1997), and can be further generalized by taking into
account additional affects.
72 Thermodynamic Relations

It can be convenient to use this equation in a slightly different form, with the densities rk0 instead
of the molar volumes vk0. Substituting into (Eqn. 3.6.7) the relation vk0 = Mk/rk0, with Mk being the
molecular weight of the k-th component, dividing by Mk and multiplying by T, we obtain

L12 ( T )  2 2   2 2   σ 1e 
− dT +  −  dp +  − d −
T  ρ k 0,1 ρ k 0,2   ρ k 0,1 ρ k 0,2   r1  0

 2 σ   C ε  RT 2
 ak ,1 
 − ρ d  is  − d  ε  + d ln   = 0. (3.6.8)
1 k 0 ,2  r2   ρ k 0,2  M k  ak ,2 

It is important to emphasize that, although we began with the chemical potentials for solutions,
the final quantities (the latent heats, molar volumes, and densities) relate to the pure component k in
the mixture, which is indicated by the subscript “0”. These quantities for pure substances are inde-
pendent on solution concentrations, which makes calculations much easier. Equations (3.6.7), (3.6.8)
describe a large variety of situations pertinent to cloud processes. Many of them are considered in
Dufour and Defay (1963), Defay, Prigogine, and Bellemans (1966), and Pruppacher and Klett (1997).
In this chapter, we will consider the most important processes and laws: the Clausius–Clapeyron
equation, the Kelvin equation, and Köhler’s equation. These three equations are required for deriva-
tion of the supersaturation equations that describes cloud kinetics. Equations (3.6.7) and (3.6.8) will
be used in Chapters 8, 9, 10 and 11 for derivations of the critical radii, energies, and nucleation rates
of homogeneous and heterogeneous nucleation processes.

3.6.2. The Gibbs–Duhem Relation

Equations (3.6.7) and (3.6.8) describe the relations between the properties of the two phases of the
same substance. However, in many cases it is desirable to use relations between the properties of two
different substances—e.g., between the solvent and solute. This can be done using the Gibbs–Duhem
relation described in Section 3.1, which is written for an isothermal (T = const) and isobaric (p = const)
process as
c

∑ x dµ k k = 0. (3.6.9)
k =1

The differential dmk follows from Equation (3.6.2), where the first two terms on the right-hand side
vanish for such a process, and the rest is
dµ k = RTd ln ak . (3.6.10)

Substitution of (Eqn. 3.6.9) into (3.6.10) yields the Gibbs–Duhem relation in the form
c

∑ x d ln a
k k = 0. (3.6.11)
k =1

In particular, for an aqueous solution that contains only two components (c = 2), water and solute,
this relation is
x s d ln as = − x w d ln aw . (3.6.12)

This equation allows determination of solute activities and concentrations with measurements of the
water activities or relative humidities over solutions of various concentrations. It has been used in
studies of aerosol liquid-solid phase transitions, as will be described in Chapter 11.
3.7. The Clausius–Clapeyron Equation 73

3.7. The Clausius–Clapeyron Equation

An important application of the general equilibrium Equation (3.6.7) is the temperature-pressure

relations for the three systems: liquid-ice, vapor-liquid, and vapor-ice.

3.7.1. Equilibrium between Liquid and Ice Bulk Phases

Consider the equilibrium of the water and ice bulk phases, where phase 1 is water (subscript “w”), and
phase 2 is ice (“i”). The radii r1 = r2 = ∝ for the bulk substances, the phase transition is melting, and
the difference of the molar enthalpies is the molar melting latent heat, hw − hi = Lˆ m = M w Lm , with
Lm being the specific melting heat [cal g−1], the molar volumes are those of liquid, vk0,1 = vw = Mw /rw,
and of ice, vk0,2 = vi = Mw /ri. No foreign substance is present, and the misfit strain is absent, e = 0. No
salt is present and both activities ak,1 = ak,2 = 1. Under these conditions, (Eqn. 3.6.7) is

Lˆ m ( v − vi )
− dT + w dp = 0 . (3.7.1)
T2 T
The number of components in this system is c = 1, the number of phases j = 2, and, according to
the phase rule (Eqn. 3.3.6), the variance Nw = 2 + 1 − 2 = 1. We have one independent variable and
can study dependence of the melting pressure pm on the temperature T. Thus, the general equilibrium
Equation (3.7.1) reduces to the Clapeyron equation used in the following forms

dpm hw − hi ∆Sη wi M w Lm Lm
= = = = , (3.7.2)
dT T ( v w − vi ) ∆vwi T ( vw − vi ) T (1/ρ w − 1/ρi )

where the second equality makes use of the relation for the enthalpies h and entropies Sh,
hw − hi = T ( Sη w − Sηi ) that follows from (Eqn. 3.1.22). This equilibrium between liquid and ice can
exist at the melting point with pm, Tm, and this Clapeyron equation describes the variation of the melt-
ing pressure pm with temperature, pm(Tm).
Rewritten as
dTm T ( vw − vi ) T (1/ρ w − 1/ρi ) (3.7.3)
= = ,
dpm M w Lm Lm

it describes variations of the melting temperature with pressure. The sign of this dependence
depends on the difference in the molar volumes of liquid and solid. Most known substances con-
tract at freezing, the relation of their liquid and solid volumes is vw > vi. Equation (3.7.3) shows that
dTm /dpm > 0 in this case (i.e., the melting temperature increases with increasing pressure, and the
slopes of the curves are positive on the p-T diagram). However, water is an anomalous substance.
When liquid water freezes, thus forming the ordinary known hexagonal ice Ih, it expands, the ice
Ih has a greater molar volume and smaller density than liquid water, and there is the reverse relation
vi > vw, or ri < rw. Therefore, dTm /dpm < 0; thus, the melting temperature decreases with increasing
pressure, and the slopes of the curves are negative on the p-T diagram. However, there are many
other forms of different ices with various molar volumes, and various signs of dTm /dpm. These will
be considered in Chapter 4.
74 Thermodynamic Relations

3.7.2. Equilibrium of a Pure Water Drop with Saturated Vapor

We can apply again the general equilibrium Equation (3.6.7) to this system. In this case, phase 1 is
water vapor; phase 2 is liquid water; the equilibrium exists with respect to evaporation or condensation;
radius r1 = ∝ for the vapor; the drop radius r2 = r; pressure p is equal to the saturated vapor pressure
ews(r) over the drop (which depends on the drop radius); the difference in enthalpies Dh12 is the molar
latent heat of evaporation Lˆ12 and is related to the specific evaporation heat Le [cal g−1] as Lˆ12 = hv − w

= v − hw = M w Le; the molar volumes are those of vapor, vk0,1 = vv, and of liquid water, vk0,2 = vw = Mw /rw; and
both activities ak ,1 = ak ,2 = 1. Thus, the general equilibrium Equation (3.6.7) is simplified as

M w Le  2σ 
− dT + ( vv − vw )dews (r ) − vw d  wv  = 0 , (3.7.4)
T  r 

where swv is the surface tension at the water-vapor interface. The number of components in this
system is c = 1, and according to the phase rule for the curved interfaces (Eqn. 3.3.12), the variance
Nw = 2. So we have two independent variables. We will vary T and r and study dependence of vapor
pressure on the temperature and the drop radius r. Equation (3.7.4) can be rewritten as

dews (r ) M w Le vw d  2σ wv 
= +  , (3.7.5)
dT T ( vv − vw ) vv − vw dT  r 

where swv is the surface tension at the water-vapor interface. The molar volume of vapor is much
greater than the volume of condensed water, vv >> vw, and vw can be neglected in the denominators.
For vv, we can write from the equation of state (Eqn. 3.4.16) vv = RT/ews, and this equation becomes

dews (r ) e M L e v d  2σ wv 
= ws w2 e + ws w  . (3.7.6)
dT RT RT dT  r 

This is the generalized Clausius–Clapeyron equation. It describes the temperature dependence

of the saturated vapor pressure. The second term on the right-hand side contains r and represents a
correction to dews/dT due to the curvature of the drop surface. It was estimated by Dufour and Defay
(1963) to be ∼10−8/r with r in cm. Thus, its contribution is less than 10% for r > 10−7 cm, and less
than 1% for r > 10−6 cm. For larger drops or for the bulk water, the r-dependence can be neglected
with the corresponding accuracy, so the rest of this equation is

1 dews d ln ews M L Le
= = w 2e = , (3.7.7)
ews dT dT RT Rv T 2

where Rv = R/Mw is the specific gas constant for the water vapor. This is the Clausius–Clapeyron
equation for water vapor pressure saturated over a plane water surface that plays an important role
in cloud physics. The application of the generalized Clausius–Clapeyron Equation (3.7.6) may be
desirable for very small droplets—that is, nanoparticles.
The Clausius–Clapeyron Equation (3.7.7) is written for the saturated vapor pressure ews. In some
applications, a modification of the Clausius–Clapeyron equation for the vapor density rws saturated
over water is desired. It can be obtained expressing rws from the equation of state (Eqn. 3.4.17) as
rws = ews/(RvT) and using the Clausius–Clapeyron equation. Thus,

dρ ws 1 d  ews  1  1 dews ews 

=   =  − 2
dT Rv dT  T  Rv  T dT T 
1  ews Le ews  ρ  L 
= ws  e − 1 , (3.7.7a)
Rv T  Rv T 2 T 
= −
T  Rv T 

where we again used the equation of state in the last equality.

3.7. The Clausius–Clapeyron Equation 75

3.7.3. Equilibrium of an Ice Crystal with Saturated Vapor

For this system, phase 1 is vapor (subscript “v”), phase 2 is ice (“i”), r1 = ∝, r2 = rc is the radius of an
ice crystal (assuming that it has a spherical shape), the environmental pressure is the pressure eis of
vapor saturated over ice, and the enthalpies difference is hv − hi = Lˆ s = M w Ls , where Ls is the specific
latent heat of sublimation or deposition. We can again apply the general equilibrium Equation (3.6.7).
As in the case with the drop earlier, the number of components in this system is c = 1, and according
to the phase rule for the curved interfaces (Eqn. 3.3.12), the variance Nw = 2. So we have two indepen-
dent variables. We will vary again T and r and study dependence of vapor pressure on the temperature
and the crystal radius r. Just as with the vapor and droplet system earlier, starting from the general
equilibrium Equation (3.6.7) we arrive at a similar generalized Clausius–Clapeyron equation for the
vapor pressure over ice eis

deis (rc ) e M L e v d  2σ iv 
= is w2 s + is i , (3.7.8)
dT RT RT dT  rc 

where siv is the surface tension at the ice-vapor interface. The second term on the right-hand side
is also typically much smaller than the first term, and can be on the order of 10% for crystals of
size ∼10−7 cm. Its contribution can be noticeable—e.g., for small ice germs nucleating in water at
very low temperatures. For larger crystals or for bulk ice, the second term can be ignored, and so
we arrive at the Clausius–Clapeyron equation for the vapor pressure eis(T) saturated over a plane
ice surface:

1 deis d ln eis M L Ls
= = w 2s = . (3.7.9)
eis dT dT RT Rv T 2

A modification of the Clausius–Clapeyron equation for the vapor density ris saturated over ice can
be derived similarly to the derivation for rws just discussed. Expressing ris from the equation of state
(Eqn. 3.4.18) as ris = eis/(RvT) and using the Clausius–Clapeyron equation, we obtain

dρis 1 d  eis  1  1 deis e 

=   =  − is2 
dT Rv dT  T  Rv  T dT T 
1  eis Ls e  ρ  L 
− is  = is  s − 1 . (3.7.9a)
Rv T  Rv T 2
=
T T  Rv T 

Equations (3.7.7a) and (3.7.9a) are used in subsequent chapters for derivation of the particle growth
rates and supersaturation equations.
The transition vapor-ice can be viewed as a sequence of transitions between vapor-liquid and
liquid-ice. Then, from the energy or enthalpy conservation,
Lˆ s = M w Ls = hv − hs = (hv − hw ) + (hw − hs ) = M w ( Le + Lm ) , (3.7.10)

we obtain a relation among the three melting heats of deposition, condensation, and melting:

Lˆ s = Lˆe + Lˆ m , Ls = Le + Lm . (3.7.11)

This relation is a constraint that allows determination of any of the three quantities, Ls, Le and Lm, if
the other two are known.
76 Thermodynamic Relations

The right-hand sides of Equations (3.7.7) and (3.7.9) are positive; therefore the saturated pressures
ews and eis increase with increasing temperatures. If it is assumed that Le, Ls do not depend on tem-
perature, Equations (3.7.7) and (3.7.9) can be easily integrated in the following manner:

 L 1 1   L ∆T 
ews (T ) = ews (T0 ) exp  − e  −   = ews (T0 ) exp  − e , (3.7.12)
 Rv  T T0    Rv TT0 

 L 1 1   L ∆T 
eis (T ) = eis (T0 ) exp  − s  −   = eis (T0 ) exp  − s , (3.7.13)
 Rv  T T0 
  Rv TT0 

where T0 is some reference point, which is usually the triple point 273.16 K, and DT = T0 − T. These
equations can be used with sufficient accuracy in many cloud physics applications where the tem-
perature change is sufficiently small.
However, in many problems, especially at low temperatures, variations of Le, Ls with tempera-
ture become substantial and should be accounted for. To calculate the derivative dL12/dt, we use
the relations (Eqn. 3.1.22) from Section 3.1, which with the condition of equilibrium m1 = m2 give
Lˆ12 = h1 − h2 = T (sη1 − sη 2 ), and (Eqn. 3.1.20), sh = −(∂m/∂T)p, and a definition (Eqn. 3.1.18) of the
molar heat capacity, Cp = (∂h/∂T)p = −T(∂sh/∂T)p. Now we take the differential

dLˆ12 d (h1 − h2 ) ∂(h1 − h2 ) ∂(h1 − h2 ) dp

= = + . (3.7.14)
dT dT ∂T ∂p dT

The first term on the right-hand side is the difference of the heat capacities between the phases 1 and
2—i.e., ∂Dh/∂T = DCp = Cp1 − Cp2. The derivative ∂hk /∂p in the second term can be transformed using
(Eqn. 3.1.22) from Section 3.1, hk = mk +Tshk, giving us

∂hk ∂( µ k + TSη k ) ∂µk ∂sη k

= = +T . (3.7.15)
∂p ∂p ∂p ∂p

Using the relation (Eqn. 3.1.21), we see that the first term on the right-hand side is vk, and the second
term can be expressed via mk, so

∂hk  ∂2 µk  ∂  ∂µk   ∂v 
= vk + T  = vk − T = vk − T  k  . (3.7.16)
∂p  ∂T ∂p  p ∂T  ∂p  p  ∂T  p

Collecting all the terms, we obtain

dLˆ12 dp
= (C p1 − C p 2 ) + [( v1 − v2 ) − T ( v1κ v1 − v2κ v 2 )] , (3.7.17)
dT dT
where kvk is the isobaric compressibility defined as

1  ∂ vk 
κ vk = . (3.7.18)
vk  ∂T  p

The second term on the right-hand side of (Eqn. 3.7.17), proportional to dp/dT, is usually much
smaller than the first term under typical cloud conditions. However, at low temperatures or at high
pressures this term can give a noticeable correction to dL /dT and to the saturated vapor pressures.
If the second term is neglected, we obtain

dLˆ12
= C p1 − C p 2 . (3.7.19)
dT
3.7. The Clausius–Clapeyron Equation 77

Dividing both sides by Mw yields the same relation for the specific latent heat L and capacity cp. For
equilibria among the three pairs of water phases, vapor, liquid and solid, this gives the relations for
the corresponding specific latent heats and isobaric heat capacities known as Kirchoff’s equations:

dLe dLs dLm

= c pv − c pw , = c pv − c pi , = c pw − c pi , (3.7.20)
dT dT dT
where subscripts “v”, “w”, and “i” mean vapor, water, and ice.
Using Kirchoff’s equations, Le(T), Ls(T), and Lm(T) can be obtained by integration of (Eqn. 3.7.20),
then they can be substituted into the Clausius–Clapeyron equations to give

 T0 L (T )dT 
ews (T ) = ews (T0 ) exp  − ∫ e 2 , (3.7.21)
 T Rv T 
 T0 L (T )dT 
eis (T ) = eis (T0 ) exp  − ∫ s 2 . (3.7.22)
 T Rv T 

The vapor pressures of water and ice coincide at the triple point T0 = 273.16 K, where ews = eis =
6.11657 hPa ≈ 6.11 mb.
Variations of cp with temperature are much smaller than that of L12 at moderate temperatures.
However, variations of cp may become important at low temperatures, when cp decreases and tends
to 0 as T approaches 0 Kelvin (Landau and Lifshitz, v.5, 1958b; Hobbs, 1974). This may influence
the saturated vapor pressures. Reviews and reconstructions of the enthalpies, entropies, saturation
pressures, heat capacities, and other quantities will be considered in Chapter 4. For most derivations
in the next chapters, it is sufficient to use the Clausius–Clapeyron Equations (3.7.7) and (3.7.9) for
bulk phases. In practical calculations used in numerical models or when analyzing measurement data,
various empirical fits are usually used that account for these additional temperature dependencies.
We will return to a discussion of the liquid-ice transitions in Chapter 4 devoted to the properties of
water, and in Chapters 8 and 9 devoted to ice nucleation in clouds.
Consider now a situation when all three water phases are in equilibrium. The number of compo-
nents c = 1, the number of phases j = 3, and according to the phase rule (Eqn. 3.3.6) for the bulk
phases, this system has Nw = c + 2 − j = 0, zero of thermodynamics degrees of freedom. The condi-
tion of equilibrium is
µ v (T , p) = µ w (T , p) = µi (T , p). (3.7.23)

These are two equations with the two unknowns, T and p, which are uniquely defined by these equa-
tions. Thus, such an equilibrium is possible in only one point T0, p0 on the T − p diagram, called the
triple point. The solution of these equations gives T0 = 273.16, p0 = 6.11 mb.
A schematic representation of the p-T phase diagram for water around the triple point Ttr is shown
in Fig. 3.3. The diagram is divided into three areas: solid ice, liquid, and vapor. Within the single-
phase areas, the system is bivariant (Nw = 2), meaning pressure and temperature can be indepen-
dently varied. The solid lines separating the areas with Nw = 2 connect the points of equilibrium
coexistence of the two phases, representing the univariant systems with Nw = 1. All the lines join
at the triple point Ttr (T = 273.16 K, p = 6.11 mb), where all three phases coexist and the system is
invariant, Nw = 0. The line “liquid-vapor” is the vapor pressure curve of liquid water at T > Ttr. This
line below Ttr denotes an extension of the vapor pressure curve to temperatures below 273.16 K.
Where water still does not freeze and can be in a liquid metastable state (as in this case), it is called
supercooled water. A large fraction of atmospheric clouds and fogs exist at temperatures below 0 °C.
Some may stay liquid down to −25 to −30 °C in this liquid supercooled metastable state without
78 Thermodynamic Relations

Pcrit,1
liquid 218 atm,

Saturated pressure (hPa)

solid Nw=2 647 K
Nw=2

Nw=1

1
w=
N
vapor
Nw=2
6.11 =1 Ttr , Nw=0
r, Nw
po = 1
va Nw
id- or,
liqu -v ap
ice

273.16
Temperature (K)

Figure 3.3. T-p phase diagram of water around the triple point Ttr. The three curves indicate the
lines of coexistence of the two phases of water in equilibrium, and Nw indicates the number of
thermodynamic degrees of freedom in the corresponding areas. At the triple point Ttr (T = 273.16 K,
p = 6.11 hPa), all three phases coexist and Nw = 0. The line “liquid-vapor” below Ttr denotes
extension of the vapor pressure curve to temperatures below 273.16 K. The line below, marked
“ice-vapor,” denotes the line of equilibrium coexistence of vapor and ice. Pcrit,1 denotes the first
critical point at pcr1 = 218 atm, Tcr1 = 647 K, and the liquid and vapor phases become indistinguishable
at p ≥ pcr1 and T ≥ Tcr1.

natural freezing. This makes them suitable for cloud seeding with crystallizing agents, as will be
described in subsequent chapters.
The line below, marked “ice-vapor,” denotes the line of equilibrium coexistence of vapor and
ice. Pcrit,1 denotes the first critical point at pcr1 = 218 atm, Tcr1 = 647 K. The liquid and vapor phases
become indistinguishable at p ≥ pcr1 and T ≥ Tcr1. Here, this critical point of water is called “first,”
because there can be another hypothesized “second” critical point at low temperatures where the
phase states of water, and the transitions between them, can be substantially different, as will be
discussed in Chapter 4.

3.7.4. Humidity Variables

Cloud formation depends on the moisture content of the air that is characterized by several humidity
variables. The absolute humidity is equal to the vapor density rv, which is the vapor mass in a unit
volume of the air. The other variables are the water vapor mixing ratio wv, its saturated values over
water and ice, wws, wis, and the mole fraction of vapor in the air, xv, which are defined via vapor pres-
sure ev or density rv, their saturated values, air density ra, and pressure p:
ρv ev ρ ws ews
wv = = εw , wws = = εw ,
ρa p − ev ρa p − ews
ρ eis nv e
wis = is = ε w , xv = = v, (3.7.24)
ρa p − eis na + nv p
3.7. The Clausius–Clapeyron Equation 79

where ew = Mw /Md = 0.622, nv and na are the number of moles of the vapor and air in a volume and we
used the equation of state for water vapor and air from Section 3.4. The air density at normal condi-
tions is on the order ra ∼ 10−3 cm−3, and the vapor density rv is 3 to 4 orders smaller. Since p >> e, p
>> ews, and p >> eis, the approximate relations are
ev ews eis
wv ≈ ε w , wws ≈ ε w , wis ≈ ε w . (3.7.24a)
p p p

The specific humidity qv and its saturated values over water and ice qws, qis are defined via the
masses mv of vapor and md of dry air or their densities:
mv ρv ev e ρ
qv = = = εw ≈ ε w v ≈ wv ≈ v , (3.7.25a)
ma + m v ρa + ρ v p − (1 − ε w )ev p ρa
mws ρ ws e ρ
qws = = ≈ ε w ws ≈ wws ≈ ws , (3.7.25b)
ma + mws ρa + ρ ws p ρa
mis ρis e ρ
qis = = ≈ ε w is ≈ wis ≈ is . (3.7.25c)
ma + mis ρa + ρis p ρa

Since rv << ra, the specific humidities are very close to the mixing ratios and are often used as qv ≈ wv =
rv /ra. Thus, specific humidity and its values saturated over water and ice are approximately equal to
the corresponding mixing ratios.
The water and ice saturation ratios, Sw, Si, are defined as
ρv e ρv e
Sw = = v , Si = = v. (3.7.26)
ρ ws ews ρis eis

The fractional relative humidities over water and ice are equal to the corresponding saturation ratios.
The relative humidities in percent are
RHW = Sw × 100%, RHI = Si × 100%. (3.7.27)

The water and ice supersaturations, sw, si, are used in cloud physics in various forms, as fractional,
absolute, and specific, depending on the problem considered or the model used. The fractional
supersaturations are
ρ v − ρ ws e − ews ρ v − ρis e − eis
sw = = v = Sw − 1, si = = v = Si − 1. (3.7.28)
ρ ws ews ρis eis

The supersaturations in percent are obtained by multiplication of these quantities by 100%. The spe-
cific supersaturations over water Dw and ice Di are defined via specific humidity qv and its saturated
values over water and ice qws, qis
∆ w = qv − qws , ∆ i = qv − qis . (3.7.29)

The absolute supersaturations over water and ice are related to the vapor densities,

δ w = ρ v − ρ ws = ∆ w ρ a , δ i = ρ v − ρis = ∆ i ρ a . (3.7.30)

The supersaturations are the small differences of the two much larger quantities, humidity and satu-
rated humidity. Therefore, solving equations directly for supersaturations yields more precise results
than solving equations for humidities. The equations for supersaturations in various forms suitable
for various models will be derived and used in the subsequent sections.
80 Thermodynamic Relations

3.8. Phase Equilibrium for a Curved Interface—The Kelvin Equation

Consider a system consisting of a pure water drop in equilibrium with an environment of humid air
and again apply the general equilibrium Equation (3.6.7). For this system, phase 1 is water vapor,
phase 2 is liquid water. Then, the latent heat of phase transition is condensation or evaporation heat
Le, the molar volumes vk0,1 and vk0,w are the molar volumes of vapor vv and water vw, r1 = ∝ (bulk
phase), r2 = r (the radius of the drop), s12 = swa (the surface tension at the water-air interface), and the
misfit strain is absent, e = 0. The activity of water vapor av, assuming that it behaves as an ideal gas,
is just its mole fraction, av = xv = ewr(r)/p, where ewr is the vapor pressure over the drop surface, and
p is the air pressure. Thus, (Eqn. 3.5.7) is reduced to the form:

Lˆe ( v − vw ) v  2σ 
− dT + v dp − w d  wa  + Rd ln(ewr /p) = 0 . (3.8.1)
T2 T T  r 

The number of components in this system is c = 2 (water and air), and according to the phase rule
(Eqn. 3.3.12) for the curved substances, the variance of the system is Nw = 3. There are 4 differ-
entials in (Eqn. 3.8.1) of 4 variables (T, p, r, ewr), but only 3 of them are independent, and for the
integration of (Eqn. 3.8.1), we have to choose any 3 of 4 variables, and the number of combinations
is C43 = 4 ⋅ 3 ⋅ 2 /1 ⋅ 2 ⋅ 3 = 4 . Integration can yield the dependencies among these 4 possible
combinations—that is, 4 possible equations.
If we consider an isobaric process and keep p = const, dp = 0, then (Eqn. 3.8.1) is simplified as

Lˆe v  2σ 
− dT − w d  wa  + Rd ln(ewr ) = 0 . (3.8.2)
T2 T  r 

If we divide it by dT and multiply by R, we obtain again the generalized Clausius–Clapeyron

equation (3.7.6). Then, neglecting the curvature term for large r, we would obtain the Clausius–
Clapeyron equation (3.7.7) describing the dependence of ews on T and ignoring its dependence on r.
If, vice versa, we assume T = const, dT = 0, and study the dependence of ewr on the curvature r, we
obtain another equation. For this case, using the relation vw = Mw/rw, (Eqn. 3.8.2) becomes

vw  2σ wa  M w 2σ wa  1 
d ln[ewr (r )] = d  = d . (3.8.3)
RT  r  ρ w RT r

Integration from (r = ∝, ews)—i.e., from the plane water surface—to (r, ewr(r)) yields
ewr (r ) 2 M wσ wa A 2 M wσ wa 2σ wa
ln = = K , AK = = , (3.8.4)
ews RTρ w r r RTρ w Rv Tρ w

or in exponential form

ewr (r )  2 M wσ wa   AK 
= exp   = exp  r  . (3.8.5)
ews  RT ρ w r 

This equation describes the dependence of the vapor pressure around the drop on its radius. It was
derived by William Thomson (Lord Kelvin) and is called the Kelvin equation; the parameter AK is
called the Kelvin curvature parameter. Since AK > 0, the Kelvin equation describes an increase of the
3.9. Solution Effects and the Köhler Equation 81

vapor pressure over the curved surface relative to the plane surface. An estimate of swa ∼ 72 dyn cm−2
gives for the Kelvin’s curvature parameter AK ∼ 1.2 × 10−7 cm at T ∼ 20 °C. Therefore, an increase of
vapor pressure over a drop with r =10−6 cm is ∼exp(0.1) ∼ 10%, and less that 1% for the drops with
r ≥ 10−5 cm.
The ratio ewr(r)/ews is the water saturation ratio Sw, and the Kelvin equation can also be written as

2 M wσ wv A
ln Sw = = K. (3.8.6)
RTρ w r r

Kelvin equations in this forms are used in many applications, as will be illustrated later in equations
for the drop activation (Chapters 6 and 7) and crystal nucleation (Chapters 8 and 9).

3.9. Solution Effects and the Köhler Equation

Consider a system consisting of a solution water drop in equilibrium with an environment of humid
air and again apply the general equilibrium Equation (3.6.7). For this system, phase 1 is water vapor,
phase 2 is aqueous solution. The latent heat of phase transition is condensation or evaporation heat
hv − hw = Lˆe = M w Le with Le being the specific evaporation heat, the molar volumes vk0,1 and vk0,w
,
are the molar volumes of vapor vv and water vw, r1 = ∝ (bulk phase), r2 = r (the radius of the drop),
s12 = ssa (the surface tension at the solution-air interface), and the misfit strain is absent, e = 0. The
activity of water vapor av, assuming its behavior as an ideal gas, is its mole fraction, av = xv = ewr(r)/p,
where ewr(r) is the vapor pressure over the drop surface, and p is the air pressure. The activity of water
aw ≠ 1, in contrast to the case of pure water, and is determined by Equations (3.5.16) or (3.5.18) and
(3.5.19). Thus, (Eqn. 3.6.7) is reduced to the form:

Lˆe ( v − vw ) v  2σ 
− dT + v dp − w d  sa  + Rd ln[ewr (r )/p] − Rd ln aw = 0 , (3.9.1)
T2 T T  r 

which is a generalization of (Eqn. 3.8.1). The number of components in this system is c = 3 (water,
salt, and air), and according to the phase rule (Eqn. 3.3.12) for the curved substances, the variance of
the system is Nw, which would be 4. However, if we assume that mass of salt ms = const (neglecting
scavenging at the earlier stages of drop growth that could change the salt mass), this imposes one
more constraint, and so the variance Nw = 3, as in the case of pure water drop. Thus, of 5 differentials
in (Eqn. 3.9.1) we have only 3 independent variables. We keep T = const, and p = const, and so this
equation is reduced to:
vw  2σ sa 
− d  + Rd ln[ewr (r )] − Rd ln aw = 0 . (3.9.2)
T  r 

Substitution vw = Mw /rw and integration from (r = ∝, ews, aw = 1)—i.e., from the plane surface of pure
water, to (r, ewr(r), aw) yields

ewr (r ) 2 M wσ sa A
ln = + ln aw = K + ln aw . (3.9.3)
ews RTρ w r r
82 Thermodynamic Relations

Using the definition of the water saturation ratio Sw = ers /ews and water activity (Eqn. 3.5.18) for fully
soluble CCN, this equation can also be written in the form
AK 2 M wσ sa ν Φ s M w ms
ln Sw = + ln aw = − 3
, (3.9.4)
r RTρ wr M s [(4/3)π rs″raw − ms ]

or

A   2 M wσ sa ν Φ s M w ms 
Sw = aw exp  K  = exp  − . (3.9.5)
 r   RT ρ w r M s [(4/3)π r ″r
s aw
3
− m s ] 
For sufficiently diluted solutions, using approximation (Eqn. 3.5.19) for aw, we obtain
2 M wσ sa 3ν Φs M w ms A B
ln Sw = − = K − 3, (3.9.6)
RTρ w r 4π M s ρ w r 3 r r

where AK is the Kelvin’s or curvature parameter defined in (Eqn. 3.8.4) and B is the nucleus activity
defined in (Eqn. 3.5.17),

M w 2σ sa 3ν Φs M w ms
AK = , B= . (3.9.7)
RTρ w 4π M s ρ w

For the aerosol particles containing insoluble fractions, substituting water activity (Eqn. 3.5.16) for
mixed CCN into (Eqn. 3.9.3), we obtain

2 M wσ sa 3ν Φs M w ms A B
ln Sw = − = K − 3 , (3.9.8)
RTρ wr 4π M s ρ w (r 3 − rd3 ) r r − rd3

and the soluble mass ms in B is expressed via the mass soluble fraction em, and the mass of a dry
nucleus md as ms = emmd.
Equations (3.9.3) to (3.9.8) are various forms of the Köhler equation, derived by the Swedish
scientist Köhler (1921, 1936). They represent an invaluable tool in atmospheric physics for calcula-
tions of the aerosol hygroscopic growth, drop activation on CCN, and in many other applications
considered in the subsequent chapters.

3.10. Thermodynamic Properties of Gas Mixtures and Solutions

3.10.1. Partial Gas Pressures in a Mixture of Gases

The partial pressure pk of a k-th component in a mixture of gases (Eqn. 3.5.4) and Raoult’s law
(Eqn. 3.5.4a) were given in Section 3.5, as in most textbooks, as empirical laws, without derivation.
The mathematical derivation can be useful since it is based on the equation of equilibrium for bulk
phases, and shows the approximations and applicability of these laws and their relation to the other
properties of gas mixtures and solutions.
Consider first a mixture of ideal gases in the volume V with partial pressures pi, number of moles
ni, and a common temperature T. We can write the equation of state (Eqn. 3.4.15a) for each gas and
then sum the equations over all Ni gases,
Ni Ni
pk V = nk RT , ∑ p V = ∑ n RT .
i i
(3.10.1)
i =1 i =1
3.10. Thermodynamic Properties of Gas Mixtures and Solutions 83

Dalton’s law states that the total pressure p in a mixture of gases is equal to the sum of the partial
pressures pi of all gases, Spi = p. Dividing the lhs and rhs of the first equation in (Eqn. 3.10.1) by the
lhs and rhs of the second equation and using Dalton’s law for the partial gas pressures pi, we obtain
pk pk nk
Ni = = Ni = xk . (3.10.2)
p
∑p i ∑n i
i =1 i =1

The expression on the right-hand side is the mole fraction xk of the k-th gas, thus
pk = px k . (3.10.3)

We have therefore derived Equation (3.5.4.a), whereby the partial pressure of a gas in the gas mixture
is proportional to the total pressure and the gas mole fraction.

3.10.2. Equilibrium of Two Bulk Phases around a Phase Transition Point

Several useful equations for bulk solutions can be derived from the general equilibrium Equation
(3.6.7). For bulk solutions, r1 = r2 = ∞, so the terms with surface tension vanish. We do not consider
effects of the misfit strain and suppose e = 0; thus the equation becomes

Lˆ12 ( vk 0,1 − vk 0,2 )  ak ,1 

− 2
dT + dp + Rd ln   = 0. (3.10.4)
T T  ak ,2 

Consider the equilibrium between two bulk phases around the phase transition point T0, p0 in a
pure solvent. Addition of solute will cause a shift of the equilibrium point towards other values T and
p. If a solution is sufficiently weak, the changes DT = T – T0 and Dp = p0 – p are small compared to
T and p. Integration of (Eqn. 3.10.4) within these small intervals DT and Dp and multiplication by
T yields

M w L12  ak ,1 
− ∆T + ( vk 0,1 − vk 0,2 ) ∆p + RT ln   = 0, (3.10.5)
T  ak ,2 

where the molar latent heat Lˆ12 is expressed via the specific latent heat L12. This equation describes
the equilibrium in bulk solvent around the phase transition point.
If we consider ideal solutions, then approximately ak1 ≈ 1 − xs1, and ak2 ≈ 1 − xs2, where xs1
and xs2 are the mole fractions of solute in phases 1 and 2. For sufficiently weak solutions, lnak1 ≈
ln(1 − xs1) ≈ −xs1, lnak2 ≈ −xs2, and ln(ak1/ak2) ≈ −(xs1 − xs2). Substituting into (Eqn. 3.10.5) yields

M w L12
− ∆T + ( vk 0,1 − vk 0,2 ) ∆p = RT ( x s1 − x s 2 ) . (3.10.6)
T
Equations (3.10.5) and (3.10.6) are in agreement with the Clapeyron equation for pure solvent since
with ak1 = ak2 = 1, or xs1 = xs2 = 0, they convert into Dp/DT = (MwL12/[(vk0,1 − vk0,2)T] (Section 3.7).
Consider three particular cases with the presence of solute.
84 Thermodynamic Relations

3.10.3. Raoult’s Law for Solutions

Case (a). Suppose that phase 1 is liquid, phase 2 is vapor, the phases are at the same temperature in
equilibrium, and DT = 0. If the liquid is pure, then the vapor pressure is equal to its saturated value.
We denote the vapor pressure over pure solvent with ews,0. If solvent is present, the vapor pressure in
solution will change by an amount Dews ≡ Dp that can be expressed with (Eqn. 3.10.6). Neglecting
the volume vw1 of the liquid that is much smaller than the vapor volume vwv ≡ vw2, (Eqn. 3.10.6) with
DT = 0 yields
∆ews vwv = − RT ( x s1 − x s 2 ). (3.10.7)

That is, pressure change in the vapor phase is determined by the difference of solute mole fractions
in both phases.
If the solute is nonvolatile and is absent in vapor, xs2 = 0, then
RT (3.10.8)
∆ews = − x s1 .
vwv

According to the equation of state in Section 3.4, for one mole of vapor, RT/vwv = ews,0 and we obtain
∆ews = − ews ,0 x s1 . (3.10.9)

This is Raoult’s law, which states that the vapor pressure over a solution is depressed compared to
the pressure over pure solvent; a depression is proportional to the saturated pressure over pure solvent
and to the molar fraction of solute in solution.
Raoult’s law can be written for a full vapor pressure:
pw = ews ,0 + ∆ews = ews ,0 − ews ,0 x s1 = ews ,0 (1 − x s1 ) = ews ,0 x w . (3.10.10)

where ews,0 is the vapor pressure over pure solvent. That is, the pressure of a solvent (e.g., water) is
proportional to its molar fraction. The same is valid for any substance in solution, as was formulated
by (Eqn. 3.5.4a), pk = xk pk0, which is another formulation of Raoult’s law. Raoult’s law is a key
starting point in derivation of Köhler’s equation, considered in Section 3.9, which governs aerosol
hygroscopic growth and drop activation in clouds (Chapters 6 and 7). This equation is also used in
derivation of the critical radii and energies of ice nucleation in Chapters 8 and 9.

3.10.4. Freezing Point Depression and Boiling Point Elevation

Consider now another particular case (b) of Equation (3.10.6), the process of freezing when Dp = 0,
− M w L12 ∆T /T = RT ( x s1 − x s 2 ). (3.10.11)

For freezing, phase 1 is water with the molar fraction of solute xs = xs1, phase 2 is ice, and assume that
the solute is rejected from ice upon freezing, xs2 = 0, since usually the salt concentration in ice is very
small. The latent heat is released upon freezing, and the enthalpy of ice is lower than that of water;
thus MwL12 = hw − hi = MwLm > 0. Equation (3.10.11) predicts negative DT, while the freezing point
depression is defined as a positive dTf = T0 − Tf. Thus, the last equation yields

RT 2
δ T f = T0 − T f = −∆T = xs , (3.10.12)
M w Lm
3.10. Thermodynamic Properties of Gas Mixtures and Solutions 85

where T0 is the freezing point of a pure solvent. This equation shows that the freezing point in the
presence of solution shifts to lower temperatures, and the depression dTf is proportional to the molar
fraction of solute in solution.
This equation is also used with the solute molality M̂ s instead of the mole fraction xs, which can be
written for dilute solutions as Mˆ s ≈ x s /M w . If we replace xs with M̂ s, this equation becomes

RT 2 ˆ RT 2
δ Tf = M s = K f Mˆ s , Kf = , (3.10.13)
Lm Lm

where Kf is the cryoscopic constant (recall that Lm is here the specific heat per unit mass, not per
1 mole). The cryoscopic constants were measured and tabulated for various substances (e.g., Atkins,
1982). For water, Kf = 1.86 K kg mol−1. It is easy to show that the same is valid for a reverse process
of melting, and then the melting point depression dTm ∼ dTf.
This effect of freezing (melting) point depression provides the basis for the preparation of “cool-
ing mixtures” consisting of milled ice or snow and cooling agents that freeze at temperatures much
lower 0 °C. For example, a mixture of snow with salt NaCl (in the ratio 2:1) freezes at −21 °C, and
a mixture of snow with CaCl2 (in the ratio 7:10) freezes at −50 °C. Cooling agents have numerous
applications. For example, when a cooling agent is dispersed over the roads covered with snow, a
cooling mixture is formed, and the snow begins to melt at temperatures much lower than 0 °C, thus
cleaning the road of snow. Natural aerosols usually contain many various salts and acids; therefore
deliquescent aerosol particles may remain in liquid state at very cold temperatures. Their freezing
point depressions and thresholds of ice nucleation in clouds can be calculated in a first approximation
with the equations given earlier.
As follows from the preceding derivation, Equations (3.10.12) and (3.10.13) are an approximation
for sufficiently weak solutions without strong non-ideality. For concentrated and non-ideal solutions,
these equations may lead to errors; more detailed equations will be considered in Chapters 8, 9, and 10.
Consider another particular case (c) of Equation (3.10.6), when the phase transition is evapora-
tion or boiling and Dp = 0. In this case, phase 1 is liquid and phase 2 is vapor. The enthalpy of
vapor is higher than that of liquid water, hv > hw; therefore the molar latent heat is negative, MwL12 =
hw − hv = −MwLe. Suppose that the solute is nonvolatile and is absent in the vapor phase, so that xs2 = 0,
its mole fraction in solute is xs, and (Eqn. 3.10.6) yields the boiling temperature increase due to solute

RT 2 (3.10.14)
δ Tb = Tb − T0 = ∆T = xs ,
M w Le

where T0 is the boiling point of pure solvent (e.g., water). This is the boiling point elevation, it shows
that the boiling point of a liquid shifts to higher temperatures in the presence of solute.
This shift is proportional to the mole fraction of solute. With molality Mˆ s ≈ x s /M w, this gives

RT 2 ˆ ˆ , RT 2
δ Tb = Ms = Kb M s Kb = ,
Le Le
(3.10.15)

where Kb is the ebullioscopic constant. The ebullioscopic constants have been measured and tabu-
lated for various substances (Atkins, 1982). For water, Kb = 0.51 K kg mol−1. Boiling point elevation
can be used to measure the relative molecular mass of soluble non-volatile materials in atmospheric
aerosols that participate in cloud formation (Atkins, 1982).
86 Thermodynamic Relations

A similar consideration shows that the condensation point shifts to higher temperatures by d Tc in
the presence of solutes. The effects of elevated boiling and condensation points may play a role
in the formation of clouds from superheated and polluted sources. When the vapor jet is ejected from
the source, it cools, eventually condenses at some distance from the source, and forms a cloud at
temperature Tc. This temperature of condensation is higher by dTc in the presence of solute, and
condensation may occur closer to the hot source.
Examples are formations of clouds from volcanic fumaroles or eruptions, from massive natural
forest and prairie fires, and from special devices such as meteotrons, which are designed for artificial
rain production. Meteotrons are constructions consisting of several vertically pointed jet engines that
can produce a powerful convective plume. Under appropriate conditions, this plume may create a
convective cloud and rain. Some native tribes in Africa and South America create such artificial fires
to make clouds and rain, and thus fight long droughts. These attempts are often successful. These
clouds may spread over long distances (up to regional and global scales) and can significantly affect
the atmosphere and surface since they contain various chemicals. Due to boiling (condensation) point
elevation, the condensation level of these clouds may be lower above the hot surface, when the pol-
lutants’ concentration is higher. This may influence the properties of these clouds, the intensity of
precipitation formation, and their subsequent effects. Another example is the formation of condensa-
tion trails or contrails from jet aircraft or shiptracks from ship exhausts, which may cause noticeable
effects on atmospheric radiation on a regional and perhaps global scale. Due to boiling or condensa-
tion point elevation, contrails and shiptracks may form closer to the hot source, which may influence
their sizes, shapes, and effects.

3.10.5. Relation of Water Activity and Freezing Point Depression

Previous consideration was valid for ideal solutions, while real liquids exhibit deviation from ideal
behavior. There are several ways to account for the non-ideality of solutions. One is to introduce van’t
Hoff’s factor i on the right-hand side of equations for freezing point depression and boiling point
elevation for ionic solutions:

RT 2 RT 2
δ Tf = i xs , δ Tb = i xs , (3.10.16)
M w Lm M w Le

Another way is to use water activity instead of the molar fraction, as described in the following.
If a pure ice (free of solute) and an aqueous solution are in equilibrium, the chemical potentials
of ice, mi(p, T), and water, mw(p, T), should be equal, mi(p, T) = mw(p, T). Using (Eqn. 3.5.21) for mw,
we obtain
µi ( p, T , aw ) = µ w 0 ( p, T ) + RT ln aw . (3.10.17)

Equation (3.10.17) allows derivation of a useful relation for the water activity. Dividing each term
by T and taking the derivative by T at p = const, we obtain

∂  µi  ∂  µw 0  ∂ln aw
  =   +R .
∂T  T  p ∂ T  T  p ∂T
(3.10.18)
3.10. Thermodynamic Properties of Gas Mixtures and Solutions 87

According to (Eqn. 3.1.23), ∂(mk/T)/∂T = −hk/T2. Substituting this relation into (Eqn. 3.10.18), we obtain

∂ln aw 1 ∂   µi   µw 0   hi − hw M L Lm
=   −   =− = w 2m = , (3.10.19)
∂T R ∂T  T p T  p  RT 2 RT Rv T 2

where Rv = R/Mw is the gas constant for water vapor. Integration of this equation by T from the triple
point T0 to T with the boundary condition aw(T0) = 1 yields

Lm 1 1 Lm δ T
ln aw (T ) = − (3.10.20)
T − T  = − RTT ,
Rv  0  v 0

where dT = T0 − T. This gives two relations, for d Tf and aw. The first one is
RT0 T
δ Tf = − ln aw (T ) . (3.10.21)
M w Lm

This equation describes the freezing point depression, taking into account non-ideality effects. Using
(Eqn. 3.5.13) for aw, we obtain

RT0 T  ms M w  RT0 T ns RT 2
δ Tf =  v Φs m M  = M L v Φs n ≈ M L v Φs x s , (3.10.22)
M w Lm  w s  w w w w m

which differs from (Eqn. 3.10.12) by the factor nΦs and from (Eqn. 3.10.16) by a more rigorous
account for non-ideality and allows more accurate calculations of the freezing point depression,
taking into account the non-ideality of solutions. Equation (3.10.22) is used in many applications.
However, this is still a linear approximation to dTf by xs or aw for sufficiently dilute solutions. We will
return to an evaluation of dTf in Chapters 8 and 9, where a non-linear approximation will be derived
for a wider range of solution concentrations.
The other equation follows from (Eqn. 3.10.20) for aw(T),

 M L δT 
aw (T ) = exp  − w m  . (3.10.23)
 RT0 T 

This equation shows that water activity aw in a bulk aqueous solution at a fixed pressure is a function
of the temperature—that is, the solution concentration in equilibrium with pure ice adjusts to the
temperature. The argument in exponent in (3.10.23) is negative and aw(T) decreases with decreasing
temperature (increasing supercooling dT). Since Lm = Ls − Le, using the Clausius–Clapeyron Equa-
tions (3.7.12) and (3.7.13) for saturated water vapor pressures over water ews and ice eis, Equation
(3.10.23) can be rewritten as
−1
 M L δT    M L δT   e
a (T ) = exp  − w s   exp  − w e   = is .
i
w
(3.10.24)
 RT0 T    RT0 T   ews

That is, the water activity in equilibrium with ice awi (T ) is expressed via the ratio of saturated
vapor pressures over water and ice, awi (T ) = eis /ews, this allows much easier calculations and param-
eterizations of aw in solutions that are in equilibrium with ice, which can be required for calculations
of ice nucleation and freezing and melting temperatures (Chapters 8 and 9).
88 Thermodynamic Relations

3.11. Adiabatic Processes

Thermodynamic processes are called adiabatic if they occur in an air parcel without exchange of
heat with the environment—that is, dQ = dq = 0 in equations of Section 3.1. A process is called a dry
adiabatic process if it proceeds without phase transitions of water. If such transitions take place in
the air with the presence of saturated water vapor, the process is called a wet adiabatic process. Dry
and wet adiabatic processes are considered in this section.

3.11.1. Dry Adiabatic Processes

The first law of thermodynamics (Eqn. 3.1.19b) for air with intensive variables is

dq = deɶ − dw , (3.11.1)

where deɶ = cv dT is the internal energy, cv is the heat capacity at constant volume, and dw = −pdv is
the work done on gas expnasion. Thus,
dq = cv dT + pdv . (3.11.2)

Considering the air as an ideal gas and using the equation of state for an ideal gas, pv = RaT, the last
term can be transformed, pdv = RadT − vdp, and substitution into (Eqn. 3.11.2) yields
dq = (cv + Ra )dT − vdp . (3.11.3)

If we consider an isobaric process, dp = 0, the second term on the right-hand side vanishes and Equa-
tion (3.11.3) shows that the first term is dq = cpdT. Thus, we obtained the relations

dq = c p dT = (cv + Ra ) dT , (3.11.4a)

c p = (cv + Ra ) . (3.11.4b)

For dry air, cv = 717 J kg−1 K−1 = 0.17 cal g−1 K−1, cp = 1004 J kg−1 K−1 = 0.24 cal g−1 K−1, the differ-
ence cp − cv = 288 J kg−1 K−1, and the ratio k = cp/cv = (cv + Ra)/cv = 1.4.
For adiabatic process with dq = 0, it follows from (Eqn. 3.11.3) using the equation of state that

c p dT = vdp = Ra T (dp/p). (3.11.5)

If an air parcel rises from a level with initial T1, p1 to a level with T2, p2, this equation allows us to
find a relation between the initial and final states. Dividing (Eqn. 3.11.5) by T and integrating yields
T2 2 p
dT dp
cp ∫ = Ra ∫ , (3.11.6)
T1
T p1
p

or
Ra/c p ( c p − cv )/c p (κ −1) /κ
T2  p2  p  p 
= =  2 =  2 , (3.11.7)
T1  p1   p1   p1 

where Ra/cp = (k − 1)/k = 0.286. This equation is called the equation of the dry adiabat or Poisson’s
equation. If we begin with Equation (3.11.2) for adiabatic processes with dq = 0,
3.11. Adiabatic Processes 89

Ra T
cv dT = − pdv = − dv , (3.11.8)
v
where we use the equation of state for p. Dividing by T, and integration from (T1, v1) to (T2, v2) gives
T2 2 v
dT dv
cv ∫ = − Ra ∫ , (3.11.9)
T1
T v1
v
Ra / cv κ −1
T2 v  v 
=  1 =  1 . (3.11.10)
T1  v2  v  2

Combining (Eqns. 3.11.7 and 3.11.10) gives

c p /cv R/cp
p2 v  T2 p 
=  1 , =  2 . (3.11.11)
p1  v2  T1  p1 

Equations (3.11.10) and (3.11.11) are other forms of the Poisson equation for dry adiabatic processes.
They show that when the temperature decreases in an air parcel with increasing height, pressure also
decreases and volume increases—that is, the parcel expands with height.
These equations allow us to determine the temperature lapse rate that would be in the atmosphere
without phase transitions and the absence of turbulent mixing and non-adiabatic heating. It follows
from (Eqn. 3.1.3) for the dry adiabatic process with dq = 0 that

dp
dq = c p dT − va dp = c p dT − Ra T = 0. (3.11.12)
p

Using the equation of state, p = raRaTe, where Te is the external temperature, and the hydrostatic equa-
tion, dp = −ra gdz, the second term can be transformed as −(RaT)(dp/p) = (T/Te)gdz, and we obtain
T
c p dT = − g dz . (3.11.13)
Te

Dividing by cpdz, assuming that the temperature inside the parcel T is equal to the external tempera-
ture Te, and denoting the gradient −dT/dz = ga, we obtain
dT g
γa = − = . (3.11.14)
dz cp

The gradient ga is called the dry adiabatic lapse rate. Its value is ≈ 9.8 °C km−1. Thus, an air parcel
cools by about 1 °C for every 100 m of lift. The values of ga depend on g and cp and are different for
various planets. For example, estimates and measurements give ga ∼ 3.5–4 °C km−1 for Mercury, ga ∼7.6–
11 °C km−1 for Venus, ∼4.5 °C km−1 for Mars, ∼2−2.5 °C km−1 for Jupiter, and ∼13.4 °C km−1 for the Sun.
The temperature of an air parcel with initial temperature T and pressure p after adiabatic ascent
or descent to the level with pressure p = 1000 hPa is called the potential temperature and is usually
denoted by q. According to (Eqn. 3.11.7),
Ra/c p Ra/c p
T  p   1000 
= , or θ = T . (3.11.15)
θ  1000   p 
90 Thermodynamic Relations

Taking the logarithm and the differential of (Eqn. 3.11.15), we obtain

dθ dT R dp
= − a . (3.11.16)
θ T cp p

The right-hand side according to (Eqn. 3.11.12) is zero, and we have

dθ = 0, or θ = const, (3.11.17)

that is, the potential temperature is conserved in adiabatic processes. This determines its usefulness
for atmospheric thermodynamics, whereby many of these equations are formulated using q.

3.11.2. Wet Adiabatic Processes

The presence of phase transitions of moisture influences the thermodynamic processes and changes
the vertical lapse rate. Consider an isolated parcel with volume v at pressure p containing one gram of
dry air (v = 1/ra), saturated water vapor with a mixing ratio qws, and some amount of liquid water mix-
ing ratio ql that can evaporate. If an amount of heat dq is added to the parcel, it will cause an increase
in the temperature dT with the corresponding increase in enthalpy dh = cpdT. The term qwscpv, where
cpv is the heat capacity of the vapor, should be added to cp, but it is typically less than 10−2 of cp and
can be neglected. The work of expansion is dw = −vdp. The vapor will become subsaturated and evap-
oration of liquid occurs, so that its amount will decrease by −dql until saturation of vapor is reached
again and the saturated vapor mixing ratio qws is increased by dqws = −dql with the energy Ledqws. For
an adiabatic process, when dq = 0, it follows from the first law of thermodynamics (Eqn. 3.11.3) that
c p dT + Le dqws − vdp = 0 . (3.11.18)

This equation can be rewritten in terms of the rates dividing by dt and using the relations v = 1/ra,
dqws = −dql, multiplying by ra and introducing the condensation rate Icon = radql/dt, thus
dT dp
ρa c p = + Le I con . (3.11.19)
dt dt
This equation of heat balance will be used in subsequent chapters for derivations of supersaturation
equations in liquid clouds.
Using the equation of state for the air, pv = RaT, and the hydrostatic equation, dp = −ragdz, the
last term on the left-hand side of (Eqn. 3.11.18) can be transformed as −vdp = −(RaT)(dp/p) = gdz,
and we obtain
c p dT + Le dqws + gdz = 0 . (3.11.20)

Dividing by cpdz and denoting the wet adiabatic gradient gw = −dT/dz, we obtain
dT g L dq
γw= − = + e ws . (3.11.21)
dz cp c p dz

Since g/cp = ga, this yields

Le dqws
γw= γa + . (3.11.22)
c pa dz
3.11. Adiabatic Processes 91

To derive a more detailed formula for gw, we take a logarithmic derivative of qws = 0.622(ews/p):
1 dqws 1 dews 1 dp
= − . (3.11.23)
qws dz ews dz p dz

Using the chain rule dews/dz = (dews/dT)(dT/dz), the Clausius–Clapeyron equation and hydrostatic
equation yield

dqws  1 dews 1 dp   L g 
= qws  − = qws  − e 2 γ w + . (3.11.24)
dz  ews dz p dz   Rv T Ra T 

Substituting this dqws/dz into (Eqn. 3.11.22) gives us

Le  L g 
γw= γa + qws  − e 2 γ w + . (3.11.25)
cp  Rv T Ra T 

Solving relative to gw, we obtain the wet adiabatic lapse rate:

Le
1+ qws
Ra T
γw= γa . (3.11.26)
L2e
1+ 2
qws
c p Rv T

At T ≈ 275 K (2 °C) and pa ∼ 1000 mb, the second term in the numerator, Le/(RaT)qws ∼ 0.046
(i.e., the numerator is close to 1). The second term in the denominator, Le2/(cpRvT2)qws ∼ 0.64,
thus gw/ga = 1.046/1.64 = 0.64 and gw ≈ 10 K km−1 × 0.64 = 6.4 K km−1. Since the numerator in
(Eqn. 3.11.26) for gw is close to 1, it can be approximately written as
1 γ
γw = γa = a, (3.11.27)
1+
Le dqws Γ1
c p dT

where
Le dqws L2e
Γ1 = 1 + = 1+ qws . (3.11.28)
c p dT c p Rv T 2

This quantity Γ1 approximately coincides with the psychrometric correction to the drop diffusion
growth rate (see Section 5.1) and will participate in many equations in the next chapters. Equation
(3.11.27) shows that the value of gw depends both on temperature and pressure via qws(T, p). The value
of gw ≈ 6.14 °K km−1 at T = 0 °C, p = 800 hPa; gw increases with decreasing temperature and increasing
pressure. The reason is that qsw = 0.622es(T)/p, and qsw decreases toward low T or high p, the numerator
and denominator of gw tend to 1, Γ1 → 1, and gw approaches ga at low T below −40 °C. For example,
gw ≈ 9.44 K km−1 at T = −40 °C, p = 800 hPa, and gw ≈ 9.59 K km−1 at T = −60 °C, p = 200 hPa, at cirrus
altitudes near the tropopause.
It follows from the mass conservation law in the condensation process that the increment dql of
the adiabatic liquid water mixing ratio is related to the dqws as dql = −dqws. Taking this into account,
(Eqn. 3.11.20) can be rewritten as
c p dT − Le dql + gdz = 0 . (3.11.29)
92 Thermodynamic Relations

This gives for the adiabatic gradient (dql/dz)ad

 dql  c p  dT g
= + . (3.11.30)
 dz  ad Le  dz cp 

Introducing the dry and wet adiabatic temperature gradients, we obtain for the adiabatic gradient of
the liquid water mixing ratio

 dql  cp
(3.11.31)
  = (γ a − γ w ) .
dz ad Le

Integration of this equation over height from the cloud base gives the adiabatic liquid water mixing
ratio at a height z. The adiabatic profile of LWC is observed sometimes in clouds with suppressed
mixing with the environment (e.g., Verlinde et al., 2007; Klein et al., 2009) or above the bases of con-
vective clouds (Pruppacher and Klett, 1997), but LWC is usually smaller than the adiabatic value. The
reason for this is that clouds form via non-adiabatic processes, and mixing with the drier environment
“dilutes” the cloud parcels and leads to a decrease in liquid water content relative to the adiabatic
value. These processes and profiles of LWC will be considered in subsequent chapters.
In pure crystalline (ice) clouds, vapor excess is deposited on the cloud crystals. If all the vapor was
deposited on the crystals, adiabatic ascent would be characterized by the wet adiabatic lapse rate in
ice clouds, −dT/dz = gis, which can be evaluated similar to water clouds. We can again use the first
thermodynamic law, which can be written for ice clouds with the heat of sublimation Ls instead of
the heat of condensation Le as
c p dT + Ls dqis − vdp = 0 , (3.11.32)

where qis = 0.622eis/p is the vapor mixing ratio saturated over ice, and eis is the vapor pressure satu-
rated over ice. This equation can also be rewritten in terms of the rates dividing by dt and using the
relations v = 1/ra, dqis = −dqi, where qi is the ice water content. Multiplying by ra and introducing the
deposition rate Idep = radqi/dt,

dT dp
ρa c p = + Ls I dep . (3.11.33)
dt dt
This equation of heat balance will be used in subsequent chapters for derivation of the supersatura-
tion equations in crystalline clouds. Using the equation of state for air, pv = RaT, and the hydrostatic
equation, dp = −ragdz, the last term on the left-hand side of (Eqn. 3.11.32) can be transformed into
vdp = −gdz, and so we obtain
c p dT + Ls dqis + gdz = 0 . (3.11.34)

Dividing by dz, we obtain the wet adiabatic lapse rate in ice clouds, −dT/dz = gis, similar to
(Eqn. 3.11.21)
g L dq L dq
γ is = + s is = γ a + s is . (3.11.35)
cp c p dz c p dz
3.11. Adiabatic Processes 93

Taking again a logarithmic derivative of qis = 0.622eis/p yields

dqis  L g 
= qis  − s γ is + . (3.11.36)
dz  pc RaT 

Using the relation for dqis/dz similar to (Eqn. 3.11.24) and substituting into (Eqn. 3.11.35) and
solving for gis, we obtain
Ls
1+ qis
Ra T
γ is = γ a . (3.11.37)
L2s
1+ q
c p Rv T 2 is

The values of qis at low T in ice clouds are substantially smaller than the values of qws in water clouds,
and the numerator of gis is closer to 1 than in the equation for gw. Thus, gis is approximately
1 γ
γ is = γ a = a , (3.11.38)
1+
Ls dqis Γ2
c p dT

where

Ls dqis L2s
Γ2 = 1 + = 1+ qis . (3.11.39)
c p dT c p Rv T 2

This quantity G2 coincides with the psychrometric correction to the crystal growth rate (Section 5.2)
and will be used many times in upcoming chapters.
The mass conservation law in the deposition process in ice clouds states that the increment dqi of
the adiabatic ice water mixing ratio is related to dqis as dqi = −dqis. Taking this into account, (Eqn.
3.11.34) can be rewritten as
c p dT − Ls dqi + gdz = 0. (3.11.40)

This gives for the adiabatic gradient (dqi/dz)ad of the ice water mixing ratio

 dqi  c p  dT g cp
  =  +  = (γ a − γ is ). (3.11.41)
dz ad Ls  dz cp  Ls

Integration of this equation over the height from the cloud base gives the adiabatic ice water mixing
ratio at a height z. This is an upper limit of the ice water content (IWC), but IWC is usually smaller
than the adiabatic value due to mixing with the environment. These processes and profiles of IWC
will be considered in subsequent chapters.
There is a fundamental difference between water and ice clouds in values of supersaturation and
saturated humidities. In water clouds, the supersaturation sw is small and humidity is close to satu-
rated over water. In ice clouds, supersaturation over ice is typically above 0.2–0.3 and can reach
0.7–0.8 or more in cirrus clouds; thus saturation ratios are 1.3 to 1.7, and humidity is substantially
higher than saturated over ice (e.g., Khvorostyanov and Sassen, 1998b, 2002; Khvorostyanov et al.,
94 Thermodynamic Relations

2001, 2006; Jensen et al., 2001, 2005; Gierens et al., 2003; Comstock et al., 2004; Krämer et al.,
2009; Spichtinger and Krämer, 2012). In mixed-phase clouds, supersaturation can be intermediate
between saturated over water and ice (e.g., Khvorostyanov et al., 2001, 2003). This is caused by the
slow deposition process and will be discussed in more detail in upcoming chapters. Therefore, the
deposition heat in ice clouds is smaller than it would be in adiabatic ascent, the lapse rate is higher
than the wet adiabatic, and closer to ga. Besides, it depends on time and is determined by the super-
saturation relaxation time in ice clouds (Section 5.3). More precise evaluation of gis requires use of
the non-stationary equations and will be discussed in subsequent chapters.
Consider now the adiabatic process in mixed-phase clouds. In this case, both condensation and
deposition latent heats are present and the first law of thermodynamics is
c p dT + Le dqws + Ls dqis − vdp = 0. (3.11.42)

This equation again can be rewritten in terms of the rates dividing by dt and using the relations
v = 1/ra, dqws = −dql, dqis = −dqi, multiplying by ra, thus giving

dT dp
ρa c p = + Le I con + Ls I dep . (3.11.43)
dt dt
This equation of heat balance will be used later for derivation of the supersaturation equations in the
mixed-phase clouds.
Calculation of Integrals with Maxwell Distribution 95

Appendix A.3 for Chapter 3. Calculation of Integrals

with Maxwell Distribution

The n-th moment integrals of the type

∞
n −α x 2
In = ∫x e
0
dx (A.3.1)

can be calculated using a substitution ax2 = z. Thus

∞
1 − ( n +1) / 2 ( n −1) / 2 − z 1  n + 1
In =
2
α ∫
0
z e dz = α − ( n +1) / 2 Γ 
2  2 
, (A.3.2)

which follows from the definition of Euler’s gamma function Γ(x) (Gradshtein and Ryzhik, 1994).
The first 3 moments are especially important in applications, since they follow from (Eqn. A.3.2) for
a particular n. For n = 0 (normalization integrals)

1 −1/ 2  1  1 π
I0 = α Γ  = . (A.3.3)
2  2 2 α

Here the relation Γ (1/2) = π was used. This gives us another integral:
∞ ∞
2 2 π
∫ e dx = 2 ∫ e dx = 2I 0 = (A.3.4)
−α x −α x
J0 = .
−∞ 0
α

For n = 1 (mean velocity components),

1 1
I1 = Γ (1) = . (A.3.5)
2α 2α
For n = 2 (mean components of kinetic energy),

1 −3/ 2  3  π −3 / 2
I2 = α Γ  = α . (A.3.6)
2  2 4
For n = 3 (mean velocity),
1 −2 1
I3 = α Γ ( 2 ) = α −2 . (A.3.7)
2 2
The 0-th moments (Eqns. A.3.3 and A.3.4). These relations are used for evaluation of normalization
constants of the Maxwell distribution in their various forms. For the momentum distribution, it is

 px2 + py2 + pz2 

dw p ( p) = a p exp  −  dpx dpy dpz . (A.3.8)
 2mkT 

The constant ap is determined from the normalization condition

∞ ∞ ∞ ∞
 px2 + py2 + pz2 
∫
−∞
dw p ( p) = a p ∫ ∫ ∫  − 2mkT  dpx dpy dpz =
−∞ −∞ −∞
exp p ∫
3 3
∞  − px2   ∞ 
dpz = a p  ∫ exp   dpx = a p  ∫ exp(−α px ) dpx = a p [ J 0 (α )] = 1.
2 3
(A.3.9)
 −∞  2 mkT    −∞ 
96 Thermodynamic Relations

We can use (Eqn. A.3.4) for J0(a) with px = x, a = (2mkT)−1. Thus, it follows from (Eqns. A.3.4
and A.3.9) that

J 0 = (2π mkT )1/ 2 , a p = J 0−3 = (2π mkT )−3 / 2 . (A.3.10)

This yields the normalized momentum distribution

 px2 + py2 + pz2 

dw p ( p) = (2π mkT )−3/2 exp  −  dpx dpy dpz . (A.3.10a)
 2mkT 

The Maxwell distribution by the velocity components is

 m( v x2 + v y2 + vz2 ) 
dwv ( v x , v y vz ) = av exp  −  dv x dv y dvz . (A.3.11)
 2 kT 

The constant av is determined from the normalization condition

∞ ∞ ∞ ∞
 v x2 + v y2 + vz2 
−∞
∫ dw (v) = a ∫ ∫ ∫ exp  −
v v
−∞ −∞ −∞
2mkT  dv x dv y dvz =

v ∫
3 3
∞  − mv x2   ∞ 
z = av  ∫ exp   dpx  = a v  ∫ exp(−α v x ) dv x  = av [ J 0 (α )] = 1.
2 3
(A.3.11a)
 −∞  2 kT    −∞ 
The constant av is again determined from (Eqn. A.3.4) with a = (m/2kT). Then, from (Eqns. A.3.4,
A.3.11a),

J 0 (α ) = (2π kT/m)1/2 , av = [ J 0 (α )]−3 = (m /2π kT )3/2 . (A.3.12)

The 1-st moment (Eqn. A.3.5). The relation (Eqn. A.3.5) could be used for evaluation of the mean
components of velocity v x, v y , vz ; however, the integrals of the odd power of velocity from −∝ to +∝
are equal to zero—that is,
∞

vx = ∫v
−∞
x dwv ( v x , v y vz ) dv x = v y = vz = 0 . (A.3.13)

The first moment can be used for evaluation of the 1st moments in the limited bounds (0, ∝).
The 2-nd moment (Eqn. A.3.6). It is used for calculation of the normalizing constant for distribu-
tion in the polar system and for calculation of the mean kinetic energy. The Maxwell distribution in
the polar system in the velocities space converts into

 mv 2  2
dwv ( v ,θ ,ϕ ) = avp exp  − v sinθ dθ dϕ dv. (A.3.14)
 2 kT 

Its integral over the angles is 4p, and this integral over v yields
∞

∫ d Ω ∫ dwv (v,θ ,ϕ ) dv = 4π avp I 2 (α ) ,

0
(A.3.15)
Calculation of Integrals with Maxwell Distribution 97

−3/ 2
π  m 
with a = (m/2kT) again. From (Eqn. A.3.6), I 2 =   . Thus, from (Eqn. A.3.15)
3/2
4  2π kT 
 m 
avp =  , which coincides with av earlier in (Eqn. A.3.12)—that is, normalizations in the
 2π kT 
components space and polar system are the same, avp = av.
The mean components of the kinetic energy along the x-axis can be calculated as
mv x2 m
∞

∫ vx dwv (vx , v y vz ) dvx

2
εx = < > =
2 2 −∞
∞ mv 2 ∞ mv 2 ∞
y mv 2
m − x − − z
= av ∫
2 −∞
dv x v x2 e 2 kT ∫ dv y e 2 kT ∫ dvz e 2 kT .
−∞ −∞
(A.3.16)

This is expressed via I2(a) and I0(a) with a = (m/2kT), as shown earlier, and
3/ 2
m  m  π −3/2 π kT
(A.3.17)
[2 I 2 (α )][2 I 0 (α )]2 =  = .
 2π kT 
ε x = av m α
2 4 α 2
This is a known result for the Maxwell distribution: the mean energy of each component of velocity
is (1/2)kT, and the full kinetic energy per three degrees of freedom is (3/2)kT.
The 3-rd moment (Eqn. A.3.7). This is used for evaluation of the mean velocity. As we saw earlier,
the velocity components have zero mean values. But the velocity module is not zero, it is calculated
using the distribution in the polar coordinate system (Eqn. A.3.14):
∞

Vv = ∫ d Ω ∫ v dwv (v,θ ,ϕ )dv,

0
∞
 mv 2 
= av ∫ sin θ dθ dϕ ∫ v 3 exp  − dv
0
 2 kT 
1/2 1/2
 8 kT   8 RT  (A.3.18)
= av 4π I 3 (α ) = 2(πα )−1/2 =  ,
 π m 
=
 π M 

where we used Equation (A.3.7) for I3 with a = (m/2kT) and (Eqn. A.3.12) for av. Here, R is the
universal gas constant, and M is the gas molecular weight. The last equation is obtained from the
previous one by multiplication of the numerator and denominator by Avogadro’s number NAv. This
equation is used in many applications of cloud physics since it determines the molecular fluxes of
cloud particles.
4
Properties of Water and Aqueous Solutions

4.1. Properties of Water at Low Temperatures and High Pressures

4.1.1. Forms of Water at Low Temperatures

A general schematic of various states and transitions of water at atmospheric pressure (1 bar) and
lower pressures is shown in Fig. 4.1. The stable state of liquid water is located in the region from
0 °C to the boiling point, Tboil = 100 °C, and a superheated metastable liquid is found at temperatures
higher than the boiling point.
A region of metastable supercooled water begins below 0 °C and extends to about −40 °C. Hetero-
geneous freezing of water drops begins mostly below −5 to −12 °C on small foreign particles called
ice nuclei (IN), although liquid drops can exist down to about −38 to −42 °C, with smaller droplets
freezing at colder temperatures (Hagen et al., 1981; Pruppacher and Klett, 1997). At these tempera-
tures, rapid homogeneous freezing begins, and the probability of existence of pure water in the liquid
phase sharply decreases at T < 235 K.
Two new forms of ice, not crystalline but amorphous, were discovered at very low temperatures:
low-density amorphous ice (LDA) and high-density amorphous ice (HDA). LDA was discovered
by Barton and Oliver (1936) who studied water vapor deposits on a cold plate at very low T. They
observed the diffraction patterns of X-rays of these deposits and found that the distinct pattern at
−80 °C characteristic of crystalline hexagonal ice Ih gradually became less perfect with lowering
temperature and converted into two diffuse rings at −110 °C, resembling the pattern for liquid water.
They concluded that it was an amorphous of vitreous solid. The term amorphous means a substance
with non-crystalline structure. The term vitreous means a solid that has amorphous structure and in
addition may undergo a glass transition with changing temperature, which is a transition from the
crystal-like to liquid-like structure with a corresponding change in the values of heat capacity or
expansion coefficients. The amorphous ice is also called glassy water, which is a solid that has a
liquid-like disordered arrangement. It was found that another way to obtain LDA is via rapid cooling
at a rate > 105 K s−1 to temperatures below about −170 °C (100 K), which produces not a crystalline but
a glassy water or LDA (Brüggeller and Mayer, 1980). Subsequent warming causes a glass transition
at about Tg = −140 °C (130 K), and ultraviscous metastable water exists between Tg and Tx ≈ −120 °C
(150 K), where again rapid crystallization begins. A region extending more than 80 K between Tx
and the spinodal limit Ts is called “No man’s land” because experiments on liquid water cannot be
performed. Particles of LDA ice may form in polar mesospheric (noctilucent) clouds (Murray and
Jensen, 2010).

99
100 Properties of Water and Aqueous Solutions

Superheated water
Tboil
100°C 373 K

Stable water
Tmelt
0°C 273 K
Supercooled water
Thom (metastable)
–45°C 235 K
Tspinod

No man's land
Tx
–120°C 150 K
Ultraviscouse water (metastable)
–140°C 130 K
Tglas

Glassy water (metastable)

Figure 4.1. Schematic diagram of different water states at atmospheric pressure 1 atm. The points
mean: Tboil = 100 °C is the boiling point, Tmelt = 0 °C is the melting point, Thom ≈ −38 °C is the
temperature of homogeneous freezing, Tspinod ≈ −45 °C is the spinodal temperature (the temperature
that separates metastable and unstable states), Tx ≈ −120 °C is the temperature of crystallization of
amorphous water at reheating, and Tglas is the temperature of the glass transition.

Using an electron diffraction camera, König (1942) found in the range −140 to −80 °C the diffrac-
tion patterns of sharp rings corresponding to the cubic structure of the diamond type. Thus, these
experiments indicated existence of the new, cubic form of ice, called ice Ic. Upon further heating
above −80 °C, this ice converted into ordinary hexagonal ice Ih. Subsequent experiments showed
that ice Ic may form simultaneously with ice Ih or amorphous LDA (Vertsner and Zhdanov, 1966),
or after cooling the other forms of high-pressure ice (ices II, III, and V, described later) and reduc-
ing the pressure to atmospheric (Hobbs, 1974). Studies of the crystalline structure of Ic showed that
its structure is similar to that of Ih (described, for example, in Hobbs, 1974; Young, 1993; Curry and
Webster, 1999), being tetrahedral around each oxygen atom. Each layer is identical to that of the
hexagonal phase, but each layer is shifted by one half of the diameter of the hexagonal ring; thus, the
oxygen atoms in Ic have the same configuration as the carbon atoms in the diamond cubic structure.
The measured unit cell parameter a0 was near 6.35 Å and density was 0.9343 g cm−3 at −130 °C, close
to ice Ih. At temperatures above −80 °C, ice Ic was unstable, having a saturated vapor pressure higher
than ice Ih, and converted into ice Ih upon heating during the times ~ 103–102 min at T = 170–190 K
to a few minutes at T > 210 K. However, the occurrence and time of transition may depend on the
environmental conditions and heating rates (Murray and Bertram, 2006; Murray et al., 2005, 2010).
The metastable state of cubic ice Ic and conversion into Ih may cause an increase in dehydration of the
upper troposphere where this temperature range is observed (Murphy, 2003).
4.1. Properties of Water at Low Temperatures and High Pressures 101

4.1.2. Forms of Water at High Pressures

A great variance of forms of various solid phases of water (ices) can occur at high pressures. Beyond
Ih, ice possesses at least 12 other equilibrium (crystalline) phases and two amorphous states (Whalley,
1969; Hobbs, 1974; Johari, 1998; Tse et al., 1999; Klug, 2002; Rosenberg, 2005), all discovered in the
laboratory. A transient formation of cubic ice Ic was observed in cirrus clouds and could be confirmed
experimentally (Mayer and Hallbrucker, 1987; Murray and Bertram, 2006; Malkin et al., 2012).
HDA was discovered almost 50 years after LDA (Mishima et al., 1984, 1985; Heide, 1984). It
was obtained by compressing hexagonal ice Ih below 150 K or by bombarding an ice Ih layer with
an electron beam. It was found that a “polyamorphic transition” LDA–HDA is possible between
these two forms of ice when the thermodynamic parameters (temperature and pressure) change
infinitesimally, but this is accompanied by sharp and large (20%) volume change and hence a first-
order phase transition. Existence of a pure substance in more than one amorphous form is called
polyamorphism.
A general schematic of these ice forms is given in Fig. 4.2 following Whalley (1969), Hobbs (1974),
and Rosenberg (2005). Besides the ordinary hexagonal ice Ih, there are another eight ices that exist at
pressures higher than 2 × 103 bar. These are labeled in Fig. 4.2 with the Roman numerals from II to
IX. The stable and metastable boundaries among these forms are indicated with the various line types.
Tammann (1900) was the first to discover this pressure-induced ice transformation. He observed Ih
in the temperature range −30 to −50 °C at increasing pressure and found that in the pressure range
2.0–2.2 kbar there was a sharp decrease in volume, which corresponded to formation of a new ice form
called ice III. At lower temperatures of −70 to −80 °C and p just below 2 kbar, Tammann observed the
transformation of ice Ih into a solid ice II slightly denser than ice III. This series of experiments was
continued later by Bridgman (1912, 1937), who extended applied pressure to 20.5 and then to 45 kbar,
and discovered several other forms of ice: ices IV, V, VI, and VII. Fig. 4.2 shows that the slopes on the
p-T diagram between various pairs of ices can be either positive or negative.
The Clapeyron Equation (3.7.3) is written for the boundary of ices “a” and “b”

dTm ∆V T (vb − va ) T (1/ρ b − 1/ρ a )

= = = , (4.1.1)
dpm ∆Sη M w Lm Lm

where Lm is the specific heat of transition, and ra and rb are the densities, all of which describe
the boundary slopes between the ices and explain the different signs of the slopes by the different
relations of the densities of the ices. Whalley and Davidson (1965) and Brown and Whalley (1966)
discovered ice VIII, and found that ice VII transforms into ice VIII below about 0 °C. Whalley et al.
(1968) discovered a new solid that they called ice IX. In contrast to ice Ih, these forms of ice have
densities greater than liquid water. The ices X and XI were discovered later and their mutual trans-
formations with other forms of ice were studied (e.g., Matsuo et al., 1986; Johari, 1998). Thus, ice
exhibits a rich variety of crystalline and glassy structures in at least 12 distinct phases or polymorphs
at different pressures and temperatures (Rosenberg, 2005), the largest number among all known
substances.
An interesting feature of ices VI and VII is that they can exist at positive Celsius temperatures,
approaching +80 to +100 °C, but this requires very high applied pressures Dp = 6–25 kbar (Fig. 4.2).
102 Properties of Water and Aqueous Solutions

80
Liquid water

VII
40

IV
Temperature (°C)

III
V VI
−40

II
Ih
−80

−120 VIII

−160 IX

−200
0 2 4 6 8 10 12 14 16 18 20 22 24
Pressure (kbar)

Figure 4.2. Phase diagrams of the solid states of water. Solid lines are measured stable lines; dash-
dotted lines are measured metastable lines; dashed lines are extrapolated or estimated stable lines;
dotted lines are extrapolated or estimated metastable lines. Ice IV is metastable in the region of
stability of ice V; the indicated field for ice IV is inferred from the D2O system. Ice Ic and vitreous ice
are not indicated. Adapted from Whalley (1969), Hobbs (1974), and Rosenberg (2005) with changes.

In contrast to ordinary ice Ih, all high-pressure forms of ice, including the ices VI and VII, have
greater density than liquid water at the same conditions. The slopes dTm/dpm at the boundaries of
the ices VI and VII with liquid water are positive, and they can transform into liquid water (melt) at
increasing temperature or decreasing pressure. Note that if creation of the ices VI and VII and other
high-temperature ices were technologically possible on aircraft, they could be considered potential
candidates for cloud seeding programs.
Many experimental studies of selected thermodynamic properties of the ambient hexagonal ice Ih
have been reviewed in several books and articles (e.g., Dorsey, 1968; Fletcher, 1970a; Hobbs, 1974;
Petrenko and Whitworth, 1999; Curry and Webster, 1999; Sastry, 2002). Reviews of the properties
of cubic ice Ic and its transformations into Ih are given in Murray et al. (2005, 2010), Murray and
Bertram, (2006), and Malkin et al. (2012).
4.2. Theories of Water 103

4.2. Theories of Water

Various models and hypotheses have been developed to explain water structure, anomalous behavior,
and numerous forms in the supercooled region. Three of the most often discussed hypotheses are
(1) stability limit conjecture, (2) the singularity free hypothesis, and (3) the liquid−liquid critical
point hypothesis. These hypotheses are illustrated in the p-T diagrams in Figs. 4.3a, b, and c. The first
hypothesis is based on the measured sharp increase near 235 K (−38 °C) in many thermodynamic
properties of water: isobaric heat capacity cp, isothermal compressibility kT, and the coefficient of
thermal expansion a p:

 ∂sη  1  ∂ρ  1  ∂ρ 
cp = T  , κT = , αp= .
ρ  ∂T  p ρ  ∂T  p
(4.2.1)
 ∂T  p

The increase of these properties toward colder temperatures is similar to the power law singular-
ity (T − Ts)−λ; that is, the characteristics of water tend to infinity as T approaches Ts (Angell, 1982),
analogous to the second- or higher-order phase transitions (Landau and Lifshitz, v.5, 1958; Lifshitz
and Pitaevskii, 1997). The stability limit hypothesis (Speedy and Angell, 1976; Angell, 1982; Speedy,
1982) suggests that these thermodynamic properties of supercooled water (cp, kT, and ap) tend to

300 Liuqid stable state

Tm(p)
270

240 Thf(p) Supercooled wa

ter
T (K)

210 Ts(p)

Unstable
180
water “No man’s land”
Tx(p)
150
LDA HDA
120
Glassy water

0.0 0.1 0.2 0.3

Pressure (GPa)
(a)

Figure 4.3. (a) The p-T diagram illustrating the thermodynamic behavior of water predicted by the
stability limit conjecture. Tm(p) is the melting temperature, Thf (p) is the temperature of homogeneous
freezing (235 K (−38 °C) at p = 1 bar). The line Ts(p) is the spinodal temperature, Ts ≈ 228 K (−45 °C)
at p = 1 bar, Tx(p) is the temperature of crystallization of ultraviscous water at warming; the glass
temperature Tg is located below Tx(p) (not shown). LDA and HDA indicate the domains where the
low-density and high-density amorphous solids may exist. Both Tm(p) and Thf (p) decrease with
increasing pressure at p < 0.2 GPa as predicted by the Clapeyron equation because the density of Ih
is smaller than the density of liquid water. At p > 0.2 GPa, dThf /dp becomes positive and grows with
increasing pressure because water freezes into the other forms of ice denser than liquid water (see
Fig. 4.2). The sign or value of dTm(p)/dp on the melting curve Tm(p) change at higher p ~ 0.6 = 0.7 GPa
and T ~ 150 K (not shown here) is where liquid water can melt into denser solids (see Chapter 8).
Adapted from Mishima and Stanley (1998), Koop (2004) and Stanley et al. (2007), with changes.
104 Properties of Water and Aqueous Solutions

300 Liuqid stable state

Tm(p)
270
Thf(p) Superco
240 oled wate
r

T (K)
210 Tmax(p)

180
“No man’s land”
Tx LDL HDL
150
LDA HDA
120
Glassy water

0.0 0.1 0.2 0.3

Pressure (GPa)
(b)

Figure 4.3. (b) The p-T diagram illustrating the thermodynamic behavior of water predicted by
the singularity-free hypotheses. Tm(p) is the melting temperature, Thf (p) is the temperature of
homogeneous freezing (235 K or −38 °C at p = 1 bar), and Tmax(p) is the temperature of the maximum
values of the thermodynamic properties (cp, kT, a v). Tx(p) is the temperature of crystallization of
ultraviscous water at warming; the glass temperature Tg is located below Tx(p) (not shown). LDL and
HDL indicate the domains where the low-density and high-density liquid waters may exist. LDA and
HDA indicate the domains where the low-density and high-density amorphous solids may exist. The
Tm(p) and Thf (p) decrease or increase with varying pressure as described in Fig. 4.3a. Adapted from
Mishima and Stanley (1998, Koop (2004) and Stanley et al. (2007).

infinity at some limiting temperature. At a normal pressure of 1 atm, this limit was hypothesized
to be near Ts ≈ −45 ± 3 °C (228 ± 3 K), called the spinodal temperature, which is located a few
degrees below the homogeneous freezing temperature Thf (Fig. 4.3a). This hypothesis assumes that
the spinodal temperature connects at negative pressures to the locus of the liquid-to-gas spinodal (the
limit of metastability) for supercooled water. However, the limit Ts cannot be reached in experiments
because liquid water rapidly crystallizes earlier, at −38 °C (235 K) or 2–4 degrees above the spinodal
temperature.
The temperature of singularities is a function of pressure, Ts(p), and decreases with increasing
pressure to about −110 °C (160 K) at p = 0.2 GPa (Fig. 4.3a), which is a result of the increase in
the freezing point depression DTf (p) with increasing pressure. The liquid water becomes unstable
and therefore cannot exist below this temperature Ts(p). The line Ts(p) that separates the metastable
and unstable water is called the spinodal line (the line with triangles in Fig. 4.3a). Existence of
the spinodal temperature was hypothesized also for aqueous solutions by Rasmussen (1982), and
Rasmussen and Liang (1993).
The second hypothesis is called the “singularity free” or percolation hypothesis. Since measure-
ments of liquid water are possible only a few degrees above the hypothesized spinodal but not at the
spinodal temperature itself, this hypothesis assumes that thermodynamic properties of water have a
4.2. Theories of Water 105

700
C, 1st crit. point

G
600 L

500

T (K) 400
Tb
Liquid stable state
300 Tm(p)
Supercooled water
200 Thf(p) C ', 2nd
cr.p.
LDL HDL
Tx(p)
100 LDA 1F HDA
Glassy water

0.0 0.1 0.2 0.3

Pressure (GPa)
(c)

Figure 4.3. (c) The p-T diagram illustrating the thermodynamic behavior of water predicted by the
liquid–liquid transition or the second critical point hypotheses. C is the first critical point of water at
T = 647 K, p = 220 atm (0.022 GPa), G and L mean the gaseous and liquid phases (“low-density
and high-density liquids”) around C. Tb = 373 K is the boiling temperature, Tm(p) is the melting
temperature, Thf (p) is the temperature of homogeneous freezing (235 K (−38 °C) at p = 1 bar), Tx(p)
is the temperature of crystallization of ultraviscous water at warming; the glass temperature Tg is
located below Tx(p) (not shown). The black square with label C′ near T = 220 K and p = 0.1 GPa
(1000 bar) denotes the hypothesized second critical point. LDL and HDL indicate the domains
where the low- and high-density liquid waters may exist. LDA and HDA indicate the domains
where the low- and high-density amorphous solids may exist. The label 1F denotes the line of first-
order phase transition that emanates from C′ and separates the high-density and low-density phases
that occur at temperatures below Thf (p). (After Mishima and Stanley (1998), Poole et al. (1992,
1994), with changes.)

sharp increase near Ts, and have local maxima near Ts at some temperature Tmax(p) (Fig. 4.3b), but
are finite without a singularity, and decrease below Tmax. This second conjecture assumes that the
polyamorphic changes between LDA and HDA are relaxation phenomena, although they resemble
genuine phase transitions.
The third hypothesis is based on an analogy with the well-known critical point C of water located
at Tcr1 = 647 K (374 °C), and pcr1 = 218 atm (22 MPa), and have a critical density rcr1 = 0.328 g cm−3
(Fig. 4.3c). Above this point, there is no difference between liquid water and vapor. It can be said
that below the point C, water is “separated” into two “liquids”: one is the “high-density liquid” (i.e.,
true liquid water), and the other is “low-density liquid”—that is, water vapor, meaning both “liquids”
can coexist. By analogy, this theory hypothesizes the existence of a second critical point C′ at low
temperature and high pressure, near Tcr2 ≈ 220 K (−53 °C) and pcr2 ≈ 0.1 GPa (1000 atm) with the
106 Properties of Water and Aqueous Solutions

density rcr2 ≈ 1 g cm−3 (Fig. 4.3c). This hypothesis is based on molecular dynamics simulations and
the equation of the state of liquid water (Poole et al., 1992, 1994) and was supported by the other
approaches (Ponyatovsky et al., 1994; Mishima, 1996; Borick et al., 1995; Moynihan, 1997; Tejero
and Baus, 1998).
By analogy with the water structure around the first critical point, this third hypothesis states that
two liquid waters exist below the second critical temperature Tcr2: a low-density liquid (LDL) at low
pressure, and a high-density liquid (HDL) at a higher pressure, with possible transitions between
them similar to transitions between liquid water and vapor below the first critical point C (Fig. 4.3c).
Therefore, this theory is also called “the liquid–liquid phase transition” hypothesis. Near the first
known critical point, water is a fluctuating mixture of the local molecule structures that resemble
structures of liquid water and vapor. The analogous structure is hypothesized to exist near the second
critical point C′, consisting of a fluctuating mixture of LDL and HDL structures.
The thermodynamic response functions (e.g., isobaric heat capacity cp) still have maxima in the
domains of the phase diagram with one phase and far enough from the critical points. These maxima
are located along the lines Tmax(p) that continue the spinodal or coexistence lines into the domains
with one phase. These asymptotic lines continuing the spinodal line are sometimes called the Widom
lines, and are often regarded as an extension of the coexistence line into the “one-phase regime.” The
lines of the maxima for different response functions asymptotically approach one another as the criti-
cal point is approached, since all response functions become expressible in terms of the correlation
length (Stanley et al., 2007).
One possible explanation of existence and coexistence of the two phases of water is the follow-
ing (Stanley et al., 2007). Because water is both tetrahedral and charged, it means that the simple
potentials of intermolecular interactions with one minimum as in the van der Waals theory considered
in Section 3.4 (e.g., Lennard-Jones potential) are not sufficient to describe the complexity of water.
One way to modify the Lennard-Jones potential and to provide at least a simplified description is to
bifurcate the single minimum (as shown in Fig. 3.2) into two minima. The first minimum, at a closer
distance, corresponds to two pentamers (a water molecule and its four neighbors) of water interact-
ing with each other in a rotated configuration. The second minimum, at a greater distance, occurs in
the unrotated position. This second position is a deeper minimum because although the pentamers
are farther apart there is the potential for hydrogen bonding between the molecules and we can see
the beginnings of an ice-like hexagonal structure. The existence of the two minima in the potential
instead of one minimum in Fig. 3.2 may cause the formation of two polymorphs or polyamorphs
of water when temperature and pressure reach some critical values, with a low-density form corre-
sponding to a second minimum at a greater distance, and a high-density form corresponding to a first
minimum at a closer distance between the molecules.
Another analogy for the coexistence of LDL and HDL can be seen in the theory of superfluidity
at very low temperatures, where two liquids also exist: a normal viscous component and a superfluid
component without viscosity. The two liquids coexist with mutual percolation without friction, owing
to the specific energy spectrum with existence of a finite threshold for an elementary energy excita-
tion (Landau and Lifshitz, v. 5, 1958; Lifshitz and Pitaevskii, 1997).
The properties and theory of the vitreous state of water (thermodynamics, structure, and crystal-
lization) are described by Gutzow and Schmelzer (1995, 2011) and Debenedetti (2003).
4.3. Temperature Ranges in Clouds and Equivalence of Pressure and Solution Effects 107

4.3. Temperature Ranges in Clouds and Equivalence of Pressure and Solution Effects

Some fraction of clouds and fogs form and evolve at “warm” temperatures above 0 °C, without par-
ticipation of ice crystals. Parameterization of microphysical processes in this temperature domain
is called “warm cloud microphysics.” However, the vast majority of clouds or cloud layers forms
entirely or partially at temperatures below 0 °C, where liquid water is metastable and is called “super-
cooled water.” Clouds with liquid drops and ice crystals coexisting below 0 °C are called mixed-
phase clouds and can exist in such state for a long time.
Pure supercooled water may exist down to about −40 °C, but droplets of aqueous supercooled solu-
tions may exist without freezing at much lower temperatures. Interest in the processes and forms of
water at low temperatures was stimulated in the 1980s up to now by the intensive studies of clouds
that form at temperatures around and below −40 °C and their importance in the climate system. These
clouds include the anvils of deep convective clouds and various cirriform clouds at altitudes from 6 to
12 km in the Arctic and midlatitudes to 15–20 km in the tropics with the corresponding temperature
range from −30 to −80 °C (CIRRUS-2002), and “pearl” clouds formed over mountains in orographic
waves at altitudes of 15–25 km at similar temperatures.
Polar stratospheric clouds may occur at temperatures of −80 to −100 °C (193 to 173 K), especially
in the Antarctic winter, and may play an important role in ozone depletion and formation of the
ozone hole. Even colder cloud types are noctilucent or polar mesospheric clouds that form in the
upper mesosphere at altitudes of 80–90 km at temperatures that can be near a climatological mean
of −150 °C (120 K) for this layer or a few tens of degrees lower (Lübken et al., 2009; Murray and
Jensen, 2010). Recent studies suggest that ice Ih is metastable at temperatures below 72 K and can
be transformed into higher-ordered, ferroelectric ice XI (Petrenko and Whitworth, 1999; Kuo et al.,
2001, 2004; Singer et al., 2005). The lowest temperatures observed in terrestrial clouds are on the
order of 80–90 K (Lübken et al., 2009), still above the supposed transition temperature to ice XI.
Clouds on other planets may form at even colder temperatures (e.g., Lewis and Prinn, 1984; Lewis,
1995; Ibragimov, 1990; Curry and Webster, 1999).
Another important area of low-temperature studies related to cloud physics is weather modifica-
tion by cloud seeding. Some earlier studies used various artificial ice nuclei like AgI, PbI, or similar
substances with a crystalline structure close to natural ice, which were active at environmental tem-
peratures (e.g., Schaeffer, 1949; Vonnegut, 1947; Hobbs, 1974; Kachurin, 1978; Dennis, 1980; Cotton
and Pielke, 2007). Subsequently, many different crystallizing or cooling agents were tested, includ-
ing solid granulated carbon dioxide (CO2), also called “dry ice” and used to keep ice cream in sum-
mer (sublimation temperature Tsubl = −78.9 °C or 194.25 K), liquefied propane (boiling temperature
Tb = −40.2 °C or 233 K), liquefied nitrogen (boiling temperature Tb = −200 °C or 73.15 K), and simi-
lar substances. These cooling agents, being relatively cheap and convenient to use, have very low
boiling or sublimation points and create huge amounts of tiny ice crystals when evaporating, with
efficiency up to 1011–1014 per 1 gram of evaporated substance.
These crystals cause rapid glaciation of a cloud or fog under appropriate conditions, which can
lead to precipitation enhancement (applied for agriculture or fighting wildfires) or decrease (applied
for decrease of snowfall in the cities in winter) or to fog dispersal in airports, seaports and along
the roads. These cooling agents and techniques were tested in laboratories and have been widely
applied in field experiments (e.g., Gaivoronsky and Seregin, 1962; Serpolay, 1969; Bigg et al., 1969;
108 Properties of Water and Aqueous Solutions

Krasnovskaya et al., 1964, 1987; Hicks and Vali, 1973; Silverman and Weinstein, 1973; Dennis,
1980; Berjulev et al., 1989; Vlasiuk et al., 1994; Cotton and Pielke, 2007).
Field experiments on cloud seeding can be expensive, time consuming, and require continuation
for many years to obtain and estimate a statistically significant effect. Therefore, cloud seeding
programs stimulated development of numerical models with detailed accounts of the microphysi-
cal processes of cloud glaciation (e.g., Orville and Chen, 1982; Cotton et al., 1986; Khvorostyanov,
1984, 1987; Bakhanov and Buikov, 1985; Khvorostyanov et al., 1989; Kondratyev et al., 1990;
Khvorostyanov and Khairoutdinov, 1990; Khairoutdinov and Khvorostyanov, 1991; Krakovskaia
and Pirnach, 2004; Cotton and Pielke, 2007). However, both field experiments and the numerical
modeling of cloud seeding are hampered by the lack of understanding of the mechanisms of action
of the seeding agents, their efficiency under various conditions, and even lack of knowledge about
the forms of ice that are nucleated by these agents. This has stimulated research on cloud micro-
physical processes at low temperatures, which may help to improve cloud seeding methods.
A closely related problem is the high-pressure effects on water forms and transitions. A similarity
was found in experiments and calculations in the freezing DTf and melting DTm point depressions caused
by the addition of solutes to pure water and by applied high pressure. The solution concentration of
~2.7 mole of NaCl caused effects similar to an applied pressure of ~103 bar; and molality of 4 moles
NaCl caused DTm ≈ 15 K and DTf ≈ 27 K, equivalent to a pressure of 1,400 bar (Kanno and Angell, 1977;
Leberman and Soper, 1995). Parameterizations of this equivalence were developed by Koop et al. (2000)
and Baker and Baker (2004), and a simple quantitative equivalence between these two effects was theo-
retically derived and discussed by Khvorostyanov and Curry (2004a) and Curry and Khvorostyanov
(2012), as described in Chapter 8. Therefore, studies of the forms and transitions of water under high
pressure can elucidate the freezing of solutions droplets and mechanisms of ice formation in clouds.

4.4. Parameterizations of Water and Ice Thermodynamic Properties

In this section, we describe empirical parameterizations of water and ice thermodynamical proper-
ties used in numerical modeling and analyses of experiments on ice nucleation and drop activation.

4.4.1. Saturated Vapor Pressures

The saturated vapor pressures are used in various units. The relations among these units are given
in the Appendix for Chapter 4 for convenience. Since the melting heats and heat capacities depend
on the temperature and pressure, the saturated humidities over water and ice obtained by integration
of the Clausius–Clapeyron equations described in Chapter 3 may require corrections. The more pre-
cise parameterizations of the saturated pressures of water, ews, and ice, eis, account for such empirical
or semi-empirical corrections or are based on various fits used in practical calculations. These include
several versions of the Magnus equation and parameterizations by Gratch and Goff, Wexler and
Hyland, and others where ews and eis were approximated with exponential functions with arguments
as the polynomial and logarithmic functions of temperature. A detailed analysis and comparison of
many of these parameterizations and their accuracy were performed by Murphy and Koop (2005).
Wexler (1976) fitted the temperature dependence of ews(T) as

ews = exp(a0T −2 + a1T −1 + a2 + a3T + a4T 2 + a5T 3 + a6T 4 + a7 log T ), (4.4.1)

4.4. Parameterizations of Water and Ice Thermodynamic Properties 109

with ews in Pa, a0 = −2.9912729 × 103, a1 = −6.0170128 × 103, a2 = 1.887643854 × 101, a3 = −2.8354721 ×
10−2, a4 = 1.7838301 × 10−5, a5 = −8.4150417 × 10−10, a6 = 4.4412543 × 10−13, and a7 = 2.858487.
The values of ews in dyn cm−2 (= 10−3 mb) are obtained using the relation 1 dyn cm−2 = 10 Pa—i.e.,
multiplying ews in (Eqn. 4.4.1) and subsequent similar equations by 10. Murphy and Koop (2005)
fitted ews(T) for the range 123 < T < 332 K as:
ln ews (T ) = a0 − a1/T − a2 ln T + a3 T + t a −
n T + tanh[a4 (T − a5 )](a6 − a7 /T − a8 ln T + a9 T ), (4.4.2)

with ews in Pa, a0 = 54.842763, a1 = 6763.22, a2 = 4.210, a3 = 3.67 × 10−4, a4 = 0.0415, a5 = 218.8,
a6 = 53.878, a7 = 1331.22, a8 = 9.44523, and a9 = 0.014025.
The saturated over ice vapor pressure was approximated by Hyland and Wexler (1983) in the range
173.16 < T < 273.16 as
eis = exp(a0 /T + a1 + a2T + a3T 2 + a4T 3 + a5T 4 + a6 logT), (4.4.3)

with eis in Pa, a0 = −5.6745359 × 103, a1 = 6.3925247, a2 = −9.6778430 × 10−3, a3 = 6.2215701 ×

10−7, a4 = 2.0747825 × 10−9, a5 = −9.4840240 × 10−13, and a6 = 4.1635019. Murphy and Koop (2005)
suggested the parameterization for eis for T > 110 K

eis = exp(a0 + a1 /T + a2 ln T + a3T ), (4.4.4)

with eis in Pa, a0 = 9.550426, a1 = −5723.265, a2 = 3.53068, and a3 = −0.00728332. A simpler expo-
nential fit is also used for eis

eis (T ) = exp(a1 + b1/T ). (4.4.5)

The values of the parameters vary slightly in the fits by various authors; Murphy and Koop (2005)
give a1 = 28.9074 and b1 = −6143.7 to fit the recent measurements in the range 164 < T < 273.16 K.
The values of eis in dyn cm−2 are obtained by multiplying by 10. For reference, the values of eis in hPa are
6.106 (0 °C), 2.597 (−10 °C), 1.032 (−20 °C), 0.3797 (−30 °C), 0.1283 (−40 °C), and 0.0393 (−50 °C).

4.4.2. Heat Capacity of Water and Ice

Pruppacher and Klett (1997) provide the following empirical fit for the heat capacity of water cw in
cal g−1,

cw = cw 0 + a1 (Tc − Tc1 )2 + a2 (Tc − Tc1 )4 , 0 ≤ Tc ≤ 35 °C

with Tc in Celsius, cw0 = 0.9979, a1 = 3.1 × 10−6, a2 = 3.8 × 10−9, Tc1 = 35, and
4
cw = ∑ anTcn , − 37 ≤ Tc ≤ 0 °C,
”C (4.4.6a)
0

with a0 = 1.000938, a1 = −2.7052 × 10−2, a2 = −2.3235 × 10−5, a3 = 4.3778 × 10−6, and a4 = 2.7136 ×
10−7. The isobaric molar heat capacity of ice cpi,m was approximated by Murphy and Koop (2005) as

c pi , m = a1 + a2T + a3T exp[ −(T/a4 )2 ], T > 20 K , (4.4.6b)

with cpi,m in J mol−1 K−1, T in Kelvins, a1 = −2.0572, a2 = 0.14644, a3 = 0.06163, and a4 = 125.1. The
values of specific heat capacity cpi in cal g−1 K−1 are obtained as cpi = cpi,m/(4.18Mw)—i.e., dividing
110 Properties of Water and Aqueous Solutions

a1, a2, and a3 by 4.18Mw ≈ 75.24, yields a1 = −0.02734, a2 = 194.6305, a3 = 8.1911 × 10−4 for
cpi. Pruppacher and Klett (1997) using the data by Flubacher et al. (1960) approximated specific
cpi (cal g−1 K−1) in the range 0 to −40 °C as

c pi = 0.503 + 0.00175Tc . (4.4.6c)

Equations (4.4.6a) and (4.4.6c) show that the heat capacity of ice near 0 °C is about half that of liquid
water, which is caused by the difference in their internal structure.
The difference in molar heat capacity in J mol−1 K−1 between vapor and ice was approximated by
Murphy and Koop (2005), similar to (Eqn. 4.4.6b), as

∆c p, m = a1 + a2T + a3T exp[ −(T/a4 )2 ], (4.4.7)

with a1 = −35.319, a2 = 0.14457, a3 = 0.06155, and a4 = 129.85. The difference in specific heat
capacities is obtained by dividing coefficients a1, a2, a3 by 4.18Mw ≈ 75.24, with a1 = −0.46941, a2 =
1.92145 × 10−3, a3 = 8.18049 × 10−4, and a4 is the same.

4.4.3. Latent Heats of Phase Transitions

The latent heat of evaporation Lv was approximated in Pruppacher and Klett (1997) based on mea-
surements of the energies of the hydrogen bonds, fractions of broken bonds, and enthalpies of the
vacancies formation as
Lv = 597.3 − 0.561Tc , − 20 < Tc < 40 °C,
”C (4.4.8a)
5
Lv = ∑= anTcn , T , − − 44T < Tc < − 2” 0 °C,
”C (4.4.8b)
0

with Lv in cal g−1, and a0 = −1412.3, a1 = −338.82, a2 = −122.347, a3 = −0.7526, a4 = −1.1595 × 10−2,
and a5 = −7.313 × 10−5. These expressions predict an increase in Lv toward low T and give
Lv = 597.2 cal g−1 at Tc = 0 °C and Lv = 625 cal g−1 at Tc = −40 °C. The limit of −44 °C in (Eqn. 4.4.8b)
is caused by the assumption in Pruppacher and Klett (1997) that −45 °C is a singularity point. As
discussed in Section 4.2, more recent experimental data and the current theories of water show the
absence of a singularity at this temperature.
Murphy and Koop (2005) suggested another approximation for supercooled water

Lv (T ) = b0 + b1T + exp[b2 (b3 − T )], 236 K < T < 273.16 K, (4.4.9)

with Lv in J mol−1, b0 = 56579, b1 = −42.212, b2 = 0.1149, and b3 = 281.6.

The molar latent heat of sublimation Ls can be obtained from (Eqn. 3.7.17) by integration of dLs/dT
over T; that is, using Kirchoff’s relations and Dcp,m in (Eqn. 4.4.7):
T

Ls = Ls 0 + ∫ [c p1,m (T ′) − c p 2,m (T ′)] dT ′ + ∫ 1

T0 0

dp   ∂( vv − vi )  
T

∫ , ′ ′+∫
T0
( v1 − v2 ) − T ′ 
dT ′   ∂T ′  p 
 dT ′. (4.4.10)
0
4.4. Parameterizations of Water and Ice Thermodynamic Properties 111

Murphy and Koop (2005) found the following fit to this integral

Ls (T ) = b0 + b1T + b2T 2 + b3 exp[ −(T/b4 )2 ], T > 30 K. (4.4.11)

with Ls in J mol−1, b0 = 46782.5, b1 = 35.8925, b2= −0.07414, b3 = 541.5, and b4 = 123.75. Ls in cal g−1
is obtained dividing b0, b1, b2, b3 by ≈ 4.18 × 18 = 75.24, and b4 remains the same. For reference, the
value of Ls is 678.5 cal g−1 near 0 °C.
Several parameterizations have been developed for the specific melting heat Lm(T). Pruppacher
and Klett (1997) approximated it as
4
Lm (T ) = ∑ anTcn , T > 229 K, (4.4.12)
0

with Lm in cal g−1, a0 = 79.7, a1 = −0.12, a2 = −8.0481 × 10−2, a3 = −3.2376 × 10−3, and a4 = −4.2553 ×
10−5. This function describes a decrease in Lm with decreasing temperature; Lm = 79.7 cal g−1
(≈1.43 kcal mole−1) at Tc = 0 °C and Lm = 53.9 cal g−1 (≈0.97 kcal mole−1) at Tc = −40 °C.
Khvorostyanov and Curry (2004a) proposed an expression for the molar and specific melting heat,
which is based on a compilation of experimental data from Johari et al. (1994) extrapolated to very
low temperatures of amorphous ice:
Lm (T ) = C LT {tanh[(T − TL1 )/TL 2 ] + cL 0}, (4.4.13)

with T in Kelvin, TL1 = 215 K, TL2 = 40 K, and cL0 = 1.6; the value CL = 8.82 for Lm in J mole−1, and
0.1172 for Lm in cal g−1. This yields Lm ≈ 79.8 cal g−1 at 0 °C, which well approximates the data from
Johari et al. (1994) down to 160 K and is suitable for calculations of ice nucleation in very cold clouds.
Hellmuth et al. (2013, Fig. 37 therein) compared four parameterizations of Lm in the range 253 < T
< 273 K: (4.4.12) by Pruppacher and Klett (1997, PK97), (Eqn. 4.4.13) by Khvorostyanov and Curry
(2004a, KC04a), Lm calculated as Lm(T) = Ls(T) − Lv(T) using (Eqns. 4.4.9) and (4.4.11) for Lv and
Ls from Murphy and Koop (2005, MK05), and Lm calculated with the Thermodynamic Equation of
State TEOS-10 (IAPWS, 2009a,b). The differences between these different parameterizations were
found to be not very large at T > 253 K, which indicate that each of them can be used in calculations
in this temperature range. However, as will be shown in Chapters 8 and 9, the differences dramati-
cally increase at lower temperatures. This is very important for correct calculations of parameters of
relevance to homogeneous and heterogeneous ice nucleation, and special attention will be paid to the
correct choice of Lm(T) and its averaging in those chapters.

4.4.4. Surface Tension between Water and Air or Vapor

Pruppacher and Klett (1997) suggested the following expression for the surface tension between
water and air, swa, at Tc > −40 °C:
6
σ wa (T ) = ∑ anTcn , (4.4.14)
n=0

with swa in erg cm−2, a0 = 75.93, a1 = 0.115, a2 = 6.818 × 10−2, a3 = 6.511 × 10−3, a4 = 2.933 ×
10−4, a5 = 6.283 × 10−6, and a6 = 5.285 × 10−8. For reference, swa ≈ swv = 75.93 erg cm−2 (0 °C) and
≈88 erg cm−2 (−40 °C).
112 Properties of Water and Aqueous Solutions

4.4.5. Surface Tension between Ice and Water or Solutions

Pruppacher and Klett (1997) recommend the following expressions for the surface tension between
ice and water, siw, in erg cm−2,
σ iw = 28 + 0.25Tc , 0 < Tc < 0 °C,
Tc- 36 (4.4.15a)
2 3
σ iw = a0 + a1Tc + a T + a T
2 c 3 c − 44 < Tc < − 36 º C, (4.4.15b)

with Tc in Celsius, a0 = 189.081, a1 = 13.1625, a2 = 0.3469, and a3 = 3.125 × 10−3.

Dufour and Defay (1963) compared calculations of the nucleation rates and freezing temperatures
with observations and suggested a linear parameterization with a smaller slope

σ iw = 23.8 − | σ iw′ | Tc , (4.4.15c)

′ | = 0.102 erg cm −2 K −1 and the limits 0.06 < | σ iw

with the average value | σ iw ′ | < 0.13 erg cm −2 K −1 . This
−2
yields siw = 23.8 at 0 °C and 19.7 erg cm at −40 °C. Dufour and Defay did not limit this parameter-
ization at −40 °C. Zobrist (2007) and Hoose and Möhler (2012) found the following fit in the T- range
of 229 K to 238 K, which can be extended over the entire supercooled region up to the melting point
T0 = 273.15 K

σ iw = a0 + a1Tr + a2Tr 2 , Tr = (T − T0 )/T0 , (4.4.16)

where Tr is the reduced temperature, siw is in erg cm−2, T is in Kelvins, a0 = 32.98, a1 = 12.048, and
a2 = −4.6705 × 102. This choice gives siw = 32.98 erg cm−2 (0 °C) in agreement with the measure-
ments described by Hobbs (1974) and siw ≈ 18 erg cm−2 at T = −44 °C; the last value is close to that
from Dufour and Defay (1963).
The concept of water-ice surface tension becomes uncertain below the temperature of homoge-
neous freezing Tfhom, about −38 to −42 °C, because pure water freezes below these temperatures,
as described in Section 4.2. Liquid aqueous solutions still can exist at lower temperatures. Sev-
eral parameterizations have been suggested for the surface tension at the solution–air interfaces ssa.
Tabazadeh et al. (1997) found the following fit to the experimental data by Sabinina and Terpugov (1935)
σ sa = a0 + a1w − T (a2 + a3 w), (4.4.17)

where ssa is in erg cm−2, T is in K, w is the percentage concentration of solute by weight, a0 = 142.35,
a1 = −0.96525, a2 = 0.22954, and a3 = −0.0033948. This gives ssa = 75.06 erg cm−2 at w = 0, T =
293.15 K, which is close to the prediction of (Eqn. 4.4.14) for the interface of pure water and vapor.
Myhre et al. (1998) performed detailed measurements of the surface tension ssa and density rsa of
aqueous solutions of sulfuric acid, approximated as the polynomials
7 3
σ sa (w, T ) = ∑ ∑ σ ij wiTcj , (4.4.18)
i =0 j =0

10 4
ρ sa (w, T ) = ∑ ∑ ρij wiTcj . (4.4.19)
i =0 j =0

The coefficients sij and rij of these polynomials were given in the Tables in Myhre et al. (1998) for
the domain −53 < Tc < 27 °C. A comparison with the earlier data by Sabinina and Terpugow (1935) at
Tc = 20 °C showed a good agreement. In particular, the behavior of ssa(w, Tc = 20 °C) was character-
ized by an increase from ≈72.5 erg cm−2 at w = 0 (pure water) to the maximum of ≈77 erg cm−2 at
w = 0.4 to 0.6, and then by monotonous decrease with increasing w to ~52.5 erg cm−2 at w = 1.
4.4. Parameterizations of Water and Ice Thermodynamic Properties 113

4.4.6. Surface Tension between Ice and Air or Vapor

Surface tension between ice and air, sia, can be determined from Antonoff’s rule, which can be con-
sidered as a limiting case of Young’s relation (see Section 9.2) and states that siw = siv − swv. Using
(Eqn. 4.4.14) for swv and (Eqn. 4.4.15a) for siw, we can write for siv = siw + swv,
6
σ iv (T ) = σ wv + σ iw = ∑ anTcn + (28 − 0.25Tc ), (4.4.20a)
n=0

where the coefficients a0 to a6 are given after (Eqn. 4.4.14). Hoose and Möhler (2012) combined the
equations from Pruppacher and Klett (1997) and found the following fit for siv = siw + swv,
σ iv = (a0 + a1Tc ) + (a2 + a3Tc ), (4.4.20b)

with siv in erg cm−2, Tc in Celsius, a0 = 76.1, a1 = −0.155, a2 = 28.5, and a3 = 0.25. More detailed
thermodynamic models (e.g., Clegg and Brimblecombe, 1995; Clegg et al., 1998) allow more precise
calculations of various properties of multicomponent aqueous solutions over the wide regions of
compositions and temperatures.

4.4.7. Density of Water

For liquid water above 0 °C, Kell (1975) suggests the following polynomial expression at p = 1 atm:
5
ρ w (Tc ) = (1 + Bρ wTc )−1 ∑ AnTcn , 0 ≤ Tc ≤ 100 °C, (4.4.21a)
n=0

with rw in g cm−3, Tc in degrees C, A0 = 0.9998396, A1 = 1.8224944 × 10−2, A2 = −7.922210 × 10−6,

A3 = −5.544846 × 10−8, A4 = 1.497562 × 10−10, A5 = −3.932952 × 10−13, and Brw = 1.8159725 × 10−2.
Hare and Sörensen (1987) found a polynomial for supercooled water to −33 °C,
6
ρ w (Tc ) = ∑ anTcn , − 33 ≤ Tc ≤ 0 °C, (4.4.21b)
n=0

with a0 = 0.99986, a1 = 6.690 × 10−5, a2 = −8.486 × 10−6, a3 = 1.518 × 10−7, a4 = −6.9984 × 10−9, a5 =
−3.6449 × 10−10, and a6 = −7.497 × 10−12. This yields rw = 0.99986 g cm−3 at 0 °C and ≈0.978 g cm−3
at −33 °C. More detailed data on water density at various temperatures and pressures can be obtained
by solving the thermodynamic equation of state (TEOS) considered in the next section.

4.4.8. Density of Ice

The density of ice can be determined either from measurements of the volume Vuc of the unit cell of
ice using the relation ri = 4Mw /(NAvVuc), or from measurements of a volume v i ¢ of a single molecule
of ice, or from direct measurements of the density. The ice density can also be calculated from the
equation of state for water in the ice phase or from the direct numerical simulations (DNS) of water
structure using various intermolecular potentials. Pruppacher and Klett (1997) obtained an empirical
fit for ri for hexagonal ice Ih
2
ρi (T ) = ∑ anTcn , (4.4.22)
0

with ri in g cm−3, a0 = 0.9167, a1 = −1.75 × 10−4, a2 = −5.0 × 10−7, for −180 ≤ Tc ≤ 0 °C.
114 Properties of Water and Aqueous Solutions

Zobrist (2007) and Hoose and Möhler (2012), based on data from Lide (2001), parameterized v i ¢
using the relations
−1
mw Mw  3 n
vi′(T ) = =  ∑ avnTr  , (4.4.23)
ρi N Av ρi 0  0 
where mw = Mw/NAv is the mass of a water molecule, v i ¢ in cm3, Tr = (T − T0)/T0 is the reduced tem-
perature, T0 = 273.15 K, av0 = 1, av1 = −0.05294, av2 = −0.05637, av3 = −0.002913. The ice density
follows from the relation

mw Mw  3 
ρi (T ) = = = ρi 0  ∑ avnTrn  , (4.4.24)
′
vi (T ) N Av vice (T )  0 

with ri0 = 0.9167 g cm−3 and vice = v i ¢.

A few other parameters used in calculations or estimates are (approximate values at nor-
mal conditions): the molar volume of water vw = Mw /rw ≈ 18 cm3 g−1; the molar volume of ice
vi = Mw /rw ≈ 19.63 cm3 g−1; the concentration of molecules in liquid Nl = NAv /vw ≈ 3.34 × 1022 cm−3;
the concentration of molecules in ice NI = NAv /vi ≈ 3.06 × 1022 cm−3; the molecular volume in liquid
water vw1 = vw /NAv ≈ 3 × 10−23 cm3; the molecular volume in ice vi1 = vi /NAv ≈ 3.27 × 10−23 cm3.

4.5. Heat Capacity and Einstein–Debye Thermodynamic Equations of State for Ice

The energy and heat capacity of a solid in classical physics is evaluated by assuming that every atom
has vibrational degrees of freedom that can be described as a linear oscillator. This model is realistic
in many cases because the displacement of an atom from the equilibrium state is accompanied by an
elastic force that tends to return it to the original state as in a real oscillator. It is assumed in classical
physics that each atom has the mean energy e = kT for each vibrational degree of freedom. If a solid
consists of N molecules with l atoms in each, and each atom has three degrees of freedom, then the
total number of degrees of freedom is 3Nl. Three degrees of freedom correspond to the translation,
and three correspond to the rotation of the body as a whole. Thus, the number of vibrational degrees
of freedom is 3Nl − 6 ≈ 3Nl since Nl is very large. The vibrational energy is Evib = 3NlkT, and the
heat capacity is therefore

dEvib d
Cv = = (3NlkT) = 3Nkl, (4.5.1)
dT dT
or the heat capacity per one molecule is c¢v = 3kl. If the amount of solid is one mole, N = NAv, then
using the relation NAvk = R, (Eqn. 4.5.1) can be written as

Cv = 3Rl (4.5.2)
Equations (4.5.1) and (4.5.2) express Dulong and Petit’s law, which predicts that the heat capacity
is independent of temperature. This law satisfactorily describes the experimental data on Cv for
many simple atomic or ionic crystals at sufficiently high temperatures and is also applicable for
some gases.
4.5. Heat Capacity and Einstein–Debye Thermodynamic Equations of State for Ice 115

However, the heat capacities of solids decrease with decreasing temperature, and tend to zero at
zero temperatures, in conflict with Dulong and Petit’s law. Einstein (1906) suggested not using the
equipartition energy distribution, kT for each oscillation, but the quantum Planck’s expression con-
sidered in Section 3.2
hν
Evib = 3 Nlε , ε = (4.5.3)
exp(hν /kT ) − 1

where n is the frequency of oscillations, and e- is the mean energy per vibration. Einstein for simplic-
ity assumed the same frequency for all oscillations in a solid. Then, the heat capacity becomes

dEvib (hν /kT )2 exp(hν /kT )

CV = = 3 Nkl . (4.5.4)
dT [exp(hν /kT ) − 1]2
This equation correctly predicts decrease Cv with decreasing T. At high temperatures, kT >> hn,
and expanding the denominator by the small quantity x = hn/kT << 1 also yields Cv = 3Nkl; that is,
Einstein’s formula contains Dulong and Petit’s law as its high temperature limit in agreement with
the correspondence principle. At low T, when kT << hn, Einstein’s formula predicts that Cv tends to
zero as exp(− hn /kT), while experimental data show that Cv ~ T 3 at low T, called Debye’s cubic law
for heat capacity. This disagreement is caused by the assumptions that all vibrations have the same
frequency and all vibrations are independent.
A more advanced thermodynamic theory of the heat properties of the solids has been developed by
Debye (1912). Debye again assumed that the major contribution to the energy of a solid comes from
the vibrations of the atoms around their equilibrium positions, and each vibration can be considered
an oscillator. However, the vibrational energy spectrum in Debye’s theory was characterized not by
a single frequency but by a spectrum of frequencies. If the number of molecules in a solid is N and
the number of atoms in each molecule is l, then the number of vibrational degrees is 3Nl − 6 ≈ 3Nl,
as discussed earlier.
The derivation of Debye’s expressions for heat capacity can be based on the Bose–Einstein energy
distribution (see Section 3.2.4) and using the concepts of quantum mechanics (Landau and Lifshitz,
v. 5, 1958). If the frequency of an oscillator is n, the quantum of energy of a vibration is hn, and the
number of an energy level is n, then the energy of each oscillator is en = hn(n + 1/2). Summation
over the frequencies leads to rather complicated expressions for the statistical sum Z and Helmholtz
free energy F. Debye (1912) derived an interpolation formula between the low and high temperature
limits based on two assumptions: introducing a continuous density of oscillators, and assuming some
maximum frequency of oscillators nm. With these assumptions, Debye obtained an expression for F

   θ   θ  
F = N ε 0 + NlkT 3 ln 1 − exp  − D   − DD  D   , (4.5.5)
   T   T  

where qD is Debye’s temperature defined as qD = hnm/k, and DD(z) is Debye’s function,

z
3 x 3 dx
z 3 ∫0 e x − 1
DD ( z ) = . (4.5.6)
116 Properties of Water and Aqueous Solutions

The integrand here represents integration over the frequencies with the Bose–Einstein distribution
and is similar to those arising in Plank’s theory of black-body radiation. As described in Section 3.1,
the entropy Sh = −(∂F/∂T)V and the energy E = F + TSh are both calculated with (Eqns. 4.5.5) and
(4.5.6), and finally, the heat capacity CV in Debye’s theory is

 ∂E    θD  θD 1 
CV =   = 3 Nlk  4  −3 . (4.5.7)
 ∂T V  T  T exp(θ D /T ) − 1 

The limits of CV can be obtained using the limits of DD(qD / T). In the high temperature limit, x = qD /T
<< 1, the function DD tends to 1. For one mole, N = Nav, this gives the molar heat capacity Cvh = 3Rl,
or for ice with l = 3, Cvh = 9R. That is, the limit of Debye’s equation gives at high T the Dulong and
Petit’s law (Eqn. 4.5.2). At low T, so that z = qD /T >> 1, the limit of Debye’s function (Eqn. 4.5.6) is
expressed via Riemann’s zeta function, and yields the low temperature limit:
3
12 Nlkπ 4  T 
CVl =   . (4.5.8)
5  θD 

Thus, the heat capacity gives the correct cubic Debye’s law Cv ~ T3 in the low temperature limit, in
agreement with experimental data (Landau and Lifshitz, v.5, 1958; Hobbs, 1974).
Debye’s formula appeared to be applicable to many solids in predicting the specific heat capacities
of many simple atomic and ionic crystals. However, as noted by Hobbs (1974), it is less successful in
the case of molecular crystals such as ice, and the entire T-curve of the heat capacity calculated with
Debye’s (Eqn. 4.5.7) cannot be fitted with a single value of qD. The values qD = 192 K or 318 K better
reproduce CV(T) either at lower or higher temperatures but cannot reproduce in the entire T-region
and the experimentally measured curves such as those approximated by the fit (Eqn. 4.4.6b). It was
clarified later that several rotational and translational vibrations can contribute to Cp of ice (Hobbs,
1974). Then, it may be necessary to introduce several of Debye’s temperatures, or qD as the function
of T for a description of ice properties in various T-regions, and the theory becomes too complicated.
A detailed analysis performed in Hobbs’ (1974) fundamental monograph showed that a unified the-
ory of ice thermodynamic properties for the entire T-range was still missing at the beginning of the
1970s. This situation existed until a substantial breakthrough occurred only in the last two decades,
as described in the next sections.

4.6. Equations of State for Ice in Terms of Gibbs Free Energy

The development of the new theory of ice was stimulated by the International Association for Prop-
erties of Water and Steam (IAPWS) and was based on construction of the thermodynamic potential
for ice. The specific Gibbs energy for hexagonal ice Ih (or the Gibbs function of ice) expressed as
a function of temperature and pressure, GIh(T, p), represents the fundamental equation of state for
ice. This definition of the equation of state differs from the equations of state for gases and liquids
described in Chapter 3, which are usually formulated as relations between the density r or volume V
with temperature and pressure, r = r(p, T), or V = V(p, T). The Gibbs function G(T, p) also represents
an equation of state of the liquid or solid and allows evaluation of various properties of the substance
using the thermodynamic derivatives described in Section 3.1.
4.6. Equations of State for Ice in Terms of Gibbs Free Energy 117

The following brief review of the history of development and of the essence of the new ice theory
follows Feistel and Wagner (2005), IAPWS (2009a) and Hellmuth et al. (2013). The first Gibbs func-
tions for ice Ih were published by Feistel and Hagen (1995, 1998, 1999) and Tillner-Roth (1998) and
were valid only in the vicinity of the melting curve of ice. A new comprehensive Gibbs function that
for the first time covered the entire range of existence of ice Ih was developed consistently with the
IAPWS-95 formulation of fluid water (Wagner and Pru , 2002; IAPWS 2009b), a detailed description
of the construction of the Gibbs function and of the experimental data used was provided by Feistel
and Wagner (2005). A second, slightly improved version was published by Feistel and Wagner (2006)
and adopted as an international standard formulation by the International Association for the Proper-
ties of Water and Steam (IAPWS, 2009a) as part of the Thermodynamic Equation of Seawater–2010
(TEOS-10) (IOC, SCOR, and IAPSO, 2010). A review of the scientific development of this standard
including a description of the literature involved in its development was given by Pawlowicz et al.
(2012) in the preface of a special issue of Ocean Science. The perfect consistency of the TEOS-10
ice formulation with those for liquid water, water vapor, humid air, and seawater (Feistel et al., 2008)
permits very accurate calculation of phase equilibria between ice and those substances, such as with
humid air (Feistel et al. 2010b) and with liquid and gaseous water (IAPWS, 2011; Wagner et al., 2011)
even at extremely low temperatures (Feistel and Wagner, 2007; Feistel, 2012; IAPWS, 2012).
In contrast to Debye’s (1912) theory that calculates first the free energy and then the entropy and
heat capacity as its derivatives (see Section 4.5), Feistel and Wagner (2005) constructed the theory in
the reverse order. First, Feistel and Wagner (2005) found a very precise approximation for the specific
heat capacity of ice cpi by interpolation between the exponents of Debye’s cubic law at low tempera-
tures and the linear behavior at high temperatures using the rational Pade’ approximation structure

c pi c1FW + c2 FW Tr2 + c3 FW Tr4

= Tr3 , (4.6.1)
c piu 1 + c4 FW Tr2 + c5 FW Tr4 + c6 FW Tr6

where Tr = T/Tt is the reduced temperature, Tt = 273.16 K, cpiu = 1 J kg−1 K−1, c1FW = 185656.573673404,
c2FW = 159038807.871411, c3FW = 2321798783.50605, c4FW = 154.188350854909, c5FW =
62945.966529576, and c6FW = 1120863.23495484. The resulting r.m.s. (root mean square) of the fit
corresponding to (Eqn. 4.6.1) is 0.8% for the data of Giauque and Stout (1936), and 3.0% for those
of Flubacher et al. (1960). So (Eqn. 4.6.1) by Feistel and Wagner (2005) approximates cpi with very
good accuracy over the entire temperature range from 0 °C to almost 0 K and can be used for high-
accuracy calculations of ice Ih properties. Feistel and Wagner’s (Eqn. 4.6.1) is in good agreement with
the empirical approximations for cpi described in Section 4.4 and extends them down to 0 K.
The heat capacity function (Eqn. 4.6.1) can be integrated analytically to obtain expressions for
entropy sh and free enthalpy (Gibbs energy) GIh for ice Ih. For this purpose, Feistel and Wagner (2005)
represented the rational function (Eqn. 4.6.1) in a mathematically equivalent way by the real part of
two pairs of complex partial fractions

c pi 2  1 1 2 
= Tr Re ∑ rk  − +  (4.6.2)
c piu k =1 T
 r − Trk Tr + Trk Trk 

This expression takes the form of (Eqn. 4.6.1) if the real part of the complex sum is outlined explic-
itly. The two complex weight factors, r1, r2, and the corresponding root pairs, Tr1, Tr2, are responsible
118 Properties of Water and Aqueous Solutions

for bell-shaped low-temperature corrections, r1 and Tr1 at about 0 K, and r2 and Tr2 centered at about
100 K, modifying the otherwise asymptotically linear behavior for high temperatures at normal pres-
sure, lim (cpi/T) = 7.583 J kg−1 K−2 at T → ∞. The low-temperature expansion of (Eqn. 4.6.2) is
2
lim(c pi /c piu ) = − 2 Re ∑ rk (Tr /Trk )3 , yielding Debye’s cubic temperature dependence.
k =1

The complex numbers r1, Tr1, and Tr2 were found by fitting to the cited experimental data. The
fourth one, r2, was obtained by Feistel and Wagner by expanding into powers of pressure leading to
the full Gibbs function, thus providing pressure-dependent heat capacities derived from the tempera-
ture dependence of compressibility. Using the relation from Section 3.1, (∂Sh/∂T)p = cpi/T, and inte-
grating once over T, Feistel and Wagner obtained the entropy Sh; using the relation Sh = −(∂GIh/∂T)p,
the second integration yields the free enthalpy or specific Gibbs energy for hexagonal ice Ih in the
following form

 2
GIh (T , p) = G0 Ih ( p) − Sη 0 Tr Tt + Tt Re ∑ rk [(Trk − Tr ) ln(Trk − Tr )
 k =1

( /Trk ]} ,
) + (Trk + Tr ) ln(Trk + Tr ) − 2Trk ln Trk − Tr2 ∑ (4.6.3)

4
G0 Ih ( p) = ∑ G0 k ( pr − p0 r )k , (4.6.4)
k =0

2
r2 ( p) = ∑ r2 k ( pr − p0 r )k , (4.6.5)
k =0

where pr = p/pt, p0r = p0/pt, and pt = 611.657 Pa. The complex numbers r1, r20 to r22, and Tr1, Tr2,
are given in Table 4.1 (Feistel and Wagner, 2005b,c, 2006; IAPWS, 2009a; IOC et al., 2010).
Here, Tr = T/Tt denotes the reduced temperature, pr = p/pt the reduced pressure, pr0 = p0/pt, the
reduced normal pressure with Tt = 273.16 K, pt = 611.657 Pa, and p0 = 101 325 Pa. The complex
logarithm ln(z) is meant as the principal value—i.e., it evaluates to imaginary parts in the interval
−π <Im [ln(z)] ≤+π.

Table 4.1. Coefficients of the Gibbs function of ice Ih in Feistel–Wagner (Eqns. 4.6.3) to (4.6.5).

Coefficient Real part Imaginary part Unit

G00 −0.632 020233 335 886 × 106 J kg−1

G01 0.655 022 213 658 955 J kg−1
G02 −0.189 369 929 326 131 × 10−7 J kg−1
G03 0.339 746 123 271 053 × 10−14 J kg−1
G04 −0.556 464 869 058 991 × 10−21 J kg−1
Sh0 (absolute) 0.189 13 × 103 J kg−1 K−1
Sh0 (IAPWS-95) −0.332 733 756 492 168 × 104 J kg−1 K−1
Tr1 0.368 017 112 855 051 × 10−1 0.510 878 114 959 572 × 10−1
r1 0.447 050 716 285 388 × 102 0.656 876 847 463 481 × 102 J kg−1 K−1
Tr2 0.337 315 741 065 416 0.335 449 415 919 309
r20 0.725 974 574 329 220 × 102 −0.781 008 427 112 870 × 102 J kg−1 K−1
r21 −0.557 107 698 030 123 × 10−4 0.464 578 634 580 806 × 10−4 J kg−1 K−1
r22 0.234 801 409 215 913 × 10−10 −0.285 651 142 904 972 × 10−10 J kg−1 K−1
4.6. Equations of State for Ice in Terms of Gibbs Free Energy 119

The list of 18 adjusted parameters in Table 4.1 contains two unnecessary ones that formally
appeared during the transformation of six real parameters describing heat capacity into four com-
plex numbers (see Feistel and Wagner (2005) for more details). Two of the parameters reported in
Table 4.1, Sh0 and G00, are adjusted to arbitrary reference-state conditions (Feistel et al., 2008). The
IAPWS-95 reference state specifies entropy and internal energy of liquid water to vanish at the triple
point (Wagner and Pru , 2002; IAPWS- 2009b). The related values of the coefficients must be used
if phase equilibria are calculated from equating the chemical potential of ice with that of liquid water
or of water vapor provided by IAPWS-95 and TEOS-10. In contrast, the “absolute” reference state
defines the residual entropy of ice Ih at 0 K to coincide with the value calculated statistically (Pauling,
1935; Nagle 1966; see also Gutzow and Schmelzer, 2011, for a review of the third law). The remain-
ing 14 adjustable coefficients were fitted to 522 measured values of 32 different groups of measure-
ments, 5 of those groups at elevated pressures (Feistel and Wagner, 2006).
The Feistel–Wagner equation of state (Eqn. 4.6.3) is valid over the entire range of naturally abun-
dant, hexagonal ice Ih of H2O, covering the temperature and pressure range 0 K ≤ T ≤ 273.16 K and
0 ≤ p ≤ 210 MPa. The function also behaves reasonably at high pressures and low temperatures where
no experimental data are available. The thermodynamic properties of ice Ih are computed from the
Gibbs function by general thermodynamic relations given in Section 3.1. Additional relations, in par-
ticular those required for the calculation of phase equilibria with liquid water, seawater, water vapor,
or humid air are available from the articles of Feistel et al. (2010a,b).
The Gibbs function of ice, together with the thermodynamic potentials of liquid water, water vapor,
seawater, and humid air, as well as numerous properties derived thereof, are implemented equivalently
in Fortran and in Visual Basic (or VBA for Excel) in the open-source Sea-Ice-Air (SIA) Library
(Feistel et al. 2010a; Wright et al. 2010), whose latest update is freely available from the TEOS-10
website (www.teos-10.org). For convenience and higher computation speed, it is often useful to cal-
culate a set of values from the full TEOS-10 equations over the particular range of interest, and then
fit a separate correlation to those points as a “secondary” equation. For the frequently used phase-
equilibrium curves of ice with liquid water and with water vapor, such simple and compact equations
are already available from an additional IAPWS formulation (IAPWS 2011; Wagner et al. 2011).
The “secondary” equation for the sublimation pressure for H2O ice Ih is (Wagner et al. 2011):
3
psubl
ln pr = (Tr )−1 ∑ ai (Tr )bi , pr = , (4.6.6)
i =1 pt

where Tr = T/Tt, Tt = 273.16 K, and pt = 611.657 Pa. The coefficients ai and exponents bi are:
a1 = −0.212 144 006 × 102, a2 = 0.273 203 819 × 102, a3 = −0.610 598 130 × 101, b1 = 0.333 333 333 ×
10−2, b2 = 0.120 666 667 × 101, and b3 = 0.170 333 333 × 101. Equation (4.6.6) is valid down to 50 K
based on a low-temperature extension for the water-vapour heat capacity (Feistel and Wagner, 2007;
Feistel et al., 2010b; Wagner et al., 2011). The “secondary” equation for the melting pressure for H2O
ice Ih is (Wagner et al., 2011):
3
pmelt
pr = 1 + ∑ ai (1 − Trbi ), pr = . (4.6.7)
i =1 pt

The coefficients ai and exponents bi are: a1 = 0.119 539 337 × 107, a2 = 0.808 183 159 × 105,
a3 = 0.333 826 860 × 104, b1 = 0.300 000 × 101, b2 = 0.257 500 × 102, and b3 = 0.103 750 × 103.
120 Properties of Water and Aqueous Solutions

The intersection point of the two curves—(Eqns. 4.6.6) and (4.6.7)—is the experimental triple point
at 273.16 K and 6.11657 hPa, which deviates slightly by 0.02 Pa from the pressure of the numerical
triple point calculated directly from the thermodynamic potentials (Feistel et al., 2008; Wagner et al.,
2011). Equations (4.6.6) and (4.6.7) describe the corresponding saturated vapor pressures with high
accuracy and can be used along with the parameterizations described in Section 4.4.
The validity of the liquid–water formulation IAPWS-95 of TEOS-10 is restricted to temperatures
above the triple point (Wagner and Pru , 2002; IAPWS-2009b). But, because the function extrapo-
lates well to lower temperatures, its use down to −20 °C is considered as safe, at least at low pressures.

4.7. Generalized Equations of State for Fluid Water

4.7.1. Equations of the van der Waals Type and in Terms of Helmholtz Free Energy

The equation of state (EOS) is one of the tools used for description of the properties of liquid water,
water vapor, and their equilibrium in the wide regions of the temperature and pressure variations.
More than thirty various versions of EOS for liquid water have been developed since the 1980s
for applications in studies of water in the atmosphere, seawater, and in the fundamental properties
of water. Reviews of EOS are provided, e.g., in IAPWS (1995), Jeffery and Austin (1997, 1999),
Curry and Webster (1999), Kiselev (2000), Kiselev and Ely (2001), Wagner and Pru (2002), IAPWS
(2008), Holten et al. (2011, 2012), and Shi and Mao (2012). The analytical formulations of EOS
have different forms; some represent generalizations of the van der Waals equation, while others are
formulated in terms of the free Helmholtz energy, or as the thermodynamic models for supercooled
water by adopting suitable physical scaling fields relative to the location of a liquid–liquid critical
point in metastable water (Section 4.2).
For example, Song and Mason (1989, 1990a, b) and Ihm et al. (1991) generalized the van der
Waals equation considered in Section 3.4. Their derivations were analogous to those described in
Section 3.4 but with a more detailed consideration of the intermolecular interaction and expanding
the free energy into a power series by the density (called virial expansion) including terms of higher
order, which resulted in additional terms in the equation. The empirically determined equation for
seawater in the form of the density as a function of temperature, pressure, and salinity adopted in
UNESCO (1981) was described in Curry and Webster (1999). These forms of EOS have been further
modified to describe the deeply supercooled water as discussed further on in this chapter.
Another approach is similar to that described in Section 4.6 for ice and is based on construction of
thermodynamic potentials for liquid water. As described in Wagner and Pru (2002), the Helmholtz
free energy equation developed by Haar et al. (1982, 1984) has been adopted as a new international
standard by the International Association for the Properties of Water and Steam (IAPWS). The fun-
damental equation of state for water developed by Saul and Wagner (1989) was optimized regarding
its functional structure and that was fitted simultaneously to the experimental data of many different
properties. In 1995, IAPWS adopted the equation of state developed by Pru and Wagner as the new
scientific standard under the name “The IAPWS Formulation 1995 for the Thermodynamic Proper-
ties of Ordinary Water Substance for General and Scientific Use.”
The IAPWS-95 formulation EOS with its subsequent modifications (Wagner and Pru , 2002;
IAPWS- 2008, IAPWS-2009b; Shi and Mao, 2012) is the most elaborate EOS in terms of the
4.7. Generalized Equations of State for Fluid Water 121

Helmholtz function. A compact description of the IAPWS-1995 formulation according to these

sources is as follows. EOS is expressed in the form of dimensionless Helmholtz free energy f (dr, tr)
0 r
that is separated into two parts, an ideal gas part φ (δ r ,τ r ) and a residual part φ (δ r ,τ r ) , so that

f ( ρ ,T )
φ (δ r ,τ r ) = = φ 0 (δ r ,τ r ) + φ r (δ r ,τ r ), (4.7.1)
RspT

where T is temperature, r is the density, fh(r, T) is the specific Helmholtz free energy, dr = r/rcr is the
reduced dimensionless density, tr = Tcr/T is the inverse reduced temperature, rcr = 322 kg m−3 is the criti-
cal density, Tcr = 647.096 K is the critical temperature, and Rsp = 0.46151805 kJ kg−1 K−1 is the specific
0
gas constant. The ideal gas part φ (δ r ,τ r ) is written as (Eqn. 6.5) in Wagner and Pru , 2002)
8
φ 0 (δ r ,τ r ) = ln δ r + n10 + n20τ r + n30 lnτ r + ∑ ni0 ln[1 − exp(−γ i0τ r )], (4.7.2)
i=4

0
where the eight parameters ni0 and five parameters g i are given in Wagner and Pru (2002, Table 6.1),
and IAPWS-2009b (Table 1). The residual part φ r (δ r ,τ r ) can be written following (Eqn. 6.6) in Wagner
and Pru (2002):
7 51
φ r (δ r ,τ r ) = ∑ ni (δ r )di (τ r )ti + ∑ ni (δ r )di (τ r )ti exp[(δ r )ci ] ∑
i =1 i =8
54 56

∑ ] + ∑ ni (δ r )di (τ r )ti exp[ −α i (δ r − ε i )2 − β i (τ r − γ i )2 ] + ∑ ni ∆ bi δ rψ r , (4.7.3)

i = 52 55

where
∆ = θr2 + Bi [(δ r − 1)2 ]ai ,θr = (1 − τ r ) + Ai [(δ r − 1)2 ]1/( 2 βi ) ,ψ
)
δ ] ,ψ r = exp[ −Ci (δ r − 1)2 − Di (τ r − 1)2 ]. (4.7.4)

About 250 parameters—ni, di, ti, ci, ai, bi, gi, ei, Ci, Di, and Ai—are given in Wagner and Pru (2002,
Table 6.2), and IAPWS (2009b) (Table 2). The optimal values of the parameters were found by
the multiparametric fits to the various properties of water over wide domains of temperature and
pressure.
Relations of thermodynamic properties (entropy, enthalpy, pressure, isohoric and isobaric heat
0
capacities, second and third virial coefficients, and others) to the ideal-gas part, φ (δ r ,τ r ), and the
r
residual part φ (δ r ,τ r ), of the dimensionless Helmholtz free energy are given in Table 6.3 of Wagner
0 r
and Pru (2002). The analytical derivatives of φ (δ r ,τ r ) and φ (δ r ,τ r ) with respect to dr and tr are
given in Tables 6.3 and 6.4, respectively, of Wagner and Pru (2002).
As a result of comprehensive tests carried out by IAPWS, the following statements on the range
of validity of IAPWS-95 were made (Wagner and Pru , 2002; IAPWS-2009b). The formulation
is valid in the entire stable fluid region of H2O from the melting curve to 1273 K at pressures up
to 1,000 MPa; the lowest temperature on the melting curve is 251.165 K at ~209.9 MPa. In the
stable fluid region, the formulation can also be extrapolated beyond these limits. Tests show that
(Eqn. 4.7.1) behaves reasonably when extrapolated to pressures up to about 100 GPa and tempera-
tures up to about 5,000 K. This holds at least for the density and enthalpy of undissociated H2O. In
the gas region at pressures below the triple-point pressure, (Eqn. 4.7.1) behaves reasonably when
122 Properties of Water and Aqueous Solutions

extrapolated to the sublimation-pressure curve for temperatures down to 130 K (IAPWS-2011). As

far as can be tested with experimental data, the formulation behaves reasonably when extrapolated
into the metastable regions. Equation (4.7.1) represents the currently available experimental data of
the supercooled liquid (solid–liquid metastable region) and of the superheated liquid (liquid–gas
metastable region) to within the experimental uncertainty. In the case of the supercooled gas (gas–
liquid metastable region), no experimental data are available. In this region, for pressures below
10 MPa, (Eqn. 4.7.1) produces reasonable values close to the saturation line. For calculations further
away from the saturation line, an alternative equation (the so-called gas equation) is given in Wagner
and Pru (2002). The modification described in the Guideline (IAPWS-2012) extends the validity of
the heat-capacity equation down to 50 K and permits the computation of the gas phase properties also
in this low-temperature range.
Holten et al. (2011, 2012) reviewed the available data on various water properties and compared
them with the calculations using the IAPWS-95 EOS. They noted that while the IAPWS-95 formula-
tion does indeed represent the experimental density data at ambient pressure, the deviations from the
formulation become larger with increasing pressure. Especially at higher pressures, there is a sizable
discrepancy between the IAPWS-95 formulation and the experimental data; the slope (or the expan-
sivity) has a different sign. As described earlier, the major domain of applicability of IAPWS-95 and
its predecessors for liquid water was mostly limited at T < 251 K, and the accuracy in predictions of
the density with IAPWS-95 decreased in the supercooled region. Therefore, several formulations of
EOS for the supercooled region were suggested, many of them based on the concept of the second
critical point for liquid water (Section 4.2).

4.7.2. Equations of State Based on the Concept of the Second Critical Point

Poole et al. (1992, 1994) proposed another extension of the van der Waals equation by incorporat-
ing the effects of the network of hydrogen bonds that exist in liquid water. They developed a simple
model for the free energy of the hydrogen bonds Fhb that was superimposed on the free energy
FEOS of a simple liquid described by the equation of state from van der Waals theory. The total free
energy was F = FEOS + 2Fhb, where the factor of 2 accounts for the fact that there are two moles of
hydrogen bonds for every mole of molecules. Based on this additivity and the relation (Eqn. 3.1.11),
p = −(∂F/∂V)T, Poole et al. presented the equation of state in a simple form:

p = pEOS + 2 phb , (4.7.5)

where p is the is the total pressure in the liquid, pEOS is the pressure determined from the van der
Waals equation of state, phb is the pressure exerted by the hydrogen bonds and again the factor of 2
reflects 2 moles of bonds for each mole of water. Equation (4.7.5) is a “mixture model” where the
hydrogen bonds act as a separate species of water exerting their own pressure phb. The hydrogen bond
fraction is temperature dependent. Above freezing point Tf, the bond fraction falls to zero and the
only contribution to the pressure is the background pressure pEOS. Poole et al. assumed that the popu-
lation of the hydrogen bonds consists of two species, strong (open) bonds with energy ehb and entropy
Sh,hb and weak bonds with energy ehb = 0 and entropy S0, the number of configurations in each species
are Zhb and Z0, respectively. They constructed the Helmholtz free energy Fhb for a combination of
4.7. Generalized Equations of State for Fluid Water 123

these two species as a simple partition function. As described in Chapter 3, the number of configura-
tions (statistical sum) in a statistical ensemble of each bond type is
Z 0 = exp(− Sη ,0 /R), Z hb = exp(− Sη ,hb /R). (4.7.6)

The total hydrogen bond free energy was assumed to be a mixture of the two bond types
Fhb = − fhb RT ln[ Z 0 + exp(− ε hb /RT )] − (1 − fhb ) RT ln( Z 0 + 1), (4.7.7)

where the mixture function fhb is a fraction of the hydrogen bonds that are capable of forming strong
(open) bonds. Poole et al. argued that strong bonds are most likely to occur when the bulk molar
volume V is equal to the specific volume Vhb of ice Ih, and approximated fhb(V) as a Gaussian function
of V with some dispersion shb.
Poole et al. (1994) found that this model was able to: 1) qualitatively reproduce the known ther-
modynamic behavior of water; 2) consolidate proposals for the behavior of supercooled water by
showing that they may be different realizations of a single behavior; 3) improve understanding liquid
and amorphous solid water.
Jeffery and Austin (1997, 1999) combined both these approaches in one model. They also assumed
that the equation of state could be written as the sum of the two terms as (Eqn. 4.7.5). For calculation
of pEOS, Jeffery and Austin (1999) modified the equations by Song and Mason (1989, 1990a, b) of the
van der Waals type and presented it in the form

pEOS  a   1 
= 1 +  α EOS − b *− EOS  ρ + α EOS ρ  − 1 . (4.7.8)
ρ RT  RT   1 − λ b
EOS EOS ρ 

The three parameters here, bEOS, b*, and aEOS were expressed via the Boyle volume vB and tempera-
ture TB as

bEOS /v B = 0.2 exp[−21.4(T/TB + 0.445)3 ] − b1 exp(1.016T/TB ) + b2 , (4.7.9)

α EOS /vB = 2.145, b */vB = 1.0823 (4.7.10)

The values of the coefficients were determined from fitting them to experimental data as described
next. For calculation of phb, Jeffery and Austin modified the free energy from Poole et al. as
Fhb = − fhb RT ln[ Z 0 + Z hb exp(− ε hb /RT )] − (1 − fhb ) RT ln( Z 0 + Z hb ), (4.7.11)

which includes the possibility that there are Zhb configurations of strong bonds. It was suggested that
the bond fraction is a function of the temperature and density. These dependencies were separated by
Jeffery and Austin as fhb(T, rw) = f *(rw)f **(T):
1 + Chb1
f * ( ρw ) = (4.7.12a)
exp[( ρ w − ρ hb )/σ hb ]2 + Chb1
f **(T ) = exp[−0.18(T/T f )8 ], (4.7.12b)

where Tf = 273.15. That is, the density dependence was approximated by a modified Gaussian func-
tion centered around density rhb, and the temperature function accounted for the fact that the maxi-
mum specific volume of water is reached near Tf . Using a sophisticated fit to the experimental data
124 Properties of Water and Aqueous Solutions

on the temperature, pressure, density, and entropy of liquid water in the extended range −34 °C
< 1,200 °C, and 1 bar < 3,000 bars, Jeffery and Austin (1997, 1999) found the best set of the parameters:
ehb = −11.490 kJ mole−1, S0 = −61.468 J mole−1 K−1, Shb = −5.128 J mole−1 K−1, rhb = 0.8447 g cm−3,
Chb1 = 0.7140, shb = 0.1425 g cm−3 = 0.1687 × rhb, b1= 0.2581, b2= 0.99859, and lEOS = 0.3241,
TB = 1408.4 K, vB = 4.1782 × 10−5 m−3 mole−1.
Having calculated pEOS from EOS (Eqn. 4.7.8) and phb from (Eqn. 4.7.11) with the use of Equation
(3.1.11), p = −(∂F/∂V)T, the total pressure p can be calculated as a function of the temperature and
density or volume, which allows a plot of the phase diagrams of water in various states. The results
of calculations of water properties in the supercooled region presented in Jeffery and Austin (1997,
1999) were in reasonable agreement with the available data.
An analogous approach for supercooled region was developed by Kiselev (2000) and Kiselev and
Ely (2002). Holten et al. (2011, 2012) developed a different model based on introducing the scaling
fields for supercooled water and the hypothesis of the second critical point and the liquid–liquid
transition. Their model makes use of the fact that fluids belong to the universality class of Ising-like
systems (Landau and Lifshitz, v.5, 1958; Lifshitz and Pitaevskii, 1997) whose critical behavior is
characterized by two independent scaling fields: a “strong” scaling field h1 (ordering field) and a
“weak” scaling field h2, and by a dependent scaling field, which asymptotically close to the critical
point becomes a generalized homogeneous function of h1 and h2. By allowing the slope of the liquid–
liquid transition line and the critical pressure to be freely adjustable parameters, their model was able
to represent almost all available thermodynamic property data for supercooled water. A compact
review of the theory by Holten et al. (2011, 2012) was given by Hellmuth et al. (2013). The theories
of water in the supercooled region and at high pressures are being extensively developed, and a sub-
stantial breakthrough in this area can be expected in the near future.
Relations among Various Pressure Units 125

Appendix A.4 for Chapter 4. Relations among

Various Pressure Units

Saturated vapor pressures are used in various units. The relations among these units are given here for
convenience. In SI units, the unit of pressure is the pascal (Pa), 1 Pa = 1 N m−2, where N is the newton,
and pressure is often measured in hectopascals (hPa), 1 hPa = 102 Pa. In high-pressure experiments, the
following units are used: megapascal (MPa), 1 MPa = 106 Pa, and gigapascal (GPa), 1 GPa = 109 Pa.
In CGS units, the pressure is often measured in dyn cm−2. The ratio between these units is
Pa = 10 dyn cm−2, and 1 hPa = 103 dyn cm−2. Alternative units of pressure include:1 bar = 105 Pa = 106 dyn
cm−2; 1 mb (millibar) = 102 Pa = 1 hPa = 103 dyn cm−2;1 atm (atmosphere) = 1.01325 bar = 1.013 × 106
dyn cm−2 = 1.013 × 105 Pa = 0.1013 MPa; 1 MPa = 10 bar = 107 dyn cm−2 ≈ 10 atm; 1 GPa = 104
bar = 1010 dyn cm−2 ≈ 104 atm.
5
Diffusion and Coagulation Growth
of Drops and Crystals

In this chapter, we consider the condensation growth and evaporation of drops and the depositional
growth and sublimation of crystals by diffusion of water vapor from or to environmental moist air.
These processes require knowledge of the water and ice supersaturation, the equations for which
are derived and studied for various cases. Cloud glaciation due to crystal growth and evaporation of
drops is considered. The kinetic equations of regular condensation and deposition are derived. The
coagulation/accretion growth of drops and crystals due to the particles’ collisions with subsequent
coalescence is considered.

5.1. Diffusional Growth of Individual Drops

The theory of drop diffusional growth and evaporation in a field of water vapor originated from
Maxwell (1890), who solved the problem for the steady-state condensational growth of a spherical
drop assuming saturated vapor pressure at the drop surface. This theory was subsequently developed
to account for various additional effects. The equations for drop growth by diffusion are derived in
the following.

5.1.1. Diffusional Growth Regime

Consider the simplest case of a water drop in a field of water vapor, with the following two assump-
tions: 1) the vapor field around a drop can be described in the diffusion approximation; 2) neglecting
the latent heat released at condensation. Then, the vapor diffusion toward (from) the drop can be
described with the convective-diffusion equation for the vapor density rv:

∂ρ v
+ u∇ρ v = Dv∇ 2 ρ v , (5.1.1)
∂t
where t is time, u is velocity relative to the drops, Dv is the vapor diffusion coefficient, and — is the
differential divergence operator. For a spherical drop in a still air and neglecting drop fall speed,
(Eqn. 5.1.1) can be written in spherical coordinates as

∂ρ v  ∂2 ρ 2 ∂ρ v 
= Dv  2v +  ρv , (5.1.2)
∂t  ∂ r r ∂r 

where r is the distance from the drop center. The initial and boundary conditions for this problem are

ρ v (r , 0) | r →∞ = ρ v∞ , ρ v (rd , t ) = ρ ws , (5.1.3)

127
128 Diffusion and Coagulation Growth of Drops and Crystals

where rd is the drop radius, rws is the saturated vapor density at the drop surface, and rvµ is the vapor
density at infinite distance from the drop. A solution to (Eqn. 5.1.2) with the conditions (Eqn. 5.1.3) is

rd   r −r 
ρ v (r , t ) = ρ v∞ + ( ρ ws − ρ v∞ ) 1 − erf  d
 , (5.1.4)
r   2 Dv t 
  

where erf(z) is the error function. The second term in the brackets accounts for the time dependence
and is much less than 1 for t = teq >> rd2/p Dv. For standard atmospheric conditions teq ~ 10−6 s for
rd ~ 100 mm, and teq ~ 10−4 s for rd ~ 1000 mm. These time scales are much shorter than the character-
istic time scales of vapor fluctuations; therefore, the second term with time can be neglected, so that
for t >> teq, the solution is close to the steady state
rd
ρ v (r ) = ρ v∞ + ( ρ ws − ρ v∞ ) . (5.1.5)
r
The solution of this type found by Maxwell resembles the expression for the electrostatic potential
outside of a conducting sphere of radius rd with electrical charge, and is therefore referred to as an
electrostatic analogy of the water vapor field around a droplet. As discussed in Section 5.2, this anal-
ogy helps to formulate an appropriate description of the vapor field around the crystals.
The diffusional vapor flux to or from the drop surface can be evaluated as a surface integral of the
vapor density gradient over the drop surface Sd

∂ρ v (r )
J c , dif |rd = − ∫ Dv dSd
Sd ∂r
∂ρ v (r )
= −4π rd2 Dv |rd = 4π rd Dv ( ρ ws − ρ v∞ ). (5.1.6)
∂r
Note that this flux is also similar to the flux of the electrostatic field around a conducting sphere with
capacitance Ce, which is equal to its radius, Ce = rd. The flux (Eqn. 5.1.6) determines the drop mass
growth rate

 dm 
mɺ dif ≡  d  = − J c , dif = 4π Dvrd ( ρ v∞ − ρ ws ) = 4π Dvrdδ w = 4π Dvrd ρ ws sw ,
 dt  dif (5.1.7)
where δ w = ( ρ v∞ − ρ ws ) and sw = ( ρ v∞ − ρ ws ) /ρ ws are the absolute and fractional water supersaturations
introduced in Chapter 3. Using the equation of state for vapor from Chapter 3, ev = RvrvT, this can
be rewritten

 dmd  M w  ev∞ ews 

  = 4π Dvrd  −  . (5.1.8)
 dt  dif R  T∞ T0 
Equation (5.1.7) yields for the radius growth rate

 dr  Dδ Ds ρ
rɺd , dif ≡  d  = v w = v w ws . (5.1.9)
 dt  dif r ρ
d w rd ρ w
5.1. Diffusional Growth of Individual Drops 129

When rv∞ > rws , and the supersaturation sw > 0, the drop grows, and when rv∞ < rws, and sw < 0, the
drop evaporates. The value of Dv depends on the temperature and pressure. Hall and Pruppacher
(1976) approximated Dv as
1.94
T   p0 
Dv = 0.211   , (5.1.10)
 T0   p 

where T0 = 273.15 K, p0 = 1013.25 mb, and Dv is in cm2 s−1. Equation (5.1.9) is the simplest form
of the equation for drd /dt. Subsequent derivations have accounted for various corrections, including
kinetic and psychrometric corrections, which are considered in the next sections.

5.1.2. The Kinetic Regime and Kinetic Corrections to the Growth Rate

We assumed earlier in this chapter that the diffusion approximation is valid for both the vapor and
temperature fields, which is characterized by abundant collisions between the vapor molecules and
the diffusion coefficient. However, this regime becomes invalid at small distances from the drop
surface on the order of the molecular mean free path length, l f ~ 0.1 mm at typical conditions. The
kinetic regime acts at distances ~l f from the drop surface, which is characterized by the absence of
collisions between the molecules. Several methods have been developed to overcome this problem,
with the best known of these being the boundary sphere method developed by Fuchs (1959, 1964),
which is illustrated in Fig. 5.1. This method assumes that the space outside the drop can be separated
into two parts by a “boundary sphere” with the radius rb = rd + Dv, where Dv is some length compa-
rable to l f. The kinetic regime acts at rd < r < rd + Dv, and the diffusion regime acts at r > rd + Dv. The
main premise of the method is that the kinetic and diffusion vapor fluxes are matched at the surface
of the boundary sphere at r = rb.

A B

rd
∆v

Figure 5.1. Illustration of the method of the boundary sphere for calculation of the drop growth.
The domain with kinetic vapor fluxes is denoted with A, the domain with diffusion fluxes is B,
the droplet radius is rd, and the thickness of the boundary sphere is Dv. The radius of the boundary
sphere is rb = rd + Dv. q is the maximum angle at which water molecules flying to the sphere still
may collide with it.
130 Diffusion and Coagulation Growth of Drops and Crystals

We can now repeat the solution of the diffusion (Eqn. 5.1.2) but with the boundary conditions at
the boundary sphere, and instead of (Eqn. 5.1.6) we obtain a solution for the diffusion flux:

J c , dif |rd + ∆ v = 4π Dv (rd + ∆ v )[ ρ v (rd + ∆ v ) − ρ v∞ ]. (5.1.11)

The kinetic flux is a sum of the condensation flux J +kin toward the drop and evaporation flux J kin
-
from
+
the drop. Fig. 5.1 illustrates the geometry of the fluxes. The molecular flux J kin is proportional to the
vapor density at r < rd + Dv, and to the thermal velocity Vw of vapor molecules (see Chapter 3), and
can be evaluated using the velocity distribution function fv(v) that is assumed to be a Maxwell dis-
tribution. We consider the polar coordinate system and assume that the polar axis is directed toward
the drop center.
The Maxwell distribution normalized to the molecular concentration cv = rv /mw in this coordinate
system can be written as (see Appendix A to Chapter 3)

 mw 
3/2
 m v2 
fv ( v )dv = cv  exp  − w  sinθ dθ dϕ , (5.1.12)
 2π kT   2 kT 

where mw is the mass of a water molecule. Consider a unit area S1 on the boundary sphere rb = rd + Dv.
The molecular density flux toward the drop through this S1 is proportional to the velocity component
vN normal to this area. We denote q as the angle between the axis normal to the surface and a direc-
tion of a vapor molecule velocity. Then, the normal projection of the velocity is vN = v cosθ , and the
concentration flux density to the unit area is
∞ θ0 2π
jc = −cv ∫ dvfv (v) ∫ sin θ cosθ dθ ∫ dϕ , (5.1.13)
0 0 0

where q0 is the maximum angle at which molecules flying from the boundary sphere still can collide
with the drop (Fig. 5.1). The minus sign occurs because the flux is directed inside and the normal to the
drop surface is directed outward. Evaluation of these integrals given in Appendix A of Chapter 3 yields

 m  1/ 2
1  mw    1 2 
−2

jc = −cv  w      sin θ 0  2π  , (5.1.14)

 2π kT  2  2 kT    2
 

where each square bracket denotes each of the three integrals in (Eqn. 5.1.13). The resulting flux
density is
1/ 2 1/2
1  8kT   8 RT 
jc = − VcvwVw sin 2 θ 0 , ∈ VwV=w   =   . (5.1.15)
4  π m w   π Mw 
Here, Vw is the mean thermal velocity of vapor molecules. It is seen from Fig. 5.1 that

rd2
sin 2 θ 0 = . (5.1.16)
(rd + ∆ v )2

The vapor density rv and concentration cv are related as rv = cvmw; thus, the vapor mass flux is
jr = mw jc, which results in replacement of cv with rv in the mass flux density:
1
jρ = − ρ vVw sin 2 θ 0 . (5.1.17)
4
5.1. Diffusional Growth of Individual Drops 131

Not all of the molecules colliding with the drop will be absorbed on its surface, some will bounce
back. The condensation coefficient, ac, is the ratio of the molecular flux jcond condensed on the water
drop to the incident molecular flux jr; that is, ac = |jcond /jr |, where | | means the absolute value.
Numerous measurements since the 1930s have shown significant variations of ac from 1 to 0.01 for
relatively pure drops, with much smaller values for polluted drops. Values ac = 0.036−1 are most
frequently used in drop growth calculations. The values of ac can decrease to 10−5–10−3 for drops
covered by films of surface-active substances like cetyl alcohol and similar agents used for artificial
fogs suppression (e.g., Deryagin and Kurgin, 1969; Bigg et al., 1969; Buikov and Khvorostyanov,
1979). The kinetic condensation flux J +kin is obtained from the product of jr , ac and the boundary
sphere surface Sb = 4π (rd + ∆ v )2 , yielding the fraction of colliding molecules absorbed by the drop.

1
+
J kin = −α c Sb jρ = −α c Sb Vw ρ v (rd + ∆ v )sin 2 θ 0
4
= −π rd2α cVw ρ v (rd + ∆ v ), (5.1.18)

where we used (Eqn. 5.1.16) for sinq 0. The evaporation flux from the drop surface is evaluated
similarly
−
J kin = π rd2α eVw ρ ws (T0 ) , (5.1.19a)

where ae is the evaporation coefficient that is the fraction of the molecules emitted from the surface.
Assuming ae = ac, we can write the total kinetic flux

J kin = J kin
+
+ J kin
−
= π rd2α cVw [ ρ ws (T0 ) − ρ v (rd + ∆ v )] (5.1.19b)

This kinetic flux should be equal to the diffusion flux (Eqn. 5.1.11) at the boundary surface. Equating
them, we obtain
4 Dv (rd + ∆ v ) ρ v∞ + α crd2Vw ρ ws (T0 )
ρ v (rd + ∆ v ) = . (5.1.20)
4 Dv (rd + ∆ v ) + α crd2Vw

Substituting this expression into (Eqn. 5.1.11), we obtain Jc, dif and dmd /dt, taking into account the
kinetic correction
dmd
= − J c , dif = 4π rd Dv* ( ρ v∞ − ρ ws ) = 4π rd Dv* ρ ws sw , (5.1.21)
dt
−1
Dv  rd ξ  4 Dv
Dv* = = Dv kkin , kkin =  + con  , ξ con = , (5.1.22a)
rd ξ
+ con  rd + ∆ v rd  α cVw
rd + ∆ v rd

where sw is the water supersaturation, and we introduced an effective diffusion coefficient D*v and the
kinetic correction xcon to the drop condensation growth rate. As mentioned before, D v ~ l f ~ 0.1 mm,
and for sufficiently large drops, rd > 0.5–1 mm, this expression is simplified
Dv rd
Dv* = = Dv kkin . kkin = , (5.1.22b)
1 + ξ con /rd rd + ξ con

where kkin is the simplified kinetic correction. Using (Eqn. 5.1.22b), the mass growth rate (Eqn. 5.1.21)
can be written as
dmd rd2
= 4π Dv ρ ws sw = 4π Dvrd ρ ws sw kkin . (5.1.23)
dt rd + ξ con
132 Diffusion and Coagulation Growth of Drops and Crystals

5.1.3. Psychrometric Correction Due to Latent Heat Release

The saturated vapor density in (Eqn. 5.1.21) for dmd /dt depends on the drop temperature, which is
influenced by the latent heat release during condensation or evaporation. This results in occurrence
of the psychrometric correction to the drop diffusion growth rate. To account for this effect, we have
to consider the heat transfer in the vicinity of the drop. The heat flux density is given by Fourier’s
law, jh = − ka∇T , where ka is the thermal conductivity coefficient of humid air parameterized as
ka = (5.69 + 0.017T) × 10−5, ka is in cal/(cm sec °C), and T is in °C (Pruppacher and Klett, 1997).
With this flux, the temperature field around a drop is described by a heat balance equation for the
temperature similar to the Equation (5.1.1) for rv

∂T 1
+ u∇ T = − ∇jh = κ T ∇ 2T , (5.1.24)
∂t ρac p

where kT is the thermal diffusivity coefficient [cm2 s−1] related to ka as kT = ka/(racp).

The heat fluxes and their relations to the mass fluxes are considered in cloud physics (as in many
other aerosol studies), introducing the dimensionless numbers referred to as Peclet (Pe), Prandtl (Pr),
and Schmidt (Sc) numbers,
Du ηa ν ηa ν
Pe = , Pr = = a, Sc = = a, (5.1.24a)
κT ρ aκ T κ T ρ a Dv Dv

where ha = va ra is the dynamic viscosity of the air, va is the air kinematic viscosity, and D is the
particle diameter, which serves here as a length scale. The Peclet number characterizes the ratio of
the convective and diffusive heat transfer processes, and the Prandtl number characterizes the ratio of
the diffusive fluxes of the mass and heat. For air, Pr ≈ 0.8 and Sc ≈ 0.71, and Dv /kT = Pr/Sc ≈ 1.12.
At T = 273.15 K and p = 1 atm, as follows from (Eqn. 5.1.10), Dv ≈ 0.21 cm2 s−1; thus kT ≈ 1.12
× Dv = 0.19 cm2 s−1. That is, the coefficients Dv and kT are close, and it is possible in many cases to
assume that kT ≈ Dv, which simplifies the growth rate equations.
Neglecting again the air and drop velocities, and using the initial and boundary conditions for the
steady state problem,
T (r , 0)| r = rd = T0 , T |r →∞ = T∞ , (5.1.25)

where T0 and Tì are the temperatures at the drop surface and at infinity. Thus, we obtain a solution
similar to (Eqn. 5.1.5) for rv:
rd
T (r ) = T∞ + (T0 − T∞ ) , (5.1.26)
r
where again we neglect the time dependence and assume steady state. The rate of heat transfer dQ/dt
is equal to the heat flux from the drop surface Jheat(rd),
dQ ∂T (r )
= − J heat (rd ) = − ∫ ka dSd
dt Sd ∂r
∂T (r )
= −4π rd2 ka = 4π kard (T0 − T∞ ). (5.1.27)
∂r rd
5.1. Diffusional Growth of Individual Drops 133

Under quasi-steady conditions, this heat flux from the drop should be equal to the condensation heat
flux Le Jc,dif with Jc,dif given by (Eqn. 5.1.6). Equating them, we obtain

∆T = T0 − T∞ = ( Dv Le /ka )( ρ v∞ − ρ ws ). (5.1.28)

This is the psychrometric temperature difference (“thermal jump”) between the drop surface and
environment, which shows that a growing droplet at rv∞ > rws is warmer than the environment, and
an evaporating drop at rv∞ < rws is cooler than the environment. This expression was obtained by
considering only the diffusion process.
Accounting for kinetic effects in the temperature field near the drop surface can be done analo-
gously to that for the vapor field, by considering the boundary sphere that separates the domains with
diffusion and kinetic fluxes. The radius of the boundary sphere is rb = rd + DT, where DT is the thick-
ness of the boundary sphere with the kinetic molecular heat flux (Fig. 5.1). Evaluating the kinetic
heat flux near the drop at the distance rb = rd + DT, and matching the diffusion and kinetic heat fluxes
leads to an equation similar to (Eqn. 5.1.22a)

ka 4 ka 4κ T
ka* = , βT = = , (5.1.29)
rd β α T c p ρ aVw α T Vw
+ T
rd + ∆T rd

where we used the relation kT = ka /(racp), b T is the kinetic correction to the growth rate in thermal
conductivity and aT is the thermal accommodation coefficient. The thermal accommodation coef-
ficient is the ratio of the number of water vapor molecules that achieve thermal equilibrium upon
collision with a drop, to a total number of the molecules colliding with the surface. The value of DT is
also ~0.1 mm, and for sufficiently large drops, rd >> DT, this expression is simplified as
ka rd
ka* = = ka . (5.1.30)
1 + βT /rd rd + βT

To account for the psychrometric correction for latent heat release to the mass or radius growth
rate, the system of (Eqns. 5.1.21) and (5.1.27) should be solved together. To solve this system and
obtain dmd /dt with a psychrometric correction, it is convenient to express first DT via dmd /dt using
the energy balance between the heat transfer dQ/dt and mass transfer dmd /dt
dQ dmd
= 4π rd ka* (T0 − T∞ ) = Le , (5.1.31)
dt dt
which gives

Le dmd
∆T = (T0 − T∞ ) = . (5.1.32)
4π rd ka* dt

The correction DT << Tì, and the saturated density rws(Tì + DT) can be expanded into a power series
by DT/ T. Using the Clausius–Clapeyron (Eqn. 3.7.7), and omitting further for brevity the subscript
“∞”, we obtain for ews(T + DT):

 L ∆T   Le ∆T 
ews (T + ∆T ) = ews (T )exp  e  ≈ ews (T )  1 + R T T  . (5.1.33)
R
 v T T   v 
134 Diffusion and Coagulation Growth of Drops and Crystals

And for rv using the equation of state ews = RvrwsT:

ews (T + ∆T ) ews (T )  Le ∆T   ∆T 
ρ ws (T + ∆T ) = ≈ 1 +  1 −  (5.1.34)
Rv (T + ∆T ) RvT  RvT T   T 

  L  ∆T 
≈ ρ ws (T ) 1 +  e − 1  . (5.1.35)
  RvT  T 

Substitution of (Eqn. 5.1.32) for DT into (Eqn. 5.1.35) yields

  L  Le dmd 
ρ ws (T + ∆T ) ≈ ρ ws (T ) 1 +  e − 1  * . (5.1.36)
  RvT  4π rd kaT dt 

Taking into account that rws in (Eqn. 5.1.21) depends on the temperature at the drop surface, (T + DT),
and substituting (Eqn. 5.1.36) into (Eqn. 5.1.21) for dm/dt, we obtain

dmd
= 4π rd Dv* [ ρ v∞ − ρ ws (T + ∆T )]
dt
Dv* Le ρ ws (T )  Le  dm
= 4π rd Dv* [ ρ v∞ − ρ ws (T )] − *  − 1  d . (5.1.37)
kT T  RvT  dt
Solving for dmd /dt and introducing the fractional supersaturation sw, we get finally

dmd 4π rd Dv* ρ ws sw
= , (5.1.38)
dt Γw

where Gw is the psychrometric correction that occurs due to the latent heat release at condensation,

Dv* Le ρ ws  Le  L ρ  L 
Γw = 1 +  − 1  ≈ 1 + e ws  e − 1  . (5.1.39a)
ka*T  RvT  c pT ρ a  RvT 
The second equality uses the relation ka* = cp rak T* and the approximate relation k T* ≈ D*v discussed
earlier. The first term in the parentheses is ~20 >> 1 and the second term, −1, can be neglected with
the error of ~5%. Then, Gw can be written in the form that coincides with G1 introduced in Section 3.11
for the wet adiabat
L2e L dq
Γw ≈ 1 + qws = 1 + e ws = Γ1 , (5.1.39b)
c p RvT 2 c p dT

where qws is the specific humidity saturated over water. The phase heat release resulted in the second
term; it would be Gw = 1 without account for this effect.
When considering growth of the small solution drops, it is necessary to account for the solution
and curvature effects. This can be done simply by adding the corresponding terms to supersaturation
as described in Chapter 3; then (Eqn. 5.1.38) becomes

dmd 4π rd Dv* ρ ws (sw − ssalt ) (5.1.40a)

= ,
dt Γw
A Br 3 
ssalt =  K − 3 d 3 , (5.1.40b)
 rd mw − mdry 
 
5.1. Diffusional Growth of Individual Drops 135

where AK and B are the Kelvin curvature parameter and the nucleus activity defined in Section 3.9,
and mdry is the mass of a dry aerosol particle. For drops with rd of a few microns, the solution and cur-
vature effects ssalt are usually ignored in simulations although more precise calculations may require
accounting for these terms.
In many papers and textbooks (e.g., Mason, 1971; Young, 1993; Pruppacher and Klett, 1997), the
equation for the mass growth rate is given in the form
dmd 4π rd (sw − ssalt )
= , (5.1.41a)
dt RT L e  Le M w 
+ − 1
Dv*ews M w ka*T  RT 

or in simplified forms with ssalt = 0 and omitting the term −1 in the parentheses. It can be shown that
this form (Eqn. 5.1.41a) is equivalent to the form (Eqn. 5.1.40a). Substituting here the equation of
state, ews = rwsRvT, using the relation Rv = R /Mw and multiplying by D*v rws, we obtain

dmd 4π rd (sw − ssalt )

=
dt RT L  Le 
+ e  − 1
Dv* ρ ws M w RvT ka*T  vR T 
4π rd Dv* (sw − ssalt ) ρ ws 4π rd Dv* (sw − ssalt ) ρ ws (5.1.41b)
= = ,
D* L ρ  L  Γw
1 + v *e ws  e − 1 
kaT  RvT 
where we used (Eqn. 5.1.39a) for Gw. Using the approximate relation ka* = k T* racp ≈ D*v racp , the
factor Gw can be replaced with G1 as in (Eqn. 5.1.39b). Thus, both forms of the growth rate equation,
derived here in a simpler form (Eqn. 5.1.40a) and commonly used (Eqn. 5.1.41a) are equivalent. The
forms (Eqns. 5.1.38) and (5.1.40a) for dmd /dt are more convenient in many cases because they are
compact and show that the growth rate is proportional to the major driving force: saturated vapor
density and supersaturation. Further, the growth rate equation is written in a factorized form, the
variables (supersaturation, kinetic, and psychrometric factors) are separated and are written as three
multipliers, which simplifies various analytical solutions as is illustrated in the following chapters.

5.1.4. Radius Growth Rate

Equation (5.1.40a) yields for the droplet radius growth rate

drd Dv* ρ ws (sw − ssalt ) Dv* ρ ws (sw − ssalt )

rɺd ≡ = ≈ , (5.1.42)
dt rd ρ w Γ w rd ρ w Γ1

or without solute and curvature effects

drd Dv* ρ ws sw Dv* ρ ws sw
rɺd ≡ = ≈ . (5.1.43)
dt rd ρ w Γ w rd ρ w Γ1

These simplified forms are equivalent to the other forms commonly used for dr/dt that follow from
(Eqn. 5.1.41a) for dmd /dt (e.g., Young, 1993; Pruppacher and Klett, 1997; Cotton et al., 2011)
drd sw − ssalt
rd = . (5.1.44)
dt ρ w RT ρ w Le  Le M w 
+ − 1
Dv*ews M w ka*T  RT 

136 Diffusion and Coagulation Growth of Drops and Crystals

The equivalence of (Eqn. 5.1.44) with (Eqns. 5.1.42) and (5.1.43) for drd /dt can be shown again sub-
stituting into (Eqn. 5.1.44) the equation of state ews = rwsRvT, the relation Rv = R/Mw, multiplying by
D*v rws, and dividing by rd,

drd sw − ssalt
=
dt ρ w RTrd ρ Lr LM 
+ w * e d  e w − 1
Dv* ρ ws RvTM w kaT  RT 
(sw − ssalt ) Dv ρ ws
*
=
 Dv* Le ρ ws  Le M w 
rd ρ w 1 + *  RT − 1  
 k a T  
(sw − ssalt ) Dv* ρ ws (sw − ssalt ) Dv* ρ ws
= ≈ , (5.1.44a)
rd ρ w Γ w rd ρ w Γ1

where we used (Eqn. 5.1.39a) for Gw, and the last equation is obtained using again the relations
ka* = k T* racp ≈ D*v racp . Equations (5.1.42) and (5.1.43) are written in the factorized form so that the
factors describing the supersaturation, kinetic, and psychrometric corrections are separated. This
factorized form of (Eqns. 5.1.42) and (5.1.43) and separation of the dependencies is especially conve-
nient in integration of the equations when developing analytical parameterizations of drop and crystal
nucleation, as will be shown in the next chapters. Equation (5.1.42) can be rewritten with explicit
dependence on the kinetic correction as
drd Dv ρ ws sw
= . (5.1.45)
dt ρ w Γ w (rd + ξ con )

It is also used in a slightly different form:

drd c s Dρ
≈ 3 w w , c3 w = v ws . (5.1.46)
dt rd + ξ con ρ w Γ1

Equation (5.1.40a) for dmd /dt and (Eqn. 5.1.46) for drd /dt shows that the droplet growth rate may
substantially depend on xcon, which is determined by ac. At T = 0 °C, p = 1013 mb, an estimate with
(Eqn. 5.1.15) gives Vw ~ 570 m s−1, then (Eqn. 5.1.22a) with Dv = 0.21 cm s−2 yields the values of the
kinetic correction of xcon ≈ 0.15 mm for ac = 1 and xcon ≈ 3.7 mm for ac = 0.04. Thus, the kinetic cor-
rection has little influence on drop growth rate for rd > 1–2 mm if ac = 1, but can substantially suppress
the drop growth rates with rd ~ 4 mm if ac = 0.04. Therefore, further measurements and refinements
of the values of the condensation coefficient under various conditions are needed. If the drops are
polluted with some substances with low condensation coefficients, the kinetic correction can be very
large. For example, some surface-active agents like cetyl alcohol have ac ~ 10−5 and xcon ~ 104 cm.
When xcon >> rd, the droplets grow in the kinetic regime
drd Dρ s
= v vs w . (5.1.47)
dt ρ wξ con Γ w

The drop radius growth is very slow in this regime. In the Maxwellian diffusion regime, drd /dt ~ 1/rd,
the smaller droplets grow faster than the larger droplets, and the size spectrum narrows with time.
In contrast, the radius growth rate in kinetic regime (Eqn. 5.1.47) does not depend on the radius, and
the size spectrum can broaden. This can be one reason for spectral broadening in polluted clouds.
5.1. Diffusional Growth of Individual Drops 137

Extensive theoretical, laboratory, and field studies of ac were performed during the 1960s and
1970s in the context of weather modification projects on warm fog suppression, and it was found
that ac can decrease by 2–5 orders of magnitude (down to 3.5 × 10−5) in the presence of surfactants
(e.g., Juisto, 1964; Deryagin et al., 1966; Bigg et al., 1969; Deryagin and Kurgin, 1972; Silverman
and Weinstein, 1974; Buikov and Khvorostyanov, 1979). The slow growth of the droplets covered
with the surface-active agents was used for artificial fog suppression. However, if supersaturation
generation continues (e.g., due to radiative or advective cooling or moistening), this leads to a sub-
stantial increase in supersaturation that compensates for the slow drop growth, thus hampering fog
development only for a short period (Buikov and Khvorostyanov, 1979).

5.1.5. Ventilation Corrections

In the preceding derivations, the effects of drop motion and convective velocities u on the drop
growth and evaporation were neglected. Large drops fall at sufficiently high velocities so that the
effects of convective velocities become significant, especially on the drop evaporation in the sub-
saturated air. These effects are accounted for by introducing the ventilation correction to the drop
growth rate or the ventilation coefficient fv. These corrections in principle can be derived analytically
by solving the convective-diffusion equation for the vapor field. However, such derivations require
detailed calculations of the airflow around a drop, are rather complicated, and may need additional
fitting to the measured evaporation rates.
Hence, it has been customary in cloud physics to use empirical expressions obtained from mea-
surements and to express them using dimensionless numbers: the Schmidt number Sc introduced in
(Eqn. 5.1.24a), the Reynolds number Re, the mean transfer coefficient kv, and the Sherwood number Sh,
uD (dmd /dt ) (dmd /dt )
Re = , fv = , kv = ,
νa (dmd /dt )0 4π rd2 ( ρ v∞ − ρ ws )
2 kvrd 2rd (dmd /dt )
Sh = = = 2 fv , (5.1.48)
Dv Dv 4π rd2 ( ρ v∞ − ρ ws )

where u is the convective velocity around the drop, D = 2rd is the drop diameter, and (dmd /dt)0 is the
mass growth rate without account for the ventilation correction.
The experimental data on the ventilation coefficient fv were approximated in Beard and Prup-
pacher (1971) as
fv = 1.0 + 0.108(Sc1/ 3 Re1/2 )2 ≈ 1.00 + 0.86 Re, (5.1.49a)

for Re < 2.46, that is, rd < 60 mm and

fv = 0.78 + 0.308(Sc1/3 Re1/2 ) ≈ 0.78 + 0.275 Re1/2 , (5.1.49b)

for 2.46 < Re < 3.34 × 102, that is, 60 mm < rd < 1500 mm. The second equalities here and the limits
by Re and rd are given for Sc ≈ 0.71 for the air—i.e., Sc1/3 = 0.89.
The mass growth rate with account for the ventilation correction is

dmd  dmd 
=  fv , (5.1.50)
dt  dt 0
138 Diffusion and Coagulation Growth of Drops and Crystals

where (dmd /dt)0 is described by (Eqn. 5.1.38). The factor fv ~ 5 at rd = 0.5 mm and fv ~ 10 at rd = 1 mm;
hence, the ventilation correction substantially increases the growth-evaporation rates of sufficiently
large drops. Equation (5.1.50) with (Eqns. 5.1.38), (5.1.48), and (5.1.49a,b) describe droplet growth
or evaporation rates in the field of the supersaturation with account for the kinetic, psychrometric,
and ventilation corrections.

5.2. Diffusional Growth of Crystals

5.2.1. Mass Growth Rates

The growth rates of crystals are derived from the electrostatic analogy following Jeffreys (1918).
This analogy was mentioned already in Section 5.1 with respect to droplet growth rates, and becomes
especially useful for consideration of the problem for nonspherical crystals. The analogy is based on
the similarity of the fields of water vapor density rv and temperature T around a crystal to the fields
and fluxes of the electrostatic potential Fe around a charged conductor with electrical charge Qe and

capacitance Ce . The relations of electrical field E to Fe and to the density of electrical charge re are
described by the Maxwell equations (e.g., Landau and Lifshitz, v. 2, 2005)

E = −∇Φ e , divE = 4πρ e . (5.2.1)

Substitution of the second equation into the first one yields

divE = div(−∇Φe ) = −∆Φe = 4πρe , or ∆Φe = −4πρe , (5.2.2)

which is the Poisson equation that relates the electrical potential and the charge. Integration of the
first equation of (Eqn. 5.2.1) over the surface surrounding the charge can be done using (Eqn. 5.2.2)
and the Gauss–Ostrogradsky equation, which expresses the integral over the surface S via the integral
over the volume V,

∫∞Ú EdS = ∫ divEdV .
sS V
(5.2.3)

This yields

∫s∞Ú ∇Φ dS = s∞∫Ú (−E )dS = −∫ divEdV = −4π ∫ ρ dV = −4π Q .
S
e
S V V
e e (5.2.4)

Here, Qe is the total integral charge that is the integral of the charge density over the volume and
can be expressed via the capacity Ce and the difference of the potentials at the surface Fes and at the
infinite distance from the conductor Fe∞:

Qe = Ce (Φ es − Φ e∞ ). (5.2.5)

Combining (Eqns. 5.2.4) and (5.2.5) yields

∫∞Ú ∇Φ edS = −4π Qe = −4π Ce (Φ es − Φ e∞ ).
sS
(5.2.6)

According to the electrostatic analogy, the water vapor density rv is analogous to Fs, the vapor flux

jv = Dv∇ρ v is analogous to the flux ∇Φ e, and we can write by analogy with (Eqn. 5.2.6)

∫∞Ú jv dSS == ∫∞Ú DDv∇∇ρv dS = −4π DvCe ( ρis − ρv ∞ ),
sS sS
(5.2.7)
5.2. Diffusional Growth of Crystals 139

where ris is the saturated over ice vapor pressure at the crystal surface, rv∞ is the vapor pressure
at infinity. The surface integral over the vapor flux jv is the crystal mass growth rate dmc /dt, and
we obtain
dmc
dt ∫s∞Ú
== jv dS == 4π DvCe ( ρ v ∞ − ρis ). (5.2.8)

Using the equation of state for the vapor from Chapter 3, ev =RvrvT, this can be rewritten

 dmc  M w  ev∞ eis 

  = 4π Dv Ce − . (5.2.9)
dt  dif R  T∞ T0 

To account for the temperature difference between the crystal and environment, we need to con-
sider the heat flux due to the latent heat release (or consumption) at deposition (or sublimation).
The psychrometric correction can be derived in the same way as in Section 5.1 for the drops, but the
particle radius should be replaced again with the capacity Ce, and this leads to a generalization of
(Eqn. 5.1.27) for the rate of heat flux transfer
dQ ∂T (r )
= − J heat = − ∫ ka dSd = 4π kaCe (T0 − T∞ ), (5.2.10)
dt Sd ∂r

where the notation is the same as in Section 5.1 but rd is replaced with Ce. This equation also shows that
a growing crystal is warmer than environment (T0 > T∞) and a sublimating crystal is colder (T0 < T∞).
Equating again the heat flux dQ/dt to the latent heat flux Ls(dmc/dt), expressing as in (Eqn. 5.1.28)
DT = (T0 − T∞) via Drv = (rv∞ − r is), expanding the saturated humidity ris(T +DT) into the power series
and rearranging the terms we obtain similar to (Eqn. 5.1.38) for the mass growth rate

dmc 4π Ce Dv ρis si
= , (5.2.11)
dt Γi
where si is the fractional ice supersaturation, and Gi is the psychrometric correction that occurs due to
the latent heat release at condensation:

Dv Ls ρis  Ls  L  L ρ
Γi = 1 +  − 1  ≈ 1 + s  s − 1 is . (5.2.12)
kaT  RvT  c pT  RvT  ρa
The second equality uses the relation ka = cprakT and the approximate equality kT ≈ Dv discussed in
Section 5.1. The second term in parentheses, −1, is approximately 4–5% of magnitude of the first
term and can be neglected in many cases.
The generalization of the spherical vapor and heat fluxes for the drops to the case of nonspherical
crystals was relatively simple. However, a generalization of the kinetic corrections is more difficult,
because the method of the boundary sphere cannot be used since spherical symmetry cannot be
applied for the crystals. For spherical drops in Section 5.1, the kinetic correction was introduced by
replacement of the diffusion Dv and heat conductivity ka coefficients with the “effective coefficients”
D*v and ka* that depend on the drop radius rd as Dv*/Dv = rd /(rd + xcon) with xcon = 4Dv /acVw. This
approach does not work for crystals since we cannot characterize a nonspherical crystal with any
fixed radius. The kinetic corrections to the crystal mass growth rate are also described in many books
and papers by introducing the “effective coefficients” D*v and ka*, but it is unclear what “radius” or
size is meant. Thus, we need some scaling length lc for D*v and ka*. The simplest option is to assume
140 Diffusion and Coagulation Growth of Drops and Crystals

that the boundary sphere is inscribed around a crystal, and then the scaling length is the crystal major
semi-axis rc, and the effective D*v and ka* can be defined similarly to Section 5.1 as
rc 4 Dv
Dv* = Dv k kin , k kin = ξ dep = , (5.2.13a)
rc + ξ dep α d Vw
rc 4 ka 4κ T
k a* = k a , βT = = . (5.2.13b)
rc + β T α T c p ρaVw α T Vw

Here xdep is the kinetic correction to the crystal deposition growth rate, kkin is the reducing factor of
the growth rate due to kinetic correction, bT is the kinetic correction to the growth rate in thermal
conductivity, and ad is the deposition coefficient, which is the ratio of the vapor molecular flux
deposited on a crystal to the incident molecular flux to the crystal; ad is analogous to the condensa-
tion coefficient ac in Section 5.1.
Another approximate evaluation of the kinetic corrections can be based on using the same elec-
trostatic analogy. We have seen that this results in the mass growth rate by replacement of the radius
by the electrical capacity. We can assume that the boundary sphere is also generalized as a surface
similar to the surface of constant electrostatic potential and rc → Ce, then
Ce Ce
Dv* = Dv , k a* = k a . (5.2.13c)
Ce + ξ dep Ce + β T

Yet another evaluation of the kinetic corrections can be based on the choice for lc as the spherically
equivalent radius of a crystal rc,equ = (3mc/4pri)1/3 or as the minor crystal semi-axis bc. Replacement
in (Eqn. 5.2.11) of Dv with D*v and substitution of (Eqn. 5.2.13a) for D*v yields

dmc 4π Ce Dv* ρis si 4π Ce Dv ρis si

= = kkin . (5.2.14)
dt Γi Γi
This equation accounts for the three major factors that govern crystal growth: ice supersaturation
si, psychrometric correction Gi and the kinetic correction xdep. The dependencies on these three factors
are separated, which can be convenient in many cases. It is easy to show that (Eqn. 5.2.14) derived
here is equivalent to the form of the mass growth rate equation that is commonly used (e.g., Young,
1993; Pruppacher and Klett, 1997),
dmc 4π Ce si
= . (5.2.15a)
dt RT L LM 
+ * s  s w − 1
Dv eis M w k a T  RT
*


Substituting here the equation of state, eis = risRvT, using the relation Rv = R/Mw, multiplying by
D*v ris, and using (Eqn. 5.2.13a) for D*v , we obtain
dmc 4π Ce si
=
dt RT L  L 
*
+ * s  s − 1
Dv ρis M w Rv T k a T  Rv T 
4π Ce Dv* si ρis 4π Ce Dv si ρis
= ≈ k kin . (5.2.15b)
DLρ  L
*
 Γi
1 + *v s is  s − 1
κ T ρ a c pT  Rv T 
5.2. Diffusional Growth of Crystals 141

where we used the definition (Eqn. 5.2.12) for Gi. This equation coincides with (Eqn. 5.2.14). Thus,
both forms of the growth rate equation, (Eqn. 5.2.14) and (Eqn. 5.2.15a) are equivalent. Using the
approximate relation ka* = k T* racp ≈ D*v racp, the factor Gi can be approximately replaced with G2
introduced in Section 3.11. The advantage of (Eqn. 5.2.14) is that the dependencies on the three
major factors, supersaturation si, psychrometric correction Gi and the kinetic correction xdep, are sepa-
rated and factorized, which makes this equation convenient for deriving analytical parameterizations.

5.2.2. Axial Growth Rates

Axial growth rates of a crystal may be required for some applications (e.g., for evaluation of the
crystal optical properties, radar reflectivities, and development of analytical parameterizations of
ice nucleation). Consideration of the crystal axes growth rates requires specification of the crystal
habit or shape. Detailed classifications of the crystal habits such as the scheme of Magono and
Lee (1966) include up to 80–100 different crystal shapes. However, analytical expressions for the
electrical capacities Ce are known only for a few shapes that can approximate crystal shapes and are
considered in the following text.
Simple ice plates can be approximated as oblate spheroids. We denote the major and minor axes
as rc and bc, and the axis ratio as xf = bc/rc < 1. The volume and mass of the oblate spheroid are
Vc = (4/3)p rc2bc = (4/3)prc3xf and mc = (4/3)p rc3xf ri. The capacitance of this spheroid is written as
rc ε c
Ce = , ε c = (1 − ξ 2f )1/2 . (5.2.16)
arcsin(ε c )

The mass and major semi-axis growth rates are related as

dmc 1 dmc
= 4π rc2 rɺc ξ f ρi , rɺc = . (5.2.17)
dt 4π rc2ξ f ρi dt

Substituting here (Eqn. 5.2.14) for dmc/dt and (Eqn. 5.2.16) for Ce, we obtain the major axis growth
rate drc/dt for a plate-like crystal:
kf Dv ρis si Ce εc
rɺc = , kf = = , (5.2.18)
ξ f ρi Γi (rc + ξ dep ) rc arcsin(ε c )

where we introduced the dimensionless shape factor kf.

Columnar crystal shapes can be approximated by prolate spheroids, with the major and minor axes
being rc and bc, respectively, and the axes ratio is xf = bc/rc < 1. Then, Vc = (4/3)prcbc2 = (4/3)prc3xf2
and mc = (4/3)prc3xf2ri. The capacitance of the prolate spheroid is written as
2rc ε c rc ε c
Ce = = , ε c = (1 − ξ 2f )1/2 . (5.2.19)
1 + εc 1 + εc
ln ln
1 − εc ξf

The mass and major axis growth rates are related as

dmc 1 dmc
= 4π rc2 rɺc ξ 2f ρi , rɺc = . (5.2.20)
dt 4π rc2ξ 2f ρi dt
142 Diffusion and Coagulation Growth of Drops and Crystals

Substituting here (Eqn. 5.2.14) for dmc/dt and (Eqn. 5.2.19) for Ce, we obtain drc/dt for a columnar
crystal
kf Dv∗ ρis si C 2ε c
rɺc = , kf = e = . (5.2.21)
ξ ρi Γ i (rc + ξ dep )
2
f rc ln  (1 + ε c ) / (1 − ε c ) 

It is easy to show that for spherical particles, as the axis ratio xf → 1, the shape factor kf → 1 and
(Eqns. 5.2.18), (5.2.21) transform to the equations for the spherical drops derived in Section 5.1.
Thus, these equations for oblate and prolate spheroids generalize the equations from Section 5.1 for
the non-spherical cases.
A thin hexagonal plate can be approximated by a disc with radius rc and height hc, so the axis ratio
xf = hc /rc < 1. The volume and mass of the disc are Vc = p rc2hc = (4/3)p rc3xf and mc = p rc3xf ri. The
electrical capacitance of the disc is Ce = (2/p)rc. The mass and major axis growth rates are related as
dmc 1 dmc
= 3π rc2 rɺc ξ f ρi , rɺc = . (5.2.22)
dt 3π rc2ξ f ρi dt

Substituting here (Eqn. 5.2.14) for dmc /dt and Ce, we obtain drc/dt for the disc like crystal
4k f Dv∗ ρis si Ce 2
rɺc = , kf = = . (5.2.23)
3ξ f ρi Γ i (rc + ξ dep ) rc π

The equations for the axial growth rates for these three crystal shapes can be written in a generalized
form similar to (Eqn. 5.1.46) for the drops as

drc c s Dv ρis k fi
≈ 3i i , c3i = ζ i , ζ i = k0 i , (5.2.24)
dt rc + ξ dep ρi Γ i ξ nf

where zi describes the effect of the shape, n = 1 for the oblate spheroids and thin plates (disks),
n = 2 for prolate spheroids, k0i = 1 for the oblate and prolate spheroids, and k0i = 4/3 for the thin plates.
For equivalent spheres, zi = 1.
These equations show that the crystal mass and axial growth rates depend on the kinetic correction
xdep that is inversely proportional to the deposition coefficient ad. The measured values of ad vary
over a wide range (Hobbs, 1974; Stephens, 1983; Pruppacher and Klett, 1997), from ad = 0.014 at
T = −2 to −13 °C, yielding xdep ≈ 11 mm, to 0.04 at −6 to −7 °C (xdep ≈ 3.9 mm), to 0.7 at T ≈ −10 to −11 °C
(xdep ≈ 0.22 mm), to values near 1 at temperatures below −40 °C (xdep ~ 0.15 mm). Experimental data on
ad are contradictory, often indicating substantially different values for the same temperature and pres-
sure. Measured values of ad are higher for pure ice and decrease substantially in the presence of impu-
rities, which are always abundant in haze particles. Another reason for lower ad in low-temperature
cirrus clouds can be adsorption of nitric acid or other foreign gases on the crystal surface (e.g., Gao
et al., 2004). Yet another reason for low ad can be the formation of liquid films on the crystal surface.
As the solution droplets are cooled and ice nucleation begins inside haze particles, a phase separation
occurs, solute and concentrated solutions are rejected from the ice, which leads to the formation of a
residual solution coating around the ice crystals formed. The coating can serve as a shield, slowing
the rate of ice growth up to ~103 in comparison with uncoated ice, and this can be one of the reasons
for the persistence of the large in-cloud RHI (Räisänen et al., 2006; Bogdan et al., 2009, 2013).
5.2. Diffusional Growth of Crystals 143

These adsorbed gases or liquid films of impurities act as surfactants and may cause a decrease of ad.
Note that there is a close analogy with the action of surfactants to decrease the condensation coef-
ficient of water drops mentioned in Section 5.1. A similar effect may be caused by the surfactants on
the surface of the cirrus crystals.
Values of ad used in the cloud models may substantially vary. In the Cirrus Parcel Models Com-
parison Project (CPMCP, see review and comparison in Lin et al., 2002), ad varied in different models
from 1 (AMES model, Jensen et al.), to 0.1 (GSFC model, Lin, and U. Michigan model, Liu), to 0.04
(CSU model, DeMott et al.), and down to 10−3 (Gierens et al., 2003). The values of the deposition coef-
ficient can substantially influence the growth rates of the crystals, especially of the small-size fraction;
these variations indicate the necessity of further experiments for quantitative assessment of ad.

5.2.3. Ventilation Corrections

Parameterizing the ventilation corrections to crystal diffusional growth can be accomplished simi-
larly to the method applied in Section 5.1 for drops. A characteristic length scale Dsc is introduced
based on the fact that ventilation depends on the particle projected area normal to the flow, which is
determined by the crystal total area At and the perimeter pc of the projected area normal to the flow.
Therefore, a natural scaling length is determined from their ratio—i.e., Dsc = At /pc.For spherical
particles with radius r, we have At = 4pr2, pc = 2pr, and Dsc = 2r, the diameter. Thus, this definition
of Dsc is a generalization for nonspherical particles. This allows generalizations of the mass transfer
coefficient kv, ventilation coefficient fv, and the Sherwood number Sh to be formulated similarly to
Section 5.1,

(dm /dt ) (dm /dt ) pc

kv = , fv = = Sh,
At ( ρ v∞ − ρ ws ) (dm /dt )0 4π Ce
kv Dsc (dm /dt ) Dsc
, Sh = = , (5.2.25)
Dv At ( ρ v∞ − ρ ws ) Dv

where (dm/dt)0 is the mass growth rate without ventilation correction defined by (Eqn. 5.2.11) or
(Eqn. 5.2.14).
Using these definitions, the crystal mass growth rate with ventilation correction can be written as

dm  dm   dm  pc
=  fv =   Sh. (5.2.26)
dt  dt 0 dt 0 4π Ce
Calculations using this equation require knowledge of the perimeter pc. For a plate or other crystal
habit approximated by an oblate spheroid with the major axis rc, a suitable expression is that for
a sphere, pc = 2prc. For prolate spheroids or other more complicated crystal shapes, At and pc can
be evaluated using the mass-dimension and area-dimension relations (e.g., Auer and Veal, 1970;
Locatelli and Hobbs, 1974)
mc = α D β , At = γ Dσ , (5.2.27)

where D is the crystal characteristic dimension. These relations and their parameters are considered
in more detail in Chapter 12 in application to ice crystal fall velocities.
144 Diffusion and Coagulation Growth of Drops and Crystals

Measurements of the ventilation corrections are scarce and are still missing for most crystal habits.
The coefficients fv were calculated theoretically solving the convective-diffusion equation for some
idealized shapes. Hall and Pruppacher (1976) approximated these calculated coefficients similar to
those for the drops described in Section 5.1 as
fv = 1.0 + 0.14(Sc1/3 Re1/2 )2 , Sc1/3 Re1/2 < 1, (5.2.28a)

fv = 0.86 + 0.28(Sc1/3 Re1/2 ), Sc1/3 Re1/2 ≥ 1. (5.2.28b)

With Sc ≈ 0.71 for the air, these equations are simplified,

fv ≈ 1.00 + 0.11 Re, , R Re1/2 < 1.12, (5.2.29a)

fv ≈ 0.86 + 0.25 Re1/2 , Re1/2 ≥ 1.12. (5.2.29b)

Subsequently, Wang and Ji (1992) parameterized the ventilation coefficient fv based on more detailed
calculations of the air flow around the crystals of various shapes. They found for the columnar crys-
tals at 0.2 ≤ Re ≤ 20
fv ≈ 1.0 − 0.00668 X1 + 2.394 X12 + 0.7341X13 − 0.7391X14 , (5.2.30a)

for simple hexagonal plates P1a at 1 ≤ Re ≤ 120

fv ≈ 1.0 − 0.6042 X 2 + 2.7982 X 22 − 0.3193 X 23 − 0.06247 X 24 , (5.2.30b)

and for broad branched crystals P1c at 1 ≤ Re ≤ 120

fv ≈ 1.0 + 0.3546 X 2 + 3.5533 X 22 , (5.2.30c)

where X1 = Sc1/3Re1/2/4 and X2 = Sc1/3Re1/2/10. The mass growth rates can be calculated with
(Eqn. 5.2.26) using these ventilation coefficients and the expressions for (dm/dt)0 derived earlier,
where a similar ventilation correction should be introduced for the temperature change.

5.3. Equations for Water and Ice Supersaturations

As we have seen in Sections 5.1 and 5.2, calculation of the droplets and crystal growth requires
knowledge of the water and ice supersaturations. Here we derive equations for the fractional water
supersaturation sw = (rv − rws)/rws and fractional ice supersaturation si = (rv − ris)/ris, where rv is the
vapor density, and rws and ris are saturated vapor densities over water and ice.

5.3.1. General Form of Equations for Fractional Water Supersaturation

Consider a mixed-phase cloud, consisting of droplets, crystals, water vapour, and air. The equation
for sw can be derived from the relation
dsw 1 d ρ v ρ v d ρ ws
= − 2 . (5.3.1)
dt ρ ws dt ρ ws dt
The continuity equation for the density rm = ra + rv of the mixture of the air and water vapor is written as
∂ρ m
+ div( ρ mV ) = − I con − I dep , (5.3.2)
∂t
5.3. Equations for Water and Ice Supersaturations 145

where Icon and Idep are the vapor fluxes onto the drops and crystals due to condensation and deposi-

tion, div means the divergence, and V is the air velocity vector. The air density continuity equation is
d ρa
+ ρ a div(V ) = 0. (5.3.3)
dt
The continuity equation for the density rv of water vapor follows from these two equations
d ρv
+ ρ v div(V ) = − I con − I dep . (5.3.4)
dt

Substituting the expression for div(V ) from (Eqn. 5.3.3) into (Eqn. 5.3.4), we obtain

d ρv ρv d ρa
− = − I con − I dep . (5.3.5)
dt ρ a dt

The term dra/dt can be transformed using the equation of state for air, p = raRaT (see Section 3.4.1),
where p is the air pressure, and Ra is the gas constant for the air, which gives us

d ρa 1 dp ρ a dT  1 dp 1 T 
= − = ρa  − . (5.3.6)
dt RaT dt T dt  p dt T dt 
Substituting (Eqn. 5.3.6) into (Eqn. 5.3.5), we obtain

d ρv  1 dp 1 dT 
= ρv  −  − I con − I dep . (5.3.7)
dt  p dt T dt 
We can transform (Eqn. 5.3.1) to express the terms via environmental temperature and pressure.
The term drws /dt in (Eqn. 5.3.1) can be expressed via the cooling rate dT/dt using (Eqn. 3.7.7a) for
the water vapor density rws that follows from the Clausius–Clapeyron equation

d ρ ws d ρ ws dT ρ ws  Le  dT
= =  − 1  , (5.3.8)
dt dT dt T  RvT  dt
where Rv is the specific gas constant for water vapor, and Le is the specific latent heat of evaporation.
Substituting (Eqns. 5.3.7) and (5.3.8) into (Eqn. 5.3.1), we obtain

dsw ρ  1 dp 1 dT  I dep + I con ρ v 1  Le  dT

= v  − − −  − 1  . (5.3.9)
dt ρ ws  p dt T dt  ρ ws ρ ws T  RvT  dt
Using the relation from the definition of fractional supersaturation, rv /rws = (sw + 1), and collecting
the terms at dT/dt, this equation can be rewritten as

dsw  1 dp L dT  I dep + I con

= (sw + 1)  − e2 − . (5.3.10)
dt  p dt RvT dt  ρ ws

Dividing by (sw + 1) and using again the relation rws(sw + 1) = rv, we obtain

1 dsw 1 dp L dT I con + I dep

= − e − . (5.3.11)
(sw + 1) dt p dt RvT 2 dt ρv
146 Diffusion and Coagulation Growth of Drops and Crystals

The term dT/dt can be excluded using the heat balance equation from Section 3.11
dT dp
ρac p = + Le I con + Ls I dep , (5.3.12)
dt dt
where Ls is the specific sublimation (deposition) latent heat rate. Substituting dT/dt from (Eqn. 5.3.12)
into (Eqn. 5.3.11) and collecting the terms at Icon and Idep, we obtain

1 dsw 1 dp L 1 dp
= − e − +
(sw + 1) dt p dt RvT 2 c p ρ a dt ρ

dp I con  L2e ρ v  I dep  LL ρ  (5.3.13)

− 1 + + 1 + e s 2 v .
ρ dt ρ v   
Rv c pT ρ a  ρ v 
2  Rv c pT ρ a 

The second term on the right-hand side can be transformed using the equation of state for air, 1/ra = RaT/p,
and definitions Ra = R/Ma, Rv = R/Mw, and then the second term on the RHS becomes
Le M w 1 dp
- . (5.3.14)
c p T M a p dt

It is convenient to use the notations G1 and G2 for the psychrometric corrections to the drop and
crystal growth rates from Section 5.1 and Section 5.2, and a similar notation G12 in the fourth term
on the RHS in (Eqn. 5.3.13)

L2e ρ v L ∂q LL ρ L ∂q
Γ1 = 1 + , = 1+ e ws , Γ12 = 1 + e s 2 v = 1+ s ws ,
2
Rv c pT ρ a c p ∂T Rv c pT ρ a c p ∂T

L2s ρ v L ∂q
, Γ2 = 1 + = 1+ s is . (5.3.15)
Rv c pT 2 ρ a c p ∂T

Then (Eqn. 5.3.13) can be rewritten using (Eqns. 5.3.14) and (5.3.15),

1 dsw 1 dp  L M w  Γ1I con Γ12 I dep

= 1 − e − − . (5.3.16)
(1 + sw ) dt p dt  c pT M a  ρv
 ρv

The vapor fluxes Icon and Idep to the droplets and crystals (the sources or sinks in the supersaturation
equation) are the integrals of the mass growth rates. The integral mass growth rates can be expressed using
equations for the growth rates drd /dt and drc /dt of the droplet radii and crystal equivalent radii over the
corresponding size spectra of the drops fd (rd, t) and crystals fc(rc, t), where rd and rc are corresponding radii:
∞ dmd ∞ dr
I con = ∫ f (rd , t ) drd = 4πρ w ∫ rd2 d f (rd , t ) drd , (5.3.17a)
0 dt 0 dt
∞ dmc ∞ dr
I dep = ∫ f (rc , t ) drc = 4πρi ∫ rc2 c f (rc , t ) drc , (5.3.17b)
0 dt 0 dt
where the second equalities assume approximate spherical symmetry of the particle. We use drd /dt
and drc/dt in the form (Eqns. 5.1.46) and (5.2.24) derived in Sections 5.1 and 5.2,
drd c s Dv ρ ws 4 Dv
= 3w w , c3 w = , ξcon = , (5.3.18a)
dt rd + ξcon ρ w Γ1 α cVw
5.3. Equations for Water and Ice Supersaturations 147

drc c s k f Dv ρis 4 Dv
= 3i i , c3i = k 0 i , ξ dep = , (5.3.18b)
dt rc + ξ dep ξ nf ρi Γ 2 α d Vw

where all notation is the same as in Sections 5.1 and 5.2.

5.3.2. Supersaturation Relaxation Times and Their Limits

Substituting (Eqns. 5.3.18a,b) into (Eqns. 5.3.17a,b), we obtain
ρ ws sw −1 ∆ w ρ a −1 ρis si −1 ∆ i ρ a −1
I con = τ fd = τ fd , I dep = τ fc = τ fd , (5.3.19)
Γ1 Γ1 Γ2 Γ2

where Dw = qv − qws and Di = qv − qis are the specific supersaturations over water and ice, and we have
introduced the supersaturation absorption or relaxation times for the droplets tfd and crystals tfc (also
called in the literature the phase relaxation times):
∞ rd2
τ −fd1 = 4π Dv ∫ fd (rd , t ) drd , (5.3.20a)
0 rd + ξcon
kf ∞ rc2
τ −fc1 = 4π Dv k 0 i
ξ n
f
∫ 0 rc + ξ dep
fc (rc , t ) drc . (5.3.20b)

This form of tfd, tfc account for the kinetic corrections and crystal shapes. The more general expres-
sions are different for cases with and without nucleation of the new droplets and crystals. If droplet
or crystal nucleation takes place, then the droplet or crystal size spectra can be expressed using the
concentration conservation laws in differential form as
fd (rd , t )drd = ϕ s (sw )dsw , fc (rc , t )drc = ψ s (sw )dsw , (5.3.21)

where js(sw) is the supersaturation activity spectrum of CCN (Chapter 6), ys(sw) is the supersaturation
activity spectrum of IN (Chapters 8 and 9). Substitution of these expressions into (Eqns. 5.3.17a,b)
gives the expressions for the relaxation times

∞ rd2
τ −fd1 = 4π Dv ∫ ϕ s (sw ) dsw , (5.3.22a)
0 rd + ξcon
kf ∞ rc2
τ −fc1 = 4π Dv k 0 i
ξ n
f
∫
0 rc + ξ dep
ψ s (sw ) dsw . (5.3.22b)

Substitution of these expressions into (Eqn. 5.3.16) gives the equations for supersaturation that con-
tain the terms with sw in the integrand—i.e. the integro-differential equations. The form of the equa-
tions including activation is more complicated but allows evaluation of the nucleation laws for the
droplets and crystals. These equations with various activity spectra js and ys and their solutions will
be considered in detail in Chapters 6, 7, 8, and 9.
Here we consider the simpler situation when nucleation is absent and the vapor fluxes Icon and
Idep are determined by preexisting droplets with fd(rd) and crystals with fc(rc), which determine the
relaxation times tfd and tfc in (Eqns. 5.3.20a,b). The expressions and values of tfd and tfc are dif-
ferent in the diffusion and kinetic regimes of particle growth. If the growth of droplets and crystals
148 Diffusion and Coagulation Growth of Drops and Crystals

Table 5.1. Supersaturation relaxation times in liquid clouds, seconds (upper line) and equilibrium
_
water supersaturations, % (lower line) for various drop concentrations Nd and mean radius rd.

Droplet concentration Nd (cm−3)

Mean radius rc (μm) 50 100 200 500

5 14.4 7.2 3.6 1.44

0.072 0.036 0.018 0.72 × 10−2
10 7.2 3.6 1.8 0.72
0.036 0.018 0.009 0.36 × 10−2

proceeds in the diffusion regime, then the expressions (Eqns. 5.3.20a,b) for the relaxation times
become
−1

( ∞
τ fd ≈ 4π Dv ∫ rd fd (rd , t ) drd
0 ) = (4π D N r ) , v d d
−1
(5.3.23a)
−1 k
≈ ( 4π D ∫ r f (r , t ) dr ) = (4π D k
∞
τ fc
f −1
N r) , (5.3.23b)
ξ
v c c c c v 0i n c c
0
f

where Nd, Nc are droplet and crystal concentrations, and rd and rc are their mean radii. Typical values of
tfd in liquid or mixed clouds vary from 1–2 seconds with large droplet concentrations to 10–15 seconds
with small concentrations (Table 5.1). Typical values of tfc in ice clouds vary from 5–10 minutes to
5–10 hours (Table 5.2). The supersaturation relaxation times in a cloud represent in general a three-
dimensional field and may vary from a few seconds to a few hours in various parts of the cloud (e.g.,
Khvorostyanov and Sassen, 1998a,b, 2002; Khvorostyanov, Curry et al., 2001, 2003, 2006; Krämer
et al., 2009).
In the kinetic growth regime, the expressions for tfd and tfc become
−1 −1
 4π Dv ∞
∞   4π Dv 
τ fd ≈ 
 ξcon
∫0
rd2 f d (rd , t ) drd  = 
  ξcon
N d < rd2 > ~ Lvis ,d ,

(5.3.24a)

−1
 4π Dv k fv ∞ 2

τ fc ≈ 
ξ
 dep
k0 i n
ξ f
∫ 0
r f (rc , t ) drd 
c c

−1
 4π Dv kf 
= k 0 i n N c < rc2 > ~ Lvis ,c , (5.3.24b)
 ξ dep ξf 

where < rd2 >, < rc2 > are the mean squared radii of the size spectra, and Lvis,d and Lvis,c are the cor-
responding visibility ranges that are inversely proportional to the second moments of the size spectra
(see Chapter 2).
5.3. Equations for Water and Ice Supersaturations 149

Table 5.2. Supersaturation relaxation _times in crystalline clouds for spherical crystals with various
concentrations Nc and mean radii rc. The units are hours (h), minutes (min), and seconds (s)

Crystal concentration Nc (L−1)

Mean radius
rc (μm) 1 5 10 100 200 500 1000 3000

2 500 h 100 h 50 h 5h 2.5 h 1h 30 min 10 min

5 200 h 40 h 20 h 2h 1h 24 min 12 min 4 min
10 100 h 20 h 10 h 1h 30 min 12 min 6 min 3 min
20 50 h 10 h 5h 30 min 15 min 6 min 3 min 1 min
50 20 h 4h 2h 12 min 6 min 144 s 72 s 24 s
100 10 h 2h 1h 6 min 3 min 72 s 36 s 12 s
500 2h 24 min 12 min 72 s 36 s 14 s 3.6 s 2.5 s
1000 1h 12 min 6 min 36 s 18 s 7.2 s 3.6 s 1.1 s

5.3.3. Equation for Water Supersaturation in Terms of Relaxation Times

Substituting Icon and Idep from (Eqn. 5.3.19 into 5.3.16), and using the relations rv /rws = 1/(1+sw),
rv /ris = 1/(1+si), we obtain the equation for sw:

1 dsw 1 dp  L Mw  1 sw 1 Γ12 si
= 1 − e − − . (5.3.25)
(1 + sw ) dt p dt  c pT M a  τ d (1 + sw ) τ c Γ2 (1 + si )
 

If the cooling rate is governed in a rising parcel by the vertical velocity w like in a Lagrangian parcel
model or at the adjustment stage of the process- and coordinate-splitting method in a multidimensional
Eulerian model, then the problem is reduced to a zero-dimensional Lagrangian task, and the term
with pressure can be expressed using the hydrostatic equation, dp = −ragdz, and the relation dp/dt =
(dp/dz)(dz/dt) = −ragw, where g is acceleration of gravity. Using equation of state for the air, the term
with pressure can be written as (1/p)(dp/dt) = −(g/RaT)w. Substitution of this into (Eqn. 5.3.25) yields:
1 dsw 1 sw 1 Γ12 si
= c1w w − − . (5.3.26a)
( w)
1 + s dt τ fd (1 + s w) τ fc Γ 2 (1 + si )

where
 L Mw  g
c1w (T ) =  e − 1 . (5.3.26b)
 c pT M a  RaT
 
Using the definitions of the dry ga and wet gw adiabatic lapse rates from Section 3.11, a simple trans-
formation yields
cp ρ a  dql  ρa
c1w (T ) = (γ a − γ w )Γ1 =  Γ1 , (5.3.26c)
Le ρ ws  dz  ad ρ ws
where (dql/dz)ad is the adiabatic gradient of the liquid water content introduced in Section 3.11.
Equation (5.3.26a) can be written in a slightly different form by multiplying by (1 + sw), and using
the relation
1 + sw ρ − ρis
si = sw + ws . (5.3.27)
1 + si ρ ws
150 Diffusion and Coagulation Growth of Drops and Crystals

Thus, we obtain

dsw  1 Γ12 1  Γ12 1 ρ ws − ρis

= (1 + sw )c1w w − sw  + − . (5.3.28a)
dt  τ fd Γ 2 τ fc  Γ 2 τ fc ρ ws
 
This supersaturation equation has a clear physical meaning. The first term on the right-hand side
of (Eqn. 5.3.26a) or (Eqn. 5.3.28a) describes the supersaturation generation rate in the parcel in
adiabatic ascent. This rate is proportional to the vertical velocity w and to c1w, and as (Eqn. 5.3.26c)
shows, to the adiabatic gradient of the liquid water content. The second term represents the rate of
supersaturation absorption or relaxation by diffusion growth of the droplets and crystals. The last
term describes the flux from the droplets to the crystals, called the Wegener–Bergeron–Findeisen
process (WBF), therefore it is proportional to the difference rws − ris in (Eqn. 5.3.28a).
We can introduce the “effective” supersaturation relaxation time in a mixed cloud as
−1
 1 Γ 1 
t f, mixix =  + 12  . (5.3.28b)
 τ fd Γ 2 τ fc 
 
Then, (Eqn. 5.3.28a) can be written as
dsw s Γ 1 ρ ws − ρis
= (1 + sw )c1w w − w − 12 . (5.3.29)
dt τ f , mix Γ 2 τ fc ρ ws

The second term on the right-hand side in (Eqn. 5.3.29), sw/tf,mix, shows that the rate of vapor absorp-
tion (relaxation) is determined by tf,mix, therefore it is termed the supersaturation “absorption” or
“relaxation” time. Equation (5.3.26a) can be written in a slightly different form that is more conve-
nient for analytical solutions:
dsw
= (1 + sw )c1w − swτ −fd1 − c2 w siτ −fc1 , (5.3.30a)
dt
Γ12 1 + sw
c2 w (T ) = . (5.3.30b)
Γ 2 1 + si
In pure liquid clouds, fc(rc) = 0 and tfc−1 = 0, and so the terms with tfc−1 on the right-hand side in
(Eqns. 5.3.26a) and (5.3.30a) vanish. Since sw << 1 and (1 + sw) ≈ 1 in such clouds, the supersaturation
(Eqn. 5.3.30a) is simplified to be
dsw s
= c1w w − w , (5.3.31a)
dt τ fd
that is, the supersaturation balance is determined by its generation c1ww and absorption sw /tfd. At small
times, or if vapor absorption is weak and the second term here is small, the solution is
sw (t) = c1w wt. (5.3.31b)
The solution of this type is used as a first iteration for parameterization of the initial stage of drop activa-
tion (see Chapter 7) and of ice nucleation in homogeneous and heterogeneous freezing (Chapters 8–10).
In the absence of supersaturation generation, if vertical velocity w = 0, and radiative and other sources
of cooling are absent, then the solution is

sw (t ) = sw (t0 )exp[ −(t − t0 ) /τ fd ]. (5.3.31c)

5.3. Equations for Water and Ice Supersaturations 151

That is, in the absence of supersaturation generation, the supersaturation e-fold decrease (relaxation)
occurs during tfd. This originated the term “relaxation time.” The same is valid for ice supersaturation
in crystalline clouds.
The equation for the water saturation ratio Sw is used in some cases instead of the equation for sw.
It is easily obtained from the previous equations and the relation sw = Sw − 1. Substitution of this rela-
tion into (Eqn. 5.3.28a) gives

dSw  1 Γ12 1  Γ12 1 ρ ws − ρis

= Sw c1w w − (Sw − 1)  + − . (5.3.32a)
dt  τ fd Γ 2 τ fc  Γ 2 τ fc ρ ws
 
In pure liquid clouds with 1/tfc = 0, the equation is simplified to
dSw S −1
= Sw c1w w − w . (5.3.32b)
dt τ fd

5.3.4. Equivalence of Various Forms of Supersaturation Equations

In most textbooks and papers, the supersaturation equation is derived and used in the following form

dsw dq
= A1w − A2 l . (5.3.33)
dt dt
Here, ql is the liquid water content (LWC), the second term on the RHS (sink or source of supersatu-
ration) is written proportional to the LWC change rate dql/dt, and the coefficients are (Pruppacher
and Klett, 1997, eq. (13-31), page 513)
Le g M w g
A1 = − , (5.3.34)
RaT 2 c p M a RaT
Ra T ( M w /M a ) L2e
A2 = + , (5.3.35)
( M w /M a )ews pTc p
where ews is the vapor pressure saturated over water. The coefficients A1 and A2 describe supersatura-
tion generation and absorption, respectively. It can be shown that this form of the supersaturation
equation for the liquid cloud is equivalent to (Eqn. 5.3.31a) derived earlier. The coefficient A1 can be
rewritten as

 L Mw  g
A1 =  e − 1 = c1w (T ). (5.3.36)
 c pT M a  RaT
 
In other words, A1 is equal to c1w defined in (Eqn. 5.3.26b). The coefficient A2 can be transformed
and simplified using the equations of state for the water vapor, ews = rwsRvT, and for the air, p = raRaT,
and the relations Ra = R/Ma and Rv = R/Mw,. Thus, A2 becomes
( Ra M a )T L2e
A2 = +
ρ ws ( M w Rv )T ρ a ( Ra M a /M w )T 2 c p

1 L2e 1  L2e ρ ws  Γ1
= + = 1 + = , (5.3.37)
2 
ρ ws ρ a RvT c p ρ ws  RvT 2 c p ρ a  ρ ws
152 Diffusion and Coagulation Growth of Drops and Crystals

where G1 is the psychrometric correction defined in (Eqn. 5.3.15). The rate of liquid water content
change, dql/dt, by definition is equal to the vapor flux of the droplets Icon, so it can be transformed
using the relations (Eqns. 5.3.17a), (5.3.19), (5.3.20a)

dql ∞ dmd ρ s
dt ∫0 dt
= fd (rd )drd = I con = ws w τ −fd1. (5.3.38)
Γ1

This expression shows that the term dql /dt is proportional to supersaturation. Thus, the second term
in (Eqn. 5.3.33) is

dql Γ ρ s s
A2 = A2 I con = 1 ws w = w . (5.3.39)
dt ρ ws Γ1τ fd τ fd

Substituting these expressions for A1 and A2dql /dt into (Eqn. 5.3.33), we obtain
dsw dρ s
= A1w − A2 L = c1w w − w , (5.3.40)
dt dt τ fd
which coincides with (Eqn. 5.3.31a). Thus, (Eqn. 5.3.33) is equivalent to (Eqn. 5.3.31a) for liquid
clouds. The convenience of (Eqn. 5.3.31a) or the second form of (Eqn. 5.3.40) is that the sink term
dql /dt is expressed via sw, thus this equation contains only one variable and does not require evalu-
ation of dql /dt. Equations (5.3.25) and (5.3.28a) generalize these equations for mixed-phase clouds
containing drops and crystals.
Water supersaturation governs crystal nucleation during the freezing of haze particles even at cold
temperatures (below −40 °C) in cirrus in the upper troposphere, when submicron solution droplets
may exist but liquid water drops are absent. Under these conditions, sw is needed for calculations of
ice nucleation rates (see Chapters 8–10). In pure crystalline clouds, fd(rd) = 0, tfd−1 = 0, and the terms
with tfd−1 on the right-hand side in (Eqns. 5.3.28a and 5.3.30a) vanish. Thus, (Eqn. 5.3.28a) becomes
dsw Γ s Γ 1 ρ ws − ρis
= (1 + sw )c1w w − 12 w − 12 . (5.3.41)
dt Γ 2 τ fc Γ 2 τ fc ρ ws

5.3.5. Equation for Fractional Ice Supersaturation

In simulations of mixed clouds or crystalline clouds like cirrus, the supersaturation over ice
si = (rv− ris)/ris is required for calculation of the crystal growth (Section 5.2). It can be determined in
two ways. One way to determine si is by solving the equation for sw given earlier (if sw is needed for
the other purposes—e.g., drop activation and crystal nucleation) and using the relation that follows
from the definitions of sw and si and the Clausius–Clapeyron equation:

ρ ws  L (T − T ) 
si = (sw + 1) − 1 = cwi (sw + 1) − 1, cwi = exp  m 0 , (5.3.42a)
ρis  Rv T0 T 
where T0 = 273.15 K is the triple point temperature. If sw and the equation for sw are not needed,
another direct way is to use the equation for si that can be derived by differentiating si:
dsi 1 d ρ v ρ v d ρis
= − 2 . (5.3.42b)
dt ρis dt ρis dt
5.3. Equations for Water and Ice Supersaturations 153

Analogously to the derivation of the equation for sw earlier, using the equations of continuity and state
for the air, water vapor, and their mixture (the Clausius–Clapeyron equation), we arrive at an equation

1 dsi 1 dp  L  I dep I
= 1 − s − Γ − con Γ . (5.3.43a)
(1 + si ) dt p dt  c pT  ρ v 2 ρ v 12

Substituting here Icon and Idep from (Eqn. 5.3.19), and using the relation rv = (1 + si)ris and then mul-
tiplying by (1 + si) yields

dsi 1 dp  L  si Γ12 (1 + si ) sw
= (1 + si ) 1 − s − − . (5.3.43b)
dt p dt  c pT  τ fc Γ 2 (1 + sw ) τ fd

Now sw can be excluded using the relation
1 + si ρ − ρ ws
sw = si + is , (5.3.43c)
1 + sw ρis

and we obtain an equation for si:

dsi 1 dp  L   1 Γ12 1  Γ12 1 ρ ws − ρis

= (1 + si ) 1 − s  − si  + + . (5.3.44)
dt p dt  c pT 

 τ fc Γ 2 τ fd  Γ 2 τ fd
  ρis

As in the case with s w earlier, (Eqn. 5.3.44) can be further transformed using the hydro-
static approximation for the case with adiabatic parcel ascent in a Lagrangian model or for
the step of adjustment in the splitting procedure in a multidimensional Eulerian model. Then,
(1/p)(dp/dt) = −(g/R aT)w, and we obtain

dsi  1 Γ12 1  Γ12 1 ρ ws − ρis

= (1 + si )c1i w − si  + + , (5.3.45)
dt  τ fc Γ 2 τ fd  Γ 2 τ fd ρis
 
where
 L Mw  g
c1i (T ) =  s − 1 . (5.3.46a)
 c pT M a  RaT
 
Using the equations for the dry ga and wet (in ice clouds) gis adiabatic lapse rates and adiabatic gradi-
ent of the ice water content (dqi/dz)ad in ice clouds introduced in Section 3.11, this coefficient also can
be expressed via the difference (ga − gis) similar to c1w in (Eqn. 5.3.26c) for the case of liquid clouds:

cp ρ a  dqi  ρa
c1i (T ) = (γ a − γ is )Γ 2 =  Γ2 . (5.3.46b)
Ls ρis  dz  ad ρis
This equation shows that the ice supersaturation generation rate in ice clouds is proportional to
the difference (ga − gis), or to the adiabatic gradient of the ice water content. For pure crystalline
clouds, or when the vapor flux to the liquid substance can be neglected, then tfd = ∞, 1/tfd = 0, and
(Eqn. 5.3.45) is simplified as
dsi s
= (1 + si )c1i w − i , (5.3.47)
dt τ fc
154 Diffusion and Coagulation Growth of Drops and Crystals

which is similar to the water supersaturation (Eqn. 5.3.31a) in liquid clouds. In contrast to liquid
clouds where sw is close to zero, si in crystalline clouds is not close to 0, so it can be 0.3–0.7 (30–70%)
or more in cold cirrus clouds, and the term (1 + si) cannot be replaced with 1.
The equation for the ice saturation ratio Si is easily obtained from the previous equations and the
relation si = Si − 1. Substitution of this relation into (Eqn. 5.3.45) gives

dSi  1 Γ12 1  Γ12 1 ρ ws − ρis

= Si c1i w − (Si − 1)  + + . (5.3.47a)
dt  τ fc Γ 2 τ fd  Γ 2 τ fd ρis
 
For a pure ice cloud, 1/tfd = 0 and it is simplified as
dSi S −1
= c1i wSi − i . (5.3.47b)
dt τ fc

5.3.6. Equilibrium Supersaturations over Water and Ice

Liquid clouds. Cloud layers may exist in quasi-steady states that can be characterized by equilibrium
supersaturations. The equilibrium supersaturation sweq in a liquid cloud is determined from (Eqn. 5.3.31a)
with the steady state condition dsw /dt = 0. Using also (Eqns. 5.3.26b,c) for c1w, we obtain

c p (γ a − γ w ) Γ1 ρ a  dq  Γ1 w
ssweq, liq = c1w wτ fd = w= l  . (5.3.48a)
Le 4π Dv N d rd ρ ws  dz  ad qws 4π Dv N d rd
This simple equation shows that the equilibrium supersaturation is proportional to the vertical veloc-
ity, the difference of the dry and wet adiabatic lapse rates, or to the adiabatic gradient of LWC, and to
the supersaturation relaxation time (which is inversely proportional to the droplet concentration and
mean radius). Hence, typical values of equilibrium water supersaturation in clouds can be estimated
from (Eqn. 5.3.48a) using a value c1w ~ 10−5 cm−1. The equilibrium supersaturation relaxation times
for various drop concentrations and two values of the mean radius are given in Table 5.1, which
shows that sweq with rd = 5 °mmmdecreases from 0.072% at Nd = 50 cm−3 (tfd = 14.4 s) to 0.72 × 10−2 %
at Nd = 500 cm−3 (tfd = 1.44 s), and sweq is a factor of two smaller for rd = 10mm.
°
The equilibrium condensation rate can be calculated substituting (Eqn. 5.3.48a) into (Eqn. 5.3.19):

ρ ws eq ρ ρ cp Γρ
eq
I con = sw,liq = ws c1w wτ fd = ws (γ a − γ w )τ fd 1 a w
Γ1τ fd Γ1τ fd Γ1τ fd Le ρ ws
cp  dq 
= (γ a − γ w ) ρ a w =  l  ρ a w. (5.3.48b)
Le  dz  ad
Ice clouds. In contrast to water supersaturation, the equilibrium ice supersaturation in crystalline
clouds like cirrus, contrails, and some As-Ac or diamond dust is not small. It can be determined from
(Eqn. 5.3.47) under the condition dsi/dt = 0,
c1i wτ fc
sieq,ice =
1 − c1i wτ fc
−1
c (γ − γ is )Γ 2 ρ a  c (γ − γ is )Γ 2 ρ a 
= p a wτ fc 1 − p a wτ fc  . (5.3.49a)
Ls ρis  L s ρ is 
5.3. Equations for Water and Ice Supersaturations 155

The crystal relaxation times tfc calculated for spherical crystals are given in Table 5.2. The values of
tfc vary over a wide range from 1–10 s to 1–10 min for high crystal concentrations ~103–3 × 103 L−1
(e.g., in cloud-seeding experiments) to several hundred hours for small crystal concentrations and
radii. The corresponding equilibrium ice supersaturations in crystalline clouds calculated with
(Eqn. 5.3.49a) are given in Table 5.3. For tfc ≤ 10–600 s and w ≤ 10–20 cm s−1, supersaturation val-
ues are smaller than one percent. For larger tfc and w, the supersaturation values increase to several
percent or tens of percent (right lower corner in Table 5.3). These values may exceed the critical
(or threshold) values of ice supersaturations si,cr, ~ 25–70%, required for homogeneous or hetero-
geneous ice nucleation (see Chapters 8 and 9). This indicates that such states are unstable and new
crystals should nucleate until equilibrium can be established.
At w > 1–2 m s−1 and tfc > 1–3 hours, when ci1wtfc > 1, the denominator in (Eqn. 5.3.49a) becomes
negative and the ice supersaturations determined from the condition dsi /dt = 0 become negative. This
means that even if equilibrium is reached at some moment in a cloud, a cloud would evaporate via
the sublimation process, and the equilibrium would be violated, because equilibrium supersaturation
cannot exist for a long time with such w and tfc. Thus, the states with positive equilibrium ice super-
saturations can be reached under two conditions: a) ci1wtfc < 1 and b) si < si,cr.
The equilibrium deposition rate Idep can be calculated by substituting the equilibrium ice super-
saturation into (Eqn. 5.3.19) for Idep. This is illustrated here for the case without high crystal concen-
trations and fast glaciation when c1iwtfc << 1. Then, the denominator in (Eqn. 5.3.49a) is unity and
the expression for equilibrium supersaturation is simplified as
c p (γ a − γ is )Γ 2 ρ a
sieq,ice ≈ c1i wτ fc = wτ fc . (5.3.49b)
Ls ρis
Substituting this expression into (Eqn. 5.3.19) for Idep, we obtain the equilibrium deposition rate

ρis eq ρ cp Γ ρ
eq
I dep = si ,ice = is (γ a − γ is )τ fc 2 a w
Γ 2τ fc Γ 2τ fc Ls ρis
cp  dq 
= (γ a − γ is ) ρ a w =  i  ρ a w, (5.3.49c)
Ls  dz  ad
where (dqi /dz)ad is the adiabatic gradient of ice water content.

Table 5.3. Approximate equilibrium ice supersaturations (%) in crystalline clouds with various crystal
supersaturation relaxation times tc (s, min) and vertical velocities w (cm s−1) for spherical ice crystals

Supersaturation Vertical velocity w (cm s−1)

relaxation
time tc (sec, min) 1 5 10 20 50 100 250

10 s 0.12E-02 0.60E-02 0.12E-01 0.024 0.060 0.12 0.30

60 s 0.72E-02 0.36E-01 0.72E-01 0.145 0.36 0.73 1.84
100 s 0.012 0.060 0.12 0.24 0.61 1.22 3.11
600 s 0.072 0.36 0.73 1.47 3.75 7.81 22.11
1000 s 0.12 0.607 1.22 2.47 6.42 13.73 43.22
30 min 0.22 1.098 2.22 4.54 12.19 27.76 118.9
60 min 0.44 2.22 4.54 9.517 27.76 76.84 −1259
120 min 0.88 4.54 9.517 21.04 76.84 663.6 −185.3
180 min 1.32 6.97 14.99 35.27 187.2 −429.4 −144.3
156 Diffusion and Coagulation Growth of Drops and Crystals

Mixed phase clouds. Equilibrium supersaturation in a mixed phase cloud can be obtained from (Eqn.
5.3.28a) with dsw/dt = 0, which yields
c1w w − (Γ12 /Γ 2 )τ −fc1 ( ρ ws − ρis )/ρ ws
sweq, mix = . (5.3.50)
τ −fd1 + (Γ12 / Γ 2 )τ −fc1 − c1w w

Since c1w ~ 10−5 cm−1 and tfd−1 ~ 0.1–1 s−1 (Table 5.1), then for w ≤ 10 m s−1, the term c1ww in the
denominator can be usually neglected. A comparison of Tables 5.1 and 5.2 shows that tfc usually
is much greater than tfd (except for the cases with very high crystal concentrations and rapid cloud
glaciation), thus tfd−1 >> tfc−1. The factor G12/G2 ~ 1, and the term (G12/G2)tfc−1 can be also neglected in
the denominator. Then, the equilibrium supersaturation in a mixed cloud becomes
τ fd ρ ws − ρis
sweq, mix = c1w wτ fd − . (5.3.51)
τ fc ρ ws

The first term coincides with the equilibrium supersaturation in a liquid cloud (Eqn. 5.3.48a), while
the second term describes the decrease of equilibrium supersaturation due to the presence of crys-
tals. This decrease is proportional to the difference Drs = rws− ris and to the ratio of the drop and
crystal relaxation times. Since usually tfd << tfc, the equilibrium supersaturation in a mixed cloud
can only be slightly lower than the supersaturation in a liquid cloud (Eqn. 5.3.48a). For example,
if tfd ≈ 2 s (Nd = 200 cm−3, rd = 10mm) ° and if tfc ≈ 1 h (Nc = 10 L−1, rc = 100mm,
° Tables 5.1.
and 5.2) and Drs /rws ≈ 0.1 at T = −10 °C, and c1w ~ 10−5 cm−1, then according to (Eqn. 5.3.51),
sweq,mix ≈ 10 −4 − 0.5 × 10 −4 = 0.5 × 10 −4 = 0.5 × 10 −2 %—i.e., the second negative term compensates for the
first term with supersaturation generation by about one half, but a mixed cloud exists at positive water
supersaturation. Note that some models calculated the supersaturation in mixed clouds as weighted
by the water and ice masses. Equations (5.3.50) and (5.3.51) show that this approach may overesti-
mate glaciation rates, and more accurate calculations should be based on the use of supersaturation
relaxation times—i.e., drop and crystal concentrations and mean sizes.
The condition when supersaturation in a mixed cloud is positive follows from (Eqn. 5.3.51),
c1w w − τ −fc1 ( ρ ws − ρis )/ρ ws ≥ 0. sweq, mix ≥ 0, (5.3.52a)

which gives two criteria for w or tfc:

w ≥ ( ∆ρis /ρ ws )/(c1wτ fc ), τ fc ≥ ( ∆ρ s /ρ ws )/(c1w w). (5.3.52b)

For example, if Nc ≈ 70 L−1 and rc = 50m ° m,m then tfc = 1,000 s (Table 5.2), and with Drs /rws ≈ 0.1 at
T = −10 °C and c1w ~ 10−5 cm−1, the first of these equations gives w ≥ 10 cm s−1 as a condition for positive
water supersaturation. At a smaller w with this microstructure, the supersaturation will be negative and
gradual cloud glaciation will occur. At a smaller Nc ~ 5−10 L−1, an estimate from (Eqns. 5.3.52a,b)
shows that sw can be positive even with a w of a few cm s−1, and a cloud may exist in a mixed state
without full glaciation for a long time, which may explain long lifetimes of polar clouds in the mixed
phase. Such supercooled clouds and fogs in liquid state can be appropriate objects for cloud seeding
with cooling agents, which cause cloud crystallization, and precipitation enhancement or dispersal of
clouds and fogs.
5.3. Equations for Water and Ice Supersaturations 157

5.3.7. Adiabatic Lapse Rates with Non zero Supersaturations

We derived in Chapter 3 the wet adiabatic gradients in liquid and ice clouds under the assumption
of instantaneous condensation and zero supersaturations. A question arises if finite condensation or
deposition rates and the nonzero supersaturations in clouds can change the values of wet adiabatic
lapse rates. Consider again (Eqn. 3.11.22) for gw and rewrite it for a process with finite rate—i.e.,
with time dependence:
Le dqws L dq dt
γw = γa + = γ a + e ws (5.3.53)
c p dz c p dt dz

In general, the value of gw can be different from the wet adiabatic value. The situation is simplified
for the case with equilibrium supersaturation. The term dqws/dt can be expressed via the condensation
rate using the relations for adiabatic process and expression (Eqn. 5.3.48a) for Icon:

dqws dq I eq cp
= − l ≈ − con = − (γ a − γ w )w. (5.3.54)
dt dt ρa Le
Substituting this equation and the relation dz/dt = 1 /w into (Eqn. 5.3.53), we obtain for the wet adia-
bat in equilibrium

Le  cp 1
γ weq = γ a +  − (γ a − γ w ) w  = γ a − (γ a − γ w ) = γ w . (5.3.55)
cp  eL w
That is, for condensation in liquid clouds with finite condensation rates and equilibrium supersatura-
tion, the wet adiabatic gradient is equal to its value in the wet adiabatic process with instantaneous
condensation.
The wet adiabatic gradient in ice clouds with equilibrium ice supersaturation can be derived in a
similar way. Consider again (Eqn. 3.11.35) for gis and rewrite it for a process with finite deposition
rate—i.e., with time dependence:
Ls dqis L dq dt
γ is = γ a + = γ a + s is . (5.3.56)
c p dz c p dt dz

In general, the value of gis can be different from the wet adiabatic value in ice clouds but is simplified
for the case with equilibrium ice supersaturation (Eqn. 5.3.49a) and deposition rate (Eqn. 5.3.49c)
valid for the case without high crystal concentrations and rapid glaciation, when c1iwtfc << 1. The
term dqis/dt can be transformed for an adiabatic process as
eq
dqis dq I dep cp
=− i ≈− = − (γ a − γ is )w. (5.3.57)
dt dt ρa Le
Substituting this expression and the relation dz/dt = 1 /w into (Eqn. 5.3.57), we obtain

Le  cp 1
γ iseq = γ a +  − (γ a − γ is ) w  = γ a − (γ a − γ is ) = γ is . (5.3.58)
cp  eL w
That is, for deposition with a finite rate in ice clouds and equilibrium ice supersaturation, and without
high crystal concentrations, the wet adiabatic temperature gradient is equal to its value in the wet
158 Diffusion and Coagulation Growth of Drops and Crystals
eq
adiabatic process with instantaneous deposition in ice clouds. The values of g is with high crystal
concentrations and negative ice supersaturations should be evaluated using time-dependent models.
eq eq
These equalities, γ w = γ w and γ is = γ is, mean that under the quasi-equilibrium conditions, the latent
heats and ice nucleation rates can be calculated in models using the equilibrium ice supersaturations.

5.4. The Wegener–Bergeron–Findeisen Process and Cloud Crystallization

After the occurrence of sufficient crystal concentrations in a mixed phase cloud, the process of cloud
crystallization (or glaciation) begins. During the first stage, a mixed cloud exists and the net vapor
flux is directed from the drops to the crystals because the saturated vapor pressure over water is higher
than over ice. This is the Wegener–Bergeron–Findeisen or WBF process (Wegener,1911; Bergeron,
1935; Findeisen, 1938), when the drops evaporate and crystals grow at their expense. If the crystal
concentration is sufficiently high and the time for this process is sufficiently long, the second stage
occurs after the drops have been completely evaporated, and then a pure crystalline cloud exists and
supersaturation relaxation continues. Detailed consideration of the evolution of a mixed phase cloud
parcel with a WBF process followed by a crystalline cloud are given in Chapters 8, 9, and 14. Here,
a simplified description is provided following Shifrin and Perelman (1960), with modifications that
help illustrate the physics of the glaciation process.
First stage. Suppose for simplicity that an adiabatic cloud parcel contains initially a monodis-
perse ensemble of drops with radius rd(0) = rd0 and concentration Nd, which exist at a temperature T,
and small water supersaturation sw. Then, a number of crystals with concentration Nc and negligibly
small radius rc0 << rd0 are nucleated at the time t = 0 and Nc is subsequently constant with time,
and so the processes of coagulation and accretion are insignificant and can be neglected. Such a
situation may occur after natural ice nucleation as described in Chapters 8 and 9, or after cloud
seeding with artificial crystallizing agents. The crystallization (WBF) process can be characterized
by the specific time that can be called “crystallization time” tcr. All drops will evaporate by the time
tcr, and the parcel will contain only crystals with the same initial concentration and the radius rcf1.
We assume that the vertical velocities or other sources of supersaturation generation are absent, so
that during drops evaporation until t = tcr, the water supersaturation is small, |sw| << 1, and can be
neglected, and vapor density is equal to the vapor saturated over water, rv = rws. It is also assumed
that the temperature change is small during evaporation, rws = const, and the crystals have a spheri-
cal shape.
The time tcr and the radius rcf1 can be evaluated using the water balance equation and the equa-
tions for growth rates of drops and crystals from Sections 5.1 and 5.2. At the beginning of the first
stage, the cloud parcel contains liquid drops with the liquid water content qL1 (0) = (4π / 3) ρ w N d rd30
and vapor saturated over water with the density rws. At the end of the first stage, when all the
drops have been evaporated, qL1(tcr) = 0, the parcel contains ice crystals with the ice water content
qL 2 (τ cr ) = (4π / 3) ρi N ircf3 1 and vapor saturated over water with the same density rws. The water balance
equation for the first stage can be written as:
4π 4π
ρ ws + ρ w N d rd30 = ρ ws + ρi N ircf3 1. (5.4.1)
3 3
5.4. The Wegener–Bergeron–Findeisen Process and Cloud Crystallization 159

The equations for the drops evaporation and crystal growth rates can be written using equations from
Sections 5.1 and 5.2, neglecting kinetic and psychrometric corrections:
drd
ρ wrd = Dv ( ρ v (t ) − ρ ws ), (5.4.2)
dt
drc
ρirc = Dv ( ρ v (t ) − ρis ). (5.4.3)
dt
The initial and final conditions for this system of equations are:

rd˙ t = 0 = rd 0 , rc˙ t = 0 = 0, r v˙ t = 0 = r ws,

rd˙ t = t cr = 0, rc˙ t = t cr = rcf 1, r v˙ t = t cr = r ws, (5.4.4)

The system (Eqns. 5.4.1–5.4.4) allows determination of two unknown quantities: rcf1 and tcr. The
final crystal radius after the first stage can be evaluated from (Eqn. 5.4.1):
1/3
ρ N 
rcf 1 = rd 0  w d  . (5.4.5)
 ρi N c 
Subtracting (Eqn. 5.4.3) from (Eqn. 5.4.2) and integration by time yields

ρ w [rd2 (τ cr ) − rd2 (0)] − ρi [rc2 (τ cr ) − rc2 (0)] = −2 Dv ( ρ ws − ρis )τ cr . (5.4.6)

Using the conditions (Eqn. 5.4.4), (Eqn. 5.4.5) for rcf1 and solving for tcr, we obtain the time of cloud
glaciation:

  ρ 1/3  N 2 /3  1/3
 ρ  N 
2 /3

τ cr = τ cr ,0 1 +  i   d   ≈ τ cr ,0  i   d  , (5.4.7a)
  ρw   Nc    ρw   Nc 
 
where

ρ wrd20
τ cr ,0 = . (5.4.7b)
2 Dv ( ρ ws − ρis )
The second approximate equality in (Eqn. 5.4.7a) makes use of the condition (Nd /Nc)2/3 >> 1, equiva-
lent to the condition rcf1/rd0 >> 1, which is usually valid for natural clouds and even in cloud-seeding
experiments. The physical meaning of tcr,0 is the time during which a drop with initial radius rd0
would evaporate if the humidity is equal to the saturation over ice. Equations (5.4.5) and (5.4.7a,b)
allow approximate estimates of the glaciation time and the crystal size after glaciation.
The second stage begins at the end of the first stage. Thus, the total water mass content at the
beginning is the sum of the ice water content qL2(tcr) and vapor saturated over water with rws, so that
the ice supersaturation si = (rws−ris)/ris. It is assumed that si relaxes to zero by the end of the second
stage due to vapor absorption by the crystals and rv = ris, the crystal concentration remains Nc, and
their radius rcf 2 after the second stage should be determined. The water balance for the second stage
is
4π 4π
ρ ws + ρi N crcf3 1 = ρis + ρi N ircf3 2 . (5.4.8)
3 3
160 Diffusion and Coagulation Growth of Drops and Crystals

Solving for rcf 2 and using (Eqn. 5.4.5) for rcf1, we obtain the crystal radius at the end of the second stage:
1/3 1/3 1/3
 ( ρ ws − ρis )   ρw N d   ρ ws − ρis 
rcf 2 = rcf3 1 +  = rd 0    1 +  . (5.4.9)
 ( 4 π / 3) ρ N
i c  ρ N
 i c   qL1 

Theoretically, the duration of the second stage is infinite since rv exponentially approaches ris as
described in Section 5.3, but the initial ice supersaturation (rws − ris) decreases e times during the
crystal phase relaxation time tf,cr = (4pDvNcrcf1)−1 and ≈ 20 times during 3tf,cr. Thus, tf,cr can serve as
a characteristic time of the second stage.
Example calculations are given in Table 5.4 for two droplet concentrations and two tempera-
tures. With rd0 = 5 mm, the ratio rcf1/rd0 varies from 35.5 to 7.7 at Nd = 500 cm−3 and from 20.8 to
4.5 at Nd = 100 cm−3 when Nc increases from 10 L−1 to 1,000 L−1. The crystallization time tcr varies
from 30–60 min to more than 7 hours at small crystal concentrations of 10–20 L−1 and decreases
to 100–150 s at very high Nc ~ 1,000 L−1. Equations (5.4.7a and b) show that tcr ~ rd02; therefore,
the glaciation time rapidly increases for larger drops. Since tcr ~ [Dv(rws − ris)]−1, the glaciation
time is minimum at the temperature with a maximum difference of vapor densities, T ≈ −12 °C, and
decreases at lower temperatures. Although the ice nucleation rates increase at low temperatures (see
Chapters 8, 9, and 10), the crystallization time tcr with the same crystal concentrations at −30 °C is
a factor of two larger than at −10 °C, and glaciation proceeds slower. This difference can explain the
relative stability and long persistence of the mixed phase arctic clouds at low temperatures and not
very high crystal concentrations.

Table 5.4. The ratio rcf1/rd0 and the crystallization time tcr (seconds) for various Nc and liquid cloud
properties: Nd = 500 cm−3, two initial drop radii, rd0 = 5 m m, (qL1 = 0.26 g m−3), and rd0 = 10 m m
(qL1 = 2.09 g m−3); Nd = 100 cm−3, the drop radius rd0 = 5 m m, (qL1 = 0.052 g m−3), at two
temperatures, −10 °C and −30 °C, and pressure p = 800 mb.

Nc, L−1
10 20 50 100 500 1000

Quantity rd0 = 5 μm, Nd = 500 cm−3, T = −10 °C

rcf 1/rd0 35.5 28.2 20.8 16.5 9.6 7.7
tcr, sec 3120 1970 1070 670 230 150
rd0 = 10 μm, Nd = 500 cm−3, T = −10 °C
tcr, sec 12480 7880 4280 2680 920 600
−3
rd0 = 5 μm, Nd = 500 cm , T = −30 °C
tcr, sec 6614 4176 2268 1420 487 318
−3
rd0 = 10 μm, Nd = 500 cm , T = −30 °C
tcr, sec 26457 16705 9073 5681 1950 1272
−3
rd0 = 5 μm, Nd = 100 cm , T = −30 °C
rcf 1/rd0 20.8 16.5 12.1 9.6 5.6 4.5
tcr, sec 2260 1430 775 485 166 110
5.5. Kinetic Equations of Condensation and Deposition in the Adiabatic Process 161

5.5. Kinetic Equations of Condensation and Deposition in the Adiabatic Process

5.5.1. Derivation of the Kinetic Equations

Temporal evolution of the droplet and crystal size spectra in clouds can be described with the dynamic
equations termed the kinetic equations for the size distributions functions. Several processes govern
transformation of the cloud particle size spectra: nucleation of water and ice, diffusion growth or
evaporation, collisions and coalescence, breakup. The general kinetic equation includes the terms
that describe all these processes, but each of these processes can be considered in isolation—that is,
using a specific kinetic equation. In this section, we introduce the kinetic equation that describes the
diffusional growth or evaporation of the drops and crystals due to their interaction with the vapor
field, which is termed the kinetic equation of condensation or deposition. We consider in this chapter
the kinetic equations in a laminar flow in an adiabatic process without turbulence or mixing, which
are also termed the kinetic equations of regular condensation.
In general, the distribution function of an ensemble of the cloud particles depends on three spatial
coordinates, with a fourth coordinate being the particle radius r (or mass m). The distribution function
may include several different parameters, such as soluble fraction, electrical charge, shape, and velocity.
We assume that there are n additional variables and denote them as xi. These 3 + 1 + n variables form a
(n + 4)-dimensional phase space. (If distributions are over only three coordinates and the radius or mass
are considered, we deal with the 4-dimensional space.) An ensemble of cloud particles represents a ther-

modynamic system that can be characterized by a distribution function of all these variables f ( x , r,xi )

in this phase space, where x denotes the vector of the three spatial coordinates. Each possible state of
the system corresponds to a uniquely determined point in this (n + 4)-dimensional space, and the tem-

poral evolution of f ( x , r, xi ) represents a trajectory in this phase space. If this system can be considered

closed, then the conservation law for the function f ( x , r,xi ) along the trajectory in this phase space is
described by the Liouville theorem, which is equivalent to the continuity equation in the phase space

df ( x, r ,ξi )
= 0. (5.5.1)
dt
Expanding the full derivative, we obtain

∂f ( x, r ,ξi , t ) ∂  ∂ ∂ ɺ
ɺ ( x, r ,ξi )  + ∑
ɺ ( x, r ,ξi )  + rf 
+ xf ξ f ( x, r ,ξi )  = 0,
(5.5.2)
∂t ∂x   ∂r i ∂ξ i

where xɺ denote the particles’ velocities, and r∙ = dr/dt and ξɺi = dξi /dt are the corresponding “veloci-
ties” in the space of radii and the variable xi. The term ∂(r∙f )/∂r represents the divergence of f(r) due
to condensation or deposition growth. If there are sources and sinks in the system, then an additional
term Js should be added to the right-hand side that describes the source or sink of the particles.

∂f ( x, r ,ξi , t ) ∂ ∂ ∂ ɺ
ɺ ( x, r ,ξi )  + ∑
ɺ ( x, r ,ξi )  + rf
+  xf ξ f ( x, r ,ξi )  = J s . (5.5.3)
∂t ∂x ∂r i ∂ξ i
 

If we consider only the size (or mass) distribution function and neglect the other variables xi, then the
phase space is 4-dimensional and this equation is simplified as

∂f ( x, r , t ) ∂ ∂
ɺ ( x, r , t ) = J s .
ɺ ( x, r , t )  + rf
+  xf (5.5.4)
∂t ∂x ∂r
162 Diffusion and Coagulation Growth of Drops and Crystals

If a particle falls at a fall speed Vt(r) along the 3rd (z) coordinate, the i-th component of its full veloc-
ity is xɺ = ui − Vt ( r )δ i3, and the kinetic equation can be written in the form
∂f ∂ ∂f
+ [(ui − Vt (r )δ i 3 ) f ] + (rf
ɺ ) = Js , (5.5.4a)
∂t ∂xi ∂r
where the usual convention of summation over double subscript i = 1, 2, 3 is assumed. If we consider
a spatially homogeneous system without dependence on the space variables, ∂/∂xi = 0, then the phase
space contains only one variable, r, and this equation is further simplified as
∂f (r , t ) ∂
ɺ (r , t )  = J s .
+ rf (5.5.5)
∂t ∂r
If we consider the size distribution by masses rather than by radii, then we should replace r with m,
rɺ with m∙ = dm /dt, and then the term ∂[r∙f (r)]/∂r becomes ∂[m∙ fm(m)]/∂m and (Eqn. 5.5.5) becomes
∂fm (m) ∂
+ ɺ m (m)  = J s .
 mf (5.5.6)
∂t ∂m 
Equations (5.5.2)–(5.5.6) represent various forms of the kinetic equation of regular condensation
or deposition in a laminar flow. The functions introduced earlier are related as

f ( x , r ) = ∫ f ( x , r , ξi ) d ξ1 d ξ 2 ...d ξ n , f (r ) = ∫ f ( x , r ) dV ,

fm (m) = ∫ f ( x , m) dV , fm (m)dm = f (r ) dr , (5.5.7)

where dV = dx1dx2dx3 is the differential of the volume. The corresponding growth rates, described in
the preceding Sections 5.1 and 5.2, are proportional to the supersaturation. Thus, the system of equa-
tions for calculations of the growth or evaporation by the condensation and deposition of an ensemble
of the cloud particles includes kinetic equations, the supersaturation equation, and the equation of
the growth of an individual particle. This system of equations will be used in the subsequent chapters
for studies of the drop and crystal nucleation. The term regular condensation here means that these
equations are written for the case of a flow without turbulence.
The kinetic equations of regular condensation (Eqns. 5.5.4–5.5.6) were introduced in cloud phys-
ics at the beginning of 1960s by Buikov (1961, 1963, 1966a,b) by analogy with the kinetic equation
formulated by Lifshitz and Slezov (1958, 1961) for the description of efflorescence in the polydis-
perse ensemble of the salt crystals in supersaturated solutions (see Chapter 11). The corresponding
kinetic equations for the turbulent atmosphere are termed the kinetic equations of stochastic con-
densation and will be considered in Chapters 13 and 14.
The method of kinetic equations is a powerful tool for calculation of the condensation growth of
polydisperse ensembles of the drops and crystals and in simulations of cloud evolution (e.g., Buikov
and Pirnach, 1973, 1975; Buikov and Khvorostyanov, 1976, 1977; Tzivion et al., 1987; Feingold
et al., 1994; Fridlind et al., 2004; Jensen et al., 1994; Khvorostyanov et al., 2001, 2003, 2006; Xue
et al., 2010; Curry and Khvorostyanov, 2012). Both numerical and analytical solutions of the kinetic
equations can be used for these calculations. The numerical solutions to the kinetic equations serve
as the basis for the spectral bin calculations of the evolution of the particles’ size spectra. The
method of moments widely used in cloud modeling (Chapter 14) can be rigorously derived from the
5.5. Kinetic Equations of Condensation and Deposition in the Adiabatic Process 163

kinetic equations, multiplying the kinetic equation by various powers of radius or mass, integrating
over the size spectrum and splitting the higher moments with various approximations. The kinetic
equation itself is equivalent to the method with an infinite number of moments. Further, the kinetic
equations can be solved analytically to provide insights into the condensation process.

5.5.2. Some Properties of Regular Condensation

Two important features of regular condensation are 1) conservation of the particle concentration
in the absence of sources and sinks, and 2) narrowing of the size spectra with time (Howell, 1949;
Mordy, 1959; Neiburger and Chien, 1960). These features can be illustrated with the kinetic
(Eqn. 5.5.5).
Integrating (Eqn. 5.5.5) by radius without the source term, Js = 0, and using the condition of nor-
malization of f(r) to the particle concentration N, we obtain
∞
∂ ∂N ∞

∂t ∫0
f (r )dr = ɺ (r )  = rɺ(0) f (0) − rɺ(∞) f (∞).
= − rf (5.5.8)
∂t 0

As seen from (Eqn. 5.1.46), the growth rate rɺ is finite at r = 0 and r = ∞, and f(r) is zero at zero and
infinite radii. The right-hand side of (Eqn. 5.5.8) is zero and this yields ∂N/∂t = 0. That is, the kinetic
equation of condensation without sources describes the temporal evolution of the size spectrum with
conservation of the particle concentration.
The second feature of the spectra, narrowing with time, is easily seen. In the diffusion regime of
the particles’ growth, when r >> xcon, which is valid in most situations, dr/dt is inversely proportional
to the particle radius (see Eqn. 5.1.46), the larger particles grow more slowly than the smaller par-
ticles, and thus the size spectrum should become narrower with time. The quantitative evaluation of
the spectral narrowing has usually been done using numerical techniques (e.g., Howell, 1949; Mordy,
1959; Neiburger and Chien, 1960).
The kinetic Equation (5.5.5) allows a simple analytical interpretation of the spectral narrowing.
Consider the spectral dispersion sr2
∞
1
N ∫0
σ r2 = (r − r )2 f (r )dr. (5.5.9)

Differentiating both sides by time yields

∂σ r2
= I1 + I 2 , (5.5.10a)
∂t
∞ ∞
1 ∂ f (r ) 1 ∂
∫ (r − r )2 ∫ f (r ) ∂t (r − r )
2
I1 = dr , I2 = dr . (5.5.10b)
N 0 ∂t N 0

It will be shown in the following text that the major contribution here comes from I1, while I2 is much
smaller or vanishes.
Substituting ∂f/∂t from the kinetic (Eqn. 5.5.5) into I1, integrating by parts and using the condition
rɺ(r ) f (r )|∞0 = 0 yields
∞ ∞
1 ∂ 2
I1 = −
N0∫ ∂r
ɺ (r )]dr = ∫ rf
(r − r )2 [rf
N0
ɺ (r )(r − r )dr. (5.5.11)
164 Diffusion and Coagulation Growth of Drops and Crystals

We use hereafter (Eqn. 5.1.46), assuming the diffusion growth regime, and so (Eqn. 5.1.46) can be
written as
drd bd Dv ρ ws sw
= , bd = , ξcon ≈ 0. (5.5.11a)
dt rd ρ w Γ1
Using this growth rate in the simplified form, we obtain
∞
2bd  r 2bd
I1 =
N ∫ f (r ) 1 − r  dr =
0 N
(
N − rM ( −1) . ) (5.5.12)

We accounted for the fact that the integral of the first term in the integrand gives N, and M(−1) is the
minus first moment of the spectrum. Further quantification requires some choice of the spectrum. We
choose the gamma distribution f(r) = cr pexp(−br); the moment M(−1) for this spectrum was calculated
in Section 2.4 as
∞
f (r ) β N
M ( −1) = ∫ dr = N = , (5.5.13)
0 r p rm

where rm = p/b is the modal radius (see Section 2.4). Substituting this into (Eqn. 5.5.12) and using an
expression for the mean radius r = ( p + 1)/β , we obtain
 r   p +1 2bd
I1 = 2bd  1 −  = 2bd  1 − =− . (5.5.14)
 rm   p  p

Thus, I1 is negative, and, as seen from (Eqn. 5.5.10a), I1 causes narrowing of the spectrum.
For calculation of I2, we first need to know ∂r−/∂t. Differentiating by time r (t ) defined as the first
moment of the spectrum f(r, t), and using (Eqn. 5.5.5) with Js = 0, integration by parts yields
∞ ∞
∂r (t ) 1 ∂ f (r , t ) 1 ∂(rf
ɺ)
= ∫r dr = − ∫ r dr
∂t N 0 ∂t N 0 ∂r
∞
1 b b
ɺ |∞0 +
= −rf ∫
N 0
ɺ dr = d M ( −1) = d ,
rf
N rm
(5.5.15)

where we again use the condition rɺ(r ) f (r )|∞0 = 0 and (Eqn. 5.5.13) for M(−1). This result shows that
the growth rate of the mean radius of the gamma spectrum at regular condensation is equal to that
in a monodisperse ensemble with the modal radius rm. Now we can evaluate I2, differentiating the
integrand by time and using (Eqn. 5.5.15):
∞
2  ∂r ∂r 
I2 =
N ∫ f (r )  −r ∂t
0
+r
∂t
 dr

2 b b  2b r 2b r
=  − M (1) d + r d  = − d + d = 0. (5.5.16)
N rm rm  rm rm

where we use the expression from Section 2.4 for the first moment, M (1) = Nr−. Thus, the term I2
vanishes and we have

∂σ r2 2b
= I1 = − d . (5.5.17)
∂t p
5.5. Kinetic Equations of Condensation and Deposition in the Adiabatic Process 165

So, using the kinetic equation, we have demonstrated that the dispersion is decreasing and the
size spectrum is narrowing with time during regular condensation. This expression can be further
clarified. As was shown in Section 2.4, the spectral dispersion of the gamma distribution can be
expressed as σ r = r /( p + 1) . We can express p as p = r /σ r − 1 . If the spectrum is not very wide,
2 2 2 2

then r 2/σ r2 >> 1, and approximately p ≈ r 2/σ r2 . Substitution of this expression into (Eqn. 5.5.17)
yields an equation for sr2,

∂σ r2 2b σ2
≈ − 2d σ r2 = − r . (5.5.18a)
∂t r τσ
Its solution is
σ r2 (t ) ≈ σ r2 (t0 )exp(−(t − t0 ) /τ σ ), (5.5.18b)

where we introduced the dispersion relaxation or narrowing time ts

r2 r2
τσ = = . (5.5.19)
2bd (2 Dv ρ ws /ρ w Γ1 )sw
Here we used (Eqn. 5.5.11a) for bd and neglected the kinetic correction xcon. Equations (5.5.18b) and
(5.5.19) show that the dispersion sr2 of the initial gamma distribution decreases with time exponen-
tially, which determines the rate of the spectral narrowing.
Thus, using the kinetic equation of regular condensation, we determined that particle growth is
accompanied by the narrowing of the size spectrum. If the spectrum can be approximated by a gamma
distribution, the characteristic narrowing time ts of the dispersion is τ σ ~ r /sw —i.e., the time is
2

proportional to the square of the mean radius and inversely proportional to the supersaturation sw.
Therefore, the rate of spectral narrowing increases for smaller mean radii and for faster growth rates
with larger supersaturations.
The theoretical prediction of spectral narrowing in regular condensation in an isolated cloud parcel
predicted by the calculations of Howell (1949), Mordy (1959), and others are in conflict with mea-
surements in clouds. Numerous experiments in situ have shown that the size spectra are sufficiently
broad at all stages of cloud developments. Therefore, it became clear that regular condensation is an
idealized model of condensation that may occur in an isolated cloud parcel or in cloud chambers.
Various hypotheses have been suggested to explain the broad size spectra in clouds. These hypoth-
eses are discussed in Chapters 13 and 14.

5.5.3. Analytical Solution of the Kinetic Equations of Regular Condensation

The analytical solution of (Eqn. 5.5.5) for a homogeneous cloud without the sources, Js = 0, can be
∙
obtained using the general method of characteristics for the differential equations, dt /1 = df /f = dr/r∙
(Buikov, 1961, 1963, 1966a,b; Sedunov, 1967, 1974; Kovetz and Olund, 1969). A simpler solution
is based on the differential conservation law, which expresses the conservation of the particles
dN(r, t) = dN(r0, t0), or
f (r, t)dr = f 0 (r0 , t0 )dr0 . (5.5.20)
166 Diffusion and Coagulation Growth of Drops and Crystals

Here r0 = r(t0), f0(r0, t0) are the radius and size spectrum at the initial time t0, and r(t), f(r, t) are the
radius and size spectrum at a subsequent time t. Integrating (Eqn. 5.1.46) for the radius growth rate
by time from t0 to t, we obtain
(r0 + ξcon )2 = (r + ξcon )2 − Qc (t ), Qc (t ) = 2c3 w yw (t ), (5.5.21)

where Qc(t) describes an increase in the squared radius, c3w and xcon were defined in Section 5.1, and
yw(t) is the integral water supersaturation
Dv ρ ws 4 Dv t
c3 w = , ξcon = , yw (t ) = ∫ sw (t ') dt '. (5.5.22)
ρ w Γ1 α cVv t0

Equation (5.5.21) expresses r0 as a function of r and we can calculate f(r, t) using (Eqn. 5.5.20):
dr0
f (r , t ) = f0 (r0 , t0 ) . (5.5.23)
dr

Finally, expressing r(t0) via r(t) from (Eqn. 5.5.21), we obtain

r + ξcon
f (r , t ) = f0 ([(r + ξcon )2 − Qc (t )]1/2 − ξcon ). (5.5.24)
[(r + ξcon )2 − Qc (t )]1/2

This is the analytical solution of the kinetic equation of the regular condensation for a spatially
homogeneous case. It expresses the size spectrum f(r, t) at any time t via the known function f0(r0, t0)
at the time t0. Note that the solution f(r, t) exists only when the denominator and argument of f0 are
positive—that is, at r > rmin = Qc1/2(t) − xcon. This means that the smaller droplets have grown above
this lower limit rmin by time t, and there are no small drops in the absence of new drop nucleation.
Thus, the solution (Eqn. 5.5.24) also predicts narrowing of the spectrum.
This solution (Eqn. 5.5.24) can be conveniently used both for analytical studies and in numerical
simulations of evolution of the size spectrum at the condensation stage. If t = t0 + Dt, where Dt is
the time step in a numerical model, (Eqn. 5.5.24) allows us to calculate f(r, t+ D t) using the function
f0(r0, t0) from the previous time step. This requires a choice of the finite-difference grid by radius r0,
a finite-difference representation of f0(r0, t0) on this grid, and a recalculation from every grid point
by r0 to the grid points by the argument [(r +xcon)2 − Qc(t)]1/2. This can be easily done using numeri-
cal recalculation between the two grids (e.g., linear, quadratic, spline interpolation, or any other that
ensures sufficient accuracy). This procedure can be repeated iteratively for every time step in the
model, and allows simulation for a long time. Examples of such numerical simulation will be given
in the subsequent chapters.
As discussed in Section 5.1 for pure drops in the absence of the surface-active substances, the
condensation coefficient ac ~ 1, the kinetic correction xcon ~ 0.2 mm, and hence these terms can be
neglected for the drops with rd > 1–2 mm that grow in the diffusion regime. Thus, (Eqn. 5.5.24) is
simplified as
r
f (r , t ) = f0 ( [r 2 − Qc (t )]1/2 ). (5.5.25)
[r − Qc (t )]
2 1/2

As discussed in Sections 5.1 and 5.2, when the drops or crystal are covered with a surface-active
substance or film, the condensation and deposition coefficients can be as low as ac ~ 10−3 to 10−5, and
5.5. Kinetic Equations of Condensation and Deposition in the Adiabatic Process 167

so xcon ~ 1/ac can be large. Then, the particles grow in the kinetic regime, and (Eqn. 5.5.24) becomes
in this limit
ξcon
f (r , t ) = 2
f0 ( ξcon2 − Qc (t ) − ξcon ). (5.5.26)
ξ con − Qc (t )

Equations (5.5.25) and (5.5.26) show that the solutions for f(r, t) exist only at r > rmin = Qc1/2(t) in the
diffusion limit and at Qc1/2(t) < xcon in the kinetic limit. It is not a limitation of the solution itself, but
it does impose a limit for the integration time steps.

5.5.4. Equation for the Integral Supersaturation

The solution (Eqn. 5.5.24) to the kinetic (Eqn. 5.5.5) or its particular cases (Eqns. 5.5.25) and (5.5.26)
require the integral supersaturation yw(t). This equation can be obtained from (Eqn. 5.3.28a) for the dif-
ferential supersaturation sw in the liquid cloud (without the crystal phase, tfc = ∞) using the analytical
solution of the kinetic equation. Replacing in (Eqn. 5.3.28a) sw = yw′(t), and using (Eqn. 5.3.20a) for
the droplet supersaturation relaxation time tf (we omit hereafter the subscript d for brevity), we obtain
dyw′ (t ) ∞ r2
= [1 + yw′ (t )]c1w w − yw′ (t )4π Dv ∫ f (r , t ) dr . (5.5.27)
dt 0 r +ξ
con

This equation expresses yw′(t) via f(r, t) at the same time t; this f(r, t) enters on the right-hand side in
the integral Icon defined in (Eqn. 5.3.17a). In numerical solution, it is convenient to express f(r, t) in
Icon via f(r, t0) at the previous time step t0. Using the relation

r2 {[(r0 + ξcon )2 − Qc ]1/2 − ξcon }2

= , (5.5.28)
r + ξcon [(r0 + ξcon )2 − Qc ]1/2

which follows from (Eqn. 5.5.21), and using the relation f(r)dr = f0(r0)dr0 and substituting the solu-
tion (Eqn. 5.5.24) into (Eqn. 5.5.27) yields the integral Icon:
∞
{[(r0 + ξcon )2 − Qc ]1/2 − ξcon }2
I con = ∫ f0 (r0 ) dr0 . (5.5.29)
0
[(r0 + ξcon )2 − Qc ]1/2

Substituting Icon into (Eqn. 5.5.27), we obtain

∞
dy 'w (t ) {[(r0 + ξcon )2 + Qc (t )]1/2 − ξcon }2
= [1 + yw′ (t )]c1w w − yw′ (t )4π Dv ∫ f0 (r0 ) dr0 . (5.5.30)
dt 0
[(r0 + ξcon )2 + Qc (t )]1/2

This is the integro-differential equation for the integral supersaturation yw(t), which includes the size
spectrum f0(r0) from the previous time step. For the drop growth in the diffusion regime, xcon << r,
the equation is simplified as
∞
dy′w (t )
= [1 + y′w (t )]c1w w − y′w (t )4π Dv ∫ r02 + Qc (t ) f0 (r0 )dr0 . (5.5.31)
dt 0

These two equations, the kinetic (Eqn. 5.5.24) and the integral supersaturation (Eqn. 5.5.30), form
a closed system of equations where the droplet growth rate equation has been incorporated. This
168 Diffusion and Coagulation Growth of Drops and Crystals

system of equations allows simulation of the cloud droplet size spectra in a Lagrangian parcel model
in a spatially homogeneous cloud during characteristic times of condensation before the particles’
collisions and coagulation become important. The kinetic equation combined with the supersatura-
tion equation constitute a platform for cloud numerical modeling with detailed accounting for the
microphysical processes. This method with direct calculation of the size spectra and their evolution
is termed the spectral microphysics method in order to distinguish it from the parameterized or bulk
microphysics that is based on calculation of the bulk cloud properties, usually of the liquid or ice
water content and particle concentration, and using some a priori prescribed size spectra and their
parameterizations considered in Sections 2.3 and 2.4.
Further generalizations of this basic system of equations are straightforward. The coagulation pro-
cesses are considered in Section 5.6 of this chapter. The source terms Js in Equations (5.5.3)–(5.5.6)
describes activation of the new droplets considered in Chapters 6 and 7, and nucleation of the crystals
is considered in Chapters 8–10, where these equations are generalized for a mixed-phase cloud. A gen-
eralization for spatially inhomogeneous clouds is done based on (Eqn. 5.5.4) in Chapters 13 and 14,
where effects of turbulent mixing are also included. These equations can be used in the Eulerian
one-, two-, and three-dimensional models. For this purpose, these equations should be presented using
finite-difference approximations and various numerical techniques can be used. The finite-difference
approximation of the size spectrum consists in dividing the entire spectrum into many small domains
by radius or mass, called bins. Therefore, this method is also called the bin microphysics method, or
sometimes these two terms are combined in the name “spectral bin microphysics method.”

5.6. Kinetic Equations of Coagulation

5.6.1. Various Forms of the Coagulation Equation

Another important process that governs evolution of the size spectra of cloud particles are the processes
of particles’ interactions: coagulation, riming, and accretion. The term coagulation denotes the process
of collision, with subsequent merging of the two liquid drops; the term riming means the collision and
merging of a drop and a crystal; and the term accretion means the collision and merging of the two
crystals. These three processes are sometimes collectively referred to as coagulation.
The coagulation of drops can be caused by various processes. Brownian coagulation occurs due
to random thermal motions of the molecules that strike large particles, so that the resulting momen-
tum forces these particles to move randomly, collide with each other, and coagulate. The kinetic
equation for Brownian coagulation was derived by Smoluchowski (1916) in the following way.
Consider an ensemble of identical particles with equal volumes v1 (monomers), and assume that the
collision of any two particles results in their coagulation and the adding of their volumes. If particle
collisions and coagulation continue for some time, a number n2 of the particles will occur with the
volume v2 = 2v1 (dimers), a number n3 of the particles with the volume v3 = 3v1 (trimers), and so on,
and a number nk of the particles with vk = kv1 (k-mers). There are two types of collisions that govern
the concentration of the k-mers: 1) their collision with the i-mers leads to formation of the particles
with the volume vik = (vi + vk), that is, to the loss of the k-mers; and 2) the collision of the i-mers
(volume vi) with the (k − i)-mers (volume vk − vi), by adding their volumes, produce k-mers.
5.6. Kinetic Equations of Coagulation 169

Obviously, the rate of loss (dnk/dt)loss of the k-mers due to their collisions with all the i-mers is pro-
portional to their concentration nk and can be written as
∞
 dnk 
  = − nk ∑ K ik ni , (5.6.1)
 dt loss i =1

where Kik is some coefficient, called the collection kernel, that depends on the physical properties of
the particles and their motion. The rate of gain of the k-mers is proportional to the concentration of
the i-mers and (k−i)-mers, thus

 dnk  1 k −1
  = ∑ K i , k − i ni nk − i . (5.6.2)
 dt  gain 2 i =1
The factor 1/2 arises here in order to avoid counting twice the same collisions (i, k-i) and (k-i, i). Now
the rate of change of the k-mers can be written by summing up these two rates:

 dnk   dnk   dnk  1 ∞ ∞

 =  +  = ∑ K i , k − i ni nk − i − nk ∑ K ik ni . (5.6.3)
 dt   dt  gain  dt loss 2 i =1 i =1

Equation (5.6.3) is the Smoluchowski (1916) coagulation equation that has been used in numerous
studies of the coagulation process. Smoluchowski derived this equation in its discrete form, and its
continuous analog was obtained by Müller (1928) for the distribution function by particles’ masses.
Based on the conservation of particle masses during collisions, Müller replaced the sums over i-mers
with the integrals over their masses dm, and the discrete variables ni with continuous function f(m).
this transformed the equation into

∂f (m, t ) 1
m ∞
= ∫ K (m
(m - m ’-− f (m ∫ K ((m,, m¢) f (m¢) dm¢,
’ f (m -− m¢) f (m¢) dm¢
− m¢,m) (5.6.4)
∂t 20 0

where K(m, m′) is the collection kernel in the mass space. The first term on the right-hand side describes
the gain of the particles with the mass m due to the collision and merging of the particles with (m-m′) and
m′, while the second term describes the particles’ loss due to collisions of m and m′. Assuming that the par-
ticles are identical and have the same density, this equation can be rewritten in terms of particle volumes:

∂fv (v, t ) 1 v ∞
= ∫ K (u, v − u) fv (u, t ) fv (v − u)du − fv (v, t )∫ K (u, v) fv (u, t )du, (5.6.5)
∂t 20 0

where again the first and second terms describe the gain and loss of the particles at collisions.
The coagulation equation is sometimes used in terms of the particles’ radii (e.g., Junge, 1963).
The transformation to radii can be done using again the differential conservation law, fv(v)dv =
fr(r)dr, where the subscripts indicate the corresponding distribution functions. Let r, r′, and r′′
denote the radii corresponding in (Eqn. 5.6.5) to the volumes v, u, and (v − u), so that v = (4/3)pr3,
u = (4/3)pr′3, and (u − v) = (4/3)pr′′3. Then, the relations among the functions are
dr ′ 1
fv (u)du = fr (r ′)dr ′, fv ( v ) = fr (r ′) = fr (r ′), (
du 4π r ′ 2 π
v

dr ′′ 1 1
r , fv ( v − u) = fr (r ′′) = fr (r ′′) = fr (r ′′) . (5.6.6)
π d ( v − u) 4π r ′′ 2 4π (r 3 − r ′ 3 )2/3
170 Diffusion and Coagulation Growth of Drops and Crystals

Substituting these relations into (Eqn. 5.6.5) and multiplying by 4pr2, we obtain a coagulation equa-
tion in terms of radii,
−2 /3
∂fr (r , t ) 1 r  r ′3 
= ∫ K [(r 3 − r ′3 )1/3 , r ′]  1 − 3  fr [(r 3 − r ′3 )1/3 ] fr (r ′)dr ′ ( ∫
∂t 20  r 
∞
′)dr ′ − fr (r , t )∫ K (r , r ′) fr (r ′)dr ′. (5.6.7)
0

5.6.2. Collection Kernels for Various Coagulation Processes

There are several types of processes that cause particle collisions with subsequent coagulation. The
processes relevant to cloud physics include Brownian coagulation, gravitational coagulation, laminar
and turbulent shear coagulation, and electrical coagulation. They differ by the collection kernels that
describe the physics of the corresponding processes. Note that the dimension of the coagulation kernel
K(r, r′) is [cm3 s−1], which characterizes it as the volume per unit time available for two particles to
collide and merge. Thus, the goal in determination of K(r, r′) is reduced to calculation of this volume in
various processes. A brief description of some processes and kernels used in cloud models is given next.
Brownian coagulation is one of the most important for cloud physics. It governs evolution of the
aerosol size spectra and aerosol fluxes to the drops, thereby influencing ice nucleation in the contact
mode (see Chapter 10). The collection kernel K(r, r′) for Brownian coagulation represents the diffu-
sion flux of the aerosol particles. The aerosol flux onto a particle with radius r can be derived from
the diffusion equation, as was done for the vapor flux in Section 5.1 and, similar to the molecular
flux in (Eqn. 5.1.6), is proportional to the Brownian diffusion coefficient Dr and particle radius. The
diffusion coefficient Dr for Brownian diffusion is described by Einstein’s formula
kT
Dr = , (5.6.8)
6πη ar
where k is the Boltzmann constant and ha is the dynamic viscosity of the air. Experimental studies
showed that the diffusion to the small particles is better described using Cunningham’s slip-flow cor-
rection asl(r) to Einstein’s diffusion coefficient,
kT
Dr = α sl (r ), α sl (r ) = AC + BC exp(−CC /N Kn ), (5.6.9)
6πη ar
where AC, BC, and CC, are the empirical constants, Kn = lf /r is the Knudsen number, and lf is the
mean free molecular path defined in Section 5.1. If we consider mutual diffusion of the aerosol
particles with radii r and r′, their diffusion coefficients, fluxes, and the collection kernels are added,

kT  α sl (r ) α sl (r ′) 
Drr ′ = Dr + Dr ′ =  + . (5.6.10)
6πη a  r r′ 
2 kT  α (r ) α sl (r ′) 
K (r , r ′) = 4π Drr ′ (r + r ′) = (r + r ′)  sl + . (5.6.11)
3η a  r r′ 
These equations are used in Chapter 10 to describe contact ice nucleation.
5.7. Thermodynamic and Kinetic Equations for Multidimensional Models 171

Gravitational coagulation. This type of coagulation process is caused by the different fall veloci-
ties of a larger drop or crystal with radius R and fall velocity Vt(R) relative to a smaller particle with
radius r and fall velocity Vt(r). The simplest model of this process is the following. The large particle
in its free fall passes in one second a path equal to Vt(R) and sweeps out a volume of air in a vertical
cylinder with the height z = Vt(R). It can touch and collect all the smaller drops that are located at a
distance from the axis of the cylinder x ≤ (R + r). The relative velocity of the two particles with R and
r is DVt = Vt(R) − Vt(r). It is clear that the larger particle can collide in unit time with all of the smaller
particles in the volume d V of the cylinder with the height DVt = Vt(R) − Vt(r) and a cross-section
p(R + r)2, so that dV = p(R + r)2[Vt(R) − Vt(r)].
However, not all of these collisions will lead to coagulation, and some smaller particles may
bounce off. The probability of coagulation after collision is characterized by the collision efficiency
E(R, r) ≤ 1, the ratio of the number of coagulation events to the number of collisions, and the kernel
KG of gravitational coagulation, which is
K G (r , r ′) = E ( R, r )δ V = π ( R + r )2 E ( R, r )[Vt ( R ) − Vt (r )]. (5.6.12)

Refinements of this model include accounting for the more complicated flow of the smaller particle
along the stream functions around the larger particle and the parameterizations of E(R, r). Fuchs
(1959, 1964) and some other authors considered this flow in more detail by accounting for the angu-
lar dependence, and so developed a parameterization of E(R, r) in terms of the ratio prR = r/R as
2
prR
E ( R, r ) = . (5.6.13)
2(1 + prR
2
)
A comparison of (Eqn. 5.6.13) with these detailed calculations showed a sufficient accuracy of
(Eqn. 5.6.13) for prR ≤ 0.5.
The methods of calculation and reviews of various approximations for E(R, r) for gravitational
Brownian coagulation, laminar and turbulent shear coagulation, and electrical coagulation are
given by Jonas (1972), Long (1974), Voloshchuk and Sedunov (1975), Hall (1980), Low and List
(1982a,b), Voloshchuk (1984), Pruppacher and Klett (1997), Bott (1998, 2000, 2001), MacFarquhar
(2004), Straka (2009), and Cotton et al. (2011). These methods and calculations can be used for
evaluation of the coagulation kernels and rates.

5.7. Thermodynamic and Kinetic Equations for Multidimensional Models

In multidimensional models, as in many cloud, mesoscale, and large-scale models, the heat and mois-
ture transfer are often calculated using the equations for the potential temperature q and the specific
humidity q and related specific variables (supersaturation, condensation rates, etc.). The equations
for q and q in the turbulent atmosphere can be written in the curvilinear coordinate system over a
complex terrain with accounting for orographic effects as
∂θ ∂uθ ∂ vθ ∂ wθ ∂θ ∂ ∂θ
+ + + − (uhx + vhy ) = kz D̂q
++ ∆
∂t ∂x ∂y ∂z ∂z ∂z ∂z
Le L L L
θ+ ε cw + s ε ci + m εf + m ε m + Rrad , (5.7.1)
cp cp cp cp
∂q ∂uq ∂vq ∂wq ∂q ∂ ∂q
+ + + − (uhx + vhy ) = kz - eccw - eci .
+ D̂ q − (5.7.2)
∂t ∂x ∂y ∂z ∂z ∂z ∂z
172 Diffusion and Coagulation Growth of Drops and Crystals

Here x, y, and z are the coordinates; t is time; u, v, and w are three components of wind speed; kz is
the coefficient of vertical turbulent diffusion, and
∂ ∂ ∂ ∂
∆ˆ = kx + ky (5.7.3)
∂x ∂x ∂y ∂y
is the operator of horizontal eddy diffusion. kx, ky are the horizontal components of the turbulent
exchange coefficient, h(x, y) is the height of surface relief, and hx = ∂h/∂x and hy= ∂h/∂y are the slopes
of the relief height. ecw and eci are the specific condensation and deposition growth rates [g g−1 s−1]
related to the condensation and deposition rates Icon and Idep considered in Section 5.3 as ecw = Icon/ra
and eci = Idep/ra; ef and em are the specific freezing and melting rates; Rrad = (∂T/∂t)rad is the radiative
temperature change rate.
The microphysics of a mixed-phase cloud in the models using spectral bin microphysics method is
calculated using the two kinetic equations for the size distribution functions of the droplets fd(x, y, z,
rd, t) and crystals fc(x, y, z, rc, t) that are solved at each time step. As discussed in Section 5.5 and later
in Chapter 13, these equations are written here in the simple form that account for the turbulent mix-
ing in clouds, as practically in all cloud models based on the spectral bin microphysics. The kinetic
equation for the drop size spectrum fd(rd) is

∂fd ∂ufd ∂vfd ∂[ w − vd (rd )] fd ∂f

+ + + − (uhx + vhy ) d
∂t ∂x ∂y ∂z ∂z z
fd ∂ ∂f  ∂f   ∂f 
= kz d + ∆ˆ fd +  d  +  d 
z ∂z ∂z  ∂ t  act  ∂t cond / evap
 ∂f   ∂f   ∂f 
+ i + i + i . (5.7.4)
p  ∂t  aggr  ∂t  frz  ∂t break / mult
The kinetic equation for the crystals size spectrum fc(rc) is

∂fc ∂ufc ∂vfc ∂[ w − vc (rc )] fc ∂f

+ + + − (uhx + vhy ) c
∂t ∂x ∂y ∂z ∂z z
fc ∂ ∂f  ∂f   ∂f 
= kz c + ∆ˆ fc +  c  +  c 
z ∂z ∂z  ∂ t  nucl  ∂t cond / evap
 ∂f   ∂f   ∂f 
+ c + c + c . (5.7.5)
p  ∂ t  aggr  ∂ t  melt  ∂t break / mult
Here, the indices d and c mean drops and crystals, rd is the droplet radius and rc is the crystal
equivalent radius (or semi-axis), rɺd and rɺc are their growth rates, and vd(rd) and vc(rc) are the ter-
minal velocities evaluated as described in Chapter 12. The last five terms on the right-hand side of
(Eqns. 5.7.4 and 5.7.5) describe various microphysical processes: drop activation (∂fd /∂t)act is consid-
ered in Chapters 6 and 7; heterogeneous and homogeneous nucleation of crystals, (∂fc /∂t)nucl and drop
freezing (∂fd/∂t)frz (Chapters 8–10); drop and crystal diffusion growth and evaporation (∂fd /∂t)cond/evap
and (∂fc/∂t)cond/evap (Sections 5.1 and 5.2); aggregation (coagulation and accretion), (∂fd /∂t)aggr and
(∂fc /∂t)aggr (Section 5.6); and crystal melting (∂fc/∂t)melt; and drop breakup and ice multiplication,
(∂fd /∂t)break/mult and (∂fc /∂t)break/mult.
5.8. Fast Algorithms for Microphysics Modules in Multidimensional Models 173

After calculating the distribution functions fd and fc, many characteristics can be calculated as the
integrals (moments) over the size spectra at each grid point and time step, such as liquid water content
(LWC), ice water content (IWC), concentrations Nd and Nc, mean radii, radar and lidar reflectivities
and visibility (as described in Section 2.3), absorption and extinction coefficients, optical thickness
and emissivity, and integral terminal velocities. Calculation of the diffusion growth of drops and crys-
tal requires supersaturation that is calculated using the splitting method described in the next section
(Section 5.8). Once the size spectra and supersaturation have been calculated, a detailed evaluation
can be done of the supersaturation budget (generation and absorption rates) along with the crystal
mass budget: the gravitational flux of crystals (precipitation rate), the regular flux due to vertical
velocities, the turbulent flux, and the total budget of crystal mass, which is the sum of four gradients
(influxes) of the corresponding fluxes defined previously (e.g., Khvorostyanov and Sassen, 1998c,
2002; Khvorostyanov, Curry, et al., 2001, 2003, 2006).
This relatively simple method for accounting for cloud microphysics described here is based on
solving the two kinetic equations for drop and crystal size distribution functions, each function,
besides the spatial variables, depends on one size parameter, radius or mass. This method can be
easily generalized for several types of crystals, but a separate size distribution function should be
added for each crystal type taking into account its shape. Another possible generalization would be to
introduce additional variables for fd and fc like the soluble and insoluble fractions, electrical charge,
surface-active substances, etc.

5.8. Fast Algorithms for Microphysics Modules in Multidimensional Models

The system of thermodynamic and kinetic equations for a multidimensional model described in
Section 5.7 can be solved by using a splitting method according to physical processes and compo-
nents as described, e.g., in Buikov and Pirnach (1973, 1975), Buikov and Khvorostyanov (1977),
Khvorostyanov (1982, 1995), Kondratyev et al. (1990a,b), Khvorostyanov and Sassen (1998a),
Khvorostyanov, Curry et al. (2001, 2003, 2006), Curry and Khvorostyanov (2012). The splitting
method provides fast algorithms that allow us to combine large and small time steps and signifi-
cantly accelerate simulations.
The equations for temperature, humidity, and for the spectra of droplets and crystals are solved
by splitting the major time step Dt into six substeps, denoted hereafter as k/6, so that the results of
calculations from the previous of these six substeps serve as initial conditions for the next substep.
The first three substeps account for the evolution of the variables due to turbulent and wind transport
along the x, y, and z directions:

∂ϕ 1/6 ∂(uϕ 1/6 ) ∂ ∂ϕ 1/6 ∂ϕ 2/6 ∂(vϕ 2/6 ) ∂ ∂ϕ 2/6 /

+ = kx , + = ky ,
∂t ∂x ∂x ∂x ∂t ∂y ∂y ∂y t
/ 3/6 3 /6 3/6
∂ϕ ∂(wɶ ϕ ) ∂ ∂ϕ
+ = kz . (5.8.1)
y ∂t ∂z ∂z ∂z
Here j denotes any of the four parameters q, q, fd, or fc, the superscripts 1/6, 2/6, and 3/6 denote the
substeps of splitting: wɶ = w − uhx − vhy for q and q, and wɶ = w − vd ,c − uhx − vhy for fd and fc.
174 Diffusion and Coagulation Growth of Drops and Crystals

During the fourth substep, the growth of droplets and crystals by condensation, deposition, or
evaporation is calculated after a transition to the equations for specific supersaturations with respect
to water Dw = q − qws(T) and with respect to ice Di = q − qis(T). These equations are being obtained in
the way similar to that in Section 5.3 for fractional supersaturations. During the fourth step of split-
ting, after removal of the space variables, a Lagrangian zero-dimensional problem is actually being
solved. Equations for the temperature and specific humidity can be written after removal of the space
variables in (Eqns. 5.7.1) and (5.7.2) as
dT Le L dq (5.8.2)
= ε cw + s ε ci − w γ a + Rrad , = − ε cw − ε ci .
dt c p cp dt

The condensation ecw and deposition eci growth rates are obtained from (Eqn. 5.3.19):

I con ∆w I dep ∆i
ε cw = = , ε ci = = , (5.8.3)
ρ a Γ1τ fd ρa Γ 2τ fc

where G1 ≈ Gw and G2 ≈ Gi are the psychrometric corrections (Eqn. 5.3.15), tfd and tfc are the relaxation
times of supersaturation by drop and crystals. Differentiating specific supersaturation Dw = qv − qws(T)
by time and substituting (Eqn. 5.8.2), we obtain:
d ∆ w dqv ∂qws dT
= −
dt dt ∂T dt
∂qws  Le Ls 
= − (ε cw + ε ci ) −  ε cw + ε ci − γ a w + Rrad 
∂T  c p cp 
 L ∂q   L ∂q  ∂q
= − ε cw  1+ e ws  − ε ci  1+ s ws  + ws ( γ a w − Rrad )
 c p ∂T   c p ∂T  ∂T
∂qws
= − ε cw Γ1 − ε ci Γ 2 + ( γ a w − Rrad ), (5.8.4)
∂T
where we used definitions (Eqn. 5.3.15) for psychrometric corrections G1 and G2. Substituting here
(Eqn. 5.8.3) for ecw and eci, we obtain an equation for the specific supersaturation Dw for a mixed-
phase cloud, containing water vapor, droplets, and crystals:
d∆ w ∆ Γ ∆ ∂q
= − w − 12 i + ws (γ a w − Rrad ), (5.8.5)
dt τd Γ2 τ c ∂T
where G12 = 1 + (Ls/cp)(∂qsw/∂T). Taking into account the relation Di = Dw + (qws − qis), (Eqn. 5.8.5)
can be rewritten for the 4/6-th substep of splitting as

d ∆ w4 / 6  Γ  Γ ∂q
= − τ −fd1 + 12 τ −fc1  ∆ w4 / 6 − 12 τ −fc1 (qws − qis ) + ws (γ a w − Rrad ). (5.8.6)
dt  Γ 2  Γ 2 ∂T

As discussed in Section 5.3, this equation has clear physical meaning. The first term on the right-
hand-side of (Eqn. 5.8.6) describes supersaturation relaxation due to absorption of the vapor by
droplets and crystals, the second term describes the vapor flux from drops to crystals (the Wegener–
Bergeron–Findeisen process), and the third term describes supersaturation generation due to upward
vertical velocities w and radiative cooling Rrad, or the occurrence of negative supersaturation and
5.8. Fast Algorithms for Microphysics Modules in Multidimensional Models 175

evaporation of the cloud, if (gaw − Rrad) < 0. Equations for the ice supersaturation Di and for the tem-
perature T at the substep 4/6 are obtained in the same way:

d ∆ i4 / 6 Γ  Γ (q − qis ) ∂qis
= −  21 τ −fd1 + τ −fc1  ∆ i4 / 6 + 21 ws + −((γ a w − Rrad ), (5.8.7)
dt  Γ1  Γ1 τ fc ∂T

dT 4/6  Le 1 L 1  4/6 Ls (qws − qis )

= + s  ∆w + − (γ a w − Rrad ), (5.8.8)
dt  c p Γ1τ fd c p Γ 2τ fc  c p Γ 2τ fc
 
where G21 = 1 + (Le/cp)(∂qsi/∂T). In (Eqn. 5.8.8), the first term is responsible for the heating due to the
condensation and deposition, the second term describes heating caused by the WBF process, and the
third term means cooling due to updraft velocities and radiative exchange or heating in the downdrafts.
The preceding equations describe the thermodynamics and kinetics of the mixed-phase cloud.
Reduction to the liquid cloud is with tfc = ∞ (Nc = 0), and reduction to the pure crystalline cloud is with
tfd = ∞ (Nd = 0). For the calculation of temporal evolution of droplet and crystal size spectra, it is conve-
nient to introduce the normalized integral specific supersaturations Qw and Qi that describe an increase
in the squared radius (see Section 5.5) and are related to the specific supersaturations as follows:

2 Dv ρ a t
2 Dv ρ aζ i t

Qw (t ) =
ρw Γ w ∫∆
tj
w (t ′) dt ′, Qi (t ) =
ρi Γ i ∫ ∆ (t ′)dt ′,
tj
i (5.8.9)

dQw 2 Dv ρ a dQi 2 Dv ρ aζ i
= ∆w , = ∆i , (5.8.10)
dt ρw Γ w dt ρi Γ i
where zi describes the effect of the crystal shape defined in (Eqn. 5.2.24). As discussed in Section
5.5, using Maxwell’s equations from Sections 5.1, 5.2 for the growth rates, and the conservation law
in the differential form f [(r(t)]dr(t) = f [(r(t0)]dr(t0), we can express the function f(t) at a time t via the
function at an initial time t0 as described in Section 5.5 by (Eqns. 5.5.20)–(5.5.24). Applying these
relations to the substep 4/6 with diffusion and deposition growth, we can simply express the function
f 4/6(r) after the end of the substep 4/6, via the function f 3/6(r) at the beginning of this substep—i.e.,
after the three substeps of spatial transport. Using (Eqn. 5.5.24), we obtain for the droplet spectrum
drd3/6
fd4/6 (rd , t ) = fd3/6 (rd3/6 )
drd4/6
rd + ξcon
= fd3/6 ([(rd + ξcon )2 − Qw (t )]1/2 − ξcon ), (5.8.11)
[(rd + ξcon )2 − Qw (t )]1/2

where fd3/6(rd) is the “old” distribution function after the 3/6 substeps of transport, and fd4/6(rd) is the
“new” distribution function after the 4/6-th substep of condensation or evaporation. The crystal size
spectrum is calculated in the same way,
drc3/6
fc4/6 (rc , t ) = fc3/6 (rc3/6 )
drc4/6
rc + ξ dep
= fc3/6 ([(rc + ξ dep )2 − Qi (t )]1/2 − ξ dep ), (5.8.12)
[(rc + ξ dep )2 − Qi (t )]1/2
176 Diffusion and Coagulation Growth of Drops and Crystals

where fc3/6(rc) is the “old” distribution function after the three substeps of transport, and fc4/6(rc) is the
“new” distribution function after the 4/6-th step of deposition or evaporation.
In cloud modeling, it is often more convenient to use equations for the integral supersaturations
Qw and Qi instead of equations for Dw, Di and to solve directly equations for Qw and Qi. The equa-
tions for Qw and Qi can be derived by the substitution of relations (Eqns. 5.8.9) and (5.8.10) into the
(Eqns. 5.8.6) and (5.8.7) for Dw and Di. To derive the equation for Qw, we first transform the expres-
sions for the relaxations times. Substitution of (Eqn. 5.8.11) into (Eqn. 5.3.20a) for tfd and accounting
also for the ventilation corrections gives (we omit here the superscripts of the substeps for brevity)
∞
rd2 fd {[(rd + ξcon )2 − Qw (t )]1/2 − ξcon }
τ −fd1 = 4π Dv ∫
rd min
[(rd + ξcon )2 − Qw (t )]1/2
Fven (rd ) drd . (5.8.13)

The lower limit here is determined from the condition that the argument of fd and the denominator
should not be negative, which yields

[(rd + ξcon )2 − Qw (t )]1/2 ≥ 0, or rd min = Qw1/2 (t ) − ξcon. (5.8.14)

It is convenient now to introduce a new variable rd′ so that

rd′ = [(rd + ξcon )2 − Qw (t )]1/2 − ξcon . (5.8.15)

Substituting (Eqn. 5.8.15) into (Eqn. 5.8.13), and taking into account that, as follows from (Eqn.
5.8.14), the limit rdmin in the integral over rd corresponds to the limit rd′ = 0 in integration over rd′, and
omitting the prime at rd′ in the final equation, we obtain
∞

τ −fd1 = 4π Dv ∫ Rd (rd , ξcon ) fd3/6 (rd , t ) Fven (rd ) drd ,

0

{[(rd + ξcon )2 + Qw (t )]1/2 − ξcon ]}2

Rd (rd , ξcon ) = (5.8.16)
[(rd + ξcon )2 + Qw (t )]1/2

where the superscript 3/6 indicates that the droplet size spectrum is taken from this substep. A similar
expression can be derived for tfc. Substitution of (Eqn. 5.8.12) into (Eqn. 5.3.20a) for tfc gives
∞
rc2 fc {[(rc + ξ dep )2 − Qi (t )]1/ 2 , t}
τ −fc1 = 4π Dvζ i ∫
rc min [(rd + ξ dep )2 − Qi (t )]1/ 2
Fven (rc )drc , (5.8.17)

where rc,min is again defined so that the expressions under square root are positive. Introducing a new
variable rc′,

rc′ = [(rc + ξ dep )2 − Qi (t )]1/2 − ξ dep . (5.8.18)

and substituting this into (Eqn. 5.8.17) and omitting the prime at rc′ in the final equation, we obtain
∞

τ −fc1 = 4π Dvζ i ∫ Rc [(rc , ξ dep ) fd3/6 (rc , t ) Fven (rc ) drc ,

0

{[(rc + ξ dep )2 + Qi (t )]1/2 − ξ dep ]}2

R c (rc , ξ dep ) = (5.8.19)
[(rc + ξ dep )2 + Qi (t )]1/2
5.8. Fast Algorithms for Microphysics Modules in Multidimensional Models 177

Thus, the quantities τ −1 −1

fd and τ fc are expressed now via the size spectra fd(rd) and fc(rc) after the sub-

step 3/6 of the splitting—i.e., after spatial transport and before the condensation substep.
Differentiating (Eqn. 5.8.10) for Qw by time and substituting into (Eqn. 5.8.6) for Dw, we obtain an
equation for Qw of the second order by time,

d 2Qw  Γ  dQ 2 Dv ρ a Γ12 −1
= − τ −fd1 + 12 τ −fc1  w − τ fc (qws − qis ) +
dt 2  Γ 2  dt ρ w Γ1Γ 2

2 Dv ρ a ∂qws
( − )+ (γ a w − Rrad ), (5.8.20a)
ρ w Γ w ∂T

where τ −1 −1
fd and τ fc are defined in (Eqns. 5.8.16) and (5.8.19). Substituting these expressions for
−1 −1
τ fd and τ fc , we obtain the equation for the integral normalized supersaturation Qw in a closed form

d 2Qw dQw  ∞ ∞

= − 4π Dv  ∫ Rd (rd , ξ con ) fd (rd , t ) Fven (rd ) drd + ∫

dt 2 dt  0
∞
Γ wi
∞

∫ d drd + ζ i
Γi ∫ R (r
0
c c, ξ dep ) fc (rc , t ) Fven (rc ) drc  −


 8π D ρ a (qsw − qsi ) Γ wiζ i

2 ∞

− ∫ R (r ξ dep ) fc (rc , t ) Fven (rc ) drc +

v

ρw Γ wΓi
c c,
 0

2 Dv ρ a ∂qsw
rc + (γ a w − Rrad ), (5.8.20b)
ρ w Γ w ∂T
c

This is the integro-differential equation for Qw of the second order by time analogous to the equations
for the integral supersaturations yw, yi derived in Section 5.5. This equation is also used for studies
of drop activation in Chapters 6 and 7 and ice nucleation and the parcel modeling in Chapters 8–10.
Despite a slightly complicated form, the solution of this equation is sufficiently simple and con-
sists of several steps.

1. The supersaturation relaxation times τ −1 −1

fd and τ fc are calculated using (Eqn. 5.8.16),

(Eqn. 5.8.19) and the size spectra after the splitting substep 3/6—that is, after the spatial transport.
2. Then a simpler (Eqn. 5.8.20a) is solved instead of (Eqn. 5.8.20b). The solution is per-
formed within a special microphysical module, which solves together a system of equa-
tions including (Eqn. 5.8.10) for dQw/dt, (Eqn. 5.8.20a) for dQw2/dt2, and (Eqn. 5.8.8) for
dT/dt. This system is solved using the Runge–Kutta method. The major advantage of this
scheme developed by M. V. Buikov with pupils (Buikov and Pirnach, 1973, 1975; Buikov and
Khvorostyanov, 1976, 1977) is that the algorithm is very economic and fast. The main (dynam-
ical) time step Dt in the model can be rather large, from 10 s to 5–10 min, comparable to those
used in mesoscale or even climate models, and (Eqns. 5.8.1) for spatial transport of tempera-
ture, humidity, and size spectra are solved with this large time step at the first three of six sub-
steps of splitting. Then, the system of (Eqns. 5.8.10) for dQw /dt, (Eqn. 5.8.20a) for dQw2/dt2,
and (Eqn. 5.8.8) for dT/dt are solved in a separate subroutine with a smaller (microphysical)
178 Diffusion and Coagulation Growth of Drops and Crystals

time step Dtmic. This small step Dtmic is chosen in this subroutine by comparison with relaxation
times tfd, tfc. It is obtained by dividing the main time step Dt by some number Nt (e.g., 2 to 5)
and is compared with tfd and tfc. If Dtmic > tfd, or Dtmic > tfc, Dt is divided again by Nt, and this
procedure is repeated until the conditions are satisfied Dtmic < tfd, and Dtmic < tfc. This ensures
computational stability in calculations of diffusion growth as was mathematically proven in
cited works by Buikov et al. After evaluation of tfd and tfc, the time step Dtmic is chosen auto-
matically in this microphysical subroutine to satisfy the described stability conditions, the
number of these small substeps is calculated as nt = Dt/Dtmic, and this system of equations is
integrated nt times with Dtmic over the entire Dt. Generally, tfd and tfc are different at every grid
point, therefore Dtmic and nt should be chosen separately at each grid point. If the liquid phase
is present, then Dtmic < tfd ~ 1–10 s, and if a cloud is pure crystalline like cirrus, then Dtmic < tfc
and can be much greater, a few tens or hundreds of seconds or a few minutes (see Section 5.3,
Tables 5.1 and 5.2). After integration, Qw(Dt), Qi(Dt), dQw(Dt)/dt, and dQi(Dt)/dt are known,
and then Dw, sw and Di, si are calculated with (Eqn. 5.8.10).
3. Finally, the “new” size spectra fd4/6 and fc4/6 after the condensation and deposition substep
4/6 are calculated with known Qw(Dt), Qi(Dt) using (Eqns. 5.8.11) and (5.8.12). The advan-
tage of this method is that the use of the integral supersaturations Qw(t), Qi(t) along with
(Eqns. 5.8.11) and (5.8.12) allows us to recalculate the distribution functions only once during
the complete and relatively large time step Dt and enables us to substantially decrease com-
putational diffusivity in the space of radii, which may occur in the other numerical techniques
with multiple recalculations at each small time step. Note that the same method for microphys-
ics is used in the parcel model simulations described in Chapters 8 and 9, where the substeps
from 1/6 to 3/6 with spatial transport are absent.

During the fifth substep 5/6, coalescence and accretion of droplets and crystals are calculated
using the kinetic equations of coagulation described in Section 5.6 using size spectra fd4/6 and fc4/6
after the condensation substep as the initial data. Various algorithms were developed for solution of
the coagulation equation, one of the best is the fast and precise effective flux method developed by
Bott (1998, 2000, 2001) that can be used for a numerical solution of the collection equations. A sim-
pler but less precise approach for calculations of the coagulation and accretion rates, the approxima-
tion of continuous growth, is still used in some cloud models. It is described in Chapter 14.
At the end of the time step, at substep 6/6, activation of droplets is calculated as described in
Chapters 6 and 7, and nucleation of crystals is calculated as described in Chapters 8, 9, and 10.
The final values of T, q, fd, and fc obtained after all six substeps are used as initial data at the begin-
ning of the next time step.
In the microphysical units of the model, a finite-difference grid is used, which includes Nx, Ny,
and Nz gridpoints in the horizontal and vertical directions with spacing of Dx, Dy, and Dz. These
parameters are varied as described in the numerical experiments. For example, in the 3D version of
the model described in Khvorostyanov, Curry et al. (2003) with simulations of fog and Sc clouds
observed over Arctic polynya in the Beaufort Sea in the SHEBA-FIRE field experiment, there were
21 × 21 horizontal grid points with the steps Dx = Dy = 3 km, and 31 vertical levels with resolution
5.8. Fast Algorithms for Microphysics Modules in Multidimensional Models 179

33.3 m. The droplet and crystal size ranges were divided into 30 intervals from 0.1 mm to 3.5 mm
with logarithmically increasing spacing. The initial T and q fields are specified for each simulated
case using the data of sounding, aircraft, and surface observations. With the configuration of this
spectral 3D model, due to fast microphysics algorithms with combinations of large and small time
steps, it was possible to perform simulations on a PC Pentium. The model satisfactorily reproduced
the characteristics of the cloudy boundary layer, evolving size spectra of drops and crystals and their
moments, supersaturation, phase state, and surface heat fluxes, as was shown in this work by com-
parison with observations for that case, and was confirmed later by Raddatz et al. (2011, 2012) in
observations of similar cloudy boundary layers and heat fluxes over Arctic polynyas.
6
Wet Aerosol Processes

6.1. Introduction

Interactions of atmospheric aerosol particles with humidity result in the transformation of aerosol
properties and size spectra. At low humidities, a thin water film can be adsorbed on the surface of an
aerosol particle. The result of this adsorption can be a monolayer of water molecules or a water film
of several water molecules thick on the surface of the aerosol particle. The particles of atmospheric
aerosol usually consist of soluble and insoluble fractions and are termed “mixed” aerosol particles.
The aerosol population of one sort with the same properties and chemical composition of each par-
ticle is called “internally mixed,” and aerosol consisting of several sorts of particles with different
composition and properties is called “externally mixed.” Detailed reviews of various types of atmo-
spheric aerosols, their properties, and the mechanisms and models of their formation are given, for
example, in Fuchs (1959, 1964), Levin (1954), Junge (1963), Pruppacher and Klett (1997), Sedunov
(1974), and Seinfeld and Pandis (1998).
Aerosol particles may have an adsorbed liquid film on the surface but are solid inside if they are
insoluble or if environmental water saturation ratio Sw (or relative humidity H = 100 Sw) is below
some critical value called the threshold of deliquescence saturation ratio Sw,del (or threshold deliques-
cence humidity). If the saturation ratio increases and exceeds the threshold of deliquescence Sw,del,
the soluble fraction deliquesces (see Chapter 11), and the hygroscopic growth of the particles begins
as they accumulate more water. These mixed aerosol particles convert into solution or haze particles
comprised of a liquid solution and an insoluble core. The solution contains water and an aerosol
soluble fraction, while the insoluble fraction or insoluble core still remains in the solid state. Haze
droplets are generally of submicron sizes.
The equilibrium size at increasing humidity is reached rapidly. The time of relaxation to
equilibrium size for a particle with wet radius rw at saturation ratio Sw can be estimated as
τ eq ≈ 0.4rw2 /[ Dv ( ρ v /ρ w )(1 − Sw )] (Sedunov, 1974), and are ~10−4, 10−2, and 1–2 s, for the submicron
particles with the radii ~0.01, 0.1, and 1 mm (Sedunov, 1974; Pruppacher and Klett, 1997). If the
relative humidity increases further and reaches values slightly above 100%, or water supersaturation
reaches some critical value scr, the aerosol particles are said to be activated and become capable of
unlimited growth. Aerosol particles that have appropriate properties to form drops by activation are
termed cloud condensation nuclei (CCN).
Hygroscopic growth of aerosol particles influences aerosol radiative properties and the direct
aerosol effect on climate. Activation of cloud drops influences cloud microphysical and radiative
properties and influences the indirect aerosol effects on climate: an increase in aerosol concentra-
tions (e.g., anthropogenic pollutions, volcanic eruptions) causes the first indirect or Twomey effect

181
182 Wet Aerosol Processes

(albedo increase, Twomey, 1977). This increase in aerosol concentrations may result in the forma-
tion of higher concentrations of smaller droplets, which hamper coagulation and cause precipitation
decrease and longer cloud life times. This is termed the second indirect or Albrecht effect (Albrecht,
1989). Both of these indirect effects are important for the studies of climate change (Intergovernmen-
tal Panel on Climate Change, IPCC-2007; Lohmann and Feichter, 2005; McFiggans et al., 2006).
Both hygroscopic growth and CCN activation are described by the Köhler equation. The Köhler
equation for the saturation ratio expresses the equilibrium size of the solution droplet as the balance be-
tween the curvature (Kelvin) effect and the solute (Raoult) effect as described in Chapter 3, Section 3.9.
Some features and previous parameterizations of aerosol hygroscopic growth and CCN activation are
briefly reviewed in this section, while theoretical descriptions of these processes based on the Köhler
theory and its generalizations are presented in other sections of this chapter.

6.1.1. Empirical Parameterizations of Hygroscopic Growth

Numerous measurements of aerosol properties at varying humidity have shown that the radii of aero-
sol particles, in general, increase with increasing humidity. This feature, called hygroscopic growth,
is usually parameterized either with equations for the dependence of the radius rw of wet aerosol on
the water saturation ratio Sw (or on the relative humidity H = 100Sw) as

rw ( Sw ) = rd [ Aw + Bw (1 − Sw )−γ 1 ], (6.1.1a)
rw ( Sw ) = α g ( Sw )rdγ 1 , (6.1.1b)

where ag(Sw) is some function of the water saturation ratio, or by the growth factor GF(Sw) = rw(Sw)/rd,
where rw and rd are the wet and dry radii, and Sw is the water saturation ratio.
The function GF(Sw) and the humidity impact on aerosol extinction coefficient sext are often pa-
rameterized with empirical relations of the type
GF ( Sw ) = Aw + Bw (1 − Sw )−γ 1 , (6.1.2)
−γ 2
σ ext ( Sw ) ~ (1 − Sw ) , (6.1.3)

or nonlinear expressions similar to (Eqn. 6.1.1b). The quantities Aw, Bw, g1, and g2 are empirical param-
eters determined by fitting experimental data (e.g., Kasten, 1969; Hegg et al., 1996; Kotchenruther
et al., 1999; Swietlicki et al., 1999; Zhou et al., 2001) or by fitting functional dependencies for
GF(Sw) found from approximate analytical solutions of the Köhler equation combined with analysis
of the experimental data (e.g., Fitzgerald, 1975; Khvorostyanov and Curry 1999a,b, 2006; Swietlicki
et al., 1999; Cohard et al., 2000; Kreidenweis et al., 2005; Rissler et al., 2006). Some parameterizations
assumed Aw = 0 (e.g., Kasten, 1969), and some tested more complicated functions of Sw and other
aerosol properties (e.g., Hänel, 1976; Kotchenruther et al., 1999).
A more detailed evaluation of hygroscopic growth and GF(Sw) was based on numerical solutions
of the Köhler equation with comprehensive parameterizations of its parameters as functions of the
solution concentration. This approach is also used to constrain aerosol physico-chemical properties
from the hygroscopic data for subsequent evaluation of the critical radii rcr and critical supersatu-
rations scr that determine activation of an aerosol particle into a cloud drop (e.g., Fitzgerald, 1975;
Hänel, 1976; Fitzgerald et al., 1982; Chen, 1994; Brechtel and Kreidenweis, 2000a,b; Hämeri et al.,
6.1. Introduction 183

2000, 2001; Snider et al., 2003). Numerical solutions may be more precise and complete, but are
more time-consuming. The analytical solutions are desirable since they provide a basis for develop-
ment of simple and fast parameterizations for cloud and climate models. Besides evaluation of the
sizes of individual wet particles, one of the major tasks in descriptions of hygroscopic growth is the
evaluation of transformation of the initially dry spectra fd(rd) by the dry radius rd into the wet spectra
fw(rw) by the wet radius rw and analytical representation of the size spectra fw(rw) of wet aerosol.

6.1.2. Empirical Parameterizations of Droplet Activation

One of the major results of the Köhler theory was the derivation of analytical expressions for the
CCN critical radii rcr and supersaturations scr. These quantities play a fundamental role in aerosol-
cloud interactions since they determine the concentration of cloud drops, and have been widely used
in cloud and climate studies for parameterizations of cloud drop formation (for overviews of earlier
works, see, for example, Mason, 1961; Dufour and Defay, 1963; Sedunov, 1974; Matveev, 1984;
Cotton et al., 2011; Rogers and Yau, 1989; Houze, 1993; Young, 1993; Pruppacher and Klett, 1997;
Seinfeld and Pandis, 1998; Curry and Webster, 1999).
The two key functions of drop activation are the differential, js(scr), and integral or cumulative,
NCCN(scr), CCN activity spectra. The differential spectrum js(scr) determines the increase in activated
CCN per a small increase of supersaturation and is a starting point for evaluation of the cumula-
tive spectrum NCCN(scr) that determines the drop concentration formed at a given scr. Knowledge of
analytical expressions for rcr and scr allow analytical evaluation of js(scr) and NCCN(scr) from the dry
aerosol size spectrum fd(rd).
The first CCN activity spectrum was suggested by Squires (1958) and Twomey (1959) in the form
of a power law by the water supersaturation sw reached in a cloud parcel:

N CCN (s) = Cswk . (6.1.4)

This parameterization has been the most commonly used parameterization of the concentration of
cloud drops or CCN activity spectrum for more than five decades. Numerous studies have provided a
wealth of data on the parameters k and C for various geographical regions (see, e.g., Hegg and Hobbs,
1992, and Table 9.1 in Pruppacher and Klett, 1997). Parameterizations of the type (Eqn. 6.1.4) were
derived by Squires (1958) and Twomey (1959) using several assumptions and similar power laws for
the differential CCN activity spectrum, j s (sw):

ϕ s (sw ) = dN CCN / dsw = Ckswk−1 . (6.1.5)

Equations (6.1.4) and (6.1.5) have been used in many cloud models with empirical values of k and C
that are assumed to be constant for a given air mass and are usually constant during model runs.
The empirically derived power law supersaturation activity spectra (Eqns. 6.1.4) and (6.1.5) ex-
plained some features of drop nucleation, but did not have a theoretical foundation. To interpret
these empirical dependencies, models were developed of partially soluble CCN with the size spectra
−( µ −1)
of Junge-type power law f(r) = CNr−m (total aerosol concentration N a ∼ rmin ) and the index k was
expressed as a function of m. Jiusto and Lala (1981) found a linear relation
k = 2( µ − 1)/3, (6.1.6)
184 Wet Aerosol Processes

which implies k = 2 for a typical Junge index m = 4, while the experimental values of k compiled in
that work varied over the range 0.2–4. Levin and Sedunov (1966a), Sedunov (1974), Smirnov (1978),
Cohard et al. (1998, 2000), and Shipway and Abel (2010) derived more general power laws or alge-
braic equations for js(sw) and expressed k as a function of m and CCN soluble fraction. Khvorostyanov
and Curry (1999a,b) derived power laws for the size spectra of the wet and interstitial aerosol, for
the activity spectra js(sw), jCCN(s) and for the Ångström (1929, 1964) wavelength l index kA of the
aerosol extinction coefficient sext and optical thickness ta

σ ext ~ λ − k A , τ a ~ λ − kA (6.1.6a)

and found linear relations among these indices expressed in terms of the index m and the aerosol
soluble fraction.
A deficiency of (Eqn. 6.1.4) is that it overestimates the droplet concentration at large sw and pre-
dicts unlimited values of droplet concentration that exceed total aerosol concentration. This occurs
because of the functional form of the power law and use of a single value of k for the entire sw range.
Many field and laboratory measurements have shown that a more realistic NCCN(sw) spectrum in log-
log coordinates is not linear as it would be with k = const, but has a concave curvature—i.e., the index
k decreases with increasing sw (e.g., Jiusto and Lala, 1981; Hudson, 1984; Yum and Hudson, 2001).
This deficiency in (Eqn. 6.1.4) has been corrected in various ways.
Braham (1976) introduced the C-k space with wide ranges for both parameters and constructed
nomograms in this space. Cohard et al. (1998, 2000) and Shipway and Abel (2010) introduced an
empirical correction to Twomey’s spectrum js(sw) that rapidly decreases at high sw:

ϕ s (sw ) = kCswk−1 (1 + ηsw2 )− λ , (6.1.7)

where the first term is Twomey’s differential power law (Eqn. 6.1.5), and the term in parentheses was
added by the authors as an empirical correction with the two additional empirical fitting parameters h,
l in order to cut js(sw) at high sw. Ji and Shaw (1998) suggested another analogous integral empirical
spectrum NCCN(sw) with two empirical parameters BJS and k:

N CCN (s) = Na [1 − exp(− BJS swk )], (6.1.8a)

which tends to a correct finite limit Na at high sw and corresponds to the differential activity spectrum

ϕ s (sw ) = Na BJS kswk−1 exp(− BJS swk ) (6.1.8b)

Khvorostyanov and Curry (1999a) considered the change in the indices m, k in different CCN size
ranges. Several authors proposed using a lognormal CCN size spectrum instead of the power law,
which yields lognormal concave activity spectra and finite Ndr at high sw (von der Emde and Wacker,
1993; Ghan et al., 1993, 1995, 1997; Feingold et al., 1994; Abdul-Razzak et al., 1998; Abdul-Razzak
and Ghan, 2000, 2004; Nenes and Seinfeld, 2003; Rissman et al., 2004; Fountoukis and Nenes,
2005). Based on these studies, the prognostic equations for the drop concentration were incorporated
into climate models (Ghan et al., 1997; Lohmann et al., 1999).
Analytical expressions for rcr and scr have usually been determined from the Köhler equation with
the following approximations: 1) high dilution in a haze drop (i.e., neglecting the insoluble CCN
fraction in the denominator of Raoult’s term); 2) soluble fraction proportional to the drop volume;
and 3) small supersaturations. Concerns about each of these three assumptions are described next.
6.1. Introduction 185

1. Many recent field experiments have found aerosols with very small aerosol soluble fractions
or aerosol particles that are nearly hydrophobic, often constituting a significant fraction of the
total aerosol load. These field experiments have been conducted over many different regions:
in desert areas (Levin et al., 1996; Rosenfeld et al., 2001), the Arctic (Curry et al., 2000; Pinto
et al., 2001; Leck et al., 2001; Bigg and Leck, 2001a,b), and the Aerosol Characterization Experi-
ments 1 and 2, ACE-1 and ACE-2, (Swietlicki et al., 2000; Snider et al., 2003). Earlier detailed
numerical calculations show that even at the time of activation, the degree of dilution (ratio of
gained water mass to the dry mass) for the aerosol particles with the small insoluble fraction
~0.01 can be as low as 0.8 and ~2 for the dry radii rd = 0.02 and 0.1 mm—i.e., near the modal
radii for many aerosols (e.g., Hänel, 1976; Pruppacher and Klett, 1997, Table 6.3). Therefore,
the high dilution approximation may not be satisfied, and therefore analytical solutions to the
Köhler equation without high dilution approximation are desirable.
2. The model of internally mixed aerosol particles with soluble fraction proportional to the particle
volume has been challenged in several papers. A surface-proportional soluble shell was found
in CCN measurements in several regions of Eastern Europe (e.g., Laktionov, 1972; Sedunov
1974). Levin et al. (1996), Falkovich et al. (2001), and Rosenfeld et al. (2001) found that min-
eral dust particles coated with thin sulfate shells are typical in the eastern Mediterranean. It was
hypothesized that several mechanisms may be responsible for such soluble shells—e.g., coagu-
lation of the mineral dust with sulfate particles, deposition of sulfate on desert particles with
oxidation of SO2 or SO4 on the particle surface, and nucleation of cloud drops on sulfate CCN
with subsequent accumulation of mineral dust and evaporation of drops leaving sulfate-coated
dust. Simulations of heterogeneous chemical reactions and soluble shells on the dust surface
showed their significant impact on the aerosol composition (Wurzler et al., 2000) and on radia-
tive forcing in the GISS GCM (Bauer and Koch, 2005).
3. In some aerosol chambers, very high supersaturations are reached, sw ~ 15–25%, violating the
assumption of small sw. Since the lower size boundary of activated CCN is inversely propor-
tional to sw (Sedunov 1974; Ghan et al., 1993; Khvorostyanov and Curry, 1999a), this may lead
to activation of very small aerosol particles with radii rd << 0.01 mm, whose rcr and scr can be
different than those in the accumulation mode. Thus, the approximation of a small sw should be
eliminated for accurate interpretation of aerosol/cloud chamber experiments.

The Köhler theory and its generalizations without these limitations are described in this chapter.
The older power law and newer lognormal parameterizations of aerosol size spectra and super-
saturation activity spectra are widely used in studies of aerosol optical and radiative properties,
cloud physics, and climate research. These two kinds of parameterizations existed in parallel, and
implicitly compete, but their relation was unclear. A bridge between these two types of the size
spectra and activity spectra was established by Khvorostyanov and Curry (2006, 2007), where a
new class of size spectra and activity spectra was found: the algebraic distributions. These new
distributions allowed: a) to show the equivalence and applicability of the power laws and lognormal
spectra; and b) to develop a generalization of the power law (Eqn. 6.1.4), and to find the k-index and
C-coefficient as continuous analytical functions of supersaturation and of the aerosol microphysics
and chemistry.
186 Wet Aerosol Processes

The approach developed by Khvorostyanov and Curry (2006, 2007) appeared to be convenient
for use in both bin and bulk cloud models (e.g., Morrison and Grabowski, 2007, 2008; Curry and
Khvorostyanov, 2012). In Sections 6.2–6.7, the Köhler theory and its modification are described.
A model of mixed (partially soluble) dry CCN is developed with parameterization of the soluble
fraction as a function of the dry nucleus radius; analytical solutions are found for the equilibrium wet
radius in the hygroscopic growth and of unactivated particles in the cloud (Section 6.2). The Köhler
theory for the critical radius and supersaturation is described and generalized, with account taken for
the insoluble fraction and various geometries of soluble fractions (Section 6.3). The lognormal size
spectrum of the dry aerosol is described and its two equivalents are derived as a power law Junge-type
spectrum and a new algebraic spectrum (Section 6.4). The analytical transformations of the aerosol
size spectra at varying humidity are derived for the general shape of the dry spectrum, lognormal, and
algebraic spectrum (Section 6.5). The differential and integral CCN activity spectra are derived in the
lognormal, equivalent algebraic, and modified power law forms (Section 6.6 and Section 6.7). Some
recent modifications of the Köhler theory are described in the next section.

6.2. Equilibrium Radii

We considered in Chapter 3 the Kelvin effect of vapor pressure increase over a droplet due to its
curvature, and the pressure decrease due to Raoult’s solution effect. Köhler (1921, 1936) wrote an
equation for water saturation ratio Sw, which accounted for the curvature and solution effects, and
considered their joint effect on a solution drop. This equation was called the Köhler equation, which
determines the critical conditions when deliquesced aerosol particles (CCN) in their hygroscopic
growth reach critical radii and supersaturations and thus “activate” into cloud droplets.
Subsequent to Köhler’s pioneering work, there have been numerous derivations of the Köhler
equation from basic thermodynamic principles with a variety of refinements (e.g., Dufour and Defay,
1963; Defay et al., 1966; Low, 1969; Sedunov, 1974; Young and Warren, 1992; Pruppacher and
Klett, 1997; Chylek and Wong, 1998; Curry and Webster, 1999). Various modifications to the Köhler
theory accounted for the solubility limitation of the soluble CCN fraction that allowed description
of deliquescence and humidity hysteresis (Chen, 1994); absorption of the soluble gases by the haze
drops that led to additional terms and yielded multimodal Köhler-type curves for CCN activation
(Kulmala et al., 1993; Schulman et al., 1996; Laaksonen et al., 1998); effects of the insoluble frac-
tion of the equilibrium CCN radii and critical saturations (Khvorostyanov and Curry, 1999a,b; 2006,
2007, 2008a, 2009a); and adsorption of the water film on the surface of insoluble aerosol particles
(e.g., Henson, 2007; Sorjamaa and Laaksonen, 2007). Prior to 2000, a detailed analysis of several
versions of the Köhler equation and of approximations in evaluation of its several basic parameters,
solvent and solute volume additivity, surface tension, osmotic potential, and other facets are given in
Brechtel and Kreidenweis (2000a), Charlson et al. (2001), and Kreidenweis et al. (2005).
In this section, we consider the version of the Köhler equation that takes into account the in-
soluble fraction, which describes the equilibrium water vapor pressure over a solution drop that
consists of soluble and insoluble components and is in equilibrium with ambient humid air. Then,
following mostly the approach developed in Khvorostyanov and Curry (2006, 2007) with convenient
parameterization of the soluble fraction, we find the analytical solutions for the equilibrium radii of
6.2. Equilibrium Radii 187

deliquescent aerosol at subsaturation, and for the equilibrium and critical radii and supersaturations
of interstitial aerosol at water saturation in a cloud. These solutions are used for derivation of the
equilibrium size spectra of the dry and wet aerosol and of the CCN activity spectra. The modifica-
tions of the Köhler equation and their solutions, as developed in the works of authors cited earlier, are
described in subsequent sections.

6.2.1. Equilibrium Radii at Subsaturation

Below a certain threshold saturation ratio Sw,th, the aerosol particles are solid. They can be covered
by a thin adsorbed water film but they do not deliquesce. The thresholds of deliquescence for the
most common substances met in the atmosphere are, for example, Sw ~ 0.75 for sodium chloride,
NaCl, and ~0.8 for ammonium sulfate, (NH4)2SO4, at room temperatures of 15 to 25 °C, which
slightly grow with decreasing temperature. The process of deliquescence and a reverse process of ef-
florescence are considered in Chapter 11. As the water saturation ratio Sw (equal to fractional relative
humidity, Sw = H) exceeds the threshold of deliquescence Sw,th of the soluble fraction, the hygroscopic
growth of the particles begins, and an initially dry CCN with radius rd converts into a wet aerosol
particle with radius rw called a “haze particle.”
The equilibrium radius of the wet aerosol rw(Sw) as a function of the ambient saturation ratio Sw (or
of the relative humidity H) and of the dry radius rd can be obtained using the Köhler equation for Sw
or supersaturation sw = (rv − rws)/rws = Sw − 1 (see Section 3.9),
2 M wσ sa ν Φs M w ms
ln Sw = − , ms = ε m md = ε v ρ sVd , (6.2.1)
RT ρ w r M s mw

where ms is the mass of the soluble fraction, em and ev are the mass and volume fractions of the
soluble fraction, rs is the density of the soluble fraction, and all the notations here are the same as in
Section 3.9. The first term here describes the Kelvin curvature effect, and the second term describes
Raoult’s solution effect. The volume fraction ev is related to the mass fraction em as ev = em(rd /rs),
where rd is the effective density of a dry aerosol particle, weighted by the densities of its soluble rs
and insoluble ru fractions, rd = e vrs + (1 − ev)ru.
Using the simplifying assumptions on the constancy of the water molar volume in solution and the
volume additivity of solvent (water) and solute (salt), V = Vw + Vd, which are good approximations
for many common ionic solutes (Dufour and Defay, 1963; Pruppacher and Klett, 1997; Brechtel and
Kreidenweis, 2000a; Kreidenweis et al., 2005), the ratio md /mw can be expressed as md /mw = (rd /rw)
[(rw /rd)3 − 1]−1. Substitution of these relations into (Eqn. 6.2.1) yields:
Ak B
ln Sw = − . (6.2.2a)
rw rw3 − rd3
2 M wσ sa 3ν Φs ε m md M w 3ν Φs ms M w
Ak = , B= = . (6.2.2b)
RT ρ w 4π M s ρ w 4π M s ρ w

Here Ak is the Kelvin curvature parameter, and the parameter B, called the activity of a nucleus,
describes effects of the soluble fraction. Note that here the dimension of parameter B is [cm3] and
this definition of B is different from the dimensionless B in Pruppacher and Klett (1997, p. 178).
188 Wet Aerosol Processes

It is written here in a form that allows generalization for various soluble fractions, proportional to the
volume or surface of CCN as clarified in the following text.
The solute effect in the second term in (Eqn. 6.2.1) is often parameterized using the hygroscopicity
parameter kh. It is introduced with an assumption that the soluble fraction is proportional to the vol-
ume of an aerosol particle, thus the mass of the soluble fraction ms = emmd = evrsVd. Then, the second
term in (Eqn. 6.2.1), equal to ln(aw), can be written as
ν Φs M w ε m md ν Φs M w ε m ρ d Vd
ln aw = − =− , (6.2.3a)
Ms mw M s ρw Vw

where Vd and Vw are the volumes of the dry particulate mass and water in a solution droplet. The
hygroscopicity parameter kh is introduced by a relation (e.g., Petters and Kreidenweis, 2007)
Vd
aw−1 = 1 + κ h . (6.2.3b)
Vw

Combining (Eqns. 6.2.3a) and (6.2.3b) yields

 ν Φs ε m M w ρ d Vd  ν Φs ε m M w ρ d Vd V
aw−1 = exp  ≈ 1+ = 1+κ h d . (6.2.3c)
 M s ρw Vw  M s ρw Vw Vw

This gives the expression for kh:

ν Φs ε m M w ρ d ν Φs ε v M w ρs
κh= = . (6.2.3d)
M s ρw M s ρw

A generalization for several substances is done by summation over n soluble components in an aero-
sol particle (e.g., Ghan et al., 2011):

∑qκ i hi /ρ di
κh= i
, (6.2.3e)
qi /ρ di

where khi is the hygroscopicity parameter for the i-th soluble species determined by (Eqn. 6.2.3d), qi
and rdi are the mass fractions, and the density of the component i.
The deficiencies of the approach based on the hygroscopicity parameter are: expansion of aw in
(Eqn. 6.2.3c) is valid for sufficiently diluted solutions, and the explicit assumption of proportional-
ity of soluble fraction to the particle volume. Both assumptions have limitations. 1) The expansion
(Eqn. 6.2.3c) for aw becomes invalid for sufficiently concentrated solutions in the drop and introduces
noticeable errors, which is especially pronounced for smaller soluble fractions. 2) The assumption
of the soluble fraction proportional to the volume is invalid for the particles whose soluble fraction
represents a shell on the surface of an insoluble core.
We employ a more general and convenient parameterization of the soluble fraction and nucleus
activity (Levin and Sedunov, 1966a; Sedunov, 1974; Smirnov, 1978; Khvorostyanov and Curry,
1999a,b, 2006, 2007, 2008a, 2009a) that easily allows incorporation of alternative assumptions
regarding the soluble fraction of the aerosol particle:

B = brd2(1+ β ) , (6.2.4)
6.2. Equilibrium Radii 189

where the parameters b and b depend on the chemical composition and physical properties of the
soluble part of an aerosol particle. According to (Eqn. 6.2.2b), B ~ ms, the mass of the soluble fraction
ms ~ rd2(1+ β ) and the parameter b describes the soluble fraction in a particle. Generally, the solubility
decreases with increasing particle size (e.g., Laktionov, 1972; Sedunov, 1974; Pruppacher and Klett,
1997), so that b decreases with increasing rd and may vary from 0.5, when the soluble fraction is pro-
portional to the volume, to 0, when the soluble fraction is proportional to the surface, and to −1, when
the soluble fraction is independent of the radius. This variation describes the change of the dominant
mechanisms of accumulation of the soluble fraction with growing particle size. A detailed analysis
of these mechanisms is given, e.g., in Junge (1963), Pruppacher and Klett (1997), and Seinfeld and
Pandis (1998), and an interested reader can find the details in these books. We consider in more detail
two particular and most important cases.

1. b = 0.5. The value b = 0.5 corresponds to the case ms ~ B = brd3. When the soluble fraction is
distributed within the particle volume, the soluble mass is proportional to the volume, and this
is usually implicitly assumed in most parameterizations of CCN deliquescence and drop activa-
tion (e.g., von der Emde and Wacker, 1993; Ghan et al., 1993, 1995; Abdul-Razzak et al., 1998;
Abdul-Razzak and Ghan, 2000; Ghan et al., 2011). The parameter b can be found by equating the
second equation of (Eqns. 6.2.2b) and (6.2.4) (Khvorostyanov and Curry, 1999a, 2006, 2007).
3ν Φs ms M w
B= = brd2(1+ β ) , (6.2.5)
4π M s ρ w

and writing the mass of the soluble fraction as ms = (4/3)pevrsrd3, where rs is the density of the
soluble fraction, and ev is its volume fraction. This gives with b = 0.5 that b is a dimensionless
parameter:
ρs M w ρ M
b = (ν Φs )ε v = (ν Φs )ε m d w , (6.2.6)
ρw M s ρw M s

where ev and em are the volume and mass fractions of a CCN. For b = 0.5, ev and em do not
depend on the dry radius rd. The value of Φs, in general, also depends on rw, however this
effect on rcr and scr is weaker than those of the other factors (Brechtel and Kreidenweis, 2000a).
When evaluating b, Φs can be assigned some appropriate mean constant value, e.g., n Φs ≈ 2.1
for ammonium sulfate, rather than 3, which yields a good approximation (Snider et al., 2003),
or the available parameterizations for Φs (e.g., Brechtel and Kreidenweis, 2000a) can be sub-
stituted into the final equations for rw, rcr, and scr. For example, using the typical parameters in
(Eqn. 6.2.6) for the case b = 0.5 yields for ammonium sulfate: b ≈ 0.5 for fully soluble nuclei
(ev = 1), and b ≈ 0.25 with ev = 0.5. For NaCl, the values are: b ≈ 1.33 with ev = 1, and b ≈ 0.67
with ev = 0.5. This case with ms ~ rd3 is analogous to that usually considered in the literature,
and b is analogous to the hygroscopicity parameter kh.
2. b = 0. Then B = brd2—i.e., mass of soluble fraction is proportional to the surface area where it is
accumulated as a soluble film or shell at the surface of an aerosol particle. The particle volume
fraction ev and b can be parameterized as
rd ,sc ρs M w
ε v = ε v0 , b = rd ,sc ε v 0 (ν Φs ) , (6.2.7)
rd ρw M s
190 Wet Aerosol Processes

where rd,sc is some scaling radius and ev0 is the reference soluble fraction (dimensionless). For
this case, b has the dimension of length and is proportional to the scaling radius rd,sc that char-
acterizes the thickness l0 of the soluble film (but is not equal to it). Such a model is based on the
experimental data by Laktionov (1972), Sedunov (1974), Levin et al. (1996), Falkovich et al.
(2001), Rosenfeld et al. (2001) and some theoretical models (Wurzler et al., 2000; Bauer and
Koch, 2005) discussed earlier. A detailed chemical analysis in Levin et al. (1996) showed that
the surface density Ps = ms /Sp (Sp = 4p rd2 is the particle surface area) of the sulfates was fairly
constant with particle size, Ps ~ (2 − 6) × 10−6 g cm−2, in the range rd = 0.15 to 10 mm. This in-
dicates that ms ~ Sp ~ rd2 and supports parameterization of soluble fraction mass ms proportional
to the surface area with b = 0. Assuming a thin shell with the thickness l0 << rd and volume
Vs = 4p rd2l0, we can estimate l0 from the relation Ps = ms /Sp ≈ 4prsrd2l0 /4p rd2 = l0 rs, or l0 = Ps /rs.
With rs ~2 g cm−2. This yields an estimate l0 ~ 0.01–0.03 m m, where l0 << rd in this radii range.

For this model of aerosol particles with a thin soluble shell, the soluble mass fraction is inversely
proportional to the dry radius

ms 4π rd2l0 ρs 3l ρ
εm = ≈ 3
= 0 s, (6.2.8)
md (4 /3)π rd ρ d rd ρ d

Substituting this relation into (Eqn. 6.2.7), we obtain the parameter b that has the dimension of length
ρd M w
b = 3l0 (ν Φs ) . (6.2.9)
ρw M s

This parameterization requires knowledge of the soluble film thickness l0 that can be obtained from
experimental data (e.g., Levin et al., 1996; Falkovich et al., 2001), or simulations (e.g., Wurzler et al.,
2000; Bauer and Koch, 2005). If the soluble and insoluble masses are known, as in many current
climate and pollution transport models, then the hygroscopicity can be expressed using parameteriza-
tion (Eqns. 6.2.4), (6.2.6), and (6.2.9) assuming some insoluble core geometry and proportionality
of the soluble mass to the volume (b = 0.5) or to the surface, (b = 0). Then, b can be determined and
the equations given next applied.
A generalization of the parameter b for several soluble substances comprising a particle is easily
done similar to this procedure for the hygroscopicity parameter in (Eqn. 6.2.3e). In the following text,
for simplicity, we consider one soluble fraction.
Using (Eqn. 6.2.4), Köhler’s equation (Eqn. 6.2.2a) can be rewritten as

Ak brd2(1+ β )
ln Sw = ln(1 + sw ) = − . (6.2.10)
rw rw3 − rd3
3 3
For dilute mixed haze particles, when lnSw = ln(1 + sw) ≈ sw = Sw − 1 and rw >> rd , this equation is
reduced to the commonly used dilute approximation

Ak brd2(1+ β )
sw = S w − 1 = − , (6.2.11)
rw rw3

where the second term is generalized for various soluble fractions. Various solutions for the humid-
ity dependence of the wet particle radius rw(Sw) at subsaturation have been obtained in algebraic
6.2. Equilibrium Radii 191

and trigonometric forms using Kohler’s equation (Eqn. 6.2.11) for dilute solutions or fully soluble
particles (e.g., Levin and Sedunov, 1966a; Sedunov, 1974; Fitzgerald et al., 1975, 1982; Hänel, 1976;
Smirnov, 1978; Khvorostyanov and Curry, 1999a, 2006, 2007; Swietlicki et al., 1999; Cohard et al.,
2000; Kreidenweis et al., 2005; Shipway and Abel, 2010). Here, we generalize the previous expres-
sions and following Khvorostyanov and Curry (2007), find analytical expressions for rw(Sw) without
assuming a dilute solution and accounting for the insoluble fraction in the Raoult term—i.e., from
(Eqn. 6.2.10).
Due to the small value of Ak, the solution for rw(Sw) can be obtained by finding a positive real root
of the cubic (Eqn. 6.2.10) with the simplifying assumption Ak = 0, and then a correction due to Ak can
be obtained by expansion into the power series:
1/3
 br 2(1+ β )−3 −3 
rw ( Sw ) = rd 1 + d 1 + Cw ( − ln Sw )−2/3   , (6.2.12)
 
 (− ln Sw ) 
Ak
Cw = . (6.2.13)
3b1/3 rd2(1+ β )/3

This expression can be simplified for a dilute wet particle, when rw >> rd and (Eqn. 6.2.11) is appli-
cable, allowing us to neglect term 1 in the figure bracket of (Eqn. 6.2.12), and with −lnSw ≈ 1 − Sw,

b1/3 rd2(1+ β )/3  −2/3 −1

rw1 ( Sw ) = 1 + Cw (1 − Sw )  . (6.2.14)
(1 − S )  
1/3
w

This solution is valid under the condition of sufficiently large subsaturation sw < slim, when the term
with Ak is smaller than 1. An estimate from (Eqn. 6.2.14) with b = 0.5, b = 0.5, and Ak = 10−7 cm yields
slim = −0.8 × 10−3 (−0.08%) for rd = 0.1 mm and slim = −2.4 × 10−2 (−2.4%) for rd = 0.01 mm. This is
the upper limit for application of (Eqns. 6.2.12)–(6.2.14), hence these equations can be used up to
Sw ≤ 0.95–0.97 (H ≤ 95–97%) for the aerosol spectrum with rd ≥ 0.01 mm.
The expression (Eqn. 6.2.14) was derived in Khvorostyanov and Curry (1999a) assuming a dilute
solution. It predicts humidity dependence for the growth factor GF(Sw) ~ (1 − Sw)−1/3 for Sw lower
than slim. The more general expression (Eqn. 6.2.12) predicts the same humidity dependence in the
intermediate region of Sw, but weaker dependencies at lower values of Sw < 0.7–0.8 (in supersaturated
solutions below deliquescence points in humidity hysteresis) and at higher values of Sw > 0.9. In con-
trast to expressions with empirical parameters, (Eqns. 6.2.12) and (6.2.14) express GF(Sw) directly in
terms of the primary variables of the Köhler equation. The additional corrections due to dependencies
on the solution concentration of the surface tension ssa (in Ak) and of the osmotic potential Φs (in b)
can be introduced in (Eqns. 6.2.12)–(6.2.14) using the known parameterizations for these quantities
(e.g., Chen, 1994; Tang and Munkelwitz, 1994; Brechtel and Kreidenweis, 2000a; Hämeri et al.,
2000, 2001). Thus, these analytical solutions can be used directly for evaluation of the equilibrium
aerosol radii or for constraints of the empirical parameterizations.
For particles with rd > 0.01 mm and saturation ratios lower than Sw ~ 0.95–0.97, the last term in the
brackets in (Eqn. 6.2.12) can be neglected and the wet radius can be approximated as

rw 2 ( Sw ) = rd [1 + brd2(1+ β )−3 (− ln Sw )−1 ]1/3 . (6.2.15)

192 Wet Aerosol Processes

For dilute particles, we can neglect the first term in the bracket, thus

rw 3 = b1/3 rd2(1+ β )/3 (1 − Sw )

−1/3
. (6.2.16)

For b = 0.5, this equation reduces to rw = rd · b1/3(1 − Sw)−1/3. This equation is similar to the empiri-
cal parameterization formulated by Kasten (1969) and used for calculation of the aerosol extinc-
tion coefficient sext(Sw) and visibility, rw(Sw) = rw(0.1)[0.9/(1 − Sw)]1/m, with 1/m = 0.25–0.3 for an
average aerosol, and is similar to Fitzgerald’s (1975) rw = αrdg, found as a parameterization of the
numerical calculations with Köhler’s theory. Thus, (Eqn. 6.2.16) provides a theoretical basis for
the empirical dependencies for rw, sext, and visibility. The empirical coefficients before the factor
(1 − Sw)−1/3 found in these works by fitting the experimental data are expressed now via the primary
aerosol parameters, and (Eqns. 6.2.12)–(6.2.15) generalize these expressions and take into account
the insoluble fraction in the wet aerosol and the different geometry of the soluble fraction-volume
and surface proportional.
A comparison of (Eqns. 6.2.12)–(6.2.15) with the empirical parameterizations and calculations of
rw(Sw) and sext(Sw) show that these equations still can be used as a reasonable approximation down to
the lower humidities (30–40%) as can be reached by the deliquescent aerosol in the humidity hyster-
esis before spontaneous salt crystallization, efflorescence (see Chapter 11).
Fig. 6.1a,b shows the humidity dependence of the wet radii rw(Sw) and the growth factor rw(Sw) /rd
calculated with the complete Equation (6.2.12) for b = 0.5 and rw1, rw2 calculated with approximate
(Eqns. 6.2.14) and (6.2.15). A comparison of the calculated growth factor with precise numerical
calculations from Kreidenweis et al. (2005) for pure ammonium sulfate particles with ev = 1 (Fig. 6.1b,
solid and open circles) shows very good agreement and indicates a sufficiently high accuracy of
(Eqn. 6.2.12). If the soluble fraction ev of ammonium sulfate is 0.3–1, rw1, rw2, and rw /rd increase
by a factor of 2 to 3 in the region 0.3 < Sw < 1, and increase especially rapidly at Sw > 0.9, in agree-
ment with numerous experimental data and previous parameterizations cited earlier. The aerosol
extinction coefficient sext (Sw) ~ rw2(Sw) and optical thickness t ~ sext (Sw) ~ rw2(Sw). This implies
that an increase in rw of 2 to 3 times causes an increase of aerosol optical thickness by a factor of
4 to 9 and illustrates the strong humidity effect on aerosol radiative properties and the direct aerosol
effect on climate. The growth is much smaller for ev = 0.1, and is negligible for ev = 0.01. The error
d1 = (rw − rw1)/rw × 100 in rw1 using the approximate (Eqn. 6.2.14) for dilute solutions increases
with decreasing soluble fraction and reaches 60–80% for ev = 0.1 to 0.01 (Fig. 6.1c). The error of
(Eqn. 6.2.15), d2 = (rw − rw2)/rw × 100, does not exceed 2–6% when Sw < 0.97 (Fig. 6.1d). Thus
(Eqn. 6.2.15), without the assumption of a dilute solution, appears to be a much better approxima-
tion than (Eqn. 6.2.14), especially for evaluation of GF for less hygroscopic or nearly hydrophobic
aerosol particles.
This shows that these analytical solutions for the equilibrium radii rw(Sw) can be used with good
accuracy for calculations of visibility, aerosol extinction, and optical thickness, and for evaluation
of the direct aerosol effects on climate with account for aerosol humidity transformation in the wide
regions of humidities and aerosol soluble fractions if an appropriate model of aerosol is chosen with
the parameters b and b.
6.2. Equilibrium Radii 193

0.30 3.0
1 1

Growth factor rw(Sw)/rd

Wet radius rw(Sw) (µm)
0.5 1, Kr05
0.25 0.3 2.5
0.5
0.1
0.3
0.20 0.01 2.0
0.1
0.01
0.15 1.5

0.10 1.0

0.4 0.5 0.6 0.7 0.8 0.9 1 0.4 0.5 0.6 0.7 0.8 0.9 1
Saturation ratio Sw Saturation ratio Sw
(a) (b)

80 1

Error (rw–rw2)/rwx100 (%)

Error (rw–rw1)/rwx100 (%)

70 0
60
−1
50
40 −2
30 −3
20
10 −4
0 −5
−10
−6
0.4 0.5 0.6 0.7 0.8 0.9 1 0.4 0.5 0.6 0.7 0.8 0.9 1
Saturation ratio Sw Saturation ratio Sw
(c) (d)

Figure 6.1. (a) Humidity dependence of the wet radii rw(Sw) calculated with (Eqn. 6.2.12), solid
circles; (b) growth factor rw /rd calculated with (Eqn. 6.2.12), solid circles, in comparison with
numerical calculations from Kreidenweis et al. (2005), open circle; (c) the errors d 1 = (rw − rw1)/rw
× 100 with rw1 calculated from (Eqn. 6.2.14) and (d) d 2 = (rw − rw2)/rw × 100 with rw2 calculated
from (Eqn. 6.2.15). The values rw, rw1, and rw2 are calculated with rd = 0.1 mm, b = 0.5, for various
volume soluble fractions ev of ammonium sulfate indicated in the legend and b evaluated with
(Eqn. 6.2.6). From Khvorostyanov and Curry (2007), J. Geophys. Res., 112(D5), D05206,
reproduced with permission of John Wiley & Sons, Inc.

6.2.2. Equilibrium Radii of Interstitial Aerosol in a Cloud

Equations (6.2.12)–(6.2.16) describe humidity transformations of the majority of wet CCN except for
the smallest particles at very high humidities close to water saturation—i.e., at values of Sw approach-
ing 1. At higher humidity within a cloud, Sw → 1 (sw → 0), an alternative approximation should be
used. Consider first the case of nearly soluble aerosol, when the insoluble fraction can be neglected.
194 Wet Aerosol Processes

At high humidity, water supersaturation sw tends to zero, and the left-hand side of (Eqn. 6.2.11) is
zero. Thus, (Eqn. 6.2.11) becomes
Ak B
sw = − = 0, (6.2.17)
rw rw3

and the radius rwi of a wet interstitial aerosol particle (subscripts w and i) can be found from the
quadratic equation
1/2 1/2
 B  b 
rwi 0 ( Sw ≅ 1) =   = rd1+ β   , (6.2.18)
 Ak   Ak 

where the subscript “0” means zero insoluble fraction. The second equality here is written with use of
(Eqn. 6.2.5) for B and generalizes the known expression, rwi0 ~ rd3/2 with b = 0.5, for the other values
of b ; in particular, rwi0 ~ rd with b = 0 (surface-proportional soluble fraction). A generalization of
this solution for rwi, taking into account the insoluble fraction, can be done with the use of Köhler’s
equation (Eqn. 6.2.10) at Sw = 1,

Ak brd2(1+ β ) rw r3 − r3
ln Sw = − = 0, or = w 2(1+ βd ) . (6.2.19)
rw rw3 − rd3 Ak brd

This gives a cubic equation for x = rw /rd,

1/2 1/2
3 2
 br 2 β   b 
β
x − 3 Z x − 1 = 0,
d with Zd =  d  =r  d  . (6.2.20)
 3 Ak   3 Ak 

This is an incomplete cubic equation for x of the form

y 3 + py + q = 0, p = −3 Z d2 , q = −1. (6.2.21)

Its solution is described in Appendix A.6 and can be chosen in trigonometric or algebraic form, de-
pending on the sign of Q,
3 2
 p  q 1
Q =   +   = − Z d6 + . (6.2.22)
 3   2 4
A trigonometric solution is convenient if Q < 0, or Zd6 > 1/4—i.e., with a sufficiently large soluble
fraction. Then, there is one physical real root; the other two roots are complex conjugated and should
be rejected. The real root is
1/2 −3/2
 p α q p
y1 = 2  −  cos , with cos α = −  −  . (6.2.23)
 3 3 2 3
Substituting here p and q from (Eqns. 6.2.21) and (6.2.20), we obtain x = y1:
1  1 
x = y1 = 2 Z d cos  arc cos  3  
 3  2 Z d  

 b 
1/2
1  1  3 A  3/2  

= 2rdβ   cos  arc cos   2kβ    . (6.2.24)
 3 Ak   3  2  brd   

6.2. Equilibrium Radii 195

Finally, the equilibrium interstitial aerosol radius rwi = xrd is

 b 
1/2
1  1  3 A  3/2  

rwi = 2rd1+ β   cos  arc cos   2kβ    . (6.2.25)
 3 Ak  3  2  brd   
 
For an aerosol particle with b = 0.5 and em = 0.5 of ammonium sulfate (b = 0.25), the condition Q < 0
is equivalent to rd > 0.01 mm, which is a typical case for many mixed CCN. For an aerosol particle
with a very small soluble fraction em = 10−2 and an insoluble fraction of SiO2 (ru = 2.65 g cm−3,
b = 8 × 10−2), the condition Q < 0 is equivalent to rd > 0.3 mm, which can be a typical case for dust
particles with a thin soluble shell. Note that the interstitial radius rwi ~ rd3/2 for the volume-propor-
tional soluble fraction, b = 0.5, and rwi ~ rd for the surface-proportional soluble fraction, b = 0.
The algebraic Cardano’s solution of (Eqn. 6.2.20) is more convenient if Q > 0, or Zd6 < 1/4—i.e.,
with the small soluble fraction. Then, the solution of incomplete cubic equation is written as de-
scribed in Appendix A.6,
1/3 1/2 1/3
 q  1  1  
y1 = Aɶ + Bɶ , Aɶ =  − + Q1/2  =  +  − Z d6   , (6.2.26)
 2  2  4  
1/3 1/2 1/3
 q  1  1  
Bɶ =  − − Q1/2  =  −  − Z d6   , (6.2.27)
 2  2  4  
rd
rwi = rd y1 = 1/3 {[1 + (1 − 4 Z d6 )1/2 ]1/3 + [1 − (1 − 4 Z d6 )1/2 ]1/3 }, (6.2.28)
2
with Zd defined in (Eqn. 6.2.20). Note that (Eqn. 6.2.28) can also be used for Q < 0, and then Q1/2
is imaginary and the expressions (−q/2 ± Q1/2) become complex. However, the expressions (−q/2 ±
Q1/2)1/3 in the brackets à and B̃ are complex-conjugate, the entire expression is real, and can be easily
calculated.
Consider the two limits for the particular cases with high and low soluble fractions.

1. The first limit is Z d2 = brd2 β/3 Ak >> 1/41/3 , or Zd >> 1, high soluble fraction. Then, the trigono-
metric solution (Eqn. 6.2.25) can be simplified. For b = 0.25, b = 0.5 (volume soluble fraction),
Ak ≈ 10−7 cm, and rd = 0.1 mm, the argument of arccos in (Eqn. 6.2.25) is ~ 0.017 << 1, and
arccos ≈ π/2, thus the last term in (Eqn. 6.2.25) is ≈ cos( π /6) = 3 /2 . Substitution of this value
into (Eqn. 6.2.25) yields
1/2 1/2 1/2
 b  π  b  3  b 
rwi ≈ 2rd1+ β   cos   = 2rd1+ β   = rd1+ β   . (6.2.29)
 3 Ak   6  3 Ak  2  Ak 

Thus, our general solution (Eqn. 6.2.25) reduces to the classical case (Eqn. 6.2.18) derived
without account for an insoluble fraction, and (Eqn. 6.2.25) generalizes it. A similar estimate is
obtained from the algebraic solution (Eqn. 6.2.28). Since Zd is large, expanding it into a power
series by 1/Zd, we obtain

rwi ≈ rd Z d [i1/3 + (− i1/3 )], (6.2.30)

π  π 
where i = −1 . Using the trigonometric Moivre’s formula i n = cos  n  + i sin  n  ,
2  2 
gives ± i1/ 3 = cos(π /6) ± i sin(π /6) = 3/2 ± i /2, and i1/ 3 + (− i1/ 3 ) = 3 . Substituting this into
(Eqn. 6.2.30) yields
196 Wet Aerosol Processes

1/2
 b 
rwi ≈ rd Z d 3 == rd1+ β   , (6.2.31)
 Ak 

that is, we arrive again at the classical case (Eqn. 6.2.18) for pure soluble CCN. Thus,
(Eqns. 6.2.25 and 6.2.28) generalize this case for the arbitrary amount of insoluble fractions.
2. The second limit is Z d2 = brd2 β /3 Ak << 1/41/ 3 , or Zd << 1, low soluble fraction b or low radius rd,
or low both. Then, expansion of (Eqn. 6.2.28) by Zd gives

 br 2 β 1  br 2 β  3 
rwi ≈ rd 1 + d −  d   . (6.2.32)
 3 Ak 3  3 Ak  

Thus, the wet interstitial radius rwi is only slightly larger than the initial dry radius rd. This case
is relevant for particles of small sizes and/or small soluble fractions.

Table 6.1 along with Fig. 6.1 illustrate rapid increase of rw in the region 0.98 < Sw < 1. Calcula-
tions are performed with (Eqns. 6.2.12) and (6.2.28) for the same parameters as in Fig. 6.1: b = 05,
rd = 0.1 mm, and various values of ev. For ev = 1 (fully soluble CCN), rw increases by a factor of 3 over
the range Sw = 0.3 to 1, and increases by a factor of 2.2 over the range Sw = 0.98 to 1. The growth fac-
tors decrease with a decreasing soluble fraction: for ev = 0.01, rw increases by 0.4% only in the range
Sw = 0.3 to 1 (Fig. 6.1), and increases by 38% from Sw = 0.98 to 1 (Table 6.1). This rapid growth just
below Sw → 1 explains the sharp decrease in visibility and growth of aerosol optical thickness ob-
served when aerosol transforms into “a milky haze” prior to activation (condensation) (e.g., Kasten,
1969; Fitzgerald, 1975) that can be seen just below the low boundaries of non-precipitating clouds.
Table 6.1 shows calculations of the relative error of the classical equation (Eqn. 6.2.18),
d3 = (rwi − rwi0)/rwi × 100, where rwi0 is calculated with (Eqn. 6.2.18), and rwi with the new equation
(Eqn. 6.2.28). The errors at ev = 1 are small (1–2%), and grow to 7–11% at ev = 0.1. For these val-
ues of ev, the accuracy of the classical equation (Eqn. 6.2.18) is acceptable. The errors grow above
10% at ev < 0.1 and to ~50% at ev = 0.01; thus, for very small ev, it is better to use the new equations
(Eqns. 6.2.28) or (6.2.25). It is interesting to note that the relative error d2 defined in previous sections
and d3 given in Table 6.1 are quite comparable, although they are calculated with completely differ-
ent equations. This indicates that the equations derived in Section 6.2.1 describe rw(Sw) as a smooth
function at transition from subsaturation to interstitial conditions despite its rapid growth as Sw → 1.

Table 6.1. Transformation of wet radii rw (m m) at high saturation ratios Sw for b = 0.5, rd = 0.1 mm,
and various soluble fractions ev and the errors in using approximate equations for rw.

ev 1 0.5 0.3 0.1 0.01

rw(Sw = 0.98) 0.32 0.25 0.21 0.15 0.10
rw(Sw = 1.0) 0.69 0.49 0.39 0.23 0.14
GF = rw(1.0)/rw(0.98) 2.19 1.99 1.84 1.53 1.38
d2 = (rw − rw2)/rw × 100, (%) Sw = 0.98 1.05 2.18 3.72 10.9 49.6
d3 = (rwi − rwi0)/rwi × 100, (%) Sw = 1.0 2.31 3.20 4.04 6.55 52.9
6.3. Critical Radius and Supersaturation 197

The expressions (Eqns. 6.2.25) and (6.2.28) and the particular cases (Eqns. 6.2.29) and (6.2.31) are
valid for Sw close to 1, and can be used at the stage of CCN activation at slight subsaturation, Sw < 1,
or for interstitial but unactivated cloud aerosol. In the latter case, Sw > 1 (sw > 0), the spectra are lim-
ited by the boundary radius rb 5 2Ak /3sw.

6.3. Critical Radius and Supersaturation

A typical behavior of water supersaturation sw(r) over a solution droplet calculated with (Eqn. 6.2.10)
is shown in Fig. 6.2. Calculations were performed for b = 0.25 (CCN with 50% soluble fraction of
ammonium sulfate), b = 0.5 (volume soluble fraction) and five masses of dry particles: md = 10−16 g,
10−15 g, 10−14 g, 10−13 g, 10−12 g (rd = 0.0238 mm, 0.0512 mm, 0.11 mm, 0.24 mm, and 0.51 mm, respec-
tively). This figure shows that the curve sw(r) consists of the two branches, ascending and descend-
ing, which is caused by the presence of two terms in Köhler’s equation: the positive curvature term
and negative solution term. The ascending branch at smallest radii approach the asymptotic formed
by Raoult’s solution term in (6.2.10), brd2(1+ β )/(rw3 − rd3 ) , which is more singular at small radii than
the Kelvin’s curvature term, Ak /rw. At large radii, vice versa, Raoult’s term is small, and the asymp-
totic is determined by the curvature term. Hence, the supersaturation curves have maxima at some
intermediate radii, about 0.04 to 10 mm in the considered examples. The maximum supersaturation

1.0

0.8

0.6
Supersaturation sw (%)

0.4

0.2

0.0

–0.2

–0.4 10–16
–0.6
10–15
–0.8
10–14 10–13 10–12
–1.0
0.10 1.00 10.00
Solution drop radius (µm)

Figure 6.2. Equilibrium supersaturation over aqueous solution drops as a function of droplet radius.
Calculations are performed with equation (Eqn. 6.2.10) for aerosol particles with dry masses
md =10−16, 10−15, 10−14, 10−13, and 10−12 g indicated near the curves, containing 50% of ammonium
sulfate as a soluble fraction (rd = 0.0238 mm, 0.0512 mm, 0.11 mm, 0.24 mm, and 0.51 mm,
respectively).
198 Wet Aerosol Processes

on Köhler’s curve sw(r) is called the critical supersaturation scr, and the corresponding radius on
the x-axis is called the critical radius rcr. The solution droplets with radii r < rcr, on the ascending
left branch, are in stable equilibrium, and those at r > rcr, on the descending right branch, are in
metastable equilibrium because a small perturbation in sw causes further growth or evaporation until
the critical values are reached. This figure shows that as the dry radius rd increases, the critical scr
decreases and shifts to greater rcr.
The expressions for the critical radius rcr and supersaturation scr for CCN activation can be found
using Köhler’s equations from the condition of the maximum, dsw /drw = 0. For dilute solutions
when rcr >> rd, or neglecting the insoluble fraction, (Eqn. 6.2.11) yields a quadratic equation relative
to rcr:

dsw Ak 3 B
=− + = 0. (6.3.1)
drw rcr
rw2 rw4

Solving for rw = rcr, we obtain the critical radius

1/2 1/2
 3B  1+ β
 3b 
rcr =   = rd  A  . (6.3.2)
 k
A  k

Substitution into (Eqn. 6.2.11) gives

1/2 1/2
Ak B  4 Ak3  2 Ak  4 A3 
scr = − 3 =  = = rd− (1+ β )  k  . (6.3.3)
rcr rcr  27 B  3 rcr  27b 

The expressions with B on the right-hand side of (Eqns. 6.3.2) and (6.3.3) are the classical Köhler’s
solutions for rcr and scr and are valid for dilute solutions or for CCN without an insoluble fraction.
The expressions with b and b on the right-hand sides of (Eqns. 6.3.2) and (6.3.3) are modifica-
tions of the Köhler expressions obtained using the preceding parameterization of B via b and b in
(Eqns. 6.2.4)–(6.2.7).
The information on the soluble fraction chemistry is in the parameter b, and information on its
geometry is in b. The latter representation shows, in particular, that rcr is proportional to rd(1+b), and
scr is inversely proportional to rd(1+b). This explains why rcr shifts to larger radii and scr decreases
with an increase of rd in Fig. 6.2. These changes are different for different b, and are stronger for the
volume-proportional soluble fraction (rd(1+b) ~ rd3/2) than for the surface-proportional soluble fraction
(rd(1+b) ~ rd). The explicit analytical dependence of these effects is seen with the parameterization
(Eqns. 6.2.4)–(6.2.7) of B via b and b, but is not seen without this parameterization, just with B. This,
in particular, illustrates the convenience of using the parameterization of B via b and b.
If the soluble fraction on CCN is small (e.g., a small volume fraction or a thin soluble shell on
the surface of an insoluble dust particle), the assumption of high dilution and the condition rcr >> rd
can be invalid even at the time of activation, then the more complete (Eqn. 6.2.10) for Sw should
be used instead of (Eqn. 6.2.11). We will obtain now an analytical solution for scr and rcr without
approximation of high dilution at activation, rcr >> rd. This will allow estimation of the accuracy and
applicability of the classical solutions (Eqns. 6.3.2) and (6.3.3). The equation ds(rw) /drw = 0 with
sw(rw) defined by (Eqn. 6.2.10) yields a condition at rw = rcr of
6.3. Critical Radius and Supersaturation 199

d ln Sw Ak 3rw2 brd2(1+ β )
=− + 3 3 2 = 0, (6.3.4)
drw rxr
rw2 (rw − rd ) rcr

which gives a sixth-order equation for rcr:

Ak 3brd2(1+ β ) rc2r (6.3.5)

= 3 .
rcr2 (rcr − rd2 )2

Taking the square root, this can be reduced to the cubic equation by rcr,
1/ 2 1/2
 br 2 β   b 
rcr3 − (3rd Z d )rcr2 − rd3 = 0, Z d =  d  = rdβ   . (6.3.6)
 3 Ak   3 Ak 

It is convenient to divide all terms by rd3 and solve an equation for a dimensionless variable x = rcr /rd:

x 3 − 3 Z d x 2 − 1 = 0. (6.3.6a)

This is an incomplete cubic equation without a linear power of x. The solution to (Eqns. 6.3.6) and
(6.3.6a) is obtained in Appendix A.6 in the algebraic Cardano’s form. It is expressed in terms of Zd
and gives a solution for rcr,
rcr = rd χ ( Z d ), x = χ ( Z d ) = Z d + P+ ( Z d ) + P− ( Z d ), (6.3.7)
1/2 1/3
  1 1
P± ( Z d ) =  Z d3 ±  Z d3 +  +  . (6.3.8)
  4  2

Equation (6.3.7) is a generalization of (Eqn. 6.3.2) for rcr without an assumption of high dilution. It
is valid for an arbitrary soluble fraction and reduces to the classical expression for the particular case
Zd >> 1 (high b or high soluble fraction). Then, expanding (Eqns. 6.3.7) and (6.3.8) into the power
series yields

rcr ≈ rd [ Z d + Z d (1 + Z d−3/ 2 /3) + Z d (1 − Z d−3 /2 /3 )]

1/2 1/2
 3brd2(1+ β )   3B 
= 3rd Z d =   =A  , (6.3.9)
 Ak   k

which is the classical expression (Eqn. 6.3.2) for rcr, confirming the validity of (Eqn. 6.3.7). In the
opposite limit, Zd << 1, which may happen at very small soluble fractions or radii, another expansion
of (Eqn. 6.3.7) by Zd yields:

2 3   br 2 β  1/2 2  br 2 β  3/2 
rcr ≈ rd (1 + Z d + Z d ) = rd 1 +  d  +  d   . (6.3.10)
3   3 Ak  3  3 Ak  

Using rcr from (Eqn. 6.3.7), the critical supersaturation is then calculated from the equation

A br 2(1+ β ) 
scr = exp  k − 3d 3  − 1. (6.3.11)
 rcr rcr − rd 
200 Wet Aerosol Processes

This equation can be simplified using the previous relations between rd and rcr as

 2A 
scr = exp  k  − 1. (6.3.11a)
 3rcr 

Fig. 6.3a, b depicts the critical supersaturations, scr, and critical radii, rcr, calculated with the new
(Eqns. 6.3.11) and (6.3.7) as functions of the dry radius rd and volume soluble fraction ev from 1 to
10−3 for ammonium sulfate. Shown in Fig. 6.3c,d are the relative errors in calculations of scr and rcr
defined as d scr = (scr,1 − scr,2) /scr,2, and d rcr = (rcr,2 − rcr,1)/rcr,2, where the subscript “1” denotes the
classical Köhler expressions (Eqns. 6.3.2) and (6.3.4) that do not account for the insoluble fraction
at the time of activation, and subscript “2” denotes the new (Eqns. 6.3.11) and (6.3.7) that account
for the insoluble fraction. The accuracy of the classical equations is reasonably good for the soluble

1E+2
Critical supersaturation (%)

εv = 1
1E+2
1, Kr05

Critical radius (µm)

1E+1
0.5 1E+1
1 0.3
1
0.1
0.1 0.01 0.1
0.001
1E–2 1E–2

1E–3 1E–3
1E–3 1E–2 0.1 1 1E+1 1E+2 1E–3 1E–2 0.1 1 1E+1 1E+2
Dry radius (µm) Dry radius (µm)
(a) (b)
Error in critical supersaturation (%)

1E+3 1E+2
Error in critical radius (%)

1E+2
1E+1
1E+1

1
1
0.1

1E–2 0.1
1E–3 1E–2 0.1 1 1E+1 1E+2 1E–3 1E–2 0.1 1 1E+1 1E+2
Dry radius (µm) Dry radius (µm)
(c) (d)

Figure 6.3. (a) Critical supersaturation scr calculated with the new (Eqn. 6.3.11). The open circle
is a precise numerical calculation from Kreidenweis et al. (2005, Kr05) for pure ammonium
sulfate (ev = 1). (b) Radius rcr (mm) calculated with the new (Eqn. 6.3.7). (c) and (d): Relative
errors (%) of calculation with the old expressions (Eqns. 6.3.3) and (6.3.2) for scr and rcr as functions
of the dry radius and volume soluble fraction ev from 1 to 10−3 indicated in the legend. From
Khvorostyanov and Curry (2007), J. Geophys. Res., 112(D5), D05206, reproduced with permission
of John Wiley & Sons, Inc.
6.3. Critical Radius and Supersaturation 201

fractions ev ≥ 0.1 in accumulation (0.1–1 mm) and coarse (>1 mm) modes. The errors in scr and rcr
are smaller than 1–2% (indicating also the correct limits of the new equations). For a particle of pure
ammonium sulfate (ev = 1), the solution (Eqn. 6.3.11) exactly coincides with the precise numerical
calculation from Kreidenweis et al. (2005, open circle in Fig. 6.3a). The errors of the classical diluted
approximation grow with decreasing rd and ev. For ev = 0.01, the errors reach 15–25% in the accumu-
lation mode. At rd = 0.01 mm, they grow to 20–30% with ev = 0.1, and to 80–200% at ev = 0.01. For
the very small solubility of 10−3, the errors are substantially greater, 100–500% for the submicron
fraction 0.01–0.1 mm, and decrease to 1–20% for the coarse fraction.
The accuracy and applicability of the classical expressions is further illustrated in Fig. 6.4a,b,c.
The ratio rcr /rd decreases with decreasing solubility. For small ev ~ 10−3 to 10−2, the values of
the critical and dry radii are comparable (lower curves in Fig. 6.4a). The ratios rcr /rd evaluated
with the new (Eqn. 6.3.7) for these small solubilities lie in accumulation mode slightly above the
curve rcr = rd. So, rcr /rd ~ 1 and the relation rcr >> rd, usually used in the derivation of rcr from
(Eqn. 6.2.11) for dilute solutions, is not satisfied, hence (Eqns. 6.2.10) and (6.3.5) and the solution
(Eqn. 6.3.7) should be used instead under these conditions. Note that values ev ~ 10−3 to 10−2 (the
lower curves in Fig. 6.4a) represent the case of mineral dust with thin soluble coating. The ratio
rcr /rd calculated for these cases of small rd and ev with the classical (Eqn. 6.3.2) lie below the curve
rcr = rd (Fig. 6.4b)—i.e., rcr < rd, and the classical expression fails as it predicts critical radii smaller
than the dry ones. According to Rosenfeld et al. (2001), the fine-dispersed fractions of dust with
small solubility may have a significant climatic effect, since they may suppress precipitation in
semi-arid and arid areas and cause a desertification feedback loop. Hence, its correct account in the
models is important, and drop activation should be calculated with (Eqns. 6.3.7) and (6.3.11) rather
than with (Eqns. 6.3.2) and (6.3.3).
For ev ≥ 0.1 and rd > 0.1 mm, the ratio rcr /rd ≥ 4, and the approximation rcr3 >> rd3 with classical
equations for rcr, scr given by (Eqns. 6.3.2) and (6.3.3) become valid. Note that the 1000-fold decrease
in the soluble fraction from 1 to 10−3 for rd = 1 mm causes rcr to decrease by only ~22 times from
37 mm to 1.6 mm—i.e., a mineral dust particle with thin soluble shell requires much less time for
growth to activation size than a fully soluble CCN of the same size. Fig. 6.4c shows that scr,new pre-
dicted by (Eqn. 6.3.11) for small ev = 10−2 to 10−3 and small rd is 3–9 times less than scr,old predicted
by the classical (Eqn. 6.3.3). Thus, calculations with the new (Eqn. 6.3.11) may substantially accelerate
the activation process of such CCN than by the old (Eqn. 6.3.3).
These estimates show that the classical expressions (Eqns. 6.3.2) and (6.3.3) should be used with
caution for particles with small solubilities and small sizes. A more precise approach for determining
rcr and scr is based on (Eqns. 6.3.7) and (6.3.11).
Fig. 6.3a shows that the values of scr required for activation of a given CCN increase with
decreasing rd from 0.1–0.3% at rd = 0.1 mm and ev = 1 to 10−2 (a typical cloud case) to 2–12%
at rd = 0.01 mm and up to 10–50% at rd = 0.003 mm. Thus, supersaturations sw = 10–25%, as
can be reached in a cloud chamber, may cause activation of accumulation and Aitken modes of CCN
with rd = 0.1 to 0.003 mm even with a very small soluble fraction of 10−2–10−3. Hence, analysis or
numerical simulations of such cloud chamber experiments may require the more precise (Eqns. 6.3.7)
and (6.3.11).
202 Wet Aerosol Processes

1E+3 1
0.5 rcr/rd = 1

1E+2 0.3

Ratio rcr/rd (new)

0.1
0.01
1E+1
0.001

0.1
1E–3 1E–2 0.1 1 1E+1 1E+2
Dry radius (µm)
(a)
1E+3

rcr/rd = 1
1E+2
Ratio rcr/rd (old)

1E+1

0.1
1E–3 1E–2 0.1 1 1E+1 1E+2
Dry radius (µm)
(b)
10
8
Ratio scr,old/scr,new

6 1
0.5
4
0.3
0.1
0.01
2
0.001

1
1E–3 1E–2 0.1 1 1E+1 1E+2
Dry radius (µm)
(c)

Figure 6.4. (a) The ratio of rcr /rd calculated with the new (Eqn. 6.3.7) (denoted “new”).
(b) Same ratio calculated with the old (Eqn. 6.3.2) (denoted “old”); the dashed line with open
circles is rcr = rd. (c) The ratio scr,old /scr,new with scr,old and scr,new is calculated with (Eqns. 6.3.3) and
(6.3.11), respectively. The various soluble fractions ev from 1 to 0.001 are indicated in the legend.
From Khvorostyanov and Curry (2007), J. Geophys. Res., 112(D5), D05206, reproduced with
permission of John Wiley & Sons, Inc.
6.4. Aerosol Size Spectra 203

6.4. Aerosol Size Spectra

6.4.1. Lognormal and Inverse Power Law Size Spectra

The atmospheric aerosol generally represents a polydisperse ensemble of internally and externally
mixed aerosol particles, each consisting of soluble and insoluble fractions. Historically, one of the
first analytical functions suggested by Junge (1952, 1963) based on measurements of aerosol size
spectra and widely used in aerosol sciences for several decades was the inverse power law:

fa (ra ) = c f ra− µ , (6.4.1)

where cf is the normalization constant, and m is the index usually determined from the fitting of
measured size spectra. The values 4 < m < 5 were found in most of the measurements, although this
index could vary in a wider range (Junge, 1963, Pruppacher and Klett, 1997; Seinfeld and Pandis,
1998). These inverse power law size spectra allow us to describe a number of aerosol properties, in-
cluding Ångström’s (1929, 1964) inverse power law dependence of the optical extinction coefficients
(Eqn. 6.1.6a) (e.g., van de Hulst, 1957; Junge, 1963; Tomasi et al., 1983, 2007; Khvorostyanov and
Curry, 1999b). The deficiencies of the power law (Eqn. 6.4.1) is that, as measurements and theory
showed, the index m depends itself on the size range and moments (integrals) of this distribution and
may diverge at small and large sizes.
At present, the most common function used to describe a polydisperse aerosol is the lognormal
distribution, which allows us to account for variations of m with size and gives us finite integrals. The
lognormal size spectrum of dry aerosol fd(rd) by the dry radii rd or spectrum fw(rw) of wet aerosol by
wet radii rw can be presented in the form:

Na  ln 2 (rd , w /rd , w 0 ) 
fd , w (rd , w ) = exp  − , (6.4.2)
2π (ln σ d , w )rd , w  2 ln 2 σ d , w 

where the subscripts “d, w” mean dry or wet aerosol, Na is the aerosol number concentration, sd0 and
sw0 are the dispersions of the dry or wet spectrum, and rd0 and rw0 are the mean geometric radii. The
properties of the lognormal distributions were considered in Chapter 2.
The measured aerosol distributions usually are multimodal—that is, have several local maxima at
several radii. To describe this feature, several versions of multimodal distributions by aerosol radius
ra were suggested of the type
n
N ai  ln 2 (ra /rai 0 ) 
fa (ra ) = ∑ exp  − , (6.4.3)
i =1 2π (ln σ ai )rai  2 ln 2 σ ai 

where n is the number of modes, Nai, rai0, and sai are respectively the number concentration, mean
geometric radius, and dispersion of the i-th mode, and summation is taken over all n modes. For
example, Jaenicke (1988) and Whitby (1978) suggested the trimodal distributions, and Vignati et al.
(2004) suggested a model with seven modes.

6.4.2. Approximation of the Lognormal Size Spectra by the Inverse Power Law

In various applications, either lognormal distributions or inverse power laws are used and it is desir-
able to establish a quantitative correspondence between them. A correspondence between them can
204 Wet Aerosol Processes

be found using the same method as for a continuous power law representation of the fall velocities
(see Chapter 12 here). Suppose f(r) is smooth and has a smooth derivative f ′(r). Then, they can be
presented at a point r as the power law functions

f (r ) = c f r − µ , f ′(r ) = − µ f (r )/r . (6.4.4)

Solving (Eqn. 6.4.3) for m and cf, we obtain:

rf ′(r )
µ (r ) = − , c f (r ) = f (r )r µ ( r ) . (6.4.5)
f (r )

The power index m and cf are here the functions of radius. If aerosol size spectrum f(r) is described
by the dry fd(rd) or wet fw(rw) lognormal distribution of the form (Eqn. 6.4.2), substitution of fd,w and
f ′d,w into (Eqn. 6.4.5) yields the power index for the dry and wet aerosol spectra
ln(rd , w /rd , w 0 )
µd , w (rd , w ) = 1 + , (6.4.6)
ln 2 σ d , w

where the indices “d, w” denote dry or wet aerosol, and rw0, sw0 are the corresponding mean geomet-
ric radii and dispersions. Thus, the lognormal dry and wet spectra of the form (Eqn. 6.4.2) can be
presented at every point rd, rw, in the power law form (Eqn. 6.4.1) with the index m d,w (Eqn. 6.4.6).
This will be illustrated in the next section for dry and wet spectra.

6.4.3. Examples of the Lognormal Size Spectra, Inverse Power Law, and Power Indices

Fig. 6.5a shows four lognormal size spectra of the dry aerosol with various modal radii and dis-
persions along with the corresponding critical radii and supersaturations calculated with b = 0.5,
b = 0.55 (~50% soluble fraction of ammonium sulfate). All spectra have a modal shape, which is
asymmetric with respect to small and large sizes with a long tail in the region of larger radii. This
modal shape of lognormal spectra along with the inverse dependence of the critical supersaturation
on dry radius described in Section 6.3 by (Eqns. 6.3.3) or (6.3.11a) are important for understanding
any quantitative description of CCN activation; this also determines the separation between activated
and unactivated CCN fractions. One can see in Fig. 6.5a that if the maximum supersaturation does
not exceed ~0.1%, the right branch of the dry spectrum with rm = 0.1 mm can be activated down to
the mode, and the left branch (rd < rm) remains unactivated. Such situations and sw may occur in
stratiform clouds. For the spectrum with rm = 0.03 mm, activation of the right branch down to rm
requires a supersaturation of 0.6%. Such a supersaturation may occur in convective clouds. Thus,
we can expect in these examples of the size spectra that the right branches of CCN will be activated
in natural clouds. Activation of the left branches with rd < 0.01–0.03 mm requires noticeably higher
supersaturations and may be typical of the CCN measurements in cloud chambers where sw ~ 5–20%
can be reached (e.g., Jiusto and Lala 1981; Hudson 1984, Yum and Hudson 2001). A more detailed
study of contributions of various ranges of the size spectra will be done in Section 6.6 in terms of the
supersaturation activity spectra.
Fig. 6.5b shows a lognormal dry aerosol size spectrum fd(rd) with modal radius rm = 0.03 mm
and dispersion sd = 2, close to Whitby (1978) for the accumulation mode, and concentration
6.4. Aerosol Size Spectra 205

rm = 0.1 µm, σd = 2.0

6E+3 scr = 0.61%
rm = 0.03 µm, σd = 2.0

Size spectra (cm–3 µm–1)

rm = 0.1 µm, σd = 1.5
rm = 0.03 µm, σd = 1.5
4E+3

2E+3 scr = 0.0937 %

0
1E–3 1E–2 1E–1 1E+0
Dry radius (µm)

1E–3 1E–2 0.1 1 1E+1 1E+2

Critical radius (µm)

1E+2 10 1 0.1 0.01 1E–3

Critical supersaturation (%)
(a)

Figure 6.5. (a) Lognormal aerosol size spectra for rm = 0.1 mm, sd = 2 (solid circles), rm = 0.1 mm,
sd = 1.5 (crosses), rm = 0.03 mm, sd = 2 (diamonds), and rm = 0.03 mm, sd = 1.5 (triangles), plotted
as the functions of dry radii and of corresponding critical radii and critical supersaturations. Critical
supersaturations scr corresponding to the maxima at 0.1 mm and 0.03 mm are shown near the
curves. From Khvorostyanov and Curry (2006), J. Geophys. Res., 111, D12202, reproduced with
permission of John Wiley & Sons, Inc.

Na = 200 cm−3. Its Junge-type inverse power law approximations calculated with (Eqn. 6.4.5) and
(Eqn. 6.4.6) shows the radius dependence of the power index m: It changes from m = −1.27 at
r1 = 0.016 mm < rm, to m = 0 at the modal radius r2 = rm, and m is positive at all r > rm; in particular,
m = 2.5 at r3 = 0.1 mm, and m = 5.0 at r4 = 0.33 mm. These results well agree with the dimensional
analysis of the coagulation equation and its asymptotic solutions that yield the inverse power laws
with the index m = 2.5 near rd ~ 0.1 mm due to the dominant effects of Brownian coagulation, and
m = 4.5 for rd > 1 mm due to prevailing sedimentation (e.g., Pruppacher and Klett, 1997, Chapter 11).
The lognormal spectrum with the described parameters is in general agreement with these power
law solutions. Thus, the lognormal size spectrum can be considered as the superposition of the power
laws with the indices from (Eqn. 6.4.6). The transition of the dry lognormal size spectrum to the limit
Sw = 1 (curve with open circles) is fairly smooth, although there is a distinct decrease of the slopes.
This resembles a corresponding effect for the power law spectra, when the transition to Sw = 1 is ac-
companied by a decrease of the Junge power index, e.g., m = 4 at Sw < 1 converts into m = 3 at Sw → 1
over a very narrow humidity range. The humidity dependence of the inverse power law size spectra
will be considered in more detail in Section 6.5.
206 Wet Aerosol Processes

Size distribution function (cm–3 µm–1)

1E+4
1E+3
1E+2
10
1 dry log., rm = 0.03 µm, σ = 2
wet log., rm = 0.03 µm, σ = 2
0.1
r1 = 0.016 µm, µ = –1.27
0.01
r2 = 0.030 µm, µ = 0
1E–3
r3 = 0.100 µm, µ = 2.5
1E–4
r4 = 0.330 µm, µ = 5.0
1E–5
0.01 0.1 1
Radius (µm)
(b)

Figure 6.5. (b) Lognormal dry (solid curve) and interstitial (open circles) aerosol size spectra with
the parameters: modal radius rm = 0.03 mm, sd,w = 2, Na = 200 cm−3, and the Junge-type power law
approximations to the dry spectrum calculated from Equation (6.4.6) at 4 points: before modal
radius, r1 = 0.016 mm, negative index m = −1.27; modal radius r2 = 0.03 mm, m = 0; r3 = 0.1 mm,
m = 2.5; and r4 = 0.33 mm, m = 5.0). From Khvorostyanov and Curry (2006), J. Geophys. Res., 111,
D12202, reproduced with permission of John Wiley & Sons, Inc.

The effective power indices calculated for lognormal distributions with various modal radii and
dispersions are shown for the dry aerosol in Fig. 6.6, which illustrates the following general features
of (Eqn. 6.4.6). The indices (the slopes of the spectra) increase with radii for all r. The indices m in-
crease with decreasing dispersions and with increasing rd0 of the dry lognormal spectrum. The calcu-
lated m intersect the average Junge’s curve m = 4 in the range of radii 0.06 mm to 0.7 mm—i.e., mostly
in the accumulation mode. Since the values chosen here for rd0 and sd are realistic (close to Whitby’s
multimodal spectra), this may explain how a superposition of several lognormal spectra may lead to
an “effective average” m = 4, observed by Junge. The growth of the indices above 4 for larger r is in
agreement with the coagulation theory that predicts steeper slopes m = 19/4 of the power laws for
greater radii r ≥ 5 mm (Pruppacher and Klett, 1997). The described relation between the lognormal
and power law size spectra might be useful for analysis and parameterizations of the measured spec-
tra and of solutions to the coagulation equation, for sectional representations of the size spectra as
well as for comparison of parameterizations based on lognormal and inverse power law distributions.

6.4.4. Algebraic Approximation of the Lognormal Distribution

A disadvantage of the lognormal size spectra is the difficulty of evaluating analytical asymptotics
and moments of this distribution. A convenient algebraic equivalent of the lognormal distribution was
obtained by Khvorostyanov and Curry (2006, 2007) using two representations of the smoothed (bell-
shaped) Dirac’s delta-function d (x). The first one was taken as (Korn and Korn, 1968):
α
δ1 ( x,α ) = exp(−α 2 x 2 ), (6.4.7)
π
6.4. Aerosol Size Spectra 207

20 rm = 0.10 µm, σ = 2.0

rm = 0.03 µm, σ = 2.0

Effective junge index µ(r)

16
12 rm = 0.10 µm, σ = 1.5
rm = 0.03 µm, σ = 1.5
8
µ=4
4
0
–4
–8
1E–3 0.01 0.1 1
Radius (µm)

Figure 6.6. Effective power indices calculated from (Eqn. 6.4.5) for lognormal distributions
with modal radii and dispersions indicated in the legend; the constant value m = 4 is given for
comparison. From Khvorostyanov and Curry (2006), J. Geophys. Res., 111, D12202, reproduced
with permission of John Wiley & Sons, Inc.

where a determines the width of the function. Another representation as an algebraic function of
exp(x/a) is given in Levich (1969). We transformed it to the following form:
α 1
δ 2 ( x,α ) = , (6.4.8)
π ch 2 (2α x / π )
It can be shown that both functions d1(x,a) and d2(x,a) are normalized to unity, tend to the Dirac’s
delta-function when a → ∞ and exactly coincide in this limit:

lim δ 1 ( x , α ) = lim δ 2 ( x , α ) = δ ( x ). (6.4.9)

α →∞ α →∞

Thus, we obtain the following approximate equality:

α α 1
exp(−α 2 x 2 ) ≈ . (6.4.10)
π π ch 2 (2α x / π )
A comparison shows that both functions are sufficiently close already at values a ~ 1, which is il-
lustrated in Fig. 6.7a. Where these functions divided by α / π are plotted, the difference generally
does not exceed 3–5%. The approximate equality of these smoothed delta-functions is used further
for an algebraic representation of the aerosol size and CCN activity spectra.
Integration of (Eqn. 6.4.10) from 0 to x yields another useful relation:

erf (α x ) ≈ tanh(2α x / π ), (6.4.11)

where erf(z) is the Gaussian function of errors:

z
2 − x2
erf ( z ) =
π ∫e
0
dx . (6.4.12)

Equation (6.4.11) with a = 1 was found by Ghan et al. (1993), who showed its accuracy, which is
also illustrated in Fig. 6.7b, for two values of a. It is known that integration of Dirac’s delta-function
208 Wet Aerosol Processes

1.0 ch, α = 1.0

ch, α = 3.0

Functions exp, ch
0.8
exp, α = 1.0
0.6 exp, α = 3.0

0.4

0.2

0.0
–3 –2 –1 0 1 2 3
X
(a)

1.00
0.75
Functions erf, tanh

0.50
erf, α = 1.0
0.25
erf, α = 3.0
0.00
–0.25 tanh α = 1.0
–0.50 tanh α = 3.0
–0.75
–1.00
–3 –2 –1 0 1 2 3
X
(b)

Figure 6.7. (a) Comparison of the smoothed Dirac delta-functions: exp(−a2x2) (denoted exp),
and its approximation 1/ch 2 (2α x / π ) (denoted ch), for two values a = 1 and 3. The difference
generally does not exceed 3–5%. (b) Comparison of the smoothed Heaviside step-functions,
n h(2α x / π ) . From Khvorostyanov and Curry (2006), J. Geophys. Res.,
erf(ax), and tanh
111, D12202, reproduced with permission of John Wiley & Sons, Inc.

yields the Heaviside step-function. Comparison of Figs. 6.7a and 6.7b shows that the same is valid
for the correspondent smoothed functions; therefore, the earlier derivation shows that the relation
(Eqn. 6.4.11) is an approximate equality of the two representations of the smoothed Heaviside step-
functions. Equation (6.4.11) is used in the following for the proof of equivalence of the lognormal
and algebraic representations of the drop concentration and k-index.
The lognormal distribution can be approximated by an algebraic form introducing in (Eqn. 6.4.10)
the new variables x = ln(r /r0 ) and α = ( 2 ln σ )−1. Thus,

2α x 1 4 r k r
= ln = 0 ln   , (6.4.13)
π 2 2π ln σ r0 2  r0 

where k0 is a parameter introduced by Ghan et al. (1993) as

4
k0 = . (6.4.14)
2π ln σ
6.4. Aerosol Size Spectra 209

Then, the left-hand side of (Eqn. 6.4.10) can be rewritten as

α 1  ln 2 (r / r0 ) 
Z1 ≡ exp(−α 2 x 2 ) = exp  − 2 . (6.4.15)
π 2π ln σ  2 ln σ 
The right-hand side of (Eqn. 6.4.10) can be rewritten using (Eqn. 6.4.13):
α 1
Z2 ≡
π ch 2 (2α x / π )
−2
k0  1   2α x   2α x   
=   exp   + exp  − 
4  2   π   π   
−2
 k r  k r 
= k 0  exp  0 ln  + exp  − 0 ln  
  2 r0   2 r0  
−2
 
− k0 /2

  r  k0 /2   r   
= k 0 exp  ln   + exp  ln    . (6.4.16)
   r0    r0   

Using the equality exp[a ln x ] = [exp(ln x )]a = x a , the expression (Eqn. 6.4.16) can be transformed as
−2
 r  k0 /2  r  − k0 / 2  k 0 (r / r0 ) k0
Z 2 = k0   +    = . (6.4.16a)
 r0   r0   [1 + (r / r0 ) k0 ]2

Equating now the left- and right-hand sides of (Eqn. 6.4.10)—that is, Z1 from (Eqn. 6.4.15) and Z2
from (Eqn. 6.4.16a), we obtain

1  ln 2 (r / r0 )  k 0 (r / r0 ) k0
exp  − 2 ≈ 2
. (6.4.17)
2π ln σ  2 ln σ  [(r / r0 ) + 1]
k0

Now, the lognormal spectrum (Eqn. 6.4.2) can be transformed using (Eqn. 6.4.17) as

N a  1  ln 2 (r / r0 )  
f (r ) =  exp  − 2 
r  2π (ln σ )  2 ln σ  
Na  k 0 (r / r0 ) k0  N a k 0 (r / r0 ) k0 −1 (6.4.18)
≈  2 
= .
r  [(r / r0 ) 0 + 1] 
k
r0 [(r / r0 ) k0 + 1]2

The left-hand side of (Eqn. 6.4.18) is a lognormal spectrum with the concentration Na, mean geomet-
ric radius r0, and dispersion s, and the right-hand side is its algebraic equivalent, which depends on
the same parameters. These two distributions are different but are equivalent representations of the
smoothed delta-function. That is, we found a new class of the size distribution functions that approxi-
mate the lognormal spectra in algebraic form. When the dispersion tends to its lower limit s → 1,
then in (Eqn. 6.4.13) a → ∞, and according to (Eqn. 6.4.9), both distributions tend to the delta-
function—i.e., become infinitely narrow (monodisperse) at s = 1. For s > 1, they represent distribu-
tions of the finite width. Using Equation (6.4.18), the dry lognormal aerosol size spectra (Eqn. 6.4.2)
with s = sd and r = rd can be rewritten in algebraic form as
210 Wet Aerosol Processes

k d 0 N a (rd /rd 0 ) kd 0 −1
fd (rd ) = , (6.4.19)
rd 0 [1 + (rd /rd 0 ) kd 0 ]2

where rd0 and sd are the geometric radius and dispersion of the dry spectrum and the index k0d is
4
kd 0 = . (6.4.20)
2π ln σ d
The size spectra (Eqns. 6.4.18) and (6.4.19) were derived in Khvorostyanov and Curry (2006), where
they were called “algebraic distributions,” and they will be called so hereafter. A comparison of the
algebraic (Eqn. 6.4.19) and lognormal (Eqn. 6.4.2) aerosol size spectra calculated for the two pairs of
spectra with the same parameters is shown in Fig. 6.8. One can see that algebraic and lognormal size
spectra are in good agreement over the sufficiently wide region from the small radii to the maxima
rm = 0.043–0.1 mm and to the larger radii. Some discrepancy is seen at larger radii in the tails, but this
region provides a small contribution into the number density and activity spectrum because fd(rd) are
here by two to three orders of magnitude smaller. An important feature of these distributions is that
they have finite asymptotics at both small and large radii, and tend to zero as (r /r0 ) k0 −1 at small r, and
(r /r0 )− ( k0 +1) at large r. Thus, at large radii, they resemble the inverse power law Junge’s spectra with
the index m = (k0 + 1), but in contrast to these, the algebraic spectra are finite at small r. In summary,
the new algebraic distributions are equivalent to both lognormal and inverse power laws, serve for
their “reconciliation,” and establish another link between them.
These algebraic representations of the size spectra are useful in various applications. Evaluation
of their analytical and asymptotic properties is simpler than those of the lognormal distributions, and
various expressions with these size spectra can be expressed via elementary functions rather than via
the Gaussian integral erf as in the case with the lognormal distributions. Being a good approximation
to the lognormal distribution but simpler in use, the algebraic functions (Eqns. 6.4.18)–(6.4.20) can be

1E+4
Size spectra (cm–3 µm–1)

algebraic, rm = 0.10 µm, σ = 2.15

1E+3 lognorm., rm = 0.10 µm, σ = 2.15
algebraic, rm = 0.043 µm, σ = 1.5
1E+2 lognorm., rm = 0.043 µm, σ = 1.5

10

1
0.5 1 1.5 2
Radius (µm)

Figure 6.8. Comparison of the algebraic and lognormal aerosol size spectra for the two pairs
of parameters: rm = 0.1 mm, sd = 2.15 (solid and open circles for the algebraic and lognormal,
respectively), and rm = 0.0.43 mm, sd = 1.5 (solid and open triangles). From Khvorostyanov and
Curry (2006), J. Geophys. Res., 111, D12202, reproduced with permission of John Wiley &
Sons, Inc.
6.5. Transformation of the Size Spectra of Wet Aerosol at Varying Humidity 211

used for approximation of the aerosol, droplet, and crystal size spectra as a supplement, and an alter-
native to the traditionally used power law, lognormal, and gamma distributions. Some applications
for calculations of the CCN activity spectra and drop activation are illustrated in the next sections.

6.5. Transformation of the Size Spectra of Wet Aerosol at Varying Humidity

6.5.1. Arbitrary Initial Spectrum of Dry Aerosol

We consider the humidity transformation of the size spectra of polydisperse ensemble of mixed
aerosol particles consisting of soluble and insoluble fractions. As the saturation ratio Sw increases
and exceeds the threshold of deliquescence Sw ,del of the soluble fraction, the hygroscopic growth of
the particles begins, and initially dry aerosol particles convert into wet “haze particles.” The initial
size spectrum fd (rd) of dry mixed aerosol particles transforms into the size spectrum fw(rw) of the wet
haze particles. The wet spectrum fw(rw) can be found from the concentration conservation equation
in differential form
fw (rw )drw = fd (rd )drd , (6.5.1)

which can be rewritten in the form that allows evaluation of fw(rw):

fw (rw ) = fd [rd (rw )](drd /drw ). (6.5.2)

This equation requires knowledge of rd as a function of rw, which is the reverse problem relative
to that considered in Section 6.2, and which again can be obtained from the cubic (Eqn. 6.2.10). For
b = 0.5 (volume-proportional soluble fraction), we obtain from (Eqn. 6.2.10)

brd3 A
= k − ln Sw . (6.5.3)
r − rd3 rw
3
w

This equation contains only rd3 and no other powers of rd, and its solution is simple. Solving for rd
we obtain
1/ 3
 (− ln Sw )rw + Ak 
rd (rw ) = rwϕ (rw ), ϕ (rw ) =   , (6.5.4)
 (− ln Sw )rw + Ak + brw 
drd r ϕ −2 (rw ) Ak b
= ϕ (rw ) − w . (6.5.5)
drw 3 [(− ln Sw )rw + Ak + brw ]2

Substitution of (Eqns. 6.5.4) and (6.5.5) into (Eqn. 6.5.2) allows calculation of the wet spectrum fw(rw)
with any arbitrary analytical expression for the dry spectrum fd (rd).
For the case b = 0 (surface-proportional soluble fraction), we obtain from (Eqn. 6.2.10) a cubic
equation for rd(rw) similar to (Eqn. 6.3.6) for rcr in Section 6.3,

brw
rd3 − rd2 − rw3 = 0.
rw ln Sw − Ak
(6.5.6)
Dividing by rd3 (Eqn. 6.5.6) can be rewritten for a dimensionless variable x = rd /rw

b
x 3 − 3 Z w x 2 − 1 = 0, Zw = . (6.5.7)
3[rw ln Sw − Ak ]
212 Wet Aerosol Processes

This incomplete cubic equation has the same form as (Eqn. 6.3.6a). Its parameter Q = Z w3 + 1/4 .
Since Zw < 0 at Sw < 1 and lnSw < 0, the solution can be chosen in algebraic or trigonometric form. If
Q > 0—i.e., −Zw3 < 1/4 or |Zw| < (1/4)1/3—then it is convenient to choose the same algebraic Cardano’s
solution for x as described in Section 6.3 and Appendix A.6 with the replacement Zd → Zw. Using
these solutions for x, we obtain for rd = xrw:
rd = rw χ (rw ), χ ( Z w ) = Z w + P+ ( Z w ) + P− ( Z w ), (6.5.8)
drd  dZ 
= χ ( Z w ) + rw  w + Z w2 [ P+−2 ( Z w )Q+ ( Z w ) + P−−2 ( Z w )Q− ( Z w )] , (6.5.9)
drw  drw 
where the functions P±(x) are defined in (Eqn. 6.3.8), and
−1/2
 1 1 
Q± ( Z w ) =  1 ±  Z w3 +   , (6.5.10)
 2 4 
dZ w b(− ln Sw )
=− . (6.5.11)
drw 3(− ln Sw )[(− ln Sw )rw + Ak ]2

As noted earlier, the functions P±, rd(rw) and Q±, are real under the condition |Zw| < (1/4)1/3, or

| Z w3 | < 1/4, or b < (3/22/3 )( Ak − rw ln Sw ). (6.5.11a)

This ensures the physical condition rd < rw. If Q < 0—i.e., −Zw3 > 1/4 or |Zw| > (1/4)1/3—then it is
convenient to choose the trigonometric solution described in Appendix A.6, which gives

1  1 
x = y1 + Z w = Z w + 2 Z w cos  arccos  1 + 2 
, (6.5.11b)
 3  2 Z w 

and rd = rwx(Zw). Substitution of (Eqns. 6.5.8)–(6.5.11b) into (Eqn. 6.5.2) yields fw(rw). The function
rd(rw) for the interstitial aerosol is obtained as the limit −lnSw ≈ 0 in the earlier equation, which gives
the smooth transition to size spectra of the wet interstitial aerosol.
It should be emphasized that this method for recalculation from the dry to the wet spectrum is not
tied to any specific shape of the spectrum, but is suitable for any dry aerosol spectrum. These equations
provide a solution and easy algorithm for analytical and numerical calculations of fw(rw) with any initial
fd(rd). This method can accommodate any analytical parameterization (e.g., Junge power law, lognor-
mal, algebraic, etc.) or a measured spectrum of any shape, e.g., a sectional representation. Despite some
algebraic complexity, these analytical equations are easy for coding and can be used for numerical
calculation of the wet spectrum from the dry spectrum. Particular cases of this approach are the calcu-
lations of hygroscopic growth of the dry power law spectra (e.g., Levin and Sedunov, 1966a; Sedunov,
1974; Fitzgerald, 1975; Khvorostyanov and Curry, 1999a; Cohard et al., 2000), or lognormal spectra
(e.g., von der Emde and Wacker, 1993; Ghan et al., 1993; Khvorostyanov and Curry, 2006; Shipway
and Abel, 2010) or sectional representation of the measured spectra (e.g., Nenes, and Seinfeld, 2003).

6.5.2. Lognormal Initial Spectrum of Dry Aerosol

As discussed in Section 6.2, for em ≥ 0.1–0.2, at sufficient dilution and not very high humidity,
Sw < 0.95–0.97, the terms with Ak can be neglected, and the relation between rw and rd can be
described by (Eqns. 6.2.15) or (6.2.16), which can be written in the form
rw = α rdγ , (6.5.12)
6.5. Transformation of the Size Spectra of Wet Aerosol at Varying Humidity 213

where a and g are determined in (Eqns. 6.2.15) and (6.2.16). The transformation to the wet spec-
tra becomes especially simple if the size spectrum of dry aerosol fd(rd) by the dry radii rd can be
represented by the lognormal distribution (Eqn. 6.4.2). We can derive the wet lognormal spectrum
substituting (Eqn. 6.5.12) into the relation (Eqn. 6.5.2) in the inverse form—that is, rd = (rw /α )1/γ
and drd /drw = (1/γ rw )(rd /α )1/γ . Thus, we can express fw(rw) via fd[rd(rw)] with rd as a function of rw:

fw (rw ) = fd [rd (rw )](drd /drw )

Na  {ln[(rw /α )1/γ/rd 0 )]}2  1  rw  1/γ
= exp −    . (6.5.13)
2π (ln σ d )(rw /α )1/γ  2 ln 2 σ d  γ rw  α 
The logarithm in the numerator of the argument in exponent here can be transformed as
2
1 1 1 
{ln[(rw /α )1/γ /rd 0 )]} 2 =  ln rw − ln α − ln rdγ0 
γ γ γ 
2
1  rw  ln 2 (rw /rw 0 )
=  ln α r γ  = , (6.5.14)
γ2  d0  γ2

where we introduced the “wet mean geometric radius” related to the dry mean geometric radius rd0
according to the same general humidity transformation (Eqn. 6.5.12):

rw 0 = α rdγ0 . (6.5.15)

Now the argument of the exponent in (Eqn. 6.5.13) can be rewritten as

{ln[(rw /α )1/γ /rd 0 )]}2 ln 2 (rw /rw 0 ) ln 2 (rw /rw 0 )

− =− =− , (6.5.16)
2 ln 2 σ d 2
2γ ln σ d2
2 ln 2 σ w

where we introduced the “wet dispersion”

σ w = σ dγ . (6.5.17)

The terms in front and after the exponent in (Eqn. 6.5.13) can be rewritten as
1/γ
Na 1  rw  Na 1 Na
  = = , (6.5.17a)
2π (ln σ d )(rw /α )1/γ γ rw α 2π (γ ln σ d ) rw 2π (ln σ w )rw

where we used again the relation for the wet dispersion g ln(sd) = ln(sdg ) = ln(sw). Substituting now
(Eqn. 6.5.16) into the exponent in (Eqn. 6.5.13) and using (Eqn. 6.5.17a) as a preexponential factor,
we obtain

Na  ln 2 (rw /rw 0 ) 
fw (rw ) = exp  − . (6.5.18)
2π (ln σ w )rw  2 ln 2 σ w 

So, we arrived again at the lognormal distribution, but with the new mean geometric radius (Eqn.
6.5.15) and dispersion (Eqn. 6.5.17) that are expressed via the corresponding properties of the initial
dry spectrum.
Thus, we derived a general and useful feature of the lognormal distributions: the invariance rela-
tive to the nonlinear transformation of the argument (radius or diameter) of the type (Eqn. 6.5.12).
This feature is hereafter referred to as “the 1st invariance property of the lognormal distribution” and
allows great simplification of calculations of the wet lognormal spectra. Using this invariance, the
214 Wet Aerosol Processes

transition to the wet spectra for a lognormal distribution can be based on the simple rule. If we have a
lognormal spectrum of radii rd with the mean geometric radius rd0 and dispersion sd (or correspond-
ing terms for diameters), then a nonlinear transformation of the variable of the form (Eqn. 6.5.12)
that satisfies the conservation law (Eqn. 6.5.2) leads again to the lognormal distribution with the new
mean geometric radius rw0 and the wet dispersion sw defined by (Eqns. 6.5.15) and (6.5.17). This is
valid not only for humidity transformation but for any other transformation of this form.
We can use this invariance to relate fd(rd) and fw(rw). For example, if the relation rw(rd) for the wet
aerosol with b = 0.5 at subsaturation is described by the hygroscopic growth law (Eqn. 6.2.15), it is
a transformation (Eqn. 6.5.12) with

α = [1 + b(− ln Sw )−1 ]1/3 , γ = 1, . (6.5.19)

In many cases for sufficiently dilute solutions, (Eqn. 6.2.16) is a good approximation as discussed in
Section 6.2, and thus
α = b1/3 (1 − Sw )−1/3 , γ = 2(1 + β ) /3. (6.5.20)

For the interstitial aerosol at Sw ~ 1, we find from (Eqn. 6.2.18) that

α = (b /Ak )1/2 , γ = 1+ β, (6.5.21)

Then, from the invariance property of the lognormal distribution, we obtain that the dry lognormal
spectrum (Eqn. 6.4.2) transforms into the wet lognormal spectrum (Eqn. 6.5.18), and its mean geo-
metric radius rw0 and dispersion sw are related to the corresponding quantities rd0 and sd of the dry
aerosol as:
rw 0 = rd 0 [1 + b(− ln Sw )−1 ]1/3 , σw = σd, Sw < 0.97, (6.5.22)

which corresponds to the relations (Eqn. 6.5.19) for rw(rd). In approximations (Eqns. 6.2.16 and
6.2.18) with a, g from (Eqns. 6.5.20) and (6.5.21), this yields another form: outside of a cloud,

rw 0 = rd2(1
0
+ β )/3 1/3
b (1 − Sw )−1/3 , σ w = σ d2(1+ β ) /3 , Sw < 0.97, (6.5.23)

and for the interstitial aerosol,

rw 0 = rd(10+ β ) (b /Ak )1/2 , σ w = σ d(1+ β ), Sw → 1. (6.5.24)

The analytic lognormal form of the size spectrum (Eqn. 6.5.18) in these cases is the same at subsatu-
ration and for the interstitial aerosol, but the values of the mean geometric radius rw0 and dispersion
sw are different, as shown by (Eqns. 6.5.22)–(6.5.24). However, the transition from the subsaturation
Sw < 1 to Sw ~1 is sufficiently smooth. The same relations allow easy recalculation between the two
saturation ratios Sw1 and Sw2, and show that a lognormal spectrum at Sw1 transforms to a lognormal
spectrum at Sw2.
The relations for hygroscopic growth rw(rd) of the form (Eqn. 6.5.12) can be used for recalculation
from the dry to the wet lognormal aerosol size spectrum or between the two wet spectra using the
invariance property described earlier.
The effect of humidity increase on the lognormal wet aerosol size spectra is shown in Fig. 6.9. As
predicted by (Eqns. 6.2.12) and (6.5.22), it results in a gradual shift of the modal radius to larger val-
ues, with a simultaneous decrease of the maxima. The transition to the limit Sw = 1 is fairly smooth,
6.5. Transformation of the Size Spectra of Wet Aerosol at Varying Humidity 215

1E+4
1E+3

Size distribution function

1E+2
Sw = 0.30

(cm–3 µm–1)
10
1 Sw = 0.70
0.1 Sw = 0.90
0.01 Sw = 0.95
1E–3 Sw = 0.97
1E–4 Sw = 1.00
1E–5
0.01 0.1 1 10
Radius (µm)
(a)

1E+4
1E+3
Size distribution function

1E+2
(cm–3 µm –1)

10 Sw = 0.30
1 Sw = 0.70
0.1 Sw = 0.90
0.01 Sw = 0.95
1E–3 Sw = 0.97
1E–4 Sw = 1.00
1E–5
0.01 0.1 1 10
Radius (µm)
(b)

60
Relartive error in wet size

50 Sw = 0.90
40 Sw = 0.95
spectra (%)

Sw = 0.97
30
Sw = 1.00
20
10
0
–10
–20
0.01 0.1 1 10
Radius (µm)
(c)

Figure 6.9. Humidity dependence of the wet aerosol size spectra. (a) full spectra fw1(rw) calculated
with (Eqns. 6.5.2)–(6.5.4) and complete equation (Eqn. 6.2.12) for rw(Sw); (b) approximate spectra
fw2(rw) calculated with (Eqn. 6.5.18) and rw0, sw from (Eqns. 6.5.15) and (6.5.17) using shortened
(Eqn. 6.2.15) for rw; (c) relative error d fw = (fw1 − fw2) / fw1 × 100 (%). Calculations are made for the
initial lognormal dry spectrum (rd0 = 0.03 mm, sd = 2.0), b = 0.5, b = 0.25 (50% of ammonium
sulfate), and several Sw indicated in the legend. In case Sw > 1 (sw > 0), the spectra should be limited
by the boundary radius rb = 2A / 3sw. From Khvorostyanov and Curry (2007), J. Geophys. Res.,
112(D5), D05206, reproduced with permission of John Wiley & Sons, Inc.
216 Wet Aerosol Processes

although there is a distinct decrease of the slopes. This resembles a corresponding effect for the
power law spectra, when the transition to Sw = 1 is accompanied by a decrease of the Junge power
index—e.g., m = 4 at Sw < 1 converts into m = 3 at Sw → 1 over a very narrow humidity range (see
previous Section 6.4 and Fig. 6.5).
The simplified (Eqns. 6.5.12) to (6.5.24) can be used in many cases for not very low dilutions
and soluble fractions, while the more complete (Eqns. 6.5.2)–(6.5.11) can be used otherwise. The
application of any of these methods depends on the specific aerosol spectra, and the choice of the
method can be justified for a given situation under consideration.

6.5.3. Inverse Power Law Spectrum

As discussed in Section 6.4, the aerosol size spectra are often represented by the inverse power laws:
− µd ,w
fd , w (rd , w ) = cd , w r , (6.5.25a)
µ −1 µ −1
cd , w = N a ( µ − 1)r min [1 − (rmin /rmax ) ], (6.5.25b)

where the subscripts “d” and “w” relate to the dry and wet aerosol, m d,w is the power index, and cd,w
is the normalizing factor. The spectrum is normalized to the aerosol concentration Na by integration
from rmin to rmax. The second term in the brackets in (Eqn. 6.5.25b) can be usually neglected since
rmin << rmax. Consider the case with b = 0.5. If Sw < 0.97 and rd ≥ 0.01 mm, then (Eqns. 6.5.2)–
(6.5.4) can be simplified by neglecting Ak in j and in the denominator of drd /drw. Substituting
(Eqns. 6.5.25a) and (6.5.25b) for the dry aerosol into (Eqn. 6.5.2), and using (Eqns. 6.5.4) and (6.5.5)
with these simplifications, we obtain after some transformations:

 bAk 
fw (rw ) = cd ϕ − ( µ −1) 1 − 2
ϕ3 
 3rw ( − ln S w ) 
( µ −1) / 3
µ −1 − µ
 b   bAk  b 
≈ N a ( µ − 1)r r  1 + − ln S  × 1 − 2 
1+  , (6.5.26)
Sw  
min w
 w   3rw ( − ln S w )  − ln

where j(rw) is defined in (Eqn. 6.5.4). Hence, the dry power law spectrum (Eqn. 6.5.25a) with the
index −m transforms at subsaturation into the wet spectrum, which is a superposition of the two power
laws with the indices −m and −(m + 1); the second of these becomes significant at Sw ≥ 0.95. The wet
inverse power law spectra were derived in Levin and Sedunov (1966a), Sedunov (1974), Fitzgerald
(1972), Smirnov (1978), and Khvorostyanov and Curry (1999a) for sufficiently diluted solutions
or when neglecting the insoluble fraction. Equation (6.5.26) is a generalization of these works that
allows using this spectrum down to substantially smaller humidities. The impact of the insoluble
fraction is described by the first term “1” in the rounded parentheses, and lower humidities are more
accurately represented using −lnSw instead of (1 − Sw) as in the previous works.
If b/(−lnSw) >> 1, then 1 can be neglected in the rounded parentheses; if also −lnSw ≈ (1 − Sw),
then using (Eqn. 6.2.14) for rw(Sw), making the corresponding simplifications in j and drd /drw in
(Eqns. 6.5.4) and (6.5.5), and substituting them into the general conservation (Eqn. 6.5.2), we obtain
after some algebraic transformations a wet spectrum valid for any b :
Rs
 b    1  Ak 
µ −1
fw (rw ) = 3 N a rmin  1− S  Rs rw− µwet −  Rs +  rw− ( µwet +1)  , (6.5.27a)
 w    3  (1 − S w ) 
6.5. Transformation of the Size Spectra of Wet Aerosol at Varying Humidity 217

3µ + 2β − 1 µ −1
µ wet = , Rs = , (6.5.27b)
2(1 + β ) 2(1 + β )
where m wet is the modified inverse power law index of the wet aerosol at subsaturation, and Rs is the
parameter that determines the major humidity dependence of the size spectrum (it could be called
the humidity index). Equation (6.5.27a) shows that the wet spectrum again consists of the two inverse
power laws with the indices m wet and (m wet + 1), but the estimates show that the second term gives a
noticeable contribution at high humidities, Sw ≥ 0.95–0.97. At lower humidities, it can be simplified as
Rs
µ −1
 b  − µ wet
fw (rw ) = 3 N a rmin  1 − S  Rs rw . (6.5.27c)
 w 

The Equations (6.5.27a) and (6.5.27c) become invalid in the cloud, at Sw → 1, but substitution of the
corresponding approximations in (Eqns. 6.5.4) and (6.5.5) for j and drd /drw into (Eqn. 6.5.2) gives
the wet size spectrum of the interstitial wet aerosol in the cloud:
Rs
 b  µ+β
µ −1
fw (rw ) = N a rmin (2 Rs )   rw− µint , µint = , (6.5.28)
 Ak  1+ β

where mint is the index of the interstitial wet aerosol. The spectra of deliquescent but not activated
interstitial aerosol at Sw > 1 are limited by the boundary radius rb = (2Ak/3)/(Sw − 1). These equations
also can be used for evaluation of the aerosol optical properties with account for the simultaneous
humidity and wavelength dependencies of aerosol extinction coefficients (e.g., Khvorostyanov and
Curry, 2007).
The Junge-type inverse power laws were and are used for evaluation of the dependence of the
wavelength l of aerosol extinction coefficients in Ångström’s law σ ext ~ λ − k A and optical depth
τ a ~ λ − k A (e.g., van de Hulst, 1957; Junge, 1963; Tomasi et al., 1983; Khvorostyanov and Curry, 1999a,b).
Substitution of the Junge inverse power law spectra f(r)~r− m into the expression (Eqn. 2.3.8a)
(see Chapter 2), for sext yields the relation between the Junge index m and Ångström’s kA coefficient,
kA = m − 3 (van de Hulst, 1957; Junge, 1963). The usual methods give the Ångström coefficients but
do not allow evaluation of the humidity dependence and a relation between the wavelength and hu-
midity dependencies. Equations (6.5.27a), (6.5.27b), and (6.5.27c) are convenient for evaluation of
the simultaneous dependencies of sext and ta on wavelength and humidity, and allow us to establish a
relation between them. Substitution of (Eqn. 6.5.27a) into (Eqn. 2.3.8a) for sext described in Sections
2.3 and 2.5 gives the expressions (Khvorostyanov and Curry, 1999b)

σ ext ( Sw , λ ) = Dext
a
,1 N a λ
− kA
(1 − Sw )− Rs [ψ ref ( Sw )]k A
a
− Dext ,2 N a λ
− ( k A +1)
(1 − Sw )− ( Rs +1) [ψ ref ( Sw )]k A , (6.5.28a)

where Dext
a
,1, Dext ,2 are the coefficients dependent on aerosol microstructure,
a

a
Dext ,1 = 3π ⋅ ( 2π )k b R rmin
A µ −1
s
 1 − (rmin / rmax ) µ −1  Rs I1ext
 1
a
Dext ,2 = 3π ⋅ ( 2π )k +1 b R rmin
A µ −1
s
 1 − (rmin / rmax ) µ −1  Ak Rs  Rs +  I 2ext , (6.5.28b)
 3
218 Wet Aerosol Processes

I1ext and I 2ext are dimensionless integrals

x max x max

∫ ∫ x ( A ) K ext ( x , nd ) dx ,
− k +2
I1ext = x − ( k A+1) K ext ( x , nd ) dx , I 2ext = (6.5.28c)
x min x min

and yref(Sw) are the corrections due to variations of the refractive index with humidity. The modified
Ångström’s coefficient kA, the power index m wet, and the humidity index Rs are linearly related

3µ − 4 β − 7
k A = µ wet − 3 = , k A = 3 Rs − 2, µ wet = 3 Rs + 1. (6.5.28d)
2 (1 + β )

These expressions establish relations between the size spectra, humidity, and wavelength depen-
dencies. For the volume-proportional soluble fraction with b = 0.5, the first of Equations (6.5.28d) for
kA reduces to the previous relation kA = m − 3. For the surface-proportional soluble fraction with b = 0,
(Eqn. 6.5.28d) gives a different relation, kA = (3m − 7)/2. For example, with m = 4, the coefficient
kA = 1 for b = 0.5 (sext ~ l−1), but kA = 2.5 for b = 0 (sext ~ l−2.5). That is, the wavelength dependence
is much stronger for b = 0—e.g., for the dust particles covered with a soluble shell. These relations
can be useful for estimates of the aerosol direct and indirect effects on climate. The expression for
sext (Eqn. 6.5.28a) depends on a single value of m. However, if the aerosol size spectrum is more com-
plicated, it can be approximated by a superposition of several power laws in various size ranges with
different m as described in the previous sections, and the equations for sext can be applied for each
part of the spectrum, the indices kA should be different in each size interval in the general case. Thus,
sext or ta in this case can be presented as a sum of several Ångström’s laws with different coefficients.
Both lognormal and inverse power laws have their own advantages and deficiencies and were used
for analysis or simulation of various aerosol properties, usually as independent tools, although in
many cases the correspondence between them is desirable. A link between the Junge and lognormal
spectra was found in Khvorostyanov and Curry (2006), as described by (Eqns. 6.4.4)–(6.4.6). The
properties of these effective power law indices for the wet aerosol are illustrated in Fig. 6.10. The
indices are negative at smaller r (corresponding to the growing branch on the left from the modal
radius of lognormal spectra) and become positive at larger r (to the right of the mode of lognormal
spectrum). An increase in Sw at Sw < 1 results in the parallel shift of the curves, since the increasing
humidity causes the growth of the mean radius but the dispersion does not depend on Sw and does not
change at Sw < 1 [see (Eqns. 6.5.22) and (6.5.23)]. When Sw ≈ 1, the m-indices decrease similarly to
the power laws for dry aerosol.

6.5.4. Algebraic Size Spectra

If the dry aerosol spectrum is described by the lognormal distribution (Eqn. 6.4.2), then its alge-
braic analog for dry aerosol is (Eqn. 6.4.19). If the wet aerosol is described by the corresponding
wet spectrum (Eqn. 6.5.18), its algebraic analog is obtained in the same way as the dry spectrum
(Eqn. 6.4.19) and is

k w 0 N a (rw /rw 0 ) kw 0 −1
fw (rw ) = , (6.5.29)
rw 0 [1 + (rw /rw 0 ) kw 0 ]2
6.6. CCN Differential Supersaturation Activity Spectrum 219

12
Sw = 0.75

Effective junge index µ(r)

8 Sw = 0.9
Sw = 0.97
4 Sw = 1.0

–4

0.01 0.1 1
Radius (µm)

Figure 6.10. Dependence on the saturation ratio Sw of the power indices m (Sw) of the wet aerosol
approximating the lognormal distributions calculated from (Eqn. 6.4.6) and rw0, sw from
(Eqns. 6.5.22) and (6.5.24); the parameters of the dry aerosol are modal radius rm = 0.03 mm,
dispersion sd = 2, b = 0.5, and b = 0.25. From Khvorostyanov and Curry (2007), J. Geophys. Res.,
112(D5), D05206, reproduced with permission of John Wiley & Sons, Inc.

4
kw0 = , (6.5.30)
2π ln σ w

where rw0 and sw = sdg are the geometric radius and dispersion of the wet spectrum defined in
(Eqns. 6.5.15) and (6.5.17) or in (Eqns. 6.5.19)–(6.5.21), and k0w is the corresponding index of the
wet spectrum. In particular, if the hygroscopic growth law (Eqn. 6.5.12) is valid and g = 1, then the
dispersion of the spectrum does not change, while the radius rw0 increases according to (Eqn. 6.5.19).
The advantage of the spectrum (Eqn. 6.5.29) is that it tends to zero at small rw as rwkw 0 −1 in contrast
to the inverse power law spectrum that tends to infinity at small rw. At large rw, the spectrum behaves
as rw− ( kw 0 +1), similar to Junge’s inverse power law. Small values at small and large radii ensure better
convergence of the integrals with the algebraic spectra at small radii than that with the inverse power
laws; no limitations are needed at small radii as with the Junge’s spectra.

6.6. CCN Differential Supersaturation Activity Spectrum

6.6.1. Arbitrary Dry Aerosol Size Spectrum

The CCN differential supersaturation activity spectrum js(scr) can be obtained from the size spectrum
of the dry CCN similar to the wet spectra in Section 6.5 using the conservation law in differential
form:
ϕ s (scr )dscr = − fd (rd )drd . (6.6.1)

Here scr is the critical supersaturation required to activate a dry particle with radius rd. The minus
sign occurs since an increase in rd (drd > 0) corresponds to a decrease in scr (dscr < 0). This is seen
from (Eqns. 6.3.3) or (6.3.11a) and was illustrated in Fig. 6.3a. The activity spectrum js(scr) can be
calculated from this equation if to rewrite it as

ϕ s (scr ) = − fd [(rd (scr ))](drd /dscr ). (6.6.2)

220 Wet Aerosol Processes

In order to use (Eqn. 6.6.2), we need to know rd as a function of scr or of rcr, since the relation of scr
and rcr is given by (Eqn. 6.3.11). This is a reverse problem relative to that considered in Section 6.3,
where we searched scr(rd). Taking the logarithm of (Eqn. 6.3.11), we obtain the equation

Ak brd2(1+ β )
ln(1 + scr ) = − . (6.6.3)
rcr rcr3 − rd3

Solving it relative to rd, we obtain

brcr
rd3 + acr rd2(1+ β ) − rcr3 = 0, acr = . (6.6.4)
Ak − rcr ln(1 + scr )

Using the relation that follows from (Eqn. 6.3.11a),

2 Ak
rcr = , (6.6.5)
3 ln(1 + scr )

we can exclude rcr and obtain the coefficient acr as

2b
acr = . (6.6.6)
ln(1 + scr )

For b = 0.5, we obtain from (Eqn. 6.6.4) an equation that contains only rd3. Thus, the solution for
rd(scr) is

2 Ak
rd (scr ) = rcr ξ (scr ) = ξ (scr ), (6.6.7)
3 ln(1 + scr )
−1/3
 2b 
ξ (rcr ) = 1 +  . (6.6.7a)
 (1 + ln scr ) 
The function drd/dscr required for (Eqn. 6.6.2) can be calculated from (Eqn. 6.6.7) as

drd 2 Ak ξ (scr )  2bξ 3 (scr ) 

=− 2 1 − . (6.6.8)
dscr 3(1 + scr ) ln (1 + scr )  3 ln(1 + scr ) 

For a CCN with rd >> 0.01 mm and a sufficiently large soluble fraction, these equations reduce to the
classical case. At these conditions, scr << b, 1 + ln(scr) ≈ scr, and approximately

ξ (scr ) ≈ (1 + 2b /scr )−1/ 3 ≈ (scr /2b)1/ 3 . (6.6.9)

Substituting this into (Eqn. 6.6.7), we obtain

rd (scr ) = (4 Ak3 / 27b)1/3 scr−2 /3 . (6.6.10)

Inverting (Eqn. 6.6.10) for scr(rd), we obtain

1/2 1/2
 4 A3   4 A3 
scr = rd− (1+ β )  k  =  k  , (6.6.11)
 27b   27 B 
6.6. CCN Differential Supersaturation Activity Spectrum 221

which coincides with the classical Köhler’s expression (Eqn. 6.3.3). Hence, (Eqn. 6.6.7) is an inver-
sion of the generalized scr − rd relation (Eqn. 6.3.11a) with rcr from (Eqn. 6.3.7). For this limiting
case, we obtain from (Eqn. 6.6.8):

drd /dscr = (32 Ak3 /729b)1/3 scr−5/3 , (6.6.12)

which can be obtained directly from (Eqn. 6.6.10) and verifies the validity of (Eqn. 6.6.8).
Now, the differential activity spectrum js (scr) (Eqn. 6.6.2) can be calculated for b = 0.5 using
(Eqns. 6.6.7) and (6.6.8) for any shape of the initial dry size spectrum fd (rd).
For the case b = 0, (Eqn. 6.6.4) becomes a cubic equation similar to (Eqn. 6.3.6) but with unknown rd,

rd3 + acr rd2 − rcr3 = 0, (6.6.13)

with acr defined in (Eqn. 6.6.6). It can be reduced to the dimensionless form for x = rd /rcr,

x 3 + ax
ɶ 2 − 1 = 0, aɶ = (acr /rcr ) = 3b / Ak . (6.6.13a)

This is a cubic equation of the type (Eqn. A.6.1) from Appendix A.6 with aɶ = 3b /Ak , bɶ = 0 , and
cɶ = −1 . It can be reduced to the incomplete cubic equation considered in Appendix A.6 with defined
there parameters p = −3(b/Ak)2, q = 2(b/Ak)3 − 1, and Q = 1/4 − (b/Ak)3. As discussed in Section 6.3
and Appendix A.6, it is convenient to choose a solution depending on the sign of Q = 1/4 − (b/Ak)3. If
Q < 0, or b/Ak > (1/4)1/3 ≈ 0.63, then it is suitable to choose a trigonometric solution

2b b
rd (scr ) = ψ (U ), U= , (6.6.14)
3 ln(1 + scr ) Ak

1  1 
ψ (U ) = 2 cos  arccos  3 − 1  − 1, (6.6.15)
 3  2U 
drd rd (scr )
=− . (6.6.16)
dscr (1 + scr ) ln(1 + scr )

If Q > 0, or b/Ak < (1/4)1/3 ≈ 0.63, then a convenient solution is Cardano’s algebraic form

rd = rcr χ ( Z cr ), χ ( Z cr ) =  Z cr + P+ ( Z cr ) + P− ( Z cr )  , Z cr = −U = − b /Ak , (6.6.17)

and the functions P±(z) are defined in (Eqn. 6.3.8), where Zd should be replaced with Zcr . The defini-
tions of Zcr and (Eqn. 6.3.8) for P±(z) show that P±(z) becomes complex for Q < 0. Although P+(z) and
P−(z) are complex-conjugate and the solution is real, it can be more convenient to use the trigonometric
solution (Eqns. 6.6.14)–(6.6.16) for this case. The functions rd(dscr), drd/dscr are expressed for this case
by (Eqns. 6.6.14) and (6.6.16), and the activity spectrum j(scr) is given by (Eqn. 6.6.2) for arbitrary fd(rd).

6.6.2. Lognormal Activity Spectrum

The calculation of the CCN activity spectrum is simpler for a dry lognormal size spectrum fd(rd) with
a mean geometric radius rd0 and dispersion sd if the critical supersaturation scr is related to the dry
radius rd by a nonlinear transformation of the variable of the form

scr = α rd−γ . (6.6.18)

222 Wet Aerosol Processes

Then, the reverse transformation, rd(scr), is

−1/γ −1/γ
s  drd 1  scr 
rd =  cr  , =−   . (6.6.19)
α  dscr γ scr  α 

The derivation of the activity spectrum is similar to the derivation of the lognormal wet spectrum in
Section 6.5. Substitution of (Eqn. 6.6.19) into (Eqn. 6.6.2) gives

ϕ s (scr ) = − fd [(rd (scr )](drd /dscr )

−1/γ
 {ln[(scr /α ) rd 0 ]}   1   scr 
−1/γ −1 2
Na
=− exp − ×−    . (6.6.20)
2π (ln σ d )(scr /α )−1/γ 
2
2 ln σ d   γ scr  α
The logarithm in the numerator of the argument in exponent here can be transformed as
2
 1 1 1 
{ln[(scr /α )−1/γ rd−01 ]}2 =  − ln scr + ln α + ln rd−0γ 
 γ γ γ 
2
1  scr  ln 2 (scr /s0 )
=  ln α r −γ  = , (6.6.21)
γ2  d0  γ2

where we introduced the “mean geometric supersaturation” s0 related to the dry mean geometric
radius rd0 according to the same relation (Eqn. 6.6.18) as in the general variable transformation

s0 = α rd−0γ . (6.6.22)

Now the argument of the exponent in (Eqn. 6.6.20) can be rewritten as

{ln[(scr /α )−1/γ rd−01 ]}2 ln 2 (scr /s0) ln 2 (scr /s0)

− =− = − , (6.6.23)
2 ln 2 σ d 2γ 2 ln 2 σ d 2 ln 2 σ s

where we introduced the “supersaturation dispersion” ss

σ s = σ dγ . (6.6.24)

The terms before and after the exponent in (Eqn. 6.6.20) can be combined as
−1/γ
Na  1   scr  Na 1 Na
−  − γ s   α  = = , (6.6.25)
2π (ln σ d )(scr /α )−1/γ  cr  2π (γ ln σ d ) scr 2π (ln σ s )scr

where we used again the relation for the supersaturation dispersion g ln(sd) = ln(sdg ) = ln(ss). Sub-
stituting now (Eqn. 6.6.23) into the exponent in (Eqns. 6.6.20) and (6.6.25) as a preexponential factor,
we obtain

Na  ln 2 (scr /s0 ) 
ϕ s (scr ) = exp  − . (6.6.26)
2π (ln σ s )scr  2 ln 2 σ s 

So, we arrive again at the lognormal distribution, but with the new mean geometric supersaturation s0
(Eqn. 6.6.22) and supersaturation dispersion ss (Eqn. 6.6.24) that are expressed via the corresponding
properties of the initial dry spectrum.
6.6. CCN Differential Supersaturation Activity Spectrum 223

Thus, if the initial CCN size spectrum is lognormal and satisfies the conservation law
(Eqn. 6.6.1), and the critical supersaturation is related to the dry radius by a nonlinear transformation
(Eqn. 6.6.18), then the differential activity spectrum js(scr) is also lognormal distribution by the vari-
able scr with the new mean geometric supersaturation s0, and supersaturation dispersion ss expressed
via the dry radius and dispersion as in (Eqns. 6.6.22) and (6.6.24). This feature is referred hereafter
to as “the 2nd invariance property of lognormal distributions” and is similar to the 1st invariance
property in Section 6.5, except for the different power of s0.
In the classical Köhler case, for dilute solutions when rcr >> rd, it follows from (Eqn. 6.3.3) that the
parameters a, g of this transformation (Eqn. 6.6.18) are
1/2
 4 A3 
α = K  , γ = 1 + β. (6.6.27)
 27b 

Using the 2nd invariance property, we find that the dry lognormal CCN size spectrum with rd0 and sd
corresponds to the lognormal CCN activity spectrum (Eqn. 6.6.26) with the mean geometric super-
saturation s0 and dispersion ss
1/2
 4 A3 
s0 = α r−γ
d0 = k rd−0(1+ β ) , σ s = σ dγ = σ d(1+ β ) . (6.6.28)
 27b 

Using the 2nd invariance property makes the transition from the dry size spectra to the activity spec-
tra automatic and very simple once we define the scr − rd relation—e.g. (Eqns. 6.6.18) and (6.6.27).
Fig. 6.11 shows a comparison of the differential activity spectra js(scr), integral (or cumulative)
activity spectra
scr

N CCN (scr ) = ∫ ϕ s (s) ds, (6.6.29)

0

and relative error dNCCN = (NCCN(f) − NCCN(K))/NCCN(f) × 100, calculated with the 2 different methods:
1) using the dry lognormal size spectrum (Eqn. 6.4.2) and the full (Eqns. 6.6.2)–(6.6.8) (symbol f),
and 2) as the lognormal distribution for js(scr) with s0 and ss based on the approximation of the
classical Köhler theory (Eqn. 6.6.28) (symbol K). Calculations are performed with b = 0.5,
Nd =150 cm−3, rm = 0.03 mm, sd = 2.15, and various volume soluble fractions of ammonium sulfate
in % from 50% to 0.1%. The approximate classical method overestimates NCCN(s) by 10–40% at
s < 0.02, but the general agreement of both methods is good enough for ev > 10−2. For smaller ev, the
classical approximation underestimates NCCN(s) by 40–55% in the region s = 0.1−0.6%, where the
major activation process occurs. Thus, the new more complete (Eqns. 6.6.2)–(6.6.8) predict much
more rapid activation at small soluble fractions than Köhler’s method.
Shown in Fig. 6.12 are the differential and cumulative CCN activity spectra calculated for
b = 0 with (Eqns. 6.6.2) and (6.6.14)–(6.6.17) for CCN with the soluble film of thickness l0 on
the surface of an insoluble core. The dry size spectra are chosen as a model of the coarse mode,
lognormal with rm = 0.3 mm and sd = 2.15. The values of b are calculated with (Eqn. 6.2.9) and l0
estimated from the data in Levin et al. (1996) as described in Section 6.2.1. The results for b = 0 are
compared with the case b = 0.5, ev = 0.1, and the same dry spectrum. Fig. 6.12 shows that NCCN with
Differential activity spectrum (cm–3 %–1)
1E+4

1E+3

1E+2

10
f, 50 %
1
K, 50 %
0.1 f, 1 %
0.01 K, 1 %

1E–3 f, 0.1 %
K, 0.1 %
1E–4
0.01 0.1 1 10
Supersaturation (%)
(a)
1E+3
Integral activity spectrum (cm–3)

1E+2

10
f, 50 %

1 K, 50 %
f, 1 %
0.1 K, 1 %
f, 0.1 %
0.01
K, 0.1 %
1E–3
0.01 0.1 1 10
Supersaturation (%)
(b)
60

40
Relative error in Nd (%)

20

–20

–40 50 %
–60 1%
–80 0.1 %

–100
0.01 0.1 1 10
Supersaturation (%)
(c)

Figure 6.11. (a) Differential activity spectra js(scr); (b) integral activity spectra NCCN (scr); and
(c) relative error defined in the text, calculated with the 2 methods: 1) for the dry lognormal size
spectrum (Eqn. 6.4.2) with the full equations (Eqns. 6.6.2)–(6.6.8) (symbol f, solid symbols), and
2) as the lognormal distribution for js(scr) with s0 and ss based on the approximation of the classical
Köhler theory (Eqn. 6.6.28) (symbol K, open symbols). Calculations are performed with b = 0.5,
Nd =150 cm−3, rm = 0.03 mm, and sd = 2.15. The numbers in the legends indicate volume soluble
fraction of ammonium sulfate in %. From Khvorostyanov and Curry (2007), J. Geophys. Res.,
112(D5), D05206, reproduced with permission of John Wiley & Sons, Inc.
224
6.6. CCN Differential Supersaturation Activity Spectrum 225

1E+4

Differential activity spectrum (cm–3 %–1)

1E+3

β = 0, l0 = 0.01 µm
1E+2
β = 0, l0 = 0.02 µm

β = 0, l0 = 0.03 µm
10
β = 0.5, εv = 0.1

1
0.01 0.1
Supersaturation (%)
(a)

1E+2
Cumulative activity spectrum (cm–3)

β = 0, l0 = 0.01 µm
1E+1
β = 0, l0 = 0.02 µm

β = 0, l0 = 0.03 µm

β = 0.5, εv = 0.1

1
0.01 0.1
Supersaturation (%)
(b)

Figure 6.12. Differential (a) and cumulative (b) CCN activity spectra calculated with b = 0,
(Eqns. 6.6.2) and (6.6.14)–(6.6.17) and various thicknesses l0 of the soluble film on the surface
of an insoluble core, and compared with the case b = 0.5 with soluble fraction ev = 0.1. The dry
size spectra are lognormal (Eqn. 6.4.2) with the modal radius rm = 0.3 mm and sd = 2.15. From
Khvorostyanov and Curry (2007), J. Geophys. Res., 112(D5), D05206, reproduced with permission
of John Wiley & Sons, Inc.
226 Wet Aerosol Processes

b = 0 (surface-proportional soluble fraction) and thicknesses l0 = 0.03, 0.02, and 0.01 mm become
greater than that with b = 0.5 (volume-proportional soluble fraction) at sw > 0.01, 0.015 and 0.04%,
respectively, although in the latter two cases the soluble fractions in CCN with b = 0 are substantially
smaller. This example shows that CCN such as dust particles coated with thin soluble films can be
more effective than CCN with soluble fractions homogeneously distributed in volume, suggesting an
important role of mineral dust in cloud nucleation.

6.6.3. Algebraic Activity Spectrum

If the dry aerosol spectrum is described by the lognormal distribution (Eqn. 6.4.2), then its algebraic
analog for dry aerosol is (Eqn. 6.4.19) and the algebraic wet spectrum is described by (Eqn. 6.5.29).
The corresponding differential activity spectrum can be obtained in various ways. The first way is
the same as was used for derivation of the lognormal activation spectrum (Eqn. 6.6.26) from the log-
normal size spectrum (Eqn. 6.4.2) of the dry aerosol—i.e., using the 2nd invariance property. As we
could see, the analytical form of the activation spectrum is the same as that of the size spectrum, with
the replacements rd 0 → s0 , σ d → σ s . Applying this simple procedure to the dry algebraic spectrum
(Eqn. 6.4.19) with an additional replacement
4 4
kd 0 = → ks 0 = , (6.6.30a)
2π ln σ d 2π ln σ s

we obtain the algebraic activity spectrum

N a k s 0 (scr /s0 ) ks 0 −1
ϕ s (scr ) = . (6.6.30b)
s0 [1 + (scr /s0 ) ks 0 ]2

The other way is to use a general transformation (Eqn. 6.6.18) in the conservation (Eqn. 6.4.2). The
advantage of this way is that it allows us to check if this transformation of the variable in the algebraic
size spectrum leads again to the algebraic activity spectrum. This is illustrated in the following text.
Substituting rd (scr) = (scr /a)−1/g and drd /dscr from (Eqn. 6.6.19) in the conservation Equation (6.6.2)
with the dry algebraic size spectrum (Eqn. 6.4.19), we obtain

k d 0 N a [(scr /α )−1/γ /rd 0 ]kd 0 −1  1   scr  −1/γ

ϕ s (scr ) = −  − γ s   α  . (6.6.31)
rd 0 [1 + [(scr /α )−1/γ /rd 0 ]kd 0 ]2  cr 

The following relation allows us to simplify this expression:

(scr /α )−1/γ /rd 0 = (scr /α rd−0γ )−1/γ = (scr /s0 )−1/γ , (6.6.32)

where
s0 = α rd−0γ (6.6.33)

is the same mean geometric supersaturation s0, and dispersion ss as introduced for lognormal distri-
bution. The factor kd0 /g in (Eqn. 6.6.31) is transformed as

kd 0 4 4
= = = ks 0 , σ s = σ dγ , (6.6.33a)
γ 2π (γ ln σ d ) 2π ln σ s
6.6. CCN Differential Supersaturation Activity Spectrum 227

where ks0 is the analog of the kd0-index and ss is the supersaturation dispersion. Substituting these
relations into (Eqn. 6.6.31), we obtain

N a ks 0 [(scr /s0 )−1/γ ]γ ks 0 −1

ϕ s (scr ) = (6.6.34)
scr (scr /s0 ) ) {1 + [scr /s0 )−1/γ ]γ ks 0 }2
1/ γ

Reducing the powers and canceling (scr/s0)1/g in the numerator and denominator, we have

N a ks 0 (scr /s0 )− ks 0 N k (scr /s0 ) ks 0 −1

ϕ s (scr ) = − ks 0 2
= a s0 . (6.6.35a)
scr [1 + (scr /s0 ) ] s0 [1 + (scr /s0 ) ks 0 ]2

So, we arrive again at the algebraic distribution (Eqn. 6.6.30b). That is, we proved that the general
transformation of the variable (Eqn. 6.6.18), scr = α rd−γ , in the algebraic size spectrum leads to the
algebraic activity spectrum. If this transformation is based on Köhler’s relations (Eqn. 6.3.3) for the
critical supersaturation, then the parameters a and g are expressed by (Eqn. 6.6.27), s0 and ss are
defined by (Eqn. 6.6.28) as in the case with lognormal spectrum, and the ks0 index is
1/2
 4 A3 
s0 =  k  rd−0(1+ β ) , σ s = σ d(1+ β ) , (6.6.35b)
 27b 
4 4
ks 0 = = . (6.6.35c)
2π ln σ s 2π (1 + β ) ln σ d

The algebraic activity spectrum (Eqn. 6.6.35a) is a generalization of Twomey’s power law activity
spectrum j s(s) = Cksk−1. It is shown in the following that ks0 is the asymptotic value of the k-index
in the CCN activity power law at small s, while at large supersaturations, js(s) decreases with s and
ensures finite drop concentrations.
A slightly different form of the algebraic activity spectrum (Eqns. 6.6.30b) and (6.6.35a) can be
more convenient for comparison with the other models (the subscript “cr” at s is omitted in the fol-
lowing text for brevity and convenience of comparison). Equation (6.6.35a) can be rewritten as

ϕ s (s) = k s 0 C0 s ks 0 −1 (1 + η0 s ks 0 )−2 . (6.6.36)

Here, taking into account (Eqns. 6.6.35b) and (6.6.35c),

ks 0 /2
 27b 
C0 = N s − ks 0
a 0 = Na  2 
(rd 0 ) ks 0 (1+ β ) , (6.6.37a)
 4 Ak 
ks 0 /2
 27b 
η0 = s0− ks 0 =  2  (rd 0 ) ks 0 (1+ β ) . (6.6.37b)
 4 Ak 

The first term on the right-hand side of (Eqn. 6.6.36), k s 0 C0 s ks 0 −1 , represents Twomey’s (1959) power
law (Eqn. 6.1.5) for the differential activity spectrum. In contrast to the C0 and k in previous empirical
parameterizations based on fits to experimental data, here the analytical dependence is derived from
the modified Köhler theory and the algebraic approximation of the lognormal functions, and param-
eters C0, ks0 are expressed directly via aerosol parameters. This first term describes drop activation at
small supersaturations s << s0 (as in the clouds with weak updrafts and in the “haze chambers”) and
grows with s as s ks 0 −1 . The second term in parentheses in (Eqn. 6.6.36) decreases at large s >> s0 as
228 Wet Aerosol Processes
− ( ks 0 +1)
s −2 ks 0, overwhelms the growth of the first term, and ensures the asymptotic decrease ϕ s (s) ~ s .
Thus, the term in parentheses serves effectively as a correction to Twomey’s law and prevents an un-
limited growth of concentration of activated drops at large supersaturations. The asymptotic behavior
can be summarized as
ϕ s (s << s0 ) ~ s ks 0 −1 , ϕ s (s >> s0 ) ~ s − ( ks 0 +1) . (6.6.37c)

The entire CCN spectrum (Eqn. 6.6.36) resembles the corresponding equation from Cohard et al.
(1998, 2000) or Shipway and Abel (2010):

ϕ s (s) = kCs k −1 (1 + η s 2 )− λ , (6.6.38)

where the first term is also Twomey’s differential power law, and the term in parentheses was added
by the cited authors as an empirical correction with the two parameters h, l, which were varied
and chosen by fitting the experimental data. Despite the general functional similarity, the powers in
the parentheses are different in (Eqns. 6.6.36) and (6.6.38). Therefore, integration of (Eqn. 6.6.36)
yields an expression as algebraic fraction for the drop concentration Nd(s) (Ghan et al., 1993, 1995;
Khvorostyanov and Curry, 2006, 2008a), and integration of (Eqn. 6.6.38) yields an expression that
contains the hypergeometric function (Cohard et al., 1998, 2000; Shipway and Abel, 2010). The al-
gebraic representations (Eqns. 6.6.36) or (6.6.35a) of js(s) found in Khvorostyanov and Curry (2006)
allow us to establish a bridge between Twomey’s power law, the lognormal parameterizations of drop
activation (Ghan et al., 1993, 1995; von der Emde and Wacker, 1993; Abdul-Razzak et al., 1998,
2000; Fountoukis and Nenes, 2005), and the modifications of the power law in Cohard et al. (1998,
2000) and Shipway and Abel (2010).
Shown in Fig. 6.13 is an example of the CCN differential algebraic activity spectrum js(scr) (Eqns.
6.6.35a) or (6.6.36) calculated with b = 0.25 (CCN with ~50% of ammonium sulfate or ~20% of
NaCl) and four combinations of modal radii and dispersions. The area beneath each curve repre-
sents the drop concentration Ndr that could be activated at any given supersaturation s, so that the

1E+3
CCN activity spectra

1E+2
1E+1
(cm–3 %–1)

1E+0
1E–1 rm = 0.10 µm, σ = 2.0
1E–2 rm = 0.03 µm, σ = 2.0
1E–3 rm = 0.10 µm, σ = 1.5
1E–4 rm = 0.03 µm, σ = 1.5
1E–5
0.01 0.10 1.00 10.00
Supersaturation (%)

Figure 6.13. CCN algebraic differential activity spectrum js(scr) calculated with (Eqn. 6.6.36),
b = 0.25, and four combinations of modal radii rm and dispersions sd of the dry aerosol spectra
indicated in the legend. From Khvorostyanov and Curry (2006), J. Geophys. Res., 111, D12202,
reproduced with permission of John Wiley & Sons, Inc.
6.6. CCN Differential Supersaturation Activity Spectrum 229

maximum of js(scr) indicates the region of scr where its increase leads to the most effective activation.
A remarkable feature of this figure is a substantial sensitivity to the variations of rm, sd. The maxi-
mum for the maritime-type spectrum with rm = 0.1 mm, sd = 2, lies at very small scr ~ 0.01%. When sd
decreases to 1.5, or rm decreases to 0.03 (closer to the continental spectrum), the maximum of js(scr)
shifts to s ~ 0.04–0.1%. With rm = 0.03 mm, sd = 1.5, the region scr ~ 0.01–0.1% becomes relatively
inactive and the maximum shifts to 0.4%. Thus, even moderate narrowing of the dry spectra or a
decrease in the modal radius may require much greater vertical velocities for activation of the drops
with the same concentrations.
A comparison of the algebraic (Eqns. 6.6.35a) and (6.6.36) and lognormal (Eqn. 6.6.26) differ-
ential activity spectra in Fig. 6.14 shows their general good agreement. The discrepancy increases
in both tails, but their contributions to the number density is small, as will be illustrated in the follow-
ing. Thus, the algebraic functions (Eqns. 6.6.35a) and (6.6.36) approximate the lognormal spectrum
(Eqn. 6.6.26) with good accuracy.
The differential activity spectrum for a multimodal aerosol consisting of I fractions is a simple
generalization of (Eqn. 6.6.35a) by summation over all modes
I
N ai k s 0 i (s /s0 i ) ks 0 i −1
ϕ s (s ) = ∑ (6.6.39)
i =1 s0 i [1 + (s /s0 i ) ks 0 i ]2

where Nai is the CCN concentration in the i-th mode, s0i and ks0i are defined as in (Eqns. 6.6.35b) and
(6.6.35c), but with Aki, bi, and bi specific for each i-th mode
1/2
 4 A3 
s0 i =  ki  rd−0(1i + βi ) , (6.6.40a)
 27bi 
4 4
ks 0 i = = . (6.6.40b)
2π ln σ si 2π (1 + β i ) ln σ di

alg., (0.10 µm, 2.15)

log., (0.10 µm, 2.15)
CCN activity spectra

1E+3
alg., (0.043 µm, 1.5)
(cm–3 %–1)

1E+2 log., (0.043 µm, 1.5)

1E+1

1E+0

1E–1
0.01 0.10 1.00 10.00
Supersaturation (%)

Figure 6.14. Comparison of the algebraic (alg.) (Eqn. 6.6.36) and lognormal (log.) (Eqn. 6.6.26)
differential CCN activity spectra js(scr). A pair of digits in the parentheses in the legend denotes
modal radius rm in mm and dispersion sd of the corresponding dry aerosol spectrum. From
Khvorostyanov and Curry (2006), J. Geophys. Res., 111, D12202, reproduced with permission of
John Wiley & Sons, Inc.
230 Wet Aerosol Processes

6.7. Droplet Concentration and the Modified Power Law for Drops Activation

6.7.1. Lognormal and Algebraic CCN Spectra

The concentration of CCN or activated drops based on the lognormal size spectrum can be obtained
by integration of the lognormal differential activity spectrum js(s) (Eqn. 6.6.26) over the supersatu-
rations to the maximum value s reached in a cloudy parcel (we omit here also the subscript “cr” for
brevity) (Ghan et al., 1993, 1995; von der Emde and Wacker, 1993; Fountoukis and Nenes, 2005;
Khvorostyanov and Curry, 2006, 2008a),
s
N a   1 ln(s /s0 )  
N d (s) = N CCN (s) = ∫ ϕ s (s ') ds ' = 1 + erf   . (6.7.1)
0
2   2 ln σ s  

Droplet or CCN concentration in algebraic form can be obtained from integration of the algebraic
CCN spectrum js(s) (Eqn. 6.6.35a) or (6.6.36) by s (Khvorostyanov and Curry, 2006, 2008a),

(s /s0 ) ks 0
N d (s ) = N a = C0 s ks 0 (1 + η0 s ks 0 )−1 . (6.7.2)
[1 + (s /s0 ) ks 0 ]

The parameters s0 and ss in (Eqns. 6.7.1) and (6.7.2) are defined by (Eqn. 6.6.28). C0 and h0 are defined
in (Eqns. 6.6.37a) and (6.6.37b) and expressed via aerosol microphysical properties.
The algebraic form allows a simple but clear physical interpretation. According to (Eqn. 6.7.2),
the asymptotic of NCCN(s) at s << s0 has the form of Twomey’s power law N CCN (s) = C0 s ks 0 . The
deficiency of the previous parameterization was an unlimited growth of NCCN(s) at high s, which
stimulated several attempts to bound NCCN(s) at high s as in the just cited works. The new algebraic
parameterization (Eqn. 6.7.2) removes this deficiency. The term in parentheses is a correction to the
power law: Its asymptotic at s >> s0 is s − ks 0 , it compensates the growth of the first term, and it pre-
vents unlimited drop concentration. The asymptotic limit of drop concentration is NCCN(s) → Na at
large s, and hence the number of activated drops is limited by the total aerosol concentration.
If the dry aerosol size spectrum is multimodal with I modes (e.g., I = 3 in three-modal distributions
in Whitby, 1978, or seven modes as in Vignati et al., 2004), then it can be written as a superposition
of I lognormal fractions (Eqn. 6.4.2) with Nai, sdi, and rd0i being the number concentration, disper-
sion, and mean geometric radius of the i-th fraction as in (Eqn. 6.4.3). The mean geometric super-
saturations s0i, dispersions ssi, and other parameters for each fraction are then defined by the same
equations as described earlier for a single fraction. Then, the algebraic dry and wet size spectra, and
the differential and integral activity spectra, are obtained for each fraction as described earlier, and
the corresponding multimodal spectra are superpositions of the I fractions. The multimodal droplet
concentration in algebraic form is derived from (Eqns. 6.6.39) or (6.7.2):
I
(s /s0 i ) ks 0 i I
N d (s) = ∑ N ai = ∑ C0 i s ks 0 i [1 + η0 i s ks 0 i ]−1 . (6.7.3)
i =1 [1 + (s /s0 i ) ] ks 0 i
i =1

The parameters Nai, s0i, bi, and bi can be different for each fraction—e.g., bi = 0.5 may correspond to
the accumulation mode, and bi = 0 may correspond to the coarse mode consisting of the dust particles
coated with the soluble film.
6.7. Droplet Concentration and the Modified Power Law for Drops Activation 231

6.7.2. Modified Power Law for the Drop Concentration

The power law NCCN = Csk is often used for parameterization of the results of CCN measurements and
of drop activation in many cloud models. An analytical function for the k-index has been found (similar
to the m -index (Eqn. 6.4.5)) by Khvorostyanov and Curry (2006) using the method for the power law
representation of the continuous functions. The power law for CCN and its derivative are written as
N CCN (s) = Cs s k , dN CCN (s)/ds = kCs s k −1 . (6.7.4)

Solving these two equations for k(s), we obtain

dN CCN (s)/ds ϕ (s )
k (s ) = s =s s . (6.7.5)
N CCN (s) N CCN (s)

Equation (6.7.5) allows evaluation of k(s) with known differential js(s) and cumulative NCCN(s) CCN
spectra. Substituting here (Eqn. 6.6.26) for js(s) and (Eqn. 6.7.1) for NCCN(s), we obtain k(s) in terms
of lognormal functions:
−1
2 1  ln 2 (s /s0 )    ln(s /s0 )  
k (s ) = exp  − 2  1 + erf   . (6.7.6)
π ln σ s  2 ln σ s    2 ln σ s  

Here s0 and ss are defined by (Eqn. 6.6.28). The algebraic form of the index k(s) is obtained by sub-
stitution of (Eqn. 6.6.30b) for js(s) and (Eqn. 6.7.2) for NCCN(s) into (Eqn. 6.7.5):
ks 0 /2 −1
ks 0   27b  
k (s ) = = k s 0 1 + s ks 0 rdk0s 0 (1+ β )  3 
 . (6.7.7)
1 + (s /s0 ) ks 0   4 Ak  

This equation shows that the effective index k(s) decreases with increasing s. If the aerosol size spec-
trum is multimodal and is given by a superposition of I algebraic distributions, then the k-index is
derived from (Eqns. 6.7.5) and (6.7.3) by summation over I modes:
−1
 I N s /s 
ks 0 i ks0i
I k s 0 i N ai ( s /s0 i )  ai ( 0i ) 
k (s ) = ∑ ∑  , (6.7.8)
i =1 [1 + (s /s0 i ) ks 0 i ]2  i =1 [1 + (s /s0 i ) ]
ks 0 i


where the parameters ks0i, s0i, and Nai are defined as before in (Eqn. 6.6.35b), but for each i-th mode.
Equations (6.7.5)–(6.7.8) provide a continuous representation of k over the entire s-range and
allow evaluation of k(s) for any s with given ss and s0 that are expressed via rd, sd, b, and b—i.e.,
directly via aerosol physico-chemical properties. That is, knowledge of the size spectra and composi-
tion of the dry or wet CCN allows direct evaluation of k(s) over the entire s-range. This solves the
problem outlined in Jiusto and Lala (1981), Yum and Hudson (2001), and other studies: various values
of the k-index at various s found experimentally show a general tendency of a decrease of k with in-
creasing s. Note that the k-index is not constant for a given air mass or aerosol type as often assumed,
but depends on a given s at which it is measured. Equation (6.7.7) shows that for small s << s0, the
asymptotic value k(s) = ks0. For large s >> s0, the index decreases with s as k (s) = k s 0 (s /s0 )− ks 0 and
tends to zero. This behavior is in agreement with the experimental data from Jiusto and Lala (1981),
Yum and Hudson (2001), and others. That is, with the same CCN properties, the values of k(s) are
different at different locations and vertical velocities in a cloud.
232 Wet Aerosol Processes

The coefficient Cs(s) can now be calculated using (Eqn. 6.7.2) for NCCN(s) and (Eqn. 6.7.7) for
k(s) as

Cs (s) = N CCN (s)s − k ( s ) = C0 s χ ( s ) [1 + (s /s0 ) ks 0 ]−1 , (6.7.9)

where C0 = N a s0− ks 0 is expressed in (Eqn. 6.6.37a) via aerosol microstructure. The power index c (s)
of s in (Eqn. 6.7.9) is

(s /s0 ) ks 0
χ (s) = k s 0 − k (s) = k s 0 . (6.7.10)
1 + (s /s0 ) ks 0

Now we can write the CCN (or droplet) concentration in the form of a modified power law as

N CCN (s) = Cs (s)s k ( s ) , s in share of unit. (6.7.11)

This equation is usually used with supersaturation s in percent, related to ssu in share of the unit as
s = 102 ssu. Substitution of this relation into (Eqn. 6.7.11) yields a more conventional form:

N CCN (s) = C pc (s)s k ( s ) , s in percent. (6.7.12)

In (Eqn. 6.7.11), both k(s) and Cs(s) depend on the ratio s/s0 and thus do not depend on units; k(s) is
calculated again from (Eqn. 6.7.7) but with s and s0 in percent, and the coefficient

C pc (s pc ) = 10 −2 k ( s ) C (s). (6.7.13)

Equation (6.7.12) is similar to power law (Eqn. 6.1.4); however, now with the parameters depend-
ing on s as just described. Hence, k(s) and C(s) are now expressed directly via the parameters of the
lognormal spectrum (Na, rd0, sd) or its algebraic equivalent and its physico-chemical properties via
simple parameterization of b in (Eqns. 6.2.5)–(6.2.7).
Finally, the modified power law for the multimodal aerosol types is described again by
(Eqns. 6.7.11) and (6.7.12) with the k(s)-index evaluated from (Eqn. 6.7.8) and the coefficient Cs(s)
I
C (s) = ∑ C0 i s χi ( s ) [1 + (s /s0 i ) ks 0 i ]−1 , (6.7.14)
i =1

where ci = ks0i − k(s), and ks0i, C0i, s0i, and Nai are defined for each i-th mode. The coefficient Cpc(s)
with supersaturation in percent is defined by (Eqn. 6.7.13). The number of modes I is determined
by the nature of aerosol and is the same as used for multimodal size spectra with the lognormal
approach.
This analytical s-dependence of Cs(s) and k(s) in (Eqns. 6.7.11) and (6.7.12) provides a theoretical
basis for many previous findings and improvements of the drop activation power law. In particular,
the C-k space constructed by Braham (1976) based on experimental data follows now from the equa-
tions for k(s) and Cs(s) with use of any relation of maximum s to vertical velocity. The decrease of
the k-slopes with increasing s analyzed by Jiusto and Lala (1981), Yum and Hudson (2001), Cohard
et al. (1998, 2000), Shipway and Abel (2010), and others is predicted by (Eqns. 6.7.5)–(6.7.8), as
well as its dependence on the nature of aerosol. The proportionality of coefficient Cs to the aerosol
concentration explains substantially greater values of Cs observed in continental rather than maritime
air masses as compiled by Twomey and Wojciechowski (1969) and Hegg and Hobbs (1992), and used
by cloud modelers.
6.7. Droplet Concentration and the Modified Power Law for Drops Activation 233

6.7.3. Supersaturation Dependence of Power Law Parameters

The equivalent power index k(s), calculated with (Eqn. 6.7.7) and a monomodal algebraic (equivalent
to lognormal) size spectrum, is shown in Fig. 6.15a and b and is compared with the experimental data
from Jiusto and Lala (1981) who collected the data from several chambers. Given here is also the
field data collected by Yum and Hudson (2001) with a continuous flow diffusion chamber (CFDC)
at two altitudes in the Arctic in May 1998 during the First International Regional Experiment-Arctic
Cloud Experiment (FIRE-ACE). It is seen that the k-index is not constant as assumed in many cloud
models. The calculated k-indices reach the largest values of 1.5–4.2 at s ≤ 0.01%, where they tend
to the asymptotic ks0 (Eqn. 6.6.35c) and increase with decreasing dispersion of the dry CCN spec-
trum since ks0 ~ (lnsd)−1. As s increases, k(s) is initially almost constant, and then decreases slowly
up to s ~ 0.03–0.05%, and then decreases more rapidly in the region s ~ 0.05–0.12% to values less
than 0.1–0.2 at s > 1%. The k-indices increase with decreasing modal radii rm and dispersions sd
indicated in the legends. Agreement of calculated k(s) with haze chamber data is reached at sd = 1.3,
rm = 0.085 mm, and with CFDC at sd = 1.5 and rm = 0.043 mm. Agreement with the Arctic field data
by Yum and Hudson (2001) is reached with rm = 0.045 mm, sd = 2.15 in the layer 960–1010 mb and
rm = 0.043 mm, and sd = 1.9 in the layer 560–660 mb.
Thus, this model explains and describes quantitatively the observed decrease in the k-index
with increasing supersaturation reported previously by many investigators (e.g., Twomey and
Wojciechowski, 1969; Braham, 1976; Jiusto and Lala, 1981) and relates it to the aerosol size spectra
and physico-chemical properties. A more detailed analysis of experimental data with these equations
should be based on simultaneous use of the measured multimodal aerosol size spectra and CCN
supersaturation activity spectra.
In contrast to most previous models where k and C are constant, the values of “effective” C(s),
Cpc(s) in this model also depend on supersaturation. The spectral behavior of Cpc(s) calculated from
(Eqn. 6.7.9) with different rm, sd and the same Na = 100 cm−3 is shown in Fig. 6.16. For s << s0,
the coefficients tend to the asymptotic limit C pc (0) = 10 −2 ks 0 C and reach values of 103–105 cm−3
caused by the dependence C0 ~ Ak−2 ks 0 rdk0s 0 (1+ β ) with Ak ~ 10−7 cm and rd0 ~ 3 × 10−6 to 10−5 cm. This
dependence causes an increase in Cpc with decreasing sd (increasing ks0) and with increasing rd0
seen at small s in Fig. 6.16; i.e., the narrower spectra and the larger modal radius, the faster the drop
activation at small s. The values of Cpc(s) decrease with increasing s by 1–3 orders of magnitude
and tend to Na at spc > 0.1–0.7%, since the asymptotics at large s is C pc (s pc ) = 10 −2 k ( s ) N a s −pck ( s ) , and
k(s) → 0 at large s. Hence, all the coefficients Cpc tend to Na at spc ≥ 0.5% as seen in Fig. 6.16. Thus,
k (s)
N CCN (s) = C pc s pc ~ 10 −2 k ( s ) N a and tends to the limiting value Na, which ensures finite values of Na
in contrast to the models with constant k, C.
The data on k and C measured at s = 1% in various air masses and geographical regions were
compiled by Hegg and Hobbs (1992) and Pruppacher and Klett (1997). The values mostly varied
in the wide ranges: in a maritime air mass, k = 0.3–1.3, C = 100–400; and in a continental air mass,
k = 0.4–0.9, C = 600–5000. Such values are often used in cloud models at much smaller than 1%
maximum supersaturations. The preceding consideration shows that these values of k and C may be
substantially higher at smaller s (Figs. 6.15 and 6.16). Equations (6.7.6)–(6.7.10) allow recalculations
between any values of supersaturation and direct calculations using the measured physico-chemical
properties of aerosol.
234 Wet Aerosol Processes

5.0 0.043 µm, 1.9

0.085 µm, 1.47

4.0
0.03 µm, 1.3
Effective power index k(s)

0.085 µm, 1.3

3.0
NRL Haze

2.0 DRI Haze

DRI CFD
1.0
NRL SDC

0.0
0.01 0.1 1 10
Supersaturation (%)
(a)

3.0
0.10 µm, 2.15

2.5
0.045 µm, 2.15
Effective power index k(s)

2.0 0.043 µm, 1.9

0.043 µm, 1.5

1.5
YH01, 960–1010 mb

1.0 YH01, 560–660 mb

0.5

0.0
0.01 0.1 1 10
Supersaturation (%)
(b)

Figure 6.15. Supersaturation dependence of the k-index (Eqn. 6.7.7) calculated for the algebraic
size spectrum equivalent to the lognormal spectrum of dry CCN with various modal radii rm and
dispersions sd indicated in the legend and comparison: (a) with the experimental data from Jiusto
and Lala (1981) from 4 chambers: haze chambers (NRL Haze and DRI Haze), continuous flow
diffusion chamber (DRI CFD), and static diffusion chamber (NRL SDC), and (b) with the data
collected in FIRE-ACE in 1998 (Yum and Hudson, 2001) (YH01) at the heights 960–1010 mb and
560–660 mb. From Khvorostyanov and Curry (2006), J. Geophys. Res., 111, D12202, reproduced
with permission of John Wiley & Sons, Inc.
6.7. Droplet Concentration and the Modified Power Law for Drops Activation 235

1E+5
rm = 0.10 µm, σ = 2.15

rm = 0.10 µm, σ = 1.9

rm = 0.10 µm, σ = 1.5

Coefficient Cpc(s) (cm–3)

1E+4
rm = 0.045 µm, σ = 2.15

rm = 0.03 µm, σ = 1.9

rm = 0.03 µm, σ = 1.5

1E+3

1E+2

1E–2 0.1 1
Supersaturation spc (%)

Figure 6.16. Equivalent coefficient Cpc(s) (Eqns. 6.7.9) and (6.7.13) in the modified power law
for NCCN (Eqns. 6.7.11) and (6.7.12) calculated for the algebraic size spectrum equivalent to the
lognormal size spectrum of dry CCN with modal radii rm and dispersions sd indicated in the legend
and other parameters described in the text. For the convenience of comparison, all curves are
calculated with Na = 102 cm−3. From Khvorostyanov and Curry (2006), J. Geophys. Res.,
111, D12202, reproduced with permission of John Wiley & Sons, Inc.

A comparison of the concentrations NCCN(s) calculated using the generalized power law
(Eqn. 6.7.11) and erf function based on the lognormal distribution (Eqn. 6.7.1) shows in Fig. 6.17
their good agreement and illustrates good accuracy of the algebraic distributions and renewed gen-
eralized power law as compared to the direct integration of the lognormal distributions. The curves
NCCN(s) calculated with the newer power law are not linear in log-log coordinates as they are with
the old power law (Eqn. 6.1.4) and constant C0, k, but are concave in agreement with the measure-
ments (e.g., Jiusto and Lala, 1981; Hudson, 1984; Yum and Hudson, 2001) and other models (e.g.,
Ghan et al., 1993; 1995; Feingold et al., 1994; Cohard et al., 1998, 2000; Shipway and Abel, 2010).
The reason for this concavity is quite clear from Figs. 6.5a,b and 6.11–6.14 for the size and activ-
ity spectra: the rate of increase in the concentration of activated drops dNd(s)/ds is greatest at small
supersaturations in the left branch of js(s) (Figs. 6.11–6.14), which correspond to the right branch
of fd(rd) at rd > rm (Fig. 6.5a,b). Thus, dNd(s)/ds decreases with growing s, especially at s > 1%—i.e.,
in the left branch of the small dry CCN with rd < 0.03 mm (Fig. 6.5a). Effectively, some “saturation”
with respect to supersaturation occurs, causing k(s), C(s), and dNd(s)/ds to decrease with s and lead-
ing to finite Nd(s) at large s.
Finally, Fig. 6.18 shows NCCN(s) calculated with the lognormal size spectra and generalized power
law (Eqn. 6.11) and compared to the corresponding field data obtained by Yum and Hudson (2001)
in the FIRE-ACE campaign in May 1998 in the Arctic. The parameters rm, sd, and Na were varied
236 Wet Aerosol Processes

Drop concentration (cm–3)

100

rm = 0.10 µm, σ = 2.15

10
rm = 0.045 µm, σ = 2.15
rm = 0.043 µm, σ = 1.9
rm = 0.030 µm, σ = 1.47
1
1E–2 0.1 1 1E+1
Supersaturation (%)

Figure 6.17. Comparison of the accumulated CCN spectra NCCN(s) calculated using the modified
power law (Eqn. 6.7.11) (solid symbols) and using (Eqn. 6.7.1) with the erf function (open
symbols). The values of the corresponding modal radii rm and dispersions sd of the dry aerosol
spectra are indicated in the legend. For convenience of comparison, NCCN is calculated with the
dry aerosol concentrations of 250, 200, 150, and 100 cm−3 from the upper to lower curves. From
Khvorostyanov and Curry (2006), J. Geophys. Res., 111, D12202, reproduced with permission of
John Wiley & Sons, Inc.
CCN concentration (cm–3)

1E+2

rm = 0.045 µm, σd = 2.15, Na = 75

1E+1
rm = 0.043 µm, σd = 2.00, Na = 180
YH01, 960–1010 mb
YH01, 860–990 mb
1
1E–2 0.1 1
Supersaturation (%)

Figure 6.18. Supersaturation dependence of the CCN integral activity spectrum NCCN(s) calculated
with the modified power law (Eqn. 6.7.11) for the lognormal size spectra with rm, sd, and Na
(in cm−3) indicated in the legend (solid diamonds and circles), compared to the corresponding field
data obtained by Yum and Hudson (2001, YH01) in the FIRE-ACE campaign in May 1998 in the
Arctic in two flights at altitudes 960–1010 mb and 860–990 mb (open diamonds and circles). From
Khvorostyanov and Curry (2006), J. Geophys. Res., 111, D12202, reproduced with permission of
John Wiley & Sons, Inc.

slightly in the calculations, although the calculations were constrained to the measured k-indices
(Fig. 6.15b), so that the values of the parameters had to provide an agreement for both k(s) and
NCCN(s). Good agreement over the entire range of supersaturations was found with the values indi-
cated in the legend. The values of modal radii and dispersions are typical for the accumulation mode.
This comparison shows that this modified power law (Eqns. 6.7.11)–(6.7.12) can reasonably reproduce
the experimental data on CCN activity spectra and concentrations of activated drops and can be used
for parameterization of drop activation in cloud models.
Solutions of Cubic Equations for Equilibrium and Critical Radii 237

Appendix A.6 for Chapter 6. Solutions of Cubic Equations

for Equilibrium and Critical Radii

A cubic equation of the form

x 3 + ax ɶ + cɶ = 0.
ɶ 2 + bx (A.6.1)
has algebraic and trigonometric solutions.
The algebraic Cardano’s solution is sought by substitution:

x = y − aɶ /3. (A.6.2)

(e.g., Korn and Korn, 1966). This gives an incomplete cubic equation for y

y 3 + py + q = 0, (A.6.3)

where p and q are expressed via the primary parameters

3
aɶ 2 ɶ  aɶ  ɶɶ
ab
p=− + b, q = 2  − + cɶ. (A.6.4)
3  3 3
The three roots y1, y2, and y3 of the incomplete cubic (Eqn. A.6.3) are

Aɶ + Bɶ Aɶ − Bɶ
y1 = Aɶ + Bɶ , y2,3 = − ±i 3, (A.6.5)
2 2
with
1/3 1/3
 q   q 
Aɶ =  − + Q1/2  , Bɶ =  − − Q1/2  , (A.6.6)
 2   2 
3 2
 p  q
Q=  +  , (A.6.7)
 3   2

where i = −1 . The choice of the cubic roots in Aɶ and Bɶ is determined by the relation AB ɶ ɶ = − p/3.
If the coefficients of (Eqn. A.6.1) are real, then the equation has: a) one real root and two complex-
conjugated roots if Q > 0; or b) three real roots, at least two of which are equal, if Q = 0; or c) three
real different roots if Q < 0.
The trigonometric solution of (Eqns. A.6.3) or (6.2.21) with real coefficients, Q < 0 and p < 0 is
1/2 1/2
 p α  p α π 
y1 = 2  −  cos , y2,3 = −2  −  cos  ±  , (A.6.8)
 3 3  3  3 3

with
−3/2
 q p 
α = arccos  −  −  . (A.6.9)
 2 3 
Only the real root y1 is physical and should be used, and the roots y2,3 are complex and should be
rejected.
These two types of solutions, algebraic (Eqns. A.6.5)–(A.6.7) and trigonometric (Eqn. A.6.8), are
used in Sections 6.2 and 6.3.
238 Wet Aerosol Processes

Solution (Eqn. 6.2.21) for the Equilibrium Radius rwi of Interstitial Aerosol

Equation (6.2.19) for the equilibrium radius rwi of interstitial aerosol is reduced to the cubic (Eqn.
6.2.20) for the dimensionless variable x = rw/rd:
1/ 2 1/2
 br 2 β   b 
x 3 − 3 Z d2 x − 1 = 0, with Zd =  d  = rdβ   . (A.6.10)
 3 Ak   3 Ak 

This is an incomplete cubic equation for x of the form (Eqn. A.6.3) with aɶ = 0 and the coefficients

p = −3 Z d2 , q = −1. (A.6.11)

A solution can be chosen in trigonometric or algebraic form, depending on the sign of Q, defined in
(Eqn. A.6.7) as
3 2
 p  q 1
Q =   +   = − Z d6 + . (A.6.12)
 3   2 4

The trigonometric solution is convenient if Q < 0, or Z d6 > 1/4 —i.e., with a sufficiently large soluble
fraction. Thus, there is one physical real root; the other two roots are complex-conjugated and should
be rejected. The real root is
1/ 2 −3 / 2
 p α q  p
y1 = 2  −  cos , with cos α = − −  . (A.6.13)
 3 3 2 3

Substituting here p and q from (Eqn. A.6.11), we obtain x = y1, since aɶ = 0 :

1  Z −3  
x = y1 = 2 Z d cos  arccos  d  
 3  2  

 b 
1/2
1  1  3 A  3/2  

= 2rdβ   cos  arccos   2kβ    . (A.6.14)
 3 Ak  3  2  brd   
 
Finally, the equilibrium interstitial aerosol radius rwi = xrd is

 b 
1/2
1  1  3 A  3/2  

rwi = rd1+ β   cos  arccos   2kβ    .
 3 Ak  3  2  brd   
  (A.6.15)
6
The algebraic Cardano’s solution is more convenient if Q > 0, or Z < 1/4 —i.e., for a small solubled

fraction. Then, the solution of an incomplete cubic equation is described by (Eqns. A.6.5) and (A.6.6)
with Q from (Eqn. A.6.12). Thus

1/3 1/2 1/3

 q  1  1  
y1 = Aɶ + Bɶ , Aɶ =  − + Q1/2  =  +  − Z d6   , (A.6.16)
 2  2  4  
1/3 1/2 1/3
 q  1  1  
Bɶ =  − − Q1/2  =  −  − Z d6   , (A.6.17)
 2  2  4  
Solutions of Cubic Equations for Equilibrium and Critical Radii 239

rd
rwi = rd y1 = {[1 + (1 − 4 Z d6 )1/2 ]1/3 + [1 − (1 − 4 Z d6 )1/2 ]1/3 }, (A.6.18)
21/3
with Zd from (Eqn. A.6.10).

Solution (Eqns. 6.3.7)–(6.3.8) for the Critical Radius rcr

Equation (6.3.6) for the critical radius

1/2
 br 2 β 
rcr3 − (3rd Z d )rcr2 − rd3 = 0, Zd =  d  , (A.6.19)
 3 Ak 

can be rewritten as an equation for a dimensionless variable x = rcr/rd as

x 3 + aɶ x 2 − 1 = 0, aɶ = −3 Z d . (A.6.20)

It is a particular case of the complete cubic (Eqn. A.6.1) for x with coefficients aɶ = −3 Z d , bɶ = 0 , and
cɶ = −1 . Then, the coefficients p, q, and Q of the general algebraic Cardano’s solution (Eqns. A.6.4)–
(A.6.7) can be expressed via the primary parameters

aɶ 2 ɶ
p=− + b = −3 Z d2 , (A.6.21)
3
3
 aɶ  ɶɶ
ab
q = 2  − + cɶ = −2 Z d3 − 1, (A.6.22)
 3 3
3 2 2
 p  q  1 1
Q =   +   = − Z d6 +  Z d3 +  = Z d3 + . (A.6.23)
 3   2  2 4
Since the coefficients of the original equation are real and Q > 0 in (Eqn. A.6.23), the case a) of the
preceding three cases is valid and the equation has one real root. Substitution of these p, q, and Q into
(Eqn. A.6.6) gives Aɶ and Bɶ after some algebraic transformations
1/3
 q 
Aɶ =  − + Q1/2  = P+ ( Z d ), (A.6.24)
 2 
1/2 1/3
  1 1
P+ ( Z d ) =  Z d3 +  Z d3 +  +  , (A.6.25)
  4 2
1/3
 q 
Bɶ =  − − Q1/2  = P− ( Z d ), (A.6.26)
 2 
1/2 1/3
  1 1
P− ( Z d ) =  Z d3 −  Z d3 +  +  , (A.6.27)
  4 2

Now, the single real solution of the incomplete cubic (Eqn. A.6.3) is

y1 = Aɶ + Bɶ = P+ ( Z d ) + P− ( Z d ). (A.6.28)
240 Wet Aerosol Processes

The solution of the original equation of the cubic (Eqn. A.6.19) for rcr is obtained after returning to
the variable x according to (Eqn. A.6.2):

aɶ
x = y1 − = y1 + Z d . (A.6.29)
3
Substituting here y1 from (Eqn. A.6.28), and the relation rcr = rdx, we finally obtain

rcr (rd ) = rd χ ( Z d ), χ ( Z d ) =  Z d + P+ ( Z d ) + P− ( Z d )  . (A.6.30)

This is the final solution (Eqn. 6.3.7) for rcr(rd) given in Section 6.3.
7
Activation of Cloud Condensation
Nuclei into Cloud Drops

7.1. Introduction

As discussed in Chapter 6, the number of cloud drops is an important determinant of cloud optical
properties and the formation of precipitation. In the initial stages of cloud formation, the number of
cloud drops is directly related to the number of cloud condensation nuclei (CCN) activated. Drop
activation schemes used prior to the 1990s were based mostly on Twomey’s (1959) power law for the
concentration of drops Ndr activated on cloud condensation nuclei (CCN). This scheme is still applied
in some atmospheric models. The drawback of Twomey’s parameterization is that Ndr is unlimited at
high supersaturations and can exceed CCN concentration Na.
A substantial revision and intensive development of new cloud drop activation parameterizations
and their effects on climate modeling began in the 1990s (see reviews in Charlson et al., 2001;
Lohmann and Feichter, 2005; McFiggans et al., 2006; Svenningsson et al., 2006; IPCC, 2007; and in
Chapter 6 of this book). Along with the analytical modifications of Twomey’s power law described
in Chapter 6, parameterizations of drop nucleation have been developed using results from parcel
models that are fit to various empirical functions of a few nondimensional parameters (Abdul-Razzak
et al., 1998; Abdul-Razzak and Ghan, 2000, 2004; Fountoukis and Nenes, 2005; Ming et al., 2006).
Saleeby and Cotton (2004) developed another approach consisting of lookup tables compiled from
several thousand runs of a parcel model. A comparison of various recent parameterizations of drop
activation and their performance was conducted by Ghan et al. (2011).
The necessity to run parcel models many times for compiling lookup tables or tuning the param-
eterizations may make the procedure time-consuming, and does not easily reveal the relevant physi-
cal relationships. Two alternative approaches were suggested by Khvorostyanov and Curry (2008a,
2009a), who derived the integro-differential equation for supersaturation using the algebraic size
and activity spectra from Khvorostyanov and Curry (2006, 2007) described in Chapter 6. In the first
approach, Khvorostyanov and Curry (2008a) found a fast numerical solution of this equation for the
time of CCN activation tm, maximum supersaturation sm, and concentration of activated droplets Ndr
as functions of the physico-chemical properties and size spectrum of the CCN and the vertical veloc-
ity w, and studied the kinetics of drop activation using this numerical solution. This method can be
much faster than methods based on running numerous parcel models and compiling the lookup tables.
A deficiency of all numerical solutions is that they do not demonstrate the general analytical
dependencies of the drop activation on various parameters. The search for analytical solutions for
tm, sm, and Ndr is desirable because they allow the following applications: a) control for the accu-
racy of various numerical solutions, especially in cases where general dependencies are unclear

241
242 Activation of Cloud Condensation Nuclei into Cloud Drops

and the spread of the parcel model runs can be significant (e.g., at strong variations of the conden-
sation coefficient or surface tension); b) development of newer parameterizations based on the
characteristic parameters occurring in these solutions; c) construction of the general solutions by
interpolation among the particular analytical solutions; and d) the design of laboratory and field
experiments. A method based on analytical solutions of the supersaturation equation was developed
in Khvorostyanov and Curry (2009a).
It has been known since the pioneering work by Twomey (1959) that the supersaturation equa-
tion does not allow general analytical solutions, even with the simplest power law activity spectrum,
unless certain simplifications are made. The situation becomes even more complicated when more
complex activity spectra are used (e.g., lognormal or algebraic) because of the impossibility of exact
analytical evaluation of the characteristic integrals of this problem. Twomey (1959) considered drop-
let growth with the condensation coefficient ac ~ 1—i.e., in the diffusion regime of droplet growth.
Subsequent laboratory and field experiments and theoretical works showed that ac can be as low as
10−5—i.e., droplets grow in the kinetic regime (Deryagin et al., 1966; Deryagin and Kurgin, 1972;
Pruppacher and Klett, 1997; Seinfeld and Pandis, 1998; Buikov and Khvorostyanov, 1979; Feingold
and Chuang, 2002; Chuang, 2003). However, parameterizations of drop activation considered mostly
the cases with ac ~ 1, with some numerical estimates of the effects of ac (Nenes et al., 2002; Ming
et al., 2006), but the general analytical dependencies of tm, sm, and Ndr on ac have not been derived.
The CCN differential activity spectrum is written as described in Chapter 6:

ϕ s (s) = dN dr (s) /ds, (7.1.1)

where Ndr is the number of cloud drops nucleated, which corresponds directly to the number of CCN
activated at supersaturation s. The number of CCN actually activated is determined by the maximum
supersaturation sm reached in a cooling cloud parcel, which is determined by two competing pro-
cesses: supersaturation generation due to cooling, and supersaturation absorption due to condensa-
tion growth of the newly formed drops. The final Ndr formed after the supersaturation has reached sm
is given by the integral CCN activity spectrum:
sm
N dr (sm ) = ∫ ϕ s (s′) ds′. (7.1.2)
0

Thus, parameterization of Ndr according to (Eqn. 7.1.2) requires knowledge of both js(s) and sm, and
therefore a solution of the supersaturation equation in order to find sm.
Among the various methods for parameterizing the differential CCN spectrum js(s), we consider
three different mathematical approaches: power law, lognormal, and algebraic. The most commonly
used power law approach was introduced by Twomey (1959) (see Chapter 6):

ϕ s (s) = CT ks k −1 , (7.1.3)

where the constant CT and the index k are typically empirically determined. Substitution of (Eqn. 7.1.3)
into (Eqn. 7.1.2) yields the corresponding power law

N dr (sm ) = CT smk , (7.1.4)

which has been widely used in cloud physics. As mentioned before, the drawbacks of this parameter-
ization are the following: the value of Ndr is not limited at high sm and can exceed total CCN concen-
tration Na; and the parameters CT and k are usually determined empirically from measurements of Ndr
7.2. Integral Supersaturation in Liquid Clouds with Drop Activation 243

at varying values of sm and are not related directly to the aerosol microphysical properties. Besides, as
shown in Chapter 6 , cloud chamber experiments have found a decrease of the index k with increas-
ing sm (e.g., Jiusto and Lala, 1981; Ji and Shaw, 1998; Yum and Hudson, 2001; Pruppacher and Klett,
1997), and hence there is no unique value of k even for the same aerosol type.
We considered in Chapter 6 the activity spectra js(s), and accumulated spectra Ndr(s) and treated
supersaturation as a continuous variable. Hence, the method developed in Chapter 6 can be used as a
refinement to the power law used in cloud models with prognostic supersaturation, or in the analysis
of chamber experiments, where the maximum supersaturation sm can be calculated or measured and
then Ndr(sm) determined. However, most cloud models, numerical weather prediction models, and
climate models do not have prognostic supersaturation equations and do not evaluate supersaturation
explicitly. Hence, they use parameterizations for sm and Ndr in terms of the predicted variables, most
often in terms of the vertical velocity w similar to Twomey’s (1959) original parameterization (e.g.,
Ghan et al., 1997; Lohmann et al., 1999; Saleeby and Cotton, 2004; Morrison et al., 2005a,b).
When s is not an independent continuous variable, but is constrained by sm due to interaction of the
dynamical and microphysical factors, the applicability of the power law (Eqn. 7.1.4) becomes unclear.
To ensure finite Ndr ≤ Na at high values of s, the indices k and coefficients CT should be different at
low and high values of sm. However, it is uncertain in general if sm and the function Ndr(sm) can be
described by the power law or quasi-power law with variable k and CT. If so, analytical expressions are
needed for sm and Ndr that relate the values of k and CT to aerosol microphysics and cloud dynamics.
For models with longer time steps that cannot accommodate a prognostic equation for supersatura-
tion, a parameterization is needed that allows us to calculate sm, along with the time tm during which
maximum supersaturation is reached and CCN activation proceeds, and the final parameterization
of Ndr(sm). This requires analysis of the dependencies of tm, sm, Ndr, and other characteristics on the
parameters of the CCN size spectra and chemical composition. Toward improving parameterization
of cloud droplet activation in cloud and climate models, Chapter 7 extends the quasi-power law for
drop activation obtained in Chapter 6. The integro-differential equation for integral water supersatu-
ration is derived and solved together with the other equations of drop activation kinetics, which yields
relatively simple equations for tm, sm, and Ndr in the form of the quasi-power laws that are functions of
the vertical velocity and parameters of aerosol size spectra and chemical composition.

7.2. Integral Supersaturation in Liquid Clouds with Drop Activation

When an air parcel rises adiabatically at a vertical velocity w, the air cools, and the relative humid-
ity increases and reaches saturation at some level. Then, the parcel becomes slightly supersaturated
and CCN activation begins. The parcel supersaturation is governed by two competing processes:
supersaturation generation by the rising motion and supersaturation absorption by the drops in the
condensation process.
This process can be described by the equation for water supersaturation, which we use in the form
from Section 5.3. Using (Eqn. 5.3.16) for a liquid cloud (Idep = 0), and the relation (1/p)(dp/dt) =
−(g/RaT)w based on the equation of state and hydrostatic approximation, we can write

1 dsw Γ
= c1w w − 1 I con , (7.2.1)
(1 + sw ) dt ρv
244 Activation of Cloud Condensation Nuclei into Cloud Drops

where
 L Mw  g
c1w (T ) =  e − 1 . (7.2.2)
 cpT Ma  Ra T

Γ1 is the psychrometric correction (Eqn. 5.3.15), and all notation is the same as in Section 5.3. The
condensation vapor flux Icon to the droplets is the integral of the mass growth rate over the size spec-
trum that is expressed via growth rate (drd /dt) of the droplet radius rd:
∞ drd
I con = 4πρ w ∫ rd2 f (rd , t ) drd , (7.2.3)
0 dt
where fd (rd) is the size distribution function of the newly formed drops. We use (drd /dt) in the form
(Eqn. 5.1.46) of Section 5.1
drd c s Dv ρ ws
= 3w w , c3 w = , (7.2.4)
dt rd + ξcon ρ w Γ1
1/2
4 Dv  8 RT 
ξcon = , Vw =   , (7.2.5)
α cVw  π Mw 

where the notation is the same as in Section 5.1.

Substitution of drd /dt from (Eqn. 7.2.4) into (Eqn. 7.2.3) yields

4π Dv ρ vs ∞ rd2 (t , t0 )
I con (t ) = sw (t )
Γ1 ∫ 0 rd (t , t0 ) + ξcon
fd (rd , t ) drd . (7.2.6)

Here rd(t,t0) denotes the radius at time t of a drop activated at time t0. The radius rd(t,t0) is evaluated
by integration of (Eqn. 7.2.4) by the time from t0 to t

rd (t , t0 ) = {[rd (t0 ) + ξcon ]2 + 2c3 w [ yw (t ) − yw (t0 )]}1/ 2 − ξcon , (7.2.7)

where rd(t0) is the initial drop radius at the activation time t0, and yw(t) is the integral supersaturation:
t

yw (t ) = ∫ sw (t ') dt '. (7.2.8)

0

To express the size spectrum f (rd) via the activity spectrum, we apply a kinetic equation for the diffu-
sion growth of the droplet size spectrum:

∂ fd (rd ) ∂  drd  ds
+  fd  = ϕ s (sw ) w δ (rd − rd (t0 )), (7.2.9)
∂t ∂r  dt  dt

where js(sw) is the differential activity spectrum, and d (x) is the Dirac delta-function. A solution to
this equation describes the conservation law for the concentration of the newly formed drops and
CCN:
dsw dt0
fd (rd ) = ϕ s (sw ) . (7.2.10)
dt0 drd
7.2. Integral Supersaturation in Liquid Clouds with Drop Activation 245

Substitution of rd2(t, t0) and [rd(t, t0) + xcon] from (Eqn. 7.2.7) and fd (rd) from (Eqn. 7.2.10) into
(Eqn. 7.2.6) yields
t
4π Dv ρ vs dsw (t0 )
I con (t ) = sw (t )
Γ1 ∫r
0
d , ef (t , t0 )ϕs (sw )
dt0
dt0 , (7.2.11a)

where the integration is performed over the initial times of activation t0 and

{[(rd (t0 ) + ξcon )2 + 2c3 w ( yw (t ) − yw (t0 ))]1/ 2 − ξcon }2

rd ,ef (t , t0 ) = . (7.2.11b)
[(rd (t0 ) + ξcon )2 + 2c3 w ( yw (t ) − yw (t0 ))]1/ 2

Note that the integrand in (Eqn. 7.2.11a) represents a product of the “source function” j(sw)dsw /dt0,
which describes the “birth of particles” at a time t0, and of rd,ef (t, t0), which plays here the role of the
Green function and describes the transformation of the particles formed at time t0 to the time t.
As shown in the following, variations of ac (or xcon) can have substantial effects on the activation pro-
cess, especially for small ac. The method developed in Khvorostyanov and Curry (2008a, 2009a) and
described here provides analytical solutions for any given value of ac as described in Sections 7.6–7.8
and allows examination of variable ac and the kinetic correction xcon without running parcel models.
Substituting the algebraic activity spectrum js(sw) from (Eqn. 6.6.36) into (Eqn. 7.2.11a) and
using the relations sw= yw′, rv=rws(1 + sw) = rws(1 + yw′), or rws/rv = (1 + sw)−1 = (1 + yw′)−1, yields the
2nd (relaxation) term on the right-hand side of the supersaturation (Eqn. 7.2.1) in the form

Γ1 yw′ (t ) y ′ (t )[1 + yw′ (t )]−1

I con (t ) = [4π Dv N a J 0 (t )] = w , (7.2.12)
ρv [1 + yw′ (t )] τ f ,ac (t )
τ f ,ac (t ) = [4π Dv Na ract (t )]−1 , (7.2.13)

where we introduced the effective supersaturation relaxation time t f,ac during this stage of drop acti-
vation, an activation radius ract(t), and an integral J0(t) that has the dimension of length
t
ks 0 [ yw′ (t0 )]ks 0 −1 y ″w (t0 )
J 0 (t ) ≡ ract (t ) =
s0ks 0 ∫ rd ,ef (t , t0 )
0
{1 + η0 [ yw′ (t0 )]ks 0 }µ
dt0 . (7.2.14)

Here η0 = s0− ks 0 is expressed via CCN microphysical properties in (Eqn. 6.6.37b), ks0 is defined in
(Eqn. 6.6.30a), k s 0 = 4/( 2π ln σ s), and s0 and σ s = σ d(1+ β ) are the mean geometric supersaturation
and its dispersion defined in (Eqn. 6.6.28). The single and double primes at yw(t0) hereafter denote the
first and second time derivatives. Note that J0(t) is written in somewhat more general form with the
parameter m in the denominator of the integrand. With the Khvorostyanov and Curry (2006) algebraic
activity spectrum (Eqns. 6.6.36 or 6.6.30b), we have m = 2 in the denominator of integrand, but m can
have different values in other models (e.g., m = 0 in the power law models by Twomey (1959), Buikov
(1966a,b), Sedunov (1967, 1974), and subsequent similar models).
Using (Eqns. 7.2.12)–(7.2.14), the integral water supersaturation equation (Eqn. 7.2.1) becomes
yw″ (t ) = c1w w[1 + yw′ (t )]
 k
t
[ yw′ (t0 )]ks 0 −1 yw″ (t0 ) 
− yw′ (t )  4π Dv N a kss00
 s 0
∫r
0
d ,ef (t , t0 )
{1 + η0 [ yw′ (t0 )]ks 0 }µ 
dt0 . (7.2.15)
246 Activation of Cloud Condensation Nuclei into Cloud Drops

This equation can be written in a more compact form via J0 or tf,ac as

yw″ (t ) = c1w w[1 + yw′ (t )] − yw′ (t )[4π Dv N a J 0 (t )].

(7.2.16)
y ″w (t ) = c1w w[1 + yw′ (t )] − yw′ (t )[τ p ,ac (t )]−1 ,
(7.2.17)
This is a nonlinear integro-differential equation for the integral supersaturation yw(t) that governs the
kinetics of the drop formation. With m = 0, neglecting the kinetic correction, xcon = 0, and the initial
radius, rd(t0) = 0, the integral J0(t) reduces to the form similar to Twomey’s formulation
t
ks 0
J 0 (t ) = (2cw 3 )1/2 ∫ [ yw (t ) − yw (t0 )]1/2 [ yw′ (t0 )]ks 0 −1 yw″ (t0 ) dt0 . (7.2.18)
s0ks 0 0

Using the definition C0 = N a s0− ks 0 from (Eqn. 6.6.37a), the supersaturation equation can be written as

y ″w (t ) = c1w w[1 + yw′ (t )]

 t

− yw′ (t )  4 π Dv C0 k s 0 ∫ [ yw (t ) − yw (t0 )]1/2 [ yw′ (t0 )]ks 0 −1 y ″w (t0) dt0  , (7.2.19)
 0 
which is close to the form used by Twomey (1959) (see also Sedunov, 1967, 1974, and
Pruppacher and Klett, 1997, Chapter 13 therein), which leads to a solution N dr (sm ) ~ C0 smks 0 .
Equations (7.2.15)–(7.2.17) generalize the previous (Eqn. 7.2.19) by the presence of the new term
{1 + h0 [ y¢w (t0)]ks0}m with m = 2 in the denominator of the integrand. This term ensures correct asymptotic
behavior of the activation spectrum and gives finite droplet concentrations at large supersaturations
sm or large vertical velocities. Besides, (Eqns. 7.2.15)–(7.2.17) account for the initial radius rd(t0), and
for the kinetic correction xcon, which allows us to study the effect of the condensation coefficient ac
on the kinetics of drop activation as will be shown next.

7.3. Analytical Solutions to the Supersaturation Equation

Solutions to the supersaturation (Eqn. 7.2.15) should yield the maximum value sm of supersaturation
in a rising parcel, the time tm when sm is reached, and the concentration Ndr of the activated drops.
This solution requires evaluation of the integral J0 in (Eqn. 7.2.14). It is convenient to introduce a new
integral J1 and rewrite (Eqn. 7.2.15) as

[1 + yw′ (t )]−1 y ″ (t ) = c1w w − c4 yw′ (t ) J1 (t ). (7.3.1)

Here
s0ks 0
J1 (t ) = J 0 (t )
(2c3 w )1/2 k s 0
t
rd ,ef (t , t0 ) [ yw′ (t0 )]ks 0 −1 y ″w (t0 )
=∫ dt0 , (7.3.2)
0
(2c3 w )1/2 {1 + η0 [ yw′ (t0 )]ks 0 }µ

with ref(t,t0) defined in (Eqn. 7.2.11b), and

c4 = 4π Dv N a (2c3 w )1/ 2 k s 0 s0− ks 0 . (7.3.3)

c3w is defined in (Eqn. 7.2.4) and we retain the general index m in the denominator. Recall that m = 2 in
KC algebraic spectra, and m = 0 (the denominator vanishes) in Twomey’s and similar activity spectra.
7.3. Analytical Solutions to the Supersaturation Equation 247

Note that the form of (Eqn. 7.3.1) differs from the usual supersaturation equations (e.g., Pruppacher
and Klett, 1997, Seinfeld and Pandis, 1998): a) It deals with the integral yw and not with the differen-
tial sw supersaturation; b) it is of 2nd order with respect to the integral supersaturation yw but operates
only with yw and its derivatives; c) the last term, which describes the sink of vapor onto the droplets, is
expressed via yw′ (i.e., directly supersaturation) in contrast to typically used derivative d(LWC)/dt with
implicit dependence on sw, as was discussed in Chapter 5, Section 5.3.4. This form of the equation is
convenient both for analytical solutions and numerical models of various complexity.
A solution to (Eqns. 7.2.15) or (7.3.1) can yield the values of time tm, sm, and Ndr(sm). As noted by
Twomey (1959), Sedunov (1967, 1974), and others, an analytical solution of the complicated non-
linear integral-differential (Eqns. 7.3.1) or (7.2.15) is a formidable task. Numerical solutions of the
supersaturation equation in parcel models may lead to substantial differences among various models
due to different numerical approximations (e.g., Lin et al., 2002).
Two approaches to the solution of (Eqn. 7.3.1) are described here: a) a direct numerical solution
with some simplifications obtained in Khvorostyanov and Curry (2008a); and b) analytical solutions
based on Khvorostyanov and Curry (2009a) similar to the approach developed by Twomey (1959)
and Sedunov (1967, 1974). Both methods of solution follow the original idea by Twomey (1959)
and are based on approximations of the right-hand side of (Eqn. 7.3.1), which allow us to obtain
analytically the lower and upper bounds for solutions to (Eqn. 7.3.1). The advantage of the analytical
approach is that it provides the general analytical dependences of solutions on the input parameters
that are often hidden in numerical solutions.
The simplest solution to (Eqn. 7.3.1) can be obtained by substituting the 1st term c1ww on the RHS
into the 2nd term—i.e., to search iteratively for a solution of the form yw′(t) = sw(t) = c1wwt. Linear
functions of this form were used by Twomey (1959) and Sedunov (1967, 1974) to obtain analytical
bounds. We transform the 2nd term on the RHS of (Eqn. 7.3.1) using the linear approximation for
yw′(t) = sw(t); then

yw′ (t ) = sw (t ) = am t , y ″w = am , yw (t ) = (am / 2)t 2 . (7.3.4)

This method with a linear approximation for sw(t) developed by Twomey (1959) and promoted later
by many authors (e.g., Sedunov, 1967, 1974; Ghan et al., 1993; Abdul-Razzak et al., 1998; Abdul-
Razzak and Ghan, 2000; Khvorostyanov and Curry, 2008a, 2009a; Shipway and Abel, 2010; Ghan
et al., 2011) gives an upper limit for J1(t), and a lower limit for sw(t), and approximates a solution to
good accuracy. The form of am will be specified in the following text; the choice (Eqn. 7.3.4) is suf-
ficiently general and allows determination of the upper and lower bounds of tm and sm. Substitution of
(Eqn. 7.3.4) into (Eqn. 7.3.1) yields after simple algebraic transformations:
ks 0 + 2
[1 + yw′ (t )]−1 yw ''(t ) = c1w w − Λ(t )t , (7.3.5)

where

Λ(t ) = c5 N a s0− ks 0 amks 0 + 3/ 2 J3 (t ) (7.3.6a)

= c5 N s − ks 0
a 0 a ks 0 + 3/ 2
m [2 J 2 (t )], (7.3.6b)

the new coefficient c5 is

c5 = (c4 /2 2 ) N a−1 s0ks 0 = 2π Dv c31/w2 k s 0 . (7.3.7)

248 Activation of Cloud Condensation Nuclei into Cloud Drops

The integral J1 in (Eqn. 7.3.2) is related to J2 and J3 as

1
J1 = (am ) ks 0 +1/ 2 t ks 0 +1 J 2 , (7.3.7a)
2
J2 and J3 are the dimensionless integrals, obtained from J1 by substitution rd,ef (t, t0) into J1, and intro-
ducing the variables x = t/t0 in J2 and x2 = z or z = x1/2 in J3, which yields
1
{[U s + (1 − x 2 )]1/ 2 − Vs }2 x k s 0 −1
J 2 (t ) = ∫ dx , (7.3.8)
0
2 1/ 2
[U s + (1 − x )] (1 + λs x ks 0 )2
1
{[U s + (1 − z )]1/ 2 − Vs }2 z k s 0 / 2 −1
J3 (t ) = 2 J 2 (t ) = ∫ dz , (7.3.9)
0
[U s + (1 − z )]1/ 2 (1 + λs z ks 0 / 2 )2

and ls, Us, and Vs are the nondimensional parameters

ks 0 ks 0
 a t  3 3 am tb1/ 2 rd10+ β 
λs =  m  =   , (7.3.10)
 s0   2 Ak3/ 2 
[rd (t0 ) + ξcon ]2 ξcon
Us = , Vs = , (7.3.11)
c3 w am t 2 (c3 w am )1/2 t

where we used (Eqn. 6.6.28) for s0. The time tm when supersaturation in the parcel reaches a maximum sm
is determined from the condition sw′(tm) = 0, or yw′′(tm) = 0. Then, the left-hand side of (Eqn. 7.3.5) is zero
and we obtain an algebraic expression
1/ ( ks 0 + 2 )
c w
Λ(t )t ks 0 + 2 = c1w w, or tm =  1w  . (7.3.12)
 Λ(tm ) 
After tm is determined, it can be substituted into Λ(tm) in (Eqn. 7.3.5), which can be integrated neglect-
ing sw = y′ << 1 on the left-hand side because of small water supersaturation in clouds, and we obtain
a time-dependent solution for sw(t)
ks 0 + 2
 1  t  
yw′ (t ) ≡ sw (t ) = c1w wt 1 −   , (7.3.13)
 k s 0 + 3  tm  

where we used (Eqn. 7.3.12) to express Λ(tm) via tm. Equation (7.3.13) is a parabola by t with the two
terms of the powers t and t ks 0 + 3; it describes with good accuracy the time evolution of supersaturation
to the time tm and slightly beyond, and gives sm at the time t = tm:

 1 
yw′ (tm ) ≡ sm (tm ) = c1w wtm  1 −  = α k 1c1w wtm , (7.3.14)
 k s0 + 3 

where
ks 0 + 2
α k1 = . (7.3.15)
ks 0 + 3

Equation (7.3.15) shows that a k1 < 1, and hence (Eqn. 7.3.14) shows that the maximum supersatura-
tion sm(tm) in the lower limit is smaller than what would be obtained without this correction.
7.3. Analytical Solutions to the Supersaturation Equation 249

0.20
Parabola (7.3.13)
sover(t) = c1wt, (7.3.16)
sun,T(t), (7.3.17a) E
0.15

Supersaturation (%)
sun,S(t), (7.3.17b)
C
sm
0.10

0.05

0.00
D A B
0 4 8 12 16 20
Time (s)

Figure 7.1. Illustration of the upper and lower bounds for the solution of supersaturation equation.
The parabolic analytical solution (Eqn. 7.3.13) (solid circles); linear approximation sover (t ) = c1wt
(Eqn. 7.3.16) yielding upper bound for the integrals J2, J3 and lower bound for sm (diamonds);
linear approximations by Twomey (1959), sun ,T (t ) = c1 w(t − tm ) + sm (Eqn. 7.3.17a) (triangles), and
Sedunov (1967, 1974) sun , S (t ) = sm (t /tm ) (Eqn. 7.3.17b) (open circles) yielding lower bound for the
integrals and upper bound for sm, tm. The last two straight lines intersect parabola (Eqn. 7.3.13) at sm.
Calculations are performed with the input parameters: Na = 500 cm−3; rd0 = 0.05 mm; sd = 1.8; b = 0.5
(soluble fraction is proportional to the volume); b = 0.25 (50% of soluble fraction of ammonium
sulfate); T = 10 °C; p = 800 hPa. From Khvorostyanov and Curry (2009a), J. Atmos. Sci., 66,
© American Meteorological Society. Used with permission.

Equations (7.3.12) and (7.3.14) form a system of two equations for the two unknown quantities,
tm and sm, that allow their evaluation in various particular cases when the integrals J2 and J3 are speci-
fied. The asymptotic expressions for the integrals J2 and J3 will be obtained later in Sections 7.7–7.10
that allow determination of 4 limits of the activation process, depending on ls and ac.
The lower and upper bounds for tm, sm, and Ndr can be evaluated using (Eqn. 7.3.4) yw′ (t ) = sw (t ) = am t,
and (Eqn. 7.3.14) to relate sm and tm. This is illustrated in Fig. 7.1, showing upper and lower bounds
for sm(t). It is usually presented as a schematic diagram (e.g., Fig. 1 in Twomey, 1959; or Fig. 13-3
in Pruppacher and Klett, 1997), but this Fig. 7.1 is plotted here based on concrete calculations of all
curves using (Eqns. 7.3.13), (7.3.16), (7.3.17a), and (7.3.17b). It was shown by Twomey (1959) and
Sedunov (1967, 1974) that a choice
am = c1w w, i.e., sover (t ) = c1w wt (7.3.16)

overestimates the integral J0 of the type (Eqn. 7.2.18). Although Twomey and Sedunov considered
the integral (Eqn. 7.2.18) and supersaturation equation (Eqn. 7.2.19) that are much simpler than
(Eqns. 7.2.14) and (7.2.15), with m = 0, xcon = 0, rd(t0) = 0, this statement is valid also for a more
complicated J0 in (Eqn. 7.2.14)—i.e., (Eqn. 7.3.16) overestimates J0 in (Eqn. 7.2.14) and therefore
underestimates sm.
The proof follows from Fig. 7.1, because the straight line sover(t) (DE in Fig. 7.1) lies above the
exact curve sw(t) (the curve DC) and the area of the triangle DEB in Fig. 7.1 is greater than the area
250 Activation of Cloud Condensation Nuclei into Cloud Drops

under the curve DC, equal to J0. Therefore, (Eqn. 7.3.16) underestimates sm and yields a lower bound
for sm. Twomey (1959) showed that another approximation,

sun ,T (t ) = c1w w(t − tm ) + sm , (7.3.17a)

underestimates the J0, because the straight line sun,T(t) (AC in Fig. 7.1) lies below s(t) and the area of
the triangle ABC is less than the area below s(t) equal to J0. Therefore, using sun,T(t) overestimates
sm(tm) and gives the upper bound for sm. Sedunov (1967, 1974) proved that another choice shown in
Fig. 7.1,
sun ,S (t ) = sm (t / tm ), am = sm / tm , (7.3.17b)

also underestimates the RHS of (Eqns. 7.2.15) or (7.3.1), and gives another upper bound for tm
and sm. Fig. 7.1 shows that this bound is better than sun,T (t) because it is closer to the exact solution,
the strait line sun,S(t) (DC) lies above sun,T(t) (AC) and better approximates J0. Owing to the coefficient
ak1 < 1, calculated with (Eqn. 7.3.14) sm, is lower than it would be in the point E and is much closer
to the point C. Thus, (Eqn. 7.3.14) would be used for evaluation of the bounds. Although the integral
J0 in (Eqn. 7.2.14) and the integrals J2, J3 in (Eqns. 7.3.8) and (7.3.9) are much more complicated
than J0 (Eqn. 7.2.18) considered by Twomey and Sedunov (which corresponds to the 1st analytical
limit considered in Section 7.7), the same proof is valid for J0 in (Eqn. 7.2.14) in the other limits:
(Eqn. 7.3.16) yields an upper bound for J0 and a lower bound for sm, while (Eqns. 7.3.17a) and
(7.3.17b) vice versa, yield a lower bound for J0 and an upper bound for sm. This is seen in Fig. 7.1 and
will be proven for all four analytical limits in the subsequent Sections 7.6–7.10.
As will be shown in the following pages, the low bound may underestimate the exact solution by
10–20%, and the upper bound overestimate the solution by the same amount (see Table. 7.1 later in
the text). The average error would be 5–10%, which is lower than in the other methods.

7.4. Analytical Solutions for the Activation Time, Maximum

Supersaturation, and Drop Concentration

As discussed in Section 7.3, the form of (Eqn. 7.3.1) suggests that the first iteration to the solution
can be sought by substituting the first term on the right-hand side into the 2nd term. Such a numerical
solution gives a lower bound for sm and Ndr. Approximation am = c1ww in (Eqn. 7.3.4) yields

y ″w = c1w w, yw′ (t ) = sw (t ) = c1 wt , yw (t ) = (c1w w /2) t 2. (7.4.1)

The numerical solution of the supersaturation equation for CCN activation is based on (Eqn. 7.3.12)
for the time tm when supersaturation in the parcel reaches a maximum sm, which is determined
from (Eqn. 7.3.5) with the condition sw′(tm) = 0, or yw′′(tm) = 0. The first of algebraic expressions in
(Eqn. 7.3.12) for tm can be written in more detail as

tmks 0 + 2 = c5−1 N a−1 s0ks 0 (c1w w)− ( ks 0 +1/2) [ J3 (tm )]−1 , (7.4.2)

Solving for tm, after some transformations we obtain

−1 ks 0 − ( ks 0 +1/ 2)

tm = K tms N a( ks 0 + 2) s0( ks 0 + 2) w ( ks 0 + 2)
, (7.4.3)
−1

K tms = [c1(wks 0 +1/ 2) c5 J3 (tm )] ( ks 0 + 2 )

. (7.4.4)
7.4. Analytical Solutions for the Activation Time 251

The maximum supersaturation can now be evaluated as sm = c1wtmw, using (Eqn. 7.4.3) for tm, which
yields
−1 ks 0 3

sm = K sms N a( ks 0 + 2) s0( ks 0 + 2) w 2( ks 0 + 2) (7.4.5)

−1
( ks 0 + 2 )
K sms = [c1−w3/ 2 c5 J3 (tm )] . (7.4.6)

The drop concentration can be calculated using (Eqn. 6.7.2) based on the algebraic activity spectrum
(Eqns. 6.6.30b) or (6.6.36) with s = sm, and can be written as a function of maximum supersaturation
sm reached in the parcel:
sm

N CCN (sm ) = N dr (sm ) = ∫ ϕ s (s′) ds′

0

( s / s0 ) k s 0 C0 smks 0
= Na = , (7.4.7)
[1 + (s /s0 ) ks 0 ] (1 + η0 smks 0 )

N CCN (sm ) = C (sm )smk( sm ) . (7.4.8)

The first form (Eqn. 7.4.7) is similar to Twomey’s power law with correction at large sm as derived
by Ghan et al. (1993, 1995), and modified in Khvorostyanov and Curry (2006, 2008a) with account
for the drop growth after activation and for various soluble fractions. The second form (Eqn. 7.4.8) is
the generalized power law, with the coefficient C(sm) and index k(sm) being continuous functions of
the maximum supersaturation or of the vertical velocity. The equations for C(sm), k(sm) are given in
Chapter 6. Now, in terms of sm, they become:

C (sm ) = C0 s χ ( sm ) [1 + (sm / s0 ) ks 0 ]−1 , (7.4.9)

k (sm ) = k s 0 [1 + (sm / s0 ) ks 0 ]−1 , (7.4.10)
ks 0 −1
χ ( sm ) = k s 0 ( sm / s0 ) ks 0
[1 + (sm / s0 ) ] . (7.4.11)

Equations (7.4.5)–(7.4.8) for sm, Ndr(sm) represent a generalization of the corresponding equations
from Twomey (1959) and Sedunov (1967, 1974) that were based on the power law (Eqns. 6.1.4) and
(6.1.5) for the activity spectrum and convert into them if ls = 0 or m = 0 instead of m = 2 in denomina-
tors of the integrals (Eqns. 7.3.8) and (7.3.9), or if it is assumed that Us = 0, and Vs = 0 (i.e., initial
radius rd (t0) = 0, and kinetic correction xcon = 0) in the integrals (Eqns. 7.3.8) and (7.3.9). Without
these simplifications, (Eqn. 7.4.3) for tm depends on the coefficient Ktms (Eqn. 7.4.4) that contains the
integrals J2(tm) or J3(tm) (Eqns. 7.3.8) or (7.3.9), which themselves depend on tm and in general cannot
be evaluated analytically without some simplifications. However, these equations are easily solved
numerically and lookup tables are easily calculated.
The primary equation is (Eqn. 7.4.3) for tm, since once we know tm, we can calculate sm and Ndr(sm).
The method of calculating tm is illustrated in Fig. 7.2. Since the terms on the RHS are functions of tm via
J3(tm) in (Eqn. 7.4.4), the algorithm of the solution is the following. First, the cycle over time t is orga-
nized from t = 0 with some step Dt ~ 0.1–0.2 s. For each t, J3(t) is calculated using (Eqns. 7.3.9)–(7.3.11),
then Ktms is calculated with (Eqn. 7.4.4). Finally, the RHS of (Eqn. 7.4.3) is calculated and compared
with the LHS of (Eqn. 7.4.3). If their difference is greater than some value—e.g., et = 0.1 − 0.2 s—the
RHS of (Eqn. 7.4.3) is calculated with another t + Dt and this procedure is continued with increasing
252 Activation of Cloud Condensation Nuclei into Cloud Drops

t until the difference between the left- and right-hand sides of (Eqn. 7.4.3) becomes smaller than et.
When the difference is smaller than et, the solution for tm is found, and tm = t at which the RHS is
evaluated. The numerical tests showed that this algorithm is very fast since it includes a minimum of
numerical operations and allows us to find a solution for tm rapidly.
This algorithm is illustrated in Fig. 7.2, where the left-hand side of (Eqn. 7.4.3)—that is, tm—is
plotted along with the terms on the right-hand side of (Eqn. 7.4.3), which are calculated as functions
of t and extended to larger t to illustrate their behavior. Calculations are performed with b = 0.5, rm =
0.03 mm, sd = 2.1, ks0 = 1.44 according to (Eqn. 6.6.30a), b = 0.25 (ammonium sulfate and solubility
50%), and with three values of w = 3.5, 21, and 101 cm s−1. As seen in Fig. 7.2, tm begins at zero and
linearly increases with time, while the right-hand side of (Eqn. 7.4.3) begins at nonzero values and
grows almost linearly but much more slowly. The intersection of these two curves is a solution of
(Eqn. 7.4.3) for tm, which are 38.7, 14.9, and 6.9 seconds, respectively, for these values of w. Then,
with known tm, we can calculate sm using (Eqns. 7.4.5) and (7.4.6) and then calculate Ndr using the
algebraic law (Eqn. 7.4.7) or the generalized power law (Eqn. 7.4.8).
Calculations using this algorithm with the generalized power law (Eqns. 7.4.8–7.4.11) were made
using the following parameters: T = 10 °C, p = 800 mbar, and updraft w = 5 m s−1. Aerosol consisted
of fully soluble ammonium sulfate particles, the size spectrum is lognormal with rd0 varied in the
range indicated on the x-axis, dispersion sd = 2.5, and total concentration Na = 200 cm−3. The results
of calculations from Khvorostyanov and Curry (2008a) using this method are presented in Figs. 7.3a,b
(labeled KC) and are compared with two methods of calculations from Abdul-Razzak et al. (1998;
hereafter AGR), using detailed parcel model simulations and based on them parameterization. The
fraction activated, Ndr/Na, is shown in Fig. 7.3a as a function of the mean geometric radius rd0 varied in

100
LHS, time tm
RHS and LHS of equation (s)

RHS, w = 3.5 cm s–1

80
RHS, w = 21 cm s–1

60 RHS, w = 101 cm s–1

40

20

0
0 10 20 30 40 50 60
Time (s)

Figure 7.2. Illustration of the method of the solution of the (Eqn. 7.4.3) for tm. The left-hand side
(LHS), time, is denoted by the solid circles. The right-hand side (RHS) is calculated with
rm = 0.03 mm, sd = 2.1, b = 0.5, b = 0.25, and 3 values of w = 3.5, 21, and 101 cm s−1, as indicated
in the legend. The intersections of the RHS and LHS, marked with the ellipses, are the solutions for
tm, here, respectively, 38.7, 14.9, and 6.9 seconds. From Khvorostyanov and Curry (2008a),
J. Atmos. Sci., 65, © American Meteorological Society. Used with permission.
7.4. Analytical Solutions for the Activation Time 253

1.0

0.8 AGR

Fraction activated KC

Parcel
0.6

0.4

0.2

0.0
1E–3 1E–2 0.1
Geometric mean radius (µm)
(a)

125

100

KC/AGR
Error in fraction activated (%)

75
AGR/parcel

KC/parcel
50

25

–25

–50
1E–3 1E–2 0.1
Geometric mean radius (µm)
(b)

Figure 7.3. Comparison of the CCN fraction activated as a function of the mean geometric radius
rd0 calculated using three methods: the modified power law (Eqn. 7.4.8) of Khvorostyanov and Curry
(2008a) (KC), the parameterization from Abdul-Razzak et al. (1998) (AGR) and the results of
detailed parcel simulations from AGR (parcel). (a) fraction activated, Ndr /Na; and (b) relative errors
in percent between each two methods as indicated in the legend. Calculations are made at T = 10 °C,
p = 800 mbar, and updraft of 5 m s−1. Aerosol consists of fully soluble ammonium sulfate particles,
the size spectrum is lognormal with rd0 varied in the range indicated on the x-axis, dispersion
sd = 2.5, total concentration Na = 200 cm−3. The error between the methods does not exceed 10%
for realistic spectra at rd0 ≥ 0.01 mm and 5% at rd0 ≥ 0.03 mm. From Khvorostyanov and Curry
(2008a), J. Atmos. Sci., 65, © American Meteorological Society. Used with permission.
254 Activation of Cloud Condensation Nuclei into Cloud Drops

the range 0.001–0.1 mm, calculated with the modified power law (Eqn. 7.4.8) here, and with the two
methods from AGR. Fig. 7.3a shows that the curve obtained with (Eqn. 7.4.8), labeled KC, is close
to those from AGR. The precise AGR parcel results lie between the parameterizations AGR and KC.
Fig. 7.3b shows the differences between the methods calculated as (x1 − x2)/x2 × 100, where x1 and
x2 represent each compared pair of results. One can see that the difference between the methods does
not exceed 10% for realistic spectra at rd0 ≥ 0.01 mm and 5% at rd0 ≥ 0.03 mm. The errors increase
toward smaller values of rd0, mostly because the fraction Ndr /Na (denominator x2) becomes small,
but these results are shown rather for illustration, and size spectra with small rd0 < 0.01 mm play
little role in drop activation. Thus, the method KC based on the algebraic size and activity spectra
is in good agreement with both methods from AGR, despite their completely different mathematical
formulations.

7.5. Calculations of CCN Activation Kinetics

Using the described numerical algorithm, a series of calculations is performed using (Eqns. 7.4.3)–
(7.4.11) to study various characteristics of CCN activation kinetics with varying vertical velocity. The
effects of variations of any other single parameter of the set (rm, sd, Na, b, ac) are studied by varying
this parameter while the others were fixed as described next. The results shown in Figs. 7.4–7.8 are
obtained with the condensation coefficient ac = 1, and the effect of variations of ac is shown in Figs. 7.9
and 7.10.
Fig. 7.4 demonstrates the effect of variations of the modal radius rm on the kinetics of drop activa-
tion. The maximum time tm (Fig. 7.4a) decreases with increasing w and with increasing rm from
50–150 s and to 5–7 seconds at w = 5 m s−1. The maximum supersaturation sm (Fig. 7.4b) increases
from 0.02–0.08% at w = 1 cm s−1 to 1–1.5% s at w = 5 m s−1, and decreases with increasing rm.
Both tm and sm when plotted versus w in double-log coordinates show nearly straight lines with
slightly changing slopes. The droplet concentrations and fraction activated (Fig. 7.4c,d) increase with
increasing w and rm, and roughly resemble smoothed Heaviside step-functions as was described in
Chapter 6. Note that Ndr is limited by Na, in contrast to the usual power law expression for the CCN
activity spectra.
The indices k(w) (or k(sm)) (Eqn. 7.4.10) of the generalized power law (Eqn. 7.4.8) substantially
decrease with increasing w (Fig. 7.4e), from 1.5–1.8 at small values of w ~ 1 cm s−1 to much smaller
values at w = 5 m s−1: k(sm) ~ 0.4 at rm = 0.02 mm and k(sm) is close to zero at rm = 0.1 mm. The
coefficients C(sm) (Eqn. 7.4.9) also decrease with w from 103–2 × 104 cm−3 at small w to values
~Na = 500 cm−3 at w > 1–2 m s−1 (Fig. 7.4f); variations of C(sm) are much smaller at smaller values
of rm. These two Figures (7.4e,f) for k(w) and C(w) may provide a physical basis for the C-k space of
drop activation suggested by Braham (1976) based on the generalization of experimental data. How-
ever, the consideration here shows that this space is actually multidimensional since Ndr(w) depends
also on several other parameters: rd0, sd, Na, ev, Fs, ac, etc. The method developed here allows fast
calculation of C(sm) and k(sm) for any given w and any fixed set of aerosol microphysical parameters
(rm, sd, Na, b, ac) that together with w form a 6-dimensional C-k space.
The values of the integral J0(w) = ract(w) defined in (Eqn. 7.2.14) and shown in Fig. 7.5a increase
from 0.04–0.2 mm at small values of w to 1–2 mm at large values of w and increase with increasing
7.5. Calculations of CCN Activation Kinetics 255

Maximum supersaturation sm (%)

rm = 0.02 µm sm
Maximum time tm (sec)
1
100 rm = 0.03 µm
rm = 0.05 µm
rm = 0.07 µm
rm = 0.10 µm
0.1
10

1 1E–2
1 10 100 1000 1 10 100 1000
Vertical velocity w (cm s–1) Vertical velocity w (cm s–1)
(a) (b)
Droplet concentration Ndr (cm–3)

500 1.0

Fraction activated Ndr/Na

400 0.8

300 0.6

200 0.4

100 0.2

0 0.0
1 10 100 1000 1 10 100 1000
Vertical velocity w (cm s–1) Vertical velocity w (cm s–1)
(c) (d)

2.0 1E+5
Coefficient Cpc(sm) (cm–3)

1.5
Index k(sm)

1E+4

1.0
1E+3
0.5

0.0 1E+2
1 10 100 1000 1 10 100 1000
Vertical velocity w (cm s–1) Vertical velocity w (cm s–1)
(e) (f)

Figure 7.4. Effect on the drop activation kinetics of variations of the modal radius rm indicated in
the legend. (a) maximum time tm, sec; (b) supersaturation sm, %; (c) droplet concentration Ndr, cm−3;
(d) fraction activated; (e), index k(sm); (f) coefficient Cpc(sm), cm−3 as functions of vertical velocity
w calculated with the KC06 algebraic CCN activity spectrum. The parameters: size dispersion sd = 1.8;
b = 0.5 (volume soluble fraction); b = 0.25 (50% of ammonium sulfate); CCN concentration is
Na = 500 cm−3. From Khvorostyanov and Curry (2008a), J. Atmos. Sci., 65, © American
Meteorological Society. Used with permission.
256 Activation of Cloud Condensation Nuclei into Cloud Drops

100

Radius of activation (µm)

1

Ratio ract/rm
rm = 0.02 µm 10
0.1 rm = 0.03 µm
rm = 0.05 µm
rm = 0.07 µm
rm = 0.10 µm
1E–2 1
1 10 100 1000 1 10 100 1000
Vertical velocity w (cm s–1) Vertical velocity w (cm s–1)
(a) (b)

Height of activation (m)

0.8 10
Integral J3

0.6

0.4 1

0.2

0 0
1 10 100 1000 1 10 100 1000
Vertical velocity w (cm s–1) Vertical velocity w (cm s–1)
(c) (d)

Figure 7.5. Additional characteristics of activation. (a) Effective radius of activation ract (integral J0);
(b) ratio ract /rm; (c) Integral J3; (d) height of activation Hlift; input parameters are the same as in
Fig. 7.4. From Khvorostyanov and Curry (2008a), J. Atmos. Sci., 65, © American Meteorological
Society. Used with permission.

values of rm. The relaxation time tf,ac during activation calculated with (Eqn. 7.2.13) decreases from
∼70 seconds at w = 1 cm s−1 to 4–10 seconds at w ≥ 0.3 m s−1. The latter value of tf,ac is quite compa-
rable to the drop relaxation time in a developed cloud—i.e., the rate of vapor absorption by the newly
formed drops is comparable to that of the “old” drops.
An important characteristic of the increase in CCN radii during activation is the ratio
ract(w)/rm. Fig. 7.5b shows that ract(w)/rm increases from 1–4 at w = 1 cm s−1 to the values ≥10 at
w ≥ 0.2–0.4 m s−1—i.e., this ratio is >>1 at the typical turbulent updrafts in Sc clouds and vertical
velocities in cumulus clouds. Fig. 7.5c shows that the defined in (Eqn. 7.3.9) integral J3 < 1 and
decreases with increasing w and rm. These dependencies are useful in analysis of the analytical limits
of solutions. The depth of the activation layer calculated as Hact = wtm (Fig. 7.5d) increases from less
than 1 m at small values of w to 20–25 m at large values of w. Recall, these results were obtained with
ac = 1, and Hact is greater for smaller values of ac as described in the following.
The effect of varying size dispersion sd is shown in Fig. 7.6a–f. The dependencies on w for all val-
ues of sd are the same as described earlier. An increase in sd (broadening of the CCN size spectra) is
7.5. Calculations of CCN Activation Kinetics 257

Maximum supersaturation sm (%)

σd = 1.5
100 1
Maximum time tm (sec)

σd = 1.7
σd = 1.9
σd = 2.1
σd = 2.5
10 0.1

1 1E–2
1 10 100 1000 1 10 100 1000
Vertical velocity w (cm s–1) Vertical velocity w (cm s–1)
(a) (b)
Droplet concentration Ndr (cm–3)

500 1.0

400 Fraction activated Ndr/Na 0.8

300 0.6

200 0.4

100 0.2

0 0.0
1 10 100 1000 1 10 100 1000
Vertical velocity w (cm s–1) Vertical velocity w (cm s–1)
(c) (d)

3.0
Coefficient Cpc(sm) (cm–3)

2.5 1E+4
Index k(sm)

2.0

1.5
1E+3
1.0

0.5

0.0 1E+2
1 10 100 1000 1 10 100 1000
Vertical velocity w (cm s–1) Vertical velocity w (cm s–1)
(e) (f)

Figure 7.6. Effect on the drop activation kinetics of variations of size dispersion sd indicated in the
legend. (a) maximum time tm, sec; (b) supersaturation sm, %; (c) droplet concentration Ndr, cm−3;
(d) fraction activated; (e), index k(sm); (f) coefficient Cpc(sm), cm−3 as functions of vertical velocity w
calculated with the KC06 CCN activity spectrum. The mean geometric radius rd0 = 0.05 mm, b = 0.5
(volume soluble fraction), b = 0.25 (50% of ammonium sulfate), and CCN concentration is Na = 500 cm−3.
From Khvorostyanov and Curry (2008a), J. Atmos. Sci., 65, © American Meteorological Society. Used
with permission.
258 Activation of Cloud Condensation Nuclei into Cloud Drops

most pronounced at small values of w, where it shortens activation time tm, reduces maximum super-
saturation, index k(sm) and coefficient C(sm), and causes an increase in droplet concentration and the
fraction activated. The effect of sd decreases at w > 1 m s−1 and almost vanishes at w > 2 m s−1—i.e.,
the width of the size spectra is important in stratiform clouds and becomes much less significant in
the large updrafts in convective clouds.
Fig. 7.7 depicts the effect of variations of CCN concentration Na in the range 100 cm−3 (e.g.,
maritime or arctic clouds) to 2000 cm−3 (continental or moderately polluted atmosphere). A 20-fold
increase in Na causes a decrease in tm and sm by 2.5 times at small values of w and 4.5 times at large
values of w (Fig. 7.7a)—i.e., the effect is smaller than linear, and increases with w. The drop concen-
tration increases with Na but more slowly than linearly, so that the fraction activated decreases with
increasing Na. This decrease is greater at moderate values of w on the order of turbulent fluctuations
~0.3–0.5 m s−1, and smaller at small and large values of w (Fig. 7.7c,d). Both the index k(w) and coeffi-
cient C(w) substantially increase at larger values of Na, and their variations are also largest at moderate
values of w.
The effect of variations of the soluble fraction ev of ammonium sulfate from fully soluble nuclei
with ev = 100% varying to 6% is shown in Fig. 7.8. The values of b calculated from (Eqn. 6.2.6) for
the soluble fraction proportional to the volume (b = 0.5) vary from ≈0.5 to 0.03, respectively. The
effect of solubility is nonlinear in w, and decreases with increasing w. A more than 16-fold decrease
in the soluble fraction leads to a decrease in tm and sm by only a factor of two at small w. This differ-
ence further decreases with increasing w, and becomes almost negligible at w = 5 m s−1. With this
16-fold decrease in ev, the drop concentration and fraction activated decrease by a factor of 3.5 at
small w, a factor of 2–2.5 at w = 0.2–1 m s−1 (turbulent fluctuations), and this difference is only
15–20% at w = 4–5 m s−1 (convective clouds). The value for convective clouds with large updrafts is
close to that in Abdul-Razzak et al. (1998). Fig. 7.8 shows the effect of solubility over a wide range of
w and its increase at smaller w indicates that the solubility of CCN may play a much more important
effect in stratiform than in convective cloud types. The index k(w) increases and the coefficient C(w)
decreases for lower solubility. An interesting feature of activation is that even CCN with very small
solubility can serve as effective nuclei for drop activation under certain conditions.
The results presented in Figs. 7.4–7.8 were obtained with the condensation coefficient ac = 1
that corresponds to drops of pure water. The values of ac in the range 1 to 0.001 and smaller have
been measured in various experiments (e.g., Pruppacher and Klett, 1997, Table 5.4); ac may become
smaller than 10−3 to 10−5 in the presence of surfactants and organic substances at the CCN surface
(Deryagin et al., 1966; Deryagin and Kurgin, 1972; Bigg et al., 1969; Silverman and Weinstein, 1974;
Buikov and Khvorostyanov, 1979; Charlson et al., 2001; Feingold and Chuang, 2002; Chuang, 2003).
To study the effects of ac, we tested five values: ac = 1010, 1, 0.1, 0.04, 0.01. The corresponding
kinetic corrections xcon in dr/dt in (Eqns. 7.2.4) and (7.2.5) can be written for the standard conditions
as x ≈ 0.15/ac mm, and for these 5 cases are respectively 0, 0.15, 1.5, 3.8, and 15 mm. (The real value
of ac is of course always ≤ 1, but the choice ac = 1010 allows us to study the case with the absence of
kinetic corrections, xcon ≈ 0—i.e., the diffusion approximation used in some works).
The impacts of varying the condensation coefficient ac are shown in Figs. 7.9 and 7.10. The
difference in tm and sm and in all the other characteristics shown in Figs. 7.9 and 7.10 for the case
7.5. Calculations of CCN Activation Kinetics 259

Maximum supersaturation sm (%)

Na = 100 cm–3
Maximum time tm (sec)
100
Na = 200 cm–3 1

10 0.1
Na = 500 cm–3
Na = 1000 cm–3
Na = 2000 cm–3
1 1E–2
1 10 100 1000 1 10 100 1000
Vertical velocity w (cm s–1) Vertical velocity w (cm s–1)
(a) (b)
Droplet concentration Ndr (cm–3)

1800 1.0

Fraction activated Ndr/Na

1600
1400 0.8
1200
0.6
1000
800
0.4
600
400 0.2
200
0 0.0
1 10 100 1000 1 10 100 1000
Vertical velocity w (cm s–1) Vertical velocity w (cm s–1)
(c) (d)
1E+5
2.0
Coefficient Cpc(sm) (cm–3)

1.5 1E+4
Index k(sm)

1.0 1E+3

0.5 1E+2

0.0 1E+1
1 10 100 1000 1 10 100 1000
Vertical velocity w (cm s–1) Vertical velocity w (cm s–1)
(e) (f)

Figure 7.7. Effect on the drop activation of CCN concentration Na indicated in the legend.
(a) maximum time tm, sec; (b) supersaturation sm, %; (c) droplet concentration Ndr, cm−3; (d) fraction
activated; (e), index k(sm); (f) coefficient Cpc(sm), cm−3 as functions of vertical velocity w calculated
with the KC06 CCN activity spectrum. The mean geometric radius rd0 = 0.05 mm, sd = 1.8, b = 0.5
(volume soluble fraction), b = 0.25 (50% of ammonium sulfate). From Khvorostyanov and Curry
(2008a), J. Atmos. Sci., 65, © American Meteorological Society. Used with permission.
260 Activation of Cloud Condensation Nuclei into Cloud Drops

Maximum supersaturation sm (%)

εv = 6 % 1
Maximum time tm (sec) 100 εv = 12 %
εv = 25 %
εv = 50 %
εv = 100 %
0.1

10

1E−2
1 10 100 1000 1 10 100 1000
Vertical velocity w (cm s−1) Vertical velocity w (cm s−1)
(a) (b)
Droplet concentration Ndr (cm−3)

1.0
500

Fraction activated Ndr/Na

400 0.8

300 0.6

200 0.4

100 0.2

0 0.0
1 10 100 1000 1 10 100 1000
Vertical velocity w (cm s−1) Vertical velocity w (cm s−1)
(c) (d)

2.0
Coefficient Cpc(sm) (cm−3)

1E+4
1.5
Index k(sm)

1.0
1E+3

0.5

0.0 1E+2
1 10 100 1000 1 10 100 1000
Vertical velocity w (cm s−1) Vertical velocity w (cm s−1)
(e) (f)

Figure 7.8. Effect on the drop activation of variations of the soluble fraction ev of ammonium
sulfate from 6% to fully soluble nuclei (100%) indicated in the legend. (a) maximum time tm, sec;
(b) supersaturation sm, %; (c) droplet concentration Ndr, cm−3; (d) fraction activated; (e), index
k(sm); (f) coefficient Cpc(sm), cm−3 as functions of vertical velocity w calculated with KC06 CCN
activity spectrum. The mean geometric radius rd0 = 0.05 mm, sd = 1.8, b = 0.5 (volume soluble
fraction), Na = 500 cm−3. From Khvorostyanov and Curry (2008a), J. Atmos. Sci., 65, © American
Meteorological Society. Used with permission.
7.5. Calculations of CCN Activation Kinetics 261

Maximum supersaturation sm (%)

1000 1E+1
αc = 1e10
αc = 1.0
Maximum time tm (s)

αc = 0.1
100 αc = 0.04 1
αc = 0.01

10 0.1

1 1E–2
1 10 100 1000 1 10 100 1000
Vertical velocity w (cm s–1) Vertical velocity w (cm s–1)
(a) (b)
Droplet concentration Ndr (cm–3)

500 1.0

Fraction activated Ndr/ Na

400 0.8

300 0.6

200 0.4

100 0.2

0 0.0
1 10 100 1000 1 10 100 1000
Vertical velocity w (cm s–1) Vertical velocity w (cm s–1)
(c) (d)

2.0
Coefficient Cpc(sm) (cm–3)

1E+4
1.5
Index k(sm)

1.0
1E+3

0.5

0.0 1E+2
1 10 100 1000 1 10 100 1000
Vertical velocity w (cm s–1) Vertical velocity w (cm s–1)
(e) (f)

Figure 7.9. Effect on the drop activation of variations of condensation coefficient ac indicated in the
legend (ac = 1010 corresponds to x = 0). (a) maximum time tm, sec; (b) supersaturation sm, %;
(c) droplet concentration Ndr, cm−3; (d) fraction activated; (e), index k(sm); (f) coefficient Cpc(sm), cm−3
as functions of vertical velocity w calculated with the KC06 algebraic CCN activity spectrum. The
mean geometric radius rd0 = 0.05 mm, sd = 1.8, b = 0.5 (volume soluble fraction), b = 0.25 (50% of
ammonium sulfate), CCN concentration is Na = 500 cm−3. From Khvorostyanov and Curry (2008a),
J. Atmos. Sci., 65, © American Meteorological Society. Used with permission.
262 Activation of Cloud Condensation Nuclei into Cloud Drops

ac = 1010 (absence of kinetic correction) and ac = 1 generally does not exceed 4–7%. That is, the
case ac = 1 is close to the absence of kinetic correction as in Twomey (1959) and subsequent simi-
lar parameterizations. A decrease in ac from 1 to 0.1 causes a significant increase in tm and sm of
50–70%; the droplet concentration and fraction activated are almost twice as large at small values of
w with a gradual decrease of the difference toward larger values of w. Both the index k(w) and coef-
ficient C(w) decrease with increasing w but in such a way that Ndr increases. A decrease in ac from
1 to 0.04 (the typical value used in many cloud models) results in 2–2.5-fold increase in tm, sm; the
corresponding increase in Ndr is 1.5–2 times at w = 10–50 cm s−1 (comparable or greater than the indi-
rect aerosol effect), and gradually vanishes at large w. When ac decreases from 1 to 0.01, which may
correspond to substantially polluted clouds, there is a 5- to 6-fold increase in tm, sm. This leads to an
increase in Ndr by 50–100% at w = 10–50 cm s−1, which tends to zero at large w. Any decrease in ac is
accompanied by a significant decrease in k(w) and C(w) similar to those just described (Fig. 7.9a–f).
The values of ract(w) = J0(w) and ract/rm become much smaller with decreasing ac (Fig. 7.10a),
and the assumption ract/rm >> 1 with ac ≤ 0.04 made in some previous works is not satisfied even
Radius of activation (µm)

1 10.0
Ratio ract/rm

0.1 αc = 1e10
αc = 1 1.0
αc = 0.1
αc = 0.04
αc = 0.01
1E–2 0.1
1 10 100 1000 1 10 100 1000
Vertical velocity w (cm s–1) Vertical velocity w (cm s–1)
(a) (b)

1
100
Height of activation (m)

0.8
Integral J3

0.6 10

0.4
1
0.2

0 0
1 10 100 1000 1 10 100 1000
Vertical velocity w (cm s–1) Vertical velocity w (cm s–1)
(c) (d)

Figure 7.10. Effect of variations of condensation coefficient ac indicated in the legend (ac = 1010
corresponds to x = 0). (a) effective radius of activation ract (integral J0); (b) ratio ract /rm; (c) Integral J3;
(d) height of activation Hlift; input parameters are the same as in Fig.7.8. From Khvorostyanov and
Curry (2008a), J. Atmos. Sci., 65, © American Meteorological Society. Used with permission.
7.6. Four Analytical Limits of Solution 263

for sufficiently high values of w. The height of activation substantially increases for small ac ≤ 0.1
(Fig. 7.10d), and may exceed 30–100 m, so that the process of activation should be distributed among
several levels in models with fine vertical resolution for polluted clouds with low ac.
Thus, a decrease in the condensation coefficient leads to slower CCN activation, and higher maxi-
mum supersaturation, droplet concentration, and CCN fraction activated. Therefore, correct measure-
ments of the condensation coefficient and use of its proper values for evaluation of the concentration
of activated drops is very important. The method developed here allows direct fast calculations of
CCN activation in a model or compilation of lookup tables for cloud and climate models for any
values of condensation coefficient.

7.6. Four Analytical Limits of Solution

Another, analytical, way of studying the kinetics of drop nucleation is based on simplifying J2 or
J3 in (Eqns. 7.3.8 and 7.3.9) and finding the asymptotic analytical limits of the solutions, and then
constructing interpolations among them. Analysis shows that there are four limiting cases for which
approximate analytical solutions for tm, sm, and Ndr can be found (Khvorostyanov and Curry, 2009a).
These cases are naturally separated by the values of the vertical velocities (or maximum supersatura-
tions sm) that are determined by the values of ls in (Eqn. 7.3.10), and of the condensation coefficients
ac that determine diffusion growth of the activated droplets (sufficiently pure water drops) or kinetic
growth regime (polluted water drops). The expression for ls(sm) for the lower bound with am = c1ww,
or sw(tm) = c1wwtm, follows from (Eqn. 7.3.10):
ks 0 ks 0 ks 0
s   c wt   3 3 b1/ 2 rd10+ β 
λ s ( sm ) =  m  =  1w m  = (c1w wtm )  ,
 s0   s0   2 Ak3/ 2 
(7.6.1)
where (Eqn. 6.6.28) was used for s0. Thus, these four limits are:

1. ls << 1 (small vertical velocities w), ac ∼ 1 (diffusion droplet growth limit);

2. ls << 1 (small vertical velocities w), ac << 1 (kinetic droplet growth limit);
3. ls >> 1 (large vertical velocities w), ac ∼ 1 (diffusion droplet growth limit);
4. ls >> 1 (large vertical velocities w), ac << 1 (kinetic droplet growth limit).

Equations (7.4.7) and (7.4.8) for Ndr(sm), and solutions for sm, represent a generalization of the
corresponding expressions from Twomey (1959) and Sedunov (1967, 1974) that were based on
the power law for js(s) and correspond to the 1st limit here as described in Section 7.1. These
4 limits, along with the situations intermediate among them, cover the vast majority of the situa-
tions that can be met in atmospheric clouds. Thus, if we find these limits and construct interpola-
tions among them, the problem of parameterization can be solved. However, these limits have
physical meaning without interpolation since each of them corresponds to some particular type of
cloud with a certain range of vertical velocities. For example, limits 1 and 2 may correspond to
stratiform clouds or fogs with low vertical velocities w, and limits 3 and 4 correspond to convective
clouds with higher w.
The applicability of these limits is determined by the scaling parameters, sm /s0, and λs = (sm / s0 ) ks 0.
Fig. 7.11 shows that the values ac = 1010 (the physical value of ac ≤ 1, but ac = 1010 means absence
264 Activation of Cloud Condensation Nuclei into Cloud Drops

1E+1

Ratio sm/s0

1E+0 αc = 1.e10

αc = 1

αc = 0.1

αc = 0.04

αc = 0.01
1E–1
1 10 100 1000
Vertical velocity w (cm s–1)
(a)
1E+2

3
1E+1
Parameter λs

1E+0
αc = 1.e10

2 αc = 1
1
1E–1 αc = 0.1

αc = 0.04

αc = 0.01

1E–2
1 10 100 1000
Vertical velocity w (cm s–1)
(b)

Figure 7.11. Scaling parameters: (a) sm /s0, and (b) λs (sm ) = (sm /s0 ) ks 0, calculated with the input
parameters: Na = 500 cm−3; rd0 = 0.05 mm; sd = 1.8; b = 0.5 (soluble fraction is proportional to
the volume); b = 0.25 (50% of soluble fraction of ammonium sulfate); T = 10 °C; p = 800 hPa, and
five values of the condensation coefficient indicated in the legend. The regions of the four limits
are approximately denoted with the ellipses in Fig. 7.11b on the ls – w diagram, the digits are the
numbers of the limits. From Khvorostyanov and Curry (2009a), J. Atmos. Sci., 66, © American
Meteorological Society. Used with permission.
7.7. Limit #1: Small Vertical Velocity, Diffusional Growth Regime 265

of kinetic correction, xcon = 0) and ac = 1 yield close results—i.e., the value ac = 1 that may be
characteristic of pure water drops is close to Twomey’s (1959) case with xcon = 0. The regions of the
four limits are depicted in Fig. 7.11b on the ls – w diagram. One can see that the 1st limit, ls << 1,
is valid with ac ∼ 1 and small w. The 2nd limit with ac << 1 is marked in Fig. 7.11 at w ≤ 1 cm s−1
around the ordinate axis. The third and fourth limits are reached at w > 1–2 m s−1. This representation
is somewhat schematic and these regions may extend to larger areas with varying parameters. The
applicability of these limits will be illustrated in more detail in the next sections by comparison of
these limits with the exact solutions.

7.7. Limit #1: Small Vertical Velocity, Diffusional Growth Regime

This limit corresponds to ls << 1 (low w or low s) and ac ∼ 1 (the diffusion growth regime of acti-
vated drops), so that the denominator of the 2nd fraction in the integrand of J3 (Eqn. 7.3.9) tends to
unity. This is equivalent to the absence of the denominator in the differential CCN activity spectrum
(Eqn. 6.6.36), which is then similar to Twomey’s (1959) power law

ϕ s ( s ) = k s 0 C 0 s k s 0 −1 . (7.7.1)

When ac ∼ 1, we can neglect small xcon, and we also assume small rd(t0). With these assumptions and
(Eqn. 7.7.1), this limit #1 is equivalent to the model of activation considered by Twomey, Sedunov,
and all subsequent similar models, but their empirical coefficient C0 and index ks0 were expressed in
(Eqns. 7.4.9)–(7.4.11) via aerosol parameters. As shown in Appendix A.7, J3 in this case is reduced
to Twomey’s integral with Euler’s beta function B(x,z):

k 3
J3(1) = Β  s 0 ,  . (7.7.2)
 2 2

7.7.1. Lower Bound

Substitution of (Eqn. 7.7.2) into (Eqns. 7.3.12) or (7.4.3) for tm, using Λ from (Eqn. 7.3.6a) with
am = c1w w from (Eqn. 7.3.16), solving for tm, and using c5 from (Eqn. 7.3.7) yields the lower bound
(1)
tml in the 1st limit:
−1 ks 0 − ( k s 0 +1/ 2)
(1)
tml = K tm
(1)
N aks 0 + 2 s0ks 0 + 2 w ks 0 + 2
, (7.7.3)
−1/ ( ks 0 + 2 )
  k 3 
(1)
K tm (T , p) = c1kws 0 +1/ 2 2π Dv c31/w2 k s 0 Β  s 0 ,   . (7.7.4)
  2 2 

(The superscripts “(i)” hereafter denote the i-th limit with i = 1–4, and the subscript “l” means lower
bound, while the subscript “m” means maximum value). The maximum supersaturation is from
(Eqn. 7.3.14) in this limit:
−1 ks 0 3
(1)
sml = α k 1 K sm
(1)
N aks 0 + 2 s0ks 0 + 2 w 2( ks 0 + 2) , (7.7.5)
−1
  k 3  ks 0 + 2
(1)
K sm (T , p) =  2π Dv c1−w3/ 2 c31/w2 k s 0 Β  s 0 ,   , (7.7.6)
  2 2 
266 Activation of Cloud Condensation Nuclei into Cloud Drops

(1)
and a k1 was defined in (Eqn. 7.3.15). Note that maxima sml (1)
and tml (1)
are related as sml = α k 1c1 wtml
(1)
—
i.e., almost as in Twomey’s upper approximation (Eqn. 7.3.16) for sover(t) but with the coefficient a k1.
(1)
Table 7.1 shows that sml is only by 11–24% lower than sover(t). The droplet concentration from
(Eqn. 7.4.7) is
2 −2 ks 0 3 ks 0

N dr(1), l (sm ) = Na (sm(1) / s0 ) ks 0 = α kk1s 0 [ K sm ] N aks 0 + 2 s0ks 0 + 2 w 2( ks 0 + 2) .

(1) ks 0
(7.7.7)

The powers of w in the expressions for sm and Ndr are the same as derived by Twomey (1959), while
his empirical indices and coefficients are expressed now via aerosol microphysical parameters. The
coefficient ak1 is similar to the 1st major term in Twomey’s power series expansion for the lower
bound of sm (Twomey, 1959, Eq. (7)). More detailed expressions can be obtained if the mean geo-
metric supersaturation s0 is expressed via the mean geometric radius rd0 from (Eqn. 6.6.35b), the
parameter of chemical composition b from (Eqn. 6.2.6), and the curvature parameter Ak is expressed
via the surface tension ssa and temperature T using (Eqn. 6.2.2b):
ks 0 −1 − ks 0 (1+ β )
(1) 2( ks 0 + 2)
(1)
tml = K tm Qa N aks 0 + 2 rd 0 ks 0 + 2
− ks 0 3 ks 0 −3 k s 0 − ( ks 0 +1/ 2)

× b 2( ks 0 + 2) σ sa2( ks 0 + 2) T 2( ks 0 + 2) w ks 0 + 2
, (7.7.8)

and Qa = (25/ 3 M w /3 R ρ w )3. Equation (7.7.8) shows that tm decreases (i.e., activation ceases more rap-
idly) with the increase of Na, rd0, solubility b (i.e., ev), updraft w, and with the decrease of the surface
tension ssa in the presence of surfactants. In particular, with ks0 ∼ 2 (sd = 1.7, b = 0.5), (Eqn. 7.7.8)
yields
(1)
tml (1)
~ K tm (T ) N a−1/ 4 rd−03/ 4 b −1/ 4σ sa3/ 4 T −3/ 4 w −5/8 . (7.7.9)

Table 7.1. Index ks0 and coefficients α k1, α up

(1)
, α low
(1)
, up , α up , α low , up , α up , α low , up, α up , α low , up at various
(2) (2) (3) (3) (4) (4)

size dispersions sd and b = 0.5 (soluble fraction proportional to volume).

sd 1.2 1.5 1.7 1.8 2.0 2.2 2.5

ks0 5.84 2.63 2.00 1.81 1.54 1.35 1.16
α k1 0.89 0.82 0.80 0.79 0.78 0.77 0.76
α (1)
up 0.993 0.979 0.972 0.969 0.966 0.961 0.957
α low
(1)
, up 1.116 1.193 1.215 1.227 1.238 1.248 1.260
α (2)
up 0.979 0.949 0.944 0.933 0.927 0.921 0.915
α low
(2)
, up 1.099 1.158 1.180 1.181 1.188 1.196 1.203
α (3)
up 0.971 0.952 0.946 0.943 0.940 0.937 0.934
α (3)
low , up 1,091 1.160 1.182 1.194 1.205 1.216 1.228
α up
(4)
0.954 0.924 0.915 0.910 0.905 0.901 0.896
α (4)
low , up 1.072 1.126 1.143 1.152 1.161 1.170 1.179
7.7. Limit #1: Small Vertical Velocity, Diffusional Growth Regime 267

The analytical dependencies for another sd can be found using the ks0 - sd relation from Table 7.1.
For sm, we obtain from (Eqn. 7.7.5), expressing again s0 via rd0 and using (Eqn. 6.2.6) for b:
ks 0 −1 − ks 0 (1+ β )
(1)
sml = α k 1 K sm
(1)
(T )Qa2( ks 0 + 2) N aks 0 + 2 rd 0 ks 0 + 2
− ks 0 3 ks 0 −3 ks 0 3

× b 2( ks 0 + 2) σ sa2( ks 0 + 2) T 2( ks 0 + 2) w2( ks 0 + 2) . (7.7.10)

Thus, sm increases with increasing w and ssa, and decreases with increasing supersaturation absorp-
tion rate—i.e., increasing Na, rd0, and b (or ev). In particular, with ks0 ∼ 2, we have
(1) (1)
sml ~ α k 1 K sm (T ) N a−1/ 4 rd−03/ 4 b −1/ 4σ sa3/ 4 T −3/ 4 w 3/8 . (7.7.10a)

For Ndr, we have from (Eqn. 7.7.7) expressing s0 via rd0 and b, and using (Eqn. 6.2.6) for b and
(Eqn. 7.7.10) for sm
− ks 0 2 2 ks 0 (1+ β )

N dr(1),l = α kk1s 0 [ K sm
(1)
(T )]ks 0 Qaks 0 + 2 N aks 0 + 2 rd 0 ks 0 + 2
ks 0 −3 ks 0 3 ks 0 3 ks 0

× b ks 0 + 2 σ sa2( ks 0 + 2) T 2( ks 0 + 2) w 2( ks 0 + 2) . (7.7.11)

The index of ssa is negative—i.e., the maximum drop concentration grows with decreasing surface
tension (as with increasing concentration of organics or surface-active substances). The other 5 power
indices are positive, thus Ndr increases with an increase of any of the 4 factors: Na, rd0, b (or ev), or w.
(1)
The temperature increase due to the positive power of T is overwhelmed by decreasing K sm (T ),
and Ndr decreases with increasing T. A similar negative temperature dependence was obtained in
Saleeby and Cotton (2004) with parcel model simulations. In particular, with ks0 ∼ 2, we have from
(Eqn. 7.7.11)
(1)
N dr ,l ~ [ K sm (T )]ks 0 N a1/2 rd3/2
0 b
1/2
σ sa−3/4 T 3/4 w 3/4 . (7.7.11a)

The variations d Ndr predicted by (Eqn. 7.7.11) at small variations of the surface tension dssa are

δ N dr( l1),l δσ sa 3k s 0
≈ −C Nσ , C Nσ = . (7.7.11b)
N dr( l1),l σ sa 2( k s 0 + 2)

In particular, with ks0 ∼ 2, then CNs = 3/4, and dNdr,l /Ndr,l ∼ (−3/4)dssa /ssa, which exactly coincides
with the expression derived in Facchini et al. (1999). For a broader size spectrum with sd = 2.5 and
b = 0.5, we have ks0 ∼ 1.16 (Table 7.1), and CNs ≈ 0.55—i.e., the dependence of Ndr,l on surface ten-
sion becomes weaker for broader CCN spectra, but the general qualitative dependence of Ndr,l on ssa
in the 1st limit is similar to that in Facchini et al. (1999), and Abdul-Razzak and Ghan (2004). Note
that these conclusions are drawn since we consider here ssa as a variable, and do not consider effects
of its variations due to redistribution of organics between the surface and volume in CCN as in Li et al.
(1998) and Abdul-Razzak and Ghan (2004). According to Facchini et al. (1999), a 30% decrease in
ssa should cause a ∼20% increase in Ndr, which should lead to an increase in top-of-the-atmosphere
albedo locally by ∼1% and could cause a global mean forcing with an upper limit of −1 W m−2. The
opposite effects of decreasing Ndr with an increasing organic coating of CCN and a decrease of ssa
were predicted by Feingold and Chuang (2002); various studies of coating effects on drop activation
268 Activation of Cloud Condensation Nuclei into Cloud Drops

were reviewed in IPCC (2007). Equations here allow estimations of the effects of surface tension
with various other CCN properties. These effects can be noticeable for small w, but it will be shown
in Sections 7.9 and 7.10 that Ndr is highly insensitive to surface tension at high w > 1–2 m s−1.

7.7.2. Upper Bound

Evaluation of the upper bound in this and other limits is a little more complicated and is done using
the system of two (Eqns. 7.3.12) and (7.3.14) to determine the two unknowns, tm and sm. Substitution
of J3(1) from (Eqn. 7.7.2) and am=sm/tm from (Eqn. 7.3.17b) into (Eqn. 7.3.6a) yields Λ(tm). Substitut-
(1) (1)
ing it into (Eqns. 7.3.12) and (7.3.14) and solving for tm, we obtain for tmu , smu , and N dr(1), u in the upper
bound (subscript “u”) of the first limit almost the same expressions as (Eqns. 7.7.8), (7.7.10), and
(7.7.11) but multiplied by the coefficient α low , up for t mu in (Eqn. 7.7.8), by α up instead of α k1 for sml
(1) (1) (1) (1)

in (Eqn. 7.7.10), and (α up ) instead of α k 1s 0 for N dr(1),u in (Eqn. 7.7.11). The relation smu
k
(1) s 0 k (1)
= α up (1)
c1w wtm(1)u
similar to Twomey’s upper approximation (Eqn. 7.3.16) arises again, but with coefficient α up ~ 1. The (1)

relation of the lower and upper bounds in the 1st limit is determined by the coefficient α low (1)
, up:

(1)
tmu = α low
(1) (1)
, up t ml ,
(1)
smu = α low
(1) (1)
, up sml ,

N dr(1), u = (α low
(1)
, up )
k so
N dr(1), l , (7.7.12)

where

α up
(1)
= α 1/[2(
k1
ks 0 + 2)]
= [( k s 0 + 2) / ( k s 0 + 3)]1/[2( ks 0 + 2)] , (7.7.13a)
α (1)
low , up =α (1)
up / α k 1 = [( k s 0 + 3) / ( k s 0 + 2)] (2 ks 0 + 3) /[2( ks 0 + 2)]
. (7.7.13b)

The coefficients α k1, α up

(1)
, and α low
(1)
, up along with the index ks0 are given in Table 7.1 for various size

dispersions sd. One can see that ks0 decreases from 5.84 at sd = 1.2 (narrow spectra) to 1.16 at
sd = 2.5 (wide spectra). All the coefficients are close to 1, and their variations are much smaller: a k1
decreases from 0.89 to 0.76, α up (1)
decreases from 0.993 to 0.957.
Thus, the lower bound for sm obtained with (Eqn. 7.3.14) is 11–24% lower than would be
obtained with the linear relation (Eqn. 7.3.16) sm = c1wwtm, and the upper bound is only 1–4% lower.
Calculated variations of the coefficients with b = 0 (not shown here) are even smaller. For all sd,
α up
(1)
> ak 1—i.e., the condition is satisfied that the upper bound is higher than the lower bound; how-
ever, the difference between the bounds is rather small. The coefficient α low (1)
, up, which characterizes

the ratio of the upper to the lower bounds, increases from 1.116 to 1.260 in this range—that is, the
difference does not exceed 12% and 26% for the narrow and wide spectra, respectively. Assuming
that the true value is close to the mean of the upper and lower bounds, the error would be a factor of
two smaller: ∼6 and 13%.
A comparison was performed of these approximate analytical limits for tm, sm, and Ndr with more
precise numerical solution of the complete supersaturation equation (Eqn. 7.2.15) with the modified
power law (Eqn. 7.4.8) and coefficients from (Eqns. 7.4.9)–(7.4.11), hereafter referred to as “exact
solution.” Fig. 7.12 shows that the agreement between the 1st limit and exact solution for tm, sm is
good for both bounds at w ≤ 30–50 cm s−1. A comparison of sm with parameterization from Abdul-
Razzak et al. (1998, hereafter AGR98) also shows a satisfactory agreement; the curve calculated
using AGR98 algorithm is closer to our lower bound for sm at small w, and coincides with the exact
solution at w > 0.5 m s−1.
Fig. 7.12c shows a comparison of Ndr calculated with three methods. The 1st limit for Ndr (Eqn. 7.7.11)—
i.e., the traditional power law (solid squares)—is close to the exact solution only at w = 1 to 4 cm s−1
(triangles). At greater w, using the power law may significantly overestimate droplet concentrations.
7.7. Limit #1: Small Vertical Velocity, Diffusional Growth Regime 269

1000
Lim. 1, lower

Maximum time tm (sec)

Lim. 1, upper
100 Exact, αc=1

10

1
1 10 100 1000
Vertical velocity w (cm s–1)
(a)
Maximum supersaturation sm (%)

0.1
Lim. 1, low
Lim. 1, up
Exact sol., αc=1
AGR98
0.01
1 10 100 1000
Vertical velocity w (cm s–1)
(b)
500
Droplet concentration Ndr (cm–3)

400

300

200
(7.4.8), sm low. b.
(7.4.8), sm up. b.
100
Lim 1, power law
Exact sol., αc=1
0
1 10 100 1000
Vertical velocity w (cm s–1)
(c)

Figure 7.12. Comparison of the lower and upper bounds of the 1st limit (solid and open circles) at
ac = 1 with the exact solutions (diamonds). (a) maximum time, tm; (b) maximum supersaturation, sm,
compared with parameterization from Abdul-Razzak et al. (1998, AGR98); (c) concentration of
activated droplets, Ndr, calculated as the power law in the 1st limit, lower bound (Eqn. 7.7.11) (solid
squares), modified power law (Eqn. 7.4.8) with the lower (Eqn. 7.7.10) and upper (Eqn. 7.7.12) bounds
for sm from Fig. 7.12b, and exact solution as modified power law (Eqn. 7.4.8) with the exact sm and
ac = 1. Calculations are performed with the same parameters as in Fig. 7.11. From Khvorostyanov and
Curry (2009a), J. Atmos. Sci., 66, © American Meteorological Society. Used with permission.
270 Activation of Cloud Condensation Nuclei into Cloud Drops

This curve and conclusion are in close agreement with those from Ghan et al. (1993, Fig. 7), and this
was the major reason of revisions of the Twomey’s theory. The modified power law (Eqn. 7.4.8) for Ndr
with the lower bound for sm (Eqn. 7.7.10) (solid circles) gives the results that are lower than both the
old power law and the exact solution. The modified power law (Eqn. 7.4.8) with the upper bound for
sm (Eqn. 7.7.12) is close to the exact solution to w ∼ 0.5 m s−1, the error does not exceed 10–15%, but
is still lower than the exact solution. The exact solution based on the modified power law (Eqn. 7.4.8)
with “exact” sm is the most precise.

7.7.3. Comparison with Twomey’s Power Law

A more detailed comparison with Twomey’s power law allows expression of Twomey’s empirical
coefficients CT and k via aerosol microphysical parameters. Twomey (1959) provided a solution
for sm and Ndr with numerical coefficients for some specified conditions, p and T. A more general
solution with analytical coefficients was given in Pruppacher and Klett (1997, PK97), and we will
compare this with the PK97 derivation and solution. The supersaturation equation in PK97 was used
in the form [PK97, eq. (13-30)],

dsw d ρL
= A1w − A2 , (7.7.14)
dt dt
where rL is the liquid water content, and the coefficients A1 and A2 (eq. (13-31) in PK97) describe
supersaturation generation and absorption in the supersaturation equation. The expression for maximum
supersaturation, derived in more general form in Pruppacher and Klett (1997, eq. (13-40)), can be
rewritten with two coefficients as

sm = CT−1/ ( ks 0 + 2)CST w 3/[2( k + 2)] , (7.7.15a)

1/ ( k + 2)
 A 3/ 2

CST =  1
 , (7.7.15b)
 2πρ w A2 A3 k Β( k / 2, 3 / 2) 
3/ 2

where CT is Twomey’s empirical constant of the activation spectrum (see Eqns. 7.1.3 and 7.1.4) and
we introduced a new coefficient CST for convenience of comparison (a misprint in PK97 in the sign
of the power index of CT is corrected), and A3 in (Eqn. 7.7.15b) is the coefficient in the drop radius
growth rate (PK97, eq. (13-32)). The equation (Eqn. 7.7.14) was compared in Chapter 5 with the
supersaturation equation (Eqn. 7.2.1) derived in Chapter 5 and used here. According to (Eqns. 5.3.36)
and (5.3.37):
A1 = c1w , A2 = Γ1 / ρ ws , A3 = c3 w , (7.7.15c)

where Γ1 is the psychrometric correction. Substitution of A1, A2, and A3 into (Eqn. 7.7.15b) yields
1/ ( k + 2 )
 c13/w2 ρ ws 
CST =   . (7.7.16a)
(
 2πρ w Γ1c3 w k Β k / 2 , 3 / 2
3/ 2
) 

It follows from (Eqns. 7.7.1) or (7.4.10) that k = ks0 in this limit (sm /s0 ) ks 0 << 1. Then, writing
c33/w2 = c31/w2 c3 w and using (Eqn. 7.2.4) for c3w = (Dvrws/Γ1rw), we see that
7.7. Limit #1: Small Vertical Velocity, Diffusional Growth Regime 271

1/ ( k + 2)
w ρ ws )
(c13/2
CST = 1/ ( k + 2 )
  Dv ρ ws   k 3  
 2πρ w Γ1c3 w  kΒ  ,  
1/ 2

  Γ1 ρ w   2 2  
−1
  k 3   k +2
=  2π Dv c1−w3/ 2 c31/w2 k s 0 Β  ,   = K sm (1)
(T , p). (7.7.16b)
  2 2 
(1)
That is, CST exactly coincides with our K sm in (Eqn. 7.7.6). Equating our expression for the lower
bound of sm (Eqn. 7.7.10) with the upper correction (Eqn. 7.7.13b), and Twomey’s sm in (Eqn. 7.7.15a),
dividing by CST = K sm
(1)
, and using the definitions of b (Eqns. 6.2.6) and (6.2.7) and Qa (defined after
Eqn. 7.7.8) we obtain for Twomey’s empirical coefficient:
−3 ks 0 /2
 25/3 M w 
CT = 10 −2 ks 0 α k−11/2   Na
 3Rρw 
k s 0 /2
−3 ks 0 3 ks 0
ks 0 (1+ β )
 ρs M w 
×σ sa
2
T 2
r
d0 ν Φs ε v ρ M  . (7.7.17)
 w s 

Equation (7.7.17) is valid for both b = 1/2 and b = 0 and sm measured in percent. Thus, Twomey’s
coefficient CT, used for more than five decades as an empirical parameter, is now expressed via
CCN microphysical parameters: Na, rd0, sd (in ks0), T, ssa, b and b (or ev), rs, and other proper-
ties of CCN. In addition, these dependencies are nonlinear, governed by the powers of ks0. It is not
surprising that measurements made over a period of decades have found such different values for
CT, varying by several orders of magnitude in various air masses and clouds (Hegg and Hobbs,
1992; Pruppacher and Klett, 1997, Table 9.1 therein; Seinfeld and Pandis, 1998). Twomey’s empiri-
cal index k, equal to ks0 at s << 1%, is also expressed with (Eqns. 6.6.35c) or (7.4.10) via sd and b,
4 4
ks 0 = = . Equations (7.7.17) and (7.4.10) explain many features of the
2π ln σ s 2π (1 + β ) ln σ d
observed values of CT and k. In particular, CT is proportional to Na, therefore CT has higher values in
continental than in maritime air masses, and greater values in polluted areas. CT also increases with
increasing soluble fraction ev as ε vks 0 / 2, with the mean geometric radius of CCN rd0 as rdk0s 0 (1+ β ), and with
decreasing surface tension in the presence of surfactants as σ sa−3 ks 0 / 2.
Drop concentration is evaluated according to Twomey as Ndr = CTsmk, which can be written using
(Eqn. 7.7.15a,b) as

N dr = CT2 / (2 + k )CST
k
w 3 k / 2( k + 2) . (7.7.18)

This expression is equivalent to that derived in Twomey (1959) and in Pruppacher and Klett (1997),
(Eqn. 13-40 therein), the power indices of CT and w are the same as in cited works, and additionally,
all the empirical parameters are expressed via CCN microphysical properties. It should be noted that
the typical calculated values of CT and k in the limit s << 1% are usually much greater (k = 1.5–2,
and up to 4) than often measured k = 0.2–0.6 at s = 0.2–1% and then used in parameterizations
(Pruppacher and Klett, 1997). This reflects a substantial difference of this model with variable k(s)
relative to Twomey’s model using typical values k ∼ 0.2–0.6.
Fig. 7.13 depicts C(sm) and k(sm) calculated with (Eqns. 7.4.9)–(7.4.11), analogous to Fig. 6.15
with k(s), but presented now as functions of sm and w simultaneously. C(sm) ≈ 8000 cm−3 at
272 Activation of Cloud Condensation Nuclei into Cloud Drops

1E+4

Coefficient Cpc(sm) (cm–3)

1E+3

1E+2
1 10 100
Vertical velocity w (cm s–1)

0.10 1.00
Supersaturation sm (%)
(a)
2.0
KC08, this work

YH01, 960–1010 mb
1.5
YH01, 560–660 mb
Index k(sm)

DRI CFD
1.0
NRL SDC

0.5

0.0
1 10 100
Vertical velocity w (cm s–1)

0.10 1.00
Supersaturation sm (%)
(b)

Figure 7.13. (a) Coefficient Cpc(sm) and Cpc(w), and (b) index k(sm) and k(w) as functions simultaneously
of the vertical velocities w and maximum supersaturations sm. Calculations are conducted with the same
parameters as in Fig. 7.12 where sm(w) is also given. Examples of measured k(s) are the data collected
in FIRE-ACE in 1998 (Yum and Hudson, 2001, YH01) at the heights 960–1010 mb and 560–660 mb,
and the data from Jiusto and Lala (1981) from 2 chambers (continuous flow diffusion chamber, CFD;
and static diffusion chamber, SDC). From Khvorostyanov and Curry (2009a), J. Atmos. Sci., 66,
© American Meteorological Society. Used with permission.
7.8. Limit #2: Small Vertical Velocity, Kinetic Growth Regime 273

w = 1 cm s−1 (sm = 0.043%) and decreases to the limit Na ≈ 500 cm−3 at w ≈ 1–2 m s−1 (sm = 0.5–1%).
Experimental data on C(sm) are not readily available. However, the calculated index k(sm), which also
decreases from 1.67 to below 0.2 in this range of sm or w (Fig. 7.13b), is in good agreement with
data both from cloud chamber and field experiments (e.g., Jiusto and Lala, 1981; Yum and Hudson,
2001). This indicates that this model generalizes Twomey’s model and correctly predicts decreasing
C(sm), k(sm) with increasing sm or increasing w. If these parameters are measured at some sm, they can
be easily recalculated for any value of sm using (Eqns. 7.4.9)–(7.4.11), but this requires additional
measurements or hypotheses on CCN size spectrum and chemical composition. If measurements of
all the variables are available, then (Eqns. 7.4.9)–(7.4.11) for C(sm), k(sm) can be verified.

7.8. Limit #2: Small Vertical Velocity, Kinetic Growth Regime

For small w, the activation spectrum is also approximated by the power law (Eqn. 7.7.1), but the first
fraction and integrand in J3 in (Eqn. 7.3.9) are substantially different than that in Twomey’s model
due to the kinetic drop growth rate. The integral J3 for this case is evaluated in Appendix A.7:

k 
J3(2) (t ) = 4 −4 Dv−3Vw3α c3 (c3 w am )3/2 t 3 B  s 0 , 3 . (7.8.1)
 2 

In contrast to the 1st limit (Eqn. 7.7.2) for J3(1) in the diffusion regime that contained only the beta
function, now J3(2) also contains several coefficients in dimensionless combination.

7.8.1. Lower Bound

Substituting (Eqn. 7.8.1) into (7.3.12) for tm with am = c1ww from (Eqn. 7.3.16), we obtain the lower
bound (superscript “2” means the 2nd limit, subscript “l” means lower bound)

−1 ks 0 − ( ks 0 + 2) −3
(2)
tml = K tm
(2)
Naks 0 +5 s0ks 0 +5 w ks 0 +5
α cks 0 +5 , (7.8.2)
−1
π k k  ks 0 + 5
(2)
K tm (T , p) =  s 0 c1kws 0 + 2 c32w Dv−2Vw3 B  s 0 , 3  . (7.8.3)
 128  2 

The lower bound for sm is calculated using (Eqn. 7.3.14):

−1 ks 0 3 −3
(2)
sml = α k 1 K sm
(2)
N aks 0 + 5 s0ks 0 + 5 w ks 0 + 5 α cks 0 + 5 , (7.8.4)
−1
π k k  ks 0 + 5
(2)
K sm (T , p) =  s 0 c1−w3 c32w Dv−2Vw3 B  s 0 , 3  . (7.8.5)
 128  2 

The lower bound for Ndr is calculated from (Eqn. 7.4.7) taking into account that sm << s0 (low s limit):
5 −5 ks 0 3 ks 0 −3 ks 0

Ndr(2), l (sm ) = (α k 1 ) ks 0 K Nd
(2)
Naks 0 +5 s0ks 0 +5 w ks 0 +5 α cks 0 +5 , (7.8.6)
− ks 0
π k k  ks 0 + 5
(2)
K Nd (T , p) =  s 0 c1−w3 c32w Dv−2Vw3 B  s 0 , 3  . (7.8.7)
 128  2 
274 Activation of Cloud Condensation Nuclei into Cloud Drops

As in the previous limit, these equations can be expressed via rd0 and b instead of s0 using
(Eqn. 6.6.35b) for s0, and via ssa and T instead of Ak using (Eqn. 6.2.2b). Thus, we obtain for tm
ks 0 −1 − (1+ β ) ks 0 − ks 0
(2)
tml (2)
= K tm Qaks 0 +5 Naks 0 +5 rd 0 ks 0 +5 b2 ( ks 0 +5)
3 ks 0 −3 ks 0 − ( ks 0 + 2) −3

× σ sa2( ks 0 + 5) T 2( ks 0 +5) w ks 0 + 5
α cks 0 +5 . (7.8.8)

For ks0 = 2, it follows from (Eqn. 7.8.8) in the kinetic regime:

(2)
tml (2)
~ K tm (T ) N a−1/ 7 rd−03/ 7 b −1/ 7σ sa3/ 7 T −3/ 7 w −4 / 7α c−3 / 7 . (7.8.8a)

Comparing with the diffusion limit (Eqn. 7.7.9), we see that all six dependencies (except for ac) are
weaker in the kinetic regime. The maximum supersaturation from (Eqns. 7.8.4), (7.8.5), and (6.3.35b)
becomes
ks 0 −1 − (1+ β ) ks 0
(2)
sml = α k 1 K sm
(2)
Qaks 0 +5 Naks 0 +5 rd 0 ks 0 +5
− ks 0 3 ks 0 −3 ks 0 3 −3

× b2 ( ks 0 +5) σ sa2( ks 0 +5) T 2( ks 0 +5) w ks 0 +5 α cks 0 +5 . (7.8.9)

For ks0 = 2, (Eqn. 7.8.9) gives in this kinetic regime

(2) (2)
sml ~ α k 1 K sm (T ) N a−1/ 7 rd−03/ 7 b −1/ 7σ sa3/ 7 T −3/ 7 w 3/ 7α c−3/ 7 . (7.8.9a)

Comparing with the diffusion limit (Eqn. 7.7.10a), we see that the dependencies on Na, rd0, ssa, T, and
b are substantially weaker in the kinetic regime, and the dependence on w is slightly stronger. The
droplet concentration from (Eqns. 7.8.6) and (7.8.7) converts into
−5 k s 0 5 5(1+ β ) k s 0

Ndr(2), l (sm ) = (α k 1 ) ks 0 K Nd
(2)
Qaks 0 +5 Naks 0 +5 rd 0 ks 0 +5
5 ks 0 −15 k s 0 15 k s 0 3 ks 0 −3 k s 0

× b 2( ks 0 +5) σ sa2( ks 0 +5) T 2( ks 0 +5) w ks 0 +5 α cks 0 +5 . (7.8.10)

In particular, for ks0 = 2, (Eqn. 7.8.10) gives in the kinetic regime:

7 5/ 7 15/ 7 −15/ 7 6 / 7 −6 / 7
N dr(2) ~ K nd
(2)
(T ) N a5/ 7 rd15/
0 b σ sa T w αc . (7.8.10a)

Comparing this with the diffusional growth limit (Eqn. 7.7.11a), we see that the dependencies on
the 6 parameters (Na, rd0, b, ssa, T, w) become somewhat stronger in the kinetic limit. In addition, this
limit includes explicit dependence on the condensation coefficient ac. An advantage of this method of
asymptotic limits is that it allows for simple estimates of the effects of variations of the condensation
coefficients on tm, sm, and Ndr. It follows from (Eqns. 7.8.8)–(7.8.10) that

tm(2) ~ sm(2) ~ α c−3/ ( ks 0 + 5) , (7.8.11)

3 ks 0 / ( ks 0 + 5)
N (2)
dr ~ ξcon ~ α c−3 ks 0 / ( ks 0 + 5) . (7.8.12)

This inverse dependence of the concentration of activated drops on the condensation coefficient
is in agreement with the results of the numerical simulation of radiative fog suppression by injection
7.8. Limit #2: Small Vertical Velocity, Kinetic Growth Regime 275

of surfactants performed in Buikov and Khvorostyanov (1979) with a 1D spectral bin model. It was
assumed that surfactants cause a decrease in the condensation coefficient by 1–3 orders of magnitude
as indicated by laboratory experiments (Juisto, 1964; Deryagin et al., 1966; Deryagin and Kurgin,
1972; Silverman and Weinstein, 1974). The simulation showed that this decrease in ac resulted in
two different stages of fog development. In the first stage, continuing for about half an hour to an
hour, the droplet growth was suppressed and visibility in the fog increased. In the second stage, due
to a continuing radiative cooling equivalent to vertical velocities of a few cm s–1 and suppressed drop
growth, supersaturation increased by 1–3 orders of magnitude (Eqn. 7.8.9), the droplet concentration
increased up to 2–3 times, as described by (Eqn. 7.8.10), and visibility decreased and became lower
than in the natural fog without artificial modification.
This inverse dependence of the drop concentration on ac provides the basis for quantitative esti-
mates of the indirect aerosol effects (Twomey’s, Albrecht’s, and others) that are caused by an increase
in drop concentration in polluted clouds due to anthropogenic, volcanic, and other emissions into the
atmosphere, which cause a decrease in the condensation coefficient.

7.8.2. Upper Bound

Derivation of the upper bound, as for the 1st limit, is based on the system of (Eqns. 7.3.12) and
(7.3.14). Substituting (Eqn. 7.8.1) for J3(2) with am = sm /tm from (Eqn. 7.3.17b) into this system and
(2) (2)
solving for tm and sm, we obtain for tmu , smu , and N dr(2), u in the upper bound (subscript “u”) of the 2nd
limit (superscript “2”) almost the same expressions as (Eqns. 7.8.8)–(7.8.10) but multiplied by the
coefficient α low
(2)
, up for t mu in (Eqn. 7.8.8), by α up instead of α k1 for sml in (Eqn. 7.8.9), and (α up )
(2) (2) (2) (2) ks 0

instead of α k 1 for N dr ,u in (Eqn. 7.8.10). That is, the relation of the limits is
ks 0 (1)

(2)
tmu = α low
(2) (2)
, up t ml ,
(2)
smu = α low
(2) (2)
, up sml , N dr(2), u = (α low
(2)
, up )
k so
N dr(2), l , (7.8.13)
where
α up
(2)
= α k21/ ( ks 0 + 5) = [( k s 0 + 2) / ( k s 0 + 3)]2 / ( ks 0 + 5) , (7.8.14)
α (2)
low , up = α /α k 1 = [( k s 0 + 3) / ( k s 0 + 2)]
(2)
up
( ks 0 + 3) / ( ks 0 + 5 )
. (7.8.15)

The coefficients α k1, α up

(2)
, and α low
(2)
, up are given in Table 7.1. As in the 1st limit, all the coefficients

are close to 1, and α up is 2–8% lower than 1. In this range of sd, α low
(2) (2)
, up increases from 1.099 to

1.20, and characterizes the ratio of tm and sm in upper to lower bounds. Shown in Fig. 7.14 is a com-
parison of the upper bound of the 2nd limit with the exact solution to the supersaturation equation
(Eqn. 7.2.15a). The agreement becomes sufficiently good at ac ≤ 0.04, and small w ≤ 2–3 cm s−1.
A surprising finding is that the value ac = 0.04, used in many cloud models, is close to the boundary
of the kinetic regime, and the values of tm, sm, and Ndr are substantially greater in this regime than in
the 1st limit with ac = 1 and the diffusion regime (compare Figs. 7.12 and 7.14).
276 Activation of Cloud Condensation Nuclei into Cloud Drops

1E+3
exact, αc = 1 2nd lim., αc = 1
exact, αc = 0.1 2nd lim., αc = 0.1
exact, αc = 0.04 2nd lim., αc = 0.04

Maximum time tm (s)

exact, αc = 0.01 2nd lim., αc = 0.01

1E+2
αc = 0.01
αc = 1
αc = 0.04
αc = 0.1

1E+1
1 10 100
Vertical velocity w (cm s–1)
(a)

1
Maximum supersaturation sm (%)

0.1

1E–2
1 10 100
Vertical velocity w (cm s–1)
(b)

1E+3
Droplet concentration Ndr (cm–3)

1E+2

1E+1

1
1 10 100
Vertical velocity w (cm s–1)
(c)

Figure 7.14. Comparison of the upper bound of the 2nd limit (solid symbols and lines) with the
corresponding exact solutions to the supersaturation equation (corresponding open symbols, dashed
lines). (a) Maximum time, tmax; (b) maximum supersaturation, smax; (c) concentration of activated
droplets, Ndr. Calculations are performed with the parameters: Na = 500 cm−3; rd0 = 0.05 mm;
sd = 1.8; b = 0.5; b = 0.25; T = 10 °C; p = 800 hPa. Agreement (accuracy of the 2nd limit)
becomes better at ac ≤ 0.04—i.e., ac = 0.04 is close to the boundary of the kinetic regime. From
Khvorostyanov and Curry (2009a), with changes, J. Atmos. Sci., 66, © American Meteorological
Society. Used with permission.
7.9. Limit #3: Large Vertical Velocity, Diffusional Growth Regime 277

7.9. Limit #3: Large Vertical Velocity, Diffusional Growth Regime

At large w—i.e., in the limit sm >> s0 (ls >> 1)—the integral J3 in (Eqn. 7.3.9) in general cannot
be reduced to the beta function, and it is more convenient to use (Eqn. 7.3.12) for evaluation of
tm with (Eqn. 7.3.6b) for Λ and (Eqn. 7.3.8) for J2. The integral J 2(3) (t ) in this limit is evaluated in
Appendix A.7 as
ks 0
1 1  s0 
J 2(3) (t ) ≈ = . (7.9.1)
k s 0 λs k s 0  am t 

The error of this analytical J 2(3) (t ) relative to the exact numerical calculation is less than 4% for
ls ≈ 30. Substituting (Eqn. 7.9.1) into (Eqn. 7.3.6b) for Λ and then in to (Eqn. 7.3.12) yields an
expression for tm

tm(3) = (4π Dv c1−w1 c31/2w am3/2 )−1/2 Na−1/2 w1/2 . (7.9.2)

7.9.1. Lower Bound

Substituting am = c1ww from (Eqn. 7.3.16), we obtain a simple asymptotic for the lower bound (sub-
script “l”) of the 3rd limit (superscript “3”) at large w:
(3)
tml = K tm
(3)
N a−1/ 2 w −1/ 4 , (7.9.3)
K (3)
tm = [4π D c c ]
1/ 2 1/ 2 −1/ 2
v 1w 3 w . (7.9.4)

This gives for sm from (Eqn. 7.3.14)

(3)
sml = α k 1 K sm
(3)
N a−1/ 2 w 3/ 4 , (7.9.5)
K (3)
sm = [4π D c −3/2
v 1w
1/ 2 −1/ 2
c ]
3w . (7.9.6)

7.9.2. Upper Bound

As in the previous sections, the upper bound is obtained by substituting am = sm /tm from (Eqn.
7.3.17b) into (Eqn. 7.9.2), and then substituting the resulting relation tm(sm) into the system of (Eqns.
7.3.12)–(7.3.14) and solving for tm, sm. Then, we obtain tmu similar to (Eqn. 7.9.3), but multiplied by
the coefficient α low
(3)
, up and smu similar to (Eqn. 7.9.5), but with the coefficient α up instead of a k1, so that
(3)

(3)
tmu = α low
(3) (3)
, up t ml ,
(3)
smu = α low
(3 ) ( 3)
, up sml , (7.9.7)

where

α up
(3)
= α 1/k 14 = [( k s 0 + 2) / ( k s 0 + 3)]1/ 4 , (7.9.8)
α (3)
low , up = α up
(3)
/α k 1 = α k−13/4 = [( k s 0 + 3) / ( k s 0 + 2)]3/ 4 .
(7.9.9)
The coefficients α k1, α , and α
(3) (3)
up are given in Table 7.1. They are also close to 1. The coefficient
low , up

a k1 for the lower bound is the same for all 4 limits, for the upper bound is lower than 1 by 3–7%, and
the ratio of the upper to lower limits, α low ,up, is 1.09–1.23. That is, the error of any solution average
(3)

between these bounds does not exceed 5–11%.

Equations (7.9.3)–(7.9.9) show that tm and sm in the limit of high w are also related by the linear
relation similar to (Eqn. 7.3.14), and also have the form of power laws but only by Na and w. The
dependencies of tm and sm on rd0, sd, b, b, and on curvature parameter Ak or surface tension ssa, which
were very substantial in the 1st and 2nd limits at small w, disappear from the coefficients and power
278 Activation of Cloud Condensation Nuclei into Cloud Drops

indices in the limit of high w. Thus, for the 3rd limit with large w and ac ∼ 1 (sufficiently pure drops),
we come to an unexpected result: the maximum supersaturation sm, and activation time tm, are inde-
pendent of the CCN size spectrum and chemical composition. Thus, tm and sm depend only on CCN
concentration Na and vertical velocities w, and the indices of these dependencies are constant and
universal for various CCN—i.e., are the same for different values of ks0. This somewhat paradoxical
result can be explained by the fact that the 3rd limit deals with the region ls >> 1, where sm is much
greater than the mean geometric s0, or the minimum radius activated rmin << rm—i.e., lies well below
the modal radius. Thus, the vast majority of CCN will be activated, no matter what their individual
properties are. This independence on the physical and chemical properties of CCN indicates that the
effects of the surface tension and chemical composition on the global albedo and radiative balance
should be evident mostly in stratiform clouds and become weaker in convective clouds.
Fig. 7.15 shows that the tm and sm in the upper bound of the 3rd limit approach the corresponding
exact solutions at w > 1–2 m s−1, but this conclusion is valid only for ac ∼ 1, and becomes invalid at
ac = 0.1. At w < 0.7–1 m s−1, the 3rd limit is invalid. This tendency to independence of tm and sm in
this analytical limit on rm, sd, and b (or ev) at high w was illustrated with numerical calculations in
Figs. 7.4–7.8, where tm(w), sm(w) in double-log coordinates represented almost straight lines with
slopes slightly increasing toward large w. The corresponding curves tm(w) and sm(w) converged at
w ≥ 0.5–2 m s−1 toward the limits with fixed slopes. The simple equations of the 3rd limit here provide
an explanation for this and exact values of the slopes. The expression (Eqn. 7.4.7) for Ndr shows
that Ndr tends to Na at ls >> 1 (sm >> s0). We can approximate it by expanding the denominator in
(Eqn. 7.4.7) into a power series by s0 /sm ∼ 1/ls and retaining two terms—i.e., Ndr or fraction activated
Ndr /Na is a parabolic function of (sm /s0 )− ks 0:

N dr = N a [1 − (sm /s0 )− ks 0 + (1/2 )(sm / s0 )−2 ks 0 ] , (7.9.10)

and sm is defined in (Eqns. 7.9.5) and (7.9.7). Fig. 7.15 shows that Ndr in the 3rd limit at ac ∼ 1 also
approaches the exact solution at w > 1–2 m s−1, but at w ≤ 0.5 m s−1, Ndr increases with decreasing w—
i.e., the number of terms in expansion (Eqn. 7.9.10) becomes insufficient and (Eqn. 7.9.10) becomes
invalid. In contrast to tm and sm, the value of Ndr depends on the CCN size spectrum and chemical
composition via s0, but this dependence is substantially weaker than in the 1st and 2nd limits.

7.10. Limit #4: Large Vertical Velocity, Kinetic Growth Regime

When ac << 1, then xcon >> rd(t0), and rd(t0) can be neglected in Us in (Eqn. 7.3.11). Then, Us = Vs2.
Further, (1 − x2) << Us1/2 in J2 (Eqn. 7.3.8) and (1 − x2) << Vs. The integral J2 in the 4th limit is evalu-
ated in Appendix A.7:

1 am s 0 c3 w tm s 0 α c Vw s0 s 0
3/2− k 3/2 3− k 3 3 k

2 J 2(4) (tm ) ≈ 3
. (7.10.1)
128 k s 0 Dv

7.10.1. Lower Bound

Substituting (Eqn. 7.10.1) into (Eqns. 7.3.6b) and (7.3.12) for Λ and using (Eqn. 7.3.16) for am, we
obtain an algebraic equation for tm, which gives the lower bound
(4)
tml = K tm
(4)
N a−1/ 5 w −2 / 5α c−3/ 5 , (7.10.2)
K (4)
tm = [(π /64)c c V D ]
2
1w
2
3w
3
w
−2 −1/5
v . (7.10.3)
7.10. Limit #4: Large Vertical Velocity, Kinetic Growth Regime 279

1000
Limit 3
Exact sol., αc = 1.e10

Activation time tm (sec)

Exact sol., αc = 1
100
Exact sol., αc = 0.1

10

1
1 10 100 1000
Vertical velocity w (cm s–1)
(a)
Maximum supersaturation sm (%)

0.1

1E–2

1E–3
1 10 100 1000
Vertical velocity w (cm s–1)
(b)
500
Droplet concentration Ndr (cm–3)

400

300

200

100

0
1 10 100 1000
Vertical velocity w (cm s–1)
(c)

Figure 7.15. Comparison of the upper bound of the 3rd limit (solid circles) with the corresponding
exact solutions to the supersaturation equation at various values of condensation coefficient
indicated in the legend. (a) Maximum time, tm; (b) maximum supersaturation, sm; (c) concentration
of activated droplets, Ndr. Calculations are performed with the same parameters as in Fig. 7.2. The
3rd limit approaches the exact solution at w > 1–2 m s−1 and is invalid at w < 0.7–1.0 m s−1. From
Khvorostyanov and Curry (2009a), J. Atmos. Sci., 66, © American Meteorological Society. Used
with permission.
280 Activation of Cloud Condensation Nuclei into Cloud Drops

The lower bound for maximum supersaturation sm is calculated from (Eqns. 7.10.2) and (7.3.14):
(4)
sml = α k 1 K sm
(4)
N a−1/ 5 w 3/ 5 α c−3/ 5 , (7.10.4a)
(4)
K sm = [(π /64)c1−w3 c32w Vw3 Dv−2 ]−1/5 . (7.10.4b

The drop concentration can be calculated similar to (Eqn. 7.9.10),

(4)
N dr = N a [1 − (sml / s0 )− ks 0 + (1 / 2)(sml
(4)
/ s0 )−2 ks 0 ], (7.10.5)

7.10.2. Upper Bound

The upper bound for tmu, smu is obtained as in the previous sections using (Eqn. 7.3.17b) for am,
substituting J2 from (Eqn. 7.10.1) into (Eqns. 7.3.12) and (7.3.14), and solving the system of the two
(4)
equations. Then, we obtain tmu similar to (Eqn. 7.10.2), but multiplied by the coefficient α low
(4)
, up and smu

similar to (Eqn. 7.10.4), but with coefficient α up instead of a k1, so that

(4)

(4)
tmu = α low
(4) (4)
, up t ml ,
(4)
smu = α low
(4 ) ( 4)
, up sml , (7.10.6)

where
α up
(4)
= α k2/15 = [( k s 0 + 2) /( k s 0 + 3)]2 / 5 , (7.10.7)
−3/ 5
α (4)
low , up = α /α k 1 = α
(4)
up k1 = [( k s 0 + 3) /( k s 0 + 2) ] .
3/ 5
(7.10.8)

The coefficients α k1, α up

(4)
, and α low
(4)
, up are given in Table 7.1. They also are close to 1. The coefficient

a k1 for the lower limit is the same, α up (4)

for the upper limit is lower than 1 by 5–10%, and the ratio of
the upper to lower limits, α low ,up, is 1.07–1.18. That is, the error of any solution mean between these
(4)

limits does not exceed 3.5–9%.

Thus, the activation time tm and maximum supersaturation sm in both bounds of the 4th limit do
not depend on the CCN size spectrum (rd, sd), surface tension, soluble fraction b, b or ev, or chemical
composition. They depend only on CCN concentration Na, vertical velocities w, and condensation
coefficient ac. These dependencies have the form of the power laws, their indices are constant and
universal for various CCN similar to the 3rd limit, and in contrast to the 1st and 2nd limits at small w,
where the indices depend on the size dispersions. The drop concentration Ndr can be calculated from
(Eqn. 7.10.5) as a parabolic function of ls below Na. It depends on physico-chemical properties of
CCN as in the 3rd limit, but the dependence is much weaker than in the 1st and 2nd limits.
The characteristics of the 4th limit are compared with the exact solution in Fig. 7.16 for various
values of ac. The 4th limit calculated with ac 5 1 is far from the exact solution at all w, which is quite
natural as ac 5 1 is characteristic of the diffusion regime. With ac 5 0.04, the tm, sm in the 4th limit
are already close to the exact solution. This means that ac 5 0.04, often used in the models, is closer
to the kinetic than to the diffusion regime. For ac5 0.01, that can be characteristic of polluted clouds:
the parameters tm, sm, and Ndr almost merge with exact solutions at w ≥ 10 cm s21.
7.10. Limit #4: Large Vertical Velocity, Kinetic Growth Regime 281

ex, αc = 1 lim. 4, αc = 1
1000 ex, αc = 0.1 lim. 4, αc = 0.1
ex, αc = 0.04 lim. 4, αc = 0.04

Activation time (s)

ex, αc = 0.01 lim. 4, αc = 0.01
100

10

1
1 10 100 1000
Vertical velocity w (cm s–1)
(a)

1E+1
Maximum supersaturation sm (%)

0.1

1E–2

1E–3
1 10 100 1000
Vertical velocity w (cm s–1)
(b)

500
Droplet concentration Ndr (cm–3)

400

300

200

100

0
1 10 100 1000
Vertical velocity w (cm s–1)
(c)

Figure 7.16. Comparison of the upper bound of the 4th limit (solid symbols) with the corresponding
exact solutions at various values of the condensation coefficient indicated in the legend (open
symbols). (a) activation time, tm; (b) maximum supersaturation, sm; (c) concentration of activated
droplets, Ndr. Calculations are performed with the same parameters as in Fig. 7.11. From
Khvorostyanov and Curry (2009a), with changes, J. Atmos. Sci., 66, © American Meteorological
Society. Used with permission.
282 Activation of Cloud Condensation Nuclei into Cloud Drops

7.11. Interpolation Equations and Comparison with Exact Solutions

General solutions for tm and sm can be constructed by interpolating between the limiting solutions
with some interpolation function Ww(w, wsc) or Wa(a, asc). For example, interpolations between the
1st and 3rd limits can be constructed as
sm(13) ( w) = sm(1) Ω w ( w, wsc ) + sm(3) [1 − Ω w ( w, wsc )]
+∆sm13 Ω w ( w, wsc )[1 − Ω w ( w, wsc )], (7.11.1)

where wsc and asc are the scaling parameters. The function Ww(w, wsc) should satisfy the conditions
Ωw(w = 0) → 1, Ωw(w >> wsc) → 0. This ensures corresponding limits at small and large w. The 3rd
term on the RHS of each equation is added to make these fitting functions closer to the exact solutions
at the intermediate w, and the product Ωw(1 − Ωw) vanishes at w → 0 and w >> wsc.
Fig. 7.17a shows sm calculated with (Eqn. 7.11.1), and Ωw(w, wsc) = exp(−w/wsc), with wsc =
1.8 m s−1, and ∆ sm13 = sm(3) (5 m s −1) − sm(3) (1 cm s −1) . The fitted interpolated curve (solid circles) tends
Maximum supersaturation sm (%)

Exact
1.00
Limit 1
Limit 3
Interp. 1–3

0.10

0.01
1 10 100 1000
Vertical velocity w (cm s–1)
(a)
500
Droplet concentration Ndr (cm–3)

400

300

200
Exact

100 Interp. 1–3

Lim 1, correc.
Lim 3, correc.
0
1 10 100 1000
Vertical velocity w (cm s–1)
(b)

Figure 7.17. Illustration of the method of interpolation between the 1st and 3rd limits and
comparison with exact solutions. (a) maximum supersaturation sm; (b) droplet concentration Ndr
calculated as described in the text. The parameters are the same as in Fig. 7.11. From Khvorostyanov
and Curry (2009a), J. Atmos. Sci., 66, © American Meteorological Society. Used with permission.
7.11. Interpolation Equations and Comparison with Exact Solutions 283

to the corresponding limits at w → 0 and w >> wsc, lies above both limits owing to addition of
the term with Dsm13, and is very close to the exact curve. The Ndr(w) calculated with this interpolated
sm(w) and the modified power laws (Eqns. 7.4.7) or (7.4.8) is also close to the exact curve. This
example indicates that more precise interpolation expressions for Ndr can be obtained using (Eqns. 7.4.7)
or (7.4.8) and interpolations among various analytical limits for sm. A detailed elaboration of this
interpolation procedure among all 4 limits requires a special careful choice of several functions Ww,
and can be done for every particular case as in the described example.
284 Activation of Cloud Condensation Nuclei into Cloud Drops

Appendix A.7 for Chapter 7. Evaluation of the Integrals J2 and J3 for Four Limiting Cases
The J2 and J3 are the dimensionless integrals introduced in Section 7.3,
1
{[U s + (1 − x 2 )]1/ 2 − Vs }2 x k s 0 −1
J 2 (t ) = ∫ dx , (A.7.1)
0
2 1/ 2
[U s + (1 − x )] (1 + λs x ks 0 )2
1
{[U s + (1 − z )]1/2 − Vs }2 z k s 0 / 2 −1
J3 (t ) = 2 J 2 (t ) = ∫ dz. (A.7.2)
0
[U s + (1 − z )] 1/ 2
(1 + λs z ks 0 / 2 )2

Here x = t/t0, z = x1/2, and the 3 nondimensional parameters ls, Us, and Vs are
ks 0 ks 0
 a t  3 3 am tb1/ 2 rd10+ β 
λs =  m  =   , (A.7.3)
 s0   2 Ak3/ 2 
[rd (t0 ) + ξcon ]2 ξcon
Us = , Vs = . (A.7.4)
c3 w am t 2 (c3 w am )1/ 2 t

The limiting values of J2 and J3 are evaluated in the following text for the four limits described in
Sections 7.6–7.10.

Limit # 1. Small w, diffusional growth regime. In this case, ls << 1, the denominator of the second
fraction in the integrand of J3 tends to unity, which corresponds to the power law activity spectrum
(Eqn. 7.7.1). We make additional approximations in (Eqn. A.7.2), consider the case ac ∼ 1, neglect
small xcon, and assume small rd(t0). Then, Us and Vs vanish, and the integral J3 (Eqn. A.7.2) is simpli-
fied and reduced to Euler’s beta function B(x,z) as in the Twomey model:
1
k 3
J3(1) = ∫ z ks 0 / 2 −1 (1 − z )1/ 2 dz = Β  s 0 ,  . (A.7.5)
0
 2 2

Limit #2: Small w, `c << 1. When ac << 1, then xcon >> rd(t0) and rd(t0) can be neglected in (Eqns.
7.3.11) or (A.7.4) for Us, and then Us ≈ xcon2/(amc3wt2) = Vs2. We also have in (Eqn. A.7.2) for J3 the
inequalities (1 − z) << Us and (1 − z) << Vs2. Expansion of the first fraction in the integrand of J3 in
(Eqn. A.7.2) by the small parameter (1 − z)/Vs2 yields

(1 − z )2 (1 − z )2 (c3 w am )3/ 2 t 3
= . (A.7.6)
4Vs3 4ξcon
3

Substituting this expression for the first fraction in the integrand in J3, we obtain

(c3 w am )3/ 2 t 3 1 z k s 0 / 2 −1
J3(2) (t ) = 3
4ξcon ∫
0
(1 − z ) 2
(1 + λs z ks 0 / 2 ) µ
dz. (A.7.7)

For ls << 1, we can neglect in the denominator of the integrand in (Eqn. A.7.7) the second term—that
is, the activation spectrum is also approximated by the power law (Eqn. 7.7.1). Then, using (Eqn. 7.2.5)
for xcon
1
(c3 w am )3/ 2 t 3
∫z
ks 0 /2 −1
J3(2) (t ) = 3
(1 − z )2 dz
4ξcon 0

−4 −3 3 k 
= 4 D V α (c3 w am )3/ 2 t 3 B  s 0 , 3 .
3
(A.7.8)
v w c
 2 
Evaluation of the Integrals J2 and J3 for Four Limiting Cases 285

Limit #3: Large w, diffusional growth regime. At large w—i.e., in the limit sm>> s0 (ls >> 1)—the
integral J3 in (Eqns. 7.3.9) or (A.7.2) in general cannot be reduced to the beta function, and it is more
convenient to use J2(t). Let us consider two functions in the subintegral expression for J2 in (Eqn. A.7.1):

x ks 0 −1 {[U s + (1 − x 2 )]1/2 − Vs }2
ϕ nd ( x ) = , ψ (x) = . (A.7.9)
(1 + λs x ks 0 )2 [U s + (1 − x 2 )]1/2

Then, J2 can be written as

1

J 2 (t ) = ∫ψ ( x )ϕ nd ( x ) dx . (A.7.10)
0

The function jnd (x) represents the algebraic CCN activity spectrum in nondimensional form. Its
maximum evaluated from the condition d[jnd(x)]/dx = 0 is located at
1/ks 0
 1 ks 0 − 1 
xm =   . (A.7.11)
 λs k s 0 + 1 

For example, if ks0 = 2, then xm ≈ 0.1 for ls ∼ 30 and xm ≈ 0.18 for ls ∼ 10—i.e., xm << 1 at ls >> 1. It
was shown in Khvorostyanov and Curry (2006) and in Chapter 6 that this differential CCN activity
spectrum has the shape of a “smoothed”, bell-shaped Dirac delta-function, and the nondimensional
function jnd(x) also has this property. This is illustrated in Fig. 7.18, which shows that jnd(x) has a
sharp maximum at x = xm, while y (x) is a smooth function. Thus, the major contribution into J2 comes

CCN spectrum, φnd(x)

φnd (x), ψ (x), and integrand in J2

0.1 1st fraction, ψ(x)

integrand = φnd(x)*ψ(x)

1E–2

1E–3

1E–4
0.0 0.2 0.4 0.6 0.8 1.0
Argument x

Figure 7.18. Functions jnd(x) (dimensionless CCN spectrum, open circles), y (x) defined in (Eqn. A.7.9),
triangles, and the integrand jnd(x) y (x) (solid circles) of the integral J2 in (Eqn. A.7.10). The values of
the parameters are similar to those used earlier: rd0 = 0.05 mm, sd = 1.8, rd(t0) = 0, b = 0.25, b = 0.5,
t =10 s, but with greater w = 200 cm s−1. Then, ls ∼ 29.7 >> 1. From Khvorostyanov and Curry (2009a),
J. Atmos. Sci., 66, © American Meteorological Society. Used with permission.
286 Activation of Cloud Condensation Nuclei into Cloud Drops

from the region around xm, and we can use for evaluation of J2 the “quasi d-function” property of
jnd(x), or “the mean value theorem” from the mathematical analysis. Thus, this limit for J2 is:
1 1

J 2(3) (t ) = ∫ψ ( x )ϕ nd ( x ) dx ≈ ψ ( x m ) ∫ϕ nd ( x ) dx . (A.7.12)
0 0

The last integral is not equal to 1 and still should be evaluated since jnd(x) is proportional to the
smoothed delta-function but not equal. To find this integral, we use the property found in KC06
and described in Chapter 6 that the CCN differential spectrum is a smoothed d-function and is a
derivative of the droplet concentration defined in (Eqn. 7.4.7), which is a smoothed Heaviside step-
function, found in a similar form by Ghan et al. (1993, 1995). The corresponding fraction activated,
Fnd(x) = Ndr(sm)/Na, can be written from (Eqn. 7.4.7) in nondimensional form as

λ s x ks 0
Fnd ( x ) = . (A.7.13)
1 + λ s x ks 0

One can see that

1 dFnd ( x )
ϕ nd ( x ) = . (A.7.14)
k s 0 λs dx

Thus,
1 1
1 dFnd ( x )
∫ϕ
0
nd ( x ) dx =
ks 0 λs ∫
0
dx
dx

1 1 1
=  Fnd (1) − Fnd (0)  = ≈ . (A.7.15)
k s 0 λs  k s 0 (1 + λs ) k s 0 λs

The last approximate equation uses the fact that ls >> 1. With ac ∼ 1 and rd(t0) = 0, the values Us << 1,
and Vs << 1, and y (xm) ≈ (1 − xm2). Fig. 7.18 shows that at ls >> 1 and xm << 1, the value of y (xm) is
very close to 1—e.g., y (xm) = 0.997 in this example. Thus, it can be assumed y (xm) = 1. Substituting
(Eqn. A.7.15) into (Eqn. A.7.12) with y (xm) = 1, and using (Eqn. 7.3.10) for ls yields
ks 0
1 1  s0 
J 2(3) (t ) ≈ = . (A.7.16)
k s 0 λs k s 0  am t 

The exact numerical calculation of J2 with the functions jnd(x) and y (x) shown in Fig. 7.18 yields
J 2(3) = 1.726 × 10 −2, and calculation with approximation (Eqn. A.7.16) and ls = 29.7, corresponding to
Fig. 7.18, yields J 2(3) = 1.795 × 10 −2 —i.e., the error is less than 4%, so the limit (Eqn. A.7.16) for J 2(3)
can be used with good accuracy in this limit.

Limit #4: Large w (ks >> 1), kinetic growth regime (`c << 1). Now we consider the analytical
evaluation of the integral J2 in (Eqns. 7.3.8) or (A.7.1) in the 4th limit, sm >> s0 (ls >> 1), and ac << 1.
When ac << 1, then xcon >> rd(t0), and rd(t0) can be neglected in Us, then Us = Vs2; besides, (1 − x2) << Us,
and (1 − x2) << Vs2. Similar to the 3rd limit in the previous section, we present the integrand of J2
(Eqn. A.7.1) as jnd(x)y (x) with functions defined in (Eqn. A.7.9). Similar to the 2nd limit, expansion
of y(x) by the small parameter (1 − x2)/Vs2 yields

(1 − x 2 )2 (am c3 w )3/2 t 3
ψ (x) ≈ = (1 − x 2 )2 . (A.7.17)
4Vs3 3
4ξcon
Evaluation of the Integrals J2 and J3 for Four Limiting Cases 287

As for the 3rd limit, the function jnd(x) has a sharp maximum at x = xm << 1 when ls >> 1, and y (x) is
a smooth function. Using again the “quasi d-function” property of jnd(x) and the mean value theorem,
we can present J 2(4) as
1 1

J 2(4) (t ) = ∫ ψ ( x )ϕ nd ( x )dx ≈ ψ ( x m ) ∫ϕnd ( x ) dx . (A.7.17a)

0 0

Substituting (Eqn. A.7.17) into (Eqn. A.7.17a) with account for (Eqn. A.7.15), yields

(am c3 w )3/ 2 t 3 1
J 2(4) (t ) ≈ 3
(1 − x m2 )2 . (A.7.18)
4ξcon ks 0 λs

Using (Eqn. 7.3.10) for ls, (Eqn. 7.2.5) for xcon, and using again the relation (1 − xm2) ≈ 1, J 2(4)
becomes finally

1 am3/2− ks 0 c33/2
wt α c Vw s0
3− k s 0 3 3 k s 0
2 J 2(4) (t ) ≈ . (A.7.19)
128 k s 0 Dv3
8
Homogeneous Nucleation

Phase transitions in a substance may proceed with or without the presence of foreign substances. If
formation (nucleation) of a new phase in the original phase is catalyzed by a foreign substance, this
process is called heterogeneous nucleation. IIn this chapter, we consider phase transitions without
participation of a foreign substance. Formation of a new phase within the original phase under such
conditions is termed homogeneous nucleation. The most important examples of homogeneous nucle-
ation for cloud physics are: formation of ice crystals (homogeneous ice nucleation) or liquid drops
from supersaturated water vapor (homogeneous drop nucleation); formation of ice crystals by the
freezing of liquid water or solution drops (homogeneous freezing); and formation of drops by the
melting of ice crystals.
In Chapters 3 and 4, we discussed phase transitions and conditions of equilibrium between various
phases. However, a phase transition from a metastable phase A into a stable phase B does not occur
instantaneously or exactly at equilibrium. A bulk phase A of some substance may exist during a sufficient
time in a metastable state; that is, not in thermodynamic equilibrium, but still without transition into a
more stable phase B. Examples of relevance to water are: a) supersaturated vapor (phase A) at a relative
humidity greater than 100% but still without condensation into the bulk liquid water (phase B); b) super-
heated liquid water (phase A) above the boiling point without full transition into the vapor (phase B);
c) supercooled liquid water at temperatures below the freezing point (phase A) without freezing into
ice (phase B); and d) a salt solution (phase A) supersaturated with respect to dissolved salt but without
crystallizing salt into a solid (phase B).
In this chapter, the concepts of metastable states and nucleation of a new phase are introduced
based on classical nucleation theory. Equations are derived for nucleation rates of condensation,
deposition, and homogeneous ice nucleation. Empirical and semi-empirical parameterizations of
homogeneous ice nucleation are reviewed. Equations for water and ice supersaturation with homo-
geneous ice nucleation are derived to study ice nucleation kinetics. The homogeneous freezing and
melting of water and aqueous solutions are examined in the framework of extended classical nucle-
ation theory. Based on thermodynamic principles, general equations for the critical germ radius and
free energy are derived that express these properties as functions of temperature, solution molality,
pressure, and the finite size of freezing and melting particles. This theory is applied to the study
of liquid–solid phase transitions: the homogeneous freezing of aqueous solutions and the surface
melting of ice. Simple analytical expressions are derived for the corresponding freezing and melting
critical temperatures Tf,hom, Tm, freezing and melting point depressions, ΔTf,hom, ΔTm, for their rela-
tion, and for the critical water and ice saturation ratios Sw,hom, Si,hom. The kinetics of homogeneous
ice nucleation and microphysical processes of formation of a cirrus-like cloud are studied with use
of a cloud parcel model with spectral bin microphysics and a detailed supersaturation equation.

289
290 Homogeneous Nucleation

Based on the general analytical equations of the classical nucleation theory and some simplifica-
tions prompted by the parcel model simulations, an analytical parameterization of homogeneous ice
nucleation is developed.

8.1. Metastable States and Nucleation of a New Phase

In a metastable phase A (called the mother or parent phase), fluctuations exist that lead to formation
of small clusters or nuclei consisting of several molecules or atoms of the stable phase B, termed
embryos. Phase transition begins with formation of the small embryos of phase B inside phase A,
which have the form of small drops, bubbles, or crystals (i.e., small embryos of a new phase B)—in
other words, generally small volumes surrounded by a newly formed surface at the interface of the
phases A and B. Before the embryos reach some critical size rcr, the energy DF of their formation
increases with size. The embryos are also metastable and disrupt in further fluctuations. But after
they reach the critical size, DF begins to decrease with the size of the embryo, and the embryos can
grow spontaneously. Such supercritical embryos are called germs, although the subcritical embryos
are sometimes also called germs.
Suppose that the molecular chemical potentials in phases A and B are mA1 and mB1, and phase A
is comprised of (NA + NB) molecules, of which NB molecules can form an embryo in phase B. Then,
the thermodynamic potentials before and after nucleation, F1 and F2, are F1 = mA1(NA + NB), and
F2 = mA1NA + mB1NB. Formation of an embryo of radius r causes two kinds of energy changes: a
decrease in the volume energy DFV = F2 − F1 = −NB (mA1 − mB1), and an increase in the surface energy
DFs = 4pr2sAB due to formation of the new surface surrounding the embryo of phase B, with sAB
being the surface tension between the two phases. The total energy change DF is

∆F = ∆FV + ∆Fs = F2 − F1 + 4π r 2σ AB = − N B ( µ A1 − µ B1 ) + 4π r 2σ AB . (8.1.1)

This expression can also be written for the molar quantities using the relation NB = NAvnB, where NAv
is Avogadro’s number, and nB is the number of moles of phase B. Thus,

∆F = ∆FV + ∆Fs = − nB ( µ A − µ B ) + 4π r 2σ AB , (8.1.1a)

where mA = NAvmA1 and mB = NAvmB1 are the molar chemical potentials of phases A and B. If phase
A is metastable, and B is stable, then mA1 > mB1, and the first term on the RHS of these equations is
negative, it causes a decrease in energy. The second term with sAB is positive and causes an energy
increase.
Now, the embryo contains NB molecules. If the volume of a germ is VB, and the volume of a mol-
ecule in phase B is vB1 = MB/(rBNAv), where MB and rB are the molecular weight and the density of
phase B, then NB can be expressed via r as NB = VB /vB1 = (4/3)pr3/vB1, and DF can be rewritten as

( µ A1 − µ B1 )
∆F = ∆FV + ∆Fs = − VB + 4π r 2σ AB
v B1
4π r 3
= − ( µ A1 − µ B1 ) + 4π r 2σ AB . (8.1.2)
3 v B1

The energy change therefore consists of two components: latent heat release and surface tension
work. At very small r, the second term proportional to r2 is greater than the first term, DF > 0, and
8.1. Metastable States and Nucleation of a New Phase 291

will increase with increasing r. However, the absolute value of the first term on the RHS, proportional
to r3, will increase faster, eventually exceeding the magnitude of the first term, and DF will reach a
maximum at some critical radius rcr and then will begin to decrease at r > rcr. The maximum or criti-
cal value of DFcr is determined from the condition d(DFcr)/dr = 0, which yields from (Eqn. 8.1.2) an
expression for rcr of
2σ AB v B1
rcr = . (8.1.3)
µ A1 − µ B1

This can be rewritten in molar quantities by multiplying the numerator and denominator in
(Eqn. 8.1.3) by the Avogadro number NAv to obtain

2σ AB v Bµ
rcr = , (8.1.4)
µ A − µB

where vBm = NAvvB1 = MB/rB is the molar volume of phase B. The difference of the molar chemical
potentials A∝ = DmAB = mA − mB is called the ordinary affinity of a phase transition, and the previous
equations show that the critical radius can be evaluated using known values of affinity A∝, surface
tension, and the molar volume of the more stable phase.
When the affinity DmAB = mA − mB is known, then rcr can be evaluated along with the corresponding
critical energy DF and the nucleation rate J. If rcr is known, then the affinity DmAB can be evaluated,
and then DFcr and J. In many cases, rcr can be evaluated without considering separately mA and mB, or
the difference DmAB; the values of rcr, DF, and J can be calculated directly from the entropy equation
or other equations. This is illustrated in the following text considering the homogeneous nucleation
of the drops from a supersaturated vapor.
In Chapter 3, we obtained Kelvin’s equation (Eqn. 3.8.4) for the equilibrium saturation ratio Sw
over a droplet of radius r in the vapor or in a humid air:

2 M wσ vw
ln Sw = . (8.1.5)
RT ρ w r

This equation can be solved for the equilibrium radius req,w of a drop at a saturation ratio Sw

2 M wσ vw 2σ vw vwµ 2σ vw vw1
req , w = = = , (8.1.6)
RT ρ w ln Sw RT ln Sw kT ln Sw

where vwm = Mw/rw and vw1 = Mw/(Navrw) are the molar and molecular volumes of water, and k is the
Boltzmann’s constant. Comparing (Eqns. 8.1.4) and (8.1.6), we see that the difference of molecular
chemical potentials of vapor mv1 and water mw1 (the affinity) is

∆µ vw ,1 = µ v1 − µ w1 = kT ln Sw . (8.1.7)

In terms of molar chemical potentials, this relation is

∆µ vw = µ v − µ w = RT ln Sw . (8.1.7a)

Substituting (Eqn. 8.1.7a) into (Eqn. 8.1.2) for DF with superheated vapor as phase A and condensed
water as phase B, we obtain the free energy DF of an embryo formation

kT ln Sw 4π r 3
∆F = − + 4π r 2σ vw . (8.1.8)
v w1 3
292 Homogeneous Nucleation

This expression has a maximum value at rcr that is determined from the condition d(DFcr)/dr = 0,
which yields

2σ vw vw1 2 M wσ vw
rcr , w = = . (8.1.9)
kT ln Sw RT ρ w ln Sw

Thus, the critical radius rcr coincides in this case with the equilibrium Kelvin’s radius (Eqn. 8.1.6).
Substituting this rcr into (Eqn. 8.1.8), we obtain the corresponding critical energy

4πσ vw rcr2 σ vw Acr 16π M w2 σ vw

3
∆Fcr = = = , (8.1.10)
3 3 3[ RT ρ w (ln Sw )]2

where Acr is the surface area of the sphere with radius rcr, and we used the first of (Eqn. 8.1.6) for rcr.
Thus, the second equality in (Eqn. 8.1.10) shows that the critical energy of a germ formation is equal
to one third of the product of the surface tension by the surface area of the germ.
Fig. 8.1a,b illustrate the radius dependence of a liquid embryo formation from supersatu-
rated vapor: an increase and subsequent decrease of the embryo energies with increasing radius r
(Fig. 8.1a) and a corresponding increase of the number of molecules g (Fig. 8.1b) inside the embryo
for various saturation ratios Sw from 0.9 to 6. It is seen that the energy maxima shift to smaller r and
g with increasing Sw—i.e., the germs’ sizes decrease with increasing Sw. These maxima correspond
to the critical energies, and are given in more detail in Table 8.1 along with the critical radii rcr and
the number of molecules gcr. Table 8.1 shows that as Sw increases from 0.9 to 6, the critical radius rcr
decreases from 40.8 Å (40.8 × 10−8 cm) to 6.2 Å, and the corresponding number of molecules in an
embryo decreases from 12496 to 43. The energy DFcr decreases almost 170 times, from 1.89 × 10−10 erg
to 1.15 × 10−12 erg as Sw increases from 0.9 to 6. The smallest radius (6.2 Å) at Sw = 6 is already com-
parable to the size of the molecules (∼3.5 Å). However, even a small germ still contains 43 molecules,
which can make justifiable to some extent application of the bulk concepts of surface tension, bulk
density, germ surface, and volume.

2.5E–11 Sw = 1.5
Energy of embryo formation (erg)

2.5E–11
Energy of embryo formation (erg)

Sw = 2.0
2.0E–11 Sw = 2.5 2.0E–11
Sw = 3.0
1.5E–11 Sw = 4.0 1.5E–11
Sw = 6
1.0E–11 1.0E–11

5.0E–12 5.0E–12

0.0E+0 0.0E+0

–5.0E–12 –5.0E–12
0 10 20 30 40 1 1E+1 1E+2 1E+3 1E+4
Radius of embryo (Angstrom) Number of molecules in embryo
(a) (b)

Figure 8.1. Dependence of the energy of a liquid embryo formation from supersaturated vapor
on the embryo radius r (a), and on the number of molecules g in the embryo (b) at various water
saturation ratios Sw indicated in the legend.
8.2. Nucleation Rates for Condensation and Deposition 293

Table 8.1. Critical radii rcr (Å), critical energies DFcr (erg), and the number of molecules gcr in the
critical germs of water droplet in supersaturated vapor at various saturation ratios Sw. The critical
values correspond to the maxima of the curves in Fig. 8.1.

Sw 0.9 1.5 2.0 2.5 3.0 4.0 6.0

rcr (Å) 40.8 27 16 12 10 8 6.2
DFcr (10−12 erg) 189 22.4 7.66 4.38 3.05 1.92 1.15
gcr (number of molecules) 12496 3702 753 317 184 94 43

The critical radius rcr,i and energy of a critical germ for ice formation from supersaturated water
vapor are derived analogously and differ from the properties of the liquid droplet germs by replacing
all liquid water parameters with ice parameters:
2 M wσ iv 2σ iv vi1
rcr ,i = = , (8.1.11)
RT ρi ln Si kT ln Si

where the subscript “i” denotes the quantities relevant to ice. The critical energy of an ice germ for-
mation instead of (Eqn. 8.1.10) is

4πσ iv rcr2 ,i σ iv Acr ,i 16π M w2 σ iv3

∆Fcr ,i = = = . (8.1.12)
3 3 3[ RT ρi (ln Si )]2

8.2. Nucleation Rates for Condensation and Deposition

8.2.1. Application of Boltzmann Statistics

The rate of formation of the new embryos of the more stable daughter phase within the unstable
parent phase (per unit volume per unit time) Jhom is termed the nucleation rate. The classical deri-
vation of the nucleation rate was given by Volmer and Weber (1926) based on thermodynamic and
kinetic arguments. It was subsequently modified by several researchers (e.g., Farkas, 1927; Becker
and Döring, 1935; Volmer, 1939; Zeldovich, 1942; Frenkel, 1946), who refined calculations of the
reverse process: evaporation of molecules from the germs. These derivations were based on two
major assumptions: 1) the germs before nucleation have a spherical form with the usual macroscopic
densities and surface tensions; and 2) the germs are distributed according to the Boltzmann statistics.
The first assumption was later revised and some correction factors were introduced to account for
the nonsphericity of ice germs (e.g., Fletcher 1962). The second assumption can also be revised, and
more general statistical distributions considered, as will be discussed later in this chapter.
Application of Boltzmann’s statistics for the number Ng of g-mers (embryos containing g mol-
ecules or atoms with g-th energy state DFg) in a volume V is

Ng = Nsat exp(− ∆Fg /kT ), (8.2.1)

or of the concentrations cg = Ng /V of the g-mers

cg = csat , w exp(− ∆Fg /kT ), (8.2.2)

where Nsat and csat,w are the number and concentration of the monomers (water molecules) in a water-
saturated environment. The nucleation rate Jg of transition from the metastable parent phase A into
294 Homogeneous Nucleation

the stable daughter phase B can be evaluated as the number of embryos (cm−3 s−1) per unit of time
entering the category containing g molecules or atoms of the parent phase. Then, Jg can be calculated
from the kinetic equation

J g = fg −1 jg( +−)1 Ag −1 − fg jg( − ) Ag , (8.2.3)

where g is the number of molecules or atoms of the parent phase in an embryo of the new phase,
Ag = 4prg2 is the surface area of an embryo with radius rg containing g particles of the parent phase,
(+)
fg is the time-dependent concentration of such embryos (different from cg), jg −1 is the molecular flux
(−)
from the (g − 1)-mer embryo into g-mer, and jg is the flux from a g-mer into a (g + 1)-mer embryo.
The first and second terms in (Eqn. 8.2.3) describe respectively the influx and depletion of the germs
of class g. In equilibrium with Jg = 0, these two fluxes are equal and the condition of equilibrium is

cg −1 jg( +−)1 Ag −1 − cg jg( − ) Ag = 0. (8.2.4)

Equation (8.2.4) allows exclusion of the depletion flux,

jg( − ) Ag = (cg −1/cg ) jg( +−)1 Ag −1 . (8.2.5)

Substituting this expression into (Eqn. 8.2.3) yields

cg − 1  f g −1 f g 
J g = fg −1 Ag −1 jg( +−)1 − fg Ag −1 jg( +−)1 = cg −1 jg( +−)1 Ag −1  − . (8.2.6)
cg  cg − 1 cg 

The time variation of the concentration fg in the g-state is determined by the equation of balance

∂ fg
= J g − J g +1 , (8.2.7)
∂t
where the first term on the RHS describes the arrival into the embryo class g, and the second term
describes outflow from class g—that is, arrival into embryo class (g + 1).
When the number g of molecules in a germ is sufficiently large (this requirement usually is fulfilled),
we can replace the discrete number g by a continuous variable g and write it as an argument of the function
instead of the subscript. The finite differences in (Eqns. 8.2.6) and (8.2.7) are replaced by the derivatives

∂ f ( g) ∂ J ( g)
= J ( g) − J ( g + 1) = − , (8.2.8)
∂t ∂g

 f g −1 f g  ∂  f ( g) 
J g = cg −1 jg( +−)1 Ag −1  −  = − cg −1 jg( +−)1 Ag −1 . (8.2.9)
 cg − 1 cg  ∂ g  c( g) 

We now introduce a diffusion coefficient in the g-space:

D( g) = jg( +−)1 Ag −1 ≈ jg( + ) Ag . (8.2.10)

The last approximate equality holds if the number g is sufficiently high. Then, J in (Eqn. 8.2.9) can
be rewritten as

∂  f ( g) 
J ( g ) = − c( g ) D ( g ) (8.2.11a)
∂ g  c( g) 
∂ f ( g) ∂[ln c( g)]
= − D ( g) + D ( g) f ( g) . (8.2.11b)
∂g ∂g
8.2. Nucleation Rates for Condensation and Deposition 295

It follows from (Eqn. 8.2.2) that

∂[ln c( g)] ∂  ∆F ( g) 
=−  . (8.2.12)
∂g ∂ g  kT 

Substituting this equation into (Eqn. 8.2.11b), we obtain

∂ f ( g)  D( g) ∂[ ∆F ( g)] 
J ( g) = − D ( g) −  f ( g). (8.2.13)
∂g  kT ∂g 

Thus, we arrive at an interesting result: the nucleation rate can be presented in the form of the flux in
the g-space. This flux can also be written in the form

∂ f ( g)
J ( g) = − D ( g) − f ( g)Vg ( g), (8.2.14)
∂g
which includes drift and diffusion. The diffusion part (the first term on the RHS) is proportional to
D(g) and describes fluxes in both directions by g, toward larger g and back to smaller g, broadening
the function f(g). Drift (the second term on the RHS) is proportional to Vg(g), which is an effective
velocity in g-space:

D( g) ∂[ ∆F ( g)]
Vg ( g) = . (8.2.15)
kT ∂g

8.2.2. The Fokker–Planck, and the Frenkel–Zeldovich Kinetic

Equations and the Zeldovich Factor

The expressions (Eqns. 8.2.13) and (8.2.14) are typical for physical kinetics, and are analogous to
the usual formulae in the Fokker–Planck kinetic equation for the flux of the particles. In the Fokker–
Planck equation, the particles are distributed along the g-axis with density f(g) and move along
the axis g by the joint action of diffusion D(g) and drift Vg(g) induced by an external potential
force DF(g), while the mobility coefficient q of the particles is determined by Einstein’s relation
q = D(g)/kT. The diffusion coefficient D(g) defined by (Eqn. 8.2.10) represents a function of g that is
related to the germ radius as

gv B = (4π /3)rg3 , or rg = g1/3 v1/B 3 (3/4π )1/3 , (8.2.16)

where vB is the volume of a molecule in phase B. According to (Eqn. 8.2.10), D(g) is proportional
to the surface area Ag. Substituting this rg from (Eqn. 8.2.16) into Ag in (Eqn. 8.2.10), D(g) can be
written via g as

D( g) = (4π )1/ 3 32 / 3 v B2 / 3 g 2 / 3 jg( + ) . (8.2.17)

Thus, D ∼ g2/3 (or D ∼ rg2 since g ∼ r3) and resembles a diffusion coefficient in an inhomogeneous
medium with coordinate dependence—e.g., the turbulent diffusion coefficient in the atmospheric
surface layer kz ∼ ze, or the Richardson turbulent diffusion coefficient with the dependence kx ∼ x4/3
(e.g., Monin and Yaglom, 2007a, b).
296 Homogeneous Nucleation

Substituting (Eqn. 8.2.13) for J into the kinetic equation (Eqn. 8.2.8) for f, we obtain a kinetic
equation for the distribution f(g) known as the Frenkel–Zeldovich kinetic equation:

∂f ∂  ∂ fg  1 ∂  ∂[ ∆F ( g)] 
= D + Df . (8.2.18)
∂t ∂ g  ∂ g  kT ∂ g  ∂ g 

This is a kinetic equation of the Fokker–Planck type with drift and diffusion, and the second deriva-
tive by g, and can be written in the form of a continuity equation:

∂f ∂ J ( g)
=− , (8.2.19)
∂t ∂g

where the flux J(g) is defined in (Eqns. 8.2.13) or (8.2.14).

The steady state distribution, ∂f/∂t = 0, corresponds to J(g) = const. Then, we can rewrite
(Eqn. 8.2.11a) as

∂  f ( g)  J
  =− . (8.2.20)
∂ g  c( g )  c( g ) D ( g )

The integration of this equation yields a solution to the Frenkel–Zeldovich equation:

G
dg′
f ( g) = Jc( g) ∫ , (8.2.21)
g
D( g′)c( g′)

where the upper limit of integration G is chosen such that f(G) = 0. Using the dependence (Eqn. 8.2.2)
c(g) = csatexp[−DF(g)/kT] in front of the integral and in the integrand, this expression can be transformed as

 ∆F ( g)   ∆F ( g′) 
G
1
kT  ∫g D( g′)
f ( g) = J exp  −  exp  dg ′. (8.2.22)
  kT 

The function exp[DF(g)/kT] in the integrand has a very sharp maximum near g = g*, which cor-
responds to a critical radius. Therefore, the value 1/D(g′) with rather weak dependence on g can be
removed out of the integral and can be taken as 1/D(g*). Then, DF can be expanded into the power
series near g = g*:

d ∆F ( g) 1 d 2 ∆F
∆F ( g) ≈ ∆Fmax + ( g − g*) + ( g − g*)2 . (8.2.23)
dg g = g*
2 dg 2 g = g*

Since dDF/dg = 0 near the maximum point at g = g*, this expansion reduces to

1  d 2 ∆F 
∆F ( g) ≈ ∆Fmax ( g*) − γ ( g − g*) 2 , γ = − . (8.2.24)
2  dg 2  g= g*

The minus sign here is chosen because d2DF/dg2 < 0 near the maximum point g = g*, so g > 0. Sub-
stituting (Eqn. 8.2.24) into (Eqn. 8.2.22), replacing 1/D(g′) in the integrand with 1/D(g*) before the
integral, and introducing a new variable x = g′ − g*, we obtain
G − g*
J  ∆F ( g*) ∆F ( g)   x2 
f ( g) =
D( g*)
exp 
 kT
−  ∫
kT  − ( g*− g )
exp  −
 (2 kT /γ ) 
dx . (8.2.25)

The quantity (kT/g)1/2 represents the width of the maximum of the integrand near g = g*.
8.2. Nucleation Rates for Condensation and Deposition 297

If (G − g*) and (g* − g) are large compared to (kT/g)1/2, then the limits of the integral can be extended
to plus and minus infinities. Then, the integral can be evaluated using the Gaussian formula as
G − g* 1/ 2 ∞ 1/ 2 1/ 2
 γ x2   2 kT  − x2  2 kT   2π kT 
∫
− ( g* − g )
exp  − 
 2 kT 
dx ≈ 
 γ  ∫−∞ e dx =  γ  π 1/ 2 = 
 γ 
. (8.2.26)

Equation (8.2.25) can be rewritten using (Eqn. 8.2.2) for c(g) and (Eqn. 8.2.26) for the integral as
1/ 2
f ( g) J  ∆F ( g*)   2π kT 
= exp  = const . (8.2.27)
c( g) csat , w D( g*)  kT   γ 

Since f(g) = c(g) at g << g*, the value of the constant is 1. Then, equating the middle part of this
equation to 1, we obtain for J
1/ 2
 ∆F ( g*)   γ 
J = csat , w D( g*) exp  −   . (8.2.28)
 kT   2π kT 

Or, using again (Eqn. 8.2.2)

1/ 2
 γ 
J = c( g*) D( g*)  = c( g*) D( g*) Z , (8.2.29)
 2π kT 

where we introduced a multiplier called the “Zeldovich factor” (Zeldovich, 1942):

1/ 2
 γ 
1/ 2
 1  − d 2 ∆F ( g*)  
Z = =    . (8.2.30)
 2π kT  
 2π kT  dg 2 
Equation (8.2.29) allows calculation of the nucleation rates for various situations and plays an impor-
tant role in cloud kinetics. Numerical calculations show that Z ∼ O (10−1)—that is, taking into account
germ evaporation decreases the nucleation rate.
For calculations of the Zeldovich factor and nucleation rates, we need to calculate d2DF/dg2, which
requires some auxiliary relations. If the masses of a germ and of a single molecule are mg and mw1,
then the following relations are valid
1/3
vg 4π 3  3v 
g= = rg , or rg = g1/3  w1  . (8.2.31)
v w1 3 v w1  4π 

These relations also yield the following equations for the surface area Ag:
1/2
 3v  dAg 2 Ag
Ag = 4π rg2 = g 2/3  w1  , = . (8.2.32)
 4π  dg 3 g
Now using the expression (Eqn. 8.1.1) for DF written for NB = g
∆F = − ( µ A1 − µ B1 ) g + Agσ vw , (8.2.33)

we can calculate the derivatives for vapor (v) as metastable phase A and water (w) as stable phase B

d ∆F 2 Ag
= ( µ w1 − µ v 1 ) + σ vw , (8.2.34)
dg 3g

d 2 ∆F 2 Agσ vw 4 Agσ vw 2 Agσ vw

=− + =− . (8.2.35)
dg 2 3g 2 9g2 9g2
298 Homogeneous Nucleation

Substituting (Eqn. 8.2.35) into (Eqn. 8.2.30) for Z and using the relation Agsvw = 3DF from
(Eqn. 8.1.10) yields
1/ 2 1/ 2
 Agσ vw   ∆Fg 
Z= 2 
=  . (8.2.36)
 9π kTg   3π kTg 2 

Substituting into (Eqn. 8.2.36) the first equality from (Eqn. 8.1.10) for DFg and (Eqn. 8.2.31) for g,
we obtain the Zeldovich factor:
1/ 2 1/ 2
2 v w1  σ vw  2Mw  σ vw 
Z=   =   , (8.2.37)
Ag kT  Ag ρ w N av kT 

where we used the relation for the molecular volume vw1 = Mw/(rwNav).
The nucleation rate for the homogeneous condensation of the drops from supersaturated vapor is
obtained from (Eqn. 8.2.29) using the Boltzmann distribution for g-mers with the critical energy DFcr:

J = c( g*) D( g*) Z z = csat , w jg( + ) Ag Z exp(−∆Fcr /kT ). (8.2.38)

Using the first form of Z in (Eqn. 8.2.37), this can be written as

1/ 2
σ 
J = 2csat , w jg( + ) vw1  vw  exp(−∆Fcr /kT ). (8.2.38a)
 kT 
(+)
The flux of the monomers jg to the germ in this case is just the molecular vapor flux, the same as
the molecular flux of condensation onto a droplet that was calculated in Chapter 5. Using also the
equation of state for water vapor, cw = ew /kT, we obtain
α c cwVw α c ew α c ews Sw
jg( + ) = = 1/ 2
= , (8.2.39)
4 (2π mw1 kT ) (2π mw1 kT )1/2

where Vw = (8RT/pMw)1/2 = (8kT/pmw1)1/2 is the mean thermal molecular speed (see Chapter 5), mw1 is
the mass of a water molecule, ew is the vapor pressure, and ac is the condensation coefficient.
(+)
Substituting (Eqn. 8.2.39) for jg into (Eqn. 8.2.38a), we obtain for the homogeneous nucleation
rate Jcond,hom of the drops from supersaturated vapor
1/2
α cew Sw vw1  σ vw 
Jcond ,hom = 2csat ,w   exp(−∆Fcr / kT ). (8.2.40)
(2π mw1kT )1/2  kT 

Using the equation of state for the saturated vapor, csat,w = ews /kT, the relation for the volume of a
water molecule vw1 = Mw/(rwNav), and the energy DFcr defined in (Eqn. 8.1.10), it can be rewritten as
1/2
α e2 M S  2σ vw   16π M w2 σ vw
3

Jcond ,hom = c ws2 w w  π m  exp  − 3kT [ RT ρ (ln S )]2  , (8.2.41)
( kT ) ρ w N av  w1   w w 

This relation is also used in several other forms. Substituting here the relations mw1 = Mw/NAv,
k = R/NAv, and rearranging the terms, we obtain
2 1/2
α c Sw N Av  ews   2 N Av M wσ vw   16π M w2 σ vw
3

Jcond ,hom =     exp  − 2 
. (8.2.41a)
ρw RT π  3kT [ RT ρ w (ln Sw )] 
8.2. Nucleation Rates for Condensation and Deposition 299

The nucleation rate of the spherical ice germs from the vapor by deposition Jdep,hom can be calcu-
lated in the same way, or, just with replacement in (Eqn. 8.2.41) of the water properties with the ice
properties:
1/2
α d eis2 M w Si  2σ iv   16π M w2 σ iv3 
J dep ,hom = exp  − , (8.2.42)
( kT )2 ρi N av  π mw1  2 
 3kT [ RT ρi (ln Si )] 

where ad is the deposition coefficient (Section 5.2), siv is the surface tension at the ice-vapor
interface, and the energy of an ice germ formation DFcr is described by (Eqn. 8.1.12) instead of
(Eqn. 8.1.10). Using the same relations as for (Eqn. 8.2.41a), mw1 = Mw/NAv, k = R/NAv, this equa-
tion can be written as
2 1/2
α d Si N Av  eis   2 N Av M wσ iv   16π M w2 σ iv3 
J dep ,hom =     exp  − 2 
. (8.2.42a)
ρi RT   π  3kT [ RT ρi (ln Si )] 

Numerical calculations with (Eqns. 8.2.41) and (8.2.41a) show that the nucleation rates of drops from
supersaturated vapor are very small at Sw < 5–6; Jcon.hom is ∼ 7 × 10−2 cm−3 s−1 at Sw = 5 and Jcon.hom
is ∼ 6 × 103 cm−3 s−1 at Sw = 6. The nucleation rates of crystals from the vapor are even smaller,
∼ 3 × 10−52 cm−3 s−1 at Si = 6, and noticeable nucleation begins at Si > 12−15. Such high saturation
ratios normally are not reached in natural clouds, thus drops and crystals do not form in clouds via
homogeneous nucleation from the vapor. However, this and higher saturation ratios can be created in
the cloud chambers, where various properties of homogeneous nucleation from the vapor are studied.

8.2.3. Application of Bose–Einstein Statistics for Condensation and Deposition

The previous derivation of the nucleation rate was based on the Boltzmann distribution of the g-mers.
However, as we have seen in Chapter 3, the Boltzmann distribution is a particular case of the more
general Bose–Einstein distribution:

1
c( g) = csat , w . (8.2.43)
exp( ∆Fg /kT ) − 1

With the Bose–Einstein statistics, the homogeneous nucleation rate of drops nucleation in supersatu-
rated vapor (Eqn. 8.2.38) can be rewritten as

1
J hom = csat , w jg( + ) Ag Z . (8.2.44)
exp( ∆Fcr /kT ) − 1

For DFcr >> kT, we have an inequality exp(DFcr/kT) >> 1, the Bose–Einstein distribution con-
verts into the Boltzmann distribution, c(g) = csat,wexp(−DFg/kT), and (Eqn. 8.2.44) converts into
(Eqn. 8.2.38). The relation DFcr >> kT is valid in most cases. However, in some cases, when svw is
small (e.g., at very low temperatures or in the presence of strong surfactants or other pollutants that
3
decrease surface tension), then ∆F ~ σ vw may become comparable to or smaller than kT. Then, all
of the previous derivations should be repeated using the Bose–Einstein statistics for particles with
integer spin as the water molecules instead of the Boltzmann statistics.
300 Homogeneous Nucleation

For the other opposite case, DFg << kT, the Bose–Einstein statistics has another limit obtained
by expanding the exponent into the power series, exp(DFg/kT) – 1 ≈ 1 + DFg/kT – 1 = DFg/kT, then

kT
c( g) = csat , w . (8.2.45)
∆Fg

The derivation of the nucleation rates should be performed for this distribution and will have the form

kT
J hom = csat , w jg( + ) Ag Z . (8.2.46)
∆Fcr

8.3. Nucleation Rates for Homogeneous Ice Nucleation

8.3.1. Nucleation Rates with the Boltzmann Distribution

The process of homogeneous ice nucleation in supercooled water has similarities and differences
from the process of droplet nucleation in supersaturated vapor. The similarity is that nucleation also
proceeds via the formation and decay of the embryos of the new stable phase (ice) within the meta-
stable phase (liquid water). The difference is in the process of growth of these g-mers. In the case of
vapor–liquid transition, growth of the embryos proceeds via the molecular flux of monomers from
the vapor. In the case of the liquid–ice transition, the water molecules have to pass through three
stages. First, they have to escape from the attraction of their neighbors in the liquid; that is, to break
the water-to-water bonds. Second, they have to pass through a position of higher energy, DFact, to
overcome some potential barrier, which is called the energy of activation. And finally, the water mol-
ecules join the crystalline structure, and align in a position of minimum energy in the solid ice lattice.
Glasstone, Laidler, and Eyring (1941) developed the theory of viscosity, where it was shown using
the methods of statistical mechanics that the shift of a molecule from its equilibrium state in viscos-
ity also requires that it overcomes some potential barrier of activation. The frequency with which a
molecule crosses this potential barrier is

kT ζ act
νm = exp(− ε act /kT ), (8.3.1)
h ζ init

where eact is the activation energy for viscosity, zinit is the partition function of molecules in the initial
state, zact is the partition function in the activated state, and h is Planck’s constant.
Turnbull and Fischer (1949) used this analogy with the theory of viscosity to show that the dif-
fusive flux of the molecules across the liquid–ice boundary can be written as

 ∆F  kT
jg( +,dif) = N contν dif , ν dif = ν 0 exp  − act  , ν0 = . (8.3.2)
 kT  h
where DFact is the energy of activation of water molecules when crossing the liquid–ice boundary,
and Ncont is the number of monomers of water in contact with the unit area of the ice’s surface, ndif is
the jump rate, and n0 is the frequency of vibration of an absorbed molecule at the surface. Now, the
nucleation rate of the crystals in supercooled water can be written by analogy with (Eqn. 8.2.38a),
replacing corresponding quantities with those for liquid and ice:
1/2
σ   ∆F 
J f ,hom = 2cw jg( + ) vi1  iv  exp  − cr  , (8.3.3)
 kT   kT 
8.3. Nucleation Rates for Homogeneous Ice Nucleation 301

where cw is the concentration of water molecules in the liquid phase. Substituting here the flux (Eqn. 8.3.2)
and using the relations for cw and volume vi1 of a water molecule in ice,

N Av N Av ρ w mi1 Mw
cw = = , vi 1 = = , (8.3.4)
vw Mw ρi N Av ρi

we obtain the homogeneous freezing nucleation rate Jf,hom—i.e., the rate of formation of ice crystals
in supercooled water:
1/ 2
N cont kT  ρ w   σ iw   ∆F ∆F 
J f ,hom = 2     exp  − act − cr 
h  ρi  kT    kT kT 
 ∆F ∆F 
= Chom exp  − act − cr  , (8.3.5)
 kT kT 

where
1/ 2
N cont kT  ρ w   σ iw 
Chom = 2     . (8.3.5a)
h  ρi  kT

The value of Ncont ∼ 5.85 × 1012 cm−2 was estimated by Dufour and Defay (1963) from classical
nucleation theory, and a close value Ncont ∼ 5.30 × 1012 cm−2 was obtained by Eady (1971) using a
molecular model.
Fig. 8.2 shows homogeneous freezing nucleation rates Jf,hom measured or estimated for pure water
with various methods by several authors: Bigg (1953), Langham and Mason (1958), Butorin and
Skripov (1972), Sassen and Dodd (1988, 1989), Krämer et al. (1996), and Stöckel et al. (2005).

1E+11
1E+10
Homogeneous nucleation rate (cm–3 s–1)

1E+9
1E+8
1E+7
1E+6
Bigg
1E+5
Butorin
1E+4 Langham
1E+3 Sassen
1E+2 Stockel
10 Kramer
Classical theory
1
0.1
–55 –50 –45 –40 –35 –30
Temperature (C)

Figure 8.2. Homogeneous freezing nucleation rates Jf,hom for pure water: old classical theory before
1995 (crosses) versus various experimental data: Bigg (1953), Langham and Mason (1958), Butorin
and Skripov (1972), Sassen and Dodd (1988, 1989), Krämer et al. (1996), Stöckel et al. (2005).
302 Homogeneous Nucleation

A comparison of these data with the predictions from the old classical theory formulated before the
1990s (crosses) shows that the old theory predicts systematically lower nucleation rates than those
measured. It was shown in the 1990s that this discrepancy can be avoided with the appropriate choice
of parameters for the classical theory, as described next.
The probability of freezing of a haze particle or a drop with radius ra and volume v(ra) during the
time interval from t0 to t is

( t
Pf ,hom (ra , t ) = 1 − exp − ∫ J f ,hom (t ′) v (ra ) dt ′ .
t0 ) (8.3.6)

If the dependence of Jf,hom and v(ra) on time is weak, this expression is simplified as

Pf ,hom (ra , t ) ≈ 1 − exp[ J f ,hom v (ra )(t − t0 )]. (8.3.7)

If the product Jf,homv(ra)t is small, as for slow freezing or small particles or small time intervals, the
argument in the exponent can be expanded into the power series, and so we have

Pf ,hom (ra , t ) ≈ J f ,hom v (ra )(t − t0 ). (8.3.8)

The crystal concentration Nc in a polydisperse aerosol with uniform size and surface properties
can be calculated by integrating the probability of freezing Pf,hom of an individual haze or cloud
droplet over the size spectrum f(ra) of aerosol or droplets normalized to the aerosol or drop con-
centration Na:
rmax

N c ,hom (t ) = ∫P
rmin
f ,hom (ra , t ) fa (ra ) dra ,

∫ 1 − exp ( − ∫ )
rmax

=  t
J f ,hom (t ′) v (ra ) dt ′  fa (ra ) dra . (8.3.9)
rmin
0 

The polydisperse freezing nucleation rate Rf,hom = dNc(t)/dt (cm−3 s−1) can be calculated as

dN c rmax
R f ,hom (t0 ) =
dt
= ∫ rmin
dra fa (ra ) v (ra )

( t
× J f ,hom (t0 ) exp − ∫ J f ,hom (t ′)v (ra )dt ′ .
0 ) (8.3.10)

The expressions (Eqns. 8.3.9) and (8.3.10) can be simplified for the processes of slow freezing
using (Eqns. 8.3.7) and (8.3.8) as discussed in the following sections. If the aerosol size spectrum is
partitioned into multiple size fractions, which in addition may have different chemical compositions,
then these equations are modified by summation over all of these size fractions as

( )
rmax,i

N c ,hom (t ) = ∑ 1 − exp − t J 
i
∫
rmin,i
 ∫0
f ,hom (t ′ ) v (rai ) dt ′  fai (rai ) drai ,

(8.3.10a)

dN ci
R f ,hom (t0 ) = ∑
rmax,i
= ∑ ∫ drai fai (rai ) v (rai )
i dt i
rmin,i

( t
× Jf ,hom (t0 ) exp − ∫ J f ,hom (t ′)v (rai )dt ′
0 ) (8.3.10b)
8.3. Nucleation Rates for Homogeneous Ice Nucleation 303

8.3.2. Application of Bose–Einstein Statistics for Freezing

If DFact ≤ kT, then the more general Bose–Einstein distribution should be used to describe the effect
of activation energy on the crystal nucleation in supercooled water. The new diffusive flux with
Bose–Einstein statistics is
N cont kT 1
jg( + ) = . (8.3.11)
h exp( ∆Fact / kT ) − 1

If DFcr ≤ kT, then the Bose–Einstein distribution should be used also for the distribution of the germs:
1
cg = cw . (8.3.12)
exp( ∆Fg /kT ) − 1

Then, the freezing nucleation rate (Eqn. 8.3.5) can be rewritten as

1 1
J f ,hom = Chom . (8.3.13)
[exp( ∆Fact /kT ) − 1] [exp( ∆Fcr /kT ) − 1]

The normalizing factor Chom and the Zeldovich factor, derived earlier with the Boltzmann distribu-
tion, should be refined for this case, taking into account the new distribution. The relations DFcr >> kT
and DFact >> kT are valid in most cases. However, as discussed earlier, when siw is small—e.g., at
3
low temperatures or in the presence of strong surfactants—then ∆Fcr ~ σ vw may become compa-
rable to or smaller than kT. Then, the Bose–Einstein distribution may give higher accuracy than the
Boltzmann distribution. For DFcr >> kT, and DFact >> kT, we have the inequalities exp(DFcr /kT) >> 1,
exp(DFact /kT) >> 1, the Bose–Einstein distribution converts into the Boltzmann distribution used in
the previous derivations, and (Eqn. 8.3.13) converts into (Eqn. 8.3.5).
For the opposite case, DFg << kT, the Bose–Einstein statistics has another limit, obtained by
expanding the exponent into the power series, exp(DFg /kT) – 1 ≈ 1 + DFg /kT – 1 = DFg /kT. Then,
cg = cw(kT/DFg) and the nucleation rate has the form

kT kT
J f ,hom = Chom . (8.3.14)
∆Fact ∆Fcr

8.3.3. Parameterizations of Activation Energy

The diffusion activation energy DFact(T) of a water molecule to cross the water–ice embryo interface
plays a fundamental role in studies of water properties and ice nucleation. DFact(T) is parameterized
most often by two methods. The first method is based on an analogy with the viscous flow of water
and its self-diffusion because both phenomena are caused by the similar structure breaking mecha-
nisms and presumably may have the same energy of activation. Using this analogy and the theory of
water viscosity, the molar energy DFact(T) is related to the self-diffusion coefficient of water Dw or to
the viscosity of water hw:

d ln(ηw /T ) d ln Dw d ln Dw
∆Fact (T ) = R = −R = N Av kT 2 , (8.3.15)
d (1/T ) d (1/T ) dT
304 Homogeneous Nucleation

where R = kNAv is the universal gas constant, k is the Boltzmann constant, and NAv is the Avogadro
number.
The values of Dw were measured and parameterized at various temperatures (Pruppacher and
Klett, 1997) as
3
Dw = ∑ aDwn Tcn , 0 º C < Tc < 50 º C, (8.3.16)
0

with Dw in cm2 s−1, Tc in degrees C, aDw0 = 1.076 × 10−5, aDw1 = 4.260 × 10−7, aDw2 = 2.667 × 10−9,
aDw3 = −2.667 × 10−11, and
3
Dw = aDw 0 exp(∑ aDwn Tcn ), − 40 º C < Tc < 0 º C, (8.3.17)
1

with Dw in cm2 s−1 and aDw0 = 1.076 × 10−5, aDw1 = 4.14 × 10−2, aDw2 = 2.048 × 10−4, and aDw3 = 2.713
× 10−5. This led to a parameterization (Pruppacher and Klett, 1997)
3
∆Fact (T ) = aFa 0 exp(∑ aFan Tcn ), (8.3.18)
1

with DFact(T) in kcal mole−1, aFa0 = 5.55, aFa1 = −8.423 × 10−3, aFa2 = 6.384 × 10−4, and aFa3 = 7.891 × 10−6
in the range at −40 °C < Tc < 40 °C—i.e., DFact ≈ 5.55 kcal mole−1 at 0 °C. For DFact(T) in erg, using the
relation 1 kcal ≈ 4.18 × 1010 erg, and dividing by NAv = 6.023 × 1023, we obtain aFa0 ≈ 3.85 × 10−13 erg,
which is DFact at 0 °C. The empirical Vogel–Fulcher–Tammann relation is also used for Dw,

 CZ 
Dw = Dw 0 exp  −  . (8.3.19)
 T − TZ

Zobrist et al. (2007) and Hoose and Möhler (2012) give CZ = 892 K and TZ = 118 K.
Dividing (Eqn. 8.3.15) by NAv gives us a DFact in ergs:

kT 2C Z
∆Fact (T ) = . (8.3.20)
(T − TZ )2

This yields ≈ 0.4 × 10−12 erg at 0 °C, close to the value estimated earlier, and increases to ≈ 0.6 × 10−12 erg
at −60 °C. The other parameterization of DFact is based on fitting calculated to the measured ice nucle-
ation rates described in Chapters 8–10. Jensen et al. (1994) suggested an exponential fit for the activa-
tion energy in ergs

∆Fact (T ) = 1.29 × 10 −12 exp[0.05(Tc + 36)]. (8.3.21)

Tabazadeh et al. (1997) suggested the following polynomial fit for Fact(T) in ergs based on the ice
nucleation rates data from Bertram et al. (1996):

∆Fact (T ) = (1.1992475202 × 10 4 − 5.2298196745 × 10 2T + 8.232842046T 2

−6.4173902638 × 10 −2T 3 + 2.6889968134 × 10 −4 T 4 − 5.8279763451 × 10 −7T 5
+5.1479983159 × 10 −10 T 6 ) × 10 −13. (8.3.22)
8.4. Semi-empirical Parameterizations of Homogeneous Ice Nucleation 305

Khvorostyanov and Sassen (1998c) and Khvorostyanov and Curry (2000) fitted the experimental
nucleation rates to those calculated with the extended classical nucleation theory (Chapters 8–10)
with DFact in ergs as

∆Fact (T ) = 0.694 × 10 −12 [1 + 0.027(Tc + 30)], Tc > −30 º C, (8.3.23a)

∆Fact (T ) = 0.694 × 10 −12 [1 + 0.027(Tc + 30)]

× exp[0.01(Tc + 30)], Tc < −30 º C. (8.3.23b)

Chen et al. (2008) fitted various experimental data with simpler fits with DFact independent on T,
assuming DFact(T) = const = 10−12 erg or DFact(T) = const = 1.57 × 10−12 erg in the temperature range
from 0 to −60 °C. Fornea et al. (2009) suggested another approximation:

∆Fact (T ) = a0 exp(a1Tc + a2 Tc2 + a2 Tc2 ), (8.3.24)

with a0 = 0.3856 × 10−12 erg, a1 = −8.423 × 10−3, a2 = 6.384 × 10−4, and a3 = 7.891 × 10−6, which yields
DFact(T) = 0.3856 × 10−12 erg at 0 8C, and increases to ≈ 1.15 × 10−12 erg at −60 8C. Hoose and Möhler
(2012) compared various parameterizations of DFact and noted that its choice as a fitting parameter
may depend on the other parameters used for calculation of the nucleation rates. This dependence of
fitted DFact on the other fitted parameters was also emphasized by Lin et al. (2002) in comparison of
various ice nucleation schemes. Therefore, measurements of DFact or its evaluation from the measure-
ments of nucleation rates are desirable for various conditions and processes.

8.4. Semi-empirical Parameterizations of Homogeneous Ice Nucleation

The homogeneous freezing of haze particles and cloud droplets plays an important role in crystal forma-
tion in cirrus, orographic, deep convective clouds, and other clouds under low temperatures. Development
of parameterizations of various features of homogeneous ice nucleation suitable for cloud and climate
models has been underway for the past several decades. These parameterizations have been mostly semi-
empirical, based on heuristic relations for various properties of ice nucleation: nucleation rates, critical
humidities, nucleated crystal concentrations, etc. These parameterizations were developed using parcel
model simulations and either experimental data or some relations of the classical nucleation theory or
alternative nucleation theories. A brief review of several such parameterizations is given in this section.
These parameterizations are separated into two types. The first type provides equations for the
characteristics of the nucleation process at any given intermediate time of nucleation—e.g., nucle-
ation rates and concentrations can be calculated over the course of simulation. A few parameteriza-
tions of the second type considered the entire nucleation process as a sub-step process (taking less
than one time step in a model) and found equations for the final characteristics of the nucleation
process after the nucleation has ceased: crystal concentrations, radii, masses.
Parameterizations of the first type. One of the most important characteristics of freezing is the
nucleation rate Jhom. Heymsfield and Miloshevich (1993) used the results from the statistical molecu-
lar model of Eadie (1971) and fitted Jf,hom0 for pure water with an expression
4
J f ,hom 0 (T ) = 10 − X ( T ) , X (T ) = ∑ Ai ,HM Tci , (8.4.1)
i=0
306 Homogeneous Nucleation

where Jf,hom0 is in cm−3 s−1, Tc the temperature in degrees Celsius, and A0,HM = 606.3952, A1,HM = 52.6611,
A2,HM = 1.7439, A3,HM = 0.0265, and A4,HM = 1.536 × 10−4. Experimental data show that the freezing
rates of the haze particles are smaller than given by this equation, since they are depressed by the pres-
ence of solute.
Sassen and Dodd (1988, 1989) describe this depression of the nucleation rate by introducing an
effective freezing temperature

T * = T + λ SD ∆Tm , or ∆T f = T f* − T = λ SD ∆Tm , (8.4.2)

where DTm and DTf are the depressions of the melting and freezing temperatures respectively, and
lSD = 1.7 was chosen as an average from experimental data obtained by Rasmussen (1982) on the
relationship between depressions of the nucleation and melting temperatures for a number of salts. It
was clarified later that the coefficient 1.7 is not a universal, and can vary in the range 1.4–2.4 depend-
ing on the chemical composition of solute in the haze particle (Martin, 2000; Chen et al., 2000;
Lin et al., 2002; DeMott, 2002), and may reach 3 to 5 for some organic substances with high molecu-
lar weight, as will be discussed in Section 8.7. Thus, the nucleation rate for haze particles can be
calculated using (Eqn. 8.4.1) but with the effective freezing temperature Tf* instead of T
DeMott et al. (1994, hereafter DMC94) suggested a parameterization of DTm for ammonium sul-
fate as a function of molality M̂:

∆Tm = 0.102453 + 3.48484 Mˆ . (8.4.3)

Molality in this work was evaluated as described in Section 3.5, in terms of the equilibrium wet
particle diameters based on Köhler’s equation, and the freezing point depression was calculated with
(Eqn. 8.4.2). DMC94 used (Eqns. 8.4.1) to (8.4.3) to calculate the frozen fraction Fhf of the haze
particles at various T and Sw

Fhf = 1 − exp(− aDsb ), a = [(πρ s )2/6]10 cD 1 +cD 2 (1− Sw ) (8.4.4a)

cD1 = −14.65 − 1.045(T − T0 ), b = 6 (8.4.4b)

2
cD 2 = −492.35 − 8.34(T − T0 ) − 0.061(T − T0 ) , (8.4.4c)

with the density of dry ammonium sulfate rs = 1.769 g cm−3, and T0 = 273.16 K. Having calculated
Fhf at various T and Sw and assuming an exponential size spectrum of the haze particles by the diam-
eters D with the maximum Dm = 1.02 × 10−4 cm, DMC94 suggested a fit for the concentration of
nucleated crystals in the form

   D   
b
ymax 
N f = Na ∫ exp(− y) 1 − exp  − y b  n   , (8.4.5)
0
   Dm   

where y = D/Dn, and Dn = 7.5 × 10−6 cm is the scaling parameter, and Dm is defined such that a = Dm− b ;
Na is the total aerosol concentration, which is taken to be 200 cm−3. This scheme reproduced the
experimental data on ice nucleation in haze particles and could be used in cloud models.
An important characteristic of homogeneous ice nucleation is the critical humidity or the critical
hom
water saturation ratio Sw ,cr . Sassen and Dodd (1988, 1989), based on a generalization of their parcel
model simulations, and Heymsfield and Miloshevich (1995), based on the field measurements in
8.4. Semi-empirical Parameterizations of Homogeneous Ice Nucleation 307

orographic and cirrus clouds at low temperatures, parameterized Swhom

, cr as a polynomial fit by the

temperature

Swhom 2
, cr = A0 T + A1T T + A2 T T , (8.4.6)

with A0T = −27.6, A1T = 5.36 × 10−1, A2T = 0 and T in degrees Kelvin in Sassen and Dodd (1989), and
A0T = 1.8892, A1T = 2.81, A2T = 0.013336, and T in degrees Celsius in Heymsfield and Miloshevich
(1995). Sassen and Benson (2000), based on parcel model simulations, generalized this equation with
account for the wind shear.
Based on the results of laboratory experiments on solutions freezing, Koop et al. (2000) suggested
a parameterization of the homogeneous nucleation rate Jf,hom similar to Heymsfield and Miloshevich
(1993) for pure water but accounted for the solute effects parameterized in terms of water activity
3
J f ,hom (T ) = 10 − X K ( T ) , X K (T ) = ∑ Ai , K ( ∆aw )i , (8.4.7)
i=0

with A0,K = 906.7, A1,K = −8502, A2,K = 26624, A3,K = −29180, and

∆aw = aw − awi , (8.4.8)

where aw is the water activity in the liquid solution and awi is the activity of water in solution in equi-
librium with ice. Koop et al. (2000) assumed that in equilibrium aw is equal to the environmental
water saturation ratio Sw and the Kelvin curvature effect can be neglected for sufficiently large drops,
and awi was parameterized as

awi = exp{[ µ wi (T , p) − µ w0 (T , p)] /RT}, (8.4.9)

where m wi and m 0w are the chemical potentials of water in pure ice and pure liquid water, respectively.
In calculation for atmospheric conditions, p ≈ 1 atm. The difference of these chemical potentials was
parameterized as a function of temperature following Johari et al. (1994):

∆µ (T ) = µ wi (T , 0) − µ w0 (T , 0) = BK 0 + BK 1T + BK 2 T −1 + BK 3 ln(T ), (8.4.10)

with BK0 = 210368, BK1 = 131.438, BK2 = −3.32373 × 106, BK3 = −41729.1, T in degrees Kelvin, and
m wi and m w0 in J mol−1. This parameterization is assumed to be valid in the range 150 < T < 273, but
exhibits a somewhat unphysical maximum around 265–270 K.
Parameterizations of homogeneous freezing of the second type as a sub-step process include more
intermediate steps and assumptions. Such parameterizations are also semi-empirical, and as exam-
ples we describe the parameterizations developed by Kärcher and Lohmann (2002a,b) and Ren and
MacKenzie (2005).
The basis of these parameterizations is the equation for the ice saturation ratio, similar to
(Eqn. 5.3.47a) described in Section 5.3,

dSi
= c1i Si − (a2 + a3 Si ) Ri , (8.4.11)
dt
where c1i was defined by (Eqn. 5.3.46a) in Section 5.3, and
−1
 ρ 
−1 L2s M w m1w
a2 = n =  is  ,
sat a3 = , (8.4.12)
 m w1  c p pTM a
308 Homogeneous Nucleation

nsat is the number density of water molecules at ice saturation, and all the notations were intro-
duced earlier. The freezing/growth term Ri is defined similar to the integrals Idep and Icon in
Chapters 5 and 7:

4π
t
∞
dni (r0 , t0 ) dri
∫ dr0 ∫ dt r
2
Ri = 0 i (t0 , t ) (t0 , t ), (8.4.13)
vi 1 rs −∞
dt0 dt

where vi1 is a specific volume of a water molecule in ice. The term dni(t0)/dt0 is an analog of the poly-
disperse nucleation rate Rf,hom in Section 8.3, and [dni(t0)/dt0]dt0 is the number of particles freezing
during the time interval (t0, t0+dt0). It was written in the form
dni (t0 ) ∞ 4π 3 dn
= ∫ dr0 r0 J f ,hom a = J f ,hom (t )Va (t ), (8.4.14)
dt0 rs 3 dr0

where dna/dr0 = fa(r0) is the aerosol size distribution function, Va is the aerosol volume in a unit vol-
ume of air.
To solve this non-linear system of equations, the authors introduce several additional hypotheses.

1. Following Ford (1998a,b), a hypothesis on the exponential time behavior of the nucleation rate
dni /dt0 was introduced

dni (t0 ) dni (t )  t − t0 

= exp  − , (8.4.15)
dt0 dt  τ nuc 

where tnuc is some characteristic time scale of the ice nucleation event, unknown for now, which
has to be determined. Integration of (Eqn. 8.4.15) by t yields
t dni dn (t )
Ni = ∫ −∞
dt0
dt
(t0 ) = i τ nuc .
dt
(8.4.16)

2. An additional heuristic relation was introduced for tnuc by Kärcher and Lohmann (2002a,b):

−1
 ∂ln J hom  dT
τ nuc = cτ   . (8.4.17)
 ∂ T  Si = Si ,cr dt

The unknown parameter ct was parameterized in Kärcher and Lohmann (2002a) as a function of
temperature, and was replaced with a constant value ct = 50 in Kärcher and Lohmann (2002b).
Ren and MacKenzie (2005), taking a logarithm of (Eqn. 8.4.15) and differentiating, arrived at
a simpler expression:
−1 d ln J hom (t ) d ln Vw (t ) dT
τ nuc = + ≈ cτ (T ) , (8.4.18)
dt dt dt
cτ (T ) ≈ −0.004T 2 + 2T − 304.4, (8.4.19)

where ct is the approximate value of dln(Jf,hom)/dt at the difference Daw ≈ 0.306.

3. The third hypothesis was that the ice saturation ratio Si changes only slightly around its critical
value Si,cr during the nucleation event. Its variations can be neglected and it can be assumed that
Si(t) ≈ Si,cr(T).
8.4. Semi-empirical Parameterizations of Homogeneous Ice Nucleation 309

4. The diffusional growth of the nucleated crystals is described by equations similar to (Eqn. 5.2.18)
for the diffusional growth regime with kinetic correction but for equivalent spherical crystals:

dri b1
= ,
dt 1 + b2ri
α V n ( S − 1) α dVw 1
b1 = d w sat i , b2 = = , (8.4.20)
4 4 Dv ξ dep
where Vw is the thermal speed of the vapor molecules, and the other notations are the same as in
(Eqn. 5.2.18). The assumption that Si ≈ const ≈ Si,cr relates to b1 in (Eqn. 8.4.20).
5. The next hypothesis was that, similar to Twomey’s theory for drop nucleation (see Chapter 7),
homogeneous ice nucleation stops when Si reaches a maximum:

dSi /dt Si ≈ Si ,cr

= 0. (8.4.21)

(This assumption needs further tuning because ice nucleation does not cease at this point, as will be
discussed in Section 8.10). From (Eqn. 8.4.11) and the condition (Eqn. 8.4.21), we obtain

c1w Si ,cr
w = Ri . (8.4.22)
a2 + a3 Si ,cr

After substituting (Eqn. 8.4.15) into (Eqn. 8.4.13) for Ri and some transformations, Ren and MacKenzie
(2005) obtained from (Eqn. 8.4.22) an equation
∞
c1w Si ,cr dna
w = ∫ Rim (r0 ) (r0 , t0 = −∞) dr0 , (8.4.23)
a2 + a3 Si ,cr rs
dr0

where the monodisperse (at radius r0) freezing/growth term is defined by

4π
t
1  t − t0  2 dri
Rim =
vi 1 ∫ dt
−∞
0
τ
exp  −
 τ
 ri (r0 , t0 , t )
dt
(r0 , t0 , t ). (8.4.24)

Solving (Eqn. 8.4.23) produces the number of nucleated crystals:

∞

N i = ∫ na (r0 , t0 = −∞) dr0 ≤ N a . (8.4.25)

rs

Integration in (Eqn. 8.4.24) by t0 yields the monodisperse Rim:

4π b1   1 + δ 1 1   1  1  
Rim (r0 ) =  κ + exp   π erfc  + δ − 1 . (8.4.26)
vi1 b22   2 1 + δ κ  κ   κ  
where
r0 2b1b2τ
δ = b2r0 = , κ= , (8.4.27)
ξ dep (1 + δ )2

and erfc(x) = 1 − erf(x) is the complimentary error function. Kärcher and Lohmann (2002b) derived
a similar expression. For studies of Rim, Ren and MacKenzie (2005, 2007) found a representation of
erfc(x) via elementary functions with error less than 0.7%:

 1  1  3
exp   π erfc  ≈ . (8.4.28)
κ   κ  2 / κ + 1 / κ + 9 / π
310 Homogeneous Nucleation

Substitution of (Eqn. 8.4.28) into (Eqn. 8.4.26) yields for Rim an expression in elementary functions

4π b1  1 + δ 1 
Rim (r0 ) = φ (κ ) + φ (κ ) + δ − 1 , (8.4.29a)
vi1 b22  2 1+ δ 
3κ
φ (κ ) = . (8.4.29b)
2 + (1 + 9κ /π )1/ 2
Substitution of (Eqn. 8.4.29a,b) into (Eqn. 8.4.23), using (Eqn. 8.4.25) and integration over the aero-
sol size spectrum yields the number of nucleated crystals Ni. The analysis becomes simpler in the
case of a monodisperse freezing aerosol with radius r0. The expression for Ni then becomes
Si ,cr c1i w
Ni = . (8.4.30)
( Si ,cr − 1) [ Rim (r0 )(b22 / b1 ) ( vi1 /4π )](4π Dv /b2 )

Kärcher and Lohmann (2002b) and Ren and MacKenzie (2005) found for Rim(r0) four various
limiting cases for k → 0, k → ∝, d → 0 (which correspond to the diffuse regime of crystal growth)
and d → ∝ (kinetic regime of crystal growth). Substitution of these limits into (Eqn. 8.4.30) shows
dependencies of Ni on w, and T. In particular, for k >> 1, approximately corresponding to the diffu-
sion growth regime,

N i ~ w 3/ 2 , N i ~ nsa−1t/2 ~ ρi−s1/2 . (8.4.31)

For k << 1, approximately corresponding to the kinetic crystal growth regime, Ren and MacKenzie (2005)
found that Ni ∼ w for large particles (r0 >> xdep), and Ni ∼ w2, Ni ∼ ris−2 for small particles (r0 << xdep).
Barahona and Nenes (2008) developed a similar substep parameterization of homogeneous ice
nucleation, using Twomey’s (1959) upper limit approximation for ice supersaturation, and a repre-
sentation for the nucleation rate similar to Khvorostyanov and Curry (2004b):
J hom ( Si )
ln = bτ (T )( Si − Si ,cr ). (8.4.32)
J hom ( Si ,cr )

Barahona and Nenes derived an empirical temperature dependence for bt(T) from Koop et al. (2000),
made several auxiliary simplifications, and arrived at a parameterization that required an iterative
numerical solution. All of the parameterizations described earlier used parcel models for tuning the
parameters of the final parameterization equations.
In the studies reviewed earlier, it was assumed that stable hexagonal ice Ih nucleates in supercooled
water or solution droplets (see Section 4.1). The thermodynamic parameters associated with ice Ih
were therefore used. Evidence was provided recently that metastable cubic ice Ic may form first in
some cases at low temperatures, especially at T < 200 K, with subsequent relaxation to the stable ice
Ih (e.g., Murray et al., 2005, 2010; Murray and Bertram, 2006; Malkin et al., 2012). However, uncer-
tainty remains in the general conceptual picture of this sequence of the processes, and is widespread
in the current data on the thermodynamic parameters for Ic, so that the nucleation rates for Ic esti-
mated with classical nucleation theory may significantly vary (e.g., Murray et al., 2010). We there-
fore assume here that hexagonal ice Ih nucleates in droplets and use the corresponding parameters
for Ih. Calculations for Ic or any other type of ice described in Chapter 4 can be done using the same
equations derived here with corresponding changes to the thermodynamic parameters: the surface
tension, melting heat, saturated vapor pressure, etc.
8.5. Equations for Water and Ice Supersaturations with Homogeneous Ice Nucleation 311

8.5. Equations for Water and Ice Supersaturations with Homogeneous Ice Nucleation

Both water and ice supersaturations govern ice nucleation kinetics: water supersaturation determines
the nucleation process as specified in Section 8.6, and the growth of ice particles is determined by
ice supersaturation. We will consider the equations for fractional water and ice supersaturations,
sw = (rv – rws)/rws, and si = (rv – ris)/ris, where rv is the environmental water vapor pressure, rws and
ris are the saturated over water and ice vapor pressures, respectively. In a rising air parcel, super-
saturation is governed by two competing processes: supersaturation generation by the cooling in an
updraft and supersaturation absorption by the crystals in the deposition process.
This process can be described by the supersaturation equations, which we use in the form
(Eqns. 5.3.16), (5.3.43a), and (5.3.47) derived and discussed in Chapter 5 with modifications that
account for homogeneous ice nucleation:
1 dsw Γ
= c1w w − 12 I dep , (8.5.1)
(1 + sw ) dt ρv
1 dsi Γ s
= c1i w − 2 I dep = c1i w − i , (8.5.2)
(1 + si ) dt ρv τ fc

where tfc is the crystal supersaturation relaxation time defined in Section 5.3 and

 L Mw  g
c1w (T ) =  e − 1 , (8.5.3)
 cpT M a  Ra T

 L Mw  g
c1i (T ) =  s − 1 . (8.5.4)
 cpT Ma  Ra T

Here Γ12 and Γ2 are the psychrometric corrections associated with the latent heat release at condensa-
tion defined by (Eqn. 5.3.15) in Chapter 5.
The deposition vapor flux Idep to the crystals is the integral of the mass growth rate over the crystal
size spectrum. We assume that crystal size can be characterized by an equivalent radius rc, and then
Idep is expressed via crystal growth rate (drc/dt) as
∞
drc (t , t0 ) 2
I dep (t ) = 4πρi ∫ rc (t , t0 ) f (rc , t0 ) drc , (8.5.5)
0
dt

where fc(rc, t0) is the size distribution function of the crystals nucleated at a time t0, and rc(t,t0)
denotes the radius at time t of a crystal nucleated at time t0. We use (drc/dt) in the form of
(Eqn. 5.2.24):

drc c s Dv ρis
= 3i i , c3i = , (8.5.6)
dt rc + ξ dep ρi Γ 2
1/2
4 Dv  8 RT 
ξ dep = , Vw =   . (8.5.7)
α dVw  π Mw 
312 Homogeneous Nucleation

where Dv is the water vapor diffusion coefficient, xdep is the kinetic correction to the radius growth
rate, Vw is the thermal speed of water vapor molecules, and ad is the deposition coefficient. Substitu-
tion of (Eqn. 8.5.6) into (Eqn. 8.5.5) yields

4π Dv ρis ∞ rc2 (t , t0 )
I dep (t ) = si (t )
Γ2 ∫ 0 rc (t , t0 ) + ξ dep
fc (rc , t ) drc . (8.5.8)

The radius rc(t, t0) at time t of a crystal nucleated at time t0 is evaluated by integrating (Eqn. 8.5.6)

rc (t , t0 ) = {(rc 0 + ξ dep )2 + 2c3i [ yi (t ) − yi (t0 )]}1/ 2 − ξ dep , (8.5.9)

where rc0 = ri(t0) is the initial crystal radius at the activation time t0, and yi(t) is the integral ice super-
saturation defined as
t
yi (t ) = ∫ s (t ′ ) dt ′.
t0
i (8.5.10)

Ice nucleation via haze freezing depends simultaneously on T and sw, and we can generalize this
relation using a kinetic equation for the crystal size spectrum and introducing two activity spectra, by
supersaturation js(sw) and by temperature jT(T):
∂ fc (rc ) ∂  drc 
+  fc 
∂t ∂r  dt 
ds dT
= [ϕ s (T , sw ) w + ϕ T (T , sw ) ]δ (rc − rc (t0 )), (8.5.11)
dt dt
where the Dirac delta-function d(rc – rc(t0)) describes nucleation of a crystal with radius rc(t0). Equa-
tion (8.5.11) can be viewed as a generalization of the known relation for the drop activation on the
CCN, where usually only the supersaturation activity spectrum is accounted for (e.g., Twomey, 1959;
Sedunov, 1974; Khvorostyanov and Curry, 2008a, 2009b; Ghan et al., 2011; Tao et al., 2012; see
Chapters 6 and 7 here). Both sw– and T– spectra for homogeneous ice nucleation will be derived and
considered simultaneously in Section 8.10, but for now a simpler and faster way is to use an equiva-
lent equation for concentration conservation:

dN fr (t0 ) = fc (rc )drc = ϕ s (T , sw )dsw + ϕ T (T , sw )dT = R f ,hom (t0 )dt0 , (8.5.12)

where Rf,hom is the homogeneous freezing rate defined in (Eqn. 8.3.10) of Section 8.3 describing the
effects of both T and sw on freezing.
Substituting the equality fc(rc)drc = Rf,hom(t0)dt0 from (Eqn. 8.5.12) into (Eqn. 8.5.8) for Idep and
using (Eqn. 8.5.9), we obtain
t
4π Dv ρis
I dep = si
Γ2 ∫r
0
c , ef (t , t0 ) R f ,hom (t0 ) dt0 , (8.5.13)

where we introduced the effective radius rc,ef(t, t0):

{[(rc 0 + ξ dep ) 2 + 2c3i ( yi (t ) − yi (t0 ))]1/ 2 − ξ dep }2
rc ,ef (t , t0 ) = . (8.5.14)
[(rc0 + ξ dep ) 2 + 2c3i ( yi (t ) − yi (t0 ))]1/ 2

Substituting (Eqn. 8.5.13) into (Eqn. 8.5.2) and using the definition of (Eqn. 8.5.10) of yi(t), we
obtain an equation for integral ice supersaturation that participates in Equation (Eqn. 8.5.9)

1 dyi′ Γ y′
= c1i w − 2 I dep = c1i w − i , (8.5.15)
(1 + yi′) dt ρv τ fc
8.6. Critical Germ Size, Energy, and Homogeneous Freezing Rate 313

where
4π Dv ρis t

I dep = yi′
Γ2 ∫r
0
c , ef (t , t0 ) R f ,hom (t0 ) dt0 , (8.5.16)

Specific application of (Eqn. 8.5.16) for homogeneous ice nucleation is considered in the next sec-
tions. Substitution of Rf,hom from (Eqn. 8.3.10) into (Eqn. 8.5.16) yields

4π Dv ρis 
t
rmax
I dep = yi′  ∫ rc ,ef (t , t0 ) ∫r fa (ra ) v(ra )
Γ 2  0 min

(t

0  )
× Jf ,hom (t0 ) exp − ∫ J f ,hom (t ′)v (ra )dt ′ dra dt0  . (8.5.17)

Substitution of this expression into the supersaturation equation (Eqn. 8.5.15) and using the relation
rv = (1 + yi′)ris yields

1 dyi′ y′ t rmax
= c1i w − i (4π Dv )  ∫ rc ,ef (t , t0 ) ∫ fa (ra ) v (ra )
(1 + yi′) dt 1 + yi′  0 rmin

(
t

0 )
× Jf ,hom (t0 ) exp − ∫ Jf ,hom (t ′)v (ra )dt ′ dra dt0  . (8.5.18)

This equation describes the evolution of integral ice supersaturation. It is analogous to the integral
supersaturation equation (Eqn. 7.2.15) for the drop activation in Chapter 7, but includes a more
complicated integrand with a description of crystal nucleation. The first term on the RHS describes
supersaturation generation by the cooling action of updrafts, and the second term accounts for its
depletion by the newly nucleated and growing crystals.

8.6. Critical Germ Size, Energy, and Homogeneous Freezing Rate

Adequate description and parameterization of homogeneous ice nucleation was hampered for many
years by the absence of the equations for the critical radius rcr, energy DFcr, and nucleation rates
Jf,hom with simultaneous analytical dependence on the temperature T and the relative humidity or the
saturation ratio Sw. Expressions for rcr(T, Sw), DFcr(T, Sw), and Jf,hom (T, Sw) can be derived by devel-
oping the classical nucleation theory and using specific features of the deliquescent haze particles
considered in Chapters 6 and 7. In this section, we derive analytical expressions for the critical radii,
energies, and homogeneous nucleation (freezing) rates taking into account solution and curvature
effects, and then compare this method with previous parameterizations.

8.6.1. Derivation of the Critical Germ Size, Energy, and Nucleation Rate

The nucleation rate and number of crystals formed by homogeneous nucleation due to the freezing
of supercooled droplets of pure water or deliquescent haze particles is determined by the equation for
Jf,hom derived in Section 8.3. It was shown that Jf,hom is determined by the activation energy DFact for
diffusion across the liquid–ice boundary, and the critical energy DFcr of nucleation which depends on
the critical radius of an ice germ formed in supercooled liquid.
314 Homogeneous Nucleation

As discussed in Section 8.3, the expression for DFcr in classical theory is related to the critical
radius of an ice germ rcr, which can be obtained from the equilibrium condition at the ice–water
interface. The theory for pure water derived by J. J. Thomson (1888) yields
2σ iw
rcr (T ) = , (8.6.1)
Lm ρi ln(T0 / T )
4 16πσ iw3
∆Fcr (T ) = πσ iw rcr2 = . (8.6.2)
3 3[ Lm ρi ln(T0 /T )]2

Here, Lm is the melting heat averaged over the temperature interval (T0, T), T0 is the triple-point
temperature, T0 and T are in degrees Kelvin, siw is the surface tension at the ice–water interface, and
ri is the bulk ice density.
These equations do not account for solution effects, and therefore in Thomson’s formulation the
critical radius and energy depend only on temperature T, and not on the humidity or saturation ratio Sw.
Dufour and Defay (1963) accounted for the effects of solution in terms of the osmotic coefficient Fs,
calculations of which are rather complicated, but still not in terms of environmental humidity or Sw.
A more general derivation of the critical radius, energy, and nucleation rate for the homogeneous
freezing of aqueous solutions was performed by Khvorostyanov and Sassen (1998c) with some sim-
plifications that allowed derivation of expressions for rcr(T, Sw), energy DFcr(T, Sw), and Jf,hom(T, Sw).
In Khvorostyanov and Curry (2000, 2004a,b, 2005a, 2009b, 2012), these expressions were general-
ized to account for dependencies on the finite size of the freezing particles and on external pressure,
a simple quantitative equivalence between the pressure and solution effects was found, and these
equations were applied for evaluation of critical temperatures and humidities for ice nucleation.
Here, extending further the cited works, we consider in more detail the processes of freezing tak-
ing into account the difference between ice nucleation in the small solution drops (haze particles) or
unactivated deliquiescent interstitial CCN in a cloud, and ice nucleation in the much larger activated
cloud drops. The difference between the freezing of the small solution drops and larger activated
cloud drops is determined by the difference in their equilibrium states. It was shown in Chapter 3,
that the equilibrium of unactivated small solution droplets is determined by the Köhler equation,
while the equilibrium of the larger cloud drops is determined by the Kelvin equation. The freezing of
unactivated solution drops around Köhler’s equilibrium is considered in Sections 8.6.1 to 8.6.3, while
the critical radii and energies of cloud drop freezing around Kelvin’s equilibrium are considered in
Section 8.6.4.
To derive the size of a critical germ that takes into account the solution effect, we use the general
equilibrium or entropy equation (Eqn. 3.6.4) for the condition of equilibrium for an aqueous solu-
tion drop with radius ras containing an ice germ of radius rcr. Here, phase 1 is liquid water and phase
2 is ice. Then, the molar volumes v1 and v2 in phases 1 and 2 are those of water and ice, vw and vi,
the molar enthalpies h1 and h2 are those of water and ice, hw and hi, the molar melting latent heat
L12,mol = hw − hi = MwLm, where Lm is the specific melting latent heat and Mw the molecular weight
of water, and the misfit strain e = 0 for homogeneous nucleation without a foreign substance. The
pressures inside the solution drop and ice crystals are ps and pi, and the activities of water and ice
are ak,1 = aw, ak,2 = ai.
8.6. Critical Germ Size, Energy, and Homogeneous Freezing Rate 315

The fraction of salt left in ice after freezing is characterized by the segregation or partition or
retention coefficient. Observations show that upon freezing, salt is mostly rejected from ice into sur-
rounding brine and the retention coefficient is generally small, ∼10−2 to 10−4, if freezing is not rapid
and the pockets of solution are not trapped in ice. We assume that the solute is rejected from the ice
crystal upon freezing, so that ai = 1 and ln(ai) = 0, while aw ≠ 1. We obtain from (Eqn. 3.6.4) for a
solution drop with embedded ice crystal
M w Lm v v
− dT + w dps − i dpi + Rd ln aw = 0. (8.6.3)
T2 T T
If an ice germ is approximated by a spherical shape, the internal pressures inside a crystal, pi, and
inside a liquid solution drop, ps, can be expressed in terms of external pressure p with use of Laplace’s
conditions of mechanical equilibrium:

 2σ   2σ 
dpi = dps + d  is  , dps = dp + d  sa  , (8.6.4)
 rcr   ras 

subscripts i and s refer to ice and solution, respectively, sis and ssa are the surface tensions at the
ice–solution and solution–air interfaces, ras is the radius of an aqueous solution droplet, and rcr is the
radius of a crystal formed inside it. Substituting Laplace’s relations (Eqn. 8.6.4) and the relations for
the molar volumes, vw = Mw/rw, vi = Mw/ri, into (Eqn. 8.6.3), and then multiplying by T and dividing
by Mw, we obtain

Lm (T )  1 1   2σ sa (T )  
− dT +  −   dp + d  
T  ρ w (T ) ρi (T )    ras  
1  2σ (T )  RT
− d  is + d ln aw = 0. (8.6.5)
ρi (T )  rcr  M w

The activity of water in solution aw was defined in (Eqn. 3.5.18) and in this case
ν Φs ms M w
ln aw = − , (8.6.6)
M s [(4π /3) ρs″ (ras3 − rcr3 ) − ms ]

where Fs is the osmotic coefficient, n is the number of ions in solution, ms and Ms are the mass and
molecular weight of solute in a droplet, and rs″ is the solution density.
The number of components in this thermodynamic system is c = 3 (water, solute, air); thus, the
number of thermodynamic degrees of freedom should be Nw = c + 1 = 4 according to the phase rule
(Eqn. 3.3.12) for a system with curved substances. If we consider the case when the mass of solute
ms is constant, this imposes an additional constraint and Nw = 3; if ms is variable due to transfer
processes, then Nw = 4. The number of variables in (Eqn. 8.6.5) is 5 (T, rcr, ras, p, aw), and only 3 or
4 of them are independent according to the phase rule. We can consider the critical radius rcr of a
crystal as a function of 3 or 4 variables and choose several possible combinations of variables and
integrate (Eqn. 8.6.5), yielding several analytical dependencies of the critical radius rcr on various
variables. To shorten and generalize calculations, we can integrate (Eqn. 8.6.5), considering all
variables as independent; a selection of the possible combinations of independent variables can be
done in the final result.
316 Homogeneous Nucleation

Integration of (Eqn. 8.6.5) from the initial conditions (T = T0, ras = ∞, rcr = ∞, aw = 1, p = p0) to
(T, ras, rcr, aw, p) yields
T0 ∆ρ 2σ sa 2σ sa 2σ is RT
Lefm (T ) ln − ∆p + − − + ln aw = 0, (8.6.7)
T ρ w ρi ρ w ras ρi ras ρi rcr M w

where Dp = p − p0, Dr = rw − ri, T is the mean temperature in the range (T0, T), and we introduce an
“effective” melting heat, averaged over the range (T0, T):
−1
 T0 L (T )   T0 dT   T0 Lm (T )    T0   −1
Lefm (T ) =  ∫ m dT  ×  ∫  = ∫ dT  ×  ln    . (8.6.8)
T T  T T  T T    T 

Using data on the temperature behavior of Lm(T), the function Lefm (T ) can be parameterized as
Lefm (T ) = Lm0 (T0 )ϕ ( T ), which depends on temperature and is related to Lm0(T0) through some alge-
braic function j(T).
If we assume that p = const and dp = 0 in (Eqn. 8.6.5), pressure is excluded from the final equation.
Substituting (Eqn. 8.6.6) for aw into (Eqn. 8.6.7), and writing ms = (4/3)prsrs3, we obtain

T0 2σ sa 2σ sa
Lefm (T ) ln =− + ,
T ρ wras ρi ras
2σ is RT ν Φs ms M w / M s
− − = 0. (8.6.9)
ρi rcr M w (4π /3)[ ρs″ (ras3 − rcr3 ) − ρs rs3 ]
This equation determines rcr as a function of T, ras, and aw, although this dependence is implicit
because rcr is also contained in the denominator of the last term. If we consider a large drop or a bulk
solution with ras → ∝, then the terms with 1/ras vanish and we obtain
2σ is
rcr = . (8.6.10)
 T RT ν Φs ms M w / M s 
ρi  Lefm ln 0 − ″ 3 3 
 T M w (4π /3) ρ (r
s as − rcr ) − m s 

The calculation of rcr with (Eqns. 8.6.9) and (8.6.10) requires knowledge of Φs, n, and rs″ as functions
of the solution molality or the droplet radius and may be a rather complicated task.
A simple algebraic transformation allows us to significantly simplify the equations for rcr and
DFcr and to avoid using chemical properties of the solutions. Equation (8.6.7) can be rewritten after
regrouping the terms as

2σ is T RT  2 M wσ sa  ∆ρ∆p 2σ sa
= Lefm (T ) ln 0 +  + ln aw  − − . (8.6.11)
ρi rcr T M w  ρ w RTras  ρ w ρi ρi ras

The expression in parentheses can be expressed via the water saturation ratio Sw using the Köhler
equation (Eqn. 3.9.4):
2 M wσ sa A
+ ln aw = K + ln aw = ln Sw , (8.6.12)
ρ w RTras ras

where AK = 2M wσ sa / ρ w RT is the Kelvin’s curvature parameter. The applicability of the Köhler

equation here is justified by the assumption made earlier that the solution drop is in equilibrium
with environmental air. A wet haze particle just before formation of an ice germ will be in Köhler’s
8.6. Critical Germ Size, Energy, and Homogeneous Freezing Rate 317

equilibrium, whereby the curvature and solution terms should be balanced and determined by Sw.
Nucleation of an ice germ cannot substantially violate this equilibrium because the size of the germ
(∼10−7 cm) is much smaller than the size of even a submicron haze particle (∼10−6–10−4 cm), so that
the volume of the germ is 103–109 smaller than the drop volume and cannot seriously violate the
thermodynamic Köhler equilibrium. For cloud drops with radii of a few microns, the curvature and
solution terms are usually sufficiently small, and saturation ratio Sw is close to 1 in the cloud environ-
ment with small water supersaturation.
Using (Eqn. 8.6.12) allows significant simplifications of the expression for the ice germ critical
radius and energy. Equation (8.6.11) is simplified as

2σ is T RT ∆ρ∆p 2σ sa
= Lefm (T ) ln 0 + ln Sw − − . (8.6.13)
ρi rcr T Mw ρ w ρi ρi ras
This gives the critical radius of an ice germ
2σ is
rcr = (8.6.14a)
T RT ∆ρ∆p 2σ sa
ρi Lefm (T ) ln 0 + ρi ln Sw − −
T Mw ρw ras
2σ is
= , (8.6.14b)
 T  Af 
ρi L  ln  0 SwGn  − Ap ∆p −
ef

m
  T  ras 

where we introduce a new dimensionless parameter Gn, which characterizes the dependence on
Sw, the coefficient Ap that characterizes pressure effect, and a new curvature parameter for freezing
Af = rfr (scaling freezing radius) that characterizes the effect of the drop radius on freezing. Af is
analogous and proportional to the Kelvin parameter

RT ∆ρ 2σ sa ρ
Gn = , Ap = , A f = rfr = = Gn w AK . (8.6.15)
M w Lefm ρ w ρi Lefm ρi Lefm ρi
An estimate at T = −40 °C yields Gn ∼ 0.4–0.5, Ap ∼ 0.44 × 10−10 cm3 erg−1 = 0.44 × 10−4 atm−1, and
rfr ∼ 0.6AK ∼ 0.8 × 10−7 cm. It is also convenient to introduce an auxiliary function Hv,fr of Dp and ras:
Af ∆ρ∆p 2σ sa
H v , fr = Ap ∆p + = + , (8.6.16)
ras ρ w ρi Lm ρi Lefm ras
ef

and to write rcr in the forms

2σ is
rcr = (8.6.17a)
 T  
ρi Lefm  ln  0 SwGn  − H v , fr 
 T  
2σ is
= . (8.6.17b)
 T 
ρi L  ln  0 SwGn exp(− H v , fr ) 
ef
m
  T 

Equations (8.6.14a, b) and (8.6.17a, b) express the critical radius as a function of 4 variables: T, Sw,
p, ras. Recall that due to the limited number of independent variables, only 3 (with ms = const) or
4 (ms ≠ const) are independent. In cases with 3 variables, the most informative are T and Sw, and we
318 Homogeneous Nucleation

can choose either pressure p or drop radius ras. It will be shown in the following text that the use of
T, Sw, and p allows us to establish equivalence between the solution and pressure effects, or describe
theoretically the decrease of the freezing and melting temperatures on the external pressure.
The critical energy DFcr can now be evaluated analogously to the cases considered in Section 8.1—
i.e., writing the volume and surface energies of an embryo, and then minimizing their sum as d[DFcr(r)]/
dr = 0. After this procedure, similar to (Eqn. 8.1.12), DFcr is equal to one-third of the product of the
surface tension sis by the crystal surface area Acr,i = 4prcr2:

4 σ A 16π σ is3
∆Fcr = πσ is rcr2 = is cr ,i = 2 . (8.6.18)
3 3 3  ef  T0 Gn 
 ρi Lm ln  Sw exp(− H v , fr )  
 T 

For the particular case when we keep the drop radius ras = const (dras = 0) or for a bulk solution
(ras → ∝) and isobaric processes with external pressure p = const (dp = 0), these expressions are sim-
plified, and rcr and DFcr can be expressed as the functions of the temperature T and saturation ratio Sw:
2σ is 2σ is
rcr = = , (8.6.19)
ρi [ Lefm (ln T0 /T + ln SwGn )] ρi Lefm (T ) ln[(T0 /T ) SwGn ]

4 16π σ is3
∆Fcr = πσ is rcr2 = . (8.6.20)
3 3 [ ρi Lm (T ) ln[(T0 / T ) SwGn ] 2
ef

The nucleation freezing rate Jf,hom follows from (Eqn. 8.3.5) with this DFcr from (Eqn. 8.6.18):
1/2
N cont kT  ρ w   σ is   ∆F 
J f ,hom = 2     exp  − act 
h  ρi  kT    kT 
 1 (16π /3) σ is3 
× exp  − 2 
. (8.6.21)
 kT {ρ Lef
i m ln[(T0 / T ) S Gn
w exp( − H v , fr )]} 

The equation for rcr yields an expression for the ordinary affinity A∝, equal to the difference Dmsi
of the chemical potentials of the phases. Applying again (Eqn. 8.1.4), here for the ice and solution
(subscripts “i” and “s”),
2σ is vi1 2σ is vi µ
rcr = = , (8.6.22)
µ s1 − µ i 1 µ s − µ i
where again the subscript “1” denotes molecular potentials, and the quantities without “1” denote the
molar properties, and vi1 and vim denote the molecular and molar volumes. Comparing (Eqns. 8.6.17b)
and (8.6.22), we obtain Dmsi
M w Lefm (T )  T0 Gn  
A∞ ,1 = ∆µsi ,1 = µs1 − µi1 = ln  Sw  exp(− H v , fr )  , (8.6.23)
N Av   T  

 T  
A∞ = ∆µsi = µs − µi = M w Lefm (T ) ln  0 SwGn  exp(− H v , fr )  , (8.6.24)
  T  

where NAv is Avogadro’s number. The corresponding differences of the chemical potentials (affinities)
for the case of pure water are obtained from (Eqns. 8.6.23) and (8.6.24) at Sw = 1.
8.6. Critical Germ Size, Energy, and Homogeneous Freezing Rate 319

8.6.2. Analysis and Properties of the Solution

Equations (8.6.14a, b) or (8.6.17a, b) for rcr and (Eqn. 8.6.18) for DFcr include several particular cases.
In the first particular case for pure water droplets (Sw = 1) at atmospheric pressure (p = p0 or Dp = 0),
and sufficiently large drops or bulk solution (ras → ∝), (Eqns. 8.6.17a, b) and (8.6.18) transform into
the classical Thomson’s expressions (Eqns. 8.6.1) and (8.6.2) for homogeneous ice nucleation in pure
water. Compared to previous parameterizations reviewed in Section 8.4, (Eqns. 8.6.17a), (8.6.17b), and
(8.6.18) do not contain such quantities as water activity, the osmotic coefficient, and droplet mass or
molality. So, this method is explicit and simpler to use. A comparison with the previous parameteriza-
tions may help to find the best fits for the parameters of classical nucleation theory: Lm, sis, DFact.
In the other particular case, at T ∼ T0 (slightly below 0 °C, which can be around melting equilibrium),
after substituting Gn from (Eqn. 8.6.15) into (Eqn. 8.6.19), it is simplified to rcr = 2sis/(RvTrilnSw).
Thus, it resembles the usual expression for the germ radius in the homogeneous nucleation of a crystal
(or droplet) directly from the supersaturated vapor in the two-phase system—i.e., a transition from
the vapor to water or ice phase, considered in Section 8.1. However, in the three-phase system (vapor,
solution, and ice germ), the surface tension at the solution–ice interface is sis ∼ 18–25 erg cm–2, while
the surface tension in the two-phase system at the ice–vapor interface is siv ∼ 100–104 erg cm−2 [see
Section 4.4, (Eqns. 4.4.20a) and (4.4.20b)]. So, the critical germ size rcr is 4 times greater, DFcr is 16 times
greater, and nucleation rate Jf,hom ∼ exp(−ΔFcr/kT) is many orders of magnitude smaller for the direct
transitions into ice from the vapor than from the liquid. Thus, homogeneous nucleation via the three-
phase system or via the two-step process (vapor–liquid and liquid–ice) is energetically easier than via
the one-step vapor–ice transition; both processes require high Sw, but homogeneous freezing requires
lower Sw than homogeneous nucleation via deposition from the vapor. This property of this equation for
rcr is in agreement with Ostvald’s rule, which predicts that the phase transformation may occur as a two-
step process: the first transition into a less stable phase (liquid), and then into a more stable phase (ice).
In summary, the equations of this theory, (Eqns. 8.6.14a), (8.6.14b), (8.6.17a), (8.6.17b), and (8.6.18)
along with (Eqn. 8.6.21) for Jf,hom, provide the quantitative tools for description of homogeneous nucle-
ation both for haze particles and pure water, and convert into the classical Thomson equations for freezing
(Eqns. 8.6.1) and (8.6.2) at Sw → 1, Dp → 0, ras → ∝. At T → T0, these equations become similar to those
for the homogeneous condensation or deposition nucleation from the vapor. Thus, this generalization of
the theory of homogeneous freezing satisfies the generalized Bohr’s correspondence principle described
in Chapter 1 of this book (Section 1.2). These newer equations: a) do not reject but generalize the
classical equations and contain them as the particular cases; b) convert into the classical equations when
the parameters of the new theory tend to the certain limits: Sw → 1, or T → T0, or Dp → 0, or rsa → ∝.
Invariance to chemical composition. The final equations for homogeneous freezing show an
important and somewhat surprising feature. The specific chemical properties (density of dry particle
rs, dry mass ms, osmotic potential Φs, number of ions n, and surface tension ssa) of an aerosol (haze)
particle were present in the initial equations but vanished from the final (Eqns. 8.6.14a,b)–(8.6.21)
for rcr, DFcr, and Jf,hom. The major quantity that accounts for all specific chemicals and describes
unified chemical action is the environmental water saturation ratio Sw. The surface tension sis is less
variable than Sw and its value also adjusts to the environmental Sw.
This dependence on the water saturation ratio and independence of the chemical composition
is caused by the basic behavior of Kohler curves (Eqn. 8.6.12), which show that the radius of a
320 Homogeneous Nucleation

deliquescent haze particle in equilibrium assumes a Kohler’s radius through the combined solution
and curvature effects in such a way that it can be expressed through relative humidity or the water
saturation ratio alone. Otherwise, supersaturation or subsaturation occurs around a droplet and it
will grow or evaporate until its radius reaches such a value that Köhler’s equation (Eqn. 8.6.12) is
satisfied.
The relaxation time teq during which equilibrium radius is reached can be estimated by:

0.4ras2
τ eq ~ , (8.6.25)
Dv ( ρ v /ρ w )(1 − Sw )

where Dv is the vapor diffusion coefficient and rv the vapor density. This gives an estimate for the
relaxation time of homogeneous ice nucleation at cirrus altitudes (p ∼ 200 mb, T ∼ −40 °C), of teq ∼
10−3 to ∼ 2 s in the range of haze particles radii 0.01 μm < ras < 0.5 μm, and 0.9 < Sw < 0.98. Thus, haze
particles adjust sufficiently rapidly to equilibrium conditions. At lower altitudes and higher vapor
pressures, teq is smaller because teq ∼ rv−1. Thus, Köhler’s equilibrium is reached very rapidly for
submicron liquid particles, therefore its application along with the equilibrium assumption is justi-
fied. Note that these assumptions can be valid even at sufficiently low temperatures and high vertical
velocities as in the upper layers of convective clouds and anvils.
The “Saturation ratio criterion” for freezing. Since the environmental saturation ratio Sw is the
major factor (along with temperature) that governs homogeneous freezing rates for solutions, this
prediction can be called the water saturation ratio criterion. The physical reason for this is the rapid
relaxation of the haze particles to Köhler’s equilibrium, so that the combined action of chemical
properties (the Raoult effect) and curvature (Kelvin) effect results in a single major parameter Sw. The
value of Sw for the haze droplets is rather close to water activity aw. Thus, this theory predicts that the
homogeneous freezing behavior of the haze droplets could also be approximately described in terms
of aw. This prediction is confirmed by Koop et al. (2000), who analyzed a good deal of experimental
data on homogeneous freezing temperatures Tf,hom of solution droplets with radii of a few microns for
18 chemical substances and showed that their behavior was close to invariant relative to aw. That is,
Tf,hom plotted as a function of the molality (solution concentration) exhibited significant differences
for various substances, but when plotted versus aw, all curves Tf,hom in Koop et al. (2000) were close
to each other and to one universal curve. Note, however, that for submicron haze particles, Sw and aw
may differ due to the curvature effects and predictions according to the water activity criterion may
be different from predictions made by the water saturation ratio.
Effects of solution, pressure, and finite drop size on homogeneous nucleation. The “saturation
ratio” or “water activity” criterion is an important criterion that regulates the freezing temperature
Tf,hom, but a few other factors may noticeably change Tf,hom. Estimates of the effects of solution, pres-
sure, and finite drop size on homogeneous nucleation can be done using (Eqn. 8.6.14b) for rcr. It is
convenient to transform the terms in the denominator of (Eqn. 8.6.14b) or Dmsi in (Eqn. 8.6.24). We
can write T = T0 − DT; at supercooling ∼ 40 K, when homogeneous nucleation begins, DT << T0, and
ln(T0/T) = ln[T0/(T0 − DT)] ≈ DT/T0. The saturation ratio is related to water supersaturation as Sw =
1 + sw; since |sw| << 1, an expansion into the power series gives SwGn = (1 + sw )Gn ≈ 1 + Gn sw . With these
simplifications, we can rewrite the denominator in (Eqn. 8.6.14b) as

 ∆T Af 
∆µsi = µs − µi = M w Lefm (T )  + Gn sw − Ap ∆p − . (8.6.26)
 T0 ras 
8.6. Critical Germ Size, Energy, and Homogeneous Freezing Rate 321

At T ≈ −40 °C, the contribution of the first term in parentheses in (Eqn. 8.6.26) is ≈ DT/T0 ≈ 0.14 and
the value of Gn ∼ 0.4. Haze particles usually freeze homogeneously in cirrus at subsaturation, and the
second term in (Eqn. 8.6.26) is always negative at Sw < 1. For example, at sw = −0.1 (RHW = −10%),
the contribution of the term with sw is Gnsw ∼ −0.04—i.e., about 25% of the temperature term. The
signs of the DT– and sw– terms are different; thus, the same values of rcr (therefore, of DFcr and Jf,hom)
are reached at greater DT, which is equivalent to the depression of the freezing point—i.e., the solution
effect (subsaturation) causes a shift of the freezing process to the lower temperatures. The contribution
of Gnsw decreases as humidity increases and tends to 100% (sw tends to 0), which is reasonable as the
concentration of the solution decreases.
An estimate for the coefficient Ap in (Eqn. 8.6.14b) at T ≈ −40 °C gives Ap ∼ 0.44 × 10−4 atm−1.
Therefore, the contribution of the pressure term is negligible at atmospheric pressure, Dp = 1 atm, and
becomes significant only at very high pressures—e.g., ApDp ≈ 0.13 at Dp = 3000 atm, which is com-
parable with the temperature term. Since the contributions of the terms with DT and Dp have different
signs, this high pressure is equivalent in rcr to the temperature increase, or freezing at high pressures
should occur at lower temperatures. The effects of solutions and high applied pressure are similar.
An estimate for Af with this Lmef yields Af = rfr ∼ 0.8 × 10−7 cm. The freezing curvature term with
Af causes the freezing process to shift to lower temperatures. The value of the parameter Af is slightly
smaller than the Kelvin parameter AK, namely, Af ∼ 0.8 × 10−7 cm ∼ (0.6–0.7) × AK; thus, the effect of
Af is comparable with the effect of AK. For the drops with radius rsa = 10−6 cm, the term Af /rsa ∼ 0.08,
or about half of the temperature term. In summary, the effects of solution, high pressure, and finite
drop size result in the freezing point depression.
The general behavior of the germ critical radius rcr and energy DFcr computed from (Eqns. 8.6.19)
and (8.6.20) for pure water at Sw = 1 and the solution (haze) particles at environmental Sw = 0.9 is
presented in Figs. 8.3a and b. Differences between the pure water and solution particles are shown,
whereby solution effects increase both quantities by ∼ 25–30%. These differences slightly decrease
with lowering temperature. Because this difference in DFcr is in the exponent of the nucleation rate

2.0E–7 4E–12
rcr, water ∆Fcr, water
Critical germ energy (erg)
Critical germ radius (cm)

1.8E–7 rcr, solution ∆Fcr, solution

1.6E–7 3E–12
1.4E–7
1.2E–7 Sw = 0.9 Sw = 0.9
2E–12
1.0E–7
8.0E–8
1E–12
6.0E–8

–60 –55 –50 –45 –40 –35 –30 –60 –55 –50 –45 –40 –35 –30
Temperature (K) Temperature (K)
(a) (b)

Figure 8.3. Effect of solution on the critical radius (a) and energy (b) of an ice germ at various
temperatures at environmental saturation ratio Sw = 0.9 (upper curves) with pure water at Sw = 1
(lower curves).
322 Homogeneous Nucleation

Jf,hom in (Eqn. 8.6.21), the solution effect causes a strong suppression of the nucleation rate by several
orders of magnitude occurs (see the following).

8.6.3. Comparison with Other Models and Observations

As described in Section 8.4, Sassen and Dodd (1988, SD88 model) parameterized the effective freez-
ing temperature of the haze particles as T f* = T + DTf, relating the freezing and melting point depres-
sions DTf = lSDDTm and lSD = 1.7. DeMott et al. (1994) related the melting point temperature ΔTm to
the molality ms of deliquesced haze particles.
It can be shown that the equations for rcr(T, Sw) derived by Khvorostyanov and Sassen (1998c)
and Khvorostyanov and Curry (2004a, b) (KS98-KC04 model) extending the classical theory yield
relations equivalent to the parameterization in the SD88 model and allow DTf to be expressed via the
primary variables. The critical radius rcr in the SD88 model can be written in the form of Thomson’s
equation (Eqn. 8.6.1), but with T f* instead of T,
2σ iw 2σ iw
rcr (T ) = = ef . (8.6.27)
Lefm ρi ln(T0 /T f* ) Lm ρi ln[T0 /(T + ∆T f )]

The term with ln(T0 /T f*) can be expanded by the small ratio DTf /T << 1,

T0 T0 T  ∆T f  T ∆T f
ln = ln ≈ ln 0 + ln  1 − ≈ ln 0 − . (8.6.28)
T + ∆T f T (1 + ∆T f / T ) T  T  T T

In the KS98 model, the term with ln(T0/T) in (Eqn. 8.6.19) for rcr(T, Sw) at (1 − Sw) << 1 (or Sw ≥ 0.85,
when homogeneous freeing mostly occurs in cirrus) can be approximated as
ln(T0 / T ) − Gn (1 − Sw ). (8.6.29)
Equating the last two expressions, we obtain

RT 2
∆T f ≈ Gn T (1 − Sw ) = (1 − Sw ). (8.6.30)
M w Lefm

Thus DTf is expressed through fundamental constants and the saturation ratio. An estimate around
−40 to −50 °C gives Gn ∼ 0.4–0.6, which yields from (Eqn. 8.6.30) for the haze solution particles
freezing at Sw = 0.95 a freezing point depression DTf ∼ 5–6 °C. It will be shown further on that this
estimate is close to more precise calculations.
Freezing and melting point depressions are often parameterized through molality (e.g., Sassen and
Dodd, 1988; DeMott et al., 1994). It can be shown that molality can be expressed via the saturation ratio.
If the solution is sufficiently dilute, the solution density rs″ ≈ rw and molality M̂ s can be written as:

Mˆ s = 10 3 (ε m ρ s /M s ρ w )[(rw / rd )3 − 1]−1 , (8.6.31)

where rd and rw are the radii of the dry and wet aerosol particles. We can use the results of Chapter 6
to calculate rw /rd. Using (Eqn. 6.2.15) with b = 0.5 (the soluble fraction proportional to the volume),
we obtain for rw /rd:

rw ( Sw ) /rd = (1 − b /ln Sw )1/ 3 θ ( Sth ) ≈ [1 + b /(1 − Sw )]1/ 3 θ ( Sth ). (8.6.32)

8.6. Critical Germ Size, Energy, and Homogeneous Freezing Rate 323

where the parameter b=nFsem(rdMw/rwMs) was introduced in (Eqn. 6.2.6). Typical values of b for
substances that can serve as the ice germs in cirrus clouds (e.g., ammonium sulfate and sulfuric
acid) were estimated from (Eqn. 6.2.6). For b = 0.5 and ammonium sulfate, b ≈ 0.5 for fully soluble
nuclei. The Heaviside step function q(x) accounts for the lower humidity threshold (subscript “th”)
of deliquescence (Sw,th ≈ 0.8 for ammonium sulfate, see Chapter 11), and the second equation in
(Eqn. 8.6.32) is valid at Sw > 0.85−0.9.
This permits evaluation of the equilibrium radius of a haze particle—e.g., for ammonium
sulfate, the ratio of the wet rw to dry radii rd calculated from (Eqn. 8.6.32) at Sw = 0.95 and b = 0.5 is
rw/rd ≈ (1 + 0.5/0.05)1/3 ≈ 2.2, or the volume grows (rw/rd)3 ∼ 10 times.
Now we can relate molality to Sw. Substituting rw/rd from (Eqn. 8.6.32) into (Eqn. 8.6.31) yields
the molality

Mˆ s ≈ 10 3 (ν Φs M w )−1 (1 − Sw ) ≈ 30(1 − Sw ) (8.6.33)

in the units (mol g−1). The second relation here is based on the fact that the osmotic coefficient for
ammonium sulfate varies slightly with Sw and Fs ∼ 0.63–0.73 for Sw > 0.9 to 0.95. Such relations
can be used to verify or simplify various numerical models. This equation can be inverted for Sw as

Sw = 1 − 10 −3 (ν Φs M w ) Mˆ s . (8.6.34)

Substituting it into (Eqn. 8.6.30), we obtain

RT 2 ˆ
∆T f ≈ 10 −3 Gn T (ν Φs M w ) Mˆ s = 10 −3 (ν Φs M w ) Ms , (8.6.35)
M w Lefm

∆T f ≈ 5.43 Mˆ s , ∆Tm ≈ ∆T f /1.7 = 3.2 Mˆ s . (8.6.36)

The estimate (Eqn. 8.6.36) was calculated for ammonium sulfate at T ≈ −40 °C for a dilute solution.
The agreement between the empirical and semi-empirical parameterizations described in Section 8.4
and the extension of the classical nucleation theory described in Section 8.6.1 can be illustrated in
calculations of Jf,hom(T) by the two methods as illustrated in Fig. 8.4. Method 1 uses an empirical fit
for Jf,hom(T) by temperature (Eqn. 8.4.1) from Heymsfield and Miloshevich (1993) for pure water
with correction d Tf for solutions from Sassen and Dodd (1988)—i.e., Jf,hom0(Tf) and Jf,hom(T f*) were
calculated. The value of d Tf was in this case calculated from (Eqn. 8.6.30) for a given Sw. Method
2 uses the theory KS98-KC04 with (Eqns. 8.6.19)–(8.6.21) and the temperature-dependent parameters
described in Chapter 4, Section 4.4. The theoretical and parameterization results presented in Fig. 8.4
are in good agreement both for pure water and haze particles with solution. The upper curves for pure
water indicate that an appropriate choice of the temperature dependence of the parameters allows us
from the theory to extend the empirical parameterizations to lower temperatures. The agreement of
the lower curves for haze particles indicates that this newer theory described in Section 8.6.1 cor-
rectly accounts for the effects of solution in a wide temperature range. The general agreement sup-
ports the validity of this extension of the classical theory for the case of solutions.
As described in Section 8.4, DeMott et al. (1994, DMC94) parameterized the frozen fraction Fhf
and the freezing rate of haze particles in the form Jf,hom ∼ (1 − Fhf) ∼ exp[2.3·{cD1+cD2(1 − Sw)}]
as indicated in (Eqn. 8.4.4a) with cD1 and cD2 being some empirical functions of T given by
(Eqns. 8.4.4b) and (8.4.4c). Comparing this Jf,hom with Equation (8.6.21) derived from the theory, we
324 Homogeneous Nucleation

1E+23
1E+22 HM93, pure water
1E+21
1E+20 KS98–KC04, pure water

Homogeneous nucleation rate (cm–3 s–1)

1E+19
1E+18 HM93–SD88, haze
1E+17
1E+16 KS98–KC04, haze
1E+15
1E+14
1E+13
1E+12
1E+11
1E+10
1E+9
1E+8 Hagen
1E+7
1E+6 Sassen
1E+5 DeMott, Rogers
1E+4
1E+3 Kramer
1E+2
10 Stockel
1
0.1 Classical theory
0.01
–55 –50 –45 –40 –35 –30
Temperature (C)

Figure 8.4. Comparison of the homogeneous nucleation rate Jf,hom(T) calculated with the two
methods. Method 1 uses an empirical fit for Jf,hom(T) by temperature (Eqn. 8.4.1) from Heymsfield
and Miloshevich (1993) for pure water (HM93, pure water), and with correction d Tf for solutions
from Sassen and Dodd (1988)—i.e., Jf,hom(Tf*) (HM93-SD88). The value of d Tf in this case was
not taken from tables but was calculated from (Eqn. 8.6.30) for a given Sw. Method 2 uses the
theory of Khvorostyanov and Sassen (1998c), and Khvorostyanov and Curry (2000, 2004a,b),
with (Eqns. 8.6.19)–(8.6.21) and the temperature-dependent parameters described in Chapter 4, also
for pure water (KS98–KC04, pure water) and haze particles (KS98-KC04, haze). Also shown are
the experimental points by various authors: Hagen et al. (1981), Sassen and Dodd (1988, 1989),
DeMott and Rogers (1990), Krämer et al. (1996), and Stöckel et al. (2001, 2005). The old classical
theory (crosses) is given for comparison.

see again the same functional dependence on Sw in the exponent, while the constants cD1 and cD2 can
be found from (Eqn. 8.6.21). Further, DMC94 suggested a parameterization of the melting point
depression DTm via the molality M̂ s as ∆Tm = 0.1 + 3.485Mˆ s based on experimental data. Compar-
ing this expression with (Eqns. 8.6.35) and (8.6.36), and the expression obtained from the classical
theory ∆Tm = 3.2Mˆ s , we see again a reasonable agreement.
Finally, Fig. 8.5 shows a comparison of the crystals concentrations nucleated per 1 s (comparable
to a cloud model time step) from the polydisperse haze of ammonium sulfate with exponential size
spectrum calculated using two methods: Jf,hom taken from DeMott et al. (1994); and Jf,hom from the
theory described here with equations for rcr(T, Sw), DFcr(T, Sw), and Jf,hom(T, Sw) in Section 8.6.1. The
comparison in Fig. 8.5 shows good agreement. The curves for haze particles are surprisingly close,
even though they were computed with completely different methods.
This good agreement of the various semi-empirical parameterizations and this approach based on
an extension of the classical nucleation theory indicates again their equivalence.
A good agreement of various empirical parameterizations with a newer theory of homogeneous ice
nucleation described in Section 8.6.1, illustrated in this Section 8.6.3 with several examples, confirms
8.6. Critical Germ Size, Energy, and Homogeneous Freezing Rate 325

–64
–62 Theory, KS98
–60 param., DMC94
–58 Pure water
–56

Temperature (C)
–54
–52
–50
–48
–46
–44
–42
–40
–38
1E–3 1E–2 0.1 1 1E+1 1E+2 1E+3
Crystal concentration frozen in 1 s (cm–3)

Figure 8.5. Crystal concentrations nucleated in 1 s from droplets of pure water (lower curve)
and from a polydisperse haze of ammonium sulfate particles with an exponential size spectrum
from DeMott et al. (1994, DMC94). Comparison of calculations based on the homogeneous
freezing theory by Khvorostyanov and Sassen (1998, KS98) using (Eqns. 8.6.17a), (8.6.18), and
(8.6.21) here with parameterization from DMC94, and (Eqns. 8.4.4a,b,c) and (8.4.5) here. From
Khvorostyanov and Sassen (1998), Geophys. Res. Lett., 25, (16), reproduced with permission of
John Wiley & Sons, Inc.

again the general conclusion following from the correspondence principle (Section 1.2) that many
empirical and seemingly independent parameterizations can be derived from a corresponding theory,
which may help unify and clarify different parameterizations and create a joint basis for them.
The method described here for parameterizing the homogeneous freezing process is relatively
simple. It has been incorporated into several bin and bulk cloud models and been used in numeri-
cal simulations of cirrus clouds and multi-layer systems, where homogeneous freezing may play an
important role (e.g., Khvorostyanov and Sassen, 1998a,b, 2002; Khvorostyanov et al., 2001, 2006;
Sassen et al., 2002; Morrison et al., 2005a,b; Comstock et al., 2008). It can also be used in parcel
models (e.g., Khvorostyanov and Curry, 2005; see Section 8.9 here), or for analysis of droplet freez-
ing experiments. Note that the effects of solution on the surface tension, melting heat, the chemical
composition of the haze particles, and other thermodynamic parameters may be important, but there
are still many uncertainties in these parameters, as is seen in numerous different parameterizations
described in Section 4.4. Therefore, further studies are desirable, especially at very low temperatures,
and more experimental data at low T are required.

8.6.4. The Freezing of Cloud Drops

Thus far, we have considered the nucleation of ice crystals inside submicron solution droplets,
haze particles. The process of the nucleation of ice crystals inside cloud drops differs in several
aspects: cloud drops have much larger radii; the solution inside the drops is very dilute; and Köhler’s
326 Homogeneous Nucleation

equilibrium is not applicable to such drops. Derivation of the critical radii and energies of ice crystals
nucleating inside cloud drops can be considered similar to the derivation of the Kelvin equation in
Section 3.8, with some generalization.
Consider again the general equilibrium or entropy equation (Eqn. 3.6.4) for the condition of equi-
librium for a cloud drop with radius rd containing an ice germ of radius rcr. As in Section 3.8, we
assume that the drop is in equilibrium with the environment’s humid air, and assume additionally
that the nucleating ice crystal inside the drop is in equilibrium with the drop. In (Eqn. 3.6.4), the
substances are, in this case: phase 1 is liquid water; phase 2 is ice. The molar volumes v1 and v2 in
phases 1 and 2 are those of water and ice, vw and vi; the molar enthalpies h1 and h2 are those of water
and ice, hw and hi; the molar melting latent heat L12,mol = hw − hi = MwLm, where Lm is the specific
melting latent heat, and Mw is the molecular weight of water; and the misfit strain is e = 0 for homoge-
neous nucleation without a foreign substance. The pressures inside the solution drop and ice crystals
are ps and pi. Since the solution in the drop is very dilute, its activity aw ≈ 1. Since solute is rejected
from ice upon freezing, we also have the condition ai ≈ 1. Thus, we can neglect the term dln(aw/ai) in
(Eqn. 3.6.4). However, since we assumed that the cloud drop is in equilibrium with the environment’s
humid air, as in the derivation of the Kelvin equation in Section 3.8, this term should be replaced with
the term describing the contribution of the water vapor activity, dln(ev/p), where ev is the vapor pres-
sure, p is the atmospheric pressure, and (ev/p) is the mole fraction of water vapor equal to its activity
av, assuming an ideal gas behavior.
Then, we obtain for a cloud drop with embedded ice crystal from (Eqn. 3.6.4) multiplying it by T,
M w Lm
− dT + vw dps − vi dpi + RTd ln(ev / p) = 0. (8.6.37)
T
Although the solution in the cloud drop is very dilute, it is called hereafter a “solution drop” for pur-
poses of uniformity with the previous consideration of haze particles. If an ice germ is approximated
by a spherical shape, the internal pressures inside a crystal, pi, and inside a liquid solution drop, ps,
can be expressed as earlier in terms of external pressure p by using Laplace’s conditions of mechani-
cal equilibrium:

 2σ   2σ 
dps = dp + d  sa  , dpi = dps + d  is  , (8.6.38)
 rd   rcr 

where subscripts i and s refer to ice and solution, respectively; sis and ssa are the surface tensions
at the ice–solution and solution–air interfaces; rd is the radius of a droplet; and rcr is the radius of a
crystal formed inside it. Substituting Laplace’s relations (Eqn. 8.6.38) and the relations for the molar
volumes, vw = Mw/rw, vi = Mw/ri, into (Eqn. 8.6.37), and dividing by Mw, we obtain

dT ∆ρ ∆ρ  2σ sa 
− Lm (T ) + dp − d
T ρ w ρi ρ w ρi  rd 
1  2σ is  RT e 
− d + d ln  v  = 0, (8.6.39)
ρi  rcr  M w  p

where Dr = rw − ri. The number of components in this thermodynamic system is c = 3 (water, solute,
air); thus, the number of thermodynamic degrees of freedom is Nw = 4 according to the phase rule
for a system with curved substances. The variables in (Eqn. 8.6.39) are T, p, ev, and one of the radii
8.6. Critical Germ Size, Energy, and Homogeneous Freezing Rate 327

(rcr or rd), the other radius is a function of the other 4 variables. If we choose rd as a variable, we can
search for the critical crystal radius rcr(T, p, ev, rd).
Suppose that the initial conditions correspond to the state T = T0, rd0 = ∞ (plane surface), rcr = ∞,
ev = ews (saturated vapor pressure over a plane water surface), and p = p0. Integration of (Eqn. 8.6.39)
from the initial conditions to (T, rd, rcr, ev, p) yields
T0 ∆ρ∆p 2 ∆ρσ sa 1
Lefm (T ) ln − −
T ρ w ρi ρ w ρi rd
2σ is RT  p 
− + ln Sw 0  = 0, (8.6.40)
ρi rcr M w  p

where Dp = p − p0, T is the mean temperature in the range (T0, T), Lefm (T ) is the effective melting
heat introduced earlier, and Sw = ev/ews is the water saturation ratio. If, as in Section 3.8, we assume
T = const, p = const, the terms with T and p vanish in (Eqn. 8.6.40). If we do not consider nucleation
of an ice crystal, then the term dpi = 0 in (Eqn. 8.6.38) and all terms related to ice (vi, ri, ssi, rcr) also
vanish in (Eqn. 8.6.40). Then, the rest of (Eqn. 8.6.40) is
2σ sa M w
ln Sw = . (8.6.41)
rd RT ρ w
That is, with these simplifying assumptions, we arrived again at the Kelvin equation, and (Eqn. 8.6.40)
can be viewed as its modification, taking into account ice nucleation inside the drop. Solving
(Eqn. 8.6.40) relative to rcr, we obtain
2σ is
rcr = , (8.6.42)
 T p  ∆ρ 2σ sa 1 
ρi Lefm  ln  0 SwGn 0  − 
 T p  ρ w ρi Lefm rd 

where Gn = RT / M w Lefm is defined as in (Eqn. 8.6.15). An estimate of the terms in (Eqn. 8.6.42) at
rd ∼ 10 – 30 μm, T ∼ 238 K using Lefm from Fig. 8.14a, and ssa from Section 4.4 shows that the second
term in the denominator of (Eqn. 8.6.42) ∼ −(1 to 3) × 10−6. It is much smaller than the first term with
ln, and can be neglected. Thus, (Eqn. 8.6.42) is simplified as

2σ is
rcr = . (8.6.43)
 T p 
ρi Lefm  ln  0 SwGn 0  
 T p 

If droplet freezing occurs with a substantial uplift, the factor p0/p > 1 in (Eqn. 8.6.43). This leads to
a smaller critical radius and energy and accelerates droplet freezing. If we consider the processes
without strong changes of pressure, then p ≈ p0, and this equation is further simplified as

2σ is
rcr = . (8.6.44)
 T 
ρi L  ln  0 SwGn  
ef

 T 
m

This equation coincides with the simplified versions of rcr in (Eqns. 8.16.14b), (8.6.17a), and (8.6.17b)
neglecting there the effects of pressure and droplet curvature (Hv,fr = 0). Thus, the effects of the tem-
perature and water saturation ratio are similar for both haze particles and activated cloud drops.
328 Homogeneous Nucleation

The effects of T and Sw can be compared if they are presented as T = T0 − DT, and Sw = 1 + sw,
where DT is supercooling and sw is the water supersaturation. The terms under the logarithm sign in
(Eqn. 8.6.44) can be presented as

T0 Gn  ∆T  ∆T ∆Tef
Sw ≈  1 +  (1 + Gn sw ) ≈ 1 + + Gn s w = 1 + , (8.6.45)
T  T0  T0 T0

where we introduced the “effective supercooling”

∆Tef = ∆T + δ s ∆T , δ s ∆T = T0 Gn sw . (8.6.46)

Thus, positive supersaturation increases effective supercooling by dsDT = T0Gnsw. Fig. 8.14c shows
that Gn ∼ 0.45 at T ≈ −40 °C, and so T0Gn ∼ 120. Therefore, if sw > 0, this leads to an increase of the
effective supercooling by dsDT ≈ 1.2 × sw (%), where the supersaturation is measured in percent. In
general, the supersaturation is small in a developed cloud with activated drops, sw ∼ 10−3 to 10−1%,
and its effect on the drop freezing is insignificant. However, there can be at least two situations when
the effect of sw can be noticeable or large. It was hypothesized by Hobbs and Rangno (1990) and
Rangno and Hobbs (1991, 2001) that sw in a cloud may reach 5% or more after intensive coagula-
tion and precipitation. Then, dsDT ∼ 6 °C, which can cause a noticeable acceleration of freezing. In
cloud chamber experiments, sw can reach 10–25%; thus, dsDT ∼ 12–30 K and may cause a significant
acceleration of freezing. If the temperature in the chamber is sufficiently low (−20 to −30 °C), DTef
may become lower than −40 °C and this may result in homogeneous drop freezing. This should be
taken into account in analyses of drop freezing experiments at high humidity.
The critical energy DFcr of cloud drop freezing and the nucleation rate Jf,hom can be calculated
using (Eqns. 8.6.20) and (8.6.21), respectively, with Hv,fr = 0 and sis ≈ siw. In subsequent sections,
the discussion will be concentrated mostly on the submicron haze particles since the processes of
their homogeneous freezing are especially important in the formation of upper tropospheric clouds
at low temperatures. Applications for cloud drops are also discussed, taking into account their larger
sizes, as well as the applications for bulk solutions, which require an appropriate modification of
the equations.

8.7. Critical Freezing and Melting Temperatures of Homogeneous Freezing

8.7.1. General Expressions Based on Classical Theory

The critical or threshold temperatures and saturation ratios of homogeneous freezing depending on
the nucleation rates can be derived from the two equations for the critical energy DFcr. One expres-
sion follows from (Eqn. 8.3.5) for the freezing nucleation rate Jf,hom:
J f ,hom
∆Fcr = − kT ln − ∆Fact , (8.7.1)
Chom

with Chom defined in (Eqn. 8.3.5a). We use the other expression for DFcr in the form (Eqn. 8.6.18):
(16π /3)σ is3
∆Fcr = 2 , (8.7.2)
 ef   T0 Gn  
 ρ i Lm  ln  T Sw  − H v , fr  
   
8.7. Critical Freezing and Melting Temperatures of Homogeneous Freezing 329

with Hv,fr defined in (Eqn. 8.6.16). Solving (Eqn. 8.7.2) relative to the logarithmic term in the denomi-
nator, we obtain
1/ 2
T  1  (16π /3)σ is3 
ln  0 SwGn  = H v , fr +   . (8.7.3)
T  ρi Lefm  ∆Fcr 
Substituting DFcr here from (Eqn. 8.7.1) yields

T 
ln  0 SwGn  = H v , fr + H f ,hom , (8.7.4)
T 

where
1/ 2
1  −(16π /3) σ is3 
H f ,hom =   . (8.7.5)
ρi Lefm  kT ln( J f ,hom /Chom ) + ∆Fact 

Equation (8.7.4) is a key relation for the threshold T and Sw, which allows expression of the critical or
threshold temperature of homogeneous freezing Tf,hom as a function of the saturation ratio, or lets us
alternatively express the critical saturation ratio Sw,cr as a function of the temperature.
Solving (Eqn. 8.7.4) for T, we obtain an equation for the critical temperature Tf,hom of homoge-
neous freezing:

(
T f ,hom ( ∆p) = T0 SwGn exp − H v , fr − H f ,hom . ) (8.7.6)

In a more expanded form, substituting Hv,fr, Hf,hom, from (Eqns. 8.6.16) and (8.7.5) yields

 ∆ρ∆p Af 
T f ,hom ( J hom , Sw , ras , ∆p) = T0 SwGn exp  − − 
 ρ w ρi Lm ras 
ef

 1  16π σ is3 
1/ 2

 
× exp − ef −  , (8.7.7)
 m ρi
L  3 kT ln( J f ,hom / C hom ) + ∆Fact 
 

where Af was defined in (Eqn. 8.6.15), Gn = RT/(MwLmef ), and Lmef, ri, Chom, sis, and DFact are func-
tions of temperature and should be evaluated at the same values of Tf,hom as on the left-hand side of
(Eqn. 8.7.7). The solution to (Eqn. 8.7.7) requires an iteration procedure, but iterations converge
rapidly as illustrated in the following text.
Note that the expression in square brackets contains a minus sign under the square root. Since
the numerator sis3 is positive, this means that the denominator should be negative, or ln(Jf,hom/Chom)
should be negative and its absolute value should be sufficiently large to satisfy the condition
|ln(Jf,hom/Chom)| > DFact. This implies that the threshold or critical temperature exists if the freezing
rate is large enough. Equation (8.7.7) shows that critical temperature depends on the freezing rate;
thus, experiments with different cooling rates should measure different freezing temperatures, which
has been found in various experiments (e.g., Cziczo and Abbatt, 1999; Martin, 2000; Kashchiev,
2000; Kashchiev et al., 2010).
A differential equation follows from (Eqn. 8.7.7):
dT f ,hom ∆ρT f ,hom
=− , (8.7.8)
dp ρ w ρi Lefm
330 Homogeneous Nucleation

which formally resembles the Clapeyron equation that is valid for the melting transition in a one-
component system, but is derived here for freezing with a finite nucleation rate and a multi-component
system. For the particular case of constant external pressure (Dp = 0) and large drops (ras → ∞), the
first exponent on the right-hand side of (Eqn. 8.7.7) vanishes. For pure water drops, Sw = 1, and only
the nucleation rate in the last exponent regulates Tf,hom. For solutions, Sw < 1, which leads to the lower-
ing of Tf,hom as shown in the next section.
For very slow freezing, (Eqn. 8.7.7) can be simplified. When Jf,hom → 0, and ln(Jf,hom) → −∝, the
square root in the second exponent tends to zero, the second exponent tends to 1, and we obtain

 ∆ρ∆p Af 
T f ,hom ( ∆p) = T0 SwGn exp  − − . (8.7.9)
 ρ w ρi Lm ras 
ef

Melting can be considered using a similar approach, whereby it is a reverse process with respect to
freezing and can be described as a formation of a melting liquid germ on the surface of an ice crystal
with radius rcr. Thus, an approximate equation for the melting temperature is similar to (Eqn. 8.7.9)
with replacement rsa → rcr:

 ∆ρ∆p Af 
Tm ( ∆p) = T0 SwGn exp  − − . (8.7.10)
 ρ w ρi Lm rcr 
ef

The expressions (Eqns. 8.7.9) and (8.7.10) do not depend on Jhom, Chom, owing to the very small
nucleation rate. Equation (8.7.10) allows for a simple calculation of the melting point depression with
increasing pressure. Differentiating (Eqn. 8.7.10) by p, we obtain

dTm ∆ρT0 Gn ( T )  1  ∆ρ∆p 2σ ia  

=− Sw exp  − ef 
+ . (8.7.11)
dp ρi ρ w Lefm  i Lm  ρ w
ρ rcr  

For a particular case of bulk pure ice (rcr → ∞), (Eqn. 8.7.11) is simplified and converts into the
generalization of the Clapeyron equation that takes into account solution effects:
dTm ∆ρT0 G ( T )
=− Sw . (8.7.11a)
dp ρi ρ w Lefm
For pure water (Sw = 1), it converts into the Clapeyron equation:
dTm ∆ρT0
=− , (8.7.11b)
dp ρi ρ w Lefm
which is used to explain the dependence Tm(p) near the triple point T0 = 273.15 K (see Chapter 4).
Substituting here the values Lmef = 79.7 cal g−1, ri = 0.92 g cm−3, and Dr = 0.08 g cm−3 at the triple
point T0 = 273.15 K, we have dTm/dp ≈ −1/138.3 K atm−1, close to the experimental values of
1/146.7 K atm−1 or 1/136 K bar−1 (Hobbs, 1974). The slopes may be different for solutions when the
relative humidity in experiments is less than 100%. It is seen from (Eqn. 8.7.11a) that the slope
dp/dTm increases with decreasing Sw—i.e., the melting point shifts to lower temperatures at the same
pressure but at a lower humidity or with increasing solution concentration.
8.7. Critical Freezing and Melting Temperatures of Homogeneous Freezing 331

8.7.2. Liquidus Curves

Equations (8.7.9) and (8.7.10) for Tf,hom, Tm at Dp = 0, large ras, and rcr or bulk solutions and very low
nucleation rates Jhom are reduced to the following:
ef ef
T f ,hom ( ∆p = 0) = T0 SwGn ( T ) = T0 SwRT / M w Lm ≈ T0 awRT / M w Lm (8.7.12a)
RT /M w Lefm RT/ M w Lefm
Tm ( ∆p = 0) = T0 SwGn ( T ) = T0 Sw ≈ T0 aw , (8.7.12b)

which indicates the reversibility of slow freezing and melting. Equations (8.7.12a) and (8.7.12b)
are nonlinear in the water saturation ratio or in the solution concentration, and are valid not only for
dilute solutions but also for concentrated solutions. The curves Tm(xs) or Tm(Sw) on the phase dia-
grams T − xs or T − Sw are called liquidus curves, which separate the domain on the phase diagrams
with a liquid solution located above the liquidus (also called brine in the case of seawater) from the
domain with a mixture of liquid solution and ice that is located beneath the liquidus curve. (See also
Chapter 11, Figs. 11.4 and 11.6).
At sufficiently small supersaturation or subsaturation, |sw|< 0.2–0.3, we can expand (Eqn. 8.7.12b)
into a Taylor series by sw = Sw − 1. Keeping only the first three terms in sw and using (Eqn. 8.6.15) for
Gn, we have a cubic polynomial by sw:

 G (G − 1) 2 Gn (Gn − 1)(Gn − 2) 3 
Tm ≈ T0 1 + Gn sw + n n sw + sw 
 2 6 
= T0 + ∆Tm1 + ∆Tm 2 + ∆Tm 3 , (8.7.12c)

Rv T02 R T2  R T 
∆Tm1 = sw , ∆Tm 2 = v 0  v 0 − 1 sw2 , (8.7.12d)
Lm 2 Lm  Lm 

Rv T02  Rv T0  R T 
∆Tm 3 =  − 1  v 0 − 2 sw3 . (8.7.12e)
6 Lm  Lm   Lm 

where Rv is the specific gas constant for water vapor.

Equations (8.7.12b)–(8.7.12e) describe the shift of the freezing or melting point temperature in a
bulk solution due to the solute effects; DTm1, DTm2, and DTm3 are corrections of the first, second, and
third order by supersaturation or solution concentration, respectively. Since Gn ∼ 0.4 < 1 and sw < 0
for solutions, (Eqn. 8.7.12c) shows that all these three corrections are negative. It is easy to see
that DTm1 is equivalent to the traditional formulation for the freezing point depression DTf in the
bulk water solution that is derived usually by the equating chemical potentials of ice and solution
(e.g., Pruppacher and Klett, 1997; Curry and Webster 1999). Using the value Gn ≈ 0.38 near T0 = 273.15
(see Fig. 8.14c), (Eqn. 8.7.12c) can be rewritten as

Tm ≈ T0 + 103.8sw − 32.18sw2 + 17.37sw3 . (8.7.12f)

For small sw, using an approximation sw ≈ ln(1 + sw) ≈ lnSw ≈ lnaw, (Eqn. 8.7.12f) can be rewritten as

Tm ≈ T0 + 103.8 ln aw − 32.18(ln aw )2 + 17.37(ln aw )3 . (8.7.12g)

This functional form is similar to the empirical relation found by Chukin et al. (2010, 2012) by fitting
the experimental data
Tm ≈ T0 + 103.6 ln aw + 15.613(ln aw )2 + 54.118(ln aw )3 , (8.7.12h)

that well approximates the function Tm(aw) (see Fig. 8.14c).

332 Homogeneous Nucleation

The liquidus curve determines the freezing or melting point depressions DTf(xs) or DTm(xs) as
a function of solution concentration or equivalent Sw. The freezing point depressions are usually
described by a linear function of solution molality, which is valid for dilute solutions. At higher
concentrations, the DTf(xs) or DTm(xs) grow much faster than the solution concentrations, and a
nonlinear description is required. Equations (8.7.12a–h) give such a nonlinear approximation, and
(Eqn. 8.7.9)–(Eqn. 8.7.10) generalize it and take into account the pressure and droplet size effects.
These equations describe liquidus curves or the freezing and melting point depressions with high
accuracy over a wide range of solution concentration, as will be illustrated in Section 8.7.4.
For a particular case of a dilute solution, the saturation ratio Sw is related to the mole fraction xs
as Sw ≈ 1 − xs, and expanding (Eqn. 8.7.12a) into the power series, Tf,hom can be presented in a linear
approximation as
T f ,hom = T0 (1 − x s )Gn T0 − Gn T0 x s T0 + ml x s ,
∆T f = T0 − T f ,hom = − ml x s , ml = − Rv T02 / Lefm = −103.1K, (8.7.13)

where (Eqn. 8.6.15) is used for Gn, and ml is a slope of the liquidus curve. Equation (8.7.13) is a known
linear approximation for the liquidus or for the ideal freezing point depression (e.g., Pruppacher and
Klett, 1997; Curry and Webster, 1999). Note that the difference between Tf,hom and Tm for ice may be
caused by the small values of the segregation coefficient ks (the ratio of the amount of salt trapped in
ice during freezing to the amount in the solution), which is typically ∼10−6 to 10−4. If a concentrated
solution exhibits strong non-ideality, a correction may be required for (Eqn. 8.7.13).

8.7.3. Relation of the Freezing and Melting Point Depressions

The freezing and melting point depressions, DTf,hom and DTm, arise due to the presence of solutes. The
relations between DTf,hom and DTm are often given as:
∆T f ,hom = λ∆Tm , (8.7.14)

∆T f ,hom = T0 − T f 0 − T f ,hom , ∆Tm = T0 − Tm , (8.7.15)

where T0 = 273.15 K and Tf 0 = 38 K. Spontaneous freezing is usually assumed to start around −38 °C,
or T0 − Tf 0 = 235 K, which is therefore a reference point for the freezing depression, and Tf,hom and
Tm are evaluated from experimental data on freezing and melting (e.g., Rasmussen and MacKenzie,
1972; Rasmussen, 1982; Bertram et al., 1996; Koop et al., 1998, 2000; Martin, 2000; DeMott, 2002;
Kimizuka and Suzuki, 2007; Koop and Zobrist, 2009). The definition of l from (Eqn. 8.7.14) is an
empirical relation, and the value of DTf,hom required for numerical cloud models or analysis of the
laboratory experiments is taken usually from experimental data on DTm. The mean value l = 1.7 is
often used (e.g., Sassen and Dodd, 1988, 1989; DeMott et al., 1994; Martin, 2000; Chen et al., 2000;
Lin et al., 2002) as an average over the experimental data by Rasmussen (1982) on the relationship
between depressions of the freezing and melting temperatures for a number of salts. As discussed in
Section 8.4, it was clarified later that the coefficient l = 1.7 is not universal, and can vary over the
range 1.4–2.4 and may reach 3–5 for some organic substances, depending on the chemical compo-
sition and increasing with molecular weight and solute concentration (e.g., Kimizuka and Suzuki,
2007; Koop and Zobrist, 2009).
8.7. Critical Freezing and Melting Temperatures of Homogeneous Freezing 333

We can now calculate l from the theory as:

T0 − T f 0 − T f ,hom ( Sw , r )
λ (T ) = , (8.7.16)
T0 − Tm ( Sw )

where Tf,hom and Tm are evaluated from (Eqns. 8.7.7) and (8.7.12b). In a more extended form, it becomes

λ (T , Sw , rsa , ∆p, J f ,hom )

  1  −(16π /3)σ is3 
1/2
 
= T0 - Tf 0 - T0 SwGn exp(− Ap ∆p − A f /rsa ) × exp  − ef   
  L ρ  kT ln( J /C ) + ∆Fact  
 m i f ,hom hom

ef
× [T0 (1 − SwRT/M w Lm )]−1 . (8.7.16a)

This expression is a generalization of l that accounts for the effects of temperature, solution concen-
tration (Sw), pressure, finite droplet size, and finite nucleation rate. In particular, l as a function of T
can be different at different pressures, cooling rates, particles sizes, or solution concentrations. Equa-
tions (8.7.16) and (8.7.16a) allow determination of these dependencies and may explain the scatter of
the experimentally derived values of l.
The equations derived here based on classical nucleation theory suggest a direct relation between
Tf,hom and Tm using (Eqns. 8.7.7) and (8.7.10):
T f ,hom ( J hom , Sw , ras , ∆p)  Af Af 
= exp  − + 
Tm ( ∆p)  ras rcr 
 1  16π σ is3 
1/ 2

× exp − ef −  . (8.7.17)
L ρi  3 kT ln( J hom /Chom ) + ∆Fact 
 m

This relation allows evaluation of Tf,hom using measured or evaluated Tm. For the bulk solutions and
large crystals, rcr → ∞, ras → ∞, the first parenthesis on the right-hand side vanishes.

8.7.4. Comparison with Observations

The equations derived in this section represent Tf,hom and Tm as functions of Sw and the nucleation
rates Jf,hom. These equations contain several functions of Tf,hom or Tm on the right-hand side. They are
transcendental algebraic equations and can be solved using an iterative procedure. Numerical tests
show that two to three iterations provide a convergent solution. Calculation of Tf,hom and Tm requires
data on the temperature dependence of the melting heat Lm(T) or Lmef(T), DFact, water and ice densities,
and data on the temperature and composition dependence of the surface tensions.
Several sets of the thermodynamic parameters lead to calculated properties that agree with those
observed, but these parameters should be mutually consistent. In the calculations described in this
section, we use analytical functions Lmef(T) and sis parameterized following Khvorostyanov and
Curry (2004a) and based on extrapolation from Johari et al. (1994) as described in Section 4.4
and their appropriate parameterization and averaging. The values of sis were approximated with siw
and calculated from Antonoff’s rule. Numerical tests show that the values of Tf,hom are less sensitive
to the DFact. The choice of DFact from Jeffery and Austin (1997) was satisfactory. In the calculations
described here, the parameters are tuned to the data that are in the middle of that diverging range.
334 Homogeneous Nucleation

If the initial concentration of drops before freezing is N0, then the concentrations of frozen Nf and
unfrozen Nu drops are determined by the relations:
Nf = N 0 − N u , dNf = − dN u
dNf = − N uVJ hom dt = ( N 0 − Nf )VJ hom dt . (8.7.18a)

(
Integration with the initial condition Nu(t = 0) = N0 yields N u = N 0 exp −VJ f ,homτ fr ,)
N f = N 0 [1 − exp(−VJ f ,homτ fr )] (8.7.18b)

where V = (4/3)pr3 is the drop volume, r is the droplet radius, and tfr is the characteristic “freezing
time.” We assumed in most calculations that Jf,hom Vtfr = 1—i.e., the freezing temperature Tf,hom is
defined by an e-folding decrease of N0 during tfr. This assumption implies that the nucleation rate
is determined by Jf,hom = (Vtfr)−1 or tfr = (Jf,homV) −1. If we suppose that 99% of drops freeze dur-
ing time t, and 1% of N0 are unfrozen, then we have a relation Nu = 10−2 N0 = N0exp(−VJf,homt), or
t = −ln(10−2)(1/VJf,hom) = 4.6(1/VJf,hom). Substituting here (Jf,homV) −1 = tfr, we obtain t = 4.6tfr; that is,
(Eqn. 8.7.18b) along with the condition Jf,hom Vtfr = 1 means that 99% of drops freeze during 4.6tfr. In
most calculations described in the following text, tfr= 1 s, r was varied, and then Jf,hom was evaluated.
For ease of comparing with observations, the results of the calculations are presented as func-
tions of the water saturation ratio Sw and mass weighted concentration w. The relations between Sw,
molality M̂, and w were given in Section 3.5. The parameterizations of water activity aw via M̂ or
w for ammonium sulfate were taken from Tang and Munkelwitz (1993), for sulfuric acid from Chen
(1994), DeMott et al. (1997), and for NaCl from (Curry and Webster, 1999, and Millero, 1978).
The homogeneous freezing temperature Tf,hom for p = 1 atm is presented in Fig. 8.6a,b. Calculations
were performed using (Eqn. 8.7.7) for sulfuric acid (Ms = 98) and ammonium sulfate (Ms = 132),
tfr = 1 s, and for the solution drop radii r = 5 μm and 0.2 μm. Fig. 8.6a,b shows that the values of
Tf,hom for pure water (w = 0, Sw = 1) are 231 K (−42 °C) for r = 0.2 μm and 235.2 K (−38 °C) for
r = 5 μm—i.e., (Eqn. 8.7.7) predicts that the freezing point depression increases with a decreasing
drop radius. Thus, (Eqn. 8.7.7) along with the fits for the parameters described earlier yields the
well-known temperatures near −40 °C, referred to as the temperature of spontaneous freezing of pure
water drops. Fig. 8.6a shows that calculated variations of Tf,hom with solute concentration w are in
good agreement with parameterizations of laboratory data from Koop et al. (1998) and Bertram et al.
(2000) and are different for ammonium sulfate and sulfuric acid, depending on the chemical nature
of the solute. However, Fig. 8.6b shows that the curves Tf,hom(Sw) for r = 5 μm plotted as functions of
saturation ratio Sw almost coincide and merge with the experimental data and parameterizations from
Koop et al. (1998), Bertram et al. (2000), and Larson and Swanson (2006) presented as functions of
Sw (or aw). That is, Tf,hom(Sw) exhibits colligative properties and does not depend on the nature of the
solute. This is a consequence of the dependence of rcr and DFcr on Sw, and not on w. Fig 8.6b shows
that the decrease in r from 5 μm to 0.2 μm results in a decrease of Tf,hom by 4 K, which is also in
agreement with experimental data (Hagen et al., 1981; Young, 1993; Pruppacher and Klett, 1997).
The curve Tf,hom calculated for r = 0.2 μm lies lower as a whole at each Sw, which can contribute to
the residual difference for polydisperse drop spectra (seemingly non-colligative—i.e., depending not
only on Sw). This is in agreement with some residual non-colligative features of freezing that were
noticed in the experiments by Miyata et al. (2001).
8.7. Critical Freezing and Melting Temperatures of Homogeneous Freezing 335

240 (NH4)2SO4 240 KC04, r = 5 µm

(NH4)2SO4, B00 KC04, r = 0.2 µm
H2SO4, rd = 5 µm 230 B00, data, am. sul.
230 B00, param.
H2SO4, K98 220 K98, data, sul. ac.
Tf,hom (K)

Tf,hom (K)
220 K98, param.
210 LS06, data
210 200
190
200
180
190 170
0 10 20 30 40 1.0 0.9 0.8 0.7
Weight concentration (%) Water saturation ratio Sw or activity aw
(a) (b)

Figure 8.6. (a) Homogeneous freezing temperature Tf,hom(w) as a function of the weight
concentration w. Calculations using the theory from Khvorostyanov and Curry (2004a) using
(Eqn. 8.7.7) for solution drops of 5 μm for ammonium sulfate (solid circles) compared to the
parameterization from Bertram et al. (2000, B00) and calculations for sulfuric acid droplets of 5 μm
(diamonds), compared to the parameterization from Koop et al. (1998, K98). (b). Homogeneous
freezing temperatures Tf,hom as functions of the water saturation ratio: calculated as
in Khvorostyanov and Curry (2004a, KC04) from (Eqn. 8.7.7) as described in the text after a
second T-iteration for the haze drop radius rd = 5 μm (diamonds), and for rd = 0.2 μm (solid
circles), compared to the experimental data and parameterizations of Tf,hom for ammonium sulfate
of Bertram et al. (2000) (B00), of Larson and Swanson (2006) (LS06), and for sulfuric acid of
Koop et al. (1998) (K98) plotted as a function of Sw ≈ aw.

This approach allows estimation of the dependence of freezing temperature on the drop radius,
Tf,hom(r), along with estimation of the lower temperature limit of freezing of water and determina-
tion of the factors that influence it. The upper solid line in Fig. 8.7 is calculated using (Eqn. 8.7.7)
with a constant freezing time tfr = 1 s, p = 1 atm, and Sw = 1 (pure water) for the drops with radii
from 10 Å to 5 mm (the drops with greater r are hydrodynamically unstable). The calculations
are in good agreement with the experimental data by Mossop et al. (1955), Hagen et al. (1981),
and DeMott and Rogers (1990), denoted by the symbols near the curve. The figure shows that
the upper limit of freezing temperature does not rise above −30 °C even for the largest drops with
r ∼ 5 mm; that is, homogeneous freezing begins only at low temperatures.
At r = 3.1 × 10−6 cm (310 Å), the curve reaches the limit Tf,th = −45 °C that was hypothesized to
be the “stability limit,” where the thermodynamic parameters tend to infinity, and below which liquid
water does not exist (Speedy and Angell, 1976; Angell, 1982; Speedy, 1982; Pruppacher and Klett,
1997; see Chapter 4 here). At r ≈ 10 Å, close to the minimum possible drop size, Tf,hom ≈ −54 °C,
well below the hypothesized stability limit. Recent measurements by Huang and Bartell (1995) found
liquid drops with rd = 30 Å near −70 °C, and molecular dynamics simulations by Tanaka (1996)
indicated the possible existence of liquid water down to T = 193 K (−80 °C), but the freezing time of
such drops was very small. To further explore the lower limit of Tf,hom, we performed another series
of calculations with a constant radius of 30 Å (same as in Huang and Bartell) and a freezing time
tfr decreasing from 1 s to 10−7 s (an almost vertical line with triangles in Fig. 8.7). The results show
336 Homogeneous Nucleation

–30
M
DR
–40 H

Temperature (C)
–50 100

–60 10–4
10–5

–70 10–6, HB-95

–80 10–7, Tan-96

1E–8 1E–7 1E–6 1E–5 1E–4 1E–3 1E–2 0.1 1

Drop radius (cm)

Figure 8.7. Homogeneous freezing temperature Tf,hom of pure water drops (Sw = 1) as a function
of drop radius calculated with (Eqn. 8.7.7) with the freezing time tfr = 1 sec, p = 1 atm for the
drop radii from 10 Å to 5 cm (upper solid line) compared to the experimental data by Hagen et al.
(1981) (H, cross), DeMott and Rogers (1990) (D, diamond), and Mossop (1955) (M, asterisks).
Dotted vertical line with triangles shows decrease of Tfhom for a drop of radius 30 Å (solid square)
with decreasing freezing time tfr, indicated by the numbers near the curve (tfr = 100 sec, 10−4 sec,
etc.). tfr = 10−6 sec with Tf ≈ −70 °C corresponds to the experiment by Huang and Bartell (1995,
HB-95), and tfr = 10−7 sec with Tf ≈ −81 °C corresponds to the molecular dynamics simulation of
Tanaka (1996, Tan-96). These cases are indicated at corresponding tfr.

a decrease of Tf,hom from −50 °C at tfr = 1 s to Tf = −81 °C at tfr = 10−7 s. Thus, (Eqn. 8.7.7) shows
that liquid drops could exist at very low temperatures but their lifetime tfr is very short, which is in
agreement with the observations by Huang and Bartell (1995) and molecular dynamics simulations
by Tanaka (1996). The calculations shown in Fig. 8.7 can explain both the older experimental data
(for larger tfr) with the new data and concepts based on computer simulations by Tanaka (1996).
Note that the increase of the nucleation rate Jf,hom or the decrease of the time tfr are not unlimited.
Since the denominator in brackets of the second exponent in (Eqn. 8.7.7) should be negative (to yield
a positive value under the square root), we have the following conditions for Jhom and tfr:

J hom ≤ Chom exp(−∆Fact / kT ), (8.7.19)

which, along with assuming Jf,hom Vtfr = 1, yields

τ fr ≥ (ChomV )−1 exp( ∆Fact /kT ). (8.7.20)

These conditions may determine the minimum (spinodal) temperature of homogeneous freezing.
Similar calculations with (Eqn. 8.7.12b) of the melting temperature Tm (liquidus curves) at
p = 1 atm for ammonium sulfate, sulfuric acid, and NaCl are shown in Fig. 8.8a,b, again exhibiting a
good agreement with experimental data. Note that these results do not depend on surface tension or
droplet radius. Again, Tm as a function of mass weighted concentration w differs for the three indi-
cated chemical species (Fig. 8.8a), but merges as a function of Sw, exhibiting a colligative property
8.7. Critical Freezing and Melting Temperatures of Homogeneous Freezing 337

amm. sulf., mod NaCl

275 amm. sulf., exp 275 amm. sulf.
sulf. acid., mod sulf. acid
sulf. acid., exp 270
270 Chukin et al. (2010)
NaCl, mod
NaCl, exp 265 Clegg et al. (1995)
265
260
Tm(K)

Tm(K)
260 255

250
255
245

250 240
0 10 20 30 40 1.0 0.9 0.8 0.7
Weight % Saturation ratio Sw (or aw)
(a) (b)

Figure 8.8. Melting temperatures Tm calculated with the KC04a model from (Eqn. 8.7.12b)
for ammonium sulfate (closed circles), sulfuric acid (closed diamonds), and NaCl (crosses).
(a) Tm calculated as functions of weight percent w (labeled “mod”) compared to the corresponding
experimental data (labeled “exp”); (b) the same Tm(Sw) calculated with (Eqn. 8.7.12b) as in
Fig 8.8a, but with weight percent recalculated to the saturation ratio Sw or water activity aw and
compared to the parameterizations from Clegg et all. (1995) and Chukin et al. (2010). Saturation
ratio Sw is assumed to be equal to water activity, which is calculated for ammonium sulfate with
Eqns. from Tang and Munkelvitz (1993), for sulfuric acid from Chen (1994) and DeMott et al.
(1997). Experimental data on Tm for ammonium sulfate and sulfuric acid are from DeMott (2002).
The experimental parameterization of Tm(s) for NaCl as a function of salt concentration s (psu) is
taken from Millero (1978) and Curry and Webster (1999) and recalculated from s to water activity.
Tm(Sw) in Fig. 8.8b is in good agreement with the experimental parameterization from Chukin et al.
(2010) and with the thermodynamic model of composite solutions from Clegg et al. (1995).

of Tm (Fig. 8.8b). Thus, Fig. 8.8 shows that (Eqn. 8.7.12b) can be used with sufficient accuracy for
calculations of Tm for standard pressure.
One of the most interesting and important applications of this theory is calculation of the freezing
and melting point depressions, DTf,hom and DTm, and their ratio, l, which is used in cloud models.
Rasmussen (1982) found that measured values of DTf,hom and DTm for micron-sized drops for several
substances exhibit a linear relation. Rasmussen hypothesized that this is in conflict with classical
nucleation theory, and it could be explained by the relation of thermodynamic and kinetic processes
and by the spinodal decomposition in ice formation of aqueous electrolytes. This conjecture has been
challenged by several researchers. Here, we use (Eqns. 8.7.7) and (8.7.12b) to calculate DTf,hom and
DTm for rd = 5 μm with the same parameters as used for Figs. 8.6 and 8.8, and then calculate l with
(Eqns. 8.7.16) and (8.7.16a) and compare with laboratory data from Rasmussen (1982) and DeMott
(2002) and with the experimental parameterization for sulfuric acid from Koop et al. (1998) (Fig. 8.9).
To also illustrate the effect of drop radii, we have chosen the freezing threshold Tf0 = 38 K. As
seen in Fig. 8.9a, the calculated freezing point depression exhibits a relation that looks quasi-linear
on the DTf,hom − DTm diagram. The experimental data for Tf,hom lie mostly between the regression lines
338 Homogeneous Nucleation

50
rd = 5 µm, H2SO4
45
K98
40 λ = 2.0
35 λ = 1.5

30 NaCl
∆Tf (K)

LiCl
25
mixture
20 NH4Cl
15
10
5

0 Figure 8.9. (a) Calculated relation

0 5 10 15 20 25 DTf = lDTm for the 5 μm solution
∆Tm (K) droplets of sulfuric acid (diamonds)
compared to the experimental data by
(a)
Koop et al. (1998) for sulfuric acid and
4.0 to the experimental data for indicated
mod, (NH4)2SO4
substances compiled by DeMott (2002);
B00-D02, (NH4)2SO4
correlation curves l = DTf /DTm = 1.5 and
mod, H2SO4
l = 2 are given for comparison.
λ = ∆Tf /∆Tm

3.0 K98-D02, H2SO4

(b) Parameter l(w) calculated with
(Eqn. 8.7.16) for the drop radii of 5 μm
2.0 as a function of weight concentration w
for ammonium sulfate and sulfuric acid
(denoted “mod”) compared to
1.0 l calculated with the experimental Tf,hom
0 10 20 30 40
from Koop et al. (1998) and DeMott
(2002) for sulfuric acid (K98-D02) and
Weight concentration (%)
from Bertram et al. (2000) and DeMott
(b)
(2002) (B00-D02) for ammonium
2.5
(NH4)2SO4 sulfate, and with Tm shown in Fig. 8.8.
H2SO4 (c) l(Sw) calculated with (Eqn. 8.7.16)
for the drop radii of 5 μm for ammonium
λ = ∆Tf /∆Tm

sulfate and sulfuric acid, the same as in

2.0 Fig. 8.9b, but as a function of the water
saturation ratio Sw. From Khvorostyanov
and Curry (2004a), Thermodynamic
theory of freezing and melting of water
and aqueous solutions. J. Phys. Chem. A,
1.5
108 (50), 11073–11085. Copyright 2004,
1.0 0.9 0.8 0.7
American Chemical Society, reprinted
Saturation ratio Sw with permission of the American
(c) Chemical Society.
8.7. Critical Freezing and Melting Temperatures of Homogeneous Freezing 339

l = 1.5 and 2 up to DTf ∼ 10 K, and the curve calculated here for r = 5 μm matches the observations.
For higher values of DTf up to ∼ 45 K, experimental data from Koop et al. (1998) lie closer to l = 2,
and so does the calculated curve. We can draw the following conclusions from Fig. 8.9a: a) classical
nucleation theory with the appropriate extension described here is capable of describing the quasi-
linear relation between the freezing and melting point depressions and can be used in cloud models
for evaluation of l or directly for Tf,hom; b) a more detailed theoretical analysis should include kinetic
simulation of the freezing of a polydisperse drop ensemble as it is done in some cloud models, since
freezing proceeds from larger to smaller drop sizes and the values of Tf,hom and l determined in
experiments may depend on the fraction and size of frozen drops.
Direct calculation of the parameter l = DTf /DTm with (Eqn. 8.7.16) (Fig. 8.9b,c) shows that it is
not a constant since it depends on the chemical composition and Sw. The calculated l(w) for ammo-
nium sulfate and sulfuric acid (Fig. 8.9b) depends on the chemical composition, but the curves are
relatively close to each other and to the curves derived from laboratory data (Koop et al., 1998;
Bertram, et al., 2000). l(w) varies mostly between 1.9–2.2 in agreement with the previous analysis of
experimental data for these substances. When plotted as l(Sw) (Fig. 8.9c), the curves almost merge,
exhibiting again colligative properties as both DTf,hom and DTm (Figs. 8.6b and 8.8b). The values l(Sw)
are not constant but exhibit a monotonous growth with decreasing Sw, and use of constant l in cloud
models may lead to errors in DTf,hom. The difference slightly increases at small w or Sw → 1, but both
calculations and measurements become less reliable at small solute concentrations (or Sw → 1) since
both DTf,hom and DTm decrease, and even a small error in each of these quantities may lead to an
increasing error in their ratio l.
Kimizuka and Suzuki (2007) tested many various chemical species and found that a good lin-
ear relationship DTf,hom(Sw) = lDTm(Sw) was observed for all samples. They noted that this relation-
ship and the slopes l were in good agreement with predictions from the Khvorostyanov and Curry
(2004a) theory for the substances with sufficiently low molar mass. Recent studies showed that l
can generally increase with increasing molar mass and may reach values of 3.5–5.1. Kimizuka and
Suzuki (2007) proposed that this large variation in l is due to the dependence of l on the solute’s dif-
fusion coefficient, which in turn depends on the solute’s molar mass. One possible way of describing
this effect within classical nucleation theory could be based on an appropriate account for the surface
tension and other thermodynamic parameters on the solute chemical composition.
Calculations with varying r (not shown here) demonstrate that l also may depend on drop size,
since Tf 0 increases with decreasing drop size r (recall, the threshold temperature Tf 0 ≈ 38 K for
r = 5 μm and 42 K for 0.2 μm, see Fig. 8.6), and no single value is representative for the polydis-
perse ensemble of drops. So, different thresholds Tf 0 should be chosen for various drop radii, which
illustrates a problem in the analysis of experimental data obtained with polydisperse drops and in the
evaluation of l using the theory as it is used here.

8.7.5. Equivalence of Solution and Pressure Effects

Calculations of freezing and melting point temperatures under conditions of variable pressure are
sensitive to variations in the density of liquid and solid water, rw(T, p) and ri(T, p). Here we use a
parameterization from Pruppacher and Klett (1997) and results from Jeffery and Austin (1997, 1999)
340 Homogeneous Nucleation

and Holten et al. (2011, 2012) for ri(T) of hexagonal ice Ih (see Chapter 4). The data on rw(T, p)
below T = −40 °C are scarce and rw(T, p) can be taken or extrapolated from the equation of state
for liquid water (e.g., Poole et al., 1994; Jeffery and Austin, 1997, 1999; Kiselev and Ely, 2002),
molecular dynamics simulations (Tse, 1992, 1999; Poole et al., 1994), or from experimental data
where possible (Mishima and Stanley, 1998) (see Chapter 4). We have used available data and (Eqn.
8.7.8) to estimate variations of rw(T, p) from the slopes dTf,hom/dp in the experimental data of Kanno
and Angell (1977) for Tf,hom. We have from (Eqn. 8.7.8) for Dr = rw − ri

ρ w ρi Lm  dT f ,hom 
∆ρ ≈ − , (8.7.21)
T f ,hom  dp 

The results described in the following were obtained using the values of Dr given in these works and
values estimated from (Eqn. 8.7.21) using the corresponding data from the cited works.
Equation (8.7.7) includes the simultaneous effects of pressure and chemical composition
(solute concentration described by Sw < 1) on Tf,hom(Dp). The effects of composition at p = const
were described in the previous section, and now Fig. 8.10 presents freezing temperatures Tf,hom(p)
calculated with (Eqn. 8.7.7) as a function of pressure for pure water (Sw = 1). A comparison of theo-
retical and experimental results in Fig. 8.10 exhibits good agreement over the entire temperature
and pressure ranges, indicating the validity of (Eqn. 8.7.7). Note that the experimental data show the
change of the sign of the slope at p ∼ 2 kb. This is caused by the nucleation of ice III, which begins

240
Tf,hom(p)
230
KA77

220
Temperature (K)

210

200

190

180

170
0.00 0.05 0.10 0.15 0.20 0.25 0.30
Pressure (GPa)

Figure 8.10. Homogeneous freezing nucleation temperatures Tf,hom calculated with (Eqn. 8.7.7) for
pure water (Sw = 1) as a function of pressure (solid circles) and compared to the experimental data from
Kanno, and Angell (1977) (KA77). From Khvorostyanov and Curry (2004a). Thermodynamic theory
of freezing and melting of water and aqueous solutions. J. Phys. Chem. A, 108 (50), 11073–11085.
Copyright 2004, American Chemical Society. Reprinted with permission of the American Chemical
Society.
8.7. Critical Freezing and Melting Temperatures of Homogeneous Freezing 341

at p ∼ 1.8 kb and prevails at pressures higher than 2 kb (Kanno and Angell, 1977; see Section 4.1
here); a possible relatively wide temperature range of coexistence of ice I and ice III at p = 1 atm was
explained by Johari (1998) by the polydisperse structure of finely dispersed ices. This transition in
Fig. 8.10 at p = 2 kb is explained simply by (Eqns. 8.7.7), (8.7.8), and (8.7.21): Since the pressure
dependence of freezing temperature is determined by the difference (rw − ri) and the density of ice III
is greater than that of ice Ih (Hobbs, 1974), the slopes dTf,hom/dp may vary and change sign at abrupt
changes of the ice densities. A more detailed analysis of this effect requires more precise data on ri,
rw in this pressure range.
Similar calculations were performed for pressure-induced melting ice temperature Tm using
(Eqn. 8.7.10) for bulk ice (rcr = ∞) and Sw = 1 (pure water). The results are compared in Fig. 8.11
with experimental data (Wagner et al., 1994; Mishima, 1996; Mishima and Stanley, 1998). One can
see that the experimental curve from (Mishima, 1996; Mishima and Stanley, 1998) has two distinct
branches and the slopes change at p ∼ 0.5 GPa, which also is explained in these works by the change
near this point of the ice type from hexagonal Ih to the other types of ice with higher densities (ice III
or ice V). Fig. 8.11 shows that the values of Tm calculated from (Eqn. 8.7.10) are very close to both
experimental curves up to p = 0.5 GPa, but the difference between the calculated and observed values
increases at higher pressures if we are to keep ri(T) = const. Agreement becomes a little better with

300
Eq. (8.7.10)
250 Eq. (8.7.10), ∆ρι = 0
MS
WSP
200
Temperature (K)

150

100

50

0
0.0 0.5 1.0 1.5
Pressure (GPa)

Figure 8.11. The melting temperature for the pressure-induced melting of ice calculated using
(Eqn. 8.7.10) with ri(T) = const (Dri = 0, crosses) and with a linear increase of ice density
ri(T) by 0.04 g cm−3 in the range p = 0.6−0.8 GPa (solid circles) compared to the experimental data
of Mishima (1996) and Mishima and Stanley (1998) down to ∼80 K (MS) and to Wagner, Saul,
and Pruss (1994) down to 251 K (triangles, WSP). Reprinted with permission of the American
Chemical Society from Khvorostyanov and Curry (2004a). Thermodynamic theory of freezing and
melting of water and aqueous solutions. J. Phys. Chem. A, 108 (50), 11073–11085. Copyright 2004,
American Chemical Society.
342 Homogeneous Nucleation

a linear increase in ri(T) by 0.04 g cm−3 over the range p = 0.6 − 0.8 GPa (this could imitate admix-
ture of the other denser ice III or ice V); however, some discrepancy still remains. Computer lattice
dynamics simulations (Tse, 1994; Tse et al., 1999) determined that melting is caused by thermody-
namic instability up to p ∼ 0.5 GPa and by mechanical instability at higher pressures. The results
shown in Fig. 8.11 are consistent with this conclusion, satisfactorily describing the upper branch
of the Tm curve to p ∼ 0.5 GPa but worsening for higher p values. Thus, (Eqn. 8.7.10) can serve for
simple calculations of Tm(p) for pure water up to p = 0.5 GPa; its predictions for pressure-induced
melting taking into account the solutions (Sw < 1) could be verified experimentally.
As discussed in Chapter 4, an interesting question on the equivalence of the pressure and solu-
tion effects on freezing and melting temperatures was explained by the similar effect of solution
and applied pressure on the hydrogen bonding network (Kanno and Angell, 1977; Leberman and
Soper, 1995), and by showing that the plots of Tf (aw) and Tf (p) are similar. This effect was described
by introducing the “effective” solution concentration (Koop et al., 2000). A simple but sufficiently
general quantitative expression for this equivalence was found by Khvorostyanov and Curry (2004a)
from (Eqns. 8.6.14a), (8.6.14b) or (8.6.17b) for rcr(T, Sw, p), and is described in the following text. It
shows that variations in the solution concentration (or in Sw) may be viewed as equivalent to pressure
variations. Recalculations from the solution molality to Sw and back can be done with (Eqns. 8.6.33)
and (8.6.34). It is seen from (Eqn. 8.6.17b) that this pressure–solution equivalence can be expressed
as SwGn = exp(− H v , fr ), which, using (Eqn. 8.6.16) for Hv,fr, can be written as

 ∆ρ∆p 2σ sa 
SwGn = exp  − − . (8.7.22)
 ρi ρ w Lm ρi Lm rd
ef ef


Equation (8.7.22) expresses Sw (or a corresponding molality) as a function of equivalent pressure Dp

or vice versa. Solving relative to Dp, we obtain
RT ρi ρ w 2σ sa ρ w
∆p = − ln Sw − = −QρT ln Sw + ∆pcur , (8.7.23)
M w ( ρ w − ρi ) rd ρ w − ρi

where QrT is the function of T, rw, ri, and Dpcur is the correction to pressure due to curvature of a
freezing drop with radius rd:

RT ρi ρ w 2σ sa ρ w
QρT (T , ρ w , ρi ) = , ∆pcur = − . (8.7.23a)
M w ( ρ w − ρi ) rd ρ w − ρi

Equations (8.7.23) and (8.7.23a) were derived in Khvorostyanov and Curry (2004a) and are gen-
eralized here by adding the term Dpcur. Equations (8.7.23)–(8.7.23a) show that a decrease in Sw or aw
(an increase in solution molality) is equivalent to an increase in Dp, with proportionality determined
by the function QrT that depends on the densities and temperature. The proportionality is Dp ∼ −T lnSw
with the constant densities, although they in turn depend on p, T. The value of QrT is very large, an esti-
mate at T ∼ −60 °C gives QrT ∼ 0.9 GPa = 0.9 × 104 atm, and QrT further increases with decreasing T.
Equation (8.7.23) shows that a solution with saturation ratio Sw = 0.9 (lnSw ≈ −0.1) is equivalent
to an applied external pressure Dp ≈ Qr T lnSw ≈ −0.9 × 104 × (−0.1) atm = 0.9×103 atm ≈ 0.9 kbar at
T ∼ −60 °C. The curvature term Dpcur is generally smaller than the first term with QrT or osmotic pres-
sure Π; an estimate yields Dpcur ∼ −10 atm for a drop with r = 1.5 μm and −100 atm for r = 0.15 μm.
8.7. Critical Freezing and Melting Temperatures of Homogeneous Freezing 343

Its sign is opposite the sign of the term with −ln(Sw), and partially compensates for the solution effect.
For the smaller drops, the derivation should be refined accounting for the dependence of the surface
tension on the drop radius. The term Dpcur vanishes for the bulk solutions (r = ∞).
Thus, (Eqns. 8.7.22)–(8.7.23a) establish the equivalence of the deformation of the hydrogen bonds
network by the chemical forces due to solutes and mechanical pressure. This is illustrated in Fig. 8.12,
which presents the Dp − Sw relation calculated with (Eqn. 8.7.23) in the same way as the previous two
figures. For comparison, we also plotted the two experimental points from Kanno and Angel (1977,
KA77) who presented the data in units R = 55.5/ Mˆ , with M̂ being the molality. We recalculated
from R to the molalities, and then to Sw for NaCl, and the two experimental points from KA77
are shown in Fig. 8.12, which shows the equivalence of p = 1000 bar (0.1 GPa) to the molality of
NaCl Mˆ = 2.75 ( R = 20 ) and p = 1500 bar (0.15 GPa) to the molality Mˆ = 4.65 ( R = 12 ) for
both freezing and melting temperatures. Fig. 8.12 shows good agreement of the curve calculated with
(Eqn. 8.7.23) with the experimental data and confirms the validity of these equations, which therefore
can be used for the prediction of the pressure effects on Tf,hom, Tm given the solution effects, or vice versa.
This agreement and thermodynamic equivalence of solution (or Sw) and pressure effects leads to
an important conclusion. Kanno and Angell (1977), Leberman and Soper (1995), Koop et al. (2000),

1.00

0.95

0.90 R = 20 (M = 2.75)
Sw

0.85
R = 12 (M = 4.65)
0.80

0.75

0.70
0.00 0.05 0.10 0.15 0.20 0.25
Pressure (GPa)

Figure 8.12. Equivalence of pressure and saturation ratio or molality expressed with (Eqns. 8.7.23)
and (8.7.23a). The curve with solid circles is calculated with (Eqn. 8.7.23) here, and two points
(squares) are experimental data for NaCl from Kanno and Angell (1977) expressed in that work
in terms of the ratio R = 55.5/Mˆ , with M̂ being the molality. These two points from Kanno and
Angell (1977) establish the equivalence of p = 1.0 kbar (0.1 GPa) to R ≈ 20 ( Mˆ = 55.5 / R = 2.75)
and p = 1.5 kbar (0.15 GPa) to R ≈ 12 ( Mˆ = 4.65) . The experimental points lie almost on the
theoretical curve (denoted by ellipses) that confirms the validity of (Eqn. 8.7.23). Reprinted
with permission of the American Chemical Society from Khvorostyanov and Curry (2004a).
Thermodynamic theory of freezing and melting of water and aqueous solutions. J. Phys. Chem. A,
108 (50), 11073–11085. Copyright 2004, American Chemical Society.
344 Homogeneous Nucleation

and others interpreted this equivalence at the molecular level in terms of the distortion of the hydrogen
bonds and quantitative relationships between the solution and pressure effects for required calculations
like molecular dynamics simulations by specifying the intermolecular potentials, or similar methods.
The consideration in Khvorostyanov and Curry (2004a) and this book shows that this equivalence can
be interpreted and evaluated more simply, without considering the molecular effects, from the general
bulk thermodynamic relations based on the new expressions for the critical radius in Section 8.6.
Equation (8.7.7) includes the simultaneous effects of pressure and chemical composition on
Tf,hom(Dp). Fig. 8.13 presents freezing temperatures Tf,hom(Dp) as a function of pressure for pure water
and three solutions of NaCl and LiCl calculated from (Eqn. 8.7.7) for varying concentrations in terms
of R units as in Kanno and Angell (1977), for R = 55.5 (molality M̂ = 1), R = 20 ( M̂ = 2.775), and
R = 12 ( M̂ = 4.625 ). A comparison of theoretical and experimental results in Fig. 8.13 exhibits gen-
erally good agreement with observations for the corresponding molalities over the entire temperature
and pressure ranges, and supports the validity of (Eqn. 8.7.7); that is, both dependencies on pressure
and solution concentration correctly describe the observations.
The experimental data from Kanno and Angell (1977) in Fig. 8.13 show an abrupt change of
slopes, labeled as the points Tg, which was interpreted in Kanno and Angell (1977) as the temperature
of glassy transition points or regions at pressures pg = 0.14 − 0.2 GPa and Tg = −95 to −115 °C. For
p > pg, the slope changes the sign, dTf,hom /dp becomes positive, and we see a second branch with a lin-
ear increase of Tf,hom with increasing p at a constant gradient. The term in (Eqn. 8.7.7) that determines
the change in slope arises from the exp(−Xp), where Xp is
Aρ ∆p ∆ρ ⋅ ∆p
Xp = − =− . (8.7.24)
ρi Lefm ρ w ρi Lefm

0.28 Pure water

0.24 R = 55.5
Tg R = 20
Pressure (GPa)

0.20 R = 12
0.16 NaCl, R55.5
Tg NaCl, R20
0.12 LiCl, R20
NaCl, R12
0.08
0.04
0.00
–110 –100 –90 –80 –70 –60 –50 –40 –30 –20
Temperature (C)

Figure 8.13. Homogeneous freezing temperatures T f ,hom ( p, Mˆ ) calculated with (Eqn. 8.7.7) for
pure water (diamonds) and solution drops as the functions of pressure p and various molalities
M̂ of NaCl. The results are presented in the form similar to Fig. 3 in Kanno and Angell (1977) in
terms of R units as in that work (R = moles water/moles salt = 55.5/ Mˆ ): for R = 55.5 (M̂ = 1,
solid circles), R = 20 ( M̂ = 2.775, triangles), and R = 12 (M̂ = 4.625, crosses). These calculations
are compared to the four sets of experimental data for the same R and M̂ from Kanno and Angell
(1977) kindly provided by Prof. Hitoshi Kanno and shown with open symbols for NaCl with
R = 55.5 (open circles), R = 20 (triangles), and R = 12 (asterisks), and LiCl, R = 20 (squares).
Tg are the temperatures of glassy transition, as described in the text.
8.8. Threshold or Critical Saturation Ratios for Homogeneous Freezing 345

Equation (8.7.21) for Dr shows that the decrease of Tf,hom or the negative gradient dTf /dp < 0 at
p < pg means that Dr = rw − ri > 0—i.e., the density of ice is less than the water density. However,
(Eqns. 8.7.21) and (8.7.24) imply that Dr changes its sign at p > pg, along with the sign of the gradient
dTf,hom /dp. Since the solution or water density is the same at T = Tg, slightly below and above pg, we
see that the ice density increases in a step-like manner in the vicinity of Tg, and the sign change of Dr
arises solely due to the change in ice density. This behavior can be explained by the formation of the
“glassy” ice germs with increased density in water or solution drops at p > pg. At these high pressures,
critical radii and free energies of the germs are described by the same (Eqns. 8.6.17a), (8.6.17b), and
(8.6.18) and the freezing temperature by (Eqn. 8.7.7); however, the increase of Tf,hom with p requires
that X in (Eqn. 8.7.24) becomes positive at p > pg, T > Tg.
Denoting the density difference as Drc = rw − ric at T < Tg (before the glass transition) and
Drg = rw − rhda at T > Tg (after transition) with ric and rhda being ice densities in crystalline Ih and
in high-density amorphous (HDA) states (see Chapter 4), and assuming that rw = const at the glassy
transition, we obtain from (Eqn. 8.7.21) the ice density increase Drice as a difference of Drc and Drg
below and above pg:

ρi ρ w Lm  dT f dT f 
∆ρice = ∆ρc − ∆ρ g ≈  − , (8.7.25)
Tg  dp Tg +
dp Tg − 

where the subscripts Tg− and Tg+ denote derivatives just before and just after Tg, pg.
Hence, analysis of the experimental data from Kanno and Angell (1977) in the context of
(Eqns. 8.7.21) and (8.7.25) implies that: 1) the sign of the ice density jump is positive—i.e., the density
of ice increases abruptly at the point or region of glassy transition; 2) since the experimental gradients
dTf,hom/dp ≈ const at p > pg, dTf,hom > Tg, the value Drice does not depend here on pressure, and the density
of amorphous ice is nearly constant in some region of p, T after the glassy transition; and 3) the increase
in ice density is 20–25% at the transition point and yields rhda ∼ 1.17–1.22 g cm−3. These consequences
are in agreement with current views on this type of glassy transition (Mishima and Stanley, 1998;
Stanley et al., 2007). The pressure Dp equivalent to the solution according to (Eqns. 8.7.23)–(8.7.23a) is
proportional to Dr = rw − ri. This quantity changes signs and becomes negative after the glassy transi-
tion. Therefore, the pressure equivalent to the solution becomes negative.
The theory described here has certain limitations. It is based on general thermodynamics, does not
consider the properties of crystalline lattices and cannot explain why formation of amorphous ice is
preferred rather than more conventional forms of ice. This theory also does not predict the transition
point Tg, pg itself, since the symmetry of a phase is not accounted for in this approach. However, this
theory based on thermodynamic expressions for the critical radii and energies explains and describes
many features of homogeneous freezing and melting without invoking more complicated methods or
empirical parameterizations with many unknown parameters that require fitting, or time consuming
molecular dynamics simulations with various potentials.

8.8. Threshold or Critical Saturation Ratios for Homogeneous Freezing

Knowledge of the critical (or threshold) humidities or saturation ratios for the onset of ice nucle-
ation is crucial for parameterization in cloud and climate models, where simulations of mixed phase
and crystalline clouds depend critically on the choice of the threshold relative humidity. Critical
346 Homogeneous Nucleation

humidities over water and ice, or the corresponding saturation ratios, for homogeneous ice nucleation
at cold temperatures below −40 °C in cirrus clouds have been studied and parameterized using results
of parcel model simulations (Sassen and Dodd, 1988, 1989; Sassen and Benson, 2000; Lin et al.,
2002; Barahona and Nenes, 2008), data collected in aircraft measurements of cirrus or wave clouds
(Heymsfield and Miloshevich, 1995; Heymsfield et al., 1998), extensions of classical homogeneous
ice nucleation theory (Khvorostyanov and Sassen, 1998, 2002; Khvorostyanov and Curry, 2000,
2004a,b, 2005a, 2009b, 2012; Curry and Khvorostyanov, 2012), and data from laboratory measure-
ments (e.g., DeMott et al., 1998, 2002; Koop et al., 1998, 1999, 2000; Bertram et al., 2000; Martin,
2000; Möhler et al., 2006; Hoose and Möhler, 2012).
Until recently, classical ice nucleation theory has not yielded simple equations for the critical
humidity because the equations for the critical radius and energy of freezing in both modes written in
the form derived by J. J. Thomson (1888) depend on temperature only and do not include humidity
dependence. Although the more detailed differential entropy equations outlined in classical theory in
principle can account for the humidity or activity dependence (Dufour and Defay, 1963, Defay et al.,
1966; Pruppacher and Klett, 1997), these equations can only be solved numerically. A generalization
of classical theory for both homogeneous and heterogeneous ice nucleation presented here provides
analytical expressions for the critical radius and energy of an ice embryo and nucleation rates as
functions of temperature, the water saturation ratio, pressure, and the finite size of freezing particles
simultaneously. This allows to invert these equations and express the critical water and ice saturation
ratios or humidities as the functions of the corresponding variables.
In this section, we consider the critical humidities and saturation ratios for homogeneous ice
nucleation. Generalized equations are derived that express the critical saturation ratios or relative
humidities as functions of temperature, nucleation rate (or cooling rate), the size of the freezing par-
ticles, and environmental pressure. Variations of the critical humidities with varying input parameters
are illustrated with an extensive series of calculations.

8.8.1. General Equations

The critical saturation ratios and humidities for homogeneous freezing can be derived from
(Eqn. 8.7.3), which accounts for the dependence on the nucleation rates Jf,hom given by (Eqn. 8.3.5).
Transforming (Eqn. 8.7.4),

T0 Gn
Sw = exp( H v , fr + H f ,hom ), (8.8.1)
T
and solving it for Sw, we obtain the critical or threshold water saturation ratio of homogeneous freezing:
1/ Gn
Swhom
, cr = [(T /T0 ) exp( H v , fr + H f ,hom )] , (8.8.2)

where Hv,fr is defined in (Eqn. 8.6.16) and Hf,hom is defined in (Eqn. 8.7.5). In a more complete form,

 T   ∆ρ∆p rfr 

Swhom
, cr =   exp  + 
 ρ w ρi Lm ras 
ef
 T0 
M w Lefm /RT
  
1/2
 1  (−16π /3)σ is3
× exp  ef    , (8.8.3)
 Lm ρi  kT ln( J f ,hom /C f ,hom ) + ∆Fact   
 
8.8. Threshold or Critical Saturation Ratios for Homogeneous Freezing 347

where Dr = rw − ri, ras is the radius of a solution drop, and rfr was defined in (Eqn. 8.6.15). Equation
(8.8.3) expresses Swhom
, cr as a function of T, ras, rfr, Dp, and nucleation rate Jf,hom. We can prescribe Jf,hom,

and then calculate Swhom , cr as a function of T and other parameters. In practice, it is more convenient to

prescribe Jf,homV, where V = (3p /4)rd3 is the volume of an aerosol particle.

8.8.2. Parameterization of Effective Melting Heat

As discussed in Chapter 4, there are still substantial uncertainties in the literature on the values of
melting heat Lm(T), especially in solutions for T < −45 °C because direct measurements are difficult
at these temperatures. The functions Lm(T) may substantially differ in various sources (e.g., Dufour
and Defay, 1963; Defay et al., 1966; Hobbs, 1974; Johari et al., 1994; Pruppacher and Klett, 1997;
Jeffery and Austin, 1997, 1999; Murphy and Koop, 2005; Feistel and Wagner, 2005a,b; Wagner et al.,
2011; see Sections 4.4 and 4.6). Evaluation of the critical radii, energies, and nucleation rates requires
effective (properly averaged) Lefm (T ); however, there were different definitions of Lefm (T ) and only
a few attempts to evaluate it. Dufour and Defay (1963, Chapter XI therein) defined it as a simple
arithmetic average, noting that it is not a true value, but rather a simple mean for estimates of rcr.
Khvorostyanov and Sassen (1998c) defined it similarly to (Eqn. 8.6.8) as a fit to a function of T using
measured Jf,hom for pure water and solution droplets.
The equations for the critical saturation ratios derived in this section from the classical nucleation
theory, applied to conditions of a slow process for a bulk substance, can be used to derive an analyti-
cal parameterization for Lefm (T ) and compare it with other parameterizations. The two similar simple
methods of calculation and parameterization of Lefm (T ) are described in the following text.
The first method follows Khvorostyanov and Curry (2009b). As discussed earlier, for very slow
processes, Jf,hom → 0 and ln(Jf,om) → −∞, it follows from (Eqn. 8.7.5) for Hf,hom that the denominator
of Hf,hom tends to −∞ and Hf,hom → 0. Then, for a bulk substance (rd = ∞) and atmospheric pressure
(Dp = 0), (Eqn. 8.8.3) is simplified as

, cr (T ) = ( T / T0 )
M w Lefm / RT
Swhom . (8.8.4)

Note that the process with Jf,hom → 0 can be identified with the equilibrium state of bulk water with
ice—i.e., melting—and (Eqn. 8.8.4) represents the equation for the melting curve Sw(Tm) or Tm(Sw)
of the aqueous solution in the bulk state, where Tm is the melting temperature (see Section 8.7). The
environmental Sw then is equal to the water activity awi (T ) of bulk solution in equilibrium with ice,
thus we obtain:

, cr (T ) = aw (T ) = aw (Tm ) = ( T / T0 )
M w Lefm / RT
Swhom i
. (8.8.5)

This simple equation describes the temperature dependence of awi (Tm ) along the melting curve. Equa-
tions (8.8.4) and (8.8.5) can also be rewritten in an explicit form relative to Tm, as in (Eqn. 8.7.12b):
ef
Tm ( Sw ) = T0 SwRT / M w Lm . (8.8.6)

Thus, (Eqns. 8.8.4)–(8.8.6) also describe the melting point temperature in the presence of solute.
Parameterizations for awi (Tm ) along with (Eqns. 8.8.4) and (8.8.5) can be used to determine Lefm (T ).
By definition,
µ wi (T ) = µ w0 (T ) + RT ln awi (T ), (8.8.6a)
348 Homogeneous Nucleation

where µ wi (T ) and µ w0 (T ) are the chemical potentials of water in pure ice and of liquid water
(see Section 3.5). Thus, awi (T ) can be expressed from (Eqn. 8.8.6a) via the difference of the chemical
potentials (ordinary affinity), ∆µ = µ wi (T ) − µ w0 (T ):

 ∆µ 
awi (T ) = exp  . (8.8.7)
 RT 

Taking the logarithm of the relation Swhom

, cr (T ) = aw (T ) , and using (Eqns. 8.8.5) and (8.8.7), we obtain
i

∆µ (T )
Lefm (T ) = . (8.8.8)
M w ln(T /T0 )

This equation expresses effective Lmef as a function of T. Khvorostyanov and Curry (2009b) used for
the evaluation of Lm (T ) an expression for Dm(T) from Koop et al. (2000), who utilized Dm(T) from
ef

Johari et al. (1994) as was described by (Eqn. 8.4.10).

The second, newer method for evaluation of Lefm (T ) is even simpler and is based on the use of the
expression (Eqn. 3.10.24) for water activity in a solution in equilibrium with ice—i.e., the water
activity along the melting curve awi (Tm ) —as
eis (T )
awi (Tm ) = . (8.8.9)
ews (T )

This expression is simpler than (Eqn. 8.8.7) based on Dm(T) and requires only saturated pressures that
are known well enough (see Chapter 4, Section 4.4). Moreover, equating (Eqns. 8.8.7) and (8.8.9),
yields a useful expression for Dm(T):

 e (T ) 
µ wi (T ) − µ w0 (T ) = ∆µ (T ) = RT ln  is , (8.8.10a)
 ews (T ) 

which allows refinement of Dm(T) and its calculation down to very low temperatures using parameter-
izations of eis(T) and ews(T) (see Sections 4.4 and 4.6). Now, we have an equation from (Eqns. 8.8.9)
and (8.8.5) for the melting curve T = Tm:
M w Lefm /RT
e (T )  T 
S hom
(T ) = a (T ) = is
i
= . (8.8.10b)
ews (T )  T0 
w , cr w

Taking a logarithm, we obtain a simple relation:

RT ln[eis (T )/ews (T )]
Lefm (T ) = . (8.8.11)
Mw ln(T / T0 )

The advantage of (Eqn. 8.8.10b) for Swhom, cr (Tm ) and the water activity aw (T ) at melting compared
i

to (Eqn. 8.8.7) and the advantage of (Eqn. 8.8.11) for Lefm (T ) compared to (Eqn. 8.8.8) is that they
do not require knowledge of Dm(T), nucleation rates, or surface tensions, and are based only on the
saturated pressures for water and ice that are known and parameterized better than the difference of
the chemical potentials Dm(T). Various precise parameterizations for eis(T)/ews(T) were described in
Chapter 4.
Figure 8.14a shows a comparison of various Lm(T) and Lefm (T ) . The three functions Lm(T) are
parameterizations from Dufour and Defay (1963, DD63) down to 220 K, from Johari et al. (1994,
8.8. Threshold or Critical Saturation Ratios for Homogeneous Freezing 349

Joh94), which is very close to DD63 but is extended down to 170 K, and from Pruppacher and Klett
(1997). The Lm(T) chosen by Pruppacher and Klett (1997) from several available data sets are lower
than in DD63 and Joh94 and are given to 228 K because PK97 assumed a stability limit conjecture
at ≈ 228 K. The four effective (averaged) Lefm (T ) include: the arithmetic mean from Dufour and
Defay (1963, DD63, Lm-aver); similar to the DD63 arithmetic mean of Johari’s (1994) parameteriza-
tion (Joh94, aver); and two newer calculations based on the definition (Eqn. 8.6.8), calculations with
(Eqn. 8.8.11) using (Eqns. 4.4.2) and (4.4.4) for eis(T) and ews(T) by Murphy and Koop (2005), and cal-
culations with (Eqn. 8.8.8) from Khvorostyanov and Curry (2009b) with (Eqn. 8.4.10) for Dm from
Koop et al. (2000) (marked KC09–K00). Fig. 8.14a shows that the last two methods, (Eqns. 8.8.8)
and (8.8.11) give very close Lefm (T ) , which is close to a linear function, while both simple arithmetic
means overestimate Lefm (T ) .
The Lefm (T ) calculated with (Eqn. 8.8.8) and Dm (Eqn. 8.4.10) from Koop et al. (2000) was
approximated in Khvorostyanov and Curry (2009b) by the polynomial of the fourth order:
Lefm (T ) = cL 0 + cL1Tc + cL 2 Tc2 + cL 4 Tc4 . (8.8.12a)

80 280 CNT, KS98–KC00–09

70 270 Paramet., K (2000)

260 Chukin et al. (2010)
Temperature (C)

60 250 Clegg et al. (1995)

Lm(cal g–1)

240 δaw,hom
50 aw(Tm) = eis/ews(HW)
230 aw(Tm) = eis/ews(MK05)
40 PK97, Lm(T)
220 δaw,hom
30 Joh94, Lm(T)
Joh94, aver.
210
20 (8.8.8), KC09–K00
200
DD63, Lm(T) (8.8.11), aw = (eis)/(ews) 190 aw(Tf,hom)
10 180
DD63, Lm–aver Param. (8.8.12b) – (8.8.11)
0 170
160 180 200 220 240 260 280 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2
Temperature (K) Water saturation ratio SW or activity aW
(a) (b)

Figure 8.14. (a) Various Lm(T) and Lmef(T). The three functions Lm(T) are parameterizations from
Dufour and Defay (1963, DD63) down to 220 K, from Johari et al. (1994) down to 170 K,
and from Pruppacher and Klett (1997) down to 228 K. The four effective (averaged) Lmef(T) are
calculated with new (Eqn. 8.8.11) with awi (T ) = eis( T ) /ews( T ) using (Eqns. 3.10.24), (4.4.2),
and (4.4.4) for eis(T) and ews(T) by Murphy and Koop (2005); calculated with (Eqn. 8.8.8) as in
Khvorostyanov and Curry (2009b) with (Eqn. 8.8.8) for Dm from Koop et al. (2000) (KC09-K00);
Johari’s (1994) parameterization averaged analytically as described in KC09b, and Lmef(T) averaged
as described in Dufour and Defay (1963, DD63). Parameterization (Eqn. 8.8.12b) is marked
with asterisks. (b) melting temperatures Tm(Sw) in equilibrium with ice calculated with various
methods: parameterization from Koop et al. (2000, param., K00); calculation with CNT from
Khvorostyanov and Sassen (1998) and Khvorostyanov and Curry (2000) with (Eqn. 8.8.10b),
,cr (T ) = ( T / T0 )
M w Lmef / RT
Swhom , and (Eqn. 8.8.8) for Lmef from KC09b shown in Fig. 8.14b (CNT,
KS98-KC00-09); parameterization from Clegg et al. (1995); parameterization from Chukin et al.
(2010); and water activity aw(Tm) in equilibrium with ice calculated with (Eqn. 3.10.24) of Section
3.10 as aw(Tm) = eis(T)/ews(T) calculated with eis(T) and ews(T) from Wexler (1976) and Hyland and
Wexler (1983) (HW-76-83) and with eis(T), ews(T) from Murphy and Koop (2005, MK05) described
in Section 4.4.
350 Homogeneous Nucleation

The newer refinement showed that (Eqn. 8.8.11) can be well approximated by a simpler linear
parameterization
Lefm (T ) = cL 0 + cL1Tc , (8.8.12b)

with L (T ) in cal g , Tc in °C, cL0 = 79.7, and cL1 = 0.463. Fig. 8.14a shows that this parameteriza-
ef
m
−1

tion practically coincides with more exact calculations using (Eqns. 8.8.8) and (8.8.11).
A verification of (Eqns. 8.8.8) and (8.8.11) for Lefm (T ) and its parameterizations (Eqn. 8.8.12a) and
(8.8.12b) can be done by substituting these Lefm (T ) into the equations for the melting curve Sw(Tm) or
aw(Tm) and comparing them with the other curves aw(Tm) or Tm(aw) evaluated with various methods.
This is illustrated in Fig. 8.14b, which presents water activities or saturation ratios along the melt-
ing curve obtained with 6 different methods: a) calculation with (Eqn. 8.8.5) derived by the authors
, cr (Tm ) = ( T / T0 )
M w Lefm /RT
from this modified CNT, as described by Swhom , and Lefm (T ) from (Eqn. 8.8.11)
shown in Fig. 8.14b (marked as CNT, KS98-KC00-09); b) parameterization from Koop et al. (2000);
c) parameterization from Clegg et al. (1995) adapted from the textbook on chemical thermodynamics
(Klotz and Rosenberg, 1972), and based on the measurements:

log(aw ) = ac1 ∆T + ac 2 ∆T 2 + ac 3 ∆T 3 + ac 4 ∆T 4 + ac 5 ∆T 5 + ac 6 ∆T 6 , (8.8.13)

where DT = T0 − Tm is the melting point depression, ac1 = −4.2091 × 10−3, ac2 = −0.2152 × 10−5,
ac3 = 0.32233 × 10−7, ac4 = 0.3446 × 10−9, ac5 = 0.1758 × 10−11, and ac6 = 0.765 × 10−14; and d) param-
eterization from Chukin et al. (2010, 2012) in (Eqn. 8.7.12h) based on experimental data. The other
two curves for aw(Tm) are calculated much more simply using (Eqn. 8.8.9) and two different param-
eterizations for eis(T) and ews(T): from Wexler (1976) and Hyland and Wexler (1983) (label HW) and
from Murphy and Koop (2005, MK05) described in Section 4.4. The homogeneous freezing curve
aw(Tf,hom) is given for comparison and illustration of the difference between the freezing and melting
curves and of the water activity shift discussed later.
Fig. 8.14b plotted as Tm(Sw) shows that all of these 6 curves aw(Tm) are sufficiently close to each
other down to about 220 K or aw = 0.60, which supports the validity of (Eqn. 8.8.8) and (Eqn. 8.8.11)
for Lefm (T ) based on classical nucleation theory and the accuracy of Lefm (T ) parameterizations
(Eqn. 8.8.12a) and (8.8.12b). The discrepancies among several curves increase a little below 220 K
and aw < 0.60. This may indicate decreasing accuracy under such extreme conditions (low T or concen-
trated solutions with small aw) of the parameterizations of Dm(T) (Eqn. 8.4.10), some earlier param-
eterizations of pressures eis, ews, and the accuracy of the data given in the books on physical chemistry
and cited by Clegg et al. (1995). However, the close agreement between Sw(T) from (Eqn. 8.8.4) with
Lefm (T ) from (Eqn. 8.8.11) and eis, ews from MK05, and a wi (T) = eis(T)/ews(T) from (Eqn. 8.8.9) is seen
down to 170 K and aw = 0.45. Thus, Lefm (T ) determined from this extended classical nucleation theory
can be used for nucleation calculations down to these T and aw with sufficient accuracy.

8.8.3. Derivation from Classical Theory of the Water Activity Shift Method

The major factors of (Eqn. 8.8.2) for Swhom

, cr can be parameterized as functions of temperature. The tem-

perature dependence of various factors in (Eqn. 8.8.2) is shown in Fig. 8.14c, whereby calculations
are performed with rd = 0.05 μm and JhomV = 1 s−1. In the range 273.15 to 170 K, variations of all
parameters are not very large, aw (Tm ) = (T /T0 )1/ Gn decreases from 1 at T0 = 273.15 to 0.45 at 170 K.
8.8. Threshold or Critical Saturation Ratios for Homogeneous Freezing 351

Gn(T), awT(m), Hf,het , Hf,hom , Hv,fr

1.0 Gn(T)
(1/G)
0.9 awT(m) = (T/T0)
0.8 Hf,hom
0.7 Hf,het
0.6 Hv,fr
0.5
0.4
0.3
0.2
0.1
0.0
–0.1
160 180 200 220 240 260 280
Temperature (C)
(c)

Figure 8.14. (c) Temperature dependence of various factors in equations for critical temperatures
and saturation ratios (or water activities) of homogeneous ice nucleation, Tf,hom, Swhom , cr (T ) (Sections
8.7 and 8.8) and heterogeneous ice nucleation Tf,het, Swhet,cr (T ) (Sections 9.11 and 9.12) calculated
with the effective Lmef(T) defined by (Eqn. 8.8.11): Gn(T) in (Eqn. 8.6.15), Hv,fr, in (Eqn. 8.6.16),
Hf,hom, in (Eqn. 8.7.5), Hf,het in (Eqn. 9.11.4), and aw (Tm ) = (T /T0 )1/ Gn . Calculations are performed
with the drop radius r = 0.05 μm, Dp = 0, and for Hf,het: ssa = 76 dyn cm−2, active sites area aa = 0,
misfit strain e = 0 (so that Hv,fr is the same for heterogeneous and homogeneous nucleation),
Jf,het = 1 s−1, Jf,homV = 1 s−1. The values of Hf,hom, Hf,het, and Hv,fr are sufficiently smaller than 1,
so that expansions by Hf,hom in Chapter 8 and by Hf,het in Chapter 9 are justified.

The other parameters increase with decreasing T: Gn increases from 0.38 to 0.58, Hf,hom increases
from 0.148 to 0.322, and Hv,fr < 0.05 over the entire temperature range. Therefore, (Eqn. 8.8.2) can be
simplified by expansion of the exponents into the power series
1/ Gn
T  H v , fr H f ,hom 
Swhom
, cr ≈   1 + G + G  . (8.8.14a)
 T0   n n 

Only the first-order terms are kept in the expansion, since an estimate shows that the next terms give
a contribution of less than 3–6%. Thus, Swhom
, cr can be presented in the form

Swhom hom hom

, cr (T f ,hom ) ≈ S w , cr (Tm )(1 + ∆S w , cr ) = S w , cr (Tm ) + δ S w , cr .
m m
(8.8.14b)
ef
Here, Swm,cr (Tm ) = (T /T0 ) M w Lm / RT corresponds to the melting curve described earlier, and

δ Swhom hom
, cr = S w , cr (Tm ) ∆S w , cr ,
m
(8.8.15a)
hom
∆S w , cr = ( ∆Sw , J + ∆Sw ,rd + ∆Sw , p ). (8.8.15b)

(The components DSw,J, DSw,rd, and DSw,p, are defined in (Eqn. 8.8.17) and analyzed later). Thus,
δ Swhom hom
, cr = δ aw = S w , cr ∆S w , cr is the activity difference or the activity shift between the critical saturation
m

ratios or activities of melting and homogeneous freezing,

δ Swhom hom
, cr = δ aw ,hom = S w , cr (T f ,hom ) − S w , cr (Tm ),
m
(8.8.16a)

or, in terms of activities,

δ aw ,hom = aw (T f ,hom ) − aw (Tm ) = aw ,hom − aw (Tm ). (8.8.16b)
352 Homogeneous Nucleation

The physical meaning of these quantities is simple: They describe the freezing point depression due
to the presence of solute at each temperature expressed in terms of d aw,hom. Fig. 8.14b shows that the
curves aw(Tf,hom) and aw(Tm) are “quasi-parallel” and the freezing curve can be obtained by shifting
the melting curve as a whole toward greater aw by a shift d aw,hom, which is illustrated at T = 235 K and
210 K in Fig. 8.14b. Koop et al. (2000), based on analysis of several empirical data sets, suggested
that an average shift daw,hom ≈ 0.305 can be representative for various substances and conditions.
Equations (8.8.2), (8.8.3), (8.8.14a), (8.8.14b), (8.8.15a), and (8.8.15b) show that the critical
humidity Swhom , cr (T f ,hom ) and the shift daw,hom in reality are more complicated quantities, depending on

several factors, and extended classical theory provides more precise descriptions. Fig. 8.14d shows
the shifts of water activity daw,hom = aw,hom(Tf,hom) − aw(Tm) calculated with (Eqns. 8.8.15a), (8.8.15b),
(8.8.16a), and (8.8.16b) for two nucleation rates, Jf,homV = 10−6 s−1 and Jf,homV = 1 s−1, with V for the
drops with two radii, r = 0.02 μm and 5 μm. Calculations are compared with the three experimental
data sets that were retrieved from the data on Tf,hom(aw,hom) by Larson and Swanson (2006) and Bertram
et al. (2000) for ammonium sulfate and Koop et al. (2000) for sulfuric acid. The experimental shifts
daw,hom were calculated as the difference in activities between each individual experimental point
Tf,hom(aw,hom) from the freezing data sets and the same temperature at the melting curve Tm(aw,m).
Given for comparison are also two average constant shifts, daw,hom = 0.305 recommended in Koop
et al. (2000), and daw = 0.246 determined by Zuberi et al. (2002) for heterogeneous nucleation.

Larson–2006 JV = 10–6 s–1, r = 5µm

0.50 Bertram–2000 JV = 1 s–1, r = 5µm
Koop–2000 JV = 1 s–1, r = 0.02µm
0.45 δaw,hom = 0.305 JV = 10
–6 –1
s , r = 0.02µm
activity shifts, δaw,hom

δaw,hom = 0.246
0.40

0.35

0.30

0.25

0.20
170 180 190 200 210 220 230 240
(d)

Figure 8.14. (d) The shifts of water activity d aw,hom = aw,hom(Tf,hom) − aw(Tm) calculated with equations
of extended CNT (Eqns. 8.8.15a), (8.8.15b), (8.8.16a), and (8.8.16b) described in Section 8.8 for two
nucleation rates, Jf,homV = 10−6 s−1 and Jf,homV = 1 s−1, with the volume V for the drops with two
radii, r = 0.02 μm and 5 μm. The three experimental data sets were retrieved from the data on
Tf,hom(aw,hom) by Bertram et al. (2000) and Larson and Swanson (2006) for ammonium sulfate and
Koop et al. (2000) for sulfuric acid. The experimental shifts d aw,hom were calculated using the
freezing Tf,hom(aw,hom) and melting Tm(aw,m) points from these data sets as the difference in activities
for each individual experimental point Tf,hom(aw,hom) on the freezing curve and the corresponding
temperature at the melting curve Tm(aw,m). Given for comparison are also two average constant
shifts, d aw,hom = 0.305 recommended in Koop et al. (2000), and d aw = 0.246 determined by Zuberi
et al. (2002) for heterogeneous nucleation.
8.8. Threshold or Critical Saturation Ratios for Homogeneous Freezing 353

Fig. 8.14d shows a noticeable scatter of the experimental points of d aw, most of them are located
in the range 0.3 < d aw,hom < 0.36. This picture agrees with Swanson (2009) who compared many
experimental data sets on Tf,hom obtained with different devices, also found a noticeable scatter in the
shifts of activities, and noticed that a better average shift could be 0.32, which is closer to Fig. 8.14d.
As could be expected, the shifts calculated from classical nucleation theory substantially depend
on both the nucleation rate Jf,hom and the radius of freezing particles and vary from a minimum of
0.27 at Jf,homV = 10−6 s−1, r = 5 μm to 0.42 at Jf,homV = 1 s−1, r = 0.02 μm. The calculated from CNT
shift d aw,hom decreases by 0.05–0.1 when Jf,hom decreases by 6 orders of magnitude, and by 0.1–0.12
when the radius increases from 0.02 μm to 5 μm. This indicates that more precise calculations of the
nucleation thresholds for polydisperse aerosols and various cooling rates should be based on classical
nucleation theory rather than on some constant average shift d aw,hom. This is especially true for small
particles with radii ∼ 0.01–0.05 μm that nucleate ice in cold clouds. The submicron haze particles in
cirrus, polar stratospheric clouds or diamond dust may freeze at substantially greater d aw,hom—i.e.,
at lower temperatures than those determined in the laboratory conditions for the larger particles with
r = 5–20 μm. The lower freezing temperature for submicron particles was illustrated in Fig. 8.6b. The
lowering of the freezing temperature with increasing cooling rate was also determined experimen-
tally (e.g., Cziczo and Abbatt, 1999; Martin, 2000; Kashchiev, 2000).

8.8.4. Effects of Various Factors on the Critical Humidity Swhom

, cr

The equations derived earlier allow estimation of the contribution of various terms to the critical
humidity and water activity shift. The correction to, or the shift in, the critical saturation ratio δ Swhom
, cr
H f ,hom ,
in (Eqns. 8.8.15a) and (8.8.15b) includes three terms, ∆Sw , J =
Gn

ρ w AK 3.6 × 10 −5 Rv ∆ρ∆p
∆Sw ,rd = ~ , ∆Sw , p = . (8.8.17)
ρi rd Trd T ρ w ρi
The terms DSw,J, DSw,rd, and DSw,p describe respectively the effects of the finite cooling rate Jf,hom, the
finite radius of the freezing particle, and the effect of external pressure. If we express the temperature
via supercooling DT, so that T = T0 − DT, and DT << T0, then the factor T/T0 in (Eqn. 8.8.14a) can be
also expanded in a power series:
Swhom
, cr ≈ 1 + ∆S w , T + ∆S w , J + ∆S w , rd + ∆S w , p ,
(8.8.18)

and DSw,T is
1 ∆T Lef ∆T
∆Sw ,T = − =− m 2 . (8.8.19)
Gn T Rv T

For very slow processes, when Jf,hom → 0 and ln(Jf,hom) → −∞, it is seen from (Eqn. 8.7.5) that Hf,hom → 0,
and at atmospheric pressure, Dp = 0, it follows from (Eqn. 8.8.3) that
M w Lefm /RT
hom
 T   rfr  
S w , cr =   exp    . (8.8.20)
 T0   rd  
354 Homogeneous Nucleation

As discussed in Section 8.7, this equation for the bulk substance (rd = ∞ and exp(rfr/rd) = 1) describes
the melting curve Sw(Tm) or Tm(Sw) and the term with rfr/rd describes the effect of the drop size. An
estimate shows that Swhom, cr increases by 0.075–0.15 for rd = 0.02–0.01 μm—i.e., the curvature correc-

tion DSw,rd = (rw /ri)AK /rd ≈ 7.5 − 15% gives a noticeable effect in the case with homogeneous nucle-
ation, and gradually vanishes at rd > 0.5−1 μm.
Each of the terms in (Eqns. 8.8.17) and (8.8.18) is a function of temperature, and these expressions
resemble previous empirical parameterizations of Swhom , cr for homogeneous ice nucleation in the form

of polynomials of temperature described in Section 8.4 (e.g., Sassen and Dodd, 1988, 1989; Heyms-
field and Miloshevich, 1995):
3

, cr = ∑ AkT T .
Swhom (8.8.21a)
k

k =0

Koop et al. (1998, 1999) and Bertram et al. (2000) parameterized the critical saturation ratio over ice
Sihom
, cr as polynomials of the saturated vapor pressure ews, and Koop et al. (2000) parameterized it via

water activity. Kärcher and Lohmann (2002a,b) suggested an empirical linear parameterization for
Sihom
, cr (T ) that is very close to Sassen and Dodd (1989). Thus, (Eqns. 8.8.17) and (8.8.18) serve as a

physical justification for previous empirical parameterizations and as a basis for their improvement.
Based on (Eqns. 8.8.17) and (8.8.18), the terms ( ∆Sw ,rd + ∆Sw , p ) can be added to the T-polynomial
(Eqn. 8.8.21a) to account for the curvature and pressure effects in the simple parameterizations, so
that it can be presented in the form
Swhom 2
,cr = A0 T + A1T T + A2 T T + ∆S w ,rd + ∆S w , p . (8.8.21b)

However, (Eqns. 8.8.2) and (8.8.3) are sufficiently simple for direct use in cloud and climate models
and analysis of the chamber experiments and show that there are several other dependencies, indicat-
ing that the critical humidities are not functions only of temperature. The dependencies on rd and Dp
show that Swhom
, cr depends on the size of a freezing particle and on the external pressure, in agreement with

experimental data (e.g., Kanno and Angell, 1977; Miyata et al., 2001, 2002). In addition, (Eqns. 8.8.2
and 8.8.3) show that the measured threshold saturation ratio depends on the nucleation rate Jf,hom—i.e.,
on the cooling rate. All these factors may at least partially explain the differences in Sihom, cr determined

by various experiments. The critical values of the ice saturation ratio can be obtained from the relation
Sihom hom
, cr = S w , cr (ews /eis ). (8.8.21c)

8.8.5. Calculations of Critical Relative Humidities over Water and Ice

Calculations of the critical values of RHW and RHI for homogeneous nucleation were performed
with (Eqn. 8.8.3) and the following set of parameters in the baseline case: ssa = 76 dyn cm−2, Dp = 0,
and two prescribed values of the homogeneous nucleation rate, so that Jf,homV = 10−6 s−1 and 1 s−1,
which characterize slow and fast freezing rates respectively, and V was calculated for rd = 5 μm. The
averaged Lm (T ) was calculated as described in the previous section.
ef

The RHW and RHI for the baseline case are shown in Fig. 8.15. The general feature of RHW is a
monotonic decrease with decreasing temperature from ∼100% at T ∼ −40 °C to ∼ 72–82% at −75 °C.
The corresponding RHI increases from 145–155% at −40 °C to 165–175% at −75 °C, which arises
from a combination of the temperature dependence of RHW and ews(T)/eis(T). Fig. 8.15a shows that
the expansion (Eqn. 8.8.18) is a reasonable approximation at these two nucleation rates. The values of
8.8. Threshold or Critical Saturation Ratios for Homogeneous Freezing 355

105
Jf,hom*V = 10–6 s–1
100 Jf,hom*V = 1 s–1
Expansion (8.8.18)
95

Critical RHW
90
SD89
85 B00
K00
80
KL02
75
–80 –70 –60 –50 –40 –30
Temperature (C)
(a)
175

170

165
Critical RHI (%)

160

155

150

145

140
–80 –70 –60 –50 –40 –30
Temperature (C)
(b)
1E+10
1E+9
1E+8
1E+7 RHW (Jf,hom
1E+6 *V = 10–6 s–1)
1E+5
Jf,hom*V (s–1)

1E+4 RHW(Jf,hom*V = 1 s–1)

1E+3
1E+2 RHW = 101 %
1E+1
1
0.1
1E–2
1E–3
1E–4
1E–5
1E–6
1E–7
–80 –70 –60 –50 –40 –30
Temperature (C)
(c)

Figure 8.15. Critical RHW (a) and RHI (b) for homogeneous ice nucleation calculated with (Eqn. 8.8.3)
for r = 5 μm and the other parameters as in Fig. 8.14, compared with expansion (Eqn. 8.8.18) and with
parameterizations by Sassen and Dodd (1989, SD89), Koop et al. (1999, 2000, K00), Bertram et al.
(2000, B00), and Kärcher and Lohmann (2002a, KL02) with their RHI or RHW recalculated to the
corresponding RHW or RHI as described in the text. (c) Verification of the solutions: homogeneous
nucleation rates Jf,homV calculated using (Eqn. 8.6.21) with these RHW(T) in Fig. 8.15a corresponding to
Jf,homV = 10−6 s−1 and 1 s−1, and with RHW = const = 101%. From Khvorostyanov and Curry (2009b),
J. Geophys. Res., 114, D04207, reproduced with permission of John Wiley & Sons, Inc.
356 Homogeneous Nucleation

RHW and RHI calculated here are compared with 4 parameterizations from (Sassen and Dodd, 1989,
SD89), (Koop et al., 1999, 2000, K00), (Bertram et al., 2000, B00), and (Kärcher and Lohmann,
2002a, KL02), whereby the RHW and RHI given in these works are recalculated to the corresponding
RHI and RHW as RHI cr = RHWcr (ews /eis ) . Agreement of the present calculations with the previous
parameterizations is sufficiently good, and the difference generally does not exceed 3–5%. The
curves calculated here with Jhom = 10−6 and 1 s−1 and rd = 5 μm differ by not more than 5% and bracket
these parameterizations—in particular, because the cited chamber experiments were performed with
particles of comparable rd ∼ 2–6 μm.
However, even this small difference in humidity causes great differences in the nucleation rates. To
illustrate the important role of humidity in the homogeneous freezing process and to verify the calcu-
lated RHWcr, the reverse calculation was performed as shown in Fig. 8.15c; that is, the product of the
nucleation rate and the volume, Jf,hom(T, RHWcr)V, for rd = 5 μm was calculated using the same equations
for Jf,hom and DFcr as in Fig. 8.15a, but with the two critical values of RHWcr (T) from Fig. 8.15a as input.
This calculation yields Jf,homV = const = 10−6 s−1, and 1 s−1 (Fig. 8.15c) for the two different critical val-
ues. This result was compared with Jf,hom(T, RHWcr)V calculated with RHWcr = const = 101% and also
presented in Fig. 8.15c. The nucleation rate with RHW = 101% is very high at T < −75 to −50 °C but falls
below 10−3 s−1 at T > −40 °C, which is similar to several experimental data sets compiled in (Pruppacher
and Klett, 1997, Chapter 7). This behavior is typical at constant relative humidity; however, if humidity
is close to the critical value or slightly above it, the T-dependence of the nucleation rate is smooth, in
contrast to the explosive increase predicted by the classical theory based on rcr with T-dependence but
without Sw-dependence.
The critical humidities also depend on the particle radius, which is illustrated in Fig. 8.16,
where the results of calculations with 0.05 mm and 5 mm for two values of JhomV = 10−6 and 1 s−1 are

10–6 s–1, 0.05µm

115 200
1 s–1, 0.05µm
110 10–6 s–1, 5µm 190
105 1 s–1, 5µm
Critical RHW (%)

Critical RHI (%)

100 180
95
170
90
85 B00, RHW(RHI) 160
80 B00, aw
SD89 150
75
KL02
70 140
–80 –70 –60 –50 –40 –30 –80 –70 –60 –50 –40 –30
Temperature (C) Temperature (C)
(a) (b)

Figure 8.16. Dependence of homogeneous freezing RHW (a) and RHI (b) on the particle radius
(0.05 μm vs. 5 μm) calculated using (Eqn. 8.8.3) at two nucleation rates Jf,homV = 10−6 s−1, and
Jf,homV = 10−6 s−1, compared to parameterizations by Sassen and Dodd (1989, SD89), Kärcher and
Lohmann (2002, KL02), and RHI and aw from Bertram et al. (2000, B00). From Khvorostyanov
and Curry (2009b), J. Geophys. Res., 114, D04207, reproduced with permission of John Wiley &
Sons, Inc.
8.9. Parcel Model Simulations of the Kinetics of Homogeneous Ice Nucleation 357

presented and again compared to parameterizations (SD89), (B00), and (KL02). Fig. 8.16 shows
that when the particle radius increases by 2 orders of magnitude, RHW decreases by 7–15%; a cor-
responding decrease is 17–27% for RHI. The dependence of the homogeneous freezing rate on the
particle radius is in agreement with experimental data (e.g., Pruppacher and Klett, 1997, Miyata et al.,
2001, 2002). It is seen in Figs. 8.15 and 8.16 that both humidities calculated with rd = 5 mm are close
to the parameterizations (SD89), (B00), (KL02), and (K00). This agreement provides empirical sup-
port for the validity of this theoretical method for evaluation of the critical humidities. However, the
critical humidities strongly depend on the prescribed nucleation rate and on the radius of freezing
particles, which is usually not accounted for in the empirical parameterizations.

8.9. Parcel Model Simulations of the Kinetics of Homogeneous Ice Nucleation

The kinetics of homogeneous ice nucleation can be studied numerically or analytically or by combin-
ing both methods. For numerical analysis, the cloud models can be used, and the major tool in these
studies is usually a cloud parcel model that is used for simulation of a cloud process involving ice
nucleation.

8.9.1. Parcel Model Description

The simplest model used in cloud physics for simulation of various cloud properties is a parcel
model. This is a model of a rising air parcel where droplets or crystals may form. A parcel model is
a zero-dimensional or Lagrangian model, where all variables depend only on time t and the depen-
dence on the coordinates is excluded. There are two major types of parcel models: with and without
entrainment. Models with entrainment account for the partial exchange of the rising or descending
parcel with environment by the air, heat, moisture, aerosol, and condensed matter, droplets, and
crystals. The rates of this exchange are parameterized with various mixing lengths. Examples of
parcel models of these types are described in Flossmann, Hall, and Pruppacher (1986), Young (1993),
and Pruppacher and Klett (1997). Models without entrainment (e.g., Lin et al., 2002 and references
herein) consider an isolated adiabatic air parcel that rises and cools, which causes nucleation and
growth of the drops and crystals.
We describe here an example of such a parcel model with spectral bin microphysics. The microphys-
ical formulation used here is similar to the Eulerian numerical 1D, 2D, and 3D models with spectral
bin microphysics developed and used previously for the simulation of mixed-phase clouds of various
types (e.g., Buikov and Pirnach, 1973, 1975; Young, 1974a; Buikov and Khvorostyanov, 1976, 1977;
Hall, 1980; Khvorostyanov, 1982, 1987, 1995; Kondratyev and Khvorostyanov, 1989; Kondratyev,
Ovtchinnikov and Khvorostyanov, 1990a,b; Khvorostyanov and Khairoutdinov, 1990; Khairoutdinov
and Khvorostyanov, 1991; Feingold et al., 1994; Pirnach and Krakovskaya, 1994, 1998; Jensen et al.,
1994, 1998, 2005; Ovtchinnikov et al., 2000; Khvorostyanov et al., 2001, 2003, 2006; Fridlind et al.,
2004; Khain et al., 2004; Flossmann and Wobrock, 2010; Curry and Khvorostyanov, 2012), with some
differences owing to the Lagrangian approach in the parcel model. The dynamics in parcel models
is usually parameterized by prescribing vertical velocity w, which is usually constant in time. The
main thermodynamic equations are the prognostic equations for supersaturation and temperature. This
358 Homogeneous Nucleation

system of equations includes terms that describe the phase transitions and is closed using the kinetic
equations of condensation and deposition for the drop and ice crystal size distribution functions that
account for nucleation, and equations for the droplet and crystal growth rates, as described in Chapter 5.
Here we exclude from consideration coagulation among droplets and aggregation between the droplets
and crystals, sedimentation, entrainment, turbulent exchange, etc. to isolate the effects directly related
to nucleation processes. We describe in the following text the parcel model based on spectral bin micro-
physics, developed by the authors of this book and used for studies of the kinetics of ice nucleation
(Khvorostyanov and Curry, 2005a, hereafter KC05a).
The heat balance is calculated using the equation for the temperature T in a wet adiabatic process
considered in Chapters 3 and 5, and has the form similar to (Eqn. 3.11.43):
dT L L
= −γ a w + e I con + s I dep . (8.9.1)
dt c p ρa c p ρa

This equation is solved along with the integral ice supersaturation (Eqn. 8.5.18) that is required to
describe crystal growth:

1 dyi′ y′ t rmax
= c1i w − i (4π Dv )  ∫ rc , ef (t, t0 ) ∫ fa (ra ) v (ra )
(1 + yi′) dt 1 + yi′  0 rmin

( t

0 )
× Jf , hom (t0 ) exp − ∫ J f , hom (t ′)v (ra )dt ′ dra dt0  .

(8.9.2)

Evolution of the crystal fc(rc) and droplet fd(rd) size spectra is described using two kinetic equations
for these spectra in the form (Eqn. 5.5.5) as in KC05a:

∂ fc ∂  drc 
+  fc  = ψ fc (rc , t ) (8.9.3a)
∂t ∂rc  dt 
∂ fd ∂  drd 
+  fd  = ψ fd (rd , t ). (8.9.3b)
∂t ∂rd  dt 

Here we consider homogeneous ice nucleation at cold temperatures and not very vigorous updrafts
when the haze solution particles freeze at water subsaturation, so that the drops do not form and
(Eqn. 8.9.3b) for drops is not used. In deep convective clouds with the stronger updrafts of sev-
eral meters per second, water saturation may be reached, homogeneous ice nucleation may occur
simultaneously with drop activation, and (Eqn. 8.9.3b) may be needed. The terms of growth rates in
(Eqn. 8.9.3a,b) are calculated using (Eqn. 5.1.46) for drd/dt and (Eqn. 5.2.24) for drc/dt:

drd c s Dv ρ ws 4 Dv
= 3w w , c3 w = , ξcon = (8.9.4a)
dt rd + ξcon ρ w Γ1 α cVw
drc c s D ρD D4 Dv
= 3i i , , ,c3i = v , is , , ξ dep = (8.9.4b)
dt rc + ξ dep ρi Γ 2 α d Vw

The crystal nucleation term can be calculated as

ψfc = ∆N c , fr ( ∆t )/∆rc /∆t . (8.9.5)

where DNc,fr is the number concentration of the crystals nucleated in a time step Dt and calculated using
(Eqn. 8.3.9). In the finite difference scheme, the crystal source term is calculated for the homogeneous
8.9. Parcel Model Simulations of the Kinetics of Homogeneous Ice Nucleation 359

freezing mode as yfc = DNc,fr /Drc /Dt, where Drc denotes the smallest size range of crystal radii
(0.1–1 μm). The crystal size spectrum includes 30 radius intervals with 10 increments of 0.1–1 μm,
and the next 20 increments increasing logarithmically to 100–350 μm. Numerical experiments show
that this size division allows coverage of both small and large size ranges without losing accuracy.

8.9.2. Simulation Results

To simulate the ice crystal nucleation process, the parcel model was run for 1 hour with most initial
conditions specified following the Cirrus Parcel Model Comparison Project (CPMCP) (Lin, Starr,
et al., 2002), and varying some parameters to estimate the sensitivity of the results. We describe and
compare the results for three values of vertical velocity, w = 4, 20, and 100 cm s−1, two values of
the initial temperature, T0 = −40 °C and −60 °C (CPMCP), and two values of the aerosol concen-
tration, Na = 200 cm−3 (CPMCP) and Na = 500 cm−3. For convenience of comparison at different
temperatures, the initial RHW0 was chosen in such a way that at both temperatures homogeneous ice
nucleation processes occurred at comparable times. This required RHW0 = 90% for T0 = −40 °C and
RHW0 = 78% for T0 = −60 °C. The initial pressure p0 was specified to be 340 hPa. The parcel model
includes the option of isolating specific ice crystal nucleation modes, by turning off the other modes.
In this chapter, we deal with the homogeneous freezing of deliquescent haze particles. The haze size
spectrum was assumed to be a lognormal size spectrum of soluble particles with a mean geometric
radius of 0.02 μm and dispersion ss = 2.5. The time steps were 0.01–0.2 s in the main program, but
the time step can be divided further in the nucleation or condensation subroutines to meet the stability
conditions. The accuracy of the calculations was controlled by comparing the total number of crystals
nucleated with those obtained by integration over the size spectrum of the grown crystals at the end of
a parcel run. If the error exceeded 5% (especially at low temperatures), the time and radius steps were
varied and several additional runs were performed until the error became less than 5%.
Figs. 8.17 and 8.18 illustrate the effect of the vertical velocity (w = 4 and 20 cm s−1) on the kinetics
of homogeneous freezing at T0 = −40 °C and Na = 200 cm−3. It is seen that the nucleation process
has two branches. At the ascending branch, the first term on the right-hand side of (Eqn. 8.9.2)
with supersaturation generation dominates. Therefore, the relative humidity and both supersatura-
tions, sw and si, increase from the initial values to the maximum values reached at the time tm. At the
descending branch at t > tm, the RHW, sw and si decrease due to domination of the second term on
the RHS of (Eqn. 8.9.2) with supersaturation depletion. This feature is similar to the drop activation
process (Chapter 7). As a result of adiabatic cooling, RHW increases in the ascending branch and
reaches at w = 4 cm s−1 a maximum of 97.7% at a time of about 35 min and then begins to decrease
(Fig. 8.17a). The water and ice supersaturation pass the first critical values in the ascending branch
of sw,cr1 = −4.2% and si,cr1 = 42% at about t ≈ 22 min, reach maxima of −2.45% and 46% respectively
at t = 33.67 min, and then decrease in the descending branch to the second critical values reached
at about t = 40 min (Fig. 8.18a). Note that the change in ice supersaturation Dsi = si,max − si,cr1 ≈ 4%,
or Dsi/si,max is less than 10%. Thus, it can be assumed that nucleation occurs at almost constant ice
supersaturation.
Noticeable ice nucleation with w = 4 cm s−1 begins after the first critical point sw,cr1 at t ≈ 22 min
(Fig. 8.17d,e,f). At the time of maximum RHW and sw, the crystal critical radius and energy reach a
minima of 1.36 × 10−7 cm and 1.38 × 10−12 erg, respectively (Fig. 8.17b,c), while the nucleation rate
360 Homogeneous Nucleation

100 1E–6

Relative humidiy over water (%)

95

Critical radius (cm)

90
85 w = 4 cm s–1
80 w = 20 cm s–1

75
70
65
60 1E–7
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(a) (b)

Nucleation rates per particle Jf,hom (s–1)

1E–10 1E–3
1E–4
Critical free energy (erg)

1E–5
1E–6
1E–11 1E–7
1E–8
1E–9
1E–10
1E–12 1E–11
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(c) (d)
0.1 1E+3
Polydisperse nucleation rates

Crystal concentration (L–1)

1E–2 1E+2
dNc/dt (cm–3 s–1)

1E–3 1E+1
1E–4 1
1E–5 0.1

1E–6 1E–2

1E–7 1E–3

1E–8 1E–4
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(e) (f)

Figure 8.17. Kinetics of homogeneous nucleation at T0c = −40 °C, RHW0 = 90%, p0 = 340 hPa,
Na = 200 cm−3 and two vertical velocities, w = 4 cm s−1, and w = 20 cm s−1. (a) Relative humidity over
water RHW; (b) critical radius rcr; (c) critical free energy DFcr; (d) homogeneous Jf,homra3 nucleation
rates for a particle with radius of 0.11 μm; (e) polydisperse nucleation rates, Rf,hom = dNfr/dt, defined
by (Eqn. 8.3.10); (f) crystal concentration. From Khvorostyanov and Curry, Atmos. Chem. Phys.
(2012), reproduced with permission.
8.9. Parcel Model Simulations of the Kinetics of Homogeneous Ice Nucleation 361

Supersaturation over water and ice (%)

50 60
si,cr
40

Crystal mean radius (µm)

50
30
si(w = 4) w=4
20 40
sw(w = 20) w = 20
10
30
0 sw,cr
–10 20
–20 sw(w = 4)
si(w = 20) 10
–30
–40 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(a) (b)
0.16
Crystal supersaturation relaxation 100
8
6
0.12 4
IWC (g m–3)

time (min)

2
0.08
10
8
6
0.04 4

0.00 1
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(c) (d)
100 0.06
Amount of condensed ice (%)

80 0.05
Vapor excess (g m–3)

60 0.04

40 0.03

20 0.02

0 0.01
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(e) (f)

Figure 8.18. Comparison (continuation) of kinetics of homogeneous ice nucleation at w = 20 cm s−1

(solid circles) and w = 4 cm s−1 (triangles) at −40 °C and the other parameters as in Fig. 8.17.
(a) Supersaturations over water, sw, and ice, si, % and corresponding critical supersaturations;
(b) crystal mean radius, μm; (c) ice water content, g m−3; (d) crystal supersaturation relaxation
time, min; (e) relative amount of condensed ice, %; (f) vapor excess, mg m−3. From Khvorostyanov
and Curry, Atmos. Chem. Phys. (2012), reproduced with permission.
362 Homogeneous Nucleation

per particle (Jf,homrd3, with rd = 0.11 μm) and the polydisperse nucleation rate Rf,hom reach a maxima
of 4.90 × 10−6 s−1 and 4.93 × 10−4 cm−3 s−1 (Fig. 8.17d,e). The values of rcr and DFcr are substantially
greater, while Jf,homrd3 and Rf,hom are smaller at the later times, although the temperature continues to
decrease. This illustrates an important key role of humidity in ice nucleation.
In contrast to the drop activation, the nucleation process continues also after tm along the descend-
ing branch till the point when the second critical values sw,cr and si,cr are reached, and ceases after that.
The entire nucleation process takes 15–20 min with w = 4 cm s−1, and the final crystal concentration is
66 L−1 (Fig. 8.17f). The crystal mean radius grows by t = 1 hour to 53 microns, the ice water content
(IWC) grows to 0.044 g m−3 and the supersaturation relaxation time tfc decreases from more than
3 hours at the beginning of nucleation to 17 min by the end of simulation. This indicates that deposition
of the vapor is not instantaneous and a significant amount of vapor is not deposited for a long time.
For quantitative illustration, it is convenient to introduce the two quantities, vapor excess, Mv, and the
relative amount, or percentage of uncondensed ice, Frcon, as

M v = ρ v si , Frcon = IWC /( IWC + M v ) × 100. (8.9.6)

These quantities characterize the mass of uncondensed ice (mass of ice supersaturation) and the frac-
tion of condensed ice. In a bulk model with instantaneous condensation and deposition, Mv = 0, and
Frcon = 100%, but it is not so in this microphysical model with explicit calculation of supersaturation.
Fig. 8.18f shows that the vapor excess is greater or comparable to IWC and the fraction of condensed
ice is less than 50% during 30 minutes. This means that optical thickness and emissivity of cirrus
clouds at the initial stages of formation are significantly smaller than would be in a bulk model, the
radiation of the cloud is not radiation of the black body, and the optical properties should be accord-
ingly corrected (decreased) in climate and weather forecast models.
The corresponding curves for the case with w = 20 cm s−1 (solid circles in Figs. 8.17 and 8.18)
show that increased w causes much faster nucleation, which takes now about 5 min. The other fea-
tures of the nucleation process are qualitatively similar, with some quantitative differences. The mini-
mum critical radius and energy become smaller, the nucleation rates increase by almost two orders of
magnitude, and the final crystal concentration increases by almost an order of magnitude to 649 L−1,
∼10 times greater than with w = 4 cm s−1; that is, Nc increases with w approximately as Nc ∼ w3/2 in this
case. Because of more numerous crystals and their competition for vapor, the mean crystal radius is
smaller than with w = 4 cm s−1, but the relaxation time tfc is also smaller with a minimum of 2.6 min.
The deposition is faster in this case, but the vapor excess and percentage of condensed ice are still
smaller for 15–20 min that would be in a bulk model (Fig. 8.18e,f).
A comparison of the results with Na = 200 cm−3 (described earlier) and 500 cm−3 at T0 = −40 °C,
w = 4 cm s−1 is shown in Figs. 8.19 and 8.20; all the other parameters are as before. This comparison
shows that a significant increase in Na causes a very weak effect on nucleation kinetics and all the
quantities. Nucleation with higher Na begins and ceases a little earlier, and the resulting crystal con-
centration is 68.6 L−1 vs. 66 L−1 with Na = 200 cm−3; that is, an increase of 2.5 times in Na causes an
increase of only 4% in Nc. This remarkable insensitivity to the initial concentration of deliquescent
freezing aerosol indicates that a “saturation” with respect to Na occurs at much smaller values of Na
than is typical for the upper troposphere.
The fraction of nucleated haze particles (the ratio Nc/Na), is really tiny (66 L−1)/(200,000 L−1) =
3.3 × 10−4, which is much smaller than the typical fraction of CCN activated into drops, ∼0.3–0.7
(see Chapter 7).
8.9. Parcel Model Simulations of the Kinetics of Homogeneous Ice Nucleation 363

100 1E–6
Relative humidiy over water (%) 95
90

Critical radius (cm)

85 Na = 200 cm–3
80 Na = 500 cm–3

75
70
65
60 1E–7
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(a) (b)

Nucleation rates per particle Jf,hom (s–1)

1E–10 1E–4

1E–5
Critical free energy (erg)

1E–6

1E–7
1E–11
1E–8

1E–9

1E–10

1E–12 1E–11
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(c) (d)

1E+2
1E–3
Polydisperse nucleation rates

Crystal concentration (L–1)

1E+1
1E–4
dNc/dt (cm–3 s–1)

1
1E–5
0.1
1E–6
1E–2

1E–7 1E–3

1E–8 1E–4
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(e) (f)

Figure 8.19. Comparison of homogeneous nucleation kinetics at Na = 200 cm−3 and 500 cm−3.
The other parameters are T0c = −40 °C, RHW0 = 90%, p0 = 340 hPa, and w = 4 cm s−1. (a) Relative
humidity over water RHW; (b) critical radius rcr; (c) critical free energy DFcr; (d) homogeneous
nucleation rates Jf,homra3 for a particle with radius ra = 0.11 μm; (e) polydisperse nucleation rates,
Rf,hom = dNfr/dt, defined by (Eqn. 8.3.10); (f) crystal concentration. From Khvorostyanov and Curry,
Atmos. Chem. Phys. (2012), reproduced with permission.
364 Homogeneous Nucleation

Supersaturation over water and ice (%)

50 60
si,cr
40

Crystal mean radius (µm)

50
30
si (Na = 200) Na = 200
20 si (Na = 500) 40 Na = 500
10 sw (Na = 200)
sw (Na = 500) 30
0 sw,cr
–10
20
–20
–30 10
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(a) (b)

0.05 2

Crystal supersaturation
relaxation time (min)
0.04 100
8
IWC (g m–3)

6
0.03
4

0.02 2

0.01 10
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(c) (d)

80 0.06
Amount of condensed ice (%)

0.05
Vapor excess (g m–3)

60

0.04
40
0.03

20
0.02

0 0.01
0 10 20 30 40 50 60 30 40 50 60
Time (min) Time (min)
(e) (f)

Figure 8.20. Comparison (continuation) of homogeneous ice nucleation kinetics at Na = 200 cm−3
(solid circles) and 500 cm−3 (triangles), at −40 °C and the other parameters as in Fig. 8.19.
(a) Supersaturations over water, sw, and ice, si, and critical supersaturations, sw,cr, and ice, si,cr, %;
(b) crystal mean radius, μm; (c) ice water content, g m−3; (d) crystal supersaturation relaxation
time, min; (e) relative amount of condensed ice, %; (f) vapor excess, mg m−3. From Khvorostyanov
and Curry, Atmos. Chem. Phys. (2012), reproduced with permission.
8.9. Parcel Model Simulations of the Kinetics of Homogeneous Ice Nucleation 365

This very small fraction of freezing solution particles is explained by the following factors:
a) very strong negative feedback by the water supersaturation: even a small decrease in sw causes a
significant decrease in the nucleation rate Jf,hom, where the dependence on sw is exponential with a
large coefficient, as will be demonstrated in Section 8.10; b) much faster crystal growth at high ice
supersaturation than drop growth at small water supersaturation, so that the second term in (Eqn. 8.9.2)
with supersaturation absorption becomes greater than the first term with production much faster than
in the case with drops activation and their much slower growth at small water supersaturation. This
explanation, based on numerical simulations, is confirmed by analytical parameterizations described
in the next section.
The effect of temperature is illustrated in Figs. 8.21 and 8.22, where a comparison is made for the
cases −40 °C and −60 °C, at w = 4 cm s−1, and all the other parameters as before. The initial RHW0 =
78% at −60 °C, and maximum RHW = 89%. The critical sw,cr = −17% and si,cr = 49% vs. −4% and 42%,
respectively, at T0 = −40 °C; maximum supersaturations are sw,max = −11% vs. −2.4% and si,max = 62.1% vs.
si,max = 46.0% at T = −40 °C. Thus, the critical and maximum water supersaturations (negative) decrease
and ice supersaturations increase with decreasing temperature. Minimum critical radius and energy are
comparable at both temperatures, while the nucleation rates increase 4–7 times at lower T. The crystal
concentration grows almost 4 times to 242 L−1 at lower T (Fig. 8.21f), but crystal growth is slower.
Therefore, the mean radius is about 4 times smaller and the fraction of condensed ice is lower by the
end of the simulation at t = 1 hour, and the supersaturation relaxation times are close, ∼15–17 min, since
the increase in crystal concentration is balanced by a decrease in the mean radius (Fig. 8.22). Thus, the
amount of condensed ice is again smaller than would be the case in a bulk model, the cloud radiates less
than a black body, and the error of the black-body approximation increases with lowering temperature.
Some properties of the nucleation rates allow simplifications of the nucleation equations. The
nucleation rates are very small at all stages of the process (Jf,homrd3 < 10−5 − 10−4 s−1 with the radius
of a deliquescent haze particle rd = 0.11 μm, and Rf,hom < 10−3 − 10−1 cm−3 s−1 even at their maxima;
see Figs. 8.17, 8.19, 8.21, units (d) and (e)). Therefore, the expressions introduced in Section 8.3 can
be substantially simplified since

( t
) t
exp − ∫ J f ,hom (t ′)v(rd )dt ′ ≈ 1 − ∫ J f ,hom (t ′)v(rd )dt ′.
0 0
(8.9.7)

The probability Pf,hom(rd, t) (Eqn. 8.3.6) of homogeneous freezing of a haze particle or a drop with
radius rd and volume v(rd) during the time interval from t0 to t can be simplified as

( t
) t
Pf ,hom (rd , t ) = 1 − exp − ∫ J f ,hom (t ′) v (rd ) dt ′ ≈ ∫ J f ,hom (t ′) v (rd ) dt ′.
t0 t0
(8.9.8)

Equation (8.3.9) for crystal concentration Nc,hom in a polydisperse aerosol (deliquescent haze particles
or drops) can be simplified as
rmax

N c ,hom (t ) = ∫
rmin
Pf ,hom (rd , t ) fd (rd ) drd ,

rmax t
≈∫ ∫ J f ,hom (t ′)v (rd ) fd (rd ) dt ′drd . (8.9.9)
rmin t0
366 Homogeneous Nucleation

Relative humidiy over water and ice (%)

100 1E–4
95
90

Critical radius (cm)

1E–5
85
80
75
1E–6
70 T = –40 C
T = –60 C
65
60 1E–7
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(a) (b)

Nucleation rates per particle Jf,hom (s–1)

1E–9 1E–4

1E–5
Critical free energy (erg)

1E–6
1E–10
1E–7

1E–8
1E–11
1E–9

1E–10

1E–12 1E–11
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(c) (d)
0.1 1E+3
Polydisperse nucleation rates

Crystal concentration (L–1)

1E–2 1E+2
dNc/dt (cm–3 s–1)

1E–3 1E+1

1E–4 1

1E–5 0.1

1E–6 1E–2

1E–7 1E–3

1E–8 1E–4
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(e) (f)

Figure 8.21. Comparison of homogeneous nucleation kinetics at T = −40 °C and −60 °C. The other
parameters are RHW0(−40 °C) = 90% and RHW0(−60 °C) = 78%, p0 = 340 hPa, and w = 4 cm s−1.
(a) Relative humidity over water RHW; (b) critical radius rcr; (c) critical free energy DFcr;
(d) homogeneous Jf,homra3 nucleation rates for a particle with radius of 0.11 μm; (e) polydisperse
nucleation rates, Rf,hom = dNfr/dt, defined by (Eqn. 8.3.10); (f) crystal concentration. From
Khvorostyanov and Curry, Atmos. Chem. Phys. (2012), reproduced with permission.
8.9. Parcel Model Simulations of the Kinetics of Homogeneous Ice Nucleation 367

70 60
Supersaturation with respect to si(–60)
60
si,cr(–60)

Crystal mean radius (µm)

50
50
water and ice (%)

40 T = –40 C
si,cr(–40) 40
30 T = –60 C
si(–40)
20 30
10
sw(–40) 20
0 sw,cr(–40)
–10 sw(–60)
10
–20 sw,cr(–60)
–30 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(a) (b)

0.1 2
Crystal supersaturation
relaxation time (min)
100
8
IWC (g m–3)

6
0.01
4

1E–3 10
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(c) (d)

80 0.10
Amount of condensed ice (%)

Vapor excess (g m–3)

60

40 0.01

20

0 0.00
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(e) (f)

Figure 8.22. Comparison of homogeneous nucleation kinetics at T = −40 °C and −60 °C (continuation).
The other parameters are RHW0(−40 °C) = 90% and RHW0(−60 °C) = 78%, p0 = 340 hPa, w = 4 cm s−1.
(a) Supersaturations over water, sw, and ice, si, and critical supersaturations, sw,cr, si,cr, %; (b) crystal
mean radius, μm; (c) ice water content, g m−3; (d) supersaturation relaxation time, min; (e) relative
amount of condensed ice, %; (f) vapor excess, mg m−3. From Khvorostyanov and Curry, Atmos.
Chem. Phys. (2012), reproduced with permission.
368 Homogeneous Nucleation

The crystal nucleation rate (Eqn. 8.3.10) in a polydisperse aerosol can be simplified as:
dN f ,hom rmax
R f ,hom (t ) = =∫ fd (rd ) v (rd ) J f ,hom (t )drd . (8.9.10)
dt rmin

These simplifications can be very useful since they significantly shorten the number of arithmetic oper-
ations in numerical modeling and allow analytical calculations. These features of the homogeneous ice
nucleation kinetics are used for development of the analytical ice nucleation parameterization derived
next in Section 8.10.

8.10. Analytical Parameterization of Homogeneous Ice Nucleation

Kinetics Based on Classical Nucleation Theory

Previous parameterizations of homogeneous ice nucleation suitable for the cloud and climate models
described in Section 8.4 have mostly been semi-empirical, whereby they used either experimental
data or elements of the classical nucleation theory along with the supersaturation equation and a
few additional heuristic relations tuned by fitting either experimental data or data from parcel model
simulations. In this section, a new parameterization of homogeneous nucleation kinetics is derived,
which is based directly on the extended classical nucleation theory and on the analytical solutions of
the supersaturation equation.

8.10.1. General Features of Homogeneous Ice Nucleation Kinetics

The general features of homogeneous ice nucleation kinetics described in Section 8.9 are illustrated
with better resolution in Fig. 8.23, which shows parcel model simulations of a typical general evo-
lution of water and ice supersaturations and crystal concentration. The symbols tcr,1 and tcr,2 denote
the 1st and 2nd times when the critical (threshold) ice supersaturations si,cr1 and si,cr2 are reached
(i.e., the start and end of nucleation), and tmax is the time when maximum ice and water supersatu-
rations, si,max and sw,max, are reached. A comparison of Fig. 8.23 with the drop nucleation kinetics
described in Chapters 6 and 7 shows that homogeneous ice nucleation has features that are both
similar to and different from drop nucleation. In both cases, supersaturation increases due to adiabatic
cooling updraft, but in contrast to drop activation, ice nucleation begins at water subsaturations of
a few percent (about −3 to −4%), at the time tcr,1, when some critical ice supersaturation si,cr1 ∼ 0.42
(42%) is reached.
As in the case with drop activation, the si(t) and sw(t) curves consist of two branches with increas-
ing and decreasing supersaturations. However, in contrast to drop activation, nucleation does not
cease at tmax, when maximum si,max and sw,max are reached. Only about 50–60% of the final crystal
concentration has been nucleated by this time (the ellipse in Fig. 8.23b), and nucleation continues
along the branch with decreasing supersaturation to the point tcr,2, si,cr2 when si(t) again intersects the
line si,cr(t). It is seen that an increase in both sw and si is linear almost to the point of maximum.
As discussed in Section 8.7, an important feature of ice nucleation is that an increase in si from
minimum si,cr1 ∼ 0.42 to the maximum smax = 0.46 is only 0.04, less than 10% of the initial crit-
ical value si,cr1; that is, crystal growth proceeds at almost constant supersaturation. With varying
8.10. Analytical Parameterization of Homogeneous 369

Supersaturation over water and ice (%)

60 70
tmax, si,max Nc(t)
50

Crystal concentration (L–1)

si,cr 60
40
tcr,1 tcr,2 50
30 si,cr1 si,cr2
40 sw,max
20
si 30
10 sw
sw,max 20
0 sw,cr
–10 sw,cr1 sw,cr2 10

–20
0 10 20 30 40 50 60 26 28 30 32 34 36 38 40
Time (min) Time (min)
(a) (b)

Figure 8.23. General features of homogeneous ice nucleation kinetics (evolution of water and ice
supersaturations and crystal concentration) illustrated with a parcel model run with the parameters:
initial temperature Tc = −40 °C, sw(t = 0) = −0.1 (−10%), lognormal size spectrum of haze
particles with mean geometric radius of 0.02 μm and concentration Na = 200 cm−3. The symbols
tcr,1 and tcr,2 (marked with ellipses) denote the first and second times when critical (threshold) ice
supersaturations si,cr1 and si,cr2 are reached—that is, the start and end of nucleation; tmax is the time
when maximum ice and water supersaturations si,max, sw,max are reached; sw,cr, si,cr, denote the curves
of critical (threshold) water and ice supersaturations. From Khvorostyanov and Curry, Atmos.
Chem. Phys. (2012), reproduced with permission.

temperature, pressure, vertical velocity, and aerosol properties, this picture varies quantitatively, but
the general qualitative features remain similar. Accounting for these features allows significant sim-
plifications of calculations of kinetics of the homogeneous ice nucleation.
The basic equations describing the kinetics of homogeneous ice nucleation include the integro-
differential equations for water and ice supersaturations derived in Section 8.5, and the equation for
crystal radius growth rate taking into account the kinetic effects, also given in Section 8.5. Addition-
ally, we need the equation for the homogeneous nucleation rate of haze particles taking into account
solution effects, the equation for the critical supersaturation sw,cr, and the equations for the critical
radius and energy of homogeneous nucleation with some simplifications that are described in the
following text.

8.10.2. The Freezing Rate and Its Simplification

The equation for the critical water supersaturation sw = Sw − 1 follows from (8.8.2):
1/ Gn
swhom hom
, cr = S w , cr − 1 = [(T/T0 ) exp( H v , fr + H f ,hom )] − 1, (8.10.1)

where Hv,fr and Hf,hom are defined in (Eqns. 8.6.16) and (8.7.5). The corresponding ice saturation
ratio Si and supersaturation si can be obtained using (Eqn. 8.8.21c). In the following text, we denote
the critical supersaturation of homogeneous freezing with the superscript “hom” to distinguish from
370 Homogeneous Nucleation

heterogeneous freezing considered in Section 10.1. Hereafter, we use a common notation ra for the
radius of the aerosol particles, and fa(ra) for their size spectra.
The polydisperse freezing rate Rf,hom = dNc(t0)/dt0 can be calculated using the classical nucle-
ation theory as described by (Eqn. 8.3.10) in Section 8.3. It was illustrated in Section 8.9
(Figs. 8.17, 8.19, and 8.21) that at typical cooling rates (w), the homogeneous nucleation rates per
particle, Jf,homra3 < 10−5 − 10−4 s−1 and Rf,hom < 10−3 − 10−1 cm−3 s−1, and the inner integral in the expo-
nent in (Eqn. 8.3.10) is close to 1. Therefore, the approximation (Eqn. 8.9.10) can be used as a good
approximation for Rf,hom:
dNfr rmax
R f ,hom (t0 ) =
dt
= ∫
rmin
dra fa (ra ) v (ra ) J f ,hom (t0 ). (8.10.2)

This expression can be further simplified if the depletion of v(ra) and fa(ra) are small during freezing,
which is usually a good approximation with abundant concentrations of the freezing particles
rmax
R f ,hom (t0 ) ≈ J f ,hom (t0 ) ∫ dra fa (ra ) v (ra ) = N a va J f ,hom (t0 ). (8.10.3)
rmin

where va is the mean aerosol volume averaged over the aerosol size spectrum:
rmax
4 1
∫r
3
va = π a af (ra )dra . (8.10.4)
3 Na rmin

In general, Na and va depend on time; however, the fraction of haze particles nucleated into crystals is
very small compared to the initial haze population. Therefore, Idep from (Eqn. 8.5.16) can be further
simplified assuming Na ≈ const, va ≈ const :
4π Dv ρis t

I dep ≈ yi′ N a va ∫ rc ,ef (t , t0 ) J f ,hom (t0 ) dt0 , (8.10.5)

Γ2 0

where rc,ef(t, t0) is defined in (Eqn. 8.5.14).

8.10.3. Separation of Temperature and Supersaturation Dependencies

The nucleation rate Jf,hom(T, sw) defined by (Eqn. 8.6.21) depends on temperature and water satu-
ration ratio or supersaturation. Analytical solution of the supersaturation equation requires some
simplifications; in particular, it is desirable to find a representation of Jf,hom with separated T- and
sw-dependencies.
The quantity Jf,hom can be calculated using (Eqn. 8.3.5) from the classical nucleation theory as
derived in Section 8.3:

 ∆F (T ) + ∆Fcr (T , Sw , ∆p, ra ) 
J f ,hom = Chom exp  − act  , (8.10.6)
 kT
where Chom is defined in (Eqn. 8.3.5a), DFact and DFcr are the activation and critical energies of an ice
germ freezing, and we wrote explicitly about their arguments according to Section 8.6. The energy
DFact is expressed as a function of temperature. The critical free energy DFcr of homogeneous freez-
ing can be expressed via the critical radius rcr of a nucleated ice germ; it is also a function of T. The
analytical expressions for rcr and DFcr were generalized in Section 8.6, taking into account the effect
8.10. Analytical Parameterization of Homogeneous 371

of the solution in haze particles, so that they can be expressed as the functions of T and the water satu-
ration ratio Sw simultaneously. The effects of pressure in (Eqn. 8.6.18) for DFcr become substantial
only at very high pressures that can be achieved in laboratory experiments and so can be neglected
under atmospheric conditions. Neglecting also the effects of curvature for submicron particles—i.e.,
assuming Hv,fr = 0 in (Eqn. 8.6.18), we can use (Eqn. 8.6.20) for DFcr. Here, we express DFcr via water
supersaturation sw using (Eqn. 8.6.20) and the relation Sw = 1 + sw:

(16π / 3)σ is3

∆Fcr = 2 , (8.10.7)
 ef  T0 G 
 ρi Lm (T ) ln  (1 + sw ) n  
 T 
where Gn(T) = RT/(MwLmef) is a dimensionless parameter defined in (Eqn. 8.6.15); the other quantities
were defined in Section 8.6.
The equation for DFcr can be transformed so that the dependencies of T and sw will be separated.
It was found in observations and model simulations (see Section 8.9) that the homogeneous freezing
of haze particles in cirrus clouds usually occurs at small water subsaturations of −2% to −10%—i.e.,
sw = −2 × 10−2 to −10 × 10−2, so that |sw| << 1. Since |sw| << 1, we can expand the denominator in
(Eqn. 8.10.7) into a power series in sw. The logarithmic term can thus be transformed as

T  T 
ln  0 (1 + sw )Gn  ≈ ln  0 (1 + Gn sw ) 
T  T 
T  T  Gn s w 
≈ ln  0  + Gn sw = ln  0   1 + , (8.10.8)
T  T  ln(T0 / T ) 
where we use a relation ln(1 + Gnsw) ≈ Gnsw for |sw| << 1 and Gn ∼ 0.4 − 0.6. Substituting this expan-
sion into (Eqn. 8.10.7), we obtain

∆Fcr (T , sw ) ≈ ∆Fchom
r ,0 (T )[1 − κ s sw ], (8.10.9)
where
2Gn 2 RT
κs = = , (8.10.9a)
ln(T0 /T ) M w Lefm ln(T0 /T )

(16π /3)σ is3

∆Fcrhom
,0 = . (8.10.10)
[ ρi L (T ) ln(T0 /T )]2
ef
m

That is, ∆Fcrhom

,0 is the critical energy for pure water defined by (Eqn. 8.10.7) but at Sw = 1 or

sw = 0—i.e., it depends only on temperature but does not depend on supersaturation. For T ∼ −50 °C,
an estimate gives Gn ∼ 0.5, and ks ∼ 5, that is, with sw = −3 × 10−2 (−3%), this yields kssw ∼ −0.15 << 1.
An estimate shows that the second-order term in expansion by kssw in (Eqn. 8.10.9) contributes ∼
2–3%; therefore, retaining only the first term in expansion (Eqn. 8.10.9) is justified. The substitution of
(Eqn. 8.10.9) into (Eqn. 8.10.6) yields

J f ,hom (T , sw ) = J (0)
f ,hom (T ) exp[us hom (T ) sw (t )], (8.10.11a)
sw ( t )
J f ,hom (T , sw ) = J (0)
f ,hom (T )[ bhom (T )] , (8.10.11b)
372 Homogeneous Nucleation

so that Jf,hom can be written such that the sw-dependence is presented in the exponential or power law
forms via the parameters bhom and ushom:

∆Fcrhom
,0 2Gn
us hom (T ) =
kT ln(T0 /T )
2R ∆Fcrhom hom
2 N Av ∆Fcr ,0
=
,0
= , (8.10.12)
kM w Lm ln(T0 /T )
ef
M w Lm ln(T0 /T )
ef

bhom (T ) = exp(us hom ), (8.10.12a)

(0)
where J (T ) is the nucleation rate for pure water—i.e., is defined by (Eqn. 8.10.6) with Sw = 1
f ,hom

or sw = 0, and NAv is the Avogadro number. Thus, Jf,hom(T, sw) is presented in a separable form as a
(0)
product of the two factors: J f ,hom depends on T but does not depend on sw, and the dependence on
sw is separated into the exponent in (Eqn. 8.10.11a). An estimate shows that at cirrus conditions
ushom ∼ (2 − 4) × 102 >> 1. Since sw < 0 in the nucleation process, the value of ushomsw is negative. If
sw ∼ − (4 to 10) × 10−2, as estimated earlier under typical nucleation conditions, the value of |ushomsw| > 10,
and we have an inequality exp(ushomsw) << 1.
Numerical simulation with the parcel model shows that changes in J (0) f ,hom (T ) in (Eqns. 8.10.11a) and

(8.10.11b) are several orders of magnitude smaller than variations in exp(ushomsw). This is illustrated in
Fig. 8.24, which shows that J (0f ,hom
)
(T ) ~ (4 − 5) × 10 5 cm −3 s −1 and only slightly varies during the nucle-
ation event, while J f ,hom (T , sw ) ~ 10 in maximum and varies (decreases from maximum) by 10 orders
of magnitude at the beginning and at the end of nucleation. This is caused by the effect of exp(ushomsw),
which reaches in maximum ∼10−5 at t = 34.5 min, the time of maximum of sw, and decreases by
10 orders of magnitude otherwise. Fig. 8.24 shows that: a) the ratio J f ,hom (T , sw )/ J (0) f ,hom (T ) is very

close to exp(ushomsw), supporting the validity of the analytical representation of the nucleation rate

1E+6
1E+5
1E+4 J(0)f,hom(T, sw = 0)
Nucleation rates (cm–3 s–1)

1E+3 Jf,hom(T, sw)

1E+2 exp(ushom*sw)
1E+1
1 Jf,hom/J(0)f,hom
0.1
1E–2
1E–3
1E–4
1E–5
1E–6
1E–7
1E–8
1E–9
0 10 20 30 40 50 60
Time (min)

Figure 8.24. Homogeneous nucleation rates J f ,hom (T , sw ), J (0) f ,hom (T , sw = 0), their ratio
J f ,hom (T , sw )/J (0)
f ,hom (T , sw = 0) , and exp(ushomsw) that determines this ratio. Calculations for the same
conditions as in Fig. 8.23. It is seen that Jf,hom/J(0)f,hom is very close to exp(ushomsw), which is a
good approximation to this ratio. From Khvorostyanov and Curry, Atmos. Chem. Phys. (2012),
reproduced with permission.
8.10. Analytical Parameterization of Homogeneous 373

in (Eqn. 8.10.11a) in the separable form by T and sw; b) the major variations in Jf ,hom (T , sw ) occur
due to variations in humidity via sw, while changes due to the temperature are several orders smaller.
Therefore, the deposition integral Idep in (Eqn. 8.10.5) can be presented in the form that substantially
simplifies calculations:
4π Dv ρis t

f ,hom ∫ rc , ef (t , t 0 ) exp[us hom sw (t 0 )] dt 0 ,

N a va J (0)
I dep = yi′ (8.10.13)
Γ2 0

or in the other form, introducing the integral J0i as

4π Dv
I dep = yi′ N a va J (0)
f ,hom J 0 i , (8.10.13a)
Γ2
t

J 0 i = ∫ rc ,ef (t , t0 ) exp[us hom sw (t0 )] dt0 . (8.10.13b)

0

8.10.4. The Evolution of the Nucleation Rate and Crystal Concentration

The integro-differential supersaturation (Eqn. 8.5.18) for the case of homogeneous ice nucleation is
similar to that used for drop activation in Chapters 6 and 7. In the theory of drop activation, the time
dependence of supersaturation from the beginning of activation to the maximum at t = tmax is often
approximated by a liner function, sw = c1ww, which is determined by the first term on the RHS of
(Eqn. 8.5.18). The initial value is assumed to be zero since drop activation begins at a very small posi-
tive sw. In contrast, as Fig. 8.23 shows, homogeneous ice nucleation begins at slightly negative water
supersaturation sw but high ice supersaturation si and proceeds at almost constant si.
We seek a solution to the supersaturation equation similar to that used for the drops as a linear by
t approximation for the differential supersaturations sw, si and a quadratic by t approximation for the
integral supersaturations yw, yi, but with the initial critical (threshold) values, which account for the
specifics of ice nucleation:

si (t ) = yi′(t ) = sihom
,cr + a1i t , yi (t ) = sihom 2
,cr t + ( a1i /2)t . (8.10.14)

sw (t ) = yw′ (t ) = swhom
,cr + a1 w t , yw (t ) = swhom 2
,cr t + (a1 w /2)t . (8.10.15)

As described in Chapter 7, the parameters a1w and a1i can be specified in various ways, which yield
the lower and upper limits of the solution. An approximation that gives a lower bound of the solu-
tion can be obtained with a1w = c1ww. The difference between the limits is on the order of 10–20% or
smaller, but for simplicity we will consider the approximations a1w = c1ww and a1i = c1iw as prompted
by the supersaturation equations (Eqns. 8.5.1), (8.5.2), and (8.5.18), and described by (Eqns. 8.10.14)
and (8.10.15). As discussed earlier, Fig. 8.23 shows that the increase Dsi = c1iw(tmax − t0) ∼ 0.04 (4%)
during ice nucleation from t0 to tmax is much smaller than the initial critical si,cr ∼ 0.042 (42%) or
maximum si,max ∼ 0.046 (46%). Since Dsi << si,cr, we can neglect Dsi in yi in (Eqn. 8.10.14), which
was also neglected in the previous parameterizations of homogeneous ice nucleation (Kärcher and
Lohmann, 2002a,b; Ren and MacKenzie, 2005). We also assume that si(t) ≈ const ≈ si,cr and neglect
increases in si during the nucleation event. In contrast, we cannot neglect increases in sw—i.e., the term
374 Homogeneous Nucleation

Dsw = c1ww(tmax − t0)—because water supersaturation varies substantially and determines variations in
Jf,hom (see Fig. 8.24). Thus, we use si, yi, sw, and yw as

si (t ) = yi′(t ) = sihom
,cr , yi (t ) = sihom
,cr t , (8.10.16a)
hom hom 2
sw (t ) = yw′ (t ) = s w ,cr + c1w wt , yw (t ) = s w ,cr t + (c1w w /2)t . (8.10.16b)

Substitution of sw(t) into the separable nucleation rate in (Eqn. 8.10.11a) yields Jf,hom(T, sw) as a func-
tion of time in the form

J f ,hom [T , sw (t )] = J (0) hom

f ,hom (Tcr ) exp(us hom s w , cr ) exp(us hom c1 w wt ), (8.10.17a)

where ushom is defined in (Eqn. 8.10.12). We assumed here, based on Fig. 8.24, that the major time
dependence is determined by sw, and the temperature dependence is determined near Tcr. Dividing
Jf,hom(t) by Jf,hom(t0) at some initial t0, we obtain the time dependence Jf,hom(t) of the form

J f ,hom (t ) = J f ,hom (t0 ) exp[us hom c1w w(t − t0 )]. (8.10.17b)

For t0 = tcr, (Eqn. 8.10.17b) can be rewritten with (Eqn. 8.10.17a) as

J f ,hom [sw (t )]
ln = us hom c1w w(t − tcr ) = us hom (T )[sw (t ) − swhom
, cr ]. (8.10.17c)
J f ,hom [swhom
, cr (tcr )]

Using the relation following from the Clausius–Clapeyron equation of Chapter 3,

sw + 1 = ciw (si + 1), ciw = exp[− Lm (T0 − T ) /Rv T0 T ], (8.10.17d)

where Rv is the vapor gas constant and T0 = 273.15, we express sw in (Eqn. 8.10.17c) via the ice satu-
ration ratio Si = si + 1 and obtain
J f ,hom [sw (t )]
ln = us hom (T )ciw (T )[ Si (t ) − Sihom
, cr ].
(8.10.17e)
J f ,hom [swhom
, cr (tcr )]

This expression has the same form as (Eqn. 8.4.32) hypothesized by Barahona and Nenes (2008, BN08)
by analogy with the separable representation of the heterogeneous nucleation rate in Khvorostyanov
and Curry (2004b). Now, this functional form is derived from the theory of homogeneous freezing and
the empirical coefficient bt introduced in BN08 and fitted with experimental data is expressed from the
extended classical nucleation theory as bt (T) = ushom(T)ciw(T).
Equation (8.10.17b) can also be written as
J f ,hom (t ) = J f ,hom (t0 ) exp[(t − t0 ) /τ nuc ,hom ], (8.10.18)

where we introduce the characteristic “homogeneous nucleation time” tnuc,hom

−1
 −1
∆Fcrhom
,0 2Gn 
τ nuc ,hom = (c1w wus hom ) = c1w w 
 kT ln( T0 /T ) 
kLef ln(T0 /T ) −1 M w Lm ln(T0 /T )
ef
= (c1w w)−1 m = ( c1 w ) . (8.10.19)
2 Rv ∆Fcrhom 2 N Av ∆Fcrhom
w
,0 ,0

The temporal dependence of Jf,hom(t) in (Eqn. 8.10.18) was hypothesized by Ford (1998a,b) and
utilized by Kärcher and Lohmann (2002a,b) and Ren and MacKenzie (2005); the time tnuc,hom was
8.10. Analytical Parameterization of Homogeneous 375

introduced as some empirical parameter and was found by fitting to some auxiliary relations (Eqns.
8.4.17)–(8.4.19). Here, the time dependence of Jf,hom(t) and the nucleation time tnuc are derived
in terms of the extended classical nucleation theory with a dependence on Sw. Equation (8.10.19)
−1
shows that τ nuc ,hom ~ c1w w; that is, according to (Eqns. 8.4.17) and (8.4.18), t nuc hom is proportional
-1

to (dT/dt), in agreement with the temperature equation, the other factors in (Eqn. 8.10.19) determine
∂lnJhom/∂T and the empirical coefficient ct in (Eqn. 8.4.18). Thus, the approach based on extended
classical nucleation theory provides a theoretical basis for the functional forms hypothesized in the
previous parameterizations by Ford (1998a,b), Kärcher and Lohmann (2002a,b), Ren and MacKenzie
(2005), and Barahona and Nenes (2008) and allows their expression in terms of fundamental ther-
modynamic parameters. This is again in agreement with the correspondence principle (Section 1.2),
which states that the particular theories and empirical parameterizations can be derived from a more
general theory, which does not reject the previous theories and parameterizations but unifies and
clarifies them and allows us to express their empirical parameters via fundamental constants and
functions.
The linear approximation (Eqn. 8.10.16b) for sw(t) allows description of the time evolution of the
polydisperse nucleation rate Rf,hom(t) and crystal concentration Nc(t). Substitution of (Eqn. 8.10.17a)
into (Eqn. 8.10.3) yields
R f ,hom (t0 ) ≈ N a va J (0) hom
f ,hom (Tcr ) exp(us hom sw , cr ) exp( β hom t )

≈ N a va J (0)
f ,hom (Tcr ) exp[us hom s w (t )],
(8.10.20)
−1
β hom = us hom c1w w = τ nuc , hom . (8.10.21)

Integration over time gives Nc(t):

t

N c (t ) = ∫ R f ,hom (t ) dt
0

≈ N a va J (0) −1 hom
f ,hom (Tcr )β hom exp(us hom s w , cr )[exp( β hom t ) − 1]

= N a va J (0) −1 hom
f ,hom (Tcr ) β hom {exp[us hom sw (t )] − exp(us hom sw , cr )}, (8.10.22a)

which is the parameterization for Nc(t) that was sought.

The separation of the dependencies of Nc on sw and T allows introduction of the supersaturation
and temperature activity spectra of ice nuclei fs(T, sw) and fT(T, sw) by sw and T defined in (Eqns.
8.5.11) and (8.5.12). Differentiation of (Eqn. 8.10.22a) by sw and T yields

∂ Nc
φs (T , sw ) = ≈ N a va J (0) −1 hom
f ,hom (Tcr )(c1 w w) exp(us hom s w , cr ) exp( β hom t ), (8.10.22b)
∂ sw
∂ Nc
φT (T , sw ) = ≈ N a va J (0)
f ,hom (Tcr )
∂T
∂ −1
× {β hom exp(us hom swhom
, cr )[exp( β hom t ) − 1]}. (8.10.22c)
∂T
The activity spectrum fs(T, sw) characterizes the rate of ice nucleation with increasing humidity and
constant temperature, (similar to that considered for drop activation in Chapters 6 and 7), and the
spectrum fT(T, sw), vice versa, characterizes the rate of ice nucleation with decreasing temperature
376 Homogeneous Nucleation

and constant humidity. Such processes may occur under natural conditions of cirrus or mid-level
Ac-As clouds formation with advection of humid air and weak variations of T, as was observed, for
example, with lidar near Fairbanks (Sassen et al., 2006; Sassen and Khvorostyanov, 2008), or with
the advection of cold air and weak changes of humidity. Using (Eqns. 8.10.22b) and (8.10.22c), the
relative role of variations of the temperature and humidity can be estimated, or these processes can
be studied in isolation in a cloud chamber.
The relation between bhom and t determines the regime of growth of Nc with time. For example, at
T = −40 °C with us ∼ 250, c1w ∼ 10−5 cm−1, and w ∼ 10 cm s−1, an estimate gives bhom ∼ 2.5 × 10−2 s−1
−1
and τ nuc,hom = β hom ~ 40 s. Thus, for small times, t << β hom
−1
~ 40 s, (Eqn. 8.10.22a) gives a linear
growth of Nc(t) with time:

N c (t ) = N a va J (0) hom
f ,hom (Tcr )t exp(us hom s w , cr ). (8.10.23)

For large times, t >> β hom

−1
= 40 s , (Eqn. 8.10.22a) produces an exponential time dependence

N c (t ) = N a va J (0) hom
f ,hom (Tcr )τ nuc ,hom exp(us hom sw ,cr + β hom t )

~ exp[us hom sw (t )]. (8.10.24)

In this regime, ln[Nc(t)] ∼ t, which may explain the linear dependence of ln[Nc(t)] with the time seen
in the Figures of Section 8.9 with parcel model simulations.
It is interesting to note that (Eqn. 8.10.24) for homogeneous nucleation can be presented in the
form similar to some empirical parameterizations. We present Nc(t) in (Eqn. 8.10.24) as

N c (sw ) = exp(ln AM + us hom sw ), AM = N a va J (0)

f ,hom (Tcr )τ nuc ,hom . (8.10.25)

Using the relation (Eqn. 8.10.17d) as sw = ciwsi + (ciw − 1), we replace sw with si and obtain

N c (si ) = exp(aM + bM si ), bM = us hom ciw , (8.10.26a)

(0)
aM = ln AM + us hom (ciw − 1) = ln[ N a va J f ,hom (Tcr )τ nuc ,hom ] + us hom (ciw − 1) (8.10.26b)

The aerosol concentration Na is included in AM but can be placed also in front of the exponent as
N c (si ) = N a exp(aɶ M + bM si ), (8.10.26c)

aɶ M = ln[ va J (0)
f ,hom (Tcr )τ nuc ,hom ] + us hom (ciw − 1). (8.10.26d)

Thus, these theoretical parameterizations (Eqns. 8.10.26a–d) are written in the form similar to Meyers
et al. (1992) for heterogeneous nucleation, or in a modified form, proportional to Na, but all the
parameters are expressed now via the primary atmospheric and aerosol quantities. They are not con-
stant and substantially vary with temperature, aerosol volume, and cooling rate via w in ushom. Similar
formulations will be given in Chapters 9 and 10 for heterogeneous nucleation.
The consideration stated earlier is valid when the effects of the vapor depletion are not strong and
are neglected. However, if we consider the nucleation process at longer times and near the point of
the maximum supersaturations in the Figures of Section 8.9, the vapor depletion becomes substantial
and finally exceeds supersaturation production. Then, a more accurate consideration should include
evaluation of the deposition integral Idep and the supersaturation equation, as we did in Chapters 6 and
7 for drop activation, which is done in the following sections.
8.10. Analytical Parameterization of Homogeneous 377

8.10.5. Evaluation of the Deposition Integral Idep

Evaluation of Idep is analogous to that developed in Khvorostyanov and Curry (2008a, 2009a) for the
drop nucleation, described in Chapter 7; however, integration for ice nucleation is more complicated
due to the exponential activity spectrum and can be done following Khvorostyanov and Curry (2012).
Substitution of yi(t) from (Eqn. 8.10.16a) into (Eqn. 8.5.14) for rc,ef(t, t0) yields

{[(r0 + ξ dep )2 + Bi hom (t − t0 )]1/ 2 − ξ dep }2

rc ,ef (t , t0 ) = , (8.10.27)
[(r0 + ξ dep )2 + Bi hom (t − t0 )]1/ 2

where
Bi hom = 2ci 3 sihom
, cr .
(8.10.28)

To evaluate the integral in Idep in (Eqn. 8.10.13), we present rc,ef(t, t0) in (Eqn. 8.10.27) in the inte-
grand of (Eqn. 8.10.13) as a sum of three terms:
r 2 (t , t0 )
rc ,ef (t , t0 ) = = rc(1) (2) (3)
,ef + rc , ef + rc , ef , (8.10.29)
r (t , t0 ) + ξ dep

where
rc(1) 2
, ef (t , t 0 ) = [(r0 + ξ dep ) + Bi hom (t − t 0 )]
1/ 2
, (8.10.30a)

rc(2)
, ef (t , t 0 ) = −2ξ dep ,
(8.10.30b)
−1/ 2
rc(3) 2 2
, ef (t , t 0 ) = ξ dep [(r0 + ξ dep ) + Bi hom (t − t 0 )] . (8.10.30c)

Substitution of (Eqns. 8.10.29) and (8.10.30a), (8.10.30b), and (8.10.30c) into (Eqn. 8.10.13) for Idep yields

4π Dv ρis
I dep (t ) = yi ′ N a va J (0) hom
f ,hom exp(us hom sw ,cr ) J 0 i ,hom (t ), (8.10.31)
Γ2

where J0i,hom(t) represents a sum of the three terms:

3 3 t

J 0 i ,hom (t ) = ∑ J 0( ki ,hom
)
= ∑∫r (k )
c , ef (t , t0 ) exp(β hom t0 ) dt0 . (8.10.32)
k =1 k =1 0

Substitution of (Eqn. 8.10.29) with (Eqns. 8.10.30a), (8.10.30b), and (8.10.30c) into (Eqn. 8.10.32)
and evaluation of the integral J 0 i ,hom (t ) given by (Eqn. A.8.21) in Appendix A.8 yields

J 0 i ,hom (t ) = exp(β hom t )Ψ hom , (8.10.33)

where Ψhom is defined by the (Eqns. A.8.22)–(A.8.26),

Ψ hom = Ψ1hom + Ψ 2 hom + Ψ 3 hom , (8.10.34)

−3/ 2   3  3 
Ψ1hom = e λhom Bi1/hom
2
β hom  Γ  2 , λhom  − Γ  2 , λhom + β hom t   , (8.10.35)
 
−1
Ψ 2 hom = 2ξ dep β hom (e − βhom t − 1), (8.10.36)

2  1  1 
Ψ 3 hom = e λhom ξ dep (β hom Bi hom )−1/ 2  Γ  , λhom  − Γ  , λhom + β hom t   , (8.10.37)
 2  2 

β hom (r0 + ξ dep )2 (us hom c1w w)(r0 + ξ dep )2

λhom = = . (8.10.38)
Bi hom 2ci 3 sihom
, cr
378 Homogeneous Nucleation

Here, Γ(a, x) is the incomplete gamma function—its properties and asymptotics are defined in
Appendix A.8. Using (Eqn. 8.10.33) for J 0 i (t ) , and the relation ushomsw,cr + bhomt = ushomsw(t), the
deposition term Idep can be written as

4π Dv ρis
I dep (t ) = yi ′ (0)
( N a va J hom ) exp[us hom sw (t )]Ψ hom . (8.10.39)
Γ2

Note that the water supersaturation sw(t) at a time t is present in the exponent.
The function Ψhom defined by (Eqns. 8.10.34)–(8.10.37) can be transformed and reduced to the
functions more convenient for calculations. Using the recurrent relation for Γ(3/2, x) (the next and
subsequent relations for the gamma functions Γ(x, a) and the error function Φ(x) = erf(x) are from
Gradshteyn and Ryzhik, 1994, see Appendix A.8)

Γ (α + 1, λ ) = αΓ (α , λ ) + λ α e − λ , (8.10.40a)

and the relation between the gamma function and error function erf(x),

Γ (1 /2, λ ) = π [1 − erf ( λ )], (8.10.40b)

we can transform the gamma function in Ψ1hom into

3  1 1  π
Γ  , λ  = Γ  , λ  + λ 1/ 2 e − λ = [1 − erf ( λ )] + λ 1/ 2 e − λ . (8.10.41)
2  2 2  2
Substituting this relation into (Eqns. 8.10.35)–(8.10.37), we can rewrite Ψ1hom and Ψ3hom with use
of only erf(x) ≡ Φ(x) and without the gamma function, which is more convenient for applications:

Ψ1hom = e λhom Bi1/hom

2 −3/ 2
β hom {( π /2)[Φ( λhom + β hom t ) − Φ( λhom )] (8.10.42)
− λhom 1/ 2 1/ 2 − β hom t )
+e [λ hom − (λhom + β hom t ) e ]},

Ψ 3 hom = e λhom ξ dep

2
(β hom Bi hom )−1/ 2 π [Φ( λhom + β hom t ) − Φ( λhom )]. (8.10.43)

Then, the function Ψhom is expressed with use of only Φ(x) = erf(x):

Ψ hom = e λhom β hom

−1/ 2
π [Φ( λhom + β hom t ) − Φ( λhom )]
−1
× [(1 / 2) Bi1/hom
2
β hom 2
+ ξdep Bi−hom
1/ 2
]
+ Bi1/hom
2 −3/ 2
β hom [λ 1/ 2 − (λhom + β hom t )1/ 2 e − βhom t ]
−1
+ 2ξdep β hom (e − βhom t − 1). (8.10.44)

This expression can be further simplified by expressing the transcendent function erf(x) via the ele-
mentary function tanh(x) as suggested in Ghan et al. (1993) and used also in Chapter 6 for derivation
of the algebraic size and activity spectra for drop activation:

erf ( x ) ≈ tanh[(2 / π ) x ]. (8.10.45)

Then, Ψhom becomes

Ψ hom = e λhom β hom

−1/2
π [tanh(2 ( λ hom + β hom t ) /π ) − tanh(2 λhom /π )]
−1 −1/2
× [(1 / 2) Bi1/2 2
hom β hom + ξ dep Bi ]
1/2 − β hom t
+ Bi1/2 −3/2 1/2
hom β hom [ λ hom − ( λ hom + β hom t ) e −1
] + 2ξ dep β hom (e − βhomt − 1). (8.10.46)
8.10. Analytical Parameterization of Homogeneous 379

Now, with this Ψhom, the deposition integral Idep (Eqn. 8.10.39) is expressed only via the elementary
functions. Another transition to the elementary functions can be done using equations for erf(x)
and erfc(x) given in Ren and MacKenzie (2005, 2007) described by (Eqn. 8.4.28). In the next sec-
tions, the solutions of equations for supersaturation and crystal concentration will be expressed
via Ψhom. Although these expressions may look a little complicated, the advantages of analytical
representation (Eqns. 8.10.44) and (8.10.46) are that they allow us to reduce the unavoidable
errors caused by the finite difference representations and numerical calculations, and enable the
derivation of solutions for the asymptotic limits of Idep and Nc for diffusion and kinetics regimes
of crystal growth.

8.10.6. Solution of Equations for the Supersaturation and for Crystal Concentration

Substituting the expression for Idep (Eqn. 8.10.39) into the integral supersaturation (Eqn. 8.5.15),
multiplying it by (1 + yi′), and using the relation rv = ris(1 + yi′) yields

dyi′ Γ
= c1i w(1 + yi′ ) − 2 I dep
dt ρis
= c1i w(1 + yi′ ) − (4π Dv ) yi′( N a va J (0)
f ,hom ) exp[us hom s w (t )]Ψ hom . (8.10.47)

At time tmax with si,max and sw,max, there is a condition dsi/dt = dyi′/dt = 0; thus, the LHS of (Eqn.
8.10.47) is zero, which yields

exp[us hom sw ,max (tmax )] = c1i w(1 + si ,max )si−,max

1
(4π Dv )−1 ( N a va J (0) −1 −1
f ,hom ) Ψ hom . (8.10.48)

Now we can rewrite (Eqn. 8.10.3) for Rf,hom(t) using (Eqn. 8.10.17a) for Jf,hom as

R f ,hom (t0 ) ≈ N a va J hom (t0 ) = N a va J (0)

f ,hom exp[us hom sw (t 0 )]

= N a va J (0) hom
f ,hom exp[us hom sw , cr + β hom t 0 ]. (8.10.49)

The crystal concentration at the time tmax is obtained by integrating over t0

tmax

N c (tmax ) = ∫
tcr ,1
R f ,hom (t0 ) dt0 ,

(0)
≈ N a va J hom (T )β −1 exp[us hom sw ,max (tmax )]
× {1 − exp[− β hom (tmax − tcr ,1 )}
(0) −1
≈ N a va J hom (T )β hom exp[us hom sw ,max (tmax )]. (8.10.50)

−1
The last equation accounts for the fact that (tmax − tcr,1 ) >> β hom or bhom(tmax − tcr,1) >> 1 and Nc can be
written as in (Eqn. 8.10.24). Substituting exp[ushomsw(tmax)] from (Eqn. 8.10.48) into (Eqn. 8.10.50)
and using the approximate equality si ,max ≈ sihom
, cr due to small variations of si during nucleation as

discussed earlier, we obtain a parameterization of the crystal concentration in homogeneous freez-

ing nucleation:
hom −1 −1
N c (tmax ) = K gen (1 + sihom
, cr )( si ,cr ) Ψ hom , (8.10.51)

K gen = (4π Dv )−1 us−hom

1
(c1i /c1w ). (8.10.52)
380 Homogeneous Nucleation

Equation (8.10.51) gives Nc at the time tmax with maximum supersaturation—i.e., at the end of the
1st stage with increasing si. Some previous parameterizations assumed that Nc(tmax) at the time
tmax of maximum supersaturations is the final crystal concentration. However, as we have seen in
Fig. 8.23, during the descending branch at tmax < t < tcr,2, sw(t) decreases but still exceeds sw,cr; there-
fore, nucleation continues after tmax until tcr,2, and Nc(tmax) is approximately half the magnitude of the
total Nc,tot(tcr,2) after nucleation ceases at t > tcr,2. Evaluation of the 2nd stage at t > tmax with decreasing
supersaturation in principle can be done in a similar way as for t < tmax, although it is somewhat more
complicated. To simplify the solution, we can use the solutions for t = tmax and slightly tune them
using results of the parcel model runs. Their detailed analysis shows that the total Nc,tot(tcr,2) at t > tcr2,
when nucleation has ceased, is proportional to Nc(tmax):
N c ,tot ≈ K cor N c (tmax ) (8.10.53a)

Numerical experiments with the parcel model show that Kcor ∼ 1.8 to 2.2 (Fig. 8.23). A more precise
fit shows that this coefficient can be chosen as a function of the vertical velocity w as
K cor ( w) = 1.85 + (2 − 1.85w/wsc ) at w < 2 m s −1 , (8.10.53b)
−1
K cor ( w) = 2.0, at w≥2ms , (8.10.53c)

and wsc = 2 m s−1. An even simpler choice of the average Kcor ∼ 2, which takes into account that
about half of the crystals nucleate at decreasing supersaturation at tmax < t < tcr,2, gives satisfactory
results.
The method developed here enables estimation of the supersaturation relaxation time tfc and the
mean crystal radius rc at the time tmax and then after the end of nucleation. This can be done by equat-
ing in the supersaturation (Eqn. 8.5.2) the two expressions for the second term Idep that describes
supersaturation relaxation, which yields (Γ2/rv)Idep = −si/tfc. Substituting here (Eqn. 8.10.39) for Idep
and (Eqn. 8.10.48) for exp[ushomsw,max(tmax)], and assuming si ,max ≈ swhom
, cr , we obtain Idep and tfc at tmax as

I dep = c1i w(1 + swhom

, cr ) ρ is / Γ 2 and
−1 hom
τ fc (tmax ) = [c1i w(1 + swhom
, cr )] sw , cr . (8.10.54)

It was shown in Section 5.3, that in the diffusion approximation of crystal growth, τ fc ≈ [4π Dv N c rc ]−1 .
Applying this equation at tmax and using (Eqn. 8.10.54), we obtain the mean crystal radius at t = tmax,

rc (tmax ) = [4π Dv N c hom (tmax )]−1 τ −fc1

= [4π Dv N c hom (tmax )]−1 c1i w(1 + sihom hom −1
, cr )( si , cr ) . (8.10.55)

Using the values from Figs. 8.17, 8.18, and 8.23, Ncm ≈ 35 L−1, at t = tmax ≈ 34.5 min, and
−1
, cr ≈ 0.42, w = 4 cm s , an estimate from (Eqn. 8.10.55) gives rc (t max ) ~ 11.8 µ m,
c1i ∼ 10−5 cm−1, sihom
which is in good agreement with rc ≈ 12.5 µm in Fig. 8.18b at 34.5 min. The final value of rc after
the end of nucleation can be evaluated as rc (tcr 2 ) ≈ K cor ( w)rc (tmax ) or simply as rc (tcr 2 ) ≈ 2rc (tmax ).
These values of Nchom and rc can be used in the models for calculation of the IWC at the end of
nucleation.
8.10. Analytical Parameterization of Homogeneous 381

8.10.7. Particular Limiting Cases

Diffusion growth limit. The important asymptotic limits can be obtained by analysis of the charac-
teristic parameters of the solution (Eqns. 8.10.51) and (8.10.52) with Ψhom from (Eqn. 8.10.44). The
parameter lhom in (Eqn. 8.10.38) can be rewritten in the form
2
β hom (r0 + ξ dep )2  r0 + ξ dep 
λhom = =  ,
Bi hom  Λ hom 
1/ 2 1/ 2
B   2ci 3 sihom
, cr 
Λ hom =  i hom  =   . (8.10.56)
 β hom   s hom 1w w 
u c

Here Λhom is a scaling length that characterizes the ratio of the crystal growth rate (Eqn. 8.5.6) to
the supersaturation generation rate (the first term on the RHS of (Eqn. 8.10.47)). Now we present
asymptotics of the solution (Eqn. 8.10.51) at lhom << 1 and lhom >> 1. The values of lhom and Λhom
and physical meaning of the asymptotics are analyzed in the following text.
The values lhom << 1 mean small xdep and r0, and are typical of the diffusion regime of crystal
growth with deposition coefficient ad ∼ 1 or ad > 0.1 at not very large w and not very low T. In
this case, we can neglect in (Eqn. 8.10.44) for Ψhom all terms with xdep and r0 and note also that
erf ( λhom ) → 0 at lhom << 1 → 0. Based on the estimates earlier, we can also assume that bhomtmax >> 1
and the terms with exp(−bhomtmax) can be neglected. Thus, Ψhom is simplified in this diffusion regime

Ψ hom,dif ≈ ( π /2) e λhom Bi1/2 −3/2

hom β hom ≈ (π /2)
1/2
(ci 3 sihom
. cr ) us hom (c1w w)−3/2 .
1/2 −3/2
(8.10.57)

Substitution of this expression into (Eqns. 8.10.51) and (8.10.52) yields for the crystal concentration
hom
N cm , dif in the diffusion regime of crystal growth at tmax

hom hom hom hom −3/ 2

N cm , dif (t max ) = K i , dif (1 + si . cr )( si . cr ) (c1i w)3/ 2 , (8.10.58)
1/ 2 1/ 2
−3/ 2
 ρi Γ 2   c1w 
K ihom
, dif = (2π Dv )  ρ  us1/hom
2
c 
 is   1i 
1/ 2 1/ 2 1/ 2
ρΓ   2 R ∆Fcrhom ,0 (T )   c1w 
= (2π Dv )−3/ 2  i 2    c  . (8.10.59)
 ρis  ln( 0 /T )   1i 
ef
 kM L
w m T

The properties of this solution are discussed in the following text and compared with the other limits.
The total crystal concentration in the diffusion regime after the end of nucleation at t > tcr,2 is
hom hom
N tot , dif ≈ 2 N cm , dif .

Kinetic growth and large particle limits. The diffusion limit was at lhom << 1, and the opposite limit
is lhom >> 1. It is seen from the definition of lhom (Eqn. 8.10.56) that this case can be typical of a
kinetic regime with large xdep (small ad) or with a large initial particle radius r0 of freezing particles.
It can be studied using the asymptotic property of erf(x) at x >> 1 (see Appendix A.8):

1 −1/ 2 − λ  1 
erf ( λ ) = 1 − λ e 1 − . (8.10.60)
π  2λ 
382 Homogeneous Nucleation

Expanding in (Eqn. 8.10.44) for Ψhom the functions erf ( λhom ) and erf ( λhom + β hom tmax ) with
(Eqn. 8.10.60), neglecting the terms with exp(−bhomtmax) and the terms (lhom)−3/2 compared to
(lhom)−1/2, and collecting the terms of the same order, Ψhom can be written as
−1/ 2 −1/ 2
Ψ hom, kin = β hom λhom [(1 / 2) Bi1/hom
2 −1
β hom 2
+ ξ dep Bi−1/ 2 ] + Bi1/hom
2 −3/ 2 1/ 2
β hom −1
λhom − 2ξ dep β hom
= (r0 + ξ dep )−1 [(1 / 2) Bi hom β hom
−2 2
+ ξ dep −1
β hom −1
] + (r0 − ξ dep )β hom . (8.10.61)

This case is divided into two subcases: a) xdep is large (small deposition coefficient ad) but r0 is small
(small particles limit)—that is, xdep >> r0; and b) r0 is large (large particles limit)—that is, xdep << r0,
which may correspond to diffusion or kinetic regimes. These limits are considered in the following text.

a. lhom >> 1, xdep >> r0, kinetic regime, small particle limit
With these conditions, r0 can be neglected compared to xdep and Ψhom in (Eqn. 8.10.61) is
simplified as
−2 −1
Ψ hom,kin ,s = (1 /2) Bi hom β hom ξ dep = ci 3 sihom −2 −2
,cr us hom (c1 w w) (α d Vw /4 Dv ).
(8.10.62)
hom
Substitution into the general (Eqn. 8.10.51) yields the crystal concentration N cm , kin , s (t max ) at

maximum swmax
hom hom hom hom −2 2
N cm ,kin ,s (t max ) = K i ,kin ,s (1 + si . cr )( si . cr ) (c1 w w ) , (8.10.63)

1 us hom  ρi Γ 2   c1i 
K ihom
,kin ,s = . (8.10.64)
(π Dv ) α d Vw  ρis   c1w 

The total crystal concentration after the end of nucleation at t ≥ tcr,2 is N chom hom
, kin , s ≈ 2 N cm , kin , s (t max ).
hom 2
Thus, in this limit N c , kin ,s ~ w , which is in agreement with Ren and McKenzie (2005), but all
coefficients are expressed now via the primary fundamental parameters, without empirical con-
stants. Note also that the crystal concentration is inversely proportional to the saturated vapor
, kin , s ~ ρ is ( T ) and to the deposition coefficient, N c , kin , s ~ α d ; that is, the smaller ad
−1 hom −1
pressure, N chom
or the more polluted the clouds, the greater the nucleated crystal concentration. The wide scat-
ter of measured ad was described in Hobbs (1974) and Pruppacher and Klett (1997). Gierens
et al. (2003) discussed possible reasons for ad as small as 10−3; in these cases, the dependence
Nc ∼ 1/ad can be significant. This is in agreement with data from the Interhemispheric Differences
in Cirrus Properties from Anthropogenic Emissions (INCA) field experiment (Ovarlez et al.,
2002; Ström et al., 2003; Haag et al., 2003; Gayet et al., 2004; Monier et al., 2006) that found
greater ice crystal concentrations in cirrus in the more polluted northern hemisphere than in
the cleaner southern hemisphere. This could be caused not only by the heterogeneous ice
nucleation mode, but also by a small deposition coefficient in homogeneous nucleation in
polluted areas.
b. Initial r0 is large and r0 >> xdep; large particles limit
Neglecting xdep compared to r0, (Eqn. 8.10.61) can be further transformed

1 −2 −1 −1
 Bi hom 
Ψ hom, kin ,l = Bi hom β hom + r0 β hom = r0 β hom  β r 2 + 1
2r0  hom 0 
−1 −1 −1
= r0 β hom (λhom + 1) ≈ r0 β hom . (8.10.65)
8.10. Analytical Parameterization of Homogeneous 383

The last equality takes into account that lhom >> 1, the first term in the parentheses is much
smaller than the second and can be neglected. Substituting Ψhom.kin,l into the general solution
(Eqn. 8.10.51), we obtain
hom −1 hom hom −1
N cm , l (t max ) = (4π Dv r0 ) (1 + si . cr )(si . cr ) (c1i w).
(8.10.66)

The total crystal concentration after the end of nucleation at t ≥ tcr,2 is N chom hom
, l ≈ 2 N cm , l (t max ) .
hom
That is, the dependence on w is linear, N c ,l ~ w, in agreement with predictions in Kärcher and
Lohmann (2002a,b) and in Ren and MacKenzie (2005). The term ris(T) is absent now, thus the
temperature dependence is much weaker than in the previous cases, and is caused now by the
T-dependence on Dv, c1i, and sihom
. cr .

8.10.8. Physical Interpretation

Two example calculations using this new parameterization are shown in Figs. 8.25 and 8.26. The
crystal concentrations Nc(w) calculated using the diffusion approximation with (Eqns. 8.10.57)–
(8.10.59) and ad = 1 (denoted KC2012) for an ascending air parcel is shown in Fig. 8.25. The
applicability of the diffusion approximation is justified by the small lhom ∼10−3 to 0.03 with ad = 1
for all w. It is compared with the parameterizations by Sassen and Benson (2000, SB2000, to
w = 1 m s−1), Liu and Penner (2005, LP2005), Kärcher and Lohmann (2002a, KL2002). Also shown
here are the results of several parcel model simulations from Lin et al. (2002) according to the
protocols of CPMCP for the three values of w = 4, 20 and 100 cm s−1. Simulations were performed
by Cotton, DeMott, Jensen, Kärcher, Lin, Sassen, and Liu as indicated in Fig. 8.25 (the models
are described in Sassen and Dodd, 1988; DeMott et al., 1994; Jensen et al., 1994; Lin, 1997;
Khvorostyanov and Sassen 1998a,b; Spice et al., 1999; Kärcher and Lohmann, 2002a,b; Liu and
Penner, 2005); the results of parcel simulations from Khvorostyanov and Curry (2005a; KC2005)
are added. This figure shows that the new parameterization KC2012 lies within the spread of the
parcel models results, being closer to the lower limit, and to the parcel simulations by Jensen,
who also used the model with spectral microphysics and supersaturation (Jensen et al., 1994). The
KC2012 is in a qualitative agreement with Sassen and Benson (2000) at small w and is especially
close to the parameterization by Kärcher and Lohmann (2002a,b) at all w and at both temperatures,
although it was based on a substantially different approach. This agreement supports the validity
of the new parameterization (Eqns. 8.10.51)–(8.10.53c), based on an extension of the classical
nucleation theory and shows that the semi-empirical approaches lead to results that can be derived
from classical nucleation theory.
Fig. 8.26 shows a comparison of the full solution (Eqns. 8.10.51)–(8.10.53c) with diffusion
limit (Eqns. 8.10.57)–(8.10.59) at ad = 1 and a kinetic limit (Eqns. 8.10.62)–(8.10.64) at ad = 0.04,
0.01, and 0.001. The diffusion approximation (solid circles) is valid at lhom << 1, and limited at
w ≤ 170 cm s−1; the kinetic limit is valid at lhom >> 1 and with ad = 0.04 is limited at w > 30 cm s−1;
both limits are denoted with ellipses. This figure illustrates good accuracy of the two approxima-
tions for corresponding values lhom and underscores the important role of the deposition coefficient.
With small ad, such as in polluted clouds, the crystal concentrations are substantially higher
(2 times at ad = 0.04, and 8 times at ad = 0.01) than with ad = 1 for relatively clean clouds. So, polluted
384 Homogeneous Nucleation

1E+2
T = –40 C

Crystal concentration Nc (cm–3)

1E+1
Parcel models
D DeMott
J Jensen
1E+0
K Karcher
Parametrizations
L Lin
KC2012
S Sassen
SB2000
1E–1 X X.-Liu

LP2005 V KC2005

KL2002
1E–2
0 100 200 300 400
Vertical velocity w (cm s–1)
(a)
1E+3
T = –60 C

1E+2
Crystal concentration Nc (cm–3)

Parcel models
1E+1
C Cotton
Parameterizations D DeMott

1E+0 J Jensen
KC2012
K Karcher
SB2000
L Lin
1E–1 LP2005 S Sassen
X X.-Liu
KL2002
V KC2005
1E–2
0 100 200 300 400
Vertical velocity w (cm s–1)
(b)

Figure 8.25. Comparison of the diffusion approximation (Eqns. 8.10.57)–(8.10.59) of the crystal
concentration Nc(w) as a function of w (KC2012) with the parameterizations by Sassen and Benson
(2000, SB2000, limited to w = 100 cm s−1), Kärcher and Lohmann (2002, KL02), Liu and Penner
(2005, LP2005), and with parcel model simulations from Lin et al. (2002) (Cotton, DeMott, Jensen,
Kärcher, Lin, Sassen, X.-Liu, as indicated in the legend) and from Khvorostyanov and Curry,
2005 (KC2005) for the three values of w = 4, 20, and 100 cm s−1. From Khvorostyanov and Curry,
Atmos. Chem. Phys. (2012), reproduced with permission.
8.10. Analytical Parameterization of Homogeneous 385

1E+3
T = –40 C

Crystal concentration (cm–3)

1E+2

1E+1

Full sol., αd = 1
1
Diff. limit, αd = 1
0.1 Full sol., αd = 0.04
Kin. lim, αd = 0.04
1E–2 Kin. lim, αd = 0.01
Kin. lim, αd = 0.001
1E–3
0 100 200 300 400
Vertical velocity w (cm s–1)

Figure 8.26. Comparison of the full solution (Eqns. 8.10.51)–(8.10.53) with Ψ defined in (Eqn. 8.10.46)
at two values of ad = 1 and 0.04 (Full sol.) with diffusion limit (Eqns. 8.10.57)–(8.10.59) and kinetic
limit (Eqns. 8.10.62)–(8.10.64). The diffusion approximation (solid circles) is valid at lhom << 1, and
limited here at w ≤ 170 cm s−1; the kinetic limit is valid at lhom >> 1 and with ad = 0.04 is limited here
at w > 30 cm s−1. Both limits are denoted with ellipses. From Khvorostyanov and Curry, Atmos. Chem.
Phys. (2012), reproduced with permission.

crystalline clouds may have substantially greater crystal concentrations and albedo effects, which is
similar to the Twomey (1997a,b) effect for liquid clouds. The possibility of this effect for crystal-
line and mixed clouds was discussed—e.g., by Lohmann and Feichter (2005). The parameteriza-
tion described here provides a quantitative tool for estimation of these effects for crystalline clouds.
Fig. 8.26 shows that these effects can be significant for small ad—e.g., if the nucleated crystals are
covered by the layers of adsorbed gases or the liquid films, which may act as the surface active sub-
stances (e.g., Gao et al., 2004; Räisänen et al., 2006; Bogdan and Molina, 2009; Bogdan et al., 2013).
The accuracy of the parameterization equations for Nc derived in this section was estimated by
comparison with the data on Nc from the International CPMCP Project (Lin et al., 2002) and parcel
simulation results described in Section 8.9. The average error of this parameterization relative to the
parcel runs described in Section 8.9 is about ±5–15%. This is a satisfactory accuracy that takes into
account the fact that the difference in Nc among various models in CPMCP was much greater.
The new analytical parameterization of homogeneous freezing derived from extended classical
nucleation theory and analytical solutions to the supersaturation equation includes the time depen-
dence, and can therefore be used for calculations of the crystal concentrations in cloud models with
small time steps (e.g., Jensen et al., 1994; Khvorostyanov and Sassen, 1998b, 2002; Spice et al.,
1999; Khvorostyanov et al., 2001, 2003, 2006; Lin et al. 2002; Sassen et al., 2002; Randall et al.,
2003; Khairoutdinov and Randall, 2003; Fridlind et al., 2004; Krakovskaia and Pirnach, 2004; Khain
et al., 2004; Morrison et al., 2005a,b; Seifert and Beheng, 2006; Monier et al., 2006; Grabowski
and Morrison, 2008; Klein et al., 2009; Spichtinger and Gierens, 2009; Xue et al., 2010; Fan et al.,
2011; Curry and Khvorostyanov, 2012; Tao et al., 2012; Spichtinger and Krämer, 2012), for substep
parameterizations in the mesoscale models like the Weather Research and Forecast Model (WRF)
386 Homogeneous Nucleation

(e.g., Zhang et al., 2011; Veltishchev et al., 2011) or the Consortium for Small-Scale Modeling
(COSMO Model) (Zubler et al., 2011), and in large-scale climate models and GCMs with time steps
that can be greater than the nucleation time tnuc (e.g., Lohmann and Kärcher, 2002; Morrison and
Gettelman, 2008; Gettelman et al., 2008; Sud et al., 2009; Hoose et al., 2010).
The analytical parameterization of homogeneous freezing derived in this section has the following
properties.

1. We can delineate three different regimes of crystal homogeneous nucleation in cold clouds,
depending on the cooling time of an air parcel in ascending motion. At small times, t << tnuc,hom =
(ushomc1ww)−1 (∼40 s in the example considered earlier), the crystal concentrations increase linearly
with time. At larger times, t >> tnuc,hom, but smaller then the time tmax of maximum supersaturation
in the parcel, t < tmax, the number Nc exponentially grows with time. Crystal concentrations in these
two regimes are proportional to the homogeneous nucleation rate and concentration of the aerosol
(haze) particles as described by (Eqns. 8.10.23) and (8.10.24). These regimes could be also cre-
ated in some diffusion chambers at slow cooling rates; the updraft w = 10 cm s−1 corresponds to the
cooling rate dT/dt ∼ −gaw ∼ −0.06 K min−1. Note that the cooling rates in the diffusion chambers
are usually greater, and the particle residence times in the chambers are smaller.
If a parcel rises and cools without mixing, so that t > tmax and t > tcr,2, the supersaturation reaches
and passes a maximum and falls below the threshold value, then a third limiting regime occurs
where the maximum possible crystal concentrations are nucleated in the parcel at the thermo-
dynamic conditions. This regime is described by (Eqns. 8.10.51), (8.10.52), and (8.10.53a),
(8.10.53b), and (8.10.53c). The dependence on the nucleation rate and haze concentration van-
ishes in this regime, although concentration of nucleated crystals is much smaller than the con-
centration of haze particles. As parcel model simulation showed (Section 8.9), the times tmax at
T= −40 °C and w = 4, 20 and 100 cm s−1 are about 530, 120, and 40 seconds, and the total times
of nucleation required for this regime are (tcr,2 − tcr,1) ∼ 800, 190, and 60 seconds, respectively.
At T = −60 °C, these times are about half the magnitude.
2. Expressions for the crystal concentration in the third limiting regime are very simple, and some-
what surprising. They do not include most of the basic factors present in the original super-
saturation equation: neither the nucleation rate Jhom(T, sw), nor the concentration Na of the haze
particles, nor any info on their volume, size spectra, or chemical composition. The reason why
Nc does not depend on Na is because Nc is usually on the order of a few or a few tens per liter
(rarely, a few hundred, and very rarely, a few thousand), while Na is typically on the order of a
few hundred per cubic centimeter. That is, only a very small fraction of haze particles freezes,
and the dependence of Nc on Na vanishes at values of Na much smaller than those in the upper
troposphere studied here. However, if Na is small, then Nc is limited by Na.
3. The major three factors that govern homogeneous ice nucleation in the third limiting regime
are the vertical velocity, w, the temperature, T, and the critical (threshold) saturation ratio sihom . cr .

The equations for Nc derived in this section show that in a first approximation in diffusion
limit, Nc ∼ w3/2, and N c ~ ρ si−1/ 2 (T ) , both dependencies are the same as in Kärcher and Lohmann
(2002a,b) and in Ren and MacKenzie (2005) in the diffusion growth limit. However, the actual
−3/ 2
dependence of Nc on w and T is more complicated and somewhat different since (sihom . cr ) also
8.11. Temperature Effects and the Homogeneous Freezing of Cloud Drops 387

includes dependence on w and T, the critical supersaturation sihom . cr also depends on T, and the

coefficient Ki,dif also depends on T via factors Dv, c1w, c1i, and ushom. In the kinetic limit or in the
large particle limit, Nc can be proportional to w2 or to w, depending on the initial particle radius,
in agreement with previous semi-empirical parameterizations. An additional explicit depen-
dence on the deposition coefficient, derived here, allows estimates of the effects of atmospheric
pollutions on the properties of the crystalline and mixed phase clouds.
4. The nucleation rate Jf,hom(T, sw), derived here, varies exponentially with time, and this depen-
dence is characterized by some scaling nucleation time tnuc,hom that is expressed here directly via
the parameters of classical nucleation theory and fundamental physical constants.

8.11. Temperature Effects and the Homogeneous Freezing of Cloud Drops

The effects of temperature on the homogeneous freezing of drops were not accounted for in
Section 8.10 since they were small compared to the supersaturation effects in the freezing of the
deliquescent haze particles. These effects may become dominant if supersaturation variations are
small, as in an ensemble of water drops, or if the temperature changes are large enough. Evalua-
tion of the temperature effects on the nucleation rates and crystal concentrations can be done in a
similar manner to the derivation for the supersaturation effects. Equation (8.10.7) shows that small
variations in the critical energy of nucleation DFcr(T) due to the temperature change DT are caused
primarily by variations in four parameters: surface tension sis, ice density ri,, effective melting
heat, and ln(T0/T).
Parcel model simulations in Section 8.9 and analysis of experimental data in the preceding sections
show that temperature changes DT during nucleation are usually much smaller than T. If DT << T,
the perturbations due to temperature decrease DT can be approximated as linear:

σ is3 (T − ∆T ) ≈ σ is3 (T )[1 − 3σ is′ (T )/σ is (T ) ∆T ], (8.11.1)

L (T − ∆T ) ≈ L (T )[1 − ( L ) ′/ L (T ) ∆T ],
ef
m
ef
m
ef
m
ef
m (8.11.2)

ρi (T − ∆T ) ≈ ρi (T )[1 − ρi′ /ρi (T ) ∆T ], (8.11.3)

T0 T  ∆T 
ln ≈ ln 0 1 + . (8.11.4)
T − ∆T T  T ln(T0 / T ) 
Here the primes indicate absolute values of the derivatives by T (i.e., the derivatives and DT are
assumed to be positive for the quantities decreasing with T), and are themselves functions of T. Sub-
stitution of these expressions in (Eqn. 8.10.10) for ∆Fcrhom
,0 with sw ≈ 0, and expanding the denominator

into the power series to the first-order terms by DT/T yields

∆Fcrhom hom
,0 (T − ∆T ) ≈ ∆Fcr ,0 (T )[1 − κ Tn (T ) ∆T (t )], (8.11.5a)
σ′  ρ ′ ( Lef ) ′  2
κ Tn (T ) = 3 is − 2  i + mef  + . (8.11.5b)
σ is  ρi Lm  T ln(T0 /T )
388 Homogeneous Nucleation

The temperature variations in the activation energy can be presented in a similar form
∆Fact (T − ∆T ) ≈ ∆Fact (T )[1 − κ Ta (T ) ∆T (t )], (8.11.6a)
κ Ta (T ) = ∆Fac′ t (T ) /∆Fact (T ). (8.11.6b)

Substituting these expressions into (Eqn. 8.10.6) for Jf,hom, and using the approximation for the
denominator 1/[k(T − DT)] ≈ 1/(kT)(1 + DT/T) yields

J f ,hom (T − ∆T ) = J f ,hom (T ) exp[ BT hom ∆T (t )], (8.11.7)

where we denoted
BT hom = uTact (T ) + uT hom (T ), (8.11.8a)

 1  ∆F (T )
uTact (T ) =  κ Ta (T ) −  act , (8.11.8b)
 T  kT
hom
 1  ∆Fcr ,0 (T )
uT hom (T ) =  κ Tn (T ) −  . (8.11.8c)
 T kT
The parameters BThom, kTa, kTn, uTact, and uThom have the dimension K−1, describe a decrease in DFcr
and increase in Jf,hom with temperature decrease DT. These parameters are the analogs of ks and ushom
introduced in Section 8.10 that describe variations in DFcr and Jf,hom due to supersaturation varia-
tions. BThom describes the major exponential increase in Jf,hom with temperature decrease DT similar to
several empirical parameterizations of ice nucleation. The values of these parameters are estimated
in the following.
The temperature decrease DT can be related to the time dependence via the temperature lapse rate
g and vertical velocity w using the temperature equations from Section 3.11, and integrating with
respect to time

dT /dt/ = Tɺ =ɺ −γ−w
γ , ∆, ∆T (t ) = − ɺ γ= γ wt .
ɺ Tt (8.11.9)

The minus sign in the second equation arises because we defined the temperature decrease as positive,
DT > 0, when dT/dt < 0. Substituting (Eqn. 8.11.9) into (Eqn. 8.11.7), we obtain the time dependent Jf,hom:

J f ,hom (t ) = J (0) (0)

f ,hom (t 0 ) exp(β T hom t ) = J f ,hom (t 0 ) exp(t /τ T hom ), (8.11.10)

where we introduce again the characteristic freezing frequency bThom and time tThom:

β T hom (T ) = (uTact + uT hom )γ w = (uTact + uT hom )(− dT /dt ), (8.11.11a)

−1 −1
τ T hom = [(uTact + uT hom )γ w] = [(uTact + uT hom )(− dT /dt )] . (8.11.11b)

The first form of these equations is convenient for analysis in numerical models where g and w are
known, and the second form can be more convenient for analysis of laboratory experiments where
dT/dt is known. As in Section 8.10, the polydisperse nucleation rate for freezing due to the tempera-
ture change can be written as

dN c
R f ,hom = ≈ N a va J f ,hom (t ) = N a va J (0)
f ,hom (t 0 ) exp(β T hom t ). (8.11.12)
dt
8.11. Temperature Effects and the Homogeneous Freezing of Cloud Drops 389

Integration over time yields

N c (t ) = N a va J (0)
f ,hom (t 0 )τ T hom [exp(β T hom t ) − 1]. (8.11.13)

So, the time dependence of the crystal concentration due to temperature decrease is similar to that due
to the supersaturation variations described in Section 8.10. If we consider the freezing of deliques-
cent haze particles, the joint effect of the supersaturation and temperature variations can be simply
accounted for by replacing of the frequency bshom with (bshom + bThom) in the equations for Jf,hom and
Nc(t) in Section 8.10. If we consider homogeneous freezing of water drops near the water saturation
with sw ≈ 0, then only the terms with bThom are essential and the equations of this section can be used.
For small times or temperature changes, if bThomt << 1, the exponent in (Eqn. 8.11.13) can be
expanded and (Eqn. 8.11.13) is reduced to

N c (t ) = N a va tJ (0)
f ,hom (t 0 ), (8.11.14)

that is, the time dependence of Nc is linear in this limit. For large times or temperature changes, if
bThomt >> 1, the time dependence becomes exponential,

N c (t ) = N a va J (0)
f ,hom (t 0 )τ T hom exp(β T hom t ). (8.11.15)

The last two equations may explain the difference in the nucleation rates at small and large DT. If a
permanent and significant cooling rate is present, the rate of crystal formation is exponential accord-
ing to (Eqn. 8.11.15). If such a source of cooling is absent, and there are only small random tempera-
ture fluctuations, the rate of crystal production is close to linear with time as in (Eqn. 8.11.14). These
features are similar to those described in experiments on the heterogeneous freezing of drops with
an alternating cooling rate by Vali (1994, 2008), who found different growth regimes of Nc(t) at high
and low cooling rates. The nature of the homogeneous and heterogeneous freezing is similar and the
last two equations provide some explanation for these observations, which will also be discussed in
Section 10.2.
It follows from (Eqn. 8.11.11a) that

β T hom ∆t = (uT hom + uTact )(− dT / dt ) ∆t = (uT hom + uTact ) ∆T = BT hom ∆T , (8.11.16)

or BThom = uThom + uTact. Using this relation, (Eqn. 8.11.15) can be rewritten for ice crystals nucleated
during interval Dt as

N c ( ∆t ) = N a va J (0)
f ,hom (t 0 )τ T hom exp( BT hom ∆T ). (8.11.17)

The exponential temperature dependence of Nc derived here is theoretically similar to the parameter-
ization Nc(T) ∼ exp(bFDT) with DT = T0 − T for heterogeneous ice nucleation derived empirically by
Fletcher (1962) and several other researchers (see Section 9.4). Equation (8.11.17) shows that there is
similarity in the temperature dependence of the homogeneous and heterogeneous ice nucleation. The
parameter BThom [K−1] is a theoretically derived analogue of the empirical parameter bF introduced by
Fletcher (1962) and others in similar parameterizations. The average value of the exponent in Fletcher
(1962) was bF ≈ 0.6 K−1, although wide variations were reported (Pruppacher and Klett, 1997).
We can compare now the T-dependencies of homogeneous and heterogeneous nucleation. The
values of the coefficients kTn, kTa, and BThom in (Eqns. 8.11.8a)–(8.11.8c) can be estimated using
390 Homogeneous Nucleation

the parameterizations of sis(T), ri(T) from Section 4.4 and of Lefm (T ) from Section 8.8 and DFact(T)
from Section 8.3. These estimates may vary depending on the parameterizations for the key param-
eters of classical nucleation theory. An estimate at T = 233 K using (Eqn. 4.4.15a) for sis(T),
(Eqn. 4.4.22) for ri(T) and (Eqn. 8.8.12a) for Lefm (T ) gives kTn − 1/T ≈ 7 × 10−2 K−1. Fig. 8.3 shows that
∆Fcrhom
,0 ≈ 1.2 × 10
−12
erg for pure water drops at 233 K; thus, ∆Fcrhom ,0 / kT ≈ 37.3. Substituting this value

into (Eqn. 8.11.8c), along with the estimated kTn yields uThom ≈ 2.1.
An estimate for kTa is more uncertain because several different parameterizations suggested for
DFact(T) differ even by the sign of d(DFact)/dT (see Section 4.4). An estimate using (Eqn. 8.3.20) for
DFact(T) from Zobrist et al. (2007) at T = −40 °C yields kTa −1/T ≈ −1.3 × 10−2 K−1, DFact/(kT) ≈ 15.6,
and uTact ≈ −0.195 K−1, so that BThom = uThom + uTact ≈ 1.92 K−1, with the small contribution of uTact being
approximately 7% of uThom. Chen et al. (2008) suggested DFact(T) = const; thus, kTa = 0, and uTact = −0.06.
Using DFact(T) as (Eqn. 8.3.23b) from Khvorostyanov and Sassen (1998c) or Khvorostyanov and
Curry (2000) also yields a small value, kTa ≈ 5 × 10−5. Thus, in these cases, the contribution of uTact is
small and the sum BThom ≈ 2 K−1, which is about a factor 3 higher than Fletcher’s mean 0.6 K−1. Using
Equation (8.3.24) for DFact(T) from Fornea et al. (2009), faster increasing to low T yields an estimate
(kTa − 1/T) ≈ −2.65 × 10−2 K−1, uTact ≈ −0.74 K−1, and BThom ≈ 1.36 K−1.
An estimate using (Eqn. 4.4.15c) from Dufour and Defay (1963) for siw(T) and (Eqn. 8.8.12b)
for Lefm (T ) gives smaller s ′is(T)/sis(T) and [ Lefm (T )]′/Lefm (T ) and with the same r ′i(T)/ri(T) this yields
kTn ≈ 4.35 × 10−2 K−1 and uThom ≈ 1.21 K−1. Using uTact ≈ −0.195 K−1, based on DFact(T) from Zobrist et al.
(2007), we obtain BThom ≈ 1.0 K−1, and using uTact ≈ −0.74 K−1, based on DFact(T) from Fornea et al.
(2009), we obtain BThom ≈ 0.47 K−1, which is closer to Fletcher’s mean bF = 0.6 K−1 for heterogeneous
nucleation.
Thus, this extended classical nucleation theory allows derivation of an exponential temperature
dependence for crystal concentrations and makes clear its physical reason: this is the exponential
time dependence of Nc in (Eqn. 8.11.15) and the temperature dependence of siw(T), Lefm (T ), ri(T), and
DFact(T). However, the parameter BThom in the exponent in (Eqn. 8.11.17) is sensitive to the param-
eters of classical theory, which emphasizes the necessity of further refining these parameters based
on newer experimental data on ice nucleation. It will be shown in Chapters 9 and 10 that a similar
analysis for heterogeneous freezing allows an explanation of the exponential temperature depen-
dence of Nc(t) and also gives the values of the coefficients closer to those experimentally derived.
Evaluation of the Integrals 391

Appendix A.8 for Chapter 8. Evaluation of the Integrals

t

J 0(ki ) = ∫ rc(,kef) (t , t0 ) exp(β t0 ) dt0

0

These integrals are defined in (Eqn. 8.10.32) with b defined in (Eqn. 8.10.21), and rc(,kef) (t , t0 ) with
(k) = 1, 2, 3 defined in (Eqns. 8.10.30a), (8.10.32b), and (8.10.32c) as

β = us c1w w, Bi = 2ci 3 si ,cr , (A.8.1)

rc(1) 2
,ef (t , t 0 ) = [(r0 + ξ dep ) + Bi (t − t 0 )]
1/ 2
, (A.8.2)

rc(2)
, ef (t , t 0 ) = −2ξ dep , (A.8.3)

rc(3) 2 2
, ef (t , t 0 ) = ξ dep [(r0 + ξ dep ) + Bi (t − t 0 )]
−1/ 2
. (A.8.4)

We omit here the subscript “hom” at b and Bi, l, J0i, Ψ, Ψ1,2,3, and other quantities for brevity.
Besides, the same integrals will occur in Chapters 9 and 10, with all these quantities specific for
heterogeneous nucleation, and the same solutions will be valid there, with the superscript “het.” The
first of these integrals is
t

J 0(1)i = ∫ rc(1)
,ef (t , t 0 ) exp( β t 0 ) dt 0
0
t

= ∫ [(r0 + ξ dep )2 + Bi (t − t0 )]1/2 exp(β t0 ) dt0 , (A.8.5)

0

Introducing a new variable x = t0/t, it is transformed into

1

J 0(1)i = Bi1/ 2 t 3/ 2 ∫ (1 − x + a)1/ 2 exp(β tx ) dx , (A.8.6)

0

(ξ dep + r0 )2
a= . (A.8.6a)
Bi t

Introducing now a new variable, z = 1 − x, this integral transforms into

1

J 0(1)i = Bi1/2t 3/2e β t J1(1)i J1(1)i = ∫ ( z + a)1/2 exp(− β tz ) dz. (A.8.7)

0

The next change of the variable, z′ = z + a, yields

1+ a

J1(1)i = e λ ∫ z′
1/2
exp[− β tz ′] dz ′, (A.8.8)
a

and l does not depend on t

(ξ dep + r0 )2 β (us c1w w)(ξ dep + r0 )2

λ = aβ t = = . (A.8.9)
Bi 2c1i si ,cr
392 Homogeneous Nucleation

We introduce a new variable x′ = b tz′. The limits z′ = a and z′ = (1 + a) transform into x′ = ab t = l

and x′ = b t(1 + a) = l + b t. Thus, we have

exp(λ )  1/ 2 
∞ λ +βt

J1(1)i = 3/2 
(β t )  λ ∫ x ′ exp( − x ′ ) dx ′ + ∫
∞
x ′1/2 exp(− x ′) dx ′  ,

exp(λ )   3  3 
= Γ  , λ  − Γ  , λ + βt  . (A.8.10)
(β t )3/2   2  2 

Here, Γ(m, l) is the incomplete Euler’s gamma function (Gradshteyn and Ryzhik, 1994):
∞
Γ ( µ , λ ) = ∫ x µ −1 exp(− x ) dx . (A.8.10a)
λ

Substitution of (Eqn. A.8.10) into (Eqn. A.8.7) yields

 3  3 
J 0(1)i = e β t Bi1/ 2 β −3/ 2 e λ  Γ  , λ  − Γ  , λ + β t   . (A.8.11)
 2  2 
(2)
Calculation of the second integral J 0 i is much easier:
t t

J 0(2)i = ∫ rc(2)
,ef (t , t 0 ) exp( β t 0 ) dt 0 = −2ξ dep ∫ exp(us c1 w wt 0 ) dt 0
0 0

exp(β t ) − 1 exp(us c1w wt ) − 1 exp(β t )

= −2ξ dep = −2ξ dep ≈ −2ξ dep . (A.8.12)
β us c1w w β

The last approximation here is valid only at bt >> 1. The third integral is
t

J 0(3)i = ∫ rc(3)
, ef (t , t 0 ) exp( β t 0 ) dt 0
0
t
exp(β t0 )
∫
2
= ξ dep dt0 . (A.8.13)
0
[ Bi (t − t0 ) + ξ d2ep ]1/ 2

Similar to evaluation of the first integral, introducing a new variable x = t0/t, and then z = 1 − x, this
integral is reduced to
2 1/ 2 β t
ξ dep t e 1
exp(− β tz )
J 0(3)i = = 1/ 2 J1(3) i = ∫
J ii , =J1(3)
i ,J dz , (A.8.14)
Bi 0
( z + a)1/ 2

where a is the same as in (Eqn. A.8.6a). Introducing now a new variable z′ = b tz, we obtain
βt
exp(− z ′)
J1(3i ) = (β t=)−1/2 J 2(3)i , J , =J 2(3)i = ∫ (z′ + λ )
0
1/2
dz ′. (A.8.15)

The integral J 2(3)i here is similar to (Eqn. A.8.7). Substituting here x = z′ + l, and accounting for the
change of the limits, (0, bt) to (l, l + bt) yields
λ +βt λ +βt
∞ 
J 2(3)i = e λ ∫λ
x −1/ 2 e − x dx = e λ  ∫ x −1/ 2 e − x dx + ∫ x −1/ 2 e − x dx 
 λ ∞ 
 1  1 
= eλ Γ  , λ  − Γ  , λ + β t   , (A.8.16)
  2   2 
Evaluation of the Integrals 393

where Γ(a, x) is again the incomplete gamma function. Substituting (Eqn. A.8.16) into (Eqn. A.8.15)
and into (Eqn. A.8.14), we obtain

 1  1 
J 0(3)i = ξ dep
2
(β Bi )−1/ 2 e β t e λ  Γ  , λ  − Γ  , λ + β t   . (A.8.17)
  2   2 

It is more convenient in many cases to use the error function Φ(x) = erf(x), defined as
x
2 − x ′2
erf ( x ) ≡ Φ( x ) =
π ∫e
0
dx ′, (A.8.17a)

instead of incomplete gamma functions, for which coding and finding asymptotics can be easier.
This can be done using the relations (Gradshteyn and Ryzhik, 1994, Chapter 8, (Eqns. 8.359) and
(8.356) therein)

Γ (1 /2 , λ ) = π [1 − erf ( λ )], (A.8.18)

Γ (α + 1, λ ) = αΓ (α , λ ) + λ α e − λ . (A.8.19)

Using these two relations, the Γ(3/2, l) in Ψ1 can be transformed as

3  1 1  π
Γ  , λ  = Γ  , λ  + λ 1/ 2 e − λ = [1 − erf ( λ )] + λ 1/ 2 e − λ . (A.8.20)
2  2 2  2

Collecting all three integrals J 0(ki ) yields the integral J0i in (Eqn. 8.10.33):
3
J 0 i (t ) = ∑ J 0(ki ) = e β t Ψ , ΨΨ , Ψ = Ψ1 + Ψ 2 +, Ψ 3 , (A.8.21)
k

 3  3 
Ψ1 = e λ Bi1/ 2 β −3/ 2  Γ  , λ  − Γ  , λ + β t   (A.8.22)
  2   2 

= e λ Bi1/2 β −3/2 {( π /2)[Φ( λ + β t ) − Φ( λ )]

+ e − λ [λ 1/2 − (λ + β t )1/2 e − β t ) ]}, (A.8.23)
−1 − βt
Ψ 2 = 2ξ dep β (e − 1), (A.8.24)

 1  1 
Ψ 3 = e λ ξ dep
2
(β Bi )−1/ 2  Γ  , λ  − Γ  , λ + β t   (A.8.25)
 2    2 

= e λ ξ dep
2
(β Bi )−1/2 π [Φ λ + β t − Φ λ ] . (A.8.26)

These expressions are used in Section 8.10 for evaluation of the deposition integral Jdep in the param-
eterization of homogeneous nucleation and in Section 10.1 for the parameterization of heterogeneous
nucleation.
The asymptotic expansion of Φ( λ ) at large l >> 1 is (Gradshteyn and Ryzhik, 1994, (Eqn. 8.254)
therein)

1 −1/ 2 − λ  1 3 
Φ( λ ) = erf ( λ ) = 1 − λ e 1 − + . (A.8.27)
π  2λ 4 λ 2 
394 Homogeneous Nucleation

It follows from this equation and (Eqn. A.8.17a) that

∞
− x ′2 π
lim Φ( x ) = 1,
x →∞ ∫e
0
dx ′ =
2
(A.8.28)

The other limit at small argument x << 1 with account taken for the first term is (Gradshteyn and
Ryzhik, 1994, (Eqn. 8.253)):

2
lim Φ( x ) = x exp(− x 2 ) (A.8.29)
x→0 π
The incomplete gamma function is related to the gamma function as

Γ ( µ , 0 ) = Γ ( µ ). (A.8.30)

The last function has the property

Γ (1 /2 ) = π (A.8.31)

These asymptotic properties of Φ(x) and Γ(m) are used in Sections 8.10 and 10.1 for evaluation of
the asymptotic behavior of the solutions to the supersaturation equations and parameterizations of
homogeneous and heterogeneous ice nucleation processes.
9
Heterogeneous Nucleation of Drops and Ice Crystals

9.1. Introduction

It was shown in the previous chapter that homogeneous nucleation of water drops from vapor becomes
effective only at very high supersaturations and homogenous nucleation of ice crystals occurs only
at temperatures lower than −35 to −38 °C. Nucleation of droplets from vapor occurs at lower super-
saturations on the surface of a foreign substrate that has the property of “wettability.” Ice formation
occurs at substantially higher temperatures, a few degrees below 0 °C, when the ice crystals form
on the surface of specific foreign particles termed “ice forming nuclei” (IFN) or simply “ice nuclei”
(IN). Nucleation of drops and crystals on the surfaces of foreign substances is called “heterogeneous
nucleation.”
Formation of the ice phase in clouds at temperatures warmer than −38 °C and small supersaturations
via heterogeneous nucleation have been reviewed extensively in previous cloud physics textbooks—
e.g., Fletcher (1962), Dufour and Defay (1963), Defay, Dufour, and Bellemans (1966), Young (1993),
Pruppacher and Klett (1997), Kashchiev (2000). Heterogeneous nucleation also can act at tempera-
tures colder than −38 °C if appropriative ice nucleating aerosols are present, although the relative
importance of heterogeneous and homogeneous nucleation at these colder temperatures is less clear
(e.g., Sassen and Dodd, 1988, 1989; DeMott et al., 1998, DeMott , 2002; Lin et al., 2002; Khvorostyanov
and Sassen, 1998a,b,c, 2002; Gierens, 2003; Kärcher and Lohmann, 2003; Khvorostyanov et al., 2006;
Barahona and Nenes, 2009; Hoose and Möhler, 2012). Heterogeneous ice nucleation dominates in
polar clouds and multilayer frontal and cyclonic cloud systems (frequently observed to be mixed
phase), and also in deep convective clouds and anvil cirrus, when large amounts of mixed aerosol par-
ticles can be brought into the middle and upper troposphere and may serve as ice nuclei.
This chapter describes heterogeneous nucleation processes. Heterogeneous nucleation of drops
on insoluble cloud condensation nuclei is considered in Section 9.2, and the rest of this chapter is
devoted to heterogeneous ice nucleation.

9.2. Nucleation of Drops by Vapor Deposition on Water-Insoluble Particles

We considered in Chapters 6 and 7 the nucleation of water drops on soluble or mixed aerosol par-
ticles, which is governed by Köhler’s equation. That was an example of heterogeneous nucleation
because of the presence of foreign substances, salt, and insoluble fractions. Another example of
heterogeneous process is the nucleation of drops on the surface of solid insoluble aerosol particles,
which also can serve as CCN. Consider a liquid germ forming on a planar surface, which has the
shape of a spherical segment (cap) or a lens shown in Fig. 9.1.

395
396 Heterogeneous Nucleation of Drops and Ice Crystals

Water vapour Liquid solution

(V) (I)

I/v
σ
σN/v σN/I SOLID
(N)
σI/V cos( N/I)

Figure 9.1. Conditions of mechanical equilibrium for a liquid drop on a horizontal solid substrate
surface surrounded by humid air. The surface tensions are: sNv at the solid–vapor interface (arrow
to the left), sNl at the solid–liquid interface (arrow to the right), and slv at the liquid–vapor interface.
Surface tension sNv is balanced by the sum of the surface tension sNl and the projection slv cos(qNl)
of slv onto the horizontal surface, sNv = sNl + slvcos(qNl).

Then, the germ is bounded by a spherical surface formed by the liquid, which is in contact with
environmental vapor, and an underlying plane surface of insoluble solid, on which it forms. The
geometry of the spherical cap is characterized by the two parameters: radius r of the sphere and a
contact angle qNl between the liquid germ and the solid surface.
The contact angle is determined by the properties of the liquid and solid surfaces or by the sur-
face tensions at the three interfaces: solid–liquid (sNl), liquid–vapor (slv), and solid–vapor (sNv) (the
subscripts N, l, and v denote solid substrate, liquid, and vapor). The cosine of the contact angle mlv =
cos(qNl) is determined by Young’s relation for the balance of forces at the boundary of the liquid
spherical cap and solid surface:

σ lv cos θ Nl + σ Nl = σ Nv , (9.2.1)

where the left-hand side represents the force directed inside the cap, and the right-hand side repre-
sents the force directed outside of the cap. This gives

mlv = cos θ Nl = (σ Nv − σ Nl )/σ lv . (9.2.2)

The parameter mlv is also called the “wetting coefficient,” the “wettability coefficient,” the “compat-
ibility parameter,” or the “contact parameter” because it characterizes how “wettable” is this surface
by this liquid, or how “compatible” are the liquid and surface. This parameter depends on the three
surface tensions in (Eqn. 9.2.2), denoted by three letters, N, l, and v. It is customary to use for m the
subscripts denoting the two outer media—here liquid and vapor—hence, it is denoted as mlv.
If qNl is small, then mlv = cos(qNl) tends to 1, and the liquid germ covers a large area on the surface
as a thin liquid film, and such a surface is hydrophilic for this liquid. In the opposite case, if qNl ≥ π/2
and mlv < 0, the germ’s volume is greater than half of a sphere and its shape tends to a sphere. Such
a surface is hydrophobic for this liquid. If qNl → −p /2, then mlv → −1, and the germ has the shape of
a sphere that is located on the surface but touches the surface only at one point. Such a surface is not
wetted, and is called completely hydrophobic or non-wettable. We will see that the smaller the qNl, the
more hydrophilic the surface, and the easier it is to form condensation on such a surface. The almost
spherical drops of dew on the leaves of some plants indicate a hydrophobic surface.
9.2. Nucleation of Drops by Vapor Deposition on Water-Insoluble Particles 397

The radius of the liquid germ on the plane surface (the segment of a sphere with radius r cut by
the planar base) is rb = rsin(qNl). The volume of this spherical liquid cap Vl, the surface area Alv of the
spherical surface and the surface area AlN of the planar base are provided by stereometry (e.g., Korn
and Korn, 1969):

πr3
Vl = (2 + mlv )(1 − mlv )2 , (9.2.3)
3
Alv = 2π r 2 (1 − mlv ), (9.2.4)

AlN = π r 2 (1 − mlv2 ). (9.2.5)

Now we can proceed to derive the nucleation rate in a manner similar to that for homogeneous
nucleation in Chapter 8. We consider nucleation of water droplets from the vapor on an insoluble
surface with the contact angle qNw and contact parameter cos(qNw) (the liquid is water in this example
and the subscript “l” is replaced further with “w” to distinguish from aqueous solutions and ice con-
sidered later). We assume that the concentration cgs of g-mers (embryos containing g molecules) is
described by the Boltzmann distribution:

cgs = c1s exp(−∆Fgs /kT ), (9.2.6)

where c1s is the concentration of single molecules adsorbed on the surface, and DFgs is the energy of
the germ formation. The surface nucleation rate Js,het—i.e., the rate of the germ formation on a unit
surface area per second [cm−2 s−1]—can be evaluated similarly to that for homogeneous nucleation
in Chapter 8:

J s ,het = cgs jg( + ) Ags Z s , (9.2.7)

where jg( + ) is the molecular flux onto this g-mer that can be written using the equation of state for
water vapor, c1s = ev/kT, and assuming that the condensation coefficient ac = 1 (see Chapter 5, and
Section 8.2):
c1sVw ev
jg( + ) = = , (9.2.8)
4 (2π mw1 kT )1/2

Ags is the surface area of the germ, and Zs is the Zeldovich factor, introduced in Section 8.2,
1/2
 ∆Fgs 
Zs =  . (9.2.9)
 3gπ kT 

The critical energy for a germ formation can be written similarly to that for homogeneous nucleation
as in (Eqns. 8.1.2) and (8.1.8), which we write again as a sum of the volume and surface terms:

∆µ vw
∆Fgs = −Vg + σ wg Awg , (9.2.10)
vw

where Dmvw = mv − mw = RTln(Sw) is the difference of molar chemical potentials (affinity) of the vapor
and liquid water, Vg = Vl is the volume of the germ defined by (Eqn. 9.2.3), and vw = Mw/rw is the
398 Heterogeneous Nucleation of Drops and Ice Crystals

molar volume of water. The surface term in (Eqn. 9.2.10) can be evaluated by taking into account the
germ geometry as

σ wg Awg = σ vw Awv + (σ Nw − σ Nv ) ANw , (9.2.11)

where the three surface tensions on the RHS relate to the three interfaces: water–vapor, substrate–
water, and substrate–vapor as defined by their subscripts, Avw and ANw are the surface areas of the
spherical and planar surfaces. Substituting (Eqns. 9.2.4) and (9.2.5) for Avw and ANw into (Eqn. 9.2.11),
we obtain
2
σ wg Awg = σ vw 2π r 2 (1 − mwv ) + (σ Nw − σ Nv )π r 2 (1 − mwv ). (9.2.12)

Using the relation (sNw − sNv) = −svwmwv that follows from (Eqn. 9.2.2), we have

σ wg Awg = π r 2σ vw (1 − mwv )[2 − mNw (1 + mwv )]

= π r 2σ vw (2 + mwv )(1 − mwv )2 . (9.2.13)

The germ energy (Eqn. 9.2.10) can be rewritten using (Eqn. 9.2.3) for Vw and (Eqn. 9.2.13) for the
surface term as

 4π r 3 ∆µ vw  [(2 + mwv )(1 − mwv )2 ]

∆Fgs =  − + 4π r 2σ vw  ,
 3 vw  4
 4π r 3 ∆µ vw 
= − + 4π r 2σ vw  f (mwv ), (9.2.14)
 3 vw 

where we introduced the geometric factor for the planar surface following Volmer (1939)

(2 + mwv )(1 − mwv )2 mwv

3
− 3mwv + 2
f (mwv ) = = . (9.2.15)
4 4
Both of these forms of f(mwv) are used in applications.
Substituting Dmvw = mv − mw = RTln(Sw) into (Eqn. 9.2.14) yields another form of DFgs:

 4π r 3 RT ln( Sw ) 
∆Fgs =  − + 4π r 2σ vw  f (mwv ). (9.2.16a)
 3 vw 

The critical energy is determined from the condition of minimum ∂DFgs(rcr)/∂r = 0, which yields from
(Eqn. 9.2.14):

∆µ vw
4π rcr (− rcr + 2σ vw ) = 0, (9.2.16b)
vw

and so we obtain the critical radius

2σ vw vw 2σ vw vw 2σ vw M w
rcr = = = . (9.2.17)
∆µ vw µ v − µ w RT ρ w ln Sw
9.2. Nucleation of Drops by Vapor Deposition on Water-Insoluble Particles 399

Note that these equations have the same form as (Eqns. 8.1.6) or (8.1.9) in Section 8.1 for rcr via
molar chemical potentials. Substituting this rcr into (Eqn. 9.2.14), we obtain DFcr:

 r ∆µ vw 
∆Fcr = 4π rcr2  − cr + σ vw  f (mwv ). (9.2.18a)
 3 v w 

Substituting here the relation −(rcr/3)Dmvw/vw = −(2/3)svw that follows from (Eqn. 9.2.16b), we obtain

4π σ A 16π M w2 σ vw
3
∆Fcr = σ vw rcr2 = vw cr = f (mwv ), (9.2.18b)
3 3 3 [ RT ρ w ln Sw ]2

where Acr is the surface area of a sphere with radius rcr. The second form of this equation has the
same form as in Chapter 8. If the insoluble substrate is completely wettable (a hydrophilic surface),
mwv = 1, according to (Eqn. 9.2.15), f(mwv) = 0, and DFgs = 0. Thus, there is no energy barrier for
nucleation. In the opposite case of a completely hydrophobic surface, mwv = −1, then (Eqn. 9.2.15)
shows that f(mwv) = 1, and the energy is the same as for homogeneous nucleation. In the intermediate
cases, 0 < f(mwv) < 1, and the energy of heterogeneous nucleation is smaller than that for homoge-
neous nucleation.
Now, the nucleation rate of drops by condensation from vapor per unit area of an insoluble
plane surface per unit time [cm−2 s−1] is obtained from (Eqn. 9.2.7) with the use of (Eqns. 9.2.6)
and (9.2.8):
c1s ev
J s ,het = π rcr2 Z s exp(− ∆Fcr /kT ), (9.2.19)
(2π mw1 kT )1/2

where mw1 is the mass of a water molecule. The expression before the exponent is termed the kinetic
coefficient. Fletcher (1958, 1962) estimated it as ∼1024 to 1027. The average value of 1025 is used
sometimes in approximate calculations of the nucleation rates.
Similar to the previous derivation for nucleation on an insoluble plane particle, Fletcher (1958,
1962) considered the spherical cap formed on the curved surface of an insoluble particle of radius rN.
The volume of this spherical cap and its two surface areas change and yield a new geometrical factor
f(mwv, x), and the critical energy becomes

16π M w2 σ vw
3
∆Fcr = f (mwv , x ). (9.2.20)
3 [ RT ρ w ln Sw ]2

Here, mwv is the same as before the contact parameter at the interface of the solid substrate and liquid
water, x = rN /rcr, and f(mwv, x) is Fletcher’s geometric factor that accounts for the radius rN of insoluble
particles, and has the form (see derivation in Fletcher, 1958; or in Pruppacher and Klett, 1997):

f (mwv , x ) = (1 / 2 ){1 + [(1 − mwv x ) / y]3 + x 3 (2 − 3ψ + ψ 3 ) + 3mwv x 2 (ψ − 1)},

ψ = ( x − mwv ) / y, y = (1 − 2mwv x + x 2 )1/ 2 . (9.2.21)

Consider the particular cases of small and large rN. In the small particle limit, x = rN /rcr << 1 (which
may correspond to a vanishing insoluble substrate, rN → 0), the value of the contact angle qls =180°,
mwv = −1, and f(mwv , x) = 1, and this case is similar to homogeneous nucleation. In the large particle
400 Heterogeneous Nucleation of Drops and Ice Crystals

limit x = rN /rcr >> 1, the geometrical factor (Eqn. 9.2.21) reduces to the expression (Eqn. 9.2.15) for
planar substrate.
Fletcher’s geometrical factor was derived for the case when a germ forms on the surface of convex
aerosol particles. For the case of spherically concave insoluble substrate with a radius of curvature
rN, the geometric factor can be derived in a similar way:

f (mwv , x ) = (1 / 2 ){1 − [(1 + mwv x ) / y]3 − x 3 (2 − 3ψ + ψ 3 ) + 3mNw x 2 (ψ − 1)},

ψ = ( x + mwv ) / y, y = (1 + 2mwv x + x 2 )1/ 2 . (9.2.22)

Calculations of the drops’ nucleation on this concave substrate showed that it can be faster than on
the convex substrate with Fletcher’s geometric factor (Eqn. 9.2.21).
The nucleation rate just shown was defined per unit area of the insoluble particle. The nucleation
rate Jp,het per particle [s−1] can be calculated in a first approximation multiplying (Eqn. 9.2.19) by the
particle surface area 4p rN2 , or:

4π rN2 c1s ev
J p ,het = π rcr2 Z s exp(− ∆Fcr / kT ). (9.2.23)
(2π mw1 kT )1/ 2

Fletcher (1958, 1962) estimated the average kinetic coefficient (the expression before the exponent)
as ∼1026rN2 .
More sophisticated models of the surface nucleation have been developed that consider adsorp-
tion, desorption, and surface diffusion of the water molecules on the substrate (e.g., Pruppacher and
Klett, 1997; Hellmuth et al., 2012, 2013, and references therein). These models require knowledge of
the adsorption and desorption energies, which are still rather uncertain. A detailed consideration of
these models is beyond the scope of this book.

9.3. Modes of Ice Nucleation and Properties of Ice Nuclei

9.3.1. Modes of Ice Nucleation

Classical cloud physics distinguishes four basic modes of heterogeneous ice nucleation when ice
forms on ice nuclei (IN): deposition mode, condensation-freezing mode, immersion mode, and con-
tact mode. The deposition mode is defined as a process that occurs at ice supersaturation, and water
vapor is directly deposited onto the surface of IN, either directly as an ice layer, or as a liquid film,
which is subsequently transformed into ice at sufficiently low temperatures. The condensation-freezing
mode is usually defined as a two-step process that begins at water supersaturation. An aerosol particle
in this mode acts first as a CCN forming a drop (condensation stage), and then this drop freezes
(freezing stage). The immersion mode is defined as a process when IN is immersed in a drop, presum-
ably at temperatures above the freezing threshold, and freezes after some time at some temperature
below the threshold temperature. The contact mode is defined as the process when an ice nucleus
is originally outside of a drop, and then is brought to the drop surface by any of the scavenging
mechanisms (Brownian diffusion, diffusiophoresis, thermophoresis), contacts the drop, and ice is
nucleated at the moment of contact. Aerosol particles initiating ice in these four modes are termed
9.3. Modes of Ice Nucleation and Properties of Ice Nuclei 401

deposition or sorption nuclei, condensation-freezing nuclei, immersion nuclei, and contact nuclei,
although the same ice nucleus may nucleate ice in different modes.
More recent research illustrates ambiguity among these four modes of ice nucleation. In many
cases, the difference between the condensation-freezing and immersion modes become unclear be-
cause both processes assume condensation with subsequent freezing on the immersed IN. While the
term condensation-freezing is defined earlier as a formation of the droplet at water supersaturation at
the first stage, the first stage often occurs at water subsaturation, when the submicron haze particles
become deliquescent but do not activate into cloud drops, and then freeze at water subsaturation
at the second stage before the formation of cloud drops as was considered in Chapter 8. This may
happen, for example, in the formation of cirrus clouds or diamond dust at water subsaturation. To
emphasize the difference between processes occurring at water sub- and supersaturations, instead
of condensation freezing, we use the term “deliquescence-heterogeneous freezing mode,” or DF or
“DhetF mode,” introduced in Khvorostyanov and Curry (2004a,b, 2005a). The DF or DhetF mode is
defined as a process of heterogeneous ice nucleation when mixed aerosol particles (CCN) become
deliquescent but do not transform into drops, and freeze as haze particles still at water subsaturation.
In contrast, immersion freezing is understood as a process of the formation of cloud drops from im-
mersed ice nuclei and subsequent freezing at water supersaturation.

9.3.2. Properties of Ice Nuclei

Ice nuclei represent a small subset of aerosol particles that can catalyze ice nucleation—i.e., they have
the ability to nucleate ice under conditions when ice would not form without these particles. Numer-
ous studies of IN properties are reviewed in a number of monographs and papers (e.g., Fletcher, 1962,
1970a; Mason, 1971; Hobbs, 1974; Young, 1993; Pruppacher and Klett, 1997; Lohmann and Diehl,
2006; Vali, 2008; DeMott et al., 2011; Hoose and Möhler, 2012; Ladino et al., 2013; and references
therein). Despite significant efforts studying IN and the collection of a vast amount of data on IN,
a complete physical understanding of their nature, properties, and the mechanisms of ice nucleation
remain elusive, and various experimental data are controversial. As emphasized by Pruppacher and
Klett (1997, Section 9.2), “Unfortunately, none of the presently available devices which count the frac-
tion of aerosol particles acting as IN is capable of allowing four different modes of action, nor can they
realistically simulate the time scale over which temperature and supersaturation vary in atmospheric
clouds. Therefore, the IN concentrations quoted in the literature have to be treated with considerable
caution.” Here we provide a brief outline of some properties of IN that are essential for understanding
the mechanisms of IN activity in heterogeneous nucleation and calculations of ice nucleation.

The Nature of IN
Among the various methods of studying IN, two techniques are used most frequently: direct physico-
chemical analyses of the substances and residues contained in ice crystals, and laboratory tests of the
ice nucleating ability of various substances. A wide array of substances has been found within snow
crystals by means of physico-chemical analyses that allow identification of the nature of ice nuclei.
Many substances have been tested in the laboratory for their ice nucleating ability, including: mineral
dust particles and clays, soot of various origin from anthropogenic and natural emissions, aerosols of
402 Heterogeneous Nucleation of Drops and Ice Crystals

biological origin (bacteria, leaf litter, fungal spores, various pollens, and diatoms), solid ammonium
sulfate, organic acids, humic-like substances, and metallic compounds. A large group of artificially
formed aerosols like AgI, CuI, and PbI has been tested in laboratories and used in cloud seeding
experiments for artificial cloud crystallization (see Chapter 4).
Hoose and Möhler (2012) performed a detailed review of more than 60 laboratory experiments with
various kinds of mineral dust particles, about 20 experiments with soot, and about 40 experiments
with bioaerosols. The experiments were conducted using various devices and under a wide range of
conditions. This comparison indicated that common clay minerals such as kaolinite, montmorillonite,
and illite may serve as good IN, while natural desert dusts are less effective as IN and may require
higher ice supersaturations or colder temperatures for activation. The conclusions on soot as IN are
less certain and there is a greater spread in the results depending on the sort and origin of soot, but
it can be confirmed that soot particles are in general less effective ice nuclei than mineral dust, also
requiring colder temperatures and higher supersaturations. The ice nucleating ability of bioaerosols
was found to be a selective property. A small fraction of bacteria was able to nucleate ice at subzero
temperatures. Abbatt et al. (2006) found that solid ammonium sulfate particles were able to nucle-
ate ice both at water subsaturation in deposition mode, and in immersion mode in solution drops.
A detailed review of the experimental research on contact nuclei was provided by Ladino et al. (2013).

Concentrations
Measured concentrations NIN of IN vary significantly. They exhibit a general tendency to increase
with decreasing temperature and increasing humidity. It was found that various IN may nucleate ice
heterogeneously over a wide temperature range from a few degrees below 0 °C to very cold tempera-
tures below −80 °C and possibly lower. The values of NIN measured prior to the 1970s vary in the
range 10−3 to 0.1 L−1 at −10 °C, and in the range from a few hundredths to a few per liter at −20 °C
(Pruppacher and Klett, 1997). Many of these measurements used static filter techniques. Newer
devices—e.g., continuous flow diffusion chambers (CFDC)—showed NIN by about one order of mag-
nitude higher (Cooper, 1986; Rogers, 1982; Al Naimi and Saunders, 1985; Meyers et al., 1992).
Some of these measurements were performed at rather high water supersaturation, up to 20–25%,
so that many new small drops could form and freeze in the immersion mode. The other experiments
were performed at positive ice supersaturation but at water subsaturation, so that deliquescence-
freezing, contact, or deposition modes could act. Thus, separation of the modes and identifying their
relative contributions and concentrations of various types of IN is not a simple task.

Partial solubility
The old concept adopted in cloud physics treated ice nuclei as highly insoluble particles. In the real
atmosphere, most ice nuclei have appreciable fractions of soluble materials, which has been empha-
sized in the field projects of the 1990s and 2000s—e.g., SUCCESS (Subsonic Aircraft: Contrail and
Cloud Effects Special Study, Special issue of the Geophysical Research Letters, v. 25, 1998); and
FIRE-SHEBA (First International Regional Experiment – Surface Heat Budget of the Arctic; Curry
et al., 2000; and Special issue of the Journal of Geophysical Research, v. 106, 2001), CRYSTAL-
FACE (Cirrus Regional Study of Tropical Anvils and Cirrus Layers – Florida Area Cirrus Experiment
case study) (Jensen et al., 2005; Fridlind et al., 2004; Czizco et al., 2004).
9.3. Modes of Ice Nucleation and Properties of Ice Nuclei 403

Detailed analysis of IN physicochemical properties has shown that IN are not necessarily totally
insoluble (Chen et al., 1998), but a significant fraction of the IN may represent mixtures of insoluble
substrates with sulfates or other soluble materials with soluble volume fractions of 0.2–0.9. Hence,
the same aerosol particles may serve both as IN and CCN. The fraction of these mixed IN has been
observed to be as high as 40% of the IN in the lower and middle troposphere, and up to 27% in the
upper troposphere (Chen et al. 1998, Rogers et al. 1998; 2001). Note that the energy-dispersive X-ray
analysis used in these experiments was not able to detect soluble mass fractions smaller than 10%;
if it had been possible to make this threshold lower (e.g., down to 1%), the fractions of these mixed
IN-CCN could be considerably higher.
These experiments indicated the necessity of modifying the traditional view of IN as completely
insoluble particles, as well as the parameterizations of heterogeneous ice nucleation. DeMott et al.
(1998) developed a model of heterogeneous ice nucleation by assuming that all heterogeneous IN are
freezing nuclei, which are deliquescent mixed cloud condensation nuclei (CCN) with 50% insoluble
and 50% soluble matter (sulfuric acid in the upper troposphere), and are contained within 10% of the
CCN population with sizes above 0.1 μm; the freezing fraction of these IN-CCN was parameterized
as a function of temperature. Khvorostyanov and Curry (2000, 2004a,b, 2005a, 2009b, hereafter
KC00, KC04a,b, KC05, KC09), and Curry and Khvorostyanov (2012, hereafter CK12) extended
classical nucleation theory and developed a theory of heterogeneous ice nucleation by freezing of
CCN containing both soluble and insoluble fractions, with the possibility of ice nucleation at both
water sub- and supersaturations.
It has been assumed in many studies that the dominant mode of crystal formation in cold cirrus
might be the homogeneous freezing of haze particles in conditions of subsaturation with respect to
water (e.g., Sassen and Dodd, 1988, 1989; Heymsfield and Sabin, 1989; DeMott et al., 1994). High
ice supersaturations in cirrus and an important role of heterogeneous freezing in cirrus and contrail
formation have been recognized recently and have been intensely studied in subsequent years (e.g.,
Jensen et al., 1994, 1996, 2001, 2005; DeMott et al., 1994, 1997, 1998; 2002; Kärcher et al., 1996,
2006; Khvorostyanov and Sassen, 1998a,b,c, 2002; Kärcher and Lohmann, 2003; Sassen and Benson,
2000; Lin et al., 2002; Gierens, 2003; Haag et al., 2003; Khvorostyanov et al., 2001, 2006; Fridlind
et al., 2004; Barahona and Nenes, 2009; Krämer et al., 2009; Spichtinger and Gierens, 2009; Hoose
and Möhler, 2012), although significant differences still exist in the description of this process owing
to the absence of adequate theories. The parameterizations and theories of heterogeneous freezing on
partially soluble IN are discussed in the subsequent sections of this chapter.

Size
Laboratory and field experiments show that the efficiency of IN increases with increasing size of
aerosol particles. Since ice nucleation occurs on the surface of aerosol particles, the catalyzing effect
of IN increases with the surface area—i.e., with the particle size. The insoluble fraction of aerosol
particles generally increases with their size, making them more efficient IN. Many substances known
as good ice nucleators, like silicates, sand, or clay particles, are contained mostly in the large particle
range. There is evidence that the IN efficiency rapidly decreases at small sizes below ∼0.01 μm; how-
ever, the exact limit of the nucleating ability is uncertain. Thus, the nucleation ability of IN increases
with size; however, the number of aerosol particles decreases with size. As a result of these two
404 Heterogeneous Nucleation of Drops and Ice Crystals

counteracting tendencies, some types of aerosol can be the most efficient IN in certain size ranges.
For example, analysis of snow crystals in some experiments showed that the sizes of IN ranged
between 0.1 and 15 μm with a mode between 0.5 and 5 μm (e.g., Pruppacher and Klett, 1997).

Chemical structure
Studies of the chemical composition of IN show that those aerosol particles having chemical bonds
at the surface similar to the bond structure in the ice lattice (O-H-O) may be more effective ice nuclei.
Many organic particles have similar hydrogen bond structures, therefore they may be efficient ice
nucleants. These include some bacteria, leaf litter, cholesterol, phloroglucinol, and many others.
Several organic substances were found to nucleate ice at temperatures warmer than −10 °C, and up to
−1 to −2 °C. It was shown that the ice nucleating ability of bioaerosols is caused by the presence on
the surface of these substances of crystalline structures similar to ice.

Crystallographic structure
Experimental studies of IN show that the ice nucleating properties of IN depend on their crystal-
lographic structure. Many substances with crystallographic structure close or similar to ice structure
appeared to be better ice nucleators than the substances with different structures. This, in particular,
explains the good ice nucleability of artificial ice nuclei used for cloud seeding—e.g., AgI, PbI, CuS,
and others that have been successfully used in weather modification programs since the 1940s as
described in Chapter 4. The parameters of their crystalline lattice are similar to that of ice.
As was mentioned in Section 3.6, if the crystallographic differences between ice and the substrate
are sufficiently small, both ice and substrate lattices may deform elastically and then join coherently.
This misfit between the ice and substrate lattices causes an elastic strain; that is, an additional energy
that hampers ice nucleation on the surface of the substrate. In general, this strain is characterized by
the multicomponent tensor of elastic strain (Landau and Lifshitz, v.5, 1958b). In applications for
nucleation problems, it is customary to use a simpler approach and to describe the effect of strain by
the relative misfit between the ice and substrate lattices—i.e., by the relative difference between the
lengths of ice and substrate lattice unit cells. A more detailed description of this effect will be given
in Sections 9.5 and 9.7.

9.4. Empirical Parameterizations of Heterogeneous Ice Nucleation

For the past four decades, ice nucleation processes and the number concentration NIN of atmospheric
aerosol particles that initiate ice phase (ice nuclei, IN) have been parameterized based on experi-
mental data mostly as two independent functions: of temperature and of supersaturation over ice or
over water. There have been some attempts at representation of experimentally derived values of IN
concentration simultaneously as a function of temperature and supersaturation.
Several authors developed parameterizations of ice nuclei concentrations NIN (T) or ice particle
concentrations Ni(T) as empirical functions of temperature T. Fletcher (1962) suggested a parameter-
ization of NIN(T) as an empirical exponential function of the temperature T:

N i (T ) = AF exp[ BF (T0 − T )], (9.4.1)

9.4. Empirical Parameterizations of Heterogeneous Ice Nucleation 405

with the parameters AF = 10−5 L−1 and BF = 0.6 (°C)−1, T0 = 0 °C and T in °C, although these param-
eters could substantially vary around these values (Pruppacher and Klett, 1997). Huffman and Vali
(1973) and Huffman (1973) offered a power law by ice supersaturation si of

N i ( Si ) = Cs sibs , (9.4.2)

with Ni in L−1, si in %, and Cs and bs being the constants for a given air mass. It was found later that
3 < bs < 8, and there was greater uncertainty in Cs.
Berezinsky and Stepanov (1986) offered a similar parameterization consisting of an exponential
function by the temperature:

N IN (T ) = N a 10 k BS ( T −T0 ) , k BS = 0.14 − 0.055log(d 2 ), (9.4.3)

where Na is the concentration of aerosols of a given size, d2 is the mean square diameter of aerosol in
μm, and log(x) is the decimal logarithm of x. Thus, the segregation of NIN by size was accounted for.
The dependence on ice supersaturation was found similar to Huffman’s (1973) power law, (Eqn. 9.4.2),
but with additional dependence of parameters on temperature. Berezinsky and Stepanov (1986) also
presented the simultaneous graphical dependences of NIN (T, si) on both T and si that showed the
comparable roles of T and si on NIN, so that the IN concentration was a function of both parameters
as NIN (T, si).
Cooper (1986) derived a temperature-dependent parameterization that refined Fletcher’s function as

N i (T ) = ATC 10 BTC ( T0 − T ) , or N i (T ) = ATC e 0.31( T0 − T ) , (9.4.4)

where T is in degrees K, BTC = 0.135 (K)−1, and ATC = 4.47 × 10−3 L−1. Cooper’s parameterization has
a smaller T-slope than Fletcher’s (Eqn. 9.4.1), produces greater Ni at warmer T > −22 °C, and more
realistic smaller IN at lower T that are closer to observations. Another modification of Fletcher’s
parameterization was suggested by Sassen (1992) to account for the depletion of IN with height z
and to make it more realistic at low T:
N i (T ) = AT 0 exp(− Az z ) exp[ BT (T0 − T )], (9.4.5)

where AT0 = 10−5 L−1 is the measured concentration of IN at the earth’s surface, Az = 0.75 km−1 deter-
mines a decrease of IN with height, and BT is the same as in Fletcher’s (Eqn. 9.4.1).
Both supersaturation and temperature dependencies were parameterized in a single equation by
Cotton et al. (1986) who combined Fletcher’s T-dependence and Huffman’s si-dependence

N i (T ) = AT (si / si 0 )bs exp[ BT (T0 − T )], (9.4.6)

where AT and BT are the same as in Fletcher’s (Eqn. 9.4.1), si is the fractional ice supersaturation, and
si0 is the fractional ice supersaturation at water saturation at T.
Meyers et al. (1992) noted that the combined T-si parameterization by Cotton et al. (1986) under-
epredicts IN concentrations because it was constructed from the parameterizations (Eqns. 9.4.1) and
(9.4.2) that were based on static filter and other measurements prior to use of continuous flow diffu-
sion chambers (CFDC) and gave lower (up to an order of magnitude) IN concentrations than were
406 Heterogeneous Nucleation of Drops and Ice Crystals

obtained later with CFDC. Meyers et al. (1992) reanalyzed the data and suggested for the combined
condensation-freezing and deposition modes another empirical parameterization of the condensation-
freezing (CF) nucleation as a supersaturation-dependent only function

N i (si ) = exp(aM + bM si ), (9.4.7)

with Ni in L , si in %, aM = −0.639, and bM = 0.1296. This was suggested to be valid at −20 < T
−1

< −7 °C, and 2 < si < 25%, but (Eqn. 9.4.7) was used later in several works outside of these regions
(e.g., Comstock et al. (2008) used it for cirrus clouds at T < −40 °C). Although the temperature
dependence was present in the original data, Meyers et al. (1992) averaged it and retained only the
supersaturation dependence. A similar si-dependent parameterization for deposition nucleation on
dust particles was suggested by Möhler et al. (2006) based on measurements in a large expansion
chamber of 84 m3. Cotton et al. (2003) modified (Eqn. 9.4.7) to include the prognostic variable NIN:

N i (si ) = N IN exp(bM si ), (9.4.7a)

with Ni in L−1, si in %, and where T < −5 °C. A comparison with MDC92 (Eqn. 9.4.7) indicates that
this could imply that NIN = exp(aM); however, (Eqn. 9.4.7a) assumes the variable NIN can be deduced
from the continuous flow diffusion chamber data.
In contrast, the contact nuclei Nac were parameterized in Meyers et al. (1992) as a temperature
power law. The supersaturation dependence was smoothed and disregarded although many data indi-
cated such dependence in contact nucleation caused by the physical mechanisms of diffusiophoresis
and thermophoresis that are governed by the supersaturation field (Young, 1993; Pruppacher and
Klett, 1997; Seinfeld and Pandis, 1998). Contact nucleation will be considered in Chapter 10.
These parameterizations were revised again for the low temperature range by DeMott et al. (1998),
who assumed that IN are mixed aerosol particles with radii over 0.1 μm, consisting of 50% solu-
ble and 50% insoluble fractions—i.e., similar to cloud nuclei (CN) or to cloud condensation nuclei
(CCN). The IN were measured simultaneously with CN using CFDC onboard of aircraft at low
temperatures, and IN were parameterized in the temperature range −25 < T < −38 °C as the freezing
fraction of CN:
N IN = N CN FIN/CN; (9.4.8)

FIN/CN = aD (T0 − T )bD , (9.4.9)

with aD = 1.3 × 10−22; bD = 11.75. This parameterization was suggested for the combined deposition
and condensation-freezing modes. The water supersaturation sw varied in these measurements in the
range from subsaturation, when deliquescent submicron mixed haze particles (unactivated CCN)
could be present, to ∼18% when mixed CCN could transform into the drops and freezing could pro-
ceed in the immersion mode (DeMott et al., 1998, Fig. 1).
Note that these high water supersaturations sw = 1–18% lead to very rapid activation of the cloud
condensation nuclei (CCN) down to very small sizes < 0.01 μm (see Chapter 6 and Fig. 6.5). This
activation takes from a few tenths of a second to a few seconds (see Chapters 6 and 7); that is, it is
much faster than heterogeneous ice nucleation that may take 10–30 min (Pruppacher and Klett, 1997;
Lin et al., 2002; Khvorostyanov and Curry, 2005a; Eidhammer et al., 2009; see Section 9.14 here), so
9.4. Empirical Parameterizations of Heterogeneous Ice Nucleation 407

that almost all mixed aerosol particles at sw > 0 may have converted into cloud drops prior to freezing.
Thus, the term “condensation” was understood literally but the condensation-freezing mode was not
isolated and was actually mixed with the immersion mode at sw > 0. This feature is pertinent to all
freezing experiments where positive sw is achieved.
Thus, Meyers et al. (1992) parameterized IN as a function of si only at T > −20 °C, and DeMott
et al. (1998) parameterized them as a function of T only at T < −25 °C. We do not expect that there
is an abrupt change of the mechanism of IN nucleation at −20 °C, and a construction of a unified
parameterization with both dependencies remained a problem.
Another empirical parameterization for the immersion mode with ice nuclei of soot, mineral dust,
and biological nuclei were suggested by Diehl and Wurzler (2004) based on laboratory experiments
and by generalizing Bigg’s (1953) conception of the median freezing temperature. Diehl and Wurzler
(2004) suggested a parameterization for the nucleation rate Jhet(T) and freezing rate dNf /dt of

J het (T ) = aDW Bh ,i exp(aDW Ts ) (9.4.10a)

dN f dN u dT dT
− = = N u J hetVd = N u aDW Bh ,iVd exp(aDW Ts ) , (9.4.10b)
dt dt dt dt
where Nf and Nu are the numbers of frozen and unfrozen drops, respectively, Ts = T0 − T is super-
cooling, Vd is the droplet volume, and Bh,i and aDW are the empirical constants. The values of Bh,i
varied from 2.91 × 10−9 cm−3 for soot particles, to 6.15 × 10−8 cm−3 for kaolinite, 3.23 × 10−5 cm−3 for
montmorillonite, and 6.19 × 10−5 cm−3 for illite, and were much greater for biological particles that
appeared to be effective IN with Bh,i = 1.01 × 10−2 cm−3 for pollen, 4.38 × 10−1 cm−3 for leaf litter, and
6.19 × 10 cm−3 for bacteria. This choice of the parameters was based on fitting to laboratory measure-
ments as described in Diehl and Wurzler (2004). The freezing point depression due to the presence
of solutes was accounted for using the parameterization by Koop et al. (2000) for homogeneous
nucleation, assuming that the depressions are similar for homogeneous and heterogeneous nucleation
processes. This parameterization by Diehl and Wurzler (2004) was tested in the GCM ECHAM4
(Lohmann and Diehl, 2006) and in a mesoscale model COSMO (Zubler et al., 2011) and showed
reasonable performance with realistic Nc.
Subsequent field experiments stimulated further revisions of the previous parameterizations.
Measurements made during the Mixed-Phase Arctic Cloud Experiment (MPACE) in autumn 2004
(Verlinde et al., 2007) and subsequent numerical simulations showed that MDC92 parameterization
(Eqn. 9.4.7) overestimates IN concentration and leads to cloud glaciation that is too rapid (Prenni
et al., 2007). A modification of MDC92 was suggested by Prenni et al. (2007), so that the functional
form was the same as in (Eqn. 9.4.7), but the coefficients were different: aM = −1.488, bM = 0.0187.
As with MDC92, this parameterization by Prenni et al. (2007) also did not contain dependencies on
temperature and aerosol concentration, had very weak si-dependence, but gave substantially smaller
IN concentrations (0.2–0.4 L−1) that were comparable to measured values in MPACE that permitted
the existence of the mixed cloud state for several hours.
The next modification of the MDC92 parameterization was performed by Philips, DeMott and
Andronache (2008, hereafter PDA08), who developed a new empirical parameterization using
MDC92 as a basis. PDA08 extended this parameterization for various T- and si-ranges and generalized
408 Heterogeneous Nucleation of Drops and Ice Crystals

the parameterization to account for the three types of freezing aerosol (dust and metallic compounds,
black carbon, and insoluble organics). This parameterization included appropriate scaling and inte-
gration over the surface areas of these aerosols, so that the concentration Nc,x of IN of the x-th kind is
∞
dnx
N c ,x = ∫ {(1 − exp[− µ ( D , S , T )]} d log D
log[0.1 µm ]
x x i
x
d log Dx , (9.4.11)

where x denotes any of the 3 aerosol types, nx is the aerosol mixing ratio, mx is the average activated
IN per aerosol of diameter Dx, and mx is proportional to Nc(si) from (Eqn. 9.4.7) multiplied by some
coefficients. For a low freezing fraction, which often takes place, Nc,x ∼ mx ∼ Ni (PDA08).
Eidhammer et al. (2009, hereafter EDK09) compared in the parcel modeling the ice schems
(PDA08; Diehl and Wurzler (2004), hereafter DW04, and Khvorostyanov and Curry (2000, 2004a,b),
hereafter, KC00-04) and showed that PDA08 parameterization produces much lower crystal concen-
trations than the parameterizations DW04 and KC00-04. Curry and Khvorostyanov (2012) analyzed
the results of simulations in EDK09 with these three ice schemes, and compared simulated in EDK09
crystal concentrations, LWC, IWC, and cloud phase state with the GCMs parameterizations and
climatological data on cloud phase state. It was shown that the PDA08 parameterization is much
less effective in ice nucleation and cloud glaciation than the parameterizations DW04, KC00-04 and
other theoretical schemes and disagrees with climatological data on cloud phase state. Nucleation of
a sensible number of crystals and transformation into a really mixed state occurs in PDA08 scheme
only when homogeneous freezing of the large drops begins at T ≤ −35 °C (see Section 9.17 and
Figs. 9.35 and 9.36). This indicates that the PDA08 scheme may require modification and it might
be necessary to increase the coefficients or surface areas in this parameterization so that it would be
able to produce mixed-phase clouds at T < −15 °C or −20 °C.
DeMott et al. (2010) proposed a new parameterization for immersion and condensation freezing
as a simple power law function by temperature:

N c = aD (− Tc )bD ( N a ,05 )cM Tc + d M , (9.4.12)

where Nc is in L , Tc is the temperature in degrees Celsius, and Na,05 is the concentration (in cm−3) of
−1

aerosol particles larger than 0.5 μm. The first set of coefficients was: aD = 1.1968 × 10−5, bD = 3.6434,
cD = −0.0167, and dD = 0.2877; the subsequent refined set was slightly changed to aD = 5.94 × 10−5,
bD = 3.334, cD = 0.0264, dD = 0.0033. In contrast to MDC92 or PDA08, this parameterization includes
only temperature and does not depend on supersaturation. Connolly et al. (2009) suggested a new
scheme of heterogeneous nucleation based on a new concept of the active sites on the surface of IN.
Niemand et al. (2012) developed a particle-surface-area-based parameterization of immersion freezing
on desert dust particles. Development of similar new empirical or semi-empirical schemes is continuing.
This brief overview shows that all empirical parameterizations still require refinements and more
experimental data—both laboratory and field—are needed.

9.5. Nucleation of Crystals in the Deposition Mode on Water-Insoluble Particles

The process of ice nucleation in the deposition mode is similar to the drop nucleation on an insoluble
surface considered in Section 9.2, but replacing all the water properties with ice properties and
replacing the water saturation ratio Sw with the ice saturation ratio Si. However, an additional effect
9.5. Nucleation of Crystals in the Deposition Mode on Water-Insoluble Particles 409

arises for the ice deposition. Since the parameters of the ice crystalline lattice are in general different
from the lattice of an insoluble substrate, this is called the lattice misfit. Thus, the ice lattice should
adjust to the substrate lattice. This causes either deformation of the ice lattice, the elastic misfit strain,
or can cause dislocations at the ice–substrate interface. The misfit strain causes an increase in the bulk
free energy, and dislocations increase the interfacial energy (see Section 3.6).
The elastic misfit strain can be characterized in terms of the relative misfit between the ice and substrate
δ mis = (an − ai ) / ai , (9.5.1)

where an is the substrate lattice vector and ai is the length of an ice unit cell. If the misfit is small—
that is, the substrate lattice is similar to the ice lattice—this is called the “epitaxy,” and such substrates
are expected to be good ice nucleants. For example, AgI, PbI, and CuI have lattice parameters suf-
ficiently close to those of ice, have good nucleating ability, and are therefore used as the crystallizing
agents for cloud seeding in the weather modification projects. If the misfit strain is small—i.e., the
condition of epitaxy is fulfilled—then the number of dislocations may be small, and the elastic strain
e is equal to the misfit dmis. If the misfit is large, it may be assumed that the ice lattice is not accom-
modated to the substrate and the elastic strain is zero. The elastic strain causes the appearance of the
additional energy in an ice embryo:

∆Fel = Vl Cε ε 2 , (9.5.2)
11
where Vl is the particle volume. An estimate for the strain coefficient is Ce ≈ 1.7 × 10 erg cm at 0 °C
−3

(Turnbull and Vonnegut, 1952), and e is measured in %.

The ice nucleation rate in the deposition mode can be written similarly to (Eqn. 9.2.7) for drop
nucleation
J s ,het = cgs jg( + ) Ags Z s , (9.5.3)

where jg( + ) is the molecular flux onto this g-mer, Ags is the surface area of the germ, Zs is the Zeldov-
ich factor, and cgs is the concentration of g-mers that is assumed to be described by the Boltzmann
distribution using critical energies DFcr similar to (Eqn. 9.2.6).
The germ critical energy and critical radius can be calculated in various ways. We present a deriva-
tion similar to that in Section 9.2 with additional accounting for the elastic strain energy. Consider
formation of an ice embryo on the surface of an insoluble particle with radius rN. We can write again
the free energy as a sum of the volume and surface terms, similar to (Eqn. 9.2.16a), but replacing
Sw → Si, and adding the term with the elastic strain energy DFel from (Eqn. 9.5.2) multiplied by
f (miv,x) for the cap geometry:

 4π r 3  RT ln( S )  
∆Fgs = f (miv , x )  − 
i
− Cε ε 2  + 4π r 2σ iv  , (9.5.4)
 3  vi µ  

where vim = Mw/ri is the molar volume of ice, ri is the ice density, and miv is the cosine of the contact
angle at the ice-vapor interface:

miv = cos θ iv = (σ Nv − σ Ni )/σ iv , (9.5.5)

410 Heterogeneous Nucleation of Drops and Ice Crystals

determined by the three surface tensions: substrate–ice (sNi), ice–vapor (siv), and substrate–vapor
(sNv) (the subscripts N, i, and v here mean the corresponding substances: solid substrate, ice, and
vapor). The shape factor f(miv, x) in (Eqn. 9.5.4) is defined by (Eqn. 9.2.21) with the replacement of
mwv → miv, which is defined by (Eqn. 9.5.5).
The critical energy of an ice germ is determined from the condition of minimum ∂DFgs(rcr)/∂r = 0,
which yields from (Eqn. 9.5.4)

 RT ln Si 
rcr  − + Cε ε 2  + 2σ iv = 0, (9.5.6)
 vi µ 

and we obtain the critical radius

2σ iv
rcr =
RT ln Si / vi µ − Cε ε 2
2σ iv M w 2σ iv
= = , (9.5.7)
RT ρi ln Si − M w Cε ε 2 Rv T ln Si − Cε ε 2

As in Section 9.2, rcr can be also written via the affinity A∝,vi = Dmvi = mv−mi:

2σ iv vi µ
rcr = (9.5.8a)
µ v − µi
Comparison with (Eqn. 9.5.7) shows that

µ v − µi = RT ln Si − Cε ε 2 vi µ (9.5.8b)

Thus, the affinity (Eqn. 8.1.7a) for vapor–water A∝,vw = Dm vw is generalized for vapor–ice with
accounting for the energy of the elastic misfit strain. The critical energy of a convex spherical ice cap
with radius rcr formed on the surface of an insoluble substrate with radius rN is obtained from (Eqns.
9.5.4) and (9.5.7) similar to (Eqn. 9.2.20):

4π σ A 16π M w2 σ iv3 f (miv , x )

∆Fcr = σ iv rcr2 = iv cr =
3 3 3 [ RT ρi ln Si − M w Cε ε 2 ]2
16π σ iv3 f (miv , x )
= , (9.5.9)
3 [ Rv T ρi ln Si − Cε ε 2 ]2

where Acr is the surface area of a spherical germ with radius rcr . Here, miv is the contact parameter of the
angle between the ice germ and substrate, and the shape factor f(miv, x) for a convex spherical ice cap
with radius rcr on the surface of an insoluble substrate with radius rN is defined similar to (Eqn. 9.2.21)
for liquid germs replacing mwv → miv:

f (miv , x ) = (1 / 2 ){1 + [(1 − miv x ) / y]3 + x 3 (2 − 3ψ + ψ 3 ) + 3miv x 2 (ψ − 1)},

ψ = ( x − miv )/ y, y = (1 − 2miv x + x 2 )1/ 2 , (9.5.10)

and x = rN/rcr. The shape factor of the concave ice germs that may form in cavities or capillaries of the
substrate is also defined by (Eqn. 9.2.22) with the replacement mwv → miv.
9.6. Ice Nucleation by Deliquescence-Freezing and Immersion 411

Now, the nucleation rate of crystals from vapor by the deposition mode per unit area of an insoluble
surface per unit time [cm−2 s−1] can be written similar to (Eqn. 9.2.19) for the drop nucleation on an
insoluble substrate:
c1s ev
J sdep = π rcr2 Z s exp(− ∆Fcr /kT ), (9.5.11)
(2π mw1 kT )1/2

where mw1 is the mass of a water molecule, c1s is the concentration of single molecules adsorbed on
the surface, and rcr and DFcr are the critical radius and energy defined in (Eqns. 9.5.7) and (9.5.9). The
nucleation rate Jdep per particle [s−1] can be calculated to a first approximation similar to (Eqn. 9.2.23)
by multiplying by the particle surface area 4prN2—i.e., Jdep = 4prN2Jsdep, or

J dep = Cdep exp(−∆Fcr /kT ), (9.5.12)

4π 2 rN2 c1s ev 4π 2 rN2 N Av c1s ev 2

Cdep = 1/2
π rcr2 Z s = π rcr Z s , (9.5.12a)
(2π mw1 kT ) (2π M w RT )1/2

where NAv is the Avogadro number. Fletcher (1958, 1962) estimated the average kinetic coefficient
(the expression before the exponent) as Cdep ∼1026rN2. This expression along with (Eqn. 9.5.9) for
DFcr and (Eqns. 9.2.21) or (9.2.22) for f(miv, x) can be used for calculations of the ice nucleation rates
in the deposition mode.
The nucleation rates by the deposition mode become noticeable when the deposition contact param-
eters miv are sufficiently close to 1, or the contact angles are small (e.g., Fletcher, 1962; Young, 1993).

9.6. Ice Nucleation by Deliquescence-Freezing and Immersion

Consider a three-phase system consisting of an ice germ of radius rcr that forms on a curved insol-
uble substrate with radius rN inside an aqueous solution drop with radius rd. The rate of heteroge-
neous germ formation in a supercooled droplet of water or solution per unit area per unit time,
JS,fr [cm−2 s−1], can be calculated similarly to that for homogeneous nucleation in Chapter 8 or to drop
nucleation in Section 9.2, using the equation of balance for JS,fr:

J S , fr = cgs jg( + ) Ags Z s , (9.6.1)

where cgs is the concentration of g-mers or ice germs on the surface of an ice nucleus, jg( + ) is the dif-
fusive flux of the molecules across the liquid–ice boundary onto this g-mer (see Chapters 5, 8), Ags is
the IN surface area adsorbing the molecular flux from the liquid, and Zs is the Zeldovich factor. We
assume that the Boltzmann distribution is valid for cgs:

cgs = c1s exp(−∆Fcr /kT ), (9.6.2)

where c1s is the concentration of water molecules adsorbed on 1 cm−2 of a surface, and DFcr is the
energy of the germ formation.
The molecular flux to the surface of IN is determined by the potential barrier due to the activation
energy DFact and is assumed to be the same as in the case of homogeneous nucleation (Eqn. 8.3.2):

N cont kT
jg( + ) = exp(− ∆Fact / kT ), (9.6.3)
h
412 Heterogeneous Nucleation of Drops and Ice Crystals

where k and h are Boltzmann’s and Planck’s constants, DFact is the activation energy at the solution–ice
interface (or water–ice interface in the case of freezing of pure water), and Ncont is the concentration of
molecules in contact with a unit area of ice. Substituting (Eqns. 9.6.2) and (9.6.3) into (Eqn. 9.6.1) we obtain

 ∆F ∆F 
J S , fr (T , rN ) = Bhet exp  − act − cr  , (9.6.4)
 kT kT 
where
kT
Bhet = Z s N cont Ags c1s . (9.6.5)
h
As in the case of homogeneous nucleation in Chapter 8, the nucleation rate is determined by the two
energy barriers formed by the activation energy DFact and the critical energy DFcr. An estimate shows
that Zs ∼ 10−1 (i.e., accounting for the reverse flux of the molecules from an ice germ to the liquid
decreases the nucleation rate by an order of magnitude), and that the product NcontAgs, ∼ the number
of molecules in contact with the ice germ, is ∼10. Thus, the product ZsNcontAgs ∼ 1 and Bhet can be
approximately simplified as

kT
Bhet ≈ c1s . (9.6.6)
h

The nucleation rate Jf,het per particle [s−1 particle−1] with surface area ArN = 4π rN2 , where rN is the
radius of an insoluble fraction of an aerosol particle that serves as IN, can be approximately evaluated
by multiplying JS,fr by ArN:

 ∆F ∆F 
(9.6.7)
J f ,het (T , rN ) = Chet exp  − act − cr  ,
 kT kT 
where Chet is the kinetic coefficient

kT
Chet ≈ c1s 4π rN2 . (9.6.8)
h
According to Fletcher (1962) and Young (1993), c1s ∼ 1015 cm−2 and Chet ∼ 1028rN2 . Fletcher (1962, p. 45)
emphasized that variation of Chet even by a few orders of magnitude has little effect on the final result
because of the primary effect on the nucleation rates of the exponential term, whose variations are
much greater.
Application of (Eqn. 9.6.7) for calculation of the nucleation rate Jf,het requires knowledge of the
critical energy DFcr that is related to the ice germ critical radius rcr. The equations for DFcr and rcr are
derived in the next section.

9.7. Critical Radius and Energy of Heterogeneous Freezing

9.7.1. Basic Dependencies of Heterogeneous Freezing

A review in Section 9.4 of the empirical parameterizations showed that these methods attempted to
describe the two major dependencies of the heterogeneous freezing process on the temperature and
humidity or saturation ratio. These parameterizations mostly considered one of these dependencies,
9.7. Critical Radius and Energy of Heterogeneous Freezing 413

but not both together, except for a few attempts at empirical parameterizations simultaneously as a
function of temperature and supersaturation. This section is devoted to derivation from the theory of
both the T- and Sw dependencies that can justify these empirical parameterizations and provide the
quantitative values of the empirical coefficients.
Earlier formulations of the classical nucleation theory for freezing (J. J. Thomson, 1888) described
the temperature dependence of the critical radius rcr, energy DFcr, but did not contain a humidity depen-
dence. Fletcher (1962) gave a formulation for rcr and DFcr in terms of ratio of the saturated humidities
over water and ice, and this is equivalent to the T-dependence, as will be shown later. Dufour and
Defay (1963) and Defay, Prigogine, and Bellemans (1966) derived from the classical nucleation theory
the expressions for rcr and DFcr, that take into account the solution effect equivalent to the humidity
dependence, but this was expressed via the osmotic potential or water activity that may require rather
complicated calculations for an ensemble of polydisperse drops in a cloud model. Fukuta and Schaller
(1982) developed a theory of condensation-freezing that proceeds in two steps: a) condensation on the
surface of an insoluble nucleus at water supersaturation as described in Section 9.2 here; and b) the
subsequent freezing of the water film formed on this insoluble nucleus following Fletcher’s (1962)
formulation taking into account the T-dependence. A similar model was suggested by Young (1993)
for the immersion-freezing mode. This approach can be suitable for description of heterogeneous ice
nucleation on insoluble IN at water supersaturation, in particular on artificial IN used in cloud seeding.
However, this treatment did not allow for calculations of ice nucleation by the freezing of solution
drops at water supersaturation, haze solution particles (deliquescent CCN) at water subsaturation and
the freezing of interstitial deliquescent CCN in a cloud. This requires a generalization of the classical
theory, which is described in the next sections. As was discussed in Section 9.3, most ice nuclei in the
real atmosphere have appreciable fractions of soluble materials (e.g., Young, 1993), which has been
emphasized in recent field projects as discussed in Section 9.4. Hence, the same aerosol particles may
serve both as IN and CCN.
The experiments and data on IN properties described in Section 9.3 indicate the necessity of modi-
fying the traditional view of IN as completely insoluble particles, as well as the parameterizations and
theories of heterogeneous ice nucleation. DeMott et al. (1998) and a few others developed empirical
parameterizations of heterogeneous nucleation based on the conception of IN as deliquescent mixed
cloud condensation nuclei (CCN) with 50% insoluble and 50% soluble matter (model of Colorado
State University or CSU model, see Section 9.4).
Khvorostyanov and Curry (2000, 2004a,b, 2005a, 2009b, hereafter, KC00-09, or KC scheme),
based on the modification of the classical nucleation theory, developed a theory of heterogeneous ice
nucleation by freezing of the CCN and cloud drops containing both soluble and insoluble fractions,
with the possibility of ice nucleation both at water sub- and supersaturations. The theory of homoge-
neous freezing of fully soluble CCN described in Chapter 8 was generalized in KC00-09 for the case
of mixed CCN, extending the concept of freezing to temperatures as high as a few degrees below
0 °C. This theory is described in this and following sections.
Equations for the critical radius and activation energy show that nucleation becomes possible
due to the catalyzing effect of insoluble substrate within CCN that counteracts the freezing point
depression by the solution effect, significantly lowering the energy barrier for freezing and permitting
freezing at smaller supercooling than that for homogeneous freezing. These equations show that ice
414 Heterogeneous Nucleation of Drops and Ice Crystals

nucleation may occur with noticeable and significant rates on the surface of the insoluble substance
embedded in a solution drop that has formed on a dry CCN.
Therefore, the basic premises of this theory are: a) the same deliquescent hygroscopic aerosol (haze
particles) that serves as cloud condensation nuclei (CCN) may also serve as ice nuclei (IN) under freez-
ing conditions; b) in contrast to the homogeneous nucleation case, these haze particles contain an insoluble
substrate (which is typical of CCN); c) in contrast to drop activation on CCN, where the aerosol soluble
fraction determines the activity of a nucleus, heterogeneous ice nucleation is determined also by the
insoluble fraction of CCN, which is a nucleation catalyzer; d) heterogeneous ice nucleation may occur
on these CCN-IN; it will be shown that this process may take place both at water supersaturations and
subsaturations; e) a similar approach is applicable for freezing of cloud drops in the immersion mode,
and, as will be shown, leads to the similar equations for the critical radius, energy, and nucleation rates.
In the next few sections, we derive and analyze the analytical dependence of the critical radius, energy,
and nucleation rate on the temperature, saturation ratio, misfit strain, pressure, and finite radius of freezing/
melting particles. We consider three particular cases under variable external pressure and solution concen-
tration: 1) volume heterogeneous freezing of aqueous solution drops (Section 9.7); 2) quasi-heterogeneous
surface freezing of solutions; and 3) quasi-heterogeneous surface melting of ice crystals; the last two
cases are considered in Section 9.8. The analysis of these relations is performed in Section 9.9.

9.7.2. Volume Heterogeneous Freezing

Heterogeneous volume freezing may be a characteristic of the deliquescence-heterogeneous-freezing

(DHF) or immersion freezing modes of the several possible modes of ice nucleation, whereby the
freezing does not initiate on the drop surface. As discussed in Chapter 8, the difference between the
freezing of unactivated small solution drops (haze particles) and larger activated cloud drops is deter-
mined by the difference in the equilibrium states of these particles. As shown in Chapter 3, the small
solution drops or unactivated interstitial CCN are close to the Köhler equilibrium, while larger cloud
drops are close to the Kelvin equilibrium. Ice nucleation inside the volumes of both droplet types and
both types of equilibrium is considered in this section.
To describe the first type of freezing, consider a three-phase system consisting of a solution or
water drop with radius rdr in humid air and an ice germ with radius rcr that forms inside the drop on
the surface of a curved insoluble foreign substrate with radius rN. The ice germ is in equilibrium with
the drop, which itself is in equilibrium with the environmental moist air; these conditions define the
critical ice germ radius rcr. Such a configuration was previously considered, e.g., by Fletcher (1962),
Dufour and Defay (1963), Defay, Prigogine, and Bellemans (1966), Young (1993), Pruppacher and
Klett (1997), and the expressions for the critical radii were derived under constant external pressure,
often neglecting the effects of misfit strain, or without explicit direct analytical description of the
solution effects. Here we consider variable pressure along with variable temperature, droplet size,
and solution concentration that is accounted for via the water saturation ratio.
The derivation of rcr and DFcr shown next mostly follows the works by Khvorostyanov and Curry
(2000, 2004a,b), where the dependencies of rcr and DFcr on temperature T, saturation ratio Sw, droplet
size rd, and pressure p were derived. The derivation is based on the entropy equation (Eqn. 3.6.4) of
Section 3.6 for this system at equilibrium. In the context of (Eqn. 3.6.4), phase 1 is the liquid solution
9.7. Critical Radius and Energy of Heterogeneous Freezing 415

or water and phase 2 is ice, the subscript “k0,1” means pure water, “1” means solution, “2” means ice,
and “e” means environmental moist air. Then, rk0,1 and rk0,1 are the densities of water rw and ice ri,
the molar melting latent heat Lˆ12 = M w Lm , where Lm is the specific melting latent heat, and the activi-
ties of water and ice are ak,1 = aw, ak,2 = ai. Following observations (e.g., Dash et al., 1995; Pruppacher
and Klett, 1997; Curry and Webster, 1999), as in the case with homogeneous freezing in Section 8.6,
we assume that the retention coefficient is zero, and then ai = 1 and ln(ai) = 0.
If an ice germ is approximated by a spherical cap at the surface of the insoluble substrate, the
internal pressures inside a crystal, pi, and inside a liquid solution drop, ps, can be expressed in terms
of external pressure p using conditions of mechanical equilibrium:

 2σ   2σ 
dpi = dps + d  is  , dps = dp + d  sa  , (9.7.1)
 rcr   rdr 

where subscripts i and s refer to ice and solution respectively, sis and ssa are the surface tensions at
the ice–solution and solution–air interfaces. Equation (9.7.1) describes the equilibrium between an
ice germ and liquid solution drop, and the equilibrium between the liquid drop and environmental air.
Then, using (Eqn. 9.7.1) and multiplying the entropy equation (Eqn. 3.6.4) by T, we can rewrite it as

Lm Aρ Aρ  2σ sa  1  2σ is 
− dT − dp − d − d
T ρi ρi  rdr  ρi  rcr 
 C ε 2  RT
−d  ε  + d ln aw = 0 (9.7.2)
 ρi  M w

where we introduced the density function Ar = 1 − ri/rw, and aw is the water activity defined in
Section 3.5 by (Eqn. 3.5.16) for a solution with an insoluble substance.
The number of components in this thermodynamic system is c = 4 (water, solute, insoluble sub-
stance, air), and the number of thermodynamic degrees of freedom (or independent variables) would
be Nw = c + 1 = 5 according to the phase rule (Eqn. 3.3.12) for the curved substances. If the mass of
solute ms is constant in the case considered here, we have an additional constraint and Nw = 4; if ms is
variable due to transfer processes (e.g., thermo- or diffusiophoresis transfer considered later), then Nw = 5.
The number of variables in (Eqn. 9.7.2) is 6 (T, rcr, rdr, p, e, aw), and only 4 or 5 of them are indepen-
dent according to this phase rule. We can consider the critical radius rcr of a crystal as a function of
3 or 4 variables, and integrate (Eqn. 9.7.2) for several various possible combinations of variables, this
would yield several analytical dependencies of the critical radius rcr on various variables. To shorten
and generalize calculations, as in Chapter 8, we will apply a method used in the theory of differential
equations and integrate (Eqn. 9.7.2), temporarily considering all variables as independent. A selec-
tion of the possible combinations of independent variables can be done in the final result.
We integrate (Eqn. 9.7.2) from the triple point temperature T0 to T, and from p0 to p with the
boundary conditions, aw = 1, rcr = rdr = ∞, p = p0, and e = 0 at T = T0, to aw, rcr, rdr, p, e, and T, and
obtain after rearranging the terms:

T0 2σ is 2σ sa Aρ C ε 2 RT  AK 
Lefm ln = + + ∆p + ε − + ln aw  , (9.7.3)
T ρi rcr ρi rdr ρi ρi M w  rdr 
416 Heterogeneous Nucleation of Drops and Ice Crystals

where Dp = p − p0, and AK = 2Mwssa/rwRT is the Köhler parameter, and we introduced the effective
average melting heat, defined by (Eqn. 8.6.8). The water activity aw is often assumed to be equal
to the water saturation ratio Sw (Tabazadeh et al., 1997; Koop et al., 2000) or is calculated from the
Köhler equation (e.g., DeMott et al., 1994).
As was discussed in Section 8.6 in the case with homogeneous freezing, an unactivated solution
drop at subsaturation Sw < 1 grows or evaporates rapidly until the Köhler’s equilibrium size and Sw are
reached. The estimates in Section 8.6 showed that the characteristic time of adjustment to equilibrium
varies from 10−4 s for rdr = 10−2 μm to a few seconds for rdr of a few microns, and this equilibrium
exists in most cases with moderate to high vertical velocities, even with rapid turbulent fluctuations.
We also assume that an unactivated solution particle is in Köhler equilibrium before freezing. There-
fore, the expression in the parentheses in the last term of (Eqn. 9.7.3), AK/rdr + lnaw, can be replaced
with lnSw according to the Köhler equation, and this lnSw can be substituted into the last term in
(Eqn. 9.7.3). For cloud drops of a few microns growing in a rising parcel at slight supersaturation,
the effects of both curvature and solution are relatively small, and also approximately lnaw ≈ lnSw.
Note that each term on the right-hand side of (Eqn. 9.7.3) is positive (−lnSw > 0 at Sw < 1), thus,
ln(T0/T) ≥ 0 and T ≤ T0—i.e., (Eqn. 9.7.3) describes lowering of the bulk triple point by all of the
above factors: rcr, rdr, p, e, −lnSw. Solving (Eqn. 9.7.3) for rcr, we obtain
2σ is
rcr = , (9.7.4)
 T  A f Cε ε 2 
ρi Lefm  ln  0 SwGn  − Ap ∆p − − 
 T  rdr ρi Lefm 

with the same Gn = RT/(Mw Lmef ), Af = 2ssa/(riL mef ), and Ap = Dr/(rwri L mef ) as in (Eqn. 8.6.15), or in the
more extended form
2σ is
rcr = . (9.7.4a)
 T  RT ∆ρ∆p 2σ sa C ε2 
ρi Lefm  ln  0  + ln Sw − − − ε ef 
  T  M w Lm ρ w ρi Lm ρi Lm rdr ρi Lm 
ef ef ef

Note that the last three terms in the denominator caused by the excess pressure Dp, finite droplet
radius rdr, and misfit e are negative—in other words, all these factors lead to an increase in rcr and
in DFcr, and to a decrease in the ice nucleation rate. (Eqn. 9.7.4) can be written in slightly different
forms that are convenient in some applications,

2σ is
rcr = (9.7.5a)
 T 
ρi Lefm  ln  0 SwGn exp(− H v , fr ) 
 T 

2σ is
rcr = , (9.7.5b)
 T  
ρi Lefm  ln  0  + Gn ln Sw − H v , fr 
 T 
These expressions are similar to (Eqns. 8.6.14b) and (8.6.17b) for the critical radius of homogeneous
freezing, with Dr = rw − ri, but the dimensionless function Hv,fr is modified compared to (Eqn. 8.6.16)
by addition of the term with misfit e:
9.7. Critical Radius and Energy of Heterogeneous Freezing 417

Af ∆ρ∆p 2σ sa Cε ε 2
H v , fr = Ap ∆p + + Cε ε 2 = + + . (9.7.6)
rdr ρ w ρi Lefm ρi Lefm rdr ρi Lefm

Equations (9.7.4), (9.7.4a), and (9.7.5a,b) account for the effects of temperature, water saturation
ratio, pressure, elastic misfit strain, and the finite size of a freezing drop on rcr (taking into account
the number of independent variables). These expressions generalize the corresponding equations for
the homogeneous freezing of unactivated solution drops derived in Chapter 8 and are valid for both
heterogeneous (e ≠ 0) and homogeneous (e = 0) freezing.
As in Sections 9.2 and 9.5, rcr can be also written via the affinity A∝,li = Dmli = ml − mi:

2σ is vi µ 2σ is M w
rcr = = , (9.7.6a)
µl − µi ρ i ( µl − µi )

where vim = Mw/ri is the molar volume, and ml = mmstab and mi = mstab are the molar chemical potentials
of the metastable liquid phase and stable ice phase. Comparison with (Eqn. 9.7.5a) shows that

 T 
µl − µi = M w Lefm  ln  0 SwGn exp(− H v , fr ) 
 T 
 T  RT ∆ρ∆p 2σ sa C ε2 
= M w Lefm  ln  0  + ln Sw − − − ε ef . (9.7.6b)
  T  M w Lm ρ w ρi Lm ρi Lm rdr ρi Lm
ef ef ef

Thus, the affinity for solution–ice A∞,li = Dmli is generalized for vapor–ice with an accounting for the
energy of the elastic misfit strain, the solution effect, final drop radius, and external pressure; the last
four terms in (Eqn. 9.7.6c) cause a decrease in the difference of chemical potentials, counteracting
the freezing process. The quantity Dm determines the transition from the metastable liquid to the
stable ice state, ml > mi. The equality ml = mi determines the equilibrium melting or freezing curves
considered in Sections 9.11 and 9.12.
We have considered in this section the nucleation of ice crystals inside unactivated submicron
solution droplets near Köhler’s equilibrium. As mentioned in Section 8.6.4, the process of ice nucle-
ation inside cloud drops differs because cloud drops have much larger radii and the solution inside
the drops is very dilute. Therefore, the Köhler equilibrium is not applicable to such drops. The critical
radii and energies of ice crystals nucleating inside cloud drops can be derived similarly to the deriva-
tion in Section 8.6.4 for homogeneous freezing.
We begin with the general equilibrium equation (Eqn. 3.6.4), assume again Kelvin’s equilibrium
of cloud drops with the environment’s humid air, and replace in (Eqn. 3.6.4) the term dln(aw) with the
term describing the contribution of the water vapor activity, dln(ev /p). Thus, (Eqn. 8.6.39) is modified
for heterogeneous freezing, taking into account the misfit strain e as

dT ∆ρ ∆ρ  2σ sa 
− Lm (T ) + dp − d
T ρ w ρi ρ w ρi  rdr 
1  2σ is   C ε 2  RT e 
− d  −d ε  + d ln  v  = 0. (9.7.6c)
ρi  rcr   ρi  M w  p
418 Heterogeneous Nucleation of Drops and Ice Crystals

Integration of (Eqn. 9.7.6c) from the initial conditions T = T0, rd0 = ∞ (plane surface), rcr = ∞,
ev = ews (saturated vapor pressure over a plane water surface), p = p0 to the state (T, rd, rcr, ev, p) yields

T0 ∆ρ∆p 2 ∆ρσ sa 1
Lefm (T ) ln − −
T ρ w ρi ρ w ρi rd
2σ is Cε ε 2 RT  p 
− − + ln Sw 0  = 0, (9.7.6d)
ρi rcr ρi M w  p

where Dp = p − p0, T is the mean temperature in the range (T0, T), and Sw = ev /ews is the water satura-
tion ratio. This modification of the Kelvin equilibrium equation accounts for the ice crystal and insol-
uble substrate inside the drop. The assumptions T = const, p = const, e = 0, and the exclusion of all the
quantities related to ice, again would yield the Kelvin equation. Solving the modified (Eqn. 9.7.6d)
relative to rcr, we obtain

2σ is
rcr = , (9.7.6e)
 T p  
ρi Lefm  ln  0 SwGn 0  − H v , fr 
  T p  

where Hv,fr is defined in (Eqn. 9.7.6) and is the same as for the case of haze solution drops.
This equation is similar to (Eqn. 9.7.4a) for the rcr of an unactivated solution drop with an
additional factor (p0/p) under the ln sign. An estimate of the terms in (Eqn. 9.7.6e) at rd ∼ 10 – 30 μm,
T ∼ 258 K using Lefm from Fig. 8.14a and ssa from Section 4.4 shows that the second term in the de-
nominator of (Eqn. 9.7.6e) under typical conditions is much smaller than the first term with ln and
can be neglected. Also neglecting for simplicity the term with the misfit e, (Eqn. 9.7.6e) is simplified
to
2σ is
rcr = . (9.7.6f)
 T p 
ρi Lefm  ln  0 SwGn 0  
 T p 

If droplet freezing occurs with a substantial pressure decrease, the factor p0/p > 1 in (Eqn. 9.7.6f)
leads to a smaller rcr and DFcr and accelerates droplet freezing. In processes without strong changes
of pressure, p ≈ p0, this equation is further simplified as

2σ is
rcr = . (9.7.6g)
 T 
ρi Lefm  ln  0 SwGn  
  T 

As in Chapter 8, this equation coincides with the simplified versions of rcr in (Eqns. 9.7.5a) and
(9.7.5b), neglecting the effects of pressure, droplet curvature, and e (Hv, fr = 0).
Thus, the effects of temperature and water saturation ratio are similar for both haze particles and
activated cloud drops. As in the case with homogeneous nucleation in Section 8.6.4, (Eqn. 9.7.6g)
allows introduction of “effective supercooling”

∆Tef = ∆T + δ s ∆T , δ s ∆T = T0 Gn sw , (9.7.6h)
9.7. Critical Radius and Energy of Heterogeneous Freezing 419

where DT is supercooling. Thus, positive supersaturation increases effective supercooling by dsDT =

T0Gnsw. Since Gn ∼ 0.4 at T ≈ −10 to −20 °C, the value T0Gn ∼ 102; thus, dsDT is equal to water
supersaturation (positive or negative) measured in percent. If sw > 0, this leads to an increase in the
effective supercooling by dsDT ≈ sw (%), and accelerates freezing in the immersion mode. At subsatu-
ration, sw < 0, as in the cloud evaporation layer, dsDT < 0, this hampers the freezing of cloud drops,
or may even prevent it if |dsDT| > DT.

9.7.3. Particular Cases of Critical Radius

As mentioned earlier, there are five variables in (Eqns. 9.7.4) and (9.7.5a), (9.7.5b), and (9.7.5c),
(T, Sw, p, e, rdr), and not all of these can be independent. If the soluble mass ms can vary, then Nw = 5, all
five variables in (Eqns. 9.7.4) and (9.7.5) can be independent. If ms = const, then the variance Nw = 4
and we can compose C54 = (5·4·3·2)/(1·2·3·4) = 5 possible combinations of four variables of the total
five by the exclusion of one variable. Thus, we can write five expressions for rcr. These are rcr(T, Sw,
p, e,), rcr(T, Sw, p, rdr), rcr(T, Sw, e, rdr), rcr(T, p, e, rdr), and rcr(Sw, p, e, rdr). If one of five variables is
absent in (Eqns. 9.7.4) and (9.7.5), the corresponding term should be set equal to zero. Then, we can
study the simultaneous dependences on the other four variables, and establish their equivalence, as
was done for pressure Dp and solution (Sw) effects in Chapter 8. If additional conditions are imposed
on the system, e.g., T = const for isothermal process, or p = const for isobaric process, then the cor-
responding terms should also be excluded from (Eqns. 9.7.4) and (9.7.5).
The expressions (Eqns. 9.7.4) and (9.7.5) can be compared with previously derived expressions by
considering particular cases. For the simplest case with constant pressure (Dp = 0), no misfit strain (e = 0),
and a bulk solution (1/rdr = 0), we have Hv,fr = 0. If additionally Sw = 1 (pure water and no external sources
of supersaturation), (Eqns. 9.7.4) and (9.7.5) are reduced to J. J. Thomson’s (1888) classical equation

2σ iw
rcr = (9.7.7)
ρi Lefm ln(T0 / T )

where siw is the surface tension at the ice–water interface. This equation is often used to describe the
triple point lowering in polycrystalline crystals, and melting point shifts due to varying crystal size, the
Gibbs-Thomson effect (Dufour and Defay, 1963; Defay et al., 1966; Dash et al., 1995; Johari, 1998).
Equation (9.7.7) is often written as

rcr = 2σ iw /[ N i kT ln(ews /eis )] (9.7.7a)

where Ni is the concentration of molecules per unit volume in ice, ews and eis are the saturated vapor
pressures over water and ice (e.g., Young, 1993, and Fletcher, 1962). Equations (9.7.7) and (9.7.7a)
are equivalent expressions for DFcr. Their equivalence can be shown using the Clausius–Clapeyron
equation for ews and eis (see Section 3.7):

d (ln ews )dT = Le /Rv T 2 , d (ln eis )dT = Ls / Rv T 2 , (9.7.7b)

where Le and Ls are the specific heats of evaporation and deposition, and Rv is the gas constant for
water vapor. Subtracting these equations, then integrating from T to T0, and using the relations ews = eis
at T = T0, and Ls − Le = Lm, we obtain
420 Heterogeneous Nucleation of Drops and Ice Crystals

ln(ews / eis ) ≈ Lm ∆T /( Rv T02 ), (9.7.7c)

where DT = T0 − T. Substituting (Eqn. 9.7.7c) into (Eqn. 9.7.7a) and using the relation Ni = NAv/vim =
NAvri /Mw with NAv and vim being the Avogadro number and molar ice volume, the denominator in
(Eqn. 9.7.7a) can be rewritten as

N i kT ln(ews /eis ) ≈ ρi Lm ∆T /T0 ≈ ρi Lm ln(T0 / T ). (9.7.7d)

The second equation is valid for a not very large supercooling, when DT << T0 and ln(T0/T) = ln[T0/
(T0 − DT)] ≈DT/T0. Substitution of (Eqn. 9.7.7d) into the denominator of (Eqn. 9.7.7a) yields

rcr = 2σ iw / [ ρi Lm ln(T0 /T )], (9.7.7e)

which coincides with (Eqn. 9.7.7). Thus, (Eqns. 9.7.7) and (9.7.7a) for rcr are equivalent for DT << T0.
Note that although (Eqn. 9.7.7a) contains two vapor pressures, they both are saturated and depend
only on the temperature but not on the saturation ratio; therefore, (Eqn. 9.7.7a) does not contain any
information on ambient humidity or solution effects.
If misfit strain is included, (Eqn. 9.7.4) becomes

2σ iw
rcr = . (9.7.8)
ρi L ln(T0 / T ) − Cε ε 2
ef
m

The equations equivalent to this generalization of Thomson’s equation for rcr for heterogeneous
freezing of pure water were considered by Fletcher (1962) and Young (1993). In the presence of
a solvent or external source of supersaturation, Sw ≠ 1, but still for e = 0 and Dp = 0, we have from
(Eqn. 9.7.5) another expression derived by Khvorostyanov and Sassen (1998), and Khvorostyanov
and Curry (2000):

2σ is
rcr = . (9.7.9)
ρi Lefm ln[(T0 / T ) SwGn ]

Similar equations were considered in Chapter 8 for the case of homogeneous nucleation. In the
earlier works (e.g., Dufour and Defay, 1963; Pruppacher and Klett, 1997), rcr was expressed in a
different form using water activity aw or molar fraction xs, or osmotic potential Φs and molality.
The use of Sw instead of aw, Φs, or xs is more convenient in applications such as cloud models
where Sw is a readily determined environmental variable. Note that although aw and Sw may be
close in many cases at Sw < 1, they may differ at Sw ∼ 1 due to the curvature effects, thus leading
to different values of rcr. The Kelvin parameter Ak ∼ 10−7 cm, and the curvature correction for a
small particle with rdr ∼ 10−6 cm, is Ak/rdr ∼ 0.1. In Köhler’s equilibrium, reached very rapidly for a
small droplet, Sw ≈ aw + Ak/rdr. Thus, Sw ≈ aw +0.1 in this case—i.e., the saturation ratio is greater
by 0.1, which is equivalent to 10% in relative humidity. For example, Sw can be 1.05, and aw =
0.95; therefore, using aw instead of Sw can give a noticeably different rcr and may lead to the error
in calculations. Thus, the “saturation ratio based criterion” seems to be preferable compared to
the “water activity based criterion,” as was discussed in Chapter 8 for homogeneous nucleation,
especially for small drops.
9.7. Critical Radius and Energy of Heterogeneous Freezing 421

In the presence of a solvent or an external source of supersaturation, Sw ≠ 1, but still for Dp = 0, we

have from (Eqn. 9.7.5) the following equation:

2σ is
rcr = . (9.7.10)
ρi Lefm ln[(T0 / T ) SwGn ] − Cε ε 2

Taking into account the solution effects, Sw < 1, and the external pressure, Dp > 0, but with the bulk
solution, rdr = ∝, (Eqn. 9.7.5) for the critical radius has the form

2σ is
rcr = . (9.7.11)
 T  C ε2 
ρi Lefm  ln  0 SwGn  − Ap ∆p + ε ef 
 T  ρ i Lm 

All of these particular cases enable the establishment of the equivalence between any two variables.
For example, (Eqn. 9.7.4) allows the quantitative relation between the solution and pressure to be
determined. The pressure dependence in (Eqns. 9.7.4) and (9.7.5) has not been previously accounted
for in this form. It will be shown in the following text that this allows for a simple evaluation of the
pressure effects on the freezing and melting points. In the case e = 0, Dp = 0, rdr = ∝, and T→T0,
(Eqns. 9.7.4) and (9.7.5) convert into

2 M wσ is
rcr = , (9.7.12)
RT ρi ln Sw

and resemble Kelvin’s expression for nucleation of a crystal from the vapor, except that it contains
sis instead of siv for nucleation from the vapor. Since sis ∼ (1/4)siv, (Eqn. 9.7.12) shows that rcr for
freezing is four times smaller; therefore ice nucleation by water freezing is energetically much more
favorable than direct nucleation from the vapor.
So, according to the correspondence principle, (Eqns. 9.7.4), (9.7.4a), (9.7.5a), (9.7.5b), and
(9.7.6e) generalize and unify all of these particular cases for the critical germ radius and are used in
the following text to generalize the critical energy of freezing and to establish equivalence between
pressure, solution, and temperature effects on freezing and melting.

9.7.4. Critical Energy of Volume Freezing

As discussed in Chapter 8, the free energy of germ formation DFcr(T, Sw) in classical nucleation theory
is written as a sum of the positive surface term, DFsurf ∼ r2, and a negative volume term DFV ∼ r3,
caused by the difference of the free energies of aqueous solution Fas and ice Fi—i.e., DFV = (Fas − Fi)
(4/3)pr3ri:

∆Fcr (r ) = −∆FV + ∆Fsurf . (9.7.13)

Similar to Section 9.2, the critical energy DFcr of volume freezing is obtained from the condition
∂DF(r)/∂r = 0. Then, (Fas − Fi) is expressed via rcr, and is substituted into (Eqn. 9.7.13) to yield for a
crystal with the geometry of a spherical cap:

4
∆Fcr = πσ is rcr2 f (mis , x ), (9.7.14)
3
422 Heterogeneous Nucleation of Drops and Ice Crystals

where f(mis, x) is a geometrical factor defined in Section 9.2. Substituting (Eqn. 9.7.5a) for rcr into the
last expression, we obtain the critical free energy for volume freezing as a function of temperature,
solution concentration (supersaturation), pressure, and misfit strain:

16π σ is3 f (mis , x )

∆Fcr = 2 , (9.7.15)
3  ef  T0 Gn 
 ρi Lm ln  Sw exp(− H v , fr )  
 T 

where Hv ,fr is defined in (Eqn. 9.7.6). The geometric factor f(mis, x) in (Eqns. 9.7.14) and (9.7.15)
arises from the geometry of the spherical ice cap freezing on an insoluble substrate core with radius
rN. As in Section 9.2, this factor can be expressed similar to (Eqn. 9.2.15) for the planar surface of the
substrate, or following Fletcher (1958), similar to (Eqns. 9.2.21) or (9.2.22) for the curved surface of
the substrate is expressed via the ratio x = rN /rcr and the contact parameter mis = cos(qiN).
For volume freezing, the parameters and geometric factor were defined by Fletcher (1958) differ-
ently than in Section 9.2 for the drops nucleation from vapor; now mis = cosqiN = (sNs−sNi)/sis, where
sNs and sNi are the surface tensions at the solution–substrate and ice–substrate interfaces. For the
convex surface of the insoluble core inside the solution drop, according to Fletcher (1958),

f (mis , x ) = (1 / 2 ){1 + [(1 − mis x ) / y]3 + x 3 (2 − 3ψ + ψ 3 ) + 3mis x 2 (ψ − 1)},

ψ = ( x − mis ) / y, y = (1 − 2mis x + x 2 )1/ 2 . (9.7.16)

It is shown in the next sections that the typical values of rcr ∼ 10−3 to 10−2 μm, while the major con-
tribution to nucleation rates comes from the particles with rN ∼ 0.05–1 μm and larger. Thus, the case
with x = rN /rcr >> 1 is practically the most important. In this large particle limit, x >> 1, the geometri-
cal factor (Eqn. 9.7.16) reduces to Volmer’s expression for planar substrate,

(2 + mis )(1 − mis )2 mis3 − 3mis + 2

f (mis , x ) ≈ f (mis ) = = . (9.7.16a)
4 4
This expression does not depend on rN. Thus, the rN-dependence in the geometric factor can be
neglected to the first approximation in many cases, which simplifies derivation for the polydisperse
ensemble of particles. For example, typical values of f(mis = 0.5) = 0.156 and f(mis = 0.36) = 0.242
characterize critical energy reduction due to cap geometry and favors heterogeneous nucleation in the
large particle limit as compared to the case of homogeneous nucleation.
For the concave insoluble core inside the solution drop, the geometric factor is similar to (Eqn. 9.2.22)
for the drop nucleation from vapor on an insoluble substance, but now with the different contact angle
and parameter mis:

f (mis , x ) = (1/ 2 ){1 − [(1 + mis x ) / y]3 − x 3 (2 − 3ψ + ψ 3 ) + 3mis x 2 (ψ − 1)},

ψ = ( x + mis )/ y, y = (1 + 2mis x + x 2 )1/ 2 . (9.7.16b)

The geometric factor f(mis, x) < 1, and thus the critical energy of heterogeneous nucleation is smaller
than the energy of homogeneous nucleation, and so heterogeneous freezing begins at much higher
temperatures (generally below −10 °C) than homogeneous freezing (below −38 °C). For small contact
angles (good wettability of the surface), mis is close to 1, and the geometric factor f(mis, x) is small,
which favors heterogeneous nucleation.
9.7. Critical Radius and Energy of Heterogeneous Freezing 423

For not very high pressure (Dp ≈ 0), and the freezing of bulk solutions or large drops (rd = ∞),
the factor Hv ,fr becomes Ce e 2/ri L mef and (Eqn. 9.7.15) reduces to the expression (Khvorostyanov and
Curry, 2000, 2004a,b)

(16π /3)σ is3 f (mis , x )

∆Fcr = 2 . (9.7.17)
 ef  T0 Gn  2
 ρi Lm ln  T Sw  − Cε ε 
 
For a particular case Sw = 1 (pure water) and neglecting misfit strain, e = 0, this is reduced to

16π σ is3 f (mis , x )

∆Fcr = , (9.7.17a)
3 [ ρi Lefm ln(T0 / T )]2

which corresponds to the classical expressions case of J. J. Thomson (1888) with rcr in (Eqn. 9.7.7).

9.7.5. Modification of Critical Energy with Active Sites

Fletcher (1969) has further modified the classical expression for the critical energy using a simple
model for the active sites on the surface of nucleating insoluble substrate. He assumed that the con-
tact parameter on the active sites is mis = 1, and mis < 1 on the rest of the surface. If the relative area
of active sites is a on an insoluble core with radius rN, then the active sites occupy a surface area of
arN2. Then, the surface energy defined as in (Eqn. 9.2.11) should be modified as

∆Fsurf = σ is Ais + (σ Ni − σ Ns ) ANi = σ is Ais − misσ is ANi , (9.7.18)

where sis, siN, and sNs are the surface tensions at the interfaces ice–solution, ice–insoluble substrate,
and solution–substrate (substrate is denoted by “N”). Transition from the first to the second equation
here is made using a definition mis = (siN − sNs)/sis. Fletcher’s (1969) active sites modification is
performed by replacement of the surface energy:

− misσ is ANi = − misσ is ( ANi − α rN2 ) + 1 × σ isα rN2 , (9.7.19)

where “1” on the right-hand side means mis = 1 on the active site. Substituting this expression into
(Eqn. 9.7.18), and then substituting DFsurf into (Eqn. 9.7.13), we obtain the total (volume plus sur-
face) energy:

∆Fcr = ∆FV + ∆Fsurf = ∆FV + σ is Ais − misσ is ( ANi − α rN2 ) − σ isα rN2 ,
= ∆FV + ∆Fsurf ,0 − ∆Faα , (9.7.20)

where we defined the surface energy DFsurf,0 without the active sites (a = 0), and the term ∆Faα :

∆Fsurf ,0 = σ is ( Ais − mis ANi ), (9.7.20a)

∆Faα = α rN2σ is (1 − mis ) = α rN2σ isδ mis , δ mis = 1 − mis . (9.7.20b)

The term ∆Faα , introduced by Fletcher (1969), is the energy decrease due to existence of the active
sites with surface fraction a on the surface of an insoluble core and with the contact parameter
mis = 1—i.e., with ideal wettability. The term ∆Faα in (Eqn. 9.7.20b) does not include the geometrical
424 Heterogeneous Nucleation of Drops and Ice Crystals

parameters of the germ, thus minimization of the total energy DFcr(r) by r does not involve the term
with a, and the term in energy without active sites is as before. It can be easily shown that if the sur-
face areas in (Eqn. 9.7.18) for DFsurf are defined similar to (Eqn. 9.2.4) and (Eqn. 9.2.5) for a planar
surface, ANi = pr2(1 − mis2), Ais = 2pr2(1 − mis), and the volume of the ice cap is as in (Eqn. 9.2.3),
then the sum (DFV + DFsurf,0) in (Eqn. 9.7.20) is proportional to Volmer’s (1939) geometric factor
(Eqn. 9.7.16a). For the cap geometry, this factor has Fletcher’s form. Therefore, the critical energy
with active sites can be written as a sum of the previously derived term and a term describing the
active sites:
∆Fcr = ∆Fcrα 0 − ∆Faα = ∆Fcrα 0 − α rN2σ is (1 − mis ), (9.7.21a)
α0
where ∆F cr is the critical energy without active sites (a = 0) described by (Eqn. 9.7.15):

4 (16π /3)σ is3 f (mis , x )

∆Fcrα 0 = πσ is rcr2 f (mis , x ) = 2 ,
(9.7.21b)
3  ef  T0 Gn 
 ρi Lm ln  Sw exp(− H v , fr )  
 T 

(16π /3)σ is3 f (mis , x )

∆Fcrα 0 = 2 , (9.7.21c)
 ef   T0 Gn  
 ρi Lm  ln  Sw  − H v , fr  
  T  

and ∆Faα is the decrease in the critical energy DFcr due to active sites described by (Eqn. 9.7.20b).
Thus, DFcr that takes into account the active sites can be written now as

(16π /3)σ is3 f (mis , x )

∆Fcr = 2 − α rN2σ is (1 − mis ). (9.7.21d)
 ef  T0 Gn 
 ρi Lm ln  Sw exp(− H v , fr )  
  T 
Various forms of DFcr are used in applications. In particular, for not very high pressure (Dp = 0),
and for the freezing of bulk solutions or large drops (rd = ∞):

(16π /3)σ is3 f (mis , x )

∆Fcr = 2 − α rN2σ is (1 − mis ). (9.7.22)
 ef  T0 Gn  2
 ρi Lm ln  T Sw  − Cε ε 
 

It is clear that a polydisperse population of ice nuclei cannot be characterized by a single value of the
active site area a. Curry and Khvorostyanov (2012) performed a further generalization of the active
site concept and introduced the temperature-dependent a(T). This model and its effects will be con-
sidered in Section 9.17. Averaging over the active sites is considered in the following text.
Fletcher’s concept of the active sites can be further generalized in the following way. The term
DFaa in (Eqn. 9.7.20b) describes the decrease of the free energy if only one type of the active sites
with “ideal” wettability, mis = 1, is present. In reality, it can be expected that several types of active
sites can be present on each IN. These sites may have different contact parameters misk that satisfy
the relation mis < misk ≤ 1 (Hobbs, 1974)—that is, are greater than the main contact parameter mis
characterizing the major IN surface, thereby ensuring greater wettability and ice nucleability, but are
9.7. Critical Radius and Energy of Heterogeneous Freezing 425

smaller than 1. Thus, (Eqn. 9.7.20b) for DFaa can be further generalized for several types of active
sites as

∆Faα = ∑ ∆Faα k = ∑ fαk α ak rN2σ isδ misk , δ misk = misk − mis , (9.7.23)
k k

where mis and α ak are the contact parameter and surface fraction of the active sites of the k-th
k

k
kind and fα is their density. It is assumed that δ misk > 0 , thus DFaa > 0, and this term −DFaa < 0 in
(Eqn. 9.7.21a) causes a decrease in DFcr and favors ice nucleation. Then, (Eqn. 9.7.21a) for DFcr can
be generalized in the same way as before—i.e., considering the sum of the volume and surface ener-
gies and finding their minimum by radius.
Since the geometry of the ice cap is not involved in introducing these sites (Fletcher, 1969), the
major first term of the RHS in (Eqns. 9.7.21b) or (9.7.22) remains the same and the expression for
DFcr can be generalized as

(16π /3)σ is3 f (mis , x )

∆Fcr = 2 − ∑ fαk α ak rN2σ isδ miks . (9.7.24)
 ef  T0 Gn  k
 ρi Lm ln  Sw exp(− H v , fr )  
 T 

Note that this generalization of classical nucleation theory with respect to the active sites introduced
here is analogous to the concept developed in Connolly et al. (2009) where the active sites were intro-
duced without invoking classical nucleation theory and their properties were studied experimentally.
The parameters of the active sites from this study can be compared to (Eqn. 9.7.24).
The freezing nucleation rates JS, fr and Jf,het can be now evaluated using (Eqns. 9.6.4) and (9.6.7)
with the kinetic coefficients Bhet and Chet defined by (Eqns. 9.6.6) and (9.6.8), and with DFcr derived
in this section. Using (Eqn. 9.7.24) for DFcr , the nucleation rate Jf,het (Eqn. 9.6.7) can be rewritten as

kT  ∆F 
J f ,het (T , rN ) = c1s 4π rN2 exp  − act 
h  kT 
 
 1 (16π / 3)σ is3 f (mis , x ) 1 k 
× exp  − + ∑ α a N is is  .
f k k 2
α r σ δ m (9.7.25)
{ }
2
kT ρ Lef ln (T / T ) S Gn exp(− H )  kT
 
k
i m  0 w v , fr 

Using a somewhat simplified (Eqn. 9.7.21d) for DFcr with only one kind of active sites, the nucleation
rate (Eqn. 9.6.7) can be rewritten as

kT  ∆F 
J f ,het (T , rN ) = c1s 4π rN2 exp  − act 
h  kT 
 
 1 (16π /3)σ is3 f (mis , x ) α rN2σ is (1 − mis ) 
× exp  − + , (9.7.26)
{ }
2
kT ρ Lef ln (T / T ) S Gn exp(− H )  kT
 i m  0 w v , fr  

with Hv, fr defined in (Eqn. 9.7.6). These nucleation rates include the effects of the temperature, the
solution concentration or saturation ratio Sw, the external pressure, misfit strain, the finite size of a
freezing drop, and active sites.
426 Heterogeneous Nucleation of Drops and Ice Crystals

9.8. Properties of the Deliquescence-Freezing Mode

9.8.1. Critical Radius, Energy, and Nucleation Rate

Properties of the critical ice germs radii, energies, and nucleation rates derived in Section 9.7 are
illustrated in this section. In the calculations described here, we use the temperature and solution
concentration parameterizations of ri, rw, Lm, ssa, and sis from Pruppacher and Klett (1997) and
Tabazadeh et al. (1997) (Section 4.4), and DFact(T) from Khvorostyanov and Curry (2004b) (Section
8.8.3), the contact parameter mis = 0.5 for the deliquescence-heterogeneous-freezing (DHF) mode,
the external pressure Dp = 0, and the misfit strain e = 0 in most calculations. If these parameters are
different in some cases, their values are indicated. Figs. 9.2–9.5 present rcr and DFcr calculated with
(Eqns. 9.7.4), (9.7.5), and (9.7.15) in two forms: as 2D fields on a T-Sw diagram, and as functions of
temperature for several humidities.
Fig. 9.2 shows isolines of the critical radius rcr for the deliquescence-freezing mode as a function of
the temperature T and saturation ratio Sw on the two-dimensional T-Sw diagram. Note that since rcr does
not depend on f(mis,x), here rcr is the same as for homogeneous nucleation, as described in Chapter 8.
The isolines of rcr extend from the lower right-hand corner to the upper left-hand corner, since the tem-
perature increase of 50 °C is approximately compensated by the humidity increase of 50%. Values of
rcr range from ∼10−7 cm at Sw ∼ 1.3, T ∼ −55 °C to 10−6 cm at warmer T or lower Sw. Thus, rcr increases
rapidly toward the left lower corner while the denominator in (Eqn. 9.7.4) for rcr goes to zero, and so
rcr tends to infinity. In the left lower corner of the T-Sw diagram with too low Sw and supercooling DT,
nucleation is prohibited since the denominator in (Eqn. 9.7.4) and rcr become negative.

1.20

1.15 rcr (T, Sw)

1.10
Saturation ratio over water, Sw

1. 1.
5 0
2.
0

1.05
3.
0

1.00
4.
0

0.95
6.
0

12
.0
0.90

0.85

0.80 Prohibited nucleation

0.75

5 10 15 20 25 30 35 40 45 50 55
Supercooling ∆T = T0–T (C)

Figure 9.2. Critical radius rcr (10−7 cm) for the freezing mode as a function of two variables:
supercooling DT = T0 − T and saturation ratio over water Sw (the T-Sw diagram) at Dp = 0 and e = 0.
rcr is the same as for homogeneous nucleation. From Khvorostyanov and Curry (2004b), J. Atmos.
Sci., 61, © American Meteorological Society. Used with permission.
9.8. Properties of the Deliquescence-Freezing Mode 427

2.4E–6 Sw = 1.001
Sw = 0.9

Critical germ radius rg (T, Sw), cm

2.0E–6 Sw = 0.97, dep

1.6E–6

1.2E–6

8.0E–7

4.0E–7

0.0E+0
–50 –40 –30 –20 –10 0
Temperature (C)

Figure 9.3. Critical germ radius rcr for the freezing mode as a function of temperature with the
contact parameter m = 0.5 for the saturation ratios over water, Sw= 1.001 (circles), Sw= 0.9 (diamonds),
and for the deposition mode with m = 0.95 and Sw= 0.97 (triangles). From Khvorostyanov and
Curry (2004b), J. Atmos. Sci., 61, © American Meteorological Society. Used with permission.

1.30
–1
–1

3.0
2.5

1.25 log10Fcr
–1
2.

1.20
0
Saturation ratio over water, Sw

–1

–1

1.15
2.

3.
5

0
–1

1.10
2.
0

–1
–1 –1 3.
1.05 1. 2. 0
0 5
–1 –1
1.00 0. 2.
0 0
–1
1. –1
0.95 0 2.5
–1 –1
0.0 2.0
0.90
–1
0.85 1.0 –12.0
–10
Prohibited .0
0.80 nucleation
–11.0
–10.0
0.75
5 10 15 20 25 30 35 40 45 50 55
Supercooling ∆T = T0–T (C)

Figure 9.4. Logarithm of the critical energy Fcr (erg) for the freezing mode as a function of two
variables: supercooling DT = T0 − T and the saturation ratio over water Sw calculated with contact
parameter m = 0.5 and rN= 0.26 μm. From Khvorostyanov and Curry (2004b), J. Atmos. Sci., 61,
© American Meteorological Society. Used with permission.
428 Heterogeneous Nucleation of Drops and Ice Crystals

1E–6
∆Fcr, Sw = 1.001
∆Fcr, Sw = 0.9
1E–7

Critical and activation energy (erg)

∆Fcr, Sw = 0.97, dep
1E–8 ∆Fact

1E–9

1E–10

1E–11

1E–12

1E–13
–50 –40 –30 –20 –10 0
Temperature (C)

Figure 9.5. Critical germ energy Fcr for the deliquescence-freezing mode as a function of
temperature with the contact parameter m = 0.5 for the saturation ratios over water, Sw = 1.001
(circles), Sw = 0.95 (diamonds), and for the deposition mode with m = 0.95 and Sw = 0.97 (crosses).
Activation energy DFact is presented for comparison (triangles). From Khvorostyanov and Curry
(2004b), J. Atmos. Sci., 61, © American Meteorological Society. Used with permission.

Fig. 9.3 shows an order of magnitude decrease of rcr over the temperature range from −3 to −10 °C
at Sw = 1.001 (supersaturation sw = 0.01%) typical of conditions in a mixed-phase cloud without
strong glaciation and from −15 to −30 °C at Sw = 0.9, typical for colder crystalline clouds or diamond
dust formation (e.g., Ohtake et al., 1982; Curry, 1983, 1995; Curry et al., 1990, 1993, 1996, 2000;
Girard and Blanchet, 2001; Gultepe et al., 2003; Khvorostyanov et al., 2003). The value of rcr may
increase with decreasing T if Sw decreases rapidly with T. The critical radius for deposition is greater
than for deliquescence-freezing for all values of T at Sw = 0.97.
The 2D field of the critical energy DFcr on the T-Sw diagram (Fig. 9.4) is similar to the field of
rcr. Nucleation is prohibited in the lower left-hand portion of the diagram because the critical radius
becomes negative here (Fig. 9.2). The T-curves for DFcr (Fig. 9.5) show that lowering humidity by
10% leads to a decrease in DFcr by 0.5–1 orders of magnitude. The critical energy of deposition is
much greater than for deliquescence-freezing, indicating a smaller probability of deposition. The
activation energy DFact is smaller than DFcr at Sw= 1.001 and Sw = 0.95 to T > −35…−38 °C, and
DFact exceeds DFcr at lower temperatures. Therefore, the role of DFact in ice nucleation increases for
very cold clouds. Since several different parameterizations were suggested for DFact (Section 8.3.3),
special studies are desirable to clarify their role relative to DFcr in the nucleation rates.
Fig. 9.6 shows the logarithm of the freezing nucleation rate Jf,het per particle (s−1) on the T-Sw dia-
gram, calculated with (Eqn. 9.6.7) and DFcr with (Eqn. 9.7.17) using contact parameter mis = 0.5 and
rN = 0.26 μm. This figure shows very high gradients of Jf,het, varying by 10–15 orders of magnitude
over the temperature range of 5 °C or a humidity range of 5%. The bold isoline “0” corresponds to
9.8. Properties of the Deliquescence-Freezing Mode 429

1.30

log10 Jf,het(T, Sw)

1.20

Saturation ratio over water, Sw

1.10

1.00
14
–2
2 12
0.90 –1 –
6 5 0 5 8

0.80

5 10 15 20 25 30 35 40 45 50 55
Supercooling ∆T = T0–T (C)

Figure 9.6. Logarithm of the freezing nucleation rate log10 Jf,het (s−1) as a function of two variables:
supercooling DT = T0 − T and the saturation ratio over water Sw calculated with contact parameter
m = 0.5 and rN = 0.26 μm. The bold isoline “0” corresponds to the rate Jf,het =1 s−1. From
Khvorostyanov and Curry (2004b), J. Atmos. Sci., 61, © American Meteorological Society. Used
with permission.

the rate Jf,het = 1 s−1 per particle and indicates the values of T, Sw where the nucleation rate becomes
significant.
Fig. 9.7 illustrates the temperature dependence of Jf,het for various humidities. Even relatively
small variations in humidity and its variation with T lead to significant changes in the nucleation rate.
At a typical cloud saturation ratio of 1.001 (supersaturation 0.1%), Jf,het reaches values of 10−5 to 1 s−1
per particle at T = −13 to −15 °C. An increase in Sw to 1.05 (sw = 5%) causes the shift to higher T by
5 °C, so that ice nucleation may occur with a noticeable rate at T of about −10 °C or warmer, which
is in agreement with observations by Hobbs and Rangno (1990) and Rangno and Hobbs (1991). It
will be shown in Section 9.13 that an increase of mis to 0.55–0.65 or the presence of active sites with
a surface fraction a ∼2 × 10−5 causes noticeable nucleation rates at warmer temperatures −5 to −9 °C,
and even at a low sw of 0.1–0.2%. At temperatures below −20 °C, ice nucleation occurs at subsatura-
tions. The nucleation rates and final crystal concentrations are discussed in more detail in Section 9.14
based on parcel model simulations.

9.8.2. Separation of the Temperature, Supersaturation, and Aerosol Dependencies

of the Critical Energy and Nucleation Rate

The dependencies of DFcr and Jf,het on the temperature T and supersaturation sw can be isolated and
determined analytically, which is useful in using the functional relationships and for developing
parameterizations similar to those described in Section 8.10 for homogeneous freezing. Ice nucleation
430 Heterogeneous Nucleation of Drops and Ice Crystals

20

15

10

5
Log10 Jf,het (s–1)

0
1.05

–5 1.001

0.95
–10

0.90

–15

–20
–60 –50 –40 –30 –20 –10 0
Temperature (C)

Figure 9.7. Freezing nucleation rate Jf,het (s−1) for the CCN freezing mode as a function of the
temperature with the contact parameter m = 0.5 for the saturation ratios over water, Sw = 1.05
(crosses), Sw = 1.001 (circles), Sw = 0.95 (diamonds), and Sw = 0.90 (triangles). The threshold of the
homogeneous freezing of drops with rdr ∼ 0.2–5 μm at Tc ∼ −42 . . . −38 °C is denoted by the ellipse.

via the deliquescence-freezing mode occurs usually at the water saturation ratio Sw close to 1—i.e., at
|sw| << 1. Using the relations Sw= 1+ sw and ln(1 + sw) ≈ sw for |sw| << 1, and expanding the denomina-
tor of rcr in (Eqn. 9.7.5b) and retaining only the term of the first order (this approximation is discussed
in the following text), we obtain
rcr ,0
rcr = ,
 Gn H v , fr 
1 + ln(1 + sw ) − 
 ln(T / T0 ) ln(T / T0 ) 
rcr ,0
≈ , (9.8.1a)
 Gn s w H v , fr 
1 + − 
 ln(T / T0 ) ln(T / T0 ) 
9.8. Properties of the Deliquescence-Freezing Mode 431

where rcr,0 is the critical radius at zero water supersaturation, sw = 0, with e = 0 and rdr = ∞,

2σ is
rcr ,0 = . (9.8.1b)
ρi L ln(T /T0 )
ef
m

For convenience, we denote in the following text the fraction of active sites with subscript “a” as aa.
Substitution of (Eqn. 9.8.1a) into (Eqn. 9.7.21a,b) yields

∆Fcrα,00 (T )
∆Fcr (T , sw , rdr , ε , α a ) = 2 − ∆Faα , (9.8.2)
 Gn s w H v , fr 
1 + − 
 ln(T0 / T ) ln(T / T0 ) 

where ∆Fcrα,00 is the critical energy at zero water supersaturation, sw = 0, with e = 0, aa = 0, and
rdr = ∞—i.e., as defined in the classical nucleation theory (see Section 9.7):

4π
∆Fcrα,00 (T ) = σ is rcr2 ,0 f (mis , x )
3
16π σ is3 f (mis , x ) 16π σ is3 f (mis )
= 2
≈ , (9.8.3)
3 [ ρi Lm ln(T /T0 )]
ef
3 [ ρi Lefm ln(T / T0 )]2

where the last equation accounts for the approximation (Eqn. 9.7.16a) for f (mis, x) ≈ f (mis). For further
transformation of (Eqn. 9.8.2), consider two examples of heterogeneous nucleation that occur via the
freezing of interstitial deliquescent aerosols and deliquescent haze particles at T < −10 °C. For super-
saturations typical in the clouds without extremely high updrafts and sufficiently far from the cloud
boundaries, sw ∼ 1 × 10−4 to 1 × 10−3 (or 10−2 to 10−1 %). The parameter Gn ∼ 0.4 (see Fig. 8.14c);
thus, the term Gnsw ∼ 0.4 × 10−4 to 0.4 × 10−3. At T < −10 °C, when heterogeneous nucleation becomes
noticeable, ln(T0/T) > 0.037, and X = Gnsw/ln(T0/T) << 1.
Consider another example, heterogeneous ice nucleation by freezing of haze particles at water
subsaturation, sw < 0, in cloudless atmosphere at low temperatures—e.g., in cirrus at T = 223 K. Then,
ln(T0/T) ≈ 0.2, the critical RHW ≈ 85% (see Section 9.12)—i.e., sw = −0.15. With Gn ∼ 0.4, the term
Gnsw /ln(T0 /T) ≈ −0.4 × (−0.15)/0.2 = −0.3. We can assume again |X| = |Gnsw /ln(T0 / T)| << 1 because the
term of the second order in expansion by |X| contributes less than 9%. A similar assumption can be
made on the term Hv,fr /ln(T0 /T). Effects of the freezing drop radius rdr and of the misfit strain e can be
considered as corrections to the main expressions for DFcr in the physically reasonable variations of
rdr and e (Young, 1993; Khvorostyanov and Curry, 2004a,b; see Section 9.11). The effects of pressure
excess become noticeable only at very high pressures ∼103 atm (Kanno and Angell, 1977; Mishima
and Stanley, 1998; Koop et al., 2000; Khvorostyanov and Curry, 2004a; Curry and Khvorostyanov,
2012) that can be created in the laboratory experiments but are not met under usual atmospheric
conditions. Therefore, we can omit here the terms with Dp. These terms can be easily included in the
final equations for analysis of the experiments at high pressures.
Thus, we can expand the denominator in (Eqn. 9.8.2) by the power series of X = Gnsw / ln(T0 /T),
keeping only the first term in the series (the second term gives us a contribution of a few percent, or
less than 1%). Thus, we obtain from (Eqn. 9.8.2)

 2 H v , fr 
∆Fcr (T , sw ) ≈ ∆Fcrα,00 (T ) 1 − (κ s ∆Fcrα,00 )sw + α
 − ∆Fa ,
 ln(T 0 / T ) 
≈ ∆Fcrα,00 (T ) − (κ s ∆Fcrα,00 )sw + ∆Fcrε − ∆Faα , (9.8.4)
432 Heterogeneous Nucleation of Drops and Ice Crystals

where

2Gn 2 RT 2 H v , fr (ε , rdr ) ∆Fcαr ,00

κs = = , ∆Fcrε = . (9.8.5)
ln(T0 /T ) M w Lm ln(T0 /T )
ef
ln(T0 / T )

The four terms on the RHS of (Eqn. 9.8.4) describe, respectively, the effects of temperature, water
saturation ratio, misfit strain and drop radius, and active sites. The range of sw for the applicability
of (Eqn. 9.8.4) can be estimated as follows. For not very large supercoolings DT = T0 − T
< 40–60 K, and a simplified case, neglecting e, rdr, and Dp, and using the approximate relation
ln(T0/T) ≈ DT/T, (Eqn. 9.8.4) can be further reduced to

 sw 
∆Fcr (T , sw ) ≈ ∆Fcαr ,00 (T ) 1 − 2Gn  . (9.8.6a)
 ∆T / T

Here the critical energy DFcr(T,sw) is separated into two factors: ∆Fcrα,00 (T ) is the critical energy
at zero water supersaturation, sw = 0 or (Sw = 1), and depends only on T, and the second term in the
brackets describes the dependence on supersaturation. A quantitative limitation on supersaturation
sw follows from the condition that keeping only the first term in expansion by X is valid when X ≈
GnT|sw|/DT << 1 or, with Gn ≈ 0.4:

∆T ∆T
sw ≪ ≈ 2.5 . (9.8.6b)
Gn T T

This criterion is usually satisfied for most situations with heterogeneous crystal nucleation. For
example, at temperatures T = 263 and 253 K, or supercoolings DT = 10 K and 20 K, the limitations
are: |sw| < 0.095 (9.5%) and |sw| < 0.20 (20%), respectively. The supersaturations are much lower in
mixed clouds with freezing drops, and subsaturations are smaller than 5–10% in the nucleation of
crystals via the freezing of haze particles without a liquid phase. Thus, the expansion (Eqn. 9.8.4) is
valid under a sufficiently wide range of cloud conditions, for most cloud types, which allows a great
simplification of the nucleation rates.
For parameterization of the concentration of nucleated crystals, similar to that for homogeneous
nucleation in Khvorostyanov and Curry (2012) (see Section 8.10), we need to separate the three
dependencies of the nucleation rate per particle Jf,het(T, sw, rN): on the temperature T, water supersatu-
ration sw, and aerosol properties, in particular, on the radius rN of the insoluble core inside a freezing
particle. Generalizing a separation method, developed in Khvorostyanov and Curry (2004b) and sub-
stituting (Eqn. 9.8.4) into (Eqn. 9.6.7) for Jf,het, we obtain after simple transformations

α 0) rN2  κ s ∆Fcrα,00   ∆F α (r ) 
J f ,het (T , sw , rN ) ≈ J (0,
f , het (T , rN ) 2
exp  sw  exp  a N 
rN  kT   kT 
α 0) α
≈ J (0,
f , het (T , rN ) J act (T , rN ) J het (T , sw , mis ),
s
(9.8.7)

where

α 0)
 ∆Fact (T ) ∆Fcrα,00 ∆Fcrε 
J (0,
f , het (T , rN ) = Chet (rN ) exp  − − + , (9.8.8)
 kT kT kT 
α
J act (T , rN ) = [(rN2 / rN2 ) exp( zα rN2 )], (9.8.9a)
9.8. Properties of the Deliquescence-Freezing Mode 433

∆Fa α aσ is (1 − mis )
zα = = , (9.8.9b)
kT kT
s
J het (T , sw , mis ) = exp(ushet sw ), (9.8.10)
α0 α0 α0
κ s ∆F ∆F (T , mis ) 2Gn (T ) 2 R ∆F (T , mis )
ushet (T , mis ) = cr ,0
= cr ,0
⋅ = ,cr ,0
(9.8.11)
kT kT ln(T0 / T ) kM w Lefm ln(T0 / T )
and rN is the average of rN over the aerosol population. If there are several active sites on the surface of
α
an IN, J act (T , rN ) is generalized using the expression for the energy of active sites (Eqn. 9.7.23). Then

α
J act (T , rN ) = (rN2 / rN2 )∑ exp( zαk rN2 ), (9.8.12a)
k
1 1
zαk =
kT
∑ ∆F a
αk
=
kT
∑f α
k
α ak rN2σ isδ miks , (9.8.12b)
k k

where δ misk = misk − mis, and fαk is the density of the active sites with the surface area α ak.
Thus, the nucleation rate is presented in (Eqn. 9.8.7) as a product of the three factors that describe
α 0)
respectively the major effects of T, rN, and sw. The first factor, J (0, f , het (T , rN ), is the nucleation rate

at sw = 0, aa = 0 (superscript “a 0”), and rN = rN , evaluated with Chet (rN )—that is, does not depend
α
on rN. The factor J act depends on za and describes the effect of the active sites area aa and rN. For
example, at T ≤ −20 °C, when diamond dust or Ac may form, and with mis = 0.5, the value of
za ∼ 0.7 × 1010 cm−2. Thus, za rN2 ∼ 0.7 for small aerosol particles with rN = 0.1 μm but grows to
za rN2 ∼ 70 for larger particles with rN = 1 μm, which results in a great enhancement of the nucleation
rate by the factor exp(za rN2 ) in (Eqn. 9.8.7) due to the active sites. The factors J het s
(T , sw , mis ) and
us,het(T, mis) depend on the supersaturation, temperature, and contact parameter and describe the
effects due to variations of humidity or supersaturation sw.
Equation (9.8.7) can be rewritten in two additional forms:

J f ,het (T , sw , rN , ε ) ≈ J (0)
f , het (T , rN , ε ) exp(ushet s w ), (9.8.13)

J f ,het (T , sw , rN , ε ) = J (0)
f , het (T , rN , ε )[ bhet (T )] ,
sw
(9.8.14)

where
(0,α 0) α
J (0)
f , het (T , rN , ε ) ≈ J f , het (T , rN , ε ) J act (T , rN ), (9.8.15)
α0
 ∆F (T , mis ) 2Gn (T ) 
cr ,0
bhet (T ) = exp(ushet ) ≈ exp  ⋅ . (9.8.16)
 kT ln(T0 / T ) 

The factor J (0)

f , het (T , rN , ε ) is the nucleation rate at water saturation, sw = 0 or Sw= 1, which describes

the effects of temperature, active sites, and misfit strain, but does not depend on supersaturation. The
second multipliers in (Eqns. 9.8.13) and (9.8.14) describe the effects of sw variations, and these equa-
tions show that the supersaturation dependence of the nucleation rate can be presented in different
forms, either as an exponential function or as a power law. The power law (Eqn. 9.8.14) could be
considered an analog of the humidity parameterization of Huffman (1973), although the functional
dependence is somewhat different here. The exponent by sw in (Eqn. 9.8.13) resembles the exponen-
tial parameterization by the ice supersaturation si of the crystal concentration of Meyers et al. (1992),
and will be derived in this form in Section 10.1.
434 Heterogeneous Nucleation of Drops and Ice Crystals

Equations (9.8.7)–(9.8.16) describe analytically the supersaturation dependence of the heteroge-

neous nucleation rate and can be used for development of parameterizations of this quantity as was
done for homogeneous nucleation in Section 8.10 and will be done for heterogeneous freezing in
Section 10.1. Equations (9.8.7) and (9.8.13) show that Jf,het ∼ exp(ushetsw), and increases exponen-
tially with sw, which can be recalculated to the exponential dependence on ice supersaturation si,
resembling empirical parameterizations of Meyers et al. (1992) and Rogers et al. (1998), but with
additional T-dependence. It will be illustrated in more detail for the crystal concentrations in the
following text. This exponential variation may explain very fast crystal nucleation rates in clouds at
and after the stage of intensive coagulation among the drops, and the decrease of their concentra-
tion when supersaturation may increase above its normal value of 0.01–0.1% and produce high Nc,
as was hypothesized by Hobbs and Rangno (1990) and Rangno and Hobbs (1991, 2001), and was
discussed in Khvorostyanov and Curry (2005a). Other reasons for possible high Nc are discussed in
the following text.

9.8.3. Separation of Insoluble Fractions between Activated Drops and Unactivated CCN

During drop activation, separation (or redistribution) of insoluble fractions occurs between activated
drops and unactivated CCN. The soluble substance of CCN before activation can be characterized
by the mass fraction em, and so the insoluble fraction is eN = 1 − em. As described in Chapters 6 and
7, the critical saturation ratio (or supersaturation sw,cr) for a drop activation depends on the CCN
dry radius rd0 and its soluble fraction em. For any given rd0, the critical saturation ratio increases with
decreasing em. So, when the maximum saturation ratio Sw,max is reached in a cooling cloud parcel dur-
ing drop activation, all CCN of the same radius rd0 with em > em,cr will be activated, and all CCN with
em < em,cr (eN > eN,cr) will remain as deliquescent but unactivated interstitial CCN (e.g., Hänel, 1976).
This leads to the natural separation of the insoluble substance during drop activation: its fraction
eN will be substantially greater in these non-activated CCN than in the cloud drops, and the insoluble
fraction in unactivated CCN increases with increasing rd0. Note also that the radii of the dry particle
rd0 and its insoluble fraction rN are related as rN ∼ rd0eN1/3, so that rN grows with increasing rd0 at constant
eN, which may explain the higher ice nucleating activity of the larger CCN.
Since the heterogeneous nucleation rate is Jf,het ∼ rN2, this accumulation of the insoluble sub-
strate in deliquescent interstitial CCN will increase their integral surface area and ice nucleating
ability relative to the activated drops. Thus, separation of insoluble fractions during drop activa-
tion may explain several effects in ice nucleation if these interstitial CCN serve as IN: a) higher
insolubility of these particles as compared to the average CCN; b) higher ice nucleating efficiency
of larger CCN that contain larger amounts of insoluble material; c) higher efficiency of the CCN
deliquescence-freezing mode than that of the immersion mode; and d) higher efficiency of the
contact mode compared to the immersion mode if these interstitial CCN collide with the drops
and serve as contact nuclei. Note that the dilution mw/md of these CCN, with mw being the mass
of accumulated water, is high enough even for small soluble fractions, and salt concentration is
low at saturation ratios close to critical (e.g., Tables 6.2, 6.3 in Pruppacher and Klett, 1997, and
Chapters 6 and 7 here). Thus, the freezing point depression due to the solution is small, and the
catalyzing freezing action of insoluble substrates can overwhelm the effects of the freezing point
depression.
9.8. Properties of the Deliquescence-Freezing Mode 435

A quantitative description of this separation and subsequent heterogeneous ice nucleation requires
knowledge of the CCN distributions by dry radii and insoluble (or soluble) fractions. Unfortunately,
information on the distribution of insoluble fractions among CCN of the same size is very scarce, since
typical measurements of soluble fractions cover some size range but not single particles (Pruppacher
and Klett, 1997). Thus, we can only hypothesize a plausible size distribution function of these inter-
stitial deliquescent aerosols.

9.8.4. Characteristic Relaxation Times of CCN Size and Solution Concentration

The characteristic relaxation times of CCN size and the solution concentration illuminate the mecha-
nism for the impact of supersaturation on an ice germ. As discussed in Section 9.7, the radius of a
deliquescent CCN adjusts to equilibrium as predicted by the Kohler curves (Eqn. 3.9.8). Otherwise,
supersaturation or subsaturation sw = Sw −1 occurs around a CCN droplet and it grows or evaporates
until its radius rd reaches such a value that the equilibrium condition in (Eqn. 3.9.8) is satisfied. The
relaxation time teq, during which a deliquescent CCN reaches equilibrium both at sub- and supersatu-
ration, can be estimated from the diffusion equation as teq ≈ 0.4 × 106 × rd2/|Sw−1| with rd in cm. Both
deliquescent CCN at Sw < 1 and interstitial CCN at Sw > 1 reach equilibrium very rapidly (generally
much less than 1 s) in response to variations of external supersaturation.
Another timescale tdif characterizes the time during which salt concentration within a CCN drop
reaches equilibrium due to diffusion processes and becomes homogeneous. It can be estimated as
tdif ∼ 0.14 rd2/Dc, where Dc ∼ 10−5 cm2 s−1 is the coefficient of mass (salt) diffusion within a drop
(Sedunov, 1974). This yields an estimate tdif ∼ 10−6 s and 10−4 s for drops of radii 0.1 μm and 1 μm,
respectively. The characteristic time of mean supersaturation variations tsup in natural clouds without
vigorous updrafts is typically 10–103 s, so that the hierarchy of the timescales is tsup >> teq ≥ tdif—i.e.,
tsup is much greater than both teq and tdif.
These estimations illustrate the main mechanism by which variations of external supersaturation
sw influence an ice germ that is embedded in a solution drop and is not in direct contact with exter-
nal supersaturation field: variations of supersaturation are immediately followed by the much faster
adjustment of the CCN size and homogenization of solution concentration in the entire drops’ volume,
including the vicinity of the insoluble substrate and ice germ. The growth of the saturation ratio Sw
(or sw) is accompanied by the rapid swelling of a deliquescent CCN and a decrease in solution con-
centration, which causes a decrease in rcr(T, Sw) as described by (Eqns. 9.7.9) and (9.7.10). Vice versa,
a decrease of Sw is followed by the shrinking of a CCN, an increase in solution concentration, and
growth of rcr(T, Sw). Thereby, the link is established between varying Sw (or sw) and rcr inside CCN.
An ice germ embedded in a CCN drop and that is “remote” to the external supersaturation is nonethe-
less influenced by it very quickly via the adjustment of the drop radius to supersaturation. Note that
the same mechanism of impact of sw on “remote” rcr in a solution drop acts in homogeneous freezing
as described by the equations for rcr derived in Chapter 8.
The characteristic freezing time tfr under conditions considered here is typically a few tens to a
few hundred seconds (see Section 9.14); thus, tfr >> τeq, and tfr >> τdif, and this rapid adjustment of rcr
to varying supersaturation also occurs during CCN freezing. For drops of a few microns, the impact
of supersaturation on rcr and the freezing point depression should be smaller because of the smaller
contribution of the term with Sw in the denominator of rcr, see Section 9.7.
436 Heterogeneous Nucleation of Drops and Ice Crystals

9.9. Surface Freezing and Melting

9.9.1. Surface Freezing

There are several possible geometrical configurations of an ice germ forming at the surface of a solu-
tion drop. In Section 9.7, we considered volume freezing, whereby an ice germ forms on the surface
of an insoluble core located inside a solution drop. In this section, we consider an ice germ located
at the interface between the humid air and solution drop, whereby a solid forms at the interface of
its own melt and gas (vapor or humid air). This quasi-heterogeneous ice germ formation was briefly
outlined by Defay et al (1966) and was referred to as “pseudo-heterogeneous freezing” (Tabazadeh
et al., 2002a,b; Djikayev et al., 2002) and as “quasi-heterogeneous freezing” in Khvorostyanov and
Curry (2004a).
Consider an ice germ represented by a spherical segment (lens or “tiny pancake ice”) and bounded
by two surfaces. An outer surface (in contact with air) has a radius rcr and the inner surface (in contact
with the solution drop) is determined by a droplet radius rdr . A specific feature of surface freezing and
melting of many substances is that the contact angle between a solid substance (e.g., ice) and its own
melt (liquid water) is small but non-zero—that is, a solid surface is not completely wettable by its
liquid. For example, the measured contact angles between ice and water were 0.5 to 2 degrees, and at
the beginning of slow melting, melted water on the ice surface does not form the continuous film and
does not spread infinitely over the surface, but rather forms many thin liquid droplet caps or lenses,
and similar situations are observed for some metals and other substances (Ketcham and Hobbs, 1969;
Knight, 1971; Hobbs, 1974; Elbaum and Schick, 1991; Elbaum, Lipson, and Dash, 1993; Dash et al.,
1995; Laaksonen et al., 1995; Oxtoby, 2003; Rosenberg, 2005).
Thus, the case of surface freezing and melting represents a mixture of homogeneous and het-
erogeneous processes because it proceeds homogeneously without a foreign substance, and due to
incomplete wettability the geometrical decrease of free energy is similar to those in heterogeneous
freezing as described in Sections 9.2 and 9.7. These processes can be called “quasi-heterogeneous
freezing and melting.”
Because both the ice germ and solution drop are in mechanical equilibrium with the environmental
air, it follows that the pressures inside the solution drop, ps, and the ice crystal cap, pi, with corre-
sponding radii rdr and rcr are described by the Laplace equation:

 2σ   2σ 
dps = dp + d  sa  , dpi = dp + d  ia  , (9.9.1)
 rdr   rcr 

where sia is the surface tension at the ice–air interface. For freezing, phase 1 is water, and phase 2
is ice. Substituting (Eqn. 9.9.1) into the entropy equation (Eqn. 3.6.4) with the same notations and
assumptions as in Section 9.7 (rk0,1 = rw, and rk0,2 = ri, vw = Mw/rw, vi = Mw/ri, Lˆ12 = M w Lm, ak,1 = aw,
ak,2 = ai = 1—i.e., ln(ai) = 0, but without the strain term (e = 0) because we do not consider undissolved
particulates here, and dividing by Mw, we obtain

Lm  1 1  2σ sa   2σ ia  RT
− dT +  −  dp + d   − d  ρ r  + M d ln aw = 0 (9.9.2)
T  ρ w ρi   ρ w rdr   i cr  w
9.9. Surface Freezing and Melting 437

Integration of (Eqn. 9.9.2) with the same boundary conditions as in Section 9.7, rcr = rdr = ∞, aw = 1,
and p = p0 at T = T0 yields

T0 2σ ia 2σ sa  1 1  RT
Lefm ln = − + −  ∆p − ln aw (9.9.3)
T ρi rcr ρ w rdr  ρi ρ w  Mw

It is interesting to note that Dufour and Defay (1963) considered a different configuration, with the
drop and crystal coexisting in air, and obtained a similar equation (except without the pressure term)
with a more complicated expression for the solution term. One can see that (Eqn. 9.9.3) contains both
positive and negative terms on the right-hand side. In particular, the terms with pressure and aw are
positive. This causes an increase of the term ln(T0/T) on the right-hand side—i.e., lowering the freezing
temperature T with increasing pressure and solution molality.
Equation (9.9.3) predicts situations with T < T0, which is a physical state, and with T > T0; that is,
the existence of ice above the bulk triple point (the superheating of crystals), which is an unobserved
state (Dufour and Defay, 1963). This problem was prescribed to limitations of the classical nucleation
theory (Oxtoby, 2003), which makes predictions that are symmetric relative to T0. This symmetry is
absent in the density functional theory that avoids freezing point elevation (Oxtoby, 2003), although
superheating above T0 before melting is observed in some metals and other solids (e.g., Hobbs, 1974;
Lifshitz and Pitaevskii, 1997). Now, replacing aw with Sw, in (Eqn. 9.9.3), we obtain finally the criti-
cal radius rcr of an ice germ at the solution–air interface:

2σ ia
rcr = , (9.9.4)
ρi L ln[(T0 / T ) SwGn exp(− H s , fr )]
ef
m

∆ρ∆p 2σ sa
H s , fr = − . (9.9.4a)
ρi ρ w Lefm rdr ρ w Lefm

Note that (Eqn. 9.9.4) for surface freezing contains the surface tension sia at the ice–air interface
instead of sis for solution–ice as in Section 9.7 for volume freezing, which reflects the difference in
freezing mechanisms.
When a solid is incompletely wettable by its own melt, the critical free energy of an ice germ
nucleating at the liquid–air interface at surface quasi-heterogeneous freezing in the absence of the
foreign substances can be written similar to (Eqns. 9.7.14) and (9.7.15). Using (Eqn. 9.9.4) for rcr ,
the critical free energy becomes

4 16π σ ia3 f (mis , x )

∆Fcr = πσ ia rcr2 f (mis , x ) = 2 ,
(9.9.5)
3 3  ef  T0 G 

ρ L ln
 i m 
T
S w exp − H ( )
s , fr  


where x = rdr/rcr for the cases of surface freezing, mis = cosqis is the corresponding wettability
parameter, qis is the contact angle at the interface of ice and its own liquid (the angle between the
plane surface of the solution and the dome-like surface of the ice, ∼0.5–2 degrees in the case of pure
water according to Ketcham and Hobbs, 1969; Knight, 1971) and f(mis, x) is the geometric factor
defined by (Eqn. 9.7.16). Since qis is small in this case, f(mis, x) is close to 1, making nucleation
easier. However, if to assume that sia ≈ siv, and recall that siv ∼ 4sis, one can see that DFcr ∼ siv3 for
438 Heterogeneous Nucleation of Drops and Ice Crystals

surface freezing can be much greater than DFcr ∼ sis3 for volume freezing. Which kind of freezing,
volume or surface, would dominate, is not clear due to uncertainty in the parameters qis and sia. A
solution of this question requires refined measurements of the parameters, comparison of the volume
and surface freezing modes in isolation, and careful calculations.

9.9.2. Surface Melting

The numerous theories of surface melting include intergranular melting in polycrystalline crystals,
melting at grain and vein junctions and evaluation of the lowering of the bulk triple points and melted
quasi-liquid film thickness with an accounting for various mechanisms of premelting (the melting or
formation of liquid and quasi-liquid layers on ice surface below 0 °C, which, in particular, explains
why ice and snow are slippery and allow skating and skiing, and how this slipperness decreases and
ends toward −40 °C), and the effects of crystal size and impurities (Defay et al., 1966; Hobbs, 1974;
Dash, et al., 1995; Laaksonen et al., 1995; Fletcher, 1968; Ketcham and Hobbs, 1969; Knight, 1971;
Elbaum and Schick, 1991; Elbaum et al., 1993; Johari, 1998; Wettlaufer, 1999; Wettlaufer and Dash,
2000; Oxtoby, 2003; Rempel et al., 2004; Rosenberg, 2005).
Here we consider one simple mechanism of surface melting: nucleation of a liquid drop at the
crystal–gas interface when melting is incomplete—i.e., drops or liquid lenses occur instead of a
liquid film. We consider a quasi-heterogeneous process of nucleation of a liquid germ at the surface
of its own solid at small but finite contact angles. This type of surface melting has been observed in
laboratory experiments (Hobbs, 1974; Dash, et al., 1995; Ketcham and Hobbs, 1969; Knight, 1971;
Elbaum et al., 1993; Elbaum and Schick, 1991). This case is similar to surface freezing considered
in the previous section except with reversed configuration of liquid and ice. To determine the droplet
critical radius rdr and the melting temperature Tm, we again begin with the entropy equation (Eqn. 3.6.4).
For melting, phase 1 is ice, phase 2 is the liquid, and −Lm = (hi0 − hw0)/Mw. We consider a liquid germ
that is located at the interface of the crystal and humid air and represents a spherical segment (lens)
bounded by two surfaces. An outer surface (in contact with vapor or humid air) is a spherical segment
with radius rdr and the bottom surface (in contact with ice crystal) has a radius rcr.
Using the conditions of mechanical equilibrium, we write for the pressures inside the liquid lens
ps and crystal pi the Laplace equations:

 2σ   2σ 
dps = dp + d  sa  , dpi = dp + d  ia  . (9.9.6)
 rdr   rcr 

Substituting (Eqn. 9.9.6) into (Eqn. 3.6.4) and dividing by Mw, we obtain

Lm  1 1   2σ   2σ sa  RT
dT +  −  dp + d  ia  − d  − d ln aw = 0. (9.9.7)
T  ρi ρ w   ρi rcr   ρ w rdr  M w

Integration of (Eqn. 9.9.7) with the same boundary conditions aw = 1, rdr = rcr = ∞, and p = p0 at
T = T0, yields

T0 2σ sa 2σ ia  1 1  RT
Lefm ln =− + + − ∆p − ln aw , (9.9.8)
T ρ w rdr ρi rcr  ρi ρ w  Mw
9.9. Surface Freezing and Melting 439

which formally coincides with (Eqn. 9.9.3), except that the unknown is here rdr. The terms with pres-
sure at Dp > 0 and the solution effects are positive, shifting the melting temperatures Tm below the
bulk triple point as in the case with homogeneous freezing in Chapter 8.
At negative pressure (Dp < 0), e.g., in the case of internal melting of ice caused by strong radia-
tive heating and the formation of “Tyndall flowers,” when ice may exist in metastable equilibrium at
up to +8 °C and Dp∼ −103 bar (Hobbs, 1974), (Eqn. 9.9.8) describes the competition of the negative
pressure, which causes elevation of Tm (possibly to well above 0 °C) and the counteracting solution
effects (aw < 1) that tend to lower Tm. Again replacing aw with Sw, we find from (Eqn. 9.9.8) the criti-
cal radius rdr of a liquid germ:

2σ sa
rdr = , (9.9.9)
− ρ w Lefm ln[(T0 /T ) SwGn exp(− H m )]
∆ρ∆p 2σ ia
Hm = + . (9.9.10)
ρ w ρi Lm rcr ρi Lefm
ef

Equation (9.9.9) differs from (Eqn. 9.9.4) for freezing by the opposite sign of the temperature term
ln(T0/T).
For physical analysis, (Eqn. 9.9.9) can be rewritten as
2σ sa
rdr = (9.9.10a)
ρ w Lefm [− ln(T0 /Tm ) + H m − ln SwGn ]

The physical condition rdr > 0 requires that the denominator should be positive, which yields

ln(T0 /Tm) ≤ Hm − Gn ln Sw . (9.9.10b)

For the bulk ice (rcr = ∞) and the absence of external pressure, Dp = 0, we have Hm = 0. If a cap of the
liquid is pure water, then Sw ≈ aw = 1. Thus, ln(Sw) = 0 and (Eqn. 9.9.10) reduces to

ln(T0 /Tm) ≤ 0, or Tm ≥ T0 . (9.9.10c)

That is, melting at these conditions may occur only above the triple point T0. Presence of the external
pressure Dp and the final radius of a melting crystal rcr cause a decrease in the melting point. If solute
penetrates into melting liquid from the environment, then Sw < 1, and this causes an additional depres-
sion of the melting point, so that the relations can be reached Tm < T0, ln(T0/Tm) > 0, and melting may
occur below the triple point. Equations (9.9.9)–(9.9.10b) allow us to study the effects of each of these
factors (Dp, rcr, Sw) separately. The effects of variations of the saturation ratio or water activity on the
melting point depression are described in more detail in Section 9.11 and 9.12.
The critical free energy for this type of surface melting can be written as for the solid/air interface
and using (Eqn. 9.9.9) for rdr as

4 16π σ sa3 f (mis , x )

∆Fcr = πσ sa rdr2 f (mis , x ) = 2 , (9.9.11)
3 3   T0 G 
− ρ w Lm ln  Sw exp ( − H m )  
ef

 T 
440 Heterogeneous Nucleation of Drops and Ice Crystals

where x= rcr/rdr for surface melting, qis is the contact angle at the interface of ice and its own liquid,
mis 5 cosqis is the wettability parameter and f(mis) is the geometric factor defined by (Eqn. 9.7.16),
but with these mis and x specific for surface melting. Because the contact angle for surface melting is
small, the geometric factor f(mis, x) is close to unity, which may favor quasi-heterogeneous surface
melting.

9.10. Nucleation in a Polydisperse Aerosol

We have considered so far single aerosol particles characterized by the radius of an insoluble sub-
stance rN. When we consider heterogeneous freezing of the size spectra, there can be two different
situations at water subsaturation, sw < 0, and water supersaturation, sw > 0. As described in Chapters 6
and 7, the size spectrum of the original dry CCN, fa(ra), transforms into the spectrum of the wet aero-
sol above the threshold of deliquescence of the soluble fraction and sw < 0. These CCN usually also
contain an insoluble fraction and may serve as IN. The freezing of these wet haze particles serving as
IN may occur at water subsaturation, sw < 0, in the deliquescence-freezing (DF) mode, as occurs at
the formation of cirrus clouds, diamond dust, and similar cloudless conditions at sw < 0 when mostly
only submicron wet haze particles produce crystals.
When the relative humidity increases further and reaches 100%, some of the CCN are activated
and cloud drops form. Then, the aerosol spectrum splits into 2 fractions: a) the interstitial aerosol of
unactivated particles with the size spectrum fa,int(ra), which governs freezing in the DF mode, and b)
aerosol immersed in the activated cloud drops with the size spectrum fa,im(ra), which governs freez-
ing in immersion mode. These two fractions are separated by the boundary radius rb. This radius is
of key importance for ice nucleation since it determines aerosol concentration in each fraction and
therefore the efficiency of each mode. At sw > 0, the boundary radius can be expressed via the water
supersaturation sw as rb = 2Ak/3sw (see Chapter 6). Thus, sw(t) defines the splitting of the original dry
CCN-IN size spectrum into interstitial and immersed fractions. An important feature of CCN at sw > 0
considered in Chapters 6 and 7 is that the equilibrium deliquescent interstitial CCN may coexist with
cloud drops. At supersaturation sw > 0, the droplets with radii rd > rb are activated cloud drops, and
those with rd < rb are non-activated CCN in equilibrium with the supersaturated environment. Since
AK ∼ 10−3 μm at the considered temperatures, the values of rb are rb ∼ 1 μm, 0.1 μm, and 0.01 μm at
sw = 0.001, 0.01, and 0.1 (0.1, 1, and 10%, respectively). The value of rb determines the well-known
gap between the CCN and the cloud drop size spectra (see Fig. 2.5 here). Further, we consider het-
erogeneous ice nucleation in both situations: at water subsaturation with nucleation of haze particles
in the DF mode, and at water supersaturation when the CCN-IN spectrum is split into two fractions,
interstiatial and immersed in the drops.

9.10.1. Freezing of Haze Particles at Water Subsaturation in the DF Mode

The probability of freezing of an aerosol particle containing an insoluble part with rN is

( t
)
Pfr (rN , t ) = 1 − exp − ∫ J f ,het (rN , t ′) dt ′ ,
0
(9.10.1)
9.10. Nucleation in a Polydisperse Aerosol 441

where Jf,het is defined in (Eqn. 9.6.7), with DFcr defined in (Eqns. 9.7.15) or (9.7.24) for volume freez-
ing. The number of particles dNdf nucleated from CCN by the deliquescence-freezing mode in the
range (rN, rN + drN) is

dN df (rN , t ) = Pfr (rN , t ) fa (rN )drN , (9.10.2)

and the total number of nucleated particles is obtained by integrating over the aerosol size spectrum:
rmax rmax
N fr (t ) = ∫ dN df (rN , t ) = ∫ Pfr (rN , t ) fa (rN ) drN . (9.10.3)
rmin rmin

The average probability of freezing Pfr,p in a polydisperse aerosol is then

N fr (t ) 1 rmax
Pfr , p (t ) =
Na
=
Na ∫ rmin
Pfr (rN , t ) fa (rN ) drN . (9.10.4)

The heterogeneous crystal nucleation rate (cm−3 s−1) in a polydisperse aerosol can be calculated as:

R f ,het =
dN fr
dt
=∫
rmax

rmin ( t
drN fa (rN ) J f ,het (t ) exp − ∫ J f ,het (t ′)dt ′ .
0 ) (9.10.5)

The preceding equations include the radius rN of the insoluble fractions but not the radius of the
haze particles ra. The reason for this is that the freezing rate in (Eqn. 9.10.1) depends on the surface
area ∼r N2 of the insoluble inclusion inside a partially soluble CCN with rN, but not on the surface
∼r d2 of the entire CCN particle. The radius ra increases during deliquescence of the CCN, and, as
described in Chapter 6, can be expressed in equilibrium via the dry radius rd0 and some function of
water saturation ratio y (Sw) as ra(Sw) = rd0y (Sw). So, the CCN hygroscopic growth can be described
by Sw; however, the effect of Sw is already accounted for in expressions for rcr and DFcr given in
Section 9.7. Unfortunately, not much is known about the size distributions and properties of insoluble
substance in CCN. We can estimate fa(rN) using data on the mass soluble fraction of CCN eN, which
varies over the range 0.1–1.0 with an average value of 0.5 (Pruppacher and Klett, 1997, Chapter 8).
As mentioned earlier, the radii rd0 and rN are related via the insoluble fraction eN as rN ∼ rd0eN1/3,
so that rN and rd0 are quite comparable for the mean eN = 0.5 and especially for the high eN = 0.9
insoluble fractions: rN ∼ 0.8rd 0 for eN = 0.5 and rN ∼ 0.97rd 0 for eN = 0.9. This means that the modal
radii and dispersions of the size spectra of the insoluble fraction fa(rN) are rather close to the aerosol
spectra. This fact is used later for averaging over rN with fa(rN).
Fig. 9.8 shows the subintegral function (cm−3 s−1) for the freezing nucleation rate Rfr in
(Eqn. 9.10.5) for various combinations of temperature and humidity. This figure illustrates that the
main contribution to the freezing rate comes from the submicron aerosol mode, around 0.1–0.5 μm,
and contributions from nucleation and giant modes are smaller. This finding is in agreement with
experimental data on the radii of IN in the central particles of snow crystals that were typically
in the range 0.05–7.5 μm with a mode rm between 0.25 and 2.5 μm (Pruppacher and Klett, 1997),
recent measurements of IN in the Arctic that found modal radii rm of 0.18–0.23 μm (Rogers et al.,
2001), and measurements in the central U.S., rm ≈ 0.2 μm (Chen et al., 1998; Rogers et al., 1998).
We considered here the simplest case of the monomodal aerosol size spectrum and did not include
the larger size fractions, which also may contribute to the freezing rate. A generalization for several
442 Heterogeneous Nucleation of Drops and Ice Crystals

1E–1
1E–2

Subintegral function (cm –3 s –1)

1E–3
1E–4
1E–5
1E–6
1E–7
1E–8 T = –15, Sw = 1.005
1E–9 T = –12, Sw = 1.04
1E–10 T = –20, Sw = 0.96
T = –25, Sw = 0.93
1E–11

0.01 0.10 1.00 10.00

CCN radius (µm)

Figure 9.8. Subintegral function (cm−3 s−1) for the freezing nucleation rate Rfr which shows the
contributions of the various aerosol radii into the freezing rate for four cases: T = −15 °C, Sw = 1.005
(circles); T = −12 °C, Sw = 1.04 (diamonds); T = −20 °C, Sw = 0.96 (triangles); T = −25 °C, Sw = 0.93
(crosses). From Khvorostyanov and Curry (2004b), J. Atmos. Sci., 61, © American Meteorological
Society. Used with permission.

aerosol fractions can be easily made through summation over several fractions as shown later in
the text. The addition of larger aerosol particles along with the variation of insoluble fractions
over the size spectrum should affect heterogeneous freezing, since the insoluble fraction of CCN
increases with size faster than the soluble fraction (e.g., Laktionov, 1972; Pruppacher and Klett,
1997), thereby increasing the catalyzing properties of large CCN in ice nucleation (e.g., Berezinsky
and Stepanov, 1986).
The aerosol size rN,max(T,Sw) with maximum contribution to the nucleation rate, illustrated in
Fig. 9.8, can be estimated analytically using this theory. First, we perform some simplifications.
Since typical values of rcr are 10−3–10−2 μm, for most aerosol particles with rN ≥ 0.1 μm, the parameter
x = rN/rcr >> 1. Then the geometrical factor f(mis,x) (Eqn. 9.7.16) equals its asymptotic value f(mis,x) ≈
(mis3−3mis + 2)/4 at x→∞. It does not depend on rN; the nucleation rate per unit area, Jf,het /rN2 ≡ y(T),
also does not depend on rN as shown in (Eqns. 9.6.7) and (9.6.8). Further, we assume that the aerosol
is monodisperse with radius rN. Then, the nucleation rate Rfr in (Eqn. 9.10.5) can be presented as
Rfr = y(T) rN2 exp(−y(T) rN2Dt) where Dt is the time interval. This is a Gaussian distribution relative
to rN, and a gamma distribution relative to y(T). Maxima are determined from the conditions dRfr /drN = 0
for rN and dRfr/dT = 0 for temperature. Both conditions lead to the equation

y(T , Sw )rN2max ∆t = 1. (9.10.6)

Thus, at some fixed T, we can calculate the radius of aerosol particles with the maximum freezing
rate
rN max (T , Sw ) = [ y(T , Sw ) ∆t ]−1/ 2 = rN ( J f ,het ∆t )−1/2 . (9.10.7)
9.10. Nucleation in a Polydisperse Aerosol 443

This equation shows that ice nucleation initiates from the largest aerosol particles for small nucle-
ation times Dt, and then the aerosol radius with maximum nucleation rate decreases with time. For
example, for y(T) ∼ 108 cm−2 s−1 (see Fig. 9.7), we have from (Eqn. 9.10.7) rN ∼ 10 μm at Dt = 0.01 s
and rN ∼ 0.1 μm at Dt = 100 s.
A general picture of the aerosol radius rN,max(T,Sw) with maximum contribution to the freezing
rate calculated with (Eqn. 9.10.7) and the same parameters as for Jf,het in Fig. 9.7 is shown as a T-Sw
diagram in Fig. 9.9. Aerosols in the size range rN from 0.1 to a few tens of μm can preferably nucleate
ice crystals in the rather narrow range of T, Sw. The dominant aerosol radius decreases rapidly at
fixed T and increasing Sw, and more slowly at fixed Sw and decreasing T. This behavior predicted
by (Eqn. 9.10.7) and illustrated in Fig. 9.9 is quite reasonable (the colder and more humid it is, the
smaller the particles that are nucleated), and is in agreement with chamber experiments (e.g., Berezinsky
and Stepanov, 1986; see Section 9.4 here), and may help identify experimentally the aerosol fractions
with a maximum nucleation rate under various conditions.
If the aerosol size spectrum consists of several size fractions that also can include particles of dif-
ferent composition, then the concentration of nucleated crystals can be evaluated by summation over
all fractions,
rmax,i rmax,i
N fr (t ) = ∑ ∫ dN df ,i (rNi , t ) = ∑∫ Pfr ,i (rNi , t ) fai (rNi ) drNi , (9.10.8)
rmin,i rmin,i
i i

1.30
1.25
log rN,max
1.20
1.15
1.10
–7

1.05 –5
–1
Sw

1.00
0.95
0.90
–5–7
0.85 –1

0.80
0.75
5 15 25 35 45 55
Supercooling (T0–T) (C)

Figure 9.9. Logarithm of the radius rN,max (cm) of the insoluble aerosol fraction with the maximum
heterogeneous freezing nucleation rate calculated with (Eqn. 9.10.7); log = −1 means rN = 10−1 cm
or 1000 μm, log = −5 means rN = 10−5 cm or 0.1 μm (bold line), and log = −7 means rN = 10−7 cm.
Aerosols in the size spectrum rN = 0.01−100 μm can preferably nucleate ice crystals in the narrow
corridor of T, Sw. From Khvorostyanov and Curry (2004b), J. Atmos. Sci., 61, © American
Meteorological Society. Used with permission.
444 Heterogeneous Nucleation of Drops and Ice Crystals

where i denotes the fraction. The probability of freezing in a polydisperse aerosol is then

∑ N (t ) 1 fr , i
rmax,i
∑
∑N ∫
Pfr , p (t ) = i
= Pfr ,i (rNi , t ) fai (rNi ) drNi . (9.10.9)
∑N ai ai i
rmin,i

i i

The heterogeneous crystal nucleation rate (cm−3 s−1) in a polydisperse aerosol with several fractions
can be calculated as a sum over all fractions:
dN fr ,i
R f ,het = ∑
i dt
= ∑∫
i
rmax,i

rmin,i ( t
drNi fai (rNi ) J fi ,het (t ) exp − ∫ J fi ,het (t ′ )dt ′ .
0 ) (9.10.10)

The values of Jfi,het are usually small, as will be shown in Section 9.14, and the expressions for Pfi, Nfr,
and Rf,het can be simplified as shown in Section 9.14.3.

9.10.2. Simultaneous Freezing in the DF and Immersion Modes at Water Supersaturation

As described in Section 9.10.1, at sw > 0, the aerosol spectrum splits into two fractions: the interstitial
aerosol of unactivated particles with the size spectrum fa,int(ra), and aerosol immersed in the activated
cloud drops with the size spectrum fa,im(ra). These two fractions govern freezing in the DF mode
and in the immersion mode respectively. The corresponding concentrations of the interstitial and
immersed in drops aerosol, Na,int and Na,imm, can be evaluated by integration over the aerosol size
spectrum fa(ra), as
rb [ sw ( t )] rmax

N a ,int = ∫ fa (ra ) dra ,

rmin
N a ,imm = ∫ f (r ) dr ,
a
rb [ sw ( t )]
a a (9.10.11)

where rmin and rmax are the lower and upper boundaries of a given aerosol fraction, and rb is the bound-
ary radius between the fraction, rb = 2Ak/3sw(t), which can change with time t along with evolving
supersaturation. All the other relevant integrals like surface areas, probabilities of freezing, etc., can
be evaluated in a similar way using the boundary rb(sw). An important feature of this spectral splitting
is that it depends on the history of a cloud parcel via sw(t). This means that different vertical velocities
in the parcel, or more generally, different advective, convective, and radiative cooling rates in the
models, or in the lab experiments, will lead to the different redistribution of the initial (input) dry
aerosol between the interstitial and immersion modes. An accurate calculation would require intro-
ducing the distribution functions for aerosol fa(ra, rN) and for drops fd(rd, rN) and solving equations
for them with tracking the amount of the insoluble fraction (rN) in each haze particle and each drop.
However, this approach would be too time-consuming for the present-day models. Thus, some sim-
plifications and additional hypotheses are required. One reasonable hypothesis is: an assumption on
the random distribution of the insoluble fraction (or rN) inside haze particles and drops; an assump-
tion discussed earlier that fa(ra) ≈ fa(rN), and introducing some average probabilities of freezing.
Then, the concentrations of haze particles Ndf freezing in deliquescence-freezing (DF) mode and
concentrations of drops Nfimm freezing in immersion mode can be calculated by integration over the
corresponding ranges of radii. The number of particles dNdf nucleated in DF mode in the range of the
aerosol radii (ra, ra + dra) is

dN df (ra , rN , t ) = Pfr (ra , rN , t ) fa (ra )dra , ra < rb . (9.10.12)

9.10. Nucleation in a Polydisperse Aerosol 445

The total number of particles nucleated in DF mode is obtained by integrating over the aerosol size
spectrum from rmin to rb[sw(t)]:
rb [ sw ( t )] rb [ sw ( t )]

N df (t ) = ∫
rmin
dN df (rd , rN , t ) = ∫
rmin
Pfr (ra , rN , t ) fa (ra ) dra . (9.10.13)

The average probability of freezing Pdf of a polydisperse aerosol in DF mode is then

rb [( sw ( t )]
N df (t ) 1
Pdf (t ) =
N a ,int
=
N a ,int ∫
rmin
Pfr (ra , rN , t ) fa (ra ) dra , (9.10.14)

where Na,int is defined in (Eqn. 9.10.11). The heterogeneous crystal nucleation rate (cm−3 s−1) in a
polydisperse aerosol in DF mode can be calculated as:

( )
rb [( sw ( t )]
dN df t
Rdf =
dt
= ∫
rmin
dra fa (ra ) J f,het (rN , t ) exp − ∫ J f,het (rN , t ′ )dt ′ .
0
(9.10.15)

Similar relations could be written for the immersion mode, and the concentrations of the drops
freezing in the range of drop radii (rd, rd+drd) could be defined as

dN f ,imm (rd , rN , t ) = Pfr (rd , rN , t ) f (rd )drd , rd > rb . (9.10.16)

However, the problem becomes more complicated in this case since it is difficult to calculate the dis-
tribution of the aerosol particles inside the drops and to determine which rN corresponds to which rd.
Thus, as discussed earlier, a reasonable approximation is to use the average over the aerosol spectrum
the probability of freezing for the drops Pimm (t ), defined similarly to (Eqn. 9.10.14):
rmax
1
Pimm (t ) =
N a ,imm ∫
rb [( sw ( t )]
Pfr (rN , t ) fa (ra ) dra , (9.10.17)

where Na,imm is defined in (Eqn. 9.10.11). The concentration of drops dNf,imm nucleated in the immer-
sion mode in the range of radii (rd, rd +drd) is

dN f ,imm (r , t ) = Pimm (t ) f (rd )drd . (9.10.18)

The total amount of drops freezing in immersion mode is

rmax rmax

N f ,imm = ∫
rb [( sw ( t )]
dN f ,imm (r , t ) = Pimm (t ) ∫
rb [( sw ( t )]
f (rd ) drd = Pimm (t ) N d . (9.10.19)

These equations can be used in the models to evaluate ice nucleation when the deliquescence-
freezing and immersion modes act simultaneously. The parcel model simulations similar to those
described in Section 9.14 showed a reasonable performance of this scheme and comparable contribu-
tions from the DF and immersion modes, although ice nucleation in the DF mode begins earlier still
at subsaturation.
There is an important difference in calculations of the probabilities of freezing Pfr for interstitial
aerosol and for drops in the DF and immersion modes at cloud evaporation or glaciation. When a
cloud contains drops, the water supersaturation is usually very close to zero, sw ≈ 0. Therefore, the
water activity in the solutions inside aerosol particles and inside drops is close to 1, aw ≈ 1. Thus,
the nucleation rate Jf,het defined in (Eqn. 9.6.7) should be calculated for both modes with the critical
446 Heterogeneous Nucleation of Drops and Ice Crystals

radius rcr (Eqns. 9.7.5a) and (9.7.5b) and with DFcr (Eqns. 9.7.15) or (9.7.24) at sw = 0 (Sw = 1). At the
stage of evaporation or intensive glaciation, when supersaturation in the cloud becomes negative, the
fraction of interstitial aerosol rapidly adjusts to sw < 0, the haze particles partially evaporate, their radii
decrease, the water activity of the solution decreases, and the freezing point depression increases.
This will hamper and eventually stop the freezing of aerosol in the DF mode. These effects are au-
tomatically accounted for by using (Eqns. 9.7.5a) and (9.7.5b) for rcr, and (Eqns. 9.7.15) or (9.7.24)
for DFcr via sw < 0 (Sw < 1).
Activated drops are very diluted and the water activity in the solution inside drops aw ≈ 1 even at
the stage of evaporation at sw < 0—i.e., aw π sw. Therefore, the calculation of rcr, DFcr, Jf,het, and Pfr
for cloud drops should be performed using the corresponding equations derived in Section 9.7.2 from
the the general equilibrium (Eqn. 3.6.4) for larger cloud drops (Eqns. 9.7.6e)−(9.7.6g). The reason for
this is that, in contrast to unactivated CCN, activated drops do not obey Köhler’s equation as unacti-
vated solution drops but are close to Kelvin’s equilibrium. Therefore the expressions derived for rcr,
DFcr for solution drops and using water activity aw are not applicable to activated drops. An attempt
to modify the classical equations for rcr valid for haze drops by introducing water activity aw < 0 in
cloud drops may lead to confusing results, as will be shown in Section 9.16. When a cloud evaporates
or crystallizes at sw < 0, the smallest drops evaporate first. Thus, the effects of subsaturation and the
evaporation on drop freezing can be accounted by using rcr for activated cloud drops as described in
Section 9.7.6 and by changing the lower limit of integration in (Eqn. 9.10.19) from rb[sw(t)] to the
lower limit of the droplet size spectrum.

9.11. Critical Freezing and Melting Temperatures

9.11.1. General Equations

The critical or threshold temperatures and saturation ratios of heterogeneous freezing depending on
the nucleation rates can be derived analogously to the derivation in Sections 8.7 and 8.8 for homoge-
neous nucleation. The critical freezing or melting temperatures depend on the mechanism of freezing
or melting. The derivation in the following text follows Khvorostyanov and Curry (2004a,b, 2009b).

Volume Heterogeneous Freezing

For volume heterogeneous freezing of an ice crystal, the heterogeneous nucleation rate is described
by (Eqn. 9.6.7). Solving equation (Eqn. 9.6.7) for Jf,het relative to the critical energy DFcr, we obtain

J f ,het
∆Fcr = − kT ln − ∆Fact , (9.11.1)
Chet

where the normalizing factor Chet for heterogeneous freezing on the surface of an insoluble core with
radius rN was defined in (Eqn. 9.6.8). The expression for DFcr is given by (Eqns. 9.7.21) and (9.7.21b)

(16π /3)σ is3 f (mis , x )

∆Fcr = 2 − α rN2σ is (1 − mis ), (9.11.2)
 ef  T0 Gn 
 ρi Lm ln  Sw exp(− H v , fr )  
  T 
9.11. Critical Freezing and Melting Temperatures 447

where Gn = RT/(MwLmef) and Hv,fr was defined in (Eqn. 9.7.6). Equating (Eqns. 9.11.1) and (9.11.2),
we obtain

T 
ln  0 SwGn  = H f ,het + H v , fr , (9.11.3)
T 

where Hf,het is
1/2
1  (−16π /3) f (mis , x )σ is3 
H f ,het =  2  . (9.11.4)
ρi Lefm  kT ln( J f ,het /Chet ) + ∆Fact − α rN σ is (1 − mis ) 

Equation (9.11.3) is a key relation for the threshold T and Sw, that allows us to express the critical
or threshold temperature of heterogeneous freezing Tf,het as a function of the saturation ratio, which
is done in this section, or, vice versa, to express the critical saturation ratio Sw,cr as a function of the
temperature, which is done in the next Section 9.12. Solving (Eqn. 9.11.3) relative to T, we obtain the
critical or threshold temperature of volume heterogeneous freezing Tf,het:

T f ,het = T0 SwGn exp(− H f ,het − H v , fr )]. (9.11.5)

In expanded form, it becomes

 ∆ρ∆p rfr Cε ε 2 
T f ,het ( J het , Sw , ras , ∆p) = T0 SwGn exp  − − − ef 
 ρ w ρi Lm rd ρi Lm 
ef

 1  (−16π /3)σ is3 f (mis , x ) 

1/ 2

 
× exp − ef  2  , (9.11.6)
 m ρi
L  kT ln( J f ,het /Chet ) + ∆Fact − α rN σ is (1 − mis )  

where, as in the case with homogeneous freezing in Chapter 8, the freezing curvature parameter rfr =
2ssa/ri Lmef, and rd is the radius of the freezing particle. The parameters Lmef, ri, Chet, sis, and DFact are
functions of temperature and should be evaluated at the same values of Tf,het as on the left-hand side
of (Eqn. 9.11.6). The solution to (Eqn. 9.11.6) requires an iteration procedure, but iterations converge
rapidly, and one to two iterations are sufficient, as was illustrated in Section 8.7 for Tf,hom.
Fig. 9.10 provides an example of the heterogeneous freezing temperature Tf,het(Sw) or Tf,het(aw) cal-
culated with (Eqn. 9.11.6) for two nucleation rates, Jf,het = 10−6 s−1 and 1 s−1, and two radii of freezing
droplets, rd = 5 and 0.02 μm. The four theoretical curves for Tf,het(Sw) are located above the homo-
geneous freezing temperature Tf,hom(Sw) due to the catalyzing action of the insoluble substrate, but
below the melting curve Tm since heterogeneous freezing also requires some degree of supercooling.
An increase in the nucleation rate Jf,het by 6 orders of magnitude, from 10−6 to 1 s−1, relatively weakly
influences Tf,het(Sw), by 1–3 K in this example. A decrease of the drop size from 5 μm to 0.02 μm
causes the shift of DT to colder freezing temperatures by about 10 K around Sw ∼ 1 (weak solutions)
and DT increases by 15–20 K in concentrated solutions at Sw < 0.8 and low T < 220 K.
The experimental points from different sources given here for comparison exhibit a wide scatter
of the freezing temperatures for various substances and conditions of experiments performed with
the drops of different sizes and cooling rates. A comparison of the experimental and theoretical results
shows their general similarity and qualitative agreement. This indicates that classical nucleation
448 Heterogeneous Nucleation of Drops and Ice Crystals

280
CNT, Jf,het = 10–6s–1, r = 5 µm
Tm(SW) CNT, Jf,het = 1 s–1, r = 5 µm
270
CNT, Jf,het = 10–6s–1, r = 0.02 µm
Heterogeneous freezing temperature (K)
260 CNT, Jf,het = 1 s–1, r = 0.02 µm

250 Zobrist, nonadec.

Zobrist, OAD
240 Zobrist, SiO2
Zobrist, AgI
230 Robins., NaCl–C17
Zuberi, montmoril.
220
Zuberi, kaolinite

210
Tf,hom

200
0.6

190
1.0 0.9 0.8 0.7 0.5 0.4
Water saturation ratio Sw or water activity aw

Figure 9.10. Heterogeneous freezing temperature Tf,het(Sw) or Tf,het(aw) calculated with (Eqn. 9.11.6)
based on the extended classical nucleation theory (CNT) with two nucleation rates, Jf,het = 10−6 s−1,
Jf,het = 1 s−1, and two radii of freezing droplets, rd = 5 and 0.02 μm. The melting Tm(Sw) and homogeneous
freezing Tf,hom(Sw) curves are given for comparison. The experimental data sets for the heterogeneous
freezing data on Tf,het(aw) for various substances and authors: from Zuberi et al. (2002, montmorrilonite
and kaolinite), Zobrist (2006, nonadecanol, oxalic acid dihydrate (OAD), SiO2, and AgI), and from
Cantrell and Robinson (2006, Robins., NaCl-C17).

theory allows us to describe the general features of heterogeneous freezing curves, Tf,het(Sw). Although
this comparison is shown just for illustration, and no special tuning of the parameters was done to
reproduce any specific experimental results, the general agreement indicates that with the appropriate
choice of the nucleation (cooling) rate, droplet size, activation energy, surface tension, and other param-
eters specific for a given substance, a better quantitative description can be reached.
For very slow processes, when Jf,het → 0, and ln Jf,het → −∞, and neglecting the term with rfr /rd,
(Eqn. 9.11.6) is simplified and we obtain the threshold freezing temperature:

 Cε ε 2 
T f ,het = T0 SwGn exp  − , (9.11.7)
 ρi Lm (T f ,het ) 
ef

which for very slow processes tends toward the melting temperature Tm(Sw) with correction for the
misfit strain. Formally, this is a nonlinear equation for Tf,het. However, the temperature dependen-
cies of Gn(T) and L mef(T) are relatively weak in the region of interest (Gn ≈ 0.4 at T = −10 °C, see
9.11. Critical Freezing and Melting Temperatures 449

Fig. 8.14c), and can be accounted for by iteration or neglected with a small error. It is convenient to
rewrite (Eqn. 9.11.7) using the relation, Sw = 1 +sw:

 Cε ε 2 
T f ,het = T0 (1 + sw )Gn exp  − . (9.11.8)
 ρi Lm (T f ,het ) 
ef

The parameter Ce 2/ri L mef << 1 for e < 1–2%, and at small sw << 1, we can expand (Eqn. 9.11.8) into
the Taylor series by sw and by Ce e 2/riLmef. Keeping only the first two terms in sw and using the defini-
tion Gn = RT/(MwLmef ), we have an expansion for Tf,het similar to that obtained in Section 8.7 for the
melting temperature, but with correction for the misfit strain effects:

T f ,het ≈ [T0 + Gn T0 sw + (1 /2)Gn (Gn − 1)sw2 ](1 − Cε ε 2 /ρi Lefm ) = T0 + ∆T f , (9.11.9)

∆T f = ∆T f 1 + ∆T f 2 + ∆Tε , (9.11.10)

Rv T02 R T2  R T  C ε2
∆T f 1 = sw , ∆T f 2 = v ef0  vef 0 − 1 sw2 , ∆Tε = − T0 ε ef , (9.11.11)
Lmef
2 Lm  Lm  ρ i Lm

where Rv is the specific gas constant for water vapor. Equations (9.11.9)–(9.11.11) describe the depres-
sion or shift to colder temperatures of the freezing (melting) point temperature in a solution drop
due to the solute effects, where DTf1 and DTf2 denote corrections of the first and second order by
supersaturation or solution concentration respectively, and DTe is associated with the misfit strain
effects of the insoluble substrate. It is easy to see that DTf1 is equivalent to the traditional formulation
for the freezing point depression DTf in the bulk water solution that is usually derived by equating
the chemical potentials of ice and the solution (e.g., Pruppacher and Klett, 1997; Curry and Webster,
1999). The first term in expansion of DTf by the mole fraction of a solute, xs = ns/nw, can be written
as (Curry and Webster, 1999, p. 122):

Rv T02
∆T f 1 = − xs . (9.11.12)
Lm

In a dilute solution, Sw ≈ 1 − xs, or xs ≈ −sw, so the expressions for DTf1 in both (Eqns. 9.11.11) and
(9.11.12) are equivalent.
The freezing point depression is an important property of nucleating aerosols—their temperature
threshold of nucleation. To estimate and compare the effects of salt DTf1 (“hygroscopic depression”) and
insoluble substrate DTe (“misfit depression”), note that Rv T02 / Lefm ≈ 103K and riLmef ≈ 3.3 × 109 erg cm −3
near T0, while Ce 2 ∼ 1.7 × 107 erg cm−3 at e = 1% and Ce 2 ∼ 6.8 × 107 erg cm−3 at e = 2%. Since CCN
serve in this freezing mode as IN, their equilibrium sizes and molalities can be easily calculated from
the Köhler theory. The mole fraction in each haze particle is adjusted to the environmental relative
humidity to determine the freezing point depression (see Sections 8.6 and 9.7). For instance, at Sw
= 0.9 (sw = −0.1 or the solute mole fraction xs ≈ −sw = 0.1), we obtain DTf1 = 103 K × (−0.1) = −10.3 K
(which well agrees with the point at Sw = 0.9 in Fig. 9.10), and DTf2 = −0.31 K is much smaller. The
misfit depression is DTe = −1.55 °C at e = 1% and DTe = −6.2 °C at e = 2%. These simple estimates of
DTe are in a good agreement with those in Young (1993). In addition, (Eqns. 9.11.10) and (9.11.11)
450 Heterogeneous Nucleation of Drops and Ice Crystals

allow a simple comparison of the freezing depression caused by the salts, induced supersaturation
(subsaturation), and misfit strain.
The effects of supersaturation on the ice nucleation rate from CCN can also be characterized
by introducing the “effective supercooling” DTef and the “effective temperature” of nucleation Tef
caused by supersaturation sw (positive or negative), which can be defined using the denominator in
(Eqn. 9.7.4) for rcr and introducing Tef with the relation

ln(T0 / Tef ) = ln[(T0 /T ) SwGn ]. (9.11.13)

Then, Tef and DTef can be defined as

Tef = TSw− Gn = T (1 + sw )− Gn ≈ T + ∆Tef , (9.11.14)

2
Rv T
∆Tef = − TGn sw = − sw . (9.11.15)
Lefm

Since Gn ∼ 0.4 at T = −20 to 0 °C, and GnT ∼ 0.4·263 ∼ 100 at T ∼ −10 °C, the value of DTef ≈
−100sw—i.e., DTef in °C is approximately equal to water supersaturation in %, but with the oppo-
site sign. For example, the value of DTef ≈ −5 °C for sw = 0.05 (Sw = 1.05), and Tef ≈ −15 °C for
T = −10 °C, which substantially increases the nucleation rate. This can be a quantitative formulation
of the Hobbs–Rangno effect (1990–1991) for high crystal production at relatively warm temperatures
and hypothesized high-water saturations of a few percent. Conversely, for sw = −0.05 (the equivalent
to solute concentration xs ≈ 0.05), the value of DTef ≈ 5 °C and Tef ≈ −5 °C for T = −10 °C—that is, the
effective temperature is higher by 5 °C at subsaturation caused by the dynamic factors of the presence
of solute, with a corresponding suppression of nucleation. A limitation of the linear approximation is
that if we consider solutions, they should be close to the ideal solutions, otherwise the freezing and
melting point depressions should be evaluated with an accounting for the non-linear behavior of the
freezing and melting curves as shown in Fig. 9.10.

Surface Quasi-Heterogeneous Freezing

When a solid is incompletely wettable by its own melt with the small but nonzero contact angle qis, as
described in Section 9.9, surface freezing in the absence of the foreign substances can be considered
as a quasi-heterogeneous nucleation of an ice germ at the drop surface. Then, the critical free energy
of an ice germ at the liquid–air interface can be written as (Eqn. 9.9.5) in Section 9.9:

16π σ ia3 f (mis , x )

∆Fcr = 2 , (9.11.16)
3  ef  T0 Gn 

ρ L ln
 i m 
T
S w exp − (
H )
s , fr  

where f(mis, x) and Hs,fr are defined by (Eqns. 9.7.16) and (9.9.4a), and mis is the cosine of the con-
tact angle qis between ice and its own liquid (water or aqueous solution). Equating (Eqn. 9.11.1) to
(Eqn. 9.11.16) for DFcr and solving for T, we obtain the surface freezing temperature:

 1  ∆p∆ρ 2σ sa  
Ts , fr ( ∆p ) = T0 SwGn ( T ) exp  − ef 
− ×
 ρ w Lm  ρi rd  
 1  16π σ ia3 f (mis , x )  
1/ 2

exp − ef  −  , (9.11.17)
 Lm ρi  3 kT ln( J s , fr /Cs , fr ) + ∆Fact  
9.11. Critical Freezing and Melting Temperatures 451

where Js,fr and Cs,fr are the nucleation rate and normalizing factor for surface freezing; their exact
appearance is not important for us now for the reason explained in the following text.

Surface Quasi-Heterogeneous Melting

For incomplete wettability, a particular case of surface melting considered in Section 9.9 is a quasi-
heterogeneous process of a liquid germ nucleation on the surface of a crystal. The critical free energy
for the type of surface melting considered here can be written as for the solid/air interface (Defay
et al., 1966) and using (Eqn. 9.9.11) as

16π σ sa3 f (mis , x )

∆Fcr = 2 ,
(9.11.18)
3   T0 Gn 
− ρ w Lm ln  Sw exp ( − H m )  
ef

 T 

where f(mis) and Hm are defined by (Eqns. 9.7.16) and (9.9.10), and mis is again the cosine of the small
contact angle between ice and its own liquid. Equating (Eqn. 9.11.1) to (Eqn. 9.11.18) for DFcr and
solving for T, we obtain the melting temperature:

 1  ∆p∆ρ 2σ ia  
Tm ( ∆p ) = T0 SwGn ( T ) exp  − ef 
+ 
 i Lm  ρ w
ρ rcr  
 1  16π σ is3 f (mis , x ) 
1/2

exp  ef −  , (9.11.19)
L ρ  3 kT ln( J s ,m /Cs ,m ) + ∆Fact 
 m w 
where Js,m and Cs,m are the nucleation rate and normalizing factor for surface melting. For complete
wettability qis = 0, mis = 1, f(mis = 1, x) = 0, and DFcr = 0, there is no energy barrier for nucleation.
For ice surface freezing or melting, qis has a nonzero yet very small value qis ∼ 0.5–2° (Hobbs,
1974; Dash, et al., 1995; Ketcham and Hobbs, 1969; Knight, 1971; Elbaum et al., 1993; Elbaum
and Schick, 1991; Rosenberg, 2005). Thus, f(mis) → 0, the arguments in the second exponents in
(Eqns. 9.11.17) and (9.11.19) tend to zero, and the exponents tend to 1. Then, the expressions for the
surface freezing and melting temperatures are simplified as

 1  ∆p∆ρ 2σ sa  
Ts , fr [ f (mis ) → 0 ] = T0 SwGn ( T ) exp  − ef 
− , (9.11.20)
 ρ w Lm  ρi rd  
 1  ∆ρ∆p 2σ ia  
Tm [ f (mis ) → 0 ] = T0 SwGn ( T ) exp  − ef 
+ . (9.11.21)
 ρi Lm  ρ w rcr  

These expressions do not depend on Js,fr, Js,m owing to the small contact angle between water and ice.
For substances when qis is not so small—e.g., some metals (Dash, et al., 1995; Elbaum et al., 1993;
Elbaum and Schick, 1991), (Eqns. 9.11.17) and (9.11.19) should be used and the last exponent can
make contributions lowering Ts,fr and raising Tm. Equation (9.11.21) allows for a simple calculation of
the melting point depression with increasing pressure. Differentiating (Eqn. 9.11.21) by p, we obtain

dTm ∆ρT0 Gn ( T )  1  ∆ρ∆p 2σ ia  

=− Sw exp  − + . (9.11.22)
ef 
dp ρi ρ w Lefm  i Lm  ρ w
ρ rcr  

For a particular case of bulk pure ice (rcr → ∞, Sw = 1), (Eqn. 9.11.22) converts into the Clapeyron
equation (Hobbs, 1974; Chapter 4 here), T0 = 273.15 K, and yields dTm/dp = −1/138 K atm−1, close to
the experimental values (Hobbs, 1974; Pruppacher and Klett, 1997; Dash et al., 1995).
452 Heterogeneous Nucleation of Drops and Ice Crystals

Liquidus Curves
Equations (9.11.20) and (9.11.21) for Ts,fr, Tm at Dp = 0 and large rd, rcr or bulk solutions are reduced to
ef ef
Ts , fr ( ∆p = 0) = Tm ( ∆p = 0) = T0 SwGn ( T ) = T0 SwRT / M w Lm = T0 awRT/M w Lm . (9.11.23)

This indicates the reversibility of slow surface freezing and melting. Equation (9.11.23) is the same
as (Eqns. 8.7.12a) and (8.7.12b) for homogeneous nucleation considered in Section 8.7, because for
very small contact angles f(mis) → 0, and heterogeneous nucleation becomes similar to the homoge-
neous process. These equations are nonlinear in the solution concentration, and are valid not only for
dilute solutions but also for concentrated solutions. They describe with high accuracy the liquidus
curves or freezing/melting point depressions over a wide range of solution concentration (for solu-
tions without strong non-ideality), as was illustrated in Chapter 8 and in Fig. 9.10. For the particular
case of a small solute mole fraction xs (dilute solution), substituting Sw ≈ 1 − xs, and expanding
(Eqn. 9.11.14) by xs in the power series, Ts,fr and Tm can be presented in a linear approximation as
in (Eqn. 8.7.13), which is a known linear approximation for the freezing/melting point depression
(e.g., Pruppacher and Klett, 1997; Curry and Webster, 1999). It was illustrated in the Figures in
Chapter 8 and in Fig. 9.10 that (Eqn. 9.11.23) can describe with good accuracy a nonlinear decrease
of the freezing or melting point to rather high values of solution concentrations.

9.12. Critical Saturation Ratios or Water Activities of Heterogeneous Freezing

The critical or threshold saturation ratios for homogeneous freezing were considered in Section 8.8.
Threshold humidities and saturation ratios Swhet,cr for heterogeneous ice nucleation are much more
variable due to the varying composition of aerosols that initiate freezing. The original parameter-
izations of the number density of ice crystals formed in clouds due to heterogeneous nucleation
were formulated as functions of temperature (Fletcher, 1962; Cooper, 1986) or ice supersaturation
(e.g., Huffman, 1973; Meyers et al., 1992) and usually did not assume any humidity thresholds for
heterogeneous ice nucleation—i.e., nucleation in most parameterizations was allowed at any positive
ice supersaturation. Later studies showed that there usually exists some critical saturation ratio that
determines the onset of heterogeneous ice nucleation, and that the saturation ratios for heterogeneous
nucleation are lower than those for homogeneous nucleation: in chamber and field experiments (e.g.,
Berezinsky and Stepanov, 1986; Sassen and Dodd, 1988, 1989; Young, 1993; Pruppacher and Klett,
1997; Rogers et al., 1998; Chen et al., 1998; Zuberi et al., 2002; DeMott et al., 2003; Shaw et al.,
2005; Archuleta et al., 2005; Knopf and Koop, 2006; Abbatt et al., 2006; Möhler et al., 2006; Zobrist,
2006; Zobrist, et al., 2008; Cantrell and Robinson, 2006; Vali, 2008; Krämer et al., 2009; Spichtinger
and Krämer, 2012; Hoose and Möhler, 2012); theoretical studies and numerical modeling (e.g.,
Khvorostyanov and Curry, 2000, 2004a,b, 2005a, 2009b; Kashchiev, 2000; Khvorostyanov and Sassen,
1998a,b, 2002; Sassen et al., 2002; Khvorostyanov, Curry et al., 2003; Kärcher and Lohmann, 2003;
Gierens, 2003; Diehl and Wurzler, 2004; Morrison et al., 2005a,b; Barahona and Nenes, 2009).
A recent INCA field experiment (INterhemispheric differences in Cirrus properties from An-
thropogenic emissions) was devoted to measurements of the properties of cirrus clouds and the
upper troposphere and found the difference in critical saturation ratios in the Northern and South-
ern hemispheres. It has been hypothesized that the difference in critical saturation ratios between
9.12. Critical Saturation Ratios or Water Activities of Heterogeneous Freezing 453

heterogeneous and homogeneous nucleation may cause global climatic effects as observed in the
INCA experiment: homogeneous freezing in the cleaner southern hemisphere atmosphere versus a
predominance of heterogeneous freezing in the more polluted northern hemisphere may be respon-
sible for observations of lower average relative humidity of the upper troposphere with cirrus clouds
in the northern hemisphere (Ovarlez et al., 2002; Ström et al., 2003; Haag et al., 2003; Gayet et al.,
2004; Monier et al., 2006).
However, the exact values of the difference in critical humidities between the homogeneous and
heterogeneous nucleation modes have not been established, nor has their dependence on various
parameters such as the size of freezing particles, their physico-chemical properties, cooling rates,
temperature, and other factors. Therefore, some recent parameterizations of the critical humidities
for heterogeneous ice nucleation were based on some hypothetical but unverified relations, such as an
assumption of constant difference in activities between the modes of homogeneous and heterogeneous
nucleation, some parameterizations neglected factors such as dependence on the particle size, cooling
rates, and chemical composition. Such assumptions introduce uncertainties and unknown errors in
parameterizations. Therefore, parameterizations could be improved based on the theoretical evalua-
tion of critical humidities for the two nucleation modes. In this section, the equations are derived for
the critical saturation ratios of heterogeneous nucleation analogous to those derived in Chapter 8 for
homogeneous nucleation, and the critical humidities of homogeneous and heterogeneous nucleation
are compared.

9.12.1. General Equations

Derivation of the critical or threshold saturation ratios of heterogeneous nucleation in this section
follows Khvorostyanov and Curry (2009b), is similar to the analogous derivation for homogeneous
freezing in Section 8.8, and begins with (Eqn. 9.11.3). Solving (Eqn. 9.11.3) relative to Sw, we obtain
the critical water saturation ratio:
Swhet,cr = [(T /T0 ) exp( H f ,het + H v , fr )]1/ Gn . (9.12.1)

Substituting Hf,het from (Eqn. 9.11.4) and Hv,fr from (Eqn. 9.7.6), we obtain an expanded form

 T   ∆ρ∆p rfr C ε 2 

Swhet,cr ( J het , T , rd , rfr , ∆p) =   exp  + + ε ef 
 ρ w ρi Lm rd ρi Lm 
ef
 T0 
1/ Gn
 1  −(16π /3) f (mis , x )σ is3 
1/2

× exp  ef     .
 Lm ρ i ln( / ) + ∆ − α 2
σ (1 − )  (9.12.2)
  kT J f , het C het Fact rN is mis  

Equation (9.12.2) expresses Swhet,cr as a function of atmospheric and aerosol variables T, rd, rfr, rN, e, mis,
p, a, and the nucleation rate Jf,het. Equation (9.12.2) depends also on a few fundamental parameters
(Lefm, ri, sis, DFact), and accounts for the effects of active sites a and variable external pressure Dp that
can be significant under certain circumstances as discussed in the following text. In applications for
the freezing of bulk water, we should choose rd = ∞, causing the term with rfr to vanish.
454 Heterogeneous Nucleation of Drops and Ice Crystals

The critical relative humidity over water is RHWcr = 100 Swhet,cr , and the critical ice saturation ratio
S and relative humidity over ice is RHIcr are
het
i , cr

,cr = S w ,cr (ews /eis ),

Sihet RHI cr = RHWcr (ews /eis ),
het
(9.12.3)

where ews(T) and eis(T) are saturated vapor pressures over water and ice. Note that in this theory, the
primary quantities are saturation ratios and humidities over water since they determine the process of
ice nucleation, and the saturation ratios and humidities over ice are secondary quantities that deter-
mine the crystal growth but not the nucleation itself. The surface tension sis can be chosen in different
ways (see Section 4.4). In the calculations in the following text it is chosen similar to Tabazadeh
et al. (2000), Khvorostyanov and Curry, (2004a), and Archuleta et al. (2005), based on Antonoff’s
rule as described in Section 4.4.

9.12.2. Simplifications of Equations for the Heterogeneous Critical Saturation Ratio

Equations (9.12.1) and (9.12.2) can be used directly for evaluation of the critical Sw of heterogeneous
nucleation and for comparison with homogeneous nucleation thresholds, as will be illustrated in the
following text. Besides, they allow us to derive the two most popular empirical methods used over
the last few decades for parameterizing the critical humidities in calculations of ice nucleation: the
polynomial parameterizations of the critical Sw as a function of temperature and the shifted water
activity method.
Equations (9.12.1) and (9.12.2) for the critical Sw of heterogeneous nucleation can be simplified
by examining the temperature dependence of various terms in (Eqn. 9.12.1), shown in Fig. 8.14c of
Chapter 8, where calculations were performed with rd = 0.05 μm, ssa = 76 dyn cm−2, a = 0, e = 0,
Dp = 0 (so that Hv,fr is the same for heterogeneous and homogeneous nucleation), and Jf,het = 1 s−1.
Fig. 8.14c shows that Gn has a weak T dependence; Gn ∼ 0.4 at 0 °C and slightly increases toward
colder T to Gn ∼ 0.6 at 170 K. The Hf,het increases in this range from 0.07 to 0.15. Both Hf,het << 1 and
Hv,fr << 1; therefore, (Eqns. 9.12.1) and (9.12.2) can be simplified by expansion of the exponents into
the power series

1/ Gn
 T  
Swhet,cr (T ) ≈   (1 + H f ,het + H v , fr ) 
 T0  
M w Lefm/RT
T  H f ,het H v , fr 
≈  1 + G + G  . (9.12.4a)
 T0   n n 

Using the definition of Hv,fr (Eqn. 9.7.6), we further obtain from (Eqn. 9.12.4a)
M w Lefm /RT
T 1
S het
w , cr (T ) =   (1 + H f ,het + ∆Sw ,rd + ∆Sw ,ε + ∆Sw , p ), (9.12.4b)
 T0  Gn

where the three corrections due to the curvature, misfit, and pressure are

1 rfr 1 Cε ε 2 1 ∆ρ∆p
∆Sw, rd = , ∆Sw, ε = , ∆Sw , p = . (9.12.5)
Gn rd Gn ρi Lefm Gn ρ w ρi Lefm

Expressing Gn via thermodynamical parameters as before, we obtain

ρ w AK 3.6 × 10 −5 Rv Cε ε 2 Rv ∆ρ∆p
∆Sw, rd = ~ , ∆Sw, ε = , ∆Sw , p = (9.12.6)
ρi rd Trd T ρi T ρ w ρi
9.12. Critical Saturation Ratios or Water Activities of Heterogeneous Freezing 455

The expansion (Eqns. 9.12.4a) and (9.12.4b) is valid down to low temperatures ∼ 200 K. If we
express the temperature via supercooling DT as T = T0 − DT, and DT << T0, then the first T-factor in
(Eqn. 9.12.4b) can also be expanded in the power series and we obtain

Swhet,cr (T ) ≈ 1 + ∆Sw ,T + (1 /Gn ) H f ,het + ( ∆Sw ,rd + ∆Sw ,ε + ∆Sw , p ), (9.12.7)

1 ∆T L ∆T ef
∆Sw ,T = − =− . m
(9.12.7a)
Gn T Rv T 2

Each of the terms in (Eqn. 9.12.7) is a function of temperature, and this expression resembles previ-
ous empirical parameterizations of Swhom hom
, cr , Si , cr for homogeneous ice nucleation as polynomials by

temperature (e.g., Sassen and Dodd, 1988, 1989; Heymsfield and Miloshevich, 1995, see Chapter 8)
or polynomials by saturated vapor pressure esw, (Koop et al., 1998, 1999; Bertram et al., 2000), or
similar parameterizations for heterogeneous nucleation (e.g., Zuberi et al., 2002; Archuleta et al.,
2005). Thus, (Eqns. 9.12.1), (9.12.2), (9.12.4), and (9.12.7) serve as a physical justification for the
previous parameterizations and as a basis for their improvement. However, these equations show that
besides the T-dependence, there are several other dependencies not captured by the empirical param-
eterizations and may at least partially explain the differences in Swhet,cr determined by various laboratory
and field experiments. In particular, the curvature correction DSw,rd in (Eqn. 9.12.6) is similar to the
slightly increased (by rw/ri ∼ 1.1) Kelvin curvature effect ∼ AK/rd on the saturated vapor pressure
over the drop surface, but that was missing in previous ice nucleation parameterizations. The theory
developed here indicates that this effect becomes noticeable for submicron particles, and neglecting it
would lead to the same errors as neglecting the Kelvin effect on the vapor pressure for small particles.
The similarity of the curvature effect on the critical humidity of freezing and of the Kelvin effect is
not coincidental: It is an important consequence of the derivation of both these effects from the gen-
eral entropy equation—for the Kelvin effect as described in Section 3.8 and for the freezing critical
humidity in this section based on the critical radii and energies from Section 9.7.
Simple estimates of the effects of these 4 factors on variations DSw of Swhet,cr can be done using
(Eqn. 9.12.7), which shows that the temperature factor causes a decrease in Swhet,cr, while each of the
other 3 factors causes an increase in Swhet,cr.

1. At DT = T0 − T << T0, the temperature factor can be simplified as in (Eqn. 9.12.7a), and an esti-
mate at T = −15 °C yields DSw,T ∼ −0.14.
2. Assuming ssa ∼76 dyn cm−1 (PK97, Fig. 5–2), we have rfr = 2ssa/riLmef ∼ 0.6 × 10−7 cm at
T ∼ 250 K and (rw/ri)AK ∼ 1.44 × 10−7. If the size of aerosol particles is rd ∼ 0.02 μm, then from
(Eqn. 9.12.6) DSw,rd ∼ +0.075, or DRHWcr ∼ 7.5%, a perceptible effect. The curvature effect decreases
with increasing rd: DRHWcr ∼ 1.5% for rd ∼ 0.1 μm and is negligible for rd ≥ 0.5–1 μm.
3. The estimate from (Eqn. 9.12.6) of the misfit term is DSw,e ∼ +0.04 (DRHWcr ∼ 4%) for e = 1%,
and DSw,e ∼ +0.16 (DRHWcr ∼ 16%) for e = 2%.
4. For Dp ∼ 1 atm (106 dyn cm−2), an estimate for the pressure term DSw,p gives ∼ 10−4, which is
negligible. However, for higher pressures of Dp ∼ 500–1000 atm, as can exist in the atmospheres
of the other planets, or are created in the laboratory devices (e.g., Kanno and Angell, 1977;
Mishima and Stanley, 1998), we get DSw,p ∼ +0.05 to +0.10 (DRHWcr ∼ 5 to 10%) —i.e., a sig-
nificant increase.

A difference of a few percent in RHW often may substantially alter the picture of cloud formation.
For example, if RHW ≈ 100%, then a liquid cloud normally forms, but if RHW is just 3–5% lower
and the temperature is cold enough (−15 to −20 °C), then a crystalline cloud may form in clear sky
via the freezing of haze particles as diamond dust, and the liquid phase may not form or form later,
456 Heterogeneous Nucleation of Drops and Ice Crystals

which was found in lidar measurements and numerical modeling (e.g., Sassen et al., 2006; Sassen
and Khvorostyanov, 2007, 2008).

9.12.3. Derivation from Classical Theory of the Water Activity Shift Method

Using the expansion of (Eqn. 9.12.4a) and (Eqn. 9.12.1) into the power series, and keeping only the
terms of the first order, the critical saturation ratio can also be presented in the form

Swhet,cr (Thet ) ≈ Sw ,cr (Tm ) + δ Swhet,cr (T ), (9.12.8a)

( H f ,het + H v , fr )
δ Swhet,cr (T ) = δ aw ,het = Sw ,cr (Tm ) . (9.12.8b)
Gn
ef
Here, Sw ,cr (Tm ) = (T /T0) M w Lm/RT is the same melting curve aw(Tm) or Sw(Tm) discussed in Sections 8.7,
8.8, and 9.11, and
δ Swhet,cr = Swhet,cr (T f ,hom ) − Sw ,cr (Tm ) (9.12.8c)

is the difference or shift in the critical saturation ratios between the melting and heterogeneous freez-
ing curves at the same temperature. It can be written in terms of activities as

δ aw ,het = aw (T f ,het ) − aw (Tm ) = aw ,het − aw (Tm ). (9.12.8d)

The quantity daw,het is the difference or shift in the activities between the melting and heterogeneous
freezing curves at the same temperature and is termed in the literature as the water activity shift for
heterogeneous freezing by analogy with the water activity shift for homogeneous freezing considered
in Section 8.8.
The daw,het is usually introduced as an empirical quantity based on the measurements of the hetero-
geneous freezing temperatures and comparison with the melting curve Tm(aw), and characterizes the
freezing point depression at heterogeneous freezing. Equations (9.12.8a)−(9.12.8d) allow expression
of δ Swhet,cr (T ) and daw,het in terms of the classical nucleation theory. Using the definition for Gn =
RT/(Mw L mef ), (Eqn. 9.11.4) for Hf,het, and (Eqn. 9.7.6) for Hv,fr , the shifts in the saturation ratio or in
the water activity can be presented in an expanded form:

 M Lef 
δ Swhet,cr (T , J f ,het ,σ is , mis ,α , ε , rN , ∆p) = δ aw ,het = Swhet,cr (Tm )  w m 
 RT 
 1  (−16π /3) f (mis , x )σ is3 
1/2

×  2 
 ρi Lm  kT ln( J f ,het /Chet ) + ∆Fact − α rN σ is (1 − mis )
ef


∆ρ∆p 2σ sa C ε2  (9.12.8e)
+ + + ε ef .
ρ w ρi Lm ρi Lm rdr ρi Lm
ef ef

This equation shows that the water activity shift for heterogeneous freezing is not a universal quan-
tity, but besides temperature, depends also on many other parameters: nucleation rate, surface ten-
sion, the contact angle of a substrate, misfit strain, the radius of a freezing drop, the shape factor and
the size of the insoluble substrate, and several thermodynamic parameters like melting heat, water
and ice densities, pressure, etc.
9.12. Critical Saturation Ratios or Water Activities of Heterogeneous Freezing 457

0.40 Zuberi–02, kaolinite Jf,het = 10–6s–1, r = 5 µm

Zobrist, nonadecanol Jf,het = 1 s–1, r = 5 µm
0.35
Zobrist, SiO2 Jf,het = 10–6s–1, r = 0.02 µm

Zobrist, AgI Jf,het = 1 s–1, r = 0.02 µm

0.30
δaw,het = aw,het(Tf,het) – aw,m(Tm)

Cant.–Rob., NaCl–C17
0.25

0.20

0.15

0.10

0.05 CNT, Jf,het = 10–6s–1, r = 25 µm

CNT, Jf,het = 1 s–1, r = 25 µm
0.00
180 200 220 240 260 280
Temperature (K)

Figure 9.11. The shifts of water activity daw,het = aw,het(Tf,het) − aw(Tm) calculated with equations of
extended CNT described in Section 9.12.3 for two nucleation rates, Jf,het = 10−6 s−1 and Jf,het = 1 s−1,
and for three drop radii, 0.02 μm, 5 μm, and 25 μm. The five experimental data sets are from the
heterogeneous freezing data on Tf,het(aw,het) for various substances by various authors: from Zuberi
et al. (2002, kaolinite), Zobrist et al. (2006, 2008), nonadecanol, SiO2, and AgI), and from Cantrell
and Robinson (2006, NaCl-C17). The shifts daw,het were calculated using the experimental points
from these data sets for freezing, Tf,het(aw,het), and melting, Tm(aw,m) as daw,het = Tf,het(aw,het) − Tm(aw,m)
at Tf,het = Tm—i.e., as the difference in activities for each individual experimental point Tf,het(aw,het)
on the freezing curve and the corresponding temperature at the melting curve Tm(aw,m).

Fig. 9.11 shows the shifts of saturation ratio dSw,het or water activity daw,het = aw,het(Tf) − aw(Tm)
calculated with (Eqn. 9.12.8e) for two nucleation rates, Jf,het = 10−6 s−1 and Jf,het = 1 s−1, and for three
drop radii, 0.02 μm, 5 μm, and 25 μm. These daw,het calculated with classical nucleation theory are
compared with five experimental data sets that were retrieved from the heterogeneous freezing data
on Tf,het(aw,het) for various substances. The experimental shifts daw,het were calculated from these data
sets using the experimental freezing points, Tf,het(aw,het), and melting, Tm(aw,m), as daw,het = Tf,het(aw,het) −
Tm(aw,m) at Tf,het = Tm—i.e., as the difference in activities for each individual experimental point
Tf,het(aw,het) and the corresponding Tm(aw,m) at the same temperature.
Fig. 9.11 shows that dSw,het = daw,het calculated with classical nucleation theory increases slightly
with increasing temperature. For the drop radii of 5−25 μm, daw,het ∼ 0.1–0.15, which is much lower
than for homogeneous freezing daw,hom ∼ 0.3–0.35 (see Sections 8.8), and agrees with most of the
experimental data from Cantrell and Robinson (2006) and Zobrist et al. (2007, 2008) for four different
IN, except for those from Zuberi et al. (2002) with kaolinite, which are located higher, near 0.25. An
increase in Jf,het from 10−6 to 1 s−1 almost does not effect daw,het for large drops 5–25 μm, but causes a
458 Heterogeneous Nucleation of Drops and Ice Crystals

noticeable increase in daw,het up to 0.17–0.27 for small drops of 0.02 μm. As in the case with homo-
geneous freezing, the freezing of small submicron particles occurs at higher solution concentrations
and at greater freezing point depressions. Thus, the laboratory results obtained for large drops should
be applied with caution for submicron haze particles freezing in cirrus or similar clouds.
The experimental data on d aw,het for various substances and experiments exhibits a rather wide
scatter, and (Eqn. 9.12.8a)–(9.12.8e) can explain at least a part of this scatter. The limitations of
the shifted activity method are caused by the multi-parametric dependencies of daw,het. However, the
general agreement of d aw,het calculated with classical nucleation theory suggests that the appropriate
choice of parameters would allow more precise quantitative description of the measured water activ-
ity shifts for heterogeneous freezing.

9.12.4. Calculations of Critical Relative Humidities for Heterogeneous Nucleation

Equations (9.12.1) and (9.12.2) explain previously developed empirical parameterizations of the
critical humidities. This is illustrated in this section with the results of calculations of critical values of
RHW and RHI for heterogeneous nucleation performed with (Eqns. 9.12.2) and (9.12.3), using the
relations RHW = 100 Swhet,cr , RHI = 100 Sihet
,cr and the following baseline set of parameters: ssa = 76 dyn

cm−2, mis = 0.5 (close to typical values for surface soil, sand, and soot), a = 0, e = 0, Dp = 0, and two
prescribed values of heterogeneous nucleation rate, Jf,het = 10−6 s−1 and 1 s−1. Additional calculations
were performed where the values of e, a, mis, and rd were varied, and sensitivity of RHW and RHI to
these parameters was studied as described in the following text.
The parameter rd in the baseline runs was chosen based on measurements in field and chamber
experiments. In studies of heterogeneous freezing, measurements at aircraft altitudes found the modal
radius of ice crystal residues of rd ≈ 0.05 μm in young cirrus clouds over Europe (Ström et al., 1997),
of 0.1 μm in cirrus over Kansas in the SUCCESS campaign (Chen et al., 1998), and of 0.15–0.5 μm
over the Florida area in the CRYSTAL-FACE campaign (Cziczo et al., 2004). Some chamber experi-
ments on heterogeneous ice nucleation used nearly monodisperse core particles of comparable radii:
0.025, 0.05, and 0.1 μm (Archuleta et al., 2005). Measurements of aircraft engine soot as potential
ice nuclei for contrail and cirrus formation found that the main soot fraction consisted of relatively
hydrophilic particles with radii of 0.015–0.025 μm (Popovicheva et al., 2004). For homogeneous
freezing, the Cirrus Parcel Model Comparison Project (CPMCP) (Lin et al., 2002) recommended the
upper troposphere polydisperse aerosol of sulfuric acid with the similar modal radius rd = 0.02 μm.
The laboratory experiments used aqueous solution drops of larger radii ∼ 0.2–5 μm (e.g., Pruppacher
and Klett, 1997, Koop et al., 1998, 1999, 2000; Bertram et al., 2000; DeMott, 2002). Therefore, the
value rd = 0.05 μm was chosen for the baseline calculations to match the most typical value in this
range; calculations and comparisons were performed also with the cases with 0.5 and 5 μm.
Critical values of RHW and RHI for heterogeneous ice nucleation calculated with the baseline set
of parameters are shown in Fig. 9.12. RHW decreases from ∼ 100–102.5% at T ∼ −18 to −20 °C to ∼
65–70% at −75 °C. RHI increases from ∼ 120–125% to 137–145% over the same temperature range,
especially rapidly at T < −50 °C. Note the relatively weak dependence of RHI on the temperature at
T > −50 °C, which agrees with experimental data (e.g., Archuleta et al., 2005).
9.12. Critical Saturation Ratios or Water Activities of Heterogeneous Freezing 459

120 RHW(Jhet = 0) = RHW(Tmelt) 145

het, Jhet = 10–6 s–1
110 parameter. (9.12.9a)
Critical RHW (%) expansion (9.12.4b)
140 het, Jhet = 1 s–1
100 Parameter. (9.12.9b)
Jhet = 10-6 s–1

Critical RHI
90 135
Jhet = 1 s–1
80 130
70
125
60
50 120
–80 –70 –60 –50 –40 –30 –20 –10 0 –80 –70 –60 –50 –40 –30 –20 –10 0
Temperature (C) Temperature (C)
(a) (b)

1E+11
Heterogeneous nucleation

1E+10
1E+9
1E+8
1E+7
1E+6
1E+5 RHW=101 %
rate (s–1)

1E+4
1E+3 RHW(Jhet = 1 s–1)
1E+2
1E+1 RHW(Jhet = 10–6 s–1)
1
0.1
1E–2
1E–3
1E–4
1E–5
1E–6
1E–7
–80 –70 –60 –50 –40 –30 –20 –10 0
Temperature (C)
(c)

Figure 9.12. Critical RHW (a) and RHI (b) for heterogeneous ice nucleation calculated with the full
(Eqn. 9.12.2) and indicated in the legend nucleated rates Jf,het = 10−6 s−1 and 1 s−1, and the parameters:
rd = 0.05 μm, mis = 0.5, a = 0, e = 0; compared with the power series expansion (Eqn. 9.12.4a,b)
and with the parameterization (Eqns. 9.12.9a) and (9.12.9b); the lower curve in Fig. 9.12a (open
triangles) shows RHW(Jf,het = 0), which coincides with the melting curve Tm(RHW); (c) Verification
of the solutions: heterogeneous nucleation rates Jf,het(T, RHW) calculated with (Eqn. 9.6.7) using
as input these RHW(T) from this figure, (a), corresponding to Jhet = 10−6 s−1 and 1 s−1, and with
RHW = const = 101%. From Khvorostyanov and Curry (2009b), J. Geophys. Res., 114, D04207,
reproduced with permission of John Wiley & Sons, Inc.

Fig. 9.12a shows that an increase in the nucleation rate by six orders of magnitude from 10−6 s−1 to
1 s is accompanied by a surprisingly small increase in critical RHW, 2–3%. However, the transition
−1

from 10−6 s−1 to the limit Jf,het → 0 causes a substantial decrease in RHW, which merges with the melt-
ing curve RHW(Tm) (lower curve with open triangles in Fig. 9.12a), and is lower than the freezing
RHW by 15–20%. The approximation (Eqn. 9.12.4b) shown in Fig. 9.12a,b (solid triangles) exhibits
good accuracy, justifying the power series expansion.
460 Heterogeneous Nucleation of Drops and Ice Crystals

We can parameterize these critical humidities as a polynomial of temperature Tc in °C, and account
also for the curvature, misfit, and pressure corrections defined in (Eqns. 9.12.4a) and (9.12.4b)–(9.12.6):

Swhet,cr = asw + bsw Tc + csw Tc2 + d sw Tc4

+ ( ∆Sw ,rd + ∆Sw ,ε + ∆Sw , p ), (9.12.9a)

, cr = S w , cr (ews /eis ).
Sihet (9.12.9b)
het

The coefficients in (Eqn. 9.12.9a) are asw = 1.21, bsw = 1.23 × 10−2, csw = 9.6 × 10−5, and dsw = 7.8 × 10−10.
Equation (9.12.9a) accounts for the newer parameterization of L mef, allowing extension to lower T,
and by accounting for the effects of finite drop size, rfr/rd, misfit strain, and pressure effects. The
parameterized critical humidities RHW = 100 Swhet,cr and RHI = 100 Sihet ,cr are also given in Fig. 9.12

(open circles) and illustrate sufficient accuracy of this parameterization for the chosen typical set of
parameters.
It is shown later in this section that critical humidities depend on various aerosol properties
and (Eqns. 9.12.9a) and (9.12.9b) may require corresponding corrections. However, variations of
RHWcr in this temperature range, ∼ 30–35%, are much greater than variations with aerosol properties,
which are typically a few percent. Therefore, these equations could be used as a first guess for simple
parameterizations of the critical humidity of heterogeneous nucleation in the models that use some
prescribed threshold value of RHIcr. The value of this simple T-parameterization for heterogeneous
nucleation is similar to those suggested in Sassen and Dodd (1989), Koop et al. (1999, 2000), Bertram
et al. (2000) for homogeneous nucleation and to that in Zuberi et al. (2002) and Archuleta et al.
(2005) for heterogeneous nucleation. A more precise evaluation of Swhet,cr that accounts for individual
aerosol properties and nucleation rates can be based directly on (Eqns. 9.12.1), (9.12.2), or (9.12.7).
To illustrate the strong dependence of nucleation rates on RHW, Fig. 9.12c shows values of
Jf,het(T, Sw) calculated with (Eqn. 9.6.7) using the critical RHW values from Fig. 9.12a as input. If
the humidities RHW are close to critical and vary with the temperature as shown in Fig. 9.12a for
the corresponding Jf,het(T, Sw), then Jf,het(T, Sw) is constant with temperature. But if we assume
RHW = 101%, or Sw ≈ 1 at all T, as would be in the classical nucleation theory that accounts for only
T-dependence, then Jf,het(T) is by many orders of magnitude greater at T < −20 °C, and is by many
orders smaller at T > 20 °C. The temperature dependence of the crystal concentrations calculated
with such Sw-independent Jf,het(T) would be substantially different than that calculated with a correct
accounting for humidity.
In particular, Fig. 9.12c shows that correctly accounting for humidity RHW < 100% does not lead
to an explosive increase in nucleation rates at low T. Thus, heterogeneous freezing can be an effec-
tive mode of ice nucleation in cirrus, which has been confirmed by numerical model simulations
(e.g., Monier et al., 2006; Khvorostyanov et al., 2006; Comstock et al., 2008; Barahona and Nenes,
2009), and may explain the sufficiently high insoluble fractions in ice crystals residuals observed in
cirrus in the field campaigns of SUCCESS (Chen et al., 1998) and CRYSTAL-FACE-2002 (Cziczo
et al., 2004). If RHW is close to 100%, which is possible at not very low T, this rapid increase in
Jf,het(T, 101%) at T below −20 to −30 °C is in agreement with chamber experiments on heterogeneous
freezing that found threshold temperatures around −25 to −30 °C (e.g., Zuberi et al., 2002; Archuleta
et al., 2005). However, Jf,het(T, RHW = 101%) rapidly decreases in the temperature range −20 °C
to −15 °C (Fig. 9.12c), which explains the slower glaciation of natural liquid clouds at T > −15 °C.
9.12. Critical Saturation Ratios or Water Activities of Heterogeneous Freezing 461

120 Jf,het = 10–6 s–1, ε = 0 160

Jf,het = 10–6 s–1, ε = 2 %
110 Jf,het = 1 s–1, ε = 0
Critical RHW (%)

Jf,het = 1 s–1, ε = 2 %

Critical RHI (%)

150
100

90 140

80
130
70

60 120
–80 –70 –60 –50 –40 –30 –20 –10 –80 –70 –60 –50 –40 –30 –20 –10
Temperature (C) Temperature (C)
(a) (b)

Figure 9.13. Dependence of the critical RHW and RHI for heterogeneous nucleation on the misfit
strain e = 0 and 2% at 2 nucleation rates, Jf,het = 10−6 s−1 and Jf,het = 1 s−1; rd = 0.05 μm, and the other
parameters are the same as in Fig. 9.12. From Khvorostyanov and Curry (2009b), J. Geophys. Res.,
114, D04207, reproduced with permission of John Wiley & Sons, Inc.

The dependence of the critical RHW and RHI for heterogeneous nucleation on the misfit strain
(e = 0 vs. 2%) is shown in Fig. 9.13, indicating that critical RHW and RHI increase by 7–8% and
8–13%, respectively, as e increases from 0 to 2%. This is a significant increase that may inhibit ice
nucleation if the crystalline lattice of the insoluble substrate substantially differs from the ice lattice.
Fig. 9.14 shows the effect of the active sites on the critical RHW and RHI for heterogeneous nucle-
ation. When a increases from 0 to 10−3, both humidities decrease by ∼9–11%. Thus, the presence
even of small active sites may substantially decrease the threshold RHW and favor heterogeneous
nucleation. This effect is in agreement with parcel model simulations in (Khvorostyanov and Curry,
2005a) that showed that a ∼ 10−4 may increase the threshold temperatures for heterogeneous ice
nucleation above −10 °C (see Section 9.14.4).
Dependence of RHW and RHI for heterogeneous nucleation on the aerosol radius is illustrated
in Fig. 9.15. When a particle radius grows 10 times from 0.05 μm to 0.5 μm, RHW decreases by
3–4% in this temperature range. When rd further grows from 0.5 μm to 5 μm, a decrease in RHW
is much less, ∼0.8–1%, since the effect of the curvature correction decreases as 1/rd according to
(Eqn. 9.12.5). The total decrease is 4–5% in these radii range: 0.05 to 5 μm.
Fig. 9.16 illustrates the effect of the contact parameter mis calculated with rd = 0.05 μm and
Jhet = 1 s−1. When mis decreases from 0.5 (the value used in most calculations here) to 0.2, RHW
increases by 6–8%, or the freezing temperature decreases by about 10 °C; corresponding increases
in RHI are 10–15%. When mis decreases to −0.5, RHW further increases by 12–15% or the freezing
temperatures decrease by almost 20 °C and RHI increases by ∼20–30%. Thus, the effect of the
wettability of the insoluble substrate is a significant factor.
The behavior of RHW and RHI at mis = 0.2 in Fig. 9.16 is close to parameterizations suggested in
Zuberi et al. (2002) and Archuleta et al. (2005) based on chamber experiments, the difference does
not exceed 3–8% in the temperature range −30 to −70 °C. Note, however, that this comparison can be
462 Heterogeneous Nucleation of Drops and Ice Crystals

Jf,het = 10–6 s–1, α = 0

120 Jf,het = 1 s–1, α = 0 160

110 Jf,het = 10–6 s–1, α = 10–3

Critical RHW (%) 150
Jf,het = 1 s–1, α = 10–3

Critical RHI (%)

100
140
90
130
80

70 120

60 110
–80 –70 –60 –50 –40 –30 –20 –10 –80 –70 –60 –50 –40 –30 –20 –10
Temperature (C) Temperature (C)
(a) (b)

Figure 9.14. Effect of the active sites (a = 10−3 vs. a = 0) on the critical RHW and RHI for
heterogeneous nucleation at two nucleation rates, Jf,het = 10−6 s−1, and Jhet = 1 s−1, and rd = 0.05 μm.
The other parameters are the same as in Figs. 9.12 and 9.13. From Khvorostyanov and Curry
(2009b), J. Geophys. Res., 114, D04207, reproduced with permission of John Wiley & Sons, Inc.

10–6 s–1, rd = 0.05 µm

10–6 s–1, rd = 0.5 µm
110 150
10–6 s–1, rd = 5 µm
100 1 s–1, rd = 0.05 µm
Critical RHW (%)

Critical RHI (%)

1 s–1, rd = 0.5 µm 140

90 1 s–1, rd = 5 µm
130
80
120
70

60 110
–80 –70 –60 –50 –40 –30 –20 –10 –80 –70 –60 –50 –40 –30 –20 –10
Temperature (C) Temperature (C)
(a) (b)

Figure 9.15. Dependence of RHW and RHI for heterogeneous nucleation on the aerosol radius rd
(0.05 μm, 0.5 μm and 5 μm) and two nucleation rates, Jf,het = 10−6 s−1 and 1 s−1. The other parameters
are the same as in Fig. 9.12. From Khvorostyanov and Curry (2009b), J. Geophys. Res., 114, D04207,
reproduced with permission of John Wiley & Sons, Inc.

considered only as qualitative since many parameters in the chamber experiments are often uncertain
(e.g., the contact parameter of the insoluble core, coverage, and properties of the soluble fraction,
etc.), and if these parameters were specified with different values, the agreement could be best at
different contact parameters.
9.12. Critical Saturation Ratios or Water Activities of Heterogeneous Freezing 463

130 190
mis = 0.5 Zuberi (2002)
Critical RHW (%) 120 mis = –0.5 Archul. (2005) 180
110 mis = 0.2 RHW(Tmelt)

Critical RHI (%)

170
100 160
90 150
80 140
70 130
60 120
50 110
–80 –70 –60 –50 –40 –30 –20 –10 0 –80 –70 –60 –50 –40 –30 –20
Temperature (C) Temperature (C)
(a) (b)

Figure 9.16. Effect of variations of the contact parameter mis on the critical RHW (a) and RHI (b).
Calculations are performed with mis = 0.5, 0.2, and −0.5. A reasonably good agreement with
experimental data from Zuberi et al. (2002) and Archuleta et al. (2005) is for calculations with
mis = 0.2. From Khvorostyanov and Curry (2009b), J. Geophys. Res., 114, D04207, reproduced
with permission of John Wiley & Sons, Inc.

9.12.5. Comparison of Critical Humidities for Heterogeneous

and Homogeneous Nucleation

A principal issue for the mechanisms of cirrus formation is the difference between the critical
humidities in homogeneous and heterogeneous modes of ice nucleation. Fig. 9.17 shows a com-
parison of RHW and RHI: homogeneous with JhomV = 1 s−1, and heterogeneous with Jhet = 1 s−1, and
their differences, DRHW = RHWhom − RHWhet, and DRHI = RHIhom − RHIhet. Comparison with the
benchmark data of Sassen and Dodd (1989, SD89) and Bertram et al. (2000, B00) indicates that
both critical humidities of homogeneous nucleation at rd = 5 μm are close to the parameterizations
(SD89) and (B00). Both critical humidities of homogeneous nucleation are seen to be higher than
the corresponding heterogeneous humidities with e = 0 at all temperatures. At warmer T of −15 to
−30 °C, the critical values of RHW of heterogeneous nucleation are ∼22–30% lower than those for
homogeneous nucleation, the RHI for heterogeneous nucleation is lower by 25–40%. This difference
decreases to 15–25% toward colder T = −75 °C for RHW, and increases to 30–55% for RHI.
Over the range of the temperatures relevant for cirrus formation, the critical RHI of heteroge-
neous nucleation is often close to 120–130%, which is 20–30% lower than the critical ice relative
humidity for homogeneous nucleation. These results provide an explanation for the lower RHI in the
upper troposphere with cirrus clouds in the Northern Hemisphere (∼130%) relative to the Southern
Hemisphere (140–155%) found in the INCA field campaign, that were ascribed to the greater
anthropogenic emissions and prevailing heterogeneous mode of cirrus formation in the Northern
Hemisphere versus the cleaner Southern Hemisphere with the prevailing homogeneous mode
(Ovarlez et al., 2001; Ström et al., 2003; Gayet et al., 2004; Monier et al., 2006).
464 Heterogeneous Nucleation of Drops and Ice Crystals

105 210
100 200
Critical RHW (%) 95 190

Critical RHI (%)

90 180
85 170
80 hom, rd0 = 0.05 µm
hom, rd0 = 5 µm 160
75
70 hom, SD89 150
65 hom, B00 140
60 het, r d0 = 0.05 µm 130
het, rd0 = 5 µm 120
55 het, rd0 = 0.05 µm, ε = 2%
50 110
–80 –70 –60 –50 –40 –30 –20 –10 –80 –70 –60 –50 –40 –30 –20 –10
Temperature (C) Temperature (C)
(a) (b)

45 Jh = 10–6, rd = 5 µm 60

40 Jh = 1, rd = 5 µm
RHWhom – RHWhet

Jh = 10–6, rd = 0.05 µm

RHIhom – RHIhet
50
35 Jh = 1, rd = 0.05 µm
30 40

25
30
20

15 20
–80 –70 –60 –50 –40 –30 –20 –10 –80 –70 –60 –50 –40 –30 –20 –10
Temperature (C) Temperature (C)
(c) (d)

Figure 9.17. Comparison of RHW and RHI for ice nucleation modes. (a) and (b): homogeneous
with Jf,homV = 1 s−1, and heterogeneous with Jf,het = 1 s−1 for radii rd = 0.05 and 5 μm. These
calculations are compared with parameterizations from Sassen and Dodd (1989, SD89) and
Bertram et al. (2000, B00). The misfit strain is varied in the heterogeneous mode: e = 0 and 2%.
(c) The difference RHWhom − RHWhet, and (d) the difference RHIhom − RHIhet for 2 radii (rd = 0.05 and
5 μm) and 2 nucleation rates (Jf,het or Jf,homV = 10−6 s−1 and 1 s−1). From Khvorostyanov and Curry
(2009b), J. Geophys. Res., 114, D04207, reproduced with permission of John Wiley & Sons, Inc.

Fig. 9.17 shows that although the heterogeneous critical humidities with misfit strain e = 2% are
higher than with e = 0, they are still lower than humidities for homogeneous nucleation over the entire
temperature range. Thus, heterogeneous ice nucleation may be favored over homogeneous nucleation
if ice nuclei consisting of mixed aerosol particles containing soluble and insoluble fractions are pres-
ent in the atmosphere and do not have a very large misfit strain (epitaxial to ice lattice).
An important implication of Fig. 9.17 is that the difference in both RHW and RHI, and therefore
the shift in water activities between the homogeneous and heterogeneous nucleation processes, is
not constant as hypothesized in some parameterizations based on the “shifted activity method” (e.g.,
Kärcher and Lohmann, 2003). Fig. 9.17 shows that these differences vary in the range 15–40% for
the critical relative humidity over water and 25–55% for the critical relative humidity over ice, and
9.13. Parcel Model for a Mixed-Phase Cloud 465

depend substantially on the temperature, nucleation (cooling) rates, and physico-chemical properties
of freezing aerosol (misfit strain, contact parameter, and others). Thus, parameterizations based on a
“shifted activity method” should be corrected accordingly.
The equations derived here are presented both in complete form and in various simplified forms,
including their expansions into power series and a simpler parameterization of the critical humid-
ity of heterogeneous nucleation in the form of the temperature polynomial with corrections for the
nucleation rate, curvature (finite size) of freezing drops, misfit strain, and external pressure. This
parameterization can be applied to mixed aerosol with parameters typical for the submicron mode.
In the simplified form, it is similar to the analogous parameterizations suggested in Sassen and Dodd
(1989), Koop et al. (1999, 2000), Bertram et al. (2000) for homogeneous nucleation, and to Zuberi
et al. (2002), Archuleta et al. (2005) for heterogeneous nucleation, but accounts also for the afore-
mentioned four corrections that substantially change the critical humidities. Such polynomials with
corrections could be used in GCMs with simple microphysics that cannot afford more sophisticated
parameterizations.
However, the equations derived here for the critical water and ice saturation ratios are sufficiently
simple even in complete form and can be directly used in many modern cloud and climate models.
If a 3D temperature field and aerosol loading with its microphysics are specified in a model, these
equations allow easy and fast calculation of the 3D fields of critical humidities for heterogeneous and
homogeneous ice nucleation. Application of both of these ice nucleation schemes in the 1D (single
column type) models with spectral bin and bulk double-moment microphysics (Khvorostyanov et al.,
2001, 2006; Morrison et al., 2005a,b; Sassen and Khvorostyanov, 2008; Curry and Khvorostyanov,
2012), and in 2D and 3D mesoscale models with spectral bin microphysics of liquid and ice phases
and detailed evaluation of supersaturation (Khvorostyanov and Sassen, 2002; Sassen et al., 2002;
Khvorostyanov, Curry, et al., 2003) showed that the calculations require only very moderate resources
of computer time and memory for simulations of mixed cloud formation and an evolution during
several hours.
A comparison of the previous polynomial parameterizations for homogeneous and heterogeneous
nucleation with the equations of extended nucleation theory described here showed that these param-
eterizations describe adequately the critical humidities on the average. However, RHWcr and RHIcr
may substantially depend on the nucleation (cooling) rates, aerosol size, and other parameters that
are now becoming available and usable in the advanced GCMs (e.g., Lohmann and Diehl, 2006; Yun
and Penner, 2012; Morrison and Gettelman, 2008; Gettelman et al., 2008; Ghan et al., 2011), and
in the chemical transport models, both global and regional (e.g., CHIMERE model, Menut et al.,
2013). The use of the critical humidities based directly on nucleation theory may improve the accuracy
of the models, and may help to refine the existing parameterizations taking into account the cooling
rates, particle size, and other properties.

9.13. Parcel Model for a Mixed-Phase Cloud

The integral water supersaturation equation for a liquid-phase cloud was derived in Section 7.2,
when droplets only are present. An analogous integral ice supersaturation equation for the crystalline
clouds was derived in Section 8.5, and was used in Section 8.9.2 to study the kinetics of homogeneous
466 Heterogeneous Nucleation of Drops and Ice Crystals

nucleation. Heterogeneous ice freezing occurs at warmer temperatures than homogeneous freezing
and usually in liquid or mixed but not fully glaciated clouds—that is, at small water supersaturation
or small subsaturation, when both the drops and crystals may form. To study the kinetics of such
mixed-phase clouds, we need a supersaturation equation for a mixed-phase cloud similar to that derived
in Section 5.3, but taking into account the sources of the new drops and crystals.
In this section, a parcel model of a mixed cloud with spectral water and ice bin microphysics
is formulated to simulate the evolution of cloud microphysical processes in adiabatic ascent.
The microphysical formulation used here is similar to the Eulerian numerical 1D, 2D, and 3D spec-
tral bin models used previously for simulation of mixed-phase Arctic clouds, orographic clouds,
and other cloud types and their artificial seeding (Khvorostyanov, 1982, 1987, 1995; Kondratyev and
Khvorostyanov, 1989; Kondratyev, Khvorostyanov, and Ovtchinnikov, 1990a,b; Khvorostyanov and
Khairoutdinov, 1990; Khvorostyanov et al., 2001, 2003; Curry and Khvorostyanov, 2012), with some
differences in equations owing to the Lagrangian approach in the parcel model, and newer schemes of
drop and crystal nucleation described earlier. In the parcel model, vertical velocity is specified. The
main thermodynamic equations are the prognostic equations for supersaturation and temperature.
This system of equations includes terms that describe the phase transitions and is closed using the
kinetic equations of condensation for the drop and ice crystal size distribution functions that account
for nucleation and diffusional growth. The supersaturation and kinetic equations for particle size
distributions are described in the following text.

9.13.1. Supersaturation Equation with Nucleation of Drops and Crystals

We begin with the general supersaturation equation derived in Section 5.3:

1 dsw ΓI Γ12 I dep

= c1w w − 1 con − , (9.13.1)
(1 + s )w
dt ρv ρv

where c1w was defined by (Eqn. 5.3.26b), and Γ1 and Γ12 are the psychrometric corrections defined
t
in (Eqn. 5.3.15). The sink terms Icon and Idep include the integral supersaturation yw = ∫ sw (t ′) dt ′.
0
Therefore, it is convenient to rewrite (Eqn. 9.13.1) for yw as

yw′ (t ) ΓI Γ12 I dep

= c1w w − 1 con − , (9.13.2)
[1 + yw′ (t )] ρv ρv

where the prime means derivative by time. The vapor fluxes Icon and Idep to the droplets and crystals
(the sinks in the supersaturation equation) are the integrals of the mass growth rates that can be
expressed using the equations of Chapter 5 for the growth rates drd /dt and drc /dt of the droplet and
crystal radii over the corresponding size spectra of the drops fd (rd, t) and crystals fc(rc, t), where rd and
rc are corresponding radii. The second term with Icon on the right-hand side of (Eqn. 9.13.1) describ-
ing the vapor flux on the activated drops was given by (Eqns. 7.2.12)–(7.2.14) with an assumption
that the dry aerosol size spectrum is described by the algebraic size and activity spectrum equivalent
to a lognormal distribution. Using the relation rws /rv = 1/(1 + sw) = (1 + yw′)−1, the term with Icon in
(Eqn. 9.13.1) can be written as

Γ1 yw′ (t ) y ′ (t )[1 + yw′ (t )]−1

I con (t ) = [4π Dv N a J 0 (t )] = w , (9.13.3)
ρv [1 + yw′ (t )] τ f ,ac (t )
9.13. Parcel Model for a Mixed-Phase Cloud 467

where τ f ,ac (t ) = [4π Dv N a ract (t )]−1 is the effective supersaturation relaxation time during the stage of
drop activation defined by (Eqn. 7.2.13); the activation radius ract(t) and an integral J0(t) with the
dimension of length are defined by (Eqn. 7.2.14) with m = 2. Substitution of J0(t) from (Eqn. 7.2.14)
into (Eqn. 9.13.3) yields

Γ1 yw′ (t )  ks 0
I con (t ) = 4π Dv N a ks 0
ρv [1 + yw′ (t )]  s0
[ yw′ (t0 )]ks 0 − 1 yw ″ (t0 ) 
t

× ∫ rd ,ef (t , t0 ) dt0  , (9.13.4)

0
{1 + η0 [ yw′ (t0 )]ks 0 }2 

where rd,ef is defined by (Eqn. 7.2.11b). The parameters of drop activation, the mean geometric supersat-
uration s0, the supersaturation dispersion σ s = σ d(1+ β ), the index k s 0 = 4 /( 2π ln σ s ) and the parameter
η0 = s0− ks 0 are expressed via CCN microphysical properties in (Eqns. 6.6.35b), (6.6.35c), and (6.6.37b).
The term describing the vapor deposition rate on the crystals can be written similar to (Eqn. 8.5.5),
as an integral of the crystal mass growth rate dmc /dt over the size spectrum rc:
∞
drc (t , t0 ) 2
I dep (t ) = 4πρi ∫ rc (t , t0 ) f (rc , t0 ) drc , (9.13.5)
0
dt

where rc(t, t0) is the radius at the time t of the crystals nucleated at t0. Substituting the crystal growth
rate (drc /dt) from (Eqn. 8.5.6) yields

4π Dv ρis ∞ rc2 (t , t0 )
I dep (t ) = si (t )
Γ2 ∫ 0 rc (t , t0 ) + ξ dep
fc (rc , t ) drc . (9.13.6)

Substituting rc(t, t0) from (Eqn. 8.5.9) and using the equality fc(rc)drc = Rf,het(t0)dt0 similar to
(Eqn. 8.5.12), we obtain an expression for Idep via the freezing rate Rf,het similar to (Eqn. 8.5.16):
t
4π Dv ρis
I dep = yi ′
Γ2 ∫0 rc,ef (t , t0 ) R f ,het (t0 ) dt0 , (9.13.7)

with Rf,het defined in (Eqn. 9.10.5),

R fr =
dN fr
dt
= ∫
rmin
rmax
( t
drN fa (rN ) J f ,het (t ) exp − ∫ J f ,het (t ′) dt ′ ,
0 ) (9.13.7a)

and the effective radius rc,ef(t, t0) defined in (Eqn. 8.5.14). Note that here, as in the case with
homogeneous nucleation, or drop nucleation, the integrand in expression (Eqn. 9.13.7) for Idep
represents the product of the two terms: the term Rf,het(t0) describes the “generation” of particles
at a time t0, and the term rc(t, t0) describes their “propagation in time between t0 and t,” and plays
the role of what is termed in physics “the propagator” or Green’s function. This structure is similar
to those arising in electrotechnique, the theory of radiation, or the theory or elementary particles
(e.g., Landau and Lifshitz, v. 2, 3, 4). This analogy may suggest various solutions for this term
used in the mentioned theories, in particular, the methods of Green function approximations or the
perturbation theory.
468 Heterogeneous Nucleation of Drops and Ice Crystals

Substitution of Rf,het from (Eqn. 9.10.5) or (Eqn. 9.13.7a) into (Eqn. 9.13.7) yields the deposition
flux expressed via heterogeneous freezing rate Jf,het, similar to (Eqn. 8.5.17) for homogeneous freezing,

4π Dv ρis 
t
rmax
I dep = yi ′  ∫ rc ,ef (t , t0 ) ∫r fa (ra )
Γ2  0 min

0 (
× J f ,het (t0 ) exp − ∫ J f ,het (t ′)dt ′ dra dt0  ,
 ) (9.13.8)

Using the relation ris /rv = 1/(1 + si) = (1 + yw′)−1, the term (Γ12/rv)Idep in (Eqn. 9.13.2) can be now
rewritten as

Γ 
t
Γ12 yi′(t ) rmax
I dep = 4π Dv 12  ∫ rc ,ef (t , t0 ) ∫ fa (ra )
ρv [1 + yi′(t )] Γ 2  0 rmin

0(
× J f ,het (t0 ) exp − ∫ J f ,het (t ′)dt ′ dra dt0  .
 ) (9.13.8a)

Substituting (Eqns. 9.13.4) and (9.13.8a) into the equation (Eqn. 9.13.2) and multiplying by (1 + yw′)
yields

dyw ′
= c1w [1 + yw′ (t )]w
dt
 k
t
[ yw′ (t0 )]ks 0 −1 yw′′(t0 ) 
− yw′ (t ) 4π Dv N a kss00
 s0 ∫ rd ,ef (t , t0 )
0
{1 + η0 [ yw′ (t0 )] } ks 0 2
dt0  ,

Γ 
t
[1 + yw′ (t )] rmax
− yi′(t ) 4π Dv 12  ∫ dt0 rc ,ef (t , t0 ) ∫ dra fa (ra )
[1 + yi′(t )] Γ 2  0 rmin

( t
× J f ,het (t0 ) exp − ∫ J f ,het (t ′)dt ′ .
0 )} (9.13.9)

This is an equation for the integral water supersaturation for a mixed-phase cloud that takes into
account the possible drop activation and crystal nucleation by freezing of CCN or drops. It includes
both integral supersaturations over water yw and ice yi, and can be written for yw only using the rela-
tion (Eqn. 5.3.27) between sw and si, which for the integral supersaturations becomes

1 + yw′ ρ − ρis
yi′ = yw′ + ws . (9.13.10)
1 + yi′ ρ ws

Substitution into (Eqn. 9.13.9) yields an equation for yw only that can be written in a more compact
form using again Idep as in (Eqn. 9.13.7) via Rf,het:

dyw′
= c1w [1 + yw′ (t )]w
dt
 k
t
[ yw′ (t0 )]ks 0 −1 yw′′(t0 ) 
− yw′ (t ) 4π Dv N a kss00
 s 0
∫r
0
d ,ef (t , t0 )
{1 + η0 [ yw′ (t0 )]ks 0 }2
dt0 

t
Γ12
Γ 2 ∫0
− yw′ 4π Dv rc ,ef (t , t0 ) R f ,het (t0 ) dt0

 ρ − ρis  Γ
t

−  ws  4π Dv 12 ∫ rc ,ef (t , t0 ) R f ,het (t0 ) dt0 . (9.13.11)

 ρ ws  Γ2 0
9.13. Parcel Model for a Mixed-Phase Cloud 469

This equation describes the vapor balance in a mixed-phase cloud and its four terms on the
right-hand side have simple physical meanings. The first term with w describes supersaturation
generation due to cooling in an updraft; the second term with rd,ef and the third term with rc,ef
describe supersaturation depletion due to droplets and crystals absorption respectively, and the
last term with (rws − ris) describes the vapor flux from the drops to the crystals due to the dif-
ference of saturated humidities over water and ice (Wegener–Bergeron–Findeisen mechanism,
WBF). The second term generalizes Twomey’s (1959) equation for the drop activation with cor-
rect asymptotic and limited drop concentration at large sw (as described in Chapters 6, 7), and the
last two terms generalize this equation with an accounting for the supersaturation depletion by the
crystals and WBF mechanism. Equation (9.13.11) can be used for analytical studies of the super-
saturation yw′ and sw and nucleated drop and crystal concentrations in a mixed-phase cloud, as was
done in Chapter 7 for a liquid cloud. Equation (9.3.11) can be also used for numerical simulations
in cloud models and advanced climate models. This equation can be simplified in many cases, as
will be shown in the next sections.
Equation (9.13.11) is written in a closed form so that the source terms are included in the integrals
Icon, Idep with an accounting for the evolution of the size spectra of nucleated drops and crystals. An
analog of (Eqn. 9.13.11) is (Eqn. 5.3.28a) rewritten for the integral supersaturation yw′ as

dyw′ (t )  1 Γ 1  Γ12 1 ρ ws − ρis

= (1 + yw′ )c1w w − yw′ (t )  + 12 − , (9.13.12)
dt  fd Γ 2 τ fc  Γ 2 τ fc
τ ρ ws

where tfd and tfc are the droplet and crystal supersaturation relaxation times

∞ rd2
τ −fd1 = 4π Dv ∫ fd (rd , t ) drd ≈ (4π DN d rd )−1 , (9.13.13)
0 rd + ξcon
∞ rc2
τ −fc1 = 4π Dv ∫ fc (rc , t ) drc ≈ (4π DN c rc )−1 . (9.13.14)
0 rc + ξ dep

The times tfd and tfc are determined by the droplet and crystal size spectra, and the second
equalities in (Eqns. 9.13.13), (9.13.14) are valid in the diffusion regime, rd << xcon, rc << xdep. In
(Eqns. 9.13.12)–(9.13.14), the source and sinks of the particles are described by the size spectra
fd(rd, t) and fc(rc, t), and kinetic equations are needed to calculate fd(rd, t) and fc(rc, t) at every time
moment.
The heat balance is calculated using the equation for the temperature T in a wet adiabatic process
considered in Chapters 3 and 5 in the form

dT Le Ls
= −γ a w + I con + I dep (9.13.15)
dt c pa ρ a c pa ρ a

This equation is solved along with the integral ice supersaturation equation (Eqns. 9.13.11) or
(9.13.12) that is required to describe droplet and crystal nucleation and growth.
470 Heterogeneous Nucleation of Drops and Ice Crystals

9.13.2. Kinetic Equations for Droplet and Crystal Size Spectra with Particle Nucleation

Evolution of the droplet and crystal spectra is described using two kinetic equations for the fd(rd, t)
and fc(rc, t) similar to that in Chapter 8,

∂ fd ∂  drd 
+  fd  = ψ fd (rd , t ), (9.13.16a)
∂t ∂rd  dt 
∂ fc ∂  drc 
+  fc  = ψ fc (rc , t ). (9.13.16b)
∂t ∂rc  dt 

As in Chapter 8, these equations are written for the simplest case, with an accounting for regular
condensation and deposition only, and without taking into account aggregation and the effects of
turbulence. As in Chapter 8, following the methodology recommended for the Cirrus Parcel Model
Comparison Project (CPMCP, Lin et al., 2002), we deliberately exclude from consideration coagula-
tion among the droplets and aggregation between the droplets and crystals, sedimentation, entrain-
ment, turbulent exchange, etc. to isolate the effects directly related to nucleation processes. (Inclusion
of these processes in multidimensional Eulerian models is described in Chapter 5, Sections 5.7 and
5.8). The source terms yfc and yfd on the right-hand side describe particle nucleation. The droplet
nucleation term yfd is calculated using the CCN activity spectrum j(sw) which is the algebraic or
modified power law, as described in Chapters 6 and 7:

dsw
ψ fd = ϕ (sw ) δ (rd − ∆rd ), (9.13.17)
dt
where Drd is the first step by droplet radius, d is Dirac’s delta function, and its simplest finite differ-
ence approximation is 1/Drd. If sw reaches 0 and increases, then Nd increases by DNd in one time step
Dt, yfd = DNd /Drd /Dt and the new drops are placed in the first size bin Drd of fd(rd).
The model includes both heterogeneous and homogeneous ice nucleation processes. The crystal
source term for the heterogeneous deliquescent-freezing and immersion modes is calculated as yfc =
DNf,het /Drc /Dt with the number DNf,het of the crystals nucleated on frozen CCN-IN or drops in a time
step Dt calculated as described in this chapter; Drc, is the first size step by the crystal radii (0.1–1 μm).
Heterogeneous freezing rate Jf,het is calculated based on Section 9.6 with Drcr and DFcr from Section 9.7,
and then DNf,het is calculated following Section 9.10. The homogeneous nucleation rate Rf,hom and DNf,hom
are calculated in a similar way, based on Chapter 8.
Both spectra include 30 points by radius: 10 steps by Drd,c = 0.1–1 μm and the next 20 steps in-
creasing logarithmically to the maximum rmax. The values of Drd,c and rmax were varied in numerical
experiments depending on the maximum size that the particles can reach, rmax = 350 μm at warmer
temperatures −12 to −20 °C and 100 μm at low T ∼ −50 °C. The experiments showed that this division
allows coverage of both small and large size ranges without losing accuracy.

9.14. Parcel Model Simulations of Ice Nucleation Kinetics

in Deliquescence-Freezing Mode

9.14.1. Introduction
The main disadvantage of many previous parameterizations of ice nucleation is that they are empiri-
cal, with parameters tuned to produce ice crystal concentrations Nc within some limited range of
temperatures and supersaturation based on field or laboratory measurements. Such an approach has
9.14. Parcel Model Simulations of Ice Nucleation Kinetics 471

led to contradictions between parameterizations of the measured concentrations of ice nuclei, NIN,
and of the crystals, Nc, so that the “ice enhancement factor” RM = Nc /NIN, can reach values as high as
104–105 at T = −5 °C (e.g., Hobbs, 1969, 1974), which has produced several hypotheses on “ice mul-
tiplication” and stimulated their studies (e.g., Hallett and Mossop, 1974; Mossop and Hallett, 1974), or
requirements for high water supersaturations (Hobbs and Rangno, 1990; Rangno and Hobbs, 1991).
Supersaturation dependence of ice nuclei concentration may produce a negative feedback and stop
nucleation even in the presence of external sources of supersaturation generation; the temperature
dependence of ice nucleation does not have this feature. If a source of cooling persists, the latent heat
release of growing crystals may hamper nucleation but cannot stop it, commonly producing unreal-
istically high values of Ni, and artificial methods may be required to prevent unlimited ice nucleation
when using a temperature-dependent parameterization (e.g., Spice et al., 1999). The heterogeneous
freezing nucleation rate of classical nucleation theory describes the temperature dependence of the
nucleation rate but does not contain supersaturation dependence (see Section 9.7). The theory
of heterogeneous condensation-freezing by Fukuta and Schaller (1982) discussed in Section 9.7
showed that a combined temperature-supersaturation dependence occurs if heterogeneous freezing
takes place as a two-step process: a) condensation on insoluble aerosol particles at positive water
supersaturation; and b) subsequent freezing that depends on temperature. A similar model for the
immersion-freezing mode was considered by Young (1993).
A theory of ice nucleation by heterogeneous freezing of deliquescent mixed CCN by Khvorostyanov
and Curry (2000, 2004a,b; Section 9.7, hereafter KC00-04) allowed to describe simultaneously both
the temperature and supersaturation dependencies of ice crystal nucleation by mixed CCN freezing.
Heterogeneous ice crystal nucleation was examined in Section 9.7 for static conditions—i.e., for
fixed temperature and supersaturation. However, nucleation rates and concentration of nucleated
crystals cannot be explored and explained without a dynamical framework. Khvorostyanov and
Curry (2005a) incorporated this KC00-04 theory of heterogeneous ice nucleation into a parcel model
with explicit water and ice bin microphysics and simulated the process of ice nucleation under a wide
range of transient thermodynamic conditions. The results of simulations in the work by Khvorostyanov
and Curry (2005a, hereafter KC05a) illustrate the kinetics of heterogeneous freezing and are described
in this section, similar to what has been done in Section 8.7 of Chapter 8 for homogeneous nucleation.
Simulations are conducted over the temperature range −4 to −60 °C, with vertical velocities vary-
ing from 1 to 100 cm s−1, for varying initial relative humidities and aerosol characteristics. It is shown
that the kinetics of heterogeneous ice nucleation exhibits a negative feedback regulated via water
supersaturation. This feedback is similar to that found for homogeneous nucleation in works cited
in Chapter 8, Section 8.7 (e.g., Lin et al., 2002) and Section 9.7, and is much stronger than the cor-
responding feedback for drop nucleation. This may partially explain discrepancies between observed
ice nuclei concentrations and ice crystal concentrations. At the end of this section, the kinetics and
the relative importance of heterogeneous versus homogeneous nucleation is examined for a variety of
cloud conditions, and possible applications of this theory for cloud modeling are discussed.

9.14.2. Simulation Characteristics

To simulate the ice crystal nucleation process, the parcel model was run for 1–3 hours, varying the
initial temperature (T0c), relative humidity (RHW0), vertical velocity (w), and aerosol characteristics.
The only two additional parameters of this model of heterogeneous freezing are the relevant aerosol
472 Heterogeneous Nucleation of Drops and Ice Crystals

characteristics (see Section 9.7): the misfit strain e and the wettability or contact parameter, mis. Most
runs were performed with e = 0, and sensitivity to e = 1–2% was tested in some experiments. The
parameter mis given in Table 5.2 in Pruppacher and Klett (1997) for surface soil (mis = 0.36–0.42)
and quartz (mis = 0.63–0.72) might be representative for mixed CCN. Kärcher et al. (1996) mea-
sured the values mis = 0.44–0.57 for soot that may constitute insoluble carbonaceous fraction of IN.
Similar ranges of the contact parameter were reported in Young (1993), Marcolli et al. (2007), and
many other studies, although smaller and even negative values of mis were sometimes detected (e.g.,
Hung et al., 2003; Archuletta et al., 2005). The average values of mis = 0.50 or 0.52 were taken in the
simulations described in detail in the following text and the sensitivity to the lower and higher values
of mis in the range 0.12– 0.75 was also tested along with some negative mis < 0 as in Section 9.12 for
the critical humidities or saturation ratios. Numerical experiments showed that the values of mis are
mostly limited to this rather narrow range, otherwise freezing may occur too rapidly (for mis ≥ 0.67)
or slowly (for small mis ≤ 0.40). This is caused by the exponential dependence of nucleation rate JS,fr
on DFcr ∼ f(mis, x), that was emphasized by Fletcher (1962) and discussed in Section 9.7. Models
with lognormal and other distributions of the contact angles were also tested and showed that such
ditribution can more smoothly describe ice nucleation in a wider temperature range (e.g., Marcolli
et al., 2007; Lüönd et al., 2010; Hoose and Möhler, 2012). The results described in the following text
and obtained with just one contact angle can be easily generalized for any statistical distributions of
the contact angles.
The parcel model used here includes the option of isolating specific ice crystal nucleation modes,
by turning off the other modes. In this section, we consider heterogeneous and homogeneous freezing
of deliquescent CCN-IN and the other modes (deposition and contact) are considered in Chapter 10.
The initial pressure p0 is specified in most runs to be 800 hPa. The cloud condensation nuclei (CCN)
concentration typical for continental clouds Na = 500 cm−3 is chosen for all runs except for simula-
tion of ice nucleation in maritime convective clouds, where Na = 100–150 cm−3, and for compari-
son of heterogeneous and homogeneous modes in cirrus clouds at low Tc and high altitudes, where
Na = 200 cm−3, as was recommended and used in CPMCP (Lin et al., 2002). Several experiments
were performed with Na = 50–100 cm−3 at Tc = −20 °C to −30 °C to test the possibility of mixed-phase
cloud existence at these temperatures. The insoluble aerosol size spectrum over rN is lognormal with
modal radius rm = 0.02 μm and dispersion s = 2.5; at sw > 0, it is limited by the boundary radius rb as
described in Section 9.8. More than 300 simulations were performed with variable combinations of
T0c, RHW0, mis, e, w, aerosol microstructure, and the mode of freezing (heterogeneous deliquescent-
freezing and/or homogeneous freezing).
The time steps were 0.01–0.2 s in the main program, but the time step can be divided further in
the condensation subroutines as described in Section 5.8 to meet the stability condition Dt << min(td, tc).
The accuracy of the calculations was controlled by comparing the total number of crystals nucleated
with those obtained by integration over the size spectrum of the grown crystals at the end of a parcel
run. If the error exceeded 5% (especially at low temperatures), the time and radius steps were varied
and several additional runs were performed until the error became less than 5%. The runs with verti-
cal velocities w 5 1–5 cm s21 described in this section were conducted for a period of 3 hours, which
was sufficient to trace all stages of supersaturation growth, nucleation, and subsequent supersaturation
relaxation. In the runs with higher w 5 30–100 cm s21, all the processes were faster, and it was
9.14. Parcel Model Simulations of Ice Nucleation Kinetics 473

sufficient to conduct simulations for a period of 0.5–1 h. The simulation results are described in the
following text.

9.14.3. Kinetics of Ice Nucleation in the Mixed and Crystalline Clouds with Weak Updrafts

In this section, we describe the temporal evolution of the ice nucleation process. Figs. 9.18–9.21 show
the results of the run with the initial T0c = −14 °C, RHW0 = 89% (sw = −11%), vertical velocity w =
2 cm s−1 (which corresponds to a cooling rate of −0.7 °C h−1), and mis = 0.52. The initial supersatura-
tion over ice is si = 11%. Figs. 9.18 and 9.19 illustrate that the temporal evolution can be separated
into 3 stages. During the first stage (up to 115 minutes), the temperature decreases due to cooling
and RHW increases (Fig. 9.18a,b), which causes a decrease in the critical radius rcr and energy DFcr
defined in Section 9.7 (Fig. 9.18c,d). During the second stage, starting at t = 115 minutes, the nucle-
ation rates reach their threshold values and grow very rapidly (Fig. 9.18e,f). At t = 117 minutes, RHW
reaches and exceeds 100%, and drop activation occurs. Until t = 145 minutes, sw slightly decreases
because of the drop formation and growth, and rcr and DFcr decrease, while Jf,het and dNc /dt increase.
Note that this occurs not at the threshold humidity RHWth, but when RHW exceeds the threshold by
∼13% (Fig. 9.18b), in agreement with estimations of the critical saturation ratio Sw,cr given in Sec-
tion 9.12. Ice nucleation rates are noticeable only for about 25 minutes, when the drops and crystals
coexist (Fig. 9.19). During the third stage (starting nominally at t = 145 minutes), the rate of vapor
absorption by the crystals increases sufficiently for complete evaporation of the drops by Wegener–
Bergeron–Findeisen mechanism (Fig. 9.19d,f). Drops evaporate, RHW abruptly decreases, and rcr
and DFcr increase rapidly, causing Jf,het and dNc /dt to decline below the threshold values, and hence
ice nucleation stops.
Evolution of the integral characteristics over these 3 stages of nucleation is shown in
Fig. 9.19. During the 1st stage, the initial subsaturation sw decreases due to cooling and reaches
−0.3% at t = 115 min (Fig. 9.19a) when the crystal formation starts (Figs. 9.19c,e,g), and crystal
concentration Nc reaches ∼1 L−1 in 5 minutes by t = 120 minutes. However, since the crystal super-
saturation relaxation time is greater than 2 hours (Fig. 9.19b), the crystals cannot absorb all
available vapor, and supersaturation generation is still faster than its absorption, so sw continues
to increase and becomes positive at t ≈ 120 minutes. During the 2nd stage, water supersaturation
becomes positive, droplets begin to form at t = 118 min (Fig. 9.19d,e,h). Their relaxation time
is a few seconds (Fig. 9.19b), thus the supersaturation generation and absorption are balanced,
sw does not grow, and drops and crystals coexist for 30 min in a mixed cloud. Meanwhile, crys-
tal nucleation is continuing, Nc reaches ∼8 L−1, and the mean radius is 60 μm by t = 145 min.
The crystal capability of supersaturation absorption gradually increases during the second stage
and finally exceeds the rate of supersaturation generation. The vapor flux is directed now from
the droplets to the crystals, and due to the intensive Wegener–Bergeron–Findeisen process, the
drops evaporate fast and disappear at t = 150 minutes, when sw becomes negative. The crystal
concentration continues to increase during the second stage (although at a slower rate) and
reaches 17.6 L−1at the end of the second stage. The third stage starts when both sw and si begin to
decrease. This stage is characterized by constant Nc, but the crystal radius and IWC still increase
since si is positive.
474 Heterogeneous Nucleation of Drops and Ice Crystals

–14.0 104
–14.2
100
–14.4 RHW
Temperature (C)

–14.6

RHW (%)
96
–14.8
–15.0 92

–15.2 RHWth
88
–15.4
–15.6 84
0 20 40 60 80 100 120 140 160 180 0 20 40 60 80 100 120 140 160 180
Time (min) Time (min)
(a) (b)

1E–5 1E–9

Critical energy (erg)

Critical radius (cm)

1E–10

1E–6

1E–11

1E–7 1E–12
0 20 40 60 80 100 120 140 160 180 0 20 40 60 80 100 120 140 160 180
Time (min) Time (min)
(c) (d)

1E–6 1E–4
Heterogeneous nucleation
Rate of germ formation

1E–7
rate dNi/dt (cm–3 s–1)
per particle Jls (s–1)

1E–5

1E–8
1E–6
1E–9

1E–7
1E–10

1E–8
0 20 40 60 80 100 120 140 160 180 0 20 40 60 80 100 120 140 160 180
Time (min) Time (min)
(e) (f)

Figure 9.18. Temporal evolution of the characteristics of heterogeneous nucleation in the parcel at
T0 = −14 °C, RHW0 = 89%, w = 2 cm s−1, mis = 0.52. (a) Temperature, T, °C; (b) RHW and threshold
humidity RHWth,%; (c) germ critical radius, rcr, cm; (d) germ critical free energy, DFcr, erg; (e) the
rate of germ formation per particle Jf,het, s−1; (f) polydisperse nucleation rate Rfr = dNfr /dt, cm−3 s−1.
From Khvorostyanov and Curry (2005a), J. Atmos. Sci., 62, © American Meteorological Society.
Used with permission.
9.14. Parcel Model Simulations of Ice Nucleation Kinetics 475

20

Supersaturation over water

16 τfc τfd
100

Total supersaturation
si

relaxation time (min)

12 τf,tot
and ice (%)
8 τfd
10
4
0
sw 1
–4 τf,tot
–8
–12 0
0 20 40 60 80 100 120 140 160 180 100 120 140 160 180
Time (min) Time (min)
(a) (b)
1E+2 200
Crystal concentration (L–1)

180

Droplet concentration
1E+1 160
140
1 120

(cm–3)
100
0.1 80
60
1E–2 40
20
1E–3 0
110 120 130 140 150 160 170 180 110 120 130 140 150 160
Time (min) Time (min)
(c) (d)
240 20
210
IWC (mg m–3)

LWC (mg m–3)

180 15
150
120 10
90
60 5
30
0 0
100 120 140 160 180 110 120 130 140 150 160
Time (min) Time (min)
(e) (f)
140 6.0
Crystal mean radius (µm)

130
120 5.0
Drop radius (µm)

110
100
90 4.0
80
70 3.0
60
50 2.0
40
30 1.0
20
10 0.0
110 120 130 140 150 160 170 180 110 120 130 140 150 160 170 180
Time (min) Time (min)
(g) (h)

Figure 9.19. Time dependence of droplets and crystals microphysical properties with T0 = −14 °C,
RHW0 = 89%, w = 2 cm s−1, m = 0.52. (a) Supersaturations over water and ice (%); (b) supersaturation
relaxation times for drops tfd, crystals tfc, and total relaxation time tf,tot (min); (c) crystal concentration
(L−1); (d) droplet concentration (cm−3); (e) IWC (mg m−3); (f) LWC (mg m−3); (g) crystal mean radius
(μm); (h) droplet mean radius (μm). From Khvorostyanov and Curry (2005a), J. Atmos. Sci., 62,
© American Meteorological Society. Used with permission.
476 Heterogeneous Nucleation of Drops and Ice Crystals

Thus, the modeled cloud is pure crystalline in the first stage (115–120 minutes), has a mixed-phase
structure during the second stage for 30 minutes, and is again pure crystalline in the third stage. In
this case, the cloud phase is governed by the relative humidity, which determines also the IN con-
centration (assuming that NIN = Nc). As water saturation is reached, there is a competition between
nucleation of the drops and crystals on the same population of the haze particles that serve at the same
time as CCN and IN.
This simulation produced a value of Ndr = 160 cm−3 out of a total NCCN = 500 cm−3 CCN. We can
define “condensation efficiency” of CCN in producing droplets as Edr = Ndr/NCCN, and it is here
Edr ≈ 0.32. The crystals are nucleating simultaneously, and only a very small fraction of the available
CCN, 18 L−1 (∼2 × 10−2 cm−3) was nucleated and would have been identified as IN in chamber experi-
ments. A similar “freezing efficiency” of deliquescent CCN in producing crystals can be defined as
Ecr = Nc/NCCN ∼ NIN/NCCN = 2 × 10−2/500 = 40 × 10−6. This estimate is close both conceptually and
quantitatively to that obtained by Rogers et al. (2001) in recent measurements of IN in the Arctic
(NIN/NCCN ∼ 20 × 10−6), in SUCCESS (Chen et al., 1998; Rogers et al., 1998) and to the estimates of
NIN/NCCN in the parcel model by DeMott et al. (1998).
Since the freezing efficiency Ecr of CCN is much less than the condensation efficiency Edr, these
results show that the present theory enables explanation at least of the observed differences between
concentrations of the drops and crystals nucleated from the same population of deliquescent mixed
CCN similar to the concepts derived from the field experiments (Hobbs and Rangno, 1990; Rangno
and Hobbs, 1991; Pruppacher and Klett, 1997; DeMott et al., 1998). In numerical experiments here,
ice nucleation on the CCN is prevented by a very strong humidity dependence of rcr, DFcr, Jf,het, and
dNc /dt. The dependence on humidity is an exponential function (see Section 9.8, Eqn. 9.8.11) that
is much stronger than the power law for drop nucleation (Chapters 6 and 7), which is why crystal
nucleation on CCN creates such a strong negative feedback via relative humidity and leads to such
dramatic differences between the concentrations of drops and crystals.
The dissimilarity between the drops and crystals nucleation on CCN and the ratio of the final
concentrations Nc and Nd in a mixed cloud can be illustrated from the analysis of the supersatura-
tion (Eqns. 9.13.1) and (9.13.12) and Fig. 9.19. The second and third terms on the right-hand side
in (Eqn. 9.13.1) are proportional to the vapor fluxes to the drops, Icon, and crystals, Idep, and describe
absorption by the drops and crystals. Note that according to (Eqns. 5.3.19), (9.13.13), and (9.13.14),
Icon ∼ sw /td ∼ sw Ndrd, and Idep ∼ si /tc ∼ siNcrc. Ice nucleation begins and proceeds at slow nucleation
rates, and Idep << Icon. Activation of drops occurs at sw ∼ 0.1%, and during most of the time of liquid
phase existence, supersaturation generation by w is balanced mostly by its absorption by the drops,
by the flux Icon. After drop activation, si ∼ 20%, the newly nucleated crystals grow much faster than
the drops and reach larger sizes, ri ∼ 20–30·rd by the end of cloud glaciation. At this time, supersatura-
tion absorption by the crystals Idep become comparable to Icon and then exceeds it, which causes the
decrease of sw and ceases ice nucleation (after 150 min in Fig. 9.19). Therefore, we can estimate the
ratio of final concentrations Nc and Nd from the condition Icon ≈ Idep, or swNdrd ∼ siNcrc, which yields
in the preceding example Nc /Nd ∼ (sw /si)(rd /rc) ∼ (0.5 × 10−2)(3 × 10−2) = 1.5 × 10−4, an estimate close
to the simulated Nc /Nd ≈ 20 L−1/160 cm−3 = 1.3 × 10−4.
Thus, the following factors determine the large difference between concentrations of crystals and
drops formed on the same population of CCN: 1) crystal nucleation rate dNc /dt is much slower than
9.14. Parcel Model Simulations of Ice Nucleation Kinetics 477

that for the drops; 2) ice supersaturation is ∼102–103 times greater than water supersaturation in a
mixed cloud and this dissimilarity determines the difference in growth rate, sizes, and supersaturation
absorption by drops and crystals; 3) therefore, the absorption of supersaturation by crystals begins
to exceed its generation by updrafts at much smaller concentrations, but at larger radii than that for
drops; and 4) this causes a supersaturation decrease and a cease of ice nucleation at Nc << Nd.
Thus, in this parcel model without the precipitation of crystals, the mixed-phase cloud exists for
half an hour and then full glaciation occurs. If the newly formed crystals were allowed to precipitate,
the cloud mixed-phase stage could continue much longer. This was confirmed in simulations with
a 3D model with spectral bin microphysics of a fog and cloud formed over the polar polynya in the
Beaufort Sea observed during the SHEBA-FIRE field experiment in 1998 in the Arctic (Khvorostyanov,
Curry, et al., 2003). The same heterogeneous ice nucleation scheme was applied at similar tempera-
tures, and crystals nucleated with concentrations of 5–15 L−1. However, crystal concentrations were
depleted due to precipitation and wind transport, and mixed-phase cloud existed at least for several
hours with very light precipitation a few tens of km away from the polynya. Simulation with a 1D model
and this ice scheme of the cloud observed during the MPACE field campaign in the Arctic also showed
the existence of the mixed-phase cloud without full glaciation for several hours. The microstructure
and phase state of the simulated cloud were close to those observed (Curry and Khvorostyanov, 2012).
Thus, this heterogeneous ice nucleation scheme allows us to explain the existence of the Arctic clouds
in the mixed-phase state for a long time and its application in multidimensional models may provide
new insights for phase transitions in clouds.
The equations of this ice nucleation theory allow significant simplifications. Note that the value
of Jf,het is very small (<2 × 10−7 s−1) at all stages of the process (Fig. 9.18e), and the expressions intro-
duced in Section 9.10 can be substantially simplified since in (Eqn. 9.10.1)

( t
) t
exp − ∫ J f ,het (rN , t ′) dt ′ ≈ 1 − ∫ J f ,het (rN , t ′) dt ′.
0 0
(9.14.1)

The probability of the freezing Pcf (rN, t) of an aerosol particle with rN in (Eqn. 9.10.1) can be simpli-
fied as

( t
) t
Pcf (rN , t ) = 1 − exp − ∫ J f ,het (rN , t ′) dt ′ ≈ ∫ J f ,het (rN , t ′) dt ′.
0 0
(9.14.2)

The total number of crystals (Eqn. 9.10.3) is also simplified as

rmax rmax t
N fr (t ) = ∫rmin
Pcf (rN , t ) fa (rN ) drN ≈ ∫ ∫
rmin 0
J f ,het (rN , t ′) fa (rN ) dt ′drN . (9.14.3)

The crystal nucleation rate in a polydisperse aerosol (Eqn. 9.10.5) can be simplified as

dNfr rmax
R fr (t ) = =∫ fa (rN ) J f ,het (rN , t ) drN (9.14.4)
dt rmin

These simplifications can be very useful for analytical parameterizations similar to those developed in
Section 8.10 for homogeneous nucleation and derived for heterogeneous nucleation in Section 10.1,
and for numerical modeling, since they significantly shorten the number of arithmetic operations.
A key issue in heterogeneous nucleation is the contribution of the various regions of aerosol size
spectra to the nucleation. Fig. 9.20 shows the subintegral functions of (Eqns. 9.10.5) and (9.10.3), or
478 Heterogeneous Nucleation of Drops and Ice Crystals

1.0
max = 10

0.8

Radius rN (µm)
0.6

0.2
0.4
2

6
0.2

0.0
110 120 130 140 150
(a)

1.0
max = 1.05

0.03 0.05
0.8
3
0.0
Radius rN (µm)

0.6 05
0.
0.3
0.4

0.2
0.9
0.03

0.6
0.05 0.3
0.0
110 120 130 140 150
Time (min)
(b)

Figure 9.20. Characteristics of contributions of various aerosol size fractions into the polydisperse
nucleation rate at various stages of nucleation. (a) Subintegral function (in 10−7 cm−3 s−1) in
polydisperse nucleation rate dNfr /dt (rN,t), (Eqns. 9.10.5) or (9.14.4); (b) Subintegral function
in polydisperse concentration Nf (rN,t) of frozen aerosol (cm−4), (Eqns. 9.10.3) and (9.14.3).
Maxima of subintegral functions are indicated on top of Figures. From Khvorostyanov and Curry
(2005a), J. Atmos. Sci., 62, © American Meteorological Society. Used with permission.

(Eqns. 9.14.4) and (9.14.3) here, for the polydisperse nucleation rate dNc /dt(t) and crystal concentration
Nc(t), illustrating the size contributions to these quantities. The maximum contributions come from
the region ra ∼ 0.1–0.6 μm, in agreement with the available experimental data that show maximum
occurrence of the IN radii ∼0.2–2.5 μm (e.g., Pruppacher and Klett, 1997, p. 327), or 0.18–0.23 μm
(Rogers et al., 1998, 2001; Chen et al. 1998). Note that we accounted here only for aerosol with
rN < 4 μm. It would be interesting to estimate the contributions from larger particles. Berezinsky and
Stepanov (1986) showed that these particles (up to 100 μm) might give contributions at higher T (in
agreement with Section 9.10), and explained their action by the easier dissolution of the hygroscopic
fraction of these IN. Accounting for such large IN requires knowledge of the distribution of soluble
and insoluble fractions inside the large CCN.
9.14. Parcel Model Simulations of Ice Nucleation Kinetics 479

0.3 160

180
0.2

Crystal size spectra (L–1µm–1)

0.2
140

0.1
130

0.1
120

0.0
0 50 100 150 200 250 300 350
Crystal radius (µm)

Figure 9.21. Temporal evolution of the crystal size spectra for the same conditions as in
Figs. 9.18–9.19 (T0 = −14 °C). The numbers at the curves indicate time in minutes. From Khvorostyanov
and Curry (2005a), J. Atmos. Sci., 62, © American Meteorological Society. Used with permission.

The temporal evolution of the ice crystal size spectra is shown in Fig. 9.21. The maximum crystal
radius grows until t = 150 minutes, corresponding to increasing Nc (see Fig. 9.19). Nucleation ceases
after 150 minutes, the small size fraction vanishes, the minimum and maximum radii at 180 minutes
are 50 and 280 μm, and the sizes increase with time. The absolute dispersion of the size spectra sabs
decreases due to the Maxwellian 1/ri growth law, and the relative dispersions sabs/ri,mean decreases
even faster because of the increasing mean radius ri,mean. Thus, the crystal size spectra produced by
a parcel model narrows with time similar to the droplet spectra in response to diffusional growth,
as was found in the previous parcel model simulations (Howell, 1949; Mordy, 1959; Neiburger and
Chien, 1960) and discussed in Section 5.5.2. In a real cloud, the spectral narrowing is overwhelmed
by turbulent mixing, accretion, and other effects (e.g., Khvorostyanov and Curry, 1999c,d, 2008b,c;
see Chapters 13 and 14).
When the initial temperature Tc0 decreases further (from −18 to −57 °C), no drops occur with
mis = 0.5 and the cloud is entirely crystalline, even initially. The kinetics of this process at Tc0 = −18 °C
and w = 2 cm s−1 is shown in Fig. 9.22. The crystals form via heterogeneous freezing of deliquescent
CCN at water subsaturations similar to homogeneous freezing but at higher temperatures due to the
catalyzing effect of the insoluble fraction. The maximum supersaturations over water, swm, and over
ice, sim, at which ice nucleation occurs are −3 and 20% respectively at Tc = −19 °C, and final Nc =
27 L−1. This case illustrates how clear-sky crystal precipitation (diamond dust) may occur due to the
heterogeneous freezing of deliquescent CCN even at relatively warm temperatures and humidities
intermediate between water and ice saturation, such as have been observed in the Arctic, particularly
near open leads with large relative humidity or are observed in winter at cold temperatures (Ohtake
et al., 1982; Curry, 1983, 1995; Curry et al., 1990, 1996, 2000; Pinto et al., 2001; Girard and Curry, 2001;
Girard and Blanchet, 2001; Gultepe et al., 2003; Khvorostyanov et al., 2003; Raddatz et al., 2011, 2012).
480 Heterogeneous Nucleation of Drops and Ice Crystals

Supersaturation over water (%)

20

Crystal concentration (L–1)

1E+2
si
16
12 T = –19.2 C 1E+1
8
4 1E+0
0
–4 sw 1E–1
–8
–12 1E–2
–16
–20 1E–3
0 20 40 60 80 100 120 140 160 180 80 100 120 140 160 180
Time (min) Time (min)
(a) (b)

300 140

Crystal mean radius (µm)

250 120
IWC (mg m–3)

100
200
80
150
60
100
40
50 20
0 0
80 100 120 140 160 180 80 100 120 140 160 180
Time (min) Time (min)
(c) (d)

240
Supersaturation relaxation

100
210
Relative amount of
condensed ice (%)

180 80
time (min)

150 60
120
90 40
60
20
30
0 0
80 100 120 140 160 180 80 100 120 140 160 180
Time (min) Time (min)
(e) (f)

Figure 9.22. Time dependence of crystals microphysical properties with T0 = −18 °C, RHW0 = 89%,
w = 2 cm s−1, m = 0.52. (a) Supersaturations over water, sw, and ice, si,%; (b) crystal concentration,
L−1; (c) ice water content, mg m−3; (d) crystal mean radius, μm; (e) crystal supersaturation relaxation
time, min; (f) relative amount of condensed ice,%. From Khvorostyanov and Curry (2005a), J. Atmos.
Sci., 62, © American Meteorological Society. Used with permission.

A very cold case at Tc = −54 °C and w = 2 cm s−1 is presented in Fig. 9.23. The crystal formation
occurs at swm = −20.4%, final concentration is 110 L−1, ice water content (IWC) increases slowly with
time and is 15 mg m−3 after 3 hours of simulation, with a mean crystal radius of 35 μm. This case may
correspond to the initial stage of cirrus cloud development. Note that crystal concentration is not very
high and matches those measured in cirrus (e.g., Heymsfield and McFarquhar, 2002), illustrating the
possible use of this theory of ice nucleation for cirrus simulations.
9.14. Parcel Model Simulations of Ice Nucleation Kinetics 481

40 1E+3

Crystal concentration (L–1)

si
Supersaturation over
water and ice (%) 30 1E+2
20 1E+1
10
1
0
0.1
–10
–20 sw 1E–2
–30 1E–3
–40 1E–4
0 20 40 60 80 100 120 140 160 180 100 120 140 160 180
Time (min) Time (min)
(a) (b)

20 40

Crystal mean radius (µm)

15 30
IWC (mg m–3)

10 20

5 10

0 0
100 120 140 160 180 100 120 140 160 180
Time (min) Time (min)
(c) (d)

Figure 9.23. Time dependence of crystals microphysical properties with T0 = −54 °C (as could be in
cirrus), RHW0 = 69%, w = 2 cm s−1, and m = 0.52. (a) Supersaturations over water, sw, and ice, si,%;
(b) crystal concentration, L−1; (c) ice water content, mg m−3; (d) crystal mean radius, μm. From
Khvorostyanov and Curry (2005a), J. Atmos. Sci., 62, © American Meteorological Society. Used
with permission.

Thus, this theory of heterogeneous crystal nucleation describes evolution of the cloud phase struc-
ture with lowering temperature and is in general agreement with observations and the climatological
data on the cloud phase state, which show the occurrence of the ice phase and mixed clouds mostly
at Tc < −10 °C, and a substantial decrease (below 10%) of occurrence of the liquid phase in clouds
below −20 °C (e.g., Borovikov et al., 1963; Pruppacher and Klett, 1997, Fig. 2.33 there; see also
Section 9.17 and Fig. 9.36 here).
Fig. 9.24 illustrates the effect of the misfit strain e at T0c = −14 °C, RHW = 93%, w = 5 cm s−1,
and m = 0.52. With e = 0, the drops form at t ≈ 30 minutes, crystals form at t = 30–75 min with
maximum Nc = 63 L−1, and they coexist in a mixed-phase cloud until 75 minutes, after which time
the drops evaporate, the cloud completely glaciates, water supersaturation decreases, and ice nucle-
ation ceases. With e = 1%, ice nucleation begins 15 min later and proceeds slowly until about 2 h.
Then, the nucleation rate becomes comparable with the case e = 0 and then exceeds it after t = 2 h
with maximum Nc = 180 L−1 due to the lower temperature of nucleation, causing full crystallization
by 150 min (recall that the parcel retains all particles, although in a real cloud precipitation would
occur and the concentration would be much smaller). Because of the slower CCN freezing and slower
482 Heterogeneous Nucleation of Drops and Ice Crystals

1E+3 1E+3

Crystal concentration (L–1)

1E+2
1E+2

IWC (mg m–3)

1E+1
1 1E+1

0.1 1
1E–2 ε=0
ε=1 % 0.1
1E–3
1E–4 1E–2
0 20 40 60 80 100 120 140 160 180 0 20 40 60 80 100 120 140 160 180
Time (min) Time (min)
(a) (b)

140 300
Crystal mean radius (µm)

120 250

LWC (mg m–3)

100
200
80
150
60
100
40
20 50

0 0
0 20 40 60 80 100 120 140 160 180 0 20 40 60 80 100 120 140 160 180
Time (min) Time (min)
(c) (d)

Figure 9.24. Comparison of the time evolution of cloud microphysical properties with T0c = −14 °C,
RHW0 = 93%, w = 5 cm s−1, m = 0.52 in deliquescence-freezing mode with e = 0 (circles) and
e = 1% (triangles). (a) crystal concentration, L−1; (b) ice water content, mg m−3; (c) crystal mean
radius, μm; (d) liquid water content, mg m−3. From Khvorostyanov and Curry (2005a), J. Atmos.
Sci., 62, © American Meteorological Society. Used with permission.

Wegener–Bergeron–Findeisen process in the run with e = 1%, maximum liquid water content is
4 times greater than in the case with e = 0. The case with e = 2% (not shown in Fig. 9.24) demonstrates
the complete absence of crystallization, since the threshold supersaturation sw,th is not reached during
simulation. This strong effect of the misfit strain indicates the necessity of laboratory measurements
of the composition, chemical, and crystallographic properties of the aerosol particles.

9.14.4. Ice Nucleation Effects with Stronger Updrafts

Hobbs and Rangno (1990, hereafter HR90) and Rangno and Hobbs (1991, hereafter RH91) observed
very rapid glaciation in maritime Cu clouds when crystal concentrations increased from ≤ 1 L−1 to
300–1100 L−1 at warm temperatures of about −5 to −10 °C, over a period of 9 to 15 minutes. Their
9.14. Parcel Model Simulations of Ice Nucleation Kinetics 483

analyses showed that the known mechanisms of ice multiplication could not explain the rapid rate of
crystal production under the observed conditions. They hypothesized, that: 1) localized pockets of
high water supersaturation of 5–10% may occur in a cloud after the stage of coalescence; 2) the less
effective CCN, not activated at the first stage of cloud development, may be activated in these pockets
and serve as condensation-freezing or deposition ice nuclei, causing rapid crystal nucleation. Rogers
et al. (1994) performed simulations of such situations with a parcel model over a range of vertical
velocities from 1–10 m s−1 and using parameterizations of IN concentration based on chamber experi-
ments. A high water supersaturation and crystal concentration at Tc = −15 °C and w = 3 m s−1 was
found just in one run of a total of 18, and the authors concluded that such a case may occur only
under very specific conditions: with very low drop concentration (supermaritime CCN spectrum),
high vertical velocities, and long duration adiabatic parcel ascent. Thus, this study raised the follow-
ing issues: what is the probability of such high supersaturations in clouds; are such supersaturations
required for high crystal concentrations; and if other possible mechanisms of high crystal concentra-
tions and nucleation rates exist.
Khvorostyanov and Curry (2005a, hereafter KC05a) attempted to reproduce the rapid ice crystal
nucleation observed by HR90 and RH91 using the CCN deliquescence-freezing model described
here, which is in general agreement with the hypothesis from HR90 and RH91 on the role of CCN
as IN. Since simulation of the whole life cycle of a convective cloud with an isolated parcel is a risky
task, KC05a tried to reproduce a glaciation stage of this process under conditions similar to those
observed. From the data in HR90 on cloud top growth and aircraft passes altitudes, the vertical velocity
can be estimated as w ∼ 0.5–0.8 m s−1 at this stage. KC05a performed several simulations with
w = 0.5–1.0 m s−1.
Fig. 9.25 shows the results of the 1 hour simulation with average w = 65 cm s−1, RHW0 = 82%,
T0c = 0 °C, mis = 0.5, a = 2 × 10−5 (a is the surface fraction of the active sites of IN, see Section 9.7),
and maritime CCN concentration Na = 150 cm−3. With these parameters, condensation begins at
7 minutes and drop concentration is 92 cm−3 (Fig. 9.25c), similar to measured in HR90 during the
aircraft passes 1–6 (90–120 cm−3). Crystal nucleation begins at 10 min (Tc ≈ −4 °C), but concentra-
tion is low, ∼0.1–0.3 L−1; nucleation accelerates at t ∼ 20 min, and Nc increases from 1 L−1 to 290 L−1
from 20 to 33 min (Fig. 9.25d)—i.e., during 13 min in the temperature range −5.5 to −9 °C. Super-
saturation generation is higher than its absorption by the drops and crystals until 37 min; LWC grows
and reaches a maximum of 2.2 g m−3 (vs. measured 1.8–2.0 g m−3 in HR90 at this stage). After that
time, absorption begins to prevail, the drops partially evaporate, LWC decreases to 1.3 g m−3 by 1 h
(Fig. 9.25e) and IWC increases due to the WBF process (Fig. 9.25f). All of these characteristics
(crystal concentrations and nucleation rates at this temperature range of −5 to −10 °C, droplet con-
centration, and LWC), along with their temporal evolution, are similar to those observed by HR90.
The effect of variations of the vertical velocity and a is as follows. Under the same initial conditions
and different w, the general picture is similar but the maxima of Nc and the cloud phase state differ:
Nc = 436 L−1 with w = 50 cm s−1, and the cloud is in the mixed phase. With w = 1 m s−1, Nc = 1700 L−1
and the cloud fully glaciates by 1 h. To study the sensitivity to the surface fraction of active sites a,
we performed several runs with the same parameters but a = 0. Rapid glaciation in these runs began
later, at temperatures 4–6 °C lower, the final crystal concentrations were higher, up to 1–4 × 104 L−1,
and were reached later at lower Tc = −14 to −20 °C. So, the agreement of the runs with a = 0 with
484 Heterogeneous Nucleation of Drops and Ice Crystals

Supersaturation over water (%)

0 20
–2 si
Temperature (C)
–4 10
–6
–8 sw
0
–10
–12
–14 –10
–16
–18 –20
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(a) (b)
Droplet concentration (cm–3)

Crystal concentration (L–1)

120 1E+3
100
1E+2
80
60 1E+1
40
1
20
0 0.1
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(c) (d)
2.5 3.0

2.0 2.5
LWC (g m–3)

IWC (g m–3)

2.0
1.5
1.5
1.0
1.0
0.5 0.5
0.0 0.0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(e) (f)
18
Droplet mean radius (µm)

Crystal mean radius (µm)

100
16
14 80
12
10 60
8
40
6
4 20
2
0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(g) (h)

Figure 9.25. Kinetics of cloud glaciation at w = 65 cm s−1 simulating the rapid crystal nucleation in
small maritime Cu cloud similar to the case observed by Hobbs and Rangno (1990): evolution of
the droplet and crystal microphysical properties with w = 65 cm s−1, RHW0 = 82%, Tc0 = 0 °C,
mis = 0.5, active sites fraction a = 2 × 10−5. (a) Temperature, °C; (b) supersaturations over water,
sw, and ice, si,%; (c) droplet concentration Nd, cm−3; (d) crystal concentration Nc, L−1; (e) liquid water
content, g m−3; (f) ice water content, g m−3; (g) droplet mean radius, μm; (h) crystal mean radius, μm.
From Khvorostyanov and Curry (2005a), J. Atmos. Sci., 62, © American Meteorological Society.
Used with permission.
9.14. Parcel Model Simulations of Ice Nucleation Kinetics 485

HR90 is worse, and this indicates that the active sites of CCN could play an important role in their
freezing and rapid crystal formation in cumulus at Tc = −5 to −9 °C described in HR90. These simula-
tions show that the action of the active site is the following: a) the CCN freezing shifts to the warmer
temperatures; b) starts earlier; and c) ceases earlier at warmer T, which leads to the decrease in the
final crystal concentration as compared to the case with a = 0.
The value a = 2 × 10−5 used here is from the range given by Fletcher (1969). A more detailed
model of temperature-dependent a (T) is tested in Section 9.17. Reviews of numerous experimental
studies of various types of aerosol active sites (morphological, chemical electrical, and others) is
given in Fletcher (1962, 1969, 1970), Hobbs (1974), Young (1993), Pruppacher and Klett (1997,
Chapters 5 and 9 therein), and in the recent papers by Connolly et al. (2009) and Hoose and Möhler
(2012), along with the conclusion that little is still known about their properties. The essential effect
of aerosol active sites on CCN freezing indicates the necessity of the detailed microscopic studies of
the CCN surface properties after sampling in the chamber and field experiments.
Note that described above the high values of Nc (>104 L−1) simulated with a = 0 at lower T are also
not unrealistic. They were observed in Ac and Cu clouds even with the older techniques (Nc > 104 L−1,
Fig. 2–42 in Pruppacher and Klett, 1997), and higher values were recently found in Arctic mixed
clouds using the newer devices that can count small crystals (from a few hundred to > 4–7 × 104 L−1,
Lawson et al. 2001; Rangno and Hobbs, 2001) and post-convective anvils (e.g., Knollenberg et al.
1993). It was under conditions when ice multiplication mechanisms could not be effective, thus CCN
freezing could also contribute to high Nc concentrations.
An important result of our simulations with w = 0.5–1 m s−1 is that water supersaturation never
exceeds 1% and is 0.15 to 0.1% during the main crystal nucleation process in Fig. 9.25b, indicating
that such high ice concentrations and nucleation rates as observed in HR90 and RH91 may occur in
this theory without pockets of high water supersaturations, just via freezing of deliquescent mixed
CCN acting as IN at small supersaturations sw < 0.2–0.5% typical of mixed clouds.

9.14.5. Comparison with Homogeneous Nucleation Theory

Until the end of 1990s, absence of a heterogeneous nucleation theory suitable for low tempera-
tures has resulted in the development and refinement of models of homogeneous nucleation (e.g.,
Sassen and Dodd, 1988, 1989; Jensen et al., 1994, 1998; DeMott et al., 1994; Pruppacher, 1995;
Khvorostyanov and Sassen, 1998c, 2002; MacKenzie et al., 1998; Koop et al., 2000). Different
models of heterogeneous nucleation were compared in the Idealized Cirrus Model Comparison
Project (ICMCP, Starr et al., 2000), and Cirrus Parcel Model Comparison Project (CPMCP, Lin
et al. 2002). All models used either homogeneous nucleation theory or various empirical parameter-
izations of heterogeneous nucleation. According to the theory presented here in Chapters 8 and 9,
both homogeneous and heterogeneous nucleation processes are similar except that the nucleation
energy barrier is lower in the presence of insoluble catalyzing substrate in the heterogeneous pro-
cess. This conception is in agreement with the models employed in CPMCP for the heterogeneous
freezing mode that also treat the freezing of deliquescent mixed CCN as discussed in Section 9.7
and in this section.
486 Heterogeneous Nucleation of Drops and Ice Crystals

For a quantitative comparison of both the heterogeneous and homogeneous nucleation processes,
Khvorostyanov and Curry (2005a, hereafter KC05a) performed 2 series of experiments using the
parcel model with either homogeneous freezing of the deliquescent CCN described in Chapter 8,
Section 8.9, or heterogeneous freezing described here in Sections 9.13, 9.14. Simulations were
done under the conditions recommended for ICMCP and CPMCP; these two modes were switched
on or off in the corresponding runs. The results from KC05a are described in the following text.
The first series of simulations is for relatively “warm” cirrus at initial T0c = −40 °C, and the second
series was for a cold cirrus at T0c = −60 °C; pressure was p = 340 hPa, w = 4 cm s−1, NCCN = 200 cm−3;
contact parameter mis = 0.5 for the heterogeneous case. The integration over the haze size spec-
trum was performed for the heterogeneous case as described in Section 9.10, and for the homoge-
neous case, as recommended by CPMCP (Lin et al. 2002), using the lognormal size spectrum with
rd0 = 0.02 μm and sd = 2.5.
Simulations for the warm cirrus are illustrated in Figs. 9.26 and 9.27. For convenience of
comparison, the initial RHW0 was chosen after several preliminary runs in such a way that both
nucleation processes occurred at approximately the same time, 30 minutes after the start of the
simulation. This required RHW0 = 90% for homogeneous nucleation and only 78% for heteroge-
neous nucleation. The nucleation reaches a significant rate at RHW ≈ 97.6% for the homogeneous
processes, and at 83% for heterogeneous processes (Fig. 9.26a). The critical radius is higher for
heterogeneous nucleation because of lower humidity (Fig. 9.26b); however, the critical energy of
heterogeneous nucleation is comparable and even a little smaller at t = 35 min than that for homo-
geneous nucleation (Fig. 9.26c). This is caused by the geometric factor f(mis), which reduces the
energy barrier for nucleation. The nucleation rates per particle [s−1], homogeneous, Jhomrd3, and het-
erogeneous, Jf,het(rN, T) calculated with (Eqns. 8.6.21) and (9.7.26), respectively, as an example for a
haze particle of 0.13 μm (Fig. 9.26d) and polydisperse nucleation rates (Fig. 9.26e) are comparable
although the maxima for heterogeneous nucleation is ∼4 times higher due to this small difference
in DFcr. The final crystal concentrations are comparable: 118 L−1 in the heterogeneous case versus
56 L−1 in the homogeneous case (Fig. 9.26f).
A comparison of the time evolution of the heterogeneous versus homogeneous processes at –40 °C
is continued in Fig. 9.27. Both processes are similar in general (IWC, Nc, supersaturation relax-
ation time), although the lower ice supersaturations in the heterogeneous case lead to a smaller
mean crystal radius and vapor excess. The percentage of condensed ice is higher with heteroge-
neous nucleation, so that the efficiency of deposition is higher in this case. The crystal size spectra
30 minutes after the main nucleation impulse (Fig. 9.28) have smaller maxima but are broader in
the homogeneous nucleation process, since the difference in crystal ages is greater due to the longer
nucleation time.
A comparison of the two ice nucleation modes in the colder case at T0c = −60 °C is shown in
Fig. 9.29. This time, both runs were started at the same RHW0 = 75% in order to determine the dif-
ference in the two modes. As in the previous case, heterogeneous nucleation starts much earlier at
t = 28 minutes at RHW ≈ 80%, and homogeneous nucleation begins 16 minutes later at t = 44 minutes
at RHW ≈ 88% (Fig. 9.29b). The impulse of nucleation in the heterogeneous case is again narrower
in time (Dthet = 5 minutes vs. Dthom = 9 minutes), with comparable maxima of the nucleation rate
(Rmax,het = 2.2 × 10−3 cm−3 s−1 vs. Rmax,hom = 2.9 × 10−3 cm−3 s−1) and comparable Nc = 188 L−1 vs. 171 L−1
for heterogeneous and homogeneous cases, respectively. The entire cirrus development proceeds
similarly in both cases but is shifted by ∼18 minutes later in the homogeneous case. The crystal size
9.14. Parcel Model Simulations of Ice Nucleation Kinetics 487

Relative humidiy over water and ice (%)

100 1E–4
95
90

Critical radius (cm)

1E–5
85
80
75
1E–6
70 Heterogen.
Homogen.
65
RHWthresh
60 1E–7
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(a) (b)

Nucleation rates per particle Jls (s–1)

1E–7 1E–5

1E–8 1E–6
Free energy (erg)

1E–9 1E–7

1E–10 1E–8

1E–11 1E–9

1E–12 1E–10
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(c) (d)
1E–3 1E+3
Polydisperse nucleation rates

Crystal concentration (L–1)

1E+2
1E–4
dNi/dt (cm–3 s–1)

1E+1

1
1E–5
0.1

1E–2
1E–6
1E–3

1E–7 1E–4
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(e) (f)

Figure 9.26. Comparison of primary properties of heterogeneous nucleation (solid circles, m = 0.50,
RHW0 = 78%) and homogeneous nucleation (triangles, RHW0 = 90%) processes at T0c = −40 °C,
w = 4 cm s−1, p0 = 340 hPa. (a) Relative humidity over water and threshold humidity RHWth, %
(crosses); (b) ice germ critical radius rcr, cm; (c) free energy DFcr, erg; (d) nucleation rates,
homogeneous Jhomrd3, (Eqn. 8.3.5), and heterogeneous Jf,het, (Eqn. 9.6.7), (per particle, sec−1);
(e) polydisperse nucleation rates, Rf,hom and Rf,het in cm−3 s−1, defined by (Eqns. 8.3.10) and (9.10.5);
crystal concentration, L−1. From Khvorostyanov and Curry (2005a), J. Atmos. Sci., 62, © American
Meteorological Society. Used with permission.
488 Heterogeneous Nucleation of Drops and Ice Crystals

Supersaturations over water and ice (%)

60 60
50
si,hom

Crystal mean radius (µm)

40 50
30
si,het 40 Heterogen.
20
Homogen.
10 30
0 T = –41.2 C
sw,hom
–10 20
–20 sw,het 10
–30
–40 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(a) (b)
50 180

40 Total supersaturation relaxation 150

IWC (mg m–3)

120
time (min)

30
90
20
60

10
30

0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(c) (d)
80 60
55
Amount of condensed ice (%)

Vapor excess (mg m–3)

50
60
45
40
40 35
30
25
20
20
15
0 10
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(e) (f)

Figure 9.27. Comparison of crystal microphysical properties with heterogeneous (circles)

and homogeneous (triangles) nucleation processes at T0c = −40 °C, w = 4 cm s−1 and the other
parameters as in Fig. 9.26. (a) Supersaturations over water, sw, and ice, si,%; (b) crystal mean
radius, μm; (c) ice water content, mg m−3; (d) crystal supersaturation relaxation time tfc, min;
(e) relative amount of condensed ice, REL-ICE,%; (f) vapor excess, mg m−3. From Khvorostyanov
and Curry (2005a), J. Atmos. Sci., 62, © American Meteorological Society. Used with permission.
9.14. Parcel Model Simulations of Ice Nucleation Kinetics 489

Crystal size spectra (L–1µm–1)

Het
4

Hom

0
0 20 40 60 80 100
Crystal radius (µm)

Figure 9.28. Comparison of the crystal size spectra at T0 = −40 °C after t = 1 h with homogeneous
and heterogeneous nucleation. From Khvorostyanov and Curry (2005a), J. Atmos. Sci., 62, ©
American Meteorological Society. Used with permission.

spectra for both heterogeneous and homogeneous nucleation at T = −60 °C (Fig. 9.30) are also closer
to each other than the spectra at warmer T0c = −40 °C (Fig. 9.28). Thus the difference between the
two ice nucleation modes decreases with lowering temperature. Note that crystal concentrations for
both heterogeneous and homogeneous nucleation are quite comparable both at −40 °C and −60 °C,
despite the fact that they were calculated with substantially different equations. This indicates that the
heterogeneous theory can be used for the calculations of ice nucleation in cirrus.
Finally, we compare the results of KC05a with the other four models from the Cirrus Parcel
Model Comparison Project (Lin et al., 2002). Table 9.1 shows that the results of KC05a for the

Table 9.1. Comparison of the crystal concentrations, cm−3, calculated here using this parcel model,
heterogeneous nucleation theory KC00-05 and homogeneous theory from Khvorostyanov and
Sassen (1998c, KS98), with the results from the parcel intercomparison project CPMCP
(Lin et al., 2002). Capital letters mean the author of the model: L-Lin, S-Sassen, X- Xiahong
Liu, D- DeMott. “W” means warm case (−40 °C), “C” means cold (−60 °C), “hom” means
homogeneous nucleation, “het” means “all modes” (actually, heterogeneous case). The models
are described in more detail in the text

Model

Case KC00-05, KS98 L S X D

Ca (het) 0.188 0.0126 1.0655 – 0.4027

Ch (hom) 0.178 0.1380 0.1640 0.281 0.4740
Wa (het) 0.118 0.0054 0.0183 – 0.0064
Wh (hom) 0.056 0.0286 0.0275 0.044 0.0810
490 Heterogeneous Nucleation of Drops and Ice Crystals

Polydisp nucl rate dNi/dt (cm–3 s–1)

Supersaturation over water (%)
100 1E–2
si,hom
80
1E–3
60
si,het
40 1E–4 Heterogen
20
Homogen
0 1E–5
sw,hom
–20
1E–6
–40 sw,het
–60 1E–7
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(a) (b)
1E+3 20
Crystal concentration (L–1)

Crystal mean radius (µm)

1E+2
1E+1 15

1E+0
10
1E–1
1E–2 5
1E–3
1E–4 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
Supersaturation relaxation time (min)

(c) (d)
6 180
160
140
IWC (mg m–3)

4 120
100
80
2 60
40
20
0 0
0 10 20 30 40 50 60 30 35 40 45 50 55 60
Time (min) Time (min)
(e) (f)
100 12
Amount of condensed ice (%)

Vapor excess (mg m–3)

80 10

8
60
6
40
4
20
2
0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)
(g) (h)

Figure 9.29. Comparison of crystal microphysical properties with heterogeneous (circles)

and homogeneous (triangles) nucleation processes at T0 = −60 °C, w = 4 cm s−1 and the other
parameters as in Fig. 9.26. (a) Supersaturations over water, sw,hom, sw,het, and ice, si,hom, si,het, (%);
(b) polydisperse nucleation rates dNc /dt (cm−3 s−1); (c) crystal concentration (L−1); (d) crystal mean
radius, μm; (e) ice water content, mg m−3; (f) crystal supersaturation relaxation time tfc, min;
(g) relative amount of condensed ice, REL-ICE,%; (h) vapor excess, mg m−3. From Khvorostyanov
and Curry (2005a), J. Atmos. Sci., 62, © American Meteorological Society. Used with permission.
9.15. Comparison of Simulated Crystal Concentrations 491

25

20

Crystal size spectra (L–1µm–1)

15

Het
10

5 Hom

0
0 5 10 15 20 25 30 35
Crystal radius (µm)

Figure 9.30. Comparison of the crystal size spectra at T0 = −60 °C after t = 1 h with homogeneous
and heterogeneous nucleation. From Khvorostyanov and Curry (2005a), J. Atmos. Sci., 62,
© American Meteorological Society. Used with permission.

Warm homogeneous case (denoted Wh), Nc = 0.056 cm−3, are in the middle of the range among
the other models (Nc = 0.0275−0.081 cm−3); the same is true for the Cold homogeneous case (Ch);
Nc = 0.178 cm−3 in KC05a is comparable to the others at Nc = 0.138–0.474 cm−3. This agreement
shows that the KC05a parcel model have sufficient accuracy and can be used for such simulations,
and the theory of homogeneous ice nucleation is sufficiently developed for quantitative descriptions.
With heterogeneous nucleation, the range of the other 4 models of the CPMCP is 0.0054–0.0183 cm−3
for Wa (Warm all-mode) and 0.0126–1.065 cm−3 for Ca (Cold all-mode, where mostly the heteroge-
neous nucleation mode acts). Heterogeneous nucleation results from KC05a are comparable with
the homogeneous nucleation method, 0.118 and 0.188 cm−3 for warm and cold cases, since both
processes are similar and proceed on the same CCN with comparable rates. However, heterogeneous
nucleation requires lower humidity and starts earlier in a cooling air parcel.

9.15. Comparison of Simulated Crystal Concentrations with Experimental

Data and Parameterizations
To illustrate the general dependence of the crystal concentration on the temperature and vertical veloc-
ities, the final crystal concentrations Nc(T, w) (after nucleation has ceased) are plotted in Fig. 9.31.
This figure includes simulations from KC05a based on several hundred runs of the parcel model with
w = 0.3, 1, 2, 5, and 50 cm s−1. The Cooper’s (1986) parameterization (Eqn. 9.4.4) is also plotted for
comparison. Each solid symbol in Fig. 9.31 corresponds to a final value of Nc after a single run of the
parcel model with the KC scheme. This figure shows a substantial variability of Nc that depends on
the initial temperature T, vertical velocity w, contact parameter mis, and the area a of the active sites.
492 Heterogeneous Nucleation of Drops and Ice Crystals

1E+4
50
50 cm s–1, mixed

1E+3 Cooper′86

0.52
5
0.55
0.52
1E+2 2 0.50 0.53
0.37
0.51
Crystal concentration (L–1)

0.6
1
0.50
1E+1 0.65
0.3 0.12 0.5

0.50
1 cm s–1, mixed 0.30
1E+0
0.50,α
1 cm s–1, cryst. 0.65
0.32
2 cm s–1, mixed
1E–1
2 cm s–1, cryst. 0.6
–1
5 cm s , mixed

1E–2 5 cm s–1, cryst. 0.50

–1 par, 0.3
50 cm s , mixed
–1
50 cm s , cryst. Cooper′86
1E–3
–60 –50 –40 –30 –20 –10 0
Temperature (C)

Figure 9.31. Temperature dependence of the crystal concentrations Nc calculated with w = 1 cm s−1
(solid and open circles), 2 cm s−1 (solid and open diamonds), 5 cm s−1 (crosses and asterisks), and
50 cm s−1 (squares). Each symbol corresponds to a final Nc after a single run of the parcel model
with the KC00-05 heterogeneous DF ice nucleation scheme. The values of the contact parameter
mis = 0.52 = const along the continuous lines, the other values of mis are shown near the points
that are outside the lines; the symbol “a” denotes the runs with active sites fraction a = 2 × 10−5,
otherwise a = 0. Solid symbols denote CCN freezing at sw > 0 in the presence of drops in a mixed
cloud, mostly at Tc > −20 °C, although mixed phase can be below −20 °C and down to −30 °C
with lower mis = 0.12–0.30. Open symbols denote ice nucleation at sw < 0 in a crystalline cloud.
The solid lines, along which the symbols are grouped, are parameterizations from KC05a of the
simulation data as described in the text (Eqn. 9.15.1) plotted for w = 0.3, 1, 2, 3, 5, and 50 cm s−1.
These lines are compared with Cooper’s (1986) parameterization (triangles). These fits might be
used as a simple parameterization of the average data in the Figure in cloud models and GCMs.
From Curry and Khvorostyanov, Atmos. Chem. Phys. (2012), with changes.

The general tendency of the cloud phase state is the transition from the liquid state at Tc ≥ −10 °C to
the mixed-phase state for −10 < Tc < −20 °C, and to the crystalline state at Tc < −20 °C. This is caused
by the increasing crystal concentrations with decreasing temperature.
However, Fig. 9.31 shows that mixed-phase clouds may exist in these simulations down to −30 °C
at lower values of mis (0.12–0.32), which produce low crystal concentrations of Nc = 0.8–3 L−1 and
9.15. Comparison of Simulated Crystal Concentrations 493

do not lead to complete cloud glaciation. The same result was obtained with lower aerosol concentra-
tions down to 50 cm−3 (not shown). This indicates that the KC scheme can be consistent with frequent
observations of the mixed-phase Arctic clouds at low temperatures below −20 °C observed in the
SHEBA-FIRE (Surface Heat Budget of the Arctic – First International Regional Experiment) of the
International Satellite Cloud Climatology Project (ISCCP) and many other experiments (e.g., Curry,
1986; Curry et al., 1990, 1993, 1996, 2000; Gultepe et al., 2003; Lawson et al., 2001; Uttal et al.,
2002; Intrieri et al. 2002; Korolev et al., 2003; Shupe et al., 2006; McFarquhar et al., 2007). This the-
ory of heterogeneous nucleation indicates that observations of the mixed-phase strongly supercooled
mixed Ac (Herman and Curry, 1984; Sassen and Campbell, 2001; Sassen and Khvorostyanov, 2007,
2008; Sassen and Wang, 2012) may also be caused by the specific chemical composition of CCN with
low contact parameter mis or low CCN concentration or low insoluble fractions.
The solid lines with the open symbols in Fig. 9.31 represent a parameterization of the simulation
data as a function of two variables, Tc (temperature in °C) and w, found in KC05a and refined in
Curry and Khvorostyanov (2012, CK12):

N c (T , w) = Cg (Tc 0 − Tc )CT wCw , (9.15.1)

where Nc is in L−1, Tc is the temperature in Celsius, Tc0 = 0 °C, Cw = 1.41; and there are two sets of the
other constants: Cg = 0.4 × 10−8, CT = 8.0, for Tc > −15 °C; and Cg = 0.535, CT = 1.05 for Tc < −15 °C.
Fig. 9.31 shows that (Eqn. 9.15.1) represents well the simulation data, the simulation points for
each w lie along the T-curves calculated with (Eqn. 9.15.1), which therefore can be used as a simple
parameterization in cloud models and GCMs. For example, Zhang et al. (2011) successfully used
(Eqn. 9.15.1) in the Weather Research and Forecast (WRF) model incorporating the microphysics scheme
from Morrison, Curry and Khvorostyanov (2005, hereafter, Morrison’s microphysics) for simulations
of dust effects on ice nucleation in the hurricane Helene-2005 development and found that dust aerosols
nucleating ice in this mode may noticeably influence hurricane dynamics and cloud microphysics.
Fig. 9.31 shows that under relatively warm conditions (Tc ≥ −10 °C) and in weak updrafts
(w = 1–2 cm s−1), the cloud is almost entirely liquid for mis = 0.5–0.55. Ice crystals could probably
form in this temperature range with values of Sw ∼ 1.03–1.05 (see Section 9.7), but do not form here
since the growing droplets do not allow supersaturations higher than ∼0.1–0.2%, which is insuf-
ficient for ice nucleation at these temperatures and contact parameters. At slightly higher values of
mis = 0.6–0.65 or in the presence of a small fraction of active sites, a = 2 × 10−5, the probability of ice
nucleation increases in this range. The simulations and Cooper’s and Fletcher’s empirical parameter-
izations described in Section 9.4 show increasing Nc with decreasing T.
It is interesting to note that although the dynamics in these simple parcel simulations is differ-
ent from that in the continuous flow chambers, simulated values of Nc at −10 °C > Tc > −20 °C are
comparable to the range of those measured in the chambers (e.g., Rogers, 1982, 1988; Al-Naimi and
Saunders, 1985; Meyers et al., 1992). For a more detailed comparison with the chamber experiments,
this theory of heterogeneous nucleation could be tested, e.g., in a 2D model that simulates a vertical
plane in a chamber or in a 3D model that simulates the microphysical processes in a chamber with
their spatial inhomogeneity.
The earlier T-parameterization by Fletcher (1962) was based on data available by the end of the
1950s, and was obtained for temperatures mostly above −25 °C. Its extrapolation down to very low
temperatures led to very high values of Nc, which forced modelers to refuse use of heterogeneous
494 Heterogeneous Nucleation of Drops and Ice Crystals

nucleation for cold cirrus and altostratus and invoke homogeneous nucleation theory for these clouds
as the main nucleation mode or introduce various modifications to Fletcher’s parameterization for
cold Tc (e.g., Sassen and Dodd, 1988, 1989; Heymsfield and Sabin, 1989; DeMott et al., 1994; Jensen
et al., 1994, 1996; Khvorostyanov and Sassen, 1998b, 2002; Spice et al., 1999; Gu and Liou, 2000;
Lin et al., 2002; Kärcher and Lohmann, 2002a,b). The theory presented here is in accord with numer-
ous observations in recent decades (e.g., Meyers et al., 1992, Fig. 2 therein), and gives reasonable
values of Nc at very cold temperatures that are in agreement with measurements in cirrus (see also the
next section)—e.g., Gayet et al. (1996), Chen et al. (1998), Rogers et al. (1998), DeMott et al. (1998),
Heymsfield and McFarquhar (2002), Lawson et al. (2001), and the other empirical parameterizations
used in CPMCP for heterogeneous ice nucleation at cirrus temperatures (Lin et al., 2002). Hence, this
theory of heterogeneous ice crystal nucleation can be used for simulation of cold altostratus, altocu-
mulus, and cirrus clouds, serving as an alternative for homogeneous nucleation, or both modes could
be included together. A comparison of the runs performed at colder temperatures (below −20 °C)
showed that Nc increases by a factor ∼3 when w increases from 1 to 2 cm s−1, and by ∼4 when w
increases from 2 to 5 cm s−1, indicating the nonlinear dependence of Nc on w, approximated in (Eqn.
9.15.1) by a power Cw = 1.41, similar to the parameterizations of homogeneous nucleation in Kärcher
and Lohmann (2002a,b), Ren and MacKenzie (2005), and here in Chapter 8 with Cw = 1.5 (a more
detailed parameterization and its coefficients for various regimes will be derived in Section 10.1).
The KC heterogeneous ice nucleation scheme was used for simulations of cirrus clouds and cold Arc-
tic clouds (Khvorostyanov et al., 2001, 2003, 2006; Khvorostyanov and Sassen, 2002; Sassen et al.,
2002; Liu and Penner, 2005; Comstock et al., 2008) and for simulation of cold altocumulus clouds
(Sassen and Khvorostyanov, 2007, 2008), and produced reasonable (not very high) crystal concentra-
tions in all these simulations. Ervens and Feingold (2012) used the KC scheme with superimposed
several kinds of random processes for simulation of the laboratory experiments on ice nucleation.
The KC parameterization (Eqn. 9.15.1) is compared in Fig. 9.32 to the experimental data from
the six field campaigns described in Eidhammer et al. (2009): INSPECT1, INSPECT2, CRYSTAL-
FACE, PACDEX, WISP, and MPACE (data kindly provided by Paul DeMott and Trude Eidhammer).
Fig. 9.32 shows that the span of the KC parameterization curves in the range w = 0.3–5 cm s−1 encloses
the majority of the field data—i.e., this ice nucleation scheme is in general agreement with the field
experiments. The tendency of KC curves is in qualitative agreement with Cooper’s (1986) parameter-
ization used in the Morrison microphysics scheme currently employed in the CAM3 GCM (Morrison
and Gettelman, 2008; Gettelman et al., 2008) but allows a greater Nc(T, w) variability caused by the
different cooling rates (–g w).
The almost vertical curve in Fig. 9.32, marked “PDA-DHF,” is from Phillips, DeMott, and Andro-
nache (2008, hereafter, PDA08). This curve was intended in PDA08 to represent the T-dependence
of the DHF mode in the KC theory . Therefore, it is labeled here “PDA-DHF.” However, Figs. 9.31
and 9.32 here clearly illustrate that this “PDA-DHF” curve from PDA08 is completely different
from the real T-dependences in the KC scheme shown in Figs. 9.31 and 9.32 and does not cor-
respond to this scheme. Although this curve PDA-DHF was an erroneous attempt in PDA08 of
representation of the DHF mode in the KC scheme, its discussion is useful because it illustrates the
difficulties of the previous classical nucleation theory. The reasons of the discrepancy between the
PDA-DHF curve and KC T-curves are: a) this curve was constructed in PDA08 without considering
9.15. Comparison of Simulated Crystal Concentrations 495

1E+5 PDA–DHF

1E+4
w = 50

1E+3 Cooper′86

w= 5
IN concentration (L–1)

1E+2
w=2
w=1
1E+1
w = 0.3

1E+0
Inspect1

Inspect2
1E–1
Crystal–face

Pacdex
1E–2
Wisp

Mpace Cooper′86
1E–3
–60 –50 –40 –30 –20 –10 0
Temperature (C)

Figure 9.32. Parameterized with (Eqn. 9.15.1) parcel model simulations using the KC scheme
with DF mode shown in Fig. 9.31 for the 5 values of w = 0.3, 1, 2, 5, and 50 cm s−1 (indicated near
the left ends of the curves at T ≈ −56 °C) are compared to the experimental data from the 6 field
campaigns (INSPECT1, INSPECT2, CRYSTAL-FACE, PACDEX, WISP, MPACE) described in
Eidhammer et al. (2009) and indicated in the legend with various symbols (data kindly provided by
Paul DeMott and Trude Eidhammer). Cooper’s (1986) parameterization is given for reference. The
almost vertical curve labeled “PDA-DHF” is from Philips et al. (2008); it was calculated in Philips
et al. (2008) without parcel simulations—i.e., with account for only T-dependence at Sw = 1;
that is, neglecting the supersaturation dependence and its negative feedback. From Curry and
Khvorostyanov, Atmos. Chem. Phys. (2012), with changes.
any time-dependent ice nucleation process (without parcel or any other simulations), just by calcu-
lating Nc(T) from (Eqn. 9.10.3); b) the critical energy DFcr and nucleation rates Jf,het were calculated
in PDA08 at Sw = 1 (or RHW = 100%), that is, neglecting the supersaturation dependence and its
strong negative feedback that stops nucleation as was discussed in Section 9.14. Therefore, this curve
essentially overestimates Nc(T) and the slopes dNc /dT.
This curve without Sw-dependence and without time evolution of the nucleation process actually
represents the old T-dependence based on the classical equations (Eqn. 8.6.1) for rcr and (Eqn. 8.6.2)
for DFcr by J. J. Thomson (1888) taking into account only the T-dependence (see Section 9.7). It has
496 Heterogeneous Nucleation of Drops and Ice Crystals

long been known that early formulations of the classical nucleation theory produce an unrealistic
behavior of Nc(T). This is well illustrated by this curve PDA-DHF, and this stimulated development of
numerous empirical parameterizations, many of which, however, could not be extended to the colder
temperatures. The use of the KC scheme which takes into account both T- and Sw-dependencies
allows calculations of crystal concentrations in the wide T-range based on this extension of the clas-
sical theory. As Figs. 9.31 and 9.32 show, the KC scheme produces the results substantially different
from the classical theory with only T-dependence represented by the curve PDA-DHF. It allows us
to describe many nucleation events that begin at different initial conditions (T, Sw), pass different
trajectories on the Sw-T phase plane, and span the wide range of final crystal concentrations nucleated
at various conditions. The strong negative feedback due to Sw-dependence bounds Nc and produces
much smoother Nc(T) and parameterization that are in good general agreement with the data from
six field campaigns as shown in Figs. 9.31 and 9.32.
A distinguishing feature of pristine Nc found in many experiments is its dependence on ice or wa-
ter supersaturation discussed in Section 9.4 (e.g., Huffman, 1973; Rogers, 1982, 1988; Hussain and
Saunders, 1984; Al-Naimi and Saunders, 1985; Berezinsky and Stepanov, 1986; Rogers, et al. 2001).
These studies found that a power law (Eqn. 9.4.2) or exponential function (Eqn. 9.4.7) of si describe
this dependence. Fig. 9.33 illustrates the ice supersaturation dependence Nc(si) calculated in KC05a
using this theory of CCN freezing; the same data as in Fig. 9.31, but grouped and plotted as the
functions of si. Each solid triangle, circle, or diamond on the curves corresponds to a final Nc (after
nucleation ceased) in a single run of the parcel model for 1–3 hours with w= 1, 2, and 5 cm s−1 plot-
ted against the maximum value of si during the run. The symbols are connected by the fitting lines
with the contact parameter mis = 0.52 along the lines; the values of mis are indicated near the points
where it is different; the symbol “a ” denotes the runs with a = 2 × 10−5. Plotted here are also two
previous empirical parameterizations described in Section 9.4, Meyers et al. (1992, MDC92, crosses)
and Huffman’s (1973) power law N c (si ) = CiH sibH (asterisks). Huffman found 3 < bH < 8, and CiH was
more uncertain. We have chosen here the values CiH = 10−5 L−1 and bH = 4.9 to match the lab data.
Fig. 9.33 shows that the simulated in KC05a with CNT values of Nc are in reasonable qualitative
and quantitative agreement with the experimental points and both previous parameterizations. The
main features of the simulated Nc(si) are: a) increasing Nc with increasing si; and b) a marked decrease
of the slopes dNc(si)/dsi at si > 15–20%—i.e., some sort of “saturation” at higher si. This feature,
convex dependence Nc(si) with decreasing slopes, is similar to the measured water supersaturation
dependence in the drop nucleation power law (e.g., Yum and Hudson, 2001; see Figs. 6.17 and 6.18
in Chapter 6) and to the ice supersaturation dependence for ice nucleation described by the empirical
power law (Eqn. 9.4.2) and measured at constant temperatures (e.g., Rogers, 1982; Al-Naimi and
Saunders, 1985; Berezinsky and Stepanov, 1986; Meyers et al., 1992), and is similar to the equiva-
lent analytical dependence of homogeneous nucleation on w derived in Section 8.8. This functional
similarity is caused by the analogous negative feedback with respect to supersaturation of both drop
and crystal nucleation, although the latter is much stronger, as discussed earlier. Note again, a more
detailed comparison with the laboratory data can be done using a more sophisticated model closer to
the chamber conditions. However, Fig. 9.33 shows that even this simple parcel simulation with calcu-
lation of heterogeneous nucleation based on extended classical nucleation theory allows a reasonable
description of the variety of experimental data.
9.16. Thermodynamic Constraints on Heterogeneous Ice Nucleation Schemes 497

1E+3

0.52

0.50
1E+2 0.52 0.52
0.37
0.50
0.6
Crystal concentration (L–1)

0.69 0.52
1E+1
0.65
0.5
0.5, α
0.6 1 cm s–1
1E+0
2 cm s–1
0.65
5 cm s–1
0.5
1E–1 CFDC experim.
0.55
MDC92
0.67
0.5 Huffman′73

1E–2
0 10 20 30 40 50 60
Ice supersaturation (%)

Figure 9.33. The simulated ice supersaturation dependence of the crystal concentration Nc(si). The
final Nc after a single run of the parcel model are denoted with solid triangles, circles, and diamonds
for w = 1, 2, and 5 cm s−1, respectively. The symbols are connected by the fitting lines, the contact
parameter mis = 0.52 along the lines; the values of mis are indicated near the points where it is
different; the symbol “a ” denotes the runs with active sites a = 2 × 10−5. Open squares (CFDC
experim.) denote laboratory data from Rogers (1982) and Al Naimi and Saunders (1985). The
parameterizations by Huffman (1973) and Meyers et al. (1992, MDC92) are marked with asterisks
and crosses. From Curry and Khvorostyanov, Atmos. Chem. Phys. (2012), with changes.

9.16. Thermodynamic Constraints on Heterogeneous Ice Nucleation Schemes

Classical nucleation theory allows us to impose certain constraints on the empirical parameteriza-
tions of IN concentrations described in Section 9.4. Here we assess the range of validity of these
parameterizations in the context of thermodynamic constraints based on the extended classical nucle-
ation theory described in the previous sections. The critical radius rcr of an ice germ in (Eqn. 9.7.5a)
should be positive; thus, the denominator should be positive, yielding a condition for the threshold
Sw,th(T) for ice particle nucleation
M w Lefm /RT
T  M  2 2σ sa ∆ρ∆p  
Sw (T ) ≥ Swhet,th (T ) =   exp  w  Cε ε + r + ρ   . (9.16.1)
 T0   ρi RT  a w  
498 Heterogeneous Nucleation of Drops and Ice Crystals

The notations were defined in Sections 9.7 and 9.12. Equation (9.16.1) represents a lower limit for
Sw for infinitesimally small nucleation rates Jhet, the more general equations for finite Jhet derived in
Section 9.12 predict somewhat higher Swhet,th .
Equations (9.7.5a) and (9.16.1) show that the value rcr > 0 if Sw > Swhet,th , or δ Sw ,th = Sw − Swhet,th > 0 at
a given T, and only these states are thermodynamically allowed in the Sw-T domain. The denominator
of rcr of ice germs in (Eqn. 9.7.5a) (affinity Dm =mmstab − mstab, where mmstab and mstab are the chemical
potentials of the metastable liquid and stable ice phases) becomes negative and the critical radii
become negative, rcr < 0, and unphysical in the Sw-T domain if Sw < Swhet , or d Sw,th < 0 at a given T, that
is, the relative humidity over water (RHW) or water saturation ratio Sw is smaller than its threshold
value (see Section 9.12), or δ ( RHWth ) = RHW − RHWth = ( Sw − Sw ,th ) × 100% < 0.
het

As pointed out earlier, the condition rcr > 0 or d Sw > 0 means that mmstab > mstab (affinity Dm > 0),
then such a transition mmstab → mstab (nucleation) is thermodynamically allowed. The reverse condition
rcr < 0 or Dm < 0 or DSw < 0 means that the transition is prohibited from the state with lower energy
mstab to the state with higher energy mmstab, and an ice germ cannot form.
Note that the constraint (Eqn. 9.16.1) is sufficiently general, it follows from the entropy equation
used for derivation of rcr in (Eqn. 9.7.5a) that is based on classical thermodynamics.
The constraint (Eqn. 9.16.1) allows us to assess the range of thermodynamic validity of the IN
parameterizations from Meyers et al. (1992, MDC92), Phillips et al. (2008, PDA08), and DeMott
et al. (2010, DM10) on the Sw-T diagrams using values of Nc calculated with parameterizations
MDC92, (Eqn. 9.4.7) here, and DM10, (Eqn. 9.4.12) here. Calculations with MDC92 and DM10
were performed over a wide range of values of si and T. For comparison with Sw,th and DSth, these
quantities were recalculated for pairs of Sw and T values. Calculated with MDC92 and DM10 values
of Nc(Si) and Nc(T) were superimposed in Fig. 9.34 on the field of d (RHWth) = RHW − RHWth =
(Sw − Sw,th) × 100% in Sw-T coordinates calculated using (Eqn. 9.16.1).
Fig. 9.34 represents an Sw-T diagram over the domain −30 < Tc < 0 °C and 0.7 < Sw < 1.0. Super-
imposed here is the threshold difference d (RHWth). The bold hatched line denotes the boundary
RHW − RHWth = 0 (d (RHWth) = 0) and separates thermodynamically allowed and prohibited states.
The states above this line (white field), as described by (Eqn. 9.7.6b) for Dm, correspond to the negative
differences of d Sth< 0 or of chemical potentials Dm = ml − mi = mmstab − mstab < 0, i.e., to mmstab < mstab,
and therefore to negative values of rcr. The ice germs cannot be nucleated above this line in this Sw-T
area, which corresponds to the reverse transition from the stable ice phase to metastable liquid phase
and is thermodynamically prohibited. Only the states with rcr > 0 or Dm > 0 below the bold hatched
line d (RHWth) = 0 (shaded fields) are thermodynamically allowed for heterogeneous ice nucleation
by freezing. Fig. 9.34 shows that the allowed T-Sw domains are located in the right lower triangles
below the temperature of −8 to −12 °C and at a water saturation ratio above 0.8 to 0.83, this area
covering only about 1∕8 of the entire domain is considered. We note here that ice nucleation in the
MDC92, PDA08, DM10, and similar empirical schemes is allowed in the thermodynamically prohib-
ited region, and certain IN concentrations are predicted here. The boundaries of the allowed domain
depend on the size ra of aerosol particles. When ra increases from 0.05 μm, typical of the fine mode,
to 1 μm, typical of the coarser mode, the allowed domain shifts to higher temperatures by about 5 °C.
It is interesting to note that the isolines of the MDC92 si-parameterization are in good correlation
(almost parallel) with the isolines of d (RHWth), indicating that MDC92 captures some basic features
9.16. Thermodynamic Constraints on Heterogeneous Ice Nucleation Schemes 499

0 0 0 0
ra = 0.05 µm 5
ra= 1.0 µm
–3 0
–5 –5 –5 –2 –5
5 0
–3 –2
0
–3

5
Temperature (C)

Temperature (C)

Temperature (C)

Temperature (C)
–1
–10 –1
5 –10 –10 –10

5
0.
0 0
–3 –1 5
–2

0
–1

–5
–15 5 Nucleation prohibited, –15 –15 Nucleation prohibited, –15
0.1

–2
rcr<0 rcr<0

0.1
0
–2
–20 –2
0 –20 –20 Nucleation –20
0.2

Nucleation allowed,

0.2
5
–1
allowed, rcr>0
–25 –25 –25 –25
0
5
2.
.5

–1

0
rcr>0

0
1.
00

1.

2.

0
5.
–5
–1

10
–5
–1

5
–30 –30 –30 –30
0.70 0.75 0.80 0.85 0.90 0.95 1.00 0.70 0.75 0.80 0.85 0.90 0.95 1.00
Water saturation ratio Sw Water saturation ratio Sw
(a) (b)

0 0 0 0
ra= 0.05 µm 5 5 ra= 1.0 µm
5 –1 –3 0
–5 –2 –5 –5 –2 –5
5
–3
0 5
–3 –1
Temperature (C)
Temperature (C)

Temperature (C)

Temperature (C)
–10 –10 –10 –10
5
–2 0
–1
5 –1 –5
–15 –2
5 Nucleation prohibited, –15 –15 Nucleation prohibited, –15
rcr<0 5
rcr<0
0

–
–2

–20 –20 –20 –20

Nucleation
5
–1

–25 Nucleation –25 –25 allowed, –25

5
–1

allowed, rcr>0
0

rcr>0
–1

–5

–30 –30 –30 –30

–5

0.70 0.75 0.80 0.85 0.90 0.95 1.00 0.70 0.75 0.80 0.85 0.90 0.95 1.00
Water saturation ratio Sw Water saturation ratio Sw
(c) (d)

Figure 9.34. Sw-T diagrams of Nc calculated with MDC92 (a, b) and DM10 (c, d) parameterizations
(solid lines) with superimposed threshold difference d (RHWth) = RHW − RHWth = (Sw − Sw,th) × 100%
calculated with KC scheme based on CNT (dashed lines), as described in the text. The bold and
hatched line d (RHW,th) = 0 or RHW = RHWth indicate the boundary between the thermodynamically
allowed and prohibited states. The physical states and Nc above this line in the white field are
thermodynamically prohibited and correspond to negative critical radii of ice germs, rcr < 0. The
states below the line d (RHW,th) = 0 in the right lower corner are thermodynamically allowed and
physical. From Curry and Khvorostyanov, Atmos. Chem. Phys. (2012), with changes.

of the nucleation process. However, the gradients dNc /dSw and dNc /dT in MDC92 are noticeably
smaller than predicted by the classical theory. This may be caused by the smoothing action of the
mixtures of aerosols in the chamber experiments with different properties, while calculations with
(Eqn. 9.16.1) are performed for only one aerosol type. The agreement of DM10 T-parameterization
with classical theory is somewhat worse because they account only for the T-dependence but do not
account for the humidity dependence.
Another thermodynamic constraint is imposed on the immersion freezing mode. In some works,
it was hypothesized (without derivation) that the effect of humidity in the immersion mode can be
500 Heterogeneous Nucleation of Drops and Ice Crystals

described by introducing a new expression for the radius of the critical germ of immersion freezing
in the form
2 vw1σ iw
rg ,imm = , (9.16.2)
 ews 
kT ln  aw
 eis 

where vw1 is the volume of a water molecule in ice, siw is the surface tension between ice and water
at the ice–water interface, ews and eis are the saturation vapor pressures over water and ice, and aw is
the water activity inside a drop containing an ice germ. It was hypothesized in these works that this
equation is based on the expression for rcr from classical nucleation theory given in Chen et al. (2008,
equation (5) and Section 2.2.2 therein) for the case of immersion freezing that can be written as
2 vw1σ iw
rg ,imm = . (9.16.3)
kT ln(ews /eis )

Using the relation vw1 = 1/Ni, where Ni is the concentrations of molecules per unit volume of ice, this
equation can be rewritten as
2σ iw
rg ,imm = . (9.16.4)
N i kT ln(ews / eis )

This equation exactly coincides with the classical equation (Eqn. 9.7.7a) of Section 9.7 given in
Fletcher (1962), Young (1993), and other descriptions of CNT. Equations (9.16.3) and (9.16.4) are
correct equations of CNT, and their equivalence to the J. J. Thomson’s formulation (Eqn. 9.7.7) in
terms of ln(T0/T) was shown in Section 9.7. Chen et al. (2008) cited this equation as applicable for
freezing in pure water—i.e., at water saturation, and it was stated further in Chen et al. (2008): “Note
that for the freezing of solution, the parameter ews should be modified by the water activity of the
solution.” Some authors modified (Eqn. 9.16.3) for the case of water subsaturation (RHW < 100%
or Sw < 1) simply multiplying the ratio ews /eis by the water activity aw < 1, and this equation got the
form (Eqn. 9.16.2).
However, it can be shown that simple multiplication of the ratio ews /eis by the water activity aw < 1
is a risky trick and leads to a confusing result. It was shown in Section 3.10 and (Eqn. 3.10.24) that
the water activity in equilibrium with ice awi(T ) (as in a drop containing ice germ), is expressed via
the ratio of saturated vapor pressures over ice and water, awi(T ) = eis ( T ) / ews ( T ), and it was illustrated
in Fig. 8.14b that this equation gives a very good description of the melting curve for solution in
agreement with the other methods. Substituting this awi (T ) into (Eqn. 9.16.2), as has been done in
several works, we obtain
2 vw1σ iw 2 vw1σ iw 2v σ 2v σ
rg ,imm = = = w1 iw = w1 iw = ∞. (9.16.5)
 e  e e  kT ln(1) 0
kT ln  awi ws  kT ln  is ws 
 eis   ews eis 

Thus, (Eqn. 9.16.2) predicts an infinite germ radius, which is a confusing result. Therefore, gen-
eralization of (Eqn. 9.16.2) for solutions or water subsaturations by simple multiplication of the
ratio ews /eis by aw < 1 leads to a wrong result. A more rigorous derivation is required for rcr. Such
a derivation for rcr for cloud drop freezing in the immersion mode was presented in this chapter
9.17. Evaluation of Ice Nucleation and Cloud Phase State Parameterizations 501

(Eqns. 9.7.6c) to (9.7.6h), based on the general equilibrium (entropy) equation and Kelvin’s equi-
librium for cloud drops. The equations for rcr for haze particles in the DF mode and for cloud drops
in the immersion mode appeared to be similar. It was shown in parcel model simulations that the
equations for rcr and DFcr can be applicable both in the deliquescence-freezing mode and in the im-
mersion mode at water subsaturation (Sw < 1) and supersaturation (Sw > 1) (Section 9.14). However,
thermodynamic constraints impose certain limitations on the physical domain in the (T-Sw) or (T-aw)
space, as illustrated in Fig. 9.34.
We do not present here similar thermodynamic analysis of the other existing parameterizations,
but this can easily be done for any function Nc(T) and Nc(si). These thermodynamic limitations also
should be accounted for when choosing and comparing the empirical and theoretical parameteriza-
tions of ice nucleation in the numerical models of various complexity as, for example, in Comstock
et al. (2008) and Eidhammer et al. (2009). The empirical parameterizations should be applied with
caution outside the ranges recommended for them and should not be applied outside of thermody-
namically allowed conditions.

9.17. Evaluation of Ice Nucleation and Cloud Phase State Parameterizations

Another verification of the empirical versus theoretical ice nucleation parameterizations can be done
by comparison of the cloud phase state predicted by various parameterizations with the climatol-
ogy of the mixed-phase clouds as is observed and parameterized in the general circulation models
(GCMs). Eidhammer et al. (2009; hereafter EDK09) compared three parameterizations of heteroge-
neous ice nucleation using a parcel model developed at Colorado State University (CSU). The model
is based on the spectral bin microphysics for the mixed and ice states with various parameterizations
of ice nucleation. The three ice nucleation schemes tested in EDK09 included the two empirical
schemes described in Section 9.4, Diehl and Wurzler (2004, hereafter DW04), Phillips et al. (2008,
hereafter PDA08), and the theoretical scheme based on the extended classical nucleation theory by
Khvorostyanov and Curry (2000, 2004a,b, 2005a, hereafter KC). EDK09 compared mostly the crys-
tal concentrations Nc produced by these schemes but not the ratio of the LWC to IWC—i.e., not the
cloud mixed-phase state.
Comparing the results of simulations for the three parameterizations, EDK09 found that for small
vertical velocities w ∼ 5 cm s−1, all three parameterizations yield similar results. For large w, only
PDA08 compares well with typical observations of ice nucleation in CFDC, producing Nc ∼ 1–20 L−1,
while the other two parameterizations (DW04 and KC) produce crystal concentrations significantly
higher than PDA08. EDK09 concluded that the empirically derived “constraint” on the upper limit of
Nc used in the PDA08 scheme should be used in cloud and climate model parameterizations.
Curry and Khvorostyanov (2012, hereafter CK12) compared further the PDA08 and KC schemes
in order to understand the sources of the discrepancies between the two parameterizations (we note
that the DW04 scheme performs comparably to KC and produces comparable values of Nc, LWC
and IWC). The results of these comparisons are described in this section. CK12 carried out simula-
tions using the parcel model described in KC05 (see Sections 9.13 and 9.14) and used the same
composition of aerosol as in EDK09, and the KC deliquescence-heterogeneous freezing (DHetF) ice
nucleation scheme (Section 9.7). The KC scheme and CNT in general were further extended in Curry
502 Heterogeneous Nucleation of Drops and Ice Crystals

and Khvorostyanov (2012) by generalizing the Fletcher’s (1969) idea and including a temperature-
dependent parameterization of the active site area a as a function of T,

α (T ) = α 0 (1 − Tc / Tv )θ (Tth − Tc )θ (Tc − Tv ), (9.17.1)

where q (x) is the Heaviside function, Tth = −5 °C is the threshold temperature of nucleation close
to that assumed in EDK09, and Tv = −20 °C is the scaling temperature that determined the rate of
decrease of a (T). The value a0 = 2 × 10−5 was chosen because it has been successfully tested in KC05
to explain the fast glaciation of polar maritime cumulus observed in Hobbs and Rangno (1990) and
Rangno and Hobbs (1991) without high water supersaturation (see Section 9.14). Equation (9.17.1)
indicates that a (T) has a maximum a0 = 2 × 10−5 at warm T, decreases to 0 at Tv = −20 °C, and a (T) = 0
at Tc < Tv. This parameterization accounts for the fact that the area of the active sites close to the
structure of water (mis = 1) that are favorable for nucleation increases toward 0 °C. We hypothesize
that these sites can be formed by crystal defects, steps, or premelted sites. Their exact origin does
not matter for now, but it is known that the number of such sites may increase toward 0 °C (Fletcher,
1970; Hobbs, 1974; Dash et al., 1995; Rosenberg, 2005).
Simulations were conducted under the following conditions: w = 50 cm s−1, RHW0 = 96%, T0 = 10 °C,
and with the two models of active sites, a = 0 and a (T), described by (Eqn. 9.17.1). The KC scheme was
used with DHetF mode in three versions. The input data for these three runs were the following: #1) only
one coarse aerosol fraction included as in EDK09, lognormal size spectrum, concentration NIN,2 = 1 cm−3
(1000 L−1), mean geometric radius rd2 = 0.4 μm, dispersion sd2 = 2, and active site area a = 0; #2) the
same coarse aerosol fraction, NIN,2 = 1 cm−3, but variable a (T) described by (Eqn. 9.17.1); #3) a = 0,
and including three IN lognormal fractions with equal concentrations NIN,1 = NIN,2 = NIN,3 = 10 L−1 =
10−2 cm−3—i.e., 100 times smaller than in runs #1 and #2 and in EDK09 for the KC scheme), with
rd1 = rd2 = rd3 = 0.4 μm, but 3 different values of contact parameter, 0.85, 0.75, and 0.5 that can mimic a
mixture of organic (bacteria or pollen), soot, and mineral IN. The IN concentration of 1 cm−3 in the runs
#1 and #2 follows the choice in EDK09 for the KC scheme, although it is not clear why this very high
concentration NIN,2 was chosen in EDK09. This is an arbitrary choice, 2–3 orders of magnitude higher
than typical IN concentrations in CFDC, and it is not related to any characteristic of the KC scheme. In
run #3, the concentrations were chosen comparable to those measured in CFDCs and used in PDA08.
The results of simulations from EDK09 with ice scheme PDA08 and from the three simulations
of our parcel model with the KC scheme are compared in Fig. 9.35. Due to high initial RHW, drop
activation occurs in a few minutes (a bit earlier than in EDK09 due to a little higher RHW0). The
drop concentration Nd is ∼90 cm−3 in the EDK09 model and 160 cm−3 in the KC model, the differ-
ence associated with different drop activation methods, but this is unimportant. Values of Nd are
constant in EDK09 simulations for 4 hours (Fig. 9.35c), and liquid water content (LWC) increases
over this period due to drop growth down to T = −34.5 °C (Fig. 9.35e). In the EDK09 model with
the PDA08 ice scheme, noticeable heterogeneous crystal nucleation begins at about 75 min when
T < −3 °C, the concentration Nc increases almost linearly and reaches ∼22 L−1 at T ∼ −32.5 °C at
a height above 6 km, and time is 240 min (Fig. 9.35d). Thus, nucleation with the PDA08 scheme
continues over almost 4 hours, much longer than in any other heterogeneous scheme (e.g., Sassen
and Benson, 2000; Lin et al., 2002; Kärcher and Lohmann, 2003; KC05; Liu and Penner, 2005),
and much longer than in CFDC experiments, 7–15 s, (Phillips et al., 2008) upon which the PDA08
5 40
35 EDK09

Water supersaturation (%)

0

Ice supersaturation (%)

30 KC, α = 0
25 KC, α(T)
–5 20
KC, 3 fract.
15
−10
10
−15 5
0
−20 –5
–10
−25 –15
10 5 0 –5 −10 −15 −20 −25 −30 −35 −40 10 5 0 –5 –10 –15 –20 –25 –30 –35 –40
Temperature (C) Temperature (C)
(a) (b)
1E+5
160
Droplet concentration (cm–3)

Crystal concentration (L–1)

1E+4
140
1E+3
120
1E+2 3
100 2
1E+1 1
80
1 EDK09
60
KC, α = 0
40 0.1
KC, α(T)
20 1E–2
KC, 3 fract.
0 1E–3
10 5 0 –5 –10 –15 –20 –25 –30 –35 10 5 0 –5 –10 –15 –20 –25 –30 –35
Temperature (C) Temperature (C)

0 30 60 90 120 150 180 210 240 0 30 60 90 120 150 180 210 240
Time (min) Time (min)
(c) (d)
10 20
Liquid water mixing ratio (g kg–1)

Ice water mixing ratio( g kg–1)

9 15

6 10

3 5

0 0
10 5 0 –5 –10 –15 –20 –25 –30 –35 10 5 0 –5 –10 –15 –20 –25 –30 –35
Temperature (C) Temperature (C)

0 30 60 90 120 150 180 210 240 0 30 60 90 120 150 180 210 240
Time (min) Time (min)

0 2 4 6 0 2 4 6
Height (km) Height (km)
(e) (f)

Figure 9.35. Comparison of the temperature and time dependencies of cloud microphysical properties
in the parcel runs obtained in simulations by Eidhammer et al. (2009, EDK09) with parameterization
of Phillips et al. (2008, PDA08, solid circles) and obtained in simulations in Curry and
Khvorostyanov (2012) using the KC scheme with DHetF mode in three runs: #1) only 2nd aerosol
mode included as in EDK09, Nd2 = 1 cm−3 (1000 L−1), sd2 = 2, rd2 = 0.4 μm, and active site area
a = 0 (crosses); #2) only the same 2nd aerosol mode and variable a(T) as a linear function of T as
described in the text (triangles); #3) including three IN lognormal fractions with equal mean radii
rd1 = rd2 = rd3 = 0.4 μm, equal concentrations NIN,1 = NIN,2 = NIN,3 = 10 L−1 = 10−2 cm−3 (i.e., 100 times
smaller than in runs #1 and #2 and in EDK09 for the KC scheme), but with three different values
of contact parameter for each fraction, mis = 0.85, 0.75, and 0.5 (diamonds). The three nucleation
impulses in Nc in the run #3 caused by nucleation of the IN fractions with different mis are denoted
by the numbers 1, 2, and 3 (Fig. 9.35d). The parameters: w = 50 cm s−1, RHW0 = 96%, and T0 =
10 °C. From Curry and Khvorostyanov, Atmos. Chem. Phys. (2012).
503
504 Heterogeneous Nucleation of Drops and Ice Crystals

parameterization is based. Then, an abrupt increase in Nc occurs by almost 3 orders of magnitude to

1.6 × 104 L−1, caused by homogeneous drop freezing, which begins in the EDK09 model at heights
above 6 km, at T ≈ −34 °C, close to the homogeneous freezing threshold for the drops with radii of
18–20 μm. At temperatures warmer than −34 °C, the nucleated ice crystals do not influence Nd and
LWC, and no signs of the Wegener–Bergeron–Findeisen process and crystallization are seen on the
EDK09 curves. Instantaneous glaciation occurs due to drop homogeneous freezing only when the
temperature falls below −35 °C; Nc rapidly increases by three orders of magnitude, and Nd and LWC
abruptly drop to zero. Thus, the crystals heterogeneously formed in the PDA08 scheme are unable
to produce any noticeable crystallization effect down to −34 °C, and the “constraints” imposed in the
PDA08 scheme lead to a substantial underestimation of heterogeneous ice nucleation and ice phase.
In contrast, crystallization in the KC scheme in simulations #1 and #2 with NIN,2 = 1 cm−3 occurs
much more smoothly with decreasing temperature, in the temperature range of ∼20 °C. With a = 0,
crystal nucleation in the KC scheme begins at −15 °C and Nc reaches a maximum ∼103 L−1 within 2 °C.
With the smooth function a (T) in simulation #2, crystal nucleation begins at about −5 °C, and ends
at −17 °C, more smoothly than with a = 0. Cloud glaciation with decreasing Nd and LWC begins at
−15 °C with a = 0 (at −7 °C with a (T), which better describes the effect of IN active at warmer temper-
atures) and ends at −35 °C with a = 0 (at −23 °C with a (T)), over the T-range of 16–20 °C and a time of
1 hour in both cases. (Note that the DW04 scheme, Fig. 1 in EDK09, is not shown here, but it performs
similarly to the KC scheme in runs #1 and #2, and produces realistic crystallization and the cloud
phase state.) In simulation #3 with 3 IN fractions and with the KC scheme, heterogeneous nucleation
occurs in the three temperature ranges, near −5, −8 to −9, and −15 to −18 °C, corresponding to nucle-
ation of each of 3 fractions, from the highest to lowest contact parameter. Each nucleation impulse
produces values of Nc almost equal to the concentration in the corresponding fractions, ∼10 L−1, and
the total is ∼30 L−1 at T < −18 °C. Each nucleation impulse is located in a relatively narrow temperature
range of 1–3 °C, but the total temperature range of ice nucleation stretches over 13 °C.
Fig. 9.35 shows that this nucleation picture and final crystal concentration with the KC scheme in
simulation #3 are close to those produced in EDK09 with the PDA08 scheme. With this small final
Nc = 30 L−1, the KC scheme also does not produce glaciation down to the homogeneous freezing
threshold of −34 °C, when rapid drop freeing and cloud crystallization occur. Thus, the conclusion in
EDK09 that the KC and DW04 schemes produce very high crystal concentrations was caused by an
arbitrary choice of very high (1000 L−1) IN concentrations for these schemes in EDK09. The conclu-
sion that nucleation in the KC scheme occurs in a very narrow temperature range was caused by the
choice of just one IN fraction with “monodisperse” properties: contact angle, a, etc. A more realistic
choice of IN properties produces nucleation with the KC scheme over a wide T-interval.
One of the major criteria for validity of ice nucleation parameterization is the cloud-phase state,
an important characteristic in weather prediction and climate models. The phase state in clouds is
characterized by the ratio of the liquid (LWC) to the total water (LWC + IWC) in mixed phase,
fl = LWC/(LWC + IWC) × 100%. Fig. 9.36 shows the observed climatology of fl compiled from a few
thousand aircraft measurements (Borovikov et al., 1963; reproduced in Pruppacher and Klett, 1997,
PK97). In pure-liquid clouds at warm temperatures slightly below 0 °C, the observed climatological
fl is close to 100%, and then decreases with decreasing temperature (22% liquid at −15 °C) and tends
to zero at T < −30 °C—i.e., the clouds become purely crystalline.
9.17. Evaluation of Ice Nucleation and Cloud Phase State Parameterizations 505

Frequency of liquid vs mixed phase (%)

100
90
EDK09
80
Bor63, PK97
70
KC05, α(T)
60
KC05, α = 0
50
NCAR CAM3
40 ECMWF
30
20
10
0
0 −5 −10 −15 −20 −25 −30 −35 −40 −45 −50
Temperature (C)

Figure 9.36. Frequency of liquid vs. mixed states. Climatological data after Borovikov et al.
(1963, Bor63) (reproduced also in Fig. 2–33 in Pruppacher and Klett, 1997, PK97), compared to
the characteristic of the liquid/mixed phase, the ratio fl = LWC/(LWC + IWC), simulated in Curry
and Khvorostyanov (2012) with the KC05 parcel model (Section 9.13) and heterogeneous KC ice
scheme as shown in Fig. 9.35: with only 2nd aerosol mode included, Nd2 = 1 cm−3, sd2= 2,
rd2 = 0.4 μm, and 2 values of active site areas: a = 0 (diamonds), variable a (T) as described in the
text (triangles), and simulated in the EDK09 parcel model with the PDA08 ice scheme with the
same aerosol (asterisks). These simulations are compared to the corresponding T-partitioning of
the liquid and ice phases in the climate models with single-moment microphysics: the NCAR
CAM3 (Boville et al., 2006), (83% liquid at −15 °C) and ECMWF (ECMWF-2007), (12% liquid
at −15 °C) as described in the text. From Curry and Khvorostyanov, Atmos. Chem. Phys. (2012).

Fig. 9.36 compares this climatological data with fl calculated from the simulations data of EDK09
and from the three runs with the KC scheme shown in Fig. 9.35 earlier comparing two forms of a (T)
and two input IN concentrations. These are also compared with the two parameterizations of fl as a
function of temperature in two general circulation models: the European Centre for Medium-Range
Weather Forecasts (ECMWF-2007) and the National Center for Atmospheric Research Community
Atmosphere Model 3 (NCAR CAM3), Boville et al. (2006). In ECMWF, the liquid fraction was
chosen as fl = [(T − Tice)/(T0 − Tice)]2, and fl = 0 at T < Tice, with T0 = 273.16 and Tice = 250.16 K
(12% liquid at −15 °C), (ECMWF-2007). In NCAR CAM3, the ice fraction was parameterized as
fi(T) = (T − Tmax)/(Tmin − Tmax) with Tmax = −10 °C, Tmin = −40 °C (Boville et al., 2006). Then, fl in
percent can be written as fl(T) = 1− fi(T) = (Tmin − T)/(Tmin − Tmax) × 100, and fl(T) = 0 at T < Tmin
(83% liquid at −15 °C). Fig. 9.36 shows that the ECMWF parameterization is very close to the cli-
matological data of Borovikov et al. (1963), but ends at slightly warmer temperatures. The CAM3
parameterization has a slope close to the climatological data, but the curve CAM3 is displaced as
a whole toward colder temperatures by about 10 °C, underestimating the ice phase at warm and
medium temperatures (note that the T-limits in NCAR CAM2 were 0 and −20 °C (Boville et al., 2006),
and fl(T) was closer to the ECMWF).
The fl(T) slopes in the KC scheme in simulations #1 and #2 with NIN,2 = 1 cm−3 are steeper than the
climatological ECMWF and CAM3 curves but are still comparable to them, and closer to CAM3.
506 Heterogeneous Nucleation of Drops and Ice Crystals

A fraction of the ice phase increases in KC scheme at −16 °C with a = 0 and at −7 °C with a (T);
the threshold with a (T) is close to the threshold in CAM3. In general, the KC scheme in simulations
#1 and #2 with NIN,2 = 1 cm−3 may underestimate the ice phase at warm temperatures and overestimate
the ice phase at cold T. However, there is a clear qualitative agreement of the KC scheme in simula-
tions #1 and #2 with the climatological data and parameterizations ECMWF and CAM3, although
a further smoothing of the KC curve over the wider T-range is desirable, which is discussed in the
following text.
In contrast, the EDK09 simulations using the PDA08 parameterization, and simulations with the
KC scheme in simulation #3 with low concentrations NIN,1 = NIN,2 = NIN,1 = 10 L−1 are in sharp conflict
with climatology. EDK09 and KC simulation #3 with low IN predict a more than 95% liquid phase
down to −34.5 °C, where homogeneous nucleation begins to act in the drops with radii of ∼20 μm.
With homogeneous nucleation, the PDA08 and KC run #3 curves are very close and exhibit abrupt
crystallization within a few tenths of a degree, and the curve fl(T) is actually vertical at Tc ≈ −35 °C,
which disagrees with climatological data and GCM parameterizations. The simulations in EDK09
show that the DW04 scheme produces ice crystals with concentrations similar to the KC scheme in
simulations #1 and #2—i.e., with the limits 300 L−1 for dust and 1000 L−1 for soot, the corresponding
limiting aerosol concentrations in the 2nd mode chosen in EDK09.
The low heterogeneous nucleation efficiency of the PDA08 scheme in ice production was somewhat
masked in Fig. 9.35, where the characteristics of the liquid and ice phases were plotted separately,
but it becomes clearer in Fig. 9.36, when considering the ratio of liquid to total water, fl(T). Fig. 9.36
illustrates that the increase in LWC during the parcel ascent is so rapid that the small amount of ice
nucleated with the PDA08 scheme did not result in any noticeable crystal growth and liquid water
depletion by the WBF mechanism. EDK09 argued that the KC and DW04 schemes produced crystal
concentrations a few orders of magnitude greater and substantially overestimate ice production. How-
ever, Figs. 9.35 and 9.36 show that high crystal concentration is not a characteristic feature of the KC
scheme. It was a result of choosing a high value of input IN concentration NIN ∼ 1 cm−3 for the KC
scheme in EDK09.
Fig. 9.36 shows that the KC scheme with higher values of NIN ∼ 1 cm−3 is much closer to reality in
reproducing the cloud phase state (and the DW04 scheme also), while the PDA08 scheme produces
unrealistically high values of liquid water down to the threshold of homogeneous nucleation. It is
not clear whether this is a consequence of the too low IN concentrations in the PDA08 scheme or a
result of an unrealistic simulation with an isolated parcel model with high constant vertical velocities
for a long time.
This question can be answered by running Eulerian models with a more realistic dynamic and
physical framework with various ice schemes. To address this question, the KC scheme was tested
with a more realistic 1D Eulerian model in simulations of the ARM Mixed Phase Arctic Cloud Exper-
iment (MPACE) in autumn 2006 (Verlinde et al., 2007; Klein et al., 2009; Morrison et al., 2009). The
results of simulation were described in Curry and Khvorostyanov (2012) and appeared to be similar
to those observed in the MPACE mixed cloud with quite realistic crystal concentrations and cloud-
phase states.
10
Parameterizations of Heterogeneous Ice Nucleation

Using the general equations derived in Chapter 9 based on extended classical nucleation theory,
parameterizations are derived suitable for use in cloud and climate models with sufficiently large
time steps. Heterogeneous freezing of haze particles and drops caused by supersaturation and tem-
perature variations are considered in Sections 10.1 and 10.2, and similar parameterizations of the
deposition nucleation is derived in Sections 10.3. In particular, it is shown that the functional forms
of previous empirical or semi-empirical parameterizations described in Section 9.4 can be obtained
and generalized from these theoretical parameterizations based on classical nucleation theory, and
their empirical parameters can be expressed via the fundamental atmospheric parameters and aerosol
properties.
In the next three sections, Sections 10.4–10.6, contact ice nucleation mode is described, its gen-
eral properties, the three major mechanisms of aerosol scavenging by drops that may lead to contact
nucleation, the collection rates, probabilities of freezing, and scavenging in polydisperse ensembles
of drops and aerosols.

10.1. Analytical Parameterization of Heterogeneous Freezing Kinetics

Based on Classical Nucleation Theory (CNT)

In this section, we consider the parameterization of heterogeneous ice nucleation by freezing, based
on the generalization of the classical nucleation theory described in the previous sections of Chapter 9.
Pure crystalline clouds are considered in detail, whereby ice crystals form by the freezing of haze
particles without formation of the liquid phase. This mechanism of heterogeneous freezing competes
with the homogeneous freezing of haze droplets in the formation of cirrus clouds (Jensen et al.,
1994, 1998; DeMott et al., 1998; Khvorostyanov et al., 2001, 2006; Lin et al., 2002; Khvorostyanov
and Sassen, 2002; Kärcher and Lohmann, 2003; Kärcher et al., 2006; Barahona and Nenes, 2009).
This phenomenon also occurs at low altitudes in the polar regions and is called “clear sky ice crystal
precipitation” or “diamond dust” (e.g., Ohtake and Huffman, 1969; Curry, 1983, 1995; Curry et al.,
1990, 1996, 2000; Girard and Blanchet, 2001). Altocumulus clouds also may form via this pathway
without the liquid phase (e.g., Sassen and Khvorostyanov, 2007, 2008; Sassen and Wang, 2012).

10.1.1. Nucleation Rates in a Polydisperse Aerosol

The nucleation rate per particle in a separable form was presented in (Eqn. 9.8.13):

f , het (T, rN , ε ) exp[ushet sw (t )],

Jf , het (T , sw ,rN , t ) ≈ J (0) (10.1.1)

507

18:23:30
508 Parameterizations of Heterogeneous Ice Nucleation

with J (0)
f , het defined in (Eqn. 9.8.15) and ushet defined in (Eqn. 9.8.11). It was shown in Section 9.14

in the parcel model simulations of ice nucleation in the deliquescence-freezing mode that the freez-
ing rate Jf,het is usually small, and expressions for the probability of freezing and heterogeneous
nucleation rate Rf,het in a polydisperse aerosol given in Section 9.10 can be simplified as described by
(Eqns. 9.14.2)–(9.14.4). Substituting (Eqn. 10.1.1) into (Eqn. 9.14.4) yields a simplified expression
for the polydisperse nucleation rate

dN fr rmax
R f , het (t ) = ≈∫ fa (rN ) J f, het (rN , t ) drN
dt rmin

α 0) α
f , het (T, rN ) J act (α a , mis , rN ) exp[us (T )sw (t )],
= J (0, (10.1.2)
α 0) α
f, het (T, rN ) and J act (α a , mis , rN ) defined in (Eqns. 9.8.8) and (9.8.9a). The dependence on rN
with J (0,
vanishes after averaging over fa(rN). In this section, we denote the active site fraction with aa to dis-
α
tinguish from the deposition coefficient ad. All other notations are the same as in Section 9.8. J act is
α
the part of the nucleation rate that describes the effect of the active sites—i.e., J act (T, rN ) defined in
(Eqns. 9.8.9a) or (9.8.12a) and integrated over the size spectrum fa(rN):
rmax
1
α
J act (α a , mis , rN ) = ∫ fa (rN )rN2 ∑ exp( zαk rN2 ) drN , (10.1.3)
rN2 rmin k

with the dimension cm−3.

The integral in (Eqn. 10.1.3) depends on the specified size spectrum by rN, and its analytical evalu-
ation is possible for some types of spectra. The simplest estimate can be done for a monodisperse
size spectrum such as the Dirac’s delta function, fa(rN) = Nad (r − rN), where Na is the concentration
of aerosol that can serve as IN, and for one type of active site with mis = 1. Substituting this spectrum
into (Eqn. 10.1.3), we obtain

α rN2 zα rN2  α σ (1 − mis )rN2 

J act (α a , mis , rN ) = N a 2
e = N a exp  a is . (10.1.4)
rN  kT 
The delta-function type spectrum is infinitely narrow, and the integral over the other size spectrum
of the finite width will contain some correction on the order of 1. We rewrite this integral with such
a shape correction coefficient csh,

α rN2 zα rN2  α aσ is (1 − mis )rN2 

J act (α a , mis , rN ) ≈ csh N a e ≈ csh N a exp  . (10.1.5)
rN2  kT 
If there are several active sites with different aa, mis, this expression is easily generalized by sum-
mation over all sites with different za as in (Eqn. 10.1.3). Equations (10.1.1) and (10.1.2) are used in
the following for parameterizations of the concentration and mean radius of the nucleated crystals.

10.1.2. Temporal Evolution of Supersaturation

The kinetics of the heterogeneous ice nucleation via deliquescence-freezing mode was described
in Section 9.14 based on simulations using a parcel model with spectral bin microphysics. These
simulations allow determination of the major features of the supersaturation evolution for developing

18:23:30
10.1. Analytical Parameterization of Heterogeneous Freezing Kinetics 509

an approximation suitable for analytical parameterizations. The nucleation rates described by (Eqns.
10.1.1 and (10.1.2) depend on T and sw. Similar to the case of homogeneous freezing described in
Section 8.10, the major time dependence is contained in sw(t) and is exponential, exp[ushetsw(t)]. The
time dependence of sw and Nc is shown in more detail in Fig. 10.1, which is an enlarged fraction
of Fig. 9.22 (T0 = −18 °C, w = 2 cm s−1) with a linear scale for Nc, which illustrates the difference
in Nc at the time tmax of maximum supersaturation and after the end of nucleation. These Figures
show that there are two branches in the supersaturation curves, with their growth (ascending branch)
and decrease (descending branch). Noticeable nucleation begins at the time tcr1 = 78.0 min when
Nc reaches Nc,cr1 = 10−3 L−1 and both water and ice supersaturations reach their first critical values,
sw,cr1 = −0.0385 (−3.85%), si,cr1 = 0.176 (17.6%).
The maximum values of both supersaturations, sw,max = −0.0281 (−2.81%) and si,max = 0.187
(18.7%), occur at tmax = 90.17 min, when Nc = 14.5 L−1. However, in contrast to drop activation
(Chapters 6, 7) and similar to homogeneous ice nucleation (Chapter 8), heterogeneous ice nucle-
ation still does not cease at time tmax with maximum supersaturations swmax and simax, when Nc(tmax)
is only about one half of the subsequent final value. Nucleation continues at t > tmax with decreasing
supersaturations, and reaches 27.1 L−1 at the second critical time tcr2 = 95 min, when sw,cr2 = −0.034
(−3.4%) and si,cr2 = 0.181 (18.1%). After that, the supersaturations fall below their critical values and
nucleation ceases, although cooling continues. This analysis shows that the relative variation of sw is
d sw /sw ∼ 27%, while the change of si is much smaller, only d si /si ∼ 0.05%. Thus, as in the case with
homogeneous nucleation, we can assume that si ≈ sihet , cr ≈ const during nucleation.

The variation of sw is d sw = swmax − sw,cr1 = −(3.85 to 2.81) × 10−2 = 1.04 × 10−2. The value of ushet is
large, and even small variations in sw lead to large variations in exp(ushetsw). For example, at T = −20 °C,
ushet ∼ 4 × 102, and the product ushet d sw ∼ (4 × 102) (1.04 × 10−2) ≈ 4.2. Thus, the factor exp(ushetsw) in

20 30 Nc = 27
Crystal concentration (L–1)

si,max
Supersaturations over

16 si si,cr1 si,cr2 25 tcr2

water and ice (%)

12
20
8 T = –19.2 C
15 Nc = 14.5 tmax
4
10
0 sw,cr1 sw,max sw,cr2
sw
–4 5
tcr1 tmax tcr2 tcr1
–8
76 78 80 82 84 86 88 90 92 94 96 76 78 80 82 84 86 88 90 92 94 96
Time (min) Time (min)
(a) (b)

Figure 10.1. Enlarged fraction of Fig. 9.22 in the parcel run with heterogeneous ice nucleation,
w = 2 cm s−1, and initial temperature T0 = −18 °C. (a) water (sw) and ice (si) supersaturations, %;
(b) crystal concentration Nc (L−1). The subscript “cr1” means the first critical time when nucleation
starts, “max” means the maxima of sw, si, at the time tmax, and “cr2” means the second critical
time, when nucleation ceases. The linear scale for Nc shows that only about half of the crystals are
nucleated by the time tmax with si,w,max and nucleation continues at t > tmax.

18:23:30
510 Parameterizations of Heterogeneous Ice Nucleation

(0,α 0)
Rf,het in (Eqns. 10.1.1) and (10.1.2) varies by exp(4.2) ≈ 67, while variations in J f , het (T , rN ) due to the
temperature change are much smaller, as it was in the case with homogeneous nucleation in Chapter 8.
Therefore, the time dependence of Rfr can be approximately accounted for via sw(t) at some average
temperature or at T = Tcr,1.
We can therefore approximate differential si and integral yi supersaturations as in Section 8.10 by
the constant values si = yi′≈ sihet ′ ≈ a1w t + swhet,cr .
,cr , and variations in sw = yw′ by the linear function sw ( t ) = yw

This is similar to a linear approximation for the drops activation described in Chapters 6 and 7 but
with initial critical (threshold) values, which account for the specifics of ice nucleation described
earlier. As discussed in Chapters 6–8, the parameter a1w can be specified in various ways, which yield
lower and upper limits of the solution. An approximation that gives a lower bound of the solution can
be obtained with a1w = c1ww:
sw (t ) = yw′ (t ) = swhet,cr + c1w wt , yw (t ) = swhet,cr t + (c1w w /2)t 2 , (10.1.6a)
het het
si (t ) = yi′(t ) ≈ s i , cr , ≈ sy , ( , = , yi (t ) = s t .
i , cr (10.1.6b)

The difference between the lower and upper bounds is on the order of 5–20% or smaller, and the dif-
ference between the lower bound and mean values is even smaller, 3–10%. The analytical equations
for the critical supersaturations swhet,cr and sihet
, cr were derived in Section 9.12.

10.1.3. Heterogeneous Nucleation Rate Derived from CNT and

Comparison with the Previous Parameterizations

Substitution of sw(t) from (Eqn. 10.1.6a) into the separable nucleation rate in (Eqn. 10.1.1) yields
Jf,het(T, sw) as a function of time in the form

J f ,het [T , sw (t ), rN , ε ] ≈ J (0)
f , het (T , rN , ε ) exp(ushet sw , cr ) exp(ushet c1 w wt ).
het
(10.1.7)

Several previous parameterizations of heterogeneous ice nucleation were based on comparisons with
the homogeneous nucleation rate Jf,hom and modifications of parameterized Jf,hom to make it suit-
able for description of heterogeneous nucleation. Kärcher and Lohmann (2003, hereafter KL03) and
Kärcher et al. (2006) hypothesized that a relation between Jf,het and Jf,hom can be established based on
the “shifted activity method” (see Sections 8.8 and 9.12). This relation from KL03 can be written as

J f ,het [T ,{X k }, aw ]
= ∆ l. (10.1.8)
J f ,hom [T , aw + δ aw ]

Here, aw is the water activity identified with ambient relative humidity divided by 100; d aw = const
= 0.32 is an independent on T shift in water activity—i.e., the difference in the critical activities for
freezing in these two modes of one particle with radius of 0.25 μm in 1 s, Δl is the parameter with the
dimension of length that was estimated in KL03 as Δl ∼ 30 nm, and {Xk} denotes the other parameters
of heterogeneous freezing.
A direct and detailed comparison of Jf,het with the homogeneous nucleation rate Jf,hom can be done
using (Eqn. 10.1.7) and an analogous expression (Eqn. 8.10.17a) for Jf,hom(t) derived in Section 8.10,
and also expressed in the form with separated temperature and saturation dependencies. Dividing

18:23:30
10.1. Analytical Parameterization of Heterogeneous Freezing Kinetics 511

Jf,het in (Eqn. 10.1.7) by Jf,hom in (Eqn. 8.10.17a) and accounting for ∆Fcr0,,0α 0 = ∆Fcrhom
,0 f ( mis ) and

ushet = ushom f(mis) (see the notations in Section 8.10) yields

J f ,het [T , sw (t ), rN ]
= RJ 1 RJ 2 RJ 3 , (10.1.9a)
J f ,hom [T , sw (t ), rN ]

where RJ1, RJ2, and RJ3 are the ratios specified next.

f ,het (T , rN , ε )  ∆ Fcrhom
,0 [ f ( mis ) − 1] ∆Fcr 
ε
J (0)
RJ 1 = =∆
ɶ l exp  − + , (10.1.9b)
J (0)
f ,hom (T ,)  kT kT 

 4π rN2 
l = Chet = c1s
∆ . (10.1.9c)
Chom  2 N cont (σ is /kT )1/2 


Since c1s ∼ Ncont, an estimate at T ∼ 250 K with sis ∼ 25 erg cm−2 gives ∆ɶ l ~ (2.3 × 10 −7 cm −1 )rN2. The
parameter ∆ ɶ l can be viewed as an analog of Δl in (Eqn. 10.1.8) from KL03, but now depends addition-
ally on rN and sis, and its dependence on T is more complicated. The factor RJ2 is

RJ 2 = exp(ushet swhet,cr − us hom swhom

, cr )

= exp[us hom f (mis )swhet,cr − us hom swhom

, cr ], (10.1.9d)

where we used the relation between ushom and ushet. This factor can be viewed as an analog of the
KL03 relation with the “shifted activity,” but is it is more complicated. The shift in water activ-
ity (or critical humidity) hypothesized in KL03 would produce an exponent in (Eqn. 10.1.8)
,cr + δ s w ,cr )], while (Eqn. 10.1.7) shows that J f ,het ~ exp(ushet sw ,cr ). Then, the equal-
het
J f ,hom ~ exp[us hom (swhom
ity Jf,het(sw) ∼ Jf,het(sw +d sw) would be valid if us hom (sw ,cr + δ sw ,cr ) = ushet sw ,cr, or using again a relation
hom het

us,het = ushom f(mis), we obtain an equation for d sw,cr:

δ sw ,cr = f (mis )swhet,cr − swhom

, cr . (10.1.9e)

This equation shows that d sw,cr strongly depends on mis; besides, swhet,cr, swhom
, cr themselves also depend

on the temperature, IN properties (mis, a, e), and the chosen critical nucleation rate—i.e., on the
cooling rate as described in Section 9.12 (see Fig. 9.17). Therefore d sw,cr cannot be constant, as was
illustrated in Fig. 9.11. The next factor, RJ3, has the form

RJ 3 = exp{us hom [ f (mis ) − 1]c1w wt}, (10.1.9f)

i.e., the ratio of Jf,het(t) and Jf,hom(t) is not constant but decreases with time, since f(mis) < 1, the argu-
ment of exp is negative, and exp < 1.
Thus, although the ratio Jf,het/Jf,hom bears some similarities with the KL03 relation (Eqn. 10.1.8),
the ratio predicted by this extended CNT theory is more complicated, so that Jf,het cannot be expressed
by a simple relation via Jf,hom and the shift in water activity or saturation ratios is not constant as was
illustrated in Sections 8.8 and 9.12 both with calculations and experimental data. Fortunately, in the
method developed here, Jf,het does not need to build upon Jf,hom and can be evaluated independently.
In some previous semi-empirical parameterizations, the exponential time dependence of Jf,het was
hypothesized and parameterized introducing some characteristic time scale tnuc,het. The exponen-
tial time dependence is described by (Eqn. 10.1.7) and now, similar to the case of homogeneous

18:23:30
512 Parameterizations of Heterogeneous Ice Nucleation

nucleation considered in Section 8.10, we can derive an analytical expression for tnuc,het. Figs. 9.18–
9.28 and 10.1 show that the major time dependence of Jf,het(t) is determined by sw(t), and the tempera-
ture change during nucleation is rather small; thus, the temperature dependence is determined near
Tcr. Dividing Jf,het(t) in (Eqn. 10.1.7) by Jf,het(t0) at some initial t0 and assuming T ≈ const, we obtain
the exponential time dependence of Jf,het(t) in the form

J f ,het (t ) = J f ,het (t0 ) exp[c1w wushet (t − t0 )]. (10.1.10)

This can be written in another form:

( t − t0 ) / τ nuc ,het
J f ,het (t ) = J f ,het (t0 )e βhet ( t − t0 ) = J f ,het (t0 )e . (10.1.11)

We introduce the parameter bhet, which can be interpreted as a characteristic “nucleation

frequency”:

β het = c1w wushet , (10.1.12)

and a characteristic “nucleation time” tnuc,het that can be expressed using (Eqn. 9.8.11) for ushet and
Gn = RT/(MwLmef ), as
−1
−1
 ∆ Fcrα,00 (T , mis ) 2Gn 
τ nuc ,het = β het = (c1w wushet )−1 = c1w w 
 kT ln(T0 /T ) 
kLefm ln(T0 /T ) M w Lefm ln(T0 /T )
= (c1w w)−1 α0
= (c1w w)−1 , (10.1.13)
2 Rv ∆Fcr ,0 (T , mis ) 2 N Av ∆Fcrα,00 (T , mis )

where Rv is the gas constant for water vapor and NAv is the Avogadro number. Equation (10.1.11)
shows that the nucleation rate of the heterogeneous ice nucleation process can be presented as an
exponential function of time with some scaling time tnuc,het given by (Eqn. 10.1.13). The time tnuc,het
characterizes the average time scale of heterogeneous nucleation, although the full time of the nucle-
ation process may be different as will be shown in the following.
It is useful to compare this time dependence with the case of homogeneous ice nucleation and
with previous parameterizations. As discussed in Section 8.10, an exponential time dependence of
the homogeneous nucleation rate Jf,hom(t) similar to (Eqn. 8.10.18) with the nucleation time scale
tnuc,hom was hypothesized by Ford (1998a,b). The tnuc,hom was parameterized as a function of tempera-
ture with auxiliary empirical relations and fitted to parcel model simulations in the parameteriza-
tions described in Section 8.10, and it was derived from CNT by Khvorostyanov and Curry (2012).
Kärcher and Lohmann (2003), Kärcher et al. (2006), and Barahona and Nenes (2009) applied a
similar exponential parameterization for the heterogeneous nucleation rate Jf,het(t) assuming the same
functional dependence of tnuc,het on Jf,het(t) as in (Eqn. 9.6.11), with subsequent fitting to the results
of the numerical parcel model. Equation (10.1.11) provides a justification for the hypothesized expo-
nential dependence of the nucleation rates, while (Eqn. 10.1.13) provides a direct expression of tnuc,het
derived from the first principles in terms of classical nucleation theory and its parameters.
Equations (8.10.19) and (10.1.13) show that both tnuc,hom and tnuc,het are inversely proportional to
the corresponding critical energies of nucleation: ∆Fcrα,00 (T , mis ) defined in (Eqn. 9.8.3), and ∆Fcrhom
,0

18:23:30
10.1. Analytical Parameterization of Heterogeneous Freezing Kinetics 513

defined in (Eqn. 8.10.10), with f(mis) = 1. From these two equations, we obtain a relationship between
the time scales of the two nucleation modes:
τ nuc ,het ∆Fcrhom 1
≈
,0
≈ . (10.1.14)
τ nuc ,hom ∆Fcrα,00 (T , mis ) f (mis )

Since f(mis) < 1, this suggests at first glance that the heterogeneous nucleation process lasts longer
than the homogeneous nucleation. However, the times tnuc,het and tnuc,hom characterize only the time
dependence of the nucleation rates Jf,het and Jf,hom, but not the overall time dependence of the nucle-
ation kinetics, which is governed by the supersaturation equation. Fig. 9.26 shows a comparison of
the nucleation rates in these two modes simulated with a parcel model as described in Section 9.14
at cirrus conditions near −40 °C. The heterogeneous nucleation rate continues for about 10 min (from
28 to 38 min), and homogeneous nucleation continues for about 16 min (from 22 to 38 min). That is,
homogeneous nucleation is slower under these conditions, which is determined by the kinetics of the
process. The same slower homogeneous nucleation is seen in Fig. 9.29 at −60 °C. Thus, tnuc,het and
tnuc,hom may be used for parameterization of the time dependence of the nucleation rates, but not for
characterizing of the entire nucleation process, which requires solving the supersaturation equation
or its parameterization.
Equation (10.1.14) also shows that a universal parameterization of tnuc,het based on the relations
like (Eqn. 8.4.17) with (tnuc,het)−1 ∼ (dT/dt) is a much more difficult task than the parameterization of
tnuc,hom because tnuc,het depends on the contact parameter mis, and may significantly vary among vari-
ous aerosol types. However, (Eqn. 10.1.13) provides a simple dependence on the contact parameter:
tnuc,het ∼ 1/f(mis).
For t0 = tcr, (Eqn. 10.1.10) can be rewritten using (Eqn. 10.1.6a) as
J f ,het [sw (t )]
ln = ushet c1w w(t − tcr ) = ushet (T )[sw (t ) − sw ,cr ]. (10.1.15)
J f ,het [sw ,cr (tcr )]

This relation is expressed in terms of the water supersaturation. Some semi-empirical parameteriza-
tions hypothesize a similar relation in terms of the ice saturation ratio, which can be derived from
(Eqn. 10.1.15). Using the relations in (Eqn. 8.10.17d) following from the Clausius–Clapeyron equa-
tion, sw = ciw(si + 1) − 1, ciw = exp[−Lm/(T0 − T)/RvT0T], we express sw in (Eqn. 10.1.15) via the ice
saturation ratio Si = si +1 and obtain
J f ,het [ Si (t )]
ln = ushet (T )ciw (T )[ Si (t ) − Si ,cr ]. (10.1.16)
J f ,het [ Si ,cr (tcr )]

This expression has the same form as hypothesized by Barahona and Nenes (2008) for homoge-
neous nucleation and Barahona and Nenes (2009) for heterogeneous nucleation, and their coefficient
bt fitted with empirical data is expressed now using the extended classical nucleation theory as
bt(T) = ushet(T)ciw(T).

18:23:30
514 Parameterizations of Heterogeneous Ice Nucleation

10.1.4. Temporal Evolution of the Crystal Concentration

Substitution of (Eqn. 10.1.6a) for sw(t) into (Eqn. 10.1.2) for Rf,het(t) and integration over time yields
the crystal concentration Nc(t) along the ascending branch of sw(t) shown in Fig. 10.1:
t

N c (t ) = ∫ R f ,het (t )dt = J (0, α 0) α

f ,het (T , rN ) J act (α a , mis , rN ) I sw (t ). (10.1.17)
0

Here, Isw(t) is the integral over time, which is easily calculated using the linear approximation (Eqn.
10.1.6a) for sw(t) and assuming as in Section 8.10 that T ≈ const:
t

I sw (t ) = ∫ exp[ushet sw (t )] dt ≈ β het
−1
exp(ushet swhet,cr )[exp(β het t ) − 1]. (10.1.18)
0

Substitution of Isw(t) into (Eqn. 10.1.17) yields

t

N c (t ) = ∫ R f ,het (t ) dt (10.1.19)
0
α 0) α −1 het
= J (0,
f , het (T , rN ) J act (α a , mis , rN ) β het exp(ushet sw , cr )[exp(β het t ) − 1] (10.1.20)
het
= J (0, α 0) α
f , het (T , rN ) J act (α a , mis , rN )τ nuc , het {exp[ushet s w (t )] − exp(ushet s w , cr )}. (10.1.21)

This is the basic parameterization of the number of ice crystals nucleated by heterogeneous freezing
via the deliquescence-freezing (or condensation-freezing) that was sought, which can be applied for
increasing sw(t).
An estimate at T = 250 K and w = 2 cm s−1 gives ushet ∼ 4 × 102, and c1w ∼ 10−5 cm−1. Thus,
bhet = ushetc1ww ∼ 8 × 10−3 s−1. At small times, t << tnuc,het = bhet−1 ∼ 125 sec, the value of bhett << 1, the
exponent can be expanded, exp(bhett) ≈ 1 + bhett, then Isw(t) and Nc(t) are simplified as
t

N c (t ) = ∫ R f ,het (t )dt = tJ (0, α 0) α

f ,het (T , rN ) J act (α a , mis , rN ) exp(ushet s w ,cr ).
het
(10.1.22)
0

α
Using the approximation (Eqn. 10.1.5) for J act (α a , mis , rN ) with one kind of active site with mis = 1,
we obtain

α 0)  α aσ is (1 − mis )rN2 
N c (t ) = csh N a tJ (0,
f , het (T , rN ) exp 
het
 exp(ushet sw ,cr ). (10.1.23)
 kT 
Without the active sites (aa = 0), the exponential term with aa is equal to 1.
Thus, at small times t << bhet−1 = tnuc,het, the crystal concentration Nc(t) increases linearly with
(0, α 0)
time, and is proportional to IN concentration Na, and to the heterogeneous nucleation rate J f ,het
het
at zero water supersaturation, but is modulated (decreased) by the critical supersaturation sw ,cr < 0.
At swhet,cr = −3.5 × 10 −2 ( −3.5%), as in Fig. 10.1, and ushet ∼ 4 × 102, the product ushet swhet,cr = −15.4 and
exp(ushet swhet,cr ) ≈ exp ( −15.4 ) ~ 10 −7. Hence, there is a substantial effect in the DF mode from the
small subsaturation on the nucleation rate and on the concentration of nucleated crystals. As esti-
mated earlier, an increase of sw to −2.8 × 10−2 (−2.8%) at tmax in Fig. 10.1 causes an increase in the
nucleation rate by a factor of exp(4.16) ∼ 102.

18:23:30
10.1. Analytical Parameterization of Heterogeneous Freezing Kinetics 515

At large times t >> bhet−1 = tnuc,het (125 sec in this example), exp(bhet t) >> 1 and (Eqn. 10.1.20)
yields

N c (t ) = J (0, α 0) α
f , het (T , rN ) J act (α a , mis , rN )τ nuc , het exp[ushet s w (t )], (10.1.24)

where sw(t) is a linear function (Eqn. 10.1.6a). With the approximation (Eqn. 10.1.5) for
α
J act (α a , mis , rN ), it becomes

α 0)  α aσ is (1 − mis )rN2 
N c (t ) = cshτ nuc ,het N a J (0,
f ,het (T , rN ) exp   exp[ushet sw (t )].
 kT 
α 0)  α aσ is (1 − mis )rN2 
= cshτ nuc ,het N a J (0,
f ,het (T , rN ) exp   × exp[ushet sw ,cr ]exp[ushet c1w wt ].
het
(10.1.25)
 kT 
Since sw(t) ∼ t, the previous two equations show that Nc(t) grows exponentially with time for tnuc,het <
t < tmax. This explains the linear growth with time of the log[Nc(t)] ∼ t as plotted in log-linear scale
figures of Nc(t) simulated by the parcel model in Figs. 9.18–9.29.

10.1.5. Comparison of Crystal Concentrations with Empirical Parameterizations

These expressions provide a theoretical explanation for the empirical parameterization by Meyers
et al. (1992, MDC92), Nc(si) = exp(aM + bMsi), (Eqn. 9.4.7), and enables the expression of empirical
parameters aM, bM via the parameters of classical nucleation theory and aerosol microphysical prop-
erties. We present Nc(t) in (Eqn. 10.1.25) as

N c (sw ) = exp(ln ADF + ushet sw ), (10.1.26a)

α 0) α
ADF = csh N aτ nuc ,het J (0,
f ,het (T , rN ) J act (α a , mis , rN ). (10.1.26b)

Similar to the derivation of (Eqn. 10.1.16), using (Eqn. 8.10.17d) we can replace sw with si and obtain
N c (si ) = exp[aDF (T , rN , mis , α a ) + bDF (T , mis )si ]. (10.1.27a)

Thus, we obtain expressions in a form similar to the MDC92 parameterization (Eqn. 9.4.7) with aDF,
bDF as

aDF (T , rN , mis , α a ) = ln ADF + ushet (ciw − 1)

α
α aσ
σ is (1 − mis )rN2
= ln[csh N a J (0, α 0)
f , het (T , rN )τ nuc , het ] + + ushet (ciw − 1), (10.1.27b)
kT
α0
2 R ∆Fcr ,0 (T , mis )  L (T − T ) 
bDF (T , mis ) = ushet ciw = ef
exp  − m 0 . (10.1.27c)
kM w Lm ln(T0 / T )  Rv T0 T 

where the subscript “DF” means the deliquescence-freezing mode, and we substituted ciw from (Eqn.
8.10.17d) and ushet from (Eqn. 9.8.11). The coefficients aDF, bDF depend on the temperature, mean
radius of IN, contact parameter, and fraction of active site aa. Being physically based, this param-
eterization is sufficiently simple and can be applied in the models. The original experimental data

18:23:30
516 Parameterizations of Heterogeneous Ice Nucleation

shown in MDC92 and used for their parameterization exhibited both T- and si-dependencies. MDC92
averaged the data over the temperatures and recommended some fixed values for aM, bM. Equations
(10.1.27a)–(10.1.27c) show that these coefficients are variable.
The dependence on the aerosol properties in aDF contains a part with lnNa, and these equations
can be rewritten as
N c (si ) = N a exp[aɶ DF (T , rN , mis , α a ) + bDF (T , mis )si ], (10.1.28a)
2
α aσ is (1 − mis )r N
aɶ DF (T , rN , mis , α a ) = ln[csh J (0, α 0)
f , het (T , rN )τ nuc , het ] + + ushet (ciw − 1). (10.1.28b)
kT
Equation (10.1.28a) shows that Nc(si) is proportional to IN concentration Na, while the other coef-
ficients contain explicit dependencies on T, aa, and other aerosol parameters.
Field and laboratory experiments show that the concentration Na of available aerosol particles that
can serve as ice nuclei (IN) and nucleate ice heterogeneously in the DF mode may vary significantly
in the atmosphere from a few per liter to a few hundred or thousands per liter. This indicates that there
can be two different modes of DF ice nucleation that may occur at small or large values of Na. These
situations are considered next.

10.1.6. Parameterization for the Large-Scale Models.

Case 1: Large Na and Crystal Concentrations Limited by Kinetics

We assume that Na is sufficiently large in this case, and the temporal behavior of supersaturations
and crystal concentration is as shown in Fig. 10.1, so that sw(t) reaches a maximum at a time tmax
and then decreases to the 2nd critical value tcr2 when nucleation ceases. Evaluation of the maximum
supersaturations sw,max and si,max and maximum Nc,max can be done similar to Section 8.10. We use
the equation for the integral ice supersaturation yi′ in the form similar to (Eqn. 8.5.15) for yi′ or to
(Eqn. 9.13.2), but with Icon = 0 since we consider a pure crystalline cloud:

dyi ′ Γ s
= c1i w(1 + yi ′ ) − 2 I dep = c1i w(1 + yi ′ ) − i . (10.1.29)
dt ρis τ fc

The deposition integral Idep defined by (Eqn. 8.5.8) is evaluated as in Section 8.10 using the conserva-
tion law, dNfr = fc(rc)drc = Rf,het(t0)dt0:
∞
4π Dv ρis rc2 (t , t0 )
I dep (t ) = si
Γ2 ∫ r (t , t ) + ξ
0 c 0 dep
fc (rc )drc .

t
4π Dv ρis
= si
Γ2 ∫0 rc,ef (t , t0 ) R f ,het (t0 )dt0 . (10.1.30)

As in Section 8.10, rc,ef(t,t0) = rc(t,t0)2/[rc(t,t0) + xdep], and rc(t,t0) is a radius at time t of a crystal nucle-
ated at time t0. It is evaluated as described in Sections 8.5 and 8.10, by integrating the equations of the

18:23:30
10.1. Analytical Parameterization of Heterogeneous Freezing Kinetics 517

crystal growth rate, and is expressed by (Eqn. 8.5.9) via yi′; rc,ef(t,t0) is expressed by (Eqn. 8.10.29),
in a form convenient for subsequent integration by time:

{[(r0 + ξ dep )2 + Bihet (t − t0 )]1/ 2 − ξ dep}2

rc, ef (t , t0 ) = ,
[(rc 0 + ξ dep )2 + Bihet (t − t0 )]1/2
= rc(1)
, ef + rc, ef + rc, ef ,
(2) (3)
Bihet = 2ci 3 sihet
,cr . (10.1.31)

The three terms of rc(,kef) on the RHS of this equation are defined as in (Eqn. 8.10.30a)–(8.10.30c) but replac-
ing Bihom → Bihet. Substituting Rf,het(t0) from (Eqn. 10.1.2) and rc,ef(t, t0) with Bihet from (Eqn. 10.1.31) into
(Eqn. 10.1.30) for Idep, we can integrate over time using the method described in detail in Section 8.10
and Appendix A.8. Then, we obtain

4π Dv ρis (0,α 0) α
I dep (t ) = si J f ,het J act (α a , mis , rN ) exp(ushet sihet
, cr ) J 0 i , het (t ), (10.1.32)
Γ2
where t 3
J 0 i ,het (t ) = ∫ rc ,ef (t , t0 ) exp(β het t0 ) dt0 = ∑ J 0( ki ,)het , (10.1.33)
0 k =1
t

J 0( ki ,)het = ∫ rc(,kef) (t , t0 ) exp(β het t0 ) dt0 . (10.1.34)

0

The integrals J 0 i ,het (t ) and J 0( ki ,)het for heterogeneous nucleation coincide with the corresponding
integrals for the case of homogeneous nucleation evaluated in Khvorostyanov and Curry (2012) and
in Section 8.10 (Appendix A.8 therein), although ushet, bhet, and Bihet differ due to different (smaller)
critical energies DFcr,het caused by the shape factor f(mis), active sites, and lower sihet , cr . Thus, we can use

the results for J 0( ki ,)het and J 0 i ,het (t ) evaluated in Section 8.10 replacing ushom→ ushet, bhom → bhet, Bihom
, cr → si , cr . Evaluating the integrals in (Eqn. 10.1.34) as described in Appendix A.8 and
het
→ Bihet, and sihom
collecting all three integrals J 0( ki ,)het yields
3
J 0 i ,het = ∑J (k )
0 i , het = e βhet t Ψ het , (10.1.35)
k

Ψ het = Ψ 1,het + Ψ 2,het + Ψ 3,het , (10.1.36a)

1/ 2 −3/ 2   3  3 
Ψ1,het = e λhet Bihet β het  Γ  , λhet − Γ  , λhet + β het t  
  2   2 
 
= e λhet Bihet
1/ 2 −3/ 2
β het {( π /2) [Φ( λhet + β het t ) − Φ( λhet )] + e [λ

t Φ( λ )] + e − λhet [λhet
1/ 2
− (λhet + β het t )1/ 2 e − βhet t ) ]}, (10.1.36b)

−1
Ψ 2 het = 2ξ dep β het (e − βhet t − 1), (10.1.36c)

 1  1 
Ψ 3 het = e λhet ξ dep
2
(β het Bihet )−1/2  Γ  , λhet  − Γ  , λhet + β het t  
  2   2 
= e λ ξ dep
2
(β het Bihet )−1/2 π [Φ( λhet + β het t ) − Φ( λhet )]. (10.1.36d)

18:23:30
518 Parameterizations of Heterogeneous Ice Nucleation

The parameter lhet here is defined similar to lhom in Section 8.10, (Eqn. 8.10.38), but with another
critical parameters:

(ξ dep + r0 )2 β het (ushet c1w w)(ξ dep + r0 )2

λhet = = . (10.1.37)
Bihet 2ci 3 sihet
,cr

Substituting (Eqn. 10.1.35) into (Eqn. 10.1.32), we obtain

4π Dv ρis (0,α 0) α
I dep (t ) = si J f ,het J act exp(ushet sw ,cr ) exp(β het t )Ψ het
Γ2
4π Dv ρis (0,α 0) α
= si J f ,het J act exp[ushet sw (t )]Ψ het . (10.1.38)
Γ2

Inserting (Eqn. 10.1.38) into (Eqn. 10.1.29) for yi′, and using the relation rv = ris(1 + yi′), we obtain

dyi′ α 0) α
= c1i w(1 + yi′) − (4π Dv )si J (0,
f , het (rN ) J act (α a , mis , rN ) exp[ushet s w (t )]Ψ het . (10.1.39)
dt
At the point with maximum supersaturations, sw = swmax and yi ′ = si = simax ≈ sihet
, cr at t = tmax, we have

the condition dsi /dt = dyi′/dt = 0, and (Eqn. 10.1.39) yields

, cr )( si , cr ) (4π Dv ) ( J f , het J act ) Ψ het .

exp[ushet sw max (tmax )] = c1i w(1 + sihet het −1 −1 (0,α 0) α −1 −1
(10.1.40)

Figures with simulation results in Section 9.14 show that the nucleation process takes thet ∼ 12–15 min,
tmax is reached in 6–8 min, and the preceding estimates showed that tnuc,het = (bhet)−1 is much smaller. Thus,
we can assume the relation bhettmax >> 1 for typical conditions and use (Eqn. 10.1.24) for Nc(tmax). After
substitution of (Eqn. 10.1.40) into (Eqn. 10.1.24), the terms with nucleation rate J (0, α 0)
f , het (T , rN ) and active
α
sites J act (α a , mis , rN ) vanish and we obtain a simple expression for Nchet(tmax):
het
N chet (tmax ) = K gen (1 + sihet het −1 −1
, cr )( si , cr ) Ψ het , (10.1.41a)
het
K gen = (4π Dv )−1 ushet
−1
(c1i /c1w ). (10.1.41b)

This solution formally has the same analytical form as the corresponding solution for Nchom(tm) in
homogeneous nucleation obtained in Section 8.10; however, the quantities ushet and Ψhet differ from
the homogeneous freezing case by the presence of the geometric factor f(mis). This significantly
reduces the energy DFcr,0, parameter ushet and all the other similar quantities relative to the case of
homogeneous freezing, and shifts the nucleation process to higher temperatures.
Equations (10.1.41a) and (10.1.41b) along with the equations of Section 8.10 enable a simple
estimate of the ratios of the crystal concentrations Nc,het and Nc,hom nucleated via heterogeneous and
homogeneous mode. In the latter case, the expressions are the same with replacement of ushet and Ψhet
with ushom and Ψhom (Eqns. 8.10.51) and (8.10.52), and the ratio is

N chet (tmax )
= Rht(1)/ hm Rht(2)/ hm , (10.1.42)
N c hom (tmax )

18:23:30
10.1. Analytical Parameterization of Heterogeneous Freezing Kinetics 519

where
het hom
K gen Ψ hom us hom Ψ hom ∆Fcr ,0 Ψ hom 1 Ψ hom
Rht(1)/ hm = hom
≈ ≈ 0,α 0
~ , (10.1.43)
K gen Ψ het ushet Ψ het ∆Fcr ,0 Ψ het f (mis ) Ψ het
(1 + sihet hom
, cr ) si ,cr
Rht(2)/hm = . (10.1.44)
(1 + sihom het
, cr ) si ,cr

Thus, the difference between the concentrations Nchet and Nchom is attributed to three factors that
are easily calculated: geometric factor f(mis), the difference in the critical supersaturations and in the
Ψ-functions. It will be shown in the following text that this ratio is simplified for the limiting cases
with the diffusion and kinetic regimes of crystal growth.
This method enables estimation of the supersaturation relaxation time tfc and the mean crystal
radius at the time tmax by equating the two expressions for the second term Idep with “relaxation” in
the supersaturation (Eqn. 10.1.29), which yields

− (Γ 2 /ρ v ) I dep = − siτ −fc1 . (10.1.45)

Substituting (Eqn. 10.1.38) for Idep, we obtain an expression for tfc−1:

τ −fc1 (t ) = (Γ 2 /ρis )( I dep /si ) (10.1.46a)

(0,α 0) 2 het
≈ (4π Dv ) N a J f , het exp( z r ) exp[u
α N s
shet w , cr (t )]exp(t /τ het )Ψ het (t ). (10.1.46b)

This is an expression for tfc at a time t ≤ tmax, and it is significantly simplified at t = tmax. After substi-
tution for exp[ushet swhet,cr (tmax )] from (Eqn. 10.1.40) at t = tmax, most terms are canceled and we obtain
simply
−1 het
τ fc (tmax ) = [c1i w(1 + sihet
,cr )] si ,cr . (10.1.47)

Another expression for tfc can be obtained from (Eqn. 10.1.30) for Idep and (Eqn. 10.1.46a):
∞
Γ 2 I dep rc2
τ −fc1 = = 4π Dv ∫ fc (rc , t )drc . (10.1.48)
ρis si r + ξ dep
0 c

In the diffusion regime of crystal growth, when rc >> xdep, the integral is reduced to N c rc, where rc is
the mean crystal radius, and we obtain as before
τ fc (tmax ) = [4π Dv N chet (tmax )rc (tmax )]−1 . (10.1.49)

Equating expressions in (Eqns. 10.1.49) and (10.1.47), we obtain an expression for the mean
crystal radius at t = tmax:

rc (tmax ) = [4π Dv N chet (tmax )]−1 τ −fc1

= [4π Dv N chet (tmax )]−1 c1i w(1 + sihet het −1
, cr )(si , cr ) . (10.1.50)

18:23:30
520 Parameterizations of Heterogeneous Ice Nucleation

Using values from Figs. 9.22 and 9.34, Ncm ≈ 15 L−1 at t = tmax ≈ 90 min, c1i ∼ 10−5 cm−1, sihet, cr ~ 0.2,

and w = 2 cm s−1, an estimate from (Eqn. 10.1.50) gives rc (tm ) ~ 26.6 µm , which is in good agreement
with Fig. 9.22d with rc ≈ 25 µm at 90 min. Equation (10.1.50) can be further simplified by substitut-
ing (Eqn. 10.1.41a) and (10.1.41b) for Nchet(tmax):

rc (tmax ) = ushet c1w wΨ −het1 (tmax ) ≈ τ nuc. het Ψ −het1 (tmax ). (10.1.51)

As in the case with homogeneous nucleation, heterogeneous freezing does not cease at tmax, but con-
tinues along the descending branch of sw, when supersaturation absorption by the crystals exceeds
its production by the cooling in updraft w, and nucleation ceases at time tcr2. Calculations show that
the final total Nc,tot = Nc(tcr2) is proportional to Nchet(tmax) and can be evaluated in a simple manner
following Section 8.10:
N chet (tcr 2 ) ≈ K cor ( w) N chet (tmax ). (10.1.52)

A comparison with parcel model simulations in Fig. 10.1b indicates that Kcor ≈ 2 can be a suitable
choice, since about half of the crystals nucleate at tmax < t < tcr2. Fig. 9.22d shows that the value of
the mean radius is also nearly doubled from tmax to tcr2. Thus, an approximate relation can be used:

rc (tcr 2 ) ≈ K cor ( w)rc (tm ). (10.1.53)

Equations (10.1.41a) and (10.1.41b)–(10.1.53) can be used to parameterize the crystal concentration,
mean radius, and ice water content in models with large time steps where the nucleation process is
a substep process that occurs within one time step (e.g., Lohmann and Kärcher, 2002; Morrison and
Gettelman, 2008; Gettelman et al., 2008; Sud et al., 2009; Hoose et al., 2010).

10.1.7. Diffusion Growth Limit

The limits of the general equations for heterogeneous ice nucleation are similar to those for homoge-
neous nucleation considered in detail in Section 8.10. The first practically important limit occurs at
lhet << 1. As seen from (Eqn. 10.1.37) and similar to the homogeneous freezing in Section 8.10, the
condition lhet << 1 implies small xdep and r0 that are typical of the diffusion regime of crystal growth
with the deposition coefficient ad ∼ 1 or ad > 0.1, not very large w and not very low T. In this case,
we can neglect in (Eqns. 10.1.36a)–(10.1.36d) for Ψhet all terms with xdep and r0. Using the estimates
from earlier, we can then assume that bhettmax >> 1, use the power series for erf [(lhet+b het tmax)1/2]
described in Section 8.10 and Appendix A.8 and neglect the terms with exp(−b hettmax). Then, Ψhet is
simplified in this diffusion regime as

Ψ dif ,het ≈ ( π /2)e λhet Bihet

1/2 −3/2
β het ≈ (π /2)1/2 (c3i sihet
,cr ) ushet (c1w w)−3/2 .
1/2 −3/2
(10.1.54)

Substitution of this expression into (Eqns. 10.1.41a) and (10.1.41b) yields for the crystal concentra-
tion Ncm,dif at tmax and Nc,dif after the cease of nucleation at tcr2:

N cm ,dif (tmax ) = K ihet het het −3/2

, dif (1 + si , cr )( si , cr ) (c1i w)3/2 , (10.1.55)

N c ,dif (tcr 2 ) ≈ 2 N cm ,dif (tmax ), (10.1.56)

18:23:30
10.1. Analytical Parameterization of Heterogeneous Freezing Kinetics 521

where
1/2 1/2
−3/2
 ρi Γ 2   c1w 
,dif = (2π Dv )
K ihet 1/2
 ρ  ushet c  (10.1.57a)
 is   1i 
1/2 1/2 1/2
−3/2
 ρi Γ 2   2 R ∆Fcr(α,00) (T )   c1w 
= (2π Dv )  ρ   ef  c  . (10.1.57b)
 is   kM w Lm ln(T0 /T )   1i 

The dependence on the vertical velocities, Nc,het ∼ w3/2 in (Eqn. 10.1.55) derived here analytically
is in good agreement with the parameterization Nc,het ∼ w1.47 found in Khvorostyanov and Curry
(2005a) and Curry and Khvorostyanov (2012) as a numerical fit to several hundred runs of the parcel
model and described by (Eqn. 9.15.1), which supports this analytical derivation. Note also that this
dependence, Nchet ∼ w3/2, is the same as the dependence of the crystal concentration in homoge-
neous freezing, Nchom ∼ w3/2, found in Kärcher and Lohmann (2002a), Ren and MacKenzie (2995), in
Khvorostyanov and Curry (2012) in the diffusion limit of crystal growth as described in Section 8.10.
A comparison of Nc,het described by (Eqns. 10.1.55) and (10.1.56) with the homogeneously nucle-
ated concentrations Nc,hom described by (Eqns. 8.10.58) and (8.10.59) show that their ratio in the dif-
fusion regime of crystal growth is simplified relative to (Eqns. 10.1.43) and (10.1.44) as
het
N cm , dif (t m ) ∆F s
hom
= Rdif Rht / hm , (10.1.58)
N cm , dif (t m )

where
1/2
∆F
K ihet
, dif
 ∆Fcrα,00 
Rdif = ~ hom 
~ [ f (mis )]1/2 , (10.1.59)
K ihom
, dif  ∆Fcr ,0 
3/2
(1 + sihet
, cr )
 sihom
, cr

Rhts / hm = hom  het 
. (10.1.60)
(1 + si ,cr )  si ,cr 

Thus, the ratio of the Ψ-functions vanished and the difference of the concentrations Nc,het and
∆F
Nc,hom is caused by two factors. The first factor, Rdif , arises from the difference in the critical ener-
gies of activation. Both concentrations are proportional to N c ,het ~ ( ∆Fcrα,00 )1/ 2 and N c ,hom ~ ( ∆Fcr ,0 ) ,
hom 1/ 2

which yields the factor Nc,het/Nc,hom ∼ f(mis)1/2 and tends to produce smaller crystal concentrations in
heterogeneous nucleation. The second factor Rhts / hm arises from the difference in the critical super-
het hom het 3/ 2
saturations. Since sihom
, cr is greater than si , cr , the ratio ( si , cr /si , cr ) > 1, and this leads to a tendency for
s
Rht / hm > 1 and greater Nc,het than Nc,hom. This is in agreement with Fig. 9.26, which shows that Nc,het >
Nc,hom, and (Eqns. 10.1.58)–(10.1.60) explain the reason of this. Which tendency will prevail depends
on the contact parameter mis, temperature, and other factors that determine critical supersaturations;
as Fig. 9.29 shows, at −60 °C, Nc,het only slightly exceeds Nc,hom. In any case, these equations allow a
simple estimate of the ratio of the crystal concentrations that can be nucleated in via homogeneous or
heterogeneous DF mode under similar conditions.

18:23:30
522 Parameterizations of Heterogeneous Ice Nucleation

10.1.8. The Kinetic Growth Limit, and Small and Large Particle Limits

The other limit occurs at lhet >> 1. Equation (10.1.37) shows that this condition means the kinetic
regime with large xdep (small ad) or the large initial particle radius r0 of freezing particles. As in Sec-
tion 8.10, the kinetic limit for Ψhet can be derived by expanding in (Eqns. 10.1.36a)–(10.1.36d) the
functions erf ( λ ) and erf ( λ + β tmax ) at lhet >> 1, and neglecting the terms with exp(−b tmax) and
the terms l−3/2 compared to l−1/2. Collecting terms of the same order, we arrive at an equation that has
the same form as (Eqn. 8.10.61) with replacement of bhom and lhom with bhet and lhet:

Ψ het ,kin = β het λhet [(1/2) Bihet

−1/2 −1/2 1/2 −1
β het 2
+ ξ dep −1/2
Bihet 1/2
] + Bihet −3/2 1/2
β het −1
λhet − 2ξ dep β het
= (r0 + ξ dep )−1 [(1/2) Bihet β het
−2 2
+ ξ dep −1
β het −1
] + (r0 − ξ dep )β het . (10.1.61)

This case contains two subcases: a) xdep is large (small deposition coefficient ad), but r0 is small
(small particle limit) and xdep >> r0; and b) r0 is large (large particle limit) and xdep << r0, which may
correspond to both the diffusion and kinetic regimes.

a. lhet >> 1, xdep >> r0, kinetic regime, small particle limit
Under these conditions, r0 can be neglected compared to xdep and (Eqn. 10.1.61) is simplified as

Bihet ci 3 sihet
, cr α d Vw
Ψ het , kin ,s = = 2 . (10.1.62)
2β het ξ dep ushet (c1w w)2 4 Dv
2

Substituting into (Eqns. 10.1.41a) and (10.1.41b) yields Nc at maximum tmax with swmax:
het het het het −2 2
N cm , kin , s = K kin , s (1 + si , cr )( si , cr ) (c1 w w) , (10.1.63a)

1 ushet  ρi Γ 2  c1i
,s =
het
K kin . (10.1.63b)
(π Dv ) α d Vw  ρis  c1w
het 2
Thus, in this limit N cm , kin ,s ~ w , which is the same functional dependence described in Section 8.10
for homogeneous nucleation. The temperature dependence is determined by several factors: Nhet,cm
∼ [ris(T)]−1, but the other factors, ushet, Vw, Γ2, c1i, c1w, and sihet
, cr, are also the functions of T. Note also

that the crystal concentration is inversely proportional to the deposition coefficient, Ncm,het ∼ ad−1; that
is, the smaller ad or the more polluted clouds, the greater nucleated crystal concentration. Small val-
ues of ad were reported in some measurements, especially at low temperatures (e.g., Hobbs, 1974;
Pruppacher and Klett, 1997) and Gierens et al. (2003) discussed possible reasons for small ad in ice
clouds down to 10−3. The dependence 1/ad can be significant in these cases and may lead to enhanced
crystal concentrations in polluted clouds with small ad. This is also in agreement with the data from the
INCA field experiment (Ovarlez et al., 2002; Ström et al., 2003; Haag et al., 2003; Gayet et al., 2004;
Monier et al., 2006) that found greater ice crystal concentrations in cirrus in the more polluted northern
hemisphere than in the cleaner southern hemisphere. This, in particular, could be caused by a small
deposition coefficient in the heterogeneous ice nucleation mode in polluted areas. Equation (8.10.63)

18:23:30
10.1. Analytical Parameterization of Heterogeneous Freezing Kinetics 523

for Nchom derived in Section 8.10 in this limit has the same form as (Eqns. 10.1.63a) and (10.1.63b), but
with ushom instead of ushet. This allows a simple estimate of the ratio Nchet/Nchom in this limit:
het
N cm , kin , s
hom
= Rhet
F s
, kin , s Rhet , kin , s , (10.1.64)
N cm , kin , s

ushet ∆Fcr0,,0α 0
, kin , s = = = f (mis ),
F
Rhet (10.1.65)
us hom ∆Fcrhom ,0

2
(1 + sihet
, cr )
 sihom
, cr

, kin , s =
s
Rhet hom  het 
. (10.1.66)
(1 + si ,cr )  si ,cr 

Here again, presence of the factor f(mis) causes the tendency for higher crystal concentration with
heterogeneous freezing, and the ratio of the critical supersaturations counteracts this tendency and
leads to higher concentrations with homogeneous freezing, but the latter factor is stronger than in the
diffusion growth limit.
b. lhet >> 1, large initial r0 >> xdep, large particle limit
This limit is particularly important when heterogeneous nucleation in DF mode occurs on large par-
ticles with a large insoluble core (e.g., mineral dust particles with sizes of several microns to tens or
hundreds of microns) covered by the shell of a soluble substance, which is deliquescent and forms
a solution. Heterogeneous freezing may occur on the surface of the core inside this solution. If the
soluble shell is thin, which is often observed (e.g., Levin et al., 1996; Wurzler et al., 2000), the solu-
tion in the shell may freeze rapidly after nucleation of a primary ice germ. Then, a large crystal may
form consisting of an insoluble core covered by a thin ice layer whose radius r0 is determined mostly
by the insoluble core (e.g., dust particle) and may constitute several tens or hundreds of microns, so
that r0 >> xdep. Neglecting xdep compared to r0, (Eqn. 10.1.61) can be further transformed as

r0  Bihet  r
Ψ het , kin ,l = + 1 = 0 [(2λhet )−1 + 1] ≈ r0 β h−et1 . (10.1.67)
β het  2β het r02  β het

The last equality takes into account that lhet >> 1, so the first term in the parentheses is much smaller
than the second one and can be neglected. Substituting Ψhet,kin,l into the general solution (Eqns.
10.1.41a) and (10.1.41b), we obtain
−1 het −1
, l = (4π Dv r0 het ) (1 + si , cr )( si , cr ) (c1i w),
het het
N cm (10.1.68)

where we denote r0 as r0het to emphasize the heterogeneous mode and to enable comparison with
homogeneous freezing. Now, the dependence on w is linear, Ncm ∼ w. This linear w-dependence is
in agreement with predictions in Kärcher and Lohmann (2002a,b), Ren and MacKenzie (2005), and
Khvorostyanov and Curry (2012) for homogeneous freezing described in Section 8.10. The term
ris(T) is absent; thus, the temperature dependence is much weaker than in the previous cases, and is
caused by the T-dependence of Dv, c1i, and sihet , cr .
het
The inverse dependence on the size, N cm , l ~ 1/r0 het , may seem unexpected because the nucleation

rate per particle in (Eqns. 9.6.7) and (9.6.8) is proportional to its surface area, Jf,het ∼ rN2 and one could
expect that larger IN would produce higher Nc. However, (Eqn. 10.1.38) for Idep clarifies this inverse

18:23:30
524 Parameterizations of Heterogeneous Ice Nucleation

dependence. The second term in the supersaturation (Eqn. 10.1.29) describes supersaturation relaxation
and contains Idep. The vapor sink term Idep ∼ Ψhet ∼ r0het in this limit; therefore, supersaturation relaxes
faster with increasing r0het, the maximum supersaturation is smaller (this is seen from (Eqn. 10.1.40)
for this limit). Therefore, the number of nucleated crystals decreases with increasing r0het. Thus, larger
IN may nucleate smaller crystal concentrations due to kinetic limitations.
The expression (Eqn. 8.10.66) derived for homogeneous freezing in this limit in Section 8.10 has
the same form with replacement sihet, cr → si , cr and r0het → r0hom. Thus, the ratio of the crystal concentra-
hom

tions in these modes under the same conditions is

r0 hom (1 + si ,cr ) si ,cr

het hom
N het ,cm ,l
= . (10.1.69)
N hom,cm ,l r0 het (1 + si ,cr ) sihet
hom
, cr

The factor due to the difference of the critical humidities can be ∼1.5–2 (see Fig. 9.17), which is much
smaller than the ratio of the initial radii. Suppose that homogeneous freezing occurs on haze particles
with a modal radius of ∼0.02 μm. If heterogeneous freezing takes place on the surface of dust, kaolinite,
or similar particles of coarse aerosol fractions with radii ∼0.5 μm, then the ratio of the crystal con-
centrations that could potentially form via these two modes is Nchet/Nchom ∼ r0hom/r0het = 0.04. If het-
erogeneous freezing via DF mode occurs on the particles with larger r0het from the coarse mode then
the ratio Nchet/Nchom ∼ r0hom/r0het would be smaller. This may explain lower crystal concentrations that
form at low temperatures in cirrus in the kinetic regime of crystal growth via heterogeneous mode in
the presence of ice nuclei than those formed via homogeneous freezing.

10.1.9. Parameterization for the Large-Scale Models.

Case 2: Small IN Concentration Na and Crystal Concentration Limited by Na

If the value of Na is small, then ice nucleation may cease before the maximum water supersaturation
is reached. Then, all available IN can be nucleated and will determine the final crystal concentration.
Such a situation was simulated in the parcel run #3 described in Section 9.17, with a 3-modal aerosol
distribution and Na = 10 L−1 in each mode, see Fig. 9.35. The time thet of the nucleation process can
be evaluated using (Eqn. 10.1.19), rewritten in the form:
t

N c (t ) = ∫ R f ,het (t )dt = N aQhet [exp(t /τ nuc ,het ) − 1], (10.1.70)

0

where we introduced the notation

α 0)
Qhet = cshτ het J (0, 2 het
f , het (T , rN ) exp( zα rN ) exp(ushet s w , cr ). (10.1.71)

When the limit Na of the available IN is reached, then Nc = Na, and (Eqn. 10.1.70) yields

1 = Qhet [exp(thet /τ nuc ,het ) − 1]. (10.1.72)

Solving for thet, we obtain

−1
thet = τ nuc ,het ln(Qhet + 1), (10.1.73a)

18:23:30
10.2. Temperature Effects and Heterogeneous Freezing of Cloud Drops 525

or in expanded form,

thet = τ nuc ,het ln{[cshτ nuc ,het J (0,

f , het (T , rN ) exp( zα rN ) exp(ushet sw , cr )] + 1}.
α 0) 2 −1
(10.1.73b)

If any of the multipliers in (Eqn. 10.1.73b) is large enough (e.g., J (0, α 0)

f , het ), then the nucleation process
−1
is rapid (for example, at large cooling rates), therefore Qhet >> 1 and Qhet << 1, so the ln term in
(Eqn. 10.1.73a) can be expanded and we obtain

thet ≈ τ nuc ,het Qh−et1 (10.1.74a)

(0,α 0)
= [csh J f , het
2
(T , rN ) exp( z r ) exp(ushet sw ,cr )] .
α N
−1
(10.1.74b)

That is, for rapid nucleation with limited Na, the nucleation time does not depend on tnuc,het
and is inversely proportional to the nucleation rate. In the opposite case of slow nucleation (small
−1
J (0, α 0)
f , het and other factors in (Eqn. 10.1.73b)), we have the condition Qhet << 1, and Qhet >> 1 then.
(Eqns. 10.1.73a) and (10.1.73b) are transformed as

thet = τ nuc ,het ln(Qh−et1 ), (10.1.75a)

α 0) −1
= τ nuc ,het ln[cshτ nuc ,het J (0, 2
f , het (T , rN ) exp( zα rN ) exp(ushet sw , cr )] , (10.1.75b)

i.e., the nucleation time is proportional to the logarithm of the inverse of the nucleation rate. As men-
tioned earlier, the final crystal concentration in this case is equal to the concentration Na of available
IN. Calculations of these nucleation times for various conditions may help in analyses of the labora-
tory and field experiments on IN measurements—in particular, to determine if the time of processing
in the experimental device is sufficient for the nucleation process if IN concentration is small.

10.2. Temperature Effects and Heterogeneous Freezing of Cloud Drops

The temperature effects in heterogeneous ice nucleation can be considered similar to homogeneous
freezing in Section 8.11. According to (Eqn. 9.8.7), near water saturation (sw ≈ 0), the temperature
variations of heterogeneous freezing are determined by changes in the nucleation rate J (0, α 0)
f , het (T , rN )
α
defined by (Eqn. 9.8.8), and in J act (T , rN ) describing the effects of active sites defined by
(Eqn. 9.8.9a):
(0,α 0) α
f , het (T , rN ) ≈ J f , het (T , rN ) J act (T , rN ),
J (0) (10.2.1)

while the factor in (Eqn. 9.8.7) describing sw-effect is J het s

(T , sw , mis ) = 1 at sw = 0. According to
(0)
(Eqn. 9.8.4), the temperature effects in J f ,het (T ) are caused mostly by changes in the critical energy
∆Fcrα,00 (T ) and in ΔFact, while T-variations in ∆Fcrε are smaller because of the small factor Hv,fr. The
temperature dependence of the critical energy ∆Fcrα,00 (T ) and activation energy ΔFact can be evaluated
assuming, as in Section 8.11, that the temperature change DT << T, and then expanding the terms
sis(T − DT), ri(T − DT), Lefm (T − ∆T ), and ln[T/(T − DT)] into the power series by DT/T to the first-
order terms. Substituting these expansions into (Eqn. 9.8.3) for ∆Fcrα,00 (T ) yields

∆Fcrα,00 (T − ∆T ) ≈ ∆Fcrα,00 (T )[1 − κ Tn (T ) ∆T (t )], (10.2.2a)

18:23:30
526 Parameterizations of Heterogeneous Ice Nucleation

where kTn is the same as in (Eqn. 8.11.5b),

σ is′  ρ ′ ( Lef ) ′  2
κ Tn (T ) = 3 − 2  i + mef  + , (10.2.2b)
σ is  ρi Lm  T ln(T0 / T )

and primes denote absolute values of the derivatives by T (i.e., the derivatives and DT are assumed to be
positive for the quantities decreasing with T). The activation energy also can be presented in a similar
form described by (Eqns. 8.11.6a) and (8.11.6b). Substituting these expressions into (Eqn. 9.8.8) yields

f , het (T − ∆T ) = J f , het (T ) exp[(uTact + uThet ) ∆T (t )],

J (0, α 0) (0,α 0)
(10.2.3a)
α0
 1  ∆Fcr ,0 (T )
uThet (T ) =  κ Tn (T ) −  , (10.2.3b)
 T kT
 1  ∆F (T )
uTact (T ) =  κ Ta (T ) −  act . (10.2.3c)
 T  kT

The quantity J acα t (T , rN ) that describes the effect of active sites averaged over the size spectrum fa(rN)
is according to (Eqn. 10.1.5):

 ∆F α (r )   α σ (1 − mis )rN2 
α
J act (α a , mis , rN ) ~ exp  a N  ≈ csh N a exp  a is . (10.2.4)
 kT   kT 

The energy of the active sites Faα = α aσ is (1 − mis )rN2 defined in (Eqn. 9.7.20b) can be presented
in the form of expansion using (Eqn. 9.17.1) for the temperature-dependent active site fraction aa(T)
from Curry and Khvorostyanov (2012), and expanding aa(T) and sis(T) by DT/T:

∆Fαα (T − ∆T ) ≈ ∆Fαα (T )[1 − κ Tas (T ) ∆T (t )], (10.2.5a)

κ Tas (T ) = α a′ (T ) /α a (T ) + σ is (T ) /σ i′s (T ). (10.2.5b)

Substituting these expressions into (Eqn. 10.2.4), we obtain for the temperature effect of the active
sites
α α
J act (T − ∆T ) = J act (T ) exp[− uTas ∆T (t )], (10.2.6)
 1  F α (T )
uTas (T ) =  κ Tas (T ) −  a . (10.2.7)
 T  kT

The parameters uThet, uTact, and uTas in [K−1] determine changes in the corresponding expressions
for nucleation rates at temperature decrease DT. Substituting these expressions into (Eqn. 10.2.1),
we obtain the combined effect of the temperature variations DT in the critical and activation energies
DFcr, DFact, and the energy of the active sites Faα on the nucleation rate J (0)
f , het in (Eqn. 9.8.15) (at

supersaturation sw ≈ 0) that can be written similar to (Eqn. 8.11.7):

J (0) (0,α 0) α
f , het (T − ∆T , rN ) ≈ J f , het (T , rN ) J act (T , rN ) exp[ BThet ∆T (t )], (10.2.8)
BThet = uTa + uThet − uTas . (10.2.9)

The parameter denoted BThet with the dimension [K−1] describes an increase in Jf,het with temperature
decrease DT at sw ≈ 0. As in Section 8.11, the temperature decrease DT can be related to the time

18:23:30
10.2. Temperature Effects and Heterogeneous Freezing of Cloud Drops 527

dependence via the temperature lapse rate g and vertical velocity w using the temperature equations
from Section 3.11, and its integration by time:

dT/dt = Tɺ = −γ w, ɺ = γ wt .
∆T (t ) = − Tt (10.2.10)

The minus sign in the second equation arises because we defined DT > 0 as the temperature decreases
and dT/dt < 0. Substituting this DT into (Eqn. 10.2.8), we obtain the time dependent J (0)
f , het and nucle-

ation rate Rf,het(t) at sw ≈ 0:

dN c
R f ,het (t ) = = J (0)
f , het (T − ∆T , rN ),
dt
≈ J f ,het (t0 , rN ) exp(β Thet t ) ≈ J (0)
(0)
f , het (t 0 , rN ) exp(t /τ Thet ), (10.2.11)

where we introduce again the characteristic freezing frequency bThet and time tThet,

β Thet (T ) = BThet γ w = BThet (− dT /dt ), (10.2.12a)

−1 −1
τ Thet = [( BThet )γ w] = [( BThet )(− dT/dt )] . (10.2.12b)

The first form of these equations with g w can be convenient in numerical models where g and w are
known, and the second form with (−dT/dt) can be more convenient for analysis of laboratory experi-
ments where dT/dt is known. Integration of (Eqn. 10.2.11) over time yields

f , het (t 0 , rN , t 0 )τ Thet [exp(β Thet t ) − 1].

N c (t ) = J (0) (10..2.13)

So, the time dependence of the crystal concentration due to temperature decreases is similar to that
due to the supersaturation variations described in Section 10.1. If we consider freezing of deliques-
cent haze particles, then the temperature correction and the joint effect of the supersaturation and
temperature variations can be simply accounted for by replacing in the equations of Section 10.1
for Jf,het and Nc(t) the frequency bshet with (bshet + bThet). If we consider the heterogeneous freezing of
water drops near water saturation, sw ≈ 0, then only the terms with bThet are essential and the equations
of this section can be used.
For small times or temperature changes, if bThett << 1, the exponent in (Eqn. 10.2.13) can be
expanded and (Eqn. 10.2.13) is reduced to
(0,α 0) α
N c (t ) = tJ (0)
f , het (t 0 , rN , t 0 ) = tJ f , het (T , rN ) J act (T , rN ), (10.2.14)

where the time dependence of Nc is linear in this limit. For large times or temperature changes, if
bThett >> 1, the time dependence in (Eqn. 10.2.13) becomes exponential,

f , het (T , rN ) J act (T , rN )τ Thet exp(β Thet t ).

N c (t ) = J (0, α 0) α
(10.2.15)

Equations (10.2.14) and (10.2.15) are analogous to those derived in Section 8.11 for homogeneous
nucleation and may explain the difference in the nucleation rates at small and large temperature
changes DT. If a permanent and significant cooling rate is present, the rate of crystal formation is
exponential according to (Eqn. 10.2.15). If a permanent source of cooling is absent, and there are
only small random temperature fluctuations, the rate of crystal production is close to linear with time
as in (Eqn. 10.2.14). Vali (1994, 2008) described the experiments on the heterogeneous freezing of

18:23:30
528 Parameterizations of Heterogeneous Ice Nucleation

drops with an alternating cooling rate and found exponential growth of Nc(t) at a constant cooling
rate and nearly constant Nc(t) with a very weak increase in the absence of the regular cooling rate.
Equations (10.2.14) and (10.2.15) may provide an explanation for these observations.
It follows from (Eqn. 10.2.12a) that

β Thet ∆t = BThet (− dT /dt ) ∆t = BThet ∆T . (10.2.16)

Using this relation, (Eqn. 10.2.15) can be rewritten for ice crystals nucleated during interval Dt as

f , het (t 0 , rN , t 0 )τ Thet exp( BThet ∆T )

N c ( ∆t ) = J (0)
exp( BThet ∆T )
= J (0, α 0) α
f , het (T , rN ) J act (T , rN ) , (10.2.17)
BThet (− dT/dt )

where we used (Eqn. 10.2.12b) for tThet.

The theoretical exponential temperature dependence of Nc in (Eqn. 10.2.15) is similar to the cor-
responding dependence for homogeneous freezing in Section 8.11 and to the empirical parameter-
izations Nc(T) ∼ exp(bFDT) for heterogeneous ice nucleation suggested by Fletcher (1962), Cooper
(1986), Sassen (1992), Diehl and Wurzler (2004), and others described in Section 9.4. The parameter
BThet [K−1] is a theoretically derived analogue of the empirical parameter bF introduced by Fletcher
(1962) and others in similar parameterizations. The average value of the exponent in Fletcher’s was
bF ≈ 0.6 K−1, although its wide variations were found; Vali (1994) determined the average value to
be ∼0.54 K−1.
We can now compare the exponential T-dependence derived from the theory with the empiri-
cal parameterizations. An estimate is done at −20 °C with the parameterization (Eqn. 4.4.15a) for
sis by Pruppacher and Klett (1997), (Eqn. 4.4.22) for ri(T), and (Eqn. 8.8.12a) for Lefm (T ), which
gives s ′is(T) /sis(T) ∼ 1.1 × 10−2 K−1, r ′i(T) /ri(T) ∼ 2.4 × 10−3 K−1, [ Lefm (T )]′ /Lefm (T ) ~ 10 −2 K −1, and
ln(T0/T) ≈ 5 × 10−2 K−1, which yields kTn ∼ 0.1 K−1. Assuming DFcr ∼ 10−12 erg and d Fcr /kT ∼ 28.6,
we get uThet ∼ 2.75 K−1. An estimate with (Eqn. 8.3.20) for DFact(T) from Zobrist et al. (2007) gives
kTa ∼ −1.2 × 10−2 K−1, and uTact ∼ −0.14 K−1. Using the model from Curry and Khvorostyanov (2012)
of T-dependent active sites described by (Eqn. 9.17.1), aa(T) = α0(1 − Tc /Tv) with α0 = 2 × 10−5,
Tc = T − T0, and Tv = −25 °C, we estimate aa ≈ 0.4 × 10−5 and aa′/aa ≈ 0.2 K−1 at Tc = −20 °C. This
gives us kTas ≈ 0.214 K−1. Assuming rN ∼ 0.5 μm, mis = 0.5, aa ≈ 0.4 × 10−5, and the energy of active
sites Faa ≈ 0.2 × 10−12 erg, then (Eqn. 10.2.7) gives uTas ≈ 1.2 K−1. Finally, we obtain BThet = uThet +
uTact − uTas ≈ 1.4 K−1. This is comparable to but still higher than Fletcher’s mean value 0.6 K−1. If
DFcr ∼ 0.7 × 10−12 erg, which corresponds to a slightly smaller contact parameter mis < 0.5 and shape
factor f(mis, x), then with the same kTn and all the other parameters, we obtain uThet ∼ 1.92 K−1 and
BThet = 0.58 K−1, very close to the mean experimental value.
Thus, classical nucleation theory explains the exponential temperature dependence of ice nucle-
ation by freezing, and the corresponding empirical parameter bF can be expressed via the param-
eters of classical theory and fundamental constants. However, it should be noted that the parameter
BThet itself is a function of temperature and may vary with T. Further, (Eqn. 10.2.15) shows that
the actual temperature dependence of Nc is more complicated. Along with this exponential depen-
dence, Nc ∼ exp(BThetDT), there is also temperature dependence of Nc in the denominator in BThet(T).
Another important fact follows from (Eqn. 10.2.15), that with the same temperature interval DT,

18:23:30
10.3. Parameterization of Deposition Ice Nucleation Based on Classical Nucleation Theory 529

the concentration of nucleated crystals is inversely proportional to the cooling rate dT/dt—i.e., the
slower the cooling rate, the larger the number of crystals nucleating at the same temperature, which
is in agreement with observations. A more detailed comparison of the theoretical description of the
temperature dependence of heterogeneous ice nucleation with the experimental data would allow
refinement of some parameters of classical nucleation theory.

10.3. Parameterization of Deposition Ice Nucleation Based on Classical Nucleation Theory

At sufficiently low temperatures (usually below −20 °C to −25 °C) and low humidities, liquid drops
may be absent and ice nucleation occurs via direct deposition of water vapor on aerosol particles that
serve as ice nuclei. Deposition nucleation has been studied in laboratory experiments by Möhler et al.
(2006) and Connolly et al. (2009), among others. The critical energies and nucleation rates for the
ice deposition process were derived in Section 9.5 and can be used in models with sufficiently small
time steps. Parameterization of this process for large-scale models is quite similar to parameteriza-
tion of homogeneous and heterogeneous freezing in Sections 8.10 and 10.1 and is based on several
assumptions.
Since the critical radius rcr of an ice germ for deposition is ∼(1–3) × 10−2 μm (see Fig. 9.3), and the
effective radii rN of IN on which deposition occurs are usually > 0.1–0.5 μm, we assume again that
rN >> rcr. Using this assumption, the geometric factor f(miv, x) in (Eqn. 9.2.21) is reduced to f(miv) in
(Eqn. 9.2.15) with replacement of mwv → miv and does not depend on rN. Numerical simulations of
deposition nucleation with parcel models show that the temporal behavior of the ice supersaturation
and crystal concentration is similar to those in the freezing process shown in Fig. 9.34. Nucleation
begins at some critical supersaturation sidep , cr , increases to maximum values simax at tmax, when Nc =

Ncmax; then, supersaturation absorption begins to exceed supersaturation production, si decreases and
reaches its second critical point, and then nucleation ceases.
As in the previous parameterizations of freezing in Sections 8.10 and 10.1, we approximate
the growing branch of si at tcr1 < t < tmax as a linear function, si ( t ) = sidep dep
, cr + c1i wt = si , cr + ∆si , where

Δsi = c1iwt, and c1i is defined in (Eqn. 5.3.46a). The critical energy of a deposition ice germ formation
can be written using (Eqn. 9.5.9) with the relation Si = 1 + si, and incorporating these assumptions:

16π σ iv3 f (miv )

∆Fcr = . (10.3.1)
3 [ Rv T ρi ln(1 + sidep 2 2
, cr + ∆si ) − Cε ε ]

Numerical simulations show that ∆si ( tmax ) << sidep

, cr , and that the second term with e in the denomina-

tor is much smaller than the first term with ln. Thus, we can expand the denominator and retain first-
order terms using the relation ln(1 + x) ≈ x and obtain
(0)
∆Fcr (si , t ) = ∆Fdep (sidep
, cr )[1 − κ dep ∆si (t )], (10.3.2)

where
κ dep = 2{(1 + sidep dep 2 −1
,cr )[ln(1 + si ,cr ) − M w Cε ε /( RT ρ i )]} , (10.3.3)
(0) 16π σ f (miv )
3
iv
∆Fdep = . (10.3.4)
3 [ Rv T ρi ln(1 + sidep 2 2
, cr ) − Cε ε ]

18:23:30
530 Parameterizations of Heterogeneous Ice Nucleation

(0)
That is, ∆Fdep is the critical energy at the beginning of nucleation. Substitution of (Eqn. 10.3.2) into
(Eqn. 9.5.11) yields the deposition nucleation rate per unit area that can be written in various forms:

 ∆Fdep
(0)
κ dep c1i wt 
J sdep = J sdep
(0)
exp 
 kT 
(0)
(
 = J sdep exp usdep c1i wt , )
= J sdep
(0)
exp(β sdep t ) = Jsdep
(0)
exp(t /τ sdep ), (10.3.5)

where
usdep = ∆Fdep
(0)
κ dep / kT , (10.3.6)
2
c1s ev π r Z s
(0)
J sdep (rN , sidep (0)
,cr ) = Csdep exp(− ∆Fdep / kT ), Csdep = cr
, (10.3.7)
(2π mw1 kT )1/2

and we introduced the “deposition frequency” bdep, and the “deposition nucleation time” tsdep,
−1
β sdep = usdepc1i w, τ sdep = β sdep = (usdepc1i w)−1 . (10.3.8)

The kinetic coefficient Csdep depends on si(t) and on time via rcr as Csdep ∼ rcr2, but this power law
time dependence of Csdep is much weaker than the exponential time dependence and we assumed
(0)
that J sdep (0)
(rN , si ) ≈ J sdep (rN , sidep
,cr ) .

The nucleation rate per particle Jdep = 4prN2 Jsdep in (Eqn. 9.5.12) can now be written as
(0)
J dep = J dep (rN , sidep
, cr ) exp( β sdep t ), (10.3.9)
(0) 4π 2 rcr2 Z s c1s ev
J dep = Cdep rN2 exp(− ∆Fi (0)
, dep /kT ), C dep = . (10.3.10)
(2π mw1 kT )1/ 2

The polydisperse nucleation rate in an ensemble of particles is obtained by integration of Jdep over
the size spectrum by rN:
rmax
dN dep
Rdep = = exp(β sdep t ) ∫ dr (rN , sidep
(0)
N f (rN ) J dep , cr )
dt rmin

= N a J dep , cr ) exp( β sdep t ),

(rN , sidep
(0)
(10.3.11)

(0)
where J dep (rN , sidep
, cr ) depends on the mean radius rN ,

, cr ) = C dep ( si , cr )rN exp( − ∆Fi , dep /kT ).

(rN , sidep
(0) dep 2 (0)
J dep (10.3.12)

Integration of (Eqn. 10.3.11) by time yields Ndep(t):

t

N dep (t ) = ∫ Rdep (t ′)dt ′ = N a J dep

(0)
(rN , sidep
, cr )τ sdep [exp(β sdep t ) − 1] (10.3.13a)
0

, cr )τ sdep exp( β sdep t ),

(rN , sidep
(0)
≈ N a J dep (10.3.13b)

18:23:30
10.3. Parameterization of Deposition Ice Nucleation Based on Classical Nucleation Theory 531

where the second equation holds if bsdept >>1. This parameterization can be used in numerical models
for evaluation of Ndep(t) nucleating by deposition mode at a time t. Equation (10.3.13b) can be pre-
sented in an alternative form using the relations β sdept = usdepc1i wt = usdep ∆si = usdep [si (t ) − sidep
,cr ]:

N dep (t ) ≈ N a exp{adep + usdep [si (t ) − sidep

, cr ]},

≈ N a exp[usdep si (t ) + (adep − usdep sidep

, cr )] (10.3.13c)
adep = ln[ J (rN , s(0)
dep
dep
i , cr )τ sdep ]. (10.3.13d)

Equation (10.3.13c) resembles an empirical parameterization of deposition nucleation (Eqn. 9.4.7)

suggested by Möhler et al. (2006) based on laboratory experiments, while the coefficients adep and
usdep are expressed here via the aerosol properties and parameters of classical nucleation theory.
If the time step in a model is greater than the duration of nucleation, we need as before to calculate
Ndep(tmax) with si = simax and then after the end of nucleation. The supersaturation equation required for
evaluation of simax(tmax) is the same as (Eqn. 10.1.29), but the deposition integral Idep is now
t
4π Dv ρis
I dep (t ) = si
Γ2 ∫r
0
c , ef (t , t0 ) Rdep (t0 ) dt0 , (10.3.14)

where rc,ef(t,t0) is the same as defined in (Eqn. 10.1.31), but replacing Bihet → Bidep. We assume
dep
again that the crystal growth rate can be calculated with si ( t ) ≈ const ≈ sidep , cr because ∆ si << si ,cr ,

then the parameter that describes the crystal growth rate is Bidep = 2ci 3 si ,cr . Substituting Rdep from
dep

(Eqn. 10.3.11) into (Eqn. 10.3.14) yields

4π Dv ρis
I dep (t ) = si (0)
N a J dep J 0 i ,dep (t ), (10.3.15)
Γ2

where, similar to Section 10.1,

t 3
J 0 i ,dep (t ) = ∫ rc ,ef (t , t0 ) exp(β sdept0 ) dt0 = ∑ J 0( ki ,)dep , (10.3.16)
0 k =1
t

J 0( ki ,)dep = ∫ rc(,kef) (t , t0 ) exp(β sdept0 ) dt0 . (10.3.17)

0

The integrals J 0( ki ,)dep are evaluated as described in Section 8.10 and Appendix A.8, or in Section 10.1
and are expressed again via the Ψ-function but with different arguments
3
β sdep t
J 0 i ,dep = ∑J (k )
0 i , dep =e Ψ dep , (10.3.18)
k =1

Ψ dep = Ψ1,dep + Ψ 2,dep + Ψ 3,dep . (10.3.19)

The three components of the function Ψdep are expressed with analytical (Eqns. 10.1.36b)–(10.1.36d)
with the parameter ldep defined similar to lhet in Section 10.1, but with different critical parameters:

(ξ dep + r0 )2 β sdep (usdep c1w w)(ξ dep + r0 )2

λdep = = . (10.3.20)
Bidep 2ci 3 sidep
,cr

Substitution of J0i,dep(t) from (Eqns. 10.3.17)–(10.3.18) into (Eqn. 10.3.14) yields

4π Dv ρis (0) β sdep t

I dep (t ) = si N a J dep e Ψ dep (t ). (10.3.21)
Γ2

18:23:30
532 Parameterizations of Heterogeneous Ice Nucleation

Using again the supersaturation equation (10.1.29) and the condition dsi(tmax)/dt = 0 when si = simax,
we obtain the integral Idep(tmax):

I dep (tmax ) = c1i w(1 + sidep

, cr ) ρ is / Γ 2 . (10.3.22)

Equating (Eqn. 10.3.21) at t = tmax and (Eqn. 10.3.22) with the approximation simax ≈ sidep
, cr yields

dep −1 −1 (0) −1 −1
exp(β sdep tmax ) = c1i w(1 + sidep
,cr )( si ,cr ) (4π Dv ) ( N a J dep ) Ψ dep . (10.3.23)

Parcel model simulations show that, as in the case with freezing in Sections 8.10 or 10.1, the duration
of the nucleation process is usually much longer than tsdep, so that bsdep tmax >> 1, and (Eqn. 10.3.13b)
can be applied. Substituting (Eqn. 10.3.23) into (Eqn. 10.3.13b) yields
gen dep −1 −1
N cdep (tmax ) = K dep (1 + sidep
,cr )( si ,cr ) Ψ dep , (10.3.24a)
gen −1 −1
K dep = (4π Dv ) u sdep . (10.3.24b)

These equations are similar to those derived for freezing in Sections 8.10 or 10.1, with replacement
of the corresponding parameters with usdep, sidep, cr , and Ψdep. The mean crystal radius at tmax can be

estimated as in Sections 8.10 and 10.1, equating the two expressions for the second term in the super-
saturation equation, which yields as in (Eqn. 10.1.46a), τ −fc1 (t ) = (Γ 2 /ρis )( I dep /si ) . Substituting here
(Eqn. 10.3.22) for Idep yields the supersaturation relaxation time at tmax:
−1 dep
τ fc (tmax ) = [c1i w(1 + sidep
,cr )] si ,cr . (10.3.25)

Assuming the diffusion crystal growth rate, and using the expression τ −fc1 ≈ (4π Dv N c rc ) , we obtain

rc (tmax ) = [4π Dv N cdep (tmax )]−1 c1i w(1 + sihet het −1

, cr )(si , cr ) . (10.3.26)

Numerical simulations with the parcel model indicate that Ncdep and the mean crystal radius after the
end of nucleation are nearly doubled relative to tmax:

N cdep (tcr 2 ) ≈ 2 N cdep (tmax ), rc (tcr 2 ) ≈ 2rc (tmax ). (10.3.27)

The equations derived here can be used for parameterization of the crystal concentration and mean
radius in the models with the large time steps where deposition nucleation is a substep process.
The asymptotics of Ncdep in various regimes are determined by the same asymptotic expressions of
the Ψ-function as in Sections 8.10 and 10.1. The diffusion and kinetic limits for the deposition mode
are determined by the values of the parameter ldep defined by (Eqn. 10.3.20).
The diffusion regime of crystal growth with the deposition coefficient ad > 0.1 implies ldep << 1.
As is seen from (Eqn. 10.3.20) and that is similar to the homogeneous freezing in Section 8.10 or
heterogeneous freezing in Section 10.1, the condition ldep << 1 implies small xdep and r0 that are
typical of the diffusion regime of crystal growth with the deposition coefficient ad ∼ 1 or ad > 0.1,
not very large w and not very low T. Using the diffusion asymptotic Ψdif from (Eqn. 10.1.54) and
replacing all the corresponding quantities with those for the deposition mode, we obtain Ncdep in the
diffusion regime:
dep dep dep dept −3/2
N cm , dif (t max ) = K i , dif (1 + si , cr )( si , cr ) (c1i w)3/2 , (10.3.28a)

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10.4. General Properties and Empirical Parameterizations of Contact Nucleation 533

1/2 1/2
−3/2
 ρi Γ 2   c1w 
,dif = (2π Dv )
K idep 1/2
 ρ  usdep c  . (10.3.28b)
 is   1i 

Another asymptotic limit with ldep >> 1, xdep >> r0, corresponds to the limit of the kinetic regime
of crystal growth and small particles. Using the asymptotic value of Ψhet,kin,s from (Eqn. 10.1.62), and
replacing all the corresponding quantities with those for the deposition mode, we obtain Ncdep:
dep dep dep dep −2 2
N cm , kin , s (t max ) = K kin , s (1 + si , cr )( si , cr ) (c1 w w) , (10.3.29a)

1 usdep  ρi Γ 2  c1i
,s =
dep
K kin . (10.3.29b)
(π Dv ) α d Vw  ρis  c1w

The large particle asymptotic limit occurs for ldep >> 1 and large initial r0 >> xdep. This limit can
be particularly important in the atmosphere when heterogeneous deposition nucleation occurs on
large particles—e.g., on large mineral dust particles with r0 ≥ 0.1–0.5 μm as often used in the lab
experiments. In contrast to the deliquescence-freezing mode described in Section 10.1, these par-
ticles should not be covered by a soluble shell to prevent the freezing mode and initiate ice nucleation
in the deposition mode. Substituting the limit (Eqn. 10.1.67) for the Ψ-function into the general
(Eqns. 10.3.24a) and (10.3.24b), we obtain
−1 dep −1 −1
,l (t max ) = (4π Dv ) (1 + si ,cr )( si ,cr ) r0 dep (c1i w),
dep dep
N cm (10.3.30)

where we denote r0 as r0dep to emphasize the deposition mode and to relieve comparison with the
freezing modes. Now, the dependence on w is linear, Ncm ∼ w.
The final crystal concentrations after nucleation ceases can be approximately calculated for these
limits, as for the general case, as Nc ≈ 2Ncm(tmax).

10.4. General Properties and Empirical Parameterizations of Contact Nucleation

10.4.1. General Properties

In Chapter 9 and Sections 10.1–10.3, we considered three of the four modes of heterogeneous ice
nucleation in clouds: deposition, deliquescence-freezing (or condensation-freezing), and immersion
freezing. The last of the major heterogeneous modes, contact nucleation, is considered in the fol-
lowing sections. The term “contact nucleation” refers usually to a process when an aerosol particle
(AP) collides with a supercooled drop and initiates freezing from outside (Young, 1974a,b, 1993;
Pruppacher and Klett, 1997). Shaw et al. (2005) and Durant and Shaw (2005) suggested recently
a more extended treatment. They observed freezing of evaporating drops, and found that some IN
particles that did not cause freezing being fully immersed in the drop, initiated freezing when these
IN reached and contacted the surface of an evaporating droplet from inside or were partially released
from the drop. This led to an increase in ice nucleation temperatures. This mechanism was termed
“contact nucleation inside out.”
The contact mode has several distinguishing features. The temperature thresholds are usually
higher in this mode than in the deposition and immersion modes and are comparable to those in the
condensation-freezing mode (Young, 1974a,b; Cooper, 1995; Table 4.1 in Young, 1993; Shaw et al.,

18:23:30
534 Parameterizations of Heterogeneous Ice Nucleation

2005, Durant and Shaw, 2005; Djikaev and Rukenshtein, 2008; Hoose and Möhler, 2012; Ladino et al.,
2013). Therefore, this mode was invoked for possible explanation of intensive ice crystal formation
in relatively warm clouds when ice multiplication mechanisms may be ineffective. In contrast to the
other modes caused by the freezing of a single aerosol particle or cloud drop, contact nucleation is
a more complicated phenomenon that includes two sub-processes: collection of aerosol particles by
cloud drops and subsequent freezing. The primary three processes that cause the collection of aerosol
particles by cloud drops and determine collection rates are Brownian diffusion, thermophoresis, and
diffusiophoresis. Young (1974b, 1993) calculated these collection rates and showed that the net rate
is higher at water subsaturation in clouds than at supersaturation. Due to these features, contact nucle-
ation has often been invoked to explain fast cloud crystallization at relatively warm temperatures
in the downdrafts near cloud edges, where mixing with the environment occurs, or in descending
branches of the waves (e.g., Cooper and Vali, 1981; Hobbs and Rangno, 1985; Rangno and Hobbs,
1991; Cotton and Field, 2002).
The mechanism of contact nucleation is still poorly understood and several hypotheses have been
suggested to explain the higher IN efficiency in this mode than in the others. Fletcher (1968, 1970b)
considered the following two mechanisms. The first mechanism may act when a dry aerosol particle
contains on its surface active sites (small areas of morphological, chemical, or electrical inhomogene-
ities stimulating ice germ formation). When such a particle is brought into contact with a supercooled
drop and the etching of active sites is slower than nucleation of freezing, then this aerosol particle
can be an effective contact nucleus. The second mechanism occurs when a small aerosol particle con-
taining both hygroscopic and insoluble parts deliquesces and the solution is concentrated so that its
freezing point can be depressed by 5–10 °C. The deliquesced particle does not freeze via condensation-
freezing mode, but when it contacts a drop, the substantial dilution eliminates this depression and
initiates freezing. Note that this mechanism includes the deliquescence-freezing heterogeneous mode
considered in Chapter 9 as a part of contact nucleation.
Cooper (1974) based his hypothesized mechanism on an assumption that a dry aerosol particle in
a saturated vapor possesses both deposition and immersion ice germs on its surface, with the critical
germ radii rcr proportional to the corresponding surface energies ssv at the ice–vapor interfaces and
ssl at the ice–water interface as described in Sections 9.5 and 9.7. The value ssv ≈ 4–5 ssl, and rcr is
much smaller in the immersion mode. Thus, even if an aerosol particle is inactive in the deposition
mode, it can be active in the contact mode when the immersion germ upon contact with a cloud drop
meets “the native” liquid medium, growing above supercritical size and then freezing. Fukuta (1975)
suggested another mechanism whereby, after contact of an aerosol particle with a drop, the water
front propagates along the nucleus surface and creates local high interface energy zones that reduce
the free energy and stimulate ice nucleation.
Djikaev and Ruckenstein (2008) compared efficiencies of the contact and immersion modes in
the framework of a thermodynamic model. To determine if and how the surface of a liquid droplet
can thermodynamically stimulate its heterogeneous crystallization, they examined crystal nucle-
ation in the immersion and contact modes by deriving and comparing with each other the reversible
works of formation of crystal nuclei in these cases. They found that the line tension of a three-phase
contact gives rise to additional terms in the formation free energy of a crystal cluster and affects
its Wulff (equilibrium) shape. The proposed model was applied to the heterogeneous nucleation of

18:23:30
10.4. General Properties and Empirical Parameterizations of Contact Nucleation 535

hexagonal ice crystals on generic macroscopic foreign particles in water droplets at T = 253 K. The
results showed that the droplet surface does thermodynamically favor the contact mode over the
immersion one.
In general, contact ice nucleation represents a two-stage process. The first stage consists of the
formation of some number of contact ice nuclei from interstitial aerosol particles that could contact
drops and potentially initiate freezing. The second stage consists of the scavenging of these potential
IN by drops and freezing. The hypotheses by Fletcher (1968), Cooper (1974), and Fukuta (1975)
dealt with ice embryos nucleation on a single aerosol particle and did not consider in detail the
scavenging and accumulation of aerosol particles by the drops. Brock (1962), Waldman and Schmidt
(1966), Slinn and Hales (1971), and Young (1974b) evaluated in detail aerosol fluxes, scavenging
and collection rates with an emphasis on contact ice nucleation. The processes of aerosol scavenging
by drops are considered in Section 10.5, and the combined processes of scavenging and freezing are
considered in Section 10.6.

10.4.2. Empirical Parameterizations

Several empirical parameterizations of contact nuclei concentrations were developed and used in
cloud and climate models. Young (1974a) suggested a parameterization of the concentration of active
contact nuclei in terms of temperature T and surface concentration Ncn0 as a power law:

N cn = N cn0 (270.15 − T )1.3 , (10.4.1)

where Ncn0 = 2 × 102 L−1 is the number of active ice nuclei at sea level, decreasing to 10 L−1 at a height
of 5000 m. This scheme was used by Young (1974a) in a cloud model for simulation of orographic
clouds. Cotton et al. (1986) simulated in a cloud model with bulk microphysics both stages of contact
nucleation—i.e., combining Ncn(T) from (Eqn. 10.4.1) with evaluation of the total rate of scavenging
of contact nuclei colliding with drops due to Brownian and phoretic aerosol fluxes, using a diagnosed
supersaturation for phoretic fluxes, and then calculating the contact freezing rate. Meyers et al. (1992)
concluded that Young’s T-dependence (Eqn. 10.4.1) may overestimate the concentration of contact
nuclei and suggested an exponential parameterization:

N cn = N cn 0 exp[acn + bcn (273.15 − Tc )], (10.4.2)

with Ncn in L−1, Tc in degrees Celsius, Ncn0 = 1 L−1, acn = −2.80, bcn = 0.262, and where ice is not
permitted to form at Tc > −2 °C. Equation (10.4.2) yields lower Ncn than (Eqn. 10.4.1), ∼0.2 L−1 at
−3 °C and ∼1 L−1 at −10 °C. These parameterizations may explain higher threshold temperatures for
contact nucleation than for the condensation-freezing mode but remain insufficient to explain contact
nucleation by some organic aerosol particles at −3 °C, with higher Nc observed by Fletcher (1972).
The parameterization (Eqn. 10.4.2) coupled with the evaluation of aerosol collection rates was used
in Meyers et al. (1992) to modify the Cotton et al. (1986) parameterization and simulate the oro-
graphic cloud system.
Similar approaches with use of submicron contact nuclei of various origin and sizes were applied
to simulate the effect of contact nucleation on the convective clouds (e.g., Ovtchinnikov and Kogan,
2000; Ovtchinnikov et al., 2000), Arctic mixed-phase stratocumulus clouds (Morrison et al., 2005a,b;

18:23:30
536 Parameterizations of Heterogeneous Ice Nucleation

Morrison and Pinto, 2005), and global cloudiness and indirect aerosol effects with the ECHAM4 cli-
mate model (Lohmann, 2002; Lohmann and Diehl, 2006). Sensitivity tests indicated that the assumed
number and size of contact nuclei can have a large impact on the evolution and characteristics of
mixed-phase clouds, particularly the partitioning of condensate between droplets and ice. How-
ever, there is currently no unified point of view on the properties and concentrations of the contact
nuclei. Although aerosol fluxes to the drops substantially vary with the aerosol radius (Slinn and
Hales, 1971; Young, 1974b, 1993; Pruppacher and Klett, 1997; see Section 10.5 here), models often
assumed a monodisperse aerosol.
The effect of the contact nuclei size on the efficiency of freezing is also not clear. Some earlier
experiments indicated an increase of the freezing probability with an increasing IN size (e.g., Young,
1993; Pruppacher and Klett, 1997). However, Hoose and Möhler (2012) analyzed the available recent
data and found contradictory results. Rzesanke et al. (2011) found a clear increase of the contact
freezing efficiency with particle size, although this effect was not observed or was much weaker in
the studies by Ladino et al. (2011) and Bunker et al. (2012). Aerosol fluxes to the drops depend on the
size of the aerosol particle; therefore, contact freezing should depend on the size of aerosol particles
with maximum fluxes to the drops. The major mechanisms of aerosol scavenging that govern the
fluxes of contact nuclei to or from the droplets, and their possible effects on the contact nucleation
process are considered in the next sections.

10.5. Aerosol Scavenging by Drops

The collection scavenging rates of aerosol particles by a drop are analogous to the coagulation rates
considered in Section 5.6. The scavenging rate is defined as the rate of accumulation of aerosol vol-
ume by a drop per unit time [cm3 s−1]. As discussed in Section 10.4, the following three mechanisms
govern the collection of aerosol particles by the drops: 1) Brownian diffusion; 2) thermophoresis;
3) diffusiophoresis. A brief description of these mechanisms is provided next.

10.5.1. Brownian Diffusion

It is a result of the random collisions of air molecules with AP that causes AP to move in the direc-
tion of the smallest concentration. The term convective Brownian diffusion is applied to the Brown-
ian diffusion enhanced by the convection of the particles. In the case of the diffusion of AP toward
the drops, this convective enhancement is caused by the drops’ fall velocity and is described by the
ventilation corrections. The collection or scavenging rates KCB [cm3 s−1] for convective Brownian
diffusion can be written as:
K CB (rd , ra ) = 4π D p (ra )rd ϕ v ,br (rd , ra ). (10.5.1)

Here, Dp(ra) is the Brownian diffusion coefficient of an aerosol particle:

kT∞
D p (ra ) = Csl ,r (ra ), (10.5.2)
6πηa ra

18:23:30
10.5. Aerosol Scavenging by Drops 537

where k is the Boltzmann constant, T∞ is the temperature far from the drop (at “infinity”), ha is the air
dynamic viscosity, the first fraction in (Eqn. 10.5.2) is Einstein’s coefficient of Brownian diffusion,
and Csl,r(ra) is Cunningham’s slip-flow correction:

Csl ,r (ra ) = 1 + α sl (ra ) N Kn (ra ). (10.5.3)

Here, NKn(ra) = la /ra is the Knudsen number, la is molecular free path, and

α sl (ra ) = Asl + Bsl exp[−Csl /N Kn (ra )]. (10.5.4)

The values of the parameters in (Eqn. 10.5.4) chosen here are Asl = 1.257, Bsl = 0.40, Csl = 1.10. These
values are somewhat different from Waldman and Schmidt (1966) and Young (1974b) and are based
on newer data (e.g., Seinfeld and Pandis, 1998, Pruppacher and Klett, 1997). The term la is a function
of temperature T and pressure p:

λa (T , p) = λa0 ( p0 /p)(T/T0 ), (10.5.5)

where la0 = 0.66 × 10−5 cm, p0 = 1013 mb, and T0 = 273.15 K. To determine the Brownian diffusion
coefficient in (Eqn. 10.5.2), the term ha is parameterized as a function of T following Pruppacher and
Klett (1997):

ηa (T ) = (1.718 + 0.0049Tc − 1.2Tc2 ) × 10 −4 , Tc < 0º C, (10.5.6)

where Tc is temperature in Celsius, and ha is in poise (1 poise = g cm-1 s-1). The ventilation correc-
tion jv,br in (Eqn. 10.5.1) arises from droplet sedimentation, and is parameterized following Slinn and
Hales (1971), Young (1974b) as

ϕ v , p (rd , ra ) = 1 + 0.3 N R1/e2 (rd ) N Sc

1/ 3
, p (ra ). (10.5.7)

Here, NRe(rd) = 2Vt(rd)rdra/ha is the Reynolds number for the drops, ra is the air density, Vt(rd) =
Cv,sl(rd)Vt0(rd) is the terminal velocity of the drops, Vt0(rd) is the drop terminal velocity without slip
correction parameterized analytically in Beard (1976, 1980), Böhm (1989, 1992), or Khvorostyanov
and Curry (2002, 2005b) (see Chapter 12), and Cv,sl(rd) is the slip correction for Vt defined in (Eqn. 10.5.4)
but with NKn(rd) for the drops. The NSc,p(ra) = na/Dp is the Schmidt number for aerosol particles,
na = ha /ra is the air kinematic viscosity.

10.5.2. Thermophoresis

It is the transport of aerosol particles in a temperature gradient in the suspending gas. A simplified
explanation of this effect is that the aerosol particles in a temperature gradient are non-uniformly
heated, and air molecules striking an aerosol particle from the warm side transfer a greater impulse to
the aerosol particle than from the cold side, resulting in a flux of aerosol particles from warm to cold.
The collection rates for this process are evaluated according to Brock (1962), Waldman and Schmidt
(1966), and Slinn and Hales (1971) as:
4π Bth (ra ) k a rd
K Th = (T∞ − Ts )ϕ v ,th (rd ), (10.5.8)
p

18:23:30
538 Parameterizations of Heterogeneous Ice Nucleation

where Ts and Tì are the temperatures on the drop surface, and far from the drop. The factor Bth is
0.4(1 + α sl ,r N Kn )( k a + 2.5k p N Kn )
Bth (ra ) = , (10.5.9)
(1 + 3 N Kn )( k p + 2 k a + 5k p N Kn )

where ka and kp are thermal conductivities of air and aerosol particles, and the slip function asl,r(ra) is
defined by (Eqn. 10.5.4). The ventilation correction for this process is

ϕ v ,th (rd ) = 1 + 0.3 N R1/2e (rd ) N Pr1/3 , (10.5.10)

where NPr = hacp / ka is the Prandtl number, cp is the isobaric specific heat capacity of the air. Slinn and
Hales (1971) and Young (1974b, 1993) expressed the temperature difference DT = T∞ − Ts via the cor-
responding difference of the vapor densities. It is more convenient, using the heat balance equation
(Eqn. 5.1.28) to express DT directly via fractional water supersaturation sw = (rv∞ − rws) /rws, where
rv∞ and rws are the water vapor densities at infinity and on the drop surface (see Chapter 5):

Dv Le DLρ
T∞ − Ts = − ( ρ v∞ − ρ ws ) = − v e ws sw . (10.5.11a)
ka ka

Here Dv is the vapor diffusion coefficient and Le is the latent heat of condensation.
The thermophoretic fluxes are often considered as in (Eqn. 10.5.8), which do not account for the
kinetic correction. As we have seen in Section 5.1, this form corresponds to the diffusion regime of
condensation. Since the thermophoretic flux is generated by and related to the condensation flux,
which may occur in both the diffusion and kinetic regimes, a generalized parameterization is desir-
able for the thermophoretic flux. A generalized parameterization for both the diffusion and kinetic
regimes is developed here based on the method of the boundary sphere as in Section 5.1. This leads
to an effective diffusion coefficient D*v defined by (Eqn. 5.1.22a,b) and gives a kinetic correction jkin
to the thermophoretic flux:

1 4 Dv
ϕ kin = , ξcon = , (10.5.11b)
1 + ξcon /rd α cVw

where ac is the condensation coefficient, and Vw is the molecular thermal velocity. Substituting
(Eqns. 10.5.9)–(10.5.11b) into (Eqn. 10.5.8) we obtain the thermophoretic collection kernel:

4π Bth rd Dv Le
K Th = (− sw ) ρ wsϕ kinϕ v ,th (rd ). (10.5.12)
p

This form of the thermophoretic collection kernel is convenient for cloud models where supersatura-
tion is evaluated solving the supersaturation equations described in the previous chapters or where it
is diagnosed as in Cotton et al. (1986). Equation (10.5.12) shows that KTh ∼ (−sw)—i.e., the direction
of the thermophoretic flux is opposite to the condensation flux. In the case of a growing drop, the
thermophoretic aerosol flux is directed from the drop and prevents collection of aerosol particles by
the drop, and in the case of an evaporating drop, the flux is directed to the drop, and increases aerosol
collection rate.

18:23:30
10.5. Aerosol Scavenging by Drops 539

10.5.3. Diffusiophoresis

It refers to the process of transport of aerosol particles by the hydrodynamic airflow, termed Stefan
flow. For a growing drop, sw > 0, the vapor pressure equals the saturated pressure ews at the drop
surface and ews(1 + sw) > ews far from the drop. Thus, the water vapor pressure decreases toward the
drop. Since the total pressure of the air–vapor mixture is roughly constant, the air pressure increases
toward the drop and causes the diffusive counterflow of air molecules from the drop. Since there is
no source of air molecules on the drop surface, this sets up a Stefan flow toward the drop when the
drop is growing. For an evaporating drop, the directions of these fluxes are reversed. That is, the dif-
fusiophoretic flux of aerosol particles is in the same direction as the vapor flux, toward a growing
drop and away from an evaporating drop.
The collection rate KDf for this process was derived in Waldman and Schmidt (1966), Slinn and
Hales (1971), and Young (1974b) in terms of the vapor densities or pressures. Here we express KDf
in a more convenient form via water supersaturation sw and also introduce the kinetic correction jkin
that accounts for both the diffusion and kinetic regimes and intermediate cases:
ρ v∞ − ρ ws
K Df = 1.2 × 4π Dv rd ϕ kinϕ v ,df (rd )
ρa
= 1.2 × 4π Dv rd sw qsϕ kinϕ v ,df (rd ), (10.5.13)

where qs is the saturated specific humidity. The ventilation correction for this case is

ϕ v ,df (rd ) = 1 + 0.3 N R1/e2 (rd ) N S1c/3 , (10.5.14)

where NSc = na /Dv is the Schmidt number. The signs of KDf and sw are the same, showing that the
directions of condensation and diffusiophoretic_flux coincide, while the directions of the thermopho-
retic and diffusiophoretic fluxes are opposite. The generalization here of the thermophoretic and dif-
fusiophoretic fluxes accounting for the kinetic correction allows us to study the effects of variations
of the condensation coefficient on contact nucleation and aerosol scavenging.
The total collection (or scavenging) rate Ksc can be evaluated as the sum of the preceding
3 processes:

K sc = K Br + K Th + K Df . (10.5.15)

Fig. 10.2 shows the three relative collection rates—Brownian, diffusiophoretic (D), and thermo-
phoretic (Th)—and the net rate (their sum) for a drop with a radius rd = 10 μm at evaporation with
sw = −2% and condensation with sw = 0.1%. Calculations are performed at T = −5 °C, p = 600 mb, and
two values of the condensation coefficient: ac = 0.04 and 1. These Figures give the absolute values of
all the collection rates. Diffusiophoresis D is negative at sw = −2%, and thermophoresis Th is negative
at sw = 0.1%, their absolute values are denoted as |D| and |Th|, respectively. The phoretic fluxes with
ac = 1 are 25–40% greater than with ac = 0.04. Thermophoresis here promotes aerosol collection at
evaporation, while diffusiophoresis opposes it. The net collection rate is positive at evaporation in the
considered range of aerosol radii 0.01 ≤ ra ≤ 1 μm, but decreases more than 10 times with increasing
aerosol size. At sw = 0.1%, which corresponds to the cloud volumes with condensation, the net col-
lection rate decreases much faster with increasing aerosol size and becomes negative at ra ≥ 0.4 μm

18:23:30
540 Parameterizations of Heterogeneous Ice Nucleation

1 1
sw = –2 % Brownian Net<0 sw = 0.1 %, condens.
evaporation Th, 0.04 Brownian
Aerosol radius (µm)

Aerosol radius (µm)

Net<0
|D|, 0.04 |Th|, 0.04
Net, 0.04 D, 0.04
Th, 1 |Net|, 0.04
0.1 |D|, 1 0.1 |Th|, 1
Net, 1 D, 1
|Net|, 1

0.01 0.01
2 3 5 2 3 5 2 3 5
1E–8 1E–7 1E–6 1E–5 1E–9 1E–8 1E–7 1E–6 1E–5
Relative collection rates (cm3 s–1) Relative collection rates (cm3 s–1)
(a) (b)

Figure 10.2. Relative collection rates. (a) Evaporation with sw = −2%; (b) condensation with
sw = 0.1%. Calculations are performed at T = −5 °C, p = 600 mb, and two values of the condensation
coefficient, ac = 0.04 and 1. The components of aerosol fluxes are denoted as: Brownian,
diffusiophoresis (D), and thermophoresis (Th). Net means the sum of these three fluxes. The digits
near notations are the values of ac (1 or 0.04). The absolute values of all the collection rates are
given in these Figures. Diffusiophoresis D is negative at sw = −2%, and thermophoresis
Th is negative at sw = 0.1%; their absolute values are denoted as |D| on the left panel and |Th| on the
right panel. The net collection rate at condensation becomes negative at ra ≥ 0.4 μm with ac = 0.04
and at ra ≥ 0.23 μm with ac = 1 as indicated in the upper left corner of (b).

with ac = 0.04 and at ra ≥ 0.23 μm with ac = 1 as indicated in the upper left corner of Fig. 10.2b. Thus,
collection of the larger particles is prohibited, and contact nucleation may be suppressed.
These features of scavenging led Young (1974b) and others to the conclusion that contact nucle-
ation is favored in the evaporation regions of clouds. Figs. 10.3a,b represent the collection rates as
isopleths for the range of aerosol radii ra = 0–1 μm and drop radii rd = 0–100 μm. Figs. 10.3a,b in
general support the conclusion that the net collection rates are greater at evaporation. The net rates are
negative at condensation at rd ≤ 10 μm for aerosol particles with ra ≥ 0.2–0.4 μm, so that such particles
cannot be collected by the small-size drop fraction. However, these figures show that the picture
of aerosol scavenging may be more complicated and condensation regions may also contribute to
contact nucleation for larger drops with rd ≥ 10–20 μm. Fig. 10.3b shows that in the condensation
regions, the net collection rates are positive except for a small range at rd ≤ 10 μm, and increase with
increasing drop radius. Collection rates are smaller at condensation, but since the probability of freez-
ing is proportional to the squared radius of the aerosol particle, this could compensate for smaller
collection rates at condensation and lead to comparable effects of aerosol in contact freezing in both
the evaporating and condensing cloud portions.
Recent field studies during CRYSTAL-FACE-2002 of the size spectra even of relatively large
dust aerosol transported from African dust storms to the Florida area showed that the submicron
size fraction may be mostly responsible for cloud glaciation (e.g., Sassen et al., 2003; DeMott et al.,
2003; Cziczo et al., 2004). Such dust particles could be captured by the clouds and initiate con-
tact freezing, which may explain glaciation of rather warm Ac clouds at −5 to −9 °C (Sassen et al.,
2003). Similar superposition of the submicron fractions of dust particles was used by Zhang et al.
(2011) in simulations of the effects of dust as ice nuclei on tropical hurricane development. Although

18:23:30
10.6. Freezing and Scavenging Rates 541

1.0
evaporation
sw = –2 %

Aerosol radius (µm)

0.8

2E–007
0.6

0.4

5E–007

06

06
6

1E–0
00

–0
0.2 – 05
–0

3E
5E 1E

0 10 20 30 40 50 60 70 80 90 100
Droplet radius (µm)
(a)

1.0
condensation
sw = 0.1 %

06
Aerosol radius (µm)

0.8

–0
1E
09

0.6
–2E–0

0.4
08
1E 0
–0

0.2 08 07
–0 –0 –00
7
006 –006
6E 2E 5E 1E– 2E 4E–006

0 10 20 30 40 50 60 70 80 90 100
Droplet radius (µm)
(b)

Figure 10.3. Net collection rates (cm3 s−1) in the form of isopleths as the functions of the drop and
aerosol radii rd and ra calculated with the same parameters as in Fig. 10.2 (T = −5 °C, p = 600 mb)
for evaporation with sw = −2% (a) and condensation with sw = 0.1% (b). The solid and dashed lines
denote positive and negative values.

Figs. 10.2 and 10.3 are based on somewhat idealized choices of the aerosol and droplet size spectra
and supersaturations, they illustrate the possibility of aerosol scavenging by droplets that may cause
contact nucleation.

10.6. Freezing and Scavenging Rates

The number Na of aerosol particles collected (scavenged) by a drop of a radius rd can be calculated
with the equation:

∂Na
= K sc (rd , ra )na∞ (ra ), K sc = K Br + K Th + K Df , (10.6.1)
∂t
where Ksc(rd,ra) is defined in Section 10.5 as the total collection (scavenging) kernel for aerosol
particles with radius ra by a drop of radius rd, and na∞(ra) is the concentration of aerosol particles
of radius ra far from the drop. When we consider a polydisperse ensemble of aerosol particles with

18:23:30
542 Parameterizations of Heterogeneous Ice Nucleation

the size spectrum fa(ra), this equation should be generalized. If we denote dNa(rd,ra) as the number
(dimensionless) of aerosol particles in the size range (ra, ra + dra) captured in unit time by a drop with
rd, then the collection rate can be written as

∂δ N a (rd , ra )
= K sc (rd , ra ) fa (ra )dra , (10.6.2)
∂t
and the number of particles captured by the drops in the radii interval (rd, rd + drd) in time Dt is
d Na = (∂d Na /∂t)d t.
The aerosol particles that have not been frozen before being captured by a drop can be of various
origins with different characteristics. For example, these can be haze solution particles with high
concentrations of solute that depress the freezing point and suppress their freezing, or the insoluble
particles without liquid film on their surface that could freeze. Another reason that could prevent
their freezing before contact can be subsaturation sw < 0 due to the factor exp[ushetsw(t)] as described
by (Eqn. 10.1.1) with ushet from (Eqn. 9.8.11). These can be interstitial aerosol particles or particles
becoming interstitial due to the mixing of cloud volumes with the environment. The effect of differ-
ent particles on contact freezing may be different depending on their nature, but the action of each
type of such IN on contact freezing can be evaluated based on any hypothesis on their properties, and
using the expressions for probabilities of freezing described in Chapter 9, Section 10.1, and evaluat-
ing collection rates as described in Section 10.5.
We illustrate these mechanisms with calculations of scavenging and freezing rates based on the
hypothesis that a haze solution particle has not been frozen before the contacting drop due to solute
effects or the freezing depression by subsaturation. When such a haze particle contacts a drop—e.g.,
in the slightly subsaturated portion of the cloud—rapid dilution of the solute occurs. Humidity around
such contact IN becomes close to 100% on the drops’ surfaces, favoring the initiation of freezing.
The probability of freezing of an aerosol particle with radius ra in a time interval Dt is

P (ra , ∆t ) = 1 − exp[− J f ,het (ra ) ∆t ], (10.6.3)

where Jf,het(ra) is the rate of ice germ formation per unit time per particle. Freezing depends on the
temperature, humidity, and radius of the aerosol particle as specified in Section 9.6, and it can be
assumed that sw ≈ 0 on the drop’s surface. The probability of freezing in time Dt of a drop with rd
that captures dNa(rd,ra) of aerosol particles with similar properties is proportional to the number of
captured particles and the probability of their freezing:

Pˆ (rd , ra , ∆t ) = P (ra , ∆t )δ N a (rd , ra ) = P (ra , ∆t ) K sc (rd , ra ) fa (ra )dra ∆t , (10.6.4)

and the drop freezing rate is Pˆ (rd , ra , ∆t )/ ∆t . The corresponding freezing rate Ψcf (rd, Dt) (s−1) of the
drops that capture aerosol particles is the integral over the aerosol size spectrum:

Ψ cf (rd , ∆t ) = ∫ P(ra , ∆t ) K sc (rd , ra ) fa (ra )dra

ra

= ∫ P(ra , ∆t )[ K Br (rd , ra ) + K Th (rd , ra ) + K Df (rd , ra )] fa (ra )dra . (10.6.5)

ra

The freezing rate of the drops in the size range (rd, rd + drd) is
dfd , fr (rd )
= Ψ cf (rd , ∆t ) fd ,uf (rd ), (10.6.6)
dt

18:23:30
10.6. Freezing and Scavenging Rates 543

where fd,uf (rd) is the size spectrum of unfrozen droplets. Depletion of the size spectrum of unfrozen
drops is

∂ fd ,uf (rd )
= −Ψ cf (rd , ∆t ) fd ,uf (rd ). (10.6.7)
∂t
Now we introduce the characteristic contact freezing time tc,fr that describes the rate of drops freezing
due to contact nucleation:
τ c , fr = Ψ cf−1 (rd , ∆t ). (10.6.8)

This characteristic time is analogous to the supersaturation absorption time and characterizes an
e-fold decrease in fd,uf (rd) if Ψcf were constant.
Fig. 10.4 shows freezing coefficients Ψcf (rd) and times τc,fr(rd) calculated with (Eqns.10.6.5)
and (10.6.8) due to Brownian diffusion, thermophoresis, and diffusiophoresis at evaporation with

0.1 0.1
sw = –2 % Net Droplet contact freezing sw = 0.1 %
Droplet contact freezing

evaporation 0.01 condensation

0.01
Th Net |Dif| |Th|
ratesΨ (s–1)
ratesΨ (s–1)

1E–3 Br
1E–3 Net
1E–4 Dif
1E–4 Br
Br Th 1E–5 Br
|Dif| |Th|
1E–5 1E–6 Dif
Net
Net
1E–6 1E–7
1 10 100 1 10 100
Droplet radius (µm) Droplet radius (µm)
(a) (b)
Droplet freezing time (min)

Droplet freezing time (min)

1.0E+3 1.0E+3 sw = 0.1 %

sw = –2 %
1.0E+2 1.0E+2

1.0E+1 1.0E+1
Brownian
1.0E+0 1.0E+0 Brownian
Thermophor.
Diffusiophor.
1.0E–1 Net 1.0E–1 Net
1.0E–2 1.0E–2
1 10 100 1 10 100
Droplet radius (µm) Droplet radius (µm)
(c) (d)

Figure 10.4. Freezing coefficients Ψcf(rd) and contact freezing times τc,fr (rd) due to Brownian
diffusion (Br), thermophoresis (Th), and diffusiophoresis (Dif) at evaporation with subsaturation
−2% (left column, (a), (c) and growth with supersaturation 0.1% (right column, (b), (d). The integral
in (Eqn. 10.6.5) of diffusiophoresis is negative at evaporation, its absolute value is denoted as |Dif|
in Fig. 10.4a; the integral from thermophoresis is negative at condensation, and its absolute value is
denoted as |Th| in Fig. 10.4b.

18:23:30
544 Parameterizations of Heterogeneous Ice Nucleation

subsaturation −2% (left column) and condensation with supersaturation 0.1% (right column). Calcu-
lations are done using the same parameters as in Fig. 10.2: T = −5 °C, p = 600 mb, and ac = 0.04. The
aerosol size spectrum fa(ra) includes 200 grid points by 0.05 μm from 0.01 to 1 μm and was chosen
close to the continental type (Seinfeld and Pandis, 1998, Table 7.3) as a 3-modal lognormal spectrum
with the mean geometric radii of 0.01, 0.058, and 0.9 μm, and dispersions 1.45, 1.65, and 2.45. The
droplet spectrum included 100 points by 1 μm to 100 μm.
Fig. 10.4 shows that in the evaporation case with sw = −2%, the net freezing rates and times are
determined mostly by the thermophoresis (positive here), with Brownian diffusion providing a minor
contribution. Negative diffusiophoresis tends to decrease the freezing rate but its contribution is much
smaller than that of thermophoresis. In the condensation case with sw = 0.1%, Brownian diffusion
dominates the net rates, with diffusiophoresis and thermophoresis (negative here) playing minor
roles. The freezing rates increase with increasing drop radius from (1–3) × 10−5 s−1 at rd = 1 μm to
0.03–0.05 s−1 at = 100 μm. The corresponding freezing times decrease with increasing radius, from
∼600 s at evaporation and ∼1000 s at condensation for rd = 1 μm to 0.3 s (sw = −2%) and 0.6 s
(sw = 0.1%) for rd = 100 μm. Thus, contact ice nucleation can be quite possible and rapid in the pres-
ence of moderately large drops, both in the subcloud layer at evaporation and in the growing cloud
portion if sufficiently large particles have been formed by coagulation. This conclusion agrees with
observations of Hobbs and Rangno (1990) and Rangno and Hobbs (1991), who observed rapid cloud
glaciation after the stage of intensive coagulation in maritime convective clouds and concluded that
contact nucleation could be one explanation for this effect. In interpreting Fig. 10.4, it should be
emphasized that freezing may significantly vary with the concentrations and size spectra of the back-
ground aerosol. More general conclusions require a series of model simulations with varying aerosol
properties and drop spectra.
The contact freezing rate initiated by the aerosol particle with radius ra, or the rate of crystal pro-
duction by this process, [dNc(ra)/dt]cont, [cm−3 s−1], is the integral over the drop size spectrum

 dN c (ra )  ∞

 dt  =
cont
∫ 0
Ψ cf (rd , ∆t ) fd (rd ) drd , (10.6.9)

and the number of crystals formed due to contact nucleation by IN with ra in a time step Δt is

 dN (r )  ∞
∆N c ,cont (ra , ∆t ) =  c a  ∆t = ∫ Ψ cf (rd , ∆t ) fd (rd ) drd ∆t . (10.6.10)
 dt  cont 0

The scavenging of aerosol particles by drops causes a decrease in aerosol concentration. The evolu-
tion of the aerosol size spectrum with an assumption of the complete capture of particles by the drops
can be evaluated by integration of (Eqn. 10.6.2) over the drop size spectrum. This leads to a kinetic
equation for fa(ra):

∂ fa (ra )
= −Λ sc (ra ) fa (ra ), (10.6.11)
∂t
where Λsc(ra) is the spectral aerosol scavenging coefficient,
∞
Λ sc (ra ) = ∫ K sc (rd , ra ) fd (rd ) drd
0
∞
= ∫ [ K Br (rd , ra ) + K Th (rd , ra ) + K Df (rd , ra )] fd (rd ) drd . (10.6.12)
0

18:23:30
10.6. Freezing and Scavenging Rates 545

The inverse quantity

τ sc (ra ) = Λ sc−1 (ra ), (10.6.13)

is the characteristic scavenging time of aerosol with radius ra.
Fig. 10.5 shows scavenging coefficients Λsc(ra) and times tsc(ra) calculated using (Eqns. 10.6.12)
and (10.6.13) due to Brownian diffusion, thermophoresis, and diffusiophoresis at evaporation with
subsaturation −2% and condensation with supersaturation 0.1%. The aerosol size spectrum included
200 grid points by 0.005 μm from 0.001 to 1 μm. The droplet spectrum included 100 points by 1 μm
to 100 μm and was approximated as a gamma distribution with the concentration 500 cm−3, mean
radius 10 μm, and an index of gamma distribution p = 6.

Scavenging coefficients Λ (s–1)

Scavenging coefficients Λ (s–1)

1.0E+0 sw = –2 % 1.0E+0 sw = 0.1 %

evaporation condensation
1.0E–1 1.0E–1
1.0E–2 1.0E–2 Br
1.0E–3 Net Th 1.0E–3
1.0E–4 |Dif| 1.0E–4 Br
Dif Net
1.0E–5 Br 1.0E–5
|Th| Net
1.0E–6 1.0E–6
1E–3 0.01 0.1 1 1E–3 0.01 0.1 1
Aerosol radius (µm) Aerosol radius (µm)
(a) (b)
Aerosol scavenging time (min)

Aerosol scavenging time (min)

1.0E+4 sw = –2 % 1.0E+4 sw = 0.1 %

1.0E+3 1.0E+3

1.0E+2 1.0E+2

1.0E+1 1.0E+1
Brownian
Brownian
1.0E+0 Thermophor. 1.0E+0 Diffusiophor.
Net Net
1.0E–1 1.0E–1
1E–3 0.01 0.1 1 1E–3 0.01 0.1 1
Aerosol radius (µm) Aerosol radius (µm)
(c) (d)

Figure 10.5. Scavenging coefficients Λsc(ra) and times tsc(ra) due to Brownian diffusion (Br),
thermophoresis, and diffusiophoresis at evaporation with subsaturation −2% (left column)
and condensation with supersaturation 0.1% (right column). The integral in (Eqn. 10.6.12) of
diffusiophoresis is negative at evaporation, and its absolute value is denoted as |Dif| in Fig. 10.5a.
The integral from thermophoresis is negative at condensation, and its absolute value is denoted as
|Th| in Fig. 10.5b.

18:23:30
546 Parameterizations of Heterogeneous Ice Nucleation

Figs. 10.5a,c show that in the evaporation case, the net scavenging rates are determined mostly
by Brownian diffusion for small aerosol particles with ra ≤ 0.03–0.04 μm, and by thermophoresis at
larger radii ra. According to (Eqn. 10.5.2), the Brownian diffusion coefficient Dp(ra) ∼ ra−1, while
thermophoresis in (Eqn. 10.5.12) very weakly depends on ra. Therefore, Λsc(ra) strongly decreases
from ∼0.1 s−1 at ra = 10−3 μm to 4 × 10−4 s−1 at ra = 0.04 μm, and is almost independent of radius at
larger sizes. The net coefficient Λsc near ra ≈ 1 μm becomes slightly smaller than the thermophoretic
integral due to the contribution of the negative diffusiophoresis. The scavenging time increases from
0.1 min at ra = 10−3 μm to 40 min at ra ≈ 0.04 μm; weaker depends on the radius at larger sizes: It
reaches ∼60 min at ra = 0.1 μm and 160 min at ra = 1 μm. Thus, scavenging by cloud of aerosol with
radii larger than 0.1 μm is a rather slow process in this example.
In the growth regime (Fig. 10.5b,d), the scavenging coefficient is determined mostly by Brown-
ian diffusion in the range ra ≈ 0.001 to 0.25 μm, where it decreases from 0.1 s−1 to less than
10−5 s−1. At ra > 0.3 μm, Brownian diffusion is small, the net coefficient Λsc(ra) is determined mostly
by diffusiophoresis and thermophoresis, which have different signs, and their sum tends to zero at
ra > 0.4 μm. Thus, Λsc(ra) becomes smaller 10−6 s−1, eventually becoming negative at ra > 0.56 μm,
making scavenging absent. The corresponding scavenging time increases with increasing aerosol
radius from ∼0.1 min at ra = 0.001 μm to 60 min at ra = 0.03 μm, and exceeds 7 hours at ra > 0.1 μm,
making scavenging of such particles very slow in this example.
The total crystal contact nucleation rate (dNc/dt)cont [cm−3 s−1] includes integrals over both aerosol
and drop size spectra and can be obtained by integration of (Eqn. 10.6.5) over the drop size spectrum
or integration of (Eqn. 10.6.9) over the aerosol spectrum:

 dN i  ∞
  = ∫0 P (ra , ∆t ) Λ sc (ra ) fa (ra ) dra
dt cont
∞ ∞
= ∫ P (ra , ∆t ) fa (ra ) dra ∫ K sc (rd , ra ) fd (rd )drd . (10.6.14)
0 0

The equations given allow calculations of the nucleation rates and concentrations of ice crystals
formed at each time step in a model for the given collection rates described in Section 10.5 and freez-
ing rates specified in Chapter 9 and Section 10.1.

18:23:30
11
Deliquescence and Efflorescence
in Atmospheric Aerosols

11.1. Phenomena of Deliquescence and Efflorescence

In Chapters 6 and 7, we considered hygroscopic growth of aerosol particles. This growth can pro-
ceed only at sufficiently high relative humidities (RHW), exceeding some critical value. At very low
humidities, atmospheric aerosol particles consisting of inorganic salts are solid. As RHW increases,
the particles begin to absorb water on their surface and grow by adsorption, but this growth is usually
insignificant.
Aerosol transformation at increase and decrease of the relative humidity is illustrated in Fig. 11.1.
When RHW reaches some threshold value, specific for each substance, the salt particle begins to deli-
quesce, whereby liquid patterns or patches of solution form on the surface. As the humidity further
increases, these patches merge and form a thin liquid film, which gradually thickens, and then the
entire solid particle dissolves and transforms into a solution drop, and its radius abruptly grows. This
is the point of deliquescence D in Fig. 11.1. If the solution is homogeneous and contains only one
solute, this solid–liquid phase transition is similar to the surface melting considered in Section 9.9: It
occurs as homogeneous or quasi-heterogeneous surface nucleation, usually at some critical relative
humidity or within a very low range of humidities. This humidity is called the deliquescence rela-
tive humidity (DRH). For example, DRH is ≈75.3% for solutions of NaCl and ≈80% for ammonium
sulfate at 298 K. If a less soluble salt or another insoluble foreign substance is contained in solution—
e.g., mineral dust inclusions, the solid–liquid transition may start earlier and occurs as heterogeneous
nucleation within some wider range of humidities as indicated by the curve with squares in Fig. 11.1
(Richardson and Snider, 1994; Tang, 1997; Oatis et al., 1998; Onasch et al., 1999, 2000). After deli-
quescence occurred, further hygroscopic growth is possible with increasing humidity as described in
Chapters 6 and 7 and as indicated by the upward arrow in Fig. 11.1 at Sw ≥ 0.8.
When relative humidity decreases, the reverse process of aerosol evaporation proceeds (downward
arrow in Fig. 11.1). However, the solution drop does not transform back into a solid particle at the
same DRH typical of deliquescence, but remains liquid down to substantially lower humidities. The
solution is then supersaturated with respect to solute concentration or solute activity and exists in
the metastable state. When decreasing humidity reaches another threshold value, called efflorescence
relative humidity (ERH), a phase transition into solid state, or salt crystallization, occurs, which is
called efflorescence. If a solution drop is homogeneous without admixture of any other substances
or impurities, then homogeneous efflorescence occurs as the homogeneous nucleation of salt crystals
at some critical ERH (point E in Fig. 11.1). For example, ERH was measured at ≈32–37% for bulk
ammonium sulfate and ≈45% for NaCl at room temperatures for homogeneous efflorescence. The

547
548 Deliquescence and Efflorescence in Atmospheric Aerosols

3.0
Kr2005, exp.
Effl., TM1994
2.5 Del., TM1994

Growth factor rw(Sw)/rd

Effl., Onasch1999
Del., Onasch1999
2.0
KC2007, mod.

D
1.5
E

1.0
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Saturation ratio Sw

Figure 11.1. Illustration of aerosol deliquescence, hygroscopic growth, and efflorescence.

The experimental data are from Kreidenweis et al. (2005, Kr2005) for hygroscopic growth,
and adjustments from Tang and Munkelwitz (1994, TM1994) and from Onasch et al. (1999,
Onasch1999) for deliquescence and efflorescence. Model calculations of hygroscopic growth
are from Khvorostyanov and Curry (2007, KC2007) described in Chapter 6. The points D and E
indicate the deliquescence and efflorescence points. The arrows indicate directions of the processes:
deliquescence at point D, growth at Sw ≥ 0.8, evaporation at Sw ≤ 0.8, and efflorescence at point E.

solution can be characterized by the solute supersaturation S* = as ,ef /as ,sat , defined as the ratio of the
salt activity as,ef at efflorescence to the saturated activity at deliquescence as,sat. At the point of homo-
geneous efflorescence, S* may reach 20–30.
If there is a foreign insoluble or partially insoluble substrate inside this supersaturated solution,
then heterogeneous efflorescence may occur as salt crystallization via the heterogeneous nucleation
process, similar to heterogeneous ice nucleation (Section 9.7). For example, Richardson and Snider
(1994) experimentally studied heterogeneous efflorescence using KCl as a catalyst in experiments
on efflorescence of NaCl, CsCl, and KF that occurred in heterogeneous mode. Oatis et al. (1998) and
Onasch et al. (2000) used CaCO3 and BaSO4 as heterogeneous catalysts of efflorescence of ammo-
nium sulfate, (NH4)2SO4, solutions. They found that ERH of heterogeneous efflorescence is 10–15%
higher than at homogeneous efflorescence and the salt supersaturation S* can be 40–70% lower
than its homogeneous value. At the efflorescence point, ternary soluble salt mixtures may exhibit
a step-wise salt crystallization at several critical values of ERH—e.g., the KCl-NaCl system (Tang
and Munkelwitz, 1994; Oatis et al., 1998). This behavior is similar to the step-wise crystallization of
seawater that contains several salts (Curry and Webster, 1999).
Thus, the process and critical humidity of the deliquescence-hygroscopic growth at increasing
humidity are different from the process and critical humidity at evaporation-efflorescence at decreas-
ing humidity. This phenomenon is called humidity hysteresis, by analogy with the phenomena of
hysteresis in the magnetic and electrical fields. This hysteresis effect and the exact values of the DRH
11.2. Theories and Models of Deliquescence and Efflorescence 549

and ERH are important for cloud physics because the aerosol optical properties, the direct and indi-
rect aerosol effects, and the processes of CCN activation or freezing are different in the liquid versus
the solid states. In particular, if the environmental humidity exceeds these thresholds, cirrus clouds
may form via homogeneous and heterogeneous freezing of solutions considered in the previous chap-
ters, and when the salts are in the solid state at low humidities below ERH ice nucleation may proceed
via deposition on the salt particles (Abbatt et al., 2006; Shilling et al., 2006).
The deliquescence and efflorescence relative humidities are temperature-dependent, and usu-
ally increase with decreasing temperature. Measurements usually indicate rather weak temperature
dependence of deliquescence—e.g., for ammonium sulfate, DRH ≈ 80% at T = 25 °C, and increases
slightly to 82–83% at −20 to −30 °C (Tang and Munkelwitz, 1993; Xu et al., 1998; Onasch et al.,
1999). Tabazadeh and Toon (1998) suggested fitting DRH(T) with a polynomial of the inverse powers
of the absolute temperature T:

 a a a 
DRH (T ) = exp  at 0 + t1 + t 22 + t 33  . (11.1.1)
 T T T 

Onasch et al. (1999) determined the coefficients at0 = 4.9015, at1 = −6.1612 × 102, at2 = −2.0656 × 105,
and at3 = −2.0716 × 107. This fit illustrates the general tendency, but is valid only for ammonium
sulfate for certain values of particle radius and environmental pressure.
Data obtained by various authors on the temperature dependencies of efflorescence critical humid-
ity differ. Xu et al. (1998) found rather significant growth of ERH toward colder temperatures, while
Onasch et al. (1999) and Czizco and Abbatt (1999) found much weaker dependence. It was found
also that the ERH increases with decreasing size. This dependence becomes especially strong at par-
ticle radii smaller than 0.1–0.2 mm. Using experimental data on the deliquescence, efflorescence, and
freezing of ammonium sulfate solutions, Xu et al. (1998) constructed a general phase diagram for the
stable and metastable equilibriums and phase transitions for ammonium sulfate.

11.2. Theories and Models of Deliquescence and Efflorescence

Several theoretical models have been developed to explain the observed features of the deliquescence
and efflorescence processes. Some of these models are described next.
Wexler and Seinfeld (1991) and Tang and Munkelwitz (1993) studied the temperature variations
of deliquescence relative humidity DRH(T) using the Clausius–Clapeyron equations for solution and
water vapor, combined with the empirical parameterizations of the salt solubilities. Xu et al. (1998)
applied this model to explain measured properties of the saturated solutions and DRH(T). This model
is described in more detail in the next section. Chen (1994) evaluated the positions of the deliques-
cence points on Köhler’s curves in a simplified manner, assuming that the deliquescence point cor-
responds to a dry particle radius, prescribing a solubility limit for a soluble substance in a particle and
using available data on solubility.
Classical homogeneous and heterogeneous nucleation theory has been applied to develop a quan-
titative description of deliquescence and efflorescence. Richardson and Snider (1994, hereafter
RS1994 model) considered efflorescence as nucleation of a salt germ with the cap shape on the flat
550 Deliquescence and Efflorescence in Atmospheric Aerosols

surface of a foreign substrate (catalyst) and derived the expressions for the critical radius rcr and
energy DFcr of a salt germ:
2σ cs vc
rcr = , (11.2.1)
kT ln S*
16πσ cs3 vc2 f (mcs )
∆Fcr = , (11.2.2)
3( kT ln S* )2

where scs is the surface tension at the interface of a salt crystal and solution, S* = as* /as0 is the
salt supersaturation, as0 and as* are the solute activities at saturation and crystallization, k is the
Boltzmann constant, vc is the specific volume of the solid salt, f (mcs) is the geometric factor, and mcs
is the cosine of the wetting angle between the salt and solid catalyst. Nucleation rates were evaluated
with equations similar to those described in Chapters 8 and 9 as

J nuc = As J 0 exp(−∆ Fcr /kT ) , (11.2.3)

where As is the surface area of the solid inclusion in cases of heterogeneous nucleation, and As = 1
for homogeneous nucleation, and J0 is the kinetic prefactor, which is different for homogeneous
and heterogeneous nucleation. The kinetic prefactors were estimated as J0 ∼ 1022 cm−2 s−1 for hetero-
geneous nucleation and J0 ∼ 7 × 1031 cm−3 s−1 for homogeneous nucleation (Newkirk and Turnbull,
1955; Oatis et al., 1998). Gao et al. (2006) estimated J0 for NaCl as 2.8 × 1032 cm−3 s−1, applying the
method of Richardson and Snyder (1994) and Onasch et al. (2000). The homogeneous nucleation in
the absence of the foreign substrate was considered in a similar way by setting mcs = −1, f (mcs) = 1,
and the nucleation rate was evaluated in a simplified manner as

J hom = J 0,hom exp(−∆Fcr / kT ), J 0,hom ≈ (ν jf /vc ) exp(−∆Fact /kT ), (11.2.4)

where njf = (kT/h) is the jump frequency of the molecules’ penetration through the potential
barrier DFact.
The critical supersaturation was calculated using measured water activities aw of solutions at various
concentrations and the Gibbs–Duhem relation derived in Section 3.1. As was shown in Section 3.6, for
the two-component solutions consisting of water and solute, this relation can be written as

d ln as = − ( x w / x s )d ln aw . (11.2.5)

Its integration for the process with varying solute concentration and corresponding changes in water
activity from the deliquescence point with the water activity awd to the efflorescence point with awef
yields

awef  xw  awef  x 
ln Sef = − ∫  x  d ln aw ≈ − ∫awd  x  d ln( RHW ),
w
(11.2.6)
awd
 s  s

where Sef = (asef /asd) is the supersaturation of the solution, asef and asd are the salt activities at the
nucleation (efflorescence) point and at the deliquescence point with saturated salt concentration,
xw /xs is the molar ratio of the water to solute, and the second equality here assumes that aw ≈ RHW.
Application of this model allowed Richardson and Snider (1994) to explain the decrease in
salt supersaturation and the increase in relative humidities in heterogeneous efflorescence in the
presence of solid inclusions in the solution particles as compared to homogeneous nucleation. An
11.2. Theories and Models of Deliquescence and Efflorescence 551

important result of the RS1994 model was estimation of several fundamental properties of the salts
that were examined (NaCl, CaCl, KF, and NaNO3). The surface tensions scs were found in the range
50–64 erg cm−2, the activation energies were estimated as DFact ∼ 6–8 kT, the critical energies were
found as DFcr ∼ 55 kT, the homogeneous nucleation rates Jhom ∼ 108 cm−3 s−1, the kinetic coefficients
were estimated as J0 ∼ 7 × 1031 cm−3 s−1 for homogeneous nucleation, and J0 ∼ 1022 cm−2 s−1 for het-
erogeneous nucleation. These results and estimates served as a basis for subsequent works on salt
crystallization.
Oatis et al. (1998) and Onasch et al. (2000) used this method for studies of homogeneous and
heterogeneous efflorescence of ammonium sulfate, and found the ERH ≈ 37% and salt supersatura-
tion Sef ≈ 25–30 for pure ammonium sulfate. In the presence of inclusions of CaCO3 and BaSO4, that
served as catalyzers, the values of ERH increased to ≈45–48% and the critical supersaturations Sef
decreased to ≈14–17. Using classical nucleation theory for calculations of the nucleation rates along
with Clegg et al.’s (1998) thermodynamic theory of solutions for calculations of salt supersaturation,
Onasch et al. (2000) determined from the measurements of efflorescence the temperature depen-
dence of the surface tension ssc at the interface between the solid ammonium crystal and solution: ssc
decreased from 54–56 erg cm−2 at 298 K to 44 erg cm−2 at 210 K.
Russell and Ming (2002) used a simple thermodynamic equilibrium model to study deliquescence
of the three soluble species (sodium chloride, ammonium sulfate, and a soluble organic compound)
and showed that the role of the surface tension is to increase the deliquescence relative humidity,
so that DRH for the very small particles (∼15 nm) is 8–10% higher than that for the bulk substance.
The two models of deliquescence were compared: deliquescence of a dry salt crystal, and a crystal
wetted with several adsorbed liquid monolayers. The surface tension of 213 erg cm−2 was tested for
the interface dry crystal–air, although there are large uncertainties in the measured data, with esti-
mates ranging from 100 to 270 erg cm−2. The values used for surface tensions at the solid–liquid and
liquid–air interfaces were 29 ± 20 erg cm−2, and 83 ± 2 erg cm−2. It was emphasized in this work that
the exact calculations for many species and mixtures are not possible since the precise values of the
surface tensions have not been measured accurately; therefore, calculations were performed for the
range of the surface tensions. However, these values tested by Russell and Ming (2002) served as a
useful starting point in several subsequent models described next.
Gao et al. (2006, 2007), based on classical nucleation theory, elaborated a model of efflorescence
for sodium chloride and ammonium sulfate at room temperature. This model considered efflores-
cence as homogeneous nucleation, similar to Richardson and Snider (1994) and Oatis et al. (1998),
but with several modifications. For calculations of the critical germ radii and energies, the parameter-
izations of the solute density from Tang and Munkelwitz (1994) and of the solute–air surface tension
from Korhonen et al. (1998) were used with a detailed accounting for the solution composition. The
salt and water activities were calculated using the parameterizations from Tang and Munkelwitz
(1994) and a more advanced parameterization from Ally et al. (2001). The last method can be more
accurate for highly supersaturated solutions with molalities that can reach and exceed at efflores-
cence 35 mol kg−1. The model developed by Ally et al. (2001) uses statistical mechanics of multilevel
adsorption based on the Brunauer–Emmett–Teller (BET) adsorption isotherm and agrees well with
experimental data even for highly supersaturated solutions with molalities greater than 35 mol kg−1.
The salt and water activities, as and aw, are given in this model as
552 Deliquescence and Efflorescence in Atmospheric Aerosols

as = [(q A Nɶ s − X aw ) /q A Nɶ s ]qA , (11.2.7)

aw = ( Nɶ w − X aw )/Nɶ w , (11.2.8)

where Nɶ s and Nɶ w represent the salt and water moles in the solution, qA is the number of adsorp-
tion sites per mole of the salt, and Xaw is the amount of adsorbed water and is determined from the
quadratic equation
2
X aw
= exp(− ε A/kT ) = c A . (11.2.9)
(q A Nɶ s − X aw )( Nɶ w − X aw )

Here eA is the internal energy for a monolayer of water adsorbed onto the salt, and k is the Boltzmann
constant. Ally et al. (2001) found the values for the aqueous solutions of these salts: for ammonium
sulfate, cA = 2.073 ± 0.293, and qA = 2.47 ± 0.476; for NaCl solutions, cA = 3.813 ± 0.2598, and
qA = 2.845 ± 0.332.
Combining Ally et al. model with classical theory, Gao et al. found the non-monotonic behavior
of the calculated ERH with varying diameters D of the dry particles. When the size of ammonium
sulfate particles decreases, the ERH first decreases from 39.1% at D = 10 μm to the minimum of 30%
at D ≈ 30 nm, and then increases at smaller sizes, which is explained by the dominance of the Kelvin
effect for the smallest particles. These results were in agreement with various measurements cited in
Gao et al. (2006) and those earlier in this text. Similar behavior was found by Gao et al. (2007) for
NaCl particles. For D larger than 70 nm, the ERH decreases with decreasing particle sizes from 48%
at D = 20 μm to a minimum RHW = 44% at 60–70 nm. When the particles are smaller than 60–70 nm,
the ERH for NaCl increases from this minimum to 57% for the particles with D = 5 nm, in agreement
with the experimental data by Hämeri et al. (2001) and Biskos et al. (2006a,b).
A more sophisticated model of the deliquescence with formation of the liquid films was developed
by Shchekin, Shabayev, and Rusanov (2008a,b) and Shchekin and Shabayev (2010) (SSRH model)
and further elaborated by Hellmuth et al. (2012, 2013). Instead of using the capillary approximation,
their model was based on the concept of disjoining pressure. McGraw and Lewis (2009) promoted
the theory of deliquescence considering the solution layer around the solid salt crystal and intro-
ducing a thin layer criterion (TLC) to define a limiting deliquescence relative humidity (DRH) for
small particles. The definition of DRH requires: 1) equality of chemical potentials between salt in an
undissolved core, and a thin adsorbed solution layer; and 2) equality of chemical potentials between
water in the thin layer and vapor phase. The solution of this system of equations enabled determina-
tion of the DRH and ERH over a wide range of particle sizes (down to the nanoscale), as well as the
construction of phase diagrams for this system.
This brief review gives a general outline of several theories of deliquescence and efflorescence that
have been developed over the last two decades. Comparing these phenomena with homogeneous and
heterogeneous freezing and melting considered in Chapters 8 and 9, we see the similarity of these
phase transitions: the solid–liquid transition at deliquescence is similar to melting and salt crystal-
lization at efflorescence is similar to freezing. This similarity motivates construction of the models of
both deliquescence and efflorescence based on the general equilibrium (or entropy) (Eqn. 3.6.4) as
was done in Chapters 8 and 9 for freezing and melting.
11.3. A Model for Deliquescence of Salt Crystals Based on the Entropy Equation 553

The approach developed here considers simultaneously the effects of temperature, particle size,
the kinetic limitations due to various nucleation rates, and the effects of external pressure. The theory
is similar to the theories of melting and freezing (Khvorostyanov and Curry, 2000, 2004a,b, 2009b)
described in Chapters 8 and 9 and is called hereafter the KC theory of deliquescence and salt crys-
tallization or the KC model for the convenience of comparison with experimental data and other
models. Application of this model to the ice–solution and solid salt–solution transitions allows us to
calculate various phase diagrams.
The KC theory is based on two simple hypotheses: 1) Deliquescence begins with formation of a
liquid solution germ on the surface of a salt crystal (similar to surface melting). 2) Salt crystallization
(efflorescence or precipitation) begins with formation of a salt germ in solution (similar to ice crystal
nucleation in solution). In Section 11.3, the equations for the deliquescence are derived based on the
entropy equation, and in Section 11.4 they are applied for calculations of the temperature dependen-
cies of the dissolution heat, solubility, and deliquescence relative humidity for ammonium sulfate and
NaCl. In Section 11.5, the equation for the eutectic point is derived and solved, and the phase diagram
is constructed. In Section 11.6, the equations of efflorescence are derived based on the entropy equa-
tion. Finally, in Section 11.7, based on the calculations of the deliquescence and efflorescence in
this chapter, and of the freezing–melting processes in Chapter 8, the general phase diagrams for an
example of ammonium sulfate are constructed that include all four branches of stable and metastable
equilibrium between the ice, solution, and the solid salt—that is, the deliquescence, efflorescence,
and melting and freezing curves are calculated from the same theory.

11.3. A Model for Deliquescence of Salt Crystals Based on the Entropy Equation

We assume that deliquescence can be described as a nucleation process analogous to surface melting
(Section 9.9) and begins with formation of a liquid solution germ on the surface of a crystal. This
germ may have the shape of a spherical segment (lens) formed in the micro-cavity or defect of the salt
crystal or may form as a thin liquid film around the crystal. Formation of the liquid lenses in the cavi-
ties or crystal defects may proceed earlier because the vapor pressure inside the cavities with negative
radii of curvature is lower due to a negative Kelvin effect, which may cause vapor condensation and
crystal deliquescence on such sites. Formation of the liquid lenses may proceed on the crystal surface
even without crystal defects due to incomplete wettability of the crystal by the solution.
The liquid film stage may occur later, when many liquid lenses merge and form a continuous film
as in McGraw and Lewis (2009), although this merging may proceed rapidly, depending on the rate
of humidity increase. Some previous models of deliquescence with formation of the liquid films
were briefly reviewed in the previous section. In the following text, we consider another model of
the deliquescence process developed by the authors (the KC model), which is based on the classical
nucleation theory and its extensions similar to our consideration of surface melting and freezing in
Section 9.9. We suppose that a solution drop (liquid germ) has the shape of a spherical segment (lens)
on the crystal surface or a liquid film around a solid crystal core bounded by the two surfaces. The
outer surface between the solution and humid air has the radius of curvature rd and surface tension
ssa, and the inner surface (bottom) between the solution and crystal has a radius of curvature rc (the
radius of the solid crystal assumed to be spherical) and surface tension scs.
554 Deliquescence and Efflorescence in Atmospheric Aerosols

Here we deal with the situation when liquid forms at the interface of its own solid and gas (vapor
or humid air). As discussed in Section 9.9 for the water–ice interface, when a liquid lens nucleates,
the contact angle qcs of such systems can be small but nonzero as in the case of water melting when
wetting is incomplete—i.e., small liquid caps (spherical segments) occur on the surface of a salt crys-
tal instead of a liquid film. Thus, at the first stage, deliquescence may occur as a quasi-heterogeneous
process similar to surface melting. Hereafter, we use the term “drop” for a liquid solution germ,
although this description is applicable also for the films.
The derivation is based on the general equilibrium (entropy) (Eqn. 3.6.4) of Section 3.6 for this
system. For such a situation, in (Eqn. 3.6.4) phase 1 is salt in the crystal with molar enthalpy hc0 and
pressure pc, and phase 2 is salt in the solution drop with the molar enthalpy hs0 and pressure ps. The
molar enthalpy difference is h10 − h20 = hc0 − hs0 = −Dhs = −MsLc. Here Ms is the salt molecular weight,
and −Dhs and Lc are the molar and specific heats (enthalpies) of salt dissolution. The sign of Lc is
defined earlier so that Lc > 0 if dissolution requires positive heat (as melting)—i.e., is an endothermic
process as for most common salts, and Lc < 0 in the opposite case for salts with exothermic dissolution.
For example, the molar dissolution heats Dhs are positive, 1.88 kJ mol−1 for NaCl, 15.34 kJ mol−1 for
KCl, and 6.32 kJ mol−1 for ammonium sulfate, but it is negative, −9.76 kJ mol−1, for Na2SO4 (Seinfeld
and Pandis, 1998). It is assumed that the activity of pure salt ac = 1, thus, the last term in (Eqn. 3.6.4),
ln(ac /as) = −ln(as). With these definitions, (Eqn. 3.6.4) can be written as

(hc 0 − hs 0 ) v v
− 2
dT + c 0 dpc − s 0 dps − Rd ln as = 0. (11.3.1)
T T T
Here vc0 and vs0 are the molar volumes of the solid crystal and solution, ps and pc are the internal pres-
sures inside the solution drop and crystal, as = gsxs is the activity of the salt in solution, gs and xs are
the activity coefficient and molar fraction of the salt.
When the solution under consideration is an ionic solution, this equation should be somewhat
modified. Defay et al. (1966) indicated that the term lnas should be replaced for an ionic solution as

ln as = ln(γ s x s ) → ν ln aɶ s , aɶ s = γ ±α s Mˆ s (11.3.2)

where n = n+ + n− is the total effective number of ions, n+ and n− are the numbers of positive and
negative ions, g± is the mean ionic activity coefficient (the mean weighted activity coefficients of
cations and anions), as is the degree of dissociation, and M̂ s is the stoichiometric molality of salt.
The non-ideality of the solution can also be represented as ln ( as ) → ν Φs ln(γ s x s ), where Φs is the
osmotic potential.
If a salt crystal is approximated by a sphere (similar to an ice crystal in the cases of freezing con-
sidered earlier and to the previous deliquescence models reviewed in Section 11.1), the internal pres-
sures inside a crystal, pc, and inside a liquid solution drop, ps, can be expressed in terms of external
pressure p with use of Laplace’s conditions of mechanical equilibrium:

 2σ   2σ 
dpc = dp + d  cs  , dps = dp + d  sa  , (11.3.3)
 rc   rd 

where subscripts c and s refer to crystal and solution respectively, scs and ssa are the surface tensions
at the crystal–solution and solution–air interfaces, and we assume that rd << rc, and the curvature
11.3. A Model for Deliquescence of Salt Crystals Based on the Entropy Equation 555

effect in dps due to rc can be neglected in the second of (Eqns. 11.3.3). Equations (11.3.3) describe the
mechanical equilibrium between a salt germ and liquid solution drop, and the equilibrium between
the liquid drop and environmental air. Substituting (Eqn. 11.3.3), (Eqn. 11.3.2), and the enthalpy dif-
ference hc0 − hs0 = −MsLc into (Eqn. 11.3.1), we obtain:

dT  vc 0 vs 0   v   2σ  v  2σ 
M s Lc + −  dp +  c 0  d  cs  − s 0 d  sa  − ν Rd ln aɶ s = 0. (11.3.4)
T 2
 T T   T   rc  T  rd 

Now, we can integrate (Eqn. 11.3.4) in two slightly different ways, with and without multiplying
first by T, which lead to the various forms of the final equation, each may be more convenient for
comparison with the known equations. Before integration, we need to evaluate the number of thermo-
dynamic degrees of freedom Nw (variance) which for a system including curved surfaces, according
to Section 3.3 of Chapter 3, is related to the number of components c as Nw = c + 1. In our case here,
the components are: 1) dry air; 2) water in liquid (solution) and gas (vapor around the drop) states;
3) salt in the dissolved and solid states. Hence, we have c = 3 components and Nw = 3 + 1 = 4 degrees
of freedom. Equation (11.3.3) includes five variables, of which only four are independent and the fifth
one is a function of these four. Thus, we have to fix any one variable in (Eqn. 11.3.3) when integrating,
and this reduces (Eqn.11.3.4) to several particular cases: there are five different combinations that cor-
respond to five different problems. If the salt is nonvolatile and its mass is constant, we have one more
constraint, and the variance reduces by 1 to Nw = 3. Then, we have to fix two variables and have three
independent variables. There are 10 combinations and 10 different situations. If the salt is volatile, its
mass may change and we have Nw = 4. If there are chemical reactions, then Nw may be different.
Multiplying (Eqn. 11.3.4) by T and integrating by analogy with the case of aqueous solutions
freezing–melting as in Section 9.7, from some reference point T*, 1/rd = 0, 1/rc = 0, p = p*, aɶ s* to the
values T, rd, rcr, p, aɶ s, we obtain:

T*  2σ   2σ 
− M s Lefc ln + ∆v ∆p + vc 0  cs  − vs 0  sa  − ν RT ln Sɶs = 0, (11.3.5)
T  rc   rd 

where we introduced the activities ratio

Sɶs = aɶ s / aɶ s* , (11.3.6)
−1
 T0 L (T )   T0 dT   T0 Lc (T )    T0   −1
Lefc (T ) =  ∫ c dT  ×  ∫  =∫ dT  ×  ln    . (11.3.6a)
T T  T T  T T    T 

The symbols with asterisks in (Eqn. 11.3.5) correspond to the quantities in the reference state, Lefc
is the specific dissolution heat averaged over the temperature range as was done in Chapters 8 and 9
for the melting heat, Dv = vc0 − vs0 is the difference of the salt molar volumes in solid and solution,
Dp = p − p* is the excess of external pressure, the bars over quantities denote mean values after
integration.
If the reference point is chosen at solute saturation, aɶ s* is the salt activity at saturation, and
Sɶs = aɶ s /aɶ s* is the solute supersaturation that can be smaller and greater than 1 since aɶ s can be smaller
than aɶ s* in diluted solutions and much greater than aɶ s* in supersaturated metastable solutions. Note
that the ratio Sɶs = aɶ s /aɶ s* under the logarithm sign in (Eqn. 11.3.5) is not very different from the
556 Deliquescence and Efflorescence in Atmospheric Aerosols

activities ratio Ss = as/as*, which therefore can be used for approximate calculations as in Defay
et al. (1966). The bars over the volumes are omitted in the following text for brevity; the factor n
(total number of ions) may be close to the van’t Hoff factor i or to the product nidFs, where nid is the
number of ions in ideal solution and Fs is the osmotic potential. Thus, accounting for n may sub-
stantially influence the results. For an isothermal (T = const) and isobaric (p = const) process, and
large radius of liquid lens, 1/rd = 0, or small ssa, and assuming that Sɶs = aɶ s /aɶ s* ≈ x s /x s*, (Eqn. 11.3.5)
is simplified:

2σ cs RT x
= ln s , (11.3.6b)
rc vc 0 xs*

where xs is the mole fraction of the solute in the crystal with radius rc, and xs* is the mole fraction
of the solute in equilibrium with a large crystal or bulk phase (rc = ∞). Equation (11.3.6b) is the
Freundlich–Ostwald equation that describes the dependence of the solubility xs/xs* on the solution
drop radius (Defay et al., 1996) and is considered in Section 11.6. Equation (11.3.5) generalizes
(Eqn. 11.3.6b) taking into account the effects of the temperature, pressure, and non-ideality of the
solution. Other generalizations of the Freundlich–Ostwald equation were derived by Shchekin,
Shabayev, and Rusanov (2008a,b, 2010) based on the concept of disjoining pressure.
The critical radius rd of the liquid germ of deliquescence on the crystal surface can be obtained
from (Eqn. 11.3.5):

2σ sa vs 0
rd = , (11.3.7)
 T*  2σ cs
− M s L ln   + ∆v ∆p + vc 0
ef
− ν RT ln Ss
c
T rc
or in a more compact form
2σ sa vs 0
rd = , (11.3.8)
 T* gs  2σ cs
− M s L ln  Ss  + ∆v ∆p + vc 0
ef
c
T  rc

where we introduced a dimensionless parameter gs analogous to Gn in ice nucleation

ν RT
gs = . (11.3.9)
Lefc M s

Dividing by Ms and introducing specific densities of salt in solution, rs0 = Ms/vs0, and in the solid
crystal, rc0 = Ms/vc0, (Eqn. 11.3.8) can be rewritten in the form

2σ sa
rd = , (11.3.10)
 T  ∆ρ s ∆p ρ s 0 2σ cs
− ρ s 0 Lefc ln  * Ssgs  + +
T  ρc 0 ρc 0 rc

where Drs = rs0 − rc0. It can be presented in a form similar to the case of surface melting, as in
Section 9.7:
2σ sa vs 0
rd = , (11.3.11a)
− M s Lefc ln  * Ssgs exp(− H del ) 
T
T 
11.3. A Model for Deliquescence of Salt Crystals Based on the Entropy Equation 557

2σ sa
rd = , (11.3.11b)
− ρ s 0 Lefc ln  * Ssgs exp(− H del ) 
T
T 
where the term Hdel describes the effects of pressure and finite crystal size

1  2σ cs  1  ∆ρ s ∆p 2σ cs 
H del = ∆v ∆p + vc 0 = + . (11.3.12)
Lefc M s  rc  Lefc ρc 0  ρ s 0 rc 

(Note that (Eqn. 11.3.11b) resembles (Eqn. 9.9.9) for surface melting.) Either of these two forms
of (Eqns. 11.3.11a) and (11.3.11b) can be used when the data on the molar (molecular) volumes or
specific densities are available. The form of these (Eqns. 11.3.11a) and (11.3.11b) enable establishing
the equivalence of effects of various externals factors of deliquescence (T, rc, Dp, as), following the
previous chapters on freezing.
The critical energy of formation of the liquid solution germ for deliquescence can be written in
terms of the classical nucleation theory similar to the surface melting in Section 9.9:

4
∆Fcr ,del = πσ sa rd2 f (mcs , x )
3
16π σ sa3 vs20 f (mcs , x ) (11.3.13)
= 2 ,
3  ef  T* gs  
 Lc M s ln  Ss exp ( − H del )  
 T 

where f(mcs, x) is Fletcher’s geometric factor, and mcs is the cosine of the contact angle between solid
salt and its solution, x = rc/rd. The contact angle can be small but nonzero in the case of the incom-
plete wettability of the salt by solution as discussed in Section 9.9 for surface melting, thus slightly
increasing the critical energy of deliquescence. Therefore, the shape factor f(mcs, x) occurs here as in
the case of heterogeneous nucleation, although we consider homogeneous nucleation without foreign
catalysts.
The nucleation rate now can be written by analogy with the surface melting (Section 9.7):

 ∆Fcr ,del ∆Fa ,del 

J del = Cdel exp  − − , (11.3.14)
 kT kT 
 kT 
Cdel ≈ N cc  c 4π rc2 .
 h  1cs
(11.3.15)

Here Cdel is the kinetic coefficient for deliquescence, DFa,del is the activation energy for transition of
the salt molecules from the solid to the liquid solution, Ncc is the number of salt molecules in crystal
in contact with the unit area of solution, and c1cs is the number of molecules adsorbed on the surface
of the solid. If one considers the formation of a thin liquid solution film around a solid salt core
instead of spherical caps or lenses, then the process can be treated as a homogeneous nucleation. In
this case, we can assume f(mcs,x) = 1, and the kinetic coefficient is as it was derived for homogeneous
nucleation in Chapter 8:

 v kT   σ cs  1/2  ρ s 0 kT   σ cs  1/2
Cdel = 2 N cc  c 0    = 2 N cc    . (11.3.16)
 vs 0 h  kT  ρc 0 h   kT 
558 Deliquescence and Efflorescence in Atmospheric Aerosols

Equations (11.3.7) to (11.3.16) constitute the model for deliquescence and, as shown next, enable
description of several essential features of this phenomenon.

11.4. Applications of the Deliquescence Model

Some useful relations can be obtained solving (Eqn. 11.3.14) relative to DFcr,del:
J del
∆Fcr ,del = − kT ln − ∆Fa ,del . (11.4.1)
Cdel

Equating (Eqn. 11.4.1) to (Eqn. 11.3.13), we obtain the temperature of deliquescence:

g
 aɶ 
s
 1  2σ sc  
Tdel = T*  s  exp  − ef 
∆p∆v + vc 0 × −
 s* 
ɶ
a  M s c 
L rc   Ms

 1  16π σ sa3 vs20 f (mcs , x )  

1/ 2

× exp − ef 
−  . (11.4.2)
rc  M s Lc  3 kT ln( J del /Cdel ) + ∆Fa ,del  

Note that this expression is similar in structure to the expressions for the critical temperatures of
freezing and melting derived in Chapters 8 and 9. If aɶ s* is the activity in a saturated solution, then
aɶ s /aɶ s* = Ss* is the solution supersaturation. This equation relates the temperature Tdel and solute
activity as at deliquescence, and can be used to express one as a function of another. If Lefc > 0 (disso-
lution requires positive heat), the arguments of both exponents are negative, the exponents are smaller
than 1 and Tdel < T*. Thus, this equation shows that the following factors leads to a decrease of the
deliquescence temperature: a) the possible existence of a small but finite contact angle qcs between
the outer surface of the solution germ and the surface of the salt crystal; b) finite crystal radius rc;
the smaller the rc, the greater the decrease in Tdel; c) external pressure; and d) finite nucleation rate
Jdel. That is, the deliquescence temperature decreases with increasing external pressure (as can be in
the atmospheres of the large planets, Curry and Webster, 1999) and with increasing nucleation rates.
In the case of water melting, the contact angle between liquid (water) and solid (ice) surfaces is
0.5–2 degrees although this angle may reach several degrees for the case of the melting of some metals.
If the contact angle for solutions is small similar to water melting, then mcs = cosqcs → 1, f(mcs,x) → 0,
and the second exponent on the right-hand side in (Eqn. 11.4.2) tends to 1. The same occurs when
the nucleation rate Jdel is very small due to a slow change of the external conditions. Then, Jdel → 0,
ln(Jdel) → −∞, the denominator in the last exponent tends to zero, and the exponent tends to 1. Thus,
(Eqn. 11.4.2) is simplified as

 1  2σ sc  
Tdel = T* Sɶsgs exp  − ef 
∆p∆v + vc 0 . (11.4.3)
 M s Lc  rc  

If we consider the process at constant pressure or at small pressure variations, Dp ≈ 0, and for the
bulk phase, 1/rc = 0, then the last exponent is also 1. Assuming also that Sɶs = (aɶ s / aɶ s* ) ~ (as / as* ) , we
obtain a simple relation:
gs gs gs
 aɶ   a   γ x 
Tdel (as ) = T* S = T*  s  ≈ T*  s  = T*  s s  .
gs
s (11.4.4)
 s* 
ɶ
a  s* 
a  γ s* x s* 
11.4. Applications of the Deliquescence Model 559

This equation relates the deliquescence temperature and solution concentration—i.e., it describes the
deliquescence curve on the phase T-xs diagrams. It can be used in several ways.

11.4.1. The Temperature Dependence of Dissolution Heat

Using definition (Eqn. 11.3.9) of gs = ν RT /( Lefc (T ) M s ) , dividing (Eqn. 11.4.4) by T*, taking the
logarithm and solving for Dhs = MsLcef, we obtain

ln Ss ln(γ s x s /γ s x s* )
M s Lefc (T ) = ν RTdel ≈ ν RTdel . (11.4.5)
ln(T /T* ) ln(T /T* )

This equation can be used to evaluate the temperature dependence of the averaged dissolution heat
using the data on solubility xs(T), with T* sufficiently close to Tdel. Such calculations can be done—
e.g., using the data on solubility from Tang and Munkelwitz (1993) and Seinfeld and Pandis (1998)
given in the polynomial form by temperature:

ns (T ) = As + Bs T + Cs T 2 , (11.4.6)

where ns is the number of moles of solute per one mole of water. For example, the coefficients for
the two most known and studied salts are the following. For NaCl, ns = 0.111 at 298.15 K in saturated
solution; As = 0.1805, Bs = −5.310 × 10−4, and Cs = 9.965 × 10−7. For ammonium sulfate, (NH4)2SO4,
ns = 0.104 at 298.15 K in saturated solution; As = 0.1149, Bs = −4.489 × 10−4, and Cs = 1.385 × 10−8.
Using (Eqn. 11.4.6), the mole fraction xs can be calculated, substituted into (Eqn. 11.4.5), and assum-
ing that gs /gs* only slightly varies, the temperature dependence of M s Lefc (T ) can be estimated.

11.4.2. The Temperature Dependence of Solubility

If we consider the temperature as the variable and the solubility as its function, then (Eqn. 11.4.2)
can be rewritten as:
1/ gs
T   1  2σ sc  
aɶ s = aɶ s*  del  exp  ef 
∆p∆v + vc 0  × ex −
 T*   M s Lc  rc   Ms

 1  16π σ sa3 vs20 f (mcs , x )  

1/ 2

× exp  ef 
−  . (11.4.7)
rc  M s Lc  3 kT ln( J del /Cdel ) + ∆Fa ,del  

This equation is an analog of the equations for the critical humidities of freezing derived in Chapters 8
and 9. It describes the temperature dependence of the salt activity (or solubility if gs /gs* ∼ 1) with a
simultaneous accounting for other effects (crystal curvature, external pressure, the finite nucleation
rate, the value of dissolution heats, and activation energy DFa,del), whose number is determined by
the variance of the system. Note that this equation is similar to that for the case of surface melting in
Chapter 9. Consider again a particular case of (Eqn. 11.4.7) with p = const (Dp = 0), bulk solution,
1/rd = 1/rc = 0, and small contact angle qsc—i.e., f(mcs, x) → 0. Then, (Eqn. 11.4.7) can be simplified.
Assuming again that aɶ s /aɶ s* ≈ as /as*, then (Eqn. 11.4.7) yields for the salt activity as = gs xs:
Lefc M s
1/ gs
T T ν RT
as (T ) = as*   = as*   . (11.4.8)
 T*   T* 
560 Deliquescence and Efflorescence in Atmospheric Aerosols

If variations of gs are substantially smaller than those of xs in the considered region, or for ideal solu-
tions with gs = 1, (Eqn. 11.4.8) yields for the solubility:
Lefc M s

x s = x s* (T /T* )1/ gs = x s* (T /T* ) ν RT . (11.4.9)

Shown in Fig. 11.2a are the solubilities of NaCl and ammonium sulfate calculated with (Eqn.
11.4.9) (open symbols) using the parameters from Seinfeld and Pandis (1998): for NaCl, n = 2,
M s Lefc = 1.88 kJ mole −1 (approximately the same as MsLc at T = 298.15 K), the reference satu-
rated mole fraction xs* = 0.098 mole mole−1 at T = 273.15 K; and for ammonium sulfate, n Φs = 2.6,
M s Lefc = 6.32 kJ mole −1 (same as at T = 298.15 K), the reference saturated mole fraction xs* = 0.088
mole mole−1 at T = 273.15 K. This figure illustrates a significant temperature dependence of ammo-
nium sulfate solubility and a rather weak dependence for NaCl. This difference can be explained by
the different values of the power indices gs for these substances. An estimate with these parameters
shows that at room temperature for NaCl, gs = 2.64, and 1/gs = Lefc M s /(ν RT ) = 0.38; for ammonium
sulfate, gs ≈ 0.98 and 1/gs ≈ 1.02. Therefore, the variation of solubility, ~ T 1/ gs, is almost linear with
temperature for ammonium sulfate and is smaller than a square root for NaCl.
A comparison with the polynomial parameterization (Eqn. 11.4.6) by Tang and Munkelwitz (1993)
of the experimental data on solubility (see also Seinfeld and Pandis, 1998, p. 510) (solid symbols)
shows a good accuracy of (Eqn. 11.4.9). This is quantitatively illustrated in Fig. 11.2b where the rela-
tive error of calculations of the mole fraction xs(T) with (Eqn. 11.4.9) is shown. One can see that the
error of calculations with (Eqn. 11.4.9) relative to the empirical parameterization (Eqn. 11.4.6) does

0.13

0.12
Mole fraction of salt xs

0.11

0.10

0.09
amm. sulf., KC model
0.08 amm. sulf., SP98 polynom
NaCl, KC model
0.07
NaCl, SP98 polynom
0.06
–20 0 20 40 60 80 100
Temperature (C)
(a)

Figure 11.2. (a) Solubility of NaCl and ammonium sulfate calculated with (Eqn. 11.4.9) of the KC
model (open symbols) using the parameters: for NaCl, n = 2, M s Lefc = 1.88 kJ mole −1 (same as at
T = 298.15 K), the reference saturated mole fraction xs* = 0.098 mole mole−1 at T = 273.15 K; for
ammonium sulfate: n = 2.6, M s Lefc = 6.32 kJ mole −1 (same as at T = 298.15 K), and the reference
saturated mole fraction xs* = 0.088 mole mole−1 at T = 273.15 K. The results are compared to the
parameterization with quadratic polynomials (Eqn. 11.4.6) from Tang and Munkelwitz (1993) and
Seinfeld and Pandis (1998, p. 510), (solid symbols, SP98).
11.4. Applications of the Deliquescence Model 561

Relative error in solubility (%)

2

–2

–4
NaCl
amm. sulf.
–6

–40 –20 0 20 40 60 80 100

Temperature (C)
(b)

Figure 11.2. (b) The error of calculations of the mole fraction xs(T) of NaCl and ammonium
sulfate for saturated solutions with (Eqn. 11.4.9) of the KC model relative to the polynomial
parameterization (Eqn. 11.4.6) by Tang and Munkelwitz (1993).

1200
amm. sulf., KC amm.sulf., exp.
1100
amm. sulf., SP98 NaCl, exp.
1000 NaCl, KC
Salt mass (g L–1)

900 NaCl, SP98

800
700
600
500
400
300
–40 –20 0 20 40 60 80 100
Temperature (C)
(c)

Figure 11.2. (c) The temperature dependence of the mass of salt (g) dissolved in 1 L of water
calculated for ammonium sulfate and NaCl with (Eqn. 11.4.9) of the KC model (KC, open
symbols) and compared to the parameterization from Tang and Munkelwitz (1993) and Seinfeld
and Pandis (1998) (solid symbols, SP98), and to the experimental data from Tang and Munkelwitz
(1993) and SP98 (crosses).

not exceed ±4%, and increases to −7% for NaCl near −40 °C. The mass of dissolved salt calculated
with the KC model from the mole fraction (open symbols) is shown in Fig. 11.2c. A comparison with
the parameterizations (diamonds and solid circles) and experimental data (crosses and asterisks) from
Seinfeld and Pandis (1998) also shows a good accuracy of (Eqn. 11.4.9).
562 Deliquescence and Efflorescence in Atmospheric Aerosols

11.4.3. The Temperature Dependence of the Deliquescence Relative Humidity

When the deliquescence mole fraction xs of the saturated salt is known, there are several ways to
calculate the water activity aw and deliquescence relative humidity, DRH. The simplest way would
be that for the ideal solutions, where aw ≈ xw ≈ 1 − xs. However, due to the strong non-ideality of
solutions, this calculation can cause substantial errors. Another still sufficiently simple way is the fol-
lowing. The solute mole fraction xs can be recalculated to the corresponding molality M̂ and weight
percent w, and then the water activity aw(T) can be easily calculated using the existing empirical
parameterizations of aw in terms of w or M̂—e.g., Tang and Munkelwitz (1993, 1994, 1997); Chen
(1994); and others. In the previous Section, we calculated the temperature dependence xs(T), which
provides the temperature dependence aw(T) via w or M̂. Since water activity in this case coincides
with the environmental RHW at deliquescence, this yields the temperature dependence DRH(T).
We calculated DRH(T) for ammonium sulfate, using the parameterization for aw(w) from Tang and
Munkelwitz (1994). Shown in Fig. 11.3 is the temperature dependence of the deliquescence water
activity aw(T) or DRH(T)/100 for ammonium sulfate calculated with (Eqn. 11.4.9) of the KC model
for xs(T). This calculation is compared to the calculation of DRH(T) from Tang and Munkelwitz
(1993) and Seinfeld and Pandis (1998). Their derivation accounted for the fact that the enthalpy of
solution Dhsol is a sum of the enthalpy of condensation of water vapor Dhv = MwLe and the enthalpy
of dissolution of ns moles of solute, nsDhs = nsMsLc—that is, Dhsol = Dhv − nsDhs = MwLe − nsMsLc.
Then, the Clausius–Clapeyron equation for solution and water vapor is a modification of this equa-
tion derived in Chapter 3:

d ln ews ∆hsol M w Lv M L
= = − ns (T ) s 2c . (11.4.10a)
dT RT 2 RT 2 RT
The Clausius–Clapeyron equation for pure water vapor is

d ln ews ,0 M w Lv
= . (11.4.10b)
dT RT 2

0.86
KC model
Water activity or DRH/100

0.84 TM93-SP98, T extended

0.82

0.80

0.78

0.76

0.74
220 240 260 280 300 320 340 360 380
Temperature (K)

Figure 11.3. Temperature dependence of deliquescence water activity aw(T) or DRH(T)/100 for
ammonium sulfate calculated with (Eqn. 11.4.9) of the KC model compared to the calculations
with (Eqn. 11.4.12b) from Tang and Munkelwitz (1993) (see also SP98), based on the Clausius–
Clapeyron equations at T = 0–50 °C, and extended here over a wider T-region.
11.5. Phase Diagram of the Solution and Evaluation of the Eutectic Point 563

Subtracting (Eqn. 11.4.10b) from (Eqn. 11.4.10a) and using the definition DRH = (ews/ews,0) × 100%,
Tang and Munkelwitz (1993) obtained an equation for DRH

d ln(ews /ews ,0 ) d ln( DRH /100) M L

= = − ns (T ) s 2c . (11.4.11)
dT dT RT
Substituting (Eqn. 11.4.6) for ns(T) in (Eqn. 11.4.11), assuming that Lc does not depend on T and
integrating from the reference point T* = 298 K to T yields

DRH (T ) M s Lc  1 1 
ln =  As  −  − Bs ln T* − Cs (T − T* )  , (11.4.12a)
DRH (T* ) R   T T*  

or

DRH (T )  M L   1 1   
= exp  s c  As  −  − Bs ln T* − Cs (T − T* )   . (11.4.12b)
DRH (T* )  R   T T*   

Wexler and Seinfeld (1991) derived this equation for constant solubility—i.e., Bs = Cs = 0, Tang and
Munkelwitz (1993, TM93 model) generalized it for variable ns(T) with nonzero Bs, Cs for the range
T = 0–50 °C. The DRH(T)/100 calculated with TM93 model (Eqn. 11.4.12b) is compared in Fig. 11.3
with calculations using the KC model for a wider T-region from 230 K to 375 K. A comparison shows
a good agreement of the KC model based on (Eqn. 11.4.9) with the TM93 model (Eqn. 11.4.12b) over
this wide temperature range despite the different equations used, although a discrepancy somewhat
increases toward the highest and lowest temperatures. Note that Wexler and Seinfeld (1991) and Tang
and Munkelwitz (1993) derived DRH(T) based on the equilibrium of water in vapor and solution,
and the T-dependence in the KC model is derived based on the equilibrium of salt in the crystal and
solution. Both methods are complimentary, and as this comparison shows, are in good agreement.

11.5. Phase Diagram of the Solution and Evaluation of the Eutectic Point

Equation (11.4.4) for the deliquescence temperature is similar to the equation for the equilibrium
melting temperature Tm(Sw) (liquidus curve) derived in Section 8.7:
ef ef
Tm (aw ) = T0 awGn = T0 awRT / M w Lm = T0 SwRT / M s Lm , (11.5.1)

where T0 = 273.15 is the triple point. Assuming that variations of the salt activity coefficients ratio
(gs /gs*) in (Eqn. 11.4.4) is smaller than variations of the mole fraction ratio (xs/xs*), (Eqn. 11.4.4) can
be rewritten as
ν RT
gs
 x   x  Lefc M s
Tdel (as ) ≈ T*  s  = T*  s  . (11.5.2)
 x s*   x s* 

The equilibrium Tdel calculated with (Eqn. 11.5.2) for ammonium sulfate is plotted in Fig. 11.4 as
a function of the water saturation ratio Sw equal to the water activity aw, which is calculated using a
parameterization of Tang and Munkelwitz (1993), and is compared to the experimental data for the
deliquescence temperature of ammonium sulfate from Tang and Munkelwitz (1993) and Seinfeld
564 Deliquescence and Efflorescence in Atmospheric Aerosols

300

Deliquiescence

liques
290
KC model

Tde
280 SP-1998, exp.
Tm
elt

Tm
270 Solution
Salt +
260 Ice + solution solution

250 Eutectic
point
240
1.0 0.9 0.8 0.7
Saturation ratio Sw (or aw)

Figure 11.4. The phase diagram in T − Sw coordinates of solution melting and deliquescence
calculated with the KC model. Right curve: temperature of solute deliquescence Tdel(Sw)
calculated with (Eqn. 11.5.2) as a function of the water saturation ratio Sw (equal to water activity
aw) for ammonium sulfate with T* = 0 °C (open circles), compared to the experimental data for
deliquescence from Seinfeld and Pandis (1998, SP-1998, exp.) and Tang and Munkelwitz (1993)
(triangles). Left curve: calculated equilibrium melting temperatures Tm(Sw) from Khvorostyanov
and Curry (2004a) described in Chapter 8 or (Eqn. 11.5.1) here. Three curves for ammonium
sulfate, NaCl, and sulfuric acid (circles, crosses, and diamonds) merge in one curve as the functions
of Sw due to colligative properties. The intersection of these curves around T ≈ 255 K and Sw ≈ 0.84
is the eutectic point for ammonium sulfate.

and Pandis (1998, SP-1998, exp). A comparison shows again a good agreement, indicating the valid-
ity of the equations for deliquescence derived in Sections 11.3 and 11.4. Fig. 11.4 also shows the
equilibrium melting temperature of ice Tm calculated with (Eqn. 11.5.1). As described in Chapter 8,
the melting curves for the three indicated substances (NaCl, ammonium sulfate, and sulfuric acid)
merge in the T–Sw coordinates due to colligative properties. These two curves for Tm and Tdel consti-
tute a phase diagram in coordinates T–Sw for ammonium sulfate, which is in good agreement with
the known from experiments phase diagrams (e.g., Landau and Lifshitz, v.5, 1958b; Xu et al., 1998;
Curry and Webster, 1999; Martin, 2000). Here, both branches of the diagram, the left curve for the
ice–solution equilibrium and the right curve for the salt-solution equilibrium, are calculated from the
same theory (extended CNT) using simple (Eqns. 11.5.1) and (11.5.2). Thus, these equations allow
a simple description of both branches of the phase diagrams of solutions: the melting and deliques-
cence branches.
This phase diagram describes the evolution of the solution with changing composition. The upper-
most point on the left with Sw = 1 corresponds to the melting point of pure water Tm = 273.15 K. As
the solution concentration increases (the water activity decreases), the melting temperature decreases
along the curve Tm(Sw). When a fraction of the solution freezes, almost pure ice forms, and solute
is rejected into the solution making it increasingly concentrated. If a vertical trajectory on the T-Sw
plane intersects the Tm curve, then with the same initial composition, the solution may exist above
the Tm curve and a mixture of ice and solution may exist below Tm as indicated in Fig. 11.4. As the
temperature falls, more and more ice forms leaving the solution increasingly saline. (When the solute
11.5. Phase Diagram of the Solution and Evaluation of the Eutectic Point 565

is NaCl or contains other components of seawater, it is called brine, and similar diagrams are used
for the salinity of seawater, Millero, 1978; Curry and Webster, 1999; Millero et al., 2008). When an
increasing solute concentration reaches saturation, this point on the phase diagram is called the eutec-
tic point, where all three phases (solution, ice, and salt) exist in equilibrium. The intersection of the
melting and deliquescence curves around T ≈ 253.65 K (−19.35 °C) and Sw = 0.83 in Fig. 11.4 is the
eutectic point for ammonium sulfate. The eutectic point for NaCl (the major component of seawater
and many sea-generated aerosols) is at −21.2 °C. Further equilibrium at a higher solute concentra-
tion (or lower Sw) is possible along the deliquescence curve Tdel(Sw). The homogeneous solution may
exist above Tdel(Sw), and a mixture of crystallized salt and solution exists below Tdel(Sw) but above
the eutectic point. Below the eutectic point, the salts form various hydrates. The salt NaCl forms
the bihydrate NaCl · 2H2O (Curry and Webster, 1999), and ammonium sulfate forms thetrahydrate
(NH4)2SO4 · 4H2O (Xu et al., 1998).
Fig. 11.4 shows that the slope of the deliquescence Tdel(Sw) branch is much steeper than that of
the melting branch Tm(Sw). This can be explained if we assume that the solution behavior is not very
different from the ideal, and x sgs ≈ (1 − aw ) gs. Then, (Eqns. 11.5.1) and (11.5.2) represent two power
laws, but with the different indices. As was shown in Chapter 8, Gn = RT /( Lefm M s ) ≈ 0.38 at these
values of T, and a calculation for ammonium sulfate gives gs = ν RT /( Lefc M s ) ≈ 0.98 . Hence, the
power index Gn in (Eqn. 11.5.1) for the Tm is much smaller than gs, and the decrease in the equilib-
rium melting (freezing) temperatures with decreasing Sw (increasing solution concentration) on the
left from the eutectic point on the phase T-Sw diagrams (liquidus curve) predicted by (Eqn. 11.5.1)
is substantially slower than the temperature increase predicted by (Eqn. 11.5.2), in agreement with
observations (see e.g., Fig. 4.8 in Curry and Webster, 1999; or Figs. 3–8 in Martin, 2000).
Equations (11.5.1) and (11.5.2) enable evaluation of the eutectic point—i.e., the mole fraction of
solute at this point of intersection—for solutions without strong non-ideality. Equating (Eqns. 11.5.1)
and (11.5.2), we obtain an equation for the eutectic point:
ef ef
T0 awRT / M s Lm = T* (as /as* ) RT / M s Lc . (11.5.3)

The water activity aw can be approximately related to the molality M̂ as in Tang and Munkelwitz
(1993, 1994), Pruppacher and Klett (1997), (see Chapter 3 here):

aw = 1 − Bs Mˆ , Bs = 10 −3 ν Φ s M w , (11.5.4)

where n is the number of ions in the solution, Fs is the osmotic potential, and Mw is the molecular
weight of water. Note that the value Bs = 0.034 in (Eqn. 11.5.4) gives a very good approximation of
the experimental data from the relation between aw and M̂ for ammonium sulfate. Molality can be
expressed via the mole fraction xs as Mˆ = ( 10 3/ M w ) x s /(1 − x s ) . Substituting this into (Eqn. 11.5.4),
and taking into account that in saturated solutions xs ∼ 0.1 << 1 (Seinfeld and Pandis, 1998), and xs
can be neglected in the denominator, we obtain an approximate linear expression of aw via xs:

aw = 1 − bs x s , bs = 10 3 Bs /M w = ν Φ s . (11.5.5)

Substituting this into (Eqn. 11.5.3), and assuming that as/as* ≈ xs/xs* (relatively small variations of the
salt activity coefficients), we obtain:

T0 (1 − bs x s )Gn = T* ( x s /x s* ) gs . (11.5.6)
566 Deliquescence and Efflorescence in Atmospheric Aerosols

Taking the power 1/gs and expanding the left-hand side by the powers of small xs, we obtain a linear
equation for xs. Its solution for the mole fraction xs,eut at the eutectic point is

λeu x s*
x s ,eut = , (11.5.7)
1 + α eu bs λeu x s*

where
1/ gs M s Lefc /(ν RT )
T  T   G   M s Lefc 
λeu =  0  =  0 , α eu =  n  =  ef 
. (11.5.8)
 T*   T*   gs   ν M w Lm 

Equation (11.5.7) yields the coordinate of the eutectic point—i.e., an expression for the solute mole
fraction xs,eut at this point via the mole fraction xs* at a reference point T = T*.
Consider the following application. Suppose we need to calculate the eutectic mole fraction for
ammonium sulfate and choose the reference point T* = 298.15 K, then the reference mole fraction
xs*(T* = 298.15) = 0.0944 mol mol−1 (Seinfeld and Pandis, 1998). The parameter bs calculated from
(Eqn. 11.5.5) with Bs = 0.034 for a saturated solution is bs ≈ 1.83; aeu = Gn/gs ≈ 0.38/1.0 = 0.38. Since
T0 = 273.15 K, and gs ≈ 1, then leu ≈ (273.15/298.15)1 = 0.916. Substituting these values into (Eqn.
11.5.7), we obtain xs,eut ≈ 0.0816 mol mol−1. Comparing this value to the experimental data xs,eut =
0.0828 (Seinfeld and Pandis, 1998), we find that the relative error Dxs,eut /xs,eut is 1.4%, which illus-
trates a good accuracy of (Eqn. 11.5.7). Calculations for the other salts can be done in the same way
given the values of the required parameters. This simple estimate for the eutectic point may be helpful
in constructing or constraining the phase diagrams for various substances.

11.6. A Model for the Efflorescence of Salt Crystals Based on the Entropy Equation

As discussed in Section 11.1, there are two types of efflorescence that proceed as homogeneous and
heterogeneous nucleation. We consider first efflorescence as a process of homogeneous nucleation of
a salt crystal in a solution supersaturated with respect to solute at decreasing humidity. The treatment
is similar to homogeneous ice nucleation in Chapter 8 and is based again on the general equilibrium
(or entropy) (Eqn. 3.6.4). The phase transition in this case is salt crystallization. Phase 1 is salt in
solution, and phase 2 is salt in the crystal. With the same definitions as in Section 11.3 for deliques-
cence, (Eqn. 3.6.4) can be rewritten for efflorescence as

(hs 0 − hc 0 ) v v a 
− dT + s 0 dpc − c 0 dps + Rd ln  s  = 0, (11.6.1)
T2 T T  ac 

where hc0 and hs0 are the enthalpies of the solid and solution, pc and ps are pressures inside a crystal
and inside a solution drop, vs0 and vc0 are the molar volumes of salt in a solution and a solid, and as
and ac are the activities of salt in a solution and a crystal. We assume again that the activity of the pure
salt ac = 1. As in the case with deliquescence, to account for the ionic dissolution and following Defay
et al. (1966), we replace ln as = ln(γ s x s ) → ν ln aɶ s . The non-ideality of solutions can be accounted for
by replacing n → nFs. We assume that crystallization occurs with positive heat release, the enthalpies
difference in (Eqn. 11.6.1) is hs0 − hc0 = MsLc, where notations are the same as in the previous section.
11.6. A Model for the Efflorescence of Salt Crystals Based on the Entropy Equation 567

Pressures pc and ps inside a crystal of radius rc and in a solution drop of radius rs are related to the
environmental pressure p in Laplace’s equations:

2σ sa 2σ cs
ps = p + , pc = ps + , (11.6.2)
rd rc
where scs and ssa are the surface tensions at the crystal–solution and solution–environment inter-
faces, respectively. Substituting the enthalpies difference and Laplace’s relations (Eqn. 11.6.2) into
(Eqn. 11.6.1) and multiplying by T, we obtain:

dT  2σ   2σ 
− M s Lc −∆vdp −∆vd  sa  − vc 0 d  cs  + RTν d ln aɶ s = 0, (11.6.3)
T  d 
r  rc 

where Dv = vc0 − vs0. Integrating as before, from some reference point T*, 1/rd = 0, 1/rc = 0, p = p*, aɶ s*
to the current values T, rd, rcr, p, aɶ s, we obtain

T*  2σ   2σ 
M s Lefc ln − ∆v ∆p − ∆v  sa  − vc 0  cs  + ν RT ln Sɶs = 0, (11.6.4)
T  rd   rc 

where we introduced the activities ratio Sɶs = aɶ s / aɶ s*. As in the previous case with deliquescence, if
we chose the reference point with saturated activity aɶ s* , then Sɶs is the solution supersaturation. The
tildes over as and Ss and the bars over volumes are omitted hereafter for brevity.
As in Section 11.3 with deliquescence, there are c = 3 components (salt, solvent, and air), and Nw =
4 degrees of freedom in this system. If the salt mass is constant, this imposes one more constraint, and
Nw = 3. If we fix three variables in (Eqn. 11.6.3), T, p, and rd, then the first three terms on the left-hand
side in (Eqn. 11.6.4) vanish. If we additionally assume that variations of the activity coefficient gs are
weaker than variations of the solution concentration xs, or the solution is close to the ideal, so that
aɶ s /aɶ s* = γ s x s /γ s* x s* ≈ x s / x s* , and there is no ion dissociation, n = 1, then the remaining two terms in
(Eqn. 11.6.4) yield

 2σ cs  RT  x s 
 r  = v ln  x  . (11.6.5)
 c  c0  s* 

This is again a known Freundlich–Ostwald equation (Defay et al., 1966) that describes the effect of
the salt crystal radius curvature on its solubility and is similar to the Kelvin (Eqns. 3.8.5) or (3.8.6). If
we assume that the surface tension of the crystal scs does not depend on the crystal size, Freundlich–
Ostwald (Eqn. 11.6.5) shows that the solution concentration in equilibrium with a small crystal is
greater than the concentration of the bulk solution and increases as the crystal size decreases. That
is, the solubility xs of small crystals increases as their size decreases—i.e., the smaller crystals are
more soluble than the larger ones. If crystals of various sizes are placed in a supersaturated solution,
the smaller crystals will dissolute and the larger crystals will grow at their expense. A detailed theory
of this process for a polydisperse salt crystal ensemble was developed by Lifshitz and Slezov (1958,
1961) (see also Lifshitz and Pitaevskii, 1997), and was called coalescence (with the other meaning
than used in meteorology). Lifshitz and Slezov introduced in this problem of coalescence a kinetic
568 Deliquescence and Efflorescence in Atmospheric Aerosols

equation for the diffusion growth of the salt crystal size spectrum. This kinetic equation was
generalized and then applied by Buikov (1961, 1963, 1966a,b), Levin and Sedunov (1966) and others
in cloud physics for the diffusion growth of the water drop and crystal size spectra as described
in Chapters 5, 13, and 14. It is interesting to note that the kinetic equations for the diffusion growth
of drops and crystals, the primary mechanism of initial cloud formation, were formulated only
40–50 years later than the Smoluchowski kinetic equation for coagulation that describes particles
growth and precipitation formation at the later stages of cloud development.
The other consequence of (Eqn. 11.6.5) is that a small crystal of radius rc cannot appear in a
solution until its mole fraction xs(rc) is greater than the equilibrium value xs* for the bulk solu-
tion; that is, the solution should be supersaturated. This fact is substantial for explanation of the
phenomenon of efflorescence considered further on. Equation (11.6.4) of this Khvorostyanov–
Curry (KC) model is a generalization of the Freundlich–Ostwald (Eqn. 11.6.5) and can be
rewritten as

 2σ cs  ν RT  aɶ s  M s Lefc T ∆v  2σ sa  ∆v
 r  = v ln  aɶ  + v ln * − −
T vc 0  rd  vc 0
∆p. (11.6.6)
 c  c0  s*  c0

The terms of the right-hand side show that besides the effect of the crystal radius on solubility, this
equation also describes the effects of the temperature T, the radius rd of the liquid solution drop
where a salt crystal nucleates, the external pressure Dp, the ion dissociation n, and the non-ideality
of solutions.
The critical radius rc of the salt crystal germ in solution can be obtained from (Eqn. 11.6.4) as
2σ cs vc 0
rc ,eff = , (11.6.7)
T  2σ
M s Lefc ln  *  − ∆v ∆p − ∆v sa + ν RT ln Ss
T rd

or, in a more compact form

2σ cs vc 0
rc ,eff = , (11.6.8)
 T* gs 
ef 2σ
M s L ln  Ss  − ∆v ∆p − ∆v sa
c
T  rd

where Dv = vc0 – vs0, and the parameter gs = ν RT /( Lefc M s ) is the same as in (Eqn. 11.3.9). More
compact forms of rc are
2σ cs vc 0
rc ,eff = , (11.6.8a)
M s L ln  * Ssgs exp(− H eff ) 
ef T
c
T 
2σ sa
rc ,eff = , (11.6.8b)
ρc 0 L ln  * Ssgs exp(− H eff ) 
ef T
c
T 
where the term Heff describes the effects of the pressure and finite size of the solution drop:

∆v  2σ sa  ∆ρ s  2σ sa 
H eff =  ∆p + r  = Lef ρ ρ  ∆p + r  . (11.6.9)
Lefc M s  d  c c0 s0  d 
11.6. A Model for the Efflorescence of Salt Crystals Based on the Entropy Equation 569

The critical energy DFcr,eff of homogeneous nucleation of the efflorescence crystalline germ in solu-
tion can be derived in terms of the classical nucleation theory from the minimum of the sum of the
volume and surface energies similar to the homogeneous freezing in Section 8.6, which yields

4 16π vc20σ cs3

∆Fcr ,eff = πσ cs rc2,eff = 2 (11.6.10)
3 3   T* S gs exp − H  
 s c 

M L ef
ln
T
s (
eff  

)
16π σ 3
= cs
2 . (11.6.10a)
3  

ef 
T
T* gs
(
 ρc Lc ln  Ss exp − H eff  


)
Equation (11.6.9) shows that the value of Heff > 0. Therefore, this factor causes a decrease of the
denominators in rc,eff and DFcr,eff, and an increase in rc,eff and DFcr,eff, and so hampers efflorescence,
making it energetically more difficult. Thus, an increase of the external pressure and a decrease in
the radius of the solution drop suppress efflorescence and shifts it to the lower humidities—i.e., ERH
decreases with increasing pressure and decreasing drop radius.
The nucleation rate of homogeneous efflorescence [cm−3 s−1] can be written by analogy with
homogeneous freezing described in Chapter 8:

 ∆Fcr ,eff ∆Fact ,eff 

Jeffhom = Ceffhom exp  − − , (11.6.11)
 kT kT 
 v kT   σ cs  1/2  ρc 0 kT   σ cs  1/2
Ceffhom = 2 N cc  s 0    = 2 N cc    , (11.6.12)
 vc 0 h  kT  ρ s 0 h   kT 

where DFact,eff is the activation energy barrier for efflorescence and all the quantities were defined in
Section 11.3 and after (Eqn. 11.3.15).
As discussed in Section 11.2, if a foreign substrate (e.g., insoluble salt or a mineral dust particle) with
a radius rN is present inside a solution drop, then efflorescence may proceed via heterogeneous mode
similar to heterogeneous freezing described in Chapter 9. The critical radius of a salt germ can be cal-
culated with (Eqns. 11.6.8a), (11.6.8b), but the critical energy should be modified by multiplication by
the geometric factor that arises due to the contact angle qcs between the salt and the foreign substance:

16π vc20σ cs3 f (mcs , x )

∆Fcr ,eff == 2 , (11.6.13)
3   T* S gs exp − H  

Lef
 s c 
M ln
T
s ( eff  

)
where mcs = cos(qcs), x = rN/rc,eff, and f(mcs, x) is described by (Eqns. 9.7.16), (9.7.16a), or (9.7.16b),
depending on the geometry of efflorescence. The heterogeneous nucleation rate on the entire surface
of a salt crystal [s−1] can be calculated similar to (Eqn. 11.6.11), but replacing Ceffhom with the kinetic
coefficient for heterogeneous nucleation:

 ∆Fcr ,eff ∆Fact ,eff 

Jeffhet = Ceffhet exp  − −  , (11.6.14)
 kT kT
 kT 
Ceff ≈ N cc 
het
c 4π rc, eff ,
2
 h  1cs (11.6.15)

where Ncc is the number of salt molecules in a crystal in contact with the unit area of a solution, c1cs
is the number of molecules adsorbed on the surface of the solid. The parameters Ncc and c1s can be
estimated using the parameters of crystalline lattice for a given salt.
570 Deliquescence and Efflorescence in Atmospheric Aerosols

11.7. Applications of the Efflorescence Model

11.7.1. The Temperature Dependence of Efflorescence

Some useful relations can be obtained by solving (Eqn. 11.6.11) relative to DFcr,eff and equating to
(Eqn. 11.6.10):

Jeff 16π vc20σ cs3

− kT ln − ∆Fa ,eff = 2 . (11.7.1)
Ceff 3   T* gs  

ef

T
(
 M s Lc ln  Ss exp − H eff  

)
Dividing the unity by both sides of (Eqn. 11.7.1), and then rearranging the terms and taking the
square root, this equation is transformed into:

T 
ln  * Ssgs exp(− H eff )  = Πeff , (11.7.2)
T 
where
1/2
1  16π vc20σ cs3 
Πeff = ef 
−  . (11.7.3)
M s Lc  3 kT ln( Jeff /Ceff ) + ∆Fa ,eff 

Equation (11.7.2) yields

gs
T*  as 
= exp( H eff ) exp(Πeff ). (11.7.4)
T  as* 

This equation expresses the salt activity as at efflorescence as a function of the temperature, or vice
versa, the temperature of efflorescence as a function of as. Solving (Eqn. 11.7.4) for T, we obtain the
temperature of efflorescence Teff in the KC model:
gs
 a 
Teff = T*  s  exp(− H eff ) exp(− Πeff ). (11.7.5)
 as* 

In expanded form, Teff becomes

g
 a 
s
 ∆v  2σ sa  
Teff = T*  s  exp  − ef 
∆p + × −
 as*   M L
s c  rd   Ms

   16π σ cs3 vc20 f (mcs , x ) 

1/ 2

 1 
  × exp − M Lef −  , (11.7.6)
rd  
 s c  3 kT ln( Jeff /Ceff ) + ∆Fact ,eff  
where the factor f(mcs, x) is added to account for the possible incomplete wettability by the solution
of its own crystal or for the possible generalization for heterogeneous efflorescence. This equation
can be applied for both homogeneous and heterogeneous efflorescence, using the corresponding
expressions for Jeff and Ceff from Section 11.5. If efflorescence occurs as homogeneous nucleation
with complete wettability, then the geometric factor f(mcs, x) 5 1.
11.7. Applications of the Efflorescence Model 571

11.7.2. The Solute Activity and Mole Fraction Dependence of Efflorescence

Solving (Eqn. 11.7.4) for as, we obtain an expression for the salt activity of efflorescence:
1/ gs
T
as ,eff =   as* [exp( H eff ) exp(Πeff )]1/ gs . (11.7.7)
 T* 

In expanded form, substituting 1/gs, this becomes

M s Lefc / (ν RT )
 Teff   ∆v  2σ sa  
as ,eff = as *  exp   ∆p + r   × −
 T*   ν RT  d   R

  1  16π vc20σ cs3 f (mcs , x )  

1/ 2

 × exp  −  . (11.7.8)
r   ν RT  3 kT ln( Jeff /Ceff ) + ∆Fact ,eff  

This equation is simplified for the process at constant pressure (Dp = 0), and bulk solutions (1/rd = 0):
ef
/ (ν RT )
as ,eff = as* (Teff /T* ) M s Lc × e
 1  16π vc20σ cs3 f (mcs , x ) 
1/ 2

 
= ) × exp  −  . (11.7.9)
ν RT  3 kT ln( Jeff /Ceff ) + ∆Fact ,eff 
 
If efflorescence proceeds via homogeneous nucleation without foreign substances, then mcs = −1, and
f(mcs, x) = 1. If variations of the activity coefficients gs are smaller than variations of the mole fraction,
then as,eff /as* ≈ xs,eff /xs*, and (Eqn. 11.7.8) can be rewritten for the mole fraction as
M s Lefc / (ν RT )
 Teff   ∆v  2σ sa  
x s ,eff = x s*  exp   ∆p + r   × −
 T*   ν RT  d   R

  1  16π vc20σ cs3 f (mcs , x ) 

1/ 2

 
  × exp  ν RT −  . (11.7.10)
r  
  3 kT ln( Jeff /Ceff ) + ∆Fact ,eff  
Similar to the estimate of ice nucleation in Chapter 8, the nucleation rate of efflorescence Jeff can
be determined as described in Section 11.2, from the particle volume Vc at efflorescence and the
induction time tind for the nucleation, assuming that a single nucleation event occurs in a droplet at
efflorescence:
1
Jeff = . (11.7.11)
tind Vc

As an example, the mole fraction xs and weight percent w were calculated for homogeneous efflo-
rescence for ammonium sulfate particles of 1 μm as the functions of temperature using (Eqn. 11.7.10)
of this KC model. Calculations were performed with f(mcs, x) = 1 (homogeneous nucleation) for
the constant pressure (Dp = 0), and the values of the parameters close to those from Snider and
Richardson (1994), Onasch et al. (2000), and others described in Section 11.2. The nucleation rate in
(Eqn. 11.7.11) was calculated with tind = 1 s, and the volume Vc for the particles with a radius of 1 μm.
The volume of a single-molecule crystal was taken as vc0(1) = 12.4 × 10−23 cm3/molecule based on the
572 Deliquescence and Efflorescence in Atmospheric Aerosols

sizes of the crystalline lattice of ammonium sulfate; thus, the molar volume used is vc0 = vc0(1)NAv =
12.4 × 10−23 cm3 × 6.02 × 1023 mol−1 = 74.4 cm3 mol−1. The activation energies were taken from the
cited works as DFact = 6 kT. The most sensitive and still uncertain parameter is the surface tension
scs at the interface of the salt crystal surface and solution. Richardson and Snider (1994) found it in
the range 50–64 erg cm−2, and Onasch et al. (2000) estimated it as 55 erg cm−3 for homogeneous efflo-
rescence at room temperatures. We selected values of scs at T = 298 K, and then slightly fitted them
to match the experimental data as clarified in the following text.
The mole fraction xs(T) calculated with (Eqn. 11.7.10) was recalculated to the weight percent w
as described in Section 3.5. The results are shown in Fig. 11.5 as the temperature-composition phase
diagram T-w. The laboratory data from Xu et al. (1998) and from Cziczo and Abbatt (1999, CA)
are also shown. These two data sets are close in the region around T = 300 K, but differ at the other
temperatures, variations in w are weaker in the Cziczo and Abbatt data set. The good agreement with
both data sets was achieved using the two temperature-dependent models for the surface tension,
and all the other parameters are the same. Thus, the two calculations with the KC model shown in
Fig. 11.5 differ only by the temperature-dependent model of the surface tension scs: calculations
close to Cziczo and Abbatt (1999) (asterisks) are with scs,1(T) = [58 + (dscs/dT)1 × (T − 298)] erg cm−2
with (dscs/dT)1 = 0.07 erg cm−2 K−1, calculations close to Xu et al. (1998) (circles) are with

380
Xu et al. (1998)
360
KC model,σcs,1(T)
340 CA (1999)
320 KC model,σcs,2(T)
Tefflor

300

280

260

240

220
40 50 60 70 80 90 100
Weight percent, amm. sul.

Figure 11.5. Measured and calculated with the KC model the temperature–composition phase
diagrams for the efflorescence of ammonium sulfate. Experimental data on the efflorescence are
from Xu et al. (1998, diamonds) obtained with the levitation technique and from Cziczo and
Abbatt (1999, triangles) obtained with the flow tube technique. The corresponding calculations
with the KC model described in the text differ only by the temperature-dependent model of the
surface tension scs: calculations close to Cziczo and Abbatt (1999) (asterisks) are with scs,1(T) =
[58 + (dscs/dT)1 × (T − 298)] erg cm−2 with (dscs/dT)1 = 0.07 erg cm−2 K−1; calculations close to Xu
et al. (1998) (circles) are with the scs,2(T) = [56 + (dscs/dT)2 × (T − 298)] erg cm−2, with (dscs/dT)2 =
0.46 erg cm−2 K−1. The values at 298 K are close, and the slopes (dscs/dT) are positive in agreement
with previous studies, but they significantly differ and may reflect the difference in the conditions
of the experiments.
11.7. Applications of the Efflorescence Model 573

scs,2(T) = [56 + (dscs/dT)2 × (T − 298)] erg cm−2, with (dscs/dT)2 = 0.46 erg cm−2 K−1. The values of
scs,2(T) vary from 84.5 erg cm−2 at T = 360 K to 20.1 erg cm−2 at T = 220 K; variations of scs,1(T) are
much smaller, from 62.3 to 52.5 erg cm−2 in this T-range. The calculated w(T) are close to both mea-
sured values near 300 K, which indicates the sufficient accuracy of this model. The composition in the
case with scs,1(T) varies from w = 82% at 294 K to 73% at T = 234 K, which is also close to the average
w ≈ 80% determined by Onasch et al. (1999). The slopes (dscs/dT) are positive in agreement with
previous studies, but significantly differ for the two experimental data sets and may reflect the differ-
ence in the conditions of experiments. There is no current agreement on the best measurements, and
the model of the surface tension can be clarified when these data are refined.
The same calculations can be performed for heterogeneous efflorescence. According to Richardson
and Snider (1994) and Onasch et al. (2000), the values of the contact angle for the tested less soluble
salts were ∼90°. Then, the contact parameter mcs(90°) is near zero, mcs(90°) ≈ 0, and Volmer’s geometric
factor in the equations of Sections 11.5 and 11.6 is described by (Eqn. 9.7.16a), f(mcs) = (mcs3 −
3mcs + 2)/4 ≈ 1/2—that is, the critical energy is decreased twice. This value can be substituted into
(Eqn. 11.7.10) and will yield the temperature or composition for the heterogeneous efflorescence.
For very small particles, the more precise Fletcher’s factor should be used, f(mcs, x) described by
(Eqn. 9.7.16) in Chapter 9 that accounts for the droplet curvature. Since f(mcs, x) < 1, its presence
in Equation (11.7.10) is equivalent to a decrease in the surface tension. As Fig. 11.5 shows, this is
equivalent to a decrease in the solution concentration, in agreement with the cited experiments and
models on the heterogeneous efflorescence.
Since Dv = vc0 − vs0 > 0 for ammonium sulfate and NaCl, (Eqn. 11.7.10) predicts an increase in xs
(solution supersaturation) with decreasing size rd of the solution drops, in agreement with the model
of Gao et al. (2006, 2007). This effect becomes especially large at very small rd for nanoparticles
since it is inversely proportional to rd. The corresponding calculations can be easily performed with
(Eqn. 11.7.10). This equation also predicts an increase in solution supersaturation with increasing
pressure. Verification of this prediction requires experimental data on efflorescence at high pressures
similar to the high-pressure experiments on water freezing and melting discussed in Chapters 4 and 8.

11.7.3. The Joint Phase Diagram

One of the most general and informative characteristics of solutions are the phase diagrams. Such
diagrams are usually constructed based on various empirical data for the solutions (e.g., Curry and
Webster, 1999; Martin, 2000, Landau and Lifshitz, v.5, 1958b). The results of Chapters 8, 9, and 11
show that these diagrams can be obtained theoretically. Collecting now the results of the calculations
of solutions freezing and melting described in Chapter 8, and the calculations of the deliquescence
and efflorescence in this chapter, we can plot the combined phase diagram for the stable and metastable
equilibriums of solutions. Fig. 11.6 shows the phase diagram for ammonium sulfate in the T – w
coordinates composed of the four temperatures: melting Tm, freezing Tf, deliquescence Tdel, and efflo-
rescence Teff—all calculated with this extension of the classical theory of ice and salt homogeneous
nucleation described in Chapters 8 and 11, and compared with the experimental data for each curve.
Melting temperature Tm from Khvorostyanov and Curry (2004b, crosses) is calculated with
(Eqn. 8.7.12b) or (Eqn. 11.5.1) and is compared with the laboratory data from Xu et al. (1998, stars)
574 Deliquescence and Efflorescence in Atmospheric Aerosols

380
Tm, KC-2004 Tdel, KC model
360
Tm, CW-1999 Tdel, Xu-1998
340
Tm, Xu-1998
320

300
Temperature (K)

280

260

240 Tf3, Xu-1998

220
Teff, KC model
200
Teff, Xu-1998
180 Tf1, KC-2004

160 Tf2, Bertram-2000

0 10 20 30 40 50 60 70 80 90 100
Ammonium sulfate (w, %),

Figure 11.6. Phase diagram for ammonium sulfate in the T – w coordinates composed of four
temperatures, melting Tm, homogeneous freezing Tf, deliquescence Tdel, and efflorescence Teff, all
calculated with this modification of the classical theory of ice and salt homogeneous nucleation
described in Chapters 8 and 11 (the KC model), and compared with the experimental data for each
curve. The melting temperature Tm from Khvorostyanov and Curry (2004b, crosses) calculated
with (Eqns. 8.7.12b) or (11.4.1), compared with the lab data from Xu et al. (1998, stars) and with
Curry and Webster (1999, asterisks); homogeneous freezing temperature Tf1 (bold squares) from
Khvorostyanov and Curry (2004a) calculated with (Eqn. 8.7.7) here and compared with the lab
data Tf 2 from Bertram et al. (2000, open squares) and with the lab data Tf 3 from Xu et al. (1998,
triangles); deliquescence temperature Tdel (KC model) calculated with (Eqn. 11.4.2) here and
compared with the experimental data from Xu et al. (1998); efflorescence temperature Teff (solid
circles, KC model) calculated with (Eqn. 11.7.6) here and compared with the experimental data
from Xu et al. (1998, open circles).

and from Curry and Webster (1999, asterisks). This curve describes the stable equilibrium between ice
and the solution. The homogeneous freezing temperature Tf 1 (bold squares) from Khvorostyanov and
Curry (2004a) is here calculated with (Eqn. 8.7.7) and compared with the lab data Tf 2 from Bertram
et al. (2000, open squares) and with the lab data Tf 3 from Xu et al. (1998, triangles). This curve
describes the metastable equilibrium between ice and the solution. The difference between the melting
and freezing temperatures describes the melting–freezing hysteresis.
The deliquescence temperature Tdel is calculated with the KC model (Eqn. 11.4.2) here, and is
compared with the experimental data from Xu et al. (1998). This curve describes the stable equilib-
rium between the salt and the solution. The efflorescence temperature Teff (solid circles) is calculated
11.7. Applications of the Efflorescence Model 575

with the KC model (Eqn. 11.7.6) here, and compared with the experimental data from Xu et al. (1998,
open circles). This curve describes the metastable equilibrium between the salt and the solution.
The difference between the deliquescence and efflorescence temperatures describes the humidity
hysteresis.
As this figure shows, the melting and deliquescence temperatures from various sources agree well,
but there is still some discrepancy among the experimental data from various sources for the freezing
and efflorescence curves. In particular, the experimental efflorescence curve Teff(w) from Xu et al.
(1998) could be replaced with that from Cziczo and Abbatt (1999) and with the corresponding cal-
culated curve Teff(w) shown in Fig. 11.5 with the different model of the crystal surface tension. Thus,
further experiments are needed to refine the exact positions for each curve.
However, a general comparison allows the following conclusions. 1) It is possible, using the
general equilibrium (entropy) (Eqn. 3.6.4) of Section 3.6 and the extended classical nucleation
theory described in Chapters 8 and 9 and in this chapter, to calculate all components of the phase
diagrams for various solutions. Such calculations can be a useful tool for constraining and refin-
ing the experimental data. 2) The extended classical nucleation theory of the deliquescence and
efflorescence developed here in Chapter 11, along with the corresponding theories of freezing
and melting from Chapters, 8, 9, and 10, can be a reliable and precise enough tool for inclusion in
numerical models of various complexities for description of the freezing–melting and deliquescence–
efflorescence phenomena. This tool may help refine or replace many existing empirical parameteriza-
tions of these effects.
12
Terminal Velocities of Drops and Crystals

12.1. Review of Previous Theories and Parameterizations

Whereas a number of factors can contribute to inaccurate simulation of the gravitational fallout of
cloud particles and hydrometeors (e.g., inaccuracies in parameterization of particle size distribution,
habit and density), a key element in the parameterization of precipitation and gravitational settling of
cloud particles and hydrometeors is the terminal velocity.
Probably the first known attempt to explain fall velocity was made by Aristotle in the 4th century
B.C. Aristotle observed that heavy stones fall much faster than light leaves falling from trees and
concluded that the fall velocity of a body is proportional to its weight. Aristotle did not clarify which
velocity was meant: the initial velocity just after initiation of the fall, or the final constant velocity
that the body can reach falling in a viscous media, which is now referred to as the terminal velocity.
Aristotle’s conclusion was not challenged for almost 2000 years. In the 16th and 17th centuries,
Galileo and then Newton performed experiments with falling bodies, discovering that the gravita-
tional acceleration g is constant and universal for all bodies. Newton discovered later the gravita-
tional law, which expresses g via the masses of two attracting bodies and the distance between them.
That is, g for various planets is proportional to the planet mass and decreases with height above the
surface. However, over distances comparable to the depths of the planetary atmospheres and clouds,
variations of g are small and usually can be neglected. Assuming that g = const, Galileo and Newton
derived the equation for the velocity of a falling body, V = gt, that does not depend on the body’s mass
without accounting for the resistance of the medium, but does depend on time t. It became clear that
the fall velocities of heavy bodies measured over short times rather weakly depended on their weight,
although there was some difference in the fall speeds for bodies of various shapes. This discovery of
the gravitation law and universal gravitational acceleration g seemingly disproved Aristotle’s theory.
Subsequently, studies of fall velocities branched into two major lines. One line of research con-
centrated on the fall velocities of the bodies falling in viscous media with a drag force. Another line
of research was devoted to the free fall of the bodies in vacuum. The studies accounting for the drag
force showed that the velocity of a body falling in a viscous medium reaches some limiting value,
called the terminal velocity Vt. Thus, if a body falls at the terminal velocity, its acceleration is close
to zero, and depends on the mass of the body. When a body falls in a gravitational field in vacuum
without resistance, Galileo and Newton found that the acceleration of a falling body does not depend
on its mass. This finding has important consequences. Einstein postulated later that free motion in a
gravitational field is equivalent to the motion in a non-inertial coordinate system, when all the bodies
move with the same acceleration. This postulate, termed the “equivalence principle”, is one of the
basic premises in the general relativistic theory formulated by Einstein since 1916 (e.g., Landau and
Lifshitz, v. 2, 2005, chapters 10 and 11 therein.)

577
578 Terminal Velocities of Drops and Crystals

Another two centuries passed after Galileo’s studies before Stokes derived and solved the hydro-
dynamic equations for a viscous fluid (the term fluid henceforth refers to any liquid or gaseous
medium), now called the Navier–Stokes equations. Stokes found that the drag force FD of a spherical
body with radius r falling with the velocity V in a liquid or air with the dynamic viscosity h is deter-
mined by the equation FD = 6phrV (e.g., Landau and Lifshitz, v.6, 1959). The motion of a falling
body with density rb is then determined by a balance of the gravitational force Fgr = mg = (4/3)pr3rb
and the drag force FD (neglecting buoyancy, electrical, and other external forces that may act on the
body). This balance of forces is written as

dV 4
m = Fgr − FD = π r 3 ρ b g − 6πηrV . (12.1.1)
dt 3
Dividing both sides of (Eqn. 12.1.1) by m yields for the acceleration

dV V 2 ρb 2
= g− , τ v ,rel = r . (12.1.2)
dt τ v ,rel 9 η

The parameter tv,rel is the velocity relaxation time, during which the falling body reaches a steady-
state terminal velocity. The terminal velocity with the Stokes drag force is determined from (Eqn.
12.1.2) with the condition dV/dt = 0:

2 g ρb 2 2 g ρb 2 g ρb η
VSt = gτ v ,rel = r = CSt r 2 , CSt = = , ν= , (12.1.3)
9 η 9 η 9 νρ F ρF
where n is the kinematic viscosity related to the dynamic viscosity h and the fluid density rF. The
velocity VSt is the Stokes terminal velocity for the sphere, the equation Vt(r) = CStr2 is Stokes’ law and
Cst is the Stokes parameter. Calculation with the standard conditions gives Cst = 1.2 × 106 cm−1 s−1.
A general time-dependent solution of (Eqn. 12.1.2) is
− t / τ v ,rel
V (t ) = VSt (1 − e ). (12.1.4)

The limit at small times is determined by the expansion 1 − exp(−t/tv,rel) ≈ t/tv,rel, and substitution
into (Eqn. 12.1.4) with the use of (Eqn. 12.1.3), yields V(t) ≈ gt. Thus, v(t) tends to the free fall limit
at t << tv,rel; that is, the viscous drag force can be neglected at t << tv,rel. The effect of the drag force
becomes significant at t ≥ tv,rel, and V(t) tends to VSt at t >> tv,rel.
If a body begins motion in the horizontal direction with initial velocity V0—e.g., in a turbulent
fluctuation—its motion can be described by (Eqn. 12.1.2) with g = 0, that is

dV V − t / τ v ,rel
=− , and V (t ) = V0 e . (12.1.5)
dt τ v ,rel

This clarifies the meaning of the relaxation time tv,rel: during this time the initial velocity decreases
by e times. The values of tv,rel are small—e.g., at the normal conditions, tv,rel(r = 50 μm) ≈ 0.03 s,
tv,rel(r = 100 μm) ≈ 0.12 s, and tv,rel(r = 200 μm) ≈ 0.5 s. Two conclusions follow from these estimates:
1) small droplets mostly follow the turbulent fluctuations of the air with very small inertia, allowing
the turbulent transport of the drops to be calculated in the same manner as other conservative sub-
stances; and 2) differences in the velocities of the particles of various sizes may effect their collisions
and accelerate the coagulation and accretion processes.
12.1. Review of Previous Theories and Parameterizations 579

Returning to Stokes’ law, we notice that since Vt ∼ r2, and the mass of a spherical body m ∼ r3, it
follows from (Eqn. 12.1.3) that Vt ∼ m2/3; thus, Aristotle’s intuitive guess Vt ∼ m was not so far from
reality. However, Stokes’ law is valid only for spherical bodies, and the size dependencies of the
terminal fall velocities of nonspherical bodies (e.g., large drops and ice crystals) are more complex.
Precise parameterization of gravitational settling and fallout of cloud particles and hydrometeors
is essential for accurate simulation of precipitation amounts, cloud dissipation, and cloud optical
properties. Problems in parameterization of the fallout of cirrus cloud particles have been highlighted
recently by the Intercomparison of the Cirrus Cloud and Parcel Models Projects performed within
the Working Group 2 on Cirrus Clouds of the GEWEX Cloud System Study (GCSS; Randall et al.,
2003). These intercomparison studies showed large differences in calculated ice crystal terminal
velocities among similar models and illustrated the high sensitivity of the simulated cloud properties
to the parameterization of fall velocity (Starr et al., 2000). The intercomparison studies stimulated
a special activity on the sensitivity and comparison studies of the fall velocities. Recent numerical
experiments with single column models (Petch et al., 1997) and with the ECMWF model (Stephens
et al., 2000) showed that relatively small variations in parameterized ice crystal terminal velocities
produce substantial differences in the simulated ice water paths, cloud boundaries, and cloud opti-
cal properties. This led to the conclusion that the discrepancies between the model simulated and
the satellite-measured global radiative balance can be caused by inaccurate parameterization of fall
velocities.
Numerous experimental studies have produced a wealth of data on terminal velocities, which are
typically parameterized in the form of power laws by analogy with Stokes’ law:

Vt = Av D Bv (12.1.6)

where Vt is the terminal velocity, D is the particle diameter or maximum length, and the coeffi-
cients Av, Bv are determined from best fits to the experimental data (e.g., Gunn and Kinzer, 1949;
Litvinov, 1956; Bashkirova and Pershina, 1964; Jayaweera and Cottis, 1969; Locatelli and Hobbs,
1974; Beard, 1976, 1980; Heymsfield and Kajikawa, 1987; Mitchell, 1996). A universal dependence
of Vt in the form (Eqn. 12.1.6) has not been found since the coefficients vary over the size spectrum;
however, several fits to the experimental data have been given with Av, Bv constant over some sub-
ranges of the size spectrum. For example, Rogers and Yau (1989), based on the data of Gunn and
Kinzer (1949), gave the following approximation for liquid drops of radius r:

Vt = k1r 2 , 0 < r < 40 µm, (12.1.7a)

Vt = k 2r , 40 µm < r < 600 µm , (12.1.7b)
1/2
Vt = k3r , r > 600 µm, (12.1.7c)

with k1 = 1.19·106 cm−1 s−1, k2 = 8·103 s−1, and k3 = 2.2·103 (ra0/ra)1/2 cm1/2 s−1. Similar parameteriza-
tions have been developed for ice crystals—for example, Starr and Cox (1985) found the best fit
for crystals in cirrus clouds using five subregions of the size spectrum with different coefficients.
Parameterizations of the power-law type (Eqns. 12.1.6) and (12.1.7) are used in many cloud models,
general circulation models, and remote sensing techniques; however, attempts to derive these coef-
ficients theoretically have been scarce.
580 Terminal Velocities of Drops and Crystals

Stokes’ theory applies to spherical drops in a laminar viscous flow. Subsequent studies showed
that a turbulent boundary layer and wake form around and behind the falling body, which influences
the terminal velocity in a manner that is characterized by the Reynolds number Re = DVt /n, where D
is the characteristic particle dimension and n is the kinematic viscosity. The thickness of the turbulent
boundary layer around the falling body can be estimated from the Navier–Stokes equations for the
vertical velocity component ui in a viscous incompressible fluid (Monin and Yaglom, 2007a)

∂ui ∂ui 1 ∂p
+ uα = Fα − + ν∆ui , (12.1.8)
∂t ∂ xα ρ F ∂ xi

where summation over three components is assumed by the repeated twice subscript a, Fa is an exter-
nal force, and p is pressure. The thickness of the boundary layer around the body can be estimated by
assuming steady-state (∂u3/∂t = 0). Then, the balance of forces exists between the nonlinear second
term on the left-hand side and the viscous force, the last term on the right-hand side. If the velocity of
the flow away from the object is V, and the object’s characteristic dimension is D, then an estimate for
the nonlinear term is u3(∂u3/∂x3) ∼ V2/D. If the depth of the boundary layer is δ, then the term ∂2u3/∂z2
∼ V/δ 2, and the viscous term is ν V/δ 2. Equating these two terms in the Navier–Stokes equation yields

V2 V νD D
~ν 2 , or, δ~ = 1/ 2 . (12.1.9)
D δ V Re
Equation (12.1.9) provides a quantitative description of the terminal velocities where the boundary
layer plays an important role (Section 12.2).
Numerous attempts have been made to extend Stokes’ law for larger values of the Reynolds num-
ber and nonspherical drops and crystals. However, a general theory remained elusive because flow
around a particle and its turbulent wake are complicated and evolve with increasing values of the
Reynolds number. The nonsphericity of a hydrometeor further complicates the flow. Some sophis-
ticated numerical models based on the solution of the Navier–Stokes equations have been applied
to study the stream functions and vorticity of the turbulent flow around the objects of the simplest
shapes: spheres, spheroids, and circular cylinders (for reviews, see Landau and Lifshitz, v.6, 1959;
Monin and Yaglom, 2007a,b; Pruppacher and Klett, 1997). However, such models have not been suc-
cessfully used to develop simple parameterizations like (Eqns. 12.1.6) and (12.1.7).
Substantial progress in finding a simple but general solution to the fall velocity problem was made
by Abraham (1970). He showed that fluid motion around a rigid sphere can be divided into two
regions: 1) a region close to the object where frictional effects are important; and 2) an outer region
where friction may be neglected. The first regime corresponds to the viscous flow around the body
with a maximum projected cross-sectional area A and the drag force FD(A) = (1/2)CD rFVt A, where
CD is the drag coefficient and rF is the fluid density. Abraham (1970) suggested considering the sec-
ond regime as the assembly of the body and the boundary layer with total projected area At so that the
assembly moves in a potential flow with the drag force FD0(At) = (1/2)C0 rFVt2At, where C0 is the drag
coefficient for the potential flow around the assembly without friction. Matching these two regimes,
Abraham found a general functional dependence of the drag on Reynolds number.
The next significant step was made by Beard (1980) and Bohm (1989; 1992) who used Abraham’s
model of the flow around a falling particle to determine a general analytical relation between the
12.1. Review of Previous Theories and Parameterizations 581

Reynolds number, Re, and Best (or Davies) number, X = CDRe2. Then, inverting the definition of
Re, Beard (1980) and Bohm (1989, 1992) obtained the general expressions for Vt as a function of
X for both the drops and crystals in algebraic form. Mitchell (1996) extended this work, assumed
a power-law representation for the X-Re relationship for four different regimes of X over the range
0.01 < X < 108, and found the power-law coefficients for the fall velocities of nonspherical ice crystals
using experimental mass-dimension (m-D) and area-dimension (A-D) relations. Mitchell’s formula-
tion led to a convenient power-law representation of Vt (D), although discontinuities are introduced
at the matching points.
The studies of Beard (1980), Bohm (1989, 1992), and Mitchell (1996) were extended by
Khvorostyanov and Curry (2002; hereafter KC02), who improved upon the discontinuous nature
of parameterization and derived a power law–type representation for the Re-X relation and for fall
velocities with coefficients as analytical continuous functions of X or the particle diameter D for the
entire size range. KC02 applied these equations for evaluation of the fall speeds and found good
agreement with experimental data for droplets and several crystal habits.
Mitchell and Heymsfield (2005; hereafter MH05) modified the Khvorostyanov and Curry (2002)
scheme. They used the equations for the power law representation of Vt from KC02, and added an
empirical correction term to the Re-X relation for turbulent effects with two new empirical constants.
The scheme MH05 (this modification of the KC02 scheme in MH05 was called in some subsequent
works the “MHKC scheme”) showed a better accuracy for large crystal aggregates, but it had a few
deficiencies: 1) presence of the two new unknown empirical constants limited its applicability since
it required additional tuning; 2) the term added to the X-Re relation to account for the turbulent
corrections was too smoothed over the wide range of sizes, from the smallest to the largest, while
the experimental data show that the turbulent effect was localized in a rather narrow region of sizes
and Re numbers as shown here in the following text; and 3) the drag and fall velocities in the MH05
scheme have incorrect asymptotics and can become negative at large particle dimensions.
Khvorostyanov and Curry (2005b; hereafter KC05) developed further their previous scheme KC02.
KC05 did not contain any empirical elements of the MH05 scheme and improved KC02 by several
modifications: 1) Instead of using the empirical corrections as in the MH05 scheme, KC05 analyti-
cally derived the turbulent corrections to the Reynolds number and to the coefficients of the power
law; 2) The constants for crystals recommended by Böhm (1989, 1992) were used in calculations;
and 3) The temperature and pressure corrections to the terminal velocities were analytically derived,
which improved the accuracy in applications in wide regions of heights and temperatures. No further
empirical corrections were needed, and the fall speeds of both droplets and crystals (including large
aggregates and hail) could be evaluated with the KC05 scheme with a sufficiently high accuracy.
This chapter, mostly based on the works by Khvorostyanov and Curry (2002, 2005b), presents
a unified treatment of cloud particle fall velocities for both liquid and crystalline cloud particles
over the wide size range observed in the atmosphere. The representation is formulated in terms of
the Best (or Davies) number, X, and the Reynolds number, Re. The fall velocities are represented
as generalized power laws. The coefficients of the power laws for the Re-X relation and for the fall
velocities are found as the continuous analytical functions of X or particle diameters over the entire
hydrometeor size range. The turbulent corrections for the drag coefficients and terminal velocities
are derived.
582 Terminal Velocities of Drops and Crystals

Analytical asymptotic solutions are obtained for these coefficients for the two regimes that repre-
sent large and small particles and correspond to potential and aerodynamic flows, respectively. The
analytical temperature and pressure corrections for the wide size ranges are derived and compared
with the previous parameterizations. The expressions for the Re-X relation and drag coefficients are
applied for spherical and nonspherical drops and several crystal habits with special attention paid to
the turbulent corrections. The accuracy of this scheme for the fall velocities is illustrated by the com-
parison with experimental data and previous formulations for small drops, large nonspherical drops,
and various ice crystal habits, from small crystals to aggregates and hail. In these calculations, pub-
lished mass-dimension and area-dimension relationships are used. Some applications are considered,
including parameterizations for the bulk and bin cloud models, climate models, remote sensing, the
atmospheres of other planets, and other fluids.

12.2. Basic Equations for Fall Velocities

The drag force FD around a rigid sphere with radius r and projected area A is obtained by matching
the drag forces for these two regions following Abraham (1970), as described in the previous section:

FD = (1 / 2) C D ρ F Vt 2 A = FD 0 = (1/2) C0 ρ F Vt 2 At , (12.2.1)

where notations are the same as in Section 12.1. The total projected area At for a sphere of radius
r according to Abraham (1970) is related to the sphere of radius r and the boundary layer depth d:

At = π (r + δ )2 = π r 2 (1 + δ /r )2 . (12.2.2)

Introducing Reynolds number:

Re = Vt D /ν = Vt D ρ F /η , (12.2.2a)

where D = 2r is the sphere diameter, n is the fluid kinematic viscosity (related to the dynamic viscos-
ity h and fluid density rF as n =h /rF), and the depth d is determined from boundary-layer theory
using the estimate (Eqn. 12.1.9) through

δ δ
= 0 . (12.2.3)
r Re1/ 2
Substitution of (Eqns. 12.2.2) and (12.2.3) into (Eqn. 12.2.1), gives the drag coefficient as in Abraham
(1970):

(
C D = C0 1 + δ 0 /Re 1/ 2 ) 2
. (12.2.4)

The constants C0 and d 0 were determined by Abraham to be C0 = 0.292 and d 0 = 9.06 for the drops.
Böhm (1989, 1992) determined the better constant for ice particles, C0 = 0.6 and d 0 = 5.83. Using
these values in (Eqn. 12.2.4) for the drops, the limiting value of CD at low Re is determined to be
CD = C0d 02/Re = 24/Re, which is the well-known expression for drag in the Stokes regime (Landau
and Lifshitz, v.6, 1959). These values of C0 and d 0 give an intermediate solution at Re > 1 between the
Stokes solution, which underestimates the drag, and Oseen’s solution to the Navier–Stokes equations,
which overestimates CD, and provides excellent agreement with experimental data.
12.2. Basic Equations for Fall Velocities 583

The equation of motion of a falling body is determined by the forces of gravitation Fgr = mg = rbvbg,
buoyancy Fb = rFvbg, drag FD, and the electrical force Fel = qE,

d v
= F gr + F b + F D + F el , (12.2.5a)

m
dt
where rb is the body density, vb is its volume, g is the acceleration of gravity, q is the electrical charge
of the particles, and E is the electrical field assumed directed upward. The terminal velocity Vt of a
falling body in the steady state dV/dt = 0, as described by (Eqn. 12.2.5a), follows from (Eqn. 12.2.5a)
by projection to the vertical direction. The force Fgr is directed downward, and the other three forces
are upward. Thus, taking into account the signs, Vt is obtained by equating the drag force FD to the
difference of the gravitational force Fgr and the sum of the buoyancy force Fb and electrical force Fel,

mg − Fb − Fel = ( ρ b − ρ F ) v b g − qE = FD = (1/2) C D ρ F Vt 2 A, (12.2.5b)

Solving for Vt, we obtain

1/ 2 1/ 2
 2 | mg − Fb − Fel |   | 2 g v b ( ρ b − ρ F ) − 2qE | 
Vt =   =  
 ρ F AC D   ρ F AC D 
1/ 2
 2g v b | ρb − ρ F | 
=  | 1 − K el |1/ 2 . (12.2.6a)
 ρ F AC D 

Kel is the ratio of the electrical force to the difference of the gravitation and buoyancy force,

qE
K el = . (12.2.6b)
| ρb − ρ F | v b g

The notation |…| refers to the absolute value, since here we consider the positive differences.
Equation (12.2.6a) shows that the effect of the electrical forces can be accounted for by multiplying
by the factor |1 − Kel|1/2, which is equal to 1 in the absence of the electrical charge. Hereafter, we omit
this factor for the sake of simplicity, keeping in mind that it can be accounted for in the final equation
for Vt. Then the expression for Vt becomes
1/ 2
 2g v b | ρb − ρ F | 
Vt =   . (12.2.6c)
 ρ F AC D 

The sign |…| of absolute value means that we consider falling bodies if they are denser than the fluid
(rb > rF) and rising bodies in the opposite case rb < rF. For hydrometeors in the air, rb >> rF, and the
term with rF under the absolute value sign can be neglected, however, if rb /rF ∼ 1, as, for example,
for sand particles in the ocean or for dropsondes or radiosondes in the air or for falling objects in
laboratory devices with dense liquids, then rF should be retained.
The dependence of CD on Vt complicates the solution of (Eqn. 12.2.6c). The problem is usually
solved by introducing the Davies or Best number, X:

X = C D Re 2 (12.2.7a)
2 2
2 (mg − Fb ) ρ F D 2v b ( ρb − ρ F ) g D
= 2
= , (12.2.7b)
Aη A ρF ν 2
584 Terminal Velocities of Drops and Crystals

where D is the maximum dimension of the body (particle), and we use (Eqn. 12.2.2a) for Re and
(Eqn. 12.2.6c) for Vt. The drag coefficient CD can then be determined as a function of Re and X,
which is a parameter that depends only on physical variables. To derive a continuous Re-X relation-
ship and hence a continuous expression for Vt, we proceed as follows. Multiplying (Eqn. 12.2.4) by
Re2, we obtain a relation

Re 2 C D = X = Re 2 C0 (1 + δ 0 /Re1/ 2 )2 . (12.2.8a)

Taking the square root, and then rearranging the terms and dividing by C01/ 2 yields

Re + δ 0 Re1/ 2 − ( X /C0 )1/ 2 = 0. (12.2.8b)

Introducing a new variable z = Re1/2 leads to a quadratic equation for z. Its positive root gives the
solution for z, and finally for Re(X) = z2:

Re( X ) = (δ 02 /4)[(1 + C1 X 1/ 2 ) 1/ 2 − 1] 2 , (12.2.8c)

where we have introduced the constant C1 = 4/(δ 02C01/ 2 ) . This equation was given by Beard (1980)
with some numerical coefficients, and Böhm (1989, 1992) refined the values of C0 and d 0 for drops
and crystals.
The Beard–Böhm relation (Eqn. 12.2.8c) is an algebraic expression by X, not a power law, but it
can be presented in the power law form by X:

Re( X ) = aRe X bRe . (12.2.9)

We will now find a representation for the coefficients aRe and bRe as continuous smooth functions of
X in the entire X range. Similar to the method used for the power law representation of the aerosol
size spectra in Chapter 6, consider a continuous function j (X) of the argument X with continuous
derivative j ′(X), where the prime means derivative. This function can be represented in a power-law
form by X with the power b and coefficient a, so the function and its derivative are

ϕ ( X ) = aX b , ϕ' ( X ) = abX b −1 ). (12.2.10a)

Solving these two equations, the coefficients a and b can be expressed via j, j ′ as

b( X ) = X (ϕ ′ /ϕ ), a( X ) = ϕ / X b . (12.2.10b)

For the terminal velocity application, j(X) = Re(X), and we can write, using (Eqn. 12.2.8c),

[(1 + C1 X 1/2 ) 1/2 − 1]

ϕ ′( X ) = Re′( X ) = , (12.2.11)
2C01/2 (1 + C1 X 1/2 ) 1/2 X 1/2

where we used the definition of C1. Substituting j (X) = Re(X) from (Eqn. 12.2.8c) and j ′(X) from
(Eqn. 12.2.11) into (12.2.10b), we obtain the following expressions for aRe, bRe:

Re ′ C1 X 1/2
bRe ( X ) = X = , (12.2.12)
Re 2[(1 + C1 X 1/2 ) 1/2 − 1](1 + C1 X 1/2 )1/2
1/ 2 1/ 2 2
Re( X ) δ 02 [(1 + C1 X ) − 1]
aRe ( X ) = = . (12.2.13)
X bRe 4 X bRe ( X )
12.2. Basic Equations for Fall Velocities 585

Equations (12.2.12) and (12.2.13) provide a power-law representation of Re(X) in (Eqn. 12.2.9)
with aRe, bRe being continuous functions of X that are consistent with the algebraic Re-X relation
(Eqn. 12.2.8c).
The drag coefficient can be determined using (Eqns. 12.2.7a), (12.2.7b), and (12.2.9) to be
1− 2 bRe
2 −2 1− 2 bRe
 2 (mg − Fb ) ρ F D 2 
−2
C D = X /Re = a X Re =a  Re  . (12.2.14)
 Aη 

Substitution of (Eqn. 12.2.14) into (Eqn. 12.2.6c) yields the following expression for the terminal velocity:

 2 ( mg − Fb ) 
bRe
1− 2 bRe
Vt = aRe ν   D 2 bRe −1 (12.2.15a)
 ρF A 
bRe
 2v g  ρ − ρF  
= aRe ν 1− 2 bRe  b  b  D 2 bRe −1 . (12.2.15b)
 A  ρ F  

It is assumed in the preceding formula that rb > rF—that is, the body is denser than the environ-
ment and falls down as the particles in the atmosphere. But the density difference in (Eqn. 12.2.15b)
should be (rF − rb) in the reverse cases, when rb < rF—that is, the body is lighter than the environ-
ment and lifts up, like a balloon in the atmosphere or a light buoy in the ocean. These cases are
discussed in the following text. In many applications, objects can be approximated by ellipsoids of
specified axis ratio x(D) as described in Sections 5.1 and 5.2 (e.g., oblate large drops or some crys-
tals), then vb = (p/6)D3x(D), A = (p/4)D2, and vb/A = (2/3)Dx(D). Then,
bRe
4 ρ 
Vt = aRe ν 1− 2 bRe  g ξ ( D)  b − 1  D 3 bRe −1 . (12.2.16)
 3  ρF  

The equations derived in the preceding text are valid for various fluids and bodies. In applications
for falling hydrometeors in the atmosphere of a planet, we consider air as the “fluid” and a drop or
a crystal as the “body”; henceforth, we use ra (the density of air) in place of rF, and rb denotes the
density of drops or crystals. We can use relationships for the particle mass and cross-sectional area
to be a function of diameter as

m = α Dβ , A = γ Dσ , (12.2.17)

where a, b, g, and s vary with particle size, phase, and habit. Incorporating the relations
(Eqn. 12.2.17) into (Eqn. 12.2.15a) and neglecting Fb compared to mg (since ra << rb), we obtain

Vt = Av D Bv , (12.2.18)

where the coefficients are

bRe
1− 2 bRe  2α g 
Av = aRe ν  ρ γ  , (12.2.19)
 a 
Bv = bRe (β − σ + 2) − 1. (12.2.20)

Since the coefficients aRe, bRe are given in (Eqns. 12.2.12) and (12.2.13) as continuous functions of
X, expressions (Eqns. 12.2.18)–(12.2.20) give a continuous power-law representation of the terminal
586 Terminal Velocities of Drops and Crystals

Table 12.1. Coefficients of mass, m = a Db, and area, A = gDs, power laws for drops and crystals
used in calculations of av, bv for the size D. The data are from Auer and Veal (1970), Locatelli
and Hobbs (1974, LH74), Matson and Higgins (1980), Heymsfield and Kajikawa (1987, HK87),
Mitchell (1996, M96), Pruppacher and Klett (1997), Heymsfield and Iaquinta (2000, HI00), and
Heymsfield (2003, H03). C0 = 0.292, d0 = 9.06 for drops; C0 = 0.6. d0 = 5.83 for crystals.

Mass Area

Particle Type α β γ σ Remark

Spherical drops (p/6)rw = 0.524 3 p/4 = 0.785 2

Nonspherical drops (p/6)rw × x(D) 3 p/4 = 0.785 2
Hex. Plates (P1a)
15 μm < D < 100 μm 0.00739 2.45 0.24 2.00 a = 0.0376, b = 3.31,
100 μm < D < 3000 μm 0.00739 2.45 0.65 1.85 Av = 297, Bv = 0.86
(HK87)
Hex. Columns
30 μm < D < 100 μm 0.1677 2.91 0.684 2.00
100 μm < D < 300 μm 0.00166 1.91 0.0696 1.50
D > 300 m 0.000907 1.74 0.0512 1.414
Rimed long columns
200 μm ≤ D ≤ 2400 μm 0.00145(old), 1.8 0.0512 1.414
0.00125(new)
Crystal w/sector-like branches (P1b)
10 μm < D < 40 μm 0.00614 2.42 0.24 1.85
40 μm < D < 2000 μm 0.00142 2.02 0.55 1.97
Broad-branched crystal (P1c)
10 μm < D < 100 μm 0.00583 2.42 0.24 1.85
100 μm <D < 1000 μm 0.000516 2.02 021 1.76
Stellar crystal with broad arms (P1d)
10 μm < D < 90 μm 0.00583 2.42 0.24 1.85
90 μm < D < 1500 μm 0.00027 1.67 0.11 1.63
Densely rimed dendrites (R2b)
1800 μm < D < 4000 μm 0.030 (old), 2.3 0.21 1.76 Av = 62, Bv = 0.33
0.015 (new) (LH74)
Bullet rosettes, 5 branches
200 μm < D < 1000 μm 0.00308 2.26 0.0869 1.57 Av = 2150, Bv = 1.225
(D < 0.06 cm),
Av = 492, Bv = 0.7
(D > 0.06 cm), (HI00)
Aggregates of thin plates 0.00145 1.8 0.2285 1.88
Crystal aggregates 0.0038 1.37 0.196 1.73 Tropical Rain
in tropical cirrus Measurement
Mission (TRMM)
Lump graupel (R4b)
500 μm < D < 3000 μm 0.049 2.8 0.50 2.0 LH74, HK87
Hail 0.466 3.0 0.625 2.0 Matson and Higgins

velocity over the entire particle size range. The parameters of m-D and A-g relations for the drops and
several crystal shapes are given in Table 12.1, based on the works by Auer and Veal (1970), Locatelli
and Hobbs (1974), Heymsfield and Kajikawa (1987), Mitchell (1996), Pruppacher and Klett (1997),
and Heymsfield and Iaquinta (2000).
12.3. Turbulent Corrections 587

12.3. Turbulent Corrections

3
When Re approaches ∼10 , CD begins to increase, which is caused by the effects of turbulence in
the flow. Böhm (1992) suggested an analytical parameterization of CD in this transitional regime,
whereby the turbulent drag coefficient CDt is related to the CDl in a laminar flow using an interpola-
tion function ytur(X):
−1
C Dt ( X ) = C Dl ( X )ψ tur ( X ), (12.3.1)
1 + (X / X0 ) k
ψ tur ( X ) = . (12.3.2)
1 + Ct ( X / X 0 ) k

Equation (12.3.2) shows that limiting values of ytur are ytur = 1 at small X << X0, and ytur = Ct−1
at large X >> X0. Bohm (1992) used fixed values Ct = 1.6, k = 2, X0 = 6.7 × 106 for drops, and X0 =
2.8 × 106 for crystals. Thus, CDt ≈ CtCDl = 1.6 CDl at large X or large Re. The value of Ct = 1.6 charac-
terizes an observed in some experiments increase of 60% in the drag coefficient caused by turbulence
(see review in Böhm, 1992), while Mitchell (1996) used Ct = 1.3 to better conform to the data from
Knight and Heymsfield (1983).
Here we generalize Böhm’s parameterization. First, substitute (Eqn. 12.3.1) into (Eqn. 12.2.7a)
and solve relative to Re:
1/ 2
Re t ( X ) = X 1/ 2 / C Dt
1/ 2
= Re l ( X )  tur ( X )  , (12.3.3)

where Ret is the turbulent Reynolds number and Rel is the “laminar” Reynolds number described
by the Beard–Böhm relation (Eqn. 12.2.8c). Following KC02, Rel can be formulated as a power law
described by (Eqns. 12.2.9)–(12.2.13) for Re(X) in Section 12.2, and then (Eqn. 12.3.3) provides an
analytical representation of the Re-X relation corrected for turbulence. Substituting (Eqn. 12.3.3) into
(Eqn. 12.2.12) for bRe, we obtain the coefficient bRe,t corrected for turbulence:

bRe,t ( X ) = X Re t ′ ( X )/Re t ( X ) = bRe,l ( X ) + ∆bRe,t ( X ), (12.3.4)

where bRe,l = X Re l ′/Re l is the value of bRe for the laminar flow defined in (Eqn. 12.2.12) and ΔbRe,t is
the turbulent correction:

X ψ tur
′ k (Ct − 1) z k
∆bRe,t = =− , (12.3.5)
2 ψ tur 2(1 + z k )(1 + Ct z k )

where z = X/X0. Substituting (Eqn. 12.3.3) into (Eqn. 12.2.13) for aRe, we find:
Re t ( X )
aRe,t ( X ) = b = aRe,l ( X )ξt ( X ), (12.3.6)
X Re,t
where aRe,l is the value for the laminar flow defined by (Eqn. 12.2.13) and xt is its turbulent correction:
1/ 2
Re l ( X ) ψ tur ( X ) 
aRe,l = b , ξt ( X ) =  ∆b . (12.3.7)
X Re,l X Re,t
The dependencies of the corrections ΔbRe,t and xt on X and D are described in more detail later in
Sections 12.4 and 12.6.
588 Terminal Velocities of Drops and Crystals

12.4. Asymptotic Values and Applications for Spherical and Nonspherical Particles

The analytical representation of aRe, bRe, Av, and Bv as given earlier allows for a straightforward esti-
mate of the asymptotic limits, which is useful for estimating the limiting behavior of the fall veloci-
ties. It is seen from (Eqns. 12.2.12) and (12.2.13) that the asymptotic values of aRe, bRe are reached at
C1X1/2 << 1 and C1X1/2 >> 1. Thus, a scaling Best parameter Xsc can be introduced from the condition
C1Xsc1/2 = 1, or

1 δ 04 C0
X sc = = , (12.4.1)
C12 16

corresponding to Xsc ≈ 123 for drops (rigid spheres) and Xsc ≈ 43 for crystals with values of C0 and
d0 cited in Section 12.2. The value of Xsc separates the two regimes for small and large particles or
the regimes of potential (X << Xsc) and aerodynamical (X >> Xsc) flows. The scheme for Vt described
earlier is based upon Abraham’s (1970) theory of the boundary layer, which should be valid for
Re >> 1. Beard (1980) showed that Abraham’s theory can be extended to the small particle limit,
which reduces to Stokes’ law for drops and appears to be valid with high accuracy for Re << 1 also.
The analytical scheme allows obtaining analytical asymptotics both at X << Xsc, and X >> Xsc.
For X << Xsc, the asymptotic values for the laminar coefficients aRe,l, bRe,l are obtained from
(Eqns. 12.2.12) and (12.2.13) by expanding into the power series by X:

bRe,l ( X ) = 1, aRe,l ( X ) = 1/(C0 δ 02 ). (12.4.2a)

This yields aRe,l = 0.0417 for drops, in a good agreement with Mitchell’s (1996) numerical fit
aRe = 0.0439, bRe = 0.97 in the range of smallest X = 0.01 to 10. Since the turbulent correction
ytur(X) = 1 at X << Xsc,, the limits of the turbulent coefficients aRe,t, bRe,t are the same.
In the opposite limit, X >> Xsc, it follows from (Eqns. 12.2.12) and (12.2.13) that

bRe,l = 1/2, aRe,l = 1/C01/ 2 , (12.4.2b)

resulting in aRe,l = 1.85 for drops (C0 = 0.292) and 1.29 for crystals (C0 = 0.6).
The turbulent corrections influence the behavior of aRe,t, bRe,t in the region of large X, which is
determined by a major change of the function ytur(X) around X0. With the choice X0 = 2.8 × 106 for
crystals in (Eqn. 12.3.2) for ytur as in Böhm (1992), evaluation of ytur(X) and of aRe,t(X), bRe,t(X)
described later in Section 12.6 shows that this region extends from X1t ∼ 3 × 104 (Re ∼ 2 × 102) to
X2t ∼ 108 (Re ∼ 104). It is seen from (Eqn. 12.3.5) that the turbulent correction DbRe,t tends to zero at
asymptotically large X as 1/zk, or 1/Xk ∼ 1/X2 and (Eqn. 12.3.4) shows that turbulence does not effect
bRe,t at very large X > X2t and its asymptotic value coincides with that for the laminar flow. Equations
(12.3.5) and (12.3.7) show that since at sufficiently large X > X2t, DbRe,t → 0, then x(X) → [ytur(X)]1/2
→ 1/Ct1/2, so that the asymptotic values of aRe,t and bRe,t are

bRe,t = 1/ 2, aRe,t = 1/(C01/ 2Ct1/ 2 ), (12.4.3)

(with Ct = 1.6).
The limit of the fall velocities at large sizes is considered in the following text. Thus, the asymp-
totic relations between the coefficients with and without turbulent corrections are

bRe,t = bRe,l , aRe,t = aRe,l /Ct1/ 2 . (12.4.4)

12.4. Asymptotic Values and Applications for Spherical and Nonspherical Particles 589

Using Ct = 1.6 (following Böhm, 1992), (Eqn. 12.4.3) gives the asymptotic values aRe,t = 1.46 for
drops (C0 = 0.292) and 1.02 for crystals (C0 = 0.6), respectively. With Ct = 1.3, as in Mitchell (1996),
we obtain aRe,t = 1.57 and 1.09 for drops and crystals, respectively. Our analytical limiting value
bRe,t = 1/2 in (Eqn. 12.4.3) gives the known hydrodynamic limit of the power index, 1/2, for Vt of
the large particles, Vt ∼ D1/2 (Landau and Lifshitz, v.6, 1959), as well as our limit of aRe,t = 1.09 with
Ct = 1.3 for ice crystals is close to Mitchell’s numerical fit aRe = 1.0865. Thus, (Eqn. 12.4.3) can be
used with a good accuracy to estimate the asymptotic regimes of the fall velocities. The Re-X relation
(Eqn. 12.2.9), taking into account (Eqn. 12.4.3), reduces for X >> Xsc and Ct = 1.6 to a simple square
root law:
1
Re( X ) = X 1/ 2 , (12.4.5)
(C0 Ct )1/ 2

which yields Re(X) = 1.46X1/2 for drops (C0 = 0.292) and Re(X) = 1.02 X1/2 for crystals (C0 = 0.6),
respectively. So, at large X > X2t, the turbulent correction with Ct = 1.6 according to (Eqn. 12.4.4)
leads to a decrease by 1/Ct1/2 = 1/1.265 in the coefficient aRe,t in the power law (Eqn. 12.2.13). Accord-
ing to (Eqns. 12.2.18) and (12.2.19), this results in a decrease of ∼26% in Vt for large crystals and
aggregates, yielding calculated values of Re and terminal velocities that are close to those observed,
as will be shown in Section 12.6. Hence, these equations with turbulent corrections yield a descrip-
tion for the large aggregates and can be used up to very large X > 1012 and Re > 106, in particular for
large hailstones, which is illustrated in Section 12.6.
Turbulence does not change the asymptotic index bRe,t which determines the asymptotic behavior
of Re(X) in (Eqn. 12.2.9) and of Vt(D) in (Eqn. 12.2.18). Note however, that the correction DbRe and
the coefficient bRe have minima at moderately large X ∼ (2–3) × 106, corresponding to D ∼ 0.3–2 cm
for the large aggregates and hail. The larger values of X ≥ X2t ∼ 108 may not be reached by many
crystal habits due to size limitations, and their asymptotic behavior is determined by the intermediate
region of transition to the turbulent regime X1t < X < X2t, as illustrated in Section 12.6. Also, at
Re > 105 or X > 1010, the asymptotic expression (Eqn. 12.4.5) may become invalid as the “drag crisis”
is encountered, which is considered in Section 12.6.2.
Note that the factor ν 1− 2 bRe in (Eqn. 12.2.19) for Av along with the asymptotic value for bRe
describes the correct dependence of Vt on viscosity: for small particles, bRe = 1, and 1–2bRe = −1, so
Vt ∼ 1/n (viscous Stokes regime, described by (Eqn. 12.1.3)); while for the large drops, bRe = 0.5, and
1–2bRe = 0, so Vt is independent of viscosity, as should true be in an aerodynamic regime.
We consider here the application for spherical particles, including drops, graupel, and hail. For
simplicity, we examine primarily drops using the water density rw, however, the same equations
are valid for spherical graupel and hail after replacing rw with the ice density ri (which may depend
also on D and crystal habit). For spherical particles, the mass and area are related to the diameter by
m = (p/6)rw D3 and A = (p D2/4); thus from m-D and A-D relations (Eqn. 12.2.17) we find that
a =(p/6)rw, b = 3, g = p /4, s = 2 (see Table 12.1). Substituting these values into (Eqns. 12.2.18)–
(12.2.20), we obtain the following expression for spherical particles:
bRe
1− 2 bRe
 4 ρw g 
Av = aRe ν 3 ρ  , Bv = 3bRe − 1. (12.4.6)
 a 
590 Terminal Velocities of Drops and Crystals

This expression can be evaluated for small and large drops using the scaling diameter from
(Eqn. 12.4.1), which yields (under standard atmospheric conditions) Dsc ≈ 122 μm.
For small droplets (D << Dcr), using the asymptotic values given in (Eqn. 12.4.2a), aRe = 1/(C0d02)
and bRe = 1, we obtain Vt in terms of radius, r, or diameter D = 2r as

Vt (r ) = Av D Bv = Avr r Bv , Avr = 2 Bv Av , (12.4.7)

4 ρw g 16 ρ w g
Av = = , =Avr = , (12.4.8)
3 δ 02C0 η 0 0 3 δ 02C0 ρ a ν
Bv = 3bRe − 1 = 3 − 1 = 2. (12.4.9)

So, with the power index Bv = 2, (Eqns. 12.4.7) and (12.4.8) yield Stokes law Vt ∼ r2 (Eqn. 12.1.3),
and using Abraham’s constants d0 = 9.06, C0 = 0.292 in (Eqn. 12.4.8) gives Avr = 1.2 × 106 cm−1 s−1 =
Cst—i.e., the Stokes constant for the drops. These expressions are used in Section 12.5 for verifica-
tion of the temperature and pressure dependence of the fall speeds for small particles. Thus, these
equations based on the Abraham’s concept of the “assembly” of the body and its boundary layer
generalize the classical Stokes’ law as the limit of small spherical particles, in agreement with the
correspondence principle.
For large droplets, (D > Dcr), aRe = 1.85 and bRe = 0.5 are evaluated from (Eqns. 12.4.2b) and
(12.4.3), and Vt is expressed as in (Eqn. 12.4.7) with coefficients
1/2
 4 ρw g 
Avr = 21/2 Av = 21/2 aRe   , Bv = 1 / 2. (12.4.10)
 3 ρa 

So, Vt ∼ r1/2, as it should be for spherical particles in aerodynamic regime when CD does not
depend on Vt (Landau and Lifshitz, v. 6, 1959). Evaluation of the coefficient with the laminar value
aRe,l = 1.85 for drops gives Avr = 2.72 × 103 cm1/2 s−1, which is higher than the corresponding value
of 2.2 × 103 cm1/2 s−1 given in Rogers and Yau (1989), based on experimental data (see Eqn. 12.1.7c).
Introducing the turbulent correction according to (Eqn. 12.4.4), aRe,t = aRe ,l /Ct1/2 = 1.46 yields smaller
Avr = 2.16 × 103 cm1/2 s−1, which is very close to Rogers and Yau’s value. Thus, the turbulent effect
causes a decrease in the fall velocity of large drops by ≈25%.
Terminal velocities of large drops are also influenced by the effects of nonsphericity. The nonsphe-
ricity of the drops becomes substantial for the fall velocity at D > 535 μm (Beard, 1976, 1980; Böhm,
1989). Large falling drops have shapes that can be approximated by an oblate spheroid or a convex
upward pancake with maximum diameter D oriented horizontally, perpendicular to the flow, and the
smaller diameter Ds oriented vertically. Measurements and models described in Pruppacher and Klett
(1997) show that the aspect ratio xf = Ds/D = 1 for small drops and decreases with D. We approximate
the aspect ratio with the interpolation formula:

1 − exp(− D /λ1 )
ξ f ( D) = exp(− D / λ1 ) + . (12.4.11)
1 + ( D /λ2 )

In Khvorostyanov and Curry (2002), the parameters of the drop shape were chosen as l1 =
l2 = 4.7 μm, this led to a slight underestimate of Vt by 2–4%. Subsequent tuning showed that a bet-
ter choice with two shape parameters, l1 and l2, leads to a better agreement with experimental data of
12.5. Corrections for Temperature and Pressure 591

Gunn and Kinzer (1949). The interpolation (Eqn. 12.4.11) has two limits, xf (D) → 1 at small D << l1,
l2—i.e., ensures the spherical shape of the small drops, and xf (D) → l2 /D at large D >> l1, which
ensures a decrease of the axes ratio xf (D) with increasing D. The parameters l1, l2 can be determined
from the condition xf ≈ 0.5 at D ∼ 8.5 mm, after which drop breakup occurs due to hydrodynamic
instability. The values l1 = 5.5 mm and l2 = 4.7 mm ensure good agreement with the experimental
data on Vt from Gunn and Kinzer (1949) and the calculations of Beard (1980), as shown in Fig. 2.4.
The factor xf (D) in (Eqn. 12.4.11) is close to the nonsphericity factor by Beard and Chuang (1987)
and the other parameterizations of xf (D) (Pruppacher and Klett, 1997). Considering the large drop
as an oblate ellipsoid, we obtain from the m-D relation (Eqn. 12.2.17) a (D) = (p /6)rwxf (D), b = 3,
g = p/4, s = 2. Using (Eqns. 12.2.18)–(12.2.20) for Vt and asymptotics at large D, bRe = 0.5 from
(Eqns. 12.4.2b) and (12.4.4) and xf (D) ∼ l2/D from (Eqn. 12.4.11), we obtain for large D:

Vt ( D) = Av D Bv ~ α bRe D bRe ( β −σ + 2) −1
~ [ξ f ( D)]bRe D bRe ( β −σ + 2) −1 ~ D −0.5 D 0.5 ~ D 0 . (12.4.12)

So, Vt is asymptotically independent on D with xf(D) as (Eqn. 12.4.11). This is in agreement with
observations of Gunn and Kinzer (1949) and calculations from Beard (1976, 1980) that show very
weak dependence of Vt on the drop size at D > 4–5 mm (see Fig. 12.4).

12.5. Corrections for Temperature and Pressure

The equations for Vt were derived earlier for fixed values of pressure p, and temperature T. As seen
from (Eqn. 12.2.18)–(12.2.20), there are two kinds of dependencies of Vt on p and T: 1) directly via
the kinematic viscosity na or the dynamic viscosity h = nra and the air density ra in Av(p, T), and
2) via dependence of aRe, bRe on X, which also depends on p, T.
Consider first the direct h and ra dependence in Av(p, T), which is defined in (Eqn. 12.2.19) as

Vt ~ Av ( p, T ) ~ ν (1− 2 bRe ) ρ a− bRe ~ η (1− 2 bRe ) ρ a( bRe −1) . (12.5.1)

The value of h is almost independent of p, and its temperature dependence is h(T) = h0j (T), where
h0 = 1.718 × 10−4 poise is the dynamic viscosity at 0 °C, and

ϕη (T ) = 1 + 0.00285Tc − 6.9 × 10 −6 Tc2 , Tc < 0 º C (12.5.2a)

ϕη (T ) = 1 + 0.00285Tc , c 0 c, Tc > 0 º C. (12.5.2b)

Tc = T − 273.15 is the temperature in °C (Beard, 1980; Pruppacher and Klett, 1997). Using these
expressions with the equation of state ra = p/(RaT), with Ra being the specific gas constant for the dry
air, and substituting them into (Eqn. 12.5.1), we obtain an expression for the velocity Vt at an altitude
with some p, T via its value Vt0 at an altitude with p = p0 and T = T0:

Vt ( p, T ) = C pT Vt 0 , (12.5.3a)
1− 2 bRe
1− bRe
 η (T )   ρ a ( p0 , T0 ) 
C pT =    ρ ( p, T )  (12.5.3b)
 η (T0 )   a 
592 Terminal Velocities of Drops and Crystals

1− bRe
1− 2 bRe
 p0 T 
= ϕη (T )   p T  . (12.5.3c)
 0 

The two asymptotic cases follow from (Eqns. 12.5.3c), (12.4.2a), and (12.4.3). For small sizes, the
index bRe = 1, and 1 − 2bRe = −1, 1 − bRe = 0, and thus the pressure or air density dependencies in
(Eqns. 12.5.3b) and (12.5.3c) vanish, and Vt weakly depends on the temperature via the function jh(T) as

C pT = [ϕη (T )]−1 = [η ( p, T )/η0 ]−1 , (12.5.4)

and its increase from 0 °C to −40 °C is ∼12%. This is confirmed by comparison of (Eqn. 12.5.4) to
the Stokes limit for the small particles (Eqn.12.1.3) or (Eqns. 12.4.7)–(12.4.9), and to this limit in
Beard (1980) where also Vt ∼ h−1, which indicates the validity of this CpT limit in the viscous regime.
For large sizes, bRe = 0.5 according to (Eqn. 12.4.3), thus 1 − 2bRe = 0, and 1 − bRe = 0.5, then the
dependence on j(T) or dynamic viscosity h in (Eqn. 12.5.3c) vanishes, and the p, T-dependencies are
described by the square root law by ra or by p, T as
1/ 2 1/ 2
 ρ ( p ,T )  p T
Vt ( p, T ) = c pT ∞Vt 0 , c pT ∞ =  a 0 0  =  0  . (12.5.5)
 ρ a ( p, T )   p T0 

The dependence (Eqn. 12.5.5) can be obtained directly from (Eqn. 12.2.6c) assuming CD = const
and rb >> ra. Then in (Eqn. 12.2.6c), Vt ∼ ra−1/2, or using the equation of state, ra = p/(RaT), we
come again to (Eqn. 12.5.5) which is typical of the aerodynamic limit and is used in many numerical
models for precipitating the hydrometeor species (e.g., Kessler, 1969, Lin et al., 1983; Rutledge and
Hobbs, 1983; Fowler et al., 1996).
A comparison of (Eqns. 12.5.4) and (12.5.5) shows that the temperature and pressure dependence
of the fall speeds is substantially different for the small (r ≤ ∼30–40 μm or D ≤ 60–80 μm) and large
particles: The velocities of the smaller sizes increase with increasing height much more slowly than
those of the large sizes. Hence, the difference in fall speeds between the small and large particles
increases with height. This increase between the surface (1000 hPa and 0 °C)—and, e.g., a height
with p = 300 hPa, T = −40 °C—is ∼12% for small sizes (due to jh−1) and 170% for the large sizes
according to (Eqn. 12.5.5). Accounting for this effect will lead to acceleration of gravitational coagu-
lation and accretion with growing altitude, which depends on the difference of fall speeds between
large and small particles (see Section 5.6).
Variations of Vt with p and T associated with changes in X and aRe, bRe can be estimated using the
relations:
∂aRe ∂bRe
δ aRe ~ δ X, δ bRe ~ δ X. (12.5.6)
∂X ∂X
For estimates of X variations, (Eqn. 12.2.7a) and (12.2.7b) can be rewritten using m-D, A-D relations
(Eqn. 12.2.17), and equations for ra(T) and h(T). Using Equations (12.2.12) and (12.2.13) for aRe, bRe,
we performed both an analytical and numerical evaluation of these variations of Vt, which are 1–3 orders
of magnitude smaller than the “direct” dependence described earlier and therefore can be neglected.
So, (Eqns. 12.5.3a)–(12.5.3c) describe the dependence of the fall velocities of the hydrometeors
on temperature and pressure with sufficient precision over a wide size range and yield correct limits
12.6. Results of Calculations 593

in both viscous and aerodynamic regimes for small and precipitating fractions, respectively. The
accuracy of the (Eqns. 12.5.3a)–(12.5.3c) for CpT correction is illustrated in Section 12.6.7 by a
comparison with Beard’s (1980) parameterization and with the direct numerical calculations of Vt at
various heights.

12.6. Results of Calculations

In this section, the fall velocity scheme described here is compared to experimental data and to other
methods. The features of the Re-X relation, drag coefficient, and of the coefficients aRe and bRe are
illustrated, and this method is applied for evaluation of fall velocities of drops and various crystal hab-
its, which facilitates the interpretation of the physical basis for the accuracy of the fall velocity scheme.

12.6.1. Re-X Relation

Understanding the influence of turbulence on the drag coefficient is explored through calculations
of the Re-X relation. Fig. 12.1 shows the Re-X relation calculated using (Eqn. 12.2.9) and con-
tinuous functions aRe(X), bRe(X) (Eqns. 12.2.12) and (12.2.13) for various cases, and illustrates the
effect of turbulence. A comparison with the Böhm (1992, B92) and Mitchell and Heymsfield (2005,
MH05) schemes is also shown. The uppermost curve with open triangles in Fig. 12.1a describes rigid
spheres or drops without account for turbulence, calculated using the constants from Abraham (1970)
C0 = 0.29, d0 = 9.06. The curve calculated for ice crystals without turbulence, using C0 = 0.6, d0 =
5.83 recommended by Böhm (1989, 1992) lies lower than the curve for drops and is almost indistin-
guishable from the corresponding curve in Böhm (1989, 1992), which indicates a good accuracy of
the power law approximation (Eqns. 12.2.9), (12.2.12), and (12.2.13) of the Re-X relation. Calcula-
tions for both drops and crystals including the turbulent corrections (Eqns. 12.3.3)–(12.3.7) leads to
a decrease in Ret(X), asymptotically by a factor of y1/2 = 1/Ct1/2 = 1/1.265. The curve calculated for
the crystals using the KC05 model with turbulence (crosses) is very close to the corresponding Re-X
relation from Böhm (1992) (solid diamonds).
The enhanced Figs. 12.1b,c,d show the comparison for the crystals in the three regions of Re
numbers. The curves Re(X) calculated with the model of Khvorostyanov and Curry, 2005, KC05)
using (Eqns. 12.2.9), (12.2.12), and (12.2.13) are very close to Böhm’s (1992, B92) model in all three
regions, both with and without turbulent corrections. The Re(X) curve from Mitchell and Heymsfield
(2005, MH05) lies below the KC05 and Böhm curves at small Re < 300, causing underestimates of
the fall velocities for the small particles (Fig. 12.1b). At the intermediate region 106 < Re < 108, the
MH05 curve lies between the curves from KC05 and Böhm calculated with and without turbulence
(Fig. 12.1c), which means that the MH05 scheme underestimates the turbulent effect and overestimates
the Re(X) and fall velocities. This difference is caused by the different accounting for the turbulent effect
in the Böhm and KC05 schemes (the transition function localized in the limited Re-range in agreement
with observations) and in MH05 (the transition function smoothed over the entire Re-range). At higher
X > 108 or Re > 8 × 103, the MH05 curve goes lower than the Böhm and KC05 curves with turbulence,
overestimating its effect, then MH05 reaches a maximum near Re ∼ 104, and then diverges with the
other curves and abruptly falls almost vertically to negative values Re < 0 (Fig. 12.1d).
594 Terminal Velocities of Drops and Crystals

1E+6 KC02, spheres, no turb. 300

Reynolds number Re
Reynolds number Re
1E+5 KC05, spheres, turb., crisis
250
1E+4 200
1E+3
KC05, cryst, no turb
150
1E+2 KC05, cryst, turb
B92, cryst, no turb 100
1E+1 KC05, cryst, turb Bohm92, cryst, turb
1E+0 B92, cryst, turb 50 MH05, aggreg.
MH05, aggreg.
1E–1 0
1E+1
1E+2
1E+3
1E+4
1E+5
1E+6
1E+7
1E+8
1E+9
1E+10
1E+11
1E+12

2E+4

4E+4

6E+4

8E+4

1E+5
Best number X Best number X
(a) (b)

KC05, cryst, no turb

1E+4

Reynolds number Re
Reynolds number Re

B92, cryst, no turb

1E+5
KC05, no turb KC05, cryst, turb
Bohm92, no turb B92, cryst, turb
MH05, aggreg.

1E+4
Bohm92, cryst, turb
KC05, cryst, turb
MH05, aggreg., turb
1E+3 1E+3
1E+6 1E+7 1E+8 1E+7 1E+8 1E+9 1E+10
Best number X Best number X
(c) (d)

Figure 12.1. The Re-X relation calculated using various models. (a) KC02 with C0, d0 for rigid
spheres or drops without turbulent corrections (KC02, open triangles), for spheres with corrections
for turbulence and drag crisis (KC05, solid triangles), with C0, d0 for crystals without turbulent
corrections (KC05, open circles) and with turbulent corrections (KC05, crosses). This is compared
to Böhm (1992) without turbulent corrections (B92, open diamonds) and with turbulent corrections
(B92, solid diamonds); and to Mitchell and Heymsfield for crystal aggregates (MH05, solid
circles). (b), (c), and (d) are the enhanced fragments of (a) in various regions of X and Re. From
Khvorostyanov and Curry (2005b) with changes, J. Atmos. Sci., 62, © American Meteorological
Society. Used with permission.

This comparison shows that the power law representation (Eqns. 12.2.9), (12.2.12), and (12.2.13)
of the Re-X relation with the parameters C0, d0 for drops and crystals found by fitting it to experi-
mental data by Böhm (1989, 1992), and with the turbulent corrections (Eqns. 12.3.1)–(12.3.7), can
be used for an accurate evaluation of crystal fall velocities.

12.6.2. The Drag Coefficient and “Crisis of Drag”

Fig. 12.2 shows calculations of the drag coefficient CD for rigid spheres and crystals using (Eqn.
12.2.14), and Re(X) using (Eqns. 12.2.9), (12.2.12), and (12.2.13), with turbulent corrections (Eqns.
12.3.1)–(12.3.7) and without these corrections. The results are compared to the calculations of Böhm
(1989, B89, and 1992, B92), showing good agreement. At small Re, the drag coefficient CD decreases
12.6. Results of Calculations 595

1E+2 B89, KC05, spher. no turb

KC05, spheres, turb., cris.
Landau, exper
KC05, cryst, no turb
1E+1
Drag coefficient CD
B92, cryst., no turb.
KC05, cryst, turb
B92, cryst. turb

0.1

0.1 1 1E+1 1E+2 1E+3 1E+4 1E+5 1E+6

Reynolds number

Figure 12.2. Drag coefficient CD vs. Reynolds number calculated for the spheres and crystals by
various methods. Rigid spheres, equations from this chapter based on the model of Khvorostyanov
and Curry (2005b, KC05), and Böhm’s (1989) for spheres (B89, KC05, crosses), (the curves
B89 and KC05 are indistinguishable); equations from this chapter with turbulent corrections and
corrections for drag crisis (KC05, solid spheres); experimental data for rigid spheres from Landau
and Lifshitz (v. 6, 1959) (Landau, exper., open circles); equations from this chapter with parameters
for crystals without turbulent corrections (KC05, asterisks), Böhm’s equations without turbulence
(B92, open triangles); KC05 model for crystals and turbulent corrections (KC05, cryst., turb.,
squares), Böhm’s equations for crystals with turbulent corrections (B92, solid triangles). From
Khvorostyanov and Curry (2005b), J. Atmos. Sci., 62, © American Meteorological Society. Used
with permission.

with increasing Re as 24/Re (Stokes’ law). At Re > 10–50, this decrease in CD continues but more
slowly, leading to an asymptotic value for rigid spheres CD = C0 = 0.29 without the turbulent correc-
tion (crosses, the curves B92 and KC05 are indistinguishable). However, this behavior diverges at
Re > 103 with the experimental data given for rigid spheres in Landau and Lifshitz (v.6, 1959) which
show a minimum of CD at Re ∼ 2–5 × 103, then CD increases to ∼ 0.5 and then becomes almost con-
stant till Re ∼ 2 × 105. A similar increase of the measured CD at Re > 2 × 102 to 103 was illustrated by
Beard (1980) for the large drops, some idealized shapes (disk, oblate, and prolate spheroids), several
crystal habits, and graupel.
These features are explained by the complex structure of the boundary layer and the turbulence
around the falling body. At Re ≥ 103, the boundary layer surrounding the falling body is becoming
turbulent and can be divided into three parts: the laminar boundary layer in the front part of the
body, then the turbulent boundary layer farther downstream, and finally, the turbulent wake after
the separation line (the roughly circular line in the plane perpendicular to the flow where the flow
separates from the body forming the wake). It was noted in Landau and Lifshitz (1959) and Beard
(1980) that the increase in CD at Re > 103 and the relative maximum CD ≈ 0.5 between Re = 104 and
596 Terminal Velocities of Drops and Crystals

105 occurs because the separation line moves upstream, but it is not described by Abraham’s theory
which assumes a constant separation point. As Fig. 12.2 shows, the description is improved with
turbulent corrections: CD increases at Re > 2 × 103 to a larger value of CD = 0.29 × 1.6 = 0.47 (KC05,
solid spheres) and merges with the experimental data. Thus, accounting for the turbulent correc-
tions lets us describe this shift of the separation line upstream at Re ≥ 103, when the boundary layer
becomes wider, increasing the drag.
An important and interesting feature of CD for rigid spheres is an abrupt decrease at Recris ∼ 2 × 105
by a factor of 4–5, which is referred to as the “crisis of drag” (Landau and Lifshitz, v. 6, 1959). At
Recris ∼ (2 to 3) × 105, the separation line moves backward to the rear part of the sphere, and the
turbulent wake behind the body abruptly becomes much narrower, causing the drag coefficient to
decrease by a factor of 4–5 (Fig. 12.2). At Re > Recris, the separation line begins to move upstream to
the front part of the sphere again, the boundary layer becomes thicker and the drag increases. KC05
found that a continuous parameterization of experimental data on CD for rigid spheres up to Re > 106
that takes into account turbulence provides the basis for the following formulation of the drag crisis.
For Re < Recris ∼ 2 × 105, CD is described by (Eqn. 12.2.7a) with Re(X) from (Eqns. 12.2.9), (12.2.12),
and (12.2.13), the coefficients C0 = 0.292, d0 = 9.06 for the spheres, and turbulent corrections
(Eqns. 12.3.1)–(12.3.7). For Re ≥ Recris, CD is described using these same equations, but with a step-
wise decrease of C0 from 0.29 to 0.12 at the crisis point Recris(Xcris).
Fig. 12.2 shows satisfactory agreement between the values of CD calculated with these equations
using the following parameter values: k = 2 (parameter in the turbulent transition function ytur(X)
(Eqn. 12.3.2), Xcris = 4.8 × 1010, Ct = 1.6 (curve KC05, solid circles) and the experimental data from
Landau and Lifshitz (v.6, 1959, open circles) over the entire region of Re up to 106. The asymptotic
value at Re ∼ 106 according to (Eqns. 12.3.1) and (12.3.2) is CD = 0.12 × 1.6 = 0.19, close to the value
given in Landau and Lifshitz (v.6, 1959).
Calculations with the KC05 scheme but with C0 = 0.6, d0 = 5.83 for the crystals and the param-
eter k = 1 in (Eqn. 12.3.2) for ytur(X) shown in Fig. 12.2 yield greater values of CD than for the
drops (KC05, asterisks), which means greater drag force and smaller crystal fall velocities. The same
increase at Re > 103 with an accounting for the turbulent correction (solid diamonds) is caused by
a displacement of the wake separation line forward to the front part of a crystal (against the flow),
and CD is again in good agreement with Böhm’s (1992) method without and with turbulence (open
and solid triangles), with the experimental data from Beard (1980) and with the field data for grau-
pel from Heymsfield and Kajikawa (1987) that also exhibited an increase in CD at the large Re. It is
not clear whether the drag crisis regime can be achieved for ice crystals falling in the atmosphere.
For the largest hailstones with D ∼ 10 cm and Vt ∼ 40 m s−1 (Matson and Huggins, 1980, Pruppacher
and Klett, 1997), Re ∼ 3 × 105 which exceeds Recris for drops. If the drag crisis occurs for crystals
near Recris ∼ 2 × 105 as for the spheres, this may mean an abrupt increase in Vt for large hailstones at
D ∼ 10 cm; however, if Recris for the crystals is greater, the drag crisis may not occur for these sizes.
This possible occurrence should be verified experimentally.

12.6.3. Application to Drops

Fig. 12.3 compares the continuous coefficients Av, Bv for the drops calculated using (Eqns. 12.2.19)
and (12.2.20) with stepwise parameterization (Eqns. 12.1.7a), (12.1.7b), and (12.1.7c) from Rogers
and Yau (1989).
12.6. Results of Calculations 597

Coefficient Av of velocity power law

1E+6

1E+5

1E+4

1E+3

1E+2
1 1E+1 1E+2 1E+3 1E+4
Droplet diameter D (µm)
(a)

2.00
Index Bv of velocity power law

1.75

1.50

1.25

1.00

0.75

0.50

1 1E+1 1E+2 1E+3 1E+4

Droplet diameter D (µm)
(b)

Figure 12.3. Comparison of the continuous coefficients Av calculated with the KC02-KC05 model,
(Eqn. 12.2.19) (a), and Bv (Eqn. 12.2.20) (b) of the velocity power law (Eqn. 12.2.18) (solid
circles) with stepwise parameterization from Rogers and Yau (1989), (Eqns. 12.1.7a), (12.1.7b), and
(12.1.7c) for the spherical drops (triangles) and oblate spheroid (curve with diamonds for Av). From
Khvorostyanov and Curry (2002), J. Atmos. Sci., 59, © American Meteorological Society. Used
with permission.

Although calculations of Av, Bv do not use any input parameters from the Rogers and Yau param-
eterization based on the experimental data, good agreement is seen.
Fig. 12.4 compares the fall velocities for liquid drops up to D = 5 mm calculated using the KC05
model (Eqns. 12.2.18)–(12.2.20) with turbulent corrections (Eqns. 12.3.3)–(12.3.7) and without them,
and the experimental data from Gunn and Kinzer (1949). The values l1 = 5.5 mm and l2 = 4.7 mm
were chosen in the nonsphericity factor x(D) in (Eqn. 12.4.11). This figure shows that: a) both calcu-
lated curves with and without turbulent corrections are concave upward, which is caused by nonsphe-
ricity increasing with growing D described by x(D) in (Eqn. 12.4.11); and b) the effect of turbulence
becomes noticeable at D ≥ 1.5–2.0 mm, the drag especially increases at D ≥ 4 mm, causes the decrease
of Vt as discussed earlier, and makes the calculated velocity close to the observed one, so that Vt at
598 Terminal Velocities of Drops and Crystals

1200

1000

Fall velocity (cm s–1)

800

600

KC-2005, turb.
400
KC-2005, no turb.
200 Gunn, Kinzer, 1949

0
0 2000 4000 6000 8000
Droplet diameter D (µm)

Figure 12.4. Drops’ terminal velocities under standard atmospheric conditions calculated using
Equation (12.2.16) for the drops with aRe, bRe from (Eqns. 12.2.12) and (12.2.13) and the newer
two-parametric nonsphericity parameter (Eqn. 12.4.11). Calculations with turbulent correction and
an accounting for nonsphericity (KC2005, turb., circles) practically coincides with the experimental
curve from Gunn and Kinzer, 1949 (diamonds). The curve calculated without turbulent corrections
(triangles) overestimates Vt at D > 3500 μm.

normal conditions tends to the finite limit of about 9 m s−1. At larger sizes, the drops become hydro-
dynamically unstable and breakup occurs (Pruppacher and Klett, 1997).

12.6.4. Turbulent Corrections and Their Application to Aggregates

The turbulent corrections are especially important for ice crystals that reach sizes of D > 1 cm,
such as aggregates and hailstones. The coefficient aRe(X) and power index bRe(X) calculated with
(Eqns. 12.2.12) and (12.2.13), and turbulent corrections aRe (Eqn. 12.3.6) and bRe (Eqn. 12.3.7) are
shown in Fig. 12.5a,b as universal functions of X, independent of crystal type. The values C0 = 0.6,
d 0 = 5.83 were used, just as for crystals in Böhm (1992), Mitchell (1996, M96), MH05, and KC05.
Although Ct = 1.3 was used in M96 to match observations from Heymsfield and Kajikawa (1987),
we found that the value Ct = 1.6 recommended by Böhm (1992) (based on observations of a 60%
increase in CD by turbulence) yields better agreement for all considered crystal types. The coeffi-
cients aRe,t(X) and bRe,t(X) with turbulent corrections exhibit a maximum and minimum respectively
in the X-range 105–108 as compared to their smooth behavior without turbulent corrections. This
non-monotonic behavior is caused by the functions D bRe,t(D) and xt(D) defined by (Eqns. 12.3.5)
and (12.3.7) shown in Fig. 12.6a,b for the three crystal habits as the functions of D. The parameters
a, b, g, and s in the m-D and A-D in calculations were taken from the sources indicated in Table 12.1.
Although these turbulent corrections are universal functions of X, they differ as functions of D
due to different crystal habits (parameters a-s). Fig. 12.6a shows that the correction DbRe,t calculated
with (Eqn. 12.3.5) has a minimum of −0.06 for all three crystal habits, centered at D = 20 mm for
12.6. Results of Calculations 599

1.50

1.25

Coefficient aRe(X)
1.00 no turb. cor.

0.75 turb. cor.

0.50

0.25

0.00
–4 –2 0 2 4 6 8 10
Log10X
(a)

1.0

0.9
Power index bRe(X)

0.8

0.7

0.6

0.5

0.4
–4 –2 0 2 4 6 8 10
Log10X
(b)

Figure 12.5. (a) Coefficient aRe(X) and (b) power index bRe(X) as functions of the Best parameter
X with (solid circles) and without (open circles) turbulent corrections. From Khvorostyanov and
Curry (2005b), J. Atmos. Sci., 62, © American Meteorological Society. Used with permission.

aggregates of thin plates, at 3 mm for hail, and at 10 mm for crystals observed in the Tropical Rain
Measurement Mission (TRMM) field campaign described in Heymsfield (2003). The location of the
minimum is determined by the X-D relation and m-D, A-D relations: The denser a crystal, the smaller
the value of D of minimum DbRe,t, as seen from the definition of X (Eqn. 12.2.7b). Asymptotically,
DbRe,t tends to zero at small and large D—i.e., turbulence does not affect the asymptotic values of
the power index bRe. The correction xt(D) begins with 1 at small D, reaches a maximum of 2.1 at the
same locations as DbRe,t for these habits, and tends to the asymptotic value ytur1/2 = 1/Ct1/2 = 0.79 at
large D according to (Eqn. 12.3.7), where DbRe,t → 0 and X ∆bRe,t → 1 . This explains why aRe(X) with
turbulence tends in Fig. 12.5a to a smaller value than without turbulence. Since Vt ∼aRe, this leads to
a decrease in Vt at large sizes due to the turbulence effect that increases the drag force.
600 Terminal Velocities of Drops and Crystals

0.02

Correction ∆bRe,t(D)
0.00

–0.02

–0.04
aggr. plates
–0.06 hail
TRMM
–0.08
0.1 1.0 10.0 100.0 1000.0
D (mm)
(a)

2.2
aggr. plates
2.0
hail
1.8
Correction ξt(D)

TRMM
1.6
1.4
1.2
1.0
0.8
0.6
0.1 1.0 10.0 100.0 1000.0
D (mm)
(b)

Figure 12.6. (a) correction DbRe,t(D) to bRe and (b) correction xt(D) to aRe as a function of D for
aggregates of thin plates (solid circles), hail (diamonds), and crystal aggregates observed in tropical
cirrus during TRMM (open circles). From Khvorostyanov and Curry (2005b), J. Atmos. Sci., 62,
© American Meteorological Society. Used with permission.

The coefficients aRe and bRe are shown in Fig. 12.7 as functions of D with and without the turbu-
lent corrections, and are compared to the corresponding calculations from MH05. Fig. 12.7 shows
that all three curves for aRe and bRe are close at values less than Log10D ∼ 3.7 (D ∼ 0.5 cm). At higher
values, the curves KC05 without the turbulent correction exhibit a monotonic increase and decrease
and tend to their limiting values, aRe → 1, and bRe → 0.5, as described in Section 12.4. The KC05
coefficients, with an accounting for turbulence, have local extrema in the range D = 1–10 cm: aRe
has a local maximum of 1.48 (∼50% greater than the asymptotic value 1) and bRe has a minimum
of 0.47 (smaller than the asymptotic 0.5), both centered at log10(D μm) ∼ 4.4 or D ∼ 2.5 cm. This is
caused by the behavior of corrections xt and DbRe,t shown in Fig. 12.6. The coefficients aRe and bRe
in the KC05 scheme tend to their asymptotic values with a turbulence of 1.02 and 0.5 defined by
(Eqn. 12.4.3).
12.6. Results of Calculations 601

1E+2 1.0
KC05, crystals, turb
KC05, crystals, no turb
MH05 0.8
1E+1

Power index bRe

Coefficient aRe

0.6
1E+0
0.4

1E–1 KC05, crystals, turb

0.2
KC05, crystals, no turb
MH05
1E–2 0.0
0 1 2 3 4 5 6 0 1 2 3 4 5 6
Log10D (µm) Log10D (µm)
(a) (b)

Figure 12.7. (a) Coefficient aRe (Eqn. 12.2.13) of Re-X power law relation; and (b) power index bRe
(Eqn. 12.2.12) calculated for aggregates of thin plates as functions of D with turbulent correction
(KC05, turb., solid circles), without correction (KC05, no turb., open circles) and compared to
MH05 (diamonds). From Khvorostyanov and Curry (2005b), J. Atmos. Sci., 62, © American
Meteorological Society. Used with permission.

The coefficients in the MH05 scheme remain sufficiently close to the KC05 coefficients with tur-
bulence until log10D ∼ 4.4 (D ∼ 2.5 cm), but at larger sizes, the coefficients in the MH05 scheme tend
to much larger and smaller values, and do not tend to the correct asymptotic values.
These variations of aRe and bRe determine the behavior of the coefficients Av, Bv of the velocity
power law shown in Fig. 12.8a,b. Coefficients calculated with both schemes, the MH05 modification
of the KC02 scheme, and the newer scheme KC05 are close in the range of Log10D (μm) from 2 to
4.5 (D from 100 μm to 3 cm), and then begin to diverge. The fall speeds (Fig. 12.8c) in both schemes
are close up to Log10D = 4.5 (D = 3.1 cm), and the Vt in the MH05 scheme decreases at larger D > 3.1 cm
faster than in the KC05 scheme. Aggregates of this and larger sizes up to 10 cm were observed in
frontal systems near 0 °C (Lawson et al., 1998). Calculated fall speeds are close in Fig. 12.8c to the
field data on Vt by Locatelli and Hobbs (1974) for aggregates of unrimed radiating assemblages and
aggregates of unrimed side planes.
An interesting feature of both the KC05 and MH05 schemes is that they predict a decrease in Vt
at D ≥ 1 cm. It is reached by subtracting an additional term from Böhm Re-X relation in the MH05
modification of the KC02 scheme and by introducing the turbulent correction in the KC05 scheme
(Section 12.3). We used the values b = 1.8, s = 1.88 from Table 12.1 for these aggregates. If the
asymptotic value is used without the turbulent correction, bRe = 0.5, then (Eqn. 12.2.20) gives Bv =
0.5 × (1.8 − 1.88 + 2) − 1 = −0.04, predicting a decrease in Vt with increasing D. However, this asymp-
totic and negative value of Bv is attained at an unrealistically large D. The situation is changed by
accounting for the turbulent correction: Due to negative DbRe (see Fig. 12.6a), Bv becomes negative at
D ∼ 1 to 10 cm, and Vt begins to decrease with D in this region. A minimum bRe = 0.47 is reached at
the more realistic value of D = 2.5 cm. The evaluation again from (Eqn. 12.2.20) with these b, s gives
Bv = −0.1 (Fig. 12.8b)—i.e., the fall speed decreases with size as Vt ∼ D−0.1 near this point. This
602 Terminal Velocities of Drops and Crystals

3500 1.0

3000 0.8
KC05, turb
Coefficient Av
2500 0.6

Velocity index Bv
KC05, no turb
2000 MH05 0.4

0.2
1500
0.0
1000 KC05, turb.
–0.2 KC05, no turb.
500 MH05
–0.4
0
0 1 2 3 4 5 6 0 1 2 3 4 5 6
Log10D (µm) Log10D (µm)
(a) (b)

1.2

1.0
Fall velocity (m s–1)

0.8

0.6

0.4 KC05, turb

KC05, no turb
0.2 LH74, planes
LH74, assem.
0.0 MH05
0 1 2 3 4 5 6
Log10D (µm)
(c)

Figure 12.8. (a) Coefficient Av; (b) power law index Bv; and (c) fall velocity Vt for unrimed
aggregates of thin plates calculated with equations (Eqns. 12.2.18)–(12.2.20), C0, d0 for crystals,
with turbulent corrections (KC05, turb., solid diamonds), and without turbulent correction (KC05,
no turb., open squares), compared to Av, Bv calculated in MH05 with modified equations of KC02
(solid circles) and to the field data on Vt by Locatelli and Hobbs (1974, LH74) for aggregates of
unrimed radiating assemblages (crosses) and aggregates of unrimed side planes (asterisks). From
Khvorostyanov and Curry (2005b), J. Atmos. Sci., 62, © American Meteorological Society. Used
with permission.

decrease continues, but somewhat slower, at larger D (Fig. 12.8c). This decrease of fall speed with
increasing aggregate size would lead to a suppressed gravitational aggregation. As shown in Fig. 12.8c,
KC05 predicts at D ≥ 1–1.5 cm a decrease in fall speeds and a partial suppression of further aggregation.
Another comparison of the MH05 and KC05 schemes was performed for aggregates observed
in tropical cirrus during the TRMM campaign (Heymsfield, 2003) using the same values of the
parameters as in Fig. 12.6. The Vt shown in Fig. 12.9 were calculated with the KC05 scheme for
12.6. Results of Calculations 603

3.0

Fall velocity (m s–1)

2.0

KC05, cirrus alt.

1.0 H03, cirrus alt.
KC05, 1000 hPa
H03, 1000 hPa
aggreg./drops
0.0
0 5 10 15
Diameter (mm)

Figure 12.9. Fall velocities calculated with equations of Sections 12.2 and 12.3 and crystal
parameters (a, b, g, s) from TRMM data by Heymsfield (2003) for the conditions of experiments at
cirrus altitudes (solid diamonds, KC05) and recalculated for the surface level at p = 1000 hPa using
the equations of Section 12.5 (solid circles, KC05). These are compared to the calculations from
Heymsfield (2003) at corresponding altitudes (open diamonds and triangles, H03). The difference
does not exceed 5% at 1000 hPa. The curve calculated with the KC02-05 scheme using the same
a, b, g, s, but C0, d0 for the drops (crosses, aggreg./drops) is given for illustration of the difference
between the drops and crystals. From Khvorostyanov and Curry (2005b), J. Atmos. Sci., 62,
© American Meteorological Society. Used with permission.

the conditions of the experiment at high cirrus altitude, and recalculated to pressure p = 1000 hPa,
using the CpT correction (Eqn. 12.5.3c), and were compared to the corresponding data in Heyms-
field (2003), where calculations were performed with an MH05 modification of the KC02 scheme.
Fig. 12.9 exhibits good agreement between the two schemes, the difference not exceeding 5%. The
curve calculated with the KC02 scheme using the same a, b, g, s but C0, d 0 for the drops (crosses) is
shown for comparison. Its difference from the other two curves illustrates the effect of the particles’
shape and the difference between the drops and crystals fall speeds. The fall speeds at these two
heights are used in Section 12.6.7 for verification of the altitude correction (Eqn. 12.5.3c).

12.6.5. Other Crystal Habits

A comparison of the KC02–KC05 schemes with the other schemes and experimental data for various
crystal habits is shown in Figs. 12.10–12.12. All calculations were performed with C0, d0 for crystals
and a-s parameters from Table 12.1. Note that for crystal habits shown in Figs. 12.8–12.10, Re < 103
and the turbulent corrections are insignificant, so that actually the KC02 scheme could be used with
C0, d0 for crystals. A very good agreement of the KC02–KC05 schemes is seen with experimental
data from Heymsfield and Kajikawa (1987) and Mitchell’s (1996) calculations for hexagonal plates
(Fig. 12.10), with field data from Locatelli and Hobbs (1974) and Mitchell’s (1996) calculations
for rimed columns and dendrites (Fig. 12.11), with experimental data from Heymsfield (1972) and
Mitchell’s (1996) calculations for hexagonal columns (Fig. 12.12), and with experimental parameter-
ization from Brown (1970) and calculations from M96 for plates with sector branches (Fig. 12.12).
604 Terminal Velocities of Drops and Crystals

2.0
hexagonal plates
at sea surface

Fall velocity (m s–1)

1.5

1.0
KC05
M96
0.5
exper. HK87

0.0
0 2 4 6 8 10 12
Diameter (mm)

Figure 12.10. Fall velocities of hexagonal plates calculated with the equations of this chapter
and parameters C0, d0 for the crystals (KC05, solid circles) and by Mitchell (1996, diamonds,
M96), compared up to 12 mm, and parameterization by Heymsfield and Kajikawa (1987) based
on experimental data and extended to 2.2 mm (HK87, triangles). From Khvorostyanov and Curry
(2005b), J. Atmos. Sci., 62, © American Meteorological Society. Used with permission.

3.0 KC05, rimed col.

2.5 LH74, rimed col.
Fall velocity (m s–1)

KC05, rimed dendr.

2.0 LH74, rimed dendr.
1.5

1.0

0.5

0.0
0 1 2 3 4
Maximum dimension D (mm)

Figure 12.11. Fall velocities for densely rimed columns and dendrites calculated with equations of
this chapter and C0, d0 parameters for crystals (KC05, solid triangles and circles) compared to the
field data by Locatelli and Hobbs (1974, LH74, asterisks and diamonds). From Khvorostyanov and
Curry (2005b), J. Atmos. Sci., 62, © American Meteorological Society. Used with permission.

Results for other dendritic crystals (plates with broad branches, stellars) are close to those for sector
branches and to those calculated in M96 for these crystal types.
Thus, the method of fall velocity calculations based on the KC02–KC05 scheme can be applied for
various crystal habits. The application of this method for snowflakes can be done with caution and
may need modifications due to the high variability of snowflake properties, in particular habits and
densities. Studies of snowflakes provide contradictory results—e.g., Magono and Nakamura (1965)
predicted a decrease in snowflake fall velocity as Vt ∼ D−1/2, which was explained by the authors by a
12.6. Results of Calculations 605

2.5
Hex. columns, KC05
Columns, H72-M96 exp.
2.0

Fall velocity (cm s–1)

Plates w/sect. branches, KC05
1.5 Plates, B70 exp.

1.0

0.5

0.0
0 1 2 3 4 5
Crystal diameter D (mm)

Figure 12.12. Fall velocities for hexagonal columns (solid triangles) and plates with sector branches
(solid circles) calculated with equations of this chapter (KC05) and compared to experimental
data for columns from Heymsfield (1972) and calculations of Mitchell (1996) (open diamonds,
H72-M96) and the parameterization of Brown (1970) for plates (open circles, B70). From
Khvorostyanov and Curry (2005b), J. Atmos. Sci., 62, © American Meteorological Society. Used
with permission.

significant density decrease with growing size. In contrast, Jiusto and Bosworth (1971) observed and
parameterized a velocity increase with size as Vt ∼ D0.2. This uncertainty in snowflake properties and
their high variability indicates a necessity of their further studies—in particular, parameterization of
the A-D, m-D, and density-D relations. These relations can be incorporated into the method described
here. The complicated shapes of snowflakes crystals may be parameterized using semi-empirical
relations based on a combination of the theoretical approach and an empirical correlation analysis.
Zawadski et al. (2010) and Szyrmer and Zawadski (2010) provided a review of the natural variability
of snow terminal velocity, and parameterizations of the fall velocities of snowflakes, and found an
average relationship between the mass of snowflakes and their terminal fall velocity.

12.6.6. Application to Hail

The final test of this scheme was performed with an application to hail. This crystal habit achieves the
greatest sizes, D ∼ 10 cm, numbers Re ∼3 × 105, X ∼ 1011, and is especially sensitive to the turbulent
corrections. Fig. 12.13 shows that calculations with the KC05 scheme and a-s parameters from Table
12.1 are again in very close agreement with the experimental data for hailstones from Matson and
Huggins (1980; hereafter MH80). The difference between MH80 and KC05 with turbulent correc-
tions is less than 3.5% at D = 50 mm and 2% at D = 100 mm. Vt without turbulent corrections is 26%
higher at D = 100 mm, which illustrates the effect of turbulence on aRe described by (Eqn. 12.4.4):
accounting for turbulence leads to a reduction in aRe and thus in Vt by a factor of 1/Ct1/2 = 1/1.26.
Fig. 12.13 shows that our choice of Ct = 1.6 recommended by Böhm (1992) leads to agreement with
the MH80 data. Note that the turbulent correction xt(D) for hail lies in the region of small D ∼ 2–5 mm
(see Fig. 12.6) and does not lead to a noticeable effect in fall speeds at large sizes in contrast to the
aggregates (compare with Fig. 12.8c).
606 Terminal Velocities of Drops and Crystals

50
KC05, turb

40 MH80 exp

Fall velocity (m s–1)

KC05, no turb
30

20

10

0
0 20 40 60 80 100
D (mm)

Figure 12.13. Terminal velocity of hailstones Vt calculated with equations from this chapter,
d0 and C0 for crystals, and Ct = 1.6 with turbulent correction (KC05 turb., solid circles) and without
correction (diamonds, no turb.) compared to the experimental data from Matson and Huggins 1980
(MH80, triangles). The difference between KC05 with turbulence and MH80 is less than 3.5% at
D = 50 mm and 2% at D = 100 mm. Vt with turbulent corrections is 26% smaller at D = 100 mm than
without account for turbulence, upper curve), which illustrates the effect of turbulent corrections
(Ct)−1/2 = 1/1.26. From Khvorostyanov and Curry (2005b), J. Atmos. Sci., 62, © American
Meteorological Society. Used with permission.

12.6.7. Altitude Correction Calculations

The altitude or pressure–temperature correction (Eqn. 12.5.3c) was verified by comparing with
results from Beard (1980), who fitted slopes of the measured or calculated CD(Re) curves or used
similarity arguments, and then parameterized by constructing an empirical interpolation func-
tion CpT(Re) linear by ln(Re) between the viscous CpT0 and aerodynamic CpT∞ limits, the same as
(Eqns. 12.5.4) and (12.5.5), but with the stepwise constraints CpT = CpT0 at Re < 0.2 and CpT = CpT∞ at
Re > 103. We performed calculations of CpT for the same altitude variation as in Beard (1980) between
the reference level with p = 770 hPa, Tc = 0 °C and the top of the atmosphere with p = 232 hPa,
Tc = −55 °C. Fig. 12.14a shows four curves of the CpT correction, calculated with the KC05 scheme
for crystals with and without turbulent correction for the spheres, and Beard’s (1980) parameteriza-
tion along with several experimental points from that work. It is seen that all four curves in the region
1 < Re < 5 × 102 lie close, the difference slightly increasing for smaller particles at Re ∼ 0.1 and
around large Re ∼ 103. The latter local maximum (absent on the curve without turbulence) is caused
by the turbulent correction in our scheme and allows explanation of an experimentally observed local
increase in CpT near Re ∼ 103 (asterisks) that is not described by Beard’s (1980) monotonous function.
This agreement in the altitude correction indicates a validity of the KC05 scheme, which provides a
theoretical justification and smoothing of Beard’s parameterization.
Another test of (Eqn. 12.5.3c) for the CpT correction was performed by comparing its values cal-
culated with (Eqn. 12.5.3c) and bRe,t from (Eqn. 12.3.4) for crystal aggregates in tropical cirrus (see
Table 12.1) with the direct calculation of the velocities ratio CpT = Vt(p,T)/Vt(p = 1000, T = −5 °C)
12.6. Results of Calculations 607

1.7
KC05, turb

1.6 KC05, no turb

B80, param.
1.5
spheres
Correction

1.4
B80, exp

1.3

1.2

1.1
1E–3 1E–2 1E–1 1E+0 1E+1 1E+2 1E+3 1E+4 1E+5
Reynolds number Re
(a)

1.3
C(p,T)

Vt(p,T)/V00

1.2
p–T correction

1.1

1.0
1E–3 1E–2 0.1 1 1E+1 1E+2
Diameter (mm)
(b)

Figure 12.14. The altitude (pressure–temperature) correction CpT. (a) Calculations using
(Eqns. 12.5.3b) and (12.5.3c) for crystals with turbulence (KC05, turb., diamonds), and without
turbulence (KC05, no turb., triangles); Beard’s (1980) general parameterization (crosses, B80),
calculations for spheres (solid circles) and some experimental points from Beard (1980), located
higher than Beard’s parameterization (B80, exp., asterisks); (b) correction C(p,T) for tropical cirrus
aggregates as in Fig. 12.9 calculated from (Eqn. 12.5.3c) and as the ratio Vt(p,T)/Vt(p = 1000,
T = −5 °C). From Khvorostyanov and Curry (2005b), J. Atmos. Sci., 62, © American Meteorological
Society. Used with permission.
608 Terminal Velocities of Drops and Crystals

calculated with the equations of Section 12.2, and Section 12.3 (see Fig. 12.9). Fig. 12.14b shows that
both methods give very close results over the entire D-range, where the CpT correction significantly
varies with D between the viscous limit (Eqn. 12.5.4) for small particles and the aerodynamic limit
(Eqn. 12.5.5) for large particles. Fig. 12.14 shows that the difference in the fall velocities of the large
and small particles increases with altitude by 30–70%, enhancing by this factor the rate of the gravi-
tational coagulation and accretion. This effect can be accounted for in various models with use of
the CpT correction (Eqns. 12.5.3a), (12.5.3b), and (12.5.3c) in calculations of precipitation intensity.

12.7. Parameterizations for Large-Scale Models

The equations described earlier are directly applicable to cloud models with explicit microphysics
that typically utilize the bin representation of the particle size spectra, with the particles in each bin
falling at their own velocities. However, parameterization of these relations is desired for applica-
tions to larger-scale models and to remote sensing. Advanced general circulation models are using
bulk cloud microphysical parameterizations (e.g., Fowler et al., 1996, hereafter FRR96). However,
the long integration periods and the large number of the grid points impose strong limitations on the
number of arithmetic operations per time step. Therefore, some simple parameterizations are desired
for large-scale models.
Such a simple parameterization is easily developed using the continuous power law representation
of the fall velocity. This parameterization is illustrated using the bulk microphysics parameterization
from Fowler et al. (1996). The size spectrum of rain is approximated by Fowler et al. (1996) with the
Marshall–Palmer distribution:
N DR = N 0 R exp(− λ R DR ), (12.7.1)

where DR is the diameter of a raindrop, N0R = 8 × 102 cm−4 is the intercept, lR = (prwN0R /raqr) is
the slope, and qr is the rain water mixing ratio. The fall velocity of a raindrop was approximated in
Fowler et al. (1996) by an expression based on the Gunn and Kinzer (1949) data,

VR ( DR ) = (c0 R + c1R DR + c2 R DR2 + c3 R DR3 )( p / p0 )0.4 (12.7.2)

with c0R = −0.267, c1R = 5.15 × 103, c2R = −1.0225 × 106, c3R = 7.55 × 107, and the average fall velocity
is defined as the mass-weighted value,
∞

VR =
∫ 0
N 0 R ( DR ) M ( DR ) VR ( DR ) dDR
. (12.7.3)
∞
∫ 0
N 0 R ( DR ) M ( DR ) dDR

Substituting (Eqns. 12.7.1) and (12.7.2) into (Eqn. 12.7.3) and analytically evaluating the integrals yields

VR ( DR ) = (b0 R + b1R λ R−1 + b2 R λ R−2 + b3 R λ R−3 )( p /p0 )0.4 , (12.7.4)

with b0R = −0.267, b1R = 206 × 102, b2R = −2.045 × 107, and b3R = −9.06 × 109. This equation is used
in Fowler et al. (1996). It can be simplified and refined using the method described in this chapter.
First, note that the subintegral functions in the numerator and denominator of (Eqn. 12.7.3) have
pronounced maxima in the rather narrow range of sizes near the drop diameter Dmax ∼ 2000–2300 μm
as shown in Fig. 12.15a. According to Section 12.2, VR (D) can be presented here by the power
12.7. Parameterizations for Large-Scale Models 609

2E–5 1E–2 Numerator

Denominator

Denominator
8E–3

Numerator
1E–5

4E–3

0E+0 0E+0
0 1500 3000 4500 6000
Drop diameter (µm )
(a)

800
This fit
FRR96
Averaged VR (cm s–1)

700

600

500

400
0.0 1.0 2.0 3.0
Mixing ratio qr (g/kg)
(b)

Figure 12.15. (a) Subintegral functions in the numerator (circles) and denominator (diamonds)
of the average velocity VR (Eqn. 12.7.3); (b) a comparison of VR calculated with the previous
equation (12.7.4) from Fowler et al. (1996) (crosses) and new (Eqn. 12.7.5) with cvt = 2.9 (triangles)
at surface pressure. From Khvorostyanov and Curry (2002), J. Atmos. Sci., 59, © American
Meteorological Society. Used with permission.

law VR ( DR ) = Av DRBv; the coefficients at the maximum Dmax are easily evaluated with (Eqns. 12.2.19)
and (12.2.20) or (Eqns. 12.4.7)–(12.4.11) and are Avm ∼ 2 × 103 cm0.25 s−1 and Bvm ∼ 0.75, as is seen in
Fig. 12.3. These expressions for VR, which are much simpler than (Eqn. 12.7.2), can be substituted
into (Eqn. 12.7.3) now with these constants Avm, Bvm, since the main contribution into the integrals
comes from this region. The integral is easily evaluated with (Eqn. 12.7.1) analytically:
Bvm /4
 ρ a qr 
VR = cvt Avm λ R− Bvm = cvt Avm   , (12.7.5)
 π ρw N 0 R 

where cvt = Γ(4.7)/Γ(4) = 3.7, Γ(x) is Euler’s gamma function and Bvm /4 = 0.188. This expression is
valid at standard atmospheric conditions. The temperature and pressure corrections can be calculated
610 Terminal Velocities of Drops and Crystals

with (Eqns. 12.5.3a), (12.5.3b), and (12.5.3c); bRe is evaluated using (Eqn. 12.2.20), bRe = (Bv + 1)/
(b − s + 2), which gives with this Bvm ≈ 0.75 and b = 3, s = 2 for spherical drops, bRe ≈ 0.58. Thus,
in the large particle limit (Eqn. 12.5.5)
0.58
 p T
VR ( p, T ) = c pT VR ( p0 , T0 ), c pT =  0  . (12.7.6)
 pT0 

Note that this correction also accounts for the temperature dependence, in addition to Gunn and
Kinzer’s formulation (Eqn. 12.7.2), and the power index of p is almost 50% higher. A more precise
T-p correction for various size fractions used in a model can be calculated directly with (Eqn. 12.5.3)
without assuming the asymptotic large-size limit. In this example, the actual values of Av, Bv vary
slightly around the mentioned maxima in (Eqn. 12.7.3), and substitution of VR with constant coef-
ficients may cause an error. Hence, the coefficient cvt arising from the gamma functions should be
considered as a parameter that needs some tuning; the calculations show that the value cvt = 2.9 is
better than cv = 3.7 in (Eqn. 12.7.5).
A comparison of VR values calculated with (Eqn. 12.7.4) from Fowler et al. (1996) (crosses) and
(Eqn. 12.7.5) with cvt = 2.9 (triangles) for the surface pressure (p0 = p) is given in Fig. 12.15b as the
functions of the rain water mixing ratio qr. Both equations are in excellent agreement, the maximum
error is −4.7% at the lowest qr and 4.1% at the highest qr. Equations (12.7.5) and (12.7.6) are simpler
and more universal for raindrop terminal velocity since the corrections for both temperature and
pressure are accounted for by (Eqn. 12.7.6). The new parameterization (Eqns. 12.7.5) and (12.7.6) is
also more economical since it contains fewer arithmetic operations, and can be recommended for use
in cloud and climate models that use bulk microphysics parameterizations. The corresponding fall
velocities for several ice crystal types accounted for in a model using a double-moment or another
parameterization of the size spectra (e.g., the modified gamma distributions, and Marshall–Palmer or
inverse power laws) can be easily calculated in a similar way.

12.8. Applications for Remote Sensing, Other Objects and Other Planets

Additional applications for parameterized fall velocities occur in remote sensing. In some algorithms
for the measurements of vertical velocities with Doppler radars, power law approximations of Vt are
used and the “statistical” or average relations between Av and Bv are established based on numerous
calculations of Av(D) and Bv(D) (e.g., Matrosov and Heymsfield, 2000). The calculation of Vt(D)
based on the stepwise representation for X may create problems because the matching points by X,
when the power law changes, correspond to different points in terms of diameter. This in turn may
create problems when calculating the reflectivity-weighted or mass-weighted velocities by integra-
tion of the power law for Vt of individual particles with the size spectra. The method described in this
chapter is free of such problems, Av−Bv relations and averaged velocities can be easily calculated by
integration using the continuous analytical form of Av(D) and Bv(D) (Eqns. 12.2.18)–(12.2.20) for the
various particles types. A comparison of the calculated values of Av and Bv for hexagonal columns
and bullet rosettes with the fit from Matrosov and Heymsfield (2000) for bullet rosettes was performed
in Khvorostyanov and Curry (2002) and showed good agreement. Note that when evaluating the
integrals for the reflectivity-weighted velocities, again the same analysis of the subintegral functions
12.8. Applications for Remote Sensing, Other Objects and Other Planets 611

described earlier in this section can be performed. This may simplify the final expressions. Note that
the integrals of the type (Eqn. 12.7.3) in remote sensing contain the higher powers of the particles’
diameters, thus the maxima in the subintegral expressions with D nexp(−l iD) should be sharper, the
accuracy of using the constant values of Av, Bv at the maximum location should be higher, which
facilitates application of this power law representation for remote sensing.
In Sections 12.3–12.6, we considered falling drops and ice crystals in the air in Earth’s atmo-
sphere. However, the equations derived in Section 12.2, as was mentioned there, are general and can
be applied to any fluid and body—e.g., to the clouds in the atmospheres of the other planets, or to
the objects falling or rising in other hydrodynamical fluids by using the appropriate densities of the
fluid rF and of the body rb, and the acceleration of gravity for a given planet. The examples of fall-
ing bodies include the clouds of aerosol particles in the air or interstitial aerosol in a cloud (rF = ra,
rb = rs, with rs being the density of the solid material); falling bodies in the cloud chambers or other
laboratory devices filled with various gases and liquids—e.g., well-known laboratory experiments for
measurements of the fall velocities in a vertical tube filled with glycerin, oil, water, or similar viscous
liquids; and sinking clouds of aerosol particles in the ocean (rF = rw, rb = rs). In these cases, rs > rF
and the velocity in (Eqns. 12.2.15a), (12.2.15b), and (12.2.16) is directed downward.
Examples of rising bodies (with rb < rF) include the rising radiosonde balloon in the atmosphere
(rF = ra, and rb is the average density of the device), and the rising of small frazil ice particles
formed in the supercooled river or ocean mixed layer (rF = rw, and rb = ri < rw) (A description of the
phenomenon of the frazil ice formation is described in Curry and Webster, 1999). An application of
the Khvorostyanov and Curry (2002, 2005) scheme for evaluation of the frazil ice rising velocities
in water was discussed by Morse and Richard (2009). The sizes of the ice particles of 1-3 mm and
their rising velocities of 0.7-0.9 cm s-1 were measured and calculated by Morse and Richard, and
the parameters d 0 and C0 specific the for frazil ice in this case were estimated. Some man-governed
objects like spherical bathyspheres (an analogy of drops) and non-spherical bathyscaphs (an analogy
of crystals) used to reach very deep layers in the ocean with very high water pressures can change
their average density by controlled changing their volumes and may be falling or rising depending
on the relation of rF and rb. Their velocities also can be described by this theory with an appropriate
parameterization of the m–D and A–D relations.
These situations and many other cases can be considered with (Eqns. 12.2.15a), (12.2.15b), and
(12.2.16) with the corresponding nonsphericity factor xf(D) when necessary. Equation (12.2.16)
shows that these velocities can be characterized by a useful similarity criterion:
bRe
1− 2 bRe
 ρb 
YOF (object / fluid ) = ν F g −1 , (12.8.1)
 ρ F 

where |x| means the absolute value, and the subscripts “O” and “F” mean the object and fluid. This
criterion YOF is independent of the particle dimension but does depend on the general properties of
the fluid (rF, nF), the object (rb), and the planet (acceleration of gravity g). From the definition (Eqns.
12.8.1) and (12.2.16), it follows that the terminal velocity for ellipsoids can be written as

Vt = aRe [(4 /3)ξ f ( D)]bRe D (3 bRe −1)YOF (object /fluid ), (12.8.2)

or Vt ∼ YOF for the particles of the same size and shape.

612 Terminal Velocities of Drops and Crystals

Thus, YOF allows us to establish simple similarity relations among the velocities of the falling or
rising objects for various environments and planets. For example, consider sedimenting small aerosol
particles with the density of 1.5 g cm−3 in the laboratory chamber designed for measurements of fall
velocities and filled with water. Then, in (Eqn. 12.8.1) rb =rs ≈ 1.5 g cm−3, rF = rw = 1 g cm−3, bRe = 1,
and according to (Eqn. 12.8.1), YOF (aerosol/water) = (1/2)(g/nw), where nw is the kinematic viscos-
ity of water. For small drops in the air, YOF (drop/air) ≈ (g/na)(rw /ra). Using for T = 5 °C the values
nw = 0.015 cm2 s−1 and na = 0.15 cm2 s−1, we find (na/nw) ∼ 10, and (ra /rw) ∼ 10−3, then YOF(aerosol/
water) /YOF(drop/air) = (1/2)(na /nw)·(ra /rw) ≈ 0.5·10−2.
Thus, the fall speeds of the small aerosol particles in water are only a half percent of the value for
the drops of the same radius in air, and measuring the fall velocities of aerosol particles with a given
radius in this device filled with water and multiplying by ≈200 we can obtain the fall velocities of
aerosol of the same size in the air. This similarity criterion also allows us to conclude that a cloud of
hydrosol particles can be transported before their fallout by the ocean currents over the distances by
two orders of magnitude greater than a cloud of an aerosol of the same size in the atmosphere. The
other processes like convection or coagulation may change this relation, but the estimates of the rela-
tive role of sedimentation can be elucidated with the criterion YOF.
Other objects, fluids, and planets can be considered in the same way. For example, the difference
in the fall velocities of the particles in the atmospheres of Earth and Mars is determined by the differ-
ence in their accelerations of gravity, gE and gM, and viscosities, na and nM. For small particles with
bRe = 1, using (Eqn. 12.8.1) and the condition rb >> rF, we obtain an estimate Vt(Mars)/Vt (Earth) ∼
(gM /gE)(na /nM). This relation is simplified for layers with close viscosities, na ≈ nM. Then, using the
values gE = 9.81 m s−2 and gM = 3.37 m s−2 (e.g., Curry and Webster, 1999, Chapter 14 therein), we
obtain Vt (Mars) = Vt (Earth) × (gM/gE) ∼ 0.34Vt(Earth). For large particles with bRe = 1/2, we have
from (Eqn. 12.8.1) Vt (Mars) = Vt (Earth) × (gM /gE)1/2 ∼ 0.59Vt (Earth). The same comparison for
Jupiter with the acceleration of gravity gJ = 26.2 m s−2 gives for the layers with similar viscosities for
the small particles Vt(Jupiter) ∼ 2.67Vt(Earth), and for the large particles, Vt (Jupiter) ∼ 1.63Vt (Earth).
The vertical structures of the planetary atmospheres (temperature, pressure, and density, and chemi-
cal composition) are known for the planets of the solar system along with the probable cloud types at
various heights (e.g., Curry and Webster, 1999, Chapter 14).
It is possible to create in the cloud chambers the conditions that correspond to various clouds on
the planets and to measure the viscosities, densities, and particle fall velocities at the Earth gravity
acceleration. Then, using the similarity criterion YOF, it is possible to estimate Vt of the particles on
the other planets with their gravity accelerations and to calculate the temperature–pressure correc-
tions CpT for the fall velocities for various planets as in Section 12.3. These data could be used in stud-
ies of the fall velocities and numerical cloud simulations on various planets (e.g., Buikov et al., 1976;
Lewis and Prinn, 1984; Ibragimov, 1990; Goody, 1995; Lewis, 1995; Curry and Webster, 1999).
13
Broad Size Spectra in Clouds and the Theory
of Stochastic Condensation

13.1. Introduction

The characteristics and evolution of the cloud droplet and crystal size spectra determines cloud
radiative properties and the formation of precipitation. Accounting for these processes in cloud-
resolving models and climate models requires correct understanding and then parameterization of
cloud microstructure and its dependence on predicted atmospheric parameters. During the past five
decades, cloud physics and cloud optics have widely used empirical parameterizations of cloud par-
ticle size spectra such as the gamma distributions or exponential spectra described in Chapter 2.
These empirical spectra were used in the remote sensing of clouds and also in the modeling and
parameterization of cloud properties and processes, both in the cloud-resolving models (CRM) and
in some advanced general circulation models (GCMs). A new impetus for bulk microphysical models
was given during the past two decades by development of the double-moment bulk schemes that
include prognostic equations for the number concentrations of hydrometeors in addition to the mixing
ratio, which allows a higher accuracy in predicting the cloud microphysical properties. The double
moment schemes are used in cloud models (e.g., Ferrier, 1994; Harrington et al., 1995; Meyers et al.,
1997; Cohard and Pinty, 2000; Girard and Curry, 2001; Seifert and Beheng, 2001, 2006; Morrison
et al. 2005a,b; Milbrandt and Yau, 2005a,b). These schemes are also incorporated into advanced
mesoscale weather prediction models such as the Weather Research and Forecast (WRF) model (e.g.,
Morrison et al. 2005a,b) and the weather prediction Consortium for Small-Scale Modeling (COSMO)
model (e.g., Zubler et al., 2011). The most advanced general circulation models (GCMs) also began
using such double-moment microphysics parameterizations that were included earlier only in cloud-
resolving models (e.g., Sud and Lee, 2007; Morrison and Gettelman, 2008; Sud et al, 2009). These
parameterizations are also based on using gamma distributions or exponential spectra with prescribed
parameters.
A deficiency of empirically derived parameterizations of particle size spectra is that the parame-
ters are generally unknown and are fixed to some prescribed values or parameterized based on experi-
mental data. The index p of the gamma distributions (see Chapters 2–5) is of key importance because
it determines the relative dispersion of the spectra, srr = (p + 1)−1/2, and thereby the cloud optical
properties and the rates of water conversion and of precipitation formation. Experimental studies
show wide variations in clouds of the relative dispersions—that is, of the indices p, which measured
values varied from 1–2 to 25–30 (e.g., Austin et al., 1985; Curry, 1986; Mitchell, 1994; Pruppacher
and Klett, 1997; Brenguier and Chaumat, 2001). As described in Chapter 2, the parameters of these

613
614 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

distributions in the models have usually been prescribed from observations and may vary consid-
erably from one model to another. Values of p have often been rather arbitrarily chosen between
0 and 10. Ideally, these parameters should be related to the local atmospheric conditions and evalu-
ated from the cloud bulk model or climate model rather than prescribed uniformly over the globe.
The accuracy of calculations can be improved if the parameters of the size spectra are calculated
with equations having a basis in theory. For example, the p-indices (and thereby spectral dispersions)
were calculated using analytical expressions from Khvorostyanov and Curry (1999d) by Morrison et al.
(2005a,b) and Morrison and Pinto (2005) in a cloud model with double-moment bulk microphysics
scheme and by Sud and Lee (2007) and Sud et al. (2009) in the Goddard General Circulation Model.
Calculated values of these p-indices showed substantial variations in time and space, resulting in
variations in the onset of coalescence and in cloud optical properties.
In this section, we briefly review the major mechanisms and theories suggested for an explanation
of the formation of the broad size spectra of cloud drops and crystals, with special emphasis on the
kinetic equations of stochastic condensation that allow us to obtain analytical solutions suitable for
parameterization of the size spectra in cloud and climate models.

13.1.1. Mechanisms and Theories of the Formation of Broad Size Spectra in Clouds

Understanding the formation of the size spectra and their parameterizations have been hampered by
the contradiction between the theory of Maxwellian condensation and observations of size spectra in
clouds. As was discussed in Chapter 5, the theory of regular condensation in a constant updraft has
been shown to narrow the droplet spectrum with time. Since broad spectra are observed in clouds and
are required to initiate collision and coalescence growth of precipitation, numerous attempts have
been made to remove this contradiction. Various hypotheses and approaches have been developed to
explain and describe broad spectra in clouds, including several attempts at analytical solutions to the
kinetic equations for stochastic condensation.
The inhomogeneous mixing theory (Baker and Latham, 1979; Baker et al., 1980) considers pen-
etration of the tongues or blobs of dry air into a cloud from the top or the sides with subsequent partial
drop evaporation. This can be viewed as a two-stage process. At the first stage, the dry parcel and
the neighboring saturated air parcels remain separated with the distinct interface surface. Complete
evaporation occurs of all drops at the interfaces of the mixing parcels, but all drops remain unaf-
fected at some distance from the interface. At the second stage, the interface breaks down and the
two air parcels mix. This mixing may lead to a supersaturation difference in the mixed volumes and
to spectral broadening, or even bimodal spectra. The essence of the interface was somewhat subtle
in this model. Broadwell and Breidenthal (1982) extended this concept with nongradient turbulent
mixing, whereby a source of supersaturation generation, instead of the vertical velocity, is determined
by the rate at which the interface between the mixed volumes is formed. Baker et al. (1984) adapted
this model of nongradient mixing in a shear layer to inhomogeneous mixing in clouds, which gave a
better conceptual and mathematical basis for the model of inhomogeneous mixing.
An important feature of the inhomogeneous mixing model is that local values of supersaturation
are much greater than in adiabatic or homogeneous mixing; thus, the largest drops grow faster. In the
inhomogeneous mixing model, more droplets are completely evaporated, and the newly activated
13.1. Introduction 615

small droplets cannot compete for the water vapor as effectively as the previous larger drops. This
leads to the local growth of the supersaturation in the vicinity of the older larger drops less effected
by mixing, resulting in their more rapid growth.
Another model of turbulence effects on droplet spectral broadening, called the theory of homoge-
neous mixing, was suggested by Telford and Chai (1980) and Telford et al. (1984). This theory views
a cloud as an ensemble of vertically coherent updrafts and downdrafts. When the entrained drier
air near the cloud top mixes with the saturated cloud air, drops evaporate and the resulting mixture
becomes denser, triggering its descent. Evaporation continues in this descending parcel, causing
droplet sizes to decrease. The smaller drops in this parcel are replaced with the larger drops that are
brought in this parcel from the neighboring undiluted parcels, providing a continuous source of the
larger drops. When this downdraft becomes an updraft in turbulent motion and eventually reaches
the cloud top, the drops in this parcel are larger than they were before the descent. Thus, according
to Telford’s hypothesis, recycling of the drops in turbulent down- and updrafts broadens the drop size
spectra. Further field experiments with measurements in convective clouds did not support Telford’s
hypothesis, since the largest drops were found in the wettest and least diluted ascending cloud por-
tions (e.g., Hill and Choularton, 1985; Paluch and Knight, 1986). Telford (1987) argued that this
mechanism could operate in some other maritime cloud types.
Another similar mechanism suggested was isobaric nongradient mixing based on the Broadwell
and Breidenthal (1982) model (e.g., Gerber, 1991). When two saturated cloud parcels at different
temperatures are completely mixed, their temperature and humidity will be equal to average values,
but due to the nonlinearity of the saturated humidity, the mixture will be supersaturated, this will
accelerate drop growth in this domain and result eventually in spectral broadening.
Belyaev (1961, 1964) and Sedunov (1965) accounted for the fact that the fields of vapor, tem-
perature, and supersaturation around a drop may experience random turbulent fluctuations. The
authors considered Maxwellian drop growth in the random supersaturation field and obtained broad
drop spectra in the form similar to Gaussian distribution. Other mechanisms have been proposed
that include horizontal inhomogeneities in cloud condensation nuclei (CCN). Kabanov et al. (1970)
assumed that the drop concentrations at a fixed cloud height is inhomogeneous due to the spatial
variability of the cloud condensation nuclei and can be described by the analytical functions (gamma
distribution or Gauss normal distribution). Using the mass balance equations, they derived the ana-
lytical size spectra, which had a finite spectral width, but were different from the observed gamma
distributions. A similar approach was developed by Smirnov and Kabanov (1970) for the spatial
inhomogeneity of the vertical velocity described by the Gauss normal distribution in agreement with
the measurements by Warner (1969a,b).
Another hypothesis was based on observations of giant and ultragiant aerosol particles with sizes
up to 100 μm (e.g., Ludwig and Robinson, 1970; Hobbs et al., 1978; Johnson, 1982) that could initi-
ate formation of the precipitation particles. Smirnov and Sergeev (1973) performed calculations of
the growth of cloud drops on the large hygroscopic aerosol particles described by the inverse power
law. They showed that such particles may rapidly grow to the sizes of precipitation and that the size
spectra of large drops formed on these CCN are also inverse power laws in good agreement with
measurements in California stratus by Ludwig and Robinson (1970). Similar conclusions on the role
of giant nuclei were made by Johnson (1982). In contrast, Woodcock et al. (1971) and Takahashi
616 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

(1976) found that giant salt nuclei do not give a substantial contribution to the process of precipita-
tion formation.
A few other approaches were developed for derivation of the analytical form of the size spectra.
Srivastava (1969) assumed that the cloud space is divided into a number of cells and the mass growth
rate of each drop by diffusion is proportional to the volume of each cell. For these drops growing
in the inhomogeneous supersaturation field, Srivastava derived the generalized gamma distribution
(Eqn. 2.4.11) with p = 2 and l = p + 1 = 3—i.e., the Weibull distribution f(r) = cNr 2exp(−r3). Liu
(1993, 1995), Liu et al. (1995), and Liu and Hallett (1998) derived the Weibull distribution for the
drop size spectrum using Shannon’s maximum entropy principle.
Srivastava (1989) introduced a concept of the microscopic and macroscopic supersaturation asso-
ciated with the random distribution of drops. This important hypothesis explains different growth
rates of various drops. It allows us to refine the kinetic equations and will be discussed in more detail
in Section 13.2. Cooper (1989) explained spectral broadening by various drops’ histories, so that
the drops that come to some level in the cloud may have different lifetimes and therefore different
sizes, which increases the spectral dispersion. Spectral broadening was also explained by averaging
over the parcels with different ages (Considine and Curry, 1996) and various sedimentation of the
cloud droplets (Baker et al., 1984; Considine and Curry, 1998). The stochastic nature of drop growth
in the turbulent atmosphere was accounted for by Kulmala et al. (1997), who calculated cloud drop
growth in the field of saturation ratio modeled as a stationary stochastic process that obeys the normal
distribution with some mean value and a dispersion ∼0.01 estimated from the measurements of the
temperature and humidity fluctuations. The authors found acceleration of drop growth in this variable
saturation ratio and appearance of bimodal spectra. Activation of new drops occurred in this work
even when the mean supersaturation was slightly negative due to the effect of positive supersatura-
tion dispersion.
Another mechanism to explain the broad cloud droplet spectra was based on observations of pref-
erential concentration of the particles in a turbulent flow in some regions (e.g., Shaw et al., 1998;
Vaillancourt and Yau, 2000; Shaw, 2003). This theory treats a turbulent flow as containing coherent
structures similar to the “vortex tubes” that have various vorticities. The size of the tubes is about
10 times the Komogorov’s scale, lK = (nf3/ed)1/4, where nf is the kinematic viscosity and ed is the dis-
sipation rate of turbulent energy—i.e., lK ∼ 0.5−1.5 cm. The particles are ejected from the regions of
higher vorticity by centrifugal forces and are accumulated in the regions with low vorticities between
the cells. Thus, the initial spatially homogeneous particle distribution becomes inhomogeneous. This
mechanism operates independent of entrainment and, therefore, can operate in adiabatic cloud cores.
Shaw et al. (1998) applied this theory for cloud drops and showed that cloud droplets of sufficient
size are not randomly dispersed in a cloud but are preferentially concentrated in regions of low vortic-
ity in the turbulent flow field. Regions of high vorticity (low droplet concentration) develop higher
supersaturation than regions of low vorticity (high droplet concentration). Therefore, on small spatial
scales, cloud droplets are growing in a strongly fluctuating supersaturation field. These fluctuations
in supersaturation exist independent of large-scale vertical velocity fluctuations. This breaks the link
between fluctuations of the supersaturation and vertical velocity. Shaw et al. (1998) adjusted a parcel
model for simulation of such turbulent vorticies with growing droplets and found that supersatura-
tion in the regions with lower drop concentrations can be up to 2–3 times higher than predicted by
13.1. Introduction 617

classical theory. Therefore, droplets growing in regions of high vorticity experience enhanced growth
rates, allowing some droplets to grow larger than predicted by the classic theory of condensational
growth. This mechanism helps to account for two common observations in clouds: the presence of
a large droplet tail in the droplet spectrum, important for the onset of collision-coalescence, and the
possibility of new nucleation above the cloud base, allowing for the formation of a bimodal droplet
spectrum. We note that this model of the vorticity cells with different supersaturations is conceptu-
ally similar to, and provides additional physical arguments, for Srivastava’s (1969) concept of cloud
microcells and Srivastava’s (1989) concept of microscale supersaturation.
Another line of research of drop growth in the turbulent atmosphere is based on direct numerical
simulations (DNSs). This is one of the most detailed and powerful models that studies 3D turbulence
and directly solves the Navier–Stokes equation as well as conservation equations for heat and water
vapor. The dynamical model is coupled with a droplet growth model that solves for the trajectories
of several tens of thousands of droplets along with their growth as a function of conditions in their
individual environments. Therefore, this method provides very detailed information on the simulated
process, but it imposes limitations on the spatial scales bounded by a few tens of centimeters and on
the time scales. Vaillancourtet al. (2002) performed a DNS for the condensation process and found
significant fluctuations of the number density and supersaturation, but accounting for drop sedimen-
tation tended to decrease these fluctuations. An unexpected result was that the drop size spectra were
narrower than without turbulence. This finding contrasted other studies of turbulence effects and the
origin of the effect is unclear. It could be a result of insufficient spatial resolution or an insufficient
intensity of simulated turbulence.
A comprehensive series of DNS simulations was performed by Paoli and Shariff (2004, 2009)
where the stochastic processes were modeled upon a set of Langevin equations for stochastic vari-
ables with various sources of fluctuations being superimposed on the mean fields. DNS simulations
were performed with small spatial and temporal steps. The authors showed that the temperature and
vapor fluctuations lead to supersaturation fluctuations, which are responsible for broadening the
droplet size distribution in qualitative agreement with in situ measurements. Based on the results
of their DNS, Paoli and Shariff formulated a set of Langevin stochastic equations for the droplet
area, supersaturation, and temperature surrounding the droplets. One important result of this work
obtained with their DNS was that there is a good correlation and scaling between the local fluctua-
tions of the drop radius r′ and supersaturation s′, which can be written as
r ′ / r ~ s ′/ s , (13.1.1)
where r and s are mean values of the radius and supersaturation. This supports Srivastava’s (1989)
hypothesis on the microscale supersaturation.
The concepts of entrainment and mixing among the cloud parcels were further developed and
quantified by introducing a supersaturation Damköhler number Da = tL /tf, where tL is a fluid time
scale, and tf is the supersaturation relaxation time (e.g., Shaw, 2003; Kumar et al., 2012). The Dam-
köhler number is a dimensionless parameter which relates the fluid time scale to the typical evapora-
tion time scale, and can capture many aspects of the initial mixing process within the range of typical
cloud parameters. Using the Damköhler number, the mixing process can be characterized by the limit
of strongly homogeneous regime (Da << 1), when the supersaturation varies much slower than the
618 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

fluid characteristics, and strongly inhomogeneous regime (Da >> 1), when the supersaturation relax-
ation time tf is much smaller than the fluid time tL. In the models of stochastic condensation consid-
ered in the following sections, the limits Da << 1 and Da >> 1 correspond to the high-frequency and
low-frequency turbulence regimes respectively. The most general case corresponds to Da ∼ 1, that is,
when the fluid time and the supersaturation relaxation time are comparable. Such a case is considered
later along with the both limits.
Some other possible mechanisms of spectral broadening, and of the effects of turbulence on the
size spectra and warm rain initiation, are reviewed in Beard and Ochs (1993), Blyth (1993), Vaillan-
court and Yau (2000), Shaw (2003), and Cotton et al. (2011).

13.1.2. Kinetic Equations of Stochastic Condensation

Simulation of the evolution of drop size spectra is enabled by kinetic equations that allow direct
simulation of the spectra as well as the development of analytical solutions to the drop size spectra.
Application of these equations in cloud models showed a fast progress over the last decades due to
increasing computer power. Several versions of the kinetic equations of stochastic condensation have
been developed and are reviewed in this section.
The theory of stochastic condensation attributes the presence of broad drop size spectra in clouds
to the occurrence of condensation in a turbulent medium. Development of this theory and derivation
of the kinetic equations of stochastic condensation began in the 1960s–1970s. These equations have
been derived for two limiting cases: the low-frequency turbulence regime when the characteristic
Lagrangian time scale of turbulent fluctuations tL (fluid time) is much greater than the supersatura-
tion relaxation time tf —i.e., tL >> tf (or Da >>1), and the high-frequency turbulence regime when
tL << tf (or Da << 1).
As mentioned in Chapter 5, the method of kinetic equations for the condensation-deposition pro-
cesses was introduced in cloud physics in the pioneering works of Buikov (1961, 1963, 1966a,b) as
described by (Eqn. 5.5.4a). Representing all quantities as the sums of mean and fluctuating values,
and applying Reynolds averaging procedure to (Eqn. 5.5.4a), Buikov arrived at the following equation:

∂f ∂ ∂ ∂ ∂
( ui − v (r )δ i 3 ) f  + ( rf
+  ∂r ) = ∂ x kij ∂ x f + J , (13.1.2)
ɺ
∂t ∂ x i  i j

where the usual summation over the indices i = 1, 2, 3 is assumed and all quantities here are averaged
over the turbulent ensemble. Buikov’s first kinetic equation of stochastic condensation is analogous
to the equations for the temperature or humidity, including terms with turbulent mixing described by
the diffusion coefficient kij and advection terms ∂(ui f )/∂xi) with the wind velocity ui. The equation
incorporates the additional terms describing sedimentation v(r) and condensational growth. The term
∂(rf
ɺ )/ ∂r for condensational growth has the form of the “advection in space of the radii,” with the
ɺ This simplified equation introduced by Buikov is equivalent to the high-
“velocity in radii space” r.
frequency approximation, tL << tf.
Another version of the kinetic equation of condensation that correspond to the low-frequency
approximation was derived by Levin and Sedunov (1966) and Sedunov (1974) who developed the
13.1. Introduction 619

theory of stochastic condensation that attributes the presence of broad drop size spectra in clouds
to turbulent fluctuations. This stochastic method treats supersaturation and droplet growth rate as
stochastic variables and replaces the usual operator of turbulent diffusion kz∂/∂z with the operator
kz(∂ / ∂z + As∂ / ∂s) for a nonconservative substance s (the droplet surface), where As is proportional to
the vertical velocity w.
The theory of stochastic condensation by Levin and Sedunov (1966) was criticized by Mazin and
Smirnov (1969), who argued that since both dr/dt and As are proportional to w, the droplet radius will
be a predetermined function of w. Therefore, the droplet radius will be a function of the height above
the cloud base z = wDt, which a cloud parcel reaches during the time Dt of its uplift, does not matter
if the uplift is in a regular flow with the mean w0 or in a turbulent flow with the sum of the mean and
fluctuation, w = w0 + w′. Thus, Mazin and Smirnov argued, the theory of stochastic condensation
by Levin and Sedunov cannot explain the formation of the broad spectra. Similar criticisms were
expressed by Warner (1969b) and Bartlett and Jonas (1972) who performed Lagrangian parcel model
simulations of the drop growth in ascending motion with superimposed fluctuations of the vertical
velocity but did not allow mixing among the parcels. In their simulations, the drop radius was highly
correlated with height, and thus they obtained narrowing of the spectra and concluded that stochastic
condensation cannot lead to spectral broadening. (These critics were answered in subsequent works,
as will be described in Section 13.10.)
The equations of Levin and Sedunov (1966) and Sedunov (1974) were further refined by a number
of authors. More rigorous and detailed derivations of the equation of stochastic condensation using
Reynolds averaging and more careful evaluation of covariances were performed by Stepanov (1975,
1976) using the method of perturbation theory similar to that used in the plasma theory, which is valid
for weak turbulence (fluctuations are smaller than the mean values), and by Voloshchuk and Sedunov
(1977), who used the extended statistical theory of turbulence.
Although these low-frequency stochastic kinetic equations could explain some features of the
drop size spectral dispersions in stratiform clouds, Manton (1979) argued that the time-dependent
solutions of the Gaussian type to the stochastic equations of Levin and Sedunov (1966) lead to dis-
persions that tend to some constant values and are still narrower than those observed in convective
clouds for the corresponding times. By hypothesizing a negative correlation between the fluctuations
in mean droplet radius and vertical velocity, Manton (1979) derived a modified version of the kinetic
equation that produced broader or bimodal size spectra with dispersions increasing for a longer time.
In a subsequent discussion of Manton’s theory (Merkulovich and Stepanov, 1981; Manton, 1981),
it was clarified that the condition of mass balance imposes some additional limitations on the basic
assumptions and analytical solutions to the kinetic equation. In particular, it was shown that the
bimodal spectra predicted by this theory should be monomodal in many cases, and the dispersions
should be smaller. Austin et al. (1985) showed that the basic assumption of Manton’s theory on the
negative correlation between the fluctuations in integral radius and vertical velocity is not observed
in the continental cumuli, while Curry (1986) found some evidence of negative correlation in Arctic
stratus. Thus, further verification or another hypothesis is required to break the link between super-
saturation and vertical velocity, which appears to be the primary requirement for deriving sufficiently
broad drop spectra using the stochastic kinetic equations.
620 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

The stochastic kinetic equations for condensation were generalized by Merkulovich and Stepanov
(1977) and by Smirnov and Nadeykina (1986) to account for curvature and solution effects in droplet
growth. The equations of Voloshchuk and Sedunov (1977) and Smirnov and Nadeykina (1986) have
the form
∂f ∂ ∂ Deff
+
∂t ∂ xi
( ui − vδ i 3 ) f  +
  ∂r r
(
a1 w + Acon f )
 ∂ ∂ Deff   ∂ ∂ Deff 
= + δ i 3 Bcon kij  + δ j 3 Bcon  f, (13.1.3)
 ∂ xi ∂r r   ∂ x j ∂r r 

where Deff is an effective coefficient of vapor diffusion (corrected Dv), Acon is a thermodynamic func-
tion that includes the effects of the salts and fluctuations of vapor density, and
ρa c p
Bcon = τ f (γ a − γ w ). (13.1.4)
ρw L

The kinetic equations of the type (Eqn. 13.1.3) are valid in the low-frequency approximation—
i.e., when tL >> tf. In this case, the fluctuations of supersaturation and droplet growth rate are highly
correlated with the vertical velocity. The solutions to these low-frequency equations generalized for
the exchange with environment were found for the quasi-steady state by Smirnov and Nadeykina
(1986) in the diffusion and kinetic regimes of drop growth that differ by the condensation coefficient
ac and the kinetic correction (Eqn. 5.1.22a), xcon = 4Dv /(acVw), to the drop growth rate. For diffusion
regime, r >> xcon—that is, for ac ∼ 1—the solution has the form of the generalized gamma distribu-
tion (Eqn. 2.4.11) but with a fixed index p = 1 and the indices related as p = l − 1—in other words,
it represents the Weibull distribution with the indices p = 1, l = 2 (see Section 2.4, (Eqn. 2.4.20a)):

f (r ) = cN 1r exp(− β1r 2 ). (13.1.5)

The relative dispersion of this spectrum is srr = 0.523 according to (Eqn. 2.4.20c), does not depend
on cloud properties, and is characteristic for broad size spectra. For the kinetic regime—that is, for
ac << 1—Smirnov and Nadeykina (1986) found the solution for the small droplet fraction in the
exponential form
f (r ) = cN 2ξcon exp(− β 2ξcon r ), (13.1.6)

with the relative spectral dispersion srr = 1.

McGraw and Liu (2006) accounted for the random turbulent fluctuations of supersaturation and
derived the kinetic equation of condensation in the form of the Fokker–Planck equation for the
squared drop radius A = r2:

∂ f ( A) ∂ f ( A) ∂ 2 f ( A)
= − vdrift + DA . (13.1.7)
∂t ∂A ∂ A2

The drift velocity vdrift is proportional to supersaturation s and the diffusion coefficient DA in the
A-space was defined in this work as proportional to the supersaturation dispersion ssA:

 dA  2 Dv ρ ws k A2σ sA
2
vdrift =   = k A s, kA = , DA = , (13.1.8)
 dt  Γρ w γσ
13.1. Introduction 621

where gs−1 is the correlation time of random supersaturation fluctuations. A stationary solution to this
equation was obtained by McGraw and Liu in the form of the Weibull distribution. It had the form
in terms of radii

N 
2/3  N  2/3

f ( A) = 2π N d  d  r exp  −π  d  r2 , (13.1.9)
 ql    ql  

where Nd is the droplet concentrations and ql is the dimensionless liquid water fraction.
An approach based on the Fokker–Planck equation was used by Jeffery et al. (2007) who derived
an equation similar to Voloshchuk and Sedunov (1977) and found that it ensures a noticeable spec-
tral broadening. Application of the Fokker–Planck equation will be discussed in more detail at the
end of this chapter. Thus, the analytical solutions to the kinetic equations of stochastic condensation
explained some features of the size spectra.
Since the supersaturation relaxation time tf ∼ 1−10 s in a developed cloud, and the Lagrangian tur-
bulent time tL ∼ 5−10 minutes, the high-frequency approximation might be representative of rapidly
changing conditions such as in an entrainment zone or during the initial phase of condensation, while
the low-frequency approximation might be representative of a developed cloud that is quasi-steady.
More detailed analysis of the turbulence in clouds showed that there are pronounced maxima in the
turbulent power spectra of vertical velocity at the frequencies w ∼ 10−3−10−2 s−1 and the long tails
extend to w ∼ 10−1 s−1 and smaller frequencies (e.g., Curry et al., 1988; Sassen et al., 1989; Quante
and Starr, 2002; Shaw, 2003; Monin and Yaglom, 2007b). As was shown in Chapter 5, the super-
saturation relaxation (absorption) time in the cloud regions with smaller particle concentrations can
be tf ∼ 30−60 s for liquid clouds and can exceed tf ∼ 30−180 min for crystalline clouds (Tables 5.1
and 5.2). Thus, the timescales tf and tL = 2p /w can be quite comparable over significant ranges of the
frequencies of turbulent spectra, and their relation can change during cloud evolution. Hence, more
general kinetic equations for arbitrary relations between tf and tL are required.
Khvorostyanov and Curry (1999c) performed the next step in development of this theory and
derived a generalized kinetic equation of stochastic condensation. The two principal features that
differentiate the new version of the kinetic equation from previous versions were the following:
1) consideration of supersaturation as a nonconservative substance with differentiation between the
macroscale and microscale supersaturation similar to the Srivastava’s (1989) concept; 2) consider-
ation of the supersaturation fluctuations of various frequencies over the whole turbulent spectrum
without assuming proportionality of supersaturation and vertical velocity, thus additional covariances
and a turbulent diffusion coefficient tensor dependent on the supersaturation relaxation time, kij(tf),
were introduced into the kinetic equation. Therefore, this version of the kinetic equation is applicable
for arbitrary relationships between the supersaturation relaxation time tf and the time scale of turbu-
lence tL or for arbitrary Damköhler numbers. These assumptions break the link between the fluctua-
tions in supersaturation and vertical velocity. The differentiation between the macro- and microscale
supersaturations produced the terms describing the diffusion in space of radii different from the pre-
vious formulations and allowed Khvorostyanov and Curry (1999d) to obtain the analytical solutions
of the gamma distributions type with variable p-indices.
These equations were further generalized in Khvorostyanov and Curry (2008c,d) to include
the effects of particle coagulation-accretion, breakup, and sedimentation and were applied to the
622 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

small-size and large-scale fractions of cloud drops and crystals. This resulted in analytical solutions
in the form of generalized gamma distributions, exponential functions, and inverse power laws.
In applying the kinetic equation for stochastic condensation in numerical cloud models, we are
faced with the following dilemmas:

1. The small characteristic time scale for the condensation process and presence of cross-
derivatives makes the numerical solution very computationally intensive. Despite development
of the stochastic condensation theory, practically all spectral cloud models that use the kinetic
equations of condensation-deposition, use them in the simplest form (Eqn. 13.1.2) suggested by
Buikov. Thus, refinement of the kinetic equation and development of the numerical schemes for
solution of the kinetic equations with cross-derivatives are required for the theory of stochastic
condensation and the practical needs of modeling.
2. Analytical solutions to stochastic kinetic equations in the low-frequency regime have been
obtained of the Weibull distribution (Eqn. 13.1.4) or of the Gaussian type, which does not agree
very well with observations that are typically in better agreement with a gamma distribution,
which is used in most cloud models with bulk parameterization of the microphysical processes.
This suggests there are deficiencies in the formulation of the kinetic equations for stochastic
condensation.

To address these concerns, a newer version of the kinetic equation for stochastic condensation for
the small-size fraction of drops and crystals spectra is derived in this chapter. This equation is valid
for arbitrary relative values of tL and tf that are suitable for numerical cloud models. Its analytical
solutions are obtained under a number of assumptions following Khvorostyanov and Curry (1999d,
2008d). A model of the condensation process in a turbulent cloud is considered, and Reynolds proce-
dure is applied to the regular and fluctuation parts of all the quantities, yielding an equation in terms
of covariances, where the concept of macro- and microscale supersaturation is introduced. Evaluation
of various covariances is performed by integration over the turbulent spectrum. Substitution of these
covariances into the original kinetic equation yields the final kinetic equation of stochastic condensa-
tion, and its particular cases for low- and high-frequencies regimes are considered.
Using some assumptions and simplifications, and neglecting the diffusional growth of larger par-
ticles, analytical solutions of the gamma distribution type are obtained for the small–size fraction and
their asymptotics are found. Additional solutions are obtained in the form of the generalized gamma
distributions with account for the diffusional growth of large particles, sedimentation, and coagula-
tion with the large–size fraction for the cases when such processes are important. An application
of the solutions for liquid clouds is illustrated by comparison of the calculated spectral indices and
size spectra with an example of a low St cloud similar to that observed in the Arctic (Curry, 1986).
Comparison with some previous theories and observations of spectral broadening shows that previ-
ous criticisms of the stochastic condensation theory were inconsistent. An example of the calculation
of the size spectra for a crystalline cloud similar to that observed during the SHEBA-FIRE field
experiment in the Arctic in 1998 is described. Finally, based on the Chapman–Kolmogorov equation
for stochastic processes, a general integral stochastic kinetic equation is formulated. Using this equa-
tion, the differential Fokker–Planck equation for stochastic condensation is derived, and it is shown
that various versions of the kinetic equations considered in this chapter are particular cases of this
Fokker–Planck equation.
13.2. Condensation in a Turbulent Cloud 623

13.2. Condensation in a Turbulent Cloud

13.2.1. Basic Equations

The kinetic equation of condensation can be written in the form described in Section 5.5 as
∂f ∂ ∂
+ [(ui − Vt (r )) f ] + (rf
ɺ ) = Js , (13.2.1)
∂t ∂ x i ∂r

where r is the droplet radius, rɺ is the droplet radius growth rate, xi and ui are the coordinates and veloc-
ity components, Vt(r) is the droplet fall velocity, Js describes droplet sources and sinks, and the usual
summation convention over doubled indices is assumed, i = 1, 2, 3. We omit in this section the sub-
script “d” in all quantities for drops. Equation (13.2.1) is a continuity equation for the drop size spec-
tra. The term ∂(rfɺ ) / ∂r in (Eqn. 13.2.1) represents the divergence of f(r) due to condensation growth.
The droplet growth rate rɺ is determined from simplified (Eqn. 5.1.43) with xcon = 0 and D*v = Dv:
Dv sw ws
rɺ = , (13.2.2)
1 w r

where all notations are the same as in Section 5.1. Equation (13.2.2) neglects for simplicity the solute
(Raoult), kinetic (accomodation coefficient), and curvature (Kelvin) effects.
The fractional water supersaturation sw in the parcel is described by (Eqn. 5.3.31a), and derived
from the equations of heat balance and the continuity for water vapor:

dsw s
= − w + c1w wef , (13.2.3)
dt τf

with c1w defined in (Eqns. 5.3.26b) and (5.3.2c) as

c p ρa  dq  ρ
c1w (T ) = (γ a − γ w )Γ1 =  l  Γ1 a , (13.2.4)
Le ρ ws  
dz ad ρ ws

where ga = g/cp is the dry adiabatic lapse rate, gw is the wet saturated over water adiabatic lapse rate
(see Chapter 3), wef is an effective vertical velocity defined in the following text, tf is the supersatura-
tion relaxation time (phase relaxation time) introduced in Section 5.1, related to the droplet concen-
tration N and mean radius r :
∞ ∞

τ f = ( 4π Dv Nr ) ,
−1
N = ∫ f ( r ) dr r = ∫ rf ( r ) dr , (13.2.5)
0 0

and all the other notations are the same as in Section 5.3.
The radiative effects on drop growth can be simply accounted for by replacing in the temperature
equation the term −gaw:

 ∂T   1  ∂T  
−γ a w +  = −γ a  w −   = −γ a wef , (13.2.6)
 ∂t  rad  γ a  ∂t  rad 
wef = w + wrad , (13.2.7)
1  ∂T 
wrad = − . (13.2.8)
γ a  ∂t  rad
624 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

Here, (∂T/∂t)rad is the radiative temperature change (K s−1) due to longwave and shortwave radia-
tive transfer, and we have introduced an effective vertical velocity wef = w + wrad , where wrad is the
radiative-effective vertical velocity related to (∂T/∂t)rad. The advantage of introducing wrad is that
it allows direct comparison of the dynamical and radiative sources of supersaturation generation.
The maximum values (∂T/∂t)rad ∼ 10−3 K s−1 (− 3.6 K s−1K h−1 or − 86 K day−1) and 2 × 10−3 K s−1
(− 7.2 K h−1) typical for the upper layer of the Arctic stratus (Curry, 1986) and other St–Sc clouds calcu-
lated with (Eqn. 13.2.8) correspond to wrad ∼ 10 − 20 cm s−1 in the upper cloud layer. Thus, the magnitude
of the radiative-effective velocity can be comparable to the turbulent updrafts and can be substantially
larger than the synoptic-scale (mean) updraft velocity or the entrainment rate at the boundary layer top,
providing the main source of condensation, instability, and turbulent kinetic energy production.
Equation (13.2.3) shows that the supersaturation change rate is determined by the sources of
supersaturation (up- and downdraft and radiative cooling), the sink of supersaturation associated
with condensation, and is inversely proportional to the phase relaxation time tf. If quasi-steady condi-
tions are assumed in (Eqn. 13.2.3) (dsw /dt = 0), the solution for equilibrium supersaturation, sw,eq, is:
c p ρ a (γ a − γ w )
sw, eq = c1w wef τ f = Γ1 wef . (13.2.9)
L ρ ws 4π DN r

13.2.2. Stochastic Equations

The kinetic (Eqn. 13.2.1), the droplet growth equation (Eqn. 13.2.2), and the supersaturation
equation (Eqn. 13.2.3) close the system of equations required to determine the evolution of the drop
size distribution if the velocity, temperature, and humidity fields are specified. To account for turbu-
lence and other fluctuations, we represent all quantities as sums of mean (denoted by overbar) and
fluctuating (denoted by prime) values:

u = u + u ′, f = f + f ′,
sw = sw + sw′ , rɺ = rɺ + rɺ ' (13.2.10)

where the mean refers to an ensemble average. Substituting (Eqn. 13.2.10) into (Eqn. 13.2.1), neglect-
ing the sedimentation for the small-size fraction for now, and averaging using the Reynolds procedure,
we derive an equation for the drop size spectra that is averaged over the ensemble of realizations:

∂f
+
∂
∂t ∂ x i
( )
ui f +
∂
∂r
( )
rɺ f = −
∂
∂ xi
∂
ui′ f ′ − rɺ ′f ′ + J s .
∂r
(13.2.11)

Henceforth, we shall omit the bars over the mean values, other than for the covariance terms. The
nucleation term J s can be calculated by appropriate averaging of the CCN activity spectra as described
in Chapters 6 and 7. Note that the averaging here can be understood also in the context of averaging
over the grid scale of a Large-Eddy Simulation (LES) model, time, or grid-volume averaging, with
the corresponding requirements on the averaging procedure.
In the case of the grid-volume average with the scale Lx, the average value of any variable is
Lx
ψ = (1/ Lx ) ∫ ψ dx . For typical LES models or a 1-Hz aircraft sampling distance, Lx ∼ 50–100 m.
0
Averaging over this spatial scale implies filtering only of the highest frequencies of motion up
13.2. Condensation in a Turbulent Cloud 625

to w max ∼ 1 Hz, while the peak of the turbulent energy may lie near the smaller values of w max
(e.g., Curry et al., 1988). Hence, the average quantities defined earlier still may contain turbulent
fluctuations at longer wavelengths with w < w max and correlations still may exist between the average
values and fluctuations denoted by primes. This should be kept in mind when defining the “mean”
supersaturation sw, the “mean” vertical velocity wef , and their relation. In this case, “mean” values
implies grid averages.
The right-hand side of (Eqn. 13.2.11) is ascribed a stochastic meaning, since u and rɺ (which
depends on supersaturation fluctuations) vary randomly. We represent the fluctuations f ′ in a form
analogous to the Prandtl mixing length concept with a generalization to the 4D phase space (xj , r):

∂f ∂
f ′ = − l j′ − lr′ f . (13.2.12)
∂ x j ∂r

The first term on the right-hand side of (Eqn. 13.2.12) corresponds to the mixing of a conservative
passive scalar, where l ′j is the Prandtl mixing length along the xj-axis. The second term arises from
the nonconservativeness of f, and the Prandtl mixing length concept is extended to the r-dimension in
the phase space following Voloshchuk and Sedunov (1977).
If tf << tL (the low frequency regime), then the fluctuations of rɺ ′ can be determined from the
Maxwellian growth rate equation. Fluctuations in droplet growth rate can be determined as

Dsw′ ρ ws
rɺ ′ = . (13.2.13)
Γ1 ρ w r

The water supersaturation sw in the presence of fluctuations is a stochastic variable. It can be described
with (Eqn. 13.2.3), which has the typical form of the Langevin equation (Rodean, 1996; Lemons,
2002). The first term on the right-hand side describes the relaxation of sw with time, while the second
term describes the stochastic source of supersaturation, and wef should be treated as a stochastic vari-
able. If the fluctuations sw′ are determined from (Eqn. 13.2.9), we have

cp ρ a (γ a − γ w )
sw′ = c1w wef′ τ f = Γ1 wef′ . (13.2.14)
L ρ ws 4π DN r

Substituting (Eqns. 13.2.9), (13.2.12), (13.2.13), and (13.2.14) into (Eqn. 13.2.11) would yield the
previous forms of the stochastic kinetic equation discussed in Section 13.1 that are valid in the low
frequency regime, with the additional assumption that both mean supersaturation and its fluctuations
are proportional to the corresponding vertical velocity. The assumption of low turbulence frequency
is implicit in (Eqn. 13.2.14) because fluctuations of supersaturation are correlated exactly with the
fluctuations of vertical velocity. Equations (13.2.13) and (13.2.14) are in conceptual agreement with
the detailed DNS simulations of Paoli and Shariff (2004, 2009).

13.2.3. Supersaturation Fluctuations

As noted in Section 13.1, the basic assumption used previously in many derivations of the stochastic
kinetic equation, that sw and sw′ are both related to the respective components of the vertical velocity,
leads to a size distribution of the Gaussian type or the Weibull distribution, which may be too narrow
626 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

relative to observations. Thus, we hypothesize and seek alternative relationships to (Eqns. 13.2.13)
and (13.2.14) that are not based on the assumption of proportionality of the fluctuations of growth
rate and vertical velocity, and account for the different growth rates in fluctuations and in regular
(low-frequency) growth.
Supersaturation fluctuations can be associated with turbulent fluctuations in temperature and
humidity, which may or may not be associated with vertical velocity. There is a hierarchy of spatial
scales of turbulent motions in the cloud, with the larger eddy sizes having a greater coherence with
supersaturation. Additional supersaturation fluctuations may occur on the drop microscale that are
unrelated to vertical velocity fluctuations, but might be induced by other turbulent fluctuations such
as those caused by the mixing of the cloudy parcels with different properties that act to break the link
between vertical velocity and supersaturation.
Suppose a supersaturation fluctuation sw′ arises in a cloudy parcel due to a turbulent fluctuation.
Vapor begins to flow to the droplets and unless the equilibrium is attained in the volume VL in the
vicinity of each droplet, there will be a nonstationary vapor concentration field rvi(r). To calculate
these vapor fields, we need to solve a complex system of many diffusion equations for rvi(r) from
all drops that influence each other in order to calculate a self-consistent vapor field formed by the
superposition of the overlapping fields from individual drops (Sedunov, 1974; Srivastava, 1989). The
exact solution to this complicated diffusion problem has not been found; thus various approximate
methods are used.
As described in Section 13.1, many models of condensation growth were developed over the last
decades that may help to break the link between sw′ and w′. The common feature of several of them is
that they predict the local growth of supersaturation fluctuations in proportion to the droplet radius,
sw′ ∼ r. Srivastava (1989) introduced the concept of the microscopic supersaturation fluctuations,
which can vary from drop to drop due to randomness in the droplet spatial distribution. The main part
of this microscopic supersaturation sw′ is proportional to the droplet radius.
The inhomogeneous mixing theory of Baker and Latham (1979), Baker et al. (1984), based on
the chamber mixing experiments by Latham and Reed (1977), predicts the local increase of super-
saturation in the vicinity of the larger drops that are less affected by mixing with entrained dry air,
because the newly activated smaller droplets (that form later in the areas of complete evaporation)
cannot compete as effectively for the available water vapor. Thus, the effective supersaturation in the
inhomogeneous mixing theory also increases with the drop radius.
Further evidence for the proportionality sw′ ∼ r for small timescales comes from the detailed cal-
culations of droplet growth that account for the kinetic correction (Fuchs, 1959, 1964; Fukuta and
*
Walter, 1970) and the concept of the modified diffusion coefficient, Dv (r), which accounts for this
correction (see Chapter 5, Section 5.1). Calculations of droplet growth show that the magnitude
of the kinetic correction depends on time and drop mass. Over short time periods comparable to
tf (10–20 seconds), the kinetic correction causes a strong suppression of the growth of the smaller
*
droplets. The value of Dv(r) ∼ r increases almost linearly with the radius for small droplets (Pruppacher
and Klett, 1997, Table 13.1). Over periods much longer than ∼20–60 s, the kinetic correction becomes
negligible and Maxwellian growth occurs. Similar calculations of supersaturation during relaxation
(∼3–10 s) were performed by Khvorostyanov and Curry (1999c) taking into account the curvature
and kinetic corrections with various accommodation coefficients (0.04–1), which also showed that
13.2. Condensation in a Turbulent Cloud 627

the effective supersaturation, sw′ (r, t) increases with radius such that it can be roughly approximated
by a linear dependence, sw′(r, t) ∼ a (t)r. The slope a (t) decreases with time; thus, the dependence of
sw′ on r weakens and the usual Maxwellian growth takes place for the larger times. Thus, accounting
for the kinetic and curvature corrections leads to the quasi-kinetic regime of growth for short time
scales comparable to the phase relaxation time tf and the diffusion regime during long time scales.
Since we do not account explicitly here for the curvature and kinetic corrections, activation, and
other effects that lead to the dependence sw′ ∼ r (i.e., suppression of the growth of smaller droplets), we
consider an approximate model of condensational growth in supersaturation fluctuations. The aver-
′ of supersaturation absorption by the i-th drop from its vicinity VL ∼ N −1 can be character-
age rate sɺwi
ized by the local relaxation time as a scaling time, similar to the total relaxation time for the ensemble
of drops (Eqn. 13.2.5). Then, sɺwi′ can be written approximately as
tfi = (4pDNri)−1 (13.2.15)
sɺwi′ = sw′ /τ fi = sw′ (4π Dv Nri ), (13.2.16)

where sw′ is the supersaturation fluctuation absorbed by all drops, so that the absorption rate of super-
saturation fluctuation by an i-th drop increases with increasing radius. This model is conceptually close
to the Srivastava’s (1989) concept of microscale supersaturation. Now, the supersaturation swi′ absorbed
by the i-th drop during the entire period of relaxation in the ensemble of the drops is proportional to
the total relaxation time tf . Using (Eqns. 13.2.16) and (13.2.5), we can determine

τf 4π Dv Nri r
swi′ = sɺwi′ τ fi = sw′ = sw′ = sw′ i . (13.2.17)
τ fi 4π Dv Nr r

So, the effective microscale supersaturation in (Eqn. 13.2.17) is approximated during relaxation as a
linear function of drop radius. Incorporation of (Eqn. 13.2.17) into (Eqn. 13.2.13) for rɺi′ yields the
desired result:
Dv sw′ ρ ws Dv ρ ws
rɺ ′ = = φr sw′ , φr = . (13.2.18)
Γ1 ρ w r Γ1 ρ w r

The physical meaning of (Eqns. 13.2.16)–(13.2.18) is that due to suppressed growth of the smaller
drops, the effective supersaturation is greater for the larger droplets, while the rate of their absorption
is faster, so during relaxation the larger droplets absorb the larger fraction of the initial supersatura-
tion fluctuation sw′ . Equation (13.2.18) shows that fluctuation of the growth rate described by this
model is independent of radius, which is equivalent to the kinetic regime in fluctuations. Another
important feature of (Eqn. 13.2.18) is that we do not assume here that sw′ ∼ w′ as in previous theories,
but simply consider sw′ as a stochastic variable.
Support for this model of microscale condensation is provided by several previous studies, as dis-
cussed earlier. After substituting into (Eqn. 13.2.13) the effective diffusivity D*v (r) ∼ r in approxima-
tion with kinetic correction for small drops (see Section 5.1), which can approximate the results by
Fukuta and Walter (1970) and Pruppacher and Klett (1997, Table 13.1), one also arrives at a formula-
tion (Eqn. 13.2.18) of rɺ ′ that is independent of radius.
From (Eqn. 13.2.18), we can infer that the droplet spectrum during Δt in the kinetic regime would
be displaced as a whole by Dr = fr sw′ Dt, whereby the displacement is independent of radius and the
628 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

shape of the spectrum is preserved. The possibility of such a spectral shift was noted by Baker et al.
(1984) when analyzing the consequences of the Broadwell–Breidenthal (1982) mixing model.
Hence, this model of condensation in a turbulent medium is naturally separated by scales: 1) the
usual Maxwellian diffusion regime controls condensational growth for longer time scales by using
(Eqn. 13.2.2) for rɺ (with the use of calculated values of supersaturation or equilibrium supersatura-
tion sw,eq (Eqn. 13.2.9) for the steady state); and 2) droplet growth occurs in the quasi-kinetic regime
(Eqns. 13.2.17) and (13.2.18) for small time scales in fluctuations. Therefore, fluctuations in super-
saturation, sw′ , and growth rate, rɺ ′, have a stochastic meaning, but they are not proportional to the
vertical velocity fluctuation w′ as in the low-frequency approximation. This model therefore breaks
the link between the fluctuations in sw′ (or growth rate) and w′.
By integrating (Eqn. 13.2.18) over the duration of a single fluctuation (∼tL), an expression for lr′ is
derived that determines an analog of Prandtl’s mixing length in radii space:
t t

lr′ = ∫ rɺ ′dt ′ = φr ∫ sw′ ( t ′ ) dt ′. (13.2.19)

0 0

As lr′ in (Eqn. 13.2.19) is independent of radius, (Eqn. 13.2.12) for f ′ then becomes

∂f ∂f
f ′ = − l j′ − lr′ . (13.2.20)
∂x j ∂r

Equations (13.2.17)–(13.2.20) allow evaluation of the covariances in the kinetic (Eqn. 13.2.11),
which is done in the next section.

13.3. Evaluation of Correlation Functions

13.3.1. Expansions of Random Characteristics over the Turbulent Frequencies

In this section, we use concepts from the statistical theory of turbulence (Kolmogorov, 1941; Rodean,
1996; Monin and Yaglom, 2007b) to evaluate the correlation functions ui′ f ′ and rɺ ′f ′ in (Eqn. 13.2.11).
We assume that the velocity fluctuation vectors u ′j , the supersaturation sw′ , and mixing lengths l ′j are
random quantities, which we represent as expansions in form of improper Fourier–Stieltjes integrals
over the frequencies w of the turbulent spectrum:
∞
u ′j (t ) = ∫ e iω t du ′j (ω )
−∞
∞

∫e
iω t
sw′ (t ) = dsw′ (ω )
−∞
t t ∞

l j′ (t ) = ∫ u ′j (t1 ) dt1 = ∫ dt ∫ e1
iω t1
du ′j (ω ), (13.3.1)
0 0 −∞

where the symbol t1 is used hereafter to denote the time variable of integration but not the fluctuation.
The complex amplitudes du ′j (ω ) , dsw′ (ω ) have an analytic continuation into the region w < 0,
with the amplitudes at w > 0 and w < 0 being the complex conjugates, du ′j (−ω ) = du ′j * (ω ) , and are
13.3. Evaluation of Correlation Functions 629

normalized to the Dirac delta-function, d (w), and a spectral function of turbulence Fij (w) (Monin and
Yaglom, 2007b):

dui′( )du ′j * ( ′) = Fij ( ) ( − ′)d d ′

∞
1
2 ∫0
Fij ( ) = e − it Bij (t ) dt , (13.3.2)

where Fij (w) is related to the frequently used spectral density Eij (w) defined at positive w > 0 as
2Fij (w) = Eij (w). Assuming stationary, locally homogeneous, isotropic turbulence, we can also define
(following Monin and Yaglom (2007b)) the velocity correlation function, Bij, and the turbulence dif-
fusion coefficient tensor, kij:
∞ ∞

∫e Fij (ω )dω = ∫ cos[ω (t − t1 )][2 Fij (ω )] d ω ,

iω ( t − t1 )
Bij (t − t1 ) =
−∞ 0
∞

kij = ∫ Bij (τ ) dτ , (13.3.3)

0

where t = t − t1. The covariance li′u ′j is readily determined from (Eqn. 13.3.1) to be
t ∞ ∞ t

li′u ′j = ∫ dt1 ∫ e iω t ∫ e 1 dui′(ω )dui (ω ′) = ∫ dt1 Bij (t − t1 ).

− iω ′t *
(13.3.4)
0 −∞ −∞ 0

13.3.2. Supersaturation as a Nonconservative Variable

Determination of covariances involving supersaturation is complicated by the fact that supersatura-
tion is nonconservative because of turbulent fluctuations of temperature and humidity, and because
of phase changes when sw ≠ 0. Nonconservativeness of supersaturation requires introduction of non-
conservative covariances and turbulence coefficients.
Separating fluctuations from the average quantities in the supersaturation (Eqn. 13.2.3), we can
write
dsw′ s′
= − w + c1w u3′ , (13.3.5)
dt τf

where the vertical velocity is denoted by u3 for further convenience. By substituting (Eqn. 13.3.1)
into (Eqn. 13.3.5), we can introduce a spectral analog of the supersaturation equation:
∞ ∞ ∞
1
∫ e (iω ) dsw′ (ω ) = − ∫ e dsw′ (ω ) + c1w ∫ e du3′ (ω ),
iω t iω t iω t
(13.3.6a)
−∞
τf −∞ −∞

c1w
dsw′ (ω ) = du3′ (ω ), (13.3.6b)
i (ω − iω p )

where we introduced the inverse quantity ω p = τ −f 1 = 4π Dv Nr that can be referred to as the “super-
saturation relaxation frequency,” which is here the imaginary part of the frequency. The complex
630 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

frequency in the denominator of (Eqn. 13.3.6b) with imaginary part wp > 0 reflects the nonconser-
vativeness of the supersaturation and is written in the form similar to that in electrodynamics for
the wave propagation in the absorbing media (e.g., Landau and Lifshitz, 1966, v. 8; Lifshitz and
Pitaevskii, 1997), describing relaxation of perturbation in a medium.
If we assume in (Eqn. 13.3.6b) that w << wp (low-frequency approximation), the amplitude dsw′ (w)
becomes proportional to the vertical velocity du′(w) at all frequencies, and we come to the previous
formulations of stochastic theory by Levin and Sedunov (1966), Voloshchuk and Sedunov (1977),
and Manton (1979). Thus, our approach generalizes the previous theories by use of (Eqn. 13.3.6b),
which breaks the links between supersaturation and vertical velocity. In deriving (Eqn. 13.3.6), we
assumed for simplicity that τ f = ω −p1 is constant; all subsequent manipulations can be readily gen-
eralized to allow for fluctuations of tf (e.g., Voloshchuk and Sedunov (1977) for the low-frequency
regime; Cooper, 1989); however, as was noted in Section 13.2, the assumption of tf ≈ const is a good
approximation when considering supersaturation relaxation on the microscale over time scales t ∼ t f .

13.3.3. Covariances with Supersaturation

By incorporating (Eqns. 13.3.6b), (13.3.1), and (13.3.2), we obtain the following expression for the
correlation function u ′j S ′ :
∞ ∞
c1w
∫e ∫e du3′ (ω )du ′j *(ω ′)
iω t − iω t1
sw′ (t )u ′j (t1 ) =
−∞ −∞
i(ω − iω p )
= δ i 3 (c1w /ω p ) Bijn (t − t1 ,τ f ), (13.3.7)

where d ik is Kronecker’s symbol, we used the normalization condition (Eqn. 13.3.2) for the velocities
amplitudes, and introduced the correlation function of velocity with supersaturation as a nonconser-
vative substance (superscript “n”) with a characteristic “nonconservativeness” time τ f = ω −p1:
∞
ωp
Bijn (t , τ f ) = ∫e
iω t
Fij (ω ) d ω (13.3.8a)
−∞
i (ω − iω p )
∞
[ω p + ω tan ω t ]
=∫ cos ω t[2 Fij (ω )] d ω . (13.3.8b)
0
1 + (ω /ω p )2

The first term in the subintegral function of (Eqn. 13.3.8b) determines the nonconservative effects,
and the rest coincides with the expansion of the conservative function (Eqn. 13.3.3). We can derive
analogously the turbulence diffusion tensor coefficient for a nonconservative substance:
∞

kijn (τ f ) = ∫ Bijn (τ , τ f ) d τ . (13.3.9)

0

Following an approach analogous to the derivation of (Eqn. 13.3.7), we can obtain an expression for
the supersaturation autocorrelation function:
∞ ∞
du3′ (ω )du3′ * (ω ′)
∫e ∫e
iω t − iω t1 2
sw′ (t )sw′ (t1 ) = c
(iω + ω p )(− iω + ω p )
1w
−∞ −∞

= (c1w /ω p )2 δ i 3δ j 3 Bijnn (t − t1 ,τ f ), (13.3.10)

13.3. Evaluation of Correlation Functions 631

where we use again (Eqn. 13.3.2) and introduce the autocorrelation function of a nonconservative
substance, and the corresponding turbulence coefficient:
∞
ω p2 ∞
cos ω t
Bijnn (t , τ f ) = ∫e Fij (ω ) d ω = ∫
iω t
[2 Fij (ω )] d ω
−∞
(ω + ω )
2 2
p 0
1 + (ω /ω p )2
∞

kijnn (τ f ) = ∫ Bijnn (t , τ f ) dt . (13.3.11)

0

The covariance of uj′ and lr′ is evaluated analogously using (Eqns. 13.2.19) and (13.3.7):

t
c  t
u ′j (t )lr′ (t1 ) = φr ∫ dt1 u ′j (t )sw′ (t1 ) = φr  1w  ∫ dt1 Bijn (t − t1 )δ i 3
0 ωp  0
t t

= φr c1wτ f δ i 3 ∫ dt1 Bijn (t − t1 ) = Gsδ i 3 ∫ dt1 Bijn (t − t1 ) (13.3.11a)

0 0

where fr is defined in (Eqn. 13.2.18) and we have introduced the parameter Gs that plays a key role
in the analytical solutions:
Dv c p γ a − γ w ρ cp γ a − γ w
Gs = φr c1wτ f = ρa = a . (13.3.12)
ρ w r L 4π DN r ρ w L 4π N r 2

13.3.4. Covariances with the Drop Size Distribution Function

For the general case of arbitrary relations between tf and tL, we obtain for the correlation function
ui′ f ′ in (Eqn. 13.2.11) using (Eqn. 13.2.20) for f ′:

∂f ∂f
ui′ f ′ = − ui′l ′j − − ui′lr′
∂x j ∂r
t
 ∂ f (t1 ) ∂ f (t1 ) 
= − ∫ dt1  Bij (t − t1 ) + Bijn (t − t1 ,τ f )δ j 3Gs , (13.3.13)
0  ∂ x j ∂r 

where we used (Eqn. 13.3.4), for ui′l ′j and (Eqn. 13.3.11a) for ui′lr′ . For rɺ ′f ′, using (Eqn. 13.2.20) for
f ′, we obtain
t
 ∂ f (t 1 ) ∂ f (t1 ) 
rɺ′f ′ = φr sw′ f ′ = −φr ∫ dt1  sw′ (t )u ′j (t1 ) + φr sw′ (t )sw′ (t1 ) 
0  ∂x j ∂r 
t
 ∂ f (t1 ) ∂ f (t1 ) 
= − ∫ dt1 Gsδ i 3 Bijn (t − t1 ,τ f ) + Gs2δ i 3δ j 3 Bijnn (t − t1 ,τ f ) , (13.3.14)
0  ∂x j ∂r 

where we used (Eqn. 13.3.7) for sw′ (t )u ′j (t1 ) and (Eqn. 13.3.10) for sw′ (t )sw′ (t1 ) . Expressions
(Eqns. 13.3.13) and (13.3.14) are integrated similar to Stepanov (1975, 1976) as is done in the sta-
tistical k-theory of turbulence (Monin and Yaglom, 2007a,b). The main contribution to the integrals
comes from the region t − t1 ∼ tL, because the correlation functions decrease rapidly beyond this
632 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

interval. During the time period t − t1 ∼ tL, the distribution function f varies much more slowly
than the correlation functions, and we can remove ∂f/∂xj and ∂f/∂r from the integrals and simplify
(Eqns. 13.3.13) and (13.3.14) to
t t
∂f ∂f
∫ dt B (t − t ) − δ ∫ dt B
n
ui′ f ′ ≈ − 1 ij 1 j3 Gs 1 ij (t − t1 , τ f ), (13.3.15)
∂x j 0
∂r 0

t t
∂f ∂f
∫ dt1 Bij (t − t1 , τ f ) − δ i 3δ j 3Gs ∫ dt B
n 2 nn
rɺ ′f ′ ≈ −δ i 3 Gs 1 ij (t − t1 , τ f ). (13.3.16)
∂x j 0
∂r 0

The integrals in (Eqns.13.3.15) and (13.3.16) can then be evaluated from t = 0 to ∞ since the inte-
grated functions decrease rapidly with time beyond tL. We can write (Eqns.13.3.15) and (13.3.16)
by including the definitions of the turbulence coefficients (Eqns.13.3.3), (13.3.9) and (13.3.11) as

∂f ∂f
ui′ f ′ = − kij − δ j 3 kijn (τ f ) Gs (13.3.17)
∂x j ∂r
∂f ∂f
rɺ ′f ′ = −δ i 3 kijn (τ f )Gs − δ i 3δ j 3 kijnn (τ f )Gs2 . (13.3.18)
∂x j ∂r

For high-frequency turbulence, only the first term of the expression for ui′ f ′ on the right-hand
side in (Eqn. 13.3.17) remains since the nonconservative turbulence coefficients vanish. In the high-
frequency approximation w >> wp (tf >> tL), we find from (Eqns. 13.3.7)–(13.3.11) that Bijn = 0 ,
kijn = 0, Bijnn = 0 , and kijnn = 0 . In the opposite case of low-frequency approximation ω << ω p (tL >> tf),
the term ω p /(i (ω − iω p )) in (Eqn. 13.3.8a) tends to unity and the supersaturation-velocity correla-
tion function reduces to (Eqn. 13.3.3), so, Bijn = Bij , and kijn = kij . It follows also from (Eqn. 13.3.11)
that Bijnn = Bij, kijnn = kij ; that is, nonconservative effects (dependence of the correlation functions and
turbulence coefficients on the supersaturation relaxation time) vanish in the low-frequency regime.
In liquid clouds, tf ∼ 1 − 10 s (see Chapter 5), while w ∼ (0.2 − 1) × 10−2 s−1 and tL ∼ 100–600 s
(e.g., Curry et al., 1988), which is closer to the low-frequency approximation; hence, the high-
frequency kinetic equation used now in most cloud models with explicit spectral microphysics is
oversimplified. The errors of neglecting the terms with kn, knn are unknown and can be significant.
In crystalline clouds like cirrus or diamond dust, for which this technique can also be applied as
described in the following text, the concentration of particles can be 1–3 orders of magnitude less
than in the liquid stratus, and the values of tf can be 10–180 min and greater (Khvorostyanov and
Sassen, 1998a,b; 2002; Khvorostyanov et al., 2001, 2006), while tL ∼ 5–15 min. Thus, the values of tf
and tL can be comparable or the situation can be closer to the high-frequency regime, which should
influence kn, knn. In particular, if the maximum in the turbulent spectrum is located near ω ∼ τ L−1, and
tf ∼ tL, then (Eqns.13.3.8b) and (13.3.11) show that kn, knn ∼ 0.5 k; these values will decrease with
increasing tf. Equations (13.3.8) and (13.3.11) allow calculations of the nonconservative correlation
functions and turbulent coefficients either with various theoretical models of the turbulence spectra or
directly with the observed-in-clouds turbulence spectra (e.g., Curry et al., 1988; Sassen et al., 1989;
Quante and Starr, 2002) with appropriate choices of limits in the integrals.
13.4. General Kinetic Equations of Stochastic Condensation 633

13.4. General Kinetic Equations of Stochastic Condensation

Substituting (Eqns. 13.3.17) and (13.3.18) into (Eqn. 13.2.11) and assuming that the droplet
growth rate rɺ is determined from (Eqn. 13.2.2), we obtain the general kinetic equation of stochastic
condensation:

∂f ∂ ∂ b s
+ ( ui − v (r )δ i 3 ) f  +  con w f 
∂t ∂ x i   ∂r  r 
∂ ∂f ∂ ∂f ∂2 f ∂2 f
= kij + δ j 3 kijn Gs + δ i3 kijn Gs + δ i 3δ j 3 kijnn Gs2 2 + J s ,
∂ xi ∂ x j ∂ xi ∂r ∂ x i ∂r ∂r
Dv ρ ws
bcon = (13.4.1)
Γ1 ρ a

Recall, all the quantities on the left-hand side ( f, ui , w, sw) indicate averaged values (in the sense
discussed in Section 13.2.2), and all fluctuations are included on the right-hand side of the equation.
If the scale of averaging (e.g., over a grid box of a numerical model) is chosen to be sufficiently
large so that the characteristic time of averaging is much larger than tf , then the mean supersaturation
sw can be equal to the equilibrium value sw,eq related in (Eqn. 13.2.9) to the “mean” vertical velocity
wef . Note, however, that when using this representation for sw , the value of wef should not be under-
stood as simply the mean (synoptic-scale) vertical velocity.
The term wef represents an “effective” subgrid-averaged vertical velocity. Since the grid-box aver-
age still contains turbulent fluctuations of the larger scales (see Section 13.2), and correlations still
exist between smaller-scale fluctuations (primes) and “mean” values (overbars), the effective subgrid
average wef can be estimated from the relation wef f ~ w ′f ′ . Multiplying this relation by (4/3) prwr3
and integrating over radii, we obtain a relation wef ∼ w ′qL′ / qL , which allows estimation of wef from
measurements of qL and the covariance of the fluctuations of the vertical velocities and qL—i.e., w ′qL′ .
Substituting the equilibrium value sw,eq (Eqn. 13.2.9) into (Eqn. 13.4.1), we obtain

∂f ∂ ∂ c
+ ( ui − v (r )δ i 3 ) f  +  con wef 
f
∂t ∂ x i   ∂r  r 
∂ ∂f ∂ ∂f ∂2 f ∂2 f
= kij + δ j 3 kijn Gs + δ i 3 kijn G + δ i 3δ j 3 kijnn Gs2 2 + J s ,
∂ xi ∂ x j ∂ xi ∂r ∂ x i ∂r ∂r
Dv c1w ρ wsτρf τ ρ c p (γ a − γ w )
ccon = = Dv a . (13.4.1a)
ρ w Γ1 ρ w L 4π Dv Nr

The representation (Eqn. 13.4.1a) with sw,eq may be suitable for models with grid boxes a few tens
or hundreds of meters or larger and/or for processes where the mean supersaturation is close to the
quasi-steady value, while the more complete form (Eqn. 13.4.1) with non-equilibrium sw is prefer-
able for models with a finer resolution (e.g., on the smaller scales of LES models), or for processes
or cloud layers where supersaturation is not quasi-steady. Note that the minimum scales of averaging
and conditions when sw ≈ sw,eq can probably only be determined with the use of the LES models with
fine resolution after a detailed analysis of the entire supersaturation field.
634 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

To represent the kinetic equation in a more compact form and compare this with the previous
equations, it is convenient to adopt a methodology from quantum field theory, functional analysis,
and operational calculus that uses left and right operators. We introduce the left operator Ĥ L and the
right operator Ĥ R , such that

Hˆ L kij = kijn , kijn = kij Hˆ R , Hˆ L kij Hˆ R = kinn

j . (13.4.2)

The left operator Ĥ L stands on the left of a quantity and acts to the right; the right operator Ĥ R stands
on the right of a quantity and acts to the left. The operators convert the conservative tensor, kij, into a
nonconservative tensor, kijn, and commute with operators ∂/∂xi and ∂/∂r. Ĥ L , R are the integral opera-
tors that convert the correlation function (Eqn. 13.3.3) into (Eqns. 13.3.8) and (13.3.11). Incorporating
these operators into the right-hand side of (Eqns. 13.4.1 and 13.4.1a), we obtain

∂f ∂ ∂ b s
+ ( ui − v (r )δ i 3 ) f  +  con w f 
∂t ∂ x i   ∂r  r 
 ∂ ∂  ∂ ∂
= + δ i 3 Gs Hˆ L  kij  + δ j 3 Gs Hˆ R  f + J s . (13.4.3a)
 ∂ xi ∂r   ∂ x j ∂r 

Equation (13.4.3a) does not use the condition sw ∼ sw,eq, and if we assume that sw ∼ sw,eq, we obtain

∂f ∂ ∂ c
+ ( ui − v (r )δ i 3 ) f  +  con w f 
∂t ∂ xi   ∂r  r 
 ∂ ∂  ∂ ∂
= + δ i 3Gs Hˆ L  kij  + δ j 3Gs Hˆ R  f + J s . (13.4.3b)
 ∂ xi ∂r   ∂ x j ∂r 

The assumption of equilibrium supersaturation sw,eq might be suitable for mesoscale models with
appropriate parameterization of subgrid wef .
For low-frequency turbulence Ĥ L , R = 1, whereas for high-frequency turbulence Ĥ L , R = 0 . The
high-frequency regime, for which generally sw ≠ sw,eq, is thus represented by

∂f ∂ ∂ b s ∂ ∂
+ ( ui − v (r )δ i 3 ) f  +  con w 
f = k f + Js . (13.4.4)
∂t ∂ x i   ∂r  r  ∂ xi ij ∂ x j

This type of equation is used in most cloud models with explicit spectral bin microphysics and
describes the evolution of the size spectra with broadening due to vertical and horizontal turbulent
mixing between the cloud parcels or regions with different properties. The low-frequency regime
with the assumption sw ≈ sw,eq is represented by

∂f ∂ ∂ c
+ ( ui − vδ i 3 ) f  +  con w f 
∂t ∂ xi   ∂r  r 
 ∂ ∂  ∂ ∂
= + δ i 3Gs  kij  + δ j 3 Gs  f + J . (13.4.5)
∂
 i x ∂ r   j∂ x ∂ r

The term (∂/∂r[(ccon/r)wf] describes “advection” in the space of radii with effective speed (ccon/r)w,
inversely proportional to the radius. Thus, this “advection” is faster for the smaller droplets and this
13.4. General Kinetic Equations of Stochastic Condensation 635

term alone causes narrowing of the size spectra. Analogous to the term −kij∂f/∂xi, the turbulent flux of
the droplets in the usual space, the term −kijGs∂f/∂r represents the turbulent flux in the space of radii.
So, the term kxr = Gskij is the effective diffusion coefficient in the combined space of coordinates–
radii, the term
kr = Gs2 kij (13.4.5a)

is the effective diffusion coefficient in the space of radii, and the parameter Gs ∼ 10−9 to 10−8 is the
scaling factor between the diffusion coefficients in xi and r spaces. Since the derivative −∂f / ∂r < 0
for the radii smaller than the modal radius, r < rm, the flux of droplets is directed along the gradient
toward the smaller radii to the left of the mode, at r < rm, and vice versa, −∂f / ∂r > 0 at r > rm, and
the flux is directed toward the larger radii. So, this “diffusion” in the space of radii tends to smooth
the gradients and broaden the size spectrum. The resulting shape of the size spectra is determined
by the relative speed of the advection and diffusion in the space of radii and in the coordinate space.
If the effects of advection dominate (e.g., in the vigorous updrafts but with weak turbulence), the
spectra may narrow even in the presence of turbulence, which alone might be insufficient to produce
the broad spectra.
When written using the left and right operators, the differences are clearer between the new equa-
tion and the earlier kinetic equations of stochastic condensation reviewed in Section 13.1. These
earlier kinetic equations can be written using our notations after some simplifications as

∂f ∂ ∂ c
+ ( ui − v (r )δ i 3 ) f  +  con w f 
∂t ∂ x i   ∂r  r 
 ∂ ∂ 1  ∂ ∂ 1
= + δ i 3ccon  kij  + δ j 3ccon  f. (13.4.6)
 ∂ xi ∂r r   ∂ x j ∂r r 

Equation (13.4.3a) from Khvorostyanov and Curry (1999a, 2008a) does not assume the quasi-
steady state supersaturation. Another version, (Eqn. 13.4.3b), assumes this approximation (although
with another interpretation of wef ), but additionally accounts for the nonconservative character of
supersaturation and can thus be used in both the low- and high-frequency regimes including the
cases when sw ≈ sw,eq, while the previous equations of the type (Eqn. 13.4.6) are applicable only in
the low frequency regime ( Ĥ L , R = 1) with sw ≈ sw,eq. Additionally, by virtue of using the microscopic
supersaturation fluctuation (Eqn. 13.2.17) instead of (Eqn. 13.2.14), the operator Gs(∂/∂r) appears
now in (Eqns. 13.4.3a) and (13.4.3b) and leads to solutions of gamma distribution, and exponential
or inverse power law types (see Sections 13.5–13.7), while the operator (∂/∂r)(ccon /r) appears in the
previous (Eqn. 13.4.6) and leads to Gaussian solutions or the Weibull distribution, which decrease
with radius faster than most observed size spectra.
In most cloud models with explicit spectral microphysics, the high-frequency form of the kinetic
equation (13.4.4) is used and only a few attempts have been made to numerically solve the more
complete kinetic equations in the low frequency approximation (e.g., Vasilyeva et al., 1984). Incor-
poration into cloud models of the more complete kinetic equations of stochastic condensation in the
forms (Eqns. 13.4.3), (13.4.5), or (13.4.6) requires development of efficient economical numerical
algorithms for solutions of equations with cross-derivatives by coordinates and radii and the small
characteristic time and spatial scales that determine the condensation process.
636 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

13.5. Assumptions and Simplifications for Analytical Solutions

The basic equations developed in Sections 13.2–13.4 are applicable to pure liquid or pure crystal-
line clouds; mixed phase clouds are not explicitly addressed here. The kinetic equation of stochastic
condensation derived in Section 13.4 can be easily generalized by adding the collection (aggregation)
and breakup terms (∂f/∂t)col and (∂f/∂t)br as

∂f ∂ ∂
+ (ui − v (r )δ i 3 ) f  + (rɺcond f )
∂t ∂ xi   ∂r

 ∂ ∂  ∂ ∂  ∂f   ∂f 
= + δ i 3Gs Hˆ L  kij  + δ j 3Gs Hˆ R  f +  + , (13.5.1)
 ∂ xi ∂r   ∂ x j ∂r   ∂t  col  ∂t  br

where it is assumed that both liquid drops and ice crystals are represented by spheres of radius r.
Hereafter in this section, we use the notations common for liquid and ice clouds—i.e., rɺcond denotes
the condensation growth rate of a drop or deposition growth of a crystal, and s denotes supersatura-
tion over water or ice, unless specific notations are used for liquid or ice.
The turbulent coefficients kijn and kijnn involved in (Eqn. 13.5.1) and the correlation functions were
derived in Sections 13.2–13.4 for pure liquid clouds. However, the equations for pure crystalline
clouds have the same form as the expressions derived previously for pure liquid clouds. The deriva-
tion for pure crystalline clouds is the same, beginning with the kinetic equation of regular deposition
for the crystal size spectrum fc(rc) and the equation for a crystal growth rate drc /dt (Chapter 5). Then,
the same consideration of fluctuations and correlation functions as in Sections 13.2 and 13.3 can
be repeated for ice clouds, and we arrive at the same stochastic kinetic equation for the crystal size
spectrum. The major difference between pure liquid and crystalline clouds is in the different values
of supersaturation over water sw, or ice si, in liquid or crystalline clouds, and in the supersaturation
relaxation times τ f = (4π Dv N r )−1 , where N and r denote hereafter the drop or crystal number con-
centrations and their mean radii, and ω p = τ −f 1 = 4π Dv N r is the supersaturation relaxation frequency
introduced in Section 13.3. The times tf determine the rates of supersaturation absorption by drops or
crystals and the degree of their “nonconservativeness” in interactions with supersaturation.
For the turbulent frequencies w that provide the major contribution into the turbulent energy (e.g.,
Curry et al., 1988; Sassen et al., 1989; Quante and Starr, 2002; Shaw, 2003; Monin and Yaglom,
2007b), the expressions derived in Section 13.3 for the nonconservative turbulence coefficients
show that kijn (τ f ) ~ ω 2p ~ τ −f 2 and kijnn (τ f ) ~ ω 2p ~ τ −f 2 . That is, the nonconservative coefficients kijn, kijnn
decrease with increasing t f and are generally smaller in crystalline clouds due to the greater tf than
that in liquid clouds, which is caused by the different N, r . The values of tf ∼ 1 − 10 s for liquid
clouds with N ∼ 1 − 5 × 102 cm−3 and r ∼ 5 ∼ 10 µm (Section 5.3, Table 5.1). Calculations of tf in
cirrus and mid-level ice clouds using spectral bin models show that it varies in the range 102–104 s
for typical N and r —e.g., Khvorostyanov and Sassen (1998a,b, 2002), Khvorostyanov, Curry et al.
(2001, 2006), Sassen et al. (2002); Sassen and Khvorostyanov (2007); Table 5.2 in this book. Thus,
the values of kijn (tf), kijnn(tf) are smaller for crystalline clouds than for liquid clouds, but estimation
from the equations in Section 13.3 shows that values of kijn (tf), kijnn(tf) are comparable for both liquid
and crystalline clouds as described in the following text.
13.5. Assumptions and Simplifications for Analytical Solutions 637

Analytical solutions to the kinetic (Eqn. 13.5.1) can be obtained with the following additional
assumptions and simplifications:

1. The cloud is in a quasi-steady state, ∂f /∂t = 0. This does not imply a complete steady state, and
the time dependence can be accounted for via the integral parameters in the solution.
2. The cloud is horizontally homogeneous, ∂f /∂x = ∂f /∂y = 0.
3. The size spectrum is divided into 2 size regions,

f (r ) = fs (r ), r < r0 (13.5.2a)
f (r ) = fl (r ), r > r0 (13.5.2b)

where fs(r) and fl (r) are the small-size and large-size fractions, and r0 is the boundary radius
between the two size fractions. The value of r0 ∼ 30−50 μm for the drops and ∼30−80 μm (or
maximum dimension D0 ∼ 60–160 μm) for the crystals; r0 separates the domain r < r0 where
accretion rates are small and particle growth is governed mostly by the condensation/deposition
from the domain r > r0 where collection rates become important and prevail (see e.g., Cotton
et al., 2011, Fig. 4.1). The functions fs(r) and fl (r) correspond to the bulk categorization of the
condensed phase into cloud water and rain for the liquid phase and cloud ice and snow for the
crystalline phase.
4. The nonconservative turbulence coefficients are parameterized following Khvorostyanov and
Curry (2008b,c) to be proportional to the conservative coefficient k as kijn = cnk, and kijnn = cnnk.
In general, cn, cnn have values that are smaller than but close to unity; they are smaller in crys-
talline than in liquid clouds. A quantitative estimate of these nonconservative coefficients was
made with the model spectrum of turbulence:

ω 1/ 3
Fij (ω ) = Aω . (13.5.3)
Bω + ω 2

The maximum of (Eqn. 13.5.3) is found from the condition dFij /dw = 0, which yields
wm = (Bw /5)1/2. It is easy to see that Fij ∼ w−5/3 at w >> wm. Thus, this spectrum satisfies the
Kolmogorov–Obukhov asymptotic turbulence power law −5/3. The parameter Bw was deter-
mined from the measured maxima in the turbulence spectrum in Curry et al. (1988) for liquid
clouds, and in Sassen et al. (1989) in ice clouds, and the parameter Aw was determined by
normalization to the turbulence kinetic energy, which is the integral of (Eqn. 13.5.3) over the
w-spectrum. Evaluation with the spectrum (Eqn. 13.5.3) and these conditions showed that
kn and knn ∼ 0.2 − 0.7 k, depending on the cloud microstructure. This gives an estimate of cn,
cnn ∼ 0.2 − 0.7 and indicates that the nonconservative terms are quite comparable with the term
k(∂2f / ∂x2) and generally cannot be neglected, although it is done in almost all cloud models with
spectral microphysics.
5. The coagulation term (∂f / ∂t)col is described in detail in Section 14.2 of Chapter 14. We assume
at this point that drop breakup does not influence the small fraction; a correction due to breakup
can be added to the solution. For this analytical solution, the coagulation–accretion growth rate
(both for the drop collision-coalescence and for the crystal aggregation with crystals) is consid-
ered in the continuous growth approximation (see Chapter 14 here; Pruppacher and Klett, 1997;
638 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

Seinfeld and Pandis, 1998), with an accounting for only the collision–coalescence between the
particles of the different fractions of the spectrum, fs(r) and fl(r). The decrease in small fraction
fs is described in this approximation as a collection of the small-size fraction by the large-size
fraction.

 ∂ fs 
 ∂t  = − I loss = −σ col fs , r < r0 , (13.5.4)
col

σ col = π Ec ∫ r 2 v (r ) fl (r ) dr , (13.5.5)
r0

where v(r) is the particle fall velocity. These equations are derived in Section 14.2 from the
Smoluchowski stochastic coagulation equation (see Section 5.6) along with the mass conserva-
tion at the transition between the small- and large-size fractions.
With these assumptions, the kinetic (Eqn. 13.5.1) can be written for fs as

∂ ∂ ∂2 f
( w − v (r ) ) fs  + ( rɺcond fs ) = k 2s
∂z ∂r ∂z
 ∂ 2 fs ∂ 2 fs  ∂ 2 fs
+ cn kG  +  + cnn kG 2 − σ col fs . (13.5.6)
 ∂r ∂ z ∂ z ∂r  ∂r 2

All of the quantities on the left-hand side ( f, w, rɺcond , s) indicate averaged values in the sense
discussed in Sections 13.2–13.4, and all fluctuations are included on the right-hand side of the
equation. The terms on the left-hand side describe convective and sedimentation fluxes and
drop (crystal) condensation (depositional) growth/evaporation, and the terms on the right-hand
side describe turbulent transport, the stochastic effects of condensation/deposition growth, and
absorption by the large-size fraction.
To enable analytic solutions to (Eqn. 13.5.6), we make the following additional assumptions:
6. The vertical gradient of fs can be parameterized as a separable function:

∂ fs (r , z )
= α s ( z )ς s (r ) fs (r , z ). (13.5.7a)
∂z
The functions a s(z) and the zs(r) can be different for each fraction, determining the magnitude
of the gradient and its possible radius dependence. If zs(r) = 1, and

dfs / dz = α s fs , (13.5.7b)

it is easily shown from the definition of liquid (ice) water content that

α s ( z ) = (1 /qls )(dqls /dz ). (13.5.8)

7. We assume that terminal velocity v(r) following Khvorostyanov and Curry (2002, 2005) can be
parameterized in the form

v (r ) = Av (r )r Bv ( r ) , (13.5.9)

where Av(r) and Bv(r) are continuous functions of particle size, that include consideration of
various crystal habits and nonspherical drops and turbulent corrections to the flow around the
particles. The derivation and details of this representation are given in Chapter 12.
13.6. Approximation Neglecting the Diffusional Growth of Larger Particles 639

8. The condensation or deposition growth/evaporation rate rɺcond is described by the simplified

Maxwell equation that we use in notations common for drops and crystals:

bcon s Dv ρ vs
rɺcond = , bcon = , (13.5.10)
r Γ p ρw

where s = (rv − rvs)/rvs is the fractional supersaturation over water (ice), rv is the environmental
vapor density, and rvs (= rws or ris) are the saturated over water (ice) vapor densities, rw is the
water (ice) density, and Γp (= Γ1 or Γ2) is the psychrometric correction associated with the latent
heat of condensation.

Various assumptions on the form of zs(r) lead to various analytical solutions, we consider the sim-
plest case zs(r) = 1. Substituting (Eqns. 13.5.7b)–(13.5.10) into (Eqn. 13.5.6) allows elimination of
z-derivatives and we obtain a differential equation that contains only derivatives by r:

d 2 fs  b s  df
cnn kGs2 + 2cn kGsα s − con  s
dr 2  r  dr
 d (α k ) dw b s
+  2cn kGsα s + α s2 k + s
− α s (w − v) − − σ col + con2  fs = 0. (13.5.11)
 dz dz r 
The quasi-equilibrium supersaturation seq can be written following (Eqn. 13.2.9):

cp ρa (γ a − γ w )
seq = c1w wef τ f = Γp wef . (13.5.12)
L ρ vs 4π DN r

Then, the condensation term (Eqn. 13.5.10) can be rewritten as

bcon seq ccon wef

rɺcond = = , (13.5.13)
r r
ρa c p (γ a − γ w )
ccon = Gs r = bcon c1wτ f = Dv . (13.5.14)
ρ w L 4π Dv Nr
Analytical solutions of (Eqn. 13.5.11) are found in Sections 13.6 and 13.7.

13.6. Approximation Neglecting the Diffusional Growth of Larger Particles

In Sections 13.6 and 13.7, we obtain the analytical solutions of (Eqn. 13.5.11) for the small-size
fraction following Khvorostyanov and Curry (1999d, 2008d), with some generalizations. In some
situations, it can be assumed that the terms in (Eqn. 13.5.11) with diffusional growth can be neglected
for the larger particles in the small-size fraction. These terms can be much smaller in the tails of the
spectra than the other terms in (Eqn. 13.5.11) for small values of super- or subsaturation, or for suf-
ficiently large gradients as in relatively thin clouds, or for sufficiently large values of Gs. This allows
for neglect in (Eqn. 13.5.11) of the diffusional growth terms in the tails of the spectra since they
decrease with radius faster than the other terms.
Equation (13.5.11) is similar in structure to the Schrödinger equation of quantum mechanics for
the radial part of the wave function in the hydrogen atom. By analogy with this problem, following
Landau and Lifsitz (v. 3, 1958), we obtain asymptotic solutions in the small and large radii limits,
640 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

and then merge these two solutions to obtain the solution for all radii. In this section, we neglect the
diffusional growth of larger particles, which is accounted for in Section 13.7.

13.6.1. Small Particle Solution

The analysis of asymptotic behavior of the individual terms in (Eqn. 13.5.11) shows that the most
singular in r for small values of r are the 1st, 3rd, and last terms, and hence we retain in (Eqn. 13.5.11)
only these terms. Dividing them by cnnkGs2 and multiplying by r2, we obtain

d 2 fs df
r2 − a1r s + a1 fs = 0, (13.6.1)
dr 2 dr
bcon s
a1 = . (13.6.2)
cnn kGs2

Equation (13.6.1) is a linear homogeneous differential Euler equation of the 2nd order and its solu-
tion can be obtained in the form of a power law:

fs (r ) ~ r p . (13.6.3)

Substitution of (Eqn. 13.6.3) into (Eqn. 13.6.1) yields

bcon s Dv ρ vs s
p= = . (13.6.4)
cnn kGs2 cnn kGs2 Γ p ρ w

As discussed in Section 13.2, (Eqn. 13.6.4) accounts in s for the effects of various possible sources
of supersaturation (advective, convective, radiative, mixing among the parcels and with environ-
ment). In cloud layers with positive supersaturation, s > 0, then p > 0, and (Eqn. 13.6.1) has the
form of the left branch of the gamma distribution, fs(r) ∼ r p (for r smaller than the modal radius). In
evaporating cloud layers with negative supersaturation, s < 0, then p < 0, and the solutions have the
form of inverse power laws, fs(r) ∼ r−| p|. Thus, the index p of the gamma distribution or inverse power
laws that is usually found from fitting experimental data is expressed now via the physical quantities.

13.6.2. Large Particle Solution

For the larger particles in the small-size fraction beyond the modal radius, at r > rm but r < r0, with
r0 being the boundary between the small- and large-size fractions defined in Section 13.5, the terms
with supersaturation and diffusional growth, proportional to r −1 and ∼ r −2, are smaller than the other
terms, and we can eliminate in (Eqn. 13.5.11) the condensation growth terms. Then, (Eqn. 13.5.11)
becomes
d 2 fs df
cnn kG s2 + 2cn kGsα s s
dr 2 dr
+ [2cn kGsα s + α s2k (1 − µ s2 )] fs = 0, (13.6.5)

where
1/ 2
 1  dw dα s k  
µs =  2  α s ( w − v) + + σ col −  . (13.6.6)
α
 s k  dz dz  
13.6. Approximation Neglecting the Diffusional Growth of Larger Particles 641

We seek a solution as the exponential tail of the gamma distribution:

fs (r ) ∝ exp(− β s r ). (13.6.7)

Substitution of (Eqn. 13.6.7) into (Eqn. 13.6.5) yields a quadratic equation for bs:

cnn kGs2 β s2 − 2cn kGsα s β s + kα s2 (1 − µs2 ) = 0, (13.6.8)

which has two solutions for bs

cn kα s ∓ [cn2 k 2α s2 − cnn k 2α s2 (1 − µs2 )]1/ 2

β s ,1,2 = . (13.6.9)
cnn kGs

Hereafter in this section, the negative and positive signs relate to the first and second solutions,
respectively. Equation (13.6.7) represents the exponential tail of the spectrum with the slopes bs.
Physical conditions require that bs,1,2 > 0, so that fs(r) → 0 at large r. The solutions (Eqn. 13.6.9) are
simplified if the nonconservativeness of the k-components is neglected, cnn = cn = 1:
αs
β s ,1,2 = (1 ∓ µs ). (13.6.10)
Gs

Equation (13.6.7) represents the exponential tail of the spectrum and the slopes (Eqns. 13.6.9) and
(13.6.10) account for the turbulence, coagulation/accretion, and vertical gradients of k, w, as.
Expression (Eqn. 13.6.6) for ms is also simplified if to neglect coagulation (scol ≈ 0—i.e., if there
are few large particles), sedimentation (v = 0, small particles), and the gradient d(ask)/dz, and thus
(Eqn. 13.6.6) yields
1/ 2
 w 1 dw 
µs =  + 2  . (13.6.10a)
 α s k α s k dz 

13.6.3. Merged Solution

The general solution to (Eqn. 13.5.11) neglecting the diffusional growth of large particles can be
found by merging the two asymptotic solutions as

f1,2 (r ) = c1,2 r p exp(− β s ,1,2 r )ψ 1,2 (r ), (13.6.11)

where y1,2(r) are some functions to be determined from the equation. The solutions for y1,2(r) are
found under two simplifying assumptions. 1) We assume for simplicity cn = cnn = 1; a solution can
be easily generalized for the other cn and cnn. 2) We assume v = const, ms = const. The correction for
fall velocity v(r) can be introduced into the final solutions using the real fall speed v(r). Substituting
(Eqn. 13.6.11) into (Eqn. 13.5.11), applying (Eqns. 13.6.4) and (13.6.7), and performing simple but
tiresome manipulations described in Appendix A.13, we obtain an equation for y, which for b = bs1 is

d 2ψ  2α µ  dψ pα s
r + p+ s s
dr 2 
r + (1 + µs )ψ = 0. (13.6.12)
Gs  dr Gs
642 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

Converting to the dimensionless variable x = (2as m s /Gs)r and dx = (2a s m s /Gs)dr, we obtain

d 2ψ dψ p( µs + 1)
x + ( p + x) + ψ = 0. (13.6.13)
dx 2 dx 2 µs

This is a confluent hypergeometric equation or Kummer equation, the solution to which, satisfying
the conditions of finiteness, is the confluent hypergeometric function, F(a, b; c) (Landau and Lifshitz,
v. 3, 1958; Gradshteyn and Ryzhik, 1994):

 p 2s 
1 = c1 F  (s + 1), p; − r . (13.6.14)
 2s Gs 

The full solution for the droplet spectrum is then obtained from (Eqns. 13.6.11) and (13.6.14) to be

   p(s + 1) 2 s s 
fs1 (r ) = c1r p exp  − s (1 − s ) r  F  , p; − r , (13.6.15)
 G s   2 s Gs 

where c1 is a normalization factor.

Substituting (Eqn. 13.6.11) into (Eqn. 13.5.11) with b = b 2 from (Eqn. 13.6.10) yields another
equation for y :

 2α µ  pα s
rψ ′′+  p − s s r ψ ′ − ( µs − 1)ψ = 0. (13.6.16)
 Gs  Gs

This is also a hypergeometric equation, with the solution

 p 2α s µs 
ψ 2 = c2′ F  ( µs − 1), p; r , (13.6.17)
 2 µs Gs 

and the complete droplet size distribution function is obtained from (Eqns. 13.6.11) and (13.6.17),

 α   p( µs − 1) 2α µ 
fs 2 (r ) = c2 r p exp  − s (1 + µs )r  F  , p; s s r . (13.6.18)
 Gs   2 µs Gs 

The constants c1 and c2 for the distribution functions (Eqns. 13.6.15) and (13.6.18) can be determined
using the integrals with Kummer functions (Landau and Lifshitz, v. 3, 1958; Gradshteyn and Ryzhik,
1994; see Appendix A.13). For solution (Eqn. 13.6.15), we obtain
−1
− ( p +1)
 α   p(1 + µs ) −2 µs  

c1 = N Γ ( p + 1)  s (1 − µs )  F , p + 1, p;  (13.6.19)
1 − µs  
,
  Gs   2 µs

where Γ(x) is the Euler gamma function, and F(a, b, g ; x) is the Gauss hypergeometric function. For
(Eqn. 13.6.18), we obtain
−1
− ( p +1)
 α   p( µs − 1) 2 µs  

c2 = N Γ ( p + 1)  s (1 + µs )  F , p + 1, p;  (13.6.20)
1 + µs  
.
  Gs   2 µs

13.6. Approximation Neglecting the Diffusional Growth of Larger Particles 643

Equations (13.6.19) and (13.6.20) define c1 and c2 for the distribution functions, normalized to the
concentration N. From Appendix A.13, we can also determine the mean radius and water content
as the 1st and 3rd moments. Alternatively, if the liquid water content is specified (say from a model
prognostic equation), then the liquid or ice water content can be used to determine the constants c1
and c2. Expressions (Eqns. 13.6.15) and (3.6.18) are similar to gamma distributions with some modi-
fications that generalize the gamma distributions. The left branch of these gamma distribution type
spectra is described by the index p, which is now sign-variable, depending on supersaturation and
allows for various sources of cooling. The right branch is a usually observed exponential tail.
Note that the existence of the two solutions can describe bimodal droplet spectra that are observed
in clouds (e.g., Warner, 1969a) and in chamber mixing experiments (e.g., Baker et al., 1984). This
possibility of bimodality of these solutions resembles Manton’s (1979) theory. The existence, posi-
tions, and relative strengths of the two modes are determined by the values of as, m s, and Gs. The
solution imposes some limitations on the relation among these parameters. In particular, the Kummer
function can become negative or grow exponentially at large values of r for some combinations of as,
m s, and Gs, and they should be properly chosen from the physical conditions.

13.6.4. Asymptotic Solutions

The derived expressions can be used for numerical calculations of the size spectra and their moments
as described in this section. However, at least two asymptotic regimes exist where these solutions
can be simplified. These asymptotic formulas can be obtained using the properties of the confluent
hypergeometric function described in Appendix A.13. Using these expressions, we can consider two
asymptotic regimes which simplify the solutions to (Eqns. 13.6.15) and (13.6.18). These regimes are
determined by the term x = 2as m sr/G, which is the third argument of the confluent hypergeometric
functions in (Eqns. 13.6.15 and 13.6.18).
First asymptotic regime, x = 2a s m s r/Gs << 1. Since F(a, b, x) → 1 at x → 0 (see Appendix A.13),
the Kummer function vanishes in solutions and we obtain from (Eqns. 3.6.15) and (3.6.18) the fol-
lowing two solutions:
αs
fs1 (r ) = c1r p exp[− (1 − µs )r ], (13.6.21)
Gs
α
fs 2 (r ) = c2 r p exp[− s (1 + µs )r ]. (13.6.22)
Gs

These expressions are the usual gamma distributions with index p. The condition x = 2as msr/Gs << 1
implies that as should not exceed some value, as << Gs /2msrmax, where rmax is the maximum radius for
which the condition holds. To estimate this value of as, we assume rmax = 10 μm, N ∼ 200 cm−3, ms ∼ 1,
and calculate Gs ∼ 6.4 × 10−9. These values give an estimation of as < 0.3 km−1, or for qL ∼ 0.8 g m−3,
a vertical gradient dqL /dz < 0.25 g m−3 km −1 (from Eqn. 13.5.8).
So the asymptotic formulae (Eqns. 13.6.21) and (13.6.22) can be valid in the center of the cloud
layer near the maximum value of the liquid water content, or in any other region where the gradient
in qL is not very large. Note, however, that when as is very small, then ms >> 1, and from the condi-
tion of finiteness, only the second solution (Eqn. 13.6.22) is valid. We call this regime the “internal
asymptotic regime,” as it is valid in the cloud interior far from the boundaries.
644 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

Second asymptotic regime, x = 2asmsr/Gs >> 1. Using the limit of the Kummer function F(a, b, x) →
[Γ(b)/Γ(a)]exp(x)xa−b at x >> 1 (see Appendix A.13), we obtain from (Eqns. 13.6.15) and (13.6.18)
the following two solutions:

 α  p
f1 (r ) = cɶ1r pɶ1 exp  − s (1 + µs )r  , pɶ1 = ( µs + 1), (13.6.23)
 Gs  2 µs
 α  p
f2 (r ) = cɶ2 r pɶ 2 exp  − s (1 − µs )r  , pɶ 2 = ( µs − 1). (13.6.24)
 G s  2 µs

This asymptotic condition should be valid for all radii, and we can rewrite it as 2as msrmin /Gs >> 1.
This criterion is satisfied when as is large enough—i.e., when qL is small and its vertical gradient is
large. These conditions are typical near cloud boundaries. We can estimate the region of validity of
this regime by approximating the qL profile as a linear function of height: qL = q′L0 × z, where z is the
height above the cloud base and q′L0 is a gradient of the liquid water content. Then, as can be simpli-
fied as as = (1/qL)(dqL /dz) = 1/z. That is, as decreases rapidly with the height above the cloud base,
and we can determine the following condition for z:
2α s µs rmin 2 µs rmin 2 µs rmin
= >> 1, z << . (13.6.25)
Gs Gs z Gs

Using the values rmin = 1 − 1.5 μm, ms = 0.5 − 1, Gs = 1.3 × 10−8, we obtain z < 200−300 m, while
for Gs = 2.6 × 10−8 we obtain z < 100−150 m. So, this asymptotic regime can be valid within several
hundred meters of the upper or lower boundary of the cloud (as long as these levels do not include
a maxima in the liquid water content). We refer to this regime as the “boundary asymptotic regime”
because it is valid near cloud boundaries.
The extent of applicability of the asymptotic solution in (Eqns. 13.6.23) and (13.6.24) is further
illustrated by the following example. As the value of ms in (Eqn. 13.6.10a) should be real, the follow-
ing condition should be satisfied by as:

w 1 dw 1 dw
+ 2 > 0, or αs > − if w > 0. (13.6.26)
α s k α s k dz w dz

This condition allows as to be either positive or negative, depending on the vertical velocity profile
in the cloud. A positive value of as indicates that qL increases with the height in the cloud, while a
negative value of as indicates that qL decreases with the height in the cloud. The value of as would
be zero at the maxima of qL. The existence of vertical profiles of qL that increase with height to a
maximum value, then decrease with height above this maximum is commonly observed (see Sections
13.8 and 13.9) and may be caused by: 1) the corresponding vertical profiles of the vertical velocity in
frontal stratiform or convective clouds; 2) the entrainment of dry air into the cloud through the cloud
top or turbulent mixing with the dry air near the lower and upper boundaries with subsequent mixing
in the cloud; and 3) the vertical profiles of radiative cooling near the cloud top in stratiform clouds.
The solution (Eqn. 13.6.23) is the usual gamma distribution, where pɶ1 = ( p /2 µs )( µs + 1) is the
effective index of the gamma distribution. The second solution (Eqn. 13.6.24) satisfies the condition
of finiteness at large r only if ms < 1 for as > 0. For the solution (Eqn. 13.6.24), the effective index
pɶ 2 = ( p / 2 µs )( µs − 1) of the gamma distribution is negative. Size spectra of the form of the inverse
power law have been observed for small ice crystals (e.g., Heymsfield and Platt, 1984; Ryan, 1996).
13.7. Solution Including the Diffusional Growth 645

The inverse power law is not typically observed in water clouds for small drops but is observed for
the large-size fraction (see Chapter 2 and the next sections). Calculations such as those presented
in Section 13.9 show that the second solution (Eqn. 13.6.24) may exist in the lower cloud layer, but
when added to (Eqn. 13.6.23), it influences the “tail” of the spectrum and does not produce the second-
ary mode. Thus, we examine primarily the first solution.
To calculate the drop size spectra in these asymptotic regimes from (Eqns. 13.6.21)–(13.6.24), we
need to define the normalization constants c2 and c1. Using Appendix A.13, we can evaluate c2 from
the normalization to the concentration N. For (Eqn. 13.6.22) we have
( p +1)
−1  α 
c2 = N [ Γ ( p + 1) ]  s (1 + µs )  . (13.6.27)
G
 s 
For the first solution f1 of the “boundary” asymptotic solution (Eqn. 13.6.23), the normalization
constant is
pɶ1 +1
−1  α 
cɶ1 = N  Γ ( pɶ1 + 1)   s (1 + µs )  , (13.6.28)
 Gs 
where pɶ1 is defined in (Eqn. 13.6.23). Using (Eqns. 13.6.22) and (3.6.27) for the interior asymptotic
solutions and (Eqns. 13.6.23) and (3.6.28) for the boundary asymptotic solutions, one can easily calcu-
late the drop size spectra as shown in Section 13.9.

13.7. Solution Including the Diffusional Growth of Large Particles,

Sedimentation, and Coagulation

The solution obtained in Section 13.6 assumed that the diffusion growth terms are small at suf-
ficiently large r. However, if these terms are still significant in the tail of the small-size fraction,
as it can be at large sub- and supersaturations, it is desirable to find another solution that accounts
for these terms. Besides, it is desirable to estimate the effects of sedimentation and coagulation on
the shapes of the spectra. In this section, we find a solution that takes into account these effects. As
in Section 13.6, we again consider the two asymptotic cases at small and large r (again, within the
small-size fraction, at r < r0).
At small r, the same most singular terms (Eqns. 13.6.1) and (13.5.11) give the main contribution,
and the solution is the same power law (Eqn. 13.6.3), fs ∼ r p, with the index p defined in (Eqn. 13.6.4).
At large r, if the diffusional growth terms are retained, and then (Eqn. 13.5.11) is a 2nd order dif-
ferential equation with rather complicated variable coefficients, and an analytical solution is not easily
obtained. Hence, we seek a simplification that will enable an analytical solution. At large r, it is
reasonable to assume that the tail of the spectrum is smooth and the r-gradients of the spectrum are
smaller than near the mode. Then, we can neglect in (Eqn. 13.5.11) the stochastic diffusion terms in
radii space (the terms with Gs), and arrive at the following equation:

dw d  f 
[ w − v (r )]α s fs + fs + bcon s  s 
dz dr  r 
 dk dα s 
= α s2 k + α s +k − σ col  fs . (13.7.1)
 dz dz 
646 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

A solution to this equation is found in Appendix B.13:

r
fs (r ) = fs (r1 ) exp{−[β s 2 (r )r 2 − β s 2 (r1 )r12 ]}, (13.7.2)
r1

where r1 is some reference point, and the slope bs2 is

1 1  d (w − α s k )  α v (r ) 
β s 2 (r ) =   α s w + + σ col − α s2 k  − s . (13.7.3)
bcon s  2 dz  Bv + 2 

This is the solution for the tail of the small fraction. Equation (13.7.2) can be written in a slightly
different form that includes the terms with r1 in the normalizing constant cN:

fs (r ) = cN r exp[− β s 2 (r )r 2 ]. (13.7.4)

The merged solution can be constructed again as in Section 13.6 as an interpolation between the two
asymptotic regimes at small and large r:

fs (r ) = cN r p exp[− β s 2 (r )r 2 ]Φ(r ). (13.7.5)

Unfortunately, the resulting equation for Φ in this case is much more complicated than the confluent
hypergeometric equation in Section 13.6 and its solutions cannot be easily reduced to Kummer func-
tions. Thus, (Eqn. 13.7.5) can be used with some interpolation formulae for Φ—for example:

Φ(r ) = exp(− r /rsc ) + (r /rsc )1− p tanh(r /rsc ),, (13.7.6)

where rsc is a scaling radius comparable with r . At r << rsc, the first term tends to 1, the 2nd term
tends to 0, and we obtain from (Eqn. 13.7.5) fs ∼ r p at small r since bs2(r)r 2 << 1 in (Eqn. 13.7.5) and
exp → 1. At r >> rsc, the first term tends to 0, the 2nd term tends to (r/rsc), and the solution (Eqn. 13.7.6)
tends to the exponent (Eqn. 13.7.4). Thus, (Eqn. 13.7.5) ensures the correct limits at both small and
large r.
An advantage of (Eqn. 13.7.5) is that the tail of the spectrum explicitly accounts for the diffusional
growth process. This results in the inverse dependence of the slope bs2 (Eqn. 13.7.3) on supersaturation;
that is, the slope becomes steeper as |s| increases. This is physically justified since more vigorous
condensation/evaporation should produce narrower spectra. At sufficiently large r, the 2nd term with
v(r) in (Eqn. 13.7.3) dominates, and the slope is

α s v (r )
βs 2 = − . (13.7.7)
bcon s( Bv + 2)

Since fs should decrease at large r, the slope bs2 should be positive. Therefore, the terms as and s
should have opposite signs—i.e., as < 0 and LWC (IWC) increases downward in the growth layer
(s > 0, as < 0), and decreases downward in the evaporation layer (s < 0, as > 0), which is physically
justified for this limit v(r) >> w. The argument in the exponent is β s 2 r 2 ~ r 2 v (r ) ~ r Bv + 2—i.e., with
v(r) ∼ r2 (Stokes regime, Bv = 2) or v(r) ∼ r (intermediate regime, Bv = 1) or v(r) ∼ r1/2 (aerody-
namic regime, Bv = 1/2) (see Chapter 12), the tails of the spectra decrease as exp(−r4), exp(−r3), and
exp(−r2.5), respectively. That is, the tail of the spectrum has the form assumed for the generalized
gamma distributions, with the power of r in exponents greater than 1 (see Chapter 2), and a larger
value of the fall velocity v(r) is associated with a greater slope and shorter tail, which is consistent
with increased precipitation from the tail.
13.8. Physical Interpretation of the Parameters 647

When v(r) is small relative to the other terms (e.g., v(r) << |w|), the exponent bs2 is determined by
the 1st term in parentheses (Eqn. 13.7.3); neglecting for simplicity dw/dz, dk/dz, das /dz, we obtain

1
βs 2 = (α s w + σ col − α s2 k ). (13.7.8)
2bcon s

Now, the signs of s and of the expression in parentheses should coincide to obtain bs2 > 0. In
particular, if s > 0, w > 0, and the term asw is greater than scol and as2k in (Eqn. 13.7.8), then
as > 0—i.e., qls increases with height, which is justified for this limit w >> v(r). In this case, the slope
becomes steeper (the spectrum narrows) when w increases (as in regular condensation), and when
scol increases (faster absorption by the large fraction), and bs2 decreases when k increases (turbulence
causes broadening of the spectra). Since bs2 does not depend on r for this case, the tail of the spectrum
decreases as exp(−r 2).
The merged solution (Eqn. 13.7.5) differs from those found previously in the following ways. At
small r, the solution is a power law with variable rather than fixed index p, allowing variable rela-
tive dispersions. Also, the slope of the tail is not constant but varies (generally increases) with r;
accounting for the greater depletion of large particles with greater sedimentation rate. The slope also
describes depletion of the small fraction due to accumulation by the large fraction via the term scol:
the larger coagulation rate and scol, the greater the slopes and the faster the decrease with r. The tail
in (Eqn. 13.7.4) at large r behaves as exp(−r l) with l varying from 2 to 4 for various situations, in
broad agreement with the range of values determined by previous analytical solutions and parameter-
izations as generalized gamma distributions (see Section 2.4.4).

13.8. Physical Interpretation of the Parameters

13.8.1. Various Forms of Solution Parameters

The dimensionless parameter Gs introduced in (Eqn. 13.3.12) in the process of averaging over the
turbulence spectrum can be written in various forms:

ρ a c p γ a − γ w c f ρ a c p (γ a − γ w ) r
Gs = ≈ , (13.8.1)
ρ w L 4π N r 2 3 L qls

where cp is the specific heat capacity, L is the latent heat of condensation or deposition, ga and gw
are the dry and wet (water or ice) adiabatic lapse rates, ra is the air density, N and r are the number
concentration and mean radius of the particles, and qls is the liquid (ice) water content of the small
fraction. The coefficient cf occurs in (Eqn. 13.8.1) since we use a relation qls = ( 4 /3 )π c f ρ w N r 3,
or (4π N r 2)−1 = (c f /3) ρ w r / qls . The value of cf depends on the shape of the spectra and is on the
order of 1. For example, for gamma distributions with the index p considered in the following text,
cf = (p + 2)(p + 3)/(p + 1)2—i.e., cf /3 = 1 for p = 1 and cf /3 = 0.5 for p = 6. In the future, we assume in
(Eqn. 13.8.1) that cf /3 ≈ 1, since its variations are several orders of magnitude smaller than variations
of qls, N, and r . Introducing the adiabatic liquid (ice) water mixing ratio qls,ad(z) = (dqls /dz)ad(z − zbot),
where (dqls/dz)ad is the adiabatic vertical gradient of the mixing ratio (see Section 3.11):

 dqls  cp
  =
dz  ad L
(γ a − γ w ) ρa , (13.8.2)
648 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

zbot is the height of cloud bottom, (z − zbot) is the altitude above zbot, and gw hereafter denotes the
wet adiabatic lapse rate in liquid or ice clouds (see Section 3.11). Gs in (Eqn. 13.8.1) can be also
rewritten as
−1
ρa 1  dqls  r  dqls  r  qls  r
Gs = 2   =   = = , (13.8.3)
ρ w 4π Nr  dz  ad qls  dz  ad ( z − z bot )  qls ,ad  χ ad ∆z

where cad = qls /qls,ad is the adiabatic liquid (ice) ratio, and Dz = z − zbot is the height above the cloud
base. If the major source of supersaturation is uplift and/or radiative cooling, then p in (Eqn. 13.6.4)
can be expressed via the “effective” vertical velocity wef, using (Eqns. 13.5.13) and (13.5.14):

bcon s ccon wef rwef

p= 2
= 2
= . (13.8.4)
cnn kGs cnn kGs cnn kGs

Using (Eqns. 13.8.1)–(13.8.3) for Gs, the index p from (Eqn. 13.8.4) can also be written in the fol-
lowing forms

wef L 4πρ w N r 3
p=
cnn k c p (γ a − γ w ) ρa
wef qls wef
≈ ≈ χ ad ∆z. (13.8.5)
cnn k (dqls, ad /dz ) cnn k

All of the parameters in (Eqn. 13.8.5) are available from bulk models, and the index p can be eas-
ily calculated. The first expression in (Eqn. 13.8.5) can be used in the double-moment models, when
both qls and N are known, then r and p can be calculated (e.g., Morrison et al., 2005a,b). The 2nd and
3rd expressions in (Eqn. 13.8.5) can be used in single-moment models, when only qls is available.
The relative dispersion of the spectra sr and parameter p are related as (Chapter 2)

σ r = ( p + 1)−1/ 2 , p = 1/σ r2 − 1.
(13.8.6)
The term “effective velocities” here means subgrid velocities with addition of the “radiative-effective”
velocities wrad that allow direct comparison of the dynamical subgrid velocity wdyn and wrad that is
determined by radiative cooling rates:

wef ≈ wdyn + wrad , wrad = − (1 / a )(∂T / ∂t )rad , (13.8.7)

where (∂T/ ∂t)rad is the radiative cooling rate caused by the total radiative flux divergence.
Since large-scale models with horizontal grid spacing ∼ 100–400 km may produce wdyn and
wef ≤ 1–2 cm s−1, the problem of the subgrid parameterization of wef was addressed in several works
and there were various definitions of the subgrid velocities in the models. Ghan et al. (1997) speci-
fied the subgrid velocities wdyn in the general circulation model (GCM) via the turbulence coefficient
k and mixing length lmix:

wdyn ≈ k /lmix . (13.8.8)

Morrison et al. (2005a,b), and Morrison and Pinto (2005) developed a model with bulk double-
moment microphysics based on gamma distributions. The p-indices in this model were not prescribed
as some a priori fixed values but were calculated using (Eqns. 13.8.4) and (13.8.5), the subgrid
13.8. Physical Interpretation of the Parameters 649

velocities wsg were specified similar to Ghan’s et al. (1997) in (Eqn. 13.8.8). Sud and Lee (2007) and
Sud et al. (2009) parameterized the particle size spectra in the form of a gamma distribution in the
Goddard Space Flight Center (GSFC) GCM and also used the solutions (Eqns. 13.8.4) and (13.8.5)
for the p-indices from Khvorostyanov and Curry (1999d) for evaluation of effective radius and cloud
optical properties. Thus, the p-indices of the gamma distributions in these models were not constant
but varied in space and time.
An alternative to these parameterizations of k, wdyn, and lmix was suggested by Dmitrieva-Arrago
and Akimov (1998) in a GCM with prognostic equations for qL and dew-point deficit. The subgrid
value of wdyn for stratiform clouds was defined in this GCM as the minimum velocity required to
support all falling droplets with radii smaller than some threshold value—e.g., ∼40 μm, close to the
estimate of r0 in Section 13.2. Assuming Stokes’ velocities gives wdyn ≈ 20 cm s−1, which is compa-
rable to the estimation by Ghan et al. (1997) and Morrison et al. (2005a,b). Tables 13.1 and 13.2
show that with k ∼ 10 m2 s−1, this would give reasonable values of p ∼ 5–10, so the method developed
here can be used for evaluation of p-indices in such GCMs with parameterizations of subgrid wdyn
similar to Dmitrieva-Arrago and Akimov (1998). Ghan et al. (1993) derived an equation for wdyn that
also includes the effects of horizontal advection of heat and moisture. This equation was used in that
work for evaluation of drop activation on CCN but can also be used for evaluation of the p-indices.
As noted in Section 13.4, another estimate of the effective velocity wef can be done from the relation
wef ~ w ′qL′ / qL using the data gained in the field experiments. The values of the flux w ′qL′ measured
in arctic stratus presented in Curry (1986) are always positive (except near the cloud base). For the
upper deck observed on 28 June 1980, the value of w ′qL′ was 25−55 × 10−4 g m−2 s−1 at z = 818 m with
corresponding qL ∼ 0.12 − 0.2 g m−3. This gives an estimate wef ∼ 12 − 20 cm s−1. For the same deck,
the covariances w ′w ′ ~ 0.1 − 0.2 m 2 s −1 (Curry et al., 1988)—i.e., w ′ ~ ( w ′w ′)1/ 2 ∼ 33 − 45 cm s −1,
which is larger than the previous estimate for wef. This is in agreement with the discussion of the
covariances in Section 13.3, which showed that the correlation function w ′f ′ or w ′s ′ due to the phase
shift between them by tf should be smaller than the autocovariance w ′w ′. Here, wef should be smaller
than w′, but still much greater than the synoptic-scale average wsyn ∼ 0.5–1 cm s−1.
The general (Eqn. 13.8.4) for p shows that the index p ∼ s, and hence p can be positive or negative.
These two cases are considered in the following text.

13.8.2. Solutions in the Form of Gamma Distributions

If wef > 0, then p is positive. Equations from Sections 13.6 and 13.7 show that the size spectrum of
the small fraction is then the power law multiplied by the exponent, with some modification—i.e., is
close to the gamma distribution. The expressions (Eqn. 13.8.5) for this case show that p depends on
5 factors: w, k, adiabatic ratio cad, height Dz, and cnn. Since cnn ∼ 1, we illustrate in the following text
the role of the other factors.
Effect of parameters Gs and p. The equations for Gs and p indicate several features that are similar
for both cloud drop and crystal size spectra. Equations (13.8.4) and (13.8.5) show that p increases and
the relative dispersion sr decreases (the spectra become narrower) when positive wef increases, which
is similar to the effect of regular condensation. The index p decreases (the spectra become broader)
when k increases, which describes the effect of turbulence in stochastic condensation.
650 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

As discussed in Section 13.4, the effective diffusion coefficient in the space of radii is kr = Gs2k.
Equation (13.8.1) for Gs shows that: 1) since Gs ~ r , the diffusion coefficient kr is proportional to
the squared mean radius r —i.e., kr ~ r 2, which thereby is an analog of “mixing length in the space
of radii,” similar to the turbulent coefficient k = l ′ 2 (∂u / ∂ z )—i.e., proportional to the squared mixing
length l′; and 2) since kr ∼ Gs, and Gs ∼ 1/cad, kr at any given height z is inversely proportional to the
liquid water ratio cad (the ratio of qL to the adiabatic value of qL,ad).
Table 13.1 shows that the values of the parameter Gs calculated from (Eqn. 13.8.3) increase from
0.32 × 10−8 at N = 400 cm−3, r = 10 µ m to 5 × 10−8 at N = 100 cm−3, r = 5µ m . Table 13.2 shows that the
values of p calculated from (Eqn. 13.8.5) for the “interior cloud” solution (Eqns. 3.6.21) and (3.6.22)
range from 2 to 8 for wef = 10 cm s−1 in a cloud with mean radius r = 5 µ m and droplet concentration
N = 1 − 4 × 102 cm−3, typical for continental, summertime arctic stratus clouds (Curry, 1986) or some
types of marine clouds near the coast (Noonkester, 1984). This value of p corresponds to dispersions
of the spectra sr ∼ 0.33 − 0.58 (Table 13.3), which is close to values observed in the central layers
of such clouds. For r = 10 µ m, typical of marine stratus clouds, the values of p increase; however,
since typical drop concentrations are usually N = 1 − 2 × 102 cm−3 for these clouds, values of p would
not normally exceed p = 8 − 16 for this cloud type and would be less for smaller values of wef. Thus,
from Table 13.2 we see that the spectra become narrower with increasing droplet concentration and
mean radius. If the value of the turbulent coefficient is k = 10 m2 s−1 or the maximum effective vertical
velocity is 5 cm s−1, the values of p in Table 13.2 would be twice as small.

Table 13.1. Parameter Gs (10−8) for gw = 6 K km−1 and various

values of droplet concentrations N and mean radii r̄.

N, cm−3

r , μm 102 2·102 4·102

5 5.1 2.6 1.27

10 1.3 0.64 0.32

Table 13.2. Parameters p of the gamma distribution for

k = 5 m2 s−1, gw = 6 K km−1, with various droplet
concentrations N, mean radii r̄, and vertical velocities wef

N, cm−3

r , μm 102 2·102 4·102

wef = 1 cm s−1
5 μm 0.2 0.4 0.8
10 μm 1.6 3.2 6.4
wef = 10 cm s−1
5 μm 2 4 8
10 μm 16 32 64
13.8. Physical Interpretation of the Parameters 651

Table 13.3. Relative dispersions σ r = (p + 1)−1/2 of the gamma

distribution for various droplet concentrations N, mean radii r̄,
and wef for the same parameters used in Table 13.2

N, cm−3

r , μm 102 2 × 102 4 × 102

wef = 1 cm s−1
5 μm 0.91 0.84 0.74
10 μm 0.62 0.49 0.37
wef = 10 cm s−1
5 μm 0.58 0.45 0.33
10 μm 0.24 0.17 0.12

These tables show that for wef = 1 − 2 cm s−1, as could be evaluated from the large-scale divergence
(i.e., with the averaging over the large areas), the values of p are too small (p < 1 for r = 5 µ m ), and
the dispersions are too large as compared to the local observations. The problem of correspondence
of the local size spectra and those averaged over the large cloud areas has been widely discussed in
the literature, and it was found that the scale of averaging influences the index p. The local (measured
over the horizontal scales Lx ∼ 30–100 m) spectra are usually narrow, with p = 6, sr = 0.38 to p = 10,
sr = 0.30 (e.g., Aleksandrov and Yudin, 1979; Curry, 1986; Liu and Hallett, 1998; Cotton et al., 2011).
This is illustrated in Table 13.4 with an example of the local drop spectra measured in low arctic
stratus over small horizontal intervals (Curry, 1986), where p = 5–10 and sr = 0.3–0.4 except for
the cloud base with wider spectra. However, the dispersions increase and the indices decrease with
increasing scale of averaging, (Lx ∼ a few km) or with averaging over many clouds (e.g., Mason,
1971; Sedunov, 1974; Pruppacher and Klett, 1997). This effect of averaging is clearly seen from
the data by Noonkester (1984) for marine stratocumulus shown in Table 13.4, which illustrates the
increase in sr (artificial “broadening” of the spectra) with averaging over the scale 6.44 km (sr,all)
as compared to the local spectra averaged over 0.529 km (sr,loc). Outside cloud top and bottom, the
local p = 6–22, (sr = 0.2–0.4), and averaged over the scale 6.44 km p ∼ 0.13–1.3 (sr = 0.66–0.94).
This impact of averaging on the width of the size spectra is described by (Eqn. 13.8.5) since p ∼ wef,
which decreases with increasing scale of averaging. Note, however, that the cloud optical and radiative
properties and the rate of precipitation formation are determined by the local (Lx ∼ 50–100 m) size
spectra, hence the local values p = 6–10 with sr = 0.3–0.4 are representative and should be used for
the parameterizations.
For convective clouds, typical values of vertical velocity are w ∼ 2.0 − 5.0 m s−1; that is, 20–30 times
larger than values used in Table 13.2 for stratiform clouds. Although the values of the turbulence
coefficient for cumulus can be about 10–20 times larger than those for stratus clouds, this shows that
the values of p should be larger and spectra narrower in cumulus, which is expected since the processes
in the vigorous updrafts are closer to the regular condensation. In convective clouds, the factor cadDz
can also influence the spectra as described in the following text.
An important feature of the solutions for p obtained here is that although (Eqn. 13.8.5) for p
includes many parameters that vary by several orders of magnitude, the expression for p leads to a
652 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

Table 13.4. Observed relative dispersions, σ r = (p + 1)−1/2 = (σabs / r )1/2,

and corresponding indices p in low stratus clouds

Arctic summertime stratus (Curry, 1986)

Deck, date Height, m qL, g m−3 sr p

#1, 20 June 1980 289 (top) 0.02 0.39 5.6

73.5 N, 241 0.42 0.30 10.1

159.3 W 183 0.35 0.31 9.4

91 0.20 0.36 6.7

#2, 28 June 1980 1082 (top) 0.03 0.38 5.9

77.7 N, 940 0.30 0.33 8.2

155.2 W 819 0.10 0.40 5.3

696 (base) 0.02 0.51 2.8

California coastal stratus (Noonkester, 1984)

sr,loc and ploc are averages over local paths of 529 m,
sr,all and pall are averages over all paths of 6.44 km.

Height above
Date cloud base, m qL, g m−3 sr,loc/sr,all ploc/pall

29 May 1981 274 (top) 0.288 0.42/0.67 4.7/1.2

167 0.217 0.21/0.66 21.7/1.3

18 0.034 0.57/0.89 2.1/0.3

18 August 1981 222 (top) 0.263 0.79/0.94 0.6/0.13

121 0.199 0.37/0.78 6.3/0.6

17 0.037 0.56/0.81 2.2/0.5

dimensionless quantity of order 1–10 for a wide variety of cloud types, and the relative dispersion
is now related directly to the meteorological factors (w, ga, k), the properties of the cloud (N, r ), and
fundamental atmospheric constants.
Effect of parameters bad and Dz. The additional factor in (Eqn. 13.8.5) is the adiabatic ratio cad,
the index p ∼ cadDz. In convective clouds, cad usually decreases with the height above the cloud base
due to entrainment, but decreases with cloud width (e.g., Pruppacher and Klett, 1997, Figs. 2–22).
A decrease in cad may cause a decrease of p in (Eqn. 13.8.5) and a broadening of the spectra with height
in the lower cloud layers. In the upper cloud half, cad may tend to nearly constant values (e.g., Prup-
pacher and Klett, 1997), while the height-factor Dz causes a counter-effect in (Eqn. 13.8.7), causing
13.8. Physical Interpretation of the Parameters 653

an increase of p and spectral narrowing. Which effect will dominate depends on the product cadDz. If
cad decreases with height faster than 1/Dz, then cad.Dz decreases and the spectra broaden with height,
as was observed in a convective cloud by Warner (1969a). It is this effect that is in contradiction with
the theory of regular condensation that predicts narrowing of the spectra with height, and stimulated
numerous attempts to explain the broad spectra, including the stochastic condensation theory as
reviewed in the Introduction to Chapter 13.
However, later experimental studies showed that broadening with height is not a common feature
of the droplet spectra, which may exhibit narrowing with height in cumulus clouds (e.g., Austin et al.,
1985) and even in the nearly adiabatic cores of convective clouds (Brenguier and Chaumat, 2001).
This feature may be explained by the factor cadDz. If cad in (Eqn. 13.8.5) decreases with height slower
than 1/Dz, then cad.Dz increases, p increases, and the spectra narrow with height, resembling the
effect of regular condensation, as observed in a shallow convective cloud by Austin et al. (1985). The
values of relative dispersion sr for a convective cloud described in Austin et al. (1985) varied from
sr = 0.2–0.3 in the middle of the cloud (corresponding p calculated from (Eqn. 13.8.6) are 13–25)
to sr = 0.17–0.21 (p = 22–35) near the cloud top. Thus, the spectra narrow with height in this case,
in contrast to the convective cloud observed by Warner (1969a). If the product cadDz is close to but
slightly lower than the adiabatic value (i. e., cadDz ≈ const), such as in convective adiabatic cores due
to lateral mixing, then the spectra can be narrow, but still wider than it would be in adiabatic ascent,
similar to the situation observed by Brenguier and Chaumat (2001) in cumulus clouds.
Note that the entrainment processes in cumulus or near the tops of stratocumulus can be easily
accounted for in this approach by addition into the RHS of the kinetic (Eqns. 13.4.3a), (13.4.3b), and
(13.5.11) of the term −τ m−1 fs, with tm being the characteristic mixing time. Then, the two solutions
(Eqn. 13.6.10) for the slope bs1,2 are modified:

α s   τ m−1 1 dw  
1/ 2
w
β s ,1,2 = 1 ±  + + . (13.8.9)
Gs   kα s2 kα s kα s2 dz  
 
The merged solution (Eqn. 13.6.11) becomes a superposition of two functions:

f1,2 (r ) = c1r p exp(− β s ,1r )ψ 1 (r ) + c2 r p exp(− β s ,2 r )ψ 2 (r ), (13.8.9a)

and can give the bimodal distributions. Equation (13.8.9) shows that with decreasing mixing time, τ m−1
increases and leads to the larger separation of the modes and to broader spectra. Recall that one of
Manton’s (1979) results was that the size spectrum of each single mode was too narrow and only their
bimodal superposition could ensure the dispersion growing with height at a rate comparable to the
measured values (Warner, 1969a). A bimodal superposition of the gamma distributions considered
here may also provide sufficient dispersion for the case of cumulus clouds.
In application of this parameterization for ice clouds, the difference of the crystal size spectra
with the drop spectra arise due to the different values of N, r , and lapse rates gw. In liquid clouds,
N ∼ 1 − 5 × 102 cm−3, r ~ 5 − 10 µ m, and according to (Eqn. 13.8.3) and Table 13.1, Gs ∼ (0.3 − 5) × 10−8.
In crystalline cirrus clouds with N ∼ (1 − 5) × 102 L−1 (∼ 3 orders of magnitude smaller
than droplet concentrations), qls ∼ 10 − 20 mg m−3, r ~ 5 − 10 µ m, and (Eqn. 13.8.3) yields
Gs ∼ 10−7 − 10−5. Thus, both Gs and r are 1–2 orders greater in cirrus than in liquid clouds.
654 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

According to (Eqn. 13.8.4), p ~ r /Gs, so that the increase in Gs is compensated by a similar growth
in r , and the indices p appear to be comparable in liquid and crystalline clouds, as illustrated in more
detailed calculations in Section 13.10.
Temperature dependence. Equation (13.8.5) for p also shows that there is a temperature depen-
dence of the drop and crystal size spectra. Liquid water clouds can occur over a large range of
temperatures, particularly since supercooled liquid clouds are sometimes observed at temperatures
as low as −35 °C and crystalline clouds are observed at −80 °C and lower (Borovikov et al., 1963;
Pruppacher and Klett, 1997; see Chapter 4). According to (Eqn. 13.8.5), p ∼ (ga − gw)−1. Since
sr = (p + 1)−1/2, then for the typical condition p >> 1, sr ≈ p−1/2 ∼ (ga − gw)1/2. The wet adiabatic lapse
rate gw tends to the dry adiabat ga with decreasing temperature; thus, p increases and sr decreases
at low T. This explains observed narrower spectra in summertime colder liquid As-Ac clouds at
T ∼ −20 °C, P = 800 hPa (ga − gw = 1.7 °C km−1) than in warmer Sc at T ∼ 0 °C (ga − gw = 4 °C km−1)
(e.g., Herman and Curry, 1984; Tsay and Jayaweera, 1984). This dependence is also strong in cirrus
clouds at low temperatures for the wet adiabat gw over ice. For example, at a pressure P = 200 hPa,
the value ga − gw = 4.14 °C km−1 at −20 °C, 1.22 °C km−1 at −40 °C, and 0.62 °C km−1 at −50 °C. Thus,
(Eqn. 13.8.5) predicts that the index p would increase by a factor of ∼7 from −20 °C to −50 °C if N,
r , and the pressure were the same, and the crystal size spectra in cirrus should become narrower with
decreasing T. This feature is clearly seen in the experimental data where the spectra are sorted by
temperature or height (e.g., Heymsfield and Platt, 1984; Sassen et al., 1989; Platt, 1997; Poellot et al.,
1999, Lawson et al., 2006). The theory described here provides a basis for the quantitative description
of the temperature dependence of the drop and crystal size spectra.
This narrowing of the spectra with decreasing temperature causes slower droplet freezing, sup-
presses coagulation and accretion, and consequently precipitation—that is, it causes greater colloidal
stability of the colder clouds. Vice versa, global atmospheric warming may lead to broader size spec-
tra, intensification of coagulation, and precipitation. This may cause a decrease in cloud albedo—i.e.,
in global albedo, and accelerate warming. Thus, (Eqn. 13.8.5) predicts that a positive feedback may
exist between warming and the broadening of the size spectra.

13.8.3. Solutions in the Form of Inverse Power Laws

Equation (13.8.4) predicts that the index p is negative in cloud layers with subsaturation, s < 0. Sub-
saturation may occur in a cloud due to downdrafts, advection of drier or warmer air, entrainment of
dry ambient air, and radiative heating. Under these conditions, the smallest particles should have been
evaporated to some boundary values r* and the left branch of the size spectra at r > r* is described by
the inverse power law

fs (r ) ~ (r /r* ) p ~ (r* /r )− | p| . (13.8.10)

Such inverse power laws have been found by fitting experimental data from crystalline cirrus and
frontal clouds in Heymsfield and Platt (1984), Platt (1997), Poellot et al. (1999), Ryan (2000), and in
the data for the larger drops in liquid clouds (Okita, 1961; Borovikov et al., 1965; Nevzorov, 1967;
Ludwig and Robinson, 1970), as described in Chapter 2. Here, this inverse power law is obtained
as a solution to the kinetic equation and its index p is expressed in (Eqn. 13.8.5) via physical cloud
parameters.
13.8. Physical Interpretation of the Parameters 655

An estimation of p from (Eqn. 13.8.5) for cirrus clouds shows that at T ∼ −40 °C with k = 5 − 10 m2 s−1
and Gs ∼ (1 − 2) × 10−7, the parameters are kGs2 ∼ (0.5 − 1) × 10−9 cm2 s−1, bcon ∼ 4 × 10−8 cm2 s−1. Then,
at subsaturation s = −0.1 (−10%), assuming cnn = 1, we obtain p = bcons/kGs2 ∼ −2 to −4. The indices
estimated here are quite comparable to those in Heymsfield and Platt (1984), Platt (1997), Poellot et al.
(1999), and Ryan (2000) that give p ∼ −1 to −8.
When size spectra are sorted by temperature, there is a distinct increase of the measured and fit-
ted slopes |p| with decreasing temperature. This can also be described using (Eqn. 13.8.5) with wef
< 0. Then again, as in the case p > 0, the slopes in the crystalline clouds |p| ∼ (ga − gis)−1, where gis is
the lapse rate at the vapor–ice transition (see Section 3.11). Comparing the spectra at two tempera-
tures, −20 °C (pressure pa = 600 hPa, ga − gis = 2.14 °C km−1) and at −50 °C (pa = 200 hPa, ga − gis =
0.62 °C km−1), we obtain that the slopes |p| should be about 2.14/0.62 = 3.5 times larger at colder
temperatures if the other parameters are the same. A more precise evaluation for various pa, T, N,
and r can be performed using (Eqn. 13.8.5) instead of fitting to the measured spectra, as is usually
done.
Subsaturated layers with negative p may constitute significant portions of crystalline clouds, par-
ticularly as falling particles enter the subsaturated regions below the cloud. Hall and Pruppacher
(1976) showed that falling from cirrus clouds crystals can survive at subsaturation over 2–6 km,
which was confirmed by later modeling studies of evolving cirrus (e.g., Jensen et al. 1994, 2001;
Khvorostyanov and Sassen, 1998a,b, 2002; Sassen et al., 2002; Khvorostyanov, Curry et al. 2001).
The life cycle of cirrus clouds usually begins with ice nucleation on haze particles that requires some
threshold supersaturation (Chapters 8 and 9). After this threshold has been reached, the rate of vapor
absorption by the nucleated crystals may exceed the rate of supersaturation generation, so that the
mean supersaturation decreases, and the thickness of the cloud evaporation layer increases and can
exceed the thickness of the growth layer. This process, governed by the crystal supersaturation relax-
ation time, is slow and may last up to several hours. This may cause a significant frequency of ice
subsaturated (evaporation) layers in crystalline clouds and explain observations of the inverse power
law spectra, based on the results of this section.
These features of the spectra discussed in this section and related to variations of the indices p are
usually ignored and missed in models with parameterizations that use constant values of p = 0–3 for
all spectra. This may reduce the accuracy of such models.
The effect of averaging is the same for ice clouds as that discussed earlier for liquid clouds. The
measured and calculated sr increase and p decrease with increasing scales of averaging Lx. It should
be emphasized that the local narrow spectra with p ∼ 6–20, as all the cited experimental data indi-
cate, are representative of the cloud processes and should be used in parameterizations, since these
local spectra govern radiative transfer, coagulation-accretion, and precipitation. Averaging over large
scales leads to an artificial broadening of the spectra, and unphysical lowering of the indices p to
the values of 0–2; use of such broad spectra may cause artificial acceleration of the coagulation pro-
cesses, unphysically faster precipitation formation and cloud dissipation, and errors in evaluation of
the radiative scattering and absorption coefficients (Section 2.5).
The relationships described here are consistent with observations in clouds (e.g., Levin, 1954;
Mason, 1971; Sedunov, 1974; Pruppacher and Klett, 1997; Cotton et al., 2011). Thus, (Eqns. 13.8.4)
and (13.8.5) establish an analytical relationship of the index p, and hence drop spectra dispersion,
with the meteorological characteristics of the atmosphere.
656 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

13.9. Applications of the Solution for Liquid Clouds

To illustrate the analytical solutions and evolution of the droplet spectra below the maximum in qL,
we consider the following characteristics typical of low stratus clouds and close to the arctic stratus
observed on 28 June 1980 in the upper layer (Curry, 1986). The vertical profile of qL is approxi-
mated by a parabolic profile of the form qL(z) = cNqL,max(z/H)a(1 − z/H)b, where H is the cloud depth,
qL,max is the maximum of LWC, cN = [a/(a + b)]a [b/(a + b)]b; qL and the parameter as are presented
in Fig. 13.1. Cloud boundaries are at 700 m and 1100 m, and the maximum value qL,max = 0.4 g m−3
is located at ∼1000 m. The vertical profile of the mean radius is chosen such that r = 2.5 µ m at the
cloud bottom and linearly increases to r = 6 µ m at the cloud top. The vertical profile of the droplet
concentration N calculated using these values of qL and r is also presented in Fig. 13.1, and exhibits
the fastest increase above the base with a much slower increase in mid cloud. Such profiles are also
in agreement with the results of LES simulations of stratocumulus (e.g., Feingold et al., 1994), aver-
aged over the domain.
To investigate the effect of vertical velocity, turbulence, and radiation on the drop size spectra,
we examine four different cases, using the definition of effective vertical velocity wef = wdyn + wrad
described in Section 13.8. The four cases are: 1) wrad is determined by accounting for the longwave
cooling rate only, wdyn = 1 cm s−1, and k = 5 m2 s−1; 2) wrad is determined by accounting for longwave
cooling only, wdyn = 10 cm s−1, and k = 5 m2 s−1; 3) wrad = 0, wdyn = 15 cm s−1, and k = 5 m2 s−1; and 4)

1100 1100

1050 LWCad 1050

LWC N
1000 1000

950 αs 950
Height (m)
Height (m)

900 900

850 850
LWC r
800 LWCad 800 N
αs r
750 750
N
700 700
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 2 3 4 5 6
LWC (g m–3) Mean radius r (µm)

–5E–4 0 5E–4 1E–3 1.5E–3 0 100 200 300 400 500

α (cm–1) Droplet concentration N (cm–3)

(a) (b)

Figure 13.1. Vertical profiles for a prototype case of Arctic stratus clouds: (a) liquid water content
(LWC), qL, adiabatic liquid water content (LWCad), and parameter as = (1/qL)(dqL/dz); (b) droplet
concentration, N(z), and mean radius, r ( z ). From Khvorostyanov and Curry (1999d). J. Atmos. Sci., 56,
© American Meteorological Society. Used with permission.
13.9. Applications of the Solution for Liquid Clouds 657

wrad is determined by accounting for longwave cooling only, wdyn = 10 cm s−1, and k = 10 m2 s−1. These
variations allow examination of the individual effects of w, k, and radiation on the drop size spectra.
Radiative heating rates are calculated as described in Khvorostyanov (1995), Khvorostyanov and
Sassen (1998a,b; 2002), and Khvorostyanov et al. (2001) using the two-stream approximations for
longwave (LW) and shortwave (SW) radiative transfer with parameterizations of the absorption and
scattering coefficients depending on the droplet size spectra (see Section 2.5). The input variables
were consistent with the observed arctic stratus clouds from Fig. 13.1. Calculated profiles of radia-
tive heating rates presented in Fig. 13.2 show maximum longwave cooling of −120 K day−1 and solar
heating of ∼40 K day−1, which is in a good agreement with those determined from measurements of
this cloud deck (Herman and Curry, 1984; Curry, 1986).
Corresponding radiative-effective vertical velocities (Fig. 13.3) calculated with (Eqn. 13.8.7)
exhibit strong maxima at heights 50–100 m below the cloud top, equivalent to updrafts of 5−8 cm s−1
for the longwave cooling and downdrafts of −3 cm s−1 for solar heating. These wrad almost vanish in
the lower half of the cloud, where the dynamic velocity plays the major role. The value of parameter
as (Fig. 13.1) shows a strong maximum near the cloud base, sharply decreases upward in the lowest
50 m of the cloud, and then continues to decrease much more slowly until it reaches zero at a height
of 1,000 m, and becomes negative above this level.
The values of parameter ms calculated from (Eqn. 13.6.10a) and shown in Fig. 13.4 exhibit a
monotonic increase upward from about 0.2–0.6 near the cloud bottom to values ms = 4–5.5 within
200–300 m above the cloud base, with values of ms significantly increasing above 900 m where radi-
ative-effective velocities and their gradients increase.

1200

1100
LW SW
Total
1000
Height (m)

900 LW

SW

800 Total

700
–120 –100 –80 –60 –40 –20 0 20 40
Radiative heating (K/day)

Figure 13.2. Vertical profiles of longwave (LW), shortwave (SW), and total (Total) radiative heating
rates for the cloud shown in Fig. 13.1. From Khvorostyanov and Curry (1999d). J. Atmos. Sci., 56,
© American Meteorological Society. Used with permission.
658 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

1100

1050
wef
1000 wrad

950

Height (m)
900

850

800 wrad
weff = wrad + wdyn
750

700
–3 0 3 6 9 12 15 18 21 24
Radiative and effective vertical velocities (cm s–1)

Figure 13.3. Vertical profiles of the “effective radiative” vertical velocities wrad = wlong + wshort
calculated with (Eqn. 13.8.7) for the cloud shown in Figs. 13.1 and 13.2 that accounts for both
longwave and shortwave cooling/ heating, and the total effective velocity weff = wdyn + wrad,
where wdyn = 10 cm s−1. From Khvorostyanov and Curry (1999d). J. Atmos. Sci., 56, © American
Meteorological Society. Used with permission.

1000

950

900
Height (m)

850

800 rad., w = 1
rad., w = 10
750 norad., w = 15
w = 10, k = 10

700
0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0
Parameter µs

Figure 13.4. Vertical profiles of the parameter ms in the analytical solutions calculated with
(Eqn. 13.6.10a) for four cases: 1) wef = wdyn + wrad; wdyn = 1 cm s−1, and wrad calculated with (Eqn. 13.8.7)
that accounts for longwave cooling only; k = 5 m2 s−1; 2) same as case 1, but wdyn = 10 cm s−1; 3)
same as case 1, but wdyn = 15 cm s−1 and wrad = 0 (norad.); 4) same as case 2, but k = 10 m2 s−1. From
Khvorostyanov and Curry (1999d). J. Atmos. Sci., 56, © American Meteorological Society. Used
with permission.
13.9. Applications of the Solution for Liquid Clouds 659

The indices p evaluated with (Eqn. 13.8.4) for the general solutions (Fig. 13.5) for the case with
wdyn = 1 cm s−1 (synoptic-scale) do not exceed 1–2 in the whole cloud but reach 20 in the thin layer of
maximum radiative cooling and maximum wrad near 1050 m. The values of p for wdyn = 10–15 cm s−1
are much greater and closer to the local observations. They also exhibit an increase from the cloud
bottom with the values 5–15 at the mid-cloud depth, reach maximum values of 20–35 near the maxi-
mum qL, and then decrease upward toward the cloud top. For the cases with wrad > 0, this increase is
especially rapid near the maximum qL where wrad is maximum.
The indices pɶ1 of the gamma distribution for the first solution (Eqn. 13.6.23) (Fig. 13.6) also
increase upward from the cloud bottom but more slowly than the indices p. This is caused by the factor
(1 + ms)/2ms in pɶ1. As discussed in Section 13.6, the asymptotic solutions (Eqn. 13.6.23) with indices pɶ1
are valid only in the lower layer of ∼100–200 m, while the larger indices p (Fig. 13.5) are more
representative of the spectral dispersions in the upper half of the cloud. Smaller values of pɶ1 than
p are in agreement with the measurements in clouds that show wider spectra near the cloud bottom
than in the cloud interior (Table 13.4). It is seen from Figs. 13.5 and 13.6 that values of both p and pɶ1
increase with increasing vertical velocity, indicating smaller sr and narrower spectra, and decrease
with increasing turbulence, indicating greater sr and wider spectra.
An example of the size spectra in the lower part of the cloud calculated with (Eqn. 13.6.23) is pre-
sented in Fig. 13.7. The shape and general behavior of the spectra are in reasonable agreement with
those typically observed in clouds. The calculated size spectra can be compared to those measured on

1100

1050

1000

950
Height (m)

900

850
w = 1, rad
800
w = 10, rad

750 w = 15, no rad

w = 10, k = 10
700
0 5 10 15 20 25 30 35
Index p of gamma distribution

Figure 13.5. Vertical profiles of the indices p of gamma-distributions evaluated with (Eqn. 13.8.4)
for the same four cases as in Fig. 13.4. Hereafter, the values of wdyn and k are shown in the Figures;
“rad” and “no rad” mean calculations with and without an accounting for the radiative velocities
wrad. From Khvorostyanov and Curry (1999d). J. Atmos. Sci., 56, © American Meteorological
Society. Used with permission.
660 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

1000

950

900

Height (m)
850

rad, w = 1
800
rad, w = 10

750 norad, w = 15
w=10, k = 10

700
0 2 4 6 8 10 12 14 16 18 20
Index of gamma-distribution,
1st solution

Figure 13.6. Vertical profiles of the indices pɶ1 of gamma-distributions for the first asymptotic
solution (Eqn. 13.6.23) (2nd boundary asymptotic regime) for the same four cases as in Fig. 13.4.
From Khvorostyanov and Curry (1999d). J. Atmos. Sci., 56, © American Meteorological Society.
Used with permission.

220 wef = 10 cm/s, radiation, k = 5 m2s–1

200
180
Size spectra (cm–3 µm)

160 z = 750m
140
z = 800m
120
z = 850m
100
z = 900m
80
60
40
20
0
0 2 4 6 8 10 12
Droplet radius (µm)

Figure 13.7. Evolution of the droplet size spectra above the cloud base calculated with the first
asymptotic solution (Eqn. 13.6.23) of the 2nd asymptotic regime for the case with wdyn = 10 cm s−1,
wrad as in Fig. 13.2, k = 5 m2 s−1, normalized to the concentration N(z) shown in Fig. 13.1. From
Khvorostyanov and Curry (1999d). J. Atmos. Sci., 56, © American Meteorological Society. Used
with permission.
13.10. Comparison with Previous Theories and Observations 661

28 June 1980 in stratus (Herman and Curry, 1984, Table 2). There were five aircraft passes through
this cloud deck at various altitudes. Although the measured spectra are slightly different at vari-
ous times, they exhibit some common features. The calculated spectra shown in Fig. 13.7 generally
reproduce the shape of the measured spectra: a) the fast increase of f(r) in the region from 0 to
1–2 μm caused by the high value p ∼ 5–10; b) the slower exponential tail; c) the displacement of the
maximum to the lager radii with height; d) the simultaneous decrease of the relative dispersion sr
upward (see Table 13.4 for the measured sr and Figs. 13.8 and 13.9 for calculated sr). The feature
of bimodality in some of the measured spectra is not reproduced in Fig. 13.7, as only one mode of
the analytical solutions was accounted for. This bimodality may probably be caused by the mixing
with the entrained dry air from above, and can be reproduced in this model by using a superposition
of the solutions (Eqn. 13.8.9a) with the two exponents bs,1,2 in (Eqn. 13.8.9) with appropriate mixing
time tm.

13.10. Comparison with Previous Theories and Observations

The theory of stochastic condensation and the stochastic kinetic equations have been criticized by
Warner (1969b), and Bartlett and Jonas (1972), who modeled the impact of turbulence on the size
spectrum with random fluctuations of the vertical velocity in a cloud parcel using Lagrangian parcel
models without exchange with environment. They found that turbulence modelled with such an iso-
lated cloud parcel is unable to account for the observed drop size broadening. Criticisms by Mazin
and Smirnov (1969) of the theory of stochastic condensation were also based on the concept of an
adiabatic parcel ascent. This criticism was answered by Stepanov (1975), Voloschuk and Sedunov
(1977), and Manton (1979), who noted that the kinetic equation under some conditions does not
cause further broadening of the spectra with time if mixing among the parcels is absent. We consider
in this section in more detail the correspondence between the approach based on the kinetic equation
and the Lagrangian parcel models. It will be shown that there is no contradiction between these two
approaches and that Warner (1969b) and Bartlett and Jonas (1972) considered a particular case of
stochastic condensation.
As we see from the low-frequency form of the stochastic kinetic (Eqn. 13.4.5), the effect of tur-
bulence vanishes when the right-hand side of the equation is zero, and (Eqn. 13.4.5) converts into
the equation of regular condensation (Eqn. 13.2.1). The right-hand side of (Eqn. 13.4.5) can be zero
if either
kij = 0 (13.10.1)
or

 ∂ ∂
 + Gs  f s = 0 (13.10.2)
∂z ∂r 

Thus, the condition (Eqn. 13.10.2) can be regarded as equivalent to the condition of zero turbulence
(Eqn. 13.10.1). Equation (13.10.2) can then be rewritten as
∂ fs ∂f
= − Gs s . (13.10.3)
∂z ∂r
662 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

Multiplying (Eqn. 13.10.3) by (4π /3) ρ w r 3 and integrating, we obtain:

∞
dqL 4π ∂f
=− ρ w Gs ∫ r 3 dr = 4π Gs ρ w N r 2 ≈ 4π Gs ρ w N r 2 , (13.10.4)
dz 3 0
∂ r

where qL is the LWC. The last approximate relation is based on the fact that r 2 is usually only slightly
(by 10–20%) larger than r 2. To interpret (Eqn. 13.10.4), we express Gs in terms of the vertical gradi-
ent of the adiabatic liquid water mixing ratio defined by (Eqn. 13.8.2) using the first of the expres-
sions (Eqn. 13.8.3):
ρa 1  dqls 
Gs =   , (13.10.5)
ρ w 4π N r 2  dz  ad

where qls is the water mixing ratio. This equation shows that the parameter Gs relates the vertical gradi-
ent of the adiabatic liquid water mixing ratio to the effective area of the droplets per unit volume—that
is, Gs characterizes the rate of absorption by the droplets of vapor excess released during adiabatic
lifting. Substituting (Eqn. 13.10.5) for Gs into (Eqn. 13.10.4), we obtain the following relation:
dqL ρ 1  dqls   dqls 
≈ 4πρ w N r 2 a   = ρ a   . (13.10.6)
dz ρ w 4π N r 2  dz  ad dz  ad

Equation (13.10.6) shows that the condition (Eqn. 13.10.2) corresponds to the adiabatic gradient of
the mixing ratio, or, as shown by (Eqns. 13.10.1) and (13.10.2), this is equivalent to kij = 0—i.e., to
the absence of turbulence and mixing among the parcels. So, we see that turbulence does not influ-
ence the drop size spectrum if the vertical profile of qL corresponds to the adiabatic value.
In the simulations made by Warner (1969b) and Bartlett and Jonas (1972) using Lagrangian parcel
models, moist adiabatic ascents were assumed and adiabatic liquid water contents were derived.
Vertical velocity fluctuations in these adiabatic parcel simulations led only to the reversible changes
in the cloud properties, when the updraft causes an increase in the mean radius and qL, and the down-
draft removes the effects of a previous updraft. The major source of spectral broadening—vertical
inhomogeneity and vertical turbulent exchange of the parcels with different spectra—is absent in the
modeling with isolated parcels. Therefore, only a small broadening of the spectra was obtained in
these parcel model simulations, probably due to the numerical diffusion.
As shown earlier, the kinetic equation of stochastic condensation leads in this wet adiabatic situa-
tion to the same results, absence of turbulent stochastic effects, and does not cause broadening of the
spectra. Hence, there is no contradiction between the treatment of the stochastic condensation pro-
cess as described here and the Lagrangian parcel models, which correspond to the adiabatic condition
(Eqn. 13.10.2) and are equivalent to the absence of turbulence (Eqn. 13.10.1). These conditions along
with the physical meaning of parameter Gs described by (Eqn. 13.10.5), mean that any vertical dis-
placement in the cloud is accompanied by a change in the drop size spectrum. Displacements of par-
cels in regions of the clouds that have adiabatic liquid water profiles will not lead to the broadening
of the drop spectra. The droplet radius will be a function of the height and the cloud will be in some
equilibrium state. However, liquid water content in a cloud is typically much less than its adiabatic
value, and the gradient dqL/dz is different from the wet adiabatic profile (see Fig. 13.1) and the condi-
tion (Eqn. 13.10.6) is not satisfied. This departure of the cloud liquid water content from the adiabatic
profile increasing upward will result in the evolution of the size spectra according to the kinetic equa-
tion of stochastic condensation. Since the adiabatic ratio cad = qL /qL,ad usually decreases upward, the
13.10. Comparison with Previous Theories and Observations 663

applicability of the parcel models without entrainment and with adiabatic gradients becomes more
limited with increasing height above the cloud base.
Another good confirmation of the fact that the adiabatic LWC or IWC profiles in clouds effect the
size spectra in a way equivalent to the absence of turbulence, k = 0, was described in Liu and Hallett
(1998), who found very narrow size spectra in a lenticular cloud over the Sierra Nevada formed
adiabatically in a laminar flow.
Considine and Curry (1996) used a simple statistical model to derive drop size spectra that have
the shape of a modified gamma distribution. As such, the p-index is not directly comparable to the
drop size spectra developed here. However, the parameters of Considine and Curry’s drop size distri-
bution are vertical velocity variance, temperature, pressure, the lapse rate in the cloud, and the lapse
rate of a rising parcel. These parameters include essentially the same meteorological variables used
in the drop size spectra developed here. Considine and Curry’s results implied that if the lapse rate
within the cloud is equal to the saturated adiabatic lapse rate, then the spectrum becomes infinitely
narrow, approaching a monomodal distribution. This is consistent with the result that a cloud with
adiabatic liquid water content will have a narrow spectrum and the spectrum will not be influenced
by turbulent motions. Considine and Curry also found that the drop size spectra broaden as the ver-
tical velocity variance increases, which is consistent with the results described here. This general
agreement with Considine and Curry supports some of the assumptions used in their derivation. The
present derivation provides a theoretical justification for some of these assumptions.
One of the most important quantities that characterizes the effect of turbulence on the size spectra
is the relative dispersion sr = (1 + p)−1/2. Its vertical profiles calculated with the values of pɶ1 from
Fig. 13.6 are given in Fig. 13.8 for the four cases considered earlier. The dispersion for the cases

1100
w = 1, rad
1050 w = 10, rad
w = 15, no rad
1000
w = 10, k = 10

950
Height (m)

900

850

800

750

700
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Relative dispersion of spectra (via p1)

Figure 13.8. Vertical profiles of the relative dispersions of the size spectra for the first asymptotic
solution (Eqn. 13.6.23) of the 2nd asymptotic regime for the same four cases as in Fig. 13.4
calculated with indices pɶ1 defined by (Eqn. 13.6.23) and shown in Fig. 13.6. From Khvorostyanov
and Curry (1999d). J. Atmos. Sci., 56, © American Meteorological Society. Used with permission.
664 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

with wdyn = 10 − 15 cm s−1 decreases from 0.45–0.6 above the cloud base to 0.3–0.4; that is, the size
spectra in low stratus are narrowing with the height above the cloud base. These values are in good
agreement with many observations, but the dispersions with small wdyn = 1 cm s−1 are 0.55–0.85,
much larger than those observed locally. Note that the effect of the decrease of sr upward is opposite
to that observed above the base in convective clouds where dispersions increase upward (Warner,
1969a); however, it is in good agreement with the observation in stratus clouds (Noonkester, 1984;
Curry, 1986) and in the upper halves of some convective clouds (e.g., Austin et al., 1985). The data
from Table 13.4 show that the relative dispersions have maxima near the cloud’s top and bottom and a
minimum in the middle of the cloud, near the maximum of qL. The calculated values of sr are similar
to the measured values shown in Table 13.4.
The indices pɶ1 corresponding to the asymptotic solution (Eqn. 13.6.23) characterize the breadth
of the size spectra only in the lower layer, while the indices p can serve as a measure of the spectral
breadth in the whole cloud. The dispersions calculated with the indices p from Fig. 13.5 are shown in
Fig. 13.9. These dispersions exhibit minima of 0.2–0.3 near maximum values of qL, and asymmetry
of sr in vertical direction with larger dispersions near the base than in the upper layer, which is in
agreement with observations shown in Table 13.4.
Hence, the analytical solutions derived in Section 13.6 provide an explanation of the observed
dispersions in clouds along with their possible different behavior with height. We emphasize that
these are only approximate estimations of the dispersions based on several simplifications. The more
accurate evaluation of sr should be based on the numerical solution of the complete kinetic equation,
with more realistic accounting for the profiles of k(z), gradients ∂f/∂z, and others.

1100

1050 w = 1, rad
w = 10, rad
1000
w = 15, norad
950 w = 10, k = 10
Height (m)

900

850

800

750

700
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Relative dispersion of spectra (via p)

Figure 13.9. Vertical profiles of the relative dispersions of the size spectra for the same four cases
as in Fig. 13.4 calculated with indices p defined by (Eqn. 13.8.4) and shown in Fig. 13.5. From
Khvorostyanov and Curry (1999d). J. Atmos. Sci., 56, © American Meteorological Society. Used
with permission.
13.11. Calculation of Size Spectra for a Crystalline Cloud 665

The technique described here can be used to study covariances of moments of the distribution
function with various quantities, as was done based on observations by Curry (1986). The simplest
is the covariance of liquid water content, qL, with vertical velocity. Using (Eqn. 13.3.13) for ui′ f ′ in
the low-frequency approximation ( kijn = kij ) and the assumption of horizontal homogeneity (only the
term ∂/∂z is kept), multiplying it by (4π /3) ρ w r 3 and integrating over radii, we obtain
∞ ∞
4 4   ∂f ∂f 
qL′ u3′ = w ∫ r 3 u3′ f ′dr = w ∫ r 3 − k  + Gs   dr
3 0
3 0   ∂ z ∂r  
∞
∂qL 4 ∂f
= −k −k w Gs ∫ r 3 dr . (13.10.7)
∂z 3 0
∂r

The last integral in (Eqn. 13.10.7) is evaluated by integration by parts and is equal to −3 N r 2 ≈ −3 N r 2 .
Including the first expression (Eqn. 13.8.3) for Gs, the covariance (Eqn. 13.10.7) is written as

  dq   dqL  
qL′ u3′ = k  ρ a  ls  −   . (13.10.8)
  dz  ad dz  

The expression (Eqn. 13.10.8) shows that covariance of qL with vertical velocity should be positive
for the cases when the vertical gradient of qL is smaller than the adiabatic gradient of qL, and is nega-
tive for the reverse situation. The first situation is met almost always, which causes a positive correla-
tion. In particular, this positive correlation of qL′ and the vertical velocity fluctuations was described
by Curry (1986) based on observations in arctic stratus (see Fig. 13.1), which means that vertical
gradients of qL were less than adiabatic, in accord with the present theory.

13.11. Calculation of Size Spectra for a Crystalline Cloud

Presented in this section are the results of calculations of the size spectra and their parameters for a
crystalline cloud similar to those for liquid clouds described in Section 13.9. Calculations are per-
formed using four different input profiles. The baseline profiles approximate a two-layer cloud of
cirrus and nimbostratus observed on July 8, 1998, in the Surface Heat Budget of the Arctic Project
(SHEBA) and the First International Satellite Cloud Climatology Project (ISCCP) Regional Experi-
ment (FIRE) field campaign in the Arctic. The vertical profiles were chosen close to observations
simulated with the spectral bin microphysics model in Khvorostyanov, Curry, et al. (2001). The cloud
shown in Fig. 13.10 is pure crystalline, the small fraction exists in the region between 4 and 10 km
with maximum IWC qL = 20 mg m−3 at 7 km, maximum crystal concentration Ni ∼ 90 L−1 at 9 km, and
the mean crystal radius r increases downward from 30 μm near the cloud top to about 90 μm at the
bottom. The following vertical profile of ice supersaturation is assumed: constant negative values s =
−15% from 3 to 7.2 km, increasing from 0 at 7.5 km to a maximum of 12% at 9 km and then decreas-
ing to −80% at 12 km (Fig. 13.10c). This design of s is consistent with observations (e.g., Jensen et al.,
2001) and detailed simulations of this and similar clouds using a model with spectral bin microphysics
and the supersaturation equation in Khvorostyanov, Curry, et al. (2001) and Khvorostyanov and Sas-
sen (1998a,b, 2002), which showed that the maximum IWC in cirrus can be located near s = 0 since
IWC increases downward in all the layers with s > 0 as crystals formed aloft grow and precipitate.
666 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

12 Base 12
11 2 IWC 11
10 2R 10

Height (km)
Height (km)
9 2K 9
8 8
7 7 Base
6 6 2IWC
5 5 2R
4 4 2K
3 3
0 5 10 15 20 25 30 35 40 45 0 25 50 75 100
IWC (mg m–3) Crystal concentration (L–1)
(a) (b)

12 12
11 11
10 10

Height (km)
Height (km)

9 9
8 8
7 7
6 6
5 5
4 4
3 3
–80 –70 –60 –50 –40 –30 –20 –10 0 10 20 –3 –2 –1 0 1 2
Ice supersaturation (%) αs (km–1)
(c) (d)

Figure 13.10. Vertical profiles of the input parameters for the four different cases with crystalline
clouds indicated in the legend and described in the text (a) ice water content, mg m−3; (b) crystal
concentration, L−1; (c) ice supersaturation, %; (d) the parameter αs, km−1. From Khvorostyanov and
Curry (2008b). J. Atmos. Sci., 65, © American Meteorological Society. Used with permission.

Maxima in s and Ni may coincide, reflecting the mechanism of ice nucleation governed by supersatu-
ration (see Chapters 8–10). The values of as calculated from (Eqn. 13.5.8) are positive below the level
of maximum IWC and are negative above, with extremes of about ±2 km−1 (Fig. 13.10d). We used the
constant values of wef = 3 cm s−1 and k = 5 m2 s−1. These profiles are referred hereafter as the baseline
(case 1) and denoted in the legends as “Base.” To test the sensitivity of the results to the input profiles,
the same calculations were performed with the following changes: doubled IWC and r (case 2);
same IWC as in the baseline case but doubled r (case 3); and same conditions as in the baseline case
but with doubled k (case 4).
Profiles of the parameter Gs calculated with (Eqn. 13.8.1) and these input data are shown in
Fig. 13.11a. The values of Gs reach a maximum ∼10−5 near the cloud base, reach a minimum of
(1–2) × 10−7 at a height of 9 km (coincident with maxima in Ni) and again increase upward. In case
3 (doubled r ), Gs is twice as large since Gs ~ r . Note that the r dependence of Gs results in much
greater values of Gs for ice clouds than for liquid clouds (compare with Section 13.9, Table 13.1).
Cases 2 and 4 both show the same values of Gs as in the baseline case since in case 2 the increase in
13.11. Calculation of Size Spectra for a Crystalline Cloud 667

12
12
11
11
10 Base 10
9
Height (km)

2IWC

Height (km)
9
8 2R 8
7 2K 7
6 Base
6
2IWC
5 5 2R
4 4 2K
3 3
1E–7 1E–6 1E–5 1E–4 –12 –9 –6 –3 0 3 6 9 12 15
Parameter G Index p
(a) (b)

Figure 13.11. Profiles of the parameter Gs (a) and (b) the index p of the crystal size spectra. From
Khvorostyanov and Curry (2008b). J. Atmos. Sci., 65, © American Meteorological Society. Used
with permission.

IWC is compensated in (Eqn. 13.8.1) by an increase in r , and the same value in case 4 is because Gs
does not depend on k.
Corresponding profiles of the index p calculated from the first of expressions (Eqn. 13.8.4) with
cnn = 1 are shown in Fig. 13.11b. In the baseline case, the values of p are negative, and increase from
−9 to 0 in the cloud evaporation layer with s < 0 below 7 km since p ∼ s. At the height ∼ 4 km, p → 0
since p ∼ Ni according to (Eqn. 13.8.5) and Ni → 0. In the crystal growth layer with s > 0, values of
p are positive, ranging from 0 to 13. These variations in p are caused by simultaneous variations in
s and Gs. As discussed in Section 13.8, the values of p for this cirrus cloud are comparable to those
in the liquid Arctic St cloud considered in Curry (1986), since larger Gs in Ci are compensated for in
(Eqn. 13.8.4) by larger r .
The values of p decrease by a factor of 2 with doubled k (case 4, asterisks) since p ∼ k−1; this causes
an increase in relative dispersions sr according to (Eqn. 13.8.6) and reflects the effect of stochastic
condensation as increasing turbulence broadens the spectra. The values of p decrease by a factor of
4 with doubled r (crosses) since p ∼ Gs−2, which is also an effect of stochastic condensation. As
follows from the stochastic kinetic equations and discussed in Sections 13.4–13.8, the diffusion coef-
ficient in radii-space is kr = cnn Gs2k, so that an increase in k causes an increase in kr, which accelerates
diffusion in radii space and leads to broader spectra.
Shown in Fig. 13.12 are the slopes bs calculated from (Eqn. 13.7.3) in the upper layer with ice
supersaturation at heights 7.5–8.7 km and in the lower layer at heights 4.8–6.0 km with s < 0. The
common feature in both layers is a substantial increase of the slopes with increasing radius, which
arises from the dominance of the second term with the fall velocity v(r) in (Eqn. 13.7.3) that tends
to the limit (Eqn. 13.7.7). In the upper layer, the slopes decrease downward causing spectral broad-
ening, which agrees with observations. This is caused by dominance of the terms with as, and a
decrease of |as| downward, toward the level with s = 0. Broadening of the spectra downward—i.e.,
with increasing temperature, also agrees with the observed temperature dependence of the spectra
as discussed in Section 13.8. In the lower layer, the values of bs2 are much smaller due to smaller as
(see Fig. 13.10d) and increase downward. The last feature would cause an incorrect narrowing of
668 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

1E+5 7.5 km 2E+4 4.8 km

S>0 S<0
7.8 km 5.1 km
8.1 km 2E+4

Slope βs2 (cm–2 )

Slope βs2 (cm–2 ) 8E+4 5.4 km
8.4 km 5.7 km
8.7 km 1E+4
6.0 km
6E+4
8E+3
4E+4
4E+3

2E+4 0E+0
0 100 200 300 0 100 200 300
Crystal radius (µm) Crystal radius (µm)
(a) (b)

Figure 13.12. Slopes bs of the crystal size spectra calculated from (Eqn. 13.7.3) at various
altitudes in the layers with: (a) ice supersaturation and (b) subsaturation. The heights in km are
indicated in the legends. From Khvorostyanov and Curry (2008b). J. Atmos. Sci., 65, © American
Meteorological Society. Used with permission.

the spectra downward, but it is overwhelmed by the effect of the negative indices p in this layer as
described in the following text.
Fig. 13.13 depicts size spectra fs(r) calculated with input profiles from the baseline case. The left
panels (a, c) show the tails of the spectra calculated from (Eqn. 13.7.4), and the right panels (b, d)
show the composite spectra (Eqn. 13.7.5) with multiplication by r pΦ(r) and Φ(r) from (Eqn. 13.7.6).
One can see that in the upper ice supersaturated layer with p > 0, the spectra resemble typical gamma
distributions. Addition of the factor r pΦ(r) allows extension of the spectra to the small radii region
but does not cause a substantial change of the spectra.
The situation is different in the lower ice subsaturated layer with p < 0. Without the factor r pΦ(r),
the small size region up to 100 μm in double log coordinates represents parallel straight lines with
positive slopes caused by the factor r before the exponent in (Eqn. 13.7.4) (recall, the solution
(Eqn. 13.7.4), fs ∼ rexp(−ar2), is typical for some previous theories of stochastic condensation with
p = 1). With multiplication by r pΦ(r) in (Eqn. 13.7.5), the spectra become inverse power laws up to
r ∼ 40−50 μm, the slopes (indices p) increase with height (i.e., with decreasing temperature), and the
spectra show bimodality with secondary maxima at r = 100−150 μm (Fig. 13.13d). Such bimodal
behavior is often observed in crystalline clouds and parameterized with superposition of the two
inverse power laws or gamma distributions that correspond to the two size fractions (e.g., Heymsfield
and Platt, 1984; Mitchell et al. 1996; Platt, 1997, Ryan, 2000). Equation (13.7.5) and Fig. 13.13d
show that this bimodality may occur within the small-size fraction: the left branch (inverse power
law) is a result of stochastic and regular condensation, while the tail is dominated by the interaction
of regular condensation, turbulent and convective transport, and sedimentation. A comparison with
experimental data shows that these calculated spectra well describe the typical features of the crystal
spectra measured in cirrus clouds and addition of the large fraction may cause multimodality. These
results illustrate applicability of this theory of stochastic condensation for crystalline clouds.
13.12. Derivation of the Generalized Stochastic Kinetic Equations 669

7.5 km 1E+1

Crystal size spectra (L–1 µm–1)

1E+1
Crystal size spectra (L–1 µm–1) 7.8 km
7.5 km
7.8 km
8.1 km 8.1 km
1E+0 8.4 km 1E+0
8.4 km
8.7 km 8.7 km
1E–1 1E–1

1E–2 1E–2

1E–3 1E–3
0 50 100 150 200 0 50 100 150 200
Crystal radius (µm) Crystal radius (µm)
(a) (b)

1E+1 1E+2
Crystal size spectra (L–1 µm–1)
Crystal size spectra (L–1 µm–1)

1E+0 1E+1

1E+0
1E–1
1E–1
4.8 km 4.8 km
1E–2
5.1 km 5.1 km
1E–2
5.4 km 5.4 km
1E–3 5.7 km
5.7 km 1E–3
6.0 km 6.0 km
1E–4 1E–4
1 10 100 1 10 100
Crystal radius (µm) Crystal radius (µm)
(c) (d)

Figure 13.13. Crystal size spectra calculated for the baseline case at the heights indicated in the
legends. (a) supersaturated layer using (Eqn. 13.7.4) for the tail; (b) supersaturated layer using
(Eqn. 13.7.5) for the composite spectra with multiplication by r pΦ(r); (c) subsaturated layer using
(Eqn. 13.7.4) for the tail; (d) subsaturated layer using (Eqn. 13.7.5) for the composite spectra with
multiplication by r pΦ(r). The temperature falls by ∼8 °C from the lower to the upper height of each
layer. From Khvorostyanov and Curry (2008b). J. Atmos. Sci., 65, © American Meteorological
Society. Used with permission.

13.12. Derivation of the Generalized Stochastic Kinetic Equations

from the Fokker–Planck Equation
13.12.1. Chapman–Kolmogorov and Fokker–Planck Equations

The kinetic equations of condensation and coagulation represent particular cases of the more general
Fokker–Planck equation, which itself is a particular case of a more general Chapman–Kolmogorov
equation (the history of these equations, detailed formulations, and bibliography can be found in
Risken, 1989; van Kampen, 1992; and Rodean, 1996). In this section, we consider derivation of the
670 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

generalized kinetic equation of condensation and coagulation that is a modification of the Chapman–
Kolmogorov equation adapted for the size spectra, and derivation of the Fokker–Planck kinetic equa-
tions. This outlines the general approach to derivation of stochastic kinetic equations for the size
spectra, allows us to establish relationships among various versions of the kinetic equations and
possible ways to generalize them.
When random processes occur in a medium, the kinetic equation contains diffusion terms. In many
fundamental derivations and applications, diffusion processes are described using the Fokker–Planck
equation for the distribution function by various variables, which form a phase space, and the Fokker–
Planck equation is a model of diffusion in this phase space (Rodean, 1996; Lifshitz and Pitaevskii,
1997). The diffusion terms are different for various processes and can be derived from this equa-
tion, as, for example, for Brownian diffusion (Levich, 1969), the mixing of gases and plasma theory
(Lifshitz and Pitaevskii, 1997), and turbulent diffusion (Obukhov, 1959; van Kampen, 1992; Rodean,
1996). Here we apply the Fokker–Planck equation to derive a generalized stochastic kinetic equation
for the cloud drops and crystals.
The Fokker–Planck equation can be derived from the more general Chapman–Kolmogorov equa-
tion, which is an integral equation that describes the evolution of the probability Pp(y1, t) of the
system to be in a state y1 at a time t if the probability of transition from y1 to y2 is W(y2, y1) and the
probability of a reverse transition from y2 to y1 is W(y1, y2). The Chapman–Kolmogorov equation is
applied to Markov processes, which is defined by two conditions (e.g., van Kampen, 1992; Rodean,
1996): 1) the present state y1 can have its origin in any of the probable states y2 in the past; 2) a
process starting at time t1 from a value y1 reaches a value y3 at time t3 by passing any intermediate
possible values of y2 at time t2. The Chapman–Kolmogorov equation can be written as (van Kampen,
1992; Rodean, 1996)
∂ Pp ( y1 , t )
= ∫ [W ( y1| y2 ) Pp( y2 , t ) − W ( y2 | y1 ) Pp ( y1 , t )]dy2 . (13.12.1a)
∂t

We consider a spatially inhomogeneous cloud where the size distribution function, f ( x , r , t ), depends

on time, the coordinate vector with three components, x ( xα ), with a = 1, 2, 3, and the particle radius r.
Then, in the spirit of the Fokker–Planck equation, (xa , r) are the parameters of a medium and form
a 4-dimensional phase space (xa , r). We consider the evolution of f due to the random processes that

cause transitions ( x − x ′, r − r ′ ) → ( x , r )—that is, changes in (xa , r) by some “jumps” (xa′, r ′). The

probability of transition, Wxr ( x − x ′, r − r ′ | x ′, r ′ ) , depends on the initial coordinates ( x − x ′, r − r ′)

and on the values of the jumps ( x ′, r ′ ).
The major assumptions usually made in derivations of the Fokker–Planck equation are: 1) the
evolution of f is sufficiently slow—that is, its relaxation time tf is much greater than the char-
acteristic time tran of the random processes that cause these changes in xa , r; 2) the probability

Wxr ( x − x ′, r − r ′ | x ′, r ′ ) decreases with increasing jumps (xa − xa′, r − r ′)—i.e., the probability of
a large jump (xa − xa′, r − r ′) is small, and the evolution of f proceeds via small jumps in (xa , r)
space. There are two equivalent types of derivation of the Fokker–Planck equation used in the
literature: from the differential and integral forms of the Chapman–Kolmogorov equation. First,
we present a brief derivation based on the differential form and then will illustrate application of
the integral form.
13.12. Derivation of the Generalized Stochastic Kinetic Equations 671

Strictly speaking, the Chapman–Kolmogorov equation is defined for the probabilities of the
states, but we will slightly modify it for the size distribution functions. If we consider evolution

of the drop or crystal size spectra, then we can define the state y1 as ( x , r ) in the four-dimensional

space. Since the size distribution function f ( x , r ) is defined as proportional to the probability to
find a particle in the radii range (r, r + dr), and f is normalized to the particle concentration N, the

probability Pp(y1, t) of this state is determined as, Pp ( x , r ) = f ( x , r ) /N. The state y2 is ( x − x ′, r − r ′ ),

its probability is Pp ( y2 , t ) = f ( x − x ′, r − r ′, t )/N, and the probability W ( y2|y1 ) of the jumps ( x ′, r ′)

can be defined as the product of the probability of transition Wxr ( x − x ′, r − r ′ | x ′, r ′) by the

probability of the initial state. Since the probability of this state ( x ′, r ′) is ~ f ( x ′, r ′, t ), we can

write W ( y2 | y1 ) = Wxr ( x − x ′, r − r ′ | x ′, r ′ ) f ( x ′, r ′, t ). This probability determines the gain of the

particles. The probability of transition from the state ( x ′, r ′) into the state ( x , r ) is W ( y1 | y2 ) = W ( ′

y ) = Wxr ( x , r | x ′, r ′) f ( x ′, r ′, t ), as the probability of the initial state is f ( x ′, r ′, t ) /N. For Markov’s process,

the probabilities of a transition from an initial state ( x − x ′, r − r ′ ) to a final state ( x , r ) should not

depend on the intermediate states, therefore integration over (dx ′dr ′) should be performed.
Then, we can write an analog of the Chapman–Kolmogorov (Eqn. 13.12.1a) in this 4-dimensional
phase space as the stochastic kinetic equation for the size spectra,

∂ f (x ,r,t)
= ∫ Wxr ( x − x ′, r − r ′ | x ′, r ′) f ( x − x ′, r − r ′, t ) f ( x ′, r ′, t ) dx ′dr ′
∂t

− f ( x , r , t ) ∫ Wxr ( x , r | x ′, r ′) f ( x ′, r ′, t ) dx ′dr ′. (13.12.1b)

Here, the first and second terms on the right-hand side represent the gain and loss of the particles per

unit time in an element of the 4D phase space, Wxr ( x − x ′, r − r ′ | x ′, r ′ ) determines the probability of

transition between the points ( x − x ′, r − r ′ ) and ( x , r ) with the jumps ( x ′, r ′ ) in the 4D phase space
(denoted by the subscript “xr”), and Wxr, according to assumption (2) earlier, sufficiently rapidly
decreases with increasing distance between these points.
The differences of this generalized stochastic kinetic (Eqn. 13.12.1b) with the original Chapman–
Kolmogorov (CK) (Eqn. 13.12.1a) are the following. The CK (Eqn. 13.12.1a) is linear by the prob-
abilities of the states, and the kinetic (Eqn. 13.12.1b) is nonlinear by the function f. The probabilities
of transition W ( y2| y1 ) in the CK equation are defined per unit time, [s−1], while the probabilities Wxr
of the transition in the kinetic equation are defined per unit time and per unit volume, [cm3 s−1]—i.e.,
their dimension coincides with the dimension of the coagulation kernels in the Smoluchowski-Müller
equation.
The generalized stochastic kinetic (Eqn. 13.12.1b), which is a modification of the Chapman–
Kolmogorov equation, has a simple form and clear physical meaning and contains in a generalized
form a wealth of the physical situations with particle transformations. It is shown in this section
that the integral kinetic (Eqn. 13.12.1b) can serve for derivation of the differential Fokker–Planck
equation in various forms—in particular, of various stochastic condensation equations considered
earlier in this chapter. This is achieved by specifying various transition probabilities Wxr. Besides,
one can see that the kinetic (Eqn. 13.12.1b) describes evolution of the size spectra due to the balance
between the gain and loss in a random process and therefore can be viewed as a generalization of the
Smoluchowski–Müller coagulation equation considered in Chapter 5.
672 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

We begin derivation of the Fokker–Planck equation for the size spectra with the generalized sto-
chastic kinetic (Eqn. 13.12.1b). With the assumption of small jumps in the 4-dimensional space (xa , r),
the subintegral expressions in (Eqn. 13.12.1b) can be expanded into the Taylor series by x′a , r′ from
the zeroth through the second order:

Wxr ( x − x ′, r − r ′ | x ′, r ′ ) f ( x − x ′, r − r ′, t ) ≈ Wxr ( x , r | x ′, r ′) f ( x , r , t )
∂ ∂
− xα′ Wxr ( x , r | x ′,r ′ ) f ( x , r , t )  − r ′ Wxr ( x , r | x ′,r ′ ) f ( x , r , t ) 
∂ xα  ∂r
1 ∂2 1 ∂2
+ xα′ x β′ Wxr ( x , r | x ′,r ′ ) f ( x , r , t )  + xα′ r ′ Wxr ( x , r | x ′, r ′) f ( x , r , t ) 
2 ∂ xα ∂ x β 2 ∂ xα ∂r
1 ∂2 1 ∂2
+ r ′xα′ Wxr ( x , r | x ′,r ′ ) f ( x , r , t )  + r ′ 2 2 Wxr ( x , r | x ′,r ′ ) f ( x , r , t )  . (13.12.2)
2 ∂r ∂ xα 2 ∂r

The summation rule is assumed over the doubled Greek subscripts, a, b = 1, 2, 3. Substituting the
expansion (Eqn. 13.12.2) into (Eqn. 13.12.1b) and rearranging the terms yields a differential kinetic
equation:

∂ f (x , r, t) ∂ ∂ ∂2
=− ( vα f ) − (rf
ɺ )+ ( kαβ f )
∂t ∂ xα ∂r ∂ xα ∂ x β
∂2 ∂2 ∂2
+ ( kα r f ) + ( krα f ) + 2 ( krr f ). (13.12.3)
∂ xα ∂ r ∂r ∂ xα ∂r

The arguments ( x , r ) of f and of coefficients on the right-hand side are omitted for brevity. We intro-
duced here the velocities va in the 3D coordinate space and the velocity rɺ in the radii space:

vα = ∫ xα′ Wxr ( x , r | x ′, r ′) dx ′dr ′ (13.12.4)

rɺ( x , r ) = ∫ r ′Wxr ( x , r | x ′, r ′ ) dx ′dr ′, (13.12.5)

and the turbulence coefficient tensor

1
kαβ ( x , r ) = ∫ xα′ x β′ Wxr ( x , r | x ′, r ′) dx ′dr ′, (13.12.6)
2
1
kα r ( x , r ) = ∫ xα′ r ′ Wxr ( x , r | x ′, r ′) d x ′dr ′, (13.12.7)
2
1
krr ( x , r ) = ∫ r ′ 2Wxr ( x , r | x ′, r ′) d x ′dr ′. (13.12.8)
2
The components kab in (Eqn. 13.12.6) are the components of the spatial turbulent diffusion ten-
sor, kar in (Eqn. 13.12.7) are the components of the mixed coordinate-radius tensor, and krr in
(Eqn. 13.12.8) are the components of the diffusion coefficient in the space of radii. The kinetic (Eqn.
13.12.3) with velocities (Eqns. 13.12.4)–(13.12.5) and turbulent diffusion tensors (Eqns. 13.12.6)–
(13.12.8) includes many various models of condensation or deposition in a turbulent atmosphere.
The specifics and physics of every model are determined by the form of Wxr, as will be shown in
the following text.
13.12. Derivation of the Generalized Stochastic Kinetic Equations 673

If particles are described by the mass distribution function, and probabilities W describe transi-

tions between the states ( x − x ′, m − m ′ ) and ( x ′, m ′ ) in the 4D phase space, then the Chapman–
Kolmogorov equation can be written as in (Eqn. 13.12.3) replacing r → m, and so the expansion into
the power series and substitution into the Chapman–Kolmogorov equation yields

∂ f ( x , m, t ) ∂ ∂ ∂2
=− ( vα f ) − (mf
ɺ )+ ( kαβ f )
∂t ∂ xα ∂r ∂ xα ∂ x β
∂2 ∂2 ∂2
+ ( kα m f ) + ( k mα f ) + ( k mm f ), (13.12.9)
∂ xα ∂ m ∂m ∂ xα ∂m 2

where the velocity in the m-space and components of the tensor of turbulence kam, kma , and kmm are
defined as in (Eqns. 13.12.7) and (13.12.8) with replacement of radii r with masses m.
If particles are described by the distribution function by the area Ar = r2, a characteristic of
the Maxwellian growth rate, and probabilities WxA describe transitions between the states, then
the Chapman–Kolmogorov equation can be written as in (Eqn. 13.12.3) replacing r → Ar, and the
Fokker–Planck equation becomes

∂ f ( x , Ar , t ) ∂ ∂ ɺ ∂2
=− ( vα f ) − ( Ar f ) + ( kα β f )
∂t ∂ xα ∂ Ar ∂ xα ∂ x β
∂2 ∂2 ∂2
+ ( kα A f ) + ( k Aα f ) + ( k AA f ). (13.12.9a)
∂ xα ∂ Ar ∂ Ar ∂ xα ∂ Ar2

One can see that the form of (Eqns. 13.12.3), (13.12.9), and (13.12.9a) is similar to the previous
stochastic kinetic equations of the Fokker-Planck type with drift and diffusion reviewed in Section
13.1.2 and to the equations derived in this chapter based on statistical and semi-empirical theories
of turbulence. The two features of these equations can be noted. On one hand, (Eqns. 13.12.3),
(13.12.9), and (13.12.9a) generalize the equations from the previous sections and contain other sto-
chastic kinetic equations derived previously as particular cases. On the other hand, the generalized
velocities and turbulence tensors (Eqns. 13.12.4)–(13.12.8) remain the formal expressions until the
models of turbulence and particle growth are specified, and a concrete form of the probabilities Wxr
is chosen. The meaning of the Fokker–Planck equations derived earlier is illustrated by considering
the particular cases in the next sections.

13.12.2. Spatially Homogeneous Cloud

For a spatially homogeneous cloud, the probability of transition depends only on radii as Wrr(r|r′), the
spatial derivatives are zero, ∂/∂xa = 0, and the Fokker–Planck (Eqn. 13.12.3) is simplified as

∂ f (r , t ) ∂ ∂2
= − (rf
ɺ ) + 2 ( Dr f ), (13.12.10)
∂t ∂r ∂r
where rɺ represents the drift velocity and the diffusion coefficient Dr is determined by (Eqn. 13.12.8):
1
2∫
Dr (r ) = r ′ 2 Wr (r | r ′ ) dr ′. (13.12.11)
674 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

If particles are described by the distribution function by the area Ar = r2, then (Eqn. 13.12.9a) for the
spatially homogeneous case is

∂ f ( Ar , t ) ∂ ɺ ∂2
=− ( Ar f ) + ( DA f ), (13.12.11a)
∂t ∂ Ar ∂ Ar2

where the diffusion coefficient DA is determined by (Eqn. 13.12.8):

1
2∫
D A ( Ar ) = A′r 2WA ( Ar | Ar′ ) dAr ′ . (13.12.11b)

Equation (13.12.11a) has the form of the Fokker–Planck equation for f(Ar) introduced by McGraw
and Liu (2006). The drift velocity Aɺ r was defined by McGraw and Liu via the mean supersaturation
s , and the diffusion coefficient DA was expressed via the supersaturation variance ss and the inverse
time gs of supersaturation relaxation. This can be written in our notations as

Aɺ r = 2bcon s , DA = (2bconσ s )2 /γ s , (13.12.11c)

where bcon = Dv rws / (Γ1ra).

Thus, the equation of McGraw and Liu is a particular case of (Eqn. 13.12.9a), which in turn is a
particular case of the generalized kinetic (Eqn. 13.12.1a).
Introducing the density flux j(r,t) in the space of radii:

∂
j (r , t ) = rf
ɺ (r , t ) −  Dr (r ) f (r , t )  , (13.12.12)
∂r 
(Eqn. 13.12.10) can be rewritten as the continuity equation

∂f ∂j
=− . (13.12.13)
∂t ∂r

Equations (13.12.10) and (13.12.13) account for the diffusion term in the space of radii and general-
ize an original kinetic (Eqn. 5.5.5) (Chapter 5) for the regular condensation introduced by Buikov
(1961, 1963). The explicit form of the diffusion coefficient Dr can be found either by specifying the
corresponding probability Wr(r|r′) or by expressing Dr via f and rɺ.
The second way of deriving Dr is briefly illustrated here for the case of Brownian diffusion. The
concentration c(x) of the particles with radius r moving along the x-axis in an external potential field
U(x) with the mean velocity v is described by the diffusion equation

∂c ∂j ∂c
=− B , jB = vc − DB , (13.12.14a)
∂t ∂x ∂x
where DB is the coefficient of Brownian diffusion defined in Chapter 10, and jB is the density flux.
For the steady state, ∂c/ ∂t = 0, and jB = 0, hence

DB = vc /(∂c / ∂ x ). (13.12.14b)

It is known that the equilibrium concentration c(x) in the potential field U(x) is described by the
Boltzmann distribution, c(x) = c0exp(−U/kT), where T is the temperature and k is the Boltzmann con-
stant, so that ∂c/∂x = c(x)(−∂U/∂x)/kT. But −∂U/∂x = F, where F is the force acting on the particle in
13.12. Derivation of the Generalized Stochastic Kinetic Equations 675

the field U. If a particle is moving in a viscous medium without acceleration, this force F is equal to the
viscosity force, which for small particles is determined by the Stokes law, F = 6phrv, where h is the vis-
cosity of the medium (see Chapter 12). Using these relations, we obtain (∂c/∂x)/c(x) = F/kT = 6phv/kT.
Substituting this expression into (Eqn. 13.12.14b), we obtain

kT
DB = , (13.12.14c)
6πηr

which is Einstein’s equation for the Brownian diffusion coefficient. Thus, the diffusion coefficient
DB in the coordinate x-space was determined by expressing it via the particles’ distribution function
c(x) and their velocity v.
We use a similar method to determine the diffusion coefficient in the space of radii. For the steady-
state conditions, ∂f/∂t = 0, the condition j(r,t) = 0 allows us to express the diffusion coefficient Dr(r)
via rɺ and f as earlier. In our case, we have from (Eqn. 13.12.12) and the condition j = 0:

dDr (r ) df (r )
j (r , t ) = rf
ɺ (r , t ) − f (r , t ) − Dr (r ) = 0, (13.12.15)
dr dr
which can be rewritten as a linear inhomogeneous differential equation for Dr:

dDr (r ) 1 df (r )
+ Dr (r ) − rɺ = 0. (13.12.16)
dr f (r , t ) dr

A solution for Dr is
r
1 f (r0 )
Dr (r ) = ∫
f (r ) r0
ɺ (r ) dr + C
rf
f (r )
, (13.12.17)

where r0 is some reference point and C is the constant of integration. It follows from (Eqn. 13.12.17)
that C = Dr(r0) ≡ Dr0 for r = r0, thus
r
1 f (r0 )
Dr (r ) = ∫
f (r ) r0
ɺ (r ) dr + Dr 0
rf
f (r )
. (13.12.18)

This equation expresses Dr via f (r), rɺ, and a reference value Dr0. A specific form of Dr depends on
the type of cloud process and the resulting model of the size spectrum f(r). For example, if f(r) is the
gamma distribution with the index p and modal radius rm,

f (r ) = cN r p exp(− pr /rm ), (13.12.19)

and the growth rate is described by Maxwell’s law (Eqn. 13.2.2), substitution of these equations into
(Eqn. 13.12.18) yields
−p
 pr   pr    pr   pr  
Dr (r ) = bcon s   exp    Γ  p, 0  − Γ  p,  
 rm   rm    rm   rm  

r 
p
 p(r0 − r ) 
+ Dr 0  0  exp  − , (13.12.20)
r  rm 
676 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

where Γ(x,a) is the incomplete gamma function. When the mean supersaturation s = 0, the regu-
lar growth rate is absent, the first term on the right-hand side vanishes, and the second term in
(Eqn. 13.12.20) shows that

f (r0 )
Dr (r ) = Dr 0 , (13.12.21)
f (r )

in agreement with (Eqn. 13.12.18). That is, Dr is in antiphase with f(r): Dr(r) decreases with increas-
ing r and r < rm, reaches a minimum at the point of modal radius rm, and then increases with r. If the
size spectra are parameterized in the form of the inverse power laws, f ~ r − β, then it follows from
(Eqn. 13.12.21) that Dr ∼ (r/r0)β at s = 0—i.e., the diffusion coefficient in the radii space resembles
Taylor’s form kx ∼ (x/x0)g of the horizontal eddy diffusion coefficient used in calculations of the dis-
persion of pollutants (Rodean, 1996; Monin and Yaglom, 2007a,b).

13.12.3. Spatially Inhomogeneous Cloud

Note first that in this case the jumps xa′ and r ′ may be not completely independent, and r ′ can be
related to xa′ in one or another way via the supersaturation equation, and the type of this dependence
determines the type of the stochastic kinetic equation. As discussed in Section 13.2, r ′ is analogous
to the mixing length lr′ in the space of radii and can be evaluated by integration over time of the cor-
responding velocity rɺ ′ of radius fluctuation. The choice of rɺ ′ is crucial; it determines the type of final
equation, and this is the major point where the differences among the theories occur. Consider now
two models of r ′ that lead to different forms of the kinetic equations.
In the first model, assume that rɺ ′ is of the Maxwellian type (Eqn. 14.3.2), thus the radius fluctua-
tion velocity rɺ ′ is

rɺ ′ = bcon s ′/ r , (13.12.22)

where bcon = Dvrvs /(Γprw), and s′ is the supersaturation fluctuation—that is, the growth rate in fluctua-
tions is the same as in the regular updrafts, the Maxwellian diffusion regime, rɺ ′ ∼ 1/r. A model for r′
in the radii space follows from (Eqn. 13.12.22). Its integration by time yields

bcon s ′(t ′ )
t t t
b
r ′ = ∫ rɺ ′(t ′) dt ′ = ∫ dt ′ ≈ con ∫ s ′(t ′) dt ′
0 0
r (t ′) r 0
B
= c δ β 3 xβ , Bc = bcon c1wτ f = Dv Bcon , (13.12.23)
r
where Bcon was defined in (Eqn. 13.1.4), and we accounted for the fact that the fluctuations are small,
r ′ << r, and r can be approximately removed out of the integral sign over the short duration of the fluctua-
tion. Substituting r ′ from (Eqn. 13.12.23) into (Eqn. 13.12.7) for kar into (Eqn. 13.12.8) for krr, we obtain
Bc 1 DB
kα r = δ β 3 ∫ xα ′ x β ′ W ( x , r | x ′, r ′ ) dx ′dr ′= v con δ β 3 kαβ , (13.12.24)
r 2 r
2 2
B  1 DB 
krr =  c  δ α 3δ β 3 ∫ xα ′ x β ′ W ( x , r | x ′, r ′) dx ′dr ′ =  v con  δ α 3δ β 3 kα β , (13.12.25)
 r  2  r 

that is, the diffusion coefficient in the radii space is inversely proportional to the squared radius.
13.12. Derivation of the Generalized Stochastic Kinetic Equations 677

Substituting these expressions into the Fokker–Planck kinetic (Eqn. 13.12.3), and accounting for
sedimentation and the regular growth rate (Eqn. 13.2.2), we obtain

∂f ∂ ∂ b s
+ ( uα − vr (r )δ α 3 ) f  +  con 
f
∂t ∂ xα   ∂r  r 
 ∂ ∂ Dv   ∂ ∂ Dv 
= + δ α 3 Bcon   ∂ x + δ β 3 Bcon ∂r r  kαβ f . (13.12.26)
∂
 α x ∂ r r  β 

This is a simplified version of the kinetic (Eqn. 13.1.3) by Levin-Sedunov (1966), Sedunov (1974),
Voloshchuk-Sedunov (1977), and Smirnov-Nadeykina (1986) considered in Section 13.1, which is
written similar to (Eqn. 13.1.3), as if Dv may depend on r. For the particular case with spatial homo-
geneity, ∂/∂xa = 0, it becomes
2
∂f ∂  b s   ∂ Dv Bcon 
+  con f  =   kαβ f . (13.12.26a)
∂t ∂r  r   ∂r r 

This equation for f(r) can be transformed to the equation for the size distribution f(Ar) by the
area Ar = r2 considered in Section 13.12.1. Using the conservation law, f(r)dr = f(Ar)dAr, and the
relation (∂/∂r) = (2r)(∂/∂Ar), (Eqn. 13.12.26a) can be transformed to a form similar to the equation
by McGraw and Liu (2006) with the drift and diffusion in radii space but with a different diffusion
coefficient.
Thus, we began with the general Fokker–Planck equation derived from the generalized integral
kinetic (Eqn. 13.12.1b) of the Chapman–Kolmogorov type, and using the Maxwellian model both
for the regular growth rate and its fluctuations, arrived at the differential stochastic kinetic equations
of the Fokker–Planck type. The analytical solutions to these equations have the Gaussian form in the
non-steady case, or the form of the Weibull distribution in the quasi-steady state (see Section 13.1).
Another model was considered by Khvorostyanov and Curry (1999c, 2008c) and was described in
Section 13.2, when the growth rate in the regular updrafts is Maxwellian diffusion (Eqn. 14.3.2), but
rɺ ' in fluctuations is parameterized as
Dv ρ ws
rɺ ′ = φr sw′ , φr = . (13.12.27)
Γρ w r

that is, rɺ ′ does not depend on r, and the growth rate in fluctuations proceed in the quasi-kinetic
regime. This relation was justified in Section 13.2 by the hypothesized proportionality s′ ∼ r for small
timescales in fluctuations. Then r′ in the radii space can be evaluated as
t t t
r ′ = ∫ rɺ′(t ′) dt ′ = φr ∫ sw′ (t ′) dt ′ = Gs ∫ u3′ (t ′) dt ′ = Gsδ α 3 xα′ , (13.12.28)
0 0 0

where dab is the Kronecker symbol and Gs is a dimensionless parameter introduced in (Eqn. 13.3.12).
Substituting this r ′ into (Eqn. 13.12.7) for kar and in (Eqn. 13.12.8) for krr, we obtain
1
2∫
kα r = Gsδ β 3 xα′ x β′ W ( x , r | x ′, r ′) dx ′dr ′ = Gsδ β 3 kα β , (13.12.29)

1
krr = Gs2δ α 3δ β 3 ∫ xα′ x β′ W ( x , r | x ′, r ′) dx ′dr ′ = Gs2δ α 3δ β 3 kαβ . (13.12.30)
2
678 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

Substituting further these coefficients and rɺ from (Eqn. 13.2.2) into the general (Eqn. 13.12.3), we
obtain
∂f ∂ ∂ b s
+ ( uα − vr (r )δ α 3 ) f  +  con f 
∂t ∂ xα   ∂r  r 
 ∂ ∂  ∂ ∂
= + Gsδ α 3   + Gsδ β 3  kα β f , (13.12.31)
 ∂ xα ∂r   ∂ x β ∂r 

where we added the term with the terminal velocity vr(r) and accounted for the symmetry of the
turbulence tensor, kab = kba. Equation (13.12.31) is a simplified version of the Khvorostyanov–Curry
(1999c, 2008c) equation for stochastic condensation derived in Sections 13.2–13.4, which is valid
for the low-frequency turbulence—i.e., with assumption on the quasi-steady supersaturation fluctua-
tions. Again, it is derived here from the Fokker–Planck equation with some specification of the drift
velocity and diffusion coefficient. The analytical solutions to this equation in the form of generalized
gamma distributions were found in Sections 13.6 and 13.7.
The other models can be considered in the same way based on the Fokker–Planck
(Eqn. 13.12.3) with various drift velocities and diffusion coefficients. These derivations and their
comparison to the previous works show equivalence of the Fokker–Planck approach to the methods
of the semi-empirical theory of turbulence with ensemble averaging. Thus, the generalized kinetic
(Eqn. 13.12.1b) derived from the Chapman–Kolmogorov equation) and the Fokker–Planck equations
may serve as a general basis for derivation of the stochastic condensation equations, but some addi-
tional arguments are needed every time to specify the drift velocity and the diffusion coefficient in
the space of radii, mass, area, or equivalent variables.
Derivation and Solution of the Kummer 679

Appendix A.13. Derivation and Solution of the Kummer

Equation in Section 13.6.3

Here, we present details of the derivation and solution of the Kummer equation for the interpolation
function Φ(r) because of the potential use of this technique for bulk cloud models. It is convenient to
rewrite the composite spectrum (Eqn. 13.6.11) with auxiliary function h(r):

fs (r ) = η (r )Φ(r ), (A.13.1)
p
η (r ) = c1,2 r exp(− β s r ). (A.13.2)

The derivatives fs′ and fs″ are then expressed as

fs′ = ( p / r − β s )η Φ + η Φ′, (A.13.3)

fs″ = ( p /r − β s ) η Φ − ( p / r )η Φ+ 2( p /r − β s )η Φ′+ η Φ″.
2 2
(A.13.4)

Substituting (Eqns. A.13.3) and (A.13.4) into (Eqn. 13.5.11), applying (Eqns. 13.6.4) and (13.6.7),
and deleting h(r) in the resulting equation yields

 p 
2
G 2kp p  
Gs2 k  − β  Φ − s 2 Φ + 2  − β s  Φ′ + Φ″
  r  r  r  
 bcon s   p   2 bcon s 
+  2Gs α s k −   − β s  Φ + Φ′ α s k (1 − µs ) + 2  = 0. Z
2
(A.13.5)
 r   r   r 

Now collecting the terms with various derivatives of Φ, we obtain the equation

d 2Φ dΦ
A1 + A2 + A3 Φ = 0, (A.13.6)
dr 2 dr
where

A1 = Gs2 k, (A.13.7)
 2G kp 2
b s
A2 =  − 2Gs2 k β s + 2Gsα s k − con  ,
s
(A.13.8)
 r r 
Gs2 kp2 2Gs2 kpβ s
A3 = − + Gs2 k β s2
r2 r
G 2 kp 2Gsα s kp bcon sp
− s2 + − 2 − 2Gsα s k β s
r r r
bsβ s b s
+ + α s2 k (1 − µs2 ) + con2 . (A.13.9)
r r
These coefficients are significantly simplified after substituting the expression bcons = Gs2kp that fol-
lows from (Eqn. 13.6.4) (with cnn = cn = 1) and (Eqn. 13.6.10) for bs. First, for bs1 = (as /Gs)(1 − ms),
we have
2Gs kpα s 2Gs kpα s µs 2Gs kpα s
A3 = − + + kα s2 − 2 kα s2 µs + kα s2 µs2 +
r r r
G kα p G k α p µ
− 2 kα s2 + 2 kα s2 µs + s s − s s s + kα s2 − kα s2 µs2 . (A.13.10)
r r
680 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

This equation contains twelve terms, but one can see that the following nine terms are mutually
cancelled: 1st and 6th; 4th and 8th; 3rd, 7th, and 11th; 5th and 12th. The remaining three terms yield

Gs k α s p
A3 = (1 + µs ). (A.13.11)
r
The coefficient A2 is also simplified after substitution of bcons via p and bs1:

2Gs2 kp α G 2 kp
A2 = − 2Gs2 k s (1 − µs ) + 2Gsα s k − s
r Gs r
 p 2α µ 
= Gs2 k  + s s  . (A.13.12)
r Gs 

Substituting these reduced terms A2, A3 into (Eqn. A.13.6), dividing by Gs2k, and multiplying by r, we
obtain the equation for Φ:

 2α µ  α p
r Φ″ +  p + s s r  Φ′ + s (1 + µs ) = 0. (A.13.13)
 G s  Gs

A solution to this equation is the confluent hypergeometric (Kummer) function F(a, b; x) (Landau
and Lifshitz, 1958, v.3; Gradshteyn and Ryzhik, 1994):

 p 2α µ 
Φ(r ) = c1 F  ( µs + 1), p; − s s r , (A.13.14)
 2 µs Gs 

where c1 is the normalization constant. Then, the full solution for fs is

 α 
fs ,1 (r ) = c1r p exp  − s (1 − µs ) ,
 Gs 
 p 2α µ 
×F  ( µs + 1), p; − s s r . (A.13.15)
 2 µs Gs 

For the second slope bs2, substituting bs2 = (as /Gs)(1 + m) from (Eqn. 13.6.10) and bcons = Gs2kp into
(Eqn. A.13.9) for A3 yields
2Gs kpα s 2Gs kpα s µs 2Gs kpα s
A3 = − − + kα s2 + 2 kα s2 µs + kα s2 µs2 +
r r r
Gs kα s p Gs kα s pµs
− 2 kα s − 2 kα s µs +
2 2
+ + kα s − kα s µs .
2 2 2
(A.13.16)
r r
Here also, of the total twelve terms, the following terms are mutually cancelled: 1st and 6th; 3rd, 7th,
and 11th; 4th and 8th; 5th and 12th. The remaining three terms yield

Gs k α s p
A3 = (1 − µs ). (A.13.17)
r
Derivation and Solution of the Kummer 681

The coefficient A2 in (Eqn. A.13.8) is simplified after substitution of bcons via p and bs2:

2Gs2 kp G 2 kp
A2 = − 2Gs2 k s (1 + s ) + 2Gs s k − s
r G r
 p 2 
= Gs2 k  + s s
. (A.13.18)
r Gs 

Again substituting reduced A2, A3 into (Eqn. A.13.6), dividing by Gs2k, and multiplying by r, we
obtain the equation for Φ:

 2α µ  α p
r Φ″ +  p − s s r  Φ′ + s (1 − µs ) = 0. (A.13.19)
 Gs  Gs

A solution to this equation is the confluent hypergeometric function F (Gradshteyn and Ryzhik,
1994):

 p 2α µ 
Φ(r ) = c2 F  ( µs − 1), p; + s s r . (A.13.20)
 2 µs Gs 

The full solution for fs is

 α 
fs ,2 (r ) = c2 r p exp  − s (1 + µs ) ,
 Gs 
 p 2α µ 
×F ( µs − 1), p; + s s r . (A.13.21)
 2 µs Gs 

The confluent hypergeometric functions F(a, b; x) have the following properties. The function
F(a,b;x) can be defined as a power series:

a x a(a + 1) x 2
F (a, b, x ) = 1 + + +. . . (A.13.22)
b 1! b(b + 1) 2!

This series is convenient for coding, rather rapidly converges, and usually does not require a large
number of terms. A few useful limits follow from this definition.
F (0, b; x ) = 1, limF ( a, b, x ) = 1, F (a, a, x ) = e x . (A.13.23)
x→0

For analysis of the asymptotic behavior of F(a, b; x) at large x, another representation of this function
is used as a contour integral over a contour C in the complex plain of the complex variable x (Landau
and Lifshitz, 1958, v.3; Gradshteyn and Ryzhik, 1994):

Γ (b) t
2π i C∫
F (a, b; x ) = e (t − x )− a t a − b dt , (A.13.24)

where Γ(b) is the Euler gamma function and i = −1 . The subintegral function in (Eqn. A.13.24) has
two singular points, at x = t and x = 0. Deforming contour C in the complex plane in such a way that
682 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

it transforms into two contours each going in a counterclockwise direction around these two singular
points, dividing subintegral function by (−x)−a, expanding it by the powers t/x, and integrating all
terms, the following expression is obtained:

Γ (b)
F (a, b; x ) = (− x )− a Y(a, a − b + 1; − x )
Γ (b − a)
Γ (b) x a − b
+ e x Y(b − a, 1 − a; − x ), (A.13.25)
Γ (a)

where the function Y(a, b; x) is a power series of the inverse powers of x:

ab a(a + 1)b(b + 1)
Y(a, b; x ) = 1 + + +. . . (A.13.26)
1! x 2! x 2
It is easy to see that Y(a,b;x) → 1 when x → ∞. Using this limit in (Eqn. A.13.25), we see that the first
term tends to zero at x → ∞ and a > 0, and the second term has the following limit

Γ (b) x a − b
limF ( a, b, x ) ≈ e x . (A.13.27)
x →∞ Γ (a)

This limit is convenient for analysis of the asymptotic behavior of the size spectra at large radii.
The spectral n-th moment of the distribution functions (e.g., number density, mean radius, liquid
or ice water content) can be evaluated using the relations (Landau and Lifshitz, 1958, v.3; Gradshteyn
and Ryzhik, 1994)
∞

M (ν ) = ∫x e
ν −λx
F (a, b, β x ) dx
0

 β
= Γ (ν + 1)λ − (ν +1) F  a,ν + 1, b;  , (A.13.28)
 λ

where F(a, b, g ; x) is the Gauss hypergeometric function. Using this equation, we obtain the follow-
ing n-th moment for the 1st solution (Eqn. A.13.15) or (Eqn. 13.6.15):
∞ − ( p+ n +1)
α 
M (n)
= ∫ r fs (r ) dr = c1Γ ( p + n + 1)  s (1 − µs ) 
n

0
G
 s 
 p 2 µs 
×F (1 + µs ), p + n + 1, p; − , (A.13.29)
 2 µs 1 − µs 

and the n-th moment for the 2nd solution (Eqn. A.13.21 or 13.6.18)
∞ − ( p+ n +1)
α 
M ( n ) = ∫ r n fs (r ) dr = c2 Γ ( p + n + 1)  s (1 + µs ) 
0  Gs 
 p 2 µs 
×F ( µs − 1), p + n + 1, p, . (A.13.30)
 s
2 µ 1 + µs 
Derivation and Solution of the Kummer 683

In particular, for n = 0, M(0) = N we obtain normalization constants c1, c2. For the solution of
(Eqn. A.13.15) or (Eqn. 13.6.15), we obtain
−1
− ( p +1)
 αs   p 2 µs  

c1 = N Γ ( p + 1)  (1 − µs )  F (1 + µs ) , p + 1, p, −  (A.13.31)
1 − µs  
.
  Gs   2 µs


For (Eqn. A.13.21) or (Eqn. 13.6.18), we obtain

−1
− ( p +1)
 α   p 2 µs  

c2 = N Γ ( p + 1)  s (1 + µs )  F ( µs − 1) , p + 1, p,  (A.13.32)
1 + µs  
.
 Gs   2 µs
 

These relations can be used for evaluation of the LWC (IWC), number densities, mean radii, extinc-
tion coefficients, and other moments of the solutions given in Section 13.6.
684 Broad Size Spectra in Clouds and the Theory of Stochastic Condensation

Appendix B.13 Solutions of Kinetic Equations of Section 13.7,

Taking into Account Diffusional Growth in the Tail

It is convenient to solve (Eqn. 13.7.1) by rewriting it as

d  fs 
  = [ξ1 + ξ 2 (r )] fs , (B.13.1)
dr  r 

where

1  2 dk dα s dw 
ξ1 = αs k + αs +k − αsw − − σ col  , (B.13.2a)
bcon s  dz dz dz 
ξ 2 = α s v (r ) / bcon s. (B.13.3a)

Introducing a new variable js = fs(r)/r, (Eqn. B.13.1) can be rewritten as

dϕ s
= [ξ1 + ξ 2 (r )]rϕ s . (B.13.4)
dr
Integration from some r1 to r yields
ϕ s (r ) = ϕ s (r1 ) exp( J s1 + J s 2 ), (B.13.5)

where
(r 2 − r12 )ξ1
r

J s1 = ∫ ξ1r dr = , (B.13.6)
r1
2
r
ξ 2 (r )r 2 − ξ 2 (r1 )r12
J s 2 = ∫ ξ 2 (r )r dr = . (B.13.7)
r1
Bv + 2

When evaluating Js2, we assume that the fall velocity v(r) at this size range can be approximated
by the power law (Eqn. 13.5.9) v (r ) = Av r Bv with constant Av, Bv. Substituting these integrals into
(Eqn. B.13.5), and again using fs = js /r, we obtain the solution for the larger portion of the small
fraction r < r0:
r
fs (r ) = fs (r1 ) exp[− β s 2 (r )r 2 − β s 2 (r1 )r12 ], (B.13.8)
r1

where the slope bs2 is

ξ ξ2 
βs 2 = −  1 + 
 2 Bv + 2 
1  α s w + dw /dz + σ col − α s2 k − α s k ′ − kα s ′ α s v (r ) 
= − , (B.13.9)
bcon s  2 Bv + 2 

and the primes here denote derivatives by z. This is the solution for the tail of the small fraction
expressed via its value at r = r1.
14
Analytical Solutions to the Stochastic
Kinetic Equation for Precipitating Clouds

14.1. Introduction

As described in Chapter 2, the most often used parameterizations of the size spectra fl (r) of precipitat-
ing cloud particles (e.g., rain, snow, graupel, hail) are the Marshall–Palmer (1948, hereafter MP) and
Gunn–Marshall (1958) exponential distributions,

fl (r ) = N 0 exp(− βl r ), (14.1.1)

where b l is the slope and N0 is the intercept. These parameterizations are widely used and routinely
incorporated into bulk cloud models and remote sensing techniques. More recently, three-parameter
gamma distributions have been suggested as a better alternative for rain and snow size spectra (Ulbrich,
1983; Willis, 1984):

fl (r ) = cN r pl exp(− βl r ), (14.1.2)

where r is the particle radius, pl is the index of the gamma distribution (shape parameter), positive
or negative, and cN is the coefficient determined from the normalization to the concentration or mass
density. The exponential MP distribution (Eqn. 14.1.1) is a particular case of (Eqn. 14.1.2) with
pl = 0, whereby (Eqn. 14.1.2) is a more general form that allows additional degrees of freedom.
Equations (14.1.1) and (14.1.2) are often formulated in terms of diameters or maximum crystal
lengths D, fl (D) ∼ exp(−ΛD), with the slope Λ = b l /2.
Since the beginning of the 1960s, numerous theoretical works have been devoted to explanations
of the observed size spectra of cloud particles by means of various analytical and numerical solutions
of the kinetic equation of coagulation. Here, we briefly review some of these studies that illustrate
the evolution of various models and concepts and create a basis for derivation of the analytical solu-
tions to the kinetic equation similar to (Eqns. 14.1.1) and (14.1.2). Such solutions are obtained in
this chapter, and the indices pl and slopes b l are expressed via the cloud and atmospheric properties.
Studies of the solutions to the coagulation equations have proceeded along four lines: a) ana-
lytical solutions; b) numerical solutions; c) refinements of the collision-coalescent efficiencies; and
d) generalizations of the coagulation kinetic equation itself.
Earlier theoretical studies of the size spectra of precipitating particles were directed toward explain-
ing the exponential shape of the MP spectra and the evolution of its parameters. Golovin (1963),
Scott (1968), Lushnikov (1973, 1974), Voloshchuk and Sedunov (1975), Lushnikov and Smirnov
(1975), Srivastava and Passarelli (1980), Lushnikov and Piskunov (1982), and Voloshchuk (1984)
obtained analytical solutions to the kinetic equation of condensation and coagulation with idealized

685
686 Analytical Solutions to the Stochastic Kinetic Equation for Precipitating Clouds

assumptions including homogeneous kernels of the coagulation integral and non-Maxwellian models
for the condensation growth rate. Srivastava (1971) hypothesized that a balance exists between the
collision-coalescence and spontaneous breakup of raindrops, which leads to the exponential MP
spectra, but the derived slopes were distinctly steeper than the observed spectra. Passarelli (1978a,b)
assumed that snow spectra are described by the MP spectrum and found an analytical expression for
the slopes via integral moments by solving the stochastic collection equation without accounting for
breakup.
Although the coagulation equation is often called “the stochastic collection equation,” accounting
for the stochastic effects of turbulence on the coagulation process is often incomplete. Extending the
theory of stochastic condensation described in Chapter 13 to the coagulation processes, Voloshchuk
(1977) derived a stochastic coagulation equation that is a generalization of Equation (5.6.5) for the
turbulent atmosphere. Applying the Reynolds procedure of decomposition into the mean and fluctu-
ating parts as described in Section 13.2, averaging, and using the non-local parameterization of the
semi-empirical theory of turbulence, Voloshchuk (1977) derived an equation for the volume distribu-
tion function fv(v):

∂ fv ( v , t ) ∂ f (v, t ) ∂ ∂ f (v, t )
+ ui v = kij v
∂t ∂ xi ∂ xi ∂ xj
v ∞
1
2 ∫0
+ K ( v ′, v − v ′) fv ( v − v ′) fv ( v ′) dv ′ − ∫ K ( v , v ′) fv ( v ) fv ( v ′) dv ′
0
∞
∂ f ( v − v ′) ∂ fv ( v ′) ∂ f ( v ) ∂ fv ( v ′)
v
1
2 ∫0
+ λij K ( v ′, v − v ′) v dv ′ − ∫ λij K ( v , v ′) v dv ′. (14.1.3)
∂ xi ∂ xj 0
∂ xi ∂ xj

Here, lij = LiLj, and Li is the effective scale of turbulence in the i-th direction, ui is the wind com-
ponent in i-th direction, summation over doubled indices is assumed, i = 1, 2, 3, and all quantities
are averaged over an ensemble of turbulent realizations. The first term and the last two terms on the
right-hand side in (Eqn. 14.1.3) are the new terms that arise due to the effects of turbulence on the
motion and collision-coalescence of the particles in the turbulent medium. Voloshchuk’s equation is
more complete and general than the original Smoluchowski–Müller (Eqn. 5.6.5); however, it is more
complicated and its detailed analysis has not been performed until now. The subsequent description
in this chapter is based on (Eqn. 5.6.5).
Numerical solutions of the stochastic collection (Eqn. 5.6.5) with more realistic kernels based
on accurate finite difference approximations (e.g., Berry and Reinhardt, 1974a,b) or on the method
of moments (e.g., Bleck, 1970; Tzivion et al., 1987) allowed more detailed studies of the tempo-
ral evolution of the size spectra of precipitating particles and created the benchmarks for testing
the analytical solutions that were developing in parallel with the numerical methods. Verlinde et al.
(1990) obtained an analytical solution to the collection growth equation for the original size spectra
described by gamma distributions (Eqn. 14.1.2). The solution was rather complicated, expressed via
the complete Gauss hypergeometric function 2F1(a,b,c; x) and the Euler gamma function and required
simplifications for application in the models. Passarelli’s model with exponential spectra was further
developed and generalized by a number of authors (e.g., Mitchell, 1994, Mitchell et al., 1996).
By the end of 1970s, it became clear that collisional rather than spontaneous breakup may be more
important in restricting drop growth and formation of the observed raindrop exponential spectra.
14.1. Introduction 687

Srivastava (1978) formulated a simplified model of collisional breakup with a fixed constant number
of fragments as a variable parameter and developed a parameterization for raindrop spectra in the
form of a general exponential, but with time varying Λ and N0. Low and List (1982a,b, hereafter
LL82) developed a complex empirical parameterization of the fragment distribution function for
collisional drop breakup. The parameterization of LL82 has been used in many numerical solutions
of the stochastic coalescence/breakup equation to explain the mechanism of formation of the MP
spectra and their slopes (e.g., Feingold et al., 1988; Hu and Srivastava, 1995; Brown, 1991, 1997;
McFarquhar, 2004; Seifert, 2005).
These numerical solutions produced somewhat different equilibrium size spectra but with com-
mon features: a small size region from ∼200 μm to ∼2 mm consisting of several peaks with shallow
troughs between them and a region beginning at ∼2–2.5 mm and comprising the MP exponential tail.
McFarquhar (2004) refined the LL82 equations and emphasized that measurement and sampling
problems impose uncertainties on the solutions, motivating more detailed laboratory studies and
improved parameterizations. Bott (1998, 2000, 2001) developed a precise flux method for a numeri-
cal solution of the collection equation that ensures mass conservation and can serve as the benchmark
for the other methods.
The numerical studies focused on analyzing the positions of the peaks and values of the slopes but
usually did not attempt to approximate the entire rain spectrum using gamma distributions. Param-
eterization of the large particle size spectrum in the form of the gamma distribution (Eqn. 14.1.2)
has been undertaken by many empirical studies that were directed toward determination of the three
parameters of the spectra, and in particular the index pl. Ulbrich (1983) found a correlation between
the type of the rain and the index pl; there was pl < 0 for orographic rain indicating broad spectra, and
0 < pl < 2 for thunderstorm rain indicating a narrower spectra. For widespread and stratiform rain, pl
was more variable but mostly positive. Willis (1984) found the best value to be pl ≈ 2.5 for raindrops
from two hurricanes.
More recently, another type of pl dependence was suggested: a Λ–pl relation, whereby Λ was
expressed as a quadratic polynomial of pl or vice versa (e.g., Zhang et al., 2001, 2003a,b; Brandes
et al., 2003). The validity of this parameterization was tested in direct simulations of convective rain
with cloud models using the LL82 kernel (e.g., Seifert, 2005). The Λ–pl relation allows reduction
of the number of independent parameters in (Eqn. 14.1.1) to two, but the general dependence of the
index pl on the rain type described by Ulbrich (1983) is still unclear. A similar relation was suggested
by Heymsfield (2003) for crystalline clouds.
Reviews of various methods and approaches in calculations of the large-size spectra can be found
in the books of Voloshchuk and Sedunov (1975), Voloshchuk (1984), Rogers and Yau (1989), Young
(1993), Pruppacher and Klett (1997), Straka (2009), and Cotton et al. (2011).
Previous research has revealed some fundamental properties of the size spectra of precipitating
particles, and has shed some light on the mechanisms of their formation. However, direct application
of these findings in cloud models and remote sensing retrievals encounters the following problems:
owing to the complexity of collision/breakup kernels, mostly numerical solutions of the stochastic
coalescence/breakup kinetic equation have been obtained for realistic representations of the gravita-
tional kernel. The numerical solutions require small time steps, are rather time consuming, and do not
provide simple analytical parameterizations for the indices and slopes of the exponential and gamma
688 Analytical Solutions to the Stochastic Kinetic Equation for Precipitating Clouds

distributions that are needed in cloud and climate models and remote sensing retrievals. Many previ-
ous analytical solutions were expressed in terms of special functions, were too complicated for direct
analysis, and did not provide the indices and slopes of the size spectra.
In Chapter 13, gamma distributions were derived for the small-size fraction as the solutions of
the kinetic equation of stochastic condensation. The objective of this chapter is to obtain sufficiently
simple yet physically-based analytical solutions of the stochastic kinetic equation for precipitating
cloud particles and to explain observed variations in the size spectra that can be used to parameterize
the size spectra for modeling and remote sensing applications (following mostly Khvorostyanov and
Curry (2008b,c), with some generalizations). The kinetic equation of coagulation in approximation
of continuous collection is derived from the general coagulation equation, and the corresponding
assumptions are discussed. The basic stochastic kinetic equation is simplified and reduced to a dif-
ferential equation in the ordinary derivatives of the second order by particle radius. Using some
assumptions and simplifications, general analytical solutions are obtained in the form that is similar
to the gamma distributions and exponential MP spectra but that contain several modifications that
better describe the observed size spectra. Four particular cases are considered: the size ranges where
fall speed is a linear function of particle size (intermediate regime of fall speeds) or is proportional to
the square root of particle size (aerodynamic regime of fall speeds, see Chapter 12); conditions where
coagulation growth is dominant; and subcloud layers with an absence of the small-size fraction. The
solutions are illustrated with calculations for a crystalline cloud; a physical interpretation is given for
these solutions, and an explanation is provided of the observed features of the size spectra that allow
improvement of existing parameterizations. The process of autoconversion is considered and the cor-
rections to the analytical size spectra that arise due to this process are described. Finally, it is shown
that the coagulation equation represents a particular case of the integral Chapman–Kolmogorov equa-
tion, as was mentioned in Chapter 13.

14.2. Derivation of Kinetic Equations in Continuous Collection Approximation

As described in Chapter 5, the stochastic collection equation is written as follows:

 ∂ f (m ) 
 = I gain − I loss , (14.2.1)
∂ t  col ,ls
m
1
2 ∫0
I gain = K (m − m ′, m ′ ) f (m − m ′) f (m ′ ) dm ′, (14.2.2a)

I loss = f (m) ∫ K (m, m′ ) f (m ′) dm ′. (14.2.2b)

0

Here m, m′, are the masses of the particles, thus

K (m, m′) = π Ec (r , r ′)(r + r ′)2 | v (r ) − v (r ′) | (14.2.2c)

is the coagulation gravitational kernel, r and r′ denote the radii of the drops (crystals) corresponding
to m and m′, Ec(r,r′) is the collection efficiency, and v(r) is the terminal velocity.
14.2. Derivation of Kinetic Equations in Continuous Collection Approximation 689

In the following sections, the continuous collection approximation is assumed for (∂fl/∂t)col,ls to
simplify the analytical solutions. In this approximation, only the collision-coalescence between par-
ticles of the different size fractions of the spectrum, fs(r) and fl (r), is considered—i.e., small particles
are collected by large particles, as in most models with bulk microphysics. The continuous collection
approximation is commonly used for evaluation of the accretion rate of the large-size fraction as in
Kessler’s (1969) and many subsequent works. If it appears in formulation of the kinetic equations,
the corresponding term (∂fl/∂t)col,ls is often written without derivation by analogy with Maxwellian
growth, with the growth rate of individual particles (dr/dt)coag or (dm/dt)coag defined in the continuous
collection approximation (e.g., Cotton et al., 2011; Pruppacher and Klett, 1997). This approach is
intuitively clear, but its accuracy and relation to the full Smoluchowski stochastic collection equation
is not clear. Therefore, the derivation of the continuous collection approximation from the integral
Smoluchowski collection equation and its simplifications are given in this section.
We represent the size spectrum as the sum of the two size fractions,

f (m) = fs (m)θ (m0 − m) + fl (m)θ (m − m0 ), (14.2.3)

where q (x) is the Heaviside step function, q (x) = 1 at x > 0 and q (x) = 0 at x < 0. Substituting this
decomposition into Igain, we have the integral that contains in the integrand four combinations of fs
and fl:
m0
1
I gain =
2 ∫ K (m − m′, m′)[ f (m − m′) f (m′) + f (m − m′) f (m′)
0
s s s l

+ fl (m − m ′) fs (m′ ) + fl (m − m ′) fl ( m′ )]dm ′. (14.2.4)

It is assumed in the continuous collection approximation that only the small-size fraction fs interacts
with the large-size fraction fl. Thus, by definition of this approximation, the integrals of the 1st term
in the square brackets with fs(m − m′)fs(m′) and of the 4th term with fl(m − m′)fl(m′) of (Eqn. 14.2.4)
vanish.
Now we proceed in the continuous collection approximation and account only for the 2nd and
3rd terms—i.e., interactions between the fractions. In the 3rd term, we introduce the new variable
m″ = m − m′ that accounts for the symmetry of the kernel, K(m − m″, m″) = K(m″, m − m″), the inte-
gral of the 3rd term becomes equal to the integral of the 2nd term, the coefficient 1/2 vanishes after
summation of the two integrals, and the sum yields
m0

I gain = ∫ K (m − m′, m′) f (m − m′) f (m′) dm′.

0
l s (14.2.5)

The upper limit is determined by definition of fs(m′). Substituting the sum (Eqn. 14.2.3) into the Iloss
yields four integrals:
m0

I loss ,ls = fl (m)θ (m − m0 ) ∫ K (m, m′) fs (m′) dm ′, (14.2.6a)

0

I loss ,sl = fs (m)θ (m0 − m) ∫ K (m, m′) fl (m′) dm ′, (14.2.6b)

0
690 Analytical Solutions to the Stochastic Kinetic Equation for Precipitating Clouds

m0

I loss , ss = fs (m)θ (m0 − m) ∫ K (m, m′) fs ( m′) dm ′, (14.2.6c)

0

I loss, ll = fl (m)θ (m − m0 ) ∫ K (m, m′) fl ( m′) dm ′ . (14.2.6d)

0

If we consider the size spectra of the large fraction fl(m) at m > m0, the 2nd integral, Iloss,sl, vanishes.
The 3rd integral, Iloss,ss, describes the process of self-collection of the small fraction called auto-
conversion that transfers the particles from fs into fl. This integral is also assumed to be zero in the
continuous collection approximation; the autoconversion will be considered in Section 14.6. The 4th
integral, Iloss,ll, represents the self-collection of the large fraction. This is also a kind of autoconversion
and would transfer the particles from fl into a larger size category, if it were present. In the continuous
collection approximation, Iloss,ll is set to zero. Thus, only the 1st integral, Iloss,ls, is non-zero at m > m0
in this approximation, which will be considered further and is denoted as Iloss.
We assume, some average value of Ec(r,r′) = const = Ec. Also, in the continuous growth
approximation

r >> r ′, v(r ) >> v (r ′), K (m, m′) ≈ K (m,0) = π Ec r 2 v (r ). (14.2.7)

Now we expand the subintegral expression in (Eqn. 14.2.5) for Igain into a Taylor power series by the
small parameter m′ up to the term of the first order:

∂
K (m − m ′, m ′) fl (m − m ′) ≈ K (m, 0) fl (m) − [ K (m, 0) fl (m)]m ′. (14.2.8)
∂m
This is a truncated first-order approximation of a more general Kramers–Moyal series considered in
Section 14.7. Substitution of this expression into (Eqn. 14.2.5) and using (Eqn. 14.2.7) yields
m0 0 m
∂
I gain = K (m, 0) fl (m) ∫ fs (m ′) dm ′ − [ K (m, 0) fl (m)] ∫ m ′fs (m ′) dm ′
0
∂m 0

∂
= fl (m)[π Ec r 2 v (r ) N s ] − [π Ec r 2 v (r )qls fl (m)] (14.2.9)
∂m
∂
= fl (m)σ col ,s − [π Ec r 2 v (r )qls fl (m)]. (14.2.9a)
∂m
Here, we used the normalization of fs(m):
m0 m0

∫
0
fs (m ′) dm ′ = N s , and ∫ m′f (m′) dm′ = q
0
s ls , (14.2.10)

where Ns and qls are the number concentration and LWC (or IWC) of the small-size fraction, and we
introduced a collection frequency
m0

σ col ,s = K (m, 0) ∫ fs (m ′) dm ′ = [π Ec r 2 v (r ) N s ], (14.2.10a)

0

which characterizes the frequency of collections of a large drop of mass m or radius r with all small
drops. Since m >> m′, the kernel K(m, m′) ≈ K(m,0) in (Eqn. 14.2.6a) for Iloss, and can be removed
outside the integral. Then, incorporating (Eqn. 14.2.7), Iloss becomes
14.2. Derivation of Kinetic Equations in Continuous Collection Approximation 691
m0

I loss = fl (m)[π Ec r 2 v(r )] ∫ fs (m ′) dm ′

0

= fl (m)[π Ec r 2 v (r ) N s ] = fl (m)σ col ,s , (14.2.11)

where we again use the normalization (Eqn. 14.2.10). Now, comparison of (Eqns. 14.2.9) and (14.2.11)
shows that the 1st term in Igain (Eqn. 14.2.9) is equal to Iloss (Eqn. 14.2.11); thus, they exactly cancel
in (Eqn. 14.2.1) for (∂fl /∂t)col,ls. Substituting Igain from (Eqn. 14.2.9) and Iloss from (Eqn. 14.2.11) into
(Eqn. 14.2.1) and cancelling these two terms yields

 ∂ fl (m)  ∂
 ∂t  =− [mɺ coag fl (m)], (14.2.12)
col , ls
∂m

where we denote

 dm 
mɺ coag ≡  = π Ec r 2 v (r )qls (14.2.13)
 dt  coag

as the coagulation mass growth rate.

Thus, the collection rate (∂fl /∂t)col,ls in the continuous collection approximation (Eqn. 14.2.12) is
derived directly from the Smoluchowski stochastic collection equation, and so this represents a first-
order approximation to the full kinetic equation. Equation (14.2.13) can be rewritten for fl (r) in terms
of radii using the relation fl (m)dm = fl (r)dr. Then, substituting into (Eqn. 14.2.12) yields

 ∂ fl (r )  dm ∂ dr
 ∂t  = − dr ∂m [mɺ coag dm fl (r )], (14.2.14)
col , ls

or

 ∂ fl (r )  ∂ ∂
 ∂t  = − ∂r [rɺcoag fl (r )] = − χ c ∂r [ v (r ) fl ], (14.2.15)
col , ls

where rɺcoag is the coagulation (accretion) radius growth rate, and so

dr Ec qls
rɺcoag = mɺ coag = χ c v (r ), χc = . (14.2.16)
dm 4 ρw

Now the coagulation terms in (Eqn. 14.2.1) (the continuous collection approximation) can be written
in a simplified differential form using the Heaviside step function q (x) as

 ∂ fs ,l (r )  ∂
 ∂r  = − χ c ∂r [ v (r ) fl ]θ (r − r0 ) − σ col fs (r )θ (r0 − r ). (14.2.17)
col

The first term is the reduced gain Igain for the large-size fraction. The second term is the reduced
loss Iloss of the small size fraction, and the coefficient scol is defined in the following text from mass
conservation.
If qll is the liquid (ice) water content of the large-size fraction, then (Eqns. 14.2.15) and (14.2.17)
yield a simple parameterization of the accretion rate, dqll /dt, that can be used in bulk microphysical
692 Analytical Solutions to the Stochastic Kinetic Equation for Precipitating Clouds

models. This expression is obtained by multiplying (Eqn. 14.2.15) by (4/3)prwr 3, and integrating
over the radius:
∞ ∞
dqll 4πρ w 3  ∂ fl  4πρ w ∂
∫0 r  ∂t  col dr = − 3 ∫r
3
= (rɺcoag fl ) dr . (14.2.18)
dt 3 0
∂r

Here the lower limit is extended from r0 to 0 noting that fl (r) = 0 in this region. Integrating by parts
and using (Eqn. 14.2.16), we obtain the gain rate (dqll /dt)col of the large-size fraction due to coagula-
tion with the small-size fraction

 dqll 
∞
 ∞

 = 4πρ w ∫ (rɺcoag fl )r dr = qls  π Ec ∫ r v (r ) fl dr  = σ col qls ,
2 2
 (14.2.19)
dt col 0  0 

where scol is the collection frequency of the large-size fraction:

∞

σ col = π Ec ∫ r 2 v (r ) fl (r ) dr . (14.2.20)
r0

Here, scol is the same collection frequency of the small-size fraction by the large-size fraction as
defined and used in Chapter 13.
If fl (rl) is a sufficiently narrow spectrum peaked near r = rdm, then approximately
∞
2
σ col ≈ π Ec rdm v (rdm ) ∫ fl (r ) dr = π Ec rdm
2
v (rdm ) N l , (14.2.20a)
r0

where Nl is the concentration of large drops. Now, using (Eqn. 14.2.17) here for the loss of small
particles, we obtain a coagulation kinetic equation for the small fraction

 ∂ fs 
 ∂t  = − I loss = −σ col fs , r < r0 . (14.2.21)
col

Multiplying by (4/3)prwr 3 and integrating by radii, we obtain the loss rate (dqls/dt)col of the small-size
fraction due to coagulation with the large-size fraction:
r
 dqls  4π 0
 ∂f 
  = ρ w ∫ r 3  s  dr
dt col 3 0
 ∂t  col
r0
4πρ w 3
= −σ col ∫ r fs dr = −σ col qls , r < r0 . (14.2.22)
0
3

Comparison of (Eqns. 14.2.19) and (14.2.22) shows that if scol is defined by (Eqn. 14.2.20) for both
small- and large-size fractions, then (dqls /dt)col = −(dqll /dt)col; that is, the loss of the mass of small-size
fraction particles is equal in magnitude to the gain of the mass of large-size fraction particles. Hence,
(dqls /dt)col + (dqll /dt)col = 0, and mass is conserved in the continuous collection approximation with
this definition of scol.

14.3. Basic Equations and Assumptions for the Large-Size Fraction

The continuous collection approximation is the simplest approximation for description of the coagu-
lation/accretion processes. A more detailed consideration of analytical solutions to the kinetic equa-
tion for the large-size fraction requires some simplifications and assumptions. As in Chapter 13,
14.3. Basic Equations and Assumptions for the Large-Size Fraction 693

we consider either pure liquid or crystalline clouds; a generalization for mixed phase clouds can
be done in a similar way considering liquid and crystalline size spectra and interactions between
them. The entire size spectrum of the drops or crystals consists of two size fractions, small, fs(r), and
large, fl (r), with the boundary radius at r = r0 between the two size fractions, where a minimum is
usually observed in the size spectra composed of both fractions. Based on this minimum, the value
r0 ∼ 30–50 μm can be assumed for the liquid phase (see e.g., Cotton et al., 2011), and ∼30–80 μm
(or maximum dimension D0 ∼ 60–160 μm) for the crystals as illustrated in Section 14.5 (see Figs. 14.3,
14.4). In the categorization of the condensed phase used in the bulk models parameterizations, the
function fs (r) corresponds to cloud water for the liquid phase and cloud ice for the crystalline phase,
and the function fl (r) corresponds to rain for the liquid phase and snow (or graupel or hail) for the
crystalline phase.
The same assumptions as in Chapter 13 for the small-size fraction are made here for the large-size
fraction size distribution function fl : 1) horizontal homogeneity or horizontal averaging over some
scale, so that horizontal derivatives are zero (the solutions can be easily generalized for the nonzero
horizontal derivatives in parametric form); 2) quasi-steady state, so that ∂fl / ∂t = 0. With these
assumptions, the kinetic (Eqn. 13.5.6) from Chapter 13 for fs can also be written for the size distribu-
tion function of the large-size fraction fl of the drops or crystals:

∂ ∂ ∂2 f
( w − v (r ) ) fl  + ( rɺcond fl ) = k 2l
∂z ∂r ∂z
 ∂ 2 fl ∂ 2 fl  2
2 ∂ fl  ∂f 
+ cn kGs  + + c kG +
 ∂ r ∂ z ∂ z ∂ r 

nn s
∂ r 2
 ∂t  col ,ls
 ∂f   ∂f   ∂f   ∂f 
+ + + + . (14.3.1)
 ∂t  col , g  ∂t  col ,l  ∂t  br , g  ∂t  br ,l

Here z is height, r is the particle radius, k is the coefficient of turbulent diffusion, w is the vertical
velocity, v(r) is the particle fall velocity, and rɺcond is the condensation (deposition) growth rate; a
dimensionless parameter Gs and cn, cnn, are the coefficients arising from the nonconservative tur-
bulence coefficients kijn, kijnn defined in Sections 13.3 and 13.8. The first three terms on the right-
hand side describe the turbulent transport and effects of stochastic condensation. The fourth term,
(∂fl /∂t)col,ls, is collection gain in the large-size fraction due to coagulation (accretion) with the small-
size fraction, and the terms (∂fl /∂t)col,g, (∂fl /∂t)col,l, (∂fl /∂t)br,g, and (∂fl /∂t)br,l denote respectively col-
lection gain, collection loss, breakup gain, and breakup loss due to interactions within the large-size
fraction alone. Such decomposition of the collection terms is similar to Srivastava (1978).
A simplified Maxwellian growth rate is assumed for condensation/deposition:

bcon s Dv ρ vs
rɺcond = , bcon = , (14.3.2)
r Γ p ρw

where all the notations are the same as in Chapter 13.

The derivation of continuous collection approximation from the integral Smoluchowski collec-
tion equation and simplifications are given in Section 14.2. It was shown there that: 1) the continu-
ous collection approximation is a first-order approximation by the mass of the small particle to the
full stochastic coagulation equation; and 2) the Smoluchowski coagulation equation allows the term
694 Analytical Solutions to the Stochastic Kinetic Equation for Precipitating Clouds

(∂fl /∂t)col,ls for the collection gain to be written analogously to the condensation term (the 2nd term
on the left-hand side in (Eqn. 14.3.1)):

 ∂ fl (r )  ∂ ∂
 ∂t  = − ∂r [rɺcoag fl (r )] = − χ c ∂r [ v (r ) fl ], (14.3.3)
col , ls

where rɺcoag is the coagulation (accretion) radius growth rate

dr Ec qls
rɺcoag = mɺ coag = χ c v (r ), χc = . (14.3.4)
dm 4 ρw

Now, the integral Smoluchowski coagulation equation can be written in the continuous collection
approximation in a simplified differential form for both small and large fractions as (Eqn. 14.2.17),
where scol is the same collection rate as introduced in Chapter 13 and used there in calculations of
small-size spectra. It was derived in Section 14.2, (Eqn. 14.2.20). This form of scol ensures mass
conservation—i.e., the mass loss of the small fraction is equal to the mass gain of the large fraction.
We can also introduce the inverse quantity:
−1
 ∞ 
τ col = σ −1
col =  π Ec ∫ r 2 v (r ) fl (r ) dr  , (14.3.5)
 r0 

which is the characteristic coagulation (accretion) time of the e-folding decrease in qls or the corre-
sponding increase in qll if the other processes are absent. Then,

qls (t ) = qls (0) exp(− t /τ col ), (14.3.6)

qll (t ) = qll (0) + qls (0)[1 − exp(− t /τ col )]. (14.3.7)

The sum qls(t) + qll(t) = qls(0) + qll(0), which ensures mass conservation. It is interesting to compare
this time scale tcol with the supersaturation relaxation time tf discussed in Chapters 5 and 13, and to
express it via the sum of fs and fl:
−1
 ∞

τ f =  4π Dv ∫ r[ fs (r ) + fl (r )] dr  = [4π Dv ( N s rs + N l rl )]−1 , (14.3.8)
 0 

where rs , rl are the mean radii of the small and large-size fraction, and Nl is the number density of
the large-size fraction. This time determines the condensation (evaporation) growth rate. The term
N s rs is usually greater than N l rl , thus the time tf at condensation is determined mostly by the small
particles. In the absence of small particles at evaporation, tf is determined by the large fraction. The
coagulation (accretion) time tcol is determined by the large particles, as follows from (Eqn. 14.3.5).
If the cloud water content of the large-size fraction is sufficiently small, the last four terms in
(Eqn. 14.3.1)—(∂fl /∂t)col,g, (∂fl /∂t)col,l, (∂fl /∂t)br,g, (∂fl /∂t)br,l —for collection and breakup are also
small and can be neglected, which is usually done in some bulk cloud models. This situation cor-
responds to sufficiently small concentrations Nl of the large drops, so that collisions among large
particles are not frequent. With increasing Nl, water content and rain or snow intensity, the error of
this approximation may increase and these terms should be accounted for; this is especially impor-
tant for convective clouds. Srivastava (1982) and Feingold et al. (1988) evaluated the coalescence
14.3. Basic Equations and Assumptions for the Large-Size Fraction 695

and breakup terms analytically, but the collision and breakup kernels were specified to be constant
(independent of radii), and the solution was expressed via Bessel functions that are difficult to ana-
lyze analytically.
We use a parameterization of coalescence and breakup based on an assumption that is justified
using the work by Hu and Srivastava (1995). The detailed analysis of various terms in the coales-
cence-breakup kinetic equation [the last four terms in (Eqn. 14.3.1)] performed in Hu and Srivastava
(1995) showed that these terms are approximately proportional to each other over the major radii
range, and are mostly mutually compensated near the equilibrium steady state. We hypothesize that
these terms are proportional to the collection (accretion) gain (∂fl /∂t)col,ls and can be roughly param-
eterized by expressing via (∂fl /∂t)col,ls with some proportionality coefficients ccg > 0, ccl < 0, cbg > 0,
cbl < 0 for the corresponding processes (the subscripts “c” and “b” mean collection and breakup; “g”
and “l” mean gain and loss). These coefficients are, in general, functions of r but are proportional to
each other. Therefore, the sum of (∂fl /∂t)col,ls and all four last terms in (Eqn. 14.3.1) can be expressed
via (∂fl /∂t)col,ls as

 ∂f   ∂f   ∂f   ∂f   ∂f 
  +   +   + ≈ ccb  , (14.3.9)
∂t  col , g  ∂t  col ,l  ∂t  br , g  ∂t  br ,l  ∂t  col ,ls

where ccb = 1 + ccg + ccl + cbg + cbl. In a box model used in Hu and Srivastava (1995), equilibrium
among these four terms is reached after some sufficient time so that they are mutually compensated,
forming equilibrium spectra; thus, ccb → 1. In our case, the balance also includes the vertical mass
gradient, and diffusion and accretion growth, so that there can be only approximate compensation
among these four terms, and ccb can slightly differ from 1. That is, the net effect of collection and
breakup gain and loss is to change the accretion growth rate rɺcoag of the large particles described
by (Eqn. 14.3.4)—i.e., the collection efficiency Ec. Then, we can introduce the correction ccb into
parameter Ec and solve the equation taking into account only (∂fl /∂t)col,ls, as in (Eqn. 14.3.3). This cor-
responds to the approximation adopted in many bulk cloud models. It will be shown in the following
text that this simple parameterization yields the functional r-dependence of the collection growth rate
that is in good agreement with more precise calculations in Hu and Srivastava (1995).
Note that the assumption (Eqn. 14.3.9) is not mandatory for analytical solutions obtained in the
following text, we just use the fact, based on Hu and Srivastava (1995), that the sum of these four
terms caused by interactions within only the large fraction can be much smaller (due to mutual com-
pensation) than the term (∂fl /∂t)col,ls caused by interactions between the small and large fractions.
When the numerical models provide new information about the relative values of the terms in the
coagulation-breakup equation, this assumption and analytical solutions can be modified accordingly.
The same closure as in Chapter 13 is chosen for the vertical gradient of the size spectra:
∂ fl (r , z )
= α l ( z )ς l (r ) fl (r , z ). (14.3.10)
∂z
In the simplest model zl (r) = 1, al can be related from (Eqn. 14.3.10) to the relative gradient of the
LWC (IWC) of the large-size fraction:

α l ( z ) = (1/qll )(dqll /dz ). (14.3.11)

696 Analytical Solutions to the Stochastic Kinetic Equation for Precipitating Clouds

Substituting (Eqn. 14.3.10) into (Eqn. 14.3.1) allows elimination of z derivatives; also using (Eqns. 14.3.2)
and (14.3.4), and assuming now zl(r) = 1, we have a differential equation that is a function only of r:

d 2 fl  bcon s  df
cnn kGc2 + − − χ c v (r )  l
dr 2  r  dr
 d (α k ) dw b s dv (r ) 
+ α l2 k + l
− α l (w − v) − + con2 − χ c fl = 0. (14.3.12)
 dz dz r dr 

This equation allows analytical solutions that are found in the next section.

14.4. Solutions for the Large-Size Fraction Taking into Account

Diffusion Growth and Coagulation

We seek analytical solutions for the general case and then for four particular cases that include the
following: the size range where fall speed is a linear function of particle size; where fall speed is pro-
portional to the square root of particle size (see Chapter 12); conditions where coagulation growth is
dominant; and in the subcloud layer where the small-size fraction is absent as it has been evaporated
in the upper subsaturated layers.

14.4.1. General Solution

The solutions in Chapter 13 indicate that stochastic condensation influences predominantly the small-
size fraction. Therefore, it is reasonable to assume that the contribution of the stochastic diffusion
terms are much smaller for the large-size fraction, and the shape of the spectra is determined mostly
by the balance between regular growth/evaporation, vertical transport, collection, and sedimentation.
Then, neglecting in (Eqn. 14.3.12) the terms with Gs and the effects of stochastic condensation, and
using (Eqns. 14.2.10) and (14.2.11), the kinetic equation can be written for the quasi-steady state as

d  fl  d
bcon s   + χ c ( fl v (r )) + [ w − v (r ) − α l k ]α l fl = 0 (14.4.1)
dr r dr

(we neglect here for simplicity the terms with dw/dz, dk/dz, and dal /dz that can be introduced into
the final equations).
Introducing a new variable jl = fl /r, and solving (Eqn. 14.4.1) relative to j l, we obtain

1 dϕ l
= −ψ l (r ), (14.4.2)
ϕ l dr
where
ul (r ) 1 dgl (r )
ψ l (r ) = β l 0 + + , (14.4.3)
gl (r ) gl (r ) dr
αl
βl 0 = − , (14.4.4)
χc
gl (r ) = bcon s + χ c rv (r ) = rrɺtot (r ), (14.4.5)
14.4. Solutions for the Large-Size Fraction Taking into Account Diffusion Growth 697

ul (r ) = − β l 0 bcon s + α l r ( w − α l k ), (14.4.6)
rɺtot (r ) = rɺcond (r ) + rɺcoag (r ), (14.4.6a)

where rɺtot (r ) is the total radius growth rate. The integral of (Eqn. 14.4.2) is
r

ϕ l (r ) = ϕ l (r0 ) exp(− Jl 0 ), Jl 0 = ∫ ψ l (r ′) dr ′, (14.4.7)

r0

where r0 is the left boundary of the large-size fraction. Substituting (Eqns. 14.4.3)–(14.4.6) into
(Eqn. 14.4.7), and integrating, we obtain the solution for fl(r):

r gl (r0 )
fl (r ) = fl (r0 ) exp  − β l 0 (r − r0 ) − Jl1 
r0 gl (r )
rɺ (r )
= fl (r0 ) tot 0 exp  − β l 0 (r − r0 ) − Jl1  , (14.4.8)
rɺtot (r )
where
r
ul (r ′)
Jl 1 = ∫ dr ′. (14.4.9)
r0
gl (r ′)

This is the general solution to the kinetic (Eqn. 14.4.1) for the large-size fraction at r > r0 taking into
account the condensation and continuous collection. For application in bulk microphysical models,
the integral Jl1 can be evaluated numerically at any value of w, k, s, al, and qls; the fall speeds v(r) for
the drops accounting for nonsphericity and for various crystal habits can be evaluated as continuous
functions of r as described in Chapter 12.
In certain particular cases, the integral Jl1 can be obtained analytically and the solutions are simpli-
fied if the quasi-power law for terminal velocity

v (r ) = Av r Bv (14.4.10)

is applicable. Substituting (Eqns. 14.4.5), (14.4.6), and (14.4.10) into (Eqn. 14.4.9) and assuming that
Av = const and Bv = const over some interval of radii (r1, r2), we obtain
Jl1 = I1 + I 2 , (14.4.11)
r2
dr
I1 = − β l 0 bcon s ∫ , (14.4.12a)
r1
bcon s + χ c Av r Bv +1
r2
rdr
I 2 = α l (w − α l k ) ∫ . (14.4.12b)
r1
bcon s + χ c Av r Bv +1

Tabulated analytical expressions for these integrals exist only for very limited values of Bv
(Gradshteyn and Ryzhik, 1994). Therefore, we will illustrate the general solution for three particular
cases: 1) when v(r) is a linear function of r (intermediate regime of fall speeds of moderately large
particles) 2) when the condensation rate is much smaller than the collection rate and can be neglected;
and 3) when v(r) is proportional to r1/2 (aerodynamic regime of fall speeds, see Chapter 12).
698 Analytical Solutions to the Stochastic Kinetic Equation for Precipitating Clouds

14.4.2. Particular Case: Fall Speed as a Linear Function of Particle Size

The linear regime for particle terminal velocity with Bv = 1; that is, v(r) = Avr, is valid in the inter-
mediate range of drop radius 60 to 600 μm (e.g., Rogers and Yau, 1989), for spherical ice particles,
and for some crystal habits in the region r = 90–300 μm (see Chapter 12; Sections 12.1 and 12.6,
(Eqn. 12.1.7b). The integrals I1 and I2 for the linear function v(r) are evaluated in Appendix A.14. The
integrals have different expressions for the cases of condensation (s > 0) and evaporation (s < 0) and
can be expressed using the new parameters:
1/2 1/2
 b | s |  | rɺcond (r ) | 
Rl =  con  = r  rɺ (r )  , (14.4.13a)
χ
 c v 
A  coag 
(α l k − w) β0 R
Ul = βl 0 , Ql = , (14.4.13b)
2 Av 2

where |s| and | rɺcond | denote the absolute values of supersaturation and condensation growth rates.
Substituting expressions for I1 and I2 at s > 0 from Appendix A.14 into (Eqns. 14.4.12a) and
(14.4.2b) and then into (Eqn. 14.4.8) yields the following fl(r) in the condensation layer:
Ul
rɺ (r )  (r /R )2 + 1 
fl (r ) = fl (r0 ) tot 0  0 l 2 
rɺtot (r )  (r /Rl ) + 1 
  r r 
× exp  − β l 0 (r − r0 ) − β l 0 Rl  arctg 0 − arctg   , s > 0. (14.4.14)
  Rl Rl  

Using expressions for I1 and I2 from Appendix A.14 for the evaporation layer (s < 0) yields two solu-
tions for the two size regions, r < Rl and r > Rl:
Ql
rɺ (r )  (1 − r0 / Rl )(1 + r / Rl ) 
fl (r ) = fl (r0 ) tot 0  
rɺtot (r )  (1 − r / Rl )(1 + r0 / Rl ) 
Ul
 (r / R )2 + 1 
× 0 l 2  exp  − β l 0 (r − r0 )  ,
 (r / Rl ) + 1 

for s < 0, r < Rl . (14.4.15)

Ql
rɺtot (r0 )  (r0 / Rl + 1)(r / Rl − 1) 
fl (r ) = fl (r0 )  
rɺtot (r )  (r / Rl + 1)(r0 / Rl − 1) 
Ul
 (r / R )2 + 1 
× 0 l 2  exp [ − βl 0 (r − r0 ) ] ,
 (r / Rl ) + 1 
for s < 0, r > Rl . (14.4.16)

The equations for s < 0 are not applicable at one point r = Rl, since then rɺcoag = − rɺcond and the total growth
rate rɺtot = 0 , in contradiction with the assumption made when deriving (Eqns. 14.4.7) and (14.4.8).
The physical meaning of the parameter Rl and of the solutions (Eqns. 14.4.14)–(14.4.16) is clear
from (Eqn. 14.4.13a): (r / Rl )2 = rɺcoag /| rɺcond | is the ratio of the collection rate to the condensation/
evaporation rate. The conditions r < Rl or r > Rl mean that the collection rate is smaller or greater
14.4. Solutions for the Large-Size Fraction Taking into Account Diffusion Growth 699

than the condensation/evaporation rate, rɺcoag < | rɺcond | for r < Rl or rɺcoag > | rɺcond | for r > Rl. The bound-
ary condition r = Rl = (bcon | s | / χ c Av )1/ 2 can be estimated for the following parameters: T ∼ 0 °C,
rvs ≈ 5 × 10−6 g cm−3, super- or subsaturation s = ±0.1 (±10%), qls = 0.1 g m−3, Ec = 0.5, Av ≈ 8 × 103 s−1
(see Chapter 12; Sections 12.1 and 12.4). Then, cc ∼ 10−8, bcon|s|∼10−7 cm2 s−1, and Rl ∼ 350 μm. For
|s| = 0.2 (or ±20%), or |s| = 0.4 (or ±40%), as can be in crystalline clouds or in evaporation layers,
Rl increases to ∼500 and 700 μm. With |s| =10−3 (± 0.1%) and qls = 1 g m−3, as can be in convective
clouds, Rl ∼ 12–15 μm at T = 0 to 10 °C. For conditions of cirrus, T = −40 to −50 °C, p = 200 hPa,
qls = 20 mg m−3, |s| = 0.10 (± 10%), the value Rl ∼ 200 μm. These estimates can be used to assess the
asymptotic solutions.
At r >> Rl (i.e., when rɺcoag >> | rɺcond | and coagulation–accretion growth prevails), these solutions
tend to the asymptotic, which is the same for both solutions (Eqns. 14.4.14)–(14.4.16) at sub- and
supersaturations:
pl
r
fl (r ) = fl (r0 )   exp[− β 0 (r − r0 )], (14.4.17a)
 r0 
(w − α l k )
pl = − (2U l + 1) = β l 0 − 1. (14.4.17b)
Av

Thus, the analytical solutions for the large-size fraction in both the growth and evaporation layers are
gamma distributions similar to those suggested and analyzed by Ulbrich (1983), Willis (1984), Zhang
et al. (2001, 2003a,b), Brandes (2003), Heymsfield (2003), and others.
If in (Eqn. 14.4.17b) the parameter (2Ul + 1) < 0, then the index pl is positive and the spectra
represent the typical gamma distributions. If (2Ul + 1) > 0, then the index pl is negative—i.e., these
generalized gamma spectra represent a product of the inverse power law and the exponential Marshall–
Palmer spectrum. Which functional type dominates depends on the combination of the parameters.
The condition w > alk usually takes place in (Eqn. 14.4.17b), and the term with w mostly determines pl.
As discussed in Chapter 13, the effective w decreases with increasing scales of spatial-temporal
averaging. At sufficiently large scales, w becomes small, pl tends to zero, and the size spectrum
(Eqn. 14.4.17a) tends to the Marshall–Palmer distribution. This prediction of our model coincides
with the observations (e.g., Joss and Gori, 1978), and statistical theories of Marshall–Palmer spectra
(e.g., Liu, 1993). However, the local spectra can be narrower than the Marshall–Palmer, and better
described by gamma distributions like (Eqn. 14.4.17a), as discussed in Section 14.1. Which type of
spectrum is preferable and what is the relation between b l and pl is still the subject of discussion in
the literature (see Section 14.5).

14.4.3. Particular Case: Coagulation Growth Rate Much Greater than Diffusion Growth Rate
For sufficiently large r and small sub- or supersaturations, when rɺcoag >> rɺcond , the condensation
rate can be neglected. Then, using the quasi-power law form (Eqn. 14.4.10) for the fall speed v(r),
assuming Av and Bv are approximately constant in some region of r and Bv < 1, the integral Jl1 in
(Eqn. 14.4.9) can be evaluated as
r
dr  w − αl k   r r0 
Jl1 = β l 0 (α l k − w) ∫ = βl 0    v (r ) − v (r )  . (14.4.18)
r0
v (r )  1 − Bv  0 
700 Analytical Solutions to the Stochastic Kinetic Equation for Precipitating Clouds

Introducing a size-dependent slope bl(r),

 w − αl k 
β l (r ) = β 0 l 1 + , (14.4.19)
 (1 − Bv ) v (r ) 

and substituting (Eqns. 14.4.18) and (14.4.19) into (Eqn. 14.4.8), we obtain

v (r0 )
fl (r ) = fl (r0 )
v (r )
{
exp −  β l (r )r − β l (r0 )r0  . } (14.4.20)

Assuming that Bv ≈ const in the power law v (r ) ≈ Av r Bv for the considered region of r, the ratio
v (r0 ) /v (r ) ≈ (r /r0 )− Bv and (Eqn. 14.4.20) becomes

f (r ) = f (r0 )(r /r0 )− Bv exp[− β (r )(r − r0 )]. (14.4.21)

Thus, we obtain again a generalized gamma distribution with the negative index pl = −Bv. This is
again a product of the inverse power law and MP-type size distributions. Which dependence domi-
nates depends on the combination of the parameters. In many cloud types, v(r) >> w and v(r) >> a l k
for the large-size fraction, then b (r) ≈ b l0 and

f (r ) = cN (r /r0 )− Bv exp(− β l 0 r ). (14.4.22)

Since Bv ≤ 0.5 for large particles, the spectrum tends to the MP exponent; however, there is also an
algebraic term that is a function of r.

14.4.4. Particular Case: Aerodynamic Regime for the Fall Speed of Large Particles

As discussed in Chapter 12 (Sections 12.4 and 12.6), for sufficiently large radii, the terminal velocity
can be approximated by the law v(r) = Av r1/2 where Av also includes a height correction (ra0 /ra)1/2
with ra0 and ra being the air densities at the surface and at a given height. This regime is approxi-
mately valid for large drops, some ice particles with shapes close to spherical (graupel, hail), and
some other crystals’ habits. The integrals I1 and I2 in (Eqns. 14.4.12a) and (14.4.12b) for this case,
with Bv = 1/2, are evaluated in Appendix B.14. Substituting them into Jl1 in (Eqn. 14.4.8) yields for
the condensation layer with s > 0:
2 Φ1 l − Φ1 l
rɺtot (r0 )  x + 1   x2 − x +1 
fl (r ) = fl (r0 )
rɺtot (r )  x 0 + 1   x2 − x +1 
 0 0 
× exp  − β l 0 (r − r0 ) − Vl ( x − x 0 ) 
 2β H 2x − 1
x
V x 3
x

× exp  l 0 l arctan + l arctan , (14.4.23)
 3 3 x0 3 2− x 
 x0 

where the vertical bar with limits is used in the equation for brevity and has the same meaning as
in the integrals (i.e., the function at the lower limit is subtracted from the function at the upper
limit), and
14.4. Solutions for the Large-Size Fraction Taking into Account Diffusion Growth 701

2/3 1/2 1/2

 b | s |  r   r 
H l =  con , x= , x0 =  0  , (14.4.24a)
 
 χ c Av   Hl   Hl 
2α l ( w − α l k ) H l1/2 Vl β l 0 H l
Vl = , Φ1l = − . (14.4.24b)
χ c Ac 6 3

Substitution of I1 and I2 for the evaporation layer with s < 0 from Appendix B.14 into (Eqn. 14.4.11)
for Jl1 and then into (Eqn. 14.4.8) yields
−2 Φ2 l Φ2 l
rɺtot (r0 )  x − 1   x2 + x +1 
fl (r ) = fl (r0 )
rɺtot (r )  x 0 − 1   x 2 + x + 1
 0 0 
× exp  − β l 0 (r − r0 ) − Vl ( x − x 0 ) 
 2β H 2x + 1
x
V x 3
x

× exp  l 0 l arctan + l arctan , (14.4.25)
 3 3 3 2 +x 
 x0 x0 

V β H
Φ2l = l + l 0 l . (14.4.26)
6 3
The parameter Hl is the characteristic length that determines the onset of the asymptotic regime.
An estimate of Hl from (Eqn. 14.4.24a) with qls = 0.1 g m−3 (stratiform clouds) with bcon and rvs at
T ∼ 0 °C, |s| = 0.1 (± 10%, ice phase cloud), Av = 2.2 × 103 (r0/r)1/2 cm1/2 s−1 (Section 12.4) yields
Hl ≈ 300 μm. For the same qls but with |s| = 10−3 (± 0.1%, liquid phase cloud), Hl ≈ 15 μm; with
qls ∼ 1 g m−3 (convective clouds), Hl ∼ 5 μm. For cirrus at T = −40 to −50 °C, p ∼ 200 mb, r/r0 ∼ 0.4,
and qls = 10–20 mg m−3, an estimate yields Hl ∼ 60–120 μm. Thus, in all these cases, r >> Hl, and
x >> 1 for the large-size fraction. We can estimate the asymptotics of various terms in (Eqn. 14.4.23)
at x >> 1. The product of two brackets with x = Vl(r/Hl)1/2 before the exponent tends at large x to a limit
x 2 Φ1l x −2 Φ1l → 1 . The arguments of arctan in the exponent tend to infinity; arctan tends to ±p /2, which
−1/2
results in a change of the normalizing constant. The term 1/rɺtot (r ) → r / [ rv ( r )] = v ( r ) → r −1/2 .
Incorporating these limits, we find the asymptotic of fl (r) at s > 0:

fl (r ) ~ r −1/2 exp[− β l 0 r − Vl (r /H l )1/2 ]. (14.4.27)

The same estimates for fl (Eqn. 14.4.25) at s < 0 yield the same asymptotic. An estimate of Vl with
qls = 0.1 g m−3 and w = 1 cm s−1 gives Vl ∼ 0.1. At r ∼ 1 mm, the value Vlx ∼ 0.3, while with b l0 ∼
40 cm−1, the value b l0r = 4. Thus, the term Vl(r/Hl)1/2 in the exponent of (Eqn. 14.4.27) can be neglected
and fl (r) ∼ r−1/2 exp(−b l0r)—i.e., its asymptotic coincides with that in Section 14.4.3 and tends to
the Marshall–Palmer spectrum with a correction r−1/2. However, for greater convective updrafts of
w ∼ 1 m s−1 and ∼ qls = 1 g m−3, an estimate yields Vl ∼ 1—i.e., the value Vl x ∼ 3 at r ∼ 1 mm, which
is comparable in magnitude to b l0r. Then, the term Vl x should be retained in the exponent, the slope
becomes nonlinear, and the spectra may be slightly concave downward in log-linear coordinates—
i.e., the slopes increase with r and the spectra decrease with r faster than for the MP spectrum. Thus,
this analytical solution explains observations of such concave downward spectra by Willis (1984) in
convective clouds.
702 Analytical Solutions to the Stochastic Kinetic Equation for Precipitating Clouds

14.4.5. Solutions for Subcloud Layers

The previous solutions were obtained for the case of large particles coexisting with cloud liquid/ice,
that is, with the small-size fraction fs. When the small-size fraction has been evaporated—e.g., fall-
ing through the subsaturated subcloud layer, or in the downdraft or near the cloud edge—and large
drops exist without the cloud particles, another regime occurs, rɺcoag << | rɺcond | . That is, the coagulation–
accretion rate is negligible and the large fraction evaporates with rate rɺcond . To address this situation, we
solve (Eqn. 14.4.1) taking into account diffusional growth (evaporation) but neglecting the accretion term
d  fl 
bcon s   + [ w − v (r ) − α l k ]α l fl = 0. (14.4.28)
dr  r 
This equation coincides with (Eqn. 13.7.1) for the tail of the small-size fraction, except that the loss
term with scol is absent and we omitted for brevity the terms with dk/dz and dal /dz (which can be
included in the final solution). Assuming again a power law for the terminal velocity with coefficients
Av, Bv, we can modify the solution (Eqn. 13.7.2) as:
r
fl (r ) = fl (rbe ) exp{−[β le (r )r − β le (rbe )rbe ]}, (14.4.29)
rbe

where rbe denotes the lower boundary of the evaporating large-size fraction, and the size-dependent
slope ble(r) for the evaporation layer is

rα l  w − α l k v (r ) 
β le (r ) =  − . (14.4.30)
bcon s  2 Bv + 2 

For large enough r and without vigorous vertical velocities, the second term in (Eqn. 14.4.30) domi-
nates and the slope is similar to that obtained in (Eqn. 13.7.7),
αl
β le (r ) = cl1rv (r ), where cl1 = − . (14.4.31)
bcon s( Bv + 2)

To ensure a decrease of fl with r, b le should be positive; thus, the signs of al and s should be different
in the evaporation layer (i.e., al > 0 and dqll /dz > 0 at s < 0) and LWC (IWC) should decrease down-
ward in the subcloud layer at s < 0, which is characterized by evaporating precipitation.
The spectra in (Eqn. 14.4.29) are generalized gamma distributions, and the behavior of the slopes
depends on the velocity power index. In particular, b le ∼ r2 and fl ∼ exp(−cl1Avr3) for v(r) = Avr and
b le ∼ r 3/2, fl ∼ exp(−cl1Avr 5/2) for v(r) = Avr1/2. In vigorous downdrafts that cause subsaturation, such
that |w| >> v(r), the asymptotic slope (Eqn. 14.4.30) becomes

α l (w − α l k )
β le = cl 2 r , cl 2 = . (14.4.32)
2bcon s

Since both w and s are negative and al > 0, then −a lk < 0. Therefore, cl2 > 0 and b le > 0, thus
fl decreases with r and (Eqn. 14.4.32) ensures a correct asymptotic. Then, the spectrum behaves as
fl ∼ exp(−cl2r2). Thus, the spectra of the precipitating particles in the evaporating subcloud layer fall
off more rapidly with r than in cases with the presence of the small fraction, qls > 0, and become
concave downward in log-linear coordinates, which can explain observations described by Ulbrich
(1983), Willis (1984), and Zawadski and de Agostinho Antonio (1988).
14.5. Interpretation of Solutions 703

14.5. Interpretation of Solutions

In this section, a physical interpretation is given for solutions for the large-size fraction obtained in
Section 14.4 and they are illustrated with calculations for a crystalline cloud.

14.5.1. General Analysis of the Parameters

The MP spectra, fl ∼ exp(−ΛD), play a fundamental role in many cloud and climate models and
remote sensing (especially radar) techniques. The values of Λ = bl0 /2 can be estimated using
(Eqn. 14.4.4) for bl0 that can be rewritten for layers with qls > 0 by using (Eqn. 14.3.4) for cc:
α l 4(−α l ) ρ w
βl 0 = − = . (14.5.1)
χc Ec qls

Note that al < 0 since al = (dqll /dz)/qll and fl and ql increase downward, which is expected for fall-
ing particles growing by collection. Under this condition, bl0 > 0 and exp(−bl0r) decreases with r.
Equation (14.5.1) reveals that bl0 decreases—i.e., the spectra stretch toward large sizes, when the
following processes occur: 1) Ec or qls increase—i.e., the rate of mass transfer from the small to the
large-size fraction increases; 2) rw decreases and the mass gained by the large-size fraction is dis-
tributed over the larger range of volumes and radii; 3) (−al) = |al| decreases—i.e., the gravitational,
convective, and turbulent fluxes of fl decrease, causing weaker outflow of fl from a given cloud level.
As an example, we can estimate from (Eqn. 14.5.1) the slope bl0 for the snow size spectra using
data from Passarelli (1978b). Taking Ec ∼ 0.5–1, snowflake bulk density rw ∼ 0.1–0.2 g cm−3, the
water content of the small-size fraction as qls ∼ 0.1 g m−3, and the thickness of the layer ∼ 0.5–2 km,
we obtain bl0 ≈ 40–160 cm−1, or Λ = bl0 /2 ≈ 20–80 cm−1. This is within the range of values of
Λ = 10–100 cm−1 given by Platt (1997), Passarelli (1978b), Houze et al. (1979), and Ryan (2000).
Equation (14.5.1) provides an explanation for some observed peculiarities of b l0 in crystalline
clouds. The analyses performed by Platt (1997), Houze et al. (1979), and Ryan (2000) show that
b l0 increases by about an order of magnitude when temperature T decreases from 0 °C to −50 °C
(Fig. 3 in Platt, 1997). The same analysis shows that the ice water content decreases in this tempera-
ture range, although somewhat faster (Fig. 4 in Platt 1997). According to (Eqn. 14.5.1), b l0 ∼ qls−1,
and this may explain the observed increase in b l0 with decreasing T and qls. The slower increase with
T by b l0 relative to the decrease in qls may be caused by decreasing cloud thickness at lower T—i.e.,
vertical gradients of IWC and al in the numerator of (Eqn. 14.5.1). This temperature dependence of
b l0 or Λ may cause the height dependence observed by Passarelli (1978b), who measured Λ ≈ 65 cm−1
at z = 3.35 km (T = −20 °C) and Λ ≈ 24 cm−1 at z = 2.55 km (T = −12 °C). This increase in Λ (or b l0)
with decreasing height can also be a consequence of the qls(T) dependence.
An interesting feature of the exponential MP spectra is that the range of slopes is similar for both
liquid and crystalline particles. Marshall and Palmer (1948) related the slopes with the rainfall rate
R0 in mm h−1 with an equation Λ = 41R0−0.21 (cm−1), yielding b l0 = 2Λ = 130 to 50 cm−1 for R0 = 0.1
to 10 mm h−1. An estimate from (Eqn. 14.5.1) with Ec ∼ 0.5, rw ∼1 g cm−3, qls ∼1 g m−3, al ∼ 0.5 km−1
yields b l0 = 40 cm−1, which is in the middle of the range of b l0 values determined for the MP spectra,
and hence (Eqn. 14.5.1) can be applicable to MP spectra in liquid clouds.
704 Analytical Solutions to the Stochastic Kinetic Equation for Precipitating Clouds

Considering convective rain and the equations in Section 14.4, the pl-index (Eqn. 14.4.17b) with
v(r) = Avr is applicable near the observed modal diameter ∼0.2–0.4 mm in warm rain (e.g., Ulbrich,
1983; Willis, 1984). Using the relation −al = bl0c from (Eqn. 14.4.4), the pl-index (Eqn. 14.4.17b)
can be written as
pl = cβ 1 β l20 + cβ 2 β l 0 − 1, (14.5.2a)
cβ 1 = χ c k /Av , cβ 2 = w /Av . (14.5.2b)

Equation (14.5.2a) can be rewritten in terms of Λ = bl0 /2 with corresponding coefficients c1Λ = 4cb1
and c2Λ = 2cb2. Equation (14.5.2a) resembles the empirical fit found by Zhang et al. (2001) from radar
and disdrometer data

pl = cΛ1 Z Λ 2 + cΛ 2 Z Λ − 1.957, (14.5.3)

cΛ1Z = −1.6 × 10−4 cm−2, cL2Z = 0.1213 cm−1. A similar relation was suggested by Heymsfield (2003)
for crystalline clouds based on aircraft measurements:
pl = cΛ1H Λ cΛ 2 H − 2, (14.5.4)

where cΛ1H = 0.076 cm−0.8, and cΛ2H = 0.8.

The estimates from (Eqns. 14.5.2a) and (14.5.2b) with typical cloud parameters show that the value
of cb1 has a smaller magnitude and is opposite in sign to cΛ1Z; hence, this relation is determined mostly
by the coefficient cb2. This is in agreement with (Eqn. 14.5.3), which predicts a nearly linear relation
except for very high values Λ, and with (Eqn. 14.5.4) where the power of Λ is 0.8, and the relation
is close to linear. Thus, (Eqns. 14.5.2a) and (14.5.2b) predict positive correlations between pl, Λ, and
vertical velocities, and is in agreement with experimental data and parameterizations. The increase
in pl and Λ with increasing w predicts narrower spectra in stronger updrafts and broader spectra in
downdrafts, which is similar to the effect of stochastic condensation described in Chapter 13.
However, it should be emphasized that this analysis is just an illustration of possible applications
of these analytical solutions and should be used with caution. The slope al in (Eqn. 14.5.1) and the
pl–bl0 relation (Eqns. 14.5.2a) and (14.5.2b) are based on solutions with the presence of qls. In vigor-
ous downdrafts, in the subcloud layer or near the surface where qls ∼ 0, the solutions from Section
14.4 can be used. Then, (Eqns. 14.4.29)–(14.4.32) show that the slopes bl0(r) or Λ(r) can be expressed
as polynomials of pl (equal to 1 in this case). These equations and the asymptotic analysis show that
Λ(r) is a 2nd-order polynomial of pl if v(r) << |w| and the slope is (Eqn. 14.4.32). Such parameteriza-
tion was suggested in Zhang et al. (2003a,b) and in Brandes et al. (2003), and a 3rd- or 2.5-order
polynomial if v(r) >> |w| and the slope is (Eqn. 14.4.31).
Unfortunately, data on vertical velocities, the turbulent coefficient, and presence of the small-size
fraction are absent in the cited papers, which precludes a more detailed comparison. Verification
of the relations (Eqns. 14.5.2a) and (14.5.2b) would require simultaneous measurements of w, qls,
qll, the turbulent coefficient, and the size spectra. However, these analytical solutions are consistent
with the general findings from experimental observations: since the slopes and indices are expressed
through related quantities, this leads to the existence of the pl–Λ relations. At the same time, solutions
in Section 14.4 for various particular cases show that these relations cannot be universal, but should
depend on the altitude and position of the measured spectra in the cloud or below the cloud base, and
specifically the sign of w, values of k and al, and the presence of qls.
14.5. Interpretation of Solutions 705

14.5.2. Example Calculations for a Crystalline Cloud

The properties of snow spectra in a crystalline cloud are illustrated here in more detail. We select a
generic case, chosen for illustration to mimic the profiles in similar clouds simulated in Khvorostya-
nov, Curry, et al. (2001) and in Khvorostyanov and Sassen (2002) using the spectral bin 1D and 2D
models. The profiles for this case of qll(z) and al(z), calculated from (Eqn. 14.3.11), are shown in
Fig. 14.1a,b, along with the IWC of the small-size fraction qls and ice supersaturation, which are the
same as shown in Fig. 13.10. The temperature decreases from about −5 °C at the lower boundary to
−60 ° at 12 km.
Shown in Fig. 14.2 are the vertical profiles of the slopes bl0 and Λ calculated for this case from
(Eqn. 14.5.1). The generalized empirically derived slope Λ for crystalline clouds from Platt (1997)
is shown in Fig. 14.2b for comparison. The calculated slopes increase with decreasing temperature,
although not linearly as predicted by the generalized experimental Λ, but somewhat faster, especially
above 7 km, since al and Λ are inversely proportional to qls, which decreases upward nonlinearly at
these heights. However, the general agreement of the calculated and experimental curves is fairly
good, both in magnitude and vertical gradients. This indicates that if a large ensemble of values of
qls and qll, measured at various temperatures, are used to calculate al and Λ, then the results would
converge to the experimental curve by Platt (1997).
An example of size spectra at ice subsaturation, si < 0, at the heights 4.8–6.0 km is shown in
Fig. 14.3. The small-size fraction (Fig. 14.3a) was calculated with the generalized gamma distribu-
tions from Section 13.6. In the spectral region from 6 to about 40–50 μm, the spectra are almost linear
in log-log coordinates, close to the inverse power laws with the indices increasing toward the cloud
top (to colder temperatures). At r = 50–130 μm, the effect of the exponential tail dominates and the
spectra have a maximum at r ∼ 100–130 μm that decreases with height.
The spectra of the large-size fraction (Fig. 14.3b) are calculated using (Eqns. 14.4.18)–(14.4.20).
The spectra plotted in log-linear coordinates are nearly linear—i.e., close to the Marshall–Palmer
exponents. The size-dependent slope bl(r) slightly decreases with r as predicted by the second term
in (Eqn. 14.4.19), but the departure from linearity is small, since the slope is determined mostly by
bl0. The composite spectra obtained by matching the small- and large-size fractions at r0 = 72 μm
(Fig. 14.3c) are seen to be bimodal. The calculated composite spectra and the experimental spectrum
from Platt (1997) shown in Fig. 14.3d are in good agreement, having minima and maxima at simi-
lar positions (note the difference in radii and diameter scales in horizontal axes). The experimental
and calculated values of fl can be compared using the relation 1 m−4 ≈ 10−9 L−1 μm−1; the maxi-
mum ∼1011 m−4 in Fig. 14.3d corresponds to ∼102 L−1 μm−1, which is comparable to the maximum in
Fig. 14.3c. In these calculations, the first bimodality occurs within the small-size fraction. If the
matching point was located at greater r0 ∼ 120–150 μm, there would be a second region of bimodal-
ity at r0 due to different slopes of the small- and large-size fractions; bimodality is often observed in
this region (e.g., Mitchell 1994, Mitchell et al. 1996), and polymodal spectra are also often observed
(Sassen et al., 1989; Poellot et al., 1999).
The spectra in the condensation layer 7.5–8.7 km with positive ice supersaturation, si > 0, are
depicted in Fig. 14.4. The indices of the small-size fraction (Fig. 14.4a) are positive since p ∼ si (see
(Eqn. 13.8.4)), and the spectra are monomodal gamma distributions with maxima at r ∼ 30–50 μm.
The portion of the spectra from ∼10 to 50–60 μm in log-log coordinates is almost linear—i.e., it
706 Analytical Solutions to the Stochastic Kinetic Equation for Precipitating Clouds

12
11 IWC-large fraction
qIS - baseline
10
9 2qIS

Height (km)
8
7
6
5
4
3
0.00 0.05 0.10 0.15
IWC (g m–3)
(a)
12
11
10
9
Height (km)

8
7
6
5
4
3
–1.0 –0.5 0.0 0.5
αl (km–1)
(b)
12
11
10
9
Height (km)

8
7
6
5
4
3
–80 –70 –60 –50 –40 –30 –20 –10 0 10 20
Ice supersaturation (%)
(c)

Figure 14.1. Profiles for calculations of the size spectra of the large-size fraction: (a) IWC of the
large fraction (solid circles), of small fraction qls (triangles), and of the small fraction with doubled
IWC, 2qls (diamonds); (b) parameter al; (c) ice supersaturation s. From Khvorostyanov and Curry
(2008c). J. Atmos. Sci., 65, © American Meteorological Society. Used with permission.
14.5. Interpretation of Solutions 707

9 9
8 8
Height (km)

Height (km)
7 7
6 6
5 1 5 1
2 2
4 4
3 3
0 100 200 300 400 500 0 50 100 150 200 250
β0,I (cm–1) Λ0,I (cm–1)
(a) (b)

Figure 14.2. (a) Exponential slope bl0 and (b) Λl0 of the size spectra of the large fraction calculated
with the IWC of small fraction qls (circles) and 2qls (diamonds) shown in Fig. 14.1. The generalized
experimental slope for crystalline clouds from Platt (1997) and Ryan (2000) recalculated from the
temperature to the height with the average lapse rate 6.5 °K km−1 is plotted in (b) with triangles.
From Khvorostyanov and Curry (2008c). J. Atmos. Sci., 65, © American Meteorological Society.
Used with permission.

obeys the power law with indices slightly increasing with height. The large-size fraction (Fig. 14.4b),
as seen in log-linear coordinates, represents the MP distributions. The slopes are much steeper than in
the lower layer and increase upward—i.e., the large-size spectra also become narrower at colder tem-
peratures. These features are mostly due to the smaller qls and the dependence bl0 ∼ qls−1. The com-
posite spectra matched at 90 μm (Fig. 14.4c) exhibit features of bimodality, but more weakly than in
the lower layer. Now the bimodality occurs between the large- and small-size fractions rather than
within the small-size fraction as shown in Fig. 14.3 at s < 0. For comparison, given in Fig. 14.4d are
the average size spectra from Lawson et al. (2006) measured in cirrus clouds at three temperatures.
One can see that the calculated spectra (Fig. 4c) are similar to the observed spectra. In particular, they
exhibit a similar bimodality, become narrower at lower temperatures, and their bimodality decreases
and vanishes with increasing height (decreasing temperature). The reason for this is the decrease with
height of IWC of the small fraction, slowing down accretion, and diminishing the large fraction. This
analysis is consistent with observations (Sassen et al., 1989; Mitchell, 1994; Platt, 1997; Ryan, 2000;
Poellot et al., 1999) that bimodality is more pronounced in the lower layers.
Note that the spectra calculated at ice sub- and supersaturation are somewhat different. The experi-
mental spectra, however, are usually presented without information about supersaturation, and may
have been obtained from mixtures sampled in both sub- and supersaturated layers. This precludes a
more detailed comparison at present and indicates that simultaneous measurements of the size spec-
tra and supersaturation are desirable.
Fig. 14.5 shows the slopes b le(r) and size spectra calculated with (Eqns. 14.4.30) and (14.4.29)
for the subsaturated subcloud layer where the small-size fraction has been evaporated. At small and
large r, the behavior of ble(r) is determined by (Eqns. 14.4.32) and (14.4.31), respectively. The slopes
rapidly increase with radius, but the rate of this growth ble(r)/dr decreases at large r, which is deter-
mined by the increasing contribution from the second term with v(r) in (Eqn. 14.4.30). This results in
708 Analytical Solutions to the Stochastic Kinetic Equation for Precipitating Clouds

1E+2 1E+0

Crystal size spectra (L–1 µm–1)

Crystal size spectra (L–1 µm–1)

4.8 km
5.1 km 1E–1
5.4 km
1E–2
1E+1 5.7 km
6.0 km 1E–3

1E–4 4.8 km
1E+0 5.1 km
1E–5
5.4 km
1E–6 5.7 km
6.0 km
1E–1 1E–7
1 10 100 0 500 1000 1500 2000 2500
Crystal radius (µm) Crystal radius (µm)
(a) (b)

1E+2
1E+1 1E+12
Crystal size spectra (L–1 µm–1)

Crystal size spectra f(D) m –4

1E+0 1E+11
1E+10
1E–1
1E+9
1E–2
4.8 km 1E+8
1E–3 5.1 km 1E+7
1E–4 5.4 km
1E+6
1E–5 5.7 km
1E+5
6.0 km
1E–6 1E+4
1E–7 1E+3
1 10 100 1000 1 10 100 1000
Crystal radius (µm) Long dimension D (µm)
(c) (d)

Figure 14.3. Crystal size spectra by radii r (L−1 μm−1) at ice subsaturation (s < 0) at the heights in
km indicated in the legends; temperature decreases from −14.9 °C at 4.8 km to −22.15 °C at 6.0 km.
Size spectra: (a) for the small fraction; (b) large fraction; (c) composite; and (d) generalization
by Platt (1997) of the observed crystal size spectra by long dimension D (m−4) in the temperature
interval of −25 °C to −30 °C. Note the different normalization of the spectra and axes scales in
(a)–(c) by radius and (d) by diameter. From Khvorostyanov and Curry (2008c). J. Atmos. Sci., 65,
© American Meteorological Society. Used with permission.

a rapid decrease in fl(r) toward the larger values of r. This feature has been observed in liquid clouds
(e.g., Willis 1984), and as Fig. 14.5 shows, can also be pertinent for subcloud layers of crystalline
clouds. Since we consider an example with spherical particles and asymptotic v(r) ∼ r1/2 (Bv = 1/2),
the asymptotic behavior of the spectra is fl ∼ exp(−cl1Avr 5/2), as described in Section 14.4.5. For some
crystal habits like aggregates or plates, the power Bv can be much smaller than 1/2 and closer to 0
(e.g., Mitchell, 1996; Khvorostyanov and Curry, 2002, 2005). Then, the decrease in fl can be much
slower and the tails in the subcloud layer can be much longer.
14.5. Interpretation of Solutions 709

1E+2
1E+1
Crystal size spectra (L–1 µm–1)

Crystal size spectra (L–1 µm–1)

1E+1 1E+0 7.5 km
7.8 km
1E–1
1E+0 8.1 km
1E–2 8.4 km
1E–1 1E–3
7.5 km
1E–2 7.8 km 1E–4
8.1 km 1E–5
1E–3 8.4 km
8.7 km 1E–6
1E–4 1E–7
1 10 100 0 200 400 600 800 1000
Crystal radius (µm) Crystal radius (µm)
(a) (b)

1E+2 1E+3
Crystal size spectra (L–1 µm–1)

Crystal size spectra (L–1 µm–1)

1E+1 1E+2 –54.8 C
–45.2 C
1E+0 1E+1
–35.7 C
1E+0
1E–1
7.5 km 1E–1
1E–2
7.8 km 1E–2
1E–3
8.1 km 1E–3
1E–4 8.4 km
1E–4
1E–5 1E–5
1E–6 1E–6
1 10 100 1000 1 10 100 1000
Crystal radius (µm) Maximum dimension D (µm)
(c) (d)

Figure 14.4. Crystal size spectra by radii (L−1 μm−1) at ice supersaturation (s > 0) at the heights
indicated in the legends. (a) small fraction extended to 200 μm; (b) large fraction; (c) composite
spectra (merged the small-size and the large-size fractions); and (d) experimental spectra in cirrus
clouds from Lawson et al. (2006) at 3 indicated temperatures. From Khvorostyanov and Curry
(2008c). J. Atmos. Sci., 65, © American Meteorological Society. Used with permission.

14.5.3. General Interpretation of the Solutions

The analytical solutions of the stochastic kinetic equations for the size spectra of the large fraction
of liquid and crystalline precipitating particles were obtained in this chapter for various cases. The
solutions are somewhat different in various situations but have common general features that allow
us to explain and interpret observations and empirically derived expressions for rain and snow size
spectra such as the Marshall–Palmer distribution, gamma distributions, or inverse power laws. This
provides the basis for development of the more physical parameterizations of cloud microphysics in
cloud and climate models. The major results can be summarized as follows.
710 Analytical Solutions to the Stochastic Kinetic Equation for Precipitating Clouds

1E+2

Crystal size spectra (L–1 µm–1)

1E+4 3.3 km
1E+1 3.6 km
3.9 km
1E+0
Slope (cm–2)

1E+3
1E–1
3.3 km
1E+2 3.6 km 1E–2
3.9 km
1E–3

1E+1 1E–4
0 200 400 600 800 0 200 400 600 800
Crystal radius (µm) Crystal radius (µm)
(a) (b)

Figure 14.5. (a) Slopes and (b) size spectra in the subcloud layer with zero IWC of the small-size
fraction qls at the heights (km) indicated in the legends. From Khvorostyanov and Curry (2008c).
J. Atmos. Sci., 65, © American Meteorological Society. Used with permission.

The general solution of the stochastic kinetic equations for the large-size fraction (precipitating
particles) is described by the product of the two major terms: a) an exponential term, ∼exp(−b lr); and
b) a prefactor before the exponent that is an algebraic function of radius like a power law or polyno-
mial. The argument bl of the exponent consists of a slope of the Marshall–Palmer type and an addi-
tional integral that depends on the condensation and accretion rates, vertical velocities, the turbulent
coefficient, terminal velocity, and vertical gradient of the liquid (ice) water content. The algebraic
function before the exponent is inversely proportional to the sum of the condensation and accretion
rates and depends on the super- or subsaturation, terminal velocity, and collection efficiency.
Several particular cases were considered in this chapter: a) terminal velocity as a linear function
of radius; b) terminal velocity as a square root function of radius; c) an accretion growth rate much
greater than the condensation growth rate; and d) a subcloud evaporation layer with a very small or
absent small-size fraction. The general solution is substantially simplified for these cases. The expo-
nential part tends to the Marshall–Palmer exponent with the slope b l0, but contains additional terms
that make the slope radius-dependent and nonlinear, causing the spectra to decrease with radius faster
than the MP exponent as observed in many experiments. This may influence the spectral moments
(e.g., cause smaller radar reflectivity and precipitation rates than those evaluated with MP spectra)
and change the relations between them.
The radius dependence of the algebraic prefactor before the exponent is weaker than that of the
exponent, converts for sufficiently large radii to the power law, and the spectra also have the form of
gamma distributions with the slope b l0 and index pl. This index correlates with the supersaturation
and in general is positive in the cloud growth layers, when the spectra tend to modified gamma dis-
tributions, and is negative in the evaporation layers, when the spectra tend to the inverse power laws
at smaller sizes multiplied by the exponential tails. However, these gamma distributions are different
from those obtained for the small-size fraction (cloud particles) described in Chapter 13.
14.5. Interpretation of Solutions 711

A simple expression is derived for the slope b l0 via four parameters: b l0 is proportional to the rela-
tive gradient al = (dqll /dz)/qll of the liquid (ice) water content of the large-size fraction, to water or
ice density, and is inversely proportional to the collection efficiency and the liquid (ice) water content
qls of the small-size fraction. All of these parameters are available in cloud-scale and large-scale
models, and these dependencies provide reasonable explanations for the observed features of b l0 with
variations of each parameter. In particular, the inverse dependence, b l0 ∼ qls−1, provides an explana-
tion of the observed strong inverse temperature dependence of b l0 since qls in general decreases with
decreasing temperature. This explains experimentally observed narrowing of the size spectra with
decreasing temperature.
Simple analytical expressions are also derived for the power indices pl of the gamma distributions
(shape parameters), which are expressed via the coefficients of the terminal velocity, the slopes bl0,
vertical velocity, and the turbulent coefficient. These features allow us to explain the observed shapes
of the rain and snow size spectra (e.g., Ulbrich, 1983; Willis, 1984).
Based on these expressions for bl0 and pl, a bl0−pl relation is derived for the case with a terminal
velocity proportional to the radius as a 2nd-order polynomial. This relation is similar to the empirical
parameterizations based on radar and disdrometer data (e.g., Zhang et al., 2001, 2003a,b; Brandes
et al., 2003). The coefficients of this relation are expressed via vertical velocity, the turbulent coef-
ficient, and the cloud liquid or ice water content.
These analytical solutions for the spectra of the large-size fraction and its parameters provide
explanations for observed dependencies of the spectra on the temperature, turbulence, vertical
velocities, liquid water or ice water content, and other cloud properties. The results are illustrated
with calculations for a crystalline cloud. These analytical expressions can be used for parameter-
ization of the size spectra and related quantities (e.g., coagulation–accretion rates, precipitation
intensities, optical properties, radar reflectivities) in bulk cloud and climate models and in remote
sensing techniques.
The solutions have been presented for liquid-only and ice-only size spectra. Treatment of mixed
phase clouds would require simultaneous consideration of the small- and large-size fractions of the
drop and crystal spectra with an accounting for their interactions (Wegener–Findeisen–Bergeron pro-
cess and transitions among the fractions). The coexistence of drops and crystals would change the
water and ice supersaturations in the three-phase system and the coagulation and accretion rates.
However, it can be expected that the general functional shapes of the size spectra will be similar
to those described earlier. The change of the spectra in a mixed-phase cloud will result in the cor-
responding change of the parameters of the spectra—in particular, of the p-indices proportional to
sub- or supersaturation, and of slopes of the exponents that are expressed via the coagulation–
accretion rates and LWC or IWC of the small fraction.
Many bulk parameterizations of cloud microphysics use schemes with the number of size cat-
egories larger than the two considered here: small- and large-size fractions. For example, the size
spectrum of ice particles may be separated into ice, snow, graupel, and hail. The parameterization of
the size spectra described in this chapter for two size fractions is easily generalized for several frac-
tions. Then, several pairs of hydrometeors should be considered, and the parameterizations described
earlier applied for each pair consisting of the smaller- and larger-size fractions.
712 Analytical Solutions to the Stochastic Kinetic Equation for Precipitating Clouds

14.6. Autoconversion and Corrections to the Analytical Solutions

As mentioned in Section 14.2, the autoconversion is a process of “self-collection” of the particles within
the same fraction or size category, which transfers them into the next size category. The hypotheses on
autoconversion and its parameterizations began developing in the 1960s along with the stochastic conden-
sation theory considered in Chapter 13. While the stochastic condensation theory attempted to describe
broadening of the originally narrow spectrum, the initiation of coagulation, and the formation of the
embryonic precipitating particles, the parameterizations of autoconversion attempted to provide the equa-
tions for the rates Paut of mass conversion from a smaller fraction into a larger fraction, usually without
detailed consideration of the mechanism of this transition. Many features and quantitative characteristics
of autoconversion are still unclear because this phenomenon is difficult to observe and it is not quite clear
in general how to describe precisely gravitational coagulation among such comparable particles within
a rather narrow size spectrum. One of the major problems in quantitative description of autoconversion
is that interactions of the hydrometeors with comparable masses and fall velocities within the same size
region make more questionable simplifications used in the other methods described in Section 14.2. Here-
after, we assume that the LWC (IWC) qll of the large size fraction is small and, in order to avoid duplica-
tion of autoconversion with the coagulation between the small- and large-size fractions, we will consider
autoconversion only within the small-size fraction. The corresponding equations in the following text are
formulated via qls rather than in terms of the total water content as in some other parameterizations.
A complete rigorous theory of autoconversion is still absent, and parameterizations of autocon-
version have been developed based either on some intuitive considerations or on simulations with
spectral bin models and the subsequent fitting of numerical results with some simple functions. One
of the first and widely used parameterizations of autoconversion of cloud water qls into rainwater qll
was suggested by Kessler (1969) as

dqll
Paut = = K Kes qlsθ (qls − qls 0 ), (14.6.1)
dt
where q (x) is the Heaviside step function, KKes is the conversion coefficient, and qls0 is the thresh-
old, from which autoconversion begins. Kessler assigned originally the values of KKes = 10−3 s−1 and
qls0 = 5 × 10−4 kg kg−1 to 1 × 10−3 kg kg−1 for the deep convection. Presence of the threshold here implicitly
accounts for the fact that autoconversion is considered as a coagulation process and begins only when
the larger particles reach some minimum values and gravitational coagulation becomes noticeable.
Kessler’s scheme was modified later by many authors who accounted for the fact that autoconversion is
a function not only of the liquid water content but also of the drop concentration and size spectrum width
(e.g., Berry, 1967; Berry and Reinhard, 1974a,b; Manton and Cotton, 1977; Tripoli and Cotton, 1980; Liou and
Ou, 1989; Baker, 1993; Khairoutdinov and Kogan, 2000; Seifert and Beheng, 2001, 2006; a review of various
schemes was given by Liu and Daum, 2004). Manton and Cotton (1977) (see also Tripoli and Cotton,
1980) suggested a modification of Kessler’s scheme that can be written for the liquid water content as

dqll 4π 3
= K MC qlsθ (qls − qls 0 ), qls 0 = rdm ρ w N d , (14.6.2a)
dt 3
K MC = π=rd2πEc2Vdt (rd ) N d , , =rd( = (3qlsπ/4πρ w N1 d )1/3 . (14.6.2b)

The threshold qls0 is determined in this scheme by the threshold radius rdm = 10 μm. The conver-
sion coefficient KMC is treated as the mean frequency of collisions among cloud droplets which
14.6. Autoconversion and Corrections to the Analytical Solutions 713

become raindrops. In contrast to Kessler’s parameterization, it is not constant but is expressed via
the mean volume radius of cloud drops rd related to the mean qls, the mean collision efficiency
Ec = 0. 55 assumed by Manton and Cotton, the terminal velocity of drops with radius rd described by
the Stokes’ law Vdt = csrd2, where cs is the Stokes constant (see Chapter 12), and the drop concentra-
tion Nd. Note that KMC here resembles the collision efficiencies (Eqn. 14.2.10a) or collection rates
(Eqns. 14.2.20) and (14.2.20a), the reason for this is discussed in the following text. After substitution
of KMC and rd from (Eqn. 14.6.2b) into (Eqn. 14.6.2a), the autoconversion rate becomes

dqll
= K MC qls = Baut qls7/3 N d−1/3 θ (qls − qls 0 ), (14.6.3a)
dt
4/3
 3 
Baut = π cs Ec   . (14.6.3b)
 4πρ w 

Baker (1993) studied autoconversion in the marine boundary layer Sc clouds and, in order to account
for the uncertainty in the self-collection rates within the same fraction, introduced an empirical mul-
tiplier gB. Thus, the autoconversion rate (Eqn. 14.6.3a) was modified as

dqll
= Baut γ B qls7/ 3 N d−1/3 θ (qls − qls 0 ). (14.6.4)
dt
The coefficient gB was varying between 0.01 and 0.1 to decrease the autoconversion rate. Berry
(1967), Khairoutdinov and Kogan (2000), and some other researchers used the results of numerical
simulations with the spectral bin models and subsequent curve fits to refine the coefficients in rela-
tions like (Eqn. 14.6.4). The numerical simulations were usually performed for some specific cloud
types. Therefore, these parameterizations are applicable for certain cloud types and may be different
for others.
A comprehensive treatment of the autoconversion rates was performed by Liu and Daum (2004).
They considered the mass growth rates in a polydisperse ensemble of drops, gave the derivations of
several previous functional forms similar to (Eqn. 14.6.4) and suggested a newer parameterization.
We will use an analogous but somewhat different way and will derive the autoconversion rate based
on the coagulation kinetic equations of Section 14.2. Consider again the loss term in (Eqn. 14.2.2b)
and represent the size spectrum as the sum (Eqn. 14.2.3) of the small and large fractions, f = fs + fl.
Then, the term for self-collection Iloss,ss of the small fraction that was omitted in (Eqn. 14.2.6) in the
continuous growth approximation occurs now and accounts for autoconversion:
m0

I loss ,ss = fs (m) ∫ K (m, m′) fs (m′) dm ′. (14.6.5)

0

It is convenient to rewrite this equation in terms of radii. Taking into account that loss of the small-
size fraction Iloss,ss due to self-collection is equal to the tendency (∂fs /∂t)aut, we obtain
r
 ∂ fs  0

 ∂t  = − I loss ,ss = − fs (r ) ∫ K (r , r ′) fs (r ′) dr ′ = − K aut fs (r ), (14.6.6)

aut 0

where we introduced the rate coefficient

r0

K aut = ∫ K (r , r ′) fs (r ′) dr ′. (14.6.7)
0
714 Analytical Solutions to the Stochastic Kinetic Equation for Precipitating Clouds

It will be shown in the following text that this Kaut coincides with the autoconversion coefficient.
Multiplying this equation by the drop mass m(r) = (4/3)prwr3, and integrating over r yields
r
 dqls 
0
 ∂ fs 
  = ∫  m (r ) dr
dt aut 0 ∂t  aut
r0 r0

= − ∫ fs (r) m (r )dr ∫ K (r , r ′) fs (r ′) dr ′. (14.6.8)

0 0

The first integral on the right-hand side is qls and we obtain the rate of the mass loss for the small
fraction due to autoconversion:

 dqls 
  = − K aut qls . (14.6.9)
dt  aut

From the mass balance, we have a relation between the autoconversion gain rate (dqll /dt)aut in the
large fraction, and the autoconversion loss (dqls /dt)aut in the small fraction:

 dqll   dqls 
  = −   = K aut qls . (14.6.10)
dt  aut dt  aut

This is the usual autoconversion equation and Kaut is the autoconversion coefficient.
In can be shown that (Eqn. 14.6.10) with the general expression for Kaut in (Eqn. 14.6.7) allows us
to obtain various forms of the autoconversion equation. For example, substituting into (Eqn. 14.6.7)
the gravitational collection kernel from (Eqn. 14.2.2c), K(r, r′) = Ec(r, r′)p (r′ + r)2)|v(r′) − v(r)|, we
obtain
r0

K aut = π ∫ Ec (r , r ′)(r + r ′)2 | vt (r ) − vt (r ′) | fs (r ′) dr ′. (14.6.11)

0

Applying now the mean-value theorem to this integral (similar to Chapter 7 for drop activation) and
removing K(r, r′) out of the integral at some value r′ = rM, we obtain
r0

K aut = π Ec (r , rM )(r + rM )2 | vt (r ) − vt (rM ) | ∫ fs (r ′) dr ′

0

= π Ec (r , rM )(r + rM )2 | vt (r ) − vt (rM ) | N s . (14.6.12)

Various versions of Kaut can be obtained by specifying various rM—e.g., by tuning to the results of
numerical models. A particular case is obtained assuming, following Liu and Daum, the approxima-
tions r >> rM, (rM + r)2 ≈ r2, and vt(r) − vt(rM) ≈ vt(r), similar to the continuous growth approximation
in Section 14.2 for the large and small drops. Thus, Kaut can be written as

K aut = π Ec (r , rM )r 2 vt (r ) N s . (14.6.13)

Equation (14.6.13) was derived by Liu and Daum (2004) and shows that the Manton and Cotton param-
eterization (Eqns. 14.6.2a) and (14.6.2b) can be derived from (Eqn. 14.6.7) with the gravitational kernel,
and this form implicitly assumes a kind of continuous growth approximation, although within the same
size fraction. Liu and Daum (2004) considered a more precise equation for Kaut using Long’s (1974)
approximation for the collection kernel, K(r, r′) ≈ kLr6 valid at r < 50 μm with kL ≈ 1.9 × 1011 cm−3 s−1,
14.6. Autoconversion and Corrections to the Analytical Solutions 715

r in cm, and K(r, r′) in cm3 s−1. Substitution of this K(r, r′) into (Eqn. 14.6.7) yields the newer para-
meterization by Liu and Daum (2004):

 dqll 
  = K aut qlsθ (r6 − r6 c )
LD LD
K aut = κ L N s r66 , (14.6.14)
dt  aut

where r6 is the mean radius of the sixth moment of the spectrum and r6c determines the threshold of
autoconversion. If the spectrum is the gamma distribution, fs (r ) = cN r p exp(− β r ) (see Chapter 2),
then r6 is
1/6
1  Γ ( p + 7) 
r6 =   . (14.6.15)
β  Γ ( p + 1) 

Expressing the mean radius via qls and Ns as was done in the cited works and substituting into
(Eqn. 14.6.4), Liu and Daum presented the autoconversion rate in the form, allowing comparison
with the previous works:

 dqll 
  = cLD qlsθ (r6 − r6 c ), (14.6.16a)
dt  aut
 dqll  −1/3 7/3
  = α LD N s qls θ (r6 − r6 c ) (14.6.16b)
dt  aut
2 2/3
 3  q 
cLD = α LD N s−1/3 qls4/3 , α LD =   κ L β 66  ls  , (14.6.17)
 4πρ w   Ns 

where b6 is related to the relative dispersion of the spectrum srr,

 (1 + 3σ rr2 )(1 + 4σ rr2 )(1 + 5σ rr2 ) 

β6 =  . (14.6.18)
 (1 + σ rr2 )(1 + 2σ rr2 ) 
Equation (14.6.16a) is a linearized by the qls form similar to (Eqns. 14.6.2a), (14.6.2b), and (14.6.16a)
and is a non-linear form by the qls and Ns, which extends the Manton and Cotton parameterization
(Eqn. 14.6.3a). Thus, (Eqns. 14.6.16)–(14.6.18) of Liu and Daum contain all the factors of the previ-
ous parameterizations and include additionally the spectral dispersion in the general form. It is clear
in advance that the autoconversion rate should depend on the width of the spectra and should be
different in clouds of various forms with different spectral dispersions. Accounting for the effect of
the spectral dispersion on the autoconversion rate in Liu and Daum’s parameterization allows greater
flexibility and higher accuracy than in the previous parameterizations. Indeed, this was demonstrated
in Liu and Daum (2004) through numerical calculations and by comparing various parameterizations.
The spectral dispersion srr, and therefore b6, are external parameters in the Liu and Daum param-
eterization that can be varied or taken from the measurements like those described in Section 13.8.
However, they can be expressed via the cloud properties. Substituting the relation (Eqn. 2.4.33)
between srr and the index of gamma distribution p, srr = (p + 1)−1/2, the expression (Eqn. 14.6.18)
can be rewritten via p as

 ( p + 4)( p + 5)( p + 6) 
β6 =  . (14.6.19)
 ( p + 1)( p + 2)( p + 3) 
716 Analytical Solutions to the Stochastic Kinetic Equation for Precipitating Clouds

Then, p can be evaluated using (Eqns. 13.8.4) and (13.8.5) analyzed in Sections 13.8–13.10, and b6
can be related to the cloud and atmospheric properties, this allows us to express b6, cLD, aLD, and
(dqll /dt)aut analytically and to study the effects on the autoconversion rates of atmospheric turbulence,
LWC and its gradients, temperature, lapse rates, etc., in various clouds.
The autoconversion kinetic (Eqn. 14.6.6) with various specifications of Kaut described earlier
lets us introduce corrections to the analytical solutions for the size spectrum of the small fraction
obtained in Section 13.7. The structure of the autoconversion term in (Eqn. 14.6.6) for the small-size
fraction, (∂fs /∂t)aut = −Kaut fs, is similar to the coagulation term in the general kinetic (Eqn. 13.7.1)
for fs, which is the last term in (Eqn. 13.7.1), (∂fs /∂t)col = −scol fs. Thus, (Eqn. 13.7.1) can be further
generalized to account for autoconversion by adding the term −Kaut fs on the right-hand side. The
terms with collection and autoconversion are similar, and the solutions (Eqns. 13.7.2) and (13.7.5)
can be modified by replacing −scol fs with the sum −[scol + Kaut q (qls − qls0)] fs. Thus, the solution for
the tail of the spectrum at large r is again (Eqn. 13.7.2), but with the slope b s2 from (Eqn. 13.7.3)
modified as

1 1  d (w − α s k )  α v (r ) 
β s 2 (r ) =  αsw + + σ col
aut
− α s2 k  − s , (14.6.20a)
bcon s  2  dz  Bv + 2 

σ col
aut
= σ col + K autθ (qls − qls 0 ). (14.6.20b)

The general solution is again (Eqn. 13.7.5) with this modified b s2(r). The physical interpretation of
this solution is clear: The effect of autoconversion is similar to the effect of coagulation; autoconver-
sion leads to an increase in the slope parameter and a faster decrease of fs with r. Equations (14.6.16a)
and (14.6.16b) allow quantitative evaluation of the effect of autoconversion on the spectra in various
situations.
Equations like (Eqns. 14.6.3a) or (14.6.16b) that contain qls7/3 are nonlinear relations relative to
qls, which may make parameterizations of the size spectra more complicated. It is more convenient
to use linearized forms like (Eqn. 14.6.16a), which can be done by splitting them into two time steps
as is often done in numerical models:
dqll( n ) ( n −1) ( n )
= K aut qls θ (qls( n −1) − qls( n0−1) ), (14.6.21a)
dt
dqls( n ) ( n −1) ( n )
= − K aut qls θ (qls( n −1) − qls( n0−1) ), (14.6.21b)
dt
where the subscript (n − 1) means the quantities from the previous time step, and n means the quanti-
ties from the current time step. These quantities can be used in (Eqn. 14.6.16b), which allows us to
account for the effect of autoconversion on the size spectra.

14.7. The Coagulation Equation as the Integral Chapman–Kolmogorov

and Differential Fokker–Planck Equations

As mentioned in Section 13.12, the integral Smoluchowski–Müller coagulation equation considered

in Sections 5.6 and 14.2 is similar in structure to the generalized integral kinetic (Eqn. 13.12.1b)
or the Chapman–Kolmogorov (Eqn. 13.12.1a). This analogy lets us derive the integral coagulation
14.7. The Coagulation Equation as the Integral Chapman–Kolmogorov 717

equation from the generalized kinetic (Eqn. 13.12.1b) and then derive the differential analog of the
coagulation equation in the form of the Fokker–Planck equation. The generalized stochastic kinetic
(Eqn. 13.12.1b) derived in Section 13.12 from the Chapman–Kolmogorov equation can be written in
the four-dimensional phase space in terms of masses instead of radii as

∂ f ( x , m, t )
= ∫ Wxm ( x − x ′, m − m′ | x ′, m′ ) f ( x − x ′, m − m ′, t ) f ( x ′, m′, t) dx ′m ′
∂t

− f ( x , m, t ) ∫ Wxm ( x , m | x ′, m′ ) f ( x , m ′, t ) dx ′ dm ′ (14.7.1)

Here, as in (Eqns. 13.12.1a) and (13.12.1b), the first and second terms represent gain and loss of the

particles per unit of time in an element of the 4D phase space ( x , m) . Recall, the probabilities of tran-
sition Wxm in (Eqn. 14.7.1) are defined per unit time and per particle and have dimension [cm3 s−1].

Let us assume that: a) the stochastic jumps ( x ′, m′) in the 4D phase space are caused by the acts

of coagulation, b) the corresponding probabilities of transition Wxr ( x − x ′, m − m′ | x ′, m′) and

Wxm ( x , m | x ′, m′) in the spatially homogeneous medium do not depend on the coordinates xa , and
c) are described by the coagulation kernels (1/2)K(m − m′, m′) and K(m, m′). Thus, (Eqn. 14.7.1)
becomes
m
 ∂ f (m )  1
∂t  col ,ls 2 ∫0
  = K (m − m′, m′) f (m − m ′) f (m′) dm ′

− f (m) ∫ K (m, m′) f (m′) dm ′. (14.7.2)

0

This is a familiar form of the coagulation equation where the first and second terms on the right-hand
side represent the gain and loss of particles, Igain and Iloss. Note that (Eqn. 14.7.2) is a particular case
of (Eqn. 14.2.1) for the spatially homogeneous case, and a more general equation can be derived from
(Eqn. 14.7.1) that would also include coordinate dependence. The coagulation kernel can be speci-
fied for various processes, as was described for gravitational coagulation in Sections 5.5 and 14.2, for
Brownian coagulation as described in Chapter 10, or for other types of coagulation.
As was shown in Section 13.12, a differential analog of this integral equation can be derived by
expansion of the kernels into the power series. We assume again, as in Section 14.2, that f(m) can
be represented as a sum of the small- and large-size fractions, f(m) = fl(m) + fs(m). Assuming in the
spirit of the Chapman–Kolmogorov equation that the stochastic “jumps” m′ are small, the subinte-
gral expression in (Eqn. 14.7.2) for Igain can be expanded into the Taylor power series by the small
parameter m′:

(−1)n ∂ n
∞
K (m − m ′, m ′) fl (m − m ′) = ∑ [K (m,0) fl (m)] m ′ n. (14.7.3)
n=0 n! ∂m n

The expansion with an infinite number of terms is called the Kramers–Moyal series. Such infinite
expansion is mathematically equivalent to the original integral (Eqn. 14.7.2) but evaluation of the
higher moments is difficult and the expansion is usually truncated at the first few terms. The continu-
ous growth approximation used in many cloud models was derived in Section 14.2 by truncating this
expansion at the first-order term, which yields the drift velocity in the m- or r-spaces but does not
describe the diffusion in these spaces. Accounting for the next terms may improve the accuracy of
718 Analytical Solutions to the Stochastic Kinetic Equation for Precipitating Clouds

the equation. Assuming as in Section 14.2 that m >> m′, expanding the kernel as in (Eqn. 14.7.3) and
truncating the series at the terms of the second order with n = 2, we have

K (m − m ′, m ′) fl (m − m ′) ≈ K (m, 0) fl (m)
∂ 1 ∂2
− [ K (m, 0) fl (m)]m ′ + [ K (m, 0) fl (m)]m ′ 2 . (14.7.4)
∂m 2 ∂m 2
Substitution of this expression into (Eqn. 14.2.5) yields the gain term

∂
I gain = K (m, 0) fl (m) N s − [ K (m, 0) fl (m)]qls
∂m
1 ∂2
+ [ K (m, 0) fl (m)]M s(2) , (14.7.5)
2 ∂m 2
where Ns and qls are the concentration and liquid (ice) water content of the small fraction as in
(Eqn. 14.2.10) and M s(2) is the second moment of the size spectrum by mass m′:
m0
M s(2) = ∫ m ′ 2 fs (m ′)dm ′. (14.7.6a)
0

If the particles of the small fraction have the shape close to spherical, then the mass m = (4/3)prwr3.
Substituting this relation into (Eqn. 14.7.6a) yields
2 2
 4πρ w  r0  4πρ w 
M s(2) = 
 3  ∫ 0
r 6 fs (r )dr = 
 3  r 6
Z , (14.7.6b)

where Zr6 is the 6th moment of the distribution by radii, proportional to the radar reflectivity. Assum-
ing that the spectrum can be approximated by the gamma distribution fs(r) ∼ r pexp(−br), and that the
upper limit here can be extended to infinity, the moment Zr6 is expressed analytically as described in
Section 2.4, (Eqn. 2.4.36), and is in these notations:

Z r 6 = < r 6 > = N s r 6 cr 6 ,
( p + 6)( p + 5)( p + 4)( p + 3)( p + 2)
cr 6 = , (14.7.6c)
( p + 1)5

where r is the mean radius of the spectrum. The coefficient cr6 = 5.65 for p = 6 and cr6 = 27.65 for
p = 2.
The loss term is in this approximation is

I loss = K (m, 0) fl (m) N s . (14.7.7)

Substituting Igain (Eqn. 14.7.5) and Iloss (Eqn. 14.7.7) into the kinetic (Eqn. 14.7.2) written for fl, we
notice that Iloss is cancelled with the first term in Igain. The rest yields
∂ fl ∂
= I gain − I loss = − [ K (m,0)qls fl (m)]
∂t ∂m
1 ∂2
+ [ K (m,0) fl (m)]M s(2) . (14.7.8)
2 ∂m 2
14.7. The Coagulation Equation as the Integral Chapman–Kolmogorov 719

Introducing now the drift velocity mɺ drift and the diffusion coefficient Ddif in the mass space:

mɺ drift = K (m, 0)qls , Ddif = (1/2) K (m, 0) M s(2) , (14.7.9)

and (Eqn. 14.7.8) can be rewritten as

∂ fl (m) ∂ ∂2
=− [mɺ drift fl (m)] + [ Ddif fl (m)] (14.7.10)
∂t ∂m ∂m 2
This is the kinetic equation of the Fokker–Planck type with drift and diffusion. It can be applied for
various types of coagulation, for which approximations made here are applicable. This can be done
by specifying different coagulation kernels K(m, 0) and will result in different drift velocities and
diffusion coefficients.
In the following text, we consider the gravitational coagulation. The gravitational kernel is defined
by (Eqn. 14.2.7), K(m, 0) = pEcr2v(r). Substituting it into (Eqn. 14.7.5), we obtain

∂
I gain = fl (m)[π Ec r 2 v (r ) N s ] − [π Ec r 2 v (r )qls fl (m)]
∂m
1 ∂2
+ [π Ec r 2 v (r ) fl (m)]M s(2) . (14.7.11)
2 ∂m 2
The loss term Iloss in the same approximation is described by (Eqn. 14.2.11), I loss = fl (m)[π Ec r 2 v (r ) N s ] .
Substituting Igain and Iloss into the kinetic (Eqn. 14.2.1) shows that the term Iloss is again mutually
cancelled with the first term in Igain, and the rest yields

∂ fl ∂
= I gain − I loss = − [π Ec r 2 v (r )qls fl (m)]
∂t ∂m
1 ∂2
+ [π Ec r 2 v (r ) fl (m)]M s( 2) (14.7.12)
2 ∂m 2
Introducing the drift velocity mɺ m ,coag and a diffusion coefficient Dm ,coag in the mass space,

mɺ m ,coag = K (m, 0)qls ≈ π Ec r 2 v (r )qls , (14.7.13)

(2 ) 2 (2)
Dm ,coag = (1/ 2) K (m, 0) M s ≈ (π /2) Ec r v (r ) M s , (14.7.14)

and so (Eqn. 14.7.12) can be rewritten as

∂ fl (m) ∂ ∂2
=−  mɺ m ,coag fl (m)  +  Dm ,coag fl (m)  . (14.7.15)
∂t ∂m ∂m 2 
Thus, we derived a differential kinetic equation of the Fokker–Planck type for coagulation with
drift and diffusion. The expression for mɺ m ,coag is the same as in the continuous growth approxima-
tion (Eqn. 14.2.13), while the diffusion coefficient Dm,coag is new. It arose from the third term in the
expansion (Eqn. 14.7.4) of the coagulation kernel. It can be written in a more explicit form using
(Eqns. 14.7.6b) and (14.7.6c) for M s(2) and Zr6,

8π 3
Dm ,coag = Ec cr 6 ρ w2 r 2 v (r ) N s r 6 . (14.7.16)
9
720 Analytical Solutions to the Stochastic Kinetic Equation for Precipitating Clouds

In particular, if v(r) ∼ r2, then Dm,coag ∼ r4 ∼ m4/3; if v(r) ∼ r, then Dm,coag ∼ r3 ∼ m. The dimension
of Dm,coag in (Eqn. 14.7.16) is [g2 s−1] which ensures the correct dimension of the diffusion term in
(Eqn. 14.7.15). The values of Dm,coag can be calculated using (Eqn. 14.7.16) or estimated from the
measurements of radar reflectivity and Zr6 of the small fraction. Equation (14.7.15) can be rewritten
in the form of a continuity equation, as was done in Section 8.2 for the nucleation theory:

∂ fl (m) ∂ jm ,coag (14.7.17)

=− ,
∂t ∂m
where the flux jm,coag in the m-space is

∂
jm ,coag = mɺ m ,coag fl (m −  Dm ,coag fl (m)  (14.7.18a)
∂m 
∂ fl ( m )
= mɶɺ m ,coag fl (m) − Dm ,coag . (14.7.18b)
∂m
The effective drift velocity introduced in the second equation is

∂ Dm ,coag
mɶɺ m ,coag = mɺ m ,coag − . (14.7.19)
∂m
The previous continuous growth approximation (Eqns. 14.2.12) and (14.2.13) of Section 14.2 pre-
dicted monotonous growth of the particles of the large-size fraction with the drift velocity mɺ m ,coag.
Equations (14.7.15)–(14.7.19) of the newer differential analog of the coagulation equation of the
Fokker–Planck type provide the corrections to the continuous growth and predict a more complicated
growth. According to (Eqn. 14.7.16), Dm,coag is a growing function of m, thus ∂Dm,coag /∂m > 0, and the
effective drift velocity mɶɺ m ,coag is smaller than mɺ m ,coag . This factor hampers particle growth by coagu-
lation. The second term in Equation (14.7.18b) for the flux, −Dm,coag(∂fl /∂m) > 0, is negative at
masses smaller than the modal mass mm, m < mm, where (∂fl /∂m) > 0, and is positive at m > mm where
(∂fl /∂m) < 0. Thus, presence of the diffusion in the mass space hampers particle growth at smaller
masses with m < mm and accelerates their growth at large masses with m > mm. Therefore, the diffu-
sion leads to broadening of the size spectrum and accelerates coagulation.
Equation (14.7.15) can be rewritten in terms of radii. Using the conservation law fl (m)dm = fl (r)dr,
we obtain

∂ fl (r ) ∂ ɺ dr  ∂  dr ∂  dr 
∂t
=−
∂r  mm ,coag dm fl (m)  + ∂r  dm ∂r  Dm ,coag dm fl (m)   . (14.7.20)
 
Using the relation for spherical particles dm/dr = 4prwr2, we can introduce the drift velocity rɺcoag (the
radius growth rate) and diffusion coefficient Dr ,coag in the radii space:

dr Ec v (r )qls
rɺcoag = mɺ m ,coag = , (14.7.21)
dm 4 ρw
dr 2π 2 2π 2
Dr ,coag = Dm ,coag = Ec ρ w v (r ) Z r 6 = Ec cr 6 ρ w v (r ) N s r 6 . (14.7.22)
dm 9 9
14.7. The Coagulation Equation as the Integral Chapman–Kolmogorov 721

Thus, we can rewrite (Eqn. 14.7.20) as

∂ fl (r ) ∂ ∂  1 ∂ 
= − [rɺcoag fl (r )] +  [ Dr ,coag fl (r )] . (14.7.23)
∂t ∂r ∂r  4πρ w r 2 ∂r 
Equation (14.7.23) is the differential equation of the Fokker–Planck type for the size spectrum tak-
ing into account the drift and diffusion in the space of the radii and generalizes (Eqn. 14.2.15) of
Section 14.2 for coagulation in the continuous growth approximation that accounts only for the drift
but does not account for the diffusion. Equation (14.7.23) contains the term with the drift velocity
which coincides with (Eqn. 14.2.16) for the radius growth rate rɺcoag , and the new term with diffusion.
As discussed earlier for this equation in terms of masses, the new term in (Eqn. 14.7.23) with dif-
fusion in the radii space Dr,coag also causes faster spectral broadening and accelerates coagulation as
compared to the previous continuous growth approximation without diffusion.
Note finally that (Eqns. 14.7.15) and (14.7.23) of the Fokker–Planck type are the differential ana-
logs of the integral coagulation equations (Eqns. 5.6.4) and (5.6.7) of Section 5.6 or (Eqns. 14.2.1)–
(14.2.1a) and (14.2.1b) of Section 14.2 and of the integral Chapman–Komogorov (Eqn. 13.7.1a).
A similar analogy exists in the atmospheric models. The majority of the models are based on using
the differential equations of the Fokker–Planck type with advective and turbulent transport, where the
drift velocity is the wind speed and the diffusion is described by the turbulent coefficient. They are used
for routine calculations of the atmospheric processes, while only a few stochastic Lagrangian models
of turbulent diffusion are based on using the integral equations of the Chapman–Kolmogorov type
(e.g., Rodean, 1996; van Kampen, 1992; Monin and Yaglom, 2007a,b). It is known that solving the
integral equations of coagulation is computationally very expensive while solving the differential
equations is simpler and faster. Even the simplest approximation of continuous growth extensively
used in cloud modeling beginning from the pioneering work of Kessler (1969), and applied in many
models for parameterizing conversion rates, appeared to be successful (Pruppacher and Klett, 1997;
Cotton et al., 2011). Accounting for the next terms in expansion of the coagulation kernel and gen-
eralization taking into account diffusion in the space of mass or radii described in this section rep-
resents the next step in developing the approach of differential equations. Testing the differential
equations for coagulation described here versus full integral equations of coagulation and further
development of this approach (e.g., by accounting for the next terms in the Kramers–Moyal expan-
sion (Eqn. 14.7.3)) may allow us to develop fast and efficient methods for calculation of coagula-
tion–accretion based on the differential equations of the Fokker–Planck type.
722 Analytical Solutions to the Stochastic Kinetic Equation for Precipitating Clouds

Appendix A.14 Evaluation of the Integrals in Section 14.4.2 for v(r) 5 Avr

If v(r) = Avr, then Bv = 1 and (Eqns. 14.4.12a) and (14.4.12b) for I1, I2 in Section 14.4.1 can be rewritten as
r2
dr
I1 = − β l 0 bcon s ∫ , (A.14.1)
r1
bcon s + χ c Av r 2
r2
rdr
I 2 = α l (w − α l k ) ∫ . (A.14.2)
r1
bcon s + χ c Av r 2

We introduce the notation

1/2 1/2
 b | s |  | rɺ (r ) | 
Rl =  con  = r  cond  , (A.14.3a)
 χ c Av   rɺcoag (r ) 
(α l k − w) β 0 Rl
Ul = βl 0 , Ql = , (A.14.3b)
2 Av 2

where |x| means the absolute value of x. Here, the dimensions in CGS units are [Av] = s−1, [Rl] = cm.
Then, I1 for s > 0 can be rewritten as
x
dx
I1 = − β l 0 Rl ∫ , (A.14.4)
x0
1+ x2

where x = r/Rl, x0 = r0/Rl. This is the standard table integral, and its evaluation yields

I1 = − β l 0 Rl [arctan(r /Rl ) − arctan(r0 /Rl )]. (A.14.5)

For s < 0, using the relation s = −|s|, we see that the terms in the denominator of (Eqn. A.14.1) have
different signs thus I1 can be rewritten as
x
dx
I1 = − β l 0 Rl ∫ . (A.14.6)
x0
1− x2

This is also the standard table integral that is different for |x| < 1 and |x| > 1—that is:
β l 0 Rl 1 + x
x

I1 = − ln , for | x |< 1 (A.14.7)

2 1− x x0

β l 0 Rl x − 1
x

I1 = − ln for | x |> 1. (A.14.8)

2 x + 1 x0

For r < Rl, we have |x| < 1, and so (Eqn. A.14.7) is reduced to
r
 1 + r / Rl 
I1 = −Ql ln  
 1 − r / Rl  r0
Q
 (1 − r / Rl )(1 + r0 / Rl ) 
l

= ln   , s < 0, r < Rl . (A.14.9)

 (1 − r0 / Rl )(1 + r / Rl ) 
Evaluation of the Integrals 723

For r > Rl, we have |x| > 1, and (Eqn. A.14.8) is reduced to
r
 r / Rl − 1 
I1 = −Ql ln  
 r /Rl + 1  r0
Ql
 (r /Rl + 1)(r0 /Rl − 1) 
= ln   , s < 0, r > Rl . (A.14.10)
 (r0 /Rl + 1)(r /Rl − 1) 
The integral I2 in (Eqn. A.14.2) can be transformed for s > 0 as
x
xdx r
I 2 = 2U l ∫ , x= , (A.14.11)
x0
x2 + 1 Rl

and (Eqn. A.14.11) is evaluated with the standard integral

Ul
x  1 + (r /Rl )2 
I 2 = U l ln(1 + x 2 ) x = ln  2 
, s > 0. (A.14.12)
0
 1 + (r0 /Rl ) 
If s < 0, then x < 0 and I2 can be transformed as
x
xdx r
I 2 = 2U l ∫ , x= . (A.14.13)
x0
x2 −1 Rl

This integral is also standard and so we finally get

Ul
 (r /Rl )2 − 1 
I 2 = ln  2  , s < 0. (A.14.14)
 (r0 /Rl ) + 1 
This yields a factor in the size spectrum
Ul
 (r /R )2 + 1 
fl ~ exp(− I 2 ) =  0 l 2  (A.14.15)
 (r /Rl ) − 1 
These expressions for I1 and I2 and the corresponding factors in fl(r) are used in Section 14.4.2 for the
size spectra of the large-size fraction.
724 Analytical Solutions to the Stochastic Kinetic Equation for Precipitating Clouds

Appendix B.14 Evaluation of the Integrals in Section 14.4.4 for v(r) 5 Avr1/2
(Aerodynamic Regime of Fall Velocities)

If v(r) = Avr1/2, then Bv = 1/2 and (Eqns. 14.4.12a) and (14.4.12b) for I1, I2 in Section 14.4.2 can be
rewritten for s > 0 as
t
dt
I1 = − β l 0 H l I11 , I11 = ∫ 1+ t
t0
3/ 2
(B.14.1)

t
Vl tdt
I2 =
2
=I 21 , I 1 I 2 =I 21 = ∫ 1+ t
t0
3/ 2
, (B.14.2)

where
2/3
r0 r  b | s |
t0 = , t= H l =  con  ,
Hl Hl  χ c Av 
2α l ( w − α l k ) H l1/2
Vl = . (B.14.3)
χ c Av

Here, the dimensions in CGS units are [Av] = cm1/2 s−1, [Hl] = cm, and Vl is dimensionless. Intro-
ducing a new variable x = t1/2, the integral I11 can be transformed into that given in Gradshteyn and
Ryzhik (1994):
t x
dt xdx
I11 = ∫ 3/2
= 2∫
t0
1 + t x0
1 + x3
x
 1 1− x + x2 1 2x − 1 
= 2  ln + arctan . (B.14.4)
 6 (1 + x ) 2
3 3  x0

Then, finally

  (1 + x )2 (1 − x + x 2 ) 1/ 6 1  2x − 1 2 x − 1  
0 0
I1 = 2β l 0 H l ln  2 
−  arctan − arctan 0  . (B.14.5)
2
(1 + x 0 ) (1 − x + x )  3 3 3  
  

Here and in subsequent equations, x = (r/Hl)1/2.

The integral I21 in (Eqn. B.14.2) can be evaluated with the same substitution, x = t1/2:

x 3 dx
t x
tdt
I 21 = ∫ 1+ t
t0
3/2
= 2∫
x0
1+ x3
x
 1 1+ x 1 x 3
= 2  x − ln 2 1/2
− arctan  . (B.14.6)
 3 (1 − x + x ) 3 2− x 
x0

The last integral is from Gradshteyn and Ryzhik (1994). Substitution into (Eqn. B.14.2) yields

  (1 + x )(1 − x 0 + x 02 )1/ 2 
1/ 3
1  x 3 x 3  
I 2 = Vl  x − ln  2 1/ 2  − arctan − arctan 0 . (B.14.7)
  (1 + x 0 )(1 − x + x )  3 2− x 2 − x0  
Evaluation of the Integrals 725

For s < 0, I1 can be transformed as

t
dt
I1 = − β l 0 H l I12 , I12 = ∫ 1− t
t0
3/ 2
. (B.14.8)

Substitution x = t1/2 allows us to reduce I12 to that given in Gradshteyn and Ryzhik (1994):
t x
dt xdx
I12 = ∫ 3/2
= 2∫
t0
1− t x0
1− x3
x
 1 (1 − x )2 1 2x + 1 
= 2  − ln − arctan . (B.14.9)
 6 1+ x + x
2
3 3  x0

Then, finally

  (1 − x )2 (1 + x + x 2 ) 1/ 6 1  2x + 1 2 x + 1  
0 0
I1 = 2β l 0 H l ln  2 
−  arctan − arctan 0 . (B.14.10)
2
  (1 − x 0 ) (1 + x + x )  3 3 3  

For s < 0, I2 can be transformed as
t
Vl tdt
I2 = − I 22 , I 22 = ∫ . (B.14.11)
2 t0
1 − t 3/ 2

Substitution x = t1/2 yields the form given in Gradshteyn and Ryzhik (1994):

x 3 dx
x

I 22 = 2 ∫
x0
1− x3
x
 1 (1 + x + x 2 )1/2 1 x 3
= 2  − x + ln + arctan  . (B.14.12)
 3 1 − x 3 2 +x
x0

Substitution into (Eqn. B.14.11) yields

  (1 + x + x 2 )1/ 2 (1 − x 0 ) 
1/ 3
1  x 3 x 3  
I 2 = Vl  x − ln  2 1/ 2  − arctan − arctan 0   . (B.14.13)
 (1 + x + x ) (1 − x )  3  2 + x 2 + x0  
 0 0

These four integrals are used in Section 14.4.4 for evaluation of the size spectra fl for v(r) = Avr1/2.
References

Abbatt, J. P. D., S. Benz, D. J. Cziczo, Z. Kanji, U. Lohmann, and O. Möhler (2006). Solid
ammonium sulfate aerosols as ice nuclei: A pathway for cirrus cloud formation. Science,
313, 1770–1773.
Abdul-Razzak, H., and S. J. Ghan (2000). A parameterization of aerosol activation: 2. Multiple
aerosol types. J. Geophys. Res., 105, 6837–6844.
Abdul-Razzak, H., and S. J. Ghan (2004). Parameterization of the influence of organic surfac-
tants on aerosol activation. J. Geophys. Res., 109, D03205, doi:10.1029/2003JD004043.
Abdul-Razzak, H., S. J. Ghan, and C. Rivera-Carpio (1998). A parameterization of aerosol
activation: 1. Single aerosol type. J. Geophys. Res., 103, 6123–6131.
Abraham, F. (1970). Functional dependence of drag coefficient of a sphere on Reynolds number.
Phys. Fluids, 13, 2194–2195.
Ackerman, S., and G. L. Stephens (1987). The absorption of solar radiation by cloud droplets:
An application of anomalous diffraction theory. J. Atmos. Sci., 44, 1574–1588.
Agee, E. M. (1985). Extratropical cloud-topped boundary layers over the oceans. Rep. JSC/CAS
Workshop on Modeling of CTBL, Fort Collins, CO, USA, WMO/TD No 75, 67 pp.
Agee, E. M. (1987). Mesoscale cellular convection over the oceans. Dyn. Atmos. Oceans, 10,
317–341.
Albrecht, B. (1989). Aerosols, cloud microphysics and fractional cloudiness. Science, 245,
1227–1230.
Aleksandrov, E. L., and K. B. Yudin (1979). On the vertical profile of the cloud microstructure
in stratiform clouds. Sov. Meteorol. Hydrol., 12, 47–61.
Ally, M. R., S. I. Clegg, J. Braunstein, and J. M. Simonson (2001). Activities and osmotic coef-
ficients of tropospheric aerosols: (NH4)2SO4 (aq) and NaCl (aq). J. Chem. Themodynamics,
33, 905–915.
Al-Naimi, R., and C. P. R. Saunders (1985). Measurements of natural deposition and condensation-
freezing ice nuclei with a continuous flow chamber. Atmos., Environ., 19, 1871–1882.
Angell, C. A. (1982). In: Water: A comprehensive treatise, vol. 7. Ed.: Franks, F., Plenum,
New York, 1–81.
Ångström, A. (1929). On the atmospheric transmission of sun radiation and on dust in the air.
Geogr. Ann., 11, 156–166.
Ångström, A. (1964). The parameters of atmospheric turbidity. Tellus, 16, 64–75.
Archuleta, C. M., P. J. DeMott, and S. M. Kreidenweis (2005). Ice nucleation by surrogates
for atmospheric mineral dust and mineral dust/sulfate particles at cirrus temperatures. Atmos.
Chem. Phys., 5, 2617–2634.
Atkins, P. W. (1982). Physical chemistry, 2nd ed., Oxford Univ. Press., 1095 pp.

727
728 References

Auer, A. H., Jr., and D. L. Veal (1970). The dimensions of ice crystals in natural clouds. J. Atmos.
Sci., 27, 919–926.
Austin, P. H., M. B. Baker, A. M. Blyth, and J. B. Jensen (1985). Small-scale variability in warm
continental cumulus clouds. J. Atmos. Sci., 42, 1123–1138.
Bakan, S. (1984). Note on cellular convection with nonisotropic eddies. Tellus, 36A, 87–89.
Baker, M. B. (1993). Variability in concentrations of CCN in the marine cloud-top boundary layer.
Tellus, Ser. B, 45, 458–472.
Baker, M. B., and M. Baker (2004). A new look at homogeneous freezing of water. Geophys.
Res. Lett., 31, L19102, doi:10.1029/2004GL020483.
Baker, M. B., and J. Latham (1979). The evolution of the droplet spectra and the rate of produc-
tion of embryonic raindrops in small cumulus clouds. J. Atmos. Sci., 36, 1612–1615.
Baker, M. B., R. G. Corbin, and J. Latham (1980). The influence of entrainment on the evolu-
tion cloud droplet spectra: I. A model of inhomogeneous mixing. Q. J. Roy. Meteor. Soc., 106,
581–598.
Baker, M. B., R. E. Briedenthal, T. W. Choularton, and J. Latham (1984). The effects of turbu-
lent mixing in clouds. J. Atmos. Sci., 41, 299–304.
Bakhanov, V. P., and M. V. Buikov (1985). Modeling artificial crystallization, precipitation for-
mation and dispersal of supercooled stratiform clouds. Review. Proc. Sov. Inst. Sci. Inf., ser.
Meteorology, No. 6, 50 pp., Obninsk, Moscow Region (in Russian).
Barahona, D., and A. Nenes (2008). Parameterization of cirrus formation in large scale models:
Homogenous nucleation. J. Geophys. Res., 113, doi:10.1029/2007JD009355.
Barahona, D., and A. Nenes (2009). Parameterizing the competition between homogeneous and
heterogeneous freezing in cirrus cloud formation monodisperse ice nuclei. Atmos. Chem.
Phys., 9, 369–381.
Bartlett J. T., and P. R. Jonas (1972). On the dispersions of the sizes of droplets growing by con-
densation in turbulent clouds. Quart. J. Roy. Meteor. Soc., 98, 150–164.
Barton, E. F., and W. F. Oliver (1936). The crystal structure of ice at low temperatures. Proc. Roy.
Soc. Lond., A 153, 166–172.
Bashkirova, T. A., and T. A. Pershina (1964). On the mass of snow crystals and their fall velocity.
Proc. Main Geophys. Observ., 165, 83–100.
Bauer, S. E. and D. Koch (2005), Impact of heterogeneous sulfate formation at mineral dust sur-
faces on aerosol loads and radiative forcing in the Goddard Institute for Space Studies general
circulation model. J. Geophys. Res., 110, http://dx.doi.org/10.1029/2005JD005870.
Beard, K. V. (1976). Terminal velocity and shape of cloud and precipitation drops aloft. J. Atmos.
Sci., 33, 851–864.
Beard, K. V. (1980). The effect of altitude and electrical force on the terminal velocity of hydrome-
teors. J. Atmos. Sci., 37, 1363–1374.
Beard, K. V., and C. Chuang (1987). A new model for the equilibrium shape of raindrops.
J. Atmos. Sci., 44, 1509–1524.
Beard K. V., and H. T. Ochs (1993). Warm-rain initiation: an overview of microphysical mecha-
nisms. J. Appl. Meteorol., 32, 608–625.
Beard, K. V., and H. R. Pruppacher (1971). A wind tunnel investigation of the rate of evaporation
of small water drops at terminal velocity in air. J. Atmos. Sci., 28, 1455–1464.
Becker, R., and W. Döring (1935). Kinetische Behandlung der Keimbildung in übersättigten
Dämpfen. Ann. Physik, 24, 719–752.
Belyaev, V. I. (1961). Size distribution of drops in a cloud during its condensation stage of develop-
ment. Izv. Acad. Sci. USSR, Geophys. Ser., 8, 1209–1213.
Belyaev, V. I. (1964). The method of Lagrange in the kinetics of cloud processes. Leningrad,
Hydrometeoizdat, 119 pp. (in Russian).
References 729

Berezinsky, N. A., and G. V. Stepanov (1986). Dependence of natural ice-forming nuclei concen-
tration of different size on the temperature and supersaturation. Izv. Acad Sci. USSR, Atmos.
Oceanic Phys., 22, 722–727.
Bergeron, T. (1935). On the physics of clouds and precipitation. Proc. Vth Assembly General of
the International Union of Geodesy and Geophysics, Lisbon, Portugal, International Union
of Geodesy and Geophysics, 156–180.
Berjulev, G. P., A. A. Chernikov, B. G. Danelyan, V. I. Khvorostyanov, Y. A. Seregin, G. R.
Toroyan, and M. V. Vlasyuk (1989). Field study and numerical simulation of an orographic
cloud system: Natural evolution and seeding. Proc. IVth International Conf. on Weather Modi-
fication, Beijing, China, 128–132.
Berlyand, T. G., and L. A. Strokina (1980). Global distribution of total cloud amount.
Hydrometeoizdat, Leningrad, 71 pp. (in Russian) (English translation by S. Warren).
Berry, E. X. (1967). Cloud drop growth by coalescence. J. Atmos. Sci., 24, 688–701.
Berry, E. X., and R. L. Reinhardt (1974a). An analysis of cloud drop growth by collection: Part I.
Double distributions. J. Atmos. Sci., 31, 1814–1824.
Berry, E. X., and R. L. Reinhardt (1974b). An analysis of cloud drop growth by collection: Part II.
Single initial distributions. J. Atmos. Sci., 31, 1825–1831.
Bertram, A. K., D. D. Patterson, and J. J. Sloan (1996). Mechanisms and temperatures for the freez-
ing of sulfuric acid aerosols measured by FTIR spectroscopy. J. Phys. Chem., 100, 2376–2383.
Bertram, A. K., T. Koop, L. T. Molina, and M. J. Molina (2000). Ice formation in (NH4)2SO4-H2O
particles. J. Phys. Chem. A, 104, 584–588.
Bigg, E. K. (1953). The supercooling of water. Proc. Phys. Soc., B 66, 688–703.
Bigg, E. K., and C. Leck (2001a). Cloud-active particles over the central Arctic Ocean. J. Geophys.
Res., 106 (D23), 32,155–32,166.
Bigg, E. K., and C. Leck (2001b). Properties of the aerosol over the central Arctic Ocean. J. Geophys.
Res., 106 (D23), 32,101–32,109.
Bigg, E. K., J. L. Brownscombe, and W. Thompson (1969). Fog modification with long-chain
alcohols. J. Appl. Met., 8, 75–82.
Biskos, G., A. Malinowski, L. M. Russell, P. R. Buseck, and S. T. Martin (2006a). Nanosize
effect on the deliquescence and the efflorescence of sodium chloride particles. Aeros. Sci.
Technol., 40, 97–106.
Biskos, G., L. M. Russell, P. R. Buseck, and S. T. Martin (2006b). Nanosize effect on the hygro-
scopic growth factor of aerosol particles. Geophys. Res. Lett., 33, (1–4), L07, 801.
Bleck, R. (1970). A fast, approximative method for integrating the stochastic coalescence equation.
J. Geophys. Res., 75, 5165–5171.
Blüthgen, J. (1966). Allgemeine klimageographie, Walter de Gruyter, Berlin, v. 2, 710 pp.
Bogdan, A., and M. J. Molina (2009). Why does large relative humidity with respect to ice persist
in cirrus ice clouds? J. Phys. Chem. A, 113, 14,123–14,130.
Bogdan, A., M. J. Molina, M. Kulmala, H. Tenhu, and T. Loerting (2013). Solution coating
around ice particles of incipient cirrus clouds. Proc. Natl. Acad. Sci., www.pnas.org/cgi/
doi/10.1073/pnas.1304471110.
Blyth, A. (1993). Entrainment in cumulus clouds. J. Appl. Meteorol. 32, 626–641.
Böhm, J. P. (1989). A general equation for the terminal fall speed of solid hydrometeors. J. Atmos.
Sci., 46, 2419–2427.
Böhm, J. P. (1992). A general hydrodynamic theory for mixed-phase microphysics. Part I: Drag
and fall speeds of hydrometeors. Atmos. Res., 27, 253–274.
Borick, S. S., P. G. Debenedetti, and S. Sastry (1995). A lattice model of network-forming fluids
with orientation-dependent bonding: Equilibrium, stability, and implications for the phase
behavior of supercooled water. J. Phys. Chem., 99, 3781–3792.
730 References

Born, M. (1963). Atomic physics, Blackie and Son, Ltd., London-Glasgow, 493 pp.
Borovikov, A. M., I. P. Mazin, and A. N. Nevzorov (1965). Some features of distribution of the
large particles in clouds of various forms. Izv. Acad. Sci. USSR, Atmos. Oceanic Phys., 1 (3),
357–369.
Borovikov, A. M., I. I. Gaivoronsky, E. G. Zak, V. V. Kostarev, I. P. Mazin, V. E. Minervin,
A. Kh. Khrgian, and S. M. Shmeter (1963). The physics of clouds. Leningrad, Hydrome-
teoizdat, 1961, Transl. by Israel Program Scientif. Translation, U.S. Dept. Commerce,
Washington, DC, 459 pp. 1963.
Bott, A. (1998). A flux method for the numerical solution of the stochastic collection equation.
J. Atmos. Sci., 55, 2284–2293.
Bott, A. (2000). A flux method for the numerical solution of the stochastic collection equation:
Extension to two-dimensional particle distributions. J. Atmos. Sci., 57, 284–294.
Bott, A. (2001). A new method for the solution of the stochastic collection equation in cloud models
with spectral aerosol and cloud drop microphysics. Atmos. Res., 59–60, 361–372.
Boville, B. A., P. J. Rasch, J. J. Hack, and J. R. McCaa (2006). Representation of clouds and
precipitation processes in the Community Atmosphere Model version 3 (CAM3). J. Climate,
19, 2184–2198.
Braham, R. R. (1976). CCN spectra in c-k space. J. Atmos. Sci., 33, 343–346.
Brandes, E. A., G. Zhang, and J. Vivekanandan (2003). An evaluation of a drop distribution-
based polarimetric radar rainfall estimator. J. Appl. Meteor., 42, 652–660.
Brechtel, F. J., and S. M. Kreidenweis (2000a). Predicting particle critical supersaturation from
hygroscopic growth measurements in the humidified TDMA. Part I: Theory and sensitivity
studies. J. Atmos. Sci., 57, 1854–1871.
Brechtel, F. J., and S. M. Kreidenweis (2000b). Predicting particle critical supersaturation from
hygroscopic growth measurements in the humidified TDMA. Part II: Laboratory and ambient
studies. J. Atmos. Sci., 57, 1872–1887.
Brenguier, J.-L., and L. Chaumat (2001). Droplet spectra broadening in cumulus clouds. Part I:
broadening in adiabatic cores. J. Atmos. Sci., 58, 628–641.
Bretherton, C. S., M. K. MacVean, P. Bechtold, A. Chlond, W. R. Cotton, et al. (1999a). An
intercomparison of radiatively-driven entrainment and turbulence in a smoke cloud, as simu-
lated by different numerical models. Quart. J. Roy. Meteor. Soc., 125, 391–423.
Bretherton, C. S., S. K. Krueger, P. Bechtold, E. van Meijgaard, B. Stevens, and J. Teixeira
(1999b). A GCSS boundary layer model intercomparison study of the first ASTEX Lagrangian
experiment. Bound.-Layer Meteor., 93, 341–380.
Bridgman, P. W. (1912). Water, in the liquid and five solid forms, under pressure. Proc. Amer.
Acad. Arts Sci., 47, 441–558.
Broadwell, J. E., and R. E. Briedenthal (1982). A simple model of mixing and chemical reaction
in a turbulent shear layer. J. Fluid. Mech., 125, 397–410.
Brock, J. R. (1962). On the theory of thermal forces acting on aerosol particles. J. Colloid Sci., 17,
768–780.
Brown, A. J., and E. Whalley (1966). Preliminary investigation of the phase boundaries between
ice VI and VII and ice VI and VIII. J. Chem. Phys., 45, 4360–4361.
Brown, P. S. (1991). Parameterization of the evolving drop-size distribution based on analytic solu-
tion of the linearized coalescence breakup equation. J. Atmos. Sci., 48, 200–210.
Brown, P. S. (1997). Mass conservation considerations in analytic representation of rain drop frag-
ment distribution. J. Atmos. Sci., 54, 1675–1687.
Brown, R. A. (1974). Analytical methods in planetary boundary layer modeling. Adam Higler,
London, 150 pp.
Brown, S. R. (1970). Terminal velocities of ice crystals. M. S. Thesis, Dept. of Atmospheric Sciences,
Fort Collins, Colorado, 52 pp.
References 731

Brüggeller, P., and E. Mayer (1980). Complete vitrification in pure water and dilute aqueous solu-
tions. Nature, 288, 569–571.
Brümmer, B. (1985). Structure, dynamics and energetics of boundary layer rolls from KonTur air-
craft observations. Contr.Atm.Phys., 58, 237–254.
Brümmer, B., B. Rump, and G. Kruspe (1992). A cold air outbreak near Spitsbergen in spring-
time: Boundary-layer modification and cloud development. Boundary Layer Meteorol.,
61, 13–46.
Bryant, F. D., and P. Latimer (1969). Optical efficiencies of large particles of arbitrary shape and
orientation. J. Colloid Interface Sci., 30, 291–304.
Buikov, M. V. (1961). Kinetics of distillation in a polydisperse fog. Izvestia Acad. Sci. USSR, Ser.
Geophys., 7, 1058–1065.
Buikov, M. V. (1963). A method of the kinetic equations in the theory of clouds. Proc. All-Union
Meteorol. Conf., Leningrad, 5, 122–128.
Buikov, M. V. (1966a). Kinetics of heterogeneous condensation at adiabatic cooling. Part 1:
Diffusion regime of droplet growth. Colloid J., 28 (5), 628–634.
Buikov, M. V. (1966b). Kinetics of heterogeneous condensation at adiabatic cooling. Part 2: Kinetic
regime of droplet growth. Colloid J., 28 (5), 635–639.
Buikov, M. V., and V. I. Khvorostyanov (1976). Numerical simulation of radiation fog and stratus
clouds formation with account for interaction among dynamic, radiative and microphysical
processes. Proc. 6th Intern. Conf. Cloud Phys., Boulder, CO, USA, 392–395.
Buikov, M. V., and V. I. Khvorostyanov (1977). Formation and evolution of radiative fog and
stratus clouds in the boundary layer of the atmosphere with explicit account for microphysical
processes. Izv. Acad. Sci. USSR, Atmos. Oceanic Phys., 13(4), 356–370.
Buikov, M. V., and V. I. Khvorostyanov (1979). Dispersal of fogs with surface-active reagents.
A review. Soviet Meteorol. Hydrol. 5, 28–35.
Buikov, M. V., and A. M. Pirnach (1973). A numerical model of a two-phase stratiform cloud
with explicit account for microstructure. Izv. Acad. Sci. USSR, Atmos. Oceanic Phys., 9 (5),
486–499.
Buikov, M. V., and A. M. Pirnach (1975). Numerical modeling of microphysical processes of
precipitation formation in stratiform mixed-phase clouds with a 1D spectral bin microphysical
model. Izv. Acad. Sci. USSR, Atmos. Oceanic Phys., 11(5), 469–480.
Buikov, M. V., K. Y. Ibragimov, A. M. Pirnach, and L. P. Sorokina (1976). A study of the two-
phase stratiform clouds in the atmosphere of Jupiter. Astrophys. J., 53, 596–602.
Bunker, K. W., S. China, C. Mazzoleni, A. Kostinski, and W. Cantrell (2012). Measurements
of ice nucleation by mineral dusts in the contact mode, Atmos. Chem. Phys. Discuss.,
12, 20,291–20,309, doi:10.5194/acpd-12-20291-2012.
Butorin, G. T., and K. P. Skripov (1972). Crystallizaton of supercooled water. Soviet Phys.
Crystallogr., 17, 322–326.
Callen, H. B. (1960). Thermodynamics: An introduction to the physical theories of equilibrium
thermostatics and irreversible thermodynamics. J. Wiley and Sons, Inc., New York, 376 pp.
Cantrell, W., and C. Robinson (2006). Heterogeneous freezing of ammonium sulfate and
sodium chloride solutions by long chain alcohols. Geophys. Res. Lett., 33, L07802,
doi:10.1029/2005GL024945.
Charlson, R. J., J. H. Seinfeld, A. Nenes, M. Kulmala, A. Laaksonen, and M. C. Faccini
(2001). Reshaping the theory of cloud formation, Science, 292, 20205–2026.
Chen, J.-P. (1994). Theory of deliquescence and modified Köhler curves, J. Atmos. Sci.,
51, 3505–3516.
Chen, J.-P., A. Hazra, and Z. Levin (2008). Parameterizing ice nucleation rates using contact
angle and activation energy derived from laboratory data, Atmos. Chem. Phys.,
8, 7431–7449.
732 References

Chen Y., P. J. DeMott, S. M. Kreidenweis, D. C. Rogers, and E. Sherman (2000). Ice formation
by sulfate and sulfur acid aerosols under upper-tropospheric conditions, J. Atmos. Sci.,
57, 3752–3766.
Chen, Y., S. M. Kreidenweis, L. M. McInnes, D. C. Rogers, and P. J. DeMott (1998). Single
particle analyses of ice nucleating aerosols in the upper troposphere and lower stratosphere.
Geophys. Res. Lett., 25, 1391–1394.
Chlond, A. (1992). Three-dimensional simulation of cloud street development during a cold air
outbreak. Boundary Layer Meteorol., 58, 161–200.
Chuang, P. (2003). Measurement of the timescale of hygroscopic growth for atmospheric aerosols.
J. Geophys. Res., 108, 4282, doi:10.1029/2002JD002757.
Chukin, V. V., and A. S. Platonova (2012). Model of crystallization of supercooled droplets of
aqueous solution. Proc. Intl. Conf. Clouds and Precipitation, Leipzig, August 2012.
Chukin, V. V., E. A. Pavlenko, and A. S. Platonova (2010). Homogeneous ice nucleation rate in
supercooled droplets of aqueous solutions. Rus. Meteorol. Hydrol., 35, No. 8, 524–529.
Chylek, P., and J. D. Klett (1991a). Extinction cross sections of non-spherical particles in the
anomalous diffraction approximation. J. Opt. Soc. Am., 8, 274–281.
Chylek, P., and J. D. Klett (1991b). Absorption and scattering of electromagnetic radiation by
prismatic columns: Anomalous diffraction approximation. J. Opt. Soc. Am., 8, 1713–1720.
Chylek, P. and Videen (1994). Longwave radiative properties of polydispersed hexagonal ice crys-
tals. J. Atmos. Sci., 51, 175–190.
Chylek, P., and J. G. D. Wong (1998), Erroneous use of the modified Köhler equation in cloud and
aerosol physics applications, J. Atmos. Sci., 55, 1473–1477.
Cirrus (2002). Eds.: Lynch, D., Sassen, K., Starr, D. O’C., and Stephens, G., Oxford University
Press, New York, 480 pp.
Clark, T. (1974). A study of cloud phase parameterization using the gamma distribution. J. Atmos.
Sci., 31, 142–155.
Clark, T. L. (1976). Use of log-normal distributions for numerical calculations of condensation and
collection. J. Atmos. Sci., 33, 810–821.
Clegg, S. L., and P. Brimblecombe (1995). Application of a multicomponent thermodynamic
model to activities and thermal properties of 0–40 mol kg−1 aqueous sulfuric acid from
<200 to 328 K, J. Chem. Eng. Ref. Data, 40, 43–64.
Clegg, S. L., P. Brimblecombe, and A. S. Wexler (1998). A thermodynamic model of the system
H+-NH4+-SO42--NO3--H2O at tropospheric temperatures. J. Phys. Chem., 102, 2137–2154.
Clegg, S. L., S. S. Ho, C. K. Chan, and P. Brimblecombe (1995). Thermodynamic properties of
aqueous (NH)2SO4 to high supersaturation as a function of temperature. J. Chem. Eng. Data,
40, 1079–1090.
Coakley, J. A., Jr., et al. (1987). Effect of ship-stack effluents on cloud reflectivity. Science,
237, 1020–1022.
Cohard, J.-M., and J.-P. Pinty (2000). A comprehensive two-moment warm microphysical bulk
scheme. I: Description and tests. Q. J. Roy. Meteorol. Soc., 126, 1815–1842.
Cohard, J.-M., J.-P. Pinty, and C. Bedos (1998). Extending Twomey’s analytical estimate of
nucleated cloud droplet concentrations from CCN spectra. J. Atmos. Sci., 55, 3348–3357.
Cohard, J.-M., J.-P. Pinty, and K. Suhre (2000). On the parameterization of activation spec-
tra from cloud condensation nuclei microphysical properties. J. Geophys. Res., 105 (D9),
11,753–11,766.
Collins, W. D., P. J. Rasch, B. A. Boville, J. J. Hack, J. R. McCaa, D. L. Williamson, B. P.
Briegleb, C. M. Bitz, S. J. Lin, and M. H. Zhang (2006). The formulation and atmospheric
simulation of the Community Atmosphere Model version 3 (CAM3), J. Clim., 19 (11),
2144–2161, doi:10.1175/JCLI3760.1.
References 733

Comstock, J. M., T. P. Ackerman, and D. D. Turner (2004). Evidence of high ice supersaturation
in cirrus clouds using ARM Raman lidar measurements, Geophys. Res. Lett., 31, L10106,
doi:10.1029/2004GL019539.
Comstock, J. M., R.-F. Lin, D. O’C. Starr, and P. Yang (2008). Understanding ice supersatura-
tion, particle growth, and number concentration in cirrus clouds. J. Geophys. Res.,
113, D23211, doi: 10.1029/2008JD010332.
Connolly, P. J., O. Möhler, P. R. Field, H. Saathoff, R. Burgess, T. Choularton, and M. Gallagher
(2009). Studies of heterogeneous freezing by three different desert dust samples, Atmos. Chem.
Phys., 9, 2805–2824, doi:10.5194/acp-9-2805-2009.
Considine, G. and J. A. Curry (1996). A statistical model of drop size spectra for stratocumulus
clouds. Quart. J. Roy. Meteor. Soc., 122, 611–634.
Considine, G. and J. A. Curry (1998). Role of entrainment and droplet sedimentation on the
microphysical structure in stratus and stratocumulus clouds. Quart. J. Roy. Meteorol. Soc.,
24, 123–150.
Cooper, W. A. (1974). A possible mechanism for contact nucleation. J. Atmos. Sci., 31, 1832–1837.
Cooper, W. A. (1986). Ice initiation in natural clouds. In: Precipitation enhancement: A scientific
challenge, Meteor. Monogr., 21, Amer. Meteor. Soc., Boston, 29–32.
Cooper, W. A. (1989). Effects of variable droplet growth histories on droplet size distributions.
Part I: Theory. J. Atmos. Sci., 46, 1301–1311.
Cooper, W. A. (1995). Ice formation in wave clouds: Observed enhancement during evaporation.
In “Proc. Conf. on Cloud Physics.” pp. 147–152. Amer. Met. Soc, Dallas.
Cooper, W. A., and G. Vali (1981). The origin of ice in mountain cap clouds. J. Atmos. Sci.,
38, 1244–1259.
Cotton, R. J., and P. R. Field (2002). Ice nucleation characteristics of an isolated wave cloud.
Quart. J. Roy. Meteorol. Soc., 128, 2417–2437.
Cotton, W. R., and R. A. Pielke (2007). Human impacts on weather and climate, 2nd ed.
Cambridge Univ. Press, 315 pp.
Cotton, W. R., G. Bryan, and S. van den Heever (2011). Storm and Cloud Dynamics, Intern.
Geophys. Ser., v. 99, Academic Press, Elsevier Publishers, The Netherlands, 809 pp.
Cotton, W. R., G. J. Tripoli, R. M. Rauber, E. A. Mulvihill (1986). Numerical simulation of the
effects of varying ice nucleation rates and aggregation process on orographic snowfall.
J. Climate Appl. Meteorol., 25, 1658–1680.
Cotton, W. R., R. A. Pielke Sr., R. L. Walko, G. E. Liston, C. J. Tremback, H. Jiang, R. L.
McAnelly, J. Y. Harrington, M. E. Nicholls, G. G. Carrio, and J. P. McFadden (2003).
RAMS 2001: Current status and future directions. Meteor. Atmos. Phys., 82, 5–29.
CTBL (1985). Report of the JSC/CAS Workshop on modeling of Cloud-Topped Boundary Layer.
Fort Collins, CO, USA, 22–26 April 1985, 96 pp.
Curry, J. A. (1983). On the formation of continental polar air. J. Atmos. Sci., 40, 2278–2292.
Curry, J. A. (1986). Interactions among turbulence, radiation and microphysics in Arctic stratus
clouds. J. Atmos. Sci., 43, 525–538.
Curry, J. A. (1995). Interactions among aerosols, clouds, and climate of the Arctic Ocean. Sci.
Total Environ., 160, 777–791.
Curry, J. A., and G. F. Herman (1985). Infrared radiative properties of summertime Arctic stratus
clouds. J. Clim. Appl. Meteorol., 24, 525–538.
Curry J. A., and V. I. Khvorostyanov (2012). Assessment of some parameterizations of heteroge-
neous ice nucleation in cloud and climate models. Atmos. Chem. Phys., 12, 1151–1172,
www.atmos-chem-phys.net/12/1151/2012/, doi:10.5194/acp-12-1151-2012.
Curry, J. A., and P. J. Webster (1999), Thermodynamics of atmospheres and oceans, Academic
Press, London, 467 pp.
734 References

Curry, J. A., E. E. Ebert, and G. F. Herman (1988). Mean and turbulent structure of the summer-
time Arctic cloudy boundary layer. Quart. J. Roy. Meteor. Soc., 114, 715–746.
Curry, J. A., J. Schramm, and E. E. Ebert (1993). Impact of clouds on the surface radiation bud-
get of the Arctic Ocean. Meteor. and Atmos. Phys, 57, 197–217.
Curry, J. A., W. B. Rossow, D. Randall, and J. L. Schramm (1996). Overview of Arctic cloud
and radiation properties. J. Clim., 9, 1731–1764.
Curry, J. A., F. G. Meyer, L. F. Radke, C. A. Brock, and E. E. Ebert (1990). The occurrence and
characteristics of lower tropospheric ice crystals in the Arctic. Int. J. Climatol., 10, 749–764.
Curry, J. A., P. V. Hobbs, M. D. King, D. A. Randall, P. Minnis, et al. (2000). FIRE Arctic clouds
experiment, Bull. Amer. Meteor. Soc., 81, 5-29.
Cziczo, D. J., and J. P. D. Abbatt (1999). Deliquescence, efflorescence and supercooling of
ammonium sulfate aerosols at low temperature: Implications for cirrus cloud formation and
aerosol phase in the atmosphere. J. Geophys. Res., 104, 13,781–13,790.
Cziczo, D. J., D. M. Murphy, P. K. Hudson, and D. S. Thomson (2004). Single particle measure-
ments of the chemical composition of cirrus ice residue during CRYSTAL-FACE, J. Geophys.
Res., 109, (D4), D04201, 10.1029/2003JD004032.
Dash, J. G., H. Fu, and J. S. Wettlaufer (1995). The premelting of ice and its environmental con-
sequences. Rep. Progr. Phys., 58, 115–167.
Debenedetti, P. K. (2003). Supercooled and glassy water. J. Phys. Condens. Matter, 15,
R1669–1726.
Debye, P. (1912). Zur theorie der spezifischen wärmen. Annaln. Phys., 39, 789–839.
Defay, R., I. Prigogine, A. Bellemans, and D. Everett (1966). Surface tension and absorption,
432 pp., Wiley, New York.
Deirmendijan, D. (1969). Electromagnetic scattering on spherical polydispersions. Elsevier,
291 pp.
DeMott, P. J. (2002). Laboratory studies of cirrus cloud processes. In: Cirrus. Eds.: Lynch, D.,
Sassen, K., Starr, D. O’C., and Stephens, G., Oxford University Press, 102–135.
DeMott, P. J., and D. C. Rogers (1990). Freezing nucleation rates of dilute solution droplets mea-
sured between −30 and −40°C in laboratory simulations of natural clouds. J. Atmos. Sci.,
47, 1056–1064.
DeMott, P. J., M. P. Meyers, and W. R. Cotton (1994). Parameterization and impact of ice initia-
tion processes relevant to numerical model simulation of cirrus clouds, J. Atmos. Sci.,
51, 77–90.
DeMott, P. J., D. C. Rogers, and S. M. Kreidenweis (1997). The susceptibility of ice formation in
upper tropospheric clouds to insoluble aerosol components. J. Geophys. Res.,
102, 19,575–19,584.
DeMott, P. J., D. C. Rogers, S. M. Kreidenweis, Y. Chen, C. H. Twohy, D. Baumgardner, A. J.
Heymsfield, and K. R. Chan (1998). The role of heterogeneous freezing nucleation in upper
tropospheric clouds: Inferences from SUCCESS. Geophys. Res. Lett., 25, 1387–1390.
DeMott, P. J., D. J. Cziczo, A. J. Prenni, D. M. Murphy, S. M. Kreidenweis, D. S. Thomson,
R. Borys, and D. C. Rogers (2003). Measurements of the concentration and composition of
nuclei for cirrus formation, Proc. Natl. Acad. Sci., 100, 14,655–14,660.
DeMott, P. J., A. J. Prenni, X. Liu, S. M. Kreidenweis, M. D. Petters, C. H. Twohy,
M. S. Richardson, T. Eidhammer, and D. C. Rogers (2010). Predicting global atmospheric
ice nuclei distributions and their impacts on climate, Proc. Natl. Acad. Sci. USA,
107, 11,217–11,222.
Denbigh, K. (1981). The principles of chemical equilibrium, Cambridge University Press, 494 pp.
Dennis, A. S. (1980). Weather modification by cloud seeding. Academic Press, New York, 274 pp.
Deryagin, B. V. and Y. S. Kurgin (1972). The theory of passivation of the droplet condensation
growth by the vapor of cetyl alcohol. Colloid. J., 35, 26–42.
References 735

Deryagin, B. V., V. A. Fedoseev, and L. A. Rosentsveig (1966). A study of the adsorption of the
cetyl alcohol vapor and its impact on evaporation of water drops. Docl. Acad. Sci. USSR,
167 (3), 616–620.
Dick, W. D., P. Saxena, and P. H. McMurry (2000). Estimation of water uptake by organic com-
pounds in submicron aerosols measured during the Southeastern Aerosol and Visibility Study,
J. Geophys. Res., 105 (D1), 1471–1479.
Diehl, K., and S. Wurzler (2004). Heterogeneous drop freezing in the immersion mode:
Model calculations considering soluble and insoluble particles in drops. J. Atmos. Sci.,
61, 2063–2072.
Djikaev, Y. S. and E. Ruckenstein (2008). Thermodynamics of heterogeneous crystal nucleation
in contact and immersion modes. J. Phys. Chem. A, 112, 11,677–11,687.
Djikaev, Y. S., A. Tabazadeh, P. Hamill, and H. Reiss (2002). Thermodynamic conditions
for the surface-stimulated crystallization of atmospheric droplets. J. Phys. Chem., A106,
10,247–10,253.
Dmitrieva-Arrago, L. R, and I. V. Akimov (1998). A method for calculation of nonconvective
precipitation on the basis of liquid water content forecast with account for cloud microphys-
ics. Sov. Meteorol. Hydrol., 11, 47–59.
Dorsey, N. E. (1968). Properties of ordinary water-substance. Hafner Publish. Co., 637 pp.
Dufour, L., and R. Defay (1963). Thermodynamics of clouds. Academic Press, New York, 255 pp.
Durant, A. J., and R. A. Shaw (2005). Evaporating freezing by contact nucleation inside-out.
Geophys. Res. Lett., 32, L20814, doi: 10.1029/2005GL025175.
Eadie, W. J. (1971). A molecular theory of the homogeneous nucleation of ice from supercooled
water. PhD Dissertation, University of Chicago, Cloud Physics Lab, Tech. Note 40, 117 pp.
Ebert, E. E., and J. A. Curry (1992). A parameterization of ice cloud optical properties for cli-
mate models. J. Geophys. Res., 97, 3831–3836.
ECMWF-2007: European Centre for Medium Range Weather Forecast (ECMWF), (2007).
“IFS documentation cycle 31rl, Part IV: Physical processes.” 155 pp., http://www.ecmwf.int/
research/ifsdocs/CY31rl/index.html.
Eidhammer, T., P. J. DeMott, and S. M. Kreidenweis (2009). A comparison of heterogeneous ice
nucleation parameterization using a parcel model framework. J. Geophys. Res., 114, D06202,
doi: 10.1029/2008JD011095.
Einstein, A. (1906). Die plancksche theorie der Strahlung und die spezifischen Wärme. Annaln.
Phys., 22, 180–190.
Elbaum, M., and M. Schick (1991). Application of the theory of dispersion forces to the surface
melting of ice. Phys. Rev. Lett. 66, 1713–1716.
Elbaum, M., S. G. Lipson, and J. D. Dash (1993). Optical study of surface melting on ice.
J. Cryst. Growth, 129, 491–505.
Ervens, B., and G. Feingold (2012). On the representation of immersion and condensation freez-
ing in cloud models using different nucleation schemes. Atmos. Chem. Phys., 12, 5807–5826.
Facchini, M. C., M. Mircea, S. Fuzzi, and R. Charlson (1999). Cloud albedo enhancement by
surface-active organic solutes in growing droplets. Nature, 401, 257–259.
Falkovich, A. H., E. Ganor, Z. Levin, P. Formenti, and Y. Rudich (2001). Chemical and
mineralogical analysis of individual mineral dust particles, J. Geophys. Res., 106 (D16),
18,029–18,036.
Fan, J., S. Ghan, M. Ovchinnikov, X. Liu, P. J. Rasch, and A. Korolev (2011). Representa-
tion of Arctic mixed-phase clouds and the Wegener-Bergeron-Findeisen process in cli-
mate models: Perspectives from a cloud-resolving study. J. Geophys. Res., 116, D00T07,
doi:10.1029/2010JD015375.
Farkas, L. (1927). Keimbildungsgeschwindigkeit in übersättigten Dämpfen. Z. Phyik Chem.,
A125, 236–242.
736 References

Feingold, G., and P. Chuang (2002). Analysis of the influence of film-forming compounds on
droplet growth: Implications for cloud microphysical processes and climate. J. Atmos. Sci.,
59, 2006–2018.
Feingold, G., and Z. Levin (1986). The lognormal fit to raindrop spectra from frontal convective
clouds in Israel. J. Clim. Appl. Meteor., 25, 1346–1363.
Feingold, G., S. Tzivion, and Z. Levin (1988). Evolution of raindrop spectra. Part I: Solution to
the collection/breakup equation using the method of moments. J. Atmos. Sci., 45, 3387–3399.
Feingold G., B. Stevens, W. R. Cotton, and R. L. Walko (1994). An explicit cloud microphysics/
LES model designed to simulate the Twomey effect. Atmos. Res., 33, 207–233.
Feistel, R. (2012). TEOS-10: A new international oceanographic standard for seawater, ice, fluid
water and humid air. Intern. J. Thermophysics, 33, doi: 10.1007/s10765-010-0901-y.
Feistel, R. and E. Hagen (1995). On the Gibbs thermodynamic potential of seawater. Progr.
Oceanogr., 36, 249–327.
Feistel, R. and E. Hagen (1998). A Gibbs thermodynamic potential of sea ice. Cold Reg. Sci.
Technol., 28, 83–142.
Feistel, R. and E. Hagen (1999). Corrigendum to “A Gibbs thermodynamic potential of sea ice.”
Cold Reg. Sci. Technol., 29, 173–176.
Feistel, R., and W. Wagner (2005). High-pressure thermodynamic Gibbs functions of ice and sea
ice. J. Marine Res., 63, 95–139.
Feistel, R., and W. Wagner (2006). A new equation of state for H2O ice Ih. J. Phys. Chem. Ref.
Data, 35, 1021–1047, doi: 10.1063/1.2183 324.
Feistel, R., and W. Wagner (2007). Sublimation pressure and sublimation enthalpy of H2O ice
Ih between 0 and 273.16 K. Geochimica et Cosmochimica Acta, 71, 36–45, doi: 10.1016/j.
gca.2006.08.034.
Feistel, R., D. G. Wright, D. R. Jackett, K. Miyagawa, J. H. Reissmann, W. Wagner, U. Overhoff,
C. Guder, A. Feistel, and G. M. Marion (2010b). Numerical implementation and oceano-
graphic application of the thermodynamic potentials of liquid water, water vapour, ice, seawater
and humid air – Part 1: Background and equations. Ocean Sci., 6, 633–677.
Feistel, R., D. G. Wright, H.-J. Kretzschmar, E. Hagen, S. Herrmann, and R. Span (2010a).
Thermodynamic properties of sea air. Ocean Sci., 6, 91–141, www.ocean–sci.net/6/91/2010/.
Feistel, R., D. G. Wright, K. Miyagawa, A. H. Harvey, J. Hruby, D. R. Jackett, T. J. McDougall,
and W. Wagner (2008). Mutually consistent thermodynamic potentials for fluid water, ice and
seawater: A new standard for oceanography. Ocean Sci., 275–291.
Ferrier, B. S. (1994). A double-moment multiple-phase four-class bulk ice scheme. Part I: Descrip-
tion. J. Atmos. Sci., 51, 249–280.
Findeisen, W. (1938). Kolloid-Meteorologische Vorgänge bei Neiderschlags-bildung. Meteor. Z.,
55, 121–133.
FIRE-SHEBA (2001). First international regional experiment: Surface heat budget of the Arctic.
FIRE Arctic Clouds Experiment (FIRE), J. Geophys. Res., 106, Special section, Ed.: Curry, J. A.,
14,985–15,376.
Fitzgerald, J. W. (1975). Approximation formulas for the equilibrium size of an aerosol particle as
function of its dry size and composition and ambient relative humidity. J. Appl. Meteorol.,
14, 1044–1049.
Fitzgerald J. W., W. A. Hoppel, and M. A. Vietty (1982). The size and scattering coefficient of
urban aerosol particles at Washington D.C. as a function of relative humidity. J. Atmos. Sci.,
39, 1838–1852.
Fletcher, N. H. (1958). Size effects in heterogeneous nucleation. J. Chem. Phys., 29, 572–576.
Fletcher, N. H. (1962). The physics of rainclouds. Cambridge University Press, Cambridge, UK, 390 pp.
References 737

Fletcher, N. H. (1968). Ice nucleation behavior of silver iodide smokes containing a soluble
component. J. Atmos. Sci., 25, 1058–1060.
Fletcher, N. H. (1969). Active sites and ice nucleation, J. Atmos. Sci., 26, 1266–1271.
Fletcher, N. H. (1970a). The chemical physics of ice. Cambridge University Press, 265 pp.
Fletcher, N. H. (1970b). On contact nucleation. J. Atmos. Sci., 27, 1098–1099.
Fletcher, A. N. (1972). High-temperature contact nucleation of supercooled water by organic
aerosols. J. Appl. Meteorol., 11, 988–993.
Flossmann, A. I., and W. Wobrock (2010). A review of our understanding of the aerosol–cloud
interaction from the perspective of a bin resolved cloud scale modeling. Atmos. Res.,
97, 478–497.
Flossman, A. I., W. D. Hall, and H. P. Pruppacher (1985). A theoretical study of the wet
removal of atmospheric pollutants. Part I: The redistribution of aerosol particles captured
through nucleation and impaction scavenging by growing cloud droplets. J. Atmos. Sci.,
42, 583–606.
Flubacher, P., A. J. Leadbetter, and J. A. Morrison (1960). Heat capacity of ice at low tempera-
tures. J. Chem. Phys., 33, 1751–1755.
Ford, I. J. (1998a). How aircraft nucleate ice particles: A simple model. J. Aerosol Sci., 29, S1117,
doi:10.1016/S0021-8502(98)90741-8.
Ford, I. J. (1998b). Ice nucleation in jet aircraft exhaust plumes. In: Air pollution research report
68: Pollution from aircraft emissions in the North Atlantic flight corridor (POLINAT2). Ed.:
Schumann, U., Report EUR 18877, European Commission, 1998, 269–287.
Fornea, A. P., S. D. Brooks, J. B. Dooley, and A. Saha (2009). Heterogeneous freezing of ice
on atmospheric aerosols containing ash, soot, and soil. J. Geophys. Res., 114, D13201,
doi:10.1029/2009JD011958.
Fountoukis, C, and A. Nenes (2005). Continued development of a cloud droplet forma-
tion parameterization for global climate models. J. Geophys. Res., 110, D11212,
doi:10.1029/2004JD005591.
Fowler, L. D., D. A. Randall, and S. A. Rutledge (1996). Liquid and ice cloud microphysics in
the CSU general circulation model. Part I: Model description and simulated microphysical
processes. J. Climate, 9, 489–529.
Frenkel, Ya. I. (1946). Kinetic theory of liquids. Oxford University Press, 592 pp.
Fridlind, A., A. S. Ackerman, E. J. Jensen, A. J. Heymsfield, M. R. Poellot, et al. (2004).
Evidence for the predominance of midtropospheric aerosols as subtropical anvil cloud nuclei.
Science, 304, 718–722.
Fu, Q. (1996). An accurate parameterization of the solar radiative properties of cirrus clouds for
climate models. J. Climate, 9, 2058–2082.
Fu, Q., and K. N. Liou (1993). Parameterization of the radiative properties of cirrus clouds.
J. Atmos. Sci., 50, 2008–2025.
Fu, Q., P. Yang, and W. B. Sun (1998). An accurate parameterization of the infrared radiative
properties of cirrus clouds for climate models. J. Climate, 11, 2223–2237.
Fuchs, N. A. (1959). Evaporation and droplet growth in gaseous media, Pergamon, 242 pp.
Fuchs, N. A. (1964). The mechanics of aerosols. Pergamon, New York, 234 pp.
Fukuta, N. (1975). A study of the mechanism of contact ice nucleation. J. Atmos. Sci.,
32, 1597–1603.
Fukuta, N., and R. C. Schaller (1982). Ice nucleation by aerosol particles: Theory of condensa-
tion-freezing nucleation. J. Atmos. Sci., 39, 648–655.
Fukuta, N., and L. A. Walter (1970). Kinetics of hydrometeors growth from a vapor-spherical
model. J. Atmos. Sci., 27, 1160–1172.
738 References

Gaivoronsly, I. I., and Y. A. Seregin (1962). Experiments on cloud dispersal over large areas.
Proc. Centr. Aerolog. Obs., 44, 15–27 (in Russian).
Gao, R. S., P. J. Popp, D. W. Fahey, T. P. Marcy, et al. (2004). Evidence that nitric acid increases
relative humidity in low-temperature cirrus clouds. Science, 303, 516–520.
Gao, Y., S. B. Chen, and L. E. Yu (2006). Efflorescence relative humidity for ammonium sulfate
particles. J. Phys. Chem., 110, 7602–7608.
Gao, Y., S. B. Chen, and L. E. Yu (2007). Efflorescence relative humidity of airborne sodium
chloride particles: A theoretical investigation. Atmos. Environ., 41, 2019–2023, doi: 10.1016/j.
atmosenv.2006.12.014.
Gayet, J.-F., J. Ovarlez, V. Shcherbakov, J. Strom, U. Schumann, A. Minikin, F. Auriol,
A. Petzold, and M. Monier (2004). Cirrus cloud microphysical and optical properties at
southern and northern midlatitudes during the INCA experiment. J. Geophys. Res.,
109, D20206, doi:10.1029/2004JD004803.
Gerber, H. (1991). Supersaturation and droplet spectral evolution in fog. J. Atmos. Sci.
48, 2569–2588.
Gettelman, A., H. Morrison, and S. J. Ghan (2008). A new two-moment bulk stratiform cloud
microphysics scheme in the community atmosphere model, Version 3 (CAM3). Part II:
Single-Column and Global Results. J. Clim., 21, 3660–3679.
Ghan, S., C. Chuang, and J. Penner (1993). A parameterization of cloud droplet nucleation.
Part 1, Single aerosol species. Atmos. Res., 30, 197–222.
Ghan, S., C. Chuang, R. Easter, and J. Penner (1995). A parameterization of cloud droplet
nucleation. Part 2, Multiple aerosol types. Atmos. Res., 36, 39–54.
Ghan, S., L. Leung, R. Easter, and H. Abdul-Razzak (1997). Prediction of cloud droplet number
in a general circulation model. J. Geophys. Res., 102, 777–794.
Ghan, S. J., H. Abdul-Razzak, A. Nenes, Y. Ming, X. Liu, M. Ovchinnikov, B. Shipway,
N. Meskhidze, J. Xu, and X. Shi (2011). Droplet nucleation: Physically-based parameteriza-
tions and comparative evaluation. J. Adv. Model. Earth Syst., 3, M10001, doi:10.1029/
2011MS000074.
Giauque, W. F. and J. W. Stout (1936). The entropy of water and the third law of
thermodynamics. The heat capacity of ice from 15 to 273 K. J. Amer. Chem. Soc.,
58, 1144–1150.
Gierens, K. M. (2003). On the transition between heterogeneous and homogeneous freezing.
Atmos. Chem. Phys., 3, 437–446.
Gierens, K. M., M. Monier, and J.-F. Gayet (2003). The deposition coefficient and its role in cir-
rus clouds. J. Geophys. Res., 108 (D2), 4069, doi:10.1029/2001JD001558.
Girard, E., and J. A. Curry (2001). Simulation of Arctic low-level clouds observed during the
FIRE Arctic Clouds Experiment using a new bulk microphysics scheme. J. Geophys. Res.,
106, 15,139–15,154.
Girard, E., and J.-P. Blanchet (2001). Simulation of Arctic diamond dust, ice fog, and thin stratus
using an explicit aerosol-cloud model. J. Atmos. Sci., 58, 1199–1221.
Glasstone, S., K. J. Laidler, and H. Eyring (1941). The theory of rate processes. McGraw-Hill,
New York, 354 pp.
Golovin, A. M. (1963). On the kinetic equation for coagulating cloud droplets with allowance for
condensation. Izv. Acad. Sci. USSR, Ser. Geophys., 10, 949–953.
Goody, R. M. (1995). Principles of atmospheric physics and chemistry. Oxford University Press,
New York, 324 pp.
Grabowski, W. W. and H. Morrison (2008). Toward the mitigation of spurious cloud-edge super-
saturation in cloud models. Mon. Weather Rev., 136, 1224–1234.
Gradshteyn, I. S., and I. M. Ryzhik (1994). Tables of integrals, series, and products, 5th ed., Ed.:
Jeffery, A., Academic Press, 1204 pp.
References 739

Grassl, H. (1991). Possible climatic effects of contrails and additional water vapor. In: Air traffic
and the environment—Background, tendencies and potential global atmospheric effects. Ed.:
Schumann, U., Springer-Verlag, 124–137.
Gu, Y., and K. N. Liou (2000). Interactions of radiation, microphysics, and turbulence in the evo-
lution of cirrus clouds. J. Atmos. Sci., 57, 2463–2479.
Gultepe I., G. A. Isaac, A. Williams, D. Marcotte, and K. B. Strawbridge (2003). Turbulent heat
fluxes over leads and polynyas and their effect on Arctic clouds during FIRE-ACE: aircraft
observations for April 1998. Atmos. Ocean, 41, 15–34.
Gunn, R., and G. D. Kinzer (1949). The terminal velocity of fall for water droplets in stagnant air.
J. Meteorol., 6, 243–248.
Gunn, R., and J. S. Marshall (1958). The distribution with size of aggregates snowflakes.
J. Meteorol., 15, 452–461.
Gutzow, I., and J. W. P. Schmelzer (1995). The vitreous state. Thermodynamics, structure,
rheology, and crystallization. Springer-Verlag, Berlin, Heidelberg.
Gutzow, I. S., and J. W. P. Schmelzer (2011). Glasses and the third law of thermodynamics.
In Glasses and the glass tradition, edited by Schmelzer, J. W. P. and Gutzow, I. S.,
Wiley-VCH, Weinheim, p. 357–378.
Haag, W., B. Kärcher, J. Ström, A. Minikin, U. Lohmann, J. Ovarlez, and A. Stohl (2003).
Freezing thresholds and cirrus cloud formation mechanisms inferred from in situ measure-
ments of relative humidity. Atmos. Chem. Phys., 3, 1791–1806.
Haar, L., J. S. Gallagher, and G. S. Kell (1982). The anatomy of the thermodynamic surface of
water: The formulation and comparison with data. Proc. 8th Symp. Thermophys. Properties.
Ed.: J. V. Sengers. The Amer. Soc. Mechan. Engineers, vol. 2, New York, pp. 298–300.
Haar, L., J. S. Gallagher, and G. S. Kell (1984). NBS/NRC steam tables: Thermodynamic and
transport properties and computer programs for vapor and liquid states of water in SI units.
Hemisphere, Washington, and McGraw-Hill, New York, 271–276.
Hagen, D. E., R. J. Anderson, and J. L. Kassner, Jr. (1981). Homogeneous condensation-freezing
nucleation rate measurement for small water droplets in an expansion clouds chamber.
J. Atmos. Sci., 38, 1236–1243.
Hahn, C. J., and S. G. Warren (2007). A gridded climatology of clouds over land (1971–96) and
ocean (1954–97) from surface observations worldwide. Report, Numeric Data Product NDP-
026E, Carbon Dioxide Information Analysis Center, Oak Ridge National Laboratory, Oak
Ridge, Tennessee, doi: 10.3334/CDIAC/cli.ndp026,
Hahn, C. J., S. G. Warren, J. London, and R. L. Jenne (1988). Climatological data for clouds
over the globe from surface observations. NDP-026, Carbon Dioxide Information Analysis
Center (CDIAC), Oak Ridge National Laboratory, Oak Ridge, TN. [Also available from Data
Support Section, National Center for Atmospheric Research (NCAR), Boulder, CO.]
Hall, W. D. (1980). A detailed microphysical model within a two-dimensional dynamic framework:
Model description and preliminary results. J. Atmos. Sci., 37, 2486–2506.
Hall, W. D. and H. R. Pruppacher (1976). The survival of ice particles falling from cirrus clouds
in subsaturated air. J. Atmos. Sci., 33, 1995–2006.
Hallett, J., and Mossop, S. C. (1974). Production of secondary ice particles during the riming
process. Nature (London) 249, 26–28.
Hämeri, K., A. Laaksonen, M. Vakeva, and T. Suni (2001). Hygroscopic growth of ultrafine
sodium chloride particles. J. Geophys. Res., 106, 20,749–20,757.
Hämeri, K., M. Vakeva, H.-C. Hansson, and A. Laaksonen (2000). Hygroscopic growth of
ultrafine ammonium sulphate aerosol measured using an ultrafine tandem differential mobility
analyzer. J. Geophys. Res., 105, 22,231–22,242.
Han, Q., W. B. Rossow, J. Chou, and R. Welch (1998). Global variation of column droplet con-
centration in low-level clouds. Geophys. Res. Lett., 25, 1419–1422.
740 References

Hänel, G. (1976). The properties of atmospheric aerosol particles as functions of the relative
humidity at thermodynamic equilibrium with the surrounding moist air, Adv. Geophys.,
19, 73–188.
Hare, D. E., and C. M. Sörensen (1987). The density of supercooled water. II. Bulk samples
cooled to the homogeneous nucleation limit. J. Chem. Phys., 87, 4840–4850.
Harrington, J. Y., M. P. Meyers, R. L. Walko, and W. R. Cotton (1995). Parameterization of
ice crystal conversion process due to vapor deposition for mesoscale models using double-
moment basis functions. Part I: Basic formulation and parcel model results. J. Atmos. Sci.,
52, 4344–4366.
Hegg, D. A., and P. V. Hobbs (1992). Cloud condensation nuclei in the marine atmosphere:
A review. In: Nucleation and atmospheric aerosols. Eds.: Fukuta N., and Wagner, P. E.,
A. Deepack Publishing, 181–192.
Hegg, D. A., D. S. Covert, M. J. Rood, and P. V. Hobbs (1996). Measurements of aerosol optical
properties in marine air. J. Geophys. Res., 101(D8), 12,893–12,903.
Heide, H.-G. (1984). Observations of ice layers. Ultramicroscopy, 14, 271–278.
Hellmuth, O., V. I. Khvorostyanov, J. A. Curry, A. K. Shchekin, J. W. P. Schmelzer, and V. G.
Baidakov (2012). Review on the phenomenology and mechanism of atmospheric ice forma-
tion: Selected questions of interest. In: Nucleation theory and applications. Eds.: Schmelzer,
J. W. P., Röpke, G., and Priezzhev, V. B., Joint Institute for Nuclear Research, Bogoliubov
Lab. Theor. Phys., Dubna, ISBN 978-5-9530-0301-8.
Hellmuth, O., V. I. Khvorostyanov, J. A. Curry, A. K. Shchekin, J. W. P. Schmelzer, R. Feistel,
Y. S. Djikaev, and V. G. Baidakov (2013). Selected aspects of atmospheric ice and salt crys-
tallization. In: Nucleation theory and applications: Special issues. Review series on selected
topics of atmospheric sol formation, vol. 1. Eds.: Schmelzer, J. W. P., and Hellmuth, O., Joint
Inst. Nuclear Res., Bogoliubov Lab. Theor. Phys., Dubna, 548 pp.
Herman G. F., and J. A. Curry (1984). Observational and theoretical studies of solar radiation in
Arctic stratus clouds. J. Clim. Appl. Met., 23, 5–24.
Herman, G. F., and R. M. Goody (1976). Formation and persistence of summertime Arctic stratus
clouds. J. Atmos Sci., 33, 1537–1553.
Heymsfield, A. J. (1972). Ice crystals terminal velocities. J. Atmos. Sci., 29, 1348–1357.
Heymsfield, A. J. (2003). Properties of tropical and midlatitude ice cloud particle ensembles.
Part 1: Median mass diameters and terminal velocities. J. Atmos. Sci., 60, 2573–2591.
Heymsfield, A. J., and J. Iaquinta (2000). Cirrus crystals terminal velocities. J. Atmos. Sci.,
57, 916–938.
Heymsfield, A. J., and M. Kajikawa (1987). An improved approach to calculating terminal veloci-
ties of plate-like crystals and graupel. J. Atmos. Sci., 44, 1088–1099.
Heymsfield, A. J., and G. M. McFarquhar (2002). Mid-latitude and tropical cirrus. In:
Cirrus. Eds.: Lynch, D., Sassen, K., Starr, D. O’C., and Stephens, G., Oxford University Press,
78–101.
Heymsfield, A. J., and L. M. Miloshevich (1993). Homogeneous ice nucleation and supercooled
liquid water in orographic wave clouds, J. Atmos. Sci., 50, 2335–2353.
Heymsfield, A. J., and L. M. Miloshevich (1995). Relative humidity and temperature influences
on cirrus formation and evolution: Observations from wave clouds and FIRE-II. J. Atmos. Sci.,
52, 4302–4303.
Heymsfield, A. J., and C. M. R. Platt (1984). A parameterization of the particle size spectrum of
ice clouds in terms of the ambient temperature and the ice water content. J. Atmos. Sci.,
41, 846–855.
Heymsfield, A. J., and R. M. Sabin (1989). Cirrus crystal nucleation by homogeneous freezing of
solution droplets. J. Atmos. Sci., 46, 2252–2264.
References 741

Heymsfield, A. J., L. M. Miloshevich, C. Twohy, G. Sachse, and S. Oltmans (1998). Upper-

tropospheric relative humidity observations and implications for cirrus ice nucleation,
Geophys. Res. Lett., 25, 1343–1346, doi:10.1029/98GL01089.
Hicks, I., and G. Vali (1973). Ice nucleation in clouds by liquefied propane spray. J. Appl. Met.,
12, 1247–1258.
Hill, T. A., and T. W. Choularton (1985). An airborne study of the microphysical structure of
cumulus clouds. Q. J. Roy. Meteor. Soc., 111, 517–544.
Hobbs, P. V. (1969). Ice multiplication in clouds. J. Atmos. Sci., 26, 315–318.
Hobbs, P. V. (1974). Ice physics. Clarendon Press, Oxford, 837 pp.
Hobbs, P. V., and A. L. Rangno (1985). Ice particle concentrations in clouds. J. Atmos. Sci.,
42, 2523–2549.
Hobbs, P. V., and A. L. Rangno (1990). Rapid development of high ice particle concentrations in
small polar maritime cumuliform cloud. J. Atmos. Sci., 47, 2710–2722.
Hobbs, P. V., M. K. Politovich, D. A. Bowdle, and L. F. Radke (1978). Airborne studies
of atmospheric aerosol in the High Plains and the structure of natural and artificially
seeded clouds in eastern Montana. Rep. No. XIII, Dep. Atmos. Sci., Univ. of Washington,
125 pp.
Holten, V., C. E. Bertrand, M. A. Anisimov, and J. V. Sengers (2011). Thermodynamic model-
ing of supercooled water. Tech. Rep., Intern. Assoc. for the Properties of Water and Steam
(IAPWS) (September 2011), Inst. Phys. Sci. Technol., Dept. Chem. Biomolec. Eng., Univ.
Maryland, College Park, MD 20742, USA, 43 pp.
Holten, V., C. E. Bertrand, M. A. Anisimov, and J. V. Sengers (2012). Thermodynamics of
supercooled water, J. Chem. Phys., 136, 094507, http://dx.doi.org/10.1063/1.3690497.
Hoose, C., and O. Möhler (2012). Heterogeneous ice nucleation on atmospheric aerosols:
A review of results from laboratory experiments. Atmos. Chem. Phys., 12, 9817–9854.
Hoose, C., J. E. Kristjansson, J.-P. Chen, and A. Hazra (2010). A classical-theory-based param-
eterization of heterogeneous ice nucleation by mineral dust, soot and biological particles in a
global climate model. J. Atmos. Sci., 67, 2483–2503.
Houze, R. A., P. V. Hobbs, P. H. Herzegh, and D. B. Parsons (1979). Size distribution of precipi-
tating particles in frontal clouds. J. Atmos. Sci., 36, 156–162.
Howell, W. E. (1949). The growth of cloud drops in uniformly cooled air. J. Meteorol.,
54, 134–149.
Hu, Z., and R. C. Srivastava (1995). Evolution of raindrop size distribution by coalescence,
breakup, and evaporation: Theory and observations. J. Atmos. Sci., 52, 1761–1783.
Huang, J., and L. S. Bartell (1995). Kinetics of homogeneous nucleation in the freezing of large
water clusters. J. Phys. Chem., 99, 3924–3931.
Hudson, J. G. (1984). Cloud condensation nuclei measurements within clouds. J. Clim. Appl.
Meteorol., 23, 42–51.
Huffman, P. J. (1973). Supersaturation spectra of AgI and natural ice nuclei. J. Appl. Meteorol.,
12, 1080–1082.
Huffman, P. J., and G. Vali (1973). The effect of vapor depletion on ice nucleus measurements
with membrane filters. J. Appl. Meteorol., 12, 1018–1024.
Hung, H., A. Malinowski, and S. T. Martin (2002). Ice nucleation kinetics of aerosols containing
aqueous and solid ammonium sulfate particles. J. Phys. Chem. A, 106, 293–306.
Hung, H., A. Malinowski, and S. T. Martin (2003). Kinetics of heterogeneous ice nucleation on
the surfaces of mineral dust cores inserted into aqueous ammonium sulfate particles. J. Phys.
Chem. A, 107, 1296–1306.
Hussain, K., and C. P. R. Saunders (1984). Ice nucleus measurement with a continuous flow
chamber, Quart. J. Roy. Meteor. Soc., 110, 75–84.
742 References

Hyland, R. W., and A. Wexler (1983). Formulations for the thermodynamic properties of the satu-
rated phases of H2O from 173.15 K to 473.15 K. Trans. Amer. Soc. Heating, Refrigerating and
Air-Conditioning Engineers (ASHRAE), 89 (2A), Atlanta, GA, USA, 500–519.
IAPWS (2009a). Revised release on the equation of state 2006 for H2O Ice Ih. Tech. Rep., The
International Association for the Properties of Water and Steam, Doorwerth, The Netherlands,
September 2009, http://www.iapws.org/relguide/Ice-Rev2009.pdf.
IAPWS (2009b). Revised release on the IAPWS formulation 1995 for the thermodynamic proper-
ties of ordinary water substance for general and scientific use. Tech. Rep., The International
Association for the Properties of Water and Steam, Doorwerth, The Netherlands, September
2009, http://www.iapws.org/relguide/IAPWS-95.htm.
IAPWS (2011). Revised release on the pressure along the melting and sublimation curves of ordi-
nary water substance. Tech. Rep., The International Association for the Properties of Water and
Steam, Pilsen, Czech Republic, September 2011,http://www.iapws.org/relguide/MeltSub.htm.
IAPWS (2012). Guideline on a low-temperature extension of the IAPWS-95 formulation for water
vapor. Tech. Rep., The International Association for the Properties of Water and Steam,
Boulder, CO, USA, September/October 2012.
Ibragimov, K. Y. (1990). Numerical modeling of stratiform cloudiness in the atmospheres of the
giant planets. Izd. Nauka, Alma-Ata, Kazakhstan, 239 pp. (in Russian).
Intrieri, J. M., M. D. Shupe, T. Uttal, and B. J. McCarty (2002). Arctic cloud statistics from
radar and lidar at SHEBA. J. Geophys., Res., 107, 8030–8039.
IOC, SCOR, and IAPSO (2010). The international thermodynamic equation of seawater—2010:
Calculation and use of thermodynamic properties. T. J. McDougall, R. Feistel, D. G. Wright,
R. Pawlowicz, F. J. Millero, D. R. Jackett, B. A. King, G. M. Marion, S. Seitz, P. Spitzer,
C. T. A. Chen. Tech. Rep., Intergovernmental Oceanographic Commission, Manuals and
Guides No. 56, UNESCO, 196 pp., Paris 2010, http://www.teos-10.org.
IPCC (2007). Contribution of Working Group I to the Fourth Assessment Report of the Intergov-
ernmental Panel on Climate Change, 2007. Eds.: Solomon, S., Qin, D., Manning, M., Chen,
Z., Marquis, M., Averyt, K. B., Tignor, M., and Miller, H. L., Cambridge University Press,
Cambridge, UK, and New York.
Jaenicke, R. (1988). Aerosol physics and chemistry. In: Numerical data and functional relation-
ships in science and technology. Eds.: Fischer, G., Landolt-Börnstein New Series, vol. 4b,
Springer, New York, pp. 391–457.
Jayaweera, L. O. L. F., and R. E. Cottis (1969). Fall velocities of plate-like and column ice
crystals. Quart. J. Roy. Meteor. Soc., 95, 703–709.
Jeffery, C. A., and P. H. Austin (1997). Homogeneous nucleation of supercooled water: Results
from a new equation of state. J. Ceophys. Res., 102 (D21), 25,269–25,279.
Jeffery, C. A., and P. H. Austin (1999). A new analytic equation of state for liquid water. J. Chem.
Phys., 110 (1), 484–496.
Jeffery, C. A., J. M. Reisner, and M. Andrejczuk (2007). Another look at stochastic condensation
for subgrid cloud modeling: Adiabatic evolution and effects. J. Atmos. Sci., 64, 3953–3973.
Jeffreys, H. (1918). Some problems of evaporation. Phil. Mag., 35, 270–280.
Jensen, E. J., O. B. Toon, D. L. Westphal, S. Kinne, and A. J. Heymsfield (1994). Microphysical
modeling of cirrus, 1. Comparison with 1986 FIRE IFO measurements. J. Geophys. Res.,
99, 10,421–10,442.
Jensen, E. J., O. B. Toon, A. Tabazadeh, G. W. Sachsse, B. E. Anderson, et al. (1998). Ice nucle-
ation processes in upper tropospheric wave-clouds observed during SUCCESS. Geophys. Res.
Lett., 25 (9), 1363–1366.
Jensen, E. J., O. B. Toon, H. B. Selkirk, J. D. Spinhirne, and M. R. Schoeberl (1996). On the
formation and persistence of subvisual cirrus near the tropical tropopause. J. Geophys. Res.,
101, 21,361–21,375.
References 743

Jensen, E., L. Pfister, T. Bui, A. Weinheimer, E. Weinstock, J. Smith, J. Pittman,

D. Baumgardner, P. Lawson, and M. J. McGill (2005). Formation of a tropopause
cirrus layer observed over Florida during CRYSTAL-FACE. J. Geophys. Res., 110, D03208,
doi:10.1029/2004JD004671.
Jensen, E. J., O. B. Toon, S. A. Vay, J. Ovarlez, R. May, T. P. Bui, C. H. Twohey, B. W. Gandrud,
R. F. Pueschel, and U. Schumann (2001). Prevalence of ice-supersaturated regions in the
upper troposphere: implications for optically thin ice cloud formation. J. Geophys. Res.,
106, 17,253–17,266.
Ji, Q., and G. E. Shaw (1998). On supersaturation spectrum and size distribution of cloud conden-
sation nuclei, Geophys. Res. Lett., 25, 1903–1906.
Jiusto, J. E., and G. E. Bosworth (1971). Fall velocity of snowflakes. J. Appl. Meteorol.,
10, 1352–1354.
Jiusto, J. E., and G. G. Lala (1981). CCN-supersaturation spectra slopes (k). J. Rech. Atmos.,
15, 303–311.
Johari, G. P. (1998). An interpretation for the thermodynamic features of ice Ih ↔ ice XI transfor-
mations. J. Chem. Phys., 109 (21), 9543–9548.
Johari, G. P., G. Fleissner, A. Hallbrucker, and E. Mayer (1994). Thermodynamic continuity
between glassy and normal water. J. Phys. Chem., 98, 4719–4725.
Johnson, D. B. (1982). The role of giant and ultragiant aerosol particles in warm rain initiation.
J. Atmos. Sci., 39, 448–460.
Jonas, P. R. (1972). The collision efficiency of small drops. Quart. J. Roy. Meteor. Soc., 98, 681–683.
Joss, J., and E. G. Gori (1978). Shapes of raindrop size distributions. J. Appl. Meteorol, 17,
1054–1061.
Junge, C. E. (1952). Die Constitution der Atmospherischen Aerosols. Ann. Meteorol., 1, 128–135.
Junge, C. E. (1963). Air chemistry and radioactivity. Academic Press, New York and London,
424 pp.
Kabanov, A. S, I. P. Mazin, and V. I. Smirnov (1970). Effect of spatial inhomogeneity of nucleat-
ing droplets on their size spectrum in a cloud. Izv. Acad. Sci. USSR, Atmos. Oceanic Phys.,
6, 265–277.
Kachurin, L. G. (1978). Physical foundations of artificial modification of the atmospheric
processes. Leningrad, Hydrometeoizdat, 456 pp. (in Russian).
Kanno, H., and C. A. Angell (1977). Homogeneous nucleation and glass formation in aqueous
alkali halide solutions at high pressures. J. Phys. Chem., 81(26), 2639–2643.
Kärcher, B., and U. Lohmann (2002a). A parameterization of cirrus cloud formation:
Homogeneous freezing of supercooled aerosols. J. Geophys. Res., 107(D2), 4010,
doi:10.1029/2001JD000470.
Kärcher, B., and U. Lohmann (2002b). A parameterization of cirrus cloud formation:
Homogeneous freezing including effects or aerosol size. J. Geophys. Res., 107(D23), 4698,
doi:10.1029/2001JD001429.
Kärcher, B., and U. Lohmann (2003). A parameterization of cirrus cloud formation: Heterogeneous
freezing, J. Geophys. Res., 108, 4402, doi:10.1029/2002JD003220.
Kärcher, B., J. Hendricks, and U. Lohmann (2006). Physically based parameterization of cirrus
cloud formation for use in global atmospheric models. J. Geophys. Res., 111, D01205, doi:
01210.01029/02005JD006219.
Kärcher, B., T. Peter, U. M. Biermann, and U. Schumann (1996). The initial composition of jet
condensation trails. J. Atmos. Sci., 53, 3066–3083.
Kashchiev, D. (2000). Nucleation: Basic theory with applications. Batterworth-Heineman, Oxford,
512 pp.
Kashchiev, D., A. Borissova, R. B. Hammond, and K. J. Roberts (2010). Effect of cooling rate
on the critical undercooling for crystallization. J. Cryst. Growth, 312, 698–704.
744 References

Kasten, F. (1969). Visibility forecast in the phase of pre-condensation. Tellus, 21(5), 631–635.
Kell, G. S. (1975). Density, thermal expansivity, and compressibility of liquid water from
0° to 150°C: Correlations and tables for atmospheric pressure and saturation reviewed
and expressed on 1968 temperature scale. J. Chem. Eng. Data, 20, 97–112.
Ketcham, W. M., and P. V. Hobbs (1969). An experimental determination of the surface energies
of ice. Phil. Mag., 19, 1161.
Kessler, E. (1969). On the distribution and continuity of water substance in atmospheric circula-
tion. Meteor. Monogr., 10 (No. 32), Amer. Meteor. Soc., 84 pp.
Khain, A. P., A. Pokrovsky, M. Pinsky, A. Seifert, and V. Phillips (2004). Simulation of effects
of atmospheric aerosols on deep turbulent convective clouds using a spectral microphysics
mixed-phase cumulus cloud model. Part I: Model description and possible applications.
J. Atmos. Sci., 61, 2963–2982.
Khairoutdinov, M. F., and V. I. Khvorostyanov (1991). Modeling of artificial dispersal of
orographic cloudiness by seeding from aircraft. Atmos. Optics, 4 (10), 650–676.
Khairoutdinov, M. F., and Y. L. Kogan (2000). A new cloud physics parameterization in a
large-eddy simulation model of marine stratocumulus. Mon. Wea. Rev., 128, 229–243.
Khairoutdinov, M. F., and D. Randall (2003). Cloud resolving modeling of the ARM summer
1997 IOP: Model formulation, results, uncertainties, and sensitivities. J. Atmos. Sci., 60 (4),
607–625, doi:10.1175/1520-0469.
Khvorostyanov, V. I. (1982). A two-dimensional time-dependent microphysical model of
advective-radiative fog and low clouds. Sov. Meteorol. Hydrol., No. 7, 16–28.
Khvorostyanov, V. I. (1984). Modeling artificial crystallization and dispersal of supercooled fogs.
Sov. Meteorol. Hydrol., No. 3, 35–45.
Khvorostyanov, V. I. (1987). Three-dimensional microphysical model of cloud crystallization after
seeding with dry ice. Sov. Meteorol. Hydrol., No. 4, 29–37.
Khvorostyanov, V. I. (1995). Mesoscale processes of cloud formation, cloud-radiation interaction
and their modelling with explicit cloud microphysics. Atmos. Res. 39, 1–67.
Khvorostyanov, V. I., A. P. Khain, and E. A. Kogteva (1989). A two-dimensional time-dependent
microphysical model of the three-phase convective cloud and evaluation of seeding with a
crystallizing agent. Sov. Meteorol. Hydrol., No. 5, 33–45.
Khvorostyanov, V. I., and J. A. Curry (1999a). A simple analytical model of aerosol properties
with account for hygroscopic growth. Part I: Equilibrium size spectra and CCN activity
spectra. J. Geophys. Res., 104 (D2), 2163–2174.
Khvorostyanov, V. I., and J. A. Curry (1999b). A simple analytical model of aerosol properties
with account for hygroscopic growth. Part II: Scattering and absorption coefficients.
J. Geophys. Res., 104 (D2), 2175–2184.
Khvorostyanov, V. I., and J. A. Curry (1999c). Toward the theory of stochastic condensation in
clouds. Part I: A general kinetic equation. J. Atmos. Sci., 56, 3985–3996.
Khvorostyanov, V. I., and J. A. Curry (1999d). Toward the theory of stochastic condensation in
clouds. Part II. Analytical solutions of gamma distribution type. J. Atmos. Sci.,
56, 3997–4013.
Khvorostyanov, V. I, and J. A. Curry (2000). A new theory of heterogeneous nucleation for appli-
cation in cloud and climate models, Geophys. Res. Lett., 27, 4081–4084.
Khvorostyanov, V. I., and J. A. Curry (2002). Terminal velocities of droplets and crystals: Power
laws with continuous parameters over the size spectrum. J. Atmos. Sci., 59, 1872–1884.
Khvorostyanov, V. I., and J. A. Curry (2004a). Thermodynamic theory of freezing and melting of
water and aqueous solutions. J. Phys. Chem. A, 108 (50), 11,073–11,085.
Khvorostyanov, V. I., and J. A. Curry (2004b). The theory of ice nucleation by heterogeneous
freezing of deliquescent mixed CCN. Part 1: Critical radius, energy and nucleation rate.
J. Atmos. Sci., 61, 2676–2691.
References 745

Khvorostyanov, V. I., and J. A. Curry (2005a). The theory of ice nucleation by heterogeneous
freezing of deliquescent mixed CCN. Part 2: Parcel model simulation. J. Atmos. Sci.,
62, 261–285.
Khvorostyanov, V. I., and J. A. Curry (2005b). Fall velocities of hydrometeors in the atmosphere:
Refinements to a continuous analytical power law. J. Atmos. Sci., 62 (12), 4343–4357.
Khvorostyanov, V. I., and J. A. Curry (2006). Aerosol size spectra and CCN activity spectra:
Reconciling the lognormal, algebraic and power laws. J. Geophys. Res., 111, D12202,
doi:10.1029/2005JD006532.
Khvorostyanov, V. I., and Curry, J. A. (2007). Refinements to the Köhler’s theory of aerosol equi-
librium radii, size spectra, and droplet activation: Effects of humidity and insoluble fraction.
J. Geophys. Res., 112 (D5), D05206, http://dx.doi.org/10.1029/2006JD007672
Khvorostyanov, V. I., and J. A. Curry (2008a). Kinetics of cloud drop formation and its param-
eterization for cloud and climate models. J. Atmos. Sci., 65, 2784–2802.
Khvorostyanov, V. I., and J. A. Curry (2008b). Analytical solutions to the stochastic kinetic equa-
tion for liquid and ice particle size spectra. Part I: Small-size fraction. J. Atmos. Sci.,
65, 2025–2043.
Khvorostyanov, V. I., and J. A. Curry (2008c). Analytical solutions to the stochastic kinetic
equation for liquid and ice particle size spectra. Part II: Large-size fraction in precipitating
clouds. J. Atmos. Sci., 65, 2044–2063.
Khvorostyanov, V. I., and J. A. Curry (2009a). Parameterization of cloud drop activation based
on analytical asymptotic solutions to the supersaturation equation. J. Atmos. Sci.,
66, 1905–1925.
Khvorostyanov, V. I., and J. A. Curry (2009b). Critical humidities of homogeneous and heteroge-
neous ice nucleation: Inferences from extended classical nucleation theory. J. Geophys. Res.,
114, D04207, http://dx.doi.org/10.1029/2008JD011197.
Khvorostyanov, V. I., and J. A. Curry (2012). Parameterization of homogeneous ice nucleation for
cloud and climate models based on classical nucleation theory. Atmos. Chem. Phys.,
12, 9275–9302, 2012, www.atmos-chem-phys.net/12/9275/2012/, doi:10.5194/acp-12-9275-2012.
Khvorostyanov, V. I., J. A. Curry, J. O. Pinto, M. Shupe, B. Baker, and K. Sassen (2001).
Modeling with explicit spectral water and ice microphysics of a two-layer cloud system of
altostratus and cirrus observed during the FIRE Arctic Clouds Experiment. J. Geophys. Res.,
106, 15,099–15,112.
Khvorostyanov, V. I., J. A. Curry, I. Gultepe, and K. Strawbridge (2003). A springtime
cloud over the Beaufort Sea polynya: Three-dimensional simulation with explicit spec-
tral microphysics and comparison with observations. J. Geophys. Res., 108 (D9), 4296,
doi:10.1029/2001JD001489.
Khvorostyanov, V. I., H. Morrison, J. A. Curry, D. Baumgardner, and P. Lawson (2006).
High supersaturation and modes of ice nucleation in thin tropopause cirrus: Simulation of the
13 July 2002 Cirrus Regional Study of Tropical Anvils and Cirrus Layers case. J. Geophys.
Res., 111 (No. D2), D02201, http://dx.doi.org/10.1029/2004JD005235.
Khvorostyanov, V. I., and M. F. Khairoutdinov (1990). Modeling precipitation enhancement over
extended mountainous country by aircraft seeding of orographic cloudiness. Sov. Meteorol.
Hydrol., No. 11, 43–54.
Khvorostyanov, V. I., and K. Sassen (1998a). Cirrus cloud simulation using explicit microphysics
and radiation: Part I: Model description, J. Atmos. Sci., 55, 1808–1821.
Khvorostyanov, V. I., and K. Sassen (1998b). Cirrus cloud simulation using explicit microphys-
ics and radiation: Part II: Microphysics, vapor and ice mass budgets, and optical and radiative
properties. J. Atmos. Sci., 55, 1822–1845.
Khvorostyanov, V. I., and K. Sassen (1998c). Towards the theory of homogeneous nucleation and
its parameterization for cloud models. Geophys. Res. Lett., 25 (16), 3155–3158.
746 References

Khvorostyanov, V. I., and K. Sassen (2002). Microphysical processes in cirrus and their impact on
radiation: A mesoscale modeling perspective. In: Cirrus. Eds.: Lynch, D., Sassen, K., Starr,
D. O’C., and Stephens, G., Oxford University Press, 397–432.
Kimizuka, N., and T. Suzuki (2007). Supercooling behavior in aqueous solutions. J. Phys. Chem.
B, 111, 2268–2273.
Kiselev, S. B. (2001). Physical limit of stability in supercooled liquids. Int. J. Thermophys., 22 (5),
1421–1433.
Kiselev, S. B., and J. F. Ely (2002). Parametric crossover model and physical limit of stability in
supercooled water. J. Chem. Phys., 116 (13), 5657–5665.
Klein, S. A., R. B. McCoy, H. Morrison, A. S. Ackerman, et al. (2009). Intercomparison of
model simulations of mixed-phase clouds observed during the ARM Mixed-Phase Arctic
Cloud Experiment. I. Single-layer cloud. Q. J. Roy. Meteor. Soc., 135, 979–1002.
Klotz, I. M., and R. M. Rosenberg (1972). Chemical thermodynamics, basic theory and methods,
3rd ed. Benjamin/Cummings: Menlo Park, CA, USA.
Klug, D. D. (2002). Dense ice in detail, Nature, 420, 749–751.
Knight, C. A. (1971). Experiments on contact angle of water on ice. Philos. Mag. 23, 153–165.
Knight, N. C., and A. J. Heymsfield (1983). Measurement and interpretation of hailstone density
and terminal velocity. J. Atmos. Sci., 40, 1510–1516.
Knopf, D. A., and T. Koop (2006). Heterogeneous nucleation of ice on surrogates of mineral dust.
J. Geophys. Res., 111, D12201, doi:10.1029/2005JD006894.
Köhler, H. (1921). Zur Kondensation des Wasserdampfes in der Atmosphäre, Geophys. Publ.,
2, 3–15.
Köhler, H. (1936). The nucleus in and the growth of hygroscopic droplets, Trans. Farad. Soc.,
32, 1152–1161.
Kolmogorov, A. N. (1941). Local structure of turbulence in an incompressible viscous fluid at very
high Reynolds numbers. Dokl. Acad. Sci. USSR, 30, 301–305. Reprinted in Sov. Phys. Usp.,
10, 734–736, 1968, and Proc. Roy. Soc., London, A, 434, 9–13, 1991.
Kondratyev, K. Ya. (1969). Radiation in the atmosphere. Academic Press, New York, 912 pp.
Kondratyev, K. Ya., and V. I. Khvorostyanov (1989). Modeling of cloud formation due to air-sea
interaction over the oceanic hydrological front. Boundary Layer Meteorol., 46, 229–249.
Kondratyev, K. Ya., M. V. Ovtchinnikov, and V. I. Khvorostyanov (1990a). Mesoscale model of
mixed-phase cloud development with account for the interaction among optical, radiative and
microphysical processes. Atmos. Optics, 3 (6), 639–646.
Kondratyev, K. Ya., M. V. Ovtchinnikov, and V. I., Khvorostyanov (1990b). Modeling the evolu-
tion of the optical, radiative and microphysical properties of the atmosphere after crystallization
of cloudiness. Part I: Complete dispersal of the clouds. Atmos. Optics, 3 (No 6), 647–654.
Koop, T. (2004). Homogeneous ice nucleation in water and aqueous solutions. Z. Phys. Chem.,
218, 1231–1258.
Koop, T., and B. Zobrist (2009). Parameterizations for ice nucleation in biological and atmospheric
systems. Phys. Chem. Chem. Phys., 11, 10,839–10,850, doi:10.1039/b914289d.
Koop, T., A. K. Bertram, L. T. Molina, and M. J. Molina (1999). Phase transitions in aqueous
NH4HSO4 solutions. J. Phys. Chem. A., 103, 9042–9048.
Koop, T., B. P. Luo, A. Tsias, and T. Peter (2000). Water activity as the determinant for homoge-
neous ice nucleation in aqueous solutions. Nature, 406, 611–614.
Koop, T., H. P. Ng, L. T. Molina, and M. J. Molina (1998). A new optical technique to study
aerosol phase transitions: The nucleation of ice from H2SO4 aerosols. J. Phys. Chem. A,
102, 8924–8931.
Korhonen, P., A. Laaksonen, E. Batris, and Y. Viisanen (1998). Thermodynamics for highly
concentrated water-ammonium sulfate solutions. J. Aerosol Sci., 29 (Suppl. 1), S379–S380.
References 747

Korn, G. A., and T. M. Korn (1968). Mathematical handbook for scientists and engineers.
McGraw-Hill Co., New York, 831 pp.
Korolev, A. V., G. A. Isaac, S. G. Cober, J. W. Strapp, and J. Hallett (2003). Microphysical
characterization of mixed-phase clouds. Q. J. Roy. Meteor. Soc., 129, 39–65.
Kovetz, A., and B. Olund (1969). The effect of coalescence and condensation on rain formation in
a cloud of finite vertical extent. J. Atmos. Sci., 26, 1060–1065.
Kotchenruther, R. A., P. V. Hobbs, and D. A. Hegg (1999). Humidification factors for atmospheric
aerosols off the mid-Atlantic coast of the United States. J. Geophys. Res., 104, 2239–2251.
Krakovskaia, S. V., and A. M. Pirnach (2004). A theoretical study of the microphysical structure
of mixed stratiform frontal clouds and their precipitation. Atmos. Res., 47–48, 491–503.
Krämer, B., M. Schwell, O. Hubner, H, Vortisch, T. Leisner, E. Ruhl, H Baumgartel, and
L. Woste (1996). Homogeneous ice nucleation observed in single levitated micro droplets.
Ber. Bunsenges Phys. Chem., 100, 1911–1914.
Krämer, M., C. Schiller, A. Afchine, R. Bauer, I. Gensch, A. Mangold, S. Schlicht, N. Spelten,
N. Sitnikov, S. Borrmann, M. de Reus, and P. Spichtinger (2009). Ice supersaturations and
cirrus cloud crystal numbers. Atmos. Chem. Phys., 9, 3505–3522, doi:10.5194/acp-9-3505-2009.
Krasnovskaya, L. I. (1964). Physical basics of artificial cloud modification with cooling agents.
Proc. Centr. Aerolog. Obs., 58, 79 pp. (in Russian).
Krasnovskaya, L. I., Y. A. Seregin, and V. I. Khvorostyanov (1987). State-of-the-art in studies of
artificial seeding of supercooled clouds and fogs with cooling agents. In: Problems of cloud
physics, weather modification. Leningrad, Hydrometeoidat, 1987, 50–64 (in Russian).
Kreidenweis, S. M., K. Koehler, P. J. DeMott, A. P. Prenni, C. Carrico, and B. Ervens (2005).
Water activity and activation diameters from hygroscopicity data—Part I: Theory and applica-
tion to inorganic salts. Atmos. Chem. Physics, 5, 1357–1370.
Kulmala, M., A. Laaksonen, P. Korhonen, T. Vesala, T. Ahonen, and J. C. Barrett (1993). The
effect of atmospheric nitric acid vapor on cloud condensation nucleus activation. J. Geophys.
Res., 98, 22,949–22,958.
Kulmala, M., U. Rannik, E. Zapadinsky, and C. Clement (1997). The effect of saturation
fluctuations on droplet growth. J. Aerosol Sci., 28, 1395–1409.
Kumar, B., F. Janetzko, J. Schumacher, and R. A Shaw (2012). Extreme responses of a coupled
scalar–particle system during turbulent mixing. New Journal of Physics, 14, 115,020–115,041,
doi:10.1088/1367-2630/14/11/115020.
Kuo, J.-L., J. V. Coe, S. J. Singer, Y. B. Band, and L. Ojamäe (2001). On the use of graph
invariants for efficiently generating hydrogen bond topologies and predicting physical
properties of water clusters and ice. J. Chem. Phys., 114, 2527–2540.
Kuo, J.-L., M. L., Klein, S. J., Singer, and L. Ojamäe (2004). Ice Ih – Ice XI phase transition.
A quantum mechanical study. In: Abstracts of papers, 227th ACS National Meeting, Anaheim,
CA, USA, March 28–April 1, 2004, PHYS-463, Amer. Chem. Soc.
Laaksonen, A., V. Talanquer, and D. Oxtoby (1995). Nucleation: Measurements, theory and
atmospheric applications. Annu. Rev. Phys. Chem., 46, 489–524.
Laaksonen, A., P. Korhonen, M. Kulmala, and R. J. Charlson (1998). Modification of the
Köhler equation to include soluble trace gases and slightly soluble substances. J. Atmos. Sci.,
55, 853–862.
Ladino, L., O. Stetzer, F. Lüönd, A. Welti, and U. Lohmann (2011). Contact freezing
experiments of kaolinite particles with cloud droplets. J. Geophys. Res., 116, D22202,
doi:10.1029/2011JD015727.
Ladino Moreno, L. A., O. Stetzer, and U. Lohmann (2013). Contact freezing: A review of exper-
imental studies. Atmos. Chem. Phys., 13, 9745–9769, www.atmos-chem-phys
.net/13/9745/2013/, doi:10.5194/acp-13-9745-2013.
748 References

Laktionov, A. G. (1972). Fraction of soluble in water substances in the particles of atmospheric

aerosol. Izv. Acad. Sci. USSR, Atmos. Oceanic Phys., 8, 389–395.
Landau, L. D., and E. M. Lifshitz (1958a). Quantum mechanics. Non-relativistic theory. Course
of theoretical physics, v. 3. Addison-Wesley, 526 pp.
Landau, L. D., and E. M. Lifshitz (1958b). Statistical physics, Part I. Course of theoretical physics,
v. 5. Pergamon Press, 544 pp.
Landau, L. M., and E. M. Lifshitz (1959). Fluid mechanics. Course of theoretical physics,
v. 6. 1st ed., Pergamon Press, 536 pp.
Landau, L. D., and E. M. Lifshitz (1966). Electrodynamics of continuous media. Course of
theoretical physics, v. 8. Addison-Wesley, 417 pp.
Landau, L. D., and E. M. Lifshitz (2005). The classical theory of fields. Course of theoretical
physics, v. 2. Pergamon Press, 428 pp.
Langham, E. J., and B. J. Mason (1958). The heterogeneous and homogeneous nucleation in
supercooled water. Proc. Roy. Soc., A247, 493–504.
Larson, B. H., and B. D. Swanson (2006). Experimental investigation of the homogeneous
freezing of aqueous ammonium sulfate droplets. J. Phys. Chem. A, 110 (5), 1907–1916.
Latham, J., and R. L. Reed (1977). Laboratory studies of the effects of mixing on the evolution of
cloud droplet spectra. Quart. J. Roy. Meteor. Soc., 103, 297–306.
Lawson, R. P., R. E. Stewart, and L. J. Agnus (1998). Observations and numerical simulations of
the origin and development of very large snowflakes. J. Atmos., Sci., 55, 3209–3229.
Lawson, R. P., B. A. Baker, C. G. Schmitt, and T. L. Jensen (2001). An overview of microphysical
properties of Arctic clouds observed in May and July 1998 during FIRE ACE. J. Geophys. Res.,
106 (D14), 14,989–15,014.
Lawson, R. P., B. Baker, B. Pilson, and Q. Mo (2006). In situ observations of the microphysical
properties of wave, cirrus, and anvil clouds. Part II: Cirrus clouds. J. Atmos. Sci., 63,
3186–3203.
Leberman, R., and A. K. Soper (1995). Effect of high salt concentrations on water structure.
Nature, 378, 364–366.
Leck, K., E. D. Nilsson, E. K. Bigg, and L. Bäcklin (2001). Atmospheric program on the Arctic
Ocean Expedition 1996 (AOE-96): An overview of scientific goals, experimental approach,
and instruments. J. Geophys. Res., 106 (D23), 32,051–32,067.
Lemons, D. S. (2002). An introduction to stochastic processes in physics. The Johns Hopkins
University Press, 110 pp.
Levich, V. G. (1969). The course of theoretical physics, v. 1. Moscow, “Nauka,” 910 pp.
(in Russian).
Levin, L. M. (1954). On the size distributions functions of the cloud and rain droplets. Dokl. Acad.
Sci. USSR, 44, 1045–1049.
Levin, L. M., and Y. S. Sedunov (1966a). A theoretical model of condensation nuclei: The mechanism
of cloud formation in clouds. J. Rech. Atmos., 2 (2–3), 416–424.
Levin, L. M., and Y. S. Sedunov (1966b). Stochastic condensation of drops and kinetics of cloud
spectrum formation. J. Rech. Atmos., 2, 425–432.
Levin, Z., E. Ganor, and V. Gladstein (1996). The effects of desert particles coated with sulfate
on rain formation in the eastern Mediterranean. J. Appl. Meteorol., 35, 1511–1523.
Lewis, J. S. (1995). Physics and chemistry of the solar system. Academic Press, San Diego, CA,
USA, 556 pp.
Lewis, J. S., and R. E. Prinn (1984). Planets and their atmospheres: Origins and evolutions.
Academic Press, New York, 470 pp.
Li, Zh., A. L. Williams, and M. J. Rood (1998). Influence of soluble surfactant properties on the
activation of aerosol particles containing inorganic solute. J. Atmos. Sci., 55, 1859–1866.
References 749

Lifshitz, E. M., and L. P. Pitaevskii (1997). Physical kinetics. Course of theoretical physics by
Landau and Lifshitz, v. 10. Butterworth Heinemann, 452 pp.
Lifshitz, I. M., and V. V. Slezov (1958). On the theory of diffusional decay of supersaturated solid
solutions. J. Exper. Theor. Phys., 35, 479–492.
Lifshitz, I. M., and V. V. Slezov (1961). On the kinetics of precipitation of supersaturated solid
solutions. J. Phys. Chem. Solids, 19, 35–50.
Lilly, D. K. (1968). Models of cloud-topped mixed layers under a strong inversion. Quart. J. Roy.
Met. Soc., (4), 292–309.
Lin, R.-F., D. O’C. Starr, P. J. DeMott, R. Cotton, K. Sassen, E. Jensen, B. Kärcher, and
X. Liu (2002). Cirrus parcel model comparison project. Phase 1: The critical components to
simulate cirrus initiation explicitly. J. Atmos. Sci., 59, 2305–2329.
Lin, Y. L., R. D. Farley, and H. D. Orville (1983). Bulk parameterization of the snow field in a
cloud model. J. Climate Appl. Meteorol., 22, 1065–1092.
Liou, K. N. (1980). An introduction to atmospheric radiation. Academic Press, 384 pp.
Liou, K. N. (1992). Radiation and cloud processes in the atmosphere. Oxford University Press, 487 pp.
Liou, K. N., and S. C. Ou (1989). The role of cloud microphysical processes in climate: An
assessment from a one-dimensional perspective. J. Geophys. Res., 94D, 8599–8607.
Liou, K.-N., S. C. Ou, and G. Koenig (1991). An investigation of the climatic effect of contrail
cirrus. In: Air traffic and the environment—Background, tendencies, and potential global
atmospheric effects. Ed.: Schumann, U., Springer-Verlag, 154–169.
Litvinov, I. V. (1956). Determination of falling velocity of snow particles. Izv. Acad. Sci. USSR,
Ser. Geophys., 7, 853–856.
Liu, X., and J. E. Penner (2005). Ice nucleation parameterization for global models. Meteorol. Z.,
14, 499–514.
Liu, Y. (1993). Statistical theory of the Marshall-Palmer distribution of raindrops. Atmos. Environ.,
27A, 15–19.
Liu, Y. (1995). On the generalized theory of atmospheric particles systems. Adv. Atmos. Sci.,
12, 419–438.
Liu, Y., and J. Hallett (1998). On size distribution of cloud drops growing by condensation:
A new conceptual model. J. Atmos. Sci., 55, 527–536.
Liu, Y., and P. H. Daum (2004). Parameterization of the autoconversion Process. Part I: Analytical
formulation of the Kessler-type parameterizations. J. Atmos. Sci., 61, 1539–1548.
Liu, Y., Y. Laiguang, Y. Weinong, and L. Feng (1995). On the size distribution of cloud droplets.
Atmos. Res., 35, 201–216.
Locatelli, J. D., and P. V. Hobbs (1974). Fall speeds and masses of solid precipitation particles.
J. Geophys. Res., 79, 2185–2197.
Lohmann, U. (2002). Possible aerosol effects on ice clouds via contact nucleation. J. Atmos. Sci.,
59, 647–656.
Lohmann, U., and B. Kärcher (2002). First interactive simulations of cirrus clouds formed by homo-
geneous freezing in the ECHAM GCM, J. Geophys. Res., 107, doi:10.1029/2001JD000 767.
Lohmann, U., and J. Feichter (2005). Global indirect aerosol effects: A review. Atmos. Chem.
Phys., 5, 715–737, www.atmos-chem-phys.org/acp/5/715/.
Lohmann, U., J. Feichter, C. C. Chuang, and J. E. Penner (1999). Predicting the number of
cloud droplets in the ECHAM GCM. J. Geophys. Res., 104, 9169–9198.
Lohmann U., and K. Diehl (2006). Sensitivity studies of the importance of dust ice nuclei for the
indirect aerosol effect on stratiform mixed-phase clouds. J Atmos Sci., 63, 968–982.
London, J. (1957). A study of the atmospheric heat balance, Final report. Contract AF19(122)-165.
Dept. Meteorol. and Oceanogr., New York Univ. (ASTIA 117227, Air Force Geophysical
Laboratory, Hanscom AFB), 99 pp.
750 References

Long, A. (1974). Solutions to the droplet collection equation for polynomial kernels. J. Atmos. Sci.,
31, 1040–1052.
Low, R. D. H. (1969). A generalized equation for the solution effect in droplet growth. J. Atmos.
Sci., 26, 608–612.
Low, T. B., and R. List (1982a). Collision, coalescence, and breakup of raindrops. Part I: Experi-
mentally established coalescence efficiencies and fragment size distributions in breakup.
J. Atmos. Sci., 39, 1591–1606.
Low, T. B., and R. List (1982b). Collision, coalescence, and breakup of raindrops. Part II: Param-
eterization of fragment size distributions. J. Atmos. Sci., 39, 1607–1618.
Lübken, F.-J., J. Lautenbach, J. Höffner, M. Rapp, and M. Zecha (2009). First continuous tem-
perature measurements within polar mesosphere summer echoes. J. Atmos. Solar-Terr. Phys.,
71, 453–463, doi: 10.1016/j.jastp.2008.06.001.
Ludwig, F. L., and E. Robinson (1970). Observations of aerosols and droplets in California stra-
tus. Tellus, 22 (1), 78–89.
Lüönd, F., O. Stetzer, A. Welti, and U. Lohmann (2010). Experimental study on the ice nucle-
ation ability of size selected kaolinite particles in the immersion mode. J. Geophys. Res.,
115, D14201, doi:10.1029/2009JD012959.
Lushnikov, A. A. (1973). Evolution of coagulating systems. J. Coll. Interface Sci., 45 (3), 549–556.
Lushnikov, A. A. (1974). Evolution of coagulating systems. II. Asymptotic size distributions and
analytical properties of generating functions. J. Coll. Interface Sci., 48 (3), 400–409.
Lushnikov, A. A., and V. N. Piskunov (1982). Three new exactly solvable models in the theory of
coagulation. Dokl. Acad. Sci. USSR, 247, 132–136.
Lushnikov, A. A., and V. I. Smirnov (1975). Stationary coagulation and size distribution of
atmospheric aerosol particles. Izv. Acad. Sci. USSR, Atmos. Oceanic Phys., 11, 139–151.
MacKenzie, A. R., A. Laaksonen, E. Batris, and M. Kulmala (1998). The Turnbull correlation
and the freezing of stratospheric aerosol droplets. J. Geophys. Res. D, 103, 10875–10884.
Magono, C., and C. Lee (1966). Meteorological classification of natural snow crystals. J. Fac. Sci.
Hokkaido Univ., Ser. VII, 2, 321–335.
Magono, C., and T. Nakamura (1965). Aerodynamic studies of falling snowflakes. J. Meteor. Soc.
Japan, Ser. 2, 43, 139–147.
Malkin, T. L., B. J. Murray, A. V. Brukhno, J. Anwar, and C. G. Salzmann (2012). Structure of
ice crystallized from supercooled water. Proc. Nat. Acad. Sci., www.pnas.org/lookup/suppl/,
doi:10.1073/pnas.1113059109.
Manton, M. J. (1979). On the broadening of a droplet distribution by turbulence near cloud base.
Quart. J. Roy. Meteor. Soc., 105, 899–914.
Manton, M. J. (1981). Reply to the comments on the paper “On the broadening of a droplet distri-
bution by turbulence near cloud base.” Quart. J. Roy. Meteor. Soc., 112, 977–978.
Manton, M. J., and W. R. Cotton (1977). Formulation of approximate equations for modeling
moist deep convection on the mesoscale. Atmospheric Science Paper No. 266, Colorado State
University, 62 pp.
Marchuk, G. I., K. Ya. Kondratyev, V. V. Kozoderov, and V. I. Khvorostyanov (1986). Clouds
and climate. Leningrad, Hydrometeoizdat, 512 pp.
Marcolli, C., S. Gedamke, T. Peter, and B. Zobrist (2007). Efficiency of immersion mode ice
nucleation on surrogates of mineral dust. Atmos. Chem. Phys., 7, 5081–5091.
Marshall, J. S., and W. M. K. Palmer (1948). The distribution of raindrops with size. J. Meteor.,
5, 165–166.
Martin, S. T. (2000). Phase transitions of aqueous atmospheric particles. Chem. Rev., 100,
3403–3453.
Mason, B. J. (1971). The physics of clouds. Oxford Univ. Press, Clarendon, London, 481 pp.
References 751

Mason, P. J. (1985). A numerical study of cloud streets in the planetary boundary layer. Boundary
Layer Meteorol., 32, 281–304.
Mason, P. J. (1989). Large-eddy simulation of the convective atmospheric boundary layer. J. Atmos.
Sci., 46, 1492–1516.
Matrosov, S. Y. (1997). Variability of microphysical parameters in high-altitude ice clouds: Results
of the remote sensing method. J. Appl. Met., 36 (6), 633–648.
Matrosov, S. Y., and A. J. Heymsfield (2000). Use of Doppler radar to assess ice cloud particle
fall velocity-size relations for remote sensing and climate studies. J. Geophys. Res.,
105, 22,427–22,436.
Matson, R. J., and A. W. Huggins (1980). The direct measurement of the sizes, shapes and kinematics
of falling hailstones. J. Atmos., Sci., 37, 797–816.
Matveev, L. T. (1984). Cloud dynamics. D. Reidel Publish Co., 212 pp.
Maxwell, J. C. (1890). Theory of the wet bulb thermometer. In: The scientific papers of James
Clerk Maxwell, vol. 2. Dover Publisher, New York, 636–640 pp.
Mayer, E., and A. Hallbrucker (1987). Cubic ice from liquid water. Nature, 325, 601–602.
Mazin, I. P., and V. I. Smirnov (1969). To the theory of formation of the size spectrum of cloud
droplets at stochastic condensation. Proc. Centr. Aerolog. Observ., 89, 92–94.
McFarquhar, G. M. (2004). A new representation of collision-induced breakup of raindrops and
its implications for the shapes of raindrop size distributions. J. Atmos. Sci., 61, 777–794.
McFarquhar, G., G. Zhang, M. R. Poellot, G. L. Kok, R. McCoy, T. Tooman, A. M. Fridlind,
and A. J. Heymsfield (2007). Ice properties of single-layer stratocumulus clouds during the
Mixed-Phase Arctic Cloud Experiment: 1. Observations, J. Geophys. Res., 112, D24202,
doi:10.1029/2007JD008633.
McFiggans, G., P. Artaxo, U. Baltensperger, H. Coe, M. C. Facchini, G. Feingold, S. Fuzzi,
M. Gysel, A. Laaksonen, U. Lohmann, T. F. Mentel, D. M. Murphy, C. D. O’Dowd,
J. R. Snider, and E. Weingartner (2006). The effect of physical and chemical aerosol
properties on warm cloud droplet activation. Atmos. Chem. Phys., 6, 2593–2649, www.atmos-
chem-phys.net/6/2593/2006/.
McGraw, R., and E. Lewis (2009). Deliquescence and efflorescence of small particles. J. Chem.
Phys., 131, 194705(1)–194705(14), doi:10.1063/1.3251056.
McGraw, R., and Y. Liu (2006). Brownian drift-diffusion model for evolution of droplet size dis-
tributions in turbulent clouds. Geophys. Res. Lett., 33, L03802, doi: 10.1029/2005GL023545.
Menut, L., B. Bessagnet, D. Khvorostyanov, M. Beekmann, A. Colette, I. Coll, G. Curci,
G. Foret, A. Hodzic, S. Mailler, F. Meleux, J.-L. Monge, I. Pison, S. Turquety, M. Valari,
R. Vautard, and M. G. Vivanco (2013). Regional atmospheric composition modeling with
CHIMERE. Geosci. Model Dev. Discuss., 6, 203–329. www.geosci-model-dev-discuss
.net/6/203/2013/, doi:10.5194/gmdd-6-203-2013.
Merkulovich, V. M., and A. S. Stepanov (1977). Hygroscopicity effects and surface tension forces
during condensational growth of cloud droplets in the presence of turbulence. Izv. Akad. Sci.
USSR, Atmos. Oceanic Phys., 13, 163–171.
Merkulovich, V. M., and A. S. Stepanov (1981). Comments on the paper “On the broadening
of a droplet distribution by turbulence near cloud base” by M. J. Manton (Q. J., 1979, 105,
899–914). Quart. J. Roy. Meteor. Soc., 112, 976–977.
Meyers, M. P., P. J. DeMott, and W. R. Cotton (1992). New primary ice-nucleation parameteriza-
tions in an explicit cloud model. J. Appl. Meteor., 31, 708–721.
Meyers, M. P., R. L. Walko, J. Y. Harrington, and W. R. Cotton (1997). New RAMS cloud
microphysics parameterization. Part II: The two-moment scheme. Atmos. Res., 45, 3–39.
Milbrandt, J. A., and M. K. Yau (2005a). A multimoment microphysics parameterization. Part I:
Analysis of the role of the spectral shape parameter. J. Atmos. Sci. 62, 3051–3064.
752 References

Milbrandt, J. A., and M. K. Yau (2005b). A multimoment bulk microphysics parameterization.

Part II: A proposed three-moment closure and scheme description. J. Atmos. Sci.
62, 3065–3081.
Millero, F. J. (1978). Freezing point of seawater. In: Eighth Report of the Joint Panel on Oceano-
graphic Tables and Standards. UNESCO Tech. Pap. Mar. Sci., No. 28, Annex 6, UNESCO,
Paris.
Millero, F. J., R. Feistel, D. G. Wright, and T. J. McDougall (2008). The composition of standard
seawater and the definition of the reference-composition salinity scale. Deep Sea Res. 55 (1),
50–72.
Ming, Y., V. Ramaswamy, L. J. Donner, and V. T. J. Phillips (2006). A new parameterization
of cloud droplet activation applicable to general circulation models. J. Atmos. Sci.,
63, 1348–1356.
Mishchenko, M. I. (1991). Light-scattering by randomly oriented axially symmetrical particles.
J. Optical Soc. Amer. A—Optics Image Sci. Vision, 8, 871–882.
Mishchenko, M. I., L. D. Travis, and D. W. Mackowski (1996). T-matrix computations of light
scattering by nonspherical particles: A review. J. Quant. Spectrosc. Radiat. Transfer,
55, 535–575.
Mishima, O. (1996). Relationship between melting and amorphization of ice. Nature,
384, 546–549.
Mishima, O., and H. E. Stanley (1998). The relationship between liquid, supercooled and glassy
water. Nature, 396, 329–335.
Mishima, O., L. D. Calvert, and E. Whalley (1984). Melting ice I at 77 K and 10 kbar: A new
method of making amorphous solids. Nature, 310, 393–395.
Mishima, O., L. D. Calvert, and E. Whalley (1985). An apparently first-order transition between
two amorphous phases of ice induced by pressure. Nature, 314, 76–78.
Mitchell, D. L. (1994). A model predicting the evolution of ice particle size spectra and radiative
properties of cirrus clouds. Part I: Microphysics. J. Atmos. Sci., 51, 797–816.
Mitchell, D. L. (1996). Use of mass- and area-dimensional power laws for determining precipita-
tion particle terminal velocities. J. Atmos. Sci., 53, 1710–1723.
Mitchell, D. L., and W. P. Arnott (1994). A model predicting the evolution of ice particle size
spectra and radiative properties of cirrus clouds. Part II: Dependence of absorption and
extintion on ice crystal morphology. J. Atmos. Sci., 51, 817–832.
Mitchell, D. L., and A. J. Heymsfield (2005). Refinements in the treatment of ice particle terminal
velocities: Highlighting aggregates. J. Atmos. Sci., 62, 1637–1644.
Mitchell, D. L., A. J. Baran, W. P. Arnott, and C. Schmitt (2006). Testing and comparing the
modified anomalous diffraction approximation. J. Atmos. Sci., 63, 2948–2962.
Mitchell, D. L., S. K. Chai, Y. Liu, A. J. Heymsfield, and Y. Dong (1996). Modeling cirrus clouds.
Part I: Treatment of bimodal spectra and case study analysis. J. Atmos. Sci., 53, 2952–2966.
Miyata, K., H. Kanno, K. Tomizawa, and Y. Yoshimura (2001). Supercooling of aqueous solu-
tions of alkali chlorides and acetates. Bull. Chem. Soc. Jpn., 74, 1629–1633.
Miyata, K., H. Kanno, Y. Niino, and K. Tomozawa (2002). Cationic and anionic effects on the
homogeneous nucleation of ice in aqueous halide solutions. Chem. Phys. Lett., 354, 51–55.
Moeng, C. H., and A. Arakawa (1980). A numerical study of a marine subtropical stratus cloud
layer and its stability. J. Atmos. Sci., 37, 2661–2676.
Möhler, O., P. R. Field, P. Connolly, S. Benz, H. Saathoff, M. Schnaiter, R. Wagner, R. Cotton,
M. Krämer, A. Mangold, and A. J. Heymsfield, (2006). Efficiency of the deposition mode
ice nucleation on mineral dust particles. Atmos. Chem. Phys., 6, 3007–3021.
Mokhov, I. I., P. F. Demchenko, A. V. Eliseev, V. Ch. Khon, and D. V. Khvorostyanov (2002).
Estimations of global and regional climate changes during the 19th–21st centuries on the basis
References 753

of the IAP RAS Model with consideration for anthropogenic forcing. Izvestia Rus. Acad. Sci.,
Atmos. Oceanic Phys., 38 (5), 629–642.
Monier, M., W. Wobrock, J.-F. Gayet, and A. Flossmann (2006). Development of a detailed
microphysics cirrus model tracking aerosol particle’s histories for interpretation of the recent
INCA campaign. J. Atmos. Sci., 63, 504–525.
Monin, A. S., and A. M. Yaglom (2007a). Statistical fluid mechanics. Mechanics of turbulence,
v. 1. Ed.: Lumley, J. L. Dover Publications Inc., Mineola, NY, USA, 769 pp.
Monin, A. S., and A. M. Yaglom (2007b). Statistical fluid mechanics. Mechanics of turbulence,
v. 2. Ed.: Lumley, J. L. Dover Publications Inc., Mineola, NY, USA, 874 pp.
Mordy, W. A. (1959). Computations of the growth by condensation of a population of cloud
droplets. Tellus, 11, 16–44.
Morrison, H., and A. Gettelman (2008). A new two-moment bulk stratiform cloud microphys-
ics scheme in the community atmosphere model, version 3(CAM3). Part I: Description and
numerical tests. J. Clim., 21, 3642–3659, doi:10.1175/2008JCLI2105.1.
Morrison, H., J. A. Curry, and V. I. Khvorostyanov (2005a). A new double-moment microphys-
ics parameterization for application in cloud and climate models, Part 1: Description.
J. Atmos. Sci., 62, 1665–1677.
Morrison, H., J. A. Curry, M. D. Shupe, and P. Zuidema (2005b). A new double-moment
microphysics scheme for application in cloud and climate models, Part 2: Single-column
modeling of arctic clouds. J. Atmos. Sci., 62, 1678–1693.
Morrison, H., and J. Pinto (2005). Mesoscale modeling of springtime Arctic mixed-phase stratiform
clouds using a new two-moment bulk microphysics scheme. J. Atmos. Sci., 62, 3683–3704.
Morrison, H., R. B. McCoy, S. A. Klein, et al. (2009). Intercomparison of model simulations of
mixed-phase clouds observed during the ARM Mixed-Phase Arctic Cloud Experiment. II.
Multilayer cloud. Quart. J. Roy. Meteor. Soc., 135, 1003–1019.
Morse, B., and M. Richard (2009). A field study of suspended frazil ice particles. Cold Regions
Sci. Technol., 55, 86–102.
Mossop, S. C. (1955). The freezing of supercooled water. Proc. Phys. Soc., 68, 193–208.
Mossop, S. C., and J. Hallett (1974). Ice crystal concentration in cumulus clouds: Influence of the
drop spectrum. Science, 186, 632–633.
Moynihan, C. T. (1997). Two species / nonideal solution model for amorphous / amorphous phase
transitions. Mater. Res. Soc., Symp. Proc., 455, 411–425.
Müller, H. (1928). Zur allgemeinen theory der raschen Koagulation. Kolloid-Chem. Beib., Bd.
27, 223–250.
Murphy, D. M. (2003). Dehydration in cold clouds is enhanced by a transition from cubic to
hexagonal ice. Geophys. Res. Lett., 30 (23), 2230, doi:10.1029/2003GL018566.
Murphy, D. M., and T. Koop (2005). Review of the vapor pressures of ice and supercooled water
for atmospheric applications. Quart. J. Roy. Meteorol. Soc., 131, 1539–1565.
Murray, B. J., and A. K. Bertram (2006). Formation and stability of cubic ice in water droplets,
Phys. Chem. Chem. Phys, 8, 186–192.
Murray B. J., and E. J. Jensen (2010). Homogeneous nucleation of amorphous solid water
particles in the upper mesosphere. J. Atmos. Solar-Terrestrial Phys., 72, 51–61.
Murray, B. J., D. A., Knopf, and A. K. Bertram (2005). The formation of cubic ice under condi-
tions relevant to Earth’s atmosphere. Nature, 434, 202–205.
Murray, B. J., S. L. Broadley, T. W. Wilson, S. J. Bull, R. H. Wills, H. K. Christenson, and
E. J. Murray (2010). Kinetics of the homogeneous freezing of water. Phys. Chem. Chem.
Phys., 12 (35), 10,380–10,387.
Myhre, C. E. L., C. J. Nielsen, and O. W. Saastad (1998). Density and surface tension of aqueous
H2SO4 at low temperature. J. Chem. Eng. Data, 43, 617–622.
754 References

Nagle, J. F. (1966). Lattice statistics of hydrogen-bonded crystals. I. The residual entropy of ice.
J. Math. Phys., 7, 1484–1491.
Neiburger, M., and C. W. Chien (1960). Computations of the growth of cloud drops by condensa-
tion using an electronic digital computer. Geophys. Monogr., No. 5, Amer. Geophys. Union,
191–208.
Nenes, A., and J. H. Seinfeld (2003). Parameterization of cloud droplet formation in global climate
models. J. Geophys. Res., 108, 4415, doi:10.1029/2002JD002911.
Nenes, A., R. J. Charlson, M. C. Facchini, M. Kulmala, A. Laaksonen, and J. H. Seinfeld
(2002). Can chemical effects on cloud droplet number rival the first indirect effect? Geophys.
Res. Lett., 29, 1848, doi:10.1029/2002GL015295.
Nevzorov, A. N. (1967). Distribution of large drops in liquid stratiform clouds. Proc. Centr. Aerolog.
Observ., 79, 57–69.
Newkirk, J. B., and D. Turnbull (1955). Nucleation of ammonium sulfate crystals from aqueous
solutions. J. Appl. Phys., 26, 579–583.
Niemand, M., O. Möhler, B. Vogel, H. Vogel, C. Hoose, P. Connolly, H. Klein, H. Bingemer,
J. Skrotzki, and T. Leisner (2012). A particle-surface-area-based parameterization of immer-
sion freezing on mineral dust particles. J. Atmos. Sci., doi:10.1175/JAS-D-11-0249.1.
Noonkester, V. R. (1984). Droplet spectra observed in marine stratus cloud layers. J. Atmos. Sci.,
41, 829–845.
Oatis, S., D. Imre, R. McGraw, and J. Xu (1998). Heterogeneous nucleation of a common
atmospheric aerosol: Ammonium sulfate. Geophys. Res. Lett., 25, 4469–4472.
Obukhov, A. M. (1959). Description of turbulence in terms of Lagrangian variables. Adv.
Geophys., 6, 113–116.
Ohtake, T., and P. T. Huffman (1969). Visual range in ice fog. J. Appl. Meteorol., 8, 499–505.
Ohtake, T., K. O. L. F. Jayaweera, and K.-I. Sakurai (1982). Observation of ice crystal forma-
tion in lower Arctic atmosphere. J. Atmos. Sci., 39, 2898–2904.
Okita, T. (1961). Size distribution of large droplets in precipitating clouds. Tellus, 13, 456–467.
Onasch, T. B., R. McGraw, and D. Imre (2000). Temperature-dependent heterogeneous
efflorescence of mixed ammonium sulfate / calcium carbonate particles. J. Phys. Chem. A,
104, 10,797–10,806.
Onasch, T. B., R. L. Siefert, S. D. Brooks, A. J. Prenni, B. Murray, M. A. Wilson, and
M. A. Tolbert (1999). Infrared spectroscopic study of the deliquescence and efflorescence of
ammonium sulfate aerosol as a function of temperature. J. Geophys. Res., 104, 21,317–21,326.
Orville, H. D., and J.-M. Chen (1982). Effects of cloud seeding. Latent heat of fusion and conden-
sate loading on cloud dynamics and precipitation evolution: A numerical study. J. Atmos. Sci.,
39, 2807–2827.
Ovarlez, J., J.-F. Gayet, K. Gierens, J. Strom, H. Ovarlez, F. Auriol, R. Busen, and
U. Schumann (2002). Water vapour measurements inside cirrus clouds in northern and
southern hemispheres during INCA. Geophys. Res. Lett., 29, 1813, 10.1029/2001GL014440.
Ovtchinnikov, M. V., and Y. L. Kogan (2000). An investigation of ice production mechanisms in
small cumuliform clouds using a 3D model with explicit microphysics. Part I: Model descrip-
tion. J. Atmos. Sci., 57, 2989–3003.
Ovtchinnikov, M. V., Y. L. Kogan, and A. M. Blyth (2000). An investigation of ice production
mechanisms in small cumuliform clouds using a 3D model with explicit microphysics. Part II:
Case study of New Mexico cumulus clouds. J. Atmos. Sci., 57, 3004–3020.
Oxtoby, D. W. (2003). Crystal nucleation in simple and complex fluids. Phil. Trans. Roy. Soc.
London, A, 361, 419–428, doi: 10.1098/rsta.2002.1145.
Paltridge, G. W., and C. M. R. Platt (1976). Radiative processes in meteorology and climatology.
Elsevier, 318 pp.
References 755

Paluch, I. R., and C. A. Knight (1986). Does mixing promote droplet growth? J. Atmos. Sci.,
43, 1994–1998.
Paoli, R., and K. Shariff (2004). Direct numerical simulation of turbulent condensation in clouds.
Annual Res. Briefs, Center for Turbul. Res., NASA Ames Res. Center, 305–316.
Paoli, R., and K. Shariff (2009). Turbulent condensation of droplets: Direct simulation and a
stochastic model. J. Atmos. Sci., 66, 723–740.
Passarelli, R. E. (1978a). An approximate analytical model of the vapor deposition and aggregation
growth of snowflakes. J. Atmos. Sci., 35, 118–124.
Passarelli, R. E. (1978b). Theoretical and observational study of snow-sized spectra and snowflake
aggregation efficiencies. J. Atmos. Sci., 35, 882–889.
Pauling, L. (1935). The structure and entropy of ice and of other crystals with some randomness
of atomic arrangement. J. Amer. Chem. Soc., 57, 2680–2684.
Pawlowicz, R., T. McDougall, R. Feistel, and R. Tailleux (2012). Preface. An historical perspec-
tive on the development of the Thermodynamic Equation of Seawater – 2010. Ocean Sci.,
8, 161–174, www.ocean–sci.net/8/161/2012/.
Penner, J. E., D. J. Bergmann, J. J. Walton, D. Kinnison, M. J. Prather, D. Rotman, C. Price,
K. E. Pickering, and S. L. Baughcum (1998). An evaluation of upper troposphere NOx with
two models. J. Geophys. Res., 103 (D17), 22,097–22,113, doi:10.1029/98JD01565.
Petch, J. C., G. C. Craig, and K. P. Shine (1997). A comparison of two bulk microphysical
schemes and their effects on radiative transfer using a single-column model. Quart. J. Roy.
Meteor. Soc., 123, 1561–1580.
Petrenko, V. F., and R. W. Whitworth (1999). Physics of ice. Oxford University Press, 373 pp.
Pinto, J. O., J. A. Curry, and J. M. Intriery (2001). Cloud-aerosol interactions during autumn
over Beaufort sea. J. Geophys. Res., 106 (D14), 15,077–15,097.
Pirnach, A. M., and S. V. Krakovskaya (1994). Numerical studies of dynamics and cloud micro-
physics of the frontal rainbands. Atmos. Res., 33, 333–365.
Pirnach, A. M., and S. V. Krakovskaya (1998). Theoretical study of the microphysical structure
of mixed stratiform frontal clouds and their precipitation. Atmos. Res., 47–48, 491–503.
Platt, C. M. R. (1997). A parameterization of the visible extinction coefficient in terms of the ice/
water content. J. Atmos. Sci., 54, 2083–2098.
Poellot, M. R., K. A. Hilburn, W. P. Arnott, and K. Sassen (1999). In situ observation of cirrus
clouds from the 1994 ARM RCS IOP. Ninth ARM Science Team Meeting Proceedings,
San Antonio, Texas, March 22–26, 1999. Sponsored by the U.S. Department of Energy.
Ponyatovsky, E. G., V. V. Senitsyn, and T. A. Pozdnyakova (1994). Second critical point and low-
temperature anomalies in the physical properties of water. J.P.T. Lett., 60, 360–364.
Ponyatovsky, E. G., V. V. Senitsyn, and T. A. Pozdnyakova (1998). The metastable T-P phase
diagram and anomalous thermodynamic properties of supercooled water. J. Chem. Phys.,
109 (6), 2413–2422.
Poole, P. H., F. Sciortino, U. Essmann, and H. E. Stanley (1992). Phase behavior of metastable
water. Nature, 360, 324–328.
Poole, P. H., F. Sciortino, T. Grande, H. E. Stanley, and C. A. Angell (1994). Effect of
hydrogen bonds on the thermodynamic behavior of liquid water. Phys. Rev. Lett., 73 (12),
1632–1635.
Popovicheva, O. B., N. M. Persiantseva, E. E. Lukhovitskaya, N. K. Shonija, N. A. Zubareva,
B. Demirdjian, D. Ferry, and J. Suzanne (2004). Aircraft engine soot as contrail nuclei.
Geophys. Res. Lett., 31, L11104, doi: 10.1029/2003/GL018888.
Prenni, A. J., J. Y. Harrington, M. Tjernström, P. J. DeMott, A. Avramov, C. N. Long,
S. M. Kreidenweis, P. Q. Olsson, and J. Verlinde (2007). Can ice-nucleating aerosols affect
Arctic seasonal climate? Bull. Am. Meteorol. Soc. 88, 541–550.
756 References

Pruppacher, H. R., and J. D. Klett (1997). Microphysics of clouds and precipitation, 2nd ed.
Kluwer Academic Publishers: Boston, MA, USA, 954 pp.
Quante, M., and D. O’C. Starr (2002). Dynamical processes in cirrus clouds. In: Cirrus. Eds.: Lynch,
D., Sassen, K., Starr, D. O’C., and Stephens, G., Oxford University Press, pp. 346–374.
Raddatz, R. L., M. G. Asplin, L. Candlish, and D. G. Barber (2011). General characteristics of
the atmospheric boundary layer in a flaw lead polynya region for winter and spring. Boundary
Layer Meteorol., 138, 321–335. doi:10.1007/s10546-010-9557-1
Raddatz, R. L., R. J. Galley, and D. G. Barber (2012). Linking the atmospheric boundary layer
to the Amundsen Gulf sea-ice cover: A mesoscale to synoptic-scale perspective from winter to
summer 2008. Boundary Layer Meteorol., 142, 123–148. doi:10.1007/s10546-011-9669-2
Räisänen, P., A. Bogdan, K. Sassen, M. Kulmala, and M. J. Molina (2006). Impact of H2SO4/
H2O coating and ice crystal size on radiative properties of sub-visible cirrus. Atmos. Chem.
Phys., 6, 4659–4667.
Randall, D. A. (1980). Conditional instability of the first kind upside-down. J.Atmos.Sci., 37,
125–139.
Randall, D. A., S. Krueger, C. S. Bretherton, J. A. Curry, P. Duynkerke, M. Moncrieff, B. Ryan,
D. Starr, M. Miller, W. Rossow, G. Tselioudis, and B. Wielicki (2003). Confronting models
with data: The GEWEX Cloud Systems Study. Bull. Am. Meteorol. Soc., 84, 455–469.
Rangno, A. L., and P. V. Hobbs (1991). Ice particle concentrations and precipitation development
in small polar maritime cumuliform clouds. Quart. J. Roy. Meteor. Soc., 117, 207–241.
Rangno, A. L., and P. V. Hobbs (2001). Ice particles in stratiform clouds in the Arctic and
possible mechanisms for the production of high ice concentrations. J. Geophys. Res.,
106 (D14), 15,065–15,075.
Rasmussen, D. H. (1982). Thermodynamic and nucleation phenomena: A set of experimental
observations. J. Cryst. Growth, 56, 56–66.
Rasmussen, D. H., and A. P. Mackenzie (1972). Effect of solute on ice-solution interfacial free
energy; calculation from measure homogeneous nucleation temperatures. In: Water structure
at the water polymer interface. Ed.: Jellinek, H. H. G., Plenum Press, New York,
pp. 126–145.
Rempel, A. W., J. S. Wettlaufer, and M. G. Worster (2004). Premelting dynamics in a continuum
model of frost heave. J. Fluid Mech., 498, 227–244.
Ren, C., and A. R. MacKenzie (2005). Cirrus parameterisation and the role of ice nuclei. Quart.
J. Roy. Meteorol. Soc., 131, 1585–1605.
Ren, C., and A. R. MacKenzie (2007). Closed-form approximations to the error and comple-
mentary error functions and their applications in atmospheric science. Atmos. Sci. Let., 8 (3),
70–73, doi: 10.1002/asl.154.
Richardson, C. B., and T. D. Snider (1994). A study of heterogeneous nucleation in aqueous
solutions. Langmuir, 10, 2462–2465.
Risken, H. (1989). The Fokker–Planck Equation, 2nd ed., Springer-Verlag, 472 pp.
Rissler, J., A. Vestin, E. Swietlicki, G. Frisch, J. Zhou, P. Artaxo, and M. O. Andreae (2006).
Size distribution and hygroscopic properties of aerosol particles from dry-season biomass
burning in Amazonia. Atmos. Chem. and Physics, 6, 471–491.
Rissman, T. A., A. Nenes, and J. H. Seinfeld (2004). Chemical amplification (or dampening) of
the Twomey effect: Conditions derived from droplet activation theory. J. Atmos. Sci.,
61, 919–930.
Robinson, R. A., and R. H. Stokes (1970). Electrolyte solutions, 2nd ed., Butterworths, 559 pp.
Rodean, H. C. (1996). Stochastic Lagrangian models of turbulent diffusion. Meteorological Mono-
graphs, Amer. Meteorol. Soc., v. 26 (48), Boston, MA, USA, 84 pp.
Rogers, D. C. (1982). Field and laboratory studies of ice nucleation in winter orographic clouds.
PhD dissertation. Dept. Atmospheric Science, Univ. of Wyoming, Laramie, WY, USA, 161 pp.
References 757

Rogers, D. C. (1988). Development of a continuous flow thermal gradient diffusion chamber for
ice nucleation studies. Atmos. Res., 22, 149–181.
Rogers, D. C., P. J. DeMott, and L. O. Grant (1994). Concerning primary ice concentration and
water supersaturations in the atmosphere. Atmos. Res., 33, 151–168.
Rogers, D. C., P. J. DeMott, and S. M. Kreidenweis (2001). Airborne measurements of
tropospheric ice-nucleating aerosol particles in the Arctic spring. J. Geophys. Res.,
106, 15,053–15,063.
Rogers, D. C., P. J. DeMott, S. M. Kreidenweis, and Y. Chen (1998). Measurements of ice nucle-
ating aerosols during SUCCESS. Geophys. Res. Lett., 25, 1383–1386.
Rogers, P. S. Z., and K. S. Pitzer (1982). Volumetric properties of aqueous NaCl solutions.
J. Phys. Chem. Ref. Data, 11, 15–81.
Rogers, R. R., and M. K. Yau (1989). A short course in cloud physics, 3rd ed., Pergamon Press,
293 pp.
Rosenberg, R. (2005). Why is ice slippery? Phys. Today, 58 (12), 50–57.
Rosenfeld, D., Y. Rudich, and R. Lahav (2001). Desert dust suppressing precipitation: A possible
desertification feedback loop. Proc. Natl. Acad. Sci., 98, 5975–5980.
Rossow, W. B., and R. A. Schiffer (1999). Advances in understanding clouds from ISCCP. Bull.
Amer. Meteorol. Soc., 80, 2261–2287.
Rotman, D. A., et al. (2004). IMPACT, the LLNL 3-D global atmospheric chemical transport
model for the combined troposphere and stratosphere: Model description and analysis of
ozone and other trace gases. J. Geophys. Res., 109, D04303, doi:10.1029/2002JD003155.
Russell, L. M. and Y. Ming (2002). Deliquescence of small particles. J. Chem. Phys., 116 (1),
311–321, doi: 10.1063/1.1420 727.
Rutledge, S. A., and Hobbs P. V. (1983). The mesoscale and microscale structure and organization
of clouds and precipitations in midlatitude cyclones. VIII. A model for the “Seeder-feeder”
process in warm frontal rainbands. J. Atmos. Sci., 40, 1185–1206.
Ryan, B. F. (1996). On the global variation of precipitating layer clouds. Bull. Amer. Meteor. Soc.,
77, 53–70.
Rzesanke, D., D. Duft, and T. Leisner (2011). Laboratory experiments on the microphysics of
electrified cloud droplets. In: Climate and weather of the Sun–Earth system (CAWSES):
Highlights from a priority program. Ed.: Lübken, F.-J., Springer, Dordrecht, The
Netherlands.
Sassen, K. (1980). Remote sensing of planar ice crystal fall attitudes. J. Meteorol. Soc. Japan,
58, 422–429.
Sassen, K. (1992). Ice nuclei availability in the higher tropospheric: Implications of a remote sens-
ing cloud phase climatology. In: Nucleation and atmospheric aerosols. Eds.: Fukuta, N., and
Wagner, P., Deepak Publishing, pp. 287–290.
Sassen, K. (1997). Contrail-Cirrus and their potential for regional climate change. Bull. Amer.
Meteorol. Soc, 78 (9), 1885–1903.
Sassen, K., and S. Benson (2000). Ice nucleation in cirrus clouds, A model study of the homogeneous
and heterogeneous nucleation modes. Geophys. Res. Lett., 27, 521–524.
Sassen, K., and J. R. Campbell (2001). A midlatitude cirrus cloud climatology from the Facility
for Atmospheric Remote Sensing. Part I: Macrophysical and synoptic properties. J. Atmos.
Sci., 58, 481–496.
Sassen, K., and G. C. Dodd (1988). Homogeneous nucleation rate for highly supercooled cirrus
cloud droplets. J. Atmos. Sci., 45, 1357–1369.
Sassen, K., and G. C. Dodd (1989). Haze particle nucleation simulation in cirrus clouds, and
application for numerical and lidar studies. J. Atmos. Sci., 46, 3005–3014.
Sassen, K., and V. I. Khvorostyanov (2007). Microphysical and radiative properties of mixed-
phase altocumulus: A model evaluation of glaciation effects. Atmos. Res., 84 (4), 390–398.
758 References

Sassen, K., and V. I. Khvorostyanov (2008). Cloud effects from boreal forest fire smoke: evidence
for ice nucleation from polarization lidar data and cloud model simulations. Environ. Res.
Lett. 3, 025006, doi: 10.1088/1748-9326/3/2/025006.
Sassen K., and Z. Wang (2012). The clouds of the middle troposphere: Composition, radiative
impact, and global distribution. Surv. Geophys., doi: 10.1007/s10712-011-9163-x.
Sassen, K., D. O’C. Starr, and T. Uttal (1989). Mesoscale and microscale sructure of cirrus
clouds: Three case studies. J. Atmos. Sci., 46, 371–396.
Sassen, K., P. Cobb, J. Zhu, and V. Khvorostyanov (2006). Polarization lidar studies of Alaskan
forest fire smoke and indirect effect of clouds. Summer Intern. Laser Radar Conf., Japan, 2006.
Sassen, K., P. J. DeMott, J. M. Prospero, and M. R. Poellot (2003). Saharan dust storms and
indirect aerosol effects on clouds: CRYSTAL-FACE results. Geophys. Res. Lett., 30, 4714,
doi:10.1029/2003GL017371.
Sassen, K., Z. Wang, V. I. Khvorostyanov, G. L. Stephens, and A. Bennedetti (2002). Cirrus
cloud ice water content radar algorithm evaluation using an explicit cloud microphysical
model. J. Appl. Meteorol., 41, 620–628.
Sastry, S. (2002). Sculpting ice out of water. Nature, 416, 376–377.
Saul, A., and W. Wagner (1989). A fundamental equation for water covering the range from the
melting line to 1273 K at pressures up to 25000 MPa. J. Phys. Chem. Ref. Data,
18, 1537–1564.
Schaeffer, V. J. (1949). The formation of the ice crystals in the laboratory and the atmosphere.
Chem. Rev., 44, 291–320.
Schiffer, R. A., and W. B. Rossow (1983). The International Satellite Cloud Climatology Project
(ISCCP): The first project of the World Climate Research Programme. Bull. Amer. Meteor.
Soc., 64, 779–784.
Schumann, U. (1994). On the effect of emissions from aircraft engines on the state of the atmo-
sphere. Ann. Geophys., 12, 365–384.
Scott, W. T. (1968). Analytic studies of cloud droplet coalescence. J. Atmos. Sci., 25, 54–65.
Sedunov, Y. S. (1965). The fine structure of the clouds and its role in formation of the cloud droplet
spectra. Izv. Acad. Sci. USSR, Atmos. Oceanic Phys., 1, 416–421.
Sedunov, Y. S. (1967). Kinetics of initial stage of condensation in clouds. Izvestia Acad. Sci. USSR,
Atmos Oceanic Phys., 3, 34–46.
Sedunov, Y. S. (1974). Physics of drop formation in the atmosphere. Wiley, New York, 234 pp.
Seifert, A. (2005). On the shape-slope relation of drop size distributions in convective rain. J. Appl.
Meteorol. 44, 1146–1151.
Seifert, A., and K. D. Beheng (2001). A double-moment parameterization for simulating autocon-
version, accretion and selfcollection. Atmos. Res., 59–60, 265–281.
Seifert, A., and K. D. Beheng (2006). A two-moment cloud microphysics parameterization for
mixed-phase clouds. Part 1: Model description, Meteorol. Atmos. Phys., 92, 45–66.
Seinfeld, J. H., and S. N. Pandis (1998). Atmospheric chemistry and physics, Wiley, New York,
1326 pp.
Serpolay, R. (1969). Perfectionnement d’une technique d’ensemencement et recherches de pro-
cedes de modification des brouillards. Météorologie, 9, 45–54.
Shaw, R. A. (2003). Particle-turbulence interactions in atmospheric clouds. Annu. Rev. Fluid Mech.,
35, 183–227.
Shaw, R. A., A. J. Durant, and Y. Mi (2005). Heterogeneous surface crystallization observed in
undercooled water. J. Phys. Chem., 109 B, 9865–9868.
Shaw, R. A., W. C. Reade, L. R. Collins, and J. Verlinde (1998). Preferential concentration of
cloud droplets by turbulence: Effects on the early evolution of cumulus cloud droplet spectra.
J. Atmos. Sci., 55, 1965–1976.
References 759

Shchekin, A. K., and A. I. Rusanov (2008a). Generalization of the Gibbs-Kelvin-Köhler and

Oswald-Freundlich equations for a liquid film on a soluble nanoparticle. J. Chem. Phys.,
129, 154116, doi: 10.1063/1.2996590.
Shchekin, A. K., and I. V. Shabaev (2010). Activation barriers for the complete dissolution of
condensation nucleus and its reverse crystallization in droplets in the undersaturated solvent
vapor. Colloid J., 72, 432–439, doi: 10.1134/S1061 933X1003 018X, 2010.
Shchekin, A. K., I. V. Shabayev, and A. I. Rusanov (2008b). Thermodynamics of droplet forma-
tion around a soluble condensation nucleus in the atmosphere of a solvent vapor. J. Chem.
Phys., 129, 214111, doi: 10.1063/1.3021 078.
Shifrin, K. S. (1955). On the calculation of radiative properties of clouds. Proc. Main Geophys.
Observatory, Leningrad, 46 (108), 5–33 (in Russian).
Shifrin, K. S., and V. Y. Perelman (1960). Kinetics of distillation in a mixed cloud. Proc. Acad.
Sci. USSR, 132, 1148–1151.
Shilling, J. E., T. J. Fortin, and M. A. Tolbert (2006). Depositional ice nucleation on crystalline
organic and inorganic solids. J. Geophys. Res., 111, D12 204, doi:10.1029/2005JD006664.
Shipway, B. J., and S. J. Abel (2010). Analytical estimation of cloud droplet nucleation based on
an underlying aerosol population. Atmos. Res., 96, 344–355.
Shulmann, M. L., M. L. Jacobson, R. J. Charlson, R. E. Synovec, and T. E. Young (1996).
Dissolution behavior and surface tension effects of organic compounds in nucleating cloud
droplets. Geophys. Res. Lett., 23, 277–280.
Shupe M. D., S. Y. Matrosov, and T. Uttal (2006). Arctic mixed-phase cloud properties derived
from surface-based sensors at SHEBA. J. Atmos. Sci., 63, 697–711.
Silverman, B. A., and A. I. Weinstein (1973). Fog modification – A technology assessment.
Air Force Surveys in Geophysics, No. 2, AFC-0159, 126 pp.
Singer, S. J., J.-L. Kuo, T. K. Hirsch, C. Knight, L. Ojamäe, and M. L. Klein (2005). Hydrogen-
bond topology and the ice VII-VIII and ice Ih-XI proton-ordering phase transitions. Phys. Rev.
Lett., 94, 135,701–135,705.
Slingo, A. (1989). A GCM parameterization for the shortwave radiative properties of water clouds.
J Atmos. Sci., 46, 1419–1427.
Slingo, A., and H. M. Schecker (1982). On the shortwave radiative properties of stratiform water
clouds. Quart. J. Roy. Meteor. Soc., 108, 407–426.
Slinn, W. G. N., and J. M. Hales (1971). A reevaluation of the role of thermophoresis as a mechanism
of in- and below-cloud scavenging. J. Atmos. Sci., 28, 1465–1471.
Smirnov, V. I. (1978). On the equilibrium sizes and size spectra of aerosol particles in a humid
atmosphere. Izv. Acad. Sci. USSR, Atmos. Oceanic Phys., 14, 1102–1106.
Smirnov, V. I., and A. S. Kabanov (1970). Effect of horizontal inhomogeneity of activated cloud
drops on their size spectrum. Izv. Acad. Sci. USSR, Atmos. Oceanic Phys., 6, 1262–1275.
Smirnov, V. I., and L. A. Nadeykina (1986). On the theory of the drop size spectrum formed by
condensation in turbulent cloud. Izv. Acad. Sci. USSR, Atmos. Oceanic Phys., 22, 478–487.
Smirnov, V. I., and B. N. Sergeev (1973). Size distribution of large cloud drops grown on
hygroscopic cloud condensation nuclei. Izv. Acad. Sci. USSR, Atmos. Oceanic Phys.,
9, 1288–1300.
Smoluchowski, M. (1916). Drei Vortäge über Diffusion, Brounische Bewegung und Koagulation
von Kolloidteilchen. Phys. Zeits., Bd. 17, 557–585.
Snider, J. R., S. Guibert, J.-L. Brenguier, and J.-P. Putaud (2003). Aerosol activation in marine
stratocumulus clouds: Köhler and parcel theory closure studies. J. Geophys. Res., 108 (D15),
8629, doi: 10.1029/2002JD0026692.
Song, Y., and E. A. Mason (1990a). Analytical equation of state for molecular fluids: Kihara
model for rodlike molecules. Phys. Rev. A, 42, 4743–4748.
760 References

Song, Y., and E. A. Mason (1990b). Analytical equation of state for molecular fluids: Comparison
with experimental data, Phys. Rev. A, 42, 4749–4758.
Song, Y., and E. Mason (1989). Statistical-mechanical theory of a new analytical equation of state.
J. Chem. Phys., 91, 7840.
Speedy, R. J. (1982). Stability-limit conjecture: An interpretation of the properties of water. J. Phys.
Chem., 86, 982–991.
Speedy, R. J. (1996). Two waters and no ice please. Nature, 380, 289–290.
Speedy, R. J., and C. A. Angell (1976). Isothermal compressibility of supercooled water and
evidence for a thermodynamic singularity at −45°C. J. Chem. Phys., 65, 851–858.
Spice, A., D. W. Johnson, P. R. A. Brown, A. G. Darlison, and C. P. R. Saunders (1999).
Primary ice nucleation in orographic cirrus cloud: A numerical simulation of the microphysics.
Quart. J. Roy. Meteor. Soc., 125, 1637–1667.
Spichtinger, P., and K. M. Gierens (2009). Modelling of cirrus clouds – Part 2: Competition of
different nucleation mechanisms. Atmos. Chem. Phys., 9, 2319–2334.
Spichtinger, P., and M. Krämer (2012). Tropical tropopause ice clouds: A dynamic approach to
the mystery of low crystal numbers. Atmos. Chem. Phys. Discuss., 12, 28,109–28,153.
Squires, P. (1958). The microstructure and colloidal stability of warm clouds, II, The causes of the
variations of microstructure. Tellus, 10, 262–271.
Srivastava, R. C. (1969). Note on the theory of growth of cloud drops by condensation. J. Atmos.
Sci., 26, 776–780.
Srivastava, R. C. (1971). Size distribution of raindrops generated by their breakup and coalescence.
J. Atmos. Sci., 28, 410–415.
Srivastava, R. C. (1978). Parameterization of raindrop size distribution. J. Atmos. Sci.,
35, 108–117.
Srivastava, R. C. (1982). A simple model of particle coalescence and breakup. J. Atmos. Sci.,
39, 1317–1322.
Srivastava, R. C. (1989). Growth of cloud drops by condensation: A criticism of currently accepted
theory and a new approach. J. Atmos. Sci., 46, 869–887.
Srivastava, R. C., and R. E. Passarelli (1980). Analytical solutions to simple models of condensa-
tion and coalescence. J. Atmos. Sci., 37, 612–621.
Stanley, H. E., P. Kumar, L. Xu, Z. Yan, M. G. Mazza, S. V. Buldyrev, S.-H. Chen, and
F. Mallamace (2007). The puzzling unsolved mysteries of liquid water: Some recent
progress. In: Proc. Pan American Sci. Inst. (PASI) Conference “Disorder and Complexity,”
Mar del Plata, Argentina, 11–20 December 2006, Physica, A, 386, 729–743.
Starr, D. O’C., et al. (2000). Comparison of cirrus cloud models: A Project of the GEWEX Cloud
System Study (GCSS) Working Group on Cirrus Cloud Systems. Proc. Int. Cloud Phys.
Conf., Reno, NV, USA, August 2000, 1–4.
Starr, D. O’C., and S. K. Cox (1985). Cirrus clouds. Part I: A cirrus cloud model. J. Atmos. Sci.,
42, 2663–2681.
Stepanov, A. S. (1975). Condensational growth of cloud droplets in a turbulized atmosphere. Izv.
Akad. Sci. USSR, Atmos. Oceanic Phys., 11, 27–42.
Stepanov, A. S. (1976). On the effect of turbulence on the size spectrum of cloud droplets at
condensation. Izv. Acad. Sci. USSR, Atmos. Oceanic Phys., 12, 281–292.
Stephens, G. L. (1983). The influence of radiative transfer on the mass and heat budgets of ice
crystals falling in the atmosphere. J. Atmos. Sci., 40, 1729–1739.
Stephens, G. L. (1984). The parameterization of radiation for numerical weather prediction and
climate models. Review. Mon. Wea. Rev., 112, 826–867.
Stephens, G. L. (2005). Cloud feedbacks in the climate system: A critical review. J. Clim.
18, 237–273.
References 761

Stephens, G. L., D. G. Vane, and S. J. Walter (2000). The CLOUDSAT mission: A new dimen-
sion to space-based observations of cloud in the coming millennium. Workshop on Cloud
Processes and Cloud Feedback in Large-Scale Models, 9–13 November 1999, Reading, UK.
Report WCRP-110, WMO/TD-No 993, Geneva, 2000.
Stephens, G. L., S. C. Tsay, P. W. Stackhouse, and P. J. Flatau (1990). The relevance of the
microphysical and radiative properties of cirrus clouds to climate and climatic feedback.
J. Atmos Sci., 47, 1742–1753.
Stöckel, P., I. M. Weidinger, H. Baumgärtel, and T. Leisner (2005). Rates of homogeneous ice
nucleation in levitated H2O and D2O droplets. J. Phys. Chem. A, 109, 2540–2546.
Straka, J. M. (2009). Cloud and precipitation microphysics. Cambridge Univ. Press, 392 pp.
Ström, J., B. Strauss, T. Anderson, F. Schröder, J. Heintzenberg, and P. Wendling (1997).
In situ observations of the microphysical properties of young cirrus clouds. J. Atmos. Sci.,
54, 2542–2553.
Ström, J., M. Seifert, B. Kärcher, J. Ovarlez, A. Minikin, J.-F. Gayet, R. Krejci, A. Petzold,
F. Auriol, W. Haag, R. Busen, U. Schumann, and H. C. Hansson (2003). Cirrus cloud
occurrence as function of ambient relative humidity: A comparison of observations obtained
during INCA experiment. Atmos. Chem. Phys., 3, 1807–1816.
Sud, Y. C., and D. Lee (2007). Parameterization of aerosol indirect effect to complement McRAS
cloud scheme and its evaluation with the 3-year ARM-SGP analyzed data for single column
models. Atmos. Res., 86, 105–125.
Sud, Y. C., E. Wilcox, W. K.-M. Lau, G. K. Walker, X.-H. Liu, A. Nenes, D. Lee, K.-M. Kim,
Y. Zhou, and P. S. Bhattacharjee (2009). Sensitivity of boreal-summer circulation and pre-
cipitation to atmospheric aerosols in selected regions – Part 1: Africa and India. Ann.
Geophys., 27, 3989–4007, www.ann-geophys.net/27/3989/2009/.
Swanson, B. D. (2009). How well does water activity determine homogeneous ice nucleation tem-
perature in aqueous sulfuric acid and ammonium sulfate droplets? J. Atmos. Sci., 66, 741–754.
Swietlicki, E., et al. (1999). A closure study of submicrometer aerosol particle behavior. Atmos.
Res., 50, 205–240.
Swietlicki, E., et al. (2000). Hygroscopic properties of aerosol particles in the north-eastern Atlantic
during ACE-2. Tellus, Ser. B, 52, 201–227.
Szyrmer, W., and I. Zawadski (2010). Snow studies. Part II: Average relationship between mass of
snowflakes and their terminal fall velocity. J. Atmos. Sci., 67, 3319–3335.
Tabazadeh, A., and O. B. Toon (1998). The role of ammoniated aerosols in cirrus cloud nucleation.
Geophys. Res. Lett., 25, 1379–1382.
Tabazadeh, A., E. J. Jensen, and O. B. Toon (1997). A model description for cirrus cloud nucle-
ation from homogeneous freezing of sulfate aerosols. J. Geophys. Res., 102 (D20),
23,845–23,850.
Tabazadeh, A., S. T. Martin, and J.-S. Lin (2000). The effect of particle size and nitric acid
uptake on the homogeneous freezing of aqueous sulfuric acid particles. Geophys. Res. Lett.,
27, 1111–1114.
Tabazadeh, A., Y. S. Djikaev, and H. Reiss (2002b). Surface crystallization of supercooled water
in clouds. Proc. Natl. Acad. Sci. (Geophysics), 99 (25), 15873–15878.
Tabazadeh, A., Y. S. Djikaev, P. Hamill, and H. Reiss (2002a). Laboratory evidence for surface
nucleation of solid polar stratospheric cloud particles. J. Phys. Chem. A, 106, 10,238–10,246.
Takahashi, T. (1976). Hail in axisymmetric cloud model. J. Atmos. Sci., 33, 1579–1601.
Takano, Y., and K.-N. Liou (1989). Solar radiative transfer in cirrus clouds, I, Single scattering
and optical properties of hexagonal ice crystals. J. Atmos. Sci., 46, 3–19.
Tammann, G. (1900). Ueber die Grenzen des festen Zustandes IV. Annaln. Phys., 2, 1–31.
Tanaka, H. (1996). A self-consistent phase diagram for supercooled water. Nature, 380, 328–330.
762 References

Tang, I. N. (1997). Thermodynamic and optical properties of mixed-salt aerosols of atmospheric

importance. J. Geophys. Res., 102 (D2), 1883–1893.
Tang, I. N., and H. R. Munkelwitz (1993). Composition and temperature dependence of the
deliquescence properties of hygroscopic aerosols. Atmos. Environ., 27A, 467–473.
Tang, I. N., and H. R. Munkelwitz (1994). Water activities, densities, surface and refractive indices
of aqueous sulfates and sodium nitrate droplets of atmospheric importance. J. Geophys. Res.,
99, 18,801–18,808.
Tang, I. N., A. C. Tridicao, and K. H. Fung (1997). Thermodynamic and optical properties of sea
salt aerosols. J. Geophys. Res., 102 (D19), 23,269–23,275.
Tao, W.-K., J.-P. Chen, Z. Li, C. Wang, and C. Zhang (2012). Impact of aerosols on convective
clouds and precipitation. Rev. Geophys., 50, RG2001, doi:10.1029/2011RG000369.
Tejero, C. F., and M. Baus (1998). Liquid polymorphism of simple fluids within a van der Waals
theory. Phys. Rev. E, 57 (4), 4821–4823.
Telford, J. W. (1987). Comment on “Does mixing promote cloud droplet growth?” J. Atmos. Sci.,
44, 2352–2354.
Telford, J. W., and S. K. Chai (1980). A new aspect of condensation theory. Pure Appl. Geophys.,
118, 720–742.
Telford, J. W., T. S. Keck, and S. K. Chai (1984). Entrainment at cloud tops and the droplet
spectra. J. Atmos. Sci., 41, 3170–3179.
Thomson, J. J. (1888). Application of dynamics to physics and chemistry, 1st ed., Cambridge
University Press, 163 pp.
Tillner-Roth, R. (1998). Fundamental equations of state, Shaker Verlag, 126 pp.
Tomasi, C., E. Caroli, and V. Vitale (1983). Study of the relationship between Ångström’s wave-
length exponent and Junge particle size distribution exponent. J. Clim. Appl. Meteorol.,
22, 1707–1716.
Tomasi, C., V. Vitale, A. Lupi, C. Di Carmine, et al. (2007). Aerosol in polar regions: A historical
overview based on optical depth and in situ observations. J. Geophys. Res., 112, D16205.
Tripoli, G. J., and W. R. Cotton (1980). A numerical investigation of several factors contributing
to the observed variable intensity of deep convection over South Florida. J. Appl. Meteor.,
19, 1037–1063.
Truskett, T. M., P. G. Debenedetti, S. Sastry, and S. Torquato (1999). A single-bond approach
to orientation-dependent interactions and its implications for liquid water. J. Chem. Phys.,
111, 2647–2656.
Tsay, S. C., and K. Jayaweera (1984). Physical characteristics of Arctic stratus clouds. J. Clim.
Appl. Met., 23, 584–596.
Tse, J. S. (1992). Mechanical instability in ice Ih: A mechanism for pressure-induced amorphization.
J. Chem. Phys., 96 (7), 5482–5487.
Tse, J. S., D. D. Klug, C. A. Tulk, I. Swainson, E. C. Svensson, C.-K. Loong, V. Shpakov,
V. R. Belosludov, R. V. Belosludov, and Y. Kawazoe (1999). The mechanism for pressure-
induced amorphization of ice Ih. Nature, 400, 647–649.
Turnbull, D., and J. C. Fisher (1949). Rate of nucleation in condensed systems. J. Chem. Phys.,
17 (1), 71–73.
Turnbull, D., and B. Vonnegut (1952). Nucleation catalysis. Industr. Eng. Chem., 44, 1292–1298.
Twomey, S. (1959). The nuclei of natural cloud formation. II. The supersaturation in natural clouds
and the variation of cloud droplet concentration. Geoph. Pura Appl., 43, 243–249.
Twomey, S. A. (1977a). The influence of pollution on the shortwave albedo of clouds. J. Atmos.
Sci., 34, 1149–1152.
Twomey, S. (1977b). Atmospheric aerosols. Elsevier, New York, 302 pp.
Twomey, S., and T. A. Wojciechowski (1969). Observations of the geographical variations of
cloud nuclei. J. Atmos. Sci., 26, 684–696.
References 763

Tzivion, S., G. Feingold, and Z. Levin (1987). An efficient numerical solution to the stochastic
collection equation. J. Atmos. Sci., 44, 3139–3149.
Ulbrich, C. W. (1983). Natural variations in the analytical form of the raindrop size distribution.
J. Climate Appl. Meteor., 22, 1764–1775.
Uttal, T., J. A. Curry, M. G. McPhee, et al. (2002). Surface heat budget of the Arctic Ocean. Bull.
Am. Meteorol. Soc., 83, 255–275.
UNESCO (1981). Tenth Report of the Joint Panel on Oceanographic Tables and Standards.
UNESCO Technical Papers in Marine Sci., No. 26, Paris, 126 pp.
Vaillancourt, P. A., and M. K. Yau (2000). Review of particle–turbulence interactions and conse-
quences for cloud physics. Bull. Amer. Meteor. Soc., 81, 285–298.
Vaillancourt, P. A., M. K. Yau, P. Bartello, and W. W. Grabowski (2002). Microscopic approach
to cloud droplet growth by condensation. Part II. Turbulence, clustering, and condensational
growth. J. Atmos. Sci., 59, 3421–3435.
Vali, G. (1974). Contact ice nucleation by natural and artificial aerosols. In: “Conf. on Cloud Phys-
ics,” Amer. Meteorol. Soc, Tucson., pp. 34–37.
Vali, G. (1976). Contact-freezing nucleation measured by the DFC instrument. In: “Third Interna-
tional Workshop on Ice Nucleus Measurements.” Laramie, University of Wyoming, WY, USA,
pp. 159–178.
Vali, G. (1985). Atmospheric ice nucleation: A review. J. Rech. Atmos., 19, 105–115.
Vali, G. (1994). Freezing rate due to heterogeneous nucleation. J. Atmos. Sci., 51, 1843–1856.
Vali, G. (2008). Repeatability and randomness in heterogeneous freezing nucleation. Atmos. Chem.
Phys., 8, 5017–5031.
van de Hulst, H. C. (1957). Light scattering by small particles. Dover, 470 pp.
van Kampen, N. G. (1992). Stochastic processes in physics and chemistry, 2nd ed. North-Holland
Publishing Company, 465 pp.
Vasilyeva, K. I., V. M. Merkulovich, and A. S. Stepanov (1984). Behavior of the droplet spectrum
in a turbulized two-phase cloud. Sov. Meteorol. Hydrol., 11, 31–42.
Veltishchev, N. F., V. D. Zhupanov, and Yu. B. Pavlyukov (2011). Short-range forecast of heavy
precipitation and strong wind using the convection-allowing WRF models. Russian Meteorol.
Hydrol., 36 (1), 47–58.
Verlinde, J., P. J. Flatau, and W. R. Cotton (1990). Analytical solutions to the collection growth
equation: Comparison with approximate methods and application to cloud microphysics
parameterization schemes. J. Atmos. Sci., 47, 2871–2880.
Verlinde, J., J. Y. Harrington, G. M. McFarquhar, V. T. Yannuzzi, et al. (2007). Overview of the
Mixed-Phase Arctic Cloud Experiment (MPACE). Bull. Am. Meteorol. Soc., 88, 205–201.
Vertsner, V. N., and G. S. Zhdanov (1966). Electron-microscope study of the low-temperature
forms of ice. Sov. Phys. Crystallogr., 10, 597–602.
Vignati, E., J. Wilson, and P. Stier (2004). An efficient size-resolved aerosol microphysics module
for large-scale aerosol transport models. J. Geophys. Res., D22 202.
Vlasiuk, M. P., N. G. Mukiy, Yu. A. Seregin, V. I. Khvorostyanov, A. A. Chernikov,
L. V. Yaroshevich (1994). Progress in the development and the use of nitrogen technology
for artificial dispersal of supercooled fogs at airports. Proc. 6th WMO Scientif. Conf. Weather
Modification, Italy, May, WMO/TD-596, pp. 665–668
Volmer, M. (1939). Kinetic der phasenbildung. Steinkopf, Drezden and Leipzig, 325 pp.
Volmer, M., and A. Weber (1926). Keimbildung in übersättigten Gebilden. Z. Phys. Chem.,
A119, 277–301.
Voloshchuk, V. M. (1977). The kinetic equation of stochastic coagulation. Sov. Meteorol. Hydrol.,
No. 5, 3–12.
Voloshchuk, V. M. (1984). The kinetic theory of coagulation. Hydrometeoizdat, Leningrad, 283
pp. (in Russian).
764 References

Voloshchuk, V. M., and Y. S. Sedunov (1975). The processes of coagulation in the disperse systems.
Leningrad, Hydrometeoizdat, 320 pp. (in Russian).
Voloshchuk, V. M., and Y. S. Sedunov (1977). The kinetic equation for the evolution of the drop-
let spectrum in the turbulent medium at the condensation stage of cloud development. Sov.
Meteorol. Hydrol., 3, 1–10.
von der Emde, K., and U. Wacker (1993). Comments on the relationship between aerosol size
spectra, equilibrium drop size spectra and CCN spectra. Contrib. Atmos., Phys., 66, 157–162.
Vonnegut, B. (1947). The nucleation of ice by silver iodide. J. Appl. Phys., 18, 593–595.
Wagner, W., and A. Prua (2002). The IAPWS formulation 1995 for the thermodynamic properties
of ordinary water substance for general and scientific use. J. Phys. Chem. Ref. Data,
31, 387–535.
Wagner, W., A. Saul, and A. Prua (1994). International equations for the pressure along the melt-
ing and along the sublimation curve of ordinary water substance. J. Phys. Chem. Ref. Data,
23 (3), 515–527.
Wagner, W., T. Riethmann, R. Feistel, and A. H. Harvey (2011). New equations for the subli-
mation pressure and melting pressure of H2O ice Ih. J. Phys. Chem. Ref. Data, 40, 043103,
doi:10.1063/1.3657937.
Waldman, L., and K. H. Schmidt (1966). Thermophoresis and diffusionphoresis of aerosols.
Academic Press, New York, 468 pp.
Wang, P. K., and W. Ji (1992). Preprints Cloud Phys. Conf. Montreal, McGill Univ., pp. 76–80.
WMO (1975). International cloud atlas, vol. I. Manual on the observations of clouds and other
meteors. World Meteorological Organization (WMO), Geneva.
WMO (1987). International cloud atlas, vol. II. Plates. World Meteorological Organization
(WMO), No. 407, Geneva.
Warner, J. (1969a). The microstructure of cumulus cloud. Part I: General features of the droplet
spectrum. J. Atmos. Sci., 26, 1049–1059.
Warner, J. (1969b). The microstructure of cumulus cloud. Part II. The effect on droplet size distri-
bution of the cloud nucleus spectrum and vertical velocity. J. Atmos. Sci., 26, 1272–1282.
Warren, S. G. (1984). Optical constants of ice from ultraviolet to the microwave. Appl. Opt.,
23, 1206–1225.
Warren, S. G., C. J. Hahn, and J. London (1985). Simultaneous occurrence of different cloud
types. J. Clim. Appl. Meteor. 24 (7), 658–667.
Warren, S. G., R. Eastman, and C. J. Hahn (2013). Cloud climatology. Encyclopedia of atmospheric
sciences. Oxford University Press, 137–147.
Wegener, A. (1911). Thermodynamik der atmosphäre. J. A. Barth, 331 pp.
Weingartner, E., H. Burtscher, and U. Baltensperger (1997). Hygroscopic properties of carbon
and diesel soot particles. Atmos. Env., 31, 3211–3227.
Wettlaufer, J. S. (1999). Impurity effects in the premelting of ice. Phys. Rev. Lett., 82, 2516–2523.
Wettlaufer, J. S., and J. G. Dash (2000). Melting below zero. Scientific American, 282 (2), 50–53.
Wexler, A. (1976). Vapor pressure formulation for water in range 0 to 100 °C: A revision. J. Res.
Nat. Bur. Stand., 80A, 775–785.
Wexler, A. S., and J. H. Seinfeld (1991). Second-generation inorganic aerosol model. Atmos.
Environ., 25A, 2731–2748.
Whalley, E. (1969). Structural problems of ice. In: Physics of ice. Eds.: Riehl, N., Bullemer, B.,
and Engelgardt, H., Plenum, New York, pp. 19–43.
Whalley, E., and D. W. Davidson (1965). Entropy changes in the phase transitions of ice. J. Chem.
Phys., 43, 2148–2149.
Whalley, E., J. B. R. Heath, and D. W. Davidson (1968). Ice IX: An antiferroelectric phase
related to ice III. J. Chem. Phys., 48, 2362–2370.
References 765

Whitby, K. (1978). The physical characteristics of sulfur aerosols. Atmos. Environ., 12, 135–159.
Willis, P. T. (1984). Functional fits to some observed drop size distributions and parameterization
of rain. J. Atmos. Sci., 41, 1648–1661.
Woodcock, A. H., R. A. Duce, and J. L. Moyers (1971). Salt particles and raindrops in Hawaii.
J. Atmos. Sci., 28, 1252–1257.
Wright, D. G., R. Feistel, J. H. Reissmann, K. Miyagawa, D. R. Jackett, W. Wagner,
U. Overhoff, C. Guder, A. Feistel, and G. M. Marion (2010). Numerical implementation
and oceanographic application of the thermodynamic potentials of liquid water, water vapour,
ice, seawater and humid air – Part 2: The library routines. Ocean Sci., 6, 695–718, doi:
10.5194/os–6–695–2010.
Wurzler, S., T. G. Reisin, and Z. Levin (2000). Modification of mineral dust particles by cloud
processing and subsequent effect on drop size distributions. J. Geophys. Res., 105 (D4),
4501–4512.
Xu, J., D. Imre, R. McGraw, and I. Tang (1998). Ammonium sulfate: Equilibrium and metasta-
bility phase diagrams from 40 to −50 °C. J. Phys. Chem., B, 102, 7462–7469.
Xue, L., A. Teller, R. Rasmussen, I. Geresdi, and Z. Pan (2010). Effects of aerosol solubility and
regeneration on warm-phase orographic clouds and precipitation simulated by a detailed bin
microphysical scheme. J. Atmos. Sci., 67, 3336–3354.
Yang, P., B.-C. Gao, B. A. Baum, Y. X. Hu, W. J. Wiscombe, S.-C. Tsay, D. M. Winker,
and S. L. Nasiri (2001). Radiative properties of cirrus clouds in the infrared (8–13 μm)
spectral region. J. Quant. Spectrosc. Radiat. Transfer, 70, 473–504.
Young, K. C. (1974a). A numerical simulation of wintertime, orographic precipitation. Part I:
Description of model microphysics and numerical techniques. J. Atmos. Sci., 31, 1735–1748.
Young, K. C. (1974b). The role of contact nucleation in ice phase initiation in clouds. J. Atmos.
Sci., 31, 768–776.
Young, K. C. (1993). Microphysical processes in clouds. Oxford University Press, 427 pp.
Young, K. C., and A. J. Warren (1992). A reexamination of the derivation of the equilibrium
supersaturation curve for soluble particles. J. Atmos. Sci., 49, 1138–1143.
Yum, S. S., and J. G. Hudson (2001). Vertical distributions of cloud condensation nuclei spectra
over the springtime Arctic Ocean. J. Geophys. Res., 106 (D14), 15,045–15,052.
Yun, Y., and J. E. Penner (2012). Global model comparison of heterogeneous ice nucleation
parameterizations in mixed phase clouds. J. Geophys. Res., 117, D07203, doi:10.1029/
2011JD016506.
Zawadski, I., and de M. A. de Agostinho (1988). Equilibrium raindrop size distributions in tropical
rain. J. Atmos. Sci., 45, 3452–3459.
Zawadski., I., E. Jung, and G. W. Lee (2010). Snow studies. Part I: A study of natural variability
of snow terminal velocity. J. Atmos. Sci., 67, 1591–1604.
Zeldovich, J. B. (1942). Toward the theory of formation of a new phase. Cavitation. J. Exper.
Theor. Phys., 12, 525.
Zhang, G., J. Vivekanandan, and E. A. Brandes (2001). A method for estimating rain rate and
drop size distribution from polarimetric radar measurements. IEEE Trans. Geosci. Remote
Sens., 39, 830–841.
Zhang, G., J. Vivekanandan, and E. A. Brandes (2003a). Constrained gamma drop size
distribution model for polarimetric radar rain estimation: Justification and development.
Preprints, 31st Int. Conf. on Radar Meteorology, Seattle, WA, USA, Amer. Meteor. Soc.,
206–225.
Zhang, G., J. Vivekanandan, E. A. Brandes, R. Meneghini, and T. Kozu (2003b). The shape-
slope relation in observed gamma raindrop size distributions: Statistical error or useful infor-
mation? J. Atmos. Oceanic Technol., 20, 1106–1119.
766 References

Zhang, H., I. N. Sokolik, and J. A. Curry (2011). Impact of dust aerosols on Hurricane Helene’s
early development through the deliquescent heterogeneous freezing mode. Atmos. Chem.
Phys. Discuss., 11, 14,339–14,381, doi:10.5194/acpd-11-14339-2011.
Zhou, J., E. Swietlicki, O. H. Berg, P. A. Aalto, K. Hämeri, E. D. Nilsson, and C. Leck (2001).
Hygroscopic properties of aerosol particles over the central Arctic Ocean during summer.
J. Geophys. Res., 106 (D23), 32,111–32,123.
Zobrist, B. (2006). Heterogeneous ice nucleation in upper tropospheric aerosols. Dr. Dissertation,
Swiss Federal Inst. Technology, Zurich, 148 pp.
Zobrist, B., C. Marcolli, T. Peter, and T. Koop (2008). Heterogeneous ice nucleation in aqueous
solutions: The role of water activity. J. Phys. Chem., A, 112, 3965–3975.
Zobrist, B., T. Koop, B. P. Luo, C. Marcolli, and T. Peter (2007). Heterogeneous ice nucleation
rate coefficient of water droplets coated by a nonadecanol monolayer. J. Phys. Chem. C, 111,
2149–2155, doi:10.1021/jp066080w.
Zuberi, B., A. K. Bertram, C. A. Cassa, L. T. Molina, and M. J. Molina (2002). Heterogeneous
nucleation of ice in (NH4)2SO4-H2O particles with mineral dust immersions. Geophys. Res.
Lett, 29 (10), 1504, doi:10.1029/2001GL014281.
Zubler, E. M., U. Lohmann, D. Lüthi, and C. Schär (2011). Statistical analysis of aerosol effects
on simulated mixed-phase clouds and precipitation in the Alps. J. Atmos. Sci., 68, 1474–1492.
Notations

A1, A2 coefficients in the commonly used 3νΦ s ms M w

supersaturation equation that describe B= = brd2(1+ β ) Raoult’s term in the
4π M s ρ w
supersaturation generation and
Köhler equation (the activity of a CCN)
absorption
and its parameterization via particle
2σ sa radius rd
A f ≡ rfr = curvature parameter for freezing
ρi Lefm Bij autocorrelation velocity function in turbu-
(scaling freezing radius) that characterizes lence diffusion
the effect of the drop radius on freezing Bijnn (t ,τ f ) autocorrelation velocity function of a
Ag = 4prg2 surface area of an embryo of new nonconservative substance
phase with radius rg containing g particles ρ Mw
b = (νΦ s )ε v s parameter describing the
2 M wσ sa ρw M s
Ak = Kelvin’s curvature parameter
RT ρ w volume-proportional soluble fraction in a
AK backscatter cross sections for spherical par- CCN for b = 1/2
ticles at radar wavelengths ρ Mw
∆ρ b = rad 1ε v 0 (νΦ s ) s parameter describing
Ap = coefficient that characterizes pres- ρw Ms
ρ w ρi Lefm the surface-proportional soluble fraction
sure effect on freezing; Dr = rw − ri in a CCN for b = 0
am parameter describing the pressure reduction Dρ
bcon = v vs parameter in the particle growth
in a non-ideal gas Γp ρ w
av activity of water vapor rate equation in stochastic condensation
aw activity of water in solution theory
aɶ s activity of solute in solution bm parameter describing the excluded volume in
aɶ s* activity of solute in saturated solution a non-ideal gas
awi (T ) water activity in bulk solution in equilib-
rium with ice CD drag coefficient
δ aw ,het = aw (T f ,het ) − aw (Tm ) difference or shift Ce electrical capacitance of a conductor
in the activities between the melting and CV heat capacity of a body at constant volume
heterogeneous freezing curves at the same CP heat capacity of a body at constant pressure
temperature Chet prefactor (kinetic coefficient) in the
δ aw ,hom = aw (T f ,hom ) − aw (Tm ) difference or shift nucleation rate of heterogeneous freezing
in the activities between the melting and Chom prefactor (kinetic coefficient) in the
homogeneous freezing curves at the same nucleation rate of homogeneous freezing
temperature

767
768 Notations

Cdel kinetic coefficient for deliquescence D2,ext , D3,ext , D4,ext the terms in the equation for
Ce ≈ 1.7 × 1011 erg cm−3 Turnbull–Vonnegut con- the extinction cross section
stant for the misfit strain energy density DD(z) Debye’s function
Cee2 increase in activation energy density Dv the vapor diffusion coefficient
[erg cm−3] of nucleation due to misfit Dv* effective vapor diffusion coefficient
strain e kT
Dr = Einstein’s coefficient of Brownian
Csl,r(ra) Cunningham’s slip-flow correction 6πηa r
Cst = (2/9)grbr2/h Stokes terminal velocity diffusion
c number of components in a thermodynamic D(g) diffusion coefficient of g-mers in the
system g-space in nucleation theory
 L Mw  g (dql/dz)ad adiabatic gradient of liquid water
c1w (T ) =  e − 1 coefficient in the mixing ratio or liquid water content
 c pT M a  Ra T
generation term in the water supersaturation (dqi/dz)ad adiabatic gradient of the ice water
equation mixing ratio or ice water content
 L Mw  g dpdq the differential element of the phase space
c1i (T ) =  s − 1 coefficient in the
 p
c T M a  Ra T E internal energy
generation term in the ice supersaturation
Ekin(pm) kinetic energy of a particle depending
equation
on momentum pm
Dρ
c3 w = v ws coefficient in the equation for E(R, r) particles collision efficiency
ρ w Γ1
droplet radius growth rate En quantum energy at the n-th level
Dρ Eij(w) spectral density of turbulent energy
c3i = ζ i v is coefficient in the equation for eɶ internal energy per mole or unit mass
ρ i Γi
crystal axis or radius growth rate ev pressure of water vapor
 L (T − T )  ews pressure of water vapor saturated over water
cwi = exp  m 0  coefficient in the eis pressure of water vapor saturated over ice
 Rv T0 T 
relation between water sw and ice si erf(z) error function
supersaturations
cpi,m isobaric molar heat capacity of ice F Helmholtz free energy of the system
cpi specific heat capacity of ice FD = 6phrV drag force of a spherical body with
cv heat capacity at constant volume per mole or radius r falling with the velocity V in a
unit mass medium with the dynamic viscosity h
cv = rv/mw molecular concentration Fgr = mg gravitational force acting on a body in
the gravitational field
cp heat capacity at constant pressure per mole or
unit mass Fid Helmholtz free energy F of an ideal gas
ci heat capacity of ice FEOS free energy of a simple liquid described
by the equation of state of van der Waals
cw heat capacity of water
theory
cg = csat ,w exp(− ∆Fg /kT ) Boltzmann’sdistribution
2Fhb free energy of the hydrogen bonds
of g-mers
DFa,del activation energy for transition of the
csat,w concentration of the monomers (water
salt molecules from the solid to the liquid
molecules) in a water-saturated
solution at deliquescence
environment
DFact activation energy for transition of the
ccon = Gs r = bcon c1wτ f parameter in the stochastic
water molecules through a potential barrier
condensation theory
at nucleation
Notations 769

DFcr,del critical energy of deliquescence hw, hi molar enthalpies of water and ice
DFcr,eff critical energy of efflorescence h(x, y) height of surface relief
DFcr critical energy of nucleation in the −Dhs molar heat (enthalpies) of salt dissolution
processes of condensation, deposition,
freezing Icon vapor flux to (from) the drops at condensation
Fij(w) spectral function of turbulence at (evaporation), the source or sink term in
frequency w the supersaturation equation
F(a, b; x) confluent hypergeometric (Kummer) Idep vapor flux to (from) the crystals at deposition
function (sublimation), the source or sink term in
F(a, b, g; x) Gauss hypergeometric function the supersaturation equation
ρ
fh specific Helmholtz free energy I con = ws sweq,liq equilibrium condensation rate
eq

Γ1τ fd
f ( x , r , ξi ) distribution function in the phase in a liquid cloud
space of (n + 4) of its variables eq ρis eq
I dep = si ,ice equilibrium deposition rate in a
f(m) size distribution function of the cloud Γ2τ fc
particles by masses crystalline cloud
f(r) size distribution function of the cloud IWC ice water content
particles by radii r i van’t Hoff’s factor
fa(ra) = CNara−n inverse power law for the size
spectra of aerosol or large drops and Jc,dif diffusional vapor flux to the drop surface
crystals + −
J kin, J kin kinetic condensation and evaporation
f(r) = cNrpexp(−brl) generalized gamma molecular fluxes to and from the drop
distributions
Jheat heat flux from the drop or crystal surface
f(r) = cNrpexp(−br) gamma distributions
Jcond,hom homogeneous nucleation rate of the
fs(r) small-size distribution function drops from supersaturated vapor
fl(r) large-size distribution function Jdep deposition nucleation freezing rate
fv. ventilation coefficient in the drop and crystal Jf,hom homogeneous freezing nucleation rate
growth rates
Jf,het heterogeneous freezing nucleation rate
jh = − k a∇T heat flux density around a drop or
G Gibbs free energy
crystal
Gn = RT/(MwLmef) non-dimensional power (+)
jg flux of the monomers to the germ (g-mer) of
index describing the effect of Sw in the
a new phase
theories of homogeneous and heterogeneous
freezing
Kb ebullioscopic constant
D cp γ d − γ w
Gs = v ρa dimensionless parameter Kf cryoscopic constant
ρ w r L 4π DNr
of the stochastic condensation theory KCB collection or scavenging rates [cm3 s−1] for
convective Brownian diffusion
g Gibbs free energy per mole or unit mass
KTh collection rates for thermophoresis
g acceleration of gravity
KDf collection rates for diffusiophoresis
gs = ν RT /( Lefc M s) dimensionless parameter
of the theories deliquescence and Ksc total aerosol collection or scavenging rate
efflorescence Kik coagulation collection kernel
K(m, m′) collection kernel in the mass space
H enthalpy or heat function Kn = lf/r Knudsen number
h enthalpy per mole or unit mass Kext, Ksc, and Kabs factors of radiation extinction,
h Planck’s constant scattering, and absorption
770 Notations

k = R/NAv = 1.38 × 10−16 erg K−1 Boltzmann’s Ma ≈ 28.96 g mole−1 molecular weight of the
constant dry air
ka thermal conductivity coefficient of humid air Ms molecular weight of the soluble fraction
[cal/(cm sec °C)] (solute) in solution
kf = Ce/rc dimensionless crystal shape factor Mw ≈ 18.015 g mole−1 molecular weight
ka0 = 4 /( 2π σ d ) index of the algebraic size of water
spectra m mass of any molecule
4 4 mw1 = Mw/NAv ≈ 3 × 10−23 g mass of a water
ks 0 = = index of the
2π ln σ s 2π (1 + β ) ln σ d molecule
algebraic activity spectra ma = Ma/NAv ≈ 4.8 × 10−23 g mass of the air
kT = ka/(racp) thermal diffusivity coefficient of molecule
air [cm2 s−1] md mass of a dry aerosol particle or mass of a
kv the mean transfer coefficient in the ventilation droplet
corrections mɺ dif = dmd /dt diffusional drop mass growth rate
kw the rational activity coefficient in solutions ms, mw the masses of the soluble fraction and
kx, ky, kz horizontal and vertical components of water in solution
the turbulent coefficient
kij turbulence diffusion tensor coefficient N total number of particles in the system
kijnn (τ f ) turbulence tensor coefficient for a non- N particle concentration (number of particles in
conservative substance a unit volume; 1 cm3 or 1 L or 1 m3)
NAv = 6.023 × 1023 molecules mole−1 Avogadro’s
Lc specific heat (enthalpy) of salt dissolution number
Lefc (T ) specific salt dissolution heat averaged Nd, Nc droplet and crystal concentrations or
over the temperature number densities, the numbers of particles
Le, Lv specific latent heat of evaporation or con- in a unit volume of a cloud
densation, [cal g−1] Ncc number of salt molecules in a salt crystal in
ˆ
Le = M w Le molar latent heat of evaporation or contact with the unit area of solution
condensation Nw number of thermodynamic degrees of
Lm specific melting heat, [cal g−1] freedom in a system
Lefm (T ) specific melting heat averaged over the Nl = NAv /vw = 1/vw1 ≈ 3.34 × 1022 cm−3 concen-
temperature tration of molecules in liquid water
Lˆ m = M w Lm molar melting heat NI = NAv /vi = 1/vi1 ≈ 3.06 × 1022 cm−3 concentra-
Ls specific latent heat of sublimation or deposition, tion of molecules in ice
[cal g−1] N dr(1),l, N dr(2),l, N dr(3),l, N dr(4),l concentrations of drops
Lˆ s = M w Ls molar latent heat of sublimation or activated on CCN in the 1st, 2nd, 3rd, and
deposition 4th limits of the lower bound
Lvis visibility or visual range in a fog N dr(1),u, N dr(2),u, N dr(3),u, N dr(4),u concentrations of drops
or cloud activated on CCN in the 1st, 2nd, 3rd, and
4th limits of the upper bound
LWC liquid water content
nk number of moles of the k-th chemical compo-
lr′ mixing length in radii space
nent in the system
lmix, lj′ Prandtl’s mixing length
nk average number of particles in each energy
state ek in statistical distributions
M̂ molality, the number of moles of salt dissolved
nk average number of particles in each k-state
in 1000 g of water
 µ − εk 
M(n) n-th moment of the size spectrum nk = exp 
 kT 
Boltzmann’s distribution
Notations 771

1 qsup,w = qv − qws specific supersaturation

nk = Bose–Einstein
exp [( ε k − µ) /kT − 1] over water
distribution qsup,i = qv – qis specific supersaturation
1 over ice
nk = Fermi–Dirac  dql  cp
exp [( ε k − µ) /kT + 1]
  =
dz  ad Le
(γ a − γ w ) ρa adiabatic vertical
distribution
nl = mil − ikil complex radiation refractive gradient of the water mixing ratio
 dqi  cp
index at the wavelength l for water (i = 1)
  =
dz  ad Ls
(γ a − γ is ) ρa adiabatic vertical gra-
and ice (i = 2); mil and kil are its real and
imaginary parts dient of the ice mixing ratio
nsolv number of moles of solvent in solution qls LWC or IWC of the small-size fraction
qll LWC or IWC of the large-size fraction
P precipitation rate
Pe = Du/kT Peclet number R = kNAv = 8.3144 × 107 erg mole−1 K−1 =
Pr = h/(rakT) Prandtl number 1.9858 cal mole−1 K−1 universal gas constant
p pressure Re = uD/na Reynolds number; D is the particle
p generalized coordinates in statistical energy diameter, u is the velocity
distributions Ra = R/Ma = 2.8706 × 106 erg g−1 K−1 gas constant
p spectral index or the shape parameter of the for the air
gamma distribution Rv = R/Mw = 4.6150 × 106 erg g−1 K−1 gas constant
pEOS pressure determined from the van der for the water vapor
Waals equation of state Rrad = (∂T/∂t)rad radiative temperature change
phb pressure exerted by the hydrogen bonds rate
px, py, pz components of the momentum RHW, RHI relative humidities over water and
ice in percent
b s rwef
p = con 2 = index of gamma distribution Rf,het Polydisperse nucleation rate in heterogeneous
cnn kGs cnn kGs
freezing
obtained in stochastic condensation theory
Rf,hom Polydisperse nucleation rate in homogeneous
freezing
Q heat in the thermodynamic processes
r radius of an aerosol or cloud particle
Qe electrical charge of a charged conductor
t
rb = rd + Dv radius of the boundary sphere
2 Dv ρ a
Qw (t ) = ∫
ρ w Γw t j
∆ w (t ′)dt ′ normalized integral rb = 2Ak/3sw boundary radius between
deliquescent but unactivated interstitial
specific water supersaturation CCN and drops
t
2 Dv ρ aζ i rd radius of a dry aerosol particle or cloud drop
ρi Γ i t∫j
Qi (t ) = ∆ i (t ′)dt ′ normalized integral
rc radius of a crystal
specific ice supersaturation
ra0 mean geometric radius of the lognormal
q heat per mole or unit mass spectra
q generalized coordinates in statistical energy rd,rc mean radius of the droplets or the effective
distributions (mean) radius of the crystals
ql liquid water mixing ratio; liquid water rɺd ,dif , rɺd = drd /dt diffusional droplet radius
content growth rate
qi ice water mixing ratio; ice water content rd,eff, rc,eff effective radius, the ratio of the 3rd to
qv specific humidity the 2nd moments of the spectrum
qws, qis saturated over water and ice specific rm modal radius of the size spectrum
humidities
772 Notations

Sc = ha/(raDv) Schmidt number T temperature

Sh = 2kvrd/Dv Sherwood number T0, Ttr triple point temperature
Sw water saturation ratio Tcr = 647.096 K critical temperature of water’s
Si ice saturation ratio first critical point
Sh entropy of the system Tf,het critical or threshold temperature of hetero-
Swhet,cr critical or threshold water saturation ratio geneous freezing
of heterogeneous nucleation Tf,hom critical or threshold temperature of homo-
Sihet het geneous freezing
,cr = S w ,cr (ews /eis ) critical or threshold
ice saturation ratio of heterogeneous Tdep critical or threshold temperature of
nucleation deposition
hom
Sw ,cr critical or threshold water saturation ratio Tg temperature of glassy transition
of homogeneous nucleation Tm melting temperature
Si ,cr = Swhom
hom
,cr (ews /eis ) critical or threshold ice satu- Tr = (T – T0)/T0 the reduced temperature
ration ratio of homogeneous nucleation Ts spinodal temperature
Swdep,cr critical or threshold water saturation ratio Tdel temperature of deliquescence
of deposition Teff temperature of efflorescence
Si ,cr = Swdep,cr (ews /eis ) critical or threshold ice satu-
dep
Teut temperature of the eutectic point
ration ratio of deposition
DT = T0 − T∞ psychrometric temperature dif-
Ss* = aɶ s /aɶ s* solution supersaturation ference between the drop surface and
δ Swhet,cr = Swhet,cr (T f ,het ) − Swm,cr (Tm ) shift or difference environment
in the critical saturation ratios between dTf, DTf freezing point depression
the melting and heterogeneous freezing dTm, DTm melting point depression
curves at the same temperature
(∂T/∂t)rad the radiative cooling rate caused by
δ Swhom hom m
,cr = S w ,cr (T f ,hom ) − S w ,cr (Tm ) shift or difference the total radiative flux divergence
in the critical saturation ratios between the
t time
melting and homogeneous freezing curves (1) (2) (3) (4)
at the same temperature tml , tml , tml , tml 1st, 2nd, 3rd, and 4th limits of
the lower bound of time of CCN activation
sw = (rv − rws)/rws fractional water
into drops
supersaturation (1) (2) (3) (4)
tmu , tmu , tmu , tmu 1st, 2nd, 3rd, and 4th limits of
sw = (rv − ris)/ris fractional ice supersaturation
the upper bound of time of CCN activation
sweq,liq = c1w wτ fd equilibrium supersaturation in a into drops
liquid cloud
c1i wτ fc
si ,ice =
eq
equilibrium supersaturation in U potential energy of the molecular interactions
1 − c1i wτfc
in a non-ideal gas
an ice cloud
eq Upot(q) potential energy of a particle depending
sw ,mix equilibrium supersaturation in a mixed
on coordinate q
phase cloud
sh molar entropy
(1) (2) (3) (4) V volume of thermodynamic system
sml , sml , sml , sml 1st, 2nd, 3rd, and 4th limits of the
lower bound of maximum supersaturation at Vd volume of the dry aerosol particle or of the
CCN activation into drops drop
(1) (2) (3) (4)
smu, smu , smu , smu 1st, 2nd, 3rd, and 4th limits of the Vt terminal velocity of a body in a medium
upper bound of maximum supersaturation Vw volume of solvent (water) in aqueous solution
at CCN activation into drops or in an aerosol particle
Notations 773

1/2 t

Vw = 
 8 RT 
 mean velocity of the water vapor
yw (t ) = ∫
t0
sw (t ') dt ' integral fractional water
 π Mw  supersaturation
molecules t

Vg(g) effective drift velocity of g-mers in g-

yi (t ) = ∫
t0
si (t ') dt ' integral fractional ice

space in nucleation theory supersaturation

v volume per mole or unit mass
vw = Mw/rw ≈ 18 cm3 g−1 molar volume of water Z statistical sum or the canonical partition
vi = Mw/rw ≈ 19.63 cm3 g−1 molar volume function
of ice ZR, ZD radar reflectivity factor
vw1 = vw/NAv ≈ 3 × 10−23 cm3 volume of a single  ∆Fg 
1/2

Z = Zeldovich factor for a g-mer

 3π kTg 2 
molecule in liquid water
vi1 = vi/NAv ≈ 3.27 × 10−23 cm3 volume of a in nucleation theory
single molecule in ice
vc0 and vs0 molar volumes of the solid crystal ac condensation coefficient
and solution at deliquescence and
ad deposition coefficient
efflorescence
aLi spectral absorption coefficients of longwave
vx, vy, vz components of the velocity
(LW) radiation at wavelength l
vk terminal velocity of the k-th substance
ap coefficient of water thermal expansion
asl(r) Cunningham’s slip-flow correction
W expansion work done on the system
aT thermal accommodation coefficient
Wxr ( x − x ', r − r '| x ', r ') probability of transition (1) (1) (2) (2) (3) (3) (4)
α k1, α up , α low ,up, α up , α low ,up , α up , α low ,up, α up ,
in the 4D phase space in a random process
(4)
α low
from the point ( x − x ', r − r ′) to the point ,up coefficients of relations between the
lower and upper bounds of tm, sm, and Ndr,m
( x , r ) due to a random jump ( x ', r ')
in drop activation (Chapter 7)
w expansion work per mole or unit mass
B(x, y) Euler’s beta function
w weight concentration or weight percent of
solute in solution b = 1/2 parameter describing the volume-pro-
portional soluble fraction in a CCN
wnN micro-canonic distribution
b = 0 parameter describing the surface-propor-
dwp and dwq energy distributions by momentum
tional soluble fraction in a CCN
and coordinates
bT = 4kT/(aTVw) kinetic correction to the growth
dwv ( v x , v y vz ) Maxwell’s differential velocity
rate in thermal conductivity
distribution
wv water vapor mixing ratio
Γ(x) Euler’s gamma function
wws, wis saturated over water and ice water vapor
Γ(x, a) incomplete Euler’s gamma function
mixing ratio
L2e ρv LL ρ
wrad = − (1/γ a )(∂T /∂t )rad “radiative-effective” Γ1 = 1 + ,Γ12 = 1 + e s 2 v ,
Rv c pT 2 ρa Rv c pT ρ a
velocities
L2s ρ v
Γ2 = 1 + psychrometric coeffi-
Rv c pT 2 ρ a
xk mole fraction for the k-th substance
cients in the water and ice supersaturation
xs, xw mole fractions of solute and water in an equations and in the radii growth rates of
aqueous solution drops and crystals
x = 2pr/l size parameter in radiation dΓ the number of states in the differential
calculations element of the phase space
774 Notations

ga dry adiabatic lapse rate l wavelength of radiation

gw wet adiabatic lapse rate in liquid clouds λa (T , p) = λa0 ( p0 /p)(T /T0 ) free molecular path
gis wet adiabatic lapse rate in ice clouds lf ∼ 0.1 mm molecular mean free path length

Dw = qv − qws specific supersaturation mk chemical potential of the k -th chemical com-

over water ponent in the system
Di = qv – qis specific supersaturation over ice µ wi (T ), µ w0 (T ) chemical potentials of water in
Dv thickness of the boundary sphere with kinetic pure ice and of liquid water
molecular flux comparable to la.
DT thickness of the boundary sphere with n frequency of radiation
kinetic molecular heat flux near the drop n the number of ions of a salt or acid in solution
n a kinematic viscosity of the air
dw = rv − rws absolute supersaturation over nm maximum frequency of oscillators in Debye’s
water energy spectrum of a solid
di = rv − ris absolute supersaturation over ice
xcon = 4Dv/(acVw) kinetic correction to the drop
e elastic strain caused by the misfit between ice radius condensation growth rate
and substrate lattices [%] xdep = 4Dv/(adVw) kinetic correction to the crystal
ecw = Icon/ra specific condensation growth rate radius or axis deposition growth rate
eci = Idep/ra specific deposition growth rate xf = b/rc crystal axes ratio (minor to major)
ef specific freezing rate
em specific melting rate r the gas or liquid density
ei cloud emissivity ra air density
em mass soluble fraction of a cloud condensation rcr = 322 kg m−3 the critical density at water’s
nucleus first critical point
ev volume soluble fraction of a cloud condensation re density of the electrical charge
nucleus rv∝ vapor density at infinite distance from the
ek quantum energy state drop
ek′ internal energy of a molecule rs″ solution density
k rws, ris densities of water vapor saturated over
ζ i = k 0 i fin factor describing the effect of the
ξf water and ice
shape on the crystal growth rate ri density of ice
rw density of water
ha = n ara dynamic viscosity of the air d ρε (ν , T ) energy density of radiation
sa dispersion of the lognormal spectrum
q potential temperature sabs absorption cross section
qD = hnm/k Debye’s temperature σɶ ext ,k, σɶsc ,k, αɶ abs ,k volume extinction, scattering,
<cosq> radiation asymmetry parameter and absorption coefficients of the k-th
substance in a cloud
kT isothermal compressibility of water sext,k, ssc,k, sabs,k mass extinction, scattering, and
kvk isobaric compressibility of water absorption coefficients of the k-th sub-
stance in a cloud
σ λs Li, α λs Li spectral scattering coefficients of
Λsc(ra) spectral aerosol scavenging coefficient
shortwave (SW) radiation at wavelength l
Notations 775

sis surface tension at the ice–solution interface tcol = (scol)−1 characteristic coagulation (accre-
siv surface tension at the ice–vapor interface tion) time of the e-folding decrease in qls
siw surface tension at the ice–water interface or corresponding increase in qll
ssa surface tension at the solution–air interface
Fe electrostatic potential around a charged
svw surface tension at the vapor–water interface
conductor
swa surface tension at the water–air interface
Φs molal or practical osmotic potential
scs surface tension at the crystal–solution interface
Φ(x) = erf(x) error function
at deliquescence or efflorescence
sra absolute spectral dispersion by radii
j number of bulk phases in a thermodynamic
srr relative spectral dispersion by radii system
scol collection frequency of the large-size fraction js(sw) supersaturation activity spectrum
in the coagulation equation of CCN
j(dr, tr) dimensionless Helmholtz free energy
tcr cloud crystallization time in the equation of state for liquid water
tfd, tfc supersaturation absorption or re-
laxation times of drops and crystals; cad = qls/qls,ad adiabatic liquid (ice) ratio
τ fd ≈ (4π Dv N d rd )−1, τ fc ≈ (4π Dv N c rc )−1 in
the diffusion regime
ycf(rd,Dt) contact freezing rate (s−1) of the drops
τ f ,mix = [τ −fd1 + (Γ12 /Γ 2 ) τ −fc1] −1 “effective” super- that capture aerosol particles
saturation relaxation time in a mixed cloud
y number of curved interfaces in a thermody-
τ c , fr = Ψ cf−1 (rd , ∆t ) characteristic contact freezing namic system
time that describes the rate of drops freez-
yh(sw) supersaturation activity spectrum of IN
ing due to contact nucleation
τ sc (ra ) = Λ sc−1 (ra ) characteristic scavenging time
W Landau thermodynamic potential
of aerosol with radius ra
text,k optical thickness of the k-th substance in
w frequency of turbulent fluctuation
a cloud
wl single-scattering albedo
tv,rel = 2rbr2/(9h) velocity relaxation time
Index

accretion, 168 Clausius–Clapeyron equation

activation of cloud condensation nucleus (CCN), 69 equilibrium of a water drop with saturated vapor, 74
adiabatic gradient of the ice water mixing ratio, 93 equilibrium of an ice crystal with saturated vapor, 75–78
adiabatic gradient of the liquid water mixing ratio, 92, 662 equilibrium of liquid and ice bulk phases, 73
adiabatic processes generalized, 79
adiabatic lapse rates with non-zero equilibrium cloud climatologies, 15
supersaturations, 157–158 cloud condensation nuclei (CCN), 69
dry adiabatic lapse rate, 89 cloud microphysical properties
dry adiabatic processes, 88–90 absolute dispersion of the spectrum, 30
wet adiabatic lapse rate, 91, 92 droplet and crystal concentrations or number densities, 20
wet adiabatic processes, 90–94 effective radius, 21
adsorption of gases on the crystal surface, 142 ice water content, 27, 30
adsorption of gases on the surface of drops and aerosol ice water path, 21
particles, 181 liquid water content, 21
aerosol size spectra liquid water path, 21
algebraic approximation of the lognormal size mean radius of the droplets or the effective (mean) radius
spectra, 206–211 of the crystals, 20
approximation of the lognormal size spectra by the inverse modal radius, 20
power law, 203–204 precipitation rate, 22
lognormal and inverse power law size spectra, 203 radar reflectivity, 22–23
affinity, 291 relative spectral dispersion, 28, 30
algorithms for microphysics module in multidimensional spectral p-index or the shape parameter of the gamma
models, 173–179 distribution, 30
altocumulus clouds, 10 supersaturation absorption (relaxation) times, 21
altostratus clouds, 10 visibility or visual range, 22
amorphous ice cloud radiative properties
high density amorphous ice (HDA), 101 asymmetry parameter, 32
low density amorphous ice (LDA), 99 backscatter cross sections, 23
Angström index of aerosol extinction coefficient, 182, 184 broadband parameterizations, 37–38
anomalous diffraction theory (ADT), 33 cloud emissivity, 39
Arctic climatic front, 16, 17 complex refractive index for water and ice, 23
artificial ice nuclei, 107, 404 efficiency factors of extinction, scattering,
Avogadro number, 291, 411 and absorption, 34
mass absorption coefficients, 39
bin microphysics method, 168 mass extinction coefficients, 36
boiling point elevation, 85 mass scattering coefficients, 36–37
boundary sphere, method of, 129–130 optical thickness, 32
broad size spectra in clouds and their theories, 613–614 single-scattering albedo, 21, 32
bulk or parameterized microphysics method, 168 volume absorption coefficients, 36
volume extinction coefficients, 36
canonical ensemble, 50 volume scattering coefficients, 36
canonical partition function, 50 cloud seeding, 78
Chapman–Kolmogorov equation, 669–673 cloud-topped boundary layers (CTBL), 18–19
characteristic relaxation times of CCN size and solution clouds
concentration, 435 cloud types
chemical potential, 45, 47, 67, 72, 307 boundary layer clouds Sc-St, 18–19
cirriform clouds, 10 convective cloudiness, 19
cirrus clouds, 10 frontal and cyclonic clouds, 16–17
Clapeyron equation, 73, 101 orographic clouds, 19–20

777