Equipment Design Dr.

Anees Abdullah

UNIVERSITY OF DAIYLA

COLLEGE OF ENGINEERING

CHEMICAL ENGINEERING DEPARTMENT

CHEMICAL ENGINEERING EQUIPMENT DESIGN

For

Third and Fourth Years Chemical Engineering Students

Arranged by

Assist. Prof. Dr. Anees A. Khadom

Ph.D, Ms.C and Bs.C. Chemical Engineering

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Equipment Design Dr. Anees Abdullah

CONTENTS

Chapter one Introduction

Chapter two Piping and Instrumentation

Chapter three Costing and Project Evaluation

Chapter four Materials of Construction

Chapter five Design Information and Data

Chapter six Safety and Loss Prevention

Chapter seven Equipment Selection, Specification, and Design

Chapter eight Separation Columns (Distillation, Absorption, and

Extraction)

Chapter nine Heat-transfer Equipment

Chapter ten Mechanical Design of Process Equipment

Chapter eleven General Site Considerations

Reference books:

1. Chemical Engineering, Volume 6, Fourth edition, Chemical Engineering Design, R. K.

Sinnott.
2. Plant Design and Economics for Chemical Engineers, Fourth edition, Max S. Peters,
Klaus D. Timmerhaus

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CHAPTER ONE

INTRODUCTION

In this modern age of industrial competition, a successful chemical engineer needs more than a
knowledge and understanding of the fundamental sciences and the related engineering subjects
such as thermodynamics, reaction kinetics, and computer technology. The engineer must also
have the ability to apply this knowledge to practical situations for the purpose of accomplishing
something that will be beneficial to society. However, in making these applications, the chemical
engineer must recognize the economic implications which are involved and proceed accordingly.
Chemical engineering design of new chemical plants and the expansion or revision of existing
ones require the use of engineering principles and theories combined with a practical realization
of the limits imposed by industrial conditions. Development of a new plant or process from
concept evaluation to profitable reality is often an enormously complex problem. A plant-design
project move to completion through a series of stages such as is shown in the following:
1. Inception
2. Preliminary evaluation of economics and market
3. Development of data necessary for final design
4. Final economic evaluation
5. Detailed engineering design
6. Procurement
7. Construction
8. Startup and trial runs
9. Production

In almost every case encountered by a chemical engineer, there are several alternative methods
which can be used for any given process or operation. For example, formaldehyde can be
produced by catalytic t dehydrogenation of methanol, by controlled oxidation of natural gas, or
by direct reaction between CO and H2, under special conditions of catalyst, temperature, and
pressure. Each of these processes contains many possible alternatives involving variables such as
gas-mixture composition, temperature, pressure, and choice of catalyst. It is the responsibility of
the chemical engineer, in this case, to choose the best process and to incorporate into the design
the equipment and methods which will give the best results. A principle responsibility of the
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chemical engineer is the design, construction, and operation of chemical plants. In this
responsibility, the engineer must continuously search for additional information to assist in these
functions. Such information is available from numerous sources, including recent publications,
operation of existing process plants, and laboratory and pilot-plant data.
Types of Designs
The methods for carrying out a design project may be divided into the following classifications,
depending on the accuracy and detail required:
1. Preliminary or quick-estimate designs
2. Detailed-estimate designs
Preliminary designs are ordinarily used as a basis for determining whether further work should
be done on the proposed process. The design is based on approximate process methods, and
rough cost estimates are prepared. Few details are included, and the time spent on calculations is
kept at a minimum. If the results of the preliminary design show that further work is justified, a
detailed-estimate design may be developed. In this type of design, the cost and-profit potential of
an established process is determined by detailed analyses and calculations.
Feasibility Survey
Before any detailed work is done on the design, the technical and economic factors of the
proposed process should be examined. Following is a list of items that should be considered in
making a feasibility survey:
1. Raw materials (availability, quantity, quality, cost)
2. Thermodynamics and kinetics of chemical reactions involved (equilibrium, yields, rates,
optimum conditions)
3. Facilities and equipment available at present
4. Facilities and equipment which must be purchased
5. Estimation of production costs and total investment
6. Profits (probable and optimum, per pound of product and per year, return on investment)
7. Materials of construction
8. Safety considerations
9. Markets (present and future supply and demand, present uses, new uses, present buying habits,
price range for products and by-products, character, location, and number of possible customers)

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10. Competition (overall production statistics, comparison of various manufacturing processes,

product specifications of competitors)
11. Properties of products (chemical and physical properties, specifications, impurities, effects of
storage)
12. Sales and sales service (method of selling and distributing, advertising required, technical
services required)
13. Shipping restrictions and containers
14. Plant location
15. Patent situation and legal restrictions
Equipment specifications
1. Columns (distillation). In addition to the number of plates and operating conditions it is also
necessary to specify the column diameter, materials of construction, plate layout, etc.
2. Vessels. In addition to size, which is often dictated by the holdup time desired materials of
construction and any packing or baffling should be specified.
3. Reactors. Catalyst type and size, bed diameter and thickness, heat-interchange facilities, cycle
and regeneration arrangements, materials of construction, etc., must be specified.
4. Heat exchangers and furnaces. Manufacturers are usually supplied with the duty, corrected
log mean-temperature difference, percent vaporized, pressure drop desired, and materials of
construction.
5. Pumps and compressors. Specify type, power requirement, pressure difference, gravities,
viscosities, and working pressures.
6. Instruments. Designate the function and any particular requirement.
7. Special equipment. Specifications for mechanical separators, mixers, driers, etc.
Flow Diagrams
The chemical engineer uses flow diagrams to show the sequence of equipment and unit
operations in the overall process, to simplify visualization of the manufacturing procedures, and
to indicate the quantities of materials and energy transfer. These diagrams may be divided into
three general types:
(1) qualitative, (2) quantitative, and (3) combined-detail.
A qualitative flow diagram indicates the flow of materials, unit operations involved, equipment
necessary, and special information on operating temperatures and pressures. A quantitative flow

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diagram shows the quantities of materials required for the process operation. An example of a
qualitative flow diagram for the production of nitric acid is shown in Fig. 2-1. Figure 2-2
presents a quantitative flow diagram for the same process.

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Literature Survey

A survey of the literature reveals that the majority of the nonbiodegradable detergents are
alkylbenzene sulfonates (ABS). Theoretically, there are over 80,000 isomeric alkylbenzenes in
the range of C,, to C,, for the alkyl side chain. Costs, however, generally favor the use of
dodecene (propylene tetramer) as the starting material for ABS. There are many different
schemes in the manufacture of ABS. Most of the schemes are variations of the one shown in Fig.
3 for the production of sodium dodecylbenzene sulfonate.

A brief description of the process is as follows:

This process involves reaction of dodecene with benzene in the presence of aluminum chloride
catalyst; fractionation of the resulting crude mixture to recover the desired boiling range of
dodecylbenzene; sulfonation of the dodecylbenzene and subsequent neutralization of the sulfonic
acid with caustic soda; blending the resulting slurry with chemical “builders”; and drying.
Dodecene is charged into a reaction vessel containing benzene and aluminum chloride. The
reaction mixture is agitated and cooled to maintain the reaction temperature of about 115°F

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maximum. An excess of benzene is used to suppress the formation of by-products. Aluminum

chloride requirement is 5 to 10 wt% of dodecene.
After removal of aluminum chloride sludge, the reaction mixture is fractionated to recover
excess benzene (which is recycled to the reaction vessel), a light alkylaryl hydrocarbon,
dodecylbenzene, and a heavy alkylaryl hydrocarbon. Sulfonation of the dodecylbenzene may be
carried out continuously or batch-wise under a variety of operating conditions using sulfuric acid
(100 percent), oleum (usually 20 percent SO,), or anhydrous sulfur trioxide. The optimum
sulfonation temperature is usually in the range of 100 to 140°F depending on the strength of acid
employed, mechanical design of the equipment, etc. Removal of the spent sulfuric acid from the
sulfonic acid is facilitated by adding water to reduce the sulfuric acid strength to about 78
percent. This dilution prior to neutralization results in a final neutralized slurry having
approximately 85 percent active agent based on the solids. The inert material in the final product
is essentially Na2SO4. The sulfonic acid is neutralized with 20 to 50 percent caustic soda solution
to a pH of 8 at a temperature of about 125°F. Chemical “builders” such as trisodium phosphate,
tetrasodium pyrophosphate, sodium silitate, sodium chloride, sodium sulfate, carbovethyl
cellulose, etc., are added to enhance the detersive, wetting, or other desired properties in the
finished product. A flaked, dried product is obtained by drum drying or a bead product is
obtained by spray drying. The basic reactions which occur in the process are the following.

A literature search indicates that yields of 85 to 95 percent have been obtained in the alkylation
step, while yields for the sulfonation process are substantially 100 percent, and yields for the
neutralization step are always 95 percent or greater. All three steps are exothermic and require
some form of jacketed cooling around the stirred reactor to maintain isothermal reaction
temperatures. Laboratory data for the sulfonation of dodecylbenzene, described in the literature,
provide additional information useful for a rapid material balance. This is summarized as
follows:

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1. Sulfonation is essentially complete if the ratio of 20 percent oleum to dodecylbenzene is

maintained at 1.25.
2. Spent sulfuric acid removal is optimized with the addition of 0.244 lb of water to the settler for
each 1.25 lb of 20 percent oleum added in the sulfonation step.
3. A 25 percent excess of 20 percent NaOH is suggested for the neutralization step.
Operating conditions for this process, as reported in the literature, vary somewhat depending
upon the particular processing procedure chosen.
Material and Energy Balance
The process selected for the manufacture of the nonbiodegradable detergent is essentially
continuous even though the alkylation, sulfonation, and neutralization steps are semicontinuous
steps. Provisions for possible shutdowns for repairs and maintenance are incorporated into the
design of the process by specifying plant operation for 300 calendar days per year. Assuming 90
percent yield in the alkylator and a sodium dodecylbenzene sulfonate product to be 85 percent
active with 15 percent sodium sulfate as inert, the overall material balance is as follows:
Input components:

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The weight of the heavy alkylaryl hydrocarbon is obtained by difference as 3516 lb/day. The
material balance summary made by the design group for the process shown in Fig. 3 is given on
a daily basis in Fig. 4. After a complete material balance is made, the mass quantities are used to
compute energy balances.

Around each piece of equipment, Temperature and pressure levels at various key points in the
process, particularly at the reactors, serve as guides in making these heat balances. The complete
calculations for the material and energy balances for each piece of equipment, because of their
length, are not presented in this discussion.
Equipment Design and Selection
Equipment design for this preliminary process evaluation involves determining the size of the
equipment in terms of the volume, flow per unit time, or surface area. Some of the calculations
associated with the alkylation unit are presented in the following to indicate the extent of the
calculations which are sometimes adequate for a preliminary design.

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Continuous and batch processes

Continuous processes are designed to operate 24 hours a day, 7 days a week, throughout the
year. Some down time will be allowed for maintenance and, for some processes, catalyst
regeneration. Batch processes are designed to operate intermittently. Some, or all, the process
units being frequently shut down and started up. Continuous processes will usually be more
economical for large scale production. Batch processes are used where some flexibility is wanted
in production rate or product specification.

CONSERVATION OF MASS
The general conservation equation for any process system can be written as:

Material out = Material in + Generation - Consumption – Accumulation

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THE ENERGY BALANCE

Consider a steady-state process represented by Figure 5. The conservation equation can be

written to include the various forms of energy.

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The suffixes 1 and 2 represent the inlet and outlet points respectively. Q is the heat transferred
across the system boundary; positive for heat entering the system, negative for heat leaving the
system. W is the work done by the system; positive for work going from the system to the
surroundings, and negative for work entering the system from the surroundings.
Example
Balance with no chemical reaction. Estimate the steam and the cooling water required for the
distillation column shown in the figure. Steam is available at 25 psig (274 kN/m2 abs), dry
saturated. The rise in cooling water temperature is limited to 300C. Column operates at 1 bar.

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Reflux ratio (see Chapter 11, Volume 6, Chemical Engineering):

From vapor liquid equilibrium data: boiling point of 99 per cent acetone/water = 56.50C. At steady state:

There are two ways of calculating the specific enthalpy of the vapor at its boiling point.
(1) Latent heat of vaporisation at the base temperature C sensible heat to heat the vapour to the
boiling point.
(2) Latent heat of vaporisation at the boiling point C sensible heat to raise liquid to the boiling
point.
Values of the latent heat of acetone and water as functions of temperature are given in Volume 1,
so the second method will be used.
Latent heat acetone at 56.50C (330 K) = 620 kJ/kg
Water at 56.50C (330 K) = 2500 kJ/kg
Taking latent heats as additive:

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CALCULATION OF SPECIFIC ENTHALPY

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Note

The student must make use and review all the principles and basics of
material and energy balance, units, dimensions, pressure, temperature,
heat of mixing, humidity, enthalpy changes, and all information of
previous years.

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CHAPTER TWO
PIPING AND INSTRUMENTATION
The process flow-sheet shows the arrangement of the major pieces of equipment and their
interconnection. It is a description of the nature of the process. The Piping and Instrument
diagram (P and I diagram or PID) shows the engineering details of the equipment, instruments,
piping, valves and fittings; and their arrangement. It is often called the Engineering Flow-sheet
or Engineering Line Diagram.
THE P AND I DIAGRAM
The P and I diagram shows the arrangement of the process equipment, piping, pumps,
instruments, valves and other fittings. It should include:
1. All process equipment identified by an equipment number. The equipment should be drawn
roughly in proportion, and the location of nozzles shown.
2. All pipes, identified by a line number. The pipe size and material of construction should be
shown. The material may be included as part of the line identification number.
3. All valves, control and block valves, with an identification number. The type and size should
be shown. The type may be shown by the symbol used for the valve or included in the code used
for the valve number.
4. Ancillary fittings that are part of the piping system, such as inline sight-glasses, strainers and
steam traps; with an identification number.
5. Pumps, identified by a suitable code number.
6. All control loops and instruments, with an identification number.
Symbols and layout
The symbols used to show the equipment, valves, instruments, and control loops will depend on
the practice of the particular design office. The equipment symbols are usually more detailed
than those used for the process flow-sheet. A typical example of a P and I diagram is shown in
Figure 6. Standard symbols for instruments, controllers, and valves are given in the British
Standard BS 1646.

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Basic symbols
The symbols illustrated below are those given in BS 1646.

Failure mode
The direction of the arrow shows the position of the valve on failure of the power supply.

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Instruments and controllers

Locally mounted means that the controller and display is located out on the plant near to the
sensing instrument location. Main panel means that they are located on a panel in the control
room. Except on small plants, most controllers would be mounted in the control room.
Type of instrument
This is indicated on the circle representing the instrument-controller by a letter code (see
Table)

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VALVE SELECTION

The valves used for chemical process plant can be divided into two broad classes, depending on
their primary function:
1. Shut-off valves (block valves), whose purpose is to close off the flow.
2. Control valves, both manual and automatic, used to regulate flow.

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The main types of valves used are:

a. Gate
b. Plug
c. Ball
d. Globe
e. Diaphragm
f. Butterfly
g. Non-return valve

A valve selected for shut-off purposes should give a positive seal in the closed position and
minimum resistance to flow when open. Gate, plug, and ball valves are most frequently used for
this purpose. If flow control is required, the valve should be capable of giving smooth control
over the full range of flow, from fully open to closed. Globe valves are normally used, though
the other types can be used. Butterfly valves are often used for the control of gas and vapour
flows. The careful selection and design of control valves is important; good flow control must be
achieved, whilst keeping the pressure drop as low as possible. The valve must also be sized to
avoid the flashing of hot liquids and the super-critical flow of gases and vapours. Non-return
valves are used to prevent back-flow of fluid in a process line. They do not normally give an
absolute shut-off of the reverse flow. A typical design is shown in Figure g.

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Pump and pump selection

Pumps can be classified into two general types:
1. Dynamic pumps, such as centrifugal pumps.
2. Positive displacement pumps, such as reciprocating and diaphragm pumps.
The single-stage, horizontal, overhung, centrifugal pump is by far the most commonly used type
in the chemical process industry. Other types are used where a high head or other special process
considerations are specified. Pump selection is made on the flow rate and head required, together
with other process considerations, such as corrosion or the presence of solids in the fluid. The
chart shown in Figure below can be used to determine the type of pump required for a particular
head and flow rate.

Centrifugal pumps are characterized by their specific speed. In the dimensionless form, specific
speed is given by:

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The specific speed for centrifugal pumps (Ns`) usually lies between 400 and 10,000, depending
on the type of impeller. Generally, pump impellers are classified as radial for specific speeds
between 400 and 1000, mixed flow between 1500 and 7000, and axial above 7000. Positive
displacement, reciprocating, pumps are normally used where a high head is required at a low
flow-rate.
Pressure drop in pipelines
The pressure drop in a pipe, due to friction, is a function of the fluid flow-rate, fluid density, and
viscosity, pipe diameter, pipe surface roughness, and the length of the pipe. It can be calculated
using the following equation:

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Example
A pipeline connecting two tanks contains four standard elbows, a plug valve that is fully open,
and a gate valve that is half open. The line is commercial steel pipe, 25 mm internal diameter,
length 120 m. The properties of the fluid are: viscosity 0.99 mNM-2 s, density 998 kg/m3.
Calculate the total pressure drop due to friction when the flow rate is 3500 kg/h.

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Example
A tanker carrying toluene is unloaded, using the ship’s pumps, to an on-shore storage tank. The
pipeline is 225 mm internal diameter and 900 m long. Miscellaneous losses due to fittings,
valves, etc., amount to 600 equivalent pipe diameters. The maximum liquid level in the storage
tank is 30 m above the lowest level in the ship’s tanks. The ship’s tanks are nitrogen blanketed
and maintained at a pressure of 1.05 bar. The storage tank has a floating roof, which exerts a
pressure of 1.1 bar on the liquid. The ship must unload 1000 tonne within 5 hours to avoid
demurrage charges. Estimate the power required by the pump. Take the pump efficiency as 70
per cent. Physical properties of toluene: density 874 kg/m3, viscosity 0.62 mNm-2 s.

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TYPICAL CONTROL SYSTEMS

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CHAPTER FOUR
MATERIALS OF CONSTRUCTION
Many factors have to be considered when selecting engineering materials, but for
chemical process plant the overriding consideration is usually the ability to resist corrosion. The
process designer will be responsible for recommending materials that will be suitable for the
process conditions.
MATERIAL PROPERTIES
The most important characteristics to be considered when selecting a material of construction
are:
1. Mechanical properties
(a) Strength tensile strength
(b) Stiffness elastic modulus (Young’s modulus)
(c) Toughness fracture resistance
(d) Hardness wear resistance
(e) Fatigue resistance
(f) Creep resistance
2. The effect of high and low temperatures on the mechanical properties.
3. Corrosion resistance
4. Any special properties required; such as, thermal conductivity, electrical resistance, magnetic
properties
5. Ease of fabrication forming, welding, and casting (see Table 7.1)
6. Availability in standard sizes plates, sections, tubes
7. Cost.

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1. MECHANICAL PROPERTIES
Typical values of the mechanical properties of the more common materials used in the
construction of chemical process equipment are given in Table 7.2.

Tensile strength
The tensile strength (tensile stress) is a measure of the basic strength of a material. It is the
maximum stress that the material will withstand, measured by a standard tensile test.
Stiffness
Stiffness is the ability to resist bending and buckling.
Toughness
Toughness is associated with tensile strength, and is a measure of the material’s resistance to
crack propagation.
Hardness
The surface hardness, as measured in a standard test, is an indication of a material’s ability to
resist wear.
Fatigue
Fatigue failure is likely to occur in equipment subject to cyclic loading; for example, rotating
equipment, such as pumps and compressors, and equipment subjected to pressure cycling.
Creep
Creep is the gradual extension of a material under a steady tensile stress, over a prolonged period
of time. It is usually only important at high temperatures; for instance, with steam and gas
turbine blades.

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2. Effect of temperature on the mechanical properties

The tensile strength and elastic modulus of metals decrease with increasing temperature. For
example, the tensile strength of mild steel (low carbon steel, C < 0.25 per cent) is 450 N/mm2 at
25oC falling to 210 at 5000C, and the value of Young’s modulus 200,000 N/mm2 at 25oC falling
to 150,000 N/mm2 at 500oC. If equipment is being designed to operate at high temperatures,
materials that retain their strength must be selected. Creep resistance will be important if the
material is subjected to high stresses at elevated temperatures.
3. CORROSION RESISTANCE
The conditions that cause corrosion can arise in a variety of ways. For this brief discussion on the
selection of materials it is convenient to classify corrosion into the following categories:
1. General wastage of material uniform corrosion.
2. Galvanic corrosion dissimilar metals in contact.
3. Pitting localized attack.
4. Intergranular corrosion.
Stress corrosion.
6. Erosion corrosion.
7. Corrosion fatigue.
8. High temperature oxidation.
9. Hydrogen embrittlement.
MATERIAL COSTS
An indication of the cost of some commonly used metals is given in Table 7.5. The actual cost of
metals and alloys will fluctuate quite widely, depending on movements in the world metal
exchanges. The quantity of a material used will depend on the material density and strength
(design stress) and these must be taken into account when comparing material costs. cost rating
factor defined by the equation:

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Commonly Used Materials of Construction

The general mechanical properties, corrosion resistance, and typical areas of use of some of the
materials commonly used in the construction of chemical plant are given in this section.
1. Iron and steel
Low carbon steel (mild steel) is the most commonly used engineering material. It is cheap; is
available in a wide range of standard forms and sizes; and can be easily worked and welded. It
has good tensile strength and ductility.
2. Stainless steel
The stainless steels are the most frequently used corrosion resistant materials in the chemical
industry.
3. Nickel
Nickel has good mechanical properties and is easily worked. The pure metal (>99 per cent) is not
generally used for chemical plant, its alloys being preferred for most applications. The main use
is for equipment handling caustic alkalies at temperatures above that at which carbon steel could
be used; above 700C. Nickel is not subject to corrosion cracking like stainless steel.
4. Monel
Monel, the classic nickel-copper alloy with the metals in the ratio 2 : 1, is probably, after the
stainless steels, the most commonly used alloy for chemical plant. It is easily worked and has
good mechanical properties up to 500ŽC. It is more expensive than stainless steel but is not
susceptible to stress-corrosion cracking in chloride solutions. Monel has good resistance to dilute
mineral acids and can be used in reducing conditions, where the stainless steels would be
unsuitable. It may be used for equipment handling, alkalies, organic acids and salts, and sea
water.

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5. Copper and copper alloys

Pure copper is not widely used for chemical equipment. It has been used traditionally in the food
industry, particularly in brewing. Copper is a relatively soft, very easily worked metal, and is
used extensively for small-bore pipes and tubes. The main alloys of copper are the brasses,
alloyed with zinc, and the bronzes, alloyed with tin. Other, so-called bronzes are the aluminium
bronzes and the silicon bronzes. Copper is attacked by mineral acids, except cold, dilute,
unaerated sulphuric acid.
6. Aluminum and its alloys
Pure aluminum lacks mechanical strength but has higher resistance to corrosion than its alloys.

Plastics as Materials of Construction for Chemical Plant

Plastics are being increasingly used as corrosion-resistant materials for chemical plant
construction. Such as, Poly-vinyl chloride (PVC).
Rubber
Rubber, particularly in the form of linings for tanks and pipes, has been extensively used in the
chemical industry for many years. Natural rubber is most commonly used, because of its good
resistance to acids (except concentrated nitric) and alkalies. It is unsuitable for use with most
organic solvents. Synthetic rubbers are also used for particular applications.

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CHAPTER FIVE
DESIGN INFORMATION AND DATA
Information on manufacturing processes, equipment parameters, materials of construction, costs
and the physical properties of process materials are needed at all stages of design; from the initial
screening of possible processes, to the plant start-up and production. When a project is largely a
repeat of a previous project, the data and information required for the design will be available in
the Company’s process files, if proper detailed records are kept. For a new project or process, the
design data will have to be obtained from the literature, or by experiment (research laboratory
and pilot plant), or purchased from other companies. The information on manufacturing
processes available in the general literature can be of use in the initial stages of process design,
for screening potential process; but is usually mainly descriptive, and too superficial to be of
much use for detailed design and evaluation.
PREDICTION OF PHYSICAL PROPERTIES
1. DENSITY
1.1 Liquid density
Values for the density of pure liquids can usually be found in the handbooks. It should be noted
that the density of most organic liquids, other than those containing a halogen or other “heavy
atom”, usually lies between 800 and 1000 kg/m3.

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2. VISCOSITY
Viscosity values will be needed for any design calculations involving the transport of fluids or
heat.
2.1 Viscosity of Liquids
A rough estimate of the viscosity of a pure liquid at its boiling point can be obtained from the
modified Arrhenius equation:

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Variation with temperature

If the viscosity is known at a particular temperature, the value at another temperature can be
estimated with reasonable accuracy by using the generalized plot Figure 8.1. The scale of the
temperature ordinate is obtained by plotting the known value, as illustrated in Example 8.3.

Example 8.3
Estimate the viscosity of toluene at 800C, using the value at 200C given in Example 8.2.

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Effect of pressure
The viscosity of a liquid is dependent on pressure as well as temperature, but the effect is not
significant except at very high pressures. A rise in pressure of 300 bar is roughly equivalent to a
decrease in temperature of 10C.
Mixtures
It is difficult to predict the viscosity of mixtures of liquids. Viscosities are rarely additive, and
the shape of the viscosity-concentration curve can be complex. The viscosity of the mixture may
be lower or, occasionally, higher than that of the pure components. For a binary mixture equation
8.9 becomes:

For heat-transfer calculations

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THERMAL CONDUCTIVITY
The experimental methods used for the determination of thermal conductivity are described in
books, which lists values for many substances.
Solids
The thermal conductivity of a solid is determined by its form and structure, as well as
composition. Values for the commonly used engineering materials are given in various
handbooks.
Liquids
The Weber equation can be used to make a rough estimate of the thermal conductivity of organic
liquids, for use in heat-transfer calculations.

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Gases
Approximate values for the thermal conductivity of pure gases, up to moderate pressures, can be
estimated from values of the gas viscosity, using Eucken’s equation:

Example
Estimate the thermal conductivity of ethane at 1 bar and 4500C.

Mixtures
In general, the thermal conductivities of liquid mixtures, and gas mixtures, are not simple
functions of composition and the thermal conductivity of the components. If the components are
all non-polar a simple weighted average is usually sufficiently accurate for design purposes.

SPECIFIC HEAT CAPACITY

The specific heats of the most common organic and inorganic materials can usually be found in
the handbooks.
Solids and liquids
Approximate values can be calculated for solids, and liquids, by using a modified form of
Kopp’s law. The heat capacity of a compound is taken as the sum of the heat capacities of the

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individual elements of which it is composed. The values attributed to each element, for liquids
and solids, at room temperature, are given in Table 8.2; the method illustrated in Example 8.6.

Kopp’s rule does not take into account the arrangement of the atoms in the molecule, and, at
best, gives only very approximate. For organic liquids, the group contribution method proposed
by Chueh and Swanson will give accurate predictions. The contributions to be assigned to each
molecular group are given in Table 8.3 and the method illustrated in Examples 8.7 and 8.8. The
specific heats of liquid mixtures can be estimated, with sufficient accuracy for most technical
calculations, by taking heat capacities of the components as additive. For dilute aqueous
solutions it is usually sufficient to take the specific heat of the solution as that of water.

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Several group contribution methods have been developed for the estimation of the constants,
such as that by Rihani and Doraiswamy (1965) for organic compounds. Their values for each
molecular group are given in Table 8.4, and the method illustrated in Example 8.9. The values
should not be used for acetylenic compounds.

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ENTHALPY OF VAPORISATION (LATENT HEAT)

The latent heats of vaporisation of the more commonly used materials can be found in the
handbooks and in Appendix C. A very rough estimate can be obtained from Trouton’s rule
(Trouton, 1884), one of the oldest prediction methods.

For organic liquids the constant can be taken as 100. More accurate estimates, suitable for most
engineering purposes, can be made from knowledge of the vapour pressure-temperature
relationship for the substance. Several correlations have been proposed and derived from the
Antoine vapour pressure equation (see Section 8.11).

If an experimental value of the latent heat at the boiling point is known, the Watson equation
(Watson, 1943), can be used to estimate the latent heat at other temperatures.

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VAPOUR PRESSURE
If the normal boiling point (vapour pressure = 1 atm) and the critical temperature and pressure
are known, then a straight line drawn through these two points on a plot of log pressure versus
reciprocal absolute temperature can be used to make a rough estimation of the vapour pressure at
intermediate temperatures. Several equations have been developed to express vapour pressure as
a function of temperature. One of the most commonly used is the three-term Antoine equation,
Antoine (1888):

DIFFUSION COEFFICIENTS (DIFFUSIVITIES)

Diffusion coefficients are needed in the design of mass transfer processes; such as gas
absorption, distillation, and liquid-liquid extraction.

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Liquids
The equation developed by Wilke and Chang (1955), given below, can be used to predict liquid
diffusivity. This equation is discussed in Volume 1, Chapter 10.

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Note: more details about other physical properties can be found in Chemical Engineering,
Volume 6, Fourth edition, Chemical Engineering Design, R. K. Sinnott, Chapter 8.

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