Basics of Catalytic Kinetics

2018

SATU OJALA
Back to basics…
Homogeneous catalytic reaction

http://spaceflight.esa.int/impress/text/education/Catalysis/index.html
Back to basics…
Heterogeneous catalytic reaction

http://spaceflight.esa.int/impress/text/education/Catalysis/index.html
Back to basics…
Enzyme catalytic reaction
The Rate of the reaction

 The rate of the reaction in the gas or liquid phase is

proportional to the reactant concentrations ci:
𝑛𝑖
ς
𝑟 = 𝑘 𝑐𝑖
where k is the rate constant
n is the reaction order
 Catalytic reactions do not take place in the gas or liquid
phase
 Heterogeneous catalysis: reactions take place at the
surface of the catalyst
 Homogeneous catalysis: reactions happen on the
metal atom on an organimetallic complex
The Rate of the reaction

 The concentrations of the reactants at the surface or

on a metal atom differ from those in the gas and
liquid phase

Since surface concentrations are very difficult to

determine, their values are derived from
the concentrations in the gas or liquid phase
by means of equilibrium isotherms
Steps of catalytic reaction

 Steps of catalytic reaction

 Diffusion of the reactant
molecules to the surface
(external and internal)
 Adsorption of the reactants
on the surface
 Reaction on the surface

 Desorption of the products

 Diffusion of the desorbed

products (internal and
external)
Raweewan Klaewkla et al. A Review of Mass Transfer Controlling the
Reaction Rate in Heterogeneous Catalytic Systems, In Tech 29, 2011.

Keith J. Laidler, Chemical Kinetics; J.F. Le Page, Applied Heterogeneous Catalysis

Apparent reaction rate?

 When studying the rate of reaction, you follow for

example production of your main product
 One possibility: Measurement of concentration at constant
temperature in a batch reactor
 How you can get the reaction rate out?
 What do you actually observe?
 External diffusion?
 Pore diffusion?
 Adsorption/desorption?
 Surface reaction?

 How the ’activation barrier’

effects the reaction rate?
www.umich.edu/~essen/html/course/lectures/ten/
Rate determining step?

 Diffusion (1, 2, 6, 7) is only sometimes rate

determining step in solid-liquid reactions (involve
physical process of mass tranfer)
 Diffusion does not involve activation energy
 Concentration gradients

However, observed reaction rate

can never be faster than
maximum rate of diffusion of
the reactants

Keith J. Laidler, Chemical Kinetics; J.F. Le Page, Applied Heterogeneous Catalysis

Diffusion during catalytic process

Di - intergranular diffusion of
reactants
D’i - intergranular diffusion of
products
DE - external diffusion of
reactants
D’E - external diffusion of
products
Ch - concentration of reactant
in the external
homogeneous phase
Cs - concentration of the
reactant on the external
surface of the particle
C - concentration of the
reactant inside the
particle’s pores
J.F. Le Page, Applied Heterogeneous Catalysis
Rate determining step?

 Adsorption-desorption are more likely the slowest

steps (need high activation energy)
 In most reactions the DESORPTION is the slowest step
 In practise, steps 4 and 5 are combined, because 4
is very difficult to determine
 Steps 3-5 involve chemical phenomena (formation
or breaking of chemical bods)

J.F. Le Page, Applied Heterogeneous Catalysis

Chemical reactions occurring during
heterogeneous catalysis

J.F. Le Page, Applied Heterogeneous Catalysis

Chemisorption of reacting substances

 The reactants arrive close to catalyst surface and react

with the surface to form new species
 The step consists of physisorption & chemisorption
 The physical adsorption reduces the activation energy for subsequent
chemical adsorption (several layers possible)
 Chemisorption can be dissociative or associative (adsorption energy
comparable to chemical bonds)
 Saturated molecules tend to chemisorb in dissociative manner
 Unsaturated molecules associative manner

CH2 = CH2 + 2M ↔ CH2 – CH2

-M–M-
 Chemisorption is limited to only one layer of molecules and it is
specific (different molecules will not be adsorbed on the same surface
to the same amount or in the same way)

J.F. Le Page, Applied Heterogeneous Catalysis

Heat Transfer

 The reactions are exothermic or endothermic

 The heat is consumed or released

 Causes temperature gradient between the catalyst

surface and the fluid
 The temperature gradient increases with:
 An increase in activity
 An increase in heat of reaction
 An increase in the resistance to heat transfer across the
reacting fluids
 How temperature is related to adsorption/
desorption?

J.F. Le Page, Applied Heterogeneous Catalysis

Transformation of the adsorbed species

 If the temperature is high enough, the molecules

become active and acquire greater mobility over the
solid surface → surface reactions occur
 Identification of exact mechanism involed in the
rearrangement of a surface complex for the
interaction of adsorbed molecules is very difficult,
even impossible
 Isotopic exchange techniques
 Operando spectroscopy
Theories for Surface Kinetics

 How to change the catalytic cycle into kinetics?

 Relate surface concentration of adsorbed species to its gas phase
pressure (concentration)
 This is done by means of EQUILIBRIUM ISOTHERMS
 Langmuir adsorption isotherm
 Langmuir isotherm is
often chosen to deduce the
Langmuir-Hinshelwood
kinetic rate equation
Langmuir Adsorption Isotherm

 Express rate of reactions in terms of surface concentrations

 Translate surface concentrations to an expression in terms of gas phase
partial pressures
Langmuir Adsorption Isotherm

𝐾𝐴 𝑝𝐴
𝜃𝐴 =
1 + σ 𝐾𝑖 𝑝𝑖
Surface reaction mechanisms (gas-solid)

 Langmuir-Hinshelwood
 Relates Langmuir adsorption
to reaction rate
 Sabatier’s principle

H
H H H
H H H H

Catalyst Catalyst Catalyst Catalyst

Step 1 Step 2 Step 3 Step 4

Surface reaction mechanisms (gas-solid)

 Eley-Rideal
Note: Surface site is very often marked with * and adsorbed
molecule with X*

H H
H
H
H H H

Catalyst Catalyst Catalyst Catalyst

Step 1 Step 2 Step 3 Step 4

Surface reaction mechanisms (gas-solid)

 Mars-van Krevelen
CO2

CO
O2

Dissociative
adsorption
O Ru O O Ru O Ru O O Ru O
Support Support Support Support
What mechanism is represented below?

Reaction: A2 + 2B = 2AB

Mechanism:

A2 + * = A2*
A2* + * = 2A*
A* + B = AB + *

www.umich.edu/~essen/html/course/lectures/ten/
Eley-Rideal or Langmuir-Hinshelwood?

For the Eley-Rideal mechanism:

the rate will increase with increasing coverage until the
surface is completely covered by A*.

For the Langmuir-Hinshelwood mechanism:

the rate will go through a maximum and end up at zero,
when the surface is completely covered by A*.

This happens because the step B + * = B*

cannot proceed when A* blocks all sites.

The step B + * = B* requires a free site.

www.umich.edu/~essen/html/course/lectures/ten/
Monomolecular reaction

k1 k2 k3 A B
A + * ↔ A* ↔ B* ↔ B + *
k -1 k -2 k -3 __ A* __ ↔__B*__

• The number of active sites is much smaller than the number of reactants
and products
• Therefore, the change in concentration of reaction intermediates A* and
B* is small compared to the concentrations of the reactants and products
 steady state approximation is valid

• It means that dθ*/dt= dθA/dt= dθB/dt=0

Monomolecular reaction

• This gives us the following equations:

𝑑𝜃∗
= −𝑘1 𝑃𝐴 𝜃∗ + 𝑘−1 𝜃𝐴 + 𝑘3 𝜃𝐵 − 𝑘−3 𝑃𝐵 𝜃∗ =−𝑟1 + 𝑟3 = 0
𝑑𝑡

𝑑𝜃𝐴
= 𝑘1 𝑃𝐴 𝜃∗ − 𝑘−1 𝜃𝐴 − 𝑘2 𝜃𝐴 + 𝑘−2 𝜃𝐵 =𝑟1 − 𝑟2 = 0
𝑑𝑡

𝑑𝜃𝐵
= 𝑘2 𝜃𝐴 − 𝑘−2 𝜃𝐵 − 𝑘3 𝜃𝐵 + 𝑘−3 𝑃𝐵 𝜃∗ =𝑟2 − 𝑟3 = 0
𝑑𝑡

k1 k2 k3
• Under steady-state conditions, the
net rates of the three reaction steps A + * ↔ A* ↔ B* ↔ B + *
are equal (r1= r2= r3) k -1 k -2 k -3

PA θA θB θ*
PB
θ*
Monomolecular reaction

• These 3 equations together with mass balance equation: θA+θB+θ*=1 enable

calculation of the rate: r = r1 = r2 = r3 as a function of the partial pressures of
A and B in the gas phase and the six rate constants ki and K-i

r = r1 = r2 = r3 =

𝑘1 𝑘2 𝑘3 𝑃𝐴 − 𝑘−1 𝑘−2 𝑘−3 𝑃𝐵

𝑘1 𝑘−1 + 𝑘2 𝑘−2 + 𝑘1 𝑘3 𝑃𝐴 + 𝑘−1 𝑘−3 + 𝑘2 𝑘−3 +𝑘−2 𝑘−3 𝑃𝐵 + 𝑘−1 𝑘−2 + 𝑘−1 𝑘3 + 𝑘2 𝑘3

• This equation is too complicated for quantitative purposes and typically

computer is used to resolve it
• IF one of the reaction steps is much slower than the others, we can make
simplifications based on this rate-determining step
Monomolecular reaction

• When the surface reaction is rate-determining:

• It means that forward and backward reactions of adsorption and
desorption are much faster than the surface reaction, and they
reach the equilibrium very rapidly
• That means, that Langmuir equation can be used to calculate the
coverage of the surface sites with A and B
A B
• The net reaction rate is then
r = r2 – r-2 = (k2θA-k-2θB)N k2
• When we use Langmuir coverage for θA and θB __ A* __ ↔__B*__
(see slide 17 for equation) we will get:
k-2
−1 𝑃
𝑘2 𝐾𝐴 𝑃𝐴 − 𝐾𝑒𝑞
𝑘2 𝐾𝐴 𝑃𝐴 − 𝑘−2 𝐾𝐵 𝑃𝐵 𝐵 𝑘2 𝐾𝐴
𝑟=𝑁 =𝑁 𝐾𝑒𝑞 =
1 + 𝐾𝐴 𝑃𝐴 + 𝐾𝐵 𝑃𝐵 1 + 𝐾𝐴 𝑃𝐴 + 𝐾𝐵 𝑃𝐵 𝑘−2 𝐾𝐵
Equilibrium constant of
overall reaction A↔B
Monomolecular reaction

−1
• At low conversion 𝐾𝑒𝑞 𝑃𝐵 ≪ 𝑃𝐴 the equation simplifies to:

𝑘2 𝐾𝐴 𝑃𝐴 𝐾𝐴 𝑝𝐴
𝑟=𝑁 𝜃𝐴 =
1 + 𝐾𝐴 𝑃𝐴 + 𝐾𝐵 𝑃𝐵 1 + σ 𝐾𝑖 𝑝𝑖
(Obsrve similarity)
There are 3 sub-cases related to the surface reaction:

1. A and B adsorb weakly

2. A adsorpbs strongly and B weakly
3. A adsorbs weakly and B strongly
−1 𝑃
𝑘2 𝐾𝐴 𝑃𝐴 − 𝐾𝑒𝑞 𝐵
𝑟=𝑁
1 + 𝐾𝐴 𝑃𝐴 + 𝐾𝐵 𝑃𝐵
(We are simplifying this equation)
Monomolecular reaction
𝑘2 𝐾𝐴 𝑃𝐴
𝑟=𝑁
1 + 𝐾𝐴 𝑃𝐴 + 𝐾𝐵 𝑃𝐵

• When both A and B adsorb weakly on the catalyst surface, KAPA « 1 and KBPB
« 1 and r = Nk2KAPA . The value of k2 can be determined with Arrhenius
equation.

• When adsorption of A is strong and that of B is weak (REACTANT

INHIBITION), then KAPA » 1 and KBPB « 1 and r = Nk2. The reaction does
not depend the concentration of A in the gas phase (zero order in A)

• When the adsorption of B is strong (PRODUCT INHIBITION) the desorption

??
of B is the rate-determing step and r is 𝑟 = 𝑁 𝑘2 𝐾𝐴 𝑃𝐴
𝐾𝐵 𝑃𝐵
Monomolecular reaction

• When adsorption of the reactant or product is rate-determining:

• It means that all other reaction steps are much faster than the rate of
adsorption / desorption
A B
• If adsorption is the rate-determining (slowest
step), A* reacts fast to B* and product B desorbs
fast from the catalyst surface __ A* __ ↔__B*__
• It results that the coverage of the surface is very
small and θ* ≈ 1. (Note, θ* is the empty site)
• Thus:
k1 k2 k3
r = r1 = k1PA θf N = k1PA N A + * ↔ A* ↔ B* ↔ B + *
k -1 k -2 k -3
Example: ammonia synthesis follows PA θA θB PB θ*
this route
θ*
Monomolecular reaction

A B
• If desorption is slow, all the steps before it are
really fast and the catalyst surface is covered by
both A and B.
• The system is pre-equilibrated (fast), meaning that __ A* __ ↔__B*__

k1 k2 k3
r1 – r-1 = (k1PAθ*-k-1θA)N = 0
A + * ↔ A* ↔ B* ↔ B + *
and k -1 k -2 k -3

r2 – r-2 = (k2θA-k-2θB)N = 0 PA θA θ*
θB PB
θ*
• Thus, you can resolve θA, θB and θ* from
above equations and you will get:
𝐾𝐴 𝐾𝐵 𝑃𝐴
𝑟 = 𝑟3 = 𝑘3 𝜃𝐵 𝑁 = 𝑘3 𝐾2 𝜃𝐴 𝑁 = 𝑘3 𝑁
1 + 𝐾𝐴 1 + 𝐾2 𝑃𝐴
Monomolecular reaction

• As a summary, in the Langmuir-Hinshelwood mechanism for a monomolecular

reaction:
• the reaction is first order in the reactant A unless the adsorption of A is
strong (then the reaction order decreases to zero)
• When product inhibition occurs, the reaction order for the product (B) is -1
• The total order (sum of all the orders) is always 0 when a reactant or
product adsorbs strongly  low or negative order thus indicates strong
adsorption

A B

__ A* __ ↔__B*__
Bimolecular reaction

• In mono-molecular reaction the reactant must be chemisorbed on the surface

for catalytic reaction to occur
• In bi-molecular reaction one (Eley-Rideal) or two (Langmuir-Hinshelwood)
reactants are chemisorbed

• Typically it is considered that Langmuir-Hinshelwood reaction occurs more

likely, since in that case the interaction of the both the molecules with the
catalyst weakens the bonds in both the molecule, which facilitates the reaction
• Only the reactions with radical (for example :adsorbed molecule + gas-phase
radical) may proceed via Eley-Rideal mechanism
• Even though there are certain other reasons too, why Langmuir-Hinshelwood
mechanism is more probable than Eley-Rideal, only few reactions have actually
been determined experimentally
Bimolecular reaction

• Similar equations as for monomolecular reactions can be formulated for

bimolecular reactions of A and B to give molecule C

𝐴 + ∗ ⇆ 𝐴∗ B + ∗ ⇆ 𝐵∗ and 𝐵 ∗ + 𝐴∗ ⟶ 𝐶 ∗ ⇆ 𝐶 + ∗

• If the reaction at the surface is the rate-determining, occurs via L-H

mechanism, and A, B and C adsorb weakly at the surface, then:
𝑘𝑁 2 ∙ 𝐾𝐴 𝑃𝐴 𝐾𝐵 𝑃𝐵
𝑟 = 𝑘𝑁𝜃𝐴 𝑁𝜃𝐵 = 2 = 𝑘𝑁 2 ∙ 𝐾𝐴 𝐾𝐵 ∙ 𝑃𝐴 𝑃𝐵
1 + 𝐾𝐴 𝑃𝐴 + 𝐾𝐵 𝑃𝐵 + 𝐾𝐶 𝑃𝐶

• What is the form of equation in the case, when adsorption of A is strong and B & C
weak?
• What about in the intermediate case of A adsorption, when adsorption of B and C
are weak?
• What about in the case of product inhibition?
Questions

1. Derive the rate equation for a bimolecular reaction that

follows the Eley-Rideal mechanism. What is the order of
reaction in the reactants A and B?
2. Polymerisation grade ethene must be ultra-pure, because
traces of acetylene cause crosslinking of polyethene.
Traces of acetylene in ethene are removed in industry by
hydrogenation over a Pd catalyst. When reacted
separately, ethene reacts faster with hydrogen than
acetylene does, but in a mixture of acetylene and ethene
the acetylene reacts faster. How this is possible?
Influence of Diffusion

• Diffusion brings the reactants to the catalytically active sites and moves the
products away from the sites
• Normally diffusion is considered much faster than chemical reaction and not
taken into account in the kinetic models
• This is not always true

cc A cc B cc C

A – rdiff >> rchem (low T)

B - rdiff ≈ rchem (intermediate T)
C - rdiff << rchem (high T)
Influence of Diffusion

• Thiele modulus determines the part of the pore that is involved in the catalytic
reaction

0.5
𝑘𝑉 Where
∅ = 𝑚𝐿 = 𝐿 kV is a volume reaction rate constant
𝐷
D is diffusion coefficient
L is length

• When Thiele modulus is large, the concentration of the reactant inside the
pore decreases fast and the overall reaction rate decreases, because the pore
is not used effectively
Influence of Diffusion

Concentration of the
reactant as a function of
distance in a catalyst
pore, depending on the
values of the Thiele
modulus ø=mL.
Influence of Diffusion

• Effectiveness factor (η) is defined as the ratio of the actual rate with rate
without diffusion limitation

Effectiveness factor as a
function of the Thiele
modulus
Catalyst
works
effectively
The pores are most effectively
used when
Reaction • the diffusion coefficient D
happens near is high,
the pore mouth
• the reaction rate constant k
is low,
• the pore radius is large and
• the pore length is small
Influence of Diffusion

• Diffusion limitation occurs at high rather than at low temperature

• At high temperature, the reaction is so fast that it happens at outer
surface of the catalyst particles
• The reaction rate is then limited by external diffusion from the gas
phase to the gas film on the outer surface of the particles
• Because the temperature coefficient of diffusion is small, the activation
energy will be about zero at very high temperature
• Diffusion limitation can be checked by changing the catalyst particle size
• The Thiele modulus is proportional to the length of the particles and
breaking the particles leads to an increase in the rate when diffusion is
slow
• Diffusion limitation can also occur on the outer surface of the particles due
to stagnant film that limits diffusion
• Occurs typically in liquid phase
Catalysis by enzymes

 Enzymes are ’biological catalysts’ that are very specific – some of the
enzymes show absolutic specificity, for example urease enzyme catalyses
only urea hydrolysis reaction
CO(NH2)2 + H2O  CO2 + 2NH3
 There exist also group specificity: the enzyme catalyze reactions which
involve reactants with have certain structural features and
 Stereochemical specificity: where the enzyme works with one
stereochemical form and not with the other one
 The enzymes are proteins that may contain another nonprotein susbtance
(coenzymes or prosthetic groups) that are essential for the action of the
enzyme
 Some enzymes are catalytically inactive without the presence of certain
metal ions
 ’Active sites’ of proteins are called as ’active centers’
 The actions of enzymes reminds the catalysis by acids and bases, but it is
more complicated
Catalysis by enzymes

 The most simple case of Enzyme catalysis involves a reaction of one

substrate
 The mechanism was explained by Michaelis and Menten

k1
𝐸 + 𝑆 ⇄ 𝐸𝑆 E and S are the enzyme and the
k-1 substrate, P is the product and ES
2k in an addition complex
𝐸𝑆 → 𝐸+𝑃

• Steady state equation for this reaction is:

𝑘1 𝐸 𝑆 − 𝑘−1 𝐸𝑆 − 𝑘2 𝐸𝑆 = 0

The concentration of the substrate is typically much higher than that of

enzyme, so only small part of the substrate is bound to the substrate.
Catalysis by enzymes

• Total concentration of the enzyme [E]0 is equal to the concentration of the

free enzyme and the bound enzyme

𝐸 0 = 𝐸 + 𝐸𝑆

• Elimination of [E] between the two presented equations gives:

𝑘1 𝐸 0 − 𝐸𝑆 𝑆 − 𝑘−1 + 𝑘2 𝐸𝑆 = 0

and therefore
𝑘1 𝐸 0 𝑆
𝐸𝑆 =
𝑘−1 + 𝑘2 + 𝑘1 𝑆
Catalysis by enzymes

The rate of reaction is:

𝑘1 𝑘2 𝐸 0 𝑆 𝑘2 𝐸 0 𝑆 𝑘2 𝐸 0 𝑆
𝑟 = 𝑘2 𝐸𝑆 = = =
𝑘−1 + 𝑘2 + 𝑘1 𝑆 𝑘−1 + 𝑘2 𝐾𝑚 + 𝑆
+ 𝑆
𝑘1

Where Km is known as Michaelis constant and the equation in its last form is
known as Michaelis-Menten equation.
Catalysis by enzymes

 The pH of the solution has a significant effect on the rate of the enzyme
reaction
 If acidity or bacisity comes too high, the tertiary structure of the protein
is destroyed and this effect is irreversible
 With certain range of pH no permanent changes to enzyme will appear,
but the rate of the reaction will go through maximum

COOH NH3+ COO- NH3+ COO- NH2

Enzyme Enzyme Enzyme

Low pH High pH
Catalysis by enzymes

• At temperatures above 35°C or higher, the enzyme may undergo very rapid
deactivation
• The rates of enzyme-catalyzed reactions frequently pass through a maximum
when temperature is raised

https://www.quora.com/Why-do-enzymes-have-different-optimal-
temperatures
Questions

1. The energy barrier of the reaction can be reduced by using the

catalysts, but what does it mean in practise? (what is improved)
2. To what purpose in practise you could use information from the
surface reaction mechanisms?
3. (A) What is meant by catalytic kinetics? (B) What kind of information
can be achieved from kinetic studies? (C) How it is related to the
different reaction steps of catalysis? (D) What is meant by rate
determining step?
4. Mention few advantages for using a catalyst in a reaction compared
with the same reaction occurring without a catalyst.