Advanced Chemical Reaction

Engineering
(ChEg 6122)

seare gebremeskel (Phd cand.)

[email protected]

Mekelle University
Ethiopian Institute of Technology-Mekelle
Department of Chemical Engineering
Process Engineering
April 7, 2021
 Lecture Outline

Catalytic
Reactions
1 Basics concepts of catalysts and catalysis
Basics concepts of 2 Action of catalysts
catalysts and
catalysis
Action of catalysts 3 Green Catalysis
Green Catalysis
Mode of Action of
Catalyst
4 Mode of Action of Catalyst
Type of Catalysts
Catalytic Reaction 5 Type of Catalysts
Mechanisms
Characteristics of
Catalyst in 6 Catalytic Reaction Mechanisms
heterogeneous
reactions
Developing the 7 Characteristics of Catalyst in heterogeneous reactions
Rate of Catalytic
Reactions
Catalyst 8 Developing the Rate of Catalytic Reactions
Deactivation

9 Catalyst Deactivation

2 / 77
 Basic concepts of catalysts and catalysis

Catalytic
Reactions What is catalyst?

Basics concepts of
catalysts and It is a substance that facilitates a chemical reaction.
catalysis
Action of catalysts
Green Catalysis
It opens a different, faster reaction pathway. i.e. it
Mode of Action of
increases the rate of reaction
Catalyst
Type of Catalysts Lowers the activation energy
Catalytic Reaction
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

3 / 77
 Catalytic
Reactions

Basics concepts of
catalysts and
catalysis
Action of catalysts
Green Catalysis
Mode of Action of
Catalyst
Type of Catalysts
Catalytic Reaction
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Figure 1: Different reaction paths.
Rate of Catalytic
Reactions
Catalyst
Deactivation The highest energy position (peak position) represents the
transition state. With the catalyst, the energy required to
enter transition state decreases, thereby decreasing the
energy required to initiate the reaction
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 Catalytic
Reactions

Basics concepts of
catalysts and
catalysis
Action of catalysts
Green Catalysis
Mode of Action of
Catalyst
Type of Catalysts
Catalytic Reaction
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Figure 2: Different reaction paths.
Rate of Catalytic
Reactions
Catalyst
Deactivation
while the catalyst lowers the activation energy, it does not
change the energies of the original reactants or products.
Rather, the reactant energy and the product energy re-
main the same and only the activation energy is altered
(lowered) 5 / 77
 Con’t...

Catalytic
Reactions A catalyst deals with reaction kinetics, not
thermodynamics
Basics concepts of
catalysts and
catalysis
That is, catalysts do not and cannot change the
Action of catalysts thermodynamic equilibrium.
Green Catalysis
Mode of Action of
Catalyst
Type of Catalysts
Catalytic Reaction
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

Figure 3: Catalysis deals with the transition between

reactants and products. It does not affect the overall
reaction thermodynamics. 6 / 77
 Con’t...

Catalytic
Reactions The reaction thermodynamics describe your
elevation at your starting point and your destination
Basics concepts of
catalysts and
catalysis
However, the reaction kinetics depend on which
Action of catalysts pathway you have taken.
Green Catalysis
Mode of Action of
Catalyst
The main advantages of catalysis is that you get
Type of Catalysts the desired product faster, using fewer resources
Catalytic Reaction and generating less waste.
Mechanisms
Characteristics of
Catalyst in
heterogeneous
Catalyst makes a reaction to go faster, without
reactions being consumed in the process.
Developing the
Rate of Catalytic
Reactions Since the catalyst is not consumed in the process,
Catalyst
Deactivation each catalyst molecule can participate in many
consecutive cycles, so we need only a small amount
of catalyst

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 Catalytic
Reactions
Catalysis is an action by catalyst which takes part in a
chemical reaction process and can alter the rate of re-
Basics concepts of
action, and by itself returns to its original form without
catalysts and
catalysis
being consumed or destroyed at the end of the reactions.
Action of catalysts
Green Catalysis Catalyst is a key to Chemical transformation in all indus-
Mode of Action of
Catalyst
trially benign processes. (>95% process)
Type of Catalysts
Catalytic Reaction
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

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 Catalytic
Reactions
Three key aspects of catalyst action

Basics concepts of
catalysts and
Taking part in the reaction: It will change itself
catalysis during the process by interacting with other
Action of catalysts reactant/product molecules
Green Catalysis
Mode of Action of
Catalyst Altering the rates of reactions: In most cases
Type of Catalysts
Catalytic Reaction
the rates of reactions are increased by the action of
Mechanisms catalysts: however, in some situations the rates of
Characteristics of
Catalyst in
undesired reactions are selectively suppressed
heterogeneous
reactions
Developing the Returning to its original form: After reaction
Rate of Catalytic
Reactions cycles a catalyst with exactly the same nature is
Catalyst reborn. In practice a catalyst has its lifespan it
Deactivation
deactivates gradually during use.

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 Catalytic
Reactions
A catalyst accelerates a chemical reaction without
affecting the position of the equilibrium
Basics concepts of
catalysts and Apart from accelerating reactions, catalysts can
catalysis
Action of catalysts
affect the selectivity of various chemical reactions;
Green Catalysis different distribution of products can be obtained
Mode of Action of from a given starting material by using different
Catalyst
Type of Catalysts
catalytic systems
Catalytic Reaction
Mechanisms Catalyst alters the rate of reaction with high
Characteristics of
Catalyst in selectivity
heterogeneous
reactions
Developing the Does it participate in the reaction?
Rate of Catalytic
Reactions
Catalyst
Deactivation
How does it change the rate?- Offers an alternate
path with low Ea

10 / 77
 Catalytic
Reactions
Does it affect ∆HR , ∆GR and Eqn constant??
Does it affect yield and selectivity??
Basics concepts of
catalysts and
catalysis
Action of catalysts
Does it initiate a reaction?
Green Catalysis
Mode of Action of
Catalyst
Type of Catalysts
Catalytic Reaction
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

11 / 77
 Catalytic
Reactions

Basics concepts of
catalysts and
catalysis
Action of catalysts
Green Catalysis
Mode of Action of
Catalyst
Type of Catalysts
Catalytic Reaction
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions Every catalytic reaction is a sequence of elementary steps,
Catalyst
Deactivation in which reactant molecules bind to the catalyst, where
they react, after which the product detaches from the
catalyst, liberating the later for the next cycle.

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 Action of catalysts

Catalytic
Reactions The reaction activation energy is altered

Basics concepts of
The intermediates formed are different from those
catalysts and
catalysis
formed in non-catalytic reactions
Action of catalysts
Green Catalysis The rates of reactions are altered (both desired and
Mode of Action of
Catalyst undesired ones)
Type of Catalysts
Catalytic Reaction
Mechanisms Reactions proceed under less demanding conditions
Characteristics of
Catalyst in
( temperature, pressure...)
heterogeneous
reactions
Developing the It is important to remember that the use of catalyst
Rate of Catalytic
Reactions does not vary the DG and Keq values of the
Catalyst
Deactivation
reaction concerned, it merely change the pace of
the process.

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 Action of catalysts

Catalytic
Reactions Whether a reaction can proceed or not and to what
extent a reaction can proceed is exclusively
Basics concepts of determined by the reaction thermodynamics, which
catalysts and
catalysis is governed by the values of DG and Keq , not by the
Action of catalysts presence of catalysts
Green Catalysis
Mode of Action of
Catalyst The reaction thermodynamics provides the driving
Type of Catalysts force for a reaction; the presence of catalysts
Catalytic Reaction
Mechanisms
changes the way how driving force acts on that
Characteristics of process
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

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 Action of catalysts

Catalytic
Reactions Example:

Basics concepts of CH4 (g)+CO2 2CO(g) +2H2

catalysts and
catalysis DG◦373 = 151kJ/mol (100 ◦ C) and DG◦973 = -16kJ/mol
Action of catalysts
Green Catalysis
(700 ◦ C)
Mode of Action of
Catalyst
Type of Catalysts
At 100 ◦ C, DG◦373 = DG◦373 = 151kJ/mol > 0
Catalytic Reaction
Mechanisms
Characteristics of
There is no thermodynamic driving force, the reaction
Catalyst in
heterogeneous
won’t proceed with or without a catalyst.
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

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 Action of catalysts

Catalytic
Reactions At 700 ◦ C, DG◦973 = -16kJ/mol < 0, the thermodynamic
driving force is there. However, simply putting CH4 and
Basics concepts of
catalysts and
CO2 together in a reactor does not mean they will react.
catalysis Without a proper catalyst heating the mixture in reac-
Action of catalysts tor results no conversion of CH4 and CO2 at all. When
Green Catalysis
Mode of Action of
Pt/ZrO2 or Ni/Al2 O3 is present in the reactor at the
Catalyst same temperature, equilibrium conversion can be achieved
Type of Catalysts
Catalytic Reaction
(<100%).
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

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 Catalytic
Reactions
Catalysis action - Reaction kinetics and mechanism:
Catalyst action leads to the rate of a reaction to
Basics concepts of
change This is realized by changing the course of
catalysts and
catalysis
reaction (compared to non-catalytic reaction)
Action of catalysts
Green Catalysis Forming complex with reactants/products:
Mode of Action of
Catalyst controlling the rate of elementary steps in the
Type of Catalysts process
Catalytic Reaction
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

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 Green Catalysis

Catalytic
Reactions Low cost and scalable

Basics concepts of
Renewable starting materials
catalysts and
catalysis
Action of catalysts Environmentally friendly operation
Green Catalysis
Mode of Action of
Catalyst
Specialty chemicals
Type of Catalysts
Catalytic Reaction Non-toxic by-products
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

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 Con’t...

Catalytic
Reactions For a comparative measurements, such as catalyst screen-
ing, determination of process parameters, optimization of
Basics concepts of catalyst production conditions, and deactivation studies,
catalysts and
catalysis the following activity measures can be used;
Action of catalysts
Green Catalysis
Mode of Action of
Conversion under constant reaction conditions
Catalyst
Type of Catalysts
Catalytic Reaction
Space velocity for a given constant conversion
Mechanisms
Characteristics of
Catalyst in
Space time-yield
heterogeneous
reactions
Developing the
Temperature required for a given conversion
Rate of Catalytic
Reactions
Catalyst
Deactivation

19 / 77
 Con’t...

Catalytic
Reactions For a comparative measurements, such as catalyst screen-
ing, determination of process parameters, optimization of
Basics concepts of catalyst production conditions, and deactivation studies,
catalysts and
catalysis the following activity measures can be used;
Action of catalysts Catalysts are often investigated in continuously
Green Catalysis operating test reactors, in which the conversion
Mode of Action of
Catalyst attained at constant space velocity are compared
Type of Catalysts
Catalytic Reaction
Mechanisms The space velocity (h−1 ): if the volume flow rate
Characteristics of
Catalyst in
relative to the mass of catalyst (how many reactor
heterogeneous
reactions volumes can be treated in a unit time?)
Developing the
Rate of Catalytic
Reactions The space time (h): is the mass of catalyst relative
Catalyst
Deactivation to the volume flow rate of the limiting reactant
(made under constant conditions of starting
material ratio, temperature, and pressure) (How
much time the FAO in the catalyst bed is found?)
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 Catalytic
Reactions
Often the performance of a reactor is given relative to the
catalyst mass or volume, so that reactors of different size
Basics concepts of
or construction can be compared with one another. This
catalysts and
catalysis
quantity is known as the space-time yield STY
Action of catalysts
Green Catalysis STY = Desired product quantity/Catalyst vol.time
Mode of Action of
Catalyst
Type of Catalysts I.e., High conversion does not mean the catalyst is good,
Catalytic Reaction because the yield may be low.
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

21 / 77
 Mode of Action of Catalysts

Catalytic
Reactions The suitability of a catalyst for an industrial process de-
pends mainly on the following three properties
Basics concepts of
catalysts and
catalysis Activity
Action of catalysts
Green Catalysis
Mode of Action of
Selectivity
Catalyst
Type of Catalysts
Catalytic Reaction
Stability (deactivation behavior)
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

22 / 77
 Catalytic
Reactions
Activity is a means of how fast one or more reactions
proceed in the presence of the catalyst. Activity can be
Basics concepts of
defined in terms of kinetics.
catalysts and
catalysis
Action of catalysts
Green Catalysis
Mode of Action of
Catalyst
Type of Catalysts
Catalytic Reaction
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

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 Con’t...

Catalytic
Reactions Definition of Turnover Numbers (TON) and Turnover fre-
quencies (TOF) based on catalysts:
Basics concepts of
catalysts and Homogeneous catalysis:Turnover Numbers (TON)
catalysis
Action of catalysts and Turnover frequencies (TOF) is the number of A
Green Catalysis molecules that one molecule of catalyst can convert
Mode of Action of
Catalyst (or turn over) into B molecules.
Type of Catalysts
Catalytic Reaction
Mechanisms Heterogeneous catalysis: TON and TOF are often
Characteristics of defined per active site, or per gram catalyst. This
Catalyst in
heterogeneous
reactions
is because one does not know exactly how many
Developing the
catalyst molecules there are on the surface.
Rate of Catalytic
Reactions
Catalyst
Biocatalysis: the TON and TOF are defined by the
Deactivation rate measured when all the enzyme molecules are
complexed with a reactant, divided by the total
enzyme concentration.
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 Turn over Frequency (TOF)

Catalytic
Reactions TOF quantifies the specific activity of a catalytic center
for a special reaction under defined reaction conditions
Basics concepts of by the number of molecular reactions or catalytic cycles
catalysts and
catalysis occurring at the center per unit time
Action of catalysts
Green Catalysis For heterogeneous catalysts the number of active centers
Mode of Action of
Catalyst
is derived usually from sorption methods
Type of Catalysts
Catalytic Reaction For most relevant industrial applications, the TOF is in
Mechanisms
Characteristics of the range (10−2 to 102 )s−1
Catalyst in
heterogeneous
reactions
Developing the
TOF = Volumetric rate of reaction/number of centers/volume
Rate of Catalytic
Reactions of total site
Catalyst
Deactivation

25 / 77
 Turn Over Number

Catalytic
Reactions TON: specifies the maximum use that can be made of a
catalyst for a special reaction under defined conditions by
Basics concepts of a number of molecular reactions or reaction cycles occur-
catalysts and
catalysis ring at the reactive center up to the decay of activity
Action of catalysts
Green Catalysis In short, TON is how many time the catalyst can be used
Mode of Action of
Catalyst
for the process
Type of Catalysts
Catalytic Reaction
Mechanisms
For industrial applications, the TON is in the range 106
Characteristics of
Catalyst in
to 107
heterogeneous
TON = TOF (h−1 )*lifetime of the catalyst (h)
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

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 Stability

Catalytic
Reactions The chemical, thermal, and mechanical stability of a
catalyst determines its lifetime in industrial reactors
Basics concepts of
catalysts and
catalysis
Catalyst stability is influenced by: decomposition,
Action of catalysts coking, and poisoning
Green Catalysis
Mode of Action of
Catalyst
Catalysts that lose activity during a process can
Type of Catalysts often be regenerated before they ultimately have to
Catalytic Reaction be replaced. The total catalyst lifetime is of crucial
Mechanisms
Characteristics of
importance for the economics of a process
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

27 / 77
 Type of Catalysts

Catalytic
Reactions Homogeneous Catalyst: the catalyst is in the same
phase as the reactants and products
Basics concepts of
catalysts and
catalysis
Heterogeneous catalysts: the catalyst and the
Action of catalysts substrate are in different phases.
Green Catalysis
Mode of Action of
Catalyst
Biocatalysts: is an enzyme, a complex protein that
Type of Catalysts catalyzes the reactions in living cells.
Catalytic Reaction
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

28 / 77
 Classification of catalysts

Catalytic
Reactions The solid catalysts are classified into two: bulk
catalysts and impregnated/supported catalysts
Basics concepts of
catalysts and
catalysis Bulk catalysts:They are (mixed) metals or oxides
Action of catalysts
Green Catalysis
and, as their name suggests, the entire catalyst is
Mode of Action of
made of active material.
Catalyst
Type of Catalysts
Catalytic Reaction The silica/ Alpha or Gamma alumina
Mechanisms
hydrocracking catalysts,
Characteristics of
Catalyst in
heterogeneous
reactions Zeolites
Developing the
Rate of Catalytic
Reactions The ammonia synthesis catalyst, and
Catalyst
Deactivation
The Raney metals(Fusion Ni)

29 / 77
 Catalytic
Reactions

Basics concepts of
catalysts and
catalysis
Action of catalysts
Green Catalysis
Mode of Action of
Catalyst
Type of Catalysts
Catalytic Reaction
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

Figure 4: Classification of Catalysts based on preparation

methods
30 / 77
 Impregnated/supported catalysts

Catalytic
Reactions Catalyst support provides a means of obtaining a
large surface area with a small amount of active
Basics concepts of ingredient.
catalysts and
catalysis
Action of catalysts It is very important to reduce the cost of catalyst,
Green Catalysis when expensive ingredient such as platinum,
Mode of Action of
Catalyst
palladium and silver are used. Depositing noble
Type of Catalysts metals on high – area oxide supports disperse the
Catalytic Reaction
Mechanisms
metal over the surface so that nearly every metal
Characteristics of
atom is on the surface.
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

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 Catalytic Reaction Mechanisms

Catalytic
Reactions A gas phase reaction, which is catalyzed by solid
surface (catalyst) occurs on the surface of the
Basics concepts of
catalysts and
catalyst.
catalysis
Action of catalysts For such reaction to take place, at least one
Green Catalysis
reactant must become attached to the surface.
Mode of Action of
Catalyst This attachment is known as adsorption
Type of Catalysts
Catalytic Reaction
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

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 Catalytic
Reactions
There are two types of adsorption, physical and chemical
adsorption.
Basics concepts of
catalysts and
catalysis Physical Adsorption
Action of catalysts
Green Catalysis The process is exothermic,
Mode of Action of
Catalyst The force of attraction between the gas molecules
Type of Catalysts and the solid surface are weak,
Catalytic Reaction The heat of adsorption is relatively small,
Mechanisms
Characteristics of
The amount of gas physically adsorbed decreases
Catalyst in
heterogeneous
rapidly with the increasing temperature
reactions
Chemical Adsorption
Developing the
Rate of Catalytic
Reactions
Catalyst
Affects the rate of chemical reaction,
Deactivation It involves a chemical bond
It is exothermic,
The heat of adsorption is of the same magnitude
as the heat of chemical reaction
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 Catalytic
Reactions
For a catalytic reaction to occur, at least one reactant
must be chemically adsorbed (attached) (i.e., chemisorbed).
Basics concepts of
catalysts and
catalysis
Action of catalysts
Green Catalysis
Mode of Action of
Catalyst
Type of Catalysts
Catalytic Reaction
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation
Fig. 5: Chemisorption view

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 Catalytic adsorption
Reactions
Substrate, (A) + Active site, (S) CA−S
desorption
Basics concepts of ka
catalysts and
catalysis
PA + CS CA−S
Action of catalysts
kd
Green Catalysis We do not know exactly how many active sites are on the
Mode of Action of
Catalyst
surface.
Type of Catalysts
Catalytic Reaction Note that: each of these simple adsorption process is
Mechanisms reversible. This is known as the principle of microscopic
Characteristics of
Catalyst in reversibility
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

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 How to find Concentration of adsorption
of species CA−S
Catalytic
Reactions There are several models to express Concentration of ad-
sorption of species on the site (catalyst)
Basics concepts of
catalysts and
catalysis The Langmuir Equation
Action of catalysts
Green Catalysis Langmuir Assumptions
Mode of Action of
Catalyst
Type of Catalysts
Catalytic Reaction
Out of the molecules striking the surface, only
Mechanisms those that strike the bare surface are considered for
Characteristics of
Catalyst in adsorption
heterogeneous
reactions
Developing the
Rate of Catalytic
There is no interaction between adsorbed molecules
Reactions
Catalyst
Deactivation
All adsorption occurs by the same mechanism, to
which all sites are the same.

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 Catalytic
Reactions
Langmuir Adsorption Postulates: Consider a single
s
gas is adsorbed on the surface, A P
Basics concepts of ka
catalysts and
catalysis A+S A-S
Action of catalysts
kd
Green Catalysis
Mode of Action of
Catalyst
Type of Catalysts
Catalytic Reaction
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

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 Catalytic
Reactions
Adsorbing mechanism for single gas adsorbed on the sur-
face of catalyst is given:
ka
Basics concepts of
catalysts and PA + CS CA−S
catalysis kd
Action of catalysts
Green Catalysis
radsorption = ka PACS (36.1)
Mode of Action of
Catalyst rdesorption = −kd CAS (36.2)
Type of Catalysts
Catalytic Reaction
Mechanisms The net rate of adsorption is equal to the rate of molecu-
Characteristics of
Catalyst in
lar attachment onto the surface minus the rate of detach-
heterogeneous
reactions
ment the surface, thus
Developing the
Rate of Catalytic
Reactions rA = −ka PACS + kd CAS (36.3)
Catalyst
Deactivation
At equilibrium, the attachment and detachment rates are
equal. Therefore,

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 Catalytic
Reactions
ka PACS = −kd CAS (37.1)
Basics concepts of ka PACS ka
catalysts and
catalysis
CAS = = PACS = keq PACS (37.2)
Action of catalysts
kd kd
Green Catalysis The total concentration of the sites on the site balance
Mode of Action of
Catalyst can be given by,
Type of Catalysts CT = CS +CAS (37.3)
Catalytic Reaction
Mechanisms
Characteristics of
CT = CS + keq PACS (37.4)
Catalyst in
heterogeneous CT
reactions CS = (37.5)
Developing the
Rate of Catalytic
1 + keq PA
Reactions
Catalyst Substituting gives, Langmuir isotherm equation,
Deactivation
keq PACT
CAS = (37.6)
1 + keq PA
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 Catalytic
Reactions
When two gases are adsorbed on the surface,
A(g) + B(g) A-S+B-S
Basics concepts of
catalysts and
catalysis
Action of catalysts
Green Catalysis
Mode of Action of
Catalyst
Type of Catalysts
Catalytic Reaction
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

occupied site vacant site

z }| { z}|{
CT = CAS +CBS + CS (38.1)
40 / 77
 Catalytic
Reactions
total moles of sites
CT = (39.1)
Basics concepts of unit mass of catalyst
catalysts and
catalysis
Action of catalysts
Moles of A adsorbed
CAS = (39.2)
Green Catalysis
Mode of Action of
Unit mass of catalyst
Catalyst
Type of Catalysts Moles of B adsorbed
Catalytic Reaction CBS = (39.3)
Mechanisms unit mass of catalyst
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

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 Catalytic
Reactions
CT
CS = (40.1)
Basics concepts of 1 + kA,eq PA + KB,eq PB
catalysts and
catalysis
Action of catalysts CAS = KA,eq PACS
Green Catalysis
Mode of Action of kA,eq PACT
Catalyst CAS = (40.2)
Type of Catalysts 1 + kA,eq + kB,eq PB
Catalytic Reaction
Mechanisms
Characteristics of CBS = kB,eq PBCS
Catalyst in
heterogeneous
reactions kB,eq PBCT
Developing the CBS = (40.3)
Rate of Catalytic
Reactions 1 + KA,eq PA + kB,eq PB
Catalyst
Deactivation

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 Catalytic
Reactions
Equations (a) and (b) shows that, when more than one
substance is present in the system, the Langmuir adsorp-
Basics concepts of
tion isotherm equation becomes some what more com-
catalysts and
catalysis
plex. The other components present in the adsorption
Action of catalysts process would also appear in the denominator as
Green Catalysis
Mode of Action of
Catalyst kX,eq PX
Type of Catalysts
Catalytic Reaction
Mechanisms for reaction product or reactant or for a trace of impurity
Characteristics of
Catalyst in
or poison or inert that is chemisorbed.
heterogeneous
reactions
Developing the kIN,eq PIN
Rate of Catalytic
Reactions
Catalyst
Deactivation kA,eq PACT
CAS =
1 + kA,eq PA + kB,eq PB + kX,eq PX + kIN,eq PIN + ...
(41.1)
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 Catalytic
Reactions
Assignment 1: 1. Consider the following reaction is
taking place A+B C+D+E
Basics concepts of
i) Find the adsorption concentration of A and B, when
catalysts and
catalysis species A,B,C,E and inert appreciably adsorbed on the
Action of catalysts surface of a catalyst and species D are not adsorbed on
Green Catalysis the surface of a catalyst.
Mode of Action of
Catalyst ii) Find the adsorption concentration of C and E, when
Type of Catalysts species A,C,D,E , inert and trace element T appreciably
Catalytic Reaction
Mechanisms adsorbed on the surface of a catalyst and species B are
Characteristics of
Catalyst in
not adsorbed on the surface of a catalyst
heterogeneous
reactions
iii) Reactant A is adsorbed on the surface and reactant
Developing the
Rate of Catalytic
B is reacted in the gas phase. The products C, D and
Reactions some Inert(In) and Trace elements(T) are all appreciably
Catalyst
Deactivation adsorbed on the surface of a catalyst. Find the adsorption
concentration of A and C,

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 Catalytic
Reactions
In Catalytic of heterogeneous reactions;

Basics concepts of
catalysts and
reactants must diffuse through the catalyst pores,
catalysis
Action of catalysts adsorb on its surface
Green Catalysis
Mode of Action of
Catalyst travel to the active site,
Type of Catalysts
Catalytic Reaction
Mechanisms
react there, and
Characteristics of
Catalyst in
heterogeneous
desorbs back to the gas phase
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

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 Catalytic
Reactions

Basics concepts of
catalysts and
catalysis
Action of catalysts
Green Catalysis
Mode of Action of
Catalyst
Type of Catalysts
Catalytic Reaction
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation
In every gas/solid catalytic cycle, at least one of the
reactants must at some point be adsorbed chemically
(Chemisorbed) on the catalyst surface.
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 Characteristics of Catalyst in
heterogeneous reactions
Catalytic
Reactions Most are in a form of porous

Basics concepts of
are supplied as cylindrical pellets with lengths and
catalysts and
catalysis
diameters in the range of 2–10 mm
Action of catalysts
Green Catalysis More complex shapes and monoliths can be used
Mode of Action of
Catalyst
when it is important to minimize pressure drop
Type of Catalysts
Catalytic Reaction The pores are structure in micro-and macro-porous
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

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 Catalytic
Reactions

Basics concepts of
catalysts and
catalysis
Action of catalysts
Green Catalysis
Mode of Action of
Catalyst
Type of Catalysts
Catalytic Reaction
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

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 Catalytic
Reactions

Basics concepts of
catalysts and
catalysis
Action of catalysts
Green Catalysis
Mode of Action of
Catalyst
Type of Catalysts
Catalytic Reaction
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation
catalyst structure

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 Catalytic
Reactions

Basics concepts of
catalysts and
catalysis
Action of catalysts
Green Catalysis
Mode of Action of
Catalyst
Type of Catalysts
Catalytic Reaction
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

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 Catalytic
Reactions
Catalytic site: The catalytic sites are atoms or molecules
on the internal surface
Basics concepts of
catalysts and Support of the Catalytic Site
catalysis
Action of catalysts
Green Catalysis The support of catalytic particle is often an oxide,
Mode of Action of
Catalyst such as alumina (Al2 O3 ) or (SiO2 )
Type of Catalysts
Catalytic Reaction
Mechanisms The support of catalytic particle may provide the
Characteristics of
Catalyst in
catalytic sites directly or it may support a more
heterogeneous
reactions
expensive substance, such as finely divided
Developing the platinum.
Rate of Catalytic
Reactions
Catalyst When heat transfer is important, the catalyst pellets
Deactivation
are randomly packed in small-diameter (10–50 mm)
tubes that are often quite long (2–10 m).

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 Catalytic
Reactions
The overall rate of reaction in, the catalytic reaction can
be summarized by the the following steps;
Basics concepts of
catalysts and
catalysis Step 1. Mass transfer of the reactant (Species A)
Action of catalysts from the bulk to the external surface of the
Green Catalysis
catalytic pellet.
Mode of Action of
Catalyst
Type of Catalysts Step 2. Transportation of the reactant (A) to the
Catalytic Reaction
Mechanisms internal surface of the catalyst particle
Characteristics of
Catalyst in
heterogeneous
reactions
Step 3. Adsorption of reactant (A) onto the
Developing the
Rate of Catalytic
catalyst surface
Reactions
Catalyst
Deactivation
Step 4. Reaction on the surface of the catalyst
Step 5. Desorption of the product (B) from the
catalyst surface
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 Catalytic
Reactions
Step 6. Transportation of the product (B) to the
external surface of the pellet.
Basics concepts of
catalysts and
catalysis
Step 7. Mass transfer of the product (B) from the
Action of catalysts external pellet surface to the bulk fluid
Green Catalysis
Mode of Action of
Catalyst
Type of Catalysts
Catalytic Reaction
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

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 Developing the Rate of Catalytic Reactions

Catalytic
Reactions The rate equations for chemical adsorption, surface
reaction and desorption can simply be developed by
Basics concepts of using the concept of rate controlling,
catalysts and
catalysis
Action of catalysts When one reaction rate is considered as the
Green Catalysis controlling one, the other remaining reaction rates
Mode of Action of
Catalyst
are taken in the state of equilibrium i.e., their rates
Type of Catalysts are considered to be zero.
Catalytic Reaction
Mechanisms Ex. Adsorption controlling reaction, kA is small,
Characteristics of
Catalyst in kS and kD are large, which means the ratio rs /ks and
heterogeneous
reactions rD /kD are very small.
Developing the
Rate of Catalytic Eventually, rs = rD = 0
Reactions
Catalyst
Whereas the ratio, rA /kA is relatively large.
Deactivation

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 Catalytic
Reactions
To obtain the rate equations

Basics concepts of
catalysts and
Assume a sequence of steps in the reaction
catalysis
Action of catalysts Prepare rate laws for each of the individual steps,
Green Catalysis
Mode of Action of
Catalyst Assuming all steps are reversible
Type of Catalysts
Catalytic Reaction
Mechanisms
Postulate a rate limiting step
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

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 Catalytic
Reactions
Consider a unimolecular reaction,
S
A B
Basics concepts of
catalysts and
Develop the rate law when
catalysis
Action of catalysts
A) Adsorption is the rate controlling
Green Catalysis B) Surface reaction is the rate controlling and,
Mode of Action of
Catalyst
C) Desorption is the rate controlling
Type of Catalysts Solution:
Catalytic Reaction
Mechanisms
Adsorption: Ag +S A-S
Characteristics of
Catalyst in
heterogeneous rA = kA PACS − K−ACA−S (54.1)
reactions
Developing the
Rate of Catalytic
Surface reaction: A-S B-S
Reactions
Catalyst
Deactivation
rS = kSCA−S − K−SCB−S (54.2)
Desorption: B-S Bg +S
rD = kDCB−S − K−D PBCS (54.3)
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 Catalytic
Reactions
A) Adsorption as the rate controlling

Basics concepts of
The rate of reaction for such case be given as,
catalysts and
catalysis
Action of catalysts r = rA = kA PACS − k−ACA−S (55.1)
Green Catalysis
Mode of Action of
Catalyst kA is small whereas kS and kD are large. i.e rS = rD = 0,
Type of Catalysts
Catalytic Reaction
Hence rA /kA is relatively large
Mechanisms The surface reaction rate, then can be given as,
Characteristics of
Catalyst in
heterogeneous
reactions rS = kSCA−S − k−SCB−S (55.2)
Developing the
Rate of Catalytic
Reactions
kS CB−S
Catalyst
Deactivation CA−S = CB−S = (55.3)
k−S KS,eq

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 Catalytic
Reactions
Similarly, desorption rate is given by:

Basics concepts of
rD = kDCB−S − K−D PBCS = 0 (56.1)
catalysts and
catalysis Solving for CB−S , thus
Action of catalysts
Green Catalysis
Mode of Action of k−D 1
Catalyst CB−S = PBCS = PBCS (56.2)
Type of Catalysts kD KD,eq
Catalytic Reaction
Mechanisms
Characteristics of
Catalyst in Then,
heterogeneous
reactions
1
Developing the
CA−S = PBCS (56.3)
Rate of Catalytic KS,eq KD,eq
Reactions
Catalyst
Deactivation

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 Catalytic
Reactions
r = rA = kA PACS − k−ACA−S (57.1)
Basics concepts of
catalysts and
1 1
catalysis r = rA = kA PACS − k−A PBCS (57.2)
Action of catalysts KS,eq KD,eq
Green Catalysis " #
Mode of Action of
Catalyst PB
Type of Catalysts r = rA = kA PA − CS (57.3)
Catalytic Reaction KA,eq KS,eq KD,eq
Mechanisms
Characteristics of
Catalyst in
heterogeneous
Suppose that
reactions
Developing the
Rate of Catalytic 1 1 1
Reactions K1,eq = (57.4)
Catalyst
Deactivation
KA,eq KS,eq KD,eq

59 / 77
 Catalytic
Reactions " #
PB
rA = kA PA − (58.1)
Basics concepts of
catalysts and K1,eq
catalysis
Action of catalysts
Green Catalysis
The total concentration of the sites is given by,
Mode of Action of
Catalyst
Type of Catalysts
CT = CS +CA−S +CB−S (58.2)
Catalytic Reaction
Mechanisms 1 1
Characteristics of CT = CS + PBCS + PBCS (58.3)
Catalyst in
heterogeneous KS,eq KD,eq KD,eq
reactions
Developing the
Rate of Catalytic
Alternatively,
Reactions
Catalyst
" #
Deactivation 1 1
CT = CS 1 + PB + PB (58.4)
KS,eq KD,eq KD,eq

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 Catalytic
Reactions
Solving for CS ,

Basics concepts of
CT
catalysts and CS = 1 1
(59.1)
catalysis 1+ KS,eq KD,eq PB + KD,eq PB
Action of catalysts
Green Catalysis
Mode of Action of
Catalyst Hence, the rate of catalytic reaction when adsorption con-
Type of Catalysts trol the reaction becomes
Catalytic Reaction
Mechanisms " #
Characteristics of
Catalyst in CT PB
heterogeneous rA = kA PA − (59.2)
reactions
Developing the
1 + K P.K
B
S,eq
+ KPB
D,eq D,eq
K1,eq
Rate of Catalytic
Reactions
Catalyst
Deactivation

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 Catalytic
Reactions
B) Surface Reaction as the rate controlling

Basics concepts of
ks is small, whereas kA and kD are large. rA = rD ; rs /ks
catalysts and
catalysis is relatively large
Action of catalysts
Green Catalysis
r = rS = kSCA−S − K−SCB−S
Mode of Action of
Catalyst Then, we get
Type of Catalysts CA−S = KA,eq PACS
Catalytic Reaction
Mechanisms 1
Characteristics of CB−S PBCS
Catalyst in
heterogeneous KD,eq
reactions
Developing the 1
Rate of Catalytic
Reactions
rS = ks .KA,eq PACS − k−S . PBCS
Catalyst
KD,eq
Deactivation " #
1
rS = ks .KA,eq PA − k−S . PB CS
KD,eq
62 / 77
 Catalytic
Reactions " #
k−S
rS = kS .KA,eq PA − PB CS
Basics concepts of
catalysts and KD,eq
catalysis
Action of catalysts " #
Green Catalysis kS
Mode of Action of rS = kS kS .KA,eq PA − PB CS
Catalyst KS,eq KD,eq
Type of Catalysts
Catalytic Reaction " #
Mechanisms
Characteristics of 1
Catalyst in rS = kS KA,eq PA − PB CS
heterogeneous
reactions KS,eq KD,eq
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

63 / 77
 Catalytic
Reactions " #
PB
rS = kS PA −
Basics concepts of
catalysts and K1,eq
catalysis
Action of catalysts
Green Catalysis
where
Mode of Action of
1 1 1
Catalyst K1,eq = . .
Type of Catalysts KA,eq KS,eq KD,eq
Catalytic Reaction
Mechanisms
1
Characteristics of
Catalyst in
CT = CS + KA,eq PACS + PBCS
heterogeneous
reactions
KD,eq
Developing the
" #
Rate of Catalytic
Reactions 1
Catalyst CT = CS 1 + KA,eq PA + PB
Deactivation KD,eq

64 / 77
 Catalytic
Reactions " #
CT PB
CS = 1
PA −
Basics concepts of
catalysts and 1 + KA,eq PA + KD,eq PB K1,eq
catalysis
Action of catalysts
Green Catalysis It is to be noted that, more than 75% of all the hetero-
Mode of Action of
Catalyst
geneous reactions, are surface reaction-limited.
Type of Catalysts
Catalytic Reaction
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

65 / 77
 Catalytic
Reactions
kD is small; kA and rS are large. i.e rA = rS = 0; Hence,
rD /kD is relatively large.
Basics concepts of
catalysts and
catalysis r = rD = kDCB−S − k−D PBCS
Action of catalysts
Green Catalysis
Mode of Action of
kSCA−S = k−SCB−S
Catalyst
Type of Catalysts kS
Catalytic Reaction CB−S = CA−S = KS,eqCA−S
Mechanisms k−S
Characteristics of
Catalyst in
heterogeneous
reactions
CB−S = KS,eq KA,eq PACS
Developing the
Rate of Catalytic rD = kD .KS,eq KA,eq PACS − k−D PBCS
Reactions
Catalyst
Deactivation kD
rD = kD .KS,eq KA,eq PACS − PBCS
KD,eq

66 / 77
 Catalytic
Reactions " #
1
rD = kD PA − PB CS
Basics concepts of
catalysts and KS,eq KA,eq KD,eq
catalysis
Action of catalysts
Green Catalysis
Mode of Action of
Catalyst
Type of Catalysts
Catalytic Reaction
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

67 / 77
 Catalytic
Reactions " #
PB
rD = kD PA − CS
Basics concepts of
catalysts and K1,eq
catalysis
Action of catalysts
Green Catalysis CT = CS + KA,eq PACS + KS,eq PACS (66.1)
Mode of Action of " #
Catalyst
Type of Catalysts
Catalytic Reaction
CT = 1 + KA,eq PA + KS,eq PA CS
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
CT
CS =
Developing the
Rate of Catalytic 1 + KA,eq PA + KS,eq PA
Reactions
Catalyst
Deactivation

68 / 77
 Catalytic
Reactions " #
CT 1
rD = kD PA − PB
Basics concepts of
catalysts and 1 + KA,eq PA + KS,eq PA K1,eq
catalysis
Action of catalysts
Green Catalysis
Generally the final rate equations can be represented in
Mode of Action of the following generalized forms,
Catalyst
Type of Catalysts
Catalytic Reaction kinetic term
Mechanisms r= [potential term] (67.1)
Characteristics of
Catalyst in
(adsorption term)n
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

69 / 77
 Catalyst Deactivation

Catalytic
Reactions Occurs when a catalyst becomes less active as the reaction
progresses.
Basics concepts of
catalysts and
catalysis
Often, the activity depends on specific ligating groups. If
Action of catalysts these are destroyed via side-reactions – the catalyst will
Green Catalysis deactivate. This is due to
Mode of Action of
Catalyst
Type of Catalysts
Catalytic Reaction
pH changes,
Mechanisms
Characteristics of
Catalyst in
oxidative degradation,
heterogeneous
reactions
Developing the
increasing temperature, or
Rate of Catalytic
Reactions
Catalyst formation of additional phases
Deactivation

70 / 77
 Catalytic
Reactions
Catalyst deactivation via thermal degradation or
sintering is a common phenomenon in
Basics concepts of
heterogeneous catalysis.
catalysts and
catalysis
Action of catalysts
At high temperatures, the support pore structure
Green Catalysis may collapse, and the size and shape of the metal
Mode of Action of crystallites can change.
Catalyst
Type of Catalysts
Catalytic Reaction
This decreases the catalyst surface area and the
Mechanisms number of active sites.
Characteristics of
Catalyst in
heterogeneous
reactions Ex. At lower temperatures (typically 600 ◦ C for
Developing the
Rate of Catalytic
noble metals) the primary sintering route is atom
Reactions
transfer from small metal particles via surface
Catalyst
Deactivation diffusion.

71 / 77
 Catalytic
Reactions
Sintering is a complex process. It depends on

Basics concepts of
catalysts and
temperature,
catalysis
Action of catalysts support composition,
Green Catalysis
Mode of Action of
Catalyst support porosity,
Type of Catalysts
Catalytic Reaction
Mechanisms
type of active metal, and
Characteristics of
Catalyst in
heterogeneous
surrounding atmosphere
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

72 / 77
 Catalytic
Reactions
At high temperatures (typically above 1000 ◦ C) Three-
way sintering take place
Basics concepts of
catalysts and
catalysis
a. Phase Transformation of the Support
Action of catalysts
Green Catalysis At high temperature the crystal phases of the
Mode of Action of
Catalyst
support transform. Such transformations collapse
Type of Catalysts the pore structure, thereby reducing the surface
Catalytic Reaction
Mechanisms
area and blocking access to active sites(Sintering)
Characteristics of
Catalyst in
heterogeneous b. Atom migration. metal atoms migrate from one
reactions
Developing the
crystallite to another via the surface or the gas
Rate of Catalytic
Reactions
phase.
Catalyst
Deactivation Smaller crystals are more likely to lose atoms this
way, because they have a higher surface area and
correspondingly a higher proportion of atoms at
high-energy sites.
73 / 77
 Catalytic
Reactions
c. Crystallite migration
Thus, the big clusters get bigger and the small
Basics concepts of
catalysts and clusters become even smaller. Conversely, in the
catalysis
Action of catalysts
crystallite migration model, entire metal crystallites
Green Catalysis migrate on the support surface, collide,
Mode of Action of
Catalyst
Type of Catalysts
Catalytic Reaction
Mechanisms
Characteristics of
Catalyst in
heterogeneous
reactions
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

74 / 77
 Catalyst Inhibition and Poisoning

Catalytic
Reactions A catalyst inhibitor is any chemical species which
can bind to the same site as the substrate
Basics concepts of
catalysts and
catalysis
This changes the properties of the active site and
Action of catalysts stops or retards the catalytic activity.
Green Catalysis
Mode of Action of
Catalyst
The structure and shape of the catalyst change,
Type of Catalysts reducing the active site.
Catalytic Reaction
Mechanisms
Characteristics of
Catalyst inhibition is traditionally associated with
Catalyst in
heterogeneous
biocatalytic processes, but can also apply to
reactions homogeneous and heterogeneous catalysis
Developing the
Rate of Catalytic
Reactions
Catalyst
Deactivation

75 / 77
 Catalyst Poisoning

Catalytic
Reactions When an inhibitor bonds irreversibly to the catalyst,
we say that it is poisons the catalyst.
Basics concepts of
catalysts and
catalysis
Like sintering and inhibition, poisoning depends on
Action of catalysts temperature and reaction conditions.
Green Catalysis
Mode of Action of
Catalyst
In heterogeneous catalysis people distinguish
Type of Catalysts between permanent poisons and temporary poisons.
Catalytic Reaction For the latter, the catalyst can be regenerated,
Mechanisms
Characteristics of
usually by re-calcining (burning off the poison at
Catalyst in
heterogeneous
reactions
high temperature).
Developing the
Rate of Catalytic
Reactions
Poisons can be selective for a certain catalyst, or for
Catalyst certain reactions. Coke, sulfur, and phosphorus are
Deactivation
common poisons in automotive catalysis, as was
lead when it was still being added to gasoline as an
anti-knocking agent .
76 / 77
 Catalytic
Reactions
2. Consider the reaction,
S
C O2
Basics concepts of
catalysts and
Develop the rate law when
catalysis
Action of catalysts
A) Adsorption is the rate controlling
Green Catalysis B) Surface reaction is the rate controlling and,
Mode of Action of
Catalyst
C) Desorption is the rate controlling
Type of Catalysts Solution:
Catalytic Reaction
Mechanisms
Adsorption: Ag +S A-S
Characteristics of
Catalyst in
heterogeneous rA = kA PACS − K−ACA−S (75.1)
reactions
Developing the
Rate of Catalytic
Surface reaction: A-S B-S
Reactions
Catalyst
Deactivation
rS = kSCA−S − K−SCB−S (75.2)
Desorption: B-S Bg +S
rD = kDCB−S − K−D PBCS (75.3)
77 / 77