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Catalysis
 Catalysis
• Catalysis is a method of controlling the rate
and direction of chemical reaction.
• A catalyst is defined as a substance which
accelerate the rate of a chemical reaction,
itself remaining chemically unchanged at the
end of the reaction.
• Catalysts are the workhorses of chemical
transformations in the industry.
Approximately 85–90% of the products of
chemical industry are made in catalytic
processes.
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Applications

Industrial Environmental Pharmaceutical

catalysis catalysis catalysis

1 Petroleum refining

2 Ammonia synthesis Automotive catalytic

 
converters

Production of some
3 Methanol synthesis
vital drugs

4 fuels
Pollution abatement
5 polymers

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How do catalyst accelerate the rate of reaction

A catalyst accelerates the rate of a

chemical reaction by providing a new
pathway for the reaction. This
alternative pathway has lower
activation energy of the reaction.
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 Arrhenius equation
• Kuncat = A e (- Ea uncat / R T)

• Kcat = A e (- Ea cat / R T)

K cat Eauncat  Eacat

ln 
K uncat RT
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 General characteristics of catalyst
1. A catalyst cannot initiate a chemical reaction but it does participate in
the mechanism of the reaction.
2. A catalyst cannot make a thermodynamically unfavorable reaction
proceeds. Rather, it can only speeds up the reaction which is
thermodynamically favorable. The free energy value does not change.
3. A catalyst does not affect the final position of equilibrium, although it
shortens the time required to establish the equilibrium. It implies that
in a reversible reaction the catalyst accelerates the forward and the
reverse reactions equally. Thus the ratio of the rates of two opposing
reactions i.e., the equilibrium constant, remains unchanged.
4. A catalyst remains unchanged in mass and chemical composition at the
end of the reaction. But, its physical form may change.
5. The catalytic activity can be enhanced by adding promoters.
6. A catalyst is specific in its action.
7. The rate of reaction is maximum at a particular temperature called the
optimum temperature of catalyst.

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• Catalyst activity
• The rate of conversion of reactants or formation
of products under a given set of conditions.
• Catalyst selectivity
• A compound may undergo several reactions
giving different products. A good catalyst should
increase the rate of only one of these reactions
leading to the desired product. This property of
catalyst is known as selectivity.

C2 H 5OH 
Cu
CH 3CHO  H 2

C2 H 5OH   C2 H 4  H 2O
Al2O3

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 TYPES OF CATALYSIS
• There are two main types of catalysis :
• (a)Homogeneous catalysis
 Enzyme catalysis
 Autocatalysis

• (b)Heterogeneous catalysis

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 HOMOGENEOUS CATALYSIS
• In homogeneous catalysis, the catalyst is in the same phase as the
reactants and is evenly distributed throughout. This type of catalysis can
occur in gas phase or the liquid (solution) phase.
• Examples of Homogeneous Catalysis in Gas Phase

2 SO2 ( g )  O2 ( g )  2 SO3 ( g )

NO ( g )

• Examples of Homogeneous Catalysis in Solution Phase

• Many reactions in solutions are catalyzed by acids (H+) and bases (OH–).
• Hydrolysis of an ester in the presence of acid or alkali

H
CH 3COOC2 H 5 (aq )  H 2O(l )  C2 H 5OH (aq )  CH 3COOH (aq )

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 AUTOCATALYSIS
• When one of the products of reaction itself acts
as a catalyst for that reaction the phenomenon
is called Autocatalysis.
• Oxidation of Oxalic acid. When oxalic acid is
oxidized by acidified potassium permanganate,
manganous sulphate produced during the
reaction acts as a catalyst for the reaction.

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 ENZYME CATALYSIS
• Numerous organic reactions are taking place in the body of
animals and plants to maintain the life process. These
reactions being slow remarkably catalyzed by the organic
compounds known as Enzymes. All enzymes have been
found to be complex protein molecules. Thus :
• Enzymes are protein molecules which act as catalysts to
speed up organic reactions in living cells.
• The catalysis brought about by enzymes is known as
Enzyme Catalysis.
• Each enzyme is produced in a particular living cell to
catalyze a reaction occurring in that cell. Many enzymes
have been identified and obtained in pure crystalline state
from the cells to which they belong. However the first
enzyme as prepared by synthesis in the laboratory in 1969.
• Examples of Enzyme Catalysis

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 HETEROGENEOUS CATALYSIS
• The catalysis in which the catalyst is in a different physical phase
from the reactants is termed Heterogeneous catalysis.
• The most important of such reactions are those in which the
reactants are in the gas phase while the catalyst is a solid. The
process is also called Contact catalysis since the reaction occurs by
contact of reactants with the catalyst surface. This form of catalysis
has great industrial importance.
• Examples of Heterogeneous Catalysis
2 SO2 ( g )  O2 ( g )  
Pt
2 SO3 ( g )

• Combination of nitrogen and hydrogen to form ammonia in the

presence of finely divided iron, (Haber Process for Ammonia).

N 2  3H 2 
Fe
2 NH 3

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 THEORIES OF CATALYSIS
• There are two main theories of catalysis :
(1) Intermediate Compound Formation theory
(2) The Adsorption theory.
• In general, the Intermediate Compound
Formation theory applies to homogeneous
catalytic reactions and the Adsorption theory
applies to heterogeneous catalytic reactions.

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The Intermediate Compound Formation Theory
• As already discussed a catalyst functions by providing a new pathway of lower activation energy.
In homogeneous catalysis, it does so by forming an intermediate compound with one of the
reactants. The highly reactive intermediate compound then reacts with the second reactant to
yield the product, releasing the catalyst. Let us illustrate it by taking the general reaction

The activation energies of the reactions (2) and (3) are lower than that of the reaction (1) Hence
the involvement of the catalyst in the formation of the intermediate compound and its subsequent
decomposition, accelerates the rate of the reaction (1) which was originally very slow.

Example 1. Catalytic oxidation of sulphur dioxide (SO2) in the presence of

nitric oxide (NO) as catalyst. (Chamber Process of Sulphuric acid)

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 MECHANISM OF ENZYME CATALYSIS
 The long chains of the enzyme (protein) molecules are
coiled on each other to make a rigid colloidal particle
with cavities on its surface.
 These cavities which are of characteristic shape and
abound in active groups (NH2, COOH, SH, OH)] are
termed Active centers. The molecules of substrate
which have complementary shape, fit into these
cavities just as key fits into a lock (Lock-and-Key
theory).
 By virtue of the presence of active groups, the enzyme
forms an activated complex with the substrate which at
once decomposes to yield the products.
 Thus the substrate molecules enters the cavities, forms
complex and reacts, and at once the products get out
of the cavities.
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Michaelis and Menten (1913) proposed the following
mechanism for enzyme catalysis

where E = enzyme; S = substrate (reactant); ES = activated

complex; P = products.

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 The Adsorption Theory
• This theory explains the mechanism of a reaction between two
gases catalyzed by a solid (Heterogeneous or Contact Catalysis).
Here the catalyst functions by adsorption of the reacting molecules
on its surface.
Generally speaking, Five steps can be put forward for heterogeneous
catalysis. For example, if the reaction is :

1. Diffusion of adsorptive reactants to the active site on the solid

surface.
2. Adsorption of one or more reactants (adsorbates) onto the
surface: if molecule A is chemically adsorbed onto one of the
active sites, a surface complex (S–A) is formed.
3. Surface reaction: A reacts with B.
4. Desorption of products from the surface:(C+ D) escapes the site,
thus regenerating site S.
5. Diffusion of products away from the surface.
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Energy diagram explaining steps in
heterogeneous catalysis.

Mechanism of the hydrogenation of

ethene on nickel surface. 20
 Catalyst Supports
• In order to increase the
surface area of a metal
catalyst, the catalyst is
distributed on the
surface of a high surface
area materials called
supports. The support is
generally catalytically
inactive.
• Example
• Alumina and silica. Catalysts are nano-materials and
Catalysis is nanotechnology.

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 PROMOTERS
• The activity of a catalyst can often be increased
by addition of a small quantity of a second
material. This second substance is either not a
catalyst itself for the reaction.
• Example of Promoters
• Molybdenum (Mo) or aluminum oxide (Al2O3)
promotes the activity of iron catalyst in the Haber
synthesis for the manufacture of ammonia.
Structural promoters stabilize the relatively large
metallic iron area.

N 2  3H 2  2 NH 3
Fe / Mo

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Physical changes in heterogeneous catalysts

1. Change form higher particle size to lower particle size.

2. Catalyst deactivation (reduction of catalytic activity).

 Catalyst Sintering (thermal degradation) :
At high temperatures, the size and shape of the metal crystallites
can change. This decreases the catalysts surface area and the
number of active sites.
 Poisoning
 Fouling
A physical blockage of the catalytically active sites by (the
deposit of dust or fine powder or carbonaceous deposits )
 Loss of active species
Transition from oxidation state to another oxidation state.

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 CATALYTIC POISONING
• A substance which destroys the activity of the heterogeneous
catalyst to accelerate a reaction, is called a poison and the process
is called Catalytic poisoning. This is due to a blocking effect of the
active free sites on the surface.
• The catalytic poisoning occurs by:
 the presence of small amounts of impurities in the reactants. The
catalyst may combine chemically with the impurity.
The iron catalyst used in the synthesis of ammonia (Haber Process) is poisoned
by H2S Fe + H2S → FeS + H2
 Strong Adsorption of one of the reacting species so that, the
surface becomes unavailable for further adsorption of the
reactants.
• 2 CO + O2 → 2 CO2
Poisoning of platinum catalyst by
carbon monoxide. 24
 Heterogeneous catalysis
• Catalysis in the chemical industry
• Almost the whole of modern chemical
industry depends on the development,
selection, and application of catalysts.

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 Catalytic Converter
• The three-way catalyst, consisting of Pt and Rh
particles supported on a ceramic monolith,
represents a remarkably successful piece of
catalytic technology. It enables the removal of
the three pollutants CO, NO and hydrocarbons.

Reactions in the three-way catalyst

Reaction

Reaction Most efficient

catalysts
CO + O2 → CO2 Pt, Pd

CxHy + O2 → CO2 Pt, Pd

NO + CO → N2 + CO2 Rh, Pd
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 Langmuir–Hinshelwood or Eley–Rideal
Mechanisms
 In Langmuir–Hinshelwood kinetics is it
assumed that all species are adsorbed and
accommodated (in thermal equilibrium) with the
surface before they take part in any reactions.
Hence, species react in the chemisorbed state
on the surface. This is the prevailing situation in
heterogeneous catalysis.
 Rate = k θA θB
 the so-called Eley–Rideal mechanism, in which one of
the reactants reacts directly out of the gas phase,
without being accommodated at the surface.
 For instance, in the reaction of A + B, a gas-phase
molecule of B might approach the surface and react with
chemisorbed A* without being adsorbed itself.
 Rate = k θA PB
 An example of an Eley–Rideal process is the reaction of
gas-phase atomic hydrogen with a surface saturated
with atomic hydrogen. The strongly activated hydrogen
atom (which is a free radical) reacts readily with one of
the adsorbed hydrogen atoms and, since molecular
hydrogen does not usually adsorb strongly to a surface,
the resultant molecule desorbs instantaneously.