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CATALYSIS

Catalyst:- A catalyst can be defined as a substance, a small amount of which alters the rate
of a chemical reaction by its presence without undergoing any change in the mass and
chemical composition of it.
Catalysis:- The phenomenon of changing the rate of a chemical reaction by the presence of
a catalyst is called Catalysis.
Types of Catalysts:Catalysts can be classified into two types. They are 1) Positive Catalyst, 2) Negative
Catalyst.
Positive Catalyst: A catalyst which enhances the rate of a reaction is called a positive
catalyst and the process is called Positive Catalysis.
Eg:- MnO2 in the decomposition of KClO3 into KCl and O2.
MnO2
2 KCl + 3O2
2 KClO3
Negative Catalyst: A catalyst which retards the rate of a reaction is called a Negative
Catalyst and the process is called Negative Catalysis.
Eg:- Alcohol retards the oxidation of chloroform to poisonous phosgene.
Types of Catalysis:There are two main types of catalysis. 1) Homogeneous catalysis 2) Heterogeneous catalysis.
(1) Homogeneous catalysis: If the reactants and catalyst are in same phase, it is called
Homogeneous catalyst and that phenomenon is called Homogeneous catalysis.
Eg:- 1) Oxidation of sulphur dioxide to sulphur trioxide with nitric oxide (NO) as catalyst
in the Leadchambers Process.
NO( g )
2SO2 ( g ) + O2 ( g )
2SO3 ( g )
2) Decomposition of acetaldehyde with iodine as catalyst.
I 2 ( vapour )
CH 3CHO( vapour )
CH 4( g ) + CO( g )
3) Hydrolysis of cane sugar in aqueous solution in the presence of mineral acid as
catalyst.
H 2 SO4 ( aq )
C12 H 22O11 (aq) + H 2O(l )
C6 H 12O6 (aq ) + C6 H 12O6 (aq )
Sucrose
Glucose
Fructose
4) Hydrolysis of an ester in the presence of acid or alkali.
+

H / OH ( aq )
CH 3COOC 2 H 5 (aq) + H 2O(l )
CH 3COOH (aq) + C 2 H 5OH (aq)
5) Decomposition of hydrogen peroxide in the presence of iodine ion as catalyst.
I (l )
2 H 2 O(l ) + O2 ( g )
2 H 2O2 (l )
(2) Heterogeneous catalysis: If the reactants and catalyst are in different phase, it is called
Heterogeneous catalyst and that phenomenon is called Heterogeneous catalysis.
Eg:- 1) Combination of sulphur dioxide and oxygen in the presence of finely divided
platinum or vanadium pentoxide in Contacts method.
2O5 ( s )
2 SO2 ( g ) + O2 ( g ) V
2 SO3 ( g )
2) Combination of Nitrogen and Hydrogen to form ammonia in the presence of
finely divided iron (Haber process)
Fe ( s )
N 2 ( g ) + 3H 2 ( g )
2 NH 3 ( g )
3) The decomposition of hydrogen peroxide in the presence of Manganese dioxide
(or) platinum.

Pt / MnO2
2 H 2O2 (l )

2 H 2O(l ) + O2 ( g )
4) Hydrogenation reactions of unsaturated organic compounds are catalysed by
finely divided nickel.
Ni ( s )
CH 2 = CH 2 ( g ) + H 2 ( g )
CH 3 CH 3 ( g )
5) Hydrogenation of animal and vegetable oils using Nickel as catalyst.

Characteristics of a catalyst:
1)
A catalyst does not initiate a reaction but will increase the speed of the reaction.
Eg:- The reaction between H2 and O2 in presence finely divided Pt as catalyst takes
place very quickly even at room temperature, but in the absence of catalyst, the
reaction is so slow that no appreciable amount of water is formed even after several
years.
2)
A catalyst does not undergo chemical change. But a slight change in its physical
state, colour etc., may occur.
Eg:- 1) Coarsely grained MnO2, used in the decomposition of KClO3, becomes
finely powdered after the reaction.
2) Platinum gauze used as catalyst for the oxidation of ammonia becomes rough after
some time.
3)
A catalyst has no influence on the position of equilibrium.
Eg:- The same position of equilibrium was reached in the reaction of SO2 and O2
using the catalysts, namely V2O5, Pt.
4)
Small amounts of catalyst is sufficient to catalyse the reaction.
Eg:- Colloidal Platinum present at a concentration of 1g. atom in 106 litres catalyse
the decomposition of H2O2.
5)
A catalyst is selective in nature i.e., for a particular reaction, the catalyst is specific. If
catalyst changes, products of the reaction will change.
Eg:- Ethanol is converted into ethanal in presence of hot copper as catalyst, while it
gives ethene when passed over hot Al2O3.
Al2O3

C 2 H 4 + H 2 O
Cu
C 2 H 5OH
CH 3CHO + H 2

Eg:- Formic Acid is converted into Carbon Monoxide in presence of Alumina,


while it gives Carbon Dioxide in presence hot copper as catalyst.
Al2O3

CO + H 2O
Cu
HCOOH
CO2 + H 2
6)

7)

8)

Activity of a catalyst can be increased by adding a small amount of another substance


called promoter.
Eg:- Mo is the promoter to Fe in Habers Process.
Activity of a catalyst can be decreased by adding a small amount of another substance
called Poison.
Eg:- As2O3 is the poison to Pt in contact process.
H2S is the poison to Fe in Habers Process.
Fe +H2S FeS + H2
Finely divided catalyst acts more effectively than bulk or lump form (coarsely
powdered).
Eg:- Finely divided Ni has been found to be more effective than pieces (or) lumps
of Nickel.

9)

A catalyst which retards the velocity of a reaction is called Negative Catalyst.


Eg:a) Decomposition of H2O2 is retarded by the presence of glycerol which acts as
negative catalyst.
b) Addition of anti-knocking substance Tetra Ethyl Lead (TEL) inhibits the rapid
and explosive combustion of the petrol. Thus, knocking in the engine is
prevented.
c) Chloroform undergo aerial oxidation forming phosgene which is highly
poisonous. When 1-2% of ethanol is added to chloroform, it acts as a negative
catalyst and suppress the formation poisonous phosgene.

AUTO CATALYSIS:
When one of the product of a reaction acts as a catalyst, then it is called auto catalyst and that
phenomenon is called Auto Catalysis.
Eg:- 1) IN the ester hydrolysis, the acid formed will act as auto catalyst.
CH 3COOC 2 H 5 + H 2O
CH 3COOH + C2 H 5OH
2) IN the oxidation of oxalic acid by acidified KMnO4 the Mn2+ ions formed acts as
autocatalysts.
2 KMnO4 + 5H 2C 2 O4 + 3H 2 SO4 K 2 SO4 + 2MnSO4 + 8 H 2 O + 10CO2
3) IN the decomposition of arsine, the arsenic formed catalyses the reaction.
2 AsH 3
2 As + 3H 2
IMPORTANT INDUSTRIAL PROCESSES USING CATALYSTS:
Process
Catalyst
S.No.
1)
Habers process for the manufacture of Ammonia
Fe. Mo as promoter
2)
Contact process for the manufacture of Sulphuric acid.
Pt (or) V2O5
3)
Ostwalds process for the manufacture of Nitric Acid
Pt gauze
4)
Hydrogenation of oils for the manufacture of Vanaspathi
Ni
5)
Deacons process for manufacture of Chlorine
CuCl2
6)
Boschs process for manufacture of Hydrogen
Fe2O3 + Cr2O3
7)
Cracking of heavy petroleum fractions.
Silica, Alumina gel
8)
Manufacture of ehyl alcohol by fermentation of sugar.
INvertase, Zymase
9)
Manufacture of ethyl alcohol by fermentation of Starch
Diastase, maltase
10)
Acetic acid from alcohol
Mycoderma Aceti
11)
Acetic acid from acetaldehyde by aerial oxidation
V2O5
12)
Acetaldehyde from acetylene
HgSO4
CHOOSING FOR A GOOD CATALYST FOR INDUSTRIAL PROCESSES:
@ It should be cheap and easily available.
@ It should be stable. It must be selective so that the desired product is major product.
@ It should be easily regenerated (or) reactivation.
@ It should possess maximum possible activity for the reaction under consideration in
terms of the yield of the desired product.

MECHANISM OF CATALYTIC ACTION: (THEORIES OF CATALYSIS):


To explain the mechanism of catalysis, the following two theories have been proposed:
1) Unstable intermediate compound formation theory:

2) Adsorption (or) contact theory:

1)

Unstable intermediate compound formation theory:


This theory was proposed by Clement and Desormes in 1806. This theory explains
the action of Homogeneous catalysis. According to this theory, the catalyst interacts
with reactant to form very reactive and unstable intermediate compound, which
immediately reacts with other reactant yielding the products of the reaction and
liberating the catalyst in its original chemical composition.

For example, a reaction of the type


Which occurs in presence of a catalyst K, may take place as,
Catalyst

Intermediate
Compound

{slow reaction}

Product

{fast reaction}

Catalyst

Example:
1)
Catalytic action of NO in the manufacture of H2SO4 by Lead-Chambers process:
O2 <=>
2SO3
Main Reaction: 2SO2 +
Reactant1 Reactant2 Product
Mechanism:

2)

2NO
+ O2 <=> 2NO2
Catalyst
reactant2 intermediate compound
2SO2 <=> 2SO3 +
2[NO]
2NO2 +
(reactant1) product
-------------------------------------------------------------------[2(NO)]
2SO2 + O2 + [2(NO)] <=> 2SO3 +
Catalyst
Catalyst
-------------------------------------------------------------------KClO3 on heating in presence of MnO2 liberates oxygen
+
Cl2
+ O2
2KClO3 + 2MnO2 <=> 2KMnO4
Catalyst
(intermediate compound)
O2
2KMnO4 <=> K2MnO4 + MnO2 +
Catalyst
K2MnO4 + Cl2 <=> 2KCl + MnO2 + O2
-------------------------------------------------------------------2KClO3 + [2MnO2] <=> 2KCl + 3O2 + [2MnO2]
--------------------------------------------------------------------

This theory fails to explain the action of catalytic promoters, catalytic poisons and action of
finely divided catalysis.

2.

Adsorption (or) Contact Theory:

1)
2)
3)

4)

This theory was postulated by Faraday in 1883 and later reviews by many others. It
explained the action of heterogeneous catalysis.
According to this theory,
The surface of the solid catalyst possesses some isolated active sites (or centers) or
free unsatisfied valencies having affinity towards substrate.
Due to these free unsatisfied valency sites on the surface of the catalyst, the molecule
of the gaseous reactants get adsorbed in an unimolecular thickness.
The chemical action is accelerated on account of increased concentration of the
reacting substances on the surface of the solid catalyst and no definite intermediate
compound formation takes place.
The forces which keep the molecules of reactants intact with catalyst also attract the
reacting molecules. The distorted molecules of a catalyst, being under more strain,
are more reactive.
A
B
A
B
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M
M
M
M

- M - M - M - M
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M
M
M
M

- M - M - M - M
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a) Reactant molecules
b) Adsorption of reactant
molecules adjacent to one another
A and B near catalyst(M)

A
B
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- M - M - M - M
|
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- M - M - M - M
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c) Formation of intermediate complex
at catalyst surface

A
B
|
| + |
|
- M - M - M - M
|
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- M - M - M - M
|
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d) Desorption of product, AB
leaving the surface for further action

Simply this theory involves five steps:


1) Diffusion of reactants to the surface of the catalyst.
2) Adsorption of reactants on to the surface of the catalyst.
3) Occurrence of chemical reaction on the catalyst surface.
4) Desorption of reaction products away from the catalyst surface.
5) Diffusion of products away from the catalyst surface.

Example:
Reaction between ethane and hydrogen in the presence of a Nickel Catalyst.
One important industrial use of this reaction is in the hydrogenation of vegetable oils to
prepare ghee, which also involves reaction of a carbon-carbon double bond in the vegetable
oil with the hydrogen in the presence of a Ni Catalyst.
Advantages of contact (or) adsorption theory:
This theory can explains about the working of promoter and catalytic poisons.
The efficiency of the catalyst is depends on the free valencies of the catalyst.
These free valencies can be increased in the following two ways:
1) Sub-division of the catalyst
2) Rough surface of the catalyst.

Sub-division of the catalyst: The number of free valancies increases on disintegration.


Finely powdered or colloidal catalyst particles having large surface area are very rich in free
valencies. Actually, it is observed that finely divided nickel and colloidal platinum act as
efficient catalysts.
Rough surface of the catalyst: There are a number of active spots in the form of edges,
corners, cracks and peaks on a rough surface. They give rise to an increase in number of free
valencies. These active spots enhance the adsorption and thereby increase the catalytic
efficiency of the catalyst.
Working of poison: The poisons are preferentially adsorbed at the active centers of the
catalyst. This effect reduces the free valencies for the reacting molecules and thus the
catalyst activity decreases.
Working of Promotor: Promoters are responsible for increasing the roughness of the
surface of a catalyst. This effect increases the free valencioes for the reacting molecules and
thus, the catalytic activity of the catalyst is increased.
ENZYMES (OR) BIOLOGICAL CATALYSTS:
Enzymes are highly complex, non-living, nitrogenous organic substances produced by living
animals and plants. They possess the incredible capacity in bringing about many complex
chemical reactions like hydrolysis, oxidation, reduction etc., They are highly specific and
each enzyme can catalyze a specific reaction. The catalytic activity of enzyme, like catalysts,
is due to their capacity to lower the activation energy for a particular reaction.

For example:
1)
Starch is catalyzed by diastase to form maltose, which in turn is hydrolyzed by
maltase into glucose.
2(C6H10O5)n + n H2O Diastase

n C12H22O11
Starch
maltose
2)

Invertase converts cane-sugar into a mixture of glucose and fructose: while zymase
converts glucose and fructose into alcohol.
Invertase

C6H12O6 + C6H12O6
C12H22O11 + H2O
Canesugar
Glucose Fructose
Zymase
C6H12O6 2C2H5OH + 2CO2
Ethyl alcohol

3)

The enzyme urease (present in the soyabeans) converts urea quantitatively into
ammonium carbonate.
NH2CONH2 + 2H2O Urease
(NH4)2CO3

4)

The enzymes pepsin (present in the gastric juice) trypsin, lipase, amylase (present in
the pancreatic juice) and carboxyeptidase, aminopeptidase, maltase lipase (present in
intestine) help the conversion of proteins into amino acids, which are absorbed by
blood for tissue building.

5)

The enzyme ptyalin present in human mouth (saliva) converts starch into glucose.
Ptyalin
n C6H12O6
(C6H10O5)n + n H2O

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