Physical Chemistry (D. Ch. Eng.

) Sem-II

CATALYSIS
Berzelius (1836) realized that there are substances which increase the rate of a reaction
without themselves being consumed. He believed that the function of such a substance was to
loosen the bonds which hold the atoms in the reacting molecules together. Thus he coined the
term Catalysis (Greek kata = wholly, lein = to loosen).
There is no doubt that usually a catalyst accelerates a reaction as was originally through
by Berzelius. But a number of cases are now known where the catalyst definitely retards (slows
down) the rate of reaction.
A catalyst is defined as a substance which alters the rate of a chemical reaction, itself
remaining chemically unchanged at the end of the reaction. The process is called Catalysis.
As evident from the above definition, a catalyst may increase or decrease the rate of a
reaction.
A catalyst which enhances the rate of a reaction is called a Positive catalyst and the
process Positive catalysis or simply Catalysis.
A catalyst which retards the rate of a reaction is called a Negative catalyst and the
process Negative catalysis.
TYPES OF CATALYSIS:-
There are two main types of catalysis:
(a) Homogeneous catalysis,
(b) Heterogeneous catalysis.
Also, there is a third type of catalysis known as Enzyme catalysis which is largely of
biological interest.
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
(a) Oxidation of sulphur dioxide (SO2) to sulphur trioxide (SO3) with nitric oxide (NO) as
catalyst,

(b) Decomposition of acetaldehyde (CH3CHO) with iodine (I2) as catalyst,

Examples of Homogeneous Catalysis in Solution Phase

Many reactions in solutions are catalyzed by acids ( ) and bases ( ).
(a) Hydrolysis of cane sugar in aqueous solution in the presence of mineral acid as catalyst,

(b) Hydrolysis of an ester in the presence of acid or alkali,

(c) Decomposition of hydrogen peroxide (H2O2) in the presence of iodide ion (I–) as catalyst,

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 Physical Chemistry (D. Ch. Eng.) Sem-II

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. In contact
catalysis, usually the catalyst is a finely divided metal or gauze. This form of catalysis has great
industrial importance.
Examples of Heterogeneous Catalysis
Some examples of heterogeneous catalysis with reactants in the gas, liquid or the solid phase are
listed below.
(1) Heterogeneous catalysis with gaseous reactants (Contact catalysis):-
(a) Combination of sulphur dioxide (SO2) and oxygen in the presence of finely divided
platinum/vanadium pentoxide, V2O5, (Contact Process for Sulphuric acid).

(b) Combination of nitrogen and hydrogen to form ammonia in the presence of finely divided
Iron (Haber process for Ammonia).

(c) Oxidation of ammonia to nitric oxide (NO) in the presence of platinum gauze (during
manufacturing of Nitric acid).

(d) Hydrogenation reactions of unsaturated organic compounds are catalyzed by finely divided
nickel.

Vegetable oils are tri-esters of glycerol with higher unsaturated acid (oleic acid). When
hydrogen is passed through the vegetable oils in the presence of nickel, the carbon-carbon double
bonds of the acid portions are hydrogenated to yield solid fats (Vanaspati ghee).
(2) Heterogeneous catalysis with liquid reactants:-
(i) The decomposition of aqueous solutions of hydrogen peroxide (H2O2) is catalyzed by
manganese dioxide (MnO2) or platinum in colloidal form,

(ii) Benzene and ethanoyl chloride (CH3COCl) react in the presence of anhydrous aluminum
chloride to form phenyl methyl ketone (C6H5COCH3),

(3) Heterogeneous catalysis with solid reactants.

The decomposition of potassium chlorate (KClO3) is catalyzed by manganese dioxide (MnO2).

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 Physical Chemistry (D. Ch. Eng.) Sem-II

Types of Catalysts:
There are many types of catalysts as follows:
1. Positive Catalyst: A catalyst which can increase the rate of any chemical reaction is
known as Positive Catalyst and the process is called positive Catalysis.
2. Negative Catalyst: When a catalyst reduces the rate of a reaction, it is called a Negative
catalyst or Inhibitor. This phenomenon is called Negative catalysis or Inhibition. Negative
catalysis is useful to slow down or stop altogether an unwanted reaction.
Examples of Negative Catalysis:
(1) Oxidation of Trichloromethane (CHCl3) Trichloromethane (or chloroform) is used as
anesthetic. Upon oxidation by air it forms carbonyl chloride (COCl2) which is a poisonous
substance.

2% of Ethanol (C2H5OH) when added to chloroform acts as a negative catalyst and suppresses
the formation of carbon chloride.
(2) Decomposition of Hydrogen peroxide,

The decomposition of hydrogen peroxide is retarded by the presence of dilute acids or glycerol.
3. Auto Catalyst: When one of the products of reaction itself acts as a catalyst for that
reaction it is called auto catalysis and the phenomenon is called Autocatalysis.
In autocatalysis the initial rate of the reaction rises as the catalytic product is formed, instead of
decreasing steadily. The curve plotted between reaction rate and time shows a maximum when
the reaction is complete.

Examples of Autocatalysis:
a) Hydrolysis of an Ester. The hydrolysis of ethyl acetate forms acetic acid (CH 3COOH)
and ethanol. Of these products, acetic acid acts as a catalyst for the reaction.

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 Physical Chemistry (D. Ch. Eng.) Sem-II

b) 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.

c) Decomposition of Arsine. The free arsenic produced by the decomposition of arsine

(AsH3) autocatalyses the reaction.

4. 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
or it may be a feeble catalyst. A substance which, though itself not a catalyst, promotes the
activity of a catalyst is called a promoter.
Example of Promoters:
Molybdenum (Mo) or aluminium oxide (Al2O3) promotes the activity of iron catalyst in the
Haber synthesis for the manufacture of ammonia.

In some reactions, mixtures of catalysts are used to obtain the maximum catalytic efficiency. For
example, in the synthesis of methanol (CH3OH) from carbon monoxide and hydrogen, a mixture
of zinc and chromium oxide is used as a catalyst.

5. Retarder / Catalytic Poisoning:

Characteristics of Catalytic reactions

Although there are different types of catalytic reactions, the following features or
characteristics are common to most of them.

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 Physical Chemistry (D. Ch. Eng.) Sem-II

(1) A catalyst remains unchanged in mass and chemical composition at the end of the
reaction. Qualitative and quantitative analysis show that a catalyst undergoes no change in mass
of chemical nature. However, it may undergo a physical change. Thus, granular manganese
dioxide (MnO2) used as a catalyst in the thermal decomposing of potassium chlorate is left as a
fine powder at the end to the reaction.
(2) A small quantity of catalyst is generally needed to produce almost unlimited reaction.
Sometimes a trace of a metal catalyst is required to affect very large amounts of reactants. For
example, one ten-millionth of its mass of finely divided platinum is all that is needed to catalyze
the decomposition of hydrogen peroxide. On the other hand, there are catalysts which need to be
present in relatively large amount to be effective. Thus in Friedel-Crafts reaction,
→
Anhydrous aluminium chloride functions as a catalyst effectively when present to the
extent of 30% of the mass of benzene.
For the acid and alkaline hydrolysis of an ester,
→
Ester the rate of reaction is proportional to the concentration of the catalyst (H + or OH–).
(3) A catalyst is more effective when finely divided in heterogeneous catalysis, the solid catalyst
is more effective when in a state of fine subdivision than it is used in bulk. Thus a lump of
platinum will have much less catalytic activity than colloidal or platinized asbestos. Finely
divided nickel is a better catalyst than lumps of solid nickel.
(4) A catalyst is specific in its action. While a particular catalyst works for one reaction, it will
not necessarily work for another reaction. Different catalysts, moreover, can bring about
completely different reactions for the same substance. For example, ethanol (C2H5OH) gives
ethene (C2H4) when passed over hot aluminium oxide,
→ (Dehydration)
Ethene
But with hot copper it gives ethanal (CH3CHO).
→ (Dehydrogenation)
Ethanal
(5) A catalyst cannot, in general, initiate a reaction. In most cases a catalyst speeds up a
reaction already in progress and does not initiate (or start) the reaction.
(6) 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.

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 Physical Chemistry (D. Ch. Eng.) Sem-II

(7) Change of temperature alters the rate of a catalytic reaction as it would do for the same
reaction witho ut a catalyst.

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