CATALYSIS

“Catalyst is a substance which speeds up and speeds down a chemical reaction without itself being used
up.”

Berzelius(1836)introduced the term catalysis and catalyst.

Ostwald(1895)redefined a catalyst as, “A substance which changes the reaction rate without affecting
the overall energetics of the reaction is termed as a catalyst and the phenomenon is known as
catalysis.”   

THEORY OF CATALYSIS

There are two theories of catalysis which is described as follows.

(1) Intermediate compound theory of catalysis

(i) This theory was proposed by Clement and Desormes in 1806. According to this theory, the desired
reaction is brought about by a path involving the formation of an unstable intermediate compound,
followed by its decomposition into the desired end products with the regeneration of the catalyst.

(ii) The intermediate compund may be formed in either of two ways

(a) When the intermediate compound is reactive and reacts with the other reactants.

(b) When the intermediate is unstable and decomposes to give the final product.

Where, A, B and C are the reactant molecules and X is the molecule of the catalyst. The first type of
reaction sums up to, AB + C —> CB + A

While the second to, A+ B —> AB  in many cases, the intermediate compounds postulated to be formed
are known compounds and often their presence is detected.

(2) Adsorption theory of catalysis

(i) This theory is applicable to reactions between gases in the presence of a solid catalyst. Some typical
examples are as follows.

(ii) The contact process for the oxidation of SO2  to SO3  with atmospheric oxygen in the presence of
platinum as the catalyst.
 

(iii) The Haber’s process for the synthesis of ammonia with iron as the catalyst.

(iv) Adsorption results in the loosening of the chemical bonds in the reactant molecules, so that their
rupture becomes easier. This is confirmed by the observed lower activation energies for heterogeneous
catalytic reactions in the presence of the catalysts as compared to that for the same reaction in the
absence of the catalyst.

TYPES OF CATALYSIS

Catalytic reactions can be broadly divided into the following types,

(1) Homogeneous catalysis : When the reactants and the catalyst are in the same phase (i.e. solid,
liquid or gas). The catalysis is said to be homogeneous. The following are some of the examples of
homogeneous catalysis.

(i) In the lead chamber process

(ii) In the hydrolysis of ester                                         

(iii) In the hydrolysis of sugar

(2) Heterogeneous catalysis : The catalytic process in which the reactants and the catalyst are in
different phases is known as heterogeneous catalysis. Some of the examples of heterogeneous
catalysis are given below.

(i) In contact process for H2SO4

(ii) In Haber’s process for NH3

(iii) In Ostwald’s process for HNO3

(3) Positive catalysis : When the rate of the reaction is accelerated by the foreign substance, it is said to
be a positive catalyst and phenomenon as positive catalysis. Some examples of positive catalysis are
given below.

(i) Decomposition of KClO3

(ii) Oxidation of SO2

(iii) Decon’s process

(4) Negative catalysis : There are certain, substance which, when added to the reaction mixture, retard
the reaction rate instead of increasing it. These are called negative catalyst or inhibitors and the
phenomenon is known as negative catalysis. Some examples are as follows.

 
(i) Oxidation of sodium sulphite

(ii) Oxidation of benzaldehyde

(iii) Tetra ethyl lead (TEL) is added to petrol to retard the ignition of petrol vapours on compression in an
internal combustion engine and thus minimise the knocking effect.

(5) Auto-catalysis : In certain reactions, one of the product acts as a catalyst. In the initial stages the
reaction is slow but as soon as the products come into existences the reaction rate increases. This type of
phenomenon is known as auto-catalysis. Some examples are as follows,

(i) The rate of oxidation of oxalic acid by acidified potassium permanganate increases as the reaction
progresses. This acceleration is due to the presence of Mn 2+  ions which are formed during reaction. Thus
Mn2+ ions act as auto-catalyst.

(ii) When nitric acid is poured on copper, the reaction is very slow in the beginning, gradually the reaction
becomes faster due to the formation of nitrous acid during the reaction which acts as an auto-catalyst.

 
(6) Induced catalysis : When one reaction influences the rate of other reaction, which does not occur
under ordinary conditions, the phenomenon is known as induced catalysis. Some examples are as
follows, 

(i) Sodium arsenite solution is not oxidised by air. If, however, air is passed through a mixture of the
solution of sodium arsenite and sodium sulphite, both of them undergo simultaneous oxidation. The
oxidation of sodium sulphite, thus, induces the oxidation of sodium arsenite.

(ii) The reduction of mercuric chloride (HgCl2) with oxalic acid is very slow, but potassium permanganate
is reduced readily with oxalic acid. If, however, oxalic acid is added to a mixture of potassium
permanganate HgCl2 and both are reduced simultaneously. The reduction of potassium permanganate,
thus, induces the reduction of mercuric chloride.

(7) Acid-base catalysis : According to the Arrheniusand Ostwald H+or H–   ion act as a catalyst.

(i) For example, Hydrolysis of an ester,

(ii) Inversion of cane sugar,

(iii) Conversion of acetone into diacetone alcohol,

 
ENZYME CATALYSIS

(1) Enzymes are complex nitrogenous substances these are actually protein molecules of higher
molecular mass.

(2) Enzymes catalyse numerous reactions, especially those connected with natural processes.  

(3) Numerous reactions occur in the bodies of animals and plants to maintain the life process. These
reactions are catalysed by enzymes. The enzymes are thus, termed as bio-chemical catalysts and the
phenomenon is known as bio-chemical catalysis.

(4) Nitrogenase an enzyme present in bacteria on the root nodules of leguminous plants such as peas
and beans, catalyses the conversion of atmospheric N 2 to NH3 .

(5) In the human body, the enzyme carbonic anhydrase catalyses the reaction of CO 2 with H2O,

     CO2(aq) + H2O H'(aq) + HCO–3(aq.)

The forward reaction occurs when the blood takes up CO2 in the tissues, and the reverse reaction occurs
when the blood releases CO2 in lungs.

(6) In manufacturing of ethyl alcohol

CHARACTERISTICS OF CATALYSIS

The following are the characteristics which are common to must of catalytic reactions.

(1) A catalyst remains unchanged in mass and chemical composition at the end of the reaction.

(2) A small quantity of the catalyst is generally sufficient to catalyses almost unlimited reactions

(i) For example, in the decomposition of hydrogen peroxide, one gram of colloidal platinum can catalyses
108 litres of hydrogen peroxide.

(ii) In Friedel craft’s reaction, anhydrous aluminium chloride is required in relatively large amount to the
extent of 30% of the mass of benzene, 

(3) The catalyst cannot initiate the reaction: The function of the catalyst is to alter the speed of the
reaction rather than to start it.

(4) The catalyst is generally specific in nature: A substance, which acts as a catalyst for a particular
reaction , fails to catalyse the other reaction , different catalysts for the same reactant may for different
products.

 
Examples :          
 

(5) The catalyst cannot change the position of equilibrium : The catalyst catalyse both forward and
backward reactions to the same extent in a reversible reaction and thus have no effect on the equilibrium
constant.

 
(6) Catalytic promoters : Substances which themselves are not catalysts, but when mixed in small
quantities with the catalysts increase their efficiency are called as promoters or activators.

(i) For example, in Haber’s process for the synthesis of ammonia, traces of molybdenum increases the
activity of finely divided iron which acts as a catalyst.

(ii) In the manufacture of methyl alcohol from water gas (CO + H 2) , chromic oxide (Cr2O3) is used as a
promoter with the catalyst zinc oxide (ZnO).

(7) Catalytic poisons : Substances which destroy the activity of the catalyst by their presence are known
as catalytic poisons.

(i) For example, the presence of traces of arsenious oxide (As 2O3) in the reacting gases reduces the
activity of platinized asbestos which is used as catalyst in contact process for the manufacture of
sulphuric acid.

(ii) The activity of iron catalyst is destroyed by the presence of H 2S  or CO  in the synthesis of ammonia
by Haber’s process.

(iii) The platinum catalyst used in the oxidation of hydrogen is poisoned by CO.

(8) Change of temperature alters the rate of catalytic reaction as it does for the same reaction in
absence of catalyst : By increasing the temperature, there is an increase in the catalytic power of a
catalyst but after a certain temperature its power begins to decrease. A catalyst has thus, a particular
temperature at which its catalytic activity is maximum. This temperature is termed as optimum
temperature.

(9) A positive catalyst lowers the activation energy

(i) According to the collision theory, a reaction occurs on account of effective collisions between the
reacting molecules.
 

(ii) For effective collision, it is necessary that the molecules must possess a minimum amount of energy
known as activation energy (Ea).

(iii) After the collision molecules form an activated complex which dissociate to yield the product
molecules.

(iv) The catalyst provides a new pathway involving lower amount of activation energy. Thus,

(vi) ER and EP   represent the average energies of reactants and products. The difference gives the value
of ?G , i.e., ?G = ER – EP

ACTIVITY AND SELECTIVITY OF CATALYSTS

(1) Activity : Activity is the ability of catalysts to accelerate chemical reaction, the degree of acceleration
can be as high as 1010  times in certain reactions. For example reaction between  H2 and O2  to form H2O
in presence of platinum as catalyst takes place with explosive violence.

In absence of catalyst, H2 and O2 can be stored indefinitely without any reaction.    

(2) Selectivity : Is the ability of catalysts to direct reaction to yield particular products (excluding other).