Surface Chemistry - 2

CATALYST
===============================================================================

Substances which alter (Increase or Decrease) the RATE of a reaction by there presence, without undergoing
any change in mass and composition, are termed catalysts and the phenomenon is known as catalysis.

Classification of Catalysis
Catalysis can be broadly classified into two main groups as:
(i) Homogeneous catalysis
(ii) Heterogeneous catalysis
(i) Homogeneous Catalysis: When the catalyst is in the same phase as the reactants and products, then
the catalyst is said to be homogeneous catalyst and such catalytic reaction is said to be homogeneous
catalysis.
NO ( g )
Examples : 2SO 2 (g )  O 2 (g )  o 2SO 3 (g)
HCl( l )
CH3COOCH3 (l )  H 2O(l )  o CH3COOH(l )  CH 3OH(l )
H 2SO 4 ( l )
C12 H 22 O11 (l )  H 2 O(l )  o C6 H12 O 6 (l )  C 6 H12 O 6 (l )
(ii) Heterogeneous Catalysis: When the catalyst is in the different phase as the reactants and
products, then the catalyst is said to be heterogeneous catalyst and such catalytic reaction is said to
be heterogeneous catalysis.
Pt (s )
Examples : 2SO 2 (g )  O 2 (g )  o 2SO 3 (g )
N 2 (g )  3H 2 (g ) Fe
 (s )
o 2 NH 3 (g )
Pt (s)
4NH 3 (g)  5O 2 (g) 
o 4NO(g)  6H 2 O(g)
Cu 2Cl2 (s)
4HCl(g)  O 2 (g) o 2H 2 O(g)  2Cl 2 (g)

TYPES OF CATALYSIS
(i) Positive catalysis : When the rate of reaction is accelerated by a foreign substance, it is said to be a
positive catalyst and the phenomenon is positive catalysis.
e.g., (i) Oxidation of sulphur dioxide in presence of nitric oxide.
2SO2(g) + O2(g)  o 2SO3(g)
NO(g)

(ii) Oxidation of ammonia in presence of platinum gauze.

Pt(s)
4NH3(g) + 5O2(g) 300
o 4NO(g) + 6H O(g)
qC 2

(ii) Negative catalysis : The substance which when added to the reaction mixture, retards the reaction rate is
termed negative catalyst and the phenomenon is known as negative catalysis.
(i) The oxidation of sodium sulphite by air is retarded
by alcohol.
2Na2SO3(s) + O2(g) Alcohol
  (l )
o 2Na2SO4(s)
(ii) The oxidation of chloroform by air is retarded if
some alcohol is added to it.
2CHCl3(l) + O2(g)  o 2COCl2(g) + 2HCl(g)
Alcohol ( l )

TOPIC : SURFACE CHEMISTRY- PART 2 (“CATALYST”) PAGE [1] of 5

 (iii) Auto-catalysis : In certain reactions, one of the products acts as a catalyst. In the initial stages the
reaction is slow but as soon as the products come into existence, the reaction rate increases. The phenomenon
in which one of the product itself acts as a catalyst is said to be auto-catalysis.
e.g., The oxidation of oxalic acid by acidified KMnO4 takes place rapidly after some time. This is due to the
presence of Mn2+ ions which are formed in the reaction.
2MnO 4  5C 2 O 24  16H  o 2Mn 2   10CO 2  8H 2 O
(iv) Induced catalysis : When one reaction influences the rate of another reaction, which does not occur
under ordinary conditions, the phenomenon is known as induced catalysis.
e.g., 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.

Characteristics of Catalysis :
These are the following characteristics which are common to most of the catalytic reactions :
(i) A catalyst remains unchanged in mass and chemical composition at the end of the reaction.
(ii) A small quality of the catalyst is generally sufficient to catalyse almost an unlimited reaction.
(iii) The catalyst cannot initiate the reaction.
(iv) The catalyst is generally specific in nature.
(v) The catalyst cannot change the position of equilibrium in a reversible reaction. However, it can help to
achieve the equilibrium state in lesser time.
(vi) promoters or activators:-
Substance which themselves are not catalysts but when mixed in small quantities with the catalysts, enhance
their efficiency are said to be promoters or activators.
Examples:
N2 + 3H2 ========> 2 NH3. Rate=2
N2 + 3H2 ==(Fe)===> 2 NH3. Rate=4 , hence Fe is a Catalyst
N2 + 3H2 ==(Mo)===> 2 NH3. Rate=2 , hence Mo{Molybdenum} is NOT a Catalyst
N2 + 3H2 ==(Fe/Mo)=> 2 NH3. Rate=10 , hence Mo is a Catalyst Promoters

(vii) catalytic poisons or catalyst inhibitors

Substances which destroy the activity of the catalyst by their presence are known as catalytic poisons or
catalyst inhibitors.
Examples:
N2 + 3H2 ==============> 2 NH3. Rate=2
N2 + 3H2 ======(Fe)=====> 2 NH3. Rate=4 , hence Fe is a Catalyst
N2 + 3H2 =(H2S or CO)====> 2 NH3. Rate=2 , hence H2S or CO is NOT a Catalyst
N2 + 3H2 ==(Fe/H2S or CO)=> 2 NH3. Rate=3 , hence H2S or COis a Catalyst Poison.

(viii) optimum temperature:-A catalyst has a particular temperature at which its activity is maximum. This
temperature is termed as optimum temperature.

TOPIC : SURFACE CHEMISTRY- PART 2 (“CATALYST”) PAGE [2] of 5

THEORIES OF CATALYSIS
Two broad theories of catalytic action have been proposed :
(i) Intermediate compound formation theory :
This was proposed by Clement and Desormes in 1806. According to this theory, the catalyst first forms an
intermediate with one of the reactants, which being unstable combines with other reactants to form the
desired product and the catalyst is regenerated.
Reaction : A + B ===(K, the catalyst)===> C+ D
Steps:
(i) A + K (catalyst) = AK (intermediate)
(ii) ABK + B = C + D + K (catalyst)

“The scope of this theory is limited as the formation of intermediate is not possible in the case of many
reactions.”
(ii) Adsorption theory :
The catalytic activity is localised on the surface of a catalyst. The molecules of the reactants are adsorbed on
the surface of the catalyst. The increase in concentration of the reactants on the surface increases the rate of
reaction (law of mass action). There are free valencies on the surface which are responsible for loose chemical
combination of the reactants with the catalyst. If different molecules are adsorbed side by side, they may
react readily and new molecules are formed which evaporate leaving the way for the fresh reactant molecules.
The free valencies can be increased in two ways :
(i) By sub-division of the catalyst.
(ii) By rough surface of the catalyst.
Adsorption theory is a better theory as it can explain a number of characteristics of the catalyst, especially a
heterogeneous catalyst.
ENZYME CATALYSIS

Enzymes are complex nitrogeneous compounds of high molecular masses ranging from 15,000 to 10,000,00 gm/
mole produced by living plants and animals. Enzymes are protein molecules, form colloidal solutions in water
and catalyse numerous reactions especially connected with natural processes. The enzymes are also termed
as bio-chemical catalysts and the phenomenon is known as bio-chemical catalysis.
The catalytic activity of enzymes is perhaps the greatest of all the catalysts. Their activity is also due to their
capacity to lower the activation energy for a reaction. Each enzyme can catalyse a specific reaction. The
enzyme reactions are sensitive to temperature and pH. Generally the optimum temperature varies between 290-
300 K and the favourable pH range is 5-7.
e.g., (i) Normal conversion of glucose into ethanol by zymase (enzyme) present in yeast.

Zymase
C 6 H12 O 6  o 2C 2 H 5OH  2CO 2
Glucose

(ii) Oxidation of alcohol to acetic acid by mycoderma aceti.

Mycoderma
C2H5OH + O2  o CH3COOH + H2O
aceti

(iii) Hydrolysis of urea (NH2CONH2) by urease (enzyme) present in soyabean.

O
||
H 2 N  C  NH 2  H 2 O Urease
o 2NH 3  CO 2
Urea

TOPIC : SURFACE CHEMISTRY- PART 2 (“CATALYST”) PAGE [3] of 5

Characteristics of Enzyme Catalysts

The important characteristics of enzyme catalysts are:

(i) High efficiency: Enzyme catalysis increase the speed of reactions by 108 to 1020 times as compared to the
uncatalysed reactions.
(ii) Extremely small quantities: Extremely small quantities of enzyme catalysts—as small as millionth of a
mole—can increase the rate of reaction by factors of 103 to 106.
(iii) Specificity: The enzyme catalysts are highly specific in nature.
Almost every biochemical reaction is controlled by its own specific enzymes. For example, urease catalyses
the hydrolysis of urea and none of the several thousand other enzymes present in the cell catalyses that
reaction.

NH2CONH2 + H2O  o 2NH3 + 2CO2

Urease

Similarly, maltase catalyses the hydrolysis of maltose. No other enzyme can catalyse its hydrolysis.
(iv) Optimum temperature and pH: The enzyme catalysts are active at moderate temperature (about 37°C)
and pH (around 7).
(v) Control of activity of enzymes: The action of enzyme catalytic reactions are controlled by various
mechanisms and are inhibited by various organic and inorganic molecules.
(vi) The activity of most enzyme catalysts is closely regulated.

Catalysts in Industry :

Process Catalyst used

(i) Haber’s process (to manufacture of ammonia) Finely divided iron as a catalyst and Mo as promoter
(ii) Ostwald’s process (to manufacture of nitric acid) Platinised asbestos
(iii) Lead chamber process (to manufacture of H2SO4) Nitric oxide
(iv) Contact process (to manufacture of H2SO4) Platinised asbestos or vanadium pentoxide
(v) Deacon’s process (to manufacture of chlorine) Cupric chloride
(vi) Bosch’s process (to manufacture of hydrogen) Ferric oxide catalyst and chromic oxide as promoter
(vii) Synthesis of methanol Zinc oxide catalyst and chromic oxide as promoter
(viii) Hydrogenation of vegetable oils Nickel
(ix) Bergius process for synthesis of petrol Ferric oxide
(x) Manufacture of ethyl alcohol from molasses Yeast (invertase and zymase)

SHAPE SELECTIVE CATALYST

These calalyst can possess active sites, as well as uniformly sized and shaped pores and voids whose pore size may
varry from 260 pm to 740 pm. Such catalyst are highly specific as reactant molecules of a peticular allowed size
& shape can enter and get adsorbed.

Eg. ZMS-5 is used to convert alcohol in to gasoline (petrol) by dehydrating the alcohol & producing a wide varity of hydrocarbon(petrol)

Zeolites as Shape selective catalyst

Zeolites are good shape-selective catalysts because of their honeycomb-like structures. Zeolites are microporous

TOPIC : SURFACE CHEMISTRY- PART 2 (“CATALYST”) PAGE [4] of 5

crystalline solids with well-defined structures. Generally they contain silicon, aluminium and oxygen in their framework
and cations, water and/or other molecules wthin their pores. these are alumino silicates with general
formula

M(x/n).[(AlO2)x.(SiO2)y].mH2O
Where
M = Metal like Na+, K+, Ca++
n = valency of metal cation
m = Molecules of water of crystallisation.

Note:-
1. Zeolities(Greek word) : means Boiling Stone, as water trapped in void space boils of, when naturally occuring
Zeolite is heated.
2. Building blocks of zeolities are
T=TRUNCATED OCTAHEDRON OR
CUBO OCTAHEDRON. This structure
is known as ECage
E or
Sodalite Cage Structure.

3. Zeolite may be considered as open structure of silica in which :

(i) Tetravalent Silicone atoms has been subtituted by
(ii) Trivalent Aluminium, in
(iii) fraction of [x/(x+y)]

4. When an atom of Silicon(Si++++) is sutituted by Aluminium(Al+++), then one -ve charge is generated on
alumono silicate framework. This charge is neutalised by exchangable cation “M” of valency “n”. The void
space which can be grater than 50% of volume occupid by “m” molecules of water in unit cell.

5. Examples

(a) Zeolite sieve of molecular porosity ( ZMS-5), Hx.[(AlO2)x.(SiO2)96-x].16.H2O

(b) Faujasite (Natural) Na56.[(AlO2)56.(SiO2)136].250.H2O
(c) Gemelinite Na2.Ca.[(AlO2)2.(SiO2)4].6H2O
(d) Erionite (Na2.K2.Ca)2.[(AlO2)4.(SiO2)14].15H2O
(e) Linde-A (Synthetic) [Na12.(AlO2)12.(SiO2)12.27.H2O]8

TOPIC : SURFACE CHEMISTRY- PART 2 (“CATALYST”) PAGE [5] of 5