Catalysis

What is Catalysis? 

Catalysis is the phenomenon by which the rate of a reaction is altered (accelerated or retarded) by the presence of a substance, which itself remains unchanged chemically in the process. The substance altering the rate of the reaction is a catalyst.

Catalytic reactions are of two types:

Homogeneous & Heterogeneous catalysis

Homogeneous catalysis: 

When the reactants and catalysts are in the same physical state  i.e. catalyst is in the same phase as the reactant is called homogenous catalysis. 

For Example

  • Lead Chamber Process:
     2SO_2(g)+O_2(g)\overset{NO(g)}{\rightarrow}2SO_3(g)

  • Inversion of Can Sugar:
     C_1_2H_2_2O_1_1+H_2O\overset{H_2SO_4(aq)}{\rightarrow}C_6H_{12}O_6+C_6H_1_2O_6

Heterogeneous catalysis: 

A catalytic process in which the catalyst and the reactants are in different phases is called heterogeneous catalysis. This process is also called contact or surface catalysis. 

For Example

  • Decomposition of H2O2
    H_2O_2(l)\overset{Pt(s)}{\rightarrow}2H_2O(l) + O_2(g)

  • Haber’s Process: 
    N_2(g)+3H_2(g)\overset{Fe(s)}{\rightarrow}2NH_3(g)

What is a catalyst?

Catalyst is a substance that alters the rate of chemical reaction without being consumed itself during the course of reaction.

Catalysts are divided into four groups

Catalysts are divided into four groups.

  • Positive catalyst: The substance which increases the rate of reaction is known as positive catalyst. It decreases the activation energy for the reaction.
    Example: Contact Process: 
    2SO_2 +O_2\overset{V_2O_5}{\rightarrow}2SO_3
  • Negative catalyst (Inhibitor or retarder): The substance which decreases the rate of reaction is known as positive catalyst. It increases the activation energy for the reaction.

    Examples : Alcohol, Acetanilide: Prevents oxidation of Na2SO3 by air 
    H3PO4: Prevents decomposition of H2O2 

  • Auto catalyst: In this type of catalysis, one of the products of the reaction catalysis the reaction. In the oxidation of oxalic acid by KMnO4, Mn2+ ion formed is known to accelerate the reaction. So, when KMnO4 solution is run into warm solution of oxalic acid (+ dil. H2SO4), initially there is a time lag before decolourisation occurs; as more KMnO4 is added, the decolourisation becomes almost instantaneous. 

  • Induced catalyst: When a chemical reaction enhances the rate of another chemical reaction , it is called induced catalysis.. 
    Examples of induced catalysis: 
    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. 
    The reduction of mercuric chloride (HgCI2) 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 KMnO4 and HgCI2, both are reduced simultaneously. The reduction of potassium permanganate, thus, induces the reduction of HgCI2

Characteristics of Catalytic Reactions

  • The catalyst remains unchanged in amount and chemical composition at the end of the reaction; it may, however, undergo considerable change in physical form. 

  • A small quantity of the catalyst is capable of producing the desired effect. 

  • The action of a catalyst is specific to a large extent. Thus, the decomposition of KCIO3 is catalyzed by MnO2 but not by platinum. 

  • The catalyst does not initiate a reaction; it merely accelerates the reaction that is already occurring. 

  • A catalyst does not alter the final state of equilibrium in a reversible reaction. 

  • A certain minimum energy must be possessed by the reactants so that they may react and produce the products. This is called the activation energy (Ea) for the reaction. A catalyst is said to lower the activation energy and thus increase the rate of the reaction. Thus, a catalyst increases the rate of a reaction by providing a pathway whose activation energy is lower than the activation energy of the uncatalysed reaction. 

A catalyst increases the rate of a reaction by providing a pathway whose activation energy is lower than the activation energy of the uncatalysed reaction.

Mechanism of Ctalytic Action

It is not possible to provide any fixed mechanism for the action of all the catalysts. This is because the catalytic reactions are of various types. However, the two theories of catalytic action which are followed are.

  • Intermediate  compound formation theory of catalysis

  • Adsorption theory of catalysis

Intermediate compound formation theory.

According to this theory, the catalysts react with one of the reactants of reaction to form an unstable intermediate compound.  The formation of this intermediate compound takes less energy than needed for the actual reaction. The intermediate compound being unstable combines with the other reactant to form the product and the catalyst is regenerated.

So we can say that, a catalyst increases the arte of any reaction by providing an alternative pathway for the reaction to proceed with lower activation energy.

A large number of catalytic reactions can be explained on the basis of this theory

For example Catalytic oxidation of SO2 to SO3 in the presence of NO as catalyst

2NO +O2 →  2MO2

NO2+SO2 →  SO3+NO

This theory provides explanation for the fact that catalyst remains unchanged in mass and chemical composition at the end of reaction and its effectiveness even in small quantities. 

Adsorption theory of catalysis:

This theory explains the mechanism of heterogeneous catalysis mainly. The old point of view was that when the catalyst is in solid state and the reactants are in gaseous state or in solutions, the molecules of the reactants are adsorbed on the surface of the catalyst. Adsorption being an exothermic process, the heat of adsorption is taken up by the surface of catalyst, which is utilized on enhancing the chemical activity of reacting molecules.

  • The modern adsorption theory is the combination of intermediate compound formation theory and the old adsorption theory.

  • The catalytic activity is located on the surface of the catalyst. The mechanism involves five steps

  • Diffusion of reactant on the surface of catalyst

  • Adsorption of reactant molecules on the surface of catalyst

  • Occurrence of chemical reaction on the catalyst surface through formation of intermediates

  • Desorption of reaction products away from the catalyst surface

  • Diffusion of reactant products away from the catalyst surface 

Catalysts in Industries:

Industrial Process

Catalyst Used

Haber’s process for manufacture of ammonia

Finely divided iron + Mo as promoter

Ostwald’s process for manufacture of nitric acid

Platinised asbestos

Lead chamber process for manufacture of H2SO4

Nitric oxide

Contact process for manufacture of H2SO4

Platinised asbestos or vanadium pentoxide

Deacon’s process for manufacture of chlorine

Cupric chloride

Bosch’s process for manufacture of hydrogen

Ferric oxide + chromic oxide as promoter

Synthesis of methanol

Zinc oxide + chromic oxide as promoter

Hydrogenation of vegetable oils

Nickel

Bergius process for synthesis of  petrol

Ferrix oxide

Manufacture of ethyl alcohol from molasses

Yeast (invertase and zymase)

Catalytic Promoters

Those substances which do not themselves act as catalyst but their presence increases the activity of a catalyst are called catalytic promoters.

Example. In the Haber’s Process, Fe is the catalyst while Mo acts as a promoter.

Catalytic Poison:

The substance whose presence decreases or destroys the activity of a catalyst is called catalytic poison.

For example: the Haber’s Process, CO or H2S acts as poison for  Fe  catalyst.

Activity of Catalyst:

Activity of a catalyst is the ability of catalyst to accelerate a chemical reaction. The degree of acceleration can be as high as 10 10 times in certain reactions.

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.

Selectivity of Catalyst:

Selectivity of a catalyst is its ability to direct a reaction to yield particular product (excluding other) 

For example:

CO(g)+2H_2(g)\overset{Ni}{\rightarrow}CH_4(g)+H_2O(l)

CO(g)+2H_2(g)\overset{Ca/ZnO-Cr_2O_3}{\rightarrow}CH_3OH(g)

CO(g)+2H_2(g)\overset{Cu}{\rightarrow}HCHO(g)

Shape-Selective Catalysis by Zeolites

The catalytic reaction that depends upon the structure of pores of the catalyst and the size of the reactant and product molecules is called shape/selective catalysis. Zeolites are good shape/selective catalysts because of their honeycomb-like structures. Zeolites are aluminosilicates i.e., three dimensional network silicates in which some silicon atoms are replaced by aluminium atoms. They are found in nature as well as synthesized for catalytic selectivity. Zeolites, before using as catalysts, are heated in vacuum so that the water of hydration is lost. As a result, zeolite becomes porous i.e., the cavities in the cage-like structure which were occupied by the water molecules become vacant. The size of the pores generally varies between 260 pm and 740 pm. Thus only those molecules can be adsorbed in these pores whose size is small enough to enter these cavities and also leave easily. 

The reactions taking place in zeolites depend upon the size and shape of reactant and product molecules as well as upon the pores and cavities of the zeolites. That is why these types of reactions are called ‘shape-selective catalysis’ reactions. 

Zeolites are being very widely used as catalysts in petrochemical industries for cracking of hydrocarbons and isomerisation. An important zeolite catalyst used in the petroleum industry is ZSM-5. It converts alcohols directly into gasoline (petrol) by dehydrating them so that a mixture of hydrocarbons in formed.

Question 1: A catalyst

a. increases the rate of reaction

b. decreases the rate of reaction

c. may increase or decrease the rate of reaction

d. does not affect the rate of reaction

Question 2: A positive catalyst

a. decreases the activation energy

b. increases the activation energy

c. does not affect the rate of reaction

d. decreases the rate of reaction

Question 3: Which of the following catalysts is used in contact process?

a. V2O5

b. Fe

c. Co

d. Ni

Question 4: Which of the following statements regarding catalyst is incorrect?

a. The catalyst remains unchanged in amount and chemical composition at the end of the reaction; it may, however, undergo considerable change in physical form. 

b. A small quantity of the catalyst is capable of producing the desired effect. 

c. The action of a catalyst is specific to a large extent. Thus, the decomposition of KCIO3 is catalyzed by MnO2 but not by platinum. 

d. A catalyst does alter the final state of equilibrium in a reversible reaction. 

Q.1

Q.2

Q.3

Q.4

c

a

c

d

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