CATALYSIS

Berzelius (1836) (Greek kata = wholly, lein = to loosen)

A catalyst is defined as a substance which alters (increase or decrease) the rate of a

chemical reaction, itself remaining chemically unchanged at the end of the reaction.

The process is called Catalysis.

A catalyst which enhances the rate of a reaction is called a Positive catalyst.

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

TYPES OF CATALYSIS
There are two main types of catalysis :
(a) Homogeneous catalysis
(b) Heterogenous catalysis

Enzyme catalysis which is largely of biological interest.

 TYPES of CATALYSIS
Homogeneous catalysis: The catalyst is in the same phase as the reactants and is evenly
distributed throughout.
Gas Phase
NO I2
(a) 2SO2 (g) + O2 (g) → 2SO3(g) (b) CH3CHO (g) → CH4 (g) + CO (g)
Solution Phase
H2SO4
(a) C12H22O11 (l) + H2O (l) → C6H12O6 (l) + C6H12O6 (l)
H+/OH −
(b) CH3COOC2H5 (l) + H2O (l) → CH3COOH (l) + C2H5OH(l)

Heterogeneous Catalysis: The catalyst is in a different physical phase from the reactants.
Gaseous Reactants (Contact Catalysis): usually catalyst is a finely divided metal/gauze.
Pt/V2O5
(a) 2SO2 (g) + O2 (g) → 2SO3 (g) (Contact Process)
Fe
(b) N2 (g) + 3H2 (g) → 2NH3 (g) (Haber Process)
Ni
(c) H2C=CH2 (g) + H2 (g) → CH3—CH3 (g) (Hydrogenation)

Liquid reactants AlCl3

Pt
(a) 2H2O2(l) → 2H2O (l)+ O2(g) (b) C6H6(l) + CH3COCl(l) → C6H5COCH3(l) + HCl (l)

Solid reactants
2KClO3 (s) MnO→ 2
2KCl (s) + 3O2 (g)
 Characteristics of Catalytic Reactions
(1) Catalyst remains unchanged in mass & chemical composition at the end of
reaction.
(2) A small quantity of catalyst is generally needed to produce almost unlimited
reaction.
(3) A catalyst is more effective when finely divided.
(4) A catalyst is specific in its action.
Al2O3 Cu
C2H5OH → CH2=CH2 + H2O but C2H5OH → CH3CHO + H2

(5) A catalyst cannot, in general, initiate a reaction.

Pt black
2H2 + O2 → 2H2O

(6) A catalyst does not affect the final position

of equilibrium, although it shortens the time
required to establish the equilibrium.

(7) Change of temperature alters the rate of

a catalytic reaction as it would do for the
same reaction without a catalyst

The rate of reaction is maximum at a particular

temperature called the optimum temperature.
 Why Catalysis Occurs

 Catalysts have unbalanced chemical

bonds on it.
 The reactant gaseous molecules are
adsorbed on the surface by these free
bonds.
 The distribution of free bonds on the
catalyst surface is not uniform.
 These are crowded at the ‘peaks’,
‘cracks’ and ‘corners’ of the
catalyst.
 The catalytic activity due to
adsorption of reacting molecules is
maximum at these spots. These are,
known as active centres.
 The active centres increase the rate
of reaction by increasing the
reactant concentration on the
surface and by activating
(stretching) the molecule adsorbed
at two such centres.
 THEORIES OF CATALYSIS
(1) Intermediate Compound Formation theory
(2) The Adsorption theory

Intermediate Compound Formation theory

NO
2SO2 (g) + O2 (g) → 2SO3(g)
1. The catalyst forms an intermediate compound with one of the reactants.

2. The highly reactive intermediate compound then reacts with the second reactant to
yield the product and releasing the catalyst as it was before the reaction.

Another Example:
 The Adsorption Theory
 This theory explains the mechanism of a reaction between two gases catalysed by a
solid (Heterogeneous or Contact Catalysis).
 Here the catalyst functions by adsorption of the reacting molecules on its surface.

 Step 1. Adsorption of Reactant molecules: The reactant molecules strike the catalyst
surface. They are held up at the surface by weak van der Waals forces (Physical
adsorption) or by partial chemical bonds (Chemisorption).

 Step 2. Formation of Activated complex: The particles of the reactants adjacent to one
another join to form an intermediate complex. The activated complex is unstable.

 Step 3. Decomposition of Activated complex: The activated complex breaks to form

the products. The separated particles of the products hold to the catalyst surface by
partial chemical bonds.

 Step 4. Desorption of Products: The particles of the products are desorbed or released
from the surface. They are stable and can lead an independent existence.
 The Adsorption Theory
Step 1. Adsorption of Hydrogen molecules Step. 2 H–H Bonds are broken

Step 3. Formation of the Activated complex Step 4. Decomposition of the Activated

complex and desorption of ethane molecules
 PROMOTERS
A substance which, itself is not
a catalyst, promotes the
activity of a catalyst is called a
promoter.
In some reactions, mixtures of
catalysts are used to obtain the
maximum catalytic efficiency.

Explanation of Promotion Action

(1) Change of Lattice Spacing. The
lattice spacing of the catalyst is
changed thus enhancing the spaces
between the catalyst particles. The
absorbed molecules of the reactant
are further weakened and cleaved.
(2) Increase of Peaks and Cracks.
The promoter increases the peaks and
cracks on the catalyst surface. This
increases the concentration of the
reactant molecules and hence the rate
of reaction.
 CATALYTIC POISONING

A substance which destroys the activity of the catalyst to accelerate a reaction, is

called a catalyst poison and the process is called Catalytic poisoning.

Explanation of Catalytic Poisoning

1) The poison is adsorbed on the catalyst surface in preference to the reactants.

2) The catalyst may combine chemically with the impurity.

 Negative Catalysis
 When a catalyst reduces the rate of a reaction - Negative catalyst/ Inhibitor.
 This phenomenon is called Negative catalysis or Inhibition.
 Negative catalysis is useful to slow down or stop altogether an unwanted reaction.

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Explanation of Negative Catalysis

(1) By poisoning a catalyst. For example, the traces of alkali dissolved from the glass
of the container, catalyse the decomposition of hydrogen peroxide (H2O2). But the
addition of an acid would destroy the alkali catalyst and thus prevent decomposition.

(2) By breaking a chain reaction.

 The Adsorption Theory Explains
Catalytic Activity

(1) Metals in a state of fine subdivision or colloidal form are rich in free valence
bonds and hence they are more efficient catalysts than the metal in lumps.

(2) Catalytic poisoning occurs because the so-called poison blocks the free
valence bonds on its surface by preferential adsorption or by chemical
combination.

(3) A promoter increases the valence bonds on the catalyst surface by changing
the crystal lattice and thereby increasing the active centres.
Energy Activation Energy And Catalysis

Activation Energy
With
Negative Catalyst

Activation Energy
With
Positive Catalyst

Reactants
Reactants Products
Products
Reaction Co-ordinate Reaction Co-ordinate
With Catalyst With Negative Catalyst
 AUTOCATALYSIS
When one of the products of reaction itself acts as a catalyst for that reaction the
phenomenon is called Autocatalysis.

ACID–BASE CATALYSIS
A number of homogeneous catalytic reactions are known which are catalyzed by acids or
bases, or both acids and bases. These are often referred to as Acid-Base catalysts.

Specific ion Catalysis

Specific H+ ion catalysis: Those reactions which can be catalyzed by H+.
Specific OH‾ ion catalysis: Those reactions which can be catalyzed by only OH‾.

Generalized Acid-Base Catalysis

Generalized Acid catalysis: Reactions which can be catalyzed by any kind of acid.
Generalized Base catalysis: Reactions which can be catalyzed by any kind of base.
 ENZYME CATALYSIS
Enzymes are complex biological molecules made up of proteins and act as catalysts to
speed up bio-chemical or biological reactions.

The catalysis brought about by enzymes is known as Enzyme Catalysis.

 MECHANISM OF ENZYME CATALYSIS
LOCK & KEY MECHANISM
Michaelis and Menten (1913)
 The long chains of the enzyme (protein) molecules are
coiled on each other to make a rigid colloidal particle with
cavities on its surface.
 These cavities which are of characteristic shape and full
of active groups (NH2, COOH, SH, OH)] are termed
Active centres.
 The molecules of substrate which have complementary
shape, fit into these cavities just as key fits into a lock
(Lock-and- Key theory).

 By virtue of the presence of active groups, the enzyme

forms an activated complex with the substrate which at
once decomposes to yield the products.

 Thus the substrate molecules enters the cavities, forms

complex and reacts, and at once the products get out of
the cavities.
 CHARACTERISTICS OF ENZYME CATALYSIS

(1) Enzymes are the most

efficient catalysts known.

(2) Enzyme catalysis is

marked by absolute
specificity.
 CHARACTERISTICS OF ENZYME CATALYSIS

3) The rate of enzyme

catalysed reactions is
maximum at the optimum
temperature

4) Rate of enzyme catalysed

reactions is maximum at
the optimum pH
 CHARACTERISTICS OF ENZYME CATALYSIS

5) Enzymes are markedly inhibited or poisoned: For example, heavy metal ions
(Ag+, Hg2+) react with the – SH groups of the enzyme and poison it.

6) Catalytic activity of enzymes is greatly enhanced by the presence of Activators

or Coenzymes.

 Activators are metal ions Na+, Mn2+, CO2+, Cu2+, etc., which get weakly bonded to
enzyme molecules and promote their catalytic action.

 Example: Addition of sodium chloride (Na+) makes amylase catalytically very

active.

 Often, a small nonprotein (vitamin) termed a coenzyme when present alongwith an

enzyme, promotes the catalytic activity of the latter.

THE END