Effect of Catalyst on the rate of a reaction

 A catalyst is a substance that alters the rate of reaction without itself undergoing any
chemical change at the end of reaction.
 e.g. MnO2 catalyses the following reaction so as to increase its rate considerably.
MnO2
2KCl3 2KCl + 3O2

 The word catalyst should not be used when the added substance reduces the rate of reaction
in this case the substance is then called inhibitor.
Characteristics of catalyst:
(i) A catalyst does not change the equilibrium constant of a reaction rather, it helps in
attaining the equilibrium faster, that is, it catalyzes the forward as well as the backward
reactions to the same extent so that the equilibrium state remains same but is reached earlier.
(ii) Does not alter the free energy change (ΔG) of a reaction.
(iii) A small amount of the catalyst can catalyze large number of reactions.
 The action of the catalyst can be explained by intermediate complex theory.

Intermediate complex theory

 The intermediate complex has a temporary existence and decomposes to yield products and
the catalyst.
 It is believed that the catalyst provides an alternate pathway or reaction mechanism by
reducing the activation energy between reactants and products and hence lowering the
potential energy barrier as shown in Fig. below.

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 Fig.: Effect of catalyst on activation energy

 According to Arrhenius equation, k = Ae-Ea/RT, the lower the value of activation energy, the
faster will be the rate of a reaction.
 Although a catalyst lowers the activation E, it does not affect the E difference between
products and reactants.
 Three main types of catalysis are;
 Heterogeneous Catalysis
 Homogeneous Catalysis
 Enzyme

Homogeneous catalysis
 In a homogeneous catalytic reaction, the catalyst is in the same phase as the reactants.
 Most industrial homogeneous catalytic processes are carried out in liquid phase e.g.
o Ester hydrolysis involving general acid-base catalysts, polyethylene production with
organometallic catalysts and enzyme catalyzed processes are some of the important
examples of industrial homogeneous catalytic processes.

Heterogeneous catalysis
 Mostly encountered in a situation involving a solid catalyst in contact with gaseous reactants
and gaseous products e.g. catalytic converters in cars, many industrial catalysts are
heterogeneous.

How do they do their job?

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Typically, heterogeneous catalysis involves four steps;
1. The first step is adsorption (the binding of reactant molecules to the catalyst surface) and
activation of the reactants.
 Adsorption occurs due to the high reactivity of atoms or ions on the surface of the solid.
 Molecules are adsorbed onto active sites on the catalyst surface.
 The number of active sites on a given amount of catalyst depends on several factors such
as:
- The nature of the catalyst.
- How the catalyst was prepared.
- How the catalyst was treated prior to use.
2. Migration of the adsorbed reactants on the surface.
3. Reaction of the adsorbed substances.
4. Escape, or desorption, of the products.
Example: C2H4(g) + H2(g)  C2H6(g)
 In the presence of a metal catalyst (Ni, Pt or Pd) the reaction occurs quickly at room
temperature.
 Here are the steps…
 First, the ethylene and hydrogen molecules are adsorbed onto active sites on the metal
surface.
 Second, the H–H bond breaks and the H atoms migrate about the metal surface and runs
into a C2H4 molecule on the surface.
 Third, when an H atom collides with a C2H4 molecule on the surface, the C−C π-bond
breaks and a C–H σ-bond forms.
 Lastly, When C2H6 forms it desorbs from the surface.
 When ethylene and hydrogen are adsorbed onto a surface, less energy is required to break the
bonds.
 The Ea for the reaction is lowered, thus the reaction rate increases.

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Enzymes as Catalysts
 Enzymes are catalysts in biological systems.
 The substrate fits into the active site of the enzyme much like a key fits into a lock.

 Enzymes are biological catalysts and may be as many as 30,000 enzymes in the human body
(ex: Lactase).
 Most enzymes are protein molecules with large molecular masses (10,000 to 106 amu).
 Enzymes have very specific shapes and catalyze very specific reactions.
 The substances that undergo reaction at the active site on enzymes are called substrates.
 A substrate locks into an enzyme and a fast reaction occurs. The products then move away
from the enzyme.
 Only substrates that fit into the enzyme lock can be involved in the reaction.
 If a molecule binds tightly to an enzyme so that another substrate cannot displace it, then the
active site is blocked and the catalyst is inhibited (enzyme inhibitors).
 Many poisons act by binding to the active site blocking the binding of substrates. The
binding can also lead to changes in the enzyme.
 Enzymes are extremely efficient catalysts.

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 The number of individual catalytic events occurring at an active site per unit time is called
the turnover number.
 Large turnover numbers correspond to very low Ea values. For enzymes, turnover numbers
are very large ≈ 103 to 107/sec.