EFFECT OF ADDITION OF CATALYST

A catalyst is a substance that alters the rate of a reaction without itself

undergoing any permanent chemical change. If the catalyst increases the rate of the
reaction, it is called a positive catalyst or simply a catalyst. However, if the catalyst
decreases the rate of the reaction, it is called a negative catalyst or inhibitor. For
example, MnO2 catalyzes the following reaction so as to increase its rate considerably.
MnO
2KCℓO3 ⎯⎯⎯⎯
2
→ 2 KCℓ + 3O2
The action of the catalyst can be explained by intermediate complex formation
theory. According to this theory, a catalyst participates in a chemical reaction by
forming temporary bonds with the reactants resulting in an intermediate complex
(transition state with different energy of activation. This new energy of activation
may be less (for positive catalyst) or more (for negative catalysis) than that for the
uncatalyzed reaction. This is shown in figure.
Transition state
(with negative catalysis)
Reaction path with
negative catalyst
Transition state
(Uncatalyzed reaction)

Eancf Reaction path

without catalyst
Eaucf
Energy

Transition state
Eaucr (with positive catalysis)

Eacf
Eacr
Reactants Reaction path with
positive catalyst
Products
Reaction progress

Fig. Energy profile for a catalyzed and

uncatalyzed reaction

The rate constant for the catalyzed ( k fc ) and uncatalyzed ( k fuc ) reaction in the
forward direction may be expressed in terms of Arrhenius equation as
f − Ea fc /RT
k c = Ae (Liii)
f − Ea fuc /RT
k uc = Ae (Liv)

where Ea fc and Ea fuc are the energy of activation of catalyzed and uncatalyzed forward
reactions respectively. The ratio between the rates of catalyzed and uncatalyzed
forward reactions then is obtained by dividing equation (Liii) with (Liv)
f
k fc e − Ea c /RT
=
k fuc
f
e − Ea uc /RT
(Ea uc − Ea c )/RT
f f
ΔEa/RT
=e = e
 k fc ΔE fa
or log = (Lv)
k fuc 2.303RT

where ΔE fa = Ea fuc – Ea fc . ΔE fa is a positive value for positive catalysis ( Ea fuc > Ea fc ) and
negative value for negative catalysis ( Ea fuc < Ea fnc ) (see figure 12).
Similarly we can arrive at the equation:
k cr ΔE ar
log = (Lvi)
k ruc 2.303RT

where k cr and k ruc are the rate constant for the catalyzed and uncatalyzed reverse
reactions respectively and ΔE ar = Ea ruc – Ea cr .

However, ΔE fa = ΔE ar , therefore, from equation (Lv) and (Lvi) we can say that

k fc k cr
=
k fuc k ruc

k fuc k fc
or =
k ruc k cr

or Kuc = Kc (Lvii)

where Kuc and Kc are the equilibrium constants for the uncatalyzed and catalyzed
reactions respectively. Thus, a catalyst does not change the equilibrium constant of a
reaction rather, it helps in attaining the equilibrium faster, that is, it catalyses the
forward as well as the backward reactions to the same extent so that the equilibrium
state remains same but is reached earlier.
A small amount of the catalyst can catalyze a reaction with large amount of reactants.
A catalyst does not alter Gibbs energy, ΔG of a reaction. It catalyzes the spontaneous
reactions but does not catalyze non-spontaneous reactions.