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2
2KCO3
2 KC + 3O2
Energy
Eancf
Reaction path
without catalyst
Eaucf
Transition state
(with positive catalysis)
Eaucr
Eacf
Eacr
Reactants
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
k c = Ae
f
Ea fc /RT
k uc = Ae
(Liii)
Ea fuc /RT
(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
=
f
k fuc
e Ea uc /RT
=e
(Ea uc Ea c )/RT
f
= e
Ea/RT
or
log
k fc
E fa
=
2.303RT
k fuc
(Lv)
where E fa = Ea fuc Ea fc . E 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:
log
E ar
k cr
=
2.303RT
k ruc
(Lvi)
where k cr and k ruc are the rate constant for the catalyzed and uncatalyzed reverse
reactions respectively and E ar = Ea ruc Ea cr .
However, E fa = E ar , therefore, from equation (Lv) and (Lvi) we can say that
k fc
k fuc
or
or
k fuc
k ruc
=
=
k cr
k ruc
k fc
k cr
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, G of a reaction. It catalyzes the spontaneous
reactions but does not catalyze non-spontaneous reactions.