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Reactions approaching equilibrium

(a) First-order reactions close to equilibrium

The concentration of A is reduced by the forward reaction (at

a rate k[A]) but it is increased by the reverse reaction (at a
rate k'[B]. The net rate of change is therefore

If the initial concentration of A is [A]o, and no B is present

initially, then at all times
[A] + [B] = [A]o. Therefore,

The solution of this first -order differential equation (as may

be checked by differentiation) is

The approach of concentrations to their equilibrium

values as predicted by eqn 1 for a reaction A B that
is firstorder in each direction, and for which k=2k'.

As t the concentrations reach their equilibrium values,

which are given by eqn 1 as:

I t follows that the equilibrium constant of the reaction is

For a more general reaction, the overall equilibrium

constant can be expressed in terms of the rate constants
for all the intermediate stages of the reaction mechanism:

(b) Relaxation methods

(b) Relaxation methods

The term relaxation denotes the return of a system to equilibrium. It is
used in chemical kinetics to indicate that an externally applied influence
has shifted the equilibrium position of a reaction, normally suddenly, and
that the reaction is adjusting to the equilibrium composition characteristic
of the new conditions.

The relaxation to the new equilibrium

composition when a reaction
initially at equilibrium at a
temperature T1 is subjected to a
sudden change of temperature,
which takes it to T2.

When the temperature of a system at equilibrium is increased suddenly,

the rate constants change from their earlier values to the new values ka
and kb characteristic of that temperature, but the concentrations of A and
B remain for an instant at their old equilibrium values. As the system is
no longer at equilibrium, it readjusts to the new equilibrium
concentrations, which are now given by

and it does so at a rate that depends on the new rate constants. We

write the deviation of [A] from its new equilibrium value as x, so [A] =x+
[A]eq and [B] = [B]eq -x. The concentration of A then changes as follows:

The temperature dependence of reaction rates

The rate constants of most reactions increase as the temperature is
(a) The Arrhenius parameters
Arrhenius equation

The parameter A, which corresponds to the intercept ofthe line at I/T=

0 (at infinite temperature is called the pre-exponential factor or the
'frequency factor'.
The parameter Ea' which is obtained from the slope of the line (-Ea/R),
is called the activation energy.

A plot of ln k against l/T is a straight line when the reaction follows the
behaviour described by the Arrhenius. The slope gives Ea/R
and the intercept at 1/T= 0 gives In A.

Self-test 6 for student Determine A and Ea from the following data:



kl(dm3 mol-1 s-1) 7.9 x 106

3.0 X 107

7.9 X 107

1.7 x 108

3.2 x108

Key :[8 x l010 dm3 mol-1 s-1, 23 kJ mol-1]