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# Reactions approaching 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
1

## 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:

## 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

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
raised.
(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.

T/K

300

350
3.0 X 107

400
7.9 X 107

450
1.7 x 108

500
3.2 x108