The Rates of Chemical

Reactions
Reaction rates depend on the concentration of reactants (and products) in
characteristic ways that can be expressed in terms of differential equations
known as rate laws. The solutions of these equations are used to predict the
concentrations of species at any time after the start of the reaction.

The rate of a chemical reaction might depend on variables under our control,
such as the pressure, the temperature, and the presence of a catalyst, and
we may be able to optimize the rate by the appropriate choice of conditions.
The study of reaction rates also leads to an understanding of the
mechanisms of reactions, their analysis into a sequence of elementary
steps.
Reactions Approaching Equilibrium

Because all the laws considered so far disregard the possibility that the
reverse reaction is important, none of them describes the overall rate when
the reaction is close to equilibrium. At that stage the products may be so
abundant that the reverse reaction must be taken into account.
In practice, however, most kinetic studies are made on reactions that are far
from equilibrium, and the reverse reactions are unimportant.
We can explore the variation of the composition with time close to chemical
equilibrium by considering the reaction in which A forms B and both forward
and reverse reactions are first-order (as in some isomerization). The
scheme we consider is
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]0, and no B is present initially, then at all
times [A] + [B] = [A]0. Therefore,
Reactions Approaching Equilibrium

[]
= + 0

[]
= + + 0

The solution of this first-order differential equation is
+
+
= []0
+
Reactions Approaching Equilibrium

As , the concentrations reach their equilibrium values, which are given

by
[]0
[] =
+
[]0
[] = []0 =
+
It follows that the equilibrium constant of the reaction is
[]
= =
[]
(This expression is only approximate because thermodynamic equilibrium
constants are expressed in terms of activities, not concentrations.)
Reactions Approaching Equilibrium

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

=

Reactions Approaching Equilibrium

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. We
shall consider the response of reaction
rates to a temperature jump, a sudden
change in temperature.
Reactions Approaching Equilibrium

When the temperature of a system at equilibrium A B equilibrium that is

first-order in each direction 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.
Reactions Approaching Equilibrium

The concentration of A then changes as follows:

[]
= [] + []

[]
= +

Because d[A]/dt = dx/dt,
= 0 /
= +
Where x0 is the departure from equilibrium immediately after the
temperature jump and x is the departure from equilibrium at the new
temperature after a time t
Example

The equilibrium constant for the autoprotolysis of water,

H2O(l) H+ (aq)+ OH (aq)

is Kw = a(H+) a(OH) = 1.0081014 at 298 K. After a temperature-jump, the

reaction returns to equilibrium with a relaxation time of 37 s at 298 K and
pH 7. Given that the forward reaction is first-order and the reverse is
second order overall, calculate the rate constants for the forward and
reverse reactions.
Answer

[2 ]
= 1 2 + 2 [ + ][ ]

= 1 2 + + 2 [ + ] [ ]

= 1 + 2 [ + ] + [ ] 1 2 + 2 [ + ] [ ] + 2 2

neglecting x2
+
1
= 1 + 2 [ ] + [ ] =

because +] ]
+
[ [
=

and [H+]eq = [OH-]eq

 1
1
= 1 + 2 2 = 2 + 2
2
we note that 1 [ + ] [ ] 2
= =
2 2 2

with = 1 mol/dm3 and molar concentration of pure water is 55.6 mol dm3,
so 2 / = 55.6 and we write K = 1.81 x 10-16, we obtain

1
= 2 + 2

hence
1 1
2 = =
+ 2 (3.7 105 )(1)(2.0 107 )

2 = 1.4 1011 dm3/(mol.s)

1 = 2 = 2.4 105 s-1
Self Test

Derive an expression for the relaxation time of a concentration when the

reaction A + B C + D is second-order in both directions.

Answer 1
= [] +[] + [] +[]

The Temperature Dependence of Reaction Rates

The rate constants of most reactions

increase as the temperature is
raised. It is found experimentally for
many reactions that a plot of ln k
against 1/T gives a straight line. This
behavior is normally expressed
mathematically by introducing two
parameters, one representing the
intercept and the other the slope of
the straight line, and writing the
Arrhenius equation
The Temperature Dependence of Reaction Rates

ln = ln

The parameter A, which corresponds to the intercept of the line at 1/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. Collectively the two quantities are
called the Arrhenius parameters