84 4.

Reaction Order and Rate Constants

4.2 RATES OF COMPLEX REACTIONS

As seen above, the majority of kinetic processes involves more than one elementary
step. However, the fact that a mechanism is in agreement with the kinetic law does not
mean that it is the correct mechanism for the reaction. The same kinetic law can, and fre-
quently does, correspond to more than one possible mechanism. A mechanism is always a
theoretical hypothesis of how a reaction occurs. We can never prove a mechanism from the
kinetic behaviour, but can only eliminate certain hypotheses. A good illustration is given
by the gas-phase reaction at 400 8C

H 2 + I 2 
→ 2 HI (4.III)

studied by Bodenstein in 1894, which was considered to be an elementary process.

However, even at this time he recognised that it was difficult to find chemically simple reac-
tions in the gas phase, i.e. reactions whose rates are proportional to the product of the con-
centrations of reactants raised to integral powers. Reaction (4.III) was presented as an
example of an elementary kinetic process in all text books until Sullivan in 1967 detected
the presence of free radicals in the system at 350 8C, and proposed an alternative mechanism

I 2 energy
 → 2I
H 2 + 2I 
→ 2HI (4.IV)
2I + M 
→ I2 + M

where M is an inert gas. In summary, there are a number of important questions needed to
test this mechanism. Mechanisms of the reactions are proposed on the basis of the
observed kinetic behaviour. Once proposed, a very detailed physical chemical study is
necessary before any mechanism can be considered as accepted. It is necessary to confirm
the feasibility of all the steps proposed in addition to demonstrating the possible existence
of the different intermediates. Because of various experimental difficulties, these tasks are
difficult to carry out for the majority of the chemical reactions. In addition to kinetic stud-
ies, involving, for example, predictions of the effects of various factors on rates and prod-
uct distributions, these studies must be complemented by other chemical and physical
studies, in particular attempts to try to trap and characterise the intermediates.
Complex reaction mechanisms can conveniently be grouped within the following clas-
sification: consecutive reactions, parallel reactions and reversible reactions. Parallel reac-
tions are those in which the same species participates in two or more competitive steps.
Consecutive reactions are characterised by the product of the first reaction being a reactant
in a subsequent process, leading to formation of the final product. Reversible reactions are
those in which the products of the initial reaction can recombine to regenerate the reactant.
As complex reactions follow a reaction mechanism involving various elementary steps, the
determination of the corresponding kinetic law involves the solution of a system of differen-
tial equations, and the complete analytical solution of these systems is only possible for the
simplest cases. In slightly more complicated cases it may still be possible to resolve the sys-
tem of corresponding differential equations using methods such as Laplace transforms or
matrix methods. However, there are systems which cannot be resolved analytically, or whose
4.2 Rates of Complex Reactions 85

analytical solution is so complex that it is not easily applied. In the absence of information on
the orders of magnitude of the rate constants involved, the treatment of these kinetic systems
is made using numerical methods. These methods allow us to obtain concentrations of the
reactants for discrete time intervals, which can then be represented graphically and compared
with experimental data to provide an insight into the changes occurring. Further, although the
results obtained numerically are inherently approximations, we can estimate and allow for the
errors involved, which can be expressed as error limits when compared with experimental
data. In some cases, it may also be possible to introduce some changes of a chemical nature
in the system to help simplify and analyse these complex systems. For example, if we know
the relative magnitudes of some of the rate constants, it may be possible to simplify the sys-
tem of complex differential equations involved by modifying the initial concentrations of
reactants and obtaining a rate equation that can be solved analytically. Finally, when these
procedures cannot be used to resolve complex systems of differential equations, it is still pos-
sible to use stochastic treatments such as Markov chains or the Monte Carlo method.

4.2.1 Parallel first-order reactions

The simplest parallel reactions involve two competitive first-order steps:

A k
1
→B
(4.V)
A k
2
→C

The rate of disappearance of A is given by the differential equation

d[ A]
= − k1 [ A] − k2 [ A] = kT [ A]
dt (4.30)
where kT = k1 + k2. Integrating this equation gives

[ A] = [ A]0 e − kT t = [ A]0 e ( 1 2 )
− k +k t
(4.31)
To determine the rate of formation of B, we have
d[ B]
= k1 [ A]
dt (4.32)
and, substituting for [A] using expression (4.31), followed by integration with the condi-
tion that for t = 0, [B] = 0, we obtain

[ B] =
k1 [ A]0
kT
(
1 − e − kT t )
(4.33)
We can obtain the variation of [C] with time in the same way:

[ C] =
k2 [ A]0
kT
(
1 − e − kT t ) (4.34)
86 4. Reaction Order and Rate Constants

Figure 4.3 Variation of the concentrations of reactant and final products for parallel first-order reac-
tions. The full lines correspond to the situation in which k1 = k2 and the dashed lines correspond to
the case in which k1 = 2k2.

From the above two expressions we see immediately that the ratio of the rate constants of
parallel first-order reactions is equal to the ratio of yields of the products.
[ B] k1
= (4.35)
[ C] k 2
This quotient is called the branching ratio of the reaction.
Figure 4.3 shows the time evolution of [A], [B] and [C] for the cases in which k1 = k2
and k1 = 2k2.
This solution can easily be extended to parallel reactions involving more than two
processes. If there are n parallel reactions, then kT = k1 + k2 + … + kn, and the expression
for the disappearance of A has the same form as eq. (4.30).

4.2.2 Consecutive first-order reactions

Another very common kinetic scheme involves a series of first-order reactions, leading first
to the formation of an intermediate B, which subsequently reacts to give the final product
A k
1
→ B k
2
→C (4.VI)
The differential equations describing this sequence of elementary steps are
d[ A]
= − k1 [ A]
dt
d[ B]
= k1 [ A] − k2 [ B]
dt (4.36)
d[C]
= k2 [ B]
dt
4.2 Rates of Complex Reactions 87

As we have seen, the integrated rate equation for the disappearance of A is given by

[ A] = [ A]0 e − k1t (4.37)

and can be substituted for [A] in the equation describing the variation of [B] with time.
After rearranging, this can be written as

d[ B]
+ k2 [ B] = k1 [ A]0 e − k1t (4.38)
dt
Multiplying both terms by exp (k2t), we obtain [2]

d[ B]
+ k2 [ B]e k2 t = k1 [ A]0 e ( 2 1 )
k −k t
e k2 t (4.39)
dt
and as

e k2 t
d[ B]
+ k2 [ B]e k2 t =
(
d [ B]e k2 t )
dt dt (4.40)
the equation can be written as the differential equation

( )
d [ B]e k2 t = k1 [ A]0 e ( 2
k − k1 ) t
dt (4.41)

which, upon integration, leads to

k1 [ A]0 e ( 2 1 )
k −k t

[ B]e k2 t = +I (4.42)
k2 − k1

where the integration constant I is obtained for the simplest case of [B] = 0 at t = 0, as

k1 [ A]0
I=− (4.43)
(k2 − k1 )
Substituting this value for I in eq. (4.42) and dividing by exp (k2t), we obtain the integrated
equation for the dependence of [B] upon time:

[ B] =
(
k1 [ A]0 e − k1t − e − k2 t ) (4.44)
k2 − k1

which is true for the case in which k1 Þ k2. When k1 = k2, we obtain

( )
d [ B]e k2 t = k1 [ A]0 dt (4.45)

whose solution is

[ B] = k1 [ A]0 e − k1t t (4.46)

88 4. Reaction Order and Rate Constants

Figure 4.4 Variation of the concentrations of reactant, intermediate and final product with time for
consecutive first-order reactions. The solid line shows the case in which k1 = k2, while the dashed
line is for the condition k1 = 10k2.

when [B] = 0 at t = 0. Figure 4.4 shows the time evolution of the concentrations of reac-
tant, intermediate and final product for the cases in which k1 = k2 and k1 = 10k2.

4.2.3 Reversible first-order reactions

The simplest reversible reactions are of the type

kf
A ↽k ⇀ B (4.VII)
r

The corresponding differential equations for this mechanism are

d[ A]
− = kf [ A] − kr [ B]
dt (4.47)
d[ B]
− = kr [ B] − kf [ A]
dt
Assuming that at time t = 0 the initial concentrations of the two species are [A]0 and [B]0,
we can write the law of conservation of mass for this system:

[A]0 + [B]0 = [A] + [B] (4.48)

and solving in terms of [B] we obtain

[B] = [A]0 + [B]0 − [A] (4.49)

4.3 Methods for Solving Kinetic Equations 89

Substituting [B] in the differential expression and rearranging, we can write

d[ A]  − kr ([ A]0 + [ B]0 ) 
− = ( kf + k r )  + [ A] (4.50)
dt  ( kf + k r ) 
where
− kr ([ A]0 + [ B]0 )
= −m (4.51)
( kf + k r )
is a constant. Thus, the integration
d[ A]
= ( k f + k r ) ∫ dt
[A] t
∫[ A ]0 m − [ A] 0
(4.52)

leads to
 k [ A] − kr [ B] 
ln  f = − ( kf + k r ) t (4.53)
 kf [ A]0 − kr [ B]0 

When equilibrium is reached, the forward and reverse reactions have the same rates. This
corresponds to a formulation of the principle of microscopic reversibility. Thus, at equi-
librium, the concentrations of reactant and product do not change with time
d[ A]e d[ B]e
=− =0 (4.54)
dt dt
i.e.
− kf [ A ]e + kr [ B]e = 0 (4.55)

where the subscript refers explicitly to the equilibrium condition. From this, the equilib-
rium constant is given by
kf [ B]e
= = K eq (4.56)
kr [ A ]e

Figure 4.5 shows the evolution of [A] and [B] for the cases in which kf = kr and kf = 3 kr.
The same ideas can be applied to reversible reactions that occur in various steps. The
principle of microscopic reversibility can help resolve more complicated systems of
kinetic equations when the system is in equilibrium.

4.3 METHODS FOR SOLVING KINETIC EQUATIONS

4.3.1 Laplace transforms

Classical methods of integration are used to solve many of the linear differential equations
that describe the kinetic behaviour of chemical reactions. However, the methods of solving