Accounting for The Rate

Laws
Elementary reactions

Most reactions occur in a sequence of steps called elementary reactions,

each of which involves only a small number of molecules or ions. The phase
of the species is not specified in the chemical equation for an elementary
reaction, and the equation represents the specific process occurring to
individual molecules. The molecularity of an elementary reaction is the
number of molecules coming together to react in an elementary reaction. In
a unimolecular reaction, a single molecule shakes itself apart or its atoms
into a new arrangement. In a bimolecular reaction, a pair of molecules
collide and exchange energy, atoms, or groups of atoms, or undergo some
other kind of change.
Elementary reactions

It is most important to distinguish molecularity from order: reaction order is

an empirical quantity, and obtained from the experimental rate law;
molecularity refers to an elementary reaction proposed as an individual step
in a mechanism. The rate law of a unimolecular elementary reaction is first-
order in the reactant:

[]
= []

A unimolecular reaction is first-order because the number of A molecules
that decay in a short interval is proportional to the number available to decay
or proportional to its molar concentration.
Elementary reactions

An elementary bimolecular reaction has a second-order rate law:

+
[]
= [][]

A bimolecular reaction is second-order because its rate is proportional to the
rate at which the reactant species meet, which in turn is proportional to their
concentrations.
For the present we emphasize that, if the reaction is an elementary
bimolecular process, then it has second-order kinetics, but if the kinetics are
second-order, then the reaction might be complex.
Consecutive Elementary Reactions

Some reactions proceed through the formation of an intermediate (I), as in

the consecutive unimolecular reactions
1 2

[]
= 1 []

[]
= 1 2

[]
= 2 []

We suppose that initially only A is present, and that its concentration is [A]0
Consecutive Elementary Reactions

Solving the first equation, we have

= []0 1
The 2nd equation become
[]
+ 2 = 1 []0 1

is the first order of ODE

+ = ()

The integral factor is

Consecutive Elementary Reactions

Multiply this factor to the equation, we have

+ )( =


= )(

so that

2 [] = 1 []0 (1 2 )

1
= []0 1 + 2
1 2
At t = 0, [I] = [I]0 = 0
Consecutive Elementary Reactions
1
= []0
1 2
1
= 2 1 []0
1 2

At all times [A] + [I] + [P] = [A]0, so it follows

that

2 1 1 2
= []0 1 +
1 2
Example

Suppose that in an industrial batch process a substance A produces the

desired compound I which goes on to decay to a worthless product C, each
step of the reaction being first-order. At what time will I be present in
greatest concentration?
Answer
1 2

1
= 2 1 []0
1 2
To get [I]max d[I]/dt = 0
1
0= 2 2 + 1 1 []0
1 2
2 2 = 1 1

1 1
= ln
1 2 2
Self-test

Calculate [I]max from example problem

Answer 2
1 2 1
[] = []0
2
The Steady-state Approximation

The steady-state approximation (which is also widely called the quasi-

steady state approximation, QSSA, to distinguish it from a true steady
state) assumes that, after an initial induction period, an interval during which
the concentrations of intermediates, I, rise from zero, and during the major
part of the reaction, the rates of change of concentrations of all reaction
intermediates are negligibly small
[]
0

when we apply the approximation to the consecutive first-order mechanism,
1 2

The Steady-state Approximation
[]
= 1 2 [] 0

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

= 1 1 []0
k2 does not have to be very much
bigger than ka for the approach to be
reasonably accurate (ka/kb<<1).
Example

Devise the rate law for the decomposition of N2O5, using the steady-state
approximation 2N2O5(g) 4NO2(g) + O2(g)
on the basis of the following mechanism:
N2O5 NO2 + NO3 ka
NO2 + NO3 N2O5 ka
NO2 + NO3 NO2 + O2 + NO kb
NO + N2O5 NO2 + NO2 + NO2 kc
Answer

First identify the intermediates (species that occur in the reaction steps
but do not appear in the overall reaction) and write expressions for their net
rates of formation. Then, all net rates of change of the concentrations of
intermediates are set equal to zero and the resulting equations are solved
algebraically
[]
= 2 3 2 5 0

[3 ]
= 2 5 2 3 2 3 0

2 5
= 2 5 + 2 3 2 5

 2 5 2 2 5
=
+