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36.2 THE PREEQUILIBRIUM APPROXIMATION 957

Substituting Equation (36.9) into Equation (36.5) results in the following predicted rate
law expression for this mechanism:

(k 3N O 4 - k-13NO243NO34)
1
R =
2 1 2 5
k13N2O54
ak13N2O54 - k-1 a bb
1
=
2 k-1 + 2k2

3N O 4 = keff 3N2O54
k1 k2
= (36.10)
k-1 + 2k2 2 5

In Equation (36.10), the collection of rate constants multiplying [N2O5] has been
renamed keff. Equation (36.10) demonstrates that the mechanism is consistent with the
experimentally observed first-order dependence on [N2O5]. However, as discussed in
Chapter 35, the consistency of a reaction mechanism with the experimental order
dependence of the reaction is not proof that the mechanism is absolutely correct but
instead demonstrates that the mechanism is consistent with the experimentally deter-
mined order dependence.
The example just presented illustrates how reaction mechanisms are used to explain
the order dependence of the reaction rate. A theme that reoccurs throughout this chap-
ter is the relation between reaction mechanisms and elementary reaction steps. As we
will see, the mechanisms for many complex reactions can be decomposed into a series
of elementary steps, and the techniques developed in the previous chapter can be read-
ily employed in the evaluation of these complex kinetic problems.

36.2 The Preequilibrium Approximation

The preequilibrium approximation is a central concept employed in the evaluation of
reaction mechanisms. This approximation is used when equilibrium among a subset of
species is established before product formation occurs. In this section, the preequilib-
rium approximation is defined. This approximation will prove to be extremely useful in
subsequent sections.

36.2.1 General Solution

Consider the following reaction:
kf kp
A + B Δ I:P (36.11)
kr

In Equation (36.11), forward and back rate constants link the reactants A and B with an
intermediate species, I. Decay of I results in the formation of product, P. If the forward
and backward reactions involving the reactants and intermediate are more rapid than
the decay of the intermediate to form products, then the reaction of Equation (36.11)
can be envisioned as occurring in two distinct steps:
1. First, equilibrium between the reactants and the intermediate is maintained during
the course of the reaction.
2. The intermediate undergoes decay to form product.
This description of events is referred to as the preequilibrium approximation. The
application of the preequilibrium approximation in evaluating reaction mechanisms
containing equilibrium steps is performed as follows. The differential rate expression
for the product is

= kp3I4
d3P4
(36.12)
dt

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958 CHAPTER 36 Complex Reaction Mechanisms

In Equation (36.12), [I] can be rewritten by recognizing that this species is in equilib-
rium with the reactants; therefore,
3I4 kf
= = Kc
3A43B4
(36.13)
kr
3I4 = Kc3A43B4 (36.14)

In the preceding equations, Kc is the equilibrium constant expressed in terms of

reactant and product concentrations. Substituting the definition of [I] provided by
Equation (36.14) into Equation (36.12), the differential rate expression for the prod-
uct becomes

= kp3I4 = kp Kc3A43B4 = keff 3A43B4

d3P4
(36.15)
dt
Equation (36.15) demonstrates that with the preequilibrium approximation, the pre-
dicted rate law is second order overall and first order with respect to both reactants
(A and B). Finally, the rate constant for product formation is not simply kp but is
instead the product of this rate constant with the equilibrium constant, which is in turn
equal to the ratio of the forward and backward rate constants.

36.2.2 A Preequilibrium Example

The reaction of NO and O2 to form product NO2 provides an example in which the
preequilibrium approximation provides insight into the mechanism of NO2 formation.
The specific reaction of interest is
2 NO(g) + O2(g) : 2 NO2(g) (36.16)
One possible mechanism for this reaction is that of a single elementary step correspon-
ding to a trimolecular reaction of two NO molecules and one O2 molecule. The experi-
mental rate law for this reaction is second order in NO and first order in O2, consistent
with this mechanism. However, this mechanism was further evaluated by measuring the
temperature dependence of the reaction rate. If correct, raising the temperature will
increase the number of collisions, and the reaction rate should increase. However, as
the temperature is increased, a reduction in the reaction rate is observed, proving that
the trimolecular-collisional mechanism is incorrect. An alternative mechanism for this
reaction was proposed:
kf
2 NO Δ N2O2 (36.17)
kr
kp
N2O2 + O2 ¡ 2 NO2 (36.18)

In the first step of this mechanism, Equation (36.17), an equilibrium between NO and
the dimer N2O2 is established rapidly compared to the rate of product formation. In the
second step, Equation (36.18), a bimolecular reaction involving the dimer and O2
results in the production of the NO2 product. The stoichiometric number for each step
is 1. To evaluate this mechanism, the preequilibrium approximation is applied to step 1
of the mechanism, and the concentration of N2O2 is expressed as
kf
3N2O24 = 3NO42 = Kc3NO42 (36.19)
kr

Using the second step of the mechanism, the reaction rate is written as

1 d3NO24
R = = kp3N2O243O24 (36.20)
2 dt
Substitution of Equation (36.19) into the differential rate expression for [NO2] yields

R = kp3N2O243O24 = kp Kc 3NO423O24 = keff 3NO423O24 (36.21)

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