17-05-2011 A reaction rate that falls with increasi…

Reaction rate always increases with increasing temperature…

Well, nearly always. Chemistry is a complicated subject and dependent

on many variables; an immense variety of compounds, reactions beyond counting,
but behind all this is a relatively small number of broad principles. However, to the
fascination of people like me and the irritation of those who'd be better studying
Physics, there's always the exception that tests the rule.

Reaction rates and the Arrhenius equation.

For a reaction between compounds A and B the rate equation could be

rate = k[A]2[B]

The equation is that for a third-order reaction - not common, but the subject of
this article. The rate equation would have to be found experimentally since it
depends on mechanism, and is not related to the stoichiometric equation – but
then everything else (including the stoichiometric equation for the reaction) has to
be found experimentally as well, so perhaps this doesn't say very much. In the rate
equation the temperature dependent quantity is the rate constant, k; the rate of
reaction changes with a change in temperature because k changes. The
quantitative effect is given by the Arrhenius equation:

k = Ae – Ea/RT

where: A= constant
Ea = activation energy for the reaction
R = gas constant
T = thermodynamic (absolute) temperature.

Since the activation energy Ea is always a positive quantity, the result is

that an increase in temperature always results in an increase in k. This should mean
that for every reaction an increase in temperature increases the rate. Excluded
from this are enzyme-mediated reactions; the rate of these will fall with increasing
temperature beyond the optimum for the enzyme since the enzyme gets cooked.

An exception: the oxidation of nitrogen monoxide, NO.

For a very small number of reactions, all involving NO, the rate of
E:/…/A reaction rate that falls with inc… 1/3
17-05-2011 A reaction rate that falls with increasi…
reaction falls with an increase in temperature. This implies a negative activation
energy. The reason for this apparent peculiarity is that although the rate constant k
does indeed increase with increasing temperature, the mechanism is such that
another constant, the equilibrium constant for one of the mechanistic steps, is also
involved in the rate equation. This falls with increasing temperature.

The reaction of nitrogen monoxide (nitric oxide, nitrogen(II) oxide) with

oxygen is:

2NO(g) + O 2(g) → 2NO2(g)

This is one of only five homogeneous gas reactions known to be third order:

rate = k[NO]2[O2]

the others being the reaction of NO with chlorine, bromine, hydrogen and
deuterium (Bodenstein, 1922 1).

The probability of a termolecular reaction, where the three species collide

simultaneously with the correct energy and the correct orientation in a single step,
is very small. The suggested mechanism for the oxidation of NO with O2 involves
an initial dimerisation in an equilibrium reaction, followed by reaction of the dimer
with the oxygen:

2NO(g) (NO)2(g) . . . . . . . . . . . . . . . . . . . . . . . . . (1)

(NO)2 (g) + O 2(g) → 2NO2(g) . . . . . . . . . . . . . . . . . . . . .(2)

The following discussion depends on two things; firstly that the rate of attainment
of the equilibrium (1) is very fast compared with reaction (2), and secondly that
reaction (2) is the rate limiting step.

Consider the equilibrium reaction (1). From usual equilibrium considerations

Kc = [(NO)2]/[NO]2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (3).

For the rate limiting step (2) we can write

rate = k'[(NO)2][O2];

but from (3)

[(NO)2] = Kc[NO]2

so rate = k'Kc[NO]2[O2]

This is the rate equation quoted with k = k'Kc.

The temperature dependence of the reaction rate.

E:/…/A reaction rate that falls with inc… 2/3
17-05-2011 A reaction rate that falls with increasi…
In the rate equation

rate = k [NO]2[O2] = k'Kc [NO]2[O2]

both k' and Kc are temperature dependent. The constant k' increases with
increasing temperature; the variation of Kc with changing temperature depends on
the thermicity of the equilibrium producing (NO)2. The reaction

2NO → (NO)2

involves bond formation and is therefore exothermic. For an equilibrium where the
reaction from left to right is exothermic, Kc decreases with an increase in
temperature. So; k' rises with temperature increase, but Kc falls. In this reaction k'
increases less than the fall in Kc, so that the overall value k'Kc also falls with an
increase in temperature. So, then, does the reaction rate. The activation energy is
only apparently negative; for the rate-limiting step it is, as is usual, positive.

The reaction and other useful ideas in kinetics can be found in Atkins 2.

References, and a caution.

1. M. Bodenstein, Z. Physik. Chem. 100, 118, 1922.

2. P.W.Atkins, Physical Chemistry, 4th edition, p 802: OUP 1990.

Take care with reading early papers or books on kinetics; the term 'molecularity'
was often used to refer to what we would call overall order. The molecularity of a
reaction is the number of particles that collide in the rate-determining step; the
overall order is the number of particles involved up to and including the rate-
determining step. The oxidation of NO is therefore a third-order, bimolecular
reaction, but is often referred to in earlier works as termolecular. It is an example
of the evolution of nomenclature.

Chemistry contents Home page

Dr Rod Beavon 17 Dean's Yard London SW1P 3PB

email: rod.beavon@westminster.org.uk

E:/…/A reaction rate that falls with inc… 3/3