1 Introduction

Chemical kinetics is conventionally regarded as a topic in physical chemistry. In this

guise it covers the measurement of rates of reaction, and the analysis of the
experimental data to give a systematic collection of information which summarises
all the quantitative kinetic information about any given reaction. This, in turn, enables
comparisons of reactions to be made and can afford a kinetic classification of
reactions. The sort of information used here is summarized in terms of

the factors influencing rates of reaction,

the dependence of the rate of the reaction on concentration, called the order of the
reaction,

the rate expression, which is an equation which summarizes the dependence of the
rate on the concentrations of substances which affect the rate of reaction,

this expression involves the rate constant which is a constant of proportionality
linking the rate with the various concentration terms,

this rate constant collects in one quantity all the information needed to calculate
the rate under specific conditions,

the effect of temperature on the rate of reaction. Increase in temperature generally
increases the rate of reaction. Knowledge of just exactly how temperature affects
the rate constant can give information leading to a deeper understanding of how
reactions occur.

All of these factors are explained in Chapters 2 and 3, and problems are given to aid
understanding of the techniques used in quantifying and systematizing experimental
data.
However, the science of kinetics does not end here. The next task is to look at the
chemical steps involved in a chemical reaction, and to develop a mechanism which
summarizes this information. Chapters 6 and 8 do this for gas phase and solution
phase reactions respectively.

An Introduction to Chemical Kinetics. Margaret Robson Wright

# 2004 John Wiley & Sons, Ltd. ISBNs: 0-470-09058-8 (hbk) 0-470-09059-6 (pbk)
2 INTRODUCTION

The final task is to develop theories as to why and how reactions occur, and to
examine the physical and chemical requirements for reaction. This is a very important
aspect of modern kinetics. Descriptions of the fundamental concepts involved in the
theories which have been put forward, along with an outline of the theoretical
development, are given in Chapter 4 for gas phase reactions, and in Chapter 7 for
solution reactions.
However, kinetics is not just an aspect of physical chemistry. It is a unifying topic
covering the whole of chemistry, and many aspects of biochemistry and biology. It is
also of supreme importance in both the chemical and pharmaceutical industries. Since
the mechanism of a reaction is intimately bound up with kinetics, and since
mechanism is a major topic of inorganic, organic and biological chemistry, the
subject of kinetics provides a unifying framework for these conventional branches of
chemistry. Surface chemistry, catalysis and solid state chemistry all rest heavily on a
knowledge of kinetic techniques, analysis and interpretation. Improvements in
computers and computing techniques have resulted in dramatic advances in quantum
mechanical calculations of the potential energy surfaces of Chapters 4 and 5, and in
theoretical descriptions of rates of reaction. Kinetics also makes substantial con-
tributions to the burgeoning subject of atmospheric chemistry and environmental
studies.
Arrhenius, in the 1880s, laid the foundations of the subject as a rigorous science
when he postulated that not all molecules can react: only those which have a certain
critical minimum energy, called the activation energy, can react. There are two ways
in which molecules can acquire energy or lose energy. The first one is by absorption
of energy when radiation is shone on to the substance and by emission of energy.
Such processes are important in photochemical reactions. The second mechanism is
by energy transfer during a collision, where energy can be acquired on collision,
activation, or lost on collision, deactivation. Such processes are of fundamental
importance in theoretical kinetics where the ‘how’ and ‘why’ of reaction is
investigated. Early theoretical work using the Maxwell–Boltzmann distribution led
to collision theory. This gave an expression for the rate of reaction in terms of the rate
of collision of the reacting molecules. This collision rate is then modified to account
for the fact that only a certain fraction of the reacting molecules will react, that
fraction being the number of molecules which have energy above the critical
minimum value. As is shown in Chapter 4, collision theory affords a physical
explanation of the exponential relationship between the rate constant and the absolute
temperature.
Collision theory encouraged more experimental work and met with considerable
success for a growing number of reactions.
However, the theory appeared not to be able to account for the behaviour
of unimolecular reactions, which showed first order behaviour at high pressures,
moving to second order behaviour at low pressures. If one of the determining
features of reaction rate is the rate at which molecules collide, unimolecular reactions
might be expected always to give second order kinetics, which is not what is
observed.
INTRODUCTION 3

This problem was resolved in 1922 when Lindemann and Christiansen proposed
their hypothesis of time lags, and this mechanistic framework has been used in all the
more sophisticated unimolecular theories. It is also common to the theoretical
framework of bimolecular and termolecular reactions. The crucial argument is that
molecules which are activated and have acquired the necessary critical minimum
energy do not have to react immediately they receive this energy by collision. There
is sufficient time after the final activating collision for the molecule to lose its critical
energy by being deactivated in another collision, or to react in a unimolecular step.
It is the existence of this time lag between activation by collision and reaction
which is basic and crucial to the theory of unimolecular reactions, and this
assumption leads inevitably to first order kinetics at high pressures, and second
order kinetics at low pressures.
Other elementary reactions can be handled in the same fundamental way:
molecules can become activated by collision and then last long enough for there to
be the same two fates open to them. The only difference lies in the molecularity of the
actual reaction step:

in a unimolecular reaction, only one molecule is involved at the actual moment of

chemical transformation;

in a bimolecular reaction, two molecules are involved in this step;

in a termolecular reaction, three molecules are now involved.
k
1
A þ A ! A þ A bimolecular activation by collision
k
A þ A ! 1
AþA bimolecular deactivation by collision
 k2
A þ bA ! products reaction step

where A is an activated molecule with enough energy to react.

b¼0 defines spontaneous breakdown of A ,

b¼1 defines bimolecular reaction involving the coming together of A with A
and
b¼2 defines termolecular reaction involving the coming together of A with two
As.

This is a mechanism common to all chemical reactions since it describes each

individual reaction step in a complex reaction where there are many steps.
Meanwhile, in the 1930s, the idea of reaction being defined in terms of the spatial
arrangements of all the atoms in the reacting system crystallized into transition state
theory. This theory has proved to be of fundamental importance. Reaction is now
defined as the acquisition of a certain critical geometrical configuration of all the
atoms involved in the reaction, and this critical configuration was shown to have a
critical maximum in potential energy with respect to reactants and products.
4 INTRODUCTION

The lowest potential energy pathway between the reactant and product configura-
tions represents the changes which take place during reaction, and is called the
reaction coordinate or minimum energy path. The critical configuration lies on this
pathway at the configuration with the highest potential energy. It is called the
transition state or activated complex, and it must be attained before reaction can
take place. The rate of reaction is the rate at which the reactants pass through this
critical configuration. Transition state theory thus deals with the third step in the
master mechanism above. It does not discuss the energy transfers of the first two steps
of activation and deactivation.
Transition state theory, especially with its recent developments, has proved a very
powerful tool, vastly superior to collision theory. It has only recently been challenged
by modern advances in molecular beams and molecular dynamics which look at the
microscopic details of a collision, and which can be regarded as a modified collision
theory. These developments along with computer techniques, and modern experi-
mental advances in spectroscopy and lasers along with fast reaction techniques, are
now revolutionizing the science of reaction rates.