Chemical kinetics

Chemical reactions, reaction rate

Chemical kinetics is the part of physical chemistry that studies reaction rates.
The reaction rate or rate of reaction for a reactant or product in a particular reaction is
intuitively defined as how fast a reaction takes place. For example, the oxidation of iron under
the atmosphere is a slow reaction which can take many years, but the combustion of butane in a
fire is a reaction that takes place in fractions of a second.

Consider a typical chemical reaction

aA + bB ĺ pP + qQ
The lowercase letters (a, b, p, and q) represent stoichiometric coefficients, while the capital
letters represent the reactants (A and B) and the products (P and Q).
According to IUPAC's Gold Book definition the reaction rate v for a chemical reaction occurring
in a closed system under constant-volume conditions, without a build-up of reaction
intermediates, is defined as:

1 dc A 1 dcB 1 dcP 1 dcQ

v=− =− = = (1)
a dt b dt p dt q dt

where cI, I=A, B, P, or Q is the concentration of substance. The IUPAC recommends that the
unit of time should always be the second. Reaction rate usually has the units of mol dm-3 s-1. It is
important to bear in mind that the previous definition is only valid for a single reaction, in a
closed system of constant volume.
The quantity

dξ
ξ = (2)
dt
defined by the equation

1 dnA 1 dnB 1 dnP 1 dnQ

ξ = − =− = = (3)
a dt b dt p dt q dt
where nI designates the amount of substance I (I=A, B, P, or Q) conventionally expressed in
units of mole, may be called the 'rate of conversion' (extent of reaction) and is appropriate
when the use of concentrations is inconvenient, e.g. under conditions of varying volume. In a
system of constant volume, the rate of reaction is equal to the rate of conversion per unit volume
throughout the reaction. For a stepwise reaction this definition of 'rate of reaction' (and 'extent of
reaction', ξ) will apply only if there is no accumulation of intermediate or formation of side
products. It is therefore recommended that the term 'rate of reaction' be used only in cases where
it is experimentally established that these conditions apply.
The rate law or rate equation for a chemical reaction is an equation which links the reaction
rate with concentrations or pressures of reactants and constant parameters (normally rate
coefficients and partial reaction orders). To determine the rate equation for a particular system
one combines the reaction rate with a mass balance for the system. For a generic reaction A + B
ĺ C the simple rate equation is of the form:
v = kc Am cBn (4)

1
the concentration is usually in mol/dm3, and k is known as the reaction rate coefficient or rate
constant, although it is not really a constant, because it includes everything that affects reaction
rate outside concentration: mainly temperature but also ionic strength, surface area of the
adsorbent or light irradiation. The exponents n and m are called reaction orders and depend on
the reaction mechanism. The stoichiometric coefficients and reaction orders are very often equal,
but only in one step reactions, molecularity (number of molecules or atoms actually colliding),
stoichiometry and reaction order must be the same.

Since many complex reactions proceed in stages via intermediates (eg. ions, molecules or free
radicals), and, since the measured rate is always that of the slowest step, a knowledge of the
overall order, or better, the separate orders with respect to the individual reactants, often enables
the steps to be elucidated. In such circumstances, the rate of reaction cannot be expressed as a
simple equation.

The Arrhenius equation is a simple, but remarkably accurate, formula for the temperature
dependence of the rate constant, and therefore rate, of a chemical reaction. Actually, the
Arrhenius equation gives "the dependence of the rate constant k of chemical reactions on the
temperature T (in Kelvin) and activation energy Ea", as shown below:
k = Ae − E a / RT (5)
where A is the pre-exponential factor or simply the prefactor and R is the gas constant. The units
of the pre-exponential factor are identical to those of the rate constant and will vary depending
on the order of the reaction. It can be seen that either increasing the temperature or decreasing
the activation energy (for example through the use of catalysts) will result in an increase in rate
of reaction. The activation energy can be interpreted as the minimal energy of the molecules to
undergo reaction. This energy is needed, either, to rupture a chemical bond, eg. in free radical
gas reactions, or to allow rearrangements when the molecules collide.
Taking the natural logarithm of the Arrhenius equation yields:

− Ea 1
ln k = + ln A (6)
R T
So, when a reaction has a rate constant which obeys the Arrhenius equation, a plot of ln k versus
T -1 gives a straight line, whose slope and intercept can be used to determine Ea and A. This
procedure has become common in experimental chemical kinetics. To determine the activation
energy of a reaction, one must know a rate constant of the reaction at least at two different
temperatures. Applying the Eq. 6, one can easy express

k1 Ea 1 1
ln = ( − ) (7)
k2 R T2 T1

where k1 and k2 correspond to temperature T1 and T2, respectively.

Since the rate of a given reaction depends upon the concentration of the reactants, the speed of
the process falls off as the reaction proceeds, for the reactants being continuously consumed.
The reaction is becoming slower and slower but theoretically never ceases. It is, therefore, not
possible to define the general rate of a reaction, and so in practice the rate is considered at a
particular instant. The rate may be defined in any convenient way, usually, the rate of change of
concentration (c) of one of the reactants or products is chosen. The experimental data then follow
a change of concentration with time (t), and the rate at any instant is given by the tangent to a
curve of the plot c=f(t).

2
Zero-order reactions are often seen for thermal chemical decompositions where the reaction rate
is independent of the concentration of the reactant (changing the concentration has no effect on
the speed of the reaction). The rate law for a zero-order reaction is
v=k (8)

where v is the reaction rate, and k is the reaction rate coefficient with units of concentration/time.
If, and only if, this zero-order reaction 1) occurs in a closed system, 2) there is no net build-up of
intermediates and 3) there are no other reactions occurring, it can be shown by solving a mass
balance for the system that:

dc A
v=− =k (9)
dt
If this differential equation is integrated it gives an equation which is often called the integrated
zero-order rate law

c A = −kt + c A0 (10)

where cA represents the concentration of the chemical of interest at a particular time, and cA0
represents the initial concentration. A reaction is zero order if concentration data are plotted
versus time and the result is a linear function. The slope is the zero order rate constant k.
The half-life of a reaction describes the time needed for half of the reactant to be depleted. For a
zero-order reaction the half-life is given by

c A0
t1 = (11)
2
2k

A first-order reaction depends on the concentration of only one reactant (a unimolecular

reaction). Other reactants can be present, but each will be zero-order.

A → Products

The rate law for an elementary reaction that is first order with respect to a reactant A is
dc A
v=− = k .c A (12)
dt
k is the first order rate constant, which has units of 1/time. The integrated first-order rate law
is

cA
ln = −k .t (13)
c0 A

A plot of ln cA vs. time t gives a linear function with a slope of − k. One can easy express the
concentration cA of reactant A at any time t

c A = c 0 A .e − k .t (14)

where c0 A is the initial concentration of reactant A.

3
The half life of a first-order reaction ( t1 2 ) is independent of the starting concentration and is
given by
ln 2
t1 2 = (15)
k
Kinetics of a first-order reaction characterizes also a radioactive decay, the Eq. 15 describes the
time taken for half the radionuclide's atoms to decay.

A second-order reaction depends on the concentrations of one second-order reactant, or two

first-order reactants. For a second order reaction, its reaction rate is given by:

v = kc A2 (16) or v = kc AcB (17)

We will deal with the bimolecular reaction

A + B → Products,
supposing the same initial concentration of A and B reactants, c0A=c0B=c0. The differential rate
law for the second-order reaction is then
dc
− = k .c 2 (18)
dt

Solving the differential equation, one can obtain

1 1
− = k .t (19)
c c0

where c is the concentration of reactant at time t (cA=cB=c), and k is the second-order constant,
which has dimension of concentration-1 time-1 (eg. dm3 mol-1s-1). In this case, a characteristic plot
which will produce a linear function is 1/c vs. time t, with a slope of k (Fig. 1).

The half-life equation for a second-order reaction dependent on one second-order reactant is

1
t1 / 2 = (20)
k .c 0

Fig. 1 Plot 1/c vs. t.