Chemical Kinetics

N.B.Singh
Research and Technology Development Centre
School of Engineering and Technology
Sharda University, Greater Noida
Why chemical reactions occur at all ?
Why do some chemical reactions occur very fast, when others require
days, months or even years to complete ?
Why do small changes in temperature have large effects on the rate
of reactions ?
How the catalysts affect the rates of chemical reactions ?
What is the effect of concentration of the reactants on the rates of
reactions ?
How does a study of the rate of a chemical reaction provide
information about the way in which the molecules combine to form
products ?
The answers to all these basic questions are given by the study of
chemical kinetics.
Chemical kinetics is concerned with the speeds of chemical
reactions and deals with the study of rates of chemical reactions
and the mechanisms (the series of steps) by which they occur.

Although thermodynamics is very powerful tool for understanding

the nature of chemical equilibrium, the possibility of chemical
reaction and the heat changes associated with it, but it gives no
information about (i) the speed of reaction and (ii) its mechanism.

Chemical kinetics does provide an approach for understanding

these two fundamental questions.
 Exo- and Endothermic Reactions
Exothermic reaction: reaction gives off energy.
reactants products + energy

Endothermic reaction: reaction takes in energy.

energy + reactants products

 Bonds and Energy
When bonds are broken: energy is absorbed.
(analogy: stretching a rubber band)

When bonds are formed : energy is released.

(analogy: releasing a stretched rubber band)
 Average bond energies, kcal/mole
C-H 98
O-H 110
C-C 80
C-O 78
H-H 103
C-N 65
O=O 116 (2 x 58)
C=O 187* (2 x 93.5)
C=C 145 (2 x 72.5)
(* as found in CO2)
Rate of Chemical Reactions: The Reaction Rate
The rate of chemical reaction, sometimes called the reaction velocity, may be
defined as the decrease in concentration of a reactant or increase in
concentration of a product during a given unit of time. In general, the rate of any
chemical reaction can be expressed as the ratio of the change in concentration of
a reactant (or product) to a change in time.
change in concentration
i.e. rate of chemical reaction = change in time

= moles / litre
sec ond
= moles litre–1 sec–1
Let us consider the following simple reaction
A B
in which one mole of reactant A is transformed into one mole of product B. At
the start of the reaction, no product ( B ) is present initially, and, as time goes on,
the concentration of B increases with a corresponding decrease in the
concentration of A
The rate of reaction at any time will be equal to the rate of formation of product ( B )
or the rate of consumption of reactant ( A ) at that time. Thus,

amount of A consumed
rate of reaction = time interval

amount of B produced
= time interval

d [ A] d [ B]
or rate =   ... (12.1)
dt dt

where [A] and [B] denotes the concentrations of A and B in moles / litre and time t
is measured in second. The negative sign ( – ve ) indicates that the reactant A is
disappearing in the reaction so the rate of change is expressed as . The rate of
d[A ] d[B]

change of B is expressed as ; the positive sign indicates the increase in
dt dt
concentration of B with time. The unit of rate is expressed in moles / litre/ second or
mol lit–1 sec–1 or mol L–1 s–1 .
Let us further assume if ' a ' be the initial concentration of the reactant A
and ' x ' be the concentration of product B after time t, then
A B
at t = 0, a 0
at t = t, (a–x) x
dx d (a  x)
rate of reaction = dt =         dt ... (12.2)
where (a – x) is the amount of A after time, t.
Now let us consider a more general hypothetical reaction :
a A + bB c C + dD

If no other reaction takes place, the changes in concentration are related to

each other. For every ‘ a ’ mol/L decrease in the concentration of A, the
concentration of B must decrease by  ' b ' mol/L, the concentration of C and
D must increase by ' c ' and ' d '  mol / L respectively. In order to describe
the rate of reaction one has to divide each change by its coefficient in the
balanced equation. Thus, the rate of reaction based on the rate of change of
concentration of each species is written as
 [ A] [B] [C] [D]
Rate of reaction =  a . dt =  b . dt = c . dt = d . dt … (12.3)
 
in terms of reactants in terms of products

where '' represents the change in concentration.

Experimental Determination of the Reaction Rate

For the experimental determination of rate of any chemical reaction several
techniques, which can measure the concentration of chemical species
involved in the reaction at different times, may be used to monitor the
concentration change depending on the nature of reaction. Generally the
chemical reactions can be divided into the following three categories ;
1. Slow reaction
2. Moderately fast reactions and
3. Fast reactions
1. Determination of Reaction Rates for Slow Reactions
Following methods are generally employed to determine the rate of slow
reactions
 
(i) Titration method
The method is useful for reaction in solution, particularly when titration
is possible. A typical example is the hydrolysis of an ester, in the presence of
mineral acid which acts as a catalyst.
  H+
CH3COOC2H5 + H2O CH3COOH + C2H5OH
 
The disappearance of ester can be followed by withdrawing a definite amount of
reaction mixture after different interval of time and then titrating it with alkali.
The volume of alkali used is equivalent to the sum of mineral acid used as a
catalyst, which remains constant throughout, plus the acetic acid produced in the
reaction. The concentration of acetic acid is determined at different time
intervals. The rate of hydrolysis can thus be obtained by plotting concentration of
acetic acid against time.
 
  

(ii) Pressure and volume change method

Gaseous reactions can sometimes be followed by means of pressure
measurements. This method can be applied to those reactions which involve a
change in the number of molecules. For example, the decomposition of nitrous
oxide on heating occurs as :
2 NO2 N 2 + 2 O2
In this reaction three molecules of products are produced for every two
molecules of nitrous oxide, so the pressure increases. The amount of
decomposition that has occurred can be calculated from the total pressure. This
method cannot be applied to reactions where there are equal number of gaseous
molecules on both sides of the equation.

This is a convenient method to measure the rate of phyrolysis of nitrogen

pentaoxide and some organic compounds in the gas phase such as acetaldehyde
and azo methane
CH3CHO CH4 + CO
and CH3N2CH3 C2 H 6 + N 2
 
The rate can also be measured by density measurements. Reactions in solution
are usually accompanied by a small change in density, and therefore, in the
volume. Thus the rates can be measured by determining the change in volume as
a function of time.
(iii) Spectroscopic method

The absorption spectroscopy ( visible U.V. and I.R. ) is very useful technique for
studying the rates of reactions taking place in solution. The concentration
change of reactant or product can be determined by absorption spectroscopy.
The characteristic absorption band of the species is selected and change in
absorption is measured with time. The concentration of the reactant or
product is calculated by using Beer's law
A =.c. … (12.6)

where A is the absorbance, c the concentration of the solution ,  the
extinction coefficient and  the optical cell path length. This equation predicts
that a plot of absorption versus
 concentration will give a straight line. Since at
constant wavelength and for a particular species,  is a constant and  is kept
fixed in the experiment, the absorbance (A) becomes directly proportional to
the concentration(c) of the reactant or product.
(iv) Methods based on the measurement of change in some physical
properties
It is noted that in certain reactions, the physical properties of reactants or
products may change due to the change in their concentrations during the
course of the reaction. This may be used to determine the reaction rate. The
following physical properties may be used for this purpose.

Refractive Index : The measurement of refractive index can be used to study

the kinetics of polymerization of some substances such as styrene. During
polymerization process, the refractive index changed with time.
 
CH CH2 CH CH

n
n
Colorimetric Measurements : Colour intensity measurements of reactants or products
with the help of colourimeter can be used to measure the rate of some reactions. For
example, in the reaction
 
2 HI + H2O2 2H2O + I2
 
the rate of production of iodine is studied by noting the change in the colour of the
solution.
 
Change in Optical Properties : – Another useful physical measurement is that of optical
rotation. It can be used for reaction involving optically active compounds, i.e., those that
have the property of rotating the plane of polarized light. An example is the hydrolysis of
sucrose; the products being glucose and fructose

  H+
C12H22O11 + H2O C6H12O6 + C6H12O6
Sucrose Glucose Fructose
 
Sucrose rotates polarised light to the right (dextro rotation) while the mixture of glucose
and fructose rotates it to the left (laevo rotatory). Because of this, the reaction is known
as the inversion of sucrose. The rate of the reaction is obtained by examining the reaction
mixture in a polarimeter.
Specific Conductance Measurement : In some reaction, the rate kinetics can be
studied with the help of conductance measurements. Electrical conductivity in
solution depends on concentration and hence kinetics can be studied by noting
the change in conductivity as a function of time. For example during
saponification of esters in an aqueous solution, conductivity decreases due to
lesser mobility of the negative ion which is produced in the reaction. The highly
mobile OH– ions are consumed.

CH3COOC2H5 + OH– CH3COO– + C2H5OH

Besides these other physical properties such as viscosity, thermal conductivity

and heat changes during a reaction can also be successfully used for monitoring
the reaction kinetics.
 2. Rate of Moderately Fast Reactions :
For reactions having a life time of the order of milliseconds, there is another
factor that must be taken into account besides the time required for
measuring the concentration. The time it takes to mix two reactants may be of
the order of several seconds to a minute. Clearly this will cause problems in a
reaction whose life time is of the order of seconds. Various kinds of flow
systems have been designed to enhance the mixing of reactants.

Linear Flow Technique : In the linear flow technique the reactants (gases) are
mixed, and they flow at constant known rate through a tube; the gas is
analyzed as it leaves the tube. The reaction time is the time between mixing
and leaving, and this can be adjusted by varying the flow rate.

Stopped Flow Technique : A modification of the linear flow technique is the

stopped–flow technique, which is useful for studying reactions between liquid
solution.
 
3. Rate of Fast Reactions
For fast reactions some special techniques are used to determine the rate. These are :
(a) Shock Tubes Technique : Shock tubes provide a useful technique for studying gas–
phase reactions in the milli to microsecond range at elevated temperatures. The tube
is a metal of glass pipe with diameter of the order of centimeters and length of several
meters. The tube is divided into two sections by a thin diaphragm usually made of
metal. The "driver gas" (usually helium or hydrogen) is placed on one side of the
diaphragm, and the reactant gas at a pressure of a few torr is placed on the other side.
When the diaphragm is ruptured, the driver gas forms a shock wave with a sharp wave
front. The shock wave travels down the tube, compressing and heating the reactant
gas, which is observed at some point down the tube. The reactants in the tube are
subjected to a very sudden increase in pressure, as much as 109 atm, with an
associated temperature rise as high as 107 K. The shock is sufficient to excite the
molecules present and to dissociate them into atoms and radicals.
(b) Flash Photolysis Technique : This technique is suitable for fast reactions in both
gas and liquid systems. It was first developed by Norrish and Porter for gas–phase
reactions, and it applies to reactions initiated by light.
Recent advances in laser technology have made it possible to extend the range of
flash photolysis from the microsecond ( 10-6 s ) and ultimately to the picosecond ( 10-12
s ) region.
 Factors that Affect Reaction Rates
Four factors have marked effect on the rates of chemical
reactions in case of homogeneous systems. They are

1. nature of reactants
2. concentrations of reacting species
3. temperature, and
4. presence of a catalyst
5. Effect of Surface Area of Reactants

By studying how various factors influence the reaction rates, it becomes

possible to control the rates of reactions. However, for reactions in
hetergeneous systems such as in case of solid state reactions, the surface
area of the reactants and in case of photochemical reactions exposure to
radiation becomes important factors which affect the reaction rates.
The Dependence of Reaction Rate on Reactant Concentration
1. The Rate Expression and Rate Constant
As the concentration of reactants change at constant temperature, the rate of
reaction changes. Therefore, if a chemical reaction is followed over a period of time, it
is found that as the reactants are consumed, the rate gradually decreases. The
dependence of rate on the concentrations of the reactants can be expressed in terms
of rate expression for a reaction. This describes how the reaction rate directly varies
with the active concentrations of the reactants. The rate law is experimentally
deduced for each reaction.
The rate expression for a homogeneous reaction
A + B Products
may be written in the general form as
d[A] d[B]
Rate = dt   = k [A] [B] moles litre–1 sec–1 ... (12.7)
dt

in which it is assumed that the active concentrations of A and B are equal to their
actual concentrations in the reacting system. The symbol of bracket [ ] in Eq. (12.7)
indicates the concentration and k is called the rate constant for the reaction at a
particular temperature. It remains unchanged throughout the course of the reaction.
The rate constant is defined as 'a measure of the rate of a chemical reaction under
specific conditions'. It is a characteristic of a given reaction but varies with
temperature.
Order of a reaction
The number of concentration terms appearing in the rate expression mentioned above are
important in obtaining the characteristic rate constant, k from the experimental data. The
number of these concentration terms determine the reaction order. The order of a particular
reaction may be determined either with respect to one of the reactants or as the overall order
of the reaction. The rate expression for the general reaction
nA+mB Products

is written as rate = k [A]n [B]m moles litre–1 sec–1 .. (12.11)

where n and m are exponents and k is the rate constant. The powers ( n and m ) to which the
concentrations [A] and [B] are raised are usually integers or zero but are occasionally fractional.
A power of one means that the rate is directly proportional to the concentration of that
reactant. A power of two means that the rate increases as the square of that concentration. A
power of zero means that the rate is in dependant of the concentration of that reactant. The
value of n is said to be the order of the reaction with respect to A, and m is the order of the
reaction with respect to B. The overall order of the reaction will then be equal to (n + m).
Thus, the order of a reaction with respect to one of the reactants is equal to the power to
which the concentration of that reactant is raised, where as, the overall order of a reaction
may be defined as the sum of powers to which the reactant concentrations are raised in that
rate expression, or in other words, it is the sum of the orders with respect to each reactant.
For example, in the above rate expression (12.11) if n = 1 and m = 2 then the
reaction is said to be of first order with respect to A, and is of second order with
respect to B. The overall order of this reaction will be the sum of n and m i.e. ( 1
+ 2 = 3 ) , three. The values of m and n can not be determined from chemical
equation but may be found from the experimental data. In general, for
reactions with rate expressions ;
rate = k [A], the order is ONE
rate = k [A] [B]
or = k [A]2, the order is TW
and if rate = k [A] [B] [C]
or = k [A]2 [B]
or = k [A]2 [C]
or = k [A]3 , the order is THREE
 [A], [B] and [C] represents various reactant concentrations. However, the
reaction is of zero order when n = m = 0. In this case [A]0 or [B]0 will be one,
(since the value of any number raised to zero power is one ) no matter what is
the value of [A] or [B].
The order of a reaction does not have to be an integer [n = 1, 2 or 3 ) always;
fractional powers are also sometimes found. For example, the decomposition of
acetaldehyde (CH3CHO) at 450 K which occurs as CH3CHO  CH4 + CO is
described by the rate expression expressed as

rate = = k [ CH3CHO ]3/2   moles litre–1 sec–1

which indicates that the reaction order is 3/2. Thus, it may be inferred that the
reaction order should be experimentally determined and then established.
 Molecularity of a Reaction
We use the term molecularity to designate the number of molecules taking
part in an elementary reaction. A unimolecular elementary reaction is one in
which single molecule undergoes decay or rearrangement, a bimolecular
elementary reaction is one in which two molecules collide and react, and so
forth.
Molecularity and order are in general different from one–another. Order refers
to the kinetics whereas molecularity has to do with mechanism. The following
are examples of unimolecular, bimolecular and termoleclar processes,
respectively,
N2O5 NO2 + NO
KClO + KClO2 KCl + KClO3
2 NO + O2 2 NO2
The molecularity of chemical reactions are whole numbers like 1, 2, 3, …. etc.
Again we sometimes meet reactions of zero in terms. There must be at least
one molecule reacting. Yet again, there are reactions of fractional order ;
fractional molecularity is more difficult to envisage.
Deduction of Rate Laws
The expression which gives the reaction rate as a function of the concentration of
each of the substances affecting the rate is called the rate law for the reaction.
We deduce below the rate laws for chemical reactions of different orders.
 
(i) Zero Order Reactions
In kinetic term, a reaction is said to be of zero order when its rate of reaction does
not depend on the concentrations of the reactant molecules. Thus, for a reaction
A Products
if the rate is independent of the concentration of A i.e. [A], then the reaction is of
zero order and the rate expression is written as
 
rate = k [A]0 = k ... (12.12)
 
If x be the concentration of the product formed at any time t, then
mathematically one can write
 dx
rate of formation of product = = k ... (12.13)
dt
or dx = k . dt ... (12.14)
In order to obtain an expression relating the concentration of reactant with
time, one will have to integrate Eq. (12.14). On doing so one can write
 dx = k .  dt ... (12.15)
or x = kt + C ... (12.16)
 
where C is a constant of integration. This integration constant C can be
evaluated by applying the condition ;
x=0 when t = 0 ( i.e. initially no product is formed )
Thus, from Eq. (12.16) it is found that C = 0

So that x = k.t 1 ... (12.17)

or k = t. x ... (12.18)

Eq. (12.17) indicates that a plot of concentrations x against time t should

yield a straight line which passes through the origin. The slope of this line will
give the value of rate constant k.
Example of Zero Order Reaction
h
  H2 + Cl2 2 H Cl
Characteristic of Zero–Order Reaction
(1) Units of the Zero–Order Rate Constant, k. Since the rate constant in the zero
order equation contains one concentration term in the numerator and time factor
in denominator. Therefore, the dimensions of k are
x concentration
k = t  time
= (concentration) (time)–1
If concentration is expressed in moles/litre and time in second, the unit of k will be
mole litre–1 second–1 for a zero order reaction.
 
(2) Half life time for a Zero Order Reaction
The time required for the completion of any fractional change is proportional to
the initial concentration of the reactant.
At half change, for instance x = a / 2 and t = t1/2 , the rate constant becomes
 
k = a/2 or t1/2 = a
1/ 2t  2k
or t1/2 a
 
Here t1/2 is half life of the reaction. Thus, for a zero order reaction the time
required for the completion of any fraction of change is proportional to the initial
concentration.
(ii) Kinetics of First Order Reaction
The first order reaction, at a given temperature, may be defined as one in which
the reaction rate depends only on the first power of the concentration of reacting
substance. For the general reaction

A Products
 
The rate expression is written as
d[A]

rate = dt = k[A] (12.19)
Let us assume that the initial concentration of A at the start of the reaction ( i.e
at t = 0 ) is ' a ' . If x moles of A have been converted into the product then
the amount of A left after time t will be ( a – x ). the rate equation (12.19)
then can be written as
d[A ] dx
– dt = dt = k (a – x )

dx
or (a  x ) = k . dt ... (12.20)
On integrating Eq. (12.20) , we can write
 
dx
 (a  x ) =  k dt
 
or – ln ( a – x) = k t + C ... (12.21)
where C is constant of integration which is evaluated by applying the conditions ;
x = 0 at t = 0 . Thus Eq. (12.21) yields
–ln ( a ) = C … (12.22)
On substituting the value of C from Eq. (12.22)  in Eq. (12.21), we get
l n ( a ) – ln ( a – x) = k t ... (12.23)
 a 
or k t = ln  (a  x ) 

1  a 
or k = t . ln   ... (12.24)
 (a  x ) 

2.303  a 
or k = log   ... (12.25)
t  (a  x ) 
Eq. (12.25) is the rate expression for the first order reaction.
 Characteristics of First Order Reactions
(1) Units of First Order Rate Constant: Since in the first order equation the
 a 
 
functions is the ratio of two concentrations, so that its value is independent
a  x of
the actual concentrations used. The rate constant k , therefore, has the units of
1
   =  time–1. If time is expressed
time in seconds, the unit of k will be second for
–1

the first order reaction.

 
(2) Half Life Time of a First Order Reaction : The time required for the completion
of any given proportion of the reaction is independent of the initial
concentration.
At half change, for instance ' x ' = a / 2 and t = t1/2
Substituting the value of ' x ' and t in equation (12.25) , we get

2.303  a 
t1/2 = log  
k a  a /2

2.303  a  2.303
 
or t1/2 = klog a /2 = k( log 2 )

0.693
So that t1/2 =
k ... (12.26)
It will be seen that the half life is independent of the initial concentration. Thus,
for a first order reaction the time required for the completion of any fraction of
change is independent of initial concentration.
(3) Change in concentration unit will not change rate constant of first order
reaction.
 a 
(4) For first order reactions, a plot of log  versus time ( t ) will yield a

 (a  x ) 

straight line which passes through the origin (Fig. 12.3). The slope of this line is
equal to 2.303/k. Thus, the value of rate constant k can easily be obtained from
the slope value.
Examples of First Order Reactions
Hydrolysis of an ester:The hydrolysis of an ester, say, ethyl acetate, in aqueous
solution in the presence of mineral acid is an example of pseudo–first order reaction.
The reaction is
H+
  CH3COOC2H5 + H2O CH3COOH + C2H5OH
 The mineral acid merely acts as a catalyst. An inspection of the equation indicates
that it should be second order. But this is a first order reaction. The rate of the
reaction is given by
dx
dt = k' [CH3COOC2H5][H2O]

But, since water is present in very large excess, its concentration is almost constant
and, therefore, the
dx
rate equation takes the form
dt = k [CH COOC H ]
1 3 2 5

so that the rate is proportional to the concentration of the ethyl acetate and hence
the reaction is of the first–order. Such reactions are some times called pseudo–first
order reactions.
Decomposition of N2O5 : The decomposition of nitrogen pentaoxide in CCl4 solution
follows first order kinetics. The reaction is
N2O5 2NO2 + O2 (g)
 (iii) Kinetics of Second Order Reactions
A reaction is kinetically said to be of second order when the reaction rate
is proportional to the square of the concentration of one of the
reactants, or to the product of the concentrations of the two reactants.
Thus, for a reaction of the type
2A Products
the rate expression is written as
d[A]
rate =  dt = k [A]2 moles litre–1 sec–1 (12.33)
whereas, for the reaction of the type
A + B Products
the rate expression is written as

d[A] d[B]
rate =  =  = k [A][B] moles litre–1 sec–1 … (12.34)
dt dt
Mathematical derivation of rate equation for a second order reaction
In order to derive a general rate equation for rate constant for a second order
reaction, we may have two situations ;
(i) When the concentrations of both the reactants are equal, and
(ii) When the concentrations of the two reactants are different.
 
Case (i) : When the concentration of the two reactants are equal :
Let us consider the first case when the initial concentrations of both the
reactants A and B are same i.e. [A]t=0 = [B]t=0 = a and x moles of each A and
B have reacted after the completion of time t. The concentrations of A and B,
after time t will, thus, be (a – x). The rate expression is then written as

rate = dx = k [A][B] moles litre–1 sec–1 ... (12.35)

dt

or dx = k (a – x) (a – x) = k (a – x)2 ... (12.36)

dt
on rearranging Eq. (12.36) we can write

dx = k . dt, ... (12.37)

(a  x ) 2
where k is the second order rate constant. On integrating Eq (12.37)
dx
 (a  x ) 2
= k  dt

one gets
1
(a  x )
= k.t + C (12.38)

where C is constant of integration. The value of C can be evaluated by

putting the condition in Eq. (12.38) that at the start of the reaction, initially
when t = 0 then x = 0. Thus,
1
= C (12.39)
a
On putting the value of C in Eq. (12.38) we get
1 1
= k.t+
(a  x ) a
Determination of the order of a Chemical Reaction
Several methods have been employed to determine the order of a chemical
reaction. Some of the methods are being discussed below –
 1. Integration Method
The experimental data of concentrations of reactants are obtained at different
time intervals during the course of the reaction and then these data are
substituted in the various rate equations of first –, second – and third–order
reactions respectively. The concentration time curves are plotted according to
rate expressions for various reaction orders and then the value of rate constant, k
is calculated. The rate equation which gives nearly almost constant value of rate
constant k, for a series of time intervals determines the correct overall order of
the reaction. But this method involves trial of one rate equation after another.
2. Graphical Method
A graphical approach is often used to ascertain the order of a reaction. In this
method from the experimental rate data the concentrations log (a – x), 1/(a – x)
and 1/(a – x)2 relevant to first, second and third orders respectively are plotted
against time ( t ) until linearity in the curve is obtained. The linear plot then
suggests the order for the reaction.
 Activation Energy
• Minimum amount of kinetic energy the
reactants must have in order to react.

• The particles form an activated complex

(transition state) that is an unstable
arrangement of atoms that lasts a few
moments. Then the products are formed.
Analogy
 Potential Energy vs Time
(Exothermic)

Heat of
Reaction H

Time
http://staff.um.edu.mt/jgri1/teaching/che2372/notes/10/theory.html
Energy vs Time (Endothermic)

Activation
Energy Heat of
Reaction H
 Catalyst Effect on Reaction Rates
A catalyst lowers the activation energy, thus the
reaction proceeds faster.