Chemical Kinetics: Rate of a reaction, molecularity and order of reaction, concentration dependence

of rates, mathematical characteristic of simple chemical reactions – zero order, first order, second
order, pseudo order, half-life and mean life. Determination of the order of reaction – differential method,
method of integration, half-life method and isolation method.

INTRODUCTION
The branch of physical chemistry which deals with the rate at which the chemical reactions
occur, the mechanism by which the chemical reactions take place and the influence of various
factors such as concentration, temperature, pressure, catalyst, etc., on the reaction rates, is called
the chemical kinetics.
RATE OF REACTION (Average and Instantaneous Rate)
We are all familiar with processes in which something changes with time. Rate is usually
expressed as the ratio of the amount of change in some quantity to the time required to produce
that change.
Rate = Change in some quantity = ∆X
Time taken for the change ∆t
∆X =X final - X initial and ∆t is the amount of time
The rate measured over a long time interval is called average rate and the rate measured for an
infinitesimally small time interval is called instantaneous rate.
The rate of reaction (average rate) is defined as the change .of concentration of anyone of its
reactants (or products) per unit time.

Average rate of reaction Rav = Change of concentration of one of the reactants or products
Time taken for the change

Consider a common hypothetical reaction, A → B

The average rate of reaction may be expressed either in terms of decrease in concentration of A
(reactants) or in terms of increase in concentration of B (product).

Average rate of reaction = Decrease in concentration of A

Time taken

OR, Average rate of reaction =Increase in concentration of B

Time taken
The concentrations of reactants or products are expressed as number of moles per litre. The
symbol [A] stands for the molar concentration of A. The symbol d[A], therefore, stands for the
change in molar concentration of A.
The rate of decrease or increase in the concentration of reactants or products may also be
expressed in terms of change in their concentration during the time interval, ∆t as:

Average rate of reaction = -- ∆A

∆t
Average rate of reaction = + ∆B
∆t
(A negative sign placed before a reaction rate symbol signifies a decrease in concentration of tile
reactant with increase of time and a positive sign before the rate symbol signifies that the
concentration of the product increases with increase in time. The concentration change may be
positive or negative but the rate, of reaction is always positive.

Instantaneous Rate
It is defined as the rate of change of concentration of anyone of the reactants or products over a
very small interval of time. If we take infinitesimal small interval of time dt, it may be assumed that the rate is
uniform through this interval; then if dx is amount of substance A transformed to B during this interval, the
rate of reaction at that instant is given as -dx /dt
RATE CONSTANT
Consider a simple reaction A→B

If CA is the molar concentration or active mass of A at a particular instant, then

dx / dt α CA or dx / dt =k CA
where, k is a proportionality constant, called velocity constant or rate constant or specific reaction rate.
At a fixed temperature, if CA = I, then Rate dx/ dt = k ... (i)
Let us consider a general reaction.
aA + bB → Product
Rate = dx / dt α A]a[B]b or, Rate= k [A]a [B]b
When [A] =[B] = 1 mol/litre, then Rate = k
Units of rate
Reaction rate has the units of concentration divided by time. We express concentration in moles
per litre (mole/litre) but time may be given in any convenient unit second(s), minutes (min),
hours (h) days (d) or possibly years. Therefore, the units of reaction rates may be mole/litre/sec
or mole l-1 s-1
mole/litre/ minute mol l-1 m-1
Factors affecting reaction velocity
There are a number of factors which affect the rate of a reaction, the most important of them are:
(a) Effect of concentration: The rate of a chemical reaction is influenced by the no. of collisions
per second between the reacting molecules. On increasing the concentration of the reactant, the
number of collisions will increase and the rate of reaction will increase and on decreasing the
concentration the rate will decrease.
(b) Effect of nature of reactants: Reactions between polar or ionic molecules occur almost
instantaneously. Those reactions in which the bonds are arranged or electrons are transferred
takes a comparatively longer time than the reaction between ionic molecules. examples of
neutralisation reactions or double displacement reactions which are very fast while the oxidation
reduction reactions are slower.
(c) Effect of catalyst: A catalyst can increase or decrease the rate of a chemical reaction. For
example the combination of hydrogen and oxygen to form water is slow at ordinary temperature,
while it proceeds rapidly in presence of platinum.
(d) Effect of surface area of reactant: Surface area of reactants is of importance only for
heterogeneous reactions. As particle size decreases, surface area for the same mass increases.
The smaller particle thus reacts more rapidly than the larger particles. For example, burning of
coal dust in air takes place more rapidly than large lump of coal.
(e) Effect of temperature: With the exception of few reactions, the rate of reaction is increased
considerably with an increase of temperature. Generally the rate of a reaction is almost doubled
or tripled by an increase of 100C in temperature.

Rate of reaction at 350C = K35 = 2 to 3

Rate of reaction at 250C K25

Order of reaction and molecularity

The total number of reactant particles involved in the overall reaction, is called as molecularity
of a reaction Thus in the reaction -
N2O5 (g) 2NO2 (g)+1/2O2(g) it is unimolecular
2HI (g) H2(g) + I2(g) it is bimolecular
and 2NO (g) + O2(g) 2NO2 it is trimolecular
Order of reaction depends only on the reactants upon which the rate of reaction depends. It
means that order is in those reactants only, by changing whose concentration, the rate of reaction
changes.
If reaction rate is independent of reactant concentration, the order is zero in that reactant. We can
say that “Order is the sum of powers of concentration of reactants as given in a rate law or rate
equation or rate expression for the reaction under consideration”.
A reaction is said to be first order if its rate r (or dx/dt) is given by the following rate expression -
R = dx/dt = kCa
The reaction is of second order and third order if its rate expressions are given by Eqn. (i) and (ii)
respectively
dx/dt = kCa2 or k Ca Cb ………………(i)
dx/dt = kCa3 or k Ca2Cb or k Ca Cb2 ……………….(ii)
The subscripts a, b and c stand for various reactants A, B and C respectively. When the rate
expression is given by
dx/dt = kCan1 Cbn2Ccn3
The order of reaction as a whole n is given by n= n1+n2+n3………….
The molecularity of any process can only be small position integers, while order of reaction can have
zero as well as fractional values.
 Difference between order of reaction and molecularity:

Molecularity Order of reaction

1. It is equal to the number of molecules of 1. It is equal to some of the power of the molar
reactants which take part in a chemical concentration of the reactants in the rate
reaction. expression.

2. It is theoretical concept. 2. It is an experimentally determined quantity,

which is obtained from the rate for the overall
reaction. It depends on rate determining step in the
reaction mechanism.
3. It is always a whole number. 3. It may be negative, zero or fractional value
generally not more than 3.
4. It is obtained from a single balanced 4. It cannot be obtained from a balanced
chemical equation. chemical equation.
5 It does not reveal anything about 5. It reveals some basic facts about a
reaction mechanism. reaction mechanism.

(1) Zero order reaction

Reactions, in which the reaction rate does not depend upon the initial concentration of the reactant,
are said to be zero order reactions. The Law of mass action fails in these reactions
A →B d [A]/ dt = kA0= k
Examples of zero order reactions:
1. Thermal decomposition of hydrogen iodide at gold surface is found to be of zero order
2HI → H2 + I2
2. The decomposition of ammonia on platinum surface at 8000C in kinetically of zero order.
NH3 →N2+3H2
3. The phosphine decomposition on the surface of molybdenum or tungsten at high pressure is of
zero order.
2PH3→ 2 P + 3H2
(2) First order reaction
A first order reaction is that in which the sum of powers to which the concentrations of reactants
must be raised while expressing the reaction rate, is one. Expression for first order reaction is given
by
A → products
A P
a 0 initially
a-x x after time t
rate expression is given as r = -d[A]/dt = d[P]/dt = dx/dt =k[A] = kCA = k. A (at zero time)
=k (a-x) (at t time)
(3) Second order reaction
A second order reaction is that in which the sum of powers to which the concentrations of reactants
must be raised while expressing the reaction rate, is two.
dx/dt = kC2A for reaction 2A →products
and dx/dt = kCACB for reaction A+B →products
Example of second order reactions are :
Hydrolysis of an ester by an alkali (Saponification of ester)
CH3COOC2H5+NaOH CH3COONa+C2H5OH
(4) Third order reaction
A third order reaction is that in which the sum of powers to which the concentrations of reactants
must be raised while expressing the reaction rate, is three. Reactions of third and higher order are
rare, but there are in fact reactions which are definitely of third or sometimes higher order. This is
due to the effect that the probability of three molecules coming to a single point simultaneously is
must less as compared to unimolecular and bimolecular reactions.
In a reaction of the third order the number of molecules where concentration alters as a result of
chemical change is three, and the change may belong to any of the following types
A + A + A →products
A + A + B →products
A + B + C→ products
Examples of third order reaction is
(i) 2 FeCl3+SnCl2 →2FeCl2+SnCl4
(ii) O2+2NO →2NO2
(iii) 2NO + Cl2→ 2NOCl
(5) Pseudo molecular reactions [pseudo means false]
These are the reactions in which order and molecularity are different. These reactions are named after
the order and not after the molecularity. Eg. if molecularity is 2 and order is 1 than the reaction is
called as pseudo first order reaction. There are several reactions which obey first order rate equation
although in reality they are bi-or tri-molecular. For example, consider the hydrolysis of methyl
acetate in presence of an acid
CH3COOCH3+H2O(Excess) →CH3COOH+CH3OH
Here molecularity is 2, while order is one in ester and zero in water i.e. overall order is 1 + 0 = 1. The
order becomes zero in the reactant which is taken in excess, because the overall rate of reaction does
not depend upon the reactant taken in excess. If we will change the concentration of reactant taken in
excess, there will not be any change in its being in excess.
INTEGRATED LAW FOR ZERO AND FIRST ORDER REACTION
(1) Integrated law for zero order reaction
Let us consider a reaction
A→ B
A 0 initially
a-x x after time t
For a zero order reaction the reaction velocity at any time t is given by -
dx/dt = k (constant) or, dx = kdt
On integrating above eqn. we get,
ʃ dx = ʃ kdt or, x = kt + I (I is integration constant)
when t=0 x=0 hence I=0 so we have x= kt
this is general rate expression for zero order reaction.
Unit of zero order reaction:
The unit of zero order rate constant is that of concentration x time -1 (as k=x/t).
Hence unit of k will be mole/litre time -1 or mole lit-1 time-1.
RATE EXPRESSION FOR FIRST ORDER REACTION
As we know that a first order reaction is that in which the reaction rate is determined by the
change of the one concentration term of reactant only.
Let us consider a first order reaction
A→B
A 0 (initially)
a-x x (after time t)
Suppose the initial concentration of the reaction A be a mole/litre. Let x mole/litre of A
decompose after time t leaving behind (a-x) mole/litre of A, the amout of B formed will be x
mole/litre. The rate of first order reaction is proportional to the concentration of A at any
particular time. Therefore
dx/dt = kCA …....(1)
where k is rate constant or velocity constant.
dx/dt =k (a-x) …..(2)
dx/a-x = kdt …..…..(3)
ʃ dx/a-x = ʃ kdt ..(4)
integrating equation (4) we get -loge(a-x) = kt+I (I= constant of integration) …….…(5)
When t=0 x=0 then -loge a =I Then equation (5) becomes
Loge a-loge (a-x) = kt or kt= loge a/a-x
k= 2.303/t log10 a/(a-x) …………………….….…(6)

Unit of velocity constant of first order reaction:

As the rate constant for first order reaction is k=1/t ln (a/a-x), hence unit will be 1/time or time-1
Half life time of a reaction
The time required for the half completion of a reaction is called half life time of a reaction. Half
life time of a reaction is represented by t 1/2.
Half life time for a first order reaction is represented as
k1 = 1/t1/2 logea/(a-a/2) = 1/t1/2 loge2 = 1/t1/2 2.303 log102
= 1/t1/2 2.303X.3010 = .693/t ½
or t1/2 = 0.693/ k
It is clear from the above discussion that
(i) Half life of a first order reaction is independent of the initial concentration.
(ii) Half life is inversely proportional to k.
Now we can calculate the time for completing any fraction of the reaction by making use of first
order reaction. We know k= 2.303/t log a/a-x
Let us calculate the time in which one third of a reaction is completed.
k = 2.303/t log a/(a-a/3) = 2.303/t log 3a/2a = 2.303 log 3/2 = 2.303/t (log 3-log 2)
If we have to calculate the time in which two third of a reaction is completed we proceed as under
K = 2.303/t log a/(a-2/3a) = 2.303/t log q/(3a-2a)/3a = 2.303/t log 3
Determination of order of reaction
(1) Integration method (Substitution in the equation)
This method consists in actually carrying out the change with known quantities of the reactants
and nothing the progress of the reaction by analyzing the reaction mixture from time to time.
These values are substituted in the velocity constant equation. When the values are substituted in
the expression for first order that is values of a, x and t are substituted and value of k always
remains constant the reaction is of first order.
Example: A solution of H2O2 when titrated against KMnO4 solution at different time intervals
gave the following results.
Time (minutes) 0 10 20
Volume of KMnO4 Used for 10 ml of H2SO4 23.8 ml 14.7 ml 9.1 ml
Show that the reaction if of first order
The integrated rate equation for first order reaction is k= 2.303/t log a/a-x
Since volume of KMnO4 used in the titration is a measure of concentration of H2O2 in solution.
a= 23.8
a-x = 14.7 in 10 minutes
a-x = 9.1 in 20 minutes
Substituting these values in the rate equation above we have
k = 2.303/10 log 23.8/14.7= 0.2303 (log 23.8-log 14.7)
= 0.2303 (1.3766- 1.1673)= 0.04794 ….(1)
k = 2.303/20 log 23.8/9.1= 0.10165 (log 23.8 – log 9.1)
= 0.10165 (1.3766 – 0.9595)= 0.04806 ……(2)
Since the value of k is almost constant hence reaction is of first order.
(2) Half life method
A general expression for the half life, (11/2 ), is given by t1/2 α 1/an-1
where, 'n' is the order of the reaction.
Starting with two different initial concentrations a1 and a2 forthe same reaction, the half
lives are (t1/2)1 and (t1/2 )2 respectively are determined. As we know that,
t1/2 α 1/a1n-1 ….(i)
and t1/2 α 1/a2 n-1
….(ii)
Dividing eq. (i) by eq. (ii),
(t1/2)1 = (1/a1)n-1 ….(iii)
(t1/2)2 (1/a2)n-1
(3) Ostwald Isolation Method

The total order of the reaction is then equal to the sum of the orders of reaction for individual
reactants. This method is based on the principle that if the concentration of all but one reactant
are taken in excess , then during the course of the reaction, the concentration of those reactants
taken in excess will remain almost constant and hence variation in rate will correspond to the
concentration of that reactant whose concentration is small. This process is repeated one by one
and order with respect to each reactant is determined.

The overall order will be the sum of all these orders.

aA + bB + c C ———> Products

Suppose we isolate A by taking B and C in large excess and get order of reaction with respect to
A. Similarly , we isolate B by taking A and C in B and and C.

Overall order of reaction n= p+ q+ r

 Theories of chemical kinetics

Effect of temperature on reaction rate

Temperature coefficient of a reaction:
Now let us consider effect of temperature on reaction rates It has been found that generally an
increase of temperature increases the rate of reaction. The ratio of rate constants of a reaction at
two temperatures differing by 100C is known as temperature coefficient of the reaction. The
temperatures usually selected for this purpose are 250C and 350C. Thus
Temperature coefficient = Rate of reaction at 350C = K35 = 2 to 3
Rate of reaction at 250C K25

The value of temperature coefficient for most of the reactants is close to 2 and in some cases it
approaches to 3.
COLLISION THEORY OF REACTION RATE
Now let us study why such small rise of temperature speeds up a reaction to such a large extent.
This can be explained on the basis of collision theory. According to collision theory for chemical
reaction to occur, there must be collisions between reacting molecules. But all collisions are not
effective. Only a small fraction of collisions produce a reaction. Two main conditions for a
collision between the reacting molecules to be productive are-
(i) The colliding molecules must possess sufficient kinetic energy to cause a reaction.
(ii) The reacting molecules must collide will proper orientation.
The molecules must collide with sufficient energy: Let us consider a reaction
A -A + B-B → 2 A-B
A chemical reaction occurs by breaking bonds between the atoms of reacting molecules and
forming new bonds in the product molecules. For breaking the bonds energy is required and in
forming the bonds energy is liberated. The energy for breaking the bonds comes from the
kinetic energy possessed by the reacting molecules, before the collision. The figure shows the
energy of molecules A2 and B2 as the reaction
A2+B2 → 2AB progresses.
Figure shows the activation energy Ea, that is minimum energy required to cause a reaction
between the colliding molecules. Only the molecules that collide will a kinetic energy greater
than Ea are able to get over the barrier and react. The molecules colliding will kinetic energies
less than Ea fail to cross the barrier.For a reaction to occur there must be collision between
molecules. And most of the collisions are ineffective. According to collision theory those
collision results in chemical reaction in which the colliding molecules are associated with a
certain minimum energy called threshold energy.

Reaction Progress
Hence there is certain minimum energy called threshold energy which the colliding molecules
must acquire before they are capable of reacting. Most of the molecules have much less kinetic
energy than the threshold energy. The excess energy that the reactant molecules having energy
less than the threshold energy must acquire in order to react to yield products is known as
activation energy.
That means
Activation energy = threshold energy – energy possessed by the molecules.
EFFECT OF CATALYST
As you have studied earlier a catalyst is a substance that can increase the rate of a reaction but
which itself remains unchanged in amount and chemical composition at the end of the reaction.
When a catalyst is added, a new reaction path with a lower energy barrier is provided (dotted
curve in the fig. Since the energy barrier is reduced in magnitude, a larger number of molecules
of the reactants can get over it. This increases the rate of the reaction.
 Fig. EFFECT OF CATALYST ON ACTIVATION ENERGY

ARRHENIUS EQUATION
For the effect of temperature Arrhenius proposed and empirical equation which is useful in
calculating energy of activation of a reaction
k = Ae-Ea/RT ….(1)
Where Ea is called Arrhenius activation energy at temperature T, k is rate constant and A is
called the Arrhenius pre exponential factor, a has the same units as the rate constant k. the units
of k for a first order reaction are S -1 which is units of frequency. Hence A is also called the
frequency factor, Ea and A are called Arrhenius parameters.
Taking logs of equation (1) we have
ln k = ln A-Ea/RT .(2)
A plot of lnk against reciprocal of absolute temperature (1/T) gives a straight line with
slope = -Ea/R and intercept = ln A, and hence energy of activation Ea be obtained.
Differentiating equation (2) with respect to temperature, we get
d lnk /dT = Ea/RT2 …(3)
Integrating equation (3) between temperature T1 and T2 when the corresponding rate constants
are k1 and k2 respectively assuming that Ea is constant over the entire range we get
ln k2/k1 = Ea/R[T2-T1/T1T2] …(4)
or log10 k2/k1 = Ea/2.303R [T2-T1/T1T2]
This is the integrated Arrhenius equation. Thus knowing the rate constants at two temperature
the energy of activation Ea can be calculated. It must be clear to you that different reactions
require different amount of energy activation energy. A reaction which has lower activation
energy will proceed at a faster rate at a given temperature. A reaction which has higher activation
energy will proceed at a slower rate. The differences in activation energy are mainly responsible
for observed difference in rate of reaction.
If the reactants posses higher total energy than the products there will be a release of energy. The
reaction is said to be exothermic reaction. If the reactants possess lower total energy than the
products energy will be absorbed and the reaction is said to be endothermic.