CHEMICAL KINETICS

Textbook:
Essentials of Physical Chemistry.
By: B.S. Bahl, G.D.Tuli
CHAPTER: 20
 Chemical Kinetics
Learning Objectives Include:
1. Definition and Implication √
2. Mathematical Expression of Rate of a reaction √
3. Order and Molecularity of reaction √
4. Classification of reaction according to order and molecularity
with examples √
5. Derivation of rate expressions (1st and 2nd order) √
6. Derivation of rate expressions for 3rd and higher orders
7. Units of rate constants
8. Half life √
9. Methods for determining rate of reaction
10. Theory of reaction rate
11. Complex reaction
12. Problems.
 REACTION RATE
The rate of a reaction tells as to what speed the reaction occurs. Let
us consider a simple reaction
A ⎯⎯→ B
The concentration of the reactant A decreases and that of B increases
as time passes. The rate of reactions is defined as the change in
concentration of any of reactant or products per unit time.

Thus
rate of reaction = rate of disappearance of A
= rate of appearance of B
Average Rate of Reaction is a Function of Time

The concentration of CO was found experimentally every 10

seconds. The results of such an experiment are listed below:

Over the first 10 seconds, the average rate is

The reaction is indeed slowing down with time
 Rate law
The rate of a reaction is directly proportional to the reactant
concentrations, each concentration being raised to some power.
Thus for a substance A undergoing reaction,
rate ∝ [A]n
or, rate = k [A]n ………………(1)
For a reaction, 2A + B ⎯⎯→ products
Thus the rate of reaction may be expressed as
rate = k [A]m [B]n ……………(2)
An expression which shows how the reaction rate is related to
concentrations is called the rate law or rate equation.

The power (exponent) of concentration n or m in the rate law is usually a

small whole number integer (1, 2, 3) or fractional. The proportionality
constant k is called the rate constant for the reaction.
 Examples of rate law :
2A + B ⎯⎯→ products
rate = k [A]m [B]n

It is apparent that the rate law for a reaction must be determined by

experiment. It cannot be written by merely looking at the equation with a
background of our knowledge of Law of Mass Action. Usually, the powers
of concentration in the rate law are different from coefficients.
Example-1
 Order of a reaction
The order of a reaction is defined as the sum of the powers of
concentrations in the rate law.
Let us consider the example of a reaction which has the rate law
rate = k [A]m [B]n
The order of such a reaction is (m + n).

Reactions may be classified according to the order.

m + n = 1, it is first order reaction
m + n = 2, it is second order reaction
m + n = 3, it is third order reaction
 MOLECULARITY
Chemical reactions may be classed into two types :
(a) Elementary reactions: An elementary reaction is a simple
reaction which occurs in a single step. These are-
i) Unimolecular (molecularity = 1)
ii) Bimolecular (molecularity = 2)
iii) Termolecular (molecularity = 3)
Examples of Molecularity of an Elementary Reaction

i) Unimolecular Reactions ii) Bimolecular Reactions

A ⎯⎯→ product A + B ⎯⎯→ products
Br2 ⎯⎯→ 2Br A + A ⎯⎯→ products
iii) Termolecular Reactions 2HI ⎯⎯→ H2 + I2
A + B + C ⎯⎯→ products
2NO + O2 ⎯⎯→ 2NO2
(b) Complex reactions: A complex reaction is that which occurs in
two or more steps
Why High Molecularity Reactions are Rare ?

According to kinetic molecular theory, the rate of a chemical reaction

is proportional to the number of collisions taking place between the
reacting molecules.
Thus the possibility of three or four molecules colliding together is
much less than in case of bimolecular collision. Hence the reactions
proceed through a series of steps, each involving two or three or less
number of molecules. Such a reaction is called a complex reaction.
 MOLECULARITY VERSUS ORDER OF REACTION

The total number of molecules or atoms which take part in a reaction

as represented by the chemical equation, is known as the molecularity
of reaction.
The sum of the powers to which the concentrations are raised in the
rate law is known as the order of reaction.

Table: Molecularity and order for elementary reactions

The molecularity and order for an elementary reaction are equal

Differences Between Order and Molecularity
 PSEUDO–ORDER REACTIONS

A reaction in which one of the reactants is present in a large excess

shows an order different from the actual order. The experimental
order which is not the actual one is referred to as the pseudo order.

CH3COOC2H5 + H2O ⎯⎯
⎯⎯→ CH3COOH + C2H5OH
ethyl acetate (excess) acetic acid ethyl alcohol
Here a large excess of water is used and the rate law can be written as
rate = k [CH3COOC2H5] [H2O]
= k′ [CH3COOC2H5]
The reaction is actually second-order but in practice it is found to be
first-order. Thus it is a pseudo-first order reaction.
 ZERO ORDER REACTION

A reactant whose concentration does not affect the reaction rate is not
included in the rate law. In effect, the concentration of such a reactant
has the power 0. Thus [A]0 = 1.
A zero order reaction is one whose rate is independent of
concentration. For example, the rate law for the reaction
NO2 + CO ⎯⎯→ NO + CO2
at 200 °C is
rate = k [NO2]2
Here the rate does not depend on [CO], so this is not included in the rate
law and the power of [CO] is understood to be zero. The reaction is
zeroth order with respect to CO. The reaction is second order with
respect to [NO2]. The overall reaction order is 2 + 0 = 2.
 ZERO ORDER REACTIONS
In a zero order reaction, rate is independent of the concentration of
the reactions. Let us consider a zero-order reaction of the type
A ⎯⎯→ Products

or

On integrating we get

where k0 is the rate constant of a zero-order reaction, the unit of which

is concentration per unit time. In zero order reaction, the rate constant
is equal to the rate of reaction at all concentrations.
 FIRST ORDER REACTIONS
Let us consider a first-order reaction of the type
A ⎯⎯→ Products
Initial conc. a 0
At time, t (a–x) x
We know that for a first order reaction, the rate of reaction, dx/dt, is directly
proportional to the concentration of the reactant. Thus,

k is the rate constant

or

By integrating,

or
where I is the integration constant
 The constant I may be evaluated by putting t = 0 and x = 0

Thus

or,

Changing into common logarithms

Sometimes the integrated rate law in the following form is also used :

Where, x1 and x2 are the amounts decomposed at time intervals t1 and t2

respectively from the start.
Solved problem: Nitrogen pentoxide in carbon tetrachloride is
decomposed to form oxygen gas, 2 N2O5 (g) = 4 NO2 (g) + O2 (g).
From the following data for the decomposition of N2O5 in CCl4 solution
at 48 0C, show that the reaction is of first order.
t(mins.) 10 15 20 ∞
Volm.of O2
evolved(ml) 6.30 8.95 11.40 34.75

Solution:
For a first order reaction the integrated rate equation is:
Solved problem: A solution of H2O2 when titrated against KMnO4 solution
at different time intervals gave the following results.
t(mins.) 0 10 20
Volm. KMnO4 Used 23.8 14.7 9.1
Give your comment whether it is a first or second order reaction and why?
Solved problem:
The following data was obtained on hydrolysis of methyl acetate at 250C in
0.35N hydrochloric acid. Establish that it is a first order reaction.
t(sec.) 0 4500 7140 ∞
Volm. alkali
Used (ml) 24.36 29.32 31.72 47.15

Solution:
 SECOND ORDER REACTIONS
Let us consider a first-order reaction of the type
2A ⎯⎯→ Products
Initial conc. a 0
At time, t (a–x) x
We know that for a second order reaction, the rate of reaction, dx/dt, is
proportional to the square of the concentration of the reactant. Thus,

k is the rate constant

or

By integrating,

where I is the integration constant

I may be evaluated by putting t = 0 and x = 0

I = 1/a
 Substituting for I in the above equation

Thus

This is the integrated rate equation for a second order reaction.

DO
For a Third order reaction
THIRD ORDER REACTIONS
 Units of Rate Constant, K

Zero order First order

= time–1
= mole litre–1 time–1

Second order Third order

= mol–2 litre–2 time–1

= mole–1 litre time–1
 Half-life of reaction

[A]0 is initial concentration and [A] is concentration at any time t. Half-

life, t1/2, is time when initial concentration reduces to ½. i.e., [A]= ½[A]0

Or, when t=t1/2 ; x= a/2

Or,

Or,

It is clear from this relation that:

1) half-life for a first order reaction is independent of the initial concentration.
2) it is inversely proportional to k, the rate-constant.
SOLVED PROBLEM 2: The half-life of a substance in a first order
reaction is 15 min. Calculate the rate constant.

SOLUTION
For a first order reaction,

Putting t1/2 = 15 min in the expression and solving for k, we have

SOLVED PROBLEM 5: For a certain first order reaction t0.5 is 100 sec.
How long will it take for the reaction to be completed 75% ?
SOLUTION
 DO
Half-life of reaction for 2nd and 3rd
Order reaction
&
Example-1,2,3,4,5,6,7
 Methods of Determining Order of Reaction
1. Method of Integration (graphical)
2. Half-Life method
3. Differential Method
4. Isolation Method
1. Integration (graphical) Method
In case of First order
We have already derived the integrated rate equation for first order as-

Slop = k

If a curve is obtained, the reaction is not first order.

In case of Second order
Integrated rate equation for second order can be written as-

Slop = k

2. Half-Life method
We know that half-life period
for a first order reaction is
independent of the initial
concentration, [A]. We also
know :
Suppose, for concentration [A1] time for consuming half of it t1 and that for
concentration [A2] is t2.
So,

and thus

or

So for n,
this is the order of reaction
3. Differential method
This method was suggested by van’t Hoff and, therefore, it is also called
van’t Hoff’s differential method. According to it, the rate of a reaction
of the nth order is proportional to the nth power of concentration.

C = Concentration
In two experiments with different initial concentrations, we can write-

Now, taking log, we can write- ------ (1)

------ (2)
 On subtracting (2) from (1), we get

------ (3)

n can be calculated by plotting concentrations against time (t) in the

two experiments, where the slopes = (– dc1/dt) and (– dc2/dt).
4. Ostwald’s Isolation method
This method is employed in determining the order of complicated
reactions by ‘isolating’ one of the reactants so far as its influence on the
rate of reaction is concerned. Suppose the reaction under consideration is :
A + B + C ⎯⎯→ products
The order of the reaction with respect to A, B and C is determined. For the
determination of the order of reaction with respect to A, B and C are taken
in a large excess so that their concentrations are not affected during the
reaction. The order of the reaction is then determined by using any of the
methods described earlier.

Similarly, the order of the reaction with respect to B and C is determined.

If nA, nB and nC are the orders of the reaction with respect to A, B and C
respectively, the order of the reaction n is given by the expression.

n = nA + nB + nC
 DO

Theory of Rate:
1. Collision theory, 2. T.S Theory, 3. Lindeman Unimolecular Theory
 Theory of reaction rate
A) Collision Theory B) Transition State Theory C) Lindeman Unimolecular Theory.
A) Collision Theory
The two main conditions for a collision between the reacting molecules to
be productive are :
1) The colliding molecules must posses sufficient kinetic energy to cause a
reaction.
2) The reacting molecules must collide with proper orientation.
1) The molecules must collide with sufficient kinetic energy
Let us consider a reaction
A – A + B – B ⎯⎯→ 2A – B
Ea = Activation Energy
The energy for the breaking
of bonds comes from the
kinetic energy possessed by
the reacting molecules before
the collision.
2) The molecules must collide with correct orientation
The correct orientation is that which ensure direct contact between the atoms
involved in the breaking and forming of bonds.

Fig: Orientations of reacting

molecules A2 and B2 which
lead to an effective and
ineffective collision

Collision Theory and Reaction Rate Expression

Taking into account the two postulates of the collision theory, the reaction rate for the
elementary process.
A + B ⎯⎯→ C + D
is given by the expression
rate = f × p × z
where f= fraction of molecules which possess sufficient energy to react; p= probable
fraction of collisions with effective orientations, and z= collision frequency.
Arrhenius Theory of Collision
1. Collision between reacting molecules is a necessary condition for a
reaction, the rate of reaction should be equal to the frequency of
collisions.
2. Calculations showed that the rate of most reactions are much smaller
than the frequency of collisions.
3. Increase of temperature by 10 0C results only 0.2-0.3% of increase in
the frequency of collisions, but the reaction rate increases 200-300%.
4. It is revealed that only a small fraction of the molecular collisions
among the molecules possessing energy higher than activation energy
causes reactions to happen.

According to Maxwell-Boltzmann distribution

Temperature Dependence of Reaction Rate and Arrhenius Equation

According to Maxwell-Boltzmann distribution

This is called the Arrhenius equation in which A is an experimentally

determined quantity, Ea is the activation energy, R is the gas constant,
and T is Kelvin temperature.
 Calculation of Activation Energy (Ea) Using Arrhenius Equation

………..(1) [Taking ln in each side

and E = Ea]

or

If k1 and k2 are the values of rate constants

at temperatures T1 and T2, then-

Equation (1) can be written as

 DO
Problem-1: The values of the rate constant (k) for the reaction 2 N2O5 (g)
= 4 NO2 (g) + O2 (g) were determined at several temperatures. A plot of lnk
versus 1/T gave a straight line of which the slope was found to be- 1.2× 104
K. What is the activation energy of the reaction?

Solution
Problem-2: The gas-phase reaction between methane and diatomic
sulphur is given by the equation, CH4 (g) + 2S2 = CS2 (g) +2H2S (g).
At 550 0C the rate constant for this reaction is 1.1 mol-1sec and at 625
0C the rate constant is 6.4 mol-1sec. Calculate E for this reaction.
a
Solution
 B)Transition State Theory

The transition state or activated complex theory was developed by

Henry Erying (1935).
This theory is also called the absolute rate theory because with its
help it is possible to get the absolute value of the rate constant. The
transition state theory assume that simply a collision between the
reactant molecules does not really causes a reaction. During the
collision, the reactant molecules form a transition state or activated
complex which decomposes to give the products. Thus

The double dagger superscript ( ) is used to identify the activated complex

 The transition state theory may be summarized as follows:
1. The kinetic energy of the two molecules is converted into potential energy.
2. As the molecules come close, the interpenetration of their electron clouds
occurs which allows the rearrangement of valence electrons.
3. A partial bond is formed between the atoms A and B with corresponding
weakening of B – C bond. This leads to formation of an activated complex
or transition state. The activated complex is momentary and decomposes to
give the products (A–B + C).
The activated complex theory may be illustrated by the reaction energy diagram