CHEMICAL KINETICS

Chemical kinetics is the branch of chemistry which deals with the study of rate of chemical
reactions, the factors affecting it and the mechanism by which the reactions proceed.

Chemical Reactions on the Basis of Rate of Reaction

(i) Very Fast/ Instantaneous reactions: These chemical reactions are so fast that it is
practically impossible to measure the speed of the reaction.
E.g. Ionic reactions, organic substitution reactions.
(ii) Moderate reactions: These chemical reactions take place at moderate and measurable
rates. Eg. Hydrolysis of cane sugar.
(iii) Slow reactions: These chemical reactions are so slow that it completes in a long time
from some minutes to some years are called slow reactions. .
E.g. Rusting of iron, transformation of diamond etc.

Rate of reaction
It is defined as change in concentration of reactants or products per unit time

For a reaction, A B

Rate = - Decrease in the concentration of reactant = - Δ [A]

Time taken Δt
Or
Rate = Increase in the concentration of product = Δ [B]
Time taken Δt

Rate of a reaction is always positive.

Average Rate of reaction

It is the rate of reaction over a certain measurable period of time during the course of
reaction.

For a reaction, A B

Average rate of reaction = Decrease in concentration of A

Time taken

rav = - [A]2 - [A]1

t2 – t1

= - Δ [A]
Δt

where [A]1 is the concentration of A at time t1

[A]2 is the concentration of A at time t2
Or
Average rate of reaction = Increase in concentration of B
Time taken

rav = [B]2 - [B]1

t2 – t1

= ΔB
Δt

For a chemical reaction,

aA + bB → cC + dD

Average rate of reaction rav = -_1_ Δ A = -_1_ Δ B = _1_ Δ C = _1_ Δ D

a Δt b Δt c Δt d Δt

Rate of disappearance of A = - Δ [A]

Δt
Rate of disappearance of B = - Δ [B]
Δt

Rate of appearance of C = Δ [C]

Δt
Rate of appearance of D = Δ [D]
Δt

Instataneous Rate of reaction

It is the rate of change of concentration of any one of the reactants or products at a given
time.

rinst = - d [A] Or rinst = d [B]

dt dt

(Note: The time interval Δ t is made very small (dt) so that the rate of the reaction remains
almost constant during the interval.)
Units of Rate of reaction
If concentration is expressed in terms of mol L-1, unit of rate of reaction will be mol L-1 s-1
For gaseous reactions, where the concentration of gases is expressed in terms of partial
pressures then unit of rate of reaction will be atm s-1

Factors Affecting Rate of Reaction

1. Concentration of Reactant
The rate of a chemical reaction is directly proportional to the concentration of reacting
species. Increase in concentration of reactant increases the number of collisions and the
activated collisions between the reactant molecules results in increased rate of reaction.

2. Temperature
The rate of a chemical reaction increases with the temperature. For every 10°C rise in
temperature, the reaction rate almost doubles.

3. Nature of reactant
A chemical reaction involves breaking of old bonds and formation of new bonds. The
reactivity of the substance can therefore be related to the ease with which the specific bonds
are broken and new bonds are formed and the number of such bonds formed.
Eg. 2NO + O2 2NO2 (Fast)
2CO + O2 2CO2 (slow)

4. Presence of Catalyst
Catalyst increases the rate of reaction

5. Surface area of the reactant

Larger the surface area of the reactant, faster is the rate of reaction.

6. Exposure to radiation
Some chemical reactions take place very fast when exposed to light radiation.
Eg. Reaction between hydrogen and chlorine takes place very slowly in the absence of light
but in presence of light, it takes place very fast.
hν
H2 + Cl2 2 HCl

Rate Law
The Rate law is the expression in which reaction rate is given in terms of molar concentration
of the reactants with each term raised to some power, which may or may not be the same as
the stoichiometric coefficient of the reacting species in the balanced chemical equation.
For a chemical reaction,
aA + bB → Products

According to the Law of Mass Action, at a given temperature, the rate of a chemical reaction
is directly proportional to the product of the molar concentration of reactants.
Rate α [A]a [B]b
Rate = k [A]a [B]b

where [A] and [B] are the molar concentrations of reactants

k is the proportionality constant called Reaction Rate Constant or Velocity
constant or Specific reaction rate.

Rate constant
It is defined as the specific rate of reaction when the molar concentrations of the reactants is
taken to be unity.
Rate = k, if [A] = [B] = 1

Characteristics of rate constant

1. Greater the value of rate constant, faster is the reaction.
2. Each reaction has a particular value of rate constant at a particular temperature.
3. The value of rate constant for the same reaction changes with temperature.
4. The value of rate constant for a reaction doesn’t depend upon the concentration of the
reactants.

Order of Reaction
It is defined as the sum of powers to which concentration terms are raised in the Rate law
expression

Consider a reaction, aA + bB + cC Product

The Rate law expression is
Rate = k [A]a [B]b [C]c
Then the order of reaction is
n= a + b+ c
If for a reaction, n = 0, the reaction is 0th order
n = 1, the reaction is 1st order
n = 2, the reaction is 2nd order
n = 3, the reaction is 3rd order

Molecularity of Reaction
The number of reacting species (molecules, atoms, ions) which collide simultaneously to
bring about a chemical reaction is called Molecularity of reaction.
Eg. 2HI H2 + I2 Molecularity = 2
NO + O3 NO2 + O2 Molecularity = 2
2NO + O2 2NO2 Molecularity = 3
 Order of Reaction
1. It is the sum of powers to which concentration
terms are raised in the Rate law expression.
2. It can be fractional as well as zero.
3. It is an experimentally determined term.
4. Order of reaction is applicable to elementary as
well as complex reactions.
5. Negative order reaction is possible.
6. Types of reactions depending upon orders
Zero order reaction
(i) H2 (g) + Cl2 (g) 2HCl
(ii) 2NH3 (g) N2 (g) + 3H2 (g)
First order reaction
(i) H2O2 → H2O + ½ O2
(ii) Radioactive disintegration
(iii) Inversion of cane sugar
Second order reaction
(i) 2HI → H2 (g) + I2 (g)
(ii) Alkaline hydrolysis of ester
Third order reaction
2NO (g) + O2 (g) → 2NO2 (g)
Molecularity of Reaction
1. The number of reacting species (molecules,
atoms, ions) which collide simultaneously to
bring about a chemical reaction is called
Molecularity of reaction.
2. It cannot be fractional or zero.
3. It is an experimentally determined term.
4. Molecularity of reaction is applicable only to
elementary reactions.
5. Molecularity can never be zero.
6. Types of reactions depending upon
molecularity
Unimolecular reaction
N2O4 (g) + 2NO2 (g) → 2NO2 (g)
Bimolecular reaction
2HI (g) → H2 (g) + I2 (g)
Termolecular reaction
2NO (g) + O2 (g) → 2NO2 (g)
Units of Reaction Rate Constant
1. For 1st Order Reaction
Rate law can be expressed as,
Rate = k [A] where A is the reactant
mol L-1 = k mol L-1
s
k = 1 = s-1
s

2. For 2nd Order Reaction

Rate law can be expressed as,
Rate = k [A]2 where A is the reactant
mol L-1 = k [mol L-1]2
s
mol L-1 = k mol2 L-2
s
k = mol L-1
mol2 L-2 x s

k = mol-1 L s-1

3. For 3rd Order Reaction

Rate law can be expressed as,
Rate = k [A]3 where A is the reactant
mol L-1 = k [mol L-1]3
s
mol L-1 = k mol3 L-3
s
k = mol L-1
mol3 L-3 x s

k = mol-2 L 2 s-1

Rate of Reaction Reaction Rate Constant

1. It is the change in concentration of
reactants or products per unit time
2. It depends on the initial concentration of
the reactant
3. The unit of rate of reaction is mol L-1s-1
1. It is the proportionality constant in the
rate law expression
2. It is independent of the initial
concentration of the reactant
3. The unit of reaction rate constant depends
upon the order of reaction
Mechanism of Reaction

A chemical reaction occurs by the series of elementary processes. The sequence of the
elementary processes leading to the overall stoichiometry is called the mechanism of the
reaction.

In the sequence of the elementary processes leading to the formation of products from the
reactants, the slow step is the rate determining step.

Eg. NO2 (g) + CO (g) CO2(g) + NO(g)

Mechanism

NO2 (g) + NO2 g) NO(g) + NO3(g) ……….. (Slow)

NO3 (g) + CO g) CO2(g) + NO2(g) ……….. (Fast)

The rate expression for the reaction is

Rate = k [NO2] [NO2]

Rate = k [NO2]2

The concentration of CO does not appear in the rate expression since CO is consumed as
soon as NO3 is formed. Hence 1st step is the rate determining step.
Integrated Rate Equations

1) Zero Order Reaction

Consider a reaction
R → Products
Rate = k [R]0
- d [R]_ = k
dt

- d [R] = k dt

Integrating both sides

- ʃ d [R] = k ʃ dt

- [R] = k t + C …… (1)
where C is the constant of integration

At t = 0, let [R] = [R]0 i.e initial concentration of the R

Substituting in equation (1)

- [R]0 = C
Substituting in equation (1)
- [R] = k t - [R]0 ……... (Multiply with –ve sign)

[R] = - k t + [R]0
The above equation is of the form y = m x + c
If we plot a graph of [R] vs t, we get a straight line with slope = - k and intercept [R]0.

Rate Constant for Zero order reaction k = _[R]0 - [R]_

t
Examples of Zero Order Reaction
1) Enzyme catalysed reactions and the reactions which occur on metal surface.
2) Decomposition of gaseous ammonia on a hot platinum surface.
1130 K
2 NH3 (g) N2 (g) + 3 H2 (g)
Pt Catalyst

3) Thermal decomposition of HI on gold surface.

2) First Order Reaction
Consider a reaction
R → Products
Rate = k [R]
- d [R]_ = k [R]
dt

- _ d [R] = k dt
[R]

Integrating both sides

- ʃ d [R] = k ʃ dt
[R]

- ln [R] = k t + C …… (1)
where C is the constant of integration

At t = 0, let [R] = [R]0 i.e initial concentration of the R

Substituting in equation (1)

- ln [R]0 = C
Substituting in equation (1)

- ln [R] = k t - ln [R]0 ……... (Multiply with –ve sign)

ln [R] = - k t + ln [R]0
The above equation is of the form y = m x + c
If we plot a graph of ln [R] v/s t, we get a straight line with slope = - k and intercept equal
to ln [R]0.

kt = ln [R]0 - ln [R]

kt = 2.303 log [R]0 - 2.303 log [R]

k = 2.303 log _[R]0 _

Rate Constant for First order reaction t [R]
• On rearranging the equation, log _[R]0_ = _ k t__
[R] 2.303

If we plot a graph of log [R]0 / [R] vs t, we get slope = _ k__

2.303

• log [R]0 - log [R] = k t__

2.303

- log [R] = _k t__ - log [R]0

2.303

log [R] = -_k t__ + log [R]0

2.303
The above equation is of the form y = m x + c with slope = - _ k__
2.303

Example of First Order Reaction

1) Hydrogenation of ethane.

2) All natural and artificial radioactive decay of unstable nuclei.

3) Decomposition of N2O5 and N2O.

Half Life of the Reaction (t1/2 )
It is the time in which the concentration of the reactants is reduced to one half of its initial
concentration.

For Zero Order Reaction

k = _[R]0 - [R]_
t

At t = t1/2 , [R] = _[R]0_

2

[R]0 - [R]0_
k = 2____
1/2
t

t1/2 = _[R]0_
2k

• t1/2 for a zero order reaction is

o Directly proportional to the initial concentration of the reactants.
o Inversely proportional to rate constant.

For First Order Reaction

k = 2.303 log _[R]0_

t [R]

At t = t1/2 , [R] = _[R]0_

2
k = 2.303 log _[R]0_
t1/2 _[R]0
2

t1/2 = _2.303_ log 2

k

t1/2 = _0.693_
k

• t1/2 for a first order reaction is

o Independent of the initial concentration of the reactant.
o Inversely proportional to rate constant.
Pseudo First Order Reaction
Chemical reactions which appear to be of first order but actually are of higher order are called
Pseudo First order reactions.

E.g. 1 Hydrolysis of Ester

CH3COOC2H5 + H2O → CH3COOH + C2H5OH

In this reaction, water is taken in excess. The concentration of water does not get altered
during the course of reaction.

Rate = k’ [CH3COOC2H5] [H2O]

Since [H2O] remains constant

k’ [H2O] = k

Rate = k [CH3COOC2H5] and the reaction behaves as first order reaction.

Eg. 2 Inversion of cane sugar

H+
C12 H22 O11 + H2O C6 H12 O6 + C6 H12 O6
Cane sugar Glucose Fructose

Rate = k [C12 H22 O11]

Dependence of Reaction rate on Temperature

The rate of chemical reaction generally increases on increasing the temperature.
For a chemical reaction with rise in temperature by 100C, the rate constant is nearly doubled.

According to Arrhenius, the rate of the reaction is given by,

k = A e –Ea / RT
where k is the rate constant
A is Proportionality constant called Arrhenius factor or Frequency factor
Ea is Activation Energy measured in Joules / mole
R is Gas constant

Activation Energy (Ea)

According to Arrhenius, a chemical reaction can take place
only when the reactant molecules collide to form unstable
intermediate. It exists for a very short time and then breaks
up to form the desired product. The energy required to form
the intermediate called activated complex is called
activation energy.
It is the minimum amount of energy required by the reactant molecules so that the collisions
between reactant molecules are effective in yielding product molecules.

Lower the activation energy, the reaction takes place faster.

Higher the activation energy, the reaction is slower.

Threshold energy (ET)

The minimum amount of energy which the reactant must possess
in order to convert into products is known as threshold energy.
Ea = ET - ER

All the molecules in the reacting species do not have the same kinetic energy and hence it
becomes difficult to predict the behavior of any one molecule with precision. Ludwig
Boltzmann and James Clark Maxwell used statistics to predict the behavior of large number of
molecules.

The peak of the curve corresponds to the most

probable kinetic energy i.e. kinetic energy of
maximum fraction of molecules. There are
decreasing number of molecules with energies
higher or lower than this value.

When the temperature is raised, the maximum of the curve moves to the higher energy value
and the curve broadens out i.e. spreads to the right such that there is greater proportion of
molecules with much higher energies. The area under the curve must be constant since total
probability must be one at all times.

Increasing the temperature of the substance increases the fraction of molecules which collide
with energies greater than Ea. In the curve at (t + 10), the area showing the fraction of molecules
having energy equal to or greater than activation energy gets doubled leading to doubling the
rate of reaction.
Taking natural logarithm on both sides of Arrhenius equation
ln k = ln A - _Ea_
RT
The plot of ln k vs 1/T gives a straight line with slope = -Ea/R and intercept = ln A

If k1 and k2 are the rate constants at temperature T1 and T2 respectively then,

ln k1 = ln A - _Ea_ …….. (1)
RT1
ln k2 = ln A - _Ea_ …….. (2)
RT2
Subtracting equation (1) from (2)
ln k2 - ln k1 = _Ea_ - _Ea_
RT1 RT2

ln _k2 _ = Ea_ _1 - 1_
k1 R T1 T2

Writing Arrhenius equation in logarithmic form

log _k2 _ = Ea____ _1 - 1_
k1 2.303 R T1 T2

log _k2 _ = Ea____ _ T2 - T1_

k1 2.303 R T1 T2

Effect of Catalyst on Rate of Reaction

A catalyst is a chemical substance which alters the rate of a reaction without itself undergoing
any permanent chemical change.

The action of catalyst can be explained by Intermediate complex theory. A catalyst participates
in a chemical reaction by forming temporary bonds with the reactants resulting in an
intermediate complex which has a transitory existence and decomposes to yield the product
and the catalyst.
In a chemical reaction, a catalyst provides an alternate pathway or reaction mechanism by
reducing the activation energy between the reactants and products and hence lowers the
potential barrier.

Theory of Reaction Rates

Collision Theory

Collision theory was developed by Max Trautz and William Lewis in 1916 – 18.

According to this theory, the reactant molecules are assumed to be hard spheres and the reaction
is postulated to occur when molecules collide with each other.
The number of collisions between the reacting molecules taking place per second per unit
volume is known as collision frequency (Z).

For a bimolecular elementary reaction, A + B → Products

Rate = ZAB e–Ea / RT
where ZAB represents the collision frequency of reactants A and B
e–Ea / RT represents the fraction of molecules with energies equal to or greater than Ea.

But only those collisions in which the colliding species are associated with certain minimum
amount of energy and collide in proper orientation result in the product formation.
The collisions in which molecules collide with sufficient kinetic energy (called threshold
energy) and proper orientation, to facilitate breaking of bonds between reacting species and
formation of new bonds to form products are called effective collisions.
To account for effective collisions, another factor P, called the probability or steric factor is
introduced.
Rate = PZAB e–Ea / RT

Thus, in collision theory, activation energy and proper orientation of molecules together
determine the criteria for an effective collision and hence the rate of a chemical reaction.
The drawback of collision theory is that, it considers atoms or molecules as hard spheres and
ignores their structural aspects.