CHEMICAL KINETICS

INTRODUCTION:
Chemical Kinetics is the study of Rates of Reactions. The rate at
which a chemical reaction occurs can be very varied. Reactions can be very fast like
precipitation reactions or very slow like corrosion in metals in atmosphere.
Chemical reactions can be studied by monitoring the change of
concentration with time. Consider the chemical reaction
A⟶B
The rate of the above reaction can be found by measuring the change
in concentration of either the reactant or product for a time interval Δt. If [A]i
is the initial concentration and [A]f is the final concentration of reactants after the
time interval Δt, then the rate of the reaction can be expressed as:

rate = – Δ[A] ( Where Δ[A] = [A] f – [A]i )

Δt
( The negative sign is necessary because the value of Δ[A] will be negative since
the final concentration of reactant will be less than that of the initial concentration.)
INTRODUCTION:
The rate of the reaction can also be represented in terms of concentration
of product B, for the reaction
A⟶B
Δ[A] Δ[B]
rate = – =
Δt Δt
However if we consider the reaction
A⟶2B
The rate of appearance of B will be double the rate at which A disappear.
Hence the rate of the reaction can be expressed as
Δ[A] 1 Δ[B]
rate = – =
Δt 2 Δt
( Unit of rate of a reaction is molL–1sec–1)
INTRODUCTION:

Consider a general reaction

aA+bB⟶cC+dD

The rate of this reaction can be expressed as

1 Δ[A] 1 Δ[B] 1 Δ[C] 1 Δ[D]
rate = – =– = =
a Δt b Δt c Δt d Δt

Here Δ[A], Δ[B] , Δ[C] and Δ[D] are the changes in concentration of A, B, C
and D respectively for the time interval Δt.
1 Δ[A] Δ[A]
Note : While the expression – represents the rate of reaction,
a Δt Δt
alone represents the rate of disappearance of A.
PROBLEM:

Question: The decomposition of N2O5 in CCl4 at 318 K has been studied by

monitoring the concentration of N2O5 in the solution. Initially the concentration of
N2O5 is 2.33 mol L–1 and after 184 minutes, it is reduced to 2.08 mol L–1.
The reaction takes place according to the equation
2 N 2O5 (g) → 4 NO2 (g) + O2 (g)
Calculate the average rate of this reaction. What is the rate of production of NO 2
during this period?

Question: In a reaction, 2A → Products, the concentration of A decreases from 0.5

mol L–1 to 0.4 mol L–1 in 10 minutes. Calculate the rate during this interval?
AVERAGE AND INSTANTANEOUS RATE:
The rate of a reaction measured for a finite interval of time is called average rate.
It is represented by Δ[A]
Δt
. However the average rate of a reaction will vary
depending upon the time period for which it is measured.
Hence a new entity called instantaneous rate is defined which the rate of the
reaction an instant of a reaction. If d[A] is the infinitesimally small change in
concentration of reaction A for a equally small time interval dt then the
instantaneous rate of the reaction is – d[A] .
dt

Experimentally, average and instantaneous rate of a reaction can be determined

by plotting a graph of concentration of reactants against time taken. Average rate
will be equal to Δ[A] divided by Δt. While instantaneous rate at time ‘t’ will be the
slope of the tangent to the curve drawn at a point on the curve corresponding to
time ‘t’.
AVERAGE AND INSTANTANEOUS RATE:

Average rate = -Δ[A] / Δt

Δ[A]

Conc. [A]
(MolL-1) Slope = Instantaneous rate = - d[A] / dt

t
Δt
Time (s)
 FACTORS AFFECTING RATE OF A REACTION:
The main factors which affect the rate of a reaction are:

i) Concentration of reactants (Pressure of reactant if they are gases)

ii) Temperature
iii) Catalyst

In the case of solid reactants, the total surface area of the reactants will also
influence the rate of the reaction. Greater the surface area, easier will it be for the
reaction to occur.
EFFECT OF CONCENTRATION ON RATE OF REACTION:
Consider a general reaction
a A + b B ⟶ c C + dD
The relationship between rate of the reaction and concentration can be expressed
as given below.
rate α [A] x [B]y
Here the important point is that the powers x and y may or may not be equal to the
stoichiometric coefficients a and b. Hence,
rate = k [A]x [B]y
This expression which relates the rate of a reaction to concentration of reactants is
called rate law, rate equation or rate expression.
Rate law is the expression in which reaction rate is given in terms of molar
concentration of reactants with each term raised to some power, which may or may
not be same as the stoichiometric coefficient of the reacting species in a balanced
chemical equation.
ORDER OF A REACTION:
For the general reaction
a A + b B ⟶ c C + dD

The rate law was expressed as

rate = k [A]x [B]y
This expression is purely an experimental entity. It cannot be written by just
knowing the equation for a reaction. The powers x and y are the orders of the
reaction with respect the reactants A and B respectively.
(x+y) is the overall order of the reaction or simply the order of the reaction.

Hence order of the reaction can be defined as the sum of the powers to which
concentration terms are raised in the rate law of a reaction.
Order is purely an experimental quantity and it can take values which are
whole numbers or fractional. Order can be even equal to zero in cases were
the rate of the reaction is independent of concentration.
Order of reaction 1 is 3/2
Order of reaction 2 is 1
Examples of zero order reaction
Pt
2NH3 N2 + 3H2 Rate = k[NH3]0

The thermal decomposition of HI on gold surface is another example of zero order

reaction.
2HI Au
H2 + I2 Rate = k[HI]0
Examples of first order reaction

N2O5 N2O3 + O2 Rate =k[N2O5]

2N2O 2N2 + O2 Rate =k[N2O]

Examples of second order reaction
CH3Br(aq) + OH-(aq) CH3OH(l) + Br-(aq)

Rate = [CH3Br][OH-]

CH3COOC2H5 + OH- CH3COO- + C2H5OH

Rate = [CH3COOC2H5][OH-]

Examples of third order reaction

2NO(g) + O2(g) 2NO2(g)

Rate = [NO] 2[O2]

The constant k is called rate constant, velocity constant or specific reaction
rate. It can be defined as the rate
of the reaction when
concentration of reactants are
unity.
Gen unit of rate constant for
an nth order reaction is

Rate = k[conc]n

conc time-1 = k[conc]n

k = [conc]1-n time-1
MOLECULARITY OF A REACTION :

The number of reacting species (atoms, ions or molecules) taking part in an

elementary reaction, which must collide simultaneously in order to bring about a
chemical reaction is called molecularity of a reaction.

Molecularity is a theoretical entity which is the sum of the stoichiometric

coefficients in the equation for an elementary reaction. Its values can be only 1, 2
or 3.
Unimolecular reaction

Bimolecular reaction

Trimolecular or termolecular reactions

Reactions with molecularity greater than 3 is very rare.

The probability that more than three molecules can collide and react simultaneously is very
small. Hence, reactions with the molecularity three are very rare and slow to proceed.
It is, therefore, evident that complex reactions involving more than three molecules in the
stoichiometric equation must take place in more than one step.
For eg.

Elementary reactions-Reactions which take place in a single step.

Complex reactions- Reactions which take place in more than one step.

This reaction which apparently seems to be of tenth order is actually a second order
reaction.The overall rate of the reaction is controlled by the slowest step in a reaction called
the rate determining step.
Thus for a simple or elementary reaction molecularity is equal to order of the reaction.
For a complex or multistep reaction, the molecularity of the slowest step or the RDS is the
order of the overall reaction.
 Slow

Both the steps are bimolecular elementary reactions. Species IO- is called as an
intermediate since it is formed during the course of the reaction but not in the overall
balanced equation. The first step, being slow, is the rate determining step.

Thus, the rate of formation of intermediate will determine the rate of this reaction.
Difference between order
and molecularity
UNIT OF RATE CONSTANT:
The unit of rate constant of a reaction varies with the order of the reaction.
Consider a reaction
A⟶B
If the reaction is zero order:
rate = k [A]o or rate = k
Here the unit of rate constant ‘k’ is the same as unit of rate of the reaction which is
MolL-1s-1.
If the reaction is first order:
rate = k [A]1
(MolL-1s-1) = k (MolL-1)
Unit of k = (MolL -1s-1) / (MolL-1) = s-1
If the reaction is second order:
rate = k [A]2
(MolL-1s-1) = k (MolL-1)2
Unit of k = (MolL -1s-1) / (MolL-1)2 = mol-1Ls-1
PROBLEMS RELATED TO UNITS OF RATE CONSTANT:

Question: What is the unit of rate constant for 3rd order and nth order reaction?

Question: For the reaction A + B → C, the rate law of the reaction was found to be
rate = k[A]1[B]1/2. What is the unit of rate constant of the reaction.

Question: For the reaction A + B → C, the value of specific reaction rate for the
reaction is 3.5 x 10-4 Lmol-1s-1. What is the order of the reaction?
INTEGRATED RATE LAW FOR ZERO ORDER REACTION:
Consider the reaction
A⟶B
Assuming the order of the reaction is zero order its rate law will be:
rate = k [A]o

or the differential rate law is – d[A] = k [A]o

dt
on rearranging we get. – d[A] = k dt

on integrating both side – d[A] = k dt

– [A] = kt + c
When t = 0 , [A] will be equal to the initial concentration [A]o, Hence c = – [A]o

– [A] = kt – [A]o or [A]o – [A]

[A]o – [A] = kt or k= t
This is the integrated rate law of zero order reaction.
 INTEGRATED RATE LAW FOR ZERO ORDER REACTION:
Graphical representation:
[A]o [A] = – kt +[A]o

Concentration [A]
Slope = - k
[A]o – [A]
k=
t

Time ‘t’

Zero order reactions are relatively uncommon. Some enzyme catalyzed reactions and reactions which occur
on metal surfaces are a few examples of zero order reactions. The decomposition of gaseous ammonia on a
hot platinum surface is a zero order reaction at high pressure.
Pt
2NH 3 (g) N2 (g) + 3 H2 (g)
Rate =k [A]0
INTEGRATED RATE LAW FOR FIRST ORDER REACTION:
Consider a first order the reaction A ⟶ B
d[A]
Its differential rate law will be – = k [A]1
dt
d[A] 1/x dx = ln x
on rearranging we get. – [A] = k dt

d[A]
on integrating both sides, – [A] = k dt

– ln [A] = kt + c
When t = 0 , [A] will be equal to the initial concentration [A]o, Hence c = – ln [A]o
[A]
– ln [A] = kt – ln [A]o or ln o = kt
[A]
This is the integrated rate law of [A]o
first order reaction. 2.303
k= log
t [A]
INTEGRATED RATE LAW FOR FIRST ORDER REACTION:
Graphical representation:

ln [A] = - kt + ln [A]o log [A] = - kt + log [A]o

2.303

ln[A]o log[A]o

Slope = -k
Slope = - k 2.303
ln[A] log[A]

Time Time
ln [R] = - kt + ln [R]o log [R]o = kt
[R] 2.303
PROBLEMS RELATED TO INTEGRATED RATE LAWS:

Question: A first order reaction is 20% complete in 40 min. Calculate the time
required for 60% completion of the reaction.
INTEGRATED RATE LAW FOR GASEOUS FIRST ORDER REACTION:
Consider a first order gaseous reaction or x = ( p t – pi )
A(g) ⟶ B(g) + C(g)
Let pi be the initial pressure of A and pt the total but pA = (pi – x) = pi – ( pt – pi)
pressure at time ‘t’. Hence pA = 2pi – pt
Then total pressure at time ‘t’
pt = p A + p B + p C According to integrated rate law for first order
reaction: 2.303 [A]o
Where pA , pB and pC are partial pressure of A, B k = log
t [A]
and C at time t.
The reactants being gases we can write this as
If ‘x’ atm is the decrease in pressure of A at time 2.303 pi
t, then increase in pressure of B and C will also k = log
t pA
be x atm each.
A(g) ⟶ B(g) + C(g) Hence the integrated law for the reaction will be
t=0 pi atm 0 atm 0 atm
At time t (pi-x) atm x atm x atm 2.303 pi
k = log
t (2pi – pt)
∴ pt = (pi – x) + x + x = pi + x
HALF LIFE OF A REACTION:
Half life of a reaction is defined as the time taken for the half the initial
concentration of reactants to get converted to products. Its denoted by t½.
Half life of a zero order reaction: Half life of a first order reaction:
For a zero order reaction For a first order reaction
[A]o – [A] 2.303 [A]o
k= k = log
t t [A]
When t = t½ , [A] = [A]o When t = t½ , [A] = [A]o
2 2
[A]o – [A]o 2.303 [A]o
∴ ∴ k = log = 2.303 . log 2
2 t½ [A]o
k= t½
t½
2
[A]o 0.693
t½ = t½ =
2k k
RELATIONSHIP BETWEEN HALF LIFE AND ORDER:
The relationship between half life of a reaction and initial concentration of reactant
depends upon the order of the reaction.
It can be seen that for a zero order reaction, the half life is directly proportional to
the initial concentration.
But for a first order reaction, the half life is independent of initial concentration, ie. It
is a constant irrespective of initial concentration. In general it can be shown that

t ½ α [A]o(1- n) (where n is the order of the reaction.)

This fact can be used as an experimental technique to determine the order of a

reaction. By monitoring the variation of half life with different initial concentration,
we can identify how the initial concentration is related to half life and hence find the
order of the reaction.
PSEUDO ORDER REACTIONS:
Consider the following reaction: H+
CH3COOC2H5 (aq) + H2O (l) CH3COOH (aq) + C2H5OH (aq)
The actual rate law of this reaction is
rate = k [CH3COOC2H5] [H2O]
Hence this reaction is a second order reaction.
However the whole reaction is in aqueous medium and therefore there is a large
excess of water present. This means that the concentration of wate will more or
less remain constant throughpout the reaction. Therefore, the rate law of this
reaction in practice becomes
rate = k’ [CH3COOC2H5]
Which makes it a first order reaction.
Such a reaction were a higher order reaction behaves as a lower order
reaction because one of the reactants is present in large excess that its
concentration remains effectively constant in the reaction, is called a pseudo
order reaction.
PROBLEMS RELATED TO HALF LIFE:

Question: A first order reaction is found to have a rate constant, k = 5.5 × 10 -14 s-1.
Find the half-life of the reaction.
PROBLEMS RELATED TO HALF LIFE:

Question: The half life of a first order reaction is 600 s. How long will 5 g of this
reactant take to reduce to 3 g?

k = 0.693 = 0.693 = 1.15 x 10-3 s-1

t1/2 600

t = 2.303 logRo
k R
t = 2.303 log 5 = 2.303 x 0.222 = 444 s
k 3 1.15 x 10-3
DETERMINATION OF ORDER REACTIONS:
The order of the reaction can be determined by different methods:
1) Graphical Method: This is a trial and error method in which the experimental
data is compared graphically with the different integrated rate laws.

2) Ostwald’s isolation method: When there are more than one reactants, The
reaction is converted into a pseudo order reaction by taking all but one
reactants in large excess. Like this order with respect to each reactant is
determined.

3) Initial rate method: In this method the initial rate of the reaction is determined
by keeping the concentration of pone of the reactant constant and changing the
concentration of the other. Using this experimental data, the rate law and order
is determined.
PROBLEMS RELATED TO INITIAL RATE METHOD:

Question: The following results have been obtained during the kinetic studies of the
reaction:
2A + B → C + D
Experiment [A] (mol L–1) [B] (mol L–1) Initial rate (mol L–1 min–1)
1 0.1 0.1 6.0 × 10–3
2 0.3 0.2 7.2 × 10–2
3 0.3 0.4 2.88 × 10–1
3 0.4 0.1 2.40 × 10–2

Determine the rate law and the rate constant for the reaction.2 + 3 H2 (g)
Temperature Dependence of the Rate of a Reaction
Most of the chemical reactions are accelerated by increase in temperature.

For example, in decomposition of N2O5 , the time taken for half of the original amount
of material to decompose is 12 min at 50oC, 5 h at 25oC and 10 days at 0oC.
A mixture of potassium permanganate (KMnO4 ) and oxalic acid (H2C2O4 ),
potassium permanganate gets decolourised faster at a higher temperature than that
at a lower temperature.
It has been found that for a chemical reaction with rise in temperature by 10°, the
rate constant is nearly doubled.

The temperature dependence of the rate of a chemical reaction can be

accurately explained by Arrhenius equation. It was first proposed by Dutch
chemist, J.H. van’t Hoff but Swedish chemist, Arrhenius provided its physical
justification and interpretation.
Arrhenius equation

-Ea/RT
k=Ae
where A is the Arrhenius factor or the frequency factor. It
is also called pre-exponential factor. It is a constant
specific to a particular reaction.
R is gas constant and
Ea is activation energy measured in joules/mole (J mol –1).
It can be understood clearly using the following simple reaction

According to Arrhenius, this reaction can take place only when a

molecule of hydrogen and a molecule of iodine collide to form an
unstable intermediate .
Formation of HI through the
intermediate

It exists for a very short time and then breaks up to form two
molecules of hydrogen iodide.
This is explained by the Activation Complex Theory or
Transition State Theory.
ACTIVATION COMPLEX THEORY OF REACTION RATES:
This theory is also called Transition Activated Complex
(Transition State)
state theory. According to this theory, all
reaction proceed through the formation
of activated complex or transition state.
The energy of the transition state is Ea
usually greater than the energy of both

Potential energy
the reactants and products.
The energy that must be supplied to the
reactants to form the activated complex Reactants
is called the activation energy Ea of the H
H2 + I2
reaction. Products
The rate of the reaction is inversely 2HI
proportional to the activation energy. Lower
the value of Ea, faster will be the reaction Reaction coordinate
rate. Reaction coordinate represents the profile of energy
change when reactants change into products
ACTIVATION COMPLEX THEORY OF REACTION RATES:
Some energy is released when the complex
decomposes to form products. So, the
final enthalpy of the reaction depends
upon the nature of reactants and products.

If the reaction is endothermic,

the diagram showing plot of
potential energy vs reaction coordinate will be Reaction coordinate

All the molecules in the reacting species do not have the same kinetic energy.
Since it is difficult to predict the behaviour of any one molecule with precision,
Ludwig Boltzmann and James Clerk Maxwell used statistics to predict the
behaviour of large number of molecules.
According to them, the distribution of
kinetic energy may be described by
plotting the fraction of molecules (NE
/NT ) with a given kinetic energy (E) vs
kinetic energy .
Here, NE is the number of molecules with
energy E and NT is total 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 a
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 . It is clear
from the diagram that 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 a
reaction.
 -Ea /RT
k=Ae
In the Arrhenius equation the factor e -Ea /RT corresponds to the
fraction of molecules that have kinetic energy greater than Ea .
Lower temperature
Fraction of molecules

More fraction of
molecules have
Ea energy greater
Higher temperature than Ea at a higher
temperature

Kinetic energy of molecules

EFFECT OF TEMPERATURE ON RATE OF REACTION:
In general, the rate of the reaction will increase with increase in temperature.
The quantitative effect of temperature change on reaction rates was studied by
Arrhenius and is called Arrhenius equation according to which:
– E /RT
k=Ae a

ln k = ln A – E a
RT
2.303 log k = 2.303 log A – Ea a
RT
log k = log A – Ea
2.303 RT
ARRHENIUS EQUATION:

ln A log A

Slope = - Ea
Slope = - Ea 2.303R
R log k
ln k

1 1
T T

Note :The term e – Ea/RT corresponds to the fraction of molecules that have kinetic energy greater than Ea
ARRHENIUS EQUATION:
According to Arrhenius equation:

log k = log A – Ea
2.303 RT
Let k1 be the rate constant of the reaction at temperature T1 and k2 be the rate
constant of the temperature T2 .Assuming that A is constant,

log k1 = log A – Ea (1)

2.303 RT1
log k2 = log A – Ea (2)
2.303 RT2
Equation (2) – (1)
log k2 - log k1 = Ea 1 1 k2 Ea T2 T1
or log =
2.303 R T1 T2 k1 2.303 R T1 T 2
EFFECT OF CATALYST ON RATE OF REACTION:
A catalyst is a substance which increases the rate of a reaction
without itself undergoing any permanent chemical change. For
example, MnO2 catalyses the following reaction so as to increase its rate
considerably.

https://youtu.be/q5VywpnZfEU
The word catalyst should not be used when the added substance
reduces the rate of reaction. The substance is then called inhibitor.
The action of the catalyst can be explained by intermediate complex
theory. According to this theory, a catalyst participates in a chemical
reaction by forming temporary bonds with the reactants resulting in
an intermediate complex. This has a transitory existence and
decomposes to yield products and the catalyst.
 EFFECT OF CATALYST ON RATE OF REACTION:
It is believed that the catalyst Activated Complex
(Without catalyst)
provides an alternate pathway or
reaction mechanism by reducing
Activated Complex
the activation energy between Ea (With catalyst)
reactants and products and E a’

Potential energy
hence lowering the potential energy
barrier.
It is clear from Arrhenius equation Reactants
that lower the value of activation H
energy faster will be the rate of a
Products
reaction. A small amount of the
catalyst can catalyse a large
amount of reactants. A catalyst Reaction coordinate
does not alter Gibbs energy, ∆G Ea - Activation energy without catalyst
of a reaction. Ea’ - Activation energy with catalyst
A catalyst does not change the equilibrium constant of a reaction
rather, it helps in attaining the equilibrium faster, that is, it catalyses the
forward as well as the backward reactions to the same extent so that the
equilibrium state remains same but is reached earlier.
COLLISION THEORY OF REACTION RATES:
Collision theory -developed by Max Trautz and William Lewis in 1916 -18
According to this theory, the reactant molecules are assumed to be hard spheres
and reaction is postulated to occur when molecules collide with each other.
The rate of the reaction depends upon:
The number of collisions per second per unit volume of the reaction mixture is
known as collision frequency (Z).
Another factor which affects the rate of chemical reactions is activation energy
For a bimolecular elementary reaction
A + B → Products
rate of reaction can be expressed as – Ea/RT
Rate = ZABe
where ZAB represents the collision frequency of reactants, A and B and
e-Ea /RT represents the fraction of molecules with energies equal to
or greater than Ea
.
Comparing this equation with Arrhenius equation, we can say that A is
related to collision frequency.

– Ea/RT
Rate = ZABe

ZAB, collision frequency = A,Arrhenius factor or pre exponential

factor.

Rate = ZABe– Ea/RT,this equation is valid for simple,elementary reactions.

For complex reactions,it is not valid.
The reason could be that all collisions do not lead to the formation of
products. The collisions in which molecules collide with sufficient kinetic
energy (called threshold energy*) and proper orientation.
Proper orientation is required to to facilitate breaking of bonds between
reacting species and formation of new bonds to form products.
Those collisions in which the reactant molecules collide with proper
energy and proper orientation are called effective collisions.

For example, formation of methanol

from bromoethane depends upon
the orientation of reactant molecules.
The proper orientation of reactant
molecules lead to bond formation
whereas improper orientation makes
them simply bounce back and
no products are formed.
To account for effective collisions, another factor P, called the
probability or steric factor is introduced. It takes into account the fact
that in a collision, molecules must be properly oriented i.e.,

– Ea/RT
Rate = PZABe
Thus, in collision theory activation energy and proper orientation of
the molecules together determine the criteria for an effective
collision and hence the rate of a chemical reaction.

Collision theory also has certain drawbacks as it considers atoms/

molecules to be hard spheres and ignores their structural aspect.
PROBLEMS RELATED TO ARRHENIUS EQUATION:
Question: The rate of a reaction quadruples when the temperature changes from
293 K to 313 K. Calculate the energy of activation of the reaction.
PROBLEMS RELATED TO ARRHENIUS EQUATION:
Question: The rate constants of a reaction at 500K and 700K are 0.02s–1 and
0.07s–1 respectively. Calculate the values of Ea and A.
End of Chapter