Chemical Kinetics

The branch of physical chemistry which deals with the rate of reaction is called chemical kinetics.
Chemical kinetics deals with the rate of a reactions and rate law, factors such as temperature,
pressure concentration and catalyst that effect the rate of chemical reaction and the sequence of
sloops by which a reaction occurs.

Rate of a Reaction: -
Rate of a chemical reaction is the measure of speed of reaction or velocity of reaction. Rate of a
reaction is defined as “the change in the concentration of any one of the reactants or products per
unit time”.
Consider a simple reaction.

Rate of reaction=rate of disappearance of A=rate of appearance of B .

d[A]
¿− ¿
dt
d [ B]
¿+ ¿.
dt
[ ]shows concentration∈moles per liters .

Units of Rate
Unit of Concentration
Unit of Rate=
Unit of time
Concentration of a substance is expressed in moles per liter ( mol / Liter ) or mol /lit or molli t −1 and
time is measured in second “ S”, min, hours (h), days (d) or years. Therefore, units of rates may be
−1 −1
Moles /liter sec ormol lit s
−1 −1
Moles /Liter minormol lit mi n
−1 −1
Moles /liter hour∨mol lit h

Expression of rate of reaction: -

Suppose dx is the small change in the concentration of reactants or product during the small
interval of time dt then the rate is expressed as,
dx
Rate of reaction=
dt
Rate Law and Rate Constant: -
An expression which shows how the reaction rate is related to concentration is called rate law or rate
equation.
Consider the following general reaction

The rate of this reaction may not depend upon all the a concentration term of A and all b
concentration term of B.
Suppose experimentally the rate of the reaction is found to depend upon α concentration term A
and β then we may write
a
Rate ∝[ A ] . ¿
a
Rate=K [ A] . ¿
This is called rate law.
K=rate constant∨velocity constant .
[ A ]=molar concentration of A .
[B]=molar concentration of B .
If all concentration is taken as unit.
¿ A∨¿∨B∨¿ mol/liter
Then rate law becomes
Rate=K
Rate constant may be defined as “The reaction rate when the concentration of each reactant is taken
as unity”, rate constant is therefore also called specific reaction rate.
Factors Affecting Rate of a Reaction: -
The following factors affect the rate of a chemical reaction.
1. Nature of reactants.
2. Concentration
3. Pressure
4. Temperature
5. Catalyst
1. Nature of Reactants: -
The rate of a chemical reaction is greatly affected by the nature of the reacting substances.
This is because a reaction involves breaking of the bonds of reactants and the formation of
new bonds in the products molecules. The energy is required for breaking bonds and energy
is released when a bond is formed. The net energies involved are different for different
reactions and hence the rates are different.
2. Concentration: -
When a reaction proceeds the reactants as consumed. Therefore, the concentration of the
reactants decreases with the passage of time. It is experimentally proved that the rate of
reaction also decreases as the time passes so the rate of the reaction is directly proportional
to the concentration of the reactants. This can be show graphically.

3. Pressure: -
 Pressure has no effect when the reacting substances are either liquid or solid.
The pressure has important role in the case, when the reactants are gases. In such case the
rate of the reaction is proportional to the pressure of the reactants.
When both the reactant and products are in gaseous state then the pressure has effect
when the number of moles of reactants and products are different when the numbers of
moles of reactants are greater than the reaction proceeds in forward direction. When
products have greater number of moles the backward reaction proceeds. There is no effect
of pressure at equilibrium when reactants and products have same number of moles.
4. Temperature: -
Temperature has a very important effect of the rate of reaction. For most of the reactions
the rate of reaction increases with rise of temperature. As a rough rule rate of a reaction
nearly double or some time even triple for every 10℃ rise of temperature.
Temperature coefficient=K ¿ ¿
Where K t and K t+10 are the specific reaction rates at t℃ and (t +10)℃ respectively.
Similarly, many reactions are known which do not take place at room temperature but occur
readily at higher temperature (endothermic reaction).
Generally endothermic reaction rates increase with increases in temperature while
exothermic reaction is not favored by increasing temperature. There is some energy which a
reactant must possess to react this called activation energy.
5. Catalyst: -
A catalyst is a substance which increases the speed of a reaction without itself undergoing
any chemical change. The presence of a catalyst provides an alternate path with lower
activation energy (energy barrier).
Thus, the energy of activation is lowered and hence a greater number of molecules can cross
the barrier and change over to products. Thereby increasing the rate of chemical reaction.
Order of Reaction: -
The order of a reaction can be defined as the sum of the power of concentration in the rate law
OR
The sum of the exponents to which the concentration terms in the rate law are raised to express the
observed rate of reaction is called order of reaction.
According to rate law
Rate=¿
Thus, in the above expression order of reaction=α + β

Depending upon whether α + β is equal to0 , 1 ,2∨3. The reaction is said to be of zero order. 1 st
order, 2nd order and 3rd order respectively, α and β are called the orders of reaction with respect to
A and B respectively.
The order of reaction may not be always a whole number and can be fractional order of reaction is
experimental quantity. It cannot be found from balanced chemical equation order of reaction is
many reacting species whose concentration determines the rate of reaction.

Molecularity of a Reaction: -
Molecularity can be defined as “The total number of molecules (reacting species) involved in
chemical reaction”.
OR
The number of reacting species (atoms, molecules or ions) which collide simultaneously to bring a
chemical reaction is called Molecularity of a reaction; Molecularity of a reaction is always a whole
number.
When the reaction involves decomposition of a single species, it will be unimolecular reaction;
Decomposition of H2O2 is a unimolecular reaction.

Similarly, when the reaction involves collision between two species it will be a bimolecular reaction
and if three species take part in the collision it is called trimolecular or termolecular reaction.
Some reaction take place through a sequence of two or more consecutive steps and are called
complex reaction. Each step has a molecularly of its own and none of the step has a molecularly of
more than three. It is over all reaction because it is made of several elementary reactions.
The slowest step is the rate determing step of the reaction and the molecularly of the rate
determing step is taken for complex reaction, which can be defined as “the number of molecular or
atom taking part in the rate determing step”.
Differences between Order and Molecularly: -
Order of Reaction Molecularity of Reaction
1. The number of molecules (atom or ions) 1. The number of molecules (atom, ions)
whose concentration changes in a chemical involved in a chemical reaction.
reaction.
2. It is the sum of powers of the rate law. 2. It is the number of reacting species
undergoing simultaneous collision in complex
or simple reaction.
3. It can be determined from balanced chemical 3. It is the sum of moles in a balanced chemical
equation. equation.
4.It is an experimentally determined value 4. It is a theoretical concept.
5.It can have fractional value 5. It is always a whole number.
6.It can assume zero value 6. It cannot have zero value.
7.Its value cannot be greater than three 7. It can have greater value than three but very
rare.
8. Order of reaction can change with conditions 8. Reaction conditions cannot affect
such as pressure, temperature, concentration. Molecularity.
9. It has no significance for a complex reaction 9. It is always the same for the overall reaction
and can be expressed for each elementary step whether the reaction is complex or simple.
in case of a complex reaction.

Zero Order Reactions: -

When the rates of chemical reactions are independent of the concentration of all reactants is called
zero order reactions.
Or
The reaction whose rate does not depend upon the concentration of any reactant is called zero order
reaction.

As the reaction proceeds the quantities of H 2 and C l 2 decrease but their amount per unit volume
remains the same or the concentration of H 2 and C l 2 remains constant, so this reaction is of zero
order in nature.

Rate Equation for Zero Order Reaction: -

Let us consider a zero-order reaction of the types.

Initial concentration a o∨( A o )=0

Final concentration ( a−x ) ∨A=x
Disapperance of A
Rate of Reaction=
Time
 dx −d [ A ] o o
= [ A ]∨[a ]
dt dt
dx −d (a−x)
= =K o [ Ao ]
dt dt
Or
dx −d (a−x)
= =K o ¿
dt dt
dx
=K o … … … (1)
dt
On integration equation (1) becomes
dx
∫ dt =∫ K o
∫ dx=K o∫ dt
x=K o t +c … … …(2)
C = constant of integration
When t=0 x=0
So, equation (2) becomes
0=K o ×o+ c
c=0
Equation (2) becomes
x=K o t
x
K o = Or x=K o t
t
Where K o =¿ rate constant of a zero-order reaction.
The rate constant K o is equal to the rate of reaction at all concentration.

Unit of K o :-(Zero order Reaction)

−3
x concentrationunits mol dm
Ko= = = = mol d m−3 se c−1
t time sec
Example: -

Reactions catalyzed enzymes are also zero order reaction.

Half Life of Zero Order Reaction: -

 Half-life is the time for a chemical reaction when the concentration of the reactants become half of
the initial concentration.
OR
The time taken for half the reaction to complete.
We know from zero order reaction.
x=K o t … … …(1)
When
a
x= ∧t=t 1
2 2
Then equation (1) becomes
a
¿ K ot 1
2 2
a
t 1=
2
2 Ko
Half-life is proportional to the initial concentration.

First Order Reactions: -

A reaction in which the rate of the reaction depends upon one concentration term or (one single
reactant concentration) is called 1st order reaction.
e.g.

Rate Equation for First Order Reaction: -

Let us consider a first order reaction.

Initial concentration a mol l-1Ot=0

Final concentration a−xxt=t
dx
According to law of mass action the rate of a reaction is directly proportional to the
dt
concentration of the reaction thus
dx
∝(a−x)
dt
dx
=K ( a−x ) … … …(1)
dt
Where K is rate constant.
Equation (1) can be written as
dx
=Kdt … … …(2)
(a−x )
Integrating equation (2)
dx
∫ a−x =∫ Kdt
−ln (a−x)=Kt + c … … …(3)
c=¿Constant of integration
When
t=0 x=0
Equation (3) becomes
 −ln(a−0)=Kxo+c
−ln a=c … … …(4)
Putting the value form (4) into equation (3)
−ln (a−x)=Kt +(−lna )
Or
−ln (a−x)=Kt −lna
−ln(a−x)+lna=Kt
lna – ln(a−x )=Kt
a
log a−log b=log
b
lna
=Kt
(a−x )
1 lna
K=
t ( a−x )
Changing to common logarithms (ln=2.303 log )
2.303 a
K= log … … …(5)
t (a−x)
(a= A o),(a−x= A)
Equation (5) is rate equation for 1st order reaction
2.303 [ Ao]
K= log
t [ A]
Unit of First Order Rate Constant: -
The rate constant of first order equation is given by,
1 ×2.303 a
K= log
t a−x
Or
2.303 [A ]
log o
t [A]
2.303 concentration units
K= log
sec concentration unit
−1
K=se c
Or
−1
K=t (sec , min , hr ,etc)

Half-life of 1st Order Reaction: -

The integrated rate equation for 1st order reaction is given
2.303 [ Ao]
K= log
t [ A]
Or
2.303 a
log
t (a−x )
When
1
[ A ]= [ A o ]∧t=t 1
2 2

2. 303 [ Ao]
K= log
t1 1
A
2
2 o
 2.303
K= log 2
t1
2
2.303
K= ×0.3010
t1
2
0.693
K=
t1
2
0.693
t 1= … … … (1)
2
K
Equation (1) shows that
i. Half-life for a first order reaction is independent of the initial concentration.
ii. Half-life is inversely proportional to (K) rate constant.
Graphical Representation of First Order Reaction: -
We know
a
ln =Kt
( a−x )
Or
−ln (a−x)=Kt – lna
Multiply by -1 we get
ln (a−x)=−Kt + lna
If ln (a−x) is plotted verse t a straight line is obtained.{(a= A o),(a−x= A)}

Second Order Reaction: -

When the rate of reaction depends upon the concentration of two terms (reactant) is known as
second order reaction.
OR
A reaction in which the rate of reaction depends upon the concentration of two reactants is called
second order reaction.
e.g.

Rate Equation for Second Order Reaction: -

Second order reaction has two types depending upon the types and concentration of reactions.
Case 1;
When only one reactant is involved.
Case 2;
When two reactants are involved.

Case 3; When only one reactant is involved: -

The general reaction involving one reactant is given.

−1
Initial concentration of A=a mol li t
−1
Decrease∈the concentration of A at any instant=x mol lit
−1
Concentration of A at theinstant of timet=(a−x)mol l ¿
According to law of Mass Action
Rate of reaction ∝¿
dx
∝¿
dt
dx
=K ¿
dt
K=rate constant of second order reaction

Equation (1) may be written as

dx
¿¿
Integrating this equation.
dx
∫ ¿¿ ¿
∫ dx . ¿ ¿
¿¿
¿¿
¿
1
=Kt + c … … …(2)
(a−x )
c=integration constant
In the beginning
when t=0 , x=0
putting the value in equation (2).
1
=K ×O+ x
a−o
1
x=
a
Putting the value of c in equation (2)
1 1
=Kt + … … … (3)
(a−x ) a
1 1
Kt = −
(a−x) a
Taking LCM
a−(a−x)
Kt =
a (a−x)
a−a+ x
¿
a(a−x )
x
Kt =
a(a−x)
 1 x
K= … … … (4)
t a(a−x )

This is the integrated rate equation for second order reaction in the case in which the reactants
involved are the same with same concentration.

Units of Second Order Rate Constant: -

Form equation (3)
1 x 1 concentrationunits
K= − = −
t a ( a−x ) Time concentration units . concentration unit

1 1
K=
sec mol dm−3
3 −1 −1
K=d m mol se c

Half Life of the Second Order Reaction: -

From equation (4)
1 x
K=
t a(a−x )
1 x
t=
K a(a−x )

When
a
x= t=t 1
2 2

a
1 2
t 1=
K a
2
a(a− )
2
a
1 2
t 1=
K a−a
2
a( )
2
a
1 2
t 1=
K a
2
a( )
2

a
t1 = 1 2
2 K a
a( )
2

1
t 1=
2
Ka
Graphical Representation: -
From equation (3)
1 1
=Kt +
(a−x ) a
1 1
Plotting Vs. “t ” then will be slope and initial
(a−x ) a

Case 2; When two different reactants are involved: -

General equation for such reaction is

−3
Initial concentration of A=a mol d m
−3
Initial concentration of B=b mole d m
−3
The amount of product produced=x mol d m
Concentration of A at timet=(a−x)
Concentration of B at Time t=(b−x)
According to the law of Mass Action.
Rate of Reaction ∝[ A ][B ]
dx
∝(a−x)(b−x )
dt
dx
=K ( a−x ) ( b−x ) … … … (1)
dt
K=rate constant
Equation (1) can be written as
dx
=Kdt
(a−x )(b−x )
Integrating this equation
dx
∫ ( a−x )(b−x) =∫ Kdt
This equation is solved by the partial fractions. Splitting as follows
1 A B
= + … … … ( 2)
( a−x ) ( b−x ) ( a−x ) ( b−x )
A∧B are constant
Multiply both sides of equation (2) by (a−x)(b−x )
1 A B
(a−x)(b−x )× =(a−x)(b−x )× +(a−x)(b−x )×
( a−x ) ( b−x ) ( a−x ) ( b−x )
 1= A (b−x)+ B(a−x)… … … ( 3 )
Lets Put (a−x)=0
So
x=a
Then equation (3) becomes
1= A (b−a)+B (a−a)
1= A (b−a)
1
A=
(b−a)
−1
A= … … … ( 4)
(a−b)
Lets put b−x=0
b=x
Equation (3) becomes
1= A (b−b)+B (a−a)
1=0+B (a−b)
1
B= … … … (5)
( a−b)
Putting the value from equation (4) and (5) in equation (2)
We get
1 −1 1
∫ ( a−x )(b−x) =∫ (a−b)(a−x ) +∫ ( a−b)(b−x ) =∫ Kdt
1 −1 dx 1 dx
∫ ( a−x )(b−x) = (a−b) ∫ (a−x ) + (a−b)∫ (b−x) =Kt +c
1 −1 1
∫ ( a−x )(b−x) = ( a−b ) [−ln ( a−x ) ] + ( a−b ) [− ln ( b−x ) ]=Kt +c
1
∫ (a−x )(b−x) =
1
(a−b) [
ln(a−x ) +
1
(a−b) ]
−ln(b−x )=Kt + c

1 1
∫ ( a−x )(b−x) = (a−b) ( ln ( a−x )−ln(b−x ))=Kt + c
1 1 (a−x)
∫ ( a−x )(b−x) = ln
(a−b) (b−x)
=Kt +c … … … ( 6 )
c=constant o integration
When
t=0 , x=0,
Then equation (6) becomes
1 (a−o)
ln =K × O+c
(a−b) (b−o)
1 a
ln =c … … … (7 )
(a−b) b
Putting the value of c in equation (6)
1 (a− x) 1 a
ln =Kt + ln
(a−b) (b− x) (a−b) b
1 (a− x) 1 a
ln − ln =Kt
(a−b) (b− x) (a−b) b
1
(a−b)
ln (
(a−x )
(b−x )
a
−ln =Kt
b )
 1 b (a−x)
ln =Kt
(a−b) a (b−x)
1 b(a−x )
K= ln … … … (8 )
t (a−b) a(b−x )
Equation (8) is rate integrated equation for second order with different reaction.

Unit of 2nd Order Reaction Rate Constant: -

From equation (8) we know
1 b(a−x )
K= ln
t (a−b) a(b−x )
2.303 b(a−x )
K= log … … … (9 )
t (a−b) a(b−x )
1 concentration× concentration
K= ln
time ×concentration concentration× concentration
1
K= −3
time units ×mol dm
−1 −1 −3
K=tim e mo l dm or
3 −1 −1
K=dm mo l tim e
3 −1 −1
K=dm mo l Sec
Half Life: -
When two different reacting species are reacting with different concentration there would be
different half-life periods for each of the reactants.
Graphical Representation: -
We know from equation (9)
2.303 b(a−x )
K= log
t (a−b) a(b−x )

b(a−x )
We log is plotted versust , A straight line graph is obtained the line passing through origin
a(b−x )
K (a−b)
with slope to .
2.303

Various Method for Determing the Order of Reaction: -

Many methods are available for the determination of order of reaction.

1. Integrated Rate Equation Method: -

 In this method, the initial concentration of the reactant and the concentration of any one of the
reactants or the products at different instants of time are determined experimentally. Now
these values are either substituted or plotted by rate equation.

a. Substitution Method: -
The values of “a ” and “ x ” are substituted into the integrated forms of the rate equations for
first order, second order and third order one by one the rate equation which gives the constant
value of K gives the order of the reaction.

b. Graphical Method: -
In this method a suitable function is plotted against time.
 If the plot of log (a− x) against time is straight line the reaction is of the first order
reaction.
1
 If the plot of against time is straight line the reaction is of the second order
a−x
reaction.
1
 If the plot of rd
2 against time is straight line the reaction is of the 3 order
(a−x )
reaction.
2. Half Life Period Method: -
In general, we can say that,
1
t1∝ n−1
2 ) (a
1
Half life ∝ n−1
(a )

Where “n ” is the order of the reaction

When n=1 then

1
t1∝ 1−1
2 a
1
t1∝ 0
2 a
1
0
a
0
a =1
1
=1
1

t 1 ∝1
2
Half-life for 1st order reaction is independent of the initial concentration.
For 2nd and 3rd order reaction.
1
t 1 ∝ 2ndorder
2
a

1
t1∝ 2 3rd order
2 a
Two separate experiments are performed by taking different initial concentration of a reactants a 1
and a2. The half-life for two different concentrations we may write.
1
( ) a
t1 ∝
2 1
n−1
1
… … … (1 )

1
( ) a
t ∝
1
2 2
n−1
2
… … … (2 )

Dividing equation (1) by equation (2)

1
( ) =a
t1
2 1
n−1
1

(t ) a1
1
2 2 n−1
2

(t ) = 1 × a
1
2 1
n−1
2

(t ) a 1
n −1
1 1
2 2

(t ) = a
1
2 1
n −1
2

(t ) a
n −1
1 1
2 2
Taking power as a common, we get

( t ) =¿
1
2 1

(t )1
2 2
Taking log of both sides

( ) ( )
log t 1 −log t 1 =(n−1)(log a 2 – log a1 )
2 1 2 2

( ) ( ) =(n−1)
log t −log t
1
2 1
1
2 2

(log a 2 – log a1 )

( n−1 )=
( )
log t 1 −log t 1
2 1
( ) 2 2

(log a 2 – log a1 )

n=1+
( )
log t 1 −log t 1
2 1
( ) 2 2

(log a2 – log a1)

Thus, starting with two different initial concentrations and finding the half-life periods in each case
the value of “n ” can be calculated.

3. Ostwald’s Isolation Method: -

This method can be used for finding the order of those reactions which involve two or more
reactants. The principle of this method is on the fact that the excess reactant does not affect
the rate of the reaction.
All reactants are taken in excess except one. The order thus observed is with respect to the
reactant that has been isolated from the others. For example, three reactants A, B and C, in first
case B and C are taken in excess and A is isolate. So, the order of reaction is due to the respect
of A. Now C and A is taken in excess the order is formed with respect to B. then A and B is taken
 in excess and order with respect to C is formed. The order of reaction found to be a , b∧c
respectively. The overall order of reaction is a+ b+c .

4. Differential Rate Equation Method: -

This method is also known as van’t Hoff’s differential method. According to this the rate of a
reaction of the nth order is to the nth power of its concentration.
dx n
Rate of Reaction (¿ ∝C
dt
dx n
r = =K C
dt
K=rate constant
C=concentration at instant of time(t).
For two different concentrations.
n
r 1=K C 1 … … …(1)
n
r 2=K C 2 … … …(2)
dividing equation ( 1 ) by equation (2)
n
r 1 C1
=( )
r 2 C2
Taking log.
n
r1 C1
log =log ( )
r2 C2

log
r1
r2
=n log
( )
C1
C2
r1
log
r2
n=
C1
log
C2
Or
log r 1 −log r 2
n=
log c1 −log c 2
Thus, to calculate the value of the order “n”, we required to know the values of the rates r 1 and
r2 at two concentration C1 and C2 respectively.
Concentration of the reactant may be plotted against time and the rate at any concentration may be
found from the slope of the tangent at that point.
Alternatively, if value of log r is plotted against log C a straight line is obtained whose slope is n and
its intercept islog K .

Dependence of Rate Constant on Temperature (Arrhenius Equation): -

The effect of temperature on the rate of a reaction was studied by Arrhenius and his formulation is
called Arrhenius Equation .
Arrhenius in 1889 found that the experimentally observed variation of the rate constant K with
temperature “T ” can be expressed by an empirical equation.
B
ln k = A− … … …(1)
T

A∧B are constants and are independent of temperature and depending on the nature of reacting
substances. The values of A and B can be obtained from the intercept and slope of the plot of log
1
K vs .
T
The exponential from of the equation (1) can be written as
−B
T
k=Ae … … … (2)
'
A
e =A
− Ea
Arrhenius involved Boltzmann’s factor RT the equation two becomes
e
−E a
RT
k = A e … … …(3)
E a=Activation Energy
 A=Frequency factor (Frequency of Collisions)
R=Gas constant
T =Temperature

Taking the log of equation(3)

Ea
ln k =ln A− … … …(4)
RT
If the values of rate constant at temperature T 1and T 2 are k 1 and k 2 respectively then equation (4)
becomes
Ea
ln k 1=ln A− … … …(5)
RT 1
Ea
ln k 2=ln A – … … …(6)
RT 2
Subtracting equation (5) from equation (6) we get

(
ln k 2 – ln k 1= ln A – )( Ea
RT 2 )
− ln A−
Ea
RT 1

2
( RT ) ( RT )
ln k – ln k = –
Ea
1 −
−Ea
2 1
Ea Ea
ln k 2 – ln k 1=– +
RT 2 RT 1
Ea Ea
ln k 2 – ln k 1= –
RT 1 RT 2
k 2 Ea Ea
ln = –
k 1 RT 1 RT 2

( )
k 2 Ea 1 1
ln = −
k1 R T 1 T 2
Taking LCM
k 2 Ea T 2−T 1
ln =
k1 R T1 T 2 ( )
k2
log =
Ea T 2−T 1
k 1 2.303 R T 1 T 2 [ ]
Arrhenius equation is a valuable because it can be used to calculate the activation energy.

Activation Energy and its Determination: -

Activation energy is the minimum energy necessary to cause a reaction between substances.
or
The minimum energy that a reactant must possesses to produce product is called activation energy.
It means that the reactants do not pass directly to the product toll they acquire an additional
amount of energy more than the average energy of the molecules of the reactants. Those molecules
which possess energy of activation are said to be activated. Let consider a hypothetical reaction.

The reaction between A and B can be shown diagram.

( Activation Energy Profile)

The molecules of the reactants must climb the energy barrier before they can roll down to form
product. The greater the energy barrier (activation energy) smaller the possibility for conversation of
reactants into products. Activation energy is one of the major factors which control the rate of the
reaction.

Determination of Activation Energy: - ( E a ¿

Activation energy can be calculated by using Arrhenius equation we know.
−Ea
ln k = + ln A … … …(1)
RT
Rearranging this equation
ln k =
−Ea 1
R T ( )+ln A … … … (2)
¿ is comparable with y=mx+b .
Which the equation of straight line the two variables in equation (2) are
k ∧1
ln .
T
1
By plotting ln k versus we get a straight line as shown below.
T
From the slope of the line we can calculate the activation energy
−Ea
Slope=
R
−E a=slope × R
E a=−(slope × R)
Similarly, the E a can be calculated when k is measured at two temperature T 1 and T2. At
temperature T1 the Arrhenius equation is given as
Ea
ln k 1=ln A− … … …(3)
RT 1
At temperature T2
Ea
ln k 2=ln A – … … …(4 )
RT 2
Subtracting equation (3) from (4)

( )( )
Ea Ea
ln k 2 – ln k 1= ln A – − ln A−
RT 2 RT 1

(
ln k 2 – ln k 1= –
Ea
RT 2 )( )
−
−Ea
RT 1
Ea Ea
ln k 2 – ln k 1=– +
RT 2 RT 1
Ea Ea
ln k 2 – ln k 1= –
RT 1 RT 2
k2 E a Ea
ln = –
k 1 RT 1 RT 2

( )
k 2 Ea 1 1
ln = −
k1 R T 1 T 2
Taking LCM

(
k 2 Ea T 2−T 1
ln =
k1 R T 1 T 2 )
 log
k2
=
Ea
[
T 2−T 1
k 1 2.303 R T 1 T 2 ]
K 1 2.303 R
E a=log ×

( )
K2 T 2 −T 1
T1 T2
Thus, having the value of K1, K2 T1 and T2 Ea. can easily be calculated.

Brief Account of Lindemann’s Mechanism for Unimolecular Reaction: -

In 1922 Lindemann’s put forward his mechanism for unimolecular reaction.
Let’s consider a general unimolecular reaction of the types.

e.g.

These reactions are found to be of the first order, if two molecules must collide to provide necessary
activation energy, a second order rate should result similarly if single molecule of the reactant take
part. Then how do molecules in a unimolecular reaction attain their energy of activation.
These problems are solved by Lindemann’s. He suggested the behavior of unimolecular reaction can
be explained based on the bimolecular collisions by assuming that there existed a time log between
activation and reaction molecules.
During this time log the activated molecules could either read or be deactivated thus

If the time lag is long, step (3) is slow the reaction should follow first order Kinetics. However, if A*
reacts as soon as formed step (2) is the slow step, the reaction should be second order.

The proof of Lindemann’s theory is given by studying the effect of change of pressure on the
reaction. At high pressure the rate of deactivation will be dominant on the other hand, at sufficiently
low pressure all the activated molecules will react before they can be deactivated. Therefore, the
reaction kinetics should change form first order to second order with decreasing pressure. The rate
of the reaction will not be proportional to all the molecules activated but only to those which remain
active.
Comparative Study of Collision Theory
And
Transition State Theory for Bimolecular Reaction: -
Collision Theory: -
According to this theory “A chemical reaction take place only by collisions between the reacting
molecules”. But not all collisions are effective only a small fraction of the collisions are productive.
This theory is bases on the following assumptions.
i. The molecules must collide together.
ii. The collisions must be with proper orientation.
iii. The colliding molecules possess enough energy at least equal to the activation energy,
before the reaction takes place.
Let consider a reaction

A chemical reaction occurs by breaking bonds between the atoms of the reacting molecules and
forming new bonds in the product molecules. The energy for the breaking the bonds comes from the
kinetic energy possessed by the reacting molecules before the collision only those molecules that
collide with kinetic energy greater than activation energy Ea can react and other molecular having
low energy do react.

Similarly, the molecules must collide with favorable orientation. The correct orientation is that which
ensures direct contact between the atoms involved breaking a forming of bonds.
So, only the molecules with kinetic energy greater than Ea, and with correct orientation can cause
the reaction.
Collision Theory and Rate of Reaction: -
For a general reaction

The rate is given

Rate K =f × p × Z
f =fractionof molecules that are activated
p=Fraction of molecules witheffective orientation
Z=Collision frequency
− Ea
∆N RT
f= =e
N
− Ea
RT
k = pZ e

Transition State OR Activated Complex Theory: -

This theory was developed by Henry Eyring in 1935. This theory is also known as absolute rate
theory. According to this theory “The reacting molecules from an intermediate called activated
complex before to change into product which has higher energy then both reactants and products”.
If is for this reason this theory is called Transition State Theory.

the transition state theory may be summarized as follows:

(1) In a collision, the fast approaching reactant molecules (A and BC) slow down due to gradual
repulsion between their electron clouds. In the process 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)
Consider the general reaction

By making use of some fundamental properties of the reacting molecules it was shown by Erying
that the rate constant k for any reaction irrespective of its molecularly or order is given by
RT
k= K … … …(1)
Nh
R=Gas constant ,
h=Planck ’ s Constant ,
N= Avogadro ’ s Number ,
T = Absolute Temperature
K=Equilibrium Constant
Equilibrium concentration will be
| X ¿|
K=
| A||B|
From thermodynamics
¿
∆ G =−RT ln K ¿
−∆ G
RT
lnk=e
Equation (1) becomes
¿
−∆ G
RT RT
k= e … … …(2)
Nh
The above equation (2) has two factors
i.e.
¿
−∆ G
RT RT
∧e
Nh
The first factor is constant at constant temperature. Hence the rate of the reaction depends only
upon the second factor involved ∆ G* with a negative sign. This means that at temperature, greater
the value of the free energy of activation for a reaction the slower will be the reaction.

Advantages of Transition State Theory over Collision Theory: -

The transition theory is better than the collision theory in many ways.
i. In Collision theory the correction factor “ p” was introduced arbitrarily while in transition
theory it is given in terms of entropy.
ii. The concept of activated complex seems to be more appropriate then assuming direct
conversion.