CHEMICAL KINETICS

Before starting chemical kinetics from syllabus point of view we have to

understand some important points in this topic
Chemical kinetics is a branch of physical chemistry which deals with two
important factors (I) Measurement of rate of reaction (ii) Mechanism of
the reaction
(I) To understand measurement of rate of reaction we plot a graph
conc. Vs time the shape will be as shown:

Irreversible Reaction
7M
6M
Product

Concentration

Reversible Reaction
Reactant
1M

Time
Fig-1 Graph of Concentration vs Time for Reversible and Irreversible Reaction
Suppose we start( at t =0 min) a reaction by taking 7M
reactant and after 10 minutes the remaining amount of
reactant is 1M then average rate of reaction is measured
as
𝐷𝑒𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 𝐶𝑜𝑛𝑐.𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 ሺ 7−1ሻ 𝑀
Average Rate = 𝐶ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑡𝑖𝑚𝑒
= ሺ 10−0ሻ 𝑚𝑖𝑛

= 0.6 M min-1

𝐼𝑛𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 𝐶𝑜𝑛𝑐.𝑜𝑓 𝑃𝑟𝑜𝑑𝑢𝑐𝑡 ሺ 6−0ሻ 𝑀

Average Rate = 𝐶ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑡𝑖𝑚𝑒
= ሺ 10−0ሻ 𝑚𝑖𝑛

= 0.6 M min-1
 Average Rate of Reaction
On the basis of this example Average Rate is
defined as the decrease in concentration of the
reactants or increase in the concentration of products
per unit time and its unit is Mol lit-1 min-1.
Average Rate ,Velocity or Speed of a reaction are
same in Chemical Kinetics
But in chemical kinetics we measure rate of reaction
at a particular moment or instantaneous rate or also
known as differential rate.
 Differential Rate of Reaction

To understand the differential rate of reaction we take example of

reaction between N2 and O2

can be written as − 𝛥𝑡2 = − 𝛥𝑡2 =

The reaction is N2 + O2 → 2NO the average rate of the reaction
𝛥[𝑁 ] 𝛥[𝑂 ] 𝛥[𝑁𝑂]
𝛥𝑡

These are average rate equations. In Chemical Kinetics

Instantaneous rate or differential rate is used, average rate becomes

differential rate when 𝛥𝑡 → 0 (it means time difference is very less)

i.e. − 𝑑𝑡2 = − 𝑑𝑡2

𝑑[𝑁 ] 𝑑[𝑂 ] 𝑑[𝑁𝑂]
𝑑𝑡
=
One important thing which we have to remember that rate cannot be
negative then why -Ve sign is put before some expressions. -Ve sign
before these expressions just indicate decrease in concentration of
reactant and +ve sign or no sign indicate increase in concentration.

4
 But these are not correct rate expression, For writing
correct rate expression ,we have to consider the
stoichiometric coefficient of the reaction. For example
N2 + O 2 → 2 NO

On the basis of this reaction we can say that N 2 and O2 are

consumed at the same rate but formation of NO takes place

−2 = −2
the twice the rate of consumption of N 2 and O2 i.e.
𝑑[𝑁2] 𝑑[𝑂2] 𝑑ሾ𝑁𝑂ሿ
𝑑𝑡 𝑑𝑡 𝑑𝑡
=
or − = −
𝑑[𝑁2] 𝑑[𝑂2] 1 𝑑[𝑁𝑂]
𝑑𝑡 𝑑𝑡 2 𝑑𝑡
=
In general for a reaction of the type

− = −
a A + bB +..→ c C + dD+.. , the rate of reaction is
1 𝑑[𝐴] 1 𝑑[𝐵] 1 𝑑[𝐶] 1 𝑑[𝐷]
𝑎 𝑑𝑡 𝑏 𝑑𝑡 𝑐 𝑑𝑡 𝑑 𝑑𝑡
= =
a,b,c and d are stoichiometric cofficients
5
 Molecularity of a reaction
Most of the chemical reactions proceed through a series
of intermediate steps. These steps are known as
elementary steps. Investigation of these steps constitute
the mechanism of the reaction. The molecularity of a
reaction is defined as the number of reactant molecules
which take part in an elementary reaction. These
reactions are said to be unimolecular , bimolecular or
termolecular depending upon whether one ,two or three
molecules involved in the a chemical reaction e.g.
N2 + O2 → 2NO this reaction has two molecularity
N2 + 3H2 → 2NH3 this reaction has four molecularity
6
 Order of a Reaction
The Order of reaction is defined as the sum of powers
of the concentrations terms in the rate equation. These
powers are not stoichiometric coefficients in the balanced
chemical equation but must be determined in the rate
experiments. Consider the following reaction
2N2O5 → 4 NO2 + O2 , The experimental rate of this
reaction is , Rate = k [N2O5]1
This relationship between rate and conc. of reactant is
known as differential rate law or differential rate equation
Here order of reaction is one but stoichiometric coefficient
is two. So order and stoichiometric coefficient are different.
The order of reaction is also equal to number of
concentration variables i.e. the number of reactants changing
their concentration in moles/lit during the reaction. If no
reactant change its concentration in moles/lit then order is
zero. If one reactant change then it is one and so on. The order
of reaction can change with change in conditions such as
temperature, pressure etc. but molecularity is invariable
7
 Mechanism of the Reaction
Sometimes it seems to be reaction is taking place in one step but
experimental rate law and theoretical rate law are not in agreement
if reaction is considered in one step. In this situation we have to see
the reaction from different point of view i.e. we have to consider
different steps for a reaction and using these steps we arrive at the
same experimental and theoretical rate.
These different steps of a reaction become mechanism of the
reaction. To understand the mechanism of a reaction we take
example of H2 and Br2 reaction. It seems to be simple reaction
H2 + Br2 → 2HBr
and rate of reaction should be
𝑑
𝑑𝑡
[HBr] = k[H2][Br2]
But experimental rate do not match with this equation. The
1
𝑘1 2
𝑑 2𝑘2ቀ 𝑘 ቁ [𝐻 2]
5
𝑑𝑡 𝑘 [𝐻 𝐵𝑟 ]
ቀ 1+ 𝑘4 ሾ𝐵𝑟 ሿ ቁ
experimental rate is equal to [HBr] =
3 2
To get this rate we have to consider the various possible steps
taking place inside the reaction. These steps are
 k1
(I) Br2 2Br
k 2
(II) Br + H2 HBr + H
k 3
(III) H + Br2 HBr + Br
k 4
(IV) H + HBr H2 + Br
k 5
(V) Br + Br Br2
If we consider these steps the following equation can be
derived
1
𝑘1 2
𝑑 2𝑘2ቀ 𝑘 ቁ [𝐻 2]
5
𝑑𝑡 𝑘 [𝐻 𝐵𝑟 ]
ቀ 1+ 𝑘4 ሾ𝐵𝑟 ሿ ቁ
[HBr] =
3 2

which is similar to experimental rate

These different steps constitutes a mechanism of a
reaction.
 ACTIVATION ENERGY
In Arrhenius equation k =
A.e−Ea / RT the appearance of Ea
suggests that the molecules must
acquire certain amount of energy
before they could undergo
chemical reactions. This means
that the molecules must be
activated i.e. they must be raised
to higher energy state.
The minimum energy which the
reacting molecules must possess
before the reaction to occur is
known as Activation Energy
The energy required by the reacting molecules to form
activated complex is known as Activation energy

f
Ea

Energy
r
ER Ea

E
EP

Reaction path
 A correct dependence of k on temperature is given by
Arrehenius equation
k = A.𝑒−𝐸𝑎 /𝑅𝑇
𝐸𝑎
Taking log of both sides
ln k = ln A - 𝑅𝑇

ቂ = 0ቃ
or
𝑑 ln 𝑘 𝑑 ln 𝐴 𝑑 𝐸𝑎 𝑑 ln 𝐴
𝑑𝑇 𝑑𝑇 𝑑𝑇 𝑅𝑇 𝑑𝑇
= - ∵

𝑑 ln 𝑘 𝐸𝑎
𝑑𝑇
= 𝑅𝑇2 ...(1)
Where Ea is activation energy. Integrating Equation(1)

d ln k = 𝑅𝑎 𝑇−2dT
𝐸
We get
‫𝑑 ׬‬ln𝑘 = ‫𝑇 ׬‬−2 𝑑𝑇
𝐸𝑎
𝑅
ቂ ቃ
𝐸𝑎 𝑇−2+1
𝑅 − 2+1
ln k = + I
−𝐸𝑎
ln k = 𝑅𝑇 + I

+ I′ …(2) ቂ𝐼 = ቃ
or
−𝐸𝑎 ′ 𝐼
2.303𝑅𝑇 2.303
log k =
where I and I′ are the integration constant
−𝐸𝑎
Eq(2) suggests that plot of log k vs 1/T
should be straight line with slope =2.303𝑅
 Slope = - Ea / 2.303RT
log k

1/T
Intercept = I'. From the slope of the plot ,the activation
energy can be determined
However, if we integrate equation(1) between the limits
k = k1 at T = T1 and k = k2 at T = T2 then

ln =
ln k2 – ln k1 =
ln =
ln =
or log =
 Arrhenius Equation
𝑑 ln 𝑘 𝐸𝑎
The variation of rate constant with temperature is given by

𝑑𝑇 𝑅𝑇2
= …(1)

d ln k = 𝑎 𝑇−2dT
𝐸
or
𝑅
…(2)

‫׬‬ 𝑑ln𝑘 ‫׬‬ 𝑇−2 𝑑𝑇

𝐸𝑎
Integrate this equation
𝑅
=
ቂ ቃ + I
𝐸𝑎 𝑇−2+1
𝑅 − 2+1
ln k =
−𝐸𝑎
𝑅𝑇
ln k = +I …(3)
Take antilog of both sides, we get
k = A.𝑒−𝐸𝑎 /𝑅𝑇 ..(4)
The Eq(4) is Arrhenius equation
Example-1
The value of rate constant for the decomposition of
nitrogen penta oxide is 3.46 x 10-5 at 25°C and
4.87 x 10-3 at 65°C. Calculate Ea of the reaction

Solution: log =

Ea = log x 2.303 x 8.314 x 298 x 338

_________________________________
338 - 298
Ea = 103584 J mol-1
Example-2
Calculate the activation energy of a reaction whose rate
constant is tripled by a 10°C rise in temperature in the
vicinity of 27°C [ R = 1.987 Cal K-1mol-1]

Solution : The given temperature is 27°C = 300K

In the vicinity of this temperature, the two temperatures
are 295 K and 305 K
log =

log 3 =

Ea = 19641 Cal mol-1

 Example-3 The activation energy of a non-catalyzed
reaction at 37°C is 20 k cal/mol and the activation energy
of the same reaction catalyzed by an enzyme is 6 kcal.
Calculate the ratio of rate constants of catalyzed and
non-catalyzed reactions.
Solution : kC = A.𝑒−𝐸1/𝑅𝑇(catalyzed)
kN = A.𝑒−𝐸2/𝑅𝑇(non-catalyzed)
=𝑒 =𝑒
−𝐸1 −(−𝐸2) 𝐸2 − 𝐸1
𝑘𝐶
𝑅𝑇 𝑅𝑇
𝑘𝑁
Example-4 The rate constant of second order reaction is
5.7 x 10-5lit mol-1s-1 at 25ºC and 1.64 x 10-4lit mol-1s-1at
40 ºC. Calculate Ea and Arrhenius factor A
[R=1.987CalK-1mol-1] Ans E=13060 cal A=2.15 x 105 lit

ቂ ቃ
mol-1s-1
𝑘2 𝐸𝑎 𝑇2−𝑇1
𝑘1 2.303 𝑅 𝑇1𝑇2
Solution: log =
Q.1 The rate constant of a reaction at 30ºC is exactly
twice that at 20 ºC. Calculate Ea
[ R = 1.987 Cal K-1mol-1] (Ans. = 12.2kcal/mol

Q.2 The rate constant of a reaction at 230 ºC is twice that

at 220 ºC. Calculate Ea[R = 1.987 Cal K-1mol-1]
(Ans. = 34.1 kcal/mol

Q.3 Two reaction have same value of frequency factor A

but different values of Ea. Calculate the ratio of rate
constant if Ea values differ by (i) 1 kcal/mol

Hint : k = e
(ii)10 kcal/mol (Ans (i) 5.4 (ii) ≈ 2 x 107
k2 (E2−E1)/RT k2
, k =e1000/1.987.298=𝑒1.688 = 5.4
1 1
Q.4Trichloroacetic acid in aniline solvent decomposes to
give chloroform and CCl4. The rate constant for this
first order reaction is 4 x 10-5 min-1at 25ºC and 8 x 10-4
at 45 ºC. Calculate Ea[R = 1.987 Cal K-1mol-1]
(Ans = 27.6 kcal/mol)
Q.5 Benzene diazonium chloride decomposes in the
presence of water according to first order kinetics ,
the velocity constant at 25ºC is 2.8 x 10 -3 min-1and
activation energy is 11.9 kcal/mol. Find the velocity
constant at 35 ºC[R = 1.987 Cal K-1mol-1]

Q.6 In the esterification of a organic acid and alcohol the

relative rate constants at 20 ºC and 30 ºC are 2.1x10-4
and 3.6 x 10-4min-1 Calculate Ea
[R = 1.987 Cal K-1mol-1]
 Collision Theory of Reaction Rates
This theory has been found to be satisfactory for gaseous
reaction and postulates that the reacting molecules must
collide . If collision is the only requirement for a reaction to
occur then rate of the reaction should be proportional to the
number of collision between the reacting molecules.
However in actual practice it is found that the rate of
reaction is much smaller than the number of collisions
between the reacting molecules. In order to explain this
discrepancy , it is assumed that molecules are activated and
only those molecules possessing energy equal to or greater
than the activation energy are able to form the products.
Furthermore in many cases it is assumed that molecules
must be properly oriented so that rearrangement of atoms
could occur with minimum expenditure of energy.
 Thus in collision theory the essential requirements for the
reaction to occur are
(i) Collision between the reacting molecules
(ii) Activation of molecules
(iii) Proper orientation at the time of collision.
For a bimolecular gaseous reaction
k
A + A → Products
The rate of the reaction is given by
= k[A]2 , If the concentration of A is 1 mol/lit,
we get = k …(1)
According to the collision theory the rate of the reaction
is
= k = Z.q = 2.Z11.q …(2)
[ Z11(no. of collision)= ]
Where Z is the number of colliding molecules per second
per lit and q is the fraction of the total number of
molecules which are activated and Z11is the number of
collision per second per lit. The values of Z 11 and q can be
calculated from the kinetic theory of gases. Z 11 is given by
= π …(3)
and
q= = …(4)
where σ is collision diameter and is the average velocity
of the molecules in litre per second, n * the number of
molecules per litre having energy equal to or more than the
activation energy Ea and is the total number of molecules
per litre. Substituting the value of in equation (3) , we get
 𝑍 ξ 2π𝜎 (𝑛′ ) ට ∵ ቆ 𝑐ҧ= ට ቇ
1 2 2 8𝑅𝑇 8𝑅𝑇
11 = 2 𝜋𝑀 𝜋𝑀

= 2𝜎2(𝑛′ )2 ට
𝜋𝑅𝑇
𝑀
…(5)
If the reactants are different, then the number of
collisions per second per litre is given by
2
𝑍 𝑛1 𝑛2 ቀ ቁ ට
′ ′ 𝜎1+ 𝜎2 8𝜋𝑘𝑇
12 = 2 µ
…(6)
Where 𝑛1 ′
, 𝑛2
′
are the number of molecules per litre of
reactants 1 and 2 , σ1 and σ2 are the collision diameters of
𝑚1𝑚2
the molecules and µ is the reduced mass of the system
and is given by µ = 𝑚 + 𝑚 Thus the expression for the
1 2
rate of a reaction involving identical molecules is given by
Rate = 2.qZ11 = 2. 2𝜎 (𝑛′ ) ට .𝑒
𝐸
2 2 𝜋𝑅𝑇 − 𝑎
𝑅𝑇
𝑀
…(7)
and for different reactant molecules
Rate = 2 q.Z12 = 2. . …(8)
Comparison of equation (7) with Arrhenius equation
(k= A ) show that the pre exponential factor A in
Arrhenius equation is equal to 2 Z 11 and depends on the
square root of temperature.
The results predicted by equation (7) and (8) can be
compared with the experimental values of the rate
constants.
We can take the example of dissociation of a mole of HI
per dm3(lit) at 556K. The value of activation energy for
reaction has been found to be 184kJ the collision diameter
for HI is 3.5 x 10-9dm., the molar mass is 1.28 x 10 -
1
kg/mol and the number of molecules per lit is 6.023x1023.
Substituting these in equation (5) we get
 Z11 = 2.99 x 1034 s-1dm-3
and Z = 2 x 2.99 x1034 s-1dm-3
The number of colliding molecules per second per dm 3 is
twice the value of Z11 , i.e. 5.98 x 1034
The fraction q of the total number of molecules which are
activated is given by q = = exp(- )
= 5.2 x 10-18 Hence
k = q.Z = 5.98 x 1034 x 5.2 x 10-18
=3.12 x 1017molecules/dm3/sec. If this value is divided by
Avogadro’s number we get the rate constant in units of
mol-1dm3/sec. Therefore k = 5.2 x 10 -7 mol-1dm3/sec.
The experimental value of k has been found to be
3.5 x 10-7 mol-1dm3/sec.
The agreement between these values is quite satisfactory
indicating the validity of this theory. However this type of
agreement between the calculated and the experimental
value is applicable only for simple gaseous reactions and
in solutions where molecules are simple. For reactions
involving complex molecules, the experimental and
calculated values are quite different. In order to explain
this discrepancy it is further postulated that molecules
must be properly oriented at the time of collision and an
additional term is introduced in the expression for the rate
of the reaction. i.e. k = P.Z. 𝑒
𝐸𝑎
−𝑅𝑇
…(9)
Where P is the probability factor or steric factor and is
related to geometry of the molecule. It measures deviation
from the calculated value. It can have values from 1 to 10 -9