1

CHEMICAL KINETICS:
 2
CHEMICAL KINETICS:
 CURRICULUM
 Concept of reaction rate
 Average rate and instantaneous rate of reaction
 Factors affecting rate of reaction
 Rate law equation, rate constants and units
 Ist order, IInd order, IIIrd order & zero order reaction
 Order and molecularity of reaction
 Integrated rate law for first order reaction
 Half-life of reaction
 The collision theory of reaction (qualitative analysis only)
 Concept of activation energy, energy barrier, energy profile diagram
Chemical kinetics is the branch of physical chemistry that is concerned with
3
understanding the rates and mechanisms of chemical reactions by which they occur.
RATE OF REACTION:
The change in concentration of the reactant or product per unit time is known as rate of
reaction.
In terms of reactant, it is defined as the decrease in concentration of reactant per unit
time.
But in terms of product, it is defined as increase in concentration of product per unit time.
Let us consider a general reaction where reactant 'A' gives a product B.
A → B
In the reaction the concentration of A decreases whereas the concentration of B
increases.
In terms of reactant,
−Δ[A] −𝜕[𝐴]
The rate of disappearance of A = or
Δ𝑡 𝜕𝑡
Δ[B] 𝜕[𝐵]
The rate of formation of B = or
Δ𝑡 𝜕𝑡
Δ𝑥 −Δ[A] Δ[B]
In general, the rate of reaction = = =
Δ𝑡 Δ𝑡 Δ𝑡
 TYPES OF RATE OF REACTION:
1. INITIAL RATE 4
If the rate of the reaction is measured at initial time of a reaction, then it is known as
initial rate.
(where t → o)
2. AVERAGE RATE
If the rate of the reaction is measured at a
large time interval, then it is called average
rate.
Δ𝑥
Average rate =
Δ𝑡
3.INSTANTANEOUS RATE
If the rate of the reaction is measured in
very small time interval, then it is called
instantaneous rate. It is denoted by the
𝑑𝑥
symbol .
𝑑𝑡
 5

Instantaneous rate of
reaction
Average rate of reaction
 6
Reaction rate and Stoichiometry:

For a general reaction To get the equivalent rate the rate

aA + bB → cC + dD expressed in terms of individual
−Δ[𝐴] species must be divided by its
Rate of disappearance of A =
Δ𝑡 stoichiometric coefficient.
−Δ[𝐵]
Rate of disappearance of B = Q. Write the rate expression for
Δ𝑡
Δ[𝐶]
Rate of formation of C = individual species and equivalent
Δ𝑡
Δ[𝐷] rate for following reactions:
Rate of formation of D = a. 2N2O5 → 4NO2 + O2
Δ𝑡
1 Δ[𝐴] 1 Δ[𝐵] 1 Δ[𝐶] 1 Δ[𝐷]
Equivalent rate = - =− = = b. N2 + 3H2 → 2NH3
𝑎 Δ𝑡 𝑏 Δ𝑡 𝑐 Δ𝑡 𝑑 Δ𝑡
c. H2 + I2 → 2HI
Equivalent rate of reaction: the rate of reaction for one mole of
reactant or product is called equivalent rate of reaction.
 7
Q. In a reaction H2 + I2 → 2HI, the rate of disappearance of I2 is found to be
10-6 mole per litre per second. What would be corresponding rate of
appearance of HI?
• Solution:
• 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑑𝑖𝑠𝑎𝑝𝑝𝑒𝑎𝑟𝑎𝑛𝑐𝑒 𝑜𝑓 𝐼2 = −∆[𝐼 2 ]/ ∆𝑡 = 10 − 6
• 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑎𝑝𝑝𝑒𝑎𝑟𝑎𝑛𝑐𝑒 𝑜𝑓 𝐻𝐼 = +∆[𝐻𝐼]/ ∆𝑡 = ?
• We have,
1 +∆[𝐻𝐼]
• 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = −∆[𝐻2 ]/ ∆𝑡 = −∆[𝐼 2 ]/ ∆𝑡 =
2 ∆𝑡
• −∆[𝐼 2 ]/ ∆𝑡 = 1/2 (+∆[𝐻𝐼] /∆𝑡 )
• 10-6= 1/2 (+∆[𝐻𝐼] /∆𝑡)
• +∆[𝐻𝐼]/ ∆𝑡 = 2 ×10-6
• Rate of appearance of HI= 2 ×10-6 mole L-1 sec-1
 Factors affecting rate of reaction:
1. Nature of reactants: 8
During chemical reaction some existing bonds are broken and some new bonds are formed. The strength of bond
determines the rate of reaction as the stronger bonds are difficult to break and more energy is required to beak them
which slows down the rate of reaction.
2. Temperature:
A rise of temperature not only increase the speed of the reaction but in many cases it initiates the reaction. The effect
of temperature on the rates of the chemical reaction can be explained by considering the following two cases:
a. For most of the reactions, the rate of reactions increases with rise in temperature. Generally, the rate of reaction
becomes nearly double or triple for every 10ºC rise in temperature. Large increase in the rate of the reaction is due
to the increase in collision frequency & increase in effective number of collision.
b. A large number of the reaction are known which do not takes place at room temperature but occur rapidly at high
temperature. The effect of temperature on the rate of reaction was studied by Arrhenius and the Arrhenius equation
is given as
K = A e-Ea/RT
Where,
K = rate constant Ea = activation energy
A = Arrhenius constant R = universal gas constant
T = absolute temperature
3. Concentration:
9
Since,
𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑎𝑟𝑡𝑖𝑜𝑛
rate of reaction =
𝑡𝑖𝑚𝑒
the rate of reaction increases with increase in concentration of the reactants.
4. Surface area:
Surface area of the reactant also alters the rate
of reaction. Larger the surface area of the
reactant, higher will be the rate of effective
collision and higher will be the rate of reaction.
5. Catalyst:
Catalyst also alters the rate of chemical
reaction. Positive catalyst increase the rate of
reaction but negative catalyst decreases the rate
of reaction
RATE LAW EXPRESSION or RATE LAW or RATE EQUATION:
An equation which expresses the relation between rate of the reaction and concentration of the
reactant present in the given chemical reaction is called the rate equation or rate law. 10
Let us consider a general reaction;
nA → Product
The rate equation for this equation is,
Rate ∝ [A]n
R = k [A]n
Where, k is proportionality constant.
Unit of rate constant:
Let us consider a general reaction;
nA → Product
The rate equation for this equation is, − −
1 1
Rate ∝ [A]n 𝑚𝑜𝑙 𝑙𝑡𝑟 𝑡𝑖𝑚𝑒
k= −
R = k [A]n 𝑚𝑜𝑙 𝑙𝑡𝑟 1 𝑛
Where, k is proportionality constant. = mol1-n ltrn-1 time-1
Now, k = 𝑛
𝑅 = (mol ltr-1)1-n time-1
𝐴
We know that unit of rate = molLit-1 time -1and unit of concentration = mol/ltr
 11
Cases:

i. For zero order reaction (n = 0) −

1
𝑚𝑜𝑙 𝑙𝑡𝑟 𝑡𝑖𝑚𝑒
−
1

k = [mol Ltr -1 ]1-0 time-1 k= −

𝑚𝑜𝑙 𝑙𝑡𝑟 1 𝑛
= mol Ltr-1 time-1 = mol1-n ltrn-1 time-1
ii. For first order reaction (n = 1) = (mol ltr-1)1-n time-1
k = [mol Ltr -1 ] 1-1 time-1
= [mol Ltr -1 ]0 time-1
= time-1
iii. For the second order reaction (n = 2)
k = [mol Ltr -1 ]1-2 time-1
= Ltr mol-1 time-1
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Half Life (t1/2 or t0.5):

A time at which half of the concentration of reactant is changed into the product or the time at
which half of the reaction is completed is called half life of the reaction. It is denoted by a symbol
t1/2 or t0.5.
 13
Order & Molecularity of Reaction:

Order of Reaction:
The sum of power of concentration terms in the rate equation on which the rate of reaction
actually depends is called the order of the reaction. In order words, it is defined as the sum of
concentration terms present in a balanced chemical equation.
Let us consider a general reaction where “x” mol/lit of A combines with “y” mol/lit of B and
gives product.
i.e. xA + yB → Product. Rate =k [A]x [B]y
Order of reaction = x + y
Molecularity of reaction:
It is the sum of the number of molecules present in the rate determining step of a balanced
chemical equation.
Difference between order & molecularity of reaction:
The basic difference between order and molecularity of reaction are: 14

Order of reaction Molecularity of reaction

It is the sum of the power of concentration
term on which the rate of reaction actually
depends.
It is an experimentally determined value.
It's value can be fractional, zero or whole
number.
It can be changed with external condition.
It has certain unit.
It is the sum of the number of molecules
present in rate determining step of balanced
chemical equation.
It is determined theoretically.
It's value can never be fractional & zero. It
is always in simple whole number.
It is invariant (can't be changed with
external condition).
It has no unit.
 Classification of reactions on the basis of order of reaction:
1. First order reaction: 15
The reaction in which the rate of reaction is directly proportional to the concentration of only one
reactant is called of first order reaction.
A reaction; A → product
is said to be first order if,
Rate, R = k[A]
−𝜕[𝐴]
or = k[A]
𝜕𝑡
If the concentration of reactant is doubled, the rate also gets doubled.
Some examples of first order reaction are,
CH3CH2Cl(g) → HCl(g)+C2H4(g) Rate = k[CH3CH2Cl]
2N2O5→ 4NO2 + O2 Rate = k[N2O5]

2.Second order reaction:

A reaction is said to be second order if the rate of reaction depends on the concentration of two reactant.
The two variable concentration terms on which the rate depends may or may not be same.
A reaction; A → product
is said to be second order if,
Rate, R = k[A]2
16
−𝜕[𝐴]
or = k[A]2
𝜕𝑡
Or for a reaction, A + B → product Rate, R = k[A][B]
If the concentration of reactant is doubled, the rate of reaction will be four times.
Some examples of second order reaction are,
H2 +I2 → 2HI Rate, R = k[H2] [I2]
2NO2 → 2NO + O2 Rate, R = k [NO2]2
3. Zero order reaction:
Reactions in which the concentrations of the reactant does not affect the rate of reaction or the
reaction in which concentrations of the reactant do not change with time are called zero order
reactions.
A reaction; A → product Some examples of zero order reaction are,
is said to be zero order if, H2 + Cl2 → 2HCl R=k
Rate, R = k[A]0 2NH3 → N2 + 3H2 R=k
−𝜕[𝐴]
or = k[A]0 = k
𝜕𝑡
4. Pseudo- order reactions:
The reactions which seem to be of some order but actually follow different order kinetics 17 are
called pseudo order reactions.
Let us consider a reaction,
CH3Br + OH− → CH3OH+Br−
Rate law for this reaction is,
Rate = k [OH−] [CH3Br] (second order)
Rate = k [OH−] [CH3Br]
= k (constant) [CH3Br]
=k ′[CH3Br] (first order)
As only the concentration of CH3Br would change during the reaction, the rate would solely
depend upon the changes in the CH3Br reaction.
Hence, the above reaction seems to be of second order but actually follows first order kinetics.
Similarly, the hydrolysis of ethyl acetate (ester)
CH3COOC2H5 + H2O → CH3COOH + C2H5OH (in acidic medium)
This reaction is first order with respect to ethyl acetate but appears to be second order.
 MOLECULARITY OF REACTION:
Chemical reactions are of two types; 18
1. Elementary reactions
2. Complex reactions
Elementary reactions:
Those reactions which occur in single step are called elementary reactions.
Molecularity of elementary reactions:
1. Unimolecular reactions: A reaction involving only one molecule in balance equation are called
unimolecular reaction. (molecularity = 1)
(COOH)2 → CO2 + CO + H2O
2. Bimolecular reactions: A reaction involving two molecules in balance equation are called
bimolecular reaction. (molecularity = 2)
H2 + I2 → 2HI
3. Trimolecular reactions: A reaction involving three molecules in balance equation are called
trimolecular reaction. (molecularity = 3)
2H2 + O2 → 2H2O
NUMERICALS:
Q. For a reaction , 2NH3⇾ N2 + 3H2 , the rate of decomposition of
-6
20
ammonia is 2.1 x 10 mole per litre per second. What are the rate of
formation of N2 & H2 ?
Solution: Given that,

21
𝑑[𝑁𝐻3]
The rate of decomposition of NH3 = - = 2.1x 10 -6 mole per litre per second
𝑑𝑡
𝑑[𝐻2]
The rate of appearance of H2 = =?
𝑑𝑡
𝑑[𝑁2]
& the rate of appearance of N2 = =?
𝑑𝑡
1 𝑑[𝑁𝐻3] 𝑑[𝑁2] 1 𝑑[𝐻2]
Now, equivalent rate = - = =
2 𝑑𝑡 𝑑𝑡 3 𝑑𝑡
𝑑[𝑁2] 1
or, = x 2.1x 10 -6
𝑑𝑡 2
𝑑[𝑁2]
⟹Rate of formation of N2= =1.05x 10 -6 mole per litre per second
𝑑𝑡

Again,
1 𝑑[𝑁𝐻3] 1 𝑑[𝐻2]
or, - =
2 𝑑𝑡 3 𝑑𝑡
1 1 𝑑[𝐻2]
Or, x 2.1x 10 -6=
2 3 𝑑𝑡
𝑑[𝐻2] 3
Or, = x 2.1x 10 -6 = 3.15x 10 -6 mole per litre per second
𝑑𝑡 2
𝑑[𝐻2]
⟹Rate of formation of H2 = = 3.15x 10 -6 mole per litre per second.
𝑑𝑡
 Q. The rate of reaction, 2A ⇾ product, becomes 3 times when concentration
of “A” is increased by 27 times. Find the order of reaction. 22

Solution,
Let the general rate equation of this reaction,
R = k [A]n ......................(i) where , n= order of reaction
By question,
3R = k[27A] n ………………(ii)
Now dividing equation (ii) by (i)
3𝑅 k[27A] n
=
𝑅 k [A]n
27A n
or, 3 =[ ]
A
or, 3 = 27n
or,3 = 33n
or, 1 =3n
1
∴n=
3
 23

Q. For a reaction, A+B⇾ C, it is found that,

a) Rate becomes double when [A] is doubled.
b) Rate becomes 16 times when concentration of both A & B
are doubled. Calculate the order of reaction with respect to
each reactant and overall order. Also write the rate expression.
Solution:
The general rate equation of the reaction, 24
R = k[A]x [B] y ………………….(i)
Where, k = rate constant
x= order of reaction with respect to A
y= order of reaction with respect to B
x + y = overall order of reaction
By question,
2R = k[2A]x [B] y ………………….(ii)
16R = k[2A]x [2B] y ……………..(iii)
Now dividing equation (ii) by (i) Again dividing equation iii by ii ∴overall order= x+y=1+3= 4
2R k[2A]x [B] y 16R k[2A]x [2B] y
𝑜𝑟, = ⟹ = ⟹∴The rate expression, R = k[A]1 [B] 3
R x
k[A] [B] y 2R x
k[2A] [B] y

Or 2 = 2x or, 8 = 2y
or, x = 1. y=3
Q. For a reaction, A+B⇾C, it is found that, 25

a)Rate becomes 32 times when [A] &[B] are doubled.

b)Rate becomes 4 times when concentration of B is doubled
keeping that of A constant . Calculate the order of reaction
with respect to each reactant and overall order. Also write
the rate expression.
Solution:
The general rate equation of the reaction,
26
R = k[A]x [B] y ………………….(i)
Where, k =rate constant
x= order of reaction with respect to A
y= order of reaction with respect to B
x + y = overall order
By question,
32R = k[2A]x [2B] y ………………….(ii)
4R = k[A]x [2B] y ……………..(iii)
Now dividing equation (iii) by (i) Again dividing equation ii by iii ∴overall order= x+y=3+2= 5
4R k[A]x [2B] y 32R k[2A]x [2B] y
𝑜𝑟, = ⟹ = ⟹∴The rate expression,
R k[A]x [B] y 4R k[A]x [2B] y
Or 4 = 2y or, 8 = 2x R = k[A]3 [B] 2
or, y = 2 x=3
.
Q. Write the rate law for the reaction which is second order with respect to A and zero order with
respect to B.
27
Solution:
R= k[A]2 [B] 0
Or, R = k[A]2

Q. The reaction, A+B⇾ C ,is a second order reaction. Write three different rate law
expression which may be true to the above reaction.
Solution: The possible rate law expression for the above second order reaction are
R = k[A]1 [B] 1
R = k[A]2 [B] 0
R = k[A]0 [B] 2
Q. For the reaction 2NO(g) + Cl2(g)⇾2NOCl(g), the following data 28
are
obtained:
Experiment [Cl2] mole L-1 [NO] mole L-1 Rate (mole L-1 sec-1)
1. 0.02 0.01 2.4x10-4
2. 0.02 0.03 2.16x10-3
3. 0.04 0.03 4.32x10-3

Determine the order of reaction w.r.t.Cl2, NO, overall order & rate law for
the reaction. Also calculate the rate constant.
Let the rate of reaction be,
R = k [Cl2]x[NO]y
2.4 X 10-4 = k [0.02]x[0.01]y……….(i)

2.16 X 10-3 = k [0.02]x[0.03]y……….(ii)

4.32 X 10-3 = k [0.04]x[0.03]y……….(iii)
Dividing equation (ii) by (i)
2.16x10−3 k[0.02]x [0.03] y
= 29
2.4x10−4 k[0.02]x [0.01] y
Or, 9 = 3y
Or 32 = 3y
∴y = 2
Again , dividing equation (iii) by (ii)
4.32x10−3 k[0.04]x [0.03] y
=
2.16x10−3 k[0.02]x [0.03] y
Or, 2= 2x
∴ x =1
And overall order= x + y = 2+1= 3
Substituting the value of x & y in equation(ii) , then
2.4x10-4 =k[0.02]1 [0.01]2
∴k =120 litre2 mole -2 sec -1
 KINETICS STUDY OF DIFFERENT ORDER OF REACTIONS:

ZERO ORDER REACTION: 30

Reactions in which the concentrations of the reactant does not affect the rate of reaction or the
reaction in which concentrations of the reactant do not change with time are called zero order
reactions.
Reaction between hydrogen & chlorine in absence of light.
H2 + Cl2 → 2HCl
Let us consider a general zero order reaction where reactant A gives product,
A → product
Initially, at t = 0 a 0
At, t = t (a – x) x
Now, rate of reaction at time t is,
𝑑𝑥
∝ (a – x)0 n = 0, for zero order reaction
𝑑𝑡
𝑑𝑥
or, = k0 (a – x)0
𝑑𝑡
𝑑𝑥
or, = k0………….. (i)
𝑑𝑡
(a – x)0 = 1 and k0 is the rate constant of zero order reaction.
 or, dx = k0dt –––––– (ii)
Integrating equation (ii) we get,
31
 dx =  k0dt
x = kot + C ––––– (iii)
Where C is integration constant and its value can be obtained by applying the initial condition i.e.
at t = 0, x = 0
So equation (iii) becomes
0 =k0×O + C
C=O
Substituting value of C in equation (iii)
Or, x = kot
𝑥
or, k0= ––––––––– (iv)
𝑡
Equation (iv) is required integrated rate equation of zero order reaction.
HALF LIFE OF ZERO ORDER REACTION:
We have integrated rate equation of zero order reaction
𝑥 32
ko = –––––– (i)
𝑡
Where,
x = concentration of product
t = time
ko = rate constant for zero order reaction
At half life, t = t1/2 and x = a/2
So equation (i) becomes
𝑎/2
ko =
t1/2
𝑎
ko =
2 t1/2

𝑎
t1/2 = 0r, t1/2α a …………….(ii)
2𝑘0
Equation (ii) shows that half life of zero order reactions is directly proportional to initial
concentration of the reaction.
 33
First order reaction
The reaction in which the rate of reaction is directly proportional to the
concentration of only one reactant is called of first order reaction. For example,
Hydrolysis of ester of acidic medium.
+
H
CH3COOC2H5 + H2O → CH3COOH + C2H5OH
This reaction is also an example of pseudo first order reaction.
Derivation:
Let us consider a general first order reaction where reactant A gives product.
A → Product
Initial at t = 0 a molL–1 0
At t = t (a – x) molL–1 x molL–1
Now, the rate of reaction at time t
dx
dt  (a – x) 1

dx
i.e. dt =k1 (a – x) –––––– (i)
Where k1 is the rate constant of first order reaction.
 34
Equation (i) is the differential rate equation of first order reaction
Rearranging equation (i)
dx
(a – x) = K1dt –––––– (ii)
On integrating equation (ii)
 dx
 = K1dt
 (a – x)
or, – ln(a – x) = k1t + c
Where C is integration constant and its value can be obtained by applying initial
condition.i.e,at t = 0 and x = 0, then
– ln(a – x) = k1t + (– lna)
– ln(a – x) + lna = k1t
 a 
ln a – x = K1t
 
 a 
2.303 log a – x = k1t where ln = 2.303 log
 
2.303  a 
K1 = log   ––––––– (iv)
t  a – x
Equation (iv) can be expressed as
2.303 Co
K1 = log   ––––––– (v)
t  Ct
Where, Co = concentration of reactant at t = 0
Ct = concentration of reactant at t = t
HALF LIFE TIME OF FIRST ORDER REACTION:
35

We have,
The integrated rate equation for first order reaction,
2.303 𝑎
K1 = log ( )………..(i)
𝑡 𝑎−𝑥
At half life,
𝑎
t = t1/2 and x =
2
Therefore, equation (i) becomes,
2.303 𝑎
K1 = log
𝑡1 2
𝑎/2
/
t1/2 = 0.693/ k1…………(ii)
Above equation shows that half life of first reaction is independent with initial
concentration of reactant.
 36

Numericals
1. A first order reaction is 40% completed in 50 min. calculate the value of
rate constant. In what time, will the reaction be 80% completed?
 Solution: 37
Given,
Product (x) = 40
Reactant (a) = 100
time (t) = 50 min
i. Rate constant (k1= ) = ?
We know that,
2.303  a 
k1 = t log  a – x
 
2.303  100 
log  
50  100 – 40
or, k1= 1.02×10–2 min–1

ii. If product (x) = 80

then time (t) = ?
We know that,
2.303  a 
k1 = t log  a – x
 
2.303  100 
or, 1.02×10–2 = t log  100 – 80
 
2.303 100
or, t = 1.02×10–2 log  20 
 
 t = 157.81 minutes.
 38

2. Show that in case of first order reaction, the time required for
99.9% of the reaction to take place is about 10 times than that
required for the half life of the reaction?
 39
Solution,
We know that,
Rate constant of a reaction is constant at a particular condition (temperature)
and is independent on concentration.
From above question
k 1 = k1
2.303  100 
or, t log 100 – 99.9 = 2.303/t ½ .log[100/50]
99.9  
100 100
or, t 1 log  0.1  = t99.9 log  50 
2    

or, t 1 × 3 = t99.9 × 3.01 ×10–1

2
or, t 1 × 10 = t99.9
2
Hence proved.
 40

3.A first order reaction is 20% complete in

20 minute. How long will it take for 80%
completion?
 41
Solution:
Given,
Initially concentration of reactant (a) = 100
concentration of product (x) = 20
time (t) = 20 min
Finally concentrationof product (x') = 80 time (t') = ?
We know that
2.303  a 
k1 = 20 log a-x
 
2.303  100 
or, k1 = 20 log 100 - 20
 
or, k1 = 1.115×10-2
Now again
2.303  a 
k1 = t' log a-x'
 
2.303  100 
or, 1.115×10-2 = t' log 100-80
 
or, t1 = 144.25 min
 42
4 If a first order reaction is one quarter complete in 100 minutes. What is
specific rate constant for a reaction?
Give
Concentration of reactant (a) = 1
1
Concentration of product (x) = 4
Time (t) = 100 min
Specific rate constant (k1) = ?
we know that
2.303  a 
k1 = t log a-x
 
2.303  1 
or, k1 = 100 log 1-1/4
 
or, k1 = 2.87 × 10-3 min-1
 43
5 A first order reaction is 20% complete in 30 minutes. How long it will take
to be 50% complete.
Given
Initial concentration of reactant (a) = 100
Concentration of production (x) = 20
Time (t) = 30min
Final concentration of product (x') = 50
Final time (t') = ?
We know that
2.303
k1 = t log (a/a-x)
2.303  100 
or, k1 = log  
30 100-20
k1 = 7.4 × 10-3 min-1
Now, again we know that
2.303  a 
k1 = log  
t' a-x'
2.303  100 
or, 7.4×10-3 = log  
t' 100-50
or, t' = 93.18min
6 44
A first order reaction is 75% completed in 60 minutes. Calculate
half-life of the reaction?
Given
Initial concentration of reactant (a) = 100
Concentration of product (x) = 75
Time taken (t) = 60min
Half life of reaction (t½) = ?
We know that
2.303  a 
k1 = log  
t a-x

k1 = 2.310×10-2 min-1
Now, again we know that
0.693 0.693
t1/2= =
k1 2.310×10-2
 Half life of the reaction (t½) = 29.96 min
 45
7 For a first order reaction it takes 5 minutes for initial
concentration of 0.6 mol lit-1 of reactant to become 0.2mol lit-1.
Find out the half life of reaction?
Given
Initial concentration of reactant (a) = 0.6 molL–1
Final concentration of reactant (a – x) = 0.2 molL–1
Time taken (t) = 5 min
Half life (t½) = ?
We know that
2.303  a 
k1 = log  
t a – x
2.303 0.6
or, k1 = log  
5 0.2
or, k1 = 2.1976×10–1 min–1
Now, again we know that
0.693
t½ =
K1
0.693
=
2.1976×10–1
 Half life (t½) = 3.1534 min
8 For a first order reaction, the rate constant is 2.2×10 –5 sec–1.
46
Calculate the fraction of reaction consumed in 1 hour and 30
minutes.
Given,
Rate constant of reaction (k1) = 2.2×10–5 sec–1
Time taken (t) = 1 hr and 30 min
= 60×60 + 30×60 = 5400 sec
x
Fraction of reactant consumed   = ?
a 
We know that,
2.303  a 
k1 = log  
t a – x
2.303  a 
or, 2.2×10–5 = log  
5400 a – x
 a 
or, 5.156 = log  
a – x
 a 
or,   = 1.126
a – x
a – x 1
or, =
a 1.126
a x
or, – = 8.86×10–1
a a
x
or, = 1.119×10–1
a
9 A first order reaction has its rate constant value 1.5×10–6 sec–1. If the reaction is allowed
for 10 hours = 36000 seconds, then what percentage of initial concentration of reaction
would be changed into product? Also calculate half-life.
Given,
47
Rate constant (K1) = 1.5×10–6 sec–1
Time taken (t) = 10 hrs = 36000 sec
Let, initial concentration of reaction (a) = 100
Then, concentration of product (x) = ?
half life (t½) = ?
We know that
2.303  a 
K1 = log a – x
t  
2.303  100 
or, 1.5×10-6 = 36000 log 100–x
 
 100 
or, 2.344×10-2 = log 100–x
 
100
or, 1.0554 = 100-x
or, 100-x = 94.74
or, x = 5.255%
 Percentage of reactant that would be change into product
(x) = 5.255%
Again,
0.693
Half–life (t½) =
k
0.693
or, t½ = 1.5×10-6
 t½ = 462000sec or 128.33hrs
10
48
A first order reaction is 20% completed in 10 minutes. Calculate time taken by the reaction for
75% completion.
Given,
Initial concentration of reactant (a) = 100
i. Initial concentration of product (x) = 20
Initial time taken (t) = 10min
ii. Concentration product (x') = 75
Time taken (t') = ?
We know that
k1 = k1
2.303
log  a  = 2.303 log  a 
t a - x t' a - x'
or,
2.303
log  100  = 2.303 log  100 
10 100 - 20 t' 100 - 75
 100 
100 - 75
or, t' 10 × 10×log
log 100 - 20
100
 
 t' = 62.125 min
❖11. At 25ºC, the half-life period of the decomposition of N2O2 is 5 hours & is independent
49
of the initial concentration of N2O2. Calculate the specific reaction rate & time required
for 90% decomposition.
Given,
Half-life (t½) = 5hours
Specific rxn rate (rate constant) (K1) = ?
If concentration of product (x) = 90%
time taken (t) = ?
We know that
0.693 0.693
t½ = 5  t½ = k1
0.693
or, K1 = = 0.1386 hr-1
5
Again, we know that
2.303  a 
K1 = log  
t  a - x
2.303  100 
or, t= log  
0.1386 100 - 90
 time taken (t) = 16.61 hours.
Second order reaction: 50
A reaction is said to be second order if the rate of reaction depends on the
concentration of two reactant. The two variable concentration terms on which
the rate depends may or may not be same.
Case-1
When two reactant molecules are same with same initial concentration:
Let us consider a general reaction as
A + A → product
Initially at t = 0 a molt-1 a mollit-1 O
finally at t=t (a-x) mollit-1 (a-x) mollit-1 2x
Now, the rate of reaction at time t
dx
dt  (a-x) (a-x)
dx
dt  (a-x) 2

dx 2
dt = k2 (a-x) ... (i)
Where k2 rate constant and equation (i) is the differential rate calculation
of second order reaction.
 Rearranging equation(i) we get

51
dx
= k2dt .......... (ii)
(a-x)2

Integrating eqn (ii) (a-x)-2+1

 dx
(a-x)2 = – -2+1
 dx 
(a-x)2 = k
 2dt
 – (a -x)-1 1
= –1 = (a-x)
or, 1/(a-x) = k2t + C ............ (iii)
When C is the integration constant whose value can be obtained by substituting the initial
condition of reaction i.e. at t = 0, x = 0

or, C = 1/a ...... (iv)

Substituting value of C in eqn (iii)
1 1
(a-x) = k 2t +
a
1 1
or, (a-x) – a = k2 t
a-a+x
or, a(a - x) = k2t
a
k2t = a(a - x)

x
or, k2 = at(a - x) ......... (v)

Equation (v) is the integrated rate eqn for second order equation when two reacting molecules
are same with same initial concentration.
Half-life of second order reaction:
52
At half-life t = t½ & x= a/2 So, eqn (i) becomes
a
/2
k2 = a t½(a-a/ )
2
1
or, k2 = 2t½ (a/2)

1
or, K2 =
at½

1
Note : t½  an-1 Relation between half-life and initial conn of reactant.

1 1 1
or, t½ = ak or, t½ = k . a
2 2

1
 t½  a

Above reaction shows that half-life of second order reaction is inversely proportional with
the initial concentration of reactant.
 1 ln  a-x b
or, k2t = (a-b)  b-x a 53
   
1 b(a-x)
or, k2 = (a-b)t ln a(b-x)
1 b (a-x)
or, k2 = (a-b)t 2.303 log a (b-x) ......... (v)
 
Where eqn (v) is the integrated rate eqn for 2nd order reaction when the
concentration of two reactants are not same.

Temperature coefficient (T)

It is the ratio of rate constants of a reaction at two different temperature different
with each other by 10ºC. It is denoted by a symbol (T). The value of T is nearly
equal to two.
T=
Where,K35=rate constant of the reaction at 350C
K25 = rate constant of the reaction at 250C
Arrhenius equation 54
The effect of temperature on the rate constant of rxn was studied by Arrhenius
and the eqn which is expressed
k = Ae(-Ea/RT) .................. (i)
Where k = rate constant of the rxn
A = collision frequency factor (Arrhenius frequency factor)
Ea = activation energy
R = Universal gas constant (8.314 jmol l-K-1
T = absolute temperature
Validity of Arrhenious equation
We have Arrhenious eqn
-Ea
k = Ae Rt .......... (i)
Taking ln common on both sides we get
lnk = lnA + lne -Ea/Rt
Ea
or, lnk = lnA – RT
Ea 1
or, lnk = lnA – . ......... (ii)
R T
Eqn (ii) is in the form of y = mx + C where y = lnK, C = lnA,
m = -Ea/R , x = 1/T 55
-Ea
So, when we plot graph between lnk verses 1/T we get a straight line with slop & intercept
R
lnA.
From intercept we can determine the value of A & from slop we can determine the value of
activation energy.

lnA
lnK

1/T
Fig: lnk Vs 1/T plot
If the rxn is carried out at two different temperature T1 & T2. Then eqn II can be modified as
Ea 1
lnk1 = lnA – ........... (iii)
R T1
Ea 1
lnk2 = lnA – ............ (iv)
R T2
 56
Now, subtracting eqn (iii) from eqn (iv) we get
Ea 1 Ea 1
lnk2 – lnk1 = lnA – – lnA +
R T2 R T1
k2 Ea 1 Ea 1
ln k = - R T + R T
1 2 1
k2 Ea  1 1 
ln k = R T – T 
1  1 2
k2 Ea T2 – T1
or, 2.303 log k = R  T T 
1  1 2
k2 Ea T2 – T1
or, log k = 2.303k  T T  ........... (v)
1  1 2 
Equation (V) is the required equation.
Activation energy: 57
For a reactant molecule to concert in to product, they must have certain amount of energy called threshold
energy. If reactant molecule originally does not have theis energy, certain extra amount of energy is to be supplied, so
as to make their energy equal to or greater than threshold energy. This extra amount of energy is called activation
energy. It is denoted by a symbol Ea.
SIGNIFICANCE:
LOWER IS THE VALUE OF ACTIVATION ENERGY HIGHER WILL BE THE RATE OF REACTION.

Ea
Eth
P.E.
reaction
Ex. product
progress 8 rxn
FIG:energy profile diagram showing the activation energy.
Energy profile diagram:
58
Eth
Ea

P.E.
reaction
product

progress of rxn
Fig: Energy profile diagram for exothermic rxn

Ea
Eth

P.E.
product
reaction

progress of rxn
Fig: Energy profile diagram for endothermic rxn
 Ea in absence of catalyst 59
Ea in presence of the catalyst

P.E.
reaction

product
progress of rxn
Fig: Energy profile diagram showing lowering of Ea in presence of the positive catalyst

Ea in presence of -ve catalyst

Ea in absence of catalyst

P.E.
reaction

product
progress of rxn
Fig: Energy profile diagram showing increasing of Ea in presence of negative catalyst.
 60
Relation between half life, initial concentration & order of rxn.
For zero order reaction t½  a
For fist order reaction
1 0.693
t2 = K
1
For second order reaction
1
t a
1
2
From above reaction use conclude that
1
t  (a)n-1
1
2
Where n = order of reaction
 Collision theory of Bi-molecular reaction:
61
According to this theory reactant molecules convert into product only when they collide to each other. Not all
the collision can gives product in a chemical reaction. The collision that can result into a product in a chemical rxn is
called effective collision. For a collision to be effective, two molecules must collide with sufficient amount of energy
i.e. energy equal to or greater than threshold energy.
Hence only effective collection is proper orientation gives product in a chemical reaction.
Example: 1
A2 + B2 → (2AB) product
Mechanissm
A B A B
+ 2AB
A B A B
Fig: Effective collection in proper orientation.

A A + B B

A A B B
No product
Fig: Collision in improper orientation
If 'k' is the specific reaction rate constant Z is the total number of collision per cc per second &
f is the fraction of molecules that are activated then K = z.f .......... (i)
• The collision theory of reaction rate can be summarized as:
1. The chemical reaction takes place only when the reactants molecules collide with each other.
2. The colliding molecules should have sufficient energy to cross the energy barrier.
62
3. Only a fraction of molecules have energy equal to threshold energy and can form products. The reactants
having average energy should be provided by some additional energy so that it can form products. The
minimum amount of additional energy is called activation energy. i.e, Ea = ET - Eav
4. Only the molecules with properly orientation are said to have effective and the molecule with improper
orientations are said to have effective collision.
5. The molecules with proper orientation can form products whereas the molecules with improper
orientation cannot form products.
6. The conversion of reactant to product is not direct. An unstable product named activated complex is
formed between reactants and products at the top of energy barrier. The decomposition of which
produces products.
7. The rate of chemical reaction by collision theory is given by,
• Rate= fpz;
where, • f= fraction of molecules which possesses sufficient kinetic energy to react
• p= probable fraction of collision with proper orientations and
• z= collision frequency.
8. The height of hill (energy of activation) determines the rate of reaction. If Ea is high reaction is slow. If
Ea is less the reaction is fast and if Ea = 0, the reaction is instantaneous.
 63

Pseudo order reaction:

The reaction which appears to be a higher order but actually follow a
lower order kinetics is called pseudo order rxn. For example:
A + B → Product
(excess)
The rate of rxn
R = K[A][B]
Here, [B] = constant
So, the actual rate , R = K'[A]
Where K' = K[B] = constant.
Specific example
Hydrolysis of ester in acidic medium is a pseudo first order reaction.
+
H
CH3OCOOC2H5 + H2O  CH3COOH + C2H5OH
excess