UNIT-7 CHEMICAL KINETICS

 What is Rate of a chemical reaction?

The change in the concentration of the reactant per unit time gives the rate of the reaction.
A ⎯⎯⎯→Products
-Δ  A 
Rate =
Δt
 What is the Unit of rate of a reaction?
molL-1
unit of rate = = molL-1s-1
s
for gas phase reaction:
unit of rate = atm s-1
 How rate of a reaction is related to its Stoichiometry?
In a reaction, A ⎯⎯→B , the stoichiometry of both reactant and product are same.
Rate of disappearance of A = Rate of appearance of B
-d[A] +d[B]
Rate = =
dt dt
In a reaction, A ⎯⎯→ 2B , the stoichiometry of reactant and product are not same.
For every mole of A that disappears two moles of B appear,
+d[B]  -d[A]
Rate = =2  
dt  dt 
 -d[A]  +1  d[B]
Rate =   =  
 dt   2  dt
The rate of formation of B is twice as fast as the rate of disappearance of A.
For a general reaction….
xA + yB ⎯⎯⎯
→ lC + mD

-1  d[A]  -1  d[B]  1  d[C]  1  d[D]

Rate=   =  =  = 
 x  dt  y  dt  l  dt  m  dt
 What are average and instantaneous rate of a chemical reaction?
 Average rate: The change in concentration of a reactant (or product) of a chemical
reaction in a given interval of time is called as an average rate.
-Δ  A 
Average Rate =
Δt
 Instantaneous rate: The change in concentration of a reactant or product of a chemical
reaction at a given instant is called an instantaneous rate.
-d A 
Instantaneous Rate =
dt

Unit – 7 chemical kinetics The Turning Point 1

 Define rate law.
The rate of the reaction depends upon the concentration of the reactant. For any general
reaction.
xA + yB ⎯⎯⎯→ products
The rate law for the above reaction is generally expressed as
Rate = k [A]m[B]n
Where k is called the rate constant.
 Define rate constant.
Rate constant of a reaction is defined as “Rate of the reaction, when the concentration of
each of the reactants in unity”.
For any general reaction.
xA + yB ⎯⎯⎯
→ products
m n
Rate = k [A][B]
Rate
k= m n
[A][B]
If [A]= 1 ; [B]= 1
k = Rate
 Differentiate between rate and rate constant of a reaction.
s.no Rate of a reaction Rate constant of a reaction
1 It represents the speed in which the It is a proportional constant
reactants are converted into products at
any instant.
2 It is measured as decrease in the conc. of It is equal to the rate of reaction, when
the reactants or increase in the the concentration of each of the
concentration of products. reactants in unity
3 It depends on the initial concentration of It does not depend on the initial
reactants. concentration of reactants.

 Define order.
It is the sum of the powers of concentration terms involved in the experimentally
determined rate law. For any general reaction,
xA + yB ⎯⎯⎯→ products
Rate = k [A]m[B]n
order = ( m +n )

Unit – 7 chemical kinetics The Turning Point 2

 Define molecularity.
The total number of reactant species that are involved in an elementary step is called
molecularity of that particular step. For example:
The decomposition of H2O2 in the presence of I− ion
−
I →2H O(l ) + O ( g )
2H2O2 (aq) ⎯⎯⎯⎯ 2 2

It is experimentally found that the reaction is first order with respect to both H2O2 and I-
-
,which indicates that I is also involved in the reaction.
The mechanism involves the following steps.
slow
Step:1 H2O2 + I- ⎯⎯⎯⎯ → H2O + OI-
fast
Step : 2 H2O2 + OI- ⎯⎯⎯⎯ → H2O + I- + O2

These two reactions are elementary reactions. Step 1 is the rate determining step, since it
involves both H2O2 and I- , the overall reaction is bimolecular.

 Give the differences between order and molecularity of a reaction.

s.no Order of a reaction Molecularity of a reaction
1 It is the sum of the powers of It is the total number of reactant species
concentration terms involved in the that are involved in an elementary step.
experimentally determined rate law.

2 It can be zero (or) fractional (or) integer It always a whole number, cannot be zero
or fractional.
3 It is assigned for an overall reaction. It is assigned for each elementary step of
mechanism.

Unit of rate constants

n
rate = k  A 
rate
k = n
 A 

unit of k =
( mol L-1s-1 )
( mol L-1 )
n

unit of k = mol1-nLn-1s-1

Unit – 7 chemical kinetics The Turning Point 3

 Order Rate Equation Rate Constant Unit of Rate Constant
rate ( molL s )
-1 -1
0
0 rate = k A  k = 0 = molL-1s-1
( molL-1 )
0
 A 

rate ( molL s )
-1 -1
1
1 rate = k A  k = 1 = s-1
( molL-1 )
1
 A 

rate ( molL s )
-1 -1
2
2 rate = k A  k = 2 = mol-1L s-1
( molL-1 )
2
A 

3
k =
rate ( molL-1s-1 )
3 rate = k A  3 = mol-2L2s-1
( molL-1 )
3
 A 

(Find the answer for mcq # 7)

 Give any three examples for the first order reaction.

Decomposition of dinitrogen pentoxide
1 N O ⎯⎯⎯→ 2NO + 1/2O
2 5 2 2

Decomposition of sulphuryl chloride

2 SO2Cl2 ⎯⎯⎯→ SO2 + Cl2
Decomposition of the Hydrogen peroxide in aqueous solution
3 H2O2 ⎯⎯⎯→ H2O + 1/2O2

 Give any three examples for the zero-order reaction.

1 Photochemical reaction between H2 and Cl2
H2 + Cl2 ⎯⎯⎯⎯⎯ light → 2HCl

2 Decomposition of N2O on hot platinum surface

N2O N2 + 1/2 O2
3 Iodination of acetone in acid medium is zero order with respect to iodine.
+
H →ICH COCH + HI
CH3COCH3 + I2 ⎯⎯⎯ 2 3
+
Rate = k [CH3COCH3] [H ]

Unit – 7 chemical kinetics The Turning Point 4

 Derive integrated rate law for a first order reaction.
A reaction whose rate depends on the reactant concentration raised to the first power is
called a first order reaction. Let us consider the following first order reaction
A ⎯⎯⎯
→ product
Rate law can be expressed as
Rate = k [A]1 ~~~~~~~ 1
-d[A]
=k[A]
dt
-d[A]
=kdt
[A]
When time changes from ( t = 0 )  (t = t)
Concentration changes from [A 0 ]  [A]
on Integrating the above equation within these limits
[𝐴] 𝑡
−𝑑 [𝐴]
∫ = 𝑘 ∫ 𝑑𝑡
[𝐴 ]
[𝐴0 ] 0

 
[A] t
-ln[A][A ] = k t 0
0

-ln[A]- (-ln[A0]) = k (t-0)

-ln[A]+ ln[A0]= kt
[A ]
ln  0  = kt ~~~~~~~ 2
 [A]
[A ]
2.303log  0  = kt
 [A] 
2.303 [A ]
k= log  0  ~~~~~~~ 3
t  [A] 
Equation (2) can be written in the form y = m x + c as below
ln[A0]-ln[A]= kt
ln[A]=-kt + ln[A0]
y = mx + c
A plot of (ln[A]) against ( t) mat be drawn. A straight line with negative slope of is
obtained. From this, the rate constant is calculated.
 What is pseudo first order reactions? Give an example.
“In a second order reaction, when one of the reactants concentrations is in excess of
the other then the reaction follows a first order kinetics, such reactions are called
Pseudo first order reactions.” Example: Acid hydrolysis of an ester.

Unit – 7 chemical kinetics The Turning Point 5

 Derive integrated rate law for a zero-order reaction.
A reaction in which the rate is independent of the concentration of the reactant over a wide
range of concentrations is called as zero order reactions. Such reactions are rare. Let us
consider the following hypothetical zero order reaction.
A ⎯⎯→ product
Rate = k[A]0 ~~~~~~~ 1
-d[A] = k
dt ([A]
0
)
=1

-d[A] = k dt
When time changes from ( t = 0 )  (t = t)
Concentration changes from [A 0 ]  [A]

On integrating the above equation within these limits

[A] t
- d[A] = k dt
[A0] 0

( )[A ] =k (t)0
[A] t
-[A]
0

-[A]- (-[A0]) =k(t-0)

[A0]-[A]=kt ~~~~~~~ 2

[A0]-[A]
k = ~~~~~~~ 3
t
Equation (2) can be written in the form y = m x + c as below

[A]=-k t + [A0]
y = mx+c
A plot of ([A] Vs t) gives a straight line with a slope of -k and y - intercept of[A0].

Unit – 7 chemical kinetics The Turning Point 6

 Define half-life of a reaction. Show that for a first order reaction half-life is independent of
initial concentration.
The half-life of a reaction is defined as the time required for the reactant concentration to
reach one half its initial value. The rate constant for a first order reaction is given by
[A ]
k = 2.303log 0
t [A]
[A ]
when t=t1/2 ; [A]=  0 
 2 
  [A0]
k =  2.303 log
 t1/2  [A ]
 0 
 2 
 

k= 2.303log2
t1/2
k= 2.303 × 0.3010 = 0.6932
t1/2 t1/2
t1/2 = 0.6932
k
Half-life period is independent on the initial concentration and it is a constant.
 Derive an equation for the half-life period of a zero-order reaction.
The rate constant for a zero-order reaction is given by
[A0]-[A] [A ]
k = when t = t1/2 ; [A]=  0 
t  2 

[A0] - [A0]
k =  2 
t1/2
[A0]
k =
2t1/2
[A0]
t1/2 =
2k
The half-life of a zero-order reaction is directly proportional to the initial concentration of
the reactant.
 Write Arrhenius equation and explains the terms involved.
 
−  Ea 
 RT 
 
The rate constant is directly proportional to e .Arrhenius proposed a relation between
the rate constant and temperature.
 
A - Frequency factor; R - gas constant;
−  Ea 
 RT 
k =A e   E a - Activation Energy; T -Temperature (in K)

Unit – 7 chemical kinetics The Turning Point 7

 Derive an equation to calculate energy of activation of a chemical reaction by graphical
method.
 Arrhenius proposed a relation between the rate constant and temperature.
 
−  Ea 
 RT 
k =A e  
~~~~~~~~ 1
 The frequency factor (A) is related to the frequency of collisions (number of collisions per
second) between the reactant molecules. The factor A does not vary significantly with
temperature and hence it may be taken as a constant.
 Ea is the activation energy of the reaction, the minimum energy that a molecule must
possess to react.
 Taking logarithm on both side of the equation {1}
 Ea 
- 
 RT 
lnk =lnA + lne
E 
lnk =lnA-  a  ( ln (e) =1)
 RT 
 Ea   1 
lnk =lnA-     ~~~~~~~ 2
 R  T
The above equation () is of the form of a straight line y = c + mx .

( )
 A plot of (lnk ) Vs 1T gives a straight line with a negative slope  − a  . From the
E
 RT 
value of slope, we can calculate the energy of activation.

 Derive an equation to calculate energy of activation of a chemical reaction from its rate
constants at different temperatures.
Arrhenius proposed a relation between the rate constant and temperature.
E 
a
- RT 
k =A e  
~~~~~~~~ 1
If the rate constant for a reaction at two different temperatures are known, we can calculate
the activation energy as follows.
At temperature T = T1 ; the rate constant k = k1
 Ea 
lnk1 =lnA-   ~~~~~~~~ 2
 RT1 
At temperature T = T2 ; the rate constant k = k2
 Ea 
lnk2 =lnA-   ~~~~~~~~ 3
 RT2 

Unit – 7 chemical kinetics The Turning Point 8

 3 − 2
 Ea   Ea 
lnk2 -lnk1 = -  +   ~~~~~~~~ 4
RT
 2  1 RT
 k2  Ea  1 1 
ln   =  - 
 k1  R  T1 T2 
 k2  Ea  T2 -T1 
2.303log   =  
k
  R  T1T2 
1

 k2  Ea  T2 -T1 
log   =   ~~~~~~~~ 5
 k1  2.303R  T1T2 
This equation can be used to calculate Ea from rate constants k1 and k2 at temperatures T1
and T2 .
EVALUATION

Choose the correct answer:

1. For a first order reaction A ⎯⎯→ B , the rate constant is x min −1 . If the initial concentration
of A is 0.01M , the concentration of A after one hour is given by the expression.
a) 0.01 e−x (
b) 110−2 1 − e−60 x )
( )
c) 110−2 e−60 x d) none of these

2. A zero-order reaction X ⎯⎯ → Product , with an initial concentration 0.02M has a half-life of

10 min. if one starts with concentration 0.04M, then the half-life is
a) 10 s b) 5 min
c) 20 min d) cannot be predicted
3. Ref text book
→ product , with initial concentration x mol L−1 , has a half-
4. For a first order reaction A ⎯⎯
 x
life period of 2.5 hours . For the same reaction with initial concentration   mol L−1 the
2
half-life is
 2.5 
a) ( 2.5  2 ) hours b)   hours
 2 
Without knowing k & t1/ 2
c) 2.5 hours d)
cannot be determined from the given data
−d  NH3  d N 
5. For the reaction, 2NH3 ⎯⎯
→ N2 + 3H2 , if = k1  NH3  ,  2  = k 2  NH3  ,
dt dt
d H2 
= k3  NH3  then the relation between k1,k 2 and k 3 is
dt

Unit – 7 chemical kinetics The Turning Point 9

 a) k1 = k 2 = k 3 b) k1 = 3 k 2 = 2 k 3
c) 1.5 k1 = 3 k 2 = k3 d) 2k1 = k 2 = 3 k 3
3
6. For a reaction Rate = k acetone 2 then unit of rate constant and rate of reaction
respectively is

( ) 
(
s −1  , mol L−1s −1 )
−1
a) mol L−1s−1 ,  mol 2 L 2 s−1 
−1 1 1
b)  mol 2 L 2
  

(
c)  mol 2 L 2 s−1  , mol L−1s−1 ) ( )  
1 1 1 1
d) mol L s−1 ,  mol
2
2 L s
  
7. In a reversible reaction, the enthalpy change and the activation energy in the forward
direction are respectively −x kJ mol−1 and y kJ mol−1 . Therefore, the energy of activation
in the backward direction is
a) ( y − x ) kJ mol−1 b) ( x + y ) J mol−1
c) ( x − y ) kJ mol−1 d) ( x + y )  103 J mol−1
8. What is the activation energy for a reaction, if its rate doubles when the temperature is
raised from 200K to 400K? (R = 8.314 JK-1mol-1)
a) 234.65 kJ mol−1K−1 b) 434.65 kJ mol−1K−1
c) 434.65 J mol−1K−1 d) 334.65 J mol−1K−1
(all are wrong answers)
# Correct answer is
2305.31 J mol−1K −1

9. ; This reaction follows first order kinetics. The rate constant at

particular temperature is 2.303  10−2 min −1 . The initial concentration of cyclopropane is
0.25 M. What will be the concentration of cyclopropane after 1806 minutes?
( log 2 = 0.3010)
a) 0.125M b) 0.215M
c) 0.25 × 2.303M d) 0.05M
10. For a first order reaction, the rate constant is 6.909 min-1.the time taken for 75% conversion
in minutes is
3 2
a)   log 2 b)   log 2
2 3
3  3 2  4
c)   log   d)   log  
2  4 3  3

Unit – 7 chemical kinetics The Turning Point 10

11. In a first order reaction x ⎯⎯
→ y ; if k is the rate constant and the initial concentration of the
reactant x is 0.1M, then, the half-life is
 log 2   0.693 
a)   b)  
 ( 0.1) k 
 k   

 ln 2 
c)   d) none of these
 k 
12. Predict the rate law of the following reaction based on the data given below
2A + B ⎯⎯→ C + 3D
Reaction [A] [B] Initial rate
number (min) (min) (M s-1)
1 0.1 0.1 x
2 0.2 0.1 2x
3 0.1 0.2 4x
4 0.2 0.2 8x

b) rate = k  A B
2
a) rate = k A  B
2

1 3
c) rate = k A  B d) rate = k A
 
2 B 2

13. Assertion: rate of reaction doubles when the concentration of the reactant is doubles if it is a
first order reaction.
Reason: rate constant also doubles
a) Both assertion and reason are true and reason is the correct explanation of assertion.
b) Both assertion and reason are true but reason is not the correct explanation of assertion.
c) Assertion is true but reason is false.
d) Both assertion and reason are false.
14. The rate constant of a reaction is 5.8 × 10−2 s−1 . The order of the reaction is
a) First order b) zero order
c) Second order d) Third order
1
15. For the reaction N 2O5 (g) ⎯⎯
→ 2NO2 (g) + O2 (g) , the value of rate of disappearance of N2O5
2
is given as 6.5  10−2 mol L−1s−1 . The rate of formation of NO2 and O2 is given respectively
as
( ) (
a) 3.25  10−2 mol L−1s −1 and 1.3  10−2 mol L−1s −1 )
b) (1.3  10 −2
) (
mol L−1s −1 and 3.25  10−2 mol L−1s −1 )
c) (1.3  10−1 mol L−1s−1 ) and ( 3.25  10−2 mol L−1s −1 )
d) None of these

Unit – 7 chemical kinetics The Turning Point 11

16. During the decomposition of H2O2 to give dioxygen, 48 g O2 is formed per minute at certain
point of time. The rate of formation of water at this point is
a) 0.75 mol min −1 b) 1.5 mol min−1
c) 2.25 mol min −1 d) 3.0 mol min −1
17. If the initial concentration of the reactant is doubled, the time for half reaction is also
doubled. Then the order of the reaction is
a) Zero b) one
c) Fraction d) none
18. If 75% of a first order reaction was completed in 60 minutes , 50% of the same reaction
under the same conditions would be completed in
a) 20 minutes b) 30 minutes
c) 35 minutes d) 75 minutes
19. The half-life period of a radioactive element is 140 days. After 560 days , 1 g of element will
be reduced to
a)   g b)   g
1 1
 
2  
4
1
c)   g
1
d)   g
 
8  16 
20. The correct difference between first and second order reactions is that (NEET)
a) A first order reaction can be catalysed; a second order reaction cannot be catalysed.
b) The half-life of a first order reaction does not depend on [A 0]; the half-life of a second
order reaction does depend on [A0].
c) The rate of a first order reaction does not depend on reactant concentrations; the rate of a
second order reaction does depend on reactant concentrations.
d) The rate of a first order reaction does depend on reactant concentrations; the rate of a
second order reaction does not depend on reactant concentrations.
th

21. After 2 hours, a radioactive substance becomes   of original amount. Then the half-life (
1

16 
in min) is
a) 60 minutes b) 120 minutes
c) 30 minutes d) 15 minutes

Unit – 7 chemical kinetics The Turning Point 12