UNIT-7 CHEMICAL KINETICS

 What is Rate of a chemical reaction?

the rate of the reaction is defined as
“The change in the concentration of the reactant per unit time”.
A ⎯⎯⎯ →Products
-  A
Rate =
t
molL-1
unit of rate = = molL-1s-1
s
 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
 Define rate constant.
Rate constant is defined as “Rate of the reaction, when the concentration of each of the
reactants in unity”.
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 It is equal to the rate of reaction, when
concentration of the reactants or increase the concentration of each of the
in 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.

Unit – 7 chemical kinetics The Turning Point 1

 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 )
 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
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
rate = k A   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 2

 Give any three examples for the first order reaction.
1. Decomposition of dinitrogen pentoxide
N2O5 ⎯⎯⎯→ 2NO2 + 1/2O2
2. Decomposition of sulphuryl chloride
SO2Cl2 ⎯⎯⎯→ SO2 + Cl2
3. Decomposition of the Hydrogen peroxide in aqueous solution
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 ]
 What is a first order reaction? Give an example.
A reaction whose rate depends on the reactant concentration raised to the first power is
called a first order reaction.
Example: Decomposition of hydrogen peroxide in aqueous solution.
 What is a zero-order reaction? Give an example.
A reaction in which the rate is independent of the concentration of the reactant over a wide
range of concentration is called a zero-order reaction.
Example: decomposition of N2O on hot platinum surface.
 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.
 Define half-life period of a reaction.
The half-life of a reaction is defined as the time required for the reactant concentration to
reach one half its initial value. For a first order reaction
t1/2 = 0.6932
k

Unit – 7 chemical kinetics The Turning Point 3

 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.

Unit – 7 chemical kinetics The Turning Point 4

 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 5

 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
[A ]
t1/2 = 0
2k
The half-life of a zero-order reaction is directly proportional to the initial concentration of
the reactant.

Unit – 7 chemical kinetics The Turning Point 6

 Explain briefly the collision theory of bimolecular reactions.

➢ Chemical reactions occur as a result of collisions between the reacting molecules. The
reaction between A 2 & B 2 proceeds through collisions between them.
A2(g) + B(g)
2 ⎯⎯⎯→2AB(g)
➢ The rate would be proportional to the number of collisions per second. The number of
collisions is directly proportional to the concentration of both A2 &B2 .
Rate  number of collisions L-1s-1
Collision rate  [A2][B2]
Collision rate = Ζ[A2][B2]
where Ζ is a constant.
➢ At STP, each molecule undergoes approximately 109 collisions s-1 thus, if every
collision resulted in reaction, the reaction would be complete in 10−9 seconds.
➢ But all collisions are not effective. In order to react, the colliding molecules must possess
a minimum energy called activation energy (Ea). The molecules that collide with less
energy than activation energy will remain intact and no reaction occurs. Fraction of
effective collisions (f) is given by the following expression
 Ea 
- RT 

f = e  

➢ This fraction of collisions is further reduced due to orientation factor i.e., even if the
reactant collides with sufficient energy, they will not react unless the orientation of the
reactants is suitable for the formation of the transition state. The fraction of effective
collisions (f) having proper orientation is given by the steric factor p.
Rate = p × f × collision rate
 Ea 
- RT 

Rate = p × e  
× Ζ [A2][B2] ~~~~~~ 1
Rate = k[A2][B2] ~~~~~~2
from (1) & ( 2 )
 Ea 
- RT 

k = pΖe  

Unit – 7 chemical kinetics The Turning Point 7

 Write Arrhenius equation and explains the terms involved.
E 
a
-  RT 
The rate constant is directly proportional to e  
.Arrhenius proposed a relation between
the rate constant and temperature.

Ea 
- RT 
 
k = Ae  

Where ,
A - Frequency factor; R - gas constant;
Ea - Activation Energy; T - Temperature (in K)
 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 
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   =  
 k1  R  T1T2 
 k2  Ea  T2 -T1 
log   =   ~~~~~~~~ 5
k
 1 2.303R  T1T2 
This equation can be used to calculate Ea from rate constants k1 and k2 at temperatures T1
and T2 .

Unit – 7 chemical kinetics The Turning Point 8

 Define energy of activation.
Activation energy is defined as the minimum amount of energy that a colliding molecule
must possess to take part in a chemical reaction.

 List the factors affecting reaction rate.

The rate of a reaction is affected by the following factors.
1) Nature and state of the reactant and product
2) Concentration of the reactant
3) Surface area of the reactant
4) Temperature of the system
5) Presence of a catalyst
 How do nature of the reactant influence rate of reaction?
 A chemical reaction involves breaking of certain existing bonds of the reactant and
forming new bonds which leads to the product.
 The net energy involved in this process is depends on the nature of the reactant and
hence the rates are different for different reactants.
 The oxidation of oxalate ion by KMnO4 is relatively slow compared to the reaction
between KMnO4 and Fe2+ ion. In fact, heating is required for the reaction between
KMnO4 and Oxalate ion and is carried out at around 600C .
 How do physical state of the reactant influence rate of reaction?
❖ The physical state of the reactant also plays an important role to influence the rate of
reactions. Gas phase reactions are faster as compared to the solid or liquid reactants.
❖ For Example, Reaction of sodium metal with iodine vapour is faster than the reaction
between solid sodium and solid iodine.
 How do surface area of the reactant influence the rate of reaction?
• In heterogeneous reactions, the surface areas of the solid reactants play an important
role in deciding the rate. Increase in surface area of reactant leads to, more collisions per
liter per second, and hence rate of reaction is increased.
• For example, powdered calcium carbonate reacts much faster with dilute HCl than with
the same mass of CaCO3 as marble

Unit – 7 chemical kinetics The Turning Point 9

 Explain the effect of catalyst on reaction rate with an example.
• A catalyst is substance which alters the rate of a reaction without itself undergoing any
permanent chemical change.
• In the presence of a catalyst, the energy of activation is lowered and hence, greater
number of molecules can cross the energy barrier and change over to products, thereby
increasing the rate of reaction.

 How do concentrations of the reactant influence the rate of reaction?

 The rate of a reaction increases with increase of concentration of the reactants.
 According to collision theory of reaction rates, the rate of a reaction depends upon the
number of collisions between the reacting molecules.
 Higher the concentration, greater is the possibility for collision and hence the rate.
EVALUATION

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 ⎯⎯
life period of 2.5 hours . For the same reaction with initial concentration ( x / 2 ) mol L−1 the
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

Unit – 7 chemical kinetics The Turning Point 10

 −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
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
6. The decomposition of phosphine (PH3) on tungsten at low pressure is a first order reaction. It
is because the (NEET)
a) rate is proportional to the surface coverage
b) rate is inversely proportional to the surface coverage
c) rate is independent of the surface coverage
d) rate of decomposition is slow
3
7. For a reaction Rate = k acetone 2 then unit of rate constant and rate of reaction
respectively is

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

  

(
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
  
8. The addition of a catalyst during a chemical reaction alters which of the following quantities?
(NEET)
a) Enthalpy b) Activation energy
c) Entropy d) Internal energy
9. Consider the following statements:
(i) increase in concentration of the reactant increases the rate of a zero-order reaction.
(ii) rate constant k is equal to collision frequency A if Ea = 0
(iii) rate constant k is equal to collision frequency A if Ea =
(iv) a plot of ( ln k ) vs (T ) is a straight line.

(v) a plot of ( ln k ) vs   is a straight line with a positive slope.

1
T 
Correct statements are
a) (ii) only b) (ii) and (iv)
c) (ii) and (v) d) (i), (ii) and (v)

Unit – 7 chemical kinetics The Turning Point 11

10. In a reversible reaction, the enthalpy changes 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
11. 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) 2.305 KJ mol−1K −1 d) 334.65 J mol−1K−1
12. Refer book**
13. For a first order reaction, the rate constant is 6.909 min-1.the time taken for 75% conversion
in minutes is
3 2 3  3 2  4
a)   log 2 b)   log 2 c)   log   d)   log  
2 3 2  4 3  3
14. 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   ln 2 
a)   b)   c)   d) none of these
 ( 0.1) k 
 k     k 
15. ***Refer book
16. 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.
17. 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
18. For the reaction N 2O5 (g) ⎯⎯
→ 2NO2 (g) + O2 (g) , the value of rate of disappearance of N 2O5
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 )

Unit – 7 chemical kinetics The Turning Point 12

 ( ) (
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
19. 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
20. 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
21. 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
22. The half-life period of a radioactive element is 140 days. After 560 days, 1 g of element will
be reduced to
1 1
a)   g b)   g
2 4
1 1
c)   g d)   g
8  16 
23. The correct difference between first and second order reactions is that (NEET)
a) A first order reaction can be catalyzed; a second order reaction cannot be catalyzed.
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
1
24. After 2 hours, a radioactive substance becomes   of original amount. Then the half-life (
 16 
in min) is
a) 60 minutes b) 120 minutes
c) 30 minutes d) 15 minutes

Unit – 7 chemical kinetics The Turning Point 13