NCERT Solution for Class 12

Chemistry
Chapter 4 - Chemical Kinetics

Intext Exercise

1. For the reaction R  P , the concentration of a reactant changes from 0.03

M to 0.02 M in 25 minutes. Calculate the average rate of reaction using units
of time both in minutes and seconds.
Ans: The average rate of the reaction can be calculated by dividing the change in
the rate of decreasing the rate of reactant by the time taken. This is given below:
d[R]
Average rate = -
dt
This can be written as:
[R]2 -[R]1
Average rate = -
t 2 -t1
R 1 = 0.03 M
R 2 = 0.02 M
t 2 - t1 = 25 min
Putting the values, we get:
0.02  0.03
Average rate = -
25
0.01
Average rate = -  4 × 104 M min 1
25
So, the average rate in minutes will be 4 × 104 M min 1
Now, to find the average rate in seconds we have to divide the above answer by 60.
So, the answer will be:
4 × 104
Average rate = -  6. 66 × 106 M s 1
60
Therefore, the average rate in seconds will be 6.66 × 106 M s1

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2. In a reaction, 2A  Products, the concentration of A decreases from
0.5 mol L-1 to 0.4 mol L-1 in 10 minutes. Calculate the rate during this
interval.
Ans: The average rate of the reaction can be calculated by dividing the change in
the rate of decreasing the rate of reactant by the time taken. This is given below:
1 Δ[A]
Average rate = -
2 Δt
This is due the fact that the reaction given is:
2A  Products
So, the average rate will be written as:
1 [A]2 -[A]1
Average rate = -
2 t 2 -t1
A1 = 0.5 M
A 2 = 0.4 M
t 2 - t1 = 10 min
Putting the values, we get:
1 0.4  0.5
Average rate = - ×
2 10
1 0.1
Average rate = - ×  5 × 103 M min 1
2 10
So, the average rate will be 5 × 103 M min1

3. For a reaction, A + B  Product , the rate law is given by: r = k [A]1/2 [B]2 .
What is the order of the reaction?
Ans: The order of the reaction can be calculated by adding the stoichiometry
coefficients of the reactants in the given rate of the reaction.
Given the rate is r = k [A]1/2 [B]2
So, the order will be:
1
Order = 2 + = 2.5
2
So, the order of the reaction is 2.5

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4. The conversion of the molecules X to Y follows second order kinetics. If
concentration of x is increased to three times how will it affect the rate of
formation of Y?
Ans: The reaction will be:
X  Y
As the question says that this reaction follows the second order reaction, we can
write the rate law equation as:
Rate = k[X]2 = ka 2
If [X] = a mol/ L
It is said that the concentration of X increases by three times, so we can write:
[X] = 3a mol/ L
Therefore, the rate of reaction will be:
Rate = k (3a)2 = 9 ka 2
Thus, the rate of the reaction will increase by 9 times or the rate formation will
increase by 9 times.

5. A first order reaction has a rate constant 1.15 × 10-3 s-1 . How long will 5 g
reactant take to reduce to 3 g?
Ans: The initial amount of the reactant is given as 5 g. We can write:
[R]0 = 5 g
The final amount of the reactant is given as 3 g. We can write:
[R] = 3 g
We are also given the value of rate constant as:
Rate constant = 1.15 × 10-3 s-1
We know that the reaction is a 1st order reaction, the time can be calculated by:
2.303 [R]
t= log 0
k [R]
Putting the values in the above formula, we get:
2.303 5
t= 3
log
1.15 x 10 3

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 2.303
t= × 0.2219
1.15 × 103
t = 444 seconds
So, the time taken will be 444 seconds.

6. Time required to decompose SO 2Cl 2 to half its initial amount is 60 minutes.

If the decomposition is a first order reaction, calculate the rate constant of
the reaction.
Ans: We are given that the decomposition of SO 2Cl2 is a first order reaction. So, we
can write:
0.693
t1/2 =
k
It is mentioned that the time required for the initial amount to become half is 60
minutes.
t1/2 = 60 min
0.693
Therefore, k =
t1/2
Putting the value, we get:
0.693
k= = 1.925 × 10-4 s-1
60 × 60
Thus, the rate constant is 1.925 × 10-4 s-1 .

7. What will be the effect of temperature on rate constant?

Ans: An increase of 10 degrees in temperature causes a reaction's rate constant to
almost double in size. In any case, the Arrhenius equation gives the exact
temperature dependency of a chemical reaction rate.
The Arrhenius equation is given below:
k = A e-E /Rt
a

Where, A is the Arrhenius factor or the frequency factor,

T is the temperature,
R is the gas constant,

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E a is the activation energy.

8. The rate of the chemical reaction doubles for an increase of 10 K in absolute

temperature from 298 K. Calculate E a .
Ans: The formula that can be used to solve the question is:
k E a  T2 -T1 
log 1 =  
k2 2.303R  T1T2 
T1 temperature given is absolute temperature and it is equal to 298 K.
T2 = 298 + 10 = 308 K
It is given that the rate of the chemical reaction double for an increase of 10 K,
therefore, we can write the values of rate constant as:
k1 = x
k 2 = 2x
Also, R = 8.314 J K-1 mol-1
Now, putting all the values in the formula, we get:
2x Ea  10 
log =
x 2.303 × 8.314  298 × 308 
Ea  10 
log2 = 
2.303 × 8.314  298 × 308 
2.303 × 8.314 × 298 × 308 × log 2
Ea =
10
Ea = 52897.78 J mol1
Ea = 52.89 kJ mol1

9. The activation energy for the reaction 2HI (g)  H 2 +I 2 is 209.5 kJ mol-1 at
(g) (g)

581 K. Calculate the fraction of molecules of molecules having energy equal

to or greater than activation energy.
Ans: We are given the activation energy as 209.5 kJ mol-1
T = 581 K

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R = 8.314 J K-1 mol-1
Now, the fraction of molecules of reactants having energy equal to or greater than
activation energy is given as:
x = eE /RT
a

-E
ln x = a
RT
-E a
log x =
2.303 RT
209500
log x =  18.8323
2.303 × 8.314 × 581
Now, taking the antilog:
x = Antilog (18.8323)
x = 1.471 × 10-19

NCERT Exercise

1. From the rate expression for the following reactions, determine their order
of reaction and the dimension of the rate constants.
(i) 3 NO(g)  N2O(g) Rate = k[NO]2
Ans: We are given:
Rate = k[NO]2
From this we can see that the order of the reaction = 2
rate
k=
[No]2
Dimensions will be:
mol L-1 s-1
k=
(mol L-1 ) 2
mol L-1 s -1
=
mol 2 L2
= L mol-1 s-1

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(ii) H2O2 (aq)+3I- (aq)+2H+  2H2O(l)+I -3 Rate=k[H2O2 ][I - ]
Ans: Rate = k[H2O2 ][I ]
From this we can see that the order of the reaction = 2
rate
k=
[H 2O 2 ][I  ]
Dimensions will be:
mol L-1 s-1
k=
(mol L-1 ) 2
mol L-1 s -1
=
mol 2 L2
= L mol-1 s-1

(iii) CH3CHO(g)  CH4 (g)+ CO(g) Rate = k[CH3CHO]3/2

Ans: Rate = k[CH3 CHO]3/2
3
From this we can see that the order of the reaction =
2
rate
k= 3

[CH 3 CHO]2
Dimensions will be:
mol L-1 s-1
k=
(mol L-1 )3/2
mol L-1 s -1
= 3 3

mol L 2 2

1 1
-
= L2 mol 2 s -1

(iv) C2 H 5Cl(g)  C2 H 4 (g)+ HCl(g) Rate = k[C2 H 5Cl]

Ans: Rate = k[C2 H 5Cl]
From this we can see that the order of the reaction = 1

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 rate
k=
[C2 H 5Cl]
Dimensions will be:
mol L-1 s-1
k=
(mol L-1 )
= s-1

2. For a reaction:
2A+B  A 2B
The rate = k[A][B]2 with k = 2.0 x 10-6 mol -2 L2 s-1 .
Calculate the initial rate of the reaction when [A] = 0.1 mol L-1 ,
[B] = 0.2 mol L-1 Calculate the rate of reaction after [A] is reduced to
0.06 mol L-1 .
Ans: We are given the rate of the reaction as:
rate = k[A][B]2
Putting the values in this, we get the rate as:
rate = 2.0 × 10-6 × 0.1 × (0.2)2
rate = 8.0 × 10-9 mol L1 s1
When [A] is reduced from 0.10 mol L1 to 0.06 mol L1 . So, the amount of [A]
reacted will be:
 0.10  0.06  0.04 mol L1
Therefore, the concentration of B reacted will be:
1
 × 0.04 = 0.02 mol L1
2
Hence, new [B] = 0.2 – 0.02 = 0.18 mol L1
Now, the new rate of the reaction will be:
rate = 2.0 × 10-6 × 0.06 × (0.18)2
rate = 3.89 × 10-9 mol L1 s1
Therefore, the rate of the reaction is 3.89 × 10-9 mol L1 s1 .

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3. The decomposition of NH 3 on the platinum surface there is zero order
reaction. What are the rates of production of N2 and H2 if
k = 2.5 × 10-4 mol -1 L s-1 ?
Ans: The following equation represents the breakdown of Ammonia on the platinum
surface.
2NH3 
(g)
Pt
 N2 +3H2
(g) (g)

Therefore, we can write the rate of the reaction as:

1 d[NH3 ] d[N 2 ] 1 d[H 2 ]
Rate = - = =
2 dt dt 3 dt
But we are given that the reaction is a zero order reaction.
1 d[NH3 ] d[N 2 ] 1 d[H 2 ]
So, Rate = - = = = 2.5 × 104 mol L1 s 1
2 dt dt 3 dt
Thus, the rate of production of N 2 will be:
d[N 2 ]
= 2.5 × 104 mol L1 s 1
dt
And the rate of production of H 2 will be:
d[H 2 ]
= 3 × 2.5 × 104 mol L1 s 1  7.5 × 104 mol L1 s 1
dt

4. The decomposition of dimethyl ether leads to the formation of CH 4 , H 2

and CO and the reaction rate is given by
Rate = k [CH3OCH3 ]3/2
The rate of reaction is followed by increase in pressure in a closed vessel, so
the rate can also be expressed in terms of the partial pressure of dimethyl
ether, i.e.,
Rate = k (PCH OCH )3/2
3 3

It the pressure is measured in bar and time in minutes, then what are the
units of rate and rate constants?
Ans: If the pressure is measured in bar and time in minutes, then unit of rate will be:
= bar min-1

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We are given the rate of the reaction as: Rate = k [CH3OCH3 ]3/2
Rate
Therefore, k =
[CH3OCH3 ]3/2
So, we can write the units of rate constant as:
bar min -1
k= 3/2
= bar -1/2 min -1
bar
So, the units are bar -1/2 min-1 .

5. Mention the factors that affect the rate of a chemical reaction.

Ans: Factors that influence a reaction's speed include.
(i) Reactant nature: The rate of reaction is affected by the kind of reactant. For
example, ionic compound reactions are quicker than covalent compound
reactions.
(ii) The state of the reactants: Solid reactions are sluggish, liquid reactions are rapid,
and gas reactions are very quick.
(iii)Temperature: In addition, temperature has a significant impact on response rate.
Every 10 degrees Celsius increase in temperature doubles the pace of reaction.
(iv) Presence of catalyst: The rate of reaction is also affected by the presence of a
catalyst in the reaction. It enhances the pace of reaction by increasing reaction
surface area, by generating unstable intermediates with the substrate, and by
offering a lower activation energy alternative path.

6. A reaction is second order with respect to a reactant. How is the rate of

reaction affected if the concentration of the reactant is:
(i) Doubled
Ans: Let us assume that the concentration of the reactant be [A] = a
Rate of the reaction will be:
R = k[A]2 = ka 2
It is said that the concentration of A increases by two times, so we can write:
[A] = 2a mol/ L
Therefore, the rate of reaction will be:
Rate = k (2a)2 = 4 ka 2

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Thus, the rate of the reaction will increase by 4 times.

(ii) Reduced to half

It is said that the concentration of A reduced to half, so we can write:
1
[X] = a mol/ L
2
Therefore, the rate of reaction will be:
2
1  1
Rate = k  a  = ka 2
2  4
Thus, the rate of the reaction will reduce by ¼ times.

7. What is the effect of temperature on the rate constant of a reaction? How can
this temperature effect on rate constant be represented quantitatively?
Ans: An increase of 10 degrees in temperature causes a reaction's rate constant to
almost double in size. In any case, the Arrhenius equation gives the exact
temperature dependency of a chemical reaction rate.
The Arrhenius equation is given below:
k = A e-E /Rt
a

Where, A is the Arrhenius factor or the frequency factor,

T is the temperature,
R is the gas constant,
E a is the activation energy.
The formula can also be written as:
k E a  T2 -T1 
log 2 =  
k1 2.303R  T1T2 
Where k 2 is the rate constant at temperature T2
k 1 is the rate constant at temperature T1

8. Ina pseudo first order hydrolysis of ester in water, the following results were
obtained

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 t/s 0 30 60 90
[Ester]mol L-1 0.55 0.31 0.17 0.085

(i) Calculate the average rate of reaction between the time interval 30 to 60
seconds.
Ans: Between the time interval of 30 to 60 sec the average rate id reaction will be
calculated as:
d[Ester]
=
dt
Putting the values from the data given in the question, we can write:
0.31  0.17 0.14
= 
60  30 30
-3
= 4.67 × 10 mol L-1 s-1

(ii) Calculate the pseudo first order rate constant for the hydrolysis of ester.
Ans: The rate law formula for pseudo first order reaction will be:
2.303 [R]
k= log 0
t [R]
Now, when t = 30 s, then we rate constant will be:
2.303 0.55
k1 = log  1.91 × 102 s 1
30 0.31

Now, when t = 60 s, then we rate constant will be:

2.303 0.55
k2 = log  1.96 × 102 s 1
60 0.17

Now, when t = 90 s, then we rate constant will be:

2.303 0.55
k3 = log  2.075 × 102 s 1
90 0.085
So, we can calculate the average rate constant as:

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 k1 + k 2 + k 3
k=
3
=1.98 × 10-2 s-1

9. A reaction is first order in A and second order in B.

(i) Write the differential rate equation
Ans: The differential rate equation can be written as:
d[R]
- = k[A][B]2
dt

(ii) How is the rate affected on increasing the concentration of B three times?
Ans: The concentration of B is increased by 3 times, then B =3B
Therefore, the rate will be:
d[R]
- = k[A][3B]2  9  [A][B]2
dt
Therefore, the rate will increase by 9 times.

(iii) How is the rate affected when the concentration of both A and B are
doubled?
Ans: The concentration of A is doubled, then A = 2A
The concentration of B is doubled, then B = 2B
Therefore, the rate will be:
d[R]
- = k[2A][2B]2  8  [A][B]2
dt
Therefore, the rate will increase by 8 times.

10. In a reaction between A and B the initial rate of reaction (r0 ) was measured
for different concentrations of A and B as given below:
A/mol L-1 0.20 0.20 0.04
B/mol L-1 0.30 0.10 0.05
r0 /mol L-1 s-1 5.07 × 10-5 5.07 × 10-5 1.43 × 10-4

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 What is the order of the reaction with respect to A and B?
Ans: Let us assume that the order of the reaction with respect to A be x and with
respect to B be y.
Therefore, we can write:
r0 = k [A]x [B]y
5.07 × 10-5 = k [0.20]x [0.30]y .........(i)
5.07 × 10-5 = k [0.20]x [0.10]y .........(ii)
1.43 × 10-5 = k [0.40]x [0.05]y .........(iii)
Let us divide (i) by (ii), we get:
5.07 × 10-5 k [0.20]x [0.30]y
=
5.07 × 10-5 k [0.20]x [0.10]y
[0.30]y
=1 =
[0.10]y
x y
 0.30   0.30 
=  = 
 0.10   0.10 
Therefore, y = 0
Now, dividing (iii) by (i), we get:
1.43 × 10-4 k [0.40]x [0.05]y
=
5.07 × 10-5 k [0.20]x [0.30]y
1.43 × 10-4 k [0.40]x
=
5.07 × 10-5 k [0.20]x
Because y = 0
= 2.821 = 2x
Now, taking log on both the sides.
log 2.821 = x log 2
log 2.821
x=
log 2
x = 1.496
x = 1.5
Thus, the order of the reaction according to A is 1.5 and according to B is 0.

Class XII Chemistry www.vedantu.com 14

11. The following results have been obtained during the kinetic studies of the
reaction.
2A + B  C + D
Experiment A/mol L-1 B/mol L-1 Initial rate of formation of
D/mol L-1min-1
I 0.1 0.1 6.0 × 10-3
II 0.3 0.2 7.3 × 10-2
III 0.3 0.4 2.88 × 10-1
IV 0.4 0.1 2.40 × 10-2
Determine the rate law and the rate constant for the reaction.
Ans: Let us assume that the order of the reaction with respect to A be x and with
respect to B be y.
Therefore, we can write:
Rate = k [A]x [B]y
6.0 × 10-3 = k [0.1]x [0.1]y .........(i)
7.2 × 10-2 = k [0.3]x [0.2]y .........(ii)
2.88 × 10-1 = k [0.3]x [0.1]y .........(iii)
2.40 × 10-2 = k [0.4]x [0.1]y .........(iv)
Let us divide (iv) by (i), we get:
2.40 × 10-2 k [0.4]x [0.1]y
=
6.0 × 10-3 k [0.1]x [0.1]y
[0.4]x
=4 =
[0.1]x
x
 0.4 
=4=  
 0.1 
Therefore, x = 1
Now, dividing (iii) by (ii), we get:
2.88 × 10-1 k [0.3]x [0.4]y
=
7.2 × 10-2 k [0.3]x [0.2]y

Class XII Chemistry www.vedantu.com 15

 y
 0.4 
=4=  
 0.2 
= 4 = 2y
= 22 = 2 y
y=2
Thus, the order of the reaction according to A is 1 and according to B is 2.
So, the rate law is:
Rate = k[A][B]2
Rate
k=
[A][B]2
Now, putting the values for each experiment, we get:
From experiment I:
6.0 × 103
k=
[0.1][0.1]2
= 6.0 L2 mol-2 min-1
From experiment II:
7.3 × 102
k=
[0.3][0.2]2
= 6.0 L2 mol-2 min-1
From experiment III:
2.88 × 101
k=
[0.3][0.4]2
= 6.0 L2 mol-2 min-1
From experiment IV:
2.40 × 102
k=
[0.4][0.1]2
= 6.0 L2 mol-2 min-1
Therefore, the rate constant will be k = 6.0 L2 mol-2 min-1

12. The reaction between A and B is first order with respect to A and zero order
with respect to B. Fill in the blanks in the following table:

Class XII Chemistry www.vedantu.com 16

 Experiment A/mol L-1 B/mol L-1 Initial rate D/mol L-1min-1
I 0.1 0.1 2.0 × 10-2
II --- 0.2 4.0 × 10-2
III 0.4 0.4 ----
IV ---- 0.2 2.0 × 10-2
Ans: We are given that, the reaction between A and B is first order with respect to
A and zero order with respect to B.
Therefore, the rate of the reaction is given by:
Rate = k[A]1[B]0
So, we can write:
Rate = k[A]
According to the experiment I we can write:
2.0 × 10-2 = k(0.1)
k = 0.2 min -1
According to the experiment II we can write:
4.0 × 102  (0.2) [A]
[A] = 0.2 mol L-1
According to the experiment III we can write:
Rate = 0.2 × 0.4
= 0.08 mol L-1 min-1
According to the experiment III we can write:
2.0 × 102  (0.2) [A]
[A] = 0.1 mol L-1

13. Calculate the half-life of a first order reaction from their rate constants
given below:
(i) 200 s-1
Ans: Half-life of the reaction can be related with the rate constant of the reaction as:
0.693
t1/2 =
k
Putting the value of time, we get:

Class XII Chemistry www.vedantu.com 17

 0.693
k= = 3.46 × 10-3 s
200
So, the rate of the reaction is 3.46 × 10-3 s

(ii) 2 min -1
Ans: Half-life of the reaction can be related with the rate constant of the reaction as:
0.693
t1/2 =
k
Putting the value of time, we get:
0.693
k= = 0.346 min
2
So, the rate of the reaction is 0.346 min.

(iii) 4 years-1
Ans: Half-life of the reaction can be related with the rate constant of the reaction as:
0.693
t1/2 =
k
Putting the value of time, we get:
0.693
k= = 0.173 years
4
So, the rate of the reaction is 0.173 years.

14. The half-life for radioactive decay of 14 C is 5730 years. An archeological

artifact containing wood had only 80% of the 14 C found in a living tree.
Estimate the age of the sample.
Ans: The given reaction in the above question is radioactive decay and the
radioactive decay follows the first order kinetics. Therefore, the decay constant:
0.693
λ=
t1/2
We are given the half-life time as 5730 years.
0.693
λ= years 1
5730
Class XII Chemistry www.vedantu.com 18
To find the age of the sample, we can write:
2.303 [R]
t= log 0
λ [R]
80% of the wood is found so, the initial amount can be taken as 100 and the final
amount as 80. Putting the values, we get:
2.303 100
t= log
0.693 80
5730
t = 1845 years
Therefore, the age of the sample is 1845 years.

15. The experiment data for decomposition of N 2O 5

[2N 2O 5  4NO 2 +O 2 ]
In gas phase at 318 K are given below:
t/s 0 400 800 1200 1600 2000 2400 1800 3200
10-2 × [N2O5 ]/mol L-1 1.63 1.36 1.14 0.93 0.78 0.64 0.53 0.43 0.35
(i) Plot [ N 2O 5 ] against t
Ans: The graph is given below:

Class XII Chemistry www.vedantu.com 19

(ii) Find the half-life period for the reaction
Ans: Time corresponding to the concentration,
1.630 × 10-2
mol L-1 =0.815 × 10-2 mol L-1 is the half-life.
2
From the graph, the half-life obtained is 1440 s.

(iii) Draw the graph between log[N 2O5 ] and t

Ans:
T(s) 10-2 × [N2O5 ]/mol L-1 log[N 2O5 ]
0 1.63 -1.79
400 1.36 -1.87
800 1.14 -1.94
1200 0.93 -2.03
1600 0.78 -2.11
2000 0.64 -2.19
2400 0.53 -2.28
2800 0.43 -2.37
3200 0.35 -2.46

Class XII Chemistry www.vedantu.com 20

(iv) What is the rate law?
Ans: The rate law of the reaction will be:
Rate = k[N 2O5 ]

(v) Calculate the rate constant.

Ans: From the plot [N 2O 5 ] v/s t, is given by:
k
=-
2.303
Therefore, we obtain:
k 0.67
=- 
2.303 3200
= 4.82 × 10-4 mol L-1 s-1

(vi) Calculate the half-life period from k and compare it will (ii)
Ans: Half-life is given by:
0.693 0.693
t1/2   s
k 4.82 × 104
= 1438 seconds.
The value of half-life calculated from the k is very close to that obtained from the
graph.

16. The rate constant for a first order reaction is 60 s-1 . How much time will it
take to reduce the initial concentration of the reactant to its 1/16th value?
Ans: As we know that:
2.303 [R]
t= log 0
k [R]
The initial value of the reactant has become 1/16th. Now, putting the values, we get:
2.303 16
t= log
60 1
2.303
t= log16 = 4.62 × 10-2 s
60

Class XII Chemistry www.vedantu.com 21

Therefore, the time required will be 4.62 × 102 s .

17. During nuclear explosion, one of the products is 90 Sr with a half-life of 28.1
years. If 1 μg of 90 Sr was absorbed in the bones of a newly born baby
instead of calcium, how much of it will remain after 10 years and 60 years
if it is not lost metabolically.
Ans: As radioactive disintegration follows first order kinetics.
0.693 0.693
Decay constant of 90 Sr (k) =   2.466 × 102 y 1
t1/2 28.1
To calculate the amount left after 10 years.
a = 1 μg
t = 10 years
k=2.466 × 10-2 y-1
(a-x) = ?
2.303 a
k= log
t a-x
2.303 1
2.466 × 102 = log
10 a-x
log(a-x) = -0.1071
(a-x) = Antilog -0.1071 = 0.7814 μg

To calculate the amount left after 60 years.

2.303 a
k= log
t a-x
2.303 1
2.466 × 102 = log
60 a-x
log(a-x) = -0.6425
(a-x) = Antilog -0.6425 = 0.2278 μg

18. For a first order reaction, show that time required for 99% completion is
twice the time required for the completion of 90% of reaction.

Class XII Chemistry www.vedantu.com 22

Ans: For first order reaction, we can write:
2.303 a
t= log
k a-x
99% completion means that x = 99% of a = 0.99 a
So, we can write:
2.303 a
t 99% = log
k a-0.99a
2.303
t 99% = log 102
k
2.303
t 99% = 2 ×
k
90% completion means that x = 90% of a = 0.90 a
2.303 a
t 99% = log
k a-0.90a
2.303
t 99% = log 10
k
2.303
t 99% =
k
Now, we can take the ratio as given below:
 2 x 2.303 
t 99%  k



t 90%  2.303 
 
 k 
t 99%  2 × t 90%
Hence, the time required for 99% completion of a first order reaction is twice the
time required for the completion of 90% of the reaction.

19. A first order reaction takes 40 min for 30% decomposition. Calculate t 1/2 .
Ans: 30% decomposition means that x = 30% of a = 0.30 a
Since, the reaction is of 1st order, we can write:
2.303 a
k= log
t a-x
Class XII Chemistry www.vedantu.com 23
Time is given as 40 min. So, putting the values, we get:
2.303 a
k= log
40 a-0.30a
2.303 10
k= log min 1
40 7
2.303
k= × 0.1549 min 1  8.918 × 10 3 min 1
40
Now, we can calculate the half-life period as we have the rate constant value.
We can write:
0.693 0.693
t1/2    7.77 min
k 8.918 × 103
So, the half-life is 7.77 min.

20. For the decomposition of azoisopropane to hexane and nitrogen at 543 K,

the following data are obtained:
T (sec) P (mm of Hg)
0 35.0
360 54.0
720 63.0
Calculate the rate constant.
Ans: The decomposition of azoisopropane to hexane and nitrogen at 54.3 k is
represent by the following equation.

Total pressure after time t, we will be:

Pt = (Po -p) + p + p
Pt =Po +p
p=Pt  Po
Now, we can substitute the value of p for the pressure of reactant at time t

Class XII Chemistry www.vedantu.com 24

=Po -p
=Po -(Pt -Po )
= 2Po - Pt
Now, we can apply the rate constant formula of 1st order reaction.
2.303 P
k= log
t 2Po -Pt
When t = 360 s,
Putting the values, we get:
2.303 35.0
k= log  2.175 × 103 s 1
360 2 × 35 - 54
When t = 720 s,
Putting the values, we get:
2.303 35.0
k= log  2.235 × 103 s 1
720 2 × 35 - 63
Now, we can find the average value:
(2.175 × 10-3 )+(2.235 × 10-3 ) -1
k= s
2
k = 2.20 × 10-3 s-1

21. The following data were obtained during the first order thermal
decomposition of SO 2Cl 2 at a constant volume.
SO 2Cl 2  SO 2 +Cl 2
(g) (g) (g)

Experiment Time/ s Total pressure/ atm

1 0 0.5
2 100 0.6
Calculate the rate of the reaction when total pressure is 0.65 atm.
Ans: The given reaction shows the thermal decomposition of SO 2Cl2 at constant
volume.

Class XII Chemistry www.vedantu.com 25

Total pressure after time t, we will be:
Pt = (Po -p) + p + p
Pt =Po +p
p=Pt  Po
Now, we can substitute the value of p for the pressure of reactant at time t
=Po -p
=Po -(Pt -Po )
= 2Po - Pt
Now, we can apply the rate constant formula of 1st order reaction.
2.303 P
k= log
t 2Po -Pt
When the t = 100 s
2.303 0.5
k= log
100 2 × 0.5 - 0.6
-3 -1
k = 2.231 × 10 s
When Pt = 0.65 atm
Therefore, pressure of SO 2Cl2 at time t total pressure is 0.65 atm, is
PSO Cl =2Po -Pt
2 2

= 2 × 0.50 – 0.65
= 0.35 atm
Therefore, the rate of equation, when total pressure is 0.65 atm, is given by:
Rate = k(PSO Cl )
2 2

Rate = (2.33 x 10-3 )(0.354) = 7.8 × 10-4atm s-1

22. The rate constant for the decomposition of N 2O 5 at various temperature is

Class XII Chemistry www.vedantu.com 26

 given below:
T/ oc 0 20 40 60 80
5
10 × k/s 0.0787 1.70 25.7 178 2140
Draw a graph between ln K and 1/T and calculate the values of A and E a .
Predict the rate constant at 30o and 50o C.
Ans: As the data is given we can write:

T/ oc 0 20 40 60 80
T/K 273 293 313 333 353
1 -1 3.66 × 10-3 3.41 × 10-3 3.19 × 10-3 3.0 × 10-3 2.83 × 10-3
/k
T
105 × k/s 0.0787 4.075 25.7 178 2140
ln K -7.147 -4.075 -1.359 -0.577 3.063

The graph is draw below:

Slope of the line, will be given as:

y2 -y1
= 12.301 K
x 2 -x1

Class XII Chemistry www.vedantu.com 27

According to the Arrhenius equation,
E
Slope = - a
R
= E a = -slope × R
= (-12.301) (8.314)
=102.27 KJ mol-1
Again,
E
ln k = ln A - a
RT
E
ln A = ln k + a
RT
As T = 273 K and ln k = -7.147
Applying this in the formula, we get:
102.27 × 103
ln A = -7.147 -  37.911
8.314 × 273
So, A=2.91 × 106
When T = 30 + 273 K = 303 K
1
= 0.0033K = 3.3 × 10-3K
T
1
Now, at = 0.0033K = 3.3 × 10-3K
T
ln k = - 2.8
Therefore, k = 6.08 × 10-2 s-1
When T = 50 + 273 K = 323 K
1
= 0.0031K = 3.1 × 10-3K
T
1
Now, at = 0.0031K = 3.1 × 10-3K
T
ln k = - 0.5
Therefore, k = 0.607 s-1

23. The rate constant for the decomposition of hydrocarbons is 2.418 × 10-5 s-1
Class XII Chemistry www.vedantu.com 28
 at 546 K. If the energy of activation is 179.9 kJ /mol, what will be the value
of the pre-exponential factor?
Ans: We are given some values as:
K = 2.418 × 10-5 s-1
T = 546 K
Ea = 179.9 kJ mol-1  179.9 × 103 J mol1
We the Arrhenius equation is:
k = A e-E /RT
a

In the log form, this can be written as:

E
ln k = ln A - a
RT
Ea
log k = log A -
2.303 RT
179.9 × 103
log k = log (2.418 × 10 5 ) -
2.303 × 8.314 × 546
= (0.3835 – 5) + 17.2082 = 12.5917
Therefore, A = antilog (12.5917)
A = 3.912 × 1012 s-1

24. Consider a certain reaction A  Products with k = 2.0 × 10-2 s-1 .

Calculate the concentration of A remaining after 100s if the initial
concentration of A is 1.0 mol L-1 .
Ans: We are given some values, that are given below:
k = 2.0 × 10-2 s-1
t = 100 s
[A]o =1.0 mol L-1
As we can see that the units of k is given in s-1 , this means that the reaction is a first
order reaction.
Therefore, we can write:
2.303 [A]
k= log 0
t [A]
Putting the values, we get:

Class XII Chemistry www.vedantu.com 29

 2.303 1.0
2.0 × 102 = log
100 [A]
2.303
2.0 × 102 = (-log[A])
100
2.0 × 102 × 100
(-log[A]) =
2.303
 2.0 × 102 × 100 
[A] =antilog  
 2.303 
 0.135 mol L1
Therefore, the remaining amount of A is 0.135 mol L1 .

25. Sucrose decomposes in acid solution into glucose and fructose according to
the first order rate law with t 1/2 = 3.00 hours . What fraction of a sample of
sucrose remains after 8 hours?
Ans: The given reaction is a first order reaction. So, we can write:
2.303 [R]
k= log 0
t [R]
We are given a half-life of 3 hours. Therefore, we can write:
0.693
k=
t1/2
So, putting the values in this, we get:
0.693
k= = 0.231 h -1
3
Now, we can put this value of rate constant in the first order reaction formula.
2.303 [R]
0.231 = log 0
8 [R]
[R] 0.231 × 8
log 0 =
[R] 2.303
[R]
log 0 = 0.8024
[R]

Class XII Chemistry www.vedantu.com 30

[R]0
= antilog (0.8024)
[R]
[R]0
= 6.3445
[R]
Or we can write:
[R]
= 0.158
[R]0
Therefore, the fraction of sample of sucrose that remains after 8 hours is 0.158.

26. The decomposition of hydrocarbon follows the equation

k = (4.5 × 1011 s-1 )e-280000K/T . Calculate E a .
Ans: According to the Arrhenius equation,
k = Ae-E /RT
a

We are given the equation as:

k = (4.5 × 1011 s-1 )e-280000K/T
Therefore, the formula can be written as:
E 28000 K
- a =-
RT T
This can be written as:
E a = 28000 × R
Ea = 28000 × 8.314 = 232.79 kJ mol-1
Therefore, the value of E a is 232.79 kJ mol-1

27. The rate constant for the first order decomposition of H 2O 2 is given by the
following equation:
log k = 14.34 - 1.25 × 104 K/T
Calculate E a for this reaction and at what temperature will its half-period
be 256 minutes?
Ans: According to the Arrhenius equation,
k = Ae-E /RT
a

Class XII Chemistry www.vedantu.com 31

This can be written as:
E
ln k = ln A - a
RT
In the log form it can be written as:
Ea
log k = log A -
2.303 RT
We are given:
log k = 14.34 - 1.25 × 104 K/T
Comparing these two, we get:
Ea 1.25 × 104 K
=
2.303 RT T
Ea = 2.303 R × 1.25 × 104 K
Ea = 2.303 × 8.314 × 1.25 × 104 K
Ea = 239.34 kJ mol1
We are given half-life time as 256 minutes.
0.693
k=
t1/2
0.693
k= = 4.51 × 10-5 s-1
256 × 60
Now, we have the value of rate constant, we can put in the equation:
1.25 × 104
log(4.51 × 10-5 ) = 14.34 -
T
T = 669 K

28. The decomposition of A into product has value of k as 4.5 × 103 s-1 at 10oC
and energy of activation 60 kJ mol -1 . At what temperature would k be
1.5 × 104 s-1 ?
Ans: We are some information:
k1 = 4.5 × 103
T1 = 10 + 273 = 283 K

Class XII Chemistry www.vedantu.com 32

k 2 = 1.5 × 104
T2  ?
Ea = 60 kJ mol-1
Applying Arrhenius equation:
k E a  T2 -T1 
log 2 =  
k1 2.303R  T1T2 
Putting the values, we can write:
1.5 × 104 60  T2 -283 
log =  
4.5 × 103 2.303 × 8.314  283T2 
 T -283 
log 3.333 = 3133.63  2 
 283T2 
0.5228  T2 -283 
 
3133.63  283T2 
0.0472T2 = T2 - 283
T2 = 297 K
Or we can write:
T2 = 24oC

29. The time required for 10% completion of a first order reaction at 298 k is
equal to that required for its 25% completion at 308 K. If the value of A is
4 × 1010 s-1 , Calculate k at 318 K and E a .
Ans: There are two cases in this question. As the reaction given is first order
reaction, we can use:
2.303 a
k= log
t a-x
For case 1:
2.303 a
k 298K = log
t1 a - 0.10a

Class XII Chemistry www.vedantu.com 33

 2.303 10
k 298K = log
t1 9
2.303
k 298K = × 0.0458
t1
0.1055
t1 =
k 298K
For case 2:
2.303 a
k 308K = log
t2 a - 0.25a
2.303 4
k 308K = log
t2 3
2.303
k 308K = × 0.125
t2
0.2879
t2 =
k 308K
But t1 = t 2
Hence,
0.1055 0.2879
=
k 298K k 308K
k 308K
= 2.7289
k 298K
Now, applying the Arrhenius equation,
k E a  T2 -T1 
log 308K =  
k 298K 2.303R  T1T2 
Ea  308-298 
log(2.7289) =  
2.303 × 8.314  298 × 308 
Ea = 76.623 kJ mol-1
Now, the calculation of k at 318 K

Class XII Chemistry www.vedantu.com 34

 Ea
log k = log A -
2.303RT
7623
log k = log (4 × 1010 ) -
2.303 × 8.314 × 318
log k = 10.6021 - 12.5843 = -1.9822
k = Antilog (-1.9822) = antilog (2.0178) = 1.042 × 10-2 s-1
Therefore, k is 1.042 × 10-2 s-1 .

30. The rate of a reaction quadruples when the temperature changes from 293
K to 313 K. Calculate the energy of activation of the reaction assuming that
it does not change with temperature.
Ans: We are given that:
k 2 = 4 k1
T1 = 293K
T2 = 313K
According the Arrhenius equation, we get:
k E a  T2 -T1 
log 2 =  
k1 2.303R  T1T2 
Putting the values, we get:
4k Ea  313-293 
log 1 =  
k1 2.303 × 8.314  293 × 313 
Ea  313-293 
0.6021 =  
2.303 × 8.314  293 × 313 
0.6021 × 2.303 × 8.314 × 293 × 313
Ea =
20
-1
Ea = 52863.00 J mol
Ea = 52.863 kJ mol-1
Therefore, the required activation energy is 52.863 kJ mol-1 .

Class XII Chemistry www.vedantu.com 35