NCERT Solutions for Class 12 Chemistry Chapter 4 Chemical kinetics

Question 4.1 For the reaction , the concentration of a reactant change

from to in minutes. Calculate the average rate of reaction using units

of time both in minutes and seconds.

e
Answer :

ut
We know that,

tit
The average rate of reaction =

s
In
=

=
sh

In seconds we need to divide it by 60. So,

ka

= 6.67
Aa

Question 4.2 In a reaction, P, the concentration of A decreases

from to in 10 minutes. Calculate the rate during this interval?
Answer :

According to the formula of an average rate

= (final concentration - initial conc.)/time interval

e
=

ut
=

tit
=

s
In
Question 4.3 For a reaction, ; the rate law is given
by, . What is the order of the reaction?
sh

Answer :

Order of reaction = Sum of power of concentration of the reactant in the rate law
ka

expressions

So, here the power of A = 0.5

Aa

and power of B = 2

order of reaction = 2+0.5 =2.5

Question 4.4 The conversion of 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
?
Answer :

The order of a reaction means the sum of the power of concentration of the reactant in
rate law expression.

So rate law expression for the second-order reaction is here R = rate

e
if the concentration is increased to 3 times means

ut
new rate law expression = = = 9R

tit
the rate of formation of Y becomes 9 times faster than before

will
s
Question 4.5 A first order reaction has a rate constant
of his reactant take to reduce to ?
. How long
In
Answer :
sh

Given data,

initial conc. = 5g
ka

final conc. = 3g

rate const. for first-order =

Aa

We know that for the first-order reaction,

[log(5/3)= 0.2219]
= 444.38 sec (approx)

Question 4.6 Time required to decompose to half of its initial amount

is minutes. If the decomposition is a first order reaction, calculate the rate constant of
the reaction.

e
Answer :

ut
We know that t(half ) for the first-order reaction is

tit
and we have given the value of half time

thus,

s
In
= 0.01155 /min

OR = 1.1925
sh

Alternative method

we can also solve this problem by using the first-order reaction equation.
ka
Aa

put

Question 4.7 What will be the effect of temperature on rate constant ?

Answer :

The rate constant of the reaction is nearly doubled on rising in 10-degree temperature.
Arrhenius equation depicts the relation between temperature and rates constant.

A= Arrhenius factor

e
Ea = Activation energy

ut
R = gas constant

T = temperature

tit
Question 4.8 The rate of the chemical reaction doubles for an increase of in
absolute temperature from

s
Calculate .
In
Answer :

Given data
sh

(initial temperature) = 298K and (final temperature)= 308K

And we know that rate of reaction is nearly doubled when temperature rise 10-degree
ka

So, and R = 8.314 J/mol/K

Aa

now,

On putting the value of given data we get,

Activation energy ( )=

=52.9 KJ/mol(approx)

Question 4.9 The activation energy for the

reaction is at . Calculate the fraction of

e
molecules of reactants having energy equal to or greater than activation energy?

ut
Answer :

tit
We have

Activation energy = 209.5KJ/mol

s
In
temperature= 581K

R = 8.314J/mol/K
sh

Now, the fraction of molecules of reactants having energy equal to or greater than
activation energy is given as
ka

taking log both sides we get

Aa

= 18.832
x = antilog(18.832)

= 1.471

NCERT Solutions for class 12 chemistry chapter 4

e
Question 4.1(i) From the rate expression for the following reactions, determine their
order of reaction and the dimensions of the rate constants.

ut
tit
Answer :

Given pieces of information

s
In
Rate =

so the order of the reaction is 2

sh

The dimension of k =
ka
Aa

Question 4.1(ii) From the rate expression for the following reactions determine their
order of reaction and the dimensions of the rate constants.

(ii)

Answer :

Given rate =
therefore the order of the reaction is 2

Dimension of k =

e
Question 4.1(iii) From the rate expression for the following reactions, determine their
order of reaction and the dimensions of the rate constants.

ut
tit
Answer :

Given

s
In
therefore the order of the reaction is 3/2

and the dimension of k

sh
ka

Question 4.1(iv) From the rate expression for the following reactions, determine their
order of reaction and the dimensions of the rate constants.
Aa

Answer :

so the order of the reaction is 1

and the dimension of k =

Question 4.2 For the reaction:

e
the rate = with . Calculate the initial rate of the

ut
reaction when . Calculate the rate of reaction
after is reduced to .

tit
Answer :

The initial rate of reaction =

s
In
substitute the given values of [A], [B] and k,
sh

rate =

=8
ka

When [A] is reduced from 0.1 mol/L to 0.06 mol/L

So, conc. of A reacted = 0.1-0.06 = 0.04 mol/L

Aa

and conc. of B reacted = 1/2(0.04) = 0.02mol/L

conc. of B left = (0.2-0.02) = 0.18 mol/L

Now, the rate of the reaction is (R) =

=

Question 4.3 The decomposition of on platinum surface is zero order reaction.

What are the rates of production of and if ?

e
Answer :

ut
The decomposition of on the platinum surface reaction

s tit
therefore,
In
Rate =

For zero order reaction rate = k

sh

therefore,
ka

So

and the rate of production of dihydrogen =3 (2.5 )

Aa

= 7.5

Question 4.4 The decomposition of dimethyl ether leads to the formation

of , and and the reaction rate is given by

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.,
 If the pressure is measured in bar and tidame in minutes, then what are the units of rate
and rate constants?

Answer :

e
Given that

ut
tit
So, the unit of rate is bar/min .( )

And thus the unit of k = unit of rate

s
In
Question 4.5 Mention the factors that affect the rate of a chemical reaction.
sh

Answer :

The following factors that affect the rate of reaction-

ka

• the concentration of reactants

• temperature, and
presence of catalyst
Aa

Question 4.6(i) A reaction is second order with respect to a reactant. How is the rate of
reaction affected if the concentration of the reactant is doubled

Answer :

Let assume the concentration of reactant be x

So, rate of reaction,

Now, if the concentration of reactant is doubled then . So the rate of reaction

would be

Hence we can say that the rate of reaction increased by 4 times.

e
Question 4.6(ii) A reaction is second order with respect to a reactant. How is the rate of

ut
reaction affected if the concentration of the reactant is reduced to half ?

tit
Answer :

Let assume the concentration of reactant be x

So, rate of reaction, R =

s
In
Now, if the concentration of reactant is doubled then . So the rate of reaction
sh

would be

Hence we can say that the rate of reaction reduced to 1/4 times.
ka

Question 4.7 What is the effect of temperature on the rate constant of a reaction? How
can this effect of temperature on rate constant be represented quantitatively?
Aa

Answer :

The rate constant is nearly double when there is a 10-degree rise in temperature in a
chemical reaction.

effect of temperature on rate constant be represented quantitatively by Arrhenius

equation,
 where k is rate constant

A is Arrhenius factor

R is gas constant

e
T is temperature and

ut
is the activation energy

tit
Question 4.8 In pseudo first order hydrolysis of ester in water, the following results
were obtained:

s
In
sh

(i) Calculate the average rate of reaction between the time interval 30 to 60 seconds.

Answer :
ka

The average rate of reaction between the time 30 s to 60 s is expressed as-

Aa

Question 4.9(i) A reaction is first order in A and second order in B.

(i)Write the differential rate equation.

Answer :

the reaction is first order in A and second order in B. it means the power of A is one and
power of B is 2

The differential rate equation will be-

e
ut
Question 4.9(ii) A reaction is first order in A and second order in B.

tit
(ii) How is the rate affected on increasing the concentration of B three times?

Answer :

s
In
If the concentration of [B] is increased by 3 times, then
sh

Therefore, the rate of reaction will increase 9 times.

ka

Question 4.9(iii) A reaction is first order in A and second order in B.

Aa

(iii) How is the rate affected when the concentrations of both A and B are doubled?

Answer :

If the concentration of [A] and[B] is increased by 2 times, then

Therefore, the rate of reaction will increase 8 times.

Question 4.10 In a reaction between A and B, the initial rate of reaction (r0) was
measure for different initial concentrations of A and B as given below:

e
ut
What is the order of the reaction with respect to A and B?

tit
Answer :

we know that
s
In
rate law ( )=
As per data
sh

these are the equation 1, 2 and 3 respectively

Now, divide eq.1 by equation2, we get

ka

from here we calculate that y = 0

Again, divide eq. 2 by Eq. 3, we get

Aa

Since y =0 also substitute the value of y

So,

=
taking log both side we get,

= 1.496

= approx 1.5

e
Hence the order of reaction w.r.t A is 1.5 and w.r.t B is 0(zero)

ut
Question 4.11 The following results have been obtained during the kinetic studies of

the reaction:

tit
2A + B C+D

s
In
sh

Determine the rate law and the rate constant for the reaction .

Answer :
ka

Let assume the rate of reaction wrt A is and wrt B is . So, the rate of reaction is

expressed as-
Aa

Rate =

According to given data,

these are the equation 1, 2, 3 and 4 respectively
Now, divide the equation(iv) by (i) we get,

from here we calculate that

Again, divide equation (iii) by (ii)

e
from here we can calculate the value of y is 2

ut
Thus, the rate law is now,

So,

s tit
Hence the rate constant of the reaction is
In
Question 4.12 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:
sh
ka

Answer :
Aa

The given reaction is first order wrt A and zero order in wrt B. So, the rate of reaction

can be expressed as;

Rate = k[A]
from exp 1,

k = 0.2 per min.

from experiment 2nd,

e
[A] =

ut
from experiment 3rd,

s tit
from the experiment 4th,
In
from here [A] = 0.1 mol/L
sh

Question 4.13 (1) Calculate the half-life of a first order reaction from their rate

constants given below:

ka

Answer :
Aa

We know that,

half-life ( ) for first-order reaction =

=
Question 4.13 (2) Calculate the half-life of a first order reaction from their rate

constants given below:

Answer :

e
the half-life for the first-order reaction is expressed as ;

ut
tit
= 0.693/2
= 0.35 min (approx)

s
In
Question 4.13 (3) Calculate the half-life of a first order reaction from their rate

constants given below:

sh

Answer :
ka

The half-life for the first-order reaction is

= 0.693/4
= 0.173 year (approximately)
Aa

Question 4.14 The half-life for radioactive decay of is 5730 years. An

archaeological artifact containing wood had only 80% of the 14C found in a living tree.
Estimate the age of the sample.

Answer :
Given ,

half-life of radioactive decay = 5730 years

So,
per year

we know that, for first-order reaction,

e
ut
tit
= 1845 years (approximately)

Thus, the age of the sample is 1845 years

s
Question 4.15 (1) The experimental data for decomposition of
In
in gas phase at 318K are given below:
sh
ka

Plot against t.
Aa

Answer :

On increasing time, the concentration of gradually decreasing exponentially.

 e
ut
s tit
Question 4.15 (2) The experimental data for decomposition
In
of in gas phase at 318K are given below:
sh

Find the half-life period for the reaction.

ka

Answer :
Aa

The half-life of the reaction is-

The time corresponding to the mol/ L = 81.5 mol /L is the half-life of the
reaction. From the graph, the answer should be in the range of 1400 s to 1500 s.
Question 4.15 (3) The experimental data for decomposition
of in gas phase at 318K are given below:

e
Draw a graph between and t.

ut
Answer :

s tit
0 1.63 -1.79
In
400 1.36 -1.87
sh

800 1.14 -1.94

1200 0.93 -2.03

ka

1600 0.78 -2.11

Aa

2000 0.64 -2.19

2400 0.53 -2.28

2800 0.43 -2.37

 3200 0.35 -2.46

e
ut
s tit
In
sh

Question 4.15 (4) The experimental data for decomposition

ka

of in gas phase at 318K are given below:

Aa

What is the rate law ?

Answer :

Here, the reaction is in first order reaction because its log graph is linear.
Thus rate law can be expessed as

Question 4.15 (5) The experimental data for decomposition

e
of in gas phase at 318K are given below:

ut
tit
Calculate the rate constant.

Answer :
s
In
From the log graph,
sh

the slope of the graph is =

= -k/2.303 ..(from log equation)
ka

On comparing both the equation we get,

Aa

Question 4.15 (6) The experimental data for decomposition

of in gas phase at 318K are given below:
Calculate the half-life period from k and compare it with (ii).

e
Answer :

ut
The half life produce =

tit
Question 4.15(7) The rate constant for a first order reaction is . How much time

s
will it take to reduce the initial concentration of the reactant to its 1/16th value?
In
Answer :

We know that,
sh

for first order reaction,

ka
Aa

(nearly)

Hence the time required is

Question 4.17 During nuclear explosion, one of the products is with half-life of

28.1 years. If of 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.

Answer :

Given,

e
half life = 21.8 years

ut
= 0.693/21.8

tit
and,

s
In
by putting the value we get,
sh

taking antilog on both sides,

[R] = antilog(-0.1071)
ka

= 0.781

Thus 0.781 of will remain after given 10 years of time.

Aa

Again,
 e
ut
Thus 0.2278 of will remain after 60 years.

tit
Question 4.18 For a first order reaction, show that time required for 99% completion is

s
twice the time required for the completion of 90% of reaction.
In
Answer :

case 1-
sh

for 99% complition,

ka
Aa

CASE- II
for 90% complition,
 e
Hence proved.

ut
Question 4.19 A first order reaction takes 40 min for 30% decomposition. Calculate

tit
Answer :

For the first-order reaction,

s
In
(30% already decomposed and remaining is 70%)
sh

therefore half life = 0.693/k

ka

=
= 77.7 (approx)
Aa

Question 4.20 For the decomposition of azoisopropane to hexane and nitrogen at

543K, the following data are obtained.
Calculate the rate constant.

Answer :

Decomposition is represented by equation-

e
ut
After t time, the total pressure =

tit
So,

thus,

s
In
for first order reaction,
sh

now putting the values of pressures,

ka

when t =360sec
Aa

when t = 270sec
So,

Question 4.21 The following data were obtained during the first order thermal

decomposition of at a constant volume.

e
ut
tit
Calculate the rate of the reaction when total pressure is 0.65 atm.

s
In
Answer :

The thermal decomposition of is shown here;

sh
ka

After t time, the total pressure =

So,
Aa

thus,

for first order reaction,

now putting the values of pressures, when t = 100s

e
when

ut
= 0.65 - 0.5

tit
= 0.15 atm

So,

s
= 0.5 - 0.15
In
= 0.35 atm

Thus, rate of reaction, when the total pressure is 0.65 atm

sh

rate = k( )

=
= 7.8
ka

Question 4.22 The rate constant for the decomposition of N2O5 at various

temperatures
Aa

is given below:
Draw a graph between ln k and 1/T and calculate the values of A and
. Predict the rate constant at 30° and 50°C.

Answer :

e
From the above data,

ut
T/ 0 20 40 60 80

tit
T/K 273 293 313 333 353

( )
s 3.66 3.41 3.19 3.0 2.83
In
0.0787 1.70 25.7 178 2140
sh

-7.147 -4.075 -1.359 -0.577 3.063

ka
Aa
 e
ut
tit
Slope of line =

According to Arrhenius equations,

s
In
Slope =

12.30 8.314
sh

= 102.27

Again,
ka
Aa
When T = 30 +273 = 303 K and 1/T =0.0033K

k=

When T = 50 + 273 = 323 K and 1/T = 3.1 K

e
ut
k = 0.607 per sec

Question 4.23 The rate constant for the decomposition of hydrocarbons

tit
is at 546 K. If the energy of activation is 179.9 kJ/mol, what will be the
value of pre-exponential factor.

Answer :
s
In
Given that,

k=
sh

= 179.9 KJ/mol
T(temp) = 546K
ka

According to Arrhenius equation,

taking log on both sides,

Aa
= (0.3835 - 5) + 17.2082

= 12.5917

Thus A = antilog (12.5917)

A = 3.9 per sec (approx)

Question 4.24 Consider a certain reaction A Products with .

e
Calculatethe concentration of A remaining after 100 s if the initial concentration of A is

ut
1.0 mol

Answer :

tit
Given that,

k=

s
t = 100 s
In
Here the unit of k is in per sec, it means it is a first-order reaction.
sh

therefore,
ka
Aa

Hence the concentration of rest test sample is 0.135 mol/L

Question 4.25 Sucrose decomposes in acid solution into glucose and fructose

according to the first order rate law, with hours. What fraction of sample of
sucrose remains after 8 hours ?

Answer :
For first order reaction,

given that half life = 3 hrs ( )

e
Therefore k = 0.693/half-life

ut
= 0.231 per hour

Now,

s tit
In
= antilog (0.8024)
= 6.3445
sh

(approx)
ka

Therefore fraction of sample of sucrose remains after 8 hrs is 0.157

Question 4.26 The decomposition of hydrocarbon follows the

Aa

equation . Calculate

Answer :

The Arrhenius equation is given by

.................................(i)
given equation,
............................(ii)

by comparing equation (i) & (ii) we get,

A= 4.51011 per sec

e
ut
Activation energy = 28000 (R = 8.314)
= 232.792 KJ/mol

tit
Question 4.27 The rate constant for the first order decomposition of is given by

the following equation:

s .
In
Calculate for this reaction and at what temperature will its half-period be 256
minutes?
sh

Answer :

The Arrhenius equation is given by

ka

taking log on both sides,

Aa

....................(i)

given equation,

.....................(ii)

On comparing both equation we get,

activation energy

half life ( ) = 256 min

e
ut
k = 0.693/256

tit
With the help of equation (ii),

s
In
T=
sh

= 669 (approx)

Question 4.28 The decomposition of A into product has value of k as at

ka

10°Cand energy of activation 60 kJ mol–1. At what temperature would k

be ?
Aa

Answer :

The decomposition of A into a product has a value of k as at 10°C and

energy of activation 60 kJ mol–1.

K1 =
K2 =
 = 60 kJ mol–1

K2 =

e
ut
s tit
In
sh
ka

Question 4.29 The time required for 10% completion of a first order reaction at 298K is

equal to that required for its 25% completion at 308K. If the value of A is .
Calculate k at 318K and Ea.
Aa

Answer :

We know that,

for a first order reaction-

Case 1

At temp. = 298 K

e
= 0.1054/k

ut
Case 2
At temp = 308 K

tit
s
= 2.2877/k'

As per the question

In
K'/K = 2.7296
sh

From Arrhenius equation,

ka
Aa

= 76640.096 J /mol
=76.64 KJ/mol
k at 318 K

we have , T =318K
A=

Now

e
After putting the calue of given variable, we get

ut
on takingantilog we get,

tit
k = antilog(-1.9855)

= 1.034

s
In
Question 4.30 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.
sh

Answer :

From the Arrhenius equation,

ka

...................................(i)
Aa

it is given that
T1= 293 K

T2 = 313 K
Putting all these values in equation (i) we get,
Activation Energy = 52.86 KJ/mo l

e
This is the required activation energy

ut
s tit
In
sh
ka
Aa