In text

3.5 A first order reaction has a rate constant 1.15 × 10--3 s—1 . How
long will 5 g of this reactant take to reduce to 3 g?
5
Given the value of log 3 as 0.2219.
Ans :
Initial amount = 5 g
Final concentration = 3 g
Rate constant = 1.15 x 10--3 s—1
T = ????
First order reaction

= 444.38 s

3.6 Time required to decompose SO2 Cl2 to half of its initial

amount is 60 minutes. If the decomposition is a first order
reaction, calculate the rate constant of the reaction.
Ans:
First order reaction
t½ ==60 min
k==?
We know that for a 1st order reaction, t½ = 0.693 / k
k = 0.693 / t½
= 0.693 / 60
= 0.01155 min-1
= 1.155 min-1
or 1.155 min-1 / 60 = 1.925 x 10—2 s—1
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Example : 3.9
The rate constants of a reaction at 500K and 700K are 0.02 s—1
and 0.07 s—1 respectively. Calculate the values of Ea and A.
Given R = 8.314 JK—1 mol—1
Ans: Given:
t1 = 500 K k1 = 0.02 s—1
t2 = 700 K k2 = 0.07 s—1
R = 8.314 JK—1 mol—1
also given log 3.5 = 0.544
also given the value of e as 2.71
also given the value of 2.71− 0.4385 as 0.012
Ea = ?
A =?

𝑘2 𝐸𝑎 𝑡2−𝑡1
log = x
𝑘1 2.303 𝑅 𝑡1 x 𝑡2

Substituting :

0.007 𝐸𝑎 700 −500

log 0.002 = x
2.303 x 8.3014 J/mol 700 x 500

𝐸𝑎 200
log 3.5 = x 350000
19.15

200
0.544 = 6702500 Ea

0.544 x 6702500 = 200 Ea . Hence Ea = 18230 J/ mol

k =Ae

k/e = A

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Calculation of e
Knowing the value of
k as : 0.02 s—1
R = 8.314 JK—1 mol—1
T = 500 K

18230 𝐽/𝑚𝑜𝑙
--Ea / RT = 𝐽 = -- 4.385
8.314𝑚𝑜𝑙 x 500𝐾

Hence A = 0.02 / e—4.385

Value of e—4.385 = 2.71− 0.4385 = 0.012
0.02
Hence A = Hence A = 1.66
0.012

Example : 3.10

Ans : Given :
k = 1.60 x 10—5 s—1
Ea = 209 kJ/mol
t1 = 600 K
t2 = 700 K
k = ???
also given the value of log 1.60 x 10—5 = -- 4.796
also given the value of the antilog of -- 2.197 as 6.36 x 10 -- 3

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Substituting :

209000 100
Hence : -- 4.796 + x
19.15 420000
Hence : -- 4.796 + 2.599 = -- 2.197
Hence : the value of k2 = 6.36 x 10 – 3 s - 1

Intext Questions
3.7 What will be the effect of temperature on rate constant ?
Ans :
The rate constant of a reaction is nearly doubled with a 10° rise in
temperature.

3.8 The rate of the chemical reaction doubles for an increase of

10K in absolute temperature from 298K. Calculate Ea.
Ans :
Given : t1 = 298 K
∴ t2 = (298 + 10) K = 308 K

We know that the rate of the reaction doubles when temperature is

increased by 10°.
Hence assume k1 = k and thus k2 = 2k
Also, R = 8.314 J K—1 mol—1

Also given the value of log 2 as 0.3010

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= 52897.78 J mol—1

Hence: the value of Ea = 52.9 kJ mol—1

3.9 The activation energy for the reaction

2 HI(g) → H2(g) + I2(g)

is 209.5 kJ mol—1 at 581K.

Calculate the fraction of molecules of reactants having energy
equal to or greater than activation energy?
Ans:
Given :
Ea = 209.5 kJ mol—1 = 209500 J mol—1
T = 581 K
R = 8.314 JK—1 mol—1
Also given the antilog of 18.8323 as 1.471 x 10 – 19
Now, the fraction of molecules of reactants having energy equal to
or greater than activation energy is given as x = e – Ea / RT

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Hence , the fraction of molecules of reactants having energy equal
to or greater than activation energy is 1.471 x 10 – 19
Lesson end Exercise
3.3 The decomposition of NH3 on platinum surface is zero order
reaction. What are the rates of production of N2 and H2
if k = 2.5 × 10—4 mol—1 L s
Ans:

= 7.5 × 10 - 4mol L - 1s – 1

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3.4 The decomposition of dimethyl ether leads to the formation of
CH4, H2 and CO and the reaction rate is given by

Rate = k [CH3 O CH3 ]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 [PCH3 O CH3 ]3/2

If the pressure is measured in bar and time in minutes, then what
are the units of rate and rate constants?
Ans :
If pressure is measured in bar and time in minutes, then

Unit of rate = bar min-1

Rate = k [PCH3 O CH3 ]3/2

⇒ k = Rate / [PCH3 O CH3 ]3/2

Therefore, unit of rate constants (k) = bar min-1 / bar3/2

= bar—1/2 min-1

3.5 Mention the factors that affect the rate of a chemical reaction.
Ans:
The factors that affect the rate of a reaction areas follows.
(i) Concentration of reactants (pressure in case of gases)
(ii) Temperature
(iii) Presence of a catalyst

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3.6 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 (ii) reduced to half ?
Ans:
Let the concentration of the reactant be [A] = x
Second order reaction….Hence
Rate of reaction, R = k [A]2 = kx2

(i) If the concentration of the reactant is doubled, i.e. [A] = 2x,

then the rate of the reaction would be
R = k (2x)2 = 4 kx2 = 4 R
Therefore, the rate of the reaction would increase by 4 times.

(ii) If the concentration of the reactant is reduced to half,

Let the concentration of the reactant be [A] = x
Second order reaction….Hence
Rate of reaction, R = k [A]2 = kx2

Hence [A] = ½ x , then the rate of the reaction would be

1 1
R = k(½ x )22 = 4 Kx2 =4R
1
Therefore, the rate of the reaction would increase by 4 times

3.7 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 :
The rate constant is nearly doubled with a rise in temperature by
10° for a chemical reaction.

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The temperature effect on the rate constant can be represented
quantitatively by Arrhenius equation,
k = A e – Ea / RT
where, k is the rate constant,
A is the Arrhenius factor or the frequency factor,
R is the gas constant,
T is the temperature, and
Ea is the energy of activation for the reaction

3.8 In a pseudo first order hydrolysis of ester in water, the

following results were obtained:

(i) Calculate the average rate of reaction between the time interval
30 to 60 seconds.
(ii) Calculate the pseudo first order rate constant for the hydrolysis
of ester.
Ans:
(i) Average rate of reaction between the time interval, 30 to 60
seconds, = d[ester] / dt
= (0.31-0.17) / (60-30) = 0.14 / 30 = 4.67 × 10 - 3mol L—1 s—1

2.303
(ii) For a pseudo first order reaction, k = log [R]º / [R]
𝑡

Substituting
For t= 30 s, find k1 . Hence t = 30s , R0 = 0.55 R = 0.31
THUS : k1 = 2.303/ 30 log 0.55 / 0.31 = 1.911 × 10—2 s—1

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Substituting
For t= 60 s, find k2 . Hence t = 60s , R0 = 0.55 R = 0.17
THUS : k2 = 2.303/ 60 log 0.55 / 0.17 = 1.957 × 10—2 s—1

Substituting
For t= 90 s, find k3 . Hence t = 90s , R0 = 0.55 R = 0.085
THUS : k3 = 2.303/ 90 log 0.55 / 0.085 = 2.075 × 10—2 s—1

Then, average rate constant, k = k1 + k2+ k3 / 3

= 1.911 × 10 --2 + 1.957 × 10 --2 + 2.075 × 10 --2 / 3
= 1.981 × 10—2 s—1

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

(i) Write the differential rate equation.
(ii) How is the rate affected on increasing the concentration of B
three times?
(iii) How is the rate affected when the concentrations of both A
and B are doubled?
Ans:

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

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

Ans : r = k [A]X [B]Y
Let the order of the reaction with respect to A be x
and Let the order of the reaction with respect to B be y.

= 1.496 = 1.5 (approximately)

Hence
r =: k [A]½ [B]0 11 | P a g e
3.11 The following results have been obtained during the kinetic studies of
the reaction:

Ans:

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3.12

The given reaction is of the first order with respect to A and of zero order
with respect to B. Therefore, the rate of the reaction is given by,

Rate = k [A]1 [B]0 ⇒ Rate = k [A]

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Experiment I, we obtain: 2.0 x 10--2 mol L-1 min-1 = k (0.1 mol L-1 )

k =2.0 x 10--2 mol L-1min-1 / 0.1 mol L-1 ⇒ k = 0.2 min-1

Experiment II, we obtain: 4.0 x 10--2 mol L-1 min-1 = 0.2 min—1 [A]

[A] = 4.0 x 10--2 mol L-1 min-1 / 0.2 min—1 ⇒ [A] = 0.2 mol L—1

Experiment III, we obtain :

Rate = 0.2 min-1 x 0.4 mol L—1 = 0.08 mol L-1 min-1

Experiment IV, we obtain : 2.0 x 10--2 mol L-1 min-1 = 0.2 min—1 [A]

[A] = 2.0 x 10--2 mol L-1 min-1 / 0.2 min—1 ⇒ [A] = 0.1 mol L—1

3.13 Calculate the half-life of a first order reaction from their rate constants
given below:

(i) 200 s—1 (ii) 2 min—1 (iii) 4 years—1

Ans : First order reaction . Hence , t½ = 0.693 / k

(i) Half life, t½ = 0.693 / k

= 0.693 / 200 s—1 = 3.47 ×10—3 s (approximately)

(ii) Half life, t½ = 0.693 / k

= 0.693 / 2 min—1 = 0.35 min (approximately)

(iii) Half life,t½ = 0.693 / k

= 0.693 / 4 years—1 = 0.173 years (approximately)

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3.14
The half-life for radioactive decay of 14C is 5730 years. An archaeological
artifact containing wood had only 80% of the 14 C found in a living tree.
Estimate the age of the sample. Given the value of log 10 / 8 = 0.125
Ans :
Radioactive decay follows first-order kinetics. Hence t½ = 0.693 / k
k = 0.693 / t½
= 0.693 / 5730 years-1
It is known that,

= 1845 years (approximately).

Hence, the age of the sample is 1845 years.

3.16
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 1/16 th value ?
given the value of log 16 as 1.2
Ans :
First order reaction.
Hence :

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3.17
During nuclear explosion, one of the products is 90Sr with half-life of
28.1 years. If 1mg of 90Sr 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.
Given the antilog of – 0.1071 as 0.7814 & the antilog of -- 0.6425 as 0.2278
Ans: First order reaction
Hence : t½ = 0.693 / k
Hence : k = 0.693 / t½

Substituting : k = 0.693 / 28.1 years – 1

But for a first order reaction :

(i ) Since t = 10 years Hence : Substituting

Therefore, 0.7814 μg of 90Sr will remain after 10 years.

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(ii ) Since t = 60 years Hence : Substituting

Therefore, 0.2278 μg of 90Sr will remain after 60 years.

3.18 For a first order reaction, show that time required for 99% completion
is twice the time required for the completion of 90% of reaction.
Given log 10 = 1 and log 100 = 2
Ans: First order reaction

For a first order reaction, the time required for 99% completion is
2.303 100 2.303 2.303
t1 = Log = log 100. Hence t1 = 2 x
𝑘 100−99 𝑘 𝑘

For a first order reaction, the time required for 90% completion is
2.303 100 2.303 2.303
t2 = Log = log 10. Hence t2 =
𝑘 100−90 𝑘 𝑘

Therefore, t1 = 2 t2

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.

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3.19
A first order reaction takes 40 min for 30% decomposition. Calculate t ½
10
Given the value of log = 0.1428
7
2.303 [𝑅]0
Ans : For a first order reaction, t = Log
𝑘 [𝑅]
2.303 100
t = 40 min . hence : k = Log = 8.918 x 10—3 min—1
40 100−30
0.693
Substituting the value of k in t ½ = , we have
𝑘
0.693
= , = 77.7 min (approximately)
8.918 x 10—3 min—1
Hence the t½ of the first order reaction is approximately 77.7 min

3.30 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.
Given : R = 8.314 J K-1 mol-1 and log 4 = 0.6021
Ans:.
Given : T1 = 293 K and T2 = 313 K
Rate becomes 4 times. Hence k2 = 4 k1
R = 8.314 J K-1 mol-1 . Energy of activation = ????
We have to use the Arrhenius equation

Substituting :

Hence, the required energy of activation is 52.86 kJ mol—1 .

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3.29 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 4 × 1010 s—1 .Calculate k at 318K and Ea. Given the value
of log 2.7296 = 0.4361 and the antilog of -1.9855 is 1.034 x 10—2

Ans: First order reaction. Hence :

At 298 K
2.303 100 0.1054
t1 = Log =
𝑘1 100−10 𝑘1
At 308 K,
2.303 100 2.2877
t2 = Log =
𝑘2 100−25 𝑘2

0.1054 2.2877
According to the question, t1 = t2 . Hence : =
𝑘1 𝑘2
𝑘2
Hence : ⇒ = 2.7296
𝑘1
From Arrhenius equation, we have :

Substituting :

To calculate k at 318 K,
It is given that, A = 4 x 1010 s—1 , T = 318K
Again, from Arrhenius equation, we obtain

k = Antilog (-1.9855) = 1.034 x 10-2 s—1

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3.28 The decomposition of A into product has value of k as 4.5 x 10 3 s-1 at
10°C and energy of activation 60 kJ mol-1 . At what temperature would k be
1.5 x 104 s-1 ?

Ans:

Given:

t1 = 100 C = 283 K

k1 = 4.5 x 103 s-1

t2 = ???

k2 = 1.5 x 104 s-1

Ea = 60 kJ mol-1 = 6 x 104 J mol – 1

From Arrhenius equation,

Substituting

= 297 K = 24°C

Hence, k would be 1.5 × 104 s - 1 at 24°C.

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3.26 The decomposition of hydrocarbon follows the equation

k = (4.5 × 1011 s – 1 ) e – 28000 K / T . Calculate Ea

Ans : Arrhenius equation says

k = A e – Ea / RT
where, k is the rate constant,
A is the Arrhenius factor or the frequency factor,
R is the gas constant,
T is the temperature, and
Ea is the energy of activation for the reaction

Hence :

k = A e – Ea / RT ……………………….. (1)

given equation :

k = (4.5 × 1011 s – 1 ) e – 28000 K / T ……………….(2)

from (1) and (2) . we get:

− 𝐸𝑎 − 28000 𝐾
=
𝑅𝑇 𝑇

Hence : Ea = 28000 K x R

= 28000 K x 8.314 J K—1 mol -- 1

= 232792 J mol - 1

Hence Ea = 232.792 kJ mol - 1

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3.27 The rate constant for the first order decomposition of H2 O2 is given by
The following equation: log k = 14.34 – 1.25 × 10 4 K/T
Calculate Ea for this reaction and at what temperature will its
half- period be 256 minutes? Given log 4.51 = 0.6542
Ans :
Arrhenius equation says : k = A e – Ea / RT
Taking log on both sides:
𝐸𝑎
log A = log A -- 2.303 𝑅𝑇
given equation :
log k = 14.34 – 1.25 × 10 4 K/T

𝐸𝑎 1.25 x 104 𝐾
we get : =
2.303 𝑅𝑇 𝑇
Hence : Ea = 2.303 R x 1.25 x 104 K
= 2.303 x 8.314 x 1.25 x 104 K
= 239339.3 J mol – 1
Ea = 239. 34 k J mol – 1
Given : t½ = 256 min = 256 x 60 s
0.693
Hence : k = 256 x 60
Hence k = 4.51 × 10 -- 5 s -- 1

Substituting the value of Ea and k in : log k = 14.34 – 1.25 × 10 4 K/T

We get :
1.25 𝑥 104 𝐾
log 4.51 × 10 -- 5 s – 1 = 14.34 -- 𝑇
1.25 𝑥 104 𝐾
-- 5 log 4.51 = 14.34 --
𝑇
1.25 𝑥 104 𝐾
-- 5 + 0.6542 = 14.34 -- 𝑇

1.25 𝑥 104 𝐾
-- 4.3458 -- 14.34 = -- 𝑇

1.25 𝑥 104 𝐾
Hence : 18.6858 = = 668.95 K
𝑇

Hence T = 669 K
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3.23 The rate constant for the decomposition of hydrocarbons is
2.418 x 10 —5 s –1 at 546 K. If the energy of activation is
179.9 kJ/mol, what will be the value of pre-exponential factor.
Given : log 2.418 = 0.3834 and antilog of 12.5924 as 3.912 x 1012
Ans : Given :

k= 2.418 x 10 —5 s –1
T= 546 K
Ea= 179.9 kJ mol—1 = 179.9 × 103 J mol –1
A = ??
Arrhenius equation says : k = A e – Ea / RT

𝐸𝑎
Taking log : we get : log k = log A -- 2.303 𝑅𝑇

𝐸
Rearranging : log A = log k + 2.303𝑎 𝑅𝑇
Substituting :

179.9 1 1
log A = log 2.418 x 10 —5 s –1 + x 8.314 𝑥 10− 3 x 546
2.303

log A = --5 log 2.418 + 17.2081

log A = --5 + 0.3834 + 17.2081

log A = 12.5924

using the antilog of 12.5924

Hence A = 3.912 x 1012 s – 1

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3.24 Consider a certain reaction A → Products
with k = 2.0 x 10-- 2 s –1
Calculate the concentration of A remaining after 100 s if the initial
concentration of A is 1.0 mol L—1 .
Ans:
T= 100 s
[A]o= 1.0 moL--1
[A] = ????
k = 2.0 x 10-- 2 s –1
hence the reaction is a first order reaction.

2.303 [𝐴]0
Hence : k = 𝑡
x log [𝐴]

2.303 1.0 mol L—1 .

Substituting : 2.0 x 10-- 2 s –1 = 100 𝑠 x log [𝐴]

2.303
Hence : 2.0 x 10-- 2 s –1 = ( -- log [A] )
100 𝑠

100 𝑠
Hence : -- log [A] = -- 2.0 x 10-- 2 s –1 x 2.303

Hence : -- log [A] = -- 0.8684

Using the anti log of -- 0.8684

We get : 0.135 mol L – 1

Hence the concentration of A remaining after 100 s is 0.135 mol L – 1

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3.25 Sucrose decomposes in acid solution into glucose and fructose
according to the first order rate law, with t½ = 3.00 hours.
What fraction of sample of sucrose remains after 8 hours?

Ans :
t½ = 3.00 hours

[𝐴]
= ????
[𝐴]0

2.303 [𝐴]0
Decomposition of sucrose is a first order reaction.: k = x log
𝑡 [𝐴]
0.693
k= 𝑡½
0.693
substituting : k = = 0.231 hr—1
3
substituting this value of k in the first order equation when t = 8 hrs , we get

2.303 [𝐴]0
0.231 = x log
8 [𝐴]

[𝐴]0 0.231 x 8
Hence log =
[𝐴] 2.303

[𝐴]0
Hence log [𝐴]
= 0.8024

[𝐴]0
Hence = antilog of 0.8024 = 6.345
[𝐴]

[𝐴] 1
Hence = = 0.158
[𝐴]0 6.345

Hence, the fraction of sample of sucrose that remains after 8 hours is 0.158

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