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Page No 98:
Question 4.1:
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.
ANSWER:
Page No 98:
Question 4.2:
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?
ANSWER:
Average rate
= 0.005 mol L−1 min−1
= 5 × 10−3 M min−1
Page No 103:
Question 4.3:
For a reaction, A + B → Product; the rate law is given by, . What is the order
of the reaction?
ANSWER:
= 2.5
Page No 103:
Question 4.4:
Rate1 = k .(a)2
= ka2
Rate = k (3a)2
= 9(ka2)
Page No 111:
Question 4.5:
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?
ANSWER:
Initial amount = 5 g
Final concentration = 3 g
= 444 s (approx)
Page No 111:
Question 4.6:
Time required to decompose SO2Cl2 to half of its initial amount is 60 minutes. If the
decomposition is a first order reaction, calculate the rate constant of the reaction.
ANSWER:
Page No 116:
Question 4.7:
The rate constant of a reaction is nearly doubled with a 10° rise in temperature. However, the
exact dependence of the rate of a chemical reaction on temperature is given by Arrhenius
equation,
Where,
T is the temperature
Page No 116:
Question 4.8:
The rate of the chemical reaction doubles for an increase of 10 K in absolute temperature
from 298 K. Calculate Ea.
ANSWER:
= 308 K
We also know that the rate of the reaction doubles when temperature is increased by 10°.
We get:
= 52897.78 J mol−1
= 52.9 kJ mol−1
Note: There is a slight variation in this answer and the one given in the NCERT textbook.
Page No 116:
Question 4.9:
2HI(g) → H2 + 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?
ANSWER:
T = 581 K
Now, the fraction of molecules of reactants having energy equal to or greater than
activation energy is given as:
x= e−Ea/RT
⇒In x= −Ea/R
T⇒log x= −Ea/2.303RT
=−18.8323
Page No 117:
Question 4.1:
From the rate expression for the following reactions, determine their order of reaction and the
dimensions of the rate constants.
Dimension of
Dimension of
Dimension of
(iv) Given rate = k [C2H5Cl]
Dimension of
Page No 117:
Question 4.2:
2A + B → A2B
the rate = k[A][B]2 with k = 2.0 × 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.
ANSWER:
Rate = k [A][B]2
= (2.0 × 10−6 mol−2 L2 s−1) (0.1 mol L−1) (0.2 mol L−1)2
When [A] is reduced from 0.1 mol L−1 to 0.06 mol−1, the concentration of A reacted = (0.1 −
0.06) mol L−1 = 0.04 mol L−1
After [A] is reduced to 0.06 mol L−1, the rate of the reaction is given by,
Rate = k [A][B]2
= (2.0 × 10−6 mol−2 L2 s−1) (0.06 mol L−1) (0.18 mol L−1)2
Page No 117:
Question 4.3:
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−1?
ANSWER:
Therefore,
Therefore,
Page No 117:
Question 4.4:
The decomposition of dimethyl ether leads to the formation of CH4, H2 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.,
If the pressure is measured in bar andtime in minutes, then what are the units of rate and rate
constants?
ANSWER:
Page No 117:
Question 4.5:
Page No 118:
Question 4.6:
A reaction is second order with respect to a reactant. How is the rate of reaction affected if
the concentration of the reactant is
= ka2
(i)If the concentration of the reactant is doubled, i.e. [A] = 2a, then the rate of the reaction
would be
= 4ka2
=4R
(ii) If the concentration of the reactant is reduced to half, i.e. , then the rate of the
reaction would be
Therefore, the rate of the reaction would be reduced to
Page No 118:
Question 4.7:
What is the effect of temperature on the rate constant of a reaction? How can this temperature
effect on rate constant be represented quantitatively?
ANSWER:
The rate constant is nearly doubled with a rise in temperature by 10° for a chemical reaction.
The temperature effect on the rate constant can be represented quantitatively by Arrhenius
equation,
Page No 118:
Question 4.8:
In a pseudo first order hydrolysis of ester in water, the following results were obtained:
t/s 0 30 60 90
(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.
ANSWER:
For t = 30 s,
For t = 60 s,
For t = 90 s,
Page No 118:
Question 4.9:
(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?
ANSWER:
(i) The differential rate equation will be
Page No 118:
Question 4.10:
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:
r0/ mol L−1 s−1 5.07 × 10−5 5.07 × 10−5 1.43 × 10−4
Let the order of the reaction with respect to A be x and with respect to B be y.
Therefore,
Dividing equation (i) by (ii), we obtain
= 1.496
= 1.5 (approximately)
Hence, the order of the reaction with respect to A is 1.5 and with respect to B is zero.
Page No 118:
Question 4.11:
The following results have been obtained during the kinetic studies of the reaction:
2A + B → C + D
Determine the rate law and the rate constant for the reaction.
ANSWER:
Let the order of the reaction with respect to A be x and with respect to B be y.
Page No 118:
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:
ANSWER:
The given reaction is of the first order with respect to A and of zero order with respect to B.
⇒ Rate = k [A]
⇒ k = 0.2 min−1
Question 4.13:
Calculate the half-life of a first order reaction from their rate constants given below:
Page No 119:
Question 4.14:
The half-life for radioactive decay of 14C 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:
Here,
It is known that,
Page No 119:
Question 4.15:
(vi) Calculate the half-life period from k and compare it with (ii).
ANSWER:
i.
(iii)
t(s)
0 1.63 − 1.79
Therefore, we obtain,
Page No 119:
Question 4.16:
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?
ANSWER:
It is known that,
Page No 119:
Question 4.17:
During nuclear explosion, one of the products is 90Sr with half-life of 28.1 years. If 1μg
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.
ANSWER:
Here,
It is known that,
Therefore, 0.7814 μg of 90Sr will remain after 10 years.
Again,
Page No 119:
Question 4.18:
For a first order reaction, show that time required for 99% completion is twice the time
required for the completion of 90% of reaction.
ANSWER:
For a first order reaction, the time required for 99% completion is
For a first order reaction, the time required for 90% completion is
Therefore, t1 = 2t2
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.
Page No 119:
Question 4.19:
A first order reaction takes 40 min for 30% decomposition. Calculate t1/2.
ANSWER:
Page No 119:
Question 4.20:
For the decomposition of azoisopropane to hexane and nitrogen at 543 K, the following data
are obtained.
0 35.0
360 54.0
720 63.0
= 2P0 − Pt
When t = 360 s,
Note: There is a slight variation in this answer and the one given in the NCERT textbook.
Page No 119:
Question 4.21:
The following data were obtained during the first order thermal decomposition of SO2Cl2 at a
constant volume.
2 100 0.6
Calculate the rate of the reaction when total pressure is 0.65 atm.
ANSWER:
Therefore,
= 2 P0 − Pt
When t = 100 s,
P0 + p = 0.65
⇒ p = 0.65 − P0
= 0.65 − 0.5
= 0.15 atm
= P0 − p
= 0.5 − 0.15
= 0.35 atm
Therefore, the rate of equation, when total pressure is 0.65 atm, is given by,
Rate = k( )
The rate constant for the decomposition of N2O5 at various temperatures is given below:
T/°C 0 20 40 60 80
T/°C 0 20 40 60 80
Again,
When ,
Then,
Again, when ,
Then, at ,
Page No 120:
Question 4.23:
The rate constant for the decomposition of hydrocarbons is 2.418 × 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.
ANSWER:
= (0.3835 − 5) + 17.2082
= 12.5917
Page No 120:
Question 4.24:
Consider a certain reaction A → Products with k = 2.0 × 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.
ANSWER:
T = 100 s
Since the unit of k is s−1, the given reaction is a first order reaction.
Therefore,
= 0.135 mol L−1 (approximately)
Page No 120:
Question 4.25:
Sucrose decomposes in acid solution into glucose and fructose according to the first order
rate law, with t1/2 = 3.00 hours. What fraction of sample of sucrose remains after 8 hours?
ANSWER:
Therefore,
= 0.231 h−1
Page No 120:
Question 4.26:
Calculate Ea.
ANSWER:
(ii)
= 232792 J mol−1
= 232.792 kJ mol−1
Page No 120:
Question 4.27:
The rate constant for the first order decomposition of H2O2 is given by the following
equation:
Calculate Ea for this reaction and at what temperature will its half-period be 256 minutes?
ANSWER:
= 239.34 kJ mol−1
= 668.95 K
= 669 K (approximately)
Page No 120:
Question 4.28:
The decomposition of A into product has value of k as 4.5 × 103 s−1 at 10°C and energy of
activation 60 kJ mol−1. At what temperature would k be 1.5 × 104 s−1?
ANSWER:
T1 = 273 + 10 = 283 K
Then,
= 297 K
= 24°C
Note: There is a slight variation in this answer and the one given in the NCERT textbook.
Page No 120:
Question 4.29:
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
At 298 K,
At 308 K,
According to the question,
To calculate k at 318 K,
It is given that,
Page No 120:
Question 4.30: