Study Important Questions for class 12 Chemistry

Chapter 3 - Chemical Kinetics

(Highly Expected Questions and Answer)

1. For the reaction R → P, the concentration of a reactant changes from 0.03 M to

0.02M in 25 minutes. Calculate the average rate of reaction using units of time both in
minutes and seconds.

R
Ans: Average rate of reaction = −
t

[R]2 − [R]1
−
t 2 − t1

0.02 − 0.03
− = 4 10−4 Mmin −1
25

Also, it can be expressed in seconds as:

4 10−4
Average rate of reaction = = 6.67 10−6
60

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.

1   A
Ans: Average rate =
2 t

1  A2 −  A1
2 t2 − t1

Class XII Chemistry www.vedantu.com 1

 1 0.4 - 0.5
= 
2 10

1 1 - 0.1
= 
2 10

0.005 mol L - 1

= 5 10 - 3M min - 1

1
3. For a reaction, A + B → Product; the rate law is given by r = k  A 2  B  . What is the
2

order of the reaction?

1 1
Ans: The order of the reaction = + 2 = 2 = 2.5
2 2

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?

Ans: Because the reaction X Y has second-order kinetics, the rate law equation will be
Rate = kC 2 , with C =  x  .

The rate law equation for the reaction X Y will be Rate = k C 2 , with C =  x  because it
possesses second-order kinetics. So,  x  = 3C mol L - 1

The rate equation is Rate = K (3C )2

= 9(kC 2 )

As a result, the reaction rate will increase by 9 times.

As a result, the rate at which Y is formed will grow by 9 times.

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5. A first order reaction has a rate constant 1.15 10 - 3s - 1 . How long will 5g this reactant
takes to reduce to 3g?

Ans: Initial amount =  R 0 = 5g

Final concentration =  R  = 3g

Rate constant = 1.15 10 - 3s - 1

For a first order reaction t =

2.303  R0
log
k R

2.303 5
= −3
log
1.15 10 3

2.303
=  0.2219
1.15 10−3

= 444.38 s or 444 s

6. Time required to decompose SO2Cl2 to half its initial amount is 60 minutes. If the
decomposition is a first order reaction, calculate the rate constant of the reaction.

0.693
Ans: First order reaction t 1 =
2
k

t 1 = 60 min
2

0.693
k=
t1
2

0.693
=
60

Class XII Chemistry www.vedantu.com 3

= 0.01155min −1

= 1.155 min −1

k = 1.925 10 - 4 s - 1

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

Ans: A 100 increase in temperature almost doubles the rate constant of a process. The
Arrhenius equation, on the other hand, gives the exact temperature dependency of the rate of
a chemical reaction.

k = Ae − Ea / RT

Where A stands for the Arrhenius factor, also known as the frequency factor.

T stands for temperature.

The gas constant is R.

The activation energy is referred to as Ea .

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

temperature from 298 K. Calculate Ea .

Ans: Given

T1 = 298K

T2 = (298 + 10)K

We also know that when the temperature is raised by 10 degrees Celsius, the reaction rate
doubles. As a result, we'll use the values k1 = k and k2 = 2k .

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R = 8.314 JK −1mol −1

k2 Ea  T2 − T1 
On substitution =  
k1 2.303R  T1T2 

2k Ea  10 
log = 
k 2.303  8.314  298  308 

2.303  8.314  298  308  log 2

Ea =
10

= 52897.78 J mol - 1

= 52.89 kJ mol - 1

9. The activation energy for the reaction 2HI( g ) → H 2 + I2( g ) is 209.5 kJ mol - 1 at 581 k.
Calculate the fraction of molecules of reactants having energy equal to or greater than
activation energy.

Ans: Ea = 209.5kJ - 1
= 209500 J mol - 1

T = 581K

R = 8.314 J k - 1
mol - 1

The percentage of reactant molecules with energy equal to or greater than activation energy
is now:

x = e Ea / RT

In = − Ea / RT

Ea
log x = −
2.303RT

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 209500 J mol - 1
log x = = 18.8323
2.303  8.314  Jk - 1mol - 1  581

x = Anti log(−18.8323) = 1.47 10−19

NCERT Exercise

1. From the rate expression for the following reactions, determine their order of
reaction and the dimensions of the rate constants.

A: 3NO ( g ) → N 2O ( g ) Rate = k  NO 
2

B: H 2O 2 (aq) + 3I - (aq) + 2H + → 2H 2O(I) + I3 Rate = k  H 2O 2  I - 

-

C: CH 3CHO(g ) → CH 4 (g ) + CO(g )Rate = k CH 3CHO 

3/2

D: C2 H5Cl(g ) → C2 H 4 (g ) + HCl(g )Rate = k C2H5Cl

Ans: Given

Rate
(i) . k =
 H 2O2   I − 

Order of the reaction= 2

Rate
k=
 NO 
2

mol L - 1s - 1
Therefore, Dimension of k =
(mol L - 1 )2

mol L - 1s - 1 - 1 - 1
= L mol s
mol2 L - 2

Class XII Chemistry www.vedantu.com 6

(ii) Given k =  H 2O2   I − 

Rate
Order of the reaction k =
 H 2O2   I − 

mol - 1s - 1
Dimension of k = -1 -1
= L - 1mol - 1s - 1
(molL )(molL )

(iii) Given rate = k CH 3CHO 

3/2

3
Order of the reaction will be
2

Rate
k= 3
CH 3CHO 2
1 -1
mol - 1s - 1 mol - 1s - 1
Dimension of 3
= 3 3
L2 mol 2 s - 1
(mol L - 1 ) 2 mol 2 L2

(iv) Given rate = k C2 H 5Cl 

Rate
Order of the reaction 1k =
C2 H 5Cl 

mol L - 1s - 1 - 1
Dimension of = s
mol L - 1

Class XII Chemistry www.vedantu.com 7

2. For the reaction: 2A + B → A2B the rate = k  A  B with k = 2.0 10 - 6 mol - 2 L2s - 1.
2

Calculate the reaction's beginning rate when  A  = 0.1 mol L - 1 ,  A  = 0.1 mol L - 1
Calculate the rate of reaction after  A  , is reduced to 0.06 mol L - 1

Ans: The initial rate of the reaction is Rate = k  A   B

2

= ( 2.0 10 - 6 mol - 2 L2s - 1 )( 0.1mol L - 1 )( 0.2 mol L - 1 )

2

= 8.0 10 - 9 molL - 1s - 1

The concentration of A responded when  A  was lowered from 0.1 mol L - 1 to 0.06 mol L - 1.

= ( 0.1 0.06 ) mol L - 1 = 0.04 mol L - 1

1
As a result, B concentration=  0.04 mol L - 1 = 0.02 mol L - 1
2

After then, the concentration of B responded.

 B = 0.2  0.02mol L - 1 = 0.18mol L - 1

The rate of the reaction is given by once  A  is lowered to 0.06 mol L - 1.

20lRate = k  A   B
2

( )( )( )
2
= 2.0 10 - 6 mol - 2 L2s - 1 0.06mol L - 1 0.8mol L - 1

= 3.89 10 - 9 mol L - 1s - 1

Class XII Chemistry www.vedantu.com 8

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 - 1L s - 1 ?

Ans: The following equation represents the breakdown of NH3 on a platinum surface.

2NH3( g ) ⎯⎯
Pt
→ N + 3H + 3H

2( g )

2( g )

2( g )

1 d  NH3  d  N 2  1 d  H 2 
Rate = − = =
2 dt dt 3 dt

It is assumed, however, that the reaction is of zero order.

1 d  NH3  d  N 2  1 d  H 2 
So, Rate = − = =
2 dt dt 3 dt

= 2.5 10 - 4 mol L - 1s - 1

d  N2  2.5 10−4
As a result, the rate of N2 production is =
dt 2

= 1.25 10 - 4 molL1s - 1

In addition, the rate of H2 production is increasing.

d  N2  3
=  2.5 10−4
dt 2

= 3.75 10 - 4 mol L - 1 s - 1

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4. The decomposition of dimethyl ether leads to the formation of CH 4 , 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 dimethy l ether, i.e Rate = k = (PCH3OCH3 )3/2 . It the pressure is
measured in bar and time in minutes, then what are the units of rate and rate
constants?

Ans: In addition, the rate of H 2 production is increasing.

Rate = k = (PCH3OCH3 )3/2

Rate
k=
PCH3OCH3

bar min −1
Hence, the unit of rate constants k = 3
bar 2

= bar −1/2 min −1

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

Ans: The rate of a reaction is influenced by several things.

(i) Reactant nature: The rate of the reaction is determined by the reactant's nature. Ionic
compound reactions, for example, are faster than covalent compound reactions.

(ii) Reactant state: Solid reactions are sluggish, liquid reactions are quick, and gas reactions
are very fast.

(iii) Temperature: The rate of reaction is heavily influenced by the temperature. Temperature
raises the pace of reaction by 2-3 times for every 1000 C increase in temperature.

rT + 10
= 2−3
rT

Class XII Chemistry www.vedantu.com 10

The temperature coefficient is the name given to this proportion.

The average kinetic energy of reactant molecules increases as the temperature rises. As a
result, the rate of collisions rises. The number of molecules with threshold energy grows as
the temperature rises. As a result, the rate of reaction accelerates.

iv) Catalyst presence: The rate of reaction also is affected by the presence of a catalyst.
Catalysts boost reaction rates by increasing reaction surface area, generating an unstable
intermediate with the substrate, and providing 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

(ii) reduced to half?

Ans: Let the reactant concentration be  A  = a.

Rate of reaction, R = k  A
2

= ka 2

(i) If the reactant concentration is doubled,  A  = a. , the reaction rate is

R = k ( 2a ) = 4ka 2 = 4 R
2

As a result, the reaction rate would increase by four times.

1
(ii) If the reactant's concentration is cut in half,  A = a the rate of reaction will
2
2
1 
be R = k  a 
2 

Class XII Chemistry www.vedantu.com 11

 1
= ka
4

1
= R
4

1th
As a result, the reaction rate would be lowered to =
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?

Ans: k = Ae− Ea / RT

Where k is the rate constant,

A denotes the Arrhenius factor or frequency factor,

R denotes the gas constant,

T denotes the temperature, and Ea denotes the activation energy for the reaction.

k2 Ea  T2 − T1 
log =  
k1 2.303  TT
1 2 

k1 = rate constant at temperature

T1 k1 = rate constant at temperature T2

Class XII Chemistry www.vedantu.com 12

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

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.

(ii) Calculate the pseudo first order rate constant for the hydrolysis of ester

Ans:

d  Ester 
(i) Average reaction time between 30 and 60 seconds=
dt

0.31 − 0.17 0.14

=
60 − 30 30

= 4.67 10 - 3mol L - 1s - 1

(ii) pseudo first order reaction 35l

2.303 [ Ester ]0
k= log
t [ Ester ]

When t = 30 s

2.303  0.55  −2
k=  log   = 1.9110 / s
30  0.31 

When t = 60 s

Class XII Chemistry www.vedantu.com 13

 2.303  0.55  −2
k=  log   = 1.96 10 / s
60  0.17 

When t = 90s

2.303  0.55  −2
k=  log   = 2.07 10 / s
90  0.085 

k1 + k2 + k3
Average rate constant k = = 1.98 10−2 / s
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 three times?

iii. How is the rate affected when the concentrations of both A and B are doubled

Ans:

d [ R]
(i) The differential rate equation will be the following: = k[ A][ B]2
dt

d [ R]
(ii) If B's concentration is three times higher, then = k[ A][3B]2 = 9.k[ A][ B]2
dt

As a result, the reaction rate will rise by 9 times.

(iii) When both A and B concentrations are doubled,

d [ R]
= k[ A][ B]2
dt

= k[2 A][2 B]2

Class XII Chemistry www.vedantu.com 14

 = 8.k  A  B 
2

As a result, the reaction rate will rise by eight times.

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:

A/mol L - 1 0.20 0.20 0.04

B /mol L - 1 0.30 0.10 0.05

romol\L - 1s - 1 5.07 10 - 5 5.07 10 - 5 1.43 10 - 4

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

Ans:

Let the reaction order be x with respect to A and y with respect to B. Therefore,
ro = k[ A]x [ B] y

5.07 10−5 = k  0.20  0.30 .. ( i )

x y

5.07 10−5 = k  0.20  0.10 . ( ii )

x y

1.43 10−5 = k  0.40  0.05 .. ( iii )

x y

5.07 10−5 k[0.20]x [0.30] y

=
5.07 10−5 k = [0.20]x [0.30]

0.30
y

I=
0.10
y

Class XII Chemistry www.vedantu.com 15

 x y
 0.30   0.30 
 0.10   0.10 

y=0

We get equation (ii) by dividing equation (ii) by equation (ii).

1.43 10−4 k [0.40]x [0.05] y

=
5.07 10−5 k [0.20] y [0.30] y

1.43 10−4 k [0.40]x

=
5.07 10−5 k [0.20] y

0.05]y = [0.30]y = 1

2.821 = 2 x

log 2.821 = x log 2

log 2.821
x=
log 2

1.496 = 1.5 ( approximately )

As a result, the reaction's order regarding A is 1.5 and zero with respect to B.

11. The following results have been obtained during the kinetic studies of the reaction:
2A + B → C + D

Experimen
t A/mol L - 1 B /mol L - 1 Initial rate of formation of D/mol L - 1min - 1

Class XII Chemistry www.vedantu.com 16

 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 the reaction order be x for reaction with respect to A and y for reaction with respect
to B. As a result, the reaction rate is given by, Rate = k  A  B 
x y

6.0 10−3 = k  0.1 0.1 ( i )

x y

7.2 10−2 = k  0.3 0.2 ( ii )

x y

2.88 10−1 = k  0.3  0.1 ( iii )

x y

2.40 10−2 = k  0.4  0.1 ( iv )

x y

When we divide equation (iv) by I we get,

2.40 10−2 k = [0.4]x [0.1] y

=
6.0 103 k = [0.1]x [0.1] y

0.4
x

4=
0.1
x

x
 0.4 
4= 
 0.1 

Class XII Chemistry www.vedantu.com 17

x =1

Divide (iii) by (i)

2.88 10−1 k  0.3  0.4

x y

=
7.2 10− 2 k  0.3x  0.2 y

y
 0.4 
4= 
 0.2 

4 = 2y

22 = 2 y

y=2

Rate law

Rate = k  A  B 
2

Rate
k=
 A B 
2

From experiment I we understand

6.0 103mol L - 1min - 1

k =
( )( )
2
= 0.1mol L - 1 0.1mol L - 1

= 6.0 L2 mol - 2 min - 1

From experiment II we understand

2.88 10 - 1
mol L - 1min - 1
k= = 6.0L2 mol - 2
min - 1

( 0.3mol L )( 0.4mol L )
2
- 1 - 1

Class XII Chemistry www.vedantu.com 18

From experiment III we understand

2.40 10 - 2
mol L - 1min - 1
k= = 6.0L2 mol - 2
min - 1

( 0.4mol L )( 0.1mol L )
2
- 1 - 1

Hence, the rate constant 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:

Experiment A/mol L - 1 B /mol L - 1 Initial rate /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: With respect to A, the given reaction is first order, whereas with respect to B, it is zero
order.

The rate of the reaction Rate = k  A  B 

1 0

Rate = k =  A

From 1st experiment,

(
2.0 10 - 2 mol L - 1min - 1 = k 0.1molL - 1 )
k = 0.2 min - 1

Class XII Chemistry www.vedantu.com 19

From 2nd experiment,

(
4.0 10 - 2 mol L - 1min - 1 = k 0.2mol L - 1 )
 A = 0.2 mol L - 1
From 3rd experiment,

Rate = 0.2 min - 1  0.4 mol L - 1

= 0.08 mol L - 1min - 1

From 4th experiment

2.0 10 - 2 mol L - 1min - 1 = 0.2 min - 1  A

 A = 0.1mol L - 1

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

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

Ans:

0.693 0.693
(i) Half life t 1 = = = 0.346 10−2
2
k 200S−1

0.693 0.693
(ii) Half life t 1 = = = 0.346 min
2
k 2 min −1

0.693 0.693
(iii) Half life t 1 = = = 0.173 years
2
k 4 years −1

Class XII Chemistry www.vedantu.com 20

14. The half-life for radioactive decay of 14C is 5730 years. An archeological artifact
containing wood had only 80% of the 14C found in a living tree. Estimate the age of the
sample.

Ans: The dynamics of radioactive decay are first order. As a result, the decay constant

0.693 0.693
Decay constant k = = = 1.209 10−4 / years
t1/2 5730 year

The rate of counts is proportional to the number of C-14 atoms in the sample.

N0 = 100, N = 80

2.303 N 
The age of the sample t = log  0 
k  N

2.303  100 
t= −4
 log   = 1846 years
1.209 10  80 

Therefore, the sample age is 1846 years.

15. The experimental data for decomposition of N2O5[2N2O5 → 4NO2 + O2 ] in gas phase
at 318K are given below:

t/s 0 400 800 1200 1600 2000 2400 1800 3200

1.63 1.36 1.14 0.93 0.78 0.64 0.53

10−2  N2O5

mol L - 1

(i) Plot log[N2O5 ] against t.

(ii) Find the half-life period for the reaction.

Class XII Chemistry www.vedantu.com 21

(iii) Draw a graph between log[N2O5 ] and t.

(iv) What is the rate law?

(v) Calculate the rate constant.

Calculate the half-life period from k and compare it with (ii)

Ans:

Image: A graph between

log[N2O5 ] and t.

The period that corresponds to the concentration

1.630 10 - 2
mol L1 = 0.815 10 - 2 mol L−1 is half- life.
2

Observing the graph, the half life is 1440s.

(iii)

t(s) 102   N 2O5  mol L - 1 Log  N 2O5 

Class XII Chemistry www.vedantu.com 22

 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

Image: A straight-line plot of log

N 2O5 v/s time

Class XII Chemistry www.vedantu.com 23

The provided reaction is of first order, as evidenced by the straight-line plot of log N 2O5

v/s t. As a result, the reaction's rate law is Rate = k[N2O5 ]

(v)From the plot N 2O5 v/s t, we get

2.46 − (−1.79) −0.67

= =
3200 − 0 3200

= 4.82 10 - 4 mol L - 1s - 1

(vi) Half life given by

2.46 − (−1.79) −0.67

= =
3200 − 0 3200

= 4.82 10 - 4 mol L - 1s - 1

= 1438 s

The value of t 1 computed from k is extremely close to the value acquired from graph.
2

16. 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: t =
2.303
log
 R
k  R
2.303 1
= - 1
log
60s 1

Class XII Chemistry www.vedantu.com 24

 2.303
= log16
60s - 1

= 4.62 10−2 s

17. During nuclear explosion, one of the products is 90Sr with half-life of 28.1 years. If 1
µg 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?

0.693 0.693 −1
Ans: k = = v
t1 28.1
2

Knowing

t=
0.303
log
 R
k  R
0.303 1
t= log 10
0.693  R
28.1

0.303 10  0.303
= (−108  R ) log  R  −  R
0.693 2.303  28.1
28.1

= anti log(−0.1071) = 0.7814 g

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

0.693 0.693 −1
Repeating k = = v
t1 28.1
2

Knowing t =
0.303
log
 R
k  R

Class XII Chemistry www.vedantu.com 25

 0.303 1
60 = log
0.693  R
28.1

10  0.303
log  R  −
2.303  28.1

 R = anti log(−0.6425)

= 0.2278 g

Thus, 0.2278µg of 90Sr will remain after 60 years

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

Ans: The time required for 99 percent completion of a first order reaction is

2.303 100
t1 = log
k 100 − 99

2.303
= log100
k

The time required for 90 percent completion of a first order reaction is

2.303 100
t2 = log
k 100 − 99

2.303
= log10
k

2.303
=
k

t1 = 2t2

Class XII Chemistry www.vedantu.com 26

As a result, the time required to complete a first order reaction at 99 percent is twice the time
required to complete the reaction at 90%.

19. A first order reaction takes 40 min for 30% decomposition. Calculate t 1
2

Ans: 1st order reaction

t2 =
2.303
log
 R
k  R
2.303 100
k= log
40 min 100 − 30

2.303 10
= log
40 min 7

= 8.918 10−3 min −1

t 1 of the decomposition reaction is

2

0.693 0.693
t1 = = min
2
k 8.918 10−3

= 77.7 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

Class XII Chemistry www.vedantu.com 27

 360 54.0

720 63.0

Calculate the rate constant

Ans: The following equation represents the breakdown of azoisopropane to hexane and
nitrogen at 54.3 k.

(CH3 )2CHN = NCH(CH3 )2 ( g ) → N 2 ( g ) + C6 H14 ( g )

At t = 0Po

t = tP0 − − p

Total pressure , ( Pt ) = ( P0 − p ) + p + p

Pt = P0 + p

when the value of p is substituted for the pressure of the reactant at time t

= Po − − p

= Po − ( Pt − Po )
= 2Po − Pt

2.303 P
1st order reaction k = log
t 2 P0 − Pt

t = 360s ,

2.303 35.0
k= log
360 2  35.0 − 54.0

= 2.175 10−3 s - 1

Class XII Chemistry www.vedantu.com 28

 2.303 35.0
when t = 720s, k = log 10−3 s - 1

720 2  35.0 − 63.0

Average value of rate constant

(2.175 10−3 ) + (2.235 10−3 ) - 1

k= s
2

= 2.20 10−3 s - 1

21. The following data were obtained during the first order thermal decomposition of
SO2Cl2 at a constant volume SO2Cl2 ( g ) → SO2 ( g ) + Cl2 ( g )

Experiment Time/ Pressure/atm

s -1

1 O 0.5

2 100 0.6

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

Ans: The following equation represents the thermal breakdown of SO2Cl2 at a constant
volume.

SO2Cl2 ( g ) → SO2 ( g ) + Cl2 ( g )

At t = 0Po

t = tP0 − − p

Total pressure , ( Pt ) = ( P0 − p ) + p + p

Class XII Chemistry www.vedantu.com 29

Pt = P0 + p

when the value of p is substituted for the pressure of the reactant at time t

= Po − − p

= Po − ( Pt − Po )

= 2Po − Pt

2.303 P0
k= log
t 2 P0 − Pt

2.303 0.5
k= log
100s 2  0.5 − 0.6

when t = 100s

K = 2.231 10−3 s - 1

When Pt = 0.65 atm,

As a result, the total pressure of SO2Cl2 at time t is 0.65 atm.

2 PSOCl = 2 Po − Pt

= 2  0.50 − 0.65

= 0.35 atm

As a result, when total pressure is 0.65 atm, the rate of equation is

Rate = k = ( PSOCl )

( )
= 2.33 10−3 s −1 ( 0.354atm ) = 7.8 10−4 atms −1

Class XII Chemistry www.vedantu.com 30

22. The rate constant for the decomposition of N2O5 at various temperatures is given
below:

T/ 0 c 0 20 40 60 80

105  k /s - 1 0.0787 0.0787 0.0787 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 50oC.

Ans: From the given data, we get

I −1 02733.66 10−3 202933.4110−3 60333 80353

T / 0 CT / K /k
T 403133.19 10 −3
3.0 10−3
2.83 10−3

0.0787 4.075 25.7 178 2140

105  k / s - 1 -7.147 -4.075 -1.359 -0.577 3.063

ln k

Class XII Chemistry www.vedantu.com 31

 Image: A graph between ln k and 1/T

y2 − y1
Slope of the line = 12.301k
x2 − x1

Arrhenius equation,

Slope = −
Ea
R
(
→ Ea = − slope  R = − ( −12.301K )  8.314 JK −1mol - 1
) = 102.27 K J mol - 1

Ea
Repeating Ink = InA −
ET

Ea
InA = Ink +
ET

Since, T = 273K , Ink = − 7.147

102.27 103
So, InA = −7.147 + = 37.911A = 2.91  106
8.314  273

T = 30 + 273K = 303K

Class XII Chemistry www.vedantu.com 32

I
= 0.0033K = 3.3 10−3 K
T

I
At, = 0.0033K = 3.3 10−3 K
T

In k = − 2.8

k = 6.08 10−2 s −1

I
= 0.0031K = 3.110−3 K
T

In k = − 0.5

k = 0.607 s −1

I
= 3.110−3
T

T = 50 + 273K = 323K

23. The rate constant for the decomposition of hydrocarbons is 2.418  10 - 5s - 1 at 546 k.
If the energy of activation is 179.9 kJ /mol, what will be the value of pre-exponential
factor.

Ans: Arrhenius equation

Ea Ea
K = Ae− E / RT Ink = InA − log k = log A
RT 2.303RT

179.9 103 jmol −1

(
= log 2.418  10−5 s −1 ) +
2.303  8.314 JKmol −1  546 K

= ( 0.3835 − 5) + 17.2082 = 12.5917

Class XII Chemistry www.vedantu.com 33

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 100 s if the initial concentration of A is 1.0 mol L - 1.

Ans: k = 2.0 10−2 s - 1 ,t = 100 s,  A0 = 1.0 mol L - 1

The given reaction is a first order reaction since the unit of k equals s −1
k=
2.303
log
 A 2.0 10−2 s - 1
=
2.303
log
1.0
2.0 10 −2 s - 1
=
2.303
( − log  A)
t  A 100s  A 100s

2.0 10−2100
− log  A =
2.303

 2.0 10−1 100 

[ A] = anti log  
 2.303 

= 0.135MolL−1

As a result, the concentration of A left is 0.135mol L - 1

25. Sucrose decomposes in acid solution into glucose and fructose according to the first
order rate law with t 1 = 3hours . What fraction of sample of sucrose remains after 8
2

hour?

Ans: 1st order reaction

2.303 [R ]
k= log 0
t [ R]

Class XII Chemistry www.vedantu.com 34

 2.303 [R ]
k= log 0
t [ R]

t 1 = 3 hours
2

0.693
k=
t1
2

0.693
So, k = = 0.231h −1
3

2.303 [ R]
= 0.231h−1 = log o
8h [ R]

[ R]0 0.231h−1  8h
log =
[ R] 2.303

[ R]0
= anti log(0.8024)
[ R]

[ R]0
= 6.3445
[ R]

[ R]0
= 0.1576
[ R]

= 0.158

As a result, after 8 hours, 0.158 percent of the sucrose sample remains.

Class XII Chemistry www.vedantu.com 35

26. The decomposition of hydrocarbon follows the equation
k = ( 4.5  1011 s −1 ) e −28000 K / T . Calculate Ea

Ans: From the given equation k = ( 4.5 1011 s −1 ) e −28000 K / T (i )

Arrhenius equation ,

k = Ae− E / RT (ii )

From equation (i) and (ii) we get

Ea 28000 K
=
RT T

Ea = R  28000K

= 8.314 J K −1 mol−1  28000k

= 232792 J mol −1

= 232.792kJmol−1

27. The rate constant for the first order decomposition of H2O2 is given by the following
equation: log k = 14.34 − 1.25  104 K / T . Calculate Ea for this reaction and at what
temperature will its half-period be 256 minutes?

Ans: The expression for the rate constant is as follows:

log k = 14.34 − 1.25 104 K / T ..(i)

Comparing it with Arrhenius equation, we get-

Ea
log k = log A −
2.303RT

Class XII Chemistry www.vedantu.com 36

 Ea
Therefore, = 1.25 104
2.303R

Ea = 1.25 104  2.303  8.314

The activation energy = Ea = 239339 J / mol = 239.339 kJ / mol

Half life period, t1/2 = 256 min = 256  60sec

0.693
k=
t1/2

0.693
k=
256  60sec

k = 4.5110−5 / s

Substitute in equation (i), we get-

log 4.5110−5 = 14.341.25 104 K / T

−4.35 = 14.341.25 104 K / T

T = 669 K

Hence, the temperature at which the half-life period is 256 minutes is 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: It is given that the decomposition of A into product has value of


k = 4.5 103 s−1 at 10 C.

 K  E a  T − T 
log   =   
 k  2.303R  TT 

Class XII Chemistry www.vedantu.com 37

  1.5 104  60 103  T − 283 
log  3 
=   
 4.5 10  2.303  8.314  283 T 

 T − 283 
0.5228 = 3132.62   
 283 T 

T − 283 = 0.0472 T

T = 297.02 K

T = 297.02 K − 273 = 24.02 C

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 Ea

Ans: 1st order reaction

2.303 a
t= log
k a−x

2.303 100
at 298K , t = log
k 90

0.1054
=
k

2.303 100
− log
k 75

2.2877
At 308k =
k

Regarding question

Class XII Chemistry www.vedantu.com 38

 0.1054 0.2877
= log
k k

k1
log = 2.7296
k

From Arrhenius equation, we get

k1 Ea  T − T 
log, log =  
k 2.303R  TT  

Ea  308 − 298 
log(2.7296) =  
2.303  8.314  298  308 

2.303  8,314  298  308  log(2.7296)

Ea =
308 − 298

= 76750.096 J mol −1

= 76.75kJmol−1

calculate k at 318 k

A = 4 1010 s −1 , T = 318K

Again, from Arrhenius equation, we get

Ea
log = log A −
2.303RT

76.75 103
log(4 10) −
2.303  8.314  318

= 10.6021 −12.6051 = −2.003

k = Anti log(−2.003)

= 9.93 10−3 s −1

Class XII Chemistry www.vedantu.com 39

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 if it does not change with
temperature.

Ans: From Arrhenius equation, we get

k2 Ea  T2 − T1 
log, log =  
k1 2.303  TT
1 2 

Given

k2 = 4k1

T1 = 293 K

T2 = 313 K

4k 2 Ea  313 − 293 
So , log =  
k1 2.303  8.314  293  313 

20  Ea
0.6021 =
2.303  8.314  293  313

0.6021 2.303  8.314  293  313

Ea =
20

= 52863.00 J mol−1

= 52.86kJmol−1

As a result, the activation energy required is 52.86kJmol−1

Class XII Chemistry www.vedantu.com 40