Chemical Kinetics

1. N 2O5 decomposes to NO2 and O2 and follows first order kinetics. After 50 minutes, the pressure inside the
vessel increases from 50 mm Hg to 87.5 mm Hg. The pressure of the gaseous mixture after 100 min at constant
temperature will be:
(a) 136.25 mm Hg
(b) 106.25 mm Hg
(c) 175.0 mm Hg
(d) 116.25 mm Hg

2. At 518 C , the rate of decomposition of a sample of gaseous acetaldehyde, initially at a pressure of

363 Torr, was 1.00 Torr s-1, when 5% had reacted and 0.5 Torr s-1 when 33% had reacted. The order of
the reaction is :
(a) 0
(b) 2
(c) 3
(d) 1

3. If 50 % of a reaction occurs in 100 second and 75 % of the reaction occurs in 200 second, the order of this
reaction is :
(a) 2
(b) 3
(c) Zero
(d) 1

4. The rate of a reaction A doubles on increasing the temperature from 300 to 310 K. By how much, the
temperature of reaction B should be increased from 300 K, so that rate doubles if activation energy of the
reaction B is twice to that of reaction A.
(a) 9.84 K
(b) 4.92 K
(c) 2.45 K
(d) 19.67 K

5. The rate of a reaction quadruples when the temperature changes from 300 to 310 K. The activation
energy of this reaction is :
(Assume activation energy and pre-exponential factor are independent of temperature;
ln2=0.693;R=8.314 J mol-1K-1 )
(a) 107.2 kJ mol −1
(b) 53.6 kJ mol −1
(c) 26.8 kJ mol −1
(d) 214.4 kJ mol −1

6. Two reactions, R1 and R2 have identical preexponential factors. Activation energy of R1 exceeds that of R2 by
10 kJ mol −1 . If k1 and k 2 are rate constants for reactions R1 and R2 respectively at 300 K, then ln(k2 / k1 ) is
equal to
(a) 12
(b) 6
(c) 4

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(d) 8

7. Decomposition of H2O2 follows a first order reaction. In fifty minutes, the concentration of
H2O2 decreases from 0.5 to 0.125 M in one such decomposition. When the concentration of H2O2 reaches
0.05 M, the rate of formation of O2 will be :
(a) 6.93 × 10-2 mol min -1
(b) 6.93 × 10-4 mol min -1
(c) 2.66 L min -1 at STP
(d) 1.34 × 10-2 mol min -1

8. 200 g water is heated from 400C to 600C. Ignoring the slight expansion of water, the change in its
internal energy is close to (Given specific heat of water=4184 J/kg/K) :
(a) 8.4 kJ
(b) 4.2 kJ
(c) 16.7 kJ
(d) 167.4 kJ

9. The rate law for the reaction below

A + B ⟶ Product is given by the expression, k [A][B].
If the concentration of B is increased from 0.1 to 0.3 mole, keeping the value of A at 0.1 mole, the rate
constant will be :
(a) k
(b) k/3
(c) 3k
(d) 9k

10. Higher order (>3) reactions are rare due to

(a) Low probability of simultaneous collision of all the reacting species.
(b) Increase in entropy and activation energy as more molecules are involved.
(c) Shifting of equilibrium towards reactants due to elastic collisions.
(d) Loss of active species on collision.

11. The reaction 2 N2O5 ( g ) → 4 NO2 ( g ) + O2 ( g ) follows first order kinetics. The pressure
of a vessel containing only N 2O5 was found to increase from 50 mm Hg to 87.5 mm Hg in 30 min. The
pressure exerted by the gases after 60 min. will be (Assume temperature remains constant):
(a) 106.25 mm Hg
(b) 116.25 mm Hg
(c) 125 mm Hg
(d) 150 mm Hg

12. A + 2B ⟶ C, the rate equation for this reaction is given as Rate = k [A][B]. If the concentration of A
is kept the same but that of B is doubled, what will happen to the rate itself?
(a) halved
(b) the same
(c) doubled
(d) quadrupled

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13. For the non-stoichiometric reaction, 2A + B ⟶C + D, the following kinetic data were
obtained in three separate experiments, all at 298 K.

The rate law for the formation of C is

dC
(a) = k[ A][ B]
dt
dC
(b) = k[ A]2 [ B]
dt
dC
(c) = k[ A][ B]2
dt
dC
(d) = k[ A]
dt

14. In the following sets of reactants which two sets best exhibit the amphoteric character of
Al2O3 .xH 2O ?
Set-1: Al2O3 .xH 2O ( s ) and OH − (aq )
Set-2: Al2O3.xH 2O(s) and H 2O(l )
Set-3: Al2O3 .xH 2O ( s ) and H + (aq )
Set-4: Al2O3.xH 2O(s) and NH3 (aq)
(a) 1 and 2
(b) 2 and 4
(c) 1 and 3
(d) 3 and 4

15. Which of the following statements about Na2O2 is not correct?

(a) Na2O2 oxidises Cr 3+ to CrO42 − in acid medium.
(b) It is diamagnetic in nature.
(c) It is the super oxide of sodium.
(d) It is a derivative of H 2O2 .


16. The standard enthalpy of formation ( f H 298 ) for methane, (CH4) is – 74.9 kJ mol -1. In order
to calculate the average energy given out in the formation of a C-H bond from this it is necessary to know
which one of the following is correct?
(a) the dissociation energy of the hydrogen molecule, H2
(b) the dissociation energy of H2 and enthalpy of sublimation of carbon (graphite)
(c) the first four ionisation energies of carbon and electron affinity of hydrogen

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(d) the first four ionisation energies of carbon

17. Which type of ‘defect’ has the presence of cations in the interstitial sites ?
(a) Metal deficiency defect
(b) Schottky defect
(c) Vacancy defect
(d) Frenkel defect

18. For a first order reaction, A → P, the temperature (T) dependent rate constant (k) was found
to follow the equation:
2000
log k = + 6.0
T
the pre-exponential factor A and the activation energy Ea, respectively, are

19. Under the same reaction conditions, initial concentration of 1.386 mol d-3 of a substance
becomes half in 40 s and 20 s through first order and zero order kinetics respectively. Ratio
 k1 
  of the rate constants for first order (k1) and zero order (ko) of the reaction is
 k0 

20. Consider a reaction, aG + bH → products. When concentration of both the reactants G and
H is doubled, the rate increases by eight times. However, when concentration of G is doubled
keeping the concentration of H fixed, the rate is doubled. The overall order of the reaction is
(a) 0
(b) 1
(c) 2
(d) 3

21. Which one of the following statement(s) is incorrect about order of reaction?
(a) Order of reaction is determined experimentally
(b) Order of reaction is equal to sum of the power of cementation terms in differential rate law
(c) It is not affected with stoichiometric coefficient of the reactants
(d) Order cannot be fractional

22. (A) follows first order reaction, (A) → product. Concentration of A, changes from 0.1 M to
0.025 M in 40 min. Find the rate of reaction of A when concentration of A is 0.01 M.

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23. In a first order reaction, the concentration of reactant decreases from 800 mol/dm3 to 50
mol/dm3 in 2 x 104 s. The rate constant of reaction in s-1 is

24. Consider the chemical reaction, N2(g )+ 3H2(g) → 2NH3(g). The rate of this reaction can be
expressed in terms of time derivatives of concentration of N2(g), H2(g) or NH3,(g ). Identify the
correct relationship amongst the rate expressions

25. If I is the intensity of absorbed light and C is the concentration of AB for a photochemical
process, then AB + hv → AB*, the rate of formation of AB* is directly proportional to
(a) C
(b) I
(c) I2
(d) C.I

26. The rate constant for the reaction, 2N2O5 → 4NO2 + O2 is 3.0 ×10-5 s-1 . If the rate is 2.40 ×
10-5 mol L-1 s-1 then the concentration of N2O5 (in mol L-1) is
(a) 1.4
(b) 1.2
(c) 0.04

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(d) 0.8

27. The half-life period of a radioactive element is 140 days. After 650 days, one gram of the
element will reduce to
1
(a) g
2
1
(b) g
4
1
(c) g
8
1
(d) g
16

28. A catalyst is a substance which

(a) increases the equilibrium concentration of the product
(b) changes the equilibrium constant of the reaction
(c) shortens the time to reach equilibrium
(d) supplies energy to the reaction

29. The specific rate constant of a first order reaction depends on the
(a) concentration of the reactant
(b) concentration of the product
(c) time
(d) temperature

30.

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31. For the first order reaction, 2N2O5(g ) → 4N2(g ) + O2(g ).
(a) the concentration of the reactant decreases exponentially with time
(b) the half-life of the reaction decreases with decreasing temperature
(c) the half-life of the reaction depends on the initial concentration of the reactant
(d) the reaction proceeds 98.6% completion in eight half-life duration

32. The following statement (s) is are correct

1
(a) A plot of log Kp vs is non-linear
T
(b) A plot of log [X] vs time is linear for a first order reaction, x → p

1
(c) A plot of log p vs is linear at constant volume
T
1
(d) A plot of p vs is non-linear at constant temperature
V

33. For the first order reaction,

(a) the degree of dissociation is equal to (1— e-kt)
(b) a plot of reciprocal concentration of the reactant vs time gives a non-straight line
(c) the time taken for the completion of 75% reaction is thrice the half-life of the reaction
(d) the pre-exponential factor in the Arrhenius equation has the dimension of time, T-1

34. A catalyst
(a) decreases the average kinetic energy of reacting molecules
(b) decreases the activation energy

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(c) alters the reaction mechanism
(d) increases the frequency of collisions of reacting species

Passage Based Questions

Passage
Carbon-14 is used to determine the age of organic material. The procedure is based or the
formation of 14C by neutron capture in the upper atmosphere.

14
C is absorbed by living organisms during photosynthesis. The 14C content is constant in living
organism once the plant or animal dies, the uptake of carbon dioxide by it ceases and the level of
14
C in the dead being, falls due to the decay which C-I4 undergoes.

The half-life period of 14C is 5770 yr.

0.693
The decay constant () can be calculated by using the following formula  =
t1/2

The comparison of the β- activity of the dead matter with that of the carbon still in circulation
enables measurement of the period of the isolation of the material from the living cycle. The
method however, ceases to be accurate over periods longer than 30,000 yr. The proportion of 14C
to 12C in living matter is 1 : 1012 .

35. Which of the following option is correct?

(a) In living organisms, circulation of 14C from atmosphere is high so the carbon content is
constant in organism.
(b) Carbon dating can be used to find out the age of earth crust and rocks.
(c) Radioactive absorption due to cosmic radiation is equal to the rate of radioactive decay, hence
the carbons content remains constant in living organisms.
(d) Carbon dating cannot be used to determine concentration of 14C in dead beings.

36. What should be the age of fossil for meaningful determination of its age?
(a) 6 yr

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(b) 6000 yr
(c) 60,000 yr
(d) It can be used to calculate any age

37. A nuclear explosion has taken place leading to increase in concentration of C14 in nearby
areas. C14 concentration is C1 in nearby areas and C2 in areas far away. If the age of the fossil is
determined to be T1 and T2 at the places respectively then
(a) the age of fossil will increase at the place where explosion has taken place and
1 C
T1 − T2 = ln 1
 C2

(b) the age of fossil will decrease at the place where explosion has taken place and
1 C
T1 − T2 = ln 1
 C2

(c) the age of fossil will be determined to be the same

T1 C1
(d) =
T2 C2

38. An organic compound undergoes first order decomposition. The time taken for its
decomposition to 1/8 and 1/10 of its initial concentration are t1/8 and t1/10 respectively. What is
the value of

t1/8   10? log 2 = 0.3

( 10 )
t1/10 
(a) 7
(b) 8
(c) 9
(d) 10

39. The concentration of R in the reaction R → P was measured as a function of time and the
following data is obtained:

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The order of the reaction is
(a) 0
(b) 1
(c) 2
(d) 1.5

40.

(a) k[A] , 1 s-1

(b) k[A] , 1.5 s-1
(c) k[A] , 0 s-1
(d) k[A] , 0.5 s-1

41. 64Cu (half-life = 12.8 h) decays by β emission (38%), β+ emission (19%) and electron capture
(43%). Write the decay products and calculate partial half-lives for each of the decay processes.
(a) 30 h
(b) 29 h
(c) 29.76 h
(d) 28 h

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42. The rate of first order reaction is 0.04 mol L-1s-1 at 10 min and 0.03 mol L-1s-1 at 20 min after
initiation. Find the half-life of the reaction.
(a) 20 min
(b) 25 min
(c) 30 min
(d) 35 min

43. A hydrogenation reaction is carried out at 500 K. If the same reaction is carried out in the
presence of a catalyst at the same rate, the temperature required is 400 K. Calculate the activation
energy of the reaction if the catalyst lowers the activation barrier by 20 kJ mol-1.
(a) 10 kJ mol -1
(b) 100 J mol -1
(c) 100 kJ mol -1
(d) 1 kJ mol -1

44. The rate constant for an isomerisation reaction, A → B is 4.5 × 10-3 min. If the initial
concentration of A is 1 M, calculate the rate of the reaction after I h.
(a) 3.42 x 10-3 mol L-1 min-1
(b) 3.42 x 10-5 mol L-1 min-1
(c) 3.42 mol L-1 min-1
(d) 3.42 x 10-2 mol L-1 min-1

45. One of the hazards of nuclear explosion is the generation of Sr90 and its subsequent
incorporation in bones. This nucleide has a half-life of 28.1 yr. Suppose one microgram was
absorbed by a new-born child, how much Sr90 will remain in his bones after 20 yr.
(a) 6 x 10-7 g
(b) 6.9 x 10-7 g
(c) 5.6 x 10-7 g
(d) 6.1 x 10-7 g

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 Answer Key

1. b 2. b 3. d 4. b 5. d 6. c 7. b 8. c 9. b 10. a
11. a 12. a 13. d 14. c 15. c 16. b 17. d 18. d 19. a 20. d
21. d 22. a 23. c 24. a 25. d 26. d 27. d 28. c 29. d 30. a
31. a 32. b 33. a 34. b 35. c 36. b 37. a 38. c 39. a 40. d
41. c 42. b 43. c 44. a 45. d

Solution

1.
Solution:
1
N 2O5 → 2 NO2 + O2
2
t=0 50 0 0
p1
t = 50 min. 50 − p1 2 p1
2
= 25
p2
t = 100 min. 50 − p2 2 p2
2
= 12.5
p
50 − p1 + 2 p1 + 1 = 87.5
2
3 p1
50 + = 87.5
2
3 p1
= 37.5
2
37.5  2
p1 = = 25
3
50 min is half-life period
For, 100 min is (2 x half-life)
50 − p1 = 12.5
p2 = 37.5 mm of Hg
Total pressure at 100 min

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 p2
= 50 − p2 + 2 p2 +
2
3 p2 3
50 + = 50 +  37.5
2 2
= 50 + 56.25
= 106.25 mm of Hg

2.
Solution:
r = k ( p) m m = order of reaction
 95 
m

1=k 363   .....(1)

 100 
 67 
0.5 = k  362   .....(2)
 100 
Equation - 1 / Equation – 2, gives
m
1  95 
=
0.5  67 
m
 95 
2= 
 67 
2 = (0.4) m
log 2 = m log1.4
0.3010
=m
log1.4
0.3010
m
0.15
m=2
Hence, the answer is option (b).

3.
Solution:

For first order reaction, the half-life is constant.

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4.
Solution:
For reaction A

For reaction B

(In this equation replace Ea by Eb.

Eb=2Ea= 2 (53.6)
T1= 300K
Putting the values in above equation and solving it for T2, we get T2 = 304.92 K
The answer is (304.92 – 300) K= 4.92K.

5.
Solution:

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 K1 − Ea  1 1 
log =  − 
K 2 2.303R  T2 T1 
K1 r1 r 1
= = 1 =
K 2 r2 4r1 4
1 − Ea  1 1 
log =  − 
4 2.303  8.314  310 300 
Ea = 214.4kJ / mol

6.
Solution:
− E / RT
k1 = Ae a1
− Ea2 / RT
k2 = Ae
k2 1
( Ea − Ea )
= e RT 1 2
k1
k2 Ea1 − Ea2
ln =
k1 RT
10  103
= 4
8.314  300

7.
Solution:
t3/ 4 = 2  t1/ 2 = 50 min
i.e., t1/ 2 = 25min
0.693 0.693
k= = min −1
t1/ 2 25
Rate of H2O2 decomposition =
0.693 d [ H 2O2 ]
k[ H 2O2 ] =  0.05 = −
25 dt
1
H 2O2 → H 2O + O2
2
d [ H 2O2 ] d [O2 ]
− =2
dt dt
d [O2 ]
 = 6.93  10−4 mol min −1
dt

8.
Solution:

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9.
Solution:
A + B → Product
Rate = K[A][B]
= K  0.1  0.1 = 0.1K
rate
K=
0.1
When [B] increased from 0.1 to 0.3 mol then,
rate = K  0.1  0.3
= 0.3k
rate
K=
0.3
rate
K=
0.01  3
1  rate 
K=  
3  0.01 
10.
Solution: Higher order (greater than 3) reaction is rare because there is low probability of
simultaneous collision of all the reacting species.

11.
Solution:

12.
Solution:

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13.
Solution: 2A + B ⟶C + D
−1 d [ A] d [ B]
Rate of Reaction = =−
2 dt dt
d [C ] d [ D]
= =
dt dt
Let rate of Reaction = k[ A]x [ B ] y
d [C ]
Or, = k[ A]x [ B] y
dt
Now from table,
1.2  10−3 = k[0.1]x [0.1] y ...(i)
1.2  10−3 = k[0.1]x [0.2] y ...(ii)
2.4  10−3 = k[0.2]x [0.1] y ...(iii )
Dividing equation (i) by (ii)
1.2  10−3 k[0.1]x [0.1] y
 =
1.2  10−3 k[0.1]x [0.2] y
y
1
1=  
2
 y=0
Now Dividing equation (i) by (iii)
1.2  10−3 k[0.1]x [0.1] y
 =
2.4  10−3 k[0.2]x [0.1] y
1 x
1 1
  = 
2 2
 x =1
d [C ]
Hence, = k[ A]1[ B]0 .
dt

14.
Solution: In set 1: Al (OH ) −4 is formed
In set 2: Al +3 and H 2O is formed.

15.
Solution: Na2O2 is a peroxide ( O22 − ) which is occupied all paired electrons with
 * 2 px and  * 2 py .

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16.
Solution:

To calculate average bond energy of (C-H) bond, both dissociation energy of H2 and enthalpy of
sublimation of carbon (graphite) are needed.

17.
Solution: Frankel defect has the presence of cation in interstitial site.
Hence the correct answer is option (d).

18.
Solution:

19.
Solution:

20.
Solution:

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21.
Solution: Order of a reaction can take any real value, i.e., negative, integer, fraction etc.

22.
Solution:

23.
Solution:

24.
Solution: For any general reaction,

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25.
Solution: Rate will be directly proportional to both concentration and intensity, i.e., rate of
formation of AB*  C.I

26.
Solution: The unit of rate constant (t-1) indicating that the decomposition reaction follows the
first order kinetics.

27.
Solution:

28.
Solution: A catalyst increases the rate of reaction but by the same factor to both forward and
backward reactions. Hence, a catalyst shortens the time requires to reach the equilibrium.

29.
Solution: Specific rate constant of reaction depends on the temperature.

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30.
Solution: The rate constant (k) of all chemical reactions depends on temperature.

Objective Questions II (One or more than one correct option)

31.
Solution:
(a) For a first order reaction, the concentration of reactant remaining after time t is given by
[A]=[A]o e-kt Therefore, concentration of reactant decreases exponentially with time.

32.
Solution:

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33.
Solution:

34
Solution: A catalyst lowers the activation energy by enabling the reaction to continue through an
alternative path, i.e. catalyst changes the reaction mechanism. However, catalyst does not affect
either avenge kinetic energies of reactants or the collision frequency.

Passage Based Questions

Passage
Carbon-14 is used to determine the age of organic material. The procedure is based or the
formation of 14C by neutron capture in the upper atmosphere.

14
C is absorbed by living organisms during photosynthesis. The 14C content is constant in living
organism once the plant or animal dies, the uptake of carbon dioxide by it ceases and the level of
14
C in the dead being, falls due to the decay which C-I4 undergoes.

The half-life period of 14C is 5770 yr.

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 0.693
The decay constant () can be calculated by using the following formula  =
t1/2

The comparison of the β- activity of the dead matter with that of the carbon still in circulation
enables measurement of the period of the isolation of the material from the living cycle. The
method however, ceases to be accurate over periods longer than 30,000 yr. The proportion of 14C
to 12C in living matter is 1 : 1012 .

35.
Solution: Living plants maintain an equilibrium between the absorption of C14 (produced due to
cosmic radiation) and the rate of decay of C14 present inside the plant. This gives a constant
amount of C14 per gram of carbon in a living plant.

36.
Solution: Fossil whose age is closest to half-life of C-14 (5770 yr) will yield the most accurate
age by C-14 dating.

37
Solution:

where No = Number of C14 in the living matter and N = Number of C14 in fossil. Due to nuclear
explosion, amount of C14 in the nearby area increases. This will increase N0 because living plants
are still taking C-l4 from atmosphere, during photosynthesis, but N will not change because
fossil will not be doing photosynthesis.
T (age) determined in the area where nuclear explosion has occurred will be greater than the
same determined in normal area.

Integer Answer Type Questions:

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38.
Solution:

39.
Solution: Rate of reaction is constant with time.

Subjective Questions:
40.
Solution:

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41.
Solution:

42.
Solution:

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43.
Solution:

44.
Solution:

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45.
Solution:

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