JEE MAIN, ADVANCED 2023

#5

DPP NO. (JEE MAIN+ADVANCED)

Max Marks: Max Time:

Rate of disappearance, Rate of appearance, Rate of reactions

1. Ammonia and Oxygen reacts at higher temperatures as
4NH3 (g) + 5O2 (g) 4NO (g) + 6H2O
In an experiment, the concentration of NO increases by 1.08 * 10-2 mol litre-1
in 3 seconds. Calculate:
(i) rate of reaction
(ii) rate of disappearance of ammonia
(iii) rate of formation of steam

2. For the reaction: N2(g) + 3H2(g) 2NH3(g). If the rate of appearance

of NH3 is 6.8 * 10 gm/min, then the rate of disappearance of H2 at the
-3

same condition will be:

3. If the rate of decomposition of N2O5 in the reaction,

2N2O5(g) 4NO2(g) + O2(g) at a particular instant is 4.2 * 10-7 M/s.
Then calculate-
(a) rate of reaction
(b) rate of appearance of NO2 and O2 at that instant.

4. Consider the chemical reaction balanced in two different ways.

2NO(g) + Cl2(g) 2NOCl(g), and
NO(g) + ½ Cl2(g) NOCl(g)
If the rate of reaction according to the first version is 8 * 10-5 mol L-1 s-1.
Then what is the rate of reaction according to the second version?

Page No. 1
5. The reaction, 2NO(g) + Cl2(g) 2NOCl(g) is carried out in a closed
vessel. If the partial pressure of NO is decreasing at the rate of 180
torr/min. What is the rate of change of total pressure of vessel (in torr/s)?

6. For the elementary reaction 2A + B2 2AB. Calculate how much the

rate of reaction will change if:
(a) the volume of vessel is reduced to one-third of its original
volume?
(b) the volume of the vessel is doubled of its original volume?

7. For the elementary reaction:

H2S(aq.) + Cl2(aq.) S(s) + 2H+(aq.) + 2Cl-(aq.)
The rate constant for disappearance of H2S at 25°C is 4 * 10-2 M-1 sec-1. If
[H2S] = 2 * 10-4 M and [Cl2] = 0.025 M. What is the rate of formation of Cl-?

8. At 27°C, it was observed during a reaction of hydrogenation that the

pressure of hydrogen gas decreases from 2 atmosphere to 1.1 atmosphere
in 75 minutes. Calculate the rate of disappearance in M sec-1.

9. The reaction A(g) + 2B(g) C(g) + D(g) is an elementary process. In

an experiment, the initial partial pressure of A and B are PA = 0.6 and PB =
0.8 atm. Calculate the ratio of rate of reaction relative to initial rate when
PC becomes 0.2 atm.

Zero Order

10. In the following reaction: A B, the rate constant is 1.2 * 10-2 M s-1.
What is the concentration of B after 10 and 20 min, if we start with 10 M of
A?

11. A zero-order reaction: X Y. At the end of 50 min, X is 75% reacted.

How much of it will be left unreacted at the end of 2 hour.

12. The initial rate of zero order reaction of gaseous reaction,

A(g) 2B(g),
is 10-3 M min-1. If the initial concentration of A is 2M. Then what would be
the rate of reaction after 120 seconds.

Page No. 2
13. For the following data for the zero order reaction A products.
Calculate the value of k.
Time (min.) [A]
0.0 0.10 M
1.0 0.09 M
2.0 0.08 M

14. Decomposition of reaction:

2A (g) 2B (g) + C(g)
Follows zero order kinetics. Initial rate of decomposition of A is 0.1 atm/s. If
initially A is taken at 2 atm pressure, then what will be the rate of reaction
after 10 seconds.

15. The rate constant for a zero-order reaction is 2 * 10-2 mol L-1 sec-1, if the
concentration of the reactant after 25 sec is 0.25 M, calculate the initial
concentration.

16. A drop of solution (volume 0.10 mL) contains 6 * 10-6 mole of H+, if the rate
constant of disappearance of H+ is 1 * 107 mol L-1 s-1. How long would it take
for H+ in drop to disappear?

17. A certain substance A is mixed with an equimolar quantity of substance

B. At the end of an hour A is 75% reacted. Calculate the time when A is
10% unreacted. (Given: order of reaction is zero)

First Order

18. A first order reaction is 75% completed in 72 min. How long time will it
take for
(i) 50% completion
(ii) 87.5% completion
(iii) Fraction of reactant left after 108 min.

19. A first order reaction is 20% complete in 10 min. Calculate:

(i) the specific rate of reaction.
(ii) the time taken for the reactions to go to 75% completion.
(iii) Fraction of reactant decomposed after 40 min.

Page No. 3
20. The rate constant for an isomerization reaction A B is 4.5 * 10-3
min-1. If the initial concentration of A is 1 M. Calculate the rate of the
reaction after 1h.

21. The rate of a first order reaction is 0.04 mole L-1 s-1 at 10 minutes and 0.03
mol L-1 s-1 at 20 minutes after initiation. Find the half-life of the reaction.

22. In the first order decomposition of A: A 2B + 3C

Concentration of A decreases from initial concentration 0.8 M to 0.2 M in
13.86 min, then calculate the rate of appearance of B (in M/s) after 13.86
min.
23. For a 1st order reaction: A 3B + 2C, with initial concentration 2M of
A, it is 20% completed in 50 min. If the initial concentration of A = 10M,
then find the concentration of B after 50 min.

24. A viral preparation was inactivated in a chemical bath. The inactivation

process was found to be first order in virus concentration. At the
beginning of the experiment 2.0% of the virus was found to be inactivated
per minute. Evaluate k (in s-1) for inactivation process.
100
Given: ln ( ) = 0.02
98

25. The reaction SO2Cl2(g) SO2(g) + Cl2(g) is a first order gas reaction
with k= 2.2 * 10 s at 320°C. What % of SO2Cl2 is decomposed on heating
-5 -1

this gas for 90 min.

Given: e-0.1188 = 0.888

26. For a first-order reaction: A Product, the concentration of A

changes 2M to 0.5M in 4 min. Then, Calculate the rate of reaction (in Ms-1)
after 6 min. [ln2 = 0.7]

27. Decomposition of 1 L H2O2 follows a first order reaction. In 46 minutes,

the concentration of H2O2 decreases from 0.5 to 0.125 M in one such
decomposition. When the concentration of H2O2 reaches 0.05M, then
calculate the rate of formation of O2 (in mol s-1). [ln 2 = 0.69]

28. The half-life for first-order decomposition of N2O4 is 1.4 * 10-5 s.

N2O4(g) 2NO2(g)

Page No. 4
 If N2O4 is introduced into an evacuated flask at a pressure of 20 mm Hg,
how many seconds are required for pressure of NO2 to reach 10 mm Hg?

29. At 500°C, cyclopropane (C3H6) rearranges to propene (CH3-CH=CH2). The

reaction is first order and the rate constant is 4 * 10-3 s-1. If the initial
concentration of cyclopropane C3H6 is 0.05 M.
[Given: ln 5 = 1.6, ln 2 = 0.7]
Then,
(a) What is the molarity of cyclopropane C3H6 after 20/3 min?
(b) How many minutes does it take for C3H6 concentration to drop to
0.01 M.?
(c) After how many minutes 20% of cyclopropane will be left?

30. The gas phase reaction:

N2O5(g) 2NO2(g) + ½ O2(g)
is found to be first order. The reaction was carried out at constant
temperature of 340 K in a constant volume container. The initial pressure
is equal to 0.1 bar and no substance is initially present except for N2O5. The
total pressure was 0.16 bar after 100 sec of reaction. Calculate:
(a) the value of rate constant
(b) The partial pressure of N2O5 after 100 sec of reaction
(c) half-life (t1/2)

Order of Reaction & Rate law

31. Initial rate data at 25°C are listed in the table for reaction.
NH4+(aq.) + NO2-1(aq.) N2(g) + 2H2O(l)

Initial rate of
Experiment Initial [NH4+] Initial [NO2-] consumption of [NH4 ]
+

(M/s)
1 0.24 0.1 7.2 * 10-6
2 0.12 0.1 3.6 * 10-6
3 0.12 0.15 5.4 * 10-6
(a) What is the rate law?
(b) What is the value of rate constant?
(c) What is the initial rate when the initial concentration is [NH4+] =
0.4 M and [NO2-] = 0.5 M?

Page No. 5
32. The following result have been obtained during kinetic studies of the
reaction: A + B C+D

Initial rate of formation

Experiment [A] / M [B] / M
of D/ M s-1

1 0.1 0.1 6.0 * 10-3

2 0.3 0.2 7.2 * 10-2
3 0.3 0.4 2.88 * 10-1
4 0.4 0.1 2.40 * 10-2
(a) Determine the rate law of the above reaction.
(b) Find the rate constant of the above reaction in (mol/ L)1-n s-1

33. The following data is obtained for the reaction

A(aq.) 2B (aq.) + C(aq.)

Time(min) 0 20 40 60
Concentration of ‘A’ 0.1 0.09 0.081 0.0729
Then calculate the order of the reaction.

34. For the reaction: A Products, the time for 75% completion of
reaction is 5 times the time for 50% completion of reaction. Then,
calculate the order of reaction.

35. For a gaseous reaction: 2A(g) 3B(g) + 4C(g) occurring in a rigid

vessel, if initially pressure is 3 atm and after 10 minutes & 20 minutes, the
pressure is 6.75 atm and 10.5 atm respectively, then what will be the order
of reaction?

36. At 300 K, the rate of decomposition of a gaseous compound initially at a

pressure of 20 kPa was 13.5 Pa s-1 when 10% had reacted and 0.5 Pa s-1
when 70% had reacted. Then calculate the order of reaction.

Calculation of Rate Constant using Different Parameters

37. The reaction AsH3(g) As(s) + 3/2 H2(g) was followed at constant
volume at 310°C by measuring the gas pressure at intervals. Show from
the following figures that the reaction is first order.

Page No. 6
 Time (in hrs.) 0 5 7.5 10
Total Pressure (in mm) 758 827 856 882

38. The decomposition of H2O2 follows first order kinetics:

H2O2(aq.) H2O2(l) + ½ O2(g)
In order to determine the rate constant of a reaction, a definite
volume of reaction mixture is titrated with standard KMnO4
solution, at different time. What is the value of ‘X’ in the following
data?
Time(min) 0 10 20
Volume of KMnO4 25 20 X

39. The thermal decomposition of dimethyl ether as measured by

finding the increase in pressure of the reaction:
(CH3)2O(g) CH4(g) + H2 + CO(g)
at 500°C as follows:
Time(s) 390 1195 3155 ∞
Pressure increase (mm Hg) 96 250 467 624
The initial pressure of ether was 312 mm Hg. Write the rate
equation for this reaction and determine the rate constant of the
reaction.

40. The polarimeter readings in an experiment to measure the rate of

inversion of cane sugar (1st order) were as follows:
Time(min.) 0 30 ∞
Rotation due to solution 60° 40° -30°
Calculate:
(a) The half-life of reaction
(b) The time at which solution becomes optically active.
[Given: log 2 = 0.3, log 3 = 0.48, log 7 = 0.84, loge10 = 2.3]

41. A first order B + C

Time t ∞
Total Pressure of (B+C) P2 P3
Find k.

42. S first order G + F

Time t ∞
Rotation of Glucose & Fructose rt r∞
Find k.

Page No. 7
43. The following data were obtained in experiment on inversion of
cane sugar.
Time(min.) 0 60 120 180 360 ∞
Angle of rotation(degree) +13.1 +11.6 +10.2 +9.0 +5.87 -3.8
Show that the reaction is of first order. After what time would you
expect a zero reading in polarimeter?

44. At 100°C the gaseous reaction A 2B + C was observed to

be first order. On starting with pure A, it is found that at the end of
10 minutes, the total pressure of system is 176 mm Hg and after a
long time 270 mm Hg. From these data, find:
(a) The initial pressure of A
(b) The pressure of A at the end of 10 minutes
(c) The specific rate of reaction
(d) The half-life period of the reaction.
[Given ln (90/47) = 0.65]

45. The decomposition of N2O5 according to the equation:

2N2O5(g) 4NO2(g) + O2(g) is a first order reaction. After 30
min from the start of decomposition in a closed vessel, the total
pressure developed is found to be 284.5 mm Hg. On complete
decomposition, the total pressure is 584.5 mm Hg. Calculate the rate
constant of the reaction. [Given: ln 1.169 = 0.156]

46. Decomposition of reaction 3A(g) 2B(g) + 2C(g) follows first

order kinetics. Starting with pure ‘A’ pressure developed after 20
min. and infinite time are 3.5 atm and 4 atm respectively. What is
the time (in minutes) taken for 75% decomposition of A?

47. For a reaction: 2A(g) 3B(g) + C(g), the pressure at different

instants is given as shown:
Time(min) 0 13.86 ∞
Total Pressure(mm) 50 80 90
Calculate value of rate constant in min .
-1

[Given: ln 2 = 0.693]

48. Acid catalyzed hydrolysis of CH3COOC2H5 is monitored by taking

equal amount of solution after certain interval of time and titrating it
with NaOH. Following data were obtained.

Page No. 8
 Rate= k[H+][CH3COOC2H5]
Time(min.) 0 20 ∞
Volume of NaOH (in mL) 20 80 100
If [H+] = 0.7 M. Find ‘K’ in M-1 s-1.
[Take: ln 2 = 0.7]

49. The reaction A(aq.) B(aq.) + C(aq.) is monitored by

measuring optical rotation of reacting mixture at different time
interval. The species A, B and C are optically active with specific
rotations 20°, 30° and -40° respectively. Starting with pure A, if the
value of optical rotation was found to be 2.5° after 6.93 minutes and
optical rotation was -5° after infinite time. Find the rate constant for
the first order conversion of A into B and C.

Parallel and Sequential Reaction

k1 x
[𝑥]
50. For a reaction x , calculate value of ratio, [𝑦]+[𝑧]
𝑡
at any given
k2 y
instant t.

k1 B
[𝐶]
51. A k1 = x hr-1; k1:k2 = 1:10. Calculate after one hour from the
k2 C [𝐴]

start of the reaction. Assuming only A was present in the

beginning.

52. How much time would be required for the B to reach maximum
concentration for the reaction:

k1 k2 ln 2 ln 2
A B C. Given: k1= min-1, k2= min-1.
4 2

53. For the first order parallel reaction, K1 and k2 are 8 and 2 min-1
respectively at 300K. If the activation energies for the formation of B
and C are respectively 20 and 28.314 kJ/mol respectively, find the
temperature at which B and C will be obtained in the molar ratio of
2:1.
k A 1

A k2
B

Page No. 9
 [Given: ln 4 = 1.4]

Temperature Dependence of Rate (Activation Energy)

54. Potential energy profile for a reaction is given as:

2HI(g) H2(g) + I2(g)

(a) Calculate activation energy for forward reaction and backward

reaction respectively.
(b) Calculate ∆E of reaction.
(c) Is the reaction endothermic or exothermic?
(d) Fraction of molecules having sufficient kinetic energy to cross
threshold barrier at 300K.
[Given: R=25/3 J/K-mol]

55. What fraction of molecules in a gas at 300K collide with an energy

equal to or greater than Ea when Ea equals 50kJ/mol.
[Given: R=25/3 J/mol-K]

56. The gas phase decomposition of N2O4 is a first order reaction:

N2O4(g) 2NO2(g)
Use the following data to calculate the activation energy.
[in kCal/mol].
[Given: ln 2 = 0.7, ln 3 = 1.1]

Temperature[°C] Initial [N2O4] Initial rate of decomposition of N2O4

[M/s]
27 0.1 5 * 103
47 0.15 2 * 104

Page No. 10
57. Rate constants for the reaction: NO2(g) + CO(g) NO(g) + CO2(g) are
1.3 M-1s-1 at 600K and 26 M-1s-1 at 800K.
[Given: ln 10 = 2.3, ln 2 = 0.7]
Calculate:
(a) Activation energy in KCal/mol.
(b) Rate constant at 1200K.

58. If the rate of reaction increases by a factor of 2, when the temperature is

raised form 27°C to 37°C. What is the value of activation energy in kJ/mol?
By what factor does the rate of reaction increase if the temperature is
increased from 127°C to 137°C.
[Given: ln 2 = 0.7, R = 8.314 Joule/mol-K, e0.4 = 1.5]
(a) If the temperature coefficient is same in the given temperature range.
(b) If the temperature coefficient is function of temperature.

59. The dependence of rate constant of a reaction on temperature may be

given as:
500
ln K [sec-1] = 12.5 – .
𝑇(𝐾)
Calculate the activation energy of reaction (in Cal/mol).

60. A catalyst lowers the activation energy for a certain reaction from 75 Kcal
mol-1 to 15 Kcal mol-1. What will be the effect on the rate of reaction at 27°C,
other things being equal?

61. Given that the temperature coefficient for the saponification of ethyl
acetate by NaOH is 1.75. Calculate activation energy for the saponification
of ethyl acetate.

62. 75% of a first order reaction occurs in 30 min at 27°C. 87.5% of the same
reaction occurs in 30 min at 57°C. The activation energy of reaction is:
[ln 2 = 0.7, ln 3 = 1.1]

63. The Arrhenius equation for the two first order equation
A B and C D is given by
k1 = 10 e
12 -81.28(kJ)/RT
; k2 = 10 e
11 -43.10(kJ)/RT

At what temperature k1 becomes equal to k2. The unit of activation energy

is kJ/mol.
Use: ln 10 = 2.3 and R = 8.3 JK-1mol-1

Page No. 11
64. At room temperature 300K, orange juice gets spoilt in about 52 hours. In a
refrigerator at 200K juice can be stored three times as long before it gets
spoilt. Estimate:
(a) The activation energy of the reaction that causes the spoiling of juice.
(b) How long should it take for juice to get spoilt at 400K?
Given: ln 3 = 1.1, e(11/20) = 1.733

65. The rate of reaction: A(g) 2B(g) increases e5 times on increasing the
temperature from 27°C to 327°C. The activation energy (in Kcal/mol) of
reaction is:
[Assuming activation energy is temperature independent]

66. A hydrogenation reaction is carried out at 500K. If the same reaction is

carried out in the presence of a catalyst at the same rate, the temperature
required is 400K. Calculate the activation energy of the reaction if the
catalyst lowers the activation barrier by 20kJmol-1.

67. For the mechanism:

k1
A+B C
k2
k
C 3
D
(a) Derive the rate law using the steady-state approximation to eliminate
the concentration of C.
(b) Assuming that k3<<k2, express the pre-exponential factor A and Ea for
the apparent second-order rate constant in terms of A1, A2 and A3 and Ea1,
Ea2 and Ea3 for the three steps.

Page No. 12
 ANSWERS

𝑑[𝑁𝑂]
1. (i) r= ¼ = 9 * 10-4 mol L-1 s-1, (ii) 36 * 10-4 mol L-1 s-1
𝑑𝑡
(iii) 54* 10-4 mol L-1s-1
2. 1.2 * 10-3 gm/min
3. (a) 2.1 * 10-7 M/s, (b) 8.4 * 10-7 M/s, 2.1 * 10-7 M/s.
4. 16 * 10-5 mol L-1s-1
5. 1.5 torr/s
6. (a) rate increases by 27 times, (b) rate decreases by 8 times
7. Rate of formation of Cl-1 = 4 * 10-7 M s-1
8. 8.12 * 10-6 M/s
9. 1/6
10. (i) 7.2 M, (ii) Think
11. 0%
12. 1.67 * 10-5 Ms-1
13. K = 0.01 M min-1
14. 0.05 atm/s
15. 0.75
16. 6 * 10-9 sec
17. 1.2 hr
18. (i) 36 min, (ii) 108 min. (iii) 1/8
19. (i) 0.0223 min -1
(ii) 62.17 min (iii) 0.6 or 0.59
20. 3.435 * 10 M/min
-3

21. t1/2 = 24.14 min

22. 6.67 * 10-4
23. 6M
24. 3.3 * 10-4 s-1
25. 11.2%
26. 1.45 * 10-3 M/s
27. 1.25 * 10-5 mol s-1
28. 6 * 10-6 s
29. (a) 0.01M (b) 20/3 min (c) 20/3 min
30. (a) 5 * 10 s -3 -1
(b) 0.06 bar (c) 1.386 * 102 s
31. (a) Rate law r = K[NH4+]1[NH2-]1; (b) 3 * 10-4 M-1s-1 (c) 6 * 10-5 Ms-1
6×10−3
32. (a) Rate law = k[A]1[B]2 (b) k = = 6 M-2s-1
10−3
33. 1
34. 3

Page No. 13
35. 0
36. 3
37. First Order
38. 16 mL
39. (i) r = K[(CH3)2O], 0.000428 s-1
40. (a) 65 min (b) 120 min
1 𝑃
41. k = ln 3
𝑡 (𝑃3 −𝑃2)
1 𝑟∞
42. k = ln
𝑡 (𝑟∞ −𝑟𝑡)
43. 966 min
44. (a) 90 mm (b) 47 min(c) 6.49 * 10-2 min-1 (d) 10.677 min
45. k1 = 2.605 * 10-3 min-1
46. 40 min
47. 0.1 min-1
48. 1.66 * 10-3 M-1 s-1
49. 0.1 min-1
1
50.
ⅇ (𝑘1+𝑘2) 𝑡−1
[𝐶] 10
51. [𝐴] = (ⅇ 11𝑥 − 1)
11
52. 𝑡 = 4 𝑚𝑖𝑛
53. 379.79 K
54. (a) 190 kJ (b) ∆H = 10kJ (c) Endothermic (d) f=e-76
55. Fraction = e-20
56. 9.6 Kcal/mol
57. (a) Ea= 14.4 Kcal (b) 528 M-1s-1
58. 54.124 kJ/mol (a) 2 (c) 1.5
59. 1000 Cal/mol
60. Rate of reaction increases e100 times
61. 10.757 Kcal/mol
62. 2.64 Kcal/mol
63. 2000 K
64. (a) 660R (b) 30 hours
65. 6 Kcal/mol
66. 100 kJ/mol
𝑑[𝐷] 𝑘1 𝑘3 [𝐴][𝐵] 𝐴1 𝐴3
67. (a) = ; (b) Ea = Ea1 + Ea3 – Ea2 ; A=
𝑑𝑡 𝑘2 + 𝑘3 𝐴2

Page No. 14