EXERCISE #S-I

RATE OF REACTION AND STOICHIOMETRIC COEFFICIENT

1. Ammonia and oxygen reacts at higher temperatures as

4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)
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 water

2. The reaction 2A + B + C  D + E is found to be first order in A second order in B and zero

order in C.
(i) Give the rate law for the reaction in the form of differential equation.
(ii)What is the effect in rate of increasing concentrations of A, B, and C two times?

3. 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 reaction (in
M sec–1) and rate of reaction in terms of pressure. [Use : R = 0.08 atm-lt/K-mole]

4. For the elementary reaction 2A + B2  2AB. Calculate how much the rate of reaction will
change if the volume of the vessel is reduced to one third of its original volume?

5. For the reaction 3BrO–  BrO3– + 2Br– in an alkaline aquesous solution, the value of the
–
d  BrO– 
second order (in BrO ) rate constant at 80°C in the rate law for – was found to be
dt
0.056 L mol–1 s–1. What is the rate of constant when the rate law is written for ,
d  BrO3  d  Br  
(a) , (b) ?
dt dt

6. A certain reaction A  B follows the given concentration (Molarity) – timed graph. Calculate
the rate for this reaction at 20 second. (ln2 = 0.7)
0.5
0.4

0.3
[A]
0.2

0.1

0 20 40 60 80 100
Time (sec)
7. The reaction A(g) + 2B(g)  C(g) + D(g) is an elementary process. In an experiment, the
initial partial pressure of A & 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.

8. The oxidation of iodide ion by peroxy disulphate ion is described by the equation :
3– (aq) + S2O82– (aq) 3– (aq) + 2SO42– (aq)
[S2O82 ] –3 –1 [  ]
(a) If – = 1.5 × 10 Ms for a particular time interval, what is the value of –
t t
for the same time interval?
(b) What is the average rate of formation of SO42– during that time interval?

9. In the following reaction 2H2O2 (aq)  2H2O() + O2 (g) rate of formation of O2 is 36 g

min–1 ,
(a) What is rate of formation of H2O? (b) What is rate of disappearance of H2O2?

ZERO ORDER REACTIONS

10. In the following reaction, rate constant is 1.2 × 10–2 M sec–1 A B. What is concentration
of B after 10 and 20 min., if we start with 10 M of A.

11. From 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

12. 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 mole litre–1 sec–1. How long would it take for H+ in drop to
disappear?

13. 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)

14. For the zero order reaction A  2B, the rate constant is 2 × 10–6 M min–1. The reaction is
started with 10 M of A

(i) What will be the concentration of A after 2 days? (ii) What is the initial half-life of the
reaction?
(iii) In what time, the reaction will complete?
 FIRST ORDER REACTIONS

15. A first order reaction is 75% completed in 72 min.. How long time will it take for
(i) 50% completion (ii) 87.5% completion
16. A first order reaction is 20% complete in 10 min. calculate (i) the specific rate constant , (ii) the
time taken for the reactions to go to 75% completion.
17. Show that in case of unimolecular reaction, the time required for 99.9% of the reaction to take
place in ten times that required for half of the reaction.
18. A drug is known to be ineffective after it has decomposed 75%. The original concentration of a
sample was 500 units/ml. When analyzed 20 months later, the concentration was found to be
250 units/ml. Assuming that decomposition is of I order, what will be the expiry time of the
drug?
19. 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 for inactivation process.

20. The reaction SO2Cl2(g) SO2(g) + Cl2(g) is a first order gas reaction with k =3.8 × 10–4
sec–1 at 320°C. What % of SO2Cl2 is decomposed on heating this gas for 90 min.

21. Substance A reacts according to a first order rate law with k = 5 x 105 s1.
(a) If the initial concentration of A is 1.0 M, what is initial rate .
(b) What is the rate after 1.0 hour. (Given e–0.18 = 0.84)
22. A and B are two different chemical species undergoing 1st order decomposition with half lives
equal to 5 sec. and 7.5 sec. respectively. If the initial concentration of A and B are in the ratio 3
C
: 2. Calculate At after three half lives of A. Report your answer after multiplying it with 100.
C Bt

EXPERIMENTAL METHODS TO CALCULATE ORDER AND RATE LAW

23. At 800° C the rate of reaction
2 NO + H2 N2 + H2O
Changes with the concentration of NO and H2 are
1 d  NO
[NO] in M [H2] in M  in M sec–1
2 dt
–4 –3
(i) 1.5 × 10 4 × 10 4.4 × 10–4
–4 –3
(ii) 1.5 × 10 2 × 10 2.2 × 10–4
(iii) 3.0 × 10–4 2 × 10–3 8.8 × 10–4
(a) What is the order of this reaction?
(b) What is the rate equation for the reaction?
(c) What is the rate when.
[H2] = 1.5 ×10–3 M and [NO] = 1.1 × 10–3M?
24. (a) The half life period and initial concentration for a reaction are as follows. What is order
of reaction?
Initial concentration 350 540 158
t1/2 425 275 941
(b) The half-life period for the thermal decomposition of PH3 at three different pressures
are given below
Initial pressure (mm Hg) 707 79 37.5
Half--life (seconds) 84 84 83
What is the order of the reaction ?

25. For the reaction A  products, the following data is given for a particular run.
time (min.) : 0 5 15 35
1
(M–1) : 1 2 4 8
[A]
Determine the order of the reaction.

26. The catalytic decomposition of N2O by gold at 900°C and at an initial pressure of 200mm is
50% complete in 53 minutes and 73% complete in 100 minutes.
(i) What is the order of the reaction?
(ii) Calculate the velocity constant.
(iii) How much of N2O will decompose in 100 min. at the same temperature but at initial
pressure of 600 mm?

27. The pressure of a gas decomposing at the surface of a solid catalyst has been measured at
different times and the results are given below
t (sec) 0 100 200 300
3 3 3
Pr. (Pascal) 4 × 10 3.5 × 10 3 × 10 2.5 × 103
Determine the order of reaction, its rate constant.

28. The half life period of decomposition of a compound is 50 minutes. If the initial concentration
is halved, the half life period is reduced to 25 minutes. What is the order of reaction?

CALCULATION OF RATE CONSTANT USING DIFFERENT PARAMETERS

29. For the Ist order reaction

A  B + C
Time t 
Total pressure of A + B + C P2 P3
Find k.
30. The kinetic of hydrolysis of methyl acetate in excess dilute HCl at 25°C were followed by
withdrawing 2 mL of the reaction mixture at intervals of (t), adding 50 mL water and titrating
with baryta water. Determine the velocity constant of hydrolysis.

t (in minute) 0 75 119 259  

Titre value (in mL) 19.24 24.20 26.60 32.23 42.03
22.79 22.79 22.79
[ln = 0.2454, ln = 0.39, ln = 0.8439]
17.83 15.43 9.8

31. The decomposition of hydrogen peroxide in an aqueous solution is a first order reaction. It can
be studied by titrating quickly 10 mL portions of reactions mixture at various times from the t =
0 of reaction against a standard solution of KMnO4. Volume of KMnO4 solution used in each
case is proportional to the remaining concentration of H2O2.
From the following data calculate the rate constant of the reaction,
Time (seconds) 0 600 1200
KMnO4 solution used (mL) 22.8 13.8 8.2

32. The thermal decomposition of dimethyl ether as measured by finding the increase in pressure of
the reaction
(CH3)2O(g) CH4(g) + H2(g) + CO(g)
at 500°C is as follows:
Time (sec.) 390 1195 
Pressure increase (mm Hg) 96 250 624
the initial pressure of ether was 312 mm Hg. Write the rate equation for this reaction and
determine the rate constant of reaction.

33. The decomposition of N2O5 according to the equation 2 N2O5 (g) 4 NO2(g) + O2(g) is a
first order reaction. After 30 min. from 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
is584.5 mm Hg. Calculate the rate constant of the reaction.

34. The reaction given below, rate constant for disappearance of A is 7.48 × 10–3 sec–1. Calculate
the time required for the total pressure in a system containing A at an initial pressure of 0.1 atm
to rise to 0.145 atm and also find the total pressure after 100 sec.
2A (g)  4B(g) + C(g)

35. For the Ist order reaction S  G + F

Time t 
Rotation of Glucose & Fructose rt r
Find k.
36. The following data were obtained in experiment on inversion of cane sugar.
Time (minutes) 0 60 120 180 360  
Angle of rotation +13.1 + 11.6 + 10.2 +9.0 +5.87 –3.8
(degree)
Show that the reaction is of first order. After what time would you expect a zero reading in
polarimeter?

37. The reaction A(aq)  B (aq) + C (aq) is monitered by measuring optical rotation of reaction
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 first order conversion of A into B and C.

PARALLEL AND SEQUENTIAL REACTION

k1 B
C
38. A , k1 = x hr–1; k1 : k2 = 1 : 10. Calculate   after one hour from the start of the
k2 C  A 
reaction. Assuming only A was present in the beginning.

39. A gaseous reactant X decompose to produce gaseous product B & C in a parallel reaction, both
by first order, as follows :
–3 –1
k1= 2×10min
B(g)
X(g)
–2 –1 C(g)
k2= 3×10min
If the decomposition is carried out in a sealed flask, partial pressure of B after very long time
was found to be 100 mm Hg. Determine the time when pressure of X(g) was 100 mm Hg.
[ln2 = 0.693]

B
40. The reaction A proceeds in parallel channels A Suppose the half life values for the two
C
branches are 60 minutes and 90 minutes, what is the overall half-life value?

41. For the given sequential reaction

k1 k2
A   B  C
Initial concentration of A is 20M. Calculate the approximate concentration of C after 10 min, if
k1 = 2 × 108 min–1 & k2 = 0.0693min–1.

42. How much time would be required for the B to reach maximum concentration for the reaction
k1 B  k2 ln 2 ln 2
A   C. Given k1 = , k2 = .
4 2
 TEMPERATURE DEPENDENCE OF RATE (ACTIVATION ENERGY)
43. In gaseous reactions important for understanding the upper atmosphere, H2O and O react
bimolecularlyto form two OH radicals. H for this reaction is 72 kJ at 500 K and Ea=77 kJ
mol–1, then calculate Ea for the bimolecular recombination of 2OH radicals to form H2O & O at
500 K

44. The specific rate constant for a reaction increases by a factor of 4, if the temperature is changed
from 27°C to 47°C. Find the activation energy (in kcal) for the reaction (Use ln 2 = 0.7)

45. 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. [Use : ln (1.75) = 0.56]

46. At 380°C, the half-life period for the first order decomposition of H2O2 is 360 min.The energy
of activation of the reaction is 200 kJ mol–1. Calculate the time required for 75% decomposition
 1 1  = 1.48 × 10–4,
at 450°C. Use :   
 653 723 
47. Find out the percentage of the reactant molecules crossing over the activation energy barrier at
325 K, given that H325 = 0.12 kcal, Ea(b) = + 0.02 kcal.

48. Consider the following figure for the reaction :

A + B  M + N
Answer the following :

A+B
E
Y

M+N
Z

Energy of activation diagram

(A) Energy level of (A + B)

(B) Energy level of (M + N)
(C) Threshold energy level for the reaction
(D) Energy of activation for the forward reaction.
(E) Energy of activation for the backward reaction.
(F) H or heat of reaction.

CATALYST DEPENDENCE OF RATE & REACTION MECHANISM

49. On introducing a catalyst at 500 K, the rate of a first order reaction increase to 1.718 times. The
activation energy in the presence of a catalyst is 6.05 KJ/mole. The slope of the plot of lnk
(sec–1) against 1/T in the absence of catalyst is :

50. Given the following steps in the mechanism for a chemical reaction :
A + B  C (fast)
B + C  D + E  slow)
D + F  A + E  fast)
At any time [C] is directly proportional to [A].
(a) What is the stoichiometric equation for the reaction ?
(b) Which species, if any, are catalysts in this reaction ?
(c) Which species, if any, are intermediates in this reaction?
(d) Write the rate law for the rate-determining step.
(e) Write the rate law for this reaction.
(f) What is overall order of the reaction ?

51. The thermal decomposition of N2O5 occurs in the following steps.

Step -  N2O5 
slow
 NO2 + NO3
Step -  N2O5 + NO3 
fast
 3NO2 + O2

2N2O5  4NO2 + O2
suggest the rate expression.

52. The reaction 2NO + Br2  2NOBr, is supposed to follow the following mechanism
(i) 
fast
NO + Br2  
 NOBr2
(ii) NOBr2 + NO  slow
 2NOBr
Suggest the rate law expression.

53. For the reaction 2H2 + 2NO N2 + 2H2O, the following mechanism has been suggested :

2NO  N2O2 equilibrium constant K1 (fast)
k2
N2O2 + H2  N2O+ H2O (slow)
k3
N2O + H2   N2 + H2O (fast)
Establish the rate law for given reaction.
 EXERCISE # S-II

1. For the reaction,

A + B Product
rate law is
rate = k [A]2 [B]
where k = 5 × 10–5 (mol/L)–2 min–1
Determine the time (in minutes) in which concentration of 'A' becomes half of its initial
concentration. If initial concentration of A and B are 0.2 M and 2 × 103 M respectively.

2. The reaction
k1

cis-Cr(en)2(OH)+2   trans – Cr(en)2(OH)+2
k2 
is first order in both directions. At 25°C the equilibrium constant is 0.16 and the rate constant is
3.3 × 10–4s–1. In an experiment starting with the pure cis form, how long would it take for half
the equilibrium amount of the trans isomer to be formed ?

3. The decomposition of a compound P, at temperature T according to the equation

2P(g) 4Q(g) + R(g) + S(l)
is the first order reaction. After 30 minutes from the start of decomposition in a closed vessel,
the total pressure developed is found to be 317 mm Hg and after a long period of time the total
pressure observed to be 617 mm Hg. Calculate the total pressure of the vessel after 75 minute,
if volume of liquid S is supposed to be negligible. Also calculate the time fraction t7/8.
Given : Vapour pressure of S (l) at temperature T = 32.5 mm Hg.

4. At room temperature (20°C) orange juice gets spoilt in about 64 hours. In a referigerator at 3°C
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 40°C?

5. An optically active compound A upon acid catalysed hydrolysis yield two optically active
compound B and C by pseudo first order kinetics. The observed rotation of the mixture after 20
min was 5° while after completion of the reaction it was – 20°. If optical rotation per mole of
A, B & C are 60°, 40° & – 80°. Calculate half life of the reaction.

6. A certain organic compound A decomposes by two parallel first order mechanism

k1 B
A
k2 C If k1 : k2 = 1 : 9 and k1 = 1.3 × 10–5 s–1.
Calculate the concentration ratio of C to A, if an experiment is started with only A and allowed
to run for one hour.
7. The rate constant for the II order ( A + B  obeys the equation
3163
log10 K = + 12
T
T is temperature in Kelvin.
Time and concentration were in minute and mol L–1 respectively. At 43.3°C initial
concentration of each of the reactant is 0.001 mol L–1. Find half life .

8. Two reations (i) A  products (ii) B  products, follow first order kinetics. The rate of the
reaction (i) is doubled when the temperature is raised from 300 K to 310K. The half life for this
reaction at 310K is 30 minutes. At the same temperature B decomposes twice as fast as A. If
the energy of activation for the reaction (ii) is half that of reaction (i), calculate the rate constant
of the reaction (ii) at 300K.

9. The reaction of formation of phosgene from CO and Cl2 is CO + Cl2  COCl2 The proposed
mechanism is

K1
(i) Cl2   2Cl
K 
(fast equilibrium)
1


K2
(ii) Cl + CO   COCl
K 
(fast equilibrium)
2

(iii) COCl + Cl2 

K3
 COCl2 + Cl (slow)
d COCl2 
Show that the above mechanism leads to the following rate law = K[CO] [Cl2]3/2.
dt
k 2  k1 1/ 2
k 2  k  1 
Where K = k3. .

k1 k2
10. For the two parallel reactions A   B and A  C, show that the activation energy E'
for the disappearance of A is given in terms of activation energies E1 and E2 for the two paths
by
k1E1  k 2E2
E=
k1  k 2

11. An organic compound dissociates into n parallel first order reactions simultaneously and
produces n different products P1, P2, P3, ......., Pn having rate constants k, 2k, 3k, ......, nk and
activation energies E, 2E, 3E ..............., nE respectively. Calculate the overall energy of
activation of the compound P.
EXERCISE # O-I
 SINGLE CORRECT
RATE OF REACTION AND STOICHIOMETRIC COEFFICIENT
1. The rate of a reaction is expressed in different ways as follows :
1 d  C 1 d  D 1 d A d  B
+ =– =+ =–
2 dt 3 dt 4 dt dt
The reaction is:
(A) 4 A + B 2C + 3D (B) B + 3 D 4 A + 2 C
(C) A + B C + D (D) B + D A + C

2. For the reaction 2A + 3B  4C

the rate of reaction may be represented as :
d  A d  B d C d  A d  B d C
(A) r = –2 =– =4 (B) r = –2 = –4 =3
dt dt dt dt dt dt
1 d  A  1 d  B 1 d  C 1 d  A 1 d  B 1 d  C 
(C) r = – = = (D) r = – =– =
2 dt 3 dt 4 dt 2 dt 3 dt 4 dt

3. In a reaction N2(g) + 3H2(g)  2NH3(g) the rate of appearance of NH3 is 2.5×10–4molL–

1
sec–1. The Rate of reaction & rate of disappearance of H2 will be(In molL–1sec–1)
(A) 3.75 × 10–4, 1.25 × 10–4 (B) 1.25 × 10–4, 2.5 × 10–4
(C) 1.25 × 10–4, 3.75 × 10–4 (D) 5.0 × 10–4, 3.75 × 10–4

4. For the reaction, 2NO(g) + 2H2(g)  N2(g) + 2H2O(g) the rate expression can be written in
the following ways:
{d [N2] / dt} = k1 [NO][H2] ; {d[H2O] / dt} = k[NO][H2] ; {– d[NO] / dt} = k1 [NO] [H2] ;
{–d[H2] / dt} = k1 [NO][H2]
The relationship between k, k1 , k1 and k1. is :
(A) k = k1 = k1 = k1 (B) k = 2k1 = k1 = k1
(C) k = 2k1 = k1 = k1 (D) k = k1 = k1 = 2 k1

5. For the reaction 4A + B  2C + 2D

The incorrect statement is :–
(A) The rate of disappearance of B is one fourth the rate of disappearance of A
(B) The rate of appearance of C is half the rate of disappearance of B
(C) The rate of formation of D is half the rate of consumption of A
(D) The rates of formation of C and D are equal
6. For a reaction A + B  products, the rate of the reaction was doubled when the concentration
of A was doubled, the rate was again doubled when the conc. of A & B were doubled the order
of the reaction with respect to A & B are:–
(A) 1, 1 (B) 2, 0 (C) 1, 0 (D) 0, 1

7. Rate of formation of product at t = 20 seconds is :

(A) 0.5 MS–1 (B) 1 M S-1 (C) 1.5 M S–1 (D) 2MS–1

8. For the irreversible process, A + B products, the rate is first–order w.r.t. A and second–
order w.r.t. B. If 1.0 mol each of A and B introduced into a 1.0 L vessel, and the initial rate was
1.0 × 10–2 mol L–1 s–1 , rate when half reactants have been turned into products is :

(A) 1.25 × 10–3 mol L–1 s–1 (B) 1.0 × 10–2 mol L–1 s–1
(C) 2.50 × 10–3 mol L–1 s–1 (D) 2.0 × 10–2 mol L–1 s–1

9. In the following reaction : xA  yB

 d[A]   d[B] 
log   = log  + 0.3
 dt   dt 
where –ve sign indicates rate of disappearance of the reactant. Thus, x : y is :
(A) 1 : 2 (B) 2 : 1 (C) 3 : 1 (D) 3 : 10

10. If concentration of reactants is increased by 'x' then the k becomes –

k k
(A) ln (B) (C) k + x (D) k
x x

ZERO ORDER REACTIONS

11. If the rate of the reaction is equal to the rate constant, the order of the reaction is:-
(A) 0 (B) 1 (C) 2 (D) 3

12. The rate constant of a zero order reaction is 0.2 mol dm–3h–1. If the concentration of the reactant
after 30 minutes is 0.05 mol dm–3. Then its initial concentration would be :
(A) 0.15 mol dm–3 (B) 1.05 mol dm–3 (C) 0.25 mol dm–3 (D) 4.00 mol dm–3

61
13. Consider the reaction A  B, graph between half life
(t1/2) is and initial concentration (a) of the reactant
d  A
Hence graph between  and time will be
dt

t1/2

d A d A
(A) – (B) –
dt dt t

d A d A
(C) – (D) –
dt t
dt t

14. The rate constant of the reaction A  2B is 1.0 × 10–3 mol L–1 min–1, if the initial concentration
of A is 1.0 mole L–1 what would be the concentration of B after 100 minutes.
(A) 0.1 mol lit–1 (B) 0.2 mol lit–1 (C) 0.9 mol lit–1 (D) 1.8 mol lit–1

15. What will be the order of reaction and rate constant for a chemical change having log t 50% vs
log A0 (A0= Initial concentration of reactant) curves as :

logA0
(A) 0, 1/2 (B) 1, 1 (C) 2, 2 (D) 3, 1

16. From different sets of data of t1/2 at different initial concentrations say 'a' for a given reaction,
the
[t1/2  a] is found to be constant. The order of reaction is :–
(A) 0 (B) 1 (C) 2 (D) 3

FIRST ORDER, SECOND ORDER & nth ORDER REACTIONS

17. If the first order reaction involves gaseous reactants and gaseous products the units of its rate
are –
(A) atm. (B) atm. sec. (C) atm.sec–1 (D) atm2 sec2
18. A reaction is found to have the rate constant X sec–1 by what factor the rate is increased if
initial conc. of A is tripled
(A) 3 (B) 9 (C) X (D) Remains same

19. The rate constant of a first order reaction is 4 × 10–3 sec–1. At a reactant concentration of 0.02
M, the rate of reaction would be –
(A) 8 × 10–5 M sec–1 (B) 4 × 10–3 M sec–1 (C) 2 × 10–1 M sec–1 (D) 4 × 10–1 M sec–1

20. In a first order reaction the concentration of the reactant is decreased from 1.0 M to 0.25 M in
20 min. The rate constant of the reaction would be –
(A) 10 min–1 (B) 6.931 min–1 (C) 0.6931 min–1 (D) 0.06931 min–1

21. A first order reaction has a half life period of 69.3 sec. At 0.10 mol lit –1 reactant concentration
rate will be –
(A) 10–4 M sec–1 (B) 10–3 M sec–1 (C) 10–1 M sec–1 (D) 6.93 × 10–1Msec–1

22. What fraction of a reactant left showing first order reaction after 40 minute if t½ is 20 minute
(A) 1/4 (B) 1/2 (C) 1/8 (D) 1/6

23. Which of the following curves represents a Ist order reaction :–

log(a–x) log(a–x) t1/2

(A) (B) (C) (D) 1 & 3 both
t 1/t a

24. After how many seconds will the conc. of the reactant in a first order reaction be halved, if the
rate constant is 1.155 × 10–3 sec–1 :–
(A) 600 (B) 100 (C) 60 (D) 10

25. Correct statement about first order reaction is:-

1
(A) tcomplition = finite (B) t1/2 
2
(C) Unit of k is mole lit–1 sec–1 (D) t t1/2 × k = const. at const. temp.

26. For a given reaction of first order it takes 20 minute for the concentration to drop from 1 M to
0.6 M. The time required for the concentration to drop from 0.6 M to 0.36 M will be :
(A) More than 20 min (B) Less than 20 min
(C) Equal to 20 min (D) Infinity
27. A reaction, which is second order, has a rate constant of 0.002 L mol–1 s–1. If the initial conc. of
the reactant is 0.2 M. how long will it take for the concentration to become 0.0400 M ?
(A) 1000 sec (B) 400 sec (C) 200 sec (D) 10, 000 sec

28. Which is not true for a second order reaction ?

(A) It can have rate constant 1 × 10–2 L mol–1 s–1
(B) Its half-life is inversely proportional to its initial concentration
(C) Time to complete 75% reaction is twice of half-life
1
(D) t50% =
k A0

29. For the reaction 2NO2  N2O2 + O2, rate expression is as follows :
d[NO2 ]
– = k [NO2]n , where k = 3 × 10–3 mol–1 L sec–1. If the rate of formation of oxygen is
dt
1.5 × 10–4 mol L–1 sec–1, then the molar concentration of NO2 in mole L–1 is
(A) 1.5 × 10–4 (B) 0.0151 (C) 0.214 (D) 0.316

30. A reaction is of first order. After 100 minutes 75 g of the reactant A are decomposed when
100g are taken initially, calculate the time required when 150 g of the reactant A are
decomposed, the initial weight taken is 200g :
(A) 100 minutes (B) 200 minutes (C) 150 minutes (D) 175 minutes

31. Consider the reaction :

A  B + C
Initial concentration of A is 1 M. 20 minutes time is required for completion of 80 % reaction.
d  B
If = k[A], then half life (t1/2 ) is (Use : ln 5 = 1.6)
dt
(A) 55.44 min (B) 50 min (C) 8.66 min (D) None of these

32. The accompanying figure depicts the change in concentration of species X and Y for the
reaction X Y as a function of time the point of intersection of the two curves represents.

1
Concentration

X
0.5

Y
0 Time

(A) t1/2 (B) t3/4

(C) t2/3 (D) Data insufficient to predict
33. At the point of intersection of the two curves shown, the conc. of B is given by.....for, A  nB :

nA0 A0 nA0  n –1 
(A) (B) (C) (D)   A0
2 n –1 n 1  n 1 

34. A graph between log t1/2 and log a (abscissa) a being the initial concentration of A0 in the
reaction For reaction A  Product, the rate law is :

log t 1/2 Slope = – 1

log A0

– d[A] – d[A] – d[A] – d[A]

(A) =k (B) = k [A] (C) = k [A]2 (D) = k [A]3
dt dt dt dt

35. In three different reactions, involving a single reactant in each case, a plot of rate of the reaction
on the yaxis, versus concentration of the reactant on the xaxis, yields three different curves
shown below.

(i) (ii) (iii)

What are the possible orders of the reactions (i), (ii), (iii).
(A) 1, 2, 3 (B) 2, 1, 1/2 (C) 0, 1, 2 (D) 0, 1, 1/2

36. Unit of rate constant of nth order reaction is.

(A) litre1–n mol1–n sec–1 (B) moln–1 litre1–n sec–1
(C) mol1–n litren–1 sec–1 (D) None

37. If decomposition reaction A (g) B (g) follows first order kinetics then the graph of rate of
formation (R) of B against time t will be
R R R R

(A) (B) (C) (D)

t t t t
38. For the first order decomposition of SO2Cl2(g), SO2Cl2(g)  SO2(g) + Cl2(g) a graph of log
(a0 – x) vs t is shown in figure. What is the rate constant (sec–1)?
Time(min)
2 4 6 8 10
(0,0)

log(a0–x)
–1

–2

–3

(A) 0.2 (B) 4.6 × 10–1 (C) 7.7 × 10–3 (D) 1.15 × 10–2

39. The rate constant for a second order reaction is 8 × 10–5 M–1 min–1 : How long will it take a 1M
solution to be reduced to 0.5 M.
(A) 8.665 × 103 min (B) 8 × 10–3 min (C) 1.25 × 104 min (D) 4 × 10–5 min
d P
40. The rate law of the reaction A + 2B  product(P) is given by   = K[A]2 [B]. If A is taken
dt
in large excess, the order of the reaction will be –
(A) Zero (B) 1 (C) 2 (D) 3
41. Time required to complete a half fraction of a reaction varies inversely to the concentration of
reactant then the order of reaction is –
(A) Zero (B) 1 (C) 2 (D) 3

EXPERIMENTAL METHODS TO CALCULATE ORDER

OF REACTION & RATE LAW
42. The data for the reaction A + B  C is :
Exp. [A]0 [B]0 initial rate
1 0.012 0.035 0.10
2 0.024 0.035 0.80
3 0.012 0.070 0.10
4 0.024 0.070 0.80
The rate law is
(A) r = k [B]3 (B) r = k [A]3 (C) r = k [A] [B]4 (D) r = k [A]2 [B]2

43. The kinetic data for the given reaction A(g) + 2B(g) C(g) is provided in the following table for
three experiments at 300 K.

In another experiment starting with intitial concentration of 0.5 and 1 M respectively for A and
B at 300 K. Find the rate of reaction after 50 minutes from start of experiment (in m/sec)?
(A) 6.93 × 10–4 (B) 0.25 × 10–7 (C) 4.33 × 10–5 (D) 3.46 × 10–9
44. At certain temperature, the half life period for the thermal decomposition of a gaseous
substance depends on the initial partial pressure of the substance as follows
Pressure (mmHg) 500 250
t1/2 (in min.) 235 950
Find the order of reaction [Given log (23.5) = 1.37 ; log (95) = 1.97; log 2 = 0.30]
(A) 1 (B) 2 (C) 2.5 (D) 3

CALCULATION OF RATE CONSTANT USING DIFFERENT PARAMETERS

45. Azo isopropane decomposes according to the equation :–

250290C
(CH3)2CHN=NCH(CH3)2(g)   N2(g) + C6H14(g)
It is found to be a first order reaction. If initial pressure is Po and pressure of the mixture at time
t is (Pt) then rate constant K would be :–
2.303 P0 2.303 P P
(A) k = log (B) k = log 0 t
t 2P0  Pt t P0
2.303 P 2.303 2P0
(C) k = log 0 (D) k = log
t P0  Pt t 2P0  Pt

1
46. Half life of reaction : H2O2(aq)  H2O(l) + O2(g) is independent of initial concentration
2
of H2O2 volume of O2 gas after 20 minute is 5L at 1 atm and 27°C and after completion of
reaction 50L. The rate constant is
1 2.303
(A) log 10min 1 (B) log 10min 1
20 20
2.303 50 2.303 45
(C) log min 1 (D) log min 1
20 45 20 50

47. At 373 K, a gaseous reaction A  2B + C is found to be of first order. Starting with pure A, the
total pressure at the end of 10 min was 176 mm of Hg and after a long time when A was
completely dissociated, it was 270 mm of Hg. The pressure of A at the end of 10 minutes was :
(A) 94 mm of Hg (B) 47 mm of Hg
(C) 43 mm of Hg (D) 90 mm of Hg

48. In the reaction NH4NO2 (aq.)  N2 (g) + 2 H2O (l) the volume of N2 after 20 min and after a
long time is 40 ml and 70 ml respectively. The value of rate constant is :
(A) (1/20) Iog (7/4) min–1 (B) (2.303 /1200) log (7/3) sec–1
–1
(C) (1/20) log (7/3) min (D) (2.303 / 20) log (11/7) min–1
49. For a reaction A  B + C, it was found that at the end of 10 minutes from the start the total
optical rotation of the system was 50° and when the reaction is complete, it was 100°.
Assuming that only B and C are optically active and dextrorotatory. Calculate the rate constant
of this first order reaction.
(A) 0.693 min–1 (B) 0.0693 sec–1 (C) 0.0693 min–1 (D) 0.00693 sec–1

50. The following data were obtained in an experiment on inversion of cane sugar (a first order
kinetics)
Time (min) 0 10 After a long time
Total angle of rotation (degree) +40 +15 – 10
–1
The rate constant (in second ) is [ln 2 = 0.693]
(A) 0.0693 (B) 1.15  10–3 (C) 0.693 (D) 1.15  10–2

PARALLEL AND SEQUENTIAL REACTION

51. The substance undergoes first order decomposition. The decomposition follows two parallel
first order reactions as :

k1 = 1.26 × 10–4 sec–1 and k2 = 3.8 × 10–5 sec–1

The percentage distribution of B and C

(A) 80% B and 20% C (B) 76.83% B and 23.17%C
(C) 90% B and 10% C (D) 60% B and 40% C

52. For a hypothetical elementary reaction.

k1

k2

k1 1
where =
k2 2
Initially only 2 moles of A are present. The total number of moles of A, B and C at the end of
75% of reaction are :
(A) 2 (B) 3 (C) 4 (D) 3.5

TEMPERATURE DEPENDENCE OF RATE (ACTIVATION ENERGY)

53. According to collision theory of reaction rates –

(A) Every collision between reactant leads to chemical reaction
(B) Rate of reaction depends upon shape of molecule
(C) All reactions which occur in gaseous phase are zero order reaction
(D) Rate of reaction is directly proportional to collision frequency.
54. Activation energy of a reaction is –
(A) The energy released during the reaction
(B) The energy evolved when activated complex is formed
(C) Minimum amount of energy needed to overcome the potential barrier of reaction
(D) The energy needed to form one mole of the product

55. The minimum energy for molecules to enter into chemical reaction is called.
(A) Kinetic energy (B) Potential energy (C) Threshold energy (D) Activation energy

56. For producing the effective collisions, the colliding molecules must posses:-
(A) A certain minimum amount of energy
(B) Energy equal to or greater than threshold energy
(C) Proper orientation
(D) Threshold energy as well as proper orientation of collision

57. A large increase in the rate of a reaction for a rise in temperature is due to –
(A) Increase in the number of collisions (B) Increase in the number of activated molecules
(C) Lowering of activation energy (D) Shortening of the mean free path

58. Which plot the slope of which can give us the value of activation energy :
1
(A) k versus T (B) versues T (C) log k versus 1/T (D) C versus T
k

59. Given that k is the rate constant for some order of any reaction at temp T then the value of
lim k_________.
T 

2
(A) (B) A (C) 2.303 A (D) log A
2.303

60. The rate constant, the activation energy and the Arrhenius parameter (A) of a chemical reaction
at 25°C are 3.0 × 10–4 s–1, 104.4 kJ mol–1 and 6.0 × 1014s–1 respectively. The value of the rate
constant at T is
(A) 2.0 × 1018 s–1 (B) 6.0 × 1014 s–1 (C) infinity (D) 3.6 × 1030 s–1

61. For a certain gaseous reaction a 10° C rise of temp. from 25° C to 35° C doubles the rate of
reaction. What is the value of activation energy :–
10 2.303 10
(A) (B)
2.303R  298  308 298  308R
0.693R 10 0.693R  298  308
(C) (D)
290  308 10
62. From the following data; the activation energy for the reaction (cal/mol) H2 + I2  2HI
T , (in K) 1/T, (in K–1) log10k
769 1.3 × 10–3 2.9
667 1.5 × 10–3 1.1
(A) 4 × 104 (B) 2 × 104 (C) 8 × 104 (D) 3 × 104

63. A first order reaction is 50% completed in 20 minutes at 27°C and in 5 min at 47°C. The
energy of activation of the reaction is
(A) 43.85 kJ/mol (B) 55.14 kJ/mol (C) 11.97 kJ/mol (D) 6.65 kJ/mol

64. For the first order reaction A  B + C, carried out at 27 ºC if 3.8 × 10–16 % of the reactant
molecules can overcome energy barrier, the Ea (activation energy) of the reaction is [log 3.8 =
0.58]
(A) 12 kJ/mole (B) 831.4 kJ/mole (C) 100 kJ/mole (D) 88.57 kJ/mole

65. The Arrhenius relationship of two different reactions is shown below. Which reaction is faster
at a lower temperature and which is more sensitive to changes of temperature ?

(A) B faster, A more sensitive (B) B in both cases

(C) A in both cases (D) A faster, B more sensitive

66. When a graph between ln K and 1/T is drawn a straight line is obtained. The point at which line
cuts y -axis and x -axis respectively correspond to the temperature :
(A) 0, Ea / 2.303 R log A (B) , Ea / (R ln A)
(C) 0, log A (D) None of these.

67. For a reaction A  B, Ea = 10 kJ mol–1 , H = 5 kJ mol–1 . Thus, potential energy profile for
this reaction is :

PE

(A) (B)
Reaction progress

PE

(C) (D)
Reaction progress Reaction progress
 CATALYST DEPENDENCE OF RATE & REACTION MECHANISM

68. The Ea of a reaction in presence of a catalyst is 4.15 kJ mol–1 and in absence of a catalyst is 8.3
1
kJ mol–1. What is slope of the plot of ln k vs in the absence of catalyst
T
(A) + 1 (B) –1 (C) + 1000 (D) –1000

69. For the reaction H2 (g) + Br2 (g)  2HBr (g) the experiment data suggested that r =
k[H2][Br2]1/2
The molecularity and order of the reaction are respectively :
(A) 2, 3/ 2 (B) 3/2 , 3/2 (C) Not defined, 3/2 (D) 1,1/2

70. Following mechanism has been proposed for a reaction : 2A + B  D + E Mechanism

A + B  C + D (slow)
A + C  E (fast)
The rate law expression for the reaction is :
(A) r = k[A]2 [B] (B) r = k[A] [B] (C) r = k[A]2 (D) r = k[A][C]

71. The reaction mechanism for the reaction P  R is as follows :


K1
P   2Q (fast) ; 2Q + P 
K3
 R (slow)
K  2

the rate law for the main reaction (P  R) is :

k k  P
2

(A) k1 [P] [Q] (B) k1k2 [P] (C) 1 3 (D) k1k2 [a]
k2

72. The following mechanism has been proposed for the exothermic catalyzed complex reaction.
k1  AB + I k2  P + A
  I AB 

fast
A + B 
If k1 is much smaller than k2. The most suitable qualitative plot of potential energy (P.E.)
versus reaction coordinate for the above reaction
P.E.

A+P
P.E.

AB+I
A+B
(A) A+B (B)
IAB IAB
A+P
AB+I
reaction coordinate reaction coordiinate
P.E.

P.E.

(C) A+B (D) A+B

AB+I A+P IAB
AB+I A+P
IAB
reaction coordinat reaction coordinat
73. Choose the correct set of identifications, for the reaction : S 
[E]
P
Mechanism S + E  ES
ES  EP
EP  E + P

Potential energy
(4)
(2) (3)
(1)
Reaction coordinate

(A) (B) (C) (D)

(A) E for Ea for Eoverall Ea for
E + S  ES ES  EP for S  P EP E + P
(B) Ea for   E for Ea for Eoverall
E + S  ES E + S  ES ES  EP for S  P
(C) Ea for Ea for Eoverall E for
ES  EP EP  E + P for S  P EP  E + P
(D) Ea for Ea for Ea for Eoverall
E + S  ES ES  EP EP  E + P for S  P
(E) E for Eoverall E forl Ea for
E + S  ES for S  P EP  E + P EP  E + P

74. The reaction of NO2 (g) and O3 (g) is first-order in NO2 (g) and O3 (g)
2 NO2 (g) + O3 (g)  N2O5 (g) + O2 (g)
The reaction can take place by mechanism :
I : NO2 + O3 
slow
 NO3 + O2
NO3 + NO2 
fast
 N2O5

ka fast
II : O3   O2 + [O]
kb 

NO2 + O 
slow
 NO3
NO3 + NO2 
fast
N2O5
Select correct mechanism.
(A) I only (B) II only
(C) both I and II (D) None of I and II
75. Reaction A + B  D + E take place as
A + B 
K1
 2C
C + B 
K2
 2D
C + A  K3
 2E
The rate of disapperance of C is given by
d[C]
(A) – = K2 [B][C] + K3[A][C] – 2K1[A][B]
dt
d[C]
(B) – = K2[B][C] + K3 [E] – K1[C]
dt
d[C]
(C) – = K2[D]O + K3[E] – K1[C]
dt
d
(D) – [C] = 2K1[A][B] – K2 [B][C] – K3[A][C]
dt
 EXERCISE # O-II
MORE THAN ONE MAY BE CORRECT
1. Which of the following is/are correct statement?
(A) Stoichiometry of a reaction tells about the order of the elementary reactions.
(B) For a zero order reaction, rate and the rate constant are identical.
(C) A zero order reaction is controlled by factors other than concentration of reactants.
(D) A zero order reaction is always elementary reaction.

d A
2. For the reaction A  B, the rate law expression is – = k [A]1/2. If initial concentration of
dt
[A] is [A]0, then

(A) The integrated rate expression is k =  A0  A1/ 2 

2 1/ 2
t

(B) The graph of A vs t will be

t
(C) The half life period t1/ 2 =
K
(D) The time taken for 75% completion of reaction t3/4 =
2 A0
1/ 2

d [C]
3. For the reaction 2A + B  C with the rate law = k [A] 1 [B] –1 and started
dt
with A and B in stoichiometric proportion. Which is/are true?
(A) unit of k is Ms –1
(B) [A], [B] and [C] all will be linear functions of time
(C) [C] = 2kt
(D) [C] = kt
4. Decomposition of 3 A(g)  2 B(g) + 2C(g) follows first order kinetics. Initially only A is
present in the container. Pressure developed after 20 min. and infinite time are 3.5 and 4 atm
respectively. Which of the following is true.
(A) t50% = 20 min (B) t75% = 40 min (C) t99% = 64/3 min (D) t87.5% = 60 min
1
5. For a second order reaction plots are made for vs time for the reaction, 2A  Product.
[A]
Pick up the correct sentences. [K = Rate constant of A]
(A) the graph will show straight line with slope K
(B) the graph will show straight line with intercept [A]0
(C) the graph will show straight line with slope [A]0
1
(D) the graph will show straight line with intercept
[A]0
6. Consider the reaction,
–1
–2
min B
3×10
k 1=6.9
A
k2 =13
.86×1 –2
0 mi –1 C
n

A, B and C all are optically active compound . If optical rotation per unit concentration of A, B
and C are 60°, –72°, 42° and initial concentration of A is 2 M then select write statement(s).
(A) Solution will be optically active and dextro after very long time
(B) Solution will be optically active and levo after very long time
(C) Half life of reaction is 15 min
(D) After 75% conversion of A into B and C angle of rotation of solution will be 36°.

7. Which of the following statements about the arrhenius equation are correct ?
(A) The pre exponential factor become equal to the rate constant of the reaction at temperature T
(B) When the activation energy of the reaction zero, the rate becomes independent of
temperature.
(C) The term e–Ea/RT represents the fractions of the molecules having energy in excess of the
threshold value.
(D) On raising temperature, rate constant of the reaction of greater activation energy increases
less rapidly than that of the reaction of smaller activation energy.

8. Select incorrect statement(s):

(A) Unit of pre-exponential factor (A) for second order reaction is mol L–1 s–1.
(B) A zero order reaction must be a complex reaction.
(C) Molecularity is defined only for RDS in a complex reaction.
(D) Rate constant (k) remain unaffected on changing temperature.

9. Which of the following statement is/are correct?

(A) A second order reaction must be a bimolecular elementary reaction
(B) A bimolecular elementary reaction must be a second order reaction
(C) Order of reaction can’t be predicted by stoichiometry of reaction.
(D) First order reaction may be complex or elementary reaction

10. For the reaction CH4 + Br2  CH3Br + HBr the experimental data give the following rate
equation:
d k1[CH4 ][Br2 ]
[CH 3 Br] =
dt 1  k 2[HBr] / [Br2 ]
Which of the following is/are true regarding this ?
(A) The reaction is a single step reaction
(B) The reaction is 2nd order in the initial stages {[HBr]  0}
(C) The reaction is 2nd order in the final stages {[Br2]  0}
(D) The molecularity of the reaction is two
 ASSERTION & REASONING TYPE QUESTIONS
11. Statement-1 : A fractional order reaction must be a complex reaction.
Statement-2 : Fractional order of RDS equals to overall order of a complex reaction.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for
statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.

12. Statement-1 : The time of completion of reactions of type A  product (order <1) may be
determined.
Statement-2 : Reactions with order  1 are either too slow or too fast and hence the time of
completion can not be determined.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for
statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.

13. Statement-1 : In a reversible endothermic reaction, Eact of forward reaction is higher than that
of backward reaction
Statement-2 : The threshold energy of forward reaction is more than that of backward reaction
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for
statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.

14. Statement-1 : A catalyst provides an alternative path to the reaction in which conversion of
reactants into products takes place quickly
Statement-2 : The catalyst forms an activated complex of lower potential energy, with the
reactants by which more number of molecules are able to cross the barrier per unit of time.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for
statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.
 COMPREHENSION
Paragraph for Question Nos. 15 & 16
Oxidation of metals is generally a slow electrochemical reaction involving many steps. These
steps involve electron transfer reactions. A particular type of oxidation involve overall first
order kinetics with respect to fraction of unoxidised metal (1– f ) surface thickness relative to
maximum thickness (T) of oxidised surface, when metal surface is exposed to air for
considerable period of time
0 200 hrs
t

–3

ln(1– f)

Rate law : = k(1 – f ), where f = x/T, x = thickness of oxide film at time 't' & T = thickness
of oxide film at t = 
A graph of ln(1 – f ) vs t is shown in the adjacent figure.

15. The time taken for thickness to grow 50% of 'T' is

(A) 23.1 hrs (B) 46.2 hrs (C) 100 hrs (D) 92.4 hrs

16. The exponential variation of 'f' with t(hrs) is given by

(A) [1- e–3t / 200 ] (B) e-3t / 200 –1 (C) e–3t / 200 (D) e3t/200

Paragraph for Question Nos. 17 & 18

k1 2B
k1 1
For a hypothetical elementary reaction A where =
k2 k2 2
2C
Initially only 2 moles of A are present.
17. The total number of moles of A, B & C at the end of 50% reaction are
(A) 2 (B) 3 (C) 4 (D) 5

18. Number of moles of B are

(A) 2 (B) 1 (C) 0.666 (D) 0.333

Paragraph for Question Nos. 19 & 20

A reaction is said to be first order if it's rate is proportional to the concentration of reactant. Let
us consider a reaction
A(g)   B(g) + C(g)
At t = 0 a 0 0
At time t a–x x x
 dx
= k(a – x) and integrated rate equation for a
The rate of reaction is given by the expression
dt
1  a 
given reaction is represented as k = ln   where a = initial concentration and (a – x) =
t ax 
concentration of A after time t.

19. Thermal decomposition of compound X is a first order reaction. If 75% of X is decomposed in

100 min. How long will it take for 90% of the compound to decompose? Given : log 2 = 0.30
(A) 190 min (B) 176.66 min (C) 166.66 min (D) 156.66 min

20. Consider a reaction A(g) 3B(g) + 2C(g) with rate constant 1.386 × 10–2 min–1. Starting
with 2 moles of A in 12.5 litre vessel initially, if reaction is allowed to takes place at constant
pressure & at 298K then find the concentration of B after 100 min.
(A) 0.04 M (B) 0.36 M (C) 0.09 M (D) None of these

Paragraph for Question Nos. 21 & 22

For the given sequential reaction
A k1  B  k2  C
the concentration of A, B & C at any time 't' is given by
k  A0
[A] = [A]0e–k1t [B]t = 1 ek1t  ek2 t  [C]t = [A0] – ( [A]t + [B]t )
k  k  2 1

21. The time at which concentration of B is maximum is

k1 1 k 1 k k2
(A) (B) ln 1 (C) ln 1 (D)
k 2  k1 k 2  k1 k 2 k1  k 2 k 2 k 2  k1

22. Select the correct option if k1 = 1000 s–1 and k2 = 20 s–1.

[C]t [C]t
conc.
Conc.

(A) (B)
[B]t
[B]t [A]t
[A]t
Time time

[C]t
[C]t
conc.
conc.

(C) [B]t
(D) [B]t

[A]t
[A]t
time time
 Paragraph for Question Nos. 23 to 26
Competing First-Order Reactions
Frequently a species can react in different ways to give a variety of products. For example,
toluene can be nitrated at the ortho, meta, or para positions, We shall consider the simplest
case, that of two competing irreversible first-order reactions :
A  k1
 C and A  k2
D
where the stoichiometric coefficients are taken as unity for simplicity. The rate law is
 d[A] 
 dt  = – k1[A] – k2[A] = – (k1 + k2) [A]   [A] = [A]0. e(k1k2 )t
 
 d[C] 
For C, we have   = k1[A] = k1[A]0 e(k1k2 )t . Multiplication by dt and integration from
 dt 
time 0
k1[A]0
(where [C]0 = 0) to an arbitary time t gives [C] = (1  e(k1k2 )t )
k1  k 2
 d[D]  k 2[A]0
Similarly, integration of gives   [D] = (1 – e(k1k2 )t )
 dt  k1  k 2
The sum of the rate constants k1 + k2 appears in the exponentials for both [C] and [D].
[C] k
At any time we also have = 1
[D] k 2

23. A starting initially with only A Which of the following is correct at time t

(A) [A]0 = [A]t +[B]t + [C]t (B) [A]0 = [A]t + 2 [B]t + 3 [C]t
[B]t [C]t 2
(C) [A]0 = [A]t + + (D) [A]0 = [A]t + [B]t + [C]t
2 3 3

[X]t
24. X starting with only 'X', ratio
[Y]t  [Z]t
(A) Independent of time
1
(B) kt
(e  1)
(C) Depends upon initial concentration of X
(D) [A]0 (ekt –1)

25. At high temperature acetic acid decomposes into CO2 & CH4 and simultaneously into CH2CO
(ketene) and H2O
1 1
k1 3s k 2 4s
(i) CH3COOH   CH4 + CO2 (ii) CH3COOH  CH2CO + H2O
What is the fraction of acetic acid reacting as per reaction (i) ?
3 3 4
(A) (B) (C) (D) none of these
4 7 7
26. For A starting with pure A ratio of rate of production of B to C is :
(A) Independent of time
(B) Independent of temperature
(C) Depends upon initial concentration of A
(D) Independent of mechanism of reaction

MATCH THE COLUMN

27. For the reaction of type A(g)  2B(g)
Column–I contains four entries and column–II contains four entries. Entry of column-I are to
be matched with ONLY ONE ENTRY of column-II
Column I Column II
d  B d  A
(A) vs for first order (P)
dt dt

(B) [A] vs t for first order (Q)

(C) [B] vs t for first order (R)

(D) [A] vs t for zero order (S)

28. Match the column :

Column-I Column-II
(A) Inversion of cane sugar in excess water. (P) Not 100% complete
(B) Saponification reaction with 1M NaOH (Q) Psuedo-first order
(C) Decomposition of HI on gold (R) Zero order
(D) Radioactive decay (S) Conc. of reactant varies exponentially

29. Match the Column :

Column-I Column-II
(Type of PLOT for reaction A products)
(A) Rate (y-axis) Vs [A]t (x-axis) for second order (P) Non-linear
reaction
(B) Half-life (y-axis) Vs initial concentration of A(x-axis) (Q) Positive slope
for second order reaction
1
(C) Rate (y-axis) Vs (x-axis) for zero order reaction (R) Zero slope
 A t
(D) Log (Rate) (y-axis) Vs time (x-axis) for first order (S) Linear
reaction
 EXERCISE # JEE MAINS
1. For the reaction 2A + B  C, the values of initial rate at different reactant concentrations are
given in the table below. The rate law for the reaction is : [JEE MAIN -2019(APR.)]
[A] (mol L–1) [B] (mol–1) Initial Rate (mol L–1s–1)
0.05 0.05 0.045
0.10 0.05 0.090
0.20 0.10 0.72
(1) Rate = k[A][B] (2) Rate = k[A]2[B]2 (3) Rate = k[A]2[B] (4) Rate = k[A][B]2

k1 k2
2. For a reaction scheme A   B  C, [JEE MAIN -2019(APR.)]
If the rate of formation of B is set to be zero then the concentration of B is given by:
k 
(1) k1k2 [A] (2)  1  [A] (3) (k1 – k2) [A] (4) (k1 + k2) [A]
 k2 

3. The given plots represent the variation of the concentration of a reactant R with time for two
different reactions (i) and (ii). The respective orders of the reactions are :
[JEE MAIN -2019(APR.)]

(1) 0, 1 (2) 1, 1 (3) 0, 2 (4) 1, 0

4. Consider the given plot of enthalpy of the following reaction between A and B.
A + B C + D [JEE MAIN -2019(APR)]
Identify the incorrect statement.

(1) Formation of A and B from C has highest enthalpy of activation.

(2) Activation enthalpy to form C is 5kJ mol–1 less than that to form D.
(3) D is kinetically stable product.
(4) C is the thermodynamically stable product.
5. A bacterial infection in an internal wound grows as N’(t) = N0 exp(l), where the time t is in
hours. A dose of antibiotic, taken orally, needs 1 hour to reach the wound. Once it reaches
dN
there, the bacterial population goes down as = – 5N2. [JEE MAIN -2019(APR.)]
dt
N0
What will be the plot of vs. t after 1 hour?
N

(1) (2)

(3) (4)

6. For the reaction of H2 with I2, the rate constant is 2.5×10–4 dm3 mol–1 s–1 at 327ºC and 1.0 dm3
mol–1 s–1 at 527ºC. The activation energy for the reaction, in kJ mol–1 is :
(R = 8.314 J K–1 mol–1) [JEE MAIN -2019(APR.)]
(1) 150 (2) 59 (3) 166 (4) 72

7. In the following reaction; xA  yB [JEE MAIN -2019(APR.)]

 d[A]   d[B] 
log10    log10   0.3010
 dt   dt 
‘A’ and ‘B’ respectively can be:
(1) C2H4 and C4H8 (2) C2H2 and C6H6
(3) N2O4 and NO2 (4) n-Butane and Iso-butane

8. NO2 required for a reaction is produced by the decomposition of N2O5 in CCl4 as per the
equation, 2 N2O5(g)  4 NO2(g) + O2(g)
The initial concentration of N2O5 is 3.00 mol L–1 and it is 2.75 mol L–1 after 30 minutes. The
rate of formation of NO2 is: [JEE MAIN -2019(APR.)]
–2 –1 –1
(1) 1.667 × 10 mol L min (2) 2.083 × 10 mol L–1 min–1
–3

(3) 4.167 × 10–3 mol L–1 min–1 (4) 8.333 × 10–3 mol L–1 min–1
9. The following results were obtained during kinetic studies of the reaction :
2A + B  Products [JEE MAIN -2019(JAN.)]
Experiment [A] (in mol L–1) [B] (in mol L–1) Initial Rate of reaction (in mol L–1 min–1)
(I) 0.10 0.20 6.93×10-3
(II) 0.10 0.25 6.93×10-3
(III) 0.20 0.30 1.386×10-2
The time (in minutes) required to consume half of A is :
(1) 10 (2) 5 (3) 100 (4) 1

10. For the reaction, 2A + B  products, when the concentrations of A and B both were doubled,
the rate of the reaction increased from 0.3 mol L–1 s–1 to 2.4 mol L–1 s–1. When the
concentration of A alone is doubled, the rate increased from 0.3 mol L–1 s–1 to 0.6 mol L–1 s–1.
[JEE MAIN -2019(JAN.)]
(1) Total order of the reaction is 4
(2) Order the reaction with respect to B is 1
(3) Order of the reaction with respect to B is 2
(4) Order of the reaction with respect to A is 2

11. Consider the given plots for a reaction obeying Arrhenius equation (0ºC < T < 300ºC) : (k and
Ea are rate constant and activation energy, respectively) [JEE MAIN -2019(JAN.)]

Choose the correct option :

(1) I is right but II is wrong (2) Both I and II are wrong
(3) I is wrong but II is right (4) Both I and II are correct


k1
 d[A]
12. For an elementary chemical reaction, A2 
k –1
 2A , the expression for is:
dt
[JEE MAIN -2019(JAN.)]
2 2
(1) 2k1[A2]–2k–1[A] (2) k1[A2]–k–1[A] (3) 2k1[A2]–k–1[A] (4) k1[A2]+k–1[A]2
2

1
13. If a reaction follows the Arrhenius equation, the plot lnk vs gives straight line with a
(RT)
gradient (–y) unit. The energy required to activate the reactant is : [JEE MAIN -2019(JAN.)]
y
(1) unit (2) yR unit (3) y unit (4) –y unit
R
14. The reaction 2X  B is a zeroth order reaction. If the initial concentration of X is 0.2 M, the
half life is 6 h. When the initial concentration of X is 0.5 M, the time required to reach its final
concentration of 0.2 M will be :- [JEE MAIN -2019(JAN.)]
(1) 18.0 h (2) 9.0 h (3) 7.2 h (4) 12.0 h

15. Decomposition of X exhibits a rate constant of 0.05 g/year. How many years are required for
the decomposition of 5 g of X into 2.5 g ? [JEE MAIN -2019(JAN.)]
(1) 25 (2) 40 (3) 50 (4) 20

16. For a reaction consider the plot of ln k versus 1/T given in the figure. If the rate constant of this
reaction at 400 K is 10–5 s–1, then the rate constant at 500 K is : [JEE MAIN -2019(JAN.)]

(1) 10–6 s–1 (2) 4×10–4 s–1 (3) 2×10–4 s–1 (4) 10–4 s–1

17. N2O5 decomposes to NO2 and O2 and follows first order kinetics. After 50 minutes, the
pressure inside the vessel increases from 50 mmHg to 87.5 mmHg. The pressure of the gaseous
mixture after 100 minutes at constant temperature will be: [JEE MAIN 2018 (Online)]
(1) 116.25 mmHg (2) 175.0 mmHg (3) 106.25 mmHg (4) 136.25 mmHg

1th
18. For a first order reaction, A  P, t½ (half-life) is 10 days. The time required for conversion
4
of A (in days) is : (ln 2 = 0.693, ln 3 = 1.1) [JEE MAIN 2018 (Online)]
(1) 5 (2) 4.1 (3) 3.2 (4) 2.5

19. If 50% of a reaction occurs in 100 second and 75% of the reaction occurs in 200 second, the
order of this reaction is: [JEE MAIN 2018 (Online)]
(1) 1 (2) 2 (3) Zero (4) 3
20. At 518º 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 : [JEE-MAIN-(Offline)2018]
(1) 0 (2) 2 (3) 3 (4) 1

21. Two reactions R1 and R2 have identical pre-exponential factors. Activation energy of R1
exceeds that of R2 by 10 kJ mol–1. If k1 and k1 are rate constants for reactions R1 and R2
respectively at 300 K, then ln(k2/k1) is equal to : (R = 8.314 J mol–1)
[JEE-MAIN-(Offline)2017]
(1) 6 (2) 4 (3) 8 (4) 12
22. 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: [JEE MAIN 2017 (Online)]
(1) 2.45 K (2) 4.92 K (3) 9.84 K (4) 19.67 K

23. The rate of a reaction quadruples when the temperature changes from 300 to 310 K. The
activation energy of this reaction is: [JEE MAIN 2017 (Online)]
(Assume Ea and A are independent of temperature In 2 = 0.693; R = 8.314 J mol–1 K–1)
(1) 107.2 kJ mol–1 (2) 53.6 kJ mol–1 (3) 214.4 kJ mol–1 (4) 26.8 kJ mol–1

24. 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 :– [JEE-MAIN-(Offline)2016]
(1) 1.34 × 10–2 mol min–1 (2) 6.93 × 10–2 mol min–1
(3) 6.93 × 10–4 mol min–1 (4) 2.66 L min–1 at STP

25. The reaction of ozone with oxygen atoms in the presence of chlorine atoms can occur by a two
step process shown below : [JEE-MAIN-(Online)2016]
O3(g) + Cl(g)  O2(g) + ClO(g) ......(i)
ki = 5.2 × 109 L mol–1s–1
ClO(g) + O×(g)  O2(g) + Cl(g)
kii = 2.6 × 1010 L mol–1s–1 ....(ii)
The closest rate constant for the overall reaction O3(g) + O(g)  2O2(g) is :
(1) 3.1 × 1010 L mol–1s–1 (2) 2.6 × 1010 L mol–1s–1
(3) 5.2 × 109 L mol–1s–1 (4) 1.4 × 1020 L mol–1s–1

26. the rate law for the reaction below is given by the expression k[A] [B]
A + B  Product
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 : [JEE-MAIN-(Online)2016]
(1) 3k (2) 9k (3) k (4) k/3

27. Higher order (>3) reactions are rare due to :- [JEE-MAIN-(Offline)2015]

(1) shifting of equilibrium towards reactants due to elastic collision
(2) loss of active species on collision
(3) low probability of simultaneous collision of all the reacting species
(4) increase in entropy and activation energy as more molecules are involved.
28. The reaction
2N2O5(g)  4NO2(g) + O2(g)
follows first order kinetics. The pressure of a vessel containing only N2O5 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) [JEE-MAIN-(Online)2015]
(1) 106.25 nm Hg (2) 116.25 nm Hg (3) 125 mm Hg (4) 150 mm Hg

29. 
For the equilibrium, A(g)  B(g), H is –40 kJ/mol. If the ratio of the activation energies
2
of the forward (Ef) and reverse (Eb) reactions is then : – [JEE-MAIN-(Online)2015]
3
(1) Ef = 60 kJ/mol; Eb = 100 kJ/mol (2) Ef = 30 kJ/mol; Eb = 70 kJ/mol
(3) Ef = 80 kJ/mol; Eb = 120 kJ/mol (4) Ef = 70kJ/mol; Eb = 30 kJ/mol

30. For the non-stoichiometre reaction 2A + B  C + D, the following kinetic data were obtained
in three separate experiments, all at 298 K. [JEE-MAIN 2014]

Initial Initial Initial rate of

concentration concentration formation of C
(A) (B) (mol L– S–)

0.1M 0.1M 1.2×10–3

0.1M 0.2M 1.2×10–3

0.2M 0.1M 2.4×10–3

dc dc dc dc
(1) = k[A] [B]2 (2) = k[A] (3) = k [A] [B] (4) = k[A]2 [B]
dt dt dt dt
31. The rate of a reaction doubles when its temperature changes from 300 K to 310 K. Activation
energy of such a reaction will be : (R = 8.314 JK–1 mol–1 and log 2 = 0.301)
[JEE MAIN-2013]
(1) 53.6 kJ mol–1 (2) 48.6 kJ mol–1
(3) 58.5 kJ mol–1 (4) 60.5 kJ mol–1

32. For a first order reaction (A)  prodicts the concentration of A changes from 0.1 M to 0.025 M
in 40 minutes.
The rate of reaction when the concentration of A is 0.01 M is : [JEE MAIN-2012]
–5 –4
(1) 1.73 × 10 M/min (2) 3.47 × 10 M/min
–5
(3) 3.47 × 10 M/min (4) 1.73 × 10–4 M/min
33. The rate of a chemical reaction doubles for every 10°C rise of temperature. If the temperature is
raised by 50°C, the rate of the reaction increases by about :- [AIEEE-2011]
(1) 32 times (2) 64 times (3) 10 times (4) 24 times

34. A reactant (A) forms two products : [AIEEE-2011]

k1
A   B, Activation Energy Ea1
k1
A   C, Activation Energy Ea2
If Ea2 = 2 Ea1, then k1 and k2 are related as :-
(1) k1  2k2eEa2 /RT (2) k1  k2eEa1 /RT (3) k2  k1eEa2 /RT (4) k1  Ak2eEa1 /RT

35. Consider the reaction:

Cl2(aq) + H2S(aq)  S(s) + 2H+(aq) + 2Cl–(aq)
The rate equation for this reaction is
rate = k[Cl2][H2S]
Which of these mechanisms is/are consistent with this rate equation ? [AIEEE-2010]
– –
A. Cl2 + H2S  H + Cl + Cl + HS (slow)
+ +

Cl+ + HS–  H+ + Cl– + S(fast)

B. H2S  H+ + HS– (fast equilibrium)
Cl2 + HS–  2Cl– + H+ + S(slow)
(1) A only (2) B only (3) Both A and B (4) Neither A nor B

36. The time for half life period of a certain reaction A Products is 1 hour, when the initial
concentration fo the reactant 'A' is 2.0 mol L–1, How much time does it take for its
concentration to come from 0.50 to 0.25 mol L–1 if it is a zero order reaction ? [AIEEE-2010]
(1) 1 h (2) 4 h (3) 0.5 h (4) 0.25 h

37. The half life period of a first order chemical reaction is 6.93 minutes. The time required for the
completion of 99% of the chemical reaction will be (log 2 = 0.301) :– [AIEEE-2009]
(1) 46.06 minutes (2) 460.6 minutes
(3) 230.3 minutes (4) 23.03 minutes

1
38. For a reaction A  2B, rate of disappearance of ‘A’ is related to the rate of appearance of
2
‘B’ by the expression. [JEE MAIN-2008]
d[A] 1 d[B] d[A] 1 d[B]
(1) –  (2) – 
dt 2 dt dt 4 dt
d[A] d[B] d[A] d[B]
(3) –  (4) – 4
dt dt dt dt
39.  2AB are 180 kJ
The energies of activation for forward and reverse reactions for A2 + B2 
mol–1 and 200 kJ mol–1 respectively. The presence of a catalyst lowers the activation energy of
both (forward and reverse) reactions by 100 kJ mol–1. The enthalpy change of the reaction
(A2 + B2  2AB) in the presence of catalyst will be (in kJ mol–1) – [AIEEE-2007]
(1) 300 (2) 120 (3) 280 (4) –20

40. A radioactive element gets spilled over the floor of a room. Its half-life period is 30 days. If the
initial velocity is ten times the permissible value, after how many days will it be safe to enter
the room ? [JEE MAIN-2007]
(1) 100 days (2) 1000 days (3) 300 days (4) 10 days

41. Which of the following nuclear reactions will generate an isotope ? [JEE MAIN-2007]
(1)  - particle emission (2) Neutron particle emission
(3) Positron emission (4)  - Particle emission

42. The following mechanism has been proposed for the reaction of NO with Br2 to form NOBr

NO(g) + Br2(g)  NOBr2 (g) [AIEEE 2006]
NOBr2(g) + NO(g)  2NOBr(g)
If the second step is the rate determining step, the order of the reaction with respect to NO(g) is :
(1) 0 (2) 1 (3) 2 (4) 3

43. A reaction was found to be second order with respect to the concentration of carbon monoxide.
If the concentration of carbon monoxide is doubled, with everything else kept the same, the rate
of reaction will - [AIEEE-2006]
(1) triple (2) increase by a factor of 4
(3) double (4) remain unchanged

44. Consider an endothermic reaction X  Y with the activation energies Eb and Ef for the
backward and forward reactions, respectively. In general [AIEEE-2005]
(1) Eb > Ef
(2) Eb < Ef
(3) there is no definite relation between Eb and Ef
(4) Eb = Ef

45. A reaction involving two different reactant can never be - [AIEEE-2005]

(1) first order reaction (2) unimolecular reaction
(3) biomolecular reaction (4) second order reaction

46. t1/4 can be taken as the time taken for the concentration of a reactant to drop to 3/4 of its initial
value. If the rate constant for a first order reaction is k, then t1/4 can be written as–
[AIEEE-2005]
(1) 0.29/k (2) 0.10/k (3) 0.75/k (4) 0.69/k
47. Rate of reaction can be expressed by Arhenius equation as k = Ae–E/RT. In this equation, E
represents [AIEEE-2005]
(1) the energy below which colliding molecules will not react
(2) the total energy of the reacting molecule at a temperature, T
(3) The fraction of molecules with energy greater than the activation energy of the reaction
(4) None of these

48. The rate equation for the reaction 2A+B  C is found to be : rate= k[A][B]. The correct
statement in relation to this reaction is that the [AIEEE–2004]
(1) rate of formation of C is twice the rate of disappearance of A.
(2) Half life is a constant
(3) unit of k must be s–1
(4) value of k is independent of the initial concentrations of A and B

49. In a first order reaction, the concentration of the reactant, decreases from 0.8 M to 0.4 M in 15
minutes. The time taken for the concentration to change from 0.1 M 0.025 M is
[JEE MAIN-2004]
(1) 7.5 minutes (2) 15 minutes (3) 30 minutes (4) 60 minutes

50. The half-life of a radioisotope is four hours. If the initial mass of the isotope was 200 g, the
mass remaining after 24 hours undecayed is [JEE MAIN-2004]
(1) 3.125 g (2) 2.084 g (3) 1.042 g (4) 4.167 g

51. In respect of the equation k = Ae–Ea/RT in chemical kinetics, which one of the following
statement is correct ? [AIEEE-2003]
(1) Ea is energy of activation (2) R is Rydberg's constant
(3) k is equilibrium constant (4) A is adsorption factor

52. For the reaction system: 2NO(g)+O2(g)2NO2(g) volume is suddenly reduced to half its value
by increasing the pressure on it. If the reaction is of first order with respect to O2 and second
order with respect to NO, the rate of reaction will – [AIEEE-2003]
(1) Increase to eight times of its initial value
(2) Increase to four times of its initial value
(3) Diminish to one-fourth of its initial value
(4) Diminish to one-eight of its initial value

53. The rate law for a reaction between substances A and B is given by Rate = k [A]n [B]m. On
doubling the concentration of A and halving the concentration of B, the ratio of the new rate to
the earlier rate of the reaction will be as : [AIEEE-2003]
1
(1) (n – m) (2) 2(n – m) (3)  m  n  (4) (m + n)
2
54. 
For the reaction H2 + I2  2HI the true relationship is – [AIEEE-2002]
d  H  d  I  d HI  d  H2  d  I  1 d HI 
(1) –  2  =  2  =   (2) = –  2 =
dt dt dt dt dt 2 dt
2d  H2  2d  I  d HI  2d  H2  2d I2  1 d HI 
(3) – = –  2 =   (4) = =
dt dt dt dt dt 2 dt

55. A chemical reaction 2A + 2B + C –– product follows the rate equation : r  [A] [B]2 then
order of reaction is - [AIEEE-2002]
(1) 0 (2) 1 (3) 2 (4) 3

56. The rate constant of first & second order reaction is respectively - [AIEEE-2002]
(1) time–1, mole–1 . litre . time–1 (2) mole–1 litre–1, time–1
(3) mole–1 . litre . time–1, time–1 (4) sec–1, litre–1

57. In the equation kt = ln C0 – ln Ct, the curve between t and ln Ct is - [AIEEE-2002]

(1) a straight line (2) a parabola (3) a hyperbola (4) none of these

58. Consider following two reactions –

d A
A —— Product —— –   = k1 [A]°
dt
d  B
B —— Product —— –   = k2 [B]
dt
k1 and k2 are expressed in terms of molarity (mol L–1) and time (sec) as - [AIEEE-2002]
(1) sec–1, M sec–1 (2) M sec–1, M sec–1 (3) sec–1, M–1 sec–1 (4) M sec–1, sec–1

59. H2 gas is adsorbed on the metal surface like tungsten. This follows ........ order reaction -
[AIEEE-2002]
(1) Third (2) Second (3) Zero (4) First
 EXERCISE # JEE ADVANCED
1. Consider the kinetic data given in the following table for the reaction A + B + C Product.

The rate of the reaction for [A] =0.15 mol dm–3, [B] = 0.25 mol dm–3 and [C] = 0.15 mol dm–3
is found to be Y × 10–5 mol dm–3s–1. The value of Y is ______ [JEE 2019]

2. The decomposition reaction 2N2O5(g)   2N2O4(g) + O2(g) is started in a closed cylinder
under isothermal isochoric condition at an initial pressure of 1atm. After Y×103 s, the pressure
inside the cylinder is found to be 1.45 atm. If the rate constant of the reaction is 5×10 –4 s–1,
assuming ideal gas behavior, the value of Y is _____ [JEE 2019]

3. For a first order reaction A(g)  2B(g) + C(g) at constant volume and 300 K, the total pressure
at the beginning (t = 0) and at time t are P0 and Pt, respectively. Initially, only A is present with
concentration [A]0, and t1/3 is the time required for the partial pressure of A to reach 1/3rd of its
initial value. The correct option(s) is (are)
(Assume that all these gases behave as ideal gases) [JEE 2018]

(A) (B)

(C) (D)

4. In a bimolecular reaction, the steric factor P was experimentally determined to be 4.5. The
correct option(s) among the following is(are) [JEE 2017]
(A) The activation energy of the reaction is unaffected by the value of the steric factor
(B) Experimentally determined value of frequency factor is higher than that predicted by
Arrhenius equation
(C) Since P = 4.5, the reaction will not proceed unless an effective catalyst is used
(D) The value of frequency factor predicted by Arrhenius equation is higher than that
determined experimentally
5. According to the Arrhenius equation, [JEE 2016]
(A) A high activation energy usually implies a fast reaction
(B) Rate constant increase with increase in temperature. This is due to a greater number of
collisions whose energy exceeds the activation energy
(C) Higher the magnitude of activation energy, stronger is the temperature dependence of the
rate constant
(D) The pre-exponential factor is a measure of the rate at which collisions occur, irrespective of
their energy.

6. The % yield of ammonia as a function of time in the reaction [JEE 2015]

 2NH3(g), H < 0
N2(g) + 3H2(g) 
at (P, T1) is given below -
% yeild

T1

time
If this reaction is conducted at (P, T2), with T2 > T1, the % yield of ammonia as a function of
time is represented by –
T2 T1
% yeild

T1
% yeild

T2
(A) (B)

time time
T1 T2
% yeild

T2
% yeild

T1

(C) (D)

time time

7. In dilute aqueous H2SO4, the complex diaquodioxalatoferrate(II) is oxidized by MnO4 . For

this reaction, the ratio of the rate of change of [H+] to the rate of change of [ MnO4 ] is.
[JEE 2015]

8. For the elementary reaction M  N, the rate of disappearance of M increases by a factor of 8

upon doubling the concentration of M. The order of the reaction with respect to M is
[JEE 2014]
(A) 4 (B) 3 (C) 2 (D) 1
9. In the reaction : [JEE 2013]
P + Q  R + S

[Q]0

[Q]

time
the time taken for 75% reaction of P is twice the time taken for 50% reaction of P. The
concentration of Q varies with reaction time as shown in the figure. The overall order of the
reaction is -
(A) 2 (B) 3 (C) 0 (D) 1

10. 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
[t1/8 ]
the value of × 10 ?
t1/10
(take log102 = 0.3) [JEE 2012]

11. For the first order reaction [JEE 2011]

2N2O5(g) 4NO2(g) + O2(g)
(A) the concentration of the reactant decreases exponentially with time
(B) the half-life of the reaction decreases with increasing temperature.
(C) the half-life of the reaction depends on the initial concentration of the reactant.
(D) the reaction proceeds to 99.6% completion in eight half-life duration.

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

[R] (molar) 1.0 0.75 0.40 0.10

t(min) 0 0.05 0.12 0.18

The order of the reaction is. [JEE 2010]

13. Plots showing the variation of the rate constant (k) with temperature (T) are given below. The
plot that follows Arrhenius equation is – [JEE 2010]

k k
(A) (B)

T T

k k
(C) (D)

T T

14. For a first order reaction AP, the temperature (T) dependent rate constant (k) was found to
1
follow the equation log k = – (2000) + 6.0 . The pre-exponential factor A and the activation
T
Ea , respectively, are [JEE-2009]
6 –1 –1 –1 –1
(A) 1.0 × 10 s and 9.2 kJ mol (B) 6.0 s and 16.6 kJ mol
6 –1 –1
(C) 1.0 × 10 s and 16.6 kJ mol (D) 1.0 × 106 s–1 and 38.3 kJ mol–1

15. Under the same reaction conditions, initial concentration of 1.386 mol dm–3 of a substance
becomes half in 40 seconds and 20 seconds through first order and zero order kinetics,
k 
respectively. Ratio  1  of the rate constants for first order (k1) and zero order (k0) of the
 k0 
reactions is [JEE 2008]
–1 3 –3 –3 –1
(A) 0.5 mol dm (B) 1.0 mol dm (C) 1.5 mol dm (D) 2.0 mol dm3

16. 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 :
[JEE 2007]
(A) 0 (B) 1 (C) 2 (D) 3

17. Which of the following statement is incorrect about order of reaction? [JEE 2005]
(A) Order of reaction is determined experimentally
(B) It is the sum of power of concentration terms in the rate law expression
(C) It does not necessarily depend on stoichiometric coefficients
(D) Order of the reaction can not have fractional value.
18. 2X(g) 3Y(g) + 2Z(g) [JEE 2005]
 Time (in Min) 0 100 200
Partial pressure of X 800 400 200
(in mm of Hg)
Assuming ideal gas condition. Calculate
(a) Order of reaction (b) Rate constant
(c) Time taken for 75% completion of reaction (d) Total pressure when PX = 700 mm.

19. For the given reactions, A + B Products, following data were obtained. [JEE-2004]
[A0] [B0] R0(mol L–1 s–1)
1. 0.1 0.2 0.05
2. 0.2 0.2 0.10
3. 0.1 0.1 0.05
(a) Write the rate law expression
(b) Find the rate constant

20. The reaction, X Product follows first order kinetics. In 40 minutes the concentration of X
changes from 0.1 M to 0.025 M. Then the rate of reaction when concentration of X is 0.01 M
[JEE 2004]
–4 –1 –5 –1
(A) 1.73 × 10 M min (B) 3.47 × 10 M min
–4 –1
(C) 3.47 × 10 M min (D) 1.73 × 10–5 M min–1

21. In a first order reaction the concentration of reactant decreases from 800 mol/dm 3 to 50
mol/dm3 in
4 –1
2 × 10 sec. The rate constant of reaction in sec is [JEE 2003]
4 –5 –4 –4
(A) 2 × 10 (B) 3.45 × 10 (C) 1.386 × 10 (D) 2 × 10

22. Consider the chemical reaction, N2(g) + 3H2(g) 2NH3(g). The rate of this reaction can be
expressed in term of time derivative of concentration of N2(g), H2(g) or NH3 (g). Identify the
correct relationship amongst the rate expressions. [JEE 2002]
(A) Rate = – d[N2]/dt = – 1/3 d[H2]/dt = 1/2d[NH3]/dt
(B) Rate = – d[N2]/dt = – 3 d[H2]/dt = 2d[NH3]/dt
(C) Rate = d[N2]/dt = 1/3 d[H2]/dt =1/2d[NH3]/dt
(D) Rate = – d[N2]/dt = – d[H2]/dt = d[NH3]/dt

23. If I is the intensity of absorbed light and C is the concentration of AB for the photochemical
process
AB + hv AB, the rate of formation of AB is directly proportional to [JEE 2001]
2
(A) C (B) I (C) I (D) Cl
24. The rate of a first order reaction is 0.04 mole litre–1 s–1 at 10 minutes and 0.03 mol litre–1 s–1 at
20 minutes after initiation. Find the half life of the reaction. [JEE 2001]
25. The rate constant for the reaction [JEE 2000]
2N2O5  4NO2 + O2
is 3.0 × 10 sec if the rate is 2.4 × 10–5 mol litre–1 sec–1, then the concentration of N2O5 (in
–5 –1

mol litre–1) is
(A) 1.4 (B) 1.2 (C) 0.004 (D) 0.8

26. 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 kJmol–1.
[JEE 2000]

27. Which of the following statement(s) is (are) correct [JEE 1999]

(A) A plot of log Kp versus 1/T is linear
(B) A plot of log [X] versus time is linear for a first order reaction, X  P
(C) A plot of log P versus 1/T is linear at constant volume.
(D) A plot of P versus 1/V is linear at constant temperature.

28. The rate constant for an isomerisation 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 1 h. [JEE 1999]
 ANSWER KEY
EXERCISE # S-I
1 d  NO 
1. Ans. (i) r = = 9 ×10–4 mol litre–1 sec–1, (ii) 36 × 10–4mol litre–1sec–1, (iii) 54×10–4 mol
4 dt
litre–1sec–1
dx
2. Ans. (i) = k[A][B]2, (ii) rate increases by 8 times
dt
3. Ans. 8.33 × 10–6 Ms–1, 0.012 atm min–1
4. Ans. rate increase by 27 times
5. Ans. (a) 0.019 mol L–1 s–1, (b) 0.037 mol L–1 s–1
6. Ans. 7 × 10–3 Ms–1 7. Ans. 1/6
–3 –1 –3 –1
8. (a) 4.5 × 10 M sec (b) 3.0 × 10 M sec 9. (a) 40.5 gm min–1 (b) 76.5 gm min–1
10. Ans. (i) 7.2 M, (ii) Think 11. Ans. K = 0.01 M min–1
12. Ans. 6 × 10–9 sec 13. Ans. 1.2 hr
10
14. (i) 9.994 M (ii) 6
(iii) 5 × 106 min 15. Ans. (i) 36 min., (ii) 108 min.
2  (2 10 )
16. Ans. (i) 0.0223 min–1, (ii) 62.17 min 17. Ans. t = 10 × t1/2
18. Ans. 40 month 19. Ans. 3.3 × 10–4s–1
20. Ans. 87.5 % 21. (a) 5 x 105 M/s (b) 4.2 x 105 M/s
22. 75 23. Ans. (a) Third order, (b) r = k[NO]2[H2], (c) 8.85 ×10–3 M sec–1.
24. (a) n = 2, (b) First Order 25. Ans. 2
–2 –1
26. Ans. (i) first order (ii) k = 1.308 × 10 min (iii) 73%
27. Ans. (i) Zero order, (ii) K = 5 Pa/s 28. Ans. Zero order
1 P3
29. Ans. k = /n 30. 3.27 × 10–3 min–1
t 2(P3  P2 )
31. 8.44 ×10–4 sec–1 32. Ans. r = K[(CH3)2 O], 0.000428 sec–1
33. Ans. k1 = 2.605 × 10–3 min–1 34. Ans. 0.180 atm, 47.69 sec
1 r
35. Ans. k = /n 36. Ans. 966 min
t  r  rt 
C
Ans.   =
10 11x
37. Ans. 0.1 min–1 38. (e – 1)
 A  11
39. Ans. 86.625 min 40. Ans. t1/2 = 36 min.
41. Ans. 10 M 42. Ans. t = 4 min
–1
43. Ans. 5 kJ mol 44. Ans. 13.44 kcal/mole
–1
45. Ans. 10.757 k cal mol 46. Ans. t = 20.4 minutes
47. 80.65% 48. (A) y + z (B) z (C) x + y + z (D) x (E) x + y
(F) – y
49. – 1000
50. (a) 2 B+F  2E; (b) A; (c) C, D; (d) rate = k [B][C]; (e) rate = k'[A][B] (f) 2.
51. k [N2O5] 52. Ans. r = K' [NO]2[Br2]
53. Ans. r = K [NO]2 [H2], where K = k2 × K1
 EXERCISE # S-II
1. 0050.00 2. 4.83 mins 3. Pt = 379.55 mm Hg, t7/8 = 399.96 min
–1
4. (a) 43.46 kJmol , (b) 20.47 hour 5. 20 min 6. 0.537
4
7. 10–19 minute 8. k = 0.0327 min–1 10. = 1.91
K3
11. Eoverall = E/3(2n+1)
EXERCISE # O-I
1. B 2. D 3. C 4. B 5. B 6. C 7. A
8. A 9. B 10. D 11. A 12. A 13. C 14. B
15. A 16. A 17. C 18. A 19. A 20. D 21. B
22. A 23. A 24. A 25. D 26. C 27. D 28. C
29. D 30. A 31. C 32. A 33. C 34. C 35. B
36. C 37. C 38. C 39. C 40. B 41. C 42. B
43. C 44. D 45. A 46. C 47. B 48. B 49. C
50. B 51. B 52. D 53. D 54. C 55. C 56. D
57. B 58. C 59. B 60. B 61. D 62. A 63. B
64. C 65. A 66. B 67. B 68. D 69. C 70. B
71. C 72. A 73. B 74. C 75. A

EXERCISE # O-II
1. ABC 2. ABD 3. ABC 4. ABD 5. AD 6. AD 7. ABC
8. ACD 9. BCD 10. BC 11. C 12. C 13. C 14. A
15. B 16. A 17. B 18. C 19. C 20. C 21. C
22. C 23. C 24. B 25. B 26. A
27. A- S ; B- R ; C- P; D - Q 28. A  P,Q,S; B P, Q,S; C R; D P
29. A P; B P; C S,R; D S

EXERCISE # JEE-MAINS
1. 4 2. 2 3. 4 4. 2 5. 3 6. 3 7. 1
8. 1 9. 2 10. 3 11. 4 12. 1 13. 3 14. 1
15. 3 16. 4 17. 3 18. 2 19. 1 20. 2 21. 2
22. 2 23. 1 24. 3 25. 3 26. 3 27. 3 28. 1
29. 3 30. 2 31. 1 32. 2 33. 1 34. 2 35. 1
36. 4 37. 4 38. 2 39. 1 40. 1 41. 2 42. 3
43. 2 44. 2 45. 2 46. 1 47. 1 48. 4 49. 3
50. 1 51. 1 52. 1 53. 2 54. 3 55. 4 56. 1
57. 1 58. 4 59. 3
 EXERCISE # JEE ADVANCED
1. 6.75 2. 2.30 3. A,D 4. A,D 5. BCD 6. B 7. 8
8. B 9. D 10. 9 11. ABD 12. Zero 13. A 14. D
–3 –1
15. A 16. D 17. D 18. (a) 1, (b) 6.93 × 10 min , (c) 200, (d) 950 mm
19. (a) R0 = K [A]0 (b) 0.5 sec–1 20. C 21. C 22. A 23. B
24. 24.14 min 25. (D) 26. 100 KJmol–1 27. ABD 28. –3
3.435 × 10 M/min