Chemical Kinetics

ABOUT EDUCATORS

DR. SHARAD KOTHARI

• MSc., PhD, NET, JRF
• 19 year experience of IIT JEE in Organic Chemistry
• Ex. Senior Faculty of Vibrant Academy, Kota and Bansal Classes, Kota

PIYUSH MAHESHWARI
• BE (Hons.)
• 12 year experience of IIT JEE in InorganicChemistry
• Author of 'Super Problems in Inorganic Chemistry',
• Ex. HOD Bansal Classes, Kota
• Ex. Senior Faculty of Vibrant Academy, Kota and Allen Career Institute, Kota

BRIJESH JINDAL
• BTech Jaipur MNIT
• 12 year experience of IIT JEE in Physical Chemistry
• Ex. Senior Faculty of Vibrant Academy, Kota, Allen Career Institute, Kota and Bansal
Classes, Kota
 CHEMICAL KINETICS

EXERCISE-1 (Subjective Questions)

r ts
t s
Rate of disappearance, Rate of appearance , Rate of Reactions
r
Ammonia and oxygen reacts atehigher temperatures as x pe
Q.1
4NH (g)x p r E
y3 seconds. Calculate.
In an experiment, y
r theE
3 + 5O (g)  4NO(g) + 6H O(g)
2 2

i s t
t
–2
concentration of NO increases by 1.08 ×10 mol litre in–1

(i)
i s of ammonia
rate of reaction.
h em
(ii)
ratee
m
rate of disappearance
C
Ch
(iii) of formation of steam

Q.2 For the reaction : N2(g) + 3H2(g)  2NH3(g). If rate of appearance of NH3 is 6.8 × 10–3 gm/min, then
rate of disappearance of H2(g) at the same condition will be :

ts r ts
er pe
Q.3 If the rate of decomposition of N2O5 in the reaction, 2N2O5(g)  4NO2(g) + O2(g) at a particular

x p
instant is 4.2 × 10–7 M/s. Then calculate -
E x
r yE
(a) rate of reaction
tr y
i s t
(b) rate of appearance of NO2 and O2 at that instant.
i s
m the chemical reaction balanced in two different ways. em
Q.4
e
Consider
h 2NO(g) + Cl (g)  2NOCl(g)
C h
C and. NO(g) +
2
1
Cl (g)  NOCl(g)
2 2
If rate of reaction according to first version is 8 × 10–5 mol L–1s–1. Then what is the rate of reaction
according to second version.
r t s t s
e
The reaction, 2NO(g) +xClp(g)  2NOCl(g) is carried out in a closed vessel. If partial pressuree r
Q.5
is decreasing at rateE
y
2 p
x (in torr/s).
of NO

tr r E
of 180 torr/min. What is the rate of change of total pressure of vessel
y gas decreases
At 27°C iit s t
sdisappearance in M sec
Q.6
e m2 atmosphere to 1.1 atmosphere in 75 minutes. Calculate the ratem i
was observed during a reaction of hydrogenation that the pressure of hydrogen

h
from
e of –1

C Rate Law Ch
Q.7 For the elementary reaction :
H2S(aq) + Cl2(aq)  S(s) + 2H+(aq) + 2Cl–(aq)

r ts
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

p e
[Cl2] = 0.025 M. What is rate of formation of Cl– ?

For the elementaryE

x
reaction 2A + B  2AB. Calculate how much the rate of reaction willr ts if
rofy e
Q.8 change
t
2

is of the vessel is doubled of its original volume?

(a) the volume the vessel is reduced to one third of its original volume?
x p
m
(b) the volume
e r y E
h
C partial
The reaction A(g) + 2B(g)  C(g) + D(g) is an elementary process. t
isIn an experiment, the initial
pressure of A & B are P = 0.6 and P = 0.8 atm. Calculatem
Q.9
A B
h e the ratio of rate of reaction relative
to initial rate when P becomes 0.2 atm.
C
C
Page # 1
 CHEMICAL KINETICS

Zero Order
r t s
Q.10 In the following reaction: A  Bt,s
r p eof B after
e10 M of A. x
–2 –1
rate constant is 1.2 × 10 M s . What is concentration
p
x Y. At the end of 50 min, X is 75% reacted. Howtrmuch
10 and 20 min., if we start with
E
y of it will be left
r y E i s
unreacted atsthe
i t
Q.11 A zero order reaction : X
end of 2 hour.
e m
e m C h
Cish10 M min A(g)
Q.12 The initial rate of zero order reaction of a gaseous reaction,
 2B(g),
–3 –1
. If initial concentration of A is 2M. Then what would be rate of reaction after
120 seconds.

ts r ts
Q.13

x
Time (min.)
p er
For the following data for the zero order reaction A  products. Calculate the value of k.
[A]
x pe
E
E try
0.0 0.10 M
r y s
st i
1.0 0.09 M
i 2.0 0.08 M
em
Q.14 hem of reaction : C h
C Decomposition
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 rate of reaction after 10 seconds.

r ts ts
e r
The rate constant for a zero order reaction is 2 × 10–2 mol L–1sec–1, if the concentration of the reactant
xp
Q.15
after 25 sec is 0.25 M, calculate the initial concentration.

y E x pe
st r r y E
A drop of solution (volume 0.10 ml) contains 6 × 10–6 mole of H+, if the rate constant of disappearance
t
Q.16

m i i s
of H+ is 1 × 107 mol L–1 s–1. How long would it take for H+ in drop to disappear?

Q.17 h
e e m
C reacted. Calculate the time when A is 10% unreacted. (Given: h
A certain substance A is mixed with an equimolar quantity of substance B. At the end of an hour A is 75%
C order of reaction is zero)
First Order
Q.18 A first order reaction is 75% completed in 72 min.. How long time will it take for
(i) 50% completion
r ts (ii) 87.5% completion

e
(iii) Fraction of reactant left after 108 min
p
E x r t s
yfor the reactions to go to 75% completion.
Q.19 A first order reaction is 20% complete in 10 min. calculate

t r
(i) the specific rate of reaction ,
p e
is of reactant decompsed after 40 min
(ii) the time
m
taken
y E x
e
(iii) Fraction
h s t r
C ATheis rate constant for an isomerisation reaction A  B is 4.5 × 10 mini . If the initial concentration of
em
–3 –1
Q.20
1 M. Calculate the rate of the reaction after 1 h.
C h
–1 –1 –1 –1
Q.21 The rate of a first order reaction is 0.04 mole L s at 10 minutes and 0.03 mol L s at 20 minutes
after initiation. Find the half life of the reaction.
Page # 2
 CHEMICAL KINETICS
Q.22 In the first order decomposition of A : A  2B + 3C

r ts
Concentration of A decrease from initial concentration 0.8M to 0.2M in 13.86 min. then calculate rate of

t s pe
appearance of B (in M/s) after 13.86 min.

Q.23 For a 1 order reaction : Ap ®e

r 20%xcompleted in
3B + 2C, with initial concentration 2M of A, it is E
x of A = 10M, then find the concentration of Btafter y50 min.
st

y E
50 min. If initial concentration
i s r
t r
is was inactivated in a chemical bath. The inactivation m
Q.24 A viral preparation
order m h e process was found to be first
e
h per minute . Evaluate k (in s ) for inactivation process.C
in virus concentration. At the beginning of the experiment 2.0 % of the virus was found to be

Cinactivated
–1

 100 
Given : ln    0.02
 98 

ts r ts
Q.25

x p er
320°C. What % of SO2Cl2 is decomposed on heating this gas for 90 min.
x pe
The reaction SO2Cl2(g)  SO2(g) + Cl2(g) is a first order gas reaction with k =2.2 × 10–5 s–1 at

E
Given : e–0.1188 = 0.888
y r y E
Q.26 For a first s
r
t reaction : A  Product the concentration of A changesi t
2sM to 0.5 M in 4 min. Then
m i order
e m
e
calculate –1
rate of reaction(M s ) after 6 min.[ln2 = 0.7]
h
ChDecomposition of 1 L H O follows a first order reaction.CIn 46 minutes the concentration of H O
Q.27 2 2
decreases from 0.5 to 0.125 M in one such decomposition. When the concentration of H2O2 reaches
2 2

0.05 M, then calculate of rate of formation of O2 (in mol s–1). (ln 2 = 0.69):

r ts ts
Q.28
e
The half-life for first order decomposition of N2O4 is 1.4 × 10–5 s.
r
E xp N2O4(g)  2NO2(g)
x pe
tr y
If N2O4 is introduced into an evacuated flask at a pressure of 20mm Hg, how many seconds are
y E
i s
required for pressure of NO2 to reach 10 mm Hg?

cyclopropane(C H ) rearranges to propene (CH –CH = CHi).

tr
sThe reaction is first order
e m
Q.29 At 500°C,
m
h
C [Given : ln 5 = 1.6, ln 2 = 0.7]
3 6
–3 –1
h e
3
and the rate constant is 4 × 10 s . If initial concentration of cyclopropane
2
C H is 0.05M.
C
3 6

Then
20
(a) What is molarity of cyclopropane C3H6 after min?
3

r ts
(b) How many minutes does it take for C3H6 concentration to drop to 0.01 M.

x pe
(c) After how many minutes 20% of cyclopropane will be left.

t s
r E
y : N O (g)  2NO (g) + O (g) e r
t reaction 2 5 2
1
itosbe first order. The reaction was carried out at constant temperatureyofE340K
Q.30 The gas phase
2 2 p
x in a constant
h m
e container. The initial pressure is equal to 0.1 bar and no substanceisistrinitially present except for
is found

C N O . The total pressure was 0.16 bar after 100 sec of reaction.eCalculate
volume
m
h
2 5
[Given : ln 10 = 2.3, ln6 = 1.8, ln2 = 0.7]
(a) value of rate constant.
(b) partial pressure of N2O5 after 100 sec of reaction.
C
(c) half life (t1/2)
Page # 3
 CHEMICAL KINETICS

Order of Reaction & Rate law

r ts
Q.31
r ts
Initial rate data at 25°C are listed in the table for reaction.
e x pe
p
NH4+(aq) + NO2–(aq)  N2(g) + 2H2O(l)
E
Experiment
E x Initial Initial
try
Initial rate of consumption
s
i s try [NH4 ] + [NO2 ]–

e m i
of [NH4+] (M/s)

em Ch3.6 ×× 1010
1 0.24 0.1 7.2 –6

Ch 2 0.12 0.1 –6

3 0.12 0.15 5.4 × 10–6

(a) What is the rate law ?
(b) What is the value of rate constant ?
ts r ts
r pe
(c) What is initial rate when initial concentration are [NH4+] = 0.4 M and [NO2–] = 0.5 M ?

p e x
x E
try
Q.32 The following result have been obtained during kinetic studies of the reaction.

ryE A + B  C + D

i st i s
em Experiment [A ] / M [B] / M
hem
Initial rate of formation

Ch
of D / M s 1
I
II
0.1
0.3
0.1
0.2
C
6.0 10 3
7.2  10  2
III 0.3 0.4 2.88  10 1
IV 0.4 0.1 2.40  10  2

r ts ts
e r
xp
(a) Determine the rate law of above reaction
(b) Find the rate constant of above reaction in (mol/L)1–n s–1

y E x pe
r
st Time (min) 0 ryE
t
Q.33 The following data is obtained for the reaction : A(aq) — 2B(aq) + C(aq)
i
m Concentration of ' A' 0.1 i s
e 20 40 60
m
ChThen calculate order of reaction : e
0.09 0.081 0.0729

Ch
Q.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 order of reaction.

r t s
pe
Q.35 For a gaseous reaction : 2A(g)  3B(g) + 4C(g) occurring in a rigid vessel, if initially pressure is 3 atm and

x
after 10 minutes & 20 minutes the pressure is 6.75 atm and 10.5 atm respectively, then what will be the
order of reaction?
E r ts
tr y of decomposition of a gaseous compound initially at a pressure pof e20 kPa was
i
Q.36 At 300 K, s the rate
E x
h e m –1 –1
t
13.5 Pa s when 10% had reacted and 0.5 Pa s when 70% had reacted. Then
r y Calculate order of
C reaction is : i s
h em
C
Page # 4
 CHEMICAL KINETICS

Calculation of Rate Constant using Different Parameters

r ts
s pe
3

e t
Q.37 The reaction AsH3(g) As(s) + H2(g) was followed at constant volume at 310°C by measuring
r 2
x
p E
the gas pressure at intervals Show from the following figures that reaction is of first order.
Time (in hrs)
E x 0 5 7.5
s try
10

i s try
Total pressure (in mm) 758 827 856

emi 882

em Ch
Q.38 The decomposition of H2O2 follows first order kinetics :

Ch HO 2 
1
 H2O(l) + 2 O2(g)
2(aq)

In order to determine the rate constant of 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?
ts r ts
x p er
Time(min)
Volume of KMnO 4
0 10
25 20
20
X
x pe
E
ry in pressure of the
yE of dimethyl ether as measured by finding theisincrease
r
Q.39 The thermaltdecomposition t
reaction is m
e m h e
ChatTime500°C
(CH ) O(g)  CH (g) + H (g) + CO(g)

(s)
3 2
is as follows:
390
4
C 3155
1195
2


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

r
the rate constant of reaction.
ts ts
e r
pan experiment to measure the rate of inversion of cane sugar (1 porder)
e
E x
Q.40 The polarimeter readings in
x
st were
as follows.
r y y E
i st Time (min) 0 30
i s t r
e m m
h e
Rotation due to solution 60 40  30

(a) The half life(t1/2) of reaction

Clogh 3 = 0.48, log 7 = 0.84, log 10 = 2.3]
C Which of the following is / are correct : [Given : log 2 = 0.3, e

(b) The time at which solution becomes optically inactive.

Q.41
st
1 order
A    B + C
r ts
Time
xpe P
t 
ts
E
Total pressure of ( B+C)
y
P3
r
pe
2
Find k.

is tr x
m
e  G + F ryE
Q.42 h
C S  
1st order
i s t
Time t 
r h
em
Rotation of Glucose & Fructose
Find k.
rt
C


Page # 5
 CHEMICAL KINETICS
Q.43 The following data were obtained in experiment on inversion of cane sugar.
Time (min) 0 60 120 180 360 
r ts
Angle of rotation (degree)
e r t
+13.1 + 11.6
s + 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
x pe
polarimeter?
x p r y E
r E t
y reaction A  2B + C was observed to be ofmfirstisorder. On starting with pure
t
sthat at the end of 10 minutes the total pressure of system
Q.44 At 100°C the gaseous
i eis 176 mm. Hg and after a long time
m
A it is found
e C h
h
270 mm Hg. From these data find

C(b) the pressure of A at the end of 10 minutes

(a) initial pressure of A

(c) the specific rate of reaction

ts
(d) the half life period of the reaction? [Given : ln
 90 
  0.65 n]
r ts
x p er  47 
x pe
y E r y E
Q.45 The decomposition of N2O5 according to the equation 2 N2O5 (g)  4 NO2(g) + O2(g) is a first

st r i s t
order reaction. After 30 min. from start of decomposition in a closed vessel the total pressure

m i em
developed is found to be 284.5 mm Hg. On complete decomposition, the total pressure is
e h
584.5 mm Hg. Calculate the rate constant of the reaction. [Given : ln 1.169 = 0.156]

ChDecomposition of reaction 3A (g)  2B (g) + 2C (g) follows

Q.46
C 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?

r ts ts
Q.47
e
For a reaction : 2A(g)  3B(g) + C(g) the pressure at different instants is given as shown :
p r
y E x x pe
Time(min)

s tr
0 13.86 

ryE
m i pressure (mm) 50
Total 80 90
i s t
h e e m
C Ch
Calculate value of rate constant in min –1 ? [Given : ln = 2 = 0.693]

Q.48 Acid catalysed 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.
Rate = K [H+] [CH3COOC2H5]

r ts 200 8020 100

e
Time(min)

x p
Volume of NaOH (in ml)
ts
+
y
If [H ] = 0.7 M. Find
r E –1 –1
'K' in M s . [Take : ln2 = 0.7]
e r
t
istimeA(aq)interval.
B (aq) + C (aq) is monitered by measuring optical rotation ofx
p
e m
Q.49 The reaction
r y E reaction mixture

Ch–minutes
at different
40° respectively. Starting with pure A if the value of optical rotation was
i s t
The species A, B and C are optically active with specific rotations 20°, 30° and
found to be 2.5° after 6.93

e
and optical rotation was –5° after infinite time. Find the ratem constant for first order conversion
of A into B and C.
Ch
Page # 6
 CHEMICAL KINETICS

Parallel and Sequential Reaction

r ts
Q.50 For a reaction
e r ts
, calculate value of ratio,
[ x ]t
x
at any given instant t. pe
x p [ y]  [ z ]
r y E
r E
y= x hr ; k : k = 1 : 10. Calculate [C] after one houri t
s the start of the reaction.
Q.51
i s t k –1
e m from

em 1 1 2 [ A]
C h
ChAssuming only A was present in the beginning.

Q.52 How much time would be required for the B to reach maximum concentration for the reaction
k1
A  k2
B  C. Given k1 =
ts
ln 2
min–1, k2 =
ln 2
min–1.
r ts
r pe
4 2
p e x
x E
E try
Q.53 For first order parallel reaction k1 and k2 are 8 and 2 min–1 respectively at
ry s
st
300 K. If the activation energies for the formation of B and C are respectively 20
i i
em
and 28.314 kJ/mol respectively find the temperature at which B and C will

em be obtained in molar ratio of 2 : 1.

h
Ch C
[Given : ln 4 = 1.4 ]

Temperature Dependence of Rate (Activation Energy)

Q.54
ts
Potential energy profile for a reaction is given as :
r ts
e 2HI(g)  H2(g) + I2(g)
r
E xp x pe
ry 240 kJ
yE
i st s tr
Potential energy

em mi
Ch
H2(g) + I2(g)
60 kJ
e
Ch
HI(g)
50 kJ

Reaction progress

(a) Calculate activation energy for forward reaction and backward reaction respectively.

r t
(b) Calculate E of reaction :s
pe
(c) Is reaction endothermic or exothermic?
x
(d) Fraction of molecules having sufficient kinetic energy to cross threshold barrier at 300K.
ts
[Given R = try
E e r
is
25
J / K  mol
]
x p
m
3
E
e fraction of molecules in a gas at 300 K collide with an energy equalistotrorygreater than E when E
Q.55 h
C What
25
em
a a

equals 50 kJ/mol. [Given : R = J / mol-K]

3
C h
Page # 7
 CHEMICAL KINETICS

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

N2O4(g)  2NO2(g)
r ts
r ts
Use the following data to calculate activation energy. [in KCal /mol]
e x pe
p
[Given : ln2 = 0.7, ln 3 = 1.1]
E
E x
Temperature[°C] Initial [N2O4]
s try
Initial rate of decomposition

i s try mi
of N2O4(M/s)
e
em Ch 10
27 0.1 5 × 3

Ch 47 0.15 2 × 104

Q.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 : ln10 = 2.3, ln2 = 0.7]
ts r ts
r pe
Calculate :

p
(a) activation energy in KCal / mol.e (b) rate constant at 1200K.
x
x
Eenergy byin kJ/mol? E
yto 37°C.
ry
Q.58 If rate of reaction increases
t s tr
a factor of 2, when temperature is raised from 27°C
i
What is the
s
increasedi from 127°C to 137°C.
value of activation By what factor does rate of reaction
m
increase if temperature is

e m h e
Ch(a) If temperature coefficient (µ) is same in given temperatureCrange
[Given : ln2 = 0.7, R = 8.314 Joule/mol-K, e = 1.5] 0.4

(b) If temperature coefficient (µ) is function of temperature.

Q.59

r ts
The dependence of rate constant of a reaction on temperature may be given as :

ts
ln Ke r
500

xp pe
–1
[sec ] = 12.5 –
T( K )

r y E
Calculate the activation energy of reaction(in Cal/mol).
E x
i t the activation energy for a certain reaction from 75 Kcaltmol
slowers r y to 15 Kcal mol .
Q.60 A catalyst
e i
mwill be the effect on the rate of reaction at 27°C, other things being s –1 –1

h
What
e m equal.

h acetate by NaOH is 1.75. Calculate

C activation
Q.61
energy for the saponification of ethyl acetate. C
Given that the temperature coefficient for the saponification of ethyl

Q.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 [ln2 = 0.7, ln3=1.1]

r ts
pe
Q.63 The Arrhenius equation for two first order equation
x
A  B and C  D is given by
E r ts
k = 10 e
1
12

t r y k becomes equal to k . The unit of activation energy is kJ/mol pe

81.28( kJ ) / RT
; k = 10 e 2
11 43.10( kJ ) / RT

m is= 2.3 and R = 8.3 J/K/mol

At what temperature 1 2

y E x
h e
Use: ln 10
tr
Q.64 At room temperature 300 K orange juice gets spoilt in about 52 hours.iInsa referigerator at 200 K juice
C can be stored three times as long before it gets spoilt. Estimate em
(b) How long should it take for juice to get spoilt at 400C
hof juice.
(a) the activation energy of the reaction that causes the spoiling
K?
Given : ln 3 = 1.1, e(11/20) = 1.733
Page # 8
 CHEMICAL KINETICS

Q.65
r ts
The rate of reaction : A(g)  2B(g) increases e5 times on increasing the temperature from 27°C to 327°C.

s pe
The activation energy (in Kcal/mol) of reaction is :

e r t
[Assuming activation energy is temperature independent]
x
p E
y in the presence of a
Q.66 A hydrogenation reactionxis carried out at 500 K. If the same reaction is carriedrout
r y Erate, the temperature required is 400 K. Calculateithe
t
s activation energy of the
reaction if i
the t
scatalyst lowers the activation barrier by 20 kJmolh.em
catalyst at the same
–1

h e m C (Note : H = E in this case). Show

Cthat equilibrium constant K = =e at 300 K. If the activation energies E & E are in the ratio 12
Q.67 For the system A(g)  B(g), H for the forward reaction is –3000R
[B] 10
[A] f b
: 17, calculate Ef and Eb at this temperature. Assume that the pre-exponential factor is the same for the
forward and backward reactions.
ts r ts
x p r
e Mechanism of Reaction x pe
y y E
EBr ¾® 2NOBr, is supposed to follow the following mechanism
r
r
s+t Br NOBr
Q.68 The reaction 2NO +
i s t
i
2
(i) NO
(ii)emNOBr + NO 
2

h e
2
m
ChSuggest the rate law expression. C
2  2NOBr slow

Q.69 For the reaction 2H2 + 2NO ¾® N2 + 2H2O, the following mechanism has been suggested:
2NO l N2O2 equilibrium constant K1 (fast)

r t s ts
e
k2
N2O2 + H2 
N O + H  N + p
N2O+ H2O (slow)
k3
x p er
x
H O (fast)
2 2

r y Efor given reaction.

Establish the rate law
2 2

E
st
Q.70 Reactionibetween NO and O to form NO is 2NO + O ¾® 2NO follows tr y mechanism
e m i sthe following

h k1
2

em 2 2 2

C N O + O  2NO (slow) Ch

NO + NO NO
k–1 2 ( in rapid equilibrium)
2
k2
2 2 2 2

Show that the rate of reaction is given by

1  d[ NO 2 ] 
 
2  dt  = K[NO] [O2]
2

r t s
x pe ts
r y E k1
er
i s t
Q.71 For the mechanism A + B C ; k2

x p
e m C D 
k3

r E
y of C.
(a)
hDerive
t
s apparent second-order rate
the rate law using the steady-state approximation to eliminate the concentration
(b)C Assuming that k << k , express the pre-exponential factor A and E forithe
constant in terms of A , A and A and E , E and E for thee
3 2

h msteps.
three
a

C
1 2 3 a1 a2 a3

Page # 9
 CHEMICAL KINETICS

Q.72 The reaction of formation of phosgene from CO and Cl2 is CO + Cl2 ¾® COCl2
r ts
s pe
The proposed mechanism is
(i) Cl2
K1

er t
2Cl (fast equilibrium)
x
K–1

x p r yE
(ii) Cl + CO ECOCl (fast equilibrium)
r y
K2

i s t
i t
s + Cl  COCl + Cl (slow)
K–2

e m
(iii) COCl
h dt ] =K[CO][Cl ]
K3

em 2 2
that the above mechanism leads to the following rateC
d[ COCl

Ch
2 3/2.
Show law 2
1/ 2
 k 
k2
Where K = k3.  1  .
k  2  k 1 
rate = k [A]n [B]m
ts r ts
x p er x pe
E
stryE
i s try
mi em
e h
Ch C

r ts ts
e r
E xp x pe
ry yE
i st i s tr
em m
Ch Ch
e

r ts
xpe ts
yE r
is tr x pe
em ryE
C h i s t
hem
C
Page # 10
 CHEMICAL KINETICS

EXERCISE-2 (Objective Questions)

r ts
s pe
Single correct

r t
e in different ways as follows : x
Q.1
x p
The rate of a reaction is expressed
r yE

1 d[C]

r y E
1 d[ D]

1 d[ A ]

d[ B]
i s t
2 dt
i t
sis:
3 dt 4 dt dt
em
4m
The reaction
(A)e (B) B + 3 C h 4A+ 2 C
C(C)h A + B  C + D
A + B  2C + 3D D 
(D) B + D A + C

Q.2 For the reaction : 2NO2(g)  2NO(g) + O2(g)

ts r ts
at a certain temperature, the initial rate of decomposition of NO2 is 0.0036 Ms–1 . What is initial rate of

r pe
formation of O2(g) in Mmin–1?

p
(A) 0.0018 e
(B) 0.0108 (C) 0.108 (D) 0.0072
x
x E
Q.3
ryE try
The gas phase decomposition of dinitrogen pentoxide is represented by this equation:
st i s
mi 2N2O5(g)  4NO2(g) + O2(g)

em
What is rate of formation of oxygen gas(in mol L–1 s–1) in an experiment where 0.08 mol of N2O5 is
e h
Ch C
consumed in a 4L container every 0.2 seconds?
(A) 0.02 (B) 0.05 (C) 0.1 (D) 0.2

Q.4 A graph of volume of hydrogen released vs time for the reaction between zinc and dil. HCl is given in
figure. On the basis of this mark the correct option for average rate of formation of H2 gas.

r ts V5
ts
e V3  V2
r
xp pe
(A) Average rate upto 40 s is V4
40

r y E V3  V2 V3
E x
i st
(B) Average rate upto 40 s is
40  30
try
e m
V2
i s
m
V1
V3

Ch e
(C) Average rate upto 40 s is

Ch
40
V3  V1
(D) Average rate upto 40 s is O 2030 40 50
40  20

s
Q.5 Consider the graph given in above figure. Which of the following options does not show instantaneous

r t
rate of formation of H2 gas at 40th second?
V5  V2
xpe V4  V2 V3  V2 V3  V1
ts
(A)
yE (B) (C) (D)
r
pe
50  30 50  30 40  30 40  20

is tr x
Q.6
em ryE
The rate of formation O3(g) is 96 × 10–7 gL–1 s–1 for the reaction.: 3O2 (g)  2O3(g)

C h What is rate of disappearance of O2(g) in mol L–1s–1 ?

(A) 96 × 10–7 (B) 1.5 × 10–7 (C) 3 × 10–7 i s t (D) 0.66 × 10–7

hem
C
Page # 11
 CHEMICAL KINETICS

Q.7 The rate law for a reaction between the substances A and B is given by
r ts
er ts
rate = k [A]n [B]m
x pe
p E
On doubling the concentration of A and halving the concentration of B, the ratio of the new rate to the
x try
earlier rate of the reaction will be as
E s
try i
(A) 2 (n–m) (B) 1 / 2 (m+n) (C) (m + n) (D) (n – m)

The rate ofis

h e m
Q.8

h e m
doubled.
the simple reaction 2NO + O  2NO , when the
2
C
2 volume of the reaction vessel is

C(A) Will grow eight times of its initial rate (B) Reduce to one-eight of its initial rate
(C) Will grow four times of its initial rate (D) Reduce to one-fourth of its initial rate

Q.9
ts r ts
The rate of a stoichiometric/elementary reaction between a solid and a gas in a container may be increased

er
by increasing all of the following factors except the________

x p x pe
E
(A) pressure of gas (B) temperature of gas

y E
(C) volume of container
r
(D) surface area of solid
tr y
Q.10 Consideriasfirst i sof A 20 torr and no other
t order reaction at 300 K, started with initial partial pressure
gas. m
e he m
ChAfter 10 sec. total pressureA(g)of gaseousB(g)mixture

 + 2C(g) C
was 40 torr.
Determine rate constant for above reaction with the help of following data :
[Take : ln2 = 0.7]
(A) 0.7 sec–1
r ts
(B) 0.07 sec–1 (C) 0.05 sec–1 (D) 0.14 sec–1
ts
p e e r
A  2BE
x
Q.11 For first order decomposition,
p
x of A
ry + 3C
y E
st20 seconds.
left after inext
Concentration of A decreases from 1 M to 0.7 M in 10 seconds. What would
i tr
be the
s0.343
concentration

e mM m
C h(A) 0.1 (B) 0.147 M (C) 0.21 M
h e (D)

Q.12 In a first order reaction, the concentration of the reactant, C

decreases from 0.8 to 0.4 M in 15 minutes.
The time taken for the concentration to change from 0.1 M to 0.025 M is
(A) 30 minutes (B) 15 minutes (C) 7.5 minutes (D) 60 minutes

Q.13
ts
The rate equation for the reaction 2A + B  C is found to be : rate = k [A] [B]. The correct statement
r
pe
in relation to this reaction is
x
(A) unit of k must be s–1
E r ts
y
(B) t1/2 is a constant
tr pe
is x
(C) rate of formation of C is twice the rate of disappearance of A

e m
(D) value of k is independent of the initial concentrations of A and B.
r E
y3/4 of its value. If the
Q.14 h
C rate constant for a first order reaction is k, the t can be writtenem
t can be taken as the time taken for the concentration of a reactant to
1/4 is t
drop to
as [ln2 = 0.695, ln3 = 1.1]
(C) 0.10 / kh
1/4
(A) 0.69 / k (B) 0.75 / k
C (D) 0.29 / k

Page # 12
 CHEMICAL KINETICS

Which graph represents zero order reaction [A(g)  B(g)] :

s
Q.15

r t
er ts x pe
p
x(B)
d[B] t1/2
r yE t3/4

E t
[B] dt
(A) (C) (D)

try i s
i s t t
em
[A]0

h
[A]0

h e m C
C
Q.16 Consider a first order reaction at 300 K, started with initial partial pressure of A 20 torr and no other
gas. A(g)   B(g) + 2C(g)
After 10 sec. total pressure of gaseous mixture was 40 torr. Determine rate constant for above reaction

s
with the help of following data :[Take : ln2 = 0.7]
t r ts
r pe
(A) 0.7 sec–1 (B) 0.07 sec–1 (C) 0.05 sec–1 (D) 0.14 sec–1
p e x
x E
y E try
Q.17 Consider the following reaction 2A(g)  3B(g) + C(g).

st r i s
Starting with pure A having pressure 2atm initially, the total pressure is exactly doubled in 2hrs. The
i em
possible order of reaction is

h e m
(A) zero (B) first (C) second (D) third
h
C
Q.18 Decomposition of reaction : 2A(g)  2B(g) + C(g)
C
Follows zero order kinetics. Initial rate of decomposition of A is 0.1 atm/sec. If initially A is taken at 2
atm pressure then what will be rate of reaction after 10 seconds.
(A) 0.1 atm/sec
r t s
(B) 0.05 atm/sec (C) zero (D) 0.5 atm/sec
t s
e r
xp of N O : 2N O  4NO +O
Q.19 The rate constant for the dissociation
is 3.0 × 10 sec E x p eof N O
isy
2 5 2 5 2 2

(in mol litre t)r E

–5 –1 –5 –1 –1
. if the rate is 2.4 × 10 mol litre sec , then the concentration

(A) 1.4 is
–1

tr y 2 5

e m (B) 1.2 (C) 0.004

i s
(D) 0.8

Q.20 h
h em
C of A is taken then what will be concentration of C after 5 minutes.
For a reaction : 2A  B + 3C , rate constant of disappearance
(g) (g) (g) of A is 10 M s . If initially 2M
C (D) 1.5 × 10 M
–3 –1

–2
(A) 0.3 M (B) 0.9 M (C) 0.45 M

Q.21 The initial rate of zero order reaction of the gaseous reaction A(g)  2B(g) is 10–2 M min–1. If the

ts
initial concentration of A is 0.1 M, after 60 s concentration of B would be
r
pe
(A) 0.09 M (B) 0.01 M (C) 0.02 M (D) 0.002 M

E x r ts
r y
Q.22 Consider the following
t
first order competing reactions:
p e
X
m
 is
k
A + B and Y C + D 
2 k

E x the ratio of
of the reaction of X was completed when 96% of the reaction of Y wasycompleted,
1

h e
if 50%
s t r
i (D) 4.65
C (A) 4.06
their rate constants (k /k ) is2
(B) 0.215
1
(C) 1.1
e m
C h
Page # 13
 CHEMICAL KINETICS

Q.23 Consider the reaction A  B, graph between half life (t1/2) and initial concentration (a) of the
r ts
ts pe
reactant is

p er x
E
E x t1/2
s try
i s try emi
m Ch
a
e
Ch graph between
d[A ]
Hence  and time will be
dt

(A) 
d[A ]

ts (B) 
d[A ]
r ts
r pe
dt dt
t
p e x
t

E x yE
r y s tr
(C) 
i st
d[A ]
(D) 
m i
d[A ]

e m dt
t
h e dt
t

ChAt certain temperature, the half life period for the thermal decomposition
Q.24
C of a gaseous substance depends
on the initial partial pressure of the substance as follows
P(mmHg) 500 250
t1 2 (in min.)
r ts ts
Find the order of reactionpe
235 940

x p e r
(A) 1
r y E (B) 2 (C) 2.5 (D) 3
E x
i s t A  B + C , the rate constant for the reaction is 3 ×t10ryM min . At what
m of A will the rate of reaction be 2 × 10 M min. mis
Q.25 For a reaction –3 –1 –1
(g) (g) (g)

e
concentration –3

Ch(A) 1 M (B) 0.52 M (C) 0.82 M h

C
e (D) 2
3
M

Q.26 From the following graph between (a – x)–1 and time 't' for a reaction, calculate rate of disappearance at
the start of the reaction.

r ts
pe
–1
(a–x) –1
 = tan (1/2)

x
E 2Lmol r ts
tr y –1

pe
m is yE x
e
t(min)
h is tr
C (C) 0.25 mol L min
(A) 1.25 mol L min –1 –1 (B) 0.5 mol L min –1 –1

(D) 0.125 mol L m

e
–1 –1 min –1 –1

C h
Page # 14
 CHEMICAL KINETICS

s
1
Q.27 For a reaction A ® Product, a graph plotted between
[A]2
vs time is found to be linear with
r t
r ts x
slope = 0.4 and y intercept equal to 4 as shown. The rate of disappearance of A at the initial stages will
e pe
be :
p E
E x1 
s try
try [A] i
tan=0.4

i s 2

em
m Ch
4
e
Ch time(min.)
[A] is in terms of molarity
(B) 4.16 × 10–4 M/s
s
(A) 0.025 M/s
(C) 1.6 M/s
r ts (D) 0.8 M/s
e r t
pbe e x p
E x
Q.28 If decomposition reaction A (g)  B (g) follows first order kinetics then the graph
y E
of rate of formation

tr y
(R) of B against time t will

i s t r
i s m(D)
(A) m
e (B) (C)
h e
Ch C
Q.29 For reaction,
2NO (g) + O2 (g)  2NO2 (g)

r ts ts
e
Rate law is : rate of reaction = K [NO]2 [O2]
r
xp
When [NO] = 0.04 M and [O2] = 0.02 M, the rate of disappearance of NO is 3.2 × 10–5 M/s.
E x pe
ry
Then value of K' in
t yE
i s i s tr
e m– = K' [NO] [O ]
d[O 2 ] 2

m
Ch(A) 0.5 min M e
dt 2

–1 –2

(C) 8.33 × 10–3 min–1 M–2

Ch
–1
(B) 30 min M
(D) 30 min–1 M–1
–2

Q.30 For the first order decomposition of SO2Cl2(g),

ts
SO2Cl2(g)  SO2(g) + Cl2(g)
r
pe
a graph of log (a0 – x) vs t is shown in figure. What is the rate constant (s–1)?

E x Time (min) 
r ts
tr y 2 4 6 8 10
pe
is x
(0,0)
| | | | |

m yE
log (a0 – x)

e r
-1–

C h -2– i s t
-3–
hem
C
(A) 0.2 (B) 4.6 × 10–1 (C) 7.7 × 10–3 (D) 1.15 × 10–2
Page # 15
 CHEMICAL KINETICS

Reaction A + B  C + D follows following rate law : rate = k [A]


1 1

r ts
pe
2 [ B] 2 . Starting with initial conc.

s
Q.31

e r t
of 1 M of A and B each, what is the time taken for concentration of A to become 0.25 M.
x
x p
Given : k = 2.303 × 10–3 s–1.
r y E
(A) 300 s
r E (B) 600 s (C) 900 s
t
(D) 1200 s
y the concentration of reactant decreases fromm800ismol/dm to 50 mol/dm in
Q.32 In a first ordert
israte constant of reaction in s is
reaction
e 3 3

2 × 10m
(A)e
4
s The
(C) 1.3864C
–1
h
C h 2 × 10 4
(B) 3.45 × 10 –5
× 10 –4
(D) 2 × 10 –4

Q.33 Units of rate constant for the first and zero order reactions in terms of molarity, M units are respectively
(A) s–1, M s–1 (B) s–1, M

ts
(C) M s–1 , s–1 (D) M, s–1

r ts
Q.34
p er pe
For a zero order reaction and a Ist order reaction half life are in ratio of 4 : 1. Calculate ratio of time taken
x x
to complete 87.5 % reaction for zero order : first order reaction respectively.

y E r y E
(A) 7 : 3

s r
(B) 3 : 7 (C) 4 : 1
t isomerisation reaction : CH NC  CH CN mis t
(D) 5 : 3

Howm
i
Q35 For first order 3
e 3

e h
do the properties of the reaction in the table below vary as reaction proceeds?

Ch  [CH 3 NC]
Rate of reaction
t
(M.s 1 ) C
Half life(s)
(a ) Re main the same Decreases
( b) Decreases Re main the same
(c )
r ts
Re main the same Re main the same
ts
e r
xp
(d ) Decreases Decreases
(A) (a)
yE
(B) (b) (C) (c) (D) (d)
x pe
Q.36
str ryE
At 1800 K ethane gas decomposes to ethene and hydrogen. Rate constant for the reaction is

mi i s t
10–3 Pa–1 sec–1. If initial pressure of ethane is 3 × 105 Pa, how many sec. would it take for the pressure
e m
Ch e
to reach 5 × 105 Pa?
(A) 1800.2 sec. (B) 3.33 × 10–2 sec. (C) 6.66 ×10–3 sec.
Ch (D) 1000.4 sec.

Q.37 The formation of oxide layer on metals follows first order kinetics and completely stops when the oxide
thickness becomes 10 nm. If one hour after exposure of oxygen to metal surface the thickness is 7.5 nm,
then what would be the thickness 120 minute after the exposure?
(A) 10 nm
r ts
(B) 5.25 nm (C) 8.475 nm (D) 9.375 nm

x p+eO (g)  2CO (g) ts

r E
Q.38 For the reaction : 2CO(g)
y
2 2

er
p
Following data is given :

S.No. i[s
t x
m CO] (mol / L) O (mol / L) Rate(mol / L  min)
e12.. 00..0204
2

ryE
h
C 3. 0.02
0.02 4 10
i s t 5
5

em
0.02 8 10
5
2 10
h
0.04
The overall order of reaction is -
(A) 0 (B) 1
C (C) 2 (D) –1
Page # 16
 CHEMICAL KINETICS
Q.39 For the reaction A + B  C; starting with different initial concentration of A and B, initial rate of
reaction were determined graphically in four experiments.
r ts
er ts x –1
pe
S.No.
p[A]0 /M (Initial conc.) [B]0/M (Initial conc.) rate/(M sec )
E
E x try
–3 –2 –3
1 1.6 × 10 5 × 10 10

try
–3 –2
i s –3

i s
2 3.2 × 10 5 × 10
em 4 × 10

m Ch
–3 –1 –3
3 1.6 × 10 10 2 × 10
e
h law for reaction from above data is
4 3.2 × 10
–3
10
–1
8 × 10
–3

CRate
(A) r = k[A]2 [B]2 (B) r = k[A]2 [B] (C) r = k[A] [B]2 (D) r = k[A] [B]

ts r ts
r pe
Q.40 For an elementary reaction : 2A(g)  B(g) + 2C(g)

p e x
If initial pressure of A(g) is 20 torr and after 20 seconds, total pressure becomes 25 torr. Then after this
x E
y E try
point how long would it take total pressure to increase to 27.5 torr.
(A) 40 s
i st r (B) 60 s (C) 30 s
i s
(D) 50 s

h e m hem
Q.41 For
C
the first order reaction
 
N  NCl Cl + N2(g)
C 8
7
log (V – V)t 65
4
following observation is made : 3

s
2

e t
where Vt(in ml) is volume of N2 collected at time t & V  (in ml)
r ts
time (min.)
is volume of N2 collected after a long time. What is the time taken

xp
(in minute) for 75% reaction ? (log2 = 0.3)
10 20 30 40

per
(A) 2.5
r y E (B) 5.0 (C) 3 (D) 10
E x
st hydrolysis of an organic compound A at 30°C has a timeisfortrhalfychange of 100 min.,
Q.42 The acidicatalysed
e m Ifm
h
when carried out in a buffer solution at pH = 5, and 10 min., when carried out at pH = 4. Both times of
half change are independent of the initial concentration of A.e
C  d[A ] a + b C h the rate constant K is given by

=K[A] [H ] , what are the values of a and b?

dt
(A) a = 1, b = 1 (B) a = 2, b = 1 (C) a = 0, b = 1 (D) a = 1, c = 0

Q.43
r ts
Decomposition of reaction 3A (g)  2 B (g) + 2C(s) follows first order kinetics. Starting with pure

xpe
A (at 6 atm), the pressure developed after 20 minute and after a long time are 5.05 atm and 4.05 atm,
ts
E
respectively. Identify the correct statement.
y r
tr
(A) Time for 75% completion is slightly more than 40 minute.
is x pe
em
(B) Time for 87.5% completion is slightly less than 60 minute.

r y E
C h
(C) Time for 93.75% completion is exactly 80 minute.
(D) Time for 90% completion is more than 80 minute.
i s t
hem
Q.44
C of 'A' was 0.2 M. The order of reaction is:
The reaction : A — Products, occur 0.01% in 20 milliseconds
(aq)
was 0.4M and 80 milliseconds when the initial concentration
(A) 0 (B) 1 (C) 2
when the initial concentration of 'A'

(D) 3
Page # 17
 CHEMICAL KINETICS

Q.45 For a first order reaction : A(g)  B(g) + C(g) + D(g). Occurring at 1 bar pressure and 300K if initial
r ts
er ts
volume of the container containing only A is V0 and after 10 minutes it is V10 then average life of A will
x pe
be(in minutes):
x p yE
E (D) tr
2 V0 V0
s
10

try
10
(A) 0.1 ln 3V  V
s
(B)
2 V0
(C) 0.1 ln V  V
mi V0
i
0 10 0 10

e
ln ln

e m
3V0  V10

C h V0  V10

h
Q.46CFirst order reaction is given : X  Y
where X and Y both are optically active compounds with specific rotation +80°/mole and –10°/mole
respectively. Initial rotation of pure sample of X was 20° and solution becomes inactive after 22 min then

s
rate constant (in min–1) of given reaction is: [Given : ln 2 = 0.7 and ln3 = 1.1]
t r ts
er pe
(A) 0.01 (B) 0.05 (C) 0.1 (D) 0.5

x p E x
E try
Q.47 For the reaction : A(aq)  2B(aq) , the concentration of 'B' at different time is given as:
r y s
st [B] (in M) 0 i
Time (min) 0 10 20 30

The m
i 0.2 0.4 0.6
em(D) 2.0
e h
Ch(A) 0
order of reaction is :
(B) 0.5 (C) 1.0 C
Q.48 The following data is obtained for the reaction : A(aq) — 2B(aq) + C(aq)
Time (min)
r ts 0 20 40 60

ts
The order of reaction is : pe
Concentration of ' A' 0.1 0.09 0.081 0.0729

x p er
(A) 0
r y E (B) 1 (C) 2 (D) 3
E x
i streaction : 2P  Q + 2S tr y
e m(min.) 0 35 
Q.49 A first order (g) (g) (g)
i s
h Time
h e m
C Then rate of reaction will be ____________ when partialC
P (torr) 100 125 150
total
pressure of P is 50 torr.
[Given : ln2 = 0.7]
(A) 1 torr/s (B) 0.5 torr/s (C) 8.33 × 10–3 torr/s (D) 30 torr/s

Q.50
r ts
For elementary reaction : H2(g) + F(g)  HF(g) + H(g) H = – 140 kJ/mol

xpe
Activation energy is 80 kJ/mol. Then correct energy diagram is :
ts
yE r
is tr x pe
e m
80kJ 80kJ

ryE
h s t
Energy

Energy

i
HF(g) + H(g) HF(g) + H(g)
C (A) 140kJ
H2(g) + F(g)
(B)

em
140kJ
H2(g) + F(g)
Reaction progress

C h
Reaction progress

Page # 18
 CHEMICAL KINETICS

r ts
80kJ
er ts 80kJ
x pe
pH2(g) + F(g) H2(g) + F(g)
E
Energy

Energy
E x try
(C) 140kJ (D) 140kJ

try
HF(g) + H(g)
i s HF(g) + H(g)

i s Reaction progress
em Reaction progress

e m a reaction can be expressed by Arrhenius equation as :h

h
Q.51 Rate of
C
C k = Ae
In this equation, E represents
–E/RT

(A) The fraction of molecules with energy greater than the activation energy of the reaction
(B) The energy above which all the colliding molecules will react
ts r ts
r pe
(C) The energy below which colliding molecules will not react

p e
(D) The total energy of the reacting molecules at a temperature, T
x
E x y E
Q.52
r y tr
The rate constant, the activation energy and the Arrhenius parameter (A) of a chemical reaction at 25°C are
s
st i
3.0 × 10–22 s–1, 104.4 kJ mol–1 and 6.0 × 1014s–1 respectively. The value of the rate constant at T   is
i m
e m
(A) 2.0 × 1018 s–1 (B) 6.0 × 1014 s–1
e
(C) infinity
h
(D) 3.6 × 1030 s–1

Q.53 h
C A first order reaction is 50% completed in 20 minutes atC27°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

r ts ts
1
e r
xp pe
Q.54 A graph of lnK vs is given :
T

ryE E x
i st try
s
slope = – 20

em lnK
mi
Ch 1 Ch
e
T
Where
K is rate constant (in s–1)
T is temperature (in K)

r ts
Then fraction of molecules having energy equal to or greater than threshold energy is
(A) e20/T
x pe (B) e20/RT (C) e–20/RT (D) e–20/T
ts
r E r
yrespectively. The presence of catalyst lowers the activation energies ofpbothe (forward
t
Q.55 The energies of activation for forward and reverse reactions for A + B 2AB are 180 kJ mol –1

and 200 kJsmol

xof the reaction
2 2

m i reactions by 100 kJ mol . The magnitude of enthalpy change

–1

y E
(Ae+ B  2AB) in the presence of catalyst will be (in kJ mol ). r
and reverse) –1

h
C (A) 300
2 2
i t
s(D) –20 –1

em
(B) 120 (C) 20

C h
Page # 19
 CHEMICAL KINETICS
Q.56 The following mechanism has been proposed for the reaction of NO with Br2 to form NOBr :
NO(g) + Br2(g) NOBr2(g)
r ts
e r t s
NOBr2(g) + NO(g)  2NOBr(g)
x pe
(A) 2 p
(B) 1 (C) 0
r
(D) 3 E
If the second step is the rate determining step, the order of the reaction with respect to NO(g) is
x y
r E
yof absorbed light and C is the concentration of AB i t
sthe photochemical proces
i t
Q.57 If I is the intensity
e m
s AB*, the rate of formation of AB* is directly proportional
for

(A)e m
AB + hv 
h
C (D) CI
to

h
2
C (B) I (C) I
C
Q.58 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 [ln2 = 0.7, ln3=1.1]
(A) 2.64 kJ/mol (B) 2.64 Kcal/mol
ts
(C) 10.97 Kcal/mol (D) zero
r ts
p
More than one may be correct
x
er x pe
E
Q.59
ryE
Select incorrect statement(s):
st i s try
mi (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.
em
e h
Ch C
(C) Molecularity is defined only for RDS in a complex reaction.
(D) None of the above statement is incorrect.

Q.60 Which of the following is/are correct statement?

(A) Stoichiometry of a reaction tells about the order of the elementary reactions.

r ts
(B) For a zero order reaction, rate and the rate constant are identical.
ts
e r
xp pe
(C) A zero order reaction is controlled by factors other than concentration of reactants.

r y E
(D) A zero order reaction is always elementary reaction.
E x
Q.61 Which of thetfollowing statement is incorrect?
i s of reaction is the sum of powers of all the concentration terms t r y rate equation.
e
(A) The order
is of logarithm of the rate
morder of reaction with respect to one reactant is the ratio of themchangein the

Chofconcentrations ethe particular reactant, keeping the

(B) The

C h
the reaction to the change in the logarithm of the concentration
of all other reactants constant.
of

(C) Orders of reactions can not be fractional.

(D) The order of a reaction can only be determined from the stoichiometric equation of the reaction.

Q.62 For the reaction :

r ts
xpe
2C2F4  C4F8

ts
yE r
is tr  = tan–14
x pe
E
1

m y
2

e r
[C2F4]

h
C Then
time(sec)
i s t
h em
(B) HalfC
3
(A) Order of reaction is 3. life is min if initially 1M C F is taken
2 4
4
(C) Reaction must be complex (D) Disapperance constant w.r.t. C2F4 is 4 min–1.
Page # 20
 CHEMICAL KINETICS
Q.63 For the gaseous reaction : A(g) Products, the rate may be expressed as

r ts
ts pe
1 dn A dPA
Method I :  ·
V dt
p e r
 k1·C nA Method II : 
dt
 k 2 ·PAn
x
nA E
xconcentration of A and P is the partial pressure oftrA yat time 't' and 'n' is the
Where C = A

r V E
y reaction is occurring at constant temperature, Tm
= molar A

i sK. Assume ideal behaviour

i t
sthe correct statement(s)
order of reaction. The = 300

km
of gas. Select
(A)e (B) k = kC
he
C(C)h k = k · (RT), when n = 0
= k for any value of 'n'
1 2
, when n =1
1 2

1 2
(D) k = k · (RT), when n = 2
1 2

Assertion & Reasoning type questions

Q.64 Statement-1 :
ts
A fractional order reaction must be a complex reaction.
r ts
Statement-2 :

x p er
Fractional order of RDS equals to overall order of a complex reaction.
x pe
yE r E
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
y
str i s t
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.

m i
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.
e m
e h
ChStatement-1 : The time of completion of reactionsCof type A  product (order <1) may be
Q.65
determined.
Statement-2 : Reactions with order  1 are either too slow or too fast and hence the time of

r ts
completion can not be determined.
ts
e r
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.

xp pe
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
E x
try
(C) Statement-1 is true, statement-2 is false.
y E
i s
(D) Statement-1 is false, statement-2 is true.

i t r
s with the increase in
e m : temperature.
Q.66 Statement-1
m
The overall rate of a reversible reaction may decrease
h
C Statement-2 : When the activation energy of forward e
hreaction is less than that of backward
C
reaction, then the increase in the rate of backward reaction is more than that of
forward reaction on increasing the temperature.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.

r t s
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.

x pe
(C) Statement-1 is true, statement-2 is false.

ts
E
(D) Statement-1 is false, statement-2 is true.

Q.67 Statement-1tr:y e r
i s x
In a reversible endothermic reaction, E of forward reaction is higherp than that
Eof backward reaction
act

h e m of backward reaction
The threshold energy of forward reaction is more thanrthat
t y
Statement-2 :
statement-2 is true and statement-2 is correct i s
C (B) Statement-1 is true, statement-2 is true and statement-2 is NOTethemcorrect explanation
(A) Statement-1 is true, explanation for statement-1.

(C) Statement-1 is true, statement-2 is false.

C h for statement-1.

(D) Statement-1 is false, statement-2 is true.

Page # 21
 CHEMICAL KINETICS
Q.68 Statement-1 : A catalyst provides an alternative path to the reaction in which conversion of
reactants into products takes place quickly
r ts
Statement-2 :
er ts pe
The catalyst forms an activated complex of lower potential energy, with the
x
p E
reactants by which more number of molecules are able to cross the barrier per

E x unit of time.
s try
i s try e
i
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
m
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.

em
(C) Statement-1 is true, statement-2 is false.
Ch
Ch
(D) Statement-1 is false, statement-2 is true.
Comprehension
Paragraph for Question Nos. 69 & 70

t s r ts
p e r k

1 1
p e
For a hypothetical elementary reaction
x
where
k 2
E x
Eof A are present. y
2

r y is t r
st
Initially only 2 moles

Q.69 The totalinumber of moles of A, B & C at the end of 50% reactionm

h e m h e are

C
(A) 2 (B) 3 (C) 4
C (D) 5

Q.70 Number of moles of B in the above question

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

r ts ts
p eParagraph for Question Nos. 71 & 72
r
e Let us
A reaction is said to bexfirst order if it's rate is proportional to the concentration of reactant.
p
r y E E x
st A(g)  B(g) + C(g)
consider a reaction
i tr y
e mAt t = 0 a i s
h 0 0
e m
C Ch
At time t a–x x x
dx
The rate of reaction is given by the expression = k(a – x) and integrated rate equation for a given
dt
1  a 
reaction is represented as k = ln   where a = initial concentration and (a – x) = concentration

r ts t ax

pe
of A after time t.
x
Q.71 Thermal decomposition of compound X is a first order reaction. If 75% of X is decomposed in 100
E r ts
r y
min. How long will it take for 90% of the compound to decompose?
t pe
m is
Given : log 2 = 0.30

y E x
he
(A) 190 min (B) 176.66 min (C) 166.66 min
r
(D) 156.66 min

i t
s × 10 min . Starting with
C 2Consider
Q.72 a reaction A(g)  3B(g) + 2C(g) with rate constant 1.386
e m place at constant pressure & at
–2 –1

298K then find the concentration of B after 100 min. C

h
moles of A in 12.5 litre vessel initially, if reaction is allowed to takes

(A) 0.04 M (B) 0.36 M (C) 0.09 M (D) None of these

Page # 22
 CHEMICAL KINETICS

Paragraph for Question Nos. 73 & 74

r ts
e r ts x pe
x Cp
For the given sequential reaction
r yE
A  BE
r yof A, B & C at any time 't' is given by
k1
 k2

i s t
i t
s= [A] e
the concentration
em
e m [A]  k1t

C h
Ch [B] =
t 0

k1[A ]0
t  
( k 2  k1 ) e
 k1t
 e k 2t

[C]t = [A0] – ( [A]t + [B]t )

t s r ts
p e r p e
Q.73 The time at which concentration
x
of B is maximum is
E x
k1
r y E tr y 1 k
ln 1
(A)
i st
k 2  k1 (B)
i s k 2  k1 k 2

e m 1 k
hem k2

C h(C) ln 1
k1  k 2 k 2 (D)
C k 2  k1

Q.74 Select the correct option if k1 = 1000 s–1 and k2 = 20 s–1.

r ts ts
e r
xp pe
[C]t
Conc.

x
[C]t

yE E
conc.

st
(A)
i r [B]t (B)
try
s
[B] t [A]t

em time [A]t

mi
time

Ch Ch
e
[C]t [C]t
Conc.

Conc.

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

r ts [A] t

time
p e time

E x r ts
tr y pe
mis yE x
he i s tr
C em
C h
Page # 23
 CHEMICAL KINETICS
Match the column :

r ts
Q.75
er ts
For the reaction of type A(g)  2B(g)
x pe
p
Column-I contains four entries and column-II contains four entries. Entry of column-I are to be matched
E
x try
with ONLY ONE ENTRY of column-II
E s
try i
Column I Column II

i s e m
(A)em
Ch(P)
d[B]  d[A ]

Ch
vs for first order
dt dt

(B) [A] vs t for first order

ts (Q)
r ts
x p er x pe
E
st r y Efirst order
i s try
(C)

m i
[B] vs t for

em
(R)

e h
Ch C
(D) [A] vs t for zero order (S)

r ts ts
e r
xp pe
Q.76 Column-I and column-II. Entry of column-I are to be matched with ONE OR MORE THAN ONE

E x
ENTRIES of column-II and vice versa.

ry y E
st
Column I Column II
i
(Graphs reaction A Products)
s t
(Co-ordinates)
i r
e m
Ch(A) ln [A]h
em
(P)
C (y-axis), t (x-axis) (order = 1)

(B)
r ts (Q) t 1/2 (y-axis), [A0] (x-axis) (order = 1)

p e
E x r ts
tr y r (y-axis), t (x-axis) (order = 0)pe

mis
(C) (R)

y E x
he i s tr
C em[A ] (x-axis) (order > 1)
(D) (S)
h
t (y-axis),
C
1/2 0

(T) r (y-axis), [A] (x-axis) (order = 1)

Page # 24
 CHEMICAL KINETICS

ANSWER KEY
r ts
ts pe
EXERCISE-1

p e r x
1 d[ NO] E
x mol L s , (ii) 36 × 10 mol L s , (iii) 54×10trymol L s
Q.1 (i) r =
r y
4 dt E
= 9 ×10 –4 –1 –1

i s
–4 –1 –1 –4 –1 –1

1.2 × 10is
t e m
Q.6h 8.12 × 10 Ms
–3 –7 –7 –7

×m
Q.2 gm/min Q.3 (a) 2.1 × 10 M/s., (b) 8.4 × 10 M/s, 2.1 × 10 M/s.
e C
ChRate of formation of Cl = 4 × 10 M s
Q.4 16 –5
10 mol L s Q.5 –1 –1
1.5 torr/s –6 –1

Q.7 –1 –7 –1

Q.8 (a) rate increase by 27 times, (b) rate decreases by 8 times

Q.9 1/6 Q.10 (i) 7.2 M, (ii) Think

ts
Q.11 0 %

r ts
r pe
Q.12 1.67 × 10–5 M s–1 Q.13 K = 0.01 M min–1 Q.14 0.05 atm/s
Q.15 0.75 M
p e
Q.16 6 × 10 sec–9 Q.17 1.2 hr
x
x E
E try
Q.19 (i) 0.0223 min–1, (ii) 62.17 min (iii)  0.6 or 0.59
y
Q.18 (i) 36 min., (ii) 108 min. (iii) 1/8
Q.20
i str
3.435 × 10–3 M/min Q.21 t1/2 = 24.14 min
i s
m
Q.22
e
6.67 × 10–4 Q.23 6M Q.24 3.3 × 104s1
em
Q.25 11.2%
h
Ch C
Q.26 –3
1.45 × 10 M s –1 –5
Q.27 1.25 × 10 mol s –1 Q.28 6 × 10–6 s

20 20
Q.29 (a) 0.01 M (b) min (c) min
3 3

r ts
Q.30 (a) 5 × 10–3 s–1 ( b) 0.06 bar (c) 1.386 × 102 s
ts
e r
xp pe
Q.31 (a) Rate law r = K[NH4+]1 [NH2–]1 ; (b) 3 × 10–4 M–1s–1 ; (c) 6 × 10–5 Ms–1

ryE 6 103
E x
y
d[A ]
st
Q.32 (a) rate law =  = k [A]1 [B]2 ; (b) k =
r
–2 –1
3 = 6 M s
i dt 10
t
s Q.36 3
1m
Q.33 e Q.35 0 mi
Ch First order e(i) r= K[(CH ) O], 0.000428 s
Q.34 3
Q.37 Q.38 16 ml
C h
Q.39 3 2
–1

l P3 l r
Q.40 (a) 75 min (b) 120 min Q.41 k = t ln ( P  P ) Q.42 k = t ln ( r  r )
3 2  t

Q.43 966 min

ts
Q.44 (a) 90 mm, (b) 47 mm, (c) 6.49 × 10–2 min1, (d) 10.677 min.
r
Q.45 k1 = 2.605 × 103 min1
xpe Q.46 40 min

ts
E r
Q.47 0.1 min –1 –3
Q.48 1.66×10 M s –1 –1 Q.49 0.1 min–1

tr y pe
Q.50 is
em t 1
1
Q.51
[C]
=
10
(e – 1) Q.52 t = 4 min 11x

y E x 379.79 K
Q.53
e r
( K1  K 2 ) [ A] 11

C h i t
s (d) f = e
Q.57em
Q.54 (a) 190 kJ, 180 kJ; (b)H = 10 kJ; (c) Endothermic (As H = +ve); –76

h
Q.55 Fraction = e –20 Q.56 9.6 KCal/mol (a) E = 14.4 KCal , (b) 528 M s –1 –1

C
a
Q.58 54.124 kJ/mol (a) 2, (b) 1.5 Q.59 1000 Cal/mol
Q.60 Rate of reaction increases e times 100 Q.61 10.757 kcal mol –1

Page # 25
 CHEMICAL KINETICS

Q.62 2.64 Kcal/mol Q.63 2000 K Q.64 (a) 660R, (b) 30 hours

r ts
s pe
Q.65 6 Kcal/mol Q.66 100 kJmol–1 Q.67 Ef = 7200R; Eb = 10200R
Q.68 r = K' [NO]2[Br2]
e r t 2
Q.69 r = K [NO] [H2], where K = k2 × K1
x
p E
E x; (b) E = E + E
s try
try
d[D] k1k 3[A ][ B] A1A 3
Q.71 (a) dt  k  k
s
a a1 a3 – Ea2. A = A2
mi
i e
2 3

em Ch
Ch EXERCISE-2

Q.1 B Q.2 C
ts Q.3 B Q.4 C Q.5
r tsB
Q.6 C

x p
Q.7 A
er Q.8 B Q.9 C
x pe
Q.10 B
Q.11 D Q.12 A Q.13 D Q.14 D
E Q.15 D
Q.16 B
stry E Q.17 A Q.18 B
i s
Q.19 D
try Q.20 C
Q.21
mi
C Q.22 D Q.23 C
em
Q.24 D Q.25 C
Q.26
e D Q.27 B Q.28 C
h Q.29 B Q.30 C

ChB
Q.31 Q.32 C Q.33 A C Q.34 A Q.35 B
Q.36 C Q.37 D Q.38 A Q.39 B Q.40 A
Q.41 C Q.42 A Q.43 C Q.44 D Q.45 B
Q.46 C Q.47 A
r ts Q.48 B Q.49 C Q.50
ts
C
e r
Q.51 C

E
Q.52
xp
B Q.53 B Q.54 D
x pe
Q.55 C
Q.56 A
try Q.57 B Q.58 B
yE
i s i s tr
em Q.60 ABC
Q.59 ACD Q.61 CD Q.62 AC
m
Q.63 BD
h e
C
Q.64 C Q.65 C Q.66 A ChQ.67 C Q.68 A

Q.69 B Q.70 C Q.71 C Q.72 C Q.73 C

r ts
pe
Q.74 C

Q.75 (A) S, (B) R, (C) P,E

x r ts
tr y (D) Q
pe
i s E x
e m
Q.76 (A) P (B) Q,R (C) S (D) T
try
Ch em
i s
C h
Page # 26