CHEMICAL KINETICS 1

EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS

Objective Questions I [Only one correct option] stoichiometric equation.
1. The rate of reaction is defined as (b) Law of mass action expression can be written from the
(a) decrease in the concentration of a reactant balanced equation.
(b) increase in the concentration of a product (c) Specific reaction rate of a reaction is constant at
constant temperature.
(c) change in the concentration of any one of the reactants
or products per unit time. (d) Rate of reaction and rate constant have same units.
(d) all the above three are correct. Ans. (d)
Ans. (c) Sol. Option d is incorrect as
Sol. The rate of reaction is defined as change in the Rate of reaction =K  Reactant 
x

concentration of any one of the reactants or products per

unit time. Where, K= Rate constant

x = Order of reaction
2. For the reaction A + 2B  C, the rate of reaction at a given
instant can be represented by Rate of reaction has the unit of mole litre-1sec-1 while unit

d[A] 1 d[B] d[C] of K depends on order of reaction.

(a)   
dt 2 dt dt
5. Rate of a reaction
d[A] 1 d[B] d[C]
(b)   (a) increases with increase in temperature
dt 2 dt dt
(b) decreases with increase in temperature
d[A] 1 d[B] d[C] (c) does not depend upon temperature
(c)   
dt 2 dt dt
(d) does not depend upon concentration.
d[A] 1 d[B] d[C] Ans. (a)
(d)   
Sol. For most of the reaction
dt 2 dt dt
Rate of a reaction increases with increase in temperature
Ans. (c) as R  k and k is dependent on temperature.
Sol. Rate of reaction is defined per mole reactant thus
d  Ad  B 1 d  C 6. What is the order of a reaction which has a rate expression
Rateof reaction =- =- × =+
dt dt 2 dt rate = k [A]3/2 [B]–1 ?
Where, ‘-’ indicates consumption or decrease in (a) 3/2 (b) 1/2
concentration of reactants with time & ‘ + ’ indicates
formation or increase in concentration of products with (c) zero (d) none of these.
time. Ans. (b)
Sol. Overall order of reaction  Sum of power to which
3. For a gaseous reaction, the units of rate of reaction are individual concentration term is raised.
(a) L atm s–1 (b) atm s–1 3
R = K  A 2  B
-1
(c) atm mol–1 s–1 (d) mol s–1
Ans. (b) 3 1
So, overall order -1=
Sol. For gaseous reaction, rate is measured in terms of partial 2 2
pressure of the reacting components.
7. Order of a reaction can be
4. Which one of the following statements is incorrect ? (a) fractional (b) zero
(a) Rate law expression cannot be written from the (c) integer (d) all the above.
 CHEMICAL KINETICS 2

Ans. (d) 1
Sol. Order of reaction can be fractional, zero, integral. ×=
3
8. The rate constant of a reaction is 2.1 × 10–2 mol–2 litre2 min–1. 10. For a given reaction half life period was found to be directly
The order of reaction is proportional to the initial concentration of the reactant.
(a) zero (b) 1 The order is
(c) 2 (d) 3. (a) Zero (b) 1
Ans. (d) (c) 2 (d) 3

Sol. Rate constant of reaction is 2.1×10-2 mol-2 litre-2 min -1 Ans. (a)
t1
Unit  mole -2 L2 min -1 Sol. General form of
2
Now,General Rate law,
t 1   A 0
1-n

 
x
R  k Reactant 2

R t 1   A 0
if
 k= 2
 Reactant x i.e. 1-n=1
moleL-1s-1 n=0
in term of unit ; k 
mole× L-×
11. In the presence of acid, the initial concentration of cane-
mole1-× L×-1s-1 sugar was reduced from 0.2 M to 0.1 M in 5 hrs and to 0.05
Comparing mole1-x Lx-1 with mole-2 L2 (from question) we M in 10 hrs. The reaction must be of
get, (a) zero order (b) first order
1-×=-2 (c) second order (d) fractional order
×=3 Ans. (b)
Sol. Half-life of the reaction is constant as in first 5 hours half-
9. When concentration of reactant in reaction A  B is of the reactant reacted
increased by 8 times, the rate increases only 2 times. The
while in next 5 hours also, half-of-the reactant reacted.
order of the reaction would be
(a) 2 (b) 1/3 t
Here, 1 is independent of concentration of reactant i.e.
2
(c) 4 (d) 1/2 reaction must be first order.
Ans. (b)
Sol. Let the order of reaction be × , 12. When concentration of reactant in reaction A  B is
increased by 9 times, the rate increases only 3 times. The
 
×
Thus, R=k A 8 times, order of the reaction would be
R =k 8A  (a) 3 (b) 1/3
×

(c) 6 (d) 1/2

R   as per question  is2R Ans. (d)
Thus,
R=K  A 
x
Sol.
k A 
x
R When A '  9A
=
2R k 8A x R '  3R
× Thus,
1 1
 =  R K  A
x

2 8 
K 9A 
' X
R
1 3×
1 1
   =  1 1
x

 2 8   
3 9
 CHEMICAL KINETICS 3

1 1
2x 15. A reaction involves two reactants. The rate of reaction is
   directly proportional to the concentration of one of them
3 3
and inversely proportional to the concentration of the
1 other. The overall order of reaction will be
x 
2 (a) one (b) two
(c) zero (d) none of these.
13. The rate of reaction between A and B increases by a factor
Ans. (c)
of 100, when the concentration of A is changed from
0.1 mol L–1 to 1 mol L–1. The order of reaction with respect Rate law, R=K  Reacatant1   Reacatant 2 
1 -1
Sol.
to A is :
overall order = 0 .
(a) 10 (b) 1
(c) 3 (d) 2
Ans. (d) 16. If order of reaction is zero. It means that
(a) rate of reaction is independent of temperature
 
x
Sol. Rate  k A (b) rate of reaction is independent of the concentration of
At, A   0.1 mole L-1 , let, R be y, then at the reacting species
(c) the rate of formation of activated complex is zero
 A =1mole L-1 (d) rate of decomposition of activated complex is zero
Ans. (b)
R1 =100 R=100y
Sol. Zero order reaction implies.
R=k  A   0.1
x ×
y R=K  Reactant 
0
 
R 1 =k  A 1
x ×
100y Rate is independent of the concentration of the reacting
species.
2 ×
 1  1
   
 10   10  17. The rate constant of a reaction has same units as the rate
x  2 of reaction. The reaction is of
(a) zero order (b) first order
14. For the reaction, A  B, the rate of reaction is quadrupled (c) second order (d) none of these.
when the concentration of A is doubled, the rate expression Ans. (a)
of the reaction is r = k [A]n, when the value of n is
Sol. Rate Law
(a) 1 (b) zero Now ,rate of
(c) 3 (d) 2
R  K  Reactant 
×
Ans. (d)
Now,rate of reaction  Rate constant when X  0
R=K  A 
n
Sol.
So , unit of rate of reaction and constants are equal for
zero order reaction.
when,  A  is doubled,rate is increased four times,
Thus,
18. Two gases A and B are filled in a container. The experimental
R=K  A 
n
rate law for the reaction between them, has been found to
be Rate = k [A]2 [B]
4R=K  2A 
n

Predict the effect on the rate of the reaction when pressure

n
1 1 is doubled :
 =  (a) the rate is doubled
4 2
2 n (b) the rate becomes four times
1 1
   =  (c) the rate becomes six times
2 2 (d) the rate becomes eight times
 CHEMICAL KINETICS 4

Ans. (d) 2
 A   B
R =K    
R=K  A   B
2
Sol. 2 2
1
We have, PV=nRT for gases = ×K  A   B
2

8
n
R= RT 1
v Thus,R = ×R
8
P = CRT
At constant temp, P  C
21. The unit of rate constant for a zero order reaction is
R  K  A  B 
2
(a) litre sec–1 (b) litre mol–1 sec–1
order = 2 + 1 = 3 (c) mol litre–1 sec–1 (d) mol sec–1.
 If the pressure is doubled by a factor of 2, rate increases Ans. (c)
by a factor of 2 3  8
Sol. Rate = K[reactants]n
 Rate becomes 8 times
K = reate content
19. The rate law expression for the hypothetical reaction n = order of reaction

dx rate
2 A + 3 B  2 C is = k [A] [B]2 K
dt
 reactant n
The order of reaction is
(a) 1 (b) 2 K = reate content

(c) 3 (d) 5 n = order of reaction

Ans. (c) Concentration
Rate   molL1 s 1
Sol. Overall order of reaction  Sum of power to which Time
individual concentration term is raised.
R=R  A   A  Concentration 1
1 2
K 
 concentration of reactent 
n
Time
So, Overall order  1  2  3
Here n = 0
20. The rate law of gaseous reaction : A(g) + B(g)  Products
Concentration mol l 1
2
is given by k[A] [B]. If the volume of the reaction vessel is K   mol liter 1 s –1
Time s
suddenly doubled, which of the following will happen ?
(a) The rate w.r.t. A will decrease two times
22. The equilibrium constant of reaction is 20.0 At equilibrium,
(b) The rate w.r.t. A will decrease four times
the rate constant of forward reaction is 10.0. The rate
(c) The rate w.r.t. B will decrease two times
constant for backward reaction is
(d) The overall rate will decrease 8 times of the original
(a) 0.5 (b) 2.0
value
(c) 10.0 (d) 200.0
Ans. (d)
Ans. (a)
Sol. R=K[A]2 [B] Sol.
1 kf
 
Concentration 
k
K eq = A f
B
volume kb k b

if volume is doubled ,concentration becomes half of initial  K eq =20, k f =10

vlaue.So, new rate will be 10
 kb = =0.5
20
 CHEMICAL KINETICS 5
23. The rate constant for the reaction 2.303 25
2N2O5  4NO2 + O2 is 3.0 × 10–5 sec–1 k= log
10 15
If the rate is 2.4×10–5 mol L–1 sec–1 the concentration of 1 5
N2O5 (in mol litre–1) is  ln
10 3
(a) 1.4 (b) 1.2
(c) 0.04 (d) 0.8 25. The activation energy of a reaction is zero. The rate
Ans. (d) constant of the reaction
-1 N 2 O5 1 dNO 2 dO (a) increases with increase of temperature
Sol. Rate of reaction = =+ =+ 2 (b) decreases with increase of temperature
2 dt 4 dt dt
(c) decreases with decrease of temperature
Rate of reaction =2.4×10-5 mole L-1sec-1
(d) is nearly independent of temperature.
Rate constant =3.0  105 sec 1
Ans. (d)
From, rate constant’s unit
-Ea
order of reaction is first order. Sol. k = Ae RT
Thus, Rate law,
Ea = 0
-1 dN 2 O 5
=k  N 2 O5 
1

2 dt k = Ae 0
 2.4×10-5 =3×10-5  N 2 O5  k= A
' A ' represents maximum rate constant where every
 N 2 O5  =0.8 mole Litre-1
collision is effective collision i.e. leads to fruitful reaction.
24. For a first order reaction P(g) 
 Q(g) + R(g). After 10 minutes Thus, rate constant is nearly independent of temperature
the volume of R gas is 10 L and after complete reaction 50L. When E a = 0.
Hence rate constant will be (in min–1). 26. The ratio of the rate constant of a reaction at any
temperature T to the rate constant T   is equal to
1 1 1
(a) ln 5 (b) ln (a) Energy of activation of the reaction
10 10 5
(b) Fraction of molecules in the activated state
1 1 5 (c) Average life of the reaction
(c) ln 4 (d) ln
10 10 3 (d) Pre-exponential factor in the Arrhenius equation
Ans. (d) Ans. (b)

Sol. P g   Q g  + R  g  K1 E 1 1
Sol. In = a  
K2 R  T2 T1 
Initial Volume V 0 0
V-V1 V1 V1 K1 E 1 1
At t=10 min In = a - 
K R  T 
Completion 0 V V
K E
Now, from Question, V1 =10 L  In = a
K1 RT
And 2V=50 L E
K a
V=25L = e RT
K1
Since, this is first order reaction,
E
V K a
kt=2.303log 0  1 = e RT
Vt K
at t=10 minutes , Represents fraction of molecules in activated state.

25
k =2.303 log
25  10
 CHEMICAL KINETICS 6
27. The half-life period of a radio active element is 30 min. One 29. The half-life period of a zero order reaction is
sixteenth the original quantity of the element will remain (a) directly proportional to initial concentration
unchanged after (b) inversely proportional to initial concentration
(a) one hour (b) sixteen hour (c) independent of initial concentration
(c) four hour (d) two hour (d) proportional to the square of initial concentration.
Ans. (d) Ans. (a)
Sol. For first order reacrtion
n Sol. General relation between
t 1 initial concentration is
Nt 1 2
= 
N0 2
t1  a 1-n

N t = Initial concentration at time t 2

Where , n  order of reaction
N 0 = Initial concentration a  initial concentration
total time  t  for zero order reaction

n = no. of half lives t1 t 1  a1
2 2
30. As the reaction progresses, the rate of reaction
in case of radioactive decay ,we can write ,
(a) increases
n
Nt  1  (b) decreases
 
N0  2  (c) remains constant
n
1 1 (d) first increases, then decreases.
 =    16 =2n  24  2 n
16  2  Ans. (b)
 n=4 Sol. In General, for any normal reaction
4 half lives  4  30 min R=k  Reaction 
x

= 2hrs Where we can write

rate  concentration of reactant
28. Half life period of 2nd order reaction is : So, as time passes, concentration of reactant decreases
(a) proportional to initial conc. of reactants and hence rate decreases.
(b) independent of initial concentration of reactants
31. For the reaction 4 A + B  2 C + 2D, which of the following
(c) inversely proportional to initial concentration of
statement is not correct ?
reactants
(a) the rate of disappearance of B is one fourth of the rate
(d) inversely proportional to square of initial concentration
of reactants. of disappearance of A
Ans. (c) (b) the rate of formation of C is one-half of the rate of
consumption of A
Sol. General relation between
t 1 and concentration of (c) the rate of appearance of D is half of the rate of
2
reactants disappearance of B
(d) the rates of formation of C and D are equal.
t 1  a1-n
2
Ans. (c)
Where , n is order of reaction , a  initial concentration Sol. 4A+B  2C+2D
Thus, for second order reaction,
1 d  A  d  B +1 d  C  +1d  D 
Rate of reaction =- =- = , =
t 1  a1-2 4 dt dt 2 dt 2 dt
2
So, relation between rate of B with that of A is
1
t1 
a 1 d  A  d  B
2 - =-
4 dt dt
 CHEMICAL KINETICS 7

d  A d  B (b) increases
- = -4×
dt dt (c) Remains unaffected
(d) First decreases, then increases.
1 d  A 1 d  C
Relation between ‘C’ and ‘A’’s rate; =- =+ Ans. (b)
4 dt 2 dt
Sol. In general, rate of reaction is directly proportional to
d  C 1 d A concentration of reactants thus with increase of
 =-
dt 2 dt concentration of reactants, rate of chemical reaction
(Equation for 2nd statement which is correct) increase.

1 d  D  d  B
Relation between rate of B and D; + =-
2 dt dt
d  D d  B
 = -2
dt dt
(Equation for 3rd statement which is incorrect because
rate of appearance of d is twice the rate of disappearance
of B)
1 d  C 1 d  D
Relation between rate of C and D; + =+ 34. For a single step reaction;
2 dt 2 dt
A + 2B  Products, the molecularity is
d  C d  D
 = (a) Zero (b) 1
dt dt
(c) 2 (d) 3
(Equation for statement 4 which is correct)
Ans. (d)
Sol. For the given reaction molecularity is 3
32. For the reaction A + B  C + D, the variation of the
concentration of the product with time is given by the 35. In the accompanied diagram, ER, EP and EX represent the
curve. energy of the reactants, products and activated complex
respectively. Which of the following is the activation
energy for the backward reaction ?
II EX
IV
A
D
B
Conc

ENERGY

EP
C
III
ER
I
Time
(a) A (b) B
(a) I (b) II
(c) C (d) D
(c) III (d) IV
Ans. (a)
Ans. (b)
Sol. In a reaction, as the reaction proceeds concentration of
product increases progressively to an equilibrium value.
After some time concentration of product remains
constant with time which is said to be in equilibrium
condition. Thus, curve II is answer..
Sol.
33. Under a given set of experimental conditions, with increase
of concentration of the reactants, the rate of a chemical
reaction
(a) Decreases
 CHEMICAL KINETICS 8
For backward reaction, =  x-y  KJ/mole
E a =E x -E p
A 39. Energy of activation of an exothermic reaction is
(a) zero (b) negative
36. In the sequence of reaction
(c) positive (d) can’t be predicted
k1 k2 k3
A   B   
 C  D Ans. (c)
k3 > k2 > k1, then the rate determining step of the reaction Sol. Energy of activation is always positive be if exothermic or
is : endothermic.
(a) A  B (b) B  C
(c) C  D (d) A  D 40. If a reaction A + B  C is exothermic to the extent of
30 kJ/mol and the forward reaction has an activation energy
Ans. (a)
70 kJ/mol, the activation energy for the reverse reaction is
Sol. Slowest step is rate determining step.
(a) 30 kJ/mol (b) 40 kJ/mol
Since, K1 is smallest, A  B is slowest step.
Smallest, A  B is slowest step. (c) 70 kJ/mol (d) 100 kJ/mol
Thus, A  B is rate determining step. Ans. (d)
Sol. A + B  C; H  -Ve
37. If Ef and Er are the activation energies of the forward and
reverse reactions and the reaction is known to be = -30 k J mol
exothermic, then
(a) Ef < Er
(b) Ef > Er
(c) Ef = Er
(d) No relation can be given between Ef and Er as data are
not sufficient.
Ans. (a)
Sol. For exothermic reaction, 0  H

  E a  r >  E a f
 E a b =  E a f  H

38. An endothermic reaction A  B has an activation energy = 70   30 

as x kJ mol–1 of A. If energy change of the reaction is y kJ, = 70 + 30
the activation energy of the reverse reactions is :
= 100 k J mole.
(a) – x (b) x – y
41. Radioactive decay is a
(c) x + y (d) y – x.
(a) zero-order reaction (b) first-order reaction
Ans. (b)
(c) second order reaction (d) third order reaction
Ans. (b)
Sol. Radioactive decay is a first-order reaction

Sol. 42. For an endothermic reaction, where H represents the

enthalpy of reaction in kJ mol, the minimum value for the
energy of activation will be
(a) Less than H (b) zero
 Ea  = x KJ/mole
(c) More than H (d) Equal to H
Now, E a of reverse reaction is  E a b =E a -ΔH
Ans. (c)
 CHEMICAL KINETICS 9
Sol. Rate of reaction is approximately same i.e. within the
acceptable error limit, value of rate is same which indicates
rate is constant over time interval thus order of reaction
is zero order reaction.

Sol. 45. Ea and H values of reactions R1, R2, R3 and R4 carried out
at the same temperature are as given below :
R1 Ea = 40 kJ mol–1, H = – 80 kJ mol–1
R2 Ea = 20 kJ mol–1, H = – 30 kJ mol–1
Activation energy is an energy barrier that needs to be
overcome for reactant to take part in relation. Thus, is R3 Ea = 60 kJ mol–1, H = + 40 kJ mol–1
endothermic reaction, as seen in figure, activation energy R4 Ea = 30 kJ mol–1, H = + 20 kJ mol–1
must be more than ΔH.
At a given temperature and assuming that the backward
reactions of all these reactions have the same frequency
43. For the decomposition of N2O5 at a particular Temperature factor, the rates of R1, R2, R3 and R4 in their respective
according to the equations backward reactions are in the increasing order of
2N2O5   4NO2 + O2 (a) R2 < R3 < R4 < R1 (b) R4 < R3 < R2 < R1
(c) R1 < R4 < R3 < R2 (d) R1 < R2 < R3 < R4
1
N2O5  2NO2 + O2 Ans. (b)
2
Sol.
the activation energies are E1 and E2 respectively, then
(a) E1 > E2 (b) E1 < E2
(c) E1 = 2E2 (d) E1 = E2
Ans. (d)
Sol. Rate constant is constant for a particular reaction at
particular temperature so is the activation energy.
Activation energy is independent of the mode of balancing
the reaction.

 dx  In R1 thus E a of
44. The rate of a reaction at different times    is found
 dt  backward reaction = 120 k J mole
as follows :
Time (in minute) Rate in (mol L–1 s–1)
0
2.80 × 10–2
10
2.78 × 10–2
20
2.81 × 10–2
30
In R 2 thus
2.79 × 10–2
The order of reaction is E a of
(a) zero (b) one backward reaction = 50 k J mole.
(c) two (d) three.
Ans. (a)
 CHEMICAL KINETICS 10

 
 t 1  at1M=100sec
 2 2
 
 t 1 
 2 1  0.5 
1-n


Thus,   1
1-n

 t 1 
 2 2
1-n
200  1 
In R 3 , E a of backward   
100  2 
Reaction  60  40
 2=  2 
n-1

= 20 k J mole
 n-1=1
n=2

47. In the decomposition of Ammonia it was found that at

50 torr pressureT1/2 was 3.64 hour while at 100 torr T1/2 was
1.82 hours. Then order of reaction would be
(a) 0 (b) 1
(c) 2 (d) 3
Ans. (c)
t1
Sol. General relation of vs initial concentration is
2

In R 4  or pressure 
E a of backward reaction t 1  P1-n
2
 30  20
 
= 10 k J mole At, P=50 torr,  t 1  =3.64hours
 2
1
As, Rate  E  
a Thus, and at P=100 torr,  t 1  =1.82 hours
 2 2
Order of  Ea  backward reaction
 
R1 < R 2 < R 3 < R 4  t 1 
 2 1  50 
1-n
Thus, rate follows the order =
  100 1-n
R 4 < R 3 < R 2 < R1  t 1 
46. The half-life period for a reaction at initial concentrations  2 2
of 0.5 and 1.0 mol lit–1 are 200 sec and 100 sec respectively.
3.64   50  
1-n
The order of the reaction is
  
(a) zero (b) 1 1.82  100 1-n 

(c) 2 (d) 3 1-n
3.64  1 
Ans. (c)   
1.82  2 
t1
Sol. General relation of with initial concentration is  2  2n-1
2

t 1   A 0
1-n n=2
[Where, n is order of reaction]
2

  48. A hypothetical reaction A2 + B2  2 AB follows the

So,  t 1  at 0.5M=200sec mechanism as given below :
 2 1
 CHEMICAL KINETICS 11

=1M
 A + A (fast)
A2 

A + B2  AB + B (slow) 50. SO2Cl2  SO2 + Cl2 is the first order as gas reaction with
A + B  AB (fast) k = 2.2 × 10–5 sec–1 at 320ºC. The percentage of SO2Cl2
The order of the over all reaction is : decomposed on heating for 90 minutes is
(a) 1.118 (b) 0.1118
(a) 2 (b) 1
(c) 18.11 (d) 11.30
1 Ans. (d)
(c) 1 (d) 0
2 Sol. For first order reaction,
Ans. (c)
Sol. Rate determining tep is the slowest step. kt=2.303log
A0 
Thus, rate law is written from second step At
R=K  A  B2 
 2.2×10-5sec-1×90×60sec=2.303log
A 0 
A is an intermediate and intermediate does not appear in A t 
rate law.
So, to remove intermediate from rate law, let’s come to the
step where intermediate was generated.

0.1188 =log  A 0 
A 2  A+A  2.303 At 
 A
2

Kc   log
 A 0  =0.0515
 A2  At 
1
 A  = K c × A 2 =K '  A 2 2
 A 0  =10 0.0515
Thus, rate law is R=K  B2 ×K '  A 2 
1
2
At 
1
=K"  A 2  2  B2 
 A t  =1.126
A0 
3
Thus, overall order of reaction is .
2

 A0  = 1
 A t  1.126
49. The rate constant for a zero order reaction is
2 × 10–2 mol L–1 sec–1. If the concentration of the reactant after 1
 At    A0 
25 sec is 0.5 M, the initial concentration must have been 1.126
(a) 0.5 M (b) 1.25 M 1
Total amount decomposed =  A 0   A 0 
(c) 12.5 M (d) 1.0 M 1.126
Ans. (d) 1.126  A0    A0  0.126
Sol. Integrated rate law for zero order reaction is  =  A0 
1.126 1.126
 A 0 -  A t =Kt
0.126
% decomposed =  100
 K=2×10-2 mole L-1 sec-1 1.126
t=25sec  11.2%
 A t =0.5 M
51. Four vessels 1, 2, 3 and 4 contain respectively, 10 mol
 A 0 =Kt+  A t atom (t1/2 = 10 hours), 1mol atom (t1/2 = 5 hours), 5 mol atom
(t1/2 = 2 hour) and 2 mol atom (t1/2 = 1 hour) of different
=2×10-2 ×25+0.5
=0.5+0.5
 CHEMICAL KINETICS 12
radioactive nuclides. In the beginning, the maximum  O 2  O
radioactivity would be exhibited by the vessel  O  =k c ×
O3
(a) 4 (b) 3
Rate law thus is
(c) 2 (d) 1
Ans. (b)  O3  O
R=k×k c ×  
Sol. Radioactive decay follows first order kinetics, O2  3
-dN =k '   O3   O 2 
2 1
  N0
dt
-dN
  K  N0  53. For a first order reaction : A  B, Whose concentration
dt vs. time curve is as shown in the figure. The rate constant
0.693 is equal to
K=
*We can represent K in 1 order reaction as
st t1 (a) 41.58 h–1 (b) 4.158 s–1
–3 –1
2 (c) 1.155 × 10 s (d) 6.93 min–1
So, for vessel 1 ,
0.693 6.93
R= ×10moleatom= =0.693moles -1
t1 10
2

For vessel 2
0.693 0.693
R= ×1= ×1=0.1386 mole sec-1
t1 5
2

For vessel 3
0.693 Ans. (b)
R= ×5=1.7325 mole sec-1
2 Sol. A  B
For vessel 4
Initial A0 0
0.693
R= ×2=1.386 molesec-1 At t=10 minutes A 0 -x x
1
Thus, initial rate is maximum in vessel 3 . From graph, at t=10 minutes
 A =  B
52. The chemical reaction, 2O3 
 3O2 proceeds as follows A 0 -x=x
O3  O2 + O (Fast) Thus, x= A o
2
O + O3 
 2O2 (slow)
t 1  10
Thus, minutes
The rate law expression should be 2

(a) Rate = K [O3]2 (b) Rate = K[O3]2 [O2]–1 0.693 0.693

K= =
(c) Rate = K [O3] [O2] (d) None for first order reaction, t1 10
2
Ans. (b)
Sol. Slowest step is RDS  0.0693min 1  4.158sec1

R=K  O  O3 
54. Milk turns sour at 40ºC three times faster at 0ºC. Hence Ea
O , is intermediate, thus needs to be removed from rate in calories of turning of milk sour is
now,
From first step, 2.303  2  313  273
(a) log 3
40
kc =
 O2 O
O3 2.303  2  313  273
(b) log(1 / 3)
40
 CHEMICAL KINETICS 13

2.303  2  40 3 × 10-5
=
(c) 273  313 log 3 1.5 × 10-6
(d) none = 20 s-1
Ans. (a)
Sol. Variation of rate constant with temperature is 56. The half-life a first order reaction is 24 hours. If we start
k1 E  1 1 with 10M initial concentration of the reactant then conc.
In = a  - 
k2 R  T2 T1  after 96 hours will be

Given; k 2 = 3k (a) 6.25 M (b) 1.25 M

T-2 = 313K (c) 0.125 M (d) 0.625 M

Ans. (d)
T1 = 273 K
Thus, t 1 =24hours
Sol.
2
k1 E  1 1  For a first order reaction, integrated rate law is
In = a  -
3k1 R  313 273 
kt=2.303 log
A0 
 1  E  -40  A t 
In   = a  
 3  R  313×273 
If  A0  =10M
E - 40 40 × Ea
 - In3  a  2.303log 3 
R 313×273 R ×313×273 Then  A t  after 96 hours

2.303 × log 3×313×273×2 10

 Ea = kt=2.303 log
40 A t 
 Where R1 = 1.987  2calories 
0.693
×96 hours = 2.303log
10
t1 At 
2
55. The rate constant of a reaction A  B + C at 27ºC is 0.693
3.0 × 10–5 s–1 and at this temperature 1.5 × 10–4 percent of as, t = 96 hours k=
the reactant molecules are able to cross-over the P.E. t1
2
barrier. The maximum rate constant of the reaction is
0.693 10
(a) 4.5 × 10–9s–1 (b) 4.5 × 10–11 s–1  ×96=2.303log
(c) 0.2 s –1
(d) 20 s–1 24 At 
Ans. (d) 2.303log 2  0.693
-5 -1
Sol. k = 3 × 10 s 10
 log2 4 =log
Fraction of molecules in activated state At 

= 1.5× 10-6 1.5× 10-4 %  10
We have,   24
 t
A
Ea
k = Ae -RT where, k = 3 × 10 -5 s -1 10
 A t  = M
A = Arrhenius constant which is in fact maximum rate 16
constant. 10
 A t  = M ...i.e. cocentration of 'A' after 96 hour
Ea 16
e -RT  Fraction of molecules in activated state = 0.625 M
Thus,
57. The half-life period of a radioactive element is 120 days.
k
A= Ea
Starting with 1 gm, the amount of element decayed in 600
e -RT
 CHEMICAL KINETICS 14
days will be reactants is more than that of the products
1 15 Ans. (a)
(a) g (b) g
16 16 T
 298 + 10 
1 31 Sol. Temperature coefficient μ = T298
is
(c) g (d) g
32 32
calculated at two temperature differing by 10o C
Ans. (d)  μ lies between 2 and 3 for most of thereactions.
Sol. For a radioactive sample , decay follows first order
kinetics , thus,
n
59. The thermal decomposition of A  B + C has rate constant
1 x mole–1/2 lit1/2 min–1 at a given temperature. How would
N t =N 0  
2
dA
N t = Number of nuclei undecayed at time t  will change if concentration of A is doubled keeping
dt
N 0 = Number of nuclei initially temperature constant
t (a) will increase by 2.828 times
n = Number of half - lives = t 1 (b) will increase by 4 times
2
(c) will increase by 11.313 times
Thus, Number  Number of moles × N A (d) will not change
=1 gm × N A Ans. (a)
Nt = X
 
×
Thus, Sol. Rate law is R=K A
600
 1  120
n=1×N A   General form for unit of K is mole1-× L1-× s1 or
2
X=1gm× N A ×
1 mole1-× L1-× min -1 ( Time can be in s,min)
32 Comparing the unit given in question with mole 1 - x
1
Thus, X = of N 0 L× -1 m in -1
32
i.e. in terms of mass , -1 3
We get , 1-x= ×=
1 2 2
Amount of element undecayed  Thus , 32 gram IF (A) is doubted then ,
Thus, total amount decayed is initial mass -undecayed R =K[2A]3/ 2
1 3
=1gm-
32
gm R '  K  A 2  23/ 2
3
31  2 2 R
= gm
32 3
To find value of
=2 2
58. Which one of the following statements is incorrect ? Taking log on both sides,
(a) The temperature coefficient of a reaction is the ratio of 3
the rate constant at any two temperatures
log×= log 2
2
(b) The temperature coefficient of a reaction is the ratio of 3
the rate constants at 298 K and 308 K log×= ×0.3
2
(c) The temperature coefficient of most of the reactions log×=0.45
lies between 2 and 3
×=2.818
(d) In an endothermic reaction, activation energy of
 CHEMICAL KINETICS 15
Thus, rate is 2.818 times that of R . the rate constant of reaction will increase to a maximum of
(a) 2.3 × 10–2 min–1 (b) 4.6 × 10–2 min–1
60. The thermal decomposition of acetaldehyde : (c) 2.30 min–1 (d) 115 min–1
CH3CHO  CH4 + CO, has rate constant of 1.8 × 10–3 mole– Ans. (d)
1/2
L 1/2 min –1 at a given temperature. How would
Sol. Maximum rate constant refers to Arrhenius constant, i.e
d[CH 3CHO]
 will change if concentration of acetaldehyde Ea
dt K = Ae -RT
is doubled keeping the temperature constant ?
A = Maximum rate constant
(a) will increase by 2.828 times
(b) will increase by 11.313 times k 2.3 × 10-3 min -1
A= =
Thus, Ea
2 × 10-5
(c) will not change e -RT
(d) will increase by 4 times  -RT
Ea

Ans. (a)  e = Fraction of molecules in activated state 
 
Sol. Generally form for unit of reaction is mole1-× L×-1 time -1
So, comparing with given rate constant’s unit . 2.3
= × 102
1 2
1-×=- 230
2 = min 1
3 2
×= = 115 min 1
2
Now , when concentration is doubled, rate increases by
3
63. For the reaction
R =K[2A] 2 CH3Cl(aq) + OH– (aq)  CH3OH(aq) + Cl–(aq)
3 3 The kinetic data are as given below :
R =2 2 ×K[A]2 [CH3Cl] [OH–] + d [CH3OH]/dt (M min–1)
3
0.2 0.1 2 × 10–3
R =2 ×R
2

0.4 0.1 4 × 10–3

Thus, rate increases by 2.828 times of original rate .
0.4 0.2 8 × 10–3
If Kc for the above reaction is 1 × 1014, then the specific
61. The decomposition of ozone is believed to occur by the
reaction rate (M–1 min–1) for the replacement of –OH group
mechanism :
of methanol by Cl atom is :
O3  O2 + O (fast)
(a) 10–18 (b) 10–15
O + O3  O2 (slow) (c) 1015 (d) 10
When the concentration of O2 is increased, then the rate Ans. (b)
(a) increases (b) decreases Sol. Rate of law;

R=k  CH 3 Cl   OH - 
y
(c) remains same (d) cannot be predicted x

Ans. (b) To find order

Sol. Rate law of given reaction is
when  CH3Cl   0.2M and
Rate  K  O3   O 2  .
2 -1
 OH -  =0.1M, R=2×10-3 Mmin -1
Thus, when concentration of O 2 is increased rate will
So, 2×10 -3 =k  0.2   0.1 ...  i 
x y
decrease.
62. The rate constant of a reaction at 27ºC is 2.3 × 10–3 min–1 and when
at this temperature 0.002% of the reactant molecules are  CH3 Cl  0.4m and  OH -  =0.1M, R=4×10-3 Mmin -1
able to cross over the energy barrier existing between the
reactants and products. By increasing the temperature,
 CHEMICAL KINETICS 16

So, 4  10 3  k  0.4 
x
 0.1
y
...  ii  Pb .
when Let, nubmer of U = Number of Pb = x atoms
*Pb is the daughter nuclide formed from the radioactive
 CH 3Cl =0.4m and  OH -  =0.2M, R=8×10-3 Mmin -1 decay of Uranium.
2
So, 8×10 -3 =k  0.4   0.2  ...  iii 
x y
U  206
238
92 82 Pb  82 He
4
 6B1
Thus, whatever, Pb we have to present that is from
Comparing  i  &  ii  Uranium.

2×10-3 k  0.2   0.1

x y
So, total uranium present originally =x+x  of Pb   2x
So, 4×10-3 =
k  0.4   0.1 Thus, time elapsed for original sample to come to present
x y

state 4.5 109 of Uranium

x
1 1
 =   4.5  109 years
2 2
Thus, Rock is 4.5 109 years old.
x=1
Comparing  ii  &  iii 
65. According to the collision model of kinetics, certain
4×10 -3
k  0.4   0.1
x y activation energy must be overcome before a reaction can
= proceed. Based on the data given below, what is a
k  0.4   0.2 
-3 x y
8×10 reasonable estimate of the activation energy for the
y decomposition of NOCl ?
1 1
   2 NOCl(g)  2 NO(g) + Cl2(g)
2 2
Temperature (K) Rate constant, k (L/mol s)
y=1
400 6.6 × 10–4
Thus, rate law is
500 2.9 × 10–1
R=K CH 3 Cl  OH 
1 1
600 1.63 × 101
Now, to find K , lets use equation  i  (a) 1.00 × 102 J/K mol (b) 1.23 × 103 J/K mol
(c) 1.05 × 105 J/K mol (d) 1.34 × 106 J/K mol
 2×10-3 =K  0.2  ×  0.1
1 1
Ans. (c)
2×10-3 Sol. Variation of rate constant with temperature can be
K= =10-1
2×10-2 represented by equation
This is for forward reaction. K 2 Ea  1 1 
In =  - 
Now, given K c for equilibrium is 11014 K1 R  T1 T2 
Kf 2.9 × 10-1 E a  1 1 
As, K c = K  In = -
b 6.6 × 10-4 R  400 500 
-1
10 2.9× 103 Ea  100 
K b = M -1min -1  2.303log =
1014  4
66 8.314J K 1mol1  20×10 
=10-15  Rate constant for backward reaction 
 29000  5
2.303log   × 8.314 × 2 × 10
 66 
64. A sample of rock from the moon contains equal number of  Ea =
100
atoms of U and Pb (t½ for uranium = 4.5×109 years). The
age of rock would be 2.303  2.642  8.314  2  105

(a) 4.5 × 109 years (b) 90 × 109 years 100
(c) 13.5 × 109 years (d) 2.25 × 109 years 101.17 × 105
=
Ans. (a) 100
Sol. Rock at present contains equal number of atoms of U and = 1.01× 105 J K-1mol-1
 CHEMICAL KINETICS 17

Objective Questions II
68. Which of the following statements about the Arrhenius
[One or more than one correct option]
equation is/are correct ?
66. When the temperature of a reaction is changed from T1 to
(a) The pre-exponential factor becomes equal to the rate
T2 half-life is found to decrease. Thus :
constant of the reaction at extremely high temperature
(a) T2 > T1
(b) When the activation energy of the reaction is zero, the
(b) The reaction is exothermic
rate becomes independent of temperature
(c) The reaction is endothermic –Ea/RT
(c) The term e represents the fraction of the molecules
(d) The reaction can be exothermic or endothermic having energy in excess of threshold value
Ans. (a, d) (d) On raising temperature, rate constant of the reaction
Sol. Rate of reaction is directiy proportional to temperature of greater activation energy increases less rapidly than
most of the reaction either it is exothermic or endothermic that of the reaction of smaller activation energy.
reaction.
Ans. (a, b, c)
t1
As decreased from T2  T1 that means Ea
2
Sol. K = Ae -RT
Rate has decreased from T2  T1
Ea 1
 In K = In A - ×
R T
67. For the hypothetical reaction
A2 + B2 2AB, the mechanism is given as below
A2 A + A(fast reaction)
A + B2 AB + B (slow reaction)
A+ B AB (fast reaction)
then
(a) the rate determining step is A + B2 AB + B
(b) the order of the reaction is 3/2
(c) the overall molecularity is 4
(d) the rate expression is Rate = k [A] [B2]
Ans. (a, b) 1
when, 0
Sol. Rate [B2] T
A  B2  AB  B  slow In k  In A
i.e. at T  , Maximum rate = A
 RDS & r  k  A B2  ..(1)
But A is intermediate so its concentration can be obtained  Also, when E a = 0, In k = In A
by eqvlibrium method
A2  A  A  fant   From graph,higher is the slope higher will be rate
sensitivity to temperature and
 A  A   K A  1 2
K eq     eq  2   Ea
 A2  slop = -
R
. Thus, higher the E a more rapidly rate
Subefitnting value of [A] is eq (1) increases with increasing energy.

R  K  A2 
1
 B2 
-Ea
e RT represent fraction of molecules with K.E in excess of
2

3 Ea thus overall energy of these molecules will be in excess

Order of Reaction 
2 of Er lie threshold energy as Er = ERT Ea where Er is
In a complex reaction, Molecularity of reaction is energy of reactant thus, a,b,c are correct
Molecularity of R.D.S, so there is no concept of overall
Molecularity.
 CHEMICAL KINETICS 18
+
69. Hydrolysis of an ester is catalysed by H ion. proportional to  H  as PH=-log  H  since, PH
+ +

Using equimolar concentrations of two acids HX and HY,

decreased by 1unit meaning  H  increased 10 times
+

both being strong acids, the rate constants of the reaction

–3 –1 –3 –1 thus rate is also increased 10 times .
are found to be 3 × 10 min and 5 × 10 min respectively
Thus,
at a fixed temperature. It can be concluded that
Rate  Sugar 
1
(a) Rate constant may be taken as the measure of degree
of ionization of the acid used as catalyst Rate   H + 
(b) HX is a stronger acid than HY, their relative strength
Rate law; Rate=K Sugar  as H + is a catalyst and is
being 1.7
maintained at particular PH .
(c) HX is a weaker acid than HY, their relative strength
being 0.6 71. Estrification of acetic anhydride by ethanol takes place as
(d) none is correct (CH3CO)2 O + C2H5OH  CH3COOC2H5 + CH3COOH
Ans. (a, c) Select the correct statements of the following :
+

CH 3 COOC 2 H 5 
H
 CH 3 COOH+C 2 H 5 OH (a) When reaction is carried out in dilute hexane solution,
Sol. the rate law is given by k [Anhydride] [Alcohol]
R= k [H + ][ CH 3 COOC 2 H 5 ]
Now, when concentration of ester is same and (b) When ethanol is the solvent, the rate law is given by
concentration of acid is also same and if rate is changing k [Anhydride]
then that is due to change is strength of acid .
Thus, difference in rate is an andication of difference in (c) The values of k in the two cases are the same
strenght of acid . (d) Using ethanol as the solvent, its concentration changes
In presence of stronger acid , rate hydrolysis will be higher. significantly during the course of the reaction
Thus,
Ans. (a, b)
R1 K a (HX)
= Sol. Whenever , any reactant itself is a solvent, then solvent
R 2 K a (HY) will be not appear in rate law expression as it is in large
Where , K, is dissociation constant . excess, thus
3×10-3 K a (HX) Ln dilute solution
Thus, =
5×10-3 K a (HY) Rate law is R=K[(CH3 CO) 2 O][ C 2 H 2 OH
K a [HY]×0.6= K a [HX] In case, C 2 H 5 OH is solvent, then [C 2 H 5 OH] remains
Thus, option a is constant and option ‘c’ is correct as K a practically constant, thus
of HX is 0.6 times that of HY. R=K [(CH 3 CO)2 O]

+ Where, K=[C 2 H 5 OH]

70. Hydrolysis of a sugar is catalysed by H ion. Half-life of
the reaction is independent of initial concentration of sugar Thus,option a and b are correct
at a particular pH. At a constant concentration of sugar Regarding option ‘c’ , its clear from above K  K 
rate increases 10 times when pH is decreased by one unit. and concentration of solvent does not change significantly
Pick out the correct statements of the following :
+
thus option ‘d’ and ‘c’ are incorrect;
(a) Rate  [sugar] (b) Rate  [H ]
72. Which of the following statements are correct ?
(c) Rate law : rate = k (sugar)
(a) Time required for 75% completion is 1.5 times of half-
+
(d) Rate law : rate = k [sugar] [H ] life for zero order reaction
Ans. (a, b, c) (b) Time needed for a definite fraction of first order reaction
t1 does not vary with the initial concentration
Sol. is independent of concentration of sugar at a particular
2
(c) Time for 25% reaction is one-third of half-life in second
PH , thus, reaction follows
order process
first order kinetics with respect to concentration of sugar.
At constant concentration of sugar, rate is directly (d) Rate of zero order reaction gets doubled if the
concentration of the reactant is increased to a two fold
 CHEMICAL KINETICS 19
value  A 0
now, when  A t =
Ans. (a, b, c) 2
Sol. From integrated rate law for zero order reaction, t  t1
 A 0 -  A t =Kt 2

2 1
At  ... i Thus, Kt 1 =  A  -  A 
 t1   2 0 0
2
2K
1
3 A0  Kt 1 = ...  i 
 t3  ... ii  2  A 0
4K
 A 0
4

t1 When  A t =3
2 2 4
=
Thus, t 3 3 t  t1
4 4

3 4 4
 t 1 =t 3 kt 1 = -
2 2 4
4
3  A 0  A 0
The option a is correct.
1
*In a first order reaction, for a definite fraction, time is kt 1 = ...  ii 
independent of initial 4
3  A 0

concentration e.g. for

1
of reaction to be complete Comparing  i  and  ii 
2
1
t r2 =0.6931k Thus, t 1 = 3 of t 1
4 2
th
3 Answer c is correct
For to be complete
4 Rate of zero order reaction is independent of concentration
t 3 =2t 1 of reactant.
4 2 Thus, only a,b and c are correct.
Thus, option b is correct.
*For a second order reaction, taking a simple hypothetical 73. Which of the following graphs plotted are true ?
reaction, A  B following a
second order kinetics, (a) For a zero order reaction
Rate law is
-d  A 
=k  A 
2

dt
Integrating both sides
-d  A 
 A 2
=k  dt
(b) For a zero order reaction
1
+ =kt+C
 A t
1
When, t=0, C=+  A 
0

1 t 1
Thus,  A  =K +  A 
t 0 (c) For a 3rd order reaction
1 1
   kt is required integrated rate law
 A t  A 0
 CHEMICAL KINETICS 20

(c) (d)

For all normal reaction For exposive reaction

(d) For a 1st order reaction Ans. (a, b)
Sol. Option a and b are correct.
For normal reaction, R increase linearly with temperature
for explosive reaction, rate becomes violently higher once
critical temperature is achieved.

75. An increase in the rate of reaction with rise in temperature

is due to
(a) an increase in the number of collisions
Ans. (b, c)
Sol. Zero order reaction is unusual reaction in which rate is (b) an increase in the number of activated molecules
independent of the external factors as long as the (c) lowering of activation energy
surface on which reaction is taking place is saturated. (d) shortening of mean free path.
e.g. Decomposition of HI on gold foil follows order
Ans. (a, b, c)
2 HI 
Au
 H 2 + l2 Sol. Temperature increases collission frequency increases and
Thus, as long as surface of Au is saturated rate is also number of molecules with energy in excess of E a
independent of any additional factors.
increases thus rate of reaction increases.
So, option a is incorrect.
Activation energy is considered to be constant for wide
t1
General relation of with initial concentration range of temperature in our calculation so no effect on E a
2
is there.
t 1  a1-n Mean free path is directly proportional to temperature
2
hence there is no shortening of mean free path.
t1  a
for zero order reaction ;
2
for 3rd fororder reaction Numerical Value Type Questions
1 76. For the reaction : A + B  P, if concentration of B is
; t 1  a2 doubled, maintaining concentration of A constant, rate of
2
reaction is also doubled. If concentration of A is tripled.
t1 maintaining concentration of B constant, rate of reaction
is in dependent of a in 1st order reaction
2
increases by a factor of nine. If concentrations both A and
B are doubled simultaneously, the rate of reaction will
74. Which of the following graphs are properly represented increase by a factor of ____.
Ans. (8.00)
Sol. (1) For A + B  P
(a) (b) Rate law
R  k  A  B 
x y
..(1)
(2) If concentration B doubled rate doubles
For normal reaction For exposive reaction
2 R  k  A  2 B 
x y
...(2)
(3) If concentration A is tripled rate increases by 9 times

 Rate law is
 CHEMICAL KINETICS 21

9 R  k  3 A  B 
x y
...(3) 78. Temperature coefficient is defined as the factor by which
the rate of reaction increases on increasing the temperature
comparing eq (1) & (2)
by 10ºC at a given temperature. If activation energy of a
2 R  k  A  2 B 
x y
reaction is 85 kJ, determine the temperature coefficient at
R  k  A  B 
x y 300 K (Rounded off to the nearest whole number).
Ans. (3.00)
 2  2y
y=1 k2 Ea  1 1 
Sol. In =  - 
comparing eq (1) & (3) k1 R  T1 T2 
9 R  k 3 A  B 
x y
T1 = 300 k
R  k  A  B 
x y
T2 = 310 k
93 x
k2 85 × 103 J  10 
x=2 Thus, In = -1 -1  
k1 8.314 Jk mol  300×310 
i.e., R = k  A   B 1
2
k2
now, when both [A] & [B] doubles In = 1.09
k1
R  k  2A   2B
2 1
k2
2.303 log = 1.09
R  8k  A   B
2 1
k1
Rate becomes 8 times. k2
log = 0.47
k1
77. For the reaction : A  P
k2
when initial concentration of reactant is halved, the half-life  = 2.95
k1
increases by a factor of eight. Order of reaction is____.
Ans. (4.00)
k 310
t1 i.e. = μ = 2.95  3
Sol. General relation of vs initial concentration is k 300
2

t 1  a1-n Assertion Reason

2
(A) If both assertion and reason are correct and reason is
a the correct explanation of assertion.
When a 
2 (B) If both assertion and reason are true but reason is not
t' =8×t 1 the correct explanation of assertion.
then, 1
2 2
(C) If assertion is true but reason is false.
t' 1
 2
=8 (D) If assertion is false but reason is true.
t1
2

1-n
79. Asseration (A): The rate of the reaction is the rate of
a change of concentration of a reactant or a product.
 
  1-n =8
2 Reason (R): Rate of reaction remains constant during the
a  complete reaction.

1
1-n Ans. (c)
  =23 Sol. As assertion is true (Definition) reason is incorrect, as
2 this is valid only for zero order reactions and zero order
2n-1 =23
n=4
 CHEMICAL KINETICS 22
reaction are not natural reactions.
83. Assertion (A): For the 2N2O5  4NO2 + O2 ; Rate =
80. Asseration (A): If in a zero order reaction, the concentration K[N2O5].
of the reactant is doubled, the half-life period is also doubled. Reason (R): Rate of decomposition of N2O5 is determined
Reason (R): For a zero order reaction, the rate of reaction by slow step.
is independent of initial concentration. Ans. (a)
Ans. (b) Sol. Decomposition of N 2 O5 follows first order kinetics. It is
 A0 fact.
Sol. t1 = Since, there is relation between order of reaction and
2
2K for zero order reaction stoichiometric coefficient of reactant suggesting the
reaction is of complex nature.
t 1   A 0
Thus, In complex reaction, rate is determined by slow step.
2

Hence, Assertion is correct. But statements are individually correct and rate law is
calculated from R.D.S.
In zero order reaction, rate is independent of initial
Thus, Answer a is correct choice.
Concentration as rate=K  A 0
0
Match the Following
Rate=K Each question has two columns. Four options are given repre-
Thus, reason is also correct. senting matching of elements from Column-I and ColumnII.
But, reason does not explain assertion. Only one of these four options corresponds to a correct match-
81. Assertion (A): According to steady state hypothesis, in a ing for each question.
multistep reaction, the change in concentration with time
for reactive intermediates is zero. 84. C0 = Initial concentration of reactant; C = Concentration
Reason (R): The intermediates are so reactive that after a of reactant at any time t; k = rate constant
brief initial period their concentrations rise from zero to a Match the following :
small value and remains constant for most of the duration
of the reaction. Colume-I Colume-I
Ans. (a) Plots Slopes
Sol. Both statements are correct and reason is correct (A) C vs (abscissa) for zero order (P) Unity
explanation of assertion as in steady state hypothesis, (B) log C vs t (abscissa) for first order (Q) Zero
rate of formation of intermediate is equal to the rate of its
 dc 
destruction as they are highly reactive. (C)    vs C for zero order (R) – k
 dt 
82. Asseration (A): If the activation energy of a reaction is (D) ln (–dc/dt) vs ln C for first order (S) -k/2.303
zero, temperature will have no effect on the rate constant.
Ans.  A-R; B-S;C-Q; D-P 
Reason (R): Lower the activation energy, faster is the
reaction. Sol.  A  For zero order reaction
Ans. (b)
Ea
k=
Sol. –S
K = Ae -RT
lop
e
When, E a = 0, k = A [C]
A represents maximum rate constant which is possible
when every collision is effective one. In this situation,
temperature will have no effect. Time
Ea C 0 -C=kt
From, K = Ae -RT
So, C=C 0 -kt
1
Its is clear, k  E thus, lower the acitvation energy y = mx + C
a
faster is the reaction.
Both statements are correct but reason is not correct
explanation of assertion
CHEMICAL KINETICS 23

Where, m=k
y=C  dc 
ln   
 dt 
Thus, C vs t in zero order reaction looks like

So, slope = -k t
dc
So, matching option of - =k  C 
dt
AR Taking in a both sides
B) For first order reaction  dc 
ln  -  =ln k+ln C
C  dt 
kt=2.303log 0
C Which is in the form of y = mx + c
kt Where, m=1
 =logC0  log C
2.303 Thus, matching option
kt DP
 =logC0  log C
2.303 Paragraph Type Questions
kt Use the following passage, to solve Q. 85 to Q. 87
 log C=logC 0 
2.303
Passage
Concentrations measured as a function of time when
gaseous N 2O 5 at initial concentration of 0.0200 M
decomposes to gaseous NO2 and O2 at 55ºC. The change
in concentration with time is given by the following graph.

Which is of the form, y=mx+c

Where, y=logC, x=t
-k
m=
2.303
C=logC0
Thus, matching option
BS
C) Rate law for zero order 85. The instantaneous rate of reaction at the beginning of the
reaction is
dc
=k  C  =k.
0
m=- –5
(a) 2.2 × 10 M/s
–5
(b) 1 × 10 M/s
dt
Thus, matching option
CQ
So, rate is constant
Slope  0
D) For 1st order reaction
 CHEMICAL KINETICS 24
–5
(c) 6.3 × 10 M/s (d) zero not be equal to the respective stoichiometric coefficients. k is the
Ans. (d) velocity constant of the reaction. The determination of rate law is
simplified by the isolation method in which the concentration of
Sol. Compression reaction; 2 N 2 O5  4 NO 2 +O2
all the reactants except one are in large excess. If B is in large
1 d  N5 O5  1 d  NO2  d  O 2  excess. we can approximate [B]by  B0
Reaction rate =- =+ =+
2 dt 4 dt dt
From graph, we can say, in interval of 100 second, Hence, Rate = k  A   B = k  A  B0 = k'  A 
a b a b a

Δ N 5 O5 =0.0037M
(k   k[B]0b )
Same as that of  NO 2 

Δ  N 5 O5  or log  initial rate  = log  0  log k   a log [A ] ...... (ii)

So, Average rate =
Δt
A plot of log (rate) against log  A values will be a straight line
as Δt  O, we have Instantaneous rate.
which enables to calculate both k and a. Similarly orders with
 i.e.Δ Δ  N O   d  N O  
5 5 5 5 respect to other reactants. taken in much smaller concentrations
At the beginning of reaction, instantaneous rate is zero turn by turn, can be determined. Consider the reaction :
as d  N 2 O-5  is negligible. 2I (g )  Ar(g ) 
 I 2(g )  Ar(g )

The following figures show the variation of log 0 against (a)

86. The rate of formation of NO2 during the period 600 – 700 s
is log I0 for a given  Ar 0 and (b) log  Ar 0 for a given  I 0
–5 –5
(a) 3.7 × 10 M/s (b) 2.2 × 10 M/s
–5 –5
(c) 4.8 × 10 M/s (d) 1.6 × 10 M/s
Ans. (b)
Sol. From graph, Δ  NO2  =0.0022
Δt =100
Δ  NO 2 
 Rate of formation= =2.2×10-5 M s
Δt

87. The rate of decomposition of N2O5 during the period 300 –

400 s is
–4 –5
(a) 3.7 × 10 M/s (b) 2.6 × 10 M/s
–5 –8
(c) 1.9 × 10 M/s (d) 3.6 × 10 M/s
Ans. (c)
Sol. The graph says, Δ  N 2 O5  =0.0019M
Δt =100sec .
 Rate of Decomposition of
Δ  N 2 O5 
N 2 O5 = =1.5×10-5 M s
Δt The rate constants of most reactions increase as the temperature
Use the following passage, to solve Q. 88 to Q. 90 is increased. The rate constant increases by about 100-200% for

The dependence of rate on concentrations of reactants is a temperature rise of 10K . It is found experimentally for many
expressed in terms of rate law, which is established experimentally. reactions that a plot of n k against 1 T gives a straight line.
This behaviour is expressed in the form of equation.
Rate = k  A   Bb
a
(Rate law) ..........(i)
Ea
The exponents a, b, etc. (determined experimentally) may or may n k  n A  .............. (iii)
RT
 CHEMICAL KINETICS 25
88. The rate of change of molar concentration of C in Reaction – 1, 1
–3 –1 –1
isfound to be3.0 × 10 mol L s . The rate of reaction and Thus, greather slope the plot of lnk against
for a reaction
T
rate of disappearance of the reactant B are respectively. shows strong dependence on temperature.
–3 –1 –1
(a) 3.0 × 10 mol L s each
–3 –1 –1
(b) 1.0 × 10 mol L s each
–3 –1 –1 –3 –1 –1
(c) 1.0 × 10 mol L s and 2.0 × 10 mol L s
(d) None of these.
Ans. (c)
d  c
Sol. = 3.0 × 10-3 mol L-1 s-1
dt
1 d  c 1
Rate of reaction  =  3 × 10-3 mol L-1 s-1
3 dt 3
d  B
Rate of disapperance of B = = 2 × Rate of reaction
dt
= 2 × 10-3 mol L-1 s-1

89. According to the fig-1 (a) and 1 (b), the rate law for the
reaction
2I(g) + Ar(g)  I2(g) + Ar(g) is given by
2
(a) Rate = k [I] [Ar] (b) Rate = k[I]
2 2 2
(c) Rate = k[I] [Ar] (d) Rate = k[I] [Ar]
Ans. (d)
Sol. Data insufficient.

90. The greater slope of the plot of n k against 1/T for a

reaction shows the rate constant to be
(a) Independent of temperature
(b) Strongly dependent on temperature
(c) Poorly dependent on temperature
(d) Insufficient information to predict
Ans. (b)
Ea
Sol. For lnk = lna -
RT
Consider following plots.
Slope of ll > Slope of l

From graph it is clear for same difference temperature,

variation of rate is higher in the plot with greater slope.
CHEMICAL KINETICS 26