11

Chemical Kinetics
Objective Questions I (Only one correct option) 5. Consider the given plot of enthalpy of the following reaction
1. NO2 required for a reaction is produced by the between A and B. A + B æÆ C+D
decomposition of N2 O5 in CCl 4 as per the equation, Identify the incorrect statement. (2019 Main, 9 April II)

2N2 O5 ( g ) æÆ 4NO2 ( g ) + O2 ( g ) 20
The initial concentration of N2 O5 is 3.00 mol L-1 and it is
Enthalpy 15
2.75 mol L -1 after 30 minutes. The rate of formation of NO2 (kJ mol–1)10
y
D
is (2019 Main, 12 April II)
r
-3 -1 -1 -2 -1 -1 5
(a) 4167
. ¥ 10 mol L min (b) 1667
. ¥ 10 mol L min
ra

A+B
C
(c) 8.333 ¥ 10-3 mol L -1 min -1 (d) 2.083 ¥ 10-3 mol L -1 min -1
Reaction
ib

coordinate
2. In the following reaction; xA Æ yB
el

È d[ A ]˘ È d[B ]˘ (a) D is kinetically stable product.

log 10 Í- ˙ = log 10 Í dt ˙ + 0.3010
je

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

Î dt ˚ Î ˚
(c) C is the thermodynamically stable product.
e/

A and B respectively can be (2019 Main, 12 April I)

(d) Activation enthalpy to form C is 5 kJ mol -1 less than that to
t.m

(a) n-butane and iso-butane (b) C2H2 and C6 H6

form D.
(c) C2H4 and C4 H8 (d) N2O4 and NO2
6. The given plots represent the variation of the concentration
3. For the reaction of H 2 with I2 , the rate constant is
of a reaction R with time for two different reactions (i) and
-4 3 -1 -1 3 -1 -1
2.5 ¥ 10 dm mol s at 327ºC and 10 . dm mol s (ii). The respective orders of the reactions are
at 527ºC. The activation energy for the reaction, in (2019 Main, 9 April I)
kJ mol- 1 is (R = 8.314 JK - 1 mol- 1 ) (2019 Main, 10 April II) (i) (ii)
(a) 59 (b) 72 (c) 150 (d) 166
In [R] [R]
4. A bacterial infection in an internal wound grows as
N ¢ ( t ) = N0 exp ( t ), where the time t is in hours. A dose of
antibiotic, taken orally, needs 1 hour to reach the wound. time time
Once it reaches there, the bacterial population goes down as
dN N (a) 1, 1 (b) 0, 2
= - 5N 2 . What will be the plot of 0 vs t after 1 hour ? (c) 0, 1 (d) 1, 0
dt N
(2019 Main, 10 April I) k1 k2
7. For a reaction scheme, A æÆ B æÆ C , if the rate of
formation of B is set to be zero then the concentration of B is
N0 N given by (2019 Main, 8 April II)
(a) (b) 0
N N Êk ˆ
(a) k1k2[ A ] (b) ÁÁ 1 ˜˜[ A ]
t(h) t(h) Ë k2 ¯
(c) (k1 - k2 )[ A ] (d) (k1 + k2 )[ A ]
N0 N0 8. For the reaction, 2 A + B Æ C , the values of initial rate at
(c) (d)
N N different reactant concentrations are given in the table below.
The rate law for the reaction is (2019 Main, 8 April I)
t(h) t(h)

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 Chemical Kinetics 169

[A](mol L-1 ) [B](mol L-1 ) Initial rate Choose the correct option.
(mol L-1s-1 ) (a) Both I and II are wrong
(b) Both I and II are correct
0.05 0.05 0.045
(c) I is wrong but II is right
0.10 0.05 0.090 (d) I is right but II is wrong
0.20 0.10 0.72
15 For the reaction, 2A + B æÆ products
2 2 2
(a) rate = k [A ][B ] (b) rate = k [A ] [B ]
When concentration of both (A and B) becomes double, then
(c) rate = k [A ][B ] (d) rate = k [A ]2[B ]
rate of reaction increases from 0.3 mol L -1 s -1 to
9. For a reaction, consider the plot of ln k versus 1/ T given in 2.4 mol L -1 s -1 .
the figure. If the rate constant of this reaction at 400 K is When concentration of only A is doubled, the rate of reaction
10- 5 s - 1 , then the rate constant at 500 K is increases from 0.3 mol L -1 s -1 to 0.6 mol L -1 s -1 .
(2019 Main, 12 Jan II) Which of the following is true? (2019 Main, 9 Jan II)
(a) The whole reaction is of 4th order
(b) The order of reaction w.r.t. B is one
Slope = –4606 (c) The order of reaction w.r.t. B is 2
ln k
(d) The order of reaction w.r.t. A is 2
16 The following results were obtained during kinetic studies of
1/ T the reaction; (2019 Main, 9 Jan I)

(a) 4 ¥ 10 -4 -1
s (b) 10 -6 -1
s
y 2A + B æÆ Products
(c) 10- 4 s- 1 (d) 2 ¥ 10- 4 s- 1 Initial rate of
[A] [B]
r
Experiment reaction
10 Decomposition of X exhibits a rate constant of 0.05 mg/year. (in mol L-1 ) (in mol L-1)
ra

(in mol L-1 min -1)

How many years are required for the decomposition of 5 mg
I. 0.10 0.20 6.93 ¥ 10-3
ib

of X into 2.5 mg? (2019 Main, 12 Jan I)

(a) 20 (b) 25 (c) 40 (d) 50 II. 0.10 0.25 6.93 ¥ 10-3
el

11. The reaction, 2 X Æ B is a zeroth order reaction. If the initial III. 0.20 0.30 1386
. ¥ 10-2
je

concentration of X is 0.2 M, the half-life is 6 h. When the

The time (in minutes) required to consume half of A is
e/

initial concentration of X is 0.5 M, the time required to reach

(a) 5 (b) 10
its final concentration of 0.2 M will be (2019 Main, 11 Jan II)
t.m

(c) 100 (d) 1

(a) 7.2 h (b) 18.0 h (c) 12.0 h (d) 9.0 h
17. Which of the following lines correctly show the temperature
12. If a reaction follows the Arrhenius equation, the plot lnk vs dependence of equilibrium constant, K , for an exothermic
1/(RT) gives straight line with a gradient (- y) unit. reaction? (2018 Main)
The energy required to activate the reactant is In K A
(2019 Main, 11 Jan I)
B 1
y
(a) unit (b) - y unit (c) yR unit (d) y unit (0, 0) T(K)
R
◊◊
◊◊
13. For an elementary chemical reaction, ◊◊
◊◊
C

= 2A , the expression for d[dtA ] is

◊◊
k1 ◊◊
D
A2
k -1 (a) A and B (b) B and C
(2019 Main, 10 Shift II) (c) C and D (d) A and D
(a) 2k1[ A2 ] - k-1[ A ]2 (b) k1[ A2 ] - k-1 [ A ]2 18. At 518°C, the rate of decomposition of a sample of gaseous
(c) 2k1[ A2 ] - 2k-1 [ A ]2 (d) k1[ A2 ] + k-1[ A ]2 acetaldehyde, initially at a pressure of 363 Torr, was 1.00
14. Consider the given plots for a reaction obeying Arrhenius Torr s -1 when 5% had reacted and 0.5 Torr s -1 when 33%
equation (0°C < T < 300°C) : ( k and E a are rate constant and had reacted. The order of the reaction is : (2018 Main)
activation energy, respectively) (2019 Main, 10 Jan I)
(a) 2 (b) 3
(c) 1 (d) 0
19. Two reactions R1 and R2 have identical pre- exponential
k k
factors. Activation energy of R1 exceeds that of R2 by 10 kJ
mol- 1 . If k1 and k2 are rate constants for reactions R1 and R2 ,
Êk ˆ
respectively at 300 K, then ln ÁÁ 2 ˜˜ is equal to
Ea T(°C)
( R = 8.314 J mol - 1K - 1 ) Ë k1 ¯ (2017 Main)
I II
(a) 8 (b) 12 (c) 6 (d) 4

Created by SIL3NT KILL3R

170 Chemical Kinetics

20. Decomposition of H2 O2 follows a first order reaction. In 50 26. Plots showing the variation of the rate constant ( k ) with
min, the concentration of H2 O2 decreases from 0.5 to 0.125 M temperature (T ) are given below. The plot that follows
in one such decomposition. When the concentration of H2 O2 Arrhenius equation is (2010)
reaches 0.05 M, the rate of formation of O2 will be (2016 Main)
(a) 6.93 ¥ 10-4 mol min -1 (b) 2.66 L min -1 at STP
k k
(c) 1.34 ¥ 10-2 mol min -1 (d) 6.93 ¥ 10-2 mol min -1 (a) (b)
21. Higher order (>3) reactions are rare due to (2015 Main)
(a) low probability of simultaneous collision of all the reacting
T T
species
(b) increase in entropy and activation energy as more molecules are
involved k k
(c) (d)
(c) shifting of equilibrium towards reactants due to elastic collisions
(d) loss of active species on collision
22. For the elementary reaction, M æÆ N , the rate of T T
disappearance of M increases by a factor of 8 upon doubling the
concentration of M . The order of the reaction with respect to M 27. For a first order reaction, A Æ P, the temperature (T )
is (2014 Adv.) dependent rate constant ( k ) was found to follow the
(a) 4 (b) 3 equation :
(c) 2 (d) 1 2000
log k = + 6.0
23. For the non-stoichiometric reaction, 2 A + B Æ C + D, the T
y
following kinetic data were obtained in three separate the pre-exponential factor A and the activation energy Ea ,
r
experiments, all at 298 K. (2014 Main) respectively, are (2009)
ra

Initial Initial Initial rate of (a) 1.0 ¥ 106 s- 1 and 9.2 kJ mol - 1
ib

concentration concentration formation of C (b) 6.0 s- 1 and 16.6 kJ mol - 1

(mol L -1s -1)
el

[A] [B]
(c) 1.0 ¥ 106 s- 1 and 16.6 kJ mol - 1
(i) 0.1 M 0.1 M 1. 2 ¥ 10-3
je

(d) 1.0 ¥ 106 s- 1 and 38.3 kJ mol - 1

(ii) 0.1 M 0.2 M 1. 2 ¥ 10-3
e/

28. Under the same reaction conditions, initial concentration

(iii) 0.2 M 0.1 M 2. 4 ¥ 10-3
t.m

of 1.386 mol dm -3 of a substance becomes half in 40 s and

The rate law for the formation of C is 20 s through first order and zero order kinetics
dC dC Êk ˆ
(a) = k[ A ][ B ] (b) = k[ A ] 2[ B ] respectively. Ratio ÁÁ 1 ˜˜ of the rate constants for first
dt dt
dC dC Ë k0 ¯
(c) = k[ A ][ B ] 2 (d) = k[ A ] order ( k1 ) and zero order ( k0 ) of the reaction is
dt dt
(2008, 3M)
24. In the reaction, P + Q æÆ R + S , the time taken for 75% (a) 0.5 mol -1 dm 3 (b) 1.0 mol dm -3
reaction of P is twice the time taken for 50% reaction of P. The (c) 1.5 mol dm -3 (d) 2.0 mol -1 dm 3
concentration of Q varies with reaction time as shown in the
figure. The overall order of the reaction is (2013 Adv.) 29. Consider a reaction, aG + bH Æ products. When
concentration of both the reactants G and H is doubled, the
rate increases by eight times. However, when
[Q]0
concentration of G is doubled keeping the concentration of
H fixed, the rate is doubled. The overall order of the
[Q]
reaction is (2007, 3M)
Time (a) 0 (b) 1
(a) 2 (b) 3 (c) 0 (d) 1 (c) 2 (d) 3

25. The rate of a reaction doubles when its temperature changes 30. Which one of the following statement(s) is incorrect about
from 300 K to 310 K. Activation energy of such a reaction will order of reaction? (2005, 1M)
(a) Order of reaction is determined experimentally
be ( R = 8.314 JK -1 mol -1 and log 2 = 0.301)
(b) Order of reaction is equal to sum of the power of
(a) 53.6 kJ mol -1 (b) 48.6 kJ mol -1 (2013 Main)
concentration terms in differential rate law
(c) 58.5 kJ mol -1 (d) 60.5 kJ mol -1
(c) It is not affected with stoichiometric coefficient of the
reactants
(d) Order cannot be fractional

Created by SIL3NT KILL3R

 Chemical Kinetics 171

31. (A) follows first order reaction, ( A ) Æ product. 39. The rate constant of a reaction depends on (1981, 1M)
Concentration of A, changes from 0.1 M to 0.025 M in (a) temperature
40 min. Find the rate of reaction of A when concentration of (b) initial concentration of the reactants
A is 0.01 M. (c) time of reaction
(2004, 1M)
(d) extent of reaction
(a) 3.47 ¥ 10–4 M min –1 (b) 3.47 ¥ 10-5 M min –1
(c) 1.73 ¥ 10 -4
M min –1
(d) 1.73 ¥ 10-5 M min –1 Objective Questions II
32. In a first order reaction the concentration of reactant (One or more than one correct option)
decreases from 800 mol/dm3 to 50 mol/dm3 in 2 ¥ 104 s. The 40. For a first order reaction A( g ) æÆ 2B( g )+ C ( g ) at
rate constant of reaction in s -1 is (2003, 1M) constant volume and 300 K, the total pressure at the
(a) 2 ¥ 104 (b) 3.45 ¥ 10-5 beginning ( t = 0 ) and at time t are p0 and pt , respectively.
(c) 1.386 ¥ 10-4 (d) 2 ¥ 10-4 Initially, only A is present with concentration [ A ]0 , and t1 / 3
33. Consider the chemical reaction, is the time required for the partial pressure of A to reach 1/3 rd
N2 ( g ) + 3H2 ( g ) æÆ 2NH3 ( g ) of its initial value. The correct option(s) is (are) (Assume that
all these gases behave as ideal gases) (2018 Adv.)
The rate of this reaction can be expressed in terms of time
derivatives of concentration of N2 ( g ), H2 ( g ) or NH3 ( g ).

In(3p0–pt)
Identify the correct relationship amongst the rate expressions (a) (b)

t1/3
d [N2 ] 1 d [H2 ] 1 d[NH3 ]
(a) Rate = - =- =
dt 3 dt 2 dt (2002, 3M)
d [N2 ] d [H2 ] d [NH3 ]
y
(b) Rate = - = -3 =2 Time [A]0
dt dt dt
r

Rate constant
d [N2 ] 1 d [H2 ] 1 d [NH3 ]
ra

(c) Rate = = =
In(p0–pt)

dt 3 dt 2 dt (c) (d)
ib

d [N2 ] d [H2 ] d [NH3 ]

(d) Rate = - =- =
dt dt dt
el

34. If I is the intensity of absorbed light and C is the

je

Time [A]0
concentration of AB for the photochemical process.
e/

AB + hn Æ AB* , the rate of formation of AB* is directly 41. In a bimolecular reaction, the steric factor P was
proportional to experimentally determined to be 4.5. the correct option(s)
t.m

(2001, 1M)
among the following is(are) (2017 Adv.)
(a) C (b) I
(a) The activation energy of the reaction is unaffected by the value
(c) I 2 (d) C ◊ I
of the steric factor
35. The rate constant for the reaction, 2N2 O5 æÆ 4NO2 + O2 (b) Experimentally determined value of frequency factor is higher
than that predicted by Arrhenius equation
is 3.0 ¥ 10-5 s -1 . If the rate is 2.40 ¥ 10-5 mol L - 1 s - 1 , then
(c) The value of frequency factor predicted by Arrhenius equation
the concentration of N2 O5 (in mol L - 1 ) is (2000, 1M) is higher than that determined experimentally
(a) 1.4 (b) 1.2 (d) Since P = 4.5, the reaction will not proceed unless an effective
(c) 0.04 (d) 0.8 catalyst is used
36. The half-life period of a radioactive element is 140 days. 42. According to the Arrhenius equation, (2016 Adv.)
After 650 days, one gram of the element will reduce to (a) a high activation energy usually implies a fast reaction
(1986) (b) rate constant increases with increase in temperature. This is
1 1 1 1
(a) g (b) g (c) g (d) g due to a greater number of collisions whose energy exceeds
2 4 8 16 the activation energy
37. A catalyst is a substance which (1983, 1M) (c) higher the magnitude of activation energy, stronger is the
(a) increases the equilibrium concentration of the product temperature dependence of the rate constant
(b) changes the equilibrium constant of the reaction (d) the pre-exponential factor is a measure of the rate at which
(c) shortens the time to reach equilibrium collisions occur, irrespective of their energy
(d) supplies energy to the reaction 43. For the first order reaction,
38. The specific rate constant of a first order reaction depends on 2N2 O5 ( g ) æÆ 4NO2 ( g ) + O2 ( g ) (2011)
the (1983, 1M) (a) the concentration of the reactant decreases exponentially with time
(a) concentration of the reactant (b) the half-life of the reaction decreases with increasing temperature
(b) concentration of the product (c) the half-life of the reaction depends on the initial concentration
(c) time of the reactant
(d) temperature (d) the reaction proceeds of 99.6% completion in eight half-life
duration

Created by SIL3NT KILL3R

172 Chemical Kinetics

44. The following statement (s) is are correct (1999, 3M) The comparison of the b- activity of the dead matter with that of the
1 carbon still in circulation enables measurement of the period of the
(a) A plot of log K p vs is linear
T isolation of the material from the living cycle. The method
(b) A plot of log [X] vs time is linear for a first order reaction, however, ceases to be accurate over periods longer than 30,000 yr.
xÆp The proportion of 14 C to 12 C in living matter is 1 : 1012.
1
(c) A plot of log p vs is linear at constant volume (2006, 3 ¥ 4M = 12M)
T
1 48. Which of the following option is correct?
(d) A plot of p vs is linear at constant temperature
V (a) In living organisms, circulation of 14 C from atmosphere is high
so the carbon content is constant in organism
45. For the first order reaction, (1998, 2M)
(b) Carbon dating can be used to find out the age of earth crust and
(a) the degree of dissociation is equal to (1 - e- kt ) rocks
(b) a plot of reciprocal concentration of the reactant vs time gives a (c) Radioactive absorption due to cosmic radiation is equal to the
straight line rate of radioactive decay, hence the carbons content remains
(c) the time taken for the completion of 75% reaction is thrice the constant in living organisms
1 (d) Carbon dating cannot be used to determine concentration of
of the reaction 14
2 C in dead beings
(d) the pre-exponential factor in the Arrhenius equation has the
49. What should be the age of fossil for meaningful
dimension of time, T -1
determination of its age?
46. A catalyst (1984, 1M) (a) 6 yr
(a) increases the average kinetic energy of reacting molecules (b) 6000 yr
(b) decreases the activation energy (c) 60,000 yr
y
(c) alters the reaction mechanism (d) It can be used to calculate any age
r
ra

(d) increases the frequency of collisions of reacting species 50. A nuclear explosion has taken place leading to increase in
concentration of C14 in nearby areas. C14 concentration is C1
ib

Numerical Value in nearby areas and C 2 in areas far away. If the age of the
el

fossil is determined to be T1 and T2 at the places respectively

47. Consider the following reversible reaction,
- then
je

A( g )+ B( g ) AB( g )
(a) the age of fossil will increase at the place where explosion has
The activation energy of the backward reaction exceeds that
e/

1 C
taken place and T1 - T2 = ln 1
of the forward reaction by 2RT (in J mol -1 ). If the l C2
t.m

pre-exponential factor of the forward reaction is 4 times that (b) the age of fossil will decrease at the place where explosion has
of the reverse reaction, the absolute value of DGs (in J 1 C
taken place and T1 - T2 = ln 1
mol -1 ) for the reaction at 300 K is ……… . l C2
(Given ; ln( 2 ) = 0.7 RT = 2500 J mol -1 at 300 K and G is the (c) the age of fossil will be determined to be the same
T C
Gibbs energy) (2018 Adv.) (d) 1 = 1
T2 C 2
Passage Based Questions
Fill in the Blanks
Passage 51. In Arrhenius equation, k = A exp (- E a / RT )
. A may be termed
Carbon-14 is used to determine the age of organic material. The
as the rate constant at ......... (1997, 1M)
procedure is based on the formation of 14 C by neutron capture in the
upper atmosphere. 52. For the reaction : N2 ( g ) + 3H2 ( g ) æÆ 2NH3 ( g )
14 1 14 1 Under certain conditions of temperature and partial pressure
7 N + 0n æÆ 6 C + 1p
14 14 of the reactants, the rate of formation of NH3 is 0.001 kg/h-1.
C is absorbed by living organisms during photosynthesis. The C
content is constant in living organism once the plant or animal dies, The rate of conversion of H2 under the same condition is ....
the uptake of carbon dioxide by it ceases and the level of 14 C in the kg /h -1 . (1994, 1M)
dead being, falls due to the decay which C-14 underoges 53. The hydrolysis of ethyl acetate in ........... medium is a ..........
14 14
6 C æÆ 7 N + b- order reaction. (1986, 1M)
14
The half-life period of C is 5770 yr. 54. The rate of chemical change is directly proportional to
The decay constant ( l ) can be calculated by using the following ............. (1985, 1M)
0.693
formula l = .
t1 / 2

Created by SIL3NT KILL3R

 Chemical Kinetics 173

True/False 63. The rate constant for an isomerisation reaction, A Æ B is

55. For a first order reaction, the rate of the reaction doubles as the 4.5 ¥ 10-3 min. If the initial concentration of A is 1 M,
concentration of the reaction (s) doubles. (1986, 1M) calculate the rate of the reaction after 1 h. (1999, 4M)

Integer Answer Type Questions 64. (i) The rate constant of a reaction is 1.5 ¥ 107 s-1 at 50∞ C and
56. An organic compound undergoes first order decomposition. 4.5 ¥ 107 s-1 at 100∞ C. Evaluate the Arrhenius parameters
The time taken for its decomposition to 1/8 and 1/10 of its A and Ea . (1998, 5M)
initial concentration are t1 / 8 and t1 / 10 respectively. What is the 1
(ii) For the reaction, N2O5 (g ) æÆ 2NO2 (g ) + O2 (g ),
[t ] 2
value of 1 / 8 ¥ 10 ? (log 10 2 = 0.3)
[ t1 / 10 ] calculate the mole fraction N2O5 (g ) decomposed at a
(2012)
constant volume and temperature, if the initial pressure is
57. The concentration of R in the reaction R æÆ P was 600 mm Hg and the pressure at any time is 960 mm Hg.
measured as a function of time and the following data is Assume ideal gas behaviour.
obtained :
65. The rate constant for the first order decomposition of a
[ R ] (molar) 1.0 0.75 0.40 0.10
certain reaction is described by the equation
t (min) 0.0 0.05 0.12 0.18
1.25 ¥ 104 K
The order of the reaction is (2010) log k (s -1 ) = 14.34 -
T
Subjective Questions (i) What is the energy of activation for the reaction?
58. 2 X ( g ) æÆ 3Y ( g ) + 2 Z ( g ) (ii) At what temperature will its half-life period be 256 min?
(1997, 5M)
y
Time 0 100 200
66. One of the hazards of nuclear explosion is the generation of
r
(in min)
Sr 90 and its subsequent incorporation in bones. This
ra

Partial pressure of 800 400 200 nucleide has a half-life of 28.1 yr. Suppose one microgram
ib

X (in mm of Hg)
was absorbed by a new-born child, how much Sr 90 will
el

Assuming ideal gas condition. Calculate remain in his bones after 20 yr. (1995, 2M)
(a) order of reaction
je

67. At 380∞ C, the half-life period for the first order

(b) rate constant
decomposition of H2 O2 is 360 min. The energy of activation
e/

(c) time taken for 75% completion of reaction

(d) total pressure when px = 700 mm (2005, 4M) of the reaction is 200 kJ mol -1 . Calculate the time required
t.m

59. For the given reaction, A + B æÆ Products for 75% decomposition at 450∞ C. (1995, 4M)

Following data are given 68. From the following data for the reaction between A and B

Initial conc. Initial conc. Initial rate [A], (mol/L) [B], (mol/L) Initial rate (mol L–1s–1) at
(m/L) (m/L) [mL–1s –1 ]
300 K 320 K
[ A ]0 [ B ]0
2. 5 ¥ 10-4 3. 0 ¥ 10-5 5. 0 ¥ 10-4 2.0 ¥ 10-3
0.1 0.1 0.05
0.2 0.1 0.1 5.0 ¥ 10-4 6.0 ¥ 10-5 4.0 ¥ 10-3 —
0.1 0.2 0.05
1. 0 ¥ 10-3 6. 0 ¥ 10-5 1. 6 ¥ 10-2 —
(a) Write the rate equation.
(b) Calculate the rate constant. (2004, 2M) Calculate
64
60. Cu (half-life = 12.8 h) decays by b emission (38%), b+ (i) the order of the reaction with respect to A and with
emission (19%) and electron capture (43%). Write the decay respect to B.
products and calculate partial half-lives for each of the decay (ii) the rate constant at 300 K.
processes. (2002) (iii) the pre-exponential factor. (1994, 5M)
61. The rate of first order reaction is 0.04 mol L–1s –1 at 10 min and
69. The gas phase decomposition of dimethyl ether follows first
0.03 mol L–1s –1 at 20 min after initiation. Find the half-life of the order kinetics
reaction. (2001, 5M)
CH3 — O— CH3 ( g ) æÆ CH4 ( g ) + H2 ( g ) + CO ( g )
62. A hydrogenation reaction is carried out at 500 K .If the same The reaction is carried out in a constant volume container at
reaction is carried out in the presence of a catalyst at the same 500∞ C and has a half-life of 14.5 min. Initially only
rate, the temperature required is 400 K. Calculate the dimethyl ether is present at a pressure of 0.40 atm. What is
activation energy of the reaction if the catalyst lowers the the total pressure of the system after 12 min? Assume ideal
activation barrier by 20 kJ mol -1 . (2000, 3M) gas behaviour. (1993, 4M)

Created by SIL3NT KILL3R

174 Chemical Kinetics
99
70. A first order reaction, A Æ B, requires activation energy of period of 42 Mo , which is a beta emitter, is 66.6 h. Find
-1 99
70 kJ mol . When a 20% solution of A was kept at 25∞ C for the minimum amount of 42 Mo required to carry out the
20 min, 25% decomposition took place. What will be the experiment in 6.909 h. (1989, 5M)
percentage decomposition in the same time in a 30% solution -6
maintained at 40°C ? Assume that activation energy remains 76. A first order gas reaction has k = 1.5 ¥ 10 per second at
constant in this range of temperature. (1993, 4M)
200∞ C. If the reaction is allowed to run for 10 h, what
percentage of the initial concentration would have change in
71. Two reactions (i) A Æ products (ii) B Æ products, follow the product? What is the half-life of this reaction?
first order [Link] rate of the reaction (i) is doubled (1987, 5M)

when the temperature is raised from 300 K to 310 K. 77. While studying the decomposition of gaseous N2 O5 , it is
The half-life for this reaction at 310 K is 30 min. At the same observed that a plot of logarithm of its partial pressure versus
temperature B decomposes twice as fast as A. If the energy of time is linear. What kinetic parameters can be obtained from
activation for the reaction (ii) is half that of reaction (i), this observation? (1985, 2M)
calculate the rate constant of the reaction (ii) at 300 K.
(1992, 3M)
78. Radioactive decay is a first order process. Radioactive
3 1
carbon in wood sample decays with a half-life of 5770 yr.
72. The nucleidic ratio, 1H to 1H in a sample of water is What is the rate constant (in yr - 1 ) for the decay? What
8.0 ¥ 10- 18 : 1. Tritium undergoes decay with a half-life fraction would remain after 11540 yr? (1984, 3M)
period of 12.3 yr. How many tritium atoms would 10.0 g of 79. A first order reaction is 20% complete in 10 min. Calculate
such a sample contain 40 yr after the original sample is (i) the specific rate constant of the reaction, and
collected.
y
(1992, 4M) (ii) the time taken for the reaction to go to 75% completion.
r
73. The decomposition of N2 O5 according to the equation, (1983, 2M)
ra

2N2 O5 ( g ) æÆ 4NO2 ( g ) + O2 ( g ) 80. Rate of reaction, A + B Æ products is given below as a

ib

is a first order reaction. After 30 min from the start of the function of different initial concentrations of A and B
el

decomposition in a closed vessel, the total pressure

[A] mol/L [B] (mol/L) Initial rate
developed is found to be 284.5 mm of Hg. On complete
je

(mol L–1 min –1 )

decomposition, the total pressure is 584.5 mm of Hg.
e/

Calculate the rate constant of the reaction. (1991, 6M)

0.01 0.01 0.005
0.02 0.01 0.010
t.m

74. In Arrhenius equation for a certain reaction, the value of A and

0.01 0.02 0.005
Ea (activation energy) are 4 ¥ 1013 s -1 and 98.6 kJ mol –1
respectively. If the reaction is of first order, at what Determine the order of the reaction with respect to A and B.
temperature will its half-life period be 10 min? (1990, 3M)
What is the half-life of A in the reaction ? (1982, 4M)

75. An experiment requires minimum beta activity produced at

the rate of 346 beta particles per minute. The half-life

Answers
1. (b) 2. (c) 3. (d) 4. (a) 48. (c) 49. (b) 50. (a) 51. T = •
5. (d) 6. (d) 7. (b) 8. (a) 52. 0.0015 53. acidic first or basic, second
9. (c) 10. (d) 11. (b) 12. (d) 54. concentration of reactant(s) at that instant
13. (c) 14. (b) 15. (c) 16. (b) 55. T 56. (9) 57. (0)
17. (a) 18. (a) 19. (d) 20. (a) 58. (960 mm Hg) 61. (25 min) 62. (100 kJ mol -1)
21. (a) 22. (b) 23. (d) 24. (d) 63. (3.26 ¥ 10 -3
mol L -1 -1
min ) 66. (6.1 ¥ 10 -7 g)
25. (a) 26. (a) 27. (d) 28. (a)
67. (20.74 min) 69. (0.75 atm) 70. (67 %)
29. (d) 30. (d) 31. (a) 32. (c)
71. (3.26 ¥ 10 -2 min -1
) 72. (5.6 ¥ 10 5)
33. (a) 34. (d) 35. (d) 36. (d) -3 -1
73. (5.2 ¥ 10 min ) 74. (311.34 K)
37. (c) 38. (d) 39. (a) 40. (a,d)
75. (3.56 ¥ 10 -16 g) 78. (0.25)
41. (a,c) 42. (b,c,d) 43. (a,b,d) 44. (a,b,d)
80. (1.386 min)
45. (a,d) 46. (b,c) 47. (+8500J/ mol)

Created by SIL3NT KILL3R

 Hints & Solutions
1. For the reaction, H2 + I2 æÆ 2HI
Key Idea The rate of a chemical reaction means the speed Given k 1 = 2.5 ¥ 10-4 dm3mol-1s -1
with which the reaction takes place.
For R æÆ P T1 = (273 + 327) K = 600 K
Rate of disappearance of R k 2 = 1 dm 3mol -1 s -1 at T2 = (273 + 527) K = 800 K
Decrease in [Link] R D[ R]
= =- k2 Ea Ê T2 - T1 ˆ
Time taken Dt Now, log = Á ˜
k 1 2.303R ÁË T1T2 ˜¯
Rate of appearance of P
Increase in conc. of P D[ P] 1 Ea Ê 800 - 600 ˆ
= =+ fi log = ÁÁ ˜˜
Time taken Dt 2.5 ¥ 10-4 2.303 ¥ 8.314 ¥ 10-3 Ë 600 ¥ 800 ¯
Given, [N2O5 ]initial = 3.00 mol L- 1 (10 ¥ 103 ) E 200
fi log = a ¥
2.5 0.019 48 ¥ 104
After 30 min, [N2O5 ] = 2 .75 mol L- 1
fi log 4 + 3 log10 -~ E ¥ 0.022
a
2N2O5 (g ) æÆ 4NO2 (g ) + O2 (g )
2 ¥ log 2 + 3
t= 0 3.0 M fi Ea =
t = 30 2.75 M
0.022
3.6 ~
From the equation, it can be concluded that = – 163.6kJ mol -1
0.022
1 - D[N2O5 ] 1 D[NO2 ]
¥ = ¥ 4. The expression for bacterial growth is
y
2 Dt 4 Dt
r
N = N 0et
ra

-1
- D[N2O5 ] - (2.75 - 3.00) mol L 0.25
= = fi N0
Dt 30 30 = e- t
ib

N
D[NO2 ] D (N2O5 ) D[NO2 ] 0.25
and =-2 fi =- 2 ¥ From 0 to 1 hour N ¢ (t ) = N 0et
el

Dt Dt Dt 30
= - 1667
. ¥ 10- 2 mol L- 1 min - 1 dN
je

From 1 hour onwards, = -5N 2

dt
e/

2. In the given reaction; x A ææÆ y B On differentiating the above equation from N ¢ to N we get.
È - d[ A ]˘ È d[ B ]˘
t.m

N t
log10 = log10 + 0.3010 -2
ÍÎ dt ˙˚ ÍÎ dt ˙˚ ÚN dN = -5Ú dt [Q At 1 hour, N ¢= eN 0]
eN0 1
Value of log 2 = 0.3010
È 1 1 ˘
Substituting 0.3010 by log2
Í N - eN ˙ = 5(t - 1)
È d[ A ]˘ È d[ B ]˘ Î 0˚
log10 - = log10 + log 2 Multiply both sides by N 0, we get
ÎÍ dt ˚˙ ÎÍ dt ˚˙
N0 1 N 1
Using logarithm rules, - = 5N 0 (t - 1) or, 0 = 5N 0 (t - 1) +
N e N e
È - d[ A ]˘ È d[ B ]˘ 1 È d [ A ]˘ È d[ B ]˘ N0 È1 ˘
= 2¥ fi- = …(i) = 5N 0t + - 5N 0
ÍÎ dt ˙˚ ÍÎ dt ˙˚ 2 ÍÎ dt ˙˚ ÍÎ dt ˙˚ ÍÎ e ˙˚
N
Using the rate equation (i) to determine the reaction involved is On comparing the above equation with equation of straight line,
2A ææÆ B y = mx + c
Option that fits correct in the above reaction is (c). 1
We get m = 5N 0, c = - 5N 0
2C2H4 ææÆ C4H8 . e
N0
\ Plot of vs t is shown aside.
3. N
Key Idea The Arrhenius equation for rate constants at two
different temperatures is
k Ea È T2 - T1 ˘
log 2 = [where, T2 > T1]
k 1 2.303R ÍÎ T1T2 ˙˚
N0
where, k 1 and k 2 are rate constants at temperatures T1 and T2, —
N
respectively.
R = Gas constant, Ea = Activation energy t(h)

Created by SIL3NT KILL3R

176 Chemical Kinetics

5. Only statement (d) is incorrect. Corrected statement is 7.

K1
A æÆ B æÆ C
K2

‘‘Activation enthalpy to form C is 15 kg mol -1 more than 5 kg

Rate of formation of B is
mol -1 that is required to form D.’’ It can be easily explained by
following graph. d[ B ]
= k 1[ A ] - k 2[ B ]
dt
È d[ B ] ˘
20 fi 0 = k 1[ A ] - k 2[ B ] Q Given, =0
ÍÎ dt ˙˚
15
Enthalpy Activation fi k 2[ B ] = k 1[ A ]
(kJ mol ) 10
–1
D enthalpy k1
fi Concentration of B, [ B ] = [A]
5 k2
A+B

Reaction C 8. Let the rate equation be k [ A ]x [ B ]y

coordinate
From Ist values,
Activation enthalpy (or energy) is the extra energy required by 0.045 = k [ 0.05 ]x [ 0.05 ]y …(i)
the reactant molecules that result into effective collision
From 2nd values,
between them to form the products.
. ]x [ 0.05 ]y
0.090 = k [ 010 …(ii)
6. In first order reaction, the rate expression depends on the
concentration of one species only having power equal to unity. From 3rd values,
nR æÆ products 0.72 = k [ 0.20 ]x [ 010
. ]y …(iii)
- d[ R ] On dividing equations (i) by (ii), we get
= k [R ] x
dt 0.045 È 0.05 ˘
y
=
0.09 ÍÎ 010
. ˙˚
r
On integration, - ln[ R ] = kt - ln[ R0 ]
ra

1 x
or ln(R ) = ln (R0 ) - kt È 0.05 ˘ È 0.05 ˘
=
ib

y = c + mx ÍÎ 010
. ˙˚ ÍÎ 010
. ˙˚
m = slope = -k (negative)
el

\ x =1
c = intercept = ln (r0 ) Similarly on dividing Eq. (ii) by (iii) we get
je

x y
The graph for first order reactions is 0.09 È 01. ˘ È 0.05 ˘
=
e/

0.72 ÍÎ 0.2 ˙˚ ÍÎ 010

. ˙˚
t.m

y
0.01 01
. È 0.05 ˘
ln (R) =
0.08 0.2 ÍÎ 01
. ˙˚
y
È 0.05 ˘
0.25 =
ÍÎ 010
. ˙˚
t
0.25 = [ 0.5 ]y
In zero order reaction,
[ 0.5 ]2 = [ 0.5 ]y
[ R ] æÆ product
- d[ R ]t \ y=2
\ = k or - d[ R ]t = kdt Hence, the rate law for the reaction
dt
Rate = k [ A ][ B ]2
On integrating, -[ R ]t = kt + c
If t = 0, [ R ]t = [ R ]0 9. The temperature dependence of a chemical reaction is expressed
by Arrhenius equation,
\ -[ R ]t = kt - [ R ]0
k = Ae- E a$ / RT …(i)
[ R ]t = [ R ]0 - kt
Thus, the graph plotted between [ r ]t and t gives a straight line Taking natural logarithm on both sides, the Arrhenius equation
with negative slope (-k ) and intercept equal to [ R ]0. becomes,
E
The graph for zero order reaction is ln k = ln A - a
RT
E
where, - a is the slope of the plot and ln A gives the intercept.
R
[R] Eq. (i) at two different temperatures for a reaction becomes,
k E Ê1 1ˆ
ln 2 = a ÁÁ - ˜˜ …(ii)
k1 R Ë T1 T2 ¯

Created by SIL3NT KILL3R

 Chemical Kinetics 177

fi In the given problem, Taking log on both sides of the Eq. (i), the equation
T1 = 400K, T2 = 500 K E
becomes ln k = ln A - a
k 1 = 10- 5 s - 1, k 2 = ? RT
E
- a (Slope) = - 4606
R
On substituting all the given values in Eq. (ii), we get ln/k
k Ê 1 1 ˆ
ln -2 5 = 4606 Á - ˜
10 Ë 400 500 ¯
k 1/RT
ln -2 5 = 2.303
10 On comparing with equation of straight line
k2 1
= 10 fi k 2 = 10- 4 s - 1 ( y = mx + c), the nature of the plot of lnk vs will be:
10- 5 RT
Therefore, rate constant for the reaction at (i) Intercept = C = ln A
500 K is 10- 4s - 1. (ii) Slope/gradient = m = - Ea = - y fi Ea = y
So, the energy required to activate the reactant, (activation
10. Given, rate constant (k) = 0.05 mg/year energy of the reaction, Ea is = y )
Thus, from the unit of k, it is clear that the reaction is zero order.
Now, we know that
a
13. The elementary reaction, A2 c k1

k -1
2A
half-life (t1/ 2 ) for zero order reaction = o follows opposing or reversible kinetics,
2k
(i) Rate of the reaction,
y
where, ao = initial concentration,
r = rforward - rbackward
r
k = rate constant
ra

5 mg = k 1[ A2 ] - k - 1[ A ]2 … (i)
t1/ 2 = = 50 years
ib

2 ¥ 0.05 mg / year (ii) Again, rate of the reaction can be expressed as,
d [ A2 ] 1 d[ A ]
el

Thus, 50 years are required for the decomposition of 5 mg of X r=- =+

into 2.5 mg. dt 2 dt
je

So, the rate of appearance of A, i.e.

11. For zero order reaction,
e/

d[ A ]
[ A0 ] - [ At ] = kt ...(i) = 2r = 2k 1[ A2 ] - 2 k - 1 [ A ]2 [from Eq. (i)]
dt
t.m

where, [ A0 ] = initial concentration

[ At ] = final concentration at time ‘t’ 14. The Arrhenius equation is,
k = rate constant k = A. e- E a / RT
[A ] where, k = rate constant,
Also, for zero order reaction, t1/ 2 = 0
2k A = Arrhenius constant, Ea = activation energy,
Given, t1/ 2 = 6 h and [ A0 ] = 0.2 M and T = temperature in K
0.2
\ 6= From the equation, it is clear that k decreases exponentially with
2k Ea . So, the plot-I is correct.
0.2 1 In the plot-II, k is plotted with temperature (in °C but not in K).
or, k= =
2 ¥ 6 60 So, at 0°C, k π 0 and k will increase exponentially with
Now, from Eq. (i) temperature upto 300°C. Therefore, the plot-II is also correct.
[ A0 ] - [ At ] = kt 15. For the reaction, 2A + B æÆ products.
Given, [ A0 ] = 0.5 M, [ At ] = 0.2 M Let, the rate expression is
1 È 1˘ r µ [ A ]a [ B ]b
\ 0.5 - 0.2 = ¥t Qk =
60 ÍÎ 60 ˙˚ a b
r2 Ê 2 A ˆ Ê 2 B ˆ
1 Expt 1 =Á ˜ Á ˜
0.3 = ¥t r1 Ë A ¯ Ë B ¯
60
2.4
t = 0.3 ¥ 60 = 18 h fi = 2a ¥ 2b fi 23 = 2a + `b
0.3
12. The temperature dependence of rate of a chemical reaction is fi 3=a+ b … (i)
expressed by Arrhenius equation as, k = Ae- E a / RT …(i) a b
r2 Ê 2 A ˆ Ê B ˆ
where, A = Arrhenius factor or frequency factor or Expt 2 =Á ˜ Á ˜
pre-exponential factor r1 Ë A ¯ Ë B ¯
R = Gas constant, Ea = Activation energy 0.6
fi = 2a ¥ 1 fi 21 = 2a fi a = 1 …(ii)
0.3

Created by SIL3NT KILL3R

178 Chemical Kinetics

\ From Eq. (i), 1 + b = 3 fi b = 2 18. For the reaction,

fi Order of the reaction (n) = a + b = 1 + 2 = 3 Decomposes
CH3CHO( g ) ææææÆ CH4 + CO
fi Order of the reaction wrt. A = 1
fi Order of the reaction wrt. B = 2 Let order of reaction with respect to CH3CHO is m.
16. Let, the rate expression is r µ [ A ] [ B ] . a b Its given, r1 = 1 torr/sec. when CH3CHO is 5% reacted i.e. 95%
unreacted. Similarly, r2 = 0.5 torr/sec when CH3CHO is 33%
From experiment I, reacted i.e., 67% unreacted.
a b
r2 Ê 0.1 ˆ Ê 0.25 ˆ Use the formula, r µ (a - x )m
=Á ˜ ¥Á ˜
r1 Ë 0.1 ¯ Ë 0.20 ¯ where (a - x ) = amount unreacted
-3 b m
6.93 ¥ 10 Ê 5ˆ r1 (a - x1 )m r1 È a - x1 ˘
fi =1 ¥ Á ˜ so, = or =
6.93 ¥ 10- 3 Ë4¯ r2 (a - x2 )m r2 ÍÎ a - x2 ˙˚
b 0 b
Ê 5ˆ Ê 5ˆ Ê 5ˆ Now putting the given values
fi 1 = Á ˜ fi Á ˜ = Á ˜ fi b =0 m
Ë4¯ Ë4¯ Ë4¯ 1 Ê 0.95 ˆ
=Á . )m or m = 2
˜ fi 2 = (141
r3 Ê 0.2 ˆ
a b 0.5 Ë 0.67 ¯
Ê 0.30 ˆ
From experiment II, =Á ˜ ¥Á ˜
r1 Ë 0.1 ¯ Ë 0.20 ¯ 19. According to Arrhenius equation
1.386 ¥ 10 -2
k = Ae- E a / RT
fi = (2)a ¥ (1.5)0
0.693 ¥ 10- 2 where, A = collision number or pre-exponential factor.
fi 2 = 2a ¥ 1 fi 21 = 2a fi a =1 R = gas constant
y
fi So, r µ [ A ]1[ B ]0 fi r µ [ A ] T = absolute temperature
r
Ea = energy of activation
ra

Order of the reaction (n) = 1

- E a1 / RT
fi Now, let for the 1st experiment, For reaction R1, k 1 = Ae …(i)
ib

r1 = k ◊ [ A ] - E a2 / RT
For reaction R2, k 2 = Ae …(ii)
el

r1 6.93 ¥ 10- 3
fi k= = = 6.93 ¥ 10- 2 s- 1 On dividing Eq. (ii) by Eq. (i), we get
je

[A] 0.1
(E a - Ea )
0.693 0.693 k2
2 1
e/

-
fi t50 = = = 10 s =e RT …(iii)
k 6.93 ¥ 10- 2 k1
t.m

17. From thermodynamics, [Q Pre-exponential factor ‘A’ is same for both

-DH ∞ DS ∞ reactions]
ln k = + …(i)
RT R Taking ln on both the sides of Eq. (iii), we get
Mathematically, the equation of straight line is Ê k ˆ E a1- E a 2
ln ÁÁ 2 ˜˜ =
y = c + mx …(ii) Ë k1 ¯ RT
After comparing Eq. (ii) with (i) we get, Given, E a 1 = E a 2 + 10 kJ mol - 1 = Ea 2 + 10,000 J mol - 1
- DH ∞ DS ∞
slope = and intercept = k2 10,000 J mol - 1
R R \ ln = =4
Now, we know for exothermic reaction DH is negative (-)ve. k 1 8.314 J mol - 1K- 1 ¥ 300 K
But here, 2.303 a
-DH ∞ 20. For first order reaction, k = log
Slope = is positive t a-x
R
Given, t = 50 min, a = 0.5 M, a - x = 0125
. M
So, lines A and B in the graph represent temperature dependence
2.303 0.5 -1
of equilibrium constant K for an exothermic reaction as shown \ k= log = 0.0277 min
below 50 0125
.
Now, as per reaction
2H2O2 æÆ 2H2O + O2
ln K A
1 d [H2O2 ] 1 d [H2O] d [O2 ]
- = =
B 2 dt 2 dt dt
1 d [H2O2 ]
Rate of reaction, - = k [H2O2 ]
(0, 0) T(K) dt
d [O2 ] 1 d [H2O2 ] 1
\ =- = k [H2O2 ] …(i)
dt 2 dt 2

Created by SIL3NT KILL3R

 Chemical Kinetics 179

When the concentration of H2O2 reaches 0.05 M, k2 - Ea Ê 1 1ˆ

25. From Arrhenius equation, log = Á - ˜
d [O2 ] 1 k1 2.303 R ÁT ˜
= ¥ 0.0277 ¥ 0.05 [from Eq. (i)] Ë 2 T1 ¯
dt 2 k2
d [O2 ] Given, = 2 T2 = 310 K
or = 6.93 ¥ 10-4 mol min -1 k1
dt
T1 = 300 K
Alternative Method
On putting values,
In fifty minutes, the concentration of H2O2 decreases from 0.5 to
0.125 M or in one half-life, concentration of H2O2 decreases - Ea Ê 1 1 ˆ
fi log 2 = Á - ˜
from 0.5 to 0.25 M. In two half-lives, concentration of H2O2 2.303 ¥ 8.314 Ë 310 300 ¯
decreases from 0.5 to 0.125 M or 2 t1/ 2 = 50 min fi Ea = 53.603 kJ/mol
t1/ 2 = 25 min
26. According to Arrehnius equation, rate constant increases
Ê 0.693 ˆ -1
exponentially with temperature :
\ k =Á ˜ min
Ë 25 ¯ k = Ae- E a / RT
d [O2 ] 1 d [H2O2 ] k [H2O2 ]
or =- = = 6.93 ¥ 10-4 mol min -1
dt 2 dt 2 27. The logarithmic form of Arrhenius equation is
Ea
21. The main conditions for the occurrence of a reaction is log k = log A -
proper orientation and effective collision of the reactants. 2.303 RT
Since, the chances of simultaneous collision with proper 2000
Given : log k = 6 -
orientation between two species in high order reactions are very T
rare, so reaction with order greater than 3 are rare. Comparing the above two equations :
y
22. For the elementary reaction, M æÆ N log A = 6 fi A = 106
r
Rate law can be written as Ea
ra

and = 2000
Rate µ [ M ] n 2.303 R
ib

Rate = k [ M ] n …(i) fi Ea = 2000 ¥ 2.303 ¥ 8.314 J

el

When we double the concentration of [ M ], = 38.3 kJ mol -1

je

rate becomes 8 times, hence new rate law can be written as ln 2

28. For first order reaction t1/ 2 = = 40 s …(i)
8 ¥ Rate = k [ 2M ] n …(ii) k1
e/

Rate k [M ]n 1 1 [ A ]0
t.m

= fi = For zero order reaction t1/ 2 = = 20 s …(ii)

8 ¥ Rate k [ 2M ] n 8 [2]n 2k 0
fi [2]n = 8 = [2]3 fi n=3 1 [ A ]0 k
fi Eq. (ii)/(i) = = ¥ 1
2 2k 0 ln 2
23. This problem can be solved by determining the order of reaction
w.r.t. each reactant and then writing rate law equation of the k 1 ln 2 0.693
fi = = = 0.5
given equation accordingly as k 0 [ A ]0 1.386
dC
R= = k [ A ]x [ B ] y 29. Rate µ [G ] m [ H ] n
dt
where, x = order of reaction w.r.t A Q Rate is double on doubling the concentration of G and
y = order of reaction w.r.t B maintaining H constant, m = 1, i.e. R µ [G ].
1. 2 ¥ 10-3 = k (0 .1)x (0 .1) y Also, when both concentration of G and H are doubled, rate
1. 2 ¥ 10-3 = k (01
. )x (0.2) y increases by a factor of 8. Here rate is increasing by a factor of 2
2.4 ¥ 10-3 = k (0.2)x (01
. )y due to G (first order in G), therefore, factor due to H is 4.
fi R µ [ H ]2
R = k [ A ]1[ B ]0
As shown above, rate of reaction remains constant as the fi Overall order = m + n = 1 + 2 = 3
concentration of reactant (B) changes from 0.1 M to 0.2 M and 30. Order of a reaction can take any real value, i.e. negative, integer,
becomes double when concentration of A change from 0.1 to 0.2, fraction etc.
(i.e. doubled).
31. For first order reaction,
24. PLAN Time of 75% reaction is twice the time taken for 50% reaction if
2.303 a 2.303 0.1
it is first order reaction w.r.t. P. From graph, [Q ] decreases k= log = log = 3.46 ¥ 10-2
linearly with time, thus it is zeroth order reaction w.r.t. Q t a-x 40 0.025
dx
= bk[ P ]a[Q ]b Rate = [ k ] A = 3.46 ¥ 10-2 ¥ 0.01 = 3.46 ¥ 10-4
dt
Order w.r.t P = a=1 [ A ]0
Order w.r.t Q =b=0
32. For a first order reaction, kt = ln
[A]
Thus, overall order of the reaction = 1 + 0 = 1

Created by SIL3NT KILL3R

180 Chemical Kinetics

1 [ A ]0 1 800 4 ln 2 - 1 2 p0
fi k= ln = ln = s or kt = ln
t [ A ] 2 ¥ 104 50 2 ¥ 104 ( 3 p0 - pt )
= 1.386 ¥ 10- 4 s- 1 or kt = ln 2 p0 - ln ( 3 p0 - pt )
33. For any general reaction, or ln ( 3 p0 - pt ) = - kt + ln 2 p0
aA + bB æÆ cC + dD It indicates graph between ln (3p0 - pt ) vs ‘t’ will be a straight
1 d [A] 1 d[ B ] line with negative slope , so option (a) is correct
Rate = - =-
a dt b dt 1 p0 1
1 d [C ] 1 d [ D ] t1/3 = ln = ln 3
= = k p0 / 3 k
c dt d dt
fi For N2 + 3H2 æÆ 2NH3 It indicates t1/ 3 is independent of initial concentration so, option
d [ N2 ] 1 d [ H2 ] 1 d [ NH3 ] (b) is incorrect.
Rate = - =- = Likewise, rate constant also does not show its dependence over
dt 3 dt 2 dt
initial concentration. Thus, graph between rate constant and
34. Rate will be directly proportional to both concentration and [ A ]0 will be a straight line parallel to X-axis.
intensity, i.e. rate of formation of AB * µ C ◊ I .
41. If steric factor is considered, the corrected Arrhenius equation
35. The unit of rate constant (t - 1) indicating that the decomposition will be
reaction following first order kinetics. -Ea

fi Rate = k[ N2O5 ] k = pAe RT where A = frequency factor by Arrhenius.

Rate 2.40 ¥ 10-5 Q p > 1, pA > A hence, (a) is correct.
[ N2O5 ] = = = 0. 8 M
k 3 ¥ 10-5 Activation energy is not related to steric factor.
y
560 k = Ae- E a / RT
r
36. 560 days = = 4 half-lives. 42. Rate constant,
ra

140
where, Ea = activation energy and A = pre-exponential factor
Amount of reactant remaining after n-half-lives
ib

n 4
(a) If Ea is high, it means lower value of k hence, slow reaction.
Ê 1ˆ Ê 1ˆ 1 Thus, incorrect.
el

= Á ˜ ¥ initial amount = Á ˜ ¥ 1.0 g = g

Ë 2¯ Ë 2¯ 16 (b ) On increasing temperature, molecules are raised to higher
je

energy (greater than Ea ), hence number of collisions

37. A catalyst increases the rate of reaction but by the same factor to
e/

increases. Thus, correct.

both forward and backward directions. Hence, a catalyst shorten
the time required to reach the equilibrium. E d (log k ) E
(c) log k = log A - a fi = a2
t.m

RT dT RT
38. Specific rate constant of reaction depends on temperature.
Thus, when Ea is high, stronger is the temperature
39. The rate constant (k ) of all chemical reactions depends on dependence of the rate constant. Thus, correct.
temperature. (d) Pre-exponential factor (A) is a measure of rate at which
k = Ae- E a / RT collisions occur. Thus, correct.
where, A = pre-exponential factor, Ea = activation energy. 43. (a) For a first order reaction, the
concentration of reactant remaining
40. Given for the reaction (at T= 300 K and constant volume = V) after time t is given by [A]
A ( g ) æÆ 2B ( g ) + C ( g ) [ A ] = [ A ] 0 e– kt
at t = 0 p0 – –
Therefore, concentration of reactant
at t = t p0 - x 2x x t
decreases exponentially with time.
È 2 p0 ˘ p0 4 p0 2 p0
at t = t1/ 3 p
Í 0 - = (b) Rise in temperature increases rate constant (k) and therefore
Î 3 ˙˚ 3 3 3
decreases half-life (t1/ 2) as
We can calculate,
ln 2
pt = p0 - x + 2x + x = p0 + 2x t1/ 2 =
p - p0 k
or 2x = pt - p0 or x = t (c) Half-life of first order reaction is independent of initial
2
concentration.
Now for first order reaction,
1 p0 (d) For a first order reaction, if 100 moles of reactant is taken
t = ln initially, after n half-lives, reactant remaining is given by
k ( p0 - x) n 8
Putting the value of x in the equation, Ê 1ˆ Ê 1ˆ
% A = 100 Á ˜ = 100 Á ˜ = 0.3906
2
Ë ¯ Ë 2¯
1 p0 1 2 p0
t = ln = ln fi A reacted = 100 – 0.3906 = 99.6%
k Ê p - p 0 ˆ k 2 p0 - pt + p0
p0 - Á t ˜
Ë 2 ¯

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 Chemical Kinetics 181

44. Equilibrium constant is related to temperature Now, DG ∞ = - RT ln K eq = - 2500 ln(4 e2 )

DH
log K p = constant - = - 2500 (ln 4 + ln e2 ) = - 2500 (1.4 + 2)
2.3 RT
fi Plot of log K p vs 1/ T will be a straight line. = - 2500 ¥ 3.4 = - 8500 J/mol
For the first order reaction X Æ P Absolute value = 8500 J/mol

log
[ X ]0
=
kt
fi log [ X ] = log [ X 0 ] -
kt
,
48. Living plants maintain an equilibrium between the absorption of
[ X ] 2.3 2.3 C14 (produced due to cosmic radiation) and the rate of decay of
C14 present inside the plant. This gives a constant amount of C14
i.e. log [ X ] vs ‘t’ will give a straight line.
per gram of carbon in a living plant.
Also at constant temperature, pV = constant
49. Fossil whose age is closest to half-life of C-14 (5770 yr) will
1
fi Plot of p vs will give a straight line. yield the most accurate age by C-14 dating.
V N
50. lT = ln 0
45. For a first order reaction : N
1 where N 0 = Number of C14 in the living matter and
kt = ln where, a = degree of dissociation. N = Number of C14 in fossil. Due to nuclear explosion,
1- a
amount of C14 in the near by area increases. This will increase
fi 1 - a = e- kt fi a = 1 - e- kt N 0 because living plants are still taking C-14 from atmosphere,
1 ekt during photosynthesis, but N will not change because fossil will
Also = , i.e. plot of reciprocal of concentration of not be doing photosynthesis.
[ A ] [ A ]0
fi T (age) determined in the area where nuclear explosion has
reactant vs time will be exponential. occurred will be greater than the same determined in normal
1 100 2 ln 2
y
Time for 75% = ln = = 2 (t1/ 2 ) area.
r
k 100 - 75 k C C 1 C
Also, lT1 = ln 1 fi lT2 = ln 2 fi T1 - T2 = = ln 1
ra

The Arrhenius equation is : C C l C2

ib

Ea C = Concentration of C-14 in fossil.

ln k = ln A -
RT
el

The dimensions of k and A must be same. For first order 51. k = A e- Ea / RT : At T = • , k = A

je

reaction, dimensions of k is t - 1. 1 d [ H2 ] 1 d [ NH3 ]

52. - =
3 dt 2 dt
e/

46. A catalyst lowers the activation energy by enabling the reaction

to continue through an alternative path, i.e. catalyst changes the - d [ H2 ] 3 d [ NH3 ] 3
fi = = ¥ 0.001 = 0.0015 kg h - 1 .
t.m

reaction mechanism. However, catalyst does not affect either dt 2 dt 2

average kinetic energies of reactants or the collision frequency.
53. acidic, first or basic, second.
47. For the reaction,
A (g ) + B (g ) - AB(g ) 54. Rate is directly proportional to concentration of reactants.
55. R µ [Reactant]
Given Ea b = Ea f + 2RT or Ea b - Ea f = 2RT
Further On doubling the concentration of reactant, rate would be double.
Af [ A ]0
A f = 4 Ab or =4 56. For a first order process kt = ln
Ab [A]
Now, rate constant for forward reaction, where, [ A ]0 = initial concentration.
- E a f / RT [ A ] = concentration of reactant remaining at time “t”.
k f = Af e
[ A ]0
Likewise, rate constant for backward reaction, fi kt1/ 8 = ln = ln 8 …(i)
[ A ]0 / 8
- E ab / RT
k b = Ab e [ A ]0
and kt1/ 10 = ln = ln 10 …(ii)
At equilibrium, [ A ]0 /10
Rate of forward reaction = Rate of backward reaction t1/ 8 ln 8
Therefore, = = log 8 = 3 log 2 = 3 ¥ 0.3 = 0.9
kf t1/ 10 ln 10
i.e., k f = k b or = k eq
kb t1/ 8
fi ¥ 10 = 0.9 ¥ 10 = 9
- E a f / RT t1/ 10
Af e Af - (E a f - E ab ) / RT
so k eq = = e
Ab e
- E ab / RT
Ab 57. Rate of reaction is constant with time.
After putting the given values 58. (a) Partial pressure becomes half of initial in every 100 min,
2 Af therefore, order = 1.
k eq = 4 e (as Ea b - Ea f = 2RT and = 4) 800
Ab (b) k ¥ 100 = ln = ln 2 fi k = 6.93 ¥ 10-3 min - 1
400

Created by SIL3NT KILL3R

182 Chemical Kinetics

(c) For 75% reaction; time required = 2 ¥ half-life = 200 min 62. k 500 = A e- E1 / RT1
(d) 2 X (g ) æÆ 3Y (g ) + 2 Z (g ) k 400 = A e- E 2 / RT2
3
800 - x x x
2 Q k 500 = k 400
3 E1 E E2 T2 400 4
Total pressure = 800 + x fi = 2 fi = = =
2 RT1 RT2 E1 T1 500 5
Also 800 - x = 700 fi x = 100 Also E1 = E2 + 20000 J
3 E1 - 20,000 4
fi Total pressure = 800 + ¥ 100 = 950 mm Hg fi = fi E1 = 100,000 J = 100 kJ mol -1
2 E1 5
a
(Rate)1 0.05 1 Ê 1 ˆ [ A ]0
59. = = = Á ˜ fi a = 1; order w.r.t A. 63. kt = ln
(Rate)2 0.10 2 Ë 2 ¯ [A]
Order w.r.t B = 0 1
fi 4.5 ¥ 10- 3 ¥ 60 = ln fi [ A ] = 0.76 M
(a) Rate = k [ A ] [A]
Rate 0.05 fi Rate = k [ A ] = 4.5 ¥ 10- 3 ¥ 0.76
(b) k = = = 0.5 s- 1
[ A ] 0.10 = 3.42 ¥ 10-3 mol L-1 min -1
64 38% 0 64 k 2 Ea Ê T2 - T1 ˆ
60. 29 Cu æÆ - 1b + 30Zn 64. (i) ln = ÁÁ ˜˜
k1
k1 R Ë T1T2 ¯
64 19% 0 64
29 Cu æÆ + 1b + 28 Ni Ê 4.5 ¥ 107 ˆ Ea Ê 50 ˆ
k2 fi ln ÁÁ ˜= ÁÁ ˜˜
7˜
Ë 1.5 ¥ 10 ¯ 8.314 Ë 323 ¥ 373 ¯
y
64 0 43% 64
29 Cu + - 1e æÆ 28 Ni
r
k3 fi Ea = 22 kJ
ra

64 Ea
Above are the parallel reactions occurring from Cu . Also ln k = ln A -
RT
ib

k 1 38 T k 1 38 T3
= = 2 = 2 and = = 22 ¥ 1000
k 2 19 T1 k 3 43 T1 At 50°C : ln A = ln (1.5 ¥ 107 ) - = 8.33
el

8.314 ¥ 323
T1 , T2 and T3 are the corresponding partial half-lives.
je

fi A = 4.15 ¥ 103 s- 1
Also k = k1 + k2 + k3
e/

1
ln 2 ln 2 ln 2 ln 3 (ii) N2O5 (g ) æÆ 2NO2 (g ) + O2 (g )
fi = + + 2
t.m

T T1 T2 T3
600 - p 2p p/ 2
1 1 1 1 1 1 43
fi = + + = + + 3
T T1 T2 T3 T1 2T1 38T1 Total pressure = 960 = 600 + p fi p = 240 mm
2
1 Ê 1 43 ˆ fi Partial pressure of N2O5 (g ) remaining = 600 – 240
= Á1 + + ˜
T1 Ë 2 38 ¯ = 360 mm
1 Ê 38 + 19 + 43 ˆ 100 360
= Á ˜= fi Mole fraction = = 0.375
T1 Ë 38 ¯ 38T1 960
100T 100 65. (i) The Arrhenius equation is
fi T1 = = ¥ 12.8 = 33.68 h Ea
38 38 log k = log A -
2.303 RT
T2 = 2T1 = 67.36 h
38T1 38 ¥ 33.68 Comparing with the given equation :
T3 = = = 29.76 h Ea
43 43 1.25 ¥ 104 = fi Ea = 239.33 kJ mol -1
2.303 R
61. R = k [A] (ii) When half-life = 256 min,
fi R1 = k [ A ]1 and R2 = k [ A ]2 ln 2 0.693 - 1
k= = s = 4.5 ¥ 10- 5 s- 1
R1 4 [ A ]1 t1/ 2 256 ¥ 60
fi = =
R2 3 [ A ]2 1.25 ¥ 104
fi = 14.34 – log 4.5 ¥ 10- 5 = 16.68
[ A ]1 4 T
Also k (t2 - t1 ) = ln = ln
[ A ]2 3 1.25 ¥ 104
fi T = = 669 K
ln 2 4 16.68
fi ¥ 10 = ln
t1/ 2 3 w
66. k t = ln 0
10 log 3 3 w
fi t1/ 2 = = = 25 min
log 4 - log 3 0.6 - 0.48 ln 2 10- 6 g
fi ¥ 20 = ln fi w = 6.1 ¥ 10- 7 g
28.1 w

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 Chemical Kinetics 183

67. For 1st order reaction : Ï k (40∞ C) ¸ Ea Ê 15 ˆ

1
70. ln Ì ˝= ÁÁ ˜˜
kµ Ó k (25 ∞ C ) ˛ R Ë 298 ¥ 313 ¯
t1/ 2 70 ¥ 1000 15
= ¥ = 1.35
Ï k (450∞ C) ¸ Ï t1/ 2 (380∞ C) ¸ Ea Ê 450 - 380 ˆ 8.314 298 ¥ 313
fi ln Ì ˝ = ln Ì ˝= ÁÁ ˜˜
Ó k (380∞ C) ˛ Ó t1/ 2 (450∞ C) ˛ R Ë 727 ¥ 653 ¯ k (40∞ C)
fi = 3.87
Ï 360 ¸ 200 ¥ 103 70 k (25∞ C)
fi ln Ì ˝= ¥ = 3.54
t
Ó 1/ 2 (450 ∞ C) ˛ 8.314 727 ¥ 653 1 100 1 4
Also k (25°C) = ln = ln
fi t1/ 2 (450°C) =10.37 min 20 75 20 3
fi Time for 75% reaction at 450°C fi k (40∞ C) = 3.87 ¥ k (25°C)
1 4
= 2 ¥ t1/ 2 = 2 ¥ 10.37 = 20.74 min = 3.87 ¥ ln = 55.66 ¥ 10- 3 min - 1
20 3
68. Comparing the data of experiment number 2 and 3 : 100
m Now k (40°C) ¥ 20 = ln
R3 1.6 ¥ 10- 2 Ê 1.0 ¥ 10- 3 ˆ 100 - x
= = ÁÁ ˜
-4 ˜ 100
R2 4 ¥ 10- 3 Ë 5 ¥ 10 ¯ fi 55.66 ¥ 10- 3 ¥ 20 = ln fi x = 67%
100 - x
fi m = 2, order w.r.t. A
A k
Now comparing the data of experiment number 1 and 2 : 71. (i) A æÆ Product
2 -5 n
R2 4 ¥ 10-3 Ê 5 ¥10- 4 ˆ Ê 6.0 ¥ 10 ˆ kB
= =Á ˜ Á ˜ (ii) B æÆ Product
R1 5 ¥ 10- 4 ÁË 2.5 ¥ 10- 4 ˜¯ Á 3.0 ¥ 10-5 ˜
Ë ¯ EaÊ 10 ˆ
For (i) ÁÁ ˜˜ = ln 2
y
fi 8 = (2)2 (2)n fi n = 1, order w.r.t. B. R Ë 300 ¥ 310 ¯
r
(i) Order with respect to A = 2, order with respect to B = 1.
ra

fi Ea (i) = 9300 R ln 2 = 53.6 kJ

(ii) At 300 K, R = k [ A ]2 [ B ] E (i )
= a
ib

fi Ea (ii) = 26.8 kJ
R 5.0 ¥ 10- 4 2
fi k= =
el

[ A ] [ B ] (2.5 ¥ 10- 4 )2 (3.0 ¥ 10- 5 )

2 At 310 K t1/ 2 (i) = 30 min
Q Rate of (ii) = 2 rate of (i)
je

= 2.66 ¥ 108 s- 1 L2 mol -2

fi t1/ 2 (ii) = 15 min
e/

(iii) From first experiment :

Now for reaction (ii) :
Rate (320 K) = k (320 K) (2.5 ¥ 10- 4 )2 (3.0 ¥ 10- 5 )
t.m

Ï k (310) ¸ Ï t1/ 2 (300) ¸ Ea (ii ) Ê 10 ˆ

ln Ì B ˝ = ln Ì ˝= ÁÁ ˜˜
2 ¥ 10-3 k (300) t (310 ) R 300 ¥ 310
fi k (320 K) = Ó B ˛ Ó 1/ 2 ˛ Ë ¯
(2.5 ¥ 10- 4 )2 (3.0 ¥ 10- 5 )
Ï t (300) ¸ ln 2
fi ln Ì 1/ 2 ˝= fi t1/ 2 (300) = 21.2 min
= 1.066 ¥ 109 s- 1 L2 mol - 2. Ó 15 ˛ 2
Ï k (320 K) ¸ Ea Ê T2 - T1 ˆ ln 2 0.693
fi ln Ì ˝= ÁÁ ˜˜ fi k B (300) = = = 3.26 ¥ 10- 2 min - 1
Ó k (300 K) ˛ R Ë T1T2 ¯ t1/ 2 21.2

Ê 1.066 ¥ 109 ˆ Ea Ê 20 ˆ 72. Initially :

fi ln ÁÁ ˜=
8 ˜
ÁÁ ˜˜ 10 20
Ë 2.66 ¥ 10 ¯ 8.314 Ë 300 ¥ 320 ¯ N (1 H3 + 1H1 ) = ¥ 2 ¥ 6 ¥ 1023 = ¥ 1023
8 3
fi Ea = 55.42 kJ mol -1 N (1 H1 ) 20 ¥ 1023
fi 1+ =
Ea N (1 H3 ) 3N (1 H3 )
Now ln k = ln A -
RT 1 20 ¥1023
3 fi 1+ = ª 1.25 ¥ 1017
55.42 ¥ 10 8 ¥ 10 - 18
3N (1 H3 )
At 300 K : ln (2.66 ¥ 108 ) = ln A -
8.314 ¥ 300 20 ¥ 1023
fi N (1 H 3 ) = = 5.33 ¥ 106
Solving : ln A = 41.62 fi A = 1.2 ¥ 1018 3 ¥ 1.25 ¥ 1017
69. CH3 æ O æ CH3 (g ) æÆ CH4 (g ) + H2 (g ) + CO (g ) N0 ln 2 5.33 ¥ 106
fi kt = ln fi ¥ 40 = ln
At 12 min : 0.40 - p p p p
N 12.3 N
Total pressure = 0.4 + 2p fi N = 5.6 ¥ 105
0.40 ln 2 73. For the reaction :
Also k ¥ 12 = ln = ¥ 12 = 1.77 fi p = 0.175
0.40 - p 14.5 2N2O5 æÆ 4NO2 + O2
fi Total pressure = 0.4 + 2p = 0.4 + 2 ¥ 0.175 = 0.75 atm If p0 is the initial pressure, the total pressure after completion of
5
reaction would be p0.
2

Created by SIL3NT KILL3R

184 Chemical Kinetics

5 100
fi 584.5 = p0 fi p0 = 233.8 mm fi = 1.055
2 100 - x
Let the pressure of N2O5 decreases by ‘p’ amount after 30 min. fi x = 5.25% reactant is converted into product.
Therefore, ln 2 0.693
Half-life = = = 462000 s = 128.33 h
2N2O5 æÆ 4NO2 + O2 k 1.5 ¥ 10- 6
p
At 30 min : p0 - p 2p
2 [ A ]0
77. For a first order process : ln = kt fi ln [ A ] = ln [ A ]0 - kt
3 [A]
Total pressure = p0 + p = 284.5
2 If the reactant is in gaseous state
2 [ A ]0
fi p= (284.5 - 233.8) = 33.8 and kt1/ 10 - ln = ln 10 …(ii)
3 [ A ]0 / 10
p0
Now, kt = ln t ln 8
p0 - p Therefore, 1/ 8 = = log 8 = 3 log 2 = 3 ¥ 0.3 = 0.9
t1/ 10 ln 10
1 233.8
fi k= ln min - 1 = 5.2 ¥ 10- 3 min - 1 t1/ 8
30 233.8 - 33.8 fi ¥ 10 = 0.9 ¥ 10 = 9
t1/ 10
74. Arrhenius equation is : ln p = ln p0 - kt …(i)
Ea where p is the partial pressure of reactant remaining unreacted at
log k = log A -
2.303 RT instant ‘t’ and p0 is its initial partial pressure.
ln 2 0.693 Also, from equation (i), ln p vs t would give a straight line.
when t1/ 2 = 10 min, k = = = 1.115 ¥ 10- 3 s- 1
t1/ 2 10 ¥ 60 Therefore, decomposition of N2O5 following first order kinetics.
y
Ea ln 2 0.693 - 1
78. k = yr = 1.2 ¥ 10- 4 yr - 1
r
fi = log A - log k =
ra

2.303 RT t1/ 2 5770

A 4 ¥ 1013 1 ln 2 1
Also kt = ln = ¥ 11540 = ln 4 fi f = = 0.25
ib

= log = log = 16.54 f 5770 4

k 1.115 ¥10- 3
el

Ea 98.6 ¥ 1000 79. For a first order reaction,

fi T = =
je

2.303 R ¥ 16.54 2.303 ¥ 16.54 ¥ 8.314 [ A ]0

kt = ln
e/

= 311.34 K [A]
where [ A ]0 = Initial concentration of reactant
t.m

75. The minimum rate of decay required after 6.909 h is

346 particles min - 1. [ A ] = Concentration of reactant remaining
unreacted at time t.
fi Rate = kN
1 [ A ]0 1 100 1 5
Rate 346 ¥ 66.6 ¥ 60 (i) fi k = ln = ln = ln
fi N = = = 1.995 ¥ 106 atoms t [ A ] 10 100 - 20 10 4
k 0.693
N ln 2 N 2.303 (log 5 - 2 log 2)
fi kt = ln 0 fi ¥ 6.909 = ln 0 = 0.0715 = min - 1 = 0.023 min –1
N 66.6 N 10
N0 1 100 2 ln 2 2 ¥ 0.693
fi = 1.074 (ii) t = ln = = = 60 min
N k 25 k 0.023
fi N 0 = 1.074 ¥ N = 1.074 ¥ 1.995 ¥ 106 80. Looking at the rate data of experiment number 1 and 2 indicates
= 2.14 ¥ 106atoms of Mo that rate is doubled on doubling concentration of A while
concentration of B is constant. Therefore, order with respect to A
2.14 ¥ 106 is 1. Similarly, comparing data of experiment number 1 and 3,
fi Mass of Mo required = ¥ 99 = 3.56 ¥ 10- 16 g
6.023 ¥ 1023 doubling concentration of B, while concentration of A is
constant, has no effect on rate.
76. k = 1.5 ¥ 10- 6 s- 1 Therefore, order with respect to B is zero.
100 fi Rate = k [ A ]
kt = ln
100 - x 0.005 0.693
fi k= = 0.5 min - 1 =
100 0.010 t1/ 2
fi ln = 1.5 ¥ 10- 6 s- 1 ¥ 10 ¥ 60 ¥ 60 s = 0.0054
100 - x 0.693
fi t1/ 2 = = 1.386 min
0.5

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