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CHEMICAL KINETICS
EXERCISE - I
Single Answer Correct Type
dx
1. rate k[A0 ]n
dt
log [Rate] = log k + n log [A0]
When n = 0, slope = 0 n order
2. CHEM ACADEMY
When n = 1 slope = 1
2NO O 2 (g) 2NO 2 (g)
Rate = k [O2] [NO]2
n O2 n NO 2
Rate = k V V
n O2 n NO 2
Rate´ = k V / 2 V / 2
n O2 n NO 2
Rate´ = 4 × 2k V V = 8 Rate
3. HA + B BH+A–
[BH A ]
Rate constant = k =
[HA][B]
Rate k f [HA][B]
Rate k b [BH A ]
k f [HA][B]
1
k b [BH A ]
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CHEM ACADEMY 2 Chemical Kinetics (Solution)
4. AP
Rate = k[A]n
k[0.01]n 10 4
R1 =
k[0.02]n 1.41104
n
0.02
1.41 n = 0.5
0.01
(2n) = (1.41) n log 2 = log 1.41
d[A]
k[A]1/ 2
dt
k
5.
1
A Bk2
d(B) d(A)
For backward Rate = k 2 (B)1 k 2 [B]
dt dt
Net reaction rate of B is = k1 – k2 [B]
6. NO H 2 N 2 H 2O
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CHEM ACADEMY 3 Chemical Kinetics (Solution)
R1 = k[PNO ]
1.5 k[350]
350 1.5
0.25 k[152] Dividing
152 0.25
=2
R 2 k[PH2 ]
d[A]
kdt
[A]
A
CHEM ACADEMY
ln kt
A0
8. Ag 2NH3 [Ag(NH3 )2 ]
k f 2 107 L2 mol2s 1
= 2×109 L2 mol–2
kb 10 2 s 1
(I) (II)
conc.
9.
time
I: Concentration of A and B are changing with respect to time. Hence, it represents kinetic region.
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CHEM ACADEMY 4 Chemical Kinetics (Solution)
II: Concentration of both the species is constant Equilibrium region.
10. A + B P
1 1 0
1 1
Rate at t = 10–2
2 4
102 1.25 103
8
11. Rate = k[CH3COCH3][Br2] [H+]r
=0
12.
dt
CHEM ACADEMY
d(NO 2 )
k(NO 2 ) 2
1 d[Br2 ] 1 [Br ]
13. = d
3 dt 5 dt
d[Br2 ] 3 [Br ]
d
dt 8 dt
14. R1 = k[A]n[B]m
m
3
R2 = k[2A]n 2
1
R2 = 2nk[A]n × m
[B]m
2
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CHEM ACADEMY 5 Chemical Kinetics (Solution)
1
R 2 2n R1
2m
R2
2n . 2 m 2n m
R1
15. I. [C] = 0.0033 M at t = 25 min
II. [C] = 0.0039 M at t = 15 min
III. [C] = 0.0077 M at t = 7.5 min
d[C] 0.0033
in I = 1.32 104 M min 1
dt 25
d[C] 0.0039
in II = 2.6 104 M min 1
dt 15
d[C] 0.0077
in III = 1.02 103 M min 1
dt 7.5
1.3 104
17.
k
k=?
CHEM ACADEMY
102 5 102
0.26
Rate = k[A]2[B]
k 2.6 101
Correct answer is (c)
18. 2N 2O5 4NO2 O 2
1 d(N 2O5 ) 1 d(NO 2 ) d(O2 )
Rate
2 dt 4 dt dt
d(N 2O5 ) d(NO 2 ) d(O 2 )
k1 k2 k3
dt dt dt
2 2
k1 k 2 k 3
2 4
k2
k1 k3 2k1 k 2 k 3
2
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CHEM ACADEMY 6 Chemical Kinetics (Solution)
d(N 2O5 )
1 mol hr 1 1 108 108 g hr 1
dt
20. Rate = k[A]
R1 = k[A]n
R2 = k[1.5 A]n = 2.25 R1
8 105 k[0.2]
22. =
3.2 104 k[0.4]
CHEM ACADEMY
1 8 105
2 32 105
=2
0.5 3.2 104 32
2.0 12.8 104 128
1 1
1
4 4
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CHEM ACADEMY 7 Chemical Kinetics (Solution)
23. Rate = k[A][B]
n n
R = Initial Rate = k A B
V V
1
If volume of reaction is suddenly reduced to of initial value.
4
nA n
k B
R1 = new rate = 1 1
V V
4 4
1
R = 16 R New rate will be affected by 16.
Correct answer is (d).
24. The rate constant of reaction does not depend on concentration of reactant & product (only on
nature of reactant & product)
25. A + B Products
H = k[A][B] [if B is taken in large excess then according to pseudo first order reaction. B is taken
as constant]
So order = 1
dA dB
2
dt dt
Correct answer is (d)
27. The rate of reaction that does not involve gases does not depend on pressure.
Correct answer is (a)
1
28. c c0e k1t Tav
K1
1
2k1
c c0e k1 2Tav c c0 e k1
c 100
100 e 2 100% 2 %
c0 e
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CHEM ACADEMY 8 Chemical Kinetics (Solution)
29. For n = 2
1
T50
k a A0
1 1
kt
A A0
4 1 3 3
k t 75 k t 75 t 75
A0 A0 A0 A 0K
1 t 75
t 50 3
kA 0 t 50
t 75 3 t 50
1
For n = 2 t 50
kA 0
but t 75 3 t 50
(c) is wrong statement for n = 2.
30.
V V0
V Vt CHEM ACADEMY
2 =
a0
a0 / 2 [When t = t1/2]
V V0 2V 2Vt
V 2Vt V0
31. A + 2B C + D
t=0 0.6 0.8 – –
t=1 0.4 0.4 0.2
R1 k[0.6][0.8]2
R 2 k[0.4][0.4]2
R1 3 3
(2) 2 2 2 6
R2 2 2
R1 6R 2
1
R2 R1
6
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CHEM ACADEMY 9 Chemical Kinetics (Solution)
1 1
32. kt
(A x) A 0
1
m = k = 0.5 2 A0 = 0.5
A0
Rate = 0.5 × (0.5)2 = 0.5 × 0.25 = 0.125
1 1
33. kt
[A] [A 0 ]
A P
A0 –
(A0 – x) (x)
x x
1 1
kt
A0 x A 0
1 1 A 0 kt
(A 0 x) A0
CHEM ACADEMY
A0 x
A0
1 A 0 kt
A0
x A0
1 A 0 kt
0.693 A0
34. k1 A 0 k 0 (20)
40 2
A0
20k 0
2
1.386 mol dm 3
k0
40
k1 0.693 40
0.5
k0 40 1.386
1.5 103
35. 0.81 M 1s 1 [4 103 ]2
2t
1.5 103
2t 6
0.115 103 = 115 s
0.8116 10
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CHEM ACADEMY 10 Chemical Kinetics (Solution)
115
t=
2
1 1
103 0.810 t
(4 1.5) 4 103
1 1
20.81 t
2.5 103 4 103
t = 0.926s
1
36. t1/ 2
(a 0 )n 1
t1 (a1 )n 1 t 2 (a 2 )n 1
37. k
2.303
t
CHEM ACADEMY
r r
log t
r r0
2.303 r r
k log 0
t r rt
2.303 10.7 24.1
k log
t 10.7 10.0
2.303
k log[1.6811]
t
2.303 0.2256
k = 0.011 min–1
t
When optical rotation = 0
r 0
2.303 rt
t log
k r0
2.303 10.0
t log 107.2 min
2.303 0.2256 24.1
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CHEM ACADEMY 11 Chemical Kinetics (Solution)
38. (a – x) vs t for zero order reaction, the plot is linear
For n = 0 A0
A = A0 – kt m=–k n=0
a – x = A0 – kt a–x
y = c + mx
c = A0 m=–k t
d[A]
39. k[A]1/ 2
dt
A
d[A] 2 A0
[A]1/ 2 kdt t 3/ 4
k 4
A0
A0
(2 A) A
A0 kt 2(A)1/ 2 kt
2
k ( A A0 )
t
When t t1/2 A A0/2
40. t10%
CHEM ACADEMY
2.303
k
100
log
90
2.303 100
t19% = log
k 81
2.303 100
log
= log 10 81
9
10
log
20 9
t19% 100
log
81
2.303 100
20 log
k 90
2.303 100
t19 log
k 81
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CHEM ACADEMY 12 Chemical Kinetics (Solution)
100
log
20 90 20
0.5
t19% 100 t19%
log
81
t19% = 40 min.
1 1.08 102 0.36 102
41. R mol L1s 1 = 0.09 × 10–2 = 9 × 10–4
4 3 4
1
42. for nth order t1/ 2
(A 0 )n 1
Varies inversely as (n – 1)th power
Correct answer is (b)
43. n = 2, t1/2 = 400 s Pi = 250 torr
1 1
kt
A A0
2 1
kt1/ 2
A 0 A0
CHEM ACADEMY
t1/ 2
1
A0k
Pi A 0
1
400
250 k
1
k 105 T 1s 1
250 400
pV = nRT
V RT V 1
K 105 T 1s 1
n P n P
105
t1/ 2 0.5 103
200
t1/2 = 500 s
44. AP
1 sec.
1 0.5 0.33 0.25
2 sec.
3 sec.
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CHEM ACADEMY 13 Chemical Kinetics (Solution)
for n = 2
1 sec. 2 sec.
1 0.5 0.25
It is 2nd order.
3 sec.
2.303
46. t 90
k
k
2.303
90
CHEM ACADEMY
A0
log
0.1A 0
2.303
k log10
90
0.693
t 50 90 = 27 min.
2.303
0.693
47. k=
10
0.693
Rate = 5 = 0.0693 × 5
10
48. Taverage Tavg, n = 1
1
Tavg A A 0c kt
K
1
k
A A 0c k
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CHEM ACADEMY 14 Chemical Kinetics (Solution)
A0 A0
A
e 2.718
A 1
0.37 ~ 37%%
A 0 2.78
Fraction of sample left
Fraction of sample reacted = 63%
tav = t63
for n = 1
t50 < tav < t75
Correct answer is (a)
H
C12 H 22O11 H 2O C6 H12O6 C6 H12O6
49. sucrose glucose fructose
d d l
r r0 a
CHEM ACADEMY
r rt a x
t 50%
2.303
log
a
2.303
log
100
... (1)
k ax k 50
2.303 r r
t 50% log 0 ... (2)
k r rt
From (1) & (2)
r r0 100
2
r rt 50
r r0 2r 2rt
r0 2rt r
Correct answer is (a)
dx
50. k[H ]n [H ]1 102 M
dt
100 [101 ]n
1 [102 ]n
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CHEM ACADEMY 15 Chemical Kinetics (Solution)
100 (10)n
(10)2 = (10)n
n=2
(t1/ 2 )1 [(a 0 )n 1 ]2
51. (t1/ 2 )2 = [(a 0 )n 1 ]1
10 (103 ) n 1
100 [102 ]n 1
1
(10) n 1
10
(10)1 (10)n 1
n – 1 = –1
n=0
1
t1/ 2
(a 0 )n 1
10
CHEM ACADEMY
(103 )n 1
100 (10 2)n 1
n 1
1 1
10 10
(10–1) = (10)–n + 1
1 – n = –1
n=2
d[sugar]
52. k[sugar]n
dt
0.12 0.06
k[0.06]n
10
0.06
(0.06) n k
10
0.09
(0.03) n k
20
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CHEM ACADEMY 16 Chemical Kinetics (Solution)
n
0.06 20 0.06
10 0.09 0.03
6 2
(2) n
9
4
(2) n
3
d[sugar]
k[0.06]n
10
d[sugar]
k[0.03]n
20
d[sugar]1 20
(2) n
10 d[sugar]2
2 = (2)n
n=1
53. t 99.9%
CHEM ACADEMY
2.303
k
log
100
0.1
For n = 1
2.303 t
t 99.9% 3 No. of half life = t
k 1/ 2
2.303
t 99.9% 3
k
No. of average life = t 63% 2.303
0.43179
k
t 99.9%
6.947 6.9
t 63%
Correct answer is (b)
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CHEM ACADEMY 17 Chemical Kinetics (Solution)
A: first
B: second
54. (I) Rate (II) t1/2 (III) (a–x)–1 C: zero
0 time [A0] t
1 1
Rate = k(A0)o t1/ 2 a 0 kt
ax a
Rate = k(A0 – kt)o For Ist order y = c + mx
1
Rate = k c m=k
a
zero order for IInd order
I II III
C A B
Correct answer is (d)
55. 3A B + C for n = 0 Rate = k(A)o Rate = k
It would be zero order reaction when rate of reaction remain same at any concentration of A.
Correct answer is (b)
56. First order:
2N2O5
CHEM ACADEMY
After dissocation
4NO2 + O2 4 =2:5
10
4 0 0
4 – 2x 4x x
0 8 2
57. 2NO 2 (g) F2 (g) 2NO 2 F(g)
k = 38 dm3 mol–1 s–1 at 300 K 1m3 = 1000 L, 1dm3 = 1 L
or k = 38 L mol–1 s–1
n=2
d[A]
58. k[A]2 For n = 2
dt
1 1
kt
A A0
y = c + mx
mk
1
c
1 A0
[A]
t
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CHEM ACADEMY 18 Chemical Kinetics (Solution)
1
Correct answer is (b) a plot of versus t is straight line.
[A]
59. SGF
0.693
n=1 t1/2 = 28.4 min. k = 0.0244 min–1
28.4 min
2.303 A
A0 = 8 mm, A = 1.0 mm t log 0
k A
0.953 1e k2
log(0.953) 2k
k
CHEM ACADEMY
log(0.953)
2
k 0.01yr 1
t1/2 = 6.93
A = 1e–k(5)
A = e–0.05
A
A0
2.303 1
k log
2 0.953
= 1.1515 log
k = 0.024 year–1
0.693
t1/2 = 28.87yr
0.024
A = 1e–0.024 × 5
A
0.886
A0
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CHEM ACADEMY 19 Chemical Kinetics (Solution)
E
0.693 0.693 0.693 RTa
t1/ 2 E
.e
61. k a A
A.e RT
0.693 E a
ln t1/ 2 ln
A RT
1
ln t1/ 2
T
200 (0.4)n 1
62.
50 (0.1)n 1
4 = (4)n – 1
n–1=1
n=2
63. Incorrect statement is (d) (order can be +ve, –ve or fraction)
0.693
64. K1
40
A A 0 kt CHEM ACADEMY
A0
kt
2
1.386
k2
2 20
k1 0.693 2 20
k2 40 1.386 = 0.5
E
65. a
k Ac RT
k
1
f (x) e x
T
Correct answer is (a)
2.303 a0
66. t 75 log
k 0.25a 0
2.303
log(4)
k
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CHEM ACADEMY 20 Chemical Kinetics (Solution)
2.303
t 50 log 2
k
32
log 2
log 4
= 32 × 0.3
t50 = 16
67. m = +1 = +ve
for n < 1
ln t1/2
n=0
Correct answer is (a) ln a0
this point represent
that at this point ½ of reactant
Concentration
x concentration in product
68.
y
Time
Correct answer is (a)
CHEM ACADEMY es es
E a1
69. k1 < k2, Ea1 E a 2 log k1 log A
2.303 R T es
es es
Ea2
log k 2 log A
2.303 R T es
Ea
log k log A
2.303RT
(1) log A 5
A = 105
Ea 2000
(2) k
2.303RT T
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CHEM ACADEMY 21 Chemical Kinetics (Solution)
2 cal
E a 2000 2.303 8.314 38294 J K 1mol1
= 9212 cal
Ea = 9.212 k cal
log A
1
(3) log k v/s is linear
T E a
m
E a 2.303RT
c = log A m= log k
2.303RT
Correct answer is (a) I, II, III 1/t
k
71.
1
A 2 B2 2AB
k2
72.
CHEM ACADEMY
H = 80 – 100 = – 20 kJ mol–1
Correct answer is (d)
A = 1.20 × 1010 dm3 mol–1 s–1
M(Cl) = 35.453 M(H2) = 2.016
73. Incorrect statement is (d)
k is not affected by change in concentration.
(As we know that k depend on temperature)
74. The increase in rate reaction with rise in temperature is mainly due to increase in no. of effective
collisions.
Correct answer is (c)
k2 Ea 1 1
log
k1 2.303R T1 T2
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CHEM ACADEMY 22 Chemical Kinetics (Solution)
2.2 101 1 1 Ea
log
2.6 103 120 360 2.303 8.314
k 1/ 2
76. k k 2 1
2k 4
E a / RT 1/ 2
E a / RT Ae 1
Ae Ea / RT Ae 2
2Ae Ea 4 / RT
E / 2RT
Ea / RT 1 Ea 2 / RT e a1
e e . E / 2RT
CHEM ACADEMY
2 e a4
Differentiating with respect to temperature and evaluating Ea.
1 1
Ea E a 2 Ea E a 4
2 2
77. 2NOCl(g) 2NO(g) Cl2 (g)
Ea
ln k ln A
RT
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CHEM ACADEMY 23 Chemical Kinetics (Solution)
80. t25% = 30 minutes, T1 = 500 k
k2 2.303Ea
log log A
k1 RT
2.303 4
k2 log 2.87 102 min 1
10 3
2.303E a 1 1
log(0.29 10)
R 500 510
2.303
0.462 E a [3.92 10 5 ]
R
Ea
CHEM ACADEMY
0.462 2 8.314 cal k 1 mol1
2.303 3.92 105
8.314 J K–1 mol–1
J mol–1 = 2 cal.
8.314 × 2 cal
Ea = 0.8509 × 105
Ea = 85 × 103
85 kcal mol–1
k1
81.
A B
AB
k2
3 Dk
AB C
Rate = k3[AB][C]
k1 [AB] k1
[AB] = k [A][B]
k 2 [A][B] 2
k 3k1
Rate [A][B][C]
k2
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CHEM ACADEMY 24 Chemical Kinetics (Solution)
k1k 3
k Ea Ea1 Ea 3 Ea 2
k2
H (E a,f ) (Ea,b ) Ea1 Ea 2
Ea H Ea3
82. At constant T
If Ea is low then
Ea
log k log A
2.303RT
1
So, II Ea 10 kJ mol
III
Ea 40 kJ mol1
fastest slowest
Fast Slowest
II III
Correct answer is (b)
83.
PE
CHEM ACADEMY B
Reaction progress
k2 Ea 1 1 Ea 313 273
log
k1 2.303R T1 T2 2.303 2 313 273
Ea 1 log k
OX = 5 & m = =
2.303RT 2.303
O
Ea = R = 2 cal. 1/T
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CHEM ACADEMY 25 Chemical Kinetics (Solution)
86. RP
Hº corresponds to the energy.
z
y B
x
A
R
Correct answer is (a)
87. NO + O2 NO2 (fast)
CO + O2 CO2 (slow)
88. Activation energy for the reaction
2NO O2 2NO 2 is less than 2CO O 2 2CO 2
H 2O O 2OH
CHEM ACADEMY
77 – (Ea)b = 72
(Ea)b = 5 kJ mol–1
89. aA bB cC dD
Rate (Reversible) = kf[A]a[B]b – kb[C]c[D]d
kf
AeH/ RT
kb
aA bB
1 d[A] 1 d[B]
a dt b dt
d[A] a d[B]
dt b dt
d[A] a d[B]
log log log
dt b dt
a
log 0.3
b
a
1.99 2
b
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CHEM ACADEMY 26 Chemical Kinetics (Solution)
kf
90. Variation of keq & k with increase in temperature.
b
[P]
es, k eq
[R]
kf
for endothermic reaction, k increases, k also increases for exothermic (H = –ve)
b
H
es log k eq log A
2.303R T
[P] es
Tes, keq , es k eq [R] es
CHEM ACADEMY kf
for exothermic reaction, k & k both decreases.
b
Correct answer is (a)
E
91. ln k ln A a
RT
Ea
12000
R
R 8.314 JK 1 mol1
R = 2 cal K–1 mol–1
92. Rate constant of reaction depends on temperature
Correct answer is (a)
93. A catalyst is a substance which alters the time to reach equilibrium.
Correct answer is (c)
94. AP
2000 E a
log k 6.0 compare to log k = log A
T RT
2000 Ea
log A = 6.0
T 2.303 R T
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CHEM ACADEMY 27 Chemical Kinetics (Solution)
A= 106 Ea = 2000 × 2.303 × 0.00831 J K–1 mol–1
A = 1 × 106 sec–1 = 38.29 38.3 kJ mol–1
A = 1 × 106 s–1 & Ea = 38.3 kJ mol–1
95. For an endothermic, (H = +ve)
H Ea
log k = log A – & log k log A
2.303RT 2.303RT
Ea = H + RT (H + ve)
Ea > H
R T 10 R R
96. T 20 T30
RT R T 10 R T 20
Multiply all
R T 30
3 15.6
RT
= 2.5
k1k 3
97. k Ea1 40 Ea 2 30 Ea3 20 kJ
k2
CHEM ACADEMY
Ea = Ea1 E a3 E a 2 = 40 + 20 – 30 = 30 kJ
Correct answer is (c)
98. Ea 12.49 kcal / mol
k E 1 1
ln 2 a
k1 R T1 T2
k
ln 2 0.6940
k1
k2
e0.6940 2 k2 = 2k1
k1
99. Correct answer is (c)
100. Activation energy for a chemical reaction depends upon nature of reacting species.
Part 4
Steady state approx.
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CHEM ACADEMY 28 Chemical Kinetics (Solution)
Ea,t Eth
R
101. H Ea,b Eth > Ea,t; Eth > Ea,b; Eth > H; Eth > Ep; Eth > ER.
A P
2 AB Bk
A B2 (slow)
k1 [A][A]
3 AB k (fast)
A B k2 [A 2 ]
k1
[A] [A 2 ]1/ 2
CHEM ACADEMY
Rate = k3[A] [B2]
k1 1/ 2
k2
1 1 3
Rate k 3 k (A) [B2 ] over all order = 1 1 or
2 2 2 2
1 1 k 2 [E 0 ][s]
103. vs RAte = [s] k
r [s] m
1 1 km
R k 2 [E 0 ] k 2 [E 0 ][s]
km 1
slope Intercept = k [E ]
k 2 [E 0 ] 2 0
k2 km 9
C.E. 40s = k (2.5 10 )
km 2
k2 109
102 109 107
k m 2.5 40
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CHEM ACADEMY 29 Chemical Kinetics (Solution)
104. Rate k 3[A 2 ][C]
k1 [A 2 ] k1
[A 2 ] [A]2
k 2 [A]2 k 1
k2 [c] k2
[c] [A][B] Rate = k´[A]3[B]
k 2 [A][B] k 2
104
105. 1.4 1012
[E 0 ][s] [E]0
1 10 4 12
1.4 10
[E
0 ][s] [E]0
1 [s]104 12
1.4 10
[E 0 ][s]
CHEM ACADEMY
1.4 108[E 0 ][s]
104 [s]
k 3 1.4 108
kM = 10–4
106. 2AB B2 2AB2
Rate = k[AB][B2]
(d) Rate = k3[AB3][AB]
k1
AB3 [AB][B2 ]
k2
k1k 3
Rate [AB]2 [B2 ]
k2
overall rate
107. Kinetic chain length = Initial rate
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CHEM ACADEMY 30 Chemical Kinetics (Solution)
ka fast
108. (II) O3 kb
O2 + [O]
Rate = k1[NO2][O]
ssa on [O]
+ ka [O3] – kb[O2][O]
– k1[NO2][O] = 0
ka[O3] – kb[O2][O] = k1[NO2][O]
k a [O3 ]
[O]
k b [O2 ] k1[NO 2 ]
k a [O3 ]
Rate k1[NO 2 ]
k b [O 2 ] k1[NO2 ]
k a [O3 ]
O
k b [O2 ]
109. Proposal B.
2H 2O SO3 H 2SO 4 H 2O
CHEM ACADEMY
Rate k 2 [SO3.2H 2O]
[SO3 .2H 2 O]
k1
k 1
[SO3 ][H 2O]2
k 2 k1
Rate [SO3 ][H 2O]2
k 1
110. Rate acc. to Mech. I.
Rate = 10–5 [A][B]
= 10–5 [10–1][10–1]
= 10–7
10–5[A][B] = 10–4[A]
[B] = 10
111. Rate has to be calculated from the slowest step, which can identified by value of k
Rate = k1 [A]
= 10–4 [1] = 10–4 mol L–1 s–1.
112. RI = RII
k1´ [A][B] = k1[A]
k1 10 4
[B] 10M
k1' 105
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CHEM ACADEMY 31 Chemical Kinetics (Solution)
113. Question Error
114. Question Error
115. 2X3 3X2
1 d(X3 ) 1 d(X 2 )
Rate =
2 dt 3 dt
d(X 2 ) 3 d(X3 )
dt 2 dt
Correct answer is (d)
No. of molecules of reactant converted into product
116. T.O.F.
No. of molecules of enzyme taken × time taken
103
= 6
10 2 s1
10 10
117. Rate = 2kb[N2O2][O2]
ka[NO]2 – ka[N2O2] – kb[N2O2][O2] = 0
k a [NO]2
[N 2O 2 ]
CHEM ACADEMY
k a k b [O 2 ]
2
k a [NO]
Rate = b k k [O ] [O 2 ]
2k
a b 2
118. Rate = k2[Br][H2]
Applying equilibrium approximation on [Br]
[Br]2 [M]
k [Br] k [Br2 ]
[Br2 ][M]
Rate = k2 [H2] × [k]1/2 [Br2]1/2
Correct answer is (a)
119. O 2 NNH 2 N 2O H 2O
[O 2 NNH 3 ] k1
(b)
[O 2 NNH 2 ][H ] k 1
[O 2 NNH ][H ] k1
(c)
[O 2 NNH 2 ] k 1
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CHEM ACADEMY 32 Chemical Kinetics (Solution)
k1 [O 2 NNH 2 ]
k 1 [H ]
k[Co 2x]3
122. (A) Rate = k1[Cl2][H2S]
(B) Rate = k2[Cl2][HS–]
CHEM ACADEMY
[HS ][H ] k1
[H 2S]
k 1
k1 [H 2S]
[HS–] = k
1 [H ]
k1
ln
123. tmax = k2
k1 k 2
ln(2)
t max 13.4
0.1 0.05
124. The following curve represents parallel mechanism
k1 B
A k
2
B
Correct answer is (c)
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CHEM ACADEMY 33 Chemical Kinetics (Solution)
125. All statement are correct
* Unimolecular gas phase reactions following
Lindemann Mechanism follows:
2nd order at low pressure and 1st order at high pressure.
126. Br2 h 2Br
Correct answer is (b)
k1 k2
127. Species Q can act as a transient species when: P Q R
k1 < k2
Correct answer is (d)
k 2 [E 0 ][S]
128. Rate
[S] K m
1 1 km
Rate k 2 [E 0 ] k 2 [E 0 ][s]
1 1
Intercept = k [E ] 5000M s
2 0
CHEM ACADEMY
[E 0 ] 109 M
1
K2 9
10 5000
2 × 10–4 × 109
T.O.F. = K2 = 2 × 105
k 2 [E 0 ][s]
129. Rate
[s] k M
1 1 km
k 2 [E 0 ] k 2[E 0 ][s]
kM
Slope = k [E ] 40
2 0
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CHEM ACADEMY 34 Chemical Kinetics (Solution)
k2 106
k M 40 2.5
k2
104
kM
130. When free radicals forms to form a product
H H H2
Correct answer is (c)
[Y] k1
131.
[X] k 2
1 104
4 k2
k 2 4 104
132. k2 > k1
133.
CHEM ACADEMY
A A 0 .e k a t for a consecutive reaction
Correct answer is (a)
134. k
a B
b k
A C
A0 C
conc. ka > kb
B A
t
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CHEM ACADEMY 35 Chemical Kinetics (Solution)
141. Thermopile
142. Absorption S h S*
Fluorescence S* S h
ISC S* T *
143. Phosphorescence T* S h
IC S* S
150.
ISC:
S1 S0
CHEM ACADEMY
S1 T1 (Change of spin)
152. T1 S0 h
153. Correct answer is 4
154. (I) and (III) are correct, whereas
order of energy required for various energy transition is
* n * * n *
155. S1 S0 h : Fluorescence
S1 S0 : IC
S1 T1 : ISC
T1 S0 h : Phosphorescence
156. G is a photo-chemical reaction may be positive or negative.
157. Using: Absorbance = E × b × conc.
WB
0.411 = (4 × 103) × (1) × M V(L)
B
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CHEM ACADEMY 36 Chemical Kinetics (Solution)
WB
0.411 = 4 × 103 ×
180 1
0.411180
WB 0.018495g
4 103
W 0.018495
% 0.1362 13.62%
W 0.1358
158. Reasons for derivation from Beer’s law
Very high concentration of analyte
Association or Dissociation of analyte
Refractive index Polychromatic light
50 1
159. Case I: Transmittance (T1) = 50% =
100 2
Case II: Optical density or Absorbance = 0.17610
A2 = 0.1761
T2 = 10 A 2 100.1761 0.67
CHEM ACADEMY
Net Transmittance ‘T’ = T1 × T2
=
1
2
0.67
= 0.33 33%
160. Refer Q. No. 158
100
161. A1 log E b (0.002M)
80
100
A 2 log E b c2
20
A1 0.0969 0.002
c2 = 0.0144 M
A 2 0.6990 c2
162. All the statements are correct.
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CHEM ACADEMY 37 Chemical Kinetics (Solution)
165. No. of quantas of radiations absorbed in 1200 seconds = 2 × 1016 × 1200
2NH3 N 2 3H 2 0.2
177. Repeated
d(HI)
178. dt 2
Iabs
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CHEM ACADEMY 38 Chemical Kinetics (Solution)
183. For a chain reaction, > 1
184. a, b, c are correct.
(d) is incorrect
Acceptor has lower energy than donor.
EXERCISE - II
One or More Than One Correct Type
1. (a) t1/ 2 a 0 for n = 0
0.693 1
t1/ 2 tav =
k k
1
t1/ 2 0.693 t av t av t1/ 2 Tav = 1.44 t1/2
0.693
t 75
(c) t 3 n=2
50
CHEM ACADEMY
t75 = 3t50
2.303 3
t 99.9% min 99.69 100 min
0.0693
Correct answer is a, b, c, d
2. Zn 2H Zn 2 H 2
R k[103 ]n
100R k[102 ]n
n
1 1
102 = 10n n=2
100 10
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CHEM ACADEMY 39 Chemical Kinetics (Solution)
dx
(b) k[Zn]1[H ]2
dt
1
(c) Rate is not effected if (Zn) is four time P[H+] =
2
(d) Rate becomes four times if concentration of [H+] ion is doubled at constant Zn concentration.
Correct answer is b, c, d.
2000 Ea
3. log k (min–1) = 5 – compare to log k = log A –
T(k) 2.303RT
(a) pre-exponential factor A is 5. log A = 5, A = 105
(b) Ea is 2000 k cal
2000 Ea
T 2.303RT
Ea = 2000 × 2.303 × 2 = 9212 cal = 9.212 k cal
(c) pre-exp. factor is 105
(d) Ea is 9.212 k cal.
Correct answer is c, d
4.
5.
CHEM ACADEMY
Correct answer is b, c
(a) Law of mass action P rate law expression are same for single step reaction.
(b) Order of slowest Reaction.
(c) Both order & molecularity have normally a maximum value of 3.
(d) M olecularity of a complex reaction A + 2B C is 3.
Incorrect statement are a, b, c
P
log k
Ea
6.
k Ae RT
Q
1/T
k[SO 2 ]
7. Rate
[SO3 ]1/ 2
(b) Overall order is 1/2
(c) The reaction slows down as the product SO3 is build up
Correct answer is b, c
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CHEM ACADEMY 40 Chemical Kinetics (Solution)
8. 2A P
For n = 2 m = 2k
1 1 1/[A0]
2kt
A A0
y = c + mx 1/[A]
1
c m = 2k t
A0
Graph will show straight line with slope 2k.
Correct answer is (a)
9. True for 2nd order
(a) k = 1 × 10–2 L mol–1 s–1
1
(b) t1/ 2 a
0
1 1 1 A0
(d) t 50 k A kt A t t1/ 2
CHEM ACADEMY
0 A A0
2
1
k t1/ 2
2
t1/ 2
1
A0 A0 k A0
Ea
Correct answer is a, b, d
k Ae RT
10. XP
1 log A
(a) A plot of log kP vs is linear Ea
T m
2.303R
Ea log k
log k log A
2.303RT
y c mx
1/T
(b) A plot of log [X] vs time is linear
for n = 1 for reaction X P
k
A A0c kt m
2.303R
kt log k
log A log A0
2.303
kt
log x log X 0 T
2.303
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CHEM ACADEMY 41 Chemical Kinetics (Solution)
11. (a) Catalyst increases the average Kinetic energy of reacting molecules.
(b) decrease Ea Energy.
(c) alters the reaction mechanism
(d) increases the frequency of collesions of reacting species.
Correct answer is (b), (c)
12. X Y
Ea,f = 15 kJ mol–1 Ea,b = 9 kJ mol–1 P.E. of X = 10 kJ mol–1
(a) Eth = Ea,f + P.E. of X = 15 + 10 = 25 kJ
(b) P.E. of Y = Eth – Ea,b = 25 – 9 = 16 kJ
(c) H = Ea,f – Ea,b = 15 – 9 = 6 kJ
(d) Reaction is endothermic H = +ve
Correct answer is (a), (b), (c), (d)
E
13. Ea = 0 a
k Ae RT
kA
14. In photophysical process of organic molecules, the process occur are
(a) Fluroscence
CHEM ACADEMY
(b) Phosphoresecence
(c) ISC
(d) IC
Correct answer is (a), (b), (c), (d)
EXERCISE - III
Numerical Answer Type & Subjective Questions
A A0e kt = 1 M e
A = e–0.270 = 0.7634 M
Rate = 4.5 × 10–3 min–1 [0.7634 M]
Rate = 3.4352 M min–1
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CHEM ACADEMY 42 Chemical Kinetics (Solution)
2. A 2B 2Z 1 2
d[A]
R 0.28 0.56
dt
0.28 0.39 0.13 but 0.39
0.18 0.250 0.0833 B is L.R.
0.2 0.139 0.28 0.39
0.2
(extent)A = 0.250 0.39 0.13
1
0.139 0.13
(extent) B 0.0695 0.25 0.25 = 0.0833
2 0.39
3. 2A + B 3Z
d[A] 1 d[A] 4 3 1
3.36 104 2 dt 1.68 10 mol dm s = Rate
dt
d[B] 1 d[Z]
1.68 104 1.68 104
dt 3 dt
d[Z]
5.04 104
4.
dt
CHEM ACADEMY
A + 2B 2Z
Rate = k[ A ] [B]
= 2 ×10–6 = k[7 × 10–2][4.6 × 10–2]
4 × 10–6 = k[7 × 10–2] [9.2 × 10–2]
9.2 102
2
4.6 10 2
= 1, = 2
5. 2 A 2 B Y 2Z Rate k [ A] [ B]
2
2.8 102 5.92 108 1.4 2.3 7.4 109
1
5.92 106 2.8 4.6 5.92 108
2.8 10
2
1 1 1 1
0.125
10 100 2 2
1
(10) (10) 2
(0.5) (0.5) (0.5)1
2
=2 =1
Answer is = 2, = 1
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CHEM ACADEMY 43 Chemical Kinetics (Solution)
6. (i) k = 5.6 ×10–4 mol L–1 s–1 Zero order
(ii) k = 4.5 × 10–2 L mol–1 s–1 second order
(iii) k = 3.2 × 10–7 s–1 First order
(iv) k = 4.0 × 10–2 atm–1 s–1 Second order
(v) k = 1.6 × 102 L2 mol–2 s–1 Third order
5
(vi) k = 3 × 10–3 L3/2 mol–3/2 s–1 order = 2.5
2
7. k = 5.0 × 10–5 s–1 A0 = 1 mol L–1
Rateinitial = k[A0]1
= 5.0 × 10–5 mol L–1 s–1
8. n=0 t = ? when A is 10% unreacted means 90% reacted.
t75% reacted in 60 min (1hr)
for n = 0
t75% 75
t90% 90
t75% 5 5
t75% = 60 min (1hr) t75% t90%
t90% 6
CHEM ACADEMY
t90% = ?
6
t90% 60 min 72 min
5
6
72
t90% hr 1.2hr
60
Answer is 1.2 hr.
9. n=1
t1/2 = 50 min. 90% completion means 90% reacted.
0.693 2.303 100
k 0.01386 min 1 t90% log
50 k 10
2.303
t90% log10 166.6 min
0.01386 min 1
10. [A] = 4[B]
0.693
[A] = [A0] e–kt 5 min .
k
0.693
[A0 ] 4[B0 ] k1 0.1386
5
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CHEM ACADEMY 44 Chemical Kinetics (Solution)
K 0.693
[A]0
[A 0 ]e k [A] [A 0 ] e0.1386t
2
[A 0 ] [A0 ] e 0.0462t
[B0 ] [B0 ] e 0.1386t
4[B0 ]
e 0.0462t 0.1386t
[B]0
4 = e0.0924t
ln4 = 0.0924 t
1.38629
t= 15 minutes
0.0924
2.303 r r 2.303 13.1 3.8 2.303 16.9
11. k
t
CHEM ACADEMY
log 0
rt r
2.303
180
log
9.0 3.8
2.303
180
log
12.8
O O
12. || H 2O / H ||
CH3 CH 2 C OH C 2 H5OH
CH 3 CH 2 C OC 2 H5
Hydrolysis
t18.17% = 60
2.303 A0
k log
60 A 0 0.1817A 0
2.303 1
k log
60 0.8183
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CHEM ACADEMY 45 Chemical Kinetics (Solution)
2.303
k (0.08708)
60
k = 0.00334 s–1
0.693
t1/ 2 207.48 minutes
0.00334
13. (PA )0 300 mm of Hg PB = 500 mm of Hg
A B A(polymerises)
(PA)solution = 400 mm of Hg
A poly poly
B X
12 mole 0.525
t=0 10
t=t n
2.303 10
k log
t n
CHEM ACADEMY
100 min
Apply Dalten’s law of partial pressure
PT PAo .x A PBo .x B
12
12.525
400 300
12.525
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CHEM ACADEMY 46 Chemical Kinetics (Solution)
0.693
t1/2 =
k
t99.9% 6.909
9.1697 10
t1/ 2 0.693
t99.9% = 10 t1/2
x = 10
0.693
16. k 0.086625 s 1 min 1
8
[A]0
[A] 1% of [A]0
100
2.303 A0
t log
0.086625 A 0 /100
2.303
2 53.1717 min .
0.086625
17. k2 = 3.33 × 10–2 L mol s–1
[A0] = 0.05 mol L–1
1
1 CHEM ACADEMY
[A] [A 0 ]
k2t
1 2
k 2t
[A0 ] [A0 ]
1
k2t
[A0 ]
100
3.33 600.6s
0.05
1 1
8 105 t
0.25 1
4 1 8 105 t
3 105
0.375 105 min .
8
= 37500 min.
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CHEM ACADEMY 47 Chemical Kinetics (Solution)
19. A P [A0] = 0.010 M t = 100 sec
t=0 0.10 – [A] = 0.001 M k = 9.0
t = 100 0.001 n=?
R.A. 0.099
1 1
20. t1/ 2 1 n 1 t1/ 2 2
(a 0 ) (a 0 ) n 1
(t1/ 2 )1 (a 0 )2n 1
(t1/ 2 ) 2 (a 0 )n 1
2t1/ 2 2(a 0 )n 1
t1/ 2 (a 0 ) n 1
2 = 2n – 1
n–1=1
n=2
21. t1/2 is double as the a0 is doubled
t1/2 a0 for n = 0 order
22.
x 20 400
x
CHEM ACADEMY
T1 = Tc = 400
500
4x = 5x – 100
x = 100 kJ mol–1
23. k1 = 1.5 × 107 s–1 at 323 k
k2 = 4.5 × 107 s–1 at 373 k
k Ea 1 1
log 2
k1 2.303R 323 373
45 Ea 1 1
log
15 2.303 8.314 323 373
Ea 1 1
24. log(2) =
2.303 R 300 310
k2
e Ea / RT Ea / RT
k1
(E a E a,c ) / RT
e
3 /8.314300
e(108.71680)10
28716
27.
300
x
CHEM ACADEMY
e 8.314300
400 x 100
3x + 300 = 4x
x = 300
Ea
ln k1 ln A
RT1
Ea , C
ln k 2 ln A
RT2
E a,c Ea
ln k1 ln k 2
RT2 RT1
Ea,c Ea
RT2 RT1
E 2 E1
T2 T1
x 100 400
x 300
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CHEM ACADEMY 49 Chemical Kinetics (Solution)
3x + 300 = 4x
x = 300
29000k
T
28. k=5× 1011 L mol–1 s–1 e
E
a
k Ae RT
Ea 29000k
RT T
Ea = 29000 × 8.314 = 241106 J / mol
Ea = 241.106 kJ/mol
1.25 104 k 1
29. logk = 14.34 – ln s
T
Ea
log k log A
2.303RT
Ea 1.25 104
2.303RT
CHEM ACADEMY
T
Ea = 1.25 × 2.303 × 8.314 × 104
= 23.934 × 104 J / mol
Ea = 239.34 kJ/mol
k at 700 k
Ea
log k = log A –
2.303 R 700
239.340
log k 14.34 14.34 17.8572 3.5217
2.303 8.314 700
k = 10–3.5217 = 10–3.52
log A = 14.34
A = 1014.34
Correct answer is (c)
30. k
1 B
A
2C k
2 A
3 Dk Total rate of disappearance of A.
3 A
dA
k1[ A] 2k2 [ A] 3k3[ A]
dt
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CHEM ACADEMY 50 Chemical Kinetics (Solution)
–4 –1
k1 1.26 104
%B
100 100
k
1 k 2 1.25 10 4
3.6 10 5
1.26 104 1.26
4
100 100 77.77%
1.26 0.36 10 1.62
% C 22.23%
33. kA
A kB
B C
k A 0.451 ; k B 0.151 ; A 0 5 mol L1
k1 0.4 4
ln ln ln
(a) t max k2 0.1 1 4.62sec .
k1 k 2 0.4 0.1 0.3
k2
1/ 3
k k 2 k1 4
(b) Bmax
CHEM ACADEMY
A0 1
k2
5
1
3.164 M
k2
34. % yield of ketene 100
k1 k 2
35. T T1 T2
72.7 40.7
0.296
100 100
100
37. A1 log c
90
100
A 2 log 5 c
I
10
log
A1 9 1 0.04576 1
A 2 log 100 5 log 100 5
I I
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CHEM ACADEMY 51 Chemical Kinetics (Solution)
100
log 0.2288
I
2 log I 0.2288
log I 1.7712
I = 59.05%
Intensity of absorbed radiation = 40.95%.
NA hC
39. Energy of one Einstein
6.022 10 6.626 10
23 34
3 108
2.492 105 J
9
480 10
1 cal 4.184 J
Number of Einstein
2.492 10 J 2.494 10 5 J
5
4.184 106
Number of moles 16.736
CHEM ACADEMY
2.494 105
Since, H 2 Cl 2 2HCl
number of moles = 16.736 × 2 = 33.472 moles
40. Overall Transmittance T1 T2
37 19
0.07
100 100
41. Same as Question No. 67
42. (a) Absorbance b c
2 1cm 0.03M
2
66.7 mol1cm 1dm 3
0.03
I0
(b) Absorbance log
I
1
I
A log
I0
I I
A log 10 A 102
I0 I0
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CHEM ACADEMY 52 Chemical Kinetics (Solution)
100
(c) log 66.7 1 0.015
I
100
log 1.0005
I
2 log I 1.0005
log I 2 1.0005 0.9995
log I 1
I = 10%
% Absorbed = 90%
1
43. N1O5 2NO 2 O 2
2
1
d N 2 O5 d NO 2 2d O
Rate 2
2
dt dt dt
1
k1 N 2 O5 k 2 N 2 O5 2k 3 N 3O5
2
CHEM ACADEMY
So, k k1
k2
2
2k 3
2k1 k 2 2k 3
1 d NH 3 1 d O2 1 d NO 1 d H 2O
Rate
4 dt 5 dt 4 dt 6 dt
1 d NO
(a) Rate
4 dt
2
1 1.08 10
Rate 9 10 4 mol L1s 1
4 3
1 d NH 3
(b) Rate
4 dt
d NH 3
4 Rate 4 9 10 4
dt
36 10 4 mol L1s1
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CHEM ACADEMY 53 Chemical Kinetics (Solution)
1 d H 2O d H 2O
(c) Rate 6 Rate 6 9 104
6 dt dt
54 104 mol L1s 1
45. 2NO H 2 N 2 H 2 O
1 d NO
Rate
2 dt
Comparing (i) and (ii) using Rate k NO H2
4.4 10 4 k NO H2
2.2 10 4 k NO H2
4.4 104 k 1.5 10 4 10
4 3
2.2 104 k 1.5 104 2 103
2 2 1
CHEM
ACADEMY
Similarly, comparing (II) and (III)
R 2 1 k 1.5 10
4
2 103
R3 4 k 3 104 2 103
1 1
2
4 2
Order = 1 + 2 = 3
2 1
Rate k NO H 2
46. A B C
t 0 pi
t t Pi P P P Pt P2 Pi P
t Pi Pi P P3 2Pi
P3
Pi
2
P3 2P2 P3
P P2 Pi P2
2 2
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CHEM ACADEMY 54 Chemical Kinetics (Solution)
1 P
k ln i
t Pi P
P3
1 2
k ln
t P3 2P2 P3
2 2
P3
1 2
k ln
t P3 2P 2 P3
2
1 P3
k ln
t 2 P3 P2
47. n=1
t1/ 2 30 minutes at 27º C T1
k 300k
CHEM ACADEMY
0.693
30
min 1 and k 320
0.693
10
min 1
k2 a 1 1
log
k1 2.303R T1 T2
0.693
a 1 1
log 10
0.693 2.303 8.314 300 320
30
a 1 1
log 3
2.303 8.314 300 320
a 43.85 kJ mol1
a1 a2
48. k1 A e RT
and k 2 A e RT
a
a 1
k1 1 2 a a
e RT RT e RT 2 1
k2
1
75000 25000
e 8.314 298
e 20.18
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CHEM ACADEMY 55 Chemical Kinetics (Solution)
49. 2H 2 2NO N 2 2H 2 O
From mechanism
Rate k 2 N 2O 2 H 2
k1
N2O 2 N 2 O 2 k1 NO
2
2
NO
2
Rate k 2 k1 NO H 2
2
k NO H 2
50. A nB
t=0 A0 0
t=t A0(1 – X) nA0.X
At intersection point O obtained after time t,
[A] = [B]
CHEM ACADEMY
A0(1 –X) = nA0.X
X=
1
1 n
nA 0
[B] =
1 n
51. For A : rate = kA [A]1 .... (i)
0.693
and (t1/2)A = kA ... (ii)
0.693 1
From Eq. (ii) and (iv) if (t1/2)A = (t1/2)B , then
kA k B .a
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CHEM ACADEMY 56 Chemical Kinetics (Solution)
kA
or kB = 0.693 × a ... (vi)
rA 0.693 a
From Eqs. (v) and (vi), = 0.693
rB a
(b) After lapse of I half, the new rates are rtA and rtB
2
a a
rtA = kA × 2
; rtB = kB ×
2
rAt kA 2
... (vii)
rBt kB a
rAt 2
By Eqs. (vi) and (vii) r t = 0.693 × a × = 1.386
B a
52. Given, A nB
0.6 0.5
Loss in concentration of A in 1 hour = = 0.1
1
0 .2 0
Gain in concentration of B in 1 hour = = 0.2
1
CHEM ACADEMY
(i) 0.1 mole of A gives to 0.2 moles of B in a given time and thus,
n=2
(ii) Equilibrium is attained after 5 hrs. where [B] = 0.6 and [A] = 0.3
B2 [ 0. 6 ] 2
Equilibrium constant, K = = 1.2 mole litree–1
[A] 0. 3
0.1
(iii) Initial rate of conversion of A = changes in conc. of A during 1 hour = = 0.1 mole litree–1
1
hour–1
2.303 a
53. k
t
log
(a x )
Hint : Use hit and trial method.
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CHEM ACADEMY 57 Chemical Kinetics (Solution)
2 .303 200
k2
100
log
200 146
(c) For a Ist order reaction t(1/n) (a)0 and therefore if initial pressure is 600 mm, the decomposition
in 100 minute will be 73%.
54. To provide a long time or heating to a reaction mixture means that reaction has gone to completion.
A B + 2C
Moles before dissociation a 0 0
Moles after dissociation (a – X) X 2X
Moles after complete diss. 0 a 2a
Total moles at a time pressure at that time
a P0 t=0 ... (i)
a + 2X 264 t = 14 minute ... (ii)
CHEM ACADEMY
3a 264
(a) By Eqs. (i) and (ii)
t=
Pº = 150 mm
(b) By Eqs. (ii) and (iii) X 57
... (iii)
2.303 150
K= log = 3.415 × 10–2 min–1
14 150 57
0.693 0.693
(c) t1/2 = = 20.29 min
K 3.415 10 2
2.303 a
55. t= log
K (a X )
a
If t = t1/2, X = ;
2
2.303 a
t1/2 = log ... (i)
K a (a / 2)
99a
If t = t99%,X = ;
100
2.303 a
t99% = log ... (ii)
K a (99a / 100 )
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CHEM ACADEMY 58 Chemical Kinetics (Solution)
log 100 2
By Eqs. (i) and (ii), t99% = × t1/2 = 0.3010 × 2.1 = 13.95 hour
log 2
2 .303 P0
k= log
t P
t
P0 = Initial pressure of A
Pt = Pressure A after time t.
A B + C + D
P0 0 0 0 at t=0
[Pt = (P0 – x)] x x x at t=t
Given (P0 – x + x + x + x) = P
CHEM ACADEMY
(P0 + 2x) = P
x=
(P – P0 )
2
(P – P0 ) (3P0 – P )
Then (P0 – x) = P0 – =
2 2
80
when Rxn completed 20% = (a – x) = 100
× [a]
Then
1 1
1 –
k= 500
80 a a
100
1 100 1
k= –
500 80 a a
1 100
k= – 1
500 a 80
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CHEM ACADEMY 59 Chemical Kinetics (Solution)
1 20 1 1 1 1
500
× 80
× a
= 500 4
× a
= 2000 a
1
k= 2000 a
Then
1 1 1
k= –
t 40 a a
100
1 1 100
= – 1
2000 a a t 40
1 1 60
2000 =
t 40
t = 3000 sec
58.
CHEM ACADEMY
Suppose order of Rxn is n
Then
n
1
t1 / 2
P
0
n
( t1/ 2 )1 (Po )2
=
( t1/ 2 )2 (P )
0 1
1.934 = (2)(n – 1)
(1.9569) = (2)(n – 1)
n = 2 IInd order Rxn.
59. (a) Rxn zero order W.R.T. to A then.
when half of A reacted
A + B + C Product
at t = 0 a0 a0 a0
a0 a0 a0
at t = 1000 sec. 2 2 2
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CHEM ACADEMY 60 Chemical Kinetics (Solution)
Then we know for zero orders Rxn (a0 – at) = kt
a0
given at = 2
.
a0
Then k × t = 2
a0 a0 a0
k= 2 t
= 2 1000
= 2000
at t= 2000 sec.
a0
a0 – at = 2000
× 2000
1 1 1
k= –
1000 a0 a0
2
1 1
k= ×
1000 a
0
CHEM ACADEMY
Then after 2000 sec.
k=
1 1
–
1
2000 at a0
1 1 1 1 1
× = –
1000 a0 a
2000 t a 0
2 1 1
=
a
0 a 0 at
3 1
a0 = at
a0
at = 3
at 1
Fraction left a0 = 3
1
60. For N2O5 2 NO2 + 2
O2
x Vt ,
a V
a – x (V – Vt)
Then for Ist order Rxn
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CHEM ACADEMY 61 Chemical Kinetics (Solution)
2 .303 V
0.008 = 20
log ( V – Vt )
2 .303 V
0.008 = log ( V
20 – 16 )
0.008 20 V
= log ( V
2.303 – 16 )
V
0.06947 = log ( V – 16)
Then
V = 108.23 mL
61. CH3OCH3(g) CH4 (g) + CO(g) + H2(g)
P0 = 4mm 0 0 0
Pt = (P0 – x) x x x
we known
Pt = p0 e–Kt
Pt
p0 = e–Kt
Pt
p0
= e
CHEM ACADEMY
–(4.78 x 10 –3 x 4.5 x 60)
Pt
p0 = e–1.29 = 0.275
62. Containing mixture of compound A and B both decomposed with first order kinetics
t1/2 for A = 54 min t1/2 for B = 18 min
At – Ao e – k1t .... (i)
Bt – Bo e – k2t .... (ii)
Ao = Bo
At – 4Bt
by (i)/(ii)
4Bt B ek1t
o
Bt = B ek 2t
o
4 = e ( k 2 k1 ) t
ln 4 = (k2 – k1) t
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CHEM ACADEMY 62 Chemical Kinetics (Solution)
ln 4
ln 4 ln 4
t= = = 0 .6932 0.6932 = 53 min.
(k 2 k1) (k 2 k1)
18 54
63. k = Ae Ea / RT
case I. k1 = Ae 100 / RT
case II. k2 = Ae 25 / RT
k1 e 100 / RT 75 / RT
25 / RT e
k2 e
k2
or loge log e 75 / RT (H in kJ)
k1
k 2 75 75 10 3
loge
k1 RT 8.314 293
(H in kJ)
K2
K1
= 2.35 × 103
Since, r = k [A]n n and [A] are same for case I and II.
CHEM ACADEMY
r2 k 2
= 2.35 × 1013
r1 k1
3163
64. log10K = T
+ 12
Then we know
– Ea
K = Ae
RT
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CHEM ACADEMY 63 Chemical Kinetics (Solution)
For uncatalysed Rxn
– Ea
K1 = Ae [T = 300 K , R = 2]
RT
– 18 10 3
K1 = Ae ....(i)
2 300
and for catalysed Rxn
– 6 103
K2 = Ae ....(ii)
2 300
K2
K1 = e20
K2
K1 = 4.85 × 108
Then catalysed reaction is 4.85 × 108 times faster than uncatalysed Rxn.
66. Intensity of incident radiation = I0
CHEM ACADEMY
Intensity of transmitted radiation ' I '
I0
4
Concentration = 0.05 molar ‘C’
Path length ‘b’ = 10 cm.
Using, Absorbance b c
I0 I
A log log 0 10 0.05
I I0
4
0.6020 0.5
1.204 dm3 mol 1cm 1
100
So, A1 log E 1cm 10 3 M
90
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CHEM ACADEMY 64 Chemical Kinetics (Solution)
100
A 2 log E 1cm C2
10
Dividing the two:
10
log E 103
9 C 2 0.0218 M
log10 E C2
68.
X Y
T1 = 80%; T2 = 60%
Since, Transmittance is a multiplicative property
T T1 T2
80 60
0.48 48%
100 100
69. Wavelength ' ' 253.7 nm
CHEM ACADEMY
Total energy = 307 J
Number of moles of HI decompose 1.30 103 mole
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CHEM ACADEMY 65 Chemical Kinetics (Solution)
EXERCISE IV
Previous Year Questions
Ea
1.
k A.e RT
5. CHEM ACADEMY
828 s
k = 3 × 10–5 s–1
2.4 × 10–5 = 3 × 10–5 × [N2O5]
[N2O5] = 0.8
6. According to Grothus Draper law
For the primary absorption step
AB h AB*
d(AB*)
Rate Intensity of Absorbed radiation
dt
Correct answer is (b)
7. N2 + 3H2 2NH3
d(N 2 ) 1 d(H 2 ) 1 d(NH3 )
Rate =
dt 3 dt 2 dt
2.303 800
8. k log 4
2 10 50
2.303
k 4 log 2
2 104
4.606 104 0.3 1.386 10 4 s 1
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CHEM ACADEMY 66 Chemical Kinetics (Solution)
2.303 0.1 1
9. k log 0.0346 min
40 0.025
Rate = 3.4 × 10–4
10. k = k1 × k2 = 6.8 × 1.6 = 10.8 × 10–6
1.08 × 10–5
11. R k[G][H]n
R1 k[2G][2H]n
R1 k 2n 1[G][H]n
R1 2n 1 R 8R
2n 1 23
n=2 3 overall order.
0.693
12. k1
40
[A 0 ]
2 CHEM ACADEMY
kt
1.386
k2
2 20
k1 0.693 40
0.5
k0 40 1.386
Ea 2000
13.
2.303RT T
Ea = 2000 × 2.303 × 8.314
Ea
K
14.
k A.e RT
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CHEM ACADEMY 67 Chemical Kinetics (Solution)
x A 0 2x A 0
A 0
2 4
3x
C0
Hence, x = 10 min. so, time required for C0 to become . = 3x = 30 min.
4
16. PQR
A0 R
conc.
P
Q
t
k k [H]2
17.
G
2H k eq
k 1 k 1 G
1 P
G H
k [H]2 k eq [G]
dp
dt
dp
k[G][H]
CHEM ACADEMY [H] {k eq [G]}1/ 2
dt
k eq k1/ 2
2 [G] [G]
1/ 2
[G]3/ 2
18. Number of moles of substrate reacted = Number of moles of product formed.
= 1.0 mM
= 1.0 × 10–3 M
Number of moles of enzyme used = 1.0 × 10–6 M.
1 103
T.O.F. = 6
100s 1
1 10 10
1 1
19. kt
A A0
A0
A = 1 A kt
0
ln A ln A 0 ln(1 A 0 kt)
E a 12000
20.
RT T
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CHEM ACADEMY 68 Chemical Kinetics (Solution)
Ea = 12000 × 8.314
= 99768 J mol–1
0.693
21. k
28.4
2.303 28.4 8
t log
0.693 1
= 85.2 min.
1 d[NO2 ]
22. 2k b [N 2O 2 ][O2 ]
2 dt
K a [NO]2
[N 2O2 ]
K a K b [O 2 ]
[NO]2
Rate K b K a [O2 ]
K a K b [O2 ]
23. k = 0.0240
CHEM ACADEMY
A = 1 × e–0.0240 × 5
= 0.886
k
24.
1
A I ; H < 0
k 1
A A 0 .e ka .t
26. for n=1
0.693
t1/2 =
k
0.693
t1/ 2 Ea
A.e RT
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CHEM ACADEMY 69 Chemical Kinetics (Solution)
Ea
0.693 RT
t1/ 2 .e
A
0.693 Ea
ln t1/ 2 ln
A RT
1
ln t1/ 2
T
27. Question error
E a
28. 50
RT
Ea = 50 × 8.314 × 300
= 124.7 kJ mol–1
0.693t
29. 14.2 15.3e 5730
14.2
e 0.000120t
15.3
CHEM ACADEMY
0.0324 2.303
2.303
x 0.000120t
270 years ×2.303
30. Using, Eddie-Hofstee equation
rate vmax rate
[s] Km Km
rate k [E ] rate
Divided by [E0] - 2 0
[E 0 ](s) [E 0 ].K m [E 0 ].K m
k2 1
On comparing - 1.4 1012 and 104
km km
k2 = 1.4 × 108
Correct answer is (c)
Overall rate 4 103
31. Kinetic Chain length = Initial rate = 2000
(2 103 ) (103 )
32. For, n = 0
A0
t1/ 2
2k
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CHEM ACADEMY 70 Chemical Kinetics (Solution)
2.303 a
33. k1 log 0 .298K
t 0.9a 0
2.303 a0
k2 log .308K
t 0.75a 0
1
log
k2 0.75 2.7304
k1 1
log
0.9
E a 1 1
log(2.7304)
2.303R 298 308
Ea
0.4362 [0.000108]
2.303 8.314
Ea = 77333.17 J mol–1
77333.17
CHEM ACADEMY
k = 3.56 × 109e
k = 0.0007051 s–1
8.314318
77333.17 J mol1
= 9 + 0.551 –
2.303 8.314 J K 1mol 1 318K
= 9.551 – 12.7009
log k = –3.1499
k = 10–3.1499
1.25 104 E a
34.
T RT
Ea = 1.25 × 104 × 8.314 = 10.3925 × 104
1.25 104
ln k = 14.34 10.66
500
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CHEM ACADEMY 71 Chemical Kinetics (Solution)
10
0.12 0.06
0.03
35. (a)
20
for n = 1
x A 0 x A0
A 0
2 4
2x
so, order = 1
0.693 0.693
k 0.0693 hour 1
t1/ 2 10
2.303 0.04
(b) t1/ 2 log
(20 10) 0.03
2.303 4
t1/ 2 log t1/ 2 24.09 min
10 3
36. 4PH3 P4 + 6H2
Pi 0 0
Pi – 4x x 6x
0 CHEM ACADEMYPi
4
2Pi
3
Pt = Pi – 4x + x + 6x
272.90 262.40
k[PH3 ]
60
275.51 272.90
k[PH 3 ]
60
k[PH3 ] 0.10925
2.303 262.40
k log
60 272.90
37. A + B Product
Rate = k(A) (B)
Comparing (i) & (ii) expt-
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CHEM ACADEMY 72 Chemical Kinetics (Solution)
2.303 Pi
k log
2t Pi 2P
2.303 800
k log
2 100 400
2.303 0.3010
k
CHEM ACADEMY
200
k = 3.46 × 10–3 min–1
for n = 1
t75 = 2 × t50
0.693
=2×
2k
2 0.693
= 200 min
2 3.46 103
39. A 2B + C
t=0 Pi – –
t=t Pi – P 2P P Pt Pi 2P
1 P
k ln i
t Pi P
1 Pi
= ln
t P P
Pi t i
2
1 2Pi
k ln
t 3Pi Pt
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CHEM ACADEMY 73 Chemical Kinetics (Solution)
40. 2A B C D
1 d(A) d(c)
Rate
2 dt dt
1 d(c)
(0.1)
2 dt
d(c)
0.05mol L1s 1
dt
41. n=0
A0
t1/ 2
2k
t1/ 2 A0
k2 Ea 1 1
42. log
k1 2.303R T1 T2
160 Ea 1 1
log
8 2.303 8.314 300 350
105
M = 5.37 µM
18, 600
Correct answer is (b)
44. 2NO 2H 2 N 2 2H 2O
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CHEM ACADEMY 74 Chemical Kinetics (Solution)
(ii) Keeping concentration of (NO) = constant, when [H2] is reduced to half, the rate of reaction
becomes half.
So, order with respect to [H2] = 1
1
45. t1/ 2
(a 0 )n 1
(a 2 )n 1
n 1
(a 3 )n 1 1
(a1 )
n 1
(0.07)
CHEM ACADEMY
(0.11) (0.05)
(0.03)n–1 = 1
1
(n – 1) log (0.03) = 0
– 1.522 n + 1.5228 = 0
n=1
46. Concentration = 2.5 × 10–4 M Concentration = 1.5 × 10–3 M
Absorbance = 0.90 Path length = 0.2 cm
Path length = 1.5 cm Absorbance = ?
A1 = E × b1 × c1 and A2 = E × b2 × c2
Ea 20
log 2
19.147 298 318
Ea = 27.99 kJ mol–1.
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CHEM ACADEMY 75 Chemical Kinetics (Solution)
k2 Ea 1 1
48. Using, log k 2.303R T T
1 1 2
160 Ea 1 1
log
8 2.303 8.314 300 350
Ea 1 1
log 20
19.147 300 350
Ea = 52.3 kJ mol–1.
CHEM ACADEMY
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