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CHEM ACADEMY 1 Chemical Kinetics (Solution)

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)

[BH  A  ] k f 2.38  104 105


   2.92
[HA].[B] k b 8.15

4. AP
Rate = k[A]n
k[0.01]n 10 4
R1 = 
k[0.02]n 1.41104
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

For forward reaction For backward reaction


[B] Rate

CHEM ACADEMY 0.01 M


0.02 M
1 × 10–2 M s–1
2 × 10–2 M s–1

Rate 1102  0.01 
 
2 102  0.02 
[A]
1 
1 1
 n=0        1
2 2

 zero order reaction  First order reaction


d(A) d(B)
For forward Rate =   k1 (A)0  k1
dt dt

 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

Rate  k[PNO ] [PH2 ]

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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 ]

1.60  k[289] 0.79  k[147]



1.60  289 
   1
0.79  147 
d[A]
7. Rate  k[A]  
dt

d[A]
kdt  
[A]

A
CHEM ACADEMY
ln    kt
 A0 

8. Ag   2NH3  [Ag(NH3 )2 ]

Rate  kf [Ag ]1[NH3 ]2  kb[Ag(NH3 )2 ]  0

k f  2  107 L2 mol2s 1 k b  102 s 1

k f 2  107 L2 mol2s 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

Initial rate = k[A 0 ][B0 ]2


10–2 = k[1][1] k = 10–2

1 1
Rate at t = 10–2    
2 4


 102  1.25  103
8
11. Rate = k[CH3COCH3][Br2] [H+]r

5.7  k[0.3] [0.5] [0.05]r


5.7  k[0.3] [0.1] [0.05]r
(1) = (5)
 log 5 = 0

=0

12. 
dt
CHEM ACADEMY
d(NO 2 )
 k(NO 2 ) 2

As we know the value of rate constant depend on temperature


so, on doubling the temperature k changes.
Correct answer is (b)

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  104 M min 1
dt 25

d[C] 0.0039
in II =  2.6  104 M min 1
dt 15

d[C] 0.0077
in III =  1.02  103 M min 1
dt 7.5

16. 1.3 104  k[0.1]2  [0.05]

1.3 104

17.
k

k=?
CHEM ACADEMY
102  5 102
 0.26

Rate = k[A]2[B]

Rate 1.32 104 1.32


 k 2
 2
  0.264
[A] [B] (0.10) (0.05) 5

 k  2.6  101
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[O 2 ] 1 d[N 2O5 ] 16 g hr 1 1


19.  16g / hr = = 1
 mol hr 1
dt 2 dt 32 g mol 2

 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

k(1.5A)n  2.25  k  [A]n

(1.5)n  [A]n  2.25  [A]n


n log(1.5)  log(2.25) n=2
21. Correct answer is (a)
A-r, B-s, C-q, D-p

8 105 k[0.2]
22. =
3.2 104 k[0.4]

CHEM ACADEMY

1 8 105
  
2 32 105
=2

 0.5  3.2 104 32
 2.0  12.8 104  128


1 1
    1
 4 4

1.28 103 [0.4]2[2]1[0.4]r



4 105 (0.1)2 (0.25)2 (1.6)r
2 r
 128  16 10  2  (0.4)
 4   2
  10  0.0625  (1.6)r
 128  32
   104  0.0512  104
 4  625
r r
128  0.4  1
      0.0625
4  512  1.6  4
(0.2)r = 0.0625

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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

26. CHEM ACADEMY


Correct answer is (b)
2A2 + B2  2A2B
1 d[A 2 ] d[B2 ] 1 d[A 2 B] 1 d[A 2 ] dB
Rate =      2 rate  
2 dt dt 2 dt 2 dt dt

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 103
35.  0.81 M 1s 1  [4 103 ]2
2t

1.5 103
2t  6
 0.115 103 = 115 s
0.8116 10

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CHEM ACADEMY 10 Chemical Kinetics (Solution)
115
t=
2
1 1
103   0.810  t
(4  1.5) 4 103
1 1
  20.81 t
2.5 103 4 103
t = 0.926s
1
36. t1/ 2 
(a 0 )n 1

t1 (a1 )n 1  t 2 (a 2 )n 1

4280  (0.5)n 1  885  (1.1)n 1


n 1
4280  1.1 
 
885  0.5 

4.836  (2.2) n 1 (n – 1) log 2.2 = log 4.836


n=3

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  102  0.36  102
41. R    mol L1s 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  105 T 1s 1
n P n P

105
t1/ 2   0.5  103
200
t1/2 = 500 s
44. AP
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.

Correct answer is (a)


45. A  B
A0 0
A0 – x x
0 A0
R.A. x x
(A0  x)  A 0  kt
x = kt
x t
t 50 50 100
 
t 75 75 150

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 ax 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  102 M
dt

100 [101 ]n

1 [102 ]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 (103 ) n 1

100 [102 ]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
(103 )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

2.303 100 2.303


tav = p t63% = log   0.43179
k 37 k

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
ax 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

mk
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. SGF
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

2.303 8 2.303  0.9031


t 1 log   85.2 min.
0.0244 min 1 0.0244 min 1
Correct answer is (c)
0.693
60. t1/ 2 
k

0.953  1e  k2
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

Correct answer is (a)  k2 will increase faster than k1


2000
70. log k(min 1 )  5  k
T

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 1mol1

= 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

(Ea)forward = 180 kJ mol–1 (Ea)backward = 200 kJ mol–1

H  E a,f  E a,b  180  200  20 kJ mol 1


In presence of catalyst
Ea,f = 80 kJ mol–1 Ea,b = 100 kJ mol–1

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)

T1  120k k1  2.6 103


75. T2  360k k 2  2.2 101

T/k  120 240 360


K  2.6 × 10–3 – 2.2 × 10–1

k2 Ea  1 1 
log    
k1 2.303R  T1 T2 

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CHEM ACADEMY 22 Chemical Kinetics (Solution)

2.2  101  1 1  Ea
log   
2.6  103  120 360  2.303  8.314

2200  360  120  Ea


log  
26  360  120  2.303  8.314 J K 1mol 1
1.927  2.303  8.314  360  120
Ea   6641.37
240
k2 Ea  1 1 
log 3
     k2 = 2.4 × 10–2
2.6  10 2.303R  120 240 

  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)

A  1013 M 1s 1 , E a  105 kJ mol1 , RT  2.5 kJ mol1


For bimolecular reaction
Ea = H + 2RT
H = 105 – 2 × 2.5 = 100
Correct answer is (d)
78. For Lindeman For Michael Menton’s
n=2 n=1 n=1 n=0
Low conc. High conc. Low conc. High conc.
E
79.  a
K Ae RT

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  A 0  2.303 4


k1  log   log  
30  3A 0 / 4  30 3
= 0.00959 = 9.59 × 10–3 min–1

2.303 4
k2  log    2.87  102 min 1
10 3

 2.87  102  2.303E a 1 1 


log     
 9.59  103  R
   T1 T2 

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 mol1
2.303  3.92 105
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 mol1
fastest slowest

Fast Slowest
II III
Correct answer is (b)

83.
PE
CHEM ACADEMY B

Reaction progress

84. k2 = 3k, T2 = 40ºC = 313 k,


k1 = k T1 = 0ºC = 273 k Ea = ?

k2 Ea  1 1  Ea  313  273 
log    
k1 2.303R  T1 T2  2.303  2  313  273 

log 3  2.303  2  313  273


 Ea 
40
Correct answer is (a)
X
Ea
85. log K = log A – 
2.303RT

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. RP
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

H  72kJ Ea = 77 kJ mol–1 T = 500 k


H = –72 kJ (Ea)f – (Ea)b = 72

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
 AeH/ 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

For endothermic (H = +ve)


es
H
es log k eq  log A 
2.303R T es


[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
 Tes, 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 mol1
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. AP
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    T30
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  0.00138 103 cal mol1 k 1


ln  2  
 k1  2 cal mol1 k 1

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

Correct answer is (c)


102. A 2  B2  2AB
Mechanism:
k

1
A 2 A A (fast)
k2

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

[E0 ] = 2.5 × 10–9 mol dm–3

k2 km 9
C.E.  40s = k (2.5  10 )
km 2

k2 109
  102  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] 

1.4 1012 [E0 ][s]



1  104 [s]

 CHEM ACADEMY
1.4 108[E 0 ][s]
104  [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

Correct answer is (a)

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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' 105

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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

103
= 6
 10 2 s1
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  ]

120. Rate  k 2 [B]


121. Rate = k1[NO]2[H2]
(d) R = k1 [CO]3
R1 =
2NO + 2H2  N2 + 2H2O
Co Co – –
Co – 2x Co – 2x x
d[N 2 ]
Rate   k[NO]2 [H 2 ]
dt

 k[Co  2x]2 [Co  2x]

 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 ]  109 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

[E0] = 2.5 × 10–6


kM
 40  2.5 106
k2

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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 104

4 k2

k 2  4  104
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

135. High quantum yields are due to formation of free radicals


Correct answer is (d)
136. Radiactive process = Fluorescence, Phosphorescence
137. Chemical Luminescence.
138. Correct answer is (b)
139. Phosphorescence
Correct answer is (b)
140. 8000 Å – 2000 Å

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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

Collision induced emission  S*  M  S  M  h


Inducer

Excited state absorption  S* h  S* (higher excited state)


144. Correct answer is (a)
145. Both fluorescence and phosphorescence are secondary effects.
146. Excitation of Molecules.
147.  Emission of Radiations  Phosphorescence
 Fluorescence
 Collision with other molecules
148. Both n   * and    *
149.

150.
ISC:

S1  S0
CHEM ACADEMY
S1  T1 (Change of spin)

151. T1  Maximum populated state

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

0.411180
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  100.1761  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.

hc 6.6 1027 erg sec  3 1010 cms1


163. E 
 3000 108 cm
= 6.6 × 10–12 erg.
164. by definition
Correct answer is (a)

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CHEM ACADEMY 37 Chemical Kinetics (Solution)
165. No. of quantas of radiations absorbed in 1200 seconds = 2 × 1016 × 1200

0.002 moles reacted  6.02  1023


‘’ quantum yield =  50
2 1016 1200
166. ln I = ln I0 – kbc
167. Photo sensitized reactions
168. a, b, d are correct.
(c) is incorrect, such reactions are photosensitized reactions.
169. Photo inhibitors
N A .h C 1
170. E  E
 
171. I and III are correct
But, II is incorrect, Absorption of a photon by a molecule may lead to a chemical reaction according
to stark-einstein law (Q. 175)
172.  (HI) = 2

173. H 2  Cl 2  2HCl   104  106

H 2  Br2  2HBr   0.01


174. CHEM ACADEMY
Michaelis Menten  Enzyme Catalyst.
Arrhenium  effect of temperature on reaction rate
Erying  T.S.T.
Einstein  Photo-chemical Reactions
175. Start-Einstein Law.
176. With reference to Q. 173.
2HI  H 2  I 2 =2

2NH3  N 2  3H 2   0.2
177. Repeated

d(HI)

178.  dt  2
Iabs

179. Grotthus-Drager law


180. Beer’s law
181. For a primary process,  = 1
 0.1
182. Rate constant =  9
 107 s1
 10 10 S

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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

(b) t av  1.44  t1/ 2 for n = 1

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

(d) k  0.0693min 1 t 99.9% 


2.303
log
100
0.0693 0.1

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

Half life is independent of concentraiton of zinc means n 1


–3 –2
+
[H ] 10 +
[H ] 10
R  100 R When pH  3 to pH  2

R  k[103 ]n
100R  k[102 ]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

(c) t 75%  2t 50 t 75%  3t 50

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. XP
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

kA
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

1. AB k  4.5  103 min 1 [A0] = [f]


n=1

Rate = k[A]1 t = 60 min (1 hr)


for n = 1 = 4.5 × 10–3 min–1 × 60 min.

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  104   2 dt  1.68  10 mol dm s  = Rate
dt  
d[B] 1 d[Z]
  1.68  104   1.68  104
dt 3 dt
d[Z]
  5.04  104

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 102 
2
 4.6 10 2 
 
  = 1,  = 2
5. 2 A  2 B  Y  2Z Rate  k [ A] [ B]
 2 
 2.8 102  5.92 108  1.4   2.3  7.4 109
 1 
  
    
 5.92 106  2.8   4.6  5.92 108
 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 ]  e0.1386t
2

[B]  [B0 ]  e 0.0462t


[A] = 4[B]

[A 0 ]e 0.1386 t  [B0 ]e 0.0462t

[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

k  log1.3203   0.120673 min 1


180 min 180
k = 0.0015439 min–1
2.303 13.1  3.8 2.303 16.9 2.303  0.648
t 1
log  log   966.6 min
0.0015439 min 3.8 0.0015439 3.8 0.0015439

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 
 

14. t25% = 40.5 min


2.303 100 2.303
k log  log1.33
45 75 45
2.303
k  0.12385  0.006338 min 1
45
15. n=1
t99.9% = x t1/2

t99.9% = 2.303 log 100  2.303  3  6.909


k 0.1 k k

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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

18. k 2  8  105 [A]  [0.25] [A 0 ]  1

1 1
  8  105  t
0.25 1

4  1  8  105 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 

3.966 104 3.966


Ea    104
9.55 9.55

Ea  1 1 
24. log(2) =   
2.303  R  300 310 

log(2)  2.303  8.314


Ea 
x
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CHEM ACADEMY 48 Chemical Kinetics (Solution)

log(2)  2.303  8.314 104



1.0752
Ea = 53.6 kJ mol–1
25. k1 = 6 × 10–5 L mol–1 s–1 T1 = 30ºC = 303 K
k2 = 3 × 10–4 L mol–1 s–1 T2 = 50ºC = 323 k

3 104 2.303  8.314  323  303


Ea  log 5
 = 65490.4 J/mol
6 10 20
Ea = 65.49 kJ/mol

26. E a  108.716 kJ mol 1

k2
 e  Ea / RT Ea / RT
k1
(E a  E a,c ) / RT
e
3 /8.314300
 e(108.71680)10
28716

27.
300

x
CHEM ACADEMY
 e 8.314300

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 
2C 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

32. k1 B k1 = 1.26 × 10 sec


A
k2 C k2 = 3.6 × 10–5 sec–1

 k1   1.26 104 
%B   
 100    100
k
 1  k 2   1.25  10 4
   3.6  10 5
 

 1.26  104  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  0.451 ; k B  0.151 ; A 0  5 mol L1
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)  Bmax
CHEM ACADEMY
  A0    1 
 k2 
 5 
1
 3.164 M

 k2 
34. % yield of ketene    100
 k1  k 2 

 4.65  4.65  100 465


  100  
 3.74  4.65  8.39 8.39

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

number of moles  2.494 105


Quantum yied '  ' 106 
4.184

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 mol1cm 1dm 3
0.03
I0
(b) Absorbance  log
I
1
 I 
A  log  
 I0 
 I  I
A   log     10 A  102
 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

44. 4NH 3  5O 2  4NO  6H 2 O

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 L1s 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 L1s1

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CHEM ACADEMY 53 Chemical Kinetics (Solution)

1 d  H 2O d  H 2O 
(c) Rate    6  Rate  6  9  104
6 dt dt
 54  104 mol L1s 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  104 k 1.5  10   4  10 
4 3

 
2.2  104 k 1.5  104    2  103 

2   2     1

CHEM
 
ACADEMY
Similarly, comparing (II) and (III)


R 2 1 k 1.5  10
4
2  103
 

   
R3 4 k  3  104   2  103 


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 

t1/ 2  10 minutes at 47º C  T2 

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 mol1
 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 

Applying equilibrium approximation to  N 2O 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)

For B : rate = kB [B]2 ... (iii)


1
and (t1/2)B = a. k B ... (iv)

where a is initial concentration.


(a) Initial rate of A, rA = kA × a
Initial rate of B, rB = kB × a2
rA k A 1
   ... (v)
rB k B a

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

B2 [ 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.

Case I : a 200 mm ;


x  200 × (50/100) mm and t1/2 = 53 minute
2 .303 200
 k1 
53
log
200  100

= 1.307 × 10–2 minute–1


Case II : a 200 mm ;
x  200 × (73/100) mm  146 mm
and t73% = 100 minute

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CHEM ACADEMY 57 Chemical Kinetics (Solution)
2 .303 200
 k2 
100
log
200  146

= 1.309 × 10–2 minute–1


(a) Since, the value of k is constant for the given data using I order reaction and thus reaction is of
I order.
k1  k 2 (1.309  1 .307 )  10 2
(b) k =  = 1.308 × 10–2
2 2

(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

Also, Moles of N2O formed = (99/100) × moles of NH2NO2 taken


99 6.2
=  = 0.099
100 62
 Volume of N2O formed at STP = 0.099 × 22.4 = 2.2117 litre
56. A  B + C + D.
We know for first order Rxn

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

57. We know for IInd order Rxn.


1  1 1
k=  –  (because concentration of both reactants are equal)
t  (a – x ) a 

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

For 60% completed


 60  40 a
(a – x) = a – a
100 
= 100

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

From (i) and (ii) data.


n 1
 3.52   100 
  =  
 1.82   50 

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

at = 0 zero fraction left.


(b) IInd order W.R.T. A then similarly 50% completed

 
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

Sine composition is same therefore


r2 P2
r1
= P = 0.275 Ans. 0.275
1

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 ek1t 
 o 
Bt =  B ek 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

at T (T ij) = (273 + 43.3) = 316.3 K


3163
log10K = + 12
316.3
log10K = (10+12) = 22
K = 1022
Then half life period
 1  1 1
t1 / 2 =   = = = 10–19
K a  1022  .001 1019

t1 / 2 = 10–19 min Ans. 10–19 minute.


65. Decomposetion of H2O2 Ist order (Rxn)
1
H2O2  H2O + 2
O2

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

Equation (2) / (1)


K2 (18 – 6)  103
K1 =e
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

67. Case-I: Concentration  103 molar  C1 

Let, I0  100; I  90; path length ‘b’ = 1 cm.

Case-II: C2  ? when I0  100; I  10

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  103
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  103 mole

Number of moles of reactant reacted or product formed


‘Quantum yield’  
Number of einstein of radiation absorbed
NA  hC
(A) Energy of one einstein 
(m)

Total energy 307 J  


(B) Number of einstein  
Energy of one einstein N A  h C
307  253.7  109

6.02  1023  6.62  1034  3 108
1.30 10 3  6.02  1023  6.62 10 34  3  108
(c)   2
307  253.7  109
number of moles of reactant reacted or prod. formed
70.   0.21 
number of einstein of radiantion absorbed

n  6.02  1023  6.6 1034  3  108


0.21 
50  313  109
  2.74  105 moles

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CHEM ACADEMY 65 Chemical Kinetics (Solution)

EXERCISE IV
Previous Year Questions
Ea
1. 
k  A.e RT

when, T   ; e–0 = 1; K=A


Correct answer is (c)
2. AP
k = 60 × 10–4 s–1 = 60 × 60 × 10–4
Rate = 60 × 60 × 10–4 [0.01] mol L–1 min–1
= 0.36 × 0.01 = 0.34 × 10–2
3. Rate = 60 × 60 × 10–4 [0.01 ml L–1]
4. 10–2 = 0.2 × k
1 10
k=  102   102 min 1
0.2 2
0.693
t1/ 2   102  13.8 min
5

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  104  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

15. For a second order reaction,


I f A 0  Initial concentration of reactant.

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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. PQR

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 103
 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  K a [N 2O 2 ]  K b [N 2O2 ][O 2 ]  0

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

As temperature increases: k1 & k–1 being rate constant


k1
Increases, where keq = k decreases accoding to Le-chatlier principle.
1

25. For a consecutive reaction


k
a  B 
b k
A  C

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
0.693t

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 103
31. Kinetic Chain length = Initial rate =  2000
(2 103 )  (103 )
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

8.314318

k = 3.56 × 109 e–29.205


Ea
log k = log A –
2.303RT

77333.17 J mol1
= 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-

0.1  k(0.2) (0.1)


0.05  k(0.1) (0.1)
2 = (2)  =1

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CHEM ACADEMY 72 Chemical Kinetics (Solution)

0.05  k(0.1) (0.1)


Comparing (i) & (ii):
0.05  k(0.1) (0.2)

1
1    =0
2
 Rate = k(A)1 (B)0
0.05 = k × 0.1
k = 5 × 10–1 sec–1
38. 2x  3y + 2z
Pi
Pi – 2P 3P 2P Pt  Pi  3P

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 103
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 L1s 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 

log 20  CHEM ACADEMY


Ea

50
19.147 300  350
Ea = 52.30 kJ mol–1
43. E = 18,600 L mol–1 cm–1
Absorbance = 0.1
Thickness = 1 cm
Using:
A=E×b×c
0.1 = 18,600 × 1 × c
0.1
C molar
18, 600

105
 M = 5.37 µM
18, 600
Correct answer is (b)
44. 2NO  2H 2  N 2  2H 2O

1 d(NO) 1 d(H 2 ) d(N 2 ) 1 d(H 2O)


(i) Rate     
2 dt 2 dt dt 2 dt

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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

1.2 106 k[0.025] [0.005]


Similarly, 
0.6 106 k[0.0125] [0.01]

 25 103   1 1
2
 125 104   2 
 
1
1
2  (2)    (2) = 4
2

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

A1 b1  c1 0.90 1.5  2.5  10 4


   
A 2 b2  c2 A 2 0.2  1.5  103
A2 = 0.72
k2 Ea  1 1 
log  
47. k1 2.303  R  298 318 

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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