(Physical Chemistry) CHEMICAL KINETICS

SOLUTIONS
EXERCISE #O-I

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RATE OF REACTION AND STOICHIOMETRIC COEFFICIENT

−d[N 2 ] 1 d[H 2 ] 1 d[NH 3 ]
3. =− =
dt 3 dt 2 dt
d[A] d[B] d[C] 1 d[D]
4. − =− = =
4dt dt dt 2 dt
1 d[A] 1 d[B]
5. − =
x dt y dt
d[A] x d[B]
− =
dt y dt

 d[A]  x  d[B] 
log  −  = log + log  
 dt  y  dt 
x
 log = 0.3
y

x
 =2
y

10
6. Rate = slope = = 0.5 M sec–1
20
7. ‘k’ depends only upon temperature and catalyst.
k1' k '' k k
8. = 1 = 1 =
2 2 1 2
9. Rate = k [A]1 [B]0
10. Rate = k [A]1 [B]2
Initial Rate = 1 × 10–2 = k × 1 × 12
K = 10–2
 Final Rate = kc [A]1 [B]1
= 10–2 × 0.5 × 0.52
= 1.25 × 10–3 M sec–1

APNI KAKSHA 1
(Physical Chemistry) CHEMICAL KINETICS

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1 d[NO2 ] d[O2 ]
11. − = = 1.5 × 10–4
2 dt dt
d[N O2 ]
 − = 3 × 10–4 = 3 × 10–3 [NO2]2
dt
[NO2] = 0.316 M
ZERO ORDER REACTIONS
13. [A]t = [A]0 – kt
[A]0 = [A]t + kt
30
= 0.05 + 0.2 ×
60
= 0.15 M
14. [B]t = 2 kt
= 2 × 10–3 × 100
= 0.2 M

15. For zero order reaction

Rate = k

16. t1 =
 A 0
2 2k
log( t 1 ) = log [A]0 – log (2k)
2

FIRST ORDER, SECOND ORDER & nth ORDER REACTIONS

19. Rate = k [A]

20. Rate = 4 × 10–3 × 0.02
= 8 × 10–5 M sec–1

1  A 0
21. k = ln
t  A t

1  1 
= n 
20  0.25 
= 0.06931 min–1

APNI KAKSHA 2
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0.693 0.693
22. k= = = 10–2 sec–1
t1 69.3
2

Rate = k × [A] = 10–2 × 0.1 = 10–3 M sec–1

n
1
23. Fraction of reactant left after n half lift =  
2
 40 min is 2 half life

2
at  1  1
 =  =
ao  2  4

0.693
24. t1 = = 600 sec.
2 1.155  10−3

k1 [D]2  1 
26. k= = ln   = 0.0255
k 2 [P]  0.6 

1  0.6 
t= n   = 20 min.
0.0225  0.36 

1  100  2ln 2
27. k= ln   =
100  100 − 75  100
1  200 
t= ln   c = 100 min.
k  200 − 150 

1  100 
28. k= ln   = 0.0805
20  100 − 80 
0.693
t1 = = 8.66 min.
2 0.0805

30. Rate = k [A]t = k [A]0 e–kt

2 2  2.303
31. | Slope | = k = × 2.303 min–1= sec–1 = 7.7 × 10–3 sec–1
10 10  60

APNI KAKSHA 3
(Physical Chemistry) CHEMICAL KINETICS

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second order reaction

1 1
33. = +kt
at ao

0.693
34. t1 = min = 8.6625 × 103 min.
2 8  10−5
nth order and pseudo order reaction

37. A ⎯→ nB
A0 0
A0– x nx
A
At intersection point [A] = [B]  A0– x =nx  x =
n +1
nA
 [B] =nx =
n +1

38. For nth order reaction

1 c
t1 × n −1
=
2 a o a on −1

log ( t 1 ) = log c – (n – 1) = log ao

2

 Slope = –(n – 1) = – 1

 n=2

40. Concentration of A remain constant because it is present in large amount so order w.r.t. A will
be zero in overall order or reaction.

1
41. t1/2   [A]0−1
[A]0

On comparing with
t1/2  [A]10−n

1 – n = –1  n = 2

APNI KAKSHA 4
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Experimental determination of order

42. r = K [A]x[B]y
from exp. 1 and 2 on increasing [A]0 2 times rate becomes 8 time, so x = 3
from exp. 2 and 4 on increasing [B]0 2 times rate does not change, so y = 0
r = K[A]3[B]0

43. r = k[A]x[B]y
from exp 1 Q 2 x = 1
from exp 2 Q 3 y = 0
r = k[A][ B]0
ln 2
t1/2 =
k
6.93×10–6 = k× 0.01
k = 6.93×10–4
0.693
t1/2 = = 1000 sec
6.93 10−4
t = 50 min = 3000 sec
[A]0 0.5 1
[A]t = = = M
23 8 16
1
r = 6.93×10–4× M sec–1
16

44. t1/2  P01−n

1− n
950  250 
= 
235  500 
950 1
log = (1 – n)log
235 2
0.6 = –(1–n)×0.3
1–n = –2  n = 3

APNI KAKSHA 5
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Experimental determination of First order rate constant

45. A ⎯→ 2B + C
t=0 Po 0 0
t=t Po–x 2x x
t= 0 2Po Po
3Po = 270  Po = 90
Pt = P0 + 2x = 176 2x = 80  x = 43
(PA)t = Po – x = 90 – 43 = 47

46. (CH3)2.CHN=NCH(CH3)2(g) ⎯→ N2(g) + C6H10(g)

t=0 Po 0 0
t=t Po–x x x
Pt = Po + x  x = Pt – Po
Po – x = Po – (Pt – Po) = 2Po – Pt
1 P 1 Po
k = ln o = ln
t Po − x t 2Po − Pt

1
47. H2O2(aq) ⎯→ H2O() + O2(g)
2
t=0 C 0 0
x
t=t C–x x
2
C
t= 0 C
2
C x
 50 and  5
2 2
1 C 1 50
k= ln = ln
20 C − x 20 45

APNI KAKSHA 6
(Physical Chemistry) CHEMICAL KINETICS

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48. NH4NO2(aq) ⎯→ N2(g) + 2H2O()

t=0 C 0 0
t=t C–x x 2x
t= 0 C 2C
C  70 and x  40
1 70
k= ln
t 30

49. A ⎯→ B + C
1 r −r 1 100 − 0 1
K = ln  0 = ln = ln 2 = 0.0693 min–1
t r − rt 10 100 − 50 10

1 r −r
50. K = ln  0
t r − rt

1 −10 − 40
= ln
10 −10 − 15
1 50
ln
10 25
0.0693 sec
parallel first order reaction
[B] k1
51. =
[C] k 2

52.

[B] k1 1
 = =
[C] k 2 2

Total moles = 0.5 + 2 + 1 = 3.5

APNI KAKSHA 7
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Collison Theory

53. r = Z11.e–Ea/RT.P

55.

56. Molecules with sufficient amount of energy and proper orientation

Effect of temperature on rate

58. k = A e–Ea/RT

59. k = A if T→.

60. k = A if T→.

 k  Ea  1 1 
61. n  2  =  − 
 k1  R  T1 T2 

 k  Ea  1 1 
62. n  2  =  − 
 k1  R  T1 T2 

3.8  10−16
63. Fraction of molecules = e–Ea/RT =
100

64. % of activated molecules= e–Ea/RT×100

APNI KAKSHA 8
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65. The reaction which has more steep curve will be more temp sensitive.

Ea  1 
66. n k = n A –  
R T

Effect of catalyst on rate

Ea 8.3  1000
68. Slope = − =− = –1000
R 8.3
mechanism of reaction
70. Rate - k [A] [B]

71. Rate = k3 [Q]2 [P]

k1 [Q]2
 Keq = =
k 2 [P]

k1
 [Q]2 = [P]
k2

k1
 Rate = k3 [P]2
k2

APNI KAKSHA 9