CLS ENG 23 24 XII Che Target 2 Level 1 Chapter 4

Step-1
Chapter 4
Chemical Kinetics and Nuclear Chemistry
Solutions
SECTION - A
1. Answer (2)
Depends on order of reaction.
2. Answer (1)
aA + bB o cC
1 A 1 B 1 C
   
a t b  t c t
3. Answer (2)
Concentration of reactant decreases with time.
4. Answer (1)
Rate = K[A][B]
5. Answer (4)
1 d[Br  ] 1 d[Br2 ]
 
5 dt 3 dt
6. Answer (4)
Rate = K[A]2
(Rate)2 = K[2A]2 = 4K[A]2
7. Answer (4)
K depends only on temperature.
8. Answer (3)
Rate = K
K = mol L–1 s–1
9. Answer (3)
Rate = K[Conc.]2
Conc. time–1 = K[Conc.]2
10. Answer (2)
For zero order,
Rate = K[Conc.]° = K
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2 Chemical Kinetics and Nuclear Chemistry Solutions of Assignment (Step-1)
11. Answer (3)

Rate = K[Conc.]
12. Answer (3)
As the concentration of H2O is much higher.
13. Answer (2)
K T  10
  [2, 3] 
KT
14. Answer (3)
10
15
5 kcal
SECTION - B
15. Answer (3)
Kc = 2Ks
 
Ae Ea /RT  2Ae Ea /RT
16. Answer (1)
For exothermic reactions,
(Ea)f + |'H| = (Ea)b
E2 + |'H| = E1
17. Answer (4)
K  Ae Ea /RT
Ea
logK  log A 
2.303RT
18. Answer (3)
K2 Ea  1 1
log    
K1 2.303R  T1 T2 
19. Answer (1)
From K  Ae Ea /RT

20. Answer (2)
Ea
logK  log A 
2.303RT
logK – Ea
logA 2.303R
1/T
Solutions of Assignment (Step-1) Chemical Kinetics and Nuclear Chemistry 3
21. Answer (3)
At = A0 – Kt
[A]0
t100% 
K
22. Answer (3)
As the concentration of water is high, so the reaction is pseudo 1st order.
23. Answer (4)
Concentration of reactants reduces to zero at life time of reaction.
24. Answer (2)
Bimolecular collisions are predominant at normal pressure conditions.
25. Answer (2)
Rate = K[A]a[B]b
Order = a + b
SECTION - C
26. Answer A(q); B(p, r); C(p); D(s)
R = K × I o zero order kinetics as it independent of concentration of reagents.
SECTION - D
27. Specific reaction rate is the rate of reaction when the molar concentration of each of the reactants is unity.
28. The rate of disintegration of a radioactive substance is directly proportional to the amount of the substance
present. Hence, it is a reaction of first order.
29. For a particular reaction at a particular temperature, rate constant is constant and does not depend upon the
concentrations of the reactants.
 3 3
30. Order = 1     1 
 2 2
3
1
 L 2
Hence, unit of k    L1/ 2 mol1/ 2 s1
 mol  s1
d[C12H22O11 ]
31. (i) Rate of reaction = −
dt
d[C6H12O6 (glucose)]
= +
dt
d[C6H12O6 (fructose)]
= +
dt
(ii) It is pseudo first order reaction :
? Rate = k[C12H22O11]
(iii) Molecularity is 2.
(iv) Order is 1.
32. Rate = k[A]m ...(i)
where m is the order of reaction.
Given, 2 × rate = k[4A]m ...(ii)
From equations (i) & (ii),

m
1  1
 
2 4
1
m=
2
33. For a first order reaction,
0.693
t1/2 =
k
k = 10–2 s–1
0.693
t1/2 = = 69.3 s
10 −2
2.303 [A ]
34. k= log 0
t [A t ]
0.693 2.303 100

= log
60 240 [A t ]
At = 6.25 %
35. k = 0.082 min–1
2.303 a
k log
t ax
2.303 0.15 2.303 2.303

t= log = log 5 =  0.694 = 19.6 min.
0.082 0.03 0.082 0.082
36. The temperature dependence of rate constant is expressed by Arrhenius equation as
Ea
ln k  ln A 
RT
Ea
Slope = 
R
Since reaction 2 has greater negative slope, it has higher activation energy.
37. Arrhenius equation of two different temperatures is given as
k2 Ea  T2  T1 
log 
k1 2.303R  T1 T2 
Ea  10 
log2   
2.303  8.31 300  310 
Ea = 53.6 kJ

Step-2
Chapter 4
Solutions
1. Answer (4)
The rate law is given
R = K[AB]
? When concentration of [AB] is reduced to half, the rate also becomes half .
2. Answer (4)
3. Answer (2)
The rate law for the reaction
A + B o C + D is given by
Rate = K [A]–1/2 [B]3/2
When [A] and [B] becomes twice
1 1 3 3
– –
Rc = K(2)– K(2) 2
[A] 2
2 2 [B] 2
1 3
– 
= K (2) 2 2
[A]–1/2 [B]3/2
2/2 –1/2 3/2
= K (2) [A] [B]
Rc = 2K [A]–1/2 [B]3/2
? Rc = 2 (rate)
Hence, the rate becomes 2 times.
4. Answer (3)
1
Rate of formation of KCl = (rate of consumption of FeSO4)
6
5. Answer (2)
Rate given is
5/2 –1/2
Rate = K [x] [y]
On doubling the concentration of x and y,
5 1

Rate = K(2)5/2 (2)–1/2 [x]5/2 [y]–1/2 = K  (2) 2 2
[x]5/2 [y]–1/2 = K.(2)2 [x]5/2 [y]–1/2 = 4 K [x]5/2 [y]–1/2
Hence, rate becomes 4 times.
6. Answer (1)
Mechanism given is
Kc

NO  Br2
NOBr2
K
NOBr2  NO   2NOBr
slow
dx
From II- reaction, = K [NOBr2] [NO] …(i)
dt
NOBr2 
Kc =
[NO][Br2 ]
[NOBr2] = Kc [NO][Br2] …(ii)
Substituting eq. (ii) in eq. (i), we get
dx 2 dx 2
= KKc [NO] [Br2] or = K’ [NO] [Br2]
dt dt
7. Answer (1)
By initial rate method.
8. Answer (3)
Same % decay in same time. So, it indicates that reaction is of first order.
9. Answer (3)
The given reaction is
A + 2B + C o 2D + E
Order = 1 w.r.t. A; 2 w.r.t. B and zero w.r.t. C
dx 2
Initially = k [A] [B]
dt
Now when concentration is doubled

 dx  2 2
 dt  = k(2) [A] (2) [B]
 
 
 dx  dx  dx 
 dt  = 8k [A] [B]
2
   = 8  
  dt
   dt 
The rate of reaction increases by 8 times.
10. Answer (2)
The given reaction is 2N2O5 o 4NO2 + O2
R = 1.02×10–4 m/s; K = 3.4×10–5s–1
Reactions follows I-order kinetics as units of K is s–1
Rate = K [N2O5]
–4 –5
1.02 × 10 = (3.4 × 10 ) [N2O5]
1.02  10 –4 1.02  10
? [N2O5] = = =3M
 3.4  10 –5  3.4
11. Answer (1)
Half life for zero order reaction is given by the expression
a
t1/2 =
2K
When ‘a’ was doubled, Half-life also doubles. Hence, the reaction follows zero order kinetics.
12. Answer (2)
0.693
For 1st order, t1/2 
k
13. Answer (3)
Order is determined from mechanism.
14. Answer (2)
rate = K[O][O3]
[O2 ][O]
K1 
[O3 ]
K1[O3 ]
[O] 
[O2 ]
15. Answer (2)
16. Answer (2)
aA o product
1 d[A]
R  k (zero order)
a dt
Integrating, we get: (A)t = (A)0 – akt
17. Answer (2)
Initial concentration is [A]0 = a M
Reaction follows zero-order kinetics
x = kt
x a
Here, x = a t = =
k k
18. Answer (3)
This reaction is zero order so rate = K
19. Answer (4)
–3 –1
Given, k = 6.93 × 10 min
[A]0 = 10 M; [A]t = 1.25 M
Hence, for 1st order reaction we can write
1 [A]0 1  10 
t= ln = ln  
k [A]t  6.93  10  –3
 1.25 
103 3ln2  103

? t= × ln (8) =
6.93 6.93
3  0.693  10 3  103 693

t= = × × 100
6.93 1000 693
? t = 300 minutes
20. Answer (4)
For second order reactions,
1
t1/2 =
K  A 0
? Half life decrease with increase in concentration of reactants.
st ln 2
For 1 order, t1/2 = and is independent of concentration.
k
For zero order,
dx
= K (both are same)
dt
21. Answer (3)
Let the initial concentration = a
Reaction follows I-order kinetics
1  a 
K= ln  
(60)  99.9 
 a– 100 a 
1  100a 
= in  
(60)  100a–99.9a 
1  100a 
= ln  
(60)  0.1a 
1 1000a 
= ln  
(60)  a 
ln(1000)
=
60
? For 50% decomposition we can write
ln2 60(ln2)
t= =
K ln(1000)
? t = (60) (0.3)
60log 2 60log2
? t= =
log (1000) log(103 )
60log2
? t= = 20 log2
3
? t = 20 × 0.3 = 6 minute
22. Answer (1)
T = 138.6 s
For 75% decomposition, we can write
1  a  1  100a 
K= ln   = ln  
t  75 a  t  100a–75a 
 a – 100 
1 100 a   ln 4 
? K= ln   =  
t  25 a  138.6 
2.303  2  0.3010
? K= = 0.01 = 10–2s–1
138.6
23. Answer (4)

mol L–1 s–1 = K (mol L–1)1
K = s–1
24. Answer (3)
The given reaction is
A(g)  B(g) + C(g)
At t = 0 P0 0 0
t = t P0–P P P
? Pt = P0 – P + P + P = P0 + P
? P = (Pt – P0)
Hence, applying I-order kinetics equation
1  P0  1  P0 
K= ln   = ln  
t  P0  P  t  P0  (Pt –P0 ) 
1  P0  2.303 P0
ln   = log
t 2P –P
 0 t t 2P0 – Pt
25. Answer (2)

[X]0 = 0.1 M; [X]t = 0.025 M
t = 40 minute
1  0.1  ln 4
? K= ln   =
40  0.025  40
Rate of reaction = K[X]
 ln 4  2ln 2
=   × (0.01)  × (0.01)
 40  40
2  0.693  0.01
= = 3.47 × 10–4 m/s
40
26. Answer (4)

A(g) o 2B(g) + C(g)
t =0 P0 0 0
t = t P0–P 2P P
? Pt = 0; = P0 ; Pt = P0 – P + P + 2P
Pt = P0 + 2P
After 10 min;
Pt = 180 mm Hg
180 = 90 + 2P 90 = 2P
P = 45 mmHg
? Applying I-order kinetics:
1  90  ln 2
? K= ln   =
10  90 – 45  10
0.693 0.693
K= = = 1.15 × 10–3 s–1
60  10 600
27. Answer (3)
Reaction is first order.
0.693
? t1/2   1 second
0.693
t t t
2 M 
1/2
1 M 
1/2
 0.5 M 
1/2
 0.25 M
i.e., 3 second
28. Answer (4)
For radioactive disintegration,
20 N0
t1/2 = 69.3 min. Nt = N =
100 0 5
ln 2 0.693
? O= = = 0.01 min–1.
t1/2 69.3
Applying I-order reaction,
1  5N0  ln 5
t= ln   =
 0.01  N0  (0.01)
2.303  0.7
? Time taken (t) =
(0.01)
t = 161 minutes
29. Answer (3)
For 2nd order reaction,
1 1
  kt
At A0
1 1  A 0kt

At A0
A0
 1  ktA 0
At
1
=1 + X
Y
(X + 1) Y = 1
Hyperbolic graph.
30. Answer (1)
loge(A0/At) = 0.693; at time = x second
At = A0/2
x represents half life
31. Answer (2)
32. Answer (1)
33. Answer (3)
34. Answer (4)
It represents parallel (or) simultaneous reactions.
35. Answer (4)
According to Arrhenius equation,
–Ea
K = A.e Rt
The rate constant is inversely related to activation energy. It is energy required to make it equal to threshold
level and it can be greater than 'H for the reaction.
36. Answer (4)
–Ea
K = A.e RT
A
When T o f, K = =A
e0
? As Tof; K = A.
37. Answer (3)
38. Answer (4)
R P
For (Ea)f = (Ea)b, 'H = 0

But 'S z 0
'G z 0 also
39. Answer (1)
K2 Ea  1 1
log10  
K1 2.303R  T1 T2 
 2  104  K  Ea  1 1 
log10   
 K  2.303  8.314  10  300 400 
3 
Ea = 98.8 kJ/mole
40. Answer (2)
 K  Ea  T   T 
log     
 K  2.303R  T T 
Kc Rate constant at Tc
K Rate constant at T
The reaction which has more value of Ea is more sensitive against temperature.
41. Answer (3)
X(s) 
 Y(g) + 2Z(g)
t=0 a
t=t a–x x 2x
t=  0 a 2a
P  3x
Pf  3a
2.303  a 
? K= log 
t  a  x 
42. Answer (4)

43. Answer (4)
Temperature coefficient for the reaction is given by
K T  10
Tc = = 2 and 3
KT
44. Answer (3)

According to Arrhenius logarithmic form,
Ea
log K = log A –
2.303 RT
1
Log K versus graph gives straight line having intercept = log A
T
–Ea
And slope (m) =
2.303R
Since Ea > 0; m < 0

Slope is negative having non-zero intercept.
45. Answer (3)
Fact
46. Answer (1)
k  Ea  T2  T1 
Arrhenius equation, log  2    
k
 1 2.303R  T1T2 
k 
log  2   1, k 2  10k1 k2 = 6.93 s–1
 k1 
0.693
t1/2 =  0.1 s
6.93 s1
47. Answer (4)

4
226
88 Ra o 2He + 222
86 Rn
4
222
86 Rn o 218
84 RaA + 2He
0
218
84 RaA o 218
85 RaB + –1E
4
218
85 RaB o 2He + 214
83 RaC
Element RaC will be lying in 15th group and 6th in period.

48. Answer (4)
Since D and E-rays are +vely and –vely charged particles, hence, they will be deflected by magnetic field in
one direction.
49. Answer (1)
92 U235 82 Pb207  7 2 He 4  4 –1 e0

50. Answer (3)
51. Answer (1)
52. Answer (3)
Number of grams atom, t = 0 of Au is equal to 1
After 260 hours (t1/2 = 65 hours)
ln 2
O=
65
ln 2 1  1
? = ln  
65 260  x 
260 ln 2  1
= ln  
65 x
 1 1
? 4 ln2 = ln   ln24 = ln
x
  x
1 1 1
? = 24 or x = 4 = g atoms
x 2 16
1 15
? Number of gram atoms after 260 hrs = 1 – =
16 16
53. Answer (3)

[N0] = 1 g atoms
? Since it is D-emitting.
Isotope it produces 2He4 (1/2 mole)
1
? Volume of gas liberated at STP = 22.4 × = 11.2 L
2
54. Answer (2)
ln 2 ln 2
 
t1/2 14
 ln 2 
Nt    30
 et  e  14   0.227
N0
55. Answer (4)
56. Answer (30)
t 87.5  3t 1  30 hr
2
57. Answer (34)

d[A]
 k1[A]  k 2 [A]  (k1  k 2 )A
dt
d[B]
 k1[A]  k1A 0 e (k1 k 2 )t
dt
k1
or [B]  [A 0  A]
k1  k 2
For maximum yield,
% yield 
[B]
 100 
 
k1 1  e(k1 k 2 )t
 100
[A 0 ] k1  k 2
For maximum yield,
k1 3.4
1  e(k1 k 2 )t  1  100   100  34%
k1  k 2 10
58. Answer (50)
A 
Kt  ln  0 
 At 
4A o B + 2C
1600
1600 – 4P P 2P
1600 – 4P + P + 2P = 1300
P = 300
? 1600 – 4P = 400
? Half life of A = 5 min
5
 1
Partial pressure of A after 25 min = 1600   = 50 torr
2
59. Answer (02)
t/t1/2
 1
NA  N0  A  
2
t/t1/2
 1
NB  N0 B  
2
t t

1  1 100 50
4  
16  2 
t t
6 
50 100
t = 600 min = 10 hr
60. Answer (10)
After time t
Nt  N0 e t (Radioactive decay follows 1st order kinetics)
N1 t N0 1 e t 1

N2 t N0 2 e t 2
? (N0)1 = (N0)2
N1 t
ln    2  1  t  –2.303  2
N2 t
N1 t
 log  –2
N2 t
Previous Years Questions

[Rates of Chemical Reaction]
61. Answer (4)
2
k eq 
kf

N 2  H 2O
k b H  2 NO 2
2
Rearranging
2
2 k b N 2  H 2O
k f NO H 2  
H 2 
On comparing Rf and Rb at equilibrium,
Rb  kb
N 2  H 2O 2
H 2 
62. Answer (3)
3
2A  3B  C  3P
2
1 dn A 1 dn B 1 dn C
rate   
2 dt 3 dt 3 / 2 dt
dn A 2 dn B 4 dn C
 
dt 3 dt 3 dt
63. Answer (2)

k1

A 2
2A
k –1
1 d A 
– = k–1 [A]2 – k1 [A2]
2 dt
d A 
= –2k–1 [A]2 + 2k1 [A2]
dt
d A 
= 2k1 [A2] – 2k–1 [A]2
dt
64. Answer (1)
xA oyB
dA 1 dB
? 
xdt y dt
dA dB x
 
dt dt y
 dA   dB  x
log    log  dt   log  y 
 dt     
x
2
y
The reaction is of type 2A o B.
65. Answer (1)
2N2O5 o 4NO2 + O2
–1 d N2O5  1 d NO2  d  O2 
rate = = =
2 dt 4 dt dt
Since, instant of finding rate of formation of NO2 is not mentioned, hence
– [N2O5 ]  2.75 – 3  0.25

∵ =– = M min–1
t 30 30
 NO2  – [N2O5 ]
? = 2×
t t
0.25
= 2×
30
= 1.67 × 10–2 M min–1
[Order and Molecularity]
66. Answer (3)
From experiment I and II, it is observed that order of reaction w.r.t. 3 is zero.
From experiment II and III,

1.386  102  0.2 
 
6.93  103  0.1 
? D=1
Rate = K[A]1
6.93 × 10–3 = K(0.1)
K = 6.93 × 10–2
For 2A + B o products
 A 0
2 Kt = ln
A
0.693
t1/2 =
2K
0.693
= =5
6.93  102  2
67. Answer (3)
r = K[A]x [B]y
r2
 2x.2y  8  x  y  3
r1
r3
 2x  2  x  1
r1
? y=2
68. Answer (4)
2A + B o C
Rate = k[A]x [B]y
Exp-1, 0.045 = k[0.05]x [0.05]y …(i)
Exp-2, 0.090 = k[0.1]x [0.05]y …(ii)
Exp-3, 0.72 = k[0.2]x [0.1]y …(iii)
Divide equation (i) by equation (ii),
x
0.045  1 
 x=1
0.090  2 
Divide equation (i) by equation (iii),
y 1
0.045  0.05   0.05 

0.72  0.1   0.2 
2 y
 1  1
2  2 y = 2
   
Rate law = k[A]1 [B]2
69. Answer (3)
Graph-(i) : In[Reactant] vs time is linear
Hence, 1st order
Graph-(ii) : [Reactant] vs time is linear
Hence, zero order
70. Answer (2)

Rate = k[A]a [B]b
6 × 10–3 = k(0.1)a (0.1)b ...(1)
2.4 × 10–3 = k(0.1)a (0.2)b ...(2)
1.2 × 10–3 = k(0.2)a (0.1)b ...(3)
Solving eq (1), (2) and (3), we get
a = 1, b = 2
6 × 10–3 = k(0.1)1 (0.1)2 [From (1)]
k=6
7.2 × 10–2 = 6(x)1 (0.2)2 x = 0.3
2.88 × 10–2 = 6(0.3)1 (y)2 y = 0.4
71. Answer (2)
Zero order reaction has complex mechanism. Zero order reaction is a multistep reaction.
72. Answer (1)
Rate = k[A]n
log[Rate] = log k + n log [A]
slope = n [n is order of the reaction]
? Correct sequence for the order of the reaction is d > b > a > c
[Integrated Rate Equations]
73. Answer (4)
For the reaction 2X o B, follow zeroth order
Rate equation is
2Kt = [A]0 – [A]
For the half-life,
 A 0
2 Kt 
2
0.2
K
226
1
K= M hr–1
120
? Time required to reach from 0.5 M to 0.2 M
2 Kt = [A]0 – [A]
t = (0.5 – 0.2) × 60 = 18 hour
74. Answer (3)
Rate constant of decomposition of X = 0.05 Pg/year From unit of rate constant, it is clear that the decomposition
follows zero order kinetics.
For zero order kinetics,
[X] = [X]0 – kt
5  2.5 2.5
t   50 years
0.05 0.05
75. Answer (2)
dN
When drug is administered bacterial growth is given by  5N2
dt
N0
 1  5t N0
Nt
N0
Thus, increases linearly with t.
Nt
76. Answer (4)
ln2
∵ A = A0e–kt k
t 1/2
ln 2
 t
4B  A 0 e 300
? ln 2 [given A0 = B0, A = 4B]
 t
B  B 0e 180
 1 1 
ln 2  t
4e  180 300 
t = 900 s
77. Answer (3)
A  Products
For a first order reaction,
ln2 0.693
t1/2  
k k
Time for 90% conversion,
1 100 ln10 2.303
t 90%  ln = 
k 10 k k
2.303
t 90%  t1/2  3.32 t1/2
0.693
78. Answer (3)
Since, half life is independent of the initial concentration of AB2. Hence, reaction is “First Order”.
2.303 log2
k=
t1/2
2.303 log2 2.303 100
= log
t1/2 t 100 – 80 
2.303  0.3 2.303
 log5
200 t
t = 467 s
[Experimental Determination of Rate Constant]
79. Answer (3)
k1 k2
A  B  C
d[B]
 k1[A] – k 2 [B]  0
dt
k1[A]
[B] 
k2
[Factors Affecting Rate of Chemical Reaction]

80. Answer (2)
K  Ae Ea /RT
So, as Ea increases, K decreases
and as T increases, K increases.
81. Answer (4)
k  Ae Ea /RT
Ea
Ink  In A 
RT
1
For Ink versus , slope = –y
RT
– y = – Ea
Ea = y
82. Answer (4)
Ea
ln K  ln A 
RT
Ea
Slope   4606 K
R
 K  E  T  T1 
ln  2   a  2
 K1  R  T1T2 
4606 100
=
400  500
= 2.303
K 
log  2   1
 K1 
K2
 10
K1
K2 = 10K1
= 10–5 × 10
= 10–4 s–1
83. Answer (1)
Activation enthalpy to form C is 5 kJ more than that to form D.
84. Answer (4)
K2 Ea  1 1
log    
K1 2.303R  T1 T2 
1 Ea  1 1 
 
8.314  2.303  600 800 

log 4
2.5  10
Ea 200
3.6  
8.314  2.303 600  800
Ea = 165.4 kJ/mol | 166 kJ/mol
85. Answer (2)
Ea
logk  log A –
2.303 RT
Ea
Slope  –
2.303 R
So, correct order of activation energies Ec > Ea > Ed > Eb

86. Answer (1)
Rate of reaction at 700 K in the absence of catalyst = Rate of reaction at 500 K in the presence of catalyst
(E a )  (E a ) c  30 kJ / mole
∵ Rate is same
? Rate constant will also be same
(Assuming same value of pre exponential factor)
k  Ae E a /RT
E a (E a ) c
 
R  700 R  500
  5E a  7(E a ) c  7(E a  30)
 2E a  210  E a  105 kJ / mol

? Activation energy in the presence of catalyst = 105 – 30 = 75 kJ/mol
[Miscellaneous]
87. Answer (1)
C + O2 o CO2 No catalyst
Ostwald process :
Pt/Rh
4NH3  5O2   4NO  6H2O
Haber’s process,
Fe
N2  3H2   2NH3
88. Answer (1)
To minimize contamination, use freshly prepared starch solution to determine end point. As KI is used in
excess to consume all the H2O2 the concentration of sodium thiosulphate solution is less than KI solution.
After appearance of blue colour record the time immediately.
[Rates of Chemical Reaction]
89. Answer (4)
2K 2Cr2O7 + 8H2SO4 + 3C2H6 O  2Cr2 (SO4 )3 + 3C2H4 O2 + 2K 2 SO4 + 11H2O
1 d[C2H6 O] 1 d[Cr2 (SO 4 )3 ]

Rate =  =
3 dt 2 dt
d[Cr2 (SO 4 )3 ]
= 2.67 mol min–1
dt
d[C2H6 O] 3 d[Cr2 (SO 4 )3 ]

 =
dt 2 dt
3
=  2.67
2
= 4 mol min–1
90. Answer (0)
K

[PtCl4 ]2   H2 O f
[Pt(H2 O)Cl3 ]  Cl
K b
d [PtCl4 ] 
2
 K f [PtCl4 ]2    K b [Pt(H2 O)Cl3 ]  [Cl ]

dt
Kf 4.8  10 5
KC    2  10 2
Kb 2.4  10 3
91. Answer (27)
2A + B2  2B
rate  [A]2 [B2 ]  (PA )2 PB2  

Now, if volume is reduced by a factor of 3, then P is increased by a factor of 3.
 1
 V  
 P
ratec v  3PA 
2
3PB   27PA2  PB
2 2
Rate increases by 27 times the previous rate.

92. Answer (4)
AoB
Increase in concentration of B
Average rate =
Time
0.2 mol L–1

=
0.5 hr
 0.4  4  10 –1 mol L–1h–1

93. Answer (1)
1  d[A]  1  d[B]  1  d[C]  1  d[D] 

     
    r4  dt 
Rate =
r1  dt  r2  dt  r3  dt 
d[D] r4  d[B] 
 
dt r2  dt 
r4 3

r2 2
d[B] r2  d[A]  r
   2 2
dt r1  dt  r1
r2  2r1
r4 = 1.5r2 = 3r1
d[C]
= 1 m.mol dm–3 s–1
dt
d[D]
= 9 m.mol dm–3 s–1
dt
d[D] r4 d[C] r
   4 9
dt r 3 dt r3
r4 = 9r3 = 3r1
 r1  3r3
3r3A + 6r3B o r3C + 9r3D
1
? Rate of reaction =  9 m.mol dm–3 s–1
9
= 1 m.mol dm–3 s–1
94. Answer (40)
Rate  [X]1[Y]0
Rate = k[X]
From Exp I and II,
1 0
4  10–3  L   0.2 
   
2  10 –3  0.1   0.1 
2 = (10 L)1
Hence L = 0.2 mol/L
From Exp III and IV,
0
M  10 –3  0.4  0.4 
  
2  10 –3  0.1  0.2 
M
4
2
M=8
M 8
  40
L 0.2
[Order and Molecularity]
95. Answer (1)
2NO(g) + 2H2(g)  N2(g)  2H2O(g)
Rate = k[NO]x [H2]y

7 × 10–9 = k(8 × 10–5)x (8 × 10–5)y ...(i)
2.1 × 10–8 = k(24 × 10–5)x (8 × 10–5)y ...(ii)
Now dividing (ii) by (i),
x
2.1 108  24  105 
 
7  109  8  105
 
3 = 3x
x=1
Similarly,
y
8.4  108  32  105 
 
2.1 108  8  105
 
y=1
Order of reaction w.r.t. NO is 1.
96. Answer (03)
Rate (r) = k[NO]x [Cl2]y
From run (2) and (3),
(r0 )3 (0.20)x (0.20)y

(r0 )2 (0.10)x (0.20)y
1.40
2x   22
0.35
? x=2
From run (1) and (2),
(r0 )2 (0.10)x (0.20)y

(r0 )1 (0.10)x (0.10)y
0.35
 2y
0.18
y|1
? r = k[NO]2 [Cl2]1
? Overall order of reaction = 2 + 1 = 3
97. Answer (0)
1
t1 
2 [P0 ]n1
 t1 2 1 P0 n21

 t1 2 2 P0 1n1
n 1
340  27.8 

170  55.5 
n 1
 1
2 
2
2 = (2)1 – n
1–n=1
n=0
98. Answer (1)
 t1/2 A  240 s when P = 500 torr
 t1/2 A = 4 min = 4 × 60 = 240 sec when P = 250 torr

If means half-life is independent of concentration of reactant present.
? Order of reaction = 1
99. Answer (2)
1
t1  n 1
2
 a0 
t1/2 = 100 s a0 = 0·5
t1/2 = 50 s a0 = 1
n 1
100  1 

50  0  5 
(2) = (2)n–1
n–1=1
n=2
100. Answer (2)
Let the rate of reaction (r) is as
r = K[NO]n[H2]m
From 1st data
0.135 = K[40]n·(65.6)m …(i)
From 2nd data
0.033 = K(20.1)n · (65.6)m …(ii)
On dividing equation (i) by equation (ii),
n
0.135  40 

0.033  20.1 
4 = (2)n
? n=2
? Order of reaction w.r.t. NO is 2.
[Integrated Rate Equations]
101. Answer (60)
Time for completion of 75% of a Ist order reaction = 90 min.
1
? Half life, t 1  t3
2
2 4
90
  45 min
2
0.693
Rate constant, K  min 1
45
Time for completion of 60% of the reaction,
2.303 10
t 60%  log
K 4
2.303  45
 [1  0.6] 60
0.693
102. Answer (2)
A  Products
Rate constant of a first order is given as
2.303 [A]
k log 0
t [A]t
2.303 100
= log = 2 × 10–3 s–1
570 32
103. Answer (108)
Initially : [A0] = [B0] = a
After time ‘t’ min : [A] = 16 [B]
[A] = [A0] e –k A t
[B] = [B0] e –kB t
a. e –k A t = 16ae –kB t
e– k A –kB  t = 16
(kB – kA)t = ln16
 1 1 
ln2  –  t  4ln2
 18 54 
54  18  4
t=  108 min
36
104. Answer (1)
a0 = 50 mol L–1
at = 10 mol L–1
1 50
K  2.303 log
120 10
= 0.01341
= 1.34 × 10–2 min–1
x = 1.34  1 (nearest integer)
105. Answer (658)

A o 2B
t=0 1 0
t = 100 min 1 – x 2x
2x = 0.2 x = 0.1
1 [A]
k  ln 0
t [A]
ln 2
k
t1
2
ln 2 1 1
 ln
t1 100 0.9
2
ln2  100
t1   (600  700) min* (depending on value of log 3)
2
ln10 – ln9
106. Answer (81)


H
Sucrose  H2O  Glucos e  Fructose
t0 a 0 0
t  9 hr ax x x
0.693 –1
k hr
3.33
2.303 a
k log
t ax
0.693  9  1
 log10  
3.33  2.303 f
 1
log10    81
f
107. Answer (26)
For a 1st order reaction,
a0
kt  ln
at
1 a0
t 40%  4
ln
3.3  10 0.6a0
104 10
 ln sec
3.3 6
10 4  0.51
 min
3.3  60
= 25.8 min
| 26
108. Answer (200)
A + B
at initially 1 1
mole mole
1 1
after 100 s
2 4
1 1
after 200 s
4 16
Ans. 200 seconds
109. Answer (16)

A0
∵ kt = ln
A
ln2 A0
t 67%  ln
t1 0.33A 0
2
log 2 1
t 67%  log
t1 0.33
2
t67% = 1.566 t1/2

x = 15.66
Nearest integer = 16
110. Answer (2)
For first order reaction,
ln A = ln A0 -– kt
Hence Slope = –k
–k = –3.465 × 104
0.693
k=
t1/2
0.693
3.465 × 104 =
t1/2
t1/2 = 2 × 10–5 s
111. Answer (165)
A  B
Reactant Product
0.693
k=  165  10 6 s1
70  60
? x = 165
112. Answer (100)
0.693
t1/ 2  t1/2 given = 0.3010
K
0.693
K
0.3010
K = 2.30
2.303 (A )
K log 0
t (A t )
A0 o initial concentration of reactant
At o concentration of reactant at time t
2.303 (A )
2.303  log 0
2 (A t )
(A 0 )
2  log
(A t )
A0
100 
At
[Experimental Determination of Rate Constant]
113. Answer (106)
Rate = k [Amount of virus]
1 1
k ln (∵ 10% of virus is inactivated)
1 min 0.9
= 2.303 (1– 0.954)
= 0.1059
= 105.9 × 10–3
| 106 × 10–3 min–1 (nearest integer)
114. Answer (7)
For the first order reaction,
[R]0
Kt  ln
[R]
(2.4  10–2 )
K  60  ln
(1.6  10 –2 )
= 2.303 × (log3 – log2)
= 2.303 × (0.477 – 0.301)
K = 6.7 × 10–3 min–1
[Factors Affecting Rate of Chemical Reaction]
115. Answer (3.98)
Using Arrhenius equation,
K  Ae E a /RT
Assuming A (pre - exponential factor remains same)
k  E  1 1 
ln  400   a   
 k 300  R  300 400 
 1 60  E a 100
ln     
 40 1  R 300  400
3 Ea
ln   0.4
2 1200R
? Ea = 0.4 × 1200 × 8.3 = 3984 J/mol
Ea = 3.984 kJ/mol = 3.98 kJ/mol
116. Answer (84297.48)
∵ k = Ae E a /RT
Assuming A and Ea to be temperature independent.
k 2 Ea  1 1 
ln  
k1 R  T1 T 2 
Ea  1 1 
 ln 5    
R  300 315 
1.6094  8.314  300  315
 Ea   84297.48 J/mol
15
117. Answer (100.00)

E
 a
k  Ae RT
Assuming A and Ea to be independent of temperature
k 2 Ea  1 1 
ln    
k1 R  T1 T 2 
Ea  1 1 
ln3.555  
8.314  303 313 
1.268  8.314  303  313
Ea   99980.7  99.98 kJ/mol
10
118. Answer (16)
k1 = 6.36 × 10–3 s–1 T1 = 700 K
Ea = 209 kJ/mol
k2 = x × 10–6 s–1 T2 = 600 K
k 2 Ea  1 1
ln    
k1 R  T1 T2 
 x  10 6  209  103  1 1 
log  3 
  700  600 
 6.36  10  8.31  2.303  
log(x  10 6 )  4.79
x  106  1.62  105

x  16.2 16 (Nearest integer)
119. Answer (2)
For first order reaction,
t75% = 2 × t50%
A0
∵ kt  ln (for first order reaction)
A
A0
At t 50%  A 
2
 kt 50%  ln 2
A0
At t 75%  A 
4
 kt 75%  ln 4
120. Answer (45)
A+B
Enthalpy change = y
Energy
M+N
Reaction Coordinate
y = 45 kJ/mol
121. Answer (47)
(2.47  103 )
log10 K  20.35  ...(i)
T
Ea
logK  log A  ...(ii)
2.303 RT
Comparing (i) and (ii),
Ea 2.47  103

2.303 RT T
Ea = 2.47 × 103 × 2.303 × 8.314
= 47293.44 J mol–1
= 47.2934 kJ mol–1
122. Answer (10)
k2 Ea  1 1
log =  – 
k1 2.303R  T1 T2 
k1 (at 200 K) = ?
k 2 (at 300 K) = 1 × 10–3 s–1
1  10 –3 11.488  103  1 
log  1
k1 2.303  8.314  600 
1  10–3
 10
k1
k1 = 10 × 10 –5 s–1
123. Answer (526)
k  Ae Ea /RT
Ea 1
logk = logA – 
2.303R T
From given graph,
–Ea
slope = –10000 =
2.303R
k2 Ea  1 1
∵ log   – 
k1 2.303R  T1 T2 
10 –4  1 1
log –5
 10000  – 
10  500 T2 
10000
 1  20 –
T2
10000
 T2   526.3  526 K
19
124. Answer (52)

K2 Ea 1 1
log    
K1 2.303 R  T1 T2 
Ea  1 1 
log5  
2.303  8.314  300 325 

0.7  2.303  8.314  300  325

Ea  J mol1
25
 52271 J  52.271kJ mol1 52
125. Answer (14)
Energy of activation, Ea = 80.9 kJ mol–1
Temperature of reaction, T = 700 K
Fraction of molecules having enough energy to react  e Ea /RT  e  x

Ea 80900
 x   13.9 14
RT 8.31 700
126. Answer (50)
XoY
'E = (Ea)f – (Ea)b
– 20 = 30 – (Ea)b
(Ea)b = 50 kJ
127. Answer (154)
Slope = –18.5
ln K
103
T
Ea
In K = In A –
RT
Ea
 Slope of the graph    18.5
R  103
 Ea  18.5  8.31 1000 154 kJ mol1
128. Answer (4)
K  Ea  Ea
ln 
K RT
10  103

8.314  300
K 100
ln 
K 8.314  3
K
 e4
K
x4
129. Answer (166)
2  10 4
lnk = 33.24 
T
Ea
?  2  104
R
Ea = 2 × 104 × 8.3 = 166 kJ/mol
130. Answer (59)
T1 = 300 K
(Rate constant)
K2 = 2K1, on increase temperature by 9K
T2 = 309 K
Ea = ?
K2 Ea  T2  T1 
log   
K1 2.3R  T2  T1 
Ea  9 
log2 
2.3  8.3  309  300 

0.3  309  300  2.3  8.3

Ea 
9
 58988.1 J / mole
59 k J/mole
131. Answer (1)
K  532611  1 1 
log  310   300  310 
 K 300  8.3  
K 310
 103  K 300  1 103  K 310
K 300
132. Answer (216)
 Ea
k = A e RT
Ea 26000

RT T
Ea = 26000 × 8.314
= 216164 J = 216 kJ
133. Answer (8)
20
ln K
5
1 (K–1)
T
20
Slope 
5
Ea
ln K  ln A 
RT
Ea 20 20 R
   E  8 cal mol–1
R 5 5
[Nuclear Chemistry]
134. Answer (23.03)
n2 0.693
Decay constant (O) = = = 0.1 yr–1
half life  6.93
 100 
Now O (t90%) = ln  
 10 
t90% = 10 ln 10
= 10 × 2.303
= 23.03 yr
135. Answer (75)
2.303 A0
O= log
t A
0.693 2.303 A
 log 0
200 83 A
A
 0.75
A0
Hence, percentage of original activity remaining after 83 days is 75%
136. Answer (1)
1
kt = ln
1 X
0.693 1
(100)  ln
30 1 X
1 1
2.303 = 2.303 log = 10
1 X 1 X
1 = 10 – 10X
9
X = = 0.9 Pg
10
Amount of X remaining = 1 – X
= 1 – 0.9 = 0.1 Pg
= 1 × 10–1 Pg

Step-3
Chapter 4
Solutions
SECTION - A
Objective Type Questions (One option is correct)
1. Answer (3)
R = K[A]a [B]b
1
From given data, a = 2 and b 
2
d[A] 2d[B]
? R 
2dt dt
2. Answer (1)
For the reaction,
1
N2O5 o 2NO2  O2
2
We can express the rate as,
d N2 O5  1 d NO2  1 d [O2 ]

= . = 1/2  .
dt 2 dt dt
1
K1 [N2O5] = K [N O ] = 2K3 [N2O5]
2 2 2 5
Hence, we can write
K2
K1 = = 2K3
2
2K1 = K2 = 4K3
3. Answer (1)
1 dY 0.5 dX
Rate =   [X]  
2 dt 2 dt
X = [X]0 e–kt
= [X]0
0.5
8
X = [X]0 e 2
e2
4. Answer (3)
The gas phase reaction is
R o A + B + C + D
t=0 x0 0 0 0 0
t = t x0–P P P P P
? x0 – P + 4P = y x0 + 3P = y
 y– x 0 
? 3P = (y – x0) P =  
 3 
Applying I-order kinetics equation
1 x0
K= ln x  P
10 0
2.303 x0
? K= log
10  y – x0 
x0 –  
 3 
2.303 3 x0
? K= log
10 3 x0  y  x0
2.303 3 x0
? K= log
10 4 x0  y
5. Answer (4)
k1 [A]2 k1
  [A]  [A 2 ]
k 1 [A 2 ] k 1
Rate = k2[A] [B] (r.d.s.)
k1
= k2  [A 2 ]  [B2 ]
k 1
k1
= k2   [A 2 ]1/2 [B2 ]
k 1
1
Order of reaction =  1  1.5
2
6. Answer (1)
X2 (g) 
 2X(g)
At t = 12 min a  x 2x
a
∵ a – x = 2x x =
3
3
? K × 12 = ln
2
ln2  12
t1/ 2   21 minutes
ln3  ln 2
K = 0.033 minutes–1
1
Average life =  30 minutes
K
7. Answer (4)
1
t1/ 2 
[A]n0 1
1
4
2n  1
1
2
(2 2)n 1
n 1
? 22 2
n=3
8. Answer (1)
Activation energy is an intensive property and it is independent of stoichiometric co-efficient of the reaction.
9. Answer (2)
Given definition is for collision frequency(Z), frequency factor is A.
10. Answer (2)
From given data :
R = K[X]1 [Y]0
4  10 3
K=  2  10 2 sec 1
0.2
11. Answer (1)
Catalyst participates in reaction but does not get consumed in the reaction.
12. Answer (1)
K  E
log  c  
 K  2.303RT
13. Answer (2)

As atomic number increases and mass number remains constant.
14. Answer (1)
Rate1 = O1N1 …(i)
Rate2 = O2N2 …(ii)
According to question,
Rate1 = Rate2
O1N1 = O2N2
N1 2 2
= =
N2 1 1
15. Answer (3)

The activity of radioactive sample decreases from 20 to 1.25
t = 2000 yrs.
1  20  ln16
O= ln   = 2000
2000  1.25 
–3 –1
O = 1.386 ×10 y
? Half life is
ln 2 ln 2
t1/2 = × 2000 = × 2000 = 500 years.
ln16 4ln 2
16. Answer (3)
Moles of 90
Y  t1/ 2  Y

Moles of 90
X  t1/ 2  X
w / 90 73

1/ 90 20  365  24
w = 4.16 × 10–4 g
17. Answer (4)
1 1 1 1 1 1 
Moles of 42 He2  at the end of 36 years =       
 2 40 4 40 8 40 
1 7
=  moles
40 8
7 1 0.0821  273  1000
Pressure =   = 43.7
8 40 11.2
18. Answer (3)
dN
  Number M2+ ions
dt
19. Answer (3)
1 watt = 1 J s–1
6 –1
Capacity of power house = 15 × 10 J s
1 day = 86400 s
6
? For 1 day (86400 sec) energy required = 86400 × 15 × 10 J
= 1.296 × 1012 J
6 –19 –11
200 MeV = 200 × 10 × 1.6 × 10 = 3.2 × 10 J
∵ 3.2 × 10–11 J energy produced by 1 atom of U-235.
1.296  1012  1
? 1.296 × 1012 J energy will be produced = = 4.05 × 1022 atoms
3.2  10 –11
 4.05  1022 
Mass of 4.05 × 1022 atoms =  23  × 235 = 15.80 g
 6.023  10 
100
Since efficiency is 75% hence actual mass required = 15.8 × = 21.06 g
75
20. Answer (4)
Rate = K[ester][OH–]
SECTION - B
Objective Type Questions (One or more than one option(s) is/are correct)
1. Answer (1, 3, 4)
We can relate rate for the reaction
A + B o 2 C + D as :
– [A] – [B] 1 [C] [D]

= = =
t t 2 t t
We can conclude that (1), (3) & (4) are correct answer. (2) is not correct because
[B] 1 [C]
=
t 2 t
2. Answer (2, 3)
The rate law is given by
Rate = K [RCl]
For reaction, RCl + NaOH o ROH + NaCl .
The rate v [RCl] hence when [RCl] reduces to half, rate also becomes half and is not affected by [NaOH].
The rate always increases with the increase in temperature.
3. Answer (1, 2, 3, 4)
For any reaction we can write the rate law,
dx D E
= K[A] [B]
dt
Order is purely an experimental quantity which cannot be determined by stoichiometry of reaction. It can be
+ve, –ve, fractional or zero and order = (D + E).
4. Answer (1, 2)
Fact.
5. Answer (2, 3)
The given reaction is A o B. Rate law is given as
dx
= K[A]2
dt
It indicates that reaction follows II order kinetics.
1
t1/2 = hence half life is inversely related to concentration,
K[A]0
M 1
K has units = 2 
s.M M.s
1 litre –1 –1
= litre mol s
moles  s
and it depends upon temperature.
6. Answer (2, 3)
The reaction given is

A 2  B2
2AB
Mechanism

A 2
A  A (fast)
A + B2 o AB + B (Slow reaction)
A + B o AB (Fast reaction)
Applying the rate equation w.r.t. slow reaction,
dx
= k [A] [B2] …(i)
dt
and we can also write
[A]2
Kc =
[A 2 ]
1/2
? [A] = {Kc[A2]} …(ii)
Substituting eq. (ii) in eq. (i)
dx 1/2
= K {Kc[A2]} [B2]
dt
dx
= K’ [A2]1/2 [B2]
dt
1/2
Here K’ = K.Kc
? According to above rate law,
1
Order = 1  = 3/2
2
And since two reactants are involved hence molecularity is equal to 2.
7. Answer (1, 2, 4)
8. Answer (1, 4)
According to Boyle’s law,
1 K
P (at constant T and no. of moles) P =
V V
 1
Between P and   the graph will be straight line
V
P versus T graph will be straight line. For zero order x = kt
i.e., x versus t graph gives straight line and not log x versus t.
 K2  H  T2  T1 
log  K  =  
 1 2.303 K  T1T2 
1
Hence the graph between log Kp versus will be linear.
T
9. Answer (2, 3)
A catalyst alters the mechanism and consequently decreases or increases the activation energy.
It does not increase the frequency of collisions, since it depends upon temperature.
10. Answer (1, 2, 3, 4)
Fact.
11. Answer (1)
(E)af
Potential (E)ab Reaction path without catalyst
Energy
R Reaction path with catalyst
Collision number
12. Answer (1, 4)

Applying mass and charge balance,
27
 q  13  2  15  0 
Al  24He  30
P  0n1  
13 15
 m  27  4  30  1
12
 12  1  13  1
C  1H1  0 n1  7N13  
6
6 1 7  0 
30 30
 m  30  30  1
P Si  e0  0n1  
15 14 1
 q  15  14  1 
241
 241  4  244  1
Am  24He  244
Bk  0n1  
 95  2  97
95 97

13. Answer (1, 4)
When 1 proton convert into neutron then E+ as well as neutrino is produced.
14. Answer (1, 2, 3)
For radioactivity, which follows first order kinetics
ln2
O= hence, it is independent of the amount of substance taken. And O (or radioactivity) is independent
t1/2
of external factors like temperature and pressure.
Nuclear isomers contains same number of protons and neutrons.
15. Answer (2, 3)

A1 = ON1
A2 = ON2
1
'n = N1 – N2 =  A1  A 2 

T
 A1  A 2 
ln 2
SECTION - C
Linked Comprehension Type Questions
Comprehension-I
1. Answer (3)
2. Answer (1)
3. Answer (2)
Comprehension-II
1. Answer (2)
r10  r20  r30
r0 a r10
 1
r a(r20  r30 )
2. Answer (1)
r20  r30
r a(r20  r30 )
  0.(∵ r  0)
r0 ar10
3. Answer (3)
1  r  r0 
k ln  
30  r  rt 
1  r0  1  1 
ln    ln 2 ∵ rt r0 
30  rt  30  2 
Comprehension-III
1. Answer (3)
226 4 222
88Ra o 2He + 86 A
222
86 A  2He 4  218
84 B
218
84 B  2He 4  214
82 C
214 214 0
82 C 83 D B
1
? Atomic number of D will be 83 and will be lying in group 15.
2. Answer (1)
234 206
90Th  82Pb
Since atomic mass decreases from 234 to 206 the difference is 28 and per D-particle emission the mass
decreases by 4 units.
28
? Number of D-particles emitted = =7
4
Atomic no. decreases by 7 × 2 = 14 or it becomes 76.
In the product, no. of protons is 82 hence 6E particles are emitted
? No. of D-particles emitted = 7
No. of E-particles emitted = 6
3. Answer (3)
238
The given radioactive element is 92U o 2He4 + 234
90 X
? Number of neutrons in X = 234 – 90 = 144
SECTION - D
Matrix-Match Type Questions
1. Answer A(s), B(r), C(q), D(p)
For III-order reaction we can write
dx 3
= k (a – x)
dt
 dx 
The graph will be straight line between   and
 dt 
(a – x)3 passing through the origin.
For II order, the equation is,
1 1
[A]t = [A]0 + kt
1
The graph between [A] versus t is a straight line 1
t
[A]
1
having +ve slope and intercept = [A] .
0
t
? The graph is for II-order reaction.
For I-order reaction the equation can be written as
dx
= k (a – x)
dt
 dx 
Hence   v (a – x)
 dt  Rate
? The graph for I-order is
For zero-order reaction, the concentration decreases
as time progresses at constant rate. (conc.)
2. Answer A(s), B(r), C(q), D(p)

Half life for the reaction is inversely related to (a)n–1 where ‘n’ is the order of the reaction.
ln2 0.693
? For I-order; t1/2 = =
k k
a
For zero order; t1/2 =
2k
For II-order reaction,
1
t1/2 =
k.a
The temperature coefficient of reaction is the ratio of rate constants differing by a temperature of 10ºC.
3. Answer A(q), B(r), C(s), D(p)
4. Answer A(q), B(r), C(p), D(s)
Applying the mass –balance and charge balance
The reactions can be written as
9 4 12 1  mass  13 
(A) 4Be + 2He o 6C + 0n  
 charge  6 
 mass  12  2  10  4 
(B) 6C
12
+ 1D o 5B
2 10
+ 2He
4
 
 charge  6  1  5  2 
 mass  14  4  17  1
(C) 7N14 + 2He4 o 8O17 + 1H1  
 charge  7  2  8  1 
40  mass  40  1  4  37 
(D) 20Ca + 1H1 o 19K
37
+ 2He4  
 charge  20  1  19  2 
SECTION - E
Assertion-Reason Type Questions
1. Answer (4)
The rate of reaction also depends upon temperature and order of the reaction can be positive, negative, zero
or even fractional.
2. Answer (1)
Rate = k [reactant].
3. Answer (3)
For acidic hydrolysis the reaction is
CH3COOCH2CH3 + H2O o CH3CH2OH + CH3COOH
dx
= K[CH3COOCH2CH3]
dt
but two species are involved in the reaction. Hence, it is bimolecular. These reactions are pseudo-unimolecular
reactions.
? Statement (1) is true but statement (2) is false.
4. Answer (2)
Half life for I-order reaction is given as
ln2
t1/2 = (independent of initial concentration & inversely proportional to K)
K
? Statement (1) & (2) both are correct but statement (2) is not the correct explanation of statement (1).
5. Answer (2)
k  Ae Ea /RT
For Ea = 0 k = A
6. Answer (2)
The rate of reaction generally increases the rate by 2 times to 3 times. We also define
K T 10
= TC (Temp. coefficient)
KT
and with the increase in temperature collision frequency increases as more molecules cross the energy barrier
and acquire activation energy.
7. Answer (2)
Only a positive catalyst lowers the activation energy and increases the rate of reaction.
And ('H) = (EA)f – (EA)b
? Statement (2) is not the correct explanation because the catalyst provides an alternate mechanism for the
conversion of reactants to products.
8. Answer (3)
Radioactivity is a nuclear phenomenon and is independent of external factors like temperature, pressure etc.
Radioactivity follows first order kinetics and number of nuclei at any time ‘t’ is given by
Nt = N0 e–Ot
? Statement (1) is correct but statement (2) is false.
9. Answer (2)
Elements with higher atomic number are more stable if they have slight excess of neutron as this increase
the attractive force and also reduces repulsion between protons.
SECTION - F
Integer Answer Type Questions
1. Answer (2)
 rSN 2  4.7  10 5 RX  OH 
% rate of SN 2     100   100 2.1 ∵ OH   0.001M

 rSN 1  rSN 2  4.7  10 5 RX OH   0.24  105 RX
2. Answer (4)
2.303 1 2.303
t 99.99%  log10 4  4 
k 10 k
2.303 1 2.303
t 90%  log10 1 
k 10 k
3. Answer (10)
[C] k1

[D] k 2
[C]
2
[D]
so, 2k2 = k1
4. Answer (1)
∵ C is low, then 1  k 2 C  1
dC
  k1C
dt
st
Hence, reaction is of 1 order.
5. Answer (7)
At = A0 – kt
A0  A t
k=
t
0.493  0.458 0.493  0.423
? k1 = , k2 
5 10
k1 = k2 = 0.007
? 1000k = 7
6. Answer (5)
Ea
H2O  O  2OH H  72 kJ
Eb
2OH  H2O  O H  72 kJ
Also, Ea – Eb = 'H
Eb = 5 kJ/mol
7. Answer (30)
x = 2, from units of k.
 2  Ea 10
ln    
 1.7  8.3 310  300
Ea = 12504.78 J/mol
A  keEa /RT
Ea  12504.78 
exp  exp    129
RT  310  8.3 
E 
y  A  exp  a   k  129  2  10 2
 RT 
= 2.58 dm2 mol–1 sec–1
2.58  1000
 30
43  2
8. Answer (4)
After 200 minutes,
a
Remaining about of X 
22
a
Remaining about of Y 
24
24
Ratio = =4
22
SECTION - G
Previous Years Questions
1. Answer (C)
23 23
11 Na  10 X  01e
2. Answer (D)
r = K[G]D [H]E
8r = K[2G]D [2H]E
2r = K[2G]D [H]E
? D=1E=2
? order of reaction = 3
3. Answer (A)
0.693
k1 =
t1/2
0.693
k1 = (first order kinetics) ....(1)
40
1.386
k0 = (zero order kinetics) ....(2)
2  20
k1
= 0.5 mol–1 dm3
k0
4. Answer (D)
1
log k = – (2000) + 6.0
7
Ea
Comparing this equation with log k = log A – , we get
2.303 RT
log A = 6
? A = 106 s–1
Ea 2000
and – =–
2.303 RT T
Ea = 2000 × 2.303 × 8.314
Ea = 38.3 kJ mol–1
5. Answer (A)
Ea

k  A e RT
Ea
ln k = ln A –
RT
6. Answer (A)
27 He4 30
13 Al 
2
 14 Si  1H1
(X)
27 He4 30
13 Al 
2
 15 P  10 n
(Y)

30 1
14 Si  1 e
(Z)
7. Answer (D)
The order of reaction with respect to P is one since t3/4 is twice of t1/2. From the given graph the order of
reaction with respect to Q is zero. Therefore, overall order of reaction is one.
8. Answer (B)

r2  [M]2 
 
r1  [M]1 
8 = (2)D
D=3
So, order of reaction is 3.
9. Answer (A, B, D)
2.303 A
t log
m 0.4  102  Α
8  0.693 2.303
 log250
k k
103
 2.303log
4
 2.303  (3  2  0.3010)
10. Answer (A)
Rate with respect to weak acid
R1 = K[H+]WA[ester]
and rate with respect to strong acid
R2 = K[H+]SA[ester]
R1 [H+ ]WA 1
? = + =
R 2 [H ]SA 100
[H ]SA 1
? H     0.01M  C
WA 100 100
D = 0.01
Ka for weak acid = CD2
= 1(0.01)2 = 1 × 10–4
11. Answer (A, B)
9
4 Be    84Be  10n
9 1
4 Be  H  84Be  12H
1
12. Answer (B, C, D)

o A high activation energy usually implies a slow reaction.
o Rate constant of a reaction increases with increasing temperature due to the increase in greater number
of collisions whose energy exceeds the activation energy.
–E /RT
o k  P Ze a
So, pre-exponential factor (A) = P × Z and it is independent of activation energy or energy of molecules.
13. Answer (B, D)
When N/P ratio is less than one, then proton changes into neutron.
Positron emission : 11 H  10n  01 
Capture : 11 H  0
1 e  10 n  X-rays
14. Answer (A, D)

A exp erimental
Steric factor =
A calculated
Steric factor = 4.5
It means Aexperimental > Acalculated
[This seems that reaction occurs more quickly than particles collide, thus concept of steric factor was
introduced]
15. Answer (A, D)
A o 2B + C
P0 – –
P0 – P 2P P
Pt = P0 + 2P
Pt  P0
P=
2
 P0  2P0
Kt  ln   ln
 Pt  P0   3P0  Pt
 P0   
  2  
Kt  ln 2P0  ln(3P0  Pt )
ln (3P0 – Pt)
Time
Rate constant of reaction is independent of initial concentration.
92U
238 o 90Th
234 + 2He4
90Th
234 o 91Pa
234 + –1e
0
91Pa
234 o 92Z
234 + –1e
0
92Z
234 o 90Th
230 + 2He4
? x1 = D ; x2 = x3 = –1E
0 ; x4 = D
Z has atomic number 92.
d[P]
rate   k[X]
dt
2X  Y  P
2 mole 1 mole
1 mole 0.5 mole 0.5 mole
d[X]
– = k1[X] = 2k[X] 2k = k1
dt
d[Y]
– = k2[X] = k[X] k2 = k
dt
1
2k  ln 2
50
1 0.693
k ln 2   6.93  10 –3 s –1
100 100
ln2 ln2  100
 t1/2 x    50 sec
k1 2  0.693
At 50 s,
d[X] 0.693
–  2k[X]  2  1
dt 100
= 13.86 × 10–3 mol L–1 s–1
At 100 s,
d[Y] 0.693 1 1
–  k 2 [X]  k[X]   (∵ Concentration of X after 2 half lives = M)
dt 100 2 2
= 3.46 × 10–3 mol L–1 s–1
18. Answer (A)
k  X
(I) rate 
Xs   X 
Case-1 : [X] >> Xs; [X] + Xs | [X]
k  X
rate  k (Zero order w.r.t. X)
 X
? I o P, S
Case-2 : [X] << Xs; [X] + Xs | Xs
k  X
rate   k   X (1st order w.r.t. X)
Xs
? I o Q, T
Case-3 : [X] | Xs
k  X
? rate 
Xs   X 
In this case, curve-R given in List-II will match.
? I o P, Q, R, S, T (The graph of half-life should start from origin)
k  X
(II) rate 
Xs   X 
∵ [X] << Xs
? Xs + [X] | Xs
k  X
? rate   k   X (1st order w.r.t. X)
Xs
? II o Q, T
k  X
(III) rate 
Xs   X 
∵ [X] >> Xs
? Xs + [X] | [X]
k  X
? rate  k (Zero order w.r.t. X)
 X
? III o P, S
2
k  X
(IV) rate 
Xs   X 
∵ [X] >> Xs
? Xs + [X] | [X]
2
k  X
? rate   k  X (1st order w.r.t. X)
 X
? IV o Q, T
19. Answer (8)

238 214
92 U 
 82 Pb  X24 He  y01 e
24 = 4x; x = 6
10 = 2x – y
y=2
? x+y=8
20. Answer (0)
For zero order reaction,
dx
k
dt
From 1 to 0.75 (M),
0.25
5
0.05
From 0.75 to 0.40,
0.35
5
0.07
From 0.40 to 0.10,
0.30
5
0.06
It mean order of this reaction is zero.
21. Answer (3)
142
92 U235  54 Xe + 38
90
Sr +3 10n
22. Answer (8)
63
29 Cu  11H  610 n  ( 24 He)  211H  X(52
26 Fe)
Fe belongs to group-8.
23. Answer (9)
2.303 1
t1/8  log10 ...(i)
k 18
2.303 1
t1/10  log10 ...(ii)
k 1 10
[t1/8 ] log8
 10   10  3  0.3  10  9
[t1/10 ] log10
24. Answer (9)
238 206 4 0
92 U  82 Pb  8 2He  6 – 
Now, number of moles in gas phase = 1 + 8 = 9 mole

At constant temperature and pressure
PF nF 9
  9
Pin nin 1
25. Answer (8)
2 
8H  5 Fe(H2O)2 (OX)2   MnO4  Mn2  5 Fe(H2O)2 (OX)2   4H2O
1 d[H ] d[MnO4 ]
Rate   
8 dt dt
rate of [H ] decay

Hence, 8
rate of [MnO4 ] decay
26. Answer (8430 – 8570)
A(g) + B(g) AB(g)
Eab – Eaf = 2RT
Af
=4
Ab
Kf
K=
Kb
–E a f /RT
Kf = Afe
K b = A b e –Eab /RT
Kf A (E –E )/RT
= f e ab af
Kb Ab
K = 4e2RT/RT
K = 4e2
'G° = – RT In K
= – RT (2 + ln 4)
= – 2500 (2 + 2 × 0.7)
= – 8500 J mol–1
Absolute value is 8500.00.
27. Answer (6.70 – 6.80)
A + B + C o Product
Rate v [A]x [B]y [C]z
R1 (0.2)x (0.1)y (0.1)z 6 ×10 –5

= =
R2 (0.2)x (0.2)y (0.1)z 6 ×10 –5
? y=0
Similarly x and z are calculated, x = 1, z = 1
6 ×10–5
Rate constant K = = 3 ×10 –3
0.2 × 0.1
? Rate at given concentrations = 3 × 10–3 × (0.15)1(0.25)0(0.15)1
= 6.75 × 10–5 mol dm–3 S–1
Y = 6.75
28. Answer (2.3)


2N2O5   2N2O4  O2 ; K  5  10 4 sec 1
Initial pressure (in atm) 1 – –
Pressure after time t sec 1 – 2x 2x x
? 1 – 2x + 2x + x = 1.45 atm
x = 0.45 atm
For 1st order reaction (taking into account of reaction stoichiometry)
a0
2Kt  ln
a0  x
∵ a0 v 1 and a0 – x v 0.1
1 1
t 4
ln  2.3  103 s
2  5  10 0.1
29. Answer (1.2)
238 206
92 U 82 Pb
Number of D-particles emitted per nuclei of
238 238  206

92 U 8
4
238
68  106
Moles of U present initially =
92
238
7 68  106
After three half lives, moles of 238
U decayed = 
92
8 238
7 68  106
? Number of D-particles emitted = 8    6.02  1023
8 238
= 12.04 × 1017
= 1.2 × 1018
? Z = 1.2


CLS ENG 23 24 XII Che Target 2 Level 1 Chapter 4

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CLS ENG 23 24 XII Che Target 2 Level 1 Chapter 4

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Step-1

Chemical Kinetics and Nuclear Chemistry

11. Answer (3)

19. Answer (1)

From K  Ae Ea /RT

From equations (i) & (ii),

0.693 2.303 100

2.303 0.15 2.303 2.303

Chemical Kinetics and Nuclear Chemistry

103 3ln2  103

3  0.693  10 3  103 693

20. Answer (4)

For second order reactions,

? Half life decrease with increase in concentration of reactants.

Let the initial concentration = a

Reaction follows I-order kinetics

23. Answer (4)

25. Answer (2)

Rate of reaction = K[X]

26. Answer (4)

Applying I-order reaction,

For (Ea)f = (Ea)b, 'H = 0

39. Answer (1)

42. Answer (4)

44. Answer (3)

Since Ea > 0; m < 0

47. Answer (4)

Element RaC will be lying in 15th group and 6th in period.

92 U235 82 Pb207  7 2 He 4  4 –1 e0

53. Answer (3)

57. Answer (34)

N1 t N0 1 e t 1

Previous Years Questions

63. Answer (2)

– [N2O5 ]  2.75 – 3  0.25

70. Answer (2)

[Factors Affecting Rate of Chemical Reaction]

So, correct order of activation energies  Ec > Ea > Ed > Eb

 2E a  210  E a  105 kJ / mol

2K 2Cr2O7 + 8H2SO4 + 3C2H6 O  2Cr2 (SO4 )3 + 3C2H4 O2 + 2K 2 SO4 + 11H2O

1 d[C2H6 O] 1 d[Cr2 (SO 4 )3 ]

d[C2H6 O] 3 d[Cr2 (SO 4 )3 ]

 K f [PtCl4 ]2    K b [Pt(H2 O)Cl3 ]  [Cl ]

rate  [A]2 [B2 ]  (PA )2 PB2  

Rate increases by 27 times the previous rate.

0.2 mol L–1

 0.4  4  10 –1 mol L–1h–1

1  d[A]  1  d[B]  1  d[C]  1  d[D] 

Rate = k[NO]x [H2]y

 t1/2 A = 4 min = 4 × 60 = 240 sec when P = 250 torr

102. Answer (2)

[B] = [B0] e –kB t

x = 1.34  1 (nearest integer)

105. Answer (658)

106. Answer (81)

109. Answer (16)

t67% = 1.566 t1/2

117. Answer (100.00)

Assuming A and Ea to be independent of temperature

x  106  1.62  105

k 2 (at 300 K) = 1 × 10–3 s–1

From given graph,

So, correct order of activation energies Ec > Ea > Ed > Eb