Chapter 11

Chemical Kinetics and Nuclear Chemistry

1. Answer (C)
23
11 Na  10
23
X  01e
2. Answer (D)

r = K[G] [H]

8r = K[2G] [2H]

2r = K[2G] [H]

 =1=2

 order of reaction = 3

3. Answer (A)

0.693
k1 = t1/2

0.693
k1 = (first order kinetics) ....(1)
40

1.386
k0 = 2  20 (zero order kinetics) ....(2)

k1
–1 3
k 0 = 0.5 mol dm .

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

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5. Answer (A)
Ea

k  A e RT

Ea
ln k = ln A –
RT
6. Answer (A)
He4
27
13 Al 
2
 30
14 Si  1H1
(X)

He4
27
13 Al 
2
 30
15 P  10 n
( Y)

14 Si 
30 1
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)
=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, B)
9
4 Be    84Be  10n
9
4 Be  1
1 H  84Be  12H
11. Answer (B, C, D)
 A high activation energy usually implies a slow reaction.
 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
 k  P Ze a
So, pre-exponential factor (A) = P × Z and it is independent of activation energy or energy of molecules.

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12. 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

13. 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]
14. Answer (A, D)
A  2B + C
P0 – –
P0 – P 2P P
Pt = P0 + 2P

Pt  P0
P=
2

 P0  2P0
Kt  ln    ln
 0 3P0  Pt
 P0   t
P P

  2  

Kt  ln 2P0  ln(3P0  Pt )
ln (3P0 – P)t

Time
Rate constant of reaction is independent of initial concentration.
15. Answer (B, C, D)

92U
238  90Th
234 + 2He4

90Th
234  91Pa
234 + –1e
0

91Pa
234  92Z
234 + –1e
0

92Z
234  90Th230 + 2He4

 x 1 =  ; x2 = x3 = –1
0 ; x4 = 

Z has atomic number 92.

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16. Answer (B, C, D)

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 sec

d[X] 0.693
–  2k[X]  2  1
dt 100

= 13.86 × 10–3 mol L–1 s–1

At 100 sec

d[Y] 0.693 1
–  k 2 [X]  k[X]  
dt 100 2

1
( Concentration of X after 2 half lives = M)
2
= 3.46 × 10–3 mol L–1 s–1
17. 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  P, S

Case-2: [X] << Xs; [X] + Xs  Xs

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k  X
 rate   k   X (1st order w.r.t. X)
Xs

I Q, T

Case-3: [X]  Xs

k  X
rate 
Xs   X 

In this case curve-R given in List-II will match.

 I  P, Q, R, S, T (The graph of half-life should start from origin)

k  X
(II) rate  X  X
s  

 [X] << Xs

 Xs + [X]  Xs

k  X
 rate   k   X (1st order w.r.t. X)
Xs

II  Q, T

k  X
(III) rate  X  X
s  

 [X] >> Xs

 Xs + [X]  [X]

k  X
 rate   k (Zero order w.r.t. X)
 X

III  P, S

k  X
2
(IV) rate 
Xs   X 

 [X] >> Xs

 Xs + [X]  [X]

k  X
2
 rate   k  X (1st order w.r.t. X)
 X
 IV  Q, T

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18. Answer (8)

238 214
92 U 
 82 Pb  X24 He  y 01 e
24 = 4x; x = 6
10 = 2x – y
y= 2
 x + y= 8
19. 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.
20. Answer (3)
142
92 U235 
 54 Xe + 38
90
Sr +3 10 n
21. Answer (8)
63
29 Cu  11H  610 n  ( 24 He)  211H  X(52
26 Fe)

Fe belongs to group-8.
22. 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
23. Answer (9)
238 206 4
92 U  82 Pb  8 2He  6 0– 
Now, number of moles in gas phase = 1 + 8 = 9 mole
At constant temperature and pressure

PF nF 9
  9
Pin nin 1

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24. Answer (8)

8H  5 Fe(H2O)2 (OX)2   MnO4  Mn2  5 Fe(H2O)2 (OX)2   4H2O

2 

1 d[H ] d[MnO4 ]
Rate   
8 dt dt

rate of [H ] decay

Hence, 8
rate of [MnO4 ] decay

25. 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.
26. Answer (6.70 – 6.80)
A + B + C  Product
Rate  [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

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27. 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)
a
2Kt  ln 0
a0  x
 a0  1 and a0 – x  0.1
1 1
 t 4
ln  2.3  103 s
2  5  10 0.1
28. Answer (1.19 to 1.21)

238
92 U 206
82 Pb

Number of -particles emitted per nucleii of

238  206
238
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 -particles emitted = 8    6.02  1023
8 238

= 12.04 × 1017

= 1.2 × 1018

 Z = 1.2



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