116 Electrochemistry Solutions of Assignment (Step-3)

19. Answer (D)

+3 +2
(P) Fe + e Fe ºG1 = – 1F × 0.77
+2
Fe + 2e Fe ºG2 = + 2F × 0.77
+3
Fe + 3e Fe ºG3 = – 3F × EºFe+3/Fe

ºG 3 = ºG 1 + ºG2

– 3F × EºFe+3 /Fe = – 0.77 F + 0.88 F

– 3EºFe+3 /Fe = 0.11 (V)

0.11 (V)
EºFe+3 /Fe = – = – 0.036 (V)
3
+
(Q) 2H2O O2 + 4H + 4e Eº = – 1.23 V
–
4e + O2 + 2H2O OH Eº = + 0.40 V

+ –
4 H2O 4H + 4OH Eº = – 0.83 V

2+
(R) Cu + 2e Cu Eº = + 0.34 V
2+
2Cu Cu + 2eu Eº = – 0.52 V

2+ +
Cu + Cu 2Cu Eº = – 0.18 V

+3
(S) Cr + 3e Cr ºG1 = + 3 × F × 0.74
+2
Cr Cr + 2e ºG2 = + 2 × F ×0.91
+3 +2
Cr + e Cr

EºCr+3 /Cr+2 = – 0.4 V

20. Answer (4)

X o Y; 'rG° = – 193 kJ mol–1

M+ o M3+ + 2e– E° = – 0.25 V

Hence 'G° for oxidation will be

'G° = – nFE°

= –2 × 96500 × (–0.25)

= 48250 J

= 48.25 kJ

48.25 kJ energy oxidises one mole M+

193
? 193 kJ energy oxidises mole M  4 mole M
48.25

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Solutions of Assignment (Step-3) Electrochemistry 117
21. Answer (3)

1 o HX 2 o HY

(m )HX (m )HY

1  o
2  o
m m

K a1  C112 K a2  C2 22

2
(m )HX
 0.01 o 2
( m )

2
(m )HY
 0.1 o 2
( m )

2
K a1 2
0.01(m )HX  ( ) 
?  2
 0.1 m HX 
K a2 0.1(m )HY  (m )HY 

2
 1
 0.1 
 10 

= 10–3

K a1
pK a (HX)  pK a (HY )   log   log10 3  3
K a2

22. Answer (6)

 l  120
  C    5  107 
A
  1

= 6 × 10–5 S cm–1

  1000 6  10 5  1000
M  
M 15  10 4

Ÿ OM = 40 S cm2 mol–1

[H+] = CD = 10–4

10 4 1
 4

15  10 15

M
Ÿ  º
M


Ÿ M = 40 × 15

= 600

= 6 × 102 S cm–1 mol–1

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118 Electrochemistry Solutions of Assignment (Step-3)

23. Answer (9.9 to 10.1)

Cell reaction :

Mg(s)  Cu2 (1 M)  Cu(s)  Mg2 (xM)

2.303T
Ecell  Ecell  log x
F/R
2.303  300
2.67  2.70  log x
11500  2
2.303  3
0.03  log x
115  2
0.03  115  2
log x  1
2.303  3
x = 10.00

24. Answer (–11.82 to –11.42)

A  A n  ne –
B2n  2ne –  B
2A  B2n  2A n  B
'H° = 2'G°, Ecell = 0

'G° = 'H° – T'S°

G
Ÿ 'G° = T'S° Ÿ S 
T

– RT ln K [A n ]2 22
S   – R ln 2n  – 8.3  ln
T [B ] 1

Ÿ 'S° = – 11.62 JK–1 mol–1

25. Answer (13.00 to 13.60)
1
H2 (g)  O2 (g)  H2 O(l)
2
Eocell  1.23 V (from given data)
o o
∵ G  nFE cell

= –2 × 96500 × 1.23 J/mol

Work derived using 70% efficiency and on consumption of 1.0 × 10–3 mol of H2(g)
W = 2 × 96500 × 1.23 × 0.7 × 1 × 10–3
= 166.17 J
This work done = Change in internal energy of monoatomic gas.
Ÿ 166.17 = nCv,m 'T
166.17  2
Ÿ T 
1 3R
T  13.32 K

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Solutions of Assignment (Step-3) Electrochemistry 119
26. Answer (0.215)
27. Answer (0.86)
Solution for Question Nos. 26 and 27 :
Molar conductivity of HX at infinite dilution

m = 4 × 102 S cm2 mol–1
Molar conductivity of HX at conc. c1 = y × 102 S cm2 mol–1
c
m1 y  102 y
1   
 2 4
m 4  10
On 20 times dilution of the solution of HX
c
m2 3y  102 3y  c1 
2 


2
 c 2  20 
m 4  10 4  

1 1
 Ÿ D2 = 3D1
2 3


  –
HX  H  X

c1(1– 1 ) c11 c11

c112 c 2 c (3 )2
Ka   2 2  1 1
1– 1 1– 2 20(1– 31 )
1 9

1– 1 20(1– 31 )
11
20 – 60D1 = 9 – 9D1 Ÿ 1   0.215
51
y = 4D1 = 0.86
28. Answer (0.77)

(1) MnO4 (aq)  4H  3e  MnO2 (s)  2H2O; E  1.68 V

G1o  3F (1.68)  5.04 F

(2) MnO2 (s)  4H  2e  Mn2  2H2O; E  1.21 V

Go2  2F (1.21)  2.42 F

(3) Mn2 (aq)  2e  Mn(s); E  1.03 V

Go3  2F ( 1.03)  2.06 F

Adding (1), (2) and (3),

MnO4 (aq)  8H  7e  Mn(s)  4H2O

G  G1o  Go2  G3o

= (–5.04 – 2.42 + 2.06) F
–7F E° = –5.4F
E° = 0.77 V

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120 Electrochemistry Solutions of Assignment (Step-3)

29. Answer (7)

o
m  m A C
For electrolyte ZmXn and from given curve,
o
m (Zm Xn )  m (Zm Xn )  A C

336  339 3
A  
0.04  0.01 0.03
Ÿ A = 100

? For m  336 S cm2 mol1

o
Ÿ 336  m (Zm Xn )  100  0.04
o
m  336  4  340 S cm2 mol1

Zm Xn  mZn   nXm 

? 50m + 80n = 340
Ÿ 5m + 8n = 34 …(i)

Um Yp  mUp   pYm

o
? 25m + 100p = m (Um Yp )  250

Ÿ m + 4p = 10 …(ii)

Vm Xn  mV n   nXm 
? 100m + 80n = 440
Ÿ 5m + 4n = 22 …(iii)
From equation (i) and (iii),
n=3
m=2
From equation (ii),
p=2
m+n+p=2+3+2=7

‰ ‰ ‰

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