UNIT # 08 (PART - II)

ELECTROCHEMISTRY EXERCISE # 1
3. + –
Ag + e  Ag 56
20. 1 F ion discharge = 3
2
0.059  1  3 F  84 g
E cell = E° – log  /
1  0.1  22. Ag + , Cu 2+ , Au 3+
= E°red – 0.059 1 1 1
4. Cu 2+ + 2e –  Cu : :
1 2 3
V 1 = 1, C1 = 1 M = 6 : 3 : 2
V 2 = 10, C 2 = 0.1 M 23. E° cell = E° cathode – E anode 0.80 = E°Ag+/Ag – E°H +
2 /H
0.0591 1 0.80 = E°Ag +/Ag – 0
E cell = E° – log E cell = E°
2 1
E°oxidation = – E°red = – 0.80 V
0.0591  1 
E cell = E° – log  25. G° = –nF E°cell ( 1 F = 96500 C)
2  0.1 
= E° – 0.059/2 = E° – 0.030 = – 2 × 0.360 × 96500 = –69480J = –69.48 kJ
5. H 2  2H + + 2e – 26. MnO 4– + 8H + + 5e –  Mn 2+ + 4H 2 O = 5F
pH = 1, [H + ] = 10 –1 E° = 0 27. Cu + + e –  Cu G 1 = –F E° = – FX 1
2 2+ –
0.0591 [H ] Cu + 2e  Cu G2 = –2F E° = –2 FX2
E = log 2 2 = 0.0591 log  1 
2 [H ] 2 10 1  Cu 2+ + e –  Cu + G 3 = –F E°
0.0591 G 3 = G 2 – G 1 –FE° = – 2FX 2 + FX 1
=  2 = 0.0591 V
2 E° = 2X 2 – X 1
0.0591 P  P  at.  14  965
6. E = E cell – log   1 =   31. W = Z I t 0.275 =
n R  R  2  96500
10. Fe 3+ + 3e –  Fe G 1 = –nF E°cell = –3F E°cell 0.550 × 100 = at. at. = 55
Fe 2+ + 2e –  Fe G 2 = –2F E°cell
 at. 
Fe 3+ + e –  Fe 2+ G 3 = –F E°cell  
w1 (E 1 ) Ag 0.5094  v.f.  Ag
required  G 3 = G 1 – G 2  
33. 0.2653  at. 
–F E cell = –3F E°cell + 2F E cell w 2 (E 2 ) metal  
 v.f. metal
–E cell = –3 × (–0.036) + 2 (–0.440)
–E cell = – 0.772 E cell = + 0.772 V 0.5094 (v.f) Ag
 v.f. = 1.9  2
11. + –
2H + 2e  H 2 pH = 10, [H +] = 10 –10 0.2653 1
E° = 0 1
 2
34. H 2  AgI  H   Ag  I  E = 0
0.0591 [H ] 0.0591 2
E red = log  2 log [10 10 ]
2 PH 2 (g) = 2 1
H 2  H   e  E = 0.151
0.0591 2
=  2  [ 10] = – 0.591 V
2
0.059
12. E° cell = E° cathod – E° anode = 0.80 – (–0.25) = 1.05 V 0.151 = – log(H  ) = 0.059 × pH
1
14. E° cell = E°cathod – E°anode = 1.50 – (–0.25) = 1.75 V
18. 2Cl –  Cl 2 + 2e – 0.151
pH =  2.5
0.059
71
W = Z I t =  2  2.5  60 = 0.110 g 35. AgI + e –  Ag + I – E° = –0.151
2  96500
Ag + + e –  Ag E° = 0.799
0.0591 [Cl  ]2 [Br2 ]
19. E cell = 0.29 – log
2 [Br  ]2 [Cl 2 ] AgI 

 Ag + + I – E° = –0.151 – 0.799
2 2 2
0.0591 [10 ] [10 ] 0.0551
= 0.29 – log E° = –0.95 E = E° – log K sp
2 [10 2 ]2 [1] 1
–16.074
–16.074 = log 10 K sp 10 = K sp
0.0591
= 0.29 + × 2 = 0.349  0.35 V 7.91 × 10 –17 = K sp
2
ELECTROCHEMISTRY EXERCISE # 2
2. G = – nFE° = H° – TS° 18. 2 Ag + + H 2  2H + + 2Ag
= – 2 F × 0.695 = H° – 273 S° ... (i) [H  ]2
0.0591
= – 2F × 0.6753 = H° – 298 S ... (ii) 1.023 = (E C – E A ) – log P [Ag  ]2
2 H2
Solue both equation.
3. Cd + 2AgCl(s)  CdCl 2 (aq) + Ag(s) 0.591  2 0.591  2
1.023=0.799–0– log[H] + log[X]2
2 2
E 63.5  2.68  3600
W= It= = 3.174g 0.06
96500 2  96500 0.294=0.06× 5.5+ log[X ]2 –0.036=0.03log 10 [X] 2
2
5. 2H + + Fe  Fe 2+ + H 2 –0.036 = 0.6 log 10 [X] 0.6 = log 10 [X]
E°cell = E°cathod – E°anode = 0 – (–0.34) = 0.34 V
Fe will oxidised emf is +ve, the reaction shall occur. E
19. w = Z I t w = It
96500
40
7. W = Z I t =  9.65  10 3  4g
96500 w 200.6  2  71 44 236.1
dE  I  I
8. G = – nFE° = H° – TS° – nF = 0 – S° t 2  96500 3600 96500
dT
dE I = 5 Amp.
nF = S° ...(i) 20. K a = 25 × 10 –6  eq = 19.6 s cm 2 eq –1
dT
C
E°= 1.1028 – 0.641 × 10 –3 T + 0.72 × 10 –5 T 2 K a  eq
C = 0.1 M  =  
C  eq
dE
= – 0.641 × 10 –3 + 1.44 × 10 –5 T
dT
25  10 6 19.6 5  10 6 19.6
at 25°C    
0.01  eq 0.01  eq
dE
=3.6502 × 10 –3
dT  eq = 392
from eq. (i) M
21.  M  M  A C
2 × F × 3.6502 = S° S°= –54.23 EU
 = C – mx
0.0591
9. E° = log K 1.1 × 2 = 0.06 log K slope = –ve
2 C
36.22 = log K 10 36.22 = K f 1
22. H 2 O  H 2 + O 2  2e –
8.314 × 10 36 = K 2
0.0591  1  2H 2 O  2 H 2 + O 2  4e –
10. E cell = 0.80 – log  3  = 0.623 V
1 10  gases [H 2 + O 2 ] = 2 × 22.4 + 22.4 = 67.2
0 1 1
1  2
11. H2 + O 2  H 2 O 2 = 2F 23.

A 1 =  BaCl2 

 Ba   eq ..........(i)
2 2 eq Cl 

0.0591
12. 0 = (E C – E A ) – K sp 1 
1 A 2 = H 2 SO 4   eq H    2 .........(ii)
2 eq SO 4
E C = –0.80 – 0.0591 (–17 + log 8.3)   
= –0.80 + 0.950 = –0.15 V A 3 =  HCl   H    Cl  ........(iii)
13. 2Fe 2+ + Sn +4  2Fe 3+ + Sn +3 1  2 1 

E° = E C° – E A° = 0.15 – 0.77 = –0.62 V eq BaCl2   Ba   SO2  ........(iv)
2 eq 2 eq 4
15. Ni(s) + 2H 2  NiSO 4 + H 2 eq. (4) = eq (i) + eq (ii) – eq(iii)
0.0591 1 = A 1 + A 2 – A 3
0.236 = E° – log 24. w = Z I t
n 1
–nFE° = G° w = ZQ
G° = –2 × 96500 × 0.236 = 45.55 kJ w  Z
17. Fe 3+  Fe 2+ 5 paise
26. Cost = × hour × 15 amp × 110
0.0591 1.5 KW H
E cell = 0.770 V – log
1 0.015 5 66000
= 8  15  110 =  66 paise
= 0.770 – 0.059 × 2 = 0.652 V 3
10  wH 10 3
28. Ag + Cl –  AgCl + e – 30. Anode : H 2  2H + + 2e –
E = E° + 0.0591 log [Cl – ] Cathode : Cl 2 + 2e –  2Cl –
–0.25 = E° + 0.0591 log 0.1 E° = –0.1909 E = E° – 0.0591 log [H +] [Cl – ]
Now for reaction on increasing concentration by 10 E will increase
AgCl + Cl –  AgCl + e – by a factor of – 0.0591 log 100 = – 0.0591 × 2
Ag + + e –  Ag = – 0.1182 V
31. 2H 2 + O 2  H 2 O H = 2X – 285.5 kJ
Ag + + Cl –  AgCl
E = E° Ag/AgCl/Cl – + E° Ag + /Ag + 0.0591 log K sp O 2 + 4H + + 4e –  2H 2 O E° = 1.23
2H 2  4H + + 4e – E° = 0
O = – 0.1909 + 0.799 + 0.0591 log K sp
K sp = 5.13 × 10 –11 for reaction :
O 2 + 2H 2  2H 2 O E° = 1.23
29. Given Au +3 + 3e –  Au E 1° = 1.5
+3 –
Au + 2e  Au +
E 2 ° = 1.4 G° = –nFE° = – 4 × 96500 × 1.23 = – 474780
G°=H°–TS° –474780 = – 571000 – 298S°
so for reaction
Au  Au + + e – E° = 2E°–3E °E°=–1.7 S° = – 322.8 J/K
2 1
–
Au+2CN Au(CN) 2 +e E° = x– – K  1000
32. M =
Au + + e –  Au E° = 1.7 M
RT 1  1  2.2  1
O = x + 1.7 – ln X – 1.7 k =   = 50  4.4   100  0.01
F R a  
RT 0.01  1000
x = ln X – 1.7 M= = 20 S cm 2 mole –1
F 0.5
For reaction = 20 × 10 –4 S m 2 mole –1 = 0.002 S m 2 mole –1
O 2 + H 2 O + 4e –  4OH – E° = 0.41 33. k a = 1.69 × 10 –5 = C 2 = 0.01  2 =  = 0.04
RT M
Au + 2CN –  Au(CN) 2– + e – E° = ln X – 1.7    M = 0.04 × 380
F  M
so for reaction k  1000
 M = 15.2 S cm 2 mole –1 M =
1 1 M
Au + 2CN– + O2 + H O  Au(CN)2– + OH–
4 2 2 k  1000
RT RT 15.2 =
E° = 0.41 + lnX – 1.7 = –1.29 + lnX 0.01
F F
G° = –nFE° (n = 1) k = 1.52 × 10 –4 S cm –1
G° = 1.29 F – RT lnX k = 1.52 × 10 –2 S cm –1

ELECTROCHEMISTRY EXERCISE # 3

COMPREHENSION BASED QUESTIONS Let [HNO 3 ] = xM so [H + ] = [NO 3– ] = x

Comprehensi on # 1 equation (i) & (ii)

1. (3e – + 4H + + NO 3–  NO + 2H 2 O) × 2
0.0591 10 9 0.0591 10 7
(Cu  Cu +2 + 2e – ) × 3 0.62 – log 10 =0.45– log 6
2 x 2 x
8H + +2NO 3– +3Cu  3Cu +2 + 2 NO + 4 H 2 O
[NO]2 [Cu 2 ]3 0.0591 0.0591
0.0591 0.17= [–9–10logx]– [–7– 6logx]
E=0.96–0.34– log ...(i) 6 2
6 [NO 3 ]2 [H  ]8
since [HNO 3 ] = 1 M so [H + ] = [NO 3–] = 1 0.0518 = 0.0788 log x
0.0591
E = 0.62 – log (10 –3 ) 2 (0.1) 3 = 0.70865 x = 10 0.657 M
6
2. (e – + 2H + + NO 3–  NO 2 + H 2 O) × 2 Comprehensi on # 2

Cu  Cu +2 + 2e – 2. Al  Al 3+ + 3e – E° = 1.66 V
+ – +2
4H + 2 NO + Cu  Cu + 2NO 2 + 2H 2 O
3
O 2 + 4H + + 4e –  2H 2 O E° = 1.23 V
2 2
0.0591 [NO 2 ] [Cu ]
E=0.79–0.34– log ...(ii)  E°cell = 2.89 V
2 [NO 3 ]2 [H  ]4
ELECTROCHEMISTRY EXERCISE # 4[A]
l 4 1 1 3
1. Cell constant ( 
) =  cm 1 =  cell constant =  0.3  mho cm 1
a 7 resistance 50 500
specific conductance = conductance × cell constant Equivalent conductance = specific conductance ×
( ) =(×  ) volume ... (8)
3
1 l 1 4 =  20000  120 mho cm 2
=  =  =2.332×10 –3 mhocm –1 500
resis tan ce a 245 7 (0.05 N = N/20  V = 20,000 cc)
equivalent conductance = sp. cond. × volume (cc) 4. Let the volume of the vessel be V cc. ( 
( ) = ( ×  (cc))  V cc  )
(containing 1 eq. of the substance) Number of equivalent of NaCl (NaCl  
–3
=2.332× 10 × 10000(for N/10 solution, wt.in grams (  
)
V = 10,000 cc) = 23.32 mho cm
2
) =
eq. weight ( 
)
2. Let K1 and K2 be the specific conductances of the
500
solutions A and B respectively and the constant =  8.547
58.5
of the cell be x.  volume of water (cc) containing 1 eq. of
 K1 
K2 
A B  V

x  NaCl =
8.547
 For solution A : sp. conductance = conductance
× cell constant (1 
NaCl  
(cc))
1 The sp. cond. of the NaCl solution (only due to
K1 =  x .........(i) + –
50 presence of Na and Cl ions)
For solution B : sp. conductance (NaCl  (Na 
+ –
Cl
1 
))
K2 = x ... (ii) –5 –5 –5
100 = 3.10 × 10 – 2.56 × 10 = 0.54 × 10
When equal volumes of A and B are mixed, both –5 V
  NaCl = 0.54 × 10 ×
the solutions get doubly diluted ; hence their in- 8.547
since the vessel is big, the resulting solution may
dividual contribution towards the sp. conductance
be supposed to be dilute.
K K
of the mixture will be 1 and 2 respectively and (
2 2
the sp. conductance of the mixture will be  )
1  NaCl = NaCl
(K 1  K 2 ) . ( A 
B 

2
 ,  –5 V
0.54 × 10 × = 149.9
 8.547
8
K K V = 2.37 × 10 cc.
 1   2    
2 2 0.50 1
1 5. Cell constant = 
 (K 1  K 2 )  ) 1.50 3
2 Specific conductance
 For the mixture : 1 (K 1  K 2 )  1  x ... (iii) =
equivalent conductance
2 R volume (cc) containing 1 eq.
(R is the resistance of mixture)
From equations (i),(ii)and(iii),we get R=66.67 ohms. 97.1
= (for 0.1 N solution V = 10,000 cc)
3. Since the electrodes of the cell are just half dipped, 10,000
the effective area will be 5 sq cm. = 0.00971 mho cm
–1

(
Conductance = specific conductance / cell constant
5 sq cm.  ) 0.00971
= 0.02913 mho
l 1.5 1/3
Cell constant =   0.3 cm 1
a 5 1
Specific conductance = conductance × cell constant  resistance = ohm
0.02913
 potential difference (volt) Since water dissociates feebly, i.e., water may be
 current in amp = +
considered to be a dilute solution of H and OH
–
resis tance (ohm )
ions,
5
(
+
(Ohm's law) =  0.1456 ampere. H
1 / 0.02913
6. From Kohlrausch's law, we have, OH–
)
 H 2 O  H 2 O  H  OH 
 NH 4 ClO 4   NH    ClO – = Fu NH   Fu ClO


4 4 4 4
–81000
= F(u NH   u ClO

 ) = 96500(6.6× 10 +5.7 × 10 )
–4 –4  5.8 × 10 × = 350 + 198 = 548
4 4 X
–7
2  X = 1.0 × 10
= 118.67 mho cm + – –7
 [H ] = [OH ] = 1 × 10
7. We have + –
For the equilibrium, H 2 O = H + OH
  349.8
u°H + = 
–3 2 –1
= 3.62 × 10 cm volt s
–1 [H  ][OH  ]
F 96500 Equilibrium constant (K) =
[H 2 O]
 a 
50.11 –4 2 –1 –1
+
K w = K × [H 2 O] = [H ] [OH ]
–
u°Na + =  = 5.20 × 10 cm volt s –7 –7 –14
F 96500 = 1.0 × 10 × 1.0 × 10 = 1 × 10
Further, we know that
Kw 1  10 14
ionic velocity (cm / s)  K =   1.8  10 –16 mole / L
u° = [H 2 O] 55.5
pot. diff. (volt) / distance between the electrodes(cm )
 1000 
2  [H 2 O]   55.5 mole / L 
 velocity of H =3.62× 10 ×
+ –3 –3
=1.45× 10 cms
–1  18 
5 c 7.36
10. Degree of dissociation (x) =   0.0188
+ –4 2 –4 –1  0 390.7
velocity of Na =5.20× 10 × =2.08× 10 cms
5 For the equilibrium
   0.05 0 0 Initial conc. (moles/litre)
8.  NH 4 Cl  NH 4
 Cl – – +
CH 3 COOH = CH 3 COO + H
 
  NH 4
 NH 4 Cl   Cl  = 150 – 76 = 74 0.05(1–x) 0.05x 0.05x Equilibrium concentration
(for CH 3 COOH, 0.05 N = 0.05 M)
  NH 4 OH  NH   OH  = 74 + 198 = 272
4 0.05 x  0.05x
Ka =
Further, 0.05(1 – x)
 since x is very small,
degree of dissociation (   
) = c = 2 2 –5
K a =0.05x =0.05 × (0.0188) =1.76× 10 mole/L

9.6 11. For equilibrium,
 0.0353 +
AgCl = Ag + Cl
– + –
K sp = [Ag ] [Cl ]
272
9. Suppose water contains X moles per L If the solubility of AgCl in water is, say, x
+ –
(or X eq. / L) of H ions (or OH ions) moles / L or x eq. / L,
(
H 
( OH
+ –
) (AgCl

, x 
/ L  x 
/
X 
( X eq. / L) )  L 
)
+ 2
 X equivalents of H ions are produced from X K sp = x . x = x
eq. of water 1000
 volume containing 1 eq. of AgCl =
(X  X H  ) x
+

–6 1000
 volume (cc) containing 1 eq. of water which  AgCl  sp. cond.× V = 2.28 × 10 ×
x
1000 Since AgCl is spari ngly soluble i n water,
dissociated into its ions =
X  AgCl  AgCl =138.3
(
(cc)  (
AgCl 
)
1000

–6
)  2.28 × 10 ×
= 138.3
x
–5
 eq. conductance of water = sp. cond. × V or x = 1.644 × 10 eq./L or mole/L
2 –5 –2 –10 2
K sp = x = (1.644 × 10 ) =2.70× 10 (mole/L)
–8 1000
= 5.8 × 10 ×
X
27. The overall battery reaction is 39. Cu
2+


+ 4NH 3  [Cu(NH 3 ) 4 ]
+2

Pb + PbO 2 + 2H 2 SO 4 = 2PbSO 4 + 2H 2 O
 two moles of electrons are involved for the reaction 12 [Cu(NH 3 ) 4 ]2 1.0
 K f = 1 × 10 = 
of two moles of H 2SO 4 , [Cu 2 ][NH 3 ]4 x(2.0) 4
(
H2SO4 
 x = 6.25 × 10 M
–14


) Note that due to high value of K f almost all of the
+2 2+
 eq. wt. of H 2 SO 4 = mol. wt. of H 2 SO 4 = 98 Cu ions are converted to Cu(NH 3) 4 ion
no. of eq. of H 2SO 4 present in 3.5 L of solution 0.059 Cu 2 
of a charged battery No w E cell =E°cell + log10
2 Zn 2
(
3.5 L H2SO4 
0.059  6.25  10 –14 

) = 1.1 +
2
log 10 
 1


39 1.294
=   3500 = 18.0235 E cell = 0.71 V
98 100 + –
No. of equivalents of H 2SO 4 present in 3.5 L of 4 6 . Ag  Ag + e E RP = 0.799 V
+
solution after getting discharged Ag(NH 3 ) 2 + e  Ag + 2 NH 3 E RP = ?
(
3.5 L H2SO4 

Ag(NH 3 ) 2 
+ +
 Ag + 2 NH 3

)
0.0591 [Ag(NH 3 ) 2 ]
20 1.139 E cell = E°cell + log10
=   3500 = 8.1357 1 [Ag  ][NH 3 ]2
98 100
0.0591
Number of eq. of H2SO4 lost (H2SO4  0 = E°cell + log(6  10 8 )  E°cell = – 0.426
1
  
) = 18.0235 – 8.1357 = 9.8878 E°cell = E C  E A
 moles of electric charge produced by the battery
= 9.8878 F –0.426 = E C  0.799  E C  0.373 V
(
4– 3–
) 47. Use Co(CN) 6  Co(CN) 6 +e; E OP
° = +0.83 V
3+ 2+
= 9.8878 × 96500 coulombs Co + e  Co ; E RP
° = 1.82 V
= 9.8878 × 96500 amp-seconds
9.8878  96500
4– 3+

Co(CN) 6 + Co   2+
 Co + Co(CN) 6
3–

= amp-hours = 265 amp-hours.

60  60
0.059 [Co 3  ][Co(CN ) 64  ]
35. The cell is, and E cell = E°cell + log10
Pt H 2 |HA 2 | |HA 1 |H 2 Pt
1 [Co 2  ][Co(CN ) 63  ]
(1atm) (1atm) 0.059 [Co 3  ][Co(CN ) 64  ][CN  ]6
0.059 + or E cell = E°cell + log10
At L.H.S. : E H/H + = E°OP + + log 10 [H ] 2 1 [Co 2  ][Co(CN ) 36  ][CN  ]6
+
H/H 1
 –log H = pH  E H/H+=E°OP + –0.059 (pH) 2 Also 6 CN + Co
– 2+


4–
H/H  Co(CN) 6
0.059
At R.H.S. : E H + /H = E°RP +
+
log 10 [H ] 1 [Co(CN ) 46  ]
H + /H 1 and K f1 
[Co 2  ][CN  ]6
 E H + /H = E RP +
–0.059 (pH) 1 – 3+ 3–
H /H
and 6 CN + Co 

 Co(CN) 6
For Acid HA 1 

HA 1  H + A1
+ –

[Co(CN ) 36  ]
and K f2 
+
[H ] = C .  = K a .C [Co 3  ][CN  ]6
1
pK a1  12 log10 C 0.059 Kf
 (pH) 1 = 2  E cell = E°cell + log10 1
1 K f2
1
Similarly, (pH) 2 = 2
pK a2  12 log10 C 0.059 1019
0 = 0.83 + 1.82 + log10
( C are same) 1 K f2
 E cell = E OP + E RP (At equilibrium E cell = 0)
H + /H H + /H

for II for I K f2
 19
 8.23  10 44
0.059 10
= 0.059  12 pK a 2  12 pK a1   [5  3]
2  K f 2 = 8.23 × 10 6 3
= + 0.059
 ELECTROCHEMISTRY EXERCISE # 4[B]

RT [H  ]2 5. In beginning ( ) : 

1. E = E°calomal + E° H + – ln At anode :
2 /H nF PH 2
2H 2 SO 4  H 2 S 2 O 8 + 2H + + 2e –
8.314  313 [H  ]2 At cathode:
0.6885 = 0.28 – ln × 760
2  96500 725 2H 2 O + 2e –  H 2 + 2OH –
[H + ] = 2.57 × 10 –7 After some time (  
) :
pH = 6.6 At anode :
2. For Fe +3 + e –  Fe +2 E° = 0.77 2H 2 O  4H + + O 2 + 4e –
so Fe +3 will reduce to Fe +3 At cathode:
 Fe+3 , Fe+3  
) 2H 2 O + 2e –  H 2 + 2OH –
Faraday of current passed ( ) 2.35
moles of O 2 evolved ( 
O 2  
) =
1.25  1.1  3600 22.4
= = 0.0513
96500 during this time moles of H2 evolved (  
meq. of Fe +2 = meq of KMnO 4 required = 51.3 2  2.35

H2 
) =
(Fe   
+2
=  KMnO4   22.4

= 51.3) volume of H2 evolved with O2 (O2  
H2
51.3 = M × 5 × 25 2  2.35
M = 0.41  ) =  22.4 = 4.7 L
22.4
3. At cathode (
) : 
+2 –
volume of H2 evolved with H2S2O8 (H2S2O8 
Sn + 2e  Sn

H 2  ) = 9.722 – 4.7 = 5.022 L
At anode () :
X  X +n + ne – 5.022
moles of H 2 evolved ( 
H2  
) =
Cell reaction ( 
) : 22.4
n Sn + 2X  2X +n + nSn moles of H 2S 2O 8 formed ( H 2S 2O 8  
+2
)
E° = – 0.14 + 0.78 = 0.64
5.022
=
0.0591 [X  n ]2 22.4
E = E° – log 2 n
2n [S ] wt. of H 2 S 2 O 8 formed ( H 2 S 2 O 8  
) =
5.022
0.0591 × 194 = 43.45 g
0.65 = 0.64 – [log 0.01 – log (0.5) n ] 22.4
2n
6. At cathode only pure copper is deposited so % of
0.0591
0.01 = – [–2 + n log 2] 22.011
2n Cu = × 100 = 98.88%
0.03384 n = 2 – 0.3010 n 22.26
0.6394 n = 2 (
Cu 
n = 3.12 ~ 3 %)
4 . ( a ) At cathode : since Cu is getting deposited, iron will also get
2e – + Cu +2  Cu reduced because it's SRP value is lesser than Cu.
At anode : (
Cu 
2H 2 O  4H + + O 2 + 4e –

SRP Cu 
)
Eq. of O 2 evolved = Eq. of Cu formed = 0.01
Charge passed ( 
)
(
O2 
= Cu 
= 0.01)
= 140 × 482.5 = 67550 coloumb
total loss in wt. (   
) =
0.1 × 8 +
67550
0.01  63.5 = = 0.7 Faraday
= 0.3975 96500
2 Faraday used for reduction of Cu (Cu  
wt. of resulting solution = 10 –0.03975= 9.6025g
22.011  2
(
)  
) = = 0.69326
+ 63.5
(b) Eq. of H = 0.01
 so Faraday used for iron (9 . In beginning (
) 

) = 0.7 – 69326 = 0.00674 F At cathode :
mass of iron ( 
) 2e – + Cu +2  Cu
0.00674  56 At anode :
= = 0.1887 g
2 2H 2 O  4H + + O 2 + 4e –
0.1887 Eq. of O 2 = Eq. of Cu +2 (O 2  
= Cu +2 
% of Fe =  100 = 0.847 %
22.26
0.4  2
7. At anode : 
) = = 0.012598
63.5
Ag + Cl –  AgCl + e –
At cathode : 0.012598  22400
AgBr + e –  Ag + Br – vol of O 2 = = 70.55 mL
4
[Br  ] Later on ( 
) :
E = E°Ag/AgCl/Cl – + E°Br – /AgBr/Ag – 0.0591 log ...(i)
[Cl  ] At cathode :
For reaction : 2H 2 O + 2e –  H 2 + 2OH –
Ag + Cl –  AgCl – e – At anode :
Ag + + e –  Ag 2H 2 O  4H + + O 2 + 4e –
E = O = E°Ag/AgCr/Cl – + E°Ag + /Ag – 0.0591
Faraday passed ( 
)
1
log
[Ag  ][Cl – ] 1.2  7  60
= = 0.00522
E°Ag/AgCl/Cl – = E°Ag/Ag + – 0.0591 log K sp (AgCl) ...(ii) 96500
for reaction
AgBr + e –  Ag + Br – 0.00522
moles of O 2 =
Ag  Ag + + e – 4
E = 0 = E°Br – /AgBr/Ag + E°Ag/Ag + – 0.0591 log [Ag + ] [Br – ]
E°Br – /AgBr/Ag = E°Ag + /Ag + 0.0591 log K sp (AgBr) ...(iii) 0.00522
moles of H 2 =
from equation (1), (2) & (3) 2

K sp (AgBr) [Br – ] 0.00522

E = 0.0591 log – 0.0591 log Volume of O 2 = × 22400 = 29.24 mL
K sp (AgCl) [Cl  ] 4

0.00522
3.3  10 13  0.2 Volume of H 2 = × 22400 = 58.464 mL
E = 0.0591 log = – 0.037 V 2
2.8  1010  0.001


2NaCl  + – Total volume of O 2 (O 2   
)
8.  2Na + 2Cl
= 29.24 + 70.55 = 99.79 mL

2H 2 O   +
 2H + 2OH
–
Total volume of H 2 (H 2   
)
At anode :
= 58.464 mL
2Cl –  Cl 2 + 2e –
At cathode : 108  5  2  3600
2H + + 2e –  H 2 10. w = = 40.29
96500
Net reaction ( 
) : but since anode is 95% pure with Ag so along with
 
2NaCl + 2H 2O  2OH – + H 2 + Cl 2 + 2Na + silver some impurities will also come out so actual
35.5 (
Ag 
95%
1000 = × 25.62 × t
96500 
)
t = 175374.83 sec = 48.74 hr.
40.29
1000 wt. coming out of anode is = 42.41 g
moles of OH – = 2 0.95
71
volume = 20 L (
2000 weight of anode now = 100 – 42.41 = 57.58g
[OH – ] = = 1.408 M
71  20 (
)
 100 15. E = Ionic mobility (  
) × 96500
11. moles of H 2 O 2 = moles of H 2 =
34  M =  E × (v.f.)
100 For k + ion v.f. = 1 so
wt. of H 2 = = Z it  E =  M = 73.52
17
Ionic mobility ( 
)
100 1  i  0.5  3600
17
=
96500 73.52 speed 
= = ( )
i = 315.36 Amp. 96500 potential gradient 
12. At anode : 2H 2 O  4H + + O 2 + 4e – 73.52 6
At cathode: 2H 2 O + 2e –  H 2 + 2OH – speed () (µ) =  = 0.000457 cm/sec
96500 10
Net reaction : 2H 2 O  2H 2 + O 2
4 Faraday  2 mole H 2 O = 36 g = 36 mL distance (
) = µ × t = 0.000457 × 7200= 3.29cm
16. pH = 1, [H + ] = 10 –1 mole/lit
4  96500
1 mL H 2O  Faraday [H + ] in 100 mL = 10 –2 mole
36
4  96500 at anode : 2H 2 O  4H + + O 2 + 4e –
8.2×10 15mL H 2O.... × 8.2×10 15 Faraday at cathode : Cu +2 + 2e –  Cu
36
4  96500  8.2  10 15 To produce 0.01 mole H+, we need 0.01 Faraday.
t= sec = 5.861 × 1013 sec. (0.01
H+ 
, 
0.01 
36  1.5  10 6
= 1.858 × 10 6 years. 
)
[H  ] Anode
13. E cell = –0.0591 log 0.965  8  t
[H  ]Cathode 0.01 =  t = 1250 sec.
96500
1
–0.188 = – 0.0591 log eq. of Cu+2 consumed (
Cu+2 
) = 0.01
[H  ]Cathode
moles of Cu +2 consumed ( 
Cu +2  
)
1 Kb 1 0.01
pH = 3.18 = 7 – P  log C = = 0.005
2 2 2
0.04  35
m moles of I 2 =
1 Kb 1 2
3.18 = 7 – P  log(1 / 32) m moles of CuSO 4 =0.04 × 35 = 1.4
2 2
k b = 7.15 × 10 –10 total moles (
) = 0.005 + 0.0014 = 0.0064
volume ( ) = 100 mL = 0.1 L
kw 10 14
kb =  = 1.39 × 10 –5
k b 7.15  10 10 0.0064
[CuSO 4 ] = = 0.064 M
0.1
kh 1.39  10 5 17. moles of Tl+1 initially (
Tl+1 
) = 0.0025
h = = = 2.1 × 10 – 2
C 1 / 32 moles of Co+3 initially (
Co+3 
) = 0.005
Tl +1 + 2Co +3   2Co +2 + Tl +3
[H  ]
14. E = E° – 0.0591 log 0.0025 0.005 0.005 0.0025
[Ag  ]
since k value is very high almost all Tl+ & Co+3 will
0.1 convert into Tl +3 & Co +2 respectively.
0.9 = E° – 0.0591 log
0.8 (
k 
Tl+  Co+3 
E° = 0.84662 Tl+3  Co+2  
)
On adding 40 mL of 0.05 M NaOH (0.05 M NaOH 0.0591
40 mL  ) E°cell = 1.84 – 1.25 = 0.59 =
2
log k
3 2 1 k = 10 20
[H + ] = 
70 70 (0.005 )2 (0.0025)
10 20 =
now (  ) 4 x3
x = 5.386 ×10 –10 mole
[H  ]
E = E° – 0.0591 log total volume (  ) = 50 mL = 0.05 L
[Ag  ]
1 2  5.386  10 10
E = 0.84662 – 0.0591 log [Co +3 ] = = 2 × 10 – 8
70  0.8 0.05
E = 0.95 V [Tl + ] = 10 – 8
18. At anode : H 2   2H + + 2e – 0.0591
0 = x – 0.8 – log K sp
E° = – 0.699 2
At cathode : Hg 2 Cl 2 + 2e –   2Hg + 2Cl – 0.0591
x = 0.8 + log 2 × 10 –49 = –0.639
E° = 0.28 2
so for equation (i)
0.0591
E cell = – 0.699 + 0.28 – log [H +] 2 [Cl – ] 2 0.0591
2 E = E° – log[S –2 ] ...(ii)
E cell = – 0.419 + 0.0591 pH 2


H 2 S  +
 2H + S
–2
k = k 1× k 2
(a) E cell = –0.419 + 0.0591 × 5
= – 0.1235 V [H  ]2 [S 2 ] (10 3 )2 (S 2 )
1.1 × 10 –21 = =
(b) O = – 0.419 + 0.0591 pH [H 2 S] (0.1)
pH = 7.1 [S –2 ] = 1.1 × 10 –16
(c) E cell = –0.419 + 0.0591 × 7.5 = 0.2425 is E cell > putting this in equation (ii) ((ii) 
0 cell is spontaneous & Calomal electrode with  )
work as cathode i.e. positive electrode.
0.0591
(E cell = –0.419 + 0.0591 × 7.5= 0.2425 E cell > 0 E = –0.639 – log 1.1 × 10–16 = – 0.1674V
2

k  1000

) 2 1 . M =
M
1 (2.06  10 6 – 4.1  10 7 )  1000
19. H2 + O 2  H 2 O H 1 = –56700 J/mole (86 × 2 + 444) =
2 s
...(i)
2H 2 O  2H + + 2OH – H 2 = 2 × 19050 s = 2.678 × 10 –6
...(ii)
K sp = 4s 3 = 7.687 × 10 – 1 7
cell reaction :
22. For KCl
at anode : H 2  2H + + 2e –
k  1000 k  1000
1 M =   138
at cathode : 2e + H 2 O + O 2  2OH –
– M 0.02
2
1 1  1 
net reaction : H 2 + H 2O + O 2  2H + + k = 2.76 × 10 –3 =    
2 R  a  85  a 
2 O H ...(iii)
(/a) = 0.2346
equation (i) + (ii) = (iii)
1
G 1 + G 2 = G 3 For H 2 O : k H O = (  / a)
2 9200
H 1 – TS 1 + H 2 – TS 2 = – nFE
1
(H 1 + H 2 ) – T (S 1 + S 2) = – 2 FE For NaCl : k NaCl = ( / a )
7600
(H 1 + H 2 ) – T (S net ) = – 2 FE
dE ( H 1  H 2 ) T DE (k NaCl  k H 2 O )  1000
S = nF so E = –  M =
dT 2F dT M
( 56700  2  19050)
E = – + 298 (0.001158)  1 1 
2  96500     0.2346  1000
 E = 0.09637 + 0.345 126.5 =  7600 9200 
M
= 0.4414 V
M = 4.2438 × 10 –5
20. 

Ag 2 S + 2e –  –2
 2Ag + S E° = x ....(i)
500


2Ag  +
 2Ag + 2e
–
E° = –0.8 M = =4.2438 × 10 –5
58.5  V


Ag 2 S  +
 2Ag + S
–2
E° = x – 0.8
V = 201400 L
0.0591
E = x – 0.8 – log [Ag +] 2 [S –2 ] V = 2.014 × 10 5 L
2