Chapter 11

Electrochemistry
1. Answer (2)
1 S u 65 m–1
3+
o
E =? 2+
o
E = – 0.439 V 260 0.4 mol u 1000 m3
Fe Fe Fe
(1) (2)
o
E = – 0.036 V = 6.25 × 10–4 S m2 mol–1
(3) 4. Answer (3)
'Go1 + 'Go2 = 'Go3 5. Answer (4)
Ÿ – n1Eo1 – n2Eo2 = – n3Eo3 Of the given values of standard reduction potential,
Ÿ – Eo + 2 × 0.439 = +3 × 0.036 the value of EqMnO /Mn2 is highest. Therefore,
4

Ÿ Eo = +0.77 V MnO4 is the strongest reducing agent.

2. Answer (4) 6. Answer (1)

For 0.2 M solution
2 4
Al2O3 o Al  O2 R = 50 :
3 3
V = 1.4 S m–1 = 1.4 × 10–2 S cm–1
'G = 966 kJ/mol
1 1
Ÿ 4e– are involved Ÿ U : cm
V 1.4 u10 2
? 'G = – nFE
Now, R U l
966 × 103 = –4 × 96500 × E a
966 l R
E  V 2.5V 50 u1.4 u102
4 u 965 Ÿ
a U
? 2.5 V potential difference is required For 0.5 M solution
3. Answer (3) R = 280 :
Case-I V=?
1 1 (S = Siemen) l
G S 50 u1.4 u102
R 50 a
K = G × cell constant
l
K 1.3 S m –1 Ÿ R U
Cell constant u 50 = 65 m–1 a
G 1S
1 1 l
Case-II Ÿ u
U R a
K
OM 1
Molarity Ÿ V= u 50 u1.4 u10 2
280
G u cell constant
OM
Molarity 1
= u 70 u102
280
1 S u 65 m–1
1 A = 10–3 m3 = 2.5 × 10–3 S cm–1
260 0.4 mol litre –1
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Vu1000 10. Answer (2)

Now, Om
M Cu+2 + 2e o Cu
3
2.5 u10 u1000 So, 2 F charge deposite 1 mol of Cu. Mass
=
0.5 deposited = 63.5 g.
= 5 S cm2 mol–1
11. Answer (3)
= 5 × 10–4 S m2 mol–1
7. Answer (3) Galvanisation is coating a layer of Zn.

According to Debye-Huckel-Onsager equation, 12. Answer (3)

OC O f  A C
For Cr3+ , E°Cr 3+ /Cr O2– = – 1.33 V
Here A = B 2 7

? OC Of  B C
For Cl–, E°Cl– /Cl = – 1.36 V
8. Answer (2) 2

On electrolysis only in case of Ca2+ salt aqueous

For Cr, E°Cr/Cr 3 = 0.74 V
solution H2 gas discharge at Cathode.
Case of Cr
For Mn2 , E°Mn2 /MnO4– = – 1.51 V
At cathode : Cr3+ + 2e– o Cr
So, Cr is deposited. Positive E° is for Cr, hence it is strongest reducing
Case of Ag agent.
At cathode : Ag+ + e– o Ag 13. Answer (3)
So, Ag is deposited. B2H6 + 3O2 o B2O3 + 3H2O
Case of Cu
27.66 of B2H6 = 1 mole of B2H6 which requires three
At cathode : Cu2+ + 2e– o Cu moles of oxygen (O2) for complete burning
Case of Ca2+
6H2O o 6H2+ 3O2 (On electrolysis)
1 Number of faradays = 12 = Amount of charge
At cathode : H2O + e– o H + OH–
2 2
12 × 96500 = i × t
9. Answer (1)
12 × 96500 = 100 × t
(1) Mn2+ + 2e o Mn; E° = –1.18V ;

'G1q 2F( 1.18) 2.36F 12 u 96500

t second
100
(2) Mn3+ + e o Mn2+ ; E° = +1.51 V;

'Gq2 F(1.51) 1.51F 12 u 96500

t hour
100 u 3600
(1) – 2 × (2)
3Mn2+ o Mn + 2Mn3+ ; t = 3.2 hours
14. Answer (1)
'Gq3 'G1q  2'Gq2
4
PbSO4 o Pb  2e –
= [2.36 – 2(–1.51)] F
= (2.36 + 3.02) F w Z uIu t
= 5.38 F
303
u 0.05F
But 'Gq3 2FEq 2uF
Ÿ 5.38F = –2FE° = 7.575
Ÿ E° = –2.69 V
| 7.6g
As E° value is negative reaction is non spontaneous.
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15. Answer (2) 18. Answer (2)

nFEqCell 0.059
InK E°cell = log K C
RT n
0.059
= log 1016
2 u 96000 u 2 2
InK
8 u 300 = 0.472 V
= 160 19. Answer (3)
K = e160
dEq
16. Answer (1) 'r Hq nFEq  nF T
dT
Cell : Pt(s)|H2(g,1bar)|HCl(aq)|AgCl(s)|Ag(s)|Pt(s)
Cell reaction :
Ecell = 0.92 V
Zn(s)  Cu2 aq o Zn2 aq  Cu(s)
q q 0.06
= EH2 ( g)|H (aq)  E AgCl(s)|Ag(s),Cl  log Q ? 'rH° = –2 × 96000 (2 + 300 × 5 × 10–4)
n
= – 2 × 96000 (2 + 0.15)
1  
Cell reaction : H2 (g) o H (aq)  e = – 412.8 × 103 J/mol
2
'rH° = – 412.8 kJ/mol
AgCl(s) + e– o Ag(s) + Cl–
20. Answer (2)
Net cell reaction:
/°m (NaCl) = 126.4 S cm2 mol–1
1  /°m (HCl) = 425.9 S cm2 mol–1
H2 (g)  AgCl(s) o Ag(s)  H(aq)  Cl (aq)
2
/°m (NaA) = 100.5 S cm2 mol–1

>H @ >Cl @ /°m (HA) = 425.9 – 126.4 + 100.5 = 400 S cm2 mol–1
? Q 1
PH2 2 K(HA) = 5 × 10–5 S cm–1

K u 1000 5 u 10 –5 u 1000
10–6 molal HCl solution is taken /c m = 50
Molarity 0.001
Assuming molality is same as molarity

10 6 u 10 6 /cm 50
Q 10 12 D= 0.125
1 /qm 400

0.06 21. Answer (3)

? 0.92 EqAgCl(s)|Ag(s),Cl  log 1012
1 More positive is the reduction potential stronger is
the oxidising agent.
? E qAgCl( s )|Ag( s ),Cl = 0.92 + [0.06 × (–12)]
Reduction potential is maximum for S2O82–.
= 0.92 – 0.72 22. Answer (3)
= 0.20 V
17. Answer (4) Ag  Fe2 o Fe3   Ag
(aq) aq (aq) (s)

Ecell EqR.P Cathode

 EqR.P Anode
Eocell EoAg /Ag – EFe
o
3
/Fe2
All electrodes act as cathode w.r.t. Zn so the ion
which has highest reduction potential will give To calculate
maximum value of E°cell so Au3+/Au produce highest
o
E°cell. EFe3
/Fe2 

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y ? Order of conductivity:

Fe HCOOH ! C6H5COOH ! CH3COOH

Fe3+ Fe2+ Ÿ
A ! C ! B
Eo = z
28. Answer (1)
o
EFe 3
/Fe 2 
3z – 2y
Conductivity of an electrolyte is the conductance of
1 cm3 of the given electrolyte. So, it increases with
EoAg / Ag x
the increase of concentration of electrolyte. Molar
conductivity (Om) is the conductance of a solution
Eocell x – 3z  2y containing 1 mole of the electrolyte. It increases
23. Answer (3) with the decrease of concentration (i) due to
increase in interionic attraction for strong
'G° = – nFE°cell
electrolytes and (ii) due to decrease in degree of
= –2 × (96000) × 2 V ionisation for weak electrolytes. Therefore, (S1) is
= –384 kJ/mole wrong and (S2) is correct.
24. Answer (4) 29. Answer (1)
0.1 F of electricity is passed through Ni(NO 3) 2
solution. Cu 2  2e – o Cu, 'G 1q –2F(0.34) ...(i)
? Amount of Ni deposited = 0.1 eq 
Cu  e o Cu, –
'G q2 –F(0.522) ...(ii)

0.1
? Moles = = 0.05 Subtract (ii) from (i)
2
25. Answer (3) Cu2   e – o Cu  , 'G3q –F(Eq )
KCl is more conducting than NaCl.
? 'G 1q – 'G q2 'G 3q

Ÿ –FE q –2F(0.34)  F(0.522)

/m KCl
Ÿ Eq 0.68 – 0.522 0.158 V
NaCl
30. Answer (3)
C
26. Answer (4)
o
/m o
NaBr  / m NaI o
/m Br   / m
o
I  …(1)

Greater the reduction potential, greater is the

oxidising power. o
/m o
KBr  / m NaBr o
/m K   /m
o
Na  …(2)
So, Co3+ > Pb4+ > Ce4+ > Bi3+
(1) and (2) are not equal.
27. Answer (2)
31. Answer (4)
HCOOH CH3COOH C6H5COOH
(A) (B) (C) E 0cell E0 E0
Cu 2  /Cu Zn 2  /Zn

Order of acidic strength = 0.34 – (–0.76)

HCOOH ! C6H5COOH ! CH3COOH = 1.10 V
pK a 3.8 4.2 4.8 if E ext < 1.1 V then Zn dissolves at anode and
copper deposits
More the acidic strength more will be the
dissociation of acid into ions and more will be if Eext > 1.1V then Zn deposited at zinc electrodes
conductivity. and copper dissolves

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32. Answer (3) 36. Answer (2.15)

Millimoles of Au+ = 0.1 × 250 = 25 At equilibrium state E cell 0 o
E cell 0.01 V

25 1 Sn s  Pb 2 aq. o Sn 2 aq.  Pb s

Mole of Au+
1000 40
0.06 [P]
Charge passed = I × t = 1 × 15 × 60 = 900 C E E ocell  log
n [R]
900 9
moles of e– passed
96500 965 0.06 [Sn 2 ]
0 0.01  log
2 [Pb 2 ]
Only gold will be deposited as quantity of charge
passed is less than the amount of Au+ present. 0.06 [Sn 2 ]
0.01 log
33. Answer (3) 2 [Pb 2 ]
The electrolyte (X) must be weak electrolyte. So X
1 [Sn 2 ]
is CH3COOH. log
3 [Pb 2 ]
34. Answer (1)
1
For the concentration cell, [Sn 2 ]
10 3 2.1544 2.15
[Pb 2 ]
2 2
Cu o Cu E ocell 0
(C 2M) (C 1M) 37. Answer (5.68)

Ag   e  o Ag
o RT C 1
E cell E cell  ln
2F C 2 108
Moles of Ag deposited = 1 mole
108
RT C 2 ? 1 mole e– or 1 F charge is required to deposite 1
ln
2F C 1 mole of Ag.

Gibb’s energy is negative only when Ecell is positive. 1

H 2O o O 2  2H   2e 
2
So, C 2 ! C 1
1
' 2 moles of e– liberate moles of O2
2
C2 = 2 C 1 is correct.
1
35. Answer (–0.93) ? 1 mole or 1 F charge will liberate mole of O2
4
The given half cell reaction is
1
? Volume of O2 at 1 bar and 273 K = u 22.7
2H 2O o O 2  4H   4e – 4
= 5.675 L
E qox –1.23 V
= 5.68 L
38. Answer (96500)
0.0591
log Po 2 >H  @
4
E ox E qox – Cu(s) + Sn2+(aq) o Cu2+(aq) + Sn(s)
4

At PO2 = 1 bar and [H+] = 10–5 M E ocell E oSn 2  /Sn  E oCu 2 /Cu

= –0.16 – 0.34 = –0.50 V

0.0591
E ox –1.23 – log10 –20
4 'G° = –nF E ocell

= –1.23 + 0.2955 = –0.93 V = –2 × 96500 (–0.50)

= 96500 J
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39. Answer (144)

2 u 52 104
2 Cu+(aq) U Cu(s) + Cu2+(aq) Mass of Cr3+ ions obtained
600 600

E0 0.16 V ; E 0 0.52 V Mass of Cr3+ ions actually obtained = 0.104 gm

Cu 2  /Cu  Cu  /Cu

6 u 0.104 u 100
E 0cell 0
E Cu – E 0Cu 2 /Cu  Efficiency 60%

/Cu 104

= 0.52 – 0.16 = 0.36 V 42. Answer (–6.00)

'G° = 17.37 kJ ; n = 3
RT
E 0cell ln K 'G° = –nFEocell
nF
17.37 u 1000
0.36 E ocell  –0.06 6.00 u 10 –2
ln K 14.4 144 u 10 1 3 u 96500
0.025
43. Answer (11)
40. Answer (142)
6OH– + Cl– o ClO3 + 3H2O + 6e–
Pt|H2(1 bar)|HCl(pH = 1)|AgCl|Ag

1 For synthesis of 1 mole of ClO3 , 6F of charge is

H 2  AgCl o H   Ag  Cl  required
2
current efficiency = 60%.
0.06
E cell E 0cell  log [H  ][Cl  ] ? To synthesise 1 mole of ClO3 , 10F of charge
1
is required.
= 0.22 – 0.06 log 10–2 = 0.34 V
Work function of Na metal = 2.3 eV 10
To synthesise moles of KClO3,
122
KE of photoelectron = 0.34 eV
Energy of incident radiation = 2.3 + 0.34 = 2.64 eV 10 u 10
charge = F
Also energy of incident radiation for K metal 122
= 2.64 eV
2 u t(hr) u 3600 100
Work function of K metal = 2.25 eV ?
96500 122
KE of photoelectrons = 2.64 – 2.25 = 0.39 eV
t  11
? Ecell = 0.39 V = 0.22 – 0.06 log [H+]2
44. Answer (3776)
= 0.22 + 0.12 × pH
MnO4–  8H  5e o Mn2  4H2O
pH  1.42 142 u 10 2

41. Answer (60.00) 0.059 [Mn2 ]

EMnO /Mn2  EºMnO /Mn2   log
4 4 5 [MnO 4 ][H ]8
Cr 2O 72 
 14H  6e o 2Cr  3
 7H 2O

I = 2 A, t = 8 min If [H+] = 1 M EMnO4 /Mn2  EºMnO /Mn2 

4

2 u 8 u 60 If [H+] = 10–4 M
Q F
96000 0.059
E MnO  EºMnO  /Mn 2   log 10 32
4 4 5
960 1
Moles of Cr2 O72  ions reduced
96000 u 6 600 EºMnO /Mn2  – 0.3776
4

1u 2 Magnitude of change in oxidising power

Moles of Cr3+ ions obtained
600 = 3776 × 10–4

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45. Answer (4)

­ ªNO3– º ªH º ½
4 4
Anode: 0.059 ° ¬ ¼ ¬ ¼ °
= ®log 4 ¾
Cu(s) o Cu+2 + 2e– 6 ° PNO2 °
¯ ¿
Cathode (1)

0.059
3e – + 4H+ + NO3– o NO + 2H2O 0.17 u 8 log HNO3
6
8H– + 2NO3– + 3Cu(s) o 3Cu+2 + 2NO + 4H2O
log (HNO3) = 2.16
3 2 [HNO3] = 102.16 = 10x
ªCu+2 º × pNO
¬ ¼
x = 2.16 Ÿ 2x = 4.32  4
Q= 2 8
ªNO3– º ªH+ º
¬ ¼ ¬ ¼ 46. Answer (25)

Eqcell 1.3 MnO 4  8H  5e – o Mn2  4H2 O , Eº = 1.51 V

' 1 mole of MnO 4 required 5 moles of electrons

3
Cu+2 pNO
2 or 5 F electricity.
0.059
Ecell 1.3 – log
6 2 8 ......(1) ? 5 moles of MnO 4 required 25 F electricity..
NO3– × H+
47. Answer (147)
Anode Cu(s) o Cu+2 + 2e–
Cathode Zn  2Ag o 2Ag  Zn2 

e – + 2n+ + NO3– o NO 2 + H2 O [Zn 2  ] (0.1)

Q 10 3
Cu s + 4H +
+ 2NO3– o 2NO2 + 2H2O + Cu +2 [Ag  ]2 (10 2 )2

Eqcell 1.13 emf 0.80  0.76 

0.059
log 103
2
2
Cu+2 pNO2 = 1.47 volt
Q= 2 4 emf = 147 × 10–2 volt
NO3– H+
x = 147
48. Answer (14)
+2 2
0.059 Cu pNO
Ecell 1.13 – log Conductivity
2 2 4 Conductance =
NO3– × H+ Cell constant

? Conductivity = 0.55 × 10–3 × 1.3 S cm–1

Ecell1 Ecell2 Molar conductivity

0.059 0.059 Conductivity (S cm1 ) u 1000

1.3 – log Q1 1.13 – log Q2 =
6 2 Molarity (mol/L)

0.059
0.17
6
^log Q1 – 3log Q2 ` =
0.55 u 10 3 u 1.3 u 100
5 u 103

­ 3 2 6 12 ½ = 143 S cm2 mol–1

0.059 ° Cu2 u pNO u NO3– H °
®log = 14.3 mS m2 mol–1
= 6 ° 2

8
2
3 6¾
NO3– H u Cu u pNO 2 °
¯ ¿ | 14 mS m2 mol1

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49. Answer (57) šf (HCl) = 426 S cm2 mol–1

For KCl šf (BaSO4) = šf (BaCl2) + šf (H2SO4) – 2šf (HCl)
k1 = 0.14 Sm–1
= 280 + 860 – 2 × 426
R1 = 4.19 :
= 288 S cm2 mol–1
For HCl
52. Answer (1)
k2 = x Sm–1 (Let)
Mass of KClO3 = 10 g
R2 = 1.03 :
10 x u 10 u 3600
Ÿ
122.6 6 u 96500
§l· §l·
R U ¨ ¸ Ÿ kR ¨a¸
©a¹ ©N¹ Ÿ x = 1.311 | 1 (nearest integer)
Cell constant
53. Answer (3)
k1R1 = k2R2 Cu + 2Ag+ 2+
o Cu + 2Ag
0.14 × 4.19 = 1.03 × k2
10–3 M 0.250 M
k2 = 0.5695 Sm–1
| 57 × 10–2 Sm–1 0.059 [Cu2+ ]
Ecell = Eocell – log
2 [Ag  ]2
50. Answer (45)

Fe2   2e  o Fe ; 'G1q 2FEqFe2  /Fe 0.059 (0.25)

= 2.97 – log = 2.81 V
2 (10 –3 )2
Fe3   3e  o Fe ; 'Gq2 3FEqFe3  /Fe
54. Answer (24)
Fe3+ + e– o Fe2+ ; 'Gq 'Gq2  'G1q Zn(s) | Zn2+(aq, 1 M) || Fe3+(aq), Fe2+(aq) | Pt(s)
Net reaction : Zn(s) + 2Fe3+(aq)
Ÿ FEqFe3  /Fe2  3FEqFe3  /Fe  2FEqFe2  /Fe
o Zn2+(aq) + 2Fe2+(aq)
Ÿ EqFe3  /Fe2 3EqFe3  /Fe  2EqFe2 /Fe
[Zn2 ][Fe2 ]2
= –3 × 0.036 + 2 × 0.440 Q
[Fe3 ]2
= 0.772 V
[Fe3+ + e– o Fe2+] × 2 0.0591
Ecell Eocell – logQ
  n
2I o I2  2e
3
2Fe  2I o 2Fe2   I2
2
0.0591 § [Fe2  ] ·
1.500 1.53 – log ¨
'r Gqm = – 2F × 0.772 – 2F (–0.539)
2 ¨ [Fe3  ] ¸¸
© ¹
= –2F(0.772 – 0.539)
= 44969 J [Fe2 ]
3.218
= 44.969 kJ [Fe3  ]
| 45 kJ
1
51. Answer (288) Fraction of Fe3+ = 0.237 23.7 u 10 –2
4.218
šf (BaCl2) = 280 S cm2 mol –1
| 24 u 10 –2
šf (H2SO4) = 860 S cm2 mol–1
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55. Answer (12) 57. Answer (2)

C = 0.001 mol L–1
K = 2 × 10–5 S cm–1
f
šm (HA) = 190 S cm2 mol–1
400
CH3COOH
K

/m /(S cm mol )
šm =

–1
×1000
C

2
2 u 10 –5 u 103 200
=
0.001
KCl
š m = 20

šm 20
D f
šm 190
0 0.2 0.4
1/2 1/2
C /(mol/L)
2
§ 20 ·
10 –3 ¨ ¸ f f f
CD2 © 190 ¹ /m (CH3COOH) = Om (CH3 COO– ) + Om (H )
Ka = 1– D 20
1– Molar conductivity increases with decrease in
190 concentration. This is because the total volume, V,
of solution containing one mole of electrolyte also
= 1.2383 × 10–5
increases. It has been found that decrease in k on
= 12.38 × 10–6 dilution of a solution is more than compensated by
56. Answer (28) increase in its volume.
58. Answer (109)
o Cu2  2e 
Cu 
Zn(s)  Cu2 (0.02 M) o Zn2 (0.04 M)  Cu(s)
2e   2Ag 
o 2Ag
2Ag  Cu 
o Cu2  2Ag
[Zn2 ] 0.04
Q 2
[Cu2 ] 0.02
RT § [Cu2  ] ·
E1 0.3095 Eq  ln ¨ ¸
nF © [Ag ]2 ¹ 0.059
Ecell Eocell  logQ
n
0.059 § 0.1 ·
0.3095 Eq  log ¨ 2 ¸
0.059
2 © (0.01) ¹ Ecell 1.1  log2
2

Eq 0.3095 
0.059
log (103 ) | 109 u 10 2 V
2
59. Answer (760)
0.059 l
0.3095  u 3 = 0.398 V 1.14 cm1
2 Cell constant =
a
For second cell, C = 0.001 M

0.059 ª 0.01 º T = 298 K

E 0.398  log « 2»
2 ¬ (0.001) ¼ R = 1500 :

= 0.28 V = 28 × 10–2 V 1§ l · 1
k u 1.14
R ¨© a ¸¹ 1500
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64. Answer (266)

k u 1000
/m
C Molarity of KCl solution = 0.1 M

Resistance = 1750 ohm

1
u 1.14 u 1000 Conductivity = 0.152 × 10–3 S cm–1
1500
=
0.001
Cell constant
Conductivity =
= 760 S cm2 mol–1 Resistance

60. Answer (25) ? Cell constant = 0.152 × 10–3 × 1750

= 266 × 10–3 cm–1
'G nFEocell 'H  T'S
65. Answer (23)
2 u 96487 u 4.315  825.2 u 10 3
Eqcell q
Ecathode q
 Eanode
'S
298
= 0.77 – 0.54
1
'S | 25 JK = 0.23 V
61. Answer (4) = 23 × 10–2 V
Parameter Unit 66. Answer (1)

Cell constant m–1 Standard Reduction

Molar conductivity S cm2 mol–1 Potential

Conductivity :–1 m–1 (A) Cl2/Cl 1.36 V

Degree of dissociation of Dimensionless (B) I2/I– 0.54 V

electrolyte (C) Ag+/Ag 0.80 V

62. Answer (26) (D) Na+/Na –2.71 V

1 (E) Li+/ Li –3.05 V

N u Cell constant
R Hence, correct order is A > C > B > D > E
67. Answer (20)
1
1.07 u 106 S m1 u (Cell constant)
0.243 Fe3+ + 3e– o Fe

Cell constant = 26 × 104 0.3482

Moles of Fe deposited = 6.2 u 10 3
63. Answer (5) 56
For 1 mole Fe, charge required is 3 F
2
ªH †º
For 6.2 × 10 –3 mole Fe, charge required is
0.06
Ecell o
Ecell  log ¬ ¼
2 ªCu2 º 3 × 6.2 × 10–3 F
¬ ¼
2
ªH† º Since, charge required = 18.6 × 10–3 × 96500 C
0.576 0.34  0.03 log ¬ ¼
>0.01@ = 1794.9 C
2 And,
0.576 – 0.34 = –0.03 log ªH† º + 0.03 log(0.01)
¬ ¼
1.5 × t = 1794.9
= 0.06 pH – 0.06
1794.9
t= min
pH  4.93  5 1.5 u 60

t  20 min
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68. Answer (3) 70. Answer (14)

We know that o
/m (AgI) o
/m o
(NaI)  /m o
(AgNO3 )  /m (NaNO3 )

2.303RT ª 1 º = 12.7 + 13.3 – 12.0

E Eo  log « »
nF ¬ (oxidized form) ¼ = 26 – 12
= 14 mS m2 mol–1
2.303 R ª 1 º
Slope log « » 71. Answer (51)
nF ¬ (oxidized form) ¼

Pt(s) H2 (g) H (aq) Ag (aq) Ag(s)

E 1
H2  Ag o Ag  H
2

n=1
T
Eqcell 0.5332
§ wE ·
Higher the value of slope ¨ wT ¸ , more the
© ¹P 'Gq nFEq
deviation between E and E°. Thus, half cell with
1u 96500 u 0.5332
§ wE ·
least value of ¨ wT ¸ can be used as reference 51.453 kJ/mole
© ¹P
electrode.  51 kJ/mole

69. Answer (983) 72. Answer (3)

Cu  Sn2 o Cu2  Sn(s) A 2 X3 U 2A  3X

2S 3S
Eqcell q
EOX q
 ERe d
Ksp = (2s)2(3s)3 = 1.1 × 10–23
0.34  0.14 S | 105
0.48 V For sparingly soluble salts

šm šmo
0.0591
q [Cu2 ]
E E  log
2 [Sn2 ] k
šm
S u 103
0.48  0.0295 log 10

3 u 105
0.5095 V u 103
105
'G nFE
3 u 10 3 Sm2 mol1
2 u 96500 u 0.5095 J/mol
73. Answer (6)
3
98333.5 u 10 kJ/mol 6
Cr2O27  
o 2Cr 3 
983.3 u 101 kJ/mol
' Each Cr is converting from +6 to +3

983 u 101 kJ/mol ? 6 faradays of charge is required

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74. Answer (16)

EqCell EqZn|Zn2  EqSn x |Sn
Sn o Sn2  2e E1o 0.140 V
Ÿ 0.763 + 0.008 = 0.771 V

Sn 4   4e  o Sn Eo2 0.010 V From Nernst equation,

Eocell –2.303 RT
Sn4   2e o Sn2  ECell EqCell logQ
nF
n2Eo2  n1E1o 4(0.010)  2(0.140)
Eocell = 0.06
n 2 0.801 0.771  log10 –2
n
Eocell = 0.16 V = 16 × 10–2 V
0.06
0.03 u2
75. Answer (127) n

3 n=4
2 F produces = mole of gas
2 78. Answer (1)
0.10 ×2 × 3600 coulomb produces
k1 × 1000 k u 1000
/ m1
3 M1 10
u 0.1u 2 u 3600 0.02
= 2
2 u 96500
k 2 × 1000
= 0.0056 moles of gas / m2
20
Volume of gas produced = 0.0056 × 22.7 L 0.08

 0.127 L It is given that k1 = k2

= 127 mL / m1 /m2
k1 = k2 =
76. Answer (7) 2 4

Applying the given condition on conductivity.

[H ]2 10 6
Q pH2 = 1
[Cu2 ]pH2 C / m1 /m2
2 4
o 0.06
E = Ecell  log Q
n /m2 2/m1

0.06 106 79. Answer (3)

0.31 = 0.34  log
2 C
For Fe3O4,

10 6
log 1 8
C x
3
C = 10–7 M
where x is oxidation state of Fe.
x=7
Fe3O4  8H  8e  o 3Fe  4H2O
77. Answer (4)
A: Zn o Zn2+ + 2e– 8 8F
Charge required = uF  3F
3 3
C: Sn+x + xe– o Sn
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80. Answer (3)

1000 u 129 u 10 –2
/2
(A) Cd(s) + 2Ni(OH)3(s) o 50 M
CdO(s) + 2Ni(OH)2(s) + H2O(l)
149 1000
(Discharging of secondary battery) M u 2 u 10 –3 M
74.5 106
(B) Zn(Hg) + HgO(s) o
1000 u 129 u 10 –2
ZnO(s) + Hg(l) (Primary battery) /2 –3
129 u 102 Scm2 mol–1
50 u 2 u 10
(C) 2PbSO4(s) + 2H2O(l) o
/1
Pb(s) + PbO2(s) + 2H2SO4(aq) 1 1000 u 10 –3
/2
(Charging of secondary battery)
Ÿ x = 1000
(D) 2H2(g) + O2(g) ® 2H2O(l) (Fuel cell) 83. Answer (34)
81. Answer (1)
0.06 ªCu2 º
The metal atom whose oxidation potential is less E = Eq  log ¬ ¼
2
2 ª Ag º
†
than that of hydrogen can release H2 from mineral ¬ ¼

acids.
0.06 0.001
= Eq  2 log
EqZn/ Zn2 0.76 EqNi/Ni2 0.25 (0.01)2

0.43 = E° – 0.03
EMn/Mn2 1.18 EqCu/Cu2 0.34
E° = 0.46 V
82. Answer (1000)
EoAg† / Ag  ECu
o
2
/Cu
0.46
1000 K
Solution 1, /m1
M ? EoCu2 /Cu 0.8  0.46

74.5 1000 = 0.34 V

M u 10 –3 M
74.5 106 = 34 × 10–2 V

[density of solution = 1 g/mol] 84. Answer (2)

For any electrolyte, molar conductivity decreases

1000 u 129 u 10 –4 2 2 –1
/1 129 u 10 Scm mol with dilution.
10 –3

ª x 129 u 10 –2 º
«K »
«¬ R 100 »¼

Solution 2, .

129 u 10 –2
K
50
Both Statements are false.

‰‰‰

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