Electrochemistry 3.

Chapter 3 Electrochemistry
INTEXT EXERCISE: 1
1. Electrolytes furnish ions on being dissolved in a 7. More negative is the reduction potential, higher will
polar solvent or in the fused state. be the reducing property, i.e. the power to give up
aq electrons
2. HCl is an electrolyte. HCl H(aq)
+
+ Cl(aq)
-

8. A can be displaced by the ion of D because D has a

3. Lower the reduction potential of the oxidized state,
lower reduction potential than A.
greater is the reducing power of the reduced state.
9. The value of the standard electrode potential of a
4. The species which has the highest reduction potential
half reaction remains unchanged on multiplying the
has the greatest tendency to get reduced and hence is
half reaction by any number.
the strongest oxidizing agent.
10. As soon as the salt bridge is removed, the circuit
5. Greater the reduction potential of the oxidized state,
breaks and thus the current becomes zero
less is the reducing power of the reduced state.
immediately.
6. In galvanic cell, the salt bridge used to complete
the circuit and maintain electrical neutrality of the
solutions in the half-cells.
INTEXT EXERCISE: 2
1. EMF of a cell is independent of size of electrodes or 6. In Daniel Cell, Cu is the cathode and Zn is the anode.
concentration of ions in salt bridge. Reduction occurs at cathode and oxidation at anode.
2. EMF for (b) is positive and = EoRed (M+) + EoOx (X-) 7. Electrode on which oxidation on occurs is written on
= 0.44 + (-0.33) = 0.11 V. L.H.S. and the other on the R.H.S. as represented by

3. Sn —→ Sn2+ + 2e- 0.14 V Zn | Zn2+ | | Cu2+ | Cu

Fe2+ + 2e- —→ Fe -0.44 V 8. Ni —→ Ni2+ + 2e- Eoanode = + 0.25 V
⇒ Eocell = 0.14 - 0.44 = - 0.3V Au3+ + 3e- —→ Au Eocathode = + 1.5 V
4. The value of Eo does not change on multiplying \ Eocell = Eoanode + Eocathode = 1.75 V
the cell reaction with any number. On reversing the
reaction, the sign of Eo changes. 9. Eocell = EoR.P. + EoO.P.
5. In the given reaction I- has been oxidized to I2 and \ E oMg/Mg = Ecell
o
2+
o
- ECu 2+
/Cu = 2.7 - 0.34 = 2.36V
Cr2O72- has been reduced to Cr3+ \ E o
=- 2.36V
Mg 2+ /Mg
o o o
\ E cell =E Cr2 O 2-
7 -E I2
10. For a Galvanic cell to be spontaneous its EMF
o o
0.79 = 1.33 - E I2 or E I2 = 0.54 V should be positive.
INTEXT EXERCISE: 3
RT C
1. Ecell = Eocell - nF in C2 and DG = - nFEcell. - 0.059 6H +@ 2

51 ?2
1 3. Ecell = 2 log
Hence DG is a function of ln (C2/C1). or, 0.59=0.059 pH or pH=10
2. Eocell = EoRed(RHS) - EoRed(LHS) = 1.5 - (0.25)=1.75V 4. Zn —→ Zn + 2e 2+ -

Cell Reaction: 3Ni + 2Au3+ —→ 3Ni2+ + 2Au 0.059

]0.01g3 E = Eo - -2
0.06 2 log10
]0.01g2
Ecell = Eocell - 6 log
E = 0.763 + 0.0591 = 0.8221V
= 1.75 - 0.01 log 0.01 = 1.75 + 0.02
\ Ecell = 1.77 V
3.2 Chemistry
0.059 8. Wmax = - n FEocell
5. E o = n log K or
= - 2 × 96500 × 1.1 J
1.10×2
log K = 0.059 = 37.2881 or K - 1037 \ Wmax = - 212300 J
6. - n FEocell = - RT ln K = - 212.3 kJ
RT \ Wmax by the cell = 212.3 kJ
Eocell = nF ln K.
1 RT 9. Calomel electrode as reference electrode is made by
Plot of Eocell vs ln K will have slope = 2 F
using Hg2 Cl2.
So, the line should have a small positive slope. 10 -6
10. Ecell =- 0.059 log =- 0.059 log10 -3
2.303 RT 0.0591 10 -3
7. E o cell = nF log K = n log K c at 298K.
\ Ecell = 0.059 × 3 = 0.177 V
INTEXT EXERCISE: 4
1. Faraday’s laws are related to equivalent weights Q 96500×4
Hence t = I = 3 s = 35.7 hrs - 36 hrs .
2. For same q, ECu = EAg now n-factors are 2 and 1
n Ag 9. 2.24 L of H2 at NTP = 0.2 g of H2
E x
\ nCu = 2 & nAg = E \ nCu = 2 = y ⇒ x = 2y
Wt of Cu Eq. wt. of Cu
Wt of H 2 = Eq. wt. of H
3. Mg and Al have lower reduction potentials than
Wt of Cu 63.5/2
H2O. Hence H2O is reduced more easily to give H2 i.e. 0.2 = 1
gas at the cathode
or Wt. of Cu = 6.35 g.
4. 108 g Ag = 1 g eq. of Ag. It requires 1 F.
10. time = 16 × 60 + 5 = 965s
5. 1 F deposits 1 eq ⇒ 2.5 F will deposit 2.5 eq.
Q = 1 × 965 = 965 C
6. 2 × 96500 C deposit Cu = 63.6 g. Hence 9650 C will Cu2+ + 2e- → Cu,
deposit Cu = 3.18 g.
2 × 96500 C decomposes 1mole CuCl2
7. One mole of electrons ( i.e, 1 F) will deposit 1 g eq. 1
\ 965 C decompose CuCl2 = 200 mole
i.e. 31.25 g Cu, 12g Mg, 23g Na and 9g Al.
= 0.005 mole.
8. Eq. wt of H2O = 1 + 8 = 9. Hence 9 g is decomposed
by 96500 C. So 36 g will be decomposed by This was present in one litre of CuCl2 solution.
Hence strength = 0.005 M.
Q = 96500 × 4 C.
INTEXT EXERCISE: 5
1 1
1. k = R × cell const 7. Molar conductivity = tM

\ b A l = k × R = 0.0212 × 55 = 1.166 cm-1.

l So its unit will be W-1 cm2 mol-1
1 1
1 1 8. Conductance = resistance = ohm = ohm -1
2. k = R × cell const = 100 × 1 = 10-2 ohm-1 cm-1.
1
1000k 1000×6.3×10 -2 9. Since molar conductance \ Molarity
3. m m = M = 0.1 = 630 ohm-1 cm2
Therefore the most dilute solution has the highest
l 3
4. Cell constant = A = 4 cm -1 Lm
ClCH 2 COONa +HCl"ClCH 2 COOH +NaCl l
10. a = 0.5 cm-1, R = 50 ohm
5. m ClCH COONa + m HCl = m ClCH COOH + m NaCl
2 2

Ra 50
224 + 203 = m ClCH COOH + 38.5 t = l = 0.5 = 100
2

m ClCH COOH = 427 - 38.5 = 388.5 ohm -1 cm 2 gmeq -1 1000 1 1000 1 1000
2
L = k × N = t × N = 100 × 1
1000 1
6. Molar conductivity = MX as k = X = 10 ohm-1 cm2 eq-1

INTEXT EXERCISE: 6
1. Practically 60-70% efficiency has been attained for
fuel cells.
2. Overall reaction of fuel cell is:
2H2(g) + O2(g) → 2H2O(l).
3. During charging of lead storage battery H2SO4 is
produced.
4. Reaction in a dry cell:
2NH4Cl + Zn → 2NH3 + ZnCl2 + H2↑
5. MnO2 is used in dry batteries cell, to seperate the
anode from the cathode - depolarizer.
6. In hydrogen–oxygen fuel cell following reactions
take place to create potential difference between two
electrodes.
2H2(g) + 4OH-(aq) → 4H2O(l) + 4e-
O 2(g) + 2H 2 O(l) + 4e - " 4OH -(aq)
Overall reaction = 2H 2(g) + O 2(g) " 2H 2 O(l)
EXERCISE - 1
1. Graphite is a good conductor. NaCl is non conducting
in solid state.
2. An electrolyte dissociates into ions when dissolved
in suitable solvent.
3. Standard electrode potential for a half- reaction is
fixed.
4. Higher the oxidation potential (or lower the
reduction potential) stronger the reducing agent.
5. A large negative reduction potential means a high
oxidation potential so that A- is easily oxidized
6. Lower the reduction potential, stronger is the
reducing agent.
7. Greater the reduction potential, stronger is the
oxidizing agent or weaker is the reducing agent
8. Greater the reduction potential, less is the reducing
power.
9. Greater the reduction potential stronger is the
oxidizing agent. Hence Y is stronger oxidizing agent
than X but weaker than Z.
10. Greater the reduction potential, stronger is the
oxidizing agent or weaker is the reducing agent
11. Cell potential
= EoRed (RHS) - EoRed (LHS)
= 0.34 - (-0.76) = + 1.10 V
Electrochemistry 3.3
The net reaction is the same as burning (Combustion)
of hydrogen to form water.
7. Since tendency to get oxidized is higher for zinc so
Zn acts as the anode and Fe as the cathode.
8. Corrosion is essentially a redox reaction. Thus, it is
an electrochemical process.
9. HgCl2 has corrosive action. It is highly poisonous.
It sublimes on heating. It is, therefore, known as
corrosive sublimate. Facts, good to remember.
10. Fe → Fe2+ + 2e (anode reaction)
O2 + 2H2O + 4e → 4OH- (cathode reaction)
The overall reaction is 2Fe + O2 + 2H2O → 2Fe(OH)2
Fe(OH)2 is dehydrated to iron oxide FeO, or further
oxidised to Fe(OH)3 and then dehydrated to iron
rust, Fe2O3.
12. EMF for (a) is positive.(c) and (d) involve only
oxidation or reduction and are impossible.
13. H2 undergoes oxidation and AgCl(Ag+) undergoes
reduction.
14. Cu → Cu2+ + 2e- (Oxidation)
Hg2+ + 2e- → Hg (Reduction)
Cu + Hg2+ —→ Cu2+ + Hg
15. Cu + 2 Ag+ —→ Cu2+ + 2 Ag.
16. See electrochemical series.
17. Reduction half reaction is Ag+ + e- → Ag
18. MnO-4 will oxidize Cl- ion according to the equation
2MnO-4 + 16H+ + 10Cl- → 2Mn2+ + 8H2O + 5Cl2
The cell corresponding to this reaction is as follows:
-
Pt, Cl2 (1 atm) |Cl || MnO-4 , Mn2+, H+ |pt
Eocell = 1.51 - 1.40 = 0.11 V
As Eocell is +ve, the above reaction is feasible. Thus
MnO-4 will not only oxidize Fe2+ ion but also Cl- ion
simultaneously. Hence, statement (a) is incorrect.
19. Oxidation takes place at anode viz (a).
20. Eocell = Eoox (Fe) + EoRed (Zn) = -0.41 + 0.76 = 0.35 V
21. Eocell = Eoox (B) + EoRed (A) = 0.42 + 0.35 = 0.77 V
3.4 Chemistry
22. E o cell = E o Red (RHS) - E o Red (LHS) 0.0591 0.01
E1 = E o = 2 log 1.0
o o
=E Cu 2+ /Cu -E Ni 2+ /Ni
0.0591 1.0
E 2 = E o - 2 log 0.01
i.e. = 0.59 = 0.34 - E o Ni 2+
/Ni or E o Ni 2+
/Ni

= 0.34 - 0.59 = - 0.25 V Thus E1 > E2.

23. The half- cell reactions of the given cell will be 34. Cu2+ + 2e- → Cu
0.0591 1
E = E o - n log
Cr → Cr3+ + 3e-, Eo = + 0.74 V 6Cu 2+@
Cu2+ + 2e- → Cu, Eo = + 0.34 V 0.0591 1
= 0.34 - 2 log 0.01
\ Ecell = 0.74 + 0.34 = 1.08 V = 0.2809 = 0.281 V.
24. AgCl (s) + e- → A Ag + Cl- (aq) 35. For the given reaction Eocell = - 0.80 V
Ag " Ag + (aq) + e - DG = -nFEocell
overall reaction: AgCl (s) " Ag + + Cl - = -2 × 96500 × (-0.80) J = 154.4 kJ.
25. For the cell reaction Cu+ 2 Ag+ → Cu2+ + 2 Ag. 36. If cathode or anode is pulled out, no electrolysis will
E o
cell =E o
Ag + / Ag - E o
Cu /Cu2+
= 0.80 – 0.34 = 0 .46 V take place. The ions will start moving randomly.
This is the difference of reduction potential of Ag 37. 1 F = Avogadro’s no. of electrons.
and Cu electrodes. Taking electrode pot. of 38. Amount of ion discharged does not depend upon
Ag = O, - E o 2+
Cu /Cu = 0.46 V resistance.
or E o
Cu/Cu 2+ = 0.46 V 39. Higher the reduction potential, more easily is the
metal deposited (Mn+ + ne- → M). Mg2+ ions will
26. At equilibrium, Q = Kc and E= 0. not be deposited because H2O is reduced more easily
0.0591 than Mg2+ ions.
27. Eocell = n log Kc
28. R.H.S. 2H+ + 2e- H2 (P2) 40. One g eq. is deposited by 1 F i.e. charge on 1 mole
of electrons.
L.H.S. H2 (P1) 2H+ + 2e-
41. At cathode, reduction takes place.
Overall reaction: H2 (P1) H2 + (P2)
RT P RT P RT P 42. Electrons flow from anode to cathode through the
E = Eo - nF ln P =2 0 - 2F ln P2 = 2F ln P1 external supply. In the solution charge flows by the
1 1 2

29. (i) E o Ag /Ag - E o Cu /Cu = 0.46

+ 2+ movement of ions and not by electrons.
(ii) E o Cu /Cu - E o Zn /Zu = 1.10
2+ 2+
43. 1 F = 96500 C.
Aim : E o Ag +
/Ag - E o Zn 2+
/Zn =?
44. In galvanic cell, cathode is positive but in electrolytic
Eqn. (i) + (ii) gives the required result. cell, cathode is negative.
0.0591 6Zn 2+@
30. Ecell = E o cell - log
n 6Cu 2+@ 45. To deposit 1 g eq. of any element, 1 F is required.
0.0591 46. Electrolysis of CuSO4 using Pt electrodes gives
o
E o cell -
2 log 1 = E cell = 1.10 V copper at cathode and oxygen at anode.
31. This is a concentraiton cell.
47. NO-3 is a stronger oxidizing agent than H+ and hence
0.059 C 0.059 10 -4
E cell = n log C2 = 1 log -6
o
NO-3 is reduced in preference to H+.
1 10
0.059 6Zn 2+@ 48. Impure sample is made the anode and pure copper as
32. Zn + Cd2 + → Zn2++ Cd, Ecell = Eocell - 2 log
6Cd 2+@ the cathode.
= 6]- 0.43g - ]- 0.763g@ -
0.059 0.004
2 log 0.2 49. Cu2+ + 2e- → Cu.
0.059 0.2 2 F will deposit Cu = 1 g atom = 63.5 g.
= 0.36 + 2 log 0.004
50. 1 F will deposit 1 g eq. of each. Eq wts. are :
33. For the given cell, Zn + Cu2+ → Zn2+ + Cu
59 52
0.0591 6Zn 2+@ Ag = 108, Ni = 2 = 29.5, Cr = 3 = 17.3
E = Eo - log
2 6Cu 2+@
 Electrochemistry 3.5
51. Q = C × t = 0.6 × (7 × 60) = 252 C, = 252 / 96500 cell const. 1.15
62. k = C × cell const. = R = 250
F = 2.6 × 10-3 F.
k×1000 1.15 1000
52. 1 g eq. of H2 i. e. 1 g or 11200 cc is obtained from Leq = Normality = 250 × 1 = 4.6X -1 cm 2 eq -1
96500 C
l 0.4
\ 112 ml will be obtained from 965 C., 63. k = R × cell const. = 40 = 10-2.
Q 965 1000k
\ i = t = 965 = 1 A. \ L = M = 103
53. 4 mole electrons ⇒ 4 Faradyas = 4 equivalents 1 1
64. k = R ×cell const = 10000 × 8.76
Eq. volume of H2 = 11.2 L at STP ⇒ 4 Eq. = 44.8 L
Eq. vol. of O2 = 5.6 L at STP ⇒ 4 Eq. = 22.4 L = 8.76×10 -4 X -1 cm -1
\ Total volume of gases evolve = 67.2 L k×1000 / m ×Molarity
65. / m = Molarity or k = 1000
it wt. of Zn
54. 96500 = Eq. wt. of Zn 1.26×10 -2 ×0.01
= 1000 = 1.26×10 -3
65
Eq. wt. of Zn = 2 = 32.5 1 l 1
66. k = R × a i.e., R \ k
5×40×60
\ wt. of Zn = 96500 × 32.5 g 67. Solubility,
= 4.04 g k1000 3.06×10 -6 ×1000
s= = 1.53 = 2×10 -3 molL-1
wt. of Cl 2 2×30×60 /o
55. 35.5 = 96500 68. L(C2H5COOH) = L(C2H5COONa)
\ wt. of Cl2 = 1.324 g + L(HCl)- L(NaCl)
h it = 91 + 426.16 - 126.45 = 390.71 ohm-1 cm2
56. No. of Faradays passed = 96500
0.6×12×3600 69. Ionic conductance of ion = Transport no. of that ion
= 96500 × Leqo of strong electrolyte containing that ion
Assuming half of this charge is used to reduce Ni2+
= (1 - 0.40) × 160.84 = 96.504 ionic mobility
and half to reduce H2O producing H2
wt. of Ni 1 0.6×12×3600 Ionic conductance 96.504
\ = = 96500 = 10 -3
58.7/2 = 2 × 96500 96500
⇒ wt. of Ni = 3.941 g 70. Lo (CX) = loc + lox
57. Eq. conductance increases with dilution and = Lo (BX) + Lo (CA) - Lo (BA) = 198 + 120 - 140
ultimately becomes constant. = 178 Scm2eq-1.
58. Conductivity water has negligible conductance of its 71. Transport number can be zero (e.g at high
own. concentrations of CdI2 solution, Cd2+ may have zero
59. In electrolytic conductors, ions flow and not the or even negative transport number due to formation
electrons. of complex ion, CdI2-4 )
60. Conductance of electrolytic solution increases with 72. When a lead storage battery is discharged, H2SO4
temperature because dissociation increases. is consumed. Discharging reaction of lead storage
Area×Conc battery: Pb + PbO2 +2H2SO4 —→ 2PbSO4 + 2H2O
61. Conductance \ Length 73. This is because zinc has higher oxidation potential
Area×Conc than Ni, Cu and Sn.
Conductance = k × Length or
74. Fuel cell converts chemical energy of H2 and O2 into
Conductance × Length S×m electrical energy.
k = Area×Conc. = 2
m ×mol m -3
75. All the given statements about the fuel cells are
= Sm2 mol-1.
correct.
3.6 Chemistry
EXERCISE - 2
o
1. E is intensive property and it does not depend on 20. H 2 $ 2H + + 2e -
(p1)

mass of F2 getting reduced.

2H + + 2e - $ H 2 (P2)

2. Lower S.R.P. containing ion can displace higher

S.R.P. containing ion. X2 $ X2
(P1) (P2)

0.0591 p2
3. M is more reactive than carbon and B is more E = 0- 2 log p1
reactive than A. Also both B and A are less reactive P2 < +1 for E to be + ve
than C.
R (T + 273)
4. Lowest S.R.P., highest reducing power. 21. E1 = Eº – nF ln 2

5. Cu can’t displace Al3+ ion from aluminium nitrate. R×(2T + 373)

E2 = Eº – nF ln 1 = Eº
6. Sn —→ Sn2+ + 2e- Eo = + 0.14 V
-
\ E2 > E1
Fe + e —→ Fe
3+ 2+
Eo = + 0.77 V
\ Sn + 2Fe3+—→Sn2+ + 2Fe2+ + Fe2+ Eo = 0.14+0.77 22. Fe3+ + 3e– —→ Fe , – 0.036 volt
= 0.91 V Fe —→ Fe2+ + 2e– , 0.44 volt

7. Lower standard reduction potential related metal Fe3+ + e– —→ Fe2+, Eo

ions can discharge higher standard reduction \ + 3 × 0.036F –2 × 0.44 × F = – 1 × E° × F
potential metal ions. E° = 0.772 Volt
8. Lowest S.R.P., highest reducing power. 0 - 0.059 10 -5
23. Ecell = 1 log = 0.059 V
9. E 0
= 0.34 E 0
=- 0.44 volt 10 -3
Cu 2+ /Cu Fe 2+ /Fe

So Cu can’t displace Fe . 2+ 24. Cu+ + e– —→ Cu , E° = x1 Volt

10. KCl can form precipitate with AgNO3, Pb(NO3)2 so Cu2+ + 2e– —→ Cu , x2 Volt
can’t be used along these electrolyte. Cu —→ Cu+ + e– – x1Volt
11. In galvanic cell / electrochemical cell electrical Cu2+ + e– —→ Cu+, Eo volt
energy is produced due to some chemical reaction.
\ – 2 × x2 × F + 1 × x1 × F = –1 × Eº × F
12. As E o Cu 2+
/Cu (= 0.337 V) > E0H +
/H 2 (= 0V)
Eº = 2x2 – x1
\ Cu2+ can be reduced by H2
C
25. Ecell = 0.059 log C1
13. Salt bridge complete the electrical circuit and 2

minimises the liquid - liquid junction potential. For Ecell to be +ve and maximum
14. Agar-Agar is a gelatin, it is commonly used in salt C1
bridge along with KCl electrolyte. C 2 < 1 or C1 < C2. Given C2 = 1M.

15. Only anode or cathode can’t work alone so absolute \ C1 should be the minimum conc. of H+.
value of reduction potential can’t be determined. \ (B) is the right answer, as CH3COOH is the
16. Ecell = E o
Ni/Ni 2+ +E o
Ag + /Ag
weakest acid.
= 0.25 + 0.80 = 1.05 Volt. 26. H2(Pt) (1 atm) | H3O+ | | Ag+(xM) | Ag
0.06 6H +@
17. For spontaneous reaction in every condition 1.0 = (0 + 0.8) – 1 log x
Ecell > 0, DG < 0 and Q (reaction quotient) < K 0.2 6H +@
- 0.06 = log x
(equilibrium constant).
10
18. E = 1.1 -
0.0591 0.1 3 = pH + log x
2 log 0.1 & E = 1.10 Volt
log x = – 1.7 = - 2 + 0.3
0.059 0.02 \ log x = log 10-2 + log 2
19. Ecell = (0.77 – 0.0713) – 1 log 0.1×0.34
= 0.713 volt. or, log x = log (2 × 10-2)
\ x = 2 × 10-2
 Electrochemistry 3.7
2+
27. Zn $ Zn(C ) + 2e
-
1
n3 = 5k
Zn 2+
+ 2e $ Zn
- 10 1 1
(C 2) n1 : n2 : n3 = 3 : 10 : 5 = 3 : 1 : 2 = 2 : 6 : 3
Zn]2C+ g Zn]2C+ g wt h it 0.237×96500×2
2 1
37. Eq. wt = 96500 & h = 63.5×2×3600
0.0591 C
E = 0 - 2 log C1
2 \ h = 0.1 = 10%
E → +ve When C1 < C2
38. Impure Cu will oxidise from anode along with Zn
log 6H +@
- 0.059
28. E1 = 1 but only Cu2+ will reduce on cathode in purification
x of Cu2+.
or pH1 = E1 /0.059 = pK a + log y
y 39. For AgNO3, at anode:- H2O is oxidized in preference
pH 2 = E 2 /0.059 = pK a + log x to NO3-
E1 + E 2 E1 + E 2
or 0.059 = 2 pK a or pK a = 0.118 2H2O —→ 4H+ + O2 + 4e- ⇒ pH decreases
29. H 2 $ 2H]+10 Mg + 2e - -2
for LiCl, at cathode :- H2O is reduced in preference
2H ]10 -3 Mg
+
+ 2e $ H 2- to Li+
2H ]10 -3 Mg
+
$ 2H]+10 -2
Mg 2H2O + 2 e- —→ H2 + 2 OH- ⇒ pH increases

c 10 m
-2 2
0.0591 wt. of Au 2×10×60
E = 0- 2 log 10 -3
40. 197/3 = 96500
E "- ve (Non spontaneous) 197×4
\ wt. of Au = 965 g
0.0591 16
30. E = 0 - 2 log 4 mass 40
\ Vol. of Au = density = 965 cc
0.0591
=- 2 ×2 log2 =- 0.0591×0.301 40
\ Area × 2 × 10-3 = 965 ⇒ Area = 20.72 cm2
= - 0.0178 Volt.
41. 2H2O + 2e– —→ H2 + 2OH-
If connected in reverse direction,E = 0.0178 volt. 9.65×1000
No. of Faraday passed = 96500 = 0.1 F
31. At anode Ag —→ Ag+ + e– nOH formed = 0.1 mol
-

At cathode Ag+ + e– —→ Ag nNaOH = 0.1 mol = 4 g.

So conc. of Ag+ will remain same. 42. Anode :- 2Br- —→ Br2 + 2 e-
1 Cathode :- Cu2+ + e- —→ Cu
32. Moles of Fe deposited = 2 × 3 = 1.5 mole
WFe = 1.5 × 56 = 84 g. 43. For iodide to iodine :
1000×2 27×24×3600×h 2I- —→ I2 + 2e- ⇒ n-factor for iodide = 1
33. ]
55 + 32g
= 96500 or h = 0.951 = 95.1%
34. equivalence of H2 = equivalence of O2 For iodate to iodine
0.224 volume of O 2 2I7+ + 14e- —→ I2 ⇒ n-factor for I2 = 14
22.4 ×2 = 22.4 ×4
0.112 litre = volume of O2. If charge passed is same then equivalents are same.
1.27 WI 1 254
35. Eq. of H2 = Eq. of O2 + Eq. of H2S2O8 \ 127/1 = 254/14 & WI = 100 × 14 = 0.181 g
2
2

9.72 2.35 WH S O
22.4 ×2 = 22.4 ×4 + 194 ×2 or W = 43.47 g
2 2 8
44. 8H+ + 5e– + MnO4– —→ Mn+2 + 4H2O
(1 mole)
36. According to Faraday’s second law
5 mole e– = 5 Faraday.
mass of A mass of B
equivalent mass of A = equivalent mass of B 45. In presence of inert electrode, the cell reaction is-
mass of C Anode: 2H2O —→ 4H+ + 4e- + O2
= equivalent mass of C
4.5 2.7 9.6 Cathode: {Cu++(eq) + 2e- —→ Cu(s)} × 2
15/n = 27/n = 48/n
1 2 3 ------------------------------
Net cell reaction 2Cu++ aq. + 2H2O —→ 4H+ +
0.3n1 = 0.1 n2 = 0.2 n3 = k
2Cu(s) + O2 -
10
n1 = 3 k Due to increase in {H ], pH decreases.
+

n2 = 10k \ (b) is answer.

3.8 Chemistry
1
46. C = R and k = C × A
l 54. / m,BaSO = ]x1 + x 2 - 2x3g
4

1 0.02 / m BaSO
\ k = 50 × 0.0004 ⇒ k = 1 Sm-1 = 10-2 Scm-1 & / eq.BaSO = n - factor
4
4

47. For strong electrolyte ]x1 + x 2 - 2x3g

/ eq.BaSO =
4
2
K CM = K3M - b C 55. Conductivity is minimum at equivalence point.
1 l 1 l 1 l \ Vol. of H2SO4 added to neutralize KOH = 15 mL
48. k1 = 50 a k2 = 100 a kmix = 80 a
Now, k1v1 + k2v2 = kmix vmix \ 20 × MKOH × 1 = 15 × 0.2 × 2
v v2 v +v \ MKOH = 0.3
\ 501 + 100 = 1 80 2
v 56. NH4OH + H+ + Cl- —→ NH+4 + Cl- + H2O
or, 6v1 = 2v2 ⇒ v12 = 3
Highly mobile H+ are replaced by less mobile NH+4,
49. Molar conductivity a no. of ions per mole of
so conductivity decreases till equivalence point. As
electrolyte.
NH4OH is a weak base so adding more of it after
50. Ka = 25 × 10–6 Leq = 19.6 Scm2 eq–1 , C = 0.01 equivalence point doesn’t increase the conductivity
25×10 -6 much.
Ka = 0.01 × a2 ⇒ a= = 5 × 10–2
10 -2 57. H2 – O2 fuel cell
19.6
a = 5 × 10–2 = o
Keq At anode : 2OH– + H2 —→ 2H2O + 2e–
o 19.6 At cathode : 2 H2O + O2 + 4e– —→ 4OH–
⇒ Keq = = 392 Scm2 eq-1.
5×10 -2
58. Discharging reaction of Lead strage battery
51. K a = Ca 2 = 0.1× b 380.8 l = 3.38×10 -5
7 2
Pb(s) + PbO2(s) + 2H2SO4 —→ 2PbSO4 + 2H2O.
52. k = 1.382 × 10–6 S cm–1 59. Rusting reaction of Fe is -
1000×1.382×10 -6
K AgCl = 61.9 + 76.3 = 138.2 = s 1
2H + + Fe + 2 O 2 $ Fe 2+ + H 2 O
\ s = 10–5 M.
60. Iron oxide formed during rusting is basic. Making
1000×3.06×10 -6
53. 1.53 = Normality the medium acidic consumes the oxide formed and
Normality = 2 × 10-3 promotes further rusting of iron.

2×10 -3
Molarity = 2 = 10 -3 M = solubility (s)
Ksp = s2 = 10-6 M
EXERCISE - 3
1. 2HSO4- → S2O82- + 2H+ + 2e- 3. Anode : Fe → Fe2+(0.1 M) + 2e-
so required rate = 1 mol/hr Cathode : 2Fe3+(0.01 M) + 2e- → 2Fe2+
= 2 mole of e-/hr Cell : 2Fe3+(0.01 M) + Fe → 2Fe2+(1 M) + Fe2+(0.1 M)
]0.01g2
2 × 96500 C 2 × 965
` Ecell = ]0.41 + 0.771g +
= 3600 sec = 36 A ; 53.6 A 0.059
4 2 log ]1 g2 ]0.1g
so required current = 3 × 53.6 A = 71.4 A
⇒ Ecell = 1.181 + 0.0295 (-3)
2. Anode Zn → Zn2+ + 2e-
⇒ Ecell = 1.0925 V.
Cathode 2H+ + 2e- → H2
4. no. of equivalents = no. of Faradays × h
Cell: Zn + 2H+ H2 + Zn2+;
no. of equivalents
Eocell = 0 - (-0.76) = 0.76 V ⇒ no. of Faradays = 0.4
0.059 0.01×1 n-factor of C6H5NO2 = 6
\ 0.701 = 0.76 - 2 log
6H +@2 123
\ [H ] = 10 M
+ -2 \ E.W. of C6H5NO2 = 6
6.15 × 6
\ mmoles of HCl = 0.01 = mmoles of NaOH \ No. of equivalents = 123
needed 6.15 × 6
\ no. of Faradays = 123 × 0.4 = 0.75
\ mass of NaOH required = 0.4 g
 Electrochemistry 3.9
5. n-factor of gold = 3 0.059 1
= 1.1 - 2 log = 0.71 V
w = Zit 6.25×10 -14
197 i × 20 × 60 10. (M —→ Mn+(0.02M) + ne-) × 2
2 = 3 × 96500
i = 2.449 A (2H+ 2e- —→ H2) × n
6. If cell is taken to be conc cell, Eocell = 0 2M + 2nH+ —→ 2Mn+ + nH2
Anode: Ag —→ Ag+a + e- 0.0591 ]0.02g2
]1 g2n
0.81 = (0.76 + 0) - 2n log
Cathode: Ag+c + e- —→ Ag
----------------------- & ]0.81 - 0.76g = 0.0591
2n log 4×10
-4

Ag+c Ag+a
n =- 2×0.5 ×log 4×10 -4 =- 0.591 ]- 4 + 0.6g = 2
From Nernst eq, 0.0591

0.059 7Ag +Aa

log 11. ksol = k Ba + k Ag + k NO
7Ag +Ac
Ecell = Ecell
o
- 1
2+ + -
3

m oBa × 6Ba 2+@ m Ag × 7Ag A m oNO × 6NO3-@

o +
7Ag +Aa
2+ + -

5.3 =
3

0.59 + +
& 0 = 0 - 1 log 10 -3 10 -3 10 -3
7Ag +Ac o
13×10 -3 ×0.1 6×10 -3 ×0.2 m^NO h ×0.4 -

\ 5.3 =
3

Ksp of AgBr Ksp of AgCl -3 + -3 +

\ [Ag ]a = [Ag ]c & 10 10 10 -3
6Br -@ 6Cl -@
+ +
=
\ m^oNO h = 7×10 -3 Sm 2 mol -1 . So, Ans = 7.
-

6Br @ 6Br @
3
-13
5×10 -
1-
= 200 & Ans = 5
6Cl -@ 6Cl -@
or, = & 12. Cathode :- 2H2O + 2e- —→ H2 + 2OH-
10 -10
7. H3O+ has highest / 3m among cations. A doubly Anode :- 2CH3COO- —→ 2CO2 + C2H6 + 2e-
charged cation has higher / 3m than unipositive \ For every mole of H2 we get 2 moles of CO2 and
cation. So, a, c, d and e are correct. 1 mole of C2H6.
8. MX M+ + X– 13. (A) H4XeO6 has more SRP, so better oxidizing agent
a+10–7 a then F2

Ksp = (a + 10–7) a (B) O3 has more SRP, so will oxidize Cl2

o
k tot = k M + k X + k NO
+ - -
(C) EClO /ClO is more in acidic medium than in basic
-
4
-
3

medium
3

Given, Ktot = 55 × 10-7 Sm-1 = 55 × 10-9 Scm-1. o

(D) E6Fe(CN) @ 3-
| 6Fe]CNg6@4- = 0.36 V
M/o 6

\ 55 × 10-9 = / 1000m Hence [Fe(CN)6]4– can be easily oxidized by

60 ^a + 10 -7h 80a 70×10 -7 ClO¯, Ce4+ Br2O– but not by Li+
= 1000 + 1000 + 1000 o
(E) EClO -
/Cl - ]OH -g is more than E oBrO -
Br - and
-9 -2 -9 -2 -9 o
or, 55×10 = 6×10 a + 6×10 + 8×10 a + 7×10 E ClO -4 /ClO 3- ]OH -g so true.
or, 42 × 10-9 = 14 × 10-2a (F) Ce can’t oxidize Cl2 in acidic medium due to
4+

\ a = 3 × 10-7 over potential.

\ Ksp = 3 × 10-7 (3 × 10-7 +10-7) 14. CH4 + 10OH¯ —→ CO32– + 7H2O + 8e–
or, Ksp = 12 × 10-14 ⇒ a = 12 and b = 14 80×3600×0.96
No. of Faradays required = 96500
⇒ Ans = 26. 1 80×3600×0.96
Hence mol. of CH4 required = 8 × 96500
9. Cu2+ + 4 NH3 → [Cu(NH3)4]2+
1 80×3600×0.96
1 a 0 VCH = 8 ×
4
96500 × 22.4 L
0 2 1
= 8.356 × 0.96 = 8.02 L
6Cu ]NH3g4@2+
Kf = 3.907
6Cu 2+@6NH3@4 15. a = 390.7 = 0.01
1 HA + aq H+ + A-
6Cu 2+@]2g4
or 1 ×1012 = or [Cu2+] = 6.25 × 10-14
Ca Ca
o 0.059 6Zn 2+@ [H+] = Ca = 0.01 × 0.01 = 10-4
Ecell = Ecell log
6Cu 2+@
Now, - 2 pH = - log [H+] = 4
3.10 Chemistry
2.977 3×1×60×60 21. l = 1.5 cm A = 10 cm2, C = 0.05 W
16. 106.4/n = 96500 & n=4
Effective area A’ = 5 cm2, R = 50 W
Ca 2 1 a2
17. K a = 1 - a & 6 = 1 - a 1 , 1 1.5
k = R × ' = 50 × 5
A
- 1 ! ]1 g2 + 4×6×1 - 1 ! 1 + 24 1
& a= 12 = 12 =3 1000 1.5
/ m = 0.05 × 50×5 = 120 Scm 2 mol -1
\ 6IO3-@ = 1× 3 = 3 M
1 1
22. H2 —→ 2H+ + 2e–

⇒ 7Ag +A = 1
3×10 -8 1 atm 10-10
= 9×10 -8 M
3 0.059 ^10 -10h 2

2e - E H /H = 0 -
2
+
2 log 1 & E H /H 2
+

Now 2 Ag + Zn +2
2Ag+ + Zn
0.06 1 = + 0.59 V = 590 mV.
Gives E =- 1.56 + 2 log
^9×10 -8h2 23. Charge passed = 0.01 Faraday
At the anode b H 2 O $ 2 O 2 + 2H + + 2e - l with 90
=- 1.1376 V 1

18. m om ]H 2 Og =
m om^Ba]OHg h + 2m om]HClg - m om]BaCl g
2 2

2 % efficientcy 0.01 × 0.9 F have been used and will

1
= 5.5 × 10-2 S m2 mol-1. produce 4 ×0.01×0.9 mole of O2 i.e. 0.00225 mol O2
+2e -
Now in SI units, At the cathode 2H2O H2 + 2OH–
k×10 -3 k×10 -3
0.01×0.8
m om = M ` m om(H O) =
2
]H 2 Ogdiss moles of H2 produced = 2 mol = 0.004 mol
5.5×10 -6 ×10 -3 Total moles produced of gases = 0.004 + 0.00225 =
\ 5.5×10 -2 = 6H 2 O@ diss
0.00625 mol
\ 6H 2 O@ diss = 6H +@ = 6OH -@ = 10 -7 M
vol. at STP = 0.00625 × 22400 mL = 140 mL
For equilibrium: H2O H+ + OH-
24. Eocell = EoRP(RHS) - EoRP(LHS)
Since the calculated value above matches the actual
value, therefore the reported answer is 20. = - 0.76 - ( - 1.36) = 0.6
dE 1.718 - 1.2 DrGo = - RT ln Keq;
19. 3 S o = nF dt = 2×96500× 20 =5000 J/K.
nFE o 2×0.6
or, log Keq = RT×2.303 = 0.06 = 20
k×1000
20. m m M 2×0.6
⇒ 0.06 ⇒ 20; Kf = 1020
k×1000
200 = 0.04
1000× ^ksol - k H Oh
25. m 0 =
2

200×0.04 s
k = 1000 = 8×10 -3 S cm -1
1000× ]3.4 - 2.02g ×10 -6
138 =
k = b a, l × R
1 s
s = 1×10 -5 mol/L = 10 mmol/m3.
8×10 = : 4 D × R
-3 8 1

2 1
R= = ×103 X
8×10 -3 4
Again ⇒ V = IR
V 10
So I = R = = 4×10 -2 A = 40 mA
b ×10 l
1 3
4
 Electrochemistry 3.11
EXERCISE - 4
1. Hg22++ 2e– —→ 2Hg, 0.789 Volt \ DGo = -285 × 103 × 0.84 = -2 F Eo
Hg —→ Hg2+ + 2e-, - 0.854 Volt 285×0.84×103
\ Eo = 2×96500
Hg22+ Hg + Hg2+ , –0.065 Volt \ E° = 1.24 Volt
DGo = – 2 × (–0.065) × 96500= –8.314 × 298 ln Keq; 8. MnO -4 + 8H + + 5e - $ Mn 2+ + 4H 2 O
Keq.= 6.3 × 10–3 0.0591 6Mn 2+@
E1 = E o - 5 log 6MnO -4 @ ×18
2. E° = 1.1028 – 0.641 × 10–3 T + 0.72 × 10–5 T2
6Mn 2+@
b dE l = –0.641 × 10–3 + 2 × 0.72 × 10–5 T
o
0.0591
E2 = Eo - log
dT 5 6MnO -4 @ × ^10 -4h8
Putting T = 25 0.0591
\ E2 - E1 =- 5 × 32 = - 0.37821 . - 0.38 V
b dE l = (–0.641 + 0.36) × 10–3 = –0.281 × 10–3
o

dT \ Potential decreases and so does the oxidizing

dE o power of MnO-4.
\ DS° = nF dT = 2 × 96500 × (–0.281 × 10–3)
dE -1
= – 54.23 9. dt =- 0.00065 Vol deg
3 S 298 = n.F. dT = 2×96500× ]- 0.00065g
3. E o298 = 1.1028 – 0.641 × 10–3 × 25 + 0.72×10–5×(25)2 dE
= 1.091275 Volt =- 125.5 J/K.
∵ –RT ln K = – n FEo 0.0591 1
10. E I -
/Ag/Ag = 0.8 - 1 log KSP
\ –8.314 × 298 ln K= – 2 × 1.091275 × 96500
11. 0 = ]- 0.151 - 0g - 6 +@
K = 1036.91 = 8.128 × 1036. 0.0591
1 log H
1 0.0591 × log [H+] = - 0.151;
4. H+ + e– —→ 2 H2 , E° = 0, DG° = 0
H+ + OH– , DG° = – 8.314 × 298 ln 10–14 0.151
H2O pH = 0.0591 = 2.56
1
H2O + e– —→ 2 H2 + OH– , –1 × E° × 96500 dE ]0.6753 - 0.6915g
Rxn.1 + Rxn.2 = Rxn.3
12. dT = ]25 - 0g =- 6.48 ×10 -4 V deg -1

\ DGo1 + DGo2 = DGo3 dE

3 H 298 =- nEF + nFT dT
\ 0 - RT ln 10-14 = - 1 F Eo
= -2×0.6753×96500+2×96500×298×(-6.48×10-4)
\ E = 0.059 log
o -14
= 2 × 96500 ( - 0.6753 - 0.1931) = - 167.6 KJ.
E° = – 0.826 Volt.
13. Na+ + e– —→ Na(s)
0.0591 1
5. 0 = (–0.771 + 0.7991) – 1 log x 1mole 1 Faraday
⇒ 0 = 0.0281 +0.0591 log x Al3+ + 3e– —→ Al(s)
0.0281 1 Faraday
log x = – 0.0591 ⇒ x = 0.335 M 1
No. of mole of Al = 3 mole.
0.0591 1
6. E0Ag | AgI | I = E0Ag
- +
| Ag - 1 log Ksp 14. For strong Base + Strong Acid, conductivity first
decreases then increase. i.e. S should be matched to 3.
0.0591 1
– 0.151 = 0.799 – 1 log Ksp \ option (d) is correct.
0.0591 log Ksp = – 0.151 –0.799
PLEASE TAKE A NOTE OF THE OTHER
log Ksp= – 16.074 VARIATIONS.

15. 3 S =- & dT ]3 Gg0 =+ nF b dT l

Ksp = 8.43 × 10–17 d dE
P P
2+
2+
7. A(s) + Baq. —→ A aq. + B(s) , DH° = – 285 KJ
b dE l = 3 S
Assuming DS to negligible, efficiency = DGo/ DHo dT P nF
3.12 Chemistry
0.059 0.01× ]0.01g2 28. H+ + Cl– + NaOH —→ Na+ + Cl– + H2O to
]0.01g2 ×1
16. Ecell = 0.29 - 2 log or conductance Ist decreases since mobility of ions
decreases after end point it inceases as the no. of
Ecell = 0.35 volt
ions increases.
17. E oMnO =
5×1.51 - 2×1.23
= 1.7 volt 0.059 6Sn 2+@
/MnO 2
3 29. Ecell = Eºcell – 2 log 7Ag +A2
-
4

18. Higher the std. reduction potential, higher is the If Ag+ increases, Ecell increases.
oxidising power. 30. AgCl + e– —→ Ag + Cl– E° = 0.2 V
o o
19. m Ag + = 62.3 Scm mol , m 2 –1
Cl - = 67.7 Scm mole 2 –1
Ag —→ Ag + e + –
E° = – 0.79 V
kAgcl = 3.4 × 10–6 Scm–1 ––––––––––––––––––––––––––––––––––––––––
e-
∵ AgCl is sparingly soluble, hence / AgCl = / 3
AgCl AgCl Ag+ + Cl– E° = – 0.59 V
0.059 0.059
1000×3.4×10 -6 E° = n log Ksp ⇒ – 0.59 = 1 log Ksp
/ 3AgCl = (62.3 + 67.5) = s ⇒ Ksp = 10–10
3.4×10 -3
\ s= ]
62.3 + 67.5g
= 2.6 × 10–5 M Now solubility of AgCl in 0.1 M AgNO3
o o o s (s + 0.1) = 10–10 ⇒ s = 10–9 mol/L
20. Ecell = 1.89 = ECe 4+
/Ce 3+ + ECo/Co = E + 0.2772+

Hence 1 mole dissolves in 109 L solution

⇒ E = 1.62 V
nFdEcell dEcell 3 S hence in 106 L amount that dissolves in 1 m mol.
21. 3 S = dt or dt = nF
31. nF b dE l = DSº = –2 × 96500 × 1.45 × 10–3
o

dT
22. Z > Y > X (Non metals like F2 > Cl2 > Br2) \ DSo = –279.85 JK–1
So, Y will oxidise X– but not Z– DGº = –nFEº = –2 × 1.36 × 96500 = –262.48 KJ.
Z will oxidise both X and Y – –
DHº = DGº + TDSº
X can’t oxidise Y or Z . – –
\ DHo = –262.48×103–300×279.85 = -346.435 kJ
0.059 1.5 i×15×60 6.72
23. Ecell = 0.77 - 32. 96500 = 22.4 ×2 ⇒ i = 64.3 amp
1 log 0.015 = 0.652 V
33. E oX
0.059
= E oAg ^ h
24. Ag —→ Ag+ + e- E' /AgX/Ag
1 log10 Ksp AgX
/Ag +
- +

E1 = Eoxid + Ecalomel Thus, salt having least value of Ksp will have least
0.0591 value of E oX /AgX/Ag and all values will be less than
-

E1 = E' - 1 log Ksp + Ecalomel 1

E oAg /Ag (since 2nd term will always have a negative
+

0.0591 values).
E 2 = E' - 1 log Ksp + Ecalomel 2

34. Q = 10 × 4825 = 48250 C

Ksp
E 2 - E1 = 0.177 = 0.0591 log K 48250
1

sp 2 No. of Faraday = 96500 = 0.5F

Ksp 6 Cu + 2Ag+ Cu2+ + 2Ag
Ksp = 10
1

1 init. - 2 2 -
6H +@
25. – 0.413 = 0 – 0 .059 log or
final - 1.5 2.25 -
0.413
0.059 = – log H = pH or pH = 7
+
0.06 2
]2g
Ecell
initial
= Eocell - 2 log 2
26. Eºcell = 0.8 – (– 0.76) = 1.56 V
6Zn 2+@ \ Ecell = Eocell + 0.03 log 2
initial
0.059
27. 1.1591 = 1.1 - 2 log
6Cu 2+@ 0.06 2.25
]1.5g2
Ecell
final
= Eocell - 2 log
6Zn 2+@
6Cu 2+@
or, = 10-2 = 0.01
\ Ecell
final
= Eocell
\ DEcell = Ecell
final
- Ecell
initial
= -0.03 log 2
= - 0.009 V
 Electrochemistry 3.13
35. ClO3– + 2H2O + 4e– —→ ClO– + 4OH– ; DG1° 45. Recharging reaction
1 2PbSO4(s) + 2H2O—→Pb(s) + PbO2(s) + 2H2SO4 (aq)
ClO– + H2O + e– —→ 2 Cl2 + 2OH– ; DG2°
1 46. Ag Cu Au
2 Cl2 + e —→ Cl
– –
; DG3°
–––––––––––––––––––––––––––––––––––––––––––––– equivalent 1 : 1 : 1
ClO3– + 3H2O + 6e– —→ Cl– + 6OH– ; DG°
–––––––––––––––––––––––––––––––––––––––––––––– ratio
\ DG° = DG1° + DG2° + DG3° 1 1 1
Mole ratio 1 : 2 : 3
– 6FE° = – 4F × 0.54 – 1F × 0.45 – 1F × 1.07 6 : 3 : 2
3.68
\ E° = + 6 = + 0.61 V 47. Electrolysis of NaBr Solution
36. Lower S.R.P. containing ion can displace higher at 2Br- —→ Br2 + 2e-
S.R.P. containing ion.
at cathode
37. Anode : Pb(s) + SO42– (aq) —→ PbSO4 + 2e– +2e -
2H2O H2 + 2OH–
Cathode : Pb (aq) + SO (aq) + 4H + 2e
2+ 2–
4
+ –
- -
—→ PbSO4(s) + 2H2O (l) It is clear that Br ion are replaced by OH . Hence
molar conductance & specific conductance increases
Over all reaction : Pb(s) + PbO2 (s) + 2H2SO4 (aq) - -
as OH has higher mobility than Br .
—→ 2PbSO4(s) + 2H2O(l), Ecell = 2.05 V
48. k a c
38. a) EoRP Cu2+ > EoRP Fe2+ so Cu cannot reduce Fe2+
Hence k1 = a × 0.1
b) Water is reduced in preference to Na+ hence H2
is obtained at cathode. k2 = a × 0.01
c) Water may be oxidized or reduced at the k3 = a × 0.005
electrodes in preference to the ions.
k4 = a × 0.0025 where a is a constant
d) If O.P. of metal is lesser, tendency of its cation to
get reduced is more. k
G = cell constant
39. DG0 = – nFE0cell a×0.1 a×0.01
So, G1 = 1 ; G2 = 10
If Ecell = +ve then DG = –ve and reaction is
spontaneous. \ G1 = 0.1a \ G2 = 0.001 a
a×0.005 a×0.0025
40. On dilution specific conductance decreases while G3 = .5 ; G4 = 25
molar conductivity increases. \ G3 = 0.001 a \ G4 = 0.0001 a
41. DG = – nFE; if E > 0 ; DG < 0 ⇒ Spontaneous Hence G1 > G2 = G3 > G4
reaction.
49. Reduction and electronation take place at cathode
Note: If Eºcell > 0, then the reaction will be elctrode, as it is the positive electrode.
spontaneous at standard conditions, not necessarily
at all condition or given condition. 50. Fe2+ + 2e– —→ Fe [in FeSO4] ;

42. Lm and Le increases on dilution while k decreases as Fe3+ + 3e– —→ Fe [in Fe2 (SO4)3]
the number of ions per unit volume decreases. Fe3+ + 3e– —→ Fe [in Fe (NO3)3]
43. (A) Anode 2H2O —→ O2 + 4H + 4e + –
Q 56
Amount of Fe deposited in FeSO4 = 96500 × 2
(B) Anode 2H2O —→ O2 + 4H+ + 4e–
Q 56
(C) Anode Cu —→ Cu2+ + 2e– Amount of Fe deposited in Fe2(SO4)3 = 96500 × 3
(D) Anode 2H2O —→ O2 + 4H+ + 4e– o 0.0591 PCl
51. Ecell = Ecell - 2 log10 P
2(anode)

Cl 2(cathode)

44. ‘A’ depends on nature of electrolyte. Electrolytes 0.0591 P

furnishing the same number and charge of ions will \ Ecell =- 2 log10 P1
2
have same value of A. If P1 < P2, Ecell = + ve (spontaneous)
3.14 Chemistry
52. (A) Cr2O2-
7
For (acidic solution) o 2.303RT ]Zn +2g
61. Ecell = Ecell log
^Cu +2h
- nF
Eº = 1.23 which is greater than E]oFe 2+
/Feg hence it can -4
2×10 ×200 2
oxidize Fe =0.76 + 0.34 - 2 log 0.2 =1.08 volt
(B) H2O2 —→ 2H+ + O2 + 2e– Eº = –0.70 V 62. Cu+2 + 4 NH3 [Cu (CH3)4]+2
O2 + 4H+ + 4e– —→ 2H2O Eº = 1.30 V 0.2 1 0
x 1–0.8 0.2
H2O2 + 2H+ —→ 2H2O
0.2 1
]- 0.70×2g + ]4×1.30g x× ]0.2g4 x× ]0.2g3
Kf = 4.0 × 1011 = =
Eº= 2 = 1.9
10 -11
]0.2g3 ×4
x=
Here Eº is grater than E]oFe /Feg hence H2O2 in acidic
2+

medium can oxides Fe. x = 3.125 × 10–10 [Cu+2] = 3.125 × 10–10

mo 0.0591 2
= Vfm Ecell = 0.75 + 0.34 – 2 log 3.125×10 -10
o
53. m eq
0.0591
Vf for cation/anion - charge; Vf for salt = total = 1.1 – 2 (10 – 0.194) = 1.1 – 0.29 = 0.81 volt
cationic / anionic charge 0.0591 52?
Also, / om (Al 2 ]SO 4g3 = 2m om ]Al3+g + 3m om ^SO 24-h
63. Ecell = 1.1 - 2 log =0
6Cu +2@

]Al3+g + meq 52?

o
(Al 2 ]SO 4g3 = m eq
o o
^SO 24-h log
1.1×2
= 37.23
6Cu +2@ 0.0591
& / eq =
54. At Cathode : Cu2+ + 2e– —→ Cu(s) 2
= 1.68×1037
6Cu +2@
[Cu+2] = 1.19 × 10-37
At Anode : Cu (s) —→ Cu2+ + 2e–
Increase in mass of cathode = decrease in mass of 64. From given latimer diagrams.Cl2 – Cl– is independent
2.68×3600 63.5 of H+ concentration.
Anode = 96500 × 2 = 3.174 g.
55. Create a cell with required cell reaction 0.42 + 1.36
65. DG0 = DG10 + DG20 , using this E0 = 2 V
O2 + 2SO42- —→2S2O2-
8
+ H2O Eocell = 1.23–2.01< 0 = 0.89 V
⇒ Non spontaneous cell reaction. So the reverse 66. Eo for disproportionation of Cl2 in acidic and basic
reaction is spontaneous. media are -0.31V and + 0.94V respectively. Thus, it
56. Greater the charge density on the ion more is the shows disproportionation in basic medium but not in
extent of hydration and more the extent of hydration, acidic medium.
more bulky is the ion and lesser is the mobility of 3 Go
67. As F is low, stability is higher.
the ions. H+ ions is an exception to this and has the
highest mobility. 3 Go 3 Go
68. As F of A+
lies above the line joining F of
57. In galvanic cell anode is the negative terminal which
A and A , so A undergoes disproportionation.
2+ +
is to be connected to the negative terminal of the
electrolytic cell i.e. cathode. 69. m Cm = m3m - b C
The reverse logic applies for the positive electrodes. when C1 = 4 × 10–4; LCm = 107
58. Reduction Potential of Cu is higher than that of and when C2 = 9 × 10–4 LCm = 97
Zn. So, Zn + Cu2+ → Zn2+ + Cu is a spontaneous so 107 = m3m – b × 2 × 10–2 ... (1)
reaction.
97 = m3m – b × 3 × 10–2 ... (2)
59. Lm, Le increases on dilution an k decreases.
b = 1000
Kohlrausch’s law is applicable for both strong as
/ m = / 3m - b C
well as weak electolytes but the equation Lm = Lom
- b c is applicable only for strong electrolytes. / 3m = / m + b C
60. Resistance of cell is not due to vibrations of ion but = 107 + 103 × 2 × 10–2
actually it is due to collisons of ions. m3m = 127 ohm–1 cm2 mole–1
 Electrochemistry 3.15
70. For 25 × 10-4 (M) NaCl solution b) E oZn /Zn < E oAg
2+ +
/Ag , so E o
> 0. At equilibrium
cell
25 × 10-4 (M) NaCl Ecell = 0
o
/ m = m3m - b C c) For concentration cell, Ecell = 0 . Also as
concentration are same at anode and cathode so
/ m = 127 - 103 ^25×10 -4h1/2 Ecell = 0 as Q = 1
/ m = 127 - 103 ×5×10 -2 d) As Fe is more reactive than Ag, so Eocell > 0.
/ m = 77 1000k
74. a) Lm = M , so ‘p’
k = b a, l × R
k×1000 1
But / m = M and b) k decreases with dilution as number of ions per
cm3 of solution decreases, so ‘s’
/ m = b a, l × R × M
1 1000
/
c) a 3m , so ‘r’
/m
/ m = 5Cell constant?× R×M
1000 d) For sparingly soluble salt, Lm = Lom and M = S
1000k
1000 ⇒S= . Hence ‘q’
⇒ 77 = [Cell constant] × / om
1000×25×10 -4
0.059 ^PH hc 6H +@a2
Cell constant = 77 × 25 × 10-4 = 0.1925 cm-1 75. (a) Ecell =- log
^PH ha 6H +@c2
2

2 2

71. For Na2SO4 solution

0.059 0.01× ]0.1g2 0.059
]0.1g × ]1 g2
E0cell =- log = 2 ×3 =+ ve
k = b a l × R = 400 = 4.81×10 -4 ohm -1 cm -1
, 1 0.1925 2

k×1000 4.81×10 -4 ×1000 (b) Cell reaction Ag +c ^10 -2h " Ag +a ^10 -9h
/m = M = 5 -3
2 ×10 Ecell =-
0.059 10 -9 0.059
1 log 10 -2 =+ 1 ×7 > 0
/ m ]Na 2 SO 4g = 192.4 ohm -1 cm 2 mole -1
E0cell = 0 and not conc. cell is in working condition.
72. At the equivalence point the concentrations will be
[Br–] = 100 mol/m3, [Na+] = 100 mol/m3 It is a concentration cell.

Therefore ktotal = k Br + k Na = 1.2 Sm–1 0.059 6Cu +2@a

(c) Ecell = 0 - log
6Cu +2@c
- +

2
\ Ans = 12 × 10–1 Sm–1. 0.059 0.1
73. a) As Mg is more reactive than Zn, so
=- 2 log 0.01 =- ve
E oZn > E oMg o
$ Ecell <0 0.059 6Cl -@c 0.059 0.1
2+
/2n 2+
/Mg (d) Ecell =- 2 log 6Cl -@a = 2 log 0.1 = 0
and E0cell = 0

1. Zn(s) → Zn2+(aq.) + 2e- 2. Eqn is MnO -4 + H 5 + 5e - " Mn +2 + 4H 2 O

2Ag +
+ 2e- → 2Ag(s)
___________________________________ Nernst equation :
5Mn +2? 1 8
(aq.)

Zn + 2Ag+(aq.) → Zn2+(aq.) + 2Ag(s) 0.059

: D
6MnO -4 @ H +
0
___________________________________
(s) E cell = E Cell - log
5
(I) given 5H ? = 1 M
0 0
E 0cell = E Ag /Ag - E Zn /Zn
+ 2+
5
= 0.80 - (-0.76)
0.059 5Mn +2?
6MnO -4 @
= 1.56 V E1 = E 0 - 5 log
5Zn 2+?
(II) Now 5H ? = 10-4 M
- 0.059
6Ag +@2
E cell = 1.56 log
5
2
0.059 5Mn +2? 1
6MnO -4 @ ]10 -4g8
0.059 0.1 E2 = E0 - log ×
2 log ]0.01g2
= 1.56 - 5
0.059 0.059 Mn +2 0.059
6MnO -4 @
= E0 - log -32
5 log 10
= 1.56 - +
2 ×3 5
= 1.56 - 0.0885 0.059
therefore : E1 - E 2 = 5 × 32
= 1.4715
= 147.15 × 10-2 = 0.3776 V = 3776 × 10-4 x = 3776
3.16 Chemistry
108 Hence
3. (n Ag) deposit = = 1 mole 12 # 96500 = i # t
108
Ag + + e - $ Ag = 100 amp # t
1F charge is required to deposit 1 mole of Ag t = 12 # 965 second
1
H 2 O $ O 2 + 2H + + 2e - 12 # 965 11580
2 t= 3600 = 3600 = 3.2 hours.
1
2F charge deposit $ mole of O2 9. E oMnO = 1.51 V ... (i)
2 /Mn +2
-
4

o
1 E Cl 2 /Cl - = 1.36 V ... (ii)
1F charge will deposit $ mole of O2
4 E o
Cr2 O 7-2 /Cr +3 = 1.33 V ...(iii)
nRT
VO = o
ECr =- 0.74 ...(iv)
2
P +3
/Cr

1 0.08314 # 273 Since Cr+3 is having least reducing potential, so Cr

= #
4 1 has greatest tendency to get oxidized and is the best
VO = 5.674 L
2 Reducing agent.
E10 10. Galvanization is applying a coating of Zn.
4. Cu
2+
Cu+ 0.522 Cu
11. Cu2+ + 2e– —→ Cu
0.34
2F 1 mole
2 # 0.34 = E1o + 1 # 0.522
= 63.5 g.
E1o = 0.68 - 0.522 & E1o = 0.158 V
12. Mn + 2e —→ Mn
2+ -
Eo1 = - 1.18 DGo1 = 2FEo1
5. PbSO 4] s g + 2OH " PbO2 + H2 SO 4 + 2e
- -

0.05
Mn2+ —→ Mn3+ + e- Eo2 = - 1.51 DGo2 = -FEo3
2 mole 0.05F _____________________
PbSO4 + 2e– + 2H+ → Pb(s) + H2SO4 3Mn2+ —→ Mn + 2 Mn3+ DGo3 + 2 DGo2 = -FEo3
2E1o + 2E o2
Total number of moles of PbSO4 = 0.05/2 \ Eo3 = 2 = Eo1 + Eo2 ⇒ Eo3 = - 2.69 V
0.05
Mass of PbSO4 = 2 × 303 = 7.6 g a Eo < 0 ⇒ Non-spontaneous.
6. DG° = – nFE°cell 13. Reason : Higher the position of element in the
= – 2 × 96,000 × 2 electrochemical series, more difficult is the reduction
= – 384,000 CV mol–1 of its cations.
Now, DG° = – RT ln K If Ca2+ (aq) is electrolysed, water is reduced
or, –384,000 = – 8 × 300 ln K in preference to it. Hence it cannot be reduced
384000 electrolytically from an aqueous solutions.
lnK = - - 2400 =160
\ K = e160 14. m c = m3 - B C (Debye Huckel equation)
7. Lesser the value of reduction potential, higher is 15. Higher the SRP, better is oxidising agent
the tendency to loose electrons. Thus, reducing Hence MnO4- is strongest oxidising agent
nature increases as the value of reduction potential
16. X + Y2+ —→ X2+ + Y
becomes more and more negative.
For reaction to be spontaneous Eº must be positive.
The reducing power of the metals increases in the
order : If X = Zn and Y = Ni, the Eo = + 0.53 V
Ni < Zn < Mg < Ca 2 4
17. 3 Al 2 O3 $ 3 Al + O 2
8. B 2 H6 + 3O 2 B 2 O3 + 3H 2 O DrG = +966 kJ mol–1 = 966 × 103 J mol–1
27.66 DG = – nFEcell
27.66
1mol 3mol 966 × 103 = – 4 × 96500 × Ecell
4e - + O 2 2O 2- Ecell = 2.5 V
therefore charge required = 12 faraday
 Electrochemistry 3.17

2.303 RT 7. & 8.
1. E = 1.1 - 2F log10
Molar conductivity of HX at infinite dilution
Now, DG = - nFE
/ 3m = 4 × 102 S cm2 mol–1
\ DG = 2.303 RT - 2.2 F Molar conductivity of HX at conc. c1 = y × 102 S cm2
2. Salt bridge is introduced to keep the solutions of two mol–1
electrodes separate, such that the ions in electrode / Cm1
y×10 2 y
a1 = / 3 = =
4
do not mix freely with each other. But it cannot stop m 4×10 2
the process of diffusion. On 20 times dilution of the solution of HX

:c 2 = c1 D
It does not participate in the chemical reaction. / Cm
2
3y×10 2 3y
However, it is not necessary for occurence of =
a1 / 3 = =
m 4×10 2 4 20
cell reaction, as we know that designs like lead a1 1
accumulator, there was no salt bridge, but still a2 = 3 ⇒ a2 = 3a1
reactions takes place. HX +
H + X!
0.059 6Fe 2+@2 c1(1!"1) c1"1 c1"1
3. E = E o - log
4 6H +@4 PO c1 (3a1) 2
2
c1 a12 c a2
^10 h -3 2 Ka = = 2 2 =
0.06 1 - a1 1 - a 2 20 (1 - 3a1)
= 1.67 - 4 log
^10 -3h4 ×0.1 1 9
20 ^1 - 3a1h
=
0.03 1 - a1
= 1.67 - 2 log 107
11
0.03 20 – 60a1 = 9 – 9a1 ⇒ a1 = 51 = 0.215
= 1.67 - 2 ×7 = 1.67 - 0.105
y = 4a1 = 0.86
= 1.565 = 1.57 V.
9. E0cell = 1.23 – 0.00 = 1.23 V
4.
DG0cell = –nF E0cell = –2 × 96500 × 1.23 J
\ Work derived from this fuel cell
70
= 100 × (-DG0cell) × 10-3 = xJ
Since insulated vessel, hence q = 0
From equation, for monoatomic gas,
w = DU ⇒ x = nC V,m 3 T &C V,m = 2 0
3R
5. X + Y2+ → X2+ + Y
70
E = E o - 2 log10 b -1 l
0.06 10 -3 or 100 × (2 × 96500 × 1.23) × 10-3
10 3
= 1 × 2 × 8.314 × DT
E = E° + 0.06
\ DT = 13.32
(a) E° = –(– 0.4) + (– 0.24) = 0.16 > 0
(b) E° = –(– 0.4) + (– 0.44) = –0.04 < 0 and Ecell 10. A(s) | An+ (aq, 2M) || B2n+ (aq, 1M) | B(s)
= –0.04 + 0.06 = +0.02 > 0 Reactions
(c) E° = –(– 0.24) + (– 0.13) = 0.11 > 0 Anode (A —→ An+ + ne) × 2
(d) E° = –(– 0.24) + (– 0.44) = –0.2 < 0 Cathode B2n+ + 2ne —→ B
___________________________
\ Ecell = –0.2 + 0.06 = –0.14 < 0 Overall reaction:
\ If Ecell > 0 then the cell construction is possible. 2A(s) + B2n+ —→ 2An+ + B
RT
6. The species having less reduction potential with E = E o - 2nF ,nQ

RT 6A n+@
respect to NO3– (Eº = 0.96 V) will be oxidised by 2
NO3–. O = E o - 2nF ,n 2n+
B
These species are V, Fe, Hg. RT
E o = 2nF ,n4
3.18 Chemistry
- 2nFRT 12. m oX . m oY
Now DGo = -2nFEo =
- -

2nF ln4
= -RTln4.
o
⇒ m + m oX . m oH + m oY
H+ - + -

o o
DGo = DHo - TDSo = -TDSo ⇒/ ./
HX HY ...(1)
/
TDSo = DGo Also mo = a, So Lm (HX) = / om a1 and
/m
3 G o - RT,n4 m m (HY) = m om a 2 (Where a1 and a2 are degrees of
DSo = T = T = - Rln4
= - 8.3 × 2 × 0.7 = - 11.62 JK-1mol-1 dissociation of HX and HY respectively.)
, Now, Given that
11. l = 120 cm A = 1cm2 & A = 120 cm-1
Lm(HY) = 10 Lm(HX).
, ⇒ / om a 2 = 10× / om a1
k = C A = 5 × 10-7 × 120 S cm-1
= 6 × 10-5 S cm-1 a 2 = 10 a1 ...(2)
2
1000k 6×10 -2 Ca
\ /m = M = = 40 Scm2 mol-1. K a = 1 - a , But a < < 1, therefore Ka = Ca2.
1.5×10 -3
K a (HX) 0.01a12 0.01
2 = 0.1 × b 10 l = 1000
No, for the acid [H+] = 10-4 M = c a 1 2 1
⇒ K (HY) =
a 0.1a 2
10 -4 1
\ a= = ⇒ log (Ka (HX) - log (Ka(HY)) = - 3.
1.5×10 -3 15
/ /
∵ a = om & / om = am 40 × 15 ⇒ pKa (HX) - pKa (HY) = 3.
/m
\ Lom = 600 S cm2 mol-1. 13. M+ —→ M3+ + 2e–
\ Lom = 6 × 102\ Ans = 6 DG0 = –nFE0 For 1 mole of m+
DG0 = –2 × 96500 × (–0.25) J
= + 48250 J/mole = 48.25 KJ/mole
Energy released by conversion of 1 mole of
X —→ Y DG = –193 KJ
193
Hence moles of M+ converted = 48.25 = 4