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 G = nFEcell. - 0.059 6H +@ 2

51 ?2
1 3. Ecell = 2 log
Hence G 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. = R × cell const 7. Molar conductivity = tM

b l l = × R = 0.0212 × 55 = 1.166 cm 1. So its unit will be 1

cm2 mol 1
A
1 1
1 1 8. Conductance = resistance = ohm = ohm -1
2. = R × cell const = 100 × 1 = 10 2 ohm 1 cm 1.
1
1000 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 m

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
= × N = t × N = 100 × 1
1000 1
6. Molar conductivity = MX as = X = 10 ohm 1 cm2 eq 1
 Electrochemistry 3.3
INTEXT EXERCISE: 6
1. Practically 60 The net reaction is the same as burning (Combustion)
fuel cells. of hydrogen to form water.
2. Overall reaction of fuel cell is: 7. Since tendency to get oxidized is higher for zinc so
2H2(g) + O2(g) 2H2O(l). Zn acts as the anode and Fe as the cathode.

3. During charging of lead storage battery H2SO4 is 8. Corrosion is essentially a redox reaction. Thus, it is
produced. an electrochemical process.

4. Reaction in a dry cell: 9. HgCl2 has corrosive action. It is highly poisonous.

It sublimes on heating. It is, therefore, known as
2NH4Cl + Zn 2NH3 + ZnCl2 + H2 corrosive sublimate. Facts, good to remember.
5. MnO2 is used in dry batteries cell, to seperate the 10. Fe Fe2+ + 2e (anode reaction)
anode from the cathode depolarizer.
O2 + 2H2O + 4e 4OH (cathode reaction)
6. In hydrogen–oxygen fuel cell following reactions
The overall reaction is 2Fe + O2 + 2H2O 2Fe(OH)2
take place to create potential difference between two
electrodes. Fe(OH)2 is dehydrated to iron oxide FeO, or further
oxidised to Fe(OH)3 and then dehydrated to iron
2H2(g) + 4OH (aq)
4H2O(l) + 4e rust, Fe2O3.
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 12. EMF for (a) is positive.(c) and (d) involve only
in solid state. oxidation or reduction and are impossible.
2. An electrolyte dissociates into ions when dissolved 13. H2 undergoes oxidation and AgCl(Ag+) undergoes
in suitable solvent. reduction.
3. Standard electrode potential for a half reaction is 14. Cu Cu2+ + 2e (Oxidation)
Hg2+ + 2e Hg (Reduction)
4. Higher the oxidation potential (or lower the
Cu + Hg — 2+
Cu2+ + Hg
reduction potential) stronger the reducing agent.
15. Cu + 2 Ag+ — Cu2+ + 2 Ag.
5. A large negative reduction potential means a high
oxidation potential so that A is easily oxidized 16. See electrochemical series.
6. Lower the reduction potential, stronger is the 17. Reduction half reaction is Ag+ + e Ag
reducing agent.
18. MnO 4 will oxidize Cl ion according to the equation
7. Greater the reduction potential, stronger is the
2MnO 4 + 16H+ + 10Cl 2Mn2+ + 8H2O + 5Cl2
oxidizing agent or weaker is the reducing agent
The cell corresponding to this reaction is as follows:
8. Greater the reduction potential, less is the reducing
power. Pt, Cl2 (1 atm) |Cl || MnO 4 , Mn2+, H+ |pt
9. Greater the reduction potential stronger is the Eocell = 1.51 1.40 = 0.11 V
oxidizing agent. Hence Y is stronger oxidizing agent As E cell is +ve, the above reaction is feasible. Thus
o

than X but weaker than Z. MnO 4 will not only oxidize Fe2+ ion but also Cl ion
10. Greater the reduction potential, stronger is the simultaneously. Hence, statement (a) is incorrect.
oxidizing agent or weaker is the reducing agent 19. Oxidation takes place at anode viz (a).
11. Cell potential 20. Eocell = Eoox (Fe) + EoRed (Zn) = 0.41 + 0.76 = 0.35 V
= EoRed (RHS) EoRed (LHS) 21. Eocell = Eoox (B) + EoRed (A) = 0.42 + 0.35 = 0.77 V
= 0.34 ( 0.76) = + 1.10 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 - G = nFEocell
overall reaction: AgCl (s) " Ag + + Cl - = 2 × 96500 × ( 0.80) J = 154.4 kJ.
25. For the cell reaction Cu+ 2 Ag+ 2+
+ 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 2+
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.
E = Eo - nF ln P =2 0 - 2F ln P2 = 2F ln P1
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
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. = C × cell const. = R = 250
F = 2.6 × 10 3 F.
×1000 1.15 1000
52. 1 g eq. of H2 i. e. 1 g or 11200 cc is obtained from eq
= Normality = 250 × 1 = 4.6X -1 cm 2 eq -1
96500 C
l 0.4
112 ml will be obtained from 965 C., 63. = R × cell const. = 40 = 10 2.
Q 965 1000k
i = t = 965 = 1 A. = M = 103
53. 4 mole electrons 4 Faradyas = 4 equivalents 1 1
64. = 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 ×1000 / m ×Molarity
65. / m = Molarity or = 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. = R × a i.e., R \
5×40×60
wt. of Zn = 96500 × 32.5 g 67. Solubility,
= 4.04 g 1000 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. (C2H5COOH) = (C2H5COONa)
wt. of Cl2 = 1.324 g + (HCl) (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 × eqo 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. o
(CX) = oc + ox
57. Eq. conductance increases with dilution and = o
(BX) + o
(CA) o
(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. or even negative transport number due to formation
electrons. of complex ion, CdI24 )
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 = × Length or
74. Fuel cell converts chemical energy of H2 and O2 into
Conductance × Length S×m electrical energy.
= 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 — Fe + 2e– , 0.44 volt
2+

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, G < 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 = 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+
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 : Cu + e —
2+
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 = 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 = C × A
l 54. / m,BaSO = ]x1 + x 2 - 2x3g
4

1 0.02 / m BaSO
= 50 × 0.0004 = 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. 1
= 50 a 2
= 100 a mix
= 80 a
Now, 1v1 + 2v2 = mix vmix 20 × MKOH × 1 = 15 × 0.2 × 2
v1 v2 v1 + v 2 MKOH = 0.3
50 + 100 = 80
v2 56. NH4OH + H+ + Cl — NH+4 + Cl + H2O
or, 6v1 = 2v2 v1 = 3
Highly mobile H+ are replaced by less mobile NH+4,
49. Molar conductivity 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 eq
= 19.6 Scm2 eq–1 , C = 0.01 equivalence point doesn’t increase the conductivity
25×10 -6 much.
Ka = 0.01 × 2
a= = 5 × 10–2
10 -2 57. H2 – O2 fuel cell
19.6
= 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. = 1.382 × 10 S cm –6 –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 the medium acidic consumes the oxide formed and
53. 1.53 = Normality
promotes further rusting of iron.
Normality = 2 × 10 3
2×10 -3
Molarity = 2 = 10 -3 M = solubility (s)
Ksp = s2 = 10 6 M
EXERCISE 3
1. Hg22++ 2e– — 2Hg, 0.789 Volt 3. E o298 = 1.1028 – 0.641 × 10–3 × 25 + 0.72×10–5×(25)2
Hg — Hg2+ + 2e , 0.854 Volt = 1.091275 Volt
Hg22+ Hg + Hg2+ , –0.065 Volt ∵ –RT ln K = – n FEo
Go = – 2 × (–0.065) × 96500= –8.314 × 298 ln Keq; –8.314 × 298 ln K= – 2 × 1.091275 × 96500

Keq.= 6.3 × 10–3 K = 1036.91 = 8.128 × 1036.

1
2. E° = 1.1028 – 0.641 × 10–3 T + 0.72 × 10–5 T2 4. H+ + e– — 2 H2 , E° = 0, G° = 0
b dE l = –0.641 × 10–3 + 2 × 0.72 × 10–5 T
o H 2O H + OH– , G° = – 8.314 × 298 ln 10–14
+

dT 1
H2O + e– — 2 H2 + OH , –1 × E° × 96500
–
Putting T = 25
Rxn.1 + Rxn.2 = Rxn.3
b dE l = (–0.641 + 0.36) × 10–3 = –0.281 × 10–3
o

dT Go1 + Go2 = Go3

dE o
S° = nF dT = 2 × 96500 × (–0.281 × 10–3) 0 RT ln 10 14
= 1 F Eo
= – 54.23 Eo = 0.059 log 14

E° = – 0.826 Volt.
 Electrochemistry 3.9
0.0591 1 13. Na+ + e– — Na(s)
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
0.0591 1 No. of mole of Al = 3 mole.
6. E0Ag | AgI | I = E0Ag
- +
| Ag -
1 log Ksp
14.
0.0591 1 decreases then increase. i.e. S should be matched to 3.
– 0.151 = 0.799 – 1 log Ksp
0.0591 log Ksp = – 0.151 –0.799 option (d) is correct.

log Ksp= – 16.074 PLEASE TAKE A NOTE OF THE OTHER

VARIATIONS.
Ksp = 8.43 × 10–17
15. 3 S =- & dT ]3 Gg0 =+ nF b dT l
d dE
2+
2+
7. A(s) + Baq. — A aq. + B(s) , H° = – 285 KJ P P

Assuming G o/ H o b dE l = 3 S
dT P nF
Go = 285 × 103 × 0.84 = 2 F Eo
285×0.84×103 0.059 0.01× ]0.01g2
]0.01g2 ×1
Eo = 16. Ecell = 0.29 - 2 log or
2×96500
E° = 1.24 Volt Ecell = 0.35 volt
2+
8. MnO + 8H + 5e $ Mn + 4H 2 O
-
4
+ -
5×1.51 - 2×1.23
17. E oMnO = = 1.7 volt
6Mn @ 3
-
4 /MnO 2
2+
0.0591
E1 = E o - 5 log 6MnO -4 @ ×18
18. Higher the std. reduction potential, higher is the
0.0591 6Mn 2+@ oxidising power.
E 2 = E o - 5 log
6MnO -4 @ × ^10 -4h8
19. m oAg = 62.3 Scm2 mol–1, m Cl
+
o
= 67.7 Scm2 mole–1 -

0.0591
E2 E1 =- 5 × 32 = 0.37821 . 0.38 V = 3.4 × 10–6 Scm–1
Agcl
Potential decreases and so does the oxidizing ∵ AgCl is sparingly soluble, hence / AgCl = / 3AgCl
power of MnO 4.
dE 1000×3.4×10 -6
9. dt =- 0.00065 Vol deg -1 / 3AgCl = (62.3 + 67.5) = s
3.4×10 -3
3 S 298 = n.F. dT = 2×96500× ]- 0.00065g
dE s= ]
62.3 + 67.5g
= 2.6 × 10–5 M

=- 125.5 J/K. o
20. Ecell o
= 1.89 = ECe 4+
/Ce 3+
o
+ ECo/Co = E + 0.277
2+

0.0591 1
10. E I -
/Ag/Ag = 0.8 - 1 log KSP E = 1.62 V
nFdEcell dEcell 3 S
11. 0 = ]- 0.151 - 0g - 6 +@
0.0591 21. 3 S = or
1 log H dt dt = nF
0.0591 × log [H+] = 0.151;
22. Z > Y > X (Non metals like F2 > Cl2 > Br2)
0.151
pH = 0.0591 = 2.56 So, Y will oxidise X– but not Z–
dE ]0.6753 - 0.6915g Z will oxidise both X– and Y–
12. dT = ]25 - 0g =- 6.48 ×10 -4 V deg -1
X can’t oxidise Y– or Z–.
dE 0.059 1.5
3 H 298 =- nEF + nFT dT 23. Ecell = 0.77 - 1 log 0.015 = 0.652 V
= 2×0.6753×96500+2×96500×298×( 6.48×10 4)
= 2 × 96500 ( 0.6753 0.1931) = 167.6 KJ.
3.10 Chemistry
24. Ag — Ag+ + e E' 33. E oX
0.059
= E oAg ^ h
/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
-

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

1
+

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

Ksp 34. Q = 10 × 4825 = 48250 C

E 2 - E1 = 0.177 = 0.0591 log K
1

sp 48250
No. of Faraday = 96500 = 0.5F
2

Ksp 6
Ksp = 10
1

2
Cu + 2Ag+ Cu2+ + 2Ag
1 init. 2 2
6H +@
25. – 0.413 = 0 – 0 .059 log or
0.413 1.5 2.25
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
0.059 6Zn 2+@ Ecell
initial
= Eocell + 0.03 log 2
27. 1.1591 = 1.1 - 2 log 6Cu 2+@ 0.06 2.25
6Zn 2+@ Ecell = Eocell - 2 log
]1.5g2
6Cu 2+@
or, = 10 2 = 0.01
Ecell = Eocell
28. H+ + Cl– + NaOH — Na+ + Cl– + H2O to
conductance Ist decreases since mobility of ions Ecell = Ecell Ecell
initial
= 0.03 log 2
decreases after end point it inceases as the no. of = 0.009 V
ions increases.
35. ClO3– + 2H2O + 4e– — ClO– + 4OH– ; G1°
0.059 6Sn 2+@
29. Ecell = Eºcell – 2 log 1
7Ag +A
2
ClO– + H2O + e– — 2 Cl2 + 2OH
–
; G2°
If Ag increases, Ecell increases.
+
1
2 Cl2 + e — Cl ; G3°
– –

30. AgCl + e — –
Ag + Cl –
E° = 0.2 V ––––––––––––––––––––––––––––––––––––––––––––––
Ag — Ag+ + e– E° = – 0.79 V ClO3– + 3H2O + 6e– — Cl– + 6OH– ; G°
––––––––––––––––––––––––––––––––––––––––––––––
––––––––––––––––––––––––––––––––––––––––
G° = G1° + G2° + G3°
e-
AgCl Ag+ + Cl– E° = – 0.59 V – 6FE° = – 4F × 0.54 – 1F × 0.45 – 1F × 1.07
0.059 0.059 3.68
E° = n log Ksp – 0.59 = 1 log Ksp E° = + 6 = + 0.61 V
Ksp = 10–10
36. Lower S.R.P. containing ion can displace higher
Now solubility of AgCl in 0.1 M AgNO3 S.R.P. containing ion.
s (s + 0.1) = 10–10 s = 10–9 mol/L 37. Anode : Pb(s) + SO42– (aq) — PbSO4 + 2e–
Hence 1 mole dissolves in 109 L solution Cathode : Pb2+(aq) + SO42– (aq) + 4H+ + 2e–
hence in 106 L amount that dissolves in 1 m mol. — PbSO4(s) + 2H2O ( )
Over all reaction : Pb(s) + PbO2 (s) + 2H2SO4 (aq)
31. nF b dE l = Sº = –2 × 96500 × 1.45 × 10–3
o

dT — 2PbSO4(s) + 2H2O( ), Ecell = 2.05 V

S = –279.85 JK
o –1
38. a) EoRP Cu2+ > EoRP Fe2+ so Cu cannot reduce Fe2+
Gº = –nFEº = –2 × 1.36 × 96500 = –262.48 KJ. b) Water is reduced in preference to Na+ hence H2
is obtained at cathode.
Hº = Gº + T Sº
c) Water may be oxidized or reduced at the
Ho = –262.48×103–300×279.85 = 346.435 kJ electrodes in preference to the ions.
i×15×60 6.72 d) If O.P. of metal is lesser, tendency of its cation to
32. 96500 = 22.4 ×2 i = 64.3 amp
get reduced is more.
 Electrochemistry 3.11
39. G0 = – nFE0cell G1 = 0.1 G2 = 0.001
If Ecell = +ve then G = –ve and reaction is a×0.005 a×0.0025
G3 = .5 ; G 4 = 25
spontaneous.
G3 = 0.001 G4 = 0.0001
40.
molar conductivity increases. Hence G1 > G2 = G3 > G4

41. G = – nFE; if E > 0 ; G < 0 Spontaneous 49. Reduction and electronation take place at cathode
reaction. elctrode, as it is the positive electrode.

Note: If Eºcell > 0, then the reaction will be 50. Fe2+ + 2e– — Fe [in FeSO4] ;
spontaneous at standard conditions, not necessarily Fe + 3e —
3+ –
Fe [in Fe2 (SO4)3]
at all condition or given condition.
Fe3+ + 3e– — Fe [in Fe (NO3)3]
42. and e increases on dilution while decreases as Q
m 56
the number of ions per unit volume decreases. Amount of Fe deposited in FeSO4 = 96500 × 2
43. (A) Anode 2H2O — O2 + 4H+ + 4e– Q 56
Amount of Fe deposited in Fe2(SO4)3 = 96500 × 3
(B) Anode 2H2O — O2 + 4H+ + 4e– o 0.0591 PCl
51. Ecell = Ecell - 2 log10 P
2(anode)

(C) Anode Cu — Cu2+ + 2e– Cl 2(cathode)

0.0591 P
(D) Anode 2H2O — O2 + 4H+ + 4e– Ecell =- 2 log10 P1
2

44. ‘A’ depends on nature of electrolyte. Electrolytes If P1 < P2, Ecell = + ve (spontaneous)
furnishing the same number and charge of ions will
52. (A) Cr2O27 For (acidic solution)
have same value of A.
Eº = 1.23 which is greater than E]oFe 2+
/Feg hence it can
45. Recharging reaction
oxidize Fe
2PbSO4(s) + 2H2O— Pb(s) + PbO2(s) + 2H2SO4 (aq)
(B) H2O2 — 2H+ + O2 + 2e– Eº = –0.70 V
46. Ag Cu Au
O2 + 4H+ + 4e– — 2H2O Eº = 1.30 V
equivalent 1 : 1 : 1
H2O2 + 2H — +
2H2O
ratio
]- 0.70×2g + ]4×1.30g
1 1 1 Eº= 2 = 1.9
Mole ratio 1 : 2 : 3 o
6 : 3 : 2 Here Eº is grater than E]Fe /Feg hence H2O2 in acidic
2+

medium can oxides Fe.

47. Electrolysis of NaBr Solution
mo
o
53. m eq = Vfm
at 2Br — Br2 + 2e
Vf for cation/anion charge; Vf for salt = total
at cathode
cationic / anionic charge
Also, / om (Al 2 ]SO 4g3 = 2m om ]Al3+g + 3m om ^SO 24-h
+2e -
2H2O H2 + 2OH–

(Al 2 ]SO 4g3 = m eq ]Al3+g + meq ^SO 24-h

It is clear that Br ion are replaced by OH . Hence o o o
& / eq
as OH has higher mobility than Br . 54. At Cathode : Cu2+ + 2e– — Cu(s)
48. c At Anode : Cu (s) — Cu2+ + 2e–
Increase in mass of cathode = decrease in mass of
Hence 1
= × 0.1 2.68×3600 63.5
Anode = 96500 × 2 = 3.174 g.
2
= × 0.01
55. Create a cell with required cell reaction
3
= × 0.005
O2 + 2SO42 — 2S2O28 + H2O Eocell = 1.23–2.01< 0
= × 0.0025 where is a constant
4 Non spontaneous cell reaction. So the reverse
G = cell constant reaction is spontaneous.

a×0.1 a×0.01
So, G1 = 1 ; G2 = 10
3.12 Chemistry
56. Greater the charge density on the ion more is the 3 Go
67. As F is low, stability is higher.
extent of hydration and more the extent of hydration,
more bulky is the ion and lesser is the mobility of 3 Go 3 Go
the ions. H+ ions is an exception to this and has the 68. As F of A lies above the line joining F of
+

highest mobility. A and A2+, so A+ undergoes disproportionation.

57. In galvanic cell anode is the negative terminal which 69. m Cm = m3m - b C
is to be connected to the negative terminal of the when C1 = 4 × 10–4; C
= 107
m
electrolytic cell i.e. cathode.
and when C2 = 9 × 10–4 C
m
= 97
The reverse logic applies for the positive electrodes. 3
so 107 = m – b × 2 × 10
m
–2
... (1)
58. Reduction Potential of Cu is higher than that of 3
97 = m – b × 3 × 10
m
–2
... (2)
Zn. So, Zn + Cu2+ Zn2+ + Cu is a spontaneous
reaction. b = 1000
59. , increases on dilution an decreases. / m = / 3m - b C
m e

Kohlrausch’s law is applicable for both strong as / 3m = / m + b C

well as weak electolytes but the equation m = m = 107 + 103 × 2 × 10–2
- b c is applicable only for strong electrolytes. m3m = 127 ohm–1 cm2 mole–1
60. Resistance of cell is not due to vibrations of ion but 70. For 25 × 10 4 (M) NaCl solution
actually it is due to collisons of ions.
]Zn +2g
25 × 10 4 (M) NaCl
o 2.303RT
61. Ecell = Ecell - nF log ^Cu +2h / m = m3m - b C
=0.76 + 0.34 -
2×10 -4 ×200 2
log 0.2 =1.08 volt / m = 127 - 103 ^25×10 -4h1/2
2
62. Cu+2 + 4 NH3 [Cu (CH3)4]+2 / m = 127 - 103 ×5×10 -2
0.2 1 0 / m = 77
x 1–0.8 0.2
= b a, l × R
×1000 1
But / m = M and
0.2 1
x× ]0.2g4 x× ]0.2g3
Kf = 4.0 × 1011
= =
/ m = b a l× R × M
, 1 1000
10 -11
]0.2g3 ×4
x=
/ m = 5Cell constant?× R×M
1000
x = 3.125 × 10–10 [Cu+2] = 3.125 × 10–10
0.0591 2 1000
77 = [Cell constant] ×
Ecell = 0.75 + 0.34 – 2 log 3.125×10 -10 1000×25×10 -4
0.0591 Cell constant = 77 × 25 × 10 4 = 0.1925 cm 1
= 1.1 – 2 (10 – 0.194) = 1.1 – 0.29 = 0.81 volt
0.0591 52? 71. For Na2SO4 solution
63. Ecell = 1.1 - 2 log =0
6Cu +2@
= b a, l × R = 400 = 4.81×10 -4 ohm -1 cm -1
1 0.1925
52? 1.1×2
log = 37.23
6Cu +2@ 0.0591
=
×1000 4.81×10 -4 ×1000
2 /m = M = 5
= 1.68×1037 2 ×10
-3
6Cu +2@
[Cu+2] = 1.19 × 10 37

64. From given latimer diagrams.Cl2 – Cl– is independent / m ]Na 2 SO 4g = 192.4 ohm -1 cm 2 mole -1
of H+ concentration. 72. At the equivalence point the concentrations will be
0.42 + 1.36 [Br–] = 100 mol/m3, [Na+] = 100 mol/m3
65. G0 = G10 + G20 , using this E0 = 2 V
Therefore = Br - + Na + = 1.2 Sm–1
= 0.89 V total

Ans = 12 × 10–1 Sm–1.

66. Eo for disproportionation of Cl2 in acidic and basic
media are 0.31V and + 0.94V respectively. Thus, it
shows disproportionation in basic medium but not in
acidic medium.
 Electrochemistry 3.13
73. If cell is taken to be conc cell, Eocell = 0 77. (M — Mn+(0.02M) + ne ) × 2
Anode: Ag — Ag+a + e (2H+ 2e — H2) × n
Cathode: Ag + e —+
c
Ag 2M + 2nH — +
2Mn+ + nH2
0.0591 ]0.02g2
]1 g2n
Ag+c Ag+a 0.81 = (0.76 + 0) - 2n log
From Nernst eq,
7Ag +Aa & ]0.81 - 0.76g = 0.0591
2n log 4×10
-4
0.059
- 1 log
7Ag +Ac
Ecell = E o

n =- 2×0.5 ×log 4×10 -4 =- 0.591 ]- 4 + 0.6g = 2

cell
0.0591
0.59 7Ag +Aa
& 0 = 0 - 1 log
7Ag +Ac 78. sol = Ba 2+ + Ag + + NO 3-

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

o +
Ksp of AgBr Ksp of AgCl 5.3 =
2+

+ +
+ -
3

6Br -@ 6Cl -@
[Ag ]a = [Ag ]c &
+ +
= 10 -3
10 -3
10 -3
o
5×10 -13 6Br -@ 6Br -@ 1 13×10 -3 ×0.1 6×10 -3 ×0.2 m^NO h ×0.4 -

5.3 =
3

= 200 & Ans = 5 + +

6Cl -@ 6Cl -@ 10 -3 10 -3 10 -3
or, = &
10 -10
m^oNO h = 7×10 -3 Sm 2 mol -1 . So, Ans = 7.
-
3
74. H3O+ has highest / 3m among cations. A doubly
charged cation has higher / 3m than unipositive 79. Cathode : 2H2O + 2e — H2 + 2OH
cation. So, a, c, d and e are correct.
Anode : 2CH3COO — 2CO2 + C2H6 + 2e
75. MX M+ + X– For every mole of H2 we get 2 moles of CO2 and
a+10–7 a 1 mole of C2H6.
Ksp = (a + 10–7) a 80. (A) H4XeO6 has more SRP, so better oxidizing agent
tot = M+ + X- + NO 3- then F2
Given, Ktot = 55 × 10 7 Sm 1 = 55 × 10 9 Scm 1. (B) O3 has more SRP, so will oxidize Cl2
M/o o
(C) EClO
55 × 10 9 = / 1000m /ClO is more in acidic medium than in basic
- -
4 3

medium
60 ^a + 10 -7h 80a 70×10 -7 o
(D) E6Fe(CN) @ = 0.36 V
= + + | 6Fe]CNg6@4-
3-

1000 1000 1000 6

Hence [Fe(CN)6] can be easily oxidized by 4–

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

or, Ksp = 12 × 10 14
a = 12 and b = 14 over potential.
Ans = 26. 81. CH4 + 10OH¯ — CO32– + 7H2O + 8e–
76. Cu2+ + 4 NH3 [Cu(NH3)4]2+ 80×3600×0.96
No. of Faradays required = 96500
1 a 0
0 2 1 1 80×3600×0.96
Hence mol. of CH4 required = 8 × 96500
6Cu ]NH3g4@2+ 1 80×3600×0.96
Kf =
6Cu 2+@6NH3@4 VCH = 8 ×
4
96500 × 22.4 L
1 = 8.356 × 0.96 = 8.02 L
6Cu 2+@]2g4
or 1 ×1012 = or [Cu2+] = 6.25 × 10 14

3.907
82. a = 390.7 = 0.01
o 0.059 6Zn 2+@
Ecell = Ecell - 2 log
6Cu 2+@
Now, HA + aq H+ + A
C C
0.059 1 [H ] = C = 0.01 × 0.01 = 10
+ 4
= 1.1 - 2 log 6.25×10 -14 = 0.71 V pH = log [H+] = 4
2.977 3×1×60×60
83. 106.4/n = 96500 & n=4
3.14 Chemistry
Ca 2 1 a2 89. H2 — 2H+ + 2e–
84. K a = 1 - a & 6 = 1 - a
1 atm 10 10

- 1 ! ]1 g2 + 4×6×1 - 1 ! 1 + 24 1
& a= 12 = 12 =3 0.059 ^10 -10h 2
E H /H = 0 -
2
+
2 log 1 & E H /H 2
+

6IO3-@ = 1× 13 = 13 M = + 0.59 V = 590 mV.

7Ag +A = 3×10 = 9×10 -8 M
-8
90. Charge passed = 0.01 Faraday
1
At the anode b H 2 O $ 2 O 2 + 2H + + 2e - l with 90
1
3
2e -

Now 2 Ag + Zn +2
2Ag+ + Zn
0.06 1 1
Gives E =- 1.56 + 2 log
^9×10 -8h2
produce 4 ×0.01×0.9 mole of O2 i.e. 0.00225 mol O2
+2e -

=- 1.1376 V At the cathode 2H2O H2 + 2OH–

85. m om ]H 2 Og =
m om^Ba]OHg h + 2m om]HClg - m om]BaCl g
2 2
moles of H2 produced =
0.01×0.8
mol = 0.004 mol
2 2
= 5.5 × 10 2 S m2 mol 1. Total moles produced of gases = 0.004 + 0.00225 =
0.00625 mol
Now in SI units,
×10 -3 ×10 -3 vol. at STP = 0.00625 × 22400 mL = 140 mL
m om = M ` m om(H O) =
2
]H 2 Ogdiss 91. Eocell = EoRP(RHS) EoRP(LHS)
-2 5.5×10 -6 ×10 -3
5.5×10 = 6
H 2 O@ diss = 0.76 ( 1.36) = 0.6
6H 2 O@ diss = 6H +@ = 6OH -@ = 10 -7 M G =
o
RT ln Keq;
r

For equilibrium: H2O H + OH

+ nFE o 2×0.6
or, log Keq = RT×2.303 = 0.06 = 20
Since the calculated value above matches the actual 2×0.6
value, therefore the reported answer is 20. 0.06 20; Kf = 1020
dE
86. 3 S o = nF dt = 2×96500×
1.718 - 1.2
=5000 J/K. 1000× ^ sol - H2 Oh
20 92. m 0 = s
1000× ]3.4 - 2.02g ×10 -6
×1000
87. m m M 138 = s
×1000
200 = 0.04 s = 1×10 -5 mol/L = 10 mmol/m3.
200×0.04
= 1000 = 8×10 -3 S cm -1 93. a) As Mg is more reactive than Zn, so
E oZn > E oMg o
$ Ecell <0
= b a, l × R
1 2+
/2n 2+
/Mg

b) E oZn /Zn < E oAg

2+ +
/Ag , so Eocell > 0. At equilibrium
8×10 -3 = : 4 D × R
8 1 Ecell = 0
o
c) For concentration cell, Ecell = 0 . Also as
2 1
R= = ×103 X concentration are same at anode and cathode so
8×10 -3 4
Ecell = 0 as Q = 1
Again V = IR
d) As Fe is more reactive than Ag, so Eocell > 0.
V 10
So I = R = = 4×10 -2 A = 40 mA 1000k
b 1 ×103 l 94. a) m
=
M , so ‘p’
4
b) k decreases with dilution as number of ions per
88. l = 1.5 cm A = 10 cm2, C = 0.05 cm3 of solution decreases, so ‘s’
Effective area A’ = 5 cm2, R = 50 /
c) a 3m , so ‘r’
/m
1 , 1 1.5
= R × ' = 50 × 5 d) For sparingly soluble salt, m = m and M = S
A
1000k
1000 1.5 S= . Hence ‘q’
/ m = 0.05 × 50×5 = 120 Scm 2 mol -1 / om
 Electrochemistry 3.15
0.059 ^PH hc 6H +@a2 E 0
cell = 0 and not conc. cell is in working condition.
95. (a) Ecell =- 2 log
^PH ha 6H +@c2
2

2
It is a concentration cell.
0.059 0.01× ]0.1g 2
0.059 0.059 6Cu +2@a
E0cell =- 2 log ]0.1g × ]1 g2 = 2 ×3 =+ ve (c) Ecell = 0 - 2 log
6Cu +2@c
(b) Cell reaction Ag +c ^10 -2h " Ag +a ^10 -9h 0.059 0.1
=- 2 log 0.01 =- ve
0.059 10 -9 0.059
Ecell =- 1 log 10 -2 =+ 1 ×7 > 0 0.059 6Cl -@c 0.059 0.1
(d) Ecell =- log = 2 log 0.1 = 0
2 6Cl -@a
and E0cell = 0

1. PbSO 4] s g + 2OH " PbO2 + H2 SO 4 + 2e

- -
5. E oMnO -
4 /Mn +2 = 1.51 V ... (i)
0.05
o
2 mole 0.05F E Cl 2 /Cl - = 1.36 V ... (ii)
o
PbSO4 + 2e + 2H
– +
Pb(s) + H2SO4 E Cr2 O 7-2 /Cr +3 = 1.33 V ...(iii)
Total number of moles of PbSO4 = 0.05/2 o
ECr +3
/Cr =- 0.74 ...(iv)
0.05
Mass of PbSO4 = 2 × 303 = 7.6 g Since Cr is having least reducing potential, so Cr
+3

2. G° = – nFE°cell has greatest tendency to get oxidized and is the best

Reducing agent.
= – 2 × 96,000 × 2
= – 384,000 CV mol–1 6. Galvanization is applying a coating of Zn.
Now, G° = – RT ln K 7. Cu2+ + 2e– — Cu
or, –384,000 = – 8 × 300 ln K 2F 1 mole
384000 = 63.5 g.
lnK = - - 2400 =160
K = e160 8. Mn + 2e —
2+
Mn Eo1 = 1.18 Go1 = 2FEo1
3. Lesser the value of reduction potential, higher is Mn2+ — Mn3+ + e Eo2 = 1.51 Go2 = FEo3
the tendency to loose electrons. Thus, reducing _____________________
nature increases as the value of reduction potential 3Mn2+ — Mn + 2 Mn3+ Go3 + 2 Go2 = FEo3
o o
becomes more and more negative. 2E1 + 2E 2
Eo3 = 2 = Eo1 + Eo2 Eo3 = 2.69 V
The reducing power of the metals increases in the
order : a Eo < 0 Non spontaneous.
Ni < Zn < Mg < Ca 9. Reason : Higher the position of element in the
4. B 2 H6 + 3O 2 B 2 O3 + 3H 2 O
of its cations.
27.66
27.66 If Ca2+ (aq) is electrolysed, water is reduced
1mol 3mol in preference to it. Hence it cannot be reduced
4e - + O 2 2O 2- electrolytically from an aqueous solutions.
therefore charge required = 12 faraday
10. m c = m3 - B C (Debye Huckel equation)
Hence
12 # 96500 = i # t 11. Higher the SRP, better is oxidising agent
= 100 amp # t Hence MnO4 is strongest oxidising agent
t = 12 # 965 second 12. X + Y2+ — X2+ + Y
12 # 965 11580 For reaction to be spontaneous Eº must be positive.
t= 3600 = 3600 = 3.2 hours. If X = Zn and Y = Ni, the Eo = + 0.53 V
3.16 Chemistry
2 4 0
Go =3×0.036 F – 2 × 0.439 × F = – 1 × E(Fe ×F
13. 3 Al 2 O3 $ 3 Al + O 2 3+
/Fe +2)
0
r
G = +966 kJ mol–1 = 966 × 103 J mol–1 E ]Fe3+ /Fe +2g = 2 × 0.439 – 3 × 0.036
G = – nFEcell = 0.878 – 0.108 = 0.770 V
966 × 103 = – 4 × 96500 × Ecell
0.059 6Cr +3@2
15. Ecell = E0cell - log
6Fe +2@3
Ecell = 2.5 V 6
14. Fe3+ + 3e– — Fe Go1 = –3 × F × E0Fe 3+
/Fe 0.056 ]0.1g2
]0.01g3
0
= 0.3 - 6 log = 0.3 - 0.4 = 0.26 V
Fe2+ — Fe Go2 = –2 × F × E Fe 2+ /Fe

Fe3+ + e– — Fe2+ Go = Go1 – Go2

2.303 RT 6. The species having less reduction potential with

1. E = 1.1 2F log10
respect to NO3– (Eº = 0.96 V) will be oxidised by
Now, G = nFE NO3–.
These species are V, Fe, Hg.
G = 2.303 RT 2.2 F
7. A(s) | An+ (aq, 2M) || B2n+ (aq, 1M) | B(s)
2. Salt bridge is introduced to keep the solutions of two
electrodes separate, such that the ions in electrode Reactions
do not mix freely with each other. But it cannot stop Anode (A — An+ + ne) × 2
the process of diffusion.
Cathode B2n+ + 2ne — B
___________________________
It does not participate in the chemical reaction. Overall reaction:
However, it is not necessary for occurence of
cell reaction, as we know that designs like lead 2A(s) + B2n+ — 2An+ + B
accumulator, there was no salt bridge, but still RT
E = E o - 2nF ,nQ
reactions takes place.
RT 6A n+@
2

0.059 6Fe 2+@2 O = E o - 2nF ,n 2n+

3. E = E o - 4 log + 4 B
6H @ PO 2
RT
E o = 2nF ,n4
0.06 ^10 -3h2
= 1.67 - 4 log - 2nFRT
^10 -3h4 ×0.1 Now Go = 2nFEo = 2nF n4
0.03 = RT n4.
= 1.67 - 2 log 107
Go = Ho T So = T So
0.03
= 1.67 - 2 ×7 = 1.67 - 0.105 T So = Go
3 G o - RT,n4
= 1.565 = 1.57 V. So = T = T = R n4
4. = 8.3 × 2 × 0.7 = 11.62 JK 1mol 1
,
8. = 120 cm = 1cm2 & A = 120 cm 1

,
= C A = 5 × 10 7 × 120 S cm 1
= 6 × 10 5 S cm 1
1000 6×10 -2
/m = M = = 40 Scm2 mol 1.
1.5×10 -3
I×t(sec) No, for the acid [H+] = 10 4 M = c
5. Faraday law equivalents of H2 produced = 96500
10 -4 1
10×10 -3 ×t = =
0.01×2 = 96500 = 96500×2 = t 1.5×10 -3 15
/ /
19.3 × 104 sec = t ∵ a = om & / om = am 40 × 15
/m
o
m
= 600 S cm2 mol 1.
o
m
= 6 × 102 Ans = 6
 Electrochemistry 3.17
9. m oX . m oY
- - 12. In+ — In3+ + 2e–, 0.42 volt.
m oH + m oX . m oH + m oY
+ - + - In 2+
+ e — In+, – 0.4 volt.
______________________________
/ oHX . / oHY ...(1) In 2+
— In3+ + e– E volt
o
______________________________
/
Also mo = a, So m (HX) = / om a1 and Eº = 0.44 volt.
/m
m m (HY) = m om a 2 (Where 1 and 2 are degrees of Eºcell = 0.15 + 0.44 = 0.59 volt.
dissociation of HX and HY respectively.) 0.059
0 = 0.59 – 1 log K.
Now, Given that
K = 10 . 10

m
(HY) = 10 m
(HX). X Y
o
/ a 2 = 10× / a1
m
o
m
13. (P) (C 2 H5) 3 N + CH3 COOH $ CH3 COO - (aq)
a 2 = 10 a1 ...(2) + (C 2 H5) 3 NH + (aq)
Ca 2 As CH3COOH is a weak acid, its conductivity
K a = 1 - a , But < < 1, therefore Ka = C 2. is already less. On addition of weak base, acid
K a (HX) 0.01a12 0.01 base reaction takes place and new ions are
b1 l = 1
2

K a (HY) = 2 = 0.1 × 10 1000 created. So conductivity increases.

0.1a 2
log (Ka (HX) log (Ka(HY)) = 3. (Q) KI (0.1 M) + AgNO3 (0.01 M)
pKa (HX) pKa (HY) = 3. — AgI . (ppt) + KNO3 (aq).
10. M —
+
M + 2e
3+ – As the only reaction taking place is precipitation
of AgI and in place of Ag+, K+ is coming in the
G = –nFE For 1 mole of m
0 0 +
solution, conductivity remain nearly constant
G0 = –2 × 96500 × (–0.25) J and then increases.
= + 48250 J/mole = 48.25 KJ/mole (R) CH3COOH + KOH — CH3COOK (aq) + H2O
Energy released by conversion of 1 mole of OH (aq) is getting replaced by CH3COO–,
–

X— Y G = –193 KJ which has poorer conductivity. So conductivity

193 decreases and then after the end point, due to
Hence moles of M+ converted = 48.25 = 4
common ion effect, no further creation of ions
11. Let solubility of AgBr in presence of 10 7 M take place. So, conductivity remain nearly same.
AgNO3 be ‘s’ (S) NaOH + HI — NaI (aq) + H2O
(s + 10 )s = 12 × 10
7 14
s = 3 × 10 M
7 As H is getting replaced by Na+ conductivity
+

[Ag ] = 4 × 10 M
+ 7 decreases and after end point, due to OH–, it
increases.
[Br ] = 3 × 10 7 M
[NO3 ] = 10 7 M
tot
= Ag + + Br - + NO 3-

m_ Ag i $ M _ Ag + i
o +
/
Ag + = 1000 and similarly for
Br and NO3
60×4×10 -7 80×3×10 -7 70×10 -7
tot
= 1000 + 1000 + 1000
= 24 × 10 + 24 × 10 + 7 × 10 9
9 9

= 55 × 10 9 s cm 1

tot
= 55 × 10 7 s cm 1
3.18 Chemistry