PROF.

RAVINDER CHADHA
: 9814102167

351, Adarsh Nagar, Jalandhar City

(XII) : Electrochemistry (28)
Answers to N.C.E.R.T. Book Intext Unsolved Questions
1. A cell is set up consisting of Mg|MgSO4 (1M) as one electrode (by dipping a magnesium wire in 1 M MgSO4
solution) and standard hydrogen electrode as the second electrode. Reading of the voltmeter gives the EMF of
the cell as 2·37 V. The direction of flow of electrons is from magnesium electrode to hydrogen electrode. Thus,
Mg rod acts as anode and SHE acts as cathode. Reduction potential of SHE is zero, so, the standard reduction
potential of Mg electrode, E oMg 2+ /Mg = 2·37 V.
2. See Notes - Page No.7
3. The electrode potential of Fe3+Fe2+ is 0·78 V. The substances having electrode potential more than
0·78 V will be reduced and can oxidise Fe2+. These are Br2 , Cℓ2 and Cr2O72– .
4. See Notes - Page No.8
5. Applying Nernst equation to the given cell reaction
0·0591 [Ni 2+ ] 0·0591 0·160 0·0591
Ecell = E cell − = 1·05 −
o
log = 1·05 V – log log (4 × 104)
n [Ag + ]2 2 (0·002) 2
2
0.0591
= 1·05 – (4·6021) = 1·05 – 0·14 V = 0·91 V
2
6. n = 2, ∆rGº = – nF E ocell = – 2 × 96500 × 0·236 J = – 45·55 kJ mol–1
− ∆ r Gº 45· 55 kJ mol −1
∆rGº = – 2·303 RT log Kc or log Kc = = = 7·983
2· 303 RT 2· 303 × 8· 314 × 10 −3 kJ K −1 mol −1 × 298 K
Kc = antilog (7·983) = 9·616 × 107
7. This is because, on dilution number of ions per unit volume decrease and conductivity depends on the number of
ions per unit volume.
8. Water (H2O) is a weak electrolyte, so according to Kohlrausch’s law
Λom (H2O) = λ oH + + λ oOH − = λ (H
o
+
)
+ λ (C
o
l− )
+ λ (Na
o
+
)
+ λ (OH
o
−
)
− λ (Na
o
+
)
− λ (C
o
l− )

= Λom (HCℓ) + Λom (NaOH) – Λom (NaCℓ)

9. Λom (HCOOH) = λº (H+) + λº(HCOO–) = 349·6 + 54·6 S cm2 mol–1 = 404·2 S cm2 mol–1; Λcm = 46·1 S cm2 mol–1 (Given)
Λ cm 46·1
∴ α= o
= = 0·114
Λ m 404·2
Dissociation constant, Ka = Cα =
2
0· 025 × (0· 114)2
∴ = 3·67 × 10– 4
1 −α 1 − 0· 114
10. Q (coulombs) = I (ampere) × t (sec) = (0·5 ampere) × (2 × 60 × 60 s) = 3600 C
Now charge flowing (Q) = no. of electrons flowing (n) × Charge on each electron (e)
3600 = n × 1·602 × 10–19; ∴ n= 3600 = 2·246 × 1022 electrons
−19
1· 602 × 10
11. Sodium, calcium, magnesium and aluminium.
12. 1 mole of Cr2O72– requires 6 mole of electrons for its reduction.
Thus, 1 mol of Cr2O72– ions require 6 F = 6 × 96500 C = 579000 C of electricity.
13. See Notes - Page No.15
14. Methane and methanol
15. See Notes – Page No.13-14

Answers to N.C.E.R.T. Book End Exercise:

1. The metal which has lower value of reduction potential is more reactive and it will displace the other (having
more value of reduction potential) from the solution of its salt. Thus, the order in which these metals displace
each other is Mg, Aℓ, Zn, Fe, Cu.
2. The metal which has more negative value of reduction potential can be easily oxidised and hence is a better
reducing agent. Thus, increasing order of reducing power will be : Ag < Hg < Cr < Mg < K
3. The cell is represented as Zn/Zn2+ (aq) ║ Ag+ (aq)/Ag
(i) Zinc electrode (anode) is negatively charged electrode.
(ii) Carriers of the current in the cell are ions.
(iii) At anode : Zn(s) → Zn2+(aq) + 2e– Oxidation half reaction.
At cathode : 2 Ag (aq) + 2e → 2 Ag(s)
+ –
Reduction half reaction
4 (i) (a) Calculation of standard cell potential
The cell is represented as Cr(s)/Cr3+(aq) ║ Cd2+(aq)/Cu(s)
The cell reaction are :
2 Cr → 2Cr3+ + 6e–
3Cd2+ + 6e– → 3Cd
Net reaction : 2 Cr + 3Cd2+ → 2Cr3+ + 3Cd here, n = 6
E cell = E c - E a = E Cd 2+ /Cd – E Cr 3+ /Cr = – 0·40 – (– 0·74) = – 0·40 + 0·74 = + 0·34 V
o o o o o

(b) Calculation of ∆rGo

∆rGº = – nF E ocell = – 6 × 96500 C × 0·34 V = – 196860 J = – 196·86 kJ mol–1
(c) Calculation of equilibrium constant
∆Gº = – 2·303 RT log Kc
PROF. RAVINDER CHADHA
: 9814102167
351, Adarsh Nagar, Jalandhar City

(XII) : Electrochemistry (29)
∆G ο − 196860 34
log K c = = = 34·501, ∴ Kc = antilog (34·501) = 3·17 × 10
− 2· 303RT − 2· 303 × 8· 314 × 298
(ii) Solve as above. Answers are:
(a) E ocell = 0·03 V (b) ∆rGº = – 2·895 kJ mol–1 (c) Kc = 3·2
2+
0· 0591 [ Mg ]
5. (i) Ecell = Eocell – log ... (i)
2 [Cu 2 + ]
Where E ocell = E oc − E oa = E Cu
º
2+
/Cu
º
– E Mg 2+
/Mg
= 0·34 – (– 2·37) = 0·34 + 2·37 = 2·71 V

[Mg2+] = 0·001 M and [Cu2+] = 0·0001 M

Put in equation (i) , we get
0· 0591 0· 001
Ecell = 2·71 – log = 2·71 – 0·0295 log10 = 2·71 – 0·0295 × 1 = 2·6805 V (Q log 10 = 1)
2 0· 0001
0· 0591 [Fe 2+ ] [pH 2 ]
(ii) Ecell = Eocell – log … (i)
2 [H+ ]2
o o
Eocell = E c – E a = E º2H + /H – E Fe
º
2+
/Fe
= 0·00V – (– 0·44 V) = + 0·44 V
2
2+ +
[Fe ] = 0·001 M and [H ] = 1 M, pH2 = 1 bar
Put in the eq (i) we get Ecell = 0·44 V –
0·0591 [0·001] = 0·44 V – 0·0295 [log10- 3]
log
2 [l]2
= 0·44 V – 0·0295 × – 3 log10 = 0·44 + 0·0885 V × 1 = 0·5285 V (Q log10 = 1)
(iii) Cell reaction : Sn + 2H → Sn2+ + H2(n = 2)
+

0· 0591 [ Sn 2 + ] 0· 0591 0· 05
Nernst equation : Ecell = Eºcell – log + 2
= [0 – (– 0·14)– log
2 [H ] 2 (0· 02)2
0· 0591 0· 0591
= 0·14 – log 125 = 0·14 – (2·0969) = 0·078 V
2 2
(iv) Cell reaction : 2 Br– + 2H+ → Br2 + H2 (Note carefully)
0· 0591 1
Nernst equation : Ecell = Eºcell – log
2 [ Br ] [H + ]2
− 2

0· 0591 1 0· 0591
∴ Ecell = (0 – 1·08) – log =– 1·08 – log (1·111 × 107)
2 [0· 01]2 [0· 03]2 2
0· 0591
(7·0457) = 1·08 – 0·208 = – 1·288 V
= – 1·08 –
2
Thus, oxidation will occur at the hydrogen electrode and reduction on the Br2 electrode. Ecell = 1·288 V
6. The cell reaction occurring in the cell are :
− −
Zn → Zn2+ + 2e (oxidation), 2Ag+(aq) + 2e → 2 Ag(s) (reduction)
E ocell = E ocathode − E oanode = E Ag
o
+
/Ag
− E oZn 2+ /Zn = 0·80 − (− 0·76) = 1·56 V
o
∆rGº = − nF E cell = − 2 × 96500 × 1·56 = – 301080 CV = – 301080 J = – 301·08kJ.
7. See Notes – Page No.1 to 3
8. See Notes – Page No.2
9. See Notes – Page No.2
1 S cm −1
10. = 1 (unit conversion factor)
100 S m −1
Conc. (M) c1/2 (M1/2) κ(S m–1) κ (S cm–1) 1000 × κ
Λ cm = (S cm2 mol–1)
Molarity
10–3 0·03146 1·237 × 10–2 1·237 × 10–4 1000 × 1· 237 × 10 −4
= 123·7
10 − 3
10–2 0·100 11·85 × 10–2 11·85 × 10–4 1000 × 11· 85 × 10 −4
= 118·5
10 − 2
2 × 10–2 0·141 23·15 × 10–2 23·15 × 10–4 1000 × 23· 15 × 10 −4
= 115·8
2 × 10 − 2
5 × 10–2 0·224 55·53 × 10–2 55·53 × 10–4 1000 × 55· 53 × 10 −4
= 111·1
5 × 10 − 2
10–1 0·316 106·74 × 10–2 106·74 × 10–4 1000 × 106· 74 × 10 −4
= 106·7
10 −1
PROF. RAVINDER CHADHA
: 9814102167
351, Adarsh Nagar, Jalandhar City

(XII) : Electrochemistry (30)

Λºm can be obtained on extrapolation to zero concentration along Y axis. It is 124·0 S cm2 mol–1.
11. Specific conductance or conductivity, κ = 7·896 × 10–5 S cm-1 , c = 0·00241 M, Λcm = ?

κ × 1000 7·896× 10 –5 S cm –1 × 1000 cm3 L–1 = 32.76 S cm 2 mol -1

c
Λm = =
c (Molarity) 0·00241 mol L–1
Λ cm 32·76
α= = = 0·0839 = 0·084
Λ om 390·5
cα 2 0· 00241 M × (0· 084)2
Now, dissociation constant (Ka) = = = 0·0000186 = 1·86 × 10–5 M
1 −α 1 − 0· 084
12. See Notes – Page No.12
13 (i) CaCℓ2 contain Ca2+ ion.
Ca2+ + 2e → Ca (ii) Aℓ3+ + 3 e– → Aℓ
2 mol 1 mol 3F 1 mol = 27g
2F (40g) (3 × 96500C)
Electricity needed to produce 40 g Ca = 2F 27g of Aℓ is deposited by electricity = 3F
3 × 40
∴ Electricity needed to produce 20 g Ca = 2 × 20 = 1F ∴ 40 g “ “ “ “ = = 4·44F
40 27
14. See Notes – Page No.12
−
15. Ni2+ + 2e → Ni
2 mol 1 mol
2 F (2 × 96500 C)
Quantity of electricity passed = Current in amperes (I) × time in seconds (t)
or Q = I t = 5A × 20 × 60s = 6000A s = 6000C [Q A × s = C]
2 × 96500 C of electricity deposit Ni = 58·7 g
58·7 × 6000
∴ 6000 C of electricity deposit Ni = = 1·825g
2 × 96500
Alternatively
Now I = 5A, t = 20 min = 20 × 60 = 1200s; E = Atomic mass/Valency = 58·7/2
Amount of Ni deposited, W = Z.I.t = E × I.t = 58· 7 × 5 × 1200 = 1·825g (Where E is equivalent mass)
96500 2 × 96500
−
16 In Cell B Ag+ + e → Ag
1 mol 1 mol = 108g
1F(96500 C)
108g of silver is deposited by = 96500C
96500 × 1·45
∴ 1·45g silver is deposited by = = 1295·6 C
108
Q 1295·6
Now, Q = It ; ∴ t= = = 863 s
I 1·5
In Cell C Cu2+ + 2e– → Cu
i.e., 2 × 96500 C deposit Cu = 63·5 g
∴ 1295·6 C will deposit Cu = 63· 5 × 1295·6 = 0·426 g
2 × 96500
In Cell A Zn2+ + 2e– → Zn
65· 3
∴ Zn deposited = × 1295·6 = 0·438 g
2 × 96500
17 (i) º
E Fe 3+
/Fe
= + 0·77 V, E oI /2 I − = + 0· 54 V
2

Since Fe3+ undergo reduction and I- undergo oxidation, 2I- + 2Fe3+ → I2 + 2Fe2+
E ocell = E oc - E oa = E Fe
º
3+
/Fe
º
– EI – = 0·77 – 0·54 = + 0·23 V
2 /2I

The EMF of the reaction in positive, thus the reaction between Fe3+ and I– is feasible
(ii) Cu(s) + Ag+(aq) → Cu2+ (aq) + Ag(s) ; E ocell = E Ago
+
/Ag
- E oCu 2+ /Cu = 0·80 – 0·34 = + 0·46 V
The reaction is also feasible because the EMF of the reaction is positive
PROF. RAVINDER CHADHA 351, Adarsh Nagar, Jalandhar City

: 9814102167
(XII) : Electrochemistry (31)
(iii) Br–(aq) + Fe3+(aq) → Fe2+(aq) + ½Br2(g); Eºcell = 0·77 – (1·09) = – 0·32 V (not feasible)
(iv) Ag(s) + Fe3+(aq) → Ag+ (aq) + Fe2+ (aq); Eocell = EFe
o
3+
/Fe 2+
− EAg
o
+
/Ag
= 0·77 – 0·80 = – 0·03 V
The reaction is not feasible because the EMF of the reaction comes to be -ve
(v) Fe2+(aq) + ½Br2(aq) → Fe3+(aq) + Br–(aq); Eºcell = 1·09 – 0·77 = 0·32 V (feasible)
18 (i) An aqueous solution of AgNO3 using silver electrodes :
Both AgNO3 and water will ionize in aqueous solution
(aq) − (aq)
AgNO3(aq) → Ag+(aq) + NO 3 (aq) ; H2O H+(aq) + OH– (aq)
At cathode: Ag+ ions have greater preference for discharging than H+ ions, so Ag will be deposited at cathode.
Ag+ + e– → Ag
At anode: Silver from anode will dissolve to form Ag+ ions which go in the solution. Ag(s) → Ag+(aq) + e–

(ii) An aqueous solution of AgNO3 with platinum electrodes (inert electrodes)

−
AgNO3(aq) l Ag+(aq) + NO 3 (aq) and H2O l H+(aq) + OH–(aq)
At cathode: Ag+ ions have greater preference for discharging than H+ ions, so Ag will be deposited at cathode.
Ag+ + e– → Ag
−
At anode: OH– ions have greater preference for discharging than NO 3 , so, 2OH– → H2O + ½O2 + 2e–
Thus, as a result of electrolysis, silver is deposited at the cathode while O2 is evolved at the anode.
(iii) A dilute solution of H2SO4 using platinum electrodes :
On passing current, both acid and water will ionize as follows :
H2SO4(ℓ) → 2H+(aq) + SO42–(aq); H2O l H+(aq) + OH–(aq)
At cathode : H+(aq) will be reduced to H2(g); 2H+(aq) + 2e– → H2(g)
At anode : OH– ions have greater preference for discharging than SO42– ions, therefore, OH–
will be discharged. 2OH-(aq) → H2O(ℓ) + ½O2(g) + 2e–
Thus, H2 is liberated at the cathode and O2 at the anode.
(iv) An aqueous solution of CuCℓ2 with platinum electrodes (inert electrodes)

(aq) (aq)
CuCℓ2 2Cu2+ + 2Cℓ– ; H2O H+ + OH–
At anode : Cℓ– ions will be discharged in preference to OH– ions, so, Cℓ2 will be evolved at anode.
2Cℓ–(aq) → Cℓ2(g) + 2e–
At cathode : Cu2+ ions will be reduced in preference of H+ ions, so, Cu will be deposited at cathode.
Cu2+(aq) + 2e– → Cu(s)

Answers to C.B.S.E. Higher Order thinking (HOT) Questions and Problems:

1. ‘B’ is a strong electrolyte because on dilution of a strong electrolyte, number of ions remains the same. Only
interionic attraction decreases and therefore increase in Λm is small.
2. An electrochemical cell in which both the electrodes are made up
of the same metal dipped in the solutions of same electrolyte of
different concentrations is called a concentration cell. In such a
cell, oxidation takes place on the electrode dipped in electrolyte
of lower concentration and it acts as anode. The reduction takes
place on the electrode dipped in electrolyte of higher
concentration and it acts as cathode.
e.g., Cu/CuSO4(C1) ║ CuSO4 (C2)/Cu
0· 0591 C
Ecell = Eºcell − 0· 0591 log C 1 =
º
log 2 (C2 > C1, E cell = 0)
n C2 n C1
3. In this cell reaction, Mg is anode (oxidation occurs) and Cu is cathode (reduction occurs)
2+ −3
Ecell = E ºcell − 0· 059 log [Mg ] = 2·71V + 0· 059 log 10 = 2·71V + 0·0295 = 2·7395V
n 2+
[Cu ] 2 10 −2
º
(i) When Eext < 2·71V ( E cell ), cell works normally i.e. Mg is oxidised and Cu2+ is reduced, so, e– flow from Mg
(anode) to Cu (cathode). The current flows in the opposite direction from Cu to Mg (cathode to anode).
º
(ii) When Eext > 2·71 ( E cell ), cell reaction is reversed. Now Cu is oxidised and Mg2+ are reduced. Electrons
flow from Cu to Mg, so, current flows from Mg to Cu (anode to cathode).
4. (a) Zinc anode acts as negative terminal while copper cathode acts as positive terminal.
(b) Function of salt bridge is to maintain the electrical neutrality of the two half cells.
(c) Current flows from copper electrode (cathode) to zinc electrode (anode).
(d) E ocell = E oc – E oa = E oCu 2+ /Cu – E oZn 2+ /Zn = 0·34 V – (– 0·76 V) = 1·10 V
5. (a) Zinc container acts as anode while a carbon rod acts as cathode.
(b) A paste of ZnO + KOH acts as the electrolyte. (c) 1·35 V.
(d) The cell potential remains constant because the overall reaction does not involve any ion in solution
whose concentration can change during its life time.
6. Charge on one mole of electrons = 1 F = 96500 C
Now, 96500 C of charge is present on electrons = 6·022 × 1023
PROF. RAVINDER CHADHA
: 9814102167
351, Adarsh Nagar, Jalandhar City

(XII) : Electrochemistry (32)
1·0 C of charge is present on electrons = 6· 022 × 10 × (1C) = 6·24 × 1018
23

( 96500 C )
7. Quantity of electricity flowing through the cross section of the wire per second = 1A × 1 sec = 1 Coulomb
1 Faraday (96,500 C) is equivalent to flow of 1 mole of electrons, i.e., 6·022 × 1023 electrons.
6· 022 × 10 23
∴ 1 C will be equivalent to flow of electrons = = 6·24 × 1018
96500
Alternatively:
Quantity of electricity flowing through the cross section of the wire per second = 1A × 1 sec = 1 Coulomb
Charge flowing (Q) = no. of electrons flowing (n) × Charge on one electron (e)
∴ n= Q = 1 = 6·24 × 1018
−19
e 1· 602 × 10
−
8. The electrode reaction written as reduction reaction is Zn2+(aq) + 2e l Zn(s); (n = 2)
95
As 0·1 M ZnSO4 solution is 95% dissociated, this means that in the solution, [Zn2+] = × 0·1 M = 0·095 M
100
Applying Nernst Equation, we get E Zn 2+ /Zn = E oZn 2+ /Zn − 0·0591 log 1
2 [Zn 2+ ]
∴ E Zn 2+ /Zn = − 0·76 − 0·0591 log 1 = − 0·7902 volts
2 0·095
1
9 (i) H2O → 2H+ + O2 + 2e–
2
1 mol 2 mol
2F
Charge required for the oxidation of 1 mole of H2O = 2F
∴ “ “ “ “ “ “ 2 mole of H2O = 4F = 4 × 96500 C
(ii) Molarity = No. of moles
Volume in litres
∴ No. of moles = M × V = 0·5 mol L–1 × 0·5 L = 0·25 mol
MnO4– + 8H+ + 5e– → Mn2+ + 4H2O
1mole 5mol
5F
For the reduction of 1 mole of MnO4–, charge required = 5F = 5 × 96500 C
“ “ “ “ 0·25 mole “ “ “ “ = 5 × 96500 × 0·25 = 120625 C
+ −
10. Electrode reaction involved is as: H (aq) + e → ½ H2(g)
Applying Nernst equation at 298 K
0· 0591 p H2
E 2 H + / H = E o2 H + / H − log (Here n = 1, pH2 = 1 atm)
2 2 n [H + ]
0· 0591 1
− 0·118 V = 0 V − pH (Q pH = log )
1 [H + ]
0· 118
or 0·0591 pH = 0·118 V or pH = = 1·9966 ≈ 2
0· 0591
E2 H + / H − 0· 118
Alternatively E 2 H + / H = – 0·0591 pH, ∴ pH = 2
= ≈2
2 − 0· 0591 − 0· 0591
11. I = 2·5A, t = 35 min = 35 × 60s
E × I.t W × 96500 3· 06 × 96500
W = Z.I.t. = or E= = = 56·25g
96500 I.t 2· 5 × 35 × 60
(Where E is equivalent mass and Z is electrochemical equivalent)

Molar mass = Equivalent mass × valency = 56·25 × 2 = 113·5 g mol–1

3· 905 × 10−5 S cm−1 × 1000 cm3 L−1
Λm or Λ m = κ × 1000 =
c
12. = 39·05 S cm2 mol– 1
Molarity 0· 001 mol L−1
CH3COOH l CH3COO– + H+; Λ om = λ oCH COO− + λ oH+ = 40·9 + 349·6 = 390·5 S cm2 mol–1
3

Λc 39· 05
∴ α = m = = 0·1
Λmo
390· 5
13. Step I Calculation of the quantity of charge passed.
We know that Power = Voltage × Current
100 W 100
∴ 100 W = 110 V × I or I= = amp
110 V 110
Now, charge passed (Q) = current × time =  
100
amp  × (4 × 60 × 60s) = 13091 C
 110 
Step II Calculation of mass of cadmium deposited. The cathodic reaction is
Cd2+(aq) + 2e– → Cd(s)
2F 1 mol = 112·2 g
2 × 96500 C
2 × 96500 C of charge deposit Cd = 122·2 g
PROF. RAVINDER CHADHA
: 9814102167
351, Adarsh Nagar, Jalandhar City

(XII) : Electrochemistry (33)
(112· 2g )
∴ 13091 C of charge deposit Cd = × (13091C) = 7·61 g.
( 2 × 96500 C )
0·0591 1
14. Ecell = E ocell – log 2+
o
= E cell + 0·0295 log C
2 [Zn ]
When solution is diluted 100 times
C
E 'cell = E ocell + 0·0295 log o
= E cell + 0·0295 log C + 0·0295 (– 2)
100
∴ Ecell will decrease by 0·0295 × 2 = 0·059 V
15. Λ º
m ( NH 4C l ) = Λ ºm( NH + ) + Λ mº (Cl− ) = (73·8 + 76·2) = 150·0 S cm2 mol–1; κ = 1·29 × 10–2 S cm–1
4

κ × 1000 1· 29 × 10 −2 × 1000 Λc 129

Λ cm = = = 1·29 × 102 = 129 S cm2 mol–1 and α = mo = = 0· 86
C 0· 1 Λ m 150
cα 2 0· 1 × (0· 86)2 0· 0739
K(Dissociation constant) = = = = 0·528
1−α 1 − 0· 86 0· 14

☺☺☺☺☺
PROF. RAVINDER CHADHA
: 9814102167
351, Adarsh Nagar, Jalandhar City

(XII) : Electrochemistry (34)
Sol. to N.3 at Page No.4
According to Kohlrausch law ∧CH
o
3COOH
= ∧ oCH3COONa + ∧ HC
o
l − ∧ NaCl
o

= 91·0 + 426·2 – 126·5 = 390·7 ohm-1 cm2 mol-1

Molar conductivity of 0·1 M CH3COOH, ∧ cm = 5·20 ohm-1 cm2 mol-1
∧m
c
5·20
Degree of dissociation, α = o = = 0·0133 = 1·33%
∧m 390·7
Sol. to N.4 at Page No.4
κ × 1000 4· 95 × 10 –5 S cm –1 × 1000 cm 3 L–1
c
Λm = = = 48·15 S cm2 mol–1
c (Molarity) 0· 001028 mol L– 1
c 2 −1
cα 2 0· 001028 mol L− 1 × (0· 1233) 2
α = Λ m = 48·15 S cm mol = 0·1233 and K = = = 1·78 × 10–5 mol L–1
Λ om 390·5 S cm 2 mol −1 (1 − α) 1 − 0·1233
Sol. to Q.3 at Page No.9
In this cell, Mg electrode acts as anode and Ag electrode acts as cathode. The cell is represented as
Mg│Mg2+ (0·100 M) ║ Ag+ (0·001M)│Ag
0· 0591 [Mg 2 + ]
Apply Nernst equation Ecell = E ocell – log (here n = 2)
n [Ag + ]2
0· 0591 (0· 1) 0· 0591
= 3·17 – log 2
= 3· 17 – log 105
2 (0· 001) 2
= 3·17 – 0·0295 × 5 log 10 = 3·17 – 0·1475 = 3·0225 V
Sol. to Q.4 at Page No.9
2Cr(s) + 3Fe2+(aq) l 2Cr3+(aq) + 3Fe(s);
0· 059 [Cr 3+ (aq)]2
Ecell = E ocell – log ; Ecell = 0·261V, n = 6
n [Fe 2 + (aq)]3
0· 059 ( 0· 01)2 0· 059 ( 0· 01)2 0· 059
0·261 = E ocell – log or E ocell = 0·261 + log = 0·261 + log 102
6 (0· 01)3 6 (0· 01) 3
6
0· 059
= 0·261 + × (2) = 0·261 + 0·0197 = 0·2807V
6
Sol. to Q.5 at Page No.9
The cell reaction is : 2Aℓ + 3Ni2+ → 2Aℓ3+ + 3Ni
E ocell = E ocathode – E oanode = E oNi 2 +/Ni – E Ao l 3+ /Al = – 0·25 – (–1·66) = 1·41 V
To find Ecell . Here n = 6
0· 059 [Al 3+ ]2 0· 059 ( 0· 001)2
Nernst equation is Ecell = E ocell – log = 1 · 41 – log
n [Ni 2 + ]3 6 (0· 1)3
0· 059 0· 059
= 1·41 – log (10–3) = 1·41 – × (–3) = 1·41 + 0·0294 = 1·44 V
6 6
Sol. to Q.2 at Page No.10
Since Eº(Fe2+/Fe) > Eº (Aℓ3+/Aℓ), so Fe electrode act as cathode and Aℓ electrode act as anode.
The cell reaction is : 2Aℓ + 3Fe2+ → 2Aℓ3+ + 3Fe
E cell = E cathode – E oanode = E oFe 2+ /Fe – E Ao l 3+ /Al = – 0·44 – (–1·66) = 1·22 V
o o

To find Ecell . Here n = 6

0· 059 [Al 3 + ]2 0· 059 (0· 01)2
Nernst equation is Ecell = E ocell – log = 1 · 22 – log
n [Fe 2 + ]3 6 (0· 02 )3
0· 059 0· 059
= 1·22 – log (12·5) = 1·22 – × 1·0969 = 1·22 – 0·0107 = 1·2093 V
6 6
To find ∆Gº. ∆Gº = – nFEºcell = – 6 × 96500 C × 1·22 V = – 706380 J mol–1 = – 706·380 kJ mol–1

Sol. to Q.3 at Page No.10

E ocell = Eoc – Eoa = EoCd2+/Cd – EoZn 2+/Zn = – 0·403 – (– 0·763) = 0·36 V
∆rGº = – n F E ocell = 2 × 96500 × 0·36 = – 69480 J
nE ºcell 2 × 0· 36 = 12·20
log K c = =
0· 0591 0· 0591
Kc = antilog (12·20) = 1·58 × 1012