Electrochemistry

(Some Important Problem of

NCERT)
Q. 1 Explain with examples the terms weak and strong electrolytes. How can these be distinguished?
Ans. A strong electrolyte is that which dissociates, completely into ion, in solution. The equivalent or
molar conductance of the solution of a strong electrolyte does not change much on dilution. e.g.
HCl, NaOH, KOH, NaCl, NaNO3 etc.
Strong electrolytes are mineral acids (like HCl, H2SO4, HNO3 etc.), alkalies or salts of mineral

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acids and alkalies.
Weak electrolytes are those electrolytes which do not ionize completely in solution.
The equivalent and molar conductance of the solutions of such electrolytes increase too much on
dilution. e.g., organic acid (like CH3 COOH), organic bases (like pyridine etc.) and some salts like
HgCl2.
We can distinguish between the two by measuring their conductance before and after dilution.
LA
Q. 2 Define conductivity and molar conductivity for the solution of an electrolyte.
Discuss their variation with concentration.
Ans. Conductivity (or Specific conductance) of any conductor is the reciprocal of specific resistance
and is denoted by  (Greek, small kappa)
=1/R.l/a
If l =1 cm and a = 1 sq. cm., then
=1/R=l
The conductivity is the conductance between opposite faces of a 1 cm cube.
A

It is expressed in Mhos per centimeter or Siemens per centimeter (S cm–1).

For strong electrolytes there is not much change in conductance with change in concentration but
is case of weak electrolytes it increases much with decreases in concentration.
Molar conductance (m). It is defined as the conducting power of all ions produced by dissolving
one gram molecule (1 mole) of an electrolyte in a certain volume (V mL)
B

m =   V
The unit of molar conductance is S cm2 mol–1.
The value of m is maximum at infinite dilution. i.e. molar conductance increase with dilution.

Q. 3 The conductivity of 0.20 M solution of KCl at 298 K is 0.0248 S cm–1. Calculate its molar
conductivity.
Ans. Using; m = 1000 K / c
= 1000  0.0248 S cm–1 / 0.2 mol L–1 = 124 S cm2 mol–1. [ L–1 = cm–3]

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 Chemistry NCERT Problems- XII
Q. 4 How much charge is required for the following reduction of
(i) 1 mol of Al3+ to Al. (ii) 1 mol of Cu2+ to Cu. (iii) 1 mol of MnO4– to Mn2+.
Ans. (i) Al3+ + 3e–  Al
1 mole 3 mole 1 mole
Thus we need 3 mole electrons to reduce 1 mole Al3+ ions or we need 3  96500 coulombs (or 3
Faraday)
(ii) Cu2+ + 2e–  Cu
1 mole 2 mole 1 mole
Thus we need 2 mole electrons or 2  96500 coulombs (or 2 Faraday)
(iii) MnO4– (aq) + 8H2O (aq) + 8H+ + 5e–  Mn2+ (aq) + 12 H2O (l)

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1 mole 5 mole
Thus we need 5 mole electrons or 5  96500 colombs or 5 Faraday.

Q. 5 How much electricity in terms of Faraday is required to produce

(i) 20.0 g of Ca from molten CaCl2 (ii) 40.0 g of Al from molten Al2O3.
Ans. (i) CaCl2  Ca2+ + 2Cl–
Ca2+ + 2e–  Ca(s)
LA
2 mole 1 mole = 40 g
Thus 40 g Ca (s) needs electrons = 2 moles = 2  96500 coulombs= 2 Faraday
 20 g of Ca(s) will need electrons = 2  20 / 40 = 1 mole or 1  96500 coulombs.= 1 Faraday
(ii) Al2O3  2 Al3+ + 3O2–
Al3+ + 3e–  Al(s)
3 mole 1 mole = 27 g
 27 g of Al needs electrons = 3 moles = 3  96500 coulombs = 3 Faradays.
So 40 g of Al will need electrons = 40 / 27  3 Faradays = 4.44 Faradays.
A

Q. 6 How much electricity is required in coulomb for the oxidation of

(i) 1 mol of H2O to O2 (ii) 1 mol of FeO to Fe2O3.
–
Ans. (i) 2H2O  4H + O2 + 4e (oxidation reaction)
+

2 mole 4 mole
B

Thus 2 moles of water liberate electrons = 4 mole

So 1 mole of water will liberate electrons = 4 / 2 = 2 moles
Hence number of coulombs liberate = 2  96500 Coulombs.
(ii) 2 FeO + H2O  Fe2O3 +2H+ + 2e– (oxidation reaction)
2 mole 2 mole
Thus 2 moles of FeO liberate electrons = 2 moles
So 1 mole of FeO will liberate electrons = 1 mole
Hence number of coulombs liberate = 1  96500 Coulombs.

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 Chemistry NCERT Problems- XII
Q. 7 A solution of Ni(NO3)2 is electrolyzed between platinum electrodes using a current of 5 amperes
for 20 minutes. What mass of Ni is deposited at the cathode?
Ans. Q = 5.0 A  (20  60) S = 6000 Coluombs
Ni2+ + 2e–  Ni
2 mole 1 mole = 58.7 g
2 moles electrons or 2  96500 C produce Ni = 58.7 g
 6000 Coulombs will produce Ni = 58.7 / 2  96500  6000 g = 1.8 g.

Q. 8 Three electrolytic cells A, B, C containing solution of ZnSO4, AgNO3 and CuSO4, respectively
are connected in series. A steady current of 1.5 amperes was passed through them until 1.45 g of

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silver deposited at the cathode of cell B. How long did the current flow? What mass of copper and
of zinc were deposited?
Ans. Ag+ + e–  Ag
1 mole 1 mol = 108 g or 96500 C
108 g of Ag needs Coulombs = 96500
 1.45 g of Ag will need = 96500  1.45 / 108 = 1295.6 C
Thus Q = 1295.6 C
LA
But Q = C  t
 1295.6 = 1.50  t
or t = 1295.6 / 1.50 s = 863.7s
Weight of copper deposited = Wt. of Ag  Eq. Wt. of Cu / Eq. Wt. of Ag
= 1.45  31.75 / 108 = 0.4263 g. [ 63.5 / 2 = 31.75]
Weight of zinc deposited = Wt. of Ag  Eq. Wt. of Zn / Eq. Wt. of Ag
= 1.45  32.7 / 108 = 0.4390 g. [ 65 / 2 = 32.7]
A

Q. 9 Using the standard electrode potentials ECS, predict if the reaction between the following is
feasible:
(a) Fe3+ (aq) and I– (aq) (b) Ag+ (aq) and Cu (s) (c) Fe3+ (aq) and Br– (aq)
(d) Ag (s) and Fe3+ (aq) (e) Br2 (aq) and Fe2+ (aq)
Ans. (a) We can represent the possible reaction as
B

Fe3+(aq) + I–(aq)  Fe2+(aq) + 1/2 I2 (aq)

The two half reaction can then be represented as
(Cathode) Fe3+(aq) + e–  Fe2+(aq); Eº = + 0.77 V
(Anode) I– (aq)  1/2 I2(s) + e–; Eº = – 0.54 V
–
Overall Fe (aq) + I (aq)  Fe (aq) + 1/2 I2; Eºcell = + 0.23 V
3+ 2+

Since Eºcell is positive, so this reaction is feasible.

(b) The possible reaction can be written as
2 Ag+ (aq) + Cu(s)  2 Ag(s) + Cu2+ (aq)
The two half reaction can then be represented as
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 Chemistry NCERT Problems- XII
–
Cathode Ag (aq) + e  Ag(s); Eº = –0.88 V
+

Anode 1 / 2 Cu(s)  1 / 2 Cu2+ (aq) + e–; Eº = – 0.34 V

Overall Ag+(aq) + 1 / 2 Cu(s)  Ag(s) + 1 / 2 Cu2+ (aq); Eºcell = + 0.54 V
Since Eºcell is positive, so this reaction is feasible.
(c) The possible reaction can be represented as
Fe3+ (aq) + Br–(aq)  Fe2+(aq) + 1 / 2 Br2 (aq)
The two half reaction can be written as
Reduction Fe3+(aq) + e–  Fe2+ (aq); Eº = +0.77 V
Oxidation Br– (aq)  1 / 2 Br2 (aq) + e–; Eº = – 1.08 V

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Overall Fe3+(aq) + Br– (aq)  Fe2+ (aq) + 1 / 2 Br2 (aq); Eºcell = –0.31 V
Since Eºcell is negative, so this reaction is not feasible.
(d) The possible reaction can be represented as
Ag(s) + Fe3+ (aq)  Ag+ (aq) + Fe3+(aq)
The two half reactions can be written as
Anode Ag(s)  Ag+ + e–; Eº = –0.80 V
LA
Cathode Fe3+ (aq) e–  Fe2+ (aq); Eº = + 0.77 V
Over all Fe3+(aq) + Ag (s)  Ag+ (aq) + Fe2+; Eº cell = –0.03 V
Since Eº cell is negative, so the given reaction is not feasible.
(e) The two half reactions can be represented as
1 / 2 Br2 (aq) + Fe2+ (aq)  Fe3+ (aq) + Br– (aq)
The two half reactions can be represented as
Cathode 1 / 2 Br2 (aq) + e–  Br– (aq); Eº = + 1.08 V
A

Anode Fe2+ (aq)  Fe3+ (aq) + e–; Eº = –0.77 V

Over all 1 / 2 Br2 (aq) + Fe2+ (aq)  Fe3+ (aq) + Br– (aq); Eº cell = + 0.31 V
Since Eº cell is positive, the reaction is feasible.
B

Q. 10 Predict the products of electrolysis in each of the following:

(i) An aqueous solution of AgNO3 with silver electrodes
(ii) An aqueous solution of AgNO3 with platinum electrodes
(iii) A dilute solution of H2SO4 with platinum electrodes
(iv) An aqueous solution of CuCl2 with platinum electrodes.
Ans. (i) On electrolysis of an aqueous solution of AgNO3 with silver electrodes, silver will get
deposited on cathode and the silver anode will be dissolved slowly.
(ii) On electrolysis of an aqueous solution of AgNO3 with inert electrodes, silver will get obtained
at cathode and oxygen will be evolved at anode.
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 Chemistry NCERT Problems- XII
(iii) Cathode – evolution of hydrogen
Anode – evolution of oxygen.
[Note: Actually in this case electrolysis of H2O occurs]
The two possible anode reactions are
2 H2O(l)  O2(g) + 4H+ (aq) + 4e–; Eº = + 1.23 V … (i)
and 2 SO42–(aq)  S2O82– (aq) + 2e–; Eº = + 1.96 V … (ii)
For dilute solution of H2SO4 reaction (i) is preferred and the product obtained at anode is O2 (g).
However at higher concentration of H2SO4 reaction (ii) is preferred.
(iv) Cathode – Copper will get deposited

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Anode – oxygen gas will be evolved.
Q. 11. Arrange the following metals in the order in which they displace each other from the solution of
their salts.
Al, Cu, Fe, Mg and Zn.
Ans. For this we look at the electrochemical series, a metal placed lower in the series can be displaced
by a metal placed higher up in the series. Thus the order we find is Mg > Al > Zn > Fe > Cu.
LA
Q. 12 Given the standard electrode potentials,
K+ / K = –2.93 V; Ag+ / Ag = 0.80 V; Hg2+ / Hg = 0.79 V;
Mg2+ / Mg = –2.37 V, Cr3+ / Cr = –0.74 V
Arrange these metals in their increasing order of reducing power.
Ans. As we move down the electrochemical series the reduction power decreases as the reduction
potential increases. Thus the arrangement of given metals in order of reducing power will be
K > Mg > Cr > Hg > Ag.

Q. 13 Depict the galvanic cell in which the reaction Zn(s) + 2 Ag+ (aq)  Zn2+ (aq) + 2 Ag (s) takes
A

place. Further show: (i) Which of the electrode is negatively charged (ii) The carries of the current
in the cell. (iii) Individual reaction at each electrode.
Ans. The cell can be depicted as follows
Zn(s) | Zn2+ (aq) || Ag+ (aq) | Ag(s)
B

Anode Cathode
(a) Anode reaction: Zn  Zn2+ + 2e–
Cathode reaction: 2 Ag+ + 2e–  2 Ag (s)
Thus Ag+ | Ag(s) is negatively charged.
(b) Zn(s) | Zn2+ (aq) || Ag+ (aq) | Ag(s)
The current in the cell is carried by the ions. Zn2+ ions go into solution, where as Ag+ ions get
deposited as Ag(s) on cathode.
(iii) Zn  Zn2+ + 2e–(at anode)
2Ag+ + 2e–  Ag(s) (at cathode)

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 Chemistry NCERT Problems- XII
Q. 14 Calculate the standard cell potentials of galvanic cell in which the following reactions take place:
(i) 2Cr(s) + 3 Cd2+ (aq)  2Cr3+ (aq) + 3Cd
(ii) Fe2+ (aq) + Ag+ (aq)  Fe3+ (aq) + Ag(s)
Calculate the rG– and equilibrium constant of the reactions.
Ans. (i) Eº cell = Eº right – Eº left = Eº Cd2+ / Cd – Eº Cr3+ / Cr = –0.4 – (–0.74) = + 0.34 V
We know Eº cell = 0.0591 / 6 log K [ n= 6]
or 0.34 = 0.0591 / 6 log K
or log K = 6  0.34 / 0.0591 or 34.5
 K = 3.16  1034 (Taking antilog)
Again Gº = –2.303 RT log K = –2.303  14  298  34.5 = –196.86 kJ mol–1

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(b) Eºcell = 0.80 – 0.77 = 0.03 V
 0.03 = 0.0591 / 1 log K ( n = 1)
or log K = 0.03 / 0.0591 or 0.507
or K = 3.2 (Taking antilog)
Again Gº = –2.303 RT log K = –2.303  8.314  298  0.507 = –2.895 kJ mol–1.
LA
Q. 15 Write the Nernst equation and e.m.f. of the following cells at 298 K:
(i) Mg(s) | Mg2+ (0.001 M) || Cu2+ (0.0001 M) | Cu(s)
(ii) Fe(s) | Fe2+ (0.001 M) || H+ (1 M) | H2(g) (1 bar) | Pt(s)
(iii) Sn(s) | Sn2+ (0.050 M) || H+ (0.020 M) | H2(g) (1 bar) | Pt(s)
(iv) Pt(s) | Br2 (l) | Br– (0.010 M) || H+ (0.030 M) | H2(g) (1 bar) | Pt(s).
Ans. (i) Nernst Equation
Ecell = Eºcell + 0.059 / 2 log [Cu2+ / Mg2+] ( n = 2)
= Eº Cu / Cu – Eº Mg / Mg + 0.059 / 2 log 10–4 / 10–3
2+ 2+

= 0.37 – (–2.36) + 0.059 / 2 log 10–1

A

= 0.34 + 2.36 – 0.059 / 2 = 0.34 + 2.36 – 0.0295 = 2.6705 V

(ii) Nernst Equation
Ecell = Eºcell + 0.059 / 2 log [1]2 / 10–3 [ n = 2]
3
= 0.44 + 0.059 / 2 log 10 = 0.44 + 3 / 2 0.059= 0.5285 V
(iii) Nernst Equation
B

Ecell = Eºcell + 0.059 log (2)2  (10–3)2 / 5  10–3 [ n = 2]

= 0.14 + 0.059 / 2 [log (4) – log 5 – 3]
= 0.14 + 0.059 / 2 (0.6020 – 0.6990 – 3)
= 0.14 + 0.059 / 2  (–3.0970) = 0.14 + 0.59  (1.0485
= 0.14 – 0.061 = 0.08 V
(iv) Nernst Equation
Ecell = Eºcell + 0.059 / 2 log (0.030)2 / (0.010)2 [ n = 2]
= 1.09 + 0.059 / 2 log 9
= 1.09 – 0.059 / 2  0.9542 = –1.09 + 0.028 = –1.062 V.

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 Chemistry NCERT Problems- XII
Q. 16 In the button cell widely used in watched and other devices the following reaction takes place:
Zn(s) + Ag2O(s) + H2O(l)  Zn2+(aq) + 2Ag(s) + OH–(aq)
Determine E– and rG– for the reaction.
Ans. We know Zn2+ + 2e–  Zn; Eº = –0.76 V
and Ag2O + H2O + 2e–  2 Ag + 2 OH–; Eº = 0.344
Eº cell = 0.344 – (–0.76) = 0.344 + 0.76 = 1.104 V
Also Gº = –nF Eºcell = –2  96500  1.104 J= –2.13  105 J [ n = 2]

Q. 17 The resistance of a conductivity cell containing 0.001 M KCl solution at 298 K is 1500 .
What is the cell constant if conductivity of 0.001 M KCl solution at 298 K is 0.146  10–3 S cm–1.
Ans. Using the relation:

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Cell constant = Resistance  Specific conductance, we get
Cell constant = 1500 ohm  (0.146  10–3) ohm–1 cm–1 = 0.219 cm–1.

Q. 18 The conductivity of sodium chloride at 298 K has been determined at different concentration and
the results are given below:
Concentration / M 0.001 0.010 0.020 0.050 0.100
–1
10   / S m
2
1.237 11.85 23.15 55.53 106.74
LA
Calculate  for all concentrations and draw a plot between  and c1/2. Find the value of –.
Ans. m = Conductivity  Volume or m = 1000  K / M
So for various concentrations the m values can be calculated. These are
(i) 1.237  102  103  103 or 123.7  106
(ii) 11.85  102  103  103 or 118.5  106
(iii) 23.15  102  103  50 or 115.75  106
(iv) 55.53  102  103  20 or 111.06  106
(v) 106.74  102  103  10 or 106.74  106
Now draw graph taking c on x – axis against m on Y axis.
A

From the graph you can find that it is straight line. The intercept of the line gives the value of 0.

Q. 19 Conductivity of 0.00241 M acetic acid is 7.896  10–5 S cm–1.

Calculate its molar conductivity and if – for acetic acid is 390.5 S cm2 mol–1, what is its
dissociation constant?
B

Ans. Using the relation

m = 1000 K / C, we get
m = 1000  7.896  10–5 / 0.00241 = 32.76 s cm2 mol–1
Again  = m / 0
  = 32.76 / 390.5 = 0.838
Now, For acetic acid, CH3COOH  CH3COO– + H+
C (1 – ) C C
K = C .  = 0.00241  0.838  0.0838 = 1.85  10–5.
2

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