1

Class 12th || (CHEMISTRY)

Electrochemistry
NCERT Solutions

2.1 How would you determine the standard electrode 2.3 Consult the table of standard electrode potentials
2+ and suggest three substances that can oxidise
potential of the system Mg ∣ Mg ?
ferrous ions under suitable conditions.
[NCERT Page-36]
[NCERT Page-36]
Sol. A cell with Mg / MgSO 4 (1M ) as one electrode
Sol. In the process of oxidation of Fe2+ to Fe3+ , i.e.,
and standard hydrogen electrode
Fe2+ → Fe3+ + e− ; the reduction potential value is
Pt, H, (1 atm ) H + (1M ) as the second electrode will
negative in nature i.e. E ox = −0.77 V . Only
be set up, and the emf of the cell will be measured
compounds with powerful oxidizing agents and
along with the direction of deflection in the
positive reduction potentials larger than 0.77 V
voltmeter. The direction of deflection indicates
may oxidize Fe2+ to Fe3+ , resulting in a positive
that e − move from the magnesium electrode to the
emf of the cell reaction. This is true for elements
hydrogen electrode, implying that oxidation
occurs on the magnesium electrode and reduction like halogens Br2 ,Cl2 and F2 in the series below
occurs on the hydrogen electrode. As a result, the Fe3+ / Fe2+ .
cell can be represented in the following way:
Mg Mg 2+ (1M ) H + (1M ) H 2 , (1 atm ) Pt 2.4 Calculate the potential of hydrogen electrode in
contact with a solution whose pH is 10.
E cell = E 1 − E Mg 2+ / Mg [NCERT Page-41]
H+
Sol. For hydrogen electrode, H + + e − → 1 / 2H 2
2

put E =0
1
H+ H2 Given: pH = 10
2
Using Nernst equation,
E = − E cell
Mg +2 + /Mg 0.0591 1
E − 1 = Eo + 1 − log
H H2 H H2 n H+ 
2 2  
2.2 Can you store copper sulphate solutions in a zinc
0.0591 1
pot? 0− log −10
1 10
[NCERT Page-36]
 pH = 10 
Sol. Cu is less reactive than Zn, so Cu is easily shifted  
 +  −10  = −0.519  10
  H  = 10 M 
from CuSO4 solution in the following reaction:
 
)
Zn ( s ) + CuSO 4 ( aq ) → ZnSO(qq + Cu ( s ) = 0.591 V
If we express it in relations of emf, it will be like: Hence, the potential of hydrogen electrode in
contact with a solution whose pH is 10 is 0.591 V.
Ecell = Ecu 2+ / Cu − E zn 2+ / Zn
= 0.34 V − ( −0.76 V ) = 1.10 V
2.5 Calculate the emf of the cell in which the
As, The positive Ecell° value indicates the following reaction takes place:
occurrence of spontaneous reactions. if CuSO4 is
Ni ( s ) + 2Ag + ( 0.002M ) → Ni 2+ ( 0.160M ) + 2Ag ( s )
stored in Zn pot, Zn will react will Cu and
originality of CuSO4 will not be maintained. Given that E 0cell = 1.05 V
[NCERT Page-41]

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Sol. Using Nernst equation, 2.8 Suggest a way to determine the Λ m value of
 Ni 2+ 
log  
0.0591 water.
E cell = E cell − 2
n  Ag +  [NCERT Page-51]
  Sol. By using Kohlrausch's law for H2O, we can
0.0519 0.160 calculate Λm .
= 1.05 V − log
2 (0.002)2 The Kohlrausch Law says that when dissociation

= 1.05 −
0.0591
2
(
log log4  104 ) is complete at infinite dilution, each ion adds a
definite amount to the electrolyte's equivalent
0.0591 conductance, regardless of the nature of the ion
= 1.05 − ( 4.6021)
2 with which it is involved, and the value of
= 1.05 − 0.14 V = 0.91 V equivalent conductance at infinite dilution for any
Therefore, the emf of the cell is 0.91 V. electrolyte is the sum of contributions of its ionic
species (cations and anions).
2.6 The cell in which the following reaction occurs: Λm = Λm ( Hcl ) + Λm ( NaOH ) − Λm ( NaCl )
2Fe 3+
( aq ) + 2I ( aq ) → 2Fe ( aq ) + I2 ( s )
− 2+
has
The Λ values of HCl, NaOH and NaCl are
E cell = 0.236 V at 298 K. known as they are strong electrolytes and
Calculate the standard Gibbs energy and the dissociates completely. By putting their values in
equilibrium constant of the cell reaction. the above equation, we can have value of Λm for
[NCERT Page-41] H2O.
Sol. 2Fe3 + ( zg ) + 2I − ( zq ) → 2Fe 2 + ( zg ) + I 2 ( g )
2.9 The molar conductivity of 0.025 mol L–1
For the given cell, the number of transacted
methanoic acid is 46.1 S cm2 mol–1. Calculate its
electrons i.e. n = 2
degree of dissociation and dissociation constant.
Using the given formula;
Given °(H+) = 349.6 S cm2 mol–1 and 0 (HCOO–)
Δ r G 0 = − FE cell
0
= 54.6 S cm2 mol–1.
= −2  96500  0.236
= −45.55 kJ mol − 1 [NCERT Page-51]
Also, Δ r G = −2.303RTlogKC ( )
Sol. Λom ( HCOOH )  H + +  o (HCOO) −
Δ,G −45.55 = 349.6 + 54.6
 logK c = =
2.303RT 2.303  8.314  10−3  298
= 404.2 S cm2 mol−1
= 7.983
Λ cm = 46.1 S cm 2 mol −1
 Kc = antilog (7.983)
= 9.616 × 107 Λcm 46.1
 = = 0.114
Λcm 404.2
2.7 Why does the conductivity of a solution decrease
HCOOH HCOO− + H+
with dilution?
Initial conc c 0 0
[NCERT Page-51]
At equi, c(1− ) c  c 
Sol. The conductance of ions contained in a unit
volume of solution is called conductivity. The c  c c 2
 Ka = =
number of ions per unit volume decreases with c (1 −  ) 1 − 
increase in dilution. As a result, the conductivity
0.025  (0.114) 2
drops. = = 3.67  10−4
1 − 0.114

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PbO2( s ) + SO 24 − ( ag ) + 4H (aq)
+
+ 2e −
2.10 If a current of 0.5 ampere flows through a metallic
wire for 2 hours, then how many electrons would ⎯⎯
→ PbSO 4( s ) + 2H 2O(I)
flow through the wire? Complete reaction:
[NCERT Page-54] Pb( s ) + PbO 2( s ) + 2H 2SO 4( aq ) → 2PbSO 4( s ) + 2H 2O( l )
Sol. As from the formula,
Q = It The reverse process occurs when the battery is
= 0.5 × (2 × 60 × 60) = 3600C charged, in which PbSO4 deposited on the
1 F ⇒ 96500C ⇒ 1 mole of e–1 s electrodes is transformed back to Pb and PbO2,
∴ 3600C is equivalent to the flow of e–1 s and H2SO4 is restored.

6.02 1023 e−1 s

2.14 Suggest two materials other than hydrogen that
6.02  1023
=  3600 = 2.246  1022 e −1 s can be used as fuels in fuel cells.
96500
[NCERT Page-58]
Sol. Methane and Methanol.
2.11 Suggest a list of metals that are extracted
electrolytically.
2.15 Explain how rusting of iron is envisaged as setting
[NCERT Page-54]
up of an electrochemical cell.
Sol. Na, Ca, Mg and Al
[NCERT Page-58]
Sol. The Water present on the surface of iron dissolves
2.12 Consider the reaction:
acidic oxides of air like CO2, SO2 etc, to form
Cr2 O7 2− +14H + + 6e − → 2Cr 3+ + 7H 2O What is acids which dissociate to give H+ ions:
the quantity of electricity in coulombs needed to H 2 O + CO 2 → H 2CO3 2H + + CO32−
reduce 1 mol of Cr2 O 7 2− ? In the presence of H+, iron Fe2+ releases e–1 to
[NCERT Page-54] form Fe3+.
Sol. For the above reaction to take place, 1 mol of Hence, this acts as anode:
+ −
Cr2 O 72− will require 6 F = 6 × 96500 = 579000 C Fe( s ) → Fe(2aq ) + 2e
of electricity. The e–1 lost then travel through the metal to reach
Hence, 579000 C of electricity are required for place where these electrons are utilized by H+ions
reduction of Cr2 O 72− to Cr3+. and dissolved oxygen and reduction takes place.
Thus acts as cathode:
2.13 Write the chemistry of recharging the lead storage O2 ( g ) + 4H + ( aq ) +4e − → 2H 2O( g )
battery, highlighting all the materials that are
The overall reaction is:
involved during recharging.
[NCERT Page-58] 2Fe( s ) + O 2( g ) + 4H(+se ) → 2Fe 2+ ( se ) +2H 2O( s )
Sol. A lead storage battery has a lead anode, a lead As a result, an electrochemical cell is established
cathode with lead dioxide packed ( PbO 2 ) in it, on the surface. The atmospheric oxygen oxidizes
and a 38% H2SO4 solution as the electrolyte. ferrous ions to ferric ions, which mix with water to
When the battery is in operation, the following produce hydrated ferric oxide., Fe2O3.XH2O
reactions occur: which is known as rust.

At Anode: Pb( s ) + SO 24− → PbSO 4( s ) + 2e −

At cathode:

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 4

EXERCISE (ii) In the external circuit, current will travel from

silver to copper.
2.1 Arrange the following metals in the order in which
they displace each other from the solution of their
(
(iii) At anode: Zn ( n ) → Zn 2+ ( q ) + 2e−

salts. At cathode: 2Ag (+zq ) + 2e − → 2Ag ( i )

Al, Cu, Fe, Mg and Zn.
[NCERT Page-59]
2.4 Calculate the standard cell potentials of galvanic
Sol. Mg, Al, Zn, Fe, Cu, Ag
cell in which the following reactions take place:
(i) 2Cr (s) +3Cd 2+ ( aq ) → 2Cr 3+ ( aq ) + 3Cd
2.2 Given the standard electrode potentials,
K + / K = −2.93 V, Ag + / Ag = 0.80 V, (ii) Fe2+ ( aq ) + Ag + ( aq ) → Fe3+ ( aq ) + Ag ( s )

Hg 2+ / Hg = 0.79 V Calculate the Δ r G and equilibrium constant of

Mg 2+ / Mg = −2.37 V,Cr 3+ / Cr = −0.74 V the reactions.

Arrange these metals in their increasing order of

[NCERT Page-59]
reducing power.
[NCERT Page-59] Sol. E = −0.74 V
Cr 3 ,Cr
Sol. The larger the oxidation potential, the easier it is
E = −0.40 V
to oxidize it, and hence the higher the reducing Cr 2 + ,Cl

power. As a result, the reducing power of the E  Ag = 0.80 V

Ag −
elements will be in the following ascending
sequence: Ag < Hg < Cl < Mg < K. E = 0.77 V
Fe3 ,se+−

2.3 Depict the galvanic cell in which the reaction E* cell = E* cathode − E* Anode
= −0.40 V − ( −0.74 V ) = +0.34 V
Zn ( s ) + 2Ag + ( aq ) → Zn 2+ ( aq ) + 2Ag ( s ) takes
place. Further show: Δ r G = nFE cell
(i) Which of the electrode is negatively charged? = −6  96500Cmol−1  0.34 V
(ii) The carriers of the current in the cell.
= 196860CVmol−1
(iii) Individual reaction at each electrode.
= 196860 J mol–1
[NCERT Page-59]
= –196.86 kJ mol–1
Sol. The set-up will be similar to the one seen below.
−Δ r G* = 2.303  8.314  298log K
v 196860 = 2.303  8.314  298log K
or log K = 34.5014
salt bridge K = Antilog 34.5014 = 3.172 × 1034
Ag(s) Zn(s) E cell = +0.80 V − 0.77 V = +0.03 V
Δ,G = nFE  cell−1

(
= −1  96500CVmol−1  ( 0.03 V ))
+ 2+ = −2.895CVmol−1 = −2895 J mol−1
Ag (aq) Zn (aq)
= 2.895 kJ mol−1
(i) The anode, or zinc electrode, will have a
negative charge. Δ r G = 2.303RTlogK
−2895 = −2.303  8.314  298  log K

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or log K = 0.5074 0.0591 0.05

E eell = Ecell − log
or K= Antilog ( 0.5074 ) = 3.22 2 (0.02)2
0.0591 0.05
= 0 − ( −0.14 ) − log
2.5 Write the Nernst equation and emf of the 2 (0.02)2
following cells at 298 K : 0.0591
= 0.14 − log125
(i) Mg ( s ) Mg 2+ ( 0.001M ) Cu 2+ ( 0.0001M ) Cu(s) 2
0.0591
(ii) Fe (s) Fe2+ ( 0.001M ) H + (1M ) H 2 ( g ) (1bar) | Pt(s) = 0.14 − ( 2.0969 ) = 0.078 V
2
(iii) Sn ( s ) Sn 2+ ( 0.050M ) H + ( 0.020M ) H 2 ( g ) (iv) Cell reaction:
2Br + 2H + → Br2 + H 2 ( n = 2 )
(1 bar) ∣ Pt ( s )
Applying Nernst equation:
(iv) Pt ( s ) Br − ( 0.010M ) Br2 (1) H + ( 0.030M )∣ H 2 (g)
0.0591 1
E cell = Ecell − log
(1 bar) ∣ Pt ( s ) 2 2
 Br −   H + 
2
   
0.0591 1
[NCERT Page-59] = ( 0 − 1.08 ) − log
2 (0.01) (0.03)2
2
Sol. (i) Cell reaction:
Mg + Cu 2+ → Mg 2+ + Cu ( n = 2 ) = −1.08 −
0.0591
2
(
log 1.111 107 )
Applying Nernst equation:
0.0591
 Mg 2+  = −1.08 − ( 7.0457 )
log  
0.0591 2
E cell = ECell −
2 Cu 2+  = –1.08 – 0.208 = –1.288 V
 
As a result, oxidation will take place at the
0.0591 10−3
E eell = 0.34 − ( −2.37 ) − log −4 hydrogen electrode, whereas reduction will take
2 10 place at the Br2 electrode.
= 2.71 – 0.02955 = 2.68 V
(ii) Cell reaction: 2.6 In the button cells widely used in watches and
Fe + 2H → Fe+ 2+
+ H2 ( n = 2) other devices the following reaction takes place:
Applying Nernst equation Zn ( s ) + Ag2O ( s ) + H2O ( l ) →
 Fe2+  Zn 2+ ( aq ) + 2Ag ( s ) + 2OH ( aq )
log  
0.0591
Ecell = Eeell − 2
2 H+  Determine Δ r G and E for the reaction.
 
[NCERT Page-59]
0.0591 10−3
E cell = 0 − ( −0.44 ) − log 2 Sol. Given
2 (1)
Zn → Zn 2+ + 2e− ,E = 0.76 V
0.0591
= 0.44 −  ( −3) Ag 2O + H 2O + 2e − → 2Ag + 2OH − , E = 0.344v
2
= 0.44 + 0.0887 = 0.5287 V Ans: In the given reaction, Zn is getting oxidized
(iii) Cell reaction: and Ag2O is being reduced.
Sn + 2H + → Sn 2+ + H 2 ( n = 2 ) E° cell = 0.344 + 0.76 = 1.104 V
Applying Nernst equation: ΔG = nFEF cell = −2  96500 1.104 J
sn 2+  ΔG = −2.13 105 J
log  
0.0591
E ell = Ecell − 2
2 +
H 
 
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2.7 Define conductivity and molar conductivity for the the cell constant if conductivity of 0.001MKCl
solution of an electrolyte. Discuss their variation solution at 298 K is 0.146 10−3 S cm−1 .
with concentration. [NCERT Page-59]
[NCERT Page-59] Sol. From the following relation:
Sol. The conductivity of a solution is defined as the Conductivity
Cell constant = = Conductivity  Resistance
conductance of a solution with a length of 1 cm Conductance

= 0.146 10−3 S cm−1 1500Ω

and a cross-sectional area of 1 s cm.
When the electrodes are one cm apart and the area
of cross-section of the electrodes is large enough = 0.218 cm−1
that the entire solution is contained between them,
the molar conductivity of a solution at a dilution 2.10 The conductivity of sodium chloride at 298 K has
(V) is the conductance of all the ions produced been determined at different concentrations and
from one mole of the electrolyte dissolved in the the results are given below:
Concentration/M 0.001 0.010 0.020 0.050 0.100
solution Vcm3 .Λ m is the most common symbol
102 × /Sm–1 1.237 11.85 23.15 55.53 106.74
for conductivity.
Calculate Am for all concentrations and draw a
The conductivity of a solution (for both strong and
weak electrolytes) diminishes as the concentration plot between Am and c1/2 . Find the value of Λ 0m .
of the electrolyte drops, i.e. as dilution occurs. [NCERT Page-60]
This is owing to the fact that when the solution is 124.0
(0.032, 123.7)
122.0
diluted, the number of ions per unit volume of the
120.0
solution decreases. 118.0 (0.10, 118.5)
Sol.
m (Sem mol )
–1

On dilution, the molar conductivity of a solution 116.0 (0.14, 115.8)

increases as with decrease in concentration of the 114.0
2

112.0 (0.22, 111.1)

electrolyte. This is owing to the fact that when the
110.0
solution is diluted, the number of ions per unit 108.0
(0.32, 106.7)
volume of the solution decreases. The molar 106.0
0.0 0.05 0.10 0.15 0.20 0.25 0.30 0.35
conductivity of a solution increases as the c1/2(mol L –1)1/2
electrolyte content drops. This is because dilution Λ cm = Intercept of Λm axis = 124.0 S cm2 mol–1,
increases both the quantity of ions and their Extrapolation to zero concentration yields this
mobility. The molar conductivity is known as result.
limiting molar conductivity as the concentration Using the following unit conversion factor,
approaches zero.
15 cm −1
=1
100Sm −1
2.8 The conductivity of 0.20 M solution of KCl at
298K is 0.0248 S cm−1. Calculate its molar
conductivity.
[NCERT Page-59]
−1 3 −1
Sol. Λ m = k  1000 = 0.2485 cm  1000 cm L
Molanity −1
0.20moL

= 124Scm2 mol−1

2.9 The resistance of a conductivity cell containing

0.001MKCl solution at 298 K is 1500Ω . What is

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 7

Al3+ + 3e → Al . The amount of charge needed for

Concentraction K(Sm–1) K(Scm–1) 1000  k C1.2(M1/2)
m = reduction of 1 mol will be:
(M) Molanity

(Scm2 mol−1 ) Al3+ = 3 F = 3  96500C = 289500C .

–3
10 1.237 × 1.237 × 1000  1.237  10−4 0.316 (ii) cupric ion needs to lose two electrons to be in
10–1 10–4 10−2
copper (0) state. The electrode reaction occurring
= 123.7
10–2 11.85 × 11.85 × 1000  11.85  10−4 0.100 is as follows: Cu 2+ + 2e− → Cu
10–2 10–4 10−2
The amount of charge required for conversion of
= 1118.5
2 × 10–2 23.15 × 23.15 × 1000  23.15  10−4 0.141 1 mol of Cu 2+ = 2 F = 2  96500 = 193000C .
10–2 10–4 2  10−2
(iii) in the compound MnO4 , manganese is in +7
= 115.8
5 × 10–2 55.53 × 55.53 × 1000  55.53  10−4 0.224 oxidation state; which is reduced to +2 oxidation
10–2 10–4 5  10−2 state with the release of five electrons.
MnO 4 → Mn 2+ i.e. Mn 7 + + 5e − → Mn 2+
= 111.1
10–1 106.74 × 106.74 × 1000  106.74  10−4 0.316
10–2 10–4 10−1 The Quantity of charge needed for reduction of
= 106.7
1 mol of MnO4 to Mn2+ = 5 F = 5 × 96500
C = 4825000 C.
2.11 Conductivity of 0.00241M acetic acid is
7.896 10−5 S cm−1. Calculate its molar
conductivity. If Λ 0m for acetic acid is 2.13 How much electricity in terms of Faraday is
2 −1 required to produce;
390.5 S cm mol , what is its dissociation
constant? (i) 20.0 g of Ca from molten CaCl2 ?
[NCERT Page-60] (ii) 40.0 g of Al from molten Al2O3 ?
  1000 [NCERT Page-60]
Sol. Λ cm =
Molarity 2+ −
Sol. (i) Ca + 2e → Ca

=
( 7.896 10 −5
S cm −1
) 1000 cm 3 −1
L As There are two electrons transacted in the above
reaction, therefore 1 mol of Ca or 40 g of Ca
0.241molL−1
will require = 2 F electricity and 20 g of Ca will
= 32.76 S cm2 mol−1
require = 1 F of electricity.
Λcm
32.76
= * = = 8.4  10−2 (ii) Al3+ + 3e− → A1
Λ 390.5
As the number of electrons transacted in the above
( )
2
C 2 0.24  8.4  10−2 reduction of aluminum ion is three,
ks = = Therefore, 1 mol of Al or 27 g of A1 will
1−  1 − 0.084
−5 require = 3 F electricity
= 1.86 10
And, 40 g of A1 will require electricity
2.12 How much charge is required for the following 3
=  40 = 4.44 F of electricity.
reductions: 27
(i) 1 mol of Al3+ to Al ?
(ii) 1 mol of Cu2+ to Cu ? 2.14 How much electricity is required in coulomb for
(iii) 1 mol of MnO4– to Mn2+ ? the oxidation of
[NCERT Page-60] (i) 1 mol of H2O to O2 ?
Sol. (i) Aluminum ion have to lose three electrons to (ii) 1 mol of FeO to Fe2O3 ?
be in aluminum elemental state and the reaction is [NCERT Page-60]

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Sol. (i) The oxidation of water occurs in the 2.16 Three electrolytic cells A, B, C containing
following way: solutions of ZnSO4 ,AgNO3 and CuSO4,
1 respectively are connected in series. A steady
H 2 O ⎯⎯ → H 2 + O2
2 current of 1.5 amperes was passed through them
1
Or O2− ⎯⎯ → O2 + 2e until 1.45 g of silver deposited at the cathode of
2 cell B. How long did the current flow? What mass
The number of electrons transacting are two. of copper and zinc were deposited?
Therefore the amount of electricity needed [NCERT Page-60]
= 2 F = 2  96500C = 193000C Sol. Given: I = 1.5 A, W = 1.5 g of
(ii) The oxidation reaction of FeO takes place in
Agt = ?,E = 108,n = 1
the following manner:
Applying Faraday's first law of electrolysis,
1 1
FeO + O 2 → Fe 2 O3 W = Zlt
2 2
Or
Or Fe2+ → Fe3+ + e− E
The electron transfer is of one electron unit, W= It
nF
therefore the Quantity of electricity essential By substituting the values provided in the about
= 1 F = 96500C formula, t can be calculated;
1.45  96500
2.15 A solution of Ni ( NO3 )2 is electrolysed between t= = 863.73 seconds.
1.5  108
platinum electrodes using a current of 5 amperes Now for Cu, W1 = 1.45 g (given) of
for 20 minutes. What mass of Ni is deposited at AgE1 = 108, W2 = ?
the cathode?
E2 = 31.75
[NCERT Page-60]
Applying Faraday's 2nd law of electrolysis
Sol. Firstly, we will find charge in coulombs using the
W1 E1
formula: Q = It =
W2 E 2
Amount of electricity passed
1.45 108
( Q) = (5 A)  ( 20  60sec) = 6000C =
W2 31.75
The reduction of nickel occurs in the following
145  31.75
way: W2 =
108
Ni2+ + 2e− ⎯⎯ → Ni Copper deposited = 0.426 g of Cu
Therefore, 2 For 2  96500C is the amount of
likewise, for Zn, W1 = 1.45 g of
charge deposit for 1 mol of Ni = 58.7 g
Ag,E1 = 108, W2 = ?E2 = 32.65
Now,
The 6000C of charge will deposit W1 E1
Using formula, =
58.7  6000 W2 E 2
= = 1.825 g of Ni
2  96500 1.45 108
=
W2 32.65
145  32.65
W2 = = 0.438 of Zn
108
Zinc deposited by 1295.6 gC is 0.438 g.

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 9

2.17 Using the standard electrode potentials given in 2.18 Predict the products of electrolysis in each of the
Table 3.1, predict if the reaction between the following:
following is feasible: (i) An aqueous solution of AgNO3 with silver
(i) Fe3+ ( aq ) and I − (aq) electrodes.
(ii) An aqueous solution of AgNO3 with
(ii) Ag + (aq) and Cu ( s )
platinum electrodes.
(iii) Fe3+ (aq) and Br − (aq) (iii) A dilute solution of H2SO4 with platinum
(iv) Ag ( s ) and Fe3+ (aq) electrodes.
2+ (iv) An aqueous solution of CuCl2 with platinum
(v) Br2 (aq) and Fe (aq).
[NCERT Page-60] electrodes.
Sol. (i) The reaction is feasible if the emf of the cell [NCERT Page-60]
reaction is positive. Sol. (i) AgNO3 ( s ) ⎯⎯
→ Ag +
( aq ) + NO3− ( aq )
1
Fe3+ ( aq ) + I(−eq ) → Fe2+ ( aq ) + I 2 ( g ) H 2O H + + OH −
2
At cathode: The discharge potential of Ag + ions is
i.e. Pt / I 2 / I − ( aq ) Fe3+ ( aq ) Fe 2+ ( aq ) Pt
lower than that of H+ ions. As a result, Ag ions
 E oecl = E  −+ − E o
1/2L2 
will be deposited as Ag rather than H+ ions.
Fe Fe

= 0.77 − 0.54 = 0.23V (Feasibles) At anode: When the Ag. anode is attacked by
(ii) 2Ag(+( s ) ) + Cu ( s ) → 2Ag( s ) + Cu (2aq
+
) NO3− ions, the Ag dissolves and forms ions in the
solution.
i.e., Cu Cu 2+ ( aq ) Ag (+a ) Ag
Ag ( s ) ⎯⎯
→ Ag + ( aq ) + e
 E oestl = E* − E ,Cu
s
Δg + (ii) At cathode: The discharge potential of Ag +
= 0.80 − 0.34 = 0.46 V (Feasible) ions is lower than that of H+ ions. As a result, Ag
1
(iii) Fe3+ ( aq ) + Br(−eq ) → Fe(2eq
+
) + 2 Br2(  ) ions will be deposited as Ag rather than H+ ions.
At anode: Because the anode is not attackable,
E cell = 0.77 − 1.09 = −0.32v (Not feasible )
OH ions have a lower discharge potential than
) → Ag ( aq ) + Fe ( aq )
+ + 2+
(iv) Ag( s ) + Fe3( aq NO3− ions. As a result, OH will be evacuated
E ocell = 0.77 − 0.80 = −0.03v (Not feasible ) first, followed by NO3− ions, which will
1
Br2( g ) + Fe2+ ( aq ) → Br(−aq ) , Fe3+ ( aq )
disintegrate and release O2.
(v)
2 4OH → 2H 2O(1) + O 2( g )
E cell = 1.09 − 0.77 = 0.32 V (Feasible)
(iii) H 2SO 4 → 2H + + SO 4 2−
H 2O H + OH −
At cathode: H+ + e− → H
H + H → H 2( g )

At anode: OH− → OH + e−
4OH → 2H 2 O + O 2( g )

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 10

Therefore, Hydrogen gas is released at the cathode

and O2 gas at the anode.

(iv) CuCl2 → Cu 2+ + 2Cl −

H 2O H + OH −
At cathode: Cu 2+ ions will be reduced more than
H+ ions, resulting in copper deposition at the
cathode.
Cu 2+ + 2e− → Cu
At anode: Clions will be released first, followed
by OH ions that will stay in solution.
Cl → Cl + e−
Cl + Cl → Cl2( g )

Hence, copper will get set down on the cathode

and Cl2 gas will be liberated at the anode.

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