Chapter 3

Electrochemistry
Intext Questions Pg-68
Q. 1 How would you determine the standard electrode potential of the
system Mg2+|Mg?
Answer:
To determine the standard electrode potential of the system Mg2+|Mg,
connect it to the standard hydrogen electrode (SHE). Keep the Mg2+|Mg
N AT IS
system as cathode and SHE as anode. This is represented as shown
below.

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Pt(s) | H2(g, 1 bar) | H+ (aq, 1 M) ||Mg2+ (aq, 1M) | Mg
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The electrode potential of a cell is given by

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E⊖ = E⊖R – E⊖L
ED PR

Where,
E⊖R- Potential of the half-cell in the right side of the above
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representation
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E⊖L- Potential of the half-cell in the left side of the above representation
It is to be noted that the potential of the standard hydrogen electrode is
zero.
Therefore, E⊖L = 0
E⊖ = E⊖R – 0
⇒ E⊖ = E⊖R
Q. 2 Can you store copper sulphate solutions in a zinc pot?
Answer:
NO, because Zn is very reactive with Cu. It reacts with copper sulphate
to form zinc sulphate i.e., Zn displaces Cu and metallic Cu is also
formed.
The reaction is given as:
Zn + CuSO4 ⇒ ZnSO4 + Cu
Q. 3 Consult the table of standard electrode potentials and suggest three
substances that can oxidize ferrous ions under suitable conditions
Answer:

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For a substance to oxidize Fe2+to Fe3+ ion, it must have high reduction
potential than Fe3+. The reduction potential of Fe3+ to Fe2+ reaction is

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0.77V, the substances which have reduction potentials higher than this
value will oxidize Fe2+ ions. Comparing the values, from the table:
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Reaction (oxidized → Reduced form) E⊖ / V
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from + ne-
F2(g) + 2e- →2F- 2.87
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Co3+ + e- →Co2+ 1.81
H2O2 + 2H+ + 2e- → 2H2O 1.78
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MnO4- + 8H+ + 5e- → Mn2+ + 4H2O 1.51

Au3+ + 3e- →Au(s) 1.40
Cl2(g) + 2e- →2CI- 1.36
Cr2O72- + 14H+ + 6e- → 2Cr3+ + 7H2O 1.33
O2(g) * 4H+ + 4e- →2H2O 1.23
MnO2(s) + 4H+ + 2e- →Mn2+ + 2H2O 1.23
Br2 + 2e- →2Br- 1.09
NO3- + 4H+ + 3e- →NO(g) + 2H2O 0.97
2Hg2+ + 2e- →Hg22+ 0.92
Ag+ + e- →Ag(s) 0.80
Fe3+ + e- → Fe2+ 0.77
F2, Br2, Cl2, H2O2 can oxidize ferrous ions.
Intext Questions Pg-73
Q. 4 Calculate the potential of hydrogen electrode in contact with a
solution whose pH is 10.
Answer:
Given:
For hydrogen electrode, pH = 10
n=1
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(n = moles of e- from balanced redox reaction)

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pH= 10
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⇒ [H+] = 10-10 M

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We know,
[𝐻 ]
ED PR

0.0591
Ecell = E0 – log [𝐻 +2 ]
1
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Here, E0 = 0 (because it is a concentration cell)
P[H2] = 1
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0.0591 1
⇒ 𝐸𝑐𝑒𝑙𝑙 = 0 − log
1 10−10
0.0591
⇒ 𝐸𝑐𝑒𝑙𝑙 = − × log(1010 )
1
0.0591
⇒ 𝐸𝑐𝑒𝑙𝑙 = − × 10 log(1)
1
0.0591
⇒ 𝐸𝑐𝑒𝑙𝑙 = − × 10
1

⇒ 𝐸𝑐𝑒𝑙𝑙 = −0.591 𝑉
Q. 5 Calculate the emf of the cell in which the following reaction takes
place:
Ni(S) + 2Ag+ (0.002M) → Ni2+ (0.160 M) + 2Ag(s)
0
Given that 𝐸(𝑐𝑒𝑙𝑙) = 1.05 V
Answer:
Given:
[Ag+] = 0.002 M
[Ni2+] = 0.160 M
n=2

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(n = moles of e- from balanced redox reaction)
E0cell= 1.05 V

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Now, using the Nernst equation we get,
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0 0.0591 [𝑁𝑖 2+ ]
𝐸𝑐𝑒𝑙𝑙 = 𝐸 − log [𝐴𝑔+]2

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1
0.0591 0.160
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⇒ 𝐸𝑐𝑒𝑙𝑙 = 1.05 − log [ ]

2 (0.002)2
0.0591
× log(4 × 104 )
T
⇒ 𝐸𝑐𝑒𝑙𝑙 = 1.05 −
2
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⇒ 𝐸𝑐𝑒𝑙𝑙 = +0.91𝑉
Q. 6 The Cell in which the following reaction occurs:
2Fe3+(aq) + 2I– (aq) → 2Fe2+(aq) + I2(s) has E0cell = 0.236V at 298 K.
Calculate the standard Gibbs energy and the equilibrium constant of the
cell reaction.
Answer:
Given:
2Fe3+(aq) + 2I– (aq) → 2Fe2+(aq) + I2(s)
E0cell = 0.236V
n = moles of e- from balanced redox reaction = 2
F = Faraday's constant = 96,485 C/mol
T = 298 K.
Using the formula, we get,
∆rG0 = – nFE0cell
⇒ ∆rG0 = – 2 × FE0cell
⇒ ∆rG0 = −2 × 96485 C mol-1 × 0.236 V
⇒ ∆rG0 = −45540 J mol−1
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⇒ ∆rG0 = −45.54 kJ mol−1

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Now,
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∆rG0 = −2.303RT log Kc

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Where, K is the equilibrium constant of the reaction.
ED PR

R is the gas constant; R = 8.314 J-mol-C-1

⇒ −45540 J mol−1 = –2.303× (8.314 J-mol-C-1) × (298 K) × (log Kc)
T
Solving for Kc we get,
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⇒ log Kc = 7.98
Taking antilog both side, we get
⇒ Kc = Antilog (7.98)
⇒ Kc = 9.6 × 107
Trick to remember:
 N AT IS Intext Questions Pg-83

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Q. 7 Why does the conductivity of a solution decrease with dilution?
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Answer:
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The conductivity of a solution depends on the amount of ions present per
volume of the solution. When diluted, the concentration of the ions
ED PR

decreases which implies that the number of ions per volume decreases
thus, in turn, conductivity decreases.
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Q. 8 Suggest a way to determine the Λ°m value of water
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Answer:
Λ°m (H2O) = Λ°m(H+) + Λ°m(OH-)
For calculation purpose, Λ°m(Na+) and Λ°m(Cl-) are added and
subtracted.
Λ°m (H2O) = Λ°m(H+) + Λ°m(OH-)+ Λ°m(Na+) - Λ°m(Na+) + Λ°m(Cl-) -
Λ°m(Cl-)
Λ°m (H2O) = Λ°m(HCl) + Λ°m(NaOH) - Λ°m(NaCl)
If we know the other values, Λ°m (H2O) can be calculated.
Q. 9 The molar conductivity of 0.025 mol L–1 Methanoic acid is 46.1 S
cm2 mol–1. Calculate its degree of dissociation and dissociation constant.
Given λ0(H+) = 349.6 S cm2 mol–1 and λ0 (HCOO–) = 54.6 S cm2 mol–1.
Answer:
C = 0.025 mol L-1
Am = 46.1 Scm2 mol-1
λ0 (H+) = 349.6 Scm2 mol-1
λ0 (HCOO-) = 54.6 Scm2 mol-1
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Λ0m (HCOOH) = Λ 0(H+) + Λ0(HCOO-)

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= 349.6 + 54.6
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= 404.2 S cm2 mol-1
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Now, the degree of dissociation:
Λ𝑚 (𝐻𝐶𝑂𝑂𝐻)
𝛼=
ED PR

Λ0 𝑚(𝐻𝐶𝑂𝑂𝐻)

46.1 𝑆 𝑐𝑚2 𝑚𝑜𝑙 −1

=𝛼=
T
404.2 𝑆 𝑐𝑚2 𝑚𝑜𝑙 −1

∴ α = 0.114(approximately)
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Thus, dissociation constant:

𝐶𝛼 2
k=
1−𝛼
(0.025𝑚𝑜𝑙 𝐿−1 )×(0.114)2
=k=
1−0.114

⇒ K = 3.67 × 10-4 mol L-1

Intext Questions Pg-86
Q. 10 If a current of 0.5 ampere flows through a metallic wire for 2
hours, then how many electrons would flow through the wire?
Answer:
Current I = 0.5A
Time t = 2hrs = 2×60×60 = 7200 seconds
Charge Q = I×t
Q = 0.5×7200 = 3600 C
Charge carried by 1 mole of electrons (6.023×1023electrons) is equal to
96487C.
No of electrons = 6.023×1023 × 3600/96487
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No of electrons = 2.25×1022 electrons.

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Q. 11 Suggest a list of metals that are extracted electrolytically.
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Answer:

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Metals with greater reactivity can be extracted electrolytically. Sodium,
potassium, calcium, lithium, magnesium, aluminium which are present
ED PR

in the top of the reactivity series are extracted electrolytically.

Q. 12 Consider the reaction: Cr2O72– + 14H+ + 6e–⇒ 2Cr3+ + 7H2O. What
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is the quantity of electricity in coulombs needed to reduce 1 mol of
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Cr2O72–?
Answer:
Cr2O72– + 14H+ + 6e–⇒ 2Cr3+ + 7H2O
For reducing one mole of Cr2O72–, 6 mole of electrons are required.
Hence, 6 faraday charge is needed. Hence, 6F = 6×96487 = 578922 C.
Thus, the quantity of electricity is needed is 578922 C.
Intext Questions Pg-90
Q. 13 Write the chemistry of recharging the lead storage battery,
highlighting all the materials that are involved during recharging
Answer:
Anode: Lead (Pb)
Cathode: a grid of lead packed with lead oxide (PbO2)
Electrolyte: 38% solution of sulphuric acid (H2SO4)
The cell reactions are as follows:
Pb (s) + SO2-4(aq) ⇒ PbSO4(s) + 2e- (anode)
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PbO2(s) + SO2-4(aq) + 4H+(aq) +2e-⇒ PbSO4(s) +2H2O(l) (cathode)

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Pb(s) + PbO2(s) +2H2SO4(aq)⇒ 2PbSO4(s) +2H2O(l)
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(overall cell reaction)

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On charging, all these reactions will be reversed.
ED PR

Q. 14 Suggest two materials other than hydrogen that can be used as

fuels in fuel cells.
T
Answer:
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Methane, oxygen & methanol can be used as fuels in fuel cells other
than hydrogen.
Q. 15 Explain how rusting of iron is envisaged as setting up of an
electrochemical cell.
Answer:
In the corrosion reaction, due to the presence of air and moisture,
oxidation takes place at a particular point of an object made of iron. That
spot behaves as the anode. The reaction at the anode is given by,
Fe(s) ⇒ Fe2+ (aq) + 2e-
Electrons released at the anodic spot move through the metal and go to
another spot of the object, wherein presence of H+ ions, the electrons
reduce oxygen. This spot behaves as the cathode. These H+ ions come
either from H2CO3, which are formed due to the dissolution of carbon
dioxide from the air into water. The cathodic reaction is given by
O2(air) + 4H(aq) +4e- ⇒ 2H2O
The overall reaction is given by,
2Fe(s) + O2(air) + 4H(aq)+⇒ 2Fe2+ + 2H2O

N AT IS Exercises

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Q. 1 Arrange the following metals in the order in which they displace
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each other from the solution of their salts.

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Al, Cu, Fe, Mg, and Zn.
Answer:
ED PR

The order in which the given metals displace each other from the
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solution of their salts is given by,
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Mg>Al> Zn> Fe> Cu

Explanation -
A metal of stronger reducing power displaces another metal of weaker
reducing power from its solution of salt. The order of increasing the
reducing power of given metals is Cu< Fe< Zn< Al<Mg. Hence, we can
interpret as Mg can displace Cu from its salt solution, but Cu cannot
displace Mg. The order in which the given metals displace each other
from the solution of their salts is given by, Mg>Al> Zn> Fe> Cu. This is
hence arranged in decreasing order of its reactivity.
Q. 2 Given the standard electrode potentials,
K+ /K = –2.93V, Ag+ /Ag = 0.80V,
Hg2+ /Hg = 0.79V
Mg2+ /Mg = –2.37 V, Cr3+ /Cr = – 0.74V
Arrange these metals in their increasing order of reducing power.
Answer:
Reducing power of metals increase with the decrease of reduction
potential. Hence, the increasing order of reducing power will be as,
Ag < Hg < Cr < Mg < K
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Explanation -

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When the reduction potential is lower, the element has more tendency to
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get oxidized and thus more will be reducing power. The metal that has
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more negative electrode potential will be the one with more reducing

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power. Thus, here potassium(K) has the highest reducing power among
the given elements.
ED PR

Q. 3 Depict the galvanic cell in which the reaction

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Zn(s) + 2Ag+ (aq) → Zn2+ (aq) + 2Ag(s) takes place. Further show:
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1) Which of the electrode is negatively charged?

2) The carriers of the current in the cell.
3) Individual reaction at each electrode.
Answer:
The galvanic cell corresponding to the given redox reaction can be
represented as:
Zn|Zn2+ (aq)||Ag+ (aq)|Ag
1) Zn electrode (anode) is negatively charged because, at this electrode,
Zn is oxidized to Zn2+, causing electron accumulation at the anode.
2) Electrons (ions) are the carriers of the current in the cell and in the
external circuit, current flows from Ag (cathode) to Zn(anode) which is
normally opposite to the electron flow which is from anode to cathode.
3) At anode:
Zn(s)⇒ Zn2+ (aq) + 2e–
At cathode:
Ag+ (aq) + e– ⇒ Ag(s)

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O C D
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ED PR

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Q. 4 Calculate the standard cell potentials of galvanic cell in which the

following reactions take place:
(i) 2Cr(s) + 3Cd2+ (aq) → 2Cr3+ (aq) + 3Cd
(ii) Fe2+ (aq) + Ag+ (aq) → Fe3+ (aq) + Ag(s)
Calculate the ΔrG0 and equilibrium constant(K) of the reactions.
Answer:
(i) Known - E0Cr3 + /Cr = - 0.74 V
E0Cd2 + /Cd = - 0.40 V
∆rG0 =?
K =?
The galvanic cell of the given reaction is written as -
Cr(s)|Cr3+ (aq)|| Cd2+ (aq)|Cd(s)→ Reaction 1
Hence, the standard cell potential is given as,
E0 = E0R - E0L
= - 0.40 - (- 0.74)
∴ E0 = + 0.34 V
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To calculate the standard Gibb’s free energy, ∆rG0, we use,

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∆rG0 = - nE0F → Equation 1
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where nF is the amount of charge passed and E0 is the standard reduction

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electrode potential.
Substituting n = 6 (no. of e - involved in the reaction 1), F = 96487 C
ED PR

mol-1,
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E0 = + 0.34 V in Equation 1, we get,
∆rG0 = - 6×0.34V×96487 C mol-1
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= - 196833.48 CV mol-1
= - 196833.48 J mol-1
∴ ∆rG0 = - 196.83348 kJ mol-1
To find out the equilibrium constant, K, we use the formula,
𝑛𝐸 0
log k =
0.0591
6×0.34𝑉
=
0.0591
log K = 34.5177
K = antilog 34.5177
∴ K = 3.294 × 1034
The standard Gibb’s free energy, ∆rG0 is - 196.83348 kJ mol – 1 and
equilibrium constant, K is 3.294 × 1034
(ii) Known -
E0Fe3+ /Fe2+ = 0.77V
E0Ag+ /Ag = 0.80 V
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∆rG0 =?

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O C D
K =?O IO
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The galvanic cell of the given reaction is written as -

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Fe2+ (aq)|Fe3+ (aq)|| Ag+ (aq)|Ag(s)→ Reaction 1
Hence, the standard cell potential is given as,
ED PR

E0 = E0R - E0L
T
= 0.80 - (0.77)
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∴ E0 = + 0.03 V
To calculate the standard Gibb’s free energy, ∆rG0, we use,
∆rG0 = - nE0F → Equation 1
where nF is the amount of charge passed and E0 is the standard reduction
electrode potential.
Substituting n = 1 (no. of e - involved in the reaction 1), F = 96487 C
mol-1, E0 = + 0.03V in Equation 1, we get,
∆rG0 = - 1×0.03V×96487 C mol-1
= - 2894.61 CV mol - 1
= - 2894.61 J mol-1
∴ ∆rG0 = - 2.89461 kJ mol-1
To find out the equilibrium constant, K, we use the formula,
𝑛𝐸 0
log k =
0.0591
1×0.03𝑉
=
0.0591

log K = 0.5076
K = Antilog 0.5076
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∴ K = 3.218

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The standard Gibb’s free energy, ∆rG0 is - 2.89461 kJ mol–1 and
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equilibrium constant, K is 3.218
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Q. 5 Write the Nernst equation and emf of the following cells at 298 K:
(i) Mg(s)|Mg2+ (0.001M) ||Cu2+ (0.0001 M) |Cu(s)
ED PR

(ii) Fe(s)|Fe2+ (0.001M) ||H+ (1M) |H2(g)(1bar) | Pt(s)

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(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).
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Answer:
Ecell =?
(i) Mg + Cu2+ → Mg2+ + Cu (n = 2)
E0Cu2+ /Cu+ = 0.34V
E0Mg2+ /Mg = - 2.37 V
E0cell = E0R - E0L
E0cell = 0.34 - (- 2.37) → Equation 1
Using Nernst equation, we get,
 0 0.0591 𝑀𝑛2+
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − log → Equation 2
2 𝐶𝑢2+

Substituting Equation 1 in equation 2, we get,

0.0591 10−3
∴ Ecell = 0.34 - (- 2.37) - log
2 10−4
0.0591
= 2.71 - log 10
2

= 2.71 - 0.02955
∴ Ecell = 2.68 V

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The e.m.f of the cell, Ecell is 2.68 V
ii) Fe + 2H+ → Fe2+ + H2 (n = 2)

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E0H+ /H2 = 0 V
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E0Fe2+ /Fe = - 0.44 V

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E0cell = E0R - E0L
ED PR

E0cell = 0 - (- 0.44) → Equation 1

Using Nernst equation, we get,
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0 0.0591 𝐹𝑒 2+
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − log (𝐻 +)2 →Equation 2
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Substituting Equation 1 in equation 2, we get,

cell 0.0591 10−3
∴E = 0 - (- 0.44) - log
2 (1)2
0.0591
= 0.44 - (−3)
2

= 0.44 - 0.0887
∴ Ecell = 0.5287 V
The e.m.f of the cell, Ecell is 0.5287 V
iii) Sn + 2H+ → Sn2+ + H2 (n = 2)
E0H + /H2 = 0 V
E0Sn2+ /Sn = - 0.14V
E0cell = E0R - E0L
E0cell = 0 - (- 0.14) → Equation 1
Using Nernst equation, we get,
0 0.0591 𝑆𝑛2+
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − log →Equation 2
2 (𝐻 + )2

Substituting Equation 1 in equation 2, we get,

N AT IS
∴ Ecell = 0 - (- 0.14) -
0.0591
2
log
0.05
(0.02)2

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O C D
00591
= 0.14 - (log 125)
O IO 2
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= 0.14 - 0.0295×2.0969

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∴ Ecell = 0.08 V
ED PR

The e.m.f of the cell, Ecell is 0.08 V

iv) 2Br- + 2H+ → Br2+ H2 (n = 2)
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E0H+ /H2 = 0 V
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E0Br2/Br- = 1.08V
E0cell = E0R - E0L
E0cell = 0 - (1.08) → Equation 1
Using Nernst equation, we get,
0 0.0591 1
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − log (𝐵𝑟 −)(𝐻 +)2 →Equation 2
2

Substituting Equation 1 in equation 2, we get,

0.0591
∴ Ecell = 0 - (1.08) - log(1.111 × 107 )
2
 0.0591
= - 1.08 - (7.0457)
2

= - 1.08 - 0.208
∴ Ecell = 1.288 V
The e.m.f of the cell, Ecell is 1.288 V
Q. 6 In the button cells widely used in watches and other devices the
following reaction takes place:
Zn(s) + Ag2O(s) + H2O(l)→ Zn2+ (aq) + 2Ag(s) + 2OH–(aq). Determine
ΔrG0 and E0 for the reaction.
N AT IS
Answer:

C N
PY
O C D
Given - Zn → Zn2+ + 2e-, E0 = 0.76V (anode)
O IO
Ag2O + H2O + 2e- →2Ag + 2OH-, E0 = 0.344V (cathode), n = 2
D U AA

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ΔrG0 =?
E0cell =?
ED PR

Zn is oxidized and Ag2O is reduced.

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Hence, the standard cell potential, E0cell is given as,
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E0cell = E0R - E0L

E0cell = 0.344 + 0.76
∴ E0cell = 1.104 V
To calculate the standard Gibb’s free energy, ∆rG0, we use,
∆rG0 = - nE0F → Equation 1
= - 2×96487×1.104 J
= - 213043.296 J
∴ ∆rG0 = - 2.13×105 J
The standard cell potential, E0cell is 1.104 V and the standard Gibb’s
free energy, ∆rG0 is - 2.13×105 J
Q. 7 Define conductivity and molar conductivity of the solution of an
electrolyte. Discuss their variation with concentration.
Answer:
The conductivity of a solution is defined as the conductance of one-unit
volume of solution kept between two platinum electrodes with a unit
area of cross-section and at a distance of unit length.
The molar conductivity of the solution is defined as the conducting
N AT IS
power of all the ions produced by one-gram mole of an electrolyte in a

C N
solution. It is denoted by ∧m.

PY
O C D
O IO
The conductivity of a solution (both for strong and weak electrolytes)
D U AA

always decreases with the decrease in concentration of the electrolyte

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i.e., on dilution. This pattern is seen because the number of ions per unit
volume that carry the current in the solution decreases on dilution. The
ED PR

molar conductivity of the solution increases with the decrease in

concentration of the electrolyte. This is because both the number of ions
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as well as mobility of ions increase with dilution.
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Q. 8 The conductivity of 0.20 M solution of KCl at 298 K is 0.0248 S

cm–1. Calculate its molar conductivity.
Answer:
Given -
Molarity, C = 0.20 M
Electrolytic conductivity of a solution, κ = 0.0248 S cm–1
Molar conductivity =?
𝑘
Molar conductivity, ∧m = × 1000 S cm2 mol-1
𝑐
 0.0248 𝑆 𝑐𝑚−1 ×1000 𝑐𝑚3 𝐿−1
=
0.20 𝑚𝑜𝑙 𝐿−1

∴ ∧m = 124 S cm2 mol-1

Molar conductivity(∧m) of 0.20 M solution of KCl at 298 K is 124 S
cm2 mol-1
Q. 9 The resistance of a conductivity cell containing 0.001M KCl
solution at 298 K is 1500 Ω. What is the cell constant if the conductivity
of 0.001M KCl solution at 298 K is 0.146 × 10–3 S cm–1.
Answer:
N AT IS
Given -

C N
PY
O C D
Resistance of a conductivity cell, R = 1500
O IO
Electrolytic conductivity of a solution, κ = 0.146 × 10–3 S cm–1
D U AA

O
Cell constant =?
𝑐𝑒𝑙 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
Conductivity, κ =
ED PR

𝑟𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒

Cell constant = κ × R
T
= 0.146 × 10–3 S cm–1×1500
©

Cell constant = 0.219 cm-1

The cell constant of the cell containing 0.001M KCl solution at 298 K is
0.219 cm-1
Q. 10 The conductivity of sodium chloride at 298 K has been determined
at different concentrations and the results are given below:
Concentration 0.001 0.010 0.020 0.050 0.100
/M
102 × k/Sm-1 1.237 11.85 23.15 55.53 106.74
Calculate Λm for all concentrations and draw a plot between Λm and
c1/2. Find the value of Λ0m.
Answer:
𝑆 𝑐𝑚−1
=1 (unit conversion factor)
100 𝑆 𝑚−1

Concentratio k (S m-1 ) k (S cm-1) 𝑘 1/2

Λm = ×1000 S cm2 C
n (M) 𝑐 (M1/2)
-1
mol
10-3 1.237×10- 1.237×10- 1000 × 1.237 × 10−4 0.031
N AT IS 2 4
10−3 6

C N
= 123.7

PY
O C D
1O-2 11 .8 5 × 11.85×10- 1000 × 11.85 × 10−4 0.100
O IO 10-2 4
10−3
D U AA

= 1185

O
2 × 102 23.15 × l0 23.15×10- 1000 × 23.15 × 10−4 0.141
-2 4
10−3
ED PR

= 115.8
5 ×10-2 55.53×10- 55.53×10- 1000 × 55.53 × 10−4 0.224
T
2 4
10−3
= 111.1
©

10-1 106.74×1 106.74×1 1000 × 106.74 × 10−4 0.316

0-2 0-4 10−3
= 106.7
 N AT IS
C N
PY
O C D
∧0m = Intercept on the ∧m axis = 124.0 S cm2 mol-1, which is obtained by
O IO
D U AA

extrapolation to zero concentration.

O
Q. 11 Conductivity of 0.00241 M acetic acid is 7.896 × 10–5 S cm–1.
Calculate its molar conductivity. If ∧0m for acetic acid is 390.5 S
ED PR

cm2mol–1, what is its dissociation constant?

Answer:
T
Given -
©

Molarity, C = 0.00241 M
Conductivity, κ = 7.896 × 10–5 S cm–1
Molar conductivity, ∧m =?
for acetic acid = 390.5 S cm2mol–1
𝑘
Molar conductivity, ∧m = × 1000 S cm2 mol-1
𝑐
7.896×10−5 𝑆 𝑐𝑚−1 ×1000 𝑐𝑚3 𝐿−1
==
0.0241 𝑚𝑜𝑙 𝐿−1

∴ ∧m = 32.76 S cm2 mol-1

To calculate the dissociation constant, Ka, we use
𝐶∝2
Ka = → Equation 1
1−∝

Here, we need to find the value of α (degree of dissociation), by the

formula,
Λ𝑐 𝑚
∝=
Λ0 𝑚
32.76
∝=
390.5

∴ α = 8.4 ×10-2 ⇒ Equation 2

N AT IS
→ Thus, substituting Equation 2 in Equation 1, we get,

C N
PY
O C D
𝐶∝2
Ka =
O IO
1−∝
D U AA

2
0.0024×(8.4×10−2 )

O
=
1−0.084

∴ Ka = 1.86×10- 5
ED PR

The molar conductivity, ∧m is 32.76 S cm2 mol-1 and the dissociation

T
constant, Ka is 1.86×10-5
©

Q. 12 How much charge is required for the following reductions:

(i) 1 mol of Al3+ to Al?
(ii) 1 mol of Cu2+ to Cu?
(iii) 1 mol of MnO–4 to Mn2+?
Answer:
(i) The electrode reaction is given as,
Al3+ (aq) + 3e- → Al(s)
∴ The quantity of charge required for the reduction of 1 mol of Al3+ = 3F
= 3×96487 C
= 289461 C
(ii) The electrode reaction is given as,
Cu2+ (aq) + 2e- → Cu(s)
∴ The quantity of charge required for the reduction of 1 mol of Cu2+ =
2F
= 2×96487 C
= 192974 C
(iii) The electrode reaction is given as,
N AT IS
MnO4→ Mn2+

C N
PY
O C D
i.e., Mn7+ + 5e- → Mn2+
O IO
D U AA

∴ The quantity of charge required for the reduction of 1 mol of Mn7+ =

O
5F
= 5×96487 C
ED PR

= 482435 C
T
Q. 13 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?
Answer:
(i) Ca2+ + 2e- → Ca
⇒ Here, 1 mole of Ca, i.e., 40g of Ca requires = 2 F electricity (F if
Faraday)
20×2
∴ 20g of Ca requires =
40

= 1 F of electricity
Electricity in terms of Faraday required to produce 20.0 g of Ca from
molten CaCl2 is 1 F of electricity.
(ii) Al3+ + 3e- → Al
⇒ 1 mole of Al, i.e., 27g of Al requires = 3 F electricity (F if Faraday)
3
∴ 40.0 g of Al will require = × 40
27

= 4.44 F of electricity
Electricity in terms of Faraday required to produce 40.0 g of Al from
molten Al2O3 is 4.44 F of electricity
N AT IS
Q. 14 How much electricity is required in coulomb for the oxidation of

C N
PY
O C D
(i) 1 mol of H2O to O2?
O IO
D U AA

(ii) 1 mol of FeO to Fe2O3?

O
Answer:
ED PR

(i)The electrode reaction for 1 mole of H2O is given as,

H2O → H2 + O2
T
i.e., O2- →O2 + 2e-
©

∴ The quantity of electricity required = 2F

= 2×96487 C
= 192974 C
The quantity of electricity required in coulomb for the oxidation of 1
mol of H2O to O2 is 192974 C
(ii) The electrode reaction for 1 mole of FeO is
FeO + O2 → Fe2O3
i.e., Fe2+ → Fe3+ + e-
∴ The quantity of electricity required = 1F
= 1×96487 C
= 96487 C
The quantity of electricity required in coulomb for the oxidation of 1
mol of FeO to Fe2O3 is 96487 C
Q. 15 A solution of Ni(NO3)2 is electrolyzed between platinum
electrodes using a current of 5 amperes for 20 minutes. What is mass of
Ni deposited at the cathode?
Given -

N AT IS
Current = 5A
Time - 20 minutes

C N
PY
O C D
Mass of Ni deposited =?
O IO
D U AA

Answer:

O
Quantity of electricity passed = 5 A × (20 × 60 sec)
ED PR

= 6000 C ⇒ Equation 1
The electrode reaction is written as,
T
Ni2+ + 2e → Ni
©

Thus, the quantity of electricity required = 2F

= 2×96487 C
= 192974 C
∵ 192974 C of electricity deposits 1 mole of Ni, which is 58.7 g ⇒
Equation 2
Thus, equating equations 1 and 2, we get,
192974 C of electricity deposits = 58.7 g
6000 C of electricity will deposit =
= 1.825g of Ni
The mass of Ni deposited at the cathode is 1.825g of Ni
Q. 16 Three electrolytic cells A, B, C containing solutions 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 silver
deposited at the cathode of cell B. How long did the current flow? What
mass of copper and zinc were deposited?
Given -
I = 1.5 A
N AT IS
W = 1.45 g of Ag

C N
PY
O C D
t =?O IO
D U AA

n=1

O
Answer:
180
ED PR

Equivalent weight is Ag, EAg = = 180

1
63.5
T
Equivalent weight is Cu, ECu = = 31.75
2
©

65
Equivalent weight is Zn, EZn= = 32.5
2

Using Faraday’s second law of electrolysis, to find the mass of Cu and

Zn, we use Equation 1,
𝑤𝑐𝑢 𝑤𝐴𝑔 𝑤𝑧𝑛
= = → Equation 1
𝐸𝑐𝑢 𝐸𝐴𝑔 𝐸𝑧𝑛

𝑊𝐴𝑔 ×𝐸𝑐𝑢
⇒ 𝑊𝑐𝑢 =
𝐸𝐴𝑔

1.45×31.75
= 𝑊𝑐𝑢 =
108

∴ WCu = 0.426 g
∴ WZn = 0.436 g
To find the time of current flow, using Faraday’s first law of electrolysis
we get,

N AT IS
M = Z ×I ×t ⇒ Equation 2
𝐸𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑤𝑒𝑖𝑔ℎ𝑡

C N
PY
∵Z= , Equation 2 becomes,
O C D
O IO 96487
108
D U AA

M= × 1.5 × t
96487

O
1.45×96487
t=
105×1.5
ED PR

t = 864 seconds.
T
The time of current flow, t = 864 seconds, the mass of Cu is 0.426 g and
mass of Zn is 0.436 g
©

Q. 17 Using the standard electrode potentials given in Table 3.1, predict

if the reaction between the following is feasible:
(i) Fe3+ (aq) and I–(aq)
(ii) Ag+ (aq) and Cu(s)
(iii) Fe3+ (aq) and Br– (aq)
(iv) Ag(s) and Fe3+ (aq)
(v) Br2 (aq) and Fe2+ (aq).
Answer:
(i) The electrode reaction is written as,
2Fe3+ + 2I- → 2Fe2+ + I2
0
E0cell = 𝐸𝐼02⁄ − 𝐸𝐹𝑒 3+
𝐼− ⁄ 2+
𝐹𝑒

= 0.54V - 0.77V
∴ E0cell = - 0.23 V
It is not feasible, as E0cell is negative, ∴ ∆G0 is positive.
(ii) The electrode reaction is written as,
N AT IS
2Ag+ (aq) + Cu(s)→ Cu2+ (aq) + Ag(s)

C N
PY
0 0
O C D
E0cell = 𝐸𝐴𝑔 + − 𝐸𝐶𝑢 2+
⁄𝐴𝑔 ⁄𝐶𝑢
O IO
D U AA

= + 0.80V - 0.34V

O
∴ E0cell = 0.46V
ED PR

It is feasible, as E0cell is positive, ∴ ∆G0 is negative.

(iii) The electrode reaction is written as,
T
2Fe3+ (aq) + 2Br- (aq)→ 2Fe2+ (aq) + Br2
©

0 0
E0cell = 𝐸𝐹𝑒 3+ − 𝐸𝐵𝑟2⁄
⁄ 2+ 𝐵𝑟 −
𝐹𝑒

= 0.77V - 1.09V
∴ E0cell = - 0.32 V
It is not feasible, as E0cell is negative, ∴ ∆G0 is positive.
(iv) The electrode reaction is written as,
Ag(s) + Fe3+ (aq) → Fe2+ (aq) + Ag+ (aq)
0 0
E0cell = 𝐸𝐹𝑒 3+ − 𝐸𝐴𝑔 +
⁄ 2+ ⁄𝐴𝑔
𝐹𝑒
= 0.77V - 0.80V
∴ E0cell = - 0.03
It is not feasible, as E0cell is negative, ∴ ∆G0 is positive.
(v) The electrode reaction is written as,
Br2 + 2Fe2+ (aq) → 2Br- (aq) + 2Fe3+ (aq)
0 0
E0cell = 𝐸𝐵𝑟2⁄
− 𝐸𝐹𝑒 3+
𝐵𝑟 − ⁄ 2+
𝐹𝑒

= 1.09V - 0.77V
N AT IS
∴ E0cell = 0.32 V

C N
PY
It is feasible, as E0cell is positive, ∴ ∆G0 is negative.
O C D
O IO
Q. 18 Predict the products of electrolysis in each of the following:
D U AA

O
(i) An aqueous solution of AgNO3 with silver electrodes.
(ii) An aqueous solution of AgNO3 with platinum electrodes.
ED PR

(iii) A dilute solution of H2SO4 with platinum electrodes.

T
(iv) An aqueous solution of CuCl2 with platinum electrodes.
©

Answer:
Given -
All the ions are in aqueous state.
(i) Reaction in solution:
AgNO3(s) + aq → Ag + + NO3-
H2O ó H + + OH-
At cathode:
Ag+ (aq) + e- →Ag(s)
Ag+ ions have lower discharge potential than H+ ions. Hence, Ag+ ions
get deposited as Ag in preference to H+ ions.
At anode:
Ag(s)→ Ag+ (aq) + e-
As Ag anode is attacked by NO3- ions, Ag of the anode will dissolve to
form Ag + ions in the aqueous solution.
(ii) Reaction in solution:
AgNO3(s)+ aq → Ag+ + NO3-
N AT IS
H2O óH + + OH -

C N
PY
At cathode:
O C D
O IO
2Ag+ (aq) + 2e- →2Ag(s)
D U AA

Ag+ ions have lower discharge potential than H + ions. Hence, Ag+ ions

O
get deposited as Ag in preference to H+ ions.
ED PR

At anode:
2OH- (aq) → O2(g) + 2H+ (aq) + 4e-
T
As anode is not attackable, out of OH - and NO3- ions, OH- having lower
©

discharge potential, will be discharged in preference to NO3- ions. These

then decompose to give out O2.
(iii) Reaction in solution:
H2SO4(aq) → 2H+ (aq) + SO42- (aq)
At cathode:
2H+ (aq) + 2e- →H2(g)
At anode:
2OH- (aq) → O2(g) + 2H+ (aq) + 4e-
∴ H2 gas is evolved at cathode and O2(g) is evolved at anode.
(iv) Reaction in solution:
CuCl2(s) + aq → Cu2+ (aq) + Cl- (aq)
H2O óH+ + OH-
At cathode:
Cu2+ (aq) + 2e- →Cu(g)
At anode:
2Cl- (aq) + e - → Cl2(g)
∴ Cu will be deposited at cathode and Cl2 gas will be liberated at anode.
N AT IS
C N
PY
O C D
O IO
D U AA

O
ED PR

T
©