ELECTROCHEMISTRY (UNIT‐2)

KEY POINTS

Resistance – obstacle to the flow of electricity.

Resistivity – resistance offered by the conductor when it is of unit length and has unit area of

cross section.

Conductivity – conductance of the ions present in 1 cubic centimetre solution. It is the reciprocal of resistivity.

1. Effect of dilution on conductivity – conductivity decreases with dilution because number of ions per ml of

solution decreases.

2. Effect of dilution on molar conductivity – molar conductivity of strong electrolyte increases with dilution

because ionic mobility increases, whereas molar conductivity of weak electrolyte increases because

degree of dissociation of it increases so number of ions increase .

3. Kohlrausch law – conductivity of an electrolyte at infinite dilution is the sum of individual contribution of

anion and cation of the electrolyte .

4. Faraday's law of electrolysis ‐ First law – amount of substance deposited at the electrode during

electrolysis is directly proportional to the quantity of electricity passed through electrolyte .

Second law – when same amount of electricity is passed through different electrolytic solution, amount of

substance deposited is proportional to the chemical equivalent weights .

5. Fuel cell – it converts combustion energy of fue l into electricity . H2 and CH4 can be used as fuel in it .

6. Corrosion – corrosion of metal is an electro chemical phenomenon .

7. Anode :‐ 2 Fe →2Fe2+ + 4 e–(oxidation)

Cathode :‐ O2 + 4 H+ + 4e– → 2H2O (reduction)

Atmospheric Oxidation:‐ 2Fe 2+(aq)+ 2H2O (l) + ½ O2 → Fe2O3 (g) + 4H+ (aq)

Rate of corrosion increase in acidic medium also increase in the presence of salt and oxygen but rate decreases

in basic medium .

Prevention of corrosion

1. By Galvanization: ‐ coating of Zn on iron

2. By Cathodic protection :‐ Mg is joined with iron which behaves like anode and iron as cathode

3. By painting and oiling

3. By painting and oiling

IMPORTANT FORMULAE
 Frequently asked question

1).What is meant by limiting molar conductivity?

Ans Molar conductivity of an electrolyte at infinite dilution.

2.) Give the relationship between molar conductivity and specific conductivity ?

Ans. ᴧm =k (1000\M)

3.) What is meant by limiting molar conductivity?

Ans. The molar conductivity of a solution at infinite dilution is called limiting molar conductivity

4.) What is the unit of molar conductivity?

Ans. ohm–1

cm2mol–1
5.) What is the effect of dilution of concentration on specific conductance?

Ans. Specific conductance decrease with dilution, because it is the conduction power of ions present in unit volume of solution
and number of ions in unit volume decreases on dilution.

Specific conductance increases withconcentration.

6.) What type of metals can be used in cathodic protection of iron against rusting?

Ans. A metal which is more electropositive than iron i.e. having lower reduction potential. ExampleZn, Mg etc.

7. Why mercury cell gives constant voltage throughout its life?

Ans. As the overall reaction does not involve any ion in solution whose conc. can change during its life.

2 marks

1. What is fuel cell? Write two chemicals which can be used as fuel.

Ans. The cell which converts combustion energy of fuel into electricity. Methane and hydrogen can be used as fuel.

2H2(g)+4OH–(aq) → 4H2O(l)+4e–

O2 + 2H2O (l) + 4e– →4OH– (aq)

2.) What type of battery is the lead storage battery?

Ans. Lead storage battery is the secondary cell. So it can be recharged by passing direct current through it.

3.) How many moles of mercury will be produced by electrolysing 1.0 M Hg (NO3)2 solution with a current of 2.00 A for three
hours?

Molar mass of Hg (NO3)2= 200.6 g/mol

Ans. Current = 2A

Time = 3h = 3(60)(60)s

w = Zit.

Z for Hg in compound =200.6/2F

w= 200.6x2x(3)(60)(60)/2(96500)

w= 22.45g number of moles = 22.45\200.6 = 0.112 mol

4.) Represent the galvanic cell in which the following reactions take place :

Zn(s) + 2Ag+ (aq) → Zn2+(aq) + 2Ag(s)

a. Which one of the electrodes is negatively charged?

b. Write the reaction taking place at each of the electrodes
c. Name the carrier of current within the cell

Ans. The cell is represented as

Zn(s) │Zn2+(aq) ││Ag+ (aq) │Ag(s) │

a. Zn electrode is negatively charged

b. At anode Zn(s) → Zn2+ + 2e– At cathode Ag+ (aq) + e– → Ag(s)
c. Ions are the carrier of current within the cell.

5.) How much charge is required for the reduction of1 mole ofCu2+ to Cu?

Ans. Cu2++2e→ Cu

Charge required for the reduction of1 mole Cu2+ =2F =2(96500 C) = 193000C.

3 marks

1.) Determine the value of equilibrium constant and ∆G0 for the following reaction :
Ni(s)+2Ag+ (aq)→Ni2+ (aq)+2Ag(S) (E0 = 1.05V).

Ans. n=2 ΔG0 = ‐nFE 0

Δ G0 = ‐2 (96500) C (1.05) V

Δ G0 = ‐202650 Jmol-1 = – 202.65 kJ mol-1.

‐nFE0 =‐2.303RT logKc

logKc=nE0 /0.0591 =2(1.05/0.0591) = 35.532 g

Kc = antilog 35.532

Kc = 3.411× 1035 .

5 marks
 QUESTION BANK
YEAR 2020
1. Kohlrausch given the following relation for strong electrolytes:
∧ = ∧0 − A√C
Which of the following equality holds?
(a) ∧ = ∧0 as C → √A (b) ∧ = ∧0 as C → ∞
(c) ∧ = ∧0 as C → 0 (d) ∧ = ∧0 as C → 1
2. In an electrochemical process, a salt bridge is
used as a reducing agent.
as an oxidizing agent.
to complete the circuit so that current can flow.
None of these
3. Assertion (A): Conductivity of an electrolyte increases with decrease in concentration.
Reason (R) : Number of ions per unit volume decreases on dilution.
4. When a steady current of 2A was passed through two electrolytic cells A and B containing electrolytes ZnSO 4 and CuSO4
connected in series, 2g of Cu were deposited at the cathode of cell B.
(a) How long did the current flow?
(b) What mass of Zn was deposited at cathode of cell A? [Atomic mass: Cu = 63.5 g mol–1, Zn = 65 g mol–1; 1F =
96500 C mol–1]
5. Name the cell used in hearing aids and watches.
6. How much charge in terms of Faraday is required to reduce one mol of MnO − to Mn2+?
4
YEAR 2019
1. E° 2+ 2+
cell for the given redox reaction is 2.71 V Mg(s) + Cu (0.01 M) → Mg (0.001 M) + Cu(s)
Calculate Ecell for the reaction. Write the direction of flow of current when an external opposite potential applied is
(i) less than 2.71 V and
(ii) greater than 2.71 V
2.
(a) A steady current of 2 amperes was passed through two electrolytic cells X and Y connected in series containing
electrolytes FeSO4 and ZnSO4 until 2.8 g of Fe deposited at the cathode of cell X. How long did thecurrent flow?
Calculate the mass of Zn deposited at the cathode of cell Y. (Molar mass : Fe = 56 g mol–1 Zn = 65.3 g mol–1, 1F =
96500 C mol–1)
(b) In the plot of molar conductivity (∧m) vs square root of concentration (c1/2), following curves are obtainedfor two
electrolytes A and B:

Answer the following:

Predict the nature of electrolytes A and B.
What happens on extrapolation of ∧m to concentration approaching zero for electrolytes A and B?
YEAR 2018
2+ +
1. (a) Write the cell reaction and calculate the e.m.f of the following cell at 298 K: Sn(s)| Sn (0.004 M)||H (0.020 M)|H2(g)(1
bar) Pt (s)
(Given : E0Sn2+/Sn= −0. 14 V)
(b)Give reasons:
(i) On the basis of E° values, O gas should be liberated at anode but it is Cl gas which is liberated in theelectrolysis of
2 2
aqueous NaCl.
(ii) Conductivity of CH COOH decreases on dilution.
3

2. (a) For the reaction. 2 AgCl +H (s) (1atm) → 2 Ag +2H+ (0. 1 M) +2 Cl− (0. 1 M), ∆G° = −43600 J at 25°C
2 (g) (s)

Calculate the e.m.f. of the cell. [log 10–n = – n]

(b) Define fuel cell and write its two advantages.
YEAR 2017
1. Calculate the degree of dissociation (α) of acetic acid if it's molar conductivity (Λm) is 39.05 S cm2 mol−1. Given, λ°(H+)
=
349.8 S cm2 mol−1 and λ°(CH3COO−) = 40.9 S cm2 mol−1
2. Calculate the mass of Ag deposited at cathode when a current of 2 amperes was passed through a solutionof

AgNO3 for 15 minutes.

(Given : Molar mass of Ag = 108 g mol−1, 1 F = 96500 C mol−1)
 Electrochemistry, BOARD Questions 2022-2014

3.(a) Define fuel cell

(b) Write the name of the cell which is generally used in transistors. Write the reactions taking
place at the anode and the cathode of this cell.
4.
The cell in which the following reaction occurs 2 Fe3+ (aq) + 2 I− (aq)−−−−−−−→ 2 Fe2+
(aq) + I2 (s)
has Eocell = 0·236 V at 298 K. Calculate the standard Gibbs energy of the cell reaction. (Given : 1
F = 96,500 C
5.
How many electrons flow through a metllic wire if a current of 0·5 A is passed for 2 hours?
(Given : 1 F =96,500 C mol−1)
2016
1. From the given cells: Lead storage cell, Mercury cell, Fuel cell and Dry cell Answer the
following:
(i) Which cell is used in hearing aids?
(ii) Which cell was used in Apollo Space Programme?
(iii) Which cell is used in automobiles and inverters?
(iv) Which cell does not have long life?
2. Calculate e.m.f of the following cell at 298 K: 2Cr(s) + 3Fe2+ (0.1M)
→ 2Cr3+ (0.01M) + 3 Fe(s) Given: E°(Cr3+/Cr) = – 0.74 V E° (Fe2+/Fe) =
– 0.44 V
2+ 3+
3. (a) Calculate E°cell for the following reaction at 298 K: 2Al(s) + 3Cu (0.01 M) → 2Al
(0.01M) + 3Cu(s)
Given: Ecell = 1.98V
(b) Using the E° values of A and B, predict which is better for coating the surface of iron
[E°(Fe2+/Fe) = –0.44V] to prevent corrosion and why?
Given: E°(A2+/A) = –2.37V : E° (B2+/B) = –0.14V
–1 –5 –1
4. The conductivity of 0.001 mol L solution of CH3COOH is 3.905 × 10 S cm .
Calculate its molarconductivity and degree of dissociation (α). [Given λ0 (H+) = 349.6 S
cm2 mol–1 and λ0 (CH3COO–) = 40.9 S cm2 mol–1]
5. Define electrochemical cell. What happens if external potential applied becomes greater
than E°cell of electrochemical cell?
2015
1. How much charge is required for the reduction of 1 mol of Zn2+ to Zn?
Calculate e.m.f. and ∆G for the following cell: Mg (s) /Mg2+(0. 001 M) // Cu2+(0. 0001 M)/Cu(s)
Given :E0 Mg2+/Mg= -2.37v. E0 Cu2+/Cu = +0.34 v)
2. The conductivity of 0.20 mol L−1 solution of KCl is 2.48 × 10−2 S cm−1. Calculate its
molar conductivity and degree of dissociation (α). [Given λ0 (K+) = 73.5 S cm2 mol−1 and
λ0 (C1−) = 76.5 S cm2 mol−1.]
3. What type of battery is mercury cell? Why is it more advantageous than dry cell?
4. Following reactions occur at cathode during the electrolysis of aqueous
copper(II) chloride solution : Cu2+ (aq) + 2e− −−−−−→ Cu (s) E° =
0. 34 V
2H+ + (aq) + e− −−−−−→H2 (g) E° = 0. 00 V
5. On the basis of their standard reduction electrode potential (E°) values, which reaction is
feasible at thecathode and why
? State Kohlrausch law of independent migration of ions. Write its one application.
2+ +
6. Calculate the emf of the following cell at 25°C : Zn | Zn (0.001 M) || H (0.01 M) | H2(g) (1
bar) | Pt(s)
[ E0 Zn2+/Zn = −0. 76 V, E0(H+/H2) = 0. 00 V ]
7. Define limiting molar conductivity. Why conductivity of an electrolyte solution
decreases with the decrease in concentration ?
Calculate emf of the following cell at 25 °C :Fe /Fe2+ (0. 001 M) // H+ (0. 01 M)/H2 (g) /(1
bar)Pt(s)

[E° (Fe2+/Fe ) = −0. 44 v E° (H+ H2 ) = 0. 00 v]

2014
2+ 2+
1. Calculate ∆rG° for the given reaction: Mg (s) + Cu (aq.) → Mg (aq.) + Cu (s)
[Given : E°cell = +2·71 V, 1 F = 96500 Cmol−1]
2. Name the type of cell which was used in Apollo space program for providing electrical
power.
3. Resistance of a conductivity cell filled with 0.1 mol L−1 KCl solution is 100 Ω. If the
resistance of the samecell when filled with 0.02 M KCl solution is 520 Ω, calculate the
conductivity and molar conductivity of 0.02 M KCl solution. The conductivity of 0.1 M KCl
solution is 1.29 × 10−2 Scm−1.
4. State Faraday's first law of electrolysis. How much charge in terms of Faraday is required
for the reduction of 1 mol of Cu2+ to Cu.
Calculate emf of the following cell at 298 K: Mg(s) | Mg2+(0.1 M) || Cu2+ (0.01) | Cu(s) [Given
Eocell = +2.71 V, 1 F = 96500 C mol–1]

5. Define the following terms :

(a) Limiting molar conductivity (b) Fuel cell
6. State Faraday's first law of electrolysis. How much charge in terms of Faraday is required
for the reduction of 1 mol of Cu2+ to Cu.
7. Why does the conductivity of a solution decrease with dilution?
----------------------------ALL THE BEST----------------------------------------------

COMPILED BY

G.SUBHA,

DEPARTEMENT OF CHEMISTRY

VELAMMAL VIDYALAYA ALAPAKKAM.