ELECTROCHEMISTRY

CASE-BASED/PASSAGE-BASED INTEGRATED QUESTIONS

JI
I. Read the given passage and answer the questions (c) When does electrochemical cell behaves like

based on passage and related studied concepts. electrolytic cell?
Metallic conductance involves movement of Ans. When Eexternal > E°cell

electrons where as electrolytic conductance (d) For an electrochemical cell Mg(s) + 2Ag+(aq)

involves movement of ions. Specific conductance → 2Ag(s) + Mg2+. Give the cell representation
increases with increase in concentration where as and write Nernst equation.
Λm (molar conductivity) decreases with increase Ans. Mg(s) | Mg2+(aq) | | Ag+(aq) | Ag(s)

in concentration. Electrochemical cell converts
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chemical energy of redox reaction into electricity.
Mercury cell, Dry cells are primary cells where as

Ecell = E°cell –
0.0591
2
log
[Mg 2+]
[Ag +] 2
Ni—Cd cell, lead storage battery are secondary (e) Which will have higher conductance, silver

cells. Electrochemical series is arrangement of wire at 30° or at 60°C?
elements in increasing order of their reduction Ans. Silver wire at 30°C. Metallic conductance

potential. Electrolytic cell converts electrical energy decreases with increase in temperature.
into chemical energy which is used in electrolysis. (f) Calculate maximum work obtained from the

Amount of products formed are decided with the cell Ni(s) + 2Ag+(aq) → Ni2+(aq) + 2Ag(s) E°cell
help of Faraday’s laws of Electrolysis. Kohlrausch = 1.05V.
law helps to determine limiting molar conductivity Ans. DG° = –nE°F = –2 × 1.05 V × 96500 C = –202.65 kJ

A
of weak electrolyte, their degree of ionisation Wmax = –DG° = –(–202.65 kJ) = +202.65 kJ

(a) and their dissociation constants. Corrosion is (g) Which cell is used in hearing aids and watches?
electrochemical phenomenon. Metal undergoing

Ans. Mercury cell
corrosion acts as anode, loses electrons to form

ions which combine with substances present in II. Read the given passage and answer the questions
atmosphere to form surface compounds. More that follow:
B

reactive metals are coated over less reactive metals Electrochemistry plays a very important part in

to prevent corrosions. H2—O2 fuel cell was used in our daily life. Primary cells like dry cell is used in
apollo space programme. torches, wall clock, mercury cell is used in hearing
(a) Out of 0.5 M, 0.01 M, 0.1 M and 1.0 M which aids, watches. Secondary cells Ni–Cd cell is used in

solution of KCl will have highest value of cordless phones, lithium battery is used in mobiles,
specific conductance? Why? lead storage battery is used in vehicle and inverter.
Ans. 1.0 M KCl solution because it will have more Fuel cells like H2—O2 cell was used in apollo space
programme. A 38% solution of sulphuric and is

number of ions per unit volume of solution.
used in lead storage battery. Its density is 1.30 g
(b) Write the product of electrolysis of aq. NaCl
mL–1. The battery holds 3.5 L of the acid. During

on cathode. Why?
the discharge of the battery, the density of H2SO4
Ans. 2H+ + 2e– → H2(g) falls to 1.14 g mL–1 (20% solution by mass) (Molar

[Q E°H+/H2 = 0, is higher than E°Na+/Na = –2.71 V] mass of H2SO4 is 98 g mol–1).

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 (a) Write the chemical reaction taking place at III. Observe the graph shown in figure between Λm

anode when lead storage battery is in use. (molar conductivity) Vs C (Molar concentration)
Ans. Pb + SO42– → PbSO4 + 2e– (At anode) and answer the questions based on graph.

(b) How much electricity in Faraday is required to

carry out the reduction of one mole of PbO2? ‘X’

Ans. PbO2 + 4H+ + 2e– + SO42– → PbSO4 + 2H2O

(Molar conductivity)

2 Faraday is required.

(c) What is molarity of sulphuric acid before

Λm

discharge?
percentage by mass × d ×10
Ans. M =

JI
Molar mass ‘Y’

38 × 1.30 × 10 494
= = = 5.041 M
98 98

(d) What is mass of sulphuric acid in solution after C

discharge? (Molar concentration)

Ans. Mass of solution after discharge = 3500 mL × (a) The curve ‘Y’ is for KCl or CH3COOH?

1.14 g mL–1 = 3990 g

Ans. It is for CH3COOH.
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Mass of H 2SO 4 present in solution (20%) =

(b) What is intercept on Λm axis for ‘X’ equal to?

20

× 3990 g = 798 g Ans. It is equal Λ° (limiting molar conductivity).
100

(e) Write the products of electrolysis when dilute (c) Give mathematical equation representing


sulphuric acid is electrolysed using platinum straight line.
electrodes. Ans. Λm = Λ°m – A C

+
Ans. H2SO4 (dil) → 2H + SO42– (d) What is slope equal to?



+ –
H2O → H + OH Ans. Slope = –A


+ –
At cathode: 2H + 2e → H2(g) (e) What happens to molar conductivity on dilution


At anode: +
2H2O → 4H + 4e + O2(g)– in case of weak electrolyte and why?

A
H2 gas is liberated at cathode and O2 gas is formed Ans. Λm for weak electrolyte increases sharply on


at anode. dilution because both number of ions as well as
mobility of ions increases.

IV. Observe the following table in which conductivity and molar conductivity of NaCl at 298 K at different
concentration for different electrolytes is given. Answer the questions based in the table that follows:
B

Conductivities and molar conductivities of NaCl at 298 K at different concentrations.

1. 0.001 1.237 × 10–4 123.7 S cm2 mol–1 NaCl 126.4 S cm2 mol–1

2. 0.010 11.85 × 10–4 118.5 S cm2 mol–1 HCl 426.1 S cm2 mol–1

3. 0.020 23.15 × 10–4 115.8 S cm2 mol–1 CH3COONa 91 S cm2 mol–1

4. 0.050 55.53 × 10–4 111.1 S cm2 mol–1 NH4Cl 129.8 S cm2 mol–1

5. 0.100 106.74 × 10–4 106.7 S cm2 mol–1

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Ans. Conductivity decreases with decrease in – Λ° NaCl

concentration (dilution) because number of ions Λ°m CH3COOH = 91.0 + 426.1 – 126.4
per unit volume decreases.

= 390.07S cm2 mol–1
(b) Why is Λ°m (limiting molar conductivity) for

(e) Calculate Ka of 0.01 M CH3COOH solution

HCl more than NaCl?

if Λ°m for CH3COOH is 390.07S cm2 mol–1,
Ans. It is because mobility of H+ is more than Na+ Λm = 39.07S cm–1.

became H+ are lighter than Na+. /m 39.07
(c) Calculate degree of dissociation (a) of NaCl of Ans. a= = = 0.1
/ m° 390.07

JI
0.001 M concentration using the table.
Ca 0.01 × (0.1) 2
/m 123.7 Ka = =
Ans. a = = = 0.978 ⇒ a = 97.8% 1– a 1 – 0.1

/ m° 126.4

10 –4
Ka = = 1.11 × 10–4
0.9

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A
B

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