CHAPTER-09

ELECTROCHEMISTRY
 Molar conductance Kohlrausch Law
𝜆𝑚 = 𝜇 = Λ𝑚 = 𝐾 × 𝑉𝑚 𝜆∞ ∞ ∞
𝑒𝑞 = 𝜆𝑒𝑞𝑐 + 𝜆𝑒𝑞𝑎
𝑉𝑚 = Molar volume in cm3 For 𝐴𝑥 𝐵𝑦 ∶ 𝐴𝑥 𝐵𝑦 → 𝑥𝐴 𝑦+ + 𝑦𝐵 𝑥−
unit of 𝜆𝑚 = 𝑜ℎ𝑚−1 𝑐𝑚2 𝑚𝑜𝑙 −1 𝜆∞ ∞
𝑚 = 𝑥𝜆𝑚𝑐 + 𝑦𝜆𝑚𝑎
∞
𝐾×1000
𝜆𝑚 = ➢ 𝛼=
𝜆𝑒𝑞
=
𝜆𝑚
𝑀
𝜆𝑒𝑞 𝜆∞
Equivalent Conductance 𝑐𝛼
𝑚

(𝜆𝑒𝑞 𝑜𝑟 Λ𝑒𝑞 ) ➢ 𝐾𝑎 = ;
(1−𝛼)
𝐾×1000
𝜆𝑒𝑞 = 𝐾 × 𝑉 = If 𝑎 ≤ 5% 𝑡ℎ𝑒𝑛 𝐾𝛼=𝑐𝛼2
𝑁
Unit of 𝜆𝑒𝑞 → 𝑜ℎ𝑚−1 𝑐𝑚2 𝑒𝑞 −1 ➢ Λ𝑚 (𝑠𝑎𝑡𝑢𝑟𝑎𝑡𝑒𝑑) = Λ∞
𝑚 =
𝐾×1000
Dilution ↑ ⇒ 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 ↓ 𝑆
⇒ 𝐾 ↓ ⇒ (𝐺, Λ𝑚 , Λ𝑒𝑞 ) S→ 𝑠𝑜𝑙𝑢𝑏𝑖𝑙𝑖𝑡𝑦

Electrolytic Conductance ↑
⇓
Solvation / Hydration of ions ↓
⇓
Inter Ionic Interactions ↓
⇓
Temperature ↑
⇓
Dilution ↑

ELECTROCHEMICAL SERIES
Electrochemical series is the arrangement of elements in order
of increasing standard reduction potential values

Values of SRP increases.

Tendency to get reduce themselves ↑
Oxidising Power ↑
Reactivity of metal ↓ 51
Reactivity of non-metals/halogens ↑
 Values of SOP ↑
Tendency to get oxidise themselves ↑
Reducing Power ↑

1
• Oxidising Power 𝛼 SRP 𝛼 𝑆𝑂𝑃 [Maximum SRP→ 𝐹2 (+2.87𝑉)]
1
• Reducing Power 𝛼 SOP 𝛼 𝑆𝑅𝑃 [Maximum SOP→ 𝐿𝑖(+3.05𝑉)]
• Metals which are placed above in series can easily displace metal ion
from their aqueous solutions which are placed below in series.
𝐶𝑢 + 𝑍𝑛𝑆𝑂4 (𝑎𝑞) → 𝑁𝑜 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛
𝐶𝑢 + 2𝐴𝑔𝑁𝑂3 (𝑎𝑞) → 𝐶𝑢(𝑁𝑂3 )2 + 2𝐴𝑔(𝑠)
• No-metals which are placed below in series can easily displace
anions of non-metal from their aqueous solutions which are placed
above in series.
2𝐴− + 𝐵2 → 2𝐵 − + 𝐴2
2𝐶 − + 𝐵 → 𝑁𝑜 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝐸°𝑐 − /𝑐2 < 𝐸°𝐵− /𝐵2 < 𝐸°𝐴−/𝐴2 < 𝐸°𝐷− /𝐷2
− −
2𝐷 + 𝐴2 → 2𝐴 + 𝐷2

• Metals placed above 𝐻2 𝐻2 (g) from aqueous solution of acid.

𝑑𝑖𝑠𝑝𝑙𝑎𝑐𝑒
Metals placed above Mg → 𝐻2 (g) from cold water.
Metals from Mg to Cr 𝐻2 (g) from hot water.
Metals Fe 𝐻2 (g) from react with steam.
• Oxides of metal which are placed below to copper are thermally
unstable and easily reduced to metal when heated.
Δ
𝐴𝑔2 𝐶𝑂3 → 𝐴𝑔2 𝑂 + 𝐶𝑂2 ↑
↓
2𝐴𝑔 + 1⁄2 𝑂2

ELECTROCHEMICAL CELL

52
• Device in which non-spontaneous redox reaction (Δ𝐺 > 0) is
used to convert electrical energy into chemical energy.
• Cation (+ve) → Cathode (–ve) → Reduction
• Anion (–ve) → Anode (+ve) → Oxidation
• Sign of cathode and anode are opposite in Galvanic cell &
Electrolytic cell.
• D.C. source is used for electrolysis.
Δ𝐺 −𝜂𝐹𝐸
• Efficiency of cell (𝜂) = Δ𝐻 = Δ𝐻

Faraday’s Law
1st Law: When electricity is passed through an electrolyte then
𝑊∞𝑄 ; W = Z × I × t
Z (Electrochemical Equivalent) : Weight of substance in gram
discharged by 1C charge
𝐸×𝑖×𝑡
𝑊=
96500
2 Law: If same amount of charge is passed through different
nd

solution of electrolyte connects in series, then

𝑊1 𝑊 𝑊 𝑊
= 2 = 3 = 4 ……constant
𝐸1 𝐸2 𝐸3 𝐸4

S.No. Electrolyte Electrode Product Product pH

at at change
anode cathode
1. Fused/molten Pt or Cl2 Na No
NaCl Graphite change
2. Aqueous NaCl Pt or Cl2 H2 pH ↑
Graphite
3. Dilute NaCl Pt or O2 H2 No
Graphite change
4. Aqueous NaCl Hg Cl2 Reduction No
of Na change
5. Fused NaOH Pt or O2 Na No
Graphite change
6. Aqueous Pt or O2 Cu pH ↓
CuSO4 Graphite
7. Aqueous Cu Cu Cu No
CuSO4 oxidises change
to Cu+2
8. Aqueous CuCl2 Cu Cu Cu No
oxidises change
to Cu+2
9. Aqueous Pt or O2 Ag pH ↓
AgNO3 Graphite
10. Aqueous Ag Ag Ag No
AgNO3 oxidises change
to Ag+
11. Aqueous Ni Ni Ni No
NiSO4/Ni(NO3)2 oxidises change
to Ni+2
12. Aqueous NiSO4 Pt or O2 Ni pH ↓
Graphite
13. Aqueous Pt or O2 H2 No
Na2SO4 Graphite change
14. Dilute H2SO4 Pt or O2 H2 No
Graphite change

Corrosion
• Corrosion is the process of change of metal surface into salts
like oxides, sulphides, carbonates etc. due to attack of
atmospheric gases.
• Rust is hydrated ferric oxide 𝐹𝑒2 𝑂3 ∙ 𝑥𝐻2 𝑂
• Factors which enhance corrosion are:
(a) Presence of impurities in metal.
(b) Presence of moisture (Ex. Rainy season)
(c) Presence of electrolyte. (Ex. Saline water)
• Corrosion can be prevented by Barrier protection (oil/grease),
sacrificial protection (Galvanization), Electrical protection.
• 𝐻2 − 𝑂2 fuel cell was the source of drinking water & electrical
energy in Appollo Moon flight.
• Mercury cell gives constant voltage throughout its life.
• Dry cell has short life because acidic NH4Cl corrodes Zn
container. 54
 CELL
• Primary cells cannot be recharged. Ex. Dry cell & Mercury Cell
• Secondary cells can be recharged. Ex. Ni–Cd Cell & Lead storage
battery.
• Fuel cell produce energy from the combustion of fuels which can
be converted into electrical energy. Ex. H2 – O2 fuel cell.

Name of the Anode Cathode Electrolyte

cell/battery
Dry Cell Zinc Graphite; MnO2 + NH4Cl + ZnCl2
C (touching (touching
cathode) anode)
Mercury cell Zinc- Paste of HgO & Paste of KOH &
(used in watches, mercury carbon ZnO
hearing aids) Amalgum
Lead storage Lead Lead Dioxide H2SO4 (38%)
battery PbO2
Ni-Cd cell Cadmium [Ni(OH)3] KOH solution
H2 – O2 fuel cell Porous Porous carbon Concentrated
carbon containing aq. NaOH
containing catalysts (O2 solution
catalysis passed)
(H2
passed)

• Reactions in lead storage battery during the discharge:

• At anode : 𝑃𝑏(𝑠) + 𝑆𝑂42− → 𝑃𝑏𝑆𝑂4(𝑠) + 2𝑒 −
• At cathode: 4𝐻 + + 𝑃𝑏𝑂2(𝑠) + 𝑆𝑂42− + 2𝑒 − → 𝑃𝑏𝑆𝑂4(𝑠) + 2𝐻2 𝑂
• complete reaction: 𝑃𝑏(𝑠) + 𝑃𝑏𝑂2(𝑠) + 2𝐻2 𝑆𝑂4 → 2𝑃𝑏𝑆𝑂4(𝑠) + 2𝐻2 𝑂
The EMF of a cell is found Given:
by adding oxidation 1. 𝐶𝑢+2 + 2𝑒 − → 𝐶𝑢, 𝐸° = 0.337𝑉
potential & reduction 2. 𝐶𝑢+2 + 𝑒 − → 𝐶𝑢+ , 𝐸° = 0.153𝑉
potential of the half-cell Aim:
reaction. 3. 𝐶𝑢+ + 𝑒 − → 𝐶𝑢, 𝐸° =?
But the electrode potential
of a half-cell from two other
half cells cannot be found
by simply adding their
electrode potential.
Subtracting 1-2 will not give the desired result. We have to calculate
their free energy change.
Let Δ𝐺°1 , Δ𝐺°2 & Δ𝐺°3 be free energy changes of the above three reaction.
Then Δ𝐺°1 − Δ𝐺°2 = Δ𝐺°3 i.e., (–2 × F × 0.337) – (–1 × F × 0.153) =
– 1 × 𝐹 × 𝐸°𝐶𝑢+ /𝐶𝑢 (Δ𝐺° =– 𝑛𝐹𝐸°)
This gives 𝐸°𝐶𝑢+/𝐶𝑢 = 0.521 𝑉