CLASS-XII CHEMISTRY

CHAPTER-ELECTROCHEMISTRY
➢ Electrochemistry is defined as a branch of chemistry which deals with
the relationship between electrical energy and chemical changes taking
place in redox reaction.
➢ Means how chemical energy produced in redox reaction can be
converted into electrical energy.
➢ Chemical changes involving production of electricity are called as
electrochemical changes.
➢ There are mainly three aspects of study in electrochemistry: -

1. Electrolysis
2. Electrolytic conduction
3. Electrochemical cell/galvanic cell/voltaic cell
ELECTROLYSIS
➢ The substances which conduct electricity in its molten state are called as
electrolytes.
Ex. Acid, Base, Salts etc.
➢ Electrolysis may be defined as a process of decomposition of an
electrolyte by the passing electricity in its aqueous solution or molten
state.
➢ The apparatus used for electrolysis process is called as electrolytic cell.
ELECTROLYTIC CELL

ELECTROLYTIC CELL

➢ It consists of glass vessel in which aq. Solution of electrolytes is taken.

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➢ Two metal rods are dipped into it and are connected to electricity
source (Battery).
➢ These rods are called electrodes.
A. Cathode : connected to – ve pole of battery.
B. Anode : connected to + ve pole of battery.
It convert the electrical energy to chemical energy.
ELECTROLYSIS PROCESS

Ex. (1) Electrolysis of molten NaCl

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(2) Electrolysis of Aqueous NaCl

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(3) Electrolysis of aq. CuSO4 solution using Cu electrode

Chemical reaction
CuSO4 → Cu2+ + SO42-
At anode
Here anode itself undergoes oxidation to form Cu2+ ion which goes into
solution. This is due to Cu is more easily oxidised than SO42- .
Cu → Cu2+ + 2 e-
At cathode
Cu2+ + 2 e- → Cu
The net result is that Cu is deposited at cathode and an equivalent amount of
Cu from anode is dissolved into solution to form Cu2+ ion.

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QUANTITATIVE ASPECT OF ELECTROLYSIS

(FARADAY’S LAW OF ELECTROLYSIS)
FIRST LAW OF FARADAY

➢ According to this law, the amount of chemical reaction or the mass of

any substance deposited or liberated at any electrode is directly
proportional to the quantity of electricity passed through the electrolytic
solution.

➢ If W gm. of substance is deposited on passing Q coulombs of electricity,

then

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Wα Q
W = Z.Q ……………………………………(1)
Z is a proportionality constant. It is called as electrochemical equivalent
of substance.
Q = I.t
W = Z.I.t …………………………………….(2)
If I = 1 Ampere, t = 1 sec.
Then W = Z …………………………………….(3)

➢ Electrochemical equivalent of a substance may be defined as the mass of

the substance (gm.) deposited when a current of 1 Ampere is passed for
1 sec., i.e. 1 Cb electricity.
Unit
𝑊
𝑍=
𝑄

gm/cb
SECOND LAW OF FARADAY

➢ When the same quantity of electricity passed through solutions of

different electrolytes connected in series, the masses of substances
deposited at the electrodes are directly proportional to their equivalent
mass.

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𝐴𝑡𝑜𝑚𝑖𝑐 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑚𝑒𝑡𝑎𝑙 𝑎𝑡𝑜𝑚

𝐸𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑎𝑡𝑜𝑚 (𝑐𝑎𝑡𝑖𝑜𝑛) =
𝑛𝑜. 𝑜𝑓 𝑒 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑡𝑜 𝑟𝑒𝑑𝑢𝑐𝑒𝑑 𝑡𝑜 𝑐𝑎𝑡𝑖𝑜𝑛

𝑀𝑎𝑠𝑠 𝑜𝑓 𝐴𝑔 𝑑𝑒𝑝𝑜𝑠𝑖𝑡𝑒𝑑 𝐸𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑚𝑎𝑠𝑠 𝑜𝑓 𝐴𝑔

=
𝑀𝑎𝑠𝑠 𝑜𝑓 𝐶𝑢 𝑑𝑒𝑝𝑜𝑠𝑖𝑡𝑒𝑑 𝐸𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑚𝑎𝑠𝑠 𝑜𝑓 𝐶𝑢
Suppose
W1 & W2 = mass of substances deposited on electrodes
E1 & E 2 = equivalent mass of substances
𝑊1 𝐸1
=
𝑊2 𝐸2

We know that
W1 = Z1.I.t
W2 = Z2.I.t
𝑊1 𝑍1. 𝐼.𝑡 𝐸1
= =
𝑊2 𝑍2. 𝐼.𝑡 𝐸2

ZαE
➢ Hence the electrochemical equivalent of substance is directly
proportional to its equivalent mass.
Note:
✓ The charged carried by 1 mole of electron = 1.6 x 10 -19 x NA
= 1.6 x 10 -19 x 6.023 x 1023 = 96487 ≈ 96500 Cb.mol-1
✓ This quantity is called as one faraday. It is constant value. This is called as
faraday constant. It is represented by F.
1 F = 96500 Cb.mol-1
✓ One faraday of electricity deposits one gm. equivalent of the substance.

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Some formula for solving numerical:

𝑊
𝐸= 𝑋 96500
𝑄

(E= Equivalent mass of substance)

𝑄.𝐸
𝑊= (Q=I.t)
96500
𝐼.𝑡.𝐸
𝑊=
96500
𝐸
𝑍=
𝐹(96500)
✓ For the calculation of amount liberated/deposited by a certain quantity
of the electricity or vice versa, write balanced electrode reaction.
✓ No. of electrons gives the no. of faradays required for the no. of moles of
that substances in balanced equation.

ELECTROLYTIC CONDUCTANCE
➢ The conduction of electricity in electrolyte solution is called as
electrolytic conductance.
➢ In these process the electrolyte undergo decomposition when current is
passed through them.
Ex. Solution of acid, base and salt in water, molten salts.
In this case, the flow of electricity is due to the movement of ions.
Factor affecting electrolytic conductance
1. Nature of electrolyte
➢ In the case of strong electrolyte ionisation property increases, hence
electric conductance increases.
Ex. Strong acid- HCl, H2SO4, HNO3 etc.
Strong base- NaOH, KOH etc.
Salts- NaCl, KCl, Na2SO4, KNO3 etc.
➢ In the case weak electrolyte ionisation property decreases, hence
electric conductance decreases.

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Ex. Weak acid- H2CO3, CH3COOH etc.

Weak base- NH4OH, Ca(OH)2, Al(OH)3 etc.
2. Size of ion produced and their solvation
➢ As size of ions increases, solvation(combination of ion with solvent)
increases, movement of ions decreases, hence electric conductance
decreases.

3. Nature of solvent
➢ Electrolytes ionize in a polar solvent.
➢ As polarity of solvent increases, ionisation of electrolytes increases,
hence electric conductance increases.

4. Concentration of electrolyte
➢ Conductance decrease as increases in concentration.
➢ At higher concentration interionic attraction increases, movement of
ions decreases, hence conductance decreases.
➢ At lower concentration interionic attraction decreases, movement of
ions increases, hence conductance increases.

5. Temperature
➢ As increase in temperature ionisation increases, hence conductance
increases.

ELECTRICAL RESISTANCE AND CONDUCTANCE

➢ Like as metallic conductors, electrolytes also follow ohm’s law.
➢ According to this law-
The current flow in any conductor is equal to the ratio of voltage (V) applied on
conductor and its resistance (R).
𝑽
𝑰= …………………………………..(1)
𝑹
𝑽
𝑹= 𝑰
…………………………………..(2)

Unit of R: SI unit:- ohm (Ω)

𝑣𝑜𝑙𝑡
𝑜ℎ𝑚 =
𝑎𝑚𝑝𝑒𝑟𝑒

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The reciprocal of the electrical resistance is called the conductance. It is

represented by G.
𝟏
𝑮= …….……………………..(3)
𝑹
Unit of G: SI unit:- ohm-1 or mho
Siemens (S)
1 S = 1 Ω-1
SPECIFIC CONDUCTIVITY
➢ The resistance R of a conductor is directly proportional to its length (l)
and inversely proportional to its area of cross-section.
𝒍
𝑹∝
𝒂
𝒍
𝑹 = 𝝆. …………………………….(4)
𝒂

here 𝝆 = Specific resistance/resistivity

If 𝑙 = 1 𝑐𝑚., a = 1 cm2
Then R=𝜌
Resistivity is defined as the resistance of a conductor whose length is 1 cm and
area of cross-section is 1 cm2.
Or
Resistivity is the resistance of 1 cm3 or 1m3 of the conductor.
Unit of 𝝆: SI unit:- ohm x m, Ωxm
ohm x cm. Ω x cm
1 Ω x m = 100 Ω x cm
The reciprocal of resistivity is called as Specific conductance or Conductivity. It
is represented by kappa (K).
1
𝐾=
𝜌

𝑙
𝑅 = 𝜌.
𝑎

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1 1 𝑎
= 𝑋 …………………………..(5)
𝑅 𝜌 𝑙
𝑎
𝐺 = 𝐾. …………………………..(6)
𝑙
𝑙
𝐾 = 𝐺. …………………………..(7)
𝑎

If l = 1 cm. a = 1 cm2
Then 𝐾=G
Conductivity of a solution may be defined as the conductance of a solution of 1
cm. length and 1 cm2 cross-section area.
Or
Conductivity is the conductance of 1 cm3/1m3 of solution of electrolytes (conductor).
We know that
𝑙 𝑙
𝐾 = 𝐺. { = 𝐺 ∗ (𝑐𝑒𝑙𝑙 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡) }
𝑎 𝑎

K = G . 𝑮∗
Conductivity = conductance x cell constant
K
G∗ = =KxR
G

1 1
Unit of K (Kappa): SI unit:- 𝐾= =
𝜌 𝑜ℎ𝑚 . 𝑚

𝑜ℎ𝑚−1 . 𝑚−1 ; Ω-1. 𝑚−1 ; S . 𝑚−1

𝑜ℎ𝑚−1 . 𝑐𝑚−1 ; Ω-1. 𝑐𝑚−1 ; S . 𝑐𝑚−1
1 S . 𝒄𝒎−𝟏 = 100 S . 𝒎−𝟏
Unit of 𝑮∗
𝑙 𝑚
𝐺∗ = = = 𝑚−1 = 𝑐𝑚−1
𝑎 𝑚2

Note:
If volume of solution is V cm3, the conductivity of such a solution at this
dilution V is written as Kv.
At concentration C, it is written as Kc.

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MOLAR CONDUCTIVITY
➢ Molar conductivity of a solution is the conductance of all the ions
produced from 1 mole of the electrolytes dissolved in Vcm3 of solution
when electrodes are 1 cm. apart.
➢ It is represented by λm or Λ0m
λm = specific conductance x V
λm = Kv x V
1000
𝜆𝑚 = 𝐾𝑐 X
𝐶
1000
𝜆𝑚 = 𝐾𝑐 X
𝑚𝑜𝑙𝑎𝑟𝑖𝑡𝑦

Note:
C = mole/lit.
mole
C= X 1000 (here 1 mole)
V(ml.)
1000
V=
C

Unit of 𝝀𝒎 SI unit
𝑜ℎ𝑚−1 .𝑚−1
𝜆𝑚 = = 𝑜ℎ𝑚−1 . 𝑚2 . 𝑚𝑜𝑙𝑒 −1
𝑚𝑜𝑙𝑒.𝑚−3

𝑆. 𝑚2 . 𝑚𝑜𝑙𝑒 −1
𝑜ℎ𝑚−1 . 𝑐𝑚−1
𝜆𝑚 = −3
= 𝑜ℎ𝑚−1 . 𝑐𝑚2 . 𝑚𝑜𝑙𝑒 −1
𝑚𝑜𝑙𝑒. 𝑐𝑚
𝑆. 𝑐𝑚2 . 𝑚𝑜𝑙𝑒 −1
1 𝑆. 𝑚2 . 𝑚𝑜𝑙𝑒 −1 = 104 𝑆. 𝑐𝑚2 . 𝑚𝑜𝑙𝑒 −1
1 𝑆. 𝑐𝑚2 . 𝑚𝑜𝑙𝑒 −1 = 10-4 𝑆. 𝑚2 . 𝑚𝑜𝑙𝑒 −1
In term of SI unit
𝐾
𝜆𝑚 = (here is no multiplication with 1000)
𝑚𝑜𝑙𝑎𝑟𝑖𝑡𝑦

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EQUIVALENT CONDUCTIVITY
➢ Equivalent conductivity of a solution is the conductance of all the ions
produced from 1 gm equivalent of the electrolytes dissolved in V cm3 of
the solution when electrodes are 1 cm apart.
➢ It is represented by 𝜆𝑒𝑞 .
𝜆𝑒𝑞 = 𝑆pecific conductance x V
λeq = Kv x V

1000
𝜆𝑒𝑞 = 𝐾𝑐 X
𝐶𝑒𝑞

1000
𝜆𝑒𝑞 = 𝐾𝑐 X
𝑁𝑜𝑟𝑚𝑎𝑙𝑖𝑡𝑦

Unit of 𝝀𝒎 SI unit
𝑜ℎ𝑚−1 .𝑚−1
𝜆𝑒𝑞 = = 𝑜ℎ𝑚−1 . 𝑚2 . 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 −1
𝑔𝑚 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 . 𝑚−3

𝑆. 𝑚2 . 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 −1
𝑜ℎ𝑚−1 . 𝑐𝑚−1
𝜆𝑒𝑞 = = 𝑜ℎ𝑚−1 . 𝑐𝑚2 . 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 −1
𝑔𝑚 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 . 𝑐𝑚−3
𝑆. 𝑐𝑚2 . 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 −1
1 𝑆. 𝑚2 . 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 −1 = 104 𝑆. 𝑐𝑚2 . 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 −1
1 𝑆. 𝑐𝑚2 . 𝑒𝑞𝑣𝑖𝑣𝑎𝑙𝑒𝑛𝑡 −1 = 10-4 𝑆. 𝑚2 . 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 −1
In term of SI unit
𝐾𝑐
𝜆𝑒𝑞 = (here is no multiplication with 1000)
𝑛𝑜𝑟𝑚𝑎𝑙𝑖𝑡𝑦

Relation between 𝝀𝒎 𝒂𝒏𝒅 𝝀𝒆𝒒

1000 1000
𝜆𝑒𝑞 = 𝐾𝑐 X = 𝐾𝑐 𝑋
𝑁𝑜𝑟𝑚𝑎𝑙𝑖𝑡𝑦 𝑚𝑜𝑙𝑎𝑟𝑖𝑡𝑦 𝑋 𝑥−𝑓𝑎𝑐𝑡𝑜𝑟

1000
𝜆𝑚 = 𝐾𝑐 X
𝑚𝑜𝑙𝑎𝑟𝑖𝑡𝑦

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𝝀𝒎
𝝀𝒆𝒒 =
𝒙 − 𝒇𝒂𝒄𝒕𝒐𝒓
MEASUREMENT OF ELECTROLYTIC CONDUCTANCE
➢ Conductance is reciprocal of resistance.
𝟏
G=
𝑹

➢ The resistance can be determined by the principal of Wheatstone bridge.

R1 and R2 = Known resistance

R3 = Variable resistance
Rx = Unknown resistance
➢ When null point is obtained, then no deflection in the galvanometer G.
𝑅1 𝑅3
=
𝑅2 𝑅𝑥

𝑅2 . 𝑅3
𝑅𝑥 =
𝑅1
IN CASE OF ELECTROLYTIC SOLUTION
Finding the resistance of electrolytic solution
I difficulty
➢ The solution cannot be connected to bridge like a metallic wire or any
other solid conductor.
Solution

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➢ A special type of vessel is used in which solution is taken between two

electrodes. This apparatus is called as CONDUCTIVITY CELL. It is made up of
pyrax glass and contain two Pt electrodes.
II difficulty
➢ If D.C. is passed then it causes electrolysis. Due to this concentration of
electrolytes near the electrode changes and this result change in the
resistance of solution. This is called as POLARIZATION EFFECT.

Solution
➢ When AC current is passed, ordinary galvanometer fails to detect the null
point. So, galvanometer is replaced by earphone as the detector.
➢ To minimize the polarization effect, the electrodes are coated with Pt
Black.
There are three modifications required in usual Wheatstone bridge method:-
a. DC source is replaced by AC source. These give more symmetrical current.
AC source – Induction coil or vacuum tube oscillator
These give more symmetrical current.
b. Galvanometer is replaced by an earphone.
c. Pt electrodes are coated by Pt black.

(Apparatus used for measurement of electrolytic conductance)

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In the position of null point

𝑅1 𝑅3
=
𝑅2 𝑅𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑅2 . 𝑅3
𝑅𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 =
𝑅1
𝟏
Conductance 𝑮=
𝑹𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏

Conductivity water

For accurate result solution should be prepared in a specially purified water

whose own conductivity is very small. Such water is called as conductivity
water.

VARIATION OF CONDUCTIVITY AND MOLAR CONDUCTIVITY WITH CONCENTRATION

➢ For both weak and strong electrolytes, conductivity decreases with

decrease in concentration (on dilution).

Reason: Deceases in the no. of ions per unit volume carrying the current in
solution.

➢ For both weak and strong electrolytes, molar conductivity increases with
decrease in concentration (on dilution).

λm = Kv x V

➢ When concentration approaches zero (infinite dilution), the molar

conductivity is known as limiting molar conductivity.
➢ Molar conductivity for strong electrolytes can be represented by
following equation:

λ𝑚 = λ𝑚 0 − 𝐴. √𝐶

➢ This is called as DEBYE-HUCKEL-ONSAGER EQUATION. It is found to hold good

at low concentration.

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λ𝑚 0 = Intercept, Molar conductivity at infinite dilution. It is called as limiting

molar conductivity

-A = Slope, it’s a constant value, depend on electrolytes

λ𝑚 = Molar conductivity at any concentration

➢ Strong electrolytes are completely ionised.

➢ At higher concentration, the greater inter-ionic attraction retards the
motion of ions, so the molar conductivity decreases with increase in
concentration.
➢ With decrease in concentration (with dilution), the ions are far apart.
The inter-ionic attractions decrease, due to this molar conductivity
increase with dilution and approaches a maximum limiting value at
infinite dilution 𝛌𝒎 𝟎 .

KOHLRAUSCH’S LAW

➢ Each ion makes a definite contribution to the total molar conductivity of

an electrolyte at infinite dilution.
➢ The individual contribution of an ion towards the total molar
conductivity of electrolyte is called MOLAR IONIC CONDUCTIVITY.
➢ According to Kohlrausch’s law- The limiting molar conductivity of an
electrolyte is the sum of the limiting ionic conductivity of the cation and
anion each multiplied with the no. of ions present in one formula unit of
electrolyte.
Or

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The molar conductivity of an electrolyte at infinite dilution is the sum of

molar conductivity of individual ions.

𝛌𝒎 𝟎 = ν+. 𝛌+ 𝟎 + ν-. 𝛌− 𝟎

Where

λ𝑚 0 = limiting molar conductivity of the electrolyte

λ+ 0 & λ− 0 = limiting molar conductivity of cation and anion

ν+ & ν- = No. of cations and anions present in one formula unit of electrolyte
Ex. For NaCl

λ0m = λ0Na+ + λ0Cl-

For BaCl2

λ0m = λ0Ba2+ + 2 λ0Cl-

For Al2(SO4)3

λ0m = 2 λ0Al3+ + 3 λ0 SO
4
-2

In terms of equivalent conductivities

The equivalent conductivity of an electrolyte at infinite dilution is the sum of

limiting ionic conductivities of cations and anions.

λ0eq = λ0c + λ0a

ABSOLUTE IONIC MOBILITY

➢ The absolute ionic mobility is defined as the speed of the ion in cm/sec
at infinite dilution under a potential gradient of 1 volt/cm.
Applied EMF
Potential gradient =
Distance between electrodes

Speed of ion
Absolute ionic mobility =
Potential gradient

𝒄𝒎 . 𝒔𝒆𝒄−𝟏
Unit = cm2. sec-1. volt-1
𝒗𝒐𝒍𝒕 . 𝒄𝒎−𝟏
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Limiting ionic conductivity α absolute ionic mobility

λ0c α uoc ; λ0c = K . uoc

λ0a α uoa ; λ0a = K . uoa

λ0c + λ0a = K (uoc + uoa)

λ0eq = K (uoc + uoa)

λ0m = K (uo+ + uo-)

➢ The value of K is found to be equal to F.

𝛌𝒄 𝟎
λ0c = F . uoc ; uoc =
𝐹

𝛌𝒂 𝟎
λ0a = F . uoa ; uoa =
𝐹

𝒊𝒐𝒏𝒊𝒄 𝒄𝒐𝒏𝒅𝒖𝒄𝒕𝒂𝒏𝒄𝒆
𝒊𝒐𝒏𝒊𝒄 𝒎𝒐𝒃𝒊𝒍𝒊𝒕𝒚 =
𝟗𝟔𝟓𝟎𝟎

APPLICATION OF KOHLRAUSCH’S LAW

(A) CALCULATION OF MOLAR CONDUCTIVITY AT INFINITE DILUTION (λ0m) FOR WEAK

ELECTROLYTES
➢ Experimentally, the molar conductivity of a weak electrolyte at infinite
dilution cannot be determined. Because conductance of these solution is
very low and dissociation of these electrolyte is not complete. Molar
conductivity of these electrolyte can be determined by Kohlrausch’s law.

Ex. Weak electrolyte CH3COOH

λ0 CH3COOH = λ0 CH3COO- + λ0 H+ ……………………………(1)

This equation can be arrived by knowing the molar conductivity at infinite

dilution for the strong electrolytes.

Eg. KCl, CH3COOK, HCl

λ0 KCl = λ0 K+ + λ0Cl- …………………………….(2)

λ0 CH3COOK = λ0 CH3COO- + λ0 K+ …………………………….(3)

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 CLASS-XII CHEMISTRY

λ0 HCl = λ0 H+ + λ0Cl- ……………………………(4)

equation (3)+(4)-(2)

λ0 CH3COOK + λ0 HCl - λ0 KCl = (λ0 CH3COO- + λ0 K+) + (λ0 H+ + λ0Cl-) – (λ0 K+ + λ0Cl-)

λ0 CH3COOK + λ0 HCl - λ0 KCl = λ0 CH3COO- + λ0 H+

λ0 CH3COOH = λ0 CH3COOK + λ0 HCl - λ0 KCl …………………………….(5)

from equation (5), we can calculate the molar conductivity at infinite dilution
of Weak electrolyte CH3COOH can be calculated.

(B) CALCULATION OF THE DEGREE OF DISSOCIATION

Suppose

α = Degree of dissociation

λ0m = Molar conductivity at infinite dilution (Zero concentration)

λcm = Molar conductivity at concentration C

𝛌𝒄𝒎
𝜶=
𝛌𝟎𝒎

This equation is used for WEAK ELECTROLYTES.

(C) CALCULATION OF DISSOCIATION CONSTANT FOR WEAK ELECTROLYTES

𝐂 . 𝛂𝟐
𝐊=
𝟏−𝛂

(D) CALCULATION OF SOLUBILITY CONSTANT OF A SPARINGLY SOLUBLE SALTS

➢ Salts like as AgCl, BaSO4, PbSO4, PbCl2 dissolve in water to very small
extent are called as sparingly soluble salts.
➢ As they are little soluble, their solutions are considered as infinitely
dilute. So whatever amount of salt is dissolved in water considered as
completely ionized. As their solution are saturated, their concentration
is equal to their solubility.

λm = λ0m (considered as infinite dilution)

molarity = solubility

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 CLASS-XII CHEMISTRY

𝐾 𝑋 1000 𝐾 𝑋 1000
λ𝑜𝑚 = =
𝑚𝑜𝑙𝑎𝑟𝑖𝑡𝑦 𝑠𝑜𝑙𝑢𝑏𝑖𝑙𝑖𝑡𝑦
𝑲 𝑿 𝟏𝟎𝟎𝟎
𝒔𝒐𝒍𝒖𝒃𝒊𝒍𝒊𝒕𝒚 =
𝛌𝒐𝒎

✓ λ𝑜𝑚 can be calculated by Kohlrausch’s law.

ELECTROCHEMICAL CELL

➢ It is defined as a device used to convert chemical energy into electrical

energy.
➢ These are firstly synthesized by Luige Galvani or Volta. So these are also
called as galvanic cell or Voltic cell.

Ex. Daniel cell, Dry cell, Battery

FEATHERS OF A ELECTROCHEMICAL CELL

➢ The Zn rod at which the oxidation occurs is called the anode and Cu rod
at which the reduction occurs is called as cathode.
➢ Each beaker constitutes a half-cell also called electrode or the redox
couple. Thus, a half-cell consists of a metal rod dipped in the solution of
its own ions.
➢ Redox couple is a combination of the oxidised and reduced form of the
same substance taking part in an oxidation or reduction half-cell reaction.
AMIT KUMAR RAKHECHA, CHEMISTRY LECTURER 21
 CLASS-XII CHEMISTRY

➢ The reaction taking place in half-cell is called as half-cell reaction.

➢ The half-cells are connected by salt-bridge.

SALT-BRIDGE
➢ Salt bridge is the inverted U-Shape tube which is filled with paste of inert
electrolyte (KCl / KNO3/ NH4Cl / NH4NO3) in agar-agar
➢ The inert electrolyte means which does not undergoes itself reduction or
oxidation process.
➢ The ionic Mobility of the counter ions of inert electrolyte is same.
➢ Salt bridge complete the electrical circuit.
➢ It allows the movement of ions from one solution to other without
mixing of two solutions.
➢ It helps to maintain the electrical neutrality of the solution due to flow
of ions.
➢ It is used to decrease the liquid junction potential.

ELECTROCHEMICAL CELL REACTION

Reaction at Anode (Zn)

Zn(s) → Zn+2(aq.) + 2e- (OXIDATION)
➢ Weight of Anode decreases
➢ Concentration of Zn+2 ion in Solution increases
➢ It is called Oxidation Half Cell

Reaction at Cathode (Cu)

Cu+2(aq) + 2e- → Cu(s) (REDUCTION)
➢ Weight of Cathode increases
➢ Concentration of Cu+2 ion in Solution decreases
➢ It is called Reduction Half cell

Note:
✓ The no. of gram equivalent of Zn+2 ions goes into the solution are
equal to the no. of gram equivalent of Cu+2 ions are deposited on Cu rod.

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 CLASS-XII CHEMISTRY

Representation of Galvanic Cell

Oxidation Half Cell ‫ װ‬Reduction Half Cell
Zn(s) / ZnSO4 ‖ CuSO4 / Cu (s)
Zn(s) / Zn2+ ‖ Cu2+/ Cu (s)
Zn(s) / ZnSO4(xM) ‖ CuSO4 (yM) / Cu (s)

Generally
M(s)/M+n (xM) ‖ Z+n(yM)/ Z(s)
M(s);M+n (xM) ‖ Z+n(yM); Z(s)
Zn(s) / ZnSO4(xM) ‖ CuSO4 (yM) / Cu (s)

ELECTRODE POTENTIAL

➢ Each electrode has tendency to lose or gain e-. Due to this a potential is
produced on electrode. This is called as electrode potential.
➢ If the electrode loses e-, then the electrode potential is termed as
oxidation potential.
➢ If the electrode gains e-, then the electrode potential is termed as
reduction potential.
➢ Oxidation and reduction potentials are reverse of each other.
➢ If the oxidation potential of an electrode is x-volts then its reduction
potential is -x volts.
➢ The electrode potential of any electrode depends upon the
concentration of the ions and temperature.
➢ If the concentration of ions is taken as unity (1 mol.L-1) (if any gas
appears in the electrode reaction, it is taken at 1 atm. pressure) and
temperature is taken as 298 K (250C), then the electrode potential is
called as STANDARD ELECTRODE POTENTIAL; E0.
➢ To determine the electrode potential of any electrode, a reference
electrode is used which is called as STANDARD HYDROGEN ELECTRODE or
NORMAL HYDROGEN ELECTRODE.

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CLASS-XII CHEMISTRY

STANDARD HYDROGEN ELECTRODE (SHE)

➢ It consists of a platinized Pt electrode dipped in 1M solution of H+ ions
(1M HCl) at 298 K temperature and pure H2 gas maintained at 1 atm.
Pressure.

➢ If this electrode acts as the anode in a cell, then oxidation takes place.
H2 → 2 H + + 2 e -
➢ If this electrode acts as cathode in a cell, then reduction takes place.
2 H+ + 2 e- → H2
➢ The electrode potential of standard hydrogen electrode is taken as zero.

DETERMINATION OF ELECTRODE POTENTIAL OF UNKNOWN ELECTRODE

➢ To determine the electrode potential of any electrode, a cell is set up

using this electrode as one of the electrodes and the second electrode is
standard hydrogen electrode.
➢ The EMF of cell is measured. EMF of cell is the difference in the
electrode potential of two half cells. Since the electrode potential of SHE
is taken as zero, so the EMF of this cell is called as the electrode
potential of the unknown electrode.

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 CLASS-XII CHEMISTRY

Cell reaction for above electrochemical cell

At anode H2 → 2 H+ + 2 e-
At cathode Cu+2(aq) + 2e- → Cu(s)
Complete cell reaction Cu+2(aq) + H2(g) → 2 H+ + Cu(s)

Cell Potential or EMF of a Cell

➢ EMF is the Potential difference between the two electrodes of the cell
when no current is flowing in Circuit (open Circuit).
➢ The EMF of Cell Depends on-
a. Nature of Reactant
b. Concentration of Solution of electrolytes
c. Temperature

Eocell = Std. reduction pot. Of cathode-std. reduction pot. Of anode

Eocell = Eocathode - Eoanode
➢ Reduction will occur at the electrode having higher Reduction Potential
and Oxidation will occur at the electrode having lower reduction
potential.

NERNST EQUATION FOR ELECTRODE POTENTIAL

(Effect of Electrolyte Concentration and Temperature on the Electrode
Potential)
➢ When Electrolyte Concentration is 1M & temperature is 298 K, then
electrode Potential is said to be Standard Electrode Potential.

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 CLASS-XII CHEMISTRY

➢ If Electrolyte Concentration is different from 1M or temperature is

different from 298K, the Electrode Potential has a different value. This
value can be obtained by Nernst Equation.
Suppose a Electrode Reduction Reaction
Mn+ + ne- → M
Nernst gave following equation for above electrode reaction
𝑹𝑻 [𝑴]
𝑬 = 𝑬𝟎 − 𝒍𝒏 [𝑴𝒏+] …………..…….(1)
𝒏𝑭

Here
E= Electrode Potential under given Concentration of M+n ion and Temperature T
E0= Standard Electrode Potential
R= Gas Constant
F= 1 Faraday
n = no. of Electron involved in Electrode Reaction
For pure Solid or liquid or Gas at 1 atm Pressure, the Molar Concentration is
taken as Unity.
[𝑴] = 𝟏
𝑹𝑻 𝟏
𝑬 = 𝑬𝟎 − 𝒍𝒏 [𝑴𝒏+ ]
𝒏𝑭
𝟐.𝟑𝟎𝟑𝑹𝑻 𝟏
𝑬 = 𝑬𝟎 − 𝒍𝒐𝒈 [𝑴𝒏+ ] ……………..………(2)
𝒏𝑭

𝟎.𝟎𝟓𝟗𝟏 𝟏
𝑬 = 𝑬𝟎 − 𝒍𝒐𝒈 [𝑴𝒏+] …………………….(3)
𝒏
(here R= 8.314 ; F= 96500 ; T= 298K (25℃) )
Note: while applying Nernst Equation , Electrode Potential is always taken as
Reduction electrode Potential.
NERNST EQUATION FOR SHE
Reduction electrode reaction
1
H+ + e- → H2
2

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 CLASS-XII CHEMISTRY

Nernst equation
𝟎.𝟎𝟓𝟗𝟏 𝟏
𝑬 = 𝑬𝟎 − 𝒍𝒐𝒈 [𝑯+]
𝟏

𝑬𝟎 = 𝟎 (for SHE)
𝟏
𝑬 = - 0.0591 𝒍𝒐𝒈 [𝑯+]

𝑬 = - 0.0591 {−𝒍𝒐𝒈 [𝑯+ ]}

𝑬 = - 0.0591 PH

NERNST EQUATION FOR EMF OF A CELL

(Effect of electrolyte Concentration and Temperature on the EMF of a Cell)
Let us take a example of a Daniel Cell:
Zn + Cu+2 → Zn+2 + Cu
For Anode ( Zn+2 /Zn):
Zn+2 + 2e- → Zn

𝑹𝑻 𝟏
𝑬 𝒁𝒏+𝟐⁄ = 𝑬𝟎 𝒁𝒏+𝟐⁄ − 𝒍𝒏 [𝒁𝒏+𝟐] ……….…..…….(1)
𝒁𝒏 𝒁𝒏 𝒏𝑭

For Cathode (Cu+2 /Cu)

Cu+2 + 2e- → Cu

𝑹𝑻 𝟏
𝑬 𝑪𝒖+𝟐⁄ = 𝑬𝟎 𝑪𝒖+𝟐⁄ − 𝒍𝒏 [𝑪𝒖+𝟐] …………….......(2)
𝑪𝒖 𝑪𝒖 𝒏𝑭

𝐸𝑐𝑒𝑙𝑙 = Reduction potential of Reduction half reaction −

Reduction potential of Oxidation half reaction
Ecell = Ecathode - Eanode
𝑬𝒄𝒆𝒍𝒍 = 𝑬𝟎 𝑪𝒖+𝟐⁄ − 𝑬𝟎 𝒁𝒏+𝟐⁄
𝑪𝒖 𝒁𝒏

𝑹𝑻 𝟏 𝑹𝑻 𝟏
𝑬𝒄𝒆𝒍𝒍 = {𝑬𝟎 𝑪𝒖+𝟐⁄ − 𝒍𝒏 [𝑪𝒖+𝟐]} − {𝑬𝟎 𝒁𝒏+𝟐⁄ − 𝒍𝒏 [𝒁𝒏+𝟐]}
𝑪𝒖 𝒏𝑭 𝒁𝒏 𝒏𝑭

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𝑹𝑻 𝟏 𝑹𝑻 𝟏
𝑬𝒄𝒆𝒍𝒍 = 𝑬𝟎 𝑪𝒖+𝟐⁄ − 𝑬𝟎 𝒁𝒏+𝟐⁄ − 𝒍𝒏 [𝑪𝒖+𝟐] + 𝒍𝒏 [𝒁𝒏+𝟐]
𝑪𝒖 𝒁𝒏 𝒏𝑭 𝒏𝑭

𝑹𝑻 [𝒁𝒏+𝟐 ]
𝑬𝒄𝒆𝒍𝒍 = 𝑬𝟎 𝑪𝒆𝒍𝒍 − 𝒍𝒏 [𝑪𝒖+𝟐] …………….……(3)
𝒏𝑭

𝟐.𝟑𝟎𝟑𝑹𝑻 [𝒁𝒏+𝟐 ]
𝑬𝒄𝒆𝒍𝒍 = 𝑬𝟎 𝑪𝒆𝒍𝒍 − 𝒍𝒐𝒈 [𝑪𝒖+𝟐]
𝒏𝑭

𝟎.𝟎𝟓𝟗𝟏 [𝒁𝒏+𝟐 ]
𝑬𝒄𝒆𝒍𝒍 = 𝑬𝟎 𝑪𝒆𝒍𝒍 − 𝒍𝒐𝒈 [𝑪𝒖+𝟐]
𝟐

Cu+2 ↑ Ecell ↑; Zn+2 ↓ Ecell ↑

Ex. Ni/Ni+2 ‖ Ag+/Ag

𝑹𝑻 [𝑵𝒊+𝟐 ]
𝑬 = 𝑬𝟎 𝑪𝒆𝒍𝒍 − 𝒍𝒏 [𝑨𝒈+ ]𝟐 (here n=2)
𝒏𝑭

For a general cell reaction

𝒏𝒆−
aA + bB → xX + yY
𝑹𝑻 [𝑿]𝒙 [𝒀]𝒚
𝑬 = 𝑬𝟎 𝑪𝒆𝒍𝒍 − 𝒍𝒏 [𝑨]𝒂[𝑩]𝒃
𝒏𝑭

EQUILLIBRIUM CONSTANT FROM NERNST EQUATION

➢ Let us Consider a Cell
Zn/ZnSO4 ‖ CuSO4/Cu
Electrons flow from Zn to Cu in external circuit

Following process takes places in internal circuit-

a. Zn from Zn rod passes into solution as Zn+2 ions

b. Cu+2 ions from CuSo4 solution are deposited on Cu rod
c. So4-2 ions from CuSo4 flow to ZnSo4 solution through Salt Bridge
➢ As concentration of CuSo4 Decreases, concentration of ZnSo4 increases
➢ As concentration of solution changes, the electrode potential also
changes.
➢ Ultimately a stage comes when the electrode potential of two electrodes
become equal and the current stops flowing in the circuit i.e. EMF of cell
becomes zero.

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 CLASS-XII CHEMISTRY

Electrochemical Reaction
Zn + Cu+2 ⇌ Zn+2 + Cu
At equilibrium
[𝑍𝑛+2 ]
𝐾𝑐 = [𝐶𝑢+2 ]
………………..…….(1)

EMf of Cell = Zero

Nernst Equation for above Reaction
𝑹𝑻 [𝒁𝒏+𝟐 ]
𝑬𝒄𝒆𝒍𝒍 = 𝑬𝟎 𝑪𝒆𝒍𝒍 − 𝒍𝒏 [𝑪𝒖+𝟐] ……………..……….(2)
𝒏𝑭

𝟐.𝟑𝟎𝟑𝑹𝑻 [𝒁𝒏+𝟐 ]
𝟎 = 𝑬𝟎 𝑪𝒆𝒍𝒍 − 𝒍𝒐𝒈 [𝑪𝒖+𝟐]
𝟐𝑭
𝟐.𝟑𝟎𝟑𝑹𝑻 [𝒁𝒏+𝟐 ]
𝑬𝟎 𝑪𝒆𝒍𝒍 = 𝒍𝒐𝒈 [𝑪𝒖+𝟐] ………………….…..(3)
𝟐𝑭

From equation (1) and (3)

𝟐.𝟑𝟎𝟑𝑹𝑻
𝑬𝟎 𝑪𝒆𝒍𝒍 = 𝒍𝒐𝒈𝑲𝒄 ……………………..(4)
𝟐𝑭
𝟎.𝟎𝟓𝟗𝟏
𝑬𝟎 𝑪𝒆𝒍𝒍 = 𝒍𝒐𝒈𝑲𝒄 ……………..….…..(5)
𝟐

(𝑬𝟎 𝑪𝒆𝒍𝒍 (𝑫𝒂𝒏𝒊𝒆𝒍𝒍) = 𝟏. 𝟏𝑽 at 298 K Temperature )

Generally

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 CLASS-XII CHEMISTRY

𝟐.𝟑𝟎𝟑𝑹𝑻
𝑬𝟎 𝑪𝒆𝒍𝒍 = 𝒍𝒐𝒈𝑲𝒄 …………………….(6)
𝒏𝑭

Q. Calculate the Equilibrium Constant for the reaction

Cu + 2Ag+ ⇌ Cu+2 + 2Ag
𝐸 0 𝐴𝑔+ = 0.80 𝑉 ; 𝐸 0 𝐶𝑢+2⁄ = 0.34𝑉
⁄𝐴𝑔 𝐶𝑢

Ans. E0cell = E0cathode - Eoanode

E0cell = 0.80 - 0.34 = 0.46V

𝟎.𝟎𝟓𝟗𝟏
𝑬𝟎 𝑪𝒆𝒍𝒍 = 𝒍𝒐𝒈𝑲𝒄 (Here n= 2)
𝒏

𝐸 0 𝑐𝑒𝑙𝑙 ×𝑛 0.46×2
logKc = = = 15.5668
0.0591 0.0591

Kc = antilog 15.5668 = 3.6×1015

Q. Calculate EMF of Following Cell (At 298K)

Co/Co+2(1.0M) ‖ Ni+2(0.01M)/Ni
E0cell= 0.03 V
ANS. Electrochemical reaction for cell
Co + Ni+2 ⇌ Co+2 + Ni
𝟎.𝟎𝟓𝟗𝟏 [𝑪𝒐+𝟐 ]
𝑬𝒄𝒆𝒍𝒍 = 𝑬𝟎 𝑪𝒆𝒍𝒍 − 𝒍𝒐𝒈 [𝑵𝒊+𝟐]
𝒏

𝟎.𝟎𝟓𝟗𝟏 𝟏
𝑬𝒄𝒆𝒍𝒍 = 𝟎. 𝟎𝟑 − 𝒍𝒐𝒈
𝟐 𝟎.𝟎𝟏

(log1/0.01 = log 100 = log10 + log10 = 1+1=2)

𝑬𝒄𝒆𝒍𝒍 = 0.03 – 0.0591 = -0.0291V
GIBB’S FREE ENERGY & CELL POTENTIAL (EMF)
Electrical Work done = Decrease in Free Energy

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 CLASS-XII CHEMISTRY

➢ In case of an electrochemical cell, the Electrical work done is equal to

Electrical Energy product
Electrical work done = Electrical Energy Product = Quantity of Electrical Flowing × EMF

If n moles of electrons are transferred in any cell then

Quantity of electricity flowing = nF

Ecell represents the EMF of the cell.

Suppose ΔG = Free Energy change

Electrical Work done = nF.Ecell
-ΔG = nF.Ecell …………………..……(1)
In Standard Condition
-ΔG0 = nFE0cell ..…………………….(2)
𝑅𝑇
𝐸 0 𝐶𝑒𝑙𝑙 = 𝑙𝑛𝐾𝑐 ..…………………….(3)
𝑛𝐹

From equation (2) & (3)

𝑅𝑇
−ΔG0 = 𝑛𝐹 𝑙𝑛𝐾𝑐
𝑛𝐹

-ΔG0 = RT.lnKc
ΔG0 = - RT.lnKc
ΔG0 = -2.303 RT log Kc …………………….(4)
BATTERIES
➢ A combination of two or more cells connected in Series is known as
Batteries.
➢ Generally these are Electrochemical Cell which convert the Chemical
energy of Redox Reaction into Electrical energy
➢ These are classified into three types:
1. Primary Cells
2. Secondary Cells
3. Fuel Cells

Primary Cells (Primary Battery)

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 CLASS-XII CHEMISTRY

➢ Primary Cells are Electrochemical Cell or Galvanic Cell which cannot be

recharged.
➢ These Cells becomes dead after using it for sometime.
➢ Electrochemical reaction cannot be reversed by passing electricity
through the Cell.

Ex. Dry Cell, Mercury Cell

DRY CELL
➢ It is also called as Lechlanche Cell. (Invented by G. Lechlanche)
➢ It consists of a Cylindrical Vessel made of Zn and is filled by a paste of
NH4Cl & ZnCl2. It is act as Anode.
➢ A Carbon rod in the Centre of Cell act as Cathode.
➢ The Cathode is Surrounded by MnO2 paste and Carbon.

Cell Reaction

At Anode
Zn → Zn+2 + 2e- (oxidation)
At Cathode
(+4) (+3)
2NH4+ + 2MnO2 + 2e- → Mn2O3 + 2NH3 + H2O (reduction)

Complete Cell Reaction

Zn + 2NH4+ + 2MnO2 → Zn+2 + Mn2O3 + 2NH3 + H2O

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 CLASS-XII CHEMISTRY

➢ A dry cell has Voltage (Potential) of 1.5 Volt.

MERCURY CELL
➢ In this Cell anode is Zn Container and C-rod acts as the Cathode.
➢ Moist HgO mixed with KOH & ZnO as electrolyte is filled between the
two electrodes.

At Anode

Zn + 2OH- → ZnO + H2O + 2e-

At Cathode

HgO + H2O + 2e- → Hg + 2OH-

Complete Cell Reaction
Zn + HgO → ZnO + Hg
➢ The electrode Potential of this Cell is 1.3 V.

FUEL CELL
➢ These are the Galvanic Cell which convert the energy of Combustion of
certain fuels into electrical energy.
➢ Such Conversions are possible because the Combustion reactions are
also Redox Reaction in nature.
➢ These are classified into two types:
1. Hydrogen- Oxygen fuel Cell
2. Hydrocarbon – Oxygen fuel Cell

HYDROGEN- OXYGEN FUEL CELL

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 CLASS-XII CHEMISTRY

➢ It consists of Porous C- electrodes.

➢ Suitable Catalyst like as finely divided Pt or Pd are added to these Porous
C-electrodes to accelerate the electrode reaction.
➢ Concentrated KOH or NaOH solution is placed between electrodes as
electrolytes.
➢ H2 & O2 gas are passed through the porous electrodes at high Pressure
into the electrolytes.

Cell Reaction
At Anode
2H2 (g) + 4OH-(aq.) → 4H2O (l) + 4e-
At Cathode
O2(g) + 2H2O(l) + 4e- → 4OH-(aq.)
Complete Cell Reaction
2H2 (g) + O2(g) → 2H2O(l)

HYDROCARBON- OXYGEN FUEL CELL

➢ In place of H2; certain Hydrocarbon such as CH4 , C2H6 , C3H8 & methanol
can also be used in the Fuel Cell.

Ex. Propane- O2 Fuel Cell

Cell Reaction
At Anode

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 CLASS-XII CHEMISTRY

C3H8 + 20 OH- → 3CO2 + 14 H2O + 20e-

At Cathode
5 O2 + 10 H2O + 2e- → 20 OH-
Complete Cell Reaction
C3H8 + 5O2 → 3 CO2 + 4 H2O

EFFICIENCY OF A FUEL CELL

ΔG
η= × 100
ΔH

➢ The efficiency of Fuel Cell is 60-70%

SECONDARY CELL
➢ These are the cells which can be recharged on passing electric current.
➢ These are known as storage cells or accumulators because Electrical
Energy can be stored in them.
➢ These are classified into two types
1. Lead-Acid Storage Cells
2. Ni – Cd Storage Cells

LEAD-ACID STORAGE CELLS

➢ It is used in automobiles and inverters.
➢ The Voltage of individual Cell is 2V. therefor 3 or 6 such cells are joined
in series to get a 6V or 12V Battery.
➢ The Anode generally consists of a no. of plates joined in Parallel. Each
Plate is a grid of Lead filled with finely divided Spongy Pb.
➢ Cathode also Consists of an equal no. of Plates Connected in Parallel.
Each plate is a grid of Lead filled with PbO2(lead Oxide).
➢ These Plate are alternatively arranged and separated by thin perforated
Plastic or fibre Glass Sheets.
➢ The electrolyte is 38% H2SO4 (density = 1.31 gm cm3) taken in Plastic or
hard rubber Vessel.

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Cell Reaction
At anode
Pb + SO4-2 → PbSO4 + 2e-
At Cathode
PbO2 + SO4-2 + 4H+ + 2e- → PbSO4 + 2H2O
Complete Cell Reaction
Pb + PbO2 + 2SO4-2 + 4H+ → 2PbSO4 + 2H2O

NI- Cd STORAGE CELL

➢ It Consists of Cd Anode and a metal grid containing NiO2 as Cathode.
➢ Electrolyte is KOH.

Cell Reaction
At Anode
Cd + 2OH- → Cd(OH)2 + 2e-
At Cathode
NiO2 + 2H2O + 2e- → Ni(OH)2 + 2OH-
Complete Cell Reaction
Cd + NiO2 + 2H2O → Cd(OH)2 + Ni(OH)2

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CORROSION
➢ The process of destroying up of a metal by the gases and water vapours
present in air due to formation of certain Chemical Compounds is called
Corrosion.

Ex. Rusting of iron, Green Coating on Copper, Tarnishing of Silver etc.

➢ Corrosion in Fe is known as RUSTING OF IRON.

RUSTING OF IRON
➢ Corrosion in Fe is known as Rusting of Iron.
➢ Rust is hydrated Ferric Oxide (Fe2O3.xH2O) and brown in colour.
➢ It is Electrochemical Phenomena.
➢ In this process, small electrochemical cell is formed on the surface of Fe.
➢ O2 and CO2 containing water sticks on Fe surface and form electrolytic
solution in which redox reaction occurs.
➢ Fe acts as anode and oxidation occurs in it. Free e- participate in
reduction process.

Cell Reaction
At anode
Fe → Fe+2 + 2e-
At Cathode
CO2 + H2O → H2CO3 (Carbonic acid)
H2CO3 ⇌ 2H+ + CO3-2
H2O ⇌ H+ + OH-
H+ + e- → H
4H + O2 → 2H2O
Complete Reaction
2 Fe + O2 + 4H+ → 2Fe+2 + 2H2O
Atmospheric Oxidation
2Fe+2 + 2H2O + ½ O2 → Fe2O3 + 4H+
↓ H2O
Fe2O3.xH2O
(Rust)

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