Faraday's Laws of Electrolysis

Michael Faraday studied the mechanism of electrolysis and

put forward two laws of electrolysis. These laws provide the
relation between the quantity of electricity passed through an
electrolyte and the amount of substance deposited or
liberated at the electrodes.
 (i) Faraday's first law of electrolysis

It states that "the amount any substance deposited or liberated

at an electrode is directly proportional to the quantity of
electricity passed through the electrolytic solution."
Let W be the amount of the substance deposited or liberated at
the electrode by passing Q quantity of electricity then, according
to this law,
WQ
W=ZQ
where Z is a proportionality constant called electrochemical
equivalent (ECE).
 W = ZIt … (i) [Q = It]
Where I = current and t = time
When I = 1 ampere and t = 1 second, we have,
W=Z
Hence, ECE may be defined as the mass of substance
deposited or liberated when 1 ampere current is passed
through the electrolyte for 1 second or by the passage of 1
coulomb of electricity.
For example, when 1 coulomb of electricity is passed through
CuSO4 solution, it liberates 0.000327 gm of Cu. Hence ECE of
Cu is 0.000327 gm/C. Similarly, ECE of hydrogen is 0.00001044
gm/C.
 (ii) Faraday's second law of electrolysis
It states that "when the same quantity of electricity is passed
through different electrolytes, the amount of different
substances deposited or liberated at the electrodes are
proportional to their equivalent weights or chemical
equivalents."
Mathematically,
WE
Where W is the weight of substance deposited or liberated by a
certain quantity of electricity and E is the equivalent weight of
the substance. The above relation can be written as,
W = Constant × E
or, W/E = Constant …. (i)
If same quantity of electricity is passed through different
electrolytes, equation (i) can be written as,

𝑊1 𝑊2
= = Constant ... (ii)
𝐸1 𝐸2

Where W1, W2, ….. be the amount of substances deposited at

the electrodes and E1, E2, …. be their equivalent weights
respectively.
 Figure : Faraday's second law.

Let us consider the electrolytic cells containing the solution of

CuSO4 and H2SO4 in series and the same quantity of electricity is
passed through them.
When the electricity is passed through different electrolytic
solution then the copper will be deposited in cell A and H2 gas is
liberated in cell B. Then from equation (ii), we can write

Weight of copper deposited Weight of hydrogen deposited

=
Equivalent weight of copper Equivalent weight of hydrogen
Faraday
ECE of an element is the mass of substance deposited or liberated
at the electrodes when 1 coulomb of electricity is passed through
the electrolytic solution.
We have, ECE of hydrogen = 0.00001044 gm/c.
ECE of silver = 0.001118 gm/c
Now,
0.00001044 gm of hydrogen is liberated by passing 1 coulomb of
electricity.
1.008
1.008 gm of hydrogen is liberated by passing coulomb
0.00001044
of electricity
= 96551 coulombs
0.001118 gm of silver is liberated by passing 1 coulomb of
electricity.
107.8
107.8 gm of silver is liberated by passing coulomb of
0.00118
electricity
= 96422 coulombs

The values obtained above can be rounded off to 96500

coulombs.
Now,
Faraday can be defined as the quantity of electricity required to
deposit 1 gram equivalent weight of substance. It is denoted by
F.
Where, F = 96500 coulombs
Again,
One faraday is equal to charge of 1 mole of electrons
Charge of 1 mole of electrons = Charge of an electron ×
Avogadro’s number
= 1.602 × 10–19 × 6.023 × 1023
= 96494 coulombs or 96500 coulombs (approx.)

Thus, 1 faraday is the charge of 1 mole of electrons.

Relation between ECE and equivalent weight
According to Faraday’s first of electrolysis,
W = ZQ
𝑊
Z =
𝑄
We know, that 96500 coulombs (1F) of electricity deposits the
amount which is equal to 1gm equivalent weight of any
substance, then we can write,
W = E(Equivalent weight)
F = 96500 coulombs (1F)
Then, E E
Z= Z=
F 96500
This gives the relation between ECE and equivalent weight of
substance.