CHE-1105

ELECTROCHEMISTRY

Electro-chemistry
The branch of physical chemistry which deals with the interconversion of electrical
energy to physical energy and physical energy to electrical energy and associate with it
is called the electro-chemistry.

Conductors
There are two types of conductors:-
1. Electronic conductors
2. Electrolytic conductors

Electrolyte is a solution through which

electricity can pass.

Electrolysis is a process of chemical

decomposition with the help of
electricity. (Electrolysis is the passage
of an through an ion substance that is
either molten or dissolved in a suitable
solvent, resulting in chemical reactions
at the electrodes and separation of materials)

Positive pole
A point of a conductor or an wire through which electricity is supposed to entered into
that conductor.

Negative pole
A point of an wire or a conductor through which electricity is supposed to leave that
conductor.

1 Ampere

1 Amp = 0.00118 gm/sec

1 ampere is an amount of current which is required to dissolve or deposit 0.00118 gm of

Ag in 1 second
Difference between electricity and current:

Electricity is denoted by Q and Current is denoted by i. We know that Q=it. That is

current × time = electricity. The unit of electricity is Coulomb and the unit of current is
Ampere. So the definition of 1 coulomb electricity can be given as follows:-

One coulomb is the amount of electric charge transported in 1 second by a steady

current of 1 ampere

Faraday’s laws of electrolysis

1st Law: In an electrolysis process the amount of substance which is dissolves from or
deposited at any electrode is proportional to the quantity of electricity passed through
the electrolyte solution.

m∝Q
⇒ m ∝it
⇒ m= zit
Here z is a constant of proportionality. It is called electro-chemical equivalent (ECE).

When i = 1 ampere and t = 1 second, then m = z. Thus we can define ECE as follows:
ECE is an amount of substance which will be dissolved or deposited by passing 1
ampere of current for 1 second.

2nd Law: For a given quantity of electricity (electric charge), the mass of an elemental
material altered at an electrode is directly proportional to the element's equivalent
weight. The equivalent weight of a substance is its molar mass divided by an integer that
depends on the reaction undergone by the material.

If we denote E for equivalent weight, then we get,

w∝ E

Equivalent weight has the dimensions and units of mass, unlike atomic weight, which is
dimensionless. Equivalent weights were originally determined by experiment, but
(insofar as they are still used) are now derived from molar masses. Additionally, the
equivalent weight of a compound can be calculated by dividing the molecular weight by
the number of positive or negative electrical charges that result from the dissolution of
the compound. So we can write-
 M
E= [Here, z is the valency number of ions of the substance]
z

Mathematical form
Faraday's laws can be summarized by
MQ EQ
m= ⇒ m= ⇒ zQ
zF F
E
that is z=
F
where
m is the mass of the substance liberated at an electrode
Q is the total electric charge passed through the substance
F = 96,485 C mol-1 is the Faraday constant

In physics and chemistry, the Faraday constant (named afterMichael Faraday) is the
magnitude of electric charge permole of electrons.[1] While most uses of the Faraday
constant, denoted F, have been replaced by the standard SI unit, the coulomb, the
Faraday is still widely used in calculations in electro-chemistry. It has the currently
accepted value:
F =96500 C mol −1

The constant F has a simple relation to two other physical constants:

F = N A×E

where
N A=6.022×10 23 mol −1
e=1.602×10−19
NA is the Avogadro constant, and e is the elementary charge or the magnitude of
the charge of an electron. This relation is true because the amount of charge of a mole
of electrons is equal to the amount of charge in one electron multiplied by the number of
electrons in a mole.
The value of F was first determined by weighing the amount of silver deposited in an
electrochemical reaction in which a measured current was passed for a measured time,
and using Faraday's law of electrolysis.[4] Research is continuing into more accurate
ways of determining the interrelated constants F, NA, and e.

M is the molar mass of the substance

 z is the valency number of ions of the substance (electrons transferred per ion)
Note that M / z is the same as the equivalent weight of the substance altered.
For Faraday's first law, M, F, and z are constants, so that the larger the value of Q the
larger m will be.
For Faraday's second law, Q, F, and z are constants, so that the larger the value of M / z
(equivalent weight) the larger m will be.
In the simple case of constant-current electrolysis, Q = It leading to
MQ
m=
zF
and then to
Mit m it it
m= ⇒ = ⇒ n=
zF M zF zF
where
n is the amount of substance ("number of moles") liberated: n = m / M
t is the total time the constant current was applied.
In the more-complicated case of a variable electrical current, the total charge Q is the
electric current I(τ) integrated over time τ:
t

Q =∫ I  d 
0
Here t is the total electrolysis time. Please note that tau is used as the current I is a
function of tau.

Explanation of equivalent weight:

Using the first law it was found that the quantity of electricity required to deposit one
mole of silver, was 96,500 coulombs. Now one ion of silver is deposited at the cathode
as an atom of silver as follows:
Ag+ + e = Ag
That is to say that one electron deposits one atom of silver. To deposit one mole of silver
one mole of electron will be required. Hence one mole of electron carries 96,500
coulombs of electricity. In honour of Michael Faraday 96,500 coulombs of electricity
was named as one Faraday of electricity. So we write
1 F = 96,500 Coulombs = 96,500 C
and we say that to deposit one mole of silver 1 F of electricity are required.
Now according to the first law of Faraday 1F will deposit one mole of silver, 2 F will
deposit 2 moles of Ag and 3 F will deposit 3 moles of silver.
Since one mole of electrons carry 96,500 coulombs of electricity the charge carried by
96,500
one electron = 23 C = 1.602×10−19 C
6.02×10
Copper and Aluminum are deposited as follows:
Cu2+ + 2e = Cu
Al3+ + 3e = Al
It follows that to deposit one mole of copper two moles of electron are required, i.e. 2 F
of electricity are required and to deposit one mole of Al 3 F are required. When 96,500
or 1 F of electricity is passed through separate electrolytic cells containing Ag+, Cu2+ and
Al3+ ions respectively the amount of metal deposited at the cathodes in the different cells
1 1
were found to be Ag, 1 mole; Cu, 2 mole; Al, 3 mole, i.e. in each case the amount of
1.0 mole
metal deposited = number of charges on the ion
. These amounts are what Faraday
referred to as the equivalent weight.

We will see later that to discharge one mole of oxygen at the anode the reaction is
4 OH -= 2H2O + O2 + 4e
and 4 F electricity will required.

The second law of Faraday may now stated as follows:

The number of Faradays required to liberate one mole of a metal or discharge one mole
of a gas is equal to the number of electrons showed in a balanced equation for the
electrode reaction.

Tanveer Hossain
KUET-0905035
tanveer.me09@gmail.com