6.

10 Electrolysis Electrolysis
Electrolysis is the process of decomposition of electrolytes by passing electricity through its aqueous solution or molten
form (Electro = electricity, lysis = break down). Electrolysis is associated with two aspects i.e. qualitative and
quantitative aspects.
In qualitative aspects of electrolysis, the normal phenomenon of electrolysis is discussed. Factors affecting the
electrolysis, the fate of the electrolytic products, choice of electrodes, concentration of electrolyte solution, presence of
impurities, etc. are discussed in qualitative aspects of electrolysis.
While in quantitative aspects of electrolysis, the amount of substance decomposed or deposited or liberated in
electrolysis process is discussed.
Redox reaction in electrolysis
Electrolysis involves the decomposition or dissociation or liberation of compound where
cations and anions are the key actors. Under the application of electricity, the ions migrate
towards the corresponding electrode.
Anion is negatively charged ion, gets attracted towards the positively charged electrode (anode)
and losses electrons to be discharged. Therefore oxidation of anions takes place at anode.
Cations are positively charged ions which migrate towards a negatively charged electrode
(cathode) and gains electrons to be reduced. Therefore reduction of cations takes place at
cathode. The oxidation reaction at anode and the reduction reaction at cathode go side by side
and complete the net reaction undergoing on the system.
Qualitative aspect of electrolysis
The apparatus used to carry out electrolysis is called electrolytic cell or voltameter.
Electrolytic cell consists of two metallic rods or metallic plates dipped into electrolyte solution. The
metallic rods or metallic plates are called electrodes. These electrodes are connected to the source of direct
current. The electrode which is connected to the positive terminal of cell is called anode and the electrode
which is connected to the negative terminal of cell is called cathode. The electrolytic solution may be
aqueous solution or molten or fused state of electrolytes. When electric current is passed, the ions migrate
towards the oppositely charged electrodes.
The products obtained during electrolysis depend upon the following factors.
i. Nature of electrolytes (Types of electrolytes)
ii. State of electrolytes (Molten or aqueous solution)
iii. Concentration of electrolyte solution
iv. Nature of electrodes (Attackable or non-attackable)
v. Charge density flown during electrolysis.
Quantitative aspect of electrolysis
The quantitative relationship between the amount of electricity passed and the mass of ion
discharged in the voltameter was first investigated by Michael Faraday and he enunciated the
following two laws in 1833. These laws are known as Faraday's law of electrolysis.
A. Faraday's first law of electrolysis
Faradays first law of electrolysis states "The amount of substance discharged or liberated at
the electrode during electrolysis is directly proportional to the quantity of electricity (charge)
passed through the electrolyte solution." According to this law,
Amount of substance discharged (W) ∝ charge supplied (Q).
or, W = ZQ . . . (i)
or, W = ZIt [Charge (Q) = current (I) × time (t)] . . . (ii)
Where, Z = proportionality constant and known as electrochemical equivalent, (ECE)
W = Amount of substance discharged
Electrochemical Equivalent, Z: We have, W = Zit.
If 1 ampere current is passed through the electrolyte solution for 1 sec (i.e. one coulomb charge) then, W = Z. Hence,
electrochemical equivalent of a substance is defined as the mass of substance (in gram) deposited or
liberated by the passage of one coulomb charge.
1 Faraday (96,500 coulomb) charge deposits 1 gram equivalent of any substance. Let E be the
equivalent weight of a substance
96,500 coulomb deposits E g of substance
1 coulomb deposits E/ 96500 g of substance.
By definition, Z = E/ 96,500
Unit of Z is gram/ coulomb or gram /ampere sec
Therefore,
Faraday's first law (W = Zit) can also be mathematically expressed as, W = Eit/ 96‚500
One of the significance of the Faraday's first law of electrolysis is that it helps to calculate the electrochemical
𝐸
equivalent (ECE) of chemical substance. The ECE of different substances can be calculated by using z =
96500
96500 . For examples,
1.008
(i) Electrochemical equivalent of H =
96500
= 0.0000104 g/coulomb
31.75
(ii) Electrochemical equivalent of Cu =
96500
= 0.0003290 g/coulomb
107.7
(iii) Electrochemical equivalent of Ag =
96500
= 0.0011160 g/coulomb
32.6
(iv) Electrochemical equivalent of Zn =
96500
= 0.0003378 g/coulomb
B. Faraday's second law of electrolysis
It states that when same quantity of electricity is passed through different electrolytic solution
connected in series, the mass of substance deposited or liberated at the respective electrodes
is directly proportional to its chemical equivalent or equivalent weight. According to this
law,