Electrolysis; Principle, Faraday’s

Laws and Applications of

Electrolysis.
• Electrolysis: Electrolysis is the process of inducing a chemical reaction which does
not occur naturally or spontaneously with the help of Direct Current or electricity.
• Terms related to Electrolysis:
• Electrolyte: Electrolytes are the chemical compound whose atoms are closely
bounded but when dissolved in solvents like water ionizes and splits into two ions
namely cations and anions. for eg:- NaCl
• Cations: A Cation is an ion or charged atom or particle which have fewer electrons
than protons or is positively charged and thus attracted to the negative terminal
or cathode during electrolysis.
• Anions: is an ion or charged atom or particle which have fewer protons than
electrons and is negatively charged thus attracted to the positive terminal or
anode during electrolysis.
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• Electrodes: Electrodes are the conductor of electricity which are used to make contact of
the circuit with the electrolytic solution.
• Anode: Anode is the positively charged electrode.
• Cathode: Cathode is the negatively charged electrode.
• Principles of Electrolysis:
• When an electrolyte is dissolved into a solution forming an electrolytic solution and the
electrodes from an external energy or current source are immersed into the electrolytic
solution.
• Then the Cations of the electrolyte gets attracted to the cathode and anions to the anode.
• Then the anions loose their electrons to the anode and cations get the deficient electron
from the cathode thus creating a flow of electrons through the external energy source
thus exchanging the atoms and charges by utilizing the energy from the external energy
source. This process is called the Electrolysis.
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• For example:
• When the electrolyte copper sulfate (CuSO4) is dissolved into water it gives
Cation Cu++ and Anion SO4– – which moves freely in the solution.
• Now if we immerse the positive and negative terminals of a battery into the
solution then the Cation Cu++ gets attracted to the cathode exchanging the
electron from the cathode and Anion SO4– – gets attracted to the anode
exchanging the electrons to the anode.
• This process causes the deposition of copper at Cathode.
• And the energy for the whole process is supplied by the Battery through
which the current flow.
 Faraday’s Laws of Electrolysis:
• Faraday’s laws are the two laws given by Michael Faraday in 1834 which
describes and defines the quantitative relationship between electricity and ions
deposited at electrodes. The two laws of Faraday’s Laws of Electrolysis are:
• Faraday’s First Law of Electrolysis: The mass of ions or substances liberated at
an electrode during electrolysis is directly proportional to the quantity of
electricity transferred to the electrode.
• If, Mass of Ions liberated = m
• Quantity of electricity = The total charge used for electrolysis = Q = I * t
• I = The current through the electrodes. & t = the time for which the process of
electrolysis is run.
• Then According to the Faraday’s first law of electrolysis:
• , So, W when I = 1 and t=1 m=Z
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• The “Z” is a constant and is known as the ElectroChemical Equivalent (ECE) of the
substance.
• The ElectroChemical Equivalent of a substance is the mass of the ions liberated
by the passage of one ampere of current through electrodes for one second.
• The ECE of a substance is a composite function of the valency and atomic
weight of the substance. And it’s value is given by:

• Where, a = Atomic weight of the substance.

• v = Valency of the substance
• & F = Faraday’s constant , which is the charge required to liberate one gram-
equivalent of any substance and is equal to 96485 C mol−1
 Faraday’s Second Law of
Electrolysis:
• If same amount of electricity is passed through different electrolytes then
the mass of substances deposited in the electrodes are proportional to
their respective equivalent weight or chemical equivalent.
• For example: If same amount of electricity is passed through two
electrolytes and in one electrolysis Nickle is deposited in electrode and in
another Silver is deposited then the mass of the respective metal deposited
is proportional to their ECE. OR,
• ECE of Ni / ECE of Ag = Mass of Nickle Deposited / Mass of Silver Deposited
 Applications of Electrolysis:
• Electrolysis being one of the most important process in electro-chemistry has a
lot of applications some of which are listed below:
• Electrometallurgy:
• Electrometallurgy is the field which is related to the processing of metals with the
help of electrolysis.
• The types of electrometallurgy are:
• Electrowinning is a process of extracting of metals from their ores. For example
aluminium can be extracted from bauxite by using electrolysis.
• Electrorefining: It is the process of purifying the metals from their impure forms.
For example highly pure copper is extracted from blister copper using electrolysis.
• Electroplating: is the process of deposition of a layer of a metal around another
metal.
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• For example metals like iron which are easily corroded by environment and
air are electroplated with nickel or chromium with the help of electrolysis.
• Electroforming is the process of manufacturing of thin sheets of metals
using electroplating or electrolysis.
• Production of Chemicals:
• Various chemicals are produced with the help of electrolysis. For example
chemicals like caustic soda , chlorine , potassium permanganate are
produced with the help of electrolysis.
 SUMMARY
• Faraday’s – First Law of Electrolysis
• It states, during electrolysis, the amount of chemical reaction which occurs at any
electrode under the influence of electrical energy is proportional to the quantity
of electricity passed through the electrolyte.
• Faraday’s – Second Law of Electrolysis
• During electrolysis, when the same quantity of electricity passes through the
electrolytic solution, a number of different substances liberated are proportional
to their chemical equivalent weights (Equivalent weight is defined as the ratio of
the atomic mass of metal and the number of electrons required for reducing the
cation).
• From these laws of electrolysis, we can deduce that the amount of electricity
needed for oxidation-reduction depends on the stoichiometry of the electrode
reaction.
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• For example,
• Na+ +e− → Na
• As we can observe, one mole of the electron is required for the reduction
of one mole of sodium ions.
• We know that charge on one electron is equal to 1.6021 × 10–19C .
• Therefore, the charge on one mole of electrons is equal to:
• NA × 1.6021 × 10–19C = 6.02 × 1023mol–1 × 1.6021 × 10–19C = 96487 C
mol–1
• This quantity of electricity is defined as one Faraday and is denoted by F.
Hence; one Faraday is defined as the charge carried per unit mole of
electrons.
 Cont’d
• The product of an electrolytic reaction depends on the nature of the
material being electrolysed and the type of electrodes used.
• In the case of an inert electrode such as platinum or gold, the electrode
does not participate in the chemical reaction and acts only as a source or
sink for electrons.
• While, in the case of a reactive electrode, the electrode participates in the
reaction.
• Hence, different products are obtained for electrolysis in the case of
reactive and inert electrodes.
• Oxidizing and reducing species present in the electrolytic cell and their
standard electrode potential too, affect the products of electrolysis.