053EE11 – ELECTRIC ENERGY

UTILISATION & CONSERVATION

4. ELECTRO CHEMICAL PROCESS

 ELECTROLYSIS
Electrolysis, process by which electric current is
passed through a substance or electrolytic solution to
effect a chemical change. The chemical change is one in
which the electrolytic solution loses or gains an electron.
This process can be normally used for the extraction of
pure metal from their ores, the refining of metals, the
building up of worn parts in metallurgical, chemical, and
in other industries.
PRINCIPLE OF ELECTROLYSIS
The basic principle of electrolysis is, whenever a
DC electric current is made to pass through the solution
of salt, some metals can be separated from them. These
separated metals can be coated on any object to form a
pure thin layer.
ELECTROLYSIS
 ELECTROLYSIS
For example, a crucible filled with water in which
two electrodes (anode and cathode) are immersed and
those are supplied from a DC source as shown in Figure.
When sodium chloride (NaCl) salt is dissolved in water,
it decomposes into positively charged Na+ ion and
negatively charge Cl– ion, moving freely in the solution.

The positively charged ion (Na+) travels toward the

cathode and the negatively charged ion (Cl– ) travels
toward the anode.
 ELECTROLYSIS
On reaching the cathode, each positively charged
sodium ion takes two electrons from it and forms a
sodium metal. Similarly, each of the negatively charged
chloride ion will give two electrons to anode. Thus,
sodium metal from the sodium chloride in the water is
deposited at the cathode. The above process is known as
‘electrolysis’.
LAWS OF ELECTROLYSIS
The laws governing the electrolytic process were
proposed by Michael Faraday. These laws are stated
below.
Faraday’s first law
This law states that ‘the mass of substance
deposited from an electrolyte is proportional to the
quantity of current passing through the electrolyte in a
given time’.
 ELECTROLYSIS
i.e., m ∝ It = ZIt,
where I is the steady current flowing through an
electrolyte in amperes, t is the duration of current
flowing through an electrolyte, Z is the constant of
proportionality, and m is the mass of substance
deposited.
Faraday’s second law
This law states that ‘when the same quantity of electric
current is passed through different electrolytes, the
masses of the substances deposited are proportional to
their respective chemical equivalents or equivalent
weights’.
 ELECTROLYSIS
VARIOUS TERMS RELATED TO ELECTROLYTE
PROCESS
Some of the important terms related to electrolytic
process are discussed below.
(i) Voltage: It is necessary term for the electrolysis. The
voltage required for the passage of current through the
electrolysis must be equal to the voltage drop across the
electrolyte and electrodes. If V1 and V2 are the voltage
drops across the electrolytes and electrodes and ‘V ’ is
the total voltage applied across the electrodes, then:
V = V1 + V2
(ii) Current efficiency: In the electrolytic process,
secondary reactions are caused due to impurities.
Therefore, the quantity of substance deposited or
liberated from the electrodes is slightly less than that of
the quantity actually calculated by Faraday’s laws.
 ELECTROLYSIS

The practical value of the current efficiency lies between

90% and 98%.
(iii) Energy Efficiency: Due to the secondary reactions
caused by the impurities present in the electrolyte, the
actual value of the voltage required for the deposition of
metal from the electrode is higher than the theoretical
value of voltage.

(iv) Equivalent weight: The equivalent weight of a

substance is defined as the ratio of atomic weight to its
valency.
 ELECTROLYSIS
Applications Of Electrolytic Process
Some of the applications of electrolysis used in the
chemical industry and metal extraction are given below.
Manufacturers of chemicals
Various industrial applications of electrolysis such as the
manufacturing of chemicals such as caustic soda,
ammonium sulfate, hydrogen, oxygen, and chlorine.
Here, the production of caustic soda and the production
of hydrogen and oxygen by electrolysis process are
explained below.
Production of caustic soda
The production of caustic soda can be done by two
processes.
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Diaphragm process
In this process, both anode and cathode compartments
are separated by a diaphragm, to prevent the mechanical
mixing of two solutions. During this process, chlorine is
formed at anode; some of it is evolved as gas and the
remaining goes into solution. And, sodium is discharged at
the cathode reacts with the hydroxyl ions forming sodium
hydroxide (NaOH) liberating hydrogen gas at the cathode. At
this stage, brain solution is fed into the anode, which opposes
the flow of hydroxyl ions toward the anode.

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 ELECTROLYSIS
Anode (positive electrode):titanium
Anode reaction (oxidation):
2Cl-(aq) → Cl2(g) + 2e-

Cathode (negative electrode):nickel

Cathode reaction (reduction):
2H2O(l) + 2e- → H2(g) + 2OH-(aq)
Na+ migrates across the membrane to cathode
2Na+(aq) + 2OH-(aq) → 2NaOH (aq)
compartment combining with OH- to form NaOH.
2Na+(aq) + 2cl-(aq) → 2Nacl (aq)

Overall cell reaction:

2H2O(l) + 2Cl-(aq) + 2Na+(aq) → 2OH-(aq) + H2(g) + Cl2(g) + 2NaOH (aq) +2Nacl (aq)

Product is concentrated sodium hydroxide.

 ELECTROLYSIS
Castner-Kellner Cell (Mercury Process)
It is another process of producing caustic soda by
electrolytic process. In this process, mercury cells are
built in various sizes from 1,000 A to very large 50,000 A
per unit. Brine solution is fed into the cells for the
reduction of salt concentration.
 ELECTROLYSIS
Anode (positive electrode): titanium Anode reaction
(oxidation): 2Cl-(aq) → Cl2(g) + 2e-
Cathode (negative electrode): mercury flowing along bottom of
cell Cathode reaction
(reduction): Na+(aq) + e- → Na(s)
Na(s) dissolves in the liquid mercury to form an amalgam
which is removed to the decomposer.
In the decomposer the amalgam reacts with water to form
sodium hydroxide, hydrogen gas and mercury.
2Na/Hg + 2H2O(l) → 2Na+ + 2OH- + H2(g) + 2Hg(l)

Sodium hydroxide solution and hydrogen gas are collected.

Mercury is recycled through the electrolytic cell.
Mercury is toxic so care must be taken to prevent mercury
losses.
 ELECTROLYSIS
Production of hydrogen and oxygen by electrolysis
Water electrolysis is the process whereby water is split
into hydrogen and oxygen through the application of
electrical energy. Typically, a water electrolysis unit
consists of an anode, a cathode separated with an
electrolyte, and a power supply.
 ELECTROLYSIS
The electrolyte can be made of an aqueous solution
containing ions, a proton exchange membrane (PEM) or
an oxygen ion exchange ceramic membrane. A direct
current (DC) is applied from the negative terminal of the
DC source to the cathode (seat of the reduction reaction),
where the hydrogen is produced. At the anode, the
electrons produced by the electrochemical reaction
return to the positive terminal of the DC source.
For the case of water electrolysis in an acid aqueous
electrolyte, the processes that occur at the anode and the
cathode are described, respectively
anode

cathode
 ELECTROLYSIS
The half reactions occurring on the cathode and anode,
respectively, can be written as:
Cathode:

Anode:

The global reaction for the two cases is:

 ELECTROLYSIS
Electro metallurgy
Electro metallurgy indicates the extraction of metals
from their ores and its refining.
Electroextraction
Electroextraction is the process by which metals
can be extracted or separated from their ores. Depending
upon the physical status of the ore, the metal can be
extracted by the two ways: (i) when the ore is in solid
state, it is to be treated with strong acid to obtain its
salt, again this salt is to be electrolyzed to liberate the
metal and (ii) when the metal is in liquid state or in
molten state, it is directly electrolyzed in a furnace to
liberate the metal.
 ELECTROLYSIS
Extraction of zinc
Zinc can be extracted from the zinc ore. The zinc
ore is in solid state that has high content of zinc oxide.
The crude zinc oxide is dissolved in dilute sulphuric acid
to produce a solution of Zinc sulphate after filtration and
purification the solution.

Anode: 𝑆𝑂4 2− --------𝑂2 (g) + 2𝑒 −

Cathode: 𝑍𝑛2+ + 2𝑒 − ------Zn(s)
 ELECTROLYSIS
O2 is released at anode, while Zinc is deposited on the
cathode. H2SO4 is regenerated at the anode and can be
used again.
The zinc is stripped periodically from the cathode
melted and cast into blocks (ingots) for many different
purposes.
Electrolytically refined zinc is generally 99.995% pure.
About 80% of the world's zinc is produced using this
process
 ELECTROLYSIS
Extraction of aluminum
Aluminium is the most abundant metal on Earth, but
it is expensive, largely because of the amount of electricity
used in the extraction process.
Aluminium ore is called bauxite (Al2O3). The bauxite
is purified to yield a white powder – aluminium oxide (also
known as alumina) – from which aluminium can be extracted.

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 ELECTROLYSIS
The extraction is done by electrolysis, but first
the aluminium oxide must be melted so that electricity
can pass through it. However, aluminium oxide has a
very high melting point (over 2,000°C) so it would be
expensive to melt it.
The use of molten cryolite as a solvent reduces
some of the energy costs involved in extracting
aluminium by allowing the ions in aluminium oxide to
move freely at a lower temperature.
The above diagram shows an aluminium oxide
electrolysis cell. Both the negative electrode (cathode)
and positive electrode (anode) are made of graphite,
which is a form of carbon.
 ELECTROLYSIS
Aluminium ions receive electrons at the negative
electrode and are reduced to aluminium atoms:
Al3+ + 3e– → Al (reduction – gain electrons)
The molten aluminium sinks to the bottom of the cell,
where it is tapped off.
Oxide ions lose electrons at the positive electrodes and
are oxidised to oxygen gas:
2O2– → O2 + 4e– (oxidation – lose electrons)
This oxygen reacts with the carbon of the positive
electrodes, forming carbon dioxide, so they gradually
burn away. As a result, the positive electrodes have to be
replaced frequently. This adds to the cost of the process.
 ELECTRO-DEPOSITION
Electrodeposition
Electro-deposition is the process by which one metal is
deposited over other metal or non-metal, by electrolysis.
Usually, electro-deposition is used for the decorative,
protective, and functional purposes and it includes
electroplating, electroforming, electrotyping, electrofacing,
electrometallization, etc.
Factors affecting the quality of electrodeposition
The quality of the deposition of the metal is governed by the
following factors.
Nature of electrolyte The smoothness of the deposited metal
over any other metal depends upon the nature of the
electrolyte. For example, cyanide solution is one of the
electrolytes that provide smooth deposit over any metal.
Current density The deposited metal is very much strong and
porous. If the rate of current is high, then the deposits are
coarse and crystalline.
 ELECTRO-DEPOSITION
Temperature
The temperature of the electrolyte is different for
different metals to have better deposit. At low
temperatures, the electrolyte forms small crystals and at
high temperatures, the electrolyte forms large crystals.
Electrolytic concentration
If the concentration of the electrolyte is more, the higher
will be the current density.
Addition of agents
Addition of agents such as glue, gum, and dextrin to the
electrolyte influences the nature of the deposited metal.
These additional agents are absorbed by the crystal that
prevent the large growth and thus deposition will be
fine-grained.
 ELECTRO-PLATING
Electroplating
Electroplating is defined as the deposition of a metal over any
metallic or non-metallic surfaces. Electroplating is usually
employed to protect the metals from corrosion by atmospheric
air, moisture, and CO2 , to give the reflecting properties to
reflectors, to replace worn out metals, to give a shiny
appearance to articles, etc.
Preparation for plating: Electroplating involves two functions.
They are: (i) cleaning operation and (ii) plating operation.
Cleaning operation In case if a metal is to be electroplated, it
should be cleaned, i.e., metal should be polished, degreased
oil, and any organic material, rust, scale, oxides, etc. is to be
removed from the metal.
Plating operation In plating process, the metal or article to be
electroplated is arranged as the cathode and the anode is
made up of the material that is to be deposited on the metal.
And, salt is taken as solution in which the electrodes are
immersed.
 ELECTRO-PLATING
Electroplating of copper sulfate with inert
graphite (carbon) electrodes
 ELECTRO-PLATING
The negative cathode reaction with graphite
electrodes
The negative cathode electrode attracts Cu2+ ions (from
copper sulfate)
A brown copper deposit forms as the positive copper
ions are attracted to the negative electrode (cathode)
Cu2+(aq) + 2e– ===> Cu(s)

The positive anode reaction with graphite

electrodes
Oxygen and sulphur di oxide gas are formed at the
positive electrode, an oxidation reaction (electron loss).
 The negative sulfate ions (SO42-) are attracted to the
positive electrode.
𝑺𝑶𝟒 𝟐− ===> 2𝒆− +𝑺𝑶𝟐 (g) +𝑶𝟐 (g)
 ELECTRO-PLATING
Copper electroplating using copper sulfate solution
and copper electrodes
 ELECTRO-PLATING
The products of electrolysing copper sulfate solution with
copper electrodes are copper metal and copper ions
(because the copper anode dissolves).
Using the simple apparatus and two copper electrodes the
products of the electrolysis of copper sulfate solution are
(i) copper deposit on the negative cathode electrode and

(ii) copper dissolves at the positive anode electrode.

This copper anode reaction differs from when you

use an inert graphite electrode for the anode.
When Copper(II) sulfate is electrolysed with
a copper anode electrode (the cathode can be carbon or
copper), the copper deposit on the cathode (–) equals the
copper dissolves at the anode (+).
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The positive anode reaction with a copper electrode
The negative sulfate ions SO42- (from copper sulfate) are
attracted to the positive electrode.
But both the sulfate ions are too stable and nothing happens to
them because the copper anode is preferentially oxidised to
discharge Cu2+ copper ions into the electrolyte solution.
This is fairly unusual, because normally electrodes are 'inert',
BUT, this technique is used in electroplating.
An oxidation electrode reaction at the positive anode
Cu(s) ===> Cu2+(aq) + 2e–

The copper dissolves, oxidation of the copper atoms, each

losing 2 electrons to form blue Cu2+ ions in solution, in this
case the electrode is NOT inert.
 ELECTRO-PLATING
The negative cathode reaction with copper or carbon
electrodes
The negative cathode electrode attracts Cu2+ ions (from copper
sulfate)
 Only the copper ion is discharged, being reduced to copper
metal.
 The less reactive a metal, the more readily its ion is reduced
on the electrode surface.
 A reduction electrode reaction at the negative cathode
Cu2+(aq) + 2e– ===> Cu(s)
 A copper deposit forms, reduction of the copper ions, each
gains 2 electrons.
 Note on 'plating' - the formation of the copper deposit:
 It doesn't matter what the cathode is made of, as long as it is
a conducting material.
 CURRENT EFFICIENCY
What is current efficiency during electro-deposition of
copper metal in which 8.8834 g copper is deposited by
passage of 3A current for 10,000s?

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 BATTERIES
All energy storage systems use batteries, but not the
same kind. There are many different types of batteries
used in battery storage systems and new types of
batteries are being introduced into the market all the
time.

These are the main types of batteries used in battery

energy storage systems:
Lithium-ion (Li-ion) batteries
Lead-acid batteries
Redox flow batteries
Sodium-sulfur batteries
Zinc-bromine flow batteries
 METHODS OF CHARGING
Battery Charging Methods
There are three common methods of charging a battery;
constant voltage, constant current and a combination of
constant voltage/constant current with or without a smart
charging circuit.