5.

Electrolytic Processes

5.1 Introduction
• The fact that electrical energy can produce chemical changes and the processes based
on it, called the “electrolytic processes”, are widely used for extraction of pure metals
from their ores (such as aluminum, zinc, copper, magnesium, sodium etc.),
manufacturing of various chemicals (such as caustic soda, potassium permanganate,
hydrogen, oxygen, chlorine etc.), electro deposition of metals including electroplating,
electrotyping, electroforming, building up of worn-out parts in metallurgical, chemical
and other industries.
5.2 Principle of electrolysis
• As discussed in the definition of electrolyte, whenever any electrolyte gets dissolved in
water, its molecules split into cations and anions moving freely in the electrolytic
solution.
• Now two metal rods are immersed in the solution and an electrical potential difference
applied between the rods externally preferably by a battery. These partly immersed
rods are technically referred as electrodes.
• The electrode connected with negative terminal of the battery is known as cathode and
the electrode connected with positive terminal of the battery is known as anode.
• The freely moving positively charged cations are attracted by cathode and negatively
charged anions are attracted by anode.

e- e-
Battery

Impure Copper Pure Copper

C
A a
n t
SO4- o Cu+ h
d Cu+ o
SO4-
e Cu+ d
e
Cu+

Electrolyte
(CuSO4)
Impurities

Figure 5.1 Electrolysis

Prof. Rajan Detroja, EE Department Utilization of Electrical Energy and Traction (2160907) 1
 5. Electrolytic Processes

• In cathode, the positive cations take electrons from negative cathode and in anode,
negative anions give electrons to the positive anode. For continually taking and giving
electrons in cathode and anode respectively, there must be flow of electrons in the
external circuit of the electrolytic.
• That means, current continues to circulate around the closed loop created by battery,
electrolytic and electrodes. This is the most basic principle of electrolysis.
• Whenever copper sulfate (CuSO4) is added to water, it gets dissolved in the water. As
the CuSO4 is an electrolyte, it splits into Cu+ + (cation) and SO4− − (anion) and move
freely in the solution.
• Now if two copper electrodes are immersed in that solution, the Cu+ + ions (cation) will
be attracted towards cathode. On reaching on the cathode, each Cu++ ion will take
electrons from it and becomes neutral copper atoms.
• Similarly the SO4− − (anion) ions will be attracted by anode. So SO4− − ions will move
towards anode where they give up two electrons and become SO4 radical but since SO4
radical cannot exist in the electrical neutral state, it will attack copper anode and will
form copper sulfate.
• If during electrolysis of copper sulfate, we use carbon electrode instead of copper or
other metal electrodes, then electrolysis reactions will be little bit different.
• Actually SO4 cannot react with carbon and in this case the SO4 will react with water of
the solution and will form sulfuric acid and liberate oxygen.
• The process described above is known as electrolysis. In the above process, after taking
electrons the neutral copper atoms get deposited on the cathode.
• At the same time, SO4 reacts with copper anode and becomes CuSO4 but in water it
cannot exist as single molecules instead of that CuSO4 will split into Cu++, SO4− − and
dissolve in water.
• So it can be concluded that, during electrolysis of copper sulfate with copper electrodes,
copper is deposited on cathode and same amount of copper is removed from anode.
5.3 Faraday's first law of electrolysis
• It States that "The chemical deposition due to flow of current through an electrolyte is
directly proportional to the quantity of electricity (coulombs) passed through it”.
Mass of chemical deposition,m ∝ Quantity of Electricity ,Q
m= Z ⋅Q
where, Q = It
so, m = ZIt
• According to this law, the chemical deposition due to flow of current through an
electrolyte is directly proportional to the quantity of electricity (coulombs) passed
through it. i.e. mass of chemical deposition, Where Z is a constant of proportionality and
is known as electrochemical equivalent of the substance.
• If we put Q = 1 coulombs in the above equation, we will get Z = m which implies that
electrochemical equivalent of any substance is the amount of the substance deposited
on passing of 1 coulomb through its solution. This constant of passing of

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 5. Electrolytic Processes

electrochemical equivalent is generally expressed in terms of milligram per coulomb or

kilogram per coulomb.
• Where I= the steady current in Ampere and t= Time (second) for which current I flows
through the electrolyte.
5.4 Faraday's second law of electrolysis
• It states that, "When the same quantity of electricity is passed through several
electrolytes, the masses of the substances deposited are proportional to their respective
chemical equivalents or equivalent weights”.
5.5 Chemical equivalent or equivalent weight
• The chemical equivalent or equivalent weight of a substance can be determined by
Faraday’s laws of electrolysis and it is defined as the weight of that substance which will
combine with or displace unit weight of hydrogen.
• The chemical equivalent of hydrogen is unity.
• Since valency of a substance is equal to the number of hydrogen atoms, which it can
replace or with which it can combine, the chemical equivalent of a substance, therefore
may be defined as the ratio of its atomic weight to its valency.
  atomic weight
The
  chemical equivalent =
valency
5.6 Terms connected with electrolytic processes
• Following terms are used in electrolytic processes:
1. Current Efficiency
• Due to impurities which cause secondary reactions, the quantity of the substance(s)
liberated is slightly less than that calculated from Faraday's laws. This is taken into
account by employing a factor, called the "Current efficiency".
• The current efficiency is defined as the ratio of the actual quantity of substance
liberated or deposited to the theoretical quantity, as calculated from Faraday's laws.
 Actual quantity of substance liberated or deposited
Current
  efficiency =
Theoretical quantity of substance liberated or deposited
2. Voltage
• The voltage that is essentially required to pass the current through any electrolytic cell
is equal to the sum of voltage drop in the resistance of the electrolyte and the voltage
drops at electrodes.
• It is, therefore, desirable that these drops are made as small as possible. This can be
achieved, in many cases, by adding special conducting agents to the electrolyte to make
it (electrolyte) a good conductor.
• For example dilute sulphuric acid is added to copper sulphate bath in copper plating.
• The normal voltage required to pass current through most electrolytes is 1 to 2 V.
3. Energy efficiency
• Owing to secondary reactions, the voltage actually required for the deposition or
liberation of metal is higher than the theoretical value which increases the actual energy
required.

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 5. Electrolytic Processes

• The ratio of theoretical energy required to the actual energy required for depositing a
given quantity of metal is known as energy efficiency.
Theoretical energy required
 Energy efficiency =
Actual enerergy requied
5.7 Applications of electrolysis
• The major applications of electrolysis are as under.
1. Electro-deposition
o Electroplating
o Electro-deposition of rubber
o Electro-metallization
o Electro-facing
o Electro-forming
o Electro-typing
2. Manufacture of chemicals
3. Anodizing
4. Electro polishing
5. Electro-cleaning or pickling
6. Electro-parting or electro stripping
7. Electro-metallurgy
o Electro-extraction
o Electro-refining
5.8 Electro-deposition
• The process of depositing a coating of one metal over another metal or non-metal
electrically is called the electro-deposition.
• It is used for protective, decorative and functional purposes and includes such processes
as electro-plating, electro-forming, electro-typing, electro-facing, electro metallization
etc.
• As earlier discussed that, the compounds in the solution dissociate into positive and
negative ions which when subjected to electric field travel towards respective
electrodes then, one of the following events may take place:
i. In case the ion, after giving off electric charge to electrode, has stable existence and
does not have chemical reaction with electrode material, it will be deposited on the
electrode. This is the principle of electro-deposition and electro-extraction.
ii. The ion after giving off electric charge to electrode may undergo chemical reaction
with electrode material, the product of reaction in turn is soluble in the electrolyte
and the electrode is gradually eaten away. This principle is employed in Electro-
refining.
iii. Ion if after giving off charge to electrode, does not react with the electrode material,
or has any independent and stable existence, will react with the water of solution,
thereby liberating oxygen or hydrogen.

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 5. Electrolytic Processes

• Factors on which quality of electro deposition depends.

1 Nature of electrolyte:
The electrolyte from which complex ions can be obtained (e.g., cyanides) provides a
smooth deposit.
2 Current density:
The deposit of metal will be uniform and fine-grained if the current density is used
at a rate higher than that at which the nuclei are formed. The deposit will be spongy
and porous if the rate of nuclei formation is very high due to very high current
density.
3 Temperature:
A low temperature of the solution favours formation of small crystals of metal and a
high temperature, large crystals.
4 Conductivity:
The solution of good conductivity provides economy in power consumption and also
reduces the tendency to form trees and rough deposits.
5 Electrolytic concentration:
By increasing the concentration of the electrolyte, higher current density can be
achieved, which is necessary to obtain uniform and fine grain deposit.
6 Additional agents:
The addition of acid or other substances to the electrolyte reduces its resistance.
Addition agents like glue, gums, dextrose, dextrin etc. influence the nature of
deposit. The crystal nuclei absorb the addition agent added in the electrolyte; this
prevents it to have large growth and thus deposition will be fine-grained.
7 Throwing power:
It is defined as the ability of the electrolyte to produce uniform deposit on an article
of irregular shape and is one of the most important characteristics of plating or
deposition bath.
Due to irregular shape of the cathode the distance between the various portions of
the cathode and anode will be different.
Due to unequal distance, the resistance of the current path through the electrolyte
for various portions of the cathode will be different but the potential difference
between the anode and any point on the article to be plate (cathode) will, of course
be the same and the result will be that the current density will be more on the
portion nearer to anode and it will cause uneven deposit of the metal.
o Copper cyanide bath is better suited for electroplating intricate articles.
o Zinc cyanide bath has better throwing power than zinc sulphate solution for zinc
plating.
8 Polarization:
With the increase in the electroplating current density, rate of metal deposition is
also increased upto certain limit after which electrolyte surrounding the base metal
becomes so much depleted of metal ions that rate of deposition does not increase
with increase in current density.
If current density more than this limit is employed, it will result in electrolysis of
water and hydrogen deposition on the cathode. This hydrogen evolved, blankets the
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 5. Electrolytic Processes

base metal which diminishes the rate of metal deposition. This phenomenon is called
“polarization”.
5.9 Electroplating
• "Electroplating" is an art of depositing a superior or a more noble metal on an inferior
or a base metal by means of electrolysis of an aqueous solution of a suitable electrolyte.
or
• "Electroplating" is defined as the electro-deposition of metal upon metallic surfaces.

• Electroplating is done to accomplish the following:

a) To protect the metals against corrosion.
b) To give reflecting properties reflectors.
c) To give a shiny appearance to articles.
d) To replace worn out material.
• Various operations involved in electroplating are
1. Cleaning operation
• In case the object to be electroplated is not cleaned, polished and degreased, the deposit
formed may not be well adherent to the base metal and is likely to peel off.
• Cleaning operation includes the following:
a) Removal of oil, grease or other organic material etc. To accomplish this, soaps, hot alkali
solutions or organic solvents such as gasoline or carbon tetrachloride are used.
b) Removal of rust, scale, oxides, or other inorganic coatings adhering to the base
metal/work piece to accomplish this various acids, alkali and salt solutions are
employed.
c) Mechanical preparation of the surface of the metal to remove the deposited metal, by
polishing, buffing etc to accomplish this mechanical abrasion and polishing are used.
2. Deposition of metal
• In all types of metal deposition processes, article to be electroplated is made cathode,
solution is made up of salt4f the metal to be deposited and anode is often of the same
metal which is to be deposited.
a) Electra-deposition of rubber
• Rubber latex obtained from the tree consists of very fine colloidal particles of rubber
suspended in water. Like other colloidal solutions, particles of rubber are negatively
charged.
• On electrolysis of the solution the rubber particles migrate towards the anode and
deposit on it.
• Current density of roughly 100 A/m2.
b) Electro-metallization
• It is the process of depositing metal on conducting base for decoration and for
protective purposes. Nonconductive base is made conductive by a coating of graphite
which is made the cathode.

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 5. Electrolytic Processes

c) Electro-facing
• It is a process of coating of metallic surface with a harder metal by electro-deposition in
order to increase its durability.
d) Electro-forming
• "Electro-forming" is the reproduction of objects by electro-deposition on some sort of a
mould or form. In the reproduction of medals, coins, engravings etc., a mould is first
made by impressing the object say in wax.
• The wax surface, which bears exact impressions of the object, is coated by powdered
graphite in order to make it conducting. The mould is then dipped in an electro-forming
cell as a cathode.
• After obtaining coating of desired thickness, the article is removed and the wax core is
melted out of the metal shell.
• Other applications of electro-forming are:
(i) Manufacture of gramophone records.
(ii) Production of seamless tube.
e) Electro-typing
• Electro-typing is a special application of electro-forming and it is used to reproduce
printing, setup type, engraving and medals etc.
• The process is same as for electro-forming.
5.10 Manufacture of chemicals
• The industrial applications of electrolysis include the manufacture of chemicals like
chlorine, caustic soda, potassium permanganate, ammonium per sulphate, hydrogen
and oxygen.
• The most important process of production caustic soda by electrolysis of brine and
production of hydrogen and oxygen gases by electrolysis of water are explained below.
1. Production of caustic soda.
• The oldest process is Diaphragm process.
• There are a number of variations, but all essentially consist of an anode compartment
separated from a cathode compartment by a porous diaphragm which prevents the
mechanical mixing of two solutions.
• Chlorine is formed at the anode, and most of it is evolved as a gas, a small part going into
solution.
• Sodium is discharged at the cathode and reacts with hydroxyl ions to form sodium
hydroxide and hydrogen gas is liberated at the cathode.
• Usually, the brine is fed into the anode compartment to resist the flow of hydroxyl ions
towards the anode.
2. Production of hydrogen and oxygen gas by electrolysis of water.
• Gases obtained by this process are of high purity and at a cheap cost because of the low
energy consumption.
• The electrolyte consists of 15-20% solution of caustic soda or its equivalent caustic
potash and electrodes are of iron.
• Sulphuric acid is no longer used.

Prof. Rajan Detroja, EE Department Utilization of Electrical Energy and Traction (2160907) 7
 5. Electrolytic Processes

• Thus hydrogen and oxygen gases are liberated at cathode and anode respectively and
water disappears while the quantity of caustic soda remains constant.
• It is therefore, necessary to add water to the solution periodically.
• The voltage requirement is 2-2.2 V per cell during operation and 2.3-2.5 V per cell
during starting period.
• Energy consumption is about 6 kWh per cubic meter of hydrogen and ½ cubic meter of
oxygen.
5.11 Anodizing
• An “anodic coating “means an oxide film deposited/created on a metal surface, with the
help of an anode and oxidation. The process of providing an oxide film is known as
Anodizing.
• The surface of the metal can be anodized to achieve one or more of the following:
i. To provide a protective coating on the surface.
ii. To provide a decorative appearance to the surface.
iii. To provide a specific color base for subsequent painting on the surface.
iv. To provide a bright and smooth surface on aluminum articles as a prior treatment to
electroplating.
v. To improve the corrosion resistance of aluminum and its products.
• Anodizing process is neither a purely electrical process nor a purely chemical process; it
is a combination of both i.e., an electrochemical process. It is completed in the following
three stages:
I. The "first stage" consists of cleaning and preparing the surface through different
cleaning methods.
II. The "second stage" consists of anodizing i.e., converting the metal surface into an
oxidized film.
III. The "third stage" consists of providing desired color and stability to the anodized
film, called sealing of oxide film.
5.12 Electro-polishing
• This process, in principle, consists of making the work as anode in a suitable position.
• This produces insoluble compounds, which are broken down by more anodic action on
the hills than on valleys of the surface.
5.13 Electro-cleaning or pickling
• Electrolytic solution of sodium phosphate is contained in iron tank which is made
anode.
• Work is suspended as cathode. When the current is passed, it produces caustic soda on
cathode has cleaning action. This is called cathodic cleansing.
• In anodic cleansing, work is made anode. Dirt particles are positively charged in alkaline
by electrophoresis process they migrate to negative pole.
5.14 Electro-parting or Electro-stripping
• Two or more metals may be separated electrolytically.
• As an example if copper is to be stripped Iris Prom steel, the work piece is made anode
in a solution of 75 gm of sodium cyanide, 25 gm of caustic n111141 in 1000 c.c. of water.

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 5. Electrolytic Processes

• Sheet of iron is made cathode and pressure used is 6 V.

5.15 Electro-metallurgy
• Electro-metallurgy includes electro-extraction and electro-refining processes.
5.16 Electro-extraction
• Extraction of metal is an electro-chemical process employed for production of metal
with commercially acceptable purity.
• Depending upon the physical state of the ore, following are the two methods of
extraction of metals:
(i) In one of the methods the ore is treated with a strong acid to obtain a salt and the
solution of such a salt is electrolyzed to liberate the metal.
(ii) The second method is used when the ore is available in molten state or can be fused
and in this method the ore, which is in a molten state is electrolyzed in a furnace.
5.17 Extraction of magnesium
• Magnesium is obtained by electrolysis of magnesium chloride, employing current
density-of 160 to 350 Aim2.
• Energy expenditure is 17 to 20 kWh/kg and operating temperature of 360 to 670°C.
5.18 Extraction of sodium
• Sodium is obtained by the electrolysis of sodium hydroxide, sodium nitrate or sodium
chloride requiring expenditure of 10 to 20 kWh/kg of sodium.
5.19 Electro-refining
• Refining is the process whereby a highly concentrated mixture of metals is subjected to
electrochemical treatment for recovering not only the principal metal in pure form, but
also the precious metals like gold, silver, bismuth etc., which may be present in the form
of minute traces.
• By electro-refining, it is possible to get metal of almost 100% purity. This is one of the
most important prerequisite expected out of copper and aluminum in order to have
high electrical conductivity.
• Electro-refining process in essence is same as electro-plating, anode being made of
impure metal and electrolyte being made of the salt of the metal to be refined.
• Pure metal is deposited at the cathode.
• Copper refining requires copper sulphate solution with electric consumption of 150 to
300 kWh/tonne of copper refined.
• Silver is refined requiring solution of nitric acid and silver nitrate with electric
consumption of 400 to 420 kWh/tonne.
• Iron is refined by using solution of iron-ammonium sulphate with electric consumption
of 1000 to 1600 kWh/tonne.
• Lead is refined by using solution of lead fluorosilicate with electric consumption of 100
to 120 kWh/tonne.
• Gold refining requires gold chloride solution with electric consumption of 300 to 350
kWh/tonne of gold refined.
• Nickel refining requires nickel-ammonium sulphate solution with electric consumption
of 2500-4000 kWh/tonne of nickel refined.

Prof. Rajan Detroja, EE Department Utilization of Electrical Energy and Traction (2160907) 9
 5. Electrolytic Processes

5.20 Power supply for electrolytic processes

• For electrolytic process, the power supply required is D. C, and at very low voltage.
• The power required for electro-deposition is usually very small (between 100 and 200A
at 10 or 12V) and can be obtained either by employing a motor-generator set consisting
of a standard induction motor driving a heavy current low voltage D.C. generator
(preferably separately excited) or by employing the copper oxide rectifier.
• The latter is preferred since it has high operating efficiency, occupies less space and its
maintenance cost is low.
• For extraction and refining of metals and large scale manufacture of chemicals a very
large amount of power is required.
• Since most of the processes are continuous and as such have a 100 percent load factor,
these plants are located near hydroelectric power stations or atomic power plants even
if extra transportation or raw material is necessitated.

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