Electrolysis Processes

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 (e.g. Al, Zn, Cu etc…),
• For manufacturing of various chemicals
(e.g. caustic soda, oxygen, hydrogen),
• For electro deposition of metals including
electroplating, electrotyping, electroforming,
building up of worn out parts in
metallurgical, chemical and other
industries.
 What is Electrolysis?
• Definition of Electrolysis:
→ A chemical process in which bonded
elements and compounds are dissociated
by the passage of an electric current.
• The electrolysis of water:
→ 2H2O + energy = 2H2 + 2O2
 A Basic Electrolyzer
• Two electrodes:
– Cathode (negatively charged)
– Anode (positively charged)

• An Electrolyte

• External circuit

• Diaphragm
 FARADAY’S LAWS OF
ELECTRO-DEPOSITION
• FARADAY’S FIRST LAW: 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,
MαQ
MαIt
M=ZIt (A)
Where, I is the steady current in amperes flowing through
the electrolyte for t seconds and Z is a constant of
proportionality and is known as the electro chemical
equivalent of the substances.
SI unit of Z is the kilogram per clulomb (kg C-1)
• FARADAY’S SECOND LAW: This law states
that when the same quantity of electricity is
passed through several electrolytes, the mass
of the substances deposited are proportional to
their respective chemical equivalents or
equivalent weights.
The chemical equivalent or equivalent weight of a
substance if defined as the weight of that
substance which will combine with or displace
unit weight of hydrogen.
The chemical equivalent of hydrogen is therefore
1. Since the valency of substance if equal to
the no. 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.
Continued…..

Chemical Equivalent = Atomic weight

Valency

From this law it follows that the constant of

proportionality Z in equation (A) is
proportional to the chemical equivalent.
 CURRENT EFFICIENCY:
• Owing to impurities, which causes the secondary
reactions, the quantity of substance or substances
liberated is slightly less than that calculated from
Faraday’s laws.
• This is taken into account by employing a factor,
called current efficiency.
• Current Efficiency is defined as the ratio of actual
quantity of substance deposited or liberated to the
theoretical quantity (from Faraday’s laws)
Current Efficiency
= actual quantity of substance deposited or liberated
theoretical quantity of substance deposited or liberated
 ENERGY EFFICIENCY:
• On account of secondary effects and
reactions the actual substance deposited is
less than that of theoretical value; Voltage
required is also higher than that determined
theoretically.
• Hence actual energy consumption is higher
than that determined theoretically.
Energy Efficiency
= Theoretical energy required
Actual energy required
 EXTRACTION OF METALS:
• Extraction Of Metal is an electro-chemical process
used for the production of metal with commercially
acceptable purity.
• There are two methods of extraction of metals
depending upon the physical state of the ore:
1) In one process the ore is treated with strong acid
to obtain a salt and the solution of such a salt is
electrolyzed to liberate the metal.
2) The second process is employed when the ore is
available in molten state or can be fused and in
this process the ore, which is in a molten state, is
electrolyzed in a furnace.
EXTRACTION OF ALUMINIUM:
Aluminium can be extracted from bauxite,
Kaolinite or nepheline.
 REFINING OF METALS:
• Refining is the process whereby a highly
concentrated mixture of metals is subjected to
electro-chemical 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 trace.
Refining is done for following metals:
1) Refining Of Copper,
2) Refining Of Gold,
3) Refining Of Silver,
4) Refining Of Nickel,
5) Refining Of Lead,
6) Refining Of Zinc,
 ELECTRO DEPOSITION:
• The process of depositing a coating of one
metal over and other 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, Electro-deposition of
rubber and building up of worn out parts for
repairs.
Quality Of ELECTRO DEPOSITION
Depends Upon Following Factors:
1) Nature of electrolyte, (smooth deposition)
2) Current density, (rate of crystal growth)
3) Temperature, (formation of small of large crystals)
4) Conductivity, (economy in power consumption and
reduce tendency to form rough deposition)
5) Electrolytic concentration, (high Current density can be
obtain)
6) Additional agents, (reduces resistance)
7) Throwing power, (it is the ability of electrolyte to produce
uniform deposit on an article of irregular shape)
8) Polarization, (it affects the rate of deposition when current
density limit reaches)
 ELECTRO-PLATING:
• Electro-plating is an art of depositing a
superior or a more noble metal on an inferior
or a base metal of electrolysis of an aqueous
solution of a suitable electrolyte.
• Preparation For Plating:
1) Removal of oil, grease or other organic
material.
2) Removal of rust, oxide or other inorganic
coatings adhering to the metal.
3) Mechanical preparation of surface of metal to
receive the deposited metal, by polishing.
 Alkaline Electrolyzers
• Similar to PEM electrolyzers, except that they use
an alkaline solution as an electrolyte.
• Usually this solution is sodium hydroxide or
potassium hydroxide.
• This type of
electrolyzer
has been in
use
commercially
for several
decades
 Solid Oxide Electrolyzers
• A solid ceramic material is used as the electrolyte.
• At the cathode, water combines with electrons from the
external circuit to produce hydrogen gas and
negatively charged oxygen ions.
• The oxygen ions move through the solid oxide
membrane and release electrons to the external circuit.
• In order for this type of electolyzer to function properly,
the solid oxide membrane must be between 500 – 800
degrees Celsius, which is much higher than the
temperatures required by the other electrolyzers
Energy Balance and Efficiency
of Electrolysis

The electricity needed for hydrogen

production by electrolysis can currently be
generated by a variety of sources,
including:
• fossil fuels
• wind power
• photovoltaic cells
• hydropower
 Necessary Water Inputs
For Electrolysis
• Amount of water needed to meet average
US person’s energy demand though
electrolysis: 3,000 liters of water per
year
• Amount of water currently used by an
average US person for indoor residential
purposes: 138,770 liters a year
 Electrolysis Efficiency
Basics
• Although hydrogen is a promising
alternative fuel, hydrogen production by
electrolysis is not extremely efficient.
• The primary energy inputs to be
considered are the energy requirements
for building and running an electrical
generating facility.
 Energy Balance - Part I
• An input of 1.4 billion kW per hour of
electricity is required to produce 1 billion
kW per hour of hydrogen by electrolysis.
• Energy balance = (Useful Energy
Output)/(Energy Input)
• = (1 kW/hr electricity)/(1.4 kW/hr
hydrogen energy)
• = 0.71, or 71% efficiency for the initial
electrolysis process.
 Energy Balance - Part II
• The other main process to consider in
production of hydrogen gas is the necessary
cooling of hydrogen to about minus 253
degrees Celsius.
• This process demands considerable energy,
resulting in a loss of approximately 30 percent
of the hydrogen energy.
• As a result of each stage of the hydrogen
production process, the total production
efficiency is approximately 30 %.
 High Temperature
Electrolysis
• Process which could increase hydrogen
efficiency to the range of 45 to 50 %
• The DOE is currently examining the use of high
temperature electrolysis powered by fossil fuel,
renewable, and even nuclear technologies.
• High temperature electrolysis utilizes the solid
oxide electrolyzer described earlier.
 High Temperature
Electrolysis
• The efficiency increase is achieved
because high temperature electrolysis
utilizes a significant amount of heat, for
example from a nuclear reactor.
• The added heat decreases the amount of
electricity required to separate the water
into hydrogen and oxygen.
 Photoelectrolysis

Photoelectrolysis: Clean and renewable means of

deriving hydrogen Also known as ‘Water Splitting’
(2 processes):
1) Conversion of solar radiation to electricity in
photovoltaic cells
2) Electrolysis of water in a separate cell

Conversion efficiency = 3% - 32%

 Photoelectrolysis

However, the 2 processes can be combined in

a single nanoscale process: Photon
absorption creates a local electron-hole pair
that electrochemically splits a neighboring
water molecule. In theory, rather than 2
sequential process, the combination can allow
for greater overall efficiency,
 Photoelectrolysis

Challenges: Finding a robust

semiconductor to satisfy the competing
requirements of nature. Solar photons
are primarily visible light, a wavelength
that requires semiconductors that require
small bandgaps < 1.7 eV - for efficient
absorption.
Photoelectrolysis
Possible solution: Oxide
based conductors -
Titanium oxide
• Advantage – robust in
aqueous environments
but have
• Disadvantage - wide
bandgaps ~ 3.0 eV
 Photoelectrolysis

Dye-sensitized photocells:
accumulate energy from multiple low-energy
photons to inject higher-energy electrons into
the semiconductor – a promising direction for
matching the solar spectrum.
 Other Applications of
Electrolysis:
• pH meters -
 Other Applications of
Electrolysis:
• Electroplating
 Other Applications of
Electrolysis:
• Anionic polymerization