Electrolysis

Introduction
Electrolysis is a promising option for carbon-free hydrogen production from renewable and
nuclear resources. Electrolysis is the process of using electricity to split water into hydrogen
and oxygen. This reaction takes place in a unit called an electrolyser. Electrolysers can range
in size from small, appliance-size equipment that is well-suited for small-scale distributed
hydrogen production to large-scale, central production facilities that could be tied directly to
renewable or other non-greenhouse-gas-emitting forms of electricity production.

How Does it Work?

Like fuel cells, electrolysers consist of an anode and a cathode separated by an electrolyte.
Different electrolysers function in different ways, mainly due to the different type of
electrolyte material involved and the ionic species it conducts.

Uses Of Electrolysis
There many uses of electrolysis but the ones being covered in this paper include:
1. Metallic Extraction
2. Electrometallurgy
3. Electroplating

Metallic Extraction
Electrolysis is involved in many industrial processes. One main process is the metallic
extraction based on the position in the electrochemical series. If the metal is more reactive
than carbon, electrolysis is used for metal extraction from and ore. An ore is a rock that
contains a metal or metallic compound that makes ex Carbon electrodes are used to pass
electrical current through the mineral. The metal (cations) is attracted to the cathode and the
pure metal is removed from the cell. For example, in aluminium oxide, the cations (Al+3) are
attracted to the cathode and gain electrons (they are reduced). The equation at the cathode is
Al3+(l) + 3e- → Al(l). The anions (O2-) are attracted to the anode and loose electrons (they are
oxidised). The equation at the anode is 2O2–(l) → O2(g) + 4e–.
Al2O3(l) → 2A(l) + 3O(g)
For metals that are less reactive than carbon, it is cheaper to extract by heating with carbon.
The carbon displaces the metal and bonds with the oxygen to form CO2. Carbon replaces the
less reactive metal in a redox reaction, where the carbon is oxidised and the metal is reduced.
For example, in Zinc Oxide, the Zinc is reduced and the carbon is oxidised.
ZnO(s) + C(s) → Zn(l) + CO(g)

Electrometallurgy
Electrolysis is a separation technique used in many industrial processes. One important
process is Electrometallurgy. This is described as the procedure for purifying or reducing
metals from metallic compounds to achieve the element's pure form using electrolysis.
Copper is the primary metal that is purified in this way.
For purifying Copper, the electrolysis of copper (II) sulphate solution using impure
copper at the anode and pure copper at the cathode, is carried out. The anode is active in this
electrolysis reaction. The ions present in this electrode are: H+, OH-, Cu2+ and SO42-. In
processes with an active anode, the anode itself ionizes and in this case would discharge and
produce Cu2+ ions. Due to the positive copper ions being produced by the anode, it is
attracted to the cathode and forms copper solid. As this reaction continues, the copper at the
anode is being diminished, therefore the size of the anode also decreases. As mentioned
before the anode’s material was impure copper. These impurities are attached to the copper,
but now since the same said copper is being ionized and attracted to the cathode, there is
nothing for the impurities to cling on. This results in the dropping of “anode sludge”, which
also aids in decreasing the size of the anode. Eventually, all the impurities, for example:
bismuth, tellurium and lead, fall to the base of the beaker. To mention again, the anode is
active, therefore it ionizes itself and forms Cu2+ ions which are attracted to the cathode. In
time, the cathode would increase in size as more and more copper solid is being produced.
This all results in the purification of copper.
At the anode: Cu(s)  Cu2+(aq) + 2e-
At the cathode: Cu2+(aq) + 2e-  Cu(s)
Electroplating
Electrolysis has a wide range of industrial applications ranging from extracting metals from
their ores and extracting non-metals from their components and even protecting them from
corrosion. One application of electrolysis is Electroplating. Electroplating is the coating of a
more reactive metal with a less reactive metal to protect it and at the same time making it
more attractive. It is quick and effective if the external power source is sufficient. Plating an
object makes it tougher and improves the corrosion resistance of the material. This method
produces a smooth thick coat enough to protect the material from damage. In electroplating,
the current is usually introduced from an external source and the anode is the positive
electrode and the cathode is a negative electrode. The anode is where the electrochemical
oxidation reaction occurs and the cathode is where the electrochemical reduction reaction
occurs. In the electrolyte there are positive ions (cations) of the metal to be deposited. These
cations are reduced at the cathode to the metal in the zero-valence state. For example, the
electrolyte for copper plating can be a solution of copper (II) sulphate, which dissociates into
Cu2+ cations and SO2−
4 anions. At the cathode, the Cu2+ is reduced to metallic copper by gaining two electrons.
The opposite reaction may occur when the anode is made of the coating metal, turning it into
dissolved cations. For example, copper would be oxidized at the anode to Cu2+ by losing two
electrons. The rate at which the anode is dissolved will be equal to the rate at which the
cathode is plated and the ions in the electrolyte bath are continuously recharged by the anode.
The net result is the effective transfer of metal from the anode to the cathode.
An example of an electrolytic cell used to electroplate copper.

At the Cathode
Copper (II) ions from the electrolyte are attracted here and discharged as copper:
Cu2 (aq) + 2e− → Cu(s)
The copper is plated onto the object.
At the Anode
Copper dissolves to form copper (II) ions:
Cu(s) → Cu2 + (aq) + 2e−

Anodising
Electrolysis is the passage of an electric current through an electrolyte with subsequent
migration of positively and negatively charged ions to the negative and positive electrodes.
There are many processes to electrolysis one of which is anodising. Anodising is a process
that makes the surface of metals resistant to corrosion. Aluminum extrusions are anodized to
delay corrosion, improve lubrication, and allow for colour dying in a process that converts
aluminum electrochemically.

Anodising is the process of making the oxide layer on the surface of aluminum thicker.
Pretreatment is needed as the surface of the aluminum product needs cleaning prior to
anodising. Exposing the surface uses acidic or alkaline cleaning agents to clean grease/dirt
from the surface. Brightening or bright finishing cleans any heavy metal residues left over
from the cleaning process. Using a concentrated mixture of nitric and phosphoric acids to
chemically smoothen the surface provides a metallic finish ready for anodising. Etching
removes a layer of aluminum from the product surface to provide a matte finish. A hot
solution of sodium hydroxide is used to remove surface imperfections.
After pretreatment, the product is ready for anodising. A range of acids may be used as the
electrolyte (organic acid, borate, tartrate, phosphoric acid, and chromic acid however, dilute
sulphuric acid (H2SO4) is most commonly used. Aluminum is the anode, while the cathode
could be copper, lead or graphite. When current is applied, the water in the electrolyte breaks
down and oxygen is deposited at the anode. This oxygen combines with the aluminum to
form aluminum oxide and thus builds on the oxide film always present on the surface. The
oxide layer then becomes thicker and stronger, making aluminum more corrosion resistant.

Reaction at the Anode:

4OH— (aq) → O2 (g) + 2H2O(l) + 4e-

Reaction at the Cathode:

2H+(aq) + 2e- → H2(g)

Conclusion
electrolysis, process by which electric current is passed through a substance to effect a
chemical change. The chemical change is one in which the substance loses or gains an
electron (oxidation or reduction). The process is carried out in an electrolytic cell, an
apparatus consisting of positive and negative electrodes held apart and dipped into a solution
containing positively and negatively charged ions. The substance to be transformed may form
the electrode, may constitute the solution, or may be dissolved in the solution. Electric
current (i.e., electrons) enters through the negatively charged electrode (cathode);
components of the solution travel to this electrode, combine with the electrons, and are
transformed (reduced). The products can be neutral elements or new molecules. Components
of the solution also travel to the other electrode (anode), give up their electrons, and are
transformed (oxidized) to neutral elements or new molecules. If the substance to be
transformed is the electrode, the reaction is often one in which the electrode dissolves by
giving up electrons.
Electrolysis is used extensively in metallurgical processes, such as in extraction
(electrowinning) or purification (electrorefining) of metals from ores or compounds and in
deposition of metals from solution (electroplating).

References
Extracting metals - How are metals with different reactivities extracted? - GCSE Combined Science
Revision - OCR 21st Century - BBC Bitesize
Electrochemical Series Characteristics, Metal Extraction (chemistryscl.com)
Extracting metal using electrolysis - Labster Theory

https://www.bbc.co.uk/bitesize/guides/zyg73k7/revision/4
https://superfund.arizona.edu/sites/superfund.cals.arizona.edu/files/
copper_electrolysis_hands_on_final.pdf
https://www.sciencedirect.com/topics/materials-science/electroplating

https://byjus.com/chemistry/electroplating-process/
https://en.wikipedia.org/wiki/Electroplating
https://www.iqsdirectory.com/articles/aluminum-anodizing/anodized-aluminum.html
https://slideplayer.com/slide/4214724/