USES OF ELECTROLYSIS

The major applications of electrolysis are;

1. Extraction of highly electropositive metals (such as Na, K, Mg, Ca, Zn)
2. Purification of metals (e.g. Cu, Hg, Ag, Au).
3. Electroplating of one metal by another.
4. Preparation of certain important compounds, such as sodium hydroxide and sodium
trioxochlorate (v).

1. EXTRACTION OF METALS:
Highly electropositive metals like sodium, potassium, and calcium are extracted by the
electrolytic reduction of their fused chlorides. For example, electrolysis of molten
sodium chloride liberates sodium at the cathode and chlorine gas at the anode.
Elements like chlorine and hydrogen are extracted by electrolysis. An example of
extraction of metals can be shown using extraction of aluminum from purified bauxite
(Al2O3) and extraction of sodium from purified bauxite.
(a) Extraction Sodium: Sodium is extracted commercially from fused sodium chloride
by electrolysis. This electrolysis is performed using a rectangular steel container
whose inside is lined with firebricks. This container is known as downs cell. The
anode used is a graphite rod which project centrally up through the base of the
container. The cathode is a steel cylinder surrounding the anode. Fused sodium
chloride is placed is placed in the downs cell and heated electrically to keep it
molten. The melting point of NaCl is 8010c.
To make the process less expensive and economically more feasible, calcium
chloride is added so as to lower the melting point of the sodium chloride to about
6000c. The anode and cathode are separated from each other by a gauze
diagphram, and the two products of electrolysis are collected separately. The sodium
ions get deposited as sodium metals as they accept one each at the cathode
Na+(aq) + e-  Na(s).
Chloride ions loses one electrons each at the anode to get liberated as chlorine gas
2Cl-(aq) + 2e-  2Cl(g)
The molten sodium collects at the anode and the gaseous chlorine is liberated at the
cathode. The overall electrolytic reaction is given as: 2Na +(aq) + 2Cl-(aq)  2Na(s) + Cl2(g)
The extraction of sodium is not considered environmental friendly because one of the
product is chlorine and chlorine is a poisonous pollutant.
(a) Extraction of Aluminum: Aluminum is extracted from bauxite ores because it is
more abundant and contains less impurities compared to other ores of aluminum.
The two major impurities in bauxite are Iron (iii) oxide, Fe 2O3 and metallic
trioxosilicates (v) (SiO32-). These impurities are removed by heating the bauxite with
a solution of caustic soda under pressure to form a soluble sodium aluminate(iii),
NaAl(OH)4.
Al2O3(s) + 2NaOH(aq) + 3H2O(l)  2NaAl(OH)4(aq)
The bauxite has formed a soluble compound which the impurities cannot react with.
As such the impurities are filtered off and the soluble NaAl(OH) 4 is collected as
filtrate. This filtrate is then crystal seeded using aluminum hydroxide crystals in order
to enhance or induce the precipitation of aluminum hydroxide
NaAl(OH)4(aq)  Al(OH)3(s) + NaOH(aq)
The aluminum hydroxide precipitate is filtered off, washed, dried and heated strongly
to obtain pure aluminum oxide commonly known alumina.
2Al(OH)3(s)  Al2O3(s) + 3H2O(l)
The sodium hydroxide can be concentrated and used again. This is one of the
economy of the process.
Pure aluminum is then extracted from this purified alumina in a molten state.
During the electrolysis, an iron container that is lined with graphite is used as the
electrolytic cell. The graphite lining serves as the cathode and a graphite rod is
used as the anode. The electrolyte is a solution of purified alumina that is dissolved
in molten cryolite, Na3AlF6. The major functions of the molten cryolite are;
(i) To serve as the solvent
(ii) To reduce the melting point of the alumina
(iii) To increase the conductivity of the electrolyte
The electrolyte must be maintained at about 950 0c by heating with a large current. This
very high temperature makes the process to be very expensive. During the electrolysis,
the aluminum ions get deposited at the cathode as aluminum metal by gaining three
electrons.
Al3+ + 3e-  Al(s)
The oxygen ions give up two electrons at the anode and get liberated as oxygen gas.
2O2-  O2 + 4e-
Since the anode material is carbon, the oxygen produced slowly reacts with it, and the
anode is slowly burnt away as carbon (iv) oxide. The anode must then be replaced at
regular interval. This also makes the process more expensive.
The overall electrolytic reaction is given as: 4Al3+(aq) + 6O2-(aq)  4Al(s) + 3O2(g)
The extraction of aluminum is considered environmentally friendly because the liberated
oxygen is not an environmental pollutant.
Anodizing of Aluminum: This is a process by which the surface coating on aluminum is
made thicker. In this process, the aluminum object is made the anode in a cell in which
the electrolyte is dilute sulfuric acid. During the electrolysis process, oxygen is produced
at the anode and combines with the aluminum. The oxide layer on the surface of the
aluminum therefore increases. Dyes can be mixed with the electrolyte and so the new
thicker coating of oxide is colorful and also decorative.

2. PURIFICATION OF COPPER:
The less electropositive metals e.g copper, mercury, silver and gold, tend to occur in
the un-combined form in their ore. These ores are usually contaminated with
impurities such as sand, limestone and iron compounds. An example is the extraction
of copper from copper ore. In this process, an electrolytic cell is used in which the
impure ore serves as the anode and a pure copper plate serves as the cathode. The
electrolyte can be any soluble copper salt, such as copper(ii) tetraxoxsulphate (vi).
At the Anode: The metallic copper atoms in the ore give up two electrons each to go
into solution as copper ions.

Cu (s)
→
Cu2+(aq) + 2e-

At Cathode: The copper ions in the solution are attracted to the cathode where they
receive two electrons each from the cathode to become neutral copper atoms which
are then deposited on the cathode.

Cu2+(aq) + 2e- →
Cu (s)

The net result is that pure copper atoms are transferred from the impure ore (anode)
to the cathode. Similar arrangements are used in the purification of silver, mercury,
and gold. In all cases,
 the electrolyte is a soluble salt of the metal being extracted or purified,
 the anode is the impure metal or metallic ore, while
 the cathode is a pure piece of metal on which the pure metallic atoms can be
deposited.

3. ELECTROPLATING OF METALS:
Electroplating is a method of coating the surface of a metal with another metal
(usually copper, silver, chromium, nickel, or gold) by the means of electrolysis, for
decoration or protection against corrosion. Articles which are usually plated include
 table-ware, cutlery, jewellery and iron or steel objects such as the metallic parts of
motorcars. The arrangement of the electrolytic cell is essentially the same as that
used in the extraction of metals. During electroplating,
 The cathode is the metallic object which is to be plated.
 The anode is the strips (rod) of the plating metal, while
 The electrolyte is a soluble salt of the plating metal.
Thus, in silver – plating a spoon, the cathode is the spoon, the anode is the silver rod
and the electrolyte is a soluble silver salt, usually silver trioxonitrate (v) solution. As
the current passes through the cell, the plating metal dissolves at the anode and the
ions produced migrate to the cathode where they are discharged and deposited as a
layer on the object.

Many articles are plated at the same time. The thickness of the plating may be
controlled by adjusting the magnitude of the current and the duration of the process.
Where the first material used for coating could not adhere, (like in the case of
chromium which does not adhere well to steel), first coat with copper to provide
adhesion, then with a layer of nickel for protection against corrosion and finally, with
a layer of chromium for a tarnish free finish.

Plating Plastics: Nowadays, it is not only metals that can are electroplated. Plastics
have been developed that are able to conduct electricity. For example, the plastic
poly(pyrrole) can be electroplated in the same way as the metals discussed earlier.

Exercise 14:
(1) If a steel spoon were to be plated with silver, state what would be suitable for use as
the (i) anode (ii) cathode (iii) electrolyte
(2) Write two equations for the reactions involved in the purification of bauxite
(3) In the commercial preparation of aluminium by electrolysis,
(a) Name (i) the electrolyte used in the process (ii) ore from which the electrolyte is
obtained (iii) electrodes used in the electrolysis
(b) Give the reason why carbon anode are changed at intervals during the electrolysis of
pure alumina in molten cryolite
(c) Give three reasons why cryolite, Na3AlF6 is added to the electrolyte?
(d) Give the reason why the electrolysis of pure alumina is considered environmentally
friendly while the electrolysis of NaCl is not.
(4) Suggest a suitable method for electroplating a leaf

CORROSION AS A REDOX PROCESS

Corrosion of metal is defined as the gradual deteroriation of metals due to its exposure
to air and water. The combined action of water and atmospheric oxygen on metals bring
about corrosion. This may be accelerated by the presence of electrolyte (such as salt) or
a gaseous pollutant such as carbon (iv) oxide or sulphur (iv) oxide which can dissolve in
water to form electrolyte. The most important example of metallic corrosion is that of
iron. Most metals corrode because they oxidized easily. However, many metals develops
a thin coating of oxide layer which protects their internal atoms from further oxidation.
The metal that best demonstrate this phenomenon is aluminum. Aluminum does not
corrode easily because it forms a thin, adherent layer of aluminum oxide which greatly
prevents further corrosion. The corrosion products of noble metals such as copper and
silver are complex and affect the use of these metals as decorative materials. Under
normal atmospheric conditions, copper forms an external layer of greenish copper
carbonate called patina. Silver tarnish is silver sulfide (Ag2S), which in thin layers gives
the silver surface a richer appearance. Gold, with a positive standard reduction potential
of 1.50 V, significantly larger than that for oxygen (1.23 V), shows no appreciable
corrosion in air.

The term “corrosion” is mainly applicable to other metals apart from iron. Corrosion in
iron is generally referred to as rusting. Iron also forms a protecting coating of oxide
called rust. However, this coating is not adherent as it tends to scale off and thereby
exposing new metal surfaces to corrosion. Iron rust by combining with oxygen in the
presence of water to form hydrated iron(iii) oxide (commonly known as rust), Fe 2O3.
xH2O. Rust is a reddish brown substance which consists mainly of hydrated iron (III)
oxide, Fe2O3.xH2O and a little quantity of iron (II) trioxocarbonate (IV) FeCO 3. The
essential conditions for rusting are: moisture and oxygen (air) which acts together
on iron. Rust is very soft and breaks off easily, thereby exposing the metals the more.
Thus, if iron is exposed to moist air for a long time, it will rust completely. 4Fe(s) + 3O2
+ 2xH2O 2Fe2O3. xH2O(s). Rusting is an electrochemical process.
Iron Oxygen Water Rust

HOW IRON RUST

Iron rust when it comes in contact with air and water because electrochemical cell are
set up at the surface of the contact. In the anodic regions each iron atom gives up two
electrons to form the Fe2+ ion:
Fe(s)  Fe2+(aq) + 2e-
The electrons that are released flow through the iron, as they do through the wire of a
galvanic cell, to the cathodic region, where they are accepted by oxygen to become
reduced as hydroxide ion, OH-:
O2(g) + 2H2O(l) + 4e-  4OH-(aq)
The Fe2+ ions formed at the anode travel to the cathode through the moisture on the
surface of the iron, just as ions travel through a salt bridge in an electrochemical cell. At
the cathode, Fe2+ ions react with oxygen to form rust, which is a hydrated iron(III) oxide
of variable composition:
 4Fe2+(aq) + O2(g) + (4+2x)H2O(l)  2Fe2O3. xH2O(s) + 8H+(aq)
(Rust)

The degree of hydration of the iron oxide affects the color of the rust, which may vary
from black to yellow to the familiar reddish brown. The electrochemical nature of the
rusting of iron explains the importance of moisture in the corrosion process. Moisture
must be present to act as a kind of salt bridge between anodic and cathodic regions.
Iron does not rust in dry air, this explains why cars last much longer in the dry weather
than in the relatively humid weather. Salt also accelerates rusting, this fact is easily
recognized by car owners in the regions where salt is used on roads to melt snow and
ice. The severity of rusting is greatly increased because the dissolved salt on the moist
iron surface increases the conductivity of the aqueous solution that is formed there and
thus accelerates the electrochemical corrosion process. Chloride ions also form very
stable complex ions with Fe3+ ions, and this factor tends to encourage the dissolving of
the iron, thus, accelerating the corrosion. Thus, iron rust faster near the sea due to the
presence of salt in the atmosphere.

The Economic Implication of Corrosion

Many things around us such as vehicles, engines, part of buildings are made of metals.
Corrosion can be viewed as the process of returning of metals to their natural state—
the ores from which they were originally obtained. Corrosion involves oxidation of the
metal.
Since corroded metal often loses its structural integrity and attractiveness, this
spontaneous process has great economic impact. Approximately one-fifth of the iron and
steel produced annually is used to replace rusted metal . Rusting is of great economic
importance because very large sum of money are expended throughout the world on the
various protective processes against rusting. Besides, a lot of money is spent every year
for the replacement of rusted iron world-wide.

PREVENTING CORROSION
Prevention of corrosion is an important way of conserving our natural resources of
energy and metals. The primary means of protection is the application of a coating, most
commonly painting or metal plating, to protect the metal from oxygen and moisture.
Chromium and tin are often used to plate iron because they oxidize to form a durable,
effective oxide coating.
Zinc, also used to coat iron in a process called galvanizing, forms a mixed oxide–
carbonate coating. Since zinc is a more active metal than iron, any oxidation that occurs
dissolves zinc rather than iron. Recall that the reaction with the most positive standard
potential has the greatest thermodynamic tendency to occur. Thus zinc acts as a
“sacrificial” coating on iron.
Alloying is also used to prevent corrosion. Stainless steel contains chromium and nickel,
both of which form oxide coatings that change steel’s reduction potential to one
characteristic of the noble metals. In addition, a new technology is now being developed
to create surface alloys. That is, instead of forming a metal alloy such as stainless steel,
which has the same composition throughout, a cheaper carbon steel is treated by ion
bombardment to produce a thin layer of stainless steel or other desirable alloy on the
surface. In this process, a “plasma” or “ion gas” of the alloying ions is formed at high
temperatures and is then directed onto the surface of the metal.
Cathodic protection is a method most often employed to protect iron in buried fuel
tanks and pipelines. An active metal, such as magnesium, is connected by a wire to the
pipeline or tank to be protected. Because the magnesium is a better reducing agent than
iron, electrons are released by the magnesium rather than by the iron, keeping the iron
from being oxidized. As oxidation occurs, the magnesium anode dissolves, and so it must
be replaced periodically. Ships’ hulls are protected in a similar way by attaching bars of
titanium metal to the iron hull. In salt water the titanium acts as the anode and is
oxidized instead of the iron hull (the cathode).

Methods of Preventing Rusting of Iron

There are many preventive methods against rusting of iron. The basic principle of the
methods is prevention of water and air from coming into direct contact with iron.
Examples of the methods are:

(i) Galvanizing: When iron is coated with zinc, it is called a galvanized iron. The
method involves spraying iron materials (such as pipes, roofing sheets, etc with
powdered zinc or dipping the materials into molten zinc after proper cleaning.
(ii) Electroplating: Electroplating involves electrolytic deposition of metals on iron
materials. When iron is coated with other metals e.g tin, copper, Chromium,
silver or gold, it is electroplated.
(iii) Painting iron parts of machinery and buildings. It involves coating layers of
paints on the iron materials and equipment such as cars, railing, agricultural
equipment, bridges e.t.c
(iv) Enameling: When iron especially those used for cooking is coated with
enamel.
(v) Greasing and Oiling the moving parts of engines. The method involves
rubbing iron or steel materials (such as tools or moving parts of machinery) with
grease or oil.
(NOTE: E.G.P.E.G)

SACRIFICIAL CATHODIC PROTECTION

Both tin and zinc can be used to coat iron to prevent it from rusting. A tin-plated iron is
a sheet of iron coated with a thin layer of tin. A galvanized iron is when the iron is
coated with zinc. Both tin and zinc used in coating iron are not equally efficient. A
galvanized iron is more efficient than a tin-plated iron. That is, a tin-plated iron
corrodes faster than a galvanized iron when they are both subjected to the same
amount of handling. If a galvanized iron is scratched, the iron does not rust, but if a tin-
coated iron is scratched and the iron is exposed, rusting is rapid and facilitated by the
presence of tin.
Why is a galvanized iron more efficient than a tin-plated iron?
The differences in lies in the relative position of zinc, iron and tin in the electrochemical
series. When a galvanized iron and a tin-coated iron is scratched, the holes in them
becomes filled with trioxocarbonate(iv) acid, formed by the dissolving of carbon(iv)oxide
in atmospheric moisture. As a result, a simple electrochemical cell is set-up.
- In a tin-plated iron, because, the iron is above tin in the electrochemical series, it
serves as the anode and the tin serves as the cathode. When the tin layer is broken
or scratched, the iron ionizes and go into solution, thereby bringing about rust. The
rusting even becomes accelerated in the presence of the tin.
- In a galvanized iron, the zinc is above iron in the electrochemical series, it therefore
serves as the anode while the iron serves as the cathode. When the zinc layer is
broken or scratched, the zinc (being the anode) dissolves and enters into solution
leaving the iron (being the cathode) intact and unaffected. Therefore, the iron
remains intact until all the zinc has completely corroded. This type of protection in
which one metal is sacrificed in place of another is known as sacrificial cathodic
protection. The zinc which is sacrificed is described as the “sacrificial metal”. Thus,
zinc forms a more efficient protective coating than tin.
The most suitable of method of preventing the rusting of petroleum pipeline is by
cathodic protection with magnesium.
 QUIZ ME

(1) Which of the following reaction is exemplified by rusting of iron (a) decomposition
(b) displacement reaction (c) neutralization (d) Redox reaction.
(2) Electrolysis is not applied in ---- (a) tin plating (b) purification of copper (c) extraction
of aluminium (d) extraction of iron (e) manufacture of sodium hydroxide
(3) The most suitable method for preventing the rusting of petroleum pipelines is (a)
cathodic protection with magnesium (b) tin-plating (c) painting (d) greasing
(4) Why is iron galvanized with zinc cathodically protected from corrosion? This is
because (a) zinc has a less negative reduction potential than iron (b) Zinc has a
more negative reduction potential than iron (c) both zinc and iron have the same
reduction potential (d) zinc is tougher than iron
(5) Which of the following metal can be used as a sacrificial cathode for preventing
corrosion of a length of iron pipe? (a) Silver (b) Copper (c) Magnesium (d)
Manganese