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Electrochemistry Form 3.2

Electrolysis
Definition - electrolysis is the breakdown of an ionic compound,
when molten or in aqueous solution, by the passage of an electric
current.
Terms used in electrolysis
1 electrolyte- is a molten or aqueous ionic substance that
undergoes electrolysis e.g. aq NaCl, aq CuSO4, dil H2SO4, aq HCl,
aq KCl, aq FeSO4, molten PbBr2,
molten SrBr2, molten ZnCl2, acidified water.
2-electrode: A metal or graphite/carbon rod by which the
current enters or leaves the electrolyte. It is a good
conductor of electricity. Examples of electrodes are Pt, silver,
copper, nickel, aluminium
3 anode: A positive electrode from which electrons leave the
electrolyte and enter the external circuit. The electrode that
is connected to the positive terminal of electricity. Oxidation
occurs at the anode.
2 Cl- Cl2 (g) + 2e- 4OH- 2H2O + O2 + 4e-
4 cathode: A negative electrode from which electrons enter
the electrolyte and leave the external circuit. The electrode
that is connected to the negative terminal of electricity.
Reduction (reactions) occurs at the cathode.
Cu2++ 2e- Cu Al3+ + 3e- Al
Na+ + e- Na Mg2+ + 2e- Mg
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5 cation: a positively charged ion attracted to the cathode

e.g. H+, NH4+ or a metal ion (like Cu2+ and Al3+).
6 anion: a negatively charged ion attracted to the anode e.g.
I-, Cl- , O2- , Br- or OH-.
7 Electrolytic cell- This is the container where the process of
electrolysis is carried out.
8 Battery- This is the source of e.m.f which acts as the
electron pump.
9 Non-electrolyte- a solution which does not conduct
electricity e.g. pure distilled water, sugar solution, ethanol,
methylbenzene, butanol, paraffin
bulb

electrolyte cathode
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What happens during electrolysis?

cathode anode

Consider electrolysis of molten

sodium chloride (NaCl(l)).
The ions present are Na+ and Cl-.
The cation Na+ goes to the
cathode while the anion Cl- goes
to the anode.

Each ion is discharged by electron gain or electron loss. The

sodium ion (Na+) is discharged at the cathode to form molten
sodium metal. Electron gain is reduction. Reduction occurs
at the cathode.
cathode reaction: Na+(l) + e- Na(l)
The chloride ion (Cl-) is discharged at the anode to form
chlorine gas. Electron loss is oxidation. Oxidation occurs at
the anode.
anode reaction: 2Cl-(l) Cl2(g) + 2e-
Write ionic equations for electrolysis of molten; lead (II)
bromide
a) lead (II) bromide, PbBr2 Pb2+ +2 Br-
cathode: Pb2+ + 2e- Pb
- -
anode: 2Br Br2 + 2e
b) aluminium oxide, Al2O3 2Al3+ + 3O2-
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cathode: Al3+ +3e- Al

2-
anode: 2O O2 + 4e-
c) copper (II) iodide, CuI2.
cathode:
anode:
d) copper (II) chloride, CuCl2.
cathode:
anode:
e) potassium fluoride, KF.
cathode:
anode:
f) iron(III) bromide FeBr3
cathode:
anode:

Electrolysis of solutions
Products of electrolysis of a solution may be different from those
obtained by electrolysis of the molten ones because produces ions H +
and OH--. The ions from water compete with ions from a salt to
receive or give up electrons. Products of electrolysis depend on
which ions win. There are four rules which affect the products of
electrolysis
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1. Position of ion in the electrochemical series

Ions lower in the electrochemical series will be discharged first.
Cations Anions
K+ hardest SO42- hardest
Na+
Ca2+ NO3-
Mg2+ Decrease of
Al3+ ease of discharge Cl-
Zn2+
Fe2+ Br- Increasing
Pb2+ ease of
H+ I- discharge
Cu2+
Ag+ easiest OH- easiest
Example 1: Electrolysis of dilute NaCl(aq) solution involves the ions
Na+, H+, Cl- and OH-.
The positive ions Na+ and H+ go to the cathode but H+ is discharged
first as it is lower than Na+.
2H+(aq) +2e- H2(g)
The negative ions Cl- and OH- go to the anode where OH- is
discharged first.
4OH- 2H2O + O2 + 4e-
The products are oxygen gas and hydrogen gas (compare with
products of electrolysis of molten NaCl which are sodium and
chlorine gas).
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Concentration of NaCl increases because water is decomposing

instead of the sodium chloride.
Example 2: Electrolysis of dilute or aqueous copper(II) sulphate
solution, using inert electrodes, involves the ions Cu2+, H+, SO42- and
OH-. The lower ions; Cu2+ and OH- are discharged off first.
Cathode: Cu2+(aq) +2e- Cu(s)
Anode: 4OH-(aq) 2H2O(l) + O2(g) + 4e-
Products are copper metal and oxygen gas. The solution
changes from copper (II) sulphate to sulphuric acid. The
colour changes from blue to colourless as Cu2+ ions are
removed from solution. The cathode gets bigger as copper
metal forms on the anode.
Dilute Ions present Cathode equation Anode equation
solution of  (discharged)
NaCl Na+ Cl- 2H+ + 2e- H2 4OH- 2H2O +O2+4e-
H+  OH-  Product: hydrogen Product: oxygen
CuSO4 Cu2+  SO42- Cu2+ +2e- Cu 4OH- 2H2O +O2+4e-
H+ OH-  Product: copper Product: oxygen
KNO3 K+ NO3- 2H+ + 2e- H2 4OH- 2H2O +O2+4e-
H+  OH-  Product: hydrogen Product: oxygen
H2SO4 H+  SO42- 2H+ + 2e- H2 4OH- 2H2O +O2+4e-
H+ OH-  Product: hydrogen Product: oxygen
-The product of electrolysis of any dilute aqueous solution is the
same at the anode because OH-, being the lowest in the
electrochemical series, is discharged first.
-When a dilute acid (e.g. sulphuric acid) is electrolysed, the result is
the decomposition of water rather than that of the acid.
2H2O(l) 2H2(g) + O2(g)
That is why the electrolysis of a dilute acid is called the electrolysis of
acidified water.
2. Concentration of electrolyte
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This rule applies to a solution containing OH- and Cl- ions only.
The ion with a higher concentration is discharged first.
When using dilute sodium chloride solution, ions present are Na+, H+,
Cl- and OH-. The H+ and OH- ions are discharged first as shown in rule
1 to give hydrogen and oxygen gases.
Using a concentrated (or saturated) solution of sodium chloride, Cl-
ions are discharged first at the anode to give chlorine gas.
Anode 2Cl-(aq) Cl2(g) + 2e-
The cathode reaction is unchanged. H+ are discharged to give
hydrogen gas.
Cathode: 2H+(aq) + 2e- H2(g)
Na+ and OH- ions remain in solution forming sodium hydroxide
solution at the cathode. NaOH(aq) is the third product of electrolysis of
(conc NaCl). If the universal indicator is added to the electrolyte it
turns colourless at the anode as the chlorine gas produced bleaches
the universal indicator. The universal indicator turns purple or dark
blue at the cathode when sodium hydroxide (an alkali) is formed.
3. The type of electrodes used - Electrolysis of copper (II) sulphate
solution using inert electrodes, like graphite or platinum, produces
copper at the cathode and oxygen at the anode. Using copper
electrodes gives a different result at the anode.
Cathode: Cu2+(aq) + 2e- Cu(s)
Inert electrode: 4OH-(aq) 2H2O(l) + O2(g) + 4e-
Using copper anode: OH- and SO42- ions are attracted but neither gets
discharged. The copper anode dissolves forming copper ions.
Copper anode: Cu(s) Cu2+(aq) + 2 e-
The copper anode wears away while the cathode gets thicker. The
electrolyte does not change colour because Cu2+ ions removed from
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the electrolyte at the cathode are replaced by the anode dissolving.

This process is used in industries to purify copper and to electroplate
objects with an unreactive metal.
4. State of the electrolyte ( aqueous or molten)-In molten
electrolytes, there is no competition of ion discharged. In aqueous
electrolysis, competition occurs with ions from water.

APPLICATIONS OF ELECTROLYSIS IN INDUSTRY

1. Electrolytic purification of copper.
2. Electrolysis of brine (conc NaCl) using a diaphragm cell.
3. Extraction of aluminium from molten aluminium oxide.
4. Extraction of sodium, magnesium and calcium metals.
5. Electroplating of objects.

Extraction of copper metal The ores of copper are malachite [ CuCO3,

Cu(OH)2 ] and chalcopyrite Cu2S. The ores are crushed and roasted to
remove impurities of iron and sulphur ( SO2 is formed). The ores are
then concentrated by froth floatation to remove impurities of other
metals. The pure ores are reduced by heating with carbon in a blast
furnace to form impure or blister copper metal. The impure copper
metal is purified to form pure copper metal by electrolysis.
Electrolytic purification of copper
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Copper made by roasting copper sulphide ore in air, is about 99.5%

purer. This 0.5% impurity cuts down electrical conduction of
copper significantly. Electrolysis is used to purify the impure copper,
to form about 99,99 % pure copper metal. Impure copper is made
the anode in an electrolytic cell containing acidified copper (II)
sulphate solution as the electrolyte. Thin sheets of pure copper are
used as the cathode.
Anode reaction: Cu(s) Cu2+(aq) + 2e-
Cathode reaction: Cu2+(aq) + 2e- Cu(s)
Pure copper is removed from the impure anodes and gets deposited
on the cathodes. Any impurities fall to the bottom of the cell as
anode sludge. Copper is effectively transferred from the anode to the
cathode. The solution colour does not fade as the Cu2+ ions removed
at the cathode are replaced by those formed at the anode. The same
process is used to electroplate objects. e.g. Chromium plating a key/
ring requires:
(i) Chromium metal anode.
(ii) Chromium nitrate or sulphate solution as the electrolyte.
(iii) The key or ring as the cathode.
Chromium is transferred from the anode to the cathode.
Diagram
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The object to be electroplated e.g. key, ring is connected to the

cathode. The metal that is plating is put at the anode. The electrolyte
is a solution/ salt of the metal at the anode
2.Electrolysis of brine using a diaphragm cell
Electrolysis of concentrated aqueous sodium chloride (brine)
produces chlorine gas at the anode, hydrogen gas at the cathode and
sodium hydroxide solution as the other by-product at the cathode.

The diaphragm cell is lined on the outside with a layer of bricks to

insulate it
The diaphragm which separates the anode and cathode
compartments is made of asbestos. The liquid level in the anode is
higher than that in the cathode side to allow for seepage. When the
electric current is passed the electrolyte dissociates as follows:
Na Cl(aq) Na+(aq) + Cl- ( aq)
H2O(l) H+(aq) + OH-(aq)
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Anode reaction: 2Cl-(aq) Cl2(g) + 2e-

Cathode reaction: 2H+(aq) + 2e- H2(g)
The Na+ and OH- ions pass through the asbestos diaphragm and
react to form sodium hydroxide ( in the cathode).
Na+ + OH- Na OH. The electrolysis of brine gives chlorine gas,
hydrogen gas and sodium hydroxide.
Chlorine formed reacts with NaOH(aq) to produce a bleach sodium
chlorate(I) [NaOCl]. A diaphragm is used to keep chlorine and sodium
hydroxide separate.
Properties of chlorine gas 1 A green gas 2 Poisonous and oxidising
agent
3 Soluble in water
Uses of chlorine gas 1 Purification of water by killing bacteria. 2 To
make bleaching powder
Experiment aim: To electrolyse molten lead(II) bromide, PbBr2
Apparatus: bulb, electrolytic cell, burner, lead(II) bromide,
connecting wires
Diagram:
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Method 1 Set the apparatus as shown on the diagram.

2 Put the lead(II)bromide salt into the crucible.

3 Apply heat.
4 Switch on the current and electrolyse the molten lead(II)bromide
salt for 20-30 minutes, using graphite electrodes.
5 Observe the results.
Results. The molten PbBr2 dissociates as follows.
PbBr2 Pb2+ +2Br-
Brown fumes of Br2 are formed at the anode.
Anode reaction 2Br- Br2+2e
Cathode reaction Pb2+ +2e- Pb Beads of lead are collected at
the cathode. The bulb lights up only when the salt PbBr2 is molten.

3. Extraction of aluminium

The major ore is bauxite which contains up to 60% Al2O3 with

impurities of Fe2O3 and SiO2. Bauxite is hydrated aluminium oxide
Al2O3, nH2O. Bauxite is purified by crushing, dissolving in sodium
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hydroxide and heating to get pure alumina, Al2O3. The impurities are
filtered off.
Pure alumina, Al2O3 has a very high melting point (2050oC). This
melting point is lowered by dissolving Al2O3 in molten cryolite,
Na3AlF6 (sodium aluminium fluoride) to 950oC. The molten solution
has about 10% Al2O3. This solution is electrolysed using
graphite/carbon electrodes to give molten aluminium metal and
oxygen gas. The electrolytic tank contains carbon anodes and a lining
of carbon cathode. When the pure aluminium oxide is electrolysed at
high current (150 000-300 000 A) it dissociates to form aluminium
ions and oxide ions. Al2O3 2 Al3+ + 3O2- . The aluminium ions
migrate to the cathode and the oxide ions migrate to the anode and
form oxygen gas.
cathode: Al3+(l) + 3e- Al(l)
Molten aluminium is removed from the bottom of the cell.
anode : 2O2-(l) O2(g) + 4e-
Oxygen gas is produced at the anodes. The oxygen formed reacts
with the carbon anodes to produce carbon dioxide gas
C(s) + O2(g) CO2
Anodes therefore wear away with time and must be replaced from
time to time.
N.B. Toxic fluorine gas is given off at the anodes
Properties of aluminium
1 It is a light shiny white lustrous metal
2- It has a melting point of 660 °C
3 Aluminium is light but strong
4 Aluminium is corrosion resistant, because of the formation of the
Al2O3 layer.
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5 Aluminium has a low density of 2,1g/cm3.

6 Aluminium is a good conductor of heat and electricity.
7 It is non-toxic.
8 Aluminium can be readily alloyed with other metals e.g. duralumin,
alnico
Uses of aluminium
use property
1.Making aircraft bodies. Low density, malleable and ductile.

2.Overhead electrical cables.[The Good conductor of electricity and

cables have a strengthening core of is ductile.
iron metal]

3. Food containers, cooking foil and Unreactive due to oxide layer,

saucepans. malleable, non-toxic and low
density.
4 It is used to make alloys Alnico Duralumin is very light but very
and Duralumin strong. It is used in air frames and
aircraft bodies.
Al + Ni +Co Alnico
Mg +Mn + Al + Cu Duralumin
5 Aluminium is used to make Light,unreactive
cooking utensils
6 Aluminium is used to make Nontoxic,light
wrapping foil.
Anodising of aluminium Anodising is the process by which the
natural film on aluminium is greatly increased in thickness.
Aluminium metal is on the anodic side of the galvanic series. Its
position is similar to zinc and magnesium i.e. it is readily oxidised.
The oxide on aluminium is naturally corrosion resistant, very hard,
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abrasion resistant, an insulator and very tenacious. In its natural

form the oxide film on aluminium is less than 0.50 microns thick.

Because the naturally occurring film is very thin and attached to a

soft ductile metal, it is easily damaged. Building up this coating
provides very useful properties for the aluminium surface.

Hydrogen–oxygen fuel cells

A hydrogen and oxygen uses the raw materials oxygen gas and
hydrogen gas to produce electricity with water as the only chemical
product.
2H2 (g) + O2(g) 2H2O(l)
Advantages of the hydrogen oxygen fuel cell
1 Fuel cells are pollution free producing only water whereas petrol
engines produce carbon dioxide and oxides nitrogen
2 Fuel cells produce more energy per kilogram than petrol or diesel.
3 No power is lost in transmission as there are no moving parts in
fuel cells, unlike in internal combustion engines
4 Fuel cells are quieter soles noise pollution compared to petrol
engines.
Disadvantages
1 Hydrogen gas is more difficult and expensive to store compared to
petrol as it is flammable and easily explodes under pressure.
2 Materials used in producing fuel cells are expensive.
3 Hydrogen gas is obtained by methods that involve combustion of
fossil fuels, therefore releasing carbon dioxide and other pollutants
into the atmosphere.
4 There are only a small number of hydrogen filling stations across
the country.
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5 Fuel cells are affected by low temperatures, becoming less

efficient.

Summary points