( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

We have learnt that ionic compounds conduct electricity when

molten or aqueous.
When an electric current passes through such compounds, the
compounds are decomposed in a chemical reaction. This is
known as electrolysis.
The ionic compound is called an electrolyte.
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In this lesson, we will learn about the electrolysis of

• Molten ionic compounds
• Aqueous ionic compounds
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 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

Let us look at the electrolysis of molten lead (II) bromide. The experimental
setup is shown below.

Carbon electrodes

Porcelain crucible
Molten
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lead(II) bromide Clay triangle

Heat

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 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

ELECTRODES
Anode
•The electrode attached to the
positive terminal of the cell.
•Anions are attracted to it.
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Cathode
•The electrode attached to the
negative terminal of the cell.
•Cations are attracted to it.

Electrodes are usually made of carbon or platinum, as they are

unreactive or inert. They do not react with the compounds in
electrolysis.
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 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

At the cathode
The lead ions take electrons from the cathode to become lead
atoms (reduction).

e-
Pb2+ + Pb
e-
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Pb2+ + 2e- Pb
Lead forms molten globules at the bottom of the crucible. We
say the lead ions have been discharged.
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 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

At the anode
The bromide ions donate electrons to the anode to become
bromide molecules (oxidation).

Br -
Br Br + e- e-
Br -
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2Br - Br 2 + 2e-

The bromine is seen as a reddish-brown gas around the anode

during the electrolysis.
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 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

The overall chemical reaction is PbBr2 Pb + Br2

cathode anode

Lead ions are Bromide ions are

attracted to the Pb2+ Br - attracted to the
cathode anode
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Pb2+ Br -

Molten lead (II) bromide

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 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

cathode anode

Lead ions move Bromide ions

near to cathode Pb2+ Br - move near to
anode
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Pb2+ Br -

Molten lead (II) bromide

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 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

cathode anode

e-
Bromide ions
Pb2+ Br - e- donate electrons
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Pb2+ Br -

Molten lead (II) bromide

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 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

e-
cathode anode
e-
Electrons flow
from anode to
battery
e-

Bromide ions
Pb2+ Br - e- donate electrons
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Pb2+ Br -

Molten lead (II) bromide

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 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

Battery pumps electrons

e- e-
cathode anode
e-

e-

Bromide ions
Pb2+ Br - e- donate electrons
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Pb2+ Br -

Molten lead (II) bromide

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 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

e- e-
cathode anode
e-
e-
Electrons flow
from battery to
cathode
e-

Bromide ions
Pb2+ Br - e- donate electrons
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Pb2+ Br -

Molten lead (II) bromide

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 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

e - e-
cathode e- anode
e-
Electrons flow e-
from battery to
cathode e-
e-
e-
Lead ions accept Bromide ions
electrons Pb2+ Br - e- donate electrons
e-
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e-
Pb2+ Br -

Molten lead (II) bromide

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 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

cathode anode

Br
Lead atoms are Bromine atoms
produced Mg
Pb Cl
Br combine to form
Br
bromine gas
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Mg
Pb Cl
Br

Molten lead (II) bromide

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 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

QUIZ 1
1. The electrolysis of molten iron (III) chloride yields iron metal
and a gas. What is the colour of this gas produced?

A. Reddish-brown.
B. Colourless.
C. Yellowish-green.
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 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

QUIZ 1
2. With reference to the previous question, at which electrode is
the gas formed?

A. Anode.
B. Cathode.
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 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

Solutions can be electrolysed using the apparatus shown

below.
test-tubes

electrolyte (solution)
carbon electrodes
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- +
to battery 4
 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

Let us look at the electrolysis of dilute hydrochloric acid. The

experimental setup is shown below.
test-tubes

dilute hydrochloric acid

carbon electrodes
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- +
to battery 4
 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

At the cathode
The hydrogen ions take electrons from the electrode to become
hydrogen atoms (reduction).

H+ + e- H

H+ + e- H
When two of the newly formed atoms combine, hydrogen gas
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is produced.
H + H H H

H + H H2 4
 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

At the anode
There are two anions in the electrolyte: hydroxide and chloride
ions. Since hydroxide ions are easier to discharge, oxygen gas
is produced at the anode.
H H
OH - -
- O e
OH
OH - O O + + e- e-
OH - e-
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-
4OH O2 + 2H2O + 4e-
4
 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

The electrolysis of dilute hydrochloric acid is will result in the production of

hydrogen gas and oxygen at the cathode and anode respectively.

hydrogen oxygen

dilute hydrochloric acid

carbon electrodes
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- +
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 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

What gas do you think will be found at the anode when

aqueous copper(II) sulphate is electrolysed?
Sulphur dioxide?
No, not quite. Oxygen gas is evolved at the anode instead and
copper metal is deposited at the cathode.
How do you explain this phenomenon?
The products can come from the electrolyte or from the water
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present. The product that is discharged depends on the nature

of the ions.

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 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

Negative ions from the electrolyte are discharged if they are

chloride, bromide or iodide ions. For sulphates and nitrates,
oxygen from water is discharged.

Positive ions from the electrolyte that are below Ni2+(aq) in the
electrochemical (or reactivity) series are discharged at the
negative cathode.
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If the positive ions are those of reactive metals above Ni2+(aq)

(e.g.. Na+, K+ and Ca2+), hydrogen gas from water is
discharged.
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 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

Anions Cations
K+ (aq) SO42- (aq)
Na+ (aq) NO3- (aq)
Ca2+ (aq) Cl - (aq)
Difficulty of
Mg2+ (aq) Br - (aq) discharge
decreases
Zn2+ (aq) I - (aq)
Fe2+ (aq) OH - (aq)
SO42- (aq)
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Pb2+ (aq)
H+ (aq)
Cu2+ (aq)
Ag+ (aq) 4
 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

QUIZ 2
1. When we electrolyse a solution, what takes place at the
cathode?

A. Oxidation.
B. Reduction.
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 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

QUIZ 2
2. During the electrolysis of sulphuric acid, hydrogen gas and
another gas are produced. What is the other gas?

A. Oxygen.
B. Sulphur dioxide.
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Click on the correct answer 4

Industrial Applications of Electrolysis

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(a) A silver-plated teapot.
(b) Schematic of the electroplating of a spoon.

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Schematic of the
electroplating of a
spoon.

AgNO3(aq)

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Molten NaCl
Observe the reactions at the electrodes
- +
battery

Cl2 (g) escapes

Na (l)
NaCl (l)
Na+
Cl- Na+

(-) Cl- (+)

electrode electrode
half-cell half-cell
Cl- Na+
Na+ + e-  Na 2Cl-  Cl2 + 2e-
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Molten NaCl Electrolytic Cell
cathode half-cell (-)
REDUCTION Na+ + e-  Na X 2

anode half-cell (+)

OXIDATION 2Cl-  Cl2 + 2e-

overall cell reaction

2Na+ + 2Cl-  2Na + Cl2

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32
 A schematic diagram of an electrolytic cell for
producing aluminum by the Hall-Heroult process.

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Fig. 22.19 A
schematic diagram
of an electrolytic
cell for producing
aluminum by the
Hall-Heroult
process.

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Production of aluminum by electrolysis
(Hall-Héroult Process)
1. Al2O3 is dissolved in cryolite, Na3AlF6.
2. The Al3+ is reduced to Al(l) and the O2- oxidized to O2,
which reacts with the carbon anode to produce CO2.
3. Molten aluminum is periodically drawn off and additional
Al2O3 is added.
4. The carbon anodes must occasionally be replaced as they are
consumed by the reaction with oxygen.

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graphite anodes e-  +
From power source

CO2
bubbles Al+3 Al+3 -
O-2  e-
O-2 O-2
Al2O3 (l)
Al (l)

Draw
carbon-lined steel vessel off
acts as cathode Al (l)
Cathode: Al+3 + 3e-  Al (l)
Anode: 2 O-2 + C (s)  CO2 (g) + 4e- 36
 The Hall Process

Cathode: Al+3 + 3e-  Al (l) x4

Anode: 2 O-2 + C (s)  CO2 (g) + 4e- x 3

4 Al+3 + 6 O-2 + 3 C (s)  4 Al (l) + 3 CO2 (g)

The graphite anode is consumed in the process.

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 Production of solid Mg
• Magnesium is used in many “light weight” structural
applications
• A major source of magnesium is seawater
• Seawater is made basic causing Mg2+ to precipitate as Mg(OH)2

• The precipitate is separated by filtration and dissolved in

hydrochloric acid:
Mg(OH)2(s)+2HCl(aq) MgCl2(aq)+2H2O
• The resulting solution is evaporated to give solid MgCl2,
which is melted and electrolyzed:
MgCl2(l) Mg(l)+Cl2(g)

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39
 Chatode Anode

pure copper impure copper become

Fe2+
produced, covering Zn2+
an anode will reduced
Cathode Cu2+ during electrolysis.
pure copper SO42-
H+ Impure copper

CuSO4/ H2SO4 Precipitation of

Solution as electrolyte impurities

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Electrolysis of brine using a mercury cell.
• At the anode, chloride ions are oxidized to chlorine.

• At the cathode, sodium ions are reduced to sodium atoms,

which dissolve in the mercury.
• The mercury is pumped into a separate compartment and
exposed to water.
• The dissolved sodium reacts with the water to form H2 and
NaOH.

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The Mercury Cell for Production of Chlorine and
Sodium Hydroxide

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 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

•The decomposition of a substance by electricity is

called electrolysis.

•An electrolyte is an ionic compound, in the molten or

aqueous state, that conducts electricity and is
decomposed by the current.
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•The rods through which the direct current enters and

leaves the cell are known as electrodes. Electrodes
are usually inert. 4
 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

•The anode is the electrode which is connected to the

positive terminal of a cell. Anions are attracted to it.
Oxidation occurs at the anode.

•The cathode is the electrode connected to the

negative terminal of the cell. Cations are attracted to
the cathode. Reduction occurs at this electrode.
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 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

When a molten electrolyte is electrolysed,

•a metal (from the positive ions) is discharged at the
cathode.

•a non-metal (from the negative ions) is discharged at

the anode.
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 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

When a aqueous electrolyte is electrolysed,

•the products come from either the electrolyte or water
present.

•The product at the cathode is a metal or hydrogen

gas.
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•The product at the anode is a non-metal.

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 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

•Reactive metals are not discharged at the cathode.

Instead, hydrogen from water is evolved.

•Sulphate and nitrate ions are not discharged at the

anode. Instead, oxygen from water is produced.
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 ( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )

Credits
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return to

micro
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4
lessons