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.

We will learn about the electrolysis of:
Molten ionic compounds
Aqueous ionic compounds
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Let us look at the electrolysis of molten lead (II) bromide. The experimental
setup is shown below.
Molten
lead(II) bromide
Carbon electrodes
Heat
Clay triangle
Porcelain crucible
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Electrodes are usually made of carbon or platinum, as they are
unreactive or inert. They do not react with the compounds in
electrolysis.
ELECTRODES
The electrode attached to the
positive terminal of the cell.
Anions are attracted to it.
The electrode attached to the
negative terminal of the cell.
Cations are attracted to it.
Anode Cathode
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At the cathode
The lead ions take electrons from the cathode to become lead
atoms (reduction).

Pb
2+

e
-

Pb +
e
-

Pb
2+
+ 2e
-
Pb
Lead forms molten globules at the bottom of the crucible. We
say the lead ions have been discharged.
( Introduction ) ( Aqueous electrolyte ) ( Summary ) ( Molten electrolyte )
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At the anode
The bromide ions donate electrons to the anode to become
bromide molecules (oxidation).
The bromine is seen as a reddish-brown gas around the anode
during the electrolysis.

Br
-

Br
-

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

( Introduction ) ( Aqueous electrolyte ) ( Summary ) ( Molten electrolyte )
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Bromide ions are
attracted to the
anode
The overall chemical reaction is PbBr
2
Pb + Br
2

Lead ions are
attracted to the
cathode
anode
( Introduction ) ( Aqueous electrolyte ) ( Summary ) ( Molten electrolyte )
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cathode
Pb
2+
Pb
2+
Br
-
Br
-
Molten lead (II) bromide
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Bromide ions
move near to
anode
Lead ions move
near to cathode
anode cathode
Pb
2+
Pb
2+
Br
-
Br
-
Molten lead (II) bromide
( Introduction ) ( Aqueous electrolyte ) ( Summary ) ( Molten electrolyte )
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Bromide ions
donate electrons
anode cathode
Pb
2+
Pb
2+
Br
-
Br
-
e
-

e
-

( Introduction ) ( Aqueous electrolyte ) ( Summary ) ( Molten electrolyte )
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Molten lead (II) bromide
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Bromide ions
donate electrons
anode cathode
Pb
2+
Pb
2+
Br
-
Br
-
Electrons flow
from anode to
battery
e
-

e
-

e
-

e
-

( Introduction ) ( Aqueous electrolyte ) ( Summary ) ( Molten electrolyte )
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Molten lead (II) bromide
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Bromide ions
donate electrons
anode cathode
Pb
2+
Pb
2+
Br
-
Br
-
e
-

e
-

e
-
e
-

Battery pumps electrons
( Introduction ) ( Aqueous electrolyte ) ( Summary ) ( Molten electrolyte )
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Molten lead (II) bromide
e
-

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Bromide ions
donate electrons
anode cathode
Pb
2+
Pb
2+
Br
-
Br
-
Electrons flow
from battery to
cathode
e
-

e
-

e
-

e
-

( Introduction ) ( Aqueous electrolyte ) ( Summary ) ( Molten electrolyte )
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Molten lead (II) bromide
e
-

e
-

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Bromide ions
donate electrons
anode cathode
Pb
2+
Pb
2+
Br
-
Br
-
Electrons flow
from battery to
cathode
Lead ions accept
electrons
e
-

e
-

e
-

e
-

e
-

e
-

e
-

e
-

( Introduction ) ( Aqueous electrolyte ) ( Summary ) ( Molten electrolyte )
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Molten lead (II) bromide
e
-
e
-

e
-

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Lead atoms are
produced
Bromine atoms
combine to form
bromine gas
Mg

Mg

Cl

Cl

anode cathode
Pb

Pb

Br

Br

Br

Br

( Introduction ) ( Aqueous electrolyte ) ( Summary ) ( Molten electrolyte )
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Molten lead (II) bromide
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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.
( Introduction ) ( Aqueous electrolyte ) ( Summary ) ( Molten electrolyte )
Click on the correct answer 4
Next question
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QUIZ 1
2. With reference to the previous question, at which electrode is
the gas formed?
A. Anode.
B. Cathode.
( Introduction ) ( Aqueous electrolyte ) ( Summary ) ( Molten electrolyte )
Click on the correct answer 4
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Solutions can be electrolysed using the apparatus shown
below.
to battery
test-tubes
carbon electrodes
electrolyte (solution)
- +
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Let us look at the electrolysis of dilute sulfuric acid. The
experimental setup is shown below.
test-tubes
carbon electrodes
dilute sulfuric acid
to battery
- +
( Introduction ) ( Aqueous electrolyte ) ( Summary ) ( Molten electrolyte )
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At the cathode
The hydrogen ions take electrons from the electrode to become
hydrogen atoms (reduction).
( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )
H
+

H + e
-

H
+
+ e
-
H
H +
H
H H
H + H

H
2

4
When two of the newly formed atoms combine, hydrogen gas
is produced.
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At the anode
There are two anions in the electrolyte: hydroxide and sulfate
ions. Since hydroxide ions are easier to discharge, oxygen gas
is produced at the anode.
O O
+
e
-

e
-

e
-

e
-

H
H
O
OH
-

OH
-

OH
-

OH
-

+
4OH
-
O
2
+ 2H
2
O + 4e
-

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The electrolysis of dilute sulfuric acid is will result in the production of
hydrogen gas and oxygen at the cathode and anode respectively.
dilute sulphuric acid
oxygen
carbon electrodes
- +
hydrogen
( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )
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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
present. The product that is discharged depends on the nature
of the ions.
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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 H
+
(aq) in the
electrochemical (or reactivity) series are discharged at the
negative cathode.

If the positive ions are those of reactive metals above H
+
(aq)
(e.g.. Na
+
, K
+
and Ca
2+
), hydrogen gas from water is
discharged.
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K
+
(aq)
Na
+
(aq)
Ca
2+
(aq)
Mg
2+
(aq)
Zn
2+
(aq)
Fe
2+
(aq)
Pb
2+
(aq)
H
+
(aq)
Cu
2+
(aq)
Ag
+
(aq)
SO
4
2-
(aq)
NO
3
-
(aq)

Cl
-
(aq)

Br
-
(aq)

I
-
(aq)

OH
-
(aq)
Cations Anions
Difficulty of
discharge
decreases
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QUIZ 2
1. When we electrolyse a solution, what takes place at the
cathode?
A. Oxidation.
B. Reduction.
( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )
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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.
( Introduction ) ( Molten electrolyte ) ( Aqueous electrolyte ) ( Summary )
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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.

The rods through which the direct current enters and
leaves the cell are known as electrodes. Electrodes
are usually inert.
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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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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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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.

The product at the anode is a non-metal.
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Reactive metals are not discharged at the cathode.
Instead, hydrogen from water is evolved.

Sulfate and nitrate ions are not discharged at the
anode. Instead, oxygen from water is produced.
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