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Electrolysis of molten compounds

2 types of electrochemical cell:

a) Electrolytic Cell
b) Voltaic Cell /Galvanic Cell

Electrolysis cell : Electricity energy chemical
Voltaic cell : Chemical energy electricity

The Electrolytic Cell

Electrode connected to the positive terminal of the cell is
positive electrode and is given a name, anode.
The electrode connected to the negative terminal of the
cell is negative electrode and is called the cathode.
When electricity is passed through an electrolyte,
chemical reaction happens.
In this reaction, chemical is splitting up into 2 new
All electrolytes are ionic, which means they are composed
of positively and negatively charged ions.
On passing an electric current through the electrolyte,
these ions move towards the oppositely charged
Most negatively charged ions are non-metal ions, such as
oxide (O
, chloride (Cl
), Iodide (I
), etc.
During electrolysis, negatively charged ions move towards
the positive electrode(anode). The negative ions lose
their electron(s) to the anode, which is positively charged.
The electron(s) is then move to the cathode through the
external circuit (the wire).
The positively charged ions move towards the negative
These positive ions are metal ions, such as copper (Cu
silver (Ag
), lead (Pb
), etc, or hydrogen (H
At cathode, positive ions gain electron(s) from the
cathode, which has an excess of electrons and therefore
an overall negative charge.
This process results in the chemical decomposition of the
electrolyte. It also allows electrons to travel from the
cathode to the anode and hence allows conduction of
During the electrolysis, electrical energy is supplied to the
system to produce a chemical reaction.
Therefore, during electrolysis, electrical energy convert
into chemical energy.
Example 1:Electrolysis of MOLTEN Lead (II) Bromide

This is composed of lead(II) ions, Pb
2 +
, and bromide ions,
. Its chemical formula is therefore PbBr
A suitable apparatus which could be used to carry out this
electrolysis is shown in Figure above.
The bulb helps to show when electricity is flowing in the
circuit, and until the lead(II) bromide is completely molten,
the bulb does not light up . This confirms that electrolytes
have to be molten for the ions to start to move to the
electrodes and thereby conduct electricity.
At the Cathode At the Anode
When electricity is
flowing, a silvery
deposit of lead metal
forms on the cathode.
In fact, as it is molten,
it is more likely to drip
off in a molten blob.
When electricity
is flowing, brown
fumes of
bromine gas are
seen at the
Half equation
+ 2e ---> Pb
Half equation
---> Br
+ e
The lead(II) ions,
as they are
positive, move to
the negative
cathode, where
each ion gains
two electrons to
form a lead atom.
Any reaction at a
The bromide
ions, as they are
negative, move
to the positive
anode, where
each loses an
electron to form
a bromine atom.
Then two of
cathode involved
is again in
electrons. This is
called reduction or
more exactly,
cathodic reduction
these newly
formed atoms
combine to form
bromine gas.
Any reaction at
an anode
involves a loss of
In summary, the lead(II) bromide is split into its
component elements :
---> Pb + Br

Electrolysis Of Molten Lead(II) Oxide
(electrolysis of aqueous solutions)
We have learnt that electrolyte can be molten ionic
compound or aqueous solution of ionic compound, acid or
An aqueous solution is solution of water of a substance.
For example, if you heat sodium chloride until it melts, it is
called molten sodium chloride, but if you dissolve sodium
chloride in water, it is called aqueous sodium chloride.
Electrolysis of aqueous solution is different from
electrolysis of molten electrolyte.
This is mainly because an aqueous solution contain more
types of ions.
Let us take the example of molten sodium chloride and
sodium chloride aqueous.
In molten sodium chloride, the ion present are sodium ion
) and chloride ion (Cl
), due to the decomposition of
the solid sodium chloride.
NaCl ---> Na
+ Cl

In sodium chloride aqueous, other than the
decomposition of sodium chloride solid to form
sodium and chloride ions, some of the water
molecule will also disassociates to form hydrogen
) and hydroxide (OH
) ions.
NaCl ---> Na
+ Cl

O ---> H
+ OH

Which means in an aqueous solution, it can be
more than 1 positive and negative ions.
When the ions move to the anode and cathode,
only 1 negative ion and 1 positive ion will be
selected to be discharged, and this is called
selective discharge.
There are a few factors that determine which ion
will be selected to be discharge, and this will be
discussed in next section.

Factors Affecting Electrolysis
There are three main factors that can affect the
electrolysis products, there are:
1. position in the electrochemical series
2. the concentration and
3. the type of electrode
Electrochemical series

The chart above lists the ions in order of difficulty of
The ions at the top of the list is more difficult to be
discharged, but as we go down the table, they
become easier to be discharged. For example, Cu

easier to be discharged compare with H
and OH
easier to be discharged compare with I
This series of ions is called the Electrochemical
Series. The lower the ion in the electrochemical
series, the easier the ion to be discharged during

Electrolysis of Aqueous Sulphuric Acid
As sulphuric acid is aqueous, it is composed not
only of hydrogen ions (H
) and sulphate ions (SO
), but also of hydroxide ions (OH
) from the water.
+ H
O --> 2H
+ SO
+ H
+ OH

The apparatus used to carry out this electrolysis
and collect the gases given off is shown in Figure
9 .8 .
When we have more than one type of ion moving
to an electrode, selective discharge (or
preferential discharge) takes place.
This means that the ion which can lose or gain
electrons with the greatest ease is discharged,
and the other ions, which are harder to
discharge, remain in solution .
With the electrolyte aqueous sulphuric acid,
migration of ions to the electrodes also occurs.
At the Cathode At the Anode
Here we have only
one ion, the
hydrogen, H+ (aq),
and each ion gains
an electron to
become a hydrogen
Two of these newly
formed atoms then
combine to form a
hydrogen gas
molecule .
Here we have a
choice of either
sulphate, SO

(aq), or hydroxide
(aq) ions.
Hydroxide is easier
to discharge, so
oxygen gas is given
off at the anode.
+ 2e ---> H

+ 4e ---> O
+ H
With electrolysis of aqueous solutions of
dilute acids or alkalis, the volume of
hydrogen given off at the cathode is roughly
twice that of the oxygen gas at the anode.
Accordingly, the elements of water are lost
and as the electrolysis continues, the
concentration of the acid or alkali increases .
Essentially, the electrolysis of aqueous
sulphuric acid is the electrolysis of water, with
hydrogen and oxygen gas being given off in a
ratio of 2 : 1 .
[edit] Concentration
If the concentration of a particular ion is high, it
will be selected to be discharged even though it
is higher in the electrochemical series compares
with another ion present in the solution.
For example, if dilute hydrochloric acid is
electrolysed, hydrogen gas is given off at the
cathode and oxygen gas at the anode.
However, when concentrated hydrochloric acid is
electrolysed, hydrogen gas is still given off at the
cathode, but chlorine rather than oxygen gas will
be released at the anode, even though chloride
is in a higher position in electrochemical series.
Electrolysis Of Diluted Or Concentrated
Hydrochloric Acid

Electrolysis of Concentrated Sodium Chloride
Solution (Brine)
The electrolytic cell used for electrolysis of
concentrated sodium chloride solution is designed to
collect gaseous products at both electrodes as
shown in Figure above.
At Cathode At Anode
The sodium and
hydrogen ions
move to the
cathode .
As the hydrogen ion
), is lower in the
reactivity series
than the sodium
ions (Na+ ), it
Both the chloride
ions (Cl
) and the
hydroxide ions (OH
) migrate to the
anode .
The chloride ions
) are
discharged because
accepts electrons
more easily.
The hydrogen ions
) are discharged.
of their higher
+ e ---> H
Hydrogen atoms join in
pairs to give
molecules :
H + H ---> H

---> Cl + e
Chlorine atoms join in
pairs to give molecules:
Cl + Cl ---> Cl

Changes in Solution
As the hydrogen ions and chloride ions are
discharged, sodium ions and hydroxide ions
remain in the solution . The solution becomes
sodium hydroxide .

Type of Electrode
This is best shown if we consider the electrolysis
of aqueous copper(II) sulphate solution.

Electrolysis of Copper(II) Sulphate by Using
Carbon Electrode
1. If we use carbon electrodes, they are inert
electrodes and do not affect the electrolysis .
2. Therefore, at the anode, we have a choice of
sulphate or hydroxide ions .
3. The hydroxide ions are easier to discharge,
so oxygen gas is given at the anode :
Partial equation 40H- (aq) p O2(g) + 2H2O (l) +
4e- (oxygen gas given off)
At the cathode, we have a choice of copper or
hydrogen ions .
The copper ions are easier to discharge, so we
see a pink deposit of copper metal on the carbon
Partial equation Cu2+ (aq) + 2e- p Cu (s) (copper
metal deposited)
Electrolysis of Copper(II) Sulphate by Using
Copper Electrode
However, if we use copper electrodes, these are
active electrodes and do affect the electrolysis.
Anode At the anode, the copper electrode dissolves
into solution :
Partial equation Cu(s) p Cu 2+ (aq) + 2e (copper
electrode dissolves )
Cathode At the cathode, the copper ions are
deposited as pink copper metal:
Partial equation Cu2+ (aq) + 2e- p Cu (s) (copper
metal deposited)
Evaluating electrolysis in industry

[edit] Industrial Applications of Electrolysis
Electrolysis has many varied industrial applications.
The major applications of electrolysis in industry are
1. Extraction of Metals
2. Purification of Metal
3. Electroplating

[edit] Extraction of Metal
The extraction of metals from their ores, in particular
aluminium and sodium, is important industrial uses of
The diagram below shows the methods of extraction for
different metals.

We can see that those metals which are less reactive than
carbon in reactivity series are extracted from their ore by
displacement reaction using carbon. This will be
discussed in detail in chapter 3, form 5, Oxidation and
Copper and mercury can be extracted from their ore by
burning directly in air.
Silver (Ag) and gold (Au) need no extraction because they
exist as element in nature.
Those metals which are more reactive than carbon are
extracted by electrolysis.

[edit] Extraction of Aluminium
Aluminium is the most abundant metal found in the earth's
crust. It makes up about 8% by weight of the Earths solid
It is also a very useful metal due to its low density and
ability to resist corrosion.
The main source of aluminium is bauxite ore (Aluminium
In industry, aluminium is extracted by electrolysis from
bauxite ore.

Adding Cryolite
In electrolysis, molten aluminium oxide must be used to
extract aluminium. Aluminium oxide decompose to form
aluminium and oxide ions when melted.
---> 2Al
+ 3O

However, the melting point of aluminium oxide is very
high (over 2 000C), so another aluminium compound
called cryolite (Na3AIF6) is added to lower down the
melting point (about 980
The diagram above shows how aluminium is extracted
from molten aluminium oxide by electrolysis.
Graphite is used as the anode and cathode.
During electrolysis, the aluminium ions are attracted
towards the graphite cathode.
The ions is discharged and become molten aluminium
The partial equation of this reaction is as follow:
+ 3e ---> Al
At the anode, oxygen gas which also has
commercial value is collected. The partial
equation of this reaction is as follow:
---> O
+ 4e

At the temperature of 980 C, the oxygen
burns the carbon anode. Therefore the
anode has to be replaced periodically.
Also, this cell uses large quantities of
electricity, and therefore needs cheap
sources of power.
[edit] Extraction of sodium chloride

In industry, sodium is extracted from molten
sodium chloride. Molten sodium chloride is
put into the apparatus as showing in the
diagram above.
When sodium chloride is melted, the sodium
and chloride ions disassociate to become
freely move ions, as shown in the chemical
equation below.
NaCl ---> Na
+ Cl

In thhis electrolytic cell, graphite was
used as anode while iron is used as
The negative chloride ions are attracted
to the anode and then discharged to
form chlorine gas.
---> Cl
+ 2e
Since chlorine gas is also
significant in industry, it is collected
and stored.
In cathode, the sodium ions are
discharged to form sodium atom.
+ e ---> Na
Due to high temperature, the
sodium metal formed is in
molten form.
Metal sodium have lower
density. Therefore it moves
upward and been collected.
[edit] Purification Of Copper

In the refining or
purification of copper, the impure copper is made the
anode and a thin, pure copper plate is used as a
The electrolyte is usually acidified copper(II) sulphate
When electricity flows, the
copper dissolves from the
impure anode and goes into
solution as copper ions.
Impurities in the copper do not
dissolve, and instead fall off
the anode as anode sludge. At
the cathode, the copper ions
are deposited as pure copper
Reaction in anode (impure
In anode, the copper atoms from
the electrode are ionised to form
copper(II) ions.
Cu ---> Cu
+ 2e
Reaction in cathode (pure
Cu ---> Cu + 2e
[edit] Electroplating

Electroplating: Coating
with a Thin Protective
Layer of Metal
A very common use
of electrolysis is to
form a thin protective
coating of a metal on
the surface of another
which is likely to
The diagram above
illustrate the
electroplating of a key
with copper.
In this process, we
need to make the
cathode the object for
plating (the key.
The anode is then
made of the metal we
wish to plate with
(copper), and the
electrolyte needs to
be a solution of a salt
of this metal
(copper(II) sulphate).
In anode, the copper
atoms from the
electrode are ionised
to form copper(II)
Cu ---> Cu
+ 2e
In cathode, the
copper ions are
discharged to
form copper
atom and then
deposit on the
surface of the
---> Cu + 2e