Chemical

Substances

Electrolyte
chemical compound that
can conduct electricity in the
molten state or in an
aqueous solution and
undergo chemical changes

molten lead (II) bromide,

aqueous hydrochloric acid,
aqueous sodium hydroxide and
sodium chloride solution, salt
solution, dilute acids and alkalis

Non - electrolyte

chemical compound that

cannot conduct electricity
in any state.

sulphur, naphthalene,
glucose,
tetrachloromethane

ELECTROLYSIS OF MOLTEN COMPOUND

Electrolysis is a process whereby a compound is decomposed by an electric current.
An electrolytic cell consists of two electrodes (anode and cathode) that are dipped in an
electrolyte and connected to batteries

Electrodes are conductors of electricity. Electric current enters or leaves the circuit
through the electrodes.

Graphite or platinum is usually used as electrodes because they are inert (do not react
with electrolytes or products of electrolysis).

Anode is the electrode connected to the positive terminal of the batteries. Anions
(negatively-charged ions) in the electrolyte are attracted to the anode (positive
electrode).

Cathode is the electrode connected to the negative terminal of the batteries. Cat ions
(positively-charged ions) in the electrolyte are attracted to the anode (negative
electrode).

All electrolytes will dissociate into cat ions and anions in the molten states or aqueous
solutions.

Example: Electrolysis of MOLTEN Lead (II) Bromide

Figure above shows the apparatus set up for electrolysis of molten lead (II) bromide.
The electrolysis process starts when lean (II) bromide starts melting.
At the Cathode

At the Anode

Ion presence:
Ion presence:
2+
Pb
BrObservation
Observation
When electricity is flowing, a silvery deposit When electricity is flowing, brown fumes of
of lead metal forms on the cathode. In fact, bromine gas are seen at the anode.
as it is molten, it is more likely to drip off in a
molten blob.
Half equation
Half equation
2+
Pb + 2e ---> Pb
2Br- ---> Br2 + e
Summary:
the lead(II) bromide is split into its component elements :
PbBr2 ---> Pb + Br2
Explanation

At the Anode
1. The negatively charged bromide ions move to the positive anode
2. Each bromine ion loses an electron to form a bromine atom.
3. Two of these newly formed atoms combine to form a bromine molecule (bromine gas).

At the Cathode
1. The positively charged lead(II) ions, move to the negative cathode,
2. Each ion gains two electrons to form a lead atom.

Electrolysis of Aqueous Solution:

1.
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.
2.
Electrolysis of aqueous solution is different from electrolysis of molten electrolyte
because an aqueous solution contains more types of ions.
Example:
Ions presence in molten sodium chloride is Na+ and ClNaCl --> Na+ + ClIons presence in sodium chloride solution is Na+, H+, O2-and ClNaCl --> Na+ + ClH2O --> 2H+ + O2Conclusion:
In an aqueous solution, it can be more than 1 positive and negative ion.
Selective Discharge
1.
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.
2.
There are three main factors that affect the selective discharge in an electrolysis:
a.
position in the electrochemical series
b.
the concentration
c.
the type of electrode
Factors Affecting the Selective Discharge - Electrochemical Series
1.
The tendency of ions to be selected to be discharged at an electrode depends on their
position in a series called the electrochemical series.
2.
The ions at the top of the list are more difficult to be discharged, but as we go down the
table, they become easier to be discharged.
3.
During electrolysis, the ion in the lower position will be selected to be discharge.
4.
Figure below shows the electrochemical series for the positive and negative ions.

Factors affecting the selective discharge - Concentration

Electrolysis of Diluted Hydrochloric

Acid
Ions presence at
Anode:
Cl-, OHCathode:
H+
Observation at
Anode:
Colour gas is produced. When a glowing
wooden splinter is inserted into the test
tube that contains the gas, the splinter
is rekindled.
Cathode
Colour gas is produced. When a lighted
wooden splinter is brought close to the
test tube that contains the gas, a "pop"
sound produced...
Half Equation of the Reaction at
Anode:
4OH- 2H2O + O2 + 4e
Cathode:
H+ + 2e H2

Electrolysis
of Concentrated Hydrochloric Acid
Ions presence at
Anode:
Cl-, OHCathode:
H+
Observation at
Anode:
A greenish yellow gas produced. When a
blue litmus paper is inserted into the
test tube that contain the gas, the blue
litmus paper turn red and then become
colourless.
Cathode
Colour gas is produced. When a lighted
wooden splinter is brought close to the
test tube that contains the gas, a "pop"
sound produced.
Half Equation of the Reaction at
Anode:
2Cl- Cl + 2e
Cathode:
H+ + 2e H2

Note: At anode, the position of hydroxide ion (OH -) is lower compare to chloride ion (Cl -).
However, chloride is selected to be discharged because its concentration is much higher than
his concentration of hydroxide ion.
Additional Note:
1.

Nevertheless, concentration is not a determining factor. It only affects the selective

discharge of the ions which is very close to each other in electrochemical series.
2.
The chart below summarises the ions that likely to be selected if they are presence with
hydrogen ions at cathode or hydroxide ions at anode with high concentration.

Electrod
e
Inert Electrode
Inert electrodes do not react
with electrolyte and does not
take part in the chemical
reaction.
(Example: Carbon,
platinum)

Active Electrode
Active electrode will react
with the electrolyte and take
part in the reaction.
(Example: Copper, Silver,
Mercury)

Example: Electrolysis of Copper (II) Sulphate with Carbon/Copper Electrodes

Using Carbon Electrode

Ions presence at

Using Copper Electrode

Ions presence at

Anode:

OH-, SO42-

Cathode:

H+, Cu2+

Anode:
Cathode:

OH-, SO42H+, Cu2+

Observation at
Anode:
Colourless gas is produced. When a
glowing wooden splinter is inserted into
the test tube that contains the gas, the
wooden splinter is rekindled.

Observation at
Anode:
The electrode becomes thinner.

Cathode
The electrode become thicker.

Colour of the Solution:

Remain unchanged

Colour of the Solution:

Become paler
Half Equation of the Reaction at
Anode:
4OH- 2H2O + O2 + 4e
Cathode:
Cu2+ + 2e Cu

Half Equation of the Reaction at

Anode:
Cu Cu2+ + 2e
Cathode:
Cu2+ + 2e Cu

Cathode
The electrode become thicker.

Note:
For the electrolysis of copper(II) sulphate solution by using copper electrodes, both the hydroxide and sulphate ions
are not selected to be discharged, Instead, the copper electrode ionise to form copper(II) ions. The electrode has
taken part in the reaction!

Industrial Applications of Electrolysis

Electroplating
1.

Electroplating is a process to coat an object with a thin protective layer of metal

2.

Electroplating is used to
a.

prevent corrosion

b.

improve the appearance of the objects

2. In electroplating,
a.

the anode is the electroplating metal

b.

the cathode is the object to be electroplated

c.

the electrolyte must contain the ions of the plating meta

Purifying Of Copper
1. Copper is a good electrical conductor and is used extensively to make electrical wiring
and components. However, the presence of impurity in copper can reduce its electrical
conductivity.
2. In industry, electrolysis processed is used to purify copper, and the process is called
electrolytic refining.

Voltaic Cell - Simple Cell

Simple Voltaic Cell

A simple voltaic cell consists of two metal plates of different metals immerse in an
electrolyte.
The metal which is higher in electrochemical series will become the negative
terminal.
The atom of the metal which is higher in electrochemical series will release electron
to form negative ions.
The electrons are then move to the other metal plate through the wire.
The metal which is lower in electrochemical series will become the positive terminal.
In positive terminal, the electrons will be released to the positive ions in the
electrolyte.
In a voltaic cell, the negative terminal is the anode while the positive terminal is the
cathode
.
Daniel Cell

The Daniell cell was invented in 1836 by a British chemist name John Frederic Daniell.
It was invented to eliminate the hydrogen bubble problem found in the simple voltaic
cell.
The Daniell cell consists of a zinc electrode and a copper electrode.
The zinc electrode is immersed in zinc sulphate solution (or sulphuric acid) whereas the
copper electrode is immersed in copper (II) sulphate solution.
Figure below shows the illustration of the Daniell cell.

The function of the porous pot is

to allow the flow of ions to complete the circuit
To separate the two electrolytes and hence prevent them from react with each other.

Weaknesses of Daniel Cell

The electrolyte can easily spill out.
Difficult to be carried around.
The voltage produced decreases rapidly owing to the polarity of the cell.
Cell with Salt Bridge

1.

A Daniel Cell can be substitute by a design as showing in diagram above. The chemical
reaction remains the same as the Daniel cell.
2.
Using salt bridge can reduce the internal resistance of the cell.
3.
The function of the salt bridge is to allow ions follow from one solution to another to
complete the circuit.

Voltage of the cell

1.
The voltage of a voltaic cell depends on the difference of the electro positivity of the
two metals.
2.
The greater the difference in electrochemical series, the bigger the voltage produced.
3.
For example, the voltage of the cell consist of zinc and copper as the electrodes is
higher than the voltage of the cell that uses iron and copper as its electrodes.

The Electrochemical Series

1.
The electrochemical series is an arrangement of metals based on the tendency of each
metal atom to donate electrons.
2.
The higher the position of a metal in the Electrochemical Series, the greater the
tendency of the metal atoms to donate electrons.
3.
The Electrochemical Series can be constructed based on
a.
The voltage between two metals
b.
The ability of a metal to displace another metal from its salt solution