6.

1 Electrolytic Cell

Electrolysis is the decomposition of a compound in the molten or aqueous state into its
constituent elements when electric current flows through it.

Electrolytes: Substances in the molten or aqueous state which allow electric current to
flow through them and undergo chemical changes

Non-electrolytes: Substances in the molten or aqueous state which do not allow electric
current to flow through them and undergo chemical changes

● Electrolytes in the solid state cannot conduct electricity because there are no
free-moving ions to conduct the electricity.

“Molten” refers to a substance that has been heated to a temperature where it changes from
a solid to a liquid state.
Electrolysis Process

During the electrolysis process,

• positively charged ions (cations +) move to the cathode (negative electrode)

• negatively charged ions (anions - ) move to the anode (positive electrode)

Electrolysis of molten lead(II) bromide, PbBr2,

● Cathode: lead(II) ions, Pb2+

● Anode: bromide ions, Br–

3 Factors Affecting the Products in Electrolysis

1. • position of ions in the electrochemical series

2. • concentration of electrolyte
3. • types of electrode

1. Position of ions in the electrochemical series

Example 1

Electrolysis of sodium sulphate solution

(a) Ions present in a sodium sulphate solution:

sodium ions (Na+), hydrogen ions (H+), sulphate ions (SO₄²⁻), hydroxide ions(OH-)

Cathode Anode

(i) Attract positive ion: sodium ions (Na+) (i) Attracts negative ions: sulphate ions
and hydrogen ions (H+) (SO₄²⁻) and hydroxide ions(OH-)

(ii) Hydrogen ions (H+) are selected to be (ii) Hydroxide ions (OH-) are selected to be
discharged because the hydrogen ion is discharged because the hydroxide ion is
less electropositive compared to the sodium less electronegative compared to the
ion sulphate ion

(iii) Hydrogen gas is produced at the (iii) Oxygen gas is produced at the anode
cathode

Example 2

Electrolysis of copper(II) sulphate solution

(a) Ions present in a copper(II) sulphate solution:

copper(II) ions(Cu²⁺),hydrogen ions (H+), sulphate ions (SO₄²⁻), hydroxide ions(OH-)

Cathode Anode

(i) Attract positive ion: copper(II) ions (Cu²⁺) (i) Attracts negative ions: sulphate ions
and hydrogen ions (H+) (SO₄²⁻) and hydroxide ions(OH-)

(ii) Copper(II) ions (Cu²⁺) are selected to be (ii) Hydroxide ions (OH-) are selected to be
discharged because the copper(II) ion is discharged because the hydroxide ion is
less electropositive compared to the less electronegative compared to the
hydrogen ion sulphate ion

(iii) Copper is deposited at the cathode (iii) Oxygen gas is produced at the anode
Test for gases

Oxygen gas : Glowing wooden splinter

Hydrogen gas: Burning wooden splinter

Test for gases

Turn Blue is alkaline.

Turn Red is acidic.

Effect of Concentration of Electrolyte
1. Anode: Negative ions which are more concentrated in an electrolyte are more
likely to be discharged at the anode.

2. Cathode: The selection of positive ions to be discharged at the cathode is still

influenced by the position of the positive ions in the electrochemical series.

Example 1

Electrolysis of concentrated sodium chloride solution and dilute sodium chloride solution

(a) Ions present in a concentrated or dilute sodium chloride solution:

sodium ions (Na+), chloride ions (Cl-), hydrogen ions (H+), hydroxide ions(OH-)

Cathode Anode

(i) Attract positive ion: sodium ions (i) Attracts negative ions: chloride ions (Cl-) and
(Na+) and hydrogen ions (H+) hydroxide ions (OH-)

(ii) Hydrogen ions (H+) are selected (ii) The negative ion discharged at the anode is
to be discharged because the influenced by the concentration of the negative
hydrogen ion is less electropositive ion in the electrolyte as follows:
compared to the sodium ion
Case 1: concentrated sodium chloride solution
(iii) Hydrogen gas is produced at the (1.0 mol dm–3 sodium chloride solution)
cathode ● the concentration of chloride ion is higher
than the concentration of hydroxide ion
● Chloride ion (Cl-) will be selected to be
discharged even though the position of the
chloride ion is higher than the hydroxide ion
in the electrochemical series.
● Chlorine gas is produced at the anode.

Case 2: concentrated sodium chloride solution

(1.0 mol dm–3 sodium chloride solution)
● the concentration of chloride ion is lower
than the concentration of hydroxide ion
● Hydroxide ions (OH-) will be selected to be
discharged because it is less
electronegative compared to the chloride
ion.
● Oxygen gas is produced at the anode.
Types of Electrode

Example 1
Electrolysis using :
● Silver nitrate solution: silver ions(Ag+), nitrate ions(NO3–), hydroxide ions(OH-),
hydrogen ions (H+)
● Silver electrode

Cathode Anode

(i) Attract positive ion: silver ions(Ag+) and (i) Forms silver ions when silver atoms at
hydrogen ions (H+) the anode ionise. Nitrate ions and
hydroxide ions are not discharged
(ii) Silver ions (Ag+) are selected to be
discharged because the silver ion is less
electropositive compared to the hydrogen ion (ii) The silver electrode dissolves in the
electrolyte
(iii) Silver is deposited at the cathode

● The concentration of silver ions in the electrolyte does not change

● because the rate of silver atoms ionised to form silver ions at the anode is the same
as the rate of silver ions discharged to form silver atoms which are deposited at the
cathode.

Example 2
Electrolysis using :
● Silver nitrate solution: silver ions(Ag+), nitrate ions(NO3–), hydroxide ions(OH-),
hydrogen ions (H+)
● Carbon electrode

Cathode Anode

(i) Attract positive ion: silver ions(Ag+) and (i) Attracts negative ions: nitrate ions(NO3–)
hydrogen ions (H+) and hydroxide ions(OH-)

(ii) Silver ions (Ag+) are selected to be (ii) Hydroxide ions (OH-) are selected to be
discharged because the silver ion is less discharged because the hydroxide ion is
electropositive compared to the hydrogen less electronegative compared to the
ion sulphate ion

(iii) Silver is deposited at the cathode (iii) Oxygen gas is produced at the anode

● The concentration of silver ions in the electrolyte decreases

● because the silver ions from the electrolyte are discharged to become silver
atoms and deposited at the cathode.
 Application of Electrolysis in Industries

(a) Extraction of metals

● Extract metals like potassium, sodium, calcium, magnesium and aluminium from their
molten ores or salts through electrolysis.

(b) Purification of metals

● impure metal is used as the anode while the pure metal is used as the cathode.
● During electrolysis, the metal at the anode will dissolve into the electrolyte to form
ions.
● These ions will move to the cathode to be discharged and deposited at the cathode
as pure metal.

(c) Electroplating of metals (making gold spoon)

● gold, platinum and silver are electroplated on other metals to make the metal look
more attractive and to withstand corrosion.

(d) Wastewater treatment using electrocoagulation

● to treat wastewater.
● involve 2 process: electrolysis and coagulation.

Electrolysis
1. At the anode, a metal electrode such as aluminium ionises in the electrolyte to produce positively
charged aluminium ions, Al3+.

2. At the cathode, hydrogen ions, H+ are selected to be discharged to form hydrogen gas. Hydrogen gas
bubbles are released from the cathode and rise to the water surface.

Coagulation
3. Coagulation occurs when aluminium ions, Al3+, hydroxide ions, OH– and pollutants in the wastewater
combine to produce coagulants known as floc.
(aluminium ions (Al3+) + hydroxide ions (OH– ) = Floc)
4. Floc, trapped in hydrogen gas bubbles released from the cathode, are brought up to the water surface.
5. The remaining flocs sinks and accumulates at the base.
6.2 Chemical Cell

● Magnesium becomes the negative terminal and copper becomes the positive
terminal.
● This is because magnesium is more electropositive than copper.
● Magnesium is more likely to donate electrons compared to copper.
Application of of Chemical Cell

Fruits and vegetables can generate electricity!