ELECTROLYSIS OF MOLTEN ELECTROLYTE USING INERT ELECTRODES.

A molten electrolyte is obtained by heating a compound(eg ionic compound) to

its melting point (does not contain water).
Example; electrolysis of molten sodium chloride using inert electrodes.

Ions present; Na+ , Cl-

No need to draw this second diagram

 Anode(+) Cathode(-)
Chloride ions migrate towards the Sodium ions migrate towards the
anode. cathode.
There, the chloride ions lose There, they gain electrons to form
electrons to form chlorine molecules. sodium atoms.
2Cl- (l) Cl2(g) + 2e- Na+(l) + e- Na (l)
Oxidation occurs. A greyish or silvery globules float at
the surface of the electrolyte near
the cathode.
Green fumes/vapour are observed. Yellow sparks may be observed
because sodium is a reactive metal
and it is oxidised by oxygen.
To prevent the oxidation of sodium
the cathode is covered with an inert
atmosphere using argon.
Reduction occurs.
Overall equation;
2Cl- Cl2 + 2e- Add the two half equations

Na+ + e- Na x 2
2Na+ + 2e- 2 Na

2Na+ + 2Cl- 2Na + Cl2

Q. Predict the products of electrolysis of molten calcium chloride.

IONS PRESENT: Ca2+ ,Cl-
Positively charged calcium ions move to the negative electrode. Here, they gain
electrons to form calcium atoms, so calcium is formed at the negative electrode.
Negatively charged chloride ions move to the positive electrode. Here, they lose
electrons to form chlorine atoms. The atoms join up in pairs to form
Cl2 molecules, so chlorine gas is formed at the positive electrode.

Q.Predict the products of electrolysis of molten aluminium oxide.

Ions present: Al3+ ,O2-
Aluminium will form at the negative electrode.
Oxygen will form at the positive electrode.
Q.Describe the electrolysis of molten sodium bromide(no need of a diagram)
using inert electrodes.(10 MARKS)
Ions present: Na + ,Br-
Anode(+) Cathode(-)
Bromide ions migrate towards the Sodium ions migrate towards the
anode. cathode.
There, the chloride ions lose There, they gain electrons to form
electrons to form chlorine sodium atoms.
molecules. Na+(l) + e- Na (l)
2Br- (l) Br2(g) + 2e-
Oxidation occurs. A greyish or silvery globules float at
the surface of the electrolyte near
the cathode.
Reddish Brown fumes/vapour are Yellow sparks may be observed
observed. because sodium is a reactive metal
and it is oxidised by oxygen.
To prevent the oxidation of sodium
the cathode is covered with an inert
atmosphere using argon.
Reduction occurs.
Overall equation;
2Br- Br2 + 2e- Add the two half equations

Na+ + e- Na x 2
2Na+ + 2e- 2 Na

2Na+ + 2Br- 2Na + Br2

2NaBr (l) 2Na(l) + Br2(l)
Q.Describe the electrolysis of molten lead (II) chloride (no need of a
diagram)using inert electrodes(10 MARKS)

Anode(+) Cathode(-)
Chloride ions migrate towards the Lead ions migrate towards the
anode. cathode.
There, the chloride ions lose There, they gain electrons to form
electrons to form chlorine lead atoms.
molecules. Pb2+(l) + 2e- Pb (l)
2Cl- (l) Cl2(g) + 2e-
Oxidation occurs. Reduction occurs
Green fumes/vapour are observed. A greyish / silvery deposit is
observed around the cathode

Overall equation;
2Cl- Cl2 + 2e- Add the two half equations

Pb2+ + 2e- Pb

Pb2+ + 2Cl- Pb + Cl2

PbCl2 Pb + Cl2
Q.Mention the products of the electrolysis of
a) Molten zinc chloride
Ions present: Zn2+ , Cl-
Anode(+) ; Chlorine
Cathode(-) ; Zinc
b)Molten magnesium iodide
Ions present : Mg2+ ,I-
Anode(+) ; iodine
Cathode(-) ; magnesium

c)Molten calcium oxide (2 x 3 marks)

Ions present : Ca2+ ,O2-
Anode(+) ; oxygen
Cathode(-) ; Calcium
ELECTROLYSIS OF AQUEOUS ELECTROLYTE.
1. Water dissociates partially giving H+ and OH- ions.
H2O(l) H+(aq) + OH-(aq)
2. An aqueous electrolyte is a mixture of a compound/s ( which dissociate
giving ions) and water, that is, an aqueous electrolyte contains ions coming
from water molecules and ions from the compound.
Examples;
1. Aq NaCl
Ions are Na+, Cl- and H+ , OH-
2. Aq CuSO4
Ions are Cu2+, SO42-and H+, OH-
3. Dilute HCl
Ions are H+ , Cl- and H+ and OH-
4. Aq CuSO4 and NaCl
Ions are Cu2+, SO42- and Na+ , Cl- and H+ , OH-
In a mixture of ions, the ions compete with each other.
Hence there is selective discharge of ions, that is, one of the cations and one of
the anions will be discharged preferentially.

SELECTIVE DISCHARGE OF CATIONS.

In a mixture of cations, the cation coming from a metal/element lower in the
reactivity series would be discharged preferentially.
This is because ions coming from reactive metals are stable and ions coming from
less reactive metals are relatively less stable and can easily accept electrons.
Example;
1. During the electrolysis of aqueous NaCl
Ions present are Na+ and Cl- and H+ , OH-
H+ ions will be discharged preferentially because hydrogen is lower in the
reactivity series relative to sodium which is a reactive metal .Hydrogen ions
can readily accept electrons.
2. During the electrolysis of aqueous copper(II) sulphate.
 Ions present are Cu2+ , SO42- and H+ , OH-
Cu2+ ions will be discharged preferentially because copper is lower in the
reactivity series relative to hydrogen .Copper ions accept electrons more
readily that hydrogen ions.

SELECTIVE DISCHARGE OF ANIONS.

a. Sulfate and nitrate ions are not discharged in the presence of hydroxide
ions (aqueous medium) because sulfate and nitrate are relatively stable
ions. Hence the hydroxide ions will be discharged preferentially.
4OH-(aq) 2H2O(l) + O2 (g) + 4e-
b. According to the series shown below hydroxide ions must be discharged
preferentially to halides (Cl-, Br-, I-). However, when a concentrated solution
of the halides is used, hydroxide ions are not discharged. Instead, the halide
ions are discharged because they are far more numerous in the solution.

Example; when concentrated sodium chloride is electrolysed:

Ions present: Na+, Cl-
H+, OH-
Chloride ions and H+ are discharged preferentially.
Chloride ions are discharged instead of hydroxide ions.
2Cl- (l) Cl2 (g) + 2e-

SO42-
NO3- EASE TO BE DISCHARGED INCREASES FROM SULFATE TO HYDROXIDE IONS.

Cl-
Br-
I-
OH-

Summary
NOTE: The factors that determine the selective discharge of ions are:
1. Position of the metal in the reactivity series.
2. Concentration of the ions in the electrolyte.
3. The nature of the electrodes (inert or reactive).

Q.Which of the ions in the following electrolytes will be discharged

preferentially?
a. Concentrated KCl
K+ Cl-
H+ OH-
H+ because hydrogen is less reactive than potassium.
Cl- will be discharged preferentially because it has a higher concentration
than OH-.
b. Aqueous AgNO3
Ag+ NO3-
H+ OH-
 Ag+ and OH- will be discharged preferentially.

ELECTROLYSIS OF CONCENTRATED NaCl (brine)USING INERT ELECTRODES

[GRAPHITE OR PLATINUM].
Ions present: Na+ Cl-
H+ OH-

Anode(+) Cathode(-)
Both chloride and hydroxide ions Both Na+ and H+ migrate.
migrate towards the anode.
However chloride ions are discharged However H+ ions will be discharged
preferentially. preferentially.
2Cl-( l) Cl2 (g) + 2e- 2H+(aq) + 2e- H2( g)
A green gas will be observed. Bubbles of a colourless gas are
observed.
Overall equation:
2H2O + 2NaCl Cl2 + H2 + NaOH
NOTE:
1)Volume hydrogen: volume chlorine
 1 : 1
Chlorine is slightly soluble in water and the volume of chlorine collected during
the electrolysis may be less than the expected.

2)The pH of the concentrated NaCl electrolyte increases during electrolysis due to

the formation of NaOH.
Or:
Because H+ ions were discharged leaving behind OH- ions and concentration of
hydroxide ions increases in the electrolyte.

ELECTROLYSIS OF DILUTE SULFURIC ACID USING INERT ELECRODES [GRAPHITE

OR PLATINUM].
Ions present: H+ SO42-
OH-
HOLFAMNN VOLTAMETER.

Anode(+) Cathode(-)
Both SO42- and OH- migrate towards H+ ions migrate towards the cathode.
the anode.
 However hydroxide ions are However hydrogen ions are
discharged preferentially. discharged preferentially.
4OH-aq 2H2O + O2 g + 4e- 2H+ + 2e- H2
Bubbles of a colourless gas are Bubbles of a colourless gas are
observed. observed.

Overall equation;
2H2OL 2H2 g + O2 g
During electrolysis of dilute sulfuric acid, water molecules are decomposed.
NOTE:
1)The concentration of the sulfuric acid increases gradually during the electrolysis
because water molecules are being decomposed and the moles of sulfuric acid
remains the same.
2)Volume hydrogen: volume oxygen.
2 : 1
As given in the overall equation, that is, for each 1 mole of oxygen formed, 2
moles of hydrogen are formed.
Or
For each 4 moles of electrons passing through the circuit,1 mole of oxygen and 2
moles of hydrogen are formed.

3)Oxygen is slightly soluble in water and the volume of oxygen collected is usually
less than expected.
4) When graphite is used as electrodes the volume of gas formed at the anode
may be greater than expected because the oxygen formed reacts with the carbon
to form carbon monoxide and carbon dioxide.
-

ELECTROLYSIS OF AQUEOUS COPPER (II) SULFATE USING INERT ELECTRODES

[GRAPHITE AND PLATINUM].
Ions present: Cu2+ SO42-
H+ OH-
 Anode(+) Cathode(-)
Both sulfate and hydroxide ions Both copper and H+ ions migrate
migrate towards the anode. towards the cathode.
However OH- ions are discharged However copper ions are discharged
preferentially. preferentially.
4OH-aq 2H2O + O2 g + 4e- Cu2+aq + 2e- Cul
Bubbles of a colourless gas are A red brown or pink deposit on the
observed. cathode. The mass of the cathode
increases with time.
NOTE 1)the pH of the electrolyte decreases due to the formation of sulfuric acid.
2) the blue solution becomes paler or fades with time (maybe become
colourless). This is because copper (II) ions are being discharged at the cathode
and the concentration of the copper ions decreases with time.
3) Sketch a graph showing how the mass of the cathode changes with time when
a CONSTANT CURRENT is used.
Mass of cathode/g

Time/s

4) Sketch a graph showing the change in the mass with time when a CONSTANT
CURRENT is used.
Change in the mass of cathode.

Time/s
5) overall equation:
2CuSO4 + 2H2O 2Cu + O2 + 2H2SO4

ELECTROLYSIS OF AQUOEUS ELECTROLYTE USING REACTIVE ELECTRODES.

Reactive electrodes (Ag, Cu, Mg, Fe) are involved in the electrolysis process.
When electrolysis is performed using reactive electrodes:
Anode(+) Cathode(-)
Anions will migrate towards the Positive ions migrate towards the
anode. cathode.
But none of them will be discharged One of the ions (cations) will be
preferentially. discharged preferentially.
Instead the metal anode will be
oxidised producing ions which go into
the solution and the electrons which
go into the circuit.
Hence the anode dissolves with time
that is the size and the mass of the
anode becomes smaller.

Example: electrolysis of aqueous copper (II) sulfate using copper electrodes.

Ions present: Cu2+ H+
 OH- SO2-4

Anode(+)
Both sulfate and hydroxide ions
migrate towards the anode.
However none of them will be
discharged.
Instead the copper atoms in the
anode will be oxidised.
Cus Cu2+aq + 2e-
The size and the mass of the anode
decreases.
Cathode(-)
Both H+ and Cu2+ ions migrate.
Copper(II) ions will be discharged
preferentially because copper is
lower in the reactivity series than
hydrogen.
Cu2+aq + 2e- Cus
There is a red brown coating formed
on the cathode.
The mass of the cathode increases.
NOTE 1) the solution remains blue because the copper (II) ions are being
continuously produced by the anode and the concentration of copper (II) ions
remains constant.
2) the net result of this electrolysis is the transfer of copper from the anode to
the cathode.

Question; a student performed electrolysis of water . However there were no

reactions occurring at the electrodes.
a. Explain why there were no reactions occurring at the electrodes.
b. What will you add into the electrolyte so that the electrolysis of water
occurs.
Answer;
a. Pure water does not conduct electricity because it dissociates to a very
small extent with very few ions.
b. Add a small amount of a soluble ionic compound to increase the
concentration of the ions in the electrolyte.
Example; sodium sulfate, potassium nitrate, NaCl or add a small amount of
dilute sulfuric acid in the water to favour dissociation of water molecules.
 Or: add a piece of sodium or potassium in the water. These metals will
react with the water producing an alkaline solution. Hence increasing the
amount of ions in the electrolyte.
Pb, Cu, Ag cannot be added because they would not react with water.
INDUSTRIAL APPLICATIONS OF ELECTROLYSIS.
The 3 main applications of electrolysis are:
1. Electroplating.
2. Refining of metals or purification of metals.
3. Extraction of reactive metals like aluminium.
ELECTROPLATING.
Electroplating is the process during which an object (metallic) is coated with
another metal by electrolysis.
Electroplating:
i)gives a good appearance to an object.
ii)it makes the object more corrosion resistant.
e.g: iron coated with chromium will not rust easily.

During electroplating:
1. The cathode must be the object to be electroplated.
2. The anode must be a pure metal that will be used for plating/coating the
object.
3. The electrolyte an aqueous solution of the metal that will be coated on the
object.
Example:
1. Silver plate a spoon.
Anode: silver.
Cathode: spoon.
Electrolyte: aqueous silver nitrate.
 2. Copper plating a decorative object.
Anode: copper.
Cathode: decorative object.
Electrolyte: copper (II)nitrate; copper (II) sulphate.
3. Chromium plating a bicycle handle bar.
Anode: chromium.
Cathode: bicycle handle bar.
Electrolyte: chromium (III)nitrate.

Question: with the help of a diagram describe the electroplating of an iron

spoon by (a) silver
(b) copper

(a)
 Anode(+) Cathode(-)
The silver metal is oxidised Ag+ ions will be discharged
Ags Ag+ + e- preferentially producing silver atoms
which will coat the object/the spoon
Ag+ + e- Ags
The net result is the transfer of silver atoms from the anode to the cathode.

(b)
 Anode(+) Cathode(-)
The copper metal is oxidised Cu2+ ions will be discharged
Cu Cu2+ +2 e- preferentially producing silver atoms
which will coat the object/the spoon
Cu2+ +2e- Cu
The net result is the transfer of copper atoms from the anode to the cathode.
NOTE:
Before electroplating an object it must be properly washed with distilled water to
remove impurities.
During electroplating the current must be kept constant to have a uniform coating
of a metal on the object.
Question; give 2 differences in terms of observations when the following
electrolysis are performed.
Aqueous copper (II) sulfate using Aqueous copper (II) sulfate using
graphite electrodes. copper electrodes.
The blue solution fades with time or The solution remains blue
becomes paler. (unchanged).
Bubbles of colourless gas observed at Anode decreases in size or mass.
the anode.
There is a decrease in the pH of the
electrolyte with time.
REFINING OF COPPER.
Copper metal obtained from extraction is not pure enough to be used in many
applications. The copper is refined or purified using electricity as follows:

Anode; impure copper.

Cathode; thin sheet of pure copper.
Electrolyte; aqueous copper (II) sulfate.
Anode(+) Cathode(-)
The copper atoms on the anode are Copper ions in the electrolyte accept
oxidised producing copper (II) ions electrons from the cathode to form
and electrons. copper atoms.
Cus Cu2+aq + 2e-
Unreactive impurities like silver, gold, The copper atoms coat or deposit on
platinum deposit at the bottom of the cathode.
the anode. Cu2+aq +2e- Cus
 Reactive impurities like zinc are also The net result of this electrolysis is
oxidised like copper atoms the transfer of copper atoms from
Zns Zn2+aq + 2e- the anode to the cathode.

EXTRACTION OF ALUMINIUM.

The main ORE of aluminium is Bauxite (impure aluminium oxide).

Aluminium is a reactive metal and is extracted by electrolysis because of the
strong ionic bonds in its compounds.
Anode (+): big blocks of graphite suspended in the electrolyte.
Cathode (-): the cathode is graphite and is coated in the steel tank.
Steel is used because it has a high melting point and can support the high
temperature of the electrolyte.

Electrolyte:
Impure Al2O3 purified pure Al2O3(s)dissolved incryolite molten aluminium oxide and
Cryolite.
The electrolyte must be in the molten state. However aluminium oxide has a very
high melting point (about 2000oC) and a large amount of energy will be needed to
melt aluminium oxide. Hence extraction of aluminium would not be cost
effective.
To solve this problem, cryolite is added to aluminium oxide to lower its melting
point (900oC). Usually it is said that aluminium oxide is dissolved in cryolite.
Question; mention the reasons why cryolite is used during extraction of
aluminium.
1. It lowers the melting point of aluminium oxide. It behaves as a solvent.
2. It improves the conductivity of the electrolyte by providing ions.
Note : Formula of cryolite is Na3AlF6; 3Na+ AlF63-
-Ionic bond between Na+ and AlF63-
-Covalent bond in AlF63-
Ions present: Al3+ and O2-
Anode(+) Cathode(-)
Oxide ions migrate toward the Aluminium ions migrate towards the
anode. cathode.
The oxide ions lose electrons to form There they accept electrons to form
oxygen gas. aluminium atoms.
2O2-g O2 g+ 4e- Al3+l +3e- All
The carbon anode must be replaced The molten aluminium is collected at
at regular time intervals because the bottom of the container.
they burn away in the presence of
oxygen and high temperature to
form gaseous carbon dioxide and
carbon monoxide.
Overall equation:
2Al2O3( l) 4Al(l) + 3O2( g)

Notes:
1. It is expensive because a high amount of energy is needed to melt
aluminium oxide and to maintain it in the molten state. There is also
replacement of the carbon anode.
2. Releases toxic gases eg; carbon monoxide. Carbon dioxide contributes to
global warming.
Question; what must be taken into consideration when identifying a site where
an aluminium plant must be situated?
1. The availability of the ORE: Bauxite.
2. Transport facilities.
3. Supply of electricity.
4. Away from residential areas.
5. Labour force.
NOTE: when extracting a reactive metal from its ORE, the electrolyte must not be
aqueous [must be molten]. This is because of the presence of H+ , an ion of a
reactive metal is never discharged.

ELECTRIC CELL.
An electric cell is a device in which chemical energy is converted into electrical
energy, that is ,a redox reaction occurs causing a flow of electrons.
Chemical reactions occur flow of electrons generating electricity
There are many different electric cells.
Example of commercial electric cell:
1. Dry cells.
2. Lead acid battery (car).
3. Lithium-ion battery (used in mobile, laptop).
4. Lithium-cadmium battery.

A simple electric cell that can be set up in the lab consist of:
1. 2 different metals having different electrode potentials.
2. An electrolyte.
3. Connecting wires.
4. A bulb or a voltmeter or an ammeter.

Note: A more reactive metal give out electrons more readily .

In these types of electric cells ,there is flow of electrons from the more reactive
electrode to the less reactive electrode.

Example:An electric cell made up of zinc and copper in dilute sulfuric acid.

-ve electrode +ve electrode

It is more reactive metal. The electrodes coming from the
Example: the zinc electrode in cell negative electrons are accepted
above. selectively by a cation in the
electrolyte, that is, a cation that
 comes from an element which is low
down the reactivity series.
Being more reactive the negative 2H+(aq) + 2e- H2 (g)
electrodes will give out electrons
easily and the metallic atoms would
be oxidised.
Zn(s ) Zn2+(aq )+2e-
The electrons go into the wire and
the ions go into the aqueous
medium.
The negative electrode decreases in
size.

Note;1) the voltage in an electric cell depends on the positions of the 2 metals in
the reactivity series. The further apart the metals are in the reactivity series, the
larger the voltage.

2) a salt bridge is made up using a filter paper soaked in an aqueous electrolyte;

example; aqueous KCl or aqueous sodium nitrate.
The salt bridge completes the circuit in the electric cell by allowing the movement
of ions from one electrolyte to the other one.

Note: An electric cell can be set up as shown below

FUEL CELL.
A fuel cell is an electric cell that uses a fuel and an oxidant (oxygen) to generate
electricity. Example of fuels:
Hydrogen, methane, hydrazine (N2H4).

In a hydrogen-oxygen fuel cell the reactions occurring are:

1. –ve: 2H2 (g) + 4OH-(aq) 4H2O(l) +4e-
 Hydrogen has been oxidised to water [oxidation reaction].
2. +ve: O2 (g) + 2H2O(l) +4e- 4OH-(aq)
Oxygen has been reduced.
Overall equation: 2H2 (g )+ O2 (g) 2H2O (l)
Fuel cells are used in rockets, buses, lorries or to supply a building with electricity.
ADVANTAGES OF FUEL CELL.
1. It does not produce harmful gases (carbon monoxide,oxides of nitrogen)as
fossil fuels as it produces water as the only product.
2. It is much more efficient than the traditional way of obtaining electricity
from a fuel.
3. Unlike batteries that may be disposed of, once there chemicals are used up,
fuel cell reactions do not degrade over time and can provide continuous
electricity as long as hydrogen and oxygen are supplied.
4. There are no moving parts in a fuel cell. Hence does not cause noise.
DISADVANTAGES OF FUEL CELLS.
1. It is relatively expensive.
2. Storage of oxygen gas and hydrogen gas is a problem because they must be
kept in specific containers under high pressure to keep them in the liquid
state (in the liquid state more particles can be transported per liquid
volume).
3. Leakage of hydrogen may be dangerous it reacts explosively with oxygen.
4. Supply of hydrogen may be a problem if it is obtained from non-renewable
resources like (hydrogen may also be obtained from renewable resources
example, electrolysis of water but it is expensive).

Example of a fuel cell using an acid:

Question: mention 2 factors which affect the amount of products formed during
electrolysis.
1. Current passing through the circuit.
Amount of product α current.
2. Time taken for electrolysis to be done or to be performed.
Amount of product α time.
3. The charge passing through the circuit.
Amount of product α charge (Q)

Q = IT

Charge current time

NOTE: usually temperature does not affect the amount of products formed.
Question; give the differences between an electric cell and an electrolytic cell.
Electric cell
Chemical energy is converted to
electrical energy.
It is exothermic.
In electric cell, electricity is generated
so only a voltmeter or an ammeter or
a bulb would be needed.
At the negative electrode oxidation
occurs.
At the positive electrode reduction
occurs.
In an electric cell, electrons move
from negative electrode to positive
electrode.
Electrolytic cell
Electrical energy is converted to
chemical energy.
It is endothermic.
In an electrolytic cell a battery is
needed to supply electricity.
At the anode (positive) oxidation
occurs.
At the cathode (negative) reduction
occurs.
In an electrolytic cell, electrons move
from anode (+ve) to cathode (-ve).