ELECTROLYSIS

 Electrolysis is a chemical process where a substance in molten or solution state is

decomposed by the passage of an electric current.

Conductors – These are substances that can allow an electric current to pass through e.g
metals, graphite.
Non-Conductors – These are substances that do not allow an electric current to pass through
e.g plastic, wood, paper.
- Non-conductors can also be referred to as insulators.
 Conductors can be classified into;
a) Solid conductors
b) Liquid conductors

a) Solid Conductors
 These are substances that conduct electricity in their solid state, e.g metals, graphite.
 Solid conductors usually conduct electricity through delocalized electrons.

NB: When metals are melted they still conduct electricity through delocalized electrons.

b) Liquid Conductors
 These are substances that conduct electricity in their liquid state (either molten or solution)
 They conduct through free ions.
Electrolytic Cell
Direction of flow of
+ - electrons

Bulb

Anode Cathode

Electrolyte

Electrodes
1
 An electrolytic cell can be used to test whether a given substance in molten or solution state
can conduct electricity.

Electrolyte
 A chemical substance in molten or solution state that can be decomposed by the passage of
an electric current.
 An electrolyte can be;
a) An ionic salt e.g sodium chloride, magnesium oxide, Lead (II) bromide e.t.c.
b) A mineral acid e.g hydrochloric acid, sulphuric acid, nitric acid e.t.c.

Electrodes

 These are the terminal through which current enters or leaves a circuit.
 There are two types of electrodes.
a) Anode – This is the electrode connected to the positive terminal of a circuit.
b) Cathode – This is the electrode connected to the negative terminal of a circuit.

NB: - Electrons usually move from the cathode to the anode (i.e negative to positive)

Properties of a good electrode

i) Should be a good conductor of electricity.

ii) Should not react with the electrolyte (unreactive / inert) e.g platinum, copper, carbon
(graphite)

Electrolysis of molten compounds

Electrolysis of molten Lead (II) Bromide (PbBr2)

- +

Bulb

Carbon anode
Carbon cathode

Lead (II) Bromide

Pyrex dish or crucible

Heat
2
 When Lead (II) bromide is in solid state, the bulb does not light since the ions are not free to
move around.
 Once the lead (II) bromide is melted, the bulb immediately lights up.
 The Lead (II) bromide decomposes into bromide ions (Br-) and lead (II) ions (Pb2+)
 The lead ions are attracted to the cathode while the bromide ions (Br-) are attracted to the
anode.

At the Cathode
 The lead (II) ions are discharged by gaining two electrons to form lead metal.
 A grey solid coating is formed around the cathode. This is lead metal.
 The ionic half equation at the cathode is as below.
−¿¿
2+¿+2 e ¿
Pb Pb

At the Anode
 The bromide ions are discharged by losing two electrons to form bromine vapour.
 There is bubbling around the anode as brown bromine gas is given off.
 The ionic half equation is as below;

−¿¿ −¿¿
2 Br Br 2+2 e

Electrolysis and Redox

 A redox reaction is a reaction where both oxidation and reduction occur at the same time.
Oxidation – This is the loss of electrons by a substance.
Reduction – This is the gain of electrons by a substance.

 The lead (II) ions ( Pb2+¿ ¿) are reduced to lead metal by gaining two electrons.
 The bromide ions ( Br−¿¿) are oxidized to bromine vapour by loosing two electrons.
 Therefore, the electrolysis of molten lead (II) bromide is a redox reaction

NB: If you electrolyze a molten ionic compound only containing two elements, you will get
the metal at the cathode and the non-metal at the anode.
 Reduction always occurs at the cathode and oxidation always occurs at the anode.

Electrolysis of aqueous solutions

3
 The electrolysis of sodium chloride solution
 A solution usually contains the ions from the compound and the ions from water.
 Water is called a weak electrolyte. It ionizes very slightly to give hydrogen ions and
hydroxide ions.
−¿¿
+¿+O H( aq) ¿
H 2 Ol H (aq)

At the Cathode
 The solution contains Na+ and Cl-, and they are both attracted to the cathode.
 Sodium is a very reactive metal and this means that it is very difficult to add an electron to a
sodium ion to convert it back to a sodium atom.
 Hydrogen is less reactive than sodium and so it is easier to add an electron to a hydrogen ion
to form a hydrogen atom.
 Each hydrogen atom formed combined with another one to make a hydrogen molecule.
−¿¿
+¿+2 e ¿
2 H(aq) H 2 (g)

 Each time a water molecule ionizes, it also produces a hydroxide ion.

 There is a build-up of these hydroxide ions around the cathode and therefore make the
solution alkaline in region around the cathode.
 Alternatively, neutral water molecules can be thought of as taking electrons directly from the
cathode.

−¿¿ −¿ ¿
2 H 2 Ol +2 e H 2 (g) +2 OH

−¿¿
 From the above equation, the solution becomes alkaline as OH (aq) ions are produced.

At the Anode
 Cl−¿¿ and OH −¿¿ are both attracted by the anode.
 It is slightly easier to remove electrons from the hydroxide ion than from the chloride ion.
 There is many more chloride ions present in the solution, and so it is mainly these that are
oxidized at the anode.

2 Cl−¿¿
(aq) Cl 2(g) +2 e−¿ ¿

4
 +¿¿ −¿¿
NB: The H and Cl ions are removed from the solution by being discharged at the
electrodes.

 Therefore, the H +¿¿ and OH −¿¿ ions are left and so sodium hydroxide is formed as the
remaining solution.

Chlorine gas

Hydrogen gas

Concentrated
Sodium Chloride Glass tube
Solution

Carbon Rubber bung

electrodes
+¿ −¿

+¿ −¿

Battery

Electrolysis of Copper (II) Sulphate solution using inert electrodes

Bubbles of Oxygen

Copper formed
Copper (II) Sulphate
solution

Carbon
 electrodes
Copper (II) ions and hydrogen ions (from water) will be attracted to the cathode.

−¿ +¿ 5
 Copper is below hydrogen in the reactivity series which means that it is easier to add
electrons to copper ions to form an atom.
 The cathode will get coated with pink brown copper.
−¿¿
2+¿+2 e ¿
Cu(aq ) Cu(s) (Reduction)

 Sulphate ions and hydroxide ions (from the water) will be attracted to the anode.
 Sulphate ions aren’t easy to oxidize. Instead, you get oxygen from the oxidation of hydroxide
ions from the water.

4 OH −¿¿
(aq) 2 H 2 O(l) +O2(g )+ 4 e−¿ ¿ (Oxidation)

 Alternatively the anode reaction can be as follows;

−¿¿
+ ¿+ 4 e ¿
2 H 2 O(l) O2( g) +4 H (aq)

+¿¿
 The formation of H (aq) ions shows why the solution becomes acidic.
 If the electrolysis is continued for a long time the copper (II) ions will eventually all be used
up, and so the colour of the solution will fade from blue to colourless.
 Copper ions and hydroxide ions are discharged at the electrodes.
 The hydrogen ions and sulphate ions left combine to form sulphuric acid.

Electrolysis of dilute sulphuric acid using inert electrodes

 The only positive ions arriving at the cathode are hydrogen ions.
 These are discharged to give hydrogen gas.
−¿¿
+¿+2 e ¿
2 H (aq) H 2 (g)

 At the anode, sulphate ion and hydroxide ions are attracted.

 The sulphate ions are too difficult to oxidize, and so you obtain oxygen from the oxidation of
hydroxide ions from the water.

−¿¿ −¿ ¿
4 OH (aq) 2 H 2 O(l) +O2(g )+ 4 e

 Twice as much hydrogen is produced as oxygen.

 For every 4 electrons that flow around the circuit, you would get 1 molecule of oxygen. But 4
electrons would produce 2 molecules of hydrogen.
 You get twice the number of molecules of hydrogen as oxygen

- 6
Dilute sulphuric
acid
 If the metal is high in the reactivity series, you get hydrogen produced at the cathode instead
of the metal.
 If the metal is below hydrogen in the reactivity series, you obtain the metal at the cathode.
 If you have solutions of halides (chlorides, bromides or iodides) you obtain the halogen
(chlorine, bromine or iodine) at the anode.
 With other common negative ions (sulphate, nitrate, hydroxide), you obtain oxygen at the
anode.