5.

05 Principles of electrolysis

Electrolysis is splitting by electricity.

For a compound to undergo electrolysis, it must be:

1. Made of ions
2. Melted or dissolved in water so the ions are free to move.

The electrolysis of molten lead bromide

The electrolysis of molten lead bromide can be carried out by using an apparatus as shown below.

New vocabulary:

 Electrolyte – The liquid you electrolyse. (In this example – lead(ii)bromide)

 Electrodes – The graphite rods that carry the charge from the battery.

When the switch is closed, the electrical energy from the battery causes a chemical change and
causes the following reaction to occur.

Lead Bromide Lead + Bromine

PbBr2 (l) Pb(s) + Br2 (g)

What you see at the electrodes:

 At the positive electrode: bromine vapor is seen bubbling.

 At the negative electrode: A bead of molten lead is seen forming.
What happens when you close the switch:

 Opposite charges attract.

 Bromine ions are negatively charged. So they move towards the positive electrode.
 Lead ions are positively charged so they move towards the negative electrode.

What happens at the electrodes:

At the negative electrode:

 Lead ions have a charge of +2.

 Lead ions receive two electrons and become lead atoms.

Pb+2 + 2e Pb

 Gaining of electrons is called reduction. We say, lead ions were reduced.

 Once lead ions become lead atoms, they collect on the electrode and drops off.

At the positive electrode:

 Bromine has a charge of -1.

 Bromine ions lose one electron and become bromine atoms.

Br- - e Br

 Losing of electrons is called oxidation. We say that bromide ions were oxidized.
 Br atoms pair up to form Br2 molecules

Br + Br Br 2

 The overall equation can be summarized as:

2Br - 2e Br 2

The electrolysis of molten lead bromide is considered as a redox reaction because both oxidation
and reduction takes place.

Remember OILRIG

Oxidation is loss

Reduction is gain
Electrolysis is used for many things, one of which is to extract metals from their ores which are
above carbon in the reactivity series.

The electrolysis of other molten compounds:

Electrolyte The decomposition What forms at the What forms at the

negative electrode positive electrode
Sodium Sodium chloride sodium + chlorine Sodium Chlorine
chloride 2NaCl 2Na Cl 2 Na+ + e Na Cl- - e Cl
(NaCl) Cl + Cl Cl2

Potassium Potassium iodide Potassium + Iodine Potassium Iodine

iodide 2KI 2K I2 K+ + e K I- - e I
(KI) I+I I2

Copper(ii) Copper(ii) bromide Copper + Bromine Copper Bromine

bromide CuBr2 Cu Br 2 Cu+2 + 2e Cu Br- - e Br
(CuBr2) Br + Br Br2

When a molten ionic compound is electrolyzed, a metal forms at the negative electrode and a
non-metal forms at the positive electrode.
The electrolysis of solutions

Ions in a compound can be made free to move by either melting or dissolving in water.

When an ionic compound is dissolved in water for electrolysis, the ions in water split too.

H2O H + + OH-

The H+ ions go to the negative electrode with the metal ions.

The OH- ions go to the positive electrode with the non-metal ions.

There is a competition at the two electrodes for the two sets of ions to become atoms.

Compound dissolved in Type of compound What forms at the What forms at the
water negative electrode? positive electrode?
Potassium Iodide Reactive metal Hydrogen gas Iodine
halide
Sodium chloride Reactive metal Hydrogen gas Chlorine
halide
Magnesium sulphate Reactive metal Hydrogen gas Oxygen
sulphate
Zinc chloride Less reactive metal Zinc Chlorine
halide
Lead nitrate Less reactive metal Lead Oxyegen
nitrate
Copper(ii) bromide Less reactive metal Copper Bromine
halide

When you electrolyze aqueous solutions of compounds:

 Hydrogen gas is released at the negative electrode in preference to a reactive metal.

 A halogen gas is released at the positive electrode if the compound is a halide. If not, you
get oxygen.