4.2 Electrolysis

Electrolysis
1 Definitions
A cathode is a negative electrode that attracts cations
An anode is a positive electrode that attracts anions
An electrolyte is a liquid or an aqueous solution, which contains mobile ions and can conduct electricity,
with chemical decomposition at the electrodes. It can either be a molten liquid of ionic salt or an aqueous
solution containing ions.1
2 Electrolysis of aqueous solutions

In aqueous solutions, water molecules 2 can also undergo self-ionisation to form H +(aq) and OH-(aq) ions
through the following reaction:
H2O(l) ⇌ H+(aq) + OH-(aq)
The ions/species that are discharged at the electrodes are those that require the least energy. This varies with
each different aqueous electrolyte and is known as selective discharge. This is affected by 3 factors,
discussed below in further detail from 3.1 to 3.3.
2.1 What happens when H+ and OH- electrons are consumed at the electrode
H+(aq) ions are consumed at the negative electrode. Therefore, the pH increases, turning the litmus paper blue
near this electrode as only OH-(aq) ions are left behind.
OH-(aq) ions are consumed at the positive electrode. Therefore, the pH decreases, turning the litmus paper red
near this electrode as only H+(aq) ions are left behind.
1 Electrical conductivity of an aqueous solution increases with increasing concentration because there would be a higher
concentration of ions to carry charges.
2 The ‘electrolysis of water’ is often conducted using a pair of inert electrodes, such as platinum, immersed in an
aqueous solution or diluted. Pure (distilled) water/deionised is not used as there are not enough/no ions in the water to
carry much of an electric current.
3 Factors affecting the selective discharge of ions during electrolysis
3.1 Position of the ion in the electrochemical series
The cation which is lower in the electrochemical series is reduced preferentially at the cathode.
K+, Ca2+, Na+, Mg2+, Al3+, (H2O), Zn2+, Fe2+, Pb2+, H+, Cu2+, Ag+
The anion which is lower in the electrochemical series is oxidised preferentially at the anode.3
F-, SO42-, NO3-, Cl-, (H2O), Br-, I-, OH-
3.2 Concentrations of ions

Certain anions which are at a higher concentration may be discharged in preference to those at a lower
concentration, even though comparison of their position in the electrochemical series says otherwise.
An increase in the concentration of an anion will shift the equilibrium to the right and thus it would be
preferentially oxidised at the anode over OH-.
3.3 Nature of electrode used

If a metal electrode used is not inert (unreactive) — such as Platinum (Pt) or graphite — like those of a
Copper or Iron anode, it may undergo oxidation itself and the anions in the electrolyte may not be discharged
at the anode.
Platinum and graphite (carbon) electrodes are inert electrodes because they are chemically inert and do not
usually take part in the reactions at the electrodes.4
3.3.1 Electrolysis of CuSO4 (aq) using copper electrodes

Species present: Cu2+, SO42-, H+(aq), OH-(aq)
At the cathode: Cu2+ is still reduced in preference over H+(aq)
Cu2+(aq) + 2e- → Cu(s)
At the anode: Cu atoms on the electrodes are oxidised to Cu2+
Cu(s) → Cu2+(aq) + 2e-
Observations: Pink solid Cu(s) is deposited on the cathode and the copper anode dissolves.
3 F-, SO42-, and NO3- ions are never oxidised.

4 If oxygen is produced at a graphite electrode, CO and CO2 would be formed together with the O2 gas, especially at
high temperatures.
4 Practical Applications of Electrolysis
4.1 Anodising of aluminium
Its purpose is to increase the thickness of Al 2O3 protective layer on the surface of aluminium metal by
electrolysis.
Aluminium metal is a reactive metal and would oxidize easily. However. aluminium metal objects are usually
resistant to corrosion because when exposed to air, aluminium forms a layer of Al 3O3 on its surface. This
oxide layer is resistant to corrosion and it acts as a protective layer which seals off the aluminium beneath it
from further reaction. Anodising is a surface treatment to increase the thickness of the corrosion resistant
Al2O3 (s) layer on the surface of the aluminium metal by electrolysis.
During anodising, the aluminium object is made the anode.
4.1.1 Case study

Electrolyte: Dilute H2SO4 (aq)
Species present: H+(aq), SO42-(aq), OH-(aq)
Electrodes: Al anode, Pt cathode
Reactions at the anode: 4OH-(aq) → O2 (g) + 2H2O(l) +4e-
4Al(s) + 3O2 (g) → 2Al2O3 (s)
Reaction at the cathode: 2H+(aq) + 2e- → H2 (g)
4.1.2 Advantages and disadvantages

It is able to increase the corrosion resistance of the metal and provide a porous surface which can be dyed to
different colours. If a dye is added in the process, it can be adsorbed on the oxide layer.
It is used as materials for window frames, drink cans, and ipods.
4.2 Purification of Copper

It is to extract pure copper from impure copper. It is purified through electrolysis and is made the anode. A
piece of pure copper is made at the cathode.
4.2.1 Case study

Electrolyte: Dilute CuSO4 (aq)
Species present: Cu.2+(aq), SO42-(aq), H+(aq), OH-(aq)
Electrodes: Impure Cu anode, pure copper cathode
At the anode, Cu is oxidised to Cu2+, thus dissolving into the electrolyte.
Cu(s) → Cu2+(aq) + 2e-
Metal impurities higher in the electrochemical series than Cu (such as Zn and Fe) are also oxidised at the
anode and they dissolve into the electrolyte as ions.
Zn(s) → Zn2+(aq) + 2e-
Fe(s) → Fe2+(aq) + 2e-

Metal impurities like Ag and Au will not be oxidised as they have a lower tendency to be oxidised than Cu
and are collected below the anode as anode sludge.
At the cathode, the Cu2+ ions present in the electrolyte are reduced to Cu(s), depositing onto the cathode
Cu2+(aq) + 2e- → Cu(s)
Zinc (II) and Iron (II) ions that were produced at the anode will not be reduced at the cathode. These ions
remain in the electrolyte since they have a lower tendency to be reduced than Cu 2+.
Hence, the overall change is the transfer of pure copper from the anode to the cathode. During the
electrolysis, copper dissolves from the anode, whilst a thickening deposit of pure copper appears at the
cathode.
4.3 Electroplating
Electrolysis is used to electroplate objects. This is useful for coating a cheaper metal with a more expensive
one, such as copper, silver, chromium, or gold.
The cathode should be the object that is to be electroplated, whilst the anode should be the metal that you
want to coat the object with. The electrolyte should be a solution of the coating metal, such as its metal
nitrate or sulfate.
4.3.1 Electroplating with silver

The object to be plated, such as a metal spoon, is connected to the negative terminal (cathode) of the power
supply. A piece of silver is connected to the positive terminal (anode). The electrolyte is a silver nitrate
solution.
At the cathode: Ag+(aq) + e- → Ag(s)
4.3.2 Electroplating with copper

The object to be plated, such as a metal pan, is connected to the negative terminal (cathode) of the power
supply. A piece of copper is connected to the positive terminal (anode). The electrolyte is a copper sulfate
solution.
At the cathode: Cu2+(aq) + 2e- → Cu(s)

4.2 Electrolysis

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Electrolysis

2 Electrolysis of aqueous solutions

F-, SO42-, NO3-, Cl-, (H2O), Br-, I-, OH-

3.2 Concentrations of ions

3.3 Nature of electrode used

3.3.1 Electrolysis of CuSO4 (aq) using copper electrodes

3 F-, SO42-, and NO3- ions are never oxidised.

4.1.1 Case study

4Al(s) + 3O2 (g) → 2Al2O3 (s)

Reaction at the cathode: 2H+(aq) + 2e- → H2 (g)

4.1.2 Advantages and disadvantages

4.2 Purification of Copper

4.2.1 Case study

Fe(s) → Fe2+(aq) + 2e-

4.3.1 Electroplating with silver

4.3.2 Electroplating with copper

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