Electrolysis

For a liquid electrolyte to be able to conduct electricity, it must contain electrically charged particles
called ions. The ions must be free to move, which is why electrolysis can’t take place in solids.

When a positive ion reaches the cathode, it accepts enough electrons to make it neutral:
Na+ + e– Na(l); Al3+ + 3e– Al(l) REDUCTIONS
At the anode, negative ions give up their extra electrons. Once neutral, they react to form the most
stable molecule:
e.g. Br– Br + e– then 2Br Br2(l)
overall: 2Br– Br2(l) + 2e– OXIDATION

Metals and hydrogen form positive ions, and are set free at the cathode.
Non-metals ( except hydrogen ) form negative ions and are set free at the anode.

Rules of Electrolysis
Molten salts
Electrolysis of molten salts is straightforward, since there is only one type of each ion present, and
these are discharged.
e.g. molten sodium chloride:
cathode: Na+ + e– Na(l) Note that 2Na are – –
anode: 2Cl Cl2(g) + 2e produced for each Cl2

Aqueous solutions
Aqueous solutions contain H+ and OH– ions from the water in addition to the ions from the solute
dissolved in water.
For example, an aqueous solution of sodium chloride contains Na+, Cl–, H+ and OH– ions. There are
rules which help to predict what will happen at the electrodes.

Rules for aqueous solutions

At the cathode:
• If the solute contains the ions of a metal high in the reactivity series (e.g. Na, Mg) or
hydrogen ions from an acid, then hydrogen will be liberated.
• If the solute contains the ions of a metal low in the reactivity series (e.g. Cu, Pb ) then the
metal will be liberated.
• In a choice between two ions, the one lower in the reactivity series will normally be
discharged (e.g. from H+, Cu2+ and Ag+, Ag will be formed).

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At the anode:
• If the solute is a concentrated solution of a chloride, then chlorine will be liberated. This
also applies to bromides (giving bromine) and iodides (giving iodine), though for these the
solution need not be concentrated.
• If the solute is a dilute solution of a chloride, or does not contain a chloride (e.g. it is a
sulphate, nitrate or hydroxide), then oxygen will be liberated from OH–
4OH – 2H2O(l) + O2(g) + 4e–

Examples

Dilute aqueous sulphuric acid - Gives hydrogen and oxygen gases in a 2:1 ratio by volume.
The solution becomes more concentrated as (in effect) water is
removed. Cathode: only H+(aq) present 2H+(aq) + 2e– H2(g)
Anode: OH and SO4 present. Easier to discharge hydroxide:
– 2–

4OH – 2H2O(l) + O2(g) + 4e–

Aqueous copper(II) sulphate - Cu is deposited at the cathode, and O2 is given off at the anode.
Cathode: Cu2+ and H+(aq) present. Cu2+ is discharged, since Cu is less reactive than H.
Cu2+(aq) + 2e– Cu(s)
Anode: OH and SO4 present. Easier to discharge hydroxide:
– 2–

4OH – 2H2O(l) + O2(g) + 4e–

Electrolysis of Brine – Sodium Chloride Solution

Brine is an aqueous solution of sodium chloride. It therefore contains Na + and Cl– ions from the
sodium chloride and H+ and OH– ions from the water.

At the cathode: Na+ and H+(aq) present. H+(aq) is discharged, since H is below Na in reactivity.
2H+(aq) + 2e– H2(g)
At the anode: OH– and Cl– present. Cl– is discharged, since it is in high concentration.
2Cl-(aq) Cl2(g) + 2e-
Note – We can test for chlorine produced using its ability to bleach indicator paper.

Therefore the electrolysis of brine gives hydrogen and chlorine gases, leaving sodium hydroxide
behind (this is how NaOH and Cl2 are made in the chloralkali industry).

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 Membrane cells

The cathode is shielded by an ion-exchange membrane. The membrane only allows sodium ions (not
Cl– or OH– ) to pass through. There is therefore no contact between the chlorine gas and the sodium
hydroxide. If they did react they would form bleach (NaClO).

Uses of the products

• Sodium hydroxide, NaOH is used as an oven cleaner, to make soap, to make bleach, and to
purify aluminium oxide in aluminium extraction.
• Chlorine as a bleach (and to make household bleach, a solution of sodium chlorate(I),
NaClO), to purify drinking water (by killing bacteria), to purify swimming pools (also by killing
bacteria).
• Hydrogen is used as a fuel and to hydrogenate oils in the manufacture of margarine.

Calculations involving electrolysis

The amount of a substance produced in electrolysis depends on the quantity of electricity passed,
and this is measured by the charge passed.

The total charge which passes during electrolysis can be worked out used the equation:
Charge (Coulombs) = current (Ampères) × time (seconds)

The charge on one mole of electrons is called the Faraday. It has a value of about 96000 C/mol.

The amount of a product produced depends on the charge on the ions involved.
Equation r.a.m. 1 mole Charge needed
(C)
Na+ + e– Na(l); Na=23 23g Na 96 000
Cu (aq) + 2e Cu(s)
2+ –
Cu=64 64g Cu 192 000
Al3+ + 3e– Al(l) Al=27 27g Al 288 000
2Cl– Cl2(g) + 2e– Cl=35.5 71g Cl2 192 000
4OH –
2H2O(l) + O2(g) + 4e –
O=16 32g O2 384 000

To find the mass of metal deposited.

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e.g. What mass of aluminium will be deposited if a current of 1.5 A is passed through aluminium
oxide (dissolved in molten cryolite) for 40 minutes?
[Data: Al = 27; 1 Faraday = 96000 C mol–1]

1. Find the total charge passed

Charge passed = 1.5 A × 40 × 60 s = 3600 C

2. Convert this to moles of electrons (divide by the Faraday) number of moles of electrons

= = 0.0375 mol

3. Write out ion-electron equation and deduce number of moles of substance per mole of
electrons
Equation is: Al3+ + 3e– Al So 1 mol of electrons deposits ⅓ mol of Al atoms

4. Convert moles of electrons passed into mass of product

So 0.0375 mol of electrons deposit ⅓ × 0.0375 = 0.0125 mol Al
So mass of Al produced = moles x molar mass = 0.0125 × 27 = 0.338 g

Note – If you are told the number of faradays involved you know the moles of electrons so you can
start at step 3.

e.g. What mass of magnesium will be deposited if 5 faradays pass through molten magnesium
chloride?

5 faradays = 5 moles of electrons

Starting at step 3 we write out ion-electron equation and deduce number of moles of substance
formed from 5 moles of electrons.

Equation is: Mg2+ + 2e– Mg So 2 mol of electrons deposits 1 mol of Mg atoms 5

moles of electrons deposits 5/2 moles of Mg atoms = 2.5 moles = 2.5 x 24 = 60 g.

Industrial Uses of Electrolysis

Electrolysis is used for;

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 • The extraction of reactive metals (those more reactive than zinc).

• The purification of metals, especially copper.

• The chloro-alkali industry. Electrolysis of brine to obtain NaOH, Cl2 and H2.

• The production of hydrogen.

Hydrogen is potentially a non-polluting fuel. At present it is expensive to make
hydrogen by electrolysis. However, if we can develop solar powered cells further, we
may be able to use the energy from the sun to give us electricity. This electricity cannot
be stored directly, but could be used to electrolyse dilute sulphuric acid. The hydrogen
and oxygen obtained could be stored, and then reacted to drive engines, or generators,
or used in fuel cells to give electrical energy again

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