Electrolysis

Electrolysis is a process in which current is passed through the electrolyte (in solution or molten
state) to be decomposed.

An electrolyte is a solution or molten compound

which conducts electricity.

The anode is the electrode where oxidation

occurs. It is connected to the positive pole of the
electricity supply.

The cathode is the electrode where reduction

occurs. It is connected to the negative pole of
the electricity supply.

During electrolysis, positive ions (cations) travel to the negative cathode and negative ions
(anions), to the positive anode.

At the anode, anions give up electrons to become neutral atoms (oxidation). These electrons
travel round the circuit to the cathode where the cations take up the electrons to become
neutral (reduction).

e.g. Electrolysis o f molten sodium chloride

At anode: 2Cl(l) Cl2(g) + 2e (oxidation)

At cathode: Na+(l) + e Na(s) (reduction)

Only one element at a time can be deposited at each electrode.

Products of Electrolysis

Candidates should be able to predict the identity of the substance liberated during electrolysis from
the state of electrolyte (molten or aqueous), position in the redox series (electrodepotential) and
concentration.

Factors affecting selective discharge during electrolysis

1. Position in the Redox Series.

Cation with the most positive is discharged first.
Anion with the most negative Eo is discharged first

2. Relative concentration of ions.

Ions of higher concentration will be selectively discharged

3. Nature of electrodes

e.g. 1: Electrolysis o f dilute H2SO4, using inert (Pt) electrodes

Electrolyte: H2SO4 2H+ + SO42

At cathode: 4H+ + 4e 2H2 (reduction of H+ to H2)

At anode: 2H2O O2 + 4H+ + 4e (oxidation of H2O to O2)
 Net result: The electrolysis of water and [H 2SO4] increases.
[NB. If carbon electrodes are used, O2 liberated at the anode will oxidise the carbon
electrode to give CO and CO2.]

e.g. 2: Electrolysis o f aqueous CuSO4, using Cu electrodes

Electrolyte: CuSO4 Cu2+ + SO42

At cathode: Cu2+(aq) + 2e Cu(s) (reduction of Cu2+ to Cu)
At anode: Cu(s) Cu (aq) + 2e
2+ (oxidation of Cu to Cu2+)
Net result: A transfer of Cu from anode to cathode and [CuSO4] does not change.

Some common electrolytic

Electrolyte Electrode Anode Reaction Cathode Reaction Remarks

molten NaCl C 2Cl Cl2 + 2e 2Na+ + 2e 2Na
2H2O O2 + 4H+ + 4e
O2 liberated oxidises C
dil. aq. NaCl C (2C + O2 2CO) 4H+ + 4e 2H2
anode to CO and CO2.
(C + O2 CO2)
conc. aq. Cl2 selectively liberated
NaCl (or C 2Cl Cl2 + 2e 2H+ + 2e H2 instead of O2 due to high
brine) concentration of Cl ions.
Na selectively liberated
instead of H2 as Hg is
C anode
2Cl Cl2 + 2e 2Na+ + 2e 2Na used as electrode.
Hg cathode
Na/Hg (amalgam)
formed.
H2SO4(aq) slowly
H2SO4(aq) Pt 2H2O O2 + 4H+ + 4e 4H+ + 4e 2H2 become more
concentrated.
2H2O O2 + 4H+ + 4e
O2 liberated oxidises C
C (2C + O2 2CO) 4H+ + 4e 2H2
anode to CO and CO2.
(C + O2 CO2)
Ag anode 2H2O O2 + 4H+ + 4e O2 liberated oxidises Ag
4H+ + 4e 2H2
Pt cathode (4Ag + O2 2Ag2O) anode to Ag2O.
Solution slowly becomes
CuSO4(aq) Pt 2H2O O2 + 4H+ + 4e 2Cu2+ + 4e 2Cu
colourless dilute H2SO4.
Transfer of Cu from
anode to
Cu Cu Cu2+ + 2e Cu2+ + 2e Cu
cathode. [CuSO4(aq)]
remains unchanged.
molten PbBr2 C 2Br Br2 + 2e Pb2+ + 2e Pb
2O2O2 + 4e
O2 liberated oxidises C
molten PbO C (2C + O2 2CO) 2Pb2+ + 4e2Pb
anode to CO and CO2.
(C + O2 CO2)
Solution slowly becomes
Na2SO4(aq) Pt 2H2O O2 + 4H+ + 4e 4H+ + 4e 2H2
more concentrated.
Industrial Uses of Electrolysis

Candidates should be able to explain, in terms of electrode reactions, the industrial processes of:
(i) the electrolysis of brine, using a diaphragm cell.
(ii) the anodising of aluminium.
(iii) the electrolytic purification of copper.

Electrolysis of brine (concentrated aqueous NaCl) using a diaphragm cell

The diaphragm cell consists essentially

of a graphite or titanium anode and a
steel cathode separated by an
asbestos diaphragm.

Electrolysis of Brine using a Diaphragm Cell

At anode: 2Cl(aq) Cl2(g) + 2e (oxidation)

At cathode: 2H2O(l) + 2e 2OH(aq) + H2(g) (reduction)

Overall reaction: 2Cl(aq) + 2H2O(l) Cl2(g) + 2OH(aq) + H2(g)

Or 2NaCl + 2H2O Cl2 + H2 + 2NaOH

At the anode, Cl(aq) is selectively discharged because of its high concentration and chlorine is
liberated at the top of the cell.
At the cathode, H2 and NaOH are produced.

Hence, during the electrolysis of brine (aqueous NaCl) in a diaphragm cell, Cl2, H2 and NaOH
are produced in the ratio 1:1:2.

NB. The caustic cell liquor from the cathode compartment contains approximately equal
amounts of NaOH and NaCl. This solution is concentrated by evaporation (NaCl crystallises out)
to produce a solution containing about 50 % NaOH and 1%NaCl by mass.

Anodising of aluminium

Anodising of aluminium is the process of coating aluminium metal with aluminium oxide, Al2O3,
during electrolysis with the Al metal as the anode.
Anode (+): Al metal
Cathode (): graphite (or any inert electrode)
Electrolyte : dilute sulphuric acid (or chromic acid, H 2CrO4).

At the anode, oxidation occurs and O2 is liberated.

H2O(l) 2H+ + O2(g) + 2e
The liberated O2 then reacts with the Al anode to form Al2O3.
2Al(s) + O2(g) Al2O3(s)
 Advantages: Anodised aluminium resists corrosion and can be decorative as well since the
oxide layer is hydrated and can absorb dyes.

Examples of anodised aluminium objects include window frames and grilles, drinks cans and
saucepan lids (with dyes incorporated).

Electrolytic purification of copper

Anode (+): impure Cu

Cathode (): pure Cu
Electrolyte : aqueous CuSO4

At the anode, copper dissolves.

Cu(s) Cu2+(aq) + 2e (oxidation)

Impurities (e.g. Zn and Fe) with Eo values which are less

positive than that of Cu also dissolve as ions.

Impurities (e.g. Ag and Au) with values which are more

positive than that of Cu remain undissolved and drop to
the bottom of the vessel as anode sludge from which
they can be recovered as valuable metals.

At the cathode, copper ions from the solution are discharged.

Cu2+(aq) + 2e Cu(s) (reduction)

Hence, the pure Cu cathode grows in size. The concentration of the electrolyte (aqueous
CuSO4) remains unchanged.