Electrolysis of Solutions

LEARNING OUTCOMES
6.24. Predict the electrode to which an ion will
drift.
6.25. Discuss the electrolysis of certain
substances.
-Inclusion of the following:
(i) concentration of the electrolyte;
(ii) type of electrode (active and inert)
(iii) position of ions in the electrochemical
series.
 Electrolysis of solutions

■ When solutions are electrolysed, gases are usually produced.

■ The gases produced can be collected in test tubes to be identified
later by simple tests.
■ The electrolysis of solutions
is more complicated than
electrolysis of molten
compounds, because the
products at the electrodes
can come from the
electrolyte as well as from
water.
 Selective discharge of ions

At the cathode:
■ Positive ions from the electrolyte are discharged if they are H+
ions or ions of less reactive metals such as Cu2+, Pb2+ or Ag+.
■ Positive ions of reactive metals such as Na+, K+ and Ca2+ are
not discharged in the presence of water. Instead, H+ ions from
water are discharged and H2 gas is produced.

At the anode:
■ Negative ions from the electrolyte are discharged if they
are halide ions such as I- , Br - , and Cl-.
■ SO42- and NO3- ions are not discharged. Instead, OH-
ions from water are discharged and O2 gas is produced.
 Selective discharge of ions
The table shows the electrode products from solutions of ions,
assuming the solutions are fairly concentrated.
Cation Product at Ease of Anion Product at
Cathode discharge Anode

K+ Difficult SO42- Oxygen from

Na+ NO32- water
Ca2+ Hydrogen from Chlorine
Mg2+ water Bromine
Cl-
Al3+ Iodine
Br-
Ni2+ Oxygen
I-
Pb2+ Lead (OH-)
(H+)
Cu2+
Ag+ Copper Easy
Silver
 Electrolysis of dilute H2SO4

■ Pure water will not conduct electricity, so some dilute sulphuric

acid is added to make it conduct electricity.
■ The electrolysis of dilute sulphuric acid is therefore essentially
the same as the electrolysis of water.
 Electrolysis of dilute H2SO4
■ Dilute sulphuric acid contains H+, SO42- and OH- ions.
H+ ions take in electrons to become H2 molecules; H+ ions are discharged:
At the cathode:
2H+(aq) + 2e- H2(g)
At the anode:
OH- ions are discharged in preference over SO42-. Oxygen gas is formed.
4OH-(aq) O2(g) + 2H2O(l) + 4e-
■ Overall reaction:
2H2O(l) 2H2(g) + O2(g)
At the cathode: 2 volumes of hydrogen are produced.
At the anode: 1 volume of oxygen is produced.
■ The electrolysis of dilute solutions is essentially the same as the electrolysis
 Electrolysis of dilute sodium chloride solution

■ The ions present in the solution are: Na+, Cl- (from sodium
chloride) and H+, OH- (from water).
At the cathode:
Both Na+ and H+ are attracted here, but due to their
relative positions in the reactivity series, H+ ions are preferentially
discharged:
2H+(aq)+ 2e- 🡪 H2(g)
At the anode:
Both Cl- and OH- are attracted here, but due to the lower
position of the hydroxide ions in the reactivity series, they are
preferentially discharged:
4OH-(aq) 🡪 O2(g) + 2H2O(l) + 4e-
■ Overall reaction:
2H2O(l) 🡪 2H2(g) + O2(g) [ Electrolysis of water ]
 Electrolysis of concentrated sodium chloride solution
(Brine)
■ The ions present in the solution are:
Na+, Cl- and H+, OH-
At the cathode:
Both Na+ and H+ are attracted here, but due to their
relative positions in the reactivity series, H+ ions
are preferentially discharged:
2H+(aq) + 2e- 🡪 H2(g)
At the anode:
Both Cl- and OH- are attracted here, but due to the high
concentration of the chloride ions, chloride ions are
preferentially discharged:
2Cl-(aq) 🡪 Cl2(g) + 2e-
■ Overall reaction:
Hydrogen gas is produced at the cathode and chlorine gas is
produced at the anode.
⮚ The Na+ and OH- ions left in the solution combine to form sodium
hydroxide, thus making the solution alkaline.
 Electrolysis of Sodium chloride

Product at Product at
Sodium chloride Ions present
Cathode Anode
Na+(aq), Cl-(aq) , hydrogen
Dilute solution oxygen gas
H+(aq), OH-(aq) gas

Concentrated Na+(aq), Cl-(aq), hydrogen

chlorine gas
solution (brine) H+(aq), OH-(aq) gas

sodium
Molten Na (l), Cl (l)
+ -
chlorine gas
metal
 Electrolysis of Solutions

Examples of electrolysis of different solutions using inert

electrodes, assuming the solutions are fairly concentrated

Product at Product at
Electrolyte Ions in Solution
Cathode Anode
Aq. hydrochloric H+(aq), Cl-(aq), hydrogen
chlorine gas
acid H+(aq), OH-(aq) gas
Aq. copper(II) Cu2+(aq), SO42-(aq), copper
oxygen gas
sulphate H+(aq), OH-(aq) metal
 Inert and reactive electrodes

■ Inert electrodes do not react with the product

produced or dissolved in the electrolyte.
■ Carbon and platinum are examples of inert
electrodes.
■ Reactive electrodes can react or dissolve in the
electrolyte.
■ Copper, silver and mercury are examples of
reactive electrodes.
 Quick check
1. Place in order the ease of discharge of the following cations (starting from
the easiest first): Ca2+, Na+, H+, Al3+, Mg2+, K+, Cu2+, Pb2+, Ag+.
2. Place in order the ease of discharge of the following anions (starting from
the easiest first): Br-, Cl-, NO3-, OH-, I-, SO42-,.
3. (a) State the products obtained when a solution of dilute sulphuric acid is
electrolysed using platinum electrodes.
(b) Write the ionic equations for the reactions taking place at the cathode
and anode.
4. (a) State the products obtained when a concentrated solution of sodium
chloride is electrolysed using inert electrodes.
(b) Write the ionic equations for the reactions taking place at the cathode
and anode.
5. (a) State the products obtained when a solution of sodium hydroxide is
electrolysed using platinum electrodes.
(b) Write the ionic equations for the reactions taking place at the cathode
and anode.
 Solution to Quick check

1. Ag+, Cu2+, H+, Pb2+, Al3+, Mg2+, Ca2+, Na+, K+

2. OH-, I-, Br-, Cl-, NO3-, SO42-
3. (a) At cathode: hydrogen; At anode: oxygen
(b) At cathode: 2H+(aq) + 2e- 🡪 H2(g)
At anode: 4OH-(aq) 🡪 2H2O(l) + O2(g)
4. (a) At cathode: hydrogen; At anode: chlorine
(b) At cathode: 2H+(aq) + 2e- 🡪 H2(g)
At anode: 2Cl-(aq) 🡪 Cl2
5. (a) At cathode: hydrogen; At anode: oxygen
(b) At cathode: 2H+(aq) + 2e- 🡪 H2(g)
-