Electrolysis of

Aqueous Solution
• Aqueous solution :
solution produced when ionic
compounds dissolved in water.
• It contains :
(a) cations & anions of the
compound
(b) H+ ions & OH− ions ( partial
dissociation of H2O molecules ).
H2O(l) H+(aq) + OH−(aq)
• Only 1 type of ion will be discharged
at the cathode & anode respectively.
• The selective discharge of ions
depends on 3 factors :
(a) position of ions in the
electrochemical series
(b) concentration of ions
(c) types of electrodes used
(a) Position of ions in electrochemical series
Cation Anion
K+ F−
Na+ SO42−
Mg2+ NO3−
Al3+ Cl−
Zn2+ Br−
Fe2+ I−
Sn2+ OH−
Pb2+
H+
Cu2+
Ag+ Ease of discharge increases
• Ions in the upper position of the
series are not selectively
discharged to form atoms or
molecules because they have
stronger tendency to exist as
ions than atoms or molecules.
 Current

+ e− e− −

e− e− H+
OH− Cl−
Na+
OH− e − e− H+
Na
+

H+ Cl−

Electrolysis of sodium chloride solution

• At cathode,
Half equation : 2H+(aq) + 2e− → H2(g)

• At anode,
Half equation : 4OH−(aq) → 2H2O(l) +
O2(g) + 4e−

Overall equation :
• 4H+(aq) + 4OH−(aq) → 2H2O(l) + O2(g)
+ 2H2(g)

O2 : H2 = 1 : 2
Electrolyte Observation
Cathode Anode Change in solution
Copper (II) Brown solid Gas bubbles Intensity of blue
sulphate deposited. released. colour of electrolyte
solution Colourless gas decreases.
relights glowing
splinter produced.

CuSO4 solution : Cu2+, SO42−, H+, OH−

Cu2+ , H+ → cathode ( terminal negative )
SO42−, OH− → anode ( terminal positive )
Cathode : Cu2+(aq) + 2e− → Cu(s)
Anode : 4OH−(aq) → 2H2O(l) + O2(g) + 4e−
(b) Concentration of ions in solution
If the concentration of a particular ion is
high, it may be discharged in preference to
the one below it in the electrochemical series.

Electrolysis of 2 mol dm−3 HCl

At anode, Cl− ions are selectively discharged
because of their higher concentration even
though Cl− ions is higher than OH− ions in
electrochemical series.

Electrolysis of 0.001 mol dm−3 HCl

At anode, OH− ions are selectively discharged
because of its lower position in electrochemical
series than Cl− ions.
* If the 2 ions are placed very far apart
in the electrochemical series, concentration
factor is unimportant.

Electrolysis of 2 mol dm−3 KNO3

At anode, OH− ions are selectively discharged
even though their concentrations are very low.
Electrolysis
concentrated NaCl ?
(c) Types of electrodes

Electrolysis of 0.1mol dm−3 copper (II) sulphate

solution
 The active anode ionises.

Electrode Observation
Cathode Anode Electrolyte
Carbon Brown solid Gas bubbles Intensity of
deposited. released. Gas blue colour of
relights glowing electrolyte
wooden splinter decreases.
produced.
Copper Brown solid Anode becomes Intensity of
deposited. thinner. blue colour of
Cathode electrolyte
becomes thicker. remains
unchanged.
• Electrode carbon (graphite),
Cathode : Cu2+(aq) + 2e− → Cu(s)
Anode : 4OH−(aq) → 2H2O(l) + O2(g)
+ 4e−

• Electrode copper,
Cathode : Cu2+(aq) + 2e− → Cu(s)
Anode : Cu(s) → Cu2+(aq) + 2e−
• Electrolysis of saturated NaCl using
graphite (anode) & mercury (cathode) :

saturated NaCl : Na+, Cl−, H+, OH−

Na+, H+ → cathode (terminal negative)
Cl−, OH− → anode (terminal positive)
Cathode : Na+(aq) + e− → Na(l)
Na(l) + Hg(l) → NaHg(l) (amalgam)
Anode : 2Cl−(aq) → Cl2 + 2e−
Only by being content
will life be rich with
happiness and peace.

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