ELECTROLYSIS OF

AN AQUEOUS
SOLUTION
In the electrolysis of aqueous
solutions only one ion is involved in
the selective discharge of ions at each
electrode during the electrolysis and
their ions are free to move.

Their ions are cation and anion.
Aqueous
Solution
Salt
Ionization
Water
Ionization
Cation Anion

NaCl(aq)

NaCl
Na
+
+ OH-

H
2
O
H
+
+ OH-

Na
+
, H
+


Cl-, OH-

CuSO
4
(aq)

CuSO
4

Cu
2+
+ SO
4
2-

H
2
O
H
+
+ OH-


Cu
2+
, H
+

SO
4
2-
, OH-

HNO
3
(aq)

HNO
3

H
+
+ NO
3
-

H
2
O
H
+
+ OH-

H
+
NO
3
-
, OH-
The positive ions are attracted to the negative electrode

The negative ions are attracted to the positive electrode
Na
+
Na
+
Na
+
OH-

OH-

OH-

NaCl Solution
Carbon
Electrode
The ion which is selected for discharge
at an electrode depends on a
number of factors, that is:

1. Position of the ions in the
electrochemical series

2. Nature of the electrode

3. Concentration of the ions in solution

Position of the ions in the
electrochemical series
The figure below shows an idealized drawing of a cell in which an
aqueous solution of sodium sulphate is electrolyzed
Na
2
SO
4
OH-
O
2
(g)

SO
4
2-
H
+

Na
+
Observation Conclusion + Chemical Equation
Anode(+):

Ion OH-

OH- ion much easier to discharge
than SO
4
2-
ion in the electrochemical
series.
The only product formed is oxygen
gas.

4OH
-
(aq)
H
2
O
(aq)
+ O
2(g)
+ 4e-


Cathode(-):

Ion H
+
H
+
ion much easier to discharge
than Na
+
ion, the only product
formed at the anode is hydrogen gas.

2H
+
(aq)
+2e- H
2(g)

Electrochemical Series
Li
+
Na
+
Mg
2+
Al
3+
Zn
2+
Fe
2+
Sn
2+
Pb
2+
H
+

Cu
2+

Hg
+

Ag
+
F-
SO
4
2
-
NO
3
-
Cl-
Br-
I-
OH-
The tendency
of cation to
discharge
increases
The tendency
of anion to
discharge
increases
Nature of the Electrode
Electrolysis of an aqueous solution of
Cuprum Sulphate: Carbon Electrode
Cuprum Sulphate
Solution
Carbon Electrode
Anode Cathode
Observation Conclusion + Chemical Equation
Anode(+):

Ion OH-

OH- ion much easier to discharge
than SO
4
2-
ion in the electrochemical
series.
The only product formed is oxygen
gas.

4OH
-
(aq)
H
2
O
(aq)
+ O
2(g)
4e-


Cathode(-):

Ion Cu
2+
Cu
2+
much easier to discharge than
H
+
ion, the only product formed at the
cathode is precipitate of brown colored.

Metal copper formed.

Cu
2+
(aq)
+ 2e- Cu
(s)

Electrolysis of an aqueous solution of
Cuprum Sulphate: Cuprum Electrode
Cuprum sulphate
Solution
Cuprum Electrode
cathode
Anode
Observation Conclusion + Chemical Equation
Anode(+):
Transfer of copper
metal from the anode
to the cathode during
electrolysis. The
copper sulphate is
ionized in aqueous
solution.



Each copper atom loses two
electrons to become copper ions,
which go into solution.

Cu
(p)
Cu
2+
(aq)
+ 2e-

Cathode(-):
The positively
charged copper ions
migrate to the cathode.
Where each gains two electrons to
become copper atoms that are
deposited on the cathode.

Cu
2+
(aq)
+ 2e- Cu
(p)


Concentration of the Ions in
Solution
KI dilute
O
2
(g)
Electrode Carbon Electrode Carbon
OH-
Electrolysis of an aqueous solution of Dilute
Potassium Iodide
K
+
I-
H
+

Observation Conclusion + Chemical Equation
Anode(+):

Ion OH-

OH- ion much easier to discharge
than I- ion.
The only product formed at the
anode is oxygen gas.

4OH
-
(aq)
H
2
O
(aq)
+ O
2(g)
4e-


Cathode(-):

Ion H
+
H
+
ion much easier to discharge than
K
+
ion.
The only product formed at the
anode is hydrogen gas.

2H
+
(aq)
+ 2e- H
2(g)

Electrolysis of an aqueous solution of
Concentrated Potassium Iodide
Electrode Carbon
Electrode Carbon
KI
I-
I
2
(g)
H
+

OH-
K
+
Observation Conclusion + Chemical Equation
Anode(+):

Ion I-

I- ion much easier to discharge than
OH- ion because concentration of iodide
ion is high.

Iodine gas formed.
2I-
(aq)
I
2(g)
+ 2e-



Cathode(-):

Ion H
+
H
+
ion much easier to discharge than
K
+
ion.
The only product formed at the anode
is hydrogen gas.

2H
+
(aq)
+2e- H
2(g)

Activity 1

Anode

Cathode

Electrolyte

Electrode

Attracted
Ion

Ionized
Ion

Product

Attracted
Ion

Ionized
Ion

Product

NaCl
(aq)

Dilute
Carbon Ions Cl-, OH- Ion OH- O
2
gas Ions Na
+
,
H
+

Ion H
+
H
2
gas
KCL
(aq)

Concentrated
Carbon Ions Cl-, OH- Ion Cl- Cl
2
gas Ions K
+
,
H
+

Ion H
+
H
2
gas
CuBr
2

(aq)

Dilute
Carbon Ions Br-, OH- Ion OH- O
2
gas Ions Cu
2+
,
H
+

Ion Cu
2+
Copper
metal
AgBr
2

(aq)

Concentrated
Carbon Ions Br-, OH- Ion Br- Br
2
gas Ion Ag
+
,
H
+

Ion Ag
+
Argentum
metal
NiCl
2

(aq)

Dilute
Nikel Ions Cl-, OH- Metal
nikel
erode
Ion Ni
2+
Ion Ni
2+
,
H
+

Ion H
+
H
2
gas