8.

5
ELECTROLYSIS
 COMPARISON OF
ELECTROLYTIC CELLS AND
ELECTROCHEMICAL CELLS
BOTH ARE INVOLVED IN THE
INTERCONVERSION OF ELECTRICAL AND
CHEMICAL ENERGIES
BOTH TYPES OF CELLS INVOLVE AN
ELECTROLYTE AND TWO ELECTRODES
BOTH CELLS INVOLVE REDOX REACTIONS
 ELECTROLYTIC CELLS
A NON-SPONTANEOUS REACTION
WHICH CONVERTS ELECTRICAL
ENERGY TO CHEMICAL ENERGY
THE NEGATIVE ELECTRODE WHICH
ATTRACTS CATIONS IS CALLED
CATHODE.
THE POSITIVE ELECTRODE WHICH
ATTRACTS ANIONS IS CALLED
ANODE.
VOLTAIC CELLS
A SPONTANEOUS REACTION THAT
GENERATES ELECTRICAL ENERGY
FROM CHEMICAL ENERGY
THE ANODE IS NEGATIVELY
CHARGED AS ELECTRONS ARE
RELEASED IN OXIDATION
REACTION.
THE CATHODE IS POSITIVELY
CHARGED AS ELECTRONS ARE
ACCEPTED IN THE REDUCTION
REACTION.
 ELECTROLYSIS
THERE ARE TWO ASPECTS TO BE
STUDIED IN ELECTROLYSIS:
1) QUALITATIVE ASPECTS: THE
VARIOUS TYPES OF PRODUCTS FORMED
IN ELECTROLYSIS
2) QUANTITATIVE: THE QUANTITY OF
PRODUCTS FORMED IN AN
ELECTROLYSIS
The type of products formed in electrolysis can
be predicted based on the 3 factors that affect
the selective discharge of ions in an electrolyte
during electrolysis.
a) E° values or positions of the ions in the
electrochemical series
b) Concentration of ions in the electrolyte
c) Nature of electrodes used in the electrolytic
cells
 The quantity of the products formed in
electrolysis can be calculated based on
Faraday’s first and second law of electrolysis.
PREDICTING THE PRODUCTS FORMED
-When a molten salt is electrolysed, the cations
will be discharged at the cathode forming metal
atoms, while the anions will be discharged at the
anode.
E° VALUES OR POSITIONS OF THE IONS IN
THE ELECTROCHEMICAL SERIES
When inert electrodes are used on the
electrolysis, the main factor that determines
the selective discharge of ions in an aqueous
solution is the E° values or positions of the
ions in the electrochemical series
a) Reduction occurs at the cathode in which the
species with the most positive E° value is easiest to
be reduced.
-the tendency of metals to release electrons
decreases but the tendency of metal ions to receive
electrons increases when the E° value increases.
-species lower in the electrochemical series are
easier to be reduced
-metal ions discharge by receiving electrons at the
cathode:
a) Oxidation occurs at the anode in which the
species with the most negative E° value or smallest
E° value will be discharged.
-the tendency of anions to release electrons
decreases when the E° value increases
-species higher in the electrochemical series are
easier to be oxidised
-anions discharged by releasing electrons at the
anode:
 CONCENTRATION OF IONS IN THE
ELECTROLYTE
A species with higher concentration is
preferentially discharged.
a) in the electrolysis of a solution containing an
equimolar of Ag+ and Cu2+ions, Ag+ ions is
preferentially discharged over Cu2+ ions as the E°
of Ag+/Ag is more positive than that of Cu2+/Cu.
As the electrolysis proceeds over a long period of
time and the concentration of Ag+ ions decreases,
Cu2+ ions will be discharged at the cathode.
b) However, the concentration factor is
unimportant if the difference of E° values is very
large.
c) Generally, in the electrolysis of halide
solutions, concentrated halide solutions produces
halogens. Dilute halide solutions produces
oxygen gas at the anode.
 NATURE OF ELECTRODES
a) The minimum voltage required for electrolytes is
called the discharge potential. For most metal ions,
the discharge potential is equal to the E° values.
b) For some electrodes, the discharge potential is
greater than E° values. The difference between
discharge potential and E° is known as the over-
voltage or over-potential. This over-potential of
electrodes changes the type of ions selected to be
discharged especially in the formation of gaseous
products at the anode.
 FARADAY’S LAW AND
QUANTITATIVE ASPECTS
The amount of substance produced during electrolysis
depends on the quantity of charge that flows through
the electrolyte.
F= NA x e-
F= (6.02 x 10^23)(1.6 x 10^-19)
F= 9.65 x 10^4 C
Hence, 1F is the quantity of electricity that must be
supplied to an electrolytic cell so as to produce 1 mol of
electrons fo the reaction to occur.
Faraday’s first law: The amount (M) of a substance
produced at an electrode is directly proportional to the
quantity of electricity (Q) that passes through the
electrolyte.
Faraday’s second law: The amount of different
substances produced by the same amount of electricity
is inversely proportional to the charge of the ions.
-the number of Faradays required to discharge one
mole of an ion at the electrode is equal to the number
of moles of electrons involved in the reaction.
EG:
1 mol of Ag+ requires 1F to be discharged
(Ag+ + e- > Ag)
1 mol of Cu2+ requires 2F to be discharged
(Cu2+ + 2e- > Cu)
1 mol of Al3+ requires 3F to be discharged
(Al3+ + 3e- > Al)
Calculating the number of moles of product, x using
Faraday’s first and second law:

x= number of mol of product formed

Q= quantity of electricity in coulomb, Q= I x t
n= number of electrons involved in the half-reaction
F= Faraday = 9.65 x 10^4
EXAMPLE 1

A current of 250mA is passed through

an aqueous solution copper (ii) sulphate
solution, CuSO4, for 20 min 20s using
copper electrodes. What is the expected
change in mass of the electrodes?
EXAMPLE 1: SOLUTION
anode: Cu > Cu2+ + 2e-
cathode: Cu2+ + 2e- > Cu
thus, 1 mol of Cu2+ requires 2F to be discharged.
Q=It
=(250 x 10^-3)(20 x 60 + 20)
=305 C
using 1/x = n x F/Q
1/x = 2F/ 305
1/x = 2(9.65 x 10^4)/ 305
x= 1.58 x 10^-3 mol
EXAMPLE 1: SOLUTION

hence,
change in mass of copper = number of moles x
molar mass
=(1.58 x 10^-3)(63.5)
=0.10g
EXAMPLE 2

When an electric current passes through a hot dilute

potassium bromide solution, Br- ion is oxidised to
BrO3- ion. A current of 1.0 A is passed through
500cm^3 of KBr solution for 1930s. Calculate the
maximum concentration of bromate ion, BrO3- that is
produced.
EXAMPLE 2: SOLUTION

half reaction:
Br- + 3H2O > BrO3- + 6H+ + 6e-
Hence, the formation of 1 mol of BrO3- requires 6F to
discharged.
Q=It
=(1.0)(1930)
=1930 C
EXAMPLE 2: SOLUTION

1/x = n x F/ Q
x = (6)(9.63 x 10^4)/ 1930
= 3.33 x 10^-3
(3.33 x 10^-3)(1000/500) = 0.0067 mol dm^-3
THANK YOU