ELECTROLYSIS

I. Definition
A process in which electrical energy, from a direct current (dc) supply, breaks down electrolytes. The
free moving ions in electrolytes are attracted to the oppositely charged electrodes which connect to
the dc supply.
Electrolytes are ionic compounds that are:
 in the molten state (heated so they become liquids), or
 in solution, dissolved in water (aqueous)

II. Guidelines
 Electrodes = 1. Inert/inactive (Pt, Au, graphite)
2. Active
 Non-metals produced at anode (+): Oxidation
occurs
 Metals & hydrogen produced at cathode (-):
Reduction occurs
 Inert anode (+) = Chlorine, Bromine, Iodine
produced rather than Oxygen
 Inert cathode (-) = Hydrogen produced rather than
metals unless there’s unreactive metals like nickel
& copper
 Ionic compounds are able to be broken down in
electrolysis and be present in cathodes/anodes
because their electrons can get mobile, covalent compounds aren’t present because the
molecules are neutral and there are no charged particles to move (non-electrolyte).

III. Redox Reaction in Electrolysis

a. Molten lead (II) bromide (PbBr2) during electrolysis using graphite electrodes:
Since it’s molten, PbBr2 is in a liquid state, consisting ONLY Pb and Br.
C (-): Pb2+(l) + 2e-  Pb(l)
A (+): 2Br(l)  Br22+(g) + 2e-
Full equation: Pb2+ + 2Br  Pb + Br2

b. Molten aluminum oxide (Al2O3) during electrolysis (Hall Heroult) using graphite electrodes:
Bauxite (impure form of Al2O3) is reacted with NaOH to obtain pure Al2O3, removing impurities
like Fe3O4 to improve conductivity.

The purified Al2O3 is then dissolved in molten cyrolite (Na3AlF6) to reduce Al2O3’s working
temperature of the Hall-Heroult cell from 2017°C to 800°C-1000°C.
C (-): Al3+(l) + 3e-  Al(l) x4 = 4Al3+(l) + 12e-  4Al(l)
A (+): 2O (l)
2-
 O2(g) + 4e -
x3 = 6O (l)
2-
 3O2(g) + 12e-
Full equation: 4Al3+ + 6O2-  4Al +3O2 = 2Al2O3  4Al + 3O2
 Molten Al2O3 collects at the bottom of the cell and is
siphoned out. Nothing goes wrong when using
cryolite since they’re largely unaffected by the flow
of electricity. But using graphite anodes at
working temperatures make oxygen react
with the graphite anodes to produce
carbon dioxide. Said anode is burnt away
and has to be replaced on regular basis.

Anodizing, a process of coating oxide on

aluminum (Al2O3). The anode is an
aluminum object and the electrolyte is
dilute sulfuric acid. Oxygen is produced at the anode and combines with the aluminum,
forming a layer on it. It makes it thicker, colorful and decorative.

c. Dilute sulfuric acid (H2SO4(aq)) + H2O

H2SO4(aq)  2H+(aq) + SO42-(aq)
H2O  H+(aq) + OH-(aq)
OH will be oxidized in preference to oxyanions (SO42-, NO3-, SO32-, NO2-, etc.)
-

C (-): 4H+(aq) + 4e-  2H2(g)

A (+): 4OH (aq)
-
 2H2O(l) + O2(g) + 4e-

d. Sodium chloride solution (Chlor-Alkali Industry)

Saturated sodium chloride solution (brine) is the basis of a major industry, obtained by mining
(rock salts) or by evaporation of sea water, consisting chlorine, sodium, hydroxide, and hydrogen.
NaCl(aq)  Na+(aq) + Cl-(aq)
H2O(l)  H+(aq) + OH-(aq)
C (-): 2H+(aq) + 2e-  H2(g)
A (+): 2Cl (aq)
-
 Cl2(g) + 2e-

NaOH is produced as well but not in cathode/anode. It can be used to make:

 Soap  Inorganic/organic  Textile (e.g. rayon,

 Paper sodium salts wool, cotton)
 Aluminum extraction  Effluent treatment

H can be used for:

 Welding  Hydrochloric acid  Hydrogen peroxide

 Food industries  Ammonia  Rocket fuel

Cl can be used for:

 Hydrochloric acid  Disinfectants

 Bromine production  Extraction of titanium
 Water treatment  Chemicals (dyes &
 Plastic pesticides)
 Solvents

e. Hydrochloric acid during electrolysis:

HCl(aq)  H+(aq) + Cl-(aq)
 H2O(l)  H+(aq) + OH-(aq)
C (-): 2H+(aq) + 2e-  H2(g) can be tested by lighting a splint will make a pop sound when
in contact with H gas.
A (+): 2Cl-  Cl2 + 2e- can be tested by putting damp blue litmus paper which will
then turn white when in contact with Cl gas.

f. Copper (II) sulfate solution during electrolysis:

CuSO4(aq)  Cu2+(aq) + SO42-(aq)
H2O(l)  H+(aq) + OH-(aq)
C (-): Cu2+(aq) + 2e-  Cu(s)
A (+): 4OH-(aq)  2H2O(l) + O2(g) + 4e-
Copper is used for electrical wiring for it is a

good conductor of electricity, pure copper is

used in the manufacture of cooking utensils because of its high thermal conductivity.

g. Chromium plating
Electrolyte: Cr(NO3)3  Cr3+ + NO3-, NO3- is non-electrolyte
C (-): Cr3+(aq) + 3e-  Cr(s)
A (+): Cr(s)  Cr3+(aq) + 3e-

h. Silver plating
Electrolyte: AgNO3, Ag2SO4, NO3- & SO42- is non-electrolyte
C (-): Ag+(aq) + e-  Ag(s)
A (+): Ag(s)  Ag+(aq) + e-