ELECTROLYSIS

PHYSICAL CHEMISTRY
Electrolytic Cell
1. The redox reaction in an electrolytic cell is non- spontaneous.
Electrical energy is required to induce the electrolysis reaction.
2. Oxidation occurs at the electrode termed the anode and reduction
occurs at the electrode called the cathode .

The anode of an electrolytic

cell is positive (cathode is
negative). The sodium ions
migrate toward the cathode,
where they are reduced to
sodium metal. Similarly,
chloride ions migrate to the
anode and are oxided to form
chlorine gas.
Electrochemical Cell
1. Spontaneous reactions occur in electrochemical cell.
2. The anode of a galvanic cell is negatively charged, since the
spontaneous oxidation at the anode is the source of the cell's
electrons or negative charge. The cathode of a galvanic cell is its
positive terminal.
Faraday’s Law
1. The quantity of electric current is measures in the unit of the
Coulomb (C).
2. One coulomb is the quantity of electric charge transferred by a
current of one ampere (A) in one second (s). Thus:
Q = It
3. The Faraday constant (F) is the charge one mole of electrons:
F = (6.02 x 1023 ) x (1.6x10-19)
= 96500 C mol-1
4. 1 Faraday (1F) is the quantity of electricity (96500C) that must
be supplied in order to produce one mole of electrons for
reactions in the cell.
Faraday’s First and Second Law
1. The mass of a substance deposited or liberated at any electrode is
directly proportional to quantity of electric current passed.
2. If W grams of a substance is deposited or liberated on passing Q
Coulomb of charge then :
WαQ

3. When the same amount of charge is made to pass through any

number of electrolytes, the mass of the substance liberated or
deposited at the electrodes are inversely proportional to their
charges on the ions
 Chemical equivalent = atomic mass / valence
 m1/m2 = E1/E2
Faraday’s First and Second Law Practice
1. An aqueous of copper (II) sulphate is electrolysed using a current
of 0.15 A for 5 hours. Calculate the mass of copper deposited.

Cu2+ + 2e  Cu
2mol e  1 mol Cu
Q = It
= 0.15 x 5 x 60x60
= 2700 C
No. of mole electron = 2700/96500
= 0.028 mol
No of mole Cu = ½ x 0.028
= 0.014
Mass of Cu = 0.014 x 63.5
= 0.889 g
2. An experiment is carried out to electrolyzed molten sodium
chloride.

a) Calculate the mass of sodium deposited when a current when a

current of 1.5 A is passed through the electrolyte for 3.0 hours.
[3.9 g]
b) Calculate the time taken to deposit of sodium, Na, if a current of
4A is used. [140 min]
c) A certain quantity of electricity used deposited 6.0 g of Na.
Calculate the mass of chlorine Cl2, evolved at the anode in the
same time. [9.3 g]
3. When a solution containing Mn+ ions was electrolyzed by a current
of 2. A flowing for 4.0 hours, 0.10 mole of the metal M was
deposited at the cathode. Calculate the charge on the metal
cation, n. [+3]

4. A metal M consists of 75% 63M and 25% 65M. When a solution

containing a salt of the metal was electrolyzed for 50 minutes b
passing a current of 1.5 A through it, 1.48 g of M was deposited.
What is the charge on M. [+2]

5. When a current of 2.0 A flows through an aqueous solution

containing silver ions for 31 minutes, 4.17 g of silver deposited.
Calculate the Avogadro constant.
Selective Discharge of Ions of Electrolysis

Electrolyte Electrodes Anode Cathode Other

changes
PbBr2 (liquid) C Br2 Pb(s) -
NaCl (s) C Cl2 Na(s) -
CuSO4(aqueous) Pt O2 Cu(s) H2SO4 formed
at anode
CuSO4(aqueous) Cu Cu(s) Cu(s) -
dissolves deposites
KI(aqueous) Pt I2 H2 KOH formed
at cathode
 Extraction of Aluminum
1. Bauxite is converted to
Fe2O3 (S), TiO2 iron (II) oxide and iron
SiO3 2- (aq) (III) oxide.
filter
Impure bauxite 2. When reacts with NaOH,
NaOH (Con.)
CO2 aluminum oxide and silicon
Al2O3 (s), Si2O2, Al(OH)4- (IV) oxide dissolves to
Al(OH)3(S)
Fe2O3, TiO2 SiO32- form aluminate (III) and
Heat silicate.
3. Iron (III) oxide and
900 C
titanium (III) oxide remain
Al3+ , O2- Al2O3(S) undissolved and id filtered
out.

Electrolysis Na3AlF6(l) 4. When CO2 is bubbled in,

aluminate (III)
decomposes to aluminium
hydroxide

Cathode Anode 5. Silicate remain unaffected. The Al(OH)3 is heated to form

Al(l) O2(g) Al2O3.
6. During electrolysis, cryolite is added to lower the melting
point of aluminum oxide.
7. Aluminium is produced at cathode while oxygen gas is
formed at anode.
Electrolysis of Aluminum oxide

1. The aluminium oxide is electrolysed in solution in molten cryolite, Na3AlF6.

2. Aluminium is released at the cathode. Aluminium ions are reduced by
gaining 3 electrons.
3. Oxygen is produced initially at the anode.
1. Oxygen liberated reacts with carbon electrode to produce carbon dioxide and
carbon monoxide gas.
C + O2  CO2
2C + O2  2CO
As a result, the carbon electrode is slowly burned away and must be replaced
from time to time.
2. Cryolite is used for 2 purposes:4
a) It reduces the melting point of aluminum oxide to 900oC.
b) It prevents the side reaction between aluminium and carbon to form
aluminium carbide Al4C3.

3. The electrolyte contains small amounts of AlF3. Hence, traces of hydrogen

fluoride are also formed during the extraction of aluminium.
2AlF3 + 3H2O  Al2O3 + 6HF

HF is very corrosive and causes air and water pollution.

Anodizing
1. Electrolysis is also used to deposit a thin layer of aluminium oxide onto the
surface of the aluminum object.
2. Anode: aluminium object
Cathode: Metal (copper or lead)
Electrolyte: sulphuric acid dilute.
3. At anode:
4OH-  2H2O + O2 + 4e
4Al + 3O2  2Al2O3

4. At cathode:
2H+ + 2e  H2

5. Unlike electroplating, in which the metal ion in the electrolyte is reduced and
the metal is coated onto the surface of the cathode, anodizing involves the
oxidation of a metal anode to produce a coat of metal oxide.
Manufacture of chlorine

Chlorine is produced at the titanium anode according to the equation:

The hydrogen is produced at the steel cathode:

1. Overall result at cathode is:
2H2O + 2Na+ + 2e  2NaOH + H2
2. A dilute solution of sodium hydroxide solution is also produced at the cathode
(see above for the explanation of what happens at the cathode). It is highly
contaminated with unchanged sodium chloride solution.
3. The sodium hydroxide solution leaving the cell is concentrated by evaporation.
During this process, most of the sodium chloride crystallises out as solid salt.
The salt can be separated, dissolved in water, and passed through the cell again.
4. Summary:
a) The overall reaction for the electrolysis of saturated
2NaCl + 2H2O  2NaOH + H2 + Cl2

b) Chlorine gas is separated from sodium hydroxide and hydrogen so that the side
reactions below cannot take place:
H2 + Cl2  2HCl
2NaOH + Cl2  NaOCl + NaCl + H2O
 Membrane Cell

The membrane is made from a polymer which only allows positive ions to
pass through it. That means that the only the sodium ions from the
sodium chloride solution can pass through the membrane - and not the
chloride ions.
Mercury Cathode Cell
1. In mercury cathode cell,
a) The flowing mercury acts as the cathode
b) The graphite blocks act as the anode
c) The electrolyte is the saturated aqueous NaCl

2. At Graphite Anode : 2Cl-  Cl2 + 2e

At Mercury Cathode: Na+ + e  Na

3. The Na produced then dissolves in Hg to form a sodium-mercury amalgam

Na(s) + Hg(l)  Na/Hg (l)
4. The amalgam the flows out of he cell into another tank of water where it
reacts to form H2 and NaOH (aq).
2Na/Hg + 2H2O  2Na+ + 2OH- + H2 + 2Hg

5. The escape into the environment contaminate fishes.

 Separation method Comments
Process
Mercury c Mercury cathode forms amalgam with Oldest method, still
ell sodium - hydrogen gas is not formed at this very much in use but
stage. Amalgam flows out of the cell where not chosen for new
water is used to release the sodium and plant
hydrogen
Diaphrag Steel and asbestos diaphragm separates More common in the
m cell anode and cathode compartment. Chlorine US than EU. Higher
forms at anode, sodium migrates through energy requirements
diaphragm to cathode compartment - rate
of liquid flow prevents hydroxyl ions
migrating to anode compartment
Membran Ion exchange membrane separates anode Most new plants opt
e cell and cathode. Chlorine forms at anode, only for this design. Least
sodium migrates through to cathode environmental impact,
compartment - membrane is not permeable lowest energy
to liquid/gas flow and only permits migration consumption
of cations (+)