Product of electrolysis

Product of electrolysis depends on :

(i) Nature of the material that is to be electrolysed

(ii) Oxidising and reducing species and their E° value
(iii) Type of electrode used (inert/reactive)

Inert electrode: Do not participate in the reaction and act as a source of electron.

Reactive electrode : It participate in the electrode reaction

Example 1: Electrolysis of Molten Sodium Chloride

2NaCl ⇌ 2Na+ +2Cl−
At cathode: 2Na+ + 2e−→2Na E∘=−2.71V
− −
At anode: 2Cl →Cl2+2e E∘=1.36V
Overall reaction:
2Na++2Cl−− electrolysis 2Na + Cl2

Electrolysis of an aqueous solution of Sodium Chloride:

NaCl(aq) →Na+(aq) + Cl−(aq)

H2O(l) ⇌H+(aq) + OH−(aq)
At cathode:
Na+ +e− → Na , E∘=−2.71V
2H2O + 2e−→H2 + 2OH− , E∘=−0.83V

Higher the value of E°is preferred thus H2 gas is deposited at cathode

Thus, the reaction taking place at cathode 2H2O + 2e−→H2 + 2OH−
At Anode:
2H2O → O2+ 4H++ 4e− , E∘= 1.23V
2Cl− → Cl2 +2e− E∘= 1.36V
Due to over voltage or over potential of oxygen oxidation of water will not take place hence chlorine gas is
liberated at anode. Thus the reaction at anode
2Cl− → Cl2 +2e−
Over Potential : During electrochemical process , some reactions are kinetically slow at low voltage and
do not seems to takes place thus an extra potential is applied to make such reaction more difficult to occur.
Electrolysis of aqueous copper sulphate solution

Copper sulphate and water ionise as:

CuSO4 (aq) ⇔ Cu2+(aq) + SO42¯

H2O (l) ⇔ H+(aq) + OH¯ (aq)

During electrolysis, copper is deposited at the cathode while oxygen is liberated at the anode.

At anode (oxidation)

2 H2O (l) ——-> 4 H+ + O2 +4 e¯

At cathode (reduction)

Cu2+ (aq) +2e‾ ———> Cu(s) x 2

The overall reaction is :

2Cu2+ (aq) + 2 H2O (l) ———> Cu(s) + 4 H+ + O2 (g)

Electrolysis Of Sulphuric acid

During the electrolysis of sulphuric acid, hydrogen is liberated at cathode:

At cathode

H+ + e¯ ——-> ½ H2

The following two reactions occur at anode:

2 H2O (l) ———–> O2 (g) + 4 e¯ Eø = 1.23 V

2 SO42¯ (aq) ——> S2O82¯ (aq) + 2 e¯ Eø = 1.96 V