Electrolysis

The process of decomposition of an electrolyte by the

passage of electricity is called electrolysis. In
electrolysis electrical energy is used to cause a
chemical reaction.
Electrolysis

For example,
Electrolysis of molten sodium chloride

NaCl ( ) Na+ ( ) Cl ( )

Na e
Na Reduction At cathode
1
Cl
Cl2 (g) e Oxidation At anode
2
Electrolysis of aqueous sodium chloride

NaCl (aq.) Na+ (aq.) + Cl (aq.)

H2O ( ) H (aq.) + OH (aq.)

H+ ions are discharged at cathode because discharge

potential of H+ ion is much lower than Na+ ion

1
H + e H2 (gas)
2
At anode, Cl is discharge as Cl2 (gas) because discharge
potential of Cl is much lower than that of OH ion.

1
Cl Cl2 g e
2
Electrolysis of aqueous copper sulphate
Electrolysis of aqueous copper sulphate solution using inert electrodes

CuSO4 (aq.) Cu2+ (aq.) + SO42 (aq.)

H2O ( ) H+ (aq.) + OH (aq.)

At cathode, Cu2+ ions are discharged in preference to H+ ions

because discharge potential of Cu2+ is much lower than H+ ions.

Cu2 aq. 2e Cu aq.

At anode, OH ions are discharged in preference to SO42 ions because

discharge potential of OH is much lower than SO42 ions.

4OH 2H2O ( ) O2 (g) 4e

Standard electrode potential

When the ions are at unit activity

and the temperature is 25C (298 K),
the potential difference is called the
standard electrode potential (E).
Electrochemical cell
Galvanic cell:-

Chemical energy electrical energy.

Daniel cell
Reactions involved
Oxidation at anode

Zn(s) Zn2(aq) 2e

Reduction at cathode

Cu2(aq) 2e Cu(s)

Cell reaction

Zn(s) Cu2(aq) Zn2(aq) Cu(s)

Electromotive force(EMF)

E0cell=E0cathode-E0anode
Electromotive force(EMF) of a cell

As per IUPAC convention if we

consider standard reduction potential
of both the electrodes then
Emf = ER.H.Electrode - EL.H.Electrode

Emf Ecathode Eanode

Salt Bridge

Salt bridge Agaragar mixed with

KCl, KNO3, NH4NO3) etc.
Eliminates liquid - liquid junction potential
Maintains the electrical neutrality of solutions.
Completes the circuit.