ELECTROLYSI

S
CHAPTER 11
 ELECTROLYSIS
The chemical change that takes place when
an electric current passes through a molten or
aqueous electrolyte.

ELECTROLYTE
A compound which when molten or dissolved
in aqueous solution conducts an electric
current and is decomposed in the process.
 ELECTRODE
A metal or graphite rod by which the
current enters or leaves an electrolyte.
ANODE ( +)
The positive electrode from which electrons
leave the electrolyte.

CATHODE (-)
The negative electrode from which electrons
enter the electrolyte.
 ANION
A negatively charged ion which is
attracted to the positively charged
electrode, the anode.
CATION
A positively charged ion that is
attracted to the negatively charged
electrode, the cathode.
Electrolysis of molten lead (II)
bromide
Electrolyte: PbBr2 (l)
Ions present: Pb 2+ , Br -

Using graphite electrodes:

At the cathode: Pb 2+ + 2e Pb

At the anode: 2Br - Br2 + 2e

Electrolysis of a binary electrolyte .

Step 1.
Break the ionic compound into its ions. X m+ and Y n -
X m+ is call the Cation

Y m- is call the Anion.

Step 2

When the switch is on , the

Cation will migrate to Cathode and accept M electrons from the battery.
(Reduction occurs)
Anion will migrate to Anode to donate N electrons (oxidation occurs)

Eg : Electrolysis of molten NaCl

Cathode: Na++ e Na or 2Na++ e 2Na
Anode: Cl-  Cl+ e
Or 2Cl-  2Cl+ 2e
Hence overall 2Na++ 2Cl-  2Na + Cl2
Selective discharge
of ions
❐ Nature of electrode.

❐ Concentration - increase of concentration

of an ion tends to promote its discharge.

❐ Position of metal or radical in the ECS - if

all other factors remain constant, all ions
will be discharged in preference to those
above it.
Electrolysis of dilute sulphuric acid
Electrolyte: H2SO4 (aq), equivalent to acidified water

Ions present: H + , SO4 2- from acid

H + , OH - from water
Using platinum electrodes:
At the cathode: H + ions migrate to it.
2H + + 2e H2
At the anode: SO4 2- and OH - ions migrate to it.

OH - ions preferentially discharged because of its lower

position in the ECS.
4 OH - (aq) 2H2O (l) + O2 (g) + 4e
Electrolysis of dilute sulphuric acid

Note
 concentration of acid
increases
 products are equivalent to
those obtained by
electrolysis of water
 volume of oxygen gas to
hydrogen gas obtained is 1 : 2
Electrolysis of concentrated hydrochloric acid
Electrolyte: HCl (aq)
Ions present: H + , Cl - from HCl
H + , OH - from H2O
Using graphite electrodes:
At the cathode: H + ions migrate to it.
2H + + 2e H2
At the anode: Cl - and OH - ions migrate to it.

Cl - ions preferentially discharged due to higher concentration.

2Cl - - 2e Cl2
Electrolysis of dilute sodium chloride
solution

Electrolyte: NaCl (aq)

Ions present: Na + , Cl - from NaCl
H + , OH - from H2O

Using graphite electrodes:

At the cathode: Na + and H + ions migrate to it.

H+ ions preferentially discharged
due to its lower position in the ECS.
2H + + 2e H2
At the graphite anode: Cl - and OH - ions
migrate to it.

OH - preferentially discharged due to its lower

position in ECS.

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

 Electrolysis of concentrated
sodium chloride solution

Electrolyte: NaCl (aq)

Ions present: Na + , Cl - from NaCl
H + , OH - from H2O
Using graphite electrodes:
At the cathode: Na + and H + ions migrate to it.
H+ ions preferentially discharged
due to its lower position in the ECS.
2H + + 2e H2
If mercury cathode is used:
• Na + and H +
ions migrate
to it.

• Na + is preferentially
discharged.
The sodium
+ forms a dilute amalgam with
Na + e Na
mercury.
The amalgam is led into iron tanks containing
water where it decomposes to produce sodium
hydroxide, hydrogen and mercury.

2Na/Hg (l) + 2H2O(l) 2NaOH(aq) + H2(g) + 2Hg(l)

In the industrial process
unreacted sodium chloride crystallised out leaving
behind a concentrated solution of sodium
hydroxide.

The concentrated sodium hydroxide solution is

then evaporated to dryness to yield sodium
hydroxide pellets.

These pellets are used to make soap by reaction

with vegetable oil.
At the graphite anode: Cl - and OH - ions
migrate to it.
Cl - ions preferentially discharged due to higher
concentration.

2Cl - - 2e Cl2

• Chlorine is observed as a
greenish-yellow gas around the
anode.
• Chlorine is used in the
manufacture of bleach, sodium
chlorate (I), by reaction with
lectrolysis of copper (II) sulphate solutio
Electrolyte: dilute CuSO4 (aq)

Ions present: Cu 2+ , SO4 2- from CuSO4

H+ , OH - from water
Using graphite electrodes:
At the cathode: H + and Cu 2+ ions migrate to it.
Cu 2+ preferentially discharged due to lower position in ECS.

Cu 2+ (aq) + 2e Cu (s)

Copper is deposited on the electrode as brown copper metal.

At the graphite anode:

• SO4 2 - and OH - ions migrate to it.

• OH - preferentially discharged due to its lower position in ECS.

• OH - (aq) OH (g) + e
• OH (g) + OH (g) H2O (l) + O (g)
• O (g) + O (g) O2 (g)

• 4OH - (aq) 2H2O (l) + O2 (g) + 4e

Blue colour of solution slowly fades due to
removal of Cu 2+ ions.
As H + and SO4 2- ions remain in the
solution, the resulting solution is sulphuric
ectrolysis of copper (II) sulphate solution
Ions present: Cu 2+ , SO4 2- from CuSO4
H+ , OH - from water
Using copper electrodes:
At the cathode: H + and Cu 2+ ions migrate to it.

Cu 2+ preferentially discharged due to lower position in ECS.

Cu 2+ (aq) + 2e Cu (s)

Copper is deposited on the electrode as brown copper metal.

At the copper anode:

• SO4 2 - and OH - ions migrate to it.

• since copper is able to lose electrons more easily than SO4 2 -

and OH - ions, copper anode “dissolves” to form Cu 2+ ions.

• Cu (s) Cu 2+ (aq) + 2e

For every Cu 2+ ion discharged at cathode,

one Cu 2+ ion is formed at the anode.
There is no change in concentration of Cu 2+
in solution; solution remains blue throughout.
Mass of cathode increases, mass of anode
decreases.