CHAPTER IV

ELECTROLYSIS Dr Tun Aung

Conductor Lecturer
A substance which conducts or allows the passage of electricity is called a conductor.

Non-Conductor or Insulator
A solid substance which does not conduct electricity, is known as a non-conductor or
insulator.

Electrolyte
Those substances, other than metals, which in the molten state or as a solution in
water, allow the passage of electricity are called electrolytes.

Non-Electrolyte
A substance in a solution that does not conduct electric current is called a non-
electrolyte.

Electrolysis
The decomposition of a compound, in solution or in the molten state, brought about
by the passage of an electric current through it, is known as electrolysis.

Ionic Theory
1. Electrolytes contain electrically charged particles called ions.
2. Electrolytes can conduct electricity due to the movement of these ions.
3. Non-electrolytes do not contain ions and so they cannot conduct electricity.

Electrolysis of molten sodium chloride using platinum (or) graphite electrodes

NaCl → Na+ + Cl-

move to cathode move to anode
Molten sodium chloride contains Na+ and Cl ions. Na+ ions are discharged and
sodium metal is deposited at the cathode.
Cathode reaction → Na+ + e- → Na
Cl- ions are discharged and Cl2 gas is liberated at the anode
 2

Anode reaction → 2Cl- → Cl2 + 2e-

(b) Electrolysis of molten lead (II) bromide using platinum electrode

PbBr2 → Pb+ + 2
move to cathode move to anode
Molten lead (II) bromide contains Pb2+ and Br ions. Pb2+ ions are discharged
and lead metal is deposited at the cathode.
Cathode reaction → Pb+ + 2e- → Pb
ions are discharged and Br2 gas is liberated at the anode
Anode reaction → 2 → Br2 + 2e-

(c) Electrolysis of aqueous copper (II) sulphate solution using

platinum electrodes

CuSO4 → Cu2+ +
H2O → H+
+ OH-
move to cathode move to anode
Aqueous copper (II) sulphate solution contains Cu2+, SO42-, H+ and OH- ions.
According to the electrochemical series, Cu2+ ions are discharged and copper
metal is deposited at the cathode.
Cathode reaction → Cu2+ + 2e- → Cu
 3

According to the electrochemical series, OH- ions are discharged and O2 gas is
liberated at the anode.
Anode reaction → 4OH- → 2H2O + O2 + 4e-

(d) Electrolysis of dilute sodium hydroxide solution using platinum electrodes

NaOH → Na+ + OH-

H2O → H+ + OH-
move to cathode move to anode
Dilute sodium hydroxide solution contains Na+, H+, OH- and H+ ions. H+ ions are
discharged and H2 gas is librated at the cathode.
Cathode reaction → 2H+ + 2e- H2
According to the electrochemical series.
OH- ions are discharged and O2 gas is librated at the anode.
Anode reaction → 4OH 2H2O + O2 + 4e-
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(e) Electrolysis of aqueous dilute sulphuric acid solution

using platinum electrode

solution

H2SO4 → 2H+ + -

H2O → H+ + OH-
move to cathode move to anode
Dilute sulphuric acid solution contains H+, OH- and ions. H+ ions are
discharged and H2 gas is librated at the cathode.
Cathode reaction → 2H+ + 2e- H2
According to the electrochemical series, OH- ions are discharged and O2 gas is
librated at the anode.
Anode reaction → 4OH 2H2O + O2 + 4e-

(f) Electrolysis of saturated aqueous sodium chloride solution (brine)

using platinum electrodes

NaCl → Na+ + Cl-

H2O → H+ + OH-
move to cathode move to anode
 5

Saturated aqueous sodium chloride solution (brine) contains Na+, Cl-, H+ and OH-
ions.
According to the electrochemical series, H+ ions are discharged and H2 gas is
librated at the cathode.
Cathode reaction → 2H+ + 2e- H2
Although Cl ions are above in the electrochemical series, Cl - ions are discharged
-

due to its high concentration and Cl2 gas is librated at the anode.
Anode reaction → 2Cl + 2e- → Cl2

(g) Electrolysis dilute aqueous copper (II) sulphate solution using

platinum electrodes

CuSO4 → Cu2+ +
H2O → H+ + OH-
move to cathode move to anode
Dilute aqueous copper (II) sulphate solution contains Cu2+, , H+ and OH-
ions.
According to the electrochemical series, Cu2+ ions are discharged and copper
metal is deposited at the cathode.
Cathode reaction → Cu2+ + 2e- Cu
Mass and size of copper cathode is gradually increased.
Both and OH- ions are not discharged. Instead of these ions copper anode is
dissolved into the solution.
Anode reaction → 2Cl → Cl2 + 2e-
Mass and size of copper cathode is gradually decreased. This process is used for
purification of crude copper.

Selective discharge of ions

i. Position of the metal or group in the electrochemical series
ii. Concentration
iii. Nature of the electrodes
 increasingly easier to discharge
6

increasingly easier
to discharge
i. Electrochemical series
Cations Anions
K+ SO
Ca2+ NO
Na+ Cl to anode
Mg2+ Br
Zn2+ I
Fe2+ to cathode OH
Pb2+
H+
Cu2+
Ag+

If all factors are equal, the ions in the lower position of the electrochemical series
is easier to discharge in preference to these about it.

(ii) Concentration
The higher the concentration of the ion the greater will be the readiness to
discharge.

(iii) Nature of electrodes

The nature of the electrodes is the deciding factor in some cases.

Chemical cell

A chemical cell produces electricity from a chemical reaction. Zinc is more

electropositive than copper. It loses electrons and these electrons move to the copper
plate along the wire. At the copper plate H+ ions are discharged.
Anode reaction → Zn →Zn2+ + 2e-
Cathode reaction → 2H+ + 2e- →H2

Electrochemical series
The series obtained by placing the metals in order of decreasing negative
potential is known as the electrochemical series.
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Faraday's Laws of Electrolysis

Faraday's first law of electrolysis
The mass of a given element liberated during electrolysis is directly proportional to:
(i) the magnitude of the steady current used and
(ii) the time for which the current passes
Q = It
where Q = quantity of electricity
I = current
T = time

Faraday's second law of electrolysis

When the same quantity of electricity is passed through solutions of different
electrolytes, the relative number of moles of the elements deposited are inversely
proportional to the charges on the ions of each of the elements, respectively.

One Faraday (1F)

The quantity of electricity required to liberate one mole of a univalent element is
96500 coulombs or one Faraday.
One mole of e = 1F = 96500 C
Electroplating
The electrical precipitation of one metal on another is called electroplating.
Note: cathode = the negative electrode electrolysis
cation = an ion with a positive charge
anode = the positive electrode in electrolysis
anion = an ion with negative charge

Mass &Smcdkif;EdkifaomowåKrsm;
1. Ag+ + e- → Ag
2. Cu 2+
+ 2e →
-
Cu
3. Ni 2+
+ 2e →
-
Ni
4. Pb 2+
+ 2e →
-
Pb
5. Zn 2+
+ 2e →
-
Zn
6. Al 3+
+ 3e →
-
Al
7. Au 3+
+ 3e →
-
Au
8. Cr 3+
+ 3e →
-
Cr
9. Pt4+
+ 4e →
-
Pt
 8

Volume ar;Edkifaom "mwfaiGUrsm;

1. 2H+ + 2e- → H2
2. 2Cl -
- 2e →
-
Cl2
3. 2Br 2-
- 2e →
-
Br2
4. 4OH -
- 4e →
-
2H2O + O2
Note : 1. Mass (or) Volume ar;cJhvQif By Eqn: ESifhwGuf&onf/
2. R.A.M ar;cJhvQif By Problem ESifhwGuf&onf/

avhvmxm;oifhaom ykpämrsm;
1. What mass of (a) copper, (b) silver, (c) aluminium and what volume at STP of (d)
oxygen and (e) chlorine will be liberated during electrolysis by a charge of one
Faraday? (Cu = 63, Al = 27, O = 16, Cl = 35.5)
(a) Cu2+ + 2e-  Cu
2 mol 1 mol
2F 63 g of copper
By Eqn:, 2F pass --------------- 63 g of Cu deposited
1F -----------------------------?

= 63 g  = 31.5 g ←

(b) Ag+ + e-  Ag
1 mol 1 mol
1F 108 g
(c) Al + 3e
3+ -
 Al
3 mol 1 mol
3F 27 g of copper
By Eqn:, 3F pass --------------- 27 g of Al deposited
1F -----------------------------?

= 27 g  =9g ←

(d) 4OH 2H2O + O2 + 4e-

1mol 4mol
22.4 dm at STP
3
4F
By Eqn:, 4F pass --------------- 22.4 dm3 of O2 at STP liberated
1F pass --------------------------------?

= 22.4 dm3  = 5.6 dm3 of O2 at STP ←

(e) 2Cl Cl2 + 2e-

1 mol 2 mol
22.4 dm at STP
3
2F
By Eqn:, 2F pass --------------- 22.4 dm3 of Cl2 at STP liberated
 9

1F pass --------------------------------?

= 22.4 dm3  = 11.2 dm3 of Cl2 at STP ←

2. On passing a steady current of 0.75 A for 25 minutes through a copper (II)

sulphate solution, 0.369 g of copper is deposited. Calculate the relative atomic
mass of copper. (One Faraday = 96500 coulombs)
Current I = 0.75 A
time t = 25 min = 25  60 s
Q = It
= 0.75 A  25 × 60 s = 1125 Columb
Cu2+ + 2e-  Cu
2mol 1mol
2F (?)g
2  96500 C (?)g
By Problem; 1125 C ----------------- 0.369g of copper deposited
2 9650 C ------------?

= 0.369  = 63.3g (1 mole)

The relative atomic mass of copper = = 63.3

3. Calculate the mass of silver in grams deposited by passing a steady current of 0.1
A for one hour through an excess of silver nitrate solution, (Ag = 108, one
Faraday = 96500 C)
Current I = 0.1 A
time t = 60 min = 60  60 s
Q = It
= 0.1 A  60 × 60 s = 360 Columb
Ag + e 
+ -
Ag
1 mol 1 mol
1F 108 g
1  96500 C 108 g
By Eqn; 96500 C ----------------- 108 g of Ag deposited
360 C ------------?

= 108  = 0.4029 g ←
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4. An electric current is passed in turn through solutions of silver nitrate and copper
(II) sulphate. If 0.5 g of silver was deposited at the cathode of the first cell,
calculate the mass of copper deposited at the cathode of the second cell.
(Ag = 108, Cu = 63, 1F = 96500 C)
Ag+ + e- → Ag
1 mole 1 mole
1F 108 g
96500 C 108 g
By Eqn; To deposite 108 g of Ag -------- 96500 C will be passed.
---------- 0.5 g of Ag -------- ?

= 96500 × = 446.8 C

Note: Series qufvQif Q wefzdk; wlnDonfudk owdjyKyg/

Cu2+ + 2e- → Cu
2 mole 1 mole
2F 63 g
2 × 96500 C 108 g
By Eqn; 2 × 96500 C pass -------- 63 g of Cu deposite.
446.8 C pass -------- ?

= 63 × = 0.1458 g of Cu ←

5. An electric current is passed in turn through solutions of silver nitrate, copper (II)
sulphate in series. If 0.5 g of silver was deposited at the cathode of the first cell,
calculate the volume of hydrogen liberated at 30 °C and 760 mmHg in the third
cell. (Ag= 108, Cu = 63, 1F = 96500 C)
Ag+ + e- → Ag
1 mole 1 mole
1F 108 g
96500 C 108 g
By Eqn; To deposite 108 g of Ag -------- 96500 C will be passed.
---------- 0.5 g of Ag -------- ?

= 96500 × = 446.8 C

2H+ + 2e- → H2
2 mole 1 mole
2F 22.4 dm3 at STP
2 ×96500C 22.4 dm3 at STP
By Eqn; 2 ×96500 C pass -------- 22.4 dm3 of H2 at STP
446.8 C pass -------- ?

= 22.4 × = 0.0818 dm3 at STP

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STP volume &Smcdkif;aomvolume wGuf&rnf/

Initial state Final state
p1 = 760 mmHg P2 = 750 mmHg
V1 = 0.0518 dm3 V2 = ?
T1 = 0 ºC + 273 T2 = 30 ºC + 273
= 273 K = 303 K
According to the combined Gas Law Equation;
=

V2 =

=
= 0.0582 dm3 ←