ELECTROLYSIS II

Laws of Electrolysis
The laws expressing the quantitative result of electrolysis were first stated by Faraday.
The quantity of products liberated at the electrodes during electrolysis is based on the factors
1. The magnitude of the steady current
2. The time of flow of steady current
3. The ionic charge of the liberated element
In 1833, Micheal Faraday put forward two laws to describe these quantitative relationships.

Faraday’s First Law of Electrolysis

Faraday’s first law of electrolysis states that the mass of an element liberated or deposited during
electrolysis is directly proportional to the quantity of electricity that passes through the electrolyte.
Mathematically M ∞ Q
Where M is mass deposited in grammes and Q is the quantity of electricity passed in coulombs.
Quantity of electricity = current(I) × time(t)
i.e Q = It
M∞Q
M ∞ It
Or M = EIt
(Where E is a constant, known as electrochemical equivalent of the substance)
Q = Quantity of electricity in coulombs (c)
M = Mass of substance deposited in grammes(g)
I = Current in Ampere (A)
t = Time in seconds (s)
E = Chemical equivalent or constant (g/c)
The electrolytic cell above is the electrolysis of copper (II) tetraoxoshulphate (IV) using copper cathode.
The magnitude of the current passed is measured by the ammeter, while a rheostat is used to adjust the
current to the required magnitude.
When an electric current is passed through the electrolyte, copper atoms are deposited at the cathode.

Procedure: weigh the copper cathode at the beginning of the experiment. Weigh it again after passing a
current of 1 ampere for 10minutes. Then determine the gain in the mass of copper deposited in
10minutes. Repeat this procedure using different time intervals.

Result: a straight line graph passing through the origin is obtained. This shows that the mass of copper
deposited is directly proportional to the time of current flow or magnitude of the current.

Conclusion
The mass of an element discharged during an electrolysis is directly proportional to:
1. The time of flow of the current
2. The magnitude of the current

Example 1
A current of 0.72 amperes was passed through a solution of an electrolyte for 3 hours 20 minutes.
Calculate the quantity of electricity passed. Current(I) = 0.72A, time = 3 hrs 20 mins
Quantity of electricity (Q) = current x time (t)
Q= 0.72 x {3 x 60 x 60} + {20 x 60}s
0.72 x 10800 + 1200
0.72 x 12000
Q = 8640 C
Example 2
Calculate the mass of silver deposited when 0.2A of electricity is passed through a Agcl solution for 2
hours. Given that the chemical equivalent of Ag = 0.000098g
T = 2hrs (2 x 60 x 60) = 7200s
I = 0.2A
E = 0.000098g/c
M = EIT = 0.000098 x 0.2 x 7200
M = 0.1411g

Faraday’s Second Law of Electrolysis

Faraday’s second law of electrolysis states that when the same quantity of electricity is passed through
different electrolytes, the relative numbers of moles of element discharged are inversely proportional to
the charges on the ion of the element respectively.
Whenever 1 mole of electrons is involved in an electrolytic cell, the total quantity of electricity involved
is 96,500Columbs. This quantity is known as one faraday
(i) 1 faraday of electricity is needed to discharge 1 mole of monovalent element during electrolysis
Ag+(aq) + e– → Ag(s)
Na+(aq) + e– → Na(s) (1 mole of atom)
(ii) 2 faradays of electricity are needed to discharge 1 mole of divalent element during electrolysis
Cu2+(aq)+ 2e– → Cu(s)
Zn2+(aq) + 2e– → Zn(s) (2 moles of atoms)
(iii) 3 faradays of electricity are needed to discharge 1 mole of trivalent element during electrolysis
Fe3+(aq) + 3e– → Fe
Al3+(aq) + 3e– → Al (3 moles of atoms)

Verification of Faraday’s second law of Electrolysis

Procedure: to verify faraday’s second law of electrolysis, two electrolytic cells were used. Copper
electrode immersed in CuSO4 and silver electrode immersed in AgNO3 solution. The copper and silver
electrodes were weighed before connecting them for the electrolytic process. A current of 0.45Amperes
is passed through the solution for 25minutes.
Switch off the current and reweigh to determine the gain in mass. Then calculate the number of moles of
atoms of each of the element deposited.

Specimen result
Current flowing = 0.45A
Time of current flow = 25minutes
Mass of copper deposited = 0.222g
Mass of silver deposited = 0.756g
Molar mass of copper = 63.5 g/mol
Molar mass of silver = 108 g/mol

Conclusion
Although the same quantity of electricity was passed through two electrolytes, the number of moles of
silver is twice that of copper. The charge on copper is +2, while that of silver is +1. Therefore the
number of moles of copper and silver deposited are inversely proportional to the charge on their ions.
Quantity of electricity = current x time
Q = IT
I = 0.45A, T = 25 minutes
Q = 0.45 x 25 x 60 = 675 coulombs
To calculate the mass of copper and silver deposited respectively.
Copper
Cu2+(aq) + 2e– → Cu(s)
(2 x 96500)C deposits 63.5g of Cu

Silver
Ag+[aq] + e– → Ag(s)
(1 x 96500)C deposits 108g of Ag

Worked Examples
1. Calculate the mass of silver deposited when a current of 2.6A is passed through a solution of silver for
70minutes. [Ag = 108, 1F = 96500C]
Solution
Quantity of electricity Q = IT
I = 2.6A
T = 70minutes
IT = (2.6 x 70 x 60)C
Ag+[aq] + e– → Ag(s)
96500c liberates 108g of Ag
(2.6 x 70 x 60)C will liberate?
2. Find the time required to deposit 3.02g of Cu from Cu(NO3)2 solution by passing a current of 2.60A
through it. (Cu = 64, 1F = 96,500C)
Solution
Q = IT
I = 2.60A T =?
Q = 2.60T
Cu2+[aq] + 2e– → Cu(s)
2F will be required to deposit 1 mole of copper mass of copper deposited = 3.02g, R.M.M of Cu = 64G
If 64g of Cu is deposited by 2 x 96500 coulombs
3.02g of Cu will be deposited by

This is the quantity of electricity Q

But Q = IT
Q = 2.60T
9107.19C = 2.60t

t = 3502.8secs.

3. A current of 45A is passed through a solution of gold salt for 1 hour 45minutes calculate
(a) The mass of gold deposited
(b) The number of moles of gold deposited
(c) If the same current is used, find the time taken for 5.5g of gold to be deposited
(Au = 197, 1F = 96500C)

Solution
(a) Quantity of electricity = IT
I = 45A, T = 1 hr x 60 mins + 45 mins = (60 + 45) = 105mins
Q = 45 x 105 x 60 = 28350 Coulombs
Au+(aq) + e– → Au(s)
It will be required to discharge 1 mole of Au
If 96500 Coulombs deposited 197g of Au
∴ 28350 Coulombs will deposit

(b) Number of moles of Au deposited

Mass of Au = 57.88g
Molar mass of Au = 197

(c) Time taken for 5.5g of Au to be deposited

57.88g of Au required 28350C of electricity
5.5g of Au will require

This is the quantity of the electricity of Q, required for 5.5g of Au to be deposited.

Q = IT
Q = 2693.9, A = 4.5A

t = 598.65 seconds or 9.98 minutes

4. If a current of 3.6A is passed for a period of 2.7 minutes through an electrolytic cell containing
Ca(OH)2 solution. Calculate the volume of oxygen evolved at 400k and 3.02 x 105 Nm-2 at the anode if
carbon electrode is used (molar volume = 22.4dm3 at s.t.p standard pressure =1.01 x 105 Nm2, 1F = 96,
500C)
Solution
Q = IT
I = 3.6A
T = (2.7 x 60) = 162 secs
Q = 3.6 x 162 = 583.2C
To calculate the volume of oxygen evolved
Ca(OH)2(aq) ⇌ Ca2+(aq) + OH–(aq)
H2O(l) ⇌ H+(aq) + OH–(aq)
OH– ions migrate and discharge at the anode (reacting mechanism of electrolysis)
OH– – e → OH
OH + OH → H2O + O
O + O → O2
4OH – 4e → 2H2O + O2
No of Faraday’s = 4F
This implies that 4F is liberated by 1 mole of O2
i.e 4F → 1 mole of O2
4F → 1 x 22.4 dm3 of O2
(4 x 96500) → 22.4 volume of O2
But Q = 583.2c
If (4 x 96500)C gives 22.4 dm3 of O2

V1 = 0.034dm3 at s.t.p
The question requires us to find the volume at 400k and 3.02x 105 Nm-2. So we use the general gas
equation.

P1 = 1.01 x 105 Nm-2 (pressure at stp)

V1 = 0.034dm3
T1 = 273k (temperature at stp)
P2 = 3.02 x 105 Nm-2
V2 = ?
T2 = 400k
V2 = 0.017dm3

Uses/Application of Electrolysis
1. Extraction of metals from their ores. (e.g. Na, Mg, Ca, Al, Zn) and non-metals (e.g. H2, F2, Cl2).
2. Purification of metals (e.g. Cu, Hg, Ag and Au)
3. Electroplating of one metals by another
4. Industrial preparation of certain chemicals (e.g. NaOH, Cl2, O2, H2, Cl2)

Extraction and Purification of Metals

Metals such as silver and copper, are refined or purified by electrolysis. The impure metals are made the
anode, while the pure metals are made the cathode, the electrolyte is an aqueous solution of the salt of
the metals.

Purification of Impure Copper by Electrolysis

An electrolytic cell in which the impure copper serves as the anode and pure copper plate serves as the
cathode is used and the electrolyte is copper(II) tetraoxosulphate (VI) solution (CuSO4)
During the electrolysis, the impure copper anode gradually dissolves as copper ions into the solution
which migrates to the cathode. The impurities which do not dissolve settled at the base of the container
i.e. At the cathode, the Cu2+ receives electrons and becomes deposited on the pure copper plate as
neutral copper atoms.
Cu2+(aq) + 2e– → Cu(s).
Electroplating
Electroplating is a method of coating the surface of one metal with another metal. e.g. copper, silver,
chromium, nickel, or gold by means of electrolysis for decoration or protection against corrosion.
In electroplating a material (spoon, car, bumper, etc) to be plated is made the cathode while the anode is
the metal to be coated on the material, the electrolyte is a solution of soluble salt of the metal to be
plated on the material.
For example in silver plating a spoon cathode is the spoon and anode is silver rod
Electrolyte is aqueous AgNO3
When the current is passed through the cell, silver rod dissolve at the anode and ions produced migrate
to the cathode where they are discharged and deposited as a layer on the spoon
At cathode
Ag(aq)+e−→Ag(s)Ag(aq)+e−→Ag(s)
At anode
Ag(l)–e−→Ag(aq)Ag(l)–e−→Ag(aq)
Advantages of Electroplating
1. Electroplating prevents rusting of iron
2. It increases the attractiveness of the object plated
3. It gives thickness to the object plated
Examples of electroplated objects:- door handles chromium-plated, hospital equipment, silver-plated
cutlery, and tin-plated cans.

Manufacture of Compounds, Electrolysis of Brine

Manufacture of Compounds
Pellets of sodium hydroxide are manufactured by the electrolysis of brine.

Electrolysis of Brine
The electrolysis of brine yields hydrogen and chlorine at the electrodes.
The electrolytic cell used is known as the Kellner-solary cell. The anode is a carbon rod (graphite)
dipped into the brine in the tank. A layer of mercury flowing at the base of the tank acts as the cathode.
Chlorine is being discharged at the anode 2Cl–(aq) → Cl2(g) + 2e-
At the cathode:- sodium ions combine with the mercury to produce sodium amalgam.
The amalgam is drained and led to a second tank.
The amalgam is treated with water at the second tanks and decomposes to produce sodium hydroxide,
hydrogen, and mercury.
2Na/Hg(l) + 2H2O(l) → NaOH(aq) + H2(g) + 2Hg(l)
The electrolysis of brine is very important because of the usefulness of its three products sodium
hydroxide, hydrogen and chlorine.
It is also a very economical process.