PREFENTIAL DISCHARGE OF IONS

During electrolysis,the product formed at the electrodes depends on the nature of the
electrolyte.The electrolyte solution is influenced by the solvent,which eventually releases it's
ions during the process.In this case,bot cations and anions of solvent and electrolyte will all
migrate to their respective electrodes .Hence,competition for discharge will be set in.The
discharge is governed by three basic conditions which are:-

(i)Position of the ion in the electrochemical/activity series.

(ii)Concentration of ions in the electrolyte.

(iii)Nature of the electrodes.

(a)Relative Position of ions:-If all factors are constant,a cation which is lower in the series will
have better chances to be discharged than another higher in the series.For example, In solution
which contains H+ and Ca²+,the hydrogen will have a better chance to be discharged since it is
lower than the calcium in the activity series.On the contrary,in a solution containing anions such
as SO4²– and OH– will be preferentially discharged to SO4²– since it is higher up in the series
than OH–.

(b)Concentration:-If other conditions are constant,increasing in concentration of an ion

influences the chances of it's discharge.However this can only be effective when the competing
ions are closely positioned to each other in the activity series.

(C)Nature of electrode:-Electrodes have strong affinity for certain ions.However,some

electrodes are inert(unreactive) such as platinum and graphite.For example,the use of mecury
cathode in the electrolysis of sodium chloride will cause the discharge of sodium rather than
hydrogen at the cathode.This is a result of the strong affinity between mercury and sodium to
form sodium amalgam.

Assignment

Draw a diagram of relative position of ions in the activity series.

Electrolytic process

(a)Electrolysis of acidified water:-Acidified water consists of tetraoxosulphate(vi)acid in

water.The elctrolytic cell needs is designed for collation of gaseous products with platinum foils
as elctrodes.The acidified water contains the following ions;

H2SO4 H2O

Cations 2H+(aq) 2H+(aq)

Anions SO4²– OH–

At the cathode:-The H+ which are the only cations migrate to the cathode where they accept
electrons to form hydrogen gas molecule as shown in the equation:

H+ + e H

H + H H2

At the anode:-The SO4²- and OH– both migrate to the anode where OH– is preferentially
discharged since it is higher than SO 4²– activity series.The OH– loses it's electrons to become
neutral OH which dissociates to form oxygen gas molecules as shown below;

4OH- 4OH + 4e

4OH 2H2O + O2

Summary; The electrolysis of acidified water gives 2 volumes of hydroge gas at the cathode and
1 volume of oxygen gas at the anode.

(b)Electrolysis of concentrated sodium chloride solution:In this solution there are four ions
present as follows;

NaCl H2O

Cations Na+ H+

Anions Cl– OH–

Concentration High Low

At the cathode:-H+ is preferentially discharged despite the high concentration of Na+.This is

because of the great distance that exist in the position of the activity series which makes their
concentration less important.

2H+ + 2e H2

At the anode:-Cl– is preferentially discharged since the concentration of Cl – is greater than

OH–.And both ions are very close in their positions on the activity series,hence the effect of
concentration is very important in this case.

2Cl- Cl2 + 2e
Summary:The electrolysis of concentrated sodium chloride gives two gaseous products of
hydrogen gas at the cathode and chlorine gas at the anode.

Overall reaction: 2H+ + 2e + Cl- H2 + Cl2 + 2e

2H+ + Cl- H2 + Cl2

LAWS OF ELECTROLYSIS

The aspect of electrolysis that studies the amount or quantities of products discharged during
electrolysis,was first investigated in 1833 by Faraday.He proposed two laws to explain his
findings which are;First and Second laws of electrolysis.

(a)first law of electrolysis

This law states that the mass of an element discharged during electrolysis is proportional to
the quantity of electricity passing through it.It is mathematically represented as:-

M Q

where Q=It

M It

(b)second law of electrolysis

This law states that when the same quantity of electricity is passed through different
electrolytes,the relative amounts of (elements) discharged are inversely proportional to the
charges on the ions of the elements.

Example 1

Calculate the mass of silver deposited when a current of 2.6A is passed through a solution of a
silver salt for 70 minutes.(Ag=108,1F=96500C)

Solution
Q= It

Q= (2.6 × 70 × 60)

Q= 10,920C

At the cathode: Ag+ + e Ag

From the equation above, 1F will deposit 1mole of Ag

96,500C = 108g of Ag

10,920C = Xg of Ag

By proportion; X= 10,920C × 108g

96,500C
X= 12.22g

Example 2

0.22g of a divalent metal is deposited when a current of 0.45A is passed through a solution of
its salt for 25minutes.Calculate the relative actomic mass of the metal.

Solution

Let the metal be represented by M

At the cathode: M2+ + 2e M

From the above equation, 2F will deposit 1mole of M

2 × 96500C = Mg

(0.45 × 25 × 60)C = 0.222g

By proportion; M = 0.222 × 2 × 96500 = 42846

0.45 × 25 × 60 675
M = 63.5g

The relative atomic mass of the metal is 63.5gmol-

Example 3
 A current is passed through three electrolytic cells connected in series containing solutions of
silvertrioxonitrate(v),copper(ii)tetraoxosulphate(vi) and brine respectively.If 12.7g of copper are
deposited in the second electrolytic cell, calculate the mass of silver deposited in the first cell.

Solution

Cathodic half equation in the first cell

Ag+ + e Ag

1F = 1 mole of Ag

Cathodic half equation in the second cell

Cu2+ + 2e Cu

2F = 1 mole of Cu

2 × 96500C = 63.5g of Cu

Q2 = 12.7 g of Cu

By proportion, Q2 = 12.7 × 2 × 96500

63.5
Q2 = 38600C
From second law of electrolysis
Q1 = Q 2 = Q 3
1 × 96500C = 108g of Ag
38600C = Mg of Ag
By proportion, M = 38600C × 108g = 43.2 g
96500C

The mass of silver deposited is 43.2 grams

Application of Electrolysis
Electrolysis is of great application in the industry as follows:-

(i)Extraction of metals such as sodium,aluminum, calcuim,potassium, magnesium.

(ii)Purification of metals such as copper,mercury, gold,silver,e.t.c.

(iii)Electroplating of metal surfaces

(iv)Manufacture of chemicals such as sodiumhydroxide e.t.c.