ELECTROLYSIS

It the decomposition of ionic compounds using electricity. For a substance to be electrolysed,

it should be a solution or in molten state so that ions are able to move, and carry the charge. A
substance which is decomposed is called an electrolyte. Cations (+) are attracted and
discharged at the cathode (negatively charged). Anions (-) are attracted and discharged at the
anode (positively charged). The flow of ions complete the circuit and the current flows
(electrolytic conductivity).

METTALLIC ELECTROLYTIC
-There is flow of electrons -There is flow of ions
-Takes place in solids and liquids -Takes place in solutions and liquids(molten)

-No chemical change takes place -Chemical decomposition takes place

SELECTIVE DISCHARGE OF IONS

When two or more ions of a similar charge are present in a solution, only one is selected for
discharge and the selection depends on the following factors:
1. Position of the ion in the electrochemical series
If all other factors are constant, an ion will be discharged from the solution in preference to
those above it.
Electrochemical series
Positive ions (Cations) Negative ions (Anions)
K+ Ease of discharge SO4 -2

Na+ of ions increases NO3 -

Ca2+ downwards OH-
Mg 2+ Cl-
H+ Br-
Cu+2 I-
Ag+

2. Concentration
Increase in concentration promotes the discharge of the ion. E.g. In concentrated HCl
containing OH- and Cl- ions, Cl- will be discharged. However if the acid is very dilute, some
discharge of OH- will also occur.
 3. Nature of electrode
It sometimes influences the choice of ion for discharge. E.g. When Sodium Chloride is
electrolysed using platinum cathode, H+ is discharged. When the same substance is
discharged using Mercury cathode, Na+ is discharged.

Electrolysis is carried out using an electrolytic cell. An electrolytic cell is a setup of apparatus
used for carrying out electrolysis.
EXAMPLES:
1. Electrolysis of Concentrated aqueous Sodium Chloride using inert electrodes (those
that do not react with the electrolyte of products of electrolysis).

Ions in solution
Positive Negative
Na+ Cl-
H+ OH-
In any solutions there are always water molecules which split up to form ions;
H2O (l) H+ (aq) + OH- (aq)
Cathode reaction: 2H+ (aq) + 2ẽ H2 (g)
Anode reaction: 2Cl- (aq) - 2ẽ Cl2 (g)
 2. Electrolysis of concentrated hydrochloric acid using inert electrodes.
Ions in solution
Positive Negative
H+ Cl-
H+ OH-
Cathode reaction: 2H+ (aq) + 2ẽ H2 (g)
Anode reaction: 2Cl- (aq) - 2ẽ Cl2 (g)

3. Electrolysis of dilute sulphuric acid (H2SO4)

Ions in solution
Positive Negative
H+ SO4 2-
H+ OH-
Cathode reaction: 2H+ (aq) + 2ẽ H2 (g)
Anode reaction: 4OH- (aq) - 4ẽ 2H2O (l) + O2 (g)
A Hoffman voltameter can be used to keep the gases produced separate. After a short time
the voume produced in each arm can be measured and tested. The ratio of the volume is
approximately 2:1 (hydrogen to oxygen).
HOFMAN VOLTAMETER
 4. Electrolysis of aqueous Copper (ii) Sulphate using inert electrodes.

Ions in solution
Positive Negative
Cu + 2 SO4 2 -
H+ OH-
Cathode reaction: Cu + 2 (aq) + 2ẽ Cu (s)
Anode reaction: 4OH- (aq) - 4ẽ 2H2O (l) + O2 (g)
OBSERVATIONS
- The cathode is coated by a brown metal (copper)
- Bubbles at the anode because of production of oxygen gas
- Colour change from blue to colourless if the experiment is carried out for a long time.
( for a short period of time the colour will turn to faint blue).

5. Electrolysis of copper (ii) Sulphate using active electrodes (those that react with the
electrolyte or products of electrolysis).

Diagram on the next page

Anode reaction: Cu (s) - 2ẽ Cu+2 (aq) or Cu (s) Cu + 2 (aq) + 2ẽ
Cathode reaction: Cu + 2 (aq) + 2ẽ Cu (s)

When Copper (ii) Sulphate solution is electrolysed using copper electrodes, the mass of both
electrodes changes as indicated in the diagram. This is because as copper atoms form at the
cathode, copper ions are lost from the anode.
6. Electrolysis of molten Lead (ii) Bromide (PbBr2) using inert electrodes.
Ions present
Positive Negative
Pb+2 Br -
When a molten compound is electrolysed, the metal is always formed at the cathode and the
non metal at the anode. Heat should continuously be supplied to keep the electrolyte molten.
Cathode reaction: Pb+2 (l) + 2ẽ Pb (i)
Anode reaction: 2Br – (l) + 2ẽ Br2 (g)

APPLICATIONS/ USES OF ELECTROLYSIS

1.ELECTROPLATING
It is coating of an object with a thin layer of a metal by electrolysis. Examples of metals used
for electroplating are:
-Copper -Nickel -Tin -Boron -Silver -Chromium
e.g Electroplating a spoon with copper metal
The basic rules for electroplating an object with metal are as follows:
-the object to be electroplated should be made the cathode.
-The electrolyte should be a solution of a salt of the metal used for electroplating (e.g. Copper
(ii) Sulphate, Copper (ii) Nitrate).
-The anode is made of a strip of the metal used for electroplating (copper).

2.REFINING OF METALS
The copper in electrical wires must be very pure. Copper made by roasting its sulphide ore in
air is about 99.5% pure (impurity level is 0.5%). The impurities cuts down its electrical
conductivity.
During the refining Process, copper is romoved from the impure anodes and deposited on the
pure cathodes. Any impurity fall to the bottom of the cell. The material is called the anode
Sludge, it contains metals such as Platinum, Gold, Silver. This can be purified from the
sludge.

3.EXTRACTION OF ALUMINIUM FROM BAUXITE

Bauxite is the ore of aluminium. Bauxite is changed into pure aluminium oxide called
Alumina. Both the cathode and the anode are carbon electrodes (graphite).
The electrolyte is the molten mixture of alumina and cryolite (Na3AlF6). The temperature of
the molten cryolite is about 9000C.
IONS PRESENT
Na + F-
Al +3 O -2
Cathode reaction: Al +3 (aq) + 3ẽ Al (l)
Anode reaction: 2O -2 (l) - 4ẽ O2 (g)
The carbon electrodes burn away in the oxygen produced and have to be replaced regularly.
C + O2 CO2

The cryolite lowers the temperature from over 20000 C (the melting point of Aluminium
Oxide) to about 9000C, this saves large amount of energy and improves the conductivity of
the electrolyte.
THE HALL-HEROULT CELL

Diagram on page 117 fig 4.75

CALCULATIONS IN ELECTROLYSIS
The amount of products formed at the electrodes can be worked out using the ide of mole.
The amount of substance produced at the electrode depends on the quantity of
electricity/charge passed and the charge on the ion being discharged.
Examples:
1 In an expeiment on electroplating, a current of 0.1 A was passed through a solution of silver
ions for 1 hour. How much silver was deposited?
Q = It
where Q is amount of electricity (coulombs), I is Current and t is time(seconds)
solution: 0.1A X 3600s
=360C
Number of mole of Electrons = Q/F.C
=360C / 96 000 C/mol = 0.00375 mol
Ag+ (aq) + ẽ Ag (s)
1mol : 1mol
0.00375 : X
X = 0.00375mol
Mass = number of moles x molar mass
= 0.375mol x 108g/mol
=0.405g
NB: Faradays = number of mole of electrons
1mole of electrons= 96 500C (faraday constant)
2. In an electrolysis experiment, a current of 19.2A was passed through the cell fro 1 miute 40
seconds.
(a) How many coulombs were passed?
Q = It
=19.2 x 100
=1920C
(b) Calculate the number of faradays passed?
Number of faradays = Q/F.C
=1920C/96 000 C/mol
= 0.02mol
(c) Calculate the number of moles of Nickel Produced
Ni+2 (aq) + 2ẽ Ni ( s )
2mol : 1mol
0.02mol : X
X = 0.01mol
(d) The number of moles of oxygen, O2, produced at the same time is half the answer to (c).
Calculate the volume of oxygen produced.
Volume = number of moles x molar volume
=0.005mol x 24dm3/mol
= O.12dm3
Exercise
1. The diagram shows how a bicycle handle bars made of steel can be electroplated with
Chromium.

(a) Complete the following sentence by choosing words from the list.
Anode cathode negative positive
The Steel handle bars from the cathode are connected to the negative terminal of the battery.
(b) Suggest the name of the Chromium Salt that can be used as the electrolyte.
-Chromium Nitrate (any soluble salt of chromium)
(C) Explain why the chromium rod is used in the electrolytic cell?
-To replace Cr+3 ions in the electrolyte which are discharged at the cathode or which
form the metal chromium at the cathode.
(d) The chromium ion has the symbol Cr+3
Write an equation to show the anode reaction
Cr (s) - 3ẽ Cr +3 (aq)
(e) How many moles of electrons are needed to liberate one mole of Chromium atoms?
3 moles
(i) Calculate the number of moles of electrons required to electroplate the handlebars
with 13g of Chromium. Ar: Cr:52
Number of moles of Chromuim = mass/molar mass
=13g/52g/mol
=0.25mol
 From the equation, the mole ratio is; Cr+3 : 3ẽ
1 : 3
0.25: x
Moles of electrons = 0.75mol
(ii) How many coulombs are needed to give 13g of Chromium?
Number of faradays = Q / FC
Q= Number of Faradays x F.C

= 0.75 x 96 000C/mol

=72 000C
(iii) Calculate the time taken to deposit 13g of Chromium if a steady current of 10
amps flows.
Q = It
t = Q/I
72000C/10A
=7 200seconds
(f) Suggest two reasons for Chromium-plating the handle bars of a bicycle.
-to make them resistant to corrosion
-to make them look attractive

SIMPLE CELLS
A simple cell contains two metallic electrodes in an electrolyte. The more reactive metal
loses electrons and goes into the solution as ions. The electrons move to the less reactive
metal where a gas or a metal is formed e.g zinc and copper cell

Diagram on the next page

Anode reaction: Zn (s) -2ẽ Zn+2 (aq) or Zn (s) Zn+2 (aq) + 2ẽ
Cathode reaction: Cu + 2 (aq) + 2ẽ Cu (s)
Use the diagram to answer the following questions;
1. Which is the most reactive metal in the cell?
Zinc
2. Would th voltage of the cell increase, decrease or stay the same if the zinc electrode
was replaced by Magnesium. Explain your answer.
-it will increase because magnesium is more reactive than zinc.
4. Calculate the voltage of the cell. (Voltage of the cathode = +0.34V and Voltage of the
anode = +0.76V)
V(cell) = V(cathode) + V(anode)
= +0.34V + 0.76V
=1.1V