Electrolysis

LESSON OBJECTIVES
 At the end of the lesson, you would be able to
 Describe electrolysis in terms of the ions
present and reactions at the electrodes in the
examples given
 State the general principle that metals or
hydrogen are formed at the negative
electrode (cathode), and that non-metals
(other than hydrogen) are formed at the
positive electrode (anode)
 Describe the electrode products in the
electrolysis of molten lead(II) bromide.
 Recall…
 Ionic compounds can conduct electricity in
which states and why?
 Ionic compounds conduct electricity in molten
and aqueous states as the ions are not held in
their fixed positions and are free to move.
Solid ionic compounds
do not conduct
electricity as the ions
are held close
together in a lattice
and cannot move
freely.
Metals can conduct
electricity in solid
state due to the
‘sea’ of mobile
electrons.
 Electrical conduction Electrolytic conduction
by metals and graphite by electrolytes

Method of Electricity is Electricity is conducted

conduction conducted by the flow by the movement of
of electrons from one positive ions and
end of the conductor negative ions across the
to the other. electrolyte.
Effect of Metals and carbon The electrolytes are
conduction remain unchanged when decomposed to form new
an electric current substances when they
flows through them. conduct electricity.
 What is Electrolysis?
 Electrolysis is the conduction of electricity
by an ionic compound, when molten or
dissolved in water, leading to its
decomposition.

 Hence, molten ionic compounds or aqueous

solutions containing free moving ions can
conduct electricity and are called
electrolytes.
 Terms to remember…
 Electrolytes:
molten ionic compounds or aqueous solutions
 Electrodes: metal plates or carbon rods used
to conduct an electric current.
Anode: electrode connected to the positive
terminal of the battery.
Cathode: electrode connected to the negative
terminal of the battery.
 Anion: negative ion that is attracted to the
anode.
 Cation: positive ion that is attracted to the
cathode.
 Inert electrodes: electrodes that do not take
part in any chemical reaction during
electrolysis.
Examples: carbon (graphite), platinum

 Used to prevent reactions from occurring

between the electrodes and the products of
electrolysis.
 Why is the anode positively charged and the
cathode negatively charged?
The battery draws the electrons away from
the anode  positively charged.
The battery supplies electrons to the cathode
 negatively charged.
 What is Happening during
Electrolysis?
 Electrical energy  chemical energy
 Ions are discharged at the cathode and
anode.
Cations receive electrons at the cathode.
Anions give up electrons at the anode.
The ions form atoms or molecules during the
process.
 Recall…
Oxidation Reduction

Oxygen Gain Loss

Hydrogen Loss Gain

Electrons Loss Gain

Oxidation state Increase Decrease

 What Type of Reactions take place
during Electrolysis?
 At the cathode:
 Reduction takes place as cations gain electrons.
metals or hydrogen are formed at the cathode
Cu2+ + 2e-  Cu
 At the anode:
 Oxidation takes place as anions lose electrons.
non-metals (other than hydrogen) are formed
at the anode
2 Cl-  Cl2 + 2e-
 Hence, redox reactions take place during
electrolysis.
 What is a Binary Compound?
 Sodium chloride, NaCl, is an example of a
binary compound.

 Many ionic compounds are binary compounds.

A binary compound is a compound containing
only two elements.
Contains a metal cation and a non-metal anion.

 Electrolysis of a molten binary compound will

yield a metal and a non-metal as products.
 Electrolysis of molten PbBr2
 Solid PbBr2 is heated strongly until it melts
 Molten PbBr2 contains Pb2+ ions and Br- ions.

 At the cathode:
Each Pb2+ ion gains electrons to form a Lead
atom.
Pb2+(l) + 2e-  Pb (l)

 At the anode:
Each Br- ion gives up an e- to form a Br atom.
2 Br atoms combine to form Br2.
2 Br- (l)  Br2 (g) + 2 e-
 Overall reaction:

PbBr2 (l)  Pb (l) + Br2 (g)

 Pb2+ ions are discharged at the cathode and

Br- ions are discharged at the anode.
 Lead metal is deposited at the cathode and
Bromine gas (reddish fumes) are released at
the anode.
 Why are carbon electrodes used in the
electrolysis of molten PbBr2?

 The use of an inert electrode prevents any

reaction from occurring between Bromine and
the electrode.
 Try this…
 Molten potassium chloride was electrolysed,
using carbon electrodes.

a) Write the formulas of the ions in the

electrolyte.

b) (i) Name the product at the cathode.

(ii) Write the half equation for the reaction
at the cathode.

c) (i) Name the product at the anode.

(ii) Write the half equation for the reaction
at the anode.
 OBJECTIVES
At the end of the lesson you should be able to
Predict the products of electrolysis of a
specific halide in dilute or concentrated
aqueous solutions
Understand the factors that affect the
selective discharge of ions
 Electrolysis of Aqueous Solutions of
Compounds
 An aqueous solution of a compound is a
mixture of two electrolytes.

 Example: Aqueous copper (II) sulphate

solution
Copper (II) sulphate
CuSO4  Cu2+ + SO42-
Water
H2O H+ + OH-
 Which are the Ions that will be
Discharged??
 The selective discharge of ions in the
electrolysis of aqueous solution using inert
electrodes depends on two factors:
The position of the metal in the reactivity
series
The concentration of the ion in the electrolyte
Potassium ions, K+ Sulphate ion, SO42-
Calcium ion, Ca2+ Nitrate ion, NO3-
Sodium ion, Na+ Carbonate ion, CO32-
Magnesium ion, Mg2+ Ease of
Chloride ion, Cl-
Zinc ion, Zn2+
discharge
increases Bromide ion, Br-
Iron ion, Fe2+ Iodide ion, I-
Lead ion, Pb2+ Hydroxide ion, OH-
Hydrogen ion, H+
Copper ion, Cu2+
 Discharge of Cations during
Electrolysis
 Positive ions from the metal lowest in the
reactivity series are discharged at the
cathode in preference to any other positive
ions present in the solution. (WHY??)

 More reactive metals form more stable ions.

 Ions therefore remain in solution and will not

be converted back to the metal.
 Example…
 If a solution containing both Na+ and H+ ions is
electrolysed, which of the two ions will be
discharged?

 H+ ions will be discharged.

Sodium is above hydrogen in the reactivity
series. Na+ has a higher tendency to exist as
an ion than an atom.
 Discharge of Anions during
Electrolysis
 OH- ions will always be discharged in
preference to SO42-, NO3- & CO32- ions.

 The OH- ions give up electrons most readily

during electrolysis.
**4 OH- (aq)  2 H2O (l) + O2 (g) + 4 e-
 Effect of Concentration on Selective
Discharge
 Applies only to discharge of anions

 In concentrated solutions, an increase in the

concentration of an anion tends to promote its
discharge.
 Case Study…
1. Electrolysis of concentrated sodium chloride
solution

2. Electrolysis of aqueous copper (II) sulphate

solution

3. Electrolysis of dilute sulphuric acid

 Electrolysis of Concentrated NaCl
Solution
 Ions present:
Cations: Na+ (aq), H+ (aq)
Anions: Cl- (aq), OH- (aq)

 At the cathode:
H+ ions are discharged as they accept
electrons more readily.
2 H+ (aq) + 2 e-  H2 (g)
 At the anode:
There is a high concentration of Cl- ions.
Cl- ions are discharged preferentially over
OH- ions.
2 Cl- (aq)  Cl2 (g) + 2 e-

 One volume of hydrogen gas is produced at

the cathode & one volume of chlorine gas is
produced at the anode.
 The resulting solution becomes alkaline.
WHY??
Electrolysis of Concentrated NaCl Solution
 Electrolysis of Aqueous Copper (II)
Sulphate
 Ions present:
Cations: Cu2+ (aq), H+ (aq)
Anions: SO42- (aq), OH- (aq)

 At the cathode:
Copper is lower than hydrogen in the reactivity
series.
Cu2+ ions accept electrons more readily.
Cu2+ is preferentially discharged to form
copper atoms.
Cu2+ (aq) + 2e-  Cu (s)
 At the anode:
OH- ions give up electrons more readily than
SO42- ions.
OH- ions are preferentially discharged to give
oxygen gas.
4 OH- (aq)  2 H2O (l) + O2 (g) + 4 e-

 Observations:
A reddish-brown solid is deposited on the
cathode.
The solution turns from blue to colourless.
 Electrolysis of dilute H2SO4
 Ions present:
H+ (aq), OH- (aq) (from water)
H+ (aq), SO42- (aq) (from acid)

 At the cathode:
H+ ions gain electrons from the cathode to
form hydrogen gas.
2 H+ (aq) + 2 e-  H2 (g)
 At the anode:
4 OH- (aq)  2 H2O (l) + O2 (g) + 4 e-

 Electrolysis of dilute H2SO4 results in the

breakdown of water to give hydrogen and
oxygen.
 2 H2O  2 H2 + O2

 The volume of hydrogen formed is twice the

volume of oxygen formed.
 hydrogen
oxygen

Dilute
H2SO4
Platinum
electrodes
Industrial Applications of Electrolysis
1. Extraction of metals
 To extract very reactive metals from their
ores.

2. Electrolytic refining
 To purify metals, such as copper

3. Electroplating
 The process of depositing a layer of metal on
another substance using electrolysis.
 Extraction of Aluminium
 Metal ore: Bauxite (Al2O3)

 The melting point of aluminium oxide is very

high (2 045°C). It is expensive and dangerous
to carry out electrolysis at this temperature.

 Hence, aluminium oxide is dissolved in cryolite

(Na3AlF6). The melting point is reduced to
950°C.
Bauxite
 Ions present:
Cations: Al3+ (l)
Anions: O2- (l)

 At the cathode:
Al3+ (l) + 3 e-  Al (l)
Molten Al is deposited at the bottom of the
tank.

 At the anode:
2 O2- (l)  O2 (g) + 4 e-
Oxygen gas is formed at the anode.

 Overall: 2 Al2O3 (l)  4 Al (l) + 3 O2 (g)

What Happens to the Anode after some
time??
 Oxygen gas reacts with the carbon anodes at
high temperature to form carbon dioxide.

 C + O2  CO2

 Hence, carbon anodes must be replaced

regularly.
 Reactive Electrodes
 If a more reactive metal is used as the
electrodes, it itself may undergo oxidation in
preference to other possible reactions.

 The electrode is thus known as a reactive

electrode.
 Electrolysis of CuSO4 using copper
electrodes
 Ions present:
Cu2+ (aq), SO42- (aq) (from copper (II) sulphate)
H+ (aq), OH- (aq) (from water)

 At the cathode:
Cu2+ (aq) + 2 e-  Cu (s)

 At the anode:
Since copper is not an inert electrode, the
anode will dissolve to form Cu2+ ions.
Cu (s)  Cu2+ (aq) + 2 e-
 Observations:
Reddish-brown solid is deposited on the
cathode.
Cathode increases in mass. Anode decreases in
mass.
The solution remains blue as one Cu 2+ is formed
at the anode whenever one Cu2+ is removed
from the cathode.

 Applied in the purification of copper and in

electroplating.
 Purification of Copper
 Anode:
Impure copper
Cu (s)  Cu2+ (aq) + 2 e-

 Cathode:
Thin sheet of pure copper
Cu2+ (aq) + 2 e-  Cu (s)

 Impure anode dissolves and impurities fall to

the bottom of the cell to form an ‘anode slime’.

 A layer of pure copper is deposited on the

cathode.
 Electroplating of Metals
 Electroplating is similar to electrolytic
refining.
 Cathode:
Object to be plated
 Anode:
Source of the plating metal.
 Electrolyte:
Aqueous solution of a salt of the plating metal.
 Conditions for good quality plating

 The metal object to be plated must be clean

and free from grease.

 The concentration of metal ions must be low.

 The electric current must not be too large,

otherwise the coating layer will form too
rapidly and peel off easily.
 Uses of Electroplating
 Give the metal object a good decorative look

 Prevent it from rusting