ELECTROLYSIS

Learning objectives

Electrolysis as a decomposition of an electrolyte by

conduction of electricity.
Electrolysis a type of electrochemical reaction.
Electrical devices used in a typical electrolytic method.
Definition and types of electrodes.
Definition of Conductors and non-conductors (insulators).
Definition of Electrolytes and non-electrolytes.
Definition of anion, cations, oxidation and reduction half
reactions.
Electrolysis of molten solids.

Learning objectives

To write half reactions for different electrolytes.

Explaination for the current flow in the
electrolytic cell. (molten lead bromide)
Rules for predicting the products at the
electrode.
Electrolysis of solutions and selective discharge.
Electrolysis of concentrated sodium chloride
solution (brine).

Conductors: Any substance that allows electric current to

pass through but is not chemically changed. E.g,
metals,graphite.
Non-conductors: Any substance that does not let current
pass through it. Mostly non-metals, glass, wood, diamond,
plastic, rubber etc.When these are especially used for
stopping electricity we call them insulators.

Electrolytes: The chemical substances that decomposes

when current passes through it. E.g acids, alkalis,
molten or solution of ionic compounds.
There are two type of electrolytes: i. Strong ii. Weak
Non-electrolytes: Which do not conduct current. E.g.,
covalent liquids or solutions.

Terms used in electrolysis

An anion is a negative ion and is attracted to the

anode.
A cation is a positive ion and is attracted to the
cathode.
Any reaction at an anode involves loss of
electrons. This is called oxidation.
Any reaction at cathode involves gain of
electrons. This is called reduction.
Half-reactions

Electrolytic Cell

Half reaction: It is defined as either the oxidation

part or the reduction part of a redox reaction.

Oxidation: it involves electron loss.(also called anodic

oxidation)
X- X + ee.g., Cl- Cl2 + eReduction: it involves electrons gain.(also called
cathodic reduction)
M+ + e- M
e.g., Na+ + e- Na

Electrolysis of molten lead(II) bromide

Solid lead(II) bromide

does not conduct
electricity because the
ions are not mobile.
Molten lead(II) bromide
contains mobile ions.

Cation

Anion

Pb2+()

Br-()

Electrolysis of molten lead(II) bromide

At anode, bromide
anions give up
electrons, they
undergo oxidation
and discharge to form
bromine atoms.
2Br-() Br2(g) + 2e-

Electrolysis of molten lead(II) bromide

Bromine atoms then

join in pair to form
bromine molecules.

Electrolysis of molten lead(II) bromide

At cathode, lead(II)
cations receive
electrons, they
undergo reduction
and discharge to form
lead atoms.
Pb2+() + 2e Pb()

Electrolysis of molten lead(II) bromide

Electron flow
Graphite
Electrode (-)

Molten lead(II)
bromide

Graphite
Electrode (+)

Write down the half reactions for the

following ionic compound.

Molten Calcium Chloride

Rules of electrolysis of molten salts:

At the cathode:
Metals are deposited.
At the anode:
Non-metals are released.

Q1.Write down the half reactions for the following

compounds.

Molten Lithium Bromide

Molten Aluminium Oxide
Molten anhydrous Zinc Chloride

Learning objectives

Electrolysis of solutions and selective

discharge.
Electrolysis of concentrated sodium
chloride solution (brine).
Electrolysis of dilute (aqueous) Sulphuric
acid.
Predicting products at the electrodes.

Electrolysis of Solutions

i.
ii.

There are two types of concentration of

solutions:
Concentrated
Dilute
When an ionic compound is dissolved in water
and used as an electrolyte and electric current
passes through it, in addition to the ions of the
compound , water will also ionize to give its
respective ions.

Electrolysis of solution:

Although water is known to be poor electrical

non-conductor, it actually ionizes slightly to give
hydrogen ions and hydroxide ions.
H2O()
H+(aq) + OH(aq)
Pure acids are covalent compounds. However
they ionize in water.
HCl(g) + water HCl(aq)
HCl(aq) H+(aq) + Cl(aq)

Electrolysis of Concentrated
Sodium Chloride (Brine)

Cation
Conc.

Anion

H+(aq) OH-(aq)
Na+(aq) Cl-(aq)

Selective Discharge/Preferential Discharge

When we have more than one type of ion

moving to an electrode, selective
discharge (preferential discharge) takes
place.
This means that the ion which can lose or
gain electrons with the greatest ease is
discharged, and the other ions, which are
harder to discharge, remain in solution.

Position of cations in the electrochemical

series (reactivity series)

Electrochemical series (Selective Discharge)

Cations (aq.)
K+
Na+
Ca 2+
Mg 2+
Zn 2+
Fe +
Pb 2+
H+
Cu 2+
Ag +

Anions (aq.)

SO4-2
NO3ClBrIOH-

Electrolysis of Concentrated
Sodium Chloride (Brine)
The sodium ions and
hydrogen ions move
towards the cathode.
At the cathode: the
position of hydrogen ions in
the electrochemical series
is lower than that of sodium
ions. Hydrogen ions are
preferentially discharged
(reduced) to form
colourless hydrogen gas.
2H+(aq) + 2e H2(g)

 The chloride ions and

hydroxide ions move
towards the anode.
At the anode: the position of
hydroxide ions in the
electrochemical series is
lower than that of chloride
ions. However, the
concentration of chloride
ions is much greater than
that of hydroxide ions.
Chloride ions are
preferentially discharged
(oxidized) to form chlorine
gas.
2Cl-(aq) Cl2(g) + 2e

Electrolysis of Concentrated
Sodium Chloride (Brine)

Overall reaction:
2H+(aq) + 2Cl(aq) H2(g) + Cl2(aq)

Water ionizes continuously to replace the

hydrogen ions discharged at the cathode. Thus
there is an excess of hydroxide ions near anode.
The solution there becomes alkaline.
The chlorine gas formed at the anode dissolves
in the solution. The solution there becomes
acidic and has a bleaching effect.

Electrolysis of Concentrated
Sodium Chloride (Brine)

Hydrogen ions and chloride ions are

consumed in the electrolysis. Sodium ions
and hydroxide ions remain in the solution.
Eventually, the solution becomes sodium
hydroxide solution.
Na+ + OH- NaOH

Electrolysis of Aqueous Sulphuric acid

Cation

Anion

H+(aq)

OH-(aq)

H+(aq)

SO4-2(aq)

Electrolysis of Aqueous Sulphuric acid

The hydrogen ions move towards the
cathode.( common ion in acid and water )
At the cathode, Hydrogen ions discharge
to form colourless hydrogen gas.

2H+(aq) + 2e H2(g)

Electrolysis of Aqueous Sulphuric acid

The sulphate ions and hydroxide ions
move towards the anode.
At the anode: the position of hydroxide
ions in the electrochemical series is higher
than that of sulphate ions. Hydroxide ions
are preferentially discharged (oxidized) to
form colourless oxygen gas.

4OH-(aq) O2(g) + 2H2O() + 4e

Electrolysis of Aqueous Sulphuric acid

At cathode, hydrogen
ions receive electrons,
they undergo
reduction and
discharge to form
hydrogen gas.
2H+(aq) + 2e H2(g)

Electrolysis of Aqueous Sulphuric acid

At anode, hydroxide
ions give up
electrons, they
undergo oxidation
and discharge to
form oxygen gas.
4OH-(aq) O2(g) +
2H2O() + 4e

Rules for predicting products for the

electrolysis of salt solutions(aqueous)

At the cathode
* if the metal in the salt is low in the reactivity
series (e.g. silver, copper or lead) the metal is
deposited.
* if the metal is high in the reactivity series (e.g.
sodium or potassium) Hydrogen is evolved.

Rules for predicting products for the

electrolysis of dilute acids
At the cathode:
* Hydrogen is released.

Rules for predicting products for the

electrolysis of salt solutions(aqueous)
and dil. acids

At the anode:
* if the non-metal in the salt is a halide ion (e.g.
chloride, bromide, iodide), then the halogen is
released if it more concentrated than OH-.
* if the non-metal is not a halogen, oxygen from
the water is given off.

Q1.Write down the half reactions for the following

solutions.

Concentrated Hydrochloric acid

Dilute aq. Copper Sulphate
Dilute aq. Sodium Chloride

Learning objectives

Factors affecting electrolysis

Industrial applications of electrolysis
Purification of copper
Electroplating

Factors affecting electrolysis

The position of ions in the electrochemical

series.
The concentration of ions in the solution.
The nature of the electrodes.

Electrolysis of dilute copper(II) sulphate

solution using carbon electrodes
Cation

Anion

H+(aq)

OH-(aq)

Cu2+(aq)

SO42-(aq)

Electrolysis of dilute copper(II) sulphate

solution using carbon electrodes

The blue colour of the solution fades out

because the concentration of copper(II) ions
decreases.

Copper(II) ions and hydroxide ions are

consumed in the electrolysis. Hydrogen ions and
sulphate ions remain in the solution. Thus the
solution eventually becomes sulphuric acid.

Electrolysis of dilute copper(II) sulphate

solution using copper electrodes

Cation

Anion

H+(aq)

OH-(aq)

Cu2+(aq)

SO42-(aq)

Cu(s)

Cu(s)

Electrolysis of dilute copper(II) sulphate

solution using copper electrodes

The copper(II) ions and hydrogen ions move

towards the cathode.
At the cathode, the position of copper(II) ions
in the electrochemical series is lower than
that of hydrogen ions. Copper(II) ions are
preferentially discharged (reduced) to form
brown copper metal.
Cu2+(aq) + 2e Cu(s)

Electrolysis of dilute copper(II) sulphate

solution using copper electrodes

The sulphate ions and hydroxide ions move

towards the anode.
At the anode: the position of hydroxide ions in
the electrochemical series is lower than that of
sulphate ions. However, copper is a stronger
reducing agent than hydroxide ions and thus
more easily oxidized. The copper anode
dissolves to form copper(II) ions (oxidized).
Cu(s) Cu2+( aq) + 2e

Electrolysis of dilute copper(II) sulphate

solution using copper electrodes

Overall reaction:
Cu(s) Cu(s)
anode
cathode
The net effect is the transfer of copper from the
anode to the cathode. The rate at which copper
deposits on the cathode is equal to the rate at
which the copper anode dissolves.
Increase in mass of cathode = decrease in mass
of anode

Electrolysis of dilute copper(II) sulphate

solution using copper electrodes

The concentration of copper(II) ions in the

solution remains the same. The blue
colour of the solution does not change.

Commercial uses of electrolysis

Manufacture of hydrogen, chlorine and
sodium hydroxide.(from electrolysis of
brine)
Refining of copper
Electroplating
Extracting reactive metals
Extraction of Aluminium

Refining of copper

Refining of copper

Copper ore contains a few impurities mostly

silver, gold, platinum, iron and zinc reduce
the electrical conductivity of copper significantly.
anode: impure copper
cathode: very pure copper
electrolyte: copper(II) sulphate solution and
sulphuric acid

Refining of copper

Impurities such as silver, gold and platinum

settle at the bottom of the container forming
anode sludge.
At the cathode, the position of copper(II) ions in
the electrochemical series is lower than that of
hydrogen ions. Copper(II) ions are preferentially
discharged (reduced) to form brown copper
metal.
At Cathode: Cu2+(aq) + 2e Cu(s)
At Anode: Cu(s) Cu2+(aq) + 2e

Electroplating

Electroplating
Electroplating is the coating of an object
with a thin layer of a metal by electrolysis.
Cathode: object to be plated
Anode: plating metal
Electrolyte: a solution of a compound of
the plating metal

Electroplating
Objects may be electroplated with copper,
nickel, chromium, gold or silver.
Typical example: electroplating of copper