ELECTROCHEMISTRY

CHEMICAL
SUBSTANCES
ELECTROLYTES
Substances that can conduct
electricity when they are in
molten state or aqueous and
undergo chemical changes

NON-ELECTROLYTES
Substances that cannot
conduct electricity either in
molten state or aqueous
Example:

Example:
Ionic substances

(i) Dilute acid solution

(ii) Dilute alkaline solution
(iii) Molten salts
(iv) Aqueous salt solution

Covalent substances
(i) Naphthalene
(ii) Sugar solution
(iii) Latex
(iv) Hydrogen chloride in organic
solvents

switch

switch

Carbon
electrodes

Bulb

Bulb

Carbon
electrodes
. .
.
. .
.

..
. ..
.

Heat

Solid lead (II) iodide

.
. .
.
.
.
.
.

Heat

Molten lead (II) iodide

IN A SOLID STATE
Do not conduct
electricity
Pb
Pb

2+

Pb

2+

I
2+

I
-

Pb

Pb

2+

Pb

2+

I
2+

I
-

Pb
I

Solid lead (II) iodide

2+

This is because the

ions are held in a
fixed crystal lattice.
They are held with
the strong
electrostatic forces
of attraction
Do not freely move

IN A MOLTEN STATE

Pb

Pb

2+

I
I

2+

Molten lead (II) iodide

Pb

2+

Can conduct
electricity
This is because the
presence of moving
ions. The ions are
free to move in the
molten or aqueous
solution

ELECTROLYTES AND NON ELECTROLYTES

Classify the following chemicals into electrolytes or nonelectrolytes

Potassium chloride, KCl solution

Molten lead (II) bromide, PbBr2
Glucose solution
Trichloromethane
Molten zinc oxide, ZnO
Sodium chloride, NaCl solution
Ammonia in tetrachloromethane

ELECTROLYSIS

A process of breaking down the chemical compounds

into their constituent elements using electric current
Example:
Molten aluminium oxide (I)
Copper (II) chloride (aq)

Electric current

aluminium (s) + oxygen (g)

Electric current

copper (s) + chlorine (g)

ELECTROLYTIC CELL
e-

ee-

e+ (anode)

- (cathode)

Electrode

Electrode

..

..

.. .

- ..
+
...

Anion

Cation

Electrolyte

ELECTROLYTIC CELL
The set of apparatus needed to conduct electrolysis
It consists of a battery, an electrolyte, and two
electrodes (anode and cathode)
Anode - the electrode which is connected to the
positive terminal of an electric source in the
electrolytic cell
Cathode - the electrode which is connected to the
negative terminal of an electric source in the
electrolytic cell

During electrolysis:

ANODE
(POSITIVE ELECTRODE)

CATHODE
(NEGATIVE ELECTRODE)

Anions (negative ions)

will be pulled towards
the anode (positive
electrode)

Cations (positive ions) will

be pulled towards the
cathode (negative
electrode)

At the anode, anions

will be discharged by
releasing the electrons
to the anode

At the cathode, cations will

be discharged by
receiving the electrons
from the cathode

ELECTROLYSIS OF MOLTEN
COMPOUNDS

QUESTIONS
Electric current
(a) Molten zinc chloride (I)
(b) Molten aluminium (III) bromide Electric current
(c) Molten zinc (II) iodide Electric current
(d) Molten lead (II) oxide Electric current

Example 1
e-

ee-

e+ (anode)

Carbon
electrode

- (cathode)

..

..

.. .

..

...

The ions that presents in electrolyte are:

(i) Anion:
(ii) Cation:

Carbon
electrode

Molten Potassium
Iodide, KI

Example 2
e-

ee-

e+ (anode)

Carbon
electrode

- (cathode)

..

..

.. .

..

...

The ions that presents in electrolyte are:

(i) Anion:
(ii) Cation:

Carbon
electrode

Molten zinc oxide,

ZnO

Example 3
e-

ee-

e+ (anode)

Carbon
electrode

- (cathode)

..

..

.. .

..

...

The ions that presents in electrolyte are:

(i) Anion:
(ii) Cation:

Carbon
electrode

Molten lead (II)

bromide, PbBr2

Example 4
e-

ee-

e+ (anode)

Carbon
electrode

- (cathode)

..

..

.. .

..

...

The ions that presents in electrolyte are:

(i) Anion:
(ii) Cation:

Carbon
electrode

Molten lead (II) oxide,

PbO

Example 5
e-

ee-

e+ (anode)

Carbon
electrode

- (cathode)

..

..

.. .

..

...

The ions that presents in electrolyte are:

(i) Anion:
(ii) Cation:

Carbon
electrode

Molten zinc (II)

chloride, ZnCl2

ELECTROLYSIS OF MOLTEN COMPOUND

e-

ee-

e+ (anode)

Carbon
electrode

- (cathode)

..

..

.. .

..

...

The ions that presents in electrolyte are:

(i) Anion:
(ii) Cation:

Carbon
electrode

Molten lead (II)

bromide, PbBr2

ELECTROLYSIS OF MOLTEN
COMPOUND
e-

e-

e-

e+ (anode)

Carbon
electrode

. Br

.. .

- (cathode)

Br-

Br

..

Br..

Pb2+

2+

Pb

..

Carbon
electrode

Pb2+

Pb2+

...

Molten lead (II)

bromide

ANODE
(POSITIVE ELECTRODE)
-

CATHODE
(NEGATIVE ELECTRODE)
Pb

Br are attracted to anode

2+

are attracted to the cathode

Br discharge by releasing electrons to the

anode
Br
Br + e

Neutral atoms form and combine to form

neutral bromine molecules

Br + Br

Br2 (g)

2+

Pb discharge by receiving electrons

(provided by the battery) at the cathode
to form neutral lead atoms

The half reaction at cathode can be

represented by the half equation
2+

Pb (l) + 2e
The half reaction at anode can be
represented by the half equation
-

2Br (l)

Br2 (g) + 2e

Pb (s)

The Half Equation:

2+
Pb
(l)
+
2e
Cathode:

Anode:

2Br- (l)

Pb (s)
Br2 (g) + 2e-

Overall Equation:
Pb2+(l) + 2Br- (l)

Pb(s) + Br2 (g)

Write the half equation and the overall equation

for the electrolysis of these molten
compounds :
(A) Molten potassium iodide, KI
(B) Molten zinc (II) chloride, ZnCl2
(C) Molten lead (II) oxide, PbO

ELECTROLYSIS OF AQUEOUS SOLUTION

Water molecules in an aqueous solution can slightly dissociate to
produce H+ and OHH 2O

H+ (aq) + OH-(aq)

So, aqueous solution contains H+ and OH- and electrolyte ions

Examples:
Ions present

Aqueous Solution

Anion

Cation

NaCl solution

Cl- , OH-

Na+ , H+

CuSO4 solution
HNO3 solution

If they are more than one cations or anions attracted,

the choice of ion to be discharged depends on :

Positions of the ions

in the electrochemical series

Concentration of ions
in the electrolyte
Types of
electrodes

Electrochemical Series (pg.101)

CATIONS

ANIONS

K
Na+
Ca2+
Mg2+
3+
Al
Zn2+
Fe2+
Sn2+
2+
Pb
H+
Cu2+
Ag+

FSO42NO3ClBrIOH
Tendency to
discharge
increases

 The tendency of ions to be selected to be discharged at an

electrode depends on their position in a series called the
electrochemical series.
The ions at the top of the list is more difficult to be discharged,
but as we go down the table, they become easier to be
discharged.

Positions of the ions

in the electrochemical series
e-

e-

e-

e+ (anode)

- (cathode)

Carbon
electrode

Carbon
electrode
Cu2+

OH

Cl

H+

OHCl-

H+

Cu2+

Copper (II) chloride

solution, CuCl2

Positions of the ions

in the electrochemical series

Ions that are

attracted

Observation
and
Product
Half equation

Anode

Cathode

OH- , ClOH- are preferred to be

discharged
(OH- is below Cl- in the ES)

H+ , Cu2+
Cu2+are preferred to be
discharged
(Cu2+ is below H+ in the ES)

Bubbles of gas, O2
is released
-

4OH (aq)

2H2O (l) + O2 (g)

+4e

Brown solid, Cu is formed

Cu

2+

(aq) + 2e

Cu (s)

Example: Electrolysis of Aqueous

Sulphuric Acid

 Figure above shows the set up of apparatus used to

investigate the electrolysis of aqueous sulphuric
acid.
Carbon electrodes are used as the anode and
cathode.
The molecules of sulphuric acid ionise to form
hydrogen ions and sulphuric ions.
H2SO4 2H+ + SO42 In an aqueous solution, water molecules will also
ionise to form hydrogen ions and hydroxide ions.
H2O H+ + OH Therefore, the ions that present in the solution
are H+ , SO42-, H+ and OH

At anode (Positive Electrode)

The negative ions (SO42- and OH-) will be attracted to the
anode.
OH- ions is lower than SO42- ions in electrochemical series,
hence the OH- ions will be selected to be discharged at
anode.
The OH- ions discharged to form water and oxygen gas.
4OH- 2H2O + O2 + 4e
Observation:
Colourless gas bubbles are released around anode. When
a glowing wooden splinter is inserted into the test tube that
contain the gas, the wooden splinter light up.

At cathode (Negative Electrode)

The positive ions (H+) are attracted to cathode.
The H+ ions are discharged to form hydrogen molecule.
2H+ + 2e H2
Observation:
Colourless gas bubbles are released around cathode. When a lighted
wooden splinter is brought close to the mouth of the test tube that
contain the gas, a "pop" sound is produced.

Concentration of ions in electrolyte solutions

Concentration of ions in electrolyte solution also can
affects the choice of ions to be discharged
An ion that is more concentrated is preferably
discharged
Anode the ions to be discharged is determined by
the concentration of ions
Cathode the ions to be discharged is determined
by the position of the ion in the E.S

Example

Electrolysis of Diluted Hydrochloric Acid

Electrolysis of Concentrated
Hydrochloric Acid

Ions presence at
Anode:
Cl-, OH-

Ions presence at
Anode:
Cl-, OH-

Cathode:
H+

Cathode:
H+

Observation at
Anode:
Colour gas is produced. When a glowing wooden splinter
is inserted into the test tube that contain the gas, the
splinter is rekindled.

Observation at
Anode:
A greenish yellow gas produced. When a blue litmus paper
is inserted into the test tube that contain the gas, the blue
litmus paper turn red and then become colourless.

Cathode
Colour gas is produced. When a lighted wooden splinter is
brought close to the test tube that contain the gas, a
"pop" sound produced..

Cathode
Colour gas is produced. When a lighted wooden splinter is
brought close to the test tube that contain the gas, a
"pop" sound produced.

Half Equation of the Reaction at

Anode:
4OH- 2H2O + O2 + 4e
Cathode:
H+ + 2e H2

Half Equation of the Reaction at

Anode:
2Cl- Cl + 2e
Cathode:
H+ + 2e H2

Note: At anode, the position of hydroxide ion (OH ) is lower

compare to chloride ion (Cl ). However, chloride is selected to be
discharged because its concentration is much higher than he
concentration of hydroxide ion.
-

Additional Note:
Nevertheless, concentration is not a determining factor. It only affect the
selective discharge of the ions which is very close to each other in
electrochemical series
.
The chart below summurises the ions that likely to be selected if they are
presence with hydrogen ions at cathode or hydroxide ions at anode with
high concentration.

Concentration of ions in electrolyte solutions

e-

e-

e-

e+ (anode)

- (cathode)

Carbon
electrode

Carbon
electrode
OHCl-

H+

Cu2+

Concentrated
copper (II) chloride
solution, CuCl2

Concentration of ions in electrolyte solutions

Anode

Cathode

OH- , Cl-

H+ , Cu2+

Cl- are preferred to be

discharged
(Cl- is more concentrated)

Cu2+are preferred to be
discharged
(Cu2+ is below H+ in the ES)

Yellow bubbles gas, Cl2

is released

Brown solid, Cu is formed

Ions that are

attracted

Observation
and
Product
Half equation

2Cl (aq)

Cl2 (g) + 2 e

Cu

2+

(aq) + 2e

Cu (s)

Types of Electrodes
e-

e-

e-

e+ (anode)

- (cathode)

Silver plate

Carbon
electrode

Ag+

Ag+

Ag

Silver nitrate, AgNO3

solution

Types of Electrodes
Anode

Cathode

Ag atom releases one

electron to form Ag+

Ag+ receives one electron to

form metal atoms

Observation
and
Product

The silver plate corrodes

Grey silver solid, Ag is

formed

Half equation

Ag (s)

Ions

Ag (aq) + e

Ag (aq) + e

Ag (s)

Exercises
Electrolysis of copper (II) sulphate, CuSO4, solution using
carbon electrodes
Anode
Ions that are
attracted
Ion that are
prefer to be
discharged

Observation
Product
Half equation

Cathode

Exercises
Electrolysis of concentrated potassium chloride, KCl, solution
using carbon electrodes
Anode
Ions that are
attracted
Ion that are
prefer to be
discharged

Observation
Product

Half equation

Cathode

Exercises
Electrolysis of nickel (II) sulphate, NiSO4, solution using
nickel plate as anode and cathode
Anode
Half equation
Observation

Product

Cathode

Factors that influence electrolysis of

aqueous solutions
POSITION OF IONS
IN THE ELECTROCHEMICAL
SERIES

CONCENTRATION OF IONS
IN THE ELECTROLYTE SOLUTION

TYPES OF ELECTRODES

EXTRACTION OF METALS

USES OF ELECTROLYSIS
IN INDUSTRIES

Reacts with a carbonate

metal
to form carbon OF
PURIFICATION
dioxide gas
(CO2),water
METALS
(H2O) and salt

ELECTROPLATING
OF METALS

Extraction of Sodium

Electrolyte
Molten sodium chloride
NaCl ---> Na+ + ClElectrode:
Anode: Graphite
Cathode: Iron
Chemical Reaction
Anode:
2Cl- ---> Cl2 + 2e
The negative chloride ions are attracted to the anode and then discharged to form
chlorine gas.
Cathode :
Na+ + e ---> Na

Note:
The sodium ions are discharged to form sodium atom.
Due to high temperature, the sodium metal formed is in molten form.
Metal sodium have lower density. Therefore it moves upward and been
collected.

Extraction of Aluminium

Electrolyte:
Molten bauxite (Aluminium Oxide).
Al2O3 2Al3+ + 3O2Electrode:
Anode: Graphite
Cathode: Graphite
Chemical Reaction
Anode:
2O2- O2 + 4e
At the anode, oxygen gas which also has commercial value is
collected.
Cathode
Al3++ + 3e Al
Note:
The aluminium ions are attracted towards the graphite cathode.
The ions is discharged and become molten aluminium metal.

Extraction of Metals
Electrolysis can be used to extract metals from
their ores
Reactive metals that are more reactive than C such
as (K, Na, Ca, Mg, Al) cannot be extracted through
heating of their metal oxides with C
They need to be extracted from their molten ores
using the electrolysis process
In this process:
Electrolyte

The molten ore

Anode

Carbon electrode

Cathode

Carbon electrode

Purification of Metals
Metals that have been extracted from their ores
are normally not pure. They contains impurities
which need to be removed
These metals can be purified by electrolysis
process
In the purification process
Electrolyte

The solution that contains

the metal ions

Anode
Cathode

The impure metal plate

The pure metal plate

Example: Purification of copper

Electrolyte:
Copper(II) sulphate
CuSO4

Cu2+ + SO42-

Electrode:
Anode: Impure copper
Cathode: Pure copper
Chemical Reaction
Anode:
Cu ---> Cu2+ + 2e
In anode, the copper atoms from the electrode are ionised to form
copper(II) ions.

Cathode
Cu2+ ---> Cu + 2e
In cathode, the copper ions are discharged to form copper atom and
then deposit on the surface of the key

Note: Impurities in the copper do not dissolve, and instead fall off the
anode as anode sludge. At the cathode, the copper ions are
deposited as pure copper metal.

Electroplating of Metals
Electroplating is a process to coat an object with a thin
protective layer of metal
Electroplating is used to
(i) making the metal more resistant to corrosion
(ii) making the metal appear more attractive in the
electroplating process
In electroplating,
the anode is the electroplating metal
the cathode is the object to be electroplated
the electrolyte must contain the ions of the plating metal

Example: Electroplate a Key with Copper

Electrolyte:
Copper(II) sulphate
CuSO4 ---> Cu2+ + SO42Electrode:
Anode: Copper
Cathode: Object to be electroplated
Chemical Reaction
Anode:
Cu ---> Cu2+ + 2e
In anode, the copper atoms from the electrode are ionised to form
copper(II) ions.

Note: The anode is then made of the metal we wish to plate with
(copper), and the electrolyte needs to be a solution of a salt of this
metal (copper(II) sulphate).

Cathode
Cu2+ ---> Cu + 2e
In cathode, the copper ions are discharged to form copper atom and
then deposit on the surface of the key
Note: we need to make the cathode the object for plating

Electroplating of Metals
Many types of metals can be plated with other
metals through electrolysis.
The aim of metal plating through electrolysis
includes:
(i) making the metal more resistant to corrosion
(ii) making the metal appear more attractive
In the electroplating process
Electrolyte
Anode

The solution which contains

ions of plating metal
Plating metal

Cathode

Metal to be plated

Example:
Electroplating of a iron spoon with copper
metal

ELECTROLYTIC CELL
e-

e-

e
Carbon
electrode

e-

- (cathode)

+ (anode)

Carbon
electrode

Copper (II)
sulphate
solution

VOLTAIC CELL
e-

e-

V
e-

e-

+ (cathode)

- (anode)

Zn
Cu
Copper (II)
sulphate
Zn (s)

Zn

2+

(aq) + 2e

2+

Cu

(aq) + 2e

Cu (s)

VOLTAIC CELL
Also known as galvanic cell
Has two different metals which are immersed into
an electrolyte and connected by wire
Produces electrical energy from the chemical
reactions occurring inside the cell
Chemical energy

Example : Daniell cell

electrical energy

DANIELL CELL
e-

e-

V
Zn (-)

e-

e-

(Anode)

Cu (+)
(Cathode)

Dilute
H2SO4
(Salt bridge)
ZnSO4
solution
Zn (s)

CuSO4
solution
Zn

2+

(aq) + 2e

2+

Cu

(aq) + 2e

Cu (s)

SALT BRIDGE
Can be made from any electrolyte that does not
react with the electrodes in Daniell Cell
Function :
(i) to allow the flow of the ions so the electric current
is completed
Example:
(i) diluted H2SO4
(ii) sodium nitrate, NaNO3 solution
(iii) Potassium chloride solution, KCl

DANIELL CELL
e-

e-

V
Zn (-)
(Anode)

e-

e-

Cu (+)
(Cathode)

CuSO4
solution
Porous
pot
contains
ZnSO4

Reactivity Series
METALS

K
Na
Ca
Mg
Al
Zn
Fe
Sn
Pb
H
Cu
Ag

MORE
ELECTROPOSITIVE
(negative terminal)

MORE
ELECTRONEGATIVE
(positive terminal)

Anode and Cathode

Anode the electrode where the process of
donation of electrons takes place
Cathode the electrode where the process of
receiving of electrons takes place

ELECTROLYTIC CELL

VOLTAIC CELL

Negative terminal Cathode

Negative terminal Anode

Positive terminal - Anode

Positive terminal - Cathode

ELECTROCHEMICAL SERIES

Electrochemical Series (pg.101)

CATIONS

ANIONS

K
Na+
Ca2+
Mg2+
3+
Al
Zn2+
Fe2+
Sn2+
2+
Pb
H+
Cu2+
Ag+

FSO42NO3ClBrIOH
Tendency to
discharge
increases

ELECTROCHEMICAL
SERIES

An arrangement of metals, based on the

tendency of each metal atom to donate electrons

ELECTROCHEMICAL SERIES
The higher the position of a metal in the
electrochemical series:

More electropositive

The greater the tendency

of the metal atoms to
donate electrons

PRINCIPLES DURING CONSTRUCTING

THE ELECTROCHEMICAL SERIES

Potential differences
between two metals in the
voltaic cell

Ability of a metal to
displace another metal
from its salt solution

Potential differences between two metals in

the voltaic cell
When two different metals are immersed in an electrolyte
solution, a potential difference is generated
The value of the potential difference of a simple voltaic
cell is affected by the position of the metals in the
electrochemical series
The further the two metals in the electrochemical series

The larger the value of the cell voltage is produced

Potential differences between two metals in

the voltaic cell
The metal that is more
electropositive

Located higher in the

electrochemical series

Act as the negative terminal

The metal that is less

electropositive

Located lower in the

electrochemical series

Act as the positive terminal

Potential differences between two metals in

the voltaic cell
Mg
Zn
Pb

3.0 V
1.1 V

0.4 V

Cu
Ag

0.5 V

Predict the negative terminal, positive terminal and cell

voltage of the following voltaic cell
(a) Magnesium and silver

(c) zinc and lead

(b) Magnesium and zinc

(d) zinc and silver

Metal Displacement
A metal that is more electropositive can displace
another metal which is less electropositive from
its salt solution

A metal that is located higher in the electrochemical

series can displace another metal which is located
lower in the electrochemical series from its salt
solution
This reaction displacement reaction

Metal Displacement
Example:
Zinc, Zn can displace copper, Cu, from copper (II) nitrate, Cu(NO3)2
solution
Zn (s) + Cu(NO3)2 (aq)

Zn(NO3)2 (aq) + Cu (s)

Zn is more electropositive than copper

Metal
displaced

Zn can displace Cu from copper (II) nitrate, Cu(NO3)2 solution

The zinc, Zn, will dissolve and brown copper solid, Cu, will form

It can determined the terminals of voltaic cells

IMPORTANCE OF THE
ELECTROCHEMICAL
SERIES

Reacts
with
a carbonate
It can
determined
the
metal
to form carbon
cell voltage
for a pair of
dioxide gasmetals
(CO2),water
(H2O) and salt

It can predicted the

potential of a metal to
displace another metal
from its solution