ELECTROCHEMISTRY

CHEMICAL
SUBSTANCES
ELECTROLYTES NON-ELECTROLYTES
Substances that can conduct
electricity when they are in
molten state or aqueous and
undergo chemical changes
Substances that cannot
conduct electricity either in
molten state or aqueous
Example:
Ionic substances
(i) Dilute acid solution
(ii) Dilute alkaline solution
(iii) Molten salts
(iv) Aqueous salt solution
Example:
Covalent substances
(i) Naphthalene
(ii) Sugar solution
(iii) Latex
(iv) Hydrogen chloride in organic
solvents
Heat
Molten lead (II) iodide
Bulb
Carbon
electrodes
Heat
Solid lead (II) iodide
Carbon
electrodes
Bulb
.

. ..
..
. .
.
. .
. . . .
.
. .
.
.
switch
switch
Do not conduct
electricity
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

I
-
Pb
2+
Pb
2+
Pb
2+
I
-
I
-
I
-
I
-
I
-
Pb
2+
Pb
2+
Pb
2+
Pb
2+
Solid lead (II) iodide
IN A SOLID STATE
Molten lead (II) iodide
I
-
Pb
2+
Pb
2+
Pb
2+
I
-
I
-
Can conduct
electricity
This is because the
presence of moving
ions. The ions are
free to move in the
molten or aqueous
solution

IN A MOLTEN STATE
ELECTROLYTES AND NON
ELECTROLYTES
Classify the following chemicals into electrolytes or non-
electrolytes

Potassium chloride, KCl solution
Molten lead (II) bromide, PbBr
2
Glucose solution
Trichloromethane
Molten zinc oxide, ZnO
Sodium chloride, NaCl solution
Ammonia in tetrachloromethane



A process of breaking down the chemical
compounds into their constituent elements using
electric current
Example:
Molten aluminium oxide (I) aluminium (s) + oxygen (g)

Copper (II) chloride (aq) copper (s) + chlorine (g)
Electric current
Electric current
ELECTROLYSIS
ELECTROLYTIC CELL
Electrolyte
e
-
e
-
e
-
e
-
Electrode
Electrode
- (cathode) + (anode)
..
. .. .
.. . ..
...
- +
Anion Cation
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
ELECTROLYTIC CELL
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

During electrolysis:
ELECTROLYSIS OF MOLTEN
COMPOUNDS
QUESTIONS
(a) Molten zinc chloride (I)
(b) Molten aluminium (III) bromide
(c) Molten zinc (II) iodide
(d) Molten lead (II) oxide
Electric current
Electric current
Electric current
Electric current
Example 1
Molten Potassium
Iodide, KI
e
-
e
-
e
-
e
-
Carbon
electrode
Carbon
electrode
- (cathode) + (anode)
..
. .. .
.. . ..
...
The ions that presents in electrolyte are:
(i) Anion:
(ii) Cation:
Example 2
e
-
e
-
e
-
e
-
Carbon
electrode
Carbon
electrode
- (cathode) + (anode)
..
. .. .
.. . ..
...
The ions that presents in electrolyte are:
(i) Anion:
(ii) Cation:
Molten zinc oxide,
ZnO
Example 3
e
-
e
-
e
-
e
-
Carbon
electrode
Carbon
electrode
- (cathode) + (anode)
..
. .. .
.. . ..
...
The ions that presents in electrolyte are:
(i) Anion:
(ii) Cation:
Molten lead (II)
bromide, PbBr
2
Example 4
e
-
e
-
e
-
e
-
Carbon
electrode
Carbon
electrode
- (cathode) + (anode)
..
. .. .
.. . ..
...
The ions that presents in electrolyte are:
(i) Anion:
(ii) Cation:
Molten lead (II) oxide,
PbO

Example 5
e
-
e
-
e
-
e
-
Carbon
electrode
Carbon
electrode
- (cathode) + (anode)
..
. .. .
.. . ..
...
The ions that presents in electrolyte are:
(i) Anion:
(ii) Cation:
Molten zinc (II)
chloride, ZnCl
2
ELECTROLYSIS OF MOLTEN
COMPOUND
e
-
e
-
e
-
e
-
Carbon
electrode
Carbon
electrode
- (cathode) + (anode)
..
. .. .
.. . ..
...
The ions that presents in electrolyte are:
(i) Anion:
(ii) Cation:
Molten lead (II)
bromide, PbBr
2
Molten lead (II)
bromide
e
-
e
-
e
-
e
-
Carbon
electrode
Carbon
electrode
- (cathode) + (anode)
..
. .. .
.. . ..
...
Pb
2+
Pb
2+
Pb
2+
Pb
2+
Br
-
Br
-
Br
-
Br
-
ELECTROLYSIS OF MOLTEN
COMPOUND
Pb
2+
are attracted to the cathode
Br
-
are attracted to anode

Br
-
discharge by releasing electrons to the
anode
CATHODE
(NEGATIVE ELECTRODE)
ANODE
(POSITIVE ELECTRODE)
Br
-
Br + e
-

Neutral atoms form and combine to form
neutral bromine molecules
Br + Br Br
2
(g)
The half reaction at anode can be
represented by the half equation



2Br
-
(l) Br
2
(g) + 2e
-

Pb
2+
discharge by receiving electrons
(provided by the battery) at the cathode
to form neutral lead atoms
Pb
2+
(l) + 2e
-
Pb (s)
The half reaction at cathode can be
represented by the half equation



The Half Equation:

Cathode:
Anode:

Overall Equation:




2Br
-
(l) Br
2
(g) + 2e
-

Pb
2+
(l) + 2e
-
Pb (s)
Pb
2+
(l) + 2Br
-
(l) Pb(s) + Br
2
(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, ZnCl
2
(C) Molten lead (II) oxide, PbO
ELECTROLYSIS OF AQUEOUS
SOLUTION
Water molecules in an aqueous solution can slightly dissociate to
produce H
+
and OH
-
H
2
O H
+
(aq) + OH
-
(aq)
So, aqueous solution contains H
+
and OH
-
and electrolyte ions
Examples:

Aqueous Solution
Ions present
Anion Cation
NaCl solution Cl
-
, OH
-
Na
+
, H
+
CuSO
4
solution
HNO
3
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
Types of
electrodes
Concentration of ions
in the electrolyte
Electrochemical Series (pg.101)
CATIONS

K
+

Na
+
Ca
2+
Mg
2+
Al
3+
Zn
2+
Fe
2+
Sn
2+
Pb
2+
H
+
Cu
2+
Ag
+


Tendency to
discharge
increases
ANIONS

F
-
SO
4
2
-
NO
3
-
Cl
-
Br
-
I
-
OH
-

Positions of the ions
in the electrochemical series
Copper (II) chloride
solution, CuCl
2
e
-
e
-
e
-
e
-
Carbon
electrode
Carbon
electrode
- (cathode) + (anode)
H
+
Cu
2+
Cu
2+
H
+
Cl
-
Cl
-
OH
-
OH
-
Positions of the ions
in the electrochemical series
Observation
and
Product

H
+
, Cu
2+
Cu
2+
are preferred to be
discharged
(Cu
2+
is below H
+
in the ES)
OH
-
, Cl
-
OH
-
are preferred to be
discharged
(OH
-
is below Cl
-
in the ES)
Ions that are
attracted
Cathode Anode
Bubbles of gas, O
2

is released
Brown solid, Cu is formed
Half equation
4OH
-
(aq) 2H
2
O (l) + O
2
(g)
+ 4 e
-
Cu
2+
(aq) + 2e
-
Cu (s)


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
Concentration of ions in
electrolyte solutions
Concentrated
copper (II) chloride
solution, CuCl
2
e
-
e
-
e
-
e
-
Carbon
electrode
Carbon
electrode
- (cathode) + (anode)
Cu
2+
H
+
Cl
-
OH
-
Concentration of ions in
electrolyte solutions

Observation
and
Product

H
+
, Cu
2+

Cu
2+
are preferred to be
discharged
(Cu
2+
is below H
+
in the ES)
OH
-
, Cl
-

Cl
-
are preferred to be
discharged
(Cl
-
is more concentrated)
Ions that are
attracted
Cathode Anode
Yellow bubbles gas, Cl
2

is released
Brown solid, Cu is formed
Half equation
2Cl
-
(aq) Cl
2
(g) + 2 e
-
Cu
2+
(aq) + 2e
-
Cu (s)


Types of Electrodes
Silver nitrate, AgNO
3

solution

e
-
e
-
e
-
e
-
Silver plate
Carbon
electrode
- (cathode) + (anode)
Ag
+
Ag

Ag
+
Types of Electrodes
Ag
+
(aq) + e
-
Ag (s)


Observation
and
Product

Ag
+
receives one electron to
form metal atoms

Ag atom releases one
electron to form Ag
+
Ions
Cathode Anode
The silver plate corrodes
Grey silver solid, Ag is
formed
Half equation
Ag (s) Ag
+
(aq) + e
-
Exercises
Electrolysis of copper (II) sulphate, CuSO
4
, solution
using carbon electrodes
Anode Cathode
Ions that are
attracted
Ion that are
prefer to be
discharged
Observation
Product
Half equation
Exercises
Electrolysis of concentrated potassium chloride, KCl,
solution using carbon electrodes
Anode Cathode
Ions that are
attracted
Ion that are
prefer to be
discharged
Observation
Product
Half equation
Exercises
Electrolysis of nickel (II) sulphate, NiSO
4
, solution
using nickel plate as anode and cathode







Anode Cathode
Half equation
Observation
Product
Factors that influence electrolysis of
aqueous solutions
TYPES OF ELECTRODES
POSITION OF IONS
IN THE ELECTROCHEMICAL
SERIES
CONCENTRATION OF IONS
IN THE ELECTROLYTE SOLUTION
USES OF ELECTROLYSIS
IN INDUSTRIES
Reacts with a carbonate
metal to form carbon
dioxide gas (CO
2
),water
(H
2
O) and salt
ELECTROPLATING
OF METALS
EXTRACTION OF METALS
PURIFICATION OF
METALS
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
Example:
Extraction of aluminium from electrolysis
of molten aluminium oxide, Al
2
O
3

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 The impure metal plate
Cathode The pure metal plate
Example:
Purification of copper
The anode is a impure copper.
The cathode is a pure copper.
When electricity is passed through the cell, the copper is
dissolved at anode where Cu
2+
ions go into solution.
Anode copper becomes thinner.



At cathode, copper ions are selectively discharge and
deposited. Cathode copper becomes thicker.

Purification of copper
The blue intensity of solution remains unchanged
because concentration of copper (II) ions in the solution
remains unchanged. The rate at which copper enter into
electrolyte from anode is equal to the rate at which the
copper ions discharged at cathode
Purification of Metals
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 The solution which contains
ions of plating metal
Anode Plating metal
Cathode Metal to be plated
Example:
Electroplating of a iron spoon with silver
metal
Anode :pure plating metal
Cathode: object to be plated
Copper (II)
sulphate
solution
ELECTROLYTIC CELL
e
-
e
-
e
-
e
-
Carbon
electrode
Carbon
electrode
- (cathode)
+ (anode)
VOLTAIC CELL
Cu
Copper (II)
sulphate
V
e
-
e
-
e
-
e
-
- (anode)
+ (cathode)
Zn
Zn (s) Zn
2+
(aq) + 2e
-
Cu
2+
(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


Example : Daniell cell
Chemical energy electrical energy

DANIELL CELL
V
Dilute
H
2
SO
4
(Salt bridge)
Zn (-) Cu (+)

CuSO
4

solution
ZnSO
4

solution
(Anode) (Cathode)
e
-
e
-
e
-
e
-
Zn (s) Zn
2+
(aq) + 2e
-
Cu
2+
(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 H
2
SO
4
(ii) sodium nitrate, NaNO
3
solution
(iii) Potassium chloride solution, KCl
DANIELL CELL
V
Porous
pot
contains
ZnSO
4
Zn (-) Cu (+)
CuSO
4
solution
(Anode)
(Cathode)
e
-
e
-
e
-
e
-
Reactivity Series

K


Na

Ca

Mg

Al

Zn

Fe

Sn

Pb

H

Cu

Ag



METALS
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
Negative terminal Cathode
Positive terminal - Anode
Negative terminal Anode
Positive terminal - Cathode
ELECTROLYTIC CELL
VOLTAIC CELL
ELECTROCHEMICAL SERIES
Electrochemical Series (pg.101)
CATIONS

K
+

Na
+
Ca
2+
Mg
2+
Al
3+
Zn
2+
Fe
2+
Sn
2+
Pb
2+
H
+
Cu
2+
Ag
+


Tendency to
discharge
increases
ANIONS

F
-
SO
4
2
-
NO
3
-
Cl
-
Br
-
I
-
OH
-

ELECTROCHEMICAL
SERIES
An arrangement of metals, based on the
tendency of each metal atom to donate electrons
The higher the position of a metal in the
electrochemical series:
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
The value of the potential difference of a simple voltaic
cell is affected by the position of the metals in the
electrochemical series
When two different metals are immersed in an electrolyte
solution, a potential difference is generated
The larger the value of the cell voltage is produced
The further the two metals in the electrochemical series

Potential differences between two
metals in the voltaic cell


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
Cu
Ag
3.0 V
1.1 V
0.4 V
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
This reaction displacement reaction
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
Metal Displacement
Example:
Zinc, Zn can displace copper, Cu, from copper (II) nitrate, Cu(NO
3
)
2
solution
Zn (s) + Cu(NO
3
)
2
(aq) Zn(NO
3
)
2
(aq) + Cu (s)


Zn is more electropositive than copper
Zn can displace Cu from copper (II) nitrate, Cu(NO
3
)
2
solution
The zinc, Zn, will dissolve and brown copper solid, Cu, will form



Metal
displaced
IMPORTANCE OF THE
ELECTROCHEMICAL
SERIES
Reacts with a carbonate
metal to form carbon
dioxide gas (CO
2
),water
(H
2
O) and salt
It can determined the terminals of voltaic cells
It can determined the
cell voltage for a pair of
metals
It can predicted the
potential of a metal to
displace another metal
from its solution