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Electrolysis: An

Introduction
VCE Chemistry
Unit 4: Chemistry at Work
Area of Study 2 Using Energy

Electrolysis
During electrolysis, electrical energy is converted into
chemical energy.
This is the reverse of the process that occurs in a
galvanic cell where spontaneous reactions are a source
of electrical energy.
Electrolysis has a variety of industrial applications.
These include electroplating and electrorefining as
well as the recharging secondary cells.
Non-spontaneous reactions are forced to occur in
electrolytic cells by passing an electric current from an
external power source through an electrolyte.
The potential energy of the system is increased as
electrical energy is forced into the cell.

Galvanic & Electrolytic Cells - A Comparison


In galvanic cells the reactions are separated so electrons can be
used as they are transferred.
Electrolytic cells have two electrodes and an electrolyte.
Electrolytic cells differ from galvanic cells in that the
anode is the positive electrode while the cathode is the
negative electrode.
The polarities of the anode and cathode change because in
galvanic cells the polarity is imposed by the reactions
themselves.
At the anode, electrons are produced and at the cathode
electrons are consumed.
In electrolytic cells the polarity is imposed by the power source.
This pulls electrons from the anode and forces electrons onto
the cathode.

Electrolytic Cells

Regardless of which cell, electron flow is


always the same from anode to
cathode!
Oxidation always occurs at the anode
and reduction always occurs at the
cathode!

Electrolytic Cells

Predicting Electrolytic Reactions


When electrons are forced into the cell, the oxidants
present at the surface of the electrode compete with
one another to accept them.
The strongest of the oxidants present preferentially
accepts the electrons and is discharged, i.e. the
oxidant highest on the electrochemical series accepts
the electrons.
Similarly, at the anode where the electrons are being
withdrawn, the reductants present at the anode
surface compete to donate electrons.
The strongest of the reductants is preferentially
discharged.

Predicting Electrolytic Reactions


Note that if two competitors have very similar E
values, they will probably both be discharged
simultaneously.
In aqueous solutions, the water may be involved in
either the oxidation or the reduction reaction or both.

Predicting Electrolytic Reactions - Questions


Predict the products at each electrode during
electrolysis for the following 1 M solutions (unreactive
electrodes used) . The nitrate ion is not involved in
any of the reactions.
a. Copper(II) bromide
b. Sodium iodide
c. Lead nitrate
d. Zinc chloride
e. Aluminium nitrate

Predicting Electrolytic Reactions - Solutions


a. 1 M copper(II) bromide
Species present at the electrodes are Cu 2+ (aq), Br- (aq) and
H2O (l)
Possible reductions:
Cu2+ (aq) + 2e- Cu (s)

+0.34 V

2H2O (l) + 2e- H2 (g) + 2OH- (aq)

-0.83 V

Here the strongest oxidant (most positive E o value) is Cu2+.


Thus, at the cathode Cu forms.
Possible oxidations:
Br2 (g) + 2e- 2Br- (aq)

+1.09 V

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

+1.23 V

Here the strongest reductant (least positive E o value) is 2Br-.


Thus at the anode Br2 forms.
Overall equation: Cu2+ (a) + 2Br- (aq) Cu (s) + Br2 (g)

Predicting Electrolytic Reactions - Solutions


b. 1 M sodium iodide
Species present at the electrodes are Na+ (aq), I- (aq) and H2O (l)
Possible reductions:
Na+ (aq) + e- Na (s)

-2.71 V

2H2O (l) + 2e- H2 (g) + 2OH- (aq)

-0.83 V

The strongest oxidant (most positive Eo value) is H2O.


Thus at the cathode H2 and 2OH- form.
Possible oxidations:
I2 (g) + 2e- 2I- (aq)

+0.54 V

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

+1.23 V

The strongest reductant (least positive E o value) is 2I-.


Thus at the anode I2 forms.
Overall equation: 2H2O (l) + 2I- (aq) H2 (g) + 2OH- (aq)
+ I2 (g)

Predicting Electrolytic Reactions - Solutions


c. 1 M lead(II) nitrate
Species present at the electrodes are Pb 2+ (aq) and H2O (l)
Possible reductions:
Pb2+ (aq) + 2e- Pb (s)

+0.13 V

2H2O (l) + 2e- H2 (g) + 2OH- (aq)

-0.83 V

The strongest oxidant (most positive E o value) is Pb2+.


Thus, at the cathode Pb forms.
Possible oxidations:
O2 (g) + 4H+ (aq) + 4e- 2H2O (aq)

+1.23 V

The strongest reductant (least positive E o value) is 2H2O.


Thus at the anode O2 and 4H+ form.
Overall equation: 2Pb2+ (aq) + 2H2O (l) 2Pb (s) + O2
(g) + 4H+ (aq)

Predicting Electrolytic Reactions - Solutions


d. 1 M zinc chloride
Species present at the electrodes are Zn2+ (aq), Cl- (aq) and H2O (l)
Possible reductions:
Zn2+ (aq) + 2e- Zn (s)

-0.76 V

2H2O (l) + 2e- H2 (g) + 2OH- (aq)

-0.83 V

The strongest oxidant (most positive Eo value) is Zn2+.


Thus, at the cathode Zn forms.
Possible oxidations:
Cl2 (g) + 2e- 2Cl- (aq)

+1.36 V

O2 (g) + 4H+ (aq) + 4e- H2O (l)

+1.23 V

The strongest reductant (least positive Eo value) is 2H2O.


Thus at the anode O2 and 4H+ form.
Overall equation: 2Zn2+ (aq) + 2H2O (aq) 2Zn (s) + O2 (g) +
4H+ (aq)

Predicting Electrolytic Reactions - Solutions


e. 1 M aluminium nitrate
Species present at the electrodes are Al3+ (aq) and H2O (l)
Possible reductions:
Al3+ (aq) + 3e- Al (s)

-1.71 V

2H2O (l) + 2e- H2 (g) + 2OH- (aq)

-0.83 V

The strongest oxidant (most positive Eo value) is 2H2O.


Thus at the cathode H2 and 2OH- form.
Possible oxidations:
O2 (g) + 4H+ (aq) + 4e- 2H2O (aq)

+1.23 V

The strongest reductant (least positive Eo value) is 2H2O.


Thus at the anode O2 and 4H+ form.
Overall equation: 6H2O (l) 2H2 (g) + 4OH- (aq) + O2
(g) + 4H+ (aq)

Applied Electrolysis - Electroplating


In this application, the cathode is coated with a thin layer
of metal from a solution containing ions of the metal.
This is done to improve the appearance or to prevent
corrosion by the application of a protective layer.
The object to be plated is attached to the negative terminal
of a power supply and becomes the cathode.
It is then placed in an electrolyte solution containing ions of
the metal that forms the plating.
The anode is made from the metal that is to form the
plating.
To ensure the coating on the surface is strongly bonded and
smooth, the electrolyte is a complex mixture of ions and
the conditions (voltage, current, time) carefully controlled.

Applied Electrolysis - Electroplating

Applied Electrolysis - Electrorefining


Metals can be purified by electrolysis.
The impure metal is used as the anode and oxidised.
Metals that are stronger reductants will also be discharged
at the electrode surface.
Any constituents of the anode that are weaker reductants
are not oxidised but fall as uncharged metal atoms to the
bottom of the cell.
This leaves an electrolyte solution containing ions of the
metal to be refined and a small amount of other ions.
The mixture of metal ions in solution compete for electrons
at the cathode surface.
As the dissolved impure ions are weaker oxidants, the
metal to be refined is preferentially reduced at the
cathode, and is in a much purer form.

Applied Electrolysis - Electrorefining

Applied Electrolysis
Sodium from Molten Sodium Chloride The Downs Cell

Applied Electrolysis
Sodium from Molten Sodium Chloride The Downs Cell
Products

Sodium metal and chlorine gas must be


kept separate otherwise they will
spontaneously react

Anode reaction
Cathode reaction
Overall reaction

2Cl- (l) Cl2 (g) + 2eNa+ (l) + e- Na (l)


2Na (l) + 2Cl- (l) 2Na (l) + Cl2 (g)

Anode (+)
Cathode (-)

Carbon in centre of cell


Cylindrical iron near edge of the cell

Conditions

Molten NaCl and CaCl2 electrolyte added to the


melt to lower the melting point from 801oC to
below 600oC
7 Volts, 30 000 Amps, electric current melts
electrolyte

Applied Electrolysis
Aluminium from Molten Alumina
The Hall-Hroult Process

Applied Electrolysis
Aluminium from Molten Alumina
The Hall-Hroult Process
Products

Aluminium metal and carbon dioxide gas must be


kept separated otherwise they will spontaneously
react

Anode reaction
Cathode reaction
Overall reaction

C (s) + 2O2- (l) CO2 (g) + 4eAl3+ (l) + 3e- Al (l)


2Al2O3 (l) + 3C (s) 4Al (l) + 3CO2 (g)

Anode (+)
Cathode (-)

Graphite, lowered into top of cell and consumed during


reaction
Graphite lining and aluminium metal at the bottom of the
cell

Conditions

Al2O3 dissolved in cryolite, Na3AlF6, which lowers the melt


point of alumina from 2045oC to ~1000oC
5 Volts, 150 000 Amps, electric current melts electrolyte

Applied Electrolysis
Sodium Hydroxide and Chlorine from Brine
The Membrane Cell

Applied Electrolysis
Sodium Hydroxide and Chlorine from Brine
The Membrane Cell
Products

Sodium hydroxide, chlorine gas and hydrogen


gas must be kept separated otherwise they will
spontaneously react

Anode reaction
Cathode reaction
Overall reaction

2Cl- (l) Cl2 (g) + 2e2H2O (l) + 2e- H2 (g) + 2OH- (aq)
2H2O (l) + 2Cl- (l) H2 (g) + 2OH- (aq) + Cl2 (g)

Anode (+)
Cathode (-)

Graphite
Steel mesh

Conditions

Cells separated by plastic semipermeable membrane


that prevents mixing of products and allows Na+ ions
to migrate but neither Cl- or OH- ions. Ensures a purer
NaOH solution.
3.5 5 Volts, up to 80 000 Amps, electric current
heats electrolyte

Faradays Laws of Electrolysis


If you wished to electroplate an object, you might ask
yourself the following questions:
How can I determine how much metal is being
plated?
How long should I leave the object being plated in the
electroplating cell?
What size electric current should be used?

Faradays Laws of Electrolysis


Michael Faraday was a 19th century English chemist.
His studies yielded two laws relating amount of
electric current and the chemicals produced by the
current or used to produce it.
These laws enable us to:
Work out the amount of energy required to discharge
a metal ion and place it out on an object or
To calculate the amount of metal produced in an
electrolytic cell.

Faradays Laws of Electrolysis First Law


The mass of metal produced at the cathode is directly
proportional to the quantity of electricity passed through
the cell
mQ
Electric charge, Q, is measured using the unit coulomb.
The electric charge passing through a cell may be
calculated from measurements of the current, I, through
the cell and the time, t, for which the current flows.
Charge (coulombs) = current (amps) x time
(seconds)
Q = It

Faradays Laws of Electrolysis Second Law


In order to produce one mole of metal, one two or
three moles of electrons must be consumed.
Faraday found that there was a certain charge
associated with one mole of electrons.
This amount of charge is now called the Faraday
and is equivalent to 96 487 (96 500) Coulomb.
1 Faraday = 96 500 Coulomb

Faradays Laws of Electrolysis Second Law


In order to produce one mole of metal, one two or
three moles of electrons must be consumed.
Ag+ (aq), Cu2+ (aq) and Cr3+ (aq) require 1, 2 and 3
moles of electrons for discharge.
The quantity of electricity required will be:
Amount of charge = no. of moles of metal
ions x charge
on an ion x 1 Faraday
Q = nzF

and

It = nzF

Q = It

Faradays Laws of Electrolysis Questions


1. Calculate the number of mole of copper produced in an
electrolytic cell if a current of 5.0 A at a voltage of 6.0 V
flows through a solution of copper ions for 10 minutes.
2. Calculate the time taken to deposit 1.00 g of copper onto
an object that is placed in a solution of copper nitrate,
Cu(NO3)2, and has a current of 2.50 A flowing through it.
3. In an operating Hall-Hroult cell, a current of 150 000 A is
used at 5.0 V. Calculate the mass of aluminium that would
be produced if this cell operates continuously for 1 day.
4. The electrolysis of a solution of chromium ions using a
current of 2.2 A for 25 minutes produced 0.60 g of
chromium. Calculate the charge on the chromium ion.
5. Calculate the masses of metal produced when 600
Faraday of charge is used to reduce the ions of
aluminium, silver and zinc.

Faradays Laws of Electrolysis Solutions


1. n (Cu) = I t / z F
n (Cu) = 5.0 x 10 x 60 / 2 x 96 500
n (Cu) = 1.6 x 10-2 mol
That is, 1.6 x 10-2 mole of copper would be produced
2. t = n (Cu) z F / I
t = (1.00 / 63.5) x 2 x 96 500 / 2.5
t = 1216 seconds
That is, it takes 20 minutes 15 seconds to deposit
1.00 g of copper
3. n (Al) = I t / z F
n (Al) = 150 000 x 24 x 60 x 60 / 3 x 96 500
n (Al) = 44 767 mol
m (Al) = 44 767 x 27 = 1 208 705 g
That is, 1.2 tonne of aluminium is produced per day

Faradays Laws of Electrolysis Solutions


4. z (Cr) = I t / n F
z (Cr) = 2.2 x 25 x 60 / (0.60 / 52) x 96 500
z (Cr) = 2.96
As the charge on an ion is a small integer, it must be
3+.
The ion is Cr3+.
5. Q = m z F / M
As Q = 600 F, then m = 600 M / z
m (Al) = 600 x 27 / 3 = 5400 g
m (Ag) = 600 x 107.9 / 1 = 64 740 g
m (Zn) = 600 x 65.4 / 2 = 19 620 g
The same 600 F of charge would produce different
masses of these metals; 5.4 kg of Al, nearly 20 kg of
Zn and almost 65 kg of Ag.

Faradays Laws of Electrolysis Application


Q. Australia leads the world in the per capita recycling of
aluminium. Explain why the production of aluminium
uses so much energy and therefore why it is so much
better to recycle aluminium.
A. Aluminium is a reactive metal - its low on the
electrochemical series. The only method of reducing Al
ions is electrolytically, hence the energy costs will be
quite high. Because Al is so low on the electrochemical
series, most other reactions will occur more easily - any
water present would be reduced in preference to Al.
From Faradays Second Law, no. of moles of Al is
inversely related to the charge of Al. Thus more charge is
required to produce Al than almost any other metal. Mass
of Al produced per mole of charge depends directly on
the molar mass of Al. Al has the lowest molar mass of the
commonly used industrial metals.