9.

Electrochemistry
9.1
An electric current is defined as a flow of electrons through a conductor.
Conductors are substances that allow an electric current to pass through them. They include
metals, graphite, ionic compounds which are molten or in aqueous solution (electrolytes), acids
and alkalis.
Non-conductors (insulators) are substances that do not allow an electric current to pass through
them. They include non-metals (except graphite), compounds with only covalent bonding, solid
ionic compounds and plastics.

To determine whether a substance is a conductor or non-conductor, attach it to the crocodile clips

in the circuit above. Turn on the switch. If the bulb lights, the substance is a conductor, and if the
bulb does no light, then the substance is a non-conductor.
9.2
Differences between electric current conduction in metals and electrolytes
Metals Electrolytes
Movement of the “sea” of delocalized Movement of positive and negative ions in
electrons in the metal lattice. When a ionic compounds that are molten or in
potential difference is experienced by a aqueous solution. In the solid state, no
battery, the electrons move in one direction electrical conduction occurs because the ions
from the negative to the positive pole of the are fixed and held by strong ionic bonds in the
battery ionic lattice.
No chemical changes occur when an electric Chemical changes occur when an electric
current passes through. current passes through. The electrolyte
decomposes.
9.3
Strong electrolytes are fully ionized in aqueous solution or when molten, and are good
conductors of electricity. There are high concentrations of ions. These include strong acids,
strong alkalis, and ionic compounds (salts) that are molten or in aqueous solution.
Weak electrolytes are partially ionized in aqueous solution and are poor conductors of electricity.
There are low concentrations of ions. These include weak acids and weak alkalis.
Non-electrolytes are substances which remain as molecules when molten or in aqueous solution.
No ions are present, so no electricity can be conducted. Hence, they are non-conductors. These
include covalent liquids like kerosene, gasoline and ethanol, molten covalent substances like
molten wax, and solutions of covalent substances like glucose and ethanol solutions.
Pure water is an extremely weak electrolyte.
9.4
Electrolysis – This is the chemical decomposition of an electrolyte by the passing of an electric
current through it.
Electrodes – These are the poles through which current enters or leaves an electrolyte.
Cathode – This is the negatively charged electrode. It is connected to the negative terminal of the
power supply. Here, electrons enter the electrolyte and reduction of ions takes place.
Anode – This is the positively charged electrode. It is connected to the positive terminal of the
power supply. Here, electrons leave the electrolyte and oxidation of ions takes place.
Cation – This is a positively charged ion formed when metal atoms lose electrons. They migrate
towards the cathode during electrolysis.
Anion – This is a negatively charged ion formed when non-metal atoms gain electrons. They
migrate towards the anode during electrolysis.
9.5
In an aqueous solution of an electrolyte, the ions present are those from the ionic compound, and
H+ and OH- ions from water.
In a molten electrolyte, the ions present are those from the ionic compound only.
9.6
When an electric current is passed through an electrolyte, cations will drift to the cathode and
anions will drift to the anode.
9.7
The electrochemical series for the different ions are:
Cations Anions
K+ F-
Ca2+ SO42-
Na+ NO3-
Mg2+ Cl-
Al3+ Br-
Zn2+ I-
Fe2+ OH-
Pb2+
H+
Cu2+
Ag+
Au+

The higher the metal cation is in the electrochemical series, the lower is its tendency to gain
electrons to become atoms, that is, the lower is its tendency to be reduced. Alternatively, the
higher the metal atom is in the electrochemical series, the greater is its tendency to lose electrons
to become cations, that is, the greater its tendency to be oxidized or the greater its strength as a
reducing agent.
Metal atoms high in this series displaces metal cations lower than it from their salts.
Eg. Zn (s) + CuSO4 (aq) → ZnSO4 (aq) + Cu (s)
The higher the non-metal atom is in the electrochemical series, the greater its strength as an
oxidizing agent, that is, the greater its tendency to gain electrons to become anions.
Non-metal atoms high in this series displaces non-metal anions lower than it from their salts.
Eg. Cl2 (g) + 2KI (aq) → 2KCl (aq) + I2 (aq)
9.8
When an electric current is passed through an aqueous electrolyte, more than one type of ion
moves towards each electrode. Here, one type of ion is discharged in preference to another. In
the case of more than one cation being present at the cathode, the one that is preferentially
discharged is determined by its position in the electrochemical series. The lower the cation is in
the electrochemical series, the more likely it is to be preferentially discharged as it requires less
energy.
In the case of more than one anion being present at the anode, the one that is preferentially
discharged is determined by:
1. The position of the anion in the electrochemical series – The lower the anion is in the
electrochemical series, the more likely it is to be preferentially discharged as it requires less
energy.
2. Concentration of electrolyte – The greater the concentration of a halide anion (Cl-, Br-, I-), the
more likely it is to be preferentially discharged.
3. Type of electrode – Electrodes can be inert or active. An inert electrode does not take part in
the decomposition reactions of an electrolyte when placed in it. They are made up of inert
materials like graphite (Carbon) or Platinum (Pt). In active electrodes, the electrode influences
what is preferentially discharged.

Electrolysis of different substances

(1) Electrolysis of dilute H2SO4 (aq) using inert graphite electrodes
Ions present: H+ and SO42- ions from H2SO4
H+ and OH- ions from H2O
At the cathode: H+ ions migrate.
2H+ (aq) + 2e- → H2 (g)
[ 4H+ (aq) + 4e- → 2H2 (g) ]
At the anode: SO42- and OH- ions migrate
4OH- (aq) → 2H2O (l) + O2 (g) + 4e-
The OH- ion is preferentially discharged because it is lower in the electrochemical series than
SO42-.
Observations: Colourless, odourless gases evolved at both the cathode and the anode.
2 moles of H2 (g) evolved at the cathode and 1 mole of O2 (g) evolved at the anode
for every 4 moles of e-.
H+ and OH- ions are removed from the electrolyte mixture leaving H+ and SO42-
ions, that is, the H2SO4 (aq) becomes more concentrated.
(2) Electrolysis of dilute NaCl (aq) using inert graphite electrodes
Ions present: Na+ and Cl- ions from NaCl
H+ and OH- ions from H2O
At the cathode: H+ and Na+ ions migrate.
2H+ (aq) + 2e- → H2 (g)
[ 4H+ (aq) + 4e- → 2H2 (g) ]
The H+ ion is preferentially discharged because it is lower in the electrochemical series than Cl-.
At the anode: Cl- and OH- ions migrate
4OH- (aq) → 2H2O (l) + O2 (g) + 4e-
The OH- ion is preferentially discharged because it is lower in the electrochemical series than Cl-
Observations: Colourless, odourless gases evolved at both the cathode and the anode.
2 moles of H2 (g) evolved at the cathode and 1 mole of O2 (g) evolved at the anode
for every 4 moles of e-.
H+ and OH- ions are removed from the electrolyte mixture leaving Na+ and Cl-
ions, that is, the NaCl (aq) becomes more concentrated.
(3) Electrolysis of concentrated NaCl (aq) using inert graphite electrodes
Ions present: Na+ and Cl- ions from NaCl
H+ and OH- ions from H2O
At the cathode: H+ and Na+ ions migrate.
2H+ (aq) + 2e- → H2 (g)
The H+ ion is preferentially discharged because it is lower in the electrochemical series than Cl-.
At the anode: Cl- and OH- ions migrate
2Cl- (aq) → Cl2 (g) + 2e-
The Cl- ion is preferentially discharged because it is a concentrated solution of a halide ion.
Observations: Colourless, odourless gas evolved at the cathode (H2 (g)).
Yellow-green gas evolved at the anode (Cl2 (g)).
H+ and Cl- ions are removed from the electrolyte mixture leaving Na+ and OH-
ions, that is, NaOH (aq) is formed.
(4) Electrolysis of CuSO4 (aq) using inert graphite electrodes
Ions present: Cu2+ and SO42- ions from CuSO4
H+ and OH- ions from H2O
At the cathode: H+ and Cu2+ ions migrate.
Cu2+ (aq) + 2e- → Cu (s)
[ 2Cu2+ (aq) + 4e- → 2Cu (s) ]
The Cu2+ ion is preferentially discharged because it is lower in the electrochemical series than H+
At the anode: SO42- and OH- ions migrate
4OH- (aq) → 2H2O (l) + O2 (g) + 4e-
The OH- ion is preferentially discharged because it is lower in the electrochemical series than
SO42-.
Observations: Pink Cu is deposited on the cathode causing it to increase in size.
The blue colour of the electrolyte gradually fades as Cu2+ ions are removed.
Colourless, odourless gas evolved at the anode (O2 (g)).
Cu2+ and OH- ions are removed from the electrolyte mixture leaving H+ and
SO42- ions, that is, H2SO4 (aq) is formed.
(5) Electrolysis of CuSO4 (aq) using active Cu electrodes
Ions present: Cu2+ and SO42- ions from CuSO4
H+ and OH- ions from H2O
At the cathode: H+ and Cu2+ ions migrate.
Cu2+ (aq) + 2e- → Cu (s)
The Cu2+ ion is preferentially discharged because it is lower in the electrochemical series than H+
At the anode: SO42- and OH- ions migrate
Cu (s) → Cu2+ (aq) + 2e-
The Cu anode becomes ionized because it is an active electrode and the production of Cu2+ ions
is the least energetic reaction that can occur at the anode.
Observations: Pink Cu is deposited on the cathode causing it to increase in size.
The Cu anode decreases in size
The electrolyte is unchanged.
(6) Electrolysis of PbBr2 (l) using inert graphite electrodes
Ions present: Pb2+ and Br- from PbBr2
At the cathode: Pb2+ ions migrate
Pb2+ (l) + 2e- → Pb (l)
At the anode: Br- ions migrate
2Br- (l) → Br2 (g) + 2e-
Observations: Pb (l) falls to the base of the electrolysis container at the cathode.
Red-brown gas of Br2 evolved at the anode.

Flow of electrons

Oxidation – Anions lose electrons Reduction – Cations gain electrons

9.9
Faraday discovered that the mass of a substance discharged at an electrode during electrolysis is
directly proportional to the quantity of electricity flowing through the electrolytic cell (m α Q).
Q – The quantity of electrical charge in Coulombs (C).
Coulomb – The quantity of electrical charge that passes a given point in a wire when an electric
current of one ampere flows for one second.
Current – The rate of flow of electric charge in Amperes (A).
Quantity of electric charge (C) = Current (A) x Time (s) or Q = It
The Faraday constant (F) is the total electric charge carried by one mole of electrons (6 x 1023
electrons) and has an approximate value of 96,500 C mol-1 of electrons.
If 1 mole of singly charged ions is discharged at an electrode, 96,500 C of electricity is required
to add or remove 1 mole of electrons.
M+ + e- → M or X- → X + e- (where M is a metal and X is a non-metal)
96,500 C required because 1 mole of electrons involved.
If 1 mole of doubly charged ions is discharged at an electrode, 2 x 96,500 C of electricity is
required to add or remove 2 moles of electrons.
M2+ + 2e- → M or X2- → X + 2e- (where M is a metal and X is a non-metal)
2 x 96,500 C = 193,000 C required because 2 moles of electrons involved.
9.10
Example #1
A solution of CuSO4 (aq) is electrolyzed using inert graphite electrodes. Find the mass of Copper
deposited on the cathode when a current of 2A is passed through the electrolyte for 6 hours, 42
minutes and 5 seconds.
Q = It = 2A x [(6 x 60 x 60) + (42 x 60) + 5] s = 2A x 24,125 s = 48,250 C
At the cathode: Cu2+ (aq) + 2e- → Cu (s)
2 x 96,500 C discharge 1 mole Cu
∴ 48,250 C will discharge [1 ÷ (2 x 96,500)] x 48,250 = 0.25 mol Cu
Mass of Cu deposited = 0.25 mol x 64g = 16g

Example #2
Calculate the volume of Oxygen produced at the anode at rtp if an electric current of 5.0 A is
passed through dilute NaCl (aq) for 3 hours, 51 minute and 36 seconds.
Q = It = 5A x [(3 x 60 x 60) + (51 x 60) + 36] = 5A x 13,896 s = 69,480 C
At the anode: 4OH- (aq) → 2H2O (l) + O2 (g) + 4e-
4 x 96,500 C discharge 1 mol O2 (g)
∴ 69,480 C will discharge [1 ÷ (4 x 96,500)] x 69,480 = 0.18 mol O2 (g)
At rtp, 1 mol O2 occupies 24 dm3
∴ 0.18 mol O2 will occupy 24 x 0.18 = 4.32 dm3

9.11
Industrial applications of electrolysis
(a) Metallic extraction based on position in the electrochemical series.
Electrolysis is used to extract metals high in the electrochemical series like Aluminium and
metals above it, from their molten ores. As these metals are high in the series, the strong method
of electrolysis is needed to reduce the metal cations in the ore to form the pure metal.
Eg. For Al, the ore is bauxite, which contains Al2O3. As Al is high in the electrochemical series,
a strong reduction method is needed to produce pure Al. Therefore, when molten Al2O3 is
electrolyzed: At the Cathode: Al3+ + 3e- → Al (l)
(b) Purification
Electrolysis can be used to purify an impure metal. This is called electro-refining. The cathode is
the pure metal, the anode is the impure metal and the electrolyte is an aqueous solution
containing the metal cations being purified.
Eg. In the purification of Cu, electrolysis is carried out where the cathode is pure Copper, the
anode is the impure Copper and the electrolyte is CuSO4 (aq).
At the Cathode: Cu2+ (aq) + 2e- → Cu (s)
At the Anode: Cu (s) → Cu2+ (aq) + 2e-
Pure Copper is deposited on the cathode making it bigger. The Copper in the impure Copper
anode is ionized to Cu2+ (aq) leaving the impurities behind which fall below the anode. The
electrolyte remains unchanged.
(c) Electroplating
Electroplating is the process of coating one metal with a layer of another metal by electrolysis.
This is done to protect the covered metal from corrosion, to make the original metal more
attractive, and to make an expensive object more inexpensive while having similar appearances
to each other. The cathode is the object to be plated. The anode is the pure plating metal. The
electrolyte is an aqueous solution containing the metal cations of the plating metal. Only metals
lower than Hydrogen in the electrochemical series can be used for electroplating.
Eg. For Nickel plating, the cathode is cleaned object to be plated, the anode is pure Nickel and
the electrolyte is NiSO4 (aq). For Silver plating, the cathode is the cleaned object to be plated, the
anode is pure Silver and the electrolyte is AgNO3 (aq). For Chromium plating, the cathode is the
cleaned object to be plated, the anode is pure Chromium and the electrolyte is Chromic (VI)
Acid solution (CrO3 (aq)) with Cr2(SO4)3 (aq).

(d) Anodising
Anodising is the process by which the thickness of the protective and unreactive Aluminium
Oxide layer covering Aluminium is increased. When exposed to air, Al reacts with Oxygen
forming Al2O3, which evenly coats and adheres to the Al metal underneath it. Therefore, the Al
is protected from further corrosion. This Oxide layer can also be coloured as it readily absorbs
dyes. The cathode is any inert electrode like graphite or Platinum. The anode is made of the pure
Al object to be anodized. The electrolyte is dilute H2SO4.
At the anode: 2Al (s) + 3H2O (l) → Al2O3 (s) + 6H+ (aq) + 6e-
At the cathode: 6H+ (aq) + 6e- → 3H2 (g)