Chapter 12

Electrochemistry

LEARNING OUTCOMES
 Describe investigations leading to the classification of substances as
conductors or non-conductors
 Distinguish between metallic and electrolytic conduction
 Define electrolysis, cathode, anode, cation and anion
 Define electrolytes as strong and weak based on their conductivity
 Predict the electrode to which an ion will drift
 Define oxidation and reduction reactions including reactions at
electrodes
 Predict chemical reactions making use of electrochemical series
 Identify ions present in electrolytes
 Discuss the electrolysis of certain substances
 Define Faraday constant
 Calculate the masses and volumes of substances liberated during
electrolyses
 Describe industrial applications of electrolysis
 Chapter 12
Electrochemistry

Conductors and electrolytes

 The movement of electrically charged particles through a medium
constitutes an electric current. The medium of conduction is known
as a conductor.
 Electrolytes can conduct electricity in their molten and aqueous
states. E.g. Metals
 Non-conductors like plastic, ceramic and rubber can be used as
insulation materials.
 Eg. The plastic coating on copper wires
 Chapter 12
Electrochemistry

Electrical conductions in conductors

 Electrical conductions in conductors can be explained through how the atoms are
bonded.

 In metals, the electrons become delocalised due to overlapping orbitals of the

tightly packed atoms in the crystal lattice.

 The valence electrons of each atom are loosely held as they are relatively distant
from the nucleus. Thus they can be easily separated and move about randomly
throughout, conducting electricity.

 The only non-metal that conducts electricity is graphite.

 In graphite, not all electrons are used in bonding. Thus, the free electrons can move
along the layers and carry the electric current.
 Chapter 12
Electrochemistry

The ionic theory

 The ionic theory proposes that it is the presence of freely-moving
charged particles called ions in the electrolyte that allows electrolysis
to occur.
 These ions are only mobile when the electrolytes are in molten or
aqueous state.
 These free moving ions arise only when an ionic solid melts or
dissolves in water or when certain polar covalent compounds
dissolve in water and their molecules ionise (dissociate into freely-
moving ions).
Chapter 12
Electrochemistry

What is Electrolysis ?
 Electrolysis is a process by which a substance is
broken up into its components by the passage of
electricity through it.
 The substance must be an ionic compound and must
be molten or dissolved in water in order for the ions to
be mobile.
 A direct current must be used for electrolysis.
 During this process, electrical energy is changed into
chemical energy.
 Chapter 12
Electrochemistry

Electrolysis
 One electrode is connected to the positive terminal of the battery. It is
called the anode. Oxidation occurs here.
 The other electrode is connected to the negative terminal of the
battery. It is called the cathode. Reduction occurs here.
 An electrolyte is a substance that is being electrolysed.
 An electrolyte is able to conduct electricity due to the presence of
mobile ions.
 Positive ions are known as cations.
 Negative ions are known as anions.
Chapter 12
Electrochemistry

Electrolysis of molten sodium chloride

 Molten sodium chloride contains Na+ and Cl- ions.
 The Na+ ions are attracted to the cathode, while the Cl- ions are attracted
to the anode.
 At the cathode, Na+ ions take in electrons to become Na atoms. We say
that the Na+ ions are discharged.
Na+(l) + e- Na(l)
 At the anode,, Cl - ions give away electrons to become Cl2 gas. We say
that Cl- ions are discharged.
2Cl-(l) Cl2(g) + 2e-
 Overall reaction:
2NaCl(l) 2Na(l) + Cl2(g)
 Chapter 12
Electrochemistry

Electrolysis of Molten Ionic Compounds

 When electricity passes through the molten ionic compound, the positive ions will
migrate to the negative electrode, also known as cathode, while the negative ions
will migrate to the positive electrode, known as anode.
 At the cathode, the positive ions will gain electrons and become metal atoms while
the negative ions will lose electrons at the anode and become non-metallic atoms.

At the Cathode
Sodium ions gain electrons and become sodium atoms, sodium ions are discharged.
Na+(l) + e- Na (l)
At the Anode
Chloride ions lose electrons and become chlorine gas, chloride ions are discharged.
2Cl- (l) Cl2 (g) + 2e-
Chapter 12
Electrochemistry

Electrolysis of other molten compounds

 When a molten binary ionic compound is electrolysed,
the metal is always produced at the cathode and non-
metal is produced at the anode.
Chapter 12
Electrochemistry

Quick check 1
1. What is meant by (i) cathode, (ii) anode ?
2. What is meant by an electrolyte? What type of compounds must
electrolytes be?
3. During electrolysis, to which electrode do:
(a) the positive ions of the electrolyte move to;
(b) the negative ions of the electrolyte move to?
4. Predict the products formed when the following substances (in the
molten state) are electrolysed.
Compound Product at Anode Product at Cathode

Potassium chloride, KCl

Calcium fluoride, CaF2

Solution
Chapter 12
Electrochemistry

Solution to Quick check 1

1. (i) Cathode: the electrode connected to the negative terminal of the
battery.
(ii) Anode: the electrode connected to the positive terminal of the
battery.
2. An electrolyte is a substance which conducts electricity when molten or
dissolved in water. Electrolytes must be ionic compounds.
3. (a) The positive ions move to the cathode.
(b) The negative ions move to the anode.
4.
Compound Product at Anode Product at Cathode
Potassium chloride, KCl Chlorine, Cl2 Potassium, K
Calcium fluoride, CaF2 Fluorine, F2 Calcium, Ca

Return
Chapter 12
Electrochemistry

Electrolysis of solutions
 When solutions are electrolysed, gases are usually produced.
 The gases produced can be collected in test tubes to be identified later
by simple tests.
The electrolysis of solutions is
more complicated than
electrolysis of molten compounds,
because the products at the
electrodes can come from the
electrolyte as well as from water.
Chapter 12
Electrochemistry

Selective discharge of ions

At the cathode:
 Positive ions from the electrolyte are discharged if they are H+ ions or
ions of less reactive metals such as Cu2+, Pb2+ or Ag+.
 Positive ions of reactive metals such as Na+, K+ and Ca2+ are not
discharged in the presence of water. Instead, H+ ions from water are
discharged and H2 gas is produced.
At the anode:
 Negative ions from the electrolyte are discharged if they are halide
ions such as I- , Br - , and Cl-.
 SO42- and NO3- ions are not discharged. Instead, OH- ions from water
are discharged and O2 gas is produced.
Chapter 12
Electrochemistry

Selective discharge of ions

The table shows the electrode products from solutions of ions, assuming the solutions
are fairly concentrated.
Cation Product at Ease of Anion Product at
Cathode discharge Anode

K+ Difficult SO42- Oxygen from

Na+ NO32- water
Ca2+ Hydrogen from Chlorine
Mg2+ water Cl- Bromine
Al3+ Br- Iodine
Ni2+ I- Oxygen
Pb2+ Lead (OH-)
(H+)
Cu2+
Ag+ Copper Easy
Silver
Chapter 12
Electrochemistry

Electrolysis of dilute H2SO4

 Pure water will not conductelectricity, so some dilute sulphuric

acid is added to make it conduct electricity.
 The electrolysis
of dilute sulphuric acid is therefore essentially
the same as the electrolysis of water.
 Chapter 12
Electrochemistry

Electrolysis of dilute H2SO4

 Dilute sulphuric acid contains H+, SO42- and OH- ions.
At the cathode:
H+ ions take in electrons to become H2 molecules; H+ ions are discharged:
2H+(aq) + 2e- H2(g)
At the anode:
OH- ions are discharged in preference over SO42-. Oxygen gas is formed.
4OH-(aq) O2(g) + 2H2O(l) + 4e-
 Overall reaction:
2H2O(l) 2H2(g) + O2(g)
At the cathode: 2 volumes of hydrogen are produced.
At the anode: 1 volume of oxygen is produced.
 The electrolysis of dilute solutions is essentially the same as the electrolysis of
water.
Chapter 12
Electrochemistry

Electrolysis of dilute sodium chloride solution

 The ions present in the solution are: Na+, Cl- (from sodium
chloride) and H+, OH- (from water).
At the cathode:
Both Na+ and H+ are attracted here, but due to their
relative positions in the reactivity series, H+ ions are preferentially
discharged:
2H+(aq)+ 2e-  H2(g)
At the anode:
Both Cl and OH- are attracted here, but due to the lower
-
position of the hydroxide ions in the reactivity series, they are
preferentially discharged:
4OH-(aq)  O2(g) + 2H2O(l) + 4e-
 Overall reaction:
2H2O(l)  2H2(g) + O2(g) [ Electrolysis of water ]
Chapter 12
Electrochemistry

Electrolysis of concentrated sodium chloride solution

 The ions present in the solution are:
Na+, Cl- and H+, OH-
At the cathode:
Both Na+ and H+ are attracted here, but due to their
relative positions in the reactivity series, H+ ions
are preferentially discharged:
2H+(aq) + 2e-  H2(g)
At the anode:
Both Cl- and OH- are attracted here, but due to the high
concentration of the chloride ions, chloride ions are
preferentially discharged:
2Cl-(aq)  Cl2(g) + 2e-
 Overall reaction:
Hydrogen gas is produced at the cathode and chlorine gas is
produced at the anode.
 The Na+ and OH- ions left in the solution combine to form sodium
hydroxide, thus making the solution alkaline.
Chapter 12
Electrochemistry

Electrolysis of Solutions
Examples of electrolysis of different solutions using inert electrodes,
assuming the solutions are fairly concentrated
Product at Product at
Electrolyte Ions in Solution
Cathode Anode
Na+(aq), Cl-(aq) ,
Aq. sodium chloride hydrogen gas chlorine gas
H+(aq), OH-(aq)

Aq. hydrochloric H+(aq), Cl-(aq),

hydrogen gas chlorine gas
acid H+(aq), OH-(aq)

Aq. copper(II) Cu2+(aq), SO42-(aq),

copper metal oxygen gas
sulphate H+(aq), OH-(aq)
Chapter 12
Electrochemistry

Inert and reactive electrodes

 Inert electrodes do not react with the product
produced or dissolved in the electrolyte.
 Carbon and platinum are examples of inert electrodes.
 Reactive electrodes can react or dissolve in the electrolyte.
 Copper, silver and mercury are examples of reactive
electrodes.
Chapter 12
Electrochemistry

Electrolysis of CuSO4 solution

Using copper (reactive) electrodes
 The ions present in the solution are: Cu2+, SO42-, H+ and OH-.
At the cathode:
Cu2+ ions are discharged in preference over the H+ ions:
Cu2+ + 2e-  Cu _ +
At the anode:
Neither SO42- nor OH- ions are discharged.
Instead the copper anode dissolves in the Copper
Copper anode
solution and produces electrons: cathode
Cu  Cu + 2e
2+ - Cu2+ OH-

 During the electrolysis the total concentration of the H+ SO42-

CuSO4 solution remains unchanged. The cathode
increases in mass while the anode decreases in mass
Aq. copper(II) sulphate
proportionately.
Chapter 12
Electrochemistry

Electrolysis of CuSO4 solution

Using copper (reactive) electrodes
 During the electrolysis the concentration of the H+ and
SO42- ions increases, and hence the solution becomes
more acidic.
 This process essentially transfers
copper metal from the anode to
the cathode.
 This process is used in the
industry for the purification of
impure copper to obtain pure copper.
Chapter 12
Electrochemistry

Quick check 2
1. Place in order the ease of discharge of the following cations (starting from the easiest
first): Ca2+, Na+, H+, Al3+, Mg2+, K+, Cu2+, Pb2+, Ag+.
2. Place in order the ease of discharge of the following anions (starting from the easiest
first): Br-, Cl-, NO3-, OH-, I-, SO42-,.
3. (a) State the products obtained when a solution of dilute sulphuric acid is electrolysed
using platinum electrodes.
(b) Write the ionic equations for the reactions taking place at the cathode and anode.
4. (a) State the products obtained when a concentrated solution of sodium chloride is
electrolysed using inert electrodes.
(b) Write the ionic equations for the reactions taking place at the cathode and anode.
5. (a) State the products obtained when a solution of sodium hydroxide is electrolysed
using platinum electrodes.
(b) Write the ionic equations for the reactions taking place at the cathode and anode.

Solution
Chapter 12
Electrochemistry

Solution to Quick check 2

1. Ag+, Cu2+, H+, Pb2+, Al3+, Mg2+, Ca2+, Na+, K+
2. OH-, I-, Br-, Cl-, NO3-, SO42-
3. (a) At cathode: hydrogen; At anode: oxygen
(b) At cathode: 2H+(aq) + 2e-  H2(g)
At anode: 4OH-(aq)  2H2O(l) + O2(g)
4. (a) At cathode: hydrogen; At anode: chlorine
(b) At cathode: 2H+(aq) + 2e-  H2(g)
At anode: 2Cl-(aq)  Cl2
5. (a) At cathode: hydrogen; At anode: oxygen
(b) At cathode: 2H+(aq) + 2e-  H2(g)
At anode: 4OH-(aq)  2H2O(l) + O2(g)
Return
 Chapter 12
Electrochemistry

Faraday’s Law of Electrolysis

 The Faraday constant, F, is the quantity of electricity carried by one
mole of electrons and is equivalent to 96500 Cmol-1.
 The amount of a substance deposited on each electrode of an
electrolytic cell is directly proportional to the quantity of electricity
passing through the cell.
 The quantity of electricity contained in a current running for a
specified time can be calculated by Q= l x t
 The quantity of electricity required to deposit an amount of metal can
be calculated by Q = n(e) x F
Chapter 12
Electrochemistry

Electroplating
Electroplating is the process in which a metallic object
is coated with another metal by electrolysis.
Electroplating with copper
Chapter 12
Electrochemistry

Electroplating with copper

 The electrolyte is copper(II) sulphate (CuSO4)solution.
 The object to be plated is made the cathode; copper is made the anode.
At the cathode:
Cu2+ ions are discharged as copper metal is deposited on the object:
Cu2+(aq) + 2e  Cu(s)

At the anode:
Copper dissolves: Cu(s)  Cu2+(aq) + 2e-

 There is a net transfer of copper from the anode to the cathode.

The concentration of the CuSO4 solution remains unchanged.
 Chapter 12
Electrochemistry

Anodising
 Anodising is the process of making the oxide layer on the
surface of the aluminium thicker. This will protect the aluminium
even better.
 The aluminium object is made the anode while the cathode
could be copper or lead or aluminium.
 When current is applied, the water in the electrolyte breaks
down and oxygen is deposited at the anode. This oxygen then
combines with the aluminium to form aluminium oxide and thus
provides a protective layer for the aluminium. This prevents
corrosion.
Chapter 12
Electrochemistry

Electroplating with other metals

 Many metallic objects can be electroplated in
the same way:
 The object is made the cathode and the metal used for
electroplating is made the anode. The electrolyte is a
solution of ions of the metal used for the plating.
 Electroplating can be used to protect iron objects from
corrosion by covering it with a less reactive metal like
chromium or copper.
 Electroplating also makes the object more attractive and
increases its value e.g. plating it with gold, silver and
platinum.
Chapter 12
Electrochemistry

Examples of electroplating
Electroplating Metal Uses
Water taps, motorcar bumpers and bicycle
Chromium
parts
Tin Tin cans

Silver-plated sports trophies, plaques,

Silver
ornaments, knives and forks

Gold Gold-plated watches, plaques, ornaments

Chapter 12
Electrochemistry

Quick check 3
1. State two uses of electrolysis in the industry.
2. (a) What is electroplating?
(b) State two advantages of electroplating
an iron object with chromium.
3. A metal spoon is to be coated with silver. Sketch a diagram to
show how you would set up the electrolytic cell for this to be
carried out. Label the material that can be used for the
cathode and anode. Also state a suitable solution for the
electrolyte.

Solution
Chapter 12
Electrochemistry

Solution to Quick check 3

1. (i) To extract reactive metals like sodium, magnesium

and aluminium from their ores;
(ii) To electroplate metallic objects with less reactive
metals for attractiveness and protection from corrosion.
2. (a) Electroplating is the coating of a more reactive metal
with a less reactive metal by electrolysis.
(b) Electroplating with chromium protects the iron from
corrosion and the silver colour of the chromium
improves its appearance.

Return
Chapter 12
Electrochemistry

Solution to Quick check 3 (cont’d)

3. Cathode: the metal object; Anode: silver metal
Electrolyte: silver nitrate solution.

Electroplating with
silver

Return
 Chapter 12
Electrochemistry

To learn more about Electrolysis,

click on the links below!
1. http://www.matter.org.uk/schools/Content/Electrolysis/ElectrolysisE
xplainApplet.html
2. http://www.nmsea.org/Curriculum/7_12/electrolysis/electrolysis.htm
3. http://inventors.about.com/library/inventors/blelectroplating.htm