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
Electrochemistry
Conductors and Non-conductors of Electricity

Conductors
Metals and graphite (non-metal)

Electrolytes

Non-conductors
Plastics

Ceramics

Rubber
 Electrochemistry
Electrical Circuit to Test Solid Materials as Conductors or
Insulators of Electricity:
 Electrochemistry

Types of Electrolytes
■ Strong Electrolyte
Molten salts, strong acids and alkalis, which dissociate completely in
water to produce a high concentration of ions in solution

■ Weak Electrolyte
Weak acids such as ethanoic acid and weak alkalis such aqueous
ammonia which partially ionize in water to produce a low
concentration of ions in solution. Pure water is a very weak electrolyte
because it produces an extremely low concentration of H+ and OH -
ions when water ionises

■ Non - Electrolyte
Sugar solutions and alcohols which do not produce ions in solution
Electrochemistry
Electrical Circuit to Test Solutions as Conductors or
Non-conductors of Electricity:
 Electrochemistry
Types of Conduction

Metallic Electrolytic
conduction conduction

Occur in metals Occur in

and graphite Electrolytes

Charge carriers Charge carriers

are are
mobile electrons mobile ions
 Electrochemistry
Types of Conduction

■ Metallic Conduction:
The flow of electrons through a metal or graphite when a
potential difference is applied. The metal remains chemically
unchanged during the process.

■ Electrolytic Conduction:
The movement of ions through a solution when a potential
difference is applied. The solution is chemically changed during
the process.
Electrochemistry

Electrolyte vs. Non-Electrolyte

Electrochemistry

What is Electrolysis?
■ Electrolysis is the process by which an
electrolyte is decomposed when an electric
current has passed through the electrolyte.
■ The electrolyte must be an ionic compound and
must be molten or dissolved in water in order for
the ions to become mobile for electrolytic
conduction to take place.
■ Electrolysis takes place in an electrolytic cell.
■ In the electrolytic cell, electrical energy is
converted into chemical energy.
Electrochemistry

The Electrolytic Cell

 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.
■ Positively charged ions are known as cations and migrate to the
cathode.
■ Negatively charged ions are known as anions and migrate to
the anode.
 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) Cl 2 (g) + 2e -
■ Overall reaction:
2NaCl (l) 2Na (l) + Cl 2 (g)
 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) Cl 2 (g) + 2e -
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.
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, CaF 2

Solution
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, CaF 2 Fluorine, F 2 Calcium, Ca

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 Electrochemistry
Electrolysis of Solutions

■ 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.

■ An aqueous solution contains H + and OH- ions from water in addition to

the other ions from the electrolyte

▪ Only one type of ion at each electrode is discharged

 Electrochemistry
Factors Affecting Selective Discharge of Ions at each Electrode:

■ Position of the ion in the electrochemical series

■ Relative concentration of the ions (halide ions)

■ Nature of the electrode (active or inactive)

 Electrochemistry
The Electrochemical Series
The table shows the electrode products from solutions containing different ions:

Cation Product at Ease of Anion Product at

Cathode discharge Anode

K+ Difficult SO 42- Oxygen from

Ca 2+ NO 3- water
Na + Hydrogen from
Mg 2+ water Cl - Chlorine
Al 3+ Br - Bromine
Zn 2+ I- Iodine
Fe 2+ Lead (OH -) Oxygen
Pb 2+
(H + )
Copper
Cu 2+ Easy
Silver
Ag +
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 Cu 2+, Pb2+ or Ag+.
■ Positive ions of reactive metals such as Na+, K+ and Ca2+ are not
discharged in the presence of water because they are stable
ions and do not readily accept electrons. Instead, H+ ions from
water are discharged and H 2 gas is produced.
At the anode:
■ Negative ions from a concentrated electrolyte are discharged if
they are halide ions such as I - , Br -, and Cl-.
2- - -
■ SO4 and NO 3 ions are not discharged. Instead, OH ions from
water are discharged because they are less stable than the SO 42-
and NO3- ions
 Electrochemistry
Electrolysis of Dilute H 2SO4

■ Pure water will not conduct electricity, so some dilute sulfuric

acid is added to improve its electrical conductivity.
■ The electrolysis of dilute sulfuric acid is therefore essentially
the same as the electrolysis of water.
Electrochemistry
Electrolysis of Acidified Water
 Electrochemistry
Electrolysis of Dilute H 2SO4
■ Dilute sulfuric acid contains H +, SO 42- and OH- ions.
At the cathode:
H+ ions take in electrons to become H 2 molecules; H + ions are discharged:
2H+ (aq) + 2e- H2 (g)
At the anode:
OH- ions are discharged in preference over SO 42-. Oxygen gas is formed.
4OH- (aq) O2 (g) + 2H 2O (l) + 4e -
■ Overall reaction:
2H2O (l) 2H 2 (g) + O 2 (g)
At the cathode: 2 volumes of hydrogen are produced.
At the anode: 1 volume of oxygen is produced.
■ Volume ratio of hydrogen : oxygen is 2:1 because for every four moles of electrons
transferred 1 mole of oxygen is produced but 2 moles of H 2 are produced since
Electrochemistry

Electrolysis of Dilute and Concentrated NaCl

 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 electrochemical 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 electrochemical series, they are
preferentially discharged:
4OH- (aq) O2 (g) + 2H 2O (l) + 4e -
■ Overall reaction:
2H2O (l) 2H2 (g) + O 2 (g) [ Electrolysis of water ]
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 electrochemical series, H + ions
are preferentially discharged:
2H+ (aq) + 2e - H 2 (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.
Electrochemistry

Inert and Active Electrodes

■ Inert electrodes do not react with the product
produced or dissolve in the electrolyte.
Carbon (graphite) and platinum are examples of inert
electrodes.
■ Active electrodes can react or dissolve in the
electrolyte.
Copper, silver and mercury are examples of reactive
electrodes.
 Electrochemistry
Electrolysis of CuSO4 Solution
Using graphite (inert) 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+(aq) + 2e - Cu (s) _ +
At the anode:
OH - ions are discharged in preference,
since the OH - ions are lower in the graphite
graphite anode
electrochemical series than the SO 42- ions cathode
Cu 2+ OH-
- -
■ 4OHthe
During O2 (g) + 2H 2the
(aq) electrolysis O (l) total
+ 4econcentration of the H+ SO42-
CuSO4 solution decreases. Hence, the blue colour of
the solution fades and the electrolyte becomes acidic. Aq. copper(II) sulphate
The cathode increases in size due to the Cu deposits
 Electrochemistry
Electrolysis of CuSO4 Solution
Using copper (active) 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+(aq) + 2e - Cu (s) _ +
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
2+ -
Cu (s) Cu (aq) + 2e Cu 2+ OH-

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

CuSO4 solution remains unchanged. The blue colour
of the solution does not fade. The cathode increases in Aq. copper(II) sulphate
size while the anode decreases in size proportionately.
 Electrochemistry
Applications of Electrolysis
Purification of Copper
■ This process essentially transfers
copper metal from the anode to
the cathode.
■ The electrolyte is aqueous copper (II) sulfate
■ This process is used in the
industry for the purification of
impure copper to obtain pure copper.
■ This process is called Electro-Refining
 Electrochemistry

Quick check 2
1. Place in order the ease of discharge of the following cations (starting from the easiest
first): Ca 2+ , Na + , H + , Al3+ , Mg 2+ , K + , Cu 2+ , Pb 2+ , Ag + .
2. Place in order the ease of discharge of the following anions (starting from the easiest
first): Br - , Cl- , NO 3- , OH - , I - , SO 42-,.
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
Electrochemistry

Solution to Quick check 2

1. Ag+, Cu2+, H+, Pb 2+, Al3+, Mg2+, Ca 2+, Na +, K+
2. OH-, I-, Br-, Cl-, NO3-, SO42-
3. (a) At cathode: hydrogen; At anode: oxygen
(b) At cathode: 2H+(aq) + 2e- H 2(g)
At anode: 4OH-(aq) 2H2O(l) + O 2(g)
4. (a) At cathode: hydrogen; At anode: chlorine
(b) At cathode: 2H+(aq) + 2e- H 2(g)
At anode: 2Cl -(aq) Cl 2
5. (a) At cathode: hydrogen; At anode: oxygen
(b) At cathode: 2H+(aq) + 2e- H 2(g)
At anode: 4OH-(aq) 2H2O(l) + O 2(g)
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Electrochemistry
Applications of Electrolysis
Electroplating

Electroplating is the process in which a metallic

object is coated with another metal by electrolysis.

Electroplating with copper

 Electrochemistry

Electroplating with Copper

■ The electrolyte is copper(II) sulphate (CuSO 4)solution.
■ The object to be plated is made the cathode; pure 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) Cu 2+ (aq) + 2e -

■ There is a net transfer of copper from the anode to the

cathode. The concentration of the CuSO 4 solution remains
unchanged.
 Electrochemistry
Applications of Electrolysis
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
is usually graphite.
■ 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.
 Electrochemistry
Anodising
At the cathode:
2H+(aq) + 2e - H2 (g) _ +

At the anode:
4OH-(aq) O 2 (g) + 2H 2O (l) + 4e - graphite
aluminum
object
cathode
OH-
Overall reaction: H+ SO42-

4Al (s) + 3O 2 (g) 2Al2O3 (s)

Aq. Sulfuric acid
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.
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

 Electrochemistry
Faraday’s Laws 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/produced at an electrode
of an electrolytic cell is directly proportional to the quantity of
electricity passing through the electrolyte.
(1st Law of Electrolysis)
■ The quantity of electricity passing for a specified time can be
calculated by Q= l x t
■ The number of Faradays required to liberate 1 mole of an ion at
an electrode is equal to the size of the charge on the ion.
(2nd Law of Electrolysis)
■ To discharge 1 mole of Na + to Na, 1 mole of electrons is required
■ Similarly 1 mole of Mg 2+ to Mg, 2 moles of electrons are required
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
 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.

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Electrochemistry

Solution to Quick check 3 (cont’d)

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

Electroplating with
silver

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 Electrochemistry

To learn more about Electrolysis,

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