ELECTROCHEMISTRY

 Is the branch of chemistry that deals with the

transformation of electrical energy and chemical energy
 Some reactions are spontaneous(exothermic reactions)-
do not need constant supply of energy
 others are non-spontaneous(endothermic)- need constant
supply of energy

REDOX REACTIONS:
- Involves transfer of electrons
-reduction and oxidation reactions occur simultaneously
-oxidation is the loss of electrons(oxidation number increases)
-reduction is the gaining of electrons(oxidation number
decreases)
 Oxidizing agent accepts electrons and causes oxidation
 Reducing agent donates electrons and causes reduction
OXIDATION NUMBERS
Calculate the oxidation numbers
of the following underlined
elements:
1. MgO
2. MnO4-
3. HSO4-
 Using the TABLE OF STANDARD
ELECTRODE POTENTIALS(Li+ on top)
 Reactions only show particles involved in
electron transfer, no spectator ions on table.
 They are reversible half reactions. All are
reduction when reading from left to right
and oxidation when reading from right to
left.
 Substances on the left are oxidizing agents
and on the right are reducing agents.
OA RA
Weak strong
, ,
, ,
WHEN WRITING HALF EQUATIONS
 Right to Left is always oxidation.
 Left to Right is always reduction.
 All reactions must be written with a single
arrow ().
 Electrons for the oxidation and reduction
half equations must be balanced.
 +ve electrode potential means
spontaneous and –ve electrode potential
means non-spontaneous.
 The overall equation is written with a
double arrow ().
 SPONTANEOUS
REACTIONS
 A spontaneous reaction is the one which
takes place without added energy. They are
exothermic.
 It takes place when a stronger oxidizing
agent is added to a stronger reducing agent.
 To determine whether a reaction is
spontaneous:
 Separate reaction into half equations and
consider the reactants, if they are both strong
reducing and oxidizing agents.
 Only spontaneous if both are strong.
TWO TYPES OF
ELECTROCHEMICAL CELLS
1. Galvanic cell(voltaic cell)
-converts chemical energy to
electrical energy
-these are batteries
-reactions are spontaneous
2. Electrolytic cell
-converts electrical energy to
chemical energy
-reactions are non-spontaneous
 GALVANIC AND
ELECTROLYTIC CELLS
 REDOX REACTIONS

OXIDATION
REDUCTION

A reaction in
which a A reaction in
substance which a
loses electrons substance gains
(increase in electrons
oxidation (decrease in
number oxidation
number
Mg → Mg2+ + 2e- oxidation
reaction

reducing agent (donates electrons and

so can cause
reduction)-
Cl2 + 2e → 2Cl- reduction reaction

oxidising agent (accepts electrons and

so can cause
oxidation)
Mg → Mg2+ + 2e- Mg is oxidised
(1)
Cl2 + 2e- → 2Cl- Cl2 is reduced (2)

Mg + Cl2 → MgCl2 Redox

reaction
The electrons cancel each other out.
MgCl2 is an ionic compound (Mg2+ 2Cl-)
The equation shows 2 half reactions (1
and 2) that add to give the full redox
reaction.
DIRECT ELECTRON TRANSFER

A coil of copper was

placed in a silver
nitrate solution

The solution became

blue because copper
ions were formed.
Solid silver deposited
on the copper wire.
From the observations we can infer that:
Cu → Cu2+ + 2e-
Ag+ + e- → Ag

Electrons are transferred from the

copper atoms on the piece of copper, to
the silver ions in the silver nitrate
solution.
This is a redox reaction.
This is a spontaneous reaction.
THE STRUCTURE OF THE GALVANIC CELL
 The galvanic cell is a spontaneous,
exothermic reaction which converts
chemical energy to electrical energy.
 The cathode is positive and the electrode
where reduction occurs (RED CAT).
 The anode is negative and the electrode
where oxidation occurs (AN OX).
 It consist of the following components:

1. Two half cells

2. An electrode in each half cell, Anode and
Cathode
3. An electrolyte in each half cell
4. A salt bridge connecting the two half cells
A GALVANIC CELL
THE ZINC-COPPER CELL
 The following observations were made:
• the zinc plate decreases in mass.
• the copper plate increases in
mass.
• the voltmeter reading indicates
that electrons flow from the zinc
plate to the copper plate.
•Electrode is a metal rod
•Electrolyte is a solution that
conducts electricity
 Anode is an electrode where oxidation
takes place. Electrons remain on
electrode while Mn+ ions go into
solution. So its mass decreases and
electrode become negatively charged.
Conc of solution increases.
 Cathode is an electrode where
reduction takes place. Mn+ ions accept
electrons from the electrode and
change to atoms. Electrode become
positively charged and increase in
mass. Conc of solution decreases.
 When the electrodes are joined
electrons flow from anode to cathode.
• Since the cell maintains a positive
and negative electrode, there is a
potential difference or emf between
the two electrodes. It can be
measured using a voltmeter.
• The potential difference between
the electrodes varies with
temperature and concentration of
solutions.
• To make comparisons of emfs we
use standard conditions of conc (1
mol.dm-3) and temperature (25oC or
298 K)
 The salt bridge:
• is a gel solution that connects the two
electrolyte solutions that the metals dip
into
 Functions of the salt bridge
 1. Maintains electrical neutrality, while
the cell is functioning( positive ions or
cations migrate to the cathode to
prevent build up of negative ions, while
negative ions or anions migrate to the
anode to prevent the build up of positive
ions
 2. completes the circuit
 CELL NOTATION:
 This summarises the essential
characteristics of a cell. By convection the
anode half cell is on the left:
reducing agent/oxidized species//oxidizing agent/reduced
species.
 Zn(s)/Zn2+(aq)//Cu2+(aq)/Cu(s)
(1 mol.dm-3)(1 mol.dm-3) at 298 K
 The redox reaction for the cell:

Oxidation half reaction: Zn(s) → Zn(aq)2+ + 2e-

Reduction half reaction: Cu(aq)2+ + 2e- → Cu(s)
Overall net reaction: Zn(s) + Cu(aq)2+ → Zn (aq)
2+
+
Cu(s)
The zinc dissolves – the mass of the
zinc plate decreases.
The copper plate increases in mass
because copper ions deposit as
copper metal.
The electrodes:

Each metal strip is an electrode.

Each electrode with its associated
electrolyte solution, is called a half cell.

The electrode where oxidation

occurs is the ANODE. It has a
negative charge.
The electrode where reduction
occurs is the CATHODE. It has a
positive charge.
Cell notation:

Zn / Zn2+ // Cu2+ / Cu

Write the anode half reaction

first – salt bridge (//) – then
the cathode half reaction

Zinc atoms are oxidised to Zn2+

ions (anode).
Cu2+ ions are reduced to copper
atoms (cathode). Reduction
written on the Right
STANDARD ELECTRODE
POTENTIALS
 THE STANDARD HYDROGEN
ELECTRODE
In order to measure the potential of an
electrode, it is compared to a reference
electrode – the standard hydrogen
electrode.
The standard half reaction is the
reduction of hydrogen:
2H+ + 2e- → H2

The electrode potential of this half cell =

0,00V
Operating conditions:

STP
Temperature = 298K
Pressure = 1 atm
or 101,3 2kPa
Concentration
= 1 mol.dm-3
Measuring the standard electrode
potential of zinc by connecting a zinc
electrode to the hydrogen electrode.
 The hydrogen electrode is the cathode.
2H+(aq) + 2e- → H2(g)
The zinc electrode is the anode.
Zn(s) → Zn2+(aq) + 2e-

The reading on the voltmeter is

0,76V and because electrons flow
from the zinc to the hydrogen
electrode
Eo for the zinc half cell = - 0,76V
Using the table of standard electrode
potentials:

• determine the emf of a cell.

• predicting whether a redox reaction
will occur spontaneously;
• balancing redox reactions.
Determining the emf of a cell:

Eᶿ cell = Eᶿ reduction – Eᶿ oxidation

= Eᶿ oxidising agent – Eᶿ reducing agent

= Eᶿ cathode – Eᶿ anode
For the cell:
Zn / Zn2+ // Cu2+ / Cu
The zinc electrode is the reducing
agent and the anode as oxidation
occurs at that electrode.
Eᶿcell = Eᶿ Cu – Eᶿ Zn
= 0,34 – (-0,76)
= +1,10V
Predicting whether a redox reaction
will occur spontaneously.
• Write down the equation as you
expect it to occur.
• from the equation decide which
half cell is the reducing/oxidising
agent.
• Determine Eᶿcell based on this
information.
• If Eᶿcell is a positive number, the
reaction, as written, is spontaneous.
 EFFECTS OF CONCENTRATIONS
OF SOLUTIONS TO EMF
 Half reactions are reversible. An increase or
decrease of concentration will shift the
equilibrium in a particular direction.
 Increase in conc in anode ions favours the reverse
rxn in the anode half cell and the negative charge
on the anode decrease. Emf decreases.
 Decreasing the conc of the cathode half cell
reverses the reaction and decreases the positive
charge on the cathode. Emf decreases.
 In a fresh cell the initial forward reaction takes
place but the conc of anode increase and that of
cathode decrease, the rate of reverse reaction
increase until equilibrium is reached. The
electrode potential for each half cell is zero and
the emf is zero. The cell is flat.
CURRENT FROM CELL AND
RATE OF REACTION
 Current is produced due to chemical
reaction.
 The larger surface area of electrode, the
higher the rate of reaction and the higher
the current.
 Current also depends on internal
resistance of the cell.
 The internal resistance of the cell is
lowered by:
 Bringing electrodes close together
 Using a short and wider salt bridge
 CLASS ACTIVITY
QUESTION 8 (Start on a new page.)

The diagram below represents a galvanic (voltaic) cell functioning under standard
conditions with magnesium and silver as electrodes. A voltmeter connected across the
electrodes shows an initial reading of 3,17 V.

Mg(s) Ag(s)
salt bridge

Mg2+(aq) Ag+(aq)

8.1 State the energy conversion that takes place in this cell. (2)

8.2 State TWO standard conditions under which this cell operates. (2)

Identify the anode of this cell. Refer to the relative strength of reducing agents
8.3 to explain how you arrived at the answer. (3)

Write down the cell notation (symbolic notation) of this cell.

8.4 (3)

Write down the balanced equation for the net (overall) cell reaction that takes
8.5 place in this cell. Omit the spectator ions. (3)

How will an increase in the concentration of the Ag+ ions influence the current
8.6 that the cell delivers? Write down only INCREASES, DECREASES or
REMAINS THE SAME and explain the answer.
(3)
[16]
APPLICATIONS OF
ELECTROCHEMISTRY
 Preventing the corrosion of iron:
A more reactive metal (like Mg or zn) can be
used to coat iron. The oxide provides an
impervious coating. The reactive metal is
called a sacrificial metal.
 Iron pipes can also be connected with lumps
of magnesium. The magnesium will readily
be oxidized and this prevents oxidation of
Iron. This is known as the cathodic
protection.
ELECTROLYTIC CELL
 Converts electrical energy to
chemical energy
 Electrolysis is a process in which
electricity is used to
decompose/break a compound
into components or is a process
that converts electrical energy
to chemical energy.
 ELECTROLYTIC CELLS

Source of energy

Positive electrode Negative electrode

A battery is always required in this type of cell.

Cl- ions are attracted to the positive
electrode, where they lose electrons.
Cl-(aq) → Cl (g) + e-

Oxidation occurs at the positive

electrode – the ANODE.
APPLICATIONS of REDOX
REACTIONS/ELECTROLYSI
S
USES OR APPLICATIONS OF
ELECTROLYSIS
1. Electroplating- to coat a metal
with another metal
2. Electro-refining of copper/
purification of metals- removal
of impurities from a metal
3. Extraction of aluminium
4. Decomposition of compounds
e.g copper chloride
ELECTROPLATING

Electroplating is the use of

electrolysis to apply a thin layer of
one metal over another.
QUESTION 11

An attractive silver appearance can be created by electroplating artefacts made from

cheaper metals, such as nickel, with silver.

The simplified diagram below represents an arrangement that can be used to

electroplate a nickel artefact with silver.

Electrode Y

Electrode X
(Nickel artefact)
 Ag+ solution

11.1 Which electrode (cathode/anode) will the nickel artefact represent? (1)

11.2 Name the metal represented by electrode Y. (1)

11.3 Write down the half-reaction responsible for the change that occurs at the
surface of the artefact. (2)

11.4 Give a reason why the concentration of the electrolyte remains constant
during electroplating. (2)

11.5 In industry some plastic articles are sometimes electroplated. Explain why
plastic must be coated with graphite before electroplating. (2)

11.6 Give a reason why, from a business point of view, it is not advisable to plate
platinum with silver. (1)
[9]
QUESTION 11/VRAAG 11

11.1 cathode/katode  [12.1.2] (1)

11.2 Silver/silwer  [12.1.2] (1)

11.3 Ag+ + e- → Ag  [12.2.3] (2)

11.4 The rate of oxidation of silver at the anode is equal to the rate of
reduction of silver ions at the cathode. 
Die tempo van oksidasie van silwer by die anode is gelyk aan die
tempo van reduksie van silwerione by die katode. [12.1.4] (2)

11.5 Plastic is a non-conductor/Graphite is a conductor 

Plastiek is ‘n nie-geleier/Grafiet is ‘n geleier [12.3.2] (2)

11.6 Platinum is expensive/more durable than other metals 

Platinum is duur/meer duursaam as ander metale [12.3.3] (1)
[9]
ELECTRO-REFINING of COPPER
-removing impurities from impure copper.
Electrolysis allows the dissolution of copper
from the impure (blister) copper anode and
deposition of pure copper on the copper
cathode.
-slime or sludge contains precious metals
like platinum
 Reactions:
At the cathode:
Cu2+(aq) + 2e- → Cu(s)
Copper ions are reduced to copper
which plates on the cathode

At the anode:
Cu(s) → Cu 2+
(aq) + 2e-
Copper atoms are oxidized and go
into solution as Cu2+ ions.
 EXTRACTION OF ALUMINIUM
 Aluminium is the most widely used metal
 It is extracted from an ore called bauxite
 Bauxite is mined in Australia
 Bauxite contains 3 compounds:

1. Aluminium oxide(alumina) Al2O3

2. Silicon oxide
3. Iron oxide
 Sodium hydroxide is used to remove the impurities
like silicon oxide and iron oxide from bauxite
 Use electrolytic cell to split Al2O3 to Al and O2
 ADVANTAGES OF ALUMINIUM:
1. Does not corrode easily
2. It is stronger
3. Excellent conductor of electricity
 EXTRACTION OF ALUMINIUM FROM
BAUXITE
Electrolysis of aluminium oxide dissolved
in cryolite (Na3AlF6) to save energy by
reducing the melting point temperature of
Al2O3 from 2000ºC to 900ºC
 Chemical reactions:
At the cathode:
Al3+ + 3e- → Al(l)
The liquid aluminium forms a layer of molten
aluminium at the bottom of the cell.
At the anode:
2O2- → O2(g) + 4e-
oxygen reacts with the carbon electrode
to form carbon dioxide.
Overall net reaction: Al3+ + 2O2- → Al(l) +
O2(g)
QUESTION 11

Aluminium is one of the most abundant metals on earth, yet it is expensive – largely
because of the amount of electricity needed to extract it. Aluminium ore is called
bauxite. The bauxite is purified to yield a white powder, aluminium oxide, from which
aluminium can be extracted.

The diagram below shows an electrolytic cell used for the extraction of aluminium at
temperatures as high as 1 000 °C.

Fe container

─ ─

+ + Carbon electrode

Purified aluminium oxide dissolved

in molten cryolite (Na3AlF6)
Drain

Molten aluminium

11.1 State the energy conversion that takes place in this electrolytic cell. (2)

11.2 Is aluminium formed at the positive or negative electrode? Write down

POSITIVE or NEGATIVE only. (1)
11.3 Use the Table of Standard Reduction Potentials (Table 4A or 4B) to write
down the half-reaction for the formation of aluminium. (2)

11.4 Explain why carbon dioxide gas is formed at one of the electrodes. (2)

11.5 Why should the carbon electrodes be replaced regularly? (2)

11.6 Write down TWO negative effects that the extraction of aluminium can have
on the environment. (2)
[11]
QUESTION 11/VRAAG 11
11.1 Electrical energy to chemical energy
Elektriese energie na chemiese energie

Only electrical or chemical energy: no marks

Slegs elektries of chemiese energie: geen punte [12.2.1] (2)
11.2 negative / negatief  [12.2.3] (1)
11.3 Aℓ3+ + 3e- → Aℓ 
Aℓ3+ + 3e-⇌ Aℓ (1 )
2
3+ -
Aℓ + 3e ← Aℓ ( 0 )
2
Aℓ ← Aℓ3+ + 3e- ( 2 )
2
3+
Aℓ ⇌ Aℓ + 3e -
( 0 )
2
[12.2.3] (2)

11.4 Carbon will burn in/react with O2 because of the high temperature 
to form CO2 / Koolstof verbrand in/reageer met O2 a.g.v. die hoë
temperatuur om CO2 te vorm
OR/OF
C(s) + O2(g) → CO2(g)

OR/OF
The carbon is oxidised according to the following half-reaction:
Die koolstof is oksideer as gevolg van die volgende halfreaksie:
C(s) + 2O2-(g) → CO2(g) + 4 e-
[12.2.3] (2)
11.5 Carbon burns away/used up/oxidised / loses e- (and needs to be
replenished)
Koolstof brand weg/opgebruik/geoksideer/ verloor e-( en moet
aangevul word) [12.2.3] (2)
11.6 Any two: 
Ecological Impact
 Loss of landscape due to the size of the chemical plant needed
 Disposal of red mud (iron(III) oxide formed during extraction of aluminium oxide
from bauxite) into lagoons causing them to become unsightly
Environmental Impact
 Carbon dioxide from the burning of the anodes contributes to the (enhanced)
greenhouse effect (air pollution /global warming)
 Carbon monoxide is poisonous
 fluorine (and fluorine compounds) lost from the cryolite during the electrolysis
process is poisonous
 Alkali of red mud dams can drain into soil and contaminate groundwater
 Pollution caused by power generation (for electrolytic process) using coal-fired
plants leads to acid rain/enhanced (greenhouse effect)
 Noise pollution

Enige twee: 
Ekologiese impak
 Groot gebied vir chemiese aanleg benodig - verlies aan landskap
 Wegdoening van rooi modder (yster(III)oksied gevorm tydens
die ekstraksie van aluminiumoksied vanaf bauxiet) ontsier
strandmere
Omgewingsimpak
 Koolstofdioksied uit die verbranding van die anode dra by tot die
kweekhuiseffek (lugbesoedeling / aardverwarming)
 Koolstofmonoksied is giftig
 fluoor (en fluoorprodukte); verlies van krioliet gedurende die elektrolise – proses
is giftig
 Alkalieë van rooi modderdamme kan in grond sypel en grondwater kontamineer
 Besoedeling veroorsaak deur kragopwekking d.m.v. steenkoolaanlegte dra by
tot suurreën/kweekhuiseffek
 Klankbesoedeling
 DECOMPOSITION OF COPPER CHLORIDE
 Copper(II) chloride dissolves in water to
form a blue solution
 Symbol is CuCl2
 Decompose CuCl2 to form Cu and Cl2
using electrolysis
 Half reaction at the anode:2 Cl- → Cl2 +
2e-
 Half reaction at the cathode:Cu2+ + 2e-
→Cu
 Overall net reaction:Cu2+ + 2 Cl- → Cl2 +
Cu
Comparison of galvanic and electrolytic cells .
Galvanic cell Electrolytic cell
Produces an emf from a Uses the emf of a cell to
chemical reaction (is the produce a chemical
battery) reaction (needs a battery)
Chemical potential energy Electrical potential energy
converted to electrical converted to chemical
potential energy potential energy

Positive terminal - cathode Positive terminal – anode

Two containers each with One container with both
an electrodes electrodes dipping in
Spontaneous reaction Non-spontaneous reaction
Exothermic reaction Endothermic reaction
THE CHLOR-ALKALI
INDUSTRY
 CHLOROALKALI INDUSTRY
 Industrial process of manufacturing
chlorine gas, sodium hydroxide and
hydrogen from sodium chloride.
 Three products are obtained:

1. Chlorine gas(Cl2)

2. Hydrogen gas(H2)
3. Sodium hydroxide(NaOH)
 Reactants(raw materials) used:

1. Water(H2O)

2. Sodium chloride(NaCl)
 There are THREE cells that can be used:
1. Membrane cell
2. Mercury cell
3. Diaphragm cell
 The only cell that is used currently is the
membrane cell, because of its advantages:
1. Less pollution/environmental friendly
2. Cheaper to operate
3. Products are more pure
Disadvantages of other two cells:
 Mercury cell:

1. Uses mercury which is poisonous

2. Expensive to operate
 Diaphragm cell:

1. Uses asbestos which is poisonous

2. High steam consumption
MEMBRANE CELL
 HOW THE CELL OPERATES
 NaCl (brine) is pumped at the anode
 Sodium ions(Na+) migrate through the cationic
membrane to the cathode
 Cl- ions (from NaCl) are oxidised to Cl2 gas that escapes
 H+ ions (from H2O in solution) are reduced to
hydrogen(H2) gas and escapes
 Na+ ions combine with OH- ions (of H2O solution) to
form NaOH
 Half reaction at the anode:2 Cl- → Cl2 + 2e-
 Half reaction at the cathode:
2 H2O+ 2e- → H2 + 2 OH-
Overall net reaction: 2 Cl- + 2 H2O → Cl2 +H2 + 2 OH-
 Functions of the cationic
membrane:
1. Allows only Na+ ions to migrate from
the anode to the cathode
compartment
2. Prevents Cl- ions from mixing with
NaOH

Uses and properties of sodium

hydroxide
- NaOH is corrosive and caustic in action

1. used in the manufacture of paper

2. Used in the process of aluminium
extraction from bauxite
3. Used in food industry
Uses and properties of chlorine gas
- Cl gas is a poisonous gas, yellow-green
2
with a pungent smell
1. Used in the manufacturing of HCl
2. Manufacturing of PVC
3. Production of CFC’s, used in
refregerators
4. Manufacturing of bleaching
agents(textile industry and paper
industrt)
5. Used in medicine to cure disease
6. Purify drinking water
7. Used as a solvent e.g tippex
NEGATIVE EFFECT OF
CHLOROALKALI INDUSTRY
1. Chlorine is poisonous
2. Hydrogen gas can result in explosion
3. Leaching of sodium hydroxide into
ground water is a health risk to
humans and the environment
Negative impact
4. Use huge amount of electricity- results
in load shedding
5. Chemical plant uses a lot of space-
that could have been used for housing/
gardens
 POSITIVE IMPACT
1. Job creation resulting in more people having a
better.
Contribution of chloroalkali industry to
greenhouse effect
2. Uses huge amount of electricity, combustion
of coal during the generation of electricity
releases huge amount of carbon dioxide
Negative impact of chlorine on humans
3. Chlorine gas is poisonous-it causes health
problems or breathing problems
4. Chlorine gas is used to make drugs- that can
be dangerous when overdosed
5. Chlorine is used as a nerve gas(weapon of
chemical warfare that affect transmission of
nerve impulses)
QUESTION 11 (Start on a new page.)

The diagram below is a simplified version of a membrane cell, one of the electrolytic
cells used in the chlor-alkali industry. The letters P and Q represent the two gases
formed during this process.

P Q
membrane

Concentrated water
salt solution

Used salt NaOH(aq)

solution

_
+
11.1 Write down the letters P and Q in your answer book. Next to each, write
down the half-reaction that shows how gas P and gas Q are respectively
formed. (4)

11.2 Water (H2O(ℓ)) and sodium ions (Na+(aq)) are both present in the cathode
side of the membrane cell. Explain why hydrogen gas, and not sodium metal,
is formed in the membrane cell. Refer to the relative strengths of oxidising
agents to explain your answer. (2)

11.3 State ONE function of the membrane. (1)

11.4 State TWO uses of chlorine. (2)

[9]
 CALCULATIONS INVOLVING
ELECTROCHEMICAL CELLS
Relationship between current and number of
electrons
 Each electron carries a charge of C
 1 mol of electrons has 96 500 C called 1
Faraday
 1 Faraday is required to release 1 mol of
electrons
 In general q = nF (number of coulombs = mols x
Faradays)
 Recall: q = It
 We can use these relationships to determine
the quantities of reactants and products
involved in an electrochemical cell