IGCSE CHEMISTRY

ELECTROCHEMISTRY

Al Ma’arifa International Private School, Sharjah

IGCSE Chemistry
KEY OBJECTIVES

4.1 ELECTROLYSIS

Define electrolysis as the decomposition of an ionic compound, when molten or in

aqueous solution, by the passage of an electric current.
Identify in simple electrolytic cells: (a) the anode as the positive electrode (b) the
cathode as the negative electrode (c) the electrolyte as the molten or aqueous
substance that undergoes electrolysis.
Describe the transfer of charge during electrolysis to include: (a) the movement of
electrons in the external Circuit (b) the loss or gain of electrons at the electrodes
(c) the movement of ions in the electrolyte..
Identify the products formed at the electrodes and describe the observations made
during the electrolysis of: (a) molten lead(II) bromide (b) concentrated aqueous
sodium chloride (c) dilute sulfuric acid using inert electrodes made of platinum or
carbon / graphite.
State that metals or hydrogen are formed at the cathode and that non-metals (other
than hydrogen) are formed at the anode.
Predict the identity of the products at each electrode for the electrolysis of a binary
compound in the molten state.
Identify the products formed at the electrodes and describe the observations made
during the electrolysis of aqueous copper(II) sulfate using inert carbon / graphite
electrodes and when using copper electrodes.
Predict the identity of the products at each electrode for the electrolysis of a halide
compound in dilute or concentrated aqueous solution.
Construct ionic half-equations for reactions at the anode (to show oxidation) and at
the cathode (to show reduction).
State that metal objects are electroplated to improve their appearance and
resistance to corrosion.
Describe how metals are electroplated.

4.2 Hydrogen–oxygen fuel cells

State that a hydrogen–oxygen fuel cell uses hydrogen and oxygen to produce
electricity with water as the only chemical product.
Describe the advantages and disadvantages of using hydrogen–oxygen fuel cells
in comparison with gasoline / petrol engines in vehicles.

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Electric Current:

Current is basically a flow of charged particles. It may be electrons or ions. In

a metal wire, electric current is due to the flow of electrons.

Ions are charged particles as they have lost or gained electrons. The
movements of these ions are responsible for the conduction of electricity in an ionic
compound.

Metals are good conductors of electricity due to the presence of free electrons.
Graphite is a nonmetal that conducts electricity due to the presence of
delocalized electrons between the hexagonal layers of carbon atoms.

Comparison of Electrical conductivity in ionic and covalent compounds

Covalent compounds do not have spare free electrons that can move and carry
the charge; and neither do they contain ions. Hence, it will not conduct
electricity.
Ionic substances form when a metal reacts with a non-metal. Ionic compounds
in their solid state will not conduct electricity, as the ions are not free to move
and carry the charge. When they are molten, the ions are free to move.

Remember in liquids the particles can slide over each other and move whereas in
solids the particles can only vibrate around a fixed position. When the ionic
compound is dissolved in a solvent to form a solution the ions are also made free
to move.

For example, sodium chloride forms when sodium reacts with chlorine. It contains
positively charged sodium ions and negatively charged chloride ions. Ionic
substances can be broken down by electricity.

ELECTROLYSIS

Passing an electric current through a compound which is either molten or in

solution causes chemical changes, the chemical reactions produce new products—
new substances.

Electrolysis is the process by which ionic substances are decomposed

(broken down) into simpler substances when an electric current is passed
through them.

For electrolysis to work, the ions must be free to move. This is possible when
an ionic substance is dissolved in water or molten (melted).

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 For example, if electricity is passed through copper chloride solution, the
copper chloride is broken down to form copper metal and chlorine gas.

An electrolytic cell is the vessel in which electrolysis takes place. An

electrolytic cell works like an electrical circuit and it has three main components. A
battery, Electrode and electrolyte.

• Electrolyte is a liquid that contains ions and therefore conducts electricity. It

is an ionic compound either in molten or aqueous solution.

Eg: Molten sodium chloride, molten copper chloride

• Electrodes – A rod of metal or graphite which leads an electric current to or
from an electrolyte. The electrolytic cell has two (usually inert) electrodes to
pass the electric current into the electrolyte.

The anode is the positive electrode connected to the positive terminal of the
battery.
The cathode is the negative electrode connected to the negative terminal of the
battery.

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 During electrolysis electrical energy is converted into chemical reactions.

Inert electrodes Active Electrodes

They carry current but are not They carry current and themselves
themselves changed during electrolysis. changed during electrolysis. The
The thickness of the electrode stays the thickness of the electrode changes
same during electrolysis. during electrolysis.

The inert electrodes are usually made of Metals such as copper, zinc, silver etc.
graphite or platinum wire. can be used as reactive electrodes.

During electrolysis:

• Positively charged ions (cations) move to the negative electrode(cathode)

during electrolysis. They receive electrons and are reduced.
Cu2+ + 2e → Cu
2H+ + 2e → H2
Al3+ + 3e → Al
• Negatively charged ions (anions) move to the positive electrode (anode)
during electrolysis. They lose electrons and are oxidised.

2Cl- - 2e → Cl2
4OH-- 4e → O2 + 2H2O
• Electrons flow from the anode to the positive terminal of the battery.

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In electrolysis
✓ Electrical energy is supplied and the reactions are endothermic
✓ Electrical energy is changed into chemical energy.

Electrolysis is a redox reaction. Oxidation takes place at the anode and reduction
takes place at the cathode.

When the cations or anions gain or lose electrons at the electrodes, they form atom
or molecules. So we say that the cation or anion is discharged.

Electrolysis of Lead Bromide

• Lead (II) bromide is an ionic compound.

• The solid consists of a giant structure of lead (II) ions and bromide ions
packed regularly in a crystal lattice. It doesn’t have any mobile electrons, and
the ions are locked tightly in the lattice and aren’t free to move.
• The solid lead (II) bromide doesn’t conduct electricity. As soon as the solid
melts, the ions do become free to move around, and it is this movement that
enables the electrons to flow in the external circuit.

Electrolysis breaks the molten ionic compound down to its elements giving
the metal at the cathode and the nonmetal at the anode.
PbBr2 → Pb + Br2
Electricity Cathode Anode

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 The positive lead (II) ions are attracted to the cathode, which is the negative
electrode. When they get there, they gain 2 electrons each from the electrode and
forms neutral lead atoms. These fall to the bottom of the container as molten lead.

Pb2+ + 2e- → Pb
(Reduction)

Bromide ions are attracted to the positive anode. When they get there, the
extra electron, which makes the bromide, ion negatively charged moves onto the
anode because this electrode is short of electrons. The loss of the extra electron
turns each bromide ion into a bromine atom. These join in pairs (bond covalently)
to form bromine molecules. Overall:
2Br- - 2e-→ Br2
(Oxidation) Bromine gas bubbles off.

The ions are discharged at the electrodes. Either discharging an ion simply means
that it loses its charge-giving up electron to the electrode or receiving electron from
it.

Overall electrolysis is a Redox reaction. In the ionic equations, see that the
lead (II) ions gain electrons at the cathode. Gain of electrons is reduction. The lead
(II) ions are reduced to lead atoms. The bromide ions lose electrons at the anode.
Loss of electrons is oxidation. The bromide ions are oxidized to bromine molecules.

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 Electrolysis of different electrolytes with inert electrodes
Electrolyte Cathode Reaction Anode Reaction Change to

Electrolyte

Molten PbI2 Lead is formed Iodine is formed Used up

Pb2+ + 2e- → Pb 2I- - 2e-→ I2

Molten NaCl Sodium is formed Chlorine is Used up

Na+ + 1e- → Na formed

2Cl- - 2e-→ Cl2

Molten LiCl Lithium is formed Chlorine is Used up

Li+ + 1e- → LI formed

2Cl- - 2e-→ Cl2

Molten RbCl Rubedium is formed Chlorine is Used up

Rb+ + 1e- → Rb formed

2Cl- - 2e-→ Cl2

Molten MgCl2 Magnesium is Chlorine is Used up

formed formed
Mg2+ + 2e- → Mg 2Cl- - 2e-→ Cl2

Molten ZnCl2 Zinc is formed Chlorine is Used up

Zn2+ + 2e- → Zn formed

2Cl- - 2e-→ Cl2

Molten ScF2 Scandium is formed Chlorine is Used up

Sc2+ + 2e- → Sc formed

2F- - 2e-→ F2

Molten Al2O3 Aluminium is formed Oxygen is formed Used up

Al3+ + 3e- → Al 2O2- - 4e-→ O2

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The products of Electrolysis when using inert electrodes
• Metal or hydrogen is formed at the cathode by reduction
• Non metals other than hydrogen is formed at the anode by oxidation

Electrolysis of Aqueous solutions of Compounds

An aqueous solution of a compound is a mixture of the compound with
water.
An aqueous solution of sodium chloride contains sodium ions and chloride
ions, along with hydrogen ions and hydroxide ions which comes from water. These
ions compete for discharge at the respective electrodes.

Reactivity Series and Selective Discharge of Ions

In electrolysis, when more than one type of cation or anion is present in a

solution, only one cation and one anion are preferentially discharged. This is known
as the selective discharge of ions.

If inert electrodes are used during electrolysis, the ions discharged and hence the
products formed depend on three factors:

1. The position of the metal (producing the cation) in the reactivity series.
2. The relative ease of discharge of an anion.
3. The concentration of the anion in the electrolyte.

Selective discharge of cations during electrolysis

More reactive metals have a greater tendency to form ions. Hence ions of more
reactive metals like sodium and potassium will remain as ions and it will not be
discharged. Ions of less reactive metals and hydrogen readily gain electrons and are
getting reduced.

In short

• If the metal is more reactive than hydrogen, hydrogen gas is formed at the
cathode. The metal ions stay in solution.
• If the metal is less reactive than hydrogen, the metal forms.

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If a solution containing Na+ and H+ ions is electrolysed, H+ ions are discharged in
preference to Na+ ions. It produces Hydrogen gas

If a solution containing Cu2+ and H+ ions is electrolysed, Cu2+ ions are discharged in
preference to H+ ions. It produces Copper Metal.

Selective discharge of anions during electrolysis

• A concentrated solution of a halide (Chloride, bromide or iodide) gives chlorine,

bromine or iodine at the anode.
• But if there is no halide ion or the halide ion is dilute, oxygen is formed at the
anode.
• The Sulphate (SO42-) and nitrate (NO3–) ions remain in the solution and are not
discharged during electrolysis.

If a solution containing SO42-, NO3– and hydroxide(OH–) ions is electrolysed,

the OH– ions will be discharged in preference to SO42- and NO3– ions. The OH– ions
give up electrons most readily during electrolysis to form water and oxygen.

4OH– (aq) - 4e– → 2H2O (l) + O2 (g)

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Effect of concentration on selective discharge of anions

An increase in the concentration of an anion tends to promote its discharge.

For example, in the electrolysis of concentrated sodium chloride solution, two types
of ions are attracted to the anode: Cl– and OH– ions. According to their relative ease
of discharge, OH– ions should be discharged preferentially. However, in
concentrated sodium chloride solution, Cl– ions are far more numerous
than OH– ions and so are discharged at the anode instead.

Electrolysis of Dilute Aqueous Sodium Chloride

Electrolysis of Concentrated Aqueous Sodium Chloride

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Electrolysis of Dilute Aqueous Copper sulfate using Inert
electrodes

Electrolysis of Dilute Sulfuric Acid

Pure water is not a good conductor of electricity but if a small amount of any
ionic compound or dilute sulfuric acid is added to water, it becomes a good
conductor of electricity.

Ions Present Hydrogen ion (H+) and Sulphate ion (SO42-)

(From Sulfuric Acid)
Hydrogen ion (H+) and Hydroxide ion (OH-)
(From water)
Cathode Hydrogen is formed
Reaction 2H+ + 2e- → H2
Anode Oxygen is formed
Reaction 4OH- - 4e- → 2H2O + O2
Water is used up
Two volumes of hydrogen at the cathode and one
volume of oxygen at the anode is formed.

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ELECTROLYSIS OF CONC. AQUEOUS SOLUTION USING INERT ELECTRODES

Electrolyte Cathode Anode Reaction Change to

Reaction Electrolyte

Aqueous NaCl Hydrogen is Chlorine is Solution changes to

formed formed sodium hydroxide
2H + 2e- → H2
+
2Cl - 2e-→ Cl2
-

Aqueous KBr Hydrogen is Bromine is Solution changes to

formed formed Potassium hydroxide
2H + 2e- → H2
+
2Br - 2e-→ Br2
-

Dilute Sulphuric Hydrogen is Oxygen is formed Water is used up

Acid formed 4OH- - 4e- →
2H + 2e- → H2
+
2H2O + O2

Aqueous silver Silver is formed Oxygen is formed H+ and NO3- are left,
Nitrate solution Ag+ + 1e- → Ag 4OH- - 4e- → solution turned to
AgNO3 2H2O + O2 Nitric Acid, HNO3

Aqueous Copper Copper is Oxygen is formed H+ and SO42- are left,

Sulphate solution formed 4OH- - 4e- → solution turned to
CuSO4 Cu + 2e- → Cu
2+
2H2O + O2 Sulphuric Acid, H2SO4

Electrolysis of HCl – A comparative study

Electrolyte Concentrated HCl Dilute HCl

Cathode H+ discharged H+ discharged

2H+ + 2e- → H2 2H+ + 2e- → H2

Anode Cl- discharged OH- discharged

2Cl- - 2e- → Cl2 4OH- - 4e- → 2H2O + O2

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Electrolysis of Sodium Chloride – A comparative Study
ELECTROLYTE Molten NaCl Dilute NaCl solution Concentrated NaCl
solution

Cathode Na+ discharged H+ discharged H+ discharged

Na+ + 1e- → Na 2H+ + 2e- → H2 2H+ + 2e- → H2

Anode Cl- discharged OH- discharged Cl- discharged

2Cl- - 2e- → Cl2 4OH- - 4e- → 2H2O + 2Cl- - 2e- → Cl2
O2

Electrolyte is used Water is decomposed Electrolyte is turned to

up to hydrogen and Sodium hydroxide
oxygen

Electrolysis of Rubidium Chloride – A comparative Study

ELECTROLYTE Molten RbCl Dilute RbCl solution Concentrated RbCl
solution

Cathode Rb+ discharged H+ discharged H+ discharged

Rb + + 1e- → Rb 2H+ + 2e- → H2 2H+ + 2e- → H2

Anode Cl- discharged OH- discharged Cl- discharged

2Cl- - 2e- → Cl2 4OH- - 4e- → 2H2O + O2 2Cl- - 2e- → Cl2

Electrolyte is Water is decomposed to Electrolyte is turned

used up hydrogen and oxygen to Rubidium
hydroxide

Active electrodes

They are the electrodes that take part in the process of electrolysis . All the metal
electrodes except platinum are examples of active electrodes. When an active
electrode is used, the concentration of the electrolyte remains the same. The role of
the electrolyte is just a medium for transfer of ions.

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 Metal from the anode dissolves in the electrolyte and gets deposited on the
cathode. When we use active electrodes, the loss in mass at the anode is equal to
the gain in mass at the cathode. That is, the anode becomes thin and cathode
becomes thick after electrolysis.

• Eg:- electrolysis of copper(II)sulphate solution using copper electrodes.

During electrolysis, copper from the anode dissolves in the electrolyte and
get deposited on the cathode.
At anode: Cu – 2e- → Cu2+
At cathode: Cu2+ + 2e- → Cu
• During dissolution, metal atom is converted to metal ion. During deposition,
metal ion is converted to metal atom.
Observation: Anode becomes thin.
Cathode becomes thick.

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Electrolysis of copper Sulphate – A comparative Study

Electrolysis Using
Inert Electrodes Copper Electrodes
Electrolyte Aqueous Copper Sulphate Aqueous Copper Sulphate
Cathode Cu2+ discharged Cu2+ discharged
Reaction Cu2+ + 2e- → Cu Cu2+ + 2e- → Cu
More copper metal deposits on it
-
Anode OH discharged Cu → Cu2+ + 2e-
Reaction 4OH- - 4e- → 2H2O + O2 Copper goes to the solution as
ions.
Observations ✓ Reddish brown metal is ✓ Thickness of cathode increases
deposited at the
cathode ✓ Thickness of copper anode
decreases
✓ Bubbles of oxygen is
formed at the anode ✓ Intensity of Blue colour
remains the same as copper
✓ Blue colour of the ions leave the anode and are
solution fades and the attracted to the cathode,
electrolyte becomes where they are deposited as
more acidic – H2SO4 is copper atoms, both processes
formed are taking place in the same
rate.

Industrial Applications of Electrolysis

1 - Electroplating

Electrolysis is used to electroplate objects. This is useful for coating a cheaper

metal with a more expensive one, such as copper or silver.

Electroplating - The process of depositing a layer of the metal with a layer of another
substance by an electrolytic reaction.

Two main reasons for electroplating are

✓ Improving the appearance – Highly polished shiny / decorative finish
✓ Protection from corrosion and scratching

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 Eg; Steel car bumpers are coated with chromium. Chromium coating gives a
pleasing appearance and because chromium is very hard it is resistant to scratching
and it protects the underlying metal from corrosion. Steel cans are coated with tin to
make tins for food. Cheap metal jewellery is coated with silver.
• The object to be electroplated is cleaned with sand paper or steel wool.
• The negative electrode should be the object that is to be electroplated
• The positive electrode should be the metal that you want to coat the object with
• The electrolyte should be a solution of the coating metal, such as its metal nitrate or
sulfate.

• After electroplating the object should be washed with distilled water and dried in an
oven.

Electroplating with Silver

1) The object to be plated, such as a metal spoon, is cleaned with a sand paper
or stool wool.
2) It is then connected to the negative terminal of the power supply. A piece of
silver metal is connected to the positive terminal. The electrolyte is silver
nitrate solution.
3) From the anode, silver goes to the solution as ions whereas it is attracted
towards cathode and gets deposited there. Concentration of silver nitrate
solution does not change during electroplating because Ag+ is removed in
one electrode and is continuously replaced at the other electrode in the same
rate.

At the cathode: Ag+ + 1e- → Ag

At the anode: Ag -1e-→ Ag+ +

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 4) The spoon is rotated during electroplating for uniform coating throughout.
5) After electroplating the object should be washed with distilled water and
dried in an oven.

Electroplating with Copper

The object to be plated, such as a metal key or pan, is connected to the negative
terminal of the power supply. A piece of copper is connected to the positive
terminal. The electrolyte is copper sulfate or copper nitrate solution.

At the cathode: Cu2+ + 2e- → Cu

At the anode: Cu -2e → Cu2+

1 – Electrorefining

Metals can be refined or purified by electrolysis. The impure metal forms the
anode, the cathode is a small piece of the pure metal and the electrolyte is an
aqueous solution of metal salt.
In the refining of copper

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 ▪ At the cathode copper ions from the solution lose their charge and copper
is deposited.
Cu2+ + 2e- → Cu
▪ At the Anode copper atoms lose their valency electrons and go into solution
as ions.
Cu -2e- → Cu2+
• The negative electrode gradually gets coated with pure copper as the positive
electrode gradually disappears.
• The pure copper is transferred from the anode to the cathode. The impurities
from the copper are left as anode sludge at the bottom of the cell and the
cathode becomes a large piece of pure copper.
• The color of the solution remains the same depth of blue because of Cu2+ ions
are removed at the cathode are replaced by those going into the solution at
the anode.

Hydrogen – Oxygen Fuel Cell

A fuel cell needs to be continuously supplied with the fuel and oxygen which
react together to produce electrical energy. In the hydrogen fuel cell, the fuel used
is hydrogen, the fuel cell produces electricity and the byproduct of this reaction is
water.

Fuels are substances that can burn easily in air to give out oxygen.
Combustion is the way to extract useful energy from a fuel.

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 A hydrogen fuel cell is made from an anode and a cathode with an electrolyte
contained between them.

The electrolyte is an alkali fuel cell is potassium hydroxide (KOH).

The anode is a platinum catalyst. Hydrogen is supplied to the anode and

it reacts with hydroxide ions from the electrolyte to make water. This is
an oxidation reaction in which electrons are lost from hydrogen.

2H2 + 4OH- - 4e-→ 4H2O

The electrons leave the anode and travel through the external circuit which
is using the electricity that is supplied by the fuel cell. The cathode is also
a platinum catalyst. Oxygen supplied to the cathode reacts with water and
gains electrons to make hydroxide ions in the electrolyte. This is
a reduction reaction.

2H2O + O2 + 4e- → 4OH-

The concentration of hydroxide ions in the electrolyte does not increase.

Adding the two half equations, gives the full equation for the redox reactions.

The overall reaction in the fuel cell is

hydrogen + oxygen water + energy

2H2 + O2 → 2H2O

It is also a redox reaction and the energy is given out as electrical current.

The hydrogen oxygen fuel cell is used as a source of electrical power in space
vehicles.

Advantages of using hydrogen as a fuel

✓ Environment Friendly fuel - Unlike petrol and diesel, hydrogen does not cause
any pollution. It will not generate carbon dioxide when burnt. Only water is
formed as the product of combustion.

2H2 + O2 → 2H2O

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✓ Efficient Fuel - Hydrogen is a more efficient fuel source than traditional sources
of energy and produces more energy per gram of fuel. This clearly means that a
car loaded with hydrogen fuel with go much farther than the one using same
amount of traditional source of energy.

✓ Renewable Source of Energy - Hydrogen is readily available unlike non

renewable resources of energy. It is made by electrolysis of water with a little
acid added. Solar power can be utilized to provide cheap electricity.

2H2O → 2H2 + O2

Disadvantages of using hydrogen as a fuel

 Hydrogen is extremely flammable and explosive. Special precautions must

be taken in the storage and transport of these gases.

 Hydrogen is very light and hence requires larger storage volumes compared
to other fuels.

 No cheap sources of hydrogen – Electrolysis is an expensive process.

Moreover, hydrogen is now obtained mainly from non-renewable sources of
energy such as petroleum.

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