5.1.

1 Electrolysis
Electrolysis: Basics
• When an electric current is passed through a molten ionic compound the compound
decomposes or breaks down
• The process also occurs for aqueous solutions of ionic compounds
• Covalent compounds cannot conduct electricity hence they do not undergo electrolysis
• Ionic compounds in the solid state cannot conduct electricity either since they have no free
ions that can move and carry the charge

Particles in ionic compounds are in fixed position in the solid state but can move around when
molten or in solution

Key terms

• Electrode is a rod of metal or graphite through which an electric current flow into or out of an
electrolyte
• Electrolyte is the ionic compound in molten or dissolved solution that conducts the electricity
• Anode is the positive electrode of an electrolysis cell
• Anion is a negatively charged ion which is attracted to the anode
• Cathode is the negative electrode of an electrolysis cell
• Cation is a positively charged ion which is attracted to the cathode
 The basic set-up of an electrolysis cell xam Tip
Use the PANIC mnemonic to remember which electrode is the positive and which is the negative:

Positive (is) Anode Negative Is Cathode

Electrolysis: General Principles

Positive electrode (anode)

• Non-metal ions (other than hydrogen) are attracted to the positive electrode
• Non-metal ions will lose electrons to form the non-metal
• The product formed depends on which ion loses electrons more readily, with the more reactive
ion remaining in solution

Negative electrode (cathode)

• H+ and metal ions attracted to the negative electrode but only one will gain electrons
• Either hydrogen or metal will be produced
• If the metal is above hydrogen in reactivity series, then hydrogen will be produced and
bubbling will be seen at the cathode
The electrolysis of molten binary ionic compounds

• A binary ionic compound is one consisting of just two elements joined together by ionic
bonding
• When these compounds undergo electrolysis, they always produce their corresponding
elements
• To predict the products made at each electrode, first identify the ions
• The positive ion will migrate towards the cathode and the negative ion will migrate towards
the anode
• Therefore, the cathode product will always be the metal, and the product formed at
the anode will always be the non-metal

Example: Electrolysis of molten lead (II) bromide

Method:

• Add lead (II) bromide into a beaker and heat so it will turn molten, allowing ions to be free to
move and conduct an electric charge
• Add two graphite rods as the electrodes and connect this to a power pack or battery
• Turn on power pack or battery and allow electrolysis to take place
• Negative bromide ions move to the positive electrode (anode) and each loses one electron to
form bromine molecules. There is bubbling at the anode as brown bromine gas is given off
• Positive lead ions move to the negative electrode (cathode) and gain electrons to form a grey
lead metal which deposits on the surface of the electrode
 Diagram showing the electrolysis of lead (II) bromide

Worked Example
Identify the product formed at the anode and cathode during the electrolysis of molten potassium
chloride.

Answer:

• The ions present are potassium (K+) and chloride (Cl-)

• The chloride ions are attracted to the anode and form chlorine gas
• The potassium ions are attracted to the cathode and form potassium metal
Electrolysis of Aqueous Solutions
• Aqueous solutions will always have water present (H2O)
• In the electrolysis of aqueous solutions, the water molecules dissociate producing H+ and
OH– ions:

H2O ⇌ H+ + OH–

• These ions are also involved in the process and their chemistry must be considered
• We now have an electrolyte that contains ions from the compound plus ions from the water
• Which ions get discharged and at which electrode depends on the relative reactivity of the
elements involved
• Concentrated and dilute solutions of the same compound give different products
• For anions, the more concentrated ion will tend to get discharged over a more dilute ion

Positive Electrode (anode)

• Negatively charged OH– ions and non-metal ions are attracted to the positive electrode
• If halide ions (Cl-, Br-, I-) and OH- are present then the halide ion is discharged at the anode,
gains electrons and forms a halogen (chlorine, bromine or iodine)
• If no halide ions are present, then OH- is discharged at the anode, gains electrons and forms
oxygen gas
• In both cases the other negative ion remains in solution
• The concentration of the solution also affects which ion is discharged:
o If a concentrated halide solution is being electrolysed, the halogen forms at the anode
o If a dilute halide solution is being electrolysed, oxygen is formed
• For example:
o For a concentrated solution of barium chloride, the Cl- ions are discharged more readily
than the OH- ions, so chlorine gas is produced at the anode
o If the solution is dilute however only the OH- ion is discharged and so oxygen would be
formed

Negative Electrode (cathode)

• Positively charged H+ and metal ions are attracted to the negative electrode but only one will
gain electrons
• Either hydrogen gas or metal will be produced
• If the metal is above hydrogen in the reactivity series, then hydrogen will be produced and
bubbling will be seen at the cathode
• This is because the more reactive ions will remain in the solution, causing the least reactive ion
to be discharged
• Therefore, at the cathode, hydrogen gas will be produced unless the positive ions from the
ionic compound are less reactive than hydrogen, in which case the metal is produced
The reactivity series of metals including hydrogen and carbon

Products formed for Common Aqueous Solutions

Determining what gas is produced

• If the gas produced at the cathode burns with a 'pop' when a sample is lit with a lighted splint
then the gas is hydrogen
• If the gas produced at the anode relights a glowing splint dipped into a sample of the gas then
the gas is oxygen
• The halogen gases all produce their own colours (bromine is red-brown, chlorine is yellow-
green and fluorine is pale yellow)

Reactions at the Electrodes & Ionic Half-Equations

Extended

• In electrochemistry we are mostly concerned with the transfer of electrons, hence the definitions
of oxidation and reduction are applied in terms of electron loss or gain rather than the addition
or removal of oxygen
• Oxidation is when a substance loses electrons and reduction is when a substance gain
electron
• As the ions come into contact with the electrode, electrons are either lost or gained and they
form neutral substances
• These are then discharged as products at the electrodes
• At the anode, negatively charged ions lose electrons and are thus oxidised
 • At the cathode, the positively charged ions gain electrons and are thus reduced
• Half equations show the oxidation and reduction of the ions involved
• It is important to make sure the charges are balanced

Table of Reduction Reactions at the Cathode

Exam Tip
To help you remember the definitions of oxidation and reduction use OIL RIG

Oxidation Is Loss (of electrons) Reduction Is Gain (of electrons)

Products of Electrolysis & Charge Transfer

Extended

Transfer of Charge

• During electrolysis the electrons move from the power supply towards the cathode
• Positive ions within the electrolyte move towards the negatively charged electrode which is the
cathode
• Here they accept electrons from the cathode and either a metal or hydrogen gas is produced
• Negative ions within the electrolyte move towards the positively charged electrode which is the
anode
• If the anode is inert (such as graphite or platinum), the ions lose electrons to the anode and
form a nonmetal or oxygen gas
• If the anode is a reactive metal, then the metal atoms of the anode lose electrons and go into
solution as ions, thinning the anode
 Diagram showing the direction of movement of electrons and ions in the electrolysis of NaCl

Copper refining

• The electrolysis of CuSO4 using inert electrodes (graphite rods) produces oxygen and copper
• By changing the electrodes from graphite to pure and impure copper, the products can be
changed at each electrode
• Electrolysis can be used to purify metals by separating them from their impurities
• In the set-up, the anode is impure copper
• The cathode is a thin sheet of pure copper
• The electrolyte used is an aqueous solution of a soluble salt, in this case copper (II)
sulfate solution
• At the anode:
o Copper atoms lose electrons and go into the solution as ions

Cu → Cu2+ + 2e-

•
o The mass of the anode decreases due to loss of atoms and the impurities fall to the
bottom of the cell as sludge
 • At the cathode:
o The copper ions in the solution are attracted to the cathode where they gain electrons
and form now purified copper atoms

Cu2+ + 2e- → Cu

•
o Copper collects on the cathode causing its mass to increase

Electrical Energy
Extended

• A simple cell is a source of electrical energy

• The simplest design consists of two electrodes made from metals of different
reactivity immersed in an electrolyte and connected to an external voltmeter by wire, creating a
complete circuit
• A common example is zinc and copper
• Zinc is the more reactive metal and forms ions more easily, readily releasing electrons
• The electrons give the more reactive electrode a negative charge and sets up a charge
difference between the electrodes
• The electrons then flow around the circuit to the copper electrode which is now the
more positive electrode
• The difference in the ability of the electrodes to release electrons causes a voltage to be
produced
• The greater the difference in the metals reactivity then the greater the voltage produced
• The electrolyte used also affects the voltage as different ions react with the electrodes in
different ways
 Simple cell made with Cu and Mg. These metals are further apart on the reactivity series than Cu
and Zn and produce a greater voltage

Exam Tip
Use the reactivity series of metals to compare different cells and deduce the relative voltages.

5.1.2 Electroplating
Electroplating
• Electroplating is a process where the surface of one metal is coated with a layer of a different
metal
• The anode is made from the pure metal you want to coat your object with
• The cathode is the object to be electroplated
• The electrolyte is an aqueous solution of a soluble salt of the pure metal at the anode
A piece of iron being electroplated with tin. The electrolyte is tin (II) chloride, a water-soluble salt
of tin

Uses of electroplating

• Electroplating is done to make metals more resistant to corrosion or damage

o e.g., chromium and nickel plating
• It is also done to improve the appearance of metals,
o e.g., coating cutlery and jewellery with silver

Conductors & insulators

Conductors

• Conductors of electricity allow electrical charge to pass through them easily

• Conductors can be:
o Solids such as metals or graphite
o Liquids such as molten lead bromide or molten metals
o Solutions such as sodium chloride solution
• Copper is used extensively in electrical wiring as it is an excellent conductor and
is malleable and easy to work with
• Aluminium is used in overhead cables which are reinforced with a steel core
• The steel core provides extra strength and prevents the cable from breaking under its own
weight
• Although not as good a conductor as copper, aluminium is less dense and cheaper than copper
Insulators

• Insulators resist the flow of electricity and do not conduct

• Most insulators are solids of plastic, rubber or ceramic
• Plastics are used as insulators and are placed around electrical wiring and for some tool and
machine handles
• Ceramics are used in very high voltage lines where contact between the power line and the
metal of the pylon would be dangerous

5.2.1 Industrial Applications

Manufacture of Aluminium, Chlorine, Hydrogen & Sodium Hydroxide
Extended

Extraction of aluminium

• The Earth’s Crust contains metals and metal compounds such as gold, iron oxide and
aluminium oxide
• To be useful, the more reactive metals have to be extracted from their ore through processes
such as electrolysis, using a blast furnace or by reacting with more reactive material
• Metals which lie above carbon have to be extracted by electrolysis as they are too reactive to
economically be extracted by displacement
Reactivity series & extraction of metals

Extraction of aluminium by electrolysis

Diagram showing the extraction of aluminium by electrolysis

Raw Materials:

• Aluminium ore (bauxite)

Explanation:

• The bauxite is first purified to produce aluminium oxide Al2O3

• Aluminium oxide has a very high melting point so it is first dissolved in
molten cryolite producing an electrolyte with a lower melting point, as well as a better
conductor of electricity than molten aluminium oxide. This also reduces expense considerably
• The electrolyte is a mixture of aluminium oxide in molten cryolite at a temperature of about
1000 °C. The molten aluminium is siphoned off from time to time and fresh aluminium oxide is
added to the cell. The cell operates at 5-6 volts and with a current of 100,000 amps. The heat
generated by the huge current keeps the electrolyte molten
• A lot of electricity is required for this process of extraction which is very expensive

Reaction at the Negative Electrode:

• Aluminium ions are attracted to the cathode where they gain electrons and form aluminium
metal

Al3+ + 3e- → Al

• The aluminium melts and collects at the bottom of the cell and is then tapped off:

Reaction at the Positive Electrode:

• Oxide ions are attracted to the anode, and lose electrons to form oxygen gas

2O2- → O2 + 4e-

• Some of the oxygen produced at the anode then reacts with the graphite (carbon) electrode to
produce carbon dioxide gas

C (s) + O2 (g) → CO2 (g)

• This causes the carbon anodes to wear away, so they must be replaced regularly.

Manufacture of chlorine, hydrogen and sodium hydroxide

• Brine is a concentrated solution of aqueous sodium chloride

• When electrolysed it produces chlorine and hydrogen at the electrodes leaving behind sodium
hydroxide solution
• These substances all have important industrial uses:
o Chlorine is used to make bleach
o Hydrogen is used to make margarine
 o Sodium hydroxide is used to make soap and detergents

• The electrolyte is concentrated sodium chloride which contains the following ions: Na +, H+,
Cl- and OH-

Reaction at the Negative Electrode:

• The H+ ions are discharged at the cathode as they are less reactive than sodium ions
• The H+ ions gain electrons to form hydrogen gas

2H+ + 2e- → H2

Reaction at the Positive Electrode:

• The Cl– ions are discharged at the anode

• They lose electrons and chlorine gas forms

2Cl- → Cl2 + 2e-

• The Na+ and OH– ions remain behind and form the NaOH solution

Diagram showing the products of the electrolysis of brine