Electrolysis

Ionic substances contain charged particles called ions. For example, lead bromide contains
positively charged lead ions and negatively charged bromide ions.
Electrolysis is the process by which ionic substances are decomposed (broken down) into
simpler substances when an electric current is passed through them.
Electricity is the flow of electrons or ions. For electrolysis to work, the compound must contain
ions. Covalent compounds cannot act as electrolytes because they contain neutral atoms.
The ions must be free to move, which is possible when an ionic substance is dissolved in water
or it is melted. For example, if electricity is passed through molten lead bromide, the lead
bromide is broken down to form lead and bromine.

This is what happens during electrolysis:

1. Positively charged ions move to the negative electrode during electrolysis. They receive electrons and
are reduced.
2. Negatively charged ions move to the positive electrode during electrolysis. They lose electrons and
are oxidised. The substance that is broken down is called the electrolyte.

Electrolytes
To be an electrolyte, a substance must be able to conduct electricity. To test for conductivity,
include a sample of the substance in a circuit that contains a source of direct current (eg a cell or
power pack) and a bulb or an ammeter. If a current flows through the substance when it is
molten or dissolved, it is an electrolyte.
 Electrolysis of molten salts
New substances form when a molten or dissolved ionic compoundconducts electricity. For
example, lead bromide can be used to produce bromine and lead using the following process:
1. place solid lead(II) bromide in a crucible and heat over a Bunsen burner until it melts
2. insert two carbon electrodes into the molten electrolyte and pass a direct current between them
Carbon electrodes are chosen because they have a high melting point and are inert (they will not
react with the reactants and products during electrolysis). The observations are summarised in
the table:

Observation Explanation
Anode Bromine vapour
(positive) Bubbles of brown gas (Br2) is produced
Silvery liquid metal present at
Cathode
this electrode underneath the Lead (Pb) is
(negative)
remaining molten electrolyte produced
It is easy to predict the products of electrolysis of molten electrolytes because they simply split
into their elements:
the metal is formed at the negative electrode because that is where the positive metal ions are attracted
the non-metal element is formed at the positive electrode where the negative non-metal ions are
attracted
For example:

Compound Anode (positive) Cathode (negative)

Zinc chloride Chlorine Zinc
Aluminium oxide Oxygen Aluminium
 Electrolysis of ionic solutions
Electrolysing aqueous solutions of ionic compounds can be more complicated than
electrolysing molten compounds, because the water molecules can provide hydrogen ions (H+)
and hydroxide ions (OH-), in addition to the ions from the ionic compounds.

At the negative electrode

Metal ions and hydrogen ions are positively charged. Whether you get the metal or hydrogen
during electrolysis depends on the position of the metal in the reactivity series:
the metal will be produced if it is less reactive than hydrogen
hydrogen will be produced if the metal is more reactive than hydrogen

The reactivity series of metal - carbon and hydrogen are not metals, but they are shown for
comparison
So, for example, the electrolysis of copper chloride solution produces copper at the
negative electrode. However, the electrolysis of sodium chloride solution produces hydrogen.

At the positive electrode

If the negative ion from the ionic compound is simple (eg Cl- or Br-), then that element is
produced. If the negative ion is a complex ion (eg NO3-, SO42-, CO32-), then oxygen is produced
from the hydroxide ion present instead.
The table summarises some of the elements you should expect to get during electrolysis.
 Negative ion in Element given off at positive
solution electrode
Chloride, Cl Chlorine, Cl2
Bromide, Br Bromine, Br2
Iodide, I Iodine, I2
Sulfate, SO42- Oxygen, O2
Nitrate, NO3- Oxygen, O2

At the negative and positive electrodes

This table shows some common ionic compounds (in solution), and the elements released when
their solutions are electrolysed using inertelectrodes, eg carbon electrodes:

Ionic substance Element at - Element at +

Copper chloride, CuCl2 Copper, Cu Chlorine, Cl2
Copper sulfate, CuSO4 Copper, Cu Oxygen, O2
Sodium chloride, NaCl Hydrogen, H2 Chlorine, Cl2
Hydrochloric acid, HCl Hydrogen, H2 Chlorine, Cl2
Sulfuric acid, H2SO4 Hydrogen, H2 Oxygen, O2

Very dilute solutions of halide compounds

If a halide solution is very dilute (eg NaCl), then oxygen will be given off instead of the halogen.
This is because the halide ions are outnumbered by the hydroxide ions from the water.
Ionic half equations
A half-equation shows you what happens at one of the electrodesduring electrolysis. Electrons
are shown as e-. A half-equation is balanced by adding, or taking away, a number of electrons
equal to the total number of charges on the ions in the equation.
When positive metal ions (cations) arrive at the negative electrode (the cathode), they gain
electrons to form neutral metal atoms. This is called reduction. For example:
Pb2+ + 2e- Pb
When negative non-metal ions (anions) arrive at the positive electrode (the anode), they lose
electrons to form neutral atoms or molecules. This is called oxidation. For example:
2Br- Br2 + 2e-

Writing half equations

Cations go to the cathode. They need to gain enough electrons to make them neutral. So an
Al3+ ion needs to gain three electrons:
Al3+ + 3e- Al
Half-equations for non-metal anions are more difficult to balance. For example, chloride ions
make chlorine gas. Most non-metal elements formed in electrolysis are diatomic molecules
(eg Cl2). For example:
Cl- Cl2
Add in two electrons to balance the charge so that both sides have the same charge. The two
electrons need to go on the right-hand side, so that both sides have an overall charge of -2. For
example:
2Cl- Cl2 + 2e-

Electrolysis calculations
Charge transferred
The amount of charge transferred during electrolysis can be calculated from the mean current
used and the time taken:
charge, Q = current, I time, t
(coulombs, C) (amperes, A) (seconds, s)

Example 1
Calculate the amount of charge transferred when a 5 A current is used for 2 minutes during
electrolysis.
2 minutes = 2 60 = 120 s
Charge = current time
Charge = 5 120 = 600 C

The faraday
One faraday represents one mole of electrons. It is equal to 96,500 coulombs. The use of the
faraday lets us work out how many moles of a substance is produced during electrolysis,
provided we know the total charge transferred.

Example 2
Sodium and chlorine are produced during the electrolysis of molten sodium chloride:
Na+ + e Na
2Cl Cl2 + 2e
9,650 coulombs of charge pass. Calculate the amount of sodium and chlorine produced.
Remember that 1 F (faraday) = 96,500 C.
Number of moles of electrons = 9,650 96,500 = 0.1 mol
1 mol of electrons are needed to produce 1 mol of sodium - so 0.1 mol of sodium is produced.
2 mol of electrons are needed to produce 1 mol of chlorine - so 0.05 mol (0.1 2) of chlorine is
produced.

Calculating masses
The mass of a substance produced during electrolysis can be calculated from the charge
transferred, the faraday, and the relative atomic mass (Ar) or relative formula mass (Mr) of the
substance.
Example 3
Bromine is produced during the electrolysis of molten lead(II) bromide:
2Br Br2 + 2e
A current of 13.4 A was used for 0.5 hours. Calculate the mass of bromine produced. 1 F =
96,500 C. Ar of Br2 = 160.
Remember: charge = current time
Charge = 13.4 1,800 = 24,120 C
Remember: One faraday represents one mole of electrons. It is equal to 96,500 coulombs.
Number of moles of electrons = 24,120 96,500 = 0.25 mol
Amount of bromine produced = 0.25 2 = 0.125 mol
Mass of bromine produced = Ar mol = 0.125 160 = 20 g

Calculating volumes
The volume of a gas produced during electrolysis can be calculated from the charge transferred
and the faraday. You also need to know the molar volume of a gas. This is the same for any gas
at room temperature and pressure (rtp) and is 24 dm3 or 24,000 cm3.

Example 4
During electrolysis of molten sodium chloride, 0.125 mol of chlorine gas was produced.
Calculate the volume of chlorine at rtp.
Volume = amount of gas molar volume
Volume of chlorine = 0.125 24 = 3 dm3 (or 3,000 cm3)

Purifying copper by electrolysis

Copper is purified by electrolysis. Electricity is passed through solutions containing copper
compounds, such as copper(II) sulfate. The anode (positive electrode) is made from impure
copper and the cathode (negative electrode) is made from pure copper.
Pure copper forms on the cathode. The slideshow shows how this works:
 1. A beaker with pure and impure copper rods dipped into copper(II) sulfate solution
2. The pure copper rod is connected to the negative terminal of a battery, and the impure rod is
connected to the positive terminal
3. The pure copper rod has increased in size, while the impure rod has deteriorated, leaving a
pool of anode sludge at the bottom of the beaker
During electrolysis, the anode loses mass as copper dissolves, and the cathode gains mass as
copper is deposited.
The slideshow shows what happens during the purification of copper by electrolysis:
 1. Four Cu ions are attached to the rod on the right, and four Cu+ ions are floating in the space
between the rods
2. A battery is connected between the rods and the Cu ions are pulled towards the left rod
3. There are now four Cu ions attached to the left rod, with four Cu+ ions floating in the middle

A half-equation shows what happens at one of the electrodes during electrolysis. Electrons are
shown as e-.
These are the half-equations:
anode: Cu Cu2+ + 2e- (oxidation)
cathode: Cu2+ + 2e- Cu (reduction)
Oxidation happens at the anode because electrons are lost. Reduction happens at the cathode
because electrons are gained.
 One way to remember this is by using the mnemonic OIL RIG:
Oxidation Is Loss of electrons, Reduction Is Gain of electrons.

Electroplating
Electrolysis is used to electroplate objects (coat them with a thin layer or metal). This is useful
for coating a cheaper metal with a more expensive one, such as copper or silver.

How it works
The negative electrode should be the object 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.
Here are two examples:

Electroplating with silver

The object to be plated, such as a metal spoon, is connected to the negative terminal of the power
supply. A piece of silver is connected to the positive terminal. The electrolyte is silver nitrate
solution.

Electroplating with copper

The object to be plated, such as a metal 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
solution.

Glossary

1. ammeterA device used to measure electric current.

2. atomAll elements are made of atoms. An atom consists of a nucleus containing
protons and neutrons, surrounded by electrons.
3. chargeProperty of matter that causes a force when near another charge. Charge
comes in two forms, positive and negative. For example, the negative charge
caused a repulsive force on a neighbouring negative charge.
4. charged particlesParticles, usually ions or electrons, that carry electrical charges.
5. compoundA substance formed by the chemical union of two or more elements.
6. covalentA covalent substance is a molecule containing one or more covalent bonds
(shared pairs of electrons).
7. electrodeA conductor used to establish electrical contact with a circuit. The
electrode attached to the negative terminal of a battery is called a negative
electrode, or cathode. The electrode attached to the positive terminal of a battery is
the positive electrode, or anode.
8. electrolysisThe decomposition (break-down) of a compound using an electric
current.
9. electrolyteA substance which, when molten or in solution, will conduct an electric
current.
10.electronSubatomic particle, with a negative charge and a negligible mass relative
to protons and neutrons.
11.elementA substance made of one type of atom only.
12.halideA halide ion is an ion formed when a halogen atom (an atom from group 7)
gains one electron. Halide ions have a single negative charge. Ionic compounds
containing halide ions may be called halides.
13.inertUnreactive.
14.ionElectrically charged particle, formed when an atom or molecule gains or loses
electrons.
15.ionic compoundAn ionic compound occurs when a negative ion (an atom that has
gained an electron) joins with a positive ion (an atom that has lost an electron).
16.moleThe unit for amount of substance, abbreviated to mol.
17.moleculeA collection of two or more atoms held together by chemical bonds.
18.moltenA term used to describe a liquid substance (eg rock, glass or metal) formed
by heating a solid.
19.oxidationThe gain of oxygen, or loss of electrons, by a substance during a
chemical reaction.
20.reactivity seriesA list of elements in order of their reactivity, usually from most
reactive to least reactive.
21.reductionThe loss of oxygen, or gain of electrons, by a substance during a
chemical reaction.