Define electrolysis as the breakdown of an ionic compound, molten or in aqueous solution, by the passage of

electricity

Describe electrolysis in terms of the ions present and reactions at the electrodes in the examples given

Describe the electrode products and the observations made during the electrolysis of:

–– molten lead(II) bromide

–– concentrated hydrochloric acid
–– concentrated aqueous sodium chloride
–– dilute sulfuric acid
between inert electrodes (platinum or carbon)

Relate the products of electrolysis to the electrolyte and electrodes used, exemplified by the specific examples
with aqueous copper(II) sulfate using carbon electrodes and using copper electrodes (as used in the refining of
copper)

State the general principle that metals or hydrogen are formed at the negative electrode
(cathode), and that non-metals (other than hydrogen) are formed at the positive electrode (anode)

Predict the products of the electrolysis of a specified binary compound in the molten state

Predict the products of electrolysis of a specified halide in dilute or concentrated aqueous solution

Construct ionic half-equations for reactions at the cathode

Describe the electroplating of metals

Outline the uses of electroplating

Describe the reasons for the use of copper and (steel-cored) aluminium in cables, and why plastics and
ceramics are used as insulators

Describe the transfer of charge during electrolysis to include:

–– the movement of electrons in the metallic conductor

–– the removal or addition of electrons from the external circuit at the electrodes
–– the movement of ions in the electrolyte

Describe the production of electrical energy from simple cells, i.e. two electrodes in an electrolyte.
(This should be linked with the reactivity series in section 10.2 and redox in section 7.4.)

Describe, in outline, the manufacture of:

–– aluminium from pure aluminium oxide in molten cryolite

–– chlorine, hydrogen and sodium hydroxide from concentrated aqueous sodium chloride
(Starting materials and essential conditions should be given but not technical details or
diagrams.)
Electrolysis
Electrolysis is the breakdown of an ionic compound, molten or in solution, by the passage of electricity
through it.

 Covalent compounds cannot conduct electricity hence they do not undergo electrolysis.
 Ionic compounds in the solid state cannot conduct electricity because they have no free ions that
can move and carry the charge.

Electrolyte:

The substance which is decomposed is called the electrolyte. An electrolyte is a substance that conducts
electricity when in the molten state or in solution.

The electricity is carried through the electrolyte by ions. In the molten state and in solution the ions are
free to move to the appropriate electrodes due to weakened forces of attraction between them.

 Substances that do not conduct electricity when in the molten state or in solution are
called nonelectrolytes.
 Substances that conduct electricity to a small extent in the molten state or in solution are
called weak electrolytes.

Electrodes:

The electric current enters and leaves the electrolyte through electrodes
They are usually made of unreactive metals such as platinum or of the nonmetal carbon (graphite). These
are said to be inert electrodes because they do not react with the products of electrolysis. The names
given to the two electrodes are cathode and anode.

 Cathode is the negative electrode which attracts cations (positively charged ions)
 Anode is the positive electrode which attracts anions (negatively charged ions).

The transfer of charge during electrolysis is by:

 the movement of electrons in the metallic or graphite electrodes

 the removal or addition of electrons from the external circuit at the electrodes
 the movement of ions in the electrolyte.

Electrolysis of lead(II) bromide:

When the electrodes are first connected, the bulb does not light, because the solid compound does not
allow electricity to pass through it. However, when the compound is heated until it is molten, the bulb
does light. The molten lead bromide contains lead ions (Pb+2) and bromide ions (Br -). This shows what
happens when the switch is closed:
The lead(ii) bromide is now behaving as an electrolyte. When this happens an orange-red vapour is seen at
the anode and lead metal is produced at the cathode.

The break-up (decomposition) of lead(ii) bromide into its constituent elements by the passage of an
electric current is called electrolysis.

molten lead(ii) bromide bromine (g) + lead (metal)

PbBr2(l) Br2 (g) + Pb(l)

1. Electrons flow from the negative terminal of the battery to the cathode.
2. In the liquid, the ions move to the electrode of opposite charge.
3. At the cathode , the Pb+2 ions accept 2 electrons. Lead begins to appear below the cathode.

lead ion+ electrons→lead atom

Pb2+(l) + 2e− → Pb(l)

This process of gaining electrons is called reduction.

4. At the anode, the Br - ions give up electrons to form neutral atoms first.
bromide ion → bromine atom + electron
Br−(l) → Br + e−

This process of losing electrons is called oxidation.

Two bromine atoms then combine to form a bromine molecule. Red-brown bromine vapour bubbles
off.

bromine atoms → bromine molecule

 2Br → Br2(g)

5. Electrons flow from the anode to the positive terminal of the battery.

Note that:

 Electrons carry the current through the wires and electrodes. But the ions carry it through the liquid.
 The graphite electrodes are inert. They carry the current into the liquid, but remain unchanged. (Electrodes
made of platinum are also inert.)

Electrolysis of aluminium oxide :

Aluminium is a reactive metal and as such was very difficult to extract from its ore. Reactive metals hold
on tightly to the element(s) they have combined with and many are extracted from their ores by
electrolysis.
The commercial extraction of aluminium involves the electrolysis of aluminium oxide (alumina).

The process involves the following stages.

 Bauxite, an impure form of aluminium oxide, is first treated with sodium hydroxide to obtain
pure aluminium oxide, removing impurities such as iron( iii) oxide and sand. This improves the
conductivity of the molten aluminium oxide.
 The purified aluminum oxide is then dissolved in molten cryolite (Na 3AlF6). Cryolite, a mineral
found naturally in Greenland, is used to reduce the working temperature of the Hall–Heroult cell
from 2017 °C (the melting point of pure aluminum oxide) to between 800 and 1000 °C. The
molten mixture is then electrolyzed in a cell.
 The Hall–Heroult cell is used in industry to extract aluminium by electrolysis.

The anodes of this process are blocks of graphite which are lowered into the molten mixture from above.
The cathode is the graphite lining of the steel vessel containing the cell.
Aluminium oxide is an ionic compound. When it is melted the ions become mobile, as the strong
electrostatic forces of attraction between them are broken by the input of heat energy.

During electrolysis the negatively charged oxide ions are attracted to the anode (the positive electrode),
where they lose electrons (oxidation).

oxide ions → oxygen molecules + electrons

2O -2(l) → O2(g) + 4e−

The positive aluminium ions are attracted to the cathode (the negative electrode). They gain electrons to
form molten aluminium metal (reduction).

aluminium ions + electrons → aluminium metal

Al3+(l) + 3e− → Al(l)

The overall reaction which takes place in the cell is:

aluminium oxide electrolysis aluminium + oxygen

2Al2O3(l) 4Al(l) + 3O2(g)

The electrolysis of other molten compounds:

The pattern is the same for all molten ionic compounds of two elements:

Electrolysis breaks the molten ionic compound down to its elements, giving the metal at the cathode, and the
non-metal at the anode.

So it is a very important process. We depend on it to obtain reactive metals such as lithium, sodium, potassium,
magnesium, and aluminium from compounds dug from the Earth.

Electrolysis of solutions
Electrolysis of acidified water
Water is a poor conductor of electricity, but it does contain some hydrogen ions, H+, and hydroxide ions, OH-.
These ions are formed when a small proportion of water molecules naturally dissociate. If water is acidified with a
little dilute sulfuric acid it becomes good conductor of electricity.

H+ ions are attracted to the cathode, gain electrons and form hydrogen gas OH- ions are attracted to the anode, lose
electrons and form oxygen gas

At the cathode:

2H+ + 2 e _ → H2

At the Anode:

4 OH_ → 4 e _ + O2 + 2H2O

The overall balanced equation for the process is:

2H2O(l) → 2H2(g) + O2(g)

The volume of hydrogen given off is twice the volume of oxygen given off.

Electrolysis of dissolved ionic compounds

An electrolyte formed by dissolving an ionic compound contains:

 hydrogen ions from the water and positive ions from the compound
 hydroxide ions from the water and negative ions from the compound

The ions compete at each electrode to gain or lose electrons.

The rules for the electrolysis of a solution

At the cathode (-), either a metal or hydrogen forms.

 the metal is produced at the cathode if it is less reactive than hydrogen such as copper and nickel
 hydrogen is produced at the cathode if the metal is more reactive than hydrogen
 Whether hydrogen or a metal is produced at the cathode depends on the position of the metal in the
metal reactivity series:

At the anode (+), a non-metal other than hydrogen forms.

1. OH– ions and non-metal ions attracted to positive electrode

2. If it is a concentrated solution of a halide (a compound containing Cl 2, Br 2 or I 2 ions), then chlorine,
bromine, or iodine form.
3. But if the halide solution is dilute, or there is no halide, oxygen forms.
4. The product formed depends on which ion loses electrons more readily, with the more reactive ion
remaining in solution. A reactivity series of anions is shown below:

More reactive SO42- → NO3– → OH– → Cl– → Br– → I–  Less reactive

Concentrated and dilute solutions

 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 

Uses of Chlorine:
Chlorine, a poisonous yellow-green gas
Used for making ...

 the plastic PVC (nearly 1/3 of it used for this)

 solvents for degreasing and drycleaning
 medical drugs (a large % of these involve chlorine)
 weedkillers and pesticides (most of these involve chlorine)
 paints and dyestuffs
 bleaches
 hydrogen chloride and hydrochloric acid
 It is also used as a sterilising agent, to kill bacteria in water
 supplies and swimming pools.

Sodium hydroxide solution, alkaline and corrosive

Used in making ...

 soaps
 detergents
 viscose (rayon) and other textiles
 paper (like the paper in this book)
 ceramics (tiles, furnace bricks, and so on)
 dyes
 medical drugs

Hydrogen, a colourless flammable gas

Used ...

 in making nylon
 to make hydrogen peroxide
 to ‘harden’ vegetable oils to make margarine
 as a fuel in hydrogen fuel cells

Electrolysis of copper(II) sulfate solution

Copper(ii) sulfate solution (CuSO4(aq)) may be electrolysed using inert graphite electrodes in a
cell. When the solution is electrolysed, oxygen gas and copper metal are formed at the anode and
cathode respectively. Four ions are present in solution:

from the water: H+(aq) OH−(aq)

from the copper(ii) sulfate: Cu2+(aq) and SO2-4 (aq)
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

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

Electroplating
Electroplating is the process involving electrolysis to plate, or coat, one metal with another or a
plastic with a metal. Often the purpose of electroplating is

 to give a protective coating to the metal beneath. For example, bath taps are chromium plated
to prevent corrosion
 to give a shiny, more attractive finish

The electroplating process is carried out in a cell. This is often known as the ‘plating bath’ and it
contains a suitable electrolyte, usually a solution of a metal salt. For silver plating the electrolyte is a
solution of a silver salt. The article to be plated is made the cathode in the cell so that the metal ions
move to it when the current is switched on.

At the anode

The silver dissolves, forming silver ions in solution:

Ag (s) → Ag + (aq) + e −

The cathode reaction in this process is:

silver ions + electrons → silver atoms

Ag (aq) + e → Ag(s)
+ −

 The anode is made from the pure metal used to coat

 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
Silverplating: electroplating with silver. When the electrodes are connected to a power source, electroplating begins

Electrochemical cells
An electrochemical 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 circuit

A common example is zinc and copper

Zinc is the more reactive metal and forms ions more easily, releasing electrons as its atoms form ions

The electrons give the more reactive electrode a negative charge and they then flow around the circuit to
the copper 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, the greater the voltage
 Electrochemical cell made with copper and magnesium. These metals are further apart on the reactivity
series than copper and zinc and would hence produce a greater voltage

A membrane, such as one made from Nafion, Flemion or Aciplex, is used to prevent the reaction between the chlorine and hydroxide ions.

Electrolysis of brine from Bryan book