IGCSE CHEMISTRY [F.A.

E]
ELECTRICITY AND CHEMISTRY

 Electricity is a stream of moving electrons.

 The diagram shows how the electrons move through the circuit. Electrons leave the
battery through the negative terminal. They are pumped through the wires, the bulb
and the rod, and enter the battery again through the positive terminal.
 When the electrons stream through the fine wire in the bulb, they cause the wire to
heat up so much that it gets white-hot and gives out light.

Conductors and Insulators

 A substance which allows electricity to pass through it is called a conductor.

 A substance that does not conduct electricity is called a non-conductor or insulator.
 The only solid elements that conduct electricity are the metals and graphite. These
conduct because of their free electrons. The free electrons get pumped out of one end
of the solid by the battery. Electrons then flow in the other end and through the spaces
left behind.
 Molecular or covalent substances are non-conductors. This is because they contain no
free electrons or other charged particles that can flow through them.

Electrolytes

 Ionic substances do not conduct electricity when solid. However they conduct electricity
when molten (melted) or dissolved in water. They are called electrolytes.
 The passage of electricity through the melt or solution is accompanied by a chemical
decomposition (i.e. they decompose at the same time).

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  The splitting up of an electrolyte, when molten or in aqueous solution is called
electrolysis.
 Electrolytes include acids, metal oxides, metal hydroxides and salts.
Electrolysis of molten lead (II) bromide

 The apparatus shown above could be used for the electrolysis of molten lead bromide.
Lead bromide is an electrolyte.
 The graphite rods are called electrodes. The electrodes carry the current into and out of
the molten lead bromide.
 The electrode joined to the negative terminal of the battery is called the cathode.
 The electrode joined to the positive terminal of the battery is called the anode.
 The positive electrode has a shortage of electrons and the negative electrode a surplus
of electrons.
 Once the switch is closed, bromine vapour starts to bubble out of the molten lead
bromide around the anode.
 After sometime molten lead forms below the cathode.
 The electrical energy from the battery has caused a chemical change.

𝐥𝐞𝐚𝐝 𝐛𝐫𝐨𝐦𝐢𝐝𝐞 → 𝐥𝐞𝐚𝐝 + 𝐛𝐫𝐨𝐦𝐢𝐧𝐞

𝑷𝒃𝑩𝒓𝟐(𝒍) → 𝑷𝒃(𝒍) + 𝑩𝒓𝟐

 Lead bromide is composed of lead ions, Pb2+ and bromide ions Br-.
 When lead bromide melts, the ions become free to move about. When the switch is
closed, the electrode become charged and ions of opposite charge are immediately
attracted to them; i.e. Pb2+ ions are attracted to the cathode (-ve electrode) and
bromide ions to the anode (+ve electrode).

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At the Cathode: the lead ions each receive two electrons and become lead atoms

Pb2+(l) + 2e- ==> Pb(s) (reduction)

The lead atoms collect together on the cathode and in time fall to the bottom of the beaker.

At the Anode: the bromide ions each give up one electron to become bromine atoms. These
pair together as molecules

2Br- ==> Br2 + 2e- (oxidation)

The bromine bubbles off as a gas.

Why the molten lead bromide conducts

 During the electrolysis, each lead ion takes two electrons from the cathode.
 At the same time two bromide ions each give an electron to the anode.
 The effect is the same as if two electrons flowed through the liquid from the cathode to
the anode. In other words, the lead bromide is acting as a conductor of electricity.

Electrolysis of concentrated hydrochloric acid

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  The apparatus shown could be used for the electrolysis of concentrated hydrochloric
acid. Hydrochloric acid is an electrolyte.
 Once the switch is closed, hydrogen molecules are formed around the anode. The
electrical energy from the battery has caused a chemical change
𝐡𝐲𝐝𝐫𝐨𝐜𝐡𝐥𝐨𝐫𝐢𝐜 𝐚𝐜𝐢𝐝 → 𝐡𝐲𝐝𝐫𝐨𝐠𝐞𝐧 + 𝐜𝐡𝐥𝐨𝐫𝐢𝐧𝐞
𝟐𝐇𝐂𝐥(𝐥) → 𝐇𝟐 + 𝐂𝐥𝟐(𝐠)

 Hydrochloric acid is composed of H+ ions and Cl- ions. When hydrochloric acid is molten,
the ions become free to move about.
 When the switch is closed, the electrodes become charged and ions of opposite charge
are immediately attracted to them. H+ ions are attracted to the cathode and Cl- ions are
attracted to the anode.

At the cathode: the hydrogen ions each receive one electron and become hydrogen atoms.
These pair together as molecules.
𝟐𝐇 + + 𝟐𝐞̅ → 𝐇𝟐 (Reduction)
The hydrogen bubbles off as a gas.

At the anode: the chloride ions each give up one electron to become chlorine atoms. These pair
together as molecules:
𝟐𝐂𝐥− → 𝐂𝐥𝟐 + 𝟐𝐞̅ (Oxidation)

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More examples of electrolysis of some electrolytes
1.
Electrolyte Decomposition
Sodium chloride (NaCl) 2NaCl(l) → Na(l) + Cl(g}

At the Cathode At the Anode

𝟐𝐍𝐚+ + 𝟐𝐞̅ → 𝟐𝐍𝐚 𝟐𝐂𝐥− → 𝐂𝐥𝟐 + 𝟐𝐞̅

2.
Electrolyte Decomposition
Potassium iodide (KI) KI(l) → 2K (l) + I2(g)

At the Cathode At the Anode

𝟐𝐊 + + 𝟐𝐞̅ → 𝟐𝐊 𝟐𝐈 − → 𝐈𝟐 + 𝟐𝐞̅
3.
Electrolyte Decomposition
Copper (II) bromide CuBr2(l) → Cu(l) + Br2(g)

At the Cathode At the Anode

𝐂𝐮𝟐+ + 𝟐𝐞̅ → 𝐂𝐮 𝟐𝐁𝐫 − → 𝐁𝐫𝟐 + 𝟐𝐞̅

Points to note
1. The electrolyte always decomposes. So electrical energy is causing a chemical change.
2. The electrodes are usually made of graphite or platinum. These substances are
unreactive or inert.
3. Metals always form positive ions. Positive ions always go to the cathode. So they are
called cations.
4. Non-metals (except hydrogen) always form negative ions. They also go to the anode so
are called anions.
5. When a molten ionic compound is electrolysed, a metal is always formed at the cathode
and a non-metal at the anode.

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Electrolysis of aqueous solutions
 When a salt such as sodium chloride is dissolved in water, its ions become free to move.
So the solution can be electrolysed.
 But the products will be different from when you electrolyse the molten salt, because
water itself also produces ions.
 Although water is molecular, a tiny fraction of its molecules split into ions:
+ −
𝐇𝟐 𝐎(𝐥) ⇌ 𝐇(𝐚𝐪) + 𝐎𝐇(𝐚𝐪)
 During electrolysis, these H+ and OH- compete with the metal and nonmetal ions from
the dissolved salt, to receive or give up electrons.
 These are the rules for which ion wins:

At the Cathode
1. The more reactive a metal, the more it ‘likes’ to exist as ions. So if a metal is very
reactive, its ions remain in solution. The H+ ions accept electrons and hydrogen
molecules are formed.
2. The ions of less reactive metals will accept electrons and form metal atoms, leaving
the H+ ions in solution.

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 At the Anode
3. If ions of a halogen are present (Cl-, Br- or I-), they will give up electrons more readily
than the OH- ions do. Molecules of chloride, bromine or iodine are formed.
4. If no halogen ions are present, OH- ions will give up electrons more readily than
other non-metal ions do and oxygen is formed.

Electrolysis of concentrated sodium chloride solution (Brine)

 In this elctrolysis, brine is the electrolyte.

 Once the switch is closed, hydrogen molecules are formed around the cathode and
chlorine molecules formed around the anode leaving sodium hydroxide in solution.
 Concentrated sodium chloride solution is composed of Na+ ions, H+ ions, Cl- ions and OH-
ions.
At the cathode At the anode

2H+(aq) + 2e- ==> H2(g) 2Cl- ==> Cl2 + 2e-

 However in very dilute solutions, OH- ions give up electrons at the anode to form oxygen
as well as chlorine gas.
At the anode

4OH-(aq) ==> 2H2O(l) + O2(g) + 4e-

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Extraction of aluminium

 Aluminium is extracted from purified aluminium oxide by electrolysis.

 However, aluminium oxide has a high melting point and is not readily soluble in water,
but it does dissolve in molten cryolite (Na3AlF6) and this produces a suitable electrolyte.

 The electrodes are made of carbon. The reactions taking place at the electrodes are as
follows:
At the cathode At the anode

Al3+(l) + 3e- ==> Al(l) 2O2-(l) ==> O2(g) + 4e-

Overall reaction

𝟒𝐀𝐥𝟑+ + 𝟔𝐎𝟐− → 𝟒𝐀𝐥 + 𝟑𝐎𝟐

 At the working temperature of the cell, the oxygen reacts with the carbon of the anode
to produce carbon dioxide. The anode therefore, has to be replaced frequently.
Electroplating of metals

 Electroplating is the process by which a metal surface is thin coated with another metal
using electrolysis.
 In general, the cathode is made the metal/conducting surface to be coated and the
anode is made of the plating metal which dissolves and replaces any deposit formed on
the cathode electrode.

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Metal electrodes dipped in aqueous salt solutions

M = metal, usually dipped in the metal sulphate solution.

 If a piece of copper is to be nickel plated the surface must be clean and grease free.
 The copper is made to be the cathode and a piece of nickel is the anode in an
electrolysis experiment with nickel (II) sulphate solution as the electrolyte.
 A nickel coating is deposited on the negative electrode (the copper) and the nickel
anode goes into solution as nickel (II) ions.
Uses of electroplating

1. It is used for decorative purposes.

2. It is used to prevent corrosion.
Reasons why copper and (steel cored) aluminium are used for electric cables
 Copper is a good conductor of electricity and also less reactive with atmospheric
oxygen, moisture and dilute acids.
 Aluminium is a good conductor of electricity but unlike copper, it is reactive. However,
when aluminium comes into contact with air, it reacts to form aluminium oxide (Al 2O3)
which forms a thin layer on the surface of the metal preventing fresh parts from coming
into contact with atmospheric oxygen.

Uses of electrolysis
1. Electroplating
2. Extraction of metals
3. Purification of copper
4. Manufacture of sodium hydroxide