Topic 1: Principle of Chemistry

1. i) Electrolysis

1.55​ ​(chemistry​ ​only)​ ​understand​ ​why​ ​covalent​ ​compounds​ ​do​ ​not​ ​conduct
electricity

● They​ ​do​ ​not​ ​have​ ​free​ ​electrons​ ​–​ ​the​ ​electrons​ ​are​ ​shared​ ​in​ ​a​ ​covalent​ ​bond

1.56​ ​(chemistry​ ​only)​ ​understand​ ​why​ ​ionic​ ​compounds​ ​conduct​ ​electricity

only​ ​when​ ​molten​ ​or​ ​in​ ​aqueous​ ​solution

● Ions​ ​are​ ​fixed​ ​when​ ​ionic​ ​compounds​ ​are​ ​solid,​ ​meaning​ ​they​ ​can’t​ ​move​ ​so​ ​can’t
conduct​ ​electricity
● when​ ​the​ ​compounds​ ​are​ ​molten​ ​or​ ​in​ ​aqueous​ ​solution,​ ​the​ ​ions​ ​(that​ ​are
electrically​ ​charged)​ ​are​ ​able​ ​to​ ​move​ ​and​ ​carry​ ​charge

1.57​ ​(chemistry​ ​only)​ ​know​ ​that​ ​anion​ ​and​ ​cation​ ​are​ ​terms​ ​used​ ​to​ ​refer​ ​to
negative​ ​and​ ​positive​ ​ions​ ​respectively

● aNion​ ​=​ ​Negatively​ ​charged​ ​ion​ ​(-)

● ca+ion​ =​ ​ ​posi+ively​ ​charged​ ​ion​ ​(+)

1.58​ ​(chemistry​ ​only)​ ​describe​ ​experiments​ ​to​ ​investigate​ ​electrolysis,​ ​using

inert​ ​electrodes,​ ​of​ ​molten​ ​compounds​ ​(including​ ​lead(II)​ ​bromide)​ ​and
aqueous​ ​solutions​ ​(including​ ​sodium​ ​chloride,​ ​dilute​ ​sulfuric​ ​acid​ ​and​ ​copper
(II)​ ​sulfate)​ ​and​ ​to​ ​predict​ ​the​ ​products

● During​ ​electrolysis,​ ​positively​ ​charged​​ ​ions​ ​move​ ​to​ ​the​ ​negative​ ​electrode
(cathode)​,​ ​and​ ​negatively​ ​charged​ ​ions​ ​move​ ​to​ ​the​ ​positive​ ​electrode​ ​(anode).
● Ions​ ​are​ ​discharged​ ​at​ ​the​ ​electrodes​ ​producing​ ​elements,​ ​this​ ​process​ ​is​ ​called
electrolysis
● When​ ​you​ ​have​ ​a​ ​ionic​ ​solution​ ​(NOT​ ​a​ ​molten​ ​ionic​ ​compound),​ ​your​ ​solution
will​ ​contain:​ ​the​ ​ions​ ​that​ ​make​ ​up​ ​the​ ​ionic​ ​compound,​ ​and​ ​the​ ​ions​ ​in​ ​water
(OH​-​​ ​and​ ​H+​​ )
● at​ ​the​ ​cathode​ ​(-):
○ hydrogen​ ​(from​ ​H+​​ ​ ​in​ ​water)​ ​is​ ​produced​ ​UNLESS​ ​the​ ​+​ ​ions​ ​in​ ​the​ ​ionic
compound​ ​are​ ​from​ ​a​ ​metal​ ​less​ ​reactive​ ​than​ ​hydrogen
○ if​ ​the​ ​metal​ ​is​ ​less​ ​reactive,​ ​it​ ​will​ ​be​ ​produced​ ​instead
● at​ ​the​ ​anode​ ​(+):
○ oxygen​ ​(from​ ​OH​-​​ ​in​ ​water)​ ​will​ ​be​ ​produced​ ​UNLESS​ ​the​ ​ionic​ ​compound
contains​ ​halide​ ​ions​ ​(Cl​-​,​ ​Br​-​,​ ​I​-​)
○ if​ ​there​ ​are​ ​halide​ ​ions,​ ​the​ ​halogen​ ​will​ ​be​ ​produced​ ​instead​ ​(e.g.​ ​Cl​2​)

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 ● Using​ ​the​ ​logic​ ​above…
● Electrolysis​ ​of:
○ Sodium​ ​chloride​ ​solution
■ H​+​​ ​ions​ ​go​ ​to​ ​cathode​,​ ​H2​​ ​ ​(g)​ ​is​ ​produced​ ​(Na​ ​is​ ​more​ ​reactive​ ​than
hydrogen)
■ Cl​-​​ ​ions​ ​go​ ​to​ ​anode​,​ ​Cl​2​​ ​(g)​ ​is​ ​produced​ ​(Cl​-​​ ​are​ ​halide​ ​ions)
○ Copper​ ​(II)​ ​sulfate​ ​solution
■ Cu​+​​ ​ions​ ​go​ ​to​ ​cathode​,​ ​Cu​ ​(s)​ ​is​ ​produced​ ​(Cu​ ​is​ ​less​ ​reactive​ ​than
hydrogen)
■ OH​-​​ ​ions​ ​go​ ​to​ ​anode​,​ ​O2​​ ​ ​(g)​ ​is​ ​produced​ ​(SO​4​2-​​ ​ions​ ​are​ ​not​ ​halide
ions)
○ Water​ ​acidified​ ​with​ ​sulfuric​ ​acid
■ H​+​​ ​to​ ​cathode​,​ ​H2​​ ​ ​(g)​ ​is​ ​produced​ ​(these​ ​are​ ​the​ ​other​ ​ions​ ​present
in​ ​sulfuric​ ​acid​ ​H​2​SO​4​)
■ OH​-​​ ​to​ ​anode​,​ ​O2​​ ​ ​(g)​ ​is​ ​produced​ ​(SO​4​2-​​ ​ions​ ​are​ ​not​ ​halide​ ​ions)
○ Molten​ ​lead​ ​(II)​ ​bromide​ ​(demonstration)
■ Pb​2+​​ ​to​ ​cathode​,​ ​Pb​ ​(s)​ ​is​ ​produced​ ​(not​ ​in​ ​solution​ ​so​ ​these​ ​are
the​ ​only​ ​+​ ​ions​ ​present)
■ Br​-​​ ​to​ ​anode​,​ ​Br​2​​ ​(l)​ ​is​ ​produced​ ​ ​(not​ ​in​ ​solution​ ​so​ ​these​ ​are​ ​the
only​ ​-​ ​ions​ ​present)

1.59​ ​(chemistry​ ​only)​ ​write​ ​ionic​ ​half-equations​ ​representing​ ​the​ ​reactions

at​ ​the​ ​electrodes​ ​during​ ​electrolysis​ ​and​ ​understand​ ​why​ ​these​ ​reactions​ ​are
classified​ ​as​ ​oxidation​ ​or​ ​reduction

● This​ ​is​ ​an​ ​example​ ​of​ ​a​ ​half​ ​equation;​ ​the​ ​small​ ​number​ ​is
always​ ​the​ ​same​ ​as​ ​the​ ​2​ ​larger​ ​numbers​ ​within​ ​the
equation.​ ​&​ ​electrons​ ​are​ ​represented​ ​by​ ​the​ ​symbol​ ​‘e-‘

● Oxidation​ ​Is​ ​Loss​ ​(of​ ​electrons)

● Reduction​ I​ s​ ​Gain​ ​(of​ ​electrons)

● writing​ ​half​ ​equations​ ​for​ ​the​ ​reactions​ ​at​ ​each​ ​electrode:

○ negative​ ​electrode:​ ​X​+​​ ​->​ ​X,​ ​so​ ​ionic​ ​equation​ ​must​ ​be:
X​+​​ ​+​ ​e-​​ ​ ​->​ ​X,​ ​electrons​ ​gained,​ ​so​ ​positive​ ​ions​ ​are​ ​reduced
○ positive​ ​electrode:​ ​X​-​​ ​->​ ​X,​ ​so​ ​ionic​ ​equation​ ​must​ ​be:
X​-​​ ​->​ ​e-​​ ​ ​+​ ​X,​ ​electrons​ ​are​ ​lost,​ ​so​ ​negative​ ​ions​ ​are​ ​oxidised

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1.60​ ​(chemistry​ ​only)​ ​practical:​ ​investigate​ ​the​ ​electrolysis​ ​of​ ​aqueous
solutions

example-​ ​copper​ ​sulfate​ ​solution​ ​using​ ​copper​ ​electrodes

● set​ ​up:
○ anode​ ​is​ ​made​ ​of​ ​impure​ ​copper​ ​(that​ ​you​ ​are​ ​purifying)
○ cathode​ ​is​ ​made​ ​of​ ​pure​ ​copper
○ the​ ​solution​ ​is​ ​copper​ ​sulfate
● what​ ​happens:
○ Cu​2+​​ ​ions​ ​from​ ​the​ ​anode​ ​move​ ​to​ ​the​ ​cathode,​ ​where​ ​they​ ​gain​ ​electrons
and​ ​are​ ​discharged​ ​as​ ​pure​ ​copper
○ impurities​ ​form​ ​as​ ​sludge​ ​below​ ​the​ ​anode
● the​ ​cathode​ ​will​ ​increase​ ​in​ ​mass​ ​as​ ​it​ ​gains​ ​pure​ ​copper,​ ​whilst​ ​the​ ​anode​ ​will
lose​ ​mass​ ​as​ ​copper​ ​ions​ ​are​ ​lost​ ​(they​ ​replace​ ​the​ ​ones​ ​from​ ​the​ ​CuSO​4​​ ​solution
that​ ​go​ ​to​ ​the​ ​cathode)​ ​and​ ​so​ ​are​ ​impurities

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 Complete Notes

TOPIC Electrolysis
Topic 1: Principle of Chemistry
14 1. i) Electrolysis

Objectives
Candidates should be able to:
(a) describe electrolysis as the conduction of electricity by an ionic compound (an electrolyte), when
molten or dissolved in water, leading to the decomposition of the electrolyte

but which are free to move when molten or in solution

(c) describe, in terms of the mobility of ions present and the electrode products, the electrolysis of
molten sodium chloride, using inert electrodes
(d) predict the likely products of the electrolysis of a molten binary compound
(e) apply the idea of selective discharge based on
(i) cations: linked to the reactivity series

(iii) concentration effects (In all cases above, inert electrodes are used.)
(f) predict the likely products of the electrolysis of an aqueous electrolyte, given relevant information
(g) construct ionic equations for the reactions occurring at the electrodes during the electrolysis,
given relevant information
(h) describe the electrolysis of aqueous copper(II) sulfate with copper electrodes as a means of
purifying copper
(i) describe the electroplating of metals
(j) describe the production of electrical energy from simple cells (i.e. two electrodes in an electrolyte)

1. Electrolytic Cell
Electrolysis is the use of electricity to break down a compound into its constituents.
The process takes place in an electrolytic cell.

battery
+ –

electrolyte
anode cathode

The battery provides a source of electricity for reactions to occur. During the process,

Electrolysis 41
 The electrodes used in electrolysis conduct electricity. Inert graphite or platinum
electrodes are usually used.
The electrode connected to the positive terminal of the battery is the anode and the
electrode connected to the negative terminal of the battery is the cathode. Reduction

usually an acid solution, or an ionic compound that is molten or dissolved in water. A

lattice structure.

2. Electrolysis of Molten Ionic Compounds

When an ionic compound is molten, it splits up into positive ions (cations) and negative
ions (anions) which are free to move to the cathode and the anode respectively.
At the cathode, electrons are taken in by cations, while at the anode, electrons are
lost by anions. To maintain a complete electrical circuit, the number of electrons taken
in at the cathode must be the same as the number of electrons lost at the anode.

electrons.

3. Electrolysis of Solutions of Ionic Compounds

When a solution of an ionic compound is used instead, the autoionisation of water
has to be taken into consideration as well.

water
H2O H+ + OH–
These ions will compete with those of the ionic compound to be discharged at each
of the electrodes.
The ease of discharge of cations can be predicted based on the reactivity series. As
reactive metals tend to form ions, their ions are not easily discharged. Ions of less
reactive metals have a higher tendency of getting discharged as they accept electrons
more easily.

OH! I! Br! Cl! NO3! SO42!

Most likely to Least likely to

be discharged be discharged

are usually not discharged and tend to stay in the solution.

However, when the solution is concentrated, halide ions are preferentially discharged

42 TOPIC 14
 electrodes. Impure copper is used as the anode while pure copper acts as the cathode.
At the anode, OH! ions are not discharged since the electrode is not inert. Instead,
2+
ions.
2+
(aq) + 2e!

are left behind to sink to the bottom of the cell as the anode dissolves.
At the cathode, Cu2+ ions in the electrolyte are discharged and deposited on the pure
copper.
Cathode: Cu2+(aq) + 2e!
The pure copper cathode gains mass as a layer of pure copper is deposited.

6. Electroplating
Electroplating is done to coat a metal with another metal to improve its appearance
or to improve its resistance to corrosion.
The metal used for plating is used as the anode and the object to be electroplated
acts as the cathode. The electrolyte used is the salt solution of the metal used for
plating.
The plating of an object with copper metal is shown below.

copper(II) sulfate
solution
copper
anode object to be
electroplated (cathode)

Copper metal acts as the anode as it is used to plate the object. The electrolyte used
is a salt solution of its salt (copper(II) sulfate solution) and the object to be plated acts
as the cathode.
2+
ions, which enter the electrolyte.
2+
At the cathode, Cu ions are discharged and deposited on the object, plating it with
copper metal.

Electrolysis 43
 7. Simple Cells
Simple cells convert chemical energy into electrical energy. The cell uses two different
metals as electrodes and the voltage produced varies depending on the metals used.
In such a cell, the more reactive metal acts as the anode while the less reactive metal
acts as the cathode.
In a zinc-copper cell, zinc metal acts as the anode while copper acts as the cathode.
2+
ions. In the process, electrons are released

2+
(aq) + 2e!
2+
ions in the
electrolyte are reduced and deposited as copper metal on the cathode.
Cathode: Cu2+(aq) + 2e!

electron flow
V
voltmeter

zinc (anode) copper (cathode)

copper (ll) sulfate

solution

cathode gains mass as Cu2+ ions are reduced and deposited. The overall equation
of the reaction is obtained by adding the half-equations.
Overall equation: Zn(s) + Cu2+ 2+
(aq) + Cu(s)
A greater voltage is produced when the two metals used are far apart in the reactivity
series. A magnesium-copper cell generates a higher voltage than a zinc-copper cell
since the difference in reactivity is greater in the magnesium-copper cell.

44 TOPIC 14