HKDSE CHEMISTRY / Topic 7 Redox reactions, chemical cells and electrolysis / Chapter 22 / Page.

1
Chapter 22.

Electrolysis
Topic 7(e) Electrolysis
- describe the materials needed to construct an electrolytic cell
- electrolysis as the decomposition of substances by electricity as exemplified by electrolysis of
i. dilute sulphuric acid
ii. sodium chloride solutions of different concentrations (very dilute Vs dilute, conc.)
iii. copper(II) sulphate solution
- describe the anodic and cathodic reactions, overall reaction and observable changes of the
electrolyte in electrolytic cells
- preferential discharge of ions in relation to the E.C.S., concentration of ions and nature of electrodes
- predict products at each electrode of an electrolytic cell with reference to the factors affecting
the preferential discharge of ions
- describe the anodic and cathodic reactions, overall reaction and observable changes of
electrolyte in electroplating
- understand the environmental impact of the electroplating industry

22.1 Definition of Electrolysis

(1) Electrolysis is a redox reaction in which electrolytes, when molten or in aqueous solutions, are
decomposed by electricity.
(2) The general setup for electrolysis:

Voltameter

(3) The set-up consists of the followings:

(a) Direct current (d.c.) power supply
• D.c. is used in electrolysis. If an alternating current (a.c.) is used, the polarities of the
electrodes change continuously and different products will be obtained at the same electrode.
(b) Ammeter
• The symbol in the circuit represents an ammeter, an instrument used to measure
the electric current passing through a circuit. The unit of current is ampere, A.
 HKDSE CHEMISTRY / Topic 7 Redox reactions, chemical cells and electrolysis / Chapter 22 / Page.2
(c) Variable resistor

• The symbol represents a variable resistor, an instrument used to vary the resistance of
the circuit and hence regulate the current.
(d) Voltameter
• It is a container in which electrolysis takes place.

22.2 Electrolysis of a molten zinc chloride (ZnCl2(l))

(1) Fig. 22.2 shows the experimental set-up for the electrolysis of molten zinc chloride.

molten ZnCl2(l)
(1000 oC)

(2) Electrolysing molten zinc chloride breaks it down to make zinc and chlorine.
(3) At the cathode (negative electrode): Zinc ions are attracted towards to the cathode and
discharged here where they gain electrons and turn into zinc atoms.
Zn2+(l) + 2e- → Zn(s)
(4) At the anode (positive electrode): Chloride ions are attracted towards the anode and
discharged here where they lose electrons to form chlorine atoms and the chlorine atoms join
together to form chlorine molecules.
2Cl-(l) → Cl2(g) + 2e-
(5) Overall reaction: Zn2+(l) + 2Cl-(l) → Zn(s) + Cl2(g)

Notices:
(i) The number of electrons gained by cations must be equal to that lost by anions.
(ii) Discharge of ions takes place only on the surface of electrodes
(iii) An electric current is conducted by delocalized electrons in the electrodes and connecting
wires, and by mobile ions in the electrolyte
 HKDSE CHEMISTRY / Topic 7 Redox reactions, chemical cells and electrolysis / Chapter 22 / Page.3
Practice 22.1:
 HKDSE CHEMISTRY / Topic 7 Redox reactions, chemical cells and electrolysis / Chapter 22 / Page.4

22.3 Comparing a chemical cell and an electrolytic cell

A Chemical cell An Electrolytic cell

Cell
(Chapters 18, 19, 20, 21) (Chapter 22)

Diagram

Negative
electrode
(cathode)

electrolyte

Generates electricity Uses electricity

Function
by chemical reactions to cause chemical reactions

Type of reaction Spontaneous Forced

Chemical energy→Electrical energy Electrical energy→Chemical energy

Energy change

Polarity cathode +ve (reduction) -ve (reduction)

of
electrode
anode -ve (oxidation) +ve (oxidation)
Tips : The following words may help you remember the concepts:

Oxidation occurs at the anode (AN OX) Reduction occurs at the cathode (RED CAT)

For Chemical cell, Anode is Negative electrode (CAN)

For Electrolytic cell, Anode is Positive electrode (EAP)

 HKDSE CHEMISTRY / Topic 7 Redox reactions, chemical cells and electrolysis / Chapter 22 / Page.5
22.4 Electrolysis of aqueous solutions
A. Basic concept (Preferential discharge of ions)
(1) Pure water does not contain water molecules only. It slightly ionizes to give H+(aq) ions
and OH-(aq) ions:

H2O(l) ⇌ H+(aq) + OH-(aq)

H2O
molecule

OH− ion

H+ ion

(2) Thus, an aqueous solution of sodium chloride NaCl(aq) contains the following ions:

Cations Anions

From sodium chloride Na+(aq) Cl-(aq)

From water H+(aq) OH-(aq)

(3) During electrolysis of aqueous solution of sodium chloride, cations (H+ and Na+) migrate to
the cathode (-ve) and anions (OH- and Cl-) migrate to the anode (+ve).

(4) The ions are preferentially discharged depending on the following factors:
(i) position of cations and anions in the E.C.S.,
(ii) concentration of ions in the solution and
(iii) nature of electrodes.
 HKDSE CHEMISTRY / Topic 7 Redox reactions, chemical cells and electrolysis / Chapter 22 / Page.6
22.5 Some examples of electrolysis
Example (A): Electrolysis of acidified water (e.g. dilute H2SO4(aq)) using platinum electrodes

(1) Pure water is a very poor conductor of electricity because pure water is only very slightly
ionized (very low concentration of mobile ions!). So, there is no observable change for the
electrolysis of pure water (i.e. distilled water).
(2) When some dilute sulphuric acid is added to water, the solution can be electrolyzed.
(3) Hofmann voltameter is used to carry out the electrolysis of acidified water.

(4) Ions attracted to the cathode Ions attracted to the anode

From sulphuric acid (H2SO4)
2H+(aq) SO42-(aq)
From water (H2O)
H+ (aq) OH-(aq)
(5) At the anode
As OH-(aq) ions are higher than SO42-(aq) ions in the E.C.S., OH-(aq) ions are preferentially discharged.

4OH-(aq) → O2 (g) + 2H2O(l) + 4e-

(6) At the cathode
H+(aq) ions are the only cation which are discharged here.

2H+(aq) + 2e- → H2(g)

(7) Overall (electrolytic) cell reaction:

2H2O(l) →2H2(g) + O2(g)

(a) The volume ratio of H2 : O2 = 2 : 1. It is because when two water molecules are decomposed,
two hydrogen molecules and one oxygen molecules are formed.
(b) When H+(aq) ions and OH-(aq) ions are discharged, more water molecules ionize. The
net effect is decomposition of water.
(c) The concentration of sulphuric acid increases as water is consumed in the electrolysis.
 HKDSE CHEMISTRY / Topic 7 Redox reactions, chemical cells and electrolysis / Chapter 22 / Page.7
Example (B): Electrolysis of very dilute sodium chloride solution using inert electrodes (graphite)

Very dilute sodium chloride

solution with universal
indicator added

(1) Ions attracted to the cathode Ions attracted to the anode

From sodium chloride (NaCl)
Na+(aq) Cl-(aq)
From water (H2O)
H+ (aq) OH-(aq)
(2) At the anode
As OH-(aq) ions are higher than Cl-(aq) ions in the E.C.S., OH-(aq) ions are preferentially
discharged.

4OH-(aq) → O2 (g) + 2H2O(l) + 4e-

(3) At the cathode
As H+(aq) ions are lower than Na+ ions in the E.C.S., H+(aq) ions are preferentially discharged.

2H+(aq) + 2e- → H2(g)

(4) Overall (electrolytic) cell reaction:

2H2O(l) →2H2(g) + O2(g)

(a) The gas volume ratio of H2 : O2 = 2 : 1. It is because when two water molecules are decomposed,
two hydrogen molecules and one oxygen molecules are formed.
(b) As the amount of water decreases, the concentration of sodium chloride solution increases.
(c) The solution around the anode becomes red (=> acidic) because when the OH-(aq) ions are
discharged, water ionizes continuously to restore the OH-(aq) ions discharged and thus there
are an increase in concentration of H+(aq) ions (excess H+(aq) ions).
(d) The solution around the cathode becomes blue (=> alkaline) because when the H+(aq) ions
are discharged, water ionizes continuously to restore the H+(aq) ions discharged and thus there
are an increase in concentration of OH-(aq) ions (excess OH-(aq) ions).
 HKDSE CHEMISTRY / Topic 7 Redox reactions, chemical cells and electrolysis / Chapter 22 / Page.8
Example (C): Electrolysis of dilute copper(II) sulphate solution using inert electrodes (graphite)

(1) Ions attracted to the cathode Ions attracted to the anode

From copper(II) sulphate (CuSO4)
Cu2+(aq) SO42-(aq)
From water (H2O)
H+(aq) OH-(aq)
(2) At the graphite anode
As OH-(aq) ions are higher than SO42-(aq) ions in the E.C.S., OH-(aq) ions are preferentially
discharged.

4OH-(aq) → O2 (g) + 2H2O(l) + 4e-

(3) At the cathode
As Cu2+(aq) ions are lower than H+ ions in the E.C.S., Cu2+(aq) ions are preferentially
discharged.

Cu2+(aq) + 2e- → Cu(s)

(4) Overall cell reaction:

2Cu2+(aq) +4OH-(aq) →2Cu(s) + O2(g) + 2H2O(l)

(a) After electrolysis, as Cu2+(aq) ions and OH-(aq) ions are removed, the solution becomes
H2SO4(aq) gradually.
(b) Colourless gas bubbles (O2(g)) are evolved at the anode.
(c) Brown deposit (Cu(s)) forms on the cathode.
(d) The blue solution fades as the concentration of Cu2+(aq) ions decreases

22.6 Position of ions in the E.C.S. and the preferential discharge of ions
(1) Table 22.2 summarises the products of electrolysis of aqueous solutions discussed above.
 HKDSE CHEMISTRY / Topic 7 Redox reactions, chemical cells and electrolysis / Chapter 22 / Page.9
(I) Cations discharged at cathode
(1) Fig. 22.7 shows the relative positions of sodium ion, hydrogen ion and copper(II) ion in the
electrochemical series.

(2) Since discharge at the cathode involves reduction, ions that accept electrons readily will be
reduced first. Thus, stronger oxidising agents will be preferentially discharged compared to
weaker oxidising agents.
(3) H+(aq) ion is a stronger oxidising agent than Na+(aq) ion. Hence H+(aq) ions are discharged
(reduced) at the cathode in preference to Na+(aq) ions during the electrolysis of very dilute
sodium chloride solution.
(4) Cu2+(aq) ion is a stronger oxidising agent than H+(aq) ion. Hence Cu2+(aq) ions are discharged
(reduced) at the cathode in preference to H+(aq) ions during the electrolysis of dilute copper(II)
sulphate solution.
(II) Anions discharged at anode
(1) Fig. 22.8 shows the relative positions of hydroxide ion, halide ions, nitrate ion and sulphate ion
in the electrochemical series.

(2) Since discharge at the anode involves oxidation, ions that lose electrons readily will be
oxidised first. Thus, stronger reducing agents will be preferentially discharged compared to
weaker reducing agents.
(3) OH–(aq) ion is a stronger reducing agent than SO42–(aq) ion and Cl–(aq) ion. Hence OH–
(aq) ions are discharged (oxidised) at the anode in preference to SO42–(aq) ions and Cl–(aq) ions
(Table 22.2).
 HKDSE CHEMISTRY / Topic 7 Redox reactions, chemical cells and electrolysis / Chapter 22 / Page.10
(III) Summary
(i) Position of ions in the electrochemical series (E.C.S): (inert electrodes: C, Pt)

Notice: In general, K+, Na+, Ca2+, Mg2+, Al3+, NO3- and SO42- are NOT discharged during
electrolysis of an aqueous solution using inert electrodes (C or Pt).
 HKDSE CHEMISTRY / Topic 7 Redox reactions, chemical cells and electrolysis / Chapter 22 / Page.11

Example 22.1

Example 22.1 solution:

 HKDSE CHEMISTRY / Topic 7 Redox reactions, chemical cells and electrolysis / Chapter 22 / Page.12

Example 22.2

Example 22.2 solution:

 HKDSE CHEMISTRY / Topic 7 Redox reactions, chemical cells and electrolysis / Chapter 22 / Page.13

Practice 22.2
 HKDSE CHEMISTRY / Topic 7 Redox reactions, chemical cells and electrolysis / Chapter 22 / Page.14
22.7 Concentration of ions in solution and the preferential discharge of ions

Example (D): Electrolysis of dilute sodium chloride solution using inert electrodes (graphite)

(1) Ions attracted to the cathode Ions attracted to the anode

From sodium chloride (NaCl)
Na+(aq) Cl-(aq)
From water (H2O)
H+ (aq) OH-(aq)
(2) At the anode
As concentration of Cl-(aq) ions is much higher than that of OH-(aq) ions, Cl-(aq) ions are
preferentially discharged.

2Cl-(aq) → Cl2(g) +2e-

(3) At the cathode
As H+(aq) ions are lower than Na+ ions in the E.C.S., H+(aq) ions are preferentially
discharged. Although the concentration of Na+(aq) ions is much higher than that of H+(aq)
ions, Na+(aq) ions are not discharged. Since Na+(aq) ions are much higher than H+(aq)
ions in the E.C.S, the concentration effect on cations can be ignored.

2H+(aq) + 2e- → H2(g)

(4) Overall cell reaction:

2H+(aq) +2Cl-(aq) →H2(g) + Cl2(g)

(a) As H+(aq) ions and Cl-(aq) ions are removed, the solution becomes sodium hydroxide
solution gradually.
(b) The theoretical gas volume ratio of H2 : Cl2 = 1:1. However, the actual volume of chlorine
collected may be smaller than that of hydrogen because chlorine is slightly soluble in water.
(c) The solution around the anode becomes red (=> acidic) and then colourless (=> bleached)
because some chlorine formed dissolves in water to give chlorine water which is acidic and is
a bleaching agent. (Cl2(g) + H2O(l) HCl(aq) + HOCl(aq))
(d) The solution around the cathode becomes blue (=> alkaline) because when the H+(aq) ions
are discharged, water ionizes continuously to restore the H+(aq) ions discharged and thus there
are an increase in concentration of OH-(aq) ions.
 HKDSE CHEMISTRY / Topic 7 Redox reactions, chemical cells and electrolysis / Chapter 22 / Page.15
(5) Summary:

(i) Table 22.3 summarises the products of electrolysing sodium chloride solutions of different
concentrations using carbon electrodes.

(ii) Concentration of ions in solution (Only for I-, Br-, Cl- solution; inert electrodes: C, Pt)
➢ In general, when two ions occupied similar positions in the E.C.S., the ion at a higher
concentration will be discharged first.
➢ The concentration effect on anions (OH-, I-, Br-, Cl- ) is significant whereas the concentration
effect on cations is insignificant.

Example 22.3
 HKDSE CHEMISTRY / Topic 7 Redox reactions, chemical cells and electrolysis / Chapter 22 / Page.16

Example 22.3 solution:

Practice 22.3
 HKDSE CHEMISTRY / Topic 7 Redox reactions, chemical cells and electrolysis / Chapter 22 / Page.17
22.8 The nature of the electrodes and the preferential discharge of ions

Example (E): Electrolysis of concentrated sodium chloride solution using mercury cathode

(1) Ions attracted to the cathode Ions attracted to the anode

From sodium chloride (NaCl)
Na+(aq) Cl-(aq)
From water (H2O)
H+ (aq) OH-(aq)
(2) At the anode
As concentration of Cl-(aq) ions is much higher than that of OH-(aq) ions, Cl-(aq) ions are
preferentially discharged.

2Cl-(aq) → Cl2(g) +2e-

(3) At the cathode
(a) As Hg electrode favours the discharge of Na+ ions, Na+(aq) ions are preferentially discharged.

Na+(aq) + e- → Na(s)
(b) The Na(s) formed then dissolves in Hg(l) to give alloy, sodium amalgam (Na/Hg).

Na(s) + Hg(l) → Na/Hg(l)

(4) Overall cell reaction:

2Na+(aq) +2Cl-(aq) + 2Hg(l) →2Na/Hg(l) + Cl2(g)

(a) During electrolysis, as Na+(aq) ions and Cl-(aq) ions are removed, the concentration of
sodium chloride solution decreases.
 HKDSE CHEMISTRY / Topic 7 Redox reactions, chemical cells and electrolysis / Chapter 22 / Page.18
Question 1:

Example (F): Electrolysis of dilute copper (II) sulphate solution using copper electrodes

(1) Ions attracted to the cathode Ions attracted to the anode

From copper(II) sulphate (CuSO4)
Cu2+(aq) SO42-(aq)
From water (H2O)
H+(aq) OH-(aq)
(2) At the copper anode
As Cu(s) is higher than OH-(aq) ions and SO42-(aq) ions in the E.C.S., Cu(s) loses electrons
more readily.

Cu(s) → Cu2+(aq) + 2e-

(3) At the cathode
As Cu2+(aq) ions are lower than H+ ions in the E.C.S., Cu2+(aq) ions are preferentially
discharged.

Cu2+(aq) + 2e- → Cu(s)

 HKDSE CHEMISTRY / Topic 7 Redox reactions, chemical cells and electrolysis / Chapter 22 / Page.19
(4) Overall cell reaction:

Cu(s) → Cu(s)
Anode Cathode
(a) Brown Cu(s) electrode becomes thinner on the anode.
(b) Brown deposit (Cu(s)) forms on the cathode.
(c) The blue colour of the solution remains unchanged as the amount of copper dissolves
at the anode is equal to the amount of copper deposits on the cathode, the
concentration of Cu2+(aq) ions remains unchanged.

(5) Summary
(i) Table 22.4 summarises the products of electrolysing dilute copper(II) sulphate solutions using
different electrodes.

(ii) The Nature of the electrodes: (Only for: Cu anode; Hg cathode)

➢ If inert electrodes [graphite (C) and platinum (Pt)] are used, the order of discharge of ions
is not affected. (Ruled by E.C.S. and concentration effect)
➢ If other materials are used to make the electrodes, they may affect the order of discharge of
ions and thus it affects the products formed. (Only for: Cu anode; Hg cathode)

Practice 22.4
 HKDSE CHEMISTRY / Topic 7 Redox reactions, chemical cells and electrolysis / Chapter 22 / Page.20

Question 2:
An electric circuit is set yup below. All the electrodes are made of graphite.

When the circuit is closed, a current flows in the external circuit. After some time, a reddish brown
fume is observed around electrode X.
(a) Which pole, A or B, is the positive pole? Explain briefly.
(b) What is observed at electrode W? Write the ionic half equation for the reaction involved.
(c) What are the gases collected in the test tubes above electrodes Y and Z respectively? Write the ionic half
equations for the reactions involved.
(d) What is the ratio of the theoretical volumes of the gases collected above electrodes Y and Z?
(e) What is the colour change of the universal indicator around the electrodes Y and Z during the electrolysis?
(f) Using the concept of preferential discharge of ions, explain the formation of the gas at electrode Y.
(g) Suggest a test for the gas collected at electrode Z.
 HKDSE CHEMISTRY / Topic 7 Redox reactions, chemical cells and electrolysis / Chapter 22 / Page.21

Question 3:
An electrical circuit is set up as shown in the figure below. Electrodes R and S are made of graphite
while electrodes T and U are made of silver.

bulb

R S T U

solid potassium iodide

silver nitrate solution

ammeter d.c. source variable resistor

(a) No current flows while the potassium iodide is in the solid state, but the bulb lights up when water
is added. Explain why this happens.
(b) When water is added to the solid potassium iodide, a current flows through the circuit.
(i) State the polarity of each of the electrodes.
(ii) State whether each electrode is the cathode or the anode.
(c)
(i)What is seen around electrode R after the current has been passed for some time?
(ii) Give the half equation for the change that occurs.
(d)
(i) After passing the current for some time, what can be observed at electrodes T and U? Explain.
(ii) Give the half equations for the changes that occur.
 HKDSE CHEMISTRY / Topic 7 Redox reactions, chemical cells and electrolysis / Chapter 22 / Page.22
22.9 Industrial applications of electrolysis

(A) Electroplating
(1) Electroplating is the process of coating a thin layer of metal (Cr, Ni, Cu, Ag, Au) on an object
by electrolysis.
(2) Electroplating is used to prevent corrosion of Fe and improve appearance.
(3) Set-up for electroplating (e.g. nickel-plating):

Component Function Remarks

Nickel (plating metal) As anode The plating metals should be low in the E.C.S.,
e.g Cu, Cr, Ni, Ag and Au
Object to be plated (e.g. Fe) As cathode • It should be first cleaned with sandpaper (or
acid) to remove metal oxide on its surface
• then cleaned with alkali to remove oil/ grease.
• Because both metal oxide and grease reduce
electrical conductivity.
Nickel(II) sulphate solution As electrolyte The electrolyte is an aqueous solution containing
the metal ions of the plating metal.

(4) Equations:
(i) At the anode: Ni(s) → Ni2+(aq) +2e-
(ii) At the cathode: Ni2+ (aq) + 2e- → Ni(s)
(iii) Overall reaction: Ni(s) (anode) → Ni(s) (cathode)
 HKDSE CHEMISTRY / Topic 7 Redox reactions, chemical cells and electrolysis / Chapter 22 / Page.23
Example 22.4

Example 22.4 solution:

 HKDSE CHEMISTRY / Topic 7 Redox reactions, chemical cells and electrolysis / Chapter 22 / Page.24

Practice 22.5
 HKDSE CHEMISTRY / Topic 7 Redox reactions, chemical cells and electrolysis / Chapter 22 / Page.25
(5) Environmental impact of the electroplating industry
The electroplating process involves pretreatment (e.g. cleaning and degreasing), plating and post
plating treatment (e.g. rinsing with water).

(a) Major pollutants from the electroplating industry include:

(i) Acids and alkalis which increase rate of corrosion of metal objects and kill aquatic lives.
(ii) Heavy metal ions (e.g Ni2+, Cr3+) and sodium cyanide (NaCN) which are highly toxic and kill
the aquatic lives.
➢ Discharge of untreated electroplating effluents (Fig. 22.15) harms water life and causes
contamination of water courses and ground water.

(b) Methods to control pollution from the electroplating industry:

(i) Neutralize acidic effluent with calcium hydroxide (Ca(OH)2(s), slaked lime).
(ii) Neutralize alkaline effluent with sulphuric acid (H2SO4(aq))
(iii) Remove heavy metal ions by addition of sodium hydroxide solution (NaOH(aq)) or sodium
carbonate solution (Na2CO3(aq)) followed by filtration of precipitate formed,
Ni2+(aq) +2OH-(aq) → Ni(OH)2(s)
Ni2+(aq) +CO32-(aq) → NiCO3(s)
(iv) Treat cyanides (e.g. NaCN / KCN) chemically to make them harmless.
(v) Recycle the effluent to extract valuable heavy metals (e.g. Cu, Ni, Cr, Ag) for later use.
(vi) Remove chromium(VI) ions (e.g. Cr2O72-(aq)), which are highly toxic to humans, by a two-step
process — first reduce these ions to less toxic Cr3+(aq) ions using a reducing agent (e.g.
sodium sulphite), then add NaOH(aq) to precipitate the ions as chromium(III) hydroxide.
 HKDSE CHEMISTRY / Topic 7 Redox reactions, chemical cells and electrolysis / Chapter 22 / Page.26
22.10 More industrial applications of electrolysis
Electrolysis has many useful applications in industry, e.g. (A) Electroplating, (B) Extraction of
reactive metals (> Al) and (C) Anodization of Al.

(B) Extraction of reactive metals

(1) Reactive metals are extracted by electrolysis of their molten ores.

(2) The ores used are usually chlorides of K, Na, Ca and Mg and oxide of Al. For example, in
the extraction of aluminum from molten aluminum oxide, the following reactions occur:
➢ At the cathode : Al3+(l) + 3e- → Al(l)
➢ At the anode : 2O2-(l) → O2(g) + 4e-

(C) Aluminum anodization

(1) Anodization is a process to increase the thickness of the aluminum oxide layer by electrolysis.
(2) The anodized aluminium is more corrosion resistant and can be dyed to give attractive colours.
(3) Aluminium objects to be anodized at the anode whereas dilute sulphuric acid is the
electrolyte.
(4) Both SO42-(aq) ions and OH-(aq) ions are attracted towards the anode. OH-(aq) ions are
preferentially discharged at the anode to form O2(g):
4OH-(aq) → O2(g) +2H2O(l) + 4e-
The oxygen produced reacts with aluminium object to form aluminium oxide
4Al(s) + 3O2(g) → 2Al2O3(s)
 HKDSE CHEMISTRY / Topic 7 Redox reactions, chemical cells and electrolysis / Chapter 22 / Page.27

More Challenging Questions (Chapter 22):

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