Chapter 29 to 32 Redox reactions, Simple chemical cells and electrolysis / notes / 43

Electrolysis (Chapter 32)

(A) Introduction
Electrolyte

- ELECTROLYSIS means decomposition by electricity. It is the process in

which a redox reaction is forced to take place by the passage of a direct electric
current through an electrolyte (molten or in aqueous solution). mobile ions
- Two electrodes are dipped into the same electrolyte
- The set-up of electrolysis is called an electrolytic cell or voltameter.
d.c.

Comparison of chemical cell and electrolytic cell

Chemical cell Electrolytic cell

It generates electrical energy It consumes electrical energy
1. Function
(or electricity). (or electricity).
Non-spontaneous (Redox
2. Spontaneity Spontaneous redox reaction reaction is forced to occur by
an external cell.)
3. Polarity and Red Cat
reaction occurring at An Ox
(a) Cathode + (reduction) – (reduction)
(b) Anode – (oxidation) + (oxidation)
4. Number of
1 or 2 1
electrolytes used
(B) Electrolysis of some compounds

(a) Electrolysis of molten ionic compounds

- A molten ionic compound only contains ions of the compound
- Only ions of the compound discharge at electrodes
- Insoluble ionic compounds are usually melted before electrolysis
e.g. In melting the lead(II) bromide solid => PbBr2 (s) ® Pb2+ (l) + 2 Br- (l)
During electrolysis:
+ve electrode
Half equation at anode (oxidation): 2Br-(l) ® Br2(g) + 2e- Reddish brown vapour evolves at +ve electrode
-ve electrode
Half equation at cathode (reduction): Pb2+(l) + 2e- ® Pb(l) Silvery grey solid / silvery grey liquid forms

Overall equation: Pb2+(l) + 2Br-(l) ® Pb(l) + Br2(g)

m.p. of CaO > CaCl2
heating
because O2- has higher
CaCO3 -----> CaO + CO2 CaCO3 + 2 HCl ---> CaCl2 + CO2 + H 2 O
charge than Cl-
electrolysis => crystallization to get CaCl2
ionic bond in CaO > CaCl2
CaO (l) => Ca (s) + O2 (g) CaCl2 -> Ca + Cl2
 Chapter 29 to 32 Redox reactions, Simple chemical cells and electrolysis / notes / 44

Classwork a.c.
1. Why is an alternating current not used in electrolysis?
If alternating current is used, the polarity of electrodes changes constantly.
Electrolysis cannot actually occur mobile ion can migrates to the oppositely

charged electrode in a constant direction.

2. Predict the products formed at each graphite electrode when a direct current is
passed into
(a) molten magnesium chloride At cathode: magnesium; at anode: chlorine
(b) solid magnesium chloride. No electrolysis because ions in solid magnesium
chloride is not mobile to conduct electricity.

(b) Electrolysis of aqueous solutions of compounds forming ions

self - ionization
- Pure water ionize slightly to produce hydrogen ions and hydroxide ions
Equation: H2O (l) H+ (aq) + OH- (aq)
- However, the concentration of ions is very low, so pure water is a poor conductor.
It conductivity can be increased by adding acid, base or soluble salt. [H+]=10-pH
aq
e.g. HCl(g) + water ® H+(aq) + Cl–(aq)
pH = -log[H+] at room temperature,
NH3(g) + H2O(l) NH4+(aq) + OH–(aq)
pH of pure of water = 7
NaCl(s) + water ® Na+(aq) + Cl–(aq) [H+] = 10 -7 mol dm-3 // [OH-]=[H+]=10 -7 mol dm-3 //

Kc = [H+][OH-]=10 -14 mol 2 dm-6 //

(C) Preferential discharge of ions in aqueous electrolytes
Kc = equilibrium constant

(a) Factors affecting the Preferential Discharge of Ions

Three main factors affecting the preferential discharge of ions
1. the positions of ions in the electrochemical series (E.C.S.)
2. the concentration of ions in the solution of electrolyte compared with hydroxide
3. the nature of the electrodes ( ion
Active electrode - Copper

(b) Relative positions of ions in E.C.S. and Preferential Discharge of Ions

K+(aq) + e- K (s)

Cu 2+ + 2e- <=> Cu reducing agent

Oxidizing agent
 Chapter 29 to 32 Redox reactions, Simple chemical cells and electrolysis / notes / 45

e.g. 1 electrolysis of dilute sulphuric acid

- Electrolysis of dilute sulphuric acid using
platinum electrodes can be carried out in a
Hoffman voltameter. Useful for
collecting gases produced at the
electrodes.
- Ions in the electrolyte :
Cation: H+(aq)
Anion: SO42-(aq) and OH-(aq) HSO42- (aq)
- At the cathode: Hydrogen ions discharge
Half equation: 2H+(aq) + 2e- ® H2(g) x2

hydrogen ion is positively charged which attract to the negative electrode to discharge.

- At the anode:
OH–(aq) is higher than SO42–(aq) in electrochemical series (E.C.S.), so OH–(aq) is
a stronger reducing agent than SO42- (aq). Therefore, OH–(aq) is preferentially
discharged
Half equation: 4OH–(aq) ® 2H2O(l) + O2(g) + 4e– x1
- Overall equations: 4H+(aq) + 4OH-(aq) ® 2H2(g) + O2(g) + 2H2O(l)
4H 2 O
i.e. 2H2O(l) ® 2H2(g) + O2(g)
same temperature and same pressure

- By Avogadro’s law, the molar volumes of gases are the same under given
conditions. So volume ratio of gases = mole ratio of the gases, so the volume of
H2 : O2 = 2 : 1
room temperature and pressure

- Note: Molar volume of all gases equal to 24 dm at r.t.p. (25 oC and 1 atm) and
3

22.4 dm3 at s.t.p. (0 oC and 1 atm)

standard temperature and pressure

- Changes in the solution: Sulphuric acid does not react but its concentration
_______increases because some water is decomposed into hydrogen and oxygen.
graphite
e.g. 2 Electrolysis of copper(II) sulphate solution using carbon electrodes
- Cation: Cu2+(aq) and H+(aq)

- Anion: SO42–(aq) and OH–(aq)

 Chapter 29 to 32 Redox reactions, Simple chemical cells and electrolysis / notes / 46
negative electrode
- At the cathode: Cu2+ (aq) is lower than H+ (aq) in electrochemical series (E.C.S.)
so that Cu2+(aq) is a stronger oxidizing agent than H+ (aq). Therefore, Cu2+
(aq) is preferentially discharged
- Half equation: Cu2+(aq) + 2e– ® Cu(s)
- Observation: Reddish brown solid forms
positive electrode
- At the anode: OH–(aq) is higher than SO42–(aq) in E.C.S. so that OH–(aq) is a
stronger reducing agent than SO42–(aq). Therefore, OH–(aq) is preferentially
discharged
- Half equation: 4OH–(aq) ® 2H2O(l) + O2(g) + 4e–
- Observation: Colourless gas evolves
- Overall equation: 2Cu2+(aq) + 4OH–(aq)® 2Cu(s) + O2(g) + 2H2O(l)
full chemical equation 2CuSO 4 (aq) + 2H2O (l) -> 2Cu (s) + O 2 (g) + 2H2SO 4 (aq)
ionic equation
2+ +
2Cu (aq) + 2H2O (l) -> 2Cu (s) + O 2 (g) + 4 H (aq)
- Net change in the solution:
(1) Blue colour of the solution becomes paler because
blue
___________________________concentration of blue Cu2+ ¯
(2) When OH–(aq) are discharged at the anode, excess of H+ in the solution at the
anode and solution becomes _________acidic.
Classwork
Add a little dilute sodium hydroxide solution to water. Then add the resulting
solution to a Hofmann voltameter and electrolyse it, using platinum electrodes.
(a) State the formulae of the cations and anions present in the solution.
(b) Name the product liberated at the (i) cathode and (ii) anode.
(c) What is the volume ratio of the products in (b)?
(a) Cations: Na+(aq), H+(aq) and Anions: OH-(aq)
(b) (i) At cathode: Hydrogen and at anode (ii) Oxygen
(c) Volume ratio of hydrogen : oxygen = 2 : 1
0.5 M

e.g. 3 Electrolysis of dilute sodium chloride solution using carbon electrodes

- Cation: Na+ (aq); H+ (aq)

- Anion: OH- (aq), Cl- (aq)

universal indicator
 Chapter 29 to 32 Redox reactions, Simple chemical cells and electrolysis / notes / 47

- At the cathode: H+ is lower than Na+ in E.C.S. so that H+ is a stronger oxidizing

agent than Na+, so H+ is preferentially discharged
- Half equation: 2H+(aq) + 2e- ® H2(g).

The excess OH-(aq) ions around the cathode make the solution there alkaline.
from green
- Observation: Colourless gas bubbles and universal indicator turns to _____ blue.
electrochemical series
– –
- At the anode: OH (aq) is higher than Cl (aq) in E.C.S. so that OH- (aq) is a
stronger reducing agent than Cl- (aq) \ OH- is preferentially discharged
- Half equation: 4OH-(aq) ® O2(g) + 2H2O(l) + 4e-
The excess H+(aq) ions around the anode make the solution there acidic.
from green
- Observation: Colourless gas bubbles and universal indicator turns to _____red./ yellow

- Overall equation: 2H2O(l) ® 2H2(g) + O2(g)

- Net change: Concentration of NaCl ____________increases

(c) Concentration effect halide ion compared hydroxide ion

- When the positions of different ions in the E.C.S. are near, the ions with much
higher concentration are discharged preferentially.
e.g. Position of OH– is higher than Cl– in the E.C.S.
(1) With similar concentration: OH– is preferentially discharged
(2) When concentration of Cl– >> OH–, Cl– is preferentially discharged

e.g. 1 Electrolysis of concentrated NaCl (2M) brine

greenish yellow gas

-
Cation: H+ and Na+
-
Anion: Cl- and OH-

- At the cathode: H+ is lower than Na+ in E.C.S. so that H+ is a stronger oxidizing

agent than Na+ \ H+ is preferentially discharged
- Half equation: 2H+(aq) + 2e– ® H2(g)
Excess of OH– ions around the cathode so that solution becomes alkaline
-
Observation: Colourless gas evolves and the universal indicator changes from
blue
pale green to ___________. When H+ ion is discharged, there is excess OH-
ion, so the solution become alkaline.
 Chapter 29 to 32 Redox reactions, Simple chemical cells and electrolysis / notes / 48

- At the anode: OH–(aq) is higher than Cl–(aq) in E.C.S., but Cl–(aq) is

preferentially discharged when concentrated NaCl is electrolyzed because
concentration of Cl–(aq) >> concentration of OH–(aq)
- Half equation: 2Cl–(aq) ® Cl2(g) + 2e–
- Observation:
Yellowish green gas evolved which is chlorine gas. It dissolves in the solution to
form chlorine water which is acidic and is a bleaching agent.
Equation: Cl2 (g) + H2O (l) HCl (aq) + HOCl (aq) hypochlorite ion
HOCl is hypochloric acid.When is ionized to give OCl- ion which is the
bleaching agent. Use moist blue litmus paper to test chlorine, it change from blue to red and then white.
red and then colourless
So the universal indicator changes from pale green to _____________________
- Overall ionic equation: 2H+(aq) + 2Cl-(aq) ® H2(g) + Cl2(g)
2H2O (l) < = > 2H + (aq) + 2 OH- (aq) 2H 2 O + 2Cl- -> H 2 + Cl2 + 2OH -

- Net change: OH-(aq) ions accumulate. The solution therefore gradually changes
to sodium hydroxide solution. Cl 2 + 2NaOH -> NaCl + NaOCl + H2O chlorine bleach

- Overall chemical equation: Disproportionation - a redox reaction where

2NaCl(aq) + 2H2O(l) ® 2NaOH(aq) + H2(g) + Cl2(g) same species undergoes oxidation and
2Na+ (aq) + 2Cl-(aq) 2Na+ (aq) + 2OH-(aq) reduction at the same time.

2Cl -(aq) + 2 H2O (l) -> 2OH- (aq) + H2 (g) + Cl 2 (g) Oxidation no of Cl 2 changes from 0 in Cl 2 to -1
Classwork
in Cl - ion and +1 in OCl - ion at same time.

1. In the electrolysis of concentrated sodium chloride solution using carbon

electrodes, the actual volume of chlorine gas collected at the anode is usually
smaller than the theoretical volume. Explain
and reacted
Some chlorine is dissolved in water or NaOH (aq) solution formed.

e.g. 2 electrolysis of 2 M KBr

Half equation at the cathode: 2H+(aq) + 2e– ® H2(g)

Observation: Excess of _____OH– ions around the cathode so that solution becomes
blue
______ alkaline and the universal indicator changes from pale green to ______

At the anode: OH–(aq) is higher than Br–(aq) in E.C.S. but Br–(aq) is preferentially
discharged. ∵ Concentration of Br–(aq) >> concentration of OH–(aq)

Half equation: 2Br–(aq) ® Br2(aq) + 2e–

Observation:
Some of the bromine formed dissolves in the solution to form yellow or brown
solution which is a bleaching agent. (Reference: Br2 + H2O => HBr + HOBr) So
the universal indicator _______________ brown
is bleached and the solution turn to __________ hypobromic acid
 Chapter 29 to 32 Redox reactions, Simple chemical cells and electrolysis / notes / 49

Overall ionic equation: 2H+(aq) + 2Br-(aq) ® H2(g) + Br2(aq)

2H2O <=> 2H+ (aq) + 2OH- (aq)

Net change: OH-(aq) ions accumulate. The solution therefore gradually changes to
potassium hydroxide solution.

Over all chemical equation:

2NaBr(aq) + 2H2O(l) ® 2NaOH(aq) + H2(g) + Br2(aq)
2Br- (aq) + 2H2O -> 2OH- (aq) + H2 (g) + Br2 (aq)

e.g. 3 electrolysis of 2 M KI

At the cathode:
Half equation: 2H+(aq) + 2e– ® H2(g)

Excess of OH– ions around the cathode so that solution becomes alkaline and the
blue
universal indicator changes from pale green to ___________
At the anode: OH–(aq) is higher than I–(aq) in E.C.S. but I–(aq) is preferentially
discharged
∵ Concentration of I–(aq) >> concentration of OH–(aq)
Half equation: 2I–(aq) ® I2(aq) + 2e– I2 + I- < = > I3 -
Some of the iodine formed dissolves in the solution to form yellow or brown
solution.
Overall ionic equation: 2H+(aq) + 2I-(aq) ® H2(g) + I2(aq)
2H2O (l) < => 2H+ (aq) + 2 OH- (aq)
-
Net change: OH (aq) ions accumulate. The solution therefore gradually changes to
potassium hydroxide solution.

Overall chemical equation: 2NaI(aq) + 2H2O (l) ® 2NaOH(aq) + H2(g) + I2(aq)

Summary 2I- (aq) + 2H2 O (l) -> 2OH- (aq) + H2 (g) + I2 (aq)

Fill in the blanks:

In any aqueous solution, __H+______ ions and __OH-______ ions are present.
-ve electrode (or cathode)
cation is stronger oxidizing agent than H+ ion
Preferential discharge of cations at an inert cathode

·If a cation is below H+(aq) in the E.C.S., the _cation_____ should be

discharged, forming the _metal______ .
in the electrochemical series,, cation is weaker oxidizing agent than H+ ion
· If a cation is above H+(aq), the_ H+__ should be discharged, forming ___H2__ .
+ve electrode (or anode)
Preferential discharge of anions at an inert anode (Pt is not used for electrolysis
of conc. NaCl. Cl2 reacts with Pt to form compound e.g. PtCl42-)
· Basically, ___OH-______ should be discharged, forming __H2O + O2_____ .

· But in a concentrated halide solution (chloride, bromide or iodide),

__halide________ may be discharged instead (because the concentration of
halide ion is _____________much higher than that of OH- ion).
 Chapter 29 to 32 Redox reactions, Simple chemical cells and electrolysis / notes / 50

(d) Nature of Electrodes

- When inert materials (e.g. Platinum, carbon or graphite) are used as electrodes,
the electrodes do not react with the solution of electrolyte or take part in the
reactions
- When electrodes are made of other materials, the order of discharge of ions may
be affected or the metal electrode involves in redox reaction.
e.g. 1 Hg cathode in electrolysis of conc. NaCl industrial set-up
e.g. 2 Cu or Ni anode in electroplating

e.g. 1. Electrolysis of concentrated sodium chloride solution using a mercury

cathode and a carbon anode
- Cation: H+ and Na+
- Anion: Cl- and OH-

U-tube set-up

tap funnel set-up

- At the cathode: In the presence of Hg cathode, Na+ is preferentially discharged.

∵ With high concentration of Na+ (aq) and Na formed immediately dissolves in
sodium amalgam Alloy
Hg to form _______________
- Half-equation: Na+(aq) + Hg(l) + e– ® Na/Hg (l) dull in colour

- At the anode: OH–(aq) is higher than Cl–(aq) in E.C.S. but Cl–(aq) is

preferentially discharged. ∵ Concentration of Cl–(aq) >> concentration of
OH–(aq) 10 -7 M 2M

- Half equation: 2Cl–(aq) ® Cl2(g) + 2e– wet

- Observation: ___________Yellowish green gas evolved which turns universal

indicator turns to _____red first and then ______bleach.

- Overall ionic equation: 2Hg(l) + 2Na+(aq) + 2Cl-(aq) ® 2Na/Hg(l) + Cl2(g)

overall chemical equation : 2Hg (l) + 2 NaCl (aq) -> 2 Na / Hg (l) + Cl2 (g)

- Change in the solution: The sodium chloride solution becomes more and more
dilute.
- Further reaction: Na in Na/Hg(l) reacts with water and Hg is not consumed in the
electrolysis. 2Na/Hg(l) + 2H2O(l) ® 2NaOH(aq) + H2(g) + 2Hg(l)
Ionic equation : 2 Na / Hg (l) + 2 H2O (l) -> 2 Na+ (aq) + 2 OH- (aq) + H2 (g) + 2 Hg (l)
 Chapter 29 to 32 Redox reactions, Simple chemical cells and electrolysis / notes / 51

Classwork
Refer to figure, do you think electrolysis occurs on the right side or the left side
of the U-shaped tube?
On the right, concentrated sodium chloride solution is in contact with both
positive and negative electrodes while water is in contact with the negative
electrode only.

e.g. 2 Electrolysis of copper(II) sulphate solution using copper electrodes

-
Cation: H+ and Cu2+
-
Anion: OH- and SO42-
not involved in

reaction

- At cathode: Cu2+ is lower than H+ in E.C.S. so that Cu2+ is a stronger oxidizing

agent than H+\ Cu2+ is preferentially discharged
- Half-equation: Cu2+(aq) + 2e– ® Cu(s)
- Observation: Reddish brown solid form / the copper cathode is thickened.

- At anode: Cu(s) is higher than OH–(aq) & SO42–(aq) in E.C.S. so that Cu(s) is a
stronger reducing agent than OH- (aq) and SO42- (aq). \ Cu(s) is preferentially lose
electrons.
- Half equation: Cu(s) ® Cu2+(aq) + 2e–
- Observation: The copper electrode gradually ____________dissolves

- Overall change: The electrolysis is actually a transfer of copper from the anode to
the cathode so that no new substance is produced.
Cu(s) at anode ® Cu(s) at cathode
- Decrease in mass of copper anode = Increase in mass of copper cathode if the
copper anode is pure.

- Change in solution: Concentration of copper(II) sulphate in the solution does not

change. (2) No change in the intensity of the blue colour.
 Chapter 29 to 32 Redox reactions, Simple chemical cells and electrolysis / notes / 52

Claswork

1. Fill in the blanks:

The material of electrodes may affect the products formed in electrolysis. In
the electrolysis of concentrated sodium chloride solution, _chlorine____ is formed
at a graphite anode, but_sodium amalgam________ is formed at a mercury
cathode. In the electrolysis of copper(II) sulphate solution, _H2 ______ is formed
at a graphite anode,
-------- but a copper anode _dissolves_______________ to give
2+ cathode
__Cu _______ ions.

Summary of the products formed in electrolysis

Classwork

1. An electric circuit is set up as below. Electrodes E and F are made of copper while
electrodes G and H are made of carbon.

+ve ion : K+ H+

-ve ion :NＯ３— ＯＨ＿

(a) State the polarity of each electrode.

(b) State whether each electrode is a cathode or an anode.
(c) Write an ionic half equation for the reaction occurring at each electrode.
(d) Describe the observable change(s) at each electrode.
(e) What are the colour of the solutions around electrodes G and H? Explain.
(f) Write an overall chemical equation to represent the reaction occurring in
beaker Y.
(g) What are the changes in the solutions in beakers X and Y?
 Chapter 29 to 32 Redox reactions, Simple chemical cells and electrolysis / notes / 53

(a) E: Negative / F: Positive / G: Negative / H: Positive

(b) E: Cathode / F: Anode / G: Cathode / H: Anode
(c) E: Cu2+(aq) + 2e– ® Cu(s)
(f) 2H2O -> 2+
s ® Cu(s)
2H2 + O2 F: Cu(aq) + 2e–
aq
G: 2H+(aq) + 2e– ® H2(g)
(g) beaker X
: no observable H: 4OH–(aq) ® O2(g) + 2H2O(l) + 4e–
change (d) E: The electrode is covered by a layer of reddish brown solid (or the
beaker Y
electrode becomes thicker/the mass of electrode increases)
: conc. of KNO3 F: The electrode gradually dissolves (or the electrode becomes
increases thinner/the mass of electrode decreases).
G: Colourless gas bubbles are given out.
H: Colourless gas bubbles are given out.
(e) At G, the solution turns from green to blue because H+ ion discharged and there is excess OH- ion left and the solution
becomes alkaline. At H, the solution turns froom green to red because OH- discharged and there is excess H+ left,
the solution becomes acidic.
2. An electric circuit is set up as below. Electrodes E and F are made of platinum.
Electrode G is made of carbon and electrode H is made of iron.

(a) Write ionic half equations for the reactions occurring at electrodes E and F.
State whether the reactions occurring at electrodes E and F are oxidation or
reduction.
(b) State the observable changes at electrodes E and F.
(c) State whether each of electrodes G and H is a cathode or an anode.
(d) Write an overall chemical equation to represent the reaction occurring in
beaker Y.
(e) State the observable change in the solution in beaker Y.

(a) E: Cu2+(aq) + 2e– ® Cu(s) (reduction)

F: 4OH–(aq) ® O2(g) + 2H2O(l) + 4e– (oxidation)
(b) E: Reddish brown solid is evolved. formed
F: Colourless gas is evolved.
(c) G: cathode; H: anode
(d) Fe (s) ® Fe2+ (aq) + 2e- x (1)
+ 2H (aq) + 2e ® H2(g)
+ -
x (1)
Fe(s) + 2H+(aq) ® Fe2+(aq) + H2(g) 2H2O < => 2H+ + 2OH-（ａｑ）
2 OH- (aq) + Fe2+(aq) ® Fe(OH)2 (s)
Overall chemical equation
Fe (s) + 2 H2O (l) ® Fe(OH)2 (s) + H2 (g)
from green to blue
(e) Indicator turns blue at G. The solution at H is green / dark green
Later dirty green precipitate ((Fe(OH)2(s)) can be seen in the beaker.
 Chapter 29 to 32 Redox reactions, Simple chemical cells and electrolysis / notes / 54

(D) Factors affecting the rate for electrolysis

ｃｕｒｒｅｎｔ - In general, we can speed up electrolysis by increasing the current for electrolysis.
＝ｃｈａｒｇｅ ／ ｔｉｍｅ Current can be increased by increasing the voltage or decreasing the resistance of
the set-up.
- Method to reduce the total resistance of the set-up for electrolysis
(1) Adjust the variable resistor (if any) to a lower resistance.
(2) Move the electrodes closer together.
(3) Use electrodes of larger surface area or push the electrodes deeper into the
electrolyte solution.
Ｖｏｌｔａｇｅ (4) Use a more concentrated electrolyte solution.
＝ｃｕｒｒｅｎｔ ｘ ｒｅｓｉｓｔａｎｃｅ

Ｖ＝ＩＲ
(E) Applications of Electrolysis

Some important applications of electrolysis:

1. electroplating;
2. purification of metals;
3. electrolysis of brine;
4. extraction of metals;
5. aluminium anodization

(a) Electroplating

- Electroplating is a process of coating a thin layer of metal on an object by

electrolysis (1) protect the object from corrosion and (2) give the object an
attractive appearance.
- Principle: In electroplating, the metal object (X) to be electroplated is made the
____________ cathode and the plating metal (Y) is made the __________ anode.
An aqueous solution containing ___________________________ions of the
plating metal (Yn+ ions) is the electrolyte solution.

Ag+
 Chapter 29 to 32 Redox reactions, Simple chemical cells and electrolysis / notes / 55
2+ 3+
Ni or Cr are weaker O.A. than H +
- Note:
e.g. Cu, Ag, Au or Pt
(1) Metals ______________________________ low in the E.C.S. are usually used
as plating metals. The solutions of electrolytes usually contain the ions of these
metals which are___________________ strong oxidizing agents and they are
preferentially discharged at the ____________cathode to coat the object.
e.g. for plating metals - copper, silver, gold, tin and chromium and nickel.

(2) In electroplating of Ag and Au, CN- (aq) (cyanide ion) is added to help anode to
dissolve. Au 3+ + 2CN - => [Au(CN)2 ]-
(3) Some non-metallic objects can be electroplated if they have been sprayed with
a layer of _________________________________ powdered metal or
graphite. The surface of these objects can conduct electricity. It is used to make
jewellery.

(b) Purification of metals (optional)

- Metals such as _______________________copper and lead are purified by
electrolysis. The process is called ___________________electrolytic refining.
e.g. In refining copper, an aqueous solution of copper(II) sulphate is electrolyzed.

- ___________________Impure copper as the anode and __________pure copper

as the cathode.

At the anode
- Metal impurities higher than copper in E.C.S. e.g. Zn, Fe, Pb are oxidized first,
copper loses electron next.
e.g. Zn(s) ® Zn2+(aq) + 2e– Fe(s) ® Fe2+(aq) + 2e–
Pb(s) ® Pb (aq) + 2e
2+ –
Cu(s) ® Cu2+(aq) + 2e–
H+

- Metal impurities lower than copper in E.C.S. which are

hardly oxidized and uncharged impurities e.g. sand are
deposited at the bottom of the electrolytic tank as metal
sludge and separated when copper dissolved.

At the cathode
- Cu2+ is preferentially discharged and weaker oxidizing
agents than Cu2+ are not discharged
Half equation: Cu2+(aq) + 2e– ® Cu(s)
 Chapter 29 to 32 Redox reactions, Simple chemical cells and electrolysis / notes / 56

- Overall reaction: Only copper can deposit on the pure copper cathode
- Net result: Transfer of pure copper from the impure anode to the pure copper
cathode. So copper is purified.
Cu(s) at anode ® Cu(s) at cathode
- Decrease in mass of copper anode > Increase in mass of copper cathode as the
copper anode is impure.
- Uses: Purify copper for making electric wire which needs high purity for better
conduction.

Classwork

Will the concentration of Cu2+ in the solution change in the purification of

copper? Explain your answer briefly.

Yes. Because the anode involved metals which are more reactive than Cu which is
dissolved more readily than Cu. So the amount of Cu dissolved at the anode is less
than that the amount of Cu formed at the cathode. The concentration of Cu2+
(aq) in the electrolyte decreases.

(c) Production of Bleach

- Electrolysis of concentrated NaCl can be carried out by different electrolysis

set-up.
(1) Using mercury cathode and graphite anode
Cathode half-equation: Na+(aq) + Hg(l) + e– ® Na/Hg (l)
Anode half equation: 2Cl–(aq) ® Cl2(g) + 2e–
Overall equation: 2 Hg (l) + 2NaCl (aq) ® 2 Na / Hg (l) + Cl2 (g)

- NaOH can be prepared by reaction of sodium amalgam with water:

Equation: 2Na/Hg (l) + 2 H2O (l) ® NaOH (aq) + H2 (g) + 2 Hg (l)

(2) Using graphite electrodes

H 2 O (l) + 2Cl- (aq) -> 2OH - (aq) + Cl2 + H 2
Cathode half-equation: 2H+ (aq) + 2e- ® H2 (g)
Anode half equation: 2Cl–(aq) ® Cl2(g) + 2e– 2H2O < => 2H+ (aq) + 2OH- (aq)
Overall equation: H2O (l) + 2NaCl (aq)®2NaOH (aq) + Cl2(g) + H2(g)
- Dissolve chlorine gas in sodium hydroxide to form chlorine bleach.
Disproportionation
Equation: Cl2 + 2NaOH ® NaCl (aq) + NaOCl (aq) + H2O (l)
0 cold Chlorine undergoes
-1 +1
oxidation and reduction at
3Cl2 + 6NaOH => 5NaCl + NaClO3 (aq) + 3H 2 O (l)
- Hazards: hot the same time.
Chlorine is toxic; Hydrogen forms explosive mixtures it mixes with air; mercury is
toxic hydrogen is flammable

Two set-up need to separate hydrogen gas and chlorine because hydrogen and chlorine can mix
together to form explosive mixture.
 Chapter 29 to 32 Redox reactions, Simple chemical cells and electrolysis / notes / 57

- Test for hypochlorite ion:

(1) Hypochlorite ion can bleach coloured dye by oxidation
Equation: OCl- + [Dye] ® Cl- + [Dye+O] oxidized form
coloured colourless
(2) It reacts with acid to give greenish yellow chlorine turns wet blue litmus paper
to red and then bleach it to white.
Equation: OCl- + Cl- + 2H+ ® Cl2 + H2O
H + + OH - => H 2 O
Cl2 + H2O HCl + HOCl

Cl2 gas ionizes in water to give HCl and HOCl. HCl is a strong acid which ionizes
to give H+ (aq) ion and turns wet blue litmus paper to red then the hypochloric
acid (HOCl) ionizes to give OCl- to bleach the litmus paper to white.

(d) Extraction of metal

- Electrolysis of molten metal oxide (for group II and III metal ore) or metal chloride
(for group I metal ore)
e.g. 2NaCl (l) ® 2Na (l) + Cl2 (g) 2 Al2O3 (l) ® 4 Al (l) + 3 O2 (g)
Group II metal ore = > metal carbonate

Classwork metal carbonate -> metal oxide + carbon dioxide

heat in air strongly
Aluminium is extracted from its molten ore by electrolysis.
(a) Give the formula of the ore used.
(b) Write the ionic half-equations involved.
(c) Write the overall ionic equation for the reaction.
(a) Al2O3
(b) At cathode: Al3+(l) + 3e- ® Al(l)
At anode: 2O2-(l) ® O2(g) + 4e-
(c) 4Al3+(l) + 6O2-(l) ® 4Al(l) + 3O2(g)
(e) Anodization of aluminium

- The resistance to corrosion of aluminium can be enhanced by anodizing it using

electrolysis. (Anodization)
- The aluminium piece to be treated is made the anode in an electrolytic cell.
Cathode is a sheet of aluminium rolled into a cylindrical shape and the electrolyte
is dilute sulphuric acid.
- During electrolysis, oxygen is formed at the anode which oxidizes the aluminium
anode and thickens the oxide layer which is more corrosion resistant.
- The oxide layer can be dyed during anodization.
- Applications: Window frames, cooking utensils, chocolate wrappings and milk
bottle caps Anode : 4OH - -> O + H O +4e-
2 2
Cathode : 2H + +2e- -> H 2
3O + 4Al -> 2Al O
2 2 3
3H 2 O + 2Al -> Al2 O3 + 3H 2
 Chapter 29 to 32 Redox reactions, Simple chemical cells and electrolysis / notes / 58

(E) Water pollution problems in Hong Kong and control

(1) Liquid wastes of electroplating

e.g. acids, alkalis, metal salts, toxic chemicals (e.g. cyanide), organic solvents,
plating sludge toxic

(a) Removal of acids and alkalis : Acid is neutralized by reaction with metal carbonate
(e.g. Na2CO3) or metal oxide or hydroxide e.g. (NaOH) Equation : CO32- + 2H+ ® CO2
(aq) (aq)
+ H2O
Alkali is neutralized by reaction with acids. (e.g. H2SO4)
(aq)

(b) Removal of toxic metal ions: Heavy metal ions other than group I are removed by
solution
precipitation with carbonate or hydroxide and then land filling. (e.g. Na2CO3 or NaOH)
(aq) (aq)
e.g. Cr3+ (aq) + 3 OH- (aq) ® Cr(OH)3 (s) filter the
solid for
Ni2+ (aq) + CO32- (aq) ® NiCO3 (s)

(c) Removal of organic solvent and cyanide : physical separation and then incineration

(d) Removal of metal sludge : land filling

(2) Control and monitor by the Environmental Protection Department (EPD).

Classwork

(a) There is a wastage of metals through the discharging of waste solutions in the
electroplating industry. Suggest what can be done to conserve metal resources.
(b) Though slaked lime (calcium hydroxide) is cheaper than sodium carbonate,
factories nowadays often use the latter to neutralize acidic effluents. Explain.
(Hint: Calcium hydroxide neutralizes sulphuric acid to form calcium sulphate,
which is only slightly soluble in water.)
(a) Remove the metal ions from effluents by chemical treatment, if it is
economical to do so.
(b) Acidic effluents usually contain sulphuric acid. The calcium sulphate formed
is only slightly soluble in water, so it would prevent the neutralization reaction
from going on.
 Chapter 29 to 32 Redox reactions, Simple chemical cells and electrolysis / notes / 59

Revision questions
1. Which of the following statements is INCORRECT? B
A In a chemical cell, oxidation occurs at the anode.
B All redox reactions involve transferring of electrons.
C Sodium oxide is an electrolyte.
D A direct current should be used in electrolysis.

2. Which of the following statements concerning electrolysis is INCORRECT? A

A During electrolysis, chemical energy is converted into electrical energy.
B Electrolysis involves decomposition of an electrolyte.
C An energy supply is required for electrolysis.
D Graphite is commonly used as the inert electrodes in electrolysis.

3. Which of the following is NOT an essential component of the set-up for electrolysis? C
A Electrolyte
B Electrodes
C Ammeter
D Energy supply

4. Which of the following substances would not be decomposed by electricity? A

A Molten silver
B Dilute sulphuric acid
C Concentrated sodium chloride solution
D Aqueous silver nitrate

5. Which of the following ions are reduced during electrolysis of molten silver chloride? A
A Silver ions B Chloride ions
C Hydrogen ions D Hydroxide ions

6. Fluorine is NOT readily obtained as a product of electrolysis because C

A fluoride ion has a small size.
B fluoride ion is readily oxidized on contact with air.
C fluoride ion is not readily oxidized.
D fluoride compounds have extremely high melting points.

7. Which of the following changes would occur at the electrodes during the electrolysis of A
dilute copper(II) chloride solution using copper electrodes?
Anode Cathode
A Copper dissolves Copper deposits
B Copper deposits Copper dissolves
C Chlorine given off Copper deposits
D Chlorine given off Hydrogen given off

8. Which of the following sets of changes would occur during the electrolysis of silver B
nitrate solution using graphite electrodes?
Number of Number of pH value of
moles of Ag＋(aq) moles of NO3－(aq) the solution
A Decreases Decreases Remains unchanged
B Decreases Remains unchanged Decreases
C Remains unchanged Remains unchanged Decreases
D Remains unchanged Decreases Remains unchanged
 Chapter 29 to 32 Redox reactions, Simple chemical cells and electrolysis / notes / 60

9. In an experiment, concentrated sodium iodide solution is electrolyzed using carbon D

electrodes. Which of the following combinations concerning the changes in the
experiment is correct?
Product at cathode Product at anode Resulting solution
A Hydrogen Iodine More concentrated sodium iodide
B Sodium Oxygen More concentrated sodium iodide
C Hydrogen Oxygen Sodium hydroxide
D Hydrogen Iodine Sodium hydroxide

10. The following diagram shows the set-up for electrolysis of concentrated sodium A
chloride solution.

Which of the following combinations is correct?

Product at cathode Product at anode Colour of indicator

A Sodium Chlorine Red
B Sodium Chlorine Yellow
C Hydrogen Oxygen Red
D Hydrogen Hydrogen Yellow

11. A

Which of the following statements concerning the above set-up is INCORRECT?

A Only hydroxide ions migrate to the anode.
B The negative electrode is the cathode.
C Gas A is oxygen.
D The electrodes can be made of platinum.
 Chapter 29 to 32 Redox reactions, Simple chemical cells and electrolysis / notes / 61

12. Questions 12 and 13 refer to the following experiment. B

The gases collected at electrodes X and Y respectively are in the volume ratio of
A 1 : 1.
B 1 : 2.
C 2 : 1.
D 1: 4.

13. Which of the following statements concerning the above experiment are correct? D
(1) The concentration of zinc ions around electrode Y increases.
(2) The pH value of zinc sulphate solution remains unchanged after electrolysis.
(3) Same products will be obtained at both electrodes if dilute zinc sulphate solution
is used instead of concentrated zinc sulphate solution.
A (1) and (2) only
B (1) and (3) only
C (2) and (3) only
D (1), (2) and (3)

14. Directions: Questions 14 and 15 refer to the following set-up. D

What is the function of the rheostat?

A To measure the current.
B To supply energy.
C To increase electrical conductivity of the conducting wire.
D To vary the current.

16. Which of the following substances is best to be used to make the electrodes in the C
electrolysis of dilute sodium chloride solution?
A Zinc B Platinum C Graphite D Calcium
 Chapter 29 to 32 Redox reactions, Simple chemical cells and electrolysis / notes / 62

17. A solution of potassium hydroxide was electrolyzed using graphite electrodes. Which B
of the following graphs correctly represents the change in mass of cathode with time?

18. Which of the following substances, when electrolyzed using graphite electrodes, will C
liberate gaseous products at both electrodes?
A Molten sodium chloride
B Sodium bromide solution
C potassium sulphate solution
D Silver nitrate solution

19. Directions: Questions 19 and 20 refer to the following set-up. B

Electrodes E and F are copper electrodes while electrodes G and H are carbon
electrodes.Which of the electrodes are cathodes?
A E and H
B E and G
C F and H
D F and G

20. Which of the following combinations concerning the resulting solutions is correct? D
Solution in beaker X Solution in beaker Y
A Becomes more concentrated Becomes more concentrated
B Remains unchanged Becomes nitric acid
C Becomes less concentrated Becomes less concentrated
D Remains unchanged Becomes more concentrated
 Chapter 29 to 32 Redox reactions, Simple chemical cells and electrolysis / notes / 63

21. Directions: Questions 21 and 22 refer to the following set-up. A

On completing the circuit, the mass of electrode B increases.

Which of the following statements about the above set-up is correct?
A X is the positive terminal of the battery.
B Electrode A is the cathode.
C Oxidation occurs at electrode B.
D The colour of the copper(II) sulphate solution fades.

22. Which of the following half-equations represents the reaction at electrode C? C

A 2H＋(aq) + 2e－ → H2(g)
B Na＋(aq) + e－ → Na(s)
C 4OH－(aq) → O2(g) + 2H2O(l) + 4e－
D NO3－(aq) + 4H＋(aq) + 3e－ → NO(g) + 2H2O(l)

23. Which of the following statements concerning the set-up below are correct? D

glass tubing

nichrome wire electrode

nichrome wire electrode

molten lead(II) bromide

heat
(1) Lead(II) ions are reduced.
(2) The experiment should be performed in a fume cupboard.
(3) A reddish-brown gas is given off at the anode.
A (1) and (2) only
B (1) and (3) only
C (2) and (3) only
D (1), (2) and (3)

24. In which of the following electrolytic processes will the electrolyte become more D
acidic?
(1) Electrolysis of dilute hydrochloric acid using carbon electrodes
(2) Electrolysis of dilute nitric acid using platinum electrodes
(3) Electrolysis of dilute silver nitrate solution using carbon electrodes
A (1) only
B (2) only
C (1) and (3) only
D (2) and (3)
Ans is D because dilute hydrochloric acid is 2M HCl where the concentration of
 Chapter 29 to 32 Redox reactions, Simple chemical cells and electrolysis / notes / 64

Cl- is sufficient high and discharged to give Cl2 gas. In (1), after electrolysis, H+
and Cl- is discharged and the concentration of HCl decreases and the solution
becomes less acidic.
When dilute nitric acid is electrolysed, H+ and OH- is discharged. Overall
equation is 2H2O ® 2H2 + O2. Since the amount of H2O decrease and the
concentration of HNO3 (aq) increases and hence the solution becomes more acidic.
When silver nitrate is electrolysed, Ag+ ion and OH- is discharged. The resulting
solution become HNO3 and the solution become more acidic.

25. Which of the following set-ups can be used to plate a layer of copper on a key? B

26. Which of the following half-equations represents the change at the negative electrode C
when electroplating an iron object with nickel?
A Fe2＋(aq) + 2e－ → Fe(s)
B Fe(s) → Fe2＋(aq) + 2e－
C Ni2＋(aq) + 2e－ → Ni(s)
D Ni(s) → Ni2＋(aq) + 2e－

27. Which of the following substances is not the product made from industrial electrolysis D
of brine?
A Sodium hydroxide
B Bleaching solution
C Hydrochloric acid
D Mercury

28. Which of the following is NOT an application of electrolysis? C

A Extraction of reactive metals from their ores
B Electroplating
C Removal of metal ions from sewage
D Anodization

29. Electrolysis is used in the extraction of C

(1) copper.
(2) sodium.
(3) aluminium.
 Chapter 29 to 32 Redox reactions, Simple chemical cells and electrolysis / notes / 65

A (1) and (2) only B (1) and (3) only

C (2) and (3) only D (1), (2) and (3)

30. To coat a layer of chromium on a copper ring, B

(1) the ring to be electroplated should be the cathode.
(2) the electrolyte should be dilute sulphuric acid.
(3) The anode should be made of chromium.
A (1) and (2) only B (1) and (3) only
C (2) and (3) only D (1), (2) and (3)
Suggested Answer

1. B 11. A 21. A
2. A 12. B 22. C
3. C 13. D 23. D
4. A 14. D 24. D
5. A 25. B
6. C 16. C 26. C
7. A 17. B 27. D
8. B 18. C 28. C
9. D 19. B 29. C
10. A 20. D 30. B