RAFFLES GIRLS’ SCHOOL (SECONDARY)

RAFFLES PROGRAMME
YEAR 4 CHEMISTRY
Established in 1879

Name : _____________________________ ( ) Class : _______

Date : ________________

3 ELECTROCHEMISTRY
Electrochemistry is the branch of chemistry that deals with inter-conversion between electrical energy and
chemical energy. Electrochemical processes are redox reactions in which the energy released by a spontaneous
reaction is converted to electricity or in which electrical energy is used to cause a non-spontaneous reaction to
occur. Electrolysis has many important industrial applications including the extraction of reactive metals.

3.1 Electrolysis & Electrolytic Cell

Electrolysis is the process by which electrical energy is used to cause a non-spontaneous chemical
reaction to occur. Electrolysis takes place in an electrolytic cell as shown in Figure 1. An electrolytic
cell has the following components:
 External power source
 Electrons flow out from the negative terminal of the battery and towards the positive terminal
of the battery.
 Electrodes
 Electrodes are made of electrical conductors e.g. platinum and graphite.
 Electrode connected to the positive terminal of the battery is called anode.
Anions (negatively-charged ions) undergo oxidation at the anode (positively-charged
electrode).
 Electrode connected to the negative terminal of the battery is called cathode.
Cations (positively-charged ions) undergo reduction at the cathode (negatively-charged
electrode).
 Electrolyte
 Electrolyte is a compound that conducts electricity in the molten state or in aqueous
solutions e.g. ionic compound.

battery
e- e-

anode cathode

anion cation
electrolyte

Fig. 1 An Electrolytic Cell

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State the differences between electrical conduction by electrical conductors e.g. metals and
graphite and that by electrolytic conductors e.g. molten ionic compounds.

Electrical conduction by metals Electrical conduction by

and graphite electrolytic conductors
(electrodes) (electrolytes)

Physical state of the conductor Solid Molten / aqueous

Type of mobile charge carriers (mobile) electrons (mobile) ions

Do not undergo any change

after conducting electricity.
Effect of conduction Electrolyte decomposes
(except reactive anodes such as
Cu anode and Ag anode)

3.2 Electrolysis of Molten Ionic Compounds

Molten salts are ionic compounds that have been heated past their melting points. Therefore, they
are in liquid state and can conduct electricity due to the presence of mobile ions.

Example 1: Let’s look at the electrolysis of molten lead(II) bromide, PbBr2.

https://www.youtube.com/watch?v=i9xS9t-KMpc (0:30 - 3:45)
Label the electrodes in the diagram below and write the corresponding half-reactions at the anode
and cathode.

Half-equation at cathode:

Pb2+(l) + 2e-  Pb(l)

cathode anode Observation(s) at cathode:

Silvery liquid collected at the bottom of the
reaction vessel.

Half-equation at anode:

2Br-(l)  Br2(g) + 2e-

Observation(s) at anode:
Reddish-brown and pungent gas evolved at
the anode.

Fig. 2 Electrolysis of molten lead(II) bromide Overall reaction:

PbBr2(l)  Pb(l) + Br2(g)

2
Example 2: Let’s look at the electrolysis of molten zinc chloride, ZnCl2.
https://www.youtube.com/watch?v=i9xS9t-KMpc (3:49 – 4:45)
Predict what you would observe happening at each electrode and write the corresponding half-
equations.

Half-equation at cathode: Half-equation at anode:

Zn2+ (l) + 2e-  Zn(l) 2Cl-(l)  Cl2(g) + 2e-

Observation(s): Observation(s):
Silvery liquid collected at Greenish-yellow and
the bottom of the pungent gas evolved at the
reaction vessel. anode.
(Gas turned moist blue
litmus paper red then
bleaches it.)

Overall reaction: ZnCl2(l)  Zn(l) + Cl2(g)

Fig. 3 Electrolysis of molten zinc chloride

Binary Ionic Compounds

Lead(II) bromide and zinc chloride are examples of binary ionic compounds that contain ions from
only two different elements. When binary compound undergoes electrolysis, it decomposes into a
metal and a non-metal (products).

3.3 Electrolysis of Aqueous Solutions of Compounds

The electrolysis of aqueous solutions is slightly more complex as there are more than one type of
cations and anions present in the electrolyte.

Consider the electrolysis of aqueous sodium chloride. The electrolytic cell contains sodium ions (Na+),
chloride ions (CI-) and small amounts of hydrogen ions (H+) and hydroxide ions (OH-) from partial
dissociation of water in the solution i.e.

H2O(l) ⇌ H+(aq) + OH-(aq)

What are the possible reduction reactions at the cathode? What are the possible oxidation reactions
at the anode? How do you know which reaction actually takes place at the respective electrodes?

Anode (oxidation) half-equations: Cathode (reduction) half-equations:

2Cl-(aq)  Cl2(g) + 2e- Na+(aq) + e-  Na(s)

4OH-(aq)  O2(g) + 2 H2O(I) + 4e- 2H+(aq) + 2e-  H2(g)

Possible products are chlorine gas or Possible products are sodium metal or
oxygen gas. hydrogen gas.

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Selective Discharge of Ions
In electrolysis, when more than one type of cations or anions is present in a solution, only one cation
and one anion are preferentially discharged at the respective electrodes. This is known as the
selective discharge of ions. If inert electrodes are used during electrolysis, the ions discharged and
hence the products formed depend on these factors:

1. The position of the ions in the electrochemical series Electrochemical Series

a. Cation
The more reactive the metal, the greater its tendency to form Cations Anions
ions. K+ SO42-
 Ions of reactive metals such as potassium and sodium (K+ ion Na+ NO3-

Increasing ease of discharge

and Na+ ion) will remain as ions and will not be discharged at Ca2+ Cl-
the cathode. Mg2+ Br-
Al3+ I-
 Ions of hydrogen and less reactive metals like copper and silver
Zn2+ OH-
(H+, Cu2+ and Ag+) will accept electrons more readily (or ions
Fe2+
are more easily reduced) and get discharged at the cathode. Sn2+
b. Anion Pb2+
Sulfate ions (SO42-) and nitrate ions (NO3-) are not discharged H+
during electrolysis and will remain in the solution. Hydroxide Cu2+
ions (OH-) give up electrons most readily (or are most easily Ag+
oxidised) at the anode during electrolysis to form water and
oxygen.

2. The concentration of the anion in the electrolyte (for Cl-, Br-, I- ions)
The anion present in greater concentration will be preferentially discharged, even if it’s higher in
the series. For example, in the electrolysis of concentrated sodium chloride solution, Cl- and OH-
ions are attracted to the anode. According to their relative ease of discharge, OH- ions should be
discharged preferentially. However, in concentrated sodium chloride solution, there are more
Cl- ions than OH- ions, so Cl- ions are preferentially discharged at the anode, not OH- ions.

3. The nature of the electrode

Usually, inert electrodes such as graphite or platinum are used for electrolysis. These
electrodes do not interfere with the reactions occurring at the surface of the electrode, they
simply act as a point of connection between the electrical circuit and the solution.

However, if metal electrodes are used in metal ion solutions, they can get involved in the
reactions by dissolving as ions, leaving their electrons behind (this can only happen when the
metal takes the place of the anode, the positive electrode). In this case, the metal electrode
is a reactive electrode. Metals such as copper and silver are reactive anodes. For example,
in the electrolysis of aqueous copper(II) sulfate solution using copper electrodes, SO42- and
OH- ions are attracted to the anode. According to their relative ease of discharge, OH- ions
should be discharged preferentially. However, the reactive copper anode oxidises to form
Cu2+ ions in aqueous solution instead. The copper anode decreases in mass.
The reaction that occurs is: Cu(s)  Cu2+ (aq) + 2e-.

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Example 1: Electrolysis of Dilute Sodium Chloride Solution Using Graphite Electrodes (Inert)
In the electrolysis of dilute sodium chloride solution, the product formed at the cathode is hydrogen
gas, because H+ ions are more easily reduced than Na+ ions. At the anode, oxygen gas is given off
because OH- ions are more easily oxidised than Cl- ions.

-
OH H+

At the anode At the cathode

1) Ions present Cl- and OH- ions Na+ and H+ ions
2) Half-equations 4OH-(aq)  O2(g) + 2 H2O(I) + 4e- 2H+(aq) + 2e-  H2(g)
3) Products formed Oxygen gas Hydrogen gas
4) Observations Effervescence is observed. Effervescence is observed.
Colourless and odourless gas Colourless and odourless gas
evolved. evolved.
Gas relights a glowing splint. Gas extinguishes lighted splint
with a ‘pop’ sound.

3.4 Electrolysis of Water

To electrolyse water, a small amount of an ionic compound or dilute sulfuric acid is added to water.
The electrolysis of water literally means, separating water by electricity, i.e., passing electricity
through water causes its decomposition.

Half-equation at negative electrode (cathode):

O gas H gas 2 H+ (aq) + 2e-  H2(g) OR

2 2 2 H2O(ℓ) + 2e-  H2(g) + 2 OH-(aq)
dilute
H2SO4 Half-equation at positive electrode (anode):
anode cathode
4 OH-(aq) O2(g) + 2 H2O(ℓ) + 4e- OR
2 H2O(ℓ)  O2(g) + 4 H+(aq) + 4e-

Overall reaction:
+ –

Fig. 4 Electrolysis of dilute sulfuric acid 2H2O(l)  2H2 (g) + O2(g)

The electrolytic cell consists of a pair of electrodes immersed in water. The electrodes are then
connected to a battery that supplies the required electrical energy. During the electrolysis of water,
a dilute acid (H2SO4 or HNO3) is added because pure water is a very poor conductor of electricity.

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Quick Review 1

1 The diagram below shows a set-up of an electrolysis.

Which of the following particles are responsible for the conduction of electricity in M and N?

M N
A negative ions positive ions
B electrons electrons
C positive ions and negative ions electrons
D electrons positive ions and negative ions ( )

Answer: D
M is a conducting wire made of metal which has delocalised electrons to act as mobile charge
carriers to conduct electricity. N is an electrolyte (usually ionic compound in molten or aqueous
state) which has mobile ions to act as mobile charge carriers to conduct electricity.

2 During the electrolysis of dilute sodium chloride solution, hydrogen gas is released at the
cathode and oxygen gas is released at the anode.

Which of the following correctly represents the reactions that take place at both electrodes?

Anode Cathode
A reduction oxidation
B oxidation reduction
C reduction reduction
D oxidation oxidation ( )

Answer: B
Oxidation takes place at the anode due to the loss of electrons. Reduction takes place at the cathode
due to the gain of electrons. Remember “An Ox; Red Cat”.

3 Which of the following products are formed during the electrolysis of concentrated
magnesium chloride using carbon electrodes?

Anode Cathode
A chlorine magnesium
B hydrogen oxygen
C chlorine hydrogen
D oxygen hydrogen ( )

Answer: C

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The selective discharge of anion depends on the concentration effect. Since concentration MgCl2 is
used, chloride ions are selectively discharged at the anode to form chlorine gas.
The selective discharge of cation depends on the position of the ion in the electrochemical series.
Since H+ ions are more easily reduced than Mg2+ ions, hydrogen ions are selectively discharged at the
cathode to form hydrogen gas.

4 The apparatus in the diagram below was set up to electrolyse concentrated nickel(II)
chloride solution.

platinum platinum
electrode X electrode Y
concentrated nickel(II)
chloride solution
Which of the following statements with regard to this electrolysis is correct?

A At electrode X, chloride ions were oxidised.

B At electrode X, chloride ions were reduced.
C At electrode Y, nickel ions were oxidised.
D The platinum electrode Y was dissolved.
( )

Answer: A
Electrode X is the anode while electrode Y is the cathode.
A and B: The selective discharge of anion at the anode depends on the concentration effect. Since
concentration NiCl2 is used, chloride ions are selectively discharged at the anode to form chlorine
gas. Oxidation occurs at the anode.
C: The selective discharge of cation at the cathode depends on the position of the ion in the
electrochemical series. Since H+ ions are more easily reduced than Ni2+ ions, hydrogen ions are
selectively discharged at the cathode to form hydrogen gas. Reduction occurs at the cathode.
D: Platinum is an inert electrode and would not dissolve.

LET’S CHECK


success criteria
  
1 I am able to apply the idea of selective discharge based on cations, anions and
concentration effects.

2 I am able to predict the products of the electrolysis of an aqueous electrolyte.

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3.5 Industrial Applications of Electrolysis
A. Purification of Copper (Electrolytic Refining)

Copper metal obtained from its ores usually contains impurities

such as zinc, iron, silver and gold. The impurities can be removed
by electrolysis in which impure copper acts as the anode and
pure copper acts as the cathode. The electrolyte used is copper
(II) sulfate solution.

Questions:
1. Write the half-equations to show the processes happening at
the anode and cathode.
Half-equation at the impure copper anode:
Cu(s)  Cu2+ (aq) + 2e-

Half-equation at the pure copper cathode:

Cu2+ (aq) + 2e-  Cu (s)

2. How will the concentration of CuSO4 solution change during the electrolysis? What will be
observed? Why?
The concentration of CuSO4 solution will remain unchanged. The blue colour of the CuSO4
solution will remain unchanged. When one copper (II) ion is reduced at the cathode, another
copper atom is oxidized at the anode to form one copper (II) ion, therefore the concentration of
the copper(II) ions in the electrolyte is unchanged, so the blue solution remains unchanged.

3. How are the metal impurities that are more reactive than copper removed by electrolysis?
The metal impurities will be oxidized to form metal ions that will enter the solutions. These ions
of metal more reactive than copper are less easily reduced than copper(II) ions and will remain in
the electrolyte solution.

4. What will happen to the metal impurities that are less reactive than copper?
The metal impurities that are less reactive than copper will not be oxidized to form metal ions.
Instead they fall to the bottom of the reaction vessel as anode sludge.

5. Calculate the increase in mass of the pure copper cathode and the percentage purity of impure
copper ore if 1 mole of electrons were passed as electricity to completely purify 40 g of impure
copper.
Cu2+ (aq) + 2e-  Cu (s)
No. of moles of pure Cu = 0.500 mol
Mass of pure Cu = 0.500 × 64 = 32.0 g
% purity of copper ore = 32.0/40 × 100% = 80.0%

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B. Electroplating

Electroplating is a technique in which a thin layer of a metal is used to

‘coat’ another object. This process is often used to protect objects
against corrosion or to improve their appearance. The figure on the
left shows an electrolytic cell that is used to plate a metal spoon with
a layer of silver coating.

Questions:
1. Write the half-equations for the processes taking place at the
anode and cathode.
At the anode (oxidation):
Ag (s)  Ag+ (aq) + e-

At the cathode (reduction):

Ag+ (aq) + e-  Ag (s)

2. Explain the choice of the electrolyte solution and the materials used for the electrodes.
plating metals
Electrolyte solution – The solution will need to contain ions of the _________________.
substance to be plated
Electrodes – The cathode must be the ___________________________ while the anode is the
_________________.
plating metal

3. Calculate the mass of silver plated onto the spoon if 3.01 × 1023 electrons were passed as
electricity through the electrolytic cell.

Ag+ (aq) + e-  Ag (s)

No. of moles of electrons = (3.01 × 1023)/(6.023 × 1023) = 0.500 mol
No. of moles of Ag plated = 0.500 mol
Mass of silver plated = 0.500 × 108 = 54.0 g

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 Extraction of Aluminium

Aluminium is usually extracted from bauxite ore by

electrolysis. Bauxite is an impure aluminium oxide
containing impurities such as oxides of iron, silicon
dioxide and titanium dioxide. The ore is first converted
into pure aluminium oxide (Al2O3), which is then
dissolved in molten cryolite (Na3AlF6).

Questions:
1. What is the purpose of dissolving aluminium ore
in cryolite (Na3AlF6)?
The melting point of pure aluminium oxide is 2054oC. Cryolite is added as an impurity to lower
the melting point of aluminium oxide to 980oC and thereby reducing energy costs involved in
extracting aluminium.

2. Write half-equations to show the reactions that take place at the electrodes.
Half-equation at the anode: 2O2- (l)  O2 (g) + 4e-
Half-equation at the cathode: Al3+ (l) + 3e-  Al (l)
Overall equation: 2Al2O3(l)  4Al(l) + 3O2(g)

3. Calculate the mass of aluminium and the volume of oxygen formed (at rtp) when 0.1 mol of
aluminium oxide is completely electrolysed.
Ratio of Al2O3 : Al = 1:2
No. of moles of Al = 2 × 0.1 = 0.200 mol
Mass of Al = 0.2 × 27 = 5.40 g

No. of moles of O2 = 0.1 × 3/2 = 0.150 mol

Volume of O2 at r.t.p = 0.150 × 24.0 = 3.60 dm3

4. Why must graphite anode be replaced after a while?

Oxygen liberated at the anode will react with the graphite anode to form carbon dioxide gas.

5. Challenge Question: Draw a labelled diagram of an electrolytic cell that could be used for the
extraction of magnesium metal from molten magnesium chloride. Write half-equations and
predict the products that would be formed at the anode and cathode.

At the anode
Half-equation: 2Cl-(l)  Cl2(g) + 2e-

Product formed: chlorine gas

At the cathode
Half-equation: Mg2+(l) + 2e- Mg(l)

Product formed: molten magnesium

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11
3.6 Simple Cells

A simple cell is a device that converts chemical energy into electrical energy. Unlike the electrolytic
cell, a spontaneous redox reaction in the simple cell generates electrical energy. A battery is made
up of simple cells. Chemical reactions occurring in these simple cells generates electricity.
Recall that in an electrolytic cell, electrical energy is used to drive a non-spontaneous redox reaction.
There is an external power supply in the set-up of an electrolytic cell.
A simple electric cell consists of two electrodes (two different metals) and an electrolyte (acid or
alkali solution or salt solution).

How a simple cell works

 The electrodes are made of two different metals.
 The more reactive metal tends to undergo oxidation and gives up electrons readily. It will
become the anode (negative electrode).
 The less reactive metal will become the cathode (positive electrode), as it has a weaker
tendency to lose electrons.
 The electrons flow from the more reactive metal to the less reactive metal.
 The potential difference or cell voltage depends on the positions of the metals in the reactivity
series. The further apart the metals are in the reactivity series, the bigger the potential
difference or cell voltage produced. This cell voltage can be registered by a voltmeter or a
galvanometer as show in the diagram below.

dilute
sulfuric
acid

At the Anode
Since magnesium is more reactive than copper, magnesium tends to lose electrons more readily and
it is the anode. Each magnesium atom loses 2 electrons to form a magnesium ion.

Oxidation half-equation: Mg (s)  Mg2+ (aq) + 2e-

Observation
The magnesium strip (anode) erodes or becomes smaller.

Note: The electrons lost are transferred to the cathode (copper) through the wire. As a result,
current is produced and the galvanometer deflects.

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At the Cathode
Since copper is less reactive than magnesium, it will become the cathode. It provides the surface for
electron transfer to occur. The positive ions that are present in the electrolyte are magnesium ions
and hydrogen ions (Mg2+ and H+). The hydrogen ions are more easily reduced than the magnesium
ions, hence it accepts the electrons flowing into the cathode to form hydrogen gas.

Reduction half-equation: 2H+ (aq) + 2e-  H2 (g)

Observation
Effervescence is observed. Colourless and odourless gas evolved around the copper metal which
extinguishes a lighted splint with a ‘pop’ sound. The gas is hydrogen (H2).

Overall ionic equation: Mg (s) + 2H+ (aq)  Mg2+ (aq) + H2 (g)

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Quick Review 2

1 Apparatus was set up as shown. -

For which pair of metals would electrons flow in the direction shown?

Metal X Metal Y
A copper zinc
B iron magnesium
C iron aluminium
D zinc silver ( )

Answer: D

This is a simple cell. Electrons flow from the more reactive metals to the less reactive metals, i.e. X is
more reactive than Y.

Zinc is more reactive than silver in the reactivity series.

2 Which pair of metals X and Y will produce the highest voltage when used as electrodes in a
simple cell?

Metal X Metal Y
A copper silver
B magnesium silver
C magnesium zinc
D zinc copper ( )

Answer: B

The further apart the metals are in the reactivity series, the larger the potential difference or cell
voltage produced.

Magnesium and silver metals are furthest in the reactivity series thus produce greatest voltage.

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LET’S CHECK


success criteria
  
1 I am able to identify the anode of a simple cell as the one containing the
more reactive metal.

2 I am able to identify the cathode of a simple cell as the one containing the
less reactive metal.

3 I understand that the further apart the metals are in the reactivity series, the
greater the production of electrical energy.

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 COMPARE & CONTRAST
https://www.youtube.com/watch?v=1tvvSUySfls
Electrolytic Cell Simple Cell
What takes Electricity is used to cause a non- A spontaneous redox reaction occurs
place in the spontaneous redox reaction to occur. resulting in the production of
cell? electricity.
A battery provides the external power
source to cause the reaction to occur.
Energy electrical energy → chemical energy chemical energy → electrical energy
conversion
that occurs

Experimental
set-up

Electrodes & Oxidation occurs at the anode.
their reactions
Anode is positive as it is connected to
positive terminal of the battery.
Anions lose electrons here and are
discharged.
Oxidation occurs at the anode.
Anode is negative as electrons are
generated continuously. It is at this
electrode that the more reactive
metal loses electrons to form its ions
which go into solution.

Therefore, this electrode has an

excess of electrons and a negative
charge relative to the other electrode.
Reduction occurs at the cathode. Reduction occurs at the cathode.

Cathode is negative as it is connected to Cathode is positive (relative to the

the negative terminal of the battery.
Cations gain electrons here and are
discharged.
Electron flow Electrons flow in the external circuit from
the anode to the cathode.
other electrode where electrons are
continuously being generated). It is
here that positive ions gain electrons.
Electrons flow from the anode (the
more reactive metal) to the cathode
(the less reactive metal).

16