Chapter 6

Electrochemistry

1
 A. Electrolytes and Non
Electrolytes

Electrolytes
• Electrolytes are substances that can
conduct electricity when they are in
molten states or aqueous solution and
undergo chemical changes.

2
 A. Electrolytes and Non
Electrolytes

• Examples of electrolytes are:

– dilute acids and alkalis
– molten zinc bromide
– sodium chloride solution

3
 A. Electrolytes and Non
Electrolytes
• Why electrolytes are able to conduct
electricity?

Electrolytes are able to conduct

electricity because there are free ions
present in the molten or aqueous state.

4
 A. Electrolytes and Non
Electrolytes
Non-electrolytes

• Non electrolytes are substances that

cannot conduct electricity either in
molten state or aqueous solution.

5
 A. Electrolytes and Non
Electrolytes
Non-electrolytes

• Examples of non-electrolytes are:

– naphthalene
– benzene
– alcohol
– tetrachloromethane

6
 A. Electrolytes and Non
Electrolytes

• In other words, all non-electrolytes are

covalent compounds which do not
contain ions and thus, they are not
able to conduct electricity.

7
 A. Electrolytes and Non
Electrolytes

Molten
PbBr2

NaCl
Solution

• Figure 6.1 An electrolyte can conduct

electricity because of the presence of free
moving ions. Experiment 8
 DIY
1. What is an electrolyte?
2. Explain why a sugar solution does not conduct electricity
while a common salt solution conducts electricity.
3. Classify the following into electrolytes and non-
electrolytes.
Hydrochloric acid, HCl
Ammonia, NH3 solution.
Glucose solution.
Molten lead.
Potassium chloride crystals.
Zinc sulphate solution.
Molten naphthalene.

9
 DIY (Answer)
1. Substances that can conduct electricity when they are in
molten state or aqueous solution and undergo chemical
changes.
2. Sugar solution does not have freely moving ions while
salt solution do have freely moving ions.
3. Hydrochloric acid, HCl electrolytes
Ammonia, NH3 solution. electrolytes
Glucose solution. non-electrolytes
Molten lead. non-electrolytes
Potassium chloride crystals. non-electrolytes
Zinc sulphate solution. electrolytes
Molten naphthalene. non-electrolytes

10
 B. Electrolysis of Molten
Compound
Electrolysis
• When electricity is passed through molten lead
(II) bromide, PbBr2 – a reaction take
place.This is called electrolysis.

• Electrolysis is a process whereby compounds

in either molten or aqueous state are broken
down into their constituent by passing electricity
through them.

11
 B. Electrolysis of Molten
Compound
• The electrolytic cell is the set of apparatus
needed to conduct electrolysis.It should
consist of the followings:
– Battery
– An electrolyte
– Two electrodes

12
 B. Electrolysis of Molten
Compound
• Remember that:
– An electrode which is connected to the
positive terminal of an electric source is
called the anode.
– An electrode which is connected to the
negative terminal of an electric source is
called the cathode.

13
 B. Electrolysis of Molten
Compound
• In molten electrolyte, the ions move freely.
• During electrolysis,
– negative ions (anions) move to anode.
– Positive ions (cations) move to cathode.

*A new substance then formed at each

electrode.

14
 B. Electrolysis of Molten
Compound
• Experiment 6.2 – To Investigate the
electrolysis of molten lead (II) bromide,
PbBr2.
1. Lead (II) bromide, PbBr2 is an ionic compound.
2. Hence, it consists of the positive lead (II) ions,
Pb2+ and the negative bromide ions, Br- .
3. In solid lead (II) bromide, PbBr2, these ions do
not move freely but are held in a fixed positions
in a lattice. When it melts, the ions are free to
move.

15
B. Electrolysis of Molten
Compound

16
 B. Electrolysis of Molten
Compound
4. During the molten lead(II) bromide, PbBr2,
i) the negative bromide ions, Br- are attracted
to the anode,
ii)the positive lead(II) ions, Pb2+ are attracted
to the cathode.

In the molten state, heat energy that is

provided breaks down the electrostatic
forces so that ions are able to move freely.
Thus we have:
PbBr2 (s)  Pb2+ + 2Br-

17
 B. Electrolysis of Molten
Compound

What happens to the

cathode and anode
during the electrolysis?
18
 B. Electrolysis of Molten
Compound
• At the anode :
Bromide ions, Br- undergo discharge, each
of the ions release an electron to form a
neutral bromine atom. Two bromine atoms
combine to form a bromine gas. The half
equation that we have are as below:
2Br-(l)  Br2 (g) + 2e-

19
 B. Electrolysis of Molten
Compound
• At the cathode :
lead(II) ions, Pb2+ undergo discharge
whereby each of the ions accepts two
electrons to form a lead atom. The half
equation are as follows:

Pb2+ (l) + 2e-  Pb(s)

20
 B. Electrolysis of Molten
Compound
• Combining the two half equations, we
get the overall equation that represents
the electrolysis of molten lead (II)
bromide.

Pb2+ (l) + 2Br- (l)  Pb (s) + Br2 (g)

21
 More to know

• Bromine gas, Br2 is red-dish brown in color

and is poisonous.
• The process of discharge can either be
donating electrons or accepting
electrons.

22
 DIY
1. State the meaning of the following terms.
a) anode
b) cathode
c) electrolysis

23
 DIY
2. A molten oxide, Q2O3 is electrolysed
using carbon electrodes.

24
 DIY
a. What ions are present in the electrolyte?
b. Write the formulae for the ions present in the
electrolyte.
c. State the ions that move to each of the
electrodes during the electrolysis.
d. Write the half equation of the reaction at each
of the electrodes.
e. Named the substances formed at each of the
electrodes.

25
 DIY (Answer)
1. a. An electrode which is connected to the
positive terminal of an electric source.
b. An electrode which is connected to the
negative terminal of an electric source.
c. A process whereby compounds in either
molten or aqueous state are broken down
into their constituent by passing electricity
through them.

26
 DIY (Answer)
2.
a. Positive ions Q: 3+, Negative ions O: 2-

b. Formulae ions are Q3+ and O2-

c. i) the negative ions, O2- are attracted to the anode,

ii) the positive ions, Q3+ are attracted to the cathode.

d. Half equations: anode terminal: 2O2-  O2 (g) + 4e-

Half equations: cathode terminal: Q3+ + 3e-  Q(s)

e. Negative electrodes: an atom of substance Q is

performed/deposited.
Positive electrodes: an oxygen gas is released.
27
 C. Electrolysis of Aqueous
Solutions
• In molten ionic compound, only one cation and
one anion are present.
• In aqueous solutions, the presence of water,
results in two types of cations (metallic cation
and hydrogen ion) and two types of anions
(non-metallic anion of salt and hydroxide ion).
• Water in aqueous solution dissociates partially
to form H+ and OH- ions.
+ -
H2O H + OH

28
 C. Electrolysis of Aqueous
Solutions
• For example: The electrolysis of copper
(II) sulphate, CuSO4 solution.
• Copper(II) sulphate, CuSO4 solution
consists of copper(II) ions,Cu2+, sulphate
ions,SO42-, hydrogen ions,H+ and
hydroxide ions,OH- that move freely.
• Cation : Cu2+, H+
• Anion : SO42-, OH-
29
 C. Electrolysis of Aqueous
Solutions
• During electrolysis :
– The cations (H+ and Cu2+) move to the cathode. Cu2+
are selectively discharged whereby each of the ions
accepts 2 two electrons.
Cu2+ (aq) + 2e-  Cu(s) ,
thus copper metal is formed at the cathode.
– The anions (OH- and SO42-) move to the anode. OH-
are selectively discharged by donating electrons.
4OH-(aq)  2H2O (l) + O2 (g) + 4e-
, bubbles of oxygen gas,O2 can be seen at the anode.

30
 Factors Which Influence the
Discharge of Ions
1. Position of Ions in the Electrochemical
Series (ES)
2. Concentration of ions in the solution
3. Types of electrodes

31
1. Position of Ions in the Electrochemical
Series (ES)

Almost never take part

(least reactive)

Take part if the solution is

concentrated

Nearly always takes part

(most reactive)

32
1. Position of Ions in the Electrochemical
Series (ES)
– The lower the ion in the ES, the easier it is
to be discharged.
– That is, ions at the bottom are easier to form
elements.
– For example in the electrolysis of PbNO3
solution, the ions present are Pb2+, NO3- , H+
and OH- .
– OH- ions are discharged by donating
electrons to form oxygen gas while H+ ions
accept electrons to form hydrogen gas.
33
2. Concentration of Ions in The Solution
– An ion will be selected for discharge if its
concentration in the aqueous solution is
high.
– Example1:
• Electrolysis of aqueous solution of halide such as
NaBr, NaCl or NaI.
• In the electrolytic cells, the halide (Br-, Cl-, I-) are
present together with the hydroxide ions (OH-).
• If the concentration of halide ions are higher than
the hydroxide ions, then the halides will be
discharged.

34
3. Types of Electrodes Used in Electrolysis
– Carbon and platinum are most commonly used
electrodes in Electrolysis. (inert to chemical
reactions)
– Sometimes other electrodes, like copper plates or
mercury, are used.
– Example : the electrolysis of dilute sodium chloride
(NaCl) using carbon electrodes. Oxygen and
Hydrogen gas will be produced.
– If mercury is used as the cathode, different reaction
occurs at the cathode. Sodium ions are selected
discharged instead of hydrogen while in the anode,
Cl gas is discharged to form chlorine gas.

35
Electrolysis of salt Using the Same
Element as the Electrodes
• Sometimes an electrolysis can be carried
out by using the same type of elements as
the cations in the solution.
• Example :
– a) Electrolysis of copper(II)sulphate using
copper as the electrode
– b) Electrolysis of silver(I)nitrate using silver
as the electrode.

36
Electrolysis of salt Using the Same
Element as the Electrodes
• At the anode :
– The electrode will dissolve. The mass of the
electrode (anode) will become smaller.
– The metal ions will be formed. The anode will
become thinner

Cu (s)  Cu2+(aq) + 2e
Ag (s)  Ag+ (aq) + e

37
Electrolysis of salt Using the Same
Element as the Electrodes
• At the cathode :
– The metal will be deposited at the cathode.
Cathode will become thicker.
– Its mass will increase. This is due to the
discharge of of the metal ions.

Cu2+(aq) + 2e  Cu (s)
Ag+ (aq) + e  Ag (s)

38
 Electrolysis of aqueous solution
Aqueous Ions Cathode Product at Anode Product at
electrolyte electrode the cathode electrode the anode

Sulphuris acid Platinum Hydrogen Platinum Oxygen

Hydrochloric acid Carbon Hydrogen Carbon Oxygen

Sodium chloride Platinum Hydrogen Platinum Oxygen

Potassium iodide Carbon Hydrogen Carbon Oxygen

Silver nitrate Silver Silver Silver Silver

deposited dissolves
Copper(II) Copper Copper Copper Copper
sulphate deposited dissolve
39
 DIY
P Q

dilute sulphuric acid

a) Name
i. Electrode P :
ii. Electrode Q :
b) What is the function of the ammeter?
c) Give the formulae of all the ions present
in dilute sulphuric acid.
40
 DIY
d) Construct a half ionic equation for the
reaction at electrode P.
e) Describe the test for the product of
electrolysis at electrode P.
f) Construct a half ionic equation for the
reaction at electrode Q.
g) Describe the test for the product of
electrolysis at electrode Q.
41
 DIY (Answer)
a) i) anode
ii) cathode
b) To measure the electric current.
c) H+, SO42-, OH-
d) 4OH-(aq)  2H2O (l) + O2 (g) + 4e-
e) Place a glowing wooden splint into the test
tube. The glowing wooden splint relights.
f) 2H+ + 2e-  H2 (g)
g) Place a burning wooden splint near the mouth
of the test tube. A ‘pop’ sound is heard.

42
43
 D. ELECTROLYSIS IN
INDUSTRIES
 In industries, electrolysis is used
to…
a) Extract reactive metals
e.g. The extraction of aluminium oxide
b) Purify metals
e.g. Purification of Copper
c) Electroplate metals
e.g. Electroplating of copper and silver

44
 a) Extract reactive metals
 Metals that are very reactive (top of
ES) such as sodium, calcium and
aluminium are extracted from their
compounds by electrolysis.
 That metals cannot be extracted
from mineral by the reduction using
carbon.

45
Extraction of aluminium metal from
the mineral bauxite.
Bauxite is a mineral that consist of aluminium
oxide, Al2O3
Cryolite is added to aluminium oxide to lower its
melting point from 2000°C to about 950°C.
Molten aluminium oxide is electrolysed using
carbon as electrodes in the electrolytic cell as
shown in next figure.
Molten aluminium oxide dissociates into ions as
follows:

46
Extraction of aluminium metal from
aluminum oxide

47
At the cathode: Al3 ions are discharged to
form aluminium metal.

At the anode: O2- ions are discharged to

form oxygen gas.

Overall equation of electrolysis:

48
The carbon anode is required to be
changed from time to time because the
oxygen gas generated oxidises the carbon
anode to form carbon dioxide.

49
 b) Purification of Metals
 Metals extracted by industrial process are
seldom pure. These metals can be purified
by using electrolysis process.
 In purification of copper, impure copper is
made as anode and pure copper is made
as cathode. The electrolyte is a dissolved
copper salt such as copper(II) sulphate.

50
 A small piece of pure copper was made the
cathode.
 The impure copper was made the anode as
shown in the diagram above.
 The electrolyte can be any aqueous solution of
copper salt such as copper(II) sulphate or
copper(II) chloride.

51
 At the anode
Copper anode will dissolve. This will form
copper ions (Cu2+).
Cu(s)  Cu2+(aq) + 2e

52
 At the cathode
The copper ions from the impure copper
electrode will migrate to the cathode. The
copper ions accept electrons to become
copper.
Cu2+(aq) + 2e  Cu(s)

53
 The pure copper cathode will become
thicker. The impure copper anode will
become thinner.
 The impurities drop to the floor of the cell.
 A pure layer of copper will stick to the
cathode.
 Finally, the cathode is removed. The
impurities at the bottom are then checked.
Sometimes, impurities contain silver and
gold too.

54
 c) Electroplating of Metals
 Electrolysis is often used to coat one metal with
another. This is called electroplating.
 The purpose of electroplating is to make the
original metal object (a) look more attractive, or
(b) to prevent it from rusting.
 During electroplating process, a small electric
current is normally used.
 The object to be plated is constantly rotated.
 Electroplating is greatly used in industry for
example, car bumpers are sometimes
electroplated with chromium. This made the car
bumpers look shiny. It also prevents the bumper
from rust. Iron is electroplated with tin so that it
will not rust. 55
 Electroplating of Nickel with Silver

• Cathode is joined to the object to be plated such

as the jug.
• The anode is made of silver.
• The electrolyte is a solution of a silver compound
such as silver nitrate.
56
 At the anode:
The silver dissolves, forming silver
ions in solution.
Ag(s)  Ag+(aq) + e
 At the cathode:

Silver ions receive electrons to form

silver. The silver is deposited on the
jug.
Ag+(aq) + e  Ag(s)
When the layer of silver is thick
enough, the jug is removed.

57
58
59
Benefits and Harmful Effects
of Electrolysis
• Benefits of Electrolysis
1. It is an effective method to extract reactive metals from
their ore. For example, magnesium and aluminium are
impossible to be extracted by using carbon or hydrogen
reduction process. Electrolysis seems to be the only
alternative.

2. Useful chemical compounds can be obtained by electrolysis

process. For example, chlorine and sodium hydroxide can
be obtained easily by electrolysis of sodium chloride.

3. Electroplating process can be used to make things more

beautiful and to prevent them from rusting. For example,
iron object can be make to look more attractive by
electroplating it with a layer of silver or a layer of
chromium. This electroplated object will not rust too.

60
• Harmful Effect of Electrolysis
1. Too much electricity consumption during
electrolysis
(a) Electrolysis process needs to use a lot
of electricity.
(b) For the generation of electricity we
need to built dam, built nuclear power
station or burn more fossil fuel.
(c) The generation of electricity will have a
big negative impact on our environment.
There will be pollution and disruption of
ecology too.

61
• Harmful Effect of Electrolysis
2. Nickel and chromium electroplating,
produce many unwanted products.
(a) These unwanted products, contain
nickel chromium. The unwanted products
are often thrown into our environment.
(b) This will pollute our water supply
system.
(c) Nickel and chromium are heavy
metals these two metals are present in
our water supply system, they will
endanger our health.

62
• Harmful Effect of Electrolysis

3. Silver plating industries produces cyanide

ions. These ions are extremely
dangerous to our health.
4. Products to be electroplated are normally
cleaned with acid first. This is to get rid
of the layer of oxides on the metal
surfaces. The used acid are normally
thrown away into our water system. This
will cause water pollution and kills
aquatic lives.

63
 Steps to Reduce Pollution
from Electrolysis Industries
1. Encourage recycling of metals that are extracted
by electrolysis. For example, we can recycle
aluminium cans and aluminium utensils.
2. Reduce the use of materials made from
electrolysis, such as aluminium products.
Substitute them with less polluting products.
3. Reuse things made of materials produced by
electrolysis. For example, we can reuse
aluminium containers instead of throwing them
away.
4. The by-products from the electroplating
industries should be treated before discharging
them into our waterways.

64
 E. Voltaic Cell
• Revision
Electrolytic Electrical energy is supplied to
cell produced chemical reaction

Chemical Chemical reaction produced

cell the electrical energy

65
V
Voltmeter

Chemical reaction from the lemon

produces the electrical energy

lemon

Simple Voltaic Cell

66
 Voltmeter detects the potential
V difference of the electricity

Simple Voltaic Cell

2 different
metal
electrodes

Electrolyte

67
 Voltaic Cell
• Voltaic cell also known as galvanic cell.
• Daniell cell is another example of a voltaic cell.
• In Daniell cell, the two solutions are connected
through a salt bridge or a porous pot.
• The solution used in the salt bridge is usually a
diluted acid or a solution of sodium or
potassium salts.
• The function of the salt bridge or porous pot is
to stop the two electrolytes from mixing.
• But allow the movement of the ions in order to
complete the electric circuit.

68
How does a voltaic cell work?

69
The set-up of a Daniell Cell
using a salt bridge

The set-up of a Daniell Cell

using a porous pot

70
• Zinc is higher than copper in the electrochemical
series. Thus it releases electrons more easily
than copper. Each zinc atom donates two
electrons to form a zinc ion.The zinc ions are
released into the electrolyte. The zinc plate
dissolves gradually.
• Since the Zinc is higher than copper in the
electrochemical series. It acts as the cathode of
the cell (negative terminal).
• The ionic equation of cathode:
Zn(s)  Zn2+ (aq) + 2e
71
• Copper as the anode of the cell (positive
terminal).The electrons are accepted by
the copper(II) ions to form copper metal.
The copper plate becomes thicker
gradually.
• The ionic equation of anode:
Cu2+ (aq) + 2e  Cu(s)
• The intensity of the blue colour of the
copper(II) sulphate solution decreases as
the concentration of copper(II) ions
decreases gradually.
72
Cells Used in Advantages Disadvantages

 Torches  No spillage  Cannot be

 Radio  Small in size recharged
 Easily carried  Not long lasting
 Electrical toys about  Electrolyte tends
 Cassette  Produces regular to leak
players current and  Low voltage is
voltage produced
 Obtained in
different sizes

 Motor  Can be recharged  Big in size

vehicles  Produces a high  Expensive
voltage and use  Leak charges
for a long period when not in used
of time  Spillage of acid
 Produces high can occurr
current(up to 75A)  Heavy and difficult
for heavy duty to carried about
purposes

73
Cassette players Last longer than Expensive
Electrical toys dry cell Cannot be
Appliances which Produces constant recharged
are in use for long current Electrolyte
periods No liquid leakage can occur
electrolyte

Cameras Small in size Very expensive

Watches Last a longer time Cannot be
Calculators Very mobile and recharged
easily used Mercury is not
environment
friendly

Electrical toys Can be recharged Expensive

Cassette players Smaller size than Transformer is
Radios accumulator needed for
No spillage recharging
Can be recharged
up to 500 times

74
 Differences between electrolytic and voltaic cell
Characteristic Electrolytic cell Chemical cell

Electrical energy produces Chemical reactions produce

Energy chemical reactions electrical energy.

Current supply into the cell. Current produced by the cell

Current

Cathode: terminal negative Cathode: terminal negative

Anode / Anode : terminal positive Anode : terminal positive
Cathode

Positive Anion gives out electrons to Electrons receive by positive

terminal anode terminal.

Negative Cation accept electron from Electrons given out from negative
Terminal negative terminal. terminal.

Type of Pairs of graphite, platinum or Pair of different metals.

electrode suitable metals.
75
 F. Electrochemical Series
• Note.
• Cation : K+ Na+ Ca2+ Mg2+ Al3+ Zn2+ Fe2+ Sn2+ Pb2+ H+ Cu+ Ag+
• Anion : F- SO42- NO3- CI- Br- I- OH-

Ease of releasing electrons increases

• An arrangement of metal based on the tendency of their atom

to donate electron.

“ The higher the position, the tendency are greater,

more electropositive”

76
 The Construction of the
Electrochemical
• Based on :
– the potential difference between two metal.
”the further the two metals, the greater the
voltage produced by the cell” ;
– the ability of a metal to displace another
metal from its salt solution.
“ the metal placed higher can displaces
a metal below it “

77
 The Construction of the
Electrochemical
• Example:

Zn (s) + Pb(NO3)2 (aq)  Zn(NO3)2 (aq) + Pb(s)

Metal displaced

Zn (s) + CuSO4 (aq)  ZnSO4(aq) + Cu(s)

Metal displaced

78
 The importance of the
electrochemical series
To determine :
• the terminals of a voltaic cell.
– metal at a higher position : negative terminal
– metal at a lower position : positive terminal
exp: Zn – Cu Cell

Negative Positive
terminal terminal

79
 The importance of the
electrochemical series
To determine :
• the standard cell voltage
– the further apart the metal, the bigger in the
voltage
• exp:
– Mg and Cu are further apart than Zn and Cu,
so,
“Mg- Cu cell has a bigger voltage than Zn-Cu
cell”

80
 The importance of the
electrochemical series
To determine :
• the ability of a metal to displace another
metal from its salt solution
exp:
Zn can displace Fe,Pb and Cu from their
salt solution because Zn is above these
metal but cannot displace Na or Al
because these metal are above Zn.
81
 DIY
1. Copy and complete Voltmeter reading Metal
(V)
the table below by
inserting the names 2.17
of the metals :
2.00
aluminium, copper,
iron, zinc and
1.10
magnesium if one of
the other electrodes
0.78
is copper.
0.00
82
 DIY
2. Write a balanced equation of zinc is added in
a test tube containing copper (II) nitrate.
3. Which of the following metal displacement
reactions will take place ?
A. Mg2+ + Zn  Mg + Zn2+
B. Cu + Pb2+  Cu2+ + Pb
C. Cu2+ + Mg  Cu + Mg2+
D. Fe2+ + Cu  Cu2+ + Fe

83
 DIY (Answer)
Voltmeter reading Metal
1. . (V)
2.17 Mg-Cu

2.00 Al-Cu

1.10 Zn-Cu

0.78 Fe-Cu

0.00 Cu-Cu
84
 DIY (Answer)
2. Write a balanced equation of zinc is added in a
test tube containing copper (II) nitrate.
Zn (s) + Cu(NO3)2 (aq)  Zn(NO3)2 (aq) + Cu (s)

2. Which of the following metal displacement

reactions will take place ?
C. Cu2+ + Mg  Cu + Mg2+

85
86