What is the name of the scientist who investigated the

theory of electrolysis in 1830?

Definition of Electrolyis
Electrolysis is the conduction of electricity by an electrolyte
(usually an ionic compound), when
molten or dissolved in water, leading to the
decomposition of the electrolyte.
Electrolytes conduct electricity because they contain
mobile ions.

During electrolysis,
electrical energy is converted into
chemical energy.
Electrolytes

Electrolytes is a compound in solution or molten

state that conducts electricity with the
decomposition at the electrodes as it does so.
Electrolytes are usually molten ionic compounds
or solutions of ionic salts.
Examples: hydrochloric acid, aqueous sodium
hydroxide, aqueous sodium chloride
 Electrolytes Non-electrolytes
Aqueous ethanoic acid Alcohol

Dilute nitric acid Sugar solution

Molten lead(II) bromide Pure deionised water

Copper(II) sulfate Pure ethanoic acid

solution
Lemon juice
Sodium carbonate solution
Why do ionic compounds conduct electricity in
molten and aqueous states but not in solid state?
In solid state, the
ions are held in fixed positions by
strong electrostatic forces.
In molten or aqueous states, the strong
electrostatic forces are weakened/overcome and
the ions are now
mobile. These mobile ions are able to conduct
electricity.
Question for discussion
1. What particles are responsible for electrical
conductivity?
Mobile electrons Mobile ions
present in conductors Present in electrolytes
such as metals & such as dilute HCl or
graphite molten NaCl
Question for discussion
2. What substance will remain unchanged when an electric
current pass through it?
Metals and graphite (elements)

3. What substance will decompose when an electric

current pass through it?
Electrolytes (E.g molten NaCl)
 Electrolysis of Molten lead (II) bromide

Electrons
Electronsflow
flowfrom
from
anode
anodetotocathode
cathode

Anode Positive Cathode Negative

electrode electrode
ADD
Molten lead(II) bromide contains:
Pb 2+
And Br -

Positive ions, Pb2+ , are attracted to negative electrode (cathode)

Always remember:
Cations are attracted to cathode

Negative ions, Br- , are attracted to positive electrode (anode)

Always remember:
Anions are attracted to anode.
 Reactions at the electrodes:
Reactions at the anode:

2 Br- (l) Br2 (g) + 2e- Recall, in balancing ionic equations,

Charge -2 0 -2 charge must also be balanced.

Bromide ions lose electrons to form bromine molecules.

Thus in general oxidation occurs at the anode.

Remember: An Ox

Anode Oxidation

Observation at anode:

Reddish-brown and pungent gas was observed.

 Reaction at cathode,
Pb2+(l) + 2e Pb(l)
-

Charge +2 -2 0

Lead(II) ions gain electrons to form lead atoms. Lead (II) ions are
said to be discharged.

In general reduction takes place at cathode.

Remember:

Red Cat
Cathode
Reduction

In the electrolysis of binary molten compounds,

a metal is discharged at the cathode;
a non-metal is produced at the anode.
A binary compound is a compound containing only two elements.
Eg NaCl , PbBr2
 Try practice 1 on page 3 of notes

Molten Ions Eqn Product Eqn

Product
electrolyte at anode at cathode

NaCl Na+, Cl- 2 Cl (l) Cl2(g) +2e

- -
Chlorine gas Na+(l) + e Na(l) Sodium
-

(yellowish- metal
Green gas)

PbO Pb2+, O2- 2 O (l) O2 (g) +4e

2- -
oxygen gas Pb2+ +2 e Pb
-
lead
metal

2 I (l) I2(g) +2e iodine Calcium

Cal2 Ca2+, l- - -
Ca2+ +2 e Ca
-

metal
Question for discussion (NOT in note)

During the electrolysis of molten lead(II) oxide, do you expect the

lead form to be solid or liquid? Why?

What information is needed?

Mp of PbO = 888 C

Mp of Pb = 327.5 C

Lead formed would be in molten/liquid form.

Aqueous electrolytes or solutions are mixtures of
two electrolytes : the compound and
water.

Water ionises to a very small extent to give a

very small amount of H+ and OH-
H2O H+ + OH-
Eg 1 : Electrolysis of concentrated hydrochloric acid
Ions present : H+, Cl-, OH-

From HCl and water From water

Ions at cathode: H+ Eqn at cathode: 2H+ (aq) +2 e- H2(g)

-

Ions at anode: Cl-, OH-

There are two anions at anode.

Which ion will discharge at anode ?
Factors in deciding which ion is discharged are:
Its position in electrochemical series

Concentration of the ion

Type of electrode
 Electrochemical Series
In an electrochemical series, metals or non-metals are arranged
in order of their reactivity.
Metallic ions Product at cathode
Least readily K+ (Group I)
discharged Hydrogen (from water)
Na+ (Group I) (Ions formed by metals
Ca2+ (Group II) above hydrogen in the
electrochemical series are not
Mg2+ (Group II) discharged.)
Al3+ (Group III)
Zn2+
Fe2+
ce Pb2+ (Depends on concentration)
r en + Hydrogen
fe H
Re int
po Cu2+ copper
Most readily +
Ag silver
discharged
 Non-metallic Ions Product at anode
Least readily Oxygen (from water)
discharged SO42-
(Sulfate and nitrate ion are not
discharged.)
NO3-
- O2 if electrolyte is
Cl
Dilute; respective
Br- Halogens if
Electrolyte is
I-
concentrated
Most readily
discharged OH- oxygen
Note:
When the non-metallic ions are close in their position in the
electrochemical series, order of discharged is influenced by
the concentration of anion.
E.g In the electrolysis of concentrated HCl, both OH- &
Cl-migrate to the anode. But concentration of Cl- is
larger than that of OH- .
Hence Cl- is preferentially discharged instead.
2 Cl- (l) Cl2(g) +2e-
Eg 2 Electrolysis of dilute sulfuric acid

Ions present in dilute sulfuric acid: H+, OH-, SO42-

Ions migrating to cathode: H+

Equation representing reaction at cathode:

2H+ (aq) +2 e- H2(g)

Products at cathode: Hydrogen gas

Observation:
Effervescence of colourless and odourless gas.
Eg 2 Electrolysis of dilute sulfuric acid

Ions migrating to anode: OH- SO42-

Equation representing reaction at anode: 4OH- (aq) 2 H2O(l)+ O2(g) +4e-

Reason:

sulfate ion which is high up in the electrochemical series is very

stable. A large amount of energy is required for sulfate to give up its
electrons, hence it is not discharged. Thus, hydroxide ions, OH- , is
preferentially discharged to give oxygen gas.

Product at anode: oxygen gas (and water)

Observation:
Effervescence of colourless and odourless gas.
The volume of H2 collected during electrolysis of dilute
sulfuric acid is twice that of oxygen. Why?

Anode: 4OH- 2H2O + O2 + 4e-

Cathode: 2H+ + 2e- H2

For 1 mole of oxygen produced at the anode, 4 moles of

electrons are released.
These 4 moles of electrons will reduce hydrogen ions at
the cathode to produce 2 moles of hydrogen gas.
Thus volume of hydrogen is twice that of oxygen.

Overall equation can be represented as:

2H2O 2H2 + O2

As water molecules are removed/decomposed,

concentration of sulfuric acid increases.
Electrolysis of Dilute sulfuric acid
Eg 2 Electrolysis of aqueous copper(II) sulfate using
graphite electrodes

Ions present : H+ Cu2+ SO42- OH-

Ions migrating to cathode: H+ Cu2+
Equation representing reaction at cathode: 2+
Cu (aq) + 2e- Cu(s)

Products at cathode: Copper (brown/pink solid deposited on cathode)

[link]
Eg 2 Electrolysis of aqueous copper (II) sulfate using
graphite electrodes

Ions migrating to anode: OH- SO4 2-

Equation representing reaction at anode:

4OH- (aq) 2 H2O(l)+ O2(g) +4e-

Products at anode: oxygen and water

Eg 2 Electrolysis of aqueous copper (II) sulfate using
graphite electrodes

What happens to the electrolyte after some time?

The blue electrolyte fades away and eventually
becomes colourless. This is due to the reduction of
copper (II) ion to copper atoms, leading to a decrease in
concentration of copper (II) ions in solution over time.
What happens to the pH of the electrolyte? Why?
The pH of electrolyte decreases. As hydroxide ions are
discharged, concentration of hydroxide ions decreases
and is less than that of hydrogen ions, hence making
the solution acidic.
Electrolyte Ions Eqn Product Eqn
Product
at cathode at anode

Conc
NaCl Na+, Cl-, 2 H (aq) +2e H2(g)
+ -
Hydrogen 2Cl (aq)Cl2(g) +2e Chlorine
- -

solution H+, OH-, Recall Na+ not gas gas

dishcarged in aq.
form.

Dilute Na+, Cl-, 2 H (aq) +2e H2(g) Hydrogen 4OH- (aq)2 H2O(l) Oxygen
+ -

NaCl H+, OH-, Recall Na+ not gas + O2(g) and

solution dishcarged in aq. +4e - water
form.

Dilute K+, Hydrogen 4OH- (aq)2 H2O(l) Oxygen

2 H (aq) +2e H2(g)
+ -

aqueous SO4 - 2
gas + O2(g) and
+ -
potassium H , OH +4e - water
sulfate
 Electrodes
Electrodes

Inert
Inert Reactive
Reactive
electrodes
electrodes electrodes
electrodes
(Electrode
(Electrodehas
hasno
noreaction
reaction (Electrode
(Electrodecan
can
with
withthe
theelectrolyte.
electrolyte. dissolve
dissolveininthe
the
electrolyte.
electrolyte.
Eg
Eggraphite
graphiteand
andplatinum)
platinum) Eg
Egcopper,
copper,silver
silver
nickel)
nickel)
Electrolysis of aqueous copper(II) sulfate using copper
electrodes
Copper
electrodes

aq. CuSO4

Ions present in aqueous copper(II) sulfate:

Cu2+, H+ , OH- , SO42-

Go to cathode
Substances at anode: Go to anode
OH- , SO42- and copper anode.

Which substance is most easily oxidised?

Copper, a metal, has the greatest tendency to lose electrons and

is most easily oxidised to copper (II) ions.
Hence at the anode, Cu electrode dissolves.

Eqn at anode: Cu (s) Cu2+ (aq) + 2e-

Hence anode loses weight and becomes smaller/thinner.
Electrolysis of aqueous copper(II) sulfate using copper
electrodes

What happens at the cathode?

Substances at cathode: H+, Cu2+, Copper cathode
Which substance is most easily reduced?
Copper(II) ions which are below hydrogen in the electrochemical
series has the greatest tendency to gain electrons.

At the cathode, brown/pink copper is deposited:

Eqn at cathode: Cu2+ (aq) + 2e- Cu (s)

Hence cathode gains weight and becomes thicker.

The concentration of the electrolyte, copper(II) sulfate,

remains unchanged.
What happens to the concentration of copper(II) sulfate?
Why?

Cu (aq) + 2e- Cu (s)

2+
Cathode
Cu (s) Cu (aq) + 2e-
2+
Anode

The concentration of the electrolyte, copper(II) sulfate,

remains unchanged.
For every mole of copper(II) ion reduced at the cathode,
there is equal no. of mole of copper(II) ions being formed in
solution due to oxidation of copper at anode.
 pure Cu
pure Cu - + (cathode) - + Impure
Impure Cu
(cathode) Cu (anode) (anode)

aq. CuSO4 Impurities

The electrolysis of copper(II) sulfate using copper

electrodes is used to refine (purify) copper.

The impure Cu is the anode.

A piece of pure Cu is used at the cathode.

Impurities on the anode will fall off. They contain
silver and gold.
Reaction at anode:
Cu (s) Cu2+ (aq) + 2e-
Each copper atom
loses 2 electrons to form a copper(II) ion. Hence anode
slowly dissolves. It loses weight/reduces in size and
becomes thinner.
Reaction at cathode:
Cu2+ (aq) + 2e- Cu (s)
At the cathode, each copper(II) ion
gains 2 electrons to form a copper atom. Hence cathode
gains weight and becomes thicker.
Concentration of electrolyte
remains unchanged.
 Electroplating
Electroplating is the process of coating a metallic
object with another metal by electrolysis.
Electroplating is used for protection against
corrosion and for decoration.
- +
copper anode
object
at copper (II) sulfate
cathode solution

At the anode, each copper atom loses 2 electrons to form

copper(II) ions, hence copper electrode dissolves.
Cu(s) Cu2+ (aq) + 2e-

At the cathode, each copper(II) ion gains 2 electrons and is

discharged to form solid copper.
Copper metal is plated on the object.
Cu2+ (aq) + 2e- Cu (s) Video clip
The overall change is for copper to be transferred
from the anode to the object.
 Electroplating
In electroplating,

the object to plated is the cathode.

the metal used for electroplating is

made the anode.

the electrolyte is a solution of ions of

the metal.
Different types of electroplating
1. Tin plating
2. Solder plating
3. Chromium plating
4. Nickel plating
5. Silver / gold plating
Before After

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