ELECTROLYSIS:

Electrolysis is the decomposition of an electrolyte by passing an electric current through

it.
Definition of related terms:
1. Conductors
Are materials that allow electricity to pass through them.
Common conductors include
a) Metals- these conduct both in the solid and liquid phase (molten) and the
conducting particles are the free and mobile electrons in their structure.
b) Graphite- it is a non-metal (carbon) but with free electrons which can move
and conduct electric current.
c) Ionic compounds- these conduct only in the liquid phase (i.e. in molten state
or aqueous solution) and the conducting particles are the ions that make
up the compound.
Note: In the solid state an ionic compound does not conduct electricity
because the ions are bound together by strong electrostatic forces and not
free to move.
2. Non-conductors
Are materials that do not allow electricity to pass through them e.g. paper, wood,
plastics e.t.c. They possess neither free electrons nor ions.
3. Electrolyte
An electrolyte is a compound which when in solution or molten state conducts
electric current and is decomposed by it.

Electrolytes are ionic compounds i.e. they are composed of oppositely charged ions.
In the solid state these compounds do not conduct electricity because the ions are
held in fixed positions by strong electrostatic forces and are not free to move.
During melting, heat breaks these forces and the ions set free to move and conduct
electricity in the molten electrolyte.
Similarly, dissolving the solid in water or any polar solvent causes breakdown of the
lattice setting the ions free to conduct electricity in the aqueous solution.

Types of electrolytes:
Electrolytes are of two types namely strong and weak electrolytes
a) Strong electrolytes
A strong electrolyte is a compound which is completely ionized in dilute
solution and in molten state.
Examples of strong electrolytes include
 Salts like Sodium chloride, copper(II) sulphate
NaCl(aq) Na+(aq) + OH-(aq)

Chemistry is fun Page 1

 CuSO4(aq) Cu2+(aq) + SO42-(aq)
 Strong acids like sulphuric acid, hydrochloric acid.
H2SO4(aq) 2H+(aq) + SO42-(aq)

HCl(aq) H+(aq) + Cl-(aq)

b) Weak electrolyte
A weak electrolyte is a compound which is only partially/slightly ionized in
dilute solution and in molten state.
Few ions exist in the solution or molten substance together with unionized
molecules and this reduces its conducting capacity compared to strong
electrolytes.
Examples of weak electrolytes include:
 Weak acids like carbonic acid, ethanoic acid
H2CO3(aq) H+(aq) + HCO3-(aq)

CH3COOH(aq) H+(aq) + CH3COO-(aq)

 Weak alkalis like ammonium hydroxide

NH4OH(aq) NH4+(aq) + OH-(aq)

NOTE: Water is also considered a weak electrolyte even though its ability to conduct
a current is very small (much smaller than any ionic compound).
H2O(l) H+(l) + OH-(l) OR 2H2O(l) H3O+(l) + OH-(l)

4. Non-electrolytes
These are compounds which in solution or molten state cannot be decomposed by
an electric current. The compounds consist only of molecules and no ions or free
electrons. The molecules have no charge and are therefore not able to carry an
electric current.
Examples of non- electrolytes include:
 Sugar
 Benzene
 Alcohol
 Most organic compounds

5. Electrodes
These are two terminals of carbon (graphite) or metal at which the current (or
electrons) leaves or enters the electrolyte. They are named cathode and anode.

a) Cathode: This is the negatively charged electrode at which electrons enter

the electrolyte (or leave the external circuit).

Chemistry is fun Page 2

 b) Anode: this is the positively charged electrode at which electrons leave the
electrolyte (or enter the external circuit)

Diagram to illustrate an electrolytic cell.

External circuit

Cathode Anode

Positive ion Negative ion

Electrolyte

THE IONIC THEORY

To explain electrolysis, the ionic theory was put forward by Arrhenius in 1880. The main
ideas in this theory are that:
1. Electrolytes contain electrically (positively and negatively) charged particles
called ions.
 Positively charged ions called cations are formed from atoms of metals
and hydrogen by loss of electrons. A metallic or hydrogen atom loses a
number of electrons equal to its valency.
 Negatively charged ions called anions are formed from atoms of non-
metals by gain of electrons or from acidic radicals. The non-metallic ion
gains a number of electrons equal to its valency.
 The ions have properties different from those of the atoms from which they
are formed.
2. When an electrolyte is in the liquid phase i.e. molten or in aqueous solution, the
positive and negative ions move freely and randomly within the liquid.
Equations of ionization to show the ions produced by some common electrolytes when
molten or in aqueous solution.
Molten lead(II) bromide: PbBr(l) Pb2+(l) + 2Br-(l)
Dilute sulphuric aid: H2SO4(aq) 2H+(aq) + SO42- (aq)
Copper(II) sulphate solution: CuSO4(aq) Cu2+(aq) + SO42-(aq)
Sodium chloride solution: NaCl(aq) Na+(aq) + Cl-(aq)

Chemistry is fun Page 3

 Sodium hydroxide solution: NaOH(aq) Na+(aq) + OH-
Copper(II) chloride solution: CuCl2(aq) Cu2+(aq) + 2Cl-

3. When an electric current is applied to the electrolyte, the negatively charged ions
(anions) are attracted by and move to the positively charged electrode (anode).
Similarly the positively charged ions (cations) are attracted by and move to the
negatively charged electrode (cathode). This is known as ionic migration.
4. When the positive ions strike the cathode, they acquire from it electrons which
turn them into atoms and therefore electrically neutral. They are discharged.
5. When the negative ions come into contact with the anode, they lose electrons
and become atoms i.e. discharged.

Experiment to show movement of ions during electrolysis

 Cut apiece of filter paper approximately the size of a microscope slide and hold it
onto a microscope slide using crocodile clips.
 Moisten the filter paper by placing a drop of water on it and allowing it to spread
to cover the whole surface.
 Place a small crystal of potassium permanganate midway between the points of
attachment of the clips.
 Connect the slide and contents in a circuit with a 20V d.c. supply, observe the
paper over a period of 10-15 minutes.

20V

Crocodile clip

Filter paper Crystal of Microscope slide

potassium
permanganate

Chemistry is fun Page 4

Observation:
Purple colour moves towards the clip connected to the positive terminal (anode).

Explanation:
The electrovalent compound (KMnO4) is being “pulled apart” by the migration of the
negative, purple-coloured permanganate ions (MnO4-) towards the positive electrode
(anode). At the same time the positive ions (K+) migrate to the negative electrode
(cathode) but this is not easily seen because K+ ions are colourless.

Activity: State what could be observed if a crystal of copper(II) sulphate was used
instead of potassium permanganate.

Electrolysis of molten substances:

Electrolysis of molten lead(II) bromide using carbon(graphite) electrodes:

Bulb
Cathode
Anode

Crucible Lead(II) bromide crystals

Heat

 Arrange the set up as shown with the crucible initially containing lead(II) bromide
crystals.
 Heat until the crystals melt.
Observations:
 Initially the bulb does not light when the lead(II) bromide is still in solid form
showing that no electric current passes through it in this form.

Explain why this is so.

Chemistry is fun Page 5

  As soon as the solid melts, the bulb lights up showing that electric current is now
passing through it.
 Fumes of a brown vapour are produced at the anode while at the cathode a grey
solid is formed.
Explanation:
 The bulb lights up after melting because heat breaks the electrostatic
forces/bonds that were holding the ions in the solid. So the molten substance
contains free ions that move and conduct the current.
In molten lead(II) bromide, the ions present are: Pb2+ and 2Br -
 The Pb2+ migrated to the cathode where they gained electrons (became
discharged) forming atoms of lead (grey solid).
Reaction at cathode: Pb2+(l) + 2e Pb(s)
The bromide ions migrated to the anode where they lost electrons forming bromine
atoms
Br -(l) Br(g) + e
Br -(l) Br(g) + e
The atoms spontaneously combine in pairs to form bromine molecules
Br(g) + Br(g) Br2(g)
Overall equation of reaction at anode:
2Br -(l) Br2(g) + 2e
Note
In a molten electrolyte only one kind of positive ion and one kind of negative ion exist
and they migrate to the opposite electrodes where they each undergo discharge. In
aqueous solutions however, the electrolyte contains more than one kind of positively or
negatively charged ion e.g. in an aqueous solution of sodium chloride, the positive ions
present are Na+ ions as well as H+ ions (from the solvent i.e. water). Similarly the
negative ions in the solution are Cl- and OH- from water. When this solution is
electrolyzed, both Na+ and H+ ions migrate to the cathode but only one of these ions get
discharged. This is known as selective/preferential discharge.
SELECTIVE/PREFERENTIAL DISCHARGE OF IONS
When two or more ions of similar charge are present in a solution under similar
conditions e.g. Na+ and H+ or Cl- and OH-, one is preferentially selected for discharge.
The following factors determine the ion to be discharged:
1. Position of the ion in the Electrochemical Series (ECS)
ECS is a list of ions in order of ease of discharge.

Chemistry is fun Page 6

 The ECS for common cations and anions is shown below:

Cations Anions
K+ SO42-
Ca2+ NO3-
Na+ Cl-
Mg2+ Br-
Al3+ I-
Zn2+ OH-
Fe2+
Pb2+
H+
Cu2+
Ag+

Keeping other factors constant, an ion that is lower in the ECS will be discharged
in preference to the one above it. For example in sodium chloride solution
containing the positive ions Na+ and H+(from water), the H+ ions are discharged
in preference to Na+.
Similarly in copper(II) sulphate solution containing the negative ions SO 42- and
OH- (from water), the OH- ions are discharged in preference to SO42- ions.
Example:
During electrolysis of sodium sulphate solution:
 Sodium ions(Na+) and hydrogen ions(H+) migrate to the cathode.
Hydrogen ions, being lower in the ECS are discharged.
Equation of reaction: 2H+ (aq) + 2e H2(g)
 Sulphate ions(SO42-) and hydroxyl/hydroxide ions(OH-) migrate to the anode.
Hydroxyl ions being lower in the ECS are discharged.
Equation of reaction at anode: 4OH-(aq) 2H2O(l) + O2(g) + 4e

Activity
For each of the electrolytes given below, state the ions which will migrate to respective
electrodes during electrolysis, identify which one will be discharged and hence write
equation of the reaction that will take place there.
a) Copper(II) chloride solution
b) Sulphuric acid solution
c) Potassium iodide solution

Chemistry is fun Page 7

2. Concentration
The higher the concentration of an ion in solution, the more likely it is to get discharged.
For example during electrolysis of concentrated sodium chloride solution containing
both Cl- and OH- as negative ions, Cl- ions are discharged in preference to OH- because
of their higher concentration.
3. Nature of the electrode
Sometimes the nature of electrode may influence the choice of ion to be discharged.
Examples:
a) Electrolysis of sodium chloride solution using platinum cathode gives a different
product from its electrolysis using mercury cathode.
 With platinum cathode, H+ ions are discharged in accordance with the order of
the ECS giving hydrogen gas as the cathode product.
 If a mercury cathode is used, less energy is required to discharge Na + ions than
H+ ions. So Na+ ions are discharged forming sodium amalgam as the cathode
product.
b) Electrolysis of copper(II) sulphate solution
 Using platinum electrodes, oxygen gas is produced at the anode as expected.
 Using copper electrodes, no oxygen is produced at the anode. Instead the
copper anode becomes smaller and smaller as copper atoms lose electrons and
enter solution as ions. (see purification of copper).

Electrolysis of Aqueous solutions:

1. Electrolysis of dilute sulphuric acid using platinum electrodes:
Also known as electrolysis of water
Diagram of apparatus used:

Hydrogen (2 volumes) Oxygen (1 volume)

Cathode (platinum foil) Anode (platinum foil)

Dilute sulphuric acid

Chemistry is fun Page 8

Ions present:
From sulphuric acid: H+(aq) and SO42-(aq)
From water: H+(aq) and OH-(aq)
At the cathode:
Observation: Bubbles of a colourless gas
Explanation: Hydrogen ions migrate to the cathode, gain electrons and become
hydrogen atoms:
H+(aq) + e- H(g)
Hydrogen atoms combine in pairs to form molecules
H(g) + H(g) H2(g)
Overall reaction at cathode may be represented as
2H+(g) + 2e- H2(g)
Note: Migration of SO42- to the anode and discharge of H+ are equivalent to decrease of
concentration of sulphuric acid. So there is decrease in acidity (or increase in pH) at the
cathode.
At the anode:
Observation: Bubbles of a colourless gas.
Explanation: Both hydroxide and sulphate ions migrate to the anode. Hydroxide ion
being lower in the electrochemical series is discharged in preference to sulphate ion.
OH-(aq) OH(aq) + e-
By interaction between the OH groups, water and oxygen are produced.
OH(aq) + OH(aq) H2O(l) + O(g)
For an oxygen molecule to be formed (O(g) + O(g) O2(g) ) the above combination
has to occur twice using up 4 hydroxide ions. Thus the overall reaction at the anode is
4OH-(aq) 2H2O(l) + O2(g) + 4e-
Note: Discharge of hydroxide ions disturbs the ionic equilibrium of water causing more
water molecules to ionize to restore it. H2O(l) H+(aq) + OH-(aq).
This leads to excess hydrogen ions causing an increase in acidity (reduction in pH) at
the anode.

Chemistry is fun Page 9

Overall equation:
To write an overall equation for the entire process, we have to combine the overall
cathode equation with the overall anode equation. However the cathode reaction has to
occur twice in order to balance out the number of electrons since the electrons acquired
at the cathode must be equal to those given up at the anode. For this reason, the
cathode equation will be multiplied by 2. It is also the reason why the volume of
hydrogen gas produced at the cathode is twice the volume of oxygen gas
produced at the anode.
Cathode reaction: 2H+(g) + 2e- H2(g) x2
Anode reaction: 4OH-(aq) 2H2O(l) + O2(g) + 4e-
Overall equation: 4H+(aq) + 4OH-(aq) 2H2(g) + 2H2O(g) + O2(g)

2. Electrolysis of sodium hydroxide solution:

The electrodes are both made of platinum.

Ions present:
From Sodium hydroxide: Sodium ions (Na+) and hydroxide ions (OH-)
From water: Hydrogen ions (H+) and hydroxide ions (OH-)

At the cathode:
Observation: Bubbles of a colourless gas, alkalinity increases
Explanation: Both sodium ions and hydrogen ions migrate to the cathode but
hydrogen ion, being lower in the electrochemical series is discharged in preference
to sodium ion.
2H+(aq) + 2e- H2(g)
Alkalinity increases because removal of hydrogen ions disturbs the ionic equilibrium
of water and more water molecules ionize to restore it. This leads to accumulation of
hydroxide ions.

At anode:
Observation: Bubbles of a colourless gas, alkalinity decreases.
Explanation: Hydroxide ions migrate to the anode and get discharged producing
water and oxygen gas.
4OH-(aq) 2H2O(l) + O2(g) + 4e-
Decrease in alkalinity is due to discharge of hydroxide ions.

Note:
 The overall pH of the system remains constant
 The volume of hydrogen produced at the cathode is twice the volume
of oxygen produced at the anode.
 The process is equivalent to the electrolysis of water.
Chemistry is fun Page 10
 3. Electrolysis of concentrated sodium chloride solution/brine using carbon
(graphite) electrodes:

Ions present:
From Sodium chloride: Na+(aq) and Cl-(aq)
From water: H+(aq) and OH-(aq)

At the cathode:
Observation: bubbles of a colourless gas.
Explanation:
Sodium ion, Na+(aq) and hydrogen ion, H+(aq) both migrate to the cathode.
Hydrogen ion being much lower in the electrochemical series is discharged in
preference to sodium ion.
2H+(aq) + 2e- H2(g)

At the anode:
Observation: Bubbles of a greenish yellow gas.
Explanation:
Chloride ion and hydroxide ion both migrate to the anode. Chloride ion is discharged
because it is present in much higher concentration than hydroxide ion.
Cl-(aq) Cl(g) + e-
2Cl-(aq) Cl2(g) + 2e-

Cl(g) + Cl(g) Cl2(g)

4. Electrolysis of concentrated sodium chloride solution/brine using a mercury

cathode and carbon anode(industrial manufacture of chlorine, sodium
hydroxide and hydrogen)- the Castner-Kellner process.

Carbon anodes +ve

Chlorine
used brine brine

Sodium amalgam mercury

ve
Mercury cathode

Chemistry is fun Page 11

 At the cathode:
The cathode is a stream of mercury which flows slowly across the bottom of the cell.
Both Na+ and H+ migrate to the cathode. Na+ ions are preferentially discharged even
though sodium ion is higher than hydrogen ion in the electrochemical series.
Na+(aq) + e- Na(s)

Sodium and mercury then form sodium amalgam.

Na(s) + Hg(l) NaHg(l)

Sodium amalgam is reacted with water to form sodium hydroxide, hydrogen and
mercury.
2NaHg(l) + 2H2O(l) 2NaOH(aq) + H2(g) + 2Hg(l)

The sodium hydroxide solution is evaporated to dryness and the molten substance
solidifies to pellets. The hydrogen is collected or converted into hydrogen chloride by
burning it with chlorine.

At the anode:
The anode is made of carbon (graphite) which is not attacked by chlorine.
Both chloride ions and hydroxide ions migrate to the anode. Chloride ions are
discharged due to their higher concentration producing chlorine gas.
2Cl-(aq) Cl2(g) + 2e-

The chlorine is dried, liquefied and stored.

5. Electrolysis of copper(II) sulphate solution using platinum electrodes:

Ions present:
From copper(II) sulphate: Cu2+(aq) and SO42-(aq)
From water: H+(aq) and OH-(aq)
At the cathode:
Observation: A brown solid is deposited.
Explanation: Both Cu2+ and H+ migrate to the cathode.
Cu2+ being lower in the electrochemical series is discharged in preference to H+
Cu2+(aq) + 2e- Cu(s)

At the anode:
Observation: Bubbles of a colourless gas.
Explanation: Both SO42-(aq) and OH-(aq) migrate to the anode.
OH- being lower in the reactivity series is discharged in preference to SO 42-
producing water and oxygen gas.
4OH-(aq) 2H2O(l) + O2(g) + 4e-

Chemistry is fun Page 12

6. Electrolysis of copper(II) sulphate solution using copper anode:

Ions present:
From copper(II) sulphate: Cu2+(aq) and SO42-(aq)
From water: H+(aq) and OH-(aq)

At the cathode:
Observation: The cathode becomes bigger in size/ a brown solid is deposited.
Explanation: Both Cu2+ and H+ migrate to the cathode.
Cu2+ being lower in the electrochemical series is discharged in preference to H+
Cu2+(aq) + 2e- Cu(s)

At the anode:
Observation: The anode decreases in size.
Explanation: Both SO42-(aq) and OH-(aq) migrate to the anode but none of them is
discharged. Instead the copper anode gradually dissolves as copper atoms are
converted to copper(II) ions by loss of electrons. The ions pass into solution.

Cu(s) Cu2+(aq) + 2e-

Note: The total concentration of the solution remains the same as the essential
change is the transfer of copper from the anode to the cathode.
This process is used in purification/refining of copper.

APPLICATIONS OF ELECTROLYSIS:
1. Extraction of metals e.g. sodium (refer to metal extraction notes)
2. Manufacture of important chemicals like sodium hydroxide, chlorine, hydrogen etc.
3. Purification/ refining of copper
4. Electroplating:
This is the coating of a metal with another metal or alloy usually to improve
appearance or prevent corrosion.
The metal to be coated is made the cathode while the coating metal is the anode
both of which are dipped in a solution (electrolyte) containing ions of the coating
metal.

For example
To silver plate a steel fork, the fork is connected to the negative terminal of a d.c.
supply and dipped in a solution of silver nitrate (cathode). A silver plate/rod is
connected to the positive terminal and dipped in the same solution (anode).

Chemistry is fun Page 13

 Illustration:

When the current is switched on, silver ions in the solution are attracted to the fork
where they gain electrons and form a layer of silver atoms on the surface of the fork.
At the same time silver atoms from the rod lose electrons forming silver ions which
pass into the solution.

ELECTROCHEMICAL CELLS.
(Up next, read ahead)

Chemistry is fun Page 14