An ionic compound or electrovalent compound is formed when metallic

atoms donate electrons and non-metallic ions accept electrons.

The word electrolysis is made up of two words “electro” which means the
flow of electrons, and “lysis” which means SEPERATING.
Electrolysis is the process by which a chemical compound in the fused state
or in aqueous solution undergoes a chemical change on the passage of
current.
During electrolysis, a chemical change is brought about by electric energy.

Electrolytic cell or voltameter is the vessel consisting of glass,

containing two electrodes and an electrolyte.
The graphite or metal rods through which electric current enters or leaves
from an electrolyte are called electrodes.
A cathode is that electrode which is connected to the negative terminal of
the battery. It has an excess of electrons.
An anode is that electrode which is connected to positive terminal of
battery. It has deficiency of electrons.

Differences between cathode and Anode

Anode Cathode

Connected to positive terminal of Connected to negative terminal of

the battery the battery

Migration of anion occurs Migration of cations occurs

Oxidation occurs Reduction occurs

Difference between Cu wire and Copper sulphate solution

Differences between metallic and electrolytic conductors

Electrolytic Conductors(copper
Metallic Conductors (Cu Wire) Sulphate sol.)
 Flow electrons from negative pole Flow of ions in solution to the
to positive pole is responsible for respective electrodes is responsible
conduction. for conduction.

Shown by aqueous solution of ionic

Shown by metals and alloys compounds

Present in both solid and liquid Present in molten or aqueous

state of metals solution of the ionic compounds

Physical process Chemical process

Electrolyte
Electrolyte refers to the compound, which in fused state or in aqueous state
conducts electric current so that chemical decomposition of the compound
takes place.
The electrolytes which allow a large amount of current to flow through them
are called strong electrolytes. The strong electrolytes in fused state are
completely dissociated and hence, their ions are free to move in any
direction.
Examples include an aqueous solution of mineral acid and caustic alkalis.
The electrolytes which allow a very small amount of current to flow through
them are called weak electrolytes. The strong electrolytes in fused state are
completely dissociated. Hence, their ions AND MOLECULES are free to
move in any direction.
Examples include aqueous solution of organic acid and bases.

Non-electrolyte
Non-electrolyte is the chemical compound which does not conduct electric
current in fused state or in aqueous solution and does not undergo any
chemical decomposition.
Examples are carbon tetrachloride, alcohol, ether, pure water, etc.
Differences between strong and weak electrolytes
 Strong electrolytes Weak electrolytes

Allows large amount of

electricity to flow through Allows small amount of electricity to flow
them through them

Good conductors Poor conductors

Undergo complete
dissociation in molten or Undergo partial dissociation in molten or
aqueous solution aqueous solution

Contain free mobile ions Contains ions and molecules

Examples are HCl, H2SO4, Examples are H2CO3, CH3COOH, HOOC

HNO3, NaOH, KOH, NaCl, COOH, NH4OH, Ca(OH)2, (NH4)2CO3,
CuSO4, etc. Pb(CH3COO)2

Ions
When a chemical compound in fused state or in aqueous solution breaks up
into electrically charged atoms or group of atoms, the charged particles are
called ions. A positively charged ion is cation. They migrate towards
cathode. A negatively charged ion is an anion. They migrate towards anode.
Ions

Differences between cation and anion

Cation Anion

Positively charged Negatively charged

Migrate to cathode Migrate to anode

Get reduced to form neutral atom Get oxidised to form neutral atom
 Examples, Na+, Al3+ Examples, Cl−, OH−

It was put forward by Avante Arrhenius, a Swedish chemist. Following are

the points given in his Theory of Electrolytic Dissociation.
Mechanism of electrolysis
• An electrolyte is a substance which in an aqueous solution breaks into
positively charged cations and negatively charged anions.
• The movement of ions within the electrolyte is responsible for the flow
of electric current.
• The degree of dissociation refers to the extent to which electrolyte
dissociates into ions.
• Cations and anions unite to form neutral ion, setting up equilibrium.
• An electrolyte is electrically neutral.
Electrolysis of water
Add a small amount of salt to water and pour this solution into a beaker.
Connect two electrical wires to the terminal of the battery as shown in the
figure. The two ends of the wires will serve as electrodes when the
insulating cladding is removed from them. Take two test tubes and fill them
with the solution of salt and water. Invert these test tubes on the electrodes
and restrict the formation of air bubbles. Switch on the power supply.

Observe the two test tubes when the electric current is passed through it.
The volume of the gas formed in one test tube is double than that of the gas
formed in the other test tube.
The gas formed at the cathode is hydrogen while the gas formed at the
anode is oxygen.
Cathode: 2H2O (l) + 2e- →H2 (g) + 2OH-(aq)
Anode: 2H2O (l) → O2 (g) + 4H+(aq) + 4e-
Characteristics of electrolysis
• On passing the electric current, cations migrate towards cathode while
the anions migrate towards the anode.
• The number of electrons accepted by an anode is equal to the number
of electrons donated by the cathode.
• The products of electrolysis are formed on the surface of the cathode
where the exchange of electrons occurs.
• The preferential discharge of ions depends upon their position in
electrochemical series and the concentration of ions.
• Neutral atoms of metals and hydrogen are liberated at the cathode.
Therefore, they are called electropositive elements.
• Neutral atoms of non-metals are liberated at the anode. Therefore, they
are called electronegative elements.
• According to Faraday's law of electrolysis, the mass of a substance
discharged at an electrode is directly proportional to the quantity of
electricity passing through the electrolyte.
• Direct current is suitable to carry out electrolysis.
• Electrolysis is a redox reaction, where reduction occurs at cathode and
oxidation occurs at anode.
Do you know solid ionic compounds do not conduct electricity while fused
ionic compound and aqueous solution do?
This happens because the electric current passes through an ionic
compound only if it has free ions for migration.
In a solid ionic compound, ions are held together by strong electrostatic
forces. Hence, the ions are not free to migrate. Therefore, solid ionic
compounds do not conduct electricity. But fused ionic compound and an
aqueous solution of a compound have free ions produced by electrolytic
dissociation of the ionic compound. These ions are free to conduct
electricity.
Example- Solid ionic lead bromide does not conduct electricity as lead ions
and bromide ions are not free to migrate. This is because they are held
together by strong electrostatic forces.
But when lead bromide is heated, ions gain kinetic energy. At one point,
ions have more kinetic energy than the electrostatic bonds holding them
and they start moving freely. Hence, the fused compound conducts
electricity.

In an aqueous solution of compounds, say lead bromide, the slight positive

charge on hydrogen atom pulls the bromine ions and slight negative charge
on oxygen atom pulls the lead ions. This weakens the electrostatic
attraction between lead and bromide ions. Thus, free ions are migrated
towards cathode and anode and thus, it conducts electricity.

Covalent compounds such as molten wax or kerosene oil do not conduct

electricity as they do not produce free ions even on heating or in solution
form. There are certain covalent compounds that form ions when dissolved
in water and thus conduct electricity.
The process of conversion of polar covalent compounds into ions in
aqueous solution is known as ionisation. For example, pure hydrogen
chloride does not contain any ion. It does not conduct electricity.
However, due to the difference in the electronegativities of H and Cl, there
exists a small charge distribution, making it a polar covalent compound.
Addition of this pure hydrogen chloride to water helps in charge separation
causing the formation of ions in the solution.

Electrochemical Series
Depending on the ease with which metals lose or gain electrons to form
ions, they are arranged in a vertical column called electrochemical series.
Electropositive series
Depending on the ease with which metals lose electrons to form ions, they
are arranged in a vertical column called electropositive series.
Metals, which ionise very easily such as potassium, are placed at the top
of electropositive series. The cations formed are not discharged easily
during electrolysis.
Metals, which do not ionise easily such as silver ion, are placed at the
bottom of electropositive series. The cations formed are discharged very
easily during electrolysis.
Electronegative series
Depending on the ease with which non-metals or group of non-metals gain
electrons to form ions, they are arranged in a vertical column called
electronegative series.
Non-metals or group of non-metals, which accept electrons very easily such
as fluorine, are placed at the top of electronegative series. The anions
formed are not discharged easily during electrolysis.
Non-metals or group of non-metals, which do not accept electrons easily
such as hydroxyl ion, are placed at the bottom of electronegative series. The
cations formed are discharged with very difficulty during electrolysis.
Selective discharge of ions
It refers to the preferential discharge of one particular cation at cathode and
one particular anion at anode when an electrolyte contains two or more
anions or cations.
Let us study the factors which influence selective discharge of ions.
1. Relative positions of cations and anions in electrochemical series
Ions which are present at lower position in the electrochemical series have
greater tendency of their discharge at respective electrode to form an
element.
For example, in an electrolyte containing silver ion and hydrogen ion, both
will migrate to cathode, but silver ions are discharged preferentially due to
its lower position in electrochemical series.
In an electrolyte containing chloride ion and hydroxyl ion, both will migrate
to cathode, but hydroxyl ions are discharged preferentially due to its lower
position in electrochemical series.
2. Concentration of ions
Higher the concentration, greater are the chances of their discharge on
respective electrodes.
3. Nature of anode
The selective discharge of anions migrating towards anode depends of the
nature of anode. The anode can be chemically inert such as iron, graphite,
etc.Active Ex- Copper,Nickel
Electrolysis of some Common Electrolytes
1. Electrolysis of lead bromide
It is carried out under following conditions:
Electrolytic cell- Silica crucible, containing fused lead bromide and graphite
electrodes, is used as it is non-reactive and a bad conductor of electricity.
Electrolyte- Molten fused lead bromide is used as solid lead bromide is a
bad conductor of electricity while molten fused lead bromide is a good
conductor of electricity.
Electrodes- Inert electrodes are used because they do not react with the
products formed. Graphite is used as cathode and anode in preference to
platinum because bromine evolved at anode can react with platinum.
Temperature- A temperature of 380ºC or above is maintained by external
heating, which is the melting point of lead bromide.

Dissociation of electrolyte
PbBr2 ↔ Pb2+ + 2Br-
Lead ions and bromide ions are formed in the process.
On passage of electric current, lead ions are attracted towards cathode
while bromide ions migrate towards anode.
At cathode
Cathode acts as electron donor. Therefore, the following reaction takes
place.
Pb2+ + 2e- → Pb
Lead metal is formed at cathode, which settles down at the base of crucible.
At anode
Anode acts as electron acceptor. Therefore, the following reaction takes
place.
Br- → Br + e-
Br + Br → Br2
Therefore, bromine vapours are formed at anode.

2. Electrolysis of acidulated water

It is carried out under the following conditions:
Electrolytic cell- Hofmann’s voltameter is used. It consists of three
interconnected glass tubes. The central tube is used for pouring acidulated
water while products are collected from side tubes.
Electrolyte − Distilled water containing 2% sulphuric acid is used.
Sulphuric acid is used because it helps in dissociation of water.
Electrodes- Inert electrodes are used because they do not react with the
products formed. Platinum strip is used as cathode and anode because the
products formed at anode do not react with platinum.
Temperature- The electrolysis is carried out at room temperature.

Dissociation of electrolyte
H2O ↔ H+ + OH-
H2SO4 ↔ 2H+ + SO42-
On passage of electric current, H+ ions are attracted towards cathode while
OH-and SO42- ions migrate towards anode.
At cathode
Cathode acts as electron donor. Therefore, the following reaction takes
place.
H+ + e- → H ] × 4
2H + 2H → 2H2
Hydrogen atoms are formed at cathode.
At anode
Anode acts as an electron acceptor. Therefore, the following reaction takes
place.
OH- → OH + e- ] × 4
4OH → 2H2O + O2 Commented [HR1]:

Hence, oxygen gas is liberated at anode.

3. Electrolysis of aqueous acidulated copper sulphate solution using

COPPER ELECTRODES
It is carried out under the following conditions:
Electrolytic cell- A glass container is used as it is a bad conductor of
electricity. It contains saturated copper sulphate solution and two copper
electrodes.
Electrolyte − Saturated aqueous copper sulphate solution acidified with
sulphuric acid is used. It is acidified to prevent hydrolysis of copper
sulphate.
Electrodes- Inert electrodes are used because they do not react with the
products formed. Copper plate or copper rod is used as cathode and anode.
Temperature- The electrolysis is carried out at room temperature.
Dissociation of electrolyte
H2O- ↔ H+ + OH-
H2SO4 ↔ 2H+ + SO42-
CuSO4 ↔ Cu2+ + SO42-
On the passage of electric current, H+ and Cu2+ ions are attracted towards
cathode while OH- and SO42- ions migrate towards anode.
At cathode
Cathode acts as electron donor. Therefore, the following reaction takes
place.
Cu2+ + 2e- → Cu
Copper metal is formed at cathode.
At anode
Anode acts as an electron acceptor. Therefore, the following reaction takes
place.
Cu – 2e- → Cu2+
The concentration of Cu2+ ions does not change. It is because the number of
ions deposited at the cathode is equal to the number of copper atoms,
which ionise at the anode.

4. Electrolysis of aqueous acidulated copper sulphate solution using

platinum anode and copper or platinum cathode
It is carried out under the following conditions:
Electrolytic cell- A glass container is used as it is a bad conductor of
electricity. It contains saturated copper sulphate solution and platinum or
copper electrodes.
Electrolyte − Saturated aqueous copper sulphate solution acidified with
sulphuric acid is used. It is acidified to prevent hydrolysis of copper
sulphate.
Electrodes- Inert electrodes are used because they do not react with the
products formed. Copper plate or copper/platinum rod is used as cathode
and platinum anode.
Temperature- The electrolysis is carried out at room temperature.
Dissociation of electrolyte
H2O ↔ H+ + OH-H2SO4 ↔ 2H+ + SO42-
CuSO4 ↔ Cu3+ + SO42-
On passage of electric current, H+ and Cu2+ ions are attracted towards
cathode while OH- and SO42- ions migrate towards anode.
At cathode
Cathode acts as electron donor. Therefore, the following reaction takes
place.
Cu 2+ + 2e- → Cu
Copper metal is formed at cathode.
At anode
Anode acts as electron acceptor. Since OH−ions are low in electrochemical
series than SO42- ions, hence they will be discharged at anode to give off
oxygen gas as shown below:
4 OH- - 4e- → 4OH
2OH + 2OH → 2H2O + O2
Note: Once the electrolysis of copper sulphate is complete, then the
electrolysis of water starts in and hydrogen gas is liberated at cathode,
while oxygen is liberated at anode. Also, in this electrolysis the blue colour
of the electrolyte fades away due to decrease in the concentration of
Cu2+ ions.
Application of Electrolysis
Electrolysis is used for the following purposes:
 • Electroplating
• Electro-refining
• Extraction of metals by electrolysis
Electroplating
The process of depositing a thin and compact layer of superior metal over
the inferior metal by the process of electrolysis is called electroplating. It
can be of many types such as silver plating and nickel plating.

It is done for the following reasons:

To prevent metallic articles from rusting
For example, articles made of iron are electroplated with nickel so as to
prevent them from rusting.
Conditions of electroplating
• Articles to be electroplated must be very clean.
• Articles to be electroplated are made cathode while the metal to be
electroplated is made anode.
• The metal to be electroplated is to be replaced periodically as it is
consumed.
• The electrolyte must be in the form of an aqueous saturated solution
and it must contain ions of metals to be electroplated.
• The electrolyte must be acidulated with some acid containing negative
ions so as to prevent hydrolysis.
• Low and direct current should be used so that the electrolyte is not
heated up.
Silver Plating
The electrolyte used is the saturated aqueous solution of sodium argento
cyanide acidified with hydrocyanic acid. A highly cleaned article is used as a
cathode while a hollow cylinder of silver surrounding cathode is used as an
anode.
Electrolyte dissociates as follows:
NaAg(CN)2 ↔ Na+ + Ag+ + 2CN-
HCN ↔ H+ + CN-
H2O ↔ H+ + OH-
At the cathode, silver ions discharge because of their low reduction
potential.
Ag+ + e- → Ag
At the anode, silver atoms discharge to form silver ions because of their low
reduction potential.
Ag - e- → Ag+
Nickel plating
The electrolyte used is the saturated aqueous solution of nickel sulphate
acidified with sulphuric acid. A highly cleaned article is used as a cathode
while a hollow cylinder of nickel surrounding cathode is used as an anode.

Electrolyte dissociates as follows:

NiSO4 ↔ Ni2+ + SO42-
H2SO4 ↔ 2H+ + SO4 2-
H2O ↔ H+ + OH-
At the cathode, nickel ions discharge because of their low reduction
potential.
Ni2+ + 2e- → Ni
At the anode, nickel atoms discharge to form nickel ions because of their
low reduction potential.
Ni – e- → Ni2+
Electro-refining
Electro-refining is the process by which impurities are removed from an
impure metal. Metals such as silver and copper are refined using electro-
refining.
Electro-refining of copper.
The electrolyte used is the saturated aqueous solution of copper sulphate
acidified with sulphuric acid. Pure copper thin sheets connected in parallel
are used as a cathode while impure copper thin sheets connected in parallel
are used as an anode.

Electrolyte dissociates as follows:

CuSO4 ↔ Cu2+ + SO42-
H2SO4 ↔ 2H+ + SO42-
H2O ↔ H+ + OH-
At the cathode, copper ions discharge because of their low reduction
potential.
Cu2+ + 2e- → Cu
At the anode, copper atoms discharge to form copper ions because of their
low reduction potential.
Cu – e- → Cu2+