ELECTROLYSIS

ELECTROLYSIS:
It is the process of decomposition of a chemical compound in molten or aqueous state by
using Direct Current.

ELECTROLYTE:
Compounds which either in molten or aqueous state allow electricity to pass through
them.
On the basis of their conductivity and their ability to dissociate, they are grouped as :
 Strong Electrolyte
 Weak Electrolyte
 Non- Electrolyte

STRONG ELECTROLYTE WEAK ELECTROLYTE

They allow large amount of electricity They allow small amount of electricity to
to flow through them flow through them

These are good conductors of electricity These are poor conductors of electricity

These are completely dissociated in These are partially dissociated in fused or

fused or aqueous state and contains aqueous state and may contain ions as
free mobile ions ONLY well as molecules

Eg: Eg:
ACIDS: dil HCl, HNO3, H2SO4 , HBr, HI ACIDS: Carbonic, Acetic, Oxalic, Formic
BASES: NaOH, KOH, LiOH BASES: NH4OH, Ca(OH)2, Mg(OH)2
SALTS: NaCl, KCl, Na2SO4, NaNO3, SALTS: Na2CO3, NaHCO3, Lead Acetate
CuCl2, PbSO4, Pb(NO3)2, PbBr2

NON ELECTROLYTE:

 It is a compound which neither in fused or aqueous state allows an electric current

to pass through it.
 They do not have ions but consists of molecules ONLY.
 They are mostly co-valent compounds.
 Eg:
Pure Water, Distilled Water, Kerosene, CCl4, Glucose, Cane Sugar, Benzene, Urea,
Alcohol, Ether, Carbon disulphide, Petroleum products

ION:

 The atoms or groups of atoms which carry a charge is an ion.

 Depending on the charge the ions carry, they are classified as:
 CATIONS ANIONS

These are positively charged ions These are negatively charged ions
which migrate towards CATHODE which migrates towards ANODE
during electrolysis during electrolysis

They gain electrons and further They lose electrons and further
gets reduced to further become a gets oxidised to become a neutral
neutral atom atom

ELECTRODES

 These are a pair which contains two metal plates or wires or graphite rods or gas
carbon rods immersed in the electrolyte which allows the electric current to enter
or leave the electrolytic cell
 The electrodes are connected to a battery and depending to the terminal/end of
the battery to which it is connected , they are classified as:
1. Cathode
2. Anode

CATHODE ANODE

It is the electrode which is It is the electrode that is

connected to the negative terminal connected to the positive
of the battery terminal of the battery

Cations migrate towards Cathode Anions migrate towards Anode

It is called Reducing Electrode as It is called Oxidising Electrode as

Reduction takes place over here Oxidation takes place over here

They accept excess electrons from They donate excess electrons to

Anions and converts them into Cation and converts them into
neutral atom neutral atom

Reduction = Gain of electron by an Oxidation = Loss of electron from

atom or ion an atom or ion

Eg; Eg;
+ -
Na + 1 electron Na Atom Cl - 1 electron Cl Atom
(Neutral) (Neutral)
 EXAMPLES OF ELECTROLYSIS

1. Molten Lead Bromide

a) Electrolytic Cell : Silica Crucible

b) Electrolyte: Molten Lead Bromide
c) Electrodes: Cathode = Graphite/Iron; Anode = Graphite
d) Temperature: Above 380 ° C
e) Current: 3 Amperes
f) Dissociation:

PbBr2 Pb2+ + 2 Br-

g) Reaction at cathode: Lead (Pb2+) ions migrates towards Cathode, gains 2 electrons
and forms a Silvery grey metal of lead at the cathode which settles down at the
base of the crucible as it is heavier.

Pb2+ + 2 electrons Pb (Silvery Grey Metal)

h) Reaction at Anode: Bromide (Br- )ions migrate towards Anode, loses 1 electron and
forms a Bromine Atom, which in turn is released as bromine gas at Anode
indicated by Reddish brown vapours.

Br- - 1 electron Br

Br + Br Br2

Give Reasons:

 Silica Crucible is used as an electrolytic Cell –

o Is non-reactive
o Can withstand high temperatures
o Nearly a bad conductor of electricity
 Solid Lead Bromide is not used as an electrolyte – As there are strong electrostatic
forces of attraction between Lead ion and Bromide ion

 Molten Lead Bromide is used as an electrolyte – As it contains free mobile ions due
to the high temperature of 380°C, thereby causing the strong electrostatic forces to
weaken and thus making it a good conductor of electricity

 Inert electrodes are used– so that they do not react with the products formed
during electrolysis

 Graphite Anode is preferred over Platinum Anode– The Bromine gas evolved at
anode reacts with platinum and does not react with graphite

 Temperature of about 380° C and above are used– as it is the m.p of Lead Bromide
2. Aqueous Copper Sulphate (Using Copper Electrodes)

a) Electrolytic Cell : Glass container

b) Electrolyte: Copper Sulphate solution acidified with Sulphuric Acid
c) Electrodes: ACTIVE i.e., Cathode = Copper ; Anode = Copper
d) Temperature: Room Temperature
e) Current: 3 Amperes
f) Dissociation:

CuSO4 Cu2+ + SO4-2

H2O H+ + OH-

H2SO4 2 H+ + SO4-

g) Reaction at cathode: Copper ion and Hydrogen ion migrates towards Cathode, but
only Copper ion is discharged as it is placed lower than Hydrogen ion in the
electro chemical series and it accepts electrons and forms a neutral Copper Metal
Atom

Cu2+ + 2 electrons Cu (Pink or Reddish brown)

h) Reaction at Anode: Although the anions migrate towards the Anode, they are not
deposited there as the Active electrode (i.e., Copper Anode) influences the process.
The Copper Anode being active participates itself by releasing Cu2+ ions and gets
reduced in size.

Cu - 2 electrons Cu2+

These Copper ions released by the Anode falls back into the electrolytic solution
and replaces the lost Cu2+ ions which had prior migrated towards the Cathode.

In this manner the blue colour of the Aqueous Copper Sulphate Solution remains
unchanged during the Electrolysis

Give Reasons

 Glass is used as an electrolytic Cell – It is a bad conductor of electricity

 Electrolyte is acidified with traces of Sulphuric Acid –

o It enhances the conductivity of electrolyte
o Prevents hydrolysis of electrolyte

 Cu2+ ion is discharged at Cathode although H+ also migrates towards it – It is

placed lower than H+ in electrochemical series
  The blue colour of Aqueous Copper Sulphate solution remains unchanged – The
Cu2+ ion released by the active Anode replaces the lost Cu2+ ion that has migrated
to Cathode and is discharged over there.

 H+ , SO42- and OH- ions are known as spectator ions – As they do not participate in
the electrolytic reaction

3. Acidulated Water [ Dilute Sulphuric Acid]

a) Electrolytic Cell : Hofmann’s Voltameter

b) Electrolyte: Distilled Water containing 2% Sulphuric Acid
c) Electrodes: INERT i.e., Cathode= Platinum; Anode= Platinum
d) Temperature: Room Temperature
e) Current: 3 Amperes
f) Dissociation:

H2O H+ + OH-

H2SO4 2 H+ + SO4-

g) Reaction at cathode: Hydrogen ions migrates towards Cathode, and being the only
positive ion it accepts an electron and gets reduced to form a neutral Hydrogen
atom.

H+ + 1 electron H

Two Hydrogen atoms unite to form a Hydrogen molecule and is liberated a

Hydrogen gas at Cathode

H+H H2

h) Reaction at Anode: Both SO42- ions as well as OH- ions migrates towards Anode
but only OH– ions are discharged as it is placed below than SO42- ion in the
electrochemical series, loses an electron and forms a neutral OH Radical.

OH- – 1 electron OH

The neutral OH Radical unites with another OH Radical to form water molecule
and Oxygen gas . The Oxygen gas is therefore released at Anode.

OH + OH H2 O + O

O+O O2

Give Reasons
 Dilute Nitric Acid is not used in the preparation of acidified water as the electrolyte
– It is volatile and the NO3- radical interferes with the electrolytic reaction

 Pure water is not used as an electrolyte – As it is a non-electrolyte which neither in

its aqueous nor fused state can conduct electricity

 Acidifed Water (Addition of traces of Sulphuric acid to Distilled Water ) acts as an

electrolyte – Pure water is a non-electrolyte but when Sulphuric acid is added to it,
it catalyses the ionisation to yield H+ and OH- ions

 Inert electrodes are used – So that they do not react with the products formed
during electrolysis

 OH– ions are discharged at Anode – As they are placed lower in the electrochemical
series
 APPLICATIONS OF ELECTROLYSIS

A. ELECTROPLATING

It is the electrolytic process of deposition of a superior metal (Eg: Ni, Ag, Au, Cr) on the
surface of a baser metal or article (Eg; Fe, Cu, etc)

Reasons:
 To prevent corrosion or rusting of the base metal
 To make the article attractive by improving its appearance

Conditions for Electroplating:

1. Article to be electroplated must be very clean – Because the impurities (oil,
grease, oxides, etc) will not allow a firm deposit on the surface of the metal

2. Article to be plated is always placed at the Cathode – During electrolytic

reaction, metal is always deposited at the cathode as reduction takes place over
there

3. The metal to be plated on the article is always made at the anode and has to
be periodically replaced
 During electrolysis the anode ionises to form positively charged ions which
enter the electrolyte
 As Anode is used in the reaction, it has to be periodically replaced

4. Electrolyte must contain ions of metal which is to be plated on the article –

During electrolysis, the desired metal ions migrate towards Cathode and gets
discharged there to form a thin film of metal on the article i.e., already placed
at/as cathode

5. Low current for a longer time should be used

 Higher current leads to uneven deposition of the metal
 Longer time initiates thicker and uniform deposition

6. Direct current should be used and not A.C – A.C current causes ionisation to
take place at alternate electrodes and no effective coating of article is achieved
NOTE: LEARN SELECTIVE DISCHARGE THEORY AND ELECTROCHEMICAL SERIES
FROM YOUR TEXT BOOK.