ELECTROLYSIS

Electrolyte
Definition
Chemical compound which conducts
electricity in the fused or aqueous
solution state and undergo chemical
decomposition due to the flow of
current through it.
 Non-electrolyte
Definition
Chemical compound which do
not conducts electricity in the
fused or aqueous solution state
and do not undergo chemical
decomposition due to the flow of
current through it.
Property
Electrolyte Non-electrolyte
Definition
Chemical compound Chemical compound
which conducts which do not
electricity in the conducts electricity
fused or aqueous in the fused or
solution state and aqueous solution
undergo chemical state and do not
decomposition due undergo chemical
to the flow of decomposition due
current through it. to the flow of
current through it.
Property
Electrolyte Non-electrolyte
Type Of
Particle
 Ions only – strong Molecules only
Present In
Electrolyte
electrolyte
 Ions and molecules
– weak electrolyte
Type Of
Compounds Ionic compounds and Covalent compounds
polar covalent (non-polar)
compounds
Examples
 Dilute acids Distilled water,
 Alkalis alcohol, carbon
 Ionic salts tetrachloride, sugar
 Property Strong electrolyte Weak electrolyte
Dissociation
They almost They partially
completely dissociate in
dissociate in fused or fused or aqueous
aqueous solution solution state
state
Type of
particles
(Almost) Contain ions as
present only free mobile ions well as molecules

Conductivity
Good conductor of Poor conductors
electricity of electricity
 Property Strong electrolyte Weak electrolyte
Amount of
Allow a large amount of Allow a small amount
electricity
electricity to flow through of electricity to flow
them through them
Bulb
Allows a bulb to glow Allows a bulb to glow
attached
brightly dimly
Example
 Strong acids-  Weak acids
Hydrochloric Acid Carbonic acid
Sulphuric Acid Acetic acid
Nitric Acid
 Weak alkali
 Strong alkali Ammonium hydroxide
Sodium hydroxide
Potassium hydroxide
 Salts of weak acids
Sodium acetate
 Salts of strong acids
sodium chloride
potassium nitrate
 Electrolytic dissociation Ionization
Definition
Electrolytic Ionization involves
dissociation is a formation of charged
process which ions form the
involves separations molecules which are
of ions which are not in ionic state.
already present in an
ionic compound
Type of
compounds Takes place in ionic Takes place in
compound covalent compound
 Electrolytic dissociation Ionization
Examples
2+ - +
PbBr2 Pb + 2Br H2SO4 2H +SO4 2-
2+ +
CuSO4 Cu + SO4 H2O H + OH
2- -
2+
NiSO4 Ni + SO4 2-
1+
NaCl Na +Cl -
 Electrolysis
Definition
Electrolysis is the decomposition of
a chemical compound (electrolyte)
in aqueous or fused state by the
passage of a direct electric current
resulting in discharge of ions as
neutral atoms at the respective
electrode.
 Electrodes
Two metal plates or wires or
graphite rods or gas carbon rods
immersed in the electrolyte through
which the current enters and leaves
the electrolytic cell.
THE ELECTRODES…. WHICH IS
WHICH? HOW TO REMEMBER:
Anode ADD = + i.e. positive
The anode (positive) hence cathode (negative)
Anion (negative) goes to Anode
Cation (positive) goes to Cathode
A to A and C to C

Note: When the current is turned on, the cathode

becomes the negative electrode by which electrons enter
the electrolyte and the anode becomes the positive
electrode by which electrons leave the electrolyte.
 ANDOE CATHODE
It is the electrode It is the electrode
connected to the positive connected to the negative
terminal (end) of the terminal (end) of the
battery. battery.
This electrode acquires a This electrode acquires a
positive charge during negative charge during
electrolysis and hence electrolysis and hence
anions (negatively cations (positively
charged ions) migrate to charged ions) migrate to
the anode. the cathode.
 ANODE CATHODE
It is an Oxidising It is the Reducing
electrode by which electrode by which
electrons leave the electrons enter the
electrolyte. Reduction
electrolyte. Oxidation takes
takes place at the cathode.
place at the anode. The The cations gain excess
anions donate excess electrons from the cathode
electrons to the anode and and are reduced to neutral
are oxidised to neutral atoms.
atoms.
 Cation Anion
They are positively charged They are negatively charged
ions. ions.
They migrate to cathode They migrate to the anode
during electrolysis and are during electrolysis and are
discharged at it. discharged at it.
They accept or gain They donate or lose
electrons from the cathode electrons to the anode
(reduction) and get reduced (oxidation) and get oxidized
to neutral atoms. to neutral atoms.
 1)

2)

3)

4)

5)

6)

7)
 Selective Discharge of Ions

When two or more ions of the same charge

are present in a solution of an electrolyte,
under identical conditions and are
competing for discharge at the same
electrode, one of them get preferentially
discharged. The Preferential Discharge of
Ions present in an electrolyte at the
respective electrodes is also known as –
Selective Discharge of Ions.
Metals which ionize most readily- are present
at the top of the series.
Cations formed (easily)- are discharged at
cathode- with most difficulty.
Metals which ionize least readily- are present at
the lower end of the series.
Cations formed (with difficulty) – are
discharged at cathode most readily.
Lower the position of an anion in the series,
more easily it gets discharged at the anode.
Higher the position of an anion in the series,
more difficult for it to lose electrons or get
oxidized.
Lower the position of the ion- forming
element in the electrochemical series, greater- the
tendency to be liberated – at the respective electrode.

Cu2+ and H+ migrate to Cathode- Cu2+ ions

discharged at Cathode.

Ag+ and H+ migrate to Cathode- Ag+ ions discharged

at Cathode.

SO42- and OH- migrate to anode- OH- ions discharged

at Anode.
Reaction -
at anode: Br - 1e
-
Br



Br + Br Br2



Reaction 2+ -
at
Cathode:
Pb + 2e Pb 


Product
at anode: Bromine
vapours
Product
at
cathode: Lead metals
Observations:
i) Reddish brown fumes
evolved at anode

ii) Grey metal deposited

on cathode
 Question Key points
1) Electrolysis of molten lead At anode oxidation –bromide ion lose electrons
bromide is considered a At cathode reduction – lead ion gains electrons
redox reaction.

2) Lead bromide is a non-  Fused state or molten state – free/mobile ions are
electrolyte in the solid state present
but is electrolyte in molten  Solid state – strong electrostatic force of
state. attraction, ions are not free/mobile

3) During electrolysis of Graphite is unaffected by the reactive bromine

molten lead bromide vapours.
graphite anode is preferred
to other electrodes.

4) Crucible made of silica is Silica crucible is:

used for the electrolysis of - non-reactive,
molten lead bromide - withstands high temperature required for melting
lead bromide,
- non-conductor of electricity
Reaction at - -
anode: OH - 1e  OH x 4
4OH  2H2O + O2
Reaction at + -
Cathode: H + 1e H x 4



2H + 2H 2H2



Product at
anode: Oxygen gas
Product at
cathode: Hydrogen gas
 Question Key points
1) Electrolysis of water is carried out Pure water is non-conductor of electricity
on water acidified with dilute Addition of acid – produces free ion
sulphuric acid/ Why is the water
acidulated?

2) In the electrolysis of acidified Nitric acid – volatile acid , decomposes to

water Dilute sulphuric acid is produce nitrate ions which may interfere
preferred to dilute nitric acid for the electrolytic reaction
acidification.

3) Why is sulphate ion not discharged Sulphate ions are above hydroxyl ions in
at anode during the electrolysis of electrochemical series.
dilute sulphuric acid?
4) Why is the electrolysis of Total concentration of sulphuric acid
acidulated water considered an remains same at the end of electrolysis
example of catalysis?
Reaction
at anode:
OH - 1e  OH
- -
x4
4OH  2H2O + O2
2+ -
Reaction
at
Cu + 2e  Cu
Cathode:
Product
at anode:
Oxygen gas
Product
at
Copper metal
cathode:
Observations:
i) Brownish pink metal
deposited at cathode./ size
of cathode increases
ii)Blue colour of electrolyte
-Copper sulphate solution
fades.
Reasons :

Question Key points

The blue colour Copper ions from

of aqueous electrolyte migrate
copper sulphate towards cathode so
fades when it is number of copper
electrolyzed ions decreases in
using platinum electrolytic solution
electrode
Reaction - 2+
at anode: Cu - 2e Cu

Reaction 2+ -
at Cu + 2e Cu 

Cathode:
Product at
anode: Nil
Product
at Copper metal
cathode:
Observations:
i) Brownish pink metal deposited at
cathode.
ii)The blue colour of aqueous
copper sulphate solution remains
unchanged.
iii) Size of anode decreases and size
of cathode increases
Reasons :
Question Key points
Anode diminishes in Anode gives Cu 2+ ions
size
The blue colour of For every copper ions
aqueous copper discharged at the cathode as
sulphate solution neutral copper atom, a copper
remains unchanged ion is added to the solution at
the anode. Therefore total
number of copper ions
remains same.
 Electroplating
Electroplating is the
electrolytic process of
deposition of a superior metal
on the surface of baser metal
or article.
Conditions – For Electroplating
 The article to be electroplated is always
placed at the Cathode.
 The metal to be plated on the article is
always made the Anode.
 The electrolyte must contain – ions of the
metal used for plating on the article.
 A low current and for a longer time should
be used.
 A direct current and not A.C should be
used.
Reaction - 1+
Ag - 1e 
 Ag
at
anode:
Reaction 1+ -
Ag + 1e 
 Ag
at
Cathode:
Product at Nil
anode:
Product at Silver metal
cathode:
deposited on the
article
Reaction 2+
Ni - 2e- 
 Ni
at anode:
Reaction 2+
Ni + 2e- 
 Ni
at
Cathode:
Product at Nil
anode:
Product at Nickel metal
cathode:
deposited on the
article
Question Key points
Article to be electroplatedCathode is negative
is always placed at the electrode so metal is
cathode always deposited at the
cathode
The metal to be plated on Anode continuously
the article is always made gives out metal ion in
the anode./ The anode the solution which
must be made of the migrate towards
metal with which the cathode
article has to be plated.
Question Key points
Low current Thickness of coating depends on
for a longer the time for which the current is
time should be passed.
used Higher current causes uneven
deposition .
Low current for longer time gives
smooth, firm , uniform and long
lasting coating
Direct current Alternate current causes discharge
should be used and ionization to alternate at the
for cathode and thus giving no
electroplating effective coating.
Question Key points

In the electroplating of an silver nitrate solution. -

article with silver, the Deposition go silver is rapid
electrolyte sodium and uneven
argento-cyanide solution sodium argento-cyanide
is preferred over silver solution- Deposition go silver
nitrate solution./ A is slow so smooth, firm ,
solution of silver nitrate is uniform and long lasting
a good electrolyte but it is coating formed
not used for electroplating
an article with silver.
Why are articles Prevent corrosion
electroplated? Make it attractive