Unit-II Electrochemistry Part-A

It is the branch of chemsitry which deal with the study of chemical and electrical
energy and their interconversion.
OR
The branch of chemistry which deals with the study of the conversion of
chemical energy into electrical energy or vice versa and their mutual relationship
is called electrochemistry.
• Chemical energy into Electrical energy
• Electrical energy into Chemical energy

Galvanic cell: It is an electrical device which is used to convert chemical energy

into electrical energy.
Electrolytic cell: It is an electrical device which is used to convert electrical
energy into chemical energy.
Conductance (G): Conductance (also known as electrical conductance) is
defined as the potential for a substance to conduct electricity.
OR
It is the reciprocal of resistance.
G = 1/R
Conductance is expressed as G and the measuring unit “mho” or ohm-1. Later
after a few years, researchers replaced the unit with “Siemens” which was
denoted by the letter S.
The conductance depends on
(i) the nature and structure of the metal
(ii) Nature of electrolyte
(iii) the number of valence electrons per atom
(iv) number of ions
(v) temperature (it decreases with increase of temperature).
Resistance:
Resistance (R) is defined as the property of the conductor which opposes the
flow of electric current. It is also defined as the ratio of the voltage applied to
the electric current flowing through it.
The resistance of a conductor depends on the length, area of cross-section, and
the nature of the material that is used in the manufacturing of the conductor.
For a conductor, the resistance is directly proportional to the length of the
conductor and inversely proportional to the area of cross-section.
Resistivity (ρ):
Resistivity is defined as the resistance offered by the material per unit length for
unit cross-section. The SI unit of resistivity is Ohm.meter. Resistivity increases
linearly with temperature.
For a conductor, the resistance is directly proportional to the length of the
conductor and inversely proportional to the area of cross-section.
R αl
R α 1/A
R α l/A
R = ρ l/A
Resistance = Resistivity x (length/area)
Cell constant = length/area

Resistance = Resistivity x Cell constant

Where
R = Resistance
A = Area of cross section
l = length
ρ = Resistivity or Specific resistance
ρ = RA/l
Conductivity (k): It is the reciprocal of resistivity.

k = 1/ ρ
 k = 1/R x l/A
Conductivity = conductance x cell constant

Factors that affect the conductivity of electrolytes

The conductivity of an electrolyte is therefore affected by the following factors:
• Concentration of ions in solution. The higher the concentration of ions in
solution, the higher its conductivity will be.
• Nature of electrolyte : The conductivity of an electrolyte depends upon
the number of ions present in the solution. Therefore, the greater the
number of ions in the solution the greater is the conductance.
• Temperature : The conductivity of an electrolyte depends upon the
temperature. With increase in temperature, the conductivity of an
electrolyte increases.
Question: Why does the conductivity of a solution decrease with dilution?
Ans: The conductivity of a solution is linked with the number of ions present per
unit volume. With dilution, these decrease and the corresponding conductivity
or specific conductance of the solution decreases.
Note: Conductivity always decreases with decrease in concentration, for both
weak and strong electrolytes. This is because the number of ions per unit volume
that carry the current in a solution decreases on dilution.
Question: The electrical resistance of a column of 0.05 mol L –1 NaOH solution
of diameter 1 cm and length 50 cm is 5.55 × 103 ohm. Calculate its
conductance, cell contant, resistivity and conductivity.
Sol: Conc. of NaOH = 0.05 mol L–1
d = 1 cm or r = ½ = 0.5 cm
A=πr2
A= 3.14 × (0.5)2 cm2 = 0.785 cm2 = 0.785 × 10-4 m2 (1cm= 10-2)
l = 50 cm = 0.5 m
R = 5.55 × 103 ohm
Conductance = 1/R = 1/5.55 × 103 =………ohm-1
Cell constant= l/A =0.5/0.785 × 10-4 =……………m-1
Resistivity (ρ) = RA/l
Resistivity= 5.55 × 103 x 0.785 × 10-4/0.5
Resistivity =……………..ohm-m
Conductivity(k) = 1/ ρ =……….ohm-1.m-1

Metallic Conduction:
• It is due to the flow of electrons.
• It involves no chemical change.
• There is no transfer of matter.
• Conductance decrease with increase temp.
Electrolytic Conduction:
• It is due to the flow of ions.
• It involves chemical change.
• It involves transfer of matter.
• Conductance increase with increase temp.

Arrhenius Theory of Ionisation:

Arrhenius proposed the theory of electrolytic ionization or dissociation, which is
known as Arrhenius theory of ionization.
The main points of Arrhenius theory are the followings:
1. Molecules of acids, bases and salts (electrolyte) when dissolved in water
dissociate into positively and negatively charged particles called ions.
The molecule of sodium chloride in solution is ionised as shown below:
NaCl ⇌ Na+ + Cl–
Cation Anion
2. The cations and anions carry equal but opposite electric charges.
H2SO4 ⇌ 2H+ + SO −4 2
3. Ions are electrically charged atoms or radicals.
4. Ionisation is a reversible process. Ions constantly attract each other and
form neutral molecules.
NaCl ⇌ Na+ + Cl–
Cation Anion
 5. The physical and chemical properties of the electrolytes depend upon the
nature and concentration of the ions they give rise to.
6. The electrical conductivity of an electrolyte depends upon the number of
ions present in the solution. The electrical conductivity increases as
ionisation increases.
7. The degree of ionisation of different electrolytes is different.

Degree of ionisation depends upon the following factors.

(i) Dilution Ionisation usually increases with dilution, and at a particular
dilution, equilibrium is attained when the rate of ionisation is equal
to the rate of formation of the neutral molecules.
(ii) Nature of the electrolyte. Some electrolytes are ionised to a great
extent. Such substances are known as strong electrolytes. For
example, hydrochloric acid, sulphuric and nitric acid, sodium
hydroxide, potassium hydroxide are strong electrolytes. But some
substances are ionised feebly. For example, acetic and carbonic acid,
aluminium hydroxide etc. These are known as weak electrolytes.
(iii) Temperature of solution. The ionisation of an electrolyte increases
with the rise of temperature.
(iv) Presence of other ions in the solution.

Electrolysis:
The process of chemical decomposition of the electrolyte by the passage
of electricity through its melt or aqueous solution is called electrolysis.

Mechanism of electrolysis:
 The process of electrolysis can be explained on the basis of theory of
ionisation. According to this theory, when an electrolyte (acid, base or salt) is
dissolve in a water, it splits up into two charged particles i.e. cations and anion.
These ions randomly move about in aqueous solution. When electricity is passed
in the solution, the +vely charged ion (cation) are attracted to the –vely charged
charged electrode (cathode) and the –vely charged ions (anions) to the +vely
charged electrode (anode).This movement of ionic charges through the liquid
brought by the application of electricity is called electrolytic conduction.
On reaching the respective electrode the ions lose their charge and form neutral
species. Cation accept electron from cathode whereas anion give electron to
anode. Therefore, oxdn occurs at the anode while reduction occurs at the
cathode.

eg. Electrolysis of molten NaCl.

Mechanism of electrolysis:
When molten NaCl is electrolysed by passing D.C current through two graphite
electrodes, sodium gets deposited at cathode and chlorine gas is released at
anode.
NaCl ⇌ Na+ + Cl–
Cation Anion
+
On passing electricity Na ions move towards cathode. On reaching the cathode
each Na+ ion picks upon electron and becomes a neutral atom. This sodium
metal is liberated at cathode.
at cathode,
Na+ + e– → Na

at anode,
Cl– → Cl + e-
2Cl- → Cl2 + 2e-

Faradays laws of electrolysis:

First law:
The amount of a substance deposited or liberated at an electrode is directly
proportional to the amount of electricity passed through the electrolyte
Solution.
mαQ (Q = it)
m α it
m = Zit
 Where m = amount of substance deposited or liberated
Q = amount of electricity
i = current (amp)
t = time (second)
Z = electrochemical equivalent

Electrochemical equivalent (Z):

It is defined as the amount of the substance deposited or liberated by passing
one mole coulomb of electricity through the electrolytic solution.
Q. A current of 0.5 amp is passed through a solution of silver nitrate for 30
minutes to ppt 1.006 gm of Ag. Calculate the electrochemical equivalent of Ag.
Sol. m = Zit m = 1.006 gm
m
Z= i = 0.5 amp
it
t= 30 mints
t= 30 x 60 Sec.
1.006
Z=
0.5  30  60

Z = 0.001118
Q. A current of 0.5 amp is passed through a solution of silver nitrate for 20
minutes to ppt 1.006 gm of Ag. Calculate the electrochemical equivalent weight
of Ag.
Sol.
Q. A current of 1.0 amp is passed through a solution of Zinc sulphate for 20
minutes to ppt 1.008 gm of Zn. Calculate the electrochemical equivalent of Zn.
Sol.

Second law of Faraday’s:

When same amount of electricity is passed through different electrolytes then
the masses of the substances liberated at the electrode are in the ratio of their
chemical equivalent masses.
Let m1 & m2 be the amount of elements A & B, E1, E2 be their chemical equivalent
respectively, According to 2nd law of faraday:
 mαE , m= KE or m/E=K or
m/E= contant
m1 m 2
=
E1 E 2
m1 E1
= →①
m2 E2
But, according to Ist law,
m=zit
m1 = Z1 it
m2 = Z2 it

Z1 & Z2 are electrochemical equivalent

The value of m1,m2 put in equation (1)
m1 Z1it
Thus, =
m2 Z2it
m1 Z1
=
m 2 Z2
From equation ①
Zi E1
= →②
Z2 E 2
It is clear from equation ②
ZαE