ELECTROCHEMISTRY

Electrolysis:
It is the process of decomposition of an electrolyte
by the passage of electricity through its aqueous solution or
molten state.

Faraday’s first law of electrolysis:

In a chemical reaction, the
amount of any substance deposited or liberated is directly
proportional to the quantity of electricity passed through it.
W∝Q
W = ZQ
W = Zit ( Q= I*t )
Where, Z = Electrochemical Equivalent.
Z = atomic weight/nF (n = no. of electron, F =
96500 )

Faraday’s second law of electrolysis:

When the same quantity of
electricity is passed through the different electrolytes
connected in series. The weights of the substance produced at
the electrodes are directly proportional to their equivalent
weights.
 Ex: AgNO2 and CuSO4 solution connected in series,

Conductance of electrolytic solution:-

Electrolytes conducts electricity by decomposition.

Electrical resistance:-

If voltage v is applied to the ends of the conductor

and current “I” floe through it, then the resistance “R” of the
conductor is V/I (ohm).
Electrical conductance:-

The reciprocal of electrical resistance is called conductance. And is represented

by G sign

Thus, G = 1/R [unit of G = mho]

Specific resistance or Resistivity:- it is observed that,

There  is constant and called as resistivity.

Specific conductance or conductivity:-

The reciprocal of resistivity is known

as conductivity. And is denoted by k (kappa).
Equivalent conductivity:-

Equivalent conductivity of a solution at a dilution v

is defined as the conductance of all the ions produced from one
gram equivalent of the electrolyte dissolved in v cm3 of the
solution when the distance between the electrode is one cm
and the area of the electrode is so large then whole the
solution is come between them.

Where, c is molar concentration.

Kohlrausch law: -
 The limiting molar conductivity of an electrolyte (i.e.
molar conductivity at infinite dilution) is the sum of the limiting
ionic conductivities of the cation and the anion each multiplied
with the number of ions present in one formula unit of the
electrolyte.

Kohlrausch law in terms of equivalent conductivity:-

The equivalent conductivity of an electrolyte at infinite

dilution is the sum of two values one depends upon cation and other upon anion.

Electrode Potential :-

The electrical potential difference set up between

metals and its ions in the solution is called electrode potential.
Cell potential or EMF of a cell:- The difference between the electrode potential of the two half cell is
known as cell potential or cell voltage it is called Electromotive Force or EMF of the cell if no current is
drawn from the cell.

Electrochemical series:-

The various electrodes have been arranged in order of their increasing value of
standard reduction potentials. This arrangement is called electrochemical series.
Nernst equation for electrode potential:-

Mn+ + ne- --> M

Then Nernst equation is,

Where, E = electrode potential under given concentration of M n+ ions and temperature T.

 E0 = standard electrode potential.

R = gas constant.

T = Temperature in K

F = one Faraday

n = No. of electrons involves in the electrode reaction.

Also put, R = 8.314 Jk-1mol-1

F = 96500 coulombs

T = 298 k

Primary Cells

Dry cell:-

It consist of a cylindrical zinc container which acts as a anode. A graphite rod is placed between
the center, acts as a cathode. The space between the cathode and the anode is so packed with the paste
of NH4Cl and ZnCl2 and graphite is surrounded by MnO2 and carbon.

Reactions,
 -->
At Anode: - Zn (s) Zn2+ (aq) + 2e-

At cathode: - 2MnO2 (s) + 2NH4+ (aq) + 2e- --> Mn O 2 3 (s) + 2NH3 (g) +H2O

These cells have voltage in range of 1.25 V to 1.50 V have no long life.

Mercury cell (Ruber Mallory cell) :-

It consists of zinc container as anode, a carbon rod as cathode and a

paste of mercuric oxide mixed with KOH as the electrolyte a lining of porous paper separate the
electrolyte from zinc container.

Cell reaction:-

At Anode : - Zn + 2OH- --> ZnO + H O + 2e

2
-

At Cathode : - HgO + H2O+2e- --> Hg + 2OH -

Secondary cell
Lead storage battery:-
cell consist of lead anode and a grid of lead
packed with lead dioxide acts as lead cathode. These electrodes
are arranged alternatively separated by fiber glass sheet and
suspended in sulfuric acid (dilute) which acts as electrolyte.

Electrode reaction occurs during discharge battery:-

At Anode :- Pb + SO42- --> PbSO4 + 2e-
At Cathode :- PbO2 + SO42- + 4H+ + 2e- --> PbSO4 +2H2O
In above reactions H2SO4 is used hence density of H2SO4 is
decreases so battery will discharge.

During charging:-
The electrode reaction is reserved.
PbSO4 + 2e- --> Pb + SO42-
PbSO4 +2H2O --> PbO2 + SO42- + 4H+ + 2e-

Nickel Cadmium Storage Cell:-

 It consists of cadmium electrode (as
Anode) and metal grid of nickel (iv) oxide as cathode immersed
in KOH solution.

Reaction occurs during discharge of cell:-

At Anode :- Cd + 2OH- --> Cd(OH)2 + 2e-
At Cathode :- NiO2 + 2H2O +2e- --> Ni(OH)2 + 2OH-
Hence,
The reaction can be reversed during charging. The potential of
each Ni-Cd cell is approximately 1.4 V

Fuel cell: -
It consists of porous carbon electrodes containing
suitable catalyst incorporated in them. Concentrated KOH or
NaOH solution is placed between the electrodes to act as the
electrolyte. The hydrogen or oxygen gases are bubbled through
the porous electrode into the KOH/NaOH solution.

Reactions:-
At Anode: - 2H2 + 4OH- --> 4H2O + 4e-
At Cathode: - O2 + 2H2O + 4e- --> 4OH-
CORROSION
Corrosion:-
The process of slowly eating away of metal due to
attack of atmospheric gases on the surface of metal resulting
into the formation of compounds such as oxides, sulphides,
carbonates, sulphates etc. is called as corrosion.
In corrosion the metal is oxidized by loss of electrons to oxygen
and formation of oxides. The corrosion of iron occurs in the
presence of air & water.
In iron sheet or object or a particular pot behaves like a where
oxidation takes place.
Anode: - 2Fe (s) --> 2Fe2+ + 4e-
And these electron moves to another spot where reduction
takes place in the presence of H+ ion (H2CO3)
At Cathode: - O2(g) + 4H+ (aq) + 4e- --> 2H O (l)
2

The overall reaction being 2Fe + O2 + 4H+ --> 2Fe 2+

+ 2H2O

E0(cell) = 1.67 v

Fe2+ (ferrous ion) oxidised by O2to form ferric ion (Fe3+) which comes out as Rust Fe2O3.xH2O.