ELECTRO ANALYTICAL CHEMISTRY - Notes
ELECTRO ANALYTICAL CHEMISTRY - Notes
ELECTRO ANALYTICAL CHEMISTRY - Notes
The redox reaction in an electrolytic cell is non spontaneous. Electrical energy is required to
induce the electrolysis reaction. An example of an electrolytic cell is shown below, in which
molten NaCl is electrolyzed to form liquid sodium and chlorine gas. The sodium ions migrate
toward the cathode, where they are reduced to sodium metal. Similarly, chloride ions migrate to
the anode and are oxided to form chlorine gas. This type of cell is used to produce sodium and
chlorine. The chlorine gas can be collected surrounding the cell. The sodium metal is less dense
than the molten salt and is removed as it floats to the top of the reaction container.
Conductometric titration
The titrations in which end point is determined by means of conductance measurements
are called conductometric titration
Potentiometric titration
The variation of potential of an electron with the concentration of ions with which it is in
equilibrium can be used as an indicator to find the end point in volumetric analysis is
known as potentiometry.
EMF
The difference of potentials between the electrodes of a cell which causes flow of current
from an electrode of higher potential to another at lower potential is known as
electromotive force or EMF or cell potential .
Electrochemical sensors
An electrochemical sensor is a device that transforms electrical information into an
analytical useful signal.
Composed of two basic components, a chemical recognition system and physiochemical
transducer which is a device that converts the chemical response into a signal that can be
detected by modern electric instrumentations.
Electrogravimetry
The goal is to determine the amount of analyte present by converting it to a product that
is weighed as a deposit on one of the electrode.
In most applications, the metal is deposited on a weighed platinum cathode, and the
increase in mass is determined. Some methods use anodic deposition such as the
determination of lead as lead oxide on platinum and of chloride as silver chloride on
silver.
Coulometric titrations
Polarography
It is a particular type of voltametry in that the working microelectrode takes the form of a
dropping mercury electrode.
CONDUCTOMETRY TITRATIONS
The titration in which end point is determined by means of conductance measurements,
are called conductometric titrations.
They are based upon the principle that the conductance of an electrolyte solution
depends upon the number of ions, their charges and mobilities.
The conductance of the solution changes with every addition of the titrant.
At the equivalent point, a sharp change in conductance is observed.
The end point can be conveniently obtained by extrapolation of straight lines obtained by
plotting conductance against volume, and finding out the point of their intersection.
Common ion effect
The common-ion effect refers to the decrease in ionization of a weak electrolyte by the
addition to the strong electrolyte with an ion in common with the weak electrolyte.
Hydrogen sulphide (H2S) is a weak electrolyte. It is weakly ionized in its aqueous solution.
There exists an equilibrium between un-ionized molecules and the ions in an aqueous medium as
follows:
H2S ⇌ H+ + HS−
To the above solution of H2S , if we add hydrochloric acid, then it ionizes completely as
HCl → H+ + Cl−
This makes H+ a common ion and creates a common ion effect. Due to the increase in
concentration of H+ ions, the equilibrium of dissociation of H2S shifts to the left .Thus the ionization
of H2S is decreased.