Assignment

Topic: “Principle of potentiometric titration and its applications’’

Introduction to Potentiometric titration

It is the procedure through which the quantity of the given test substance is determined by the
measured addition of titrant until the entire test substance undergoes reaction. After
the titration process, the potential difference between the two electrodes (namely the reference
and indicator electrode) is measured in conditions where a thermodynamic equilibrium is
maintained and the current passing through the electrodes does not disturb this equilibrium.

Figure: Potentiometric titration

Principle of Potentiometric titration

A typical cell for potentiometric analysis consists of a reference electrode, an indicator electrode
and a salt bridge. This cell can be represented as
Reference electrode | salt bridge | analyte solution| indicator electrode
Eref Ej Eind
A reference electrode, Eref, is a half-cell having a known potential that remains constant at
constant temperature and independent of the composition of the analyte solution. The reference
electrode is always treated as the left-hand electrode in potentiometric measurements. Calomel
electrodes and silver/silver chloride electrodes are types of reference electrodes.
An indicator electrode has a potential that varies with variations in the concentration of an
analyte. Most indicator electrodes used in potentiometry are selective in their responses. Metallic
indicator electrode and membrane electrodes are types of indicator electrodes.
The third component of a potentiometric cell is a salt bridge that prevents the components of the
analyte solution from mixing with those reference electrodes. A potential develops across the
liquid junctions at each end of the salt bridge. The junction’s potential across the salt bridge, Ej,
is small enough to be neglected.
The potential of the cell is given by the equation;
Ecell = Eind – Eref + Ej
Where,
Ecell= electromotive force of the complete titration
Eind= electromotive forces of the indicatior
Eref = electromotive force of the reference
Ej= electromotive force at the junction across the salt bridge.

Application of Potentiometric titration

The most widely used technique to characterize the acid/base and complexing properties of
hydrous particle surfaces is based on potentiometric titrations. Properly applied it provides
accurate data over wide concentration ranges and, with help of automatic measuring and data
collecting systems, it has become possible to collect large amounts of data within a reasonably
short time period. However, collection and interpretation of experimental data is beset with
difficulties. Some of these difficulties are identified and discussed with special reference to some
goethite systems. The application of potentiometric titration are following in-
 Neutralization: Glass /calomel electrode for determination of of pH
 Precipitation reaction: membrane electrodes are for the determination of the
halogens using silver nitrate agent.
 Complex formation titration: metal and membrane electrodes for the determination
of many cations (mixture of Bi3+, Cd2+ and Co2+ using EDTA)
 Redox titration: platinum electrode for example for reaction of Fe3+/Fe2+ with
Ce4+/Ce3+)
Besides that
 It is used in clinical chemistry for analysis metal
 It is used for analysis of cyanide, ammonia etc in water or wastewater.
 It is used in agriculture for detection of different elements in soils, fertilizers etc.
 It is used in detergent manufacturing , food processing etc.