INTRODUCTION TO

ELECTROCHEMICAL METHODS

INSTRUMENTAL ANALYSIS AND TECHNIQUES-II

PHC-804
Course Incharge: Prof. Dr. Somia Gul
 Learning Objectives of Current Lecture
To learn about the introduction to Polarography.

 To learn about the difference between Polarography and potentiometry.

 To learn about the difference between Polarography and Polarimetry.

 To learn about the difference between Polarograph and Polarogram.

 To make students familiar with Standard electrode- saturated calomel electrode, Dropping
Mercury electrode/ micro electrode/ working electrode.

 Finally to have better understanding of the technique use for pharmaceutical analysis.
•
Previous Lecture
Before going further, recall that we have learnt that

 A titration is a technique where a solution of known concentration is used to determine the concentration of an unknown solution.

 Potentiometric titration is a volumetric method in which the potential between two electrodes is measured (referent and indicator
electrode) as a function of the added reagent volume.

 The Nernst equation tells us that a measurable quantity -voltage or potential -is related to the concentration of species in solution.

 In many cases, the measured potential is due to a number of species, and hence the concentration of one can be difficult or impossible
to determine.

 Electrodes have been designed to respond only to one (or a very small number of) species, thus allowing the measurement of its
concentration. This is known as direct potentiometry.

 In other cases, the analyte can be determined by means of a titration, and the change in its concentration monitored by measurement
of the solution potential. This is known as a potentiometric titration.

 Automatic titrators are available which can perform either form of a potentiometric titration: collection of data and calculation of
endpoint, and titration to a set pH.

• Now after all these details, we have to move forward for details of Polarography.
 Polarography
Polarography is an electro
analytical method in which time
dependent potential is applied to
an electrochemical cell and current
passing through the cell is
measured as a function of total
potential.

It is the only method in which

liquid electrode is used.

The apparatus used is called

Polarograph.
Difference B/W Potentiometry, Polarography and Polarimetry

Potentiometry: measures the change

in electrode potential during a
chemical reaction.

Polarography: measure the current at

different time dependent potential.

Polarimetry: sensitive, nondestructive

technique for measuring the optical
activity exhibited by inorganic and
organic compounds.
 Polarography Instrumentation
ELECTROCHEMICAL CELL:
a device capable of either generating electrical
energy from chemical reactions or using
electrical energy to cause chemical reaction.

Instrumentation and Apparatus of Polarograph:

•In this method the cell setup system of an electrochemical cell is
present.
•The two electrodes are present i.e.: SCE (Saturated Calomel
Electrode) and DME ( Dropping Mercury Electrode).
•The DME consist of small droplets of mercury emerging from
the lower tip of small bore capillary tube attached to the bottom
of stand tube and mercury reservoir.
•The resulting mercury drops are constant in diameter (0.05mm).
•The drop rate is controlled by adjusting the height of reservoir.
Polarography Instrumentation
 Polarography Instrumentation
Instrumentation and Apparatus of Polarograph:

VOLTAGE DRIVER: The voltage is applied to the polarography

cell is varied by means of the slide wire that act as voltage
divider.

NITROGEN INLET: The nitrogen is bubbled into the analytic

solution in the polrography cell to remove any oxygen.

there’s another inert electrode present to complete the circuit.

This apparatus is designed in such a way that the electrolysis of

electro active species take place at the DME and the potential of
DME is calculated relative to SCE.
 Polarography Instrumentation
Instrumentation and Apparatus of Polarograph:

REFERENCE ELECTRODE:
 Saturated calomel electrode is used.
 Also called as positive electrode.
 Has large surface area & so its current density is negligible.
 Therefore, its potential is constant unaffected by the applied
potential.

INDICATOR/ MICROELECTRODE:
 Dropping mercury electrode.
 Also called as negative electrode
 Electrolysis occurs & its potential is measured relative to
reference electrode.
 Polarography Instrumentation

FACTORS AFFECTING THE WORKING OF

POLAROGRAPHY:

 No stirring is allowed. It may causes disturbance in

the concentration gradient.

 Since it is an only technique in which liquid

electrode is used so there's a controlled dropping of
mercury.
 Polarography Instrumentation
WORKING OF POLAROGRAPHY:

 RESIDUAL CURRENT: (ir)

Low potential (0.5) causes the charging of electrodes
and reduction of impurities and the current flowing
through the cell is residual current.

 DIFFUSION CURRENT: (id)

When potential is increased to 1, the current flowing
through the cell increases. And the reduction of specie
occurs in the vicinity of microelectrode. They start
moving from the bulk of solution to the surface of
electrode.
 Polarography Instrumentation
WORKING OF POLAROGRAPHY:

 CONCENTRATION POLARIZATION:
Once all of the specie is reduced, the increase in potential does not bring about
any increase in the current. This is called concentration polarization. The current
measured in this region is diffusion controlled and is a function of concentration.

 LIMITING CURRENT:
Current passing through the cell when concentration of reducible species at the
electrode surface is zero.

 MIGRATION CURRENT: (im)

It is the current due to migration of cations from the bulk of solution towards
cathode due to diffusive forces.
Undesirable
Non-reducible electrolyte (KCl) is added to the solution to eliminate this current.

12
Polarogram
 Polarogram
Polarogram is a graphical representation
It is divided into three regions that are A, B, C.

REGION A is the charging current of the electrical

conductor (electrode) and therefore reduces impurities traces
present in the solution. This current is known as Residual current
(Ir).

REGION B is the diffusion current results from the

reduction of the electro active species in the solution. In this
region as the potential increases, more will be the specie is
reduced and a concentration difference gradient can be observed.

REGION C is the concentration polarization region where

limiting current is measured and no further current is increased
because all of the specie has been reduced.
Summary
Potentiometry is use to measures the change in electrode potential during a
chemical reaction.

Polarography is an electro analytical method in which time dependent potential is

applied to an electrochemical cell and current passing through the cell is measured
as a function of total potential.

Polarimetry is a sensitive, nondestructive technique for measuring the optical

activity exhibited by inorganic and organic compounds.

The two electrodes are present i.e.: SCE (Saturated Calomel Electrode) and DME
(Dropping Mercury Electrode).

The DME consist of small droplets of mercury emerging from the lower tip of
small bore capillary tube attached to the bottom of stand tube and mercury
reservoir. 15
Summary

The resulting mercury drops are constant in diameter (0.05mm).

The drop rate is controlled by adjusting the height of reservoir.

No stirring is allowed during polarography as it may causes

disturbance in the concentration gradient.

Polarogram is a graphical representation of Polarography and is

divided into three regions that are region A, region B and region C.

16
Further Reading and References
• Pharmaceutical Analysis Vol II by Dr. Anees Ahmad Siddiqui.

• A.H Beckett, J.B. stenlake, Practical Pharmaceutical Chemistry,

Fourth edition -part two

• Pharmaceutical Analysis Vol I & II by Asotosh Kar.

 Analytical Aspects of Drug testing. Edt. Dale G Deutsch, John Wiley

& Sons.
 Analytical Profiles of Drug substances and excipients. Rosenstock, J,
Academic Press, New York.