PRESENTATION

ON
POLAROGRAPHY

PRESENTED BY:- ROMA DAS

M.SC 1ST YEAR (CHEMISTRY DEPARTMENT)
GUIDED BY:- MAM DR.NIDHI GOVIL
CONTENTS
1. Polarography
2. Principle
3. Instrumentation
4. Mercury electrodes
5. Methods of analysis
6. Polarographic data
7. Ilkovic equation
8. Different types of currents of polagraphy
9. Factors affecting diffusion current
10. Polarographic maxima
11. Advantages of polarography
12. Applications
POLAROGRAPHY

It is an electrochemical technique of analysing solutions that measure the current flowing

between two electrodes in the solution as well as the gradually increasing applied voltage
to determine respectively the concentration of solute and its nature.

Created by: Jaroslav Heyrovsky for that he awarded Nobel Prize in 1959
 PRINCIPLE

Polarography is a voltammetric technique in which chemical species (ions or molecules) undergo

oxidation (lose electrons) or reduction (gain electrons) at the surface of a dropping mercury electrode
(DME) at an applied potential.

-Polarizable Electrode& WE:- Dropping mercury Electrode

-Non-polarizable Electrode& RE:- Calomel Electrode

From the current-voltage curve qualitative and quantitative analysis can be done. The instrument is
called Polarograph and the curve is called as Polarogram and the technique is called Polarography
• The point of inflection in the current- voltage curve is known as
Half-wave potential and is characteristic or typical for every
element or functional group Qualtitative aspect

• The diffusion current measured is proportional to the

concentration of that particular compound- Quantitative
aspect

• Thus, polarography can be used for both qualitative and

quantitative analysis of compounds.
Instrumentation

Working electrode Dropping Mercury Electrode(DME), a microelectrode

Reference electrode saturated calomel electrode (SCE)

Counter electrode /current- carrier auxiliary electrode Pt wire ( Hg – pool)

Supporting electrolyte KCI

Mercury electrodes

In polarography, mercury is used as a working electrode,

because mercury is a liquid. The working electrode is often
a drop suspended from the end of a capillary tube.

Three examples of electrodes:

1. HMDE (Hanging mercury drop electrode)

2. DME (dropping mercury electrode)- Most commonly
used electrode. Mercury drops form at the end of the
capillary tube as a result of gravity. The optimum
interval between drops for most analysis is between 2
to 5 seconds.
3. DSME (static mercury drop electrode.
Why Mercury electrode?

Mercury as a working electrode is useful because:

1. It displays a wide negative potential range.

2. It's surface is readily regenerated by producing a new drop or film.

3. Many metals ions can be reverisbly reduced into it.

METHOD OF ANALYSIS
•

• The polarographic apparatus consists of a polarisable

electrode (DME) and a reference electrode (SCE).
•
• Between these electrodes, the required potential range (0 to -3
V) can be applied.
•
• It consists of a sample cell made up of glass, in which the
sample solution to be analysed is kept.
•
• The capillary is dipped into the solution to be analysed and the
height of the mercury reservoir is adjusted so that droptime of
about 2- 5 sec is set.
• Supporting electrolytes like potassium chloride is added to the sample solution to
eliminate migration current

• The oxygen present in the sample solution is removed by passing Nitrogen or using
alkaline pyrogallol solution.

• Maximum suppressors are added in the required concentration range. When all
these things are done, the initial and final potential is set in the instrument and the
current-voltage curve is recorded.

• From the polarogram, half wave potential and diffusion current is determined and
thus qualitative and quantitative analysis is performed.
POLAROGRAPHIC DATA

Obtained from an automatic recording instrument is called a polarogram,

and the trace a polarographic wave.
POLAROGRAM
It is a sigmoid type graph of current versus potential in a polarographic
analysis.In thiswe get to see 3 categories of current:-
• The residual current (due to impurities)
• The diffusion current resulting from the redox rxn of the sample
• The limiting current
From this graph half wave potential as well as diffusion current is
calculated. Diffusion current is used for determination of concentration
of substance.Half wave potential is characteristic of every element. Since
every electrochemical species have specific half wave potential.
• In half wave potential the concentration of oxidised and reduced
forms at electrode surface is equal. i.e., 50% of oxidised and 50% of
reduced forms are present.
 ILKOVIC EQUATION
Ilkovic equation is a relation used in polarography relating the
diffusion current (id) and the concentration of the non- polarisable
electrode, i.e., the substance reduced or oxidised at the dropping
mercury electrode (polarisable electrode)
id = 607 nD1/2 Cm2/3 t 1/6
Where,
• id = Diffusion current in microamperes
• 607 = Constant of various numerical factors including: Faraday
constant (П), density of Hg, etc.
• n = Number of electrons duly involved in the electrode reaction
• D = Diffusion coefficient in cm2 .sec-1,
• C = Concentration in mmol/L.
• m = Weight of Hg flowing via the capillary in mg.sec-1,
• t = Drop time in seconds,
DIFFERENT TYPES OF CURRENTS IN POLAROGRAPHY
• Residual current (ir):This. Is the current due to presence of impurities in the analyte solution,
before reaching the redox potential of the anlayte.
• Migration current (im):It is due to migration of cations from the bulk of the solution towards
cathode due to diffusive force, irrespective of concentration gradient.

• Diffusion current (id):The difference between Residual current and Limiting current is called
Diffusion Current (id).Diffusion current is due to the actual diffusion of electroreducible ion
from the bulk of the sample to the surface of the mercury droplet due to concentration
gradient.

• Limiting current (il):Beyond a certain potential, the current reaches a steady state value
called as the limiting current. At this point, the rate of the diffusion of ions is equal to the
rate of reduction of ions, and the state of electrode is said to be concentration polarised.
FACTORS AFFECTING DIFFUSION CURRENT

• Concentrations: Diffusion current is directly proportional to the concentration of the

electroreducible ions .
• Temperature : Diffusion current also varies with respect to temperature (directly
proportional).
• Viscosity of the medium : Diffusion coefficient depends on the viscosity of the medium.
Hence, diffusion current also varies.
• Capillary characteristics : The bore size of the capillary, drop time in seconds and the pressure
of the mercury will all affect the diffusion current as they alter the flow characteristics of
mercury droplet.

• Presence of maximum suppressors: Maximum suppressors like gelatin, dye stuff’s and
surfactants will affect the diffusion current.
POLAROGRAPHIC MAXIMA
An increase of current above the limiting value in the form of a maximum. Abnormal peak appears on the
polarogram usually in concentrated solution. Maxima may occur on waves due to anions, cations, or
neutral molecules.• Also this maxima distorts the waveforms and complicate the measurement of the
diffusion currents.

This maxima can be eliminated by using maximum

suppressors which increases the viscosity eliminate
the polarographic maxima such as:
• Gelatin (0.002% to 0.01%)
• Dyes (methyl red)
• Surfactants (triton)
ADVANTAGES OF POLAROGRAPHY
• Only small volume of sample is required.
• Turbid and coloured solutions can be analyzed.
• Its sensitivity is sufficient for the determination trace elements and toxic
impurities.
APPLICATIONS OF POLAROGRAPHY
1. Polarography is used for determination of Oxygen content of fluids including
whole body fluids, fermentation liquors &milk for studying the respiration
rates of microorganisms.

2. Several mercury containing antiseptics and insecticides were determined

polarographically.

3. Hormones like thyroxine,insulin,adrenaline and several sex hormones are

estimated by polarography.

4. It is used for the determination of antibiotics such as pencillin,streptomycin

and chloramphenicol.

5. Several Alkaloids can also be estimated by polarography.

Thank you