Polarography

ENVIRONMENTAL TECHNIQUES
ENS CC 521
POLAROGRAPHY
BY
SUNIL
POLAROGRAPHY
Polarography is an electrochemical method

of analysis based on the measurement of
current flow resulting from the electrolysis of
a solution at a polarisable microelectrode as
a function of applied voltage.
.
Principle:
➢ Polarography is based upon the principle that

gradually increasing voltage is applied between two
electrodes, one of which is polarisable (dropping
mercury electrode) and other is non-polarisable and
current flowing between the two electrodes is recorded
➢ A sigmoid shape current-voltage curve is obtained
from which 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.
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 m2/3 t 1/6 C

Where,
Id = Diffusion current in microampere
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 ,
m = Weight of Hg flowing via the capillary in
mg.sec-1 ,
T = Drop time in seconds,
C = Concentration in mmol/L.
➢ The Ilkovic Equation holds good for the ‘drop-time’
to vary between 2 to 8 seconds.
➢ In order to accomplish this aim and objective the
following two critical adjustments may be done
carefully:
▪ Length of capillary
▪ Manouvering the Hg-pressure to bring the drop
time very much within the range (i.e., 2-8 sec)
The factors that influence the Ilkovic equation:
1) Both ‘m’ and ‘t’ shall change with the dimensions of the capillary (its
length) and the applied pressure of Hg reservoir to form the ‘drop’.
2. Height of Hg column must be maintained constantly as the ‘drop

time’ solely depends upon the applied pressure by the column of Hg
at the tip of DME and ‘analyte’ solution interface.
3. Applied voltage in a DME-assembly is responsible for causing possible

changes occurring in the prevailing ‘surface tension’ of a drop at the
tip of electrode.
4. Evidently, the variations in temperature and viscosity must be at bare

minimum level because it disturbs the ‘diffusion coefficient’ most
significantly.
Dropping Mercury Electrode (DME):
Dropping mercury electrode

(DME) is a working electrode
arrangement for
polarography in which
mercury continuously drops
from a reservoir through a
capillary tube (internal
diameter 0.03 - 0.05 mm)
into the solution.
• The optimum interval between drops for most
analyses is between 1 and 5 s.
• The unique advantage to the use of the DME is that
the constant renewal of the electrode surface,
exposed to the test solution, eliminates the effects
of electrode poisoning.
Construction:
➢ The assembly consists of a mercury reservoir.

➢ It consists of fine capillary having bore size
ranged from 20-50 µ and 10-15 cm long.
➢ The capillary is connected to mercury reservoir
by rubber tubing.
➢ A small glass electrolysis cell in which the
unknown solution is placed.
➢ The height of the mercury reservoir is adjusted
such that drop time is 1-5 seconds.
Working:
❖ Dropping mercury electrode (DME) is a polarisable

electrode and can act as both anode and cathode.
❖ The pool of mercury acts as counter electrode, i.e.,
anode if DME is cathode or cathode if DME is anode.
❖ The counter electrode is a non-polarisable electrode.
❖ To the analyte solution, electrolyte like KCl is added i.e.,
50-100 times of sample concentration.
❖ Pure nitrogen or hydrogen gas is bubbled through the
solution, to expel (remove) out oxygen.
-Eg: If the analyte solution contains cadmium ions,
then cadmium ions are discharged at cathode.
Cd2+ + 2e- → Cd
❖ Then, gradually increasing voltage is applied to the
polarographic cell and current is recorded.
❖ Graph is plotted between voltage applied and
current. This graph is called Polarograph and the
apparatus is known as Polarogram.
❖ The diffusion current produced is directly
proportional to concentration of analyte and this is
used in quantitative analysis.
❖ The half wave potential is characteristic of every
compound and this is used in qualitative analysis.
Disadvantages:
1. Capillary is very small and thus can be easily

blocked.
2. Mercury is very toxic.
3. Surface area of each drop of mercury is never
constant.
4. It cannot be used at higher positive potential due
to oxidation of mercury
Applications of Polarography:
1. Qualitative analysis:
It helps in characterization of organic matter and
various metal interactions from half wave potential of
the current v/s voltage graph.
2. Qualitative analysis:
Polarography is used in the determination of
concentration of drugs, metal ions etc. in the given
sample.
3. Determination of inorganic compounds:
Polarography is used in determination of cations and
anions in the presence of interfering ions.
4. Determination of organic compounds:
Polarography is used in determination of structure,
quantitative analysis of mixture of organic
compounds.
5. Estimation of dissolved oxygen:
Amount of oxygen dissolved in aqueous solution or
organic solvent can be calculated with the help of
Polarography.
6. Pharmaceutical applications:
Tetracycline antibiotics, sulphonamides can be
analysed by Polarography.
CONCLUSION
Polarography is a techniqe that is part of
voltametric analysis. This techniques is used to do
qualitative and quantitative determination of electro
active substances. This is explains polarographic
principle and the applications of polarography
References:
- Milner, G W C,1957,Principles and applications
of polarography and other electroanalytical
process,Long man Green andCo
- https//www.wikipedia.org
- Roa.V.Surynarayana.2002,Polarography allied
techniqes/university press
Thank you:-)

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ENVIRONMENTAL TECHNIQUES

Polarography is an electrochemical method

➢ Polarography is based upon the principle that

id = 607 nD1/2 m2/3 t 1/6 C

607 = Constant of various numerical factors

2. Height of Hg column must be maintained constantly as the ‘drop

3. Applied voltage in a DME-assembly is responsible for causing possible

4. Evidently, the variations in temperature and viscosity must be at bare

Dropping mercury electrode

➢ The assembly consists of a mercury reservoir.

❖ Dropping mercury electrode (DME) is a polarisable

1. Capillary is very small and thus can be easily

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