Polarography

Presented by:
Alsha Mehwish
Msc Chemistry-III
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Table of contents:
✓ Introduction…………………………………………………………………………3
✓ Principle…………………………………………………………………………….…4
✓ Mercury electrodes……………………………………………………………...6
✓ Why dropping mercury electrode………………………………………...7
✓ Problems with mercury electrode…………………………………………9
✓ Working and Method of analysis………………………………………....11
✓ Different types of current in polarography…………………………...13
✓ Factors affecting Diffusion current………………………………………..16
✓ Polarographic measurements………………………………………………..18
✓ Polarographic maxima…………………………………………………………..19
✓ Advantages of Polarography………………………………………………….21
✓ References…………………………………………………………………………...22
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Introduction:
 In 1922, Heyrovsky discovered this technique.
 Polarographic technique is applied for the qualitative or
quantitative analysis of electroreducible or oxidisable
elements or groups.
 It is an electromechanical technique of analyzing
solutions that measures the current flowing between two
electrodes in the solution as well as the gradually
increasing applied voltage to determine respectively the
concentration of a solute and its nature.
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Principle:
 The principle in polarography is that a gradually increasing negative
potential (voltage) is applied between a polarisable and non-
polarisable electrode and the corresponding current is recorded.
 Polarisable electrode: Dropping Mercury electrode
 Non-polarisable electrode: Saturated Calomel electrode
 From the current-voltage curve (Sigmoid shape), qualitative and
quantitative analysis can be performed. This technique is called as
polarography, the instrument used is called as polarograph and the
current-voltage curve recorded is called as polarogram.
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Continue..
 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.
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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. 3 examples of
electrodes:
 HMDE (Hanging mercury drop electrode)
 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.
 DSME (static mercury drop electrode)
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Why Dropping Mercury Electrode?

 Hg yields reproducible current-potential data.

 This reproducibility can be attributed to the continuous exposure of
fresh surface on the growing mercury drop.
 With any other electrode (such as Pt in various forms), the Figure :1 Drop
potential depends on its surface condition and therefore on its of dropping
previous treatment. mercury
electrode
 The vast majority of reactions studied with the mercury electrode https://glossary.
are reductions. periodni.com/gl
ossary.php?en
=
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 At a Pt surface, reduction of solvent is expected to
compete with reduction of many analyte species,
especially in acidic solutions.
 The high overpotential for H+ reduction at the
mercury surface. Therefore, H+ reduction does not
interfere with many reductions.
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Problems with Mercury electrode
 A mercury electrode is not very useful for performing oxidations,
because Hg is too easily oxidized.
 The electrode cannot be used over +0.4 V (vs S.C.E.), because Hg
dissolves and anodic wave is recorded. Lesser than -1.8 V, hydrogen
is liberated.
 The capillary is difficult to maintain since dust or other articulate
matter can block the capillary.
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Figure:2 Working and Construction of Polarography

https://www.slideshare.net/SaisreeNimma/polarography-141732582
 Method of Analysis: 11

 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 adusted so that droptime of
about 2- 7 sec is set.
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 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.
Different types of current in 13

polarography
 Residual current (ir):
It is the sum of the relatively larger condensor current and a very small
Faradic current. Condensor current is due to the formation of
Helmholtz double layer at the mercury surface and Faradic current is
due to the traces of impurities.
➢ 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.
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Figure:3 Polarogram
https://glossary.periodni.com/glossary.php?en=polarogram
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Continue..
 Diffusion current (id):
Diffusion current is due to the actual diffusion of electroreducible ion
from the bulk of the sample to the surface os the mercury droplet due
to concentration gradient.
 Limiting current (id):
Beyind a certain potential, the current reaches a steady value called as
the limiting current. At this point, the rate of diffusion of ions is equal
to the rate of reduction and the state of electrode is said to be
concentration polarised.
Factors affecting Diffusion Current 16

 Concentration:
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.
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 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 stuffs and surfactants will
affect the diffusion current.
Polarographic measurements: 18

 Polarographic measurements are governed by ilkovic equation Ilkovic Equation

— The linear relationship between the diffusion current (id) and the
concentration of electroactive species is shown by the Ilkovic equation:
 id = 607 nCD1/2m2/3t1/6,
 id = diffusion current in microamperes;
 n = number of electrons required per molecule of electroactive Substance,
 D = diffusion coefficient, in square cm per second,
 C = concentration, in millimoles per L,
 m = mass of mercury flow from the DME, in mg per second,
 t = drop time, in seconds.
 Polarographic Maxima 19

 An increase of current above the limiting value in the

form of a maximum is often noticed on polarographic
waves known as polarographic maxima.
 The origin of the maximum is sometimes connected
with the mechanism of the electrode process as in
the case of catalytic discharge of ions, while in many
cases, it is caused by the increased transport of the
depolarizer towards the electrode by a streaming
motion of the solution.
 The presence of this reproducible polarographic
maxima leads to error in determining half wave
potential and diffusion current. Figure : Polarographic Maxima
https://upload.wikimedia.org/wikipedia/commons/c/c
7/D%C3%A9formation_de_la_courbe_par_le_maxi
ma.jpg
Elimination of Polarographic 20

maxima
 Maximum suppressors which increases the viscosity eliminate the
polarographic maxima such as:
 Gelatin (0.002% to 0.01%)
 Dyes (methyl red)
 Surfactants (triton)
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Advantages of Polarography
 Only small volume of sample is required.
 Turbid and coloured solutions can be analyzed.
 It can be used for the determination of substances, which are not
electrochemical active (indirect).
 Prior separation of excepients is not required.
 Its sensitivity is sufficient for the determination trace elements and toxic
impurities.
 High speed analysis which is important for QC
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References:
 https://www.slideshare.net/ISFCPISFCollegeofPha/polarography-
102585040 Visited at 20/02/22) at 10:00am
 https://www.slideshare.net/chelsisoliva1/polarography-61782546
 https://www.slideshare.net/SaisreeNimma/polarography-141732582
 https://www.slideserve.com/wes/polarography Visited at
19/02/2022
 https://www.powershow.com/view2b/3efd6d-
NzE3O/Voltammetry_and_Polarography_powerpoint_ppt_presentati
on Visited at 20/02/2022
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Thank you