Polarography, its types

and dropping mercury

electrodes
Subtitled by Syed Ali Hassan Shah 20014 107-001
Zaid Zaffar 20014107-002
Asma Siddiqa 20014107-10
Subtitled to Dr. Nadeem Zaffar
Table of contents

1- Polarography………………………………………………………………………………………………(3-15)

2- AC polarography………………………………………………………………………………………(16-18)

3- Pulse polarography…………………………………………………………………………………(19-21)

4-Mercury electrode……………………………………………………………………………………(22-33)
 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.
 Polarography is a type of voltametry where the working electrode is a dropping mercury
electrode (DME) or a static mercury drop electrode (SMDE), which are useful for their
wide cathodic ranges and renewable surfaces.
 It was invented in 1922 by Czechoslovak chemist Jaroslav Heyrovský, for which he won the
Nobel prize in 1959.
 The main advantages of mercury as electrode material are as follows: 1) a large voltage window:
ca. from +0.2 V to -1.8 V vs reversible hydrogen electrode (RHE).
 Hg electrode is particularly well-suited for studying electroreduction reactions. very reproducible
electrode surface, since mercury is liquid.
 Very easy cleaning of the electrode surface by making a new drop of mercury from a large Hg pool
connected by a glass capillary.

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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.

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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.

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 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.

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UNIT%20VII.pdf
 Qualitative analysis

•Qualitative analysis means the identification of the the unknown compoud.

•In case of polarography the half wave potential is characteristic for each element.
•Every element have specific value of half wave potential which we can view from literature and analyze
qualitatively any analyte.

Half wave potential

Half wave potential:-
•Half wave potential is the potential at which the concentration of oxidised and reduced forms at electrode
surface is equal. i.e., 50% of oxidised and 50% of reduced forms are present.
• It is the potential of active ions when the diffusion current is half of the total current if diffusion current is Id.
• At E1/2 diffusion current is half.
• E1/2 is the characteristic feature of the element and thus it gives the qualitative analysis, knowing the value of
E1/2 one can predict the element present in the solution.
•In the usual current-voltage polarogram the total Id current is given by the difference in height of platue and
base line current.
• By the convection at cathode reduction of oxidant and is taken as the positive value while for the anode it is
negative.

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 Quantitative analysis

Quantitative analysis is performed by calculating the diffusion current.

•The diffusion current can be calculated by the ilkovic equation.
Def.
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.
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 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 ,
• m = Weight of Hg flowing via the capillary in mg.sec-1 ,
•t = Drop time in seconds,
•C = Concentration in mmol/L.
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 Limiting current
Decomposition potential

Diffusion current
Current

Half wave potential

Residual current

Potential

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 Factor affecting
diffusion current

• Temperature also effects the Id as the ionic mobility is changed. For most of cases the temperature coefficient lies in between
1.5-2%. To control the temperature it is advisable to keep active electrolyte in a bath having a constant temperature about 25 °C.
• Pressure also influences the Id either by changing the mass flow of mercury and affecting its speed. This can be controlled by
adjusting the height of reservoir and adjusting the speed.
• Time alone factor doesn’t affect the diffusion current because it has sixth root power coupled with mass flow, the diffusion
current is affected. So, by choosing the size of capillary hole and adjusting the pressure one can get accurate result of Id.
• Complex formation diffusion current is also greatly affected if active species from the complex in the solution.

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(e) Interfacial surface tension the diffusion current is effected by interfacial tension at mercury surface i.e. there is some gap
between the surface of dme and solution phase containing active ions. As a result the current may decrease by decreasing the size
of droplets as its interfacial tension can be reduced.
(f) Diffusion coefficient is related to both viscosity and concentration of the electrolyte. Viscosity depends on temperature and
concentration of active electrolyte. If concentration of solution is low the viscosity will be low and diffusion current high.
Alternatively, by increasing the temperature one can have high Id. An empirical relation between Id and ƞ has been derived from
the diffusion coefficient has been derived from stoke’s

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 Residual current

•The current that flows in the absence of the depolarizer (i.e. due to the supporting electrolyte) is called residual
current.
•This has to be taken into consideration while interpreting the polarograms.
•It is the sum of the relatively larger condenser current (ic) and a very small faradic current (if).
ir = if + ic
• ic (condenser current) – is due to the formation of Helmholtz double layer at the mercury surface. if (faradic
current) – is due to the traces of impurities.

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 Migration and limiting
current

•Migration current is due to migration of cations from the bulk of the solution towards cathode due to diffusive
force, irrespective of concentration gradient.

•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.

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 Applications

https://ebooks.inflibnet.ac.in/esp02/chapter/polarography/

https://ebooks.inflibnet.ac.in/esp02/chapter/polarography/
 AC polarography

 A normal current voltage curve is obtained when the concentration of active

electrolyte is minimum upto 10-4 M because at lower concentration curve is
not defined well.
 Due to the changing size of mercury drop at DME current fluctuate which
causes wrong estimation.
 Condenser current causes an error in the determination of Id as it is non
faradic in nature.
 Very dilute solution is not correctly estimated as resistance by solvent crops
up. For the determination of mixture of ions one needs the E1/2 potential
difference 200 mV at least required otherwise there will be no clear separation
of wave height.

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 Principle

 In order to have a clear separation of wave height for the different ions in
solution and to know corrected Id and E1/2 etc.
 A modified method or modification in DC polarography is achieved by
incorporating in alternative (AC) in the (DC) polarography.
 As AC polarography a constant sinusoidal current is fed to the cell containing
active electrolyte with ac potential and dc potential superimposed on it.
 The purpose of dc is to give correct reduction/oxidation current in which there
is no attraction/repulsion.

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https://ebooks.inflibnet.ac.in/esp02/chapter/polarography/
Pulse polarography

 In pulse polarography, one can measure the changes in diffusion current

produce by rectangular pulses of quiet ling duration.
 The pulse synchronized with the maximum growth of mercury drop.
 If a dropping mercury electrode is employed then the current is measured
from 40 to 60 millisec after the application of pulse to allow the time for the
charging current to decay to a very low value.
 The capacitive current actually decays exponentially at a rate governed by
magnitude of capacitance and series of resistance of the system.

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 Cont.

 During this time interval, the faradic current also decays somewhat but
doesn’t reach the diffusion control level because the concentration gradient
at the instant of current measurement is considerably large.
 Each succeeding drop is polarized with somewhat large pulse.


 The method gives a current-voltage curve similar to that of DC polarography

and sensitivity of method is 6-8 V times than that of classical DC
polarography. The measured signal is the faradic current that flow at the plus
potential and minus any faradic current flowing to the fixed DC potential.

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 Limitations of polarography

 It is said that the solution should not be disturbed throughout the

polarographic experiment, although Hg itself disturbs the solution.
 Capillaries are quite small and thus readily clogged.
 Mercury is extremely poisonous.
 Polarography cannot measure solutions with concentrations fewer than 10-5
M. Electrical noise and residual current are found at low concentrations,
hence no good signal can be observed.
 The surface area of a drop of mercury is never consistent.
 It cannot be used at greater positive potentials due to mercury oxidation.

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Mercury electrode
There are two types of working electrodes
• Solid working electrode
• Liquid working electrode
Hg-electrode
It is a type of liquid working electrode. The polarography is
just like voltammetry, only difference is that here mercury
electrode is used.
Polarography is an earlier develop technique.
It is preferable for cathodic side
In this we measure high negative potential.
Diagram
Advantages of mercury electrode

 The every mercury drop have a renewable surface.

 Every drop is reproduceable.
 We utilize complete surface area for carrying out the
reaction.
 Zinc have high negative potential we measure the
quantity of zinc in the sample by using mercury
electrode
Drawbacks of using Hg-electrode
 Hydronium ion is a common interfering species while using
mercury electrode.
 Because when we run the polarography at more negative potential
this causes the reduction of hydronium ion along with the reduction
of analyte.
 As mercury electrode have extend cathodic window it cause the
reduction of hydronium ion.
 We cannot run mercury electrode at the anodic side because this
will cause the oxidation of mercury and no more electrode will
exist.
Types of Hg-electode
Hanging mercury drop electrode
(HMDE)

Dropping mercury electrode (DME)

Thin film mercury electrode (TFME)

Static mercury drop electrode (SMDE)

1.Dropping mercury electrode

Dropping mercury electrode is used in Polarography to get quantitative and qualitative analyses of substances.
In this electrode, the mercury is constantly dropped into the solution from a reserve with the help of capillary tubes.
The diameter of these tubes is 0.03- 0.05 mm.
Diagram
2.Hanging mercury drop electrode

 An electrode formed of a partial mercury drop of

controlled geometry and surface area at the end of
a capillary. The hanging mercury drop electrode
(HMDE) is a useful device for laboratory
experiments in various fields as, for example,
trace analysis by stripping voltammetry
 periodical renewal of its surface area, which
minimizes surface contamination, thus permitting
highly reproducible measurements.
Diagram
3.Static mercury drop electrode

 The static mercury drop electrode (SMDE) is a

significant new electrode for use in
polarography. Mercury flow from a reservoir of
mercury to a mercury drop capillary extending
vertically downward from the reservoir is
governed by selective engagement of a sealing
surface immersed in the mercury reservoir with
a valve seat also immersed in the mercury
reservoir to allow for controlled formation of
mercury drops at the lower end of the capillary
which drops, after formation, are held non-
growing or static.
Diagram
4.Thin film mercury electrode

 This electrode is used when there is small concentration

of analyte is present in sample.
 When concentration is below than micro level than we
use thin film mercury electrode.