Polarography

By Dr. Irfan Pervaiz

Introduction
 It is an electroanalytical method of analysis where
time dependent potential is applied to an
electrochemical cell and the current flowing through
the cell is measured as a function of total potential.
History
 The earliest voltammetric method, polarographic
method of analysis was first developed by Jaroslav
Heyrovsky in 1922, for that, he received Nobel Prize
in 1952 for developing this technique using dropping
mercury electrode as the working electrode.
Potentiometry vs Polarography
 In potentiometry, zero current is maintained. But
in polarography, limited current is produced by
limited electrolysis. Hence, it is based on the
measurement of current resulting from reduction
or oxidation of an electro active species, at a given
electrode potential under controlled condition.
Electrodes
 As in potentiometry, there is a reference electrode,
saturated calomel electrode (SCE) and an indicator
electrode or microelectrode in this technique.
Indicator Electrode
 The microelectrode or indicator electrode assumes
the potential impressed upon in. The indicator
electrodes may be made from quite a large number
of materials.
Example
 For instance, mercury, platinum, gold and
graphite, having varying shapes and construction
can be used.
 Mostly, DME (Dropping mercury electrode) is
used as indicator electrode. The apparatus is
designed in such a manner that electrolysis of
electroactive species take place at the indicator
electrode and the potential of micro electrode is
always measured relative to reference electrode.
Reference Electrode
 The SCE consists of large surface area so that
current density (current per unit area) is small at
this electrode. Its potential will then essentially
constant and unaffected by applied potential (emf).
Definition
 The electrode potential of growing mercury
electrode in electrolyte containing electroactive
species is varied as a function of time and
resulting current is measured.
Theoretical Concept
 The principle of polarography can be explained
with help of simplified polarographic apparatus
which contain a reducible species (RS) such as
nitrofurantoin and supporting electrolyte (KCI) in
a electrolysis cell. When the movable contact ‘m’
is placed at the extreme left position (say zero), the
potential in the voltameter ‘V’ will be zero and the
current measured in microamp (m amp) on the
ammeter ‘A’ will also register zero.
Diagram
Theoretical Concept
 If the contact ‘m’ is now moved to the light, say to
0.5, a certain voltage will be impressed across the
electrode (readable in Voltameter V). Since the
microelectrode is negative, ions (impurities in the
salt and H2O) capable of picking up electrons at
this low potential and will be reduced and the
current flowing through the cell will be registered.
Theoretical Concept
 If the movable contact is advanced to 1, a greater
voltage will be impressed it across the electrode
(more ions will be reduced) and increase in current
flowing through the cell will be observed. If we
continue moving the contact, we will eventually
reach a potential, which will reduce electroactive
species.
Theoretical Concept
This effect will be reflected in a relatively large
increase in the current flowing through the cell on
increasing the voltage shows an increase in the
current flowing through the cell because a greater
number of reducible species RS (nitro-furantoin) are
reduced in the vicinity of electrode. As there is
decrease in the concentration of ion in the vicinity of
microelectrode, the potential of this electrode will
decrease. This is called concentration polarization.
Theoretical Concept
 However, increasing the potential does not bring
about an increase in the current. In other words,
the current, which is measured in this region, is
diffusion controlled and depends on the rates at
which the reducible species (nitrofurantion) Move
(diffuse) from the bulk of solution to the surface of
electrode. The diffusion controlled current
(diffusion current of limiting current) is a function
of concentration.
Instrumentation
Cathode
 It is a dropping mercury electrode.
 It carries negative charge.
 The diameter of capillary tube is 20-50 µm.
 The droplet time is 2-12 seconds so 5-30 drops per
minute can be produced.
 Applied voltage range is + 0.4 to – 1.8 V.
Instrumentation
Advantages of DME
 The surface area is always renewable and
eliminate toxic effects.
 The surface is smooth.

Disadvantages of DME
 Capillary can be blocked easily
 Potential range is only + 0.4 to – 1.8 V.
Instrumentation
Anode
 Mercury pool act as a anode.
 It has high surface area.
 No change in potential occur.
 It is a non-polarizable electrode.
 It carries positive charge.
Instrumentation
Solution
 Solution contains electroactive species and supporting
electrolyte.
Electroactive species
 The species which are under investigation are electroactive
species. For instance Pb+2.
 
Supporting electrolyte
 As we want ions should be transferred by diffusion only, we have
to avoid the transfer of ion (migration) due to potential gradient.
Instrumentation
Supporting electrolyte (Continued)
 A potential gradient exists between the electrodes with
the microelectrode (usually, dropping mercury
electrode, DME) negative relative to reference
electrode (usually saturated calomel electrode, SCE).
Cations will move towards the DME under the
influence of this potential and their reduction give rise
to the migration current (undesirable). Therefore, to
reduce the current carried by the reducible ion, a large
concentration of non-reducible electrolyte is added to
the solution.
Instrumentation
Supporting electrolyte (Continued)
 This substance, the indifferent electrolyte (or
supporting electrolyte) then carries essentially all
of the current and migration current is eliminated.
Commonly used supporting electrolytes are
potassium or sodium salts. The potassium ions
cannot be discharged at cathode until the
impressed voltage becomes large.
Instrumentation
Supporting electrolyte (Continued)
 The large number of potassium ions therefore remains
as a crowd around cathode and restrict the potential
gradient to a region so very close to the electrode
surface. So there is no longer an electrostatic
attraction operative to attract other reducible ions from
the bulk of the solution. Under these circumstances
the limiting current is solely controlled by the
diffusion of the electroactive species through the
concentration gradient adjacent to the electrode.
Diagram
Polarogram
 The data in polarography are best expressed
graphically in which current flow (in amperes)
versus potential variation is plotted along the
ordinate. This graph is called polarogram. A
polarogram has the S shape. The polarogram is
conveniently divided into three regions as A, B
and C.
Diagram
Polarogram
Residual current
 Region A results from the charging current of the electrode
and reduction of traces of impurities present in the solution.
This current is referred to as residual current. It include
 Faradic current, the current due to impurities
 Non-faradic current or capacitive current, the current due to
electrical double layer (Helmholtz double layer)
 ir = if + ic
 ir = Residual current
 if = Faradic current
 ic = Capacitive current
Polarogram
Migration current
 This current is due to migration of ions.
 By increasing the concentration of supporting
electrolyte, we can reduce the migration current.
Polarogram
Diffusion current
 Region B results from the reduction of the electro
active species in solution. The shape of the curve
in the region indicates that there are more
reducible species in the vicinity of electrode that
can be reduced.
Polarogram
 As the potential of the electrode is increased, more and
more of the reducible species are reduced (indicated by
the sharp rise in the current) until that point in the curve
is reached where an increase in the potential does not
give an increase in the current. This indicates that the
area in the vicinity of electrode is depleted of reducible
species and the reduction is then controlled by the rate
at which the species diffuse into this area. It is directly
proportional to the concentration of electro active
species.
Polarogram
Limiting current
 Beyond the certain potential, the current the steady
value called as the limiting current.
Half wave potential, E1/2
 The electro-active material in polarography is characterized
by its half-wave potential, E1/2.Under any defined set of
experimental conditions, each substance has its own
characteristic E1/2 and this is the basis of qualitative
polarographic analysis. The half-wave potential is defined as
the potential at which the current due t the reduction or
oxidation of the substance responsible for the wave is half as
large as on the plateau. The half-wave potential is also
independent of the electrode characteristics and
concentration of the electroactive substance, therefore serves
for the qualitative identification of an unknown substance.
IIkovic equation
In the presence of excess supporting electrolyte, the electrical force
on the reducible/oxidizable ions is nullified and therefore, the
limiting current is solely a diffusion current. Ilkovic (1934)
examined the various factors which govern the diffusion current
and deduced a theoretical equation as:
iD = 607 n cD1/2 m2/3 t1/6
 Where
 id = average diffusion current in microamperes during the life of
the drop
 n = the number of electrons consumed in the reduction or
oxidation of one mole of the electroactive species
 D = diffusion coefficient of the reducible or oxidizable
substance expressed as cm2/second
IIkovic equation
 c = concentration of electroactive species in millimoles
per dm3
 m = the rate of flow of mercury from the dropping
mercury electrode expressed in mg/second
 t = drop time of mercury in seconds
 The constant 607 is a combination of natural constants,
including the Faraday. This is an important equation
because it accounts for the linear dependence of i d upon c
keeping all other factors constant. It is useful in
quantitative polarographic analysis.
Polarographic maxima: Maxima
suppressors
 Current-voltage curves obtained with electro-
reducible ions at DME are frequently distorted by
increasing the current beyond the diffusion current
value and rapidly decrease to the normal diffusion
plateau after a critical value is reached as the
applied potential is increased. This abnormal
increase in current is referred as maxima which
vary in shape from sharp peaks to rounded humps.
Polarographic maxima: Maxima
suppressors
 To measure the true diffusion currents, the
maximum must be eliminated. This can be done by
adding small amount of surface-active agents such
as gelatin, dye stuff, Triton X-100 etc. which are
likely to form an adsorbed layer on the mercury-
solution interface to prevent streaming movement
of the diffusion layer at the interface.
Polarographic maxima: Maxima
suppressors
 Gelatin is widely used in the concentration range
of 0.002 to 0.01%. Higher concentration will
suppress the diffusion currents also. Others
frequently used are, Trition X-100 (a non-ionic
detergent) in the range of 0.002 to 0.004% and
methyl cellulose (0.005%).
Applications of Polarography
 Polarography is used predominantly for trace
metal analysis of alloys, ultra-pure
metals,minerals/metallurgy,environmental analysis
(air, water, soil and sea water contaminations),
food stuffs, beverages and body-fluids, toxicology
and clinical analysis.
Applications of Polarography
 It is also useful in the analysis of vitamins,
alkaloids, hormones, terpenoid substances and
natural coloring substances, analysis of drugs and
pharmaceutical preparations, determination of
pesticide or herbicide residues in the foods, in the
structure determination of many organic
compounds etc.
Applications of Polarography
 This technique is used in organic chemistry for
qualitative and quantitative analysis and structure
determinations. Most of the organic compounds
are insoluble in pure aqueous medium and also in
mercury amalgam. Therefore, the solvent in which
the organic compounds and its electrode product is
soluble is added to the supporting electrolyte.
Applications of Polarography
 These solvents include various alcohols and
ketones, dimethyl formamide, acetonitrile,
ethylene diamine and others. The commonly used
supporting electrolytes which are easily mixed
with organic solvents are various quaternary
ammonium salts such as tetrabutyl ammonium
iodide.
Thank You
Q&A