Polarography
Voltammetry
• Involves measurement of current which is caused to flow as a result of application of a linear
potential to an electro-active system incorporating the species to be analysed
• Form of voltammetry most commonly used in Pharmaceutical analysis is polarography
Polarography
• Investigates the solution composition by reducing or oxidising metals, organic compounds or ions at
dropping mercury electrode (dme) which is a working electrode (indicator electrode/polarisable
electrode/ cathode)
• The sample in the suitable solution form is placed in an electrolytic cell which has polarisable (dme) and
non-polarisable electrode ( Anode/ calomel electrode or large mercury pool). This cell is known as a
polarographic cell. Large mercury pool is non polarisable because of its large surface area)
• The surface of the working electrode (dropping mercury electrode) is constantly renewed under dropping
conditions.
• A linear voltage ramp (in microvoltage) is applied progressing typically at 2-5mV/sec and the
corresponding current is measured and the current voltage data (CV data) is recorded graphically
• Depolarisation potential enables identification of ions present in the solution, and by measuring the
diffusion current (id) their concentration is calculated.
• The CV data (The S-shaped curve is called a polarogram and the associated electrical apparatus is called
the polarograph
Internal diameter: 0.05mm
Drop rate of Hg: one drop every 3-6 seconds.
Polarographic cell Potential: negative
Advantages of dme: constantly renewal of surface
Nitrogen gas eliminates presence of oxygen in the sample
Polarographic Wave Residual current (iR) :or background current: Current
produced by reducible impurities (iF= Faradic current)
which produces current at potential lesser than that
required for analyte ions
and due to Helmholtz double layer (K+ ions from
supporting electrolyte migrate towards the negatively
charged dme forming a double layer)Conc. Of
supporting electrolyte is 50-100 times greater than that
of analyte ion (iC) and voltage at working electrode is
not yet sufficient to reduce the analyte ions.
Migration current : Due to migration of K+ ions (from
supporting electrolyte towards DME). Because of high
concentration of supporting electrolyte the effect of
migration current due to analyte ions become
negligible)
Diffusion current (iD): Due to diffusion of analyte ion,
due to concentration gradient and the applied potential.
Based on Ilkovik equation, quantification of analyte ion
can be done.
Limiting current: As all the analyte ions have been
reduced, the current at working electrode becomes
limited or reaches a plateau.
Apparatus (Polarograph)
• Simple d.c polarography:
Requires potentiometer connected via a microammeter, to two electrodes, one of which is dme,
consisting of a mercury reservoir connected by a flexible polythene tube to a short length of very
fine capillary tubing and the other one a mercury pool anode.
The DME will continuously release mercury drops that range in diameter from 0.1 to 1mm in a
preset frequency. In case of analyses that involve metal ions, metal ions are reduced at the
negatively charged mercury drops due to diffusion of positive ions.
The third reference electrode is included in the cell, thereby fixing the relative voltages applied
between the electrodes.
Role of supporting electrolyte
• To suppress migration of analyte ions (mass transport of analyte ions due to electric field) , so
that diffusion remains the only kind of mass transfer of analyte ions in the reduction process at
the dme.
• It also enhances the conductivity of the solution
• The supporting electrolyte ions are not electrolysed at the applied potential range
• Eg KCl, KNO3
Applications and advantages
• Identification and quantification of metals (reducible substances) at micro scale (10-6 to10-2 M)
• When the solution contains several substances that are reduced or oxidised at different voltages,
the current voltage curve shows a separate current increase and separate limiting current for each
Hence several substances can be simultaneously determined .
Instrumentation
• Mercury cannot be used as electrode at positive potentials because of its oxidation.
• Therefore rotating platinum electrode at 600 revolutions per minute is used
• With platinum as electrode, the attainment of steady state diffusion current is slow and one has to wait for a
considerable time after each addition of the reagent and therefore platinum electrode is rotated.
• It consist of a glass tube of length 15 – 20 cm in length and 6 mm in diameter.
• The platinum wire extends 5-10 mm from the wall of glass tubing.
• The electrode is mounted on shaft of the motor and rotated at constant speed of 600 RPM .
• Electrical connection is made to the electrode by copper wire passing through the tubing to the mercury
covering the platinum wire seal.
