Polarography, Chemistry tutorial


Voltametry encompasses a sophisticated collection of analytical techniques in that the connection between voltage and current is examined during electrochemical procedures. The main subdivision of voltametry is polarography, a sensitive electro-analytical method that is especially helpful for trace analysis. The 2nd main categorization within voltametry is amperometry.

In polarography, the present flowing through the cell is computed as a function of the potential of the working electrode. Usually, this current is proportional to the concentration of the analyte. The most sensitive polarographic procedures have a detection limit near 10-9 M and a precision around 5%. Less sensitive polarographic techniques operating by ~10-3 M analyte are capable of a accuracy of a few tenths of percent, though 2.3% is most ordinary.


Polarography is a method in that the current flowing into an electrolysis cell is determined as a function of the applied potential.

Mode of Operation of a Simple Polarograph

Equipment for a direct-current polarograph experiment is revealed below. The mercury pool gives a huge area anode through little polarization. The attached mercury drop is the cathode and the stable detachment of the drops minimizes contamination. The nitrogen remains the solution free from oxygen that influences the performance harmfully. Potassium chloride electrolyte is utilized to enhance the conductivity since of huge negative discharge potential of the potassium ion. The applied voltage is steadily enlarged and the difference in current is computed. The potential of the cathode is computed through inserting into the solution, a standard electrode. Therefore:

Shape of a Polarogram

A graph of current vs. potential in a polarographic experiment is termed a polarogram, and for a solution enclosing only 1 dischargeable species, Mn+, it has the form revealed below: Theoretically, the current should be zero whenever the voltage is insufficient to generate the discharge potential in the cathode, but in practice, there will be several tiny current. When the discharge potential of the ion Mn+ is attained, the current enhances quickly as the voltage is enhanced until the concentration polarization becomes so huge that the limiting current is reached. Any further enhance in the applied voltage will generate little or no charge in the current. It has been revealed that the half wave potential P is independent of the ionic concentration, and for a specified potassium chloride concentration, there is a joined value of P that corresponds to a specified ionic species. This enables qualitative determinations to be carried out. ID is recognized as the limiting diffusion current that is dependent on the concentration of Mn+. Therefore, quantitative determinations can as well be possible.

Applications of Polarography

  • The method is effectual in the qualitative identification of an unknown.
  • Polarographic procedure can be utilized to learn the rates of chemical reactions that compete through the electrode reactions.
  • It can as well be utilized to find out more than one ionic species in solution; but this needs a series of steps of the similar form that occurs when the discharge potential of each species is reached.
  • The technique is as well effective in the determination of extremely dilute solutions.

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