CHEMISTRY GLOSSARY

polarography    →   polarografija

Polarography is a volumetric technique which is based on a diffusion controlled analyte travel to the surface of dropping mercury electrode (DME). The surface of the working electrode (dropping mercury electrode) is constantly renewed under dropping conditions and, thus, the conditions under which reaction takes place are readily reproducible. Depolarisation potential enables identification of ions present in the solution, and by measuring the diffusion current their concentration is calculated. Polarography was discovered in 1922 by the Czech chemist Jaroslav Heyrovský (1890-1967).

dropping mercury electrode    →   kapajuća živina elektroda

Dropping mercury electrode (DME) is a working electrode arrangement for polarography in which mercury continuously drops from a reservoir through a capillary tube (internal diameter 0.03 - 0.05 mm) into the solution. The optimum interval between drops for most analyses is between 2 and 5 s. The unique advantage to the use of the DME is that the constant renewal of the electrode surface, exposed to the test solution, eliminates the effects of electrode poisoning.

Ilkovic equation    →   Ilkovičeva jednadžba

Ilkovic equation is a relation used in polarography relating the diffusion current (i_d) and the concentration of the depolarizer (c), which is the substance reduced or oxidized at the dropping mercury electrode. The Ilkovic equation has the form

Where k is a constant which includes Faraday constant, π and the density of mercury, and has been evaluated at 708 for max current and 607 for average current, D is the diffusion coefficient of the depolarizer in the medium (cm²/s), n is the number of electrons exchanged in the electrode reaction, m is the mass flow rate of Hg through the capillary (mg/sec), and t is the drop lifetime in seconds, and c is depolarizer concentration in mol/cm³.

The equation is named after the scientist who derived it, the Slovak chemist, Dionýz Ilkovič 1907-1980).

Heyrovsky-Ilkovic equation    →   Heyrovsky-Ilkovičeva jednadžba

The Heyrovsky-Ilkovic equation describes the entire current-potential curve (polarographic wave) of a reversible redox system in polarography

where R is the gas constant, T is the absolute temperature, F is the Faraday constant, n denotes the number of electrons taking part in the electrode reaction. E_1/2 is a unique potential (for a given reaction and supporting electrolyte) termed the half-wave potential.

In order to obtain E_1/2 from the above equation, we plot a graph of ln[(i_d-i)/i] against E. The intercept on the x-axis gives then an accurate value of E_1/2. The slope of the obtained straight line is equal to nF/RT from which n is determined.