ISSN print edition: 0366-6352 ISSN electronic edition: 1336-9075 Registr. No.: MK SR 9/7 Published monthly

The method of dimensionless parameters for the calculation of polarographic currents governed by a chemical reaction in the solution

J. Koutecký

Czechoslovak Academy of Sciences, Prague

Abstract: The method of dimensionless parameters, in which the differential equations defining the problem are transformed into the forms with dimensionless independent variables, is described. A substantial simplification can be accomplished if the participating chem. reactions are very rapid. In such a case the influence of the reaction in the soln. can be respected under the boundary conditions. This is of utmost importance in nonunimol. reactions where the differential equations are not linear. If the depolarizer is formed by the reversible monomerization from an inactive dimer, then the problem of limiting currents and the problem of polarographic waves at the dimerization of the depolarization product can be formulated readily. The boundary conditions are nonlinear for the surface electrode, and the differential equations have a simple form of diffusion equation. In the theoretical research, the mechanism of depolarization and the processes in the immediate vicinity of the electrode require the most attention, as the problem of the transportation of the depolarizer to the surface of the electrodes seems to be solved in principle even for complicated depolarization schemes. There are only a few cases where the theory of depolarizer transformation is applicable, because the correct depolarization scheme is not known with a proper amt. of certainty.

Full paper in Portable Document Format: 810a693.pdf (in Czech)

Chemical Papers 8 (10) 693–701 (1954)