M. Ciszkowska, Chem. Anal.  1999, 44, 391-403.

Volume 44, Number 3a (Special Issue)
Dedicated to Professor Adam Hulanicki on the occasion of 70th birthaday

Steady-State Current at Microelectrodes for Arbitrarily Charged Species and Various Concentrations of Supporting Electrolytes
by Malgorzata Ciszkowska
Department of Chemistry, Brooklyn College, The City University of New York, Brooklyn, NY 11210-2889

Key words: voltammetry, migration, stedy-state current, supporting electrolyte

Equations for the dependence of the limiting steady-state current on concentration of supporting electrolyte for arbitrarily charged species were developed based on the general theory of steady-state voltammetry by Myland and Oldham. The only limitations of the proposed model are that the electrode reaction must result in the neutral product and that diffusion coefficients of all species do not differ significantly. Theoretical predictions presented as a ratio of the limiting current, Il, to diffusional current, Id, are compared with experimental data for reduction of Tl+ and Cd+2 at mercury film microelectrodes in solutions of various concentrations and types of supporting electrolyte.  Experimental results agree well with theoretical predictions.