Abstract
The effect of electrode curvature on E− t curves obtained in Chronopotentiometry with non-linear perturbation of the form I(itt) = I 0t w ( w ⩾ − 1 2 ) after a blank period, t 1, at the DME, is presented. The cases where the reduction product dissolves both in the electrolyte solution and in the electrode are considered. Concentration profiles have been obtained, and reversibility criteria and methods for determining kinetic parameters of the charge transfer reaction are proposed. The theory has been experimentally verified with Fe(C 2O 4) 3− 3/Fe(C 2O 4) 4− 3, Tl +/Tl(Hg), Cr 3+/Cr 2+ and Zn 2+/Zn(Hg) using a linear currrent scan and a current step. The kinetic parameters of the two last systems have been determined.
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