GENERAL ANALYTICAL SOLUTION FOR A REVERSIBLE I T RESPONSE TO A DOUBLEPOTENTIAL STEP AT SPHERICAL ELECTRODES IN THE ABSENCE/PRESENCE OF AMALGAMATION EFFECTS/

The general rigorous theory corresponding to double potential step chr onoamperometry for a reversible charge transfer reaction in a spherica l electrode whose area increases with t(z), where z greater than or eq ual to 0, is presented. The static mercury drop electrode (z = 0) and the dropping mercury electrode (z = 2/3) are addressed specifically. T he explicit equations for the current versus time response assuming un equal diffusion coefficients for the oxidized and reduced species are valid when the product is soluble in both the electrolytic solution an d the electrode. Comparisons with previous general treatments in the l iterature are made. The theory is applied to the detection of amalgama tion in RP and DNP techniques. Moreover, in this work we show the orig in of errors appearing in some general treatments in the literature, t hese errors lead to physically meaningless results when amalgamation t akes place.