Electrochimica Acta, Vol.39, No.14, 2129-2142, 1994
Comparative-Study Between the General-Solutions Presented in the Literature for the Double-Pulse Problem for a Slow Charge-Transfer Reaction
A detailed comparative study between the three general solutions in closed form for the double-pulse problem for a slow charge transfer reaction derived in the literature (M. Lovric and J. Osteryoung, Electrochim Acta 25, 96 (1982); Fatouros et al., J. electrcanal. Chem. 247, 37 (1988); and J. Galvez and M. L. Alcaraz, Electrochim. Acta (submitted)) is presented. Representative voltammograms to six significant figures for the most widely used pulse techniques, differential pulse polarography, differential normal pulse polarography, and reverse pulse polarography, as well as for the less familiar forward reaction rate controlled, backward reaction diffusion controlled mode, have been obtained. These results make clear that although an analytical correspondence between these solutions has not been established, they can be considered equivalent, at least numerically. For computation purposes, however, the behavior of these solutions is quite different, and their strengths and weaknesses are discussed. Finally, by comparing the results obtained with our former solution to this problem (J. Galvez et al., J. electroanal. Chem. 205, 21 (1986)) with those calculated from the general solution, allowed us to establish the conditions where the simplified equation can be used with certainty.