Modes of triple-pulse voltammetry for a slow charge transfer reaction: Analysis of the zeroth-order solution for these modes

Recently the rigorous solution for the triple-pulse problem has been derived (J. Galvez, J. Electroanal. Chem. 482 (2000) 66). This solution can be applied for any pulse height and duration and involves a main contribution, the zeroth-order solution, and higher-order corrections so that we can compute the response to any degree of accuracy by adding to the zeroth-order solution as many of these corrections as are necessary. In this work a study of the different modes of pulse voltammetry derived from that solution is presented. To this end, representative voltammograms to four significant figures are given. This allows us to establish the conditions where the zeroth-order equation can be used. Also, a comparative study with the simplified equation previously derived for this problem (Serna et al., Anal. Chem. 69 (1993) 215) has been performed and some issues that arise in this type of studies are discussed.