Reactions of Amalgam-Forming Metals on Thin Mercury Film Electrodes

Reactions of Amalgam-Forming Metals on Thin Mercury Film Electrodes 

At a thin mercury film electrode, the dimensionless net peak current A p of a reversible redox reaction + m ti M(Hg) depends on the dimensionless film thickness A = where / is the real film thickness [55]. A classical 

At a very thin film (A 0.1), the real peak current of the reversible reaction (II.3.1) is linearly proportional to the frequency because A p linearly depends on the parameter A [59, 60]. In reaction (II.3.1) it is assumed that only the species Red is initially present in the solution. This is the condition usually encountered in anodic stripping square-wave voltammetry [Red s M(Hg)]. In the range 0.1 A 5, A p monotonously increases with A from 0.03 to 0.74, without a maximum for A = 1. The peak width changes from 99In mV (for A 0.3) to 124/n mV, for A 3 [60,61]. Simulations of SWV in the restricted diffusion space were extended to a thin layer cell [62]. The influence of electrode kinetics on direct and anodic stripping SWV on thin mercury film electrodes was analyzed recently [63-65]. 

SWV can be applied to systems complicated by preceding, subsequent, or catalytic homogeneous chemical reactions [38, 66-69]. Theoretical relationships between the measurable parameters, such as peak shifts, heights and widths, and the appropriate rate constants, were calculated and used for the extraction of kinetic information from the experimental data [66,67]. 

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