Title: Semiintegral Electroanalysis in the Absence of Supporting Electrolyte
Abstract: Abstract The limiting semiintegral of the current which flows when a stationary electrode is progressively polarized in the presence of electroactive species has been investigated under the condition of no supporting electrolyte present in the solution. The semiintegral, m(t), of the current, i(t), is defined by m(t)=\fracd^-1/2dt^-1/2i(t)=\frac1π^1/2∫_0^t\fraci(λ)(t-λ)^1/2dλ. The electroreduction of a number of heavy metal ions has been studied at a mercury drop electrode and it was found that the limiting semiintegral is larger than that observed with excess supporting electrolyte present. The finding is in agreement with a simple theory which considers both diffusion and migration mass transfer processes. The factor by which the limiting semiintegral increases has been shown to depend on the diffusion coefficients and charge numbers of the cation and anion.