Electrochemical Measurement of Interfacial Distribution and Diffusion Coefficients of Electroactive Species for Ion-Exchange Membranes: Application to Br 2 /Br - Redox Couple.

A novel method has been proposed for rapid determination of principal transmembrane transport parameters for solute electroactive co-ions/molecules, in relation to the crossover problem in power sources. It is based on direct measurements of current for the electrode, separated from solution by an ion-exchange membrane, under voltammetric and chronoamperometric regimes. An electroactive reagent is initially distributed within the membrane/solution space under equilibrium. Then, potential change induces its transformation into the product at the electrode under the diffusion-limited regime. For the chronoamperometric experiment, the electrode potential steps backward after the current stabilization, thus inducing an opposite redox transformation. Novel analytical solutions for nonstationary concentrations and current have been derived for such two-stage regime. The comparison of theoretical predictions with experimental data for the Br 2 /Br - redox couple (where only Br - is initially present) has provided the diffusion coefficients of the Br - and Br 2 species inside the membrane, D(Br - ) = (2.98 ± 0.27) 10 -6 cm 2 /s and D(Br 2 ) = (1.10 ± 0.07) 10 -6 cm 2 /s, and the distribution coefficient of the Br - species at the membrane/solution boundary, K(Br - ) = 0.190 ± 0.005, for various HBr additions (0.125-0.75 M) to aqueous 2 M H 2 SO 4 solution. This possibility to determine transport characteristics of two electroactive species, the initial solute component and its redox product, within a single experiment, represents a unique feature of this study.