Quantitative aspects of normalized differential reflectance spectroscopy: Pt(111) in aqueous electrolytes

A theoretical model is herein proposed to account for changes in the normalized differential reflectance, ΔR/R, of well-defined single crystal Pt(111) surfaces|aqueous electrolyte interfaces. It assumes that ΔR/R is proportional to the area of the electrode either bare or covered by neutral and/or nominally charged species and, for a specific type of site, is modulated by the applied potential, E. Correlations between the coverage of the various species and E were obtained from data reported in the literature or by coulometric analysis of linear voltammetric scans. Excellent agreement was found for the adsorption/desorption of hydrogen and that of bisulfate from acidic electrolytes both on bare, and cyanide-modified Pt(111). Also discussed are extensions of this technique in the transient mode involving the reduction of adsorbed nitric oxide, NO, on Pt(111).