Insight Into The Ionizing Surface Potential Method And Aqueous Sodium Halide Surfaces

Complementing the microscopic picture of the surface structure of electrolyte solutions set out by previous theoretical and experimental studies, the ionizing surface potential technique offers a unique approach to quantifying the impact of aqueous inorganic ions upon the interfacial electric field of the air-aqueous interface. In this Feature Article, we review the vulnerability of theoretical and empirically derived chi(water) values as a normative reference for aqueous ion surface potentials. Instead, we recognize and evaluate aqueous ion surface potentials relative to well-known ionic surfactants cetyltrimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS). Additionally, we also explore factors that impact the magnitude of the measured surface potentials using the ionizing method, particularly in the type of reference electrode and ionizing gas environment. With potential measurements of sodium halide solutions, we show that iodide has a dominant effect on the air-aqueous electric field. Compared to chloride and bromide, iodide is directly observed with a net negatively charged surface electric field at all salt concentrations measured (0.2 to 3.0 mol/kg water). Also, above the 2 M region, bromide is observed with a net negatively charged surface. Although several scenarios contribute to this effect, it is most likely due to the surface enrichment of bromide and iodide. While the results of this study are pertinent to determining the specific interfacial reactivity of aqueous halides, these anions seldom transpire as single-halide systems in the natural environment. Therefore, we also provide an outlook on future research concerning surface potential methods and more complex aqueous electrolyte systems.