Surface chemistry and potential response of copper sulfide based ion-selective membrane in ligand solutions

Abstract

Dissolution of membraneous composite ions of copper sulfide precipitate-based ion-selective electrodes (ISEs) has been measured in various ligand solutions by ICP atomic emission spectrometry and atomic absorption spectrometry from the solution side and by X-ray photoelectron spectrometry on the electrode surface. Asymmetric dissolution, amount of copper dissolved is higher than that of sulfur, was generally observed. The copper dissolution is correlated with the potential response as well as conditional stability constants. The results are discussed in terms of the charge separation caused by the asymmetric dissolution and electrostatic interaction of charged ligands with the space charge on the electrode surface in view of microscopic characterization of ISEs in metal buffer solutions in general. The results were also used to clarify the reason for some discrepancies of complex stability constants obtained by precipitate-based ISEs and other methods.