Assignment of reference pH-values to primary standard buffer solutions for standardization of potentiometric sensors in acetonitrile-water mixtures.

Abstract

Standard pH-values pH(PS) for seven primary standard buffer solutions in 0, 10, 30, 40, 50, 70 and 100% (w/w) acetonitrile-water mixed solvents at 298.15 K were determined according to the criteria recently endorsed by IUPAC. The preferential solvation of the ions in acetonitrile-water mixtures was studied in order to clarify the acid-base behaviour of the solutes in such mixtures. The influence of variation in the solvent composition on pH(PS) values was considered with a view to obtaining correlations that can be used to determine the pH(PS) values in any acetonitrile-water mixture up to 70% (w/w) acetonitrile. The pH(PS) values were then correlated with the weight and volume percentages and molar fraction of acetonitrile and with the Kamlet-Taft, pi(*), alpha and beta solvatochromic parameters of the acetonitrile-water mixtures. The equations obtained permit the standardization of potentiometric sensors in these mixtures.