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It was observed by Grunwald that acid-base equilibria in several pure and mixed hydroxylic solvents could be treated by the relation log f/sub A//f/sub AH/ -- m/sub A/Y wherein f/sub A/and f/sub AH/ are degenerate activity coeifficients of a base and its conjugate acid, respectively, m/sub A/ is a parameter depending only upon the base, and Y is a parameter depending only on the solvent and charge type of the base. It is shown in this work that the proton donating ability of a solvent can be related to a suitable function of appropriate m values. Utilizing Grunwald's data for mixtures of water and ethanol, values of m/sub A/ are derived for the solvent components. In addition, a relationship is derived between the proton donating ability of a solvent and the Hammett acidity function. This relationship is shown to correlate data already available in the literature on the Hammett acidity function in water- ethanol mixtures. (auth)

Substituent effects on the stability of metal chelates and further relationships in the Grunwald treatment of acid-base equilibria in hydroxylic solvents