Abstract
The values of the solvatochromic parameters α and β were determined at 25°C for dioxane-water mixtures from 0 to 100% of dioxane. These values as well as those of the Reichardt polarity parameter E T (30) and the polarity-polarizability π* are correlated with acid dissociation constants and other equilibrium constants in solvent mixtures of the same composition. As a general rule, two linear zones with different slopes are obtained, one zone covering water-rich solutions, and the other dioxane-rich solutions. The change in behavior takes place at about 55% (v/v) dioxane for all equilibria studied. A fit of pK to an equation of the multiparametric form proposed by Kamlet and Taft shows in most cases a linear dependence on π* alone, in other cases a dependence on π* and β.
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Casassas, E., Fonrodona, G. & de Juan, A. Solvatochromic parameters for binary mixtures and a correlation with equilibrium constants. Part I. Dioxane-water mixtures. J Solution Chem 21, 147–162 (1992). https://doi.org/10.1007/BF00647004
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DOI: https://doi.org/10.1007/BF00647004