Effects of Solvent, Structure, and Temperature on the Ionization Equilibrium Constants of Phenols and Pyridinium Ions in Mixtures of Water and 1,4-Dioxane

An extensive collection of data has been used to study the effects of solvent, structure, and temperature on the ionization equilibrium constants of some substituted phenols and pyridinium ions in water–1,4-dioxane mixtures (0–70% weight fraction in dioxane) and temperatures ranging from 10 to 50◦C. The effects of structure and solvent are explained using Hammett’s equation and the Marshall–Quist model at all temperatures. An equation allowing an analysis of the three effects together on the pK values has been developed. The pK data under all experimental conditions fit this equation well, with standard errors of less than 0.3 pH units. Hammett’s reaction constant for the ionization of phenols and pyridinium ions has been obtained for all the experimental conditions. The pK and Hammett’s reaction constants for the different ionizations in water–1,4dioxane mixtures correlate well with Kamlet and Taft’s solvatochromic parameters π∗ and α, which measure the dipolarity/polarizability and hydrogen-bonding capacity of the solvent, respectively. These correlations explain more thoroughly the different contributions and origin of the effects of the solvent on the pK.