Binary solvent mixtures: Characterization of molecular environments throughmultiparametric empirical scales. Concerns about relationships between kineticdata and microscopic solvent properties

Abstract

The microscopic solvent properties dipolarity/polarizability SPP, basicity SB and acidity SA were determined for binary mixtures of ethyl acetate with chloroform or acetonitrile or methanol as cosolvent. Each solvent system was analyzed according to its deviation from ideal behavior due to the preferential solvation phenomenon. The results were related to the dipolarity/polarizability π*, basicity β and acidity α evaluating, in each case, the concordance between both multiparametric scales. The solvent properties were correlated with the kinetic properties corresponding to a nucleophilic aromatic substitution reaction through linear free energy relationships. The adequacy of the multiparametric scales as appropriate approaches to describe the solvent features in microscopic environments was analyzed.