Solvent selection is key in extractive distillation process development and solvent effects are often predicted based on the activity coefficients at infinite dilution. For close-boiling polar systems with strong or specific interacting species, standard simulation tools, e.g. using UNIFAC or COSMO-RS, often predict poor as the activity coefficients at infinite dilution not always reflect the selectivity in the process. For these systems, a heuristic solvent selection method in which molecular properties such as acidity, hydrogen bonding and polarity are applied is desired as first estimate in the solvent selection. To explore the key parameters for such a first selection, solvent effects on the relative volatility (a) were measured for three different industrially relevant polar mixtures, valeric acid-2-methylbutyric acid, diethylmethylamine - diisopropylether, and 2-butanol- 2-butanone. For each of the cases the effect of potential solvents on a was measured in an ebulliometer. For the acids, the difference in pK(a) of 0.1 was too small to separate based on acidity with a moderately basic solvent. Stronger basic solvents resulted in thermal and chemical instability. Although the solvent methyl-2-methyl butyrate is not suitable as a solvent because of reactivity, this structurally similar solvent showed selectivity, indicating also in extractive distillation the like dissolves like phenomenon can be applied to induce selectivity. A larger difference in basicity of the mixture components (amine-ether mixture) and a difference in hydrogen bonding affinity between the mixture components (ketone-alcohol mixture) allowed for increasing a based on differences in acidity and hydrogen bonding, respectively. (C) 2019 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.