Empirical correlations of partial molar volumes at infinite dilution of organic solutes and transition states for SN1 and SN2 ethanolysis of alkyl halides

Abstract

Activation volumes are measured to be –21 to –29 cm³ mol^–1 for the ethanolysis of t-butyl chloride and bromide and methyl bromide in ethanol at 318.15 K. Partial molar volumes at infinite dilution are measured for 34 organic solutes. Partial molar volumes of the transition states can be treated in the same way as those of common solutes, in which the partial molar volume of each solute is compared with that of an alkane having the same van der Waals volume. The volume changes caused by the molecularity of reaction and the intermolecular interaction during the activation process are discussed.