"Void" and "expansion" volume contributions to reaction and activation volumes of nearly nonpolar reactions

Abstract

The reaction volume, ΔV, (and the activation volume, ΔV≠) of nearly nonpolar reactions are divided into three terms: i) van der Waals volume change, ΔV_W, ii) void volume change, ΔV_v and iii) expansion volume change, ΔV_E. Each contribution is estimated by means of Bondi's V_W, Miller's V_0 (volume of the hypothetical liquid at 0°K) and the known densities of hydrocarbons for the reactions of pure liquids. Unexpectedly the results clearly indicate that ΔV_W is a rather minor factor.