Relationships between computed and experimentally determined molecular volumes and radii

Abstract

Theoretically computed molecular volumes and radii based on overlapping van der Waals spheres have been derived for a wide range of inorganic molecular ions and compared with experimentally determined partial molal volumes and thermochemical radii. The correlations are remarkably good and may be used to estimate with some confidence either the partial molal volumes of ions which have not been experimentally determined or the lattice energies of molecular salts. The accuracy of the calculated partial molar volumes may be sufficient to calculate the molar volumes of activation for transition states.