Molecular polarizability of organic compounds and their complexes: LII. Molar volumes of polymeric compounds in solutions, extrapolated to infinite dilution, and steric structure of their molecules

Abstract

The molar volumes in solutions at infinite dilution were determined for a series of vinyl, glycol, isoprene, and cyclopentadiene polymers and oligomers with various degrees of polymerization. An additive analysis of the molar volumes showed that molecules of vinyl, ethylene glycol, and isoprene polymers exist in solutions in elongated helical conformations. In the majority of polymer molecules, except polystyrenes, polyisoprenes, and polycyclopentadienes, there are randomly disordered regions creating additional volumes inaccessible to solvation with solvent molecules. Cyclopentadiene oligomers formed by the Diels-Alder reaction have in solution the conformation of corrugated bands. The additive scheme for calculating the molar volumes considerably simplifies the determination of the dipole moments and Kerr constants of the compounds for which this scheme has been constructed.