Abstract
A computer program was written to calculate and display graphically the van der Waals volume (Vw) and surface area (Sw) of molecules. Using van der Waals radii of C, H, Cl, and Br, and geometries optimised by the force-field method, Vw and Sw were obtained for about a hundred simple molecules: alkanes, cycloalkanes, and chlorinated and brominated derivatives thereof. Sw is more sensitive than Vw to stereochemical and positional isomerism. It was found that Vw correlates with the molar refraction and with the constant b in the equation of state, and can be used to estimate the molar volume. For very similar species, Sw correlates with the free volume that encapsulates the molecule in the bulk, so that a combined usage of Vw and Sw leads to the difference in molar volume between conformers. Numbers obtained by the procedure bear upon the ‘conformational rule’ of organic stereochemistry, and suggest a novel interpretation of the torsional term in the molecular-mechanical force field.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callMore From: Journal of the Chemical Society, Perkin Transactions 2
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
