Generalized treatment of alkanes

Abstract

A generalized procedure for predicting the energies of the paraffinic hydrocarbons is given taking into consideration (i) interactions between pairs of bonds attached to a carbon atom, (ii) interactions between trios of bonds attached to a carbon atom, (iii) interactions between pairs of bonds separated by a C—C bond, and (iv) steric terms corresponding to higher order interactions. This model without the steric terms is justified by the molecular orbital treatment of paraffins given by Brown, in which the molecular orbitals were represented as linear combination of bond orbitals (L.C.B.O. approximation). The derived equation for the energies of the paraffinic hydrocarbons without the steric terms justifies Tatevskii's empirical approach and can also be reduced to Laidler's equation. Further, the derived equation reveals the limitations of the Allen's scheme. A new approach based on Skinner's angle release mechanism has been suggested for the calculation of the steric repulsion energies.