Hydrogen atom bond increments for calculation of thermodynamic properties of hydrocarbon radical species

Abstract

Hydrogen atom bond increments (HBI) are defined and a data base is derived for accurately estimating ΔHf°298, S°298, and Cp(T) (300 ≤ T/K ≤ 1500) on generic classes of hydrocarbon (HC) radical species relevant to combustion and atmospheric chemistry, using these thermodynamic property increments. The HBI group technique is based on known thermodynamic properties of the parent molecule and calculated changes that occur upon formation of a radical via loss of a H atom. The HBI approach incorporates (i) evaluated literature bond energies, (ii) calculated entropy and heat capacity increments resulting from loss and/or change in vibrational frequencies including frequencies corresponding to inversion of the radical center, (iii) increments from changes in barriers to internal rotation, and (iv) spin degeneracy. Twenty five HBI groups corresponding to alkyl (primary, secondary, and tertiary), vinyl, allenic, allylic, benzyl, acetylenic, and other conjugated hydrocarbon radicals are defined, and their group values are calculated. The HBI groups, when coupled with thermodynamic properties of the appropriate "parent" molecule, yield accurate thermodynamic properties for the respective radicals. © 1995 American Chemical Society.