Towards a general scheme for estimating the heats of formation of organic ions in the gas phase. Part I. Odd-electron cations

Abstract

It is shown that gas-phase heats of formation of homologous odd-electron organic cations can be well represented by an equation of the form ΔHf[ion]+• = A − Bn + C/n, where A, B, and C are constants and n is the total number of atoms in the molecule. Values for A, B, and C have been determined for the linear homologous series: alkanes, olefins, alkynes, alkanols, aliphatic ethers, aliphatic aldehydes, aliphatic ketones, alkanoic acids, alkyl chlorides, bromides, and iodides. For each of these series, correction terms for chain branching, double-bond position, and asymmetry effects are also given. These equations can be applied to molecules containing 40 or more atoms. The data base for this work is also presented.