A program has been undertaken to develop a new group contribution method, based on Benson’s group additivity technique, estimate as precisely as possible solid state enthalpies of formation, at 298.15K, of C–H compounds, C–H–O compounds, and C–H–N–O compounds. A set of 1017 experimental values of the enthalpy of formation has been studied and compared to the predicted values of this new method as well as the method of Domalski and Hearing. This new estimation technique leads to a higher precision and reliability. With the inclusion of additional group values, a wider range of compounds can be studied (compared to the Domalski and Hearing technique). Comparison with a quantum mechanical method [Rice et al., Combust. Flame 118, 445 (1999)] shows that the list of group contribution values, ring strain corrections, and non-nearest neighbor interactions provided here yields better estimates overall.

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A predictive method, based on Benson's group additivity technique, is developed for calculating the enthalpy of formation in the solid phase, at 298.15 K, of carbon-hydrogen compounds and carbon-hydrogen-oxygen compounds. A complete database compiles 398 experimental enthalpies of formation. The whole group contribution values, ring strain corrections, and nonnearest neighbor interactions evaluated are listed. Finally a comparison with Cohen's method indicates that this new estimation method leads to higher precision and reliability.