A second order group contribution method for the prediction of critical temperatures and enthalpies of vaporization of organic compounds

Didier Dalmazzone (1) , Anna Salmon (1) , Sofiane Guella (1)

1 UCP - Unité de Chimie et Procédés

A new method based on group contribution additivity, and using Benson's second order groups, is proposed for the prediction of critical temperatures and enthalpies of vaporization of covalent compounds. Contributions for hydrocarbons and hydrocarbon derivatives containing oxygen, nitrogen, chlorine, bromine and/or sulphur, are given. Results are compared to predictions made using the most common existing first or second order group contribution methods. The overall precision for Tc predictions of 381 compounds is 5.8 K, compared to 23.6 K with the method of Joback and 9.2 K with the method of Constantinou. The precision for predicted ΔHvap of 319 compounds, at 298 K and at the normal boiling point, is improved by a factor 2 when comparing to the results of the method of Svoboda. Furthermore, one single group decomposition may now be used for the computation of gas phase properties, Tc, and ΔHvap at any temperature lower than Tc, leading to liquid phase thermochemical functions with better precision and simplicity.

Mots clés: Critical temperature; Enthalpy of vaporization; Prediction; Group contribution

Domaines: Génie des procédés; Génie chimique; Chimie théorique et/ou physique

Didier Dalmazzone, Anna Salmon, Sofiane Guella. A second order group contribution method for the prediction of critical temperatures and enthalpies of vaporization of organic compounds. Fluid Phase Equilibria, 2006, 242 (1), pp.29-42. ⟨10.1016/j.fluid.2005.12.034⟩. ⟨hal-01179685⟩