Mise au point et analyse critique de méthodes de calcul prédictif des grandeurs thermochimiques des composés du soufre : approches empirique et ab initio

Abstract : The aim of this study is to provide a critical analysis of predictive methods for calculating thermochemical quantities via two approaches, one based on empirical group contributions and a second based on ab initio quantum mechanics. Our work consisted in comparing both approaches in the particular case of the prediction of standard formation enthalpies of organic sulphur compounds in the liquid state. An extension of the Benson's group contribution method based on a set of 400 sulphur containing molecules leaded to identify 53 new group contributions and 11 structure corrections for the prediction of liquid phase enthalpies of formation. These results were validated with a set of 18 molecules and a comparison with an existing analogous method was performed. On the other hand, electronic and thermal contributions to molecular energies were calculated using DFT quantum chemistry. Molecular energies were then converted to standard molar enthalpies of formation by optimizing conversion parameters using experimental data of a set of 195 reference molecules. Finally, a correlation between vaporization enthalpies and the variance of electrical potential on the molecular surface was used to access the liquid phase enthalpies of formation. Comparing the results of the different methods allowed discussing the applicability of both approaches for chemical engineering applications. This work also included an experimental study, which consisted in adapting a rotating oxygen bomb combustion calorimeter to the measurement of combustion energies of sulphur compounds.
Complete list of metadatas

Cited literature [14 references]  Display  Hide  Download

https://pastel.archives-ouvertes.fr/pastel-00623806
Contributor : Bibliothèque Mines Paristech <>
Submitted on : Thursday, September 15, 2011 - 10:53:26 AM
Last modification on : Wednesday, July 3, 2019 - 10:48:04 AM
Long-term archiving on : Friday, December 16, 2011 - 2:21:21 AM

Identifiers

  • HAL Id : pastel-00623806, version 1

Citation

Mohammed Ellaite. Mise au point et analyse critique de méthodes de calcul prédictif des grandeurs thermochimiques des composés du soufre : approches empirique et ab initio. Génie des procédés. École Nationale Supérieure des Mines de Paris, 2010. Français. ⟨NNT : 2010ENMP0072⟩. ⟨pastel-00623806⟩

Share

Metrics

Record views

689

Files downloads

214