| Titre : | Mechanism of formation of volatile organic compounds from oxidation of linseed oil (2012) |
| Auteurs : | Juita, Auteur ; Bogdan Z. Dlugogorski, Auteur ; Eric M. Kennedy, Auteur |
| Type de document : | Article : texte imprimé |
| Dans : | Industrial & engineering chemistry research (Vol. 51 N° 16, Avril 2012) |
| Article en page(s) : | pp. 5653-5661 |
| Note générale : | Industrial chemistry |
| Langues : | Anglais |
| Tags : | Oxidation Volatile organic compound |
| Résumé : | The pathways of volatile organic compound (VOC) formation have been investigated through a computational study, employing the Gaussian 03 suite of programs. We optimized geometries and zero-point vibrational energies (ZPVEs) at the B3LYP/6-31G(d) level of theory and improved electronic energies by conducting single-point energy calculations using the large 6-311++G(3df,3pd) basis set. To describe the predominant mechanism of the linseed oil oxidation, the following sequence is proposed: hydrogen abstraction of unsaturated fatty compounds as the initiation reaction followed by the reaction of allylic-type radicals with molecular oxygen to form peroxyl radicals and finally intramolecular rearrangement through four- and five-membered rings. Quantum calculations identified low-energy pathways following cyclization resulting in the formation of major products observed, especially aldehydes and ketones. The overall energy changes taking place through the four- and five-membered rings were found to be 78 and 93 kJ mol-1 exothermic, respectively. Metal catalysts decompose hydroperoxides based on the Fenton-like mechanism into alkoxyl and peroxyl radicals. |
| ISSN : | 0888-5885 |
| En ligne : | http://cat.inist.fr/?aModele=afficheN&cpsidt=25834477 |
