- Title
- Mechanism of formation of volatile organic compounds from oxidation of linseed oil
- Creator
- Juita,; Dlugogorski, Bogdan Z.; Kennedy, Eric M.; Mackie, John C.
- Relation
- ARC
- Relation
- Industrial & Engineering Chemistry Research Vol. 51, Issue 16, p. 5653-5661
- Publisher Link
- http://dx.doi.org/10.1021/ie202536n
- Publisher
- American Chemical Society
- Resource Type
- journal article
- Date
- 2012
- Description
- 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.
- Subject
- volatile organic compounds; oxidation; linseed oil
- Identifier
- http://hdl.handle.net/1959.13/1309241
- Identifier
- uon:21813
- Identifier
- ISSN:0888-5885
- Language
- eng
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