Mechanism of formation of volatile organic compounds from oxidation of linseed oil
Juita, , Dlugogorski, B.Z., Kennedy, E.M. and Mackie, J.C. (2012) Mechanism of formation of volatile organic compounds from oxidation of linseed oil. Industrial & Engineering Chemistry Research, 51 (16). pp. 5653-5661.
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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.
|Publication Type:||Journal Article|
|Publisher:||American Chemical Society|
|Copyright:||© 2012 American Chemical Society.|
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