title: Rate constants of oxidation of unsaturated fatty esters studied by chemiluminescence.
abstract: This study deals with oxidation kinetics of three unsaturated fatty esters: methyl oleate, methyl linoleate and methyl linolenate at temperatures ranging from 90 to 150 °C. The reaction was monitored by chemiluminescence. A kinetic model was derived from a simple mechanistic scheme, in which initiation is due to hydroperoxides decomposition, whereas propagation results from the abstraction of the most labile hydrogen and termination results only from the bimolecular combination of peroxyl radicals. Analysis of induction period duration indicated that hydroperoxides mainly decompose by a bimolecular process. The model well predicts the main features of the experimental chemiluminescence curves. Kinetic parameters of the three unsaturated fatty esters were assessed from inverse method and discussed.
authors.affiliation: Arts et Metiers ParisTech, CNRS, PIMM UMR 8006, 151 bd de l'Hôpital, 75013 Paris, France. emmanuel.richaud@ensam.eu
authors.forename: Emmanuel
authors.initials: E
authors.lastname: Richaud
authors.forename: Ludmila
authors.initials: L
authors.lastname: Audouin
authors.forename: Bruno
authors.initials: B
authors.lastname: Fayolle
authors.forename: Jacques
authors.initials: J
authors.lastname: Verdu
authors.forename: Lyda
authors.initials: L
authors.lastname: Matisová-Rychlá
authors.forename: Jozef
authors.initials: J
authors.lastname: Rychlý
mesh_terms: D004952:Esters; D006358:Hot Temperature; D007700:Kinetics; D008041:Linoleic Acids / Q000737:chemistry*; D008042:Linolenic Acids / Q000737:chemistry*; D008163:Luminescent Measurements; D008956:Models, Chemical; D015394:Molecular Structure; D009829:Oleic Acids / Q000737:chemistry*; D010084:Oxidation-Reduction; D020959:Polyethylene / Q000737:chemistry; D013329:Structure-Activity Relationship
chemical_list: D004952:Esters; D008041:Linoleic Acids; D008042:Linolenic Acids; D009829:Oleic Acids; C047376:methyl linolenate; C005575:methyl linoleate; C005576:methyl oleate; D020959:Polyethylene