Thermochemistry and kinetics for 2-butanone-3yl radical (CH 3C(=O)CH·CH3) reactions with O2
Document Type
Article
Publication Date
10-1-2011
Abstract
Thermochemistry and chemical activation kinetics for the reaction of the secondary radical of 2-butanone, 2-butanone-3yl, with 3O2 are reported. Thermochemical and kinetic parameters are determined for reactants, transition states structures and intermediates. Standard enthalpies and kinetic parameters are evaluated using ab initio (G3MP2B3 and G3), density functional (B3LYP/6-311g(d, p)) calculations and group additivity (GA). The C-H bond energies are determined for the three carbons of the 2-butanone, showing that the C-H bond energy (BE) on the secondary carbon is low at 90.5 kcal mol-1. The CH3C(=O)CH·CH3 radical + O2 association results in chemicallyactivated peroxy radical with 26 kcal mol-1 excess of energy. The chemically activated adduct can dissociate to butanone-oxy radical + O, react back to butanone-3yl + O 2, form cyclic ethers or lactones, eliminate HO2 to form an olefinic ketone, or undergo rearrangement via intramolecular abstraction of hydrogen to form hydroperoxide and/or OH radicals. The hydroperoxide-alkyl radical intermediates can undergo further reactions forming cyclic ethers (lactones) and OH radicals. Quantum RRK analysis is used to calculate k(E) and master equation analysis is used for evaluation of pressure fall-off in these chemical activated reaction systems. © by Oldenbourg Wissenschaftsverlag, München.
Identifier
80054922314 (Scopus)
Publication Title
Zeitschrift Fur Physikalische Chemie
External Full Text Location
https://doi.org/10.1524/zpch.2011.0144
ISSN
09429352
First Page
993
Last Page
1018
Issue
9-10
Volume
225
Recommended Citation
Sebbar, Nadia; Bozzelli, Joseph William; and Bockhorn, Henning, "Thermochemistry and kinetics for 2-butanone-3yl radical (CH 3C(=O)CH·CH3) reactions with O2" (2011). Faculty Publications. 11148.
https://digitalcommons.njit.edu/fac_pubs/11148