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

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