Thermochemistry and Kinetics for 2-Butanone-3yl Radical (CH3C(=O)CH•CH3) Reactions with O2
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Nadia Sebbar
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 chemically-activated 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-yl + O2, 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, Karlsruhe, Germany
Articles in the same Issue
- Preface
- OH and NH Stretching Vibrational Relaxation of Liquid Ethanolamine
- Transient anisotropy in degenerate systems: A semi-classical approach
- First Cavity Ring-Down Spectroscopy HO2 Measurements in a Large Photoreactor
- Relaxation Dynamics of Electronically Excited C60− in o-Dichlorobenzene and Tetrahydrofuran Solution
- 3CH2 + O2: Kinetics and Product Channel Branching Ratios
- What Do We Know About the Iconic System CH3 + CH3 + M ↔ C2H6 + M?
- Thermochemistry and Kinetics for 2-Butanone-3yl Radical (CH3C(=O)CH•CH3) Reactions with O2
- Experimental and Modelling Study of the Unimolecular Thermal Decompostion of CHF3
- Combustion Chemistry of the Butane Isomers in Premixed Low-Pressure Flames
- Characterization of Rhodamine 6G Release in Electrospray Ionization by Means of Spatially Resolved Fluorescence Spectroscopy
- Femtosecond interferometry of molecular dynamics – the role of relative and absolute phase of two individual laser pulses
- Photodecarbonylation of Diphenylcyclopropenone – a Direct Pathway to Electronically Excited Diphenylacetylene?
- Yield of HO2 Radicals in the OH-Initiated Oxidation of SO2
- Pyrolysis of Ethyl Iodide as Hydrogen Atom Source: Kinetics and Mechanism in the Temperature Range 950–1200 K
- Reaction of OH and NO at Low Temperatures in the Presence of Water: the Role of Clusters
Articles in the same Issue
- Preface
- OH and NH Stretching Vibrational Relaxation of Liquid Ethanolamine
- Transient anisotropy in degenerate systems: A semi-classical approach
- First Cavity Ring-Down Spectroscopy HO2 Measurements in a Large Photoreactor
- Relaxation Dynamics of Electronically Excited C60− in o-Dichlorobenzene and Tetrahydrofuran Solution
- 3CH2 + O2: Kinetics and Product Channel Branching Ratios
- What Do We Know About the Iconic System CH3 + CH3 + M ↔ C2H6 + M?
- Thermochemistry and Kinetics for 2-Butanone-3yl Radical (CH3C(=O)CH•CH3) Reactions with O2
- Experimental and Modelling Study of the Unimolecular Thermal Decompostion of CHF3
- Combustion Chemistry of the Butane Isomers in Premixed Low-Pressure Flames
- Characterization of Rhodamine 6G Release in Electrospray Ionization by Means of Spatially Resolved Fluorescence Spectroscopy
- Femtosecond interferometry of molecular dynamics – the role of relative and absolute phase of two individual laser pulses
- Photodecarbonylation of Diphenylcyclopropenone – a Direct Pathway to Electronically Excited Diphenylacetylene?
- Yield of HO2 Radicals in the OH-Initiated Oxidation of SO2
- Pyrolysis of Ethyl Iodide as Hydrogen Atom Source: Kinetics and Mechanism in the Temperature Range 950–1200 K
- Reaction of OH and NO at Low Temperatures in the Presence of Water: the Role of Clusters
