Combustion and atmospheric oxidation of hydrocarbons: Theoretical study of the methyl peroxyl self-reaction

Ghigo, Giovanni; Maranzana, Andrea; Tonachini, Glauco

doi:10.1063/1.1574316

Cited by 50 publications

(75 citation statements)

References 39 publications

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“…[29,28,34] The branching fractions reported in Scheme 5 are the result of numerical simulation (see below) of the experimentally observed product distribution of b-pinene. The reported values are in agreement with the quantitative struc-ture-activity relationship (QSAR) suggested by Capouet et al (i.e., (50 AE 20) % non-terminating cross-reactions for primary peroxyl radicals).…”

Section: O 2 ð3þmentioning

confidence: 99%

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Peculiarities of β‐Pinene Autoxidation

2011

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The thermal oxidation of the renewable olefin β-pinene with molecular oxygen was experimentally and computationally investigated. Peroxyl radicals abstract weakly bonded allylic hydrogen atoms from the substrate, yielding allylic hydroperoxides (i.e., myrtenyl and pinocarvyl hydroperoxide). In addition, peroxyl radicals add to the C=C bond of the substrate to form an epoxide. It was found that a relatively high peroxyl radical concentration, together with the high rate of peroxyl cross-reactions, make radical-radical reactions surprisingly important for this particular substrate. Approximately 60 % of these peroxyl cross-reactions lead to termination (radical destruction), keeping a radical chain length of approximately 4 at 10 % conversion. Numerical simulation of the reaction-based on the proposed reaction mechanism and known or predicted rate constants-demonstrate the importance of peroxyl cross-reactions for the formation of alkoxyl radicals, which are the precursor of alcohol and ketone products.

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Section: O 2 ð3þmentioning

confidence: 99%

“…According to Ghigo et al, [29] this leads to a loose complex, consisting of triplet oxygen and two alkoxyl radicals [Reaction (3)]. Hasson et al described the complex rather as alkoxyl and trioxyl radicals, with ROOOC decaying into 3 O 2 and ROC.…”

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confidence: 98%

Peculiarities of β‐Pinene Autoxidation

2011

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“…A second kind of kinetic study involves the destruction of the butyl peroxy radicals, which is generally via a self-reaction mechanism. 21 Simple kinetic experiments using CRDS spectral lines as a diagnostic enable us to follow the isomer, and possibly conformer, dependent kinetics.…”

Section: Reaction Chemistry and Kineticsmentioning

confidence: 99%

Near-IR Cavity Ringdown Spectroscopy and Kinetics of the Isomers and Conformers of the Butyl Peroxy Radical

Glover

Miller

2005

J. Phys. Chem. A

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Cavity ringdown spectra of butyl peroxy radicals have been obtained for their A − X electronic transition in the near IR. The radicals were produced by two independent chemical methods, allowing unambiguous assignment of the spectra of the four butyl peroxy isomers with probable conformer assignments also possible for a number of cases. Using the analyzed spectra semi-quantative, isomer specific rate constants for butyl peroxy self-reaction were measured, as was the relative reactivity of the various sorts of H atoms in butane to Cl atom attack.

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“…[1][2][3][4] Both categories have been comprehensively studied in this laboratory. (See, for example, Ref.…”

Section: Introductionmentioning

confidence: 99%

Rotationally resolved ${\tilde{B}} \leftarrow {\tilde{X}}$B̃←X̃ electronic spectra of the isopropoxy radical: A comparative study

Liu

Melnik

Miller

2013

The Journal of Chemical Physics

112

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The B̃-X̃ laser-induced-fluorescence spectrum of jet-cooled isopropoxy radical (i-C3H7O[middle dot]) has been recorded. Using an isolated state model the observed rotational and fine structure of the origin band has been well simulated to determine rotational constants for both the X̃ and B̃ states and the electron spin-rotation constants of the X̃ state. The line intensities are well simulated with a parallel transition type, requiring the same symmetry for the levels involved of each the X̃ and B̃ state, which confirms the previous suggestion that going from ethoxy (C2H5O[middle dot]) to isopropoxy, the energy ordering of the electron configurations with in- and out-of-plane half-filled p-orbitals of the oxygen atom is reversed and the ground vibronic symmetry changes from a" to a'. However, the observed spin-rotation coupling constants are not consistent with their predication from either semi-empirical theory or quantum chemical calculations. Additionally, the lack of observed transitions involving the out-of-plane transition moment component is not consistent with high level electronic structure calculations suggesting mixing of vibronic levels by strong spin-orbit coupling. A new twofold model has been developed that explicitly includes Coriolis and spin-orbit coupling between different vibronic levels. This model renders the discrepancy between theoretical and experimental spin-rotation constants moot. Moreover, it determines independently the contributions to the observed splitting between the lowest two levels, resulting from non-relativistic kinetic and Coulombic effects, and that due to the relativistic spin-orbit interaction. The experimental values show that these effects are comparable, but that the vibronic one is slightly more important. This result is at variance with state-of-the-art electronic structure calculations which otherwise do a remarkably good job of describing the ground state of isopropoxy.

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Combustion and atmospheric oxidation of hydrocarbons: Theoretical study of the methyl peroxyl self-reaction

Cited by 50 publications

References 39 publications

Peculiarities of β‐Pinene Autoxidation

Peculiarities of β‐Pinene Autoxidation

Near-IR Cavity Ringdown Spectroscopy and Kinetics of the Isomers and Conformers of the Butyl Peroxy Radical

Rotationally resolved ${\tilde{B}} \leftarrow {\tilde{X}}$B̃←X̃ electronic spectra of the isopropoxy radical: A comparative study

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