Gas phase addition kinetics of the <i>tert</i>‐butyl radical to oxygen

Dilger, Herbert; Stolmár, Martina; Tregenna‐Piggott, Philip L. W.; Roduner, Emil; Reid, I. D.

doi:10.1002/bbpc.19971010610

Cited by 15 publications

(18 citation statements)

References 22 publications

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“…1,2 For the QOOH species investigated in this work, the rate coefficient for QOOH + O2 is less than that for the analogous R + O2 reaction by a factor of ~10. [27][28][29][30] In contrast, the rate coefficient for QOOH + O2 for the QOOH species derived from 1,3-cycloheptadiene was shown to be greater than that for the analogous R + O2 by a factor of ~10. 7 The use of R + O2 kinetics to estimate QOOH + O2 reaction rates may therefore require greater consideration of the effects of any resonance stabilisation and more detailed examination of the relevant potential energy surfaces.…”

Section: Qooh (Ch2(ch3)2cooh) + O2 Kineticsmentioning

confidence: 80%

Temperature and Pressure Dependent Kinetics of QOOH Decomposition and Reaction with O₂: Experimental and Theoretical Investigations of QOOH Radicals Derived from Cl + (CH₃)₃COOH

et al. 2019

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QOOH radicals are key species in autoignition, produced by internal isomerisations of RO2 radicals, and are central to chain branching reactions in low temperature combustion. The kinetics of QOOH radical decomposition and reaction with O2 have been determined as a function of temperature and pressure, using observations of OH radical production and decay following H-atom abstraction from tertiary-butyl hydroperoxide ((CH3)3COOH) by Cl atoms to produce QOOH ( . CH2(CH3)2COOH) radicals. The kinetics of QOOH decomposition have been investigated as a function of temperature (251 to 298 K), and pressure (10 to 350 Torr), in helium and nitrogen bath gases, and those of the reaction between QOOH and O2 have been investigated as a function of temperature (251 to 304 K), and pressure (10 to 100 Torr) in He and N2. Decomposition of the QOOH radicals was observed to display temperature and pressure dependence, with a barrier height for decomposition of (44.7 ± 4.0) kJ mol -1 determined by master equation fitting to the experimental data. The rate coefficient for the reaction between QOOH and O2 was determined to be (5.6 ± 1.7) × 10 -13 cm 3 s -1 at 298 K, with no significant dependence on pressure, and can be described by the Arrhenius parameters A = (7.3 ± 6.8) × 10 -14 cm 3 s -1 and Ea = -(5.4 ± 2.1) kJ mol -1 in the temperature range 251 to 304 K. This work represents the first measurements of any QOOH radical kinetics as a function of temperature and pressure.

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Section: Qooh (Ch2(ch3)2cooh) + O2 Kineticsmentioning

confidence: 80%

Temperature and Pressure Dependent Kinetics of QOOH Decomposition and Reaction with O₂: Experimental and Theoretical Investigations of QOOH Radicals Derived from Cl + (CH₃)₃COOH

et al. 2019

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“…For 1°and 3°a lkyl radical addition we use the Lenhardt et al [61] measured rates of addition for n-butyl and tert-butyl radicals to O 2 which are 4.52 ϫ 10 12 and 1.41 ϫ 10 13 cm 3 mol Ϫ1 s Ϫ1 , respectively. Dilger et al [62] measured the rate of tert-butyl radical addition to be 4.09 ϫ 10 12 exp(ϩ572 cal/RT) cm 3 mol Ϫ1 s Ϫ1 , which is is a little less than half Lenhardt's value at 700 K.…”

Section: Reaction Type 10: ṙ ؉ O 2 Additionmentioning

confidence: 96%

A comprehensive modeling study of iso-octane oxidation

Curran

2002

Combustion and Flame

1,234

722

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A detailed chemical kinetic mechanism has been developed and used to study the oxidation of iso-octane in a jet-stirred reactor, flow reactors, shock tubes and in a motored engine. Over the series of experiments investigated, the initial pressure ranged from 1 to 45 atm, the temperature from 550 K to 1700 K, the equivalence ratio from 0.3 to 1.5, with nitrogen-argon dilution from 70% to 99%. This range of physical conditions, together with the measurements of ignition delay time and concentrations, provide a broad-ranging test of the chemical kinetic mechanism. This mechanism was based on our previous modeling of alkane combustion and, in particular, on our study of the oxidation of n-heptane. Experimental results of ignition behind reflected shock waves were used to develop and validate the predictive capability of the reaction mechanism at both low and high temperatures. Moreover, species' concentrations from flow reactors and a jet-stirred reactor were used to help complement and refine the low and intermediate temperature portions of the reaction mechanism, leading to good predictions of intermediate products in most cases. In addition, a sensitivity analysis was performed for each of the combustion environments in an attempt to identify the most important reactions under the relevant conditions of study.

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“…4 and 5 are quantitatively converted to the corresponding peroxy isomer. [22][23][24] To a first approximation, it is also reasonable to assume that the oscillator strength of the A − X transition is isomer independent. In this case the intensity of the respective CRDS peroxy radical spectra is a good measure of…”

Section: Atom Attack On Butanementioning

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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Gas phase addition kinetics of the tert‐butyl radical to oxygen

Cited by 15 publications

References 22 publications

Temperature and Pressure Dependent Kinetics of QOOH Decomposition and Reaction with O₂: Experimental and Theoretical Investigations of QOOH Radicals Derived from Cl + (CH₃)₃COOH

Temperature and Pressure Dependent Kinetics of QOOH Decomposition and Reaction with O₂: Experimental and Theoretical Investigations of QOOH Radicals Derived from Cl + (CH₃)₃COOH

A comprehensive modeling study of iso-octane oxidation

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

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Gas phase addition kinetics of the tert‐butyl radical to oxygen

Cited by 15 publications

References 22 publications

Temperature and Pressure Dependent Kinetics of QOOH Decomposition and Reaction with O2: Experimental and Theoretical Investigations of QOOH Radicals Derived from Cl + (CH3)3COOH

Temperature and Pressure Dependent Kinetics of QOOH Decomposition and Reaction with O2: Experimental and Theoretical Investigations of QOOH Radicals Derived from Cl + (CH3)3COOH

A comprehensive modeling study of iso-octane oxidation

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

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Temperature and Pressure Dependent Kinetics of QOOH Decomposition and Reaction with O₂: Experimental and Theoretical Investigations of QOOH Radicals Derived from Cl + (CH₃)₃COOH

Temperature and Pressure Dependent Kinetics of QOOH Decomposition and Reaction with O₂: Experimental and Theoretical Investigations of QOOH Radicals Derived from Cl + (CH₃)₃COOH