Whelan, CA, Blitz, MA orcid.org/0000-0001-6710-4021, Shannon, R et al. (4 more authors) (2019) Temperature and Pressure Dependent Kinetics of QOOH Decomposition and Reaction with O2: Experimental and Theoretical Investigations of QOOH Radicals Derived from Cl + (CH3)3COOH. The Journal of Physical Chemistry A, 123 (47). acs.jpca.9b08785. pp. 10254-10262. ISSN 1089-5639
Abstract
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 cm3 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 cm3 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.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2019 American Chemical Society. This is an author produced version of a journal article published in Journal of Physical Chemistry A. Uploaded in accordance with the publisher's self-archiving policy. |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemistry (Leeds) > Physical Chemistry (Leeds) |
Funding Information: | Funder Grant number NERC NE/L010798/1 |
Depositing User: | Symplectic Publications |
Date Deposited: | 31 Oct 2019 11:27 |
Last Modified: | 29 Oct 2020 01:38 |
Status: | Published |
Publisher: | American Chemical Society |
Identification Number: | 10.1021/acs.jpca.9b08785 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:152873 |