Kinetics of the cross-reaction of CH3O2 + HO2 radicals measured in the Highly Instrumented Reactor for Atmospheric Chemistry
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Kinetics of the cross-reaction of CH3O2 + HO2 radicals measured in the Highly Instrumented Reactor for Atmospheric Chemistry. / Østerstrøm, Freja F.; Onel, Lavinia; Brennan, Alexander; Parr, Joseph M.; Whalley, Lisa K.; Seakins, Paul W.; Heard, Dwayne E.
I: International Journal of Chemical Kinetics, 2023, s. 489-500.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
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TY - JOUR
T1 - Kinetics of the cross-reaction of CH3O2 + HO2 radicals measured in the Highly Instrumented Reactor for Atmospheric Chemistry
AU - Østerstrøm, Freja F.
AU - Onel, Lavinia
AU - Brennan, Alexander
AU - Parr, Joseph M.
AU - Whalley, Lisa K.
AU - Seakins, Paul W.
AU - Heard, Dwayne E.
N1 - Publisher Copyright: © 2023 The Authors. International Journal of Chemical Kinetics published by Wiley Periodicals LLC.
PY - 2023
Y1 - 2023
N2 - The sensitive Fluorescence Assay by Gas Expansion (FAGE) method has been used to detect methyl peroxy (CH3O2) and hydroperoxyl (HO2) radicals after their conversion by titration with excess NO to methoxy (CH3O) and hydroxyl (OH) radicals, respectively, to study the kinetics of the reaction of CH3O2 + HO2 radicals. The rate coefficient of the reaction was measured in the Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC) at 1000 mbar of synthetic air at T = 268–344 K, selectively detecting both radicals. Using a numerical model to fit both CH3O2 and HO2 radical temporal decays globally at each temperature investigated, rate coefficients for the reaction have been obtained. The room temperature rate coefficient was found to be kCH3O2 +HO2(295 K) = (4.6 ± 0.7) × 10−12 molecule−1 cm3 s−1 (2σ errors) and the temperature dependence of the rate coefficient can be characterized in Arrhenius form by kCH3O2 + HO2(268 K < T < 344 K) = (5.1 ± 2.1) × 10−13 × exp((637 ± 121)/T) cm3 molecule−1 s−1. The rate coefficients obtained here are 14%–16% lower than the literature recommended values with an uncertainty which is reduced significantly compared to previous reports.
AB - The sensitive Fluorescence Assay by Gas Expansion (FAGE) method has been used to detect methyl peroxy (CH3O2) and hydroperoxyl (HO2) radicals after their conversion by titration with excess NO to methoxy (CH3O) and hydroxyl (OH) radicals, respectively, to study the kinetics of the reaction of CH3O2 + HO2 radicals. The rate coefficient of the reaction was measured in the Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC) at 1000 mbar of synthetic air at T = 268–344 K, selectively detecting both radicals. Using a numerical model to fit both CH3O2 and HO2 radical temporal decays globally at each temperature investigated, rate coefficients for the reaction have been obtained. The room temperature rate coefficient was found to be kCH3O2 +HO2(295 K) = (4.6 ± 0.7) × 10−12 molecule−1 cm3 s−1 (2σ errors) and the temperature dependence of the rate coefficient can be characterized in Arrhenius form by kCH3O2 + HO2(268 K < T < 344 K) = (5.1 ± 2.1) × 10−13 × exp((637 ± 121)/T) cm3 molecule−1 s−1. The rate coefficients obtained here are 14%–16% lower than the literature recommended values with an uncertainty which is reduced significantly compared to previous reports.
KW - gas phase reactions
KW - global fitting
KW - kinetics
KW - radical-radical reactions
KW - temperature dependence
U2 - 10.1002/kin.21651
DO - 10.1002/kin.21651
M3 - Journal article
AN - SCOPUS:85159068215
SP - 489
EP - 500
JO - International Journal of Chemical Kinetics
JF - International Journal of Chemical Kinetics
SN - 0538-8066
ER -
ID: 347804703