The atmospheric chemistry of the HC(O)CO radical

Tyndall, Geoffrey S.

doi:10.1002/1097-4601(200103)33:3<149::aid-kin1008>3.0.co;2-1

Cited by 60 publications

(82 citation statements)

References 28 publications

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“…than the decomposition pathway HOCH 2 CO→CH 2 OH+CO. Conversely, decomposition is predicted to be much more rapid for the case of HC(O)CO, in agreement with the experiments of Orlando and Tyndall (2001).…”

Section: Introductionsupporting

confidence: 85%

Total Peroxy Nitrates (ΣPNs) in the atmosphere: the Thermal Dissociation-Laser Induced Fluorescence (TD-LIF) technique and comparisons to speciated PAN measurements

et al. 2010

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Abstract. Peroxyacetyl nitrate (PAN) and its chemical analogues are increasingly being quantified in the ambient atmosphere by thermal dissociation (TD) followed by detection of either the peroxyacyl radical or the NO 2 product. Here we present details of the technique developed at University of California, Berkeley which detects the sum of all peroxynitrates ( PNs) via laser-induced fluorescence (LIF) of the NO 2 product. We review the various deployments and compare the Berkeley PNs measurements with the sums of PAN and its homologue species detected individually by other instruments. The observed TD-LIF PNs usually agree to within 10% with the summed individual species, thus arguing against the presence of significant concentrations of unmeasured PAN-type compounds in the atmosphere, as suggested by some photochemical mechanisms. Examples of poorer agreement are attributed to a sampling inlet design that is shown to be inappropriate for high NO x conditions. Interferences to the TD-LIF measurements are described along with strategies to minimize their effects.

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Section: Introductionsupporting

confidence: 85%

Total Peroxy Nitrates (ΣPNs) in the atmosphere: the Thermal Dissociation-Laser Induced Fluorescence (TD-LIF) technique and comparisons to speciated PAN measurements

et al. 2010

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“…The rate constant calculated by da Silva is considerably lower than the experimental value reported by Orlando and Tyndall 42 for 0.92 atm and 224−370 K. However, the latter determination was affected by the use of a too large rate constant value for OCHCO + O 2 , as pointed out by da Silva.…”

Section: ■ Detailed Kinetic Modelmentioning

confidence: 60%

Glyoxal Oxidation Mechanism: Implications for the Reactions HCO + O₂ and OCHCHO + HO₂

et al. 2015

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A detailed mechanism for the thermal decomposition and oxidation of the flame intermediate glyoxal (OCHCHO) has been assembled from available theoretical and experimental literature data. The modeling capabilities of this extensive mechanism have been tested by simulating experimental HCO profiles measured at intermediate and high temperatures in previous glyoxal photolysis and pyrolysis studies. Additionally, new experiments on glyoxal pyrolysis and oxidation have been performed with glyoxal and glyoxal/oxygen mixtures in Ar behind shock waves at temperatures of 1285−1760 K at two different total density ranges. HCO concentration−time profiles have been detected by frequency modulation spectroscopy at a wavelength of λ = 614.752 nm. The temperature range of available direct rate constant data of the hightemperature key reaction HCO + O 2 → CO + HO 2 has been extended up to 1705 K and confirms a temperature dependence consistent with a dominating direct abstraction channel. Taking into account available literature data obtained at lower temperatures, the following rate constant expression is recommended over the temperature range 295 K < T < 1705 K: k 1 /(cm 3 mol −1 s −1 ) = 6.92 × 10 6 × T 1.90 × exp(+5.73 kJ/mol/RT). At intermediate temperatures, the reaction OCHCHO + HO 2 becomes more important. A detailed reanalysis of previous experimental data as well as more recent theoretical predictions favor the formation of a recombination product in contrast to the formerly assumed dominating and fast OH-forming channel. Modeling results of the present study support the formation of HOCH(OO)CHO and provide a 2 orders of magnitude lower rate constant estimate for the OH channel. Hence, low-temperature generation of chain carriers has to be attributed to secondary reactions of HOCH(OO)CHO.

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“…A structureactivity relationship (SAR) method is used to determine unknown reaction rate coefficients (Kwok and Atkinson, 1995). Following the studies of Orlando and Tyndall (2001) and Méreau et al (2001), acylradicals are assumed to decompose promptly when the alkyl group features a carbonyl or an alcohol (with R secondary or tertiary) in β to the carbonyl:…”

Section: A11 Homentioning

confidence: 99%

Isoprene photooxidation: new insights into the production of acids and organic nitrates

et al. 2009

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Abstract. We describe a nearly explicit chemical mechanism for isoprene photooxidation guided by chamber studies that include time-resolved observation of an extensive suite of volatile compounds. We provide new constraints on the chemistry of the poorly-understood isoprene δ-hydroxy channels, which account for more than one third of the total isoprene carbon flux and a larger fraction of the nitrate yields. We show that the cis branch dominates the chemistry of the δ-hydroxy channel with less than 5% of the carbon following the trans branch. The modelled yield of isoprene nitrates is 12±3% with a large difference between the δ and β branches. The oxidation of these nitrates releases about 50% of the NO x . Methacrolein nitrates (modelled yield 15±3% from methacrolein) and methylvinylketone nitrates (modelled yield 11±3% yield from methylvinylketone) are also observed. Propanone nitrate, produced with a yield of 1% from isoprene, appears to be the longest-lived nitrate formed in the total oxidation of isoprene. We find a large molar yield of formic acid and suggest a novel mechanism leading to its formation from the organic nitrates. Finally, the most important features of this mechanism are summarized in a condensed scheme appropriate for use in global chemical transport models.

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The atmospheric chemistry of the HC(O)CO radical

Cited by 60 publications

References 28 publications

Total Peroxy Nitrates (ΣPNs) in the atmosphere: the Thermal Dissociation-Laser Induced Fluorescence (TD-LIF) technique and comparisons to speciated PAN measurements

Total Peroxy Nitrates (ΣPNs) in the atmosphere: the Thermal Dissociation-Laser Induced Fluorescence (TD-LIF) technique and comparisons to speciated PAN measurements

Glyoxal Oxidation Mechanism: Implications for the Reactions HCO + O₂ and OCHCHO + HO₂

Isoprene photooxidation: new insights into the production of acids and organic nitrates

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The atmospheric chemistry of the HC(O)CO radical

Cited by 60 publications

References 28 publications

Total Peroxy Nitrates (ΣPNs) in the atmosphere: the Thermal Dissociation-Laser Induced Fluorescence (TD-LIF) technique and comparisons to speciated PAN measurements

Total Peroxy Nitrates (ΣPNs) in the atmosphere: the Thermal Dissociation-Laser Induced Fluorescence (TD-LIF) technique and comparisons to speciated PAN measurements

Glyoxal Oxidation Mechanism: Implications for the Reactions HCO + O2 and OCHCHO + HO2

Isoprene photooxidation: new insights into the production of acids and organic nitrates

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Glyoxal Oxidation Mechanism: Implications for the Reactions HCO + O₂ and OCHCHO + HO₂