Atmospheric Chemistry of Unsaturated Carbonyls: Butenedial, 4-Oxo-2-pentenal, 3-Hexene-2,5-dione, Maleic Anhydride, 3H-Furan-2-one, and 5-Methyl-3H-furan-2-one

Bierbach, A.; Barnes, Ian; Becker, K. H.; Wiesen, E.

doi:10.1021/es00053a028

Cited by 127 publications

(200 citation statements)

References 24 publications

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“…The mechanistic yield of 20% for this compound comes close to experimental values published more recently by Klotz et al (1998) and Smith et al (1998). For benzaldehyde, the spread in literature yields is a factor of two and the model gives a yield of 6% that is supported by several studies published in the nineties by Klotz et al (1998), Bierbach et al (1994), and Seuwen and Warneck (1996). Literature values for the glyoxal yield vary between 8% and 39% (Atkinson, 1992;Volkamer et al, 2001 and references therein).…”

Section: Product Yieldsmentioning

confidence: 58%

“…In the MCM v3, generic photolysis rates are applied for the photolysis of conjugated γ -dicarbonyls derived from experimental data published by Sørensen et al (1998), Liu et al (1999) and Bierbach et al (1994). For two γ -dicarbonyls, butenedial and 4-oxo-2-pentenal, which are oxidation products of toluene, experimental data are available and we have set the photolysis rates for all γ -dicarbonyls in TOL MCM3a accordingly.…”

Section: The Mechanismmentioning

confidence: 99%

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Modelling of the photooxidation of toluene: conceptual ideas for validating detailed mechanisms

et al. 2003

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Abstract. Toluene photooxidation is chosen as an example to examine how simulations of smog-chamber experiments can be used to unravel shortcomings in detailed mechanisms and to provide information on complex reaction systems that will be crucial for the design of future validation experiments. The mechanism used in this study is extracted from the Master Chemical Mechanism Version 3 (MCM v3) and has been updated with new modules for cresol and γ -dicarbonyl chemistry. Model simulations are carried out for a toluene-NO x experiment undertaken at the European Photoreactor (EUPHORE). The comparison of the simulation with the experimental data reveals two fundamental shortcomings in the mechanism: OH production is too low by about 44%, and the ozone concentration at the end of the experiment is over-predicted by 55%. The radical budget was analysed to identify the key intermediates governing the radical transformation in the toluene system. Ring-opening products, particularly conjugated γ -dicarbonyls, were identified as dominant radical sources in the early stages of the experiment. The analysis of the time evolution of radical production points to a missing OH source that peaks when the system reaches highest reactivity. First generation products are also of major importance for the ozone production in the system. The analysis of the radical budget suggests two options to explain the concurrent under-prediction of OH and overprediction of ozone in the model: (1) missing oxidation processes that produce or regenerate OH without or with little NO to NO 2 conversion or (2) NO 3 chemistry that sequesters reactive nitrogen oxides into stable nitrogen compounds and at the same time produces peroxy radicals. Sensitivity analyCorrespondence to: M. J. Pilling (M.J.Pilling@chem.leeds.ac.uk sis was employed to identify significant contributors to ozone production and it is shown how this technique, in combination with ozone isopleth plots, can be used for the design of validation experiments.

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Section: Product Yieldsmentioning

confidence: 58%

Section: The Mechanismmentioning

confidence: 99%

Modelling of the photooxidation of toluene: conceptual ideas for validating detailed mechanisms

et al. 2003

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“…Rate coefficients have been determined for the reactions of OH with butenedial, 4-oxo-2-pentenal and 3-hexene-2,5-dione (Tuazon et al, 1985;Bierbach et al, 1994;Calvert et al, 2002), and these values are applied accordingly. In other cases, rate coefficients are estimated using the method described previously for unsaturated carbonyls , with this methodology also being used to infer the relative importance of addition to the double bond and abstraction of H from the aldehyde group (where applicable).…”

Section: α β-Unsaturated-γ -Dicarbonylsmentioning

confidence: 99%

“…The chemistry following abstraction of H from the aldehyde group also largely follows the conventional methodology, but with incorporation of an additional route to generate a furandione product in appropriate cases, as has been observed in laboratory studies of the oxidation of α, β-unsaturated-γ -dicarbonyls (Bierbach et al, 1994), and also as products of aromatic hydrocarbon oxidation (e.g. Forstner et al, 1997).…”

Section: α β-Unsaturated-γ -Dicarbonylsmentioning

confidence: 99%

Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part B): tropospheric degradation of aromatic volatile organic compounds

et al. 2003

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Abstract. Kinetic and mechanistic data relevant to the tropospheric degradation of aromatic volatile organic compounds (VOC) have been used to define a mechanism development protocol, which has been used to construct degradation schemes for 18 aromatic VOC as part of version 3 of the Master Chemical Mechanism (MCM v3). This is complementary to the treatment of 107 non-aromatic VOC, presented in a companion paper. The protocol is divided into a series of subsections describing initiation reactions, the degradation chemistry to first generation products via a number of competitive routes, and the further degradation of first and subsequent generation products. Emphasis is placed on describing where the treatment differs from that applied to the non-aromatic VOC. The protocol is based on work available in the open literature up to the beginning of 2001, and some other studies known by the authors which were under review at the time. Photochemical Ozone Creation Potentials (POCP) have been calculated for the 18 aromatic VOC in MCM v3 for idealised conditions appropriate to north-west Europe, using a photochemical trajectory model. The POCP values provide a measure of the relative ozone forming abilities of the VOC. These show distinct differences from POCP values calculated previously for the aromatics, using earlier versions of the MCM, and reasons for these differences are discussed.

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“…The rate constant for OH reaction with benzaldehyde (Calvert et al, 2002) is a factor of 5 lower than for α-angelicalactone and a factor of 4 lower than for 4-oxo-2-pentenal, which also undergoes significant loss by photolysis (Bierbach et al, 1994). The lactone/oxopentenal pair is formed earlier in the reaction than the 2-methylbenzoquinone, maleic and citraconic anhydride, suggesting the latter are second or higher generation products, as indicated in the degradation mechanism shown in Fig.…”

Section: Toluene Oxidation Productsmentioning

confidence: 99%

Measurements of photo-oxidation products from the reaction of a series of alkyl-benzenes with hydroxyl radicals during EXACT using comprehensive gas chromatography

et al. 2003

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Abstract. Photo-oxidation products from the reaction of a series of alkyl-benzenes, (benzene, toluene, p-xylene and 1,3,5-trimethyl-benzene) with hydroxyl radicals in the presence of NO x have been investigated using comprehensive gas chromatography (GC×GC). A GC×GC system has been developed which utilises valve modulation and independent separations as a function of both volatility and polarity. A number of carbonyl-type compounds were identified during a series of reactions carried out at the European Photoreactor (EUPHORE), a large volume outdoor reaction chamber in Valencia, Spain. Experiments were carried as part of the EXACT project (Effects of the oXidation of Aromatic Compounds in the Troposphere). Two litre chamber air samples were cryo-focused, with a sampling frequency of 30 minutes, allowing the evolution of species to be followed over oxidation periods of 3-6 hours. To facilitate product identification, several carbonyl compounds, which were possible products of the photo-oxidation, were synthesised and used as reference standards.For toluene reactions, observed oxygenated intermediates found included the co-eluting pair α-angelicalactone/4-oxo-2-pentenal, maleic anhydride, citraconic anhydride, benzaldehyde and p-methyl benzoquinone. In the p-xylene experiment, the products identified were E/Z-hex-3-en-2,5-dione and citraconic anhydride. For 1,3,5-TMB reactions, the products identified were 3,5-dimethylbenzaldehyde, 3,5-dimethyl-3H-furan-2-one and 3-methyl-5-methylene-5H-furan-2-one. Preliminary quantification was carried out on identified compounds using liquid standards. Comparison of FTIR and GC×GC for the measurement of the parent aroCorrespondence to: J. F. Hamilton (jacquih@chemistry.leeds.ac.uk) matics generally showed good agreement. Comparison of the concentrations observed by GC×GC to concentrationtime profiles simulated using the Master Chemical Mechanism, MCMv3, demonstrates that this mechanism significantly over-predicts the concentrations of many product compounds and highlights the uncertainties which exist in our understanding of the atmospheric oxidation of aromatics.

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Atmospheric Chemistry of Unsaturated Carbonyls: Butenedial, 4-Oxo-2-pentenal, 3-Hexene-2,5-dione, Maleic Anhydride, 3H-Furan-2-one, and 5-Methyl-3H-furan-2-one

Cited by 127 publications

References 24 publications

Modelling of the photooxidation of toluene: conceptual ideas for validating detailed mechanisms

Modelling of the photooxidation of toluene: conceptual ideas for validating detailed mechanisms

Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part B): tropospheric degradation of aromatic volatile organic compounds

Measurements of photo-oxidation products from the reaction of a series of alkyl-benzenes with hydroxyl radicals during EXACT using comprehensive gas chromatography

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