Kinetics and Mechanisms for the Reactions of Ozone with Unsaturated Oxygenated Compounds

Mulla, Ismael Al; Viera, Lisa; Morris, R. D.; Sidebottom, Howard; Treacy, Jack; Mellouki, Abdelwahid

doi:10.1002/cphc.201000404

Cited by 30 publications

(40 citation statements)

References 33 publications

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“…The availability of kinetic data for the reaction of these compounds with other tropospheric oxidants is very scarce. As far as we know, only the reaction of AEE with O 3 is reported in the literature, with a rate coefficient k O3, AEE ¼ 8.69 Â 10 À18 cm 3 molecule À1 s À1 (Al Mulla et al, 2010). Assuming an average O 3 concentration, [O 3 ] 24h ¼ 7 Â 10 11 molecule cm À3 (Logan, 1985), t O3, AEE is estimated to be ca.…”

Section: Atmospheric Implicationsmentioning

confidence: 98%

Atmospheric degradation of 2-chloroethyl vinyl ether, allyl ether and allyl ethyl ether: Kinetics with OH radicals and UV photochemistry

et al. 2017

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Section: Atmospheric Implicationsmentioning

confidence: 98%

Atmospheric degradation of 2-chloroethyl vinyl ether, allyl ether and allyl ethyl ether: Kinetics with OH radicals and UV photochemistry

et al. 2017

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“…We use the rate coefficients at 298 K, as a single value is needed in the analysis and 298 K was close to the average daytime high. Reactions with ozone and NO 3 are inefficient for all measured OVOCs (Atkinson, ; Atkinson & Arey, ; Al Mulla et al, ; Bernard et al, ) except for 3‐furaldehyde, which reacts efficiently with NO 3 (Colmenar et al, ). Rate coefficients for the reactions of the unsaturated OVOCs studied here with ozone and NO 3 are given in Table S1 in the supporting information.…”

Section: Measurements and Data Descriptionmentioning

confidence: 99%

Chemistry of Volatile Organic Compounds in the Los Angeles Basin: Formation of Oxygenated Compounds and Determination of Emission Ratios

et al. 2018

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We analyze an expanded data set of oxygenated volatile organic compounds (OVOCs) in air measured by several instruments at a surface site in Pasadena near Los Angeles during the National Oceanic and Atmospheric Administration California Nexus study in 2010. The contributions of emissions, chemical formation, and removal are quantified for each OVOC using CO as a tracer of emissions and the OH exposure of the sampled air masses calculated from hydrocarbon ratios. The method for separating emissions from chemical formation is evaluated using output for Pasadena from the Weather Research and Forecasting‐Chemistry model. The model is analyzed by the same method as the measurement data, and the emission ratios versus CO calculated from the model output agree for ketones with the inventory used in the model but overestimate aldehydes by ~70%. In contrast with the measurements, nighttime formation of OVOCs is significant in the model and is attributed to overestimated precursor emissions and overestimated rate coefficients for the reactions of the precursors with ozone and NO3. Most measured aldehydes correlated strongly with CO at night, suggesting a contribution from motor vehicle emissions. However, the emission ratios of most aldehydes versus CO are higher than those reported in motor vehicle emissions and the aldehyde sources remain unclear. Formation of several OVOCs is investigated in terms of the removal of specific precursors. Direct emissions of alcohols and aldehydes contribute significantly to OH reactivity throughout the day, and these emissions should be accurately represented in models describing ozone formation.

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“…The lifetime for a heterogeneous reaction can be compared to that for the gaseous oxidation by OH and O 3 . Taking the global concentration of OH (10 6 molecules cm -3 ) and O 3 (10 12 molecules cm -3 ) [Seinfeld and Pandis, 2006], and assuming a rate constant close to vinyl ethers [Al Mulla et al, 2010;Zhou et al, 2006], the lifetime of isoprene oxide against OH is found to be 3-6 hours and against O 3 > 1day. Similarly, for α-pinene oxide lifetime against OH and O 3 would be 1 day to several days assuming a rate constant similar to that of a cyclic ether 1,8-cineole [Atkinson and Arey, 2003;Atkinson et al, 1990;Corchnoy and Atkinson, 1990].…”

Section: Atmospheric Implicationsmentioning

confidence: 99%

Heterogeneous Reactions of Epoxides in Acidic Media

et al. 2012

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Epoxides have recently been identified as important intermediates in the gas phase oxidation of hydrocarbons, and their hydrolysis products have been observed in ambient aerosols. To evaluate the role of epoxides in the formation of secondary organic aerosols (SOA), the kinetics and mechanism of heterogeneous reactions of two model epoxides, isoprene oxide and α-pinene oxide, with sulfuric acid, ammonium bisulfate, and ammonium sulfate have been investigated using complementary experimental techniques. Kinetic experiments using a fast flow reactor coupled to an ion drift-chemical ionization mass spectrometer (ID-CIMS) show a fast irreversible loss of the epoxides with the uptake coefficients (γ) of (1.7 ± 0.1) × 10(-2) and (4.6 ± 0.3) × 10(-2) for isoprene oxide and α-pinene oxide, respectively, for 90 wt % H(2)SO(4) and at room temperature. Experiments using attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) reveal that diols are the major products in ammonium bisulfate and dilute H(2)SO(4) (<25 wt %) solutions for both epoxides. In concentrated H(2)SO(4) (>65 wt %), acetals are formed from isoprene oxide, whereas organosulfates are produced from α-pinene oxide. The reaction of the epoxides with ammonium sulfate is slow and no products are observed. The epoxide reactions using bulk samples and Nuclear Magnetic Resonance (NMR) spectroscopy reveal the presence of diols as the major products for isoprene oxide, accompanied by aldehyde formation. For α-pinene oxide, organosulfate formation is observed with a yield increasing with the acidity. Large yields of organosulfates in all NMR experiments with α-pinene oxide are attributed to the kinetic isotope effect (KIE) from the use of deuterated sulfuric acid and water. Our results suggest that acid-catalyzed hydrolysis of epoxides results in the formation of a wide range of products, and some of the products have low volatility and contribute to SOA growth under ambient conditions prevailing in the urban atmosphere.

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Kinetics and Mechanisms for the Reactions of Ozone with Unsaturated Oxygenated Compounds

Cited by 30 publications

References 33 publications

Atmospheric degradation of 2-chloroethyl vinyl ether, allyl ether and allyl ethyl ether: Kinetics with OH radicals and UV photochemistry

Atmospheric degradation of 2-chloroethyl vinyl ether, allyl ether and allyl ethyl ether: Kinetics with OH radicals and UV photochemistry

Chemistry of Volatile Organic Compounds in the Los Angeles Basin: Formation of Oxygenated Compounds and Determination of Emission Ratios

Heterogeneous Reactions of Epoxides in Acidic Media

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