A kinetic study of the reactions of NO3 with methyl vinyl ketone, methacrolein, acrolein, methyl acrylate and methyl methacrylate

Canosa‐Mas, Carlos E.; Carr, Sinéad; King, Martin D.; Shallcross, Dudley E.; Thompson, Katherine C.; Wayne, Richard P.

doi:10.1039/a904613e

Cited by 51 publications

(52 citation statements)

References 18 publications

(6 reference statements)

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“…Indeed, many mechanistic studies on the reaction of unsaturated compounds with NO 3 have shown that abstraction pathways generally correspond to less than 10 % of the overall NO 3 reaction. [6,7,39,40] Nevertheless, the sum of their contribution may compete with addition processes. Hence, even for the parametrization of unsaturated compounds H-atom abstraction must be taken into account.…”

Section: H-atom Abstractionmentioning

confidence: 99%

“…These effects could be attributed to the electron-withdrawing mesomeric effect of these groups, which lowers the electron density around the double bond and thus reduces the reactivity. [10,39] Consequently ester groups ÀC(O)OR and ÀOC(O)R have been shown to decrease the reactivity of these compounds by factors of 70 and 1.2, respectively. Hence, the factors G(C(O)OR) and G(OC(O)R) were calculated and are presented in Table 5.…”

Section: Estersmentioning

confidence: 99%

“…[d] Ref. [39], rate constants re-evaluated with k ethene = 1.96 10 À16 cm 3 molecule À1 s À1 [37] at 296 K.…”

Section: Internal Validationmentioning

confidence: 99%

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Prediction of Rate Constants for Gas‐Phase Reactions of Nitrate Radical with Organic Compounds: A New Structure–Activity Relationship

2010

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A new structure-activity relationship (SAR), based on parametrization of the molecular structure according to the group-additivity method, is presented. On the basis of existing experimental data for the degradability of approximately 150 organic compounds by the NO(3) radical, this new SAR is developed to estimate the rate constants for reactions with NO(3) radical. At night, nitrate radicals are the most important oxidant of volatile organic compounds. The rate constants for their reactions are therefore essential to the understanding of VOC degradation and atmospheric modelling. The database used for the SAR development includes most classes of compounds such as alkanes, alkenes (acyclic and cyclic), dienes, terpenes and saturated and unsaturated oxygenated compounds (including alcohols, ketones, ethers and esters). The proposed SAR shows good efficiency, as 91% of the rate constants are reproduced within a factor of two. The overall agreement between measured and predicted rate constants is very good for most of the unsaturated and saturated compounds, although for saturated alcohols it is less reliable.

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Section: H-atom Abstractionmentioning

confidence: 99%

Section: Estersmentioning

confidence: 99%

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Prediction of Rate Constants for Gas‐Phase Reactions of Nitrate Radical with Organic Compounds: A New Structure–Activity Relationship

2010

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“…The same authors measured the quantum effi ciency of acetaldehyde formation using the same wavelength to be Φ′ = 0.48. 302) k NO 3 = 8.9E-15, measured by Canosa-Mas et al 1999 [399] at 293 K, replaces an older, much lower value. 298) k OH = 5.5E-12 (R) confi rmed by Wu et al 2003 [489]: 5.47 ± 0.25 at 295 K, 1000 hPa.…”

Section: )mentioning

confidence: 82%

Table of Reaction Rate Constants of Photo‐Degradation Processes

Klöpffer¹,

Wagner²

2007

Atmospheric Degradation of Organic Substances

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“…For Cl reactions, there are several kinetic studies for a series of acrylate esters (Blanco et al , 2009aMartín et al, 2010), including temperature dependence for methyl acrylate, methyl methacrylate, and n-butyl methacrylate. However, kinetic information of methacrylates reactions with NO 3 is especially scarce (Canosa-Mas et al 1999, Wang et al 2010, and no product determination has been developed to date. Degradation pathways of these compounds at night time in the presence of NO 3 have not previously been proposed and this information is also necessary in order to determine the effect and potential impact of methacrylate emissions on the air quality of the troposphere.…”

mentioning

confidence: 99%