Reevaluation of the rate constant for the reaction propene + NO3 by absolute rate determination

Picquet‐Varrault, B.; Scarfogliero, M.; Helal, W. Ait; Doussin, Jean‐François

doi:10.1002/kin.20371

Cited by 8 publications

(7 citation statements)

References 38 publications

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“…Hence, the factors G(C(O)OR) and G(OC(O)R) were calculated and are presented in Table 5. The G(OC(O)R) were determined by using the rate constants obtained in recent studies on the reactions of vinyl acetate [72] and isopropenyl acetate [73] with NO 3 radical.…”

Section: Estersmentioning

confidence: 99%

“…The thus-obtained factor G(COC(O)R) is about ten times more deactivating than that for the a position, G(OC(O)R). This factor is based on the experimental study carried out for the reactivity with NO 3 radical of allyl acetate, [73] in order to determine the influence of an ester group ÀOC(O)R in b position. Thus, the less deactivating behaviour of this group in a position may be the consequence of competition between two effects.…”

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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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: Estersmentioning

confidence: 99%

Section: Estersmentioning

confidence: 99%

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

2010

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“…2 and 3) adapted from Atkinson et al (1984a) and Schott and Davidson (1958). The detailed protocol is presented in Picquet-Varrault et al (2009).…”

Section: Introductionmentioning

confidence: 99%

A comparative and experimental study of the reactivity with nitrate radical of two terpenes: α-terpinene and γ-terpinene

et al. 2020

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Abstract. Biogenic volatile organic compounds (BVOCs) are intensely emitted by forests and crops into the atmosphere. During the night, they react very rapidly with the nitrate radical (NO3), leading to the formation of a variety of functionalized products including organic nitrates and to large amounts of secondary organic aerosols (SOAs). Organic nitrates (ONs) have been shown not only to play a key role in the transport of reactive nitrogen and consequently in the ozone budget but also to be important components of the total organic-aerosol mass, while SOAs are known to play a direct and indirect role in the climate. However, the reactivity of BVOCs with NO3 remains poorly studied. The aim of this work is to provide new kinetic and mechanistic data for two monoterpenes (C10H16), α- and γ-terpinene, through experiments in simulation chambers. These two compounds, which have very similar chemical structures, have been chosen in order not only to overcome the lack of experimental data but also to highlight the influence of the chemical structure on the reactivity. Rate constants have been measured using both relative and absolute methods. They were found to be (1.2±0.5)×10-10 and (2.9±1.1)×10-11 cm3 molecule−1 s−1 for α- and γ-terpinene respectively. Mechanistic studies have also been conducted in order to identify and quantify the main reaction products. Total organic nitrate and SOA yields have been determined. While organic nitrate formation yields appear to be similar, SOA yields exhibit large differences with γ-terpinene being a much more efficient precursor of aerosols. In order to provide explanations for this difference, chemical analysis of the gas-phase products was performed at the molecular scale. Detected products allowed for proposing chemical mechanisms and providing explanations through peroxy and alkoxy reaction pathways.

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“…(3)) adapted from (Atkinson et al, 1984a;Schott and Davidson, 1958). The detailed protocol is presented in Picquet-Varrault et al, 2009. Doussin et al, 1997) and being equipped with a homogenization system that allows a mixing time below one minute.…”

mentioning

confidence: 99%

A comparative and experimental study of the reactivity with nitrate radical of two terpenes: α-terpinene and γ-terpinene

Fouqueau¹,

Cirtog²,

Cazaunau³

et al. 2020

Preprint

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Abstract. Biogenic volatile organic compounds (BVOCs) are intensely emitted by forests and crops into the atmosphere. During the night, they react very rapidly with the nitrate radical (NO3), leading to the formation of a variety of functionalized products including organic nitrates and to large amounts of secondary organic aerosols (SOA). Organic nitrates (ONs) have been shown to play a key role in the transport of reactive nitrogen and consequently in the ozone budget, but also to be important components of the total organic aerosol while SOA are known to play a direct and indirect role on the climate. However, the reactivity of BVOCs with NO3 remains poorly studied. The aim of this work is to provide new kinetic and mechanistic data for two monoterpenes (C10H16), α- and γ-terpinene, through experiments in simulation chambers. These two compounds, which have very similar chemical structures, have been chosen in order to fill the lack of experimental data but also to highlight the influence of the chemical structure on the reactivity. Rate constants have been measured using both relative and absolute methods. They were found to be (1.2 ± 0.5) x 10-10 and (2.9 ± 1.1) x 10-11 cm3 molecule-1 s-1 for α- and γ-terpinene respectively. Mechanistic studies have also been conducted in order to identify and quantify the main reaction products. Total organic nitrate and SOA yields have been determined. While organic nitrate formation yields appear to be similar, SOA yields exhibit large differences with γ-terpinene being a much more efficient precursor of aerosols. In order to provide explanations for this difference, chemical analysis of the gas phase products were performed at the molecular scale. Detected products allowed proposing chemical mechanisms and providing explanations through peroxy and alkoxy reaction pathways.

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Reevaluation of the rate constant for the reaction propene + NO₃ by absolute rate determination

Cited by 8 publications

References 38 publications

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

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

A comparative and experimental study of the reactivity with nitrate radical of two terpenes: <i>α</i>-terpinene and <i>γ</i>-terpinene

A comparative and experimental study of the reactivity with nitrate radical of two terpenes: α-terpinene and γ-terpinene

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Reevaluation of the rate constant for the reaction propene + NO3 by absolute rate determination

Cited by 8 publications

References 38 publications

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

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

A comparative and experimental study of the reactivity with nitrate radical of two terpenes: &lt;i&gt;α&lt;/i&gt;-terpinene and &lt;i&gt;γ&lt;/i&gt;-terpinene

A comparative and experimental study of the reactivity with nitrate radical of two terpenes: α-terpinene and γ-terpinene

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Reevaluation of the rate constant for the reaction propene + NO₃ by absolute rate determination

A comparative and experimental study of the reactivity with nitrate radical of two terpenes: <i>α</i>-terpinene and <i>γ</i>-terpinene