Kinetic and product study of the gas‐phase reaction of sabinaketone with OH radical

Carrasco, Nathalie; Picquet‐Varrault, Bénédicte; Doussin, Jean‐François

doi:10.1002/kin.20252

Cited by 4 publications

(3 citation statements)

References 26 publications

(28 reference statements)

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“…The branching ratios could be inferred from the experimental rate coefficients. Experimental study had obtained the overall rate coefficient as 1.18 × 10 –10 cm 3 molecule –1 s –1 at 296 ± 2 K for reaction between Sab and the OH radical and 7.1 × 10 –12 cm 3 molecule –1 s –1 for reaction of sabinaketone and the OH radical . At room temperatures, reaction of sabinaketone and OH proceeds almost exclusively via H-abstraction.…”

Section: Results and Discussionmentioning

confidence: 99%

“…Experimental study had obtained the overall rate coefficient as 1.18 × 10 −10 cm 3 molecule −1 s −1 at 296 ± 2 K for reaction between Sab and the OH radical 8 and 7.1 × 10 −12 cm 3 molecule −1 s −1 for reaction of sabinaketone and the OH radical. 35 At room temperatures, reaction of sabinaketone and OH proceeds almost exclusively via H-abstraction. According to the structure−activity relationship by Kwok and Atkinson, 36 rate coefficients for H-abstraction could be obtained as 4.4 and 6.3 × 10 −12 cm 3 molecule −1 s −1 for Sab and sabinaketone, respectively.…”

Section: Resultsmentioning

confidence: 99%

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Atmospheric Oxidation Mechanism of Sabinene Initiated by the Hydroxyl Radicals

Wang

2018

J. Phys. Chem. A

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The atmospheric oxidation mechanism of sabinene initiated by the OH radical has been studied using quantum chemistry calculations at the CBS-QB3 level and reaction kinetic calculations using transition state theory and unimolecular rate theory coupled with collisional energy transfer. The oxidation is initiated by OH radical additions to the CH 2 C< bond with a branching ratio of ∼(92−96)%, while all the hydrogen atom abstractions count for ∼(4−8)% of branching ratio, which was estimated by comparing the rate coefficients of the reactions of sabinene and sabinaketon with the OH radical. Addition of OH to the C< carbon forms radical adduct Ra, while addition of OH to the terminal CH 2  carbon forms radical adduct Rb, which would break the three-membered ring promptly and almost completely to radical Re. RRKM-ME calculations obtained fractional yields of 0.40, 0.09, and 0.51 for radicals syn-Ra, anti-Ra, and Re, respectively, at 298 K and 760 Torr. In the atmosphere, the syn/anti-Ra radical would ultimately transform to sabinaketone in the presence of ppbv levels of NO, while in the transformation of the Re radical, both bimolecular reactions and unimolecular H-migrations could occur competitively for the peroxy radicals formed. The H-migrations in peroxy radicals result in the formation of unsaturated multifunctional compounds containing >CO, −OH, and/or −OOH groups. Formation of sabinaketone from syn-and anti-Ra and formation of acetone from Re are predicted with yields of ∼0.37 and ∼0.38 in the presence of high NO, being larger than while in reasonable agreement with the experimental values of 0.19−0.23 and of 0.21−0.27, respectively.

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Section: Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Atmospheric Oxidation Mechanism of Sabinene Initiated by the Hydroxyl Radicals

Wang

2018

J. Phys. Chem. A

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“…Photolysis rates and dilution rates were measured and reaction rate constants with OH radicals for acetone and HCHO were retrieved from IUPAC recommendations (Atkinson et al, 2006). The reaction rate constant of the reaction of sabinaketone and OH radicals is taken from measurements by Alvarado et al (1998) and Carrasco et al (2007) giving a value of 6 × 10 -12 cm 3 s -1 . The potential loss of sabinaketone by photolysis is estimated using photolysis rates of ketones calculated in the MCM model.…”

Section: Calculation Of Yields Of Oxidation Productsmentioning

confidence: 99%

Atmospheric photooxidation and ozonolysis of sabinene: Reaction rate constants, product yields and chemical budget of radicals

Pang¹,

Berg²,

Novelli³

et al. 2023

Preprint

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Abstract. The oxidation of sabinene by the hydroxyl radical (OH) and ozone (O3) was investigated under atmospherically relevant conditions in the atmospheric simulation chamber SAPHIR at Forschungszentrum Jülich, Germany. The rate constants of the reactions of sabinene with OH and with O3 were determined. The temperature dependence between 284 K to 340 K of the rate constant of the reaction of sabinene with OH, kSAB+OH, was measured for the first time using an OH reactivity instrument, resulting in an Arrhenius expression of (1.67 ± 0.16) × 10−11 × exp((575 ± 30) T−1) cm3 s−1. The values agree with those determined in chamber experiments in this work and reported in the literature for ~298 K within the uncertainties of measurements. The ozonolysis reaction rate constant of sabinene (kSAB+O3) determined in chamber experiments at a temperature of (278 ± 2) K is (3.7 ± 0.5) × 10−17 cm3 s−1, which is 55 % lower than the value reported in the literature for room temperature. The measurement of products from the oxidation of sabinene by OH resulted in an acetone yield of (21 ± 15) %, a formaldehyde yield of (46 ± 25) %, and a sabinaketone yield of (19 ± 16) %. All yields determined in the chamber experiments agree well with values from previous laboratory studies within their uncertainties. In addition, the formaldehyde yield determined in this study is consistent with that predicted by the sabinene OH-oxidation mechanism which was devised from quantum chemical calculations by Wang and Wang (2018), whereas the acetone yield is about 15 % absolute higher than that predicted by the mechanism. In the ozonolysis experiments, the analysis if product measurements results in an acetone yield of (5 ± 2) %, a formaldehyde yield of (48 ± 15) %, a sabinaketone yield of (31 ± 15) %, and an OH radical yield of (18 ± 25) %. The OH radical yield is lower than expected from the theoretical mechanism in Wang and Wang (2017), but the value still agrees within the uncertainty. An analysis of the chemical budget of OH radicals was performed for the chamber experiments. The analysis reveals that the destruction rate of OH radcials matches the production rate of OH suggesting that there is no significant missing OH source for example from isomerization reactions of peroxy radicals for the experimental conditions in this work.

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Biogenic volatile organic compound emissions from vegetation fires

Ciccioli

Centritto

Loreto

2014

Plant Cell & Environment

111

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The aim of this paper was to provide an overview of the current state of the art on research into the emission of biogenic volatile organic compounds (BVOCs) from vegetation fires. Significant amounts of VOCs are emitted from vegetation fires, including several reactive compounds, the majority belonging to the isoprenoid family, which rapidly disappear in the plume to yield pollutants such as secondary organic aerosol and ozone. This makes determination of fire-induced BVOC emission difficult, particularly in areas where the ratio between VOCs and anthropogenic NOx is favourable to the production of ozone, such as Mediterranean areas and highly anthropic temperate (and fire-prone) regions of the Earth. Fire emissions affecting relatively pristine areas, such as the Amazon and the African savannah, are representative of emissions of undisturbed plant communities. We also examined expected BVOC emissions at different stages of fire development and combustion, from drying to flaming, and from heatwaves coming into contact with unburned vegetation at the edge of fires. We conclude that forest fires may dramatically change emission factors and the profile of emitted BVOCs, thereby influencing the chemistry and physics of the atmosphere, the physiology of plants and the evolution of plant communities within the ecosystem.

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Kinetic and product study of the gas‐phase reaction of sabinaketone with OH radical

Cited by 4 publications

References 26 publications

Atmospheric Oxidation Mechanism of Sabinene Initiated by the Hydroxyl Radicals

Atmospheric Oxidation Mechanism of Sabinene Initiated by the Hydroxyl Radicals

Atmospheric photooxidation and ozonolysis of sabinene: Reaction rate constants, product yields and chemical budget of radicals

Biogenic volatile organic compound emissions from vegetation fires

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