Gas‐phase chemistry of dihydromyrcenol with ozone and OH radical: Rate constants and products

Forester, Crystal D.; Ham, Jason E.; Wells, J. R.

doi:10.1002/kin.20174

Cited by 17 publications

(7 citation statements)

References 37 publications

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“…Reaction rates of O 3 and indoor-emitted terpenoids have been widely studied, for instance with d -limonene, α- and β-pinene, terpinolene, γ-terpinene, α-terpineol, linalool, and dihydromyrcenol, among others (e.g. Arey et al, 1990; Atkinson, 1990; Atkinson et al, 1990, 1992b; Forester et al, 2006; Grosjean and Grosjean, 1999; Wells, 2005). …”

Section: Introductionmentioning

confidence: 99%

Volatile organic compound conversion by ozone, hydroxyl radicals, and nitrate radicals in residential indoor air: Magnitudes and impacts of oxidant sources

Waring

Wells

2015

Atmospheric Environment

128

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Indoor chemistry may be initiated by reactions of ozone (O3), the hydroxyl radical (OH), or the nitrate radical (NO3) with volatile organic compounds (VOC). The principal indoor source of O3 is air exchange, while OH and NO3 formation are considered as primarily from O3 reactions with alkenes and nitrogen dioxide (NO2), respectively. Herein, we used time-averaged models for residences to predict O3, OH, and NO3 concentrations and their impacts on conversion of typical residential VOC profiles, within a Monte Carlo framework that varied inputs probabilistically. We accounted for established oxidant sources, as well as explored the importance of two newly realized indoor sources: (i) the photolysis of nitrous acid (HONO) indoors to generate OH and (ii) the reaction of stabilized Criegee intermediates (SCI) with NO2 to generate NO3. We found total VOC conversion to be dominated by reactions both with O3, which almost solely reacted with d-limonene, and also with OH, which reacted with d-limonene, other terpenes, alcohols, aldehydes, and aromatics. VOC oxidation rates increased with air exchange, outdoor O3, NO2 and d-limonene sources, and indoor photolysis rates; and they decreased with O3 deposition and nitric oxide (NO) sources. Photolysis was a strong OH formation mechanism for high NO, NO2, and HONO settings, but SCI/NO2 reactions weakly generated NO3 except for only a few cases.

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Section: Introductionmentioning

confidence: 99%

Volatile organic compound conversion by ozone, hydroxyl radicals, and nitrate radicals in residential indoor air: Magnitudes and impacts of oxidant sources

Waring

Wells

2015

Atmospheric Environment

128

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“…16 Acetone and its oxidation product 2-oxopropanal, CH 3 C(O)CHO, are formed indoors and may be implicated in work-related asthma. 17 Atmospheric loss processes for acetone include photolysis 18,19 and reaction with O H: [20][21][22]…”

Section: Introductionmentioning

confidence: 99%

Thermochemistry and kinetics of acetonylperoxy radical isomerisation and decomposition: a quantum chemistry and CVT/SCT approach

El‐Nahas

Simmie

Navarro

et al. 2008

Phys. Chem. Chem. Phys.

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CBS-QB3 calculations have been used to determine thermochemical and kinetic parameters of the isomerisation and decomposition reactions of the acetonylperoxy radical, CH3C(O)CH2OO* , which has been formed via the reaction of acetonyl radical with O2 leading to the formation of an energised peroxy adduct with a calculated well depth of near 111 kJ mol(-1). This species can undergo subsequent 1,5 and 1,3 H-shifts to give the primary and secondary radicals: C*H2C(O)CH2OOH and CH3C(O)C*HOOH, respectively, or rearrange to give a 3-methyl-1,2-dioxetan-3-yloxy radical. Rate constants for isomerisation and subsequent decomposition have been estimated using canonical variational transition state theory with small curvature tunneling cvt/sct. The variational effect for the isomerisation channels is only moderate but the tunneling correction is significant at temperatures up to 1000 K; the formation of a primary radical by a 1,5-shift is the main reaction channel and the competition with the secondary one starts only at around 1500 K. The fate of the primary acetonylhydroperoxy radical is predominantly to form oxetan-3-one while the ketene and 1-oxy-3-hydroxyacetonyl radical channels only compete with the formation of oxetan-3-one at temperatures >1200 K. In addition, consistent and reliable enthalpies of formation have been computed for the molecules acetonylhydroperoxide, 1,3-dihydroxyacetone, methylglyoxal and cyclobutanone, and for some related radicals.

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“…The experimental procedures for determining the valencene and farnesol + O 3 /

{NO}_{3}^{•}

reaction kinetics were similar to those described previously .

Valencene + {normalO}_{3} \overset{k_{O_{3}} + Valencene}{- - - - - } Products

Reference + {normalO}_{3} \overset{k_{Ref}}{} Products

The rate equations for reactions (1) and (2) are combined and integrated, resulting in the following equation:

\ln (\frac{{[Valencene]}_{0}}{[{Valencene]}_{t}}) = \frac{K_{O_{3} + Valencene}}{K_{Ref}} \ln (\frac{{[Ref]}_{0}}{{[Ref]}_{t}})

If reaction with O 3 is the only removal mechanism for valencene and reference, a plot of ln([valencene] 0 /[valencene] t ) versus ln ([Ref] 0 /[Ref] t ) yields a straight line with an intercept of zero.…”

Section: Methodsmentioning

confidence: 99%

Rate Constants for the Gas‐Phase Reactions of Ozone and Nitrate Radicals with the Sesquiterpenes: Valencene and Farnesol

Ham

2013

Int J of Chemical Kinetics

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Sesquiterpenes are constituents of a variety of essential oils that are used in flavorings, perfumes, personal care, and cleaning products. Two sesquiterpenes that are commonly used as indoor fragrances are valencene and farnesol. Knowing the reaction rate constants of these chemicals with ozone (O 3 ) and nitrate radical (NO • 3 ) is an important factor in determining their fate indoors. In this study, the bimolecular rate constants of k O 3 +valencene (0.35 ± 0.9) × 10 −16 , k O 3 +farnesol (21 ± 5.2) × 10 −16 , k NO • 3 +valencene (7.9 ± 2.0) × 10 −12 , and k NO • 3 +farnesol (44 ± 11) × 10 −12 cm 3 molecule −1 s −1 were measured using the relative rate technique at 297 ± 3 K and 1 atm total pressure. Using the rate constants reported here and measured/modeled indoor concentrations of O 3 and NO • 3 (20 ppb and 1 ppt, respectively), pseudo-first-order-rate lifetimes k O 3 +valencene (0.06), k O 3 +farnesol (3.8), k NO 3 +valencene(0.7), and k NO 3 ·+farnesol (3.9)h −1 were determined. C 2013 Wiley Periodicals, Inc.

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Gas‐phase chemistry of dihydromyrcenol with ozone and OH radical: Rate constants and products

Cited by 17 publications

References 37 publications

Volatile organic compound conversion by ozone, hydroxyl radicals, and nitrate radicals in residential indoor air: Magnitudes and impacts of oxidant sources

Volatile organic compound conversion by ozone, hydroxyl radicals, and nitrate radicals in residential indoor air: Magnitudes and impacts of oxidant sources

Thermochemistry and kinetics of acetonylperoxy radical isomerisation and decomposition: a quantum chemistry and CVT/SCT approach

Rate Constants for the Gas‐Phase Reactions of Ozone and Nitrate Radicals with the Sesquiterpenes: Valencene and Farnesol

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