Kinetic studies of the self-reaction and reaction with HO2 of a tertiary ?-brominated peroxy radical between 298 and 393 K

Villenave, Éric; Lesclaux, R.

doi:10.1002/1097-4601(20010101)33:1<41::aid-kin5>3.0.co;2-j

Cited by 4 publications

(2 citation statements)

References 21 publications

(19 reference statements)

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“…We evaluate the balance between HHLoss and NHLoss using observations of NO 2 and NO, of OH and HO 2 , and the inferred RO 2 concentrations in and . There are few measurements of rate constants for reactions between HO 2 and RO 2 ( k RO2+HO2 ) for R larger than 3 carbons [e.g., Villenave and Lesclaux , 2001] and even fewer quantitative studies of product yields. We use the rate constant recommended by Atkinson [1994] for generic RO 2 ( k RO2+HO2 ∼ 1 × 10 −11 cm −3 s −1 at 298 K) and an ROOH yield of unity.…”

Section: Nox Limited Versus Nox Saturated Po3mentioning

confidence: 99%

Ozone production rates as a function of NO_x abundances and HO_x production rates in the Nashville urban plume

et al. 2002

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[1] Tropospheric O 3 concentrations are functions of the chain lengths of NO x (NO x NO + NO 2 ) and HO x (HO x OH + HO 2 + RO 2 ) radical catalytic cycles. For a fixed HO x source at low NO x concentrations, kinetic models indicate the rate of O 3 production increases linearly with increases in NO x concentrations (NO x limited). At higher NO x concentrations, kinetic models predict ozone production rates decrease with increasing NO x (NO x saturated). We present observations of NO, NO 2 , O 3 , OH, HO 2 , H 2 CO, actinic flux, and temperature obtained during the 1999 Southern Oxidant Study from June 15 to July 15, 1999, at Cornelia Fort Airpark, Nashville, Tennessee. The observations are used to evaluate the instantaneous ozone production rate (P O3 ) as a function of NO abundances and the primary HO x production rate (P HOx ). These observations provide quantitative evidence for the response of P O3 to NO x . For high P HOx (0.5 < P HOx < 0.7 ppt/s), O 3 production at this site increases linearly with NO to $500 ppt. P O3 levels out in the range 500-1000 ppt NO and decreases for NO above 1000 ppt. An analysis along chemical coordinates indicates that models of chemistry controlling peroxy radical abundances, and consequently P O3 , have a large error in the rate or product yield of the RO 2 + HO 2 reaction for the classes of RO 2 that predominate in Nashville. Photochemical models and our measurements can be forced into agreement if the product of the branching ratio and rate constant for organic peroxide formation, via RO 2 + HO 2 ! ROOH + O 2 , is reduced by a factor of 3-12. Alternatively, these peroxides could be rapidly photolyzed under atmospheric conditions making them at best a temporary HO x reservoir. This result implies that O 3 production in or near urban areas with similar hydrocarbon reactivity and HO x production rates may be NO x saturated more often than current models suggest.

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Section: Nox Limited Versus Nox Saturated Po3mentioning

confidence: 99%

Ozone production rates as a function of NO_x abundances and HO_x production rates in the Nashville urban plume

et al. 2002

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“…There have been a number of experimental and computational studies on reactions between RO 2 and HO 2 . − Branching ratios of product channels change with the functional groups in −R. For the alkyl peroxy radicals, the reactions go through almost exclusively the R1a channel; while for the acyl and acetonyl peroxy radicals, the R1c channel becomes more significant.…”

Section: Introductionmentioning

confidence: 99%

Computational Study on the Reaction of β-Hydroxyethylperoxy Radical with HO₂ and Effects of Water Vapor

Wang

2022

J. Phys. Chem. A

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The reaction of β-hydroxyethylperoxy radical (β-HEP) and HO 2 with and without water was studied using quantum chemistry and kinetic calculations. The main products are HOCH 2 CH 2 OOH and 3 O 2 for the reaction with and without water, while all other reaction channels can be neglected. The rate coefficients of the reaction follow negative temperature dependence. The pseudo-second-order rate coefficients are 2−4 orders of magnitude smaller for the reaction with saturated water vapor, indicating the negligible contribution of water in this reaction. This is probably also true for other peroxy radicals (except for HO 2 ), indicating that a large part of previous results on the water enhancement of reaction rate coefficients might have overestimated the influence of water.

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Theoretical study of PhCH2O4CH2Ph: intermediate in the PhCH2O2 self-reaction

2019

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Kinetic studies of the self-reaction and reaction with HO2 of a tertiary ?-brominated peroxy radical between 298 and 393 K

Cited by 4 publications

References 21 publications

Ozone production rates as a function of NO_x abundances and HO_x production rates in the Nashville urban plume

Ozone production rates as a function of NO_x abundances and HO_x production rates in the Nashville urban plume

Computational Study on the Reaction of β-Hydroxyethylperoxy Radical with HO₂ and Effects of Water Vapor

Theoretical study of PhCH2O4CH2Ph: intermediate in the PhCH2O2 self-reaction

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Kinetic studies of the self-reaction and reaction with HO2 of a tertiary ?-brominated peroxy radical between 298 and 393 K

Cited by 4 publications

References 21 publications

Ozone production rates as a function of NOx abundances and HOx production rates in the Nashville urban plume

Ozone production rates as a function of NOx abundances and HOx production rates in the Nashville urban plume

Computational Study on the Reaction of β-Hydroxyethylperoxy Radical with HO2 and Effects of Water Vapor

Theoretical study of PhCH2O4CH2Ph: intermediate in the PhCH2O2 self-reaction

Contact Info

Product

Resources

About

Ozone production rates as a function of NO_x abundances and HO_x production rates in the Nashville urban plume

Ozone production rates as a function of NO_x abundances and HO_x production rates in the Nashville urban plume

Computational Study on the Reaction of β-Hydroxyethylperoxy Radical with HO₂ and Effects of Water Vapor