Atmospheric chemistry of alkanes

Carter, William; Atkinson, Roger

doi:10.1007/bf00122525

Cited by 99 publications

(98 citation statements)

References 46 publications

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“…On the other hand, if ROOR formation is analogous to RONO 2 formation from RO 2 + NO reactions, then the ROOR yield from terpene RO 2 + RO 2 reactions may be higher, particularly for secondary RO 2 . RONO 2 yields for secondary RO 2 are about a factor of 2 higher than for primary or tertiary RO 2 , which have similar yields (Carter and Atkinson, 1985;Atkinson et al, 1987). …”

Section: Discussionmentioning

confidence: 90%

Peroxy radical chemistry and OH radical production during the NO3-initiated oxidation of isoprene

et al. 2012

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Abstract. Peroxy radical reactions (RO 2 + RO 2 ) from the NO 3 -initiated oxidation of isoprene are studied with both gas chromatography and a chemical ionization mass spectrometry technique that allows for more specific speciation of products than in previous studies of this system. We find high nitrate yields (∼ 80 %), consistent with other studies. We further see evidence of significant hydroxyl radical (OH) formation in this system, which we propose comes from RO 2 + HO 2 reactions with a yield of ∼ 38-58 %. An additional OH source is the second generation oxidation of the nitrooxyhydroperoxide, which produces OH and a dinitrooxyepoxide with a yield of ∼ 35 %. The branching ratio of the radical propagating, carbonyl-and alcohol-forming, and organic peroxide-forming channels of the RO 2 + RO 2 reaction are found to be ∼ 18-38 %, ∼ 59-77 %, and ∼ 3-4 %, respectively. HO 2 formation in this system is lower than has been previously assumed. Addition of RO 2 to isoprene is suggested as a possible route to the formation of several isoprene C 10 -organic peroxide compounds (ROOR). The nitrooxy, allylic, and C 5 peroxy radicals present in this system exhibit different behavior than the limited suite of peroxy radicals that have been studied to date.

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Section: Discussionmentioning

confidence: 90%

Peroxy radical chemistry and OH radical production during the NO3-initiated oxidation of isoprene

et al. 2012

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“…(by analogy to n-pentylperoxy and 2-methyl-3-butylperoxy, respectively) can be estimated [Carter and Atkinson, 1985]. Thus the formation of organic nitrates may account for about 10% of the reaction product and may represent a significant fraction of the remaining carbon not accounted for in our measured product yields.…”

Section: However Nitrate Yields Of About 4% For (Ch3)2c(oh)-choh-ch2mentioning

confidence: 90%

Rate and mechanism of the reactions of OH and Cl with 2‐methyl‐3‐buten‐2‐ol

Ferronato¹,

Orlando²,

Tyndall³

1998

J. Geophys. Res.

114

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“…One of the possible explanations for the higher SOA yield under high-NO x conditions is the formation of large alkoxy radicals that isomerize rather than fragment. Isomerization is plausible if the alkoxy radical has four or more carbon atoms and can form a 6-membered transition state (Baldwin et al, 1977;Carter and Atkinson, 1985). The isomerization pathway leads to the formation of large hydroxycarbonyls, multifunctional products that are likely low in volatility.…”

Section: Effect Of Hydrocarbon Size On No X Dependencementioning

confidence: 99%

Effect of NOx level on secondary organic aerosol (SOA) formation from the photooxidation of terpenes

et al. 2007

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Abstract. Secondary organic aerosol (SOA) formation from the photooxidation of one monoterpene (α-pinene) and two sesquiterpenes (longifolene and aromadendrene) is investigated in the Caltech environmental chambers. The effect of NO x on SOA formation for these biogenic hydrocarbons is evaluated by performing photooxidation experiments under varying NO x conditions. The NO x dependence of α-pinene SOA formation follows the same trend as that observed previously for a number of SOA precursors, including isoprene, in which SOA yield (defined as the ratio of the mass of organic aerosol formed to the mass of parent hydrocarbon reacted) decreases as NO x level increases. The NO x dependence of SOA yield for the sesquiterpenes, longifolene and aromadendrene, however, differs from that determined for isoprene and α-pinene; the aerosol yield under high-NO x conditions substantially exceeds that under low-NO x conditions. The reversal of the NO x dependence of SOA formation for the sesquiterpenes is consistent with formation of relatively low-volatility organic nitrates, and/or the isomerization of large alkoxy radicals leading to less volatile products. Analysis of the aerosol chemical composition for longifolene confirms the presence of organic nitrates under high-NO x conditions. Consequently the formation of SOA from certain biogenic hydrocarbons such as sesquiterpenes (and possibly large anthropogenic hydrocarbons as well) may be more efficient in polluted air.

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Atmospheric chemistry of alkanes

Cited by 99 publications

References 46 publications

Peroxy radical chemistry and OH radical production during the NO<sub>3</sub>-initiated oxidation of isoprene

Peroxy radical chemistry and OH radical production during the NO<sub>3</sub>-initiated oxidation of isoprene

Rate and mechanism of the reactions of OH and Cl with 2‐methyl‐3‐buten‐2‐ol

Effect of NO<sub>x</sub> level on secondary organic aerosol (SOA) formation from the photooxidation of terpenes

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Atmospheric chemistry of alkanes

Cited by 99 publications

References 46 publications

Peroxy radical chemistry and OH radical production during the NO&lt;sub&gt;3&lt;/sub&gt;-initiated oxidation of isoprene

Peroxy radical chemistry and OH radical production during the NO&lt;sub&gt;3&lt;/sub&gt;-initiated oxidation of isoprene

Rate and mechanism of the reactions of OH and Cl with 2‐methyl‐3‐buten‐2‐ol

Effect of NO&lt;sub&gt;x&lt;/sub&gt; level on secondary organic aerosol (SOA) formation from the photooxidation of terpenes

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Peroxy radical chemistry and OH radical production during the NO<sub>3</sub>-initiated oxidation of isoprene

Peroxy radical chemistry and OH radical production during the NO<sub>3</sub>-initiated oxidation of isoprene

Effect of NO<sub>x</sub> level on secondary organic aerosol (SOA) formation from the photooxidation of terpenes