The production of organic nitrates from atmospheric oxidation of ethers and glycol ethers

Espada, Cyntia; Shepson, P. B.

doi:10.1002/kin.20121

Cited by 20 publications

(14 citation statements)

References 33 publications

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“…methyl butenol, long chain aldehydes, and other reactive biogenic VOCs. In the companion paper [36], we discuss the impact of oxygen-containing substituents on the organic nitrate branching ratios.…”

Section: Discussionmentioning

confidence: 99%

The production of organic nitrates from various anthropogenic volatile organic compounds

Espada

Grossenbacher

Ford

et al. 2005

Int J of Chemical Kinetics

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Production of organic nitrates from OH reaction with cyclohexane, cyclohexene, n-butane, 1-bromopropane, and p-xylene in the presence of NO was studied. The total organic nitrate yields for cyclohexane and n-butane were determined to be 17 ± 4 and 7 ± 2% respectively, which is in good agreement with previous determinations. Total yields for cyclohexene, 1-bromopropane, and p-xylene were 2.5 ± 0.5, 1.2 ± 0.3, and 3.2 ± 0.7 respectively. The yield for cyclohexene was five times smaller than that for cyclohexane. The 1-bromopropane yield is three times smaller that that for n-propane, but similar to that for propene, indicating that the effect of Br substitution in the reactant may be similar to that for OH substitution. The only nitrooxy product detected for p-xylene was 4-methylbenzylnitrate, which was formed following H abstraction from either methyl group. No organic nitrate was detected for peroxy radicals produced from OH addition to the ring, which accounts for 90% of the OH oxidation of p-xylene. The calculated k 3b /k 3 value for p-methyl benzyl peroxy radicals (0.32) was slightly smaller than for n-octyl peroxy radicals (0.39). These data imply that substituent inductive effects impact the k 3b /k 3 ratios. We found no significant difference in the k 3b /k 3 ratios for primary vs. secondary peroxy radicals of the same carbon chain. C 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: [675][676][677][678][679][680][681][682][683][684][685] 2005

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Section: Discussionmentioning

confidence: 99%

The production of organic nitrates from various anthropogenic volatile organic compounds

Espada

Grossenbacher

Ford

et al. 2005

Int J of Chemical Kinetics

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“…As discussed in Giacopelli et al (2005), based on the work of Espada and Shepson (2005), we previously estimated that the branching ratio, α i , for α, β-hydroxyperoxy radicals for isoprene is ∼0.058, and for the δ-hydroxyperoxy radicals, 0.15. If we accept these values for α i , we can calculate values for the yield of each precursor RO 2,i , γ i ; the results are shown in Table 1.…”

Section: Isoprene Nitrate Yieldsmentioning

confidence: 99%

Isoprene nitrates: preparation, separation, identification, yields, and atmospheric chemistry

et al. 2010

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Abstract.Isoprene is an important atmospheric volatile organic compound involved in ozone production and NO x (NO+NO 2 ) sequestration and transport. Isoprene reaction with OH in the presence of NO can form either isoprene hydroxy nitrates ("isoprene nitrates") or convert NO to NO 2 which can photolyze to form ozone. While it has been shown that isoprene nitrate production can represent an important sink for NO x in forest impacted environments, there is little experimental knowledge of the relative importance of the individual isoprene nitrate isomers, each of which has a different fate and reactivity. In this work, we have identified the 8 individual isomers and determined their total and individual production yields. The overall yield of isoprene nitrates at atmospheric pressure and 295 K was found to be 0.070(+0.025/−0.015). Three isomers, representing nitrates resulting from OH addition to a terminal carbon, represent 90% of the total IN yield. We also determined the ozone rate constants for three of the isomers, and have calculated their atmospheric lifetimes, which range from ∼1-2 h, making their oxidation products likely more important as atmospheric organic nitrates and sinks for nitrogen.

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“…Organic nitrate formation from NO X and peroxide radical may compete with the cyclization pathway (Stemmler et al, 1996). Espada and Shepson (2005) discussed -OR′ impact on ether organic nitrate product stability and yields. However, previous studies were mostly conducted with NO X concentrations higher than hundreds ppb, which is less atmospherically relevant (Stemmler et al, 1996;Aschmann and Atkinson, 1999;Orlando, 2007).…”

Section: Introductionmentioning

confidence: 99%

Molecular structure impacts on secondary organic aerosol formation from glycol ethers

Cocker

2018

Atmospheric Environment

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Glycol ethers, a class of widely used solvents in consumer products, are often considered exempt as volatile organic compounds based on their vapor pressure or boiling points by regulatory agencies. However, recent studies found that glycol ethers volatilize at ambient conditions nearly as rapidly as the traditional high-volatility solvents indicating the potential of glycol ethers to form secondary organic aerosol (SOA). This is the first work on SOA formation from glycol ethers. The impact of molecular structure, specifically-OH, on SOA formation from glycol ethers and related ethers are investigated in the work. Ethers with and without-OH, with methyl group hindrance on-OH and with-OH at different location are studied in the presence of NO X and under "NO X free" conditions. Photooxidation experiments under different oxidation conditions confirm that the processing of ethers is a combination of carbonyl formation, cyclization and fragmentation. Bulk SOA chemical composition analysis and oxidation products identified in both gas and particle phase suggests that the presence and location of-OH in the carbon bond of ethers determine the occurrence of cyclization mechanism during ether oxidation. The cyclization is proposed as a critical SOA formation mechanism to prevent the formation of volatile compounds from fragmentation during the oxidation of ethers. Glycol ethers with-CH 2-O-CH 2 CH 2 OH structure is found to readily form cyclization products, especially with the presence of NOx, which is more relevant to urban atmospheric conditions than without NOx. Glycol ethers are evaluated as dominating SOA precursors among all ethers studied. It is estimated that the contribution of glycol ethers to anthropogenic SOA is roughly 1% of the current organic aerosol from mobile sources. The contribution of glycol ethers to anthropogenic SOA is roughly 1% of the current organic aerosol from mobile sources and will play a more important role in future anthropogenic SOA formation.

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The production of organic nitrates from atmospheric oxidation of ethers and glycol ethers

Cited by 20 publications

References 33 publications

The production of organic nitrates from various anthropogenic volatile organic compounds

The production of organic nitrates from various anthropogenic volatile organic compounds

Isoprene nitrates: preparation, separation, identification, yields, and atmospheric chemistry

Molecular structure impacts on secondary organic aerosol formation from glycol ethers

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