Products of the gas-phase reactions of the OH radical withn-butyl methyl ether and 2-isopropoxyethanol: Reactions of ROC(??) &lt; radicals

Aschmann, Sara M.; Atkinson, Roger

doi:10.1002/(sici)1097-4601(1999)31:7<501::aid-kin5>3.0.co;2-h

Cited by 35 publications

(2 citation statements)

References 31 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Further, hydroperoxides oxidation product formation is expected in absence of NO X (Jenkin et al, 1993;Sehested et al, 1996). The presence of NO X leads to nitrate formation including peroxynitrate and peroxyacyl nitrate (Aschmann and Atkinson, 1999;Orlando, 2007;Malanca et al, 2009) and affects alkoxy radical decomposition (Collins et al, 2005;Orlando, 2007). Reaction with NO 3 radical may also contribute to a small extent ofether removal during night-time, while photolysis and reaction with O 3 are negligible (Chew et al, 1998;Mellouki et al, 2003).…”

Section: Introductionmentioning

confidence: 99%

“…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). It is important to study ether oxidation under atmospherically relevant NO X conditions in order to extend laboratory data to ambient prediction.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Molecular structure impacts on secondary organic aerosol formation from glycol ethers

Cocker

2018

Atmospheric Environment

View full text Add to dashboard Cite

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.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Molecular structure impacts on secondary organic aerosol formation from glycol ethers

Cocker

2018

Atmospheric Environment

View full text Add to dashboard Cite

show abstract

Laboratory studies of the ^·OH‐initiated photooxidation of ethyl‐n‐butyl ether and di‐n‐butyl ether

Johnson

Andino

2001

Int J of Chemical Kinetics

View full text Add to dashboard Cite

Oxygenated compounds such as ethers and alcohols are used as gasoline additives and industrial solvents. However, despite their widespread use, the atmospheric reaction mechanisms of some of these compounds are unknown. This study examines the иOH-initiated gas-phase removal mechanisms of ethyl-n-butyl ether (ENBE) and di-n-butyl ether (DNBE) utilizing gas chromatography-mass spectrometry techniques. The primary products and molar yields from the hydroxyl-radical-initiated photooxidation of ENBE in the presence of nitric oxide were acetaldehyde (0.173 Ϯ 0.012), ethyl formate (0.219 Ϯ 0.033), butyraldehyde (0.076 Ϯ 0.004), butyl formate (0.241 Ϯ 0.009), butyl acetate (0.032 Ϯ 0.001), and ethyl butyrate (0.0044 Ϯ 0.0006). From the calculated molar yields, approximately 45.5% of the reacted carbon were recovered. The primary products and molar yields from the DNBE and hydroxyl radical reaction in the presence of nitric oxide were propionaldehyde (0.379 Ϯ 0.022), butyraldehyde (0.119 Ϯ 0.003), butyl formate (0.410 Ϯ 0.009), and butyl butyrate (0.019 Ϯ 0.001). Approximately 47.7% of the reacted DNBE were recovered. The chemical mechanisms are presented to explain the formation of these products. In addition, the importance of the isomerization and nitrate/nitrite formation pathways in the reactions of large ethers are discussed.

show abstract

Rate constant estimation for C₁ to C₄ alkyl and alkoxyl radical decomposition

Curran

2006

Int J of Chemical Kinetics

220

200

View full text Add to dashboard Cite

Rate coefficients for alkyl and alkoxy radical decomposition are important in combustion, biological, and atmospheric processes. In this paper, rate constant expressions for C 1 C 4 alkyl and alkoxy radicals decomposition via β-scission are recommended based on the reverse, exothermic reaction, the addition of a hydrogen atom or an alkyl radical to an olefin or carbonyl species with the decomposition reaction calculated using microscopic reversibility. The rate expressions have been estimated based on a wide-range study of available experimental data. Rate coefficients for hydrogen atom and alkyl radical addition to an olefin show a strong temperature curvature. In addition, it is found that there is a correlation between the activation energy for addition and (i) the type of atom undergoing addition and (ii) whether this radical adds to the internal or terminal carbon atom of the olefin. Rate coefficients for alkoxy radical decomposition show a strong correlation to the ionization potential of the alkyl radical leaving group and on the enthalpy of reaction. It is shown that the activation energy for alkyl radical addition to a carbonyl species can be estimated as a function of the alkyl radical ionization potential and enthalpy of reaction.

show abstract

Products of the gas-phase reactions of the OH radical withn-butyl methyl ether and 2-isopropoxyethanol: Reactions of ROC(??) < radicals

Cited by 35 publications

References 31 publications

Molecular structure impacts on secondary organic aerosol formation from glycol ethers

Molecular structure impacts on secondary organic aerosol formation from glycol ethers

Laboratory studies of the ^·OH‐initiated photooxidation of ethyl‐n‐butyl ether and di‐n‐butyl ether

Rate constant estimation for C₁ to C₄ alkyl and alkoxyl radical decomposition

Contact Info

Product

Resources

About

Products of the gas-phase reactions of the OH radical withn-butyl methyl ether and 2-isopropoxyethanol: Reactions of ROC(??) < radicals

Cited by 35 publications

References 31 publications

Molecular structure impacts on secondary organic aerosol formation from glycol ethers

Molecular structure impacts on secondary organic aerosol formation from glycol ethers

Laboratory studies of the ·OH‐initiated photooxidation of ethyl‐n‐butyl ether and di‐n‐butyl ether

Rate constant estimation for C1 to C4 alkyl and alkoxyl radical decomposition

Contact Info

Product

Resources

About

Laboratory studies of the ^·OH‐initiated photooxidation of ethyl‐n‐butyl ether and di‐n‐butyl ether

Rate constant estimation for C₁ to C₄ alkyl and alkoxyl radical decomposition