Effects of Molecular Structure on Aerosol Yields from OH Radical-Initiated Reactions of Linear, Branched, and Cyclic Alkanes in the Presence of NOx.
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| Title: | Effects of Molecular Structure on Aerosol Yields from OH Radical-Initiated Reactions of Linear, Branched, and Cyclic Alkanes in the Presence of NO |
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| Authors: | LIM, YONG B.1, ZIEMANN, PAUL J.2 paul.ziemann@ucr.edu |
| Source: | Environmental Science & Technology. 4/1/2009, Vol. 43 Issue 7, p2328-2334. 7p. |
| Subjects: | Molecular structure, Aerosols & the environment, Alkanes, Nitrogen oxides, Hydrocarbons & the environment, Hydroxides, Radicals (Chemistry) |
| Abstract: | The effect of hydrocarbon molecular structure on the measured yield and volatility of secondary organic aerosol (SOA) formed from OH radical-initiated reactions of linear, branched, and cyclic alkanes in the presence of NOx was investigated in an environmental chamber. SOA yields from reactions of homologous series of linear and cyclic alkanes increased monotonically with increasing carbon number due to the decreasing volatility of the parent alkanes and thus the reaction products. For a given carbon number, yields followed the order cyclic > linear > branched, a trend that appears to be determined primarily by the extent to which alkoxy radical intermediates decompose and the nature of the resulting products, with parent alkane volatility being of secondary importance. The trend was investigated quantitatively by correlating SOA yields with the fraction of OH radical reactions that lead to alkoxy radical decomposition (the remainder isomerize), calculated using structure-reactivity relationships. For alkoxy radicals with branched or strained cyclic structures, decomposition can compete with isomerization, whereas for those with linear structures it cannot Branched alkoxy radicals fragment to form pairs of smaller, more volatile products, whereas cyclic alkoxy radicals undergo ring opening to form products similar to those formed from reactions of linear alkanes, but with an additional aldehyde group. The lower volatility of multifunctional aldehydes, and their tendency to form oligomers, appears to enhance SOA yields. [ABSTRACT FROM AUTHOR] |
| Copyright of Environmental Science & Technology is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
| Database: | Engineering Source |
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| Items | – Name: Title Label: Title Group: Ti Data: Effects of Molecular Structure on Aerosol Yields from OH Radical-Initiated Reactions of Linear, Branched, and Cyclic Alkanes in the Presence of NO<subscript>x</subscript>. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22LIM%2C+YONG+B%2E%22">LIM, YONG B.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22ZIEMANN%2C+PAUL+J%2E%22">ZIEMANN, PAUL J.</searchLink><relatesTo>2</relatesTo><i> paul.ziemann@ucr.edu</i> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Environmental+Science+%26+Technology%22">Environmental Science & Technology</searchLink>. 4/1/2009, Vol. 43 Issue 7, p2328-2334. 7p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Molecular+structure%22">Molecular structure</searchLink><br /><searchLink fieldCode="DE" term="%22Aerosols+%26+the+environment%22">Aerosols & the environment</searchLink><br /><searchLink fieldCode="DE" term="%22Alkanes%22">Alkanes</searchLink><br /><searchLink fieldCode="DE" term="%22Nitrogen+oxides%22">Nitrogen oxides</searchLink><br /><searchLink fieldCode="DE" term="%22Hydrocarbons+%26+the+environment%22">Hydrocarbons & the environment</searchLink><br /><searchLink fieldCode="DE" term="%22Hydroxides%22">Hydroxides</searchLink><br /><searchLink fieldCode="DE" term="%22Radicals+%28Chemistry%29%22">Radicals (Chemistry)</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: The effect of hydrocarbon molecular structure on the measured yield and volatility of secondary organic aerosol (SOA) formed from OH radical-initiated reactions of linear, branched, and cyclic alkanes in the presence of NOx was investigated in an environmental chamber. SOA yields from reactions of homologous series of linear and cyclic alkanes increased monotonically with increasing carbon number due to the decreasing volatility of the parent alkanes and thus the reaction products. For a given carbon number, yields followed the order cyclic > linear > branched, a trend that appears to be determined primarily by the extent to which alkoxy radical intermediates decompose and the nature of the resulting products, with parent alkane volatility being of secondary importance. The trend was investigated quantitatively by correlating SOA yields with the fraction of OH radical reactions that lead to alkoxy radical decomposition (the remainder isomerize), calculated using structure-reactivity relationships. For alkoxy radicals with branched or strained cyclic structures, decomposition can compete with isomerization, whereas for those with linear structures it cannot Branched alkoxy radicals fragment to form pairs of smaller, more volatile products, whereas cyclic alkoxy radicals undergo ring opening to form products similar to those formed from reactions of linear alkanes, but with an additional aldehyde group. The lower volatility of multifunctional aldehydes, and their tendency to form oligomers, appears to enhance SOA yields. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Environmental Science & Technology is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1021/es803389s Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 7 StartPage: 2328 Subjects: – SubjectFull: Molecular structure Type: general – SubjectFull: Aerosols & the environment Type: general – SubjectFull: Alkanes Type: general – SubjectFull: Nitrogen oxides Type: general – SubjectFull: Hydrocarbons & the environment Type: general – SubjectFull: Hydroxides Type: general – SubjectFull: Radicals (Chemistry) Type: general Titles: – TitleFull: Effects of Molecular Structure on Aerosol Yields from OH Radical-Initiated Reactions of Linear, Branched, and Cyclic Alkanes in the Presence of NOx. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: LIM, YONG B. – PersonEntity: Name: NameFull: ZIEMANN, PAUL J. IsPartOfRelationships: – BibEntity: Dates: – D: 01 M: 04 Text: 4/1/2009 Type: published Y: 2009 Identifiers: – Type: issn-print Value: 0013936X Numbering: – Type: volume Value: 43 – Type: issue Value: 7 Titles: – TitleFull: Environmental Science & Technology Type: main |
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