Publication: Effects of Molecular Structure on Aerosol Yields from OH Radical-Initiated Reactions of Linear, Branched, and Cyclic Alkanes in the Presence of NOx

Publication - Effects of Molecular Structure on Aerosol Yields from OH Radical-Initiated Reactions of Linear, Branched, and Cyclic Alkanes in the Presence of NOx

Title: Effects of Molecular Structure on Aerosol Yields from OH Radical-Initiated Reactions of Linear, Branched, and Cyclic Alkanes in the Presence of NOx
DOI: 10.1021/es803389s
Publication Year: 2009
Author list: Lim, Y. B. and Ziemann, P. J.
Journal Short Name: Environ. Sci. Technol.
Publisher: American Chemical Society

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‚ąíreactivity 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.

Additional Notes



Experiments (29)

ID Name Start date Experiment Category Reaction Type Reactant(s) Oxidant Name Temperature Humidity Type of Seed RO2 Main Fate Data Sets (count) Actions
659 Ziemann_20071102_Heptane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-02 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation Heptane, Methyl nitrite, Nitric oxide Hydroxyl radical 25 1 DOS NO 1 Download
660 Ziemann_20071103_Octane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-03 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation Octane, Methyl nitrite, Nitric oxide Hydroxyl radical 25 1 DOS NO 1 Download
661 Ziemann_20071104_Nonane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-04 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation Nonane, Methyl nitrite, Nitric oxide Hydroxyl radical 23 1 DOS NO 1 Download
662 Ziemann_20071105_Decane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-05 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation Decane, Methyl nitrite, Nitric oxide Hydroxyl radical 25 1 DOS NO 1 Download
663 Ziemann_20071106_Undecane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-06 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation Undecane, Methyl nitrite, Nitric oxide Hydroxyl radical 25 1 DOS NO 1 Download
664 Ziemann_20071107_Dodecane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-07 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation Dodecane, Methyl nitrite, Nitric oxide Hydroxyl radical 25 1 DOS NO 1 Download
665 Ziemann_20071108_Tridecane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-08 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation Tridecane, Methyl nitrite, Nitric oxide Hydroxyl radical 23 1 DOS NO 1 Download
666 Ziemann_20071109_Tetradecane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-09 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation Tetradecane, Methyl nitrite, Nitric oxide Hydroxyl radical 25 1 DOS NO 1 Download
667 Ziemann_20071110_Pentadecane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-10 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation Pentadecane, Methyl nitrite, Nitric oxide Hydroxyl radical 25 1 DOS NO 1 Download
668 Ziemann_20071111_Hexadecane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-11 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation Hexadecane, Methyl nitrite, Nitric oxide Hydroxyl radical 25 1 DOS NO 1 Download
669 Ziemann_20071112_Heptadecane_Hydroxyl radical_DOS 2007-11-12 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation Heptadecane Hydroxyl radical 23 1 DOS NO 1 Download
671 Ziemann_20071113_Cyclohexane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-13 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation Cyclohexane, Methyl nitrite, Nitric oxide Hydroxyl radical 25 1 DOS NO 1 Download
672 Ziemann_20071114_Cycloheptane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-14 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation Cycloheptane, Methyl nitrite, Nitric oxide Hydroxyl radical 25 1 DOS NO 1 Download
673 Ziemann_20071115_Cyclooctane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-15 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation Cyclooctane, Methyl nitrite, Nitric oxide Hydroxyl radical 25 1 DOS NO 1 Download
674 Ziemann_20071116_Cyclodecane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-16 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation Cyclodecane, Methyl nitrite, Nitric oxide Hydroxyl radical 25 1 DOS NO 1 Download
675 Ziemann_20071117_Cyclododecane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-17 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation Cyclododecane, Methyl nitrite, Nitric oxide Hydroxyl radical 25 1 DOS NO 1 Download
676 Ziemann_20071118_Cyclopentadecane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-18 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation Cyclopentadecane, Methyl nitrite, Nitric oxide Hydroxyl radical 25 1 DOS NO 1 Download
678 Ziemann_20071119_Butylcyclohexane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-19 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation Butylcyclohexane, Methyl nitrite, Nitric oxide Hydroxyl radical 25 1 DOS NO 1 Download
679 Ziemann_20071120_3,4-Diethylhexane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-20 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation 3,4-Diethylhexane, Methyl nitrite, Nitric oxide Hydroxyl radical 25 1 DOS NO 1 Download
680 Ziemann_20071121_2-Methylundecane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-21 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation 2-Methylundecane, Methyl nitrite, Nitric oxide Hydroxyl radical 25 1 DOS NO 1 Download
681 Ziemann_20071122_2,3-Dimethyldecane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-22 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation 2,3-Dimethyldecane, Methyl nitrite, Nitric oxide Hydroxyl radical 25 1 DOS NO 1 Download
682 Ziemann_20071123_2,6-Dimethyldecane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-23 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation 2,6-Dimethyldecane, Methyl nitrite, Nitric oxide Hydroxyl radical 25 1 DOS NO 1 Download
683 Ziemann_20071124_2,2,4,4-Tetramethyloctane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-24 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation 2,2,4,4-Tetramethyloctane, Methyl nitrite, Nitric oxide Hydroxyl radical 25 1 DOS NO 1 Download
684 Ziemann_20071125_2,3,6,7-Tetramethyloctane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-25 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation 2,3,6,7-Tetramethyloctane, Methyl nitrite, Nitric oxide Hydroxyl radical 25 1 DOS NO 1 Download
685 Ziemann_20071126_2,2,4,6,6-Pentamethylheptane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-26 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation 2,2,4,6,6-Pentamethylheptane, Methyl nitrite, Nitric oxide Hydroxyl radical 25 1 DOS NO 1 Download
687 Ziemann_20071127_4,4-Dipropylheptane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-27 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation 4,4-Dipropylheptane, Methyl nitrite, Nitric oxide Hydroxyl radical 25 1 DOS NO 1 Download
688 Ziemann_20071128_2,3,3-Trimethyldecane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-28 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation 2,3,3-Trimethyldecane, Methyl nitrite, Nitric oxide Hydroxyl radical 25 1 DOS NO 1 Download
689 Ziemann_20071129_2,6,10-Trimethyldodecane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-29 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation 2,6,10-Trimethyldodecane, Methyl nitrite, Nitric oxide Hydroxyl radical 25 1 DOS NO 1 Download
690 Ziemann_20071130_Decylcyclohexane/Methyl nitrite/Nitric oxide_Hydroxyl radical_DOS 2007-11-30 Gas phase chemical reaction, Photolysis, any phase, Aerosol formation, Aerosol aging Photooxidation Decylcyclohexane, Methyl nitrite, Nitric oxide Hydroxyl radical 25 1 DOS NO 1 Download