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J Phys Chem A

Title:		Effect of the Keto Group on Yields and Composition of Organic Aerosol Formed from OH Radical-Initiated Reactions of Ketones in the Presence of NOx
Author(s):		Algrim LB; Ziemann PJ;
Address:		"Department of Chemistry and Biochemistry, University of Colorado , Boulder, Colorado 80309, United States. Cooperative Institute for Research in Environmental Sciences (CIRES), University of Colorado , Boulder, Colorado 80309, United States"
Journal Title:		J Phys Chem A
Year:		2016
Volume:		20160826
Issue:		35
Page Number:		6978 - 6989
DOI:		10.1021/acs.jpca.6b05839
ISSN/ISBN:		1520-5215 (Electronic) 1089-5639 (Linking)
Abstract:		"Yields of secondary organic aerosol (SOA) were measured for OH radical-initiated reactions of the 2- through 6-dodecanone positional isomers and also n-dodecane and n-tetradecane in the presence of NOx. Yields decreased in the order n-tetradecane > dodecanone isomer average > n-dodecane, and the dodecanone isomer yields decreased as the keto group moved toward the center of the molecule, with 6-dodecanone being an exception. Trends in the yields can be explained by the effect of carbon number and keto group presence and position on product vapor pressures, and by the isomer-specific effects of the keto group on branching ratios for keto alkoxy radical isomerization, decomposition, and reaction with O2. Most importantly, results indicate that isomerization of keto alkoxy radicals via 1,5- and 1,6-H shifts are significantly hindered by the presence of a keto group whereas decomposition is enhanced. Analysis of particle composition indicates that the SOA products are similar for all isomers, and that compared to those formed from the corresponding reactions of alkanes the presence of a pre-existing keto group opens up additional heterogeneous/multiphase reaction pathways that can lead to the formation of new products. The results demonstrate that the presence of a keto group alters gas and particle phase chemistry and provide new insights into the potential effects of molecular structure on the products of the atmospheric oxidation of volatile organic compounds and subsequent formation of SOA"
Keywords:
Notes:		"PubMed-not-MEDLINEAlgrim, Lucas B Ziemann, Paul J eng 2016/08/11 J Phys Chem A. 2016 Sep 8; 120(35):6978-89. doi: 10.1021/acs.jpca.6b05839. Epub 2016 Aug 26"