Oxidation of isoprene through reaction with NO3 radicals is a significant sink for isoprene that persists after dark. The main products of the reaction are multifunctional nitrates. These nitrates constitute a significant NOx sink in the nocturnal boundary layer and they likely play an important role in formation of secondary organic aerosol. Products of the isoprene+NO3 reaction will, in many locations, be abundant enough to affect nighttime radical chemistry and to persist into daytime where they may represent a source of NOx. Product formation in the isoprene + NO3 reaction was studied in a smog chamber at Purdue University. Isoprene nitrates and other hydrocarbon products were observed using Proton Transfer Reaction-Mass Spectrometry (PTR-MS) and reactive nitrogen products were observed using Thermal Dissociation-Laser Induced Fluorescence (TD-LIF). The organic nitrate yield is found to be 65 +/- 12% of which the majority was nitrooxy carbonyls and the combined yield of methacrolein and methyl vinyl ketone (MACR+MVK) is found to be similar to 10%. PTR-MS measurements of nitrooxy carbonyls and TD-LIF measurements of total organic nitrates agreed well. The PTR-MS also observed a series of minor oxidation products which were tentatively identified and their yields quantified These other oxidation products are used as additional constraints on the reaction mechanism.
%0 Journal Article
%1 Perring:2009p3595
%A Perring, A. E
%A Wisthaler, A
%A Graus, M
%A Wooldridge, P. J
%A Lockwood, A. L
%A Mielke, L. H
%A Shepson, P. B
%A Hansel, A
%A Cohen, R. C
%D 2009
%J Atmospheric Chemistry and Physics
%K Alkyl Chemistry, Constants Gas-Phase Mass-Spectrometry, Mixing Nitrates, No3, Oh, Organic-Compounds, Ptr-Ms, Rate Ratios, Reactions, Spectrometry Volatile
%N 14
%P 4945--4956
%T A product study of the isoprene+NO3 reaction
%U http://apps.isiknowledge.com/InboundService.do?product=WOS&action=retrieve&SrcApp=Papers&UT=000268535500027&SID=3DBHInNJkJI5ndObejb&SrcAuth=mekentosj&mode=FullRecord&customersID=mekentosj&DestFail=http%253A%252F%252Faccess.isiproducts.com%252Fcustom_images%252Fwok_failed_auth.html
%V 9
%X Oxidation of isoprene through reaction with NO3 radicals is a significant sink for isoprene that persists after dark. The main products of the reaction are multifunctional nitrates. These nitrates constitute a significant NOx sink in the nocturnal boundary layer and they likely play an important role in formation of secondary organic aerosol. Products of the isoprene+NO3 reaction will, in many locations, be abundant enough to affect nighttime radical chemistry and to persist into daytime where they may represent a source of NOx. Product formation in the isoprene + NO3 reaction was studied in a smog chamber at Purdue University. Isoprene nitrates and other hydrocarbon products were observed using Proton Transfer Reaction-Mass Spectrometry (PTR-MS) and reactive nitrogen products were observed using Thermal Dissociation-Laser Induced Fluorescence (TD-LIF). The organic nitrate yield is found to be 65 +/- 12% of which the majority was nitrooxy carbonyls and the combined yield of methacrolein and methyl vinyl ketone (MACR+MVK) is found to be similar to 10%. PTR-MS measurements of nitrooxy carbonyls and TD-LIF measurements of total organic nitrates agreed well. The PTR-MS also observed a series of minor oxidation products which were tentatively identified and their yields quantified These other oxidation products are used as additional constraints on the reaction mechanism.
@article{Perring:2009p3595,
abstract = {Oxidation of isoprene through reaction with NO3 radicals is a significant sink for isoprene that persists after dark. The main products of the reaction are multifunctional nitrates. These nitrates constitute a significant NOx sink in the nocturnal boundary layer and they likely play an important role in formation of secondary organic aerosol. Products of the isoprene+NO3 reaction will, in many locations, be abundant enough to affect nighttime radical chemistry and to persist into daytime where they may represent a source of NOx. Product formation in the isoprene + NO3 reaction was studied in a smog chamber at Purdue University. Isoprene nitrates and other hydrocarbon products were observed using Proton Transfer Reaction-Mass Spectrometry (PTR-MS) and reactive nitrogen products were observed using Thermal Dissociation-Laser Induced Fluorescence (TD-LIF). The organic nitrate yield is found to be 65 +/- 12% of which the majority was nitrooxy carbonyls and the combined yield of methacrolein and methyl vinyl ketone (MACR+MVK) is found to be similar to 10%. PTR-MS measurements of nitrooxy carbonyls and TD-LIF measurements of total organic nitrates agreed well. The PTR-MS also observed a series of minor oxidation products which were tentatively identified and their yields quantified These other oxidation products are used as additional constraints on the reaction mechanism.},
added-at = {2010-06-22T19:38:37.000+0200},
affiliation = {Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA},
author = {Perring, A. E and Wisthaler, A and Graus, M and Wooldridge, P. J and Lockwood, A. L and Mielke, L. H and Shepson, P. B and Hansel, A and Cohen, R. C},
biburl = {https://www.bibsonomy.org/bibtex/210c69fa974440434d9d89eac6ce31e25/gsmith},
date-added = {2010-05-05 16:57:43 -0400},
date-modified = {2010-05-05 16:57:50 -0400},
interhash = {2f0ed78614949b1060af56ab25e11442},
intrahash = {10c69fa974440434d9d89eac6ce31e25},
journal = {Atmospheric Chemistry and Physics},
keywords = {Alkyl Chemistry, Constants Gas-Phase Mass-Spectrometry, Mixing Nitrates, No3, Oh, Organic-Compounds, Ptr-Ms, Rate Ratios, Reactions, Spectrometry Volatile},
language = {English},
local-url = {file://localhost/Users/geoffreysmith/Documents/Papers/Atmospheric%20Chemistry%20and%20Physics/2009/Atmospheric%20Chemistry%20and%20Physics,%209,%204945-4956%202009.pdf},
month = Jan,
number = 14,
pages = {4945--4956},
pmid = {000268535500027},
rating = {0},
timestamp = {2010-06-22T19:39:27.000+0200},
title = {A product study of the isoprene+NO3 reaction},
uri = {papers://E88B624E-D406-46FF-9D95-BB9C1AAE3FDC/Paper/p3595},
url = {http://apps.isiknowledge.com/InboundService.do?product=WOS&action=retrieve&SrcApp=Papers&UT=000268535500027&SID=3DBHInNJkJI5ndObejb&SrcAuth=mekentosj&mode=FullRecord&customersID=mekentosj&DestFail=http%253A%252F%252Faccess.isiproducts.com%252Fcustom_images%252Fwok_failed_auth.html},
volume = 9,
year = 2009
}