Atmospheric fate of two relevant unsaturated ketoethers: kinetics, products and mechanisms for the reaction of hydroxyl radicals with (E)-4-methoxy-3-buten-2-one and (1E)-1-methoxy-2-methyl-1-penten-3-one

The kinetics of the gas phase reactions of hydroxyl radicals with two unsaturated ketoethers (UKEs) at (298±3) K and 1 atm of synthetic air have been studied for the first time using the relative-rate technique in an environmental reaction chamber by in situ Fourier...

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Main Authors:	R. G. Gibilisco, I. Barnes, I. G. Bejan, P. Wiesen
Format:	Article
Language:	English
Published:	Copernicus Publications 2020-07-01
Series:	Atmospheric Chemistry and Physics
Online Access:	https://www.atmos-chem-phys.net/20/8939/2020/acp-20-8939-2020.pdf

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spelling	doaj-4a31f060f5c8444eb65d951ff30c67d72020-11-25T02:56:32ZengCopernicus PublicationsAtmospheric Chemistry and Physics1680-73161680-73242020-07-01208939895110.5194/acp-20-8939-2020Atmospheric fate of two relevant unsaturated ketoethers: kinetics, products and mechanisms for the reaction of hydroxyl radicals with (<i>E</i>)-4-methoxy-3-buten-2-one and (1<i>E</i>)-1-methoxy-2-methyl-1-penten-3-oneR. G. Gibilisco0I. Barnes1I. G. Bejan2I. G. Bejan3P. Wiesen4Institute for Atmospheric and Environmental Research, Bergische Universität Wuppertal, 42097 Wuppertal, GermanyInstitute for Atmospheric and Environmental Research, Bergische Universität Wuppertal, 42097 Wuppertal, GermanyFaculty of Chemistry, Department of Chemistry, Alexandru Ioan Cuza University of Iasi, 11 Carol I, Iasi 700506, RomaniaIntegrated Centre of Environmental Science Studies in the North Eastern Region, Alexandru Ioan Cuza University of Iasi, 11 Carol I, Iasi 700506, RomaniaInstitute for Atmospheric and Environmental Research, Bergische Universität Wuppertal, 42097 Wuppertal, Germany<p>The kinetics of the gas phase reactions of hydroxyl radicals with two unsaturated ketoethers (UKEs) at (298±3) K and 1 atm of synthetic air have been studied for the first time using the relative-rate technique in an environmental reaction chamber by in situ Fourier-transform infrared spectroscopy (FTIR). The rate coefficients obtained using propene and isobutene as reference compounds were (in units of 10<sup>−10</sup> cm<sup>3</sup> molecule<sup>−1</sup> s<sup>−1</sup>) as follows: <i>k</i><sub>TMBO</sub> (OH + (<i>E</i>)-4-methoxy-3-buten-2-one)  =  (1.41±0.11) and <i>k</i><sub>MMPO</sub> (OH + (1<i>E</i>)-1-methoxy-2-methyl-1-penten-3-one)  =  (3.34±0.43). In addition, quantification of the main oxidation products in the presence of NO<sub><i>x</i></sub> has been performed, and degradation mechanisms for these reactions were developed. Methyl formate, methyl glyoxal, peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN) were identified as main reaction products and quantified for both reactions. The results of the present study provide new insights regarding the contribution of these multifunctional volatile organic compounds (VOCs) in the generation of secondary organic aerosols (SOAs) and long-lived nitrogen containing compounds in the atmosphere. Atmospheric lifetimes and implications are discussed in light of the obtained results.</p>https://www.atmos-chem-phys.net/20/8939/2020/acp-20-8939-2020.pdf
collection	DOAJ
language	English
format	Article
sources	DOAJ
author	R. G. Gibilisco I. Barnes I. G. Bejan I. G. Bejan P. Wiesen
spellingShingle	R. G. Gibilisco I. Barnes I. G. Bejan I. G. Bejan P. Wiesen Atmospheric fate of two relevant unsaturated ketoethers: kinetics, products and mechanisms for the reaction of hydroxyl radicals with (<i>E</i>)-4-methoxy-3-buten-2-one and (1<i>E</i>)-1-methoxy-2-methyl-1-penten-3-one Atmospheric Chemistry and Physics
author_facet	R. G. Gibilisco I. Barnes I. G. Bejan I. G. Bejan P. Wiesen
author_sort	R. G. Gibilisco
title	Atmospheric fate of two relevant unsaturated ketoethers: kinetics, products and mechanisms for the reaction of hydroxyl radicals with (<i>E</i>)-4-methoxy-3-buten-2-one and (1<i>E</i>)-1-methoxy-2-methyl-1-penten-3-one
title_short	Atmospheric fate of two relevant unsaturated ketoethers: kinetics, products and mechanisms for the reaction of hydroxyl radicals with (<i>E</i>)-4-methoxy-3-buten-2-one and (1<i>E</i>)-1-methoxy-2-methyl-1-penten-3-one
title_full	Atmospheric fate of two relevant unsaturated ketoethers: kinetics, products and mechanisms for the reaction of hydroxyl radicals with (<i>E</i>)-4-methoxy-3-buten-2-one and (1<i>E</i>)-1-methoxy-2-methyl-1-penten-3-one
title_fullStr	Atmospheric fate of two relevant unsaturated ketoethers: kinetics, products and mechanisms for the reaction of hydroxyl radicals with (<i>E</i>)-4-methoxy-3-buten-2-one and (1<i>E</i>)-1-methoxy-2-methyl-1-penten-3-one
title_full_unstemmed	Atmospheric fate of two relevant unsaturated ketoethers: kinetics, products and mechanisms for the reaction of hydroxyl radicals with (<i>E</i>)-4-methoxy-3-buten-2-one and (1<i>E</i>)-1-methoxy-2-methyl-1-penten-3-one
title_sort	atmospheric fate of two relevant unsaturated ketoethers: kinetics, products and mechanisms for the reaction of hydroxyl radicals with (<i>e</i>)-4-methoxy-3-buten-2-one and (1<i>e</i>)-1-methoxy-2-methyl-1-penten-3-one
publisher	Copernicus Publications
series	Atmospheric Chemistry and Physics
issn	1680-7316 1680-7324
publishDate	2020-07-01
description	<p>The kinetics of the gas phase reactions of hydroxyl radicals with two unsaturated ketoethers (UKEs) at (298±3) K and 1 atm of synthetic air have been studied for the first time using the relative-rate technique in an environmental reaction chamber by in situ Fourier-transform infrared spectroscopy (FTIR). The rate coefficients obtained using propene and isobutene as reference compounds were (in units of 10<sup>−10</sup> cm<sup>3</sup> molecule<sup>−1</sup> s<sup>−1</sup>) as follows: <i>k</i><sub>TMBO</sub> (OH + (<i>E</i>)-4-methoxy-3-buten-2-one)  =  (1.41±0.11) and <i>k</i><sub>MMPO</sub> (OH + (1<i>E</i>)-1-methoxy-2-methyl-1-penten-3-one)  =  (3.34±0.43). In addition, quantification of the main oxidation products in the presence of NO<sub><i>x</i></sub> has been performed, and degradation mechanisms for these reactions were developed. Methyl formate, methyl glyoxal, peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN) were identified as main reaction products and quantified for both reactions. The results of the present study provide new insights regarding the contribution of these multifunctional volatile organic compounds (VOCs) in the generation of secondary organic aerosols (SOAs) and long-lived nitrogen containing compounds in the atmosphere. Atmospheric lifetimes and implications are discussed in light of the obtained results.</p>
url	https://www.atmos-chem-phys.net/20/8939/2020/acp-20-8939-2020.pdf
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Atmospheric fate of two relevant unsaturated ketoethers: kinetics, products and mechanisms for the reaction of hydroxyl radicals with (<i>E</i>)-4-methoxy-3-buten-2-one and (1<i>E</i>)-1-methoxy-2-methyl-1-penten-3-one

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