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Kinetics studies of the OH-initiated oxidation of 2-butyne, propyne, and acetylene were conducted at 100 Torr and 298 K using turbulent flow chemical ionization mass spectrometry. The major oxidation products were identified, and with the aid of supporting electronic structure thermodynamics calculations, a general OH-initiated oxidation mechanism for the alkynes is proposed. The major product branching ratio and the product-forming rate constants for the 2-butyne-OH adduct + O(2) reaction were experimentally determined as well. The atmospheric implications of the chemical oxidation mechanism and kinetics results are discussed.
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http://dx.doi.org/10.1021/jp0454671 | DOI Listing |
Environ Sci Technol
December 2024
Department of Environmental Sciences and Engineering, Gillings School of Global Public Health, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States.
3-Methylenebutane-1,2,4-triol and 3-methyltetrahydrofuran-2,4-diols, previously designated "C-alkene triols", were recently confirmed as in-particle isomerization products of isoprene-derived β-IEPOX isomers that are formed upon acid-driven uptake and partition back into the gas phase. In chamber experiments, we have systematically explored their gas phase oxidation by hydroxyl radical (OH) as a potential source of secondary organic aerosol (SOA). OH-initiated oxidation of both compounds in the presence of ammonium bisulfate aerosol resulted in substantial aerosol volume growth.
View Article and Find Full Text PDFNew particle formation (NPF) in the tropical upper troposphere is a globally important source of atmospheric aerosols. It is known to occur over the Amazon basin, but the nucleation mechanism and chemical precursors have yet to be identified. Here we present comprehensive in situ aircraft measurements showing that extremely low-volatile oxidation products of isoprene, particularly certain organonitrates, drive NPF in the Amazonian upper troposphere.
View Article and Find Full Text PDFJ Phys Chem A
December 2024
Department of Physics, Bharathiar University, Coimbatore 641046, India.
The hydrogen shift reactions of peroxy radicals derived from the ȮH-initiated oxidation of three atmospherically important monoterpenes, limonene, α-pinene, and β-pinene, have been studied. The Bell-Evans-Polanyi relationship (BEPR), Marcus cross relationship (MCR), and Robert-Steel relationship (RSR) are employed to study the factors that contribute to the kinetics of the H-shift reactions. Our results show distinct kinetic behaviors based on the size of the transition-state ring, the functional group present at the H atom abstraction site, and the type of carbon-centered radical formed.
View Article and Find Full Text PDFPhys Chem Chem Phys
October 2024
Department of Chemistry, KU Leuven, Celestijnenlaan, 200F, Leuven 3001, Belgium.
In this study, we revisited the mechanism of isoprene oxidation by OH radicals, focusing on the formation of hydroperoxyaldehydes (HPALDs) in the reactions following O-addition at the α-position to ,'-OH-allyl radical products of the 1,6-H shift of the 1st-generation -δ-OH-isoprenylperoxy radicals. Utilizing high-level quantum chemical calculations and a master equation approach, we provide theoretical confirmation that the formation of δ-HPALDs dominates by far and show that production of β-HPALDs by the mechanism proposed by Wennberg (, 2018, , 3337-3390) is negligible. Besides the dominance of the δ-HPALD formation channel, our investigation also reveals a novel though minor reaction channel resulting in the formation of an allylic δ-hydroperoxy acid and OH radical.
View Article and Find Full Text PDFEnviron Sci Technol
October 2024
Center for Computational Toxicology and Exposure, U.S. Environmental Protection Agency, Research Triangle Park, North Carolina 27711, United States.
Photooxidation products resulting from volatile organic compounds (VOCs) reacting with sunlight are important contributors to gas-phase air pollution. We characterized the product-weighted mutagenic potencies (rev m mgC h) in TA100 of atmospheres resulting from the hydroxyl radical (OH)-initiated photochemical oxidation of 11 C or C alkenes or dienes in the presence of nitric oxide (NO) and from the ozonolysis of four VOCs without NO (isoprene; 1,3-pentadiene; 1,4-pentadiene; and 1,3-butadiene). Irradiated atmospheres from precursors with a single C═C bond (3-methyl-1-butene, 2-methyl-1-butene, -2-pentene, 2-methyl-2-butene, 1-butene, and 1-pentene) had low potencies (<5), whereas linear dienes with terminal C═C bonds had high potencies (50-65).
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