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Reactions of OH radicals with 2-methyl-1-butyl, neopentyl and 1-hexyl nitrates. Structure-activity relationship for gas-phase reactions of OH with alkyl nitrates: An update

Abstract : The kinetics of the reactions 2-methyl-1-butyl (2M1BNT), neopentyl (NPTNT) and 1-hexyl nitrates (1HXNT) with OH radicals has been studied using a low pressure flow tube reactor combined with a quadrupole mass spectrometer. The rate constants of the title reactions were determined under pseudo-first order conditions from kinetics of OH consumption in excess of nitrates. The overall rate coefficients, k2M1BNT = 1.54 × 10−14 (T/298)4.85 exp (1463/T) (T = 278–538 K), kNPTNT = 1.39 × 10−14 (T/298)4.89 exp (1189/T) (T = 278–500 K) and k1HXNT = 2.23 × 10−13 (T/298)2.83 exp (853/T) cm3molecule−1s−1 (T = 306–538 K) (with conservative 15% uncertainty), were determined at a total pressure of 1 Torr of helium. The yield of trimethylacetaldehyde ((CH3)3CCHO), resulting from the abstraction by OH of an α-hydrogen atom in neopentyl nitrate, followed by α-substituted alkyl radical decomposition, was determined as 0.31 ± 0.06 at T = 298 K. The calculated tropospheric lifetimes of 2M1BNT, NPTNT and 1HXNT indicate that reaction of these nitrates with OH represents an important sink of these compounds in the atmosphere. Based on the available kinetic data, we have updated the structure-activity relationship (SAR) for reactions of alkyl nitrates with OH at T = 298 K. Good agreement (within 20%) is obtained between experimentally measured rate constants (total and that for H-atom abstraction from α carbon) and those calculated from SAR using new substituents factors for almost all the experimental data available.
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https://hal.archives-ouvertes.fr/hal-01804174
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Submitted on : Wednesday, January 12, 2022 - 5:55:52 PM
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Yuri Bedjanian, Julien Morin, Manolis Romanias. Reactions of OH radicals with 2-methyl-1-butyl, neopentyl and 1-hexyl nitrates. Structure-activity relationship for gas-phase reactions of OH with alkyl nitrates: An update. Atmospheric Environment, Elsevier, 2018, 180, pp.167 - 172. ⟨10.1016/j.atmosenv.2018.03.002⟩. ⟨hal-01804174⟩

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