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近大气条件下α-蒎烯在羟基自由基引发氧化过程中的过氧自由基过程及产物形成

Peroxy Radical Processes and Product Formation in the OH Radical-Initiated Oxidation of α-Pinene for Near-Atmospheric Conditions.

作者信息

Berndt Torsten

机构信息

Atmospheric Chemistry Department (ACD), Leibniz Institute for Tropospheric Research (TROPOS), Permoserstraße 15, 04318 Leipzig, Germany.

出版信息

J Phys Chem A. 2021 Oct 21;125(41):9151-9160. doi: 10.1021/acs.jpca.1c05576. Epub 2021 Oct 12.

Abstract

α-Pinene, CH, represents one of the most important biogenic emissions into the atmosphere. The formation of RO radicals HO-CHO, = 2-6, and their closed-shell products from the OH + α-pinene reaction has been measured for close to atmospheric reaction conditions in the presence of NO with concentrations of (1.7-490) × 10 molecules cm. Main closed-shell products are substances with the composition CHO and CHO, most likely carbonyls, obtained with molar yields in the range 0.42-0.45 and 0.17-0.19, respectively, for NO concentrations >5 × 10 molecules cm. The corresponding total product yields amount to 0.75-0.81, indicating efficient product detection by the mass spectrometric method applied. All stated molar yields represent lower limit values affected with an uncertainty of [Formula: see text]. Kinetic and product analysis consistently revealed the suppression of the formation of highly oxygenated organic molecules (HOMs) by a factor of 2-2.2 for the highest NO concentration used. The findings of this study provide insights into the RO radical processes of the OH + α-pinene reaction for atmospheric conditions and give an overview about the first-generation products.

摘要

α-蒎烯(CH)是大气中最重要的生物源排放物之一。在接近大气反应条件下,于存在浓度为(1.7 - 490)×10分子/cm³的NO的情况下,已对OH + α-蒎烯反应中RO自由基HO-CHO(= 2 - 6)及其闭壳产物的形成进行了测量。主要的闭壳产物是组成分别为CHO和CHO的物质,很可能是羰基化合物,对于NO浓度>5×10分子/cm³的情况,其摩尔产率分别在0.42 - 0.45和0.17 - 0.19范围内。相应的总产物产率为0.75 - 0.81,表明所应用的质谱方法能有效检测产物。所有所述的摩尔产率均代表下限值,受[公式:见原文]的不确定性影响。动力学和产物分析一致表明,对于所使用的最高NO浓度,高度氧化有机分子(HOMs)的形成被抑制了2至2.2倍。本研究的结果为大气条件下OH + α-蒎烯反应的RO自由基过程提供了见解,并给出了第一代产物的概述。

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