Atmospheric Degradation of CH2═C(CH3)C(O)O[CH2]4CH3 by •OH Radicals: Reactivity, POCP, and Carbonyl Formation

IF 2.7 2区 化学 Q3 CHEMISTRY, PHYSICAL
Vianni Giovanna Straccia Cepeda, María. B. Blanco and Mariano Teruel*, 
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Abstract

Relative rate studies of the gas-phase reaction of amyl methacrylate, CH2═C(CH3)C(O)O[CH2]4CH3, with OH radicals were performed at (298 ± 2) K and 1000 mbar. The experiments were conducted in an atmospheric Pyrex chamber coupled to in situ Fourier transform infrared spectroscopy (FTIR). The rate coefficient obtained from the average of several experiments was kAMMA+•OH = (8.10 ± 1.98) × 10–11 cm3 molecule–1 s–1. Additionally, product studies were conducted under conditions similar to those of the kinetic experiments by using in situ FTIR spectroscopy. Pentanal, butanal, and hydroxyacetone were identified as the main reaction products. The initial pathway for the degradation of amyl methacrylate with OH radicals occurs via addition of OH to the >C═C< bond or hydrogen abstraction from the alkyl chain of the ester. The likelihood of hydrogen atom abstraction is 25%, while the addition of hydroxyl radicals to the double bond occurs with a probability of 75%. Based on these outcomes, a degradation mechanism is postulated. Furthermore, the atmospheric implications of the studied reaction were evaluated by estimating the tropospheric lifetime of amyl methacrylate toward OH radicals as τOH = 3.43 h. Additionally, the Photochemical Ozone Creation Potential (POCP) of 84 was calculated for the reaction studied. Carbonyl compounds found as reaction products can exert a substantial influence on both air quality and public health.

Abstract Image

大气中 -OH 自由基对 CH2═C(CH3)C(O)O[CH2]4CH3 的降解:反应性、POCP 和羰基的形成
在 (298 ± 2) K 和 1000 毫巴条件下,对甲基丙烯酸戊酯(CH2═C(CH3)C(O)O[CH2]4CH3)与 -OH 自由基的气相反应进行了相对速率研究。实验是在大气环境中的一个 Pyrex 室中进行的,并结合了原位傅立叶变换红外光谱仪(FTIR)。多次实验的平均速率系数为 kAMMA+-OH = (8.10 ± 1.98) × 10-11 cm3 molecule-1 s-1。此外,在与动力学实验类似的条件下,还利用原位傅立叶变换红外光谱进行了产物研究。结果表明,戊醛、丁醛和羟基丙酮是主要的反应产物。甲基丙烯酸戊酯与-OH 自由基降解的最初途径是-OH 与>C═C<键相加或从酯的烷基链中抽取氢原子。氢原子抽取的可能性为 25%,而羟基自由基加到双键上的可能性为 75%。根据这些结果,推测出了一种降解机制。此外,通过估算对流层中甲基丙烯酸戊酯向-OH 自由基的生命周期 τOH = 3.43 小时,评估了所研究反应对大气的影响。作为反应产物发现的羰基化合物会对空气质量和公众健康产生重大影响。
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来源期刊
The Journal of Physical Chemistry A
The Journal of Physical Chemistry A 化学-物理:原子、分子和化学物理
CiteScore
5.20
自引率
10.30%
发文量
922
审稿时长
1.3 months
期刊介绍: The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.
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