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OH自由基引发的CH═C(CH)C(O)O[CH]CH的大气降解:反应活性、光化学臭氧生成潜势及羰基生成

Atmospheric Degradation of CH═C(CH)C(O)O[CH]CH by OH Radicals: Reactivity, POCP, and Carbonyl Formation.

作者信息

Straccia Cepeda Vianni Giovanna, Blanco María B, Teruel Mariano

机构信息

(L.U.Q.C.A), Laboratorio Universitario de Química y Contaminación del Aire, Instituto de Investigaciones en Fisicoquímica de Córdoba (I.N.F.I.Q.C.), Dpto. de Fisicoquímica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, 5000 Córdoba, Argentina.

Institute for Atmospheric and Environmental Research, University of Wuppertal, DE-42097 Wuppertal, Germany.

出版信息

J Phys Chem A. 2024 Nov 14;128(45):9782-9791. doi: 10.1021/acs.jpca.4c04393. Epub 2024 Nov 1.

Abstract

Relative rate studies of the gas-phase reaction of amyl methacrylate, CH═C(CH)C(O)O[CH]CH, with OH radicals were performed at (298 ± 2) K and 1000 mbar. The experiments were conducted in an atmospheric Pyrex chamber coupled to Fourier transform infrared spectroscopy (FTIR). The rate coefficient obtained from the average of several experiments was = (8.10 ± 1.98) × 10 cm molecule s. Additionally, product studies were conducted under conditions similar to those of the kinetic experiments by using 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 τ = 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.

摘要

在(298±2)K和1000毫巴的条件下,对甲基丙烯酸戊酯(CH═C(CH)C(O)O[CH]CH)与羟基自由基的气相反应进行了相对速率研究。实验在与傅里叶变换红外光谱仪(FTIR)相连的常压派热克斯玻璃腔中进行。通过多次实验的平均值得到的速率系数为 = (8.10 ± 1.98) × 10 cm³分子⁻¹·秒⁻¹。此外,在与动力学实验相似的条件下,使用FTIR光谱进行了产物研究。已鉴定出戊醛、丁醛和羟基丙酮为主要反应产物。甲基丙烯酸戊酯与羟基自由基降解的初始途径是通过羟基加成到>C═C<键上或从酯的烷基链上夺取氢。夺取氢原子的可能性为25%,而羟基自由基加成到双键上的概率为75%。基于这些结果,提出了一种降解机制。此外,通过估计甲基丙烯酸戊酯对羟基自由基的对流层寿命为τ = 3.43小时,评估了所研究反应对大气的影响。此外,还计算了所研究反应的光化学臭氧生成潜力(POCP)为84。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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