Relative Humidity and Altitude Effects on the Water-Mediated Hydrogen Abstraction Reaction of Furan by the Hydroxyl Radical

IF 2.9 3区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

ACS Earth and Space Chemistry Pub Date : 2024-10-15 DOI:10.1021/acsearthspacechem.4c0021610.1021/acsearthspacechem.4c00216

Joel Leitão Nascimento, Bruno Santana Sampaio, Murillo H. Queiroz, Roberto Rivelino* and Tiago Vinicius Alves*,

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Abstract

Despite the relevance of furanic compounds as atmospheric pollutants, the role of the water molecule in their oxidation mechanisms still needs to be comprehended. Here, we present new insights into furan’s water-mediated hydrogen abstraction mechanism by the OH radical and its atmospheric implications. Compared to the naked mechanism, the addition of the water monomer increases the chemical complexity, yielding three and six pathways for the hydrogen abstraction on the α and β carbons, respectively. Employing the pre-equilibrium model, we calculate the termolecular rate constants and then estimate the effective reaction rate as a function of the relative humidity. Our results suggest that the effect of water on the hydrogen abstraction rate is negligible. In addition, we also determined that the reaction rate at the stratosphere is 5 orders of magnitude slower compared to the troposphere.

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相对湿度和海拔高度对羟基自由基水介导的呋喃析氢反应的影响

尽管呋喃类化合物与大气污染物息息相关，但水分子在其氧化机制中的作用仍有待了解。在此，我们对呋喃的水介导氢氧自由基抽取氢的机理及其对大气的影响提出了新的见解。与裸机制相比，水单体的加入增加了化学复杂性，在 α 和 β 碳上分别产生了三种和六种取氢途径。利用前平衡模型，我们计算了分子速率常数，然后估算了有效反应速率与相对湿度的函数关系。结果表明，水对取氢速率的影响可以忽略不计。此外，我们还确定平流层的反应速率比对流层慢 5 个数量级。

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来源期刊

ACS Earth and Space Chemistry Earth and Planetary Sciences-Geochemistry and Petrology

CiteScore

5.30

自引率

11.80%

发文量

249

期刊介绍： The scope of ACS Earth and Space Chemistry includes the application of analytical, experimental and theoretical chemistry to investigate research questions relevant to the Earth and Space. The journal encompasses the highly interdisciplinary nature of research in this area, while emphasizing chemistry and chemical research tools as the unifying theme. The journal publishes broadly in the domains of high- and low-temperature geochemistry, atmospheric chemistry, marine chemistry, planetary chemistry, astrochemistry, and analytical geochemistry. ACS Earth and Space Chemistry publishes Articles, Letters, Reviews, and Features to provide flexible formats to readily communicate all aspects of research in these fields.