Theoretical and experimental study of the OH radical with 3-bromopropene gas phase reaction rate coefficients temperature dependence

IF 1.9 4区 化学 Q2 CHEMISTRY, ORGANIC Journal of Physical Organic Chemistry Pub Date : 2023-06-16 DOI:10.1002/poc.4555
Mauro González Vera, Pablo Marcelo Cometto, Juan Manuel Casañas, Glauco F. Bauerfeldt, Abdelwahid Mellouki
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Abstract

In this work, the rate-determining steps of the OH radical + 3-bromopropene gas phase reaction were studied, which could explain for the possible negative activation energy observed in experiments. To obtain new kinetic parameters and data for critical revisions, a reinvestigation of the rate coefficient (k) and its temperature dependence was carried out using the PLP-LIF technique, in the 254- to 371-K range. Moreover, quantum-mechanical and canonical variational transition state theory calculations were performed, taking into consideration four OH addition and two β-hydrogen atom abstraction reaction channels. The proposed kinetic model fits to the observed experimental Arrhenius behavior, and three not negligible reaction pathways are described for the first time.

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OH自由基与3-溴丙烷气相反应速率系数温度相关性的理论和实验研究。
本工作研究了OH自由基+ 3-溴丙烯气相反应的速率决定步骤,这可以解释实验中观察到的可能的负活化能。为了获得新的动力学参数和关键修正数据,使用PLP-LIF技术重新研究了速率系数(k)及其在254至371 k范围内的温度依赖性。此外,考虑4个OH加成反应通道和2个β-氢原子抽离反应通道,进行了量子力学和正则变分过渡态理论计算。提出的动力学模型与实验观察到的阿伦尼乌斯行为相吻合,并首次描述了三个不可忽略的反应途径。
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来源期刊
CiteScore
3.60
自引率
11.10%
发文量
161
审稿时长
2.3 months
期刊介绍: The Journal of Physical Organic Chemistry is the foremost international journal devoted to the relationship between molecular structure and chemical reactivity in organic systems. It publishes Research Articles, Reviews and Mini Reviews based on research striving to understand the principles governing chemical structures in relation to activity and transformation with physical and mathematical rigor, using results derived from experimental and computational methods. Physical Organic Chemistry is a central and fundamental field with multiple applications in fields such as molecular recognition, supramolecular chemistry, catalysis, photochemistry, biological and material sciences, nanotechnology and surface science.
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