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
{"title":"Theoretical and experimental study of the OH radical with 3-bromopropene gas phase reaction rate coefficients temperature dependence","authors":"Mauro González Vera,&nbsp;Pablo Marcelo Cometto,&nbsp;Juan Manuel Casañas,&nbsp;Glauco F. Bauerfeldt,&nbsp;Abdelwahid Mellouki","doi":"10.1002/poc.4555","DOIUrl":null,"url":null,"abstract":"<p>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 (<i>k</i>) 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.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":1.9000,"publicationDate":"2023-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Physical Organic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/poc.4555","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
引用次数: 0

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.

Abstract Image

查看原文
分享 分享
微信好友 朋友圈 QQ好友 复制链接
本刊更多论文
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。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
求助全文
约1分钟内获得全文 去求助
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.
期刊最新文献
Issue Information Cover Image Cover Image Issue Information Enhanced Hyperpolarizabilities Through p‐Phenylene Bridges: Computational Studies on Metamerism and Functional Molecular Properties of Pyridinium–Dicyanomethanide‐Based Zwitterions
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
现在去查看 取消
×
提示
确定
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
已复制链接
已复制链接
快去分享给好友吧!
我知道了
×
扫码分享
扫码分享
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术
文献互助 智能选刊 最新文献 互助须知 联系我们:info@booksci.cn
Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。
Copyright © 2023 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1