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首页> 外文期刊>Combustion and Flame >Rate constants for reactions of ethylbenzene with hydroperoxyl radical
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Rate constants for reactions of ethylbenzene with hydroperoxyl radical

机译：乙苯与氢过氧自由基反应的速率常数

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摘要

Acentral step in the low-temperature oxidation of hydrocarbons is the abstraction of H by the hydroperoxyl radical (HO_2). In this study, reaction rate constants are derived theoretically for H abstraction by HO_2 from the three distinct locations of H in ethylbenzene (primary, secondary and aromatic H, with H on the ortho carbon taken as an example of unreactive aromatic H) as well as for the addition of HO_2 at the four possible aromatic sites. Potential energy surface is mapped out based on the results of computations performed with the composite CBS-QB3 theoretical method. Rate constants are fitted to modified Arrhenius forms in the wide temperature range of 300-2000 K. The dominant channel at all temperatures is found to be H abstraction from the secondary C of the ethyl chain with a rate constant expression of k = 1.28 × 10~(-24)T~(3.70) exp(_T/~(T5100)= cm3~ molecule~(-1) s~(-1). Abstraction from the primary C also contributes significantly at higher temperatures (>800 K) with a rate constant expression of k = 2.90 × 10~(-24)T~(3.78) exp (_T/~(-8400)) cm~3 molecule~(-1) s~(-1). Reasonable agreement was obtained with the limited experimental data available in the literature. Addition at the four sites of the aromatic ring and abstraction of one of the C-H aromatic bonds are relatively unimportant over the temperature range studied. We also investigate the abstraction of H from the secondary C on the ethyl chain by triplet oxygen and report the associated rate expression. The results presented herein should be useful in modelling the oxidation of alkylbenzenes at lower temperatures.
机译：碳氢化合物低温氧化的关键步骤是氢过氧自由基（HO_2）提取H。在这项研究中，理论上通过HO_2从乙苯中H的三个不同位置（伯，仲和芳族H，邻碳上的H作为非反应性芳族H的例子）得出了H_2提取H的反应速率常数，以及在四个可能的芳香位点添加HO_2。根据使用复合CBS-QB3理论方法执行的计算结果，绘制出势能面。将速率常数拟合到300-2000 K的宽温度范围内的修饰的Arrhenius形式。发现在所有温度下，主要通道是从乙基链的仲C提取的H，速率常数表示为k = 1.28×10 〜（-24）T〜（3.70）exp（_T /〜（T5100）= cm3〜分子〜（-1）s〜（-1）。在较高温度（> 800 K）下从一次C的提取也有显着贡献速率常数为k = 2.90×10〜（-24）T〜（3.78）exp（_T /〜（-8400））cm〜3分子〜（-1）s〜（-1）。在有限的实验数据下获得，在所研究的温度范围内，芳环的四个位点的加成和一个CH芳族键的抽象相对不重要，我们还研究了从C上的仲C提取H并通过三重态氧连接乙基链并报告相关的速率表达，此处给出的结果应可用于模拟烷基的氧化在较低温度下进入。

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  • 来源
    《Combustion and Flame》 |2013年第1期|9-16|共8页
  • 作者

    Mohammednoor Khalil Altarawneh; Bogdan Z. Dlugogorski; Eric M. Kennedy; John C. Mackie;

  • 作者单位

    Priority Research Centre for Energy, Faculty of Engineering & Built Environment, The University of Newcastle, Callaghan, NSW 2308, Australia,Chemical Engineering Department, Al-Hussein Bin Talal University, Ma'an, Jordan;

    Priority Research Centre for Energy, Faculty of Engineering & Built Environment, The University of Newcastle, Callaghan, NSW 2308, Australia;

    Priority Research Centre for Energy, Faculty of Engineering & Built Environment, The University of Newcastle, Callaghan, NSW 2308, Australia;

    Priority Research Centre for Energy, Faculty of Engineering & Built Environment, The University of Newcastle, Callaghan, NSW 2308, Australia,School of Chemistry, The University of Sydney, Australia;

  • 收录信息 美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

    HO_2 radicals; alkylbenzene; TST; ethylbenzene; cool flames; negative temperature coefficient;

    机译：HO_2基团;烷基苯TST;乙苯;凉爽的火焰;负温度系数;

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