...
  • 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Kinetics of OH radical reaction with anthracene and anthracene-d(10)
【24h】

Kinetics of OH radical reaction with anthracene and anthracene-d(10)

机译：蒽与蒽-d（10​​）的OH自由基反应动力学

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

Using a refined pulsed laser photolysis/pulsed laser-induced fluorescence (PLP/PLIF) technique, the kinetics of the reaction of a surrogate three-ring polynuclear aromatic hydrocarbons (PAH), anthracene (and its deuterated form), with hydroxyl (OH) radicals was investigated over the temperature range of 373 to 1200 K. This study represents the first examination of the OH kinetics for this class of reactions at elevated temperatures (> 470 K). The results indicate a complex temperature dependence similar to that observed for simpler aromatic compounds, e.g., benzene. At low temperatures (373-498 K), the rate measurements exhibited Arrhenius behavior (k = 1.82 x 10(-11) exp(542.35/T) in units of cm(3) molecule(-1) s(-1)), and the kinetic isotope effect (KIE) measurements were consistent with an OH-addition mechanism. The low-temperature results are extrapolated to atmospheric temperatures and compared with previous measurements. Rate measurements between 673 and 923 K exhibited a sharp decrease in the magnitude of the rate coefficients (a factor of 9). KIE measurements under these conditions were still consistent with an OH-addition mechanism. The following modified Arrhenius equation is the best fit to our anthracene measurements between 373 and 923 K (in units Of cm(3) molecule(-1) s(-1)): k(1) (373-923 K) = 8.17 x 10(14) T-8.3 exp(-3171.71/T). For a limited temperature range between 1000 and 1200 K, the rate measurements exhibited an apparent positive temperature dependence with the following Arrhenius equation, the best fit to the data (in units of cm(3) molecule(-1) s(-1)): k(1) (999-1200 K) = 2.18 x 10(-11) exp(- 1734.11/T). KIE measurements above 999 K were slightly larger than unity but inclusive regarding the mechanism of the reaction. Theoretical calculations of the KIE indicate the mechanism of reaction at these elevated temperatures is dominated by OH addition with H abstraction being a minor contributor.
机译：使用精细的脉冲激光光解/脉冲激光诱导荧光（PLP / PLIF）技术，替代三环多核芳香烃（PAH），蒽（及其氘代形式）与羟基（OH）的反应动力学在373至1200 K的温度范围内对自由基进行了研究。该研究代表了在高温（> 470 K）下此类反应的OH动力学的首次研究。结果表明，复杂的温度依赖性类似于对较简单的芳族化合物如苯所观察到的依赖性。在低温（373-498 K）下，速率测量显示了Arrhenius行为（k = 1.82 x 10（-11）exp（542.35 / T）以cm（3）分子（-1）s（-1）为单位） ，并且动力学同位素效应（KIE）的测量结果与OH加成机理一致。将低温结果外推至大气温度，并与先前的测量结果进行比较。 673和923 K之间的速率测量结果显示速率系数的幅度急剧下降（系数为9）。在这些条件下的KIE测量仍与OH加成机理一致。以下经修改的Arrhenius方程最适合我们在373至923 K之间的蒽测量（以cm（3）分子（-1）s（-1）为单位）：k（1）（373-923 K）= 8.17 x 10（14）T-8.3 exp（-3171.71 / T）。在1000至1200 K的有限温度范围内，速率测量结果显示出明显的正温度依赖性，并符合以下Arrhenius方程，最适合数据（以cm（3）分子（-1）s（-1）为单位） ）：k（1）（999-1200 K）= 2.18 x 10（-11）exp（-1734.11 / T）。高于999 K的KIE测量值略大于1，但包括反应机理在内。 KIE的理论计算表明，在这些升高的温度下，反应机理主要是OH的添加，而H的提取则占很小的比例。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号