Theoretically predicted rate constants for mercury oxidation by hydrogen chloride in coal combustion flue gases.
Theoretically predicted rate constants for mercury oxidation by hydrogen chloride in coal combustion flue gases.
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DOI：
10.1021/es034025k
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发表时间：
2003-08
影响因子：
11.4
通讯作者：
J. Wilcox;J. Robles;David C. J. Marsden;P. Blowers
中科院分区：
文献类型：
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作者：
J. Wilcox;J. Robles;David C. J. Marsden;P. Blowers
在这项工作中，估计了煤燃烧烟气中可能发生的氯化氢汞氧化反应的理论速率常数。利用过渡态理论计算了单激发和双激发的二次组态相互作用（QCI）水平的速率常数，并与密度泛函理论的结果进行了比较，两者都包括汞的高水平伪势。热力学和动力学数据从文献被用来评估理论计算的准确性时，可能的。所选方法和基组的验证是基于以前和目前对涉及氯的汞反应的研究。目前的研究表明，采用1992年Stevens等人的基集的QCISD方法可以得到含氯分子氧化汞的最准确的动力学和热力学结果。此外，对一系列汞氧化反应的反应热数据的比较表明，密度泛函方法B3LYP与1997年的Stuttgart基集可以为这些大型体系提供相当准确的结果。
In this work, theoretical rate constants are estimated for mercury oxidation reactions by hydrogen chloride that may occur in the flue gases of coal combustion. Rate constants are calculated using transition state theory at the quadratic configuration interaction (QCI) level of theory with single and double excitations, and are compared to results obtained from density functional theory, both including high level pseudopotentials for mercury. Thermodynamic and kinetic data from the literature are used to assess the accuracy of the theoretical calculations when possible. Validation of the chosen methods and basis sets is based upon previous and current research on mercury reactions involving chlorine. The present research shows that the QCISD method with the 1992 Stevens et al. basis set leads to the most accurate kinetic and thermodynamic results for the oxidation of mercury via chlorine containing molecules. Also, a comparison of the heats of reaction data for a series of mercury oxidation reactions reveals that the density functional method, B3LYP, with the 1997 Stuttgart basis set provides reasonably accurate results for these large systems.