Bath Gas Mixture Effects on Multichannel Reactions: Insights and Representations for Systems beyond Single-Channel Reactions
Bath Gas Mixture Effects on Multichannel Reactions: Insights and Representations for Systems beyond Single-Channel Reactions
复制标题
浴气体混合物对多通道反应的影响：对单通道反应之外的系统的见解和表示
DOI：
10.1021/acs.jpca.8b10581
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发表时间：
2018
期刊：
影响因子：
--
通讯作者：
Burke, Michael P.
中科院分区：
文献类型：
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作者：
Lei, Lei;Burke, Michael P.
几乎所有的研究和现有的数据压力依赖性反应集中在纯浴气体。在相对较少的研究浴气体混合物，重要的燃烧和行星大气，几乎所有的重点是单通道反应。本研究探讨，并寻求可靠的表示，浴气体混合物对多通道反应的影响。主方程的解析解和数值解揭示了多通道反应混合效应的几种独特表现，包括与单通道反应观察到的趋势完全相反的行为。从纯组分的数据中计算混合物速率常数的最常用方法，即经典的线性混合规则，被发现产生的误差超过10倍。一个新的线性混合规则的基础上减少的压力，而不是绝对压力，被发现是准确的？30%的速率常数（和？50%的分支比）。一个新的非线性混合规则，另外采用解析推导的活性系数被发现是准确的速率常数和分支比在10%以内。因此，这些新的混合物规则建议使用在基础和应用化学动力学调查的反应混合物，包括反应流代码和第三体效率的实验解释。
Nearly all studies of and available data for pressure-dependent reactions focus on pure bath gases. Of the comparatively fewer studies on bath gas mixtures, important to combustion and planetary atmospheres, nearly all focus on single-channel reactions. The present study explores, and seeks reliable representations of, bath gas mixture effects on multichannel reactions. Analytical and numerical solutions of the master equation here reveal several unique manifestations of mixture effects for multichannel reactions, including behavior completely opposite to trends observed for single-channel reactions. The most common way of evaluating mixture rate constants from data for pure components, the classic linear mixture rule, is found to yield errors exceeding a factor of ∼10. A new linear mixture rule based on the reduced pressure, instead of the absolute pressure, is found to be accurate within ∼30% for rate constants (and ∼50% for the branching ratio). A new nonlinear mixture rule that additionally incorporates analytically derived activity coefficients is found to be accurate within ∼10% for rate constants and branching ratios. These new mixture rules are therefore recommended for use in fundamental and applied chemical kinetics investigations of reacting mixtures, including reacting flow codes and experimental interpretations of third-body efficiencies.