Leveraging De Donder relations for a thermodynamically rigorous analysis of reaction kinetics in liquid media
Leveraging De Donder relations for a thermodynamically rigorous analysis of reaction kinetics in liquid media
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利用 De Donder 关系对液体介质中的反应动力学进行热力学严格分析
DOI：
10.1016/j.jcat.2021.09.026
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发表时间：
2021
影响因子：
7.3
通讯作者：
Bond, Jesse Q.
中科院分区：
文献类型：
--
作者：
Schwartz, Thomas J.;Bond, Jesse Q.
这个迷你审查认为使用德唐德关系，以促进严格的讨论液相反应动力学通过分析的基本步骤。在量化“溶剂效应”时，纯物质参考态是方便的。速率表达式开发与此公约捕获所有的影响，在溶剂的特定的活性系数或过剩的自由能的热力学非理想性，而通常应用的无限稀释参考状态导致溶剂和组合物依赖的标准状态的速率和平衡常数。描述了两种溶剂效应：“动力学”效应，其包括在基本步骤中相对于反应物的过渡态的溶剂化，和“热力学”效应，其包括在基本步骤中相对于反应物的产物的溶剂化。前者影响远期汇率常数，后者影响可逆性。这些效应在De Donder速率表达式中被正式编码;因此，它们内在地解释了溶剂化，同时保持了基本速率和平衡常数的热力学一致性。一系列的案例研究。这些结果表明，溶剂效应可能导致在液相反应的常规分析过程中与预期行为的实质性偏差。此外，我们发现，表面反应和多反应序列中的速率控制程度可以受到本体溶剂化的影响，但这种影响是难以预测的先验。
This Mini-review considers the use of De Donder relations to facilitate a thermodynamically rigorous discussion of liquid-phase reaction kinetics through the analysis of elementary steps. In quantifying “solvent effects,” pure species reference states are convenient. Rate expressions developed with this convention capture all effects of thermodynamic non-ideality in solvent-specific activity coefficients or excess free energies, whereas commonly applied infinite dilution reference states lead to solvent- and composition-dependent standard-state rate and equilibrium constants. Two solvent effects are described: a “kinetic” effect, which comprises solvation of a transition state relative to reactants in an elementary step, and a “thermodynamic” effect, which comprises solvation of products relative to reactants in an elementary step. The former impacts the forward rate constant, and the latter impacts the reversibility. These effects are formally encoded in De Donder rate expressions; thus, they inherently account for solvation while maintaining thermodynamic consistency with respect to elementary rate and equilibrium constants. A series of case studies are presented. These demonstrate that solvent effects can lead to substantial deviations from anticipated behavior during routine analysis of liquid-phase reactions. Additionally, we find that surface reactions and degree of rate control in multi-reaction sequences can be impacted by bulk solvation, but such effects are difficult to predicta priori.