化学
三维旋转形式
非平衡态热力学
化学动力学
反应速率
化学反应
热力学
背景(考古学)
可逆反应
动能
动力学
统计物理学
基本反应
计算化学
催化作用
物理
经典力学
有机化学
古生物学
几何学
数学
生物
作者
Neil K. Razdan,Ting Lin,Aditya Bhan
出处
期刊:Chemical Reviews
[American Chemical Society]
日期:2023-02-21
卷期号:123 (6): 2950-3006
被引量:6
标识
DOI:10.1021/acs.chemrev.2c00510
摘要
The net rate of a reversible chemical reaction is the difference between unidirectional rates of traversal along forward and reverse reaction paths. In a multistep reaction sequence, the forward and reverse trajectories, in general, are not the microscopic reverse of one another; rather, each unidirectional route is comprised of distinct rate-controlling steps, intermediates, and transition states. Consequently, traditional descriptors of rate (e.g., reaction orders) do not reflect intrinsic kinetic information but instead conflate unidirectional contributions determined by (i) the microscopic occurrence of forward/reverse reactions (i.e., unidirectional kinetics) and (ii) the reversibility of reaction (i.e., nonequilibrium thermodynamics). This review aims to provide a comprehensive resource of analytical and conceptual tools which deconvolute the contributions of reaction kinetics and thermodynamics to disambiguate unidirectional reaction trajectories and precisely identify rate- and reversibility-controlling molecular species and steps in reversible reaction systems. The extrication of mechanistic and kinetic information from bidirectional reactions is accomplished through equation-based formalisms (e.g., De Donder relations) grounded in principles of thermodynamics and interpreted in the context of theories of chemical kinetics developed in the past 25 years. The aggregate of mathematical formalisms detailed herein is general to thermochemical and electrochemical reactions and encapsulates a diverse body of scientific literature encompassing chemical physics, thermodynamics, chemical kinetics, catalysis, and kinetic modeling.
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