可逆反应系统动力学分析的相关概念,Chemical Reviews

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可逆反应系统动力学分析的相关概念
Chemical Reviews ( IF 51.4 ) Pub Date : 2023-02-21 , DOI: 10.1021/acs.chemrev.2c00510
Neil K Razdan ₁ , Ting C Lin ₁ , Aditya Bhan ₁

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可逆化学反应的净速率是沿正向和反向反应路径的单向遍历速率之间的差异。在多步反应序列中，正向和反向轨迹通常不是彼此的微观反向；相反，每条单向路线都由不同的速率控制步骤、中间体和过渡状态组成。因此，传统的速率描述符（例如，反应级数）不反映内在动力学信息，而是将单向贡献混为一谈（i）正向/反向反应的微观发生（即单向动力学）和（ii）反应的可逆性（即非平衡热力学）。本综述旨在提供分析和概念工具的综合资源，这些工具可以解卷积反应动力学和热力学的贡献，以消除单向反应轨迹的歧义，并精确识别可逆反应系统中控制速率和可逆性的分子种类和步骤。从双向反应中提取机械和动力学信息是通过以热力学原理为基础并在过去 25 年发展的化学动力学理论背景下进行解释的基于方程的形式主义（例如，德唐德关系）来实现的。此处详述的数学形式的集合对于热化学和电化学反应是通用的，并且囊括了包括化学物理学、热力学、

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Concepts Relevant for the Kinetic Analysis of Reversible Reaction Systems

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.

更新日期：2023-02-21

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