Steady State Kinetics of Any Catalytic Network: Graph Theory, the Energy Span Model, the Analogy between Catalysis and Electrical Circuits, and the Meaning of "Mechanism"
Steady State Kinetics of Any Catalytic Network: Graph Theory, the Energy Span Model, the Analogy between Catalysis and Electrical Circuits, and the Meaning of "Mechanism"
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DOI：
10.1021/acscatal.5b00694
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发表时间：
2015-09-01
期刊：
影响因子：
12.9
通讯作者：
Kozuch, Sebastian
中科院分区：
文献类型：
--
作者：
Kozuch, Sebastian
正如King和Altman最初指出的那样，图论，特别是生成树的使用，提供了以所有速率常数作为输入数据来求解稳态区域中任何催化网络的动力学的方法。结果表明，速率常数到吉布斯能的转换提供了一种更简单的方法来估计任何和所有催化网络的能量跨度(即完全反应的表观活化能)、决定态和周转频率(TOF)。通过严格的数学处理重新审视化学动力学的概念，提出了“化学机理”一词的另一种定义。此外，与电路类似，将化学电阻术语(这里称为“激励器”)识别为串联和并联化学电路，为催化提供了一种新的欧姆解释。
As originally shown by King and Altman, graph theory, and specifically the use of spanning trees, provides the means to solve the kinetics of any catalytic network in a steady state regime, taking as input data all the rate constants. Herein, it is shown that the translation of the rate constants to Gibbs energies provides a simpler way to estimate the energy span (i.e., the apparent activation energy of the full reaction), the determining states, and the turnover frequency (TOF) of any and all catalytic networks. By re-examining the concepts of chemical kinetics through rigorous mathematical treatment, an alternative definition is suggested for the term "chemical mechanism". In addition, and in analogy to electrical circuits, the chemical resistor terms (called here "kinestors") are identified for parallel and series chemical circuits, providing a new Ohmic interpretation for catalysis.