TOWARD A SYSTEMATIC DETERMINATION OF COMPLEX-REACTION MECHANISMS
TOWARD A SYSTEMATIC DETERMINATION OF COMPLEX-REACTION MECHANISMS
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DOI：
10.1021/j100128a006
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发表时间：
1993-07-01
影响因子：
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通讯作者：
ROSS, J
中科院分区：
文献类型：
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作者：
CHEVALIER, T;SCHREIBER, I;ROSS, J
给出一个具有未知或部分已知机制的复杂化学反应，我们考察了通过一些实验方法确定该机制本质部分的可能性，所有这些方法都依赖于对定态雅可比矩阵元(JME)的实验评估。如果能够测量到所有物种对其中一个物种的脉冲扰动的反应，那么就有可能确定所有的JME。另一种不同的实验方法是浓度变化实验，它依赖于测量每种物质的流入改变后化学反应器中稳态浓度的变化。另一种技术是利用对流入物种施加延迟反馈所引起的振荡的诱导(或停止)。如果我们假定动力学为幂定律，则可以根据JME的迹象来确定反应网络的连通性。一旦建立了反应网络的连通性，那么，有了一些基本的化学知识，就可以构建该机理的基本部分。此外，可以根据测量的JME计算出建议的反应速率的速率系数。用从辣根过氧化物酶反应模型计算的JME来说明构造机制的方法。如果能测量到雅可比的逆(浓度移动矩阵)或振荡物种对之间的相移，就可以对振荡反应中的物种进行分类，并对反应机理进行分类。如果由于实验限制，无法评估整个雅可比，这些方法提供了一系列新的测试，任何拟议的机制都必须通过这些测试。定性确定，例如JME的迹象，也可能是有用的。
Given a complex chemical reaction with an unknown or a partially known mechanism, we examine the possibility of determining the essential parts of the mechanism by a number of experimental methods, all of which rely upon the experimental evaluation of the stationary-state Jacobian matrix elements (JMEs). If the response by all species to a pulse perturbation of one of the species can be measured, then it is possible to determine all of the JMEs. A different experimental method, a concentration shift experiment, relies on measuring the change of steady-state concentrations in a chemical reactor after the inflow of each species has been altered. Another technique employs the induction (or cessation) of oscillations caused by a delayed feedback imposed on an inflow species. If we assume power law kinetics, the connectivity of the reaction network can be determined on the basis of the signs of the JMEs. Once the connectivity of the reaction network has been established, then, with some knowledge of basic chemistry, the essential parts of the mechanism can be constructed. Furthermore, the rate coefficients of the suggested reaction rates can be calculated from the measured JMEs. The method of constructing a mechanism is illustrated with JMEs calculated from a model of the horseradish peroxidase reaction. If the inverse of the Jacobian (the concentration shift matrix) or the phase shifts between pairs of oscillating species can be measured, the species in the oscillatory reaction can be classified and the reaction mechanism can be categorized. If, due to experimental constraints, the entire Jacobian cannot be evaluated, these methods offer a new series of tests that must be passed by any proposed mechanism. Qualitative determination, such as the signs of JMEs, can also be useful.