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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Systematic Application of the Principle of Detailed Balancing to Complex Homogeneous Chemical Reaction Mechanisms
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Systematic Application of the Principle of Detailed Balancing to Complex Homogeneous Chemical Reaction Mechanisms

机译：系统应用对复杂均相化学反应机制的详细平衡原理

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摘要

It is not uncommon for proposed complex reaction mechanisms to violate the principle of detailed balancing. Here, we draw attention to three ways in which such violations can occur: reversible reaction loops where the rate constants do not attain closure, illegal loops, and reversible steps having rate equations in the forward and reverse directions that are inconsistent with the equilibrium expressions. We present two simple methods to test whether a proposed mechanism is consistent with the first two aspects of the principle of detailed balancing. Both methods are restricted to closed homogeneous isothermal reactions having mechanisms that consist of stoichiometrically balanced reaction steps. The first method is restricted to mechanisms in which all reaction steps are reversible; values of Delta(f)G degrees are assigned to all reaction species, equilibrium constants are then computed for all steps, and all rate constants for elementary steps are constrained by the relationship K-eq = k(f)/k(r). The second method is applicable to mechanisms that can consist of a series of reversible and/or irreversible reaction steps. One first examines the subset of reversible steps to determine whether any of these steps are stoichiometrically equivalent to a combination of any of the other steps. If so, the forward and reverse rate expressions must yield equilibrium constants that are in agreement with the stoichiometric relationships. Next, the complete set of steps is examined to look for "illegal reaction loops". Both of these procedures are performed by constructing matrices that represent the stoichiometries of the various reaction steps and then performing row reductions to identify basis sets of loops. A method based on linear programming is described that determines whether a mechanism contains any illegal loops. These methods are applied in the analysis of several published reaction mechanisms.
机译：提出复杂的反应机制并不罕见，以违反详细平衡的原则。在这里，我们注意到三种方式，其中可能发生这种违规行为：可逆反应循环，其中速率常数不达到闭合，非法环绕和具有与均衡表达不一致的向前和反向方向上的速率方程的可逆步骤。我们提出了两种简单的方法来测试拟议机制是否与详细平衡原则的前两个方面一致。两种方法都仅限于闭合均匀的等温反应，该机制由由化学计量平衡的反应步骤组成的机制。第一种方法仅限于所有反应步骤是可逆的机制; δ（F）G度的值被分配给所有反应物种，然后计算所有步骤的平衡常数，并且基本步骤的所有速率常数受到关系K-EQ = K（F）/ K（R）的约束。第二种方法适用于可由一系列可逆和/或不可逆的反应步骤组成的机制。首先检查可逆步骤的子集，以确定这些步骤中的任何一种是否是化学计量等同于任何其他步骤的组合。如果是，则前向和反向速率表达必须产生与化学计量关系一致的平衡常数。接下来，检查完整的步骤，以寻找“非法反应环”。这两种过程都是通过构建代表各种反作步步骤的化学测定物的矩阵来执行，然后执行行减少以识别基组环。描述了一种基于线性编程的方法，其确定机制是否包含任何非法循环。这些方法用于分析几种公开的反应机制。

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