Xi Yiming, Liu Xinquan, Constales Denis, Yablonsky Gregory S
McKelvey School of Engineering, Department of Energy, Environmental and Chemical Engineering, Washington University in St Louis, St. Louis, MO 63130, USA.
Department of Electronics and Information Systems, Ghent University, Building S-8, Krijgslaan 281, B-9000 Ghent, Belgium.
Entropy (Basel). 2020 Oct 15;22(10):1160. doi: 10.3390/e22101160.
The "conservatively perturbed equilibrium" (CPE) technique for a complex chemical system is computationally analyzed in a batch reactor considering different linear mechanisms with three and four species. Contrary to traditional chemical relaxation procedures, in CPE experiments only some initial concentrations are modified; other conditions, including the total amount of chemical elements and temperature are kept unchanged. Generally, for "unperturbed" species with initial concentrations equal to their corresponding equilibrium concentrations, unavoidable extreme values are observed during relaxation to the equilibrium. If the unperturbed species is involved in one step only, this extremum is a momentary equilibrium of the step; if the unperturbed species is involved in more reactions, the extremum is not a momentary equilibrium. The acyclic mechanism with four species may exhibit two extrema and an inflection point, which corresponds to an extremum of the rate of the species change. These facts provide essential information about the detailed mechanism of the complex reaction.
在间歇反应器中，针对具有三种和四种物质的不同线性反应机理，对复杂化学体系的“保守微扰平衡”（CPE）技术进行了计算分析。与传统的化学弛豫程序不同，在CPE实验中，仅修改一些初始浓度；其他条件，包括化学元素总量和温度保持不变。通常，对于初始浓度等于其相应平衡浓度的“未微扰”物质，在弛豫至平衡的过程中会观察到不可避免的极值。如果未微扰物质仅参与一步反应，此极值是该步骤的瞬时平衡；如果未微扰物质参与更多反应，该极值则不是瞬时平衡。具有四种物质的无环反应机理可能表现出两个极值和一个拐点，这对应于物质变化速率的一个极值。这些事实提供了有关复杂反应详细机理的重要信息。
