Yablonsky Gregory S, Branco Daniel, Marin Guy B, Constales Denis
McKelvey School of Engineering, Department of Energy, Environmental and Chemical Engineering, Washington University in St. Louis, 1 Brookings Dr., St. Louis, MO 63130, USA.
Department of Separation and Conversion Technology, VITO (Flemish Institute for Technological Research), Boeretang 200, B-2400 Mol, Belgium.
Entropy (Basel). 2020 Mar 24;22(3):373. doi: 10.3390/e22030373.
This paper presents a review of our original results obtained during the last decade. These results have been found theoretically for classical mass-action-law models of chemical kinetics and justified experimentally. In contrast with the traditional invariances, they relate to a special battery of kinetic experiments, not a single experiment. Two types of invariances are distinguished and described in detail: thermodynamic invariants, i.e., special combinations of kinetic dependences that yield the equilibrium constants, or simple functions of the equilibrium constants; and "mixed" kinetico-thermodynamic invariances, functions both of equilibrium constants and non-thermodynamic ratios of kinetic coefficients.
本文回顾了我们在过去十年中取得的原创性成果。这些成果已从理论上在化学动力学的经典质量作用定律模型中得出,并通过实验得到了验证。与传统的不变性不同,它们涉及一组特殊的动力学实验,而非单个实验。区分并详细描述了两种类型的不变性:热力学不变性,即产生平衡常数的动力学依赖性的特殊组合,或平衡常数的简单函数;以及“混合”动力学 - 热力学不变性,它是平衡常数和动力学系数的非热力学比值的函数。