Emami Fereshteh, Maeder Marcel, Abdollahi Hamid
Faculty of Chemistry, Institute for Advanced Studies in Basic Sciences, P.O. Box 45195-1159, Zanjan, Iran.
Analyst. 2015 May 7;140(9):3121-35. doi: 10.1039/c4an02279c. Epub 2015 Feb 27.
Thermodynamic studies of equilibrium chemical reactions linked with kinetic procedures are mostly impossible by traditional approaches. In this work, the new concept of generalized kinetic study of thermodynamic parameters is introduced for dynamic data. The examples of equilibria intertwined with kinetic chemical mechanisms include molecular charge transfer complex formation reactions, pH-dependent degradation of chemical compounds and tautomerization kinetics in micellar solutions. Model-based global analysis with the possibility of calculating and embedding the equilibrium and kinetic parameters into the fitting algorithm has allowed the complete analysis of the complex reaction mechanisms. After the fitting process, the optimal equilibrium and kinetic parameters together with an estimate of their standard deviations have been obtained. This work opens up a promising new avenue for obtaining equilibrium constants through the kinetic data analysis for the kinetic reactions that involve equilibrium processes.
用传统方法对与动力学过程相关的平衡化学反应进行热力学研究大多是不可能的。在这项工作中，引入了热力学参数广义动力学研究的新概念来处理动态数据。与动力学化学机制交织的平衡实例包括分子电荷转移络合物形成反应、化合物的pH依赖性降解以及胶束溶液中的互变异构动力学。基于模型的全局分析能够将平衡和动力学参数计算并嵌入到拟合算法中，从而对复杂反应机制进行完整分析。拟合过程完成后，获得了最佳平衡和动力学参数及其标准偏差估计值。这项工作为通过对涉及平衡过程的动力学反应进行动力学数据分析来获得平衡常数开辟了一条有前景的新途径。
