Martínez-Carrión Alicia, Howlett Michael G, Alamillo-Ferrer Carla, Clayton Adam D, Bourne Richard A, Codina Anna, Vidal-Ferran Anton, Adams Ralph W, Burés Jordi
The University of Manchester, School of Chemistry, Oxford Road, Manchester, M13 9PL, UK.
Institute of Chemical Research of Catalonia (ICIQ) and, The Barcelona Institute of Science and Technology (BIST), Av. Països Catalans 16, 43007, Tarragona, Spain.
Angew Chem Int Ed Engl. 2019 Jul 22;58(30):10189-10193. doi: 10.1002/anie.201903878. Epub 2019 Jun 7.
Progress reaction profiles are affected by both catalyst activation and deactivation processes occurring alongside the main reaction. These processes complicate the kinetic analysis of reactions, often directing researchers toward incorrect conclusions. We report the application of two kinetic treatments, based on variable time normalization analysis, to reactions involving catalyst activation and deactivation processes. The first kinetic treatment allows the removal of induction periods or the effect of rate perturbations associated with catalyst deactivation from kinetic profiles when the quantity of active catalyst can be measured. The second treatment allows the estimation of the activation or deactivation profile of the catalyst when the order of the reactants for the main reaction is known. Both treatments facilitate kinetic analysis of reactions suffering catalyst activation or deactivation processes.
进展反应曲线受到与主反应同时发生的催化剂活化和失活过程的影响。这些过程使反应的动力学分析变得复杂，常常导致研究人员得出错误的结论。我们报告了基于可变时间归一化分析的两种动力学处理方法在涉及催化剂活化和失活过程的反应中的应用。第一种动力学处理方法允许在可以测量活性催化剂数量时，从动力学曲线中去除诱导期或与催化剂失活相关的速率扰动的影响。第二种处理方法允许在已知主反应反应物的级数时，估计催化剂的活化或失活曲线。这两种处理方法都有助于对经历催化剂活化或失活过程的反应进行动力学分析。
