Khawam Ammar, Flanagan Douglas R
Division of Pharmaceutics, College of Pharmacy, University of Iowa, 115 South Grand Avenue, Iowa City, Iowa 52242, USA.
J Phys Chem B. 2005 May 26;109(20):10073-80. doi: 10.1021/jp050589u.
There are many methods for analyzing solid-state kinetic data. They are generally grouped into two categories, model-fitting and isoconversional (model-free) methods. Historically, model-fitting methods were widely used because of their ability to directly determine the kinetic triplet (i.e., frequency factor [A], activation energy [E(a)], and model). However, these methods suffer from several problems among which is their inability to uniquely determine the reaction model. This has led to the decline of these methods in favor of isoconversional methods that evaluate kinetics without modelistic assumptions. This work proposes an approach that combines the power of isoconversional methods with model-fitting methods. It is based on using isoconversional methods instead of traditional statistical fitting methods to select the reaction model. Once a reaction model has been selected, the activation energy and frequency factor can be determined for that model. This approach was investigated for simulated and real experimental data for desolvation reactions of sulfameter solvates.
分析固态动力学数据有许多方法。它们通常分为两类，即模型拟合方法和等转化率（无模型）方法。从历史上看，模型拟合方法因其能够直接确定动力学三元组（即频率因子[A]、活化能[E(a)]和模型）而被广泛使用。然而，这些方法存在几个问题，其中之一是它们无法唯一确定反应模型。这导致这些方法逐渐被等转化率方法所取代，等转化率方法在不做模型假设的情况下评估动力学。这项工作提出了一种将等转化率方法的优势与模型拟合方法相结合的方法。它基于使用等转化率方法而非传统的统计拟合方法来选择反应模型。一旦选择了反应模型，就可以确定该模型的活化能和频率因子。针对磺胺间甲氧嘧啶溶剂化物去溶剂化反应的模拟和实际实验数据，对该方法进行了研究。
