Principal component analysis for automaticextraction of solid-state kinetics from combinedin situ experiments

摘要

Solid-state reactivity is often studied by in situ experiments with a multi-technique approaccomplementarity of different probes is exploited n situ data are usually analysed using a complex pirst the reaction model most suited to describe the specific solid-state reaction is chosen, second the reactioncoordinate is obtained from the data. the order of reaction is then calculated by applying a specific kineticequation. and finally kinetic parameters are obtained with an Arrhenius plot. The approach is both timeconsuming and subject to errors due to the arbitrariness of extraction of the reaction coordinate, typicallym individual peak intensity varations during e eacton n additon application of the different kineticequations to obtain the best fitting one is tedious and no gereral method to select the best model withunbiased approach is available. Here we propose a new procedure based on principal component analysget kinetic information from in tu data, which simplifies and speeds up the process of kinetic parameterlculation from a three- to a two- or even a one-step form, reaching a high degree of automation andability to manage the huge ammount of data produced by inew approach treats data as a whole, without biases introduced by manual methods of obtaining theeaction coordinate by peak intensity evaluation from individual patterns typical of the traditionalapproach. The procedure is described in its theoretical framework and appied to the formation of amolecular complex, monitored by in situ X-ray powder diffraction and Raman measurements.