Combined kinetics and iterative target transformation factor analysis for spectroscopic monitoring of reactions

Abstract

Obtaining rate constants and concentration profiles from spectroscopy is important in reaction monitoring. In this paper, we combined kinetic equations and Iterative Target Transformation Factor Analysis (ITTFA) to resolve spectroscopic data acquired during the course of a reaction. This approach is based on the fact that ITTFA needs a first guess (test vectors) of the parameters that will be estimated (target vectors). Three methods are compared. In the first, originally proposed by Furusjö and Danielsson, kinetic modelling is only used to provide the initial test vectors for ITTFA. In the second the rate constant used to provide the test vectors is optimised until a best fit is reached. In the third, a guess of the rate constant is used to provide the test vectors to ITTFA. The outcome of ITTFA is then used to fit the kinetic model and obtain a new guess of the rate constant. With this constant new concentration profiles are generated and provided to the ITTFA algorithm as new test vectors, in an iterative manner, minimising the residuals of the predicted dataset, until convergence. The second and third methods are new implementations of ITTFA and are compared to the first, established, method. First order (both one and two step) and second order reactions were simulated and instrumental noise was introduced. An experimental second order reaction was also employed to test the methods.