Estimating kinetic parameters of complex catalytic reactions using a curve resolution based method

A Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) based algorithm is used to extract kinetic parameters from on-line FT - NIR data of a series of Heck reactions between iodobenzene and n-butyl acrylate (NBA), measured at different temperatures with different catalysts. Four catalysts are prepared in situ from a Pd(OAc)(2) (precursor), and a ligand (triphenyl-phosphine and triphenyl-phosphite) in different ligand/Pd ratios. The entire dataset for all reactions is then used to calculate the kinetic parameters directly from the spectra. The algorithm is first validated using simulated data and then applied to the experimental data. The results are compared with those from a calibration model. Coupled with a kinetic model and some a priori information over the system, the algorithm yields good results within a range of feasible starting values of the model parameters. (c) 2007 Elsevier B.V. All rights reserved.