title: Comparison of PLS and kinetic models for a second-order reaction as monitored using ultraviolet visible and mid-infrared spectroscopy.
abstract: A second-order reaction between benzophenone and phenylhydrazine to give benzophenone phenylhydrazone was followed using UV/vis and mid-infrared spectroscopic probes. Established kinetic (hard) and partial least squares (soft) modelling chemometrics methods were applied to both datasets in order to compare the information acquired with each probe. To this purpose, an experimental design with 25 samples and a test set with 5 samples were used to build a partial least squares calibration model to predict the concentration profiles of the compounds present in the reaction vessel. In addition, multivariate kinetic modelling was also performed on the spectroscopic data. Using a guess of the rate constant, concentration profiles were estimated. The profiles are then used to calculate the estimated spectroscopic profile, which is compared to the data acquired experimentally. The residual is minimised and the rate constant estimated; this procedure is iterated until convergence. A total of four profiles were obtained for each compound, corresponding to two sets of probes and two sets of models. The results were compared and discussed. It is shown that several different spectroscopic techniques can be used in reaction monitoring, with increasing benefits in terms of information and interpretation of the results. The profiles obtained agreed well which was also demonstrated when comparing the different rate constants obtained.
authors.affiliation: School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS, UK.
authors.forename: Antonio R
authors.initials: AR
authors.lastname: de Carvalho
authors.forename: Miguel Del Nogal
authors.initials: Mdel N
authors.lastname: Sánchez
authors.forename: Jirut
authors.initials: J
authors.lastname: Wattoom
authors.forename: Richard G
authors.initials: RG
authors.lastname: Brereton