Monitoring of a second‐order reaction by electronic absorption spectroscopy using combined chemometric and kinetic models

This paper reports the application of 11 methods for obtaining kinetic constants from a second‐order reaction, that between phenylhydrazine and benzophenone. In this type of reaction the number of absorbing species is lower than the number of steps in the reaction minus one, resulting in a rank‐deficient response matrix. The methods used include traditional univariate curve fitting, classical least squares using previously recorded pure spectra, alternating least squares methods with both kinetic and non‐negativity constraints, and target‐testing methods using principal component scores. An additional recently proposed method based on difference spectra is also examined, suitable for any single‐step closed reaction. The methods that performed best were difference spectra, kinetically constrained alternating least squares, and target‐testing approaches. Limitations of the traditional methods are described. Copyright © 2003 John Wiley & Sons, Ltd.

[1]  R. Brereton,et al.  Estimation of second order rate constants using chemometric methods with kinetic constraints. , 2002, The Analyst.

[2]  Sarah C. Rutan,et al.  Multivariate curve resolution with non-linear fitting of kinetic profiles , 2001 .

[3]  Age K. Smilde,et al.  Modelling of spectroscopic batch process data using grey models to incorporate external information , 2001 .

[4]  R. Poppi,et al.  Modeling kinetic spectrophotometric data of aminophenol isomers by PARAFAC2 , 2001 .

[5]  R. Tauler,et al.  Combining hard- and soft-modelling to solve kinetic problems , 2000 .

[6]  A. Smilde,et al.  Estimating reaction rate constants: comparison between traditional curve fitting and curve resolution , 2000 .

[7]  Marcel Maeder,et al.  Modern tools for reaction monitoring: hard and soft modelling of ‘non‐ideal’, on‐line acquired spectra , 2000 .

[8]  Richard G. Brereton,et al.  Introduction to multivariate calibration in analytical chemistry , 2000 .

[9]  O. Svensson,et al.  Reaction monitoring using Raman spectroscopy and chemometrics , 1999 .

[10]  D. Walker,et al.  Real time quantitation of a chemical reaction by fiber optic near-infrared spectroscopy , 1999 .

[11]  A. Smilde,et al.  Estimating rate constants and pure UV‐vis spectra of a two‐step reaction using trilinear models , 1999 .

[12]  K. J. Molloy,et al.  Hard modelling of spectroscopic measurements. Applications in non-ideal industrial reaction systems , 1999 .

[13]  H. Haario,et al.  COMBINING SOFT AND HARD MODELLING IN CHEMICAL KINETIC MODELS , 1998 .

[14]  Erik Furusjö,et al.  A method for the determination of reaction mechanisms and rate constants from two-way spectroscopic data , 1998 .

[15]  N. Sidiropoulos,et al.  Least squares algorithms under unimodality and non‐negativity constraints , 1998 .

[16]  Romà Tauler,et al.  Multivariate resolution of rank‐deficient spectrophotometric data from first‐order kinetic decomposition reactions , 1998 .

[17]  J. A. Howell,et al.  Ultraviolet and Absorption Light Spectrometry , 1998 .

[18]  R. Bro,et al.  A fast non‐negativity‐constrained least squares algorithm , 1997 .

[19]  Romà Tauler,et al.  Assessment of new constraints applied to the alternating least squares method , 1997 .

[20]  Yu-Long Xie,et al.  Kinetic spectrophotometric resolution of binary mixtures using three-way partial least squares , 1995 .

[21]  Dominique Bonvin,et al.  On the Rank Deficiency and Rank Augmentation of the Spectral Measurement Matrix , 1996 .

[22]  Jerry Workman.  A Review of Process near Infrared Spectroscopy: 1980–1994 , 1993 .

[23]  H. R. Keller,et al.  Peak purity control in liquid chromatography with photodiode-array detection by a fixed size moving window evolving factor analysis , 1991 .

[24]  George H. Dunteman,et al.  Principal Components Analysis , 1990 .

[25]  H. Mark.  Chemometrics in near-infrared spectroscopy , 1989 .

[26]  E. Thomas,et al.  Kinetic analysis by the method of nonlinear least squares: A reaction involving consecutive steps , 1986 .

[27]  Chris W. Brown,et al.  Matrix representations and criteria for selecting analytical wavelengths for multicomponent spectroscopic analysis , 1982 .

[28]  James H. Espenson,et al.  Chemical kinetics and reaction mechanisms , 1981 .

[29]  E. A. Sylvestre,et al.  Curve Resolution Using a Postulated Chemical Reaction , 1974 .

[30]  E. A. Guggenheim.  XLVI. On the determination of the velocity constant of a unimolecular reaction , 1926 .