J. Saurina et al., MULTIVARIATE RESOLUTION OF RANK-DEFICIENT SPECTROPHOTOMETRIC DATA FROM FIRST-ORDER KINETIC DECOMPOSITION REACTIONS, Journal of chemometrics, 12(3), 1998, pp. 183-203
The effect of a rank deficiency upon curve resolution in simple kineti
c reaction-based systems is studied. Firstly, simulated rank-deficient
spectrophotometric data of a mixture of two reagents, each one yieldi
ng its own reaction product by a first-order kinetic reaction, are ana
lysed. Four different situations are considered according to the diffe
rences in the spectral responses of the reaction constituents and to t
he differences in the rate constants between the two kinetic processes
. A variation of the rate constant between runs for a certain kinetic
process is also taken into account. Secondly, the resolution of a real
rank-deficient data system, corresponding to the study of the pH-depe
ndent decomposition of 1,2-naphthoquinone-4-sulphonate, is investigate
d. All these studies were carried out using a multivariate curve resol
ution method based on the alternating least squares optimization of th
e kinetic and spectral profiles of the species present in the system.
(C) 1998 John Wiley & Sons, Ltd.