title: Optimization method for simultaneous kinetic analysis.
abstract: Kinetic analysis is often carried out for simultaneous determinations; thus, a theory to establish its optimal conditions is necessary. A very simple and fast model to find conditions for optimum analytical performance and to predict the quality of simultaneous kinetic analysis has been developed. It is general and applicable to any reaction order or rate constant. The model has been based on the angle between the kinetic vectors and on their norm ratio, which are readily calculated for any kinetic scheme. Evaluation of the proposed model has been carried out by detailed simulations of numerous experimental conditions and analysis by full PCR calculations (when applicable) or nonlinear least-squares fitting. An important conclusion is that analytical performance is determined to a large extent by the stability of the space spanned by the relevant component vectors (in addition to experimental noise and other factors). The quality of the analysis is governed by the angle between the kinetic vectors, while the norm ratio determines the error distribution between components. Optimum conditions for simultaneous kinetic analysis have been studied in several representative examples, regarding the timing of the kinetic monitoring and the effects of concentrations and of rate constant ratios, as well as several other factors of experimental relevance.
authors: Department of Chemistry, Technion [Formula: see text] Israel Institute of Technology, Haifa 32000, Israel.
authors: L
authors: L
authors: Xu
authors: I
authors: I
authors: Schechter