D- and T-optimum designs for the kinetics of a reversible chemical reaction

The purpose of our paper is to exemplify D-optimum designs for parameter es timation in the kinetics of a reversible chemical reaction and to find T-op timum designs for model discrimination, as a method of determining the orde r of reaction. Although the statistical methods are similar for consecutive and reversible reactions, the designs have markedly different properties. As a chemical example we use the esterification of ethanol and acetic acid. On the basis of this example we discuss the geometrical interpretation of D-optimum designs, which is strictly connected with the course of reaction and permits instructive comparisons of reversible and consecutive chemical processes, The methods of optimum experimental design provide an alternativ e to conventional designs for parameter estimation and model discrimination . We show how much more efficient the optimum design can be for parameter e stimation than relying on a conventional design. We calculate a sequential T-optimum design and propose a statistical test verifying a hypothesis on t he order of reaction. We also present the theoretical background of informa tion matrices for non-linear models, D-optimum designs for parameter estima tion and T-optimum designs for model discrimination. (C) 1998 Elsevier Scie nce B.V, All rights reserved.