Optimal experimental design for estimating the kinetic parameters of processes described by the first-order Arrhenius model under linearly increasingtemperature profiles

The optimum experimental design for systems following the first-order Arrhe nius model under linearly increasing temperature profiles was studied by de termining the sampling conditions that lead to a minimum confidence region of the model parameters. It was found that experiments should be started at the lowest possible temperature and, for each initial temperature, there i s an optimal heating rate. This heating rate is often too high to be feasib le, implying that experiments have to be conducted at a lower practicable h eating rate. In this situation the experiments should be replicated in orde r to improve the precision of the estimates. If both the initial temperatur e and the heating rate are fixed at their optimal values, the optimal sampl ing times correspond to fractional concentrations that are irrational numbe rs (approximately 0.70 and 0.19) whose product is exactly 1/e(2), as earlie r found for the Bigelow model. A case study based on the estimation of the kinetic parameters of the acid hydrolysis of sucrose is also presented. (C) 2000 Elsevier Science Ltd. All rights reserved.