Optimal experimental design for estimating the kinetic parameters of processes described by the first-order Arrhenius model under linearly increasing temperature profiles Original Research Article

The optimum experimental design for systems following the first-order Arrhenius model under linearly increasing temperature profiles was studied by determining 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 is an optimal heating rate. This heating rate is often too high to be feasible, implying that experiments have to be conducted at a lower practicable heating rate. In this situation the experiments should be replicated in order to improve the precision of the estimates. If both the initial temperature and the heating rate are fixed at their optimal values, the optimal sampling times correspond to fractional concentrations that are irrational numbers (approximately 0.70 and 0.19) whose product is exactly 1/e2, as earlier 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.