Nonlinear least squares analysis of catalytic rate models

Conventional data generation and analysis procedures used to select a descriptive Hougen‐Watson reaction rate model have been reviewed and some statistical objections to these conventional procedures have been presented. In an attempt to assess the practical importance of these objections, a recently published example was analyzed with both conventional techniques and nonlinear least squares procedures, which more closely conform to theoretical weighting requirements. Comparisons were made between the results of the conventional linear least squares analysis of isothermal data and those of nonlinear least squares analyses of both isothermal and nonisothermal data. It was found that the nonlinear least squares procedures were useful for a rational selection of an acceptable model and estimation of its parameters. General observations were made concerning good regions for further experimentation if a discrimination among rival models is desired. Additional well‐designed experiments were found to be necessary to allow a reduction of the confidence region of the parameters of the Hougen‐Watson models to an acceptable size.