Mathematical problems in fitting kinetic models - Some new perspectives

Fitting kinetic data with kinetic rate expressions has been a challenge for many years. In hopes of providing some guidelines for tackling this proble m, kinetic parameter estimation is revisited, covering such topics as data transformations, nonlinear single and multi-response techniques, optimizati on techniques, and parameter confidence measures. Among the optimization te chniques discussed are direct and indirect methods, use of higher-order der ivatives, and global optimization. New perspectives on statistical tests fo r model and parameter confidence are discussed, paying particular attention to exact, nonlinear methods and pointing out the distinct lack of these te sts throughout the kinetics literature. In each section, either a single-si te or a dual-site Langmuir-Hinshelwood (L-H) example model is shown for ill ustration of the aforementioned concepts.