ABSTRACT

This chapter examines difficult problems of finding an appropriate kinetic scheme and associated parameters from experimentally obtained reaction profiles. One of the problems of distinguishing mechanisms is that the experimental data are subject to error. The problem becomes assessing whether the residuals observed between the data and scheme arise from experimental error or because the model is inappropriate. In the days before personal computers, most kinetic data were transformed into linear functions for analysis. With modern stopped-flow equipment, it is possible to go from reaction initiation to final analysis with just two clicks of the mouse, the first to activate the stopped-flow device and the second to select "fit" from the analysis menu. Global fitting is the process of fitting more than one data set at a time using one or more shared parameters. Error analysis is particularly important when fitting data to kinetic models because there is a high likelihood of including poorly constrained parameters in the fit.