Comparison of several computational procedures for evaluating the kinetics of thermally stimulated condensed phase reactions

A process involving two parallel reactions has been simulated to test several computational procedures of kinetic analysis of both isothermal and nonisothermal data. It is demonstrated that the popular procedures of fitting isothermal and/or nonisothermal data to single step reaction models tend to conceal the reaction complexity. The isoconversional method allows the reaction complexity to be easily revealed in the form of a dependence of the activation energy on the extent of conversion. The extreme values of the variation in the activation energy are found to be reasonable estimates of the activation energies of the individual reactions. The commercial software ForK has shown significant numerical instability, which is revealed in estimating essentially random Arrhenius parameters.