TABLE OF CONTENTS It is also useful to be able to test different methods of kinetic analysis on a "reference" data set. Isothermal and nonisothermal data sets have been provided [91] and the kinetic analysis of these data sets by a variety of volunteer participants, using computational methods of their choice, has been discussed in considerable detail [92]. Some of the sets are actual experimental results for the thermal decompositions of ammonium perchlorate and calcium carbonate. The data sets 7 and 8 (illustrated in Figures 10.10 and 10.11, respectively) were simulated using a system of two equally-weighted, parallel, first-order reactions:
The Arrhenius parameters of the individual steps were taken to be A 1 = 10 10 min ?1, E 1 = 80 kJ mol ?1; A 2 = 10 15 min ?1, E 2 = 120 kJ mol ?1.
The kinetic results produced from data sets 1 4 are discussed by Maciejewski [60] and for data sets 5 8 by Vyazovkin [93]. There is ample computational machinery available for testing the "goodness-of-fit" of experimental data to the limited set of kinetic equations. Provided that the methods of kinetic analysis are computationally sound, they should be seen as complementary. Confidence in the resulting parameters is vastly increased if similar values are obtained using different approaches It is a considerable advantage to remove the influence of the kinetic model from the kinetic analysis while estimating the Arrhenius parameters, but...
