The ‘Theorem of common kinetic runs’ in homogeneous non-isothermal reaction kinetics

Abstract

The kinetic features of the fundamental homogeneous two-reaction models for linearly increasing temperature have been studied systematically by the analysis of 2500 signal curves (organized in 250 series), obtained from computer simulations and compared with numerous TA experiments. For methods based on a proportionality between the particular reaction rates and their contribution to the derivative overall signal, it has been found that characteristicbehaviour sets of three order-dependent parameters which refer to definite intervals of the starting concentration in series, can be extracted from the halfwidth and shape index of the curves. Such thermoanalytical patterns agree with those obtained from the distribution lists of some thousand DTA- and UV-experiments. They are presented for the 21 most important two-step model and almost independent of the activation data and of the method-dependent proportionality factors. Therefore, they allow for the direct kinetic identification of the complex reaction involved.