No abstract

The interpretation of the term "compensation" obscures a logical contradiction, the catalytic paradox, which is caused by inconsistent validity ranges of the Arrhenius parameters, the preexponential factor and the activation energy. For this reason, a theory which contains the Arrhenius parameters cannot be established for the entire system (whole temperature range) on the basis of classical logic. Only the subsystems can be consistent and complete. One subsystem is the range of the topocatalytic concept which is relevant for thermal deactivation, thermal bistability and for all reactions with surface dependence of activity. The other is the range of the energetic concept which is preferred in fundamental research. In order to complete the subsystems, new consistent symbols are introduced. The change of particle size caused by thermal deactivation can result in four possible particle size effects, two of which have been discussed in the literature.

Thermal deactivation can be described either by deactivation kinetics or by the isokinetic effect. The latter expression is used synonymously with the "compensation effect" and the "ThetaRule". An examination of the original literature shows that only the compensation effect is applicable to thermal deactivation but not the Theta-Rule. The introduction of the preparation temperature as a parameter of the compensation effect results in a "modified Theta-Rule", which describes the experimental data and is proposed for the non-separable kinetics. The consequence of the observed deviations from the validity range of the Theta-Rule is that the activation energy cannot be used as a universal activity criterion.

No abstract

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.