Zeitschriftenartikel:
A. Yelon, E. Sacher, W. Linert:
"Multi-Excitation Entropy, Entropy-Enthalpy Relations, and their Impact on Catalysis";
Catalysis Letters,
141
(2011),
7;
S. 954
- 957.
Kurzfassung englisch:
Catalyzed reactions involve large activation enthalpies, requiring a fluctuation in which many excitations, in the form of infrared vibrations or phonons, are needed to surmount the activation barrier. It was previously shown that this results in a multiexcitation entropy (MEE) term in the free energy of activation. For a series of related reactions, this leads to an isokinetic rule. We show here that this almost always implies that the series will also obey an isoequilibrium relation. This provides a necessary and sufficient condition for the Hammett substituent constant equation to be obeyed. Finally, we discuss the importance of MEE in catalysis. This has not generally been recognized.
Schlagworte:
Multi-excitation; Entropy; Isokinetic, Isoequilibrium
"Offizielle" elektronische Version der Publikation (entsprechend ihrem Digital Object Identifier - DOI)
http://dx.doi.org/10.1007/s10562-011-0645-8
Erstellt aus der Publikationsdatenbank der Technischen Universität Wien.