Single Quality Factor for Enthalpy-Entropy Compensation, Isoequilibrium and Isokinetic Relationships
R. Griessen (Vrije Universiteit Amsterdam)
Christiaan Boelsma (Tata Steel Europe Limited)
Herman Schreuders (TU Delft - ChemE/Afdelingsbureau)
Chase P. Broedersz (Ludwig Maximilians University)
R. Gremaud (ABB (Switzerland))
Bernard Dam (TU Delft - ChemE/Materials for Energy Conversion and Storage)
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Abstract
Enthalpy-entropy compensation (EEC) is very often encountered in chemistry, biology and physics. Its origin is widely discussed since it would allow, for example, a very accurate tuning of the thermodynamic properties as a function of the reactants. However, EEC is often discarded as a statistical artefact, especially when only a limited temperature range is considered. We show that the likeliness of a statistical origin of an EEC can be established with a compensation quality factor (CQF) that depends only on the measured enthalpies and entropies and the experimental temperature range. This is directly derived from a comparison of the CQF with threshold values obtained from a large number of simulations with randomly generated Van ‘t Hoff plots. The value of CQF is furthermore a direct measure of the existence of a genuine isoequilibrium or isokinetic relationship.