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Griessen, Ronald; Boelsma, Christiaan; Schreuders, Herman; Broedersz, Chase P.; Gremaud, Robin and Dam, Bernard (2020): Single Quality Factor for Enthalpy-Entropy Compensation, Isoequilibrium and Isokinetic Relationships. In: Chemphyschem, Vol. 21, No. 15: pp. 1632-1643

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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 ofCQFis furthermore a direct measure of the existence of a genuine isoequilibrium or isokinetic relationship.

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