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In various chemical systems enthalpy-entropy compensation (EEC) is awell-known rule of behavior, although the physical roots of it are still notcompletely understood. It has been frequently questioned whether EEC is a trulyphysical phenomenon or a coincidence due to trivial mathematical connectionsbetween statistical-mechanical parameters - or even simpler: A phantom effectresulting from the misinterpretation of experimental data. Here, we review EECfrom a new standpoint using the notion of correlation which is essential forthe method of factor analysis, but is not conventional in physics andchemistry. We conclude that the EEC may be rationalized in terms of hidden (notdirectly measurable with the help of the current experimental set-up) butphysically real factors, implying a Carnot-cycle model in which a micro-phasetransition (MPT) plays a crucial role. Examples of such MPTs underlyingphysically valid EEC should be typically cooperative processes insupramolecular aggregates, like changes of structured water at hydrophobicsurfaces, conformational transitions upon ligand-biopolymer binding, and so on,so forth. The MPT notion could help rationalize the occurrence of EEC inconnection with hydration and folding of proteins,enzymatic reactions,functioning of molecular motors, DNA de- and rehybridization, as well assimilar phenomena.

Entropy-Enthalpy Compensation May Be a Useful Interpretation Tool for Complex Systems Like Protein-DNA Complexes: An Appeal to Experimentalists