Search

In various chemical systems enthalpy-entropy compensation (EEC) is a well-known rule of behavior, although the physical roots of it are still not completely understood. It has been frequently questioned whether EEC is a truly physical phenomenon or a coincidence due to trivial mathematical connections between statistical-mechanical parameters - or even simpler: A phantom effect resulting from the misinterpretation of experimental data. Here, we review EEC from a new standpoint using the notion of correlation which is essential for the method of factor analysis, but is not conventional in physics and chemistry. We conclude that the EEC may be rationalized in terms of hidden (not directly measurable with the help of the current experimental set-up) but physically real factors, implying a Carnot-cycle model in which a micro-phase transition (MPT) plays a crucial role. Examples of such MPTs underlying physically valid EEC should be typically cooperative processes in supramolecular aggregates, like changes of structured water at hydrophobic surfaces, conformational transitions upon ligand-biopolymer binding, and so on, so forth. The MPT notion could help rationalize the occurrence of EEC in connection with hydration and folding of proteins,enzymatic reactions, functioning of molecular motors, DNA de- and rehybridization, as well as similar phenomena., Comment: 8 pages, 2 Figures, Submitted for publication

The name of George Augustus Linhart is in fact "widely unknown". In effect, he was a Viennese-born USA-American physicist-chemist, partially associated with the Gilbert Newton Lewis' school of thermodynamics at the University of California in Berkeley. As a lone small boy, he had arrived (from Austria via Hamburg) at New York in 1896, but was officially USA-naturalized only in 1912. He was able to pick up English in the streets of New York and Philadelphia, when occasionally working as a waiter and/or as a tailor - just to somehow survive. But, nonetheless, he could successfully graduate a high school in about one year - and then went to the universities for his further education. After obtaining his BS from the University of Pennsylvania, he could manage getting both MA and then PhD from the Yale University, Kent Chemical Laboratory. George Augustus Linhart was afterwards definitely able to successfully work out the true foundations of thermodynamics and could thus outdistance many famous thermodynamicists of his time and even the later ones. Linhart's view of the Second Law of Thermodynamics was and is extremely fruitful. The interconnection of Linhart's ideas with those of Gilbert Newton Lewis, as well as with the modern standpoints are discussed here in detail., Comment: Submitted

Some 80-90 years ago, George A. Linhart, unlike A. Einstein, P. Debye, M. Planck and W. Nernst, has managed to derive a very simple, but ultimately general mathematical formula for heat capacity vs. temperature from the fundamental thermodynamical principles, using what we would nowadays dub a "Bayesian approach to probability". Moreover, he has successfully applied his result to fit the experimental data for diverse substances in their solid state in a rather broad temperature range. Nevertheless, Linhart's work was undeservedly forgotten, although it does represent a valid and fresh standpoint on thermodynamics and statistical physics, which may have a significant implication for academic and applied science., Comment: submitted