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Thermodynamics

Philosophical Transactions of the Royal Society A Mathematical Physical and Engineering Sciences

When thermodynamics is understood as the science (or art) of constructing effective models of natural phenomena by choosing a minimal level of description capable of capturing the essential features of the physical reality of interest, the scientific community has identified a set of general rules that the model must incorporate if it aspires to be consistent with the body of known experimental evidence. Some of these rules are believed to be so general that we think of them as laws of Nature, such as the great conservation principles, whose "greatness" derives from their generality, as masterfully explained by Feynman in one of his legendary lectures. The second law of thermodynamics is universally contemplated among the great laws of Nature. In this paper we show that, in the past four decades, an enormous body of scientific research devoted to modeling the essential features of nonequilibrium natural phenomena has converged from many different directions and frameworks towards the general recognition (albeit still expressed in different but equivalent forms and language) that another rule is also indispensable and reveals another great law of Nature that we propose to call the \caporali{fourth law of thermodynamics}. We state it as follows: every nonequilibrium state of a system or local subsystem for which entropy is well-defined must be equipped with a metric in state space with respect to which the irreversible component of its time evolution is in the direction of steepest entropy ascent compatible with the conservation constraints. To illustrate the power of the fourth law, we derive (nonlinear) extensions of Onsager reciprocity and fluctuation-dissipation relations to the far-nonequilibrium realm within the framework of the rate-controlled constrained-equilibrium (RCCE) approximation (also known as the quasi-equilibrium approximation).

The fourth law of thermodynamics: steepest entropy ascent