The stumbling block of the Gibbs entropy: the reality of the negative absolute temperatures

Abstract: The second Tisza-Callen postulate of equilibrium thermodynamics states that for any system exists a function of the system's extensive parameters, called entropy, defined for all equilibrium states and having the property that the values assumed by the extensive parameters in the absence of a constraint are those that maximize the entropy over the manifold of constrained equilibrium states. By analyzing the evolution of systems of positive and negative absolute temperatures, we show that this postulate is satisfied by the Boltzmann formula for the entropy and is violated by the Gibbs formula. Therefore the Gibbs formula is not a generally valid expression for the entropy. Viceversa, if we assume, by reductio ad absurdum, that for some thermodynamic systems the equilibrium state is determined by the Gibbs' prescription and not by Boltzmann's, this implies that such systems have macroscopic fluctuations and therefore do not reach thermodynamic equilibrium.