The Latent Heat of Supercritical Fluids

Abstract

The article discusses the notion of a supercritical latent heat during 'pseudoboiling': Experimental, numerical, and theoretical evidence show that the supercritical state space is not homogeneous, but can be divided into liquid-like and gas-like domains, separated by an extension to the coexistence line -- the Widom line. The key concept are two limit states of ideal liquid and ideal gas, characterized by constant heat capacities, and analyze the transition between them. Then, analogous to subcritical vaporization, a supercritical state transition from liquid to gaseous overcomes intermolecular attractive forces, albeit over a finite temperature interval rather than at an equilibrium temperature. This distributed latent heat is in fact approximately invariant with respect to pressure for (0 < p < 3 p_cr) and is thus valid at subcritical and supercritical conditions. This view also changes the perspective on subcritical latent heat: while it is an accurate representation of the required energy at very low pressures, the contribution of the distributed latent heat dominates the equilibrium latent heat as the critical pressure is approached.