Crossing the Widom-line – Supercritical pseudo-boiling

•A vaporization-like process at supercritical pressure exists: pseudoboiling.•This nonlinear state transition is relevant at pcr < p < 3pcr.•It involves overcoming molecular forces while raising the temperature.•An equation for the supercritical coexistence line is given.•At p > pcr, a transition occurs at pseudoboiling and not at the critical temperature.

Recent publications in the open literature have shown that supercritical fluid states are not homogeneously distributed but, in fact, can be differentiated into two distinct regions with gas-like and liquid-like properties, respectively. These regions are divided by an extension of the coexistence line, commonly called Widom line. This paper shows that a supercritical analog to subcritical phase change, pseudoboiling, does exist when crossing this demarcation. The supercritical state transition does not occur in a phase equilibrium but takes place over a finite temperature interval. While subcritical vaporization requires energy to overcome intermolecular attraction, supercritical state transitions additionally require energy to increase the temperature. It could be shown that the attractive potential is the dominant energy sink up to a reduced pressure of 1.5 for argon, nitrogen, oxygen, and water. The effect reduces with growing pressure and becomes negligible for p/pcr > 3. Furthermore, a new equation for this Widom- or pseudoboiling-line is given. It exhibits improved accuracy over previously published equations; performing a limit analysis of the Clapeyron equation allows to express its sole parameter purely in terms of thermodynamic variables. This parameter can then be evaluated from an equation of state or from fluid data - no nonphysical fitting is required.

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