The stability-limit conjecture revisited.

Abstract

The stability-limit conjecture (SLC) proposes that the liquid spinodal of water returns to positive pressure in the supercooled region and that the apparent divergence of water's thermodynamic response functions as temperature decreases are explained by the approach to this re-entrant spinodal. Subsequently, it has been argued that the predictions of the SLC are inconsistent with general thermodynamic principles. Here, we reconsider the thermodynamic viability of the SLC by examining a model equation of state for water which was first studied to clarify the relationship of the SLC to the proposed liquid-liquid phase transition in supercooled water. By demonstrating that a binodal may terminate on a spinodal at a point that is not a critical point, we show that the SLC is thermodynamically permissible in a system that has both a liquid-gas and a liquid-liquid phase transition. We also describe and clarify other unusual thermodynamic behavior that may arise in such a system, particularly that associated with the so-called "critical-point-free" scenario for a liquid-liquid phase transition, which may apply to the case of liquid Si.