On the equilibrium limit of liquid stability in pressurized aqueous systems.

Abstract

Phase stability, and the limits thereof, are a central concern of materials thermodynamics. However, the temperature limits of equilibrium liquid stability in chemical systems have only been widely characterized under constant (typically atmospheric) pressure conditions, whereunder these limits are represented by the eutectic. At higher pressures, the eutectic will shift in both temperature and chemical composition, opening a wide thermodynamic parameter space over which the absolute limit of liquid stability, i.e., the limit under arbitrary values of the thermodynamic forces at play (here pressure and concentration), might exist. In this work, we use isochoric freezing and melting to measure this absolute limit for the first time in several binary aqueous brines, and nodding to the etymology of "eutectic", we name it the "cenotectic" (from Greek "κοινός-τῆξῐς", meaning "universal-melt"). We discuss the implications of our findings on ocean worlds within our solar system and cold ocean exoplanets; estimate thermodynamic limits on ice crust thickness and final ocean depth (of the cenotectic or "endgame" ocean) using measured cenotectic pressures; and finally provide a generalized thermodynamic perspective on (and definition for) this fundamental thermodynamic invariant point.