Spontaneous freezing of supercooled water under isochoric and adiabatic conditions.

The return of a supercooled liquid to equilibrium usually begins with a fast heating up of the sample which ends when the system reaches the equilibrium freezing temperature. At this stage, the system is still a microsegregated mixture of solid and liquid. Only later is solidification completed through the exchange of energy with the surroundings. Using the IAPWS-95 formulation, we investigate the adiabatic freezing of supercooled water in a closed and rigid vessel, i.e., under thermally and mechanically isolated conditions, which captures the initial stage of the decay of metastable water to equilibrium. To improve realism further, we also account for a fixed amount of foreign gas in the vessel. Under the simplifying assumption that the system is at equilibrium immediately after the nominal freezing temperature has been attained, we determine-as a function of undercooling and gas mole number-the final temperature and pressure of the system, the fraction of ice at equilibrium, and the entropy increase. Assuming a nonzero energy cost for the ice-water interface, we also show that, unless sufficiently undercooled, perfectly isolated pure-water droplets cannot start freezing in the bulk.