Physical limit of stability in supercooled D2O and D2O¿H2O mixtures

The fluctuation theory of homogeneous nucleation was applied for calculating the physical boundary of metastable states, the kinetic spinodal, in supercooled D2O and D2O1H2O mixtures. The kinetic spinodal in our approach is completely determined by the surface tension and equation of state of the supercooled liquid. We developed a crossover equation of state for supercooled D2O, which predicts a second critical point of low density water–high density water equilibrium, CP2, and represents all available experimental data in supercooled D2O within experimental accuracy. Using Turnbull’s expression for the surface tension we calculated with the crossover equation of state for supercooled D2O the kinetic spinodal, TKS , which lies below the homogeneous nucleation temperature, TH . We show that CP2 always lies inside in the so-called ‘‘nonthermodynamic habitat’’ and physically does not exist. However, the concept of a second ‘‘virtual’’ critical point is physical and very useful. Using this concept we have extended this approach to supercooled D2O1H2O mixtures. As an example, we consider here an equimolar D2O1H2O mixture in normal and supercooled states at atmospheric pressure, P50.1 MPa. © 2003 American Institute of Physics. @DOI: 10.1063/1.1526634#