Thermodynamics of ice polymorphs and ‘ice-like’ water in hydrates and hydroxides

Thermodynamic properties of water, in various families of hydroxides, oxihydroxides and hydrates (chlorides, chlorates, sulfates and sulfites …), have been calculated by using a large number of data available in the literature. A phase diagram of water has been used to find the first complete set of thermodynamic properties at 298 K, 1 bar of 8 ice polymorphs, from Ih (hexagonal ice, the common polymorph) to IX (very low temperature and high pressure polymorph). These results are used to illustrate the concept of ‘ice-like water’ available for a very large number of hydrated phases (noted X.H2O) in which water is attached to the corresponding anhydrous substrate (noted X) within a large spectrum of different enthalpies (ΔfH°) or Gibbs free energies (ΔfG°), but within a relatively small range of others properties. Heat capacity (Cp°), entropy (S°), and volume (V°) of hydration water (X.H2O−X=H2O) appeared to be very close to those characterizing ice polymorphs such as ice II or ice VIII. This concept allows the authors to propose a classification of minerals in terms of affinity for water and to predict the relative stability of hydrated and dehydrated phases under climatic variations.