The wet solidus of silica: predictions from the scaled particle theory and polarized continuum model.

We present an application of the Scaling Particle Theory (SPT) coupled with an ab initio assessment of the electronic, dispersive, and repulsive energy terms based on the Polarized Continuum Model (PCM) aimed at reproducing the observed solubility behavior of OH2 over the entire compositional range from pure molten silica to pure water and wide pressure and temperature regimes. It is shown that the solution energy is dominated by cavitation terms, mainly entropic in nature, which cause a large negative solution entropy and a consequent marked increase of gas phase fugacity with increasing temperatures. Besides, the solution enthalpy is negative and dominated by electrostatic terms which depict a pseudopotential well whose minimum occurs at a low water fraction (XH2O) of about 6 mol. %. The fine tuning of the solute-solvent interaction is achieved through very limited adjustments of the electrostatic scaling factor γel which, in pure water, is slightly higher than the nominal value (i.e., γel = 1.224 against 1.2), it attains its minimum at low H2O content (γel = 0.9958) and then rises again at infinite dilution (γel = 1.0945). The complex solution behavior is interpreted as due to the formation of energetically efficient hydrogen bonding when OH functionals are in appropriate amount and relative positioning with respect to the discrete OH2 molecules, reinforcing in this way the nominal solute-solvent inductive interaction. The interaction energy derived from the SPT-PCM calculations is then recast in terms of a sub-regular Redlich-Kister expansion of appropriate order whereas the thermodynamic properties of the H2O component at its standard state (1-molal solution referred to infinite dilution) are calculated from partial differentiation of the solution energy over the intensive variables.

Water as a dense icelike component in silicate glasses

Density and Brillouin-scattering measurements of hydrous andesite glasses at ambient conditions showed that dissolved water has a concentration-independent partial molar volume of 12 +/- 0.5 cubic centimeters per mole and a bulk modulus of 18 +/- 3 gigapascals. Dissolved as hydroxyl ions or as molecular water, water has volume properties similar to those of ice VII, the densest form of ice. These properties point to hydrogen bonding as an important factor in water dissolution, and they indicate that changes of water speciation are driven by the entropy and not by the volume of the system. Water in a concentration greater than 1 percent by weight also causes a marked decrease of the shear modulus of the glass.