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

Abstract : 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.
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https://hal-insu.archives-ouvertes.fr/insu-01445657
Contributor : Eva Fareau <>
Submitted on : Wednesday, January 25, 2017 - 11:06:19 AM
Last modification on : Saturday, March 28, 2020 - 2:05:00 AM

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G. Ottonello, P. Richet, M. Vetuschi Zuccolini. The wet solidus of silica: Predictions from the scaled particle theory and polarized continuum model . Journal of Chemical Physics, American Institute of Physics, 2015, 142 (5), ⟨10.1063/1.4906745⟩. ⟨insu-01445657⟩

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