An equation of state for silicate melts.: II.: Calibration of volumetric properties at 105 Pa

Reference pressure (10(5) Pa) parameters for the silicate liquid equation of state of Ghiorso (2004a) are calibrated from literature data on measurements of densities and sound speeds. A model for the temperature- and compositionally-dependent, reference-pressure volume (density) in the system K2O-Na2O-CaO-MgO-FeO-NiO-CoO-Fe2O3-Al2O3-TiO2-SiO2 is obtained. Precision of data recovery is 0.76 percent (one root-mean-square residual). Linear mixing relations for model parameters are utilized in this calibration with the inclusion of quadratic terms between soda and titania and potash and titania to account for the effect of alkali metals on the partial molar volume of TiO2. Liquids in the system CaO-Al2O3-SiO2 with molar ratios of CaO/SiO2 < 0.5 are excluded from this analysis in order to avoid the inclusion of additional non-linear terms. Iron-bearing systems are modeled by first "speciating" the liquid to obtain molecular proportions of FeO, FeO1.5 (Fe2O3) and FeO1.3 (Fe0.42+Fe0.63+O1.3). Partial molar properties are extracted for all three iron oxides. This procedure is followed because (1) it affords an internally consistent means of extrapolating previously calibrated models of iron-redox equilibria in silicate melts to elevated pressure, and (2) it results in significant improvements in model recovery of density measurements on Fe-bearing systems. The model partial molar volume of FeO1.3 is similar to12 percent smaller than a linear combination of the fully oxidized and reduced endmembers. Internally consistent expressions for the reference pressure compressibility and its temperature dependence are formulated from a calibration of sound speeds in molten liquids. A model for the temperature- and compositionally-dependent sound speed in the system K2O-Na2O-CaO-MgO-FeO-Fe2O3-Al2O3-TiO2-SiO2, is obtained. Precision of data recovery is 1.7 percent. Mixing relations identical to the volume model are adopted for consistency with the inclusion of an additional quadratic composition term in soda and alumina.