Partial Molar Volumes of Components and Species in O-S-Fe-Ni Oxide and Sulfide Liquids

High-quality thermochemical models are now available for sulfide liquids at one bar pressure. An accurate description of the volume mixing properties of these liquids is required in order to apply these one-bar models to important problems at elevated pressure, including sulfide-hosted ore formation, sulfur cycling in convergent margin settings and core formation. Our experimental data have been combined with select density data from other laboratories to calibrate a comprehensive model for density and partial molar volumes of liquids in the O-S- Fe-Ni system. Our results indicate significant negative deviation from linear mixing across the Fe-S, Ni-S and Cu-S binaries. This result is in qualitative agreement with those from prior studies. In the context of associated homogeneous speciation models for sulfide liquids (Kress, 2000, 2007), this negative volume of mixing can be interpreted as a strongly negative volume of reaction for the formation for intermediate melt species from end member elemental components (Δ Vf). Our regression yields Δ Vf values of -6.2, -9.4 and -9.1 cc/mol for FeS, NiS and CuS respectively. There is insufficient oxygen in experimental liquids to resolve a composition dependence for v¯O, but the unrealistic negative regressed value for oxygen partial molar volume suggests a negative Δ Vf for FeO and FeO1.5. Partial molar volumes of Fe, Ni and Cu liquid species are calculated from Nash and Steinemann (1995). All other v¯i are assumed to be linear mixtures of component species volumes. This assumption also implies a moderate negative Δ Vf for the species in question. The resulting model reproduces experimental densities from our laboratory with a 3.6% average error. This is comparable to the estimated measurement error. The larger 5.1% error for the full data set can be attributed to lower precision in some of the other studies and the effects of inter-laboratory error. The sulfide volume model can be applied to calculate thermochemical properties of sulfide liquids to moderate pressures. This model is used in conjunction with literature experiments on coexisting sulfide and silicate liquids at pressure to explore complex interactions between the pressure dependences of oxygen fugacity, sulfur fugacity and sulfide saturation.