Partial molar volumes of NiO and CoO liquids: implications for the pressure dependence of metal-silicate partitioning

Volumetric measurements have been conducted on 7 Ni- and Co-containing sodium disilicate liquids within a compositional range varying from 0 to 9 mol% of NiO and from 0 to 23 mol% of CoO and over a large temperature interval (i.e., above their respective glass transition temperature and up to at least 1473 K). Their molar volumes and thermal expansivities have been determined by combining high-temperature measurements using the Pt-based double-bob Archimedean method and low-temperature measurements using the method described by Webb et al. [S.L. Webb, R. Knoche, D.B. Dingwell, Determination of silicate liquid thermal expansivity using dilatometry and calorimetry, Eur. J. Mineral. 4 (1992) 95-104] based on an assumed equivalence of the relaxation of volume and enthalpy at the glass transition. The molar volume of the present liquids decreases with increasing NiO and CoO contents and the Co-containing liquids exhibit a greater molar volume than the Ni-containing liquids at equivalent molar concentrations. The present results were analysed using a regression equation from which the partial molar volume of NiO and CoO liquids was obtained by the least squares method. This procedure yields partial molar volumes valid over the entire temperature range of 11.506 ± 0.687 and 14.884 ± 0.149 cm3/mol and temperature derivatives of 2.684 ± 1.6 × 10−3 and 1.441 ± 0.4 × 10−3 cm3/mol K, respectively for NiO and CoO at 800 K. The behavior of M-Fe metal-silicate exchange partition coefficient (M = Ni, Co), based on present molar volume determinations, has been estimated as a function of pressure over a wide temperature range. The metal-silicate exchange partition coefficients of both Ni and Co decrease with increasing pressure within the entire temperature range considered in this study (i.e., 800–3000 K).