Partial molar volumes ( V¯) of SiO2, K2O, Na2O, Li2O and BaO have been re-evaluated in binary silicate melts at 1673 K. Volumetrically, the SiO2 component mixes ideally in K2O-SiO2 melts but mixes non-ideally in Li, Na and Ba melts, with V¯SiO2 displaying maxima between ~80–95 mole% SiO2. K2O partial molar volumes ( V¯K2O) display weak, non-ideal behaviour in K2O-SiO2 melts due to electrostriction, where tetrahedra collapse around the modifier cation, K+, in response to K-O Coulombic attraction. V¯Na2O, V¯Li2O and V¯BaO also behave non-ideally in their respective binary melts due to electrostriction. The combined effects of non-ideal mixing of SiO2 and electrostriction associated with the modifier cations result in molar volumes of the four melts being less than expected for ideal mixing. The extent of non-ideal volumetric mixing in the binary melts increases in the order K<Na<Li<Ba, which is the same as the order of the consolute temperatures of the miscibility gaps for these binary melts. The similar order leads us to suggest that non-ideal volumetric mixing results from the same chemical interactions that give rise to melt immiscibility and that these interactions are due primarily to non-ideal behaviour of the SiO2 component. The non-ideal volumetric mixing behaviour required use of quadratic expressions to fit molar volume-compositional trends of the four melt systems studied. Although mixing is non-ideal, the partial molar volumes of SiO2 and modifier oxides are remarkably similar to values obtained from linear mixing models for melts containing ~45–70 wt.% SiO2. Pronounced effects of non-ideal mixing are mostly restricted to highly siliceous melts (XSiO2>0.75) where V¯SiO2 values are appreciably greater than the molar volume of liquid SiO2 (V°SiO2), which is ~26.75 cm3/mole at 1673 K. The findings are consistent with volumetric (density) studies of highly siliceous (haplogranitic) melts.
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