Densities and volumes of hydrous silicate melts: New measurements and predictions

The equilibrium molar volumes of four series of anhydrous and hydrous aluminosilicate glasses and liquids (0 to 11 mol% H2O) were determined at 1 bar between 300 and 1050 K. The anhydrous compositions range from highly polymerized NaAlSi3O8 to depolymerized synthetic iron-free analogs of tephrite and foidite magma compositions (NBO/T = 0.8 and 1.5, respectively). For each sample the volume was derived from the room-temperature density of the glass and the thermal expansivity of the glass and supercooled liquid from 300 K to a temperature about 50 K higher than the standard glass transition. The partial molar coefficient of thermal expansion of water in hydrous silicate glasses is about (6.2 +/- 3.5) x 10(-5) K-1, and in the melts ranges from 11 x 10(-5) to 36 x 10(-5) K-1. The present molar volumes of hydrous supercooled liquids are reproduced with the model of Ochs and Lange (1999) to within 1.1%, except for the hydrous foidite series. This agreement confirms that the partial molar volume of water ((V) over bar (H2O)) near the glass transition cannot depend strongly on the chemical composition of the silicate end-member, nor on water speciation. In order to reproduce the molar volumes of the foidite series, a combined model (using Lange, 1997 and Courtial and Dingwell, 1999 models and values derived from the new data) is used where an excess volume term between SiO2 and CaO is introduced. Finally, our experimental data are better fit if (V) over bar (H2O) = 23.8 +/- 0.5 cm(3) mol(-1) at 1273 K, and d (V) over bar (H2O)/dT = 15.9 +/- 1.6 cm(3) mol(-1) K-1. Contrasting trends are also observed for the configurational contributions to the expansivity with a positive slope of dV(i)(conf)/dT versus water for the most polymerized base compositions (NBO/T <= 0.21) and a negative slope for the two most depolymerized base compositions with NBO/T of 0.86 and 1.51. (C) 2015 Elsevier B.V. All rights reserved.