An associated solution model for albite-water melts

Abstract

An associated solution model linking microscopic and macroscopic data is developed to describe the thermodynamic properties of NaAlSi 3O 8-H 2O melt mixture. The model is based upon the following two homogeneous melt speciation reactions: Na 0.75Al 0.75Si 2.25O 60.3Na 2Al 2SiO 6 + 0.15NaAlSi 2O 6 + 0.55Si 3O 6; Na 2Al 2SiO 6, + H 2ONa 2Al 2(OH) 2SiO 5, where the first reaction represents the formation of three-membered rings in albite melt and the second one represents hydrolysis of Al-O-Al linkages. The equilibrium constants of these two reactions are calibrated on the basis of available water speciation data, phase equilibrium data; thermodynamic data, solubility data, and P-V-T data. The calculated thermodynamic mixing properties show that relative to our standard states, albite and H 2O melt components exhibit strong negative deviation from ideality. The value for G ex for any given P and T reaches a minimum at approximately 33 mol% water, which coincides with the composition at which there is a significant change in many microscopic and macroscopic properties in this system. For all P, T conditions, it is calculated that hydroxyl-bearing species dominate over molecular water at low water contents but the latter becomes dominant after the total water content exceeds about 33 mol%. When the total water content in the albite melt increases, the abundance of molecular water increases and that of albite species decreases, while the abundances of both three-membered rings and hydroxyl-bearing species (Na 2Al 2(OH) 2SiO 5) first increase, then decrease. The calculated water solubility is positively correlated with P and negatively correlated with T for pressures lower than approximately 5 kb but positively correlated with T for pressures higher than this, consistent with the behavior suggested by previous workers. The water solubility has been readily modeled by hydrolysis of Al-O-Al linkages in spite of their very small abundance in these melts. The calculated hypersolidus phase relations are consistent with available experimental data. In addition, critical phenomena are predicted within the system, in agreement with the implications of available experimental data.