Experimental study and modeling of the thermodynamic properties of magnesium silicates

摘要

The thermodynamic properties of all MgO-SiO2 system phases were studied by Knudsen mass spectrometry over a wide temperature range (1571–1873 K) and the whole range of compositions. An approach based on the generation of volatile interaction products formed in the reduction of oxide components was used. The reducing agents were Nb, Ta, and Mo. The observed ion current intensity ratios I(Mg+)/I(SiO+) were used to calculate the activities and partial thermodynamic functions of the components in liquid and crystalline MgO-SiO2 mixtures and the integral thermodynamic functions of formation of magnesium ortho-and metasilicates. For the first time, direct and reliable information about the thermodynamic properties of all system phases at high temperatures was obtained. These results in combination with all the available data on the thermodynamic properties and phase equilibria in the MgO-SiO2 system were used to develop a statistical-thermodynamic model of liquid magnesium silicates based on treating them as associated liquids. Simultaneously, the problem of obtaining self-consistent data on the thermodynamic functions of all phases and conditions of equilibria between them was solved. In addition to polymeric silicon-oxygen structures of arbitrary sizes and spatial configurations, heteromolecular complexes such as MS, M2S, and M3S (S=SiO2 and M=MgO) were found to exist in liquid MgO-SiO2 mixtures. The correctness of the results obtained was substantiated by the virtually complete coincidence of the calculated thermodynamic properties and phase equilibrium conditions with experimental data and their conformity to the general patterns characteristic of binary silicate systems.