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Experimental determination of solubilities of sodium polyborates in MgCl2 solutions: Solubility constant of di-sodium hexaborate tetrahydrate, and implications for the diagenetic formation of ameghinite

Xiong, Yongliang X.; Kirkes, Leslie D.; Knox, Jandi L.; Marrs, Cassandra M.

In this study, solubility measurements were conducted for sodium polyborates in MgCl2 solutions at 22.5 ± 0.5 °C. According to solution chemistry and XRD patterns, di-sodium tetraborate decahydrate (borax) dissolves congruently, and is the sole solubility-controlling phase, in a 0.01 mol/kg MgCl2 solution: {equation presented} However, in a 0.1 mol/kg MgCl2 solution borax dissolves incongruently and is in equilibrium with di-sodium hexaborate tetrahydrate: {equation presented} In this study, the equilibrium constant (log K0) for Reaction 2 at 25 °C and infinite dilution was determined to be -16.44 ± 0.13 (2σ) based on the experimental data and the Pitzer model for calculations of activity coefficients of aqueous species. In accordance with the log K0 for Reaction 1 from a previous publication from this research group, and log K0 for Reaction 2 from this study, the equilibrium constant for dissolution of di-sodium hexaborate tetrahydrate at 25 °C and at infinite dilution, {equation presented} was derived to be -45.42 ± 0.16 (2σ). The equilibrium constants determined in this study can find applications in many fields. For example, in the field of nuclear waste management, the formation of di-sodium hexaborate tetrahydrate in brines containing magnesium will decrease borate concentrations, making less borate available for interactions with Am(III). In the field of experimental investigations, based on the equilibrium constant for Reaction 2, the experimental systems can be controlled in terms of acidity around neutral pH by using the equilibrium assemblage of borax and di-sodium hexaborate tetrahydrate at 25 °C. As salt lakes and natural brines contain both borate and magnesium as well as sodium, the formation of sodium hexaborate tetrahydrate may influence the chemical evolution of salt lakes and natural brines. Di-sodium hexaborate tetrahydrate is a polymorph of the mineral ameghinite [chemical formula Na2B6O10·4H2O; structural formula NaB3O3(OH)4 or Na2B6O6(OH)8]. Di-sodium hexaborate tetrahydrate could be a precursor of ameghinite and could be transformed when borate deposits are subject to diagenesis.