A Raman spectroscopic and ab initio investigation of aqueous boron speciation under alkaline hydrothermal conditions: evidence for the structure and thermodynamic stability of the diborate ion

Abstract

Raman spectra of aqueous sodium borate solutions, with and without excess NaOH, NaCl, and LiCl, have been obtained from perpendicular and parallel polarization measurements acquired using a custom-built sapphire flow cell over the temperature range 25 to 300 °C at 20 MPa. The solvent-corrected reduced isotropic spectra include a large well-defined band at 865 cm⁻¹ which overlaps with the boric acid B(OH)₃ band at 879 cm⁻¹, and becomes increasingly intense at elevated temperatures. This band does not correspond to the spectrum of any other previously reported aqueous polyborate ions, all of which have symmetric stretching bands at frequencies below that of borate, [B(OH)₄]⁻, at 745 cm⁻¹. Based on the classic high-temperature potentiometric titration study by R. E. Mesmer, C. F. Baes and F. H. Sweeton, Acidity measurements at elevated temperatures. VI. Boric acid equilibriums, Inorg. Chem., 1972, 11, 537–543, the new band was postulated to arise from a diborate ion, [B₂(OH)₇]⁻ or [B₂O(OH)₅]⁻. Ab initio density functional theory (DFT), together with chemical modelling studies, suggest that it is most likely [B₂(OH)₇]⁻. Thermodynamic formation quotients derived from the peak areas showed variations with ionic strength as well as charge-balance discrepancies, which suggest one or more unidentified minor equilibrium species may also be present. The most likely candidate is the divalent diborate species [B₂O₂(OH)₄]²⁻ which is also predicted to have a band near 865 cm⁻¹ and is postulated to be present as a sodium ion pair. These are the first quantitative Raman spectra ever reported for borate-rich solutions under such conditions and provide the first spectroscopic evidence of a diborate species at PWR reactor coolant temperatures.