Ionization of boric acid in water from 298K to 623K by AC conductivity and Raman spectroscopy

• Published in: The Journal of chemical thermodynamics 2017-03, Vol.106, p.187-198
• Main Authors: Arcis, H., Ferguson, J.P., Applegarth, L.M.S.G.A., Zimmerman, G.H., Tremaine, P.R.
• Format: Article
• Language: English
• Subjects: Boric acid; Conductivity; Equilibrium constant; Hydrothermal solution; Raman spectroscopy
• ISSN: 0021-9614; 1096-3626
• DOI: 10.1016/j.jct.2016.11.007

•Boric acid ionization constants were measured up to T=623K to an accuracy of ±10% at T=623K and ±5% at T⩽600K.•Quantitative reduced isotropic Raman spectra for aqueous boric acid up to T=623K show only B(OH)3, with no evidence of metaboric acid species.•The results confirm the validity of the new 2006 IAPWS formulation for the ionization constant of water, pKw. Boric acid is used in the primary coolant of pressurized water nuclear reactors (PWRs) as a neutron absorber to control the reactor efficiency. Accurate thermodynamic and transport properties are needed to model the boron precipitation reactions in fuel deposit crevices, which adversely affect the neutron flux. Here, we report (i) new values for the boric acid ionization constant that have been measured from T=298K to T=623K at a constant pressure p∼20MPa using a unique high-precision flow-through AC electrical conductance instrument and (ii) quantitative reduced isotropic Raman spectra for a ∼1molal boric acid aqueous solution from T=298K to T=623K at a constant pressure p=25MPa. Frequency-dependent electrical conductivities of aqueous solutions of boric acid have been determined over ionic strengths from 10−4 to 10−1mol·kg−1. The concentration-dependent experimental molar conductivities, Λ, were analysed with the Turq-Blum-Bernard-Kunz (“TBBK”) ionic conductivity model to yield values for the ionization constant of boric acid, Kb11, to an accuracy of ±10% at T=623K and ±5% at T⩽600K. These compare well with extrapolated values from accurate potentiometric measurements at temperatures up to 563K and steam saturation pressures. These results also confirm the validity of the new 2006 IAPWS (International Association for the Properties of Water and Steam) formulation for the ionization constant of water, pKw. The Raman results did not show any evidence of metaboric acid formation under hydrothermal conditions.