Solvent-corrected reduced isotropic
Raman spectra of aqueous boric
acid + sodium borate solutions have been obtained from perpendicular and parallel polarization
measurements in a novel custom-made titanium flow cell with sapphire
windows over the temperature range 25 to 300 °C at 20 MPa using
the perchlorate anion, ClO4
–, as an internal
standard. The reduced isotropic spectra of solutions yielded the first
reported quantitative speciation results for polyborate ions in equilibrium
with boric acid and borate in high-temperature aqueous solutions above
200 °C. The spectra obtained from solutions at low sodium/boron
ratios, 0 < m
Na
ST/m
B
ST < 0.254, displayed well-defined
bands at 880, 747, 615, and 532 cm−1, corresponding
to the species B(OH)3 > [B(OH)4]− > [B3O3(OH)4]− ≫ [B5O6(OH)4]−, respectively. The triborate ion, [B3O3(OH)4]−, was found to be the major polyborate
species in these boric acid-rich solutions in the range 25 to 300
°C. Thermodynamic formation constants for the triborate species,
[B3O3(OH)4]−, calculated
from the peak areas, are in agreement with the literature values reported
by Mesmer et al at 50, 100, and 200 °C to within the combined
experimental uncertainties. At 300 °C, the value for the formation
constant, log K
31,m
b
= 2.259 ±
0.060, is larger than the value extrapolated from the results of Mesmer
et al. by a factor of ∼3.