Characterization of Orthophosphate and Orthovanadate in Aqueous Solution Using Polarized Raman Spectroscopy.

Polarized Raman spectroscopy was used to analyze aqueous solutions of sodium orthophosphate and orthovanadate over a wide concentration range (0.00891-0.702 mol/L) at 23 °C. The isotropic scattering profiles were obtained by measuring polarized Raman scattering spectra. Furthermore, R-normalized spectra were calculated and presented. The tetrahedral ions, VO₄^3-(aq) and PO₄^3-(aq), demand four Raman active bands which have been subsequently characterized and assigned. For the PO₄^3-(aq) ion, the deformation modes ν₂(e) and ν₄(f₂) appear at 415 and 557 cm^-1, and these modes are depolarized. In the P-O stretching region, the strongest Raman band appears at 936.5 cm^-1, which is totally polarized with a depolarization ratio (ρ-value) of 0.002. The broad and depolarized mode at 1010 cm^-1 constitutes the antisymmetric stretching band ν₃(f₂). The Raman spectrum of VO₄^3- shows two depolarized deformation modes ν₂(e) and ν₄(f₂) at 327 and 345.6 cm^-1, which are severely overlapped. These bands are very weak. The strongest band in the Raman spectrum of VO₄^3-(aq) is the symmetric stretching mode ν₁(a₁) at 820.2 cm^-1 which is totally polarized with a ρ-value at 0.004. The depolarized antisymmetric stretching mode ν₃(f₂) appeared at 785 cm^-1 as a broad and weak band. Both anions are strongly hydrated and showed extensive hydrolysis in an aqueous solution. Orthovanadate is a much stronger base than orthophosphate in aqueous solution. Therefore, a large amount of NaOH was used to suppress the hydrolysis of VO₄^3-(aq) sufficiently, so, it was possible to characterize the VO₄^3- modes. Quantitative Raman spectroscopy was applied to follow the hydrolysis of PO₄^3- over a wide concentration range from 0.00891 to 0.592 mol/L. The hydrolysis data allowed the calculation of the pK_a3 value for H₃PO₄ to be 12.330 ± 0.02 (25 °C). The hydrolysis of the VO₄^3- ion is ∼21 times larger than that of the PO₄^3-. The pK_a3 value for H₃VO₄ is estimated to be 13.65 ± 0.1 (25 °C).