Raman- and infrared-spectroscopic investigations of dilute aqueous phosphoric acid solutions

Abstract

Phosphoric acid in water and heavy water has been studied by Raman and infrared spectroscopy over a broad concentration range (0.00873-1.560 mol kg(-1)) at 23 °C. The vibrational modes of the PO(4) skeleton (C(3v) symmetry) of H(3)PO(4)(aq) and D(3)PO(4)(D(2)O) have been assigned. In addition to the P-O stretching modes a deformation mode has been detected, δPO-H(D) at 1250 and 935 cm(-1), respectively. In addition to the modes of the phosphoric acid and heavy phosphoric acid a mode of the dissociation product H(2)PO(4)(-) and D(2)PO(4)(-) has been detected at 1077 cm(-1) and 1084 cm(-1) respectively. H(3)PO(4) and D(3)PO(4) is hydrated in aqueous solution which could be verified by Raman spectroscopy following the νP[double bond, length as m-dash]O and ν(s)P(OH)(3) mode as a function of temperature. These modes show a pronounced temperature dependence inasmuch as νP[double bond, length as m-dash]O shifts to higher wavenumbers with temperature increase and ν(s)P(OH)(3) to lower wavenumbers. In the range between 300-600 cm(-1) the deformation modes have been observed. In very dilute H(3)PO(4) solutions however, the dissociation product is the dominant species. The dissociation degree, α for H(3)PO(4)(aq) and D(3)PO(4)(D(2)O) as a function of dilution has been measured at 23 °C. In these dilute H(3)PO(4)(aq) and D(3)PO(4)(D(2)O) solutions no spectroscopic features for a dimeric species of the formula H(6)P(2)O(8) and D(6)P(2)O(8) could be detected. Quantitative Raman measurements have been carried out to follow the dissociation of H(3)PO(4) and D(3)PO(4) over a very broad concentration range and also as a function of temperature. From the dissociation data, the pK(1) value for H(3)PO(4) has been determined to 2.14(1) and for D(3)PO(4) to 2.42(1) at 23 °C. In the temperature interval from 24.5 to 99.7 °C the pK(1) values for H(3)PO(4)(aq) have been determined and thermodynamic data have been derived.