Structure Determination of Phosphoric Acid and Phosphate Ions in Aqueous Solution Using EXAFS Spectroscopy and Large Angle X‑ray Scattering

The structures of hydrated phosphoric acid and phosphate ions (H2PO4, HPO42–, and PO43–) in aqueous solution have been determined by P K-edge EXAFS and large angle X-ray scattering (LAXS). The P–O bond distance in all phosphate species studied is close to 1.53 Å. The P–(O)···Oaq distances have been refined to ca. 3.6 Å from the LAXS data giving a P–O···Oaq bond angle close to tetrahedral, suggesting that each oxygen or OH group of phosphoric acid and dihydrogen phosphate, on average, hydrogen bind three water molecules. The (P−)­O­(−H)···Oaq and (P−)­O···(H−)­Oaq hydrogen bonds in hydrated phosphoric acid and the H2PO4 ion are shorter than the hydrogen bonds in neat water. This supports previous infrared spectroscopic studies claiming that the hydrogen bonds in hydrated phosphoric acid and phosphate ions are stronger than the hydrogen bonds in neat water. Phosphoric acid and phosphate ions can therefore be regarded as structure making solutes. This is the first study applying transmission mode X-ray absorption spectroscopy (XAS) data collection on the P K-edge. It shows that XAS spectra collected in transmission mode have a much better S/N ratio than data collected in fluorescence mode, allowing accurate determination of P–O bond distances. Furthermore, P K-edge EXAFS data collected in fluorescence mode display a higher amplitude at high k than expected due to increasing radiated volume of the sample with increasing energy as the total absorption decreases sharply with increasing energy of the X-rays. As a result, the fluorescence signal becomes nonproportional to the intensity of the X-ray beam over the EXAFS spectrum. This results in an increasing amplitude of the EXAFS function with increasing energy of the X-ray beam resulting in too small Debye–Waller coefficients.