Fourier transform infrared (FTIR) spectroscopy of the OD band of HDO molecules has been applied to perform a systematic study of various phosphate forms in the order of decreasing protonation: H3PO4, KH2PO4, K2HPO4, K3PO4. HDO isotopically diluted in H2O has been prepared by adding adequate amounts of D2O to aqueous solutions in ordinary water. The difference spectra procedure has been applied to remove the contribution of bulk water and thus to separate the spectra of solute-affected HDO. The position at maximum of the principal anion-affected HDO band for potassium phosphates moves in the order KH2PO4 (2478 cm(-1)) > K2HPO4 (2363 cm(-1)) > K3PO4 (2301 cm(-1)), that is, decreases with increasing solute basicity and charge. The number of moles of water affected by one mote of solute (N) equals 11.0, 13.8 and 16.2, respectively. Phosphoric acid affects statistically 13.9 water molecules and appears to be a "structure making" solute in water. The isotopic substitution with deuterium occurs also on the phosphate anions and phosphoric acid. The thus formed P-O-D groups interact with water molecules via strong hydrogen bonds and the relative strength of this interaction increases with increasing solute acidity. The plausible assignments of OD bands of HDO have been confirmed by calculating equilibrium structures of small aqueous clusters of the studied individua utilizing density functional theory. Further interpretation of the energetic and structural properties of hydrating water is enabled by calculating intermolecular interaction energy of water and probability distributions for interatomic oxygen-oxygen distance.