Two model compounds, sodium pyrophosphate (pyro-P) and sodium tripolyphosphate (tripoly-P), were employed to elucidate the binding mechanisms of condensed phosphate on aluminum hydroxide by utilizing attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. Peak assignments for the condensed phosphates in the solution phase and those adsorbed on the surface of aluminum hydroxide were made. Electron delocalization and polarization were employed to explain the peak shifts and the complexation of condensed phosphate with aluminum hydroxide. The tripoly-P and pyro-P were adsorbed on aluminum hydroxide by forming inner-sphere complexes. The adsorbed condensed phosphates were deprotonated in the pH range from 4 to 10. Monodentate, bidentate, and binuclear complexes were formed when pyro-P was adsorbed on aluminum hydroxide, while monodentate and binuclear complexes were formed when tripoly-P was adsorbed. Based on the FTIR data, we proposed that when either bidentate or binuclear complexes were formed, the two oxygen atoms participating in the complexation with aluminum hydroxide could not be originated from the same terminal phosphate moiety. The Al-O bond formed in the complexation of pyro-P or tripoly-P with aluminum hydroxide (&3bond; AlPO3-) was not as strong as the H-O bond in terminal HPO3-. The bridging PO2- of tripoly-P did not coordinate with aluminum hydroxide. The real-time ATR-FTIR study on condensed phosphate adsorption revealed that a long contact time between condensed phosphates and aluminum hydroxide particles can result in a transformation of an initially formed species into a thermodynamically more stable phase. (c) 2004 Published by Elsevier Inc.