Samples of rutile prepared by hydrolysis of TiCl₄ and by combustion of Ti(isoPrO)₄ have been investigated by infra-red spectroscopic techniques to provide information on their surface hydroxylation and hydration. After outgassing at ambient temperatures the rutile surface carries both hydroxyl ions and adsorbed molecular water. The depopulation of the surface caused by raising the outgassing temperature follows a pattern that suggests there are two types of surface site for the adsorbed molecular species. Complementary studies of pyridine adsorption indicate that the molecular water is held on the surface as a coordinating ligand and also show the presence of two types of hydroxyl species on the ambiently outgassed oxide. Further studies of the adsorption of thionyl chloride, sulphur dioxide and hydrogen chloride vapours support the contention that the surface hydroxyls are ionic in character. In the case of HCl adsorption, evidence for two types of coordinately bonded water was found after exposure of the oxide to the dry acid gas. It was also found that the sample prepared from TiCl₄, which carried chlorine in its surface layers, was more readily dehydroxylated than the “chlorine free” material prepared from the metal alkoxide. The chlorine containing sample also aggregated on storage whereas the pure material did not.