<p> Techniques have been developed for making cryoscopic and vapour pressure measurements in anhydrous hydrogen fluoride. The cryoscopic constant for the solvent has been determined. </p> <p> The techniques developed have been used to determine the mode and extent of the ionization of some acids and bases of the HF system. The formation and stability of polymeric ions in the solvent has been investigated and the formation of the previously unknown anion As₂F₁₁⁻ has been shown. Cryoscopy has been used to detect a new polymeric 1:1 adduct of XeF₂ and SbF₅. Solutions of cyanides in HF have been investigated and the formation of a new polymeric cation Hg₂CN₃⁺, formed when mercury cyanide dissolves in HF, has been suggested. The results of some experiments on solvolysis reactions are also reported. </p> / Thesis / Doctor of Philosophy (PhD)