This paper describes an apparatus which was developed to study solid-vapour equilibria and presents results which were obtained during a study of the FeCI3-AlCI3-CI2 system. Analysis of the results showsthat fractional desublimation might offer a means of achieving a useful separation of the iron and aluminium chlorides produced by the chlorination of bauxite. The results, presented in the form of isothermal vapour pressure curves covering the range of temperature 160-200C, support the earlier findings of Semenenko et al (Dokl Akad Nauk SSSR, 154: 42-43 (1964)) that the solid phase contains two terminal solid solutions.The equilibrium constant for the formation of the mixed dimer, FeAICI6, was approximately 4. The latent heat of sublimation of aluminium chloride varied from 18 to 26 kcal/mole AI2CI6 for solid compositionsfrom 0.9 to 05 mole fraction FeCls3.