A process is disclosed for making CF 3 CF=CHF. The process involves reacting CF 3 CCIFCCI 2 F with H 2 in a reaction zone in the presence of a catalyst to produce a product mixture comprising CF 3 CF=CHF. The catalyst has a catalytically effective amount of palladium supported on a support selected from the group consisting of alumina, fluorided alumina, aluminum fluoride and mixtures thereof and the mole ratio of H 2 to CF 3 CCIFCCI 2 F fed to the reaction zone is between about 1 :1 and about 5:1.. Also disclosed are azeotropic compositions of CF 3 CCIFCCI 2 F and HF and azeotropic composition of CF 3 CHFCH 2 F and HF.