Disclosed herein is a process to produce an azeotrope composition comprising a hydrofluoroolefin and hydrogen fluoride, said process comprising, dehydrofluorinating a hydrofluorocarbon containing at least one hydrogen and at least one fluorine on adjacent carbons, thereby forming a mixture comprising said hydrofluoroolefin, unreacted hydrofluorocarbon and hydrogen fluoride, and distilling the mixture to produce a distillate composition comprising an azeotrope composition containing said hydrofluoroolefin and hydrogen fluoride and a column bottoms composition comprising said hydrofluorocarbon essentially free of hydrogen fluoride. Also disclosed herein are processes for separation of hydrofluoroolefins from hydrofluorocarbons and from hydrogen fluoride.