There is described the separation of aliphatically-unsaturated hydrocarbons from mixtures by the combined use of liquid barrier permeation and metal complexing techniques. The liquid barrier is within a hydrophilic film membrane, and the barrier contains complex-forming metal ions in aqueous solution. The metal ions may be, for example, noble metal, nickel, mercurous, cuprous or other metal ions, and mixtures of these metal ions, with or without other cations, may be used. The separation of ethy...