The reactions between molten aluminium and cryoIite have been determined from a material balance of all components involved in the process. The interpretation of results were supported by x-ray diffraction studies of the evolved vapours, quenched electrolyte samples, and side-reaction products.The most important reaction involves the formation of both Na2F (sodium subfluoride) and chiolite in the fused electrolyte. The Na2F accelerates vaporization of the melt. Some AIF (aluminium monofluoride) may also be formed but the proportion of this is much less than for the former subvalent compound.