Technical Papers and Notes - Extractive Metallurgy Division - Interpretation of the Literature on The Mechanism of The Hall Process

Literature on the electrolysis of aluminum from cryolite melts and on the structure of these melts is surveyed critically. Data on density, freezing point, and other properties are reviewed. Theories of the electrolysis are examined in the light of these data. Two theories are presented which account equally well for the observations. ALTHOUGH the production of aluminum is a large-scale industrial process, consuming approximately 3 pet of all of the electric current generated in this country, the mechanism of the Hall Process remains a 70-year-old mystery. It is a remarkable fact that the aluminum industry, which was established largely through research and owes much of its growth to research, still employs as its basic process the one developed by Charles Martin Hall while he was still a young man working in a woodshed. There are, of course, modifications in detail and a tremendous expansion of the size of the units used, but basically the process employs carbon anodes and a carbon-lined iron vessel as a cathode for the electrolysis of alumina dissolved in molten salt. Of the almost infinite variety of salts available, the relatively minor Greenland mineral, cryolite, 3NaF.A1F3, is still the only one which gives good performance in the electrolysis. In the early days, the process was thought of as a simple one. The dissolved alumina dissociated and, during the electrolysis, the aluminum was carried to the cathode where it was discharged and collected in a pool of metal. The oxygen was carried to the carbon anode where it reacted to form primarily carbon dioxide together with some carbon monoxide. About the only virtue that can be claimed for this hypothesis is that of simplicity. The actual mechanisms must be tremendously more complex. This paper is devoted to a rather narrow part of the whole subject, namely, what ions are present in the bath, and by what mechanism the current is carried. The complexity of the literature on this system is demonstrated in Table I, which shows the ions postulated as being present during the process. This system is not easy to investigate. Cryolite melts at about 1000°C, so that all the investigations are at relatively high temperatures. Molten cryolite fumes in air, particularly if excess aluminum fluoride is present. The cryolite changes composition on heating at 1000°C, principally by reaction with moisture in the air, but apparently also by reaction with oxygen. Cryolite reacts with most of the customary materials of construction, and those that are not attacked by cryolite seem inevitably to react with molten aluminum. Graphite is the only common material that is inert to the electrolytic bath. Pure cryolite can be held in platinum. There is hope that some of the newer refractories will stand up in bath, and their development for this purpose would be a major advance in the field. The techniques to be discussed, then, are not the most advanced ones. Rather, they are examples of old standardized methods applied under difficult conditions. The principal methods that shed real light on the mechanism are density, electrical conductivity, freezing-point lowering, transport number, viscosity measurements, and reactivity of bath with carbon dioxide. The first measurement to be discussed is density. This procedure is relatively straightforward. A hollow platinum bob is suspended by fine platinum wire from an analytical balance into the melt being investigated. Density1-4 of the system sodium fluoride-aluminum fluoride is shown in Fig. 1. There is a maximum in the density near the cryolite composition, but actually the maximum is on the NaF-rich side of cryolite, close to the composition NaF - Na3AlF8. Density measurements are also useful in giving a clue to the nature of cryolite-alumina melts.1, 4 On the first addition of alumina, density decreases, Fig. 2, although the density of alumina, either solid or liquid, is higher than that of cryolite. These density results indicate that the systems are not simple. A great deal of effort has been spent in measuring the electrical conductivity of molten cryolite and of cryolite with various additives. Conductivity measurements are quite easy for fused salts that can be measured in a dip cell, but no successful dip cell has been made available yet for cryolite. Recourse is had