Abstract - 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. In the early days, the process was thought of as a simple one. 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. Using cryoscopic data, Rolin has determined the following composition for molten cryolite. Na2,AlF 3Na + 3F + AlF [1] He postulates the following equation for the ioniza-tion of alumina at low concentrations Al2O3 Al + AlO2 +O. [2] At concentrations above 0.025M he supposes the ionization of alumina to proceed as follows Al2O3 AlO + AlO2. [3] Rolin's mechanism of electrolysis for the more concentrated solution in Eq. 3 is as follows. The AlO' ion migrates to the cathode. where it is dis- charged, giving metallic aluminum and 0' ions which migrate to the anode. The AlO2- ion migrates to the anode, where it is discharged, giving Al ions and oxygen which reacts with carbon to form CO2 In the case of the extremely dilute solution in Eq. 2 the Al ion migrates to the cathode and the AlO2-and 0 migrate to the anode as before. Another possible mechanism for the electrolysis follows. Ionization of Cryolite Na3AlF4 = 2Na + 2F + NaAlF, Na + AlF-AlF+Na + F [4] Addition of Alumina 2Na2AlF+ 2AL2O4 6Na + 3A12O3F4 [5a] Al2O2F 2AlOF2 [5b] Cathode Process AlF, + 3e+ 4F + Al. [6] Anode Process AlOF2 + 2F AlF1 + 1/20, + 2e or A12O2F + 4F-2A1F; + 0, + 4e. [7] Although both Rolin's and the present mechanism of the Hall process may be qualitatively satisfactory, present data are not adequate for quantitative tests of the theories.