Anodic Processes During Betts Refining in a Small-Scale Electrore fining Cell.

During the electrorefining of lead by the Betts process, ionic concentration gradients become established within the slimes layer. These gradients contribute to precipitation of secondary products and to gradients in electrode potential applied to slimes filaments, and thereby affect the dissolution of noble impurities. This paper describes the experimental results obtained when a typical lead anode was dissolved under galvanostatic conditions with concurrent interruption of current at preset slimes thicknesses. Reference electrodes were incorporated within the lead anode to follow the potential gradients across the slimes electrolyte. Samples of the slimes electrolyte were withdrawn in-situ and their compositional changes were related to transport processes across the slimes layer. Upon current interruption the anodic overpotential decays, first abruptly (as the uncompensated ohmic drop disappears), and then slowly (due to the presence of a back E.M.F. created by ionic concentration gradients that decay slowly). Current interruption measurements showed that: (A) concentration gradients exist across the slimes layer, (B) inner solution potentials within the slimes layer can be larger than those measured from reference electrodes located in the bulk electrolyte, (C) secondary products can shift the inner solution potential to negative values that reverse upon re-dissolution and (D) ionic diffusion is seen upon current interruption but it is complex and difficult to model due to the presence of processes that can support the passage of internal currents. SEM and X-ray diffraction analysis of the slimes filaments indicated that secondary reactions leading to the formation of Si02 and PbF2 take place (mainly at the anodelslimes interface). The onset of these reactions and their relationship to the Pb-F-Si-H20 Eh-pH diagram are linked to the industrial operation of the Betts process.