nickel is less noble than copper and can dissolve anodically, but its reduction requires a much more negative cathodic electrode potential. It therefore normally accumulates in solution rather than codepositing with copper. lead can also oxidize, but sulfate can precipitate the resulting lead ions as poorly soluble lead sulfate, contributing to anode slime or passivation. gold normally remains in the solid residue. silver is normally recovered predominantly in anode slime, but its path can include dissolution and reprecipitation or cementation: a permanent refusal of every silver atom to dissolve is not the mechanism. Experiments with controlled Cu–Ag–Pb anodes, a fixed sulfate electrolyte and SEM/EDS plus diffraction analysis explicitly find metallic silver and sulfate-containing slime phases.[ref]
Selective electrode potential, solution management and physical exclusion of slime permit purer copper deposition. However, the unusually large printed anodic slope prevents an unconditional silver-retention claim here. The preceding calculation places the anode near V versus the standard hydrogen electrode, above the tabulated /Ag value. silver oxidation is then thermodynamically possible; any silver ions reaching the cathode can be reduced preferentially to copper. Actual activities, precipitation, cementation and transport determine contamination. The requested 99.999 wt% purity cannot be established from the listed standard potentials alone. Monitor anode potential against a reference, assay the electrolyte and deposit, and prevent slime entrainment; do not silently replace the printed 0.295 V/decade with a smaller number to remove this issue.
First hold the production rate fixed, so total electric current remains . If only the impure anode receives a factor increase in accessible area, its local current density becomes , far below . Extrapolating the large-current Tafel equation would give a negative anodic overpotential, which is physically the wrong regime. Near equilibrium the Butler-Volmer equation instead gives, in the same conditional two-electron model,
The anode activation loss nearly disappears; the 1.20 V ohmic loss does not disappear. The cathode still operates close to its original transport limit if it is unchanged. The conditional kinetic model gives V for anode-only enlargement. Its anodic potential returns close to 0.34 V, making retention of noble silver and gold more favorable, while less noble nickel dissolution and lead sulfate formation remain relevant.
If both active areas increase by and their independent mass-transfer capacity scales by the same factor, both local kinetic losses become small and the conditional prediction is about V. Porous internal area does not generally multiply an external diffusion-limited flux by : pore access, ion depletion, tortuosity, electrical connectivity and slime blockage must be checked. If the specified 200 A/m² is instead held per true enlarged area, total current rises to A and the unchanged electrolyte resistance would give V, so this is an entirely different operating condition.
For the same refining rate and the same effective kinetic model, the anode-only estimate is therefore . The robust conclusion at fixed total current is reduced local activation polarization on the genuinely accessible enlarged surface, with an unchanged ohmic floor unless cell geometry or conductivity also changes. Increased geometric area alone does not prove a proportionate decrease in energy cost or improved purity. The distinct area and current conventions above specify how to interpret the prediction; they must not be mixed in one calculation.