Solution

ID: past-exam-of-the-mphil-in-micro-and-nanotechnology-enterprise-course-of-the-university-of-cambridge/2017/paper-1/section-b/11/iii/solution

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.

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