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]
The Role of Lead in Suppressing Passivation of High Silver-Containing Copper Anodes During Electrorefining by Labone L. Godirilwe and others. printed pp.137–138 and 141, experimental design and identification of silver/lead-containing slime
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.
Gas formation is decided by each interfacial electrode potential and reaction kinetics, rather than by comparing the terminal cell voltage directly with 1.23 V. On the conditional model above, the cathode potential is V versus the standard hydrogen electrode. At unit proton activity and unit hydrogen pressure this is above the hydrogen equilibrium potential, so hydrogen evolution is not favored there. The anode is at V, below the unit-activity oxygen equilibrium potential of 1.23 V, so oxygen evolution is likewise not favored at the intended point. Neither gas is expected in that model, despite a terminal voltage near 2 V; 1.2 V is lost in the electrolyte.
Without the missing cathodic kinetic information, the exact cathode potential is not fixed, so the hydrogen conclusion is conditional. Locally depleted copper ions, increased current, electrode blocking or strong passivation can move an interface into gas evolution. Actual proton/oxygen/hydrogen activities shift equilibrium through the Nernst equation, and gas nucleation and activation barriers further affect observable bubbles. A reference electrode at each interface and direct gas observation distinguish these effects from an increased solution-resistance drop.
The equilibrium written in the reduction direction isWith pure-solid activities set to one, the Nernst equation givesMaintaining sulfate activity fixes the reference potential; protonation to bisulfate in strongly acidic filling solutions must be included in specifying that activity.
Calibrate against, or use a reliable tabulated potential relative to, the standard hydrogen electrode for the same filling solution and temperature. With the voltmeter sign specified above and a corrected or negligible junction potential,There is no universal numerical offset for every silver reference: silver/silver-chloride, silver/silver-sulfate and different sulfate filling solutions define different potentials.