Study of simultaneous codeposition of metals at solid electrodes Public Deposited

http://ir.library.oregonstate.edu/concern/graduate_thesis_or_dissertations/x920g014h

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  • As with many pairs of metals, the electrodeposition of Pb-Tl, Cu-Cd, and Cu-Ni at solid electrodes yielded partial polarization curves shifted from the polarization curves of the single metals. The curves for the more noble metals (Pb, Cu) were shifted negatively while the less noble metals'(Tl, Cd, Ni) curves were shifted positively. Such shifts are found to be related to the difference in the binding energy between atoms of the same metals and between atoms of different metals. Thermodynamic calculation shows that the heat of sublimation, and subsequently the strength of the metallic bond, of the alloy is typically higher than the heat of sublimation of the less noble component, but lower than that of the more noble component. Thus, the incorporation of the atoms of the less noble metal into the alloy lattice is energetically more favorable than the incorporation into the same lattice of the less noble metal. Similarly, the incorporation of the atoms of the more noble metal into the alloy lattice is energetically less favorable than incorporation into the same crystal lattice of the more noble metal. The heats of sublimation of the alloys of Ag-Cd, Ag-Zn, Au-Cu, Co-Fe, Cu-Cd, Cu-Ni, Cu-Sn, Cu-Zn, Fe-Zn, Ni-Fe, and Pb -Tl have been calculated and tabulated together with the heats of sublimation of the parent metals. The direction of the shift of the partial polarization curves of these metals during codeposition indeed, confirm the thermodynamic considerations. The principles developed here should be useful in the study of codeposition of alloys and in analytical applications of solid electrodes. The simultaneous codeposition of Pb-Tl, Cu-Cd, and Cu-Ni were explored by cyclic voltammetry and stripping analysis. In support of this, a Cyclic Voltammetry Programmer, an Anodic Stripping Voltammetry Timer, and associated hardware were constructed. Shift in stripping potentials were observed during anodic dissolution of alloys. The stripping potentials shifted in the same direction as the deposition potentials shifted in partial polarization curves.
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