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By Abner Brenner
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On the other hand, the reversible potential of an electrode is a definite quantity, and even though it may not be capable of direct measurement, it can be calculated from thermodynamic data. 5 CONVENTIONS REGARDING SIGNS OF ELECTRODES 29 fundamental significance than polarization, as herein defined, because it repre sents the excess of potential above a certain definite reference potential. Or stated in another way, it is one factor that measures the wasted energy of the process. For most electrochemical studies involving metals, polarizations are more frequently reported than overvoltages, because the static potential of an electrode can always be directly measured but not the equilibrium potential.
The equihbrium is disturbed to some extent by the chemical displacement of hydrogen from the solution by the metals. The conditions for the chemical or mutual equihbrium between two metals which form a solid solution or intermetallic compound are more complicated than those for a simple eutectic type of alloy as previously described. If an electrode of each metal were placed in a solution of its ions, and the solutions connected by a salt bridge to form a cell, and the external leads of the cell were shorted, the potential between the electrodes would eventually drop to zero and the system would be in equilibrium.
3. Equilibrium. The two metals composing the alloy are in chemical equili brium with the bath. 4. Anomalous. The less noble metal deposits preferentially. 5. Induced. Elements which cannot be deposited individually can codeposit with another metal. Types 1-3 are collectively referred to as normal alloy plating systems and are characterized by the preferential deposition of the more noble metal. Types 4 and 5 are referred to as abnormal codeposition because the more noble metal does not necessarily deposit preferentially.