Electrode Potentials And Potentiometry

Use of the potential of a galvanic cell to measure the concentration of an electroactive species developed later than a number of other electrochemical methods. In part, this was because a rational relation between electrode potential and the concentration of an electroactive species required the development of thermodynamics, and, in particular, its application to electrochemical phenomena. The work of J. Willard Gibbs in the 1870s provided the foundation for the Nernst equation. The latter provides a quantitative relationship between potential and the ratio of effective ther-modynamic concentrations [activities] for a redox couple ([ox]/[rei]) and is the basis for potentiometry and poten-tiometric titrations. The utility of potentiometric measurements for the characterization of ionic solutions was established with the invention of the glass electrode in 1909 for a selective potentiometric response to hydronium-ion concentrations. Another milestone in the development of potentiometric measurements was the introduction of the hydrogen electrode for the measurement of hydronium-ion concentrations; one of many important contributions by Professor Joel Hildebrand. Subsequent development of special glass formulations has made possible electrodes that are selective to different monovalent cations. The idea is so attractive that intense effort has led to the development of electrodes that are selective for many cations and anions, as well as several gas- and bioselective electrodes. The use of these electrodes and the potentiometric measurement of pH continue to be among the most important applications of electrochemistry.

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