Abstract
The basics of redox equilibria are presented.
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- 1.
A Galvani potential difference is established across all possible interfaces between two phases. This cannot be discussed here in detail but we refer the reader to the paragraph about glass electrodes in Chap. 7.5.3.1 .
- 2.
In the case of the Nernst equation, a problem occurs that is similar to the problem of defining pH: since at least one of the two forms of Ox or Red are ionic, and because single ion activities are, for principle reasons, inaccessible and only approximately determinable, the Galvani potential differences of half-cells and the potential differences of Galvani cells are not precisely defined, which, fortunately, is not a serious issue for applications.
- 3.
Platinum black is highly active in catalyzing the oxidation of hydrogen gas with air; a property used by the German chemist Wolfgang Döbereiner (1780–1849) in constructing a lighter (“Döbereiner’s lamp” or “Döbereiner’s tinderbox”).
- 4.
Strictly speaking, the combination of half-cells will only then give thermodynamically based potential differences, when both half-cells operate reversibly, i.e., reduction and oxidation need to be unhindered. In reality, this is rare. See subsequent discussion on redox systems coupled to acid–base equilibria and also the discussion on redox titrations in Chap. 7.
- 5.
\(2.303RT/F\) equals 0.05916 V at 25 °C. For simplicity we use here 0.059 V.
- 6.
Robert Thomas Dietrich Luther (1868–1945) was a German physical chemist, coworker of Wilhelm Ostwald, and distant descendant of the German church reformer Martin Luther.
- 7.
These diagrams are named in honor of the US physical chemist Wendell Mitchell Latimer (1893–1955).
- 8.
Marcel Pourbaix (1904–1998) Belgian physical chemist.
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Scholz, F., Kahlert, H. (2019). Redox Equilibria. In: Chemical Equilibria in Analytical Chemistry. Springer, Cham. https://doi.org/10.1007/978-3-030-17180-3_6
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DOI: https://doi.org/10.1007/978-3-030-17180-3_6
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