Abstract
Here we extend on the brief introduction of the surface tension given in Chap. 4. To a large extent, our treatment is based on the works of Grahame [1] and Parsons [2] and, like all proper thermodynamics, is exact. However, our way of defining the surface tension and deriving its differential is different, and is based on a discussion with H. Ibach, whose book contains an alternative derivation directed at solid electrodes [3]. In the classical derivation, the surface tension is introduced ad hoc, and it is not clear that it has the potential as its natural variable. For liquid electrodes thermodynamics offers a precise way to determine the surface charge and the surface excesses of a species. This is one of the reasons why much of the early work in electrochemistry was performed on liquid electrodes, particularly on mercury – another reason is that it is easier to generate clean liquid surfaces than clean solid surfaces. With some caveats and modifications, thermodynamic relations can also be applied to solid surfaces, and it is still the most exact way to obtain surface excesses.
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Notes
- 1.
From here on we follow the classical derivation.
- 2.
We thank our colleagues Juan Feliu and Jacek Lipkowski for enlightening discussions on these concepts.
References
D.C. Grahame, Chem. Revs. 41 (1947) 441; D.C. Grahame and B.A. Soderberg, J. Chem. Phys. 22 (1954) 449.
R. Parsons, Comprehensive Treatise of Electrochemistry, Vol. I, edited by J. O’M. Bockris, B.E. Conway, and E. Yeager, Plenum Press, New York, NY, 1980.
H. Ibach, Physics of Surfaces and Interfaces, Springer, Berlin, Heidelberg, 2006.
J. Lipkowski and L. Stolberg, Adsorption of Molecules at Electrodes, edited by J. Lipkowski and P.N. Ross. VCH, New York, 1992.
R.G. Linford, Chem. Rev. 78 (1978) 81.
H. Ibach, C.E. Bach, M. Giesen, and A. Grossmann, Surf. Sci. 375 (1997) 107.
V. Climent, R. Gomez, and J.M. Feliu, Electrochim. Acta 45 (1999) 629.
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Schmickler, W., Santos, E. (2010). Thermodynamics of ideal polarizable interfaces. In: Interfacial Electrochemistry. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-04937-8_8
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