Thermodynamics of the Electrocapillary Effect

Thermodynamics of the Electrocapillary Effect The basic equations of electrocapillarity are the Lippmann equation [110] 

A number of more or less equivalent derivations of the electrocapillary Eq. V-49 have been given, and these have been reviewed by Grahame [113]. Lippmann based his derivation on the supposition that the interface was analogous to a parallel-plate condenser, so that the reversible work dG, associated with changes in area and in charge, was given by 

Equation V-52 may now be redifferentiated, and on comparing the results with Eq. V-51, one obtains 

The treatments that are concerned in more detail with the nature of the adsorbed layer make use of the general thermodynamic framework of the derivation of the Gibbs equation (Section III-5B) but differ in the handling of the electrochemical potential and the surface excess of the ionic species [114-117]. The derivation given here is after that of Grahame and Whitney [117]. Equation III-76 gives the combined first- and second-law statements for the surface excess quantities 

The chemical potential pi, has been generalized to the electrochemical potential Hj since we will be dealing with phases whose charge may be varied. The problem that now arises is that one desires to deal with individual ionic species and that these are not independently variable. In the present treatment, the difficulty is handled by regarding the electrons of the metallic phase as the dependent component whose amount varies with the addition or removal of charged components in such a way that electroneutrality is preserved. One then writes, for the ith charged species. 

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