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The surface phase at the ideal polarized mercury electrode. I. General thermodynamic and hydrostatic considerations of ionic adsorption

par Hurwitz, Heinz Dieter ;D'Alkaine, Carlos C.V.
Référence Journal of electroanalytical chemistry, 42, 1, page (77-103)
Publication Publié, 1973-02

Article révisé par les pairs

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Résumé :

A thermodynamic derivation is presented for temperature and pressure coefficients of the surface tension at the ideal polarized electrode in systems of mixed common ion symmetrical strong electrolytes at constant ionic strength. Based upon these coefficients, an evaluation of partial molar surface phase entropies and volumes is suggested. The treatment requires a convenient transformation of the system state variables and an adequate choice of conventions compatible with a concept of electrochemical inner and diffuse layers. A complementary insight into the problem of surface phases is gained from consideration of hydrostatic and electrostatic forces and stresses at the boundary of the liquid metal electrode. Expressions yielding the electrochemical potentials are derived, revealing the non-autonomy of the inner layer as regards adjacent surface phases. Finally, the relevance of given expressions of the partial molar surface phase entropy of the solvent in relation to some isotherms of ionic specific adsorption, is discussed. © 1973.