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

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.SCOPUS: ar.jinfo:eu-repo/semantics/publishe

The surface phase at the ideal polarized mercury electrode. 2. Coulostatic measurements at the Hg electrode in dilute NaF aqueous solutions at various temperatures

Electrocapillary measurements in NaF aqueous solution at the Hg electrode are reported. Charge densities obtained by the coulostatic technique in the case of 10-1 mol kg-1 mol kg-1 aqueous NaF solution at 15, 25, 35 °C agree well with values measured by the bridge method (for 10-1 mol kg-1) and conform with calculated valued based on the Gouy-Chapman model. Results of surface tension are obtained by means of the maximum bubble pressure technique. Comparison is made between these results and data derived from coulostatic measurements. The partial molar surface entropies of water in function of the density of charge are computed from the temperature coefficients of the surface tension. © 1974.SCOPUS: ar.jinfo:eu-repo/semantics/publishe