The free energies of specific adsorption (AG°) for Br-, Cl-, F-, and OHin aqueous solution on Hg, Ag, and Au electrodes are calculated. The model includes metal-ion interactions, ion-water interactions, watermetal interactions, and Born energy contributions. For the halide ions, the calculated AG°a gree with previously reported experimental trends in adsorption although the magnitudes of AG°are too great. For QHadsorption, the calculated AG°do not agree with experimental data; reasons for the discrepancy are discussed. Adsorption for Brand Clis accompanied by loss of primary waters of hydration and the ions situate in the inner Helmholtz plane. The Fand OHions are negligibly dehydrated and adsorb in the outer Helmholtz plane.(1) This work was performed under the auspices of the U. 8. Atomic Energy Commission.
The potentials of zero charge of the mercury, silver, and gold electrodes were measured in aqueous salt solutions containing tetra‐alkylammonium and some other cations. The open‐circuit scrape method was used in the case of the solid electrodes, and the streaming electrode method was used for mercury. For mercury the potential of zero charge (pzc) shifts either positive or negative with increasing electrolyte concentration, depending on the relative adsorbabilities of the cation and anion. In the case of gold and silver the pzc is more cathodic in tetra‐alkylammonium or cesium salt solutions than in solutions containing sodium ions. This difference in trend for mercury from the gold or silver electrode, with cation variation, reflects the variance in metal‐anion vs. metal‐cation interactions on the different metals.
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