A Wedge Effect at Amalgam/Electrolyte Surfaces

Physics

Scientific paper

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Scientific paper

When amalgams are formed by discharge of the ions Li+, Na+, K+, Ca++, Mg++, NH4+ at a mercury cathode in a glass vessel, a wedge of electrolyte penetrates between the amalgam and the glass. The effect is not observed for the discharge of Ag+, Zn++, Cd++ or OH3+ ions. To elucidate the origin of the forces maintaining the wedge in equilibrium, the wedge thickness and the curvature of the mercury/electrolyte interface have been investigated in various ways. The apex of the wedge was studied by interferometry. Measurements have been made during electrolysis of the interfacial tensions mercury/electrolyte and mercury/gaseous nitrogen. Possible theoretical interpretations are discussed. A marked reduction of the surface tension which is observed at certain amalgam/electrolyte interfaces is attributed to strong surface adsorption of the metal especially when the atom is more readily polarized than mercury. The electro-positive character of the amalgams and this reduction of surface tension explain some of the phenomena of the wedge effect.

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