Solvent Structure and Molecular Orientation in the Double-Layer at the Mercury- Water Interface

Abstract

Solvent structure and molecular orientation in the Hg-water interphase is an important and previously little investigated aspect of the electrical double-layer at charged metal interfaces. By using pyrazine and pyridine in critical comparative experiments on a) changes of surface dipole potential difference (Esin and Markov effects), b) surface pressure changes and c) charge dependence of free energy of adsorption, it is shown how the surface dipole contribution from oriented solvent molecules may be evaluated together with the charge-dependent distribution function for water orientation. In the case of pyridine, orientation of the adsorbate molecule itself occurs in a manner dependent on surface charge on the metal and interaction with oriented and bulk solvent molecules

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