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Following previous studies on solid metals, electrocapillary measurements are reported for the adsorption of a series of heterocyclic and aromatic bases (and their ions) at the mercury electrode. The adsorption isotherms are derived for various electrode potentials and standard free energies ΔG⁰ of adsorption are deduced and related to molecular and electronic structure of the adsorbates. Specific π-orbital interaction effects are indicated which determine the orientation of the bases at the electrode. It is shown that dipole interaction effects lead to variations of ΔG⁰ with the 3/2 power of surface coverage θ; this prediction is confirmed experimentally. The variation of …
