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Une théorie est proposée dans laquelle on suppose que les coefficients d'activité des électrolytes sont dus à trois principales interactions entre les ions: a) forces électriques, b) hydratation, c) relargage mutuel. Les valeurs expérimentales des coefficients d'activité à 25°C furent corrigées pour les effets d'hydratation et de relargage mutuel afin d'obtenir la contribution des forces électriques. Une étude de la dépendance de cette contribution sur la concentration démontre la supériorité du modèle d'un réseau désordonné à celui d'une atmosphère ionique de Debye-Hückel pour les concentrations entre 0.1 et 1 molaire.
Colloque
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 …
Colloque
Methods available for study of adsorption of ions at electrodes are briefly reviewed and results obtained for the adsorption of alkaloid ions at mercury are described. The necessity for development of a thermodynamically rigorous technique for determination of adsorption at solid electrodes is stressed. For organic ions and molecules which absorb in a convenient wave length region (visible or u.v.), adsorption of the ions may be followed directly at solid electrodes in situ in a special cell in which both u.v. extinction and potential measurements can be made simultaneously. Results obtained with acridine, acridinium chloride, quinolinium chloride, quinoline and pyridine …
Colloque
Methods available for study of adsorption of ions at electrodes are briefly reviewed and results obtained for the adsorption of alkaloid ions at mercury are described. The necessity for development of a thermodynamically rigorous technique for determination of adsorption at solid electrodes is stressed. For organic ions and molecules which absorb in a convenient wave length region (visible or u.v.), adsorption of the ions may be followed directly at solid electrodes in situ in a special cell in which both u.v. extinction and potential measurements can be made simultaneously. Results obtained with acridine, acridinium chloride, quinolinium chloride, quinoline and pyridine …
Colloque
Methods available for study of adsorption of ions at electrodes are briefly reviewed and results obtained for the adsorption of alkaloid ions at mercury are described. The necessity for development of a thermodynamically rigorous technique for determination of adsorption at solid electrodes is stressed. For organic ions and molecules which absorb in a convenient wave length region (visible or u.v.), adsorption of the ions may be followed directly at solid electrodes in situ in a special cell in which both u.v. extinction and potential measurements can be made simultaneously. Results obtained with acridine, acridinium chloride, quinolinium chloride, quinoline and pyridine …
