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Electrocapillary studies of tetrahydrofurfuryl alcohol (THFA) in aqueous specifically and non-specifically adsorbed base electrolytes were carried out. The primary results will be compared with those using a Kowalski impedance bridge method. Derived results comprising of standard electro-chemical free energies of adsorption, isotherms, surface excesses and other parameters will be presented to demonstrate unusual distinctive two-point orientation effects not hitherto reported in the literature for saturated heterocyclic compounds. Calculations of the fraction of adsorbed THFA in varying positions on the Hg surface as a function of changing bulk concentrations at constant potential will be discussed.
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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 …
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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 …
