Journal of Electroanalytical Chemistry, Vol.469, No.2, 182-188, 1999
Calculation of thermodynamic and inner layer characteristics of halide ions adsorbed on bismuth single crystal planes from solutions in methanol
The values of the surface excess and the Gibbs energy of adsorption of halide ions on the (111), (001) and (01 (1) over bar) Bi single crystal planes in methanolic solutions have been calculated from the previously obtained experimental data using electrode potential as the independent electrical variable. It was found that under comparable conditions the results obtained at constant electrode potential and at constant electrode charge are coincident. The electrosorption valency and the dipole moment of the dipole formed by an adsorbed halide ion and its image charge in the Bi plane have been calculated. It was found that on the Bi(111) lane, where the chemical bonds are all saturated, the electrosorption valency does not depend on electrode charge and in the measured range of potentials a weak, dependence of;he dipole value formed by an adsorbed halide ion and its image charge in Bi on the electrode charge was found. In contrast, on the more active Bi planes there is noticeable dependence of both characteristics on electrode charge and at higher positive charges, covalent bonding between Bi(01 (1) over bar) surface atoms and I- anions is probable. It was concluded that the dipole formed is screened significantly by the solvent molecules and the metal electron gas.