Electrochimica Acta, Vol.45, No.21, 3543-3554, 2000
Adsorption of halide anions on bismuth single crystal plane electrodes
Adsorption behaviour of Cl-, Br- and I- anions on Bi single crystal plane electrodes from aqueous, methanol and 2-propanol solutions has been studied by impedance spectroscopy and chronocoulometry methods. The values of surface excess and the Gibbs energy of adsorption of halide ions on the Bi(111), Bi(001) and Bi(01(1) over bar) single crystal planes have been calculated using the electrode potential E and the surface charge density sigma as the independent electrical variables. It was found that under comparable conditions the result obtained at constant E and at constant sigma are coincident, The formal charge transfer coefficient (so called electrosorption valency) and the dipole moment of the dipole formed by an adsorbed halide ion and its image charge in Bi plane have been calculated. It was found that on the Bi(111) plane, where the chemical bonds are all saturated, the formal charge transfer coefficient and the dipole moment of adsorbed anion are independent of electrode potential. For more active Bi planes there is noticeable dependence of both characteristics on electrode charge and at higher positive charges the covalent bonding between Bi(01(1) over bar) surface atoms and I- is probable. It was concluded that the dipole formed is significantly screened by the solvent molecules and the metal electron gas, but the influence of the solvent dielectrical and other characteristics on the effective dipole moment values is comparatively small.