Adsorption of anions on bismuth single crystal plane electrodes from various solvents

The kinetics of electroreduction of hexaamminecobalt(III) cation on Bi planes in aqueous HClO4 solutions

“…It should be noted that there is a good agreement of these data with the data of specific adsorption of various anions from aqueous electrolytes with constant ionic strength [31][32][33] as well as from various non-aqueous solvents [34][35][36][37]. It is very well established fact that the virial adsorption isotherms for Bi(h k l) j Cl À , Br À and I À interfaces are nearly linear [31][32][33][34][35][36][37] but the isotherms corrected for the diffuse layer effect (i.e. corrected for the classical diffuse layer potential) are noticeably more nonlinear.…”

In situ infrared spectroscopic characterization of a bismuth–ethanol interface

“…The zero charge potential values in aqueous solution (E q=0 = −0.61 V vs. Ag|AgCl) and in ethanol (E q=0 = −0.385 V) were obtained in our earlier works [8,31] by measuring the diffuse layer minimum potential in the C s ,E curves in dilute electrolyte solutions. The lower capacitance values for ethanol at negative surface charge densities are caused by the lower dielectric constant as well as the larger dimensions of ethanol molecules compared to water molecules [9][10]. At positive surface charge densities, the capacitance values are higher than at negative surface charge densities for both ethanol and aqueous media, which indicates that the anions approach closer to the bismuth electrode surface than the cations.…”

“…Adsorption phenomena at metal-electrolyte interfaces have been studied on Hg [1][2][3] and mercury-like metals (mostly Bi) over many years, using mainly electrochemical methods [4][5][6][7][8][9][10][11][12][13][14][15][16]. Currently, the use of bismuth provides several advantages over the toxic mercury electrode-the solid surface of Bi can be studied using several modern in situ methods including STM and infrared spectroscopy more easily than the liquid metal surface of mercury [2][3][4]16].…”

“…The adsorption of linear alcohols at bismuth from aqueous electrolyte solutions is substantial and the adsorption activity of an alcohol depends on the hydrocarbon chain length (the increase in the absolute value of the Gibbs adsorption energy is approximately 3.5 kJ mol −1 for each additional CH 2 group) [5][6][7][8][13][14][15]. Adsorption of different halides and alkali metal cations from ethanol solution has been studied in detail by chronocoulonometry, cyclic voltammetry and impedance methods [5][6][7][8][9][10][11][12]. Anions (I − > Br − > Cl − > ClO 4 − > F − ) tend to adsorb much more strongly to bismuth electrodes than do alkali metal cations (Cs + > K + > Na + > Li + ) [5][6][7][8][9].…”

“…Anions (I − > Br − > Cl − > ClO 4 − > F − ) tend to adsorb much more strongly to bismuth electrodes than do alkali metal cations (Cs + > K + > Na + > Li + ) [5][6][7][8][9]. Iodide ions even form a surface compound at large positive surface charge density [10][11][12]. Others have shown [6] that a very small amount of residual water in ethanol does not influence the electrode capacitance in the low-current potential region.…”