Specific adsorption of bromide and iodide ions from N-methyl formamide solutions with constant ionic strength on liquid ga electrode

The differential capacitance curves were measured with an ac bridge in the Ga/[N-MF + 0.1 m M KBr + 0.1 (1 − m) M KClO4] and Ga/[N-MF + 0.1 m M KI + 0.1 (1 − m) M KClO4] systems at the following fractions m of surface-active anions: 0, 0.01, 0.02, 0.05, 0.1, 0.2, 0.5, and 1. As compared with other solvents, N-methyl formamide (N-MF) enables one to realize the largest positive charges of Ga electrode, at which it remains ideally polarizable (up to 20 μ/cm2). The data on the specific adsorption of Br− and I− anions in the system can be quantitatively described by the Frumkin’s isotherm; to the first approximation, free energy of halide ion (Hal−) adsorption \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$\Delta G_{adsHal^{ - 1} } $\end{document} is a linear function of electrode charge. It is found that, in contrast to the Hg/N-MF interface, \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$\Delta G_{adsHal^{ - 1} } $\end{document} at the Ga/N-MF interface varies in the reverse order: Brt— ∼ I− < Cl−. From the measured results, we can conclude that the energy of metal-Hal− interaction increases in series: \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$\Delta G_{M - Cl^ - } > \Delta G_{M - Br^ - } > \Delta G_{M - I^ - } $\end{document} and the difference \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$(\Delta G_{Ga - Hal_1^ - } - \Delta G_{Ga - Hal_2^ - } )$\end{document} is larger than the difference between the solvation energies of \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$Hal^ - (\Delta G_{S - Hal_1^ - } - \Delta G_{S - Hal_2^ - } )$\end{document}.