Comparison study of adsorption of Cl−, Br−, and I− ions from dimethyl formamide on In-Ga and Tl-Ga electrodes

The adsorption of Cl−, Br−, and I− ions on the renewable liquid In-Ga and Tl-Ga electrodes from 0.1 M solutions in dimethyl formamide (DMF) is investigated by using the method of differential capacitance measurements. The results are compared with similar data obtained on Hg and Ga electrodes in DMF and with the corresponding data obtained in acetonitrile (AN). It is shown that, in DMF, the adsorption parameters and the series of surface activity of halide ions (Hal−) significantly depend on the metal nature. In contrast to Hg electrode, on which the surface activity of halide ions increases in the series: Cl− < Br− < I−, on In-Ga, as well as on the Ga electrode, it varies in the reverse order: I− < Br− < Cl−, whereas on the Tl-Ga electrode, partially reversed series of surface activity is observed: Br− < I− < Cl−. The results are explained within the framework of Andersen-Bockris model. An analysis of experimental results leads to the following qualitative conclusions: (1) on the In-Ga and Tl-Ga electrodes, as well as on Ga electrode, free energy of metal-Hal− interaction ( \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$ \Delta G_{_{M - Hal^ - } } $$\end{document}) increases in series I− < Br− < Cl−; (2) for Cl−, Br−, and I−, \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$ \Delta G_{_{M - Hal^ - } } $$\end{document}) grows in series Tl-Ga < In-Ga < Ga; (3) an absolute magnitude of \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$ \Delta G_{_{M - Hal_1^ - } } - \Delta G_{_{M - Hal_2^ - } } $$\end{document} (Hal1−, and Hal2− are any ions of Cl−, Br−, and I−) increases in series Hg < Tl-Ga < In-Ga < Ga; (4) the metal-DMF chemisorption interaction is much stronger than the metal-AN interaction and increases in series Tl-Ga < In-Ga < Ga.