초록
Electrochemical studies of alkali metal cations $(Na^+, K^+, Rb^+, Cs^+)$ were performed in methanolic solutions of 18-crown-6 and tetrabutylammonium salts at dropping mercury electrodes (DME) and thin mercury film electrodes (TMFE). All the cations investigated were reduced reversibly at DME in the absence and presence of 18-crown-6, and in the latter the limiting currents were decreased and the reduction potentials shifted to the negative direction. The reduction potentials of the metal ions (0.2 mM) in the presence of the crown (10 mM) were - 2.14 $(Na^+)$, - 2.26 $(K^+)$, - 2.20 $(Rb^+) and - 2.14 $(Cs^+)$ V vs. SCE, respectively. The measured potentials were rationalized with ion recognition of the cations by the crown. Electroreduction at TMFE were highly irreversible. A new representation method of ion recognition is presented. In aqueous solutions, electroreduction of the alkali metal ions were characterized by adsorption.