Facilitated transfer of alkali-metal cations by dibenzo-18-crown-6 across the electrochemically polarized interface between an aqueous solution and a hydrophobic room-temperature ionic liquid

Naoya Nishi; Hiroshi Murakami; Seiichi Imakura; Takashi Kakiuchi

doi:10.1021/ac060797y

Facilitated transfer of alkali-metal cations by dibenzo-18-crown-6 across the electrochemically polarized interface between an aqueous solution and a hydrophobic room-temperature ionic liquid

Anal Chem. 2006 Aug 15;78(16):5805-12. doi: 10.1021/ac060797y.

Authors

Naoya Nishi¹, Hiroshi Murakami, Seiichi Imakura, Takashi Kakiuchi

Affiliation

¹ Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan.

PMID: 16906727
DOI: 10.1021/ac060797y

Abstract

The facilitated transfer of alkali metal cations (Li+, Na+, K+, Rb+, Cs+) by dibenzo-18-crown-6 (DB18C6) across the electrochemically polarizable interface between an aqueous solution (W) and a hydrophobic ionic liquid, N-octadecylisoquinolinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate ([C18Iq][TFPB]), has been studied using cyclic voltammetry at the interface formed at the tip of a micropipet. In cyclic voltammograms (CVs), the current due to the facilitated transfer of the cations by DB18C6 from W to [C18Iq][TFPB] can be measured within the polarized potential window of the [C(18)Iq][TFPB]|W interface. The stoichiometry of the complexes in [C18Iq][TFPB] for Li+, Na+, K+, and Rb+ are found to be 1:1 while for the Cs+ transfer both 1:1 and 1:2 complexes are likely to be formed. The formation constants of the 1:1 complexes for Li+, Na+, K+, and Rb+ in [C18Iq][TFPB], , evaluated from CVs are log = 5.0, 7.0, 8.2, and 7.3, respectively. The value for K+ is 1 order of magnitude greater than that for Na+. This higher selectivity of DB18C6 to K+ over Na+ in [C18Iq][TFPB] compared with that in molecular solvents suggests that the RTIL provides a unique solvation environment for the complexations of DB18C6 with the ions.