Nishi Naoya, Murakami Hiroshi, Yasui Yukinori, Kakiuchi Takashi
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Japan.
Anal Sci. 2008 Oct;24(10):1315-20. doi: 10.2116/analsci.24.1315.
The phase-boundary potential at the interface between an aqueous KCl solution (W) and a hydrophobic room-temperature ionic liquid (RTIL), trioctylmethylammonium bis(nonafluorobutylsulfonyl)imide ([TOMA(+)][C(4)C(4)N(-)]), containing dicyclohexano-18-crown-6 (DCH18C6), shows the nernstian response to K(+) in W within a polarized potential window of 500 mV between [TOMA(+)][C(4)C(4)N(-)] and W, demonstrating that hydrophobic RTILs can be used as a nonvolatile ionic medium for liquid-membrane ion-selective electrodes. The complex formation constant of K(+) with DCH18C6 in [TOMA(+)][C(4)C(4)N(-)] is estimated to be on the order of 10(9) from the upper detection limit using a partition equilibrium model in the presence of a neutral ionophore. The response time of the phase-boundary potential is approximately 20 min. Gelled [TOMA(+)][C(4)C(4)N(-)] also shows the nernstian response to K(+), although the upper limit is lower probably due to a change in the solvent properties from the non-gelled [TOMA(+)][C(4)C(4)N(-)]. The response time of the gelled [TOMA(+)][C(4)C(4)N(-)] is approximately 5 min, shorter than that of the non-gelled [TOMA(+)][C(4)C(4)N(-)].
在含有二环己基-18-冠-6(DCH18C6)的疏水性室温离子液体(RTIL)三辛基甲基铵双(九氟丁基磺酰基)亚胺([TOMA(+)][C(4)C(4)N(-)])与氯化钾水溶液(W)的界面处,相界电位在[TOMA(+)][C(4)C(4)N(-)]和W之间500 mV的极化电位窗口内对W中的K(+)呈现能斯特响应,这表明疏水性RTILs可作为液膜离子选择性电极的非挥发性离子介质。利用中性离子载体存在下的分配平衡模型,从检测上限估计K(+)与[TOMA(+)][C(4)C(4)N(-)]中DCH18C6的络合形成常数约为10(9)。相界电位的响应时间约为20分钟。凝胶化的[TOMA(+)][C(4)C(4)N(-)]也对K(+)呈现能斯特响应,尽管上限较低,这可能是由于溶剂性质与非凝胶化的[TOMA(+)][C(4)C(4)N(-)]有所不同。凝胶化的[TOMA(+)][C(4)C(4)N(-)]的响应时间约为5分钟,比非凝胶化的[TOMA(+)][C(4)C(4)N(-)]短。