The liquid-junction potential at the contact of two immiscible electrolyte solutions in the absence of supporting electrolytes. Reference electrodes reversible to alkylammonium ions and tetraphenylborate ion in nitrobenzene.
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概要
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The liquid-junction potentials between two immiscible electrolyte solutions have been studied for the interface: R<SUB>1</SUB><SUP>+</SUP>TPB<SUP>−</SUP>(nitrobenzene)/R<SUB>1</SUB><SUP>+</SUP>X<SUP>−</SUP>(water) and R<SUB>1</SUB><SUP>+</SUP>TPB<SUP>−</SUP> (nitrobenzene)/Li<SUP>+</SUP>TPB<SUP>−</SUP>(water), where R<SUB>1</SUB><SUP>+</SUP> is a tetraalkylammonium ion, TPB<SUP>−</SUP> is tetraphenylborate ion, and X<SUP>−</SUP> is a halide ion. These interfaces may be seen as a simplest form of either a liquid ion-exchange membrane ion-selective electrode sensing the activity of the ion in the aqueous phase or a reference electrode of a liquid membrane type reversible to the ion in the nonaqueous phase. The effects of the cationic species(R<SUB>1</SUB><SUP>+</SUP>), the anionic species(X<SUP>−</SUP>) and the concentration of the electrolytes on the electrical potential difference developed at the interface have been studied. These properties of the interfaces were compared with a simplified theoretical treatment of the liquid-junction potential between the two immiscible solutions. The theory can predict the basic features of the system by knowing the standard ion-transfer potentials and the diffusion coefficients of the relevant ions as well as its concentration. In the concentration range where a significant deviation from the Nernstian response of the liquid-junction potential occurred, the diffusion potential has been demonstrated to contribute significantly to the liquid-junction potential.
- 公益社団法人 日本化学会の論文
著者
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Senda Mitsugi
Department Of Agricultural Chemistry College Of Agriculture Kyoto University
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Kakiuchi Takashi
Department of Agricultural Chemistry and Research Center for Cell and Tissue Culture, Faculty of Agriculture, Kyoto University
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