Experimental studies of the liquid junction potential between electrolyte solutions in different solvents. I. Water-organic solvent junctions.
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概要
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The liquid junction potential (ljp) between water and organic solvents was investigated by measuring the emfs of cells with free-diffusion junctions of various electrolyte solutions. In most experiments, the concentration of the electrolyte on one side of a junction was kept much larger than that on the other side (<I>c</I> MX in S⁄⁄<I>c</I>′ M′X′ in S′; S or S′ is H<SUB>2</SUB>O and <I>c</I>>><I>c</I>′; thus the ljp was mainly determined by MX. The ljp may practically be expressed by the sum of <I>E</I><SUB>j,ion</SUB> (concn)(I), <I>E</I><SUB>j,ion</SUB> (ion-solv.)(II), and <I>E</I><SUB>j,solv.</SUB> (III). I and II are contributions from ionic species: I is the concentration term, which can be estimated approximately from the Henderson equation, and II is the term due to the difference in ionic solvations in S and S′. III is the contribution from the transfer of solvent molecules. The sum of II and III for the case in which S=H<SUB>2</SUB>O is approximately equal in absolute value but opposite in sign to that for the case in which S′=H<SUB>2</SUB>O. The change of II with the anion X<SUP>−</SUP> is in linear relation with free energy of transfer of the anion from S to S′. The change of III with the bridge solvent is also a linear function of the heat (or free energy) of solution of S into S′. The rate of the change with the heat of solution can be divided in two classes by the species of the cation M<SUP>+</SUP>: the rate for R<SUB>4</SUB>N<SUP>+</SUP> ions is just a half of that for such ions as Li<SUP>+</SUP>, Na<SUP>+</SUP>, Mg<SUP>2+</SUP>, and Ba<SUP>2+</SUP>. The effect of the mixed bridge electrolytes and the mixed bridge solvents was also examined.
- 公益社団法人 日本化学会の論文
著者
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Nakamura Toshio
Department Of Biophysics Neuroinformation Research Institute School Of Medicine Kanazawa University
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Izutsu Kosuke
Department Of Chemistry Faculty Of Science Shinshu University
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Kitano Toshihiko
Department of Chemistry, Faculty of Science, Shinshu University
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Hirasawa Chieko
Department of Chemistry, Faculty of Science, Shinshu University
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- Experimental studies of the liquid junction potential between electrolyte solutions in different solvents. I. Water-organic solvent junctions.