Liquid Junction Potential between Electrolyte Solutions in Different Solvents Studied by Use of Mixed Solvent/Pure Solvent Junctions

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  • Izutsu Kosuke
    Department of Chemistry, Faculty of Science, Shinshu University

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Of the three components of the liquid junction potential between electrolyte solutions in different solvents, the component due to the interaction between different solvents (component (c)) was studied using mixed solvent/pure solvent junctions. According to our model of component (c), the component at a mixed solvent/pure solvent junction should vary linearly with the volume fraction of the mixed solvent. We previously confirmed this experimentally. However, there are exceptional cases in which nonlinear (curved) relationships are observed. In the present work, I found that most of the curved relationships are obtained for mixtures between an amphiprotic solvent (water, formamide, or N-methylformamide) and an aprotic solvent of very low acceptor number (N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, acetone, or hexamethylphosphoric triamide). In contrast, for an aprotic solvent of moderate acceptor number (nitromethane, dimethyl sulfoxide, acetonitrile, or propylene carbonate), linear or near-linear relationships are observed. The observed curved relationships were concluded to be due to that the structure-forming amphiprotic solvent is more likely to and the aprotic solvent less likely to settle at the interphasial region than in the bulk, because the dipolar molecules of the aprotic solvent of very low acceptor number have a vague positive charge-center.

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