The complexing of the ammonium ion in acetonitrile with other solvents. Investigation using a cation-sensitive glass electrode.

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概要

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• As a part of potentiometric studies of the complexing of univalent cations in acetonitrile with other solvents by the use of a cation-sensitive glass electrode, investigations were carried out of the complexing of the ammonium ion in acetonitrile with such solvents as water, methanol, <I>N</I>-methylformamide, <I>N</I>,<I>N</I>-dimethylformamide, <I>N</I>,<I>N</I>-dimethylacetamide, dimethyl sulfoxide, 1-methyl-2-pyrrolidone, and hexamethylphosphoric triamide, and also with dibenzo-18-crown-6. Prior to the study of the complexing, the cation-sensitive glass electrode was confirmed to respond in a Nernstian way to the change in the ammonium-ion activity which occurs due to the change of the solvent (solvent effect). The ammonium ion in acetonitrile formed complexes of mono- and di-solvated species with methanol and water. Formations of up to tri-solvated species were formed with DMF, DMA, and DMSO, and up to tetra-solvated species with 1-methyl-2-pyrrolidone and NMF. With HMPA, even penta-solvated species were formed. The complex formation constants of the mono-solvated ammonium ion, β<SUB>1</SUB> (mol <SUP>−1</SUP> dm<SUP>3</SUP>), were 1<SUB>.7</SUB> with methanol, 5.6 with DMF, 14 with DMSO, 17 with DMA, 31 with 1-methyl-2-pyrrolidone, 3.0×10<SUP>2</SUP> with NMF, and 1.2×10<SUP>3</SUP> with HMPA. The association constant of ammonium perchlorate in acetonitrile was determined conductometrically to be 25 mol <SUP>−1</SUP> dm<SUP>3</SUP>.

• 公益社団法人 日本化学会の論文

著者

• FUJINAGA Taitiro

  Chemistry Institute, Faculty of Science, University of Kyoto

• Izutsu Kosuke

  Chemistry Department, Faculty of Science, Shinshu University

• Nakamura Toshio

  Chemistry Department, Faculty of Science, Shinshu University

• Murayama Taiji

  Chemistry Department, Faculty of Science, Shinshu University

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• The complexing of the ammonium ion in acetonitrile with other solvents. Investigation using a cation-sensitive glass electrode.
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