Some properties of higher tetraalkylammonium salts as the supporting electrolytes in hexamethylphosphoric triamide solution

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  • SAKURA Sachiko
    Department of Chemistry, Faculty of Medicine, Hamamatsu University School of Medicine

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Other Title
  • ヘキサメチルホスホルアミド溶媒中における高級テトラアルキルアンモニウム塩類の支持電解質としての性質
  • ヘキサメチルホスホルアミド ヨウバイチュウ ニ オケル コウキュウ テトラアル
  • ヘキサメチルホスホルアミド中における電気化学的研究(第8報)

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Abstract

New higher homologue of tetraalkylammonium salts such as tetradodecylammonium (Dod4N-), tetradecylammonium (Dec4N-), tetrahexylammonium (Hex4N-) and tetraheptylammonium (Hep4N-) perchlorates were synthesized and their properties as the supporting electrolyte for polarographic measurements in hexamethylphosphoric triamide (HMPA) were compared with those of the lower ones. The difference of the melting point of these higher homologue by the increase of the carbon number in their alkyl groups was much smaller than that for the lower homologue. When these salts were used as the supporting electrolyte, the potential range where polarogram was obtained the widest when Hex4N+ ion was usec and the smallest when Dec4N+ or Dod4N+ ions was used. In HMPA solution, the use of the large ion such as Hex4N+ promotes the reduction of sodium ion more than that of the smaller ion such as Et4N+. Electrocapillary curves at negative potential showed that Et4N+ ion was adsorbed on mercury more strongly than Bu4N+ or Hex4N+ ion. On the other hand these new large ions such as Dod4N+, Dec4N+were found to be adsorbed even at more positive potential (>-1.3 V). From the conductivity measurement of these higher homologue salts in HMPA solution, the effective radii of Dec4N+ and Dod4N+in the solution were found to be smaller that of Hex4N+; almost equal to that of NH4+ or Me4N+.

Journal

  • BUNSEKI KAGAKU

    BUNSEKI KAGAKU 28 (4), 274-277, 1979

    The Japan Society for Analytical Chemistry

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