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

概要

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New higher homologue of tetraalkylammonium salts such as tetradodecylammonium (Dod_4N^-), tetradecyl-ammonium (Dec_4N^-), tetrahexylammonium (Hex_4N^-) and tetraheptylammonium (Hep_4N^-) perchlorates were synthesized and their properties as the supporting clectrolyte 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 was the widest when Hex_4N^+ ion was used and the smallest when Dec_4N^+ or Dod_N^+ ions was used. In HMPA solution, the use of the large ion such as Hex_4N^+ promotes the reduction of sodium ion more than that of the smaller ion such as Et_4N^+ Electrocapillary curves at negative potential showed that Et_aN^+ ion was adsorbed on mercury more strongly than Bu_4N^+ or Hex_4N^+ ion. On the other hand these new large ions such as Dod_4N^+, Dec_4N^+ 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 Dec_4N^+ and Dod_4N^+ in the solution were found to be smaller that of Hex_4N^+; almost equal to that of NH_4^+ or Me_4N^+.
社団法人日本分析化学会の論文
1979-04-05