The specific effects of tetraalkylammonium and alkali metal ions on the polarographic reduction of nitroalkanes and nitrobenzenes in acetonitrile.
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概要
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The polarographic behavior of 2-methyl-2-nitropropane ((CH<SUB>3</SUB>)<SUB>3</SUB>CNO<SUB>2</SUB>) was examined at DME in acetonitrile with various supporting electrolytes. The addition of Et<SUB>4</SUB>N<SUP>+</SUP> or <I>n</I>-Bu<SUB>4</SUB>N<SUP>+</SUP> caused the half-wave potential (<I>E</I><SUB>1⁄2</SUB>) of (CH<SUB>3</SUB>)<SUB>3</SUB>CNO<SUB>2</SUB> to shift negatively in the presence of a fixed concentration of NaClO<SUB>4</SUB>. The negative shift was explained in terms of the interaction between tetraalkylammonium cations and the unreduced molecule of (CH<SUB>3</SUB>)<SUB>3</SUB>CNO<SUB>2</SUB>. The formation of (CH<SUB>3</SUB>)<SUB>3</SUB>CNO<SUB>2</SUB><SUP>\newdot</SUP>(Na<SUP>+</SUP>)<SUB>2</SUB> was also suggested, and the conditional formation constants of the species were obtained by the positive shift in the <I>E</I><SUB>1⁄2</SUB> of (CH<SUB>3</SUB>)<SUB>3</SUB>CNO<SUB>2</SUB> with increasing concentration of Na<SUP>+</SUP> at certain concentrations of Et<SUB>4</SUB>N<SUP>+</SUP> and <I>n</I>-Bu<SUB>4</SUB>N<SUP>+</SUP>. Other nitroalkanes and nitrobenzenes were also examined. The effect of water on the half-wave potentials of the first waves of the nitro compounds suggested the formation of RNO<SUB>2</SUB><SUP>\newdot</SUP>(H<SUB>2</SUB>O)<SUB>2</SUB>-type species.
- 公益社団法人 日本化学会の論文
著者
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Imai Yoshihiko
Department Of Applied Physics University Of Tokyo
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Hojo Masashi
Department Of Chemistry Faculty Of Science Kochi University
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Nishikawa Kazukiyo
Department of Chemistry, Faculty of Science, Kochi University
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Akita Yoshihiro
Department of Chemistry, Faculty of Science, Kochi University
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