Polarographic studies of the ion-pair formation and conjugation reactions of acetate and benzoate ions in acetonitrile.
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概要
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An acetate ion (A<SUP>−</SUP>) formed a homoconjugated species, A<SUP>−</SUP> (HA)<SUB>2</SUB>, with 2 molecules of acetic acid (HA) in the presence of a large excess of HA in an acetonitrile solution. In the presence of both acetic acid and LiClO<SUB>4</SUB>, one molecule of HA was derived from A<SUP>−</SUP> (HA)<SUB>2</SUB> by means of a lithium ion to from an ion-paired species, HA<SUB>2</SUB><SUP>−</SUP>Li, as follows: A<SUP>−</SUP>(HA)<SUB>2</SUB>+Li<SUP>+</SUP>\overset<I>K</I><SUB>ex</SUB>\rightleftharpoonsHA<SUB>2</SUB><SUP>−</SUP>Li<SUP>+</SUP>+HA. The equilibrium constant, <I>K</I><SUB>ex</SUB>, was evaluated as 1.1×10<SUP>4</SUP> from the shift in the anodic half-wave potential of the acetate ion. As for the benzoate ion (A′<SUP>−</SUP>) and HA′, similar reactions occured, and the constant of the exchange reaction was evaluated as 6×10<SUP>3</SUP>. The effect of the sodium ion and HA (or HA′) on the A<SUP>−</SUP> (or A′<SUP>−</SUP>) ion was complicated. On the other hand, the presence of [M(A′)<SUB>2</SUB>]<SUP>−</SUP> (M=Li, Na, K) was proved by the shift of the cathodic wave of the alkali metal.The addition of water caused the apparent stability constant of [Li(A′)<SUB>2</SUB>]<SUP>−</SUP> to decrease extremely.
- 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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