Potentiometric and calorimetric studies on the formation of ethylenediamine complexes of nickel(II) ion in water and dioxane-water mixtures.
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概要
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Equilibria between ethylenediamine and protons or nickel(II) ions have been investigated at 25 °C by means of potentiometric and calorimetric titrations in water and in dioxane–water mixtures (the dioxane contents are 0.1 and 0.2 mole fractions, which correspond to 35.2 and 55.0%w/w, respectively) containing 3 mol dm<SUP>−3</SUP> LiClO<SUB>4</SUB> as a constant ionic medium. Thermodynamic parameters (Δ<I>G</I><SUP>°</SUP>, Δ<I>H</I><SUP>°</SUP>, and Δ<I>S</I><SUP>°</SUP>) referring to the formation of the species HL<SUP>+</SUP>, H<SUB>2</SUB>L<SUP>2+</SUP>, NiL<SUP>2+</SUP>, NiL<SUB>2</SUB><SUP>2+</SUP>, and NiL<SUB>3</SUB><SUP>2+</SUP> (L denotes ethylenediamine) have been determined in the solutions. All the formation constants of the nickel(II)–ethylenediamine complexes increased with increasing dioxane content in the solvent mixtures, although the formation constants of the ethylenediammonium ions remained practically unchanged. On the other hand, enthalpies referring to the formation of the nickel(II)–ethylenediamine complexes became less negative, and thus entropies for the corresponding reactions increased remarkably with increasing dioxane content in the mixtures. The solvent effects on the thermodynamic parameters of the complex formation of nickel(II) ions with ethylenediamine are discussed in terms of enhancement of solvation of the complexes due to weakening of the hydrogen-bonded structure of the bulk water by the addition of dioxane.
- 公益社団法人 日本化学会の論文
著者
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Ohtaki Hitoshi
Department Of Chemistry Faculty Of Science And Engineering Ritsumeikan University
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Ishiguro Shin-ichi
Department Of Chemistry Faculty Of Science Kyushu University
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Oka Yoshihiro
Department of Electronic Chemistry, Tokyo Institute of Technology at Nagatsuta
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