Design of useful methods for separation and analysis based on ion association reactions

イオン会合を利用する新しい分離法と分析法の開発に関する研究を行った.イオン会合の概念をより明確にするための基礎検討を行い,イオン会合のしやすさ,抽出のされやすさについて考察した.イオン会合の様式を静電引力型と疎水構造型に分け,それぞれ静電引力型イオン会合性試薬と疎水構造型イオン会合性試薬を対応させた.疎水構造型イオン会合性試薬を用いる抽出分離法において,イオン会合体の抽出性に及ぼす抽出溶媒の影響,イオン会合性試薬の影響について検討し,それらを基に抽出定数(log K(ex))の推算法について考察した.四塩化炭素を基準にした場合の溶媒の抽出能(イオン会合体の抽出のしやすさ)はE(T)値と良好な直線関係を示す.抽出定数はlog K(ex)=C+A(C:対陽イオンの抽出性の尺度,A:対陰イオンの抽出性の尺度)で表されるものとし,各種陽,陰イオンのC値,A値を決定した.又イオン骨格と置換基の寄与(π値)を用いるC値,A値の概算法も示した.log K(ex)を推算し,あるいは実測値を用いて,新しい抽出分離法と吸光光度法を設計し,実際にも有用な方法多数を開発した.溶媒抽出を用いない方法についても検討した.水溶液での疎水構造型イオン会合体生成に基づく新規定量法として,酸-塩基反応を伴う吸光光度法2方法を検討した.一つはイオン会合体の可溶化現象を用いるもので,リン,ケイ素の定量例が示された.もう一つはイオン会合体のミセル抽出現象を用いるもので,アルキルアミン,第四級アンモニウムイオンについての検討例を示した.更に,イオン会合の概念が適用できる例として,逆相分配クロマトグラフィー及びイオン交換クロマトグラフィーによる疎水構造型イオンの分離定量例も示した.Methods for the separation and analysis of ionic and nonionic species based on ion association reactions were developed. A concept for ion association reactions and ion association reagents was proposed. The ion association reactions may be divided into two categories : an electrostatic interaction-induced ion association and a hydrophobic interaction-induced ion association. The latter ion association reaction has been often used in solvent extraction procedures. The effect of extraction solvents on the extractability of ion association complexes was examined : the differences in the extraction constant (log K(ex)) between two extraction solvents were almost equal in various ion association complexes. The difference in log K(ex) between the standard solvent (carbontet-rachloride) and a given solvent may be defined as S(ex) : a parameter for the extraction ability of a solvent for an ion association complex. The extraction constant was divided into two parameters, C and A, assigned to the cation and anion; thus log K(ex)= C + A. A method for estimating C and A was proposed. By using log K(ex) predicted or experimentally obtained, novel solvent extraction/spectrophotometrical methods were designed and used in practical analysis, for example, in the determination of anionic surfactants, alkaline metals and other metal ions, phosphorus, arsenic and silicon, boron, and organic ionic species. Applications of ion association reactions to analytical use in an aqueous medium were developed. One was based on the solubilization of ion association complexes, and the other on the micelle extraction of ion association complexes. Chromatographic separations and determination of chelate anions were also mentioned