Kinetic and structural study of interfacial reaction in analytical separation system

(1)用高速搅拌法测定了金属(II，III)-卟啉的界面吸附性能。结果表明，锌(II)络合物在中性络合物界面上的吸附能力最强，而金属(III)络合物由于带正电荷而一般是可吸附的。(2)疏水性吡啶偶氮配体萃取Ni(II)的速率控制步骤是在界面形成1：1的络合物。界面速率常数在正庚烷/水中大于在甲苯/水中。这种溶剂效应是由于分子动力学模拟描述的被吸附配体位置的不同而引起的，配体在庚烷-水界面的位置比在甲苯/水界面更接近水相，更有利于与水相中的金属离子反应。(3)发现阴离子卟啉和阳离子表面活性剂在水溶液中形成1：4的络合物。(4)发展了分子动力学模拟预测界面吸附能力的新方法，并将其应用于解释疏水羟胺的吸附能力。因此，本论文不仅用实验方法考察了界面反应，还用计算模拟的方法研究了界面反应。

(1) Interfacial adsorptivity of metal(II,III) -porphyrins was determined by means of high-speed stirring method. The results showed that Zn(II) complex was most adsorbable at the interface among neutral complexes and that metal(III) complexes were generally adsorbable because of their positive charges. Iron(III) complex inverted to mu -oxo complex at the interface.(2) The rate-controlling step of the extraction of Ni(II) with a hydrophobic pyridylazo ligand was the formation of 1 : 1 complex at the interface. The magnitude of the interfacial rate constant was larger in heptane/water than that in toluene/water. This solvent effect was explained from the difference in the location of the adsorbed ligand which was depicted by MD simulation ; the location of the ligand at the heptane.water interface is closer to the aqueous phase than that in toluene/water interface and is more favorable to react with metal ions in aqueous phase.(3) It was found that an anionic porphyrin and a cationic surfactant formed a 1 : 4 complex in aqueous solution.(4) New approach to predict an interfacial adsorptivity by MD simulation was developed and applied for the explanation of the adsorptivity of hydrophobic hydroxyoximes.Thus, in this year, the interfacial reaction was examined not only by experimental approach but also by computational simulation.