Kinetic and structural study of interfacial reaction in analytical separation system

(1)采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，Zn（II）配合物在中性配合物界面上的吸附性能最好，而金属（III）配合物由于带正电荷一般具有吸附性能。铁（III）配合物在界面处转化为mu -o配合物。(2)疏水吡啶偶氮配体萃取Ni（II）的速率控制步骤是在界面处形成1:1配合物。庚烷/水的界面速率常数比甲苯/水的界面速率常数大。这种溶剂效应可以从MD模拟所描述的吸附配体位置的差异来解释；配体在庚烷上的位置。水界面比甲苯/水界面更接近水相，更有利于与水相中的金属离子反应。(3)发现阴离子卟啉与阳离子表面活性剂在水溶液中形成1:4的配合物。(4)提出了用MD模拟预测界面吸附性能的新方法，并将其应用于疏水羟基肟的吸附性能的解释。因此，在这一年里，界面反应不仅通过实验方法而且通过计算模拟进行了研究。

(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.