液液二相系における界面特異的反応過程の研究

1.交流伏安法和交流调制界面伏安法表明，黄杂环型染料阴离子在液-液界面的转移速率较慢是由于这些离子在液-液界面上的瞬时吸附。即使被认为没有表面活性的离子也会在界面上停留一段时间，导致界面离子转移的速度变慢。2.从理论上证明了离子表面活性剂的电势依赖性吸附和分配导致在其标准离子转移电势附近的电势处有最大的吸附。这一结论的一般性表明，它对于处理含碘表面活性剂存在的液-液两相体系中的各种界面现象具有重要意义。3.提出了含离子表面活性剂的液-液两相体系不稳定性的新判据。吸附对相边界势的依赖可以导致t…的正曲率。更多的是电毛细管曲线，这意味着界面的负电容。在这种物理上不现实的情况下，界面会变得不稳定。自发乳化是表面化学中一个长期存在的谜团，可以用这个新概念来解释。4.可以用电化学方法监测乳状液粒子与极化液液界面的熔融过程。聚变事件的离散性质表现为一系列电流尖峰。当界面面积在平方厘米量级时，熔融以雪崩的形式发生，即由大的乳化液颗粒熔合引发的多个小颗粒的转移，而当采用微观液-液界面时，则监测到单一的熔融事件。5.利用电化学技术可以对两相偶氮耦合进行定量研究。这个反应最好的描述是ErCiEr，即可逆的离子转移，随后是在均相溶液中的不可逆化学反应，然后是质子向水相的反向转移。芳基偶氮阳离子在含有还原剂的有机相中被还原。生成的芳基自由基能在界面引发自由基聚合。6.从实验和理论两方面研究了液-液界面上电子转移反应和离子转移反应的耦合方式。在薄层有机涂层电极浸泡在水溶液中的情况下，建立了准确测定液-液界面电子转移反应速率的判据。较少

1. Ac-voltammetry and ac-modulated interfacial voltfluorometry revealed that the slower rate of the transfer of xanthene-type dye anions across the liquid-liuqid interface is ascribed to the transient adsorption of these ions at the interface. Even ions that are considered to have no surface activity can stay some time at the interface, resulting in the slower rate of the interfacial ion transfer. 2. It is demonstrated theoretically that the potential dependent adsorption and partition of ionic surfactants results in the maximum adsorption at the potential around its standard ion-transfer potential. The generality of the conclusion signifies its importance in dealing with various interfacial phenomena in the presence of ioinic surfactants in liquid-liquid two-phase systems. 3. A new criterion of instability of liquid-liquid two-phase systems containing ionic surfactants is proposed. The dependence of the adsorption on the phase-boundary potential can lead to the positive curvature of t … More he electrocapillary curve, which means the negative capacitance of the interface. The interface becomes unstable under this physically unrealistic condition. The spontaneous emulsification, a long-standing riddle in surface chemistry, can be explained by this new concept. 4. The fusion of emulsion particles to the polarized liquid-liquid interface can be monitored electrochemically. The discrete nature of the fusion event is exhibited as a train of current spikes. When the area of the interface is on the order of square centimeter, the fusion takes place as an avalanche, that is, the transfer of many smaller particles triggered by the fusion of a large emulsion particle, whereas a single fusion event is monitored when a micro liquid-liquid interface is employed. 5. A two-phase azo coupling can be quantitatively studied using electrochemical techniques. This reaction is best described as ErCiEr, that is, the reversible ion transfer, a succeeding irreversible chemical reaction in a homogeneous bulk solution phase, and the following back transfer of protons to the aqueous phase. Aryl-azo cations are reduced in the organic phase containing a reductant. The produced aryl-radicals can initiate the radical polymerization at the interface. 6. The mode of the coupling of electron transfer and ion transfer reactions at the liquid-liquid interface has been studied both experimentally and theoretically. In the case of thin-organic-layer covered electrodes dipped in an aqueous solution, the criterion has been quantitatively established for accurately determining the rate of electron tranfer reactions at the liquid-liquid interface. Less