Journal of Physical Chemistry B, Vol.101, No.20, 4024-4029, 1997
Connection of Ion and Water Exchange Between an Aqueous and a Microemulsion Phase
The exchange of ions and water between an aqueous and a micellar Me-AOT phase (AOT = bis(2-ethylhexyl)sulfosuccinate dissolved in isooctane) was measured in a stirred cell for different states of convection. It was proved experimentally that the water as well as the ion fluxes were controlled by an interfacial process, which therefore can be studied by mass transfer kinetics. The limitation of mass transfer by the interfacial process was manifested by always realized regions of convection independent fluxes (plateau mass transfer rates). In this work it was shown that the water concentration in the micellar phase was controlled by the specific pair and phase distribution of the exchanging cations. In this case, if in both phases cations of main group elements (Na-AOT(o)/Sr-aq) and cations of the transition elements (Zn-AOT(o)/Ni-aq) were present and exchanging with each other, the equilibration took place without change of the concentration of water (equilibrium value); that is, the micellar sizes remained constant. In the case that Na-AOT in isooctane solution was in contact with an aqueous solution of different transition cations, the water concentration exhibited a pronounced minimum in the micellar phase during mass transfer. In contrast the exchange of a micellar transition cation by sodium ions from the aqueous phase was accompanied by a maximum of the micellar water content during the course of equilibration. The differences in behavior of the micellar water content during equilibration can be related to the known characteristic differences in the micellar AOT head group area for main and transition group counterions. In the system with a pair of two main group or two transition cations undergoing ion exchange, the micelles docking at the interface maintain their individuality, due to the same AOT packing at the micellar and at the macroscopic interface (clocking mechanism). However, if an AOT gradient existed between the docked micelles and the interface, caused by the combination of main group and transition cations, partial merging of the micelles accompanied by AOT spreading takes place with an increase or a decrease of the micellar sizes depending on the ion pair and the direction of ion exchange (Marangoni mechanism). In this work some characteristic examples of mass transfer behavior were presented. This behavior could be explained by the two different mechanisms of interfacial solubilization.
Keywords:IN-OIL MICROEMULSION;REVERSE MICELLES;AEROSOL-OT;KINETICS;SYSTEMS;SOLUBILIZATION;COUNTERION