A Combined Experimental and Molecular Dynamics Study of Iodide-Based Ionic Liquid and Water Mixtures.

Iodide-based ionic liquids have been widely employed as iodide sources in electrolytes for applications utilizing the triiodide/iodide redox couple. While adding a low-viscosity solvent such as water to ionic liquids can greatly enhance their usefulness, mixtures of highly viscous iodide-containing ILs with water have never been studied. This paper investigates, for the first time, mixtures of water and the ionic liquid 1-butyl-3-methylimidazolium iodide ([BMIM][I]) through a combined experimental and molecular dynamics study. The density, melting point, viscosity, and conductivity of these mixtures were measured by experiment. The composition region below 50% water by mole was found to differ dramatically from the region above 50% water, with trends in density and melting point differing before and after that point. Water was found to have a profound effect on viscosity and conductivity of the IL, and the effect of hydrogen bonding was discussed. Molecular dynamics simulations representing the same mixture compositions were performed. Molecular ordering was observed, as were changes in this ordering corresponding to water content. Molecular ordering was related to the experimentally measured mixture properties, providing a possible explanation for the two distinct composition regions identified by experiment.

Spontaneous transport of microparticles across liquid-liquid interfaces.

Transporting micrometer-sized particles through the liquid-liquid interface generally requires high shear force and sometimes surfactant functionalization. Without these aids, particles adhere to the interface due to strong capillary forces (can be on the order of 10(6) kT). Thus, spontaneous transport of microparticles through the liquid-liquid interface has not yet been reported. However, we present a new phenomenon here: some ionic liquids (ILs) possess powerful extraction capabilities and can cause microparticles to migrate across the interface without the aid of any shear forces. Both single particles and clusters of particles were observed to adsorb to, then "jump" across the interface and finally detach. In the absence of external mixing, particles as large as 4 µm (in diameter) could completely penetrate the IL/water interface, despite the significant adhesive forces. We have presented a hypothesis that these forces were overcome by ions dissolved in the non-IL phase, which helped by covering the particle surfaces, allowing for more favorable interactions with the IL.