Towards Aqueous – Fluorous – Hydrogenous emulsions: Phase equilibria and liquid structure of (water + 1H,1H-Perfluorobutanol + 1-butanol) ternary mixture

Modeling the Fluid-Phase Equilibria of Semifluorinated Alkanes and Mixtures of (n-Alkanes + n-Perfluoroalkanes) with the SAFT-γ Mie Group-Contribution Approach

“…Using the united atom version of the TraPPE force field, Zhang and Siepmann found that a 1% increase of the unlike segment size parameter and an 11% reduction of the unlike attractive well depth were necessary to obtain an adequate description of envelope of liquid–liquid equilibria (LLE) and the corresponding upper critical solution temperature (UCST) for the CH 4 + CF 4 mixture. Following a similar line of reasoning, in recent work we have systematically demonstrated that increasing unlike-size parameters is essential to account for the large excess volumes displayed by these systems. ,,, More than mere empirical refinement, these adjustments highlight that the peculiar properties of these systems are not only a consequence of weak relative attractive interactions, but are also related to the repulsive part of the intermolecular potential. Moreover, at the molecular level, the simulations clearly demonstrate segregation between the two mutually phobic chains.…”

Perfluorinated Alcohols at High Pressure: Experimental Liquid Density and Computer Simulations

“…Indeed, it is well known that perfluorinated and hydrogenated chains are mutually phobic and tend to phase-separate, giving rise to large volumetric, dynamic, and conformational anomalies . This mutual phobicity also leads to inhomogeneities in the fluids and the formation of nano-domains as well as different levels of supramolecular organization. − In the case of mixtures of hydrogenated and fluorinated alcohols, we have demonstrated that they display nano-segregation. − Thus, in addition to the previously mentioned network of H-bonds zigzagging throughout the liquid, the simultaneous presence of the mutually phobic alkyl and perfluoroalkyl segments introduces a new important constraint to the organization of the fluid. The result is a highly nano-segregated structure, reflecting the difficult balance between maximizing H-bonding and the tendency to isolate fluorinated from hydrogenated chains.…”

“…Mixtures of fluorinated and hydrogenated alcohols have also been studied in both the liquid and gaseous phases. − These mixtures display a very complex behavior when compared with mixtures of hydrogenated alcohols. For example, excess volumes are large and positive, whereas those of mixtures of hydrogenated alcohols are practically zero .…”

The path towards type V deep eutectic solvents: inductive effects and steric hindrance in the system tert-butanol + perfluoro tert-butanol

“…39 In recent work we have shown that mixtures of hydrogenated and perfluorinated alcohols display clear evidence of coexisting polar, hydrogenated and perfluorinated domains. [40][41][42] A network of hydrogen bonds are formed, zigzagging throughout the liquid, while the hydrogenated and perfluorinated segments occupy the remaining space while trying to avoid each other. The TBH-TBF mixture studied in this work is a further example of this type of mixtures.…”