Alkane coiling in perfluoroalkane solutions: a new primitive solvophobic effect

• Main Author: Morgado, Pedro
• Publication Date: 2017
• Other Authors: Garcia, Ana, Martins, Luis F. G., Illiarco, Laura M., Filipe, Eduardo J. M.
• Format: Article
• Language: eng
• Source: Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
• Download full: http://hdl.handle.net/10400.1/11877
• topic: Liquid phase behavior; Binary mixtures; N-Alkanes; Semifluorinated alkanes; Vibrational spectra; Ternary mixtures; Oxygen delivery; Volume changes; Hexane; Fluorocarbon

In this work, we demonstrate that n-alkanes coil when mixed with perfluoroalkanes, changing their conformational equilibria to more globular states, with a higher number of gauche conformations. The new coiling effect is here observed in fluids governed exclusively by dispersion interactions, contrary to other examples in which hydrogen bonding and polarity play important roles. FTIR spectra of liquid mixtures of n-hexane and perfluorohexane unambiguously reveal that the population of n-hexane molecules in all-trans conformation reduces from 32% in the pure n-alkane to practically zero. The spectra of peffluorohexane remain unchanged, suggesting nanosegregatiori of the hydrogenated and fluorinated chains. Molecular dynamics simulatiOns support this analysis. The new solvophobic effect is prone to have a major impact on the structure, organization, and therefore thermodynamic properties and phase equilibria of, fluids involving mixed hydrogenated and fluorinated chains.