Phase Separation in Binary Mixtures Containing Linear Perfluoroalkanes

Nostro, Pierandrea Lo; Scalise, Luca; Baglioni, Piero

doi:10.1021/je049620w

Cited by 25 publications

(25 citation statements)

References 23 publications

(40 reference statements)

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“…The unlike interactions between FE − CE, FE − CM, FE − C4, FM − CE, FM − CM, FM − C4 pairs of groups are estimated from the experimental liquid-liquid phaseequilibrium data for the C 6 F 14 + C 6 H 14 , C 8 F 18 + C 6 H 14 , C 8 F 18 + C 9 H 20 , and C 8 F 18 + C 8 H 18 binary mixtures [67,70,[93][94][95][96][97][98][99][100][101][102]. The connecting groups (FH and FHE), which bridge the alkyl and the perfluoroalkyl chains, are introduced to account for the presence of the dipole moment between the two chemical moieties in an effective manner; the FH and FHE groups are characterized by dispersion energies which differ markedly from the values for the alkyl (CE, CM, C4) or perfluoroalkyl (FE, FM) groups.…”

Section: Saft-γ Cg Mie Force Fieldmentioning

confidence: 99%

SAFT-γ force field for the simulation of molecular fluids: 8. Hetero-segmented coarse-grained models of perfluoroalkylalkanes assessed with new vapour–liquid interfacial tension data

et al. 2016

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The air-liquid interfacial behaviour of linear perfluoroalkylalkanes (PFAAs) is reported through a combined experimental and computer simulation study. The surface tensions of seven liquid PFAAs (perfluorobutylethane, F 4 H 2 ; perfluorobutylpentane, F 4 H 5 ; perfluorobutylhexane, F 4 H 6 , perfluorobutyloctane, F 4 H 8 ; perfluorohexylethane, F 6 H 2 ; perfluorohexylhexane, F 6 H 6 ; and perfluorohexyloctane, F 6 H 8 ) are experimentally determined over a wide temperature range (276-350 K). The corresponding surface thermodynamic properties and the critical temperatures of the studied compounds are estimated from the temperature dependence of the surface tension. Experimental density and vapour pressure data are employed to parameterize a generic heteronuclear coarse-grained intermolecular potential of the SAFT-γ family for PFAAs. The resulting force field is used in direct molecular-dynamics simulations to predict the experimental tensions with quantitative agreement and to explore the conformations of the molecules in the interfacial region revealing a preferential alignment of the PFAA molecules towards the interface and an enrichment of the perfluoro groups at the outer interface region.

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Section: Saft-γ Cg Mie Force Fieldmentioning

confidence: 99%

SAFT-γ force field for the simulation of molecular fluids: 8. Hetero-segmented coarse-grained models of perfluoroalkylalkanes assessed with new vapour–liquid interfacial tension data

et al. 2016

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“…[10][11][12][13][14] There are minimal data covering solubility and phase equilibrium of fluorinated compounds. 8,[10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25] The study of water solubility is of particular interest, since the solvation properties and the molecular interactions of fluorocompounds with water are important to understand the FC-in-water or reversed emulsions formation and aging. 9,[25][26][27][28] The objective of the present work is to provide experimental and theoretical information about the unlike water-FC compound molecular interactions and to evaluate the effect of R-(ω-)fluorine substitution by H, Cl, Br, and I on this interaction.…”

Section: Introductionmentioning

confidence: 99%

Water Solubility in Linear Fluoroalkanes Used in Blood Substitute Formulations

et al. 2006

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The interactions between water and n-perfluoroalkanes or substituted R-(ω-)fluoroalkanes used in blood substitute formulations were investigated experimentally and using ab initio calculations. The solubility of water in C 6 -C 9 perfluoroalkanes and five C 8 analogues of substituted fluoroalkanes was measured in the temperature range between 288 and 318 K at atmospheric pressure, using a Karl Fischer coulometer. From these data, the thermodynamic functions and partial molar solvation quantities such as Gibbs energy, enthalpy, and entropy were determined and compared with the interaction energies in 1:1 water-fluoroalkane complexes in vacuum, obtained using B3LYP/6-311++G(d,p). The experimental solubility data indicates a significant specific interaction between the water and the R-(ω-)substitute atom (H, I, Br, or Cl) in the fluoroalkanes.

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“…For example, on the π* scale of solvent polarity/polarizability [8], where dimethylsulfoxide is defined as 1 and cyclohexane 0, perfluorooctane can be found at −0.41. In fact, octane and perfluorooctane do not mix at room temperature precisely because octane is too polarizable [9]. …”

Section: Introductionmentioning

confidence: 99%

Electrochemistry in media of exceptionally low polarity: Voltammetry with a fluorous solvent

Olson¹,

Boswell²,

Givot³

et al. 2010

Journal of Electroanalytical Chemistry

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This work demonstrates the first cyclic voltammetry in a perfluorocarbon solvent without use of a cosolvent. The novel electrolyte tetrabutylammonium tetrakis [3,5-bis(perfluorohexyl)phenyl]borate (NBu 4 BArF 104 ; 80 mM) allows for voltammetry of ferrocene in perfluoro(methylcyclohexane) by lowering the specific resistance to Ω268 k cm at 20.8 °C. Despite significant solution resistance, the resulting voltammograms can be fitted quantitatively without difficulty. The thus determined standard electron transfer rate constant, k°, for the oxidation of ferrocene in perfluoro (methylcyclohexane) is somewhat smaller than for many solvents commonly used in electrochemistry, but can be explained readily as the result of the viscosity and size of the solvent using Marcus theory. Dielectric dispersion spectroscopy verifies that addition of NBu 4 BArF 104 does not significantly raise the overall polarity of the solution over that of neat perfluoro (methylcyclohexane).

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Phase Separation in Binary Mixtures Containing Linear Perfluoroalkanes

Cited by 25 publications

References 23 publications

SAFT-γ force field for the simulation of molecular fluids: 8. Hetero-segmented coarse-grained models of perfluoroalkylalkanes assessed with new vapour–liquid interfacial tension data

SAFT-γ force field for the simulation of molecular fluids: 8. Hetero-segmented coarse-grained models of perfluoroalkylalkanes assessed with new vapour–liquid interfacial tension data

Water Solubility in Linear Fluoroalkanes Used in Blood Substitute Formulations

Electrochemistry in media of exceptionally low polarity: Voltammetry with a fluorous solvent

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