Perfluoroalkanes and perfluoroalkylalkane surfactants in solution: Partial molar volumes in n-octane and hetero-SAFT-VR modelling

Morgado, Pedro; Rodrigues, Hugo; Blas, Felipe J.; McCabe, Clare; Filipe, Eduardo J. M.

doi:10.1016/j.fluid.2011.02.020

Cited by 31 publications

(26 citation statements)

References 34 publications

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“…Using this approach, experimental densities were predicted within 1% at atmospheric pressure and 3.5% for higher pressures. In a later study [1], the molar volumes and partial molar volumes at infinite dilution of PFA and PFAA molecules in n-octane were predicted, again utilizing the hetero-SAFT-VR approach [28]. Using the same parameters and molecular model as the previous study [28], the molar volume and partial molar volumes at infinite dilution of the PFA molecules were found to have deviations from experiment of less than 5% in all cases.…”

Section: Introductionmentioning

confidence: 87%

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Predicting the phase behavior of fluorinated organic molecules using the GC-SAFT-VR equation of state

Haley

McCabe

2017

Fluid Phase Equilibria

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Fluorinated molecules such as perfluoroalkanes (PFA), perfluoroalkylalkanes (PFAA), fluoroalkanes, and hydrofluoroethers (HFE) possess attractive physical properties that have resulted in their use in a wide range of applications. However, while there is an abundance of thermophysical data for alkanes in the literature, only limited studies have been performed that report the properties of the corresponding fluorinated species. Predictive approaches are therefore needed to accurately and reliably determine the physical properties of these molecules. The statistical associating fluid theory (SAFT) is a commonly used molecular-based equation of state that in its various forms has been applied to study a wide range of fluid systems. In recent work, several group contribution (GC) SAFT equations of state have been proposed, such as the GC-SAFT-VR equation that combines the SAFT equation for potentials of variable range (VR) with a group contribution approach that uniquely allows for the description of hetero-segmented chains. The GC-SAFT-VR equation has been shown to provide an excellent description of the phase behavior of pure associating and non-associating fluids and their mixtures, with a minimal reliance on fitting the model parameters to experimental data. Specifically, parameters for key functional groups (such as CH 3 , CH 2 , CH, CH 2 =CH, C=O, C 6 H 5 , ether and ester, OH, NH 2 , CH=O, COOH) have been obtained by fitting to experimental vapor pressure and saturated liquid density data for selected low molecular weight fluids and then used to predict the phase behavior of pure fluids and their mixtures without further adjusting the group parameters. To expand upon this effort, here we report parameters for the CF 3 , CF 2 , CF, CH 2 F, CHF 2 , and CHF functional groups and their cross interactions. The theoretical predictions are compared with experimental data for pure PFAs, PFAAs, and HFEs, as well as binary mixtures of alkanes, alkenes, PFAs, PFAAs, and CO 2 in order to test the transferability of the new group parameters. The GC-SAFT-VR approach is found to accurately predict the phase behavior of the systems studied.

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Section: Introductionmentioning

confidence: 87%

“…As an additional test of the fluorinated group parameters, the apparent molal volumes, V Φ, , of several PFAA and alkane binary mixtures have been investigated. In the work of Morgado et al [1], the apparent molal volumes, V Φ, , of the solutes in all solutions was measured and then calculated from the equation:…”

Section: Binary Mixturesmentioning

confidence: 99%

Predicting the phase behavior of fluorinated organic molecules using the GC-SAFT-VR equation of state

Haley

McCabe

2017

Fluid Phase Equilibria

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“…For instance, the fluid-phase behaviour of the binary alkane -perfluoroalkane mixtures has been investigated extensively with the SAFT-HS [66,67], SAFT-VR [68,69], soft-SAFT [70], PC-SAFT [71], and hetero-SAFT VR [72] EoSs. The properties of the PFAA molecules including the volumetric properties [73,74], vapour pressures [75], and solution behaviour of mixtures with n-alkanes and perfluoro-n-alkanes [72,76,77] have also been examined with the hetero-SAFT VR EoS [78]. These EoSs cannot, however, be used on their own to describe the interfacial tension of the systems unless they are incorporated within other approaches such as density functional [79][80][81] or square gradient [52,82,83] theories.…”

Section: Introductionmentioning

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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“…In addition to that, the authors also determined molar and molal volumes at infinite dilution of several perfluoroalkane and perfluoroalkylalkane molecules over a wide range of temperature and pressure. 63,64 In all cases, the authors obtained the experimental data and used the SAFT-VR approach to interpret the results. The importance of the results is due to the way in which the molecular formalism was used: all the molecular parameters were used in a transferable way, i.e., the parameters for alkyl and perfluoroalkyl chemical groups in surfactants were the same as those used for describing pure alkanes and perfluoroalkanes in previous works.…”

Section: Molecular Modelsmentioning

confidence: 99%

CHAPTER 16. SAFT and Molecular Simulation Techniques: Application to Determination of Volumetric Excess Properties

Blas¹,

Piñeiro²

2014

Volume Properties

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Perfluoroalkanes and perfluoroalkylalkane surfactants in solution: Partial molar volumes in n-octane and hetero-SAFT-VR modelling

Cited by 31 publications

References 34 publications

Predicting the phase behavior of fluorinated organic molecules using the GC-SAFT-VR equation of state

Predicting the phase behavior of fluorinated organic molecules using the GC-SAFT-VR equation of state

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

CHAPTER 16. SAFT and Molecular Simulation Techniques: Application to Determination of Volumetric Excess Properties

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