Abstract:This work represents an essential step towards the understanding of the dynamics and thermodynamic characteristics of a novel family of ionic liquids, namely fluorinated ionic liquids based on the combination of 1-alkyl-3-methylimidazolium cations with perfluoroalkylsulfonates or perfluoroalkylcarboxylates anions. The so far scarce information about these fluids constitutes a limiting factor for their potential applications. In this work, we provide detailed evidence on the influence of hydrogenated and fluori… Show more
“…SO 3 ]a re presented in Ta ble S2 (in the Supporting Information) as afunction of temperature.D ensity is one of the mostr elevant properties required for the design of different products related to biomedical applications,w hereas the determination of conductivity and viscosity provides additional knowledge about the transport properties of thesec ompounds. [74,75] The thermophysicalp roperties for the other previously studied [10,45] The analysis of the results reveals that the increment of the hydrogenated alkyl side chain length leads to ad ecrease of the density (see Figure 3). Ac omparison between these densities and those of other PFC compoundsc ommonly used in biomedical applications ( % 5.0 mol L À1 ), [78] indicates that [C 2 C 1 Im][C 4 F 9 SO 3 ]i st he FIL that has the closest density to that of PFCs values.…”
Section: Thermal and Thermophysical Propertiesmentioning
confidence: 96%
“…The syntheses of 1-butyl-3-methylimidazolium perfluorobutanesulfonate ([C 4 C 1 Im][C 4 F 9 SO 3 ]) and 1-decyl-3-methylimidazolium perfluorobutanesulfonate ([C 10 C 1 Im][C 4 F 9 SO 3 ]) were carried out by the ion exchange resin method. [45] Details concerning the procedure are described in the Supporting Information. These compounds were completely characterized by 1 Ha nd 19 FNMR spectroscopy and elemental analysis (results in the Supporting Information) to check their purity.E ach FIL sample was dried for at least 48 hours immediately prior to its use at moderate temperature ( % 323 K) and vacuum ( % 0.1 Pa).…”
Section: Experimental Section Materialsmentioning
confidence: 99%
“…Once the number of association sites has been chosen, we have obtained the set of molecular parameter values by fitting to available temperature-density experimental data at atmospheric pressure. [10,45] To reduce the parameters degeneracy and increase the transferability between compounds, several assumptions have been made. The most important restriction affects the parameters describing the strength and volume of association, which have been fixed to constant values for the whole family,u nder the assumption that their effect is independent of the alkyl chain length of the imidazolium tail.…”
Section: Soft-saftmolecular Model For Filsmentioning
confidence: 99%
“…These results were compared (see Figure 2) with those of FILs of the same family, [C 2 C 1 Im][C 4 F 9 SO 3 ], [C 6 C 1 Im][C 4 F 9 SO 3 ], [C 8 C 1 Im][C 4 F 9 SO 3 ], and [C 12 C 1 Im][C 4 F 9 SO 3 ], previously published. [10,45] Ta king into account the availabled ata, it is possible to analyze the effect of the increment of the hydrogenated alkyl side chain on these imidazolium-based FILs.T oe valuate the use of these FILs for biomedical purposes, the most relevant temperature is 310.15 K, which is accepted to be the average body temperature in humans. High thermals tabilities are characteristic of these compounds and an advantage for severala pplications.…”
Section: Thermal and Thermophysical Propertiesmentioning
confidence: 99%
“…The current experimental data have also been theoretically modeled by using FVT coupled with soft-SAFT (solid lines , dark grey hexagons). [10,45] Solid lines represent the soft-SAFTcalculations. ChemPhysChem 2017ChemPhysChem , 18,2012ChemPhysChem -2023 www.chemphyschem.org 2017 Wiley-VCH Verlag GmbH &Co. KGaA, Weinheim in Figure 5).…”
Section: Thermal and Thermophysical Propertiesmentioning
Fluorinated ionic liquids (FILs) exhibit complex molecular behavior, where three different nanodomains (polar, hydrogenated nonpolar, and fluorinated nonpolar) have been identified by molecular simulations. Given the high number of possible anion/cation combinations, a theoretical tool able to describe the thermophysical properties of these compounds in a systematic, rapid, and accurate manner is highly desirable. We present here a combined experimental-theoretical methodology to obtain the phase, interface, and transport properties of the 1-alkyl-3-methylimidazolium perfluorobutanesulfonate ([C C Im][C F SO ]) family. In addition to providing new experimental data, an extended version of the Statistical Associating Fluid Theory (soft-SAFT) is used to describe the physicochemical behavior of the [C C Im][C F SO ] family. A mesoscopic molecular model is built based on the analysis of the chemical structures of these FILs, and supported by quantum chemical calculations to study the charge distribution of the anion, where only the basic physical features are considered. The resulting molecular parameters are related to the molecular weight, providing the basis for thermophysical predictions of similar compounds. The theory is also able to predict the minimum in the surface tension versus the length of the hydrogenated alkyl chain, experimentally found at n=8. The viscosity parameters are also in agreement with the free-volume calculations obtained from experiments.
“…SO 3 ]a re presented in Ta ble S2 (in the Supporting Information) as afunction of temperature.D ensity is one of the mostr elevant properties required for the design of different products related to biomedical applications,w hereas the determination of conductivity and viscosity provides additional knowledge about the transport properties of thesec ompounds. [74,75] The thermophysicalp roperties for the other previously studied [10,45] The analysis of the results reveals that the increment of the hydrogenated alkyl side chain length leads to ad ecrease of the density (see Figure 3). Ac omparison between these densities and those of other PFC compoundsc ommonly used in biomedical applications ( % 5.0 mol L À1 ), [78] indicates that [C 2 C 1 Im][C 4 F 9 SO 3 ]i st he FIL that has the closest density to that of PFCs values.…”
Section: Thermal and Thermophysical Propertiesmentioning
confidence: 96%
“…The syntheses of 1-butyl-3-methylimidazolium perfluorobutanesulfonate ([C 4 C 1 Im][C 4 F 9 SO 3 ]) and 1-decyl-3-methylimidazolium perfluorobutanesulfonate ([C 10 C 1 Im][C 4 F 9 SO 3 ]) were carried out by the ion exchange resin method. [45] Details concerning the procedure are described in the Supporting Information. These compounds were completely characterized by 1 Ha nd 19 FNMR spectroscopy and elemental analysis (results in the Supporting Information) to check their purity.E ach FIL sample was dried for at least 48 hours immediately prior to its use at moderate temperature ( % 323 K) and vacuum ( % 0.1 Pa).…”
Section: Experimental Section Materialsmentioning
confidence: 99%
“…Once the number of association sites has been chosen, we have obtained the set of molecular parameter values by fitting to available temperature-density experimental data at atmospheric pressure. [10,45] To reduce the parameters degeneracy and increase the transferability between compounds, several assumptions have been made. The most important restriction affects the parameters describing the strength and volume of association, which have been fixed to constant values for the whole family,u nder the assumption that their effect is independent of the alkyl chain length of the imidazolium tail.…”
Section: Soft-saftmolecular Model For Filsmentioning
confidence: 99%
“…These results were compared (see Figure 2) with those of FILs of the same family, [C 2 C 1 Im][C 4 F 9 SO 3 ], [C 6 C 1 Im][C 4 F 9 SO 3 ], [C 8 C 1 Im][C 4 F 9 SO 3 ], and [C 12 C 1 Im][C 4 F 9 SO 3 ], previously published. [10,45] Ta king into account the availabled ata, it is possible to analyze the effect of the increment of the hydrogenated alkyl side chain on these imidazolium-based FILs.T oe valuate the use of these FILs for biomedical purposes, the most relevant temperature is 310.15 K, which is accepted to be the average body temperature in humans. High thermals tabilities are characteristic of these compounds and an advantage for severala pplications.…”
Section: Thermal and Thermophysical Propertiesmentioning
confidence: 99%
“…The current experimental data have also been theoretically modeled by using FVT coupled with soft-SAFT (solid lines , dark grey hexagons). [10,45] Solid lines represent the soft-SAFTcalculations. ChemPhysChem 2017ChemPhysChem , 18,2012ChemPhysChem -2023 www.chemphyschem.org 2017 Wiley-VCH Verlag GmbH &Co. KGaA, Weinheim in Figure 5).…”
Section: Thermal and Thermophysical Propertiesmentioning
Fluorinated ionic liquids (FILs) exhibit complex molecular behavior, where three different nanodomains (polar, hydrogenated nonpolar, and fluorinated nonpolar) have been identified by molecular simulations. Given the high number of possible anion/cation combinations, a theoretical tool able to describe the thermophysical properties of these compounds in a systematic, rapid, and accurate manner is highly desirable. We present here a combined experimental-theoretical methodology to obtain the phase, interface, and transport properties of the 1-alkyl-3-methylimidazolium perfluorobutanesulfonate ([C C Im][C F SO ]) family. In addition to providing new experimental data, an extended version of the Statistical Associating Fluid Theory (soft-SAFT) is used to describe the physicochemical behavior of the [C C Im][C F SO ] family. A mesoscopic molecular model is built based on the analysis of the chemical structures of these FILs, and supported by quantum chemical calculations to study the charge distribution of the anion, where only the basic physical features are considered. The resulting molecular parameters are related to the molecular weight, providing the basis for thermophysical predictions of similar compounds. The theory is also able to predict the minimum in the surface tension versus the length of the hydrogenated alkyl chain, experimentally found at n=8. The viscosity parameters are also in agreement with the free-volume calculations obtained from experiments.
Two series of aromatic compounds with perfluoroalkyl (R ) groups of increasing length, 1,3,5,7-naphthalene(R ) and 1,3,5,7,9-corannulene(R ) , have been prepared and their electronic properties studied by low-temperature photoelectron spectroscopy (PES) (for gas-phase electron affinity measurements). These and many related compounds were also studied by DFT calculations. The data demonstrate unambiguously that the electron-withdrawing ability of R substituents increases significantly and uniformly from CF to C F to n-C F to n-C F .
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