Development of a robust soft-SAFT model for protic ionic liquids using new high-pressure density data

Crespo, Emanuel A.; Silva, Liliana P.; Correia, Cristina I.P.; Martins, Mónia A.R.; Gardas, Ramesh L.; Vega, Lourdes F.; Carvalho, Pedro J.; Coutinho, João A. P.

doi:10.1016/j.fluid.2021.113036

Cited by 11 publications

(4 citation statements)

References 61 publications

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“… 47 At atmospheric pressure, α p is monotonically increasing with increasing temperature for all the DBU-based PILs studied ( Figure S14 and Table S4 ). Similar behavior is expected for organic solvents, 48 and it is also reported for other protic 49 and aprotic ionic liquids. 50 A more pronounced temperature dependence is observed for the DBUH-IM14 ( Table S5 ), which contains the largest anion.…”

Section: Resultssupporting

confidence: 85%

Implications of Anion Structure on Physicochemical Properties of DBU-Based Protic Ionic Liquids

et al. 2022

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Protic ionic liquids (PILs) are potential candidates as electrolyte components in energy storage devices. When replacing flammable and volatile organic solvents, PILs are expected to improve the safety and performance of electrochemical devices. Considering their technical application, a challenging task is the understanding of the key factors governing their intermolecular interactions and physicochemical properties. The present work intends to investigate the effects of the structural features on the properties of a promising PIL based on the 1,8-diazabicyclo[5.4.0]undec-7-ene (DBUH + ) cation and the (trifluoromethanesulfonyl)(nonafluorobutanesulfonyl)imide (IM14 – ) anion, the latter being a remarkably large anion with an uneven distribution of the C–F pool between the two sides of the sulfonylimide moieties. For comparison purposes, the experimental investigations were extended to PILs composed of the same DBU-based cation and the trifluoromethanesulfonate (TFO – ) or bis(trifluoromethanesulfonyl)imide (TFSI – ) anion. The combined use of multiple NMR methods, thermal analyses, density, viscosity, and conductivity measurements provides a deep characterization of the PILs, unveiling peculiar behaviors in DBUH-IM14, which cannot be predicted solely on the basis of differences between aqueous p K a values of the protonated base and the acid (Δp K a ). Interestingly, the thermal and electrochemical properties of DBUH-IM14 turn out to be markedly governed by the size and asymmetric nature of the anion. This observation highlights that the structural features of the precursors are an important tool to tailor the PIL’s properties according to the specific application.

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Section: Resultssupporting

confidence: 85%

Implications of Anion Structure on Physicochemical Properties of DBU-Based Protic Ionic Liquids

et al. 2022

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“…Although soft-SAFT can successfully predict such an effect using only the pure-component parameters (see Figure S9, in the Supporting Information), the need for a BIP to obtain a quantitative agreement with the experimental data is expected; the main reason being the use of constant association parameters in the carboxylate-based PIL model developed in our previous work . Although such a simplification is necessary given the constrained parameterization of ILs in EoS models (i.e., vapor pressures, vaporization enthalpies, and other data commonly used for parameterization are not measurable for ILs), the resulting association parameters typically represent the average behavior of the homologous series of compounds being parameterized and not the value that best represents each IL.…”

Section: Results and Discussionmentioning

confidence: 99%

Encapsulated Protic Ionic Liquids as Sustainable Materials for CO₂ Separation

Silva

Crespo

Martins

et al. 2022

Ind. Eng. Chem. Res.

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Protic ionic liquids (PILs) have been suggested as promising solvents for CO2 capture; however, their high viscosity and consequent poor mass transfer coefficients hinder their large-scale industrial application. To overcome this limitation, PILs (neat or encapsulated) can be incorporated into polymers coated on hollow fiber membranes, to be implemented in gas–liquid contactor units. However, before the immobilization of PIL-based solvents on membranes, fundamental studies on the CO2 sorption process in PILs are still mandatory. Here, the carboxylate-based PILs’ ability for CO2 absorption was evaluated using an isochoric solubility cell in a wide range of temperatures (303–343 K) and CO2 partial pressures (0–0.8 MPa). The experimental data revealed the existence of a distinct sorption mechanism than that typically observed in other low-volatile physical solvents, where the solubility was mainly affected by entropic effects. The soft-SAFT equation of state was further applied for modeling of the solubility data, which allowed us to infer the influence of the anion’s structure on the system’s interactions. Aiming to improve the process kinetics, the PILs were encapsulated in carbonaceous submicrocapsules, herein proposed as an efficient material for CO2 separation. To characterize the composition, morphology, porous structure, and thermal stability of the solvents used, SEM, TEM, TGA, BET, and elemental analyses were performed. The adsorption of CO2 on these materials showed that these materials retained the same sorption capacity as their neat counterparts and with considerably increased sorption rates. These materials also retained their performance after various sorption–desorption cycles and showed fast and complete regeneration and high sorption capacity, thus indicating their potential for CO2 capture.

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“…Among the most reported models for VLE descriptions are excess Gibbs energy-based models and cubic Equations of State (cEoS) based models. Other models, such as cEoS Plus Association (CPA) based models and models based on Statistical Associating Fluid Theory (SAFT) including soft SAFT and Perturbed Chain Statistical Associating Fluid Theory (PC-SAFT) , have recently received more attention.…”

Section: Introductionmentioning

confidence: 99%

Isobaric Vapor–Liquid Equilibrium Prediction from Excess Molar Enthalpy Using Cubic Equations of State and PC-SAFT

Brouwer

Crespo

Kate³

et al. 2023

Ind. Eng. Chem. Res.

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Vapor−liquid equilibrium (VLE) data, essential for an accurate design of distillation columns, are not always readily available. This work has systematically assessed the feasibility of determining VLE data based on excess molar enthalpy (h E ) results. Twelve cubic Equation of State (cEoS) models combined with eight mixing rules and the Perturbed Chain Statistical Associating Fluid Theory (PC-SAFT) have been assessed. cEoS models are robust and applicable to a significant number of solvent families, while the PC-SAFT model is typically applied for strongly nonideal systems exhibiting molecular association behavior. VLE predictions based on the Peng−Robinson cEoS with the 2-parameter Stryjek− Vera−Margules-type mixing rule, one of the best cEoS−mixing rule combinations, was reasonably accurate, but less accurate than predictions based on the standard modified (mod.) UNIFAC (Do) model. This makes the developed h E −cEoS−VLE methodology relevant only for systems whose binary interaction parameters in UNIFAC (Do) and VLE data are not available. For the most nonideal self-associating systems evaluated, the PC-SAFT model parametrized with experimental h E data provided isobaric VLE results with similar or even higher accuracy than the mod. UNIFAC (Do) model. This indicates the potential of the h E −PC-SAFT− VLE model for accurately predicting VLE data for highly nonideal and associating systems. Therefore, this methodology can be used as a quick evaluation method for the separation of complex systems, including ionic liquids and deep eutectic solvents, for which the mod. UNIFAC (Do) model does not provide sufficiently accurate VLE predictions.

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Development of a robust soft-SAFT model for protic ionic liquids using new high-pressure density data

Cited by 11 publications

References 61 publications

Implications of Anion Structure on Physicochemical Properties of DBU-Based Protic Ionic Liquids

Implications of Anion Structure on Physicochemical Properties of DBU-Based Protic Ionic Liquids

Encapsulated Protic Ionic Liquids as Sustainable Materials for CO₂ Separation

Isobaric Vapor–Liquid Equilibrium Prediction from Excess Molar Enthalpy Using Cubic Equations of State and PC-SAFT

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Development of a robust soft-SAFT model for protic ionic liquids using new high-pressure density data

Cited by 11 publications

References 61 publications

Implications of Anion Structure on Physicochemical Properties of DBU-Based Protic Ionic Liquids

Implications of Anion Structure on Physicochemical Properties of DBU-Based Protic Ionic Liquids

Encapsulated Protic Ionic Liquids as Sustainable Materials for CO2 Separation

Isobaric Vapor–Liquid Equilibrium Prediction from Excess Molar Enthalpy Using Cubic Equations of State and PC-SAFT

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Product

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Encapsulated Protic Ionic Liquids as Sustainable Materials for CO₂ Separation