The Origin of the LCST on the Liquid–Liquid Equilibrium of Thiophene with Ionic Liquids

Batista, Marta L. S.; Tomé, Luciana I.N.; Neves, Catarina M. S. S.; Rocha, Eugénio M.; Gomes, José R. B.; Coutinho, João A. P.

doi:10.1021/jp303187z

Cited by 16 publications

(17 citation statements)

References 49 publications

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“…As already apparent from the discussion so far, UCST and LCST are not exclusive features of IL/water solutions but can be observed in systems made of IL in a variety of organic molecular solvents. Interesting, in this respect, is the study in reference [ 128 ], comparing the solubility in thiophene of [bmim][SCN] and [bmim][NTf

], whose temperature dependence displays a LCST for the former, and a UCST for the latter. The analysis of interactions by the experimental determination of the molar volumes and by NMR in the mixed and demixed phases and by MD simulations highlights an attractive interaction between a thiophene proton and the S atom in [bmim][SCN], and a solvophobic character of [bmim][NTf

] in thiophene.…”

Section: Overview Of Experimental and Computational Studiesmentioning

confidence: 99%

“…Atomistic MD simulations of thermoresponsive IL/water solutions have, until now, played different roles from that of thermodynamic models, since MD cannot be used for the extensive screening of hundred of compounds, although MD has contributed significant insight into these systems and phenomena. A clear distinction between the contribution of experiments and simulations to the understanding of thermoresponsive IL solutions is not really possible, at least because several studies combine both approaches (see, for instance, references [ 32 , 76 , 128 ]). Nevertheless, it is also possible to observe that, in this field, the strength of simulation has been in providing structural details and mechanisms down to the atomistic level.…”

Section: The Role Of Computational Modelingmentioning

confidence: 99%

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Thermoresponsive Ionic Liquid/Water Mixtures: From Nanostructuring to Phase Separation

et al. 2022

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The thermodynamics, structures, and applications of thermoresponsive systems, consisting primarily of water solutions of organic salts, are reviewed. The focus is on organic salts of low melting temperatures, belonging to the ionic liquid (IL) family. The thermo-responsiveness is represented by a temperature driven transition between a homogeneous liquid state and a biphasic state, comprising an IL-rich phase and a solvent-rich phase, divided by a relatively sharp interface. Demixing occurs either with decreasing temperatures, developing from an upper critical solution temperature (UCST), or, less often, with increasing temperatures, arising from a lower critical solution temperature (LCST). In the former case, the enthalpy and entropy of mixing are both positive, and enthalpy prevails at low T. In the latter case, the enthalpy and entropy of mixing are both negative, and entropy drives the demixing with increasing T. Experiments and computer simulations highlight the contiguity of these phase separations with the nanoscale inhomogeneity (nanostructuring), displayed by several ILs and IL solutions. Current applications in extraction, separation, and catalysis are briefly reviewed. Moreover, future applications in forward osmosis desalination, low-enthalpy thermal storage, and water harvesting from the atmosphere are discussed in more detail.

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] in thiophene.…”

Section: Overview Of Experimental and Computational Studiesmentioning

confidence: 99%

Section: The Role Of Computational Modelingmentioning

confidence: 99%

Thermoresponsive Ionic Liquid/Water Mixtures: From Nanostructuring to Phase Separation

et al. 2022

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“…However, compared with polymeric LCST systems, only a limited number of smaller molecules-containing systems has been developed exhibiting LCST behavior and adjustable thermo-responsive properties. These include ionic liquids [27–30], macrocycles [31–34], and supramolecular pairs [26,35–38]. For example, the combination of macrocycles and supramolecular interactions can realize controlled release and product separation in complex supramolecular systems [35].…”

Section: Introductionmentioning

confidence: 99%

LCST phase behavior of benzo-21-crown-7 with different alkyl chains

Deng¹,

Li²,

Zhang³

et al. 2019

Beilstein J. Org. Chem.

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“…Molecular dynamics (MD) simulation is a general method in researching the LCST phase behavior on an atomic or a molecular level . For example, Batista et al studied the mixture system of thiophene and 1-butyl-3-methylimidazolium thiocyanate ([C 4 C 1 im][SCN]) by using MD simulation. It was found that the LCST phase behavior of mixture was caused by the interactions of [SCN] − with thiophene.…”

Section: Introductionmentioning

confidence: 99%

“…Molecular dynamics (MD) simulation is a general method in researching the LCST phase behavior on an atomic or a molecular level. 17 For example, Batista et al 18 S1), the reported AMBER all-atom force field parameters were used, 20,21 and the SPC model of H 2 O was adopted. 22 By using the Gaussian 09 D.01 version, 23 the ion pair structures were optimized at the B3LYP/6-31+G* level.…”

Section: Introductionmentioning

confidence: 99%

Effect of Anionic Structure on the LCST Phase Behavior of Phosphonium Ionic Liquids in Water

Zhang¹,

Liu²,

Pei³

et al. 2018

Ind. Eng. Chem. Res.

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To shed light on the mechanism of lowest critical solution temperature (LCST) phase behavior, the phosphonium-based ionic liquids (ILs) with different anions ([CF3COO]−, [CH3COO]−, and [PF6]−) were chosen and studied in this work by molecular dynamics (MD) simulations. In this work, a set of MD simulations on IL/H2O systems were implemented at different temperatures. It was found that, among these systems, H-bonds between [CF3COO]− and water molecules in the [P4444][CF3COO]/H2O system were most seriously destroyed with increasing temperature, leading to the aggregation of cations and anions and phase separation. Furthermore, the simulations for [P4444][CF3COO]/H2O and [P4444][CH3COO]/H2O systems were also performed to reveal the effect of water contents on phase separation. It was shown that each unit volume of anion–water interaction change with temperature (ΔE inter/V) can well describe the change of experimental lowest critical solution temperature in the [P4444][CF3COO]–H2O system, which is an important predictive factor for the phase transition behavior. These findings are useful for a deeper understanding of LCST phase behavior of IL/H2O systems and would accelerate further studies on the design and application of new LCST-type ILs.

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The Origin of the LCST on the Liquid–Liquid Equilibrium of Thiophene with Ionic Liquids

Cited by 16 publications

References 49 publications

Thermoresponsive Ionic Liquid/Water Mixtures: From Nanostructuring to Phase Separation

Thermoresponsive Ionic Liquid/Water Mixtures: From Nanostructuring to Phase Separation

LCST phase behavior of benzo-21-crown-7 with different alkyl chains

Effect of Anionic Structure on the LCST Phase Behavior of Phosphonium Ionic Liquids in Water

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