Probing the structure of gas expanded liquids using relative permittivity, density and polarity measurements

Abbott, Andrew P.; Hope, Eric G.; Mistry, Reena; Stuart, Alison M.

doi:10.1039/b915570h

Cited by 33 publications

(23 citation statements)

References 46 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However, this concentration threshold varies considerably with temperature. This behavior is consistent with the literature 3 and was related to the increase in free volume, which would be responsible for changes in transport and solvation properties. Indeed, intermolecular voids in the pure solvent can accept CO 2 molecules to a certain extent, producing a very small increase in volume.…”

Section: Introductionsupporting

confidence: 92%

“…The experimental determinations were carried out in a highpressure variable-volume visualization cell (9.6−31.3 cm 3 , Top Industrie, France) equipped with three sapphire windows and a magnetic stirrer. The temperature of the cell was maintained at the desired value with a thermostatic bath and measured with a thermocouple (type J, accuracy of ±0.1 K) placed inside the cell.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Controlling Solvation and Mass Transport Properties of Biobased Solvents through CO₂ Expansion: A Physicochemical and Molecular Modeling Study

Granero-Fernandez

Lacaze‐Dufaure

Condoret

et al. 2019

Ind. Eng. Chem. Res.

View full text Add to dashboard Cite

Gas-expanded liquids have been studied during past years; however, the physicochemical properties of some of these fluids still need to be characterized and understood. In particular, the study of properties concerning solvation and mass transport is key for industrial applications. This work presents the characterization of eight CO 2-expanded biosourced solvents: organic carbonates (dimethyl, diethyl, ethylene, and propylene carbonates), anisole, veratrole, γvalerolactone, and 2-methyltetrahydrofuran. Two approaches have been used: spectroscopic measurements and molecular modeling. Phase equilibrium was determined for each CO 2 / biosourced solvent system, and then the solvatochromic probe Nile Red was used to determine changes in dipolarity/ polarizability (π* Kamlet−Taft parameter) by CO 2 pressure. Molecular dynamics calculations were performed to determine the density and viscosity changes with CO 2 pressure. It is shown in this study that the degree of modulation of dipolarity/polarizability parameter can go from that of pure solvent (around 0.4 for linear organic carbonates) to negative values, close to that of pure CO 2 at the T and P used in this study. Concerning transport properties, such as density and viscosity, a great decrease in both these properties' values was observed after swelling of the solvent by CO 2 , for instance, in linear organic carbonates where density can decrease to 50% the density of pure solvent; concerning viscosity a decrease of up to 90% was measured for these compounds. It was observed that the solubility of CO 2 and then modulation of properties were higher in linear organic carbonates than in the cyclic ones. This study shows once more that CO 2 has a great capacity to be used as a knob for triggering changes in the physicochemical properties of green biosourced solvents that can help to implement these solvents in industrial applications.

show abstract

Section: Introductionsupporting

confidence: 92%

Section: Introductionmentioning

confidence: 99%

Controlling Solvation and Mass Transport Properties of Biobased Solvents through CO₂ Expansion: A Physicochemical and Molecular Modeling Study

Granero-Fernandez

Lacaze‐Dufaure

Condoret

et al. 2019

Ind. Eng. Chem. Res.

View full text Add to dashboard Cite

show abstract

“…41,42 ', e r of a mixture of CO 2 + CH 3 CN measured at 25 1C and 5.0 MPa. 43 The composition of the mixture is interpolated from the vapour-liquid phase equilibrium data reported by Reighard et al 44 This journal is © the Owner Societies 2014 and high-pressure safety. (Safety note: the illustrations shown here are purely schematic and should not be regarded as engineering drawings for the construction of safe high-pressure cells.…”

Section: Properties Of Scfs and Measurement Of Solubility And Conductmentioning

confidence: 99%

Electrodeposition from supercritical fluids

Bartlett

Cook

George

et al. 2014

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

Recent studies have shown that it is possible to electrodeposit a range of materials, such as Cu, Ag and Ge, from various supercritical fluids, including hydrofluorocarbons and mixtures of CO2 with suitable co-solvents. In this perspective we discuss the relatively new field of electrodeposition from supercritical fluids. The perspective focuses on some of the underlying physical chemistry and covers both practical and scientific aspects of electrodeposition from supercritical fluids. We also discuss possible applications for supercritical fluid electrodeposition and suggest some key developments that are required to take the field to the next stage.

show abstract

“…[18][19][20][21][22][23][24][25][26][27] In earlier studies, Yoshida et al investigated the hydrogenation of nitrostyrene in CO 2 -expanded ethanol and toluene at 323 K over Pt/TiO 2 , 28 but either the conversion or the selectivity was not satisfactory (< 50%), probably due to the intrinsic nature of Pt/TiO 2 . Among others, CO 2 -expanded liquids (also called gas expanded liquids, GXLs) offers prominent advantages due to greatly reduced solvent amount and tunable solvent properties in a wide range.…”

Section: Introductionmentioning

confidence: 99%

Chemoselective hydrogenation of 3-nitrostyrene over a Pt/FeO_x pseudo-single-atom-catalyst in CO₂-expanded liquids

Wei

Ren

et al. 2016

Green Chem.

View full text Add to dashboard Cite

Chemoselective hydrogenation of substituted nitroarenes containing two reducible groups in one molecule is a highly desired approach to the synthesis of functionalized anilines. To make this process environmentally benign, we used pseudo-single-atom-catalyst Pt/FeOx and investigated the reaction in supercritical CO2 and CO2-expanded toluene. The results showed that supercritical CO2 afforded excellent selectivity but low reactivity due to the limit of substrate solubility in the reaction medium. By contrast, when the reaction proceeded in CO2 expanded toluene, both the conversion of 3nitrostyrene and the selectivity of 3-vinylaniline reached above 95% under optimum conditions while the organic tolune amount could be reduced by 90% comparied to that without CO2. The thermodynamic calculations revealed that the solubility of H2 increased while the viscosity of the reaction system decreased with the CO2 pressure, which facilitated the mass transfer and therefore increased the reaction rate meanwhile kept the selectivity at a high level.

show abstract

Probing the structure of gas expanded liquids using relative permittivity, density and polarity measurements

Cited by 33 publications

References 46 publications

Controlling Solvation and Mass Transport Properties of Biobased Solvents through CO₂ Expansion: A Physicochemical and Molecular Modeling Study

Controlling Solvation and Mass Transport Properties of Biobased Solvents through CO₂ Expansion: A Physicochemical and Molecular Modeling Study

Electrodeposition from supercritical fluids

Chemoselective hydrogenation of 3-nitrostyrene over a Pt/FeO_x pseudo-single-atom-catalyst in CO₂-expanded liquids

Contact Info

Product

Resources

About

Probing the structure of gas expanded liquids using relative permittivity, density and polarity measurements

Cited by 33 publications

References 46 publications

Controlling Solvation and Mass Transport Properties of Biobased Solvents through CO2 Expansion: A Physicochemical and Molecular Modeling Study

Controlling Solvation and Mass Transport Properties of Biobased Solvents through CO2 Expansion: A Physicochemical and Molecular Modeling Study

Electrodeposition from supercritical fluids

Chemoselective hydrogenation of 3-nitrostyrene over a Pt/FeOx pseudo-single-atom-catalyst in CO2-expanded liquids

Contact Info

Product

Resources

About

Controlling Solvation and Mass Transport Properties of Biobased Solvents through CO₂ Expansion: A Physicochemical and Molecular Modeling Study

Controlling Solvation and Mass Transport Properties of Biobased Solvents through CO₂ Expansion: A Physicochemical and Molecular Modeling Study

Chemoselective hydrogenation of 3-nitrostyrene over a Pt/FeO_x pseudo-single-atom-catalyst in CO₂-expanded liquids