Cosolvent interactions in supercritical fluid solutions

Ekart, Michael P.; Bennett, Karen; Ekart, Susan M.; Gurdial, Gurdev S.; Liotta, Charles L.; Eckert, Charles A.

doi:10.1002/aic.690390206

Cited by 137 publications

(101 citation statements)

References 47 publications

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“…It is well known that the addition of a polar co-solvent (methanol, for example) to supercritical H 2 O or CO 2 often leads to an enhancement in the solubility of a solute and can improve the selectivity of a supercritical solvent (effective polar modifiers) [11][12][13][14][15][16][17][18]. Thus, Methanol is often used as an effective modifier for H 2 O and CO 2 in supercritical fluid extraction and in supercritical chromatography.…”

Section: Introductionmentioning

confidence: 99%

Thermodynamic Properties of Methanol in the Critical and Supercritical Regions

et al. 2005

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The isochoric heat capacity of pure methanol in the temperature range from 482 to 533 K, at near-critical densities between 274.87 and 331.59 kg · m −3 , has been measured by using a high-temperature and high-pressure nearly constant volume adiabatic calorimeter. The measurements were performed in the singleand two-phase regions including along the coexistence curve. Uncertainties of the isochoric heat capacity measurements are estimated to be within 2%. The single-and two-phase isochoric heat capacities, temperatures, and densities at saturation were extracted from experimental data for each measured isochore. The critical temperature (T c = 512.78 ± 0.02 K) and the critical density (ρ c = 277.49 ± 2 kg · m −3 ) for pure methanol were derived from the isochoric heat-capacity measurements by using the well-established method of quasi-static thermograms. The results of the C V V T measurements together with recent new experimental PVT data for pure methanol were used to develop a thermodynamically self-consistent Helmholtz free-energy parametric crossover model, CREOS97-04. The accuracy of the crossover model was confirmed by a comprehensive comparison with available experimental data for pure methanol and values calculated with various multiparameter equations of state and correlations. In the critical and supercritical regions at 0.98T c T 1.5T c and in the density range 0.35ρ c ρ 1.65ρ c , CREOS97-04 represents all available experimental thermodynamic data for pure methanol to within their experimental uncertainties.

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Section: Introductionmentioning

confidence: 99%

Thermodynamic Properties of Methanol in the Critical and Supercritical Regions

et al. 2005

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“…Solubilities and cosolvent effects have been studied for the various solutes shown in Table 5 (Ekart et al, 1993b). These include nonpolar compounds such as anthracene and phenanthrene, oxygen compounds like 9-hydroxyfluorene and the phenolic 2-naphthol, and amines such as carbazole, with a pyrollic nitrogen, and acridine, with a pyridinic nitrogen.…”

Section: Chromatographic Technique and Cosolvent Effectsmentioning

confidence: 99%

Supercritical thermodynamics of sulfur and nitrogen species. Final technical report, October 1, 1991--September 30, 1994

Eckert¹

1994

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“…Cosolvent-solvent specific interactions, such as hydrogen bonding, charge transfer complex formation and dipole-dipole couplings appear to be important [50].…”

Section: Solute Solubilitymentioning

confidence: 99%

Thermodynamic Aspects of Supercritical Fluids Processing: Applications of Polymers and Wastes Treatment

Cansell

Rey

Beslin

1998

Rev. Inst. Fr. Pét.

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La mise en Ïuvre des fluides supercritiques est d'un intŽr•t croissant dans de nombreux domaines : pour la sŽparation (sŽparation et purification en pŽtrochimie, industrie alimentaire) et la chromatographie par fluides supercritiques (sŽparation analytique et prŽ-paratoire, dŽtermination des propriŽtŽs physicochimiques), comme milieux rŽactifs aux propriŽtŽs continžment ajustables allant du gaz au liquide (polyŽthyl•ne de faible densitŽ, Žlimination des dŽchets, recyclage des polym•res), en gŽologie et en minŽralogie (volcanologie, Žnergie gŽothermique, synth•se hydrothermique), dans la formation des particules, fibres et substrats (produits pharmaceutiques, explosifs, rev•tements), pour le sŽchage des matŽriaux (gels).Cet article prŽsente les propriŽtŽs physicochimiques exceptionnelles des fluides supercritiques en rapport avec leurs applications en ingŽnierie. Apr•s un bref rappel des concepts fondamentaux relatifs au comportement critique des fluides purs, nous dŽvelop-pons d'une mani•re plus dŽtaillŽe les propriŽtŽs physicochimiques ajustables des fluides dans le domaine supercritique. La deuxi•me partie de lÕarticle dŽcrit les applications en ingŽnierie des fluides supercritiques relatives aux rŽactions chimiques et au traitement des polym•res. Chaque prŽsentation d'application est divisŽe en deux parties : la premi•re rappelle les concepts de base et le contexte gŽnŽral ainsi que les propriŽtŽs physicochimiques, la seconde dŽveloppe les applications en ingŽnierie se rapportant au domaine concernŽ. THERMODYNAMIC ASPECTS OF SUPERCRITICAL FLUIDS PROCESSING: APPLICATIONS TO POLYMERS AND WASTES TREATMENTSupercritical fluid processes are of increasing interest for many fields: in supercritical fluid separation (petroleum-chemistry separation and purification, food industry) and supercritical fluid chromatography (analytical and preparative separation, determination of physicochemical properties); as reaction media with continuously adjustable properties from gas to liquid (lowdensity polyethylene, waste destruction, polymer recycling); in This paper presents the unusual physicochemical properties of supercritical fluids in relation to their engineering applications. After a short report of fundamental concepts of critical behavior in pure fluids, we develop in more details the tunable physicochemical properties of fluid in the supercritical domain. The second part of this paper describes the engineering applications of supercritical fluids relevant of chemical reactions and polymer processing. Each application presentation is divided in two parts: the first one recalls the basic concepts including general background, physicochemical properties and the second one develops the engineering applications relevant of the advocated domain. ASPECTOS TERMODINçMICOS DEL TRATAMIENTO DE LOS FLUIDOS SUPERCRêTICOS : APLICACIONES PARA LOS TRATAMIENTOS DE LOS POLêMEROS Y DE LOS RESIDUOSLa implementaci-n de los fluidos supercr'ticos presenta un interŽs cada vez mayor en numerosos campos : para la separaci-n (separaci-n y purific...

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Cosolvent interactions in supercritical fluid solutions

Cited by 137 publications

References 47 publications

Thermodynamic Properties of Methanol in the Critical and Supercritical Regions

Thermodynamic Properties of Methanol in the Critical and Supercritical Regions

Supercritical thermodynamics of sulfur and nitrogen species. Final technical report, October 1, 1991--September 30, 1994

Thermodynamic Aspects of Supercritical Fluids Processing: Applications of Polymers and Wastes Treatment

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