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1.
Supercritical carbon dioxide has been considered an appropriate alternative for extraction and purification process of cosmetics, pharmaceuticals, food supplements and natural products. Solubility information of biological compounds is essential for choosing supercritical fluid (SCF) processes. The solubility of iodopropynyl butylcarbamate (IPBC), a fungicide and anti-dandruff agent, was measured in supercritical carbon dioxide with a high pressure apparatus equipped with a variable volume view cell at 313.15, 323.15, and 333.15 K and at pressure between 80 and 35 MPa. The experimental data were correlated well with Peng–Robinson equation of state (PR EOS) and quasi-chemical nonrandom lattice fluid model. 相似文献
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《Fluid Phase Equilibria》1998,152(2):299-305
The equilibrium solubilities of dihydroxybenzene isomers pyrocatechol, resorcinol and hydroquinone have been measured in supercritical carbon dioxide using a simple static method. The measurements were performed in the pressure range from 120 to 400 atm at temperatures 35, 45, 55 and 65°C for pyrocatechol and resorcinol and in the pressure range from 120 to 200 atm at temperature 35°C for hydroquinone. The solubility of the isomers in supercritical CO2 was found to vary in the order pyrocatechol>resorcinol≫hydroquinone. The experimental data were correlated by use of the density based model proposed by Chrastil. 相似文献
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In an analysis of the solubility of a wide range of phthalocyanines (Pcs) and its analogues (SubPcs) in liquid and/or supercritical CO2, compounds with trifluoroethoxy substituents were found to exhibit high solubility. To our knowledge, this is the first example of Pc compounds soluble in 100% CO2. This unprecedented unique property of trifluoroethoxy substituted Pcs might have particular applications in catalysis in organic reactions as well as dyes for solar cells by CO2 delivering coatings. 相似文献
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The solubility of 49 metal-containing compounds and 15 "free" ligands in supercritical fluid carbon dioxide is reviewed. Solubilities were found to range over eight orders of magnitude, with the highest value of solubility being 56 g l(-1). Metals complexed with fluorine substituted ligands were found to be the most soluble, and metals complexed with phenyl-substituted ligands the least soluble. A general trend for increasing solubility with increasing oxidation state is observed and this is correlated with the increased number of coordinating ligands protecting the metal center from interaction with the supercritical fluid and also due to the increased number of solvation interactions with the increased number of ligand groups. 相似文献
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The supercritical technology has been considered as an appropriate alternative for separation of biomaterials from cosmetic, food, and pharmaceutical products. The solid solubility of biological compounds is the most important thermodynamic parameter in the supercritical extraction and purification. The equilibrium solubility of two biocides, climbazole, and triclocarban was measured in supercritical carbon dioxide with static method in the pressure range from (10 to 40) MPa and at temperatures equal to (313.2, 323.2, and 333.2) K. The experimental data were correlated by Peng–Robinson equation of state and quasi-chemical nonrandom lattice fluid model. 相似文献
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The solubility of newly synthesized chelating agents, i.e., tetraethylene glycol bis (2-ethylhexyl) dimethyl diphosphate (EG4EH), tetraethylene glycol bis (n-octyl) dimethyl diphosphate (EG4Oct), and tetraethylene glycol bis (2-butoxyethyl) dimethyl diphosphate (EG4BOE) in supercritical carbon dioxide (scCO2) were determined at temperatures ranging from (318.15 to 333.15) K and pressures ranging from (12 to 21) MPa. Solubility increases in the order of EG4Oct (MW = 606.33) < EG4BOE (MW = 582.26) < EG4EH (MW = 606.33), indicating that branched side chains of the ligands play an important part in increasing solubility in scCO2. Semi empirical density-based models proposed by Bartle and Chrastil were used to correlate the experimental data, and AARD values were calculated to be (1.2 to 2.9)% and (0.40 to 0.93)% for Bartle and Chrastil model, respectively. Additionally, the partial molar volumes of those compounds were estimated following the theory developed by Kumar and Johnston. 相似文献
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《Fluid Phase Equilibria》2006,239(1):63-68
In this work, the solubility of chlorobutane, ethyl methacrylate and trifluoroethyl acrylate in supercritical carbon dioxide (SC CO2) was determined. The solubility of hexane, styrene and chlorobenzene was also measured for comparison. The effect of the polar substitute on the solubility of different kind of compound in SC CO2 was discussed. The dependence of the solubility of the solute on the density of the binary system was also investigated and a proximate linear relationship existed between this solubility and density. 相似文献
9.
Extraction of disperse yellow 54 with supercritical carbon dioxide was conducted at 393.2 K and 30 MPa over a wide range of contact times. Saturated solubilities of the disperse dyestuff in supercritical carbon dioxide with or without cosolvent were also measured over the temperature and pressure ranges of 353.2 K to 393.2 K and 15 MPa to 30 MPa. Either ethanol or dimethyl sulfoxide, up to 5 mol%, was used as a cosolvent. As evidenced from the experimental results, the magnitudes of equilibrium solubility can be effectively enhanced in the presence of both two cosolvents. Dimethyl sulfoxide was found to yield higher solubility enhancement. Cosolvent effects were discussed on the basis of the Kamlet-Taft solvatochromic solvent parameters of cosolvents. The saturated solubility data were correlated with the Chrastil and the Mendez-Santiago and Teja equations. The Chrastil model correlated the solubility data to about within the experimental uncertainty. The correlated results of the Mendez-Santiago–Teja model supported the consistency of the solubility data over the entire experimental conditions. 相似文献
10.
Gibbs ensemble Monte Carlo simulations were used to investigate the effect of pressure and of entrainers on the solubility of low-volatility species in CO 2. Two entrainers were examined, n-octane and methanol, as well as two solutes, hexamethylbenzene and benzoic acid. For the three pressures studied (12, 20, and 28 MPa), the simulations demonstrate that the increase in the solubility with increasing pressure is mostly due to an increase in the solute's chemical potential (as expressed by the Poynting correction) and not due to an increase in the solvent strength of supercritical CO 2. The presence of an entrainer enhances solubility, particularly when the solute and entrainer can form hydrogen bonds. The solubility of benzoic acid is enhanced by an order of magnitude upon addition of methanol entrainer, whereas the enhancements are less than 2 for the other systems. 相似文献
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《Fluid Phase Equilibria》2005,238(1):120-128
The measurement and correlation of the experimental solubility of a spiroindolinonaphthoxazine photochromic dye (1,3-dihydro-3,3-dimethyl-1-isopropyl-6′-(2,3)-(dihydroindole-1-yl)spiro[2H-indole-2,3′-3H-naphtho[2,1-b] [1,4] oxazine]) in supercritical carbon dioxide (scCO2) is reported. Results were obtained using a static analytical method, at 308.0, 318.0 and 328.0 K, and in a pressure range from 10.0 to 26.0 MPa. Solubility experimental data were correlated with three density-based models (Chrastil, Bartle and Méndez-Santiago–Teja models), with the Ziger–Eckert semi-empirical correlation and with two cubic equation-of-state (EOS) models, namely the Peng–Robinson EOS (PR-EOS) and the Soave–Redlich–Kwong EOS (SRK-EOS), together with the conventional van der Waals mixing and combining rules. Good correlation results were obtained between the calculated and experimental solubility, to all fitted models. Solubility results clearly indicate the feasibility of processing this dye, and possibly this class of photochromic dyes, using supercritical fluid technologies and processes, for example, supercritical fluid dye impregnation of polymer host materials. 相似文献
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Laura Fedele Francesco Pernechele Sergio Bobbo Mauro Scattolini Roman Stryjek 《Fluid Phase Equilibria》2009
In this paper, solubility measurements of CO2 in pure pentaerythritol tetraoctanoate (PEC8) between 273 and 343 K are presented. The experiments were performed according to the static, synthetic method. The data are represented using the Peng–Robinson equation of state with the Huron–Vidal mixing rules and the UNIQUAC equation for the excess Gibbs Energy (gE) at infinite pressure. This system shows immiscibility in liquid phase, with lower critical end point (LCEP) at T = 268 ± 0.1 K and xCO2=0.98±0.001 and upper critical end point (UCEP) at the critical point of pure CO2. 相似文献
14.
Samsonov MD Wai CM Lee SC Kulyako Y Smart NG 《Chemical communications (Cambridge, England)》2001,(18):1868-1869
Uranium dioxide can be dissolved in supercritical CO2 with a CO2-philic TBP-HNO3 complexant to form a highly soluble UO2(NO3)(2).2TBP complex; this new method of dissolving UO2 that requires no water or organic solvent may have important applications for reprocessing of spent nuclear fuels and for treatment of nuclear wastes. 相似文献
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V. N. Khrustalev L. N. Nikitin A. Yu. Vasil’kov A. R. Khokhlov 《Russian Chemical Bulletin》2006,55(3):576-578
An organometallic compound, monoacetylferrocene, was for the first time obtained as single crystals by crystallization from
supercritical carbon dioxide. This offers the possibility of utilizing supercritical media for efficient crystallization and
purification of organometallic compounds without using organic solvents.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 555–557, March, 2006. 相似文献
16.
Fürstner A Ackermann L Beck K Hori H Koch D Langemann K Liebl M Six C Leitner W 《Journal of the American Chemical Society》2001,123(37):9000-9006
Liquid or supercritical carbon dioxide (scCO(2)) is a versatile reaction medium for ring-opening metathesis polymerization (ROMP) and ring-closing olefin metathesis (RCM) reactions using well-defined metal catalysts. The molybdenum alkylidene complex 1 and ruthenium carbenes 2 and 3 bearing PCy(3) or N-heterocyclic carbene ligands, respectively, can be used and are found to exhibit efficiency similar to that in chlorinated organic solvents. While compound 1 is readily soluble in scCO(2), complexes 2 and 3 behave like heterogeneous catalysts in this reaction medium. Importantly, however, the unique properties of scCO(2) provide significant advantages beyond simple solvent replacement. This pertains to highly convenient workup procedures both for polymeric and low molecular weight products, to catalyst immobilization, to reaction tuning by density control (RCM versus acyclic diene metathesis polymerization), and to applications of scCO(2) as a protective medium for basic amine functions. The latter phenomenon is explained by the reversible formation of the corresponding carbamic acid as evidenced by (1)H NMR data obtained in compressed CO(2). Together with its environmentally and toxicologically benign character, these unique physicochemical features sum up to a very attractive solvent profile of carbon dioxide for sustainable synthesis and production. 相似文献
17.
超临界二氧化碳介质中有机化学反应研究 总被引:3,自引:0,他引:3
综述了本研究小组近年来在超临界二氧化碳介质中过渡金属催化的有机化学反应的研究结果,主要包括烯烃和炔烃的羰基化反应、氧化反应、自由基反应、低聚反应。 相似文献
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A. L. Novozhilov V. G. Bamburov N. N. Fedotova 《Russian Journal of Inorganic Chemistry》2007,52(11):1679-1681
The solubility of CO2 in the series of molten alkali-metal nitrates is volumetrically measured on improved equipment, and the thermodynamic characteristics of dissolution are calculated. 相似文献
20.
Wang J Khlobystov AN Wang W Howdle SM Poliakoff M 《Chemical communications (Cambridge, England)》2006,(15):1670-1672
A facile and efficient method has been developed for coating MWNTs with solvent resistant polymer in scCO2, which permits the selective deposition of high molecular weight fluorinated graft poly(methyl vinyl ether-alt-maleic anhydride) polymer onto MWNTs in scCO2 under 100-170 bar at 40 degrees C and forms quasi one-dimensional nanostructures with conducting cores and insulating surfaces. 相似文献