Derivatives In Supercritical Carbon Dioxide Research Articles

Computation of the Solubility of 1,2,4-Thiadiazole Derivatives in Supercritical Carbon Dioxide

Computation of the Solubility of 1,2,4-Thiadiazole Derivatives in Supercritical Carbon Dioxide

A new semi empirical model for the solubility of dyestuffs in supercritical carbon dioxide

Solubility determination and prediction of azobenzene and anthraquinone derivatives in supercritical carbon dioxide (ScCO2) is a challenging and tedious task. Therefore, proper prediction of these solutes are quite important for application of ScCO2 technologies to dyeing industries. In this work, a new semi-empirical model is developed to correlate industrially important dye compounds solubility in ScCO2. The proposed model successfully correlated solute solubility of 22 industrial dye compounds in supercritical carbon dioxide (ScCO2). The correlating ability of the new model is compared with 16 existing literature solubility models in terms of various statistical parameters (AARD, R2, adj. R2, SSE, and RMSE). Furthermore, Akaike’s information criterion was employed to evaluate the relative goodness of the model. We found that the proposed model is correlating better than existing models considered.

Solubility of Anthraquinone Derivatives in Supercritical Carbon Dioxide: New Correlations.

Solubility of several anthraquinone derivatives in supercritical carbon dioxide was readily available in the literature, but correcting ability of the existing models was poor. Therefore, in this work, two new models have been developed for better correlation based on solid–liquid phase equilibria. The new model has five adjustable parameters correlating the solubility isotherms as a function of temperature. The accuracy of the proposed models was evaluated by correlating 25 binary systems. The proposed models observed provide the best overall correlations. The overall deviation between the experimental and the correlated results was less than 11.46% in averaged absolute relative deviation (AARD). Moreover, exiting solubility models were also evaluated for all the compounds for the comparison purpose.

Modelling of solubility of vitamin K3 derivatives in supercritical carbon dioxide using cubic and SAFT equations of state

In this work, the cubic Peng–Robinson and two versions of the SAFT (-HR and -VR Mie) equations of state are applied to study the solubility of six vitamin K3 derivatives in supercritical carbon dioxide. For these molecules, most of their thermophysical properties are unknown, hence, group contribution methods are applied to estimate the needed properties involved in the computation of solubility as well as the parameters of the equations of state. The performance of the equations of state to describe bulk densities, as well as the ability to correlate the experimental solubility of the compounds and their relationship with the molecular structure is studied. It is found that all the equations of state describe acceptably the density in the supercritical region of interest, but the solubility prediction from the SAFT-VR Mie model presents the best performance.

The solubility correlation of azobenzene derivatives in supercritical carbon dioxide: a short review

This short review highlights the solubility and correlation of four azobenzene derivatives, which have similar chemical structures, available in the literature. At the same phase equilibrium (at the temperature of 353.15 K), the solubilities of four azobenzene derivatives in supercritical carbon dioxide followed in the order of Disperse Red 82 > Disperse Red 13 > Disperse Blue 79:1 > Disperse Red 1. Five different kinds of density-based models were used to correlate the solubility data. Moreover, the solubilities of four azobenzene derivatives were also correlated thermodynamically by the model of the regular solution with the Flory–Huggins theory. It was found the Sung-Shim model (four parameters) has the lowest median AARD of 12.02 % of the solubility data over the entire conditions.

Solubility of 1-aminoanthraquinone and 1-nitroanthraquinone in supercritical carbon dioxide

The solubility of 1-aminoanthraquinone (Smoke Orange G) and 1-nitroanthraquinone in supercritical carbon dioxide (scCO2) was measured at the temperatures (323.15, 353.15 and 383.15)K and over the pressure range of (12.5–25.0)MPa by a flow type apparatus. Mole fraction solubility of 1-aminoanthraquinone, 3.51×10−5, was significantly higher than that of 1-nitroanthraquinone, 2.52×10−5, as compared at 383.15K and 25MPa. It was found that amino group in 1-aminoanthraquinone effects to enhance the solubility of anthraquinone derivatives in supercritical carbon dioxide in comparison with nitro group in 1-nitroanthraquinone. Seven different kinds of semi-empirical models, expressed in terms of CO2 density, were used to correlate the experimental results. Moreover, the solubilities of anthraquinone derivatives were analysed thermodynamically by the regular solution model with the Flory–Huggins theory and by the Peng–Robinson equation of state with a modification of Stryjek and Vera (PRSV-EOS). Good agreement with slightly less than 15 per cent of relative deviation between the experimental and calculated solubilities of the anthraquinone derivatives was obtained.

Experimental solubilities of two lipid derivatives in supercritical carbon dioxide and new correlations based on activity coefficient models

Solubilities of 10-undecen-1-ol and geranyl butyrate were determined and correlated based on new models by combinations of solution/association theories.

Solubilities and partial molar volumes of three bis(2-ethoxyethyl) ethanedioate derivatives in supercritical carbon dioxide

Three new CO2-philic bis(2-ethoxyethyl) ethanedioate derivatives, bis(2-(2-methoxyethoxy)ethyl) ethanedioate (compound 1), bis(2-(2-ethoxyethoxy)ethyl) ethanedioate (compound 2), and bis(2-(2-butoxyethoxy)ethyl) ethanedioate (compound 3), were designed and synthesized and their solubilities in supercritical carbon dioxide (scCO2) were then measured at different temperatures (313, 323, 333)K over the pressure range (8.9 to 13.9)MPa. The measured solubility data were correlated with five different theoretical semi-empirical models (Chrastil, kJ, SS, MST, JCF) and satisfactory agreements were obtained. The JCF model provided the best fit and the lowest average absolute relative deviation (AARD) varied from (3.58 to 6.80)%. Furthermore, the partial molar volumes of three compounds in the supercritical phase were also calculated according to the Kumar and Johnston theory, and the values were between −(19105 and 3510)cm3·mol−1.

Solubility of anthraquinone derivatives in supercritical carbon dioxide

Abstract Solubility data of 1-amino-4-hydroxyanthraquinone and 1-hydroxy-4-nitroanthraquinone in supercritical carbon dioxide have been measured at the temperature of 323.15, 353.15 and 383.15 K and over pressure ranges 12.5–25.0 MPa by a flow – type apparatus. The solubility of 1-amino-4-hydroxyanthraquinone was significantly higher than that of 1-hydroxy-4-nitroanthraquinone. It was found that amino group in 1-amino-4-hydroxyanthraquinone can enhance the solubility of anthraquinone derivatives in supercritical carbon dioxide compared with nitro group in 1-hydroxy-4-nitroanthraquinone. The experimental results were correlated satisfactorily by four types of the density-based models, namely, Mendez-Santiago–Teja, Kumar–Johnston, Chrastil, and Sung–Shim. Moreover accurate representation of the solubility of anthraquinone dyestuffs was obtained by the regular solution model with the Flory–Huggins theory as well as the Peng–Robinson equation of state modified by Stryjek and Vera with the van der Waals one-fluid mixing rule.

Correlation of solid solubility of 1‐hydroxy‐9,10‐anthraquinone derivatives in supercritical carbon dioxide

ABSTRACTIn this study, the solid solubilities of four 1‐hydroxy‐9,10‐anthraquinone derivatives (HAQs) in supercritical carbon dioxide (CO2) have been correlated using a two solid‐dependent parameter solution model developed from the regular solution model coupled with the Flory–Huggins equation. The correlated results show satisfactory agreement with the experimental data. In addition, with appropriate model simplification and generalization, a generalized solution model is proposed in this study to predict the solubility behavior of HAQs in supercritical CO2. By applying our generalized solution model, satisfactory calculated results are obtained and the average deviation of predicted solubilities is only about 10%. © 2014 Curtin University of Technology and John Wiley & Sons, Ltd.

Solubilities and partial molar volumes of new CO2-philic propane derivatives in supercritical carbon dioxide

Three new potent CO2-philic propane derivatives were designed and synthesized. Their structures were characterized by NMR, FTIR, and elemental analysis. Phase behavior of the three compounds was investigated at T=(313, 323, 333, 343 or 353)K and pressures from (7.7 to 12.1)MPa in supercritical carbon dioxide. The measured solubility data were correlated using three models: Chrastil, Sung and Shim (SS), and Jouyban–Chan–Foster (JCF) semi-empirical models, and satisfied agreements were obtained. Solubility data were also utilized to estimate the partial molar volume V¯2 for each compound in the supercritical phase using the theory developed by Kumar and Johnston.

Solubility of 2-methyl-2-propyl-1,3-propanediol and its derivatives in supercritical carbon dioxide: measurement and mathematical modeling

The modifications for the end group of 2-methyl-2-propyl-1,3-propanediol (compound 1) were achieved by reacting with methyl oxalyl chloride and methyl malonyl chloride to generate two new CO2-philic compounds: bis(methoxyoxalic)-2-methyl-2-propyl propylene glycol ester (compound 2) and bis(methoxymalonic)-2-methyl-2-propyl propylene glycol ester (compound 3). After that, the solubilities of these three compounds were tested and compared in supercritical carbon dioxide (scCO2) within the temperature range of (313 to 353)K and in the pressure range of (9.3 to 19.0)MPa. The influence of molar mass and end group on the solubility of compound was also studied. In addition, the experimental solubility data were correlated according to Bartle, Chrastil and JCF model, and good consistencies were obtained. The average absolute relative deviation (AARD) of the measured values were (5.83, 8.98, 8.77)% when using Bartle’s method, (10.95, 7.53, 7.55)% for Chrastil’s method, and (6.89, 4.10, 4.19)% for the JCF method, respectively. It is obvious that the JCF model was proven to be the best model because it had more adjustable parameters of temperature and pressure. Finally, the partial molar volumes V¯2 for each compound in the supercritical phase were estimated in accordance with Kumar and Johnston’s theory.

Solubilities and partial molar volumes of 1-methypropanedioate derivatives in supercritical carbon dioxide

In present study, five new CO2-philic 1-methypropanedioate derivatives containing nonfluorous alkyl groups had been designed and synthesized. The solubilities of these compounds in supercritical carbon dioxide (scCO2) were investigated with a static analytical method at the temperature from 323K to 343K and in the pressure range of 9.3–13.7MPa. All compounds showed high solubilities in supercritical CO2 at easily accessible temperatures and pressures. To correlate the experimental data, two density-based models proposed by Bartle and Chrastil were investigated. The correlation results showed good self-consistency between the calculated and the measured values, which were in the range of 7.79–21.99% by Bartle model and 4.09–11.15% by Chrastil model. Additionally, according to the Kumar and Johnston theory, the partial molar volume V¯2 of each compound in scCO2 was also calculated and the results were between −10788.4 and −1585.84.

Application of a new amidophosphite ligand to Rh‐catalyzed asymmetric hydrogenation of β‐dehydroamino acid derivatives in supercritical carbon dioxide: Activation effect of protic co‐solvents

New chiral amidophosphite ligand was synthesized and tested in the Rh-catalyzed asymmetric hydrogenation of (Z)-β-(acylamino)acrylates in protic solvents and supercritical carbon dioxide (scCO(2) ) The catalytic performance is affected greatly by the acidity of the solvents. Better enantioselectivity (up to 88% ee) was achieved in scCO(2) containing 1,1,1,3,3,3-hexafluoro-2-propanol, compared to neat protic solvents.

Solubilities of Benzene Derivatives in Supercritical Carbon Dioxide

The solubilities of benzene derivatives in supercritical carbon dioxide was determined by the saturation method over the pressure range (9.5 to 14.5) MPa. The solubilities were determined at (308 and 313) K for 1-chloro-2,4-dinitrobenzene and (308, 318, and 328) K for m-dinitrobenzene. At 308 K, the solubility (in mole fraction) of 1-chloro-2,4-dinitrobenzene varied from (2.83 to 5.88)·10−3 while the solubility of m-dinitrobenzene increased from (2.05 to 5.54)·10−3 as the pressure increased from (9.5 to 14.5) MPa. However, the solubilities of both compounds decreased with increasing temperature. Models based on the solubility parameter and semiempirical models such as the Méndez-Santiago−Teja model, the Gordillo model, and the association model, were used to correlate the experimental solubility data for the benzene derivatives.

Heterogeneous palladium-catalyzed telomerization of myrcene with glycerol derivatives in supercritical carbon dioxide: a facile route to new building blocks

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Asymmetric hydrogenation with the use of chiral carborane amidophosphite derivatives in supercritical carbon dioxide and CH2Cl2

New chiral carborane-containing amidophosphites containing the BINOL fragment (BINOL stands for 2,2′-dihydroxy-1,1′-binaphthyl) have been synthesized. The study of efficiency of these compounds as ligands in the Rh-catalyzed asymmetric hydrogenation of enamides in supercritical carbon dioxide (scCO2) and CH2Cl2 showed that enantioselectivity of the process is considerably higher in scCO2.

Synthesis of chiral amino acid derivatives in supercritical carbon dioxide using Rh-PipPhos catalyst

PipPhos ligand was used in the asymmetric Rh-catalysed hydrogenation of N-acyldehydroamino acid esters in supercritical carbon dioxide with enantioselectivities attained up to 97%. The catalytic performance is affected greatly by temperature and both hydrogen and total pressures.

Solubilities of some 9,10-anthraquinone derivatives in supercritical carbon dioxide: A cubic equation of state correlation

The solubilities of some 9,10-anthraquinone derivatives in supercritical carbon dioxide were measured at 308, 318, 328, 338 and 348 K over the pressure range from 15.2 to 35.5 MPa, using a simple static method. The solubilities were found to be in the range 8.1 × 10 −6 and 5.8 × 10 −4 mole fractions. The experimental results were correlated by the Peng–Robinson equation of state (PR-EOS) with the one and two adjustable parameter conventional mixing rules. The physical properties of pure components, critical temperatures and pressures and sublimation pressures were estimated using the group contribution methods. The proposed model was able to correlate the experimental solubility data with good agreement by adjusting binary interaction parameters k ij and l ij . Deviations of calculated results from experimental data were presented as averaged absolute relative deviation percentage, AARD (%), the values of which being in the range of 3.9–13.9%.

Linear and nonlinear quantitative structure–property relationship models for solubility of some anthraquinone, anthrone and xanthone derivatives in supercritical carbon dioxide

A quantitative structure–property relation (QSPR) study was conducted on the solubility in supercritical fluid carbon dioxide (SCF-CO 2) of some recently synthesized anthraquinone, anthrone and xanthone derivatives. The data set consisted of 29 molecules in various temperatures and pressures, which form 1190 solubility data. The combined data splitting-feature selection (CDFS) strategy, which previously developed in our research group, was used as descriptor selection and model development method. Modeling of the relationship between selected molecular descriptors and solubility data was achieved by linear (multiple linear regression; MLR) and nonlinear (artificial neural network; ANN) methods. The QSPR models were validated by cross-validation as well as application of the models to predict the solubility of three external set compounds, which did not have contribution in model development steps. Both linear and nonlinear methods resulted in accurate prediction whereas more accurate results were obtained by ANN model. The respective root mean square error of prediction obtained by MLR and ANN models were 0.284 and 0.095 in the term of logarithm of g solute m −3 of SCF-CO 2. A comparison was made between the models selected by CDFS method and the conventional stepwise feature selection method. It was found that the latter produced models with higher number of descriptors and lowered prediction ability, thus it can be considered as an over-fitted model.