Solubility of chemical warfare agent simulants in supercritical carbon dioxide: experiments and modeling

Solubility data are reported for ethyl phenyl sulfide (EPS) and 2-chloroethyl ethyl sulfide (CEES) in CO₂ at temperatures from 25 to 100 °C. These two sulfide-based compounds are homomorphs for chemical warfare agents (CWAs). Both sulfide–CO₂ mixtures exhibit type-I phase behavior. The maximum in the 100 °C isotherm is approximately 2600 psia for the CEES–CO₂ system and approximately 3400 psia for the EPS–CO₂ system. The Peng–Robinson equation of state (PREOS) is used to model both sulfide–CO₂ mixtures as well as the phase behavior of the 2-chloroethyl methyl sulfide (CEMS)–CO₂ system previously reported in the literature. The Joback–Lydersen group contribution method is used to estimate the critical temperature, critical pressure, and acentric factor for the sulfides. Semi-quantitative estimates of the phase behavior are obtained for the CEES–CO₂ and EPS–CO₂ systems with a constant value of k_ij, the binary interaction parameter, fit to the 75 °C isotherms. However, very poor fits are obtained for the 2-chloroethyl methyl sulfide–CO₂ system regardless of the value of k_ij. On the basis of the high solubility of EPS and CEES in CO₂, supercritical fluid (SCF)-based technology could be used to recycle or recover chemical warfare materials.     

Measurement and calculation of solubility of quinine in supercritical carbon dioxide

Solubility of quinine in supercritical carbon dioxide(SCCO_2) was experimentally measured in the pressure range of 8 to 24 MPa, at three constant temperatures: 308.15 K, 318.15 K and 328.15 K. Measurement was carried out in a semi-dynamic system. Experimental data were correlated by iso-fugacity model(based on cubic equations of state, CEOS), Modified Mendez–Santiago–Teja(MST) and Modified Bartle semi-empirical models. Two cubic equations of state: Peng–Robinson(PR) and Dashtizadeh–Pazuki–Ghotbi–Taghikhani(DPTG) were adopted for calculation of equilibrium parameters in CEOS modeling. Interaction coefficients(k_(ij) l_(ij)) of van der Waals(vdW) mixing rules were considered as the correlation parameters in CEOS-based modeling and their contribution to the accuracy of model was investigated. Average Absolute Relative Deviation(AARD) between correlated and experimental data was calculated and compared as the index of validity and accuracy for different modeling systems. In this basis it was realized that the semi-empirical equations especially Modified MST can accurately support the theoretical studies on phase equilibrium behavior of quinine–SCCO_2 media. Among the cubic equations of state DPGT within two-parametric vd W mixing rules provided the best data fitting and PR within one-parametric vd W mixing rules demonstrated the highest deviation respecting to the experimental data. Overall, in each individual modeling system the best fitting was observed on the data points attained at 318 K, which could be perhaps due to the moderate thermodynamic state of supercritical phase.     

Density correlation of solubility of C. I. disperse orange 30 dye in supercritical carbon dioxide

The solubility of C. I. Disperse Orange 30 (O30) dye in CO₂ has been measured by using a closed-loop (batch) solid-fluid equilibrium apparatus at temperatures between 313 and 393 K and at pressures between 11 and 33 MPa. Kumar and Johnston’s equation based on Chrastil’s concept has been used to describe the experimental solubility data. The solubility versus density plot appears much simpler than the solubility versus pressure plot. The isotherms are nearly straight and parallel to each other, as seen in the previous studies. Peng-Robinson equation of state (PR EOS) has also been used successfully in modeling the dye solubility in supercritical carbon dioxide as a function of pressure or density of the fluid phase. The validity of this method has been verified by the vapor pressure calculation. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

A new model for predicting solute solubility in supercritical fluids based on the Wilson equation

In this work, a new model based on the Wilson solution theory was proposed for predicting the solubility of solids in supercritical fluid (SCF) with and without cosolvent(s) of binary and ternary systems via computation of activity coefficients. For binary systems the model contains two adjustable parameters, while for ternary systems there are four adjustable parameters. The calculated results of the proposed model were compared with that of the literature models, and it is shown that the proposed model is a more accurate one.     

Modeling of the solubility of solid solutes in supercritical CO<Subscript>2</Subscript> with and without cosolvent using solution theory

In this work, regular solution theory was applied to study the solubility of solids in a supercritical fluid (SCF) with and without cosolvent, and a new model for binary and ternary systems was proposed. The activity coefficient can be obtained from the model and the solubility can then be calculated easily. For a binary system there are two adjustable parameters and for a ternary system, four adjustable parameters; the parameters are related to the interactions between molecules in solution. The proposed model was compared with the HSVDW1 and HSVDW2 models. The calculated results show that the proposed model is more accurate, and the AAD for the three models is 4.5%, 7.9% and 18.5%, respectively. The model was further used to correlate the solubility data of 2-naphthol in SC CO₂ with and without cosolvent measured by us before, and the overall AAD is 3.23%.     

Mutual solubility study for 94.2:5.8 of ethanol to octane with supercritical carbon dioxide solvent

Solubility data of a mixture containing 94.2% ethanol and 5.8% octane was measured in carbon dioxide solvent using a high-pressure type phase equilibrium apparatus at pressures up to 103.5 bar and at temperature of 75 °C. The results showed that considerable separation was not achieved in this ethanol and octane ratio. However, the experimental data were then compared with the theoretical data which were obtained from two models which are regular solution theory and Redlich-Kwong equation of state. Regular solution theory is employed to each phase by applying activity coefficient expressions. Redlich-Kwong equation of state is employed to the vapor phase and then with applying fugacity coefficient, liquid phase data is obtained. The regular solution theory as a novel model approach has been found to be encouraging for the prediction of phase equilibria solubilities. It concluded that the regular solution theory model could predict two phases equilibrium data better than Redlich-Kwong equation of state.     

A study on the predictive capability of the SAFT-VR equation of state for solubility of solids in supercritical CO2

In this study, a version of the SAFT-VR equation of state based on the Yukawa potential is used for modeling the solubility of diverse organic compounds, mostly drugs, in supercritical carbon dioxide. Prior to any calculations, the SAFT parameters of pure CO₂ were obtained by correlating the vapor–liquid equilibrium data within the range of 220–300 K. The validity of these parameters was examined by applying them in prediction of the compressibility factor and density in wide temperature and pressure ranges. Due to dependence of the rest of the calculations on the sublimation pressure and lack of its experimental values for most of the solids, it was estimated through two main approaches: application of a group contribution method prior to correlating the solubility data, and calculating it in relation with temperature while correlating the solubility data. For each compound, the first isothermal set of the available experimental data was used for correlation and the rest were predicted. Adopting the same procedure for three empirical models and comparing the resulting deviation percents validated the superiority and high capability of this equation of state in correlating and particularly predicting the solubility in supercritical region. The predicted densities were also in very good agreement with the available experimental values.     

Modeling of drug solubility in supercritical carbon dioxide using equation of state based on hole theory with molecular surface charge density

Equation of state based on hole theory with molecular surface charge density was developed for the modeling of drug solubility in supercritical carbon dioxide. In the hole theory, the density change of supercritical carbon dioxide can be represented by the number of holes in the system. The molecular interaction energy parameter was estimated using the interactions of segments on the molecular surface given by a quantum calculation using conductor-like screening model. The only one parameter, coordination number around a molecule was fitted to the experimental data of the drug solubility in supercritical carbon dioxide. The solubilities of the eighteen drugs in supercritical carbon dioxide were modeled by the equation of state with the molecular surface charge density. The effect of the molecular pair for the coordination number on the correlated results was investigated. It is found that the results using the fitted parameter of the solute–solute pair coordination number result in the modeling performance better than those of carbon dioxide–solute coordination number. The results of the modeling of drug solubility in supercritical carbon dioxide are compared with the experimental data. The average absolute relative deviation between the experimental and calculated results of the solubility for the drug composed of C, H and O atoms acetylsalicylic acid, benzoic acid, ferulic acid, (S)-naproxen, p-benzoquinone, propyl gallate, salicylic acid and vanillic acid is 0.38 smaller than those for compounds including N, F, I and S atoms, amical-48, benzocaine, caffeine, carbamazepine, (±)-flurbiprofen, methimazole, phenazopyridine, theobromine, theophylline and uracil, 0.59.     

Effect of menthol as solid cosolvent on the solubility enhancement of clozapine and lamorigine in supercritical CO2

The solubilities of mixed clozapine and menthol also lamotrigine and menthol in supercritical carbon dioxide were determined at 313 and 323 K and over pressure ranging from 123 to 337 bar. The solubility of both solutes with solid cosolvent system is observed to increase relative to the value of the corresponding without solid cosolvent system. As compared with their respective binary system (without solid cosolvent), the mixed clozapine (with solid cosolvent) solubility enhancement greatly by around 56 times and the lamotrigine one does by approximately eight times. In presence of menthol these chemicals have solubilities with values ranging from 1.88 × 10⁻⁴ to 4.48 × 10⁻⁴ (clozapine) and 0.09 × 10⁻⁴ to 0.36 × 10⁻⁴ (lamotrigine) mole fraction. The solubility data were correlated using five semi-empirical density-based models (Chrastil, Bartle, K-J, M-T and Thakur models). Correlated results for clozapine with the Chrastil, M-T, K-J, and Bartle models and for lamotrigine with the Chrastil, M-T and Bartel models are in excellent agreement with the experimental data.     

Dye solubility in supercritical carbon dioxide. Effect of hydrogen bonding with cosolvents

The use of supercritical carbon dioxide is emerging as a potential method for achieving pollution-free dyeing. An important factor in supercritical fluid dyeing is the solubility of the dye in supercritical carbon dioxide. Our measurements show that the solubility of C. I. Disperse Red-60 dye in supercritical carbon dioxide is significantly enhanced upon addition of polar csolvents : ethanol and acetone. The solubility enhancement is attributed to the formation of hydrogen bonds between cosolvent and dye molecules. Observed solubility behavior is correlated using dilute-solution theory with lattice-fluid-hydrogen-bonding model. Needed physical and hydrogen-bonding molecular parameters are estimated using the experimental data.     

Experimental investigation and modeling of the solubility of carvedilol in supercritical carbon dioxide

This study was aimed to measure the solubility of carvedilol in the temperature and pressure ranges of 308⿿338 K and 160 bar to 400 bar, respectively. In this direction, a homemade high pressure visual equilibrium cell was used to measure the solubility of carvedilol using a static method coupled with gravimetric technique. The results revealed that the carvedilol solubility was ranged between 1.12 ÿ 10^⿿5 and 5.01 ÿ 10^⿿3 based on the mole fraction (mole of carvedilol/mole of carvedilol + mole of CO₂) in this study as the temperature and pressure was changed. Finally, the results were correlated using four density-based semi-empirical correlations including Chrastil, Mendez⿿Santiago⿿Teja (MST), Bartle et al., and Kumar and Johnston (K-J) models. Results revealed that although the K-J model leads to the lowest average absolute relative deviation percent (AARD %) of 6.27%, but it could not be considered as the most accurate correlation since all the used four correlations introduces AARD % of about 6⿿10% which may be in the same range as the experimental error.     

平均吸引势模型状态方程用于固体在超临界流体中溶解度的计算

基于膨胀液体概念，把超临界流体看作是被气体膨胀了的液体，并假设体系的分子吸引势为范德华气体和凝聚液体吸引势的体积平均值、导出了一个平均吸引势模型状态方程。该方程较好地关联了纯溶剂蒸汽压及超临界二氧化碳的Ｐ－Ｖ－Ｔ关系；并关联了１４种固体溶质在超临界二氧化碳中的溶解度数据，结果优于ＲＫ、ＳＲＫ及ＰＲ方程。     

Cetirizine solubility in supercritical CO2 at different pressures and temperatures

A simple static technique was used to obtain the solubility of cetirizine in supercritical carbon dioxide. The solubility measurements were performed at temperatures and pressures ranging from 308.15 to 338.15 K and 160 to 400 bar, respectively; resulting in mole fractions in the 1.05 × 10⁻⁵ to 4.92 × 10⁻³ range. The Chrastil, Bartle, Kumar & Johnston and the Mendez-Santiago and Teja (MST) models were used to correlate the experimental data. The calculated solubilities showed good agreement with the experimental data in the temperature and pressure ranges studied.     

Determination and calculation of solubility of bisphenol A in supercritical carbon dioxide

Supercritical fluid technology (SFT) as a new technique is very important for clean environment and removal of chemical pollutants. The lack of solubility data of solid solute in certain supercritical fluid is a great obstacle to the successful implementation of SFT. In this work, the solubility of bisphenol A in supercritical carbon dioxide was determined by the dynamic method at the temperatures ranging from 308 to 328 K and pressure range of 11.0–21.0 MPa. The effects of temperature and pressure on solubility were analyzed according to molecular motion theory. The solubility data were correlated using eight different semi-empirical models (Chrastil, Adachi–Lu, Kumar–Johnston, Tang, Sung–Shim, Bartle, Méndez Santiago–Teja and Yu). The comparison between different models was discussed. The thermodynamic properties (total enthalpy ΔH, enthalpy of sublimation Δ_subH and enthalpy of solvation Δ_solvH) of the solid solute were obtained.     

Evaluation of density-based models for the solubility of solids in supercritical carbon dioxide and formulation of a new model

Many models have been developed to calculate supercritical solubility behavior and most can be either a semi-empirical relationship or based on an equation of state. In this work, density-based, semi-empirical models were evaluated in terms of their ability to accurately correlate solid solubility in supercritical carbon dioxide. The models considered were the methods of Chrastil, del Valle and Aguilera, Adachi and Lu, Méndez-Santiago and Teja, and Bartle. Six binary systems (solid + supercritical carbon dioxide), each with three isotherms, were selected for this evaluation. The average error was calculated for all 18 isotherms with each of the models evaluated. The solid compounds used in this study were naphthalene, anthracene, fluorene, hydroquinone, 1,5-naphthalenediamine, and cholesterol. The solubility data were obtained from literature. Of the previously mentioned models, the Adachi-Lu and del Valle-Aguilera equations provided, in general, lower average error than the other models. Since the Adachi-Lu equation and the del Valle-Aguilera equation correct for different effects, a new model is proposed in this work as a combination of the previous two methods. The proposed equation provided the least overall average error compared to all other models considered in this study. The new model is particularly useful when the reduced density of the solvent is below 1 where previous models tend to fail. This work also emphasizes on the advantages of expressing density-based models in dimensionless form to avoid dimensional inconsistencies in Chrastil-type models. One of the benefits, for example, is that parameters obtained by different authors can be readily compared, regardless of the units used.     

Prediction of solute solubility in supercritical carbon dioxide: A novel semi-empirical model

Solubility data of solutes in supercritical fluids (SCF) are crucial for designing extraction processes, such as extraction using SCF or micronization of drug powders. A new empirical equation is proposed to correlate solute solubility in supercritical carbon dioxide (SC CO₂) with temperature, pressure and density of pure SC CO₂. The proposed equation is ln y₂ = J₀ + J₁P² + J₂T² + J₃ ln ρ where y₂ is the mole fraction solubility of the solute in the supercritical phase, J₀ − J₃ are the model constants calculated by least squares method, P (bar) is the applied pressure, T is temperature (K) and ρ is the density of pure SC CO₂. The accuracy of the proposed model and three other empirical equations employing P, T and ρ variables was evaluated using 16 published solubility data sets by calculating the average of absolute relative deviation (AARD). The mean AARD for the proposed model is 7.46 (±4.54) %, which is an acceptable error when compared with the experimental uncertainty. The AARD values for other equations were 11.70 (±23.10), 6.895 (± 3.81) and 6.39 (±6.41). The mean AARD of the new equation is significantly lower than that obtained from Chrastil et al. model and has the same accuracy as compared with Bartle et al. and Mèndez-Santiago–Teja model. The proposed model presents more accurate correlation for solubility data in SC CO₂. It can be employed to speed up the process of SCF applications in industry.     

Improved Density Correlation for Supercritical CO2

An experimental apparatus was designed to measure accurately the density of supercritical CO₂ in wide temperature and pressure ranges. Based on experimental results, the curves for CO₂ density as function of pressure at certain temperatures were divided into linear‐growth, rapid‐growth, and slow‐growth intervals. The relative error between the experimental and calculated density values for a number of frequently used equations of state was evaluated. These equations were corrected after analyzing the accuracy of each equation in the different intervals. A new method for calculating the density of supercritical CO₂ that includes 28 constant parameters is proposed to determine the density at a known temperature and pressure.     

Estimation of H2S solubility in ionic liquids using a rigorous method

Prediction of acid gases solubilities in ionic liquids (ILs), have recently emerged as promising mediums for refining of natural gas, using powerful paradigms is of great importance from technical and economical point of view. In this respect, this study aims at appraising the effectiveness of one of the new generation soft computing methodologies called gene-expression programming (GEP) for estimating the hydrogen sulfide (H₂S) solubility in ionic liquids (ILs). A total data set of 465 experimental data belonging to 11 ionic liquids, which gathered from literatures, were used to develop a general correlation. The temperature and pressure accompanied with acentric factors and critical temperature and pressure of ILs were used as independent input variables, while H₂S solubility as dependent output variables. The modeling results showed the coefficient of determination (R²) of 0.9902 and 0.0438% mean absolute relative error (MARE) for the predicted solubilities from the corresponding experimental values. Therefore, the model is comprehensive and accurate enough to be used to predict the H₂S solubility in various ILs. In addition, the GEP-model predictions were compared with the outputs of two well-known engineering approaches named Soave–Redlich–Kwong (SRK) and Peng–Robinson (PR). Results showed that the proposed evolutionary-based method was more accurate than the widely used aforementioned thermodynamic models.     

Ternary solubility of mono- and di-tert-butyl ethers of glycerol in supercritical carbon dioxide

Using a continuous flow apparatus, the ternary solubility of mono- and di-tert-butyl ethers of glycerol (MTBG and DTBG, respectively) in supercritical carbon dioxide was measured at the temperatures of 313.15, 333.15, and 348.15 K; a pressure range of 80-200 bar; and an expanded gas flow rate of 180 ± 10 mL min⁻¹ at average laboratory temperature of 300.15 K and pressure of 0.89 bar. The ternary solubility of the ethers at the constant temperatures of 333.15 and 348.15 K increased with increasing pressure up to the crossover point (i.e., 152 bar for MTBG and 170 bar for DTBG). MTBG exhibited a higher solubility than DTBG in scCO₂. The experimental data for the ternary solubility of MTBG and DTBG were correlated using the Bartle equation.