Journal of Chemical & Engineering Data最新文献

Here, we presenta simple and computationally efficient procedureto determine the eutectic temperatures of ideal binary, ternary, andhigher-order mixtures, providing a quantitative reference for evaluatingdeep eutectic solvent (DES) behavior. In the DES literature, ternarysystems are often simplified as pseudo-binaries by fixing the molarratio of two components and varying only the third along a fixed-compositionline (isopleth). Although this reduces the experimental effort, itrestricts liquidus mapping to a single compositionalpathway and may fail to identify the global ideal eutectic. In contrast,our implementation solves the classical ideal liquidus equations for all components, assuming Raoult-law ideality and pure,mutually immiscible solid phases. Using pure-component melting temperaturesand molar fusion enthalpies, the method enables multidimensional liquidus-surface mapping. The root-finding implementationwas verified against analytical symmetric-mixture solutions, independent80-digit calculations, a MATLAB implementation, permutation tests,3,521 stress-test systems, and published benchmarks. All stress-testsystems converged, and published ideal eutectic temperatures werereproduced within 0.7 K. Application to literature-reported binaryand ternary mixtures further showed that comparison with the globalideal eutectic combines an apparent local thermal deviation with anonnegative ideal-composition penalty. The framework therefore providesa transparent and extensible ideal-equilibrium baseline for multicomponenteutectic screening.

Biodieselis a renewable, green alternative fuel derived from diversefeedstocks and consisting primarily of fatty acid esters. In thisstudy, the isobaric specific heat capacities of methyl decanoate andethyl decanoate were measured using flow calorimetry at temperaturesfrom 313 to 453 K and pressures up to 10 MPa. The measurements wereconducted along isotherms with a 20 K interval, yielding 88 experimentaldata per substance with a relative expanded uncertainty of 0.95% (k = 2). At atmospheric pressure, the absolute average deviation(AAD) between the measured values and literature data was 0.47% formethyl decanoate and 0.25% for ethyl decanoate. For ethyl decanoateunder high pressure, the AAD was 0.09%. Based on the experimentalresults, correlating equations as a function of pressure and temperaturewere developed, yielding mean absolute deviations of 0.28% and 0.25%between the calculated and experimental values for methyl decanoateand ethyl decanoate, respectively.

In view of the high calcium characteristicsof deep brine and thetemperature change during its mining, transportation, and storageprocess, the solid–liquid phase equilibria of the quaternarysystem Li⁺, K⁺, Ca²⁺ // Cl^––H₂O at 323.2 and 348.2 K were studied by the isothermaldissolution equilibrium method, and the multitemperature phase diagramswere compared with the literature data at 273.2 and 298.2 K. The resultsshow that the crystal forms of lithium chloride and calcium chloridechange as follows: LiCl·2H₂O (273.2 K) → LiCl·H₂O (≥298.2 K); CaCl₂·6H₂O(273.2 K) → CaCl₂·6H₂O + CaCl₂·4H₂O (298.2 K) → CaCl₂·2H₂O (≥323.2 K); LiCl·CaCl₂·5H₂O (≤298.2 K) was formed at low temperature, and KCl·CaCl₂ (≥323.2 K) was formed at high temperature. With theincrease of temperature, the crystalline phase region of KCl decreases,and the crystalline regions of LiCl·H₂O and KCl·CaCl₂ increase. The above phase diagram reveals the temperaturestep-by-step control separation route of “high temperaturepreferential precipitation of KCl·CaCl₂, low temperatureextraction of potassium, high temperature extraction of lithium”,which provides a theoretical basis for the classification and utilizationof Li/K resources in high calcium deep brine.

Methyl tert-butyl ether (MTBE) is anexcellentadditive for gasoline. Because of the formation of an azeotropic mixtureby MTBE and methanol during its production, it is a challenge to separatethe azeotrope. To investigate the effect of hydrogen bond donor (HBD)functional groups on extraction performance, three choline chloride-baseddeep eutectic solvents (DESs) were prepared using ethylene glycol,ethanolamine and glycolic acid, which contain –OH, –NH₂, and –COOH, respectively. For separating the azeotropicmixture MTBE and methanol by an extraction process, liquid–liquidequilibrium (LLE) data for the pseudoternary mixtures MTBE + methanol+ DESs were ascertained at 298.15 K. Distribution coefficient (D) and selectivity (S) were derived andcompared among the different systems. The optimal DES ChCl:MEA attaineda distribution coefficient of 8.85 and a selectivity of 436.21. TheNRTL model was employed to regress the LLE data. The reliability ofthe binary parameters of the thermodynamic model was validated throughGibbs energy topology analysis. In addition, quantum chemical calculationsand molecular dynamics simulations were applied to investigate theinteractions underlying the differences in extractant performance.This multiscale analysis revealed hydrogen bonding Cl···OHplays a crucial function, while van der Waals interactions serve asa secondary contributing factor.

The world’sgrowing energy needs and the depletion of fossilfuels have driven demand for renewable alternatives, such as biofuels.Propan-1-ol is a valuable biofuel component; however, the presenceof water during its production remains a significant challenge. Aviable solution is liquid–liquid extraction to selectivelyrecover propan-1-ol from a water mixture. Ethyl acetate is considereda promising solvent due to its chemical stability, eco-friendly nature,moderate water immiscibility, and favorable density difference forphase separation in a water-propan-1-ol mixture. In this study, ternaryLLE measurements for water (1), propan-1-ol (2), and ethyl acetate(3) were conducted at 298.15, 313.15, and 328.15 K to evaluate ethylacetate as a solvent for extracting propan-1-ol. The selectivity andcapacity of the solvent were calculated. The experimental data weremodeled using the NRTL and UNIQUAC activity models, both of whichadequately describe the phase behavior, with NRTL slightly betterthan UNIQUAC. The group method of data handling (GMDH) neural networkwas also employed to complement the thermodynamic model, accuratelypredicting phase composition. The findings of this study show thatethyl acetate has excellent potential for selectively extracting propan-1-olfrom water, with the extraction efficiency increasing with temperature.

A low-cost, low-viscosity, easily synthesized, and environmentallyfriendly deep eutectic solvent (DES) was fabricated using acetamide(AA) and 1-amino-2-propanol (MIPA) as materials. Performance studiesdemonstrated that when the molar ratio of AA to MIPA was 1:5, thesystem exhibited a CO₂ adsorption capacity of 0.2198 g_CO2/g_DES at 303.15 K, at which condition the viscosityand density were measured to be 19.05 mPa·s and 0.9650 g·cm^–3. Furthermore, the desorption efficiency remainedat 94% after 5 adsorption–desorption cycles, indicating excellentcyclic stability. Through infrared spectroscopy, nuclear magneticresonance hydrogen spectrum, and quantum chemical calculations, itwas found that the DES was primarily stabilized by a hydrogen-bondednetwork between AA and MIPA molecules, with the amino groups in MIPAserving as the main active sites for the CO₂ reaction.The absorption process exhibited a synergistic mechanism combiningchemical adsorption (formation of carbamate) and physical adsorption.This study provides theoretical and experimental foundations for thedevelopment of efficient and recyclable CO₂ capture materials.

Theturbidity technology was employed to determine the solubility,supersolubility, and metastable zone width of Li₂CO₃ in the mixed solution of the LiCl–CaCl₂–NdCl₃–PrCl₃–FeCl₃ environment over a temperature span from 293.15 to 363.15K. The experimental data show that the solubility, supersolubility,and metastable zone width of Li₂CO₃ in a LiClsolution are mainly affected by temperature and concentration of LiClsolution. In addition, increasing the concentration of the Na₂CO₃ solution significantly alters the supersolubilityand metastable zone width of Li₂CO₃. The additionof impurity ions (Ca²⁺, Nd³⁺, Pr³⁺, Fe³⁺) noticeably increases the solubility, supersolubility,and metastable zone width of Li₂CO₃. The effectmechanism of impurity ions on the solubility, supersolubility, andmetastable zone width of Li₂CO₃ in solutionis the salting out of LiCl and salting in of CaCl₂, NdCl₃, PrCl₃, and FeCl₃. Overall, this researchprovides fundamental data for the industrial-scale manufacture ofLi₂CO₃ via crystallization technology.

In this study, the gravimetric method was applied tomeasure thesolubility of 4-isopropylbenzoic acid in 12 pure solvents (2-methoxyethanol,2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, methyl acetate,ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutylacetate, acetonitrile, and N,N-dimethylformamide(DMF)) at the temperature range of 278.15–323.15 K under atmosphericpressure. The experimental results showed that the solubility of 4-isopropylbenzoicacid had a significant positive correlation with temperature, andthe mole fraction solubility (x) order of 4-isopropylbenzoicacid at the temperature of 298.15 K was: DMF (0.4498) > 2-propoxyethanol(0.2474) > 2-butoxyethanol (0.2382) ≈ 2-ethoxyethanol (0.2371)> 2-methoxyethanol (0.2242) > ethyl acetate (0.1801) > methylacetate(0.1461) > isobutyl acetate (0.1391) > propyl acetate (0.1231)≈butyl acetate (0.1202) > isopropyl acetate (0.1114) > acetonitrile(0.02216). The experimental solubility data correlated well with calculatedones from the modified Apelblat equation, the van’t Hoff equation,and the Yaws equation. Based on the principle of similar compatibility,the law of solubility and miscibility of 4-isopropylbenzoic acid inpure solvents were discussed through Hansen solubility parametersand solvent effects for predicting solubility behavior.

The apparent mole fraction solubility of glucono-δ-lactone(GDL) was determined by a gravimetric method in four binary solventsystems: water + ethanol, water + i-propanol, water + n-propanol,and water + acetic acid. The experiments were carried out at atmosphericpressure over a temperature range from 288.15 K to 328.15 K. The resultsindicate that the solubility of GDL is positively correlated withtemperature and with the mole fraction of water in the binary solventsystems. In addition, the structural characteristics of GDL moleculesand intermolecular interactions were clarified by molecular electrostaticpotential surface (MEPS) analysis and Hirshfeld surface (HS) analysis.For correlating the solubility data, the modified Apelblat equation,the van’t Hoff equation, and the λh equation were compared.Based on an evaluation using relative deviation (RD), average relativedeviation (ARD), and root-mean-square deviation (RMSD), the modifiedApelblat equation was identified as the most suitable correlationmodel. Finally, this study provides a mechanistic explanation forthe creeping phenomenon observed during the experiments.

This study examines the diffusioncoefficients of ethanethioland n-propanethiol in model hydrocarbon phases (n-pentane and n-octane) and aqueous alkalinephases(NaOH and KOH solutions). A theoretical analysis shows that, at lowthiol concentrations, the multicomponent diffusion matrices reduceto the Einstein self-diffusion coefficients, supporting their usein interphase mass-transfer modeling. Thiol diffusion coefficientswere determined by NMR diffusometry and molecular dynamics simulations.The predictive performance of the Wilke–Chang and Lusis–Ratcliffequations was also evaluated, and thiol diffusion coefficients atinfinite dilution in hydrocarbon mixtures were predicted. The resultsshow that these computational approaches can be used to predict thioldiffusion coefficients for mass-transfer modeling of thiol-removalprocesses.