JOURNAL OF CHEMICAL THERMODYNAMICS
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2019
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IF 2.29
Yanyan Zhou,Jiaxin Wu,Ali Farajtabar,Jian Wang,Hongkun Zhao
Investigation upon the solubility of monobenzone in aqueous co-solvent mixtures of isopropanol, n -propanol, ethylene glycol (EG) and ethanol was performed via a saturation shake-flask technique at temperatures from 283.15 K to 328.15 K under pressure of p = 101.2 kPa. Experimental solubility magnitude presented positive dependence upon the mass fraction of each co-solvent and temperature. The greatest solubility value on the mole fraction scale was observed in the neat co-solvents. The equilibrated solids with corresponding co-solvent mixtures were characterized through an X -ray power diffraction (XRD) technique, demonstrating the absence of polymorphic transformation or solvate formation. The Jouyban-Acree model was adopted to mathematically describe the monobenzone solubility data. The maximum magnitudes of RAD and RMSD were 3.17 × 10 −2 and 7.64 × 10 −4 , respectively. The local mole fractions of isopropanol ( n -propanol, EG or ethanol) and water adjacent monobenzone were quantitatively studied by the Inverse Kirkwood–Buff integrals method. The parameters of preferential solvation for the isopropanol ( n -propanol, EG or ethanol) were positive in the isopropanol ( n -propanol, EG or ethanol) mixtures in intermediate and alcohol-rich compositions, indicating that monobenzone was preferentially solvated by the isopropanol ( n -propanol, EG or ethanol). Monobenzone mainly acted as a Lewis acid which interacted with proton-acceptor functional group of the alcohols. Furthermore, the analysis of linear solvation energy relationships was made with a suitable combination of the solvent polarity descriptors to reveal the nature of intermolecular interactions bringing about the solubility variation in the co-solvent mixtures.
研究领域:
化学工程
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物理化学
✓ 已验证
DOI
高影响因子
JOURNAL OF CHEMICAL AND ENGINEERING DATA
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2025
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IF 2.1
Wenjie Cai,Yingchun Xie,Yutong Liu,Yang Cong,Cheli Wang
The solubility remains critical in drugs development, manufacturing, and application. S-Ketoprofen (SKTP) solubility in methanol/ethanol/2-propanol/acetone + water (278.15–318.15 K) was measured by the isothermal saturation technique. The impacts of solvent effect, Hansen solubility parameters (HSPs), and preferential solvation on solubility and model correlation were analyzed. The SKTP solubility increased with decreasing water content in alcohols–water but exhibited cosolvency at w = 0.80 in acetone–water; the maximum mole fraction solubility is 0.1072. The HSPs explained the occurrence of cosolvency molecularly (minimum Δδt = 0.08 at w = 0.80, acetone composition). The solvent effect analysis showed that solute–solvent or solvent–solvent interactions account for 63.44 and 32.60% of solvent effect. Thus, hydrogen bonding and nonspecific dipolarity/polarizability interactions dominate SKTP dissolution. The preferential solvation investigation indicated that SKTP was preferentially dissolved by cosolvents within 0.32 < x1 < 1 for methanol–water, 0.23 < x1 < 1 for ethanol–water, 0.17 < x1 < 1 for 2-propanol–water, and 0.21 < x1 < 0.55 for acetone–water but preferentially dissolved by water in other region. The correlation results suggested that the maximum values of relative average deviation and root-mean-square deviation were 4.84% and 9.45 × 10–4, thus Apelbat–Jouyban–Acree, Jouyban–Acree, and van’t Hoff–Jouyban–Acree models can correlate the solubility data accurately.
研究领域:
药学
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物理化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CHEMICAL THERMODYNAMICS
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2023
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IF 2.6
Chaobin Ren,Abolghasem Jouyban,Hongkun Zhao
At the microscopic level, quantitative analysis of molecular surface was used to highlight the electrostatic properties of acidity/basicity of bisacodyl. The -C = O and -N = groups are the principal targets of electrophilic attack because they have the lowest global electrostatic potentials, ranging from −157.6 kJmol −1 to −144.8 kJmol −1 . The Hirshfeld partition analysis-based independent gradient model was used to visually examine the weak interactions between bisacodyl and the solvents, including methanol, ethanol, isopropanol, and water. The isothermal shake-flask method was used to evaluate the bisacodyl solubility in three aqueous co-solvent blends of isopropanol, methanol, and ethanol, under 101.2 kPa. The solubility data of bisacodyl in neat methanol is increased from 5.507 to 44.86 to 10 -4 when the temperature rose from 278.15 to 323.15 K, whereas it climbed from 1.134 to 17.94 to 10 -4 in neat isopropanol. The solubility variation is mostly caused by solvent–solvent interactions, which are explained by the solubility parameter, and solute–solvent interactions, which are explained by the dipolarity-polarizability of the solute. Three models—the Jouyban-Acree model, the modified van't Hoff-Jouyban-Acree-model, and the modified Wilson model were used to analyze the connection between solubility and experimental temperature and cosolvent composition, producing the largest relative average deviation of 9.41%. At temperatures between 293.15 K and 313.15 K, the preferred solvation of bisacodyl was examined using a method based on inverse Kirkwood-Buff integrals. The preferred solvation parameters of bisacodyl had positive values in the medium and rich concentrations of isopropanol/NMP (taken from a published work)/methanol/ethanol, suggesting that bisacodyl was preferentially solvated by these solvents. A quartic polynomial formulation of the interaction term as a function of the Hildebrand solubility parameter using an EHSA was used to accurately describe the solubility of bisacodyl in the four solutions. The dissolution of bisacodyl was entropy-driven process in all solvent mixtures.
研究领域:
药学
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物理化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CHEMICAL THERMODYNAMICS
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2023
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IF 2.6
Yanxun Li,Congcong Li,Xiaoqiang Gao,Hekun Lv
Quantitative analysis of molecular surface was applied at the microscopic level to emphasize the electrostatic characteristics of acidity/basicity of 3,4,5-trimethoxycinnamic acid (TMCA). The primary sites of electrophilic and nucleophilic assault are the –C=O and >OH groups owing to global maximum and lowest electrostatic potentials of −155.5 kJmol −1 and +185.8 kJmol −1 , respectively. Using the independent gradient model based on Hirshfeld partition analysis, the weak interactions between TMCA and solvent were visually inspected. The solubility of TMCA in four co-solvent blends, namely isopropanol + water, methanol + water, acetone + water and ethanol + water, was determined under 101.2 kPa by the isothermal shake-flask technique. As the temperature increased from 278.15 to 323.15 K, the TMCA solubility in neat methanol increased from 66.20 × 10 −4 to 942.9 × 10 −4 ; while in neat acetone, it increased from 175.1 × 10 −4 to 555.1 × 10 −4 . Two solubility curves intersect at about 305.8 K. According to the research based on KAT- linear solvation energy relationships, the solvent–solvent interactions are mostly responsible for the solubility fluctuation. The relationship between solubility and experimental conditions was established using three models: the Jouyban–Acree model, the modified Wilson model, and the modified Jouyban–Acree-van't Hoff model, yielding the highest relative average deviation of 9.56 %. A technique based on inverse Kirkwood–Buff integrals was used to investigate the preferential solvation of TMCA at 298.15 K. The preferential solvation parameters of TMCA showed positive values in isopropanol/acetone/methanol/ethanol -medium and -rich compositions, indicating that isopropanol/acetone/methanol/ethanol preferentially solvated TMCA. Dissolution of TMCA in these aqueous cosolvent solutions was an endothermic process.
研究领域:
化学
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药学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MOLECULAR LIQUIDS
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2023
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IF 6
Zhenghui Li,Renjie Xu
The equilibrium solubility of florasulam in solvent mixtures (methanol/ethanol / n -propanol/propylene glycol (PG) + water) was determined experimentally by isothermal saturation method at 278.15 K to 323.15 K under 101.2 kPa. Both high temperature and low water content of solvent promoted the dissolution of florasulam. Under given conditions, the mole fraction of florasulam was greater in ( n -propanol + water) than other three solvent mixtures. Besides, the solubility of florasulam was correlated with the Jouyban-Acree (J-A) model and van’t Hoff-Jouyban-Acree (V-J-A) model. The obtained average relative deviations ( RAD ) and root mean square deviations ( RMSD ) were no >4.04 % and 1.73 × 10 -4 . The calculated preferential solvation parameter δx 1,3 was used to analyze the preferential dissolution of florasulam between water and alcohols from the molecular perspective. The result is that in the intervals 1 > x methanol > 0.32, 1 > x ethanol > 0.23 and 1 > x n-propanol > 0.19, the florasulam was preferentially dissolved by methanol/ethanol/ n -propanol. In other concentration ranges, the florasulam was preferentially dissolved by water. The reason for the special existence of PG + water is that | δx 1,3 | < 1 × 10 -2 and the dissolution of florasulam in it conformed to the uncertainty propagation rather than preferential solvation theory. The parameters (Δ sol H o , Δ sol G o , Δ sol S o , Δ tr G o , Δ tr H o and Δ tr S o ) that could reflect the apparent and transfer thermodynamic properties were obtained. It was concluded that the solubility change of florasulam was dominated by entropy and the transfer of florasulam from pure water to mixtures was an exothermic process. Finally, the enthalpy–entropy compensation analysis further studied the mechanism of enthalpy and entropy in the dissolution process.
研究领域:
化学
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环境科学
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热力学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CHEMICAL THERMODYNAMICS
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2019
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IF 2.29
Yuxin Bao,Ali Farajtabar,Min Zheng,Hongkun Zhao
Solubilities of 5-nitrofurazone (form γ ) in aqueous co-solvents mixtures of isopropanol, N -methyl pyrrolidone (NMP), ethanol and dimethyl sulfoxide (DMSO) were experimentally investigated via the saturation shake-flask technique at temperatures from 278.15 K to 323.15 K under ambient pressure of p = 101.2 kPa. The solubility of 5-nitrofurazone increased to a maximum value with 100% mass fractions of NMP and DMSO in aqueous solutions of NMP and DMSO, while with 80% mass fractions of isopropanol and ethanol in aqueous solutions of isopropanol and ethanol. The solids equilibrated with liquor were characterized by X-ray power diffraction, indicating that no solvate formation or polymorphic transformation occurred. The Jouyban-Acree model was accepted to correlate the obtained solubility. The acquired highest relative average deviation and root-mean-square deviation values were, respectively, 5.62 × 10 −2 and 11.18 × 10 −4 . Quantitative values for local mole fractions of NMP (ethanol, DMSO, DMF or isopropanol) and water nearby 5-nitrofurazone were obtained by the method of Inverse Kirkwood–Buff integrals. The parameters of preferential solvation were positive for isopropanol/ethanol in the isopropanol/ethanol mixtures in intermediate compositions, and for NMP/DMF/DMSO in the NMP/DMF/DMSO mixtures in intermediate and NMP/DMF/DMSO-rich compositions, which indicated that 5-nitrofurazone was preferentially solvated by the co-solvents. Linear solvation energy relationships were used to model the solvent effect through the analysis of correlations between solubility data and solvent polarity quantified by suitable descriptors.
研究领域:
药学
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化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CHEMICAL THERMODYNAMICS
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2023
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IF 2.6
Zhenghui Li,Yue Shen,Chunjuan Huang
Equilibrium solubility of 2-amino-6-chloropyrazine in ten pure solvents (methanol, ethanol, n -propanol, isopropanol, N,N -Dimethylformamide (DMF), acetonitrile, acetone, propylene glycol (PG), ethylene glycol (EG) and water) and four binary blends of ethanol/ n -propanol/PG/DMF plus water was experimentally measured by isothermal saturation method at 278.15 K to 323.15 K under p = 101.2 kPa. The maximum mole fraction of 2-amino-6-chloropyrazine in mono-solvents was obtained in neat acetone (5.053 × 10 -2 ) at 323.15 K. For four binary mixed systems, the amount of 2-amino-6-chloropyrazine dissolved in DMF + water was more than other three systems. For pure solvent systems, the temperature was the only factor that affected the dissolution of 2-amino-6-chloropyrazine, while temperature and solvent composition were both the factors that affected the dissolution of 2-amino-6-chloropyrazine. The solubility data of 2-amino-6-chloropyrazine in pure solvents was correlated with apelblat model, van’t Hoff model and Buchowski–Książczak λh model. The Jouyban-Acree model, Apelblat-Jouyban-Acree model and van’t Hoff-Jouyban-Acree model were applied to calculate the solubility data of 2-amino-6-chloropyrazine in mixtures. The van’t Hoff plots of the solubility of 2-amino-6-chloropyrazine was adopted as a method to show the relationship between ln × and 1 /T- 1 /T hm , which was the basis for calculating thermodynamic properties. The preferential solvation performance in mixed systems was estimated by the values of δx 1,3 , in 0.19 < x n-propanol/PG/DMF < 1 and 0.23 < x ethanol < 1, the 2-amino-6-chloropyrazine was preferentially dissolved in organic solvents. In contrast, the 2-amino-6-chloropyrazine was dissolved preferentially in water in other intervals. What’s more, the solvent effect of 2-amino-6-chloropyrazine in mixed systems was obtained, the hydrogen bond interaction was the only factor that affects dissolution in alcohols + water and the solvent–solvent molecular interaction was dominant in DMF + water.
研究领域:
化学工程
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物理化学
✓ 已验证
产品关联
DOI
高影响因子
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