Journal of Chemical Thermodynamics最新文献

Thermochemical investigation of three 5-R-thio-1,3,4-thiadiazole derivatives: R = methyl, ethyl 三种 5-R 硫代-1,3,4-噻二唑衍生物的热化学研究：R = 甲基、乙基

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2024-11-19 DOI: 10.1016/j.jct.2024.107423

Ana L.R. Silva , Ana C.M.O. Lima , Jorge M. Gonçalves , Victor M.F. Morais , Maria D.M.C. Ribeiro da Silva

An experimental and computational thermochemical study is reported focus on the relationship between the energetic properties, the structural characteristics and the inherent reactivity of three thiothiadiazoles: 2-amino-5-(methylthio-)-1,3,4-thiadiazole, 2-amino-5-(ethylthio-)-1,3,4-thiadiazole and 2-mercapto-5-methylthio-1,3,4-thiadiazole. From the DSC measurements, the enthalpies of fusion and the respective onset temperatures were determined. The standard molar energies of combustion of the (alkylthio)-1,3,4-thiadiazoles were determined by rotating bomb combustion calorimetry. The corresponding standard molar enthalpies of sublimation, at T = 298.15 K, were derived from high-temperature Calvet microcalorimetry measurements and the study of the dependence of the compound’s vapour pressures with the temperature, using the Knudsen-effusion technique. The combination of these experimental results enables the calculation of the standard molar enthalpies of formation in the gaseous state, at T = 298.15 K, which are discussed in terms of structural contributions. The latter property was also determined from high-level ab initio molecular orbital calculations at the G3(MP2)//B3LYP level of theory. The computed values are in good agreement with the experimental ones. In addition, a conformational and tautomeric study was conducted using the same approach, in order to provide insight on the amino/imino and thiol/thione tautomerism of the compounds studied. The amino form predominates in amino-thiadiazoles, while the thione form prevails in mercaptothiadiazole. Moreover, the relative thermodynamic stability of each compound was also evaluated showing that in both solid and gas phases, the most stable species is the mercaptothiadiazole (in its thione form). The thermochemical results of the (alkylthio)-1,3,4-thiadiazoles show a good agreement with the NBO (natural bond orbitals) analysis results.

本报告主要针对三种噻二唑（2-氨基-5-(甲硫基-)-1,3,4-噻二唑、2-氨基-5-(乙硫基-)-1,3,4-噻二唑和 2-巯基-5-甲硫基-1,3,4-噻二唑）的能量特性、结构特征和固有反应活性之间的关系，进行了实验和计算热化学研究。通过 DSC 测量，确定了熔化焓和各自的起始温度。通过旋转弹燃烧量热法确定了（烷基硫代）-1,3,4-噻二唑的标准摩尔燃烧能量。相应的标准摩尔升华焓（T = 298.15 K）是通过高温卡尔维特微量热仪测量和利用克努森扩散技术研究化合物蒸汽压力与温度的关系得出的。结合这些实验结果，可以计算出 T = 298.15 K 时气态的标准摩尔形成焓，并从结构贡献的角度对其进行了讨论。后一种性质也是通过 G3(MP2)//B3LYP 理论水平的高水平 ab initio 分子轨道计算确定的。计算值与实验值十分吻合。此外，为了深入了解所研究化合物的氨基/亚氨基和硫醇/硫酮同分异构现象，还采用相同的方法进行了构象和同分异构研究。在氨基噻二唑中，氨基形式占主导地位，而在巯基噻二唑中，硫酮形式占主导地位。此外，还对每种化合物的相对热力学稳定性进行了评估，结果表明，在固相和气相中，最稳定的物种是巯基噻二唑（硫酮形式）。(烷基硫基)-1,3,4-噻二唑的热化学结果与 NBO（天然键轨道）分析结果显示出良好的一致性。

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引用次数: 0

Phase equilibria of ternary systems: LiCl–MClx (M = Na+, Mg2+, Sr2+)–H2O systems at 1 bar and volume properties from 1 to 1000 bar (T = 298.2 K) 三元体系的相平衡：LiCl-MClx （M = Na+、Mg2+、Sr2+）-H2O 系统在 1 巴和 1 至 1000 巴（T = 298.2 K）的体积特性下的相平衡

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2024-11-07 DOI: 10.1016/j.jct.2024.107413

Yu-Qiu Cen, Shi-Hua Sang, Guo-Liang Nie, Chun-Tao Hu, Kuang-Yi Zhu

There are abundant lithium resources in seawater and brines. The thermodynamic phase equilibria of salt-water systems containing lithium have significant advantages to separation lithium from brines. Consequently, measurement and prediction of phase equilibria of LiCl–MCl_x (M = Na⁺, Mg²⁺, Sr²⁺)–H₂O ternary systems are investigated at 298.2 K and 1 bar. The phase equilibria are determined using the isothermal dissolution equilibrium method and the solubilities of salts in the ternary systems are predicted using the Pitzer model. The predicted solubilities agree well with experimental data at 298.2 K and 1 bar.

Then, the changes of volume property (

Δ {\bar{V}}_{dis}^{0}

) and compressibility (

Δ {\bar{κ}}_{dis}^{0}

) of three ternary mixed solutions at high pressure of 1–1000 bar were obtained in this work. The solubility product constants K_sp of salts at high pressure are calculated in detail. The thermodynamic prediction model of the phase equilibria is developed at high pressure of 1–1000 bar accordingly. The predicted phase equilibria at high pressure of 1–1000 bar are discussed and compared detailly.

海水和卤水中有丰富的锂资源。含锂盐水体系的热力学相平衡对于从卤水中分离锂具有显著优势。因此，研究了在 298.2 K 和 1 bar 条件下 LiCl-MClx （M = Na+、Mg2+、Sr2+）-H2O 三元体系相平衡的测量和预测。使用等温溶解平衡法确定了相平衡，并使用皮策模型预测了三元体系中盐类的溶解度。预测的溶解度与在 298.2 K 和 1 bar 条件下的实验数据吻合得很好。详细计算了高压下盐类的溶度积常数 Ksp。据此建立了 1-1000 bar 高压下相平衡的热力学预测模型。对预测的 1-1000 bar 高压下的相平衡进行了详细讨论和比较。

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引用次数: 0

Solubility measurement, correlation, and thermodynamic analysis of ε-CL-20 in four binary solvents (ethyl acetate + halogenated hydrocarbon) from 288.15 to 328.15 K ε-CL-20 在 288.15 至 328.15 K 四种二元溶剂（乙酸乙酯 + 卤代烃）中的溶解度测量、相关性和热力学分析

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2024-11-04 DOI: 10.1016/j.jct.2024.107414

Hongyu Wang, Guozhao Liu, Guanwen Su, Hongyuan Wei, Leping Dang

In this work, the solubility of ε-CL-20 in four binary solvents composed of ethyl acetate and halogenated hydrocarbons (bromobenzene, chlorobenzene, dibromomethane, 1,1,2,2-tetrachloroethane) was measured over the temperature range of 288.15–328.15 K at 0.101 MPa by gravimetric method. Under similar conditions, the order of solubility of ε-CL-20 is ethyl acetate + bromobenzene ≈ ethyl acetate + chlorobenzene > ethyl acetate + dibromomethane > ethyl acetate + 1,1,2,2-tetrachloroethane and the solubility decreases with the increase of halogenated hydrocarbon content. The results also reveal that the solubility is negatively correlated with temperature when the mole fraction of halogenated hydrocarbons is low, otherwise the result is opposite. The modified Apelblat model, van’t Hoff model, CNIBS/R-K model, Jouyban-Acree model and Jouyban-Acree-van’t Hoff model were used to correlate the experimental solubility data and all of the models perform well. The modified Apelblat model and Jouyban-Acree-van’t Hoff model are relatively excellent. The dissolution thermodynamic properties of ε-CL-20 in four binary solvents were calculated and analyzed. The results show that the dissolution processes of ε-CL-20 are entropy-driven non-spontaneous processes. This work is significant to the design and optimization of the crystallization of ε-CL-20.

本研究采用重量法测定了ε-CL-20 在由醋酸乙酯和卤代烃（溴苯、氯苯、二溴甲烷、1,1,2,2-四氯乙烷）组成的四种二元溶剂中的溶解度，温度范围为 288.15-328.15 K，压力为 0.101 MPa。在类似条件下，ε-CL-20 的溶解度顺序为：乙酸乙酯 + 溴苯 ≈ 乙酸乙酯 + 氯苯 > 乙酸乙酯 + 二溴甲烷 > 乙酸乙酯 + 1,1,2,2-四氯乙烷，且溶解度随卤代烃含量的增加而降低。结果还显示，当卤代烃的摩尔分数较低时，溶解度与温度呈负相关，反之则相反。修正的 Apelblat 模型、van't Hoff 模型、CNIBS/R-K 模型、Jouyban-Acree 模型和 Jouyban-Acree-van't Hoff 模型被用来关联实验溶解度数据，所有模型均表现良好。修正的 Apelblat 模型和 Jouyban-Acree-van't Hoff 模型相对较好。计算并分析了ε-CL-20 在四种二元溶剂中的溶解热力学性质。结果表明，ε-CL-20 的溶解过程是熵驱动的非自发过程。这项工作对ε-CL-20 的结晶设计和优化具有重要意义。

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引用次数: 0

Experimental and predicted aqueous solubility and vapor pressures of food packaging migrants: 4-n-octylphenol, 4-tert-octylphenol and 4-n-nonylphenol 食品包装迁移物的实验和预测水溶性和蒸汽压：4-正辛基苯酚、4-叔辛基苯酚和 4-正壬基苯酚

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2024-10-28 DOI: 10.1016/j.jct.2024.107410

Joanna Farhat , Ilham Mokbel , Georgio Bassil , Batoul F.Z. Sari-Ali , Latifa Negadi , Jacques Jose , Joseph Saab

4-n-octylphenol (4-n-OP), 4-n-nonylphenol (4-n-NP) and 4-tert-octylphenol (4-tert-OP) are dangerous chemicals available in food contact materials. In order to be able to evaluate their health risk assessment in terms of exposure pathway, chemodynamic (fate) and transport (migration processes), we studied their physicochemical properties: the aqueous solubility and vapor pressure as a function of temperature. The literature suffers from a lack of data related to these properties. The aqueous solubilities for these molecules were carried out using the dynamic saturation method between 298.15 and 328.15 K. The experimental data are low and range between 10⁻⁶ and 10⁻⁸ in mole fraction. The vapor pressures of alkylphenols were measured using the static and dynamic gas saturation methods. 4-n-OP and 4-n-NP showed the lowest vapor pressure at 298.15 K (lower than 10⁻³ Pa). In a second step, Henry’s law constant and air–water partition coefficient were calculated using experimental aqueous solubility and vapor pressure measurements. All experimental data were compared with available literature data and then with calculated properties issued from UNIFAC thermodynamic model.

4-正辛基苯酚（4-n-OP）、4-正壬基苯酚（4-n-NP）和 4-叔辛基苯酚（4-tert-OP）是食品接触材料中的危险化学品。为了能够从接触途径、化学动力学（归宿）和迁移（迁移过程）等方面对它们的健康风险进行评估，我们研究了它们的物理化学特性：水溶性和蒸汽压与温度的函数关系。文献中缺乏与这些特性相关的数据。我们采用动态饱和法在 298.15 至 328.15 K 之间测定了这些分子的水溶性。使用静态和动态气体饱和法测量了烷基酚的蒸汽压。4-n-OP 和 4-n-NP 在 298.15 K 时的蒸气压最低（低于 10-3 Pa）。第二步，利用实验水溶性和蒸汽压测量值计算亨利定律常数和空气-水分配系数。所有实验数据都与现有文献数据进行了比较，然后与 UNIFAC 热力学模型得出的计算特性进行了比较。

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引用次数: 0

New thermodynamic insights into pregabalin interactions with H+, Na+, Mg2+, Ca2+, Cu2+, Zn2+: Equilibrium constants, enthalpy changes and sequestering ability 普瑞巴林与 H+、Na+、Mg2+、Ca2+、Cu2+、Zn2+ 相互作用的热力学新见解：平衡常数、焓变和螯合能力

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2024-10-26 DOI: 10.1016/j.jct.2024.107411

Kavosh Majlesi , Concetta De Stefano , Francesco Crea , Clemente Bretti

The thermodynamics of the interaction between (S)-(+)-3-aminomethyl-5-methylhexanoic acid (pregabalin) and protons was studied potentiometrically at different temperatures (288.15 ≤ T/K ≤ 310.15), ionic strengths (0.16 ≤ I/mol kg⁻¹(H₂O) ≤ 0.97, NaCl), (0.11 ≤ I/mol kg⁻¹(H₂O) ≤ 1.11, (C₂H₅)₄NI), (0.10 ≤ I/mol kg⁻¹(H₂O) ≤ 1.03, NaClO₄, only at T = 298.15 K). The protonation constants at infinite dilution and the corresponding enthalpy change values were determined, as well as their parameters for the dependence on the temperature and ionic strength. The results showed that the protonation reactions are exothermic, and that the entropic contribution is the driving force of the processes. Formation constants of pregabalin (L) with Zn²⁺, Cu²⁺, Ca²⁺, and Mg²⁺ were determined in NaCl(aq) at different ionic strength values, at 298.15 K. Different speciation models were proposed for the various metal/Pregabalin systems: ZnHL²⁺, ZnLOH⁰_(aq), CuL⁺, CuL₂⁰_(aq), CaL⁺, CaHL²⁺, and MgL⁺, depending on the different acid–base properties of the metals and the possible formation of sparingly soluble species. The modelling of the thermodynamic formation parameters respect to the temperature and ionic strength variation was carried out by using both the Specific Ion Interaction Theory (SIT) and an extended Debye-Hückel type equation. Being Pregabalin an emerging contaminant, it was interesting to investigate its distribution in presence of the investigated metal cations in aqueous solution simulating both biological fluid (urine) and natural water (seawater).

在不同温度（288.15 ≤ T/K ≤ 310.15）、离子强度（0.16 ≤ I/mol kg-1(H2O) ≤ 0.97，NaCl）、（0.11 ≤ I/mol kg-1(H2O) ≤ 1.11，(C2H5)4NI）、（0.10 ≤ I/mol kg-1(H2O) ≤ 1.03，NaClO4，仅在 T = 298.15 K 时）。测定了无限稀释时的质子化常数和相应的焓变值，以及它们与温度和离子强度有关的参数。结果表明，质子化反应是放热反应，熵贡献是过程的驱动力。在 298.15 K 的 NaCl（aq）中，测定了不同离子强度值下普瑞巴林（L）与 Zn2+、Cu2+、Ca2+ 和 Mg2+ 的形成常数：ZnHL2+、ZnLOH0(aq)、CuL+、CuL20(aq)、CaL+、CaHL2+ 和 MgL+。通过使用特定离子相互作用理论（SIT）和扩展的 Debye-Hückel 型方程，对温度和离子强度变化的热力学形成参数进行了建模。由于普瑞巴林是一种新出现的污染物，因此有必要研究其在模拟生物液体（尿液）和天然水（海水）的水溶液中与所研究的金属阳离子存在时的分布情况。

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引用次数: 0

Oiling out and solubility measurement, molecular simulation and thermodynamic properties of d-tagatose in four aqueous binary solvent systems at 283.15 to 323.15 K 283.15 至 323.15 K 温度下 d-塔格糖在四种水性二元溶剂体系中的出油和溶解度测量、分子模拟和热力学性质

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2024-10-24 DOI: 10.1016/j.jct.2024.107407

Yuan Zou , Jiaqi Luo , Xinyue Zhai , Yingchen Wang , Qiutong Zhang , Wenhao Yan , Chuncheng Shi , Qifan Su , Qiushuo Yu

Solubility of D-Tagatose in four aqueous binary solvent systems from 278.15 K to 323.15 K was determined using the anti-solvent assisted gravimetric method. The solubility increases with temperature in all four binary solvents, with water, a good solvent, exhibiting a similar trend. In addition, the dissolution process generally follows the ’like dissolves like’ rule. The study indicates that the oiling out occurs when water exhibits a high molar fraction in water + 1-propanol, and water + isopropanol. Furthermore, we study the charge of the molecule using the molecular electrostatic potential surface (MEPS), aiming to analyze the molecular interactions. Then, to explain the dissolution behaviors of D-tagatose, the radial distribution function (RDF) by molecular dynamics simulations (MD) revealed a strong correlation between solute–solvent interactions and solubility, with significant solvent–solvent interactions. The solubility data was correlated using the modified Apelblat equation, Van’t Hoff equation, λh equation, and Jouyban-Acree model, with demonstrating the high consistency in the data. Finally, the thermodynamic properties revealed that the dissolution process of D-Tagatose is endothermic, and entropy-driven based on all positive values for

Δ_{s o l} H^{o}

,

Δ_{s o l} S^{o}

,

Δ_{s o l} G^{o}

.

采用反溶剂辅助重量法测定了 D-塔格糖在 278.15 K 至 323.15 K 四种水性二元溶剂体系中的溶解度。在所有四种二元溶剂中，溶解度都随温度升高而增加，而作为良好溶剂的水也表现出类似的趋势。此外，溶解过程一般遵循 "同类相溶 "的规则。研究表明，当水+1-丙醇和水+异丙醇中水的摩尔分数较高时，就会出现出油现象。此外，我们还利用分子静电位面（MEPS）研究了分子的电荷，旨在分析分子间的相互作用。然后，为了解释 D-塔格糖的溶解行为，分子动力学模拟（MD）的径向分布函数（RDF）显示了溶质-溶剂相互作用与溶解度之间的强相关性，其中溶剂-溶剂相互作用显著。利用改进的 Apelblat 方程、Van't Hoff 方程、λh 方程和 Jouyban-Acree 模型对溶解度数据进行了关联分析，结果表明数据具有很高的一致性。最后，热力学性质表明 D-塔格糖的溶解过程是内热和熵驱动的，ΔsolHo、ΔsolSo、ΔsolGo 均为正值。

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引用次数: 0

Thermodynamic analysis of excess molar enthalpy dynamics in mixtures containing ethanol, methanol, and alkoxyethanols as biofuels for enhanced combustion performance 含有乙醇、甲醇和烷氧基乙醇的混合物中过量摩尔焓动态的热力学分析，作为生物燃料提高燃烧性能

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2024-10-24 DOI: 10.1016/j.jct.2024.107406

Houda Lifi , Rachid Aitbelale , Mohamed Lifi , Natalia Muñoz-Rujas , Fatima Ezzahrae M’hamdi. Alaoui , Fernando Aguilar

The pressing need to find alternative fuels for environmental reasons has spurred the development of biofuels derived from biomass. These renewable energy sources reduce reliance on petroleum and lower greenhouse gas emissions. Ethanol and methanol are key biofuels that act as oxygenated additives, improving combustion efficiency and reducing air pollution. Ethanol, with its high oxygen content, boosts engine performance and cuts emissions, while methanol offers a cost-effective and versatile option. Research on alkoxyethanols-gasoline blends has shown substantial decreases in toxic pollutants, highlighting the importance of thermodynamic insights for advancing cleaner energy solutions. This study presents experimental data on excess molar enthalpies of fluid mixtures, encompassing ethanol and methanol combined with various alkoxyethanols, measured at two temperatures: 298.15 K and 313.15 K. Excess molar enthalpies were determined using a quasi-isothermal flow calorimeter at p = 0.1 MPa. Furthermore, the measured data were analyzed using a Redlich-Kister equation for fitting and correlated using Non-Random Two-Liquid (NRTL) and Universal Quasi-Chemical (UNIQUAC) models. The molecular interactions and thermodynamic behavior of the various studied binary mixtures at different temperatures are thoroughly examined and discussed.

出于环保原因，人们迫切需要寻找替代燃料，这推动了从生物质中提取的生物燃料的发展。这些可再生能源减少了对石油的依赖，降低了温室气体排放。乙醇和甲醇是主要的生物燃料，可作为含氧添加剂，提高燃烧效率，减少空气污染。乙醇含氧量高，可提高发动机性能并减少排放，而甲醇则是一种具有成本效益的多功能选择。有关烷氧基乙醇汽油混合物的研究表明，有毒污染物大幅减少，这突出了热力学研究对于推进清洁能源解决方案的重要性。本研究提供了在两种温度下测量的流体混合物过量摩尔焓的实验数据，包括乙醇和甲醇与各种烷氧基乙醇的混合物：过量摩尔焓是在 p = 0.1 兆帕的条件下使用准等温流动量热仪测定的。此外，还使用 Redlich-Kister 方程对测量数据进行了拟合分析，并使用非随机双液（NRTL）和通用准化学（UNIQUAC）模型对测量数据进行了相关分析。对所研究的各种二元混合物在不同温度下的分子相互作用和热力学行为进行了深入研究和讨论。

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引用次数: 0

Surface tension measurement and modeling for ternary aqueous solutions of N, N-diethylethanolamine + 2-amino-2-methyl-1-propanol/piperazine + water at T = (293.15 to 318.15) K N, N-二乙基乙醇胺 + 2-氨基-2-甲基-1-丙醇/哌嗪 + 水的三元水溶液在 T = (293.15 至 318.15) K 时的表面张力测量与建模

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2024-10-24 DOI: 10.1016/j.jct.2024.107405

Xueli Zhou, Qingyuan Song, Yuhuan Chen, Fang Yang

The surface tensions of ternary aqueous mixtures composed of N, N-diethylethanolamine (DEEA) (1), 2-amino-2-methyl-1-propanol (AMP) or piperazine (PZ) (2) and H₂O (3) was measured at temperatures ranging from (293.15 to 318.15) K and 101 kPa. The systems with mass fractions of w₁ = (0.20, 0.25, 0.30 and 0.35) DEEA, and w₂ = (0.02 to 0.10) AMP/PZ were investigated. According to the experimental data, the surface tension deviation (Δγ) was obtained and the values were negative under the studied condition. Δγ values were fitted using a polynomial based on the Scatchard model with the average absolute deviation (AAD) ＜ 0.099 mN∙m⁻¹ and the average relative deviations (ARD) ＜ 0.31 %. Moreover, the surface tension values were fitted using Fu-Li-Wang (FLW) and the extended Wilson models. The results revealed that both models can well correlate the surface tension as a function of temperature and composition. FLW model exhibited better fitting results with smaller AAD of less than 0.24 mN∙m⁻¹ and ARD less than 0.68 %, respectively. Additionally, surface enthalpy (H^γ) and surface entropy (S^γ) were estimated based on the temperature dependence of surface tension.

在（293.15 至 318.15）K 和 101 kPa 温度范围内测量了由 N，N-二乙基乙醇胺（DEEA）（1）、2-氨基-2-甲基-1-丙醇（AMP）或哌嗪（PZ）（2）和 H2O（3）组成的三元水性混合物的表面张力。研究了质量分数为 w1 = (0.20、0.25、0.30 和 0.35) 的 DEEA 和 w2 = (0.02 至 0.10) 的 AMP/PZ 体系。根据实验数据，得出了表面张力偏差（Δγ），在研究条件下，其值为负。利用基于 Scatchard 模型的多项式对 Δγ 值进行了拟合，平均绝对偏差 (AAD) ＜ 0.099 mN∙m-1 ，平均相对偏差 (ARD) ＜ 0.31 %。此外，还使用傅里旺（FLW）模型和扩展威尔逊模型对表面张力值进行了拟合。结果表明，这两种模型都能很好地将表面张力与温度和成分的函数联系起来。FLW 模型的拟合结果更好，AAD 分别小于 0.24 mN∙m-1 和 ARD 小于 0.68 %。此外，还根据表面张力的温度依赖性估算了表面焓（Hγ）和表面熵（Sγ）。

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引用次数: 0

Vaporization enthalpies of self-associated aromatic compounds at 298.15 K: A review of existing data and the features of heat capacity correction. Part III. Polyphenols, polyanilines and aminophenols 298.15 K 时自结合芳香族化合物的汽化焓：现有数据回顾与热容量修正的特点。第三部分.多酚、多苯胺和氨基酚

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2024-10-22 DOI: 10.1016/j.jct.2024.107408

Dmitrii N. Bolmatenkov, Mikhail I. Yagofarov, Andrey A. Sokolov, Airat A. Notfullin, Boris N. Solomonov

The experimental data on the phase transition enthalpies and heat capacities of numerous polyphenols, polyanilines and aminophenols in the condensed and ideal gas state were analyzed to obtain the reliable values at 298.15 K. For this purpose, we combined experimental data on the crystal, liquid, and ideal gas heat capacities and fusion, sublimation and vaporization enthalpies. Significant part of these data, including the ideal gas heat capacities of 16 molecules, vapor pressures and vaporization enthalpies of 1,3-diaminobenzene and 1,6-dihydroxynaphthalene, were obtained in this work. A modified approach for the estimation of the temperature dependence of vaporization enthalpies of polyphenols, polyanilines and aminophenols showing performance competitive with the experimental one was proposed based on the analysis performed.

为此，我们综合了有关晶体、液体和理想气体热容量以及熔融、升华和汽化焓的实验数据。其中大部分数据，包括 16 个分子的理想气体热容、1,3-二氨基苯和 1,6-二羟基萘的蒸汽压和汽化焓，都是在这项工作中获得的。根据所做的分析，提出了一种估算多酚、多苯胺和氨基酚汽化焓随温度变化的修正方法，其性能与实验方法相当。

引用次数: 0

Solubility of letrozole in eight pure and five mixed solvents: Measurement, thermodynamic and molecular simulation analysis 来曲唑在八种纯溶剂和五种混合溶剂中的溶解度：测量、热力学和分子模拟分析

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2024-10-22 DOI: 10.1016/j.jct.2024.107409

Yaxin Yi , Yue Xu , Min Wei, Zhiruo Li, Yini Wang, Xijian Liu, Lijuan Zhang, Haikuan Yuan, Jie Lu

In this work, the solubility of letrozole within eight single and five binary solvents was first systematically investigated at 283.15 K to 323.15 K via the gravimetric method. Subsequently, four thermodynamics formulas including modified Apelblat, λh, GSM and Jouyban-Acree were utilized to link the experimental outcomes of letrozole, all models achieved the good fitting performance and the ARD% was less than 2 %. The dissolvability of letrozole in chosen solvents exhibited a positive correlation with temperature, and co-solvency was observed in such mixed solvent systems as ethyl acetate + 1-propanol, and acetonitrile + 1-propanol. Furthermore, the sites of hydrogen bonding donor and acceptor of letrozole and solvents were analyzed through the molecular electrostatic potential surfaces (MEPs). Then solvent effect, solvation free energy and radial distribution function (RDF) analysis gained via molecular simulation were utilized to illuminate experimental phenomena, the outcomes manifested the polarity, cohesive energy density and other properties of solvents along with both solvent–solvent and solute–solvent interactions contributed differently to the dissolution processes. In the end, the apparent thermodynamic identities concerning letrozole within chosen solvent systems were computed under the van’t Hoff and Gibbs formulas, and outcomes showed that dissolution concerning letrozole was a procedure of endothermic and entropy mainly driven.

在这项工作中，首先通过重量法系统研究了来曲唑在 283.15 K 至 323.15 K 温度下在八种单一溶剂和五种二元溶剂中的溶解度。随后，利用改良阿佩尔布拉特公式、λh公式、GSM公式和Jouyban-Acree公式等四种热力学公式将来曲唑的实验结果联系起来，所有模型都达到了良好的拟合效果，ARD%小于2%。来曲唑在所选溶剂中的溶解度与温度呈正相关，在乙酸乙酯+1-丙醇和乙腈+1-丙醇等混合溶剂体系中观察到了共溶性。此外，还通过分子静电位面（MEPs）分析了来曲唑和溶剂的氢键供体和受体位点。结果表明，溶剂的极性、内聚能密度等特性以及溶剂与溶剂、溶剂与溶剂之间的相互作用对溶解过程产生了不同的影响。最后，根据范特霍夫公式和吉布斯公式计算了来曲唑在所选溶剂体系中的表观热力学特性，结果表明来曲唑的溶解是一个主要由内热和熵驱动的过程。

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