Journal of Chemical Thermodynamics最新文献_第9页

VLE of binary mixtures of tri-substituted imidazolium ionic liquids with ethanol or water: Experimental and molecular-level insights 三取代咪唑离子液体与乙醇或水二元混合物的VLE：实验和分子水平的见解

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-04-28 DOI: 10.1016/j.jct.2025.107504

Jingli Han , Yu Cui , Alexandra Elena Plesu Popescu , Jordi Bonet Ruiz , Joan Llorens Llacuna

This study investigates the vapor-liquid equilibrium behavior of binary mixtures comprising tri-substituted imidazolium ionic liquids with either ethanol or water, combining experimental analysis with molecular-level insights. The ionic liquids used in this research are 1-ethyl-2,3-dimethylimidazolium bromide ([C₂MMIm][Br]) and 1-ethyl-2,3-dimethylimidazolium chloride ([C₂MMIm][Cl]). The investigation focuses on the effects of temperature, the type of ionic liquid, and the amount of ionic liquid added on the vapor pressure of these binary systems. The experimental data are fitted using the NRTL, Electrolyte NRTL and Wilson models to determine the binary interaction parameters. Furthermore, this study evaluates the influence of different ionic liquids on the vapor pressure of the binary systems to assess the strength of intermolecular interactions between the ionic liquids and ethanol or water. Molecular-level analyses, including surface charge density, dipole moment, and excess enthalpy, are conducted using the COSMO-RS model to explore the interactions between the ionic liquids and solvents, thereby providing theoretical insights into the phase equilibrium behavior. These investigations offer fundamental data essential for the engineering design and large-scale application of ionic liquid extractive distillation processes.

本研究结合实验分析和分子水平的见解，研究了由三取代咪唑离子液体与乙醇或水组成的二元混合物的汽液平衡行为。本研究使用的离子液体为1-乙基-2,3-二甲基咪唑溴（[C2MMIm][Br]）和1-乙基-2,3-二甲基咪唑氯（[C2MMIm][Cl]）。研究了温度、离子液体种类和离子液体加入量对二元体系蒸汽压的影响。采用NRTL、电解质NRTL和Wilson模型拟合实验数据，确定二元相互作用参数。此外，本研究还评估了不同离子液体对二元体系蒸汽压的影响，以评估离子液体与乙醇或水的分子间相互作用的强度。使用cosmos - rs模型进行分子水平分析，包括表面电荷密度、偶极矩和过量焓，以探索离子液体和溶剂之间的相互作用，从而为相平衡行为提供理论见解。这些研究为离子液体萃取精馏工艺的工程设计和大规模应用提供了必要的基础数据。

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引用次数: 0

Molecular interaction and esterase activity of bovine serum albumin with Pazopanib using multi-spectroscopic techniques and molecular docking 利用多光谱技术和分子对接研究牛血清白蛋白与帕唑帕尼的分子相互作用和酯酶活性

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-04-25 DOI: 10.1016/j.jct.2025.107503

Ankita Jalan, Madhumita Patar, N. Shaemningwar Moyon

This work delves into the binding dynamics of a promising anti-cancer drug Pazopanib (PZB) with bovine serum albumin (BSA), a mammalian plasma protein carrier with incredible ligand-binding properties. PZB is a tyrosine kinase inhibitor (TKI) used as a monotherapy against advanced renal cell carcinoma, soft tissue sarcoma, and liver fibrosis. Drug-albumin interactions vary with concentration, affecting drug efficacy and toxicity. Herein, we have investigated the binding mechanism of PZB with BSA at higher drug concentrations (5 × 10⁻⁶ mol/kg - 4 × 10⁻⁵ mol/kg) than albumin (3 × 10⁻⁶ mol/kg) using techniques like absorption, steady-state fluorescence, FRET, FT-IR, synchronous fluorescence, CD, and molecular docking. The intrinsic BSA fluorescence quenches with gradual increase in concentration of PZB via static quenching. The binding constant was found to be moderate (6.497 × 10⁴ mol ⁻¹.kg) and it has only one binding site. The Förster distance (r) indicated probable transfer of energy between the donor BSA and acceptor PZB. The major interacting forces are hydrophobic forces and hydrogen bonding. Conformational change in the protein framework was revealed from synchronous fluorescence, FT-IR, and CD studies. Competitive binding experiments as well as docking studies suggest that PZB binds to site I (subdomain IIA) of BSA. The increase in kinetic parameters reveals that the catalytic efficiency of BSA is enhanced on PZB interaction.

这项工作深入研究了一种有前途的抗癌药物Pazopanib （PZB）与牛血清白蛋白（BSA）的结合动力学，牛血清白蛋白是一种具有令人难以置信的配体结合特性的哺乳动物血浆蛋白载体。PZB是一种酪氨酸激酶抑制剂（TKI），用于治疗晚期肾细胞癌、软组织肉瘤和肝纤维化。药物与白蛋白的相互作用随浓度的变化而变化，影响药物的疗效和毒性。本研究利用吸收、稳态荧光、FRET、FT-IR、同步荧光、CD和分子对接等技术，研究了PZB在较高药物浓度（5 × 10−6 mol/kg - 4 × 10−5 mol/kg）下与白蛋白（3 × 10−6 mol/kg）的结合机制。随着PZB浓度的逐渐增加，BSA本征荧光通过静态猝灭而猝灭。结合常数为6.497 × 104 mol−1 kg，且只有一个结合位点。Förster距离(r)表明供体BSA和受体PZB之间可能存在能量转移。主要的相互作用力是疏水力和氢键。同步荧光、FT-IR和CD研究揭示了蛋白质框架的构象变化。竞争结合实验和对接研究表明，PZB结合到BSA的I位点（亚结构域IIA）。动力学参数的增加表明BSA对PZB相互作用的催化效率提高。

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引用次数: 0

Volumetric properties modeling of unsaturated solutions in the Li–Na–K–Cl–H2O system from 288.15 to 323.15 K and at 101.3 kPa using the Pitzer equations 288.15 ~ 323.15 K和101.3 kPa下Li-Na-K-Cl-H2O体系中不饱和溶液的体积性质用Pitzer方程建模

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-04-23 DOI: 10.1016/j.jct.2025.107501

Aldo N. Fuentes , José D. Arriagada , Yecid P. Jiménez , Jesús M. Casas , Francisca J. Justel

This work presents a modeling approach to describe the volumetric properties of unsaturated solutions in the quaternary Li–Na–K–Cl–H₂O system from 288.15 to 323.15 K and at 101.3 kPa using the Pitzer equations. This system is a key component of the electrolytic environment found in brines extracted from the Salar de Atacama in Chile, which are used to produce lithium compounds.

The densities measured in this study, validated against data from the literature, showed trends consistent with changes in concentration and temperature, where KCl(aq) exerts the greatest influence on solution density.

New volumetric parameters for the LiCl – H₂O system at 323.15 K were obtained, and volumetric interaction coefficients in ternary mixtures were determined as a function of temperature, thereby expanding the existing database. The resulting standard deviations were low (below 1 %), demonstrating the model robustness in predicting volumetric properties for complex multi–component systems.

The volumes of mixing analysis revealed significant structural changes in these solutions: NaCl(aq) and LiCl(aq) act as structure breakers of water, while KCl(aq) exhibits dual behavior depending on the solution composition and total ionic strength. This information is valuable for understanding the structural nature of concentrated solutions and their impact on industrial processes to produce lithium compounds from brines.

本文提出了一种利用Pitzer方程来描述在288.15 ~ 323.15 K和101.3 kPa条件下，四元Li-Na-K-Cl-H2O体系中不饱和溶液的体积特性的建模方法。该系统是智利阿塔卡马盐湖（Salar de Atacama）提取的盐水中电解环境的关键组成部分，用于生产锂化合物。本研究中测量的密度，与文献数据相对照，显示出与浓度和温度变化一致的趋势，其中KCl（aq）对溶液密度的影响最大。在323.15 K下获得了LiCl - H2O体系的新体积参数，并确定了三元混合物中体积相互作用系数随温度的函数，从而扩展了现有数据库。得到的标准偏差很低（低于1%），表明该模型在预测复杂多组分体系的体积特性方面具有稳健性。混合体积分析表明，这些溶液的结构发生了显著变化：NaCl（aq）和LiCl（aq）是水的结构破坏者，而KCl（aq）则根据溶液组成和总离子强度表现出双重行为。这些信息对于理解浓缩溶液的结构性质及其对从盐水中生产锂化合物的工业过程的影响是有价值的。

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引用次数: 0

Freezing point depression in the binary NaVO3–H2O and NH4VO3–H2O Systems at p=0.1MPa p=0.1MPa时NaVO3-H2O和NH4VO3-H2O二元体系凝固点下降

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-04-22 DOI: 10.1016/j.jct.2025.107491

Mikael A.E. Manninen, Tuomas J. Vielma, Ulla M. Lassi

The freezing point depressions in the

and

systems have been determined at

p = 0.1 M P a

from molalities of ca.

0.005 {m o l k g}^{- 1}

up to near saturation. The present data significantly expand the almost non-existent database of excess thermodynamic properties of binary

systems. The data could be explained within their experimental uncertainties by a thermodynamic model considering the association of the dihydrogenvanadate ion (

) to

and representing the excess Gibbs free energy (

G^{Ex}

) by the Pitzer equations with two adjustable parameters. The magnitudes of the determined parameters for the second virial coefficient of

-

interaction were typical for 4-1 electrolytes. The same model could describe also the data for the

system as even the saturated solution is sufficiently dilute that the contribution of short range interactions to

G^{Ex}

is small.

在p=0.1MPa的条件下，从约0.005molkg - 1的摩尔浓度到接近饱和，测定了两种体系的凝固点下降。目前的数据极大地扩展了几乎不存在的二元系统超额热力学性质数据库。这些数据可以用一个热力学模型来解释，该模型考虑了钒酸二氢离子（）与过量吉布斯自由能（GEx）的关联，并用两个可调参数的Pitzer方程来表示。所确定的第2维里相互作用系数的大小是典型的4-1电解质。同样的模型也可以描述系统的数据，因为即使饱和溶液足够稀释，短程相互作用对GEx的贡献也很小。

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引用次数: 0

Thermodynamic studies of binary liquid mixtures of 2-(2-butoxyethoxy) ethanol with diisopropylamine, di-n-butylamine and tri-n-butylamine at 298.15, 303.15 and 308.15 K 298.15、303.15和308.15 K下2-（2-丁氧乙氧基）乙醇与二异丙胺、二正丁胺和三正丁胺二元液体混合物的热力学研究

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-04-21 DOI: 10.1016/j.jct.2025.107488

Likhish Dhingra, Gyan Prakash Dubey

Present discussion embodies the studies on binary mixtures containing 2-(2-butoxyethoxy) ethanol with secondary amines (diisopropylamine, di-n-butylamine) and tertiary amine (tri-n-butylamine).ρ, u and η of these binary mixtures were measured at temperatures T = 298.15, 303.15 and 308.15 K and at atmospheric pressure. Various excess, deviation and thermo acoustic parameters were calculated using the experimentally measured data. Results were investigated for type and ease of intermolecular interactions among unlike molecules in these mixtures. Presence of strong interactions among unlike molecules has been confirmed by the calculated parameters. Excess and deviation parameters were fitted to Redlich-Kister polynomial. Ability of this equation was tested using the standard deviation calculated with the help of least square method.

本文讨论了2-（2-丁氧乙氧基）乙醇与仲胺（二异丙胺、二正丁胺）和叔胺（三正丁胺）二元混合物的研究。分别在温度T = 298.15、303.15和308.15 K和常压下测量了这些二元混合物的ρ、u和η。利用实验测量数据计算了各种多余、偏差和热声参数。研究了这些混合物中不同分子间相互作用的类型和容易程度。计算的参数证实了不同分子之间存在强相互作用。多余参数和偏差参数拟合为Redlich-Kister多项式。利用最小二乘法计算的标准差检验了该方程的适用性。

引用次数: 0

Investigating ethyl laurate and 2-alkanol systems: Application of significant structure theory 研究月桂酸乙酯和 2-烷醇体系：重要结构理论的应用

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-04-17 DOI: 10.1016/j.jct.2025.107502

Mohammad Almasi

The study examines the liquid density and viscosity behavior of ethyl laurate (EL) mixed with different 2-alkanols (2-propanol, 2-butanol, 2-pentanol, and 2-hexanol) over the temperature range of 293.15 to 323.15 K, with the goal of clarifying the intermolecular interactions and deviations from ideality. Our experimental observations showed that all tested mixtures displayed positive excess molar volumes and negative viscosity deviations, implying that the forces between EL and each 2-alkanol are relatively weak. The significant structure theory was then utilized to represent the pure-component viscosities, yielding a maximum viscosity discrepancy of 1.691 % for 2-pentanol. For the binary systems, we introduced a new correlation whose calculated values aligned closely with the measurements, demonstrating a maximum variation of only 2.01 % for the EL + 2-hexanol mixture, which highlights the predictive capability of the proposed model. The performance of this model was compared to earlier models such as Nissan-Grunberg, Hind, Kendall-Monroe, Arrhenius, and other models. Our results demonstrate that the new model offers improved accuracy, albeit with more complex parameters.

在293.15 ~ 323.15 K的温度范围内，研究了月桂酸乙酯（EL）与不同的2-烷醇（2-丙醇、2-丁醇、2-戊醇和2-己醇）混合的液体密度和粘度行为，目的是澄清分子间相互作用和偏离理想的情况。我们的实验观察表明，所有被测试的混合物都显示出正的过量摩尔体积和负的粘度偏差，这意味着EL与每种2-烷醇之间的作用力相对较弱。然后利用显著结构理论来表示纯组分粘度，得到2-戊醇的最大粘度差异为1.691%。对于二元体系，我们引入了一个新的相关性，其计算值与测量值密切相关，表明EL + 2-己醇混合物的最大变化仅为2.01%，这突出了所提出模型的预测能力。将该模型的性能与nissangrunberg、Hind、Kendall-Monroe、Arrhenius等早期模型进行了比较。我们的结果表明，新模型提供了更高的精度，尽管更复杂的参数。

{"title":"Investigating ethyl laurate and 2-alkanol systems: Application of significant structure theory","authors":"Mohammad Almasi","doi":"10.1016/j.jct.2025.107502","DOIUrl":"10.1016/j.jct.2025.107502","url":null,"abstract":"<div><div>The study examines the liquid density and viscosity behavior of ethyl laurate (EL) mixed with different 2-alkanols (2-propanol, 2-butanol, 2-pentanol, and 2-hexanol) over the temperature range of 293.15 to 323.15 K, with the goal of clarifying the intermolecular interactions and deviations from ideality. Our experimental observations showed that all tested mixtures displayed positive excess molar volumes and negative viscosity deviations, implying that the forces between EL and each 2-alkanol are relatively weak. The significant structure theory was then utilized to represent the pure-component viscosities, yielding a maximum viscosity discrepancy of 1.691 % for 2-pentanol. For the binary systems, we introduced a new correlation whose calculated values aligned closely with the measurements, demonstrating a maximum variation of only 2.01 % for the EL + 2-hexanol mixture, which highlights the predictive capability of the proposed model. The performance of this model was compared to earlier models such as Nissan-Grunberg, Hind, Kendall-Monroe, Arrhenius, and other models. Our results demonstrate that the new model offers improved accuracy, albeit with more complex parameters.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"207 ","pages":"Article 107502"},"PeriodicalIF":2.2,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143852085","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Ionic speciation and volumetric properties modeling of the ternary system CuCl2 – HCl – H2O from 273.15 to 373.15 K and at 101.3 kPa using the Pitzer equations 在273.15 ~ 373.15 K和101.3 kPa条件下，CuCl2 - HCl - H2O三元体系的离子形态和体积性质用Pitzer方程建模

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-04-15 DOI: 10.1016/j.jct.2025.107500

Aldo N. Fuentes , Jesús M. Casas , Francisca J. Justel , Yecid P. Jiménez

This work develops a thermodynamic model for ionic speciation and volumetric properties of the ternary system CuCl₂ – HCl – H₂O from 273.15 to 373.15 K and at 101.3 kPa, a system relevant to chalcopyrite leaching in chloride media and hydrogen production via the copper–chlorine thermochemical cycle. The Pitzer equations were used to estimate water activities, CuCl₂·2H₂O(cr) solubilities, and densities, calibrated using published experimental data. The speciation model includes Cu²⁺, H⁺, CuCl⁺, Cl^–,

{CuCl}_{2}^{0}

, and HCl⁰, showing reasonable species distribution results as a function of temperature and total concentration. Based on volume of mixing calculations at 298.15 K, CuCl₂ acts as a structure breaker of water, while HCl behaves as a structure maker. New Pitzer parameters and the solubility product constant of CuCl₂·2H₂O(cr) are provided as temperature–dependent functions. The model demonstrates high accuracy in reproducing experimental data and offers insights into the physicochemical behavior of concentrated CuCl₂ + HCl + H₂O solutions.

本研究建立了在273.15 ~ 373.15 K和101.3 kPa范围内CuCl2 - HCl - H2O三元体系离子形态和体积性质的热力学模型，该体系与氯化物介质中黄铜矿的浸出和通过铜-氯热化学循环产氢有关。Pitzer方程用于估算水活度、CuCl2·2H2O（cr）溶解度和密度，并使用已发表的实验数据进行校准。物种形成模型包括Cu2+、H+、CuCl+、Cl -、CuCl20和HCl0，物种分布结果随温度和总浓度的变化较为合理。根据298.15 K下的混合体积计算，CuCl2是水的结构破坏者，而HCl则是结构制造者。给出了CuCl2·2H2O（cr）的新Pitzer参数和溶解度积常数作为温度相关函数。该模型在再现实验数据方面具有较高的准确性，并为CuCl2 + HCl + H2O浓溶液的物理化学行为提供了见解。

{"title":"Ionic speciation and volumetric properties modeling of the ternary system CuCl2 – HCl – H2O from 273.15 to 373.15 K and at 101.3 kPa using the Pitzer equations","authors":"Aldo N. Fuentes , Jesús M. Casas , Francisca J. Justel , Yecid P. Jiménez","doi":"10.1016/j.jct.2025.107500","DOIUrl":"10.1016/j.jct.2025.107500","url":null,"abstract":"<div><div>This work develops a thermodynamic model for ionic speciation and volumetric properties of the ternary system CuCl<sub>2</sub> – HCl – H<sub>2</sub>O from 273.15 to 373.15 K and at 101.3 kPa, a system relevant to chalcopyrite leaching in chloride media and hydrogen production via the copper–chlorine thermochemical cycle. The Pitzer equations were used to estimate water activities, CuCl<sub>2</sub>·2H<sub>2</sub>O(cr) solubilities, and densities, calibrated using published experimental data. The speciation model includes Cu<sup>2+</sup>, H<sup>+</sup>, CuCl<sup>+</sup>, Cl<sup>–</sup>, <span><math><msubsup><mi>CuCl</mi><mn>2</mn><mn>0</mn></msubsup></math></span>, and HCl<sup>0</sup>, showing reasonable species distribution results as a function of temperature and total concentration. Based on volume of mixing calculations at 298.15 K, CuCl<sub>2</sub> acts as a structure breaker of water, while HCl behaves as a structure maker. New Pitzer parameters and the solubility product constant of CuCl<sub>2</sub>·2H<sub>2</sub>O(cr) are provided as temperature–dependent functions. The model demonstrates high accuracy in reproducing experimental data and offers insights into the physicochemical behavior of concentrated CuCl<sub>2</sub> + HCl + H<sub>2</sub>O solutions.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"207 ","pages":"Article 107500"},"PeriodicalIF":2.2,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143843673","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Apparent molar volumes of methanol, ethanol, and 2-propanol in dense phase CO2 甲醇、乙醇和2-丙醇在致密相CO2中的表观摩尔体积

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-04-15 DOI: 10.1016/j.jct.2025.107499

Safeer S. Nanji, Connor E. Deering, Kevin L. Lesage, Robert A. Marriott

Despite the increasing importance of CO₂ processing and the use of aliphatic alcohols as cosolvents in supercritical fluid extraction, there is an apparent lack of densimetric or volumetric data for dilute alcohols in near-critical CO₂ within the literature. To this end, apparent molar volumes of binary solutions for methanol, ethanol, and 2-propanol in CO₂ were calculated from measured density differences (δΔρ = 0.01–1.60 kg m⁻³) determined from T = 298–313 K and p = 8–13 MPa using a flow densimeter modified for high pressure measurement. This temperature and pressure range was chosen for the proximity to the critical point of pure CO₂, where volumetric changes are very sensitive and allow for better calibration of binary parameters. The apparent molar volumes of the mixtures were then used to optimize mixing coefficients with reference quality pure component Helmholtz equations-of-state and Fluctuation Solution Theory. Apparent molar volumes of these alcohol solutes resulted in poorer fits of the binary mixing coefficients for reference quality reduced Helmholtz Equations of State when compared to Fluctuation Solution Theory; however, excess functions with more parameters may be developed by future researchers. With the Fluctuation Solution Theory equations, Krichevskii parameters were determined for each alcohol in CO₂. These values were similar to a previous study of H₂O in CO₂; however, variance was noted from literature values with different methods of extrapolation.

尽管CO2处理和在超临界流体萃取中使用脂肪族醇作为助溶剂的重要性日益增加，但在文献中明显缺乏近临界CO2中稀醇的密度或体积数据。为此，在T = 298-313 K和p = 8-13 MPa的条件下，使用改进的高压测量流量密度计，通过测量密度差（δΔρ = 0.01-1.60 kg m - 3），计算出甲醇、乙醇和2-丙醇在CO2中的二元溶液的表观摩尔体积。选择这个温度和压力范围是为了接近纯二氧化碳的临界点，在那里，体积变化非常敏感，可以更好地校准二进制参数。采用纯组分亥姆霍兹状态方程和涨落解理论，利用混合物的表观摩尔体积来优化混合系数。与波动解理论相比，这些醇溶质的表观摩尔体积导致二元混合系数的拟合较差，参比质量降低了亥姆霍兹状态方程；然而，未来的研究人员可能会开发出具有更多参数的过剩函数。利用波动解理论方程，确定了CO2中每种醇的克里切夫斯基参数。这些数值与之前对CO2中H2O的研究相似；然而，不同外推方法的文献值存在差异。

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引用次数: 0

Comments regarding “Solubility determination, model evaluation, molecular simulation and thermodynamic analysis of sulfentrazone (form I) in single and binary solvents” 关于“磺胺曲酮（形式I）在单一和二元溶剂中的溶解度测定、模型评价、分子模拟和热力学分析”的评论

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-04-03 DOI: 10.1016/j.jct.2025.107490

Bradley Lin, Saikiran Motati, William E. Acree

A polemic is given regarding the van't Hoff curve-fit parameters and apparent thermodynamic properties of solution of sulfentrazone (form I) that Mao and coworkers reported in their recently published paper. The van't Hoff parameters were found to be inconsistent with the tabulated thermodynamic quantities. New sets of curve-fit parameters were determined by reanalysis of the authors' published mole fraction solubility data.

对Mao和同事在最近发表的论文中报道的磺胺酮溶液（形式I）的范霍夫曲线拟合参数和表观热力学性质进行了争论。发现范霍夫参数与表中的热力学量不一致。通过重新分析作者发表的摩尔分数溶解度数据，确定了新的曲线拟合参数集。

引用次数: 0

Effect of the solvent H/D isotope substitution on enthalpy-interaction parameters for the pharmaceutical urotropine (hexamethylenetetramine) in aqueous solutions at 298.15 K 在 298.15 K 的水溶液中，溶剂 H/D 同位素置换对药物乌洛托品（六亚甲基四胺）焓-相互作用参数的影响

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-03-28 DOI: 10.1016/j.jct.2025.107489

Evgeniy V. Ivanov , Dmitriy V. Batov , Andrey V. Kustov , Alexander F. Syschenko

The enthalpies of dilution of solutions of hexamethylenetetramine (HMTA), the well-known pharmaceutical urotropine, in water (H₂O) and heavy water (D₂O) were determined with a new heat conduction calorimeter at 298.15 K. The enthalpy-related homotactic coefficients of pairwise,

h_{22}

, and triplet,

h_{222}

, interactions between hydrated solute molecules were computed using the excess thermodynamic function concept (based on the McMillan-Mayer theory formalism). The

h_{22}

and

h_{222}

values were found to be large and positive in both H₂O and D₂O due to a partial overlapping of solute hydrophobic hydration shells and appearance of solute – solute correlations at rather large distances. This phenomenon is stronger pronounced in heavy water both for pairwise and for triplet HMTA – HMTA interactions indicating a highly ordered hydration structure in D₂O. The established correlation between the

h_{22}

values and the corresponding solvent isotope effects,

{δh}_{22}

(H₂O → D₂O), for HMTA and tetramethylurea mono- and bicyclic derivatives as solute species confirms the hypothesis of the differentiating effect of a solvent isotopic substitution on both the energetics of solvation and solute – solute interactions in aqueous solutions of proton-accepting non-electrolytes. In other words, the more negative or positive the

h_{22}

value due to stronger homo- and heterocomponent D-bonds, the more negative or positive the corresponding isotopic effect is.

用新型热传导量热计在298.15 K下测定了六亚甲基四胺（HMTA）溶液在水（H2O）和重水（D2O）中的稀释焓。利用超额热力学函数概念（基于McMillan-Mayer理论的形式主义）计算了水合溶质分子之间的双态h22和三重态h22相互作用的焓相关同规系数。在H2O和D2O中，由于溶质疏水水化壳的部分重叠以及在相当大的距离上出现溶质-溶质相关性，h22和h22值都很大且为正。这种现象在重水中更为明显，无论是双相互作用还是三重相互作用，都表明在D2O中存在高度有序的水化结构。hta和四甲基脲单环和双环衍生物的溶质δh22（H2O→D2O）值与相应的溶剂同位素效应之间建立的相关性证实了溶剂同位素取代对质子非电解质水溶液中溶剂化和溶质-溶质相互作用的能量学有区分作用的假设。也就是说，由于更强的同质和异质d键，h22值越负或越正，相应的同位素效应就越负或越正。

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引用次数: 0