Solubility behavior and thermodynamic analysis of hexamethylenetetramine in alcohol-water mixed solvents (methanol/ethanol/1-propanol/isopropanol + water) from 283.15 K to 323.15 K

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics Pub Date : 2026-05-01 Epub Date: 2026-02-05 DOI:10.1016/j.jct.2026.107643

Yimin Jia , Mingting Yuan , Mei Ma , Qiutong Zhang , Wenhao Yan , Yingchen Wang , Jiaqi Luo , Qiushuo Yu

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Abstract

The solubility of hexamethylenetetramine (HMTA) in four binary solvent systems (water + methanol/ethanol/1-propanol/isopropanol) was determined by gravimetric method in the temperature range of 283.15–323.15 K at atmospheric pressure. The mole fraction solubility of HMTA ranged from 20.29 × 10⁻³ to 89.88 × 10⁻³ in water + methanol, from 10.06 × 10⁻³ to 91.84 × 10⁻³ in water + ethanol, from 12.64 × 10⁻³ to 93.09 × 10⁻³ in water +1-propanol, and from 7.65 × 10⁻³ to 93.64 × 10⁻³ in water + isopropanol. In all systems, solubility increased with both temperature and water mole fraction, though the extent of increase varied with alcohol type and content. Molecular electrostatic potential surface (MEPS) analysis was used to investigate the intermolecular interactions. The solubility data were correlated with four models: the Apelblat equation, van't Hoff equation, λh equation, and Jouyban-Acree model, all of which showed good consistency. Among these, the Apelblat equation provided the best correlation, with an average relative average deviation (RAD) of 7.264 × 10⁻³ and a root-mean-square deviation (RMSD) of 0.355 × 10⁻³. Thermodynamic properties were calculated using the modified van't Hoff equation: the dissolution enthalpy change (

Δ_{sol} H^{o}

) ranged from 1.69 to 18.04 kJ·mol⁻¹, the dissolution entropy change (

Δ_{sol} S^{o}

) from −14.55 to 22.34 J·mol⁻¹·K⁻¹, and the dissolution Gibbs free energy change (

Δ_{sol} G^{o}

) from 6.10 to 11.28 kJ·mol⁻¹. The positive values of both

Δ_{sol} H^{o}

and

Δ_{sol} G^{o}

indicate that the dissolution process is endothermic and non-spontaneous under the given conditions. These solubility and thermodynamic results provide critical information for the design of crystallization and purification processes for HMTA.

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六亚甲基四胺在283.15 ~ 323.15 K的醇-水混合溶剂（甲醇/乙醇/1-丙醇/异丙醇+水）中的溶解度行为及热力学分析

用重量法测定了六亚甲基四胺（HMTA）在水+甲醇/乙醇/1-丙醇/异丙醇四种二元溶剂体系中的溶解度，温度范围为283.15 ~ 323.15 K。HMTA在水+甲醇中的溶解度为20.29 × 10−3 ~ 89.88 × 10−3，在水+乙醇中的溶解度为10.06 × 10−3 ~ 91.84 × 10−3，在水+1-丙醇中的溶解度为12.64 × 10−3 ~ 93.09 × 10−3，在水+异丙醇中的溶解度为7.65 × 10−3 ~ 93.64 × 10−3。在所有体系中，溶解度随温度和水摩尔分数的增加而增加，但增加的程度随酒精类型和含量的不同而不同。利用分子静电势面（MEPS）分析分子间相互作用。溶解度数据与Apelblat方程、van't Hoff方程、λh方程和Jouyban-Acree模型4种模型相关，均表现出较好的一致性。其中，Apelblat方程相关性最好，平均相对平均偏差（RAD）为7.264 × 10−3，均方根偏差（RMSD）为0.355 × 10−3。利用修正的van't Hoff方程计算了溶解焓变（ΔsolHo）在1.69 ~ 18.04 kJ·mol−1之间，溶解熵变（ΔsolSo）在- 14.55 ~ 22.34 J·mol−1之间，溶解吉布斯自由能（ΔsolGo）在6.10 ~ 11.28 kJ·mol−1之间。ΔsolHo和ΔsolGo均为正值，表明在给定条件下，溶解过程是吸热的，非自发的。这些溶解度和热力学结果为HMTA的结晶和纯化过程的设计提供了关键信息。

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来源期刊

Journal of Chemical Thermodynamics 工程技术-热力学

CiteScore

5.60

自引率

15.40%

发文量

199

审稿时长

79 days

期刊介绍： The Journal of Chemical Thermodynamics exists primarily for dissemination of significant new knowledge in experimental equilibrium thermodynamics and transport properties of chemical systems. The defining attributes of The Journal are the quality and relevance of the papers published. The Journal publishes work relating to gases, liquids, solids, polymers, mixtures, solutions and interfaces. Studies on systems with variability, such as biological or bio-based materials, gas hydrates, among others, will also be considered provided these are well characterized and reproducible where possible. Experimental methods should be described in sufficient detail to allow critical assessment of the accuracy claimed. Authors are encouraged to provide physical or chemical interpretations of the results. Articles can contain modelling sections providing representations of data or molecular insights into the properties or transformations studied. Theoretical papers on chemical thermodynamics using molecular theory or modelling are also considered. The Journal welcomes review articles in the field of chemical thermodynamics but prospective authors should first consult one of the Editors concerning the suitability of the proposed review. Contributions of a routine nature or reporting on uncharacterised materials are not accepted.