Journal of Chemical Thermodynamics最新文献

{"title":"Multi-model synergy for hypergravity silica gel–water vapor adsorption isotherms: experimental validation and predictive modeling.","authors":"Dezhi Li ,&nbsp;Xu Zheng ,&nbsp;Suyun Yi ,&nbsp;Ning Mei","doi":"10.1016/j.jct.2026.107644","DOIUrl":"10.1016/j.jct.2026.107644","url":null,"abstract":"<div><div>Abstract</div><div>Hypergravity significantly enhances gas–solid mass transfer, yet systematic equilibrium data and reliable predictive models remain scarce. To address this gap, we conducted a comprehensive set of 256 adsorption experiments for silica gel and water vapor under a full-factorial design, spanning hypergravity factors (β) from 0 to 40, temperatures (T) from 298.2 to 308.2 K, and relative humidities (φ) from 20% to 95%. Compared with the fixed bed (β = 0), hypergravity at β = 16 increased the adsorption capacity by 39%.</div><div>Six classical adsorption isotherm models were evaluated, among which the Sips and Dubinin–Radushkevich (DR) equations delivered the best fits. Based on adsorption potential theory, we developed a modified DR model by correlating the affinity coefficient with T, β, and φ, yielding an explicit functional relation q = f(T, β, φ). This model preserves clear mechanistic interpretability while achieving high accuracy (R² = 0.992–0.999) and stable performance within a practical hypergravity range of β = 10–50, making it particularly suitable for mechanistic analysis and process simulation under moderate-to-high hypergravity conditions.</div><div>Complementing this theoretical approach, we also proposed a dimensionless correlation and two machine learning models—support vector machine (SVM) and backpropagation (BP) neural network. The BP model, trained on a combined dataset comprising experimental data, modified DR predictions, and characteristic-curve extrapolation results, attained the highest predictive accuracy (test R² = 0.9994).</div><div>Collectively, the integrated framework—combining the modified DR, dimensionless, and machine learning models—offers a reliable suite of tools for predicting hypergravity adsorption isotherms and provides a methodological blueprint extendable to other adsorbent–adsorbate gas–solid systems.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"215 ","pages":"Article 107644"},"PeriodicalIF":2.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146190081","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}

{"title":"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","authors":"Yimin Jia ,&nbsp;Mingting Yuan ,&nbsp;Mei Ma ,&nbsp;Qiutong Zhang ,&nbsp;Wenhao Yan ,&nbsp;Yingchen Wang ,&nbsp;Jiaqi Luo ,&nbsp;Qiushuo Yu","doi":"10.1016/j.jct.2026.107643","DOIUrl":"10.1016/j.jct.2026.107643","url":null,"abstract":"<div><div>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 (<span><math><msub><mi>Δ</mi><mi>sol</mi></msub><msup><mi>H</mi><mi>o</mi></msup></math></span>) ranged from 1.69 to 18.04 kJ·mol⁻¹, the dissolution entropy change (<span><math><msub><mi>Δ</mi><mi>sol</mi></msub><msup><mi>S</mi><mi>o</mi></msup></math></span>) from −14.55 to 22.34 J·mol⁻¹·K⁻¹, and the dissolution Gibbs free energy change (<span><math><msub><mi>Δ</mi><mi>sol</mi></msub><msup><mi>G</mi><mi>o</mi></msup></math></span>) from 6.10 to 11.28 kJ·mol⁻¹. The positive values of both <span><math><msub><mi>Δ</mi><mi>sol</mi></msub><msup><mi>H</mi><mi>o</mi></msup></math></span> and <span><math><msub><mi>Δ</mi><mi>sol</mi></msub><msup><mi>G</mi><mi>o</mi></msup></math></span> 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.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"215 ","pages":"Article 107643"},"PeriodicalIF":2.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146190085","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}

{"title":"New thermodynamic aspects and speciation properties of the angiotensin-converting enzyme inhibitor drug, lisinopril with Cu2+, Zn2+, Ca2+, Mg2+ in sodium chloride aqueous solution","authors":"Kavosh Majlesi ,&nbsp;Concetta De Stefano ,&nbsp;Francesco Crea ,&nbsp;Clemente Bretti","doi":"10.1016/j.jct.2026.107632","DOIUrl":"10.1016/j.jct.2026.107632","url":null,"abstract":"<div><div>(2<em>S</em>)-1-[(2<em>S</em>)-6-amino-2-[[(1<em>S</em>)-1-carboxy-3-phenylpropyl]amino]hexanoyl]pyrrolidine-2- carboxylic acid (Lisinopril) is a drug commonly used to treat hypertension and heart failure. In recent years, it has also been identified as an emerging environmental contaminant. In this study, the thermodynamic behavior of lisinopril in aqueous solution was investigated. The protonation constants of lisinopril were determined potentiometrically at different temperatures (288.15 ≤ <em>T</em>/K ≤ 310.15) and ionic strengths (0.16 ≤ <em>I</em>/mol kg⁻¹(H₂O) ≤ 0.97, NaCl). The findings indicate that the first two and the fourth protonation steps are driven by enthalpic contributions, whereas the third is slightly entropy driven. Furthermore, based on the distinct acid-base characteristics of the metal ions and the possible formation of sparingly soluble species, different speciation models were proposed for the various metal/lisinopril systems, including: ZnH₂L⁺², ZnHL⁺, CuHL⁺, CuL, CaL, CaHL⁺, MgL and MgHL⁺. The Specific Ion Interaction Theory (SIT) and a modified extended Debye–Hückel equation were employed to model the thermodynamic formation parameters as a function of ionic strength and temperature. Finally, the distribution of lisinopril species (protonation and complex formation constants) under conditions simulating real systems, such as seawater, was evaluated.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"215 ","pages":"Article 107632"},"PeriodicalIF":2.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146190083","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}

{"title":"Development and prospect of low-temperature adiabatic calorimetry","authors":"Katie Yue Liu ,&nbsp;Xiyu Zhao ,&nbsp;Brian F. Woodfield ,&nbsp;Siyuan Zhao ,&nbsp;Ji-Peng Luo ,&nbsp;Quan Shi","doi":"10.1016/j.jct.2026.107630","DOIUrl":"10.1016/j.jct.2026.107630","url":null,"abstract":"<div><div>Heat capacity is a fundamental thermodynamic property that provides essential insights into the behavior of phase transitions, quantum effects, and the molecular thermal motion of matter. Adiabatic calorimetry is one of the most reliable methods for obtaining precise and accurate heat capacity data and for studying the fundamental properties of materials. In this context, this review traces the development of adiabatic calorimetry over the past 120 years, from the earliest prototype instruments to successive generations with advances toward smaller sample size, improved cooling, and enhanced automation. We then emphasize the need for measurements under extreme conditions, including high external fields or ultra-low temperatures. Furthermore, this review highlights the ongoing developments in commercial implementation, modular system design, and integration with machine learning. By consolidating existing knowledge and outlining future directions, we hope to raise awareness of adiabatic calorimetry as a vital tool for modern materials research and encourage the scientific community to pay greater attention to promoting the development and capabilities of calorimetric techniques.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"215 ","pages":"Article 107630"},"PeriodicalIF":2.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146079521","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}

{"title":"Experimental and theoretical investigation on viscosity of carbonated piperazine (PZ) activated 1-dimethylamino-2-propanol (DMA2P) aqueous blends","authors":"Jianjun Chen ,&nbsp;Jian Ma ,&nbsp;Jichao Hu ,&nbsp;Pan Zhang ,&nbsp;Dong Fu ,&nbsp;Lemeng Wang","doi":"10.1016/j.jct.2026.107627","DOIUrl":"10.1016/j.jct.2026.107627","url":null,"abstract":"<div><div>In this study, we investigated the viscosity data of carbonated aqueous blends of 1-dimethylamino-2-propanol (DMA2P) and piperazine (PZ) over a temperature range of 303.2 to 323.2 K at atmospheric pressure. The concentration of DMA2P and PZ ranged from 30 wt% to 50 wt% and 2.5 wt% to 7.5 wt%, respectively. The experimental viscosities were calculated and predicted using the Weiland equation. The calculations showed good agreement with the experimental results, yielding an average relative deviation of 2.18%. Furthermore, the viscosity activation energy (<em>E</em>a) and the estimated diffusion coefficient of CO₂ (<em>D</em>_CO2) into the carbonated DMA2P-PZ aqueous blends were derived using the Arrhenius-type expression and the modified Stokes-Einstein equation, respectively. The results indicate that the DMA2P-PZ absorbent exhibits promising potential for industrial application in CO₂ capture processes.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"215 ","pages":"Article 107627"},"PeriodicalIF":2.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145981924","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}

{"title":"Phase equilibria in the system Fe-Cu-Sn-FeO at iron saturation","authors":"Bayu Anto ,&nbsp;Lassi Klemettinen ,&nbsp;Pekka Taskinen ,&nbsp;Matti Kurhila ,&nbsp;Mia Tiljander ,&nbsp;Daniel Lindberg","doi":"10.1016/j.jct.2026.107628","DOIUrl":"10.1016/j.jct.2026.107628","url":null,"abstract":"<div><div>The equilibria between tin and ferrous oxide were approached at 1100–1300 °C by experiments using copper‑tin alloys as sources of tin. The experiments were carried out in closed iron ampoules sealed with laser welding to avoid tin and tin oxide volatilization during equilibration. The phase composition analyses were conducted by electron probe X-ray microanalysis for the major and minor components and laser ablation-inductively coupled plasma-mass spectrometry for the trace concentrations directly from polished sections. The copper‑iron‑tin phase diagram was measured at FeO saturation up to 20 wt% Sn in the liquid copper alloy. The thermodynamic properties of tin and copper in solid iron were evaluated. Additionally, the dissolution of tin and copper in ferrous oxide was measured at iron saturation.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"215 ","pages":"Article 107628"},"PeriodicalIF":2.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146079520","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}

{"title":"Neural circuit policies for accurate prediction of interfacial tensions between liquid mixture of hydrocarbons and brine","authors":"Yan-Ling Yang ,&nbsp;Belinda Kezia Purwanto ,&nbsp;Pannuru Venkatesu","doi":"10.1016/j.jct.2026.107626","DOIUrl":"10.1016/j.jct.2026.107626","url":null,"abstract":"<div><div>Interfacial tension (IFT) between hydrocarbons and brines plays a key role in the process of enhanced oil recovery. Although various experimental and simulation studies have been conducted on hydrocarbons-brine systems, a comprehensive empirical correlation for IFT in hydrocarbon-brine systems remains not fully understood. This study develops three architectures for IFT prediction: deep neural network (DNN), long short-term memory (LSTM), and neural circuit policies (NCP). It is common for the input vector of a two-phase system to contain several numerical parameters, including pressure (P), temperature (T), specific gravity (ρ), sodium chloride (NaCl) equivalent salinity, and pH. In addition to utilizing the DNN approach, the LSTM and NCP approaches also incorporate a simplified molecular input-line entry system (SMILES) as input data. Of the three approaches, the NCP approach with all six parameters and SMILES had the lowest root mean squared error (RMSE) among all the tested methods, with a value of 0.048 mN/m. Furthermore, the number of trainable weights in the NCP approach is 8.3–15 times smaller than that in the DNN and LSTM approaches. Therefore, our proposed NCP approach demonstrates better generalizability and robustness than significantly larger black-box learning systems. Increasing brine salinity raises IFT due to the preferential retention of salt ions in the bulk water, which limits their ability to disrupt the cohesive structure of water molecules at the interface, ultimately stabilizing IFT at high salinity levels.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"215 ","pages":"Article 107626"},"PeriodicalIF":2.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146039750","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}

{"title":"Low temperature heat capacity and thermodynamic functions of zirconium (IV) sulfate in the tetrahydrate and anhydrous forms","authors":"Emma Esplin,&nbsp;Natalie Parkinson,&nbsp;Brian F. Woodfield","doi":"10.1016/j.jct.2026.107631","DOIUrl":"10.1016/j.jct.2026.107631","url":null,"abstract":"<div><div>The heat capacities of alpha zirconium (IV) sulfate in its tetrahydrate and anhydrous forms were measured from 1.8 K to 300 K via relaxation calorimetry. The measured heat capacities have been fit to theoretical functions and compared to the available literature. Smoothed entropy and enthalpy increments from 0 K to 300 K were calculated from the fits of the data, and the absolute entropies for Zr(SO₄)₂ ∙ 4.02H₂O and Zr(SO₄)₂ at 298.15 K are 298.80 J∙K⁻¹ mol⁻¹ and 170.57 J∙K⁻¹ mol⁻¹, respectively. The Gibbs energies of formation relative to the elements and to the oxides at 298.15 K were calculated using available enthalpy of formation data. For Zr(SO₄)₂ ∙ 4.02H₂O and Zr(SO₄)₂, respectively, the Gibbs energies of formation at 298.15 K from the elements are −2990.6 kJ∙mol⁻¹ and − 2006.7 kJ∙mol⁻¹ and from the oxides are −270.2 kJ∙mol⁻¹ and − 237.9 kJ∙mol⁻¹.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"215 ","pages":"Article 107631"},"PeriodicalIF":2.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146190028","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}

{"title":"Insight of thermodynamic properties by the substitution of alkali metal ions in X2InGaCl6 (X = K, Rb, Cs) perovskites: DFT calculation and AIMD simulation","authors":"Asghar Hussain ,&nbsp;Ijaz Hussain ,&nbsp;Muhammad Khuram Shahzad ,&nbsp;Ghulam Abbas Ashraf ,&nbsp;Naoufel Ben Hamadi ,&nbsp;Kenja Ruzimov ,&nbsp;Yedluri Anil Kumar ,&nbsp;Yusufbay Yusupov ,&nbsp;Vineet Tirth ,&nbsp;Mostafa A.H. Abdelmohimen","doi":"10.1016/j.jct.2026.107629","DOIUrl":"10.1016/j.jct.2026.107629","url":null,"abstract":"<div><div>To address the crucial problems of lead toxicity and stability, we must find environmentally benign substitutes to conventional perovskite solar cells. This study aims to provide a comprehensive first-principles evaluation of lead-free halide double perovskite series X₂InGaCl₆ (X = K, Rb, Cs) as tunable semiconductors for optoelectronics. Using density functional theory (DFT) calculations within the CASTEP code, we analytically investigated their structural, electronic, mechanical, and optical properties, alongside phonon dispersion and ab initio molecular dynamics for stability assessment. The calculated tolerance factors (0.89–0.97) and negative formation energies confirm thermodynamic stability, while AIMD confirms robust thermal stability at 300 K. The results reveal tunable indirect bandgaps of 1.38 eV for K₂InGaCl₆, 1.48 eV for Rb₂InGaCl₆ and 1.71 eV for Cs₂InGaCl₆. Mechanically, all materials are stable, with K₂InGaCl₆ being ductile (<span><math><mi>B</mi><mo>/</mo><mi>G</mi><mo>=</mo></math></span>2.23), while Rb₂InGaCl₆ (<span><math><mi>B</mi><mo>/</mo><mi>G</mi><mo>=</mo></math></span>1.77) and Cs₂InGaCl₆ (<span><math><mi>B</mi><mo>/</mo><mi>G</mi><mo>=</mo></math></span>1.79) are brittle. Optical investigations show robust absorption from the ultraviolet to infrared regions. In conclusion, these environmentally benign perovskites indicate highly tunable and favorable features for applications in photovoltaics, UV photodetectors, and flexible optoelectronic devices.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"215 ","pages":"Article 107629"},"PeriodicalIF":2.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146079519","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}

{"title":"Behaviors salts of diammonium hydrogenphosphate or sulfate containing in fertilizers, solubility and thermodynamic study in aqueous solutions at various temperatures","authors":"S.M. Aboufaris El Alaoui,&nbsp;M. EL Guendouzi","doi":"10.1016/j.jct.2026.107641","DOIUrl":"10.1016/j.jct.2026.107641","url":null,"abstract":"<div><div>In this study, both experimental and calculated solubilities of binary aqueous solutions of diammonium (hydrogenphosphate or sulfate) were determined at various temperatures. The experimental solubilities of <span><math><msub><mfenced><msub><mi>NH</mi><mn>4</mn></msub></mfenced><mn>2</mn></msub><mi>HP</mi><msub><mi>O</mi><mn>4</mn></msub><mfenced><mi>aq</mi></mfenced></math></span> and <span><math><msub><mfenced><msub><mi>NH</mi><mn>4</mn></msub></mfenced><mn>2</mn></msub><mi>S</mi><msub><mi>O</mi><mn>4</mn></msub><mfenced><mi>aq</mi></mfenced></math></span> ranged from <span><math><msub><mi>m</mi><mrow><mi>s</mi><mspace></mspace><mfenced><mi>exp</mi></mfenced></mrow></msub></math></span> = 5.260 to 8.641 <span><math><mi>mol</mi><mo>·</mo><msup><mi>kg</mi><mrow><mo>−</mo><mn>1</mn></mrow></msup></math></span> and <span><math><msub><mi>m</mi><mrow><mi>s</mi><mspace></mspace><mfenced><mi>exp</mi></mfenced></mrow></msub></math></span> = 5.799 to 7.122 <span><math><mi>mol</mi><mo>·</mo><msup><mi>kg</mi><mrow><mo>−</mo><mn>1</mn></mrow></msup></math></span>, respectively, between the temperatures of 298.15 K and 353.15 K. The thermodynamic properties of the studied systems were derived from water activity measurements. Thus, the water activities of these aqueous solutions were measured from dilute to saturated solutions using the hygrometric method at different temperatures. From the new experimental water activities, the osmotic coefficients of water for the electrolyte solutions were obtained at the temperature range. The treatment of the obtained coefficients was made by the expanded ion interaction models. The related thermodynamic properties of the sub-binary systems were assessed using the developed models of Pitzer and Clegg–Pitzer–Brimblecombe. Indeed, the binary parameters of diammonium hydrogenphosphate or sulfate aqueous solutions were calculated and used for the computation of solute activity and osmotic coefficients; a good description of the calculated activity coefficients is acquired by the adequate models. The dissolution Gibbs energies and the solubility product of <span><math><msub><mfenced><msub><mi>NH</mi><mn>4</mn></msub></mfenced><mn>2</mn></msub><mi>HP</mi><msub><mi>O</mi><mn>4</mn></msub><mfenced><mi>s</mi></mfenced></math></span> and <span><math><msub><mfenced><msub><mi>NH</mi><mn>4</mn></msub></mfenced><mn>2</mn></msub><mi>S</mi><msub><mi>O</mi><mn>4</mn></msub><mfenced><mi>s</mi></mfenced></math></span> were also evaluated at different temperatures. In addition, excess thermodynamic functions such as <span><math><mo>∆</mo><msup><mi>G</mi><mi>E</mi></msup><mo>,</mo><mo>∆</mo><msup><mi>H</mi><mi>E</mi></msup></math></span>, and <span><math><mo>∆</mo><msup><mi>S</mi><mi>E</mi></msup></math></span>, along with the partial molar entropies of solvent and solute, were obtained. Based on these results, the sulfate and phosphate systems exhibit opposite hydration behavior and thermodynamic stability.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"215 ","pages":"Article 107641"},"PeriodicalIF":2.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146190082","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}