Pub Date : 2026-01-24DOI: 10.1016/j.jct.2026.107630
Katie Yue Liu , Xiyu Zhao , Brian F. Woodfield , Siyuan Zhao , Ji-Peng Luo , Quan Shi
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.
{"title":"Development and prospect of low-temperature adiabatic calorimetry","authors":"Katie Yue Liu , Xiyu Zhao , Brian F. Woodfield , Siyuan Zhao , Ji-Peng Luo , 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":"2026-01-24","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}
Pub Date : 2026-01-23DOI: 10.1016/j.jct.2026.107628
Bayu Anto , Lassi Klemettinen , Pekka Taskinen , Matti Kurhila , Mia Tiljander , Daniel Lindberg
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.
{"title":"Phase equilibria in the system Fe-Cu-Sn-FeO at iron saturation","authors":"Bayu Anto , Lassi Klemettinen , Pekka Taskinen , Matti Kurhila , Mia Tiljander , 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":"2026-01-23","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}
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 (2.23), while Rb2InGaCl6 (1.77) and Cs2InGaCl6 (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.
{"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 , Ijaz Hussain , Muhammad Khuram Shahzad , Ghulam Abbas Ashraf , Naoufel Ben Hamadi , Kenja Ruzimov , Yedluri Anil Kumar , Yusufbay Yusupov , Vineet Tirth , 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 X<sub>2</sub>InGaCl<sub>6</sub> (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 K<sub>2</sub>InGaCl<sub>6</sub>, 1.48 eV for Rb<sub>2</sub>InGaCl<sub>6</sub> and 1.71 eV for Cs<sub>2</sub>InGaCl<sub>6</sub>. Mechanically, all materials are stable, with K<sub>2</sub>InGaCl<sub>6</sub> being ductile (<span><math><mi>B</mi><mo>/</mo><mi>G</mi><mo>=</mo></math></span>2.23), while Rb<sub>2</sub>InGaCl<sub>6</sub> (<span><math><mi>B</mi><mo>/</mo><mi>G</mi><mo>=</mo></math></span>1.77) and Cs<sub>2</sub>InGaCl<sub>6</sub> (<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":"2026-01-21","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}
Pub Date : 2026-01-14DOI: 10.1016/j.jct.2026.107627
Jianjun Chen , Jian Ma , Jichao Hu , Pan Zhang , Dong Fu , Lemeng Wang
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 (Ea) and the estimated diffusion coefficient of CO2 (DCO2) 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.
{"title":"Experimental and theoretical investigation on viscosity of carbonated piperazine (PZ) activated 1-dimethylamino-2-propanol (DMA2P) aqueous blends","authors":"Jianjun Chen , Jian Ma , Jichao Hu , Pan Zhang , Dong Fu , 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 CO<sub>2</sub> (<em>D</em><sub>CO2</sub>) 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 CO<sub>2</sub> capture processes.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"215 ","pages":"Article 107627"},"PeriodicalIF":2.2,"publicationDate":"2026-01-14","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}
Pub Date : 2026-01-14DOI: 10.1016/j.jct.2026.107626
Yan-Ling Yang , Belinda Kezia Purwanto , Pannuru Venkatesu
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.
{"title":"Neural circuit policies for accurate prediction of interfacial tensions between liquid mixture of hydrocarbons and brine","authors":"Yan-Ling Yang , Belinda Kezia Purwanto , 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":"2026-01-14","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}
Pub Date : 2026-01-06DOI: 10.1016/j.jct.2026.107625
El Houssaine Benaddi, My Rachid Laamari
This study aims to develop a high-performance activated carbon (AC) from prickly pear seed cake powder (PPSC) to address current limitations in the removal of cationic dyes from water. The optimized adsorbent, produced through H₃PO₄ impregnation at a 1:1 (g:mL) ratio (AC-PPSC1–1) and followed by carbonization at optimal conditions, was extensively characterized to determine its structural, chemical, and surface properties. SEM analyses revealed a well-developed microporous structure, while EDX confirmed its elemental composition. BET measurements showed a high specific surface area of 433.5647 m2·g−1 with dominant microporosity. FT-IR spectroscopy identified key functional groups including OH, CO, CH, phosphorus bands (PO, P-O-C, POOH), and CO supporting the proposed adsorption mechanisms. XRD analysis confirmed the amorphous nature of the material, and pHPZC and zeta potential measurements clarified the surface charge characteristics. Batch experiments, supported by kinetic and isotherm modeling, showed that methylene blue (MB) adsorption onto AC-PPSC1–1 follows pseudo-second-order kinetics and fits the Freundlich isotherm, indicating multilayer physisorption. Thermodynamic analysis further demonstrated that the process is rapid, favorable, and exothermic. Under optimized conditions (pH 6, 0.02 g of AC-PPSC1–1, MB concentration 9.38 × 10−5 mol·kg−1, 298 K, and 50 mL of solution), the adsorbent achieved a removal efficiency of 97.32 % and an equilibrium adsorption capacity of 85.65 mg·g−1 (0.2678 mol.kg−1). Overall, AC-PPSC1–1 emerges as a highly efficient, low-cost, and environmentally friendly adsorbent, offering a valuable contribution to the literature on biomass-derived activated carbons and providing an effective solution for the removal of cationic organic pollutants from aqueous environments.
{"title":"Facile synthesis of low-cost porous activated carbon and the adsorption properties: Characterization, optimization, kinetic models, and thermodynamic study","authors":"El Houssaine Benaddi, My Rachid Laamari","doi":"10.1016/j.jct.2026.107625","DOIUrl":"10.1016/j.jct.2026.107625","url":null,"abstract":"<div><div>This study aims to develop a high-performance activated carbon (AC) from prickly pear seed cake powder (PPSC) to address current limitations in the removal of cationic dyes from water. The optimized adsorbent, produced through H₃PO₄ impregnation at a 1:1 (g:mL) ratio (AC-PPSC<sub>1–1</sub>) and followed by carbonization at optimal conditions, was extensively characterized to determine its structural, chemical, and surface properties. SEM analyses revealed a well-developed microporous structure, while EDX confirmed its elemental composition. BET measurements showed a high specific surface area of 433.5647 m<sup>2</sup>·g<sup>−1</sup> with dominant microporosity. FT-IR spectroscopy identified key functional groups including O<img>H, C<img>O, C<img>H, phosphorus bands (P<img>O, P-O-C, P<img>OOH), and C<img>O supporting the proposed adsorption mechanisms. XRD analysis confirmed the amorphous nature of the material, and pH<sub>PZC</sub> and zeta potential measurements clarified the surface charge characteristics. Batch experiments, supported by kinetic and isotherm modeling, showed that methylene blue (MB) adsorption onto AC-PPSC<sub>1–1</sub> follows pseudo-second-order kinetics and fits the Freundlich isotherm, indicating multilayer physisorption. Thermodynamic analysis further demonstrated that the process is rapid, favorable, and exothermic. Under optimized conditions (pH 6, 0.02 g of AC-PPSC<sub>1–1</sub>, MB concentration 9.38 × 10<sup>−5</sup> mol·kg<sup>−1</sup>, 298 K, and 50 mL of solution), the adsorbent achieved a removal efficiency of 97.32 % and an equilibrium adsorption capacity of 85.65 mg·g<sup>−1</sup> (0.2678 mol.kg<sup>−1</sup>). Overall, AC-PPSC<sub>1–1</sub> emerges as a highly efficient, low-cost, and environmentally friendly adsorbent, offering a valuable contribution to the literature on biomass-derived activated carbons and providing an effective solution for the removal of cationic organic pollutants from aqueous environments.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"214 ","pages":"Article 107625"},"PeriodicalIF":2.2,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145938422","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}
Pub Date : 2026-01-05DOI: 10.1016/j.jct.2026.107624
Mariana B.S. Felgueiras, Ana Rita Querido, Manuel F.R. Pereira, Olívia S.G.P. Soares
Carbon dioxide (CO2) is the primary contributor to the greenhouse effect. Its emissions have increased in recent years, primarily due to the burning of fossil fuels for energy production and transportation. Therefore, developing processes capable of converting CO2 into value-added products that can serve as alternative fuels is crucial. As thermodynamic equilibrium analysis offers key insights into species stability, reactant conversion, and product selectivity, a thermodynamic equilibrium study of the RWGS reaction, CO2 methanation, CO2 hydrogenation to methanol, ethanol and ethylene glycol was conducted using Aspen Plus V12.1 simulation software, with the Peng-Robinson equation of state as the thermodynamic model. The influence of temperature, pressure and H2:CO2 ratio on reaction equilibrium was assessed via an RGIBBS reactor model. This research evaluated the thermodynamic behavior of ethanol and ethylene glycol synthesis via CO2 hydrogenation, as these compounds have not yet received significant attention in literature. While the hydrogenation of CO2 to ethanol is thermodynamically feasible over a wide range of temperatures and pressures, the production of ethylene glycol is only favorable at temperatures below 200 °C. Kinetic studies indicated that most catalysts operated near thermodynamic equilibrium; however, the catalyst for the RWGS and for the CO2 hydrogenation to methanol were likely operating under kinetic control rather than being close to thermodynamic equilibrium.
二氧化碳（CO2）是温室效应的主要贡献者。近年来，其排放量有所增加，主要是由于能源生产和运输燃烧化石燃料。因此，开发能够将二氧化碳转化为可作为替代燃料的增值产品的工艺至关重要。由于热力学平衡分析是了解物种稳定性、反应物转化和产物选择性的关键，因此采用Aspen Plus V12.1模拟软件，以Peng-Robinson状态方程为热力学模型，对RWGS反应、CO2甲烷化、CO2加氢制甲醇、乙醇和乙二醇的热力学平衡进行了研究。通过RGIBBS反应器模型评估了温度、压力和H2:CO2比对反应平衡的影响。本研究评估了通过CO2加氢合成乙醇和乙二醇的热力学行为，因为这些化合物尚未得到文献的重视。虽然从热力学角度来看，二氧化碳加氢制乙醇在很大的温度和压力范围内都是可行的，但乙二醇的生产只有在低于200°C的温度下才有利。动力学研究表明，大多数催化剂在热力学平衡附近运行；然而，RWGS和CO2加氢制甲醇的催化剂可能在动力学控制下运行，而不是接近热力学平衡。
{"title":"Thermodynamic analysis and kinetics studies of CO2 hydrogenation to alcohols by reverse water--gas shift and Fischer-Tropsch reactions","authors":"Mariana B.S. Felgueiras, Ana Rita Querido, Manuel F.R. Pereira, Olívia S.G.P. Soares","doi":"10.1016/j.jct.2026.107624","DOIUrl":"10.1016/j.jct.2026.107624","url":null,"abstract":"<div><div>Carbon dioxide (CO<sub>2</sub>) is the primary contributor to the greenhouse effect. Its emissions have increased in recent years, primarily due to the burning of fossil fuels for energy production and transportation. Therefore, developing processes capable of converting CO<sub>2</sub> into value-added products that can serve as alternative fuels is crucial. As thermodynamic equilibrium analysis offers key insights into species stability, reactant conversion, and product selectivity, a thermodynamic equilibrium study of the RWGS reaction, CO<sub>2</sub> methanation, CO<sub>2</sub> hydrogenation to methanol, ethanol and ethylene glycol was conducted using Aspen Plus V12.1 simulation software, with the Peng-Robinson equation of state as the thermodynamic model. The influence of temperature, pressure and H<sub>2</sub>:CO<sub>2</sub> ratio on reaction equilibrium was assessed via an RGIBBS reactor model. This research evaluated the thermodynamic behavior of ethanol and ethylene glycol synthesis via CO<sub>2</sub> hydrogenation, as these compounds have not yet received significant attention in literature. While the hydrogenation of CO<sub>2</sub> to ethanol is thermodynamically feasible over a wide range of temperatures and pressures, the production of ethylene glycol is only favorable at temperatures below 200 °C. Kinetic studies indicated that most catalysts operated near thermodynamic equilibrium; however, the catalyst for the RWGS and for the CO<sub>2</sub> hydrogenation to methanol were likely operating under kinetic control rather than being close to thermodynamic equilibrium.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"214 ","pages":"Article 107624"},"PeriodicalIF":2.2,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145977057","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}
trans-1,1,1,4,4,4-hexafluoro-2-butene (R1336mzz(E)) is a hydrofluoroolefin with 4 carbon atoms and low global warming potential. It is suitable for application as a refrigerant, but its thermophysical properties need further investigation. In this work, experimental measurements for R1336mzz(E) of the vapor pressure from 303.17 K to the critical point and the pvT property up to 850 kg/m3 from 323.15 K to 423.15 K were conducted by using the Burnett method. An improved Burnett apparatus with variable volume constants has evolved from the classical two-chamber apparatus, and the 2,3,3,3-tetrafluoroprop-1-ene (R1234yf) as a typical hydrofluoroolefin was used to validate the improved variable-volume-constant Burnett method. The vapor pressure of R1234yf was measured from 313.15 K to 367.15 K and the pvT property was measured up to 800 kg/m3 from 325.00 K to 403.15 K. The expanded measurement uncertainties (k = 2) of temperature, pressure and density are 0.014 K, 0.2–0.4 kPa and 0.0014·ρ for the classical two-chamber Burnett apparatus, and are 0.014 K, 0.2–0.5 kPa and 0.0020·ρ for the improved Burnett apparatus, respectively. The experimental data is compared with the literature data and the existing equations of state. For R1336mzz(E), the experiment measured the near-critical region and updated the critical pressure at the critical temperature of 403.37 K to be 2.7788 MPa. A new critical isochore method for critical density measurement is proposed and verified in this work and the critical density of R1336mzz(E) is measured to be 513 kg/m3.
{"title":"Experimental measurement of vapor pressure and pvT property for trans-1,1,1,4,4,4-hexafluoro-2-butene (R1336mzz(E)) and 2,3,3,3-tetrafluoroprop-1-ene (R1234yf) by using the Burnett method","authors":"Erqi Wang, Ruiqi Wang, Shuzhou Peng, Zhen Yang, Yuanyuan Duan","doi":"10.1016/j.jct.2025.107623","DOIUrl":"10.1016/j.jct.2025.107623","url":null,"abstract":"<div><div><em>trans</em>-1,1,1,4,4,4-hexafluoro-2-butene (R1336mzz(E)) is a hydrofluoroolefin with 4 carbon atoms and low global warming potential. It is suitable for application as a refrigerant, but its thermophysical properties need further investigation. In this work, experimental measurements for R1336mzz(E) of the vapor pressure from 303.17 K to the critical point and the <em>pvT</em> property up to 850 kg/m<sup>3</sup> from 323.15 K to 423.15 K were conducted by using the Burnett method. An improved Burnett apparatus with variable volume constants has evolved from the classical two-chamber apparatus, and the 2,3,3,3-tetrafluoroprop-1-ene (R1234yf) as a typical hydrofluoroolefin was used to validate the improved variable-volume-constant Burnett method. The vapor pressure of R1234yf was measured from 313.15 K to 367.15 K and the <em>pvT</em> property was measured up to 800 kg/m<sup>3</sup> from 325.00 K to 403.15 K. The expanded measurement uncertainties (<em>k</em> = 2) of temperature, pressure and density are 0.014 K, 0.2–0.4 kPa and 0.0014·<em>ρ</em> for the classical two-chamber Burnett apparatus, and are 0.014 K, 0.2–0.5 kPa and 0.0020·<em>ρ</em> for the improved Burnett apparatus, respectively. The experimental data is compared with the literature data and the existing equations of state. For R1336mzz(E), the experiment measured the near-critical region and updated the critical pressure at the critical temperature of 403.37 K to be 2.7788 MPa. A new critical isochore method for critical density measurement is proposed and verified in this work and the critical density of R1336mzz(E) is measured to be 513 kg/m<sup>3</sup>.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"214 ","pages":"Article 107623"},"PeriodicalIF":2.2,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145797355","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}
Pub Date : 2025-12-15DOI: 10.1016/j.jct.2025.107621
Gennadiy I. Egorov
For the first time, the coefficients of compression (relative volume change) of the binary liquid {glycerol (1) + dimethyl sulfoxide (2)} mixture have been measured at temperatures ranging from 278.15 K to 323.15 K (278.15, 288.15, 288.15, 308.15, 323.15) and pressures up to 100 MPa (10, 25, 50, 75 and 100). The measurements at temperatures below 298.15 were carried out in a limited composition range up to = 0.55 ( is the mole fraction of dimethyl sulfoxide) due to the mixture transition to the solid phase. The obtained compression values of the pure mixture components were compared with the literature data. The excess molar volumes, , molar isothermal compressibilities,, molar isobaric thermal expansions, , coefficients of isochoric thermal pressure, , of the mixture, as well as partial molar volumes of the mixture components, , including their limiting values, were calculated. The excess molar volumes were fitted with the Redlich-Kister equation. The formation of the glycerol + dimethyl sulfoxide mixture was shown to reduce the volume, whereas a pressure increase and a temperature decrease led to a smaller deviation from ideality, . Pressure and temperature were shown to produce the opposite effects on the partial molar volumes of both mixture components. The pressure coefficient of the limiting partial molar volumes of glycerol in dimethyl sulfoxide changes its sign in the studied temperature range. The molar isothermal compressibility and molar isobaric thermal expansion of the mixture grew exponentially as the mole fraction of dimethyl sulfoxide increased. The concentration dependencies of the isochoric thermal pressure coefficient of the mixture were found to have no extremum.
{"title":"Effect of high pressure and temperature on the volumetric properties of the liquid-phase {glycerol (1) + dimethyl sulfoxide (2)} mixture","authors":"Gennadiy I. Egorov","doi":"10.1016/j.jct.2025.107621","DOIUrl":"10.1016/j.jct.2025.107621","url":null,"abstract":"<div><div>For the first time, the coefficients of compression <span><math><mi>k</mi><mo>=</mo><mi>ΔV</mi><mo>/</mo><msub><mi>V</mi><mi>o</mi></msub></math></span> (relative volume change) of the binary liquid {glycerol (1) + dimethyl sulfoxide (2)} mixture have been measured at temperatures ranging from 278.15 K to 323.15 K (278.15, 288.15, 288.15, 308.15, 323.15) and pressures up to 100 MPa (10, 25, 50, 75 and 100). The measurements at temperatures below 298.15 were carried out in a limited composition range up to <span><math><msub><mi>x</mi><mn>2</mn></msub></math></span> = 0.55 (<span><math><msub><mi>x</mi><mn>2</mn></msub></math></span> is the mole fraction of dimethyl sulfoxide) due to the mixture transition to the solid phase. The obtained compression values of the pure mixture components were compared with the literature data. The excess molar volumes, <span><math><msubsup><mi>V</mi><mi>m</mi><mi>E</mi></msubsup></math></span>, molar isothermal compressibilities,<span><math><msub><mi>K</mi><mrow><mi>T</mi><mo>,</mo><mi>m</mi></mrow></msub></math></span>, molar isobaric thermal expansions, <span><math><msub><mi>E</mi><mrow><mi>P</mi><mo>,</mo><mi>m</mi></mrow></msub></math></span>, coefficients of isochoric thermal pressure, <span><math><msub><mi>β</mi><mi>V</mi></msub></math></span>, of the mixture, as well as partial molar volumes of the mixture components, <span><math><msub><mover><mi>V</mi><mo>̄</mo></mover><mi>i</mi></msub></math></span>, including their limiting values, were calculated. The excess molar volumes were fitted with the Redlich-Kister equation. The formation of the glycerol + dimethyl sulfoxide mixture was shown to reduce the volume, whereas a pressure increase and a temperature decrease led to a smaller deviation from ideality, <span><math><msubsup><mi>V</mi><mi>m</mi><mi>E</mi></msubsup></math></span>. Pressure and temperature were shown to produce the opposite effects on the partial molar volumes of both mixture components. The pressure coefficient of the limiting partial molar volumes of glycerol in dimethyl sulfoxide changes its sign in the studied temperature range. The molar isothermal compressibility and molar isobaric thermal expansion of the mixture grew exponentially as the mole fraction of dimethyl sulfoxide increased. The concentration dependencies of the isochoric thermal pressure coefficient of the mixture were found to have no extremum.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"214 ","pages":"Article 107621"},"PeriodicalIF":2.2,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145797354","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}
Pub Date : 2025-12-15DOI: 10.1016/j.jct.2025.107622
Xinchen Zhang , Ali Farajtabar , Min Zheng , Abolghasem Jouyban , Hongkun Zhao
The equilibrium solubility of anti-allergic drug, tranilast, in ten mono-solvents, including methanol, acetonitrile, ethyl acetate, ethanol, n-propanol, N,N-dimethylacetamide (DMAC), isopropanol, n-butanol, N,N-dimethylformamide (DMF), and water, as well as solvent blends of ethanol + water and ethyl acetate + ethanol, were determined for the first time by means of the shake-flask saturation means. The solubility (×1000) of tranilast at 298.15 K was demonstrated by the order: DMF (76.7, mole fraction, the following together) > DMAC (35.4) > ethyl acetate (1.83) > n-butanol (1.63) > n-propanol (1.38) > ethanol (1.12) > isopropanol (0.959) > methanol (0.785) > acetonitrile (0.534) > water (0.000657). Owing to the chameleonic effect in the two mixed solvent systems, tranilast exhibits the solubilization phenomenon. There was no evidence of solvation or crystal transition in trial procedure, as proved by the XRD scans. The Apelblat and λh representations were employed to mathematically associate the equilibration solubility magnitudes in above mono-solvents, yielding the maximum relative average error of RAD = 7.39 × 10−2. While the Jouyban-Acree, Hildebrand solubility parameter, and modified van't Hoff-Jouyban-Acree models produced the largest RAD of 2.34 × 10−2 for the two solvent blends. The inverse Kirkwood-Buff integrals approach were practiced to analyze the preferred solvation of tranilast, on the basis of the tranilast solubility in blended solvents. Blends with water-rich compositions for ethanol + water mixture and ethanol-rich compositions for ethyl acetate + ethanol mixture had positive values for tranilast solvation parameter. This suggests that ethanol and ethyl acetate preferentially solvate tranilast in the composition ranges for the two blends, respectively. Employing solubility data, the Krug approach was implemented to derive the thermodynamic dissolution properties. In addition, the global minimum negative and global maximum positive electrostatic potential were employed to illustrate the acidity-basicity features of the tranilast molecule surface. The inter-molecular interactions between tranilast and solvents were qualitatively investigated by the use of Hirshfeld partition-based independent gradient analysis.
{"title":"Solubility of tranilast in a number of pure and solvent blends: Determination, correlation and quantum chemical analysis","authors":"Xinchen Zhang , Ali Farajtabar , Min Zheng , Abolghasem Jouyban , Hongkun Zhao","doi":"10.1016/j.jct.2025.107622","DOIUrl":"10.1016/j.jct.2025.107622","url":null,"abstract":"<div><div>The equilibrium solubility of anti-allergic drug, tranilast, in ten mono-solvents, including methanol, acetonitrile, ethyl acetate, ethanol, <em>n</em>-propanol, <em>N</em>,<em>N</em>-dimethylacetamide (DMAC), isopropanol, <em>n</em>-butanol, <em>N</em>,<em>N</em>-dimethylformamide (DMF), and water, as well as solvent blends of ethanol + water and ethyl acetate + ethanol, were determined for the first time by means of the shake-flask saturation means. The solubility (×1000) of tranilast at 298.15 K was demonstrated by the order: DMF (76.7, mole fraction, the following together) > DMAC (35.4) > ethyl acetate (1.83) > <em>n</em>-butanol (1.63) > <em>n</em>-propanol (1.38) > ethanol (1.12) > isopropanol (0.959) > methanol (0.785) > acetonitrile (0.534) > water (0.000657). Owing to the chameleonic effect in the two mixed solvent systems, tranilast exhibits the solubilization phenomenon. There was no evidence of solvation or crystal transition in trial procedure, as proved by the XRD scans. The Apelblat and <em>λh</em> representations were employed to mathematically associate the equilibration solubility magnitudes in above mono-solvents, yielding the maximum relative average error of <em>RAD</em> = 7.39 × 10<sup>−2</sup>. While the Jouyban-Acree, Hildebrand solubility parameter, and modified van't Hoff-Jouyban-Acree models produced the largest <em>RAD</em> of 2.34 × 10<sup>−2</sup> for the two solvent blends. The inverse Kirkwood-Buff integrals approach were practiced to analyze the preferred solvation of tranilast, on the basis of the tranilast solubility in blended solvents. Blends with water-rich compositions for ethanol + water mixture and ethanol-rich compositions for ethyl acetate + ethanol mixture had positive values for tranilast solvation parameter. This suggests that ethanol and ethyl acetate preferentially solvate tranilast in the composition ranges for the two blends, respectively. Employing solubility data, the Krug approach was implemented to derive the thermodynamic dissolution properties. In addition, the global minimum negative and global maximum positive electrostatic potential were employed to illustrate the acidity-basicity features of the tranilast molecule surface. The inter-molecular interactions between tranilast and solvents were qualitatively investigated by the use of Hirshfeld partition-based independent gradient analysis.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"214 ","pages":"Article 107622"},"PeriodicalIF":2.2,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145839925","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}
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