Journal of Chemical Thermodynamics最新文献

Multi-model synergy for hypergravity silica gel–water vapor adsorption isotherms: experimental validation and predictive modeling. 超重力硅胶-水蒸气吸附等温线的多模型协同作用：实验验证和预测建模。

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2026-05-01 Epub Date: 2026-02-06 DOI: 10.1016/j.jct.2026.107644

Dezhi Li , Xu Zheng , Suyun Yi , Ning Mei

Abstract

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%.

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.

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).

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.

超重力显著增强气固传质，但系统的平衡数据和可靠的预测模型仍然缺乏。为了解决这一问题，我们在全因子设计下对硅胶和水蒸气进行了256个全面的吸附实验，超重力因子（β）从0到40，温度(T)从298.2到308.2 K，相对湿度（φ）从20%到95%。与固定床（β = 0）相比，β = 16时的超重力吸附量提高了39%。对6种经典吸附等温线模型进行了评价，其中Sips方程和Dubinin-Radushkevich （DR）方程拟合效果最好。基于吸附势理论，将亲和系数与T、β和φ关联，建立了改进的DR模型，得到了显式函数关系q = f（T, β, φ）。该模型具有较高的精度（R2 = 0.992-0.999），在β = 10-50的实际超重力范围内具有稳定的性能，特别适用于中至高超重力条件下的机理分析和过程模拟。为了补充这一理论方法，我们还提出了一种无量纲相关性和两种机器学习模型——支持向量机（SVM）和反向传播（BP）神经网络。BP模型在包含实验数据、修正DR预测和特征曲线外推结果的组合数据集上进行训练，获得了最高的预测精度（检验R2 = 0.9994）。总的来说，集成框架-结合改进的DR，无量纲和机器学习模型-为预测超重力吸附等温线提供了一套可靠的工具，并提供了可扩展到其他吸附剂-吸附质气固系统的方法蓝图。

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引用次数: 0

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 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

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

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.

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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引用次数: 0

Experimental and theoretical investigation on viscosity of carbonated piperazine (PZ) activated 1-dimethylamino-2-propanol (DMA2P) aqueous blends 碳酸哌嗪（PZ）活化1-二甲氨基-2-丙醇（DMA2P）水溶液共混物粘度的实验与理论研究

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2026-05-01 Epub Date: 2026-01-14 DOI: 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 (D_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.

在本研究中，我们研究了1-二甲氨基-2-丙醇（DMA2P）和哌嗪（PZ）的碳酸水共混物在303.2 ~ 323.2 K的常压下的粘度数据。DMA2P和PZ的浓度分别为30 ~ 50 wt%和2.5 ~ 7.5 wt%。用Weiland方程对实验粘度进行了计算和预测。计算结果与实验结果吻合较好，平均相对偏差为2.18%。利用Arrhenius-type表达式和修正的Stokes-Einstein方程，分别推导了DMA2P-PZ碳酸化共混物的黏度活化能Ea和CO2扩散系数DCO2。结果表明，DMA2P-PZ吸附剂在CO2捕集过程中具有良好的工业应用潜力。

引用次数: 0

New thermodynamic aspects and speciation properties of the angiotensin-converting enzyme inhibitor drug, lisinopril with Cu2+, Zn2+, Ca2+, Mg2+ in sodium chloride aqueous solution 血管紧张素转换酶抑制剂赖诺普利在氯化钠水溶液中Cu2+， Zn2+, Ca2+， Mg2+的新热力学方面和形态性质

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.2026.107632

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

(2S)-1-[(2S)-6-amino-2-[[(1S)-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 ≤ T/K ≤ 310.15) and ionic strengths (0.16 ≤ I/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.

（2S）-1-[(2S)-6-氨基-2-[[(1S)-1-羧基-3-苯基丙基]氨基]己醇基]吡罗烷-2-羧酸（赖诺普利）是一种常用的治疗高血压和心力衰竭的药物。近年来，它也被确定为一种新兴的环境污染物。研究了赖诺普利在水溶液中的热力学行为。采用电位法测定了赖诺普利在不同温度（288.15≤T/K≤310.15）和离子强度（0.16≤I/mol kg−1(H2O)≤0.97,NaCl）下的质子化常数。结果表明，前两个和第四个质子化步骤是由焓驱动的，而第三个则是由熵驱动的。此外，基于金属离子不同的酸碱特性和可能形成的少溶态，提出了不同金属/赖诺普利体系的形态形成模型，包括：ZnH2L+2、ZnHL+、CuHL+、CuL、CaL、CaHL+、MgL和MgHL+。利用特定离子相互作用理论（SIT）和改进的扩展debye - h ckel方程，建立了离子强度和温度对热力学形成参数的影响模型。最后，评估了赖诺普利在模拟真实系统（如海水）条件下的质子化和络合物形成常数的分布。

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引用次数: 0

Development and prospect of low-temperature adiabatic calorimetry 低温绝热量热法的发展与展望

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2026-05-01 Epub Date: 2026-01-24 DOI: 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.

热容是一种基本的热力学性质，它为相变、量子效应和物质的分子热运动的行为提供了基本的见解。绝热量热法是获得精确的热容数据和研究材料基本性质最可靠的方法之一。在此背景下，本文回顾了过去120年来绝热量热法的发展，从最早的原型仪器到后来的几代，并朝着更小的样本量、改进的冷却和增强的自动化方向发展。然后，我们强调需要在极端条件下进行测量，包括高外场或超低温。此外，本综述还强调了在商业实施、模块化系统设计和与机器学习集成方面的持续发展。通过巩固现有知识和概述未来的方向，我们希望提高人们对绝热量热法作为现代材料研究的重要工具的认识，并鼓励科学界更加重视促进热法技术的发展和能力。

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引用次数: 0

Phase equilibria in the system Fe-Cu-Sn-FeO at iron saturation 铁饱和时Fe-Cu-Sn-FeO体系的相平衡

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2026-05-01 Epub Date: 2026-01-23 DOI: 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.

用铜锡合金作为锡源，在1100 ~ 1300℃的温度下研究了锡和氧化亚铁的平衡。为了避免平衡过程中锡和氧化锡的挥发，在封闭的铁安瓿中进行了激光焊接密封实验。通过电子探针x射线显微分析对主要成分和次要成分进行了相组成分析，激光烧蚀-电感耦合等离子体质谱法对直接从抛光切片中提取的痕量浓度进行了相组成分析。在液态铜合金中，当FeO饱和度达到20wt % Sn时，测量了铜-铁-锡相图。考察了锡和铜在固体铁中的热力学性质。此外，测定了铁饱和时锡和铜在氧化亚铁中的溶解。

引用次数: 0

Neural circuit policies for accurate prediction of interfacial tensions between liquid mixture of hydrocarbons and brine 用于精确预测烃类和卤水液体混合物界面张力的神经回路策略

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2026-05-01 Epub Date: 2026-01-14 DOI: 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.

烃类与卤水之间的界面张力（IFT）在提高采收率的过程中起着关键作用。尽管对油气-盐水系统进行了各种实验和模拟研究，但对油气-盐水系统中IFT的综合经验相关性仍未完全了解。本研究开发了三种IFT预测架构：深度神经网络（DNN）、长短期记忆（LSTM）和神经回路策略（NCP）。两相系统的输入向量通常包含几个数值参数，包括压力(P)、温度(T)、比重（ρ）、氯化钠（NaCl）等效盐度和ph。除了利用DNN方法外，LSTM和NCP方法还将简化的分子输入线输入系统（SMILES）作为输入数据。在3种方法中，包含所有6个参数和SMILES的NCP方法的均方根误差（RMSE）最低，为0.048 mN/m。此外，NCP方法的可训练权值数量比DNN和LSTM方法少8.3-15倍。因此，我们提出的NCP方法比更大的黑盒学习系统具有更好的泛化性和鲁棒性。盐水盐度的增加提高了IFT，因为盐离子优先保留在大块水中，这限制了它们破坏界面水分子内聚结构的能力，最终稳定了高盐度水平下的IFT。

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引用次数: 0

Low temperature heat capacity and thermodynamic functions of zirconium (IV) sulfate in the tetrahydrate and anhydrous forms 硫酸锆在四水和无水状态下的低温热容量和热力学函数

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2026-05-01 Epub Date: 2026-01-24 DOI: 10.1016/j.jct.2026.107631

Emma Esplin, Natalie Parkinson, Brian F. Woodfield

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.

在1.8 ~ 300 K范围内，用松弛量热法测定了四水和无水硫酸锆的热容。所测热容符合理论函数，并与现有文献进行了比较。根据数据拟合计算0 ~ 300 K的平滑熵和焓增量，得到Zr(SO4)2∙4.02H2O和Zr(SO4)2在298.15 K下的绝对熵分别为298.80 J∙K−1 mol−1和170.57 J∙K−1 mol−1。利用现有的生成焓数据计算了298.15 K时相对于元素和氧化物的吉布斯生成能。Zr(SO4)2∙4.02H2O和Zr(SO4)2在298.15 K时的吉布斯生成能分别为−2990.6 kJ∙mol−1和−2006.7 kJ∙mol−1，氧化物的吉布斯生成能分别为−270.2 kJ∙mol−1和−237.9 kJ∙mol−1。

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引用次数: 0

Insight of thermodynamic properties by the substitution of alkali metal ions in X2InGaCl6 (X = K, Rb, Cs) perovskites: DFT calculation and AIMD simulation 碱金属离子取代X2InGaCl6 （X = K, Rb, Cs）钙钛矿的热力学性质：DFT计算和AIMD模拟

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2026-05-01 Epub Date: 2026-01-21 DOI: 10.1016/j.jct.2026.107629

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

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 (

B / G =

2.23), while Rb₂InGaCl₆ (

B / G =

1.77) and Cs₂InGaCl₆ (

B / G =

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.

为了解决铅毒性和稳定性的关键问题，我们必须找到对环境无害的替代品来替代传统的钙钛矿太阳能电池。本研究旨在为无铅卤化物双钙钛矿系列X2InGaCl6 （X = K, Rb, Cs）作为光电子可调谐半导体提供全面的第一性原理评估。利用CASTEP代码中的密度泛函理论（DFT）计算，我们分析研究了它们的结构、电子、机械和光学性质，以及声子色散和从头算分子动力学来进行稳定性评估。计算出的容差系数（0.89-0.97）和负地层能量证实了热力学稳定性，而AIMD证实了300 K下的强劲热稳定性。结果表明，K2InGaCl6的可调间接带隙为1.38 eV， Rb2InGaCl6为1.48 eV， Cs2InGaCl6为1.71 eV。力学上，所有材料都是稳定的，其中k2ingacl16具有延展性（B/G=2.23），而rb2ingacl16 （B/G=1.77）和cs2ingacl16 （B/G=1.79）具有脆性。光学研究表明，从紫外到红外区域都有很强的吸收。总之，这些环境友好的钙钛矿具有高度可调和有利的特性，可用于光伏，紫外光电探测器和柔性光电器件。

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引用次数: 0

Behaviors salts of diammonium hydrogenphosphate or sulfate containing in fertilizers, solubility and thermodynamic study in aqueous solutions at various temperatures 肥料中含磷酸氢二铵盐或硫酸盐的行为，在不同温度下水溶液的溶解度和热力学研究

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.2026.107641

S.M. Aboufaris El Alaoui, M. EL Guendouzi

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

{({NH}_{4})}_{2} HP O_{4} (aq)

and

{({NH}_{4})}_{2} S O_{4} (aq)

ranged from

m_{s (\exp)}

= 5.260 to 8.641

mol \cdot {kg}^{- 1}

and

m_{s (\exp)}

= 5.799 to 7.122

mol \cdot {kg}^{- 1}

, 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

{({NH}_{4})}_{2} HP O_{4} (s)

and

{({NH}_{4})}_{2} S O_{4} (s)

were also evaluated at different temperatures. In addition, excess thermodynamic functions such as

∆ G^{E}, ∆ H^{E}

, and

∆ S^{E}

, 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.

在这项研究中，实验和计算的溶解度的二元水溶液（氢磷酸或硫酸）在不同的温度下进行了测定。在298.15 ~ 353.15 K范围内，NH42HPO4aq和NH42SO4aq的实验溶解度分别为msexp = 5.260 ~ 8.641 mol·kg−1和msexp = 5.799 ~ 7.122 mol·kg−1。所研究体系的热力学性质是由水活度测量得出的。因此，用湿度计法在不同温度下测量了这些水溶液从稀溶液到饱和溶液的水活度。根据新的实验水活度，得到了电解质溶液在温度范围内的渗透系数。用扩展的离子相互作用模型对所得系数进行处理。利用开发的Pitzer和Clegg-Pitzer-Brimblecombe模型评估了亚二元系统的相关热力学性质。实际上，计算了磷酸氢二铵或硫酸盐水溶液的二元参数，并将其用于计算溶质活度和渗透系数；适当的模型可以很好地描述计算出的活度系数。测定了不同温度下NH42HPO4s和NH42SO4s的溶解吉布斯能和溶解度积。此外，还得到了过量热力学函数∆GE、∆HE和∆SE，以及溶剂和溶质的偏摩尔熵。基于这些结果，硫酸盐和磷酸盐体系表现出相反的水化行为和热力学稳定性。

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引用次数: 0