Fluid Phase Equilibria最新文献_第2页

Using Physical Property Models and Artificial Intelligence to Design Chemical Products 利用物理性质模型和人工智能设计化工产品

IF 2.8 3区工程技术

Fluid Phase Equilibria Pub Date : 2025-04-11 DOI: 10.1016/j.fluid.2025.114441

Kevin G. Joback

引用次数: 0

Artificial neural network-based estimation of interaction parameters between carbon dioxide and organic solvents using the Peng–Robinson equation of state with the van der Waals one-fluid mixing rule and quantum chemical data 基于van der Waals单流体混合规则的Peng-Robinson状态方程和量子化学数据的二氧化碳与有机溶剂相互作用参数的人工神经网络估计

IF 2.8 3区工程技术

Fluid Phase Equilibria Pub Date : 2025-04-11 DOI: 10.1016/j.fluid.2025.114443

Hiroaki Matsukawa, Emiri Kobayashi, Katsuto Otake

{"title":"Artificial neural network-based estimation of interaction parameters between carbon dioxide and organic solvents using the Peng–Robinson equation of state with the van der Waals one-fluid mixing rule and quantum chemical data","authors":"Hiroaki Matsukawa, Emiri Kobayashi, Katsuto Otake","doi":"10.1016/j.fluid.2025.114443","DOIUrl":"10.1016/j.fluid.2025.114443","url":null,"abstract":"<div><div>The Peng–Robinson (PR)-van der Waals (vdW) model, which combines the PR equation of state with the vdW one-fluid mixing rule, is often used to estimate the physical properties of CO<sub>2</sub>/organic solvent mixtures. Calculating these properties using the PR-vdW model requires interaction parameters <em>k<sub>ij</sub></em>; however, reports on these parameters are limited. This article introduces an artificial neural network (ANN) to predict <em>k<sub>ij</sub></em> between CO<sub>2</sub> and organic solvents, using pure-component parameters and molecular information as inputs. The molecular information is obtained through the general-purpose quantum chemical calculation software Gaussian. In addition, the ANN is optimized by varying the transfer function, number of neurons, and number of hidden layers. The optimized ANN employs a tanh function as the transfer function for the hidden layers, with two hidden layers containing 40 and 10 neurons. This model effectively predicts <em>k<sub>ij</sub></em> for a wide range of substances and temperature conditions. Furthermore, SHapley Additive exPlanations analysis of the optimized ANN reveals a significant contribution from the quadrupole moment, likely due to quadrupole interactions between CO<sub>2</sub> and the organic solvents. These results support the estimation of the physical properties of CO<sub>2</sub>/organic solvent mixtures.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"596 ","pages":"Article 114443"},"PeriodicalIF":2.8,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143834443","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Vapor–liquid interfacial properties of the system acetone + CO2: Experiments, molecular simulation, density gradient theory, and density functional theory 丙酮+ CO2体系的气液界面性质：实验、分子模拟、密度梯度理论和密度泛函理论

IF 2.8 3区工程技术

Fluid Phase Equilibria Pub Date : 2025-04-11 DOI: 10.1016/j.fluid.2025.114436

Florian Fleckenstein, Stefan Becker, Hans Hasse, Simon Stephan

{"title":"Vapor–liquid interfacial properties of the system acetone + CO2: Experiments, molecular simulation, density gradient theory, and density functional theory","authors":"Florian Fleckenstein, Stefan Becker, Hans Hasse, Simon Stephan","doi":"10.1016/j.fluid.2025.114436","DOIUrl":"10.1016/j.fluid.2025.114436","url":null,"abstract":"<div><div>Vapor–liquid interfacial properties of the system acetone + CO<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> were studied using pendant drop experiments as well as multiple theoretical approaches, namely molecular dynamics (MD) simulations, density gradient theory (DGT), and density functional theory (DFT). The surface tension as well as relative adsorption of CO<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> were obtained from the experiments for temperatures between 303.15 K and 373.15 K. The experimental results were compared to predictions from the three theoretical approaches, which also provide insights into the structure of the interface and data on the interfacial enrichment of CO<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> and the interfacial thickness, which is not feasible by the experiments alone. The results from all three theoretical approaches are found to be in good mutual agreement as well as in agreement with the experimental results. Additionally, MD, DGT, and DFT were used to study the nanoscopic structure at the interface.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"596 ","pages":"Article 114436"},"PeriodicalIF":2.8,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143834441","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Modeling flash points of biofuels using neural networks 用神经网络模拟生物燃料的闪点

IF 2.8 3区工程技术

Fluid Phase Equilibria Pub Date : 2025-04-01 DOI: 10.1016/j.fluid.2025.114439

Maurício Prado de Omena Souza , Débora Costa do Nascimento , Diego Tavares Volpatto , Gustavo Gondran Ribeiro , Antonio Marinho Barbosa Neto , Mariana Conceição da Costa

{"title":"Modeling flash points of biofuels using neural networks","authors":"Maurício Prado de Omena Souza , Débora Costa do Nascimento , Diego Tavares Volpatto , Gustavo Gondran Ribeiro , Antonio Marinho Barbosa Neto , Mariana Conceição da Costa","doi":"10.1016/j.fluid.2025.114439","DOIUrl":"10.1016/j.fluid.2025.114439","url":null,"abstract":"<div><div>The search for renewable energy resources is driven by environmental hazards caused by petroleum derivatives, price fluctuations, and the unsustainability of fossil fuels. In Brazil, biodiesel and bioethanol are established renewable fuels, while butanol shows promise as an alternative fuel, requiring research into their safety and efficiency. The Flash Point (FP) is crucial for flammability assessment and safety in combustion processes, but its experimental measurement is resource-intensive. This study evaluates the capability of artificial neural networks (ANNs) to predict FP for some biofuels and their blends, using a dataset of 490 points. Notably, 24 of these points were newly acquired, while the remaining 466 were sourced from literature. A robust ANN model was trained using a 5-fold cross-validation with an 80/20 data split, incorporating average molar mass, vapor pressure natural logarithmic, and experimental method as input features. The final model, featuring three hidden layers determined through a parametric analysis, achieved a Root Mean Square Error (RMSE) of 4.22 K and a Mean Absolute Error (MAE) of 3.09 K for 98 unknown points. The model achieved satisfactory accuracy, with MAE ranging from 1.51 K to 3.63 K, and performed comparably to traditional UNIFAC thermodynamic models. These results highlight the potential of ANNs for FP prediction across diverse datasets.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"596 ","pages":"Article 114439"},"PeriodicalIF":2.8,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806862","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Development of equation of state for a double square-well fluid 双方井流体状态方程的发展

IF 2.8 3区工程技术

Fluid Phase Equilibria Pub Date : 2025-03-31 DOI: 10.1016/j.fluid.2025.114437

Mohammad Hossein Hadipanah, Seyed Hossein Mazloumi

{"title":"Development of equation of state for a double square-well fluid","authors":"Mohammad Hossein Hadipanah, Seyed Hossein Mazloumi","doi":"10.1016/j.fluid.2025.114437","DOIUrl":"10.1016/j.fluid.2025.114437","url":null,"abstract":"<div><div>A double square-well potential function is proposed to describe the interaction between unbounded particles. This model is constructed based on the Lennard-Jones potential function and has three adjustable parameters. Based on the two-layers local composition model, a coordination number model for this double square-well fluid is developed and then by using the generalized van der Waals partition function a new expression for the attractive part of equation of state is derived. Two new equations of state are presented by sum of the attractive term and repulsive expressions of Carnahan-Starling and van der Waals. These models have three adjustable parameters, which are obtained by simultaneously fitting vapor pressures and liquid densities of pure substances. The capability of these two models in correlation of the vapour pressure and liquid density and in prediction of the vapour molar volume and heat of vaporization of pure compounds is investigated. Good results obtained especially with the new EOS in which Carnahan-Starling repulsive term has been used. The results of this EOS are excellent even for large molecules such as long- chain alkanes from C<sub>10</sub> to C<sub>20</sub>.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"596 ","pages":"Article 114437"},"PeriodicalIF":2.8,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143800237","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Speed-of-sound measurements in liquid n-heptane and 2,2,4-trimethylpentane (isooctane) 液体正庚烷和2,2,4-三甲基戊烷（异辛烷）的声速测量

IF 2.8 3区工程技术

Fluid Phase Equilibria Pub Date : 2025-03-29 DOI: 10.1016/j.fluid.2025.114432

T. Dietl, A. El Hawary, K. Meier

{"title":"Speed-of-sound measurements in liquid n-heptane and 2,2,4-trimethylpentane (isooctane)","authors":"T. Dietl, A. El Hawary, K. Meier","doi":"10.1016/j.fluid.2025.114432","DOIUrl":"10.1016/j.fluid.2025.114432","url":null,"abstract":"<div><div>This paper reports comprehensive and accurate measurements of the speed of sound in liquid <em>n</em>-heptane and 2,2,4-trimethylpentane (isooctane). The measurements were carried out by a double-path-length pulse-echo technique and cover the temperature range between 200 K and 420 K with pressures up to 100 MPa. The expanded uncertainties (coverage factor <span><math><mrow><mi>k</mi><mo>=</mo><mn>2</mn></mrow></math></span>) amount to 2.1 mK in temperature, 0.005% in pressure, 0.02% in speed of sound in <span><math><mi>n</mi></math></span>-heptane, and 0.015% in speed of sound in isooctane, with the exception of a few state points at low pressures, where it increases up to 0.03% for <span><math><mi>n</mi></math></span>-heptane and up to 0.035% for isooctane. Our data are more accurate than previously published data for both fluids. The measurements for isooctane extend the range in which the speed of sound had been measured before from 293 K down to 200 K and from 373 K up to 420 K. We also provide accurate correlations for the speed of sound as a function of temperature and pressure in the range of our measurements. Our data can contribute to developing new, more accurate equations of state for both fluids.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"596 ","pages":"Article 114432"},"PeriodicalIF":2.8,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143747738","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Crystallization risk of aromatic compounds in LNG production Part III: The solubility of o-xylene in methane down to cryogenic temperatures 液化天然气生产中芳香族化合物的结晶风险第三部分：邻二甲苯在甲烷中低温下的溶解度

IF 2.8 3区工程技术

Fluid Phase Equilibria Pub Date : 2025-03-28 DOI: 10.1016/j.fluid.2025.114434

Salem Hoceini, Marco Campestrini, Paolo Stringari

{"title":"Crystallization risk of aromatic compounds in LNG production Part III: The solubility of o-xylene in methane down to cryogenic temperatures","authors":"Salem Hoceini, Marco Campestrini, Paolo Stringari","doi":"10.1016/j.fluid.2025.114434","DOIUrl":"10.1016/j.fluid.2025.114434","url":null,"abstract":"<div><div>Following a series of works dealing with the experimental determination of the solubility limits of the BTEX components in methane rich-mixtures down to cryogenic temperatures, this work presents new measurements for the solubility of solid o-xylene in solvent methane. The measurements have been obtained using a static-analytic method that allows sampling of the fluid phase at equilibrium with the solid one at temperatures from 242 K down to 123 K and at nominal pressures of 3 and 6 MPa. Despite the importance of BTEX in assessing the risk of crystallization during the liquefaction of natural gas, the solubility of o-xylene in methane rich mixtures was not known in the literature before this work. As a consequence, these original data will give new insights into the solid-fluid equilibrium behaviour of the o-xylene + methane mixture down to LNG temperatures and then provide crucial information for the proper tailoring of the purification units upstream of the liquefaction unit. Measured solid-liquid and solid-vapor equilibria have been compared to the modelling results obtained by coupling a cubic equation of state and a model for the solid phase, and good agreement has been observed.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"596 ","pages":"Article 114434"},"PeriodicalIF":2.8,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806861","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Thermochemical parameters of formation and vaporisation of alkanethiols: From experiment to prediction 烷烃硫醇形成和汽化的热化学参数：从实验到预测

IF 2.8 3区工程技术

Fluid Phase Equilibria Pub Date : 2025-03-28 DOI: 10.1016/j.fluid.2025.114435

Ruslan N. Nagrimanov , Aliya R. Ibragimova , Dmitry A. Kornilov , Aizat A. Samatov , Boris N. Solomonov , Dzmitry H. Zaitsau , Vladimir V. Turovsev

{"title":"Thermochemical parameters of formation and vaporisation of alkanethiols: From experiment to prediction","authors":"Ruslan N. Nagrimanov , Aliya R. Ibragimova , Dmitry A. Kornilov , Aizat A. Samatov , Boris N. Solomonov , Dzmitry H. Zaitsau , Vladimir V. Turovsev","doi":"10.1016/j.fluid.2025.114435","DOIUrl":"10.1016/j.fluid.2025.114435","url":null,"abstract":"<div><div>Alkanethiols are an important class of organic compounds and are used in materials science. In some cases, the production of materials based on alkanethiols requires knowledge of reliable values for vapour pressures and thermochemical parameters of phase transitions. Reliable enthalpies of vaporisation and enthalpies of formation in the condensed state are also required in order to obtain the enthalpy of formation in the gas phase. The experimental determination of enthalpies of formation in condensed state for sulfur-containing compounds is a challenging experimental task. The development of accurate predictive approaches is therefore a relevant task. In the present study, the available saturation vapour pressures at different temperatures and enthalpies of vaporisation of the alkanethiols were critically reviewed. In addition, the solution calorimetry method was developed and used to determine the enthalpy of vaporisation of alkanethiols. These data were also used to determine reliable experimental enthalpies of formation in the gas phase. Reliable experimental enthalpies of formation were then used to find the most accurate functional and basis set for estimation of the unknown enthalpy of formation in the gas phase using quantum chemical methods. In summary, the most consistent functional and basis set for calculating the enthalpies of formation of alkanethiols and the enthalpies of vaporisation obtained by solution calorimetry approach were used to estimate the enthalpies of formation of alkanethiols in the condensed state.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"596 ","pages":"Article 114435"},"PeriodicalIF":2.8,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143768824","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Development of a new electrolyte equation of state based on Cubic Two State model 基于三次双态模型的电解质状态方程的建立

IF 2.8 3区工程技术

Fluid Phase Equilibria Pub Date : 2025-03-27 DOI: 10.1016/j.fluid.2025.114433

Farag M.A. Altalbawy , Laith Saheb , Ramdevsinh Jhala , Ramachandran T , Aman Shankhyan , Karthikeyan A , Dhirendra Nath Thatoi , Deepak Gupta

{"title":"Development of a new electrolyte equation of state based on Cubic Two State model","authors":"Farag M.A. Altalbawy , Laith Saheb , Ramdevsinh Jhala , Ramachandran T , Aman Shankhyan , Karthikeyan A , Dhirendra Nath Thatoi , Deepak Gupta","doi":"10.1016/j.fluid.2025.114433","DOIUrl":"10.1016/j.fluid.2025.114433","url":null,"abstract":"<div><div>In this study, a new electrolyte equation of state (EoS) based on the Cubic Two State (CTS) model has been developed to study the activity coefficient, solution density, Gibbs free energy of hydration, and Solid-Liquid equilibrium (SLE) calculations of strong electrolyte solutions. The primitive Mean Spherical Approximation (MSA) has been used to model the long-range electrostatic interaction between counter ions. The association interaction between ions and water has been considered using the association contribution in CTS EoS. As well, the Born solvation term has been incorporated into the electrolyte CTS (eCTS) to model the solvation of ions in water. Model parameters have been adjusted using the mean ionic activity coefficient (MIAC) and solution density data up to high temperatures. The average ARD values of MIAC, density, osmotic coefficient, and water activity have been obtained 3.9 %, 3.08 %, 4.6 %, and 3.8 %, respectively. The ion-specific parameters have been used for the prediction of the MIAC of the mixed electrolyte solution. As well, the proposed model has been utilized to predict the SLE calculations of binary salts, and the hydration energy of solvation at 298.15 K. The results demonstrate that the eCTS EoS can be used for the prediction of SLE calculations over a wide range of temperatures.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"596 ","pages":"Article 114433"},"PeriodicalIF":2.8,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143759449","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Liquid-liquid equilibria of biodiesel + glycerol and biodiesel + water binary systems 生物柴油+甘油和生物柴油+水二元体系的液-液平衡

IF 2.8 3区工程技术

Fluid Phase Equilibria Pub Date : 2025-03-21 DOI: 10.1016/j.fluid.2025.114431

Sebastiano Tomassetti , Giovanni Di Nicola , Fabio Polonara , Matteo Moglie , Giulio Santori

{"title":"Liquid-liquid equilibria of biodiesel + glycerol and biodiesel + water binary systems","authors":"Sebastiano Tomassetti , Giovanni Di Nicola , Fabio Polonara , Matteo Moglie , Giulio Santori","doi":"10.1016/j.fluid.2025.114431","DOIUrl":"10.1016/j.fluid.2025.114431","url":null,"abstract":"<div><div>The liquid-liquid equilibria (LLE) of the biodiesel + glycerol and biodiesel + water binary systems are experimentally measured at atmospheric pressure and in the temperature range from 310.35 K to 338.15 K, conditions relevant to the industrial process, solving the experimental challenges related to their direct measurement. The LLE data of these binary systems are pivotal for designing the biodiesel purification processes and determine the chemical equilibrium constant of the transesterification reaction of vegetable oil into biodiesel. However, unlike to the present study, this information is typically indirectly extrapolated from models regressed on ternary systems, undermining the reliability of the results. The experimental data were compared against the calculations provided by the UNIQUAC and UNIFAC models, with the binary interactions parameters (BIPs) of the UNIQUAC model validated on the experimental data. To ensure a thermodynamically consistent representation of the phase behaviour and smooth the experimental scattering of trace components, the BIPs are regressed by means of an algorithm that considers the experimental uncertainty. The results are compared with LLE data for biodiesel + glycerol and biodiesel + water from ternary systems measured by other laboratories.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"595 ","pages":"Article 114431"},"PeriodicalIF":2.8,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143696827","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0