Article
Chemistry, Physical
Damien Degoulange, Nicolas Dubouis, Alexis Grimaud
Summary: The study investigates the application of highly concentrated electrolytes in aqueous electrochemical systems, finding that the potential shift from diluted to highly concentrated electrolytes mainly comes from an increased junction potential. As the concentration increases, the activity coefficients of cations also increase, leading to higher proton activity in highly concentrated solutions.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Kunal R. Patil, Sarika K. Patil, Vasim R. Shaikh, Dilip H. Dagade, Kesharsingh J. Patil
Summary: The triethylammonium-based carboxylate protic ionic liquids are considered as truly bio-ionic liquids and can be used in various applications, including green solvents and biphasic catalysis, especially in relation to nano-materials and biomolecules. Research findings show that these studied PILs exhibit positive deviations from the Debye-Huckel limiting law in aqueous solutions, indicating a dominant hydration effect through cooperative H-bonding with water structure formation.
JOURNAL OF MOLECULAR LIQUIDS
(2021)
Article
Medicine, Research & Experimental
Martin Klajmon
Summary: This study thoroughly benchmarks two popular thermodynamic models, PC-SAFT and COSMO-RS, for predicting the solubility of active pharmaceutical ingredients (APIs) in pure solvents. The results show that COSMO-RS outperforms PC-SAFT both qualitatively and quantitatively, even though COSMO-RS does not rely on experimental data. Interestingly, both models were found to often incorrectly predict the direction of deviations from ideality.
MOLECULAR PHARMACEUTICS
(2022)
Article
Chemistry, Physical
Tianwen Luo, Reza Shariyati
Summary: In this study, the solubility parameters of three families of ionic liquids (ILs) were predicted using the PCSAFT equation of state (EoS). The effect of association interaction between ILs molecules on solubility parameters was investigated. Four scenarios were considered to optimize the model parameters. The results showed that the PC-SAFT EoS satisfactorily predicted the solubility parameters of ILs, making it a valuable tool for engineers in solvent selection and process design.
JOURNAL OF MOLECULAR LIQUIDS
(2023)
Article
Thermodynamics
Francisco J. Passamonti, Maria R. Gennero de Chialvo, Abel C. Chialvo
Summary: A method is proposed for evaluating the activity coefficients of solutes in a ternary solution based on the osmotic coefficient and composition. The method derives an analytical expression to describe the dependence between osmotic coefficient and composition, and uses the Gibbs-Duhem differential equation to evaluate the activity coefficients in ideal dilute solution reference state. Comparative analysis of three ternary systems confirms the feasibility of the proposed method and establishes the relationships between reference states and concentration scales for further correlation with molecular solution modelling equations.
FLUID PHASE EQUILIBRIA
(2022)
Article
Medicine, Research & Experimental
Jachym Pavlis, Alex Mathers, Michal Fulem, Martin Klajmon
Summary: The bioavailability of poorly water-soluble APIs can be enhanced by formulating them into amorphous solid dispersions (ASDs) with suitable polymeric carriers. Traditional experimental methods for identifying optimal carriers are time-consuming and costly. In this study, the perturbed-chain statistical associating fluid theory (PC-SAFT) equation of state was evaluated for its ability to predict API-polymer compatibility without any fitted binary interaction parameters. The PC-SAFT predictions were compared to experimental data for 40 API-polymer combinations, and while the total average error was around 50%, the qualitative ranking of polymer compatibility was reasonably predicted.
MOLECULAR PHARMACEUTICS
(2023)
Article
Engineering, Chemical
Elmira Behboudi, Hemayat Shekaari, Mohammed Taghi Zafarani-Moattar
Summary: This study measured vapor-liquid equilibrium data of ternary systems containing deep eutectic solvents using the isopiestic method, and successfully predicted water activity and vapor pressure of water using PC-SAFT EOS. The results indicated stronger interactions between glycerol-based DES and D-mannose, suggesting favorable interactions for the transfer of D-mannose from water to aqueous solution of DES.
JOURNAL OF THE TAIWAN INSTITUTE OF CHEMICAL ENGINEERS
(2021)
Article
Thermodynamics
Lifu Zhang, Zhe Wang, Wanjun Lu, Yahui Li
Summary: This paper investigates the mass transfer process of methane in aqueous solution under the effect of temperature gradient using quantitative Raman spectroscopy. It is observed that thermodynamic factors play a dominant role in the diffusion of CH4. The Soret and thermal diffusion coefficients of dissolved CH4 are calculated within a certain range of pressure and temperature. Based on the temperature gradient distribution in a specific geological body, the CH4 solubility distribution is estimated and provides new insights into the formation mechanism of CH4 accumulation, leakage, and related geological disasters.
INTERNATIONAL JOURNAL OF HEAT AND MASS TRANSFER
(2023)
Article
Thermodynamics
Daniel Schick, Mouad Arrad, Paul Figiel, Gabriele Sadowski, Christoph Held
Summary: This paper proposes a novel modeling approach that combines the Pitzer model and the equation of state ePC-SAFT to simulate the temperature-dependent solubility of salts in organic solvents. The approach accurately correlates the temperature-dependent osmotic coefficients and determines the thermodynamic solubility product KSP of the salts. Missing data were measured experimentally, and the approach was successfully applied to model the solubility of salts in organic solvents over the temperature range.
FLUID PHASE EQUILIBRIA
(2023)
Article
Chemistry, Medicinal
Samane Zarei Mahmoudabadi, Gholamreza Pazuki
Summary: This study evaluated the applicability of the PC-SAFT theory for pharmaceutical compounds, utilizing experimental solubility data and regression parameters. The study explored prediction accuracy, co-crystal formation, and purification efficiencies for acetaminophen production, all showing promising results for the PC-SAFT EOS.
JOURNAL OF PHARMACEUTICAL SCIENCES
(2021)
Article
Thermodynamics
Francisco J. Passamonti, Maria R. Gennero de Chialvo, Abel C. Chialvo
Summary: An alternative method independent of physicochemical models is presented to evaluate the mean ionic activity coefficients of solutes in a ternary solution using experimental data. The method involves integration and precise correlation for high accuracy, resulting in an expression for the activity coefficients.
FLUID PHASE EQUILIBRIA
(2021)
Article
Thermodynamics
Malak Wehbe, Andrew J. Haslam, George Jackson, Amparo Galindo
Summary: The study uses the SAFT-gamma Mie group-contribution equation of state to predict the phase diagrams and pH-dependent solubility of acidic APIs. The predictions are in good agreement with experimental data and accurately capture the solid-liquid solubility and liquid-liquid separation of the compounds.
FLUID PHASE EQUILIBRIA
(2022)
Article
Engineering, Chemical
Bennett D. Marshall, J. R. Johnson
Summary: In this paper, a new model is proposed to predict the pervaporation separation of solvent mixtures using glassy polymer membranes. The model is based on the diffusion theory of Maxwell-Stefan diffusion with a concentration gradient driving. The approach combines the perturbed-chain statistical associating fluid theory (PC-SAFT) and the dry glass reference perturbation theory (DGRPT) to evaluate the solubilities of guest species in the membrane. The model demonstrates accurate predictions of pervaporation for binary solvent mixtures and has the potential for implementation in process simulators.
JOURNAL OF MEMBRANE SCIENCE
(2023)
Article
Chemistry, Physical
Rajshree J. Gavhane, Babasaheb D. Bhosale, Dilip H. Dagade
Summary: This study reports experimental density and osmotic pressure measurements of aqueous nucleobases ionic liquids (NBILs) at 298.15 K. The results indicate that NBILs exist in a liquid state due to their large standard entropies and small lattice potential energies. The hydration numbers are mainly determined by anion hydration, while cation hydration is negligible. The negative excess molar volumes confirm the hydrophobic nature of NBILs. The aqueous systems show negative deviation from the limiting law, with hydrophobic hydration dominating at low concentration and hydrophobic ion-association occurring at higher concentration. The osmotic second virial coefficients indicate attractive ion-ion-ion pair interactions.
JOURNAL OF MOLECULAR LIQUIDS
(2022)
Article
Medicine, Research & Experimental
Dominik Borrmann, Andreas Danzer, Gabriele Sadowski
Summary: This study investigated the changes in amorphous state of an active pharmaceutical ingredient (API) during water sorption process. PC-SAFT model demonstrated better performance in describing water sorption process, while free-volume theory explained the relationship between Stefan-Maxwell diffusion coefficients and water concentration.
MOLECULAR PHARMACEUTICS
(2022)
Article
Chemistry, Physical
Marcel Klinksiek, Sindi Baco, Sebastien Leveneur, Julien Legros, Christoph Held
Summary: The solvent plays a crucial role in biomass conversion by influencing dissolution, reaction kinetics, catalyst activity, and thermodynamic equilibrium. This study used the advanced thermodynamic model ePC-SAFT to predict the activities of reactants and catalyst in the acid-catalyzed esterification of levulinic acid (LA) with ethanol. By simultaneously solving the dissociation equilibrium of the catalyst and relating reaction kinetics to proton activity, the influence of the catalyst on kinetics was successfully predicted.
Article
Engineering, Chemical
Gangqiang Yu, Nicolas F. Gajardo-Parra, Min Chen, Biaohua Chen, Gabriele Sadowski, Christoph Held
Summary: The suitability of phenyl-based deep eutectic solvents (DESs) as absorbents for toluene absorption was investigated using thermodynamic modeling and molecular dynamics (MD). The thermodynamic models PC-SAFT and COSMO-RS were used to predict the vapor-liquid equilibrium of DES-toluene systems. Among the DESs studied, [TEBAC][PhOH] consisting of TEBAC and PhOH was found to be the most suitable absorbent based on its thermodynamic characteristics and molecular-level interactions. This work provides guidance for designing efficient DESs for the absorption of aromatic volatile organic compounds.
Article
Engineering, Environmental
Alexandre Cordier, Marcel Klinksiek, Christoph Held, Julien Legros, Sebastien Leveneur
Summary: The use of enzymes for chemical reactions has increased in recent years, leading to the development of various models to describe their kinetics. The Michaelis-Menten model is commonly used for reactions with only one substrate, while more complex models like the Ping-Pong Bi-Bi model are needed for bimolecular systems like esterification. These advanced models are crucial for scaling up reactors and optimizing production. However, these models typically do not take into account the reaction temperature.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Thermodynamics
Jonas Habicht, Christoph Brandenbusch, Gabriele Sadowski
Summary: In this study, a machine learning approach based on deep neural networks was developed to predict PC-SAFT pure-component parameters for non-associating molecules. The use of extended-connectivity fingerprints as input and optimization of bit collisions improved the accuracy of predictions. The results were validated by comparing calculated physical properties to experimental data. This predictive machine learning approach can be used in early process synthesis.
FLUID PHASE EQUILIBRIA
(2023)
Article
Thermodynamics
Mehriban Aliyeva, Paula Brandao, Jose R. B. Gomes, Joao A. P. Coutinho, Christoph Held, Olga Ferreira, Simao P. Pinho
Summary: This study investigated the effect of KCl and (NH4)2SO4 salts on the solubility of L-aspartic acid, L-glutamic acid, L-tryptophan, and L-tyrosine. The results showed that both salts had a salting-in effect on glutamic acid and aspartic acid, with (NH4)2SO4 having a stronger effect. For the aromatic amino acids, there was a slight increase in solubility at low salt concentrations, followed by a stronger salting-out effect, particularly with (NH4)2SO4. Furthermore, the relative solubility data were compared and a ranking connected to the amino acids' structure was established.
JOURNAL OF CHEMICAL THERMODYNAMICS
(2023)
Article
Medicine, Research & Experimental
Peter Kroll, Lara Exner, Christoph Brandenbusch, Gabriele Sadowski
Summary: Up to 90% of newly developed APIs are poorly water soluble and have low oral bioavailability. Surfactants are promising excipients to improve solubility and bioavailability. This study investigated the influence of hydrophobic and hydrophilic chain lengths of CiEj surfactants on the solubilization of fenofibrate, naproxen, and lidocaine. The results provide valuable insights into the solubilization mechanisms of APIs in surfactant aggregates.
MOLECULAR PHARMACEUTICS
(2023)
Article
Biochemistry & Molecular Biology
Moreno Ascani, Gabriele Sadowski, Christoph Held
Summary: In this study, an algorithm was implemented in the PC-SAFT framework to predict the thermodynamic equilibrium behavior of two multicomponent esterification systems. The results showed that PC-SAFT could accurately predict the chemical equilibrium composition and liquid-liquid phase behavior of the systems. This study highlights the potential of a physical sound model for thermodynamic-based modeling of chemical reacting systems undergoing liquid-liquid phase separation.
Article
Pharmacology & Pharmacy
Adrian Krummnow, Andreas Danzer, Kristin Voges, Samuel O. O. Kyeremateng, Matthias Degenhardt, Gabriele Sadowski
Summary: The poor bioavailability of an API can be improved by dissolving it in a polymeric matrix through the formation of an amorphous solid dispersion (ASD). Crystallization and amorphous phase separation of the API can decrease its bioavailability. This study quantified the kinetics of water-induced amorphous phase separation in RIT/PVPVA ASDs and determined the compositions of the evolving amorphous phases using confocal Raman spectroscopy.
Article
Pharmacology & Pharmacy
Stefanie Dohrn, Samuel O. Kyeremateng, Esther Bochmann, Ekaterina Sobich, Andrea Wahl, Bernd Liepold, Gabriele Sadowski, Matthias Degenhardt
Summary: This study systematically classifies the release mechanisms of amorphous solid dispersion (ASD) formulations and relates them to the loss of release (LoR) phenomenon. The thermodynamic modeling approach using a modeled ternary phase diagram is used to explain and predict LoR. The experimental results validate the modeling predictions and show that this approach can be applied to classify and quantitatively predict the release mechanism of PVPVA64-based ASDs in water.
Article
Biochemistry & Molecular Biology
Fatima Anjum, Maximilian Wessner, Gabriele Sadowski
Summary: Membrane-based diafiltration was used to remove ethanol from the API crystal suspension, reducing the solvent concentration below the specified limit. The size and form of the crystals remained unchanged during the solvent exchange process. This work is significant for bottom-up API production and provides a foundation for further experimental design in solvent exchange processes.
Article
Engineering, Chemical
Rouven Loll, Lisa Nordhausen, Andre Bieberle, Markus Schubert, Tobias Pyka, Jorg Koop, Christoph Held, Gerhard Schembecker
Summary: This study characterized the fluid dynamics of a water-air system in ZZ packings and found that liquid maldistribution occurred at low rotational speeds. It also demonstrated the use of X-ray CT to investigate the liquid distribution inside rotating ZZ packings.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2023)
Article
Chemistry, Physical
Paulo Aravena, Esteban Cea-Klapp, Nicolas F. Gajardo-Parra, Christoph Held, Jose Matias Garrido, Roberto I. Canales
Summary: Deep eutectic solvents (DESs) with betaine as the hydrogen bond acceptor (HBA) and glycol as the hydrogen bond donor (HBD) were studied for their physicochemical and transport properties. Density and viscosity were measured over a temperature range, and models were used to assess the effects of temperature, HBD chain length, and water content. Molecular dynamics simulations provided insights into the mixtures and their solvation with water, reducing the need for further experimental load in chemical process design.
JOURNAL OF MOLECULAR LIQUIDS
(2023)
Article
Engineering, Chemical
Tobias Hubach, Stefan Schlueter, Christoph Held
Summary: Nanofiltration is a suitable technique for separating monovalent ions and multivalent ions, such as lithium ions and magnesium ions from seawater, which can be used as a potential lithium source for lithium-ion battery production. This study proposes a method for modeling predefined membrane interconnections using discretization along the membrane length and across the membrane thickness. The solution-diffusion-electromigration model is employed in a fundamental membrane flowsheet to optimize the given flowsheet with a flexible objective function.
Article
Engineering, Chemical
Nicolas F. Gajardo-Parra, Gabriel Rodriguez, Andres F. Arroyo-Avirama, Astrit Veliju, Thomas Happe, Roberto I. Canales, Gabriele Sadowski, Christoph Held
Summary: This study evaluated the effects of various co-solvents and deep eutectic solvents (DESs) on the kinetics and stability of Candida boidinii Formate dehydrogenase. The results showed that certain co-solvents and DESs enhanced the catalytic efficiency and thermal protection of the enzyme. Additionally, DESs improved the NAD+ binding affinity of the enzyme.
Article
Thermodynamics
Haolei Yang, Xiaoqiang Bian, Lianguo Wang
Summary: A new association model, CPA-MHV1, combining the SRK equation of state with the CPA equation based on Michelsen's improved Huron-Vidal mixing rule, is developed. The model is used to investigate the vapor-liquid equilibrium of binary mixtures involving CH4, CO2, and H2O, as well as ternary mixtures containing NaCl. The results show that considering the solvation between CO2 and H2O yields the best performance, while CH4 with a pseudo-association scheme has the highest comprehensive prediction performance.
FLUID PHASE EQUILIBRIA
(2024)
Article
Thermodynamics
Vikas K. Sinha, Atanu K. Metya, Chandan K. Das
Summary: In this study, the solid-liquid coexistence curve for water was developed using coarse-grained mW and machine-learned ML-BOP water models. The ML-BOP model exhibited lower densities, a broader density-temperature hysteresis loop, and higher free energy compared to the mW model. The pressure dependence fusion curve for both models aligned with previous literature. This analysis demonstrates that the free energy method accurately captures the solid-liquid transformation and the thermodynamic melting point of water.
FLUID PHASE EQUILIBRIA
(2024)
Article
Thermodynamics
Curtis Hays Whitson
Summary: This article tells the story of an extraordinary individual who made numerous and valued contributions, portrayed through a few images and short stories.
FLUID PHASE EQUILIBRIA
(2024)
Article
Thermodynamics
Joe Hajjar, Sabine Enders
Summary: A generalized theoretical framework is introduced for multicomponent reactive nonuniform systems, combining the modified and generalized Cahn-Hilliard equation with a chemical kinetics model. The framework allows for the modelling and investigation of the combined reaction and diffusion in reactive liquid-liquid systems. It is found that for reacting mixtures with much smaller reaction rates than diffusion rates, the mixture will remain in phase equilibrium upon reaction and the interfacial chemical reaction will not affect the overall system dynamics, which are only influenced by the kinetics of the bulk phases.
FLUID PHASE EQUILIBRIA
(2024)
Article
Thermodynamics
Keycianne da Cruz Silva, Leticia Daniela de Souza, Vinicius Azevedo Gomes, Leandro Rodrigues de Lemos
Summary: Phase diagrams of four aqueous two-phase systems were determined experimentally, and conclusions were drawn regarding the effect of temperature on system enthalpy change and the influence of macromolecules on phase separation.
FLUID PHASE EQUILIBRIA
(2024)
Article
Thermodynamics
Yuanqing Wu, Shuyu Sun
Summary: The sparse-grid guided PINN training method improves the accuracy of the PINN surrogate model by rearranging collocation points and reduces the training time complexity. Experimental results demonstrate its clear advantages in terms of convergence, stability, and accuracy.
FLUID PHASE EQUILIBRIA
(2024)
Article
Thermodynamics
Peter Englezos
Summary: This article discusses the research progress and challenges in the field of canonical clathrate or gas hydrate phase equilibria, as well as the application of computational methods and models. It also explores the potential of machine learning techniques in hydrate and thermodynamic calculations.
FLUID PHASE EQUILIBRIA
(2024)
Article
Thermodynamics
Ying-Chieh Hung, Shao-Wei Su, Jia-Wei Yan, Gui-Bing Hong
Summary: In this study, VLE data for five binary systems were measured and successfully correlated using models. The predictive models were used to predict the binary VLE phase diagram and explain the mechanism of separation efficiency. The strength of electrostatic interactions and temperature-dependent separation behavior were determined through the analysis of molecular surface charge distribution.
FLUID PHASE EQUILIBRIA
(2024)
Article
Thermodynamics
Matevz Turk, Tomaz Urbic
Summary: By molecular dynamics and Monte Carlo simulations, this study determined the regions and hierarchy of anomalies in a purely repulsive core-softened system. It was found that in two dimensional systems, a size of 100 particles is sufficient for obtaining accurate details.
FLUID PHASE EQUILIBRIA
(2024)
Article
Thermodynamics
Adnan Jaradat, Rakan Al-Salman, Abdalla Obeidat
Summary: The vapor-liquid equilibrium of six primary alcohols were studied using molecular dynamics simulations and compared with experimental results. The study found that neglecting the Lennard-Jones interaction significantly reduced the critical temperature values and determining the critical temperature using surface tension gave more accurate results. The TraPPE-UA potential field showed good accuracy in predicting the critical temperature.
FLUID PHASE EQUILIBRIA
(2024)
Article
Thermodynamics
Michele Valsecchi, Amparo Galindo, George Jackson
Summary: The thermodynamic properties of aqueous mixtures of polyethylene glycol (PEG) are described using the SAFT-gamma Mie group-contribution equation of state. The model successfully predicts the miscibility gaps in a temperature range and shows good agreement with experimental results.
FLUID PHASE EQUILIBRIA
(2024)
Article
Thermodynamics
Roman Tomaschitz
Summary: Analytic closed-form expressions for the liquid and vapor saturation densities defining the coexistence curve are obtained. The coexistence curves of nitrogen, ethene, and sulfur hexafluoride are derived using high-precision data, and the critical power-law scaling of the order parameter and coexistence-curve diameter is examined. The Log-Log slopes of various quantities are used to determine the ideal power-law scaling regime and illustrate the slope evolution in the subcritical regime.
FLUID PHASE EQUILIBRIA
(2024)
Article
Thermodynamics
Nivaar Brijmohan, Kuveneshan Moodley, Caleb Narasigadu
Summary: An artificial neural network-based QSPR model was developed to estimate binary interaction parameters for the temperature-dependant form of the NRTL model. This model serves as a supplement to overcome limitations of group contribution methods in solvent screening and has been proven to be effective in improving the robustness of the screening process.
FLUID PHASE EQUILIBRIA
(2024)
Article
Thermodynamics
Marco Campestrini, Paolo Stringari, Salem Hoceini
Summary: In this paper, the solubility of benzene in different phases of methane was predicted using the GERG-2008 equation of state and the Gibbs free energy equation. The obtained results were in good agreement with experimental data and emphasized the significance of accurately representing the density of the fluid phase for predicting the solubility of solids in fluids.
FLUID PHASE EQUILIBRIA
(2024)
Article
Thermodynamics
Nefeli Novak, Georgios M. Kontogeorgis, Marcelo Castier, Ioannis G. Economou
Summary: This paper discusses theoretical considerations on electrolyte thermodynamic models for single and mixed solvent solutions. The authors find that there is no consensus among researchers on many fundamental issues in this field. They point out the need to convert electrolyte terms to the framework of the physical model and emphasize the importance of the Born term for liquid-liquid equilibrium calculations.
FLUID PHASE EQUILIBRIA
(2024)
