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At least 19 records

Activity coefficient acquisition with thermodynamics–informed active learning for phase diagram construction

This work explores the use of thermodynamics-informed Gaussian processes (GPs) and active learning (AL) to model activity coefficients and construct phase diagrams. Relying on synthetic data generated from an excess Gibbs energy model, GPs were found to accurately describe the activity coefficients of several binary mixtures across large composition and temperature ranges. Moreover, GPs could estimate their own uncertainty and identify composition/temperature regions where activity coefficient data provide the most information to the models. This was leveraged to build AL algorithms targeted at modeling phase equilibria. In many cases, a single active-learning-acquired data point was sufficient to describe the phase diagrams studied. Lastly, the ability of AL to greatly reduce the amount of data needed to obtain accurate models was further verified on experimental case studies, namely individual ion activity coefficients, the solid–liquid and vapor–liquid equilibrium of deep eutectic solvents, and phase equilibria in ternary mixtures.

25 ENERGY STORAGE↗

Investigation into Na and Cs activity coefficients in high salt solutions to support Cs removal in Hanford tank waste

The treatment of Hanford tank waste is one of the most technically challenging environmental cleanup activities for the U.S. Department of Energy to date. To expedite the processing of liquid waste stored in underground tanks in southeastern Washington state, it is necessary to remove the significant dose contributor, 137 Cs. Toward this effort, ion exchange with crystalline silicotitanate (CST) has been employed as part of the Tank Side Cesium Removal system. The model used to predict Cs exchange onto CST was developed using activity coefficients calculated from the Bromley equation. A series of batch contact tests that varied in [Na] were conducted to look at the impact of Na concentration on Cs distribution. Experimental distribution ratios ( K d ) were compared to the distribution ratios predicted using three different activity coefficient models: (1) commercially available HSC software, (2) the Bromley equation, and (3) a simplified approach adapted from Marcos-Arroyo et al. Ultimately, the Bromley method underpredicted the effect of ionic strength on the Na activity coefficient ( γ Na+ ), HSC overestimated the impact of ionic strength on the expected performance due to the Cs activity coefficient ( γ Cs+ ), but the simplified approach predicted the experimental K d values quite well in a binary matrix. In conclusion, expansion of this approach in complex matrices is necessary for application to Hanford tank waste.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Association‐based activity coefficient model for electrolyte solutions

Abstract This work presents an association‐based activity coefficient model that explicitly considers the solution nonideality due to associations among ions and solvent species. Built upon the electrolyte nonrandom two‐liquid (eNRTL) model, the model greatly improves the accuracy of eNRTL model for strongly associating electrolyte solutions due to presence of ionic species with high surface charge density. The model successfully correlates mean ionic activity coefficients of 46 aqueous single‐salt systems from 10 cations and 5 anions at 298.15 K up to their solubility limits. With the ion‐specific association parameters identified, the model accurately predicts activity and osmotic coefficients for aqueous mixed‐salt systems at 298.15 K. The temperature dependence of the model results has also been examined at 273–373 K. With superior accuracy over a wide range of concentration and temperature, the model represents a major advancement over eNRTL model and has a great potential to be a next‐generation model for electrolyte solutions.

Lin, Yu‐Jeng↗

Activity coefficients of siderophile elements in Fe-Si liquids at high pressure

Metallic core formation in differentiated bodies in the inner solar system can take place between low pressures (near 1 bar) to much higher pressures (up to 100 GPa). Most thermodynamic models of metal-silicate equilibria utilise activity coefficients for metallic tracers in Fe liquids, nearly all of which have been carried out at low pressures. This study focuses on the effect of pressure on activity coefficients for Au, P, V, Mn, Ga, Zn, Cd, Sn, W, Pb, and Nb in liquid Fe-Si alloys. From a series of experiments at 10 GPa, 2373 K containing variable Si content in a metallic liquid we have derived epsilon interaction parameters in Fe-Si liquids ($ε^{Si}_{M}$). Comparison of 1 GPa and 10 GPa data shows no difference except for Nb. Epsilon parameters derived from low pressure experiments can thus be used to calculate activity coefficients for application to higher pressure processes (at least to 10 GPa).

58 GEOSCIENCES↗

Thermodynamic modeling of aqueous lithium salt solutions with association electrolyte nonrandom two-liquid activity coefficient model

The high charge density of lithium ion and the resulting strong association phenomena make thermodynamic modeling of aqueous lithium electrolyte solutions extremely challenging. In this study, the association electrolyte nonrandom two-liquid activity coefficient model of Lin et al. (AIChE J. 2022, 68(2), e17422) is utilized to correlate and predict thermodynamic properties and solubility behavior of aqueous single electrolyte solutions of LiCl, LiBr, LiI, and LiNO 3 , and their mixed electrolyte solutions. Capturing self-association of water, cross-association of ion and water for hydration, and cross-association of cation and anion for ion-pairing, the association model accurately represents the literature experimental data up to saturation concentrations and at the temperature ranging from 263 K to 523 K. Here, this study further investigated the effect of anions of the lithium salts, and re-confirmed that the order of solution non-ideality as LiI > LiBr > LiCl > LiNO 3 because the anions with stronger association strengths are more likely to form ion pairs and thus lower the mean ionic activity coefficients.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Simultaneous Absorption and Desorption Isotherms of Various Hydrogen and Deuterium Mixtures between 20 and 120 °C Are Used to Determine the Activity Coefficients for Palladium-Hydride Solutions

A test bed was constructed to measure the absorption and desorption isotherms for palladium hydride using H 2 , D 2 , and various H 2 /D 2 mixtures for temperatures in the range 20 °C ≤ T ≤ 120 °C. The pressure–composition–temperature isotherms were measured. The pressures obtained with mixtures between each pure isotope were monotonic, yet nonlinear. This nonlinear dependence of total pressure with feed gas protium concentration reveals the mixed isotope hydride system behaves nonideally. A thermodynamic model was adapted from the literature, which accounts for the nonideal nature of the mixed-isotope system. The measured data were used as constraints in this model in order to calculate the protium mole fractions in the hydride phase and the protium activity coefficients for palladium hydride at various temperatures and protium concentrations in the system. Knowing the protium mole fraction and activity coefficients allows for a priori calculation of the isotopologue distribution in the gas phase and the isotope distribution in the hydride phase, given a palladium temperature and equilibrium pressure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Determining Activity Coefficients of SOA from Isothermal Evaporation in a Laboratory Chamber

Nonideal molecular interactions in aerosol particles influence the partitioning of semivolatile organic compounds (SVOCs). However, few direct measurements exist that determine activity coefficients (γ), which quantify nonideality, for individual organic compounds in different atmospheric mixtures. By measuring the isothermal evaporation of SOA formed from multifunctional SVOCs in an environmental chamber, this study determines the mole-fraction-based γ of the bulk SOA in a variety of pre-existing chemically complex particles, approximated as if the bulk SOA behaved like a single SVOC. These multicomponent mixtures contain molecular structures commonly found in the atmosphere. When treated as a single liquid phase, γ of the bulk SOA tends to increase from ~1 to ~5 as the organic seeds and the SOA have more differing polarities. A high computed γ value of 74 for a wet ammonium sulfate-SOA system indicates phase separation. The γ for some individual species was also quantified based on gas-phase measurements and AIOMFAC model predictions. However, the bulk SOA γ cannot be explained by the simplified speciated SVOC–seed interactions, suggesting incomplete compositional understanding of the bulk SOA. In this work, these results demonstrate a method to quantify nonideal behavior and show that it can occur in multicomponent mixtures and therefore influence OA formation, evolution, and lifetimes.

54 ENVIRONMENTAL SCIENCES↗

Determination of Infinite Dilution Activity Coefficients of Molecular Solutes in Ionic Liquids and Deep Eutectic Solvents by Factorization-Machine-Based Neural Networks

Widely known as “green solvents,” ionic liquids (ILs) and deep eutectic solvents (DESs) have been used as substitutes for traditional organic solvents in separation science. To achieve better separations using ILs and DESs, this work aimed to predict the infinite dilution activity coefficients (IDACs) of molecular solutes in these solvents with the state-of-the-art factorization-machine-based neural network (DeepFM). DeepFM combines the benefits of factorization machines and deep neural networks to learn both low-order and high-order interactions among features. The IDAC prediction model was established with 52,372 experimental IDAC datapoints including 260 solvents (252 ILs and 8 DESs) and 112 molecular solutes collected at various temperatures from 288.15 to 428.15 K. Chemical information describing the ILs, DESs, and molecular solutes was included in the IDAC prediction model, including chemical functional groups, molecular weights, and Abraham solvation parameters. The IDAC prediction model showed an improved accuracy compared with alternative models; additionally, DESs were included in the IDAC prediction model for the first time. Here, the model will reduce the energy and resources needed to optimize the selection of ILs and DESs for specific separations, which will promote the development of these green solvents for sustainable chemical processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nonrandom two‐liquid activity coefficient model with association theory

Abstract Considered one of the most versatile and widely used classical thermodynamic models to correlate phase equilibria behavior of nonideal systems, the nonrandom two‐liquid (NRTL) theory does not explicitly account for specific chemical associations such as hydrogen bonding. This deficiency has been recognized as the cause for unsatisfactory representation of association systems like methanol–alkanes binaries. This work presents a practical approach to integrate Wertheim's perturbation theory for association contribution with the classical NRTL model. Specifically, the association contribution is calculated from pre‐determined molecule‐specific association strengths while the physical interaction contribution is captured with NRTL binary interaction parameters. The resulting association NRTL model correlates fluid phase equilibria of association systems with few adjustable parameters and offers improved predictive capability for higher order systems.

Hao, Yifan↗

Modeling ethanol/water adsorption in all-silica zeolites using the real adsorbed solution theory

A comprehensive set of single-component and binary isotherms were collected for ethanol/water adsorption into the siliceous forms of 185 known zeolites using grand-canonical Monte Carlo simulations. Using these data, a systematic analysis of ideal/real adsorbed-solution theory (IAST/RAST) was conducted and activity coefficients were derived for ethanol/water mixtures adsorbed in different zeolites based on RAST. It was found that activity coefficients of ethanol are close to unity while activity coefficients of water are larger in most zeolites, indicating a positive excess free energy of the mixture. This observation can be attributed to water/ethanol interactions being less favorable than water/water interactions in the single-component adsorption of water at comparable loadings. The deviation from ideal behavior can be highly structure-dependent but no clear correlation with pore diameters was identified. Furthermore, our analysis also demonstrates the following: (1) accurate unary isotherms in the low-loading regime are critical for obtaining physically sensible activity coefficients; (2) the global regression scheme to solve for activity model parameters performs better than fitting activity models to activity coefficients calculated locally at each binary state point; and (3) including the dependence on adsorption potential offers only a minor benefit for describing binary adsorption at the lowest fugacities. Finally, the Margules activity model was found incapable of capturing the non-ideal adsorption behavior over the entire range of fugacities and compositions in all zeolites, but for conditions typical of solution-phase adsorption, RAST predictions using zeolite-specific or even bulk Margules parameters provide an improved description compared to IAST.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Screening of metal complexes and organic solvents using the COSMOSAC-LANL model to enhance the energy density in a non-aqueous redox flow cell: an insight into the solubility

In this paper, we have proposed a first-principles methodology to screen transition metal complexes against a particular organic solvent and organic solvents against a particular transition metal complex based on their solubility information without the knowledge of heat of fusion and melting temperature. The energy density of a non-aqueous redox flow cell directly depends on the solubility of the redox active species in the non-aqueous medium. Here, we have used the “COSMOSAC-LANL” activity coefficient model which is based on first-principles COSMO calculations where the microscopic information is passed to the macroscopic world via a dielectric continuum solvation model, followed by a post-statistical thermodynamic treatment of the self-consistent properties of the solute particle to calculate the solubility. To model the activity coefficient at infinite dilution for the binary mixtures, a 3-suffix Margules (3sM) function is introduced for the quantitative estimation of the asymmetric interactions and, for the combinatorial term, the Staverman–Guggenheim (SG) form is used. The new activity coefficient model is separately called the “LANL” activity coefficient model. The metal complex and the organic solvent have been treated as a simple binary mixture. The present model has been applied to a set of 14 different organic solvents and 16 different transition metal complexes. Using the new LANL activity coefficient model in combination with the ADF-COSMOSAC-2013 model, we have shown how one can improve the solubility of a transition metal complex in an organic solvent. We applied our model to screen 84 binary mixtures to predict the compatible pair of redox active species and organic solvent to increase the energy density. The solvation mechanism of the transition metal complexes in the organic solvents was obtained using the new model. The results have been compared with the experimental and theoretical results where they are available.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Generalization of thermodynamic Langmuir isotherm for mixed‐gas adsorption equilibria

Abstract This work presents a comprehensive thermodynamic model for both pure component isotherms and mixed‐gas adsorption equilibria. A generalization of thermodynamic Langmuir isotherm, the proposed model assumes competitive adsorption of multiple adsorbates on adsorbent surface for mixed‐gas adsorption equilibria, and it applies an area‐based adsorption nonrandom two‐liquid activity coefficient model in the activity coefficient calculations for the adsorbate phase. The resulting generalized Langmuir isotherm properly captures both surface loading dependence and adsorbate phase composition dependence for mixed‐gas adsorption equilibria. The model is validated with accurate representations of gas adsorption equilibrium data for varieties of unary, binary, and ternary gas systems. The model results are further compared with those calculated from extended Langmuir isotherm and Ideal Adsorbed Solution Theory.

Hamid, Usman↗

Thermodynamic modeling of adsorption at the liquid-solid interface

Adsorptive separation techniques are significantly energy efficient in comparison to conventional thermal separation techniques such as distillation. Despite extensive research and development activities undertaken for mixed-gas adsorption, the use of adsorption techniques for the separation of multicomponent liquid mixtures is still limited. A major barrier is the lack of accurate adsorption thermodynamic models, which form the scientific foundation of process simulation of such systems, making the translation to industrial scale challenging. In this work, we have rigorously computed the surface excess of adsorption for six binary liquid mixtures on silica gel at 303 K using the frameworks of the generalized Langmuir isotherm (gL) and the adsorbed solution theory (AST). The six binary liquid mixtures were formed by the pair-wise combinations of four components: benzene, 1,2-dichloroethane, cyclohexane, and n-heptane. We have based our calculations by considering simultaneous equilibria of three phases: saturated vapor phase, bulk liquid phase, and adsorbed phase. Further, the composition of the corresponding saturated vapor phase was estimated by the Nonrandom Two-Liquid activity coefficient model and experimental vapor-liquid equilibria data. The activity coefficients of the adsorbed phase, the central issue of multicomponent adsorption thermodynamics, were calculated using the adsorption Nonrandom Two-Liquid activity coefficient model. Devoid of simplifying assumptions, gL and AST provide rigorous thermodynamic frameworks for adsorption equilibria of multicomponent liquid mixtures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of Metal Chloride Impurities on Equilibrium Potential of Fe/FeCl 2 in Eutectic LiCl-KCl

In this study, interaction of dilute metal chloride solutes in molten eutectic LiCl-KCl was studied via equilibrium potential measurements. Open circuit potential (OCP) was measured between a pure iron rod and a Ag/AgCl reference electrode with concentration of FeCl 2 varying from 0.2–1 mol% at 530 °C. The Nernst equation was used to calculate activity coefficient of FeCl 2 based on OCP. Measurements were made in LiCl-KCl-FeCl 2 with and without additions of 0.5 mol% CsCl, NaCl, and LaCl 3 . The activity coefficient of FeCl 2 was found to be unaffected by these small concentrations of CsCl, LaCl 3 , and NaCl. However, there was observed evidence that the activity coefficient of FeCl 2 , above 0.8 mol% Fe, may be affected by the presence of LaCl 3 at higher concentrations beginning around 0.5 mol% La. Over the full range of conditions tested, the activity coefficient of FeCl 2 in molten LiCl-KCl ranged from 2.95 × 10 −5 to 1.01 × 10 −4 .

Electrochemistry↗