Thermodynamic Tool Research Articles

Investigation of metal-H2O systems at elevated temperatures: Part III. solubility data and new Zr Pourbaix diagrams at 298.15 K and 373.15 K.

Abstract The fuel bundles in coolant systems of CANDUTM reactors operate between 533 to 583 K (260 to 310°C). Given these extreme conditions and because of its neutronic properties, zirconium and Zircaloy-4 are used in these applications which require corrosion resistance at elevated temperatures. However, thermodynamic and hydrolysis properties of aqueous zirconium species have not been measured above standard conditions, making prediction using standard thermodynamic tools, such as the Pourbaix (E-pH) diagram difficult. This lack of information is addressed through solubility measurements and the development of elevated temperature Pourbaix diagrams for zirconium and Zircaloy-4. These Pourbaix diagrams of zirconium and a multi-element diagram (Sn, Zr, Cr) of Zircaloy-4 were developed at 373.15 K (100°C) and are presented in this work. Solubility measurements were made using a batch-style pressure vessel and concentration measurements were made using ICP-OES and ICP-MS, for zirconium and Zircaloy-4, respectively. For Zr(OH)6(2-); Zr(OH)4 (aq); Zr(OH)3+; and Zr(OH)2(2+) the Gibbs energy of formation (ΔG(°f,373.15 K)°) were found to be: -2177.4±8.5 kJ/mol, -1704.9±1.5 kJ/mol, -1808.8±8.9 kJ/mol, and -1095.1±2.7 kJ/mol, respectively.

Valorization of lithium containing slags from pyrometallurgical recycling route of spent lithium-ion batteries: The enrichment of γ-LiAlO2 phase from thermodynamic controlled and modified slags

Pyro-metallurgical processing technology is widely used in the spent lithium-ion batteries recycling to recover valuable metals such as cobalt, nickel and copper, while lithium primarily remains in the slag. The effective valorization of slag, especially lithium recovery, constitutes a significant issue in contemporary pyrometallurgical processes due to the paucity of studies. This paper proposes a novel perspective by defining slag as an aggregate of engineered artificial minerals. Thus, not only the parameters of the beneficiation process can be studied to optimize the separation efficiency during treatment, but also the slag can be re-designed to optimize the carrier minerals of target elements and gangue mineral composition in the initial step with thermodynamic tools. In this paper, the engineering of artificial minerals (EnAM) method was applied to the slag design of the Li2O-CaO-Al2O3-SiO2-MnO system, and an initial attempt was made to apply EnAM method to the flotation study. A flotation study on enrichment effect of the target phase γ-LiAlO2 from thermodynamic controlled slags is conducted.

Resetting as a swift equilibration protocol in an anharmonic potential

We present and characterize a method to accelerate the relaxation of a Brownian object between two distinct equilibrium states. Instead of relying on a deterministic time-dependent control parameter, we use stochastic resetting to guide and accelerate the transient evolution. The protocol is investigated theoretically, and its thermodynamic cost is evaluated with the tools of stochastic thermodynamics. Remarkably, we show that stochastic resetting significantly accelerates the relaxation to the final state. This stochastic protocol exhibits energetic and temporal characteristics that align with the scales observed in previously investigated deterministic protocols. Moreover, it expands the spectrum of stationary states that can be manipulated, incorporating new potential profiles achievable through experimentally viable protocols. Published by the American Physical Society 2024

Electrostatics Choreographs the Aggregation Dynamics of Full-Length TDP-43 via a Monomeric Amyloid Precursor.

TDP-43 is a ubiquitously expressed, multidomain functional protein that is distinctively known to form aggregates in many fatal neurodegenerative disorders. However, the information for arresting TDP-43 aggregation is missing due to a lack of understanding of the molecular mechanism of the aggregation and structural properties of TDP-43. TDP-43 is inherently prone to aggregation and has minimal protein solubility. Multiple studies have been performed on the smaller parts of TDP-43 or the full-length protein attached to a large solubilization tag. However, the presence of co-solutes or solubilization tags is observed to interfere with the molecular properties and aggregation mechanism of full-length TDP-43. Notably, this study populated and characterized the native, dimeric state of TDP-43 without the interference of co-solutes or protein modifications. We observed that the electrostatics of the local environment is capable of the partial unfolding and monomerization of the native dimeric state of TDP-43 into an amyloidogenic molten globule. By employing the tools of thermodynamics and kinetics, we reveal the structural characteristics and temporal order of the early intermediates and transition states during the transition of the molten globule to β-rich, amyloid-like aggregates of TDP-43, which is governed by the electrostatics of the environment. The current advanced understanding of the nature of native and early aggregation-prone intermediates, early steps, and the influence of electrostatics in TDP-43 aggregation is essential for drug design.

COSMO-RS-based assessment of thermodynamic tools in predicting the polar and non-polar solvents efficiency in vegetable oil extraction.

One of the prevalent methods for evaluating separation performance is to predict the interactions of solvent and solute molecules. The infinite dilution activity coefficient, Gibbs free energy, and sigma profiles provided insights into the solubilization of a solute and revealed the intensity of the solution's molecular interactions. The effective thermodynamic tools (infinite dilution activity coefficient, Gibbs free energy) were evaluated for predicting the efficiency of 18 polar and non-polar organic solvents in rubber seed oil (RSO) extraction. An infinite dilution activity coefficient was computed to evaluate the solubility of the rubber seed oil model compound (linoleic acid) in the organic solvents. Gibbs free energy was evaluated to show the energy change associated with the molecules mixing process and forecast the miscibility of linoleic acid molecules in the solvents. Moreover, the study examined the sigma profiles and sigma surfaces of organic solvents and linoleic acid to acquire a deeper insight into their similarities and how they interact molecularly. According to the computational prediction and experimental verification, the thermodynamic properties of Gibbs free energy and activity coefficient proved to be highly effective tools for screening polar and moderately polar solvents, predicting the molecular interactions with solute. Whereas the sigma profile and sigma surface were found to be the most efficient tools for evaluating the efficacy of non-polar solvents. Solvents with moderate polarity, such as tetrahydrofuran and diethyl ether, as well as non-polar solvents like pentane, heptane, and n-hexane, proved to be effective and favorable for oil extraction, resulting in the highest oil yields of approximately 27.0%. Overall, the COSMO-RS method demonstrates its utility in estimating the solubility of RSO in organic solvents, enabling early identification of the most effective solvent. The initial geometry optimization of every component was conducted through density functional theory (DFT) using TmoleX software. A single-point density functional theory (DFT) computation using Becke Perdew 86 (BP86) and the Triple-Zeta Valence Potential (TZVPD) was performed to produce.cosmo files. COSMO-RS calculations were performed by applying the parameterization file BP_TZVPD_FINE_19.ctd using COSMOthermX software. The practical extraction of oil from plant seeds was performed using a sonicator bath to verify the accuracy of the COSMO-RS predictions.

Slowdown of thermalization and the emergence of prethermal dynamics in disordered optical lattices

By utilizing the theoretical tools of optical thermodynamics, we investigate thermalization in nonlinear disordered lattices beyond the diffusion regime. Even under extreme levels of disorder, we analytically predict the expected thermal value of entropy and the associated Rayleigh-Jeans distribution, once thermalization ensues. In this context, we reveal a crossover point of disorder beyond which we observe a pronounced slowdown of thermalization in a regime characterized by a logarithmic scaling of equilibration times. By employing the same analytical and numerical tools, we investigate the scaling of thermalization times with respect to both the number of sites and optical temperatures. By exploring the physics of the underlying nonequilibrium response, we unveil a multitude of emerging thermal phenomena, including the development of prethermal Rayleigh-Jeans states in the presence of an optical heat bath and the deceleration of self-heating in Floquet photonic lattices. Published by the American Physical Society 2024

The effect of hydrostatic pressure on lipid membrane lateral structure.

High pressure is both an environmental challenge to which deep sea biology has to adapt, and a highly sensitive thermodynamic tool that can be used to trigger structural changes in biological molecules and assemblies. Lipid membranes are amongst the most pressure sensitive biological assemblies and pressure can have a large influence on their structure and properties. In this chapter, we will explore the use of high pressure small angle X-ray diffraction and high pressure microscopy to measure and quantify changes in the lateral structure of lipid membranes under both equilibrium high pressure conditions and in response to pressure jumps.

Integrated Experimental Phase Equilibria and Thermodynamic Modelling Research and Implementation in support of progress of process pyrometallurgy towards sustainability

Responding to the many sustainability challenges facing the metallurgical industry, we report progress that has been made on the development of predictive tools that can be applied to a wide range of technologies. The aim is to provide accurate, fundamentally-based thermodynamic tools that can be used by industry to improve process efficiencies, metal recoveries and productivities, and reduce energy requirements of pyrometallurgical systems. The program involves an integrated experimental and thermodynamic modelling research on phase equilibria in complex multi-component, multi-phase gas-slag-matte-speiss-metal-solids system with the Cu2O-PbO-ZnO-FeO-Fe2O3-CaO-Al2O3-MgO-SiO2-S major and As-Sn-Sb-Bi-Ag-Au-Ni-Co-Cr-Na minor elements. The experiments involve high temperature equilibration in controlled gas atmospheres, rapid quenching and direct measurement of equilibrium phase compositions with quantitative microanalytical techniques, including electron probe X-ray microanalysis and Laser Ablation ICP-MS. The thermodynamic modelling is undertaken using FactSage software package with advanced thermodynamic solution models. The continuing development of analytical and research methodologies has resulted in significant advances in predictive capability. Implementation of the results of fundamental studies involves ongoing collaboration of researchers and industry technologists, and the provision of advanced professional training. An overview of recent progress in research, implementation and applications in industrial practice will be presented in the paper.

Sustainable pathways to generate hydrogen: A thermodynamic view

We hereby share our perspective and experience regarding hydrogen thermodynamics. The thermodynamic modeling of hydrogen and hydrogen-containing mixtures seen from a historical perspective, beginning in 1979 with the publication of Daubert and Graboski on the modification of SRK EoS to systems containing hydrogen, up to nowadays where different tools as molecular simulations are in place, is shortly presented. The selected milestones are directly connected with the vision of the company to be one of the largest low-carbon hydrogen technology licensors in the world and has been the foundation for the design of safe and reliable chemical manufacturing processes in 8 decades. With our technical knowhow in hydrogen technologies, we are currently further developing and optimizing next gen blue and green technologies, thereby needing thermodynamic tools for a wide range of hydrogen-containing systems, over a wide range of conditions, and for different properties. We see in general a need for standardization and guidelines on how to perform the thermodynamic part of this type of new projects, and embrace all relevant efforts, especially when it comes to properties and fluid behavior related to safety issues. The existing status both in terms of experimental data and thermodynamic models will be discussed and evaluated.Finally, some scientific areas will be mentioned where we see much promise in the future and we believe they can contribute to the modeling of the new processes, from a broader perspective, going “beyond” thermodynamic analysis and allowing a more holistic assessment of new projects.

Bound on annealing performance from stochastic thermodynamics, with application to simulated annealing.

Annealing is the process of gradually lowering the temperature of a system to guide it towards its lowest energy states. In an accompanying paper [Y. Luo etal., Phys. Rev. E 108, L052105 (2023)10.1103/PhysRevE.108.L052105], we derived a general bound on annealing performance by connecting annealing with stochastic thermodynamics tools, including a speed limit on state transformation from entropy production. We here describe the derivation of the general bound in detail. In addition, we analyze the case of simulated annealing with Glauber dynamics in depth. We show how to bound the two case-specific quantities appearing in the bound, namely the activity, a measure of the number of microstate jumps, and the change in relative entropy between the state and the instantaneous thermal state, which is due to temperature variation. We exemplify the arguments by numerical simulations on the Sherrington-Kirkpatrick (SK) model of spin glasses.

Design and thermodynamic analysis of a pathway enabling anaerobic production of poly-3-hydroxybutyrate in Escherichia coli

Utilizing anaerobic metabolisms for the production of biotechnologically relevant products presents potential advantages, such as increased yields and reduced energy dissipation. However, lower energy dissipation may indicate that certain reactions are operating closer to their thermodynamic equilibrium. While stoichiometric analyses and genetic modifications are frequently employed in metabolic engineering, the use of thermodynamic tools to evaluate the feasibility of planned interventions is less documented. In this study, we propose a novel metabolic engineering strategy to achieve an efficient anaerobic production of poly-(R)-3-hydroxybutyrate (PHB) in the model organism Escherichia coli. Our approach involves re-routing of two-thirds of the glycolytic flux through non-oxidative glycolysis and coupling PHB synthesis with NADH re-oxidation. We complemented our stoichiometric analysis with various thermodynamic approaches to assess the feasibility and the bottlenecks in the proposed engineered pathway. According to our calculations, the main thermodynamic bottleneck are the reactions catalyzed by the acetoacetyl-CoA β-ketothiolase (EC 2.3.1.9) and the acetoacetyl-CoA reductase (EC 1.1.1.36). Furthermore, we calculated thermodynamically consistent sets of kinetic parameters to determine the enzyme amounts required for sustaining the conversion fluxes. In the case of the engineered conversion route, the protein pool necessary to sustain the desired fluxes could account for 20% of the whole cell dry weight.

Modeling phase equilibria and speciation in aqueous solutions of rare earth elements with hydroxide and organic ligands

A thermodynamic model has been developed for calculating speciation and phase equilibria in aqueous solutions of rare earth elements (REEs) with hydroxide, acetate, citrate, and oxalate anions. The computational framework is based on the Mixed-Solvent Electrolyte (MSE) framework, which has been previously used to establish a systematic treatment of binary and multicomponent systems containing REE sulfates and chlorides up to solid–liquid saturation at temperatures up to 300 °C. The model has been parametrized by performing a multi-property analysis of critically evaluated speciation and solubility data. For rare earth hydroxides, a comprehensive model has been developed for fourteen REEs (i.e., for yttrium and all lanthanides except promethium). The effect of the crystallinity of rare earth hydroxides on their solubility has been analyzed. Model parameters have been determined for two limiting cases, i.e., for crystalline and amorphous hydroxides, while recognizing that the hydroxides may span a range of degrees of crystallinity. For the organic ligands, the model has been established for neodymium with additional analysis for other selected REEs. The model accurately reproduces the effects of pH, temperature, and complexation with organic ligands on the behavior of rare earth elements in aqueous solutions. When coupled with previously developed models for inorganic rare earth salts, it provides a thermodynamic tool for the design and optimization of separation processes for the production and recycling of REEs and for predicting the properties of REEs in geological and biological settings.

Design of a Ti–V–Nb–Cr alloy with room temperature hydrogen absorption/desorption reversibility

Computational thermodynamic tools are employed to design Ti–V–Nb–Cr alloys for hydrogen storage. Calculation of phase diagrams (CALPHAD) is employed to find compositions prone to form body centered cubic (BCC) alloys. A thermodynamic model to calculate pressure-composition-temperature (PCT) diagrams is used to select compositions with plateau pressure above 1 bar at room temperature. Three alloys are synthesized via arc melting and present predominantly BCC structures. The alloys show capacity to absorb hydrogen with fast kinetic without any activation treatment. PCT diagrams demonstrate reasonable values of plateau pressures and thermodynamic properties compared to calculated ones. Cycling experiments are measured to evaluate room-temperature reversibility in the Ti11V30Nb28Cr31 alloy. A continuous reduction in capacity is observed due to stabilization of the face centered cubic (FCC) hydride. The resistance to air exposure of the Ti11V30Nb28Cr31 alloy is investigated. The alloy demonstrated to be easily reactivated after air exposure by a heat treatment under dynamic vacuum.

Evaluating the abiotic synthesis potential and the stability of building blocks of life beneath an impact-induced steam atmosphere.

A prerequisite for prebiotic chemistry is the accumulation of critical building blocks of life. Some studies argue that more frequent impact events on the primitive Earth could have induced a more reducing steam atmosphere and thus favor widespread and more efficient synthesis of life building blocks. However, elevated temperature is also proposed to threaten the stability of organics and whether life building blocks could accumulate to appreciable levels in the reducing yet hot surface seawater beneath the steam atmosphere is still poorly examined. Here, we used a thermodynamic tool to examine the synthesis affinity of various life building blocks using inorganic gasses as reactants at elevated temperatures and corresponding steam pressures relevant with the steam-seawater interface. Our calculations show that although the synthesis affinity of all life building blocks decreases when temperature increases, many organics, including methane, methanol, and carboxylic acids, have positive synthesis affinity over a wide range of temperatures, implying that these species were favorable to form (>10-6 molal) in the surface seawater. However, cyanide and formaldehyde have overall negative affinities, suggesting that these critical compounds would tend to undergo hydrolysis in the surface seawaters. Most of the 18 investigated amino acids have positive affinities at temperature <220°C and their synthesis affinity increases under more alkaline conditions. Sugars, ribose, and nucleobases have overall negative synthesis affinities at the investigated range of temperatures. Synthesis affinities are shown to be sensitive to the hydrogen fugacity. Higher hydrogen fugacity (in equilibrium with FQI or IW) favors the synthesis and accumulation of nearly all the investigated compounds, except for HCN and its derivate products. In summary, our results suggest that reducing conditions induced by primitive impacts could indeed favor the synthesis/accumulation of some life building blocks, but some critical species, particularly HCN and nucleosides, were still unfavorable to accumulate to appreciable levels. Our results can provide helpful guidance for future efforts to search for or understand the stability of biomolecules on other planets like Mars and icy moons. We advocate examining craters formed by more reducing impactors to look for the preservation of prebiotic materials.

Ellingham diagram: A new look at an old tool

Ellingham diagrams are thermodynamic tools that allow comparing the relative stability among oxides. They are well established for pure metals, but they can be obtained for any multi-element system if the chemical activity of each component is known. However, chemical activities are very difficult to obtain experimentally and, because of the lack of these data, Ellingham diagrams have never been reported for complex industrial alloys. This work aims to show how nowadays advanced thermodynamic databases can be used to supply for this lack. Herein, the Ellingham diagrams of four wildly used alloys- TiAl 48–2–2, TA6V, Inconel 718 and 304 steel- have been computed. The results are discussed in respect to the oxidation behavior of these alloys and important differences in respect to the Ellingham diagram of pure metals are highlighted.

Modeling the Solubility of Monoterpenoids with Hybrid and Predictive Thermodynamic Tools.

The Abraham and NRTL-SAC semipredictive models were employed to represent the solubility of (-)-borneol, (1R)-(+)-camphor, l-(-)-menthol, and thymol in water and organic solvents, using data measured in this work and collected from the literature. A reduced set of solubility data was used to estimate the model parameters of the solutes, and global average relative deviations (ARDs) of 27% for the Abraham model and 15% for the NRTL-SAC model were obtained. The predictive capability of these models was tested by estimating the solubilities in solvents not included in the correlation step. Global ARDs of 8% (Abraham model) and 14% (NRTL-SAC model) were obtained. Finally, the predictive COSMO-RS model was used to describe the solubility data in organic solvents, with ARD of 16%. These results show the overall better performance of NRTL-SAC in a hybrid correlation/prediction approach, while COSMO-RS can produce very satisfactory predictions even in the absence of any experimental data.

Energy production in one-qubit quantum Agrawal machines

AbstractWe obtain the power and Ω-function of one-qubit Agrawal quantum heat engines solving the Lindbland equation and using the tools of Finite Time Thermodynamics. We prove that these two thermodynamic functions have their maximum values for efficiencies different to zero and the Carnot efficiency. Finally, analyzing the high temperature limit of AQHEs we discover the range of temperatures for which the quantum behaviour is valid.

A comprehensive investigation of the (Ti0.5Zr0.5)1(Fe0.33Mn0.33Cr0.33)2 multicomponent alloy for room-temperature hydrogen storage designed by computational thermodynamic tools

(Ti0.5Zr0.5)1(Fe0.33Mn0.33Cr0.33)2 multicomponent alloy designed by computational thermodynamic tools shows excellent room-temperature hydrogen storage properties.

A thermodynamic tool for designing efficient syntheses of monodisperse and size-tuned nanocrystals

A thermodynamic model based on a modified Classical Nucleation Theory is applied to the formation of colloidal metal and semiconductor nanocrystals. The predictions of the model are compared to experimental results published in the literature and well-established kinetic models, indicating an overall good accuracy. The definition of a potential energy curve that characterizes the system allows the prediction of the final (equilibrium) size of crystals as well as their size distribution. Furthermore, the nucleation process is studied in terms of key parameters affecting the concentration of crystals and is found to be related to the change in critical energy of stable nuclei during nucleation. Threshold values for the nuclei concentrations are predicted, defining instability and metastability conditions for the nucleation process. This model can help in refining our understanding of the mechanisms behind nucleation and growth of nanocrystals, with the goal of optimizing the fabrication process for industrial-scale production of nanocrystals and nanocrystal-based devices.

Development of a Model to Estimate the Thermodynamic Stability of Organic Substances in Leaching Processes

The leaching processes for metals using organic substances represent a sustainable approach to recover precious minerals from solid matrices. However, the generation of organometallic species and the lack of thermodynamic diagrams make it difficult to advance the understanding of their behavior and optimize the process. In this work, a thermodynamically and stoichiometrically consistent mathematical model was developed to estimate the thermodynamic stability of organic substances during the leaching process, and iron leaching with oxalic acid was used as a case study. The Pourbaix and the global thermodynamic stability diagrams for the system were developed in this study. Using a Gaussian®, it was estimated that the Gibbs free energy formation for Fe(C2O4)22−, Fe(C2O4)21−, and Fe(C2O4)33− was −1407.51, −2308.38, and −3068.89 kcal/mol. A set of eleven independent reactions was formulated for the sixteen species involved in the leaching process, and its stability functions in terms of Eh and pH were calculated to generate a 3D global thermodynamic stability diagram. According to the Eh-pH diagrams for the leaching process, ferrioxalate was identified as the most stable and predominant species in the leaching process at pH above 6.6 under reductive conditions. The mathematical model developed in this work resulted in a thermodynamic tool for predicting leaching processes.