Thermodynamics Of Solutions Research Articles

Black hole solutions to Einstein-Bel-Robinson gravity

In this paper, we study the physical properties of black holes in the framework of the recently proposed Einstien-Bel-Robinson gravity. We show that interestingly the theory propagates a transverse and massless graviton on a maximally symmetric background with positive energy. There is also a single ghost-free branch that returns to the Einstein case when β → 0. We find new black hole solutions to the equations, both approximate and exact, the latter being a constant curvature black hole solution, and discuss inconsistencies with metrics that were previously claimed to be approximate solutions to the equations. We obtain the conserved charges of the theory and briefly study the thermodynamics of the black hole solutions.

Towards a sustainable thermodynamic optimization solution for preparing unburned low-carbon bricks from low-activity tailings

Basalt tailings, as an important type of solid waste in the mining industry and quarries, are mainly stacked in the open air or buried, causing huge potential harm to the environment and society. In this work, we propose a sustainable and promising utilization method for such low alkali activated tailings. A thermodynamic optimization solution and a design model for unburned low-carbon bricks composed entirely of solid waste were established, and the macro-microscopic mechanisms of hydrate formation and durability were comprehensively analyzed. Firstly, the thermodynamic reaction kinetics of the full chemical composition of basalt tailings modulated by fly ash were used to investigate the effects of different reaction material ratios on hydration products. Then, a new optimization design method of chemical thermodynamics model of alkali excitation was proposed. Further, the hydration mechanism of geopolymer was qualitatively and quantitatively analyzed via test of mechanics, XRD, FTIR, SEM and AFM. The calculation results were very consistent with experimental research, and the basalt-based fly ash-modulated geopolymer brick through optimization met the requirements of durability, especially from the viewpoint of excellent high-temperature resistance. Finally, the life cycle assessment (LCA) method was adopted to analyze the carbon emission reduction potential of current eco-friendly bricks. The carbon emissions were approximately 15.6 % of that of sintered shale hollow bricks and 19.4 % of that of aerated concrete building blocks. Thermodynamic optimization design of alkali activated low-activity tailings unburned bricks technology is one-stone-for-two-birds strategy, which can effectively optimize the process of making bricks from tailings.

Thermodynamics of Aqueous Lithium Nitrate Solutions at 298.15 to 398.15 K and 0.1 to 60 MPa

Thermodynamics of Aqueous Lithium Nitrate Solutions at 298.15 to 398.15 K and 0.1 to 60 MPa

Thermodynamics, phase diagram, structure and anomalies of supercooled aqueous solutions of trehalose: A molecular dynamics study

We perform molecular dynamics simulations of supercooled solutions of trehalose in TIP4P/2005 water, with concentrations of 20 and 40 wt% (weight percentage) in trehalose, a disaccharide often used in cryopreserving solutions. We analyze the thermodynamics and the structure of these solutions. From the isochores we find that in the 20 wt% solution the temperature of maximum density (TMD) line is still present and it is shifted to lower temperatures with respect to that of pure water. We also find that the Widom line and the liquid-liquid critical point (LLCP) are still present for this concentration and we estimate the position of the LLCP to be shifted at lower temperatures and slightly lower pressures with respect to that of pure water. In the 40 wt% solution we find that the TMD line still persists, but the region of density anomaly shrinks. No LLCP is observed down to the lowest temperature investigated, and maxima of the isothermal compressibility, used as proxy for the Widom line, become weaker. The water oxygen - water oxygen radial distribution functions keep on showing the typical distinction between high density and low density liquid found in pure water, but at low temperatures the presence of trehalose appears to favor the high density phase of water more than in pure water. The number of water molecules of the solvation shell confirms this picture.

Sorption of Se(VI) and Se(IV) on AFm phases

Selenate and selenite can sorb on AFm phases such as monosulfate, monocarbonate or hemicarbonate. Sorption and co-precipitation experiments were performed to determine their potential for the immobilization of two of the main aqueous species of selenium: SeVIO42− and SeIVO32−. A preferential uptake by hemicarbonate over monosulfate, and a much weaker sorption on monocarbonate was observed for both Se(IV) and Se(VI). Increased sulfate and carbonate concentrations as present at higher pH lowered the uptake of Se(VI) and Se(IV).Experimentally obtained sorption isotherms on hemicarbonate and monosulfate were reproduced with thermodynamic solid solution models, considering both surface sorption and interlayer bonding. For monocarbonate interlayer sorption was suppressed by the rigid structure and narrow interlayer distance. The observed limited uptake could be described by an anion exchange model on the outer surfaces only. This study shows that both anion exchange in the interlayer as well as sorption on outer surface sites can determine Se uptake by AFm phases.

(Invited) Thermodynamics of Oxygen Transport in Resistive and Electrochemical Memory

Many neuromorphic computing architectures contain emerging memory devices that function through oxygen migration. Examples include resistive memory1 (ReRAM) and electrochemical memory2 (ECRAM), where tuning the distribution of oxygen vacancies enables analog information states. In this presentation, we discuss how oxygen transport in many metal oxides do not obey the drift-diffusion equation, which assumes ideal solution thermodynamics. Instead, the metal oxides undergo composition phase separation into oxygen-rich and oxygen-poor phases. This phase separation explains the long information retention time of ReRAM3. We further use this phase separation to improve the information retention time of oxygen-based ECRAM4,5 by at least ten orders of magnitude, yielding the highest temperature analog nonvolatile memory.

Toward an Understanding of Uric Acid Particle Dissolution: Surface and Bulk-Driven Water Activity.

Uric acid particles contribute to kidney stones, and natural processes for the elimination of stones depend on solute-solvent interactions. The process of uric acid dissolution has previously been understood via the lens of solubility; however, for pure and mixed salt solutions, these approaches do not provide a comprehensive picture of nanoscale particle solution thermodynamics. Unlike solubility measurements, water activity measurements provide us with information about the chemical potential responsible for the migration of water molecules driving the dissolution of particles. In this work, we used in situ experimental tools to estimate water activity values for pure uric acid aqueous droplets at different stages of droplet growth. The process of cloud formation, i.e., water condensation on a solute particle resulting in aqueous droplet formation, was leveraged to compare the water affinity for nanosized uric acid particles with a well-studied inorganic salt, sodium chloride. Specifically, we investigated microscopic uric acid particles (nanoparticles <300 nm, amorphous and super micron particles >5 μm, crystalline) and the mechanism of water uptake. The growth of droplet volume (Growth Factor, GF) for uric acid particles is experimentally observed for supermicrometer crystalline particles (>1 μm) at subsaturated humidity conditions (<100% RH). In addition, the water activity of submicrometer-size uric acid particles is estimated under subsaturated and supersaturated humidity conditions. These measurements provide us with information about the volume growth of droplets as water condenses in particles exposed to different humidity conditions. Our observations under subsaturated humidity conditions show that the uric acid particles have limited volume growth (<1% change per volume and <10% change per volume for crystalline and amorphous measurement, respectively). From the experimental data, the affinity of uric acid solute with water as a solvent is quantified in terms of water activity.

H3trica: Versatile Macrocyclic Chelator for [225Ac]Ac3+ and [155/161Tb]Tb3+ Theranostics.

H3trica is a nonadentate chelating ligand intended for coordinating large radiometal ions, such as those used in nuclear medicine. This chelator, featuring a triaza-18-crown-6 macrocycle with three pendant carboxylic acid functional groups, was synthesized and characterized. Complementary nuclear magnetic resonance (NMR) spectroscopy and high-resolution electrospray-ionization mass spectroscopy (HR-ESI-MS) studies were used to explore the coordination of H3trica with metal ions such as La3+, Y3+ (as a model for Tb3+), and Lu3+ at the bulk scale. Thermodynamic solution studies provided valuable insights, highlighting robust metal complexation of H3trica with La3+, Tb3+, and Lu3+, with the most noteworthy log KML value observed for Tb3+ (log KTbL = 17.08), followed by La3+ (log KLaL = 16.64) and Lu3+ (log KLuL = 16.25). Concentration-dependent radiolabeling studies with [225Ac]Ac3+, [155Tb]Tb3+, and [161Tb]Tb3+ demonstrated rapid complexation (5-30 min) under mild conditions (pH 6-7, 25 °C). Importantly, the radiolabeled complexes exhibited stability during incubation in human serum for one-half-life of the corresponding radiometal. Thus, H3trica emerges as a valuable chelator, demonstrating its potential to coordinate the theranostic couple [225Ac]Ac3+/[155Tb]Tb3+ as well as the powerful terbium quartet ([149/152/155/161Tb]Tb3+) with efficiency and stability.

Improved solution thermodynamics modeling in pervaporation

The current work features a system-level design of pervaporation processes (typically utilized to break azeotropes) that is solution thermodynamics-based (inclusive of validated excess thermodynamic properties). Unlike the standard pervaporation modeling methodology in the literature, the current method (referred to here as PervapS3) deconstructs the membrane module into its constituent units, and the material and energy flows were mathematically validated. These amendments to the previous methodology (i.e., leaf-wise modeling, mathematical validation, and inclusion of excess thermodynamic properties) revealed significant deviations in key parameter values. For a given large-scale pervaporation process dehydrating aqueous isopropanol, the total membrane area and energy requirement calculated were up to 22% and 19% less than the values calculated using the previous methodology. Moreover, due to the inclusion of excess thermodynamic properties in the PervapS3 method, the minimum separation work and the second law (thermodynamic) efficiency were up to 94% and 78% less. In other words, the previous pervaporation modeling methodology overestimated membrane area, energy requirement, minimum separation work, and second law efficiency. Considering a conventional azeotropic distillation process for comparison with pervaporation, it was observed that the simulation-based distillation models from the literature were inclusive of the system non-idealities. Per the previous method, the non-ideal second law efficiency of azeotropic distillation would be compared against the ideal second law efficiency of pervaporation, overestimating the latter. The non-ideal second law efficiency must be employed to facilitate a fairer and more accurate comparison of disparate separation technologies.

Thermodynamics of molecular multicomponent solutions: Evaluation of the partial molar volume at infinite dilution

The present work deals with the evaluation of the partial molar volumes at infinite dilution (v¯i∞) of n-components systems based on the dependence of the experimental density (ρ) on composition without involving binary systems. To do this, the multicomponent solution is interpreted by defining the component (1) as the solvent and the mixture of the remaining (n-1) components as the pseudocomponent (2n), characterized by the inner mole fraction xio. After the analysis of the concept of infinite dilution, equations are derived that allow evaluating the partial molar volumes at infinite dilution of the pseudocomponent (v¯2n∞), based on both the dependence of ln ρ(x2n) and the apparent molar volume ϕv2n(x2n). Then, on the basis of experimental evidences about the linear variation of v¯2n∞ on xio, the relationship between v¯i∞ and v¯2n∞ was established.The applicability of the derived expressions was verified in 36 different cases corresponding to 11 ternary systems in the temperature range of 293.15 ≤ T/K ≤ 323.15.Furthermore, the invariance of the partial molar volume at infinite dilution of the (n-1) components with the proportion in which they are mixed is verified.

Evaluation and thermodynamic optimization of phase diagram of lithium niobate tantalate solid solutions

The lithium niobate–lithium tantalate solid solution’s phase diagram was investigated using experimental data from differential thermal analysis (DTA) and crystal growth. We used XRF analysis to determine the elemental composition of the crystals. The Neumann–Kopp rule provided essential data for the end members lithium niobate (LN) and lithium tantalate (LT). The heats of fusion of the end members, given by DTA measurements, are 103 kJ/mol at 1531 K for LN and 289 kJ/mol at 1913 K for LT. These values were used as input parameters to generate the data. This data served as the basis for calculating a phase diagram for LN-LT solid solutions. Finally, based on the experimental data and a thermodynamic solution model, the Calphad Factsage module optimized the phase diagram. We also generated thermodynamic parameters for Gibbs’ excess energy of the solid solution. A plot of the segregation coefficient as a function of Ta concentration was derived from the phase diagram.

Coupled Experimental Study and Thermodynamic Modeling of the Fe–Si–N System

Some key experiments are carried out to determine the solubility of N in Fe–Si liquid solutions at various compositions, temperatures, and N2 pressures using the sampling method. The Fe–Si–N system is thermodynamically modeled using the CALculation of PHAse Diagrams (CALPHAD) approach for the first time based on critical evaluation of all available experimental data. In the present thermodynamic modeling, the liquid and solid solutions of the Fe–Si–N system are described using the modified quasichemical model and compound energy formalism, respectively. In particular, the Gibbs energies of liquid, FCC_A1, and BCC_A2 solutions are carefully determined to resolve the discrepancies among existing experimental data. The solubility product of β‐Si3N4(s) in Si steels and ferrosilicon alloys, activity coefficients, and interaction parameters of N in liquid and solid Fe–Si–N solutions are determined over a wide temperature range. As an application of the database, the N solubility in Si steels and phase constitution of nitrided ferrosilicon alloys in a wide composition, temperature, and N2 pressure ranges are predicted.

Diffusion mediated thermally induced phase separation for preparing poly(vinylidene fluoride) membranes with enhanced separation performances

Thermally induced phase separation (TIPS) process is an appealing method for preparing poly(vinylidene fluoride) (PVDF) membranes for separation. In this work, we developed a diffusion mediated thermally induced phase separation (d-TIPS) to prepare PVDF membranes with great molecules separation performances. We investigated the thermodynamics of ternary polymer solutions including PVDF, caprolactam (CPL), and Polyethylene glycol (PEG). We controlled liquid–liquid phase separation and the CPL diffusion by adjusting the addition of PEG and molecular weight to modulate the evolution of morphology from spherulitic to bicontinuous structure. The resulting membrane was characterized by morphology, surface chemistry, tensile strength, water contact angle, and perm-selectivity. The membrane was further stretched for enhanced strength, permeance, and rejection. This work provides a fundamental understanding of the diffusion mediated thermally induced phase separation and shows the great potential of PVDF membranes in macromolecules separation.

Coupling Constants as Conserved Charges in Black Hole Thermodynamics.

In a generic theory of gravity coupled to matter fields, the Smarr formula for black holes does not work properly if the contributions of the coupling constants defining the theory are not incorporated. However, these couplings, such as the cosmological constant or the dimensionful parameters that appear in the Lagrangian, are fixed parameters defining the theory, and they cannot be varied. Here, we present a robust method, applicable to any covariant Lagrangian, that upgrades the role of the couplings from being constants in the theory to being free parameters of the solutions. To this end, for each one of the couplings in a theory, a pair of auxiliary scalar and gauge fields is introduced. The couplings are shown to be conserved charges of the global part of the implemented gauge symmetry. Besides, their conjugate chemical potentials are defined as the electric potential of the corresponding gauge fields on the black hole horizon. Using this method, we systematically extend the first law and the Smarr formula by coupling conserved charges and their conjugate potentials. The thermodynamics of a black hole solution in a quadratic gravity theory is given as an example.

Coordination competency of a flexible polyfunctional tripodal framework: an insight on solution thermodynamics and DFT studies

Coordination competency of a flexible polyfunctional tripodal framework: an insight on solution thermodynamics and DFT studies

Scaling symmetry, Smarr relation, and the extended first law in lower-dimensional Lovelock gravity

Recently, it was discovered that lower-dimensional versions of Lovelock gravity exist as scalar-tensor theories that are examples of Horndeski gravity. We study the thermodynamics of the static black hole solutions in these theories up to cubic order through Euclidean methods. Considering solutions with spherical, planar and hyperbolic event horizons (k=+1,0,−1), we show that the universality of the thermodynamics for planar black holes (k=0) and the extended first law that include the variation of the couplings together with their associated potentials hold also in lower dimensions. We find that in D=4,6 where the 2nd- and the 3rd-order Lovelock Lagrangians are boundary terms respectively, the Smarr relation is modified since the entropy is not a homogenous function in these dimensions. We also present a derivation of the Smarr relation and its modified version based on the global scaling properties of the reduced action that is used to obtain the solutions consistently. Unlike the other hairy black hole solutions that have been analyzed before, despite the terms in the reduced action that break the scaling symmetry, the derivation still follows from a conserved Noether charge.

Bridging the Gap in Cryopreservation Mechanism: Unraveling the Interplay between Structure, Dynamics, and Thermodynamics in Cryoprotectant Aqueous Solutions.

Cryoprotectants play a crucial role in preserving biological material, ensuring their viability during storage and facilitating crucial applications such as the conservation of medical compounds, tissues, and organs for transplantation. However, the precise mechanism by which cryoprotectants modulate the thermodynamic properties of water to impede the formation and growth of ice crystals, thus preventing long-term damage, remains elusive. This is evident in the use of empirically optimized recipes for mixtures that typically contain DMSO, glycerol, and various sugar constituents. Here, we use terahertz calorimetry, Overhauser nuclear polarization, and molecular dynamics simulations to show that DMSO exhibits a robust structuring effect on water around its methyl groups, reaching a maximum at a DMSO mole fraction of XDMSO = 0.33. In contrast, glycerol exerts a smaller water-structuring effect, even at higher concentrations (Scheme 1). These results potentially suggest that the wrapped water around DMSO's methyl group, which can be evicted upon ligand binding, may render DMSO a more surface-active cryoprotectant than glycerol, while glycerol may participate more as a viscogen that acts on the entire sample. These findings shed light on the molecular intricacies of cryoprotectant solvation behavior and have potentially significant implications for optimizing cryopreservation protocols.

Acoustical Analysis of Dextran+urea: Insights into Molecular Interactions

Introduction:: The aim of this study is to determine the acoustic parameters of polymer dextran with urea. Recent years have seen an increase in the use of ultrasonic research to describe the physiochemical and thermodynamic characteristics of liquid solutions at various temperatures and frequencies. The size of the pure component and the mixtures had an impact on various interactions, molecular mobility, and kinds of interaction. Which were studied using the acoustical and thermodynamic characteristics? To ascertain how the solvent urea interacts with the solute dextran at the molecular level. Materials and Method: Dextran (molecular weight of 70000) with 6(M)urea was used. The solution's density using a pycnometer, viscosity using an Ostwald viscometer, and ultrasonic velocity using an ultrasonic interferometer were examined. Results:: The physical properties of the medium are affected by the transmission of ultrasonic waves, which also teaches us about the physics of liquids and solutions. Understanding the interactions between the solutes and the solvent in the solution of dextran and urea, both the evaluated parameters were used, such as free volume, internal pressure, absorption coefficient, Rao's constant, and Wada's constant, as well as the observed values, such as ultrasonic velocity, density, and viscosity. Conclusion:: Based on the modification of these parameters with varied temperature and frequency, molecular mobility, different types of intermolecular interaction, and the strength of the bond between the solute (dextran 0.5%) and solvent (6(M) urea) are investigated. The findings have been explained in terms of a structural reorganisation in the aqueous dextran solution. At all the temperatures used for the investigation, the solute-solvent interactions are more significant. The change in the acoustic properties is small because the frequency variation causes the molecules to move swiftly and have little chance to interact. Investigating molecular interactions, including electrostriction, acceptor-donor association, dipole-dipole association, and hydrogen bonding, has used these properties. Understanding molecular interactions helps one to comprehend the core issues surrounding the mechanisms of chemical and biological catalysis and the routes of chemical reactions.

Ionic Pairing and Selective Solvation of Butylmethylimidazolium Chloride Ion Pairs in DMSO-Water Mixtures: A Comprehensive Examination via Molecular Dynamics Simulations and Potentials of Mean Force Analysis.

Ionic liquids (ILs) with dimethyl sulfoxide (DMSO) and water act as a promising solvent medium for the dissolution of cellulose in an efficient manner. To develop a proper solvent system, it is really important to understand the thermodynamics of the molecular solutions consisting of ILs, DMSO, and water. The ion-pairing propensity of the ILs in the presence of DMSO and water plays a crucial role in governing the property of the solvent mixtures. Employing all-atom molecular dynamics simulations, we estimate the potentials of mean force between BMIM+ and Cl- ions in DMSO-water mixtures. Analysis reveals a significant increase in the thermodynamic stability of both contact ion pair (CIP) and solvent-assisted ion pair (SAIP) states with a rising DMSO mole fraction. Thermodynamic assessments highlight the entropic stabilization of CIP states and SAIP states in pure water, in DMSO-water mixtures, and in pure DMSO. The structural analysis reveals that in comparison to the DMSO local density, the local water density is relatively very high around ion pairs, more specifically in the solvation shell of a chloride ion. Preferential binding coefficients also consistently indicate exclusion of DMSO from the ion pair in DMSO-water mixtures. To enhance our understanding regarding the solvent molecules kinetics around the ion pairs, the survival probabilities of DMSO and water are computed. The calculations reveal that the water molecules prefer a prolonged stay in the solvation shell of Cl- ions.

TMACH-1,2-HOPO, a versatile tripodal metal chelator: complexation, solution thermodynamics, spectroscopic and DFT studies

TMACH-1,2-HOPO, a versatile tripodal metal chelator: complexation, solution thermodynamics, spectroscopic and DFT studies