Search Results (60)

We present a framework that aims to investigate the role of thermal fluctuations in matter composition and color superconductivity in the nucleation of three-flavor deconfined quark matter in the typical conditions of high-energy astrophysical systems related to compact stars. It is usually assumed that the flavor composition is locally fixed during the formation of the first seed of deconfined quark matter, since a weak interaction acts too slowly to re-equilibrate flavors. However, the matter composition fluctuates around its average equilibrium values at the typical temperatures of high-energy astrophysical processes. Here, we extend our previous two-flavor nucleation formalism to a three-flavor case. We develop a thermodynamic framework incorporating finite-size effects and thermal fluctuations in the local composition to compute the nucleation probability as the product of droplet formation and composition fluctuation rates. Moreover, we discuss the role of color superconductivity in nucleation, arguing that it can play a role only in systems larger than the typical coherence length of diquark pairs. We found that thermal fluctuations in the matter composition led to lowering the potential barrier between the metastable hadronic phase and the stable quark phase. Moreover, the formation of diquark pairs reduced the critical radius and thus the potential barrier in the low baryon density and temperature regime. Full article

The mechanism for the upscale deposition of energy into the atmosphere from molecules and photons up to organized wind systems is examined. This analysis rests on the statistical multifractal analysis of airborne observations. The results show that the persistence of molecular velocity after collision in breaking the continuous translational symmetry of an equilibrated gas is causative. The symmetry breaking may be caused by excited photofragments with the associated persistence of molecular velocity after collision, interaction with condensed phase surfaces (solid or liquid), or, in a scaling environment, an adjacent scale having a different velocity and temperature. The relationship of these factors for the solution to the Navier–Stokes equation in an atmospheric context is considered. The scale invariant version of Gibbs free energy, carried by the most energetic molecules, enables the acceleration of organized flow (winds) from the smallest planetary scales by virtue of the nonlinearity of the mechanism, subject to dissipation by the more numerous average molecules maintaining an operational temperature via infrared radiation to the cold sink of space. The fastest moving molecules also affect the transfer of infrared radiation because their higher kinetic energy and the associated more-energetic collisions contribute more to the far wings of the spectral lines, where the collisional displacement from the central energy level gap is greatest and the lines are less self-absorbed. The relationship of events at these scales to macroscopic variables such as the thermal wind equation and its components will be considered in the Discussion section. An attempt is made to synthesize the mechanisms by which winds are generated and sustained, on all scales, by appealing to published works since 2003. This synthesis produces a view of the general circulation that includes thermodynamics and the defining role of turbulence in driving it. Full article

Herein, we present a comprehensive study on the dissolution behaviour of two sodium–cerium(IV) phosphate phases synthesised hydrothermally from CeO₂ nanoparticles: crystalline Na₂Ce(PO₄)₂ and nanocrystalline NaCe₂(PO₄)₃. For the first time, experimental dissolution data were obtained for both compounds over a wide pH range (1.5–10) under long-term equilibration. The crystalline phase undergoes pH-dependent transformation, including recrystallisation at a near-neutral pH and the formation of secondary CeO₂ nanoparticles above pH 7. In contrast, the nanophase NaCe₂(PO₄)₃ exhibits exceptional structural and chemical stability, showing no signs of recrystallisation, phase transformation, or CeO₂ formation, even after extended ageing. The experimental results help refine the thermodynamic stability conditions for cerium phosphate and oxide phases, providing insights into the reversible transformation pathways between CeO₂ and Ce(IV) phosphates as governed by pH. Full article

The thermodynamic equilibrium of the gas-phase system in lead smelting flue gas was studied using FactSage 8.2 software, and the effects of temperature, the main components of the gas phase, and other factors on the SO₃ content in the equilibrated flue gas were investigated. In addition, experimental research was conducted on a solid-phase catalysis experimental platform to investigate the effect of lead smelting ash on SO₂ catalytic oxidation. The results show that temperature and initial O₂ content in flue gas have a significant impact on the equilibrium concentration of SO₃, while the initial SO₂ content in flue gas has a relatively small impact on the equilibrium concentration of SO₃; the fly ash from the lead smelting flue promotes the conversion of SO₂ to SO₃ in the flue gas. SO₃-suppression experiments show that PbS can adequately inhibit SO₃ formation in a simulated flue gas environment, and the content of SO₃ after adding PbS under different oxygen contents and SO₂ atmospheres does not exceed 0.6%. Through the method of thermodynamic simulation and experimental verification, this study reveals the catalytic oxidation mechanism of SO₂ in lead dust and proposes the use of PbS as an in situ SO₃ inhibitor. Full article

The aim of the present study is to investigate the solubility of nitrogen in super or hyper duplex stainless steel, which is characterized by a very high Cr content, as well as the activity interaction parameters between N and other alloy elements. The chemical equilibrium method was employed in the present experiment. High Cr, Ni, and Mo content Fe−Cr−N−O and Fe−Cr−Ni−Mo−N−O melt are equilibrated at 1873 K under atmospheres of pure nitrogen and Ar/N₂ gas mixture. The melts were placed in Al₂O₃ crucibles and coated with graphite crucibles. The experimental results showed that the solubility of N significantly increased with increasing Cr content, reaching over 1 wt pct at a Cr content of about 40 wt pct. In addition, the solubility of Cr increased slightly with a decrease in Ni content and an increase in Mo content. The activity interaction parameters were fitted using WIPF (Wagner’s Interaction Parameter Formalism), as shown as follows: $e_N^{Cr}=-0.07083$, $r_N^{Cr}=+0.0005888$, $r_N^N=-0.00926$, $e_N^{Ni}=+0.30885$, $r_N^{Ni}=-0.03963$, $e_N^{Mo}=-0.05882$, $r_N^{Mo}=+0.00616$; the comprehensive set of thermodynamic basic parameters obtained in this study can be effectively used to assess the N solubility in USSD with a Cr content exceeding 30 wt pct. Full article

Nucleation is a fundamental and general process at the initial stage of first-order phase transition. Although various models based on the classical nucleation theory (CNT) have been proposed to explain the energetics and kinetics of nucleation, detailed understanding at nanoscale is still required. Here, in view of the homogeneous bubble nucleation, we focus on cavity formation, in which evaluation of the size dependence of free energy change is the key issue. We propose the application of a formula in stochastic thermodynamics, the Jarzynski equality, for data analysis of molecular dynamics (MD) simulation to evaluate the free energy of cavity formation. As a test case, we performed a series of MD simulations with a Lennard-Jones (LJ) fluid system. By applying an external spherical force field to equilibrated LJ liquid, we evaluated the free energy change during cavity growth as the Jarzynski’s ensemble average of required works. A fairly smooth free energy curve was obtained as a function of bubble radius in metastable liquid of mildly negative pressure conditions. Full article

The genome is continuously exposed to a variety of harmful factors that result in a significant amount of DNA damage. This article examines the influence of a multi-damage site containing oxidized imino-allantoin (^OXIa) and 7,8-dihydro-8-oxo-2′-deoxyguanosine (^OXOdG) on the spatial geometry, electronic properties, and ds-DNA charge transfer. The ground stage of a d[A₁^OXIa₂A₃^OXOG₄A₅]*d[T₅C₄T₃C₂T₁] structure was obtained at the M06-2X/6-D95**//M06-2X/sto-3G level of theory in the condensed phase, with the energies obtained at the M06-2X/6-31++G** level. The non-equilibrated and equilibrated solvent-solute interactions were also considered. Theoretical studies reveal that the radical cation prefers to settle on the ^OXOG moiety, irrespective of the presence of ^OXIa in a ds-oligo. The lowest vertical and adiabatic ionization potential values were found for the ^OXOG:::C base pair (5.94 and 5.52 [eV], respectively). Conversely, the highest vertical and adiabatic electron affinity was assigned for ^OXIaC as follows: 3.15 and 3.49 [eV]. The charge transfers were analyzed according to Marcus’ theory. The highest value of charge transfer rate constant for hole and excess electron migration was found for the process towards the ^OXOGC moiety. Surprisingly, the values obtained for the driving force and activation energy of electro-transfer towards ^OXIa₂C₄ located this process in the Marcus inverted region, which is thermodynamically unfavorable. Therefore, the presence of ^OXIa can slow down the recognition and removal processes of other DNA lesions. However, with regard to anticancer therapy (radio/chemo), the presence of ^OXIa in the structure of clustered DNA damage can result in improved cancer treatment outcomes. Full article

We establish a general kinetic scheme for the energy transfer and radical-pair dynamics in photosystem I (PSI) of Chlamydomonas reinhardtii, Synechocystis PCC6803, Thermosynechococcus elongatus and Spirulina platensis grown under white-light conditions. With the help of simultaneous target analysis of transient-absorption data sets measured with two selective excitations, we resolved the spectral and kinetic properties of the different species present in PSI. WL-PSI can be described as a Bulk Chl a in equilibrium with a higher-energy Chl a, one or two Red Chl a and a reaction-center compartment (WL-RC). Three radical pairs (RPs) have been resolved with very similar properties in the four model organisms. The charge separation is virtually irreversible with a rate of ≈900 ns⁻¹. The second rate, of RP1 → RP2, ranges from 70–90 ns⁻¹ and the third rate, of RP2 → RP3, is ≈30 ns⁻¹. Since RP1 and the Red Chl a are simultaneously present, resolving the RP1 properties is challenging. In Chlamydomonas reinhardtii, the excited WL-RC and Bulk Chl a compartments equilibrate with a lifetime of ≈0.28 ps, whereas the Red and the Bulk Chl a compartments equilibrate with a lifetime of ≈2.65 ps. We present a description of the thermodynamic properties of the model organisms at room temperature. Full article

This work aims to theoretically investigate the effect of both the fixed charge density of ion exchange membranes and the ionic strength of the treated aqueous NaCl solution on the generated Donnan potential at thermodynamic equilibrium conditions. The direct objective of our work is to calculate the equilibrium concentration of the Cl⁻ co-ion inside a swelled cation-exchange membrane equilibrated with a water/NaCl system. Two activity coefficient models are employed, i.e., the Debye–Huckel (DH) model (as a reference model) and the Meissner model, which is known for its applicability in treating concentrated solutions. Experimental data available in the literature for Donnan potential are used to verify model predictions. Our study confirms that a high fixed charge density is required to counterbalance the deterioration in membrane selectivity encountered in high-salinity systems. The DH model can be safely used to predict the Donnan potential for feed compositions up to 0.1 M. At higher compositions, the DH model significantly overestimates the predicted (absolute) Donnan potential compared to the Meissner model. The osmotic pressure resulting from the difference in ionic concentration between the membrane phase and the feed phase is found to have insignificant effects on the Donnan potential. The equilibrium computations and methodology are presented in a general way that enables handling multivalent electrolyte systems such as CaCl₂. Full article

Some amino acid systems are known to exhibit solid solution and/or co-crystal behavior upon crystallization, which significantly affects their phase diagrams and complicates the design of their purification processes. Such behaviors are observed in the l-valine/l-leucine system. In this work, the formation and stability of a 3:1 co-crystal of the two amino acids (designated as V₃L) is further investigated. To accomplish the formation, liquid-assisted grinding, slurry equilibration, and sublimation experiments were performed and analyzed via HPLC and PXRD. Additionally, periodic DFT calculations were used to calculate lattice energies and determine the thermodynamics of possible solid phases. Experimental results show a clear metastability of the investigated V₃L co-crystals when compared to its stable solid solution. The calculations underline the metastability and the possible formation of continuous solid solutions between l-valine and l-leucine since lattice energy differences between pure amino acids and mixed compositions are negligible. This previously unknown phase behavior can be used to assess the influence of V₃L on the amino acid purification process and provides a basis for investigating similar systems with small energy differences between pure and mixed compositions in future studies. In addition, it demonstrates the particular variability of solid phases and their relationships in such simple but biologically important amino acid systems. Full article

For the purpose of determining the interaction parameters between Mn and Al, and the influence of Mn on Al₂O₃ inclusions formation in the Fe-Mn-Al-O melts with high Mn and Al contents, three groups of Fe-Mn-Al-O melts with the initial Al content of 3, 5, and 7 mass% and different Mn contents were equilibrated with pure solid Al₂O₃ in an Al₂O₃ crucible at 1873 K and Ar-H₂ atmosphere. Then, the interaction parameters between Mn and Al were deduced using the WIPF (Wagner’s Interaction Parameter Formalism) and the R-K polynomial (Redlich-Kister type polynomial), respectively. From the WIPF, the first- and second-order interaction parameters, $e_{\mathrm{Al}}^{\mathrm{Mn}}$ and $r_{\mathrm{Al}}^{\mathrm{Mn}}$, were determined to be 0.0292 and −0.00016, respectively. From the R-K polynomial, the binary interaction parameters, $\Omega _{\mathrm{Mn}-\mathrm{Al}}^0$ and $\Omega _{\mathrm{Mn}-\mathrm{Al}}^1$, were determined to be 73,439 J/mol and −34,919 J/mol, respectively. The applicability of the WIPF to high Mn and Al content Fe-Mn-Al-O melts was investigated by comparing the Al activity calculated by the WIPF and the R-K polynomial using the obtained data. The results showed that WIPF can be used in high Mn and Al content melts in the current concentration range. Further from the iso-activity contours of Al, the activity of Al increases with increasing Al or Mn content. Finally, the thermodynamic calculations show that the addition of Mn decreases the equilibrium O content at the same Al content, making the formation of Al₂O₃ inclusions easier. Full article

Ruthenium addition inhibits the formation of the topologically close-packed phases in Ni-based superalloys and improves the solid solution strength of Ni–Ti shape memory alloys. Therefore, the Ni–Ti–Ru phase stability is a very valuable indicator of the effects of Ru in Ni-based superalloys and Ni–Ti shape memory alloys. In this study, the isothermal section at 1150 °C and liquidus surface projection of the Ni–Ti–Ru ternary system were determined experimentally using the equilibrated alloy method and diffusion couple method, respectively. Alloys were prepared through the arc-melting of Ni, Ti, and Ru (all 99.99% purity), and then vacuum encapsulation in quartz tubes, followed by annealing at 1150 °C for 36 to 1080 h depending on the alloy composition. Diffusion couples were fabricated by joining one single-phase block (τ1) with one two-phase block (Ni₃Ti + γ(Ni)), and the couples were annealed under vacuum at 1150 °C for 168 h. Reaction temperatures of as-cast alloys were determined by differential scanning calorimetry performed with heating and cooling rates of 10 °C/min. Scanning electron microscopy and X-ray diffraction were used to analyze the microstructure. Seven three-phase regions were found at the 1150 °C isothermal section. Seven primary solidification regions and five ternary invariant reactions were deduced in the liquidus surface projection. A new ternary compound τ1 was discovered in both the isothermal section at 1150 °C and liquidus surface projection. The results aid in thermodynamic modeling of the system and provide guidance for designing Ni-based superalloys and Ni–Ti shape memory alloys. Full article

The crystalline basement aquifer of the Pra Basin in Ghana is essential to the water supply systems of the region. This region is experiencing the ongoing pollution of major river networks from illegal mining activities. Water management is difficult due to the limited knowledge of hydrochemical controls on the groundwater. This study investigates its evolution based on analyses from a previous groundwater sampling campaign and mineralogical investigation of outcrops. The dominant reactions driving the average groundwater composition were identified by means of a combinatorial inverse modelling approach under the hypothesis of local thermodynamical equilibrium. The weathering of silicate minerals, including albite, anorthite, plagioclase, K-feldspar, and chalcedony, explains the observed median groundwater composition in the transition and discharge zones. Additional site-specific hypotheses were needed to match the observed composition of the main recharge area, including equilibration with carbon dioxide, kaolinite, and hematite in the soil and unsaturated zones, respectively, and the degradation of organic matter controlling the sulfate/sulfide content, thus pointing towards kinetic effects during water–rock interactions in this zone. Even though an averaged water composition was used, the inverse models can “bridge” the knowledge gap on the large basin scale to come up with quite distinct “best” mineral assemblages that explain observed field conditions. This study provides a conceptual framework of the hydrogeochemical evolution for managing groundwater resources in the Pra Basin and presents modelling techniques that can be applied to similar regions with comparable levels of heterogeneity in water chemistry and limited knowledge of aquifer mineralogy. The combinatorial inverse model approach offers enhanced flexibility by systematically generating all plausible combinations of mineral assemblages from a given pool of mineral phases, thereby allowing for a comprehensive exploration of the reactions driving the chemical evolution of the groundwater. Full article

The adsorption of polymer microspheres in a stratum can directly affect its action mode and performance in the actual application process. Understanding the adsorption pattern of polymer microspheres and their adsorption mechanism can facilitate optimization of the application mode and enhance the use efficiency. Ultraviolet spectrophotometry was employed to measure the static adsorption characteristics of polymer microspheres (PMS) on the surface of quartz sand. The PMS adsorption capacity on the surface of quartz sand increased with increasing concentration. When the concentration was 1000 mg/L, the static equilibrium adsorption capacity was 402 μg/g, and monolayer adsorption was dominant. The effect of the contact time on the adsorption was investigated, and the fitting was performed using the isothermal adsorption thermodynamic equilibrium model and the adsorption kinetic model. The adsorption of 800 mg/L PMS tended to equilibrate after 0.8 h of adsorption on the surface of quartz sand, and the adsorption of 1400 mg/L PMS tended to equilibrate after 1 h of adsorption on the surface of quartz sand. Good fitting results of the kinetic adsorption process were obtained using the pseudo-first-order (PFO) model, pseudo-second-order (PSO) model, Elovich model, and mixed-order (MO) model. The effects of the temperature, particle size of the quartz sand, solid–liquid ratio, and salinity on the adsorption of PMS on the surface of quartz sand were examined. The PMS adsorption capacity on the surface of quartz sand decreased with increasing environmental temperature. The adsorption of PMS at the solid–liquid interface was an exothermic process, and the enthalpy of adsorption was negative. As the mass of the quartz sand in the solid–liquid ratio increased, the adsorption capacity decreased; a low salinity and neutral pH were conducive to the adsorption of PMS on the surface of quartz sand. Full article

Al–Ni–Er is an essential system in heat-resistant Al alloys. However, the aluminum-rich corner of this system, which has the most practical application significance, has not been fully studied. In this work, the phase equilibria of the Al–Ni–Er system are investigated via experiments and thermodynamic modeling. The isothermal sections of the Al-rich corner of this ternary system at 600 and 700 °C were determined through equilibrated alloys combined with scanning electron microscopy (SEM), electron probe microanalysis (EPMA) and X-ray diffractometry (XRD). In addition, the vertical sections of the Al–Ni–Er system at Al_0.7Ni_0.3–Al_0.7Er_0.3 and Al_0.8Ni_0.2–Al_0.8Er_0.2 were measured via differential scanning calorimetry (DSC) analysis. A new ternary compound, τ14-Al₁₂Ni₂Er₃, was discovered. On the basis of the experimental results of this and previous studies, the ternary Al–Ni–Er system was optimized with the calculation of phase diagrams (CALPHAD) method. The calculated isothermal and vertical section phase diagrams of the ternary system are in good agreement with experimental and literature data. Full article