Thermodynamic Equilibrium Research Articles

Microscopic state equation for oscillator chains

Systems allowing anomalous transport of mass, momentum energy, etc., such as low-dimensional particles systems or highly confining media, are hard to characterize thermodynamically. Indeed, local thermodynamic equilibrium may not be established and their behaviour often strongly depends on many microscopic parameters, including the symmetry of the interaction potentials. Thermodynamic state equations, on the other hand, involve a small set of observables, which are obtained averaging in time and over the large number of particles that populate mesoscopic cells in which local equilibrium can be realized. In this work we show that a linear relation discovered earlier, that connects the average distance between pairs of consecutive particles with their kinetic energy, applies to quite a large set of 1-dimensional particle systems known to produce anomalous transport. This relation is microscopic in nature, since the quantities involved are neither averaged over many particles, neither over very large times. Nevertheless, its robustness is under variations of the external parameters, and the limited set of quantities it involves qualify it as a state equation, analogously to thermodynamic relations. We provide conditions for which the relation can be violated within a limited range of parameters values, and we find that it can be extended to two-dimensional networks of coupled oscillators. The validity of this relation further shows that the states of aggregation of matter in low-dimensional systems are often different from standard macroscopic ones.

Biosolid Gasification Performance Prediction Using a Stoichiometric Thermodynamic Model.

The gasification process can recover energy from biosolids produced in wastewater treatment. This paper developed a stoichiometric thermodynamic equilibrium model for biosolid gasification based on the biosolid properties, thermodynamic database, and equilibrium constants. If the calculation result showed that the quantity of char was negative, the quantity of char was put to zero, and the simulation was carried out again. The model was first verified by woody gasification under isothermal conditions, and the influence of a given temperature on biosolid gasification was simulated. The model further investigated the effects of different feedstock types, moisture contents, equivalence ratios, and reaction extensions on the adiabatic temperature, exergy efficiency, and syngas properties under autothermal conditions. The four factors were all the main factors for adiabatic temperature. The exergy efficiency depended more on the operation conditions than on the feedstock type. The H2 concentration of the dry syngas in biosolid gasification exhibited a curve both against the given temperature under isothermal conditions and against the moisture content under autothermal conditions.

Fast, approximation-free molecular simulation of the SPC/Fw water model using non-reversible Markov chains

In a world made of atoms, computer simulations of molecular systems such as proteins in water play an enormous role in science. Software packages for molecular simulation have been developed for decades. They all discretize Hamilton’s equations of motion and treat long-range potentials through cutoffs or discretization of reciprocal space. This introduces severe approximations and artifacts that must be controlled algorithmically. Here, we bring to fruition a paradigm for molecular simulation that relies on modern concepts in statistics to explore the thermodynamic equilibrium with an exact and efficient non-reversible Markov process. It is free of all discretizations, approximations, and cutoffs. We explicitly demonstrate that this approach reaches a break-even point with traditional molecular simulation performed at high precision, but without any of its approximations. We stress the potential of our paradigm for crucial applications in biophysics and other fields, and as a practical approach to molecular simulation. We set out a strategy to reach our goal of rigorous molecular simulation.

Understanding the deficiency in inertial confinement fusion hohlraum x-ray flux predictions using experiments at the National Ignition Facility.

The predicted implosion performance of deuterium-tritium fuel capsules in indirect-drive inertial confinement fusion experiments relies on precise calculations of the x-ray drive in laser-heated cavities (hohlraums). This requires accurate, spectrally dependent simulations of laser to x-ray conversion efficiencies and x-ray absorption losses to the hohlraum wall. A set of National Ignition Facility experiments have identified a cause for the long-standing hohlraum "drive deficit" as the overprediction of gold emission at ∼2.5 keV in nonlocal thermodynamic equilibrium coronal plasma regions within the hohlraum. Reducing the emission and absorption opacity in this spectral region by ∼20% brings simulations into agreement with measured x-ray fluxes and spectra.

The Fate of Fluorine Post Per- and Polyfluoroalkyl Substances Destruction during the Thermal Treatment of Biosolids: A Thermodynamic Study

Per- and polyfluoroalkyl substances (PFAS) are a group of fluorinated synthetic chemicals that are highly recalcitrant, toxic, and bio-accumulative and have been detected in biosolids worldwide, posing potential risks to humans and the environment. Recent studies suggest that the organic C-F bond in PFAS can be destructed and potentially mineralised into inorganic fluorides during thermal treatment. This study focuses on thermodynamic equilibrium investigations and the fate of fluorine compounds post-PFAS destruction during biosolid thermal treatment. The results indicate that gas-phase fluorine compounds are mainly hydrogen fluoride (HF) and alkali fluorides, whereas solid-phase fluorine compounds include alkaline earth fluorides and their spinels. High moisture and oxygen content in the volatiles increased the concentration of HF in the gas phase. However, adding minerals reduced the emission of HF in the gas phase significantly and enhanced the capture of fluorine as CaF2 spinel in the solid phase. This study also investigates the effect of feedstock composition on the fate of fluorine. High ash content and low volatile matter in the feedstock reduced HF gas emissions and increased fluorine capture in the solid product. The findings of this work are useful in designing thermal systems with optimised operating conditions for minimising the release of fluorinated species during the thermal treatment of PFAS-containing biosolids.

Fabricating Ion Sieves by 3D Printing for Selective Lithium Adsorption from Brines

AbstractThis work presents the formation of a stable 3D monolith based on manganese oxide for the adsorption of lithium from brine. The precursor phase was prepared by microwave‐assisted hydrothermal synthesis and a subsequent calcination process to achieve the desired crystalline phase LiMn2O4. The monolith was formed using additive manufacturing, which allowed its size and shape to be controlled. Subsequently, this monolith was washed with a HCl solution to generate adsorption sites for lithium. The prepared materials were characterized by XRD, FTIR, TGA, N2 physisorption, and SEM‐EDS. Analysis confirmed that the 3D monolith retained its crystalline structure throughout the process. The kinetic characteristics of the adsorption process were evaluated using pseudo‐first and pseudo‐second order equations, as well as Freundlich and Langmuir equations, to describe thermodynamic equilibrium. Monoliths were able to capture lithium up to 13.84 mg/g and the Freundlich equation described the equilibrium (R2=0.9751), while the second‐order equation better described the kinetic behavior (R2=0.9130). Results showed that monoliths are selective towards lithium in the presence of competing cations. The stability of the materials was evaluated in adsorption‐desorption cycles, demonstrating a competitive reuse after five cycles. This research presents a promising new approach for developing efficient lithium extraction methods from brine.

Experiment and simulation assessment of supercritical underground coal gasification in deep coal seam

To explain the impact of geological and process factors on underground coal gasification in deep coal seam (>2200 m) and promote the efficient and clean extraction and conversion of coal, this study employs the orthogonal experimental design method to investigate the impact of CO2 coefficient (0–1), moisture content (30–80 wt%), calcite content (0–10 wt%), albite content (0–10 wt%), kaolinite content (0–20 wt%), reaction temperature (550–650 °C), and reaction pressure (23–27 MPa) on the characteristics of coal underground gasification under supercritical H2O/CO2 conditions. Furthermore, range analysis and variance analysis are utilized to determine the degree of influence of each factor and the interaction between factors. Finally, the Gibbs free energy minimization method is used to conduct a thermodynamic equilibrium analysis of coal supercritical H2O/CO2 gasification at high temperatures (750–1000 °C). The results indicate that the three most significant factors affecting the process of coal supercritical H2O/CO2 gasification are the CO2 coefficient, moisture content, and reaction temperature. The maximum carbon gasification efficiency at 650 °C in experimental cases and 1000 °C in simulation cases is 22.2% and 88.1%, respectively. Although the addition of CO2 at lower temperatures reduces the carbon gasification efficiency, at high temperatures (>900 °C), a higher initial CO2 concentration increases the carbon gasification efficiency. The addition of CO2 under conditions of low moisture content increases the mole fraction of H2, but reduces it under conditions of high moisture content (≥70 wt%). Among the three minerals, calcite has the most significant influence on the gasification process.

Current Status and Development Trend of Research on Polymer-Based Kinetic Inhibitors for Natural Gas Hydrates.

As the understanding of natural gas hydrates as a vast potential resource deepens, their importance as a future clean energy source becomes increasingly evident. However, natural gas hydrates trend towards secondary generation during extraction and transportation, leading to safety issues such as pipeline blockages. Consequently, developing new and efficient natural gas hydrate inhibitors has become a focal point in hydrate research. Kinetic hydrate inhibitors (KHIs) offer an effective solution by disrupting the nucleation and growth processes of hydrates without altering their thermodynamic equilibrium conditions. This paper systematically reviews the latest research progress and development trends in KHIs for natural gas hydrates, covering their development history, classification, and inhibition mechanisms. It particularly focuses on the chemical properties, inhibition effects, and mechanisms of polymer inhibitors such as polyvinylpyrrolidone (PVP) and polyvinylcaprolactam (PVCap). Studies indicate that these polymer inhibitors provide an economical and efficient solution due to their low dosage and environmental friendliness. Additionally, this paper explores the environmental impact and biodegradability of these inhibitors, offering guidance for future research, including the development, optimization, and environmental assessment of new inhibitors. Through a comprehensive analysis of existing research, this work aims to provide a theoretical foundation and technical reference for the commercial development of natural gas hydrates, promoting their safe and efficient use as a clean energy resource.

Development of a Meshless Kernel-Based Scheme for Particle-Field Brownian Dynamics Simulations.

We develop a meshless discretization scheme for particle-field Brownian dynamics simulations. The density is assigned on the particle level using a weighting kernel with finite support. The system's free energy density is derived from an equation of state (EoS) and includes a square gradient term. The numerical stability of the scheme is evaluated in terms of reproducing the thermodynamics (equilibrium density and compressibility) and dynamics (diffusion coefficient) of homogeneous samples. Using a reduced description to simplify our analysis, we find that numerical stability depends strictly on reduced reference compressibility, kernel range, time step in relation to the friction factor, and reduced external pressure, the latter being relevant under isobaric conditions. Appropriate parametrization yields precise thermodynamics, further improved through a simple renormalization protocol. The dynamics can be restored exactly through a trivial manipulation of the time step and friction coefficient. A semiempirical formula for the upper bound on the time step is derived, which takes into account variations in compressibility, friction factor, and kernel range. We test the scheme on realistic mesoscopic models of fluids, involving both simple (Helfand) and more sophisticated (Sanchez-Lacombe) equations of state.

Mesoscale molecular assembly is favored by the active, crowded cytoplasm

The mesoscale organization of molecules into membraneless biomolecular condensates is emerging as a key mechanism of rapid spatiotemporal control in cells. Principles of biomolecular condensation have been revealed through reconstitution. However, intracellular environments are much more complex than test-tube environments: they are viscoelastic, highly crowded at the mesoscale, and are far from thermodynamic equilibrium due to the constant action of energy-consuming processes. We developed synDrops, a synthetic phase separation system, to study how the cellular environment affects condensate formation. Three key features enable physical analysis: synDrops are inducible, bioorthogonal, and have well-defined geometry. This design allows kinetic analysis of synDrop assembly and facilitates computational simulation of the process. We compared experiments and simulations to determine that macromolecular crowding promotes condensate nucleation but inhibits droplet growth through coalescence. ATP-dependent cellular activities help overcome the frustration of growth. In particular, stirring of the cytoplasm by actomyosin dynamics is the dominant mechanism that potentiates droplet growth in the mammalian cytoplasm by reducing confinement and elasticity. Our results demonstrate that mesoscale molecular assembly is favored by the combined effects of crowding and active matter in the cytoplasm. These results move toward a better predictive understanding of condensate formation . Published by the American Physical Society 2024

A hybrid Euclidean–Lorentzian universe

The limited velocity in a geometry of Lorentzian signature seem to prevent the universe to reach thermodynamic equilibrium as suggested by the cosmic microwave background. Thus it was suggested that the universe which was initially minuscule has reached a more considerable radius in a short duration by a process known as cosmic inflation. However, to drive such a process have led to the suggestion of an ad-hoc scalar field the inflaton, which has no purpose in nature other than driving the cosmic inflation field and then stopping it once the universe reached the right size. In a recent paper it was shown that rapid expansion can occur without postulating an inflation by following Hawking’s suggestion and assuming that primordially the metric of the universe had an Euclidean signature, in which case velocity is not limited and thermalization and rapid expansion are derived without the need to assume an ad-hoc field. However, while in the previous work emphasis was put on the dynamics and physical statistics of the particles in a Euclidean space versus Lorentzian space in which both spaces were given. No mathematical model was given regarding the development of current Lorentzian space-time from the early Euclidean space-time, and how fundamental problems such as the space-time singularity and the homogeneity of the CMB can be solved in the hybrid Euclidean–Lorentzian picture. This lacuna is to be rectified in this paper.

Analysis of electromagnetic and radiative heat source on tangential hyperbolic fluid under Arrhenius kinetic with convective cooling

The global threat of environmental degradation from harmful waste discharge is evident, leading to unusual diseases and natural disasters. Some of these toxic emissions result from human activities, such as the incomplete combustion of hydrocarbons. As such, this study aims to explore the analysis of electromagnetic and radiative heat sources on tangential hyperbolic fluid under Arrhenius kinetic with convective cooling. The transformed momentum and heat equations are solved using a rigorous computational approach called the Galerkin integration approximation with weighted residual method. This computational methodology ensures the reliability and accuracy of the results. Various graphs illustrate the results, showing parametric sensitivity profiles for the velocity, temperature, skin friction, thermal gradient, Bejan, and entropy generation. As noticed from the outcomes, electric field loading increases heat dispersion by about 3.25 % as heat source terms are enhanced. Increasing magnetic field, radiation, and electric field loading parameters strengthened thermodynamic equilibrium and minimized entropy generation. The tangential hyperbolic combustion process is 6.11 % increased with rising Brinkman number and electric field loading terms. The flow rate and temperature field are increased to the peak along the middle of the channel for increasing pressure gradient.

Experimental and numerical investigations of cake baking in mold

This article deals with the in-mold cake baking process. The methodology relies on numerical and experimental investigations to validate a multiphysics developed model. This numerical model is next exploited to enhance the comprehension of the physical processes that occur during a typical cake baking phase. Based on the governing equations for heat and mass transport and under few assumptions (deformable porous medium, local thermodynamic equilibrium, ideal gas mixture …), the problem consists in solving a system of five coupled partial derivative equations. Temperature, moisture content, total gas pressure, porosity and displacement are used as state variables in this study. The swelling of the dough caused by the increase in total gas pressure is predicted by a viscoelastic model. This thermo-hydro-mechanical model is implemented in a finite element code. Moreover, an experimental laboratory set-up was developed to continually acquire temperatures, water losses and gas pressure inside the product. The browning kinetic is also studied. Furthermore, the cake deformation is tracked by camera. The numerical model is validated based on the conducted experiments. Different operating conditions are tested to verify the robustness of the model. Finally, a sensitivity analysis is performed to understand the impact of estimated parameters on the outputs of the developed model.

Development Models of Stoichiometric Thermodynamic Equilibrium for Predicting Gas Composition from Biomass Gasification: Correction Factors for Reaction Equilibrium Constants

Development Models of Stoichiometric Thermodynamic Equilibrium for Predicting Gas Composition from Biomass Gasification: Correction Factors for Reaction Equilibrium Constants

New rotational rate coefficients computation of the linear NaC3N(X1Σ+) by collision with He(1S) and astrophysical implication

ABSTRACT For a better understanding of the physico-chemistry in the interstellar medium, collisional data are needed. In this work, we provide rate coefficients for the recently detected by Cabezas and collaborators in 2023 sodium cyanoacetylide molecule NaC$_{3}$N($X^{1}\Sigma ^{+}$) induced by collisions with He. A new two-dimensional potential energy surface (2D-PES) is derived by adopting the high-level theory of the explicitly correlated coupled cluster with single, double, and perturbative triple excitations (CCSD(T)-F12) in conjunction with the aug-cc-pVTZ basis sets. Our 2D-PES presents two minima: the global one with a well depth of $-86.58$ cm$^{-1}$ and the second well with a $-47.01$ cm$^{-1}$ depth. This was expected by the Natural Bond Orbital analysis showing two electrophilic zones located on Na and N linked Carbon with respective atomic charges : $+0.96575$ and $+0.28910$. This PES was used to calculate inelastic cross-sections within the framework of the close-coupling theory for total energies $\le 170$ cm$^{-1}$ and $J\le 22$. Using the Maxwell–Boltzmann distribution of kinetic energies, these cross-sections were integrated to generate the collisional (de)-excitation rate coefficients for temperatures below 30 K. In order to estimate the impact of the computed collisional rates, a non-local thermodynamical equilibrium radiative transfer calculation was performed. The new collisional data can allow accurate NaC$_{3}$N abundance determination in the interstellar medium.

Investigation of the rotational spectrum of CH$_3$17OH and its tentative detection toward Sagittarius B2(N)

Methanol is an abundant and widespread molecule in the interstellar medium. The column density of its 18O isotopolog, CH$_3$18OH, is in some star-forming regions so high that the search for CH$_3$17OH is promising. But only very few transition frequencies of CH$_3$17OH with a microwave accuracy have been published prior to our investigation. We want to extend the very limited rotational line list of CH$_3$17OH to be able to search for this isotopolog in the interstellar medium. We recorded the rotational spectrum of CH$_3$17OH between 38 and 1095 GHz employing a methanol sample enriched in 17O to 20<!PCT!>. A torsion-rotation Hamiltonian model based on the rho-axis method was employed to fit the data, as in our previous studies. We searched for rotational transitions of CH$_3$17OH in the imaging spectral line survey ReMoCA obtained with the Atacama Large Millimeter/submillimeter Array (ALMA) toward the high-mass star-forming region Sgr B2(N). The observed spectra were modeled under the assumption of local thermodynamic equilibrium (LTE). The assignments cover $0 J 45$, $K_a 16$, and mainly the $ t = 0$ and 1 torsional states. The Hamiltonian model describes our data well. The model was applied to derive a line list for radio-astronomical observations. We report a tentative detection of CH$_3$17OH along with secure detections of the more abundant isotopologs of methanol toward Sgr B2(N2b). The derived column densities yield isotopic ratios 12C/13C = 25, 16O/18O = 240, and 18O/17O = 3.3, which are consistent with values found earlier for other molecules in Sgr B2. The agreement between the 18O/17O isotopic ratio that we obtained for methanol and the 18O/17O ratios reported in the past for other molecules in Sgr B2(N) strongly supports our tentative interstellar identification of CH$_3$17OH. The accuracy of the derived line list is sufficient for further radio astronomical searches for this methanol isotopolog toward other star-forming regions.

Synthesis, Photophysical and Electronic Properties of a D-π-A Julolidine-Like Pyrenyl-o-Carborane.

We synthesized 2-(1-1,2-dicarbadodecaboranyl(12))-6,6,12,12-tetramethyl-7,8,11,12-tetrahydro-6H,10H-phenaleno[1,9-fg]pyrido[3,2,1-ij]quinoline (4), a julolidine-like pyrenyl-o-carborane, with pyrene substituted at the 2,7-positions on the HOMO/LUMO nodal plane. Using solid state molecular structures, photophysical data, cyclic voltammetry, DFT and LR-TDDFT calculations, we compare o-carborane and B(Mes)2 (Mes=2,4,6-Me3C6H2) as acceptor groups. Whereas the π-acceptor strength of B(Mes)2 is sufficient to drop the pyrene LUMO+1 below the LUMO, the carborane does not do this. We confirm the π-donor strength of the julolidine-like moiety, however, which raises the pyrene HOMO-1 above the HOMO. In contrast to the analogous pyrene-2-yl-o-carborane, 2-(1-1,2-dicarbadodecaboranyl(12))-pyrene VI, which exhibits dual fluorescence, because the rate of internal conversion between locally-excited (LE) and charge transfer (CT) (from the pyrene to the carborane) states is faster than the radiative decay rate, leading to a thermodynamic equilibrium between the 2 states, 4 shows only single fluorescence, as the CT state involving the carborane as the acceptor moiety in not kinetically accessible, so a more localized CT emission involving the julolidine-like pyrene moiety is observed.

Stellar Characterization and a Chromospheric Activity Analysis of a K2 Sample of Planet-hosting Stars

Effective temperatures, surface gravities, and iron abundances were derived for 109 stars observed by the K2 mission using equivalent width measurements of Fe i and Fe ii lines. Calculations were carried out in local thermodynamic equilibrium using Kurucz model atmospheres. Stellar masses and radii were derived by combining the stellar parameters with Gaia Data Release 3 parallaxes, V magnitudes, and isochrones. The derived stellar and planetary radii have a median internal precision of 1.8% and 2.3%, respectively. The radius gap near R planet ∼ 1.9 R ⊕ was detected in this K2 sample. Chromospheric activity was measured from the Ca ii H and K lines using the values of logRHK′ , which were investigated as a function of stellar rotational period (P rot), and we found that chromospheric activity decreases with increasing P rot, although there is a large scatter in logRHK′ (∼0.5) for a given P rot. The activity levels in this sample reveal a paucity of F and G dwarfs with intermediate activity levels (the Vaughan–Preston gap). The effect that stellar activity might have on the derivation of stellar parameters was investigated by including magnetically sensitive Fe i lines in the analysis and we find no significant differences between parameters with and without magnetically sensitive lines, although the more active stars ( logRHK′>−5.0 ) exhibit a larger scatter in the differences in T eff and [Fe/H].

Chemical inventory of the envelope of the Class I protostar L1551 IRS 5

Episodic accretion in protostars leads to luminosity outbursts that end up heating their surroundings. This rise in temperature pushes the snow lines back, enabling the desorption of chemical species from dust grain surfaces, which may significantly alter the chemical history of the accreting envelope. However, a limited number of extensive chemical surveys of eruptive young stars have been performed thus far. In the present study, we carry out a large spectral survey of the binary Class I protostar L1551 IRS 5, known to be a FUor-like object, in the 3 mm and 2mm bands with the IRAM-30m telescope. As a result, we detected more than 400 molecular lines. The source displays a great chemical richness with the detection of 75 species, including isotopologues. Among these species, there are 13 hydrocarbons, 25 N-bearing species, 30 O-bearing species, 15 S-bearing species, 12 deuterated molecules, and a total of 10 complex organic molecules (l-C4H2, CH3CCH, CH2DCCH, CH3CHO, CH3CN, CH3OCH3, CH3OCHO, CH3OH, CH2DOH, and HC5N). With the help of local thermodynamic equilibrium (LTE) and non-LTE models, we determined the column densities of most molecules as well as excitation and kinetic temperatures. While most of those molecules trace the cold envelope (≲20 K), the OCS and CH3OH emission arise from the warm (>100 K) innermost (<2″) regions. We compared the chemical inventory of L1551 IRS 5 and its column density ratios, including isotopic ratios, with other protostellar sources. A broad chemical diversity is seen among Class I objects. More observations with both single-dish telescopes and interferometers are needed to characterize the diversity in a larger sample of protostars, while more astrochemical models would help explain this diversity, in addition to the impact of luminosity outbursts on the chemistry of protostellar envelopes.

Lithium recovery from Mexican geothermal brine via microwave-synthesized ion sieves

This paper investigates for the first time the feasibility of lithium recovery using lithium ion-sieves from a Mexican geothermal brine from a well of Cerro Prieto power plant. The materials were prepared following the microwave-assisted hydrothermal route to favor their sustainability. Also, the effect of the three manganese-based compounds as precursors was evaluated in which the vacancies were generated by acid treatment, by varying the acid concentration and the contact time. The structural characterizations showed that manganese sulfate was an efficient precursor for synthesizing LiMn2O4 spinel. The results of the uptake experiments, varying the pH of the Li solution showed that the highest sorption capacity is obtained at pH 12. The adsorption kinetics was better described by a pseudo second order equation (R2=0.9392). According to the Weber-Morris model, the process seems to be governed by film diffusion rather by intraparticle diffusion. The maximum adsorption capacity that was achieved was 9.64 mg/g and the thermodynamic equilibrium was best described by the Freundlich isotherm (R2=0.9769). Finally, the material was able to retain a competitive uptake capacity after five adsorption-desorption cycles.