Temperature-dependent solubility of Rebaudioside A in methanol/ethanol and ethyl acetate mixtures:Experimental measurements and thermodynamic modeling

The equilibrium solubility of Rebaudioside A(Reb A)FormⅡin binary mixtures of methanol/ethanol and ethyl acetate was quantitatively determined within the temperature range of 283.15—328.15 K at ambient pressure.The experimental findings indicate a positive correlation between the solubility of Reb A(FormⅡ)and both the temperature and the methanol/ethanol content in the solvent system.To describe the solubility data,six distinct models were employed:the modified Apelblat equation,theλh model,the combined nearly ideal binary solvent/Redlich—Kister(CNIBS/R—K)model,the van't HoffJouyban-Acree(VJA)model,the Apelblat-Jouyban-Acree(AJA)model,and the non-random two-liquid(NRTL)model.The combined nearly ideal binary solvent/Redlich—Kister model exhibited the most precise fit for solubility in methanol+ethyl acetate mixtures,reflected by an average relative deviation(ARD)of 0.0011 and a root mean square deviation(RMSD)of 12×10^(-7).Conversely,for ethanol+ethyl acetate mixtures,the modified Apelblat equation provided a superior correlation(ARD=0.0014,RMSD=4×10^(-7)).Furthermore,thermodynamic parameters associated with the dissolution of Reb A(FormⅡ),including enthalpy,entropy,and the Gibbs energy change,were inferred from the data.The findings underscore that the dissolution process is predominantly endothermic across the solvent systems examined.Notably,the entropy changes appear to have a significant influence on the Gibbs free energy associated with the dissolution of Reb A(FormⅡ),suggesting that entropic factors may play a pivotal role in the studied systems.

FLOCKING OF A THERMODYNAMIC CUCKER-SMALE MODEL WITH LOCAL VELOCITY INTERACTIONS

In this paper, we study the flocking behavior of a thermodynamic Cucker–Smale model with local velocity interactions. Using the spectral gap of a connected stochastic matrix, together with an elaborate estimate on perturbations of a linearized system, we provide a sufficient framework in terms of initial data and model parameters to guarantee flocking. Moreover, it is shown that the system achieves a consensus at an exponential rate.

Recent advances in studies on changes in Arctic sea ice microstructure and implications to thermodynamic modeling

The study of Arctic sea ice has traditionally been focused on large-scale such as reductions of ice coverage,thickness,volumes and sea ice regime shift.Research has primarily concentrated on the impact of large-scale external factors such as atmospheric and oceanic circulations,and solar radiation.Additionally,Arctic sea ice also undergoes rapid micro-scale evolution such as gas bubbles formation,brine pockets migration and massive formation of surface scattering layer.Field studies like CHINARE(2008-2018)and MOSAiC(2019-2020)have confirmed these observations,yet the full understanding of those changes remain insufficient and superficial.In order to cope better with the rapidly changing Arctic Ocean,this study reviews the recent advances in the microstructure of Arctic sea ice in both field observations and laboratory experiments,and looks forward to the future objectives on the microscale processes of sea ice.The significant porosity and the cyclical annual and seasonal shifts likely modify the ice's thermal,optical,and mechanical characteristics,impacting its energy dynamics and mass balance.Current thermodynamic models,both single-phase and dual-phase,fail to accurately capture these microstructural changes in sea ice,leading to uncertainties in the results.The discrepancy between model predictions and actual observations strongly motivates the parameterization on the evolution in ice microstructure and development of next-generation sea ice models,accounting for changes in ice crystals,brine pockets,and gas bubbles under the background of global warming.It helps to finally achieve a thorough comprehension of Arctic sea ice changes,encompassing both macro and micro perspectives,as well as externaland internal factors.

Crystallization thermodynamics of 2,4(5)-dinitroimidazole in binary solvents

2,4(5)-Dinitroimidazole(2,4(5)-DNI)is an important organic intermediate,and itself can also be used for energetic material.In this work,the solubility of 2,4(5)-DNI in(methanol+water,acetonitrile+water,acetone+water)binary solvents were measured by using a dynamic test method from 278.15 K to 323.15 K under 101.1 k Pa.The Jouyban–Acree model,van't Hoff–Jouyban–Acree model,Apelblat–Jouyb an–Acree model,Ma model,and Sun model were used to correlate the experimental data.The values of relative average deviation(RAD)and root-mean-square deviation(RMSD)were very small,indicating that the error between the experimental value and the correlated value was very small.The thermodynamic parameters such as dissolution enthalpy,dissolution entropy and Gibbs energy were calculated based on solubility data.High-purity of 2,4(5)-DNI was efficiently obtained by using cooling and dilution crystallization method.

Pseudo-rapidity distributions of charged particles in asymmetric collisions using Tsallis thermodynamics

The pseudo-rapidity distributions of the charged particles produced in the asymmetric collision systems p+Al,p+Au and ^(3)He+Au at√S_(NN)=200 GeV GeV are evaluated in the framework of a fireball model with Tsallis thermodynamics.The fireball model assumes that the experimentally measured particles are produced by fireballs following the Tsallis distribution and it can effectively describe the experimental data.Our results as well as previous results for d+Au collisions at√S_(NN)=200 GeV GeV and p+Pb collisions at√S_(NN)=5.02 TeV TeV validate that the fireball model based on Tsallis thermodynamics can provide a universal framework for pseudo-rapidity distribution of the charged particles produced in asymmetric collision systems.We predict the centrality dependence of the total charged particle multiplicity in the p+Al,p+Au and 3He+Au collisions.Additionally,the dependences of the fireball model parameters(y_(0a),y_(0A),σ_(a) and σ_(A))on the centrality and system size are studied.

Thermodynamic limit of the XXZ central spin model with an arbitrary central magnetic field

The U(1)symmetry of the X X Z central spin model with an arbitrary central magnetic field B is broken,since its total spin in the z-direction is not conserved.We obtain the exact solutions of the system by using the off-diagonal Bethe ansatz method.The thermodynamic limit is investigated based on the solutions.We find that the contribution of the inhomogeneous term in the associated T-Q relation to the ground state energy satisfies an N^(-1)scaling law,where N is the total number of spins.This result makes it possible to investigate the properties of the system in the thermodynamic limit.By assuming the structural form of the Bethe roots in the thermodynamic limit,we obtain the contribution of the direction of B to the ground state energy.It is shown that the contribution of the direction of the central magnetic field is a finite value in the thermodynamic limit.This is the phenomenon caused by the U(1)symmetry breaking of the system.

Interface kinetics modeling of binary alloy solidification by considering correlation between thermodynamics and kinetics

By considering collision-limited growth mode and short-range diffusion-limited growth mode simultaneously,an extended kinetic model for solid−liquid interface with varied kinetic prefactor was developed for binary alloys.Four potential correlations arising from effective kinetics coupling the two growth modes were proposed and studied by application to planar interface migration and dendritic solidification,where the linear correlation between the effective thermodynamic driving force and the effective kinetic energy barrier seems physically realistic.A better agreement between the results of free dendritic growth model and the available experiment data for Ni−0.7at.%B alloy was obtained based on correlation between the thermodynamics and kinetics.As compared to previous models assuming constant kinetic prefactor,a common phenomenon occurring at relatively low undercoolings,i.e.the interface migration slowdown,can be ascribed to both the thermodynamic and the kinetic factors.By considering universality of the correlation between the thermodynamics and kinetics,it is concluded that the correlation should be considered to model the interface kinetics in alloy solidification.

Investigations of methane adsorption characteristics on marine-continental transitional shales and gas storage capacity models considering pore evolution

Methane adsorption is a critical assessment of the gas storage capacity(GSC)of shales with geological conditions.Although the related research of marine shales has been well-illustrated,the methane adsorption of marine-continental transitional(MCT)shales is still ambiguous.In this study,a method of combining experimental data with analytical models was used to investigate the methane adsorption characteristics and GSC of MCT shales collected from the Qinshui Basin,China.The Ono-Kondo model was used to fit the adsorption data to obtain the adsorption parameters.Subsequently,the geological model of GSC based on pore evolution was constructed using a representative shale sample with a total organic carbon(TOC)content of 1.71%,and the effects of reservoir pressure coefficient and water saturation on GSC were explored.In experimental results,compared to the composition of the MCT shale,the pore structure dominates the methane adsorption,and meanwhile,the maturity mainly governs the pore structure.Besides,maturity in the middle-eastern region of the Qinshui Basin shows a strong positive correlation with burial depth.The two parameters,micropore pore volume and non-micropore surface area,induce a good fit for the adsorption capacity data of the shale.In simulation results,the depth,pressure coefficient,and water saturation of the shale all affect the GSC.It demonstrates a promising shale gas potential of the MCT shale in a deeper block,especially with low water saturation.Specifically,the economic feasibility of shale gas could be a major consideration for the shale with a depth of<800 m and/or water saturation>60%in the Yushe-Wuxiang area.This study provides a valuable reference for the reservoir evaluation and favorable block search of MCT shale gas.

Machine learning prediction of methane,ethane,and propane solubility in pure water and electrolyte solutions:Implications for stray gas migration modeling

Hydraulic fracturing is an effective technology for hydrocarbon extraction from unconventional shale and tight gas reservoirs.A potential risk of hydraulic fracturing is the upward migration of stray gas from the deep subsurface to shallow aquifers.The stray gas can dissolve in groundwater leading to chemical and biological reactions,which could negatively affect groundwater quality and contribute to atmospheric emissions.The knowledge oflight hydrocarbon solubility in the aqueous environment is essential for the numerical modelling offlow and transport in the subsurface.Herein,we compiled a database containing 2129experimental data of methane,ethane,and propane solubility in pure water and various electrolyte solutions over wide ranges of operating temperature and pressure.Two machine learning algorithms,namely regression tree(RT)and boosted regression tree(BRT)tuned with a Bayesian optimization algorithm(BO)were employed to determine the solubility of gases.The predictions were compared with the experimental data as well as four well-established thermodynamic models.Our analysis shows that the BRT-BO is sufficiently accurate,and the predicted values agree well with those obtained from the thermodynamic models.The coefficient of determination(R2)between experimental and predicted values is 0.99 and the mean squared error(MSE)is 9.97×10^(-8).The leverage statistical approach further confirmed the validity of the model developed.

Radiative heat transfer analysis of a concave porous fin under the local thermal non-equilibrium condition:application of the clique polynomial method and physics-informed neural networks

The heat transfer through a concave permeable fin is analyzed by the local thermal non-equilibrium(LTNE)model.The governing dimensional temperature equations for the solid and fluid phases of the porous extended surface are modeled,and then are nondimensionalized by suitable dimensionless terms.Further,the obtained nondimensional equations are solved by the clique polynomial method(CPM).The effects of several dimensionless parameters on the fin's thermal profiles are shown by graphical illustrations.Additionally,the current study implements deep neural structures to solve physics-governed coupled equations,and the best-suited hyperparameters are attained by comparison with various network combinations.The results of the CPM and physicsinformed neural network(PINN)exhibit good agreement,signifying that both methods effectively solve the thermal modeling problem.

Parameterization, sensitivity, and uncertainty of 1-D thermodynamic thin-ice thickness retrieval

Retrieval of Thin-Ice Thickness(TIT)using thermodynamic modeling is sensitive to the parameterization of the independent variables(coded in the model)and the uncertainty of the measured input variables.This article examines the deviation of the classical model’s TIT output when using different parameterization schemes and the sensitivity of the output to the ice thickness.Moreover,it estimates the uncertainty of the output in response to the uncertainties of the input variables.The parameterized independent variables include atmospheric longwave emissivity,air density,specific heat of air,latent heat of ice,conductivity of ice,snow depth,and snow conductivity.Measured input parameters include air temperature,ice surface temperature,and wind speed.Among the independent variables,the results show that the highest deviation is caused by adjusting the parameterization of snow conductivity and depth,followed ice conductivity.The sensitivity of the output TIT to ice thickness is highest when using parameterization of ice conductivity,atmospheric emissivity,and snow conductivity and depth.The retrieved TIT obtained using each parameterization scheme is validated using in situ measurements and satellite-retrieved data.From in situ measurements,the uncertainties of the measured air temperature and surface temperature are found to be high.The resulting uncertainties of TIT are evaluated using perturbations of the input data selected based on the probability distribution of the measurement error.The results show that the overall uncertainty of TIT to air temperature,surface temperature,and wind speed uncertainty is around 0.09 m,0.049 m,and−0.005 m,respectively.

CONTINUOUS THERMODYNAMICS FOR POLYMER SOLUTIONS I.CLOSE-PACKED LATTICE MODEL

using close-packed lattice models,a continuous thermodynamic framework is presented forphase-equilibrium calculations for binary solutions with a polydisperse polymer solute.An expressionfor the Helmholtz function of mixing is based on the revised Freed model developed previously.Asize parameter c_r and an energy parameter ε are used;the former can be temperature dependent,while the latter can depend on both temperature and chain-length of the polymer.The discretemulticomponent approach is adopted to derive expressions for chemical potentials,spinodals and criti-cal points.The continuous distribution function is then used in calculations of moments occurring inthose expressions.Computation programs are established for cloud-point-curve,shadow-curve,spinodal and critical-point calculations for polymer solutions with standard distribution or arbitrarydistribution of polymer.In the latter case,the derivative method developed previously is applied.lllustrations for phase-equilibrium calculations are

Variable-mass Thermodynamics Calculation Model for Gas-operated Automatic Weapon

Aiming at the fact that the energy and mass exchange phenomena exist between barrel and gas-operated device of the automatic weapon, for describing its interior ballistics and dynamic characteristics of the gas-operated device accurately, a new variable-mass thermodynamics model is built. It is used to calculate the automatic mechanism velocity of a certain automatic weapon, the calculation results coincide with the experimental results better, and thus the model is validated. The influences of structure parameters on gas-operated device's dynamic characteristics are discussed. It shows that the model is valuable for design and accurate performance prediction of gas-operated automatic weapon.

The Cloud Model for Climate Change

In 1995, the Intergovernmental Panel on Climate Change (IPCC) released a thermodynamic model based on the Greenhouse Effect, aiming to forecast global temperatures. This study delves into the intricacies of that model. Some interesting observations are revealed. The IPCC model equated average temperatures with average energy fluxes, which can cause significant errors. The model assumed that all energy fluxes remained constant, and the Earth emitted infrared radiation as if it were a blackbody. Neither of those conditions exists. The IPCC’s definition of Climate Change only includes events caused by human actions, excluding most causes. Satellite data aimed at the tops of clouds may have inferred a high Greenhouse Gas absorption flux. The model showed more energy coming from the atmosphere than absorbed from the sun, which may have caused a violation of the First and Second Laws of Thermodynamics. There were unexpectedly large gaps in the satellite data that aligned with various absorption bands of Greenhouse Gases, possibly caused by photon scattering associated with re-emissions. Based on science, we developed a cloud-based climate model that complied with the Radiation Laws and the First and Second Laws of Thermodynamics. The Cloud Model showed that 81.3% of the outgoing reflected and infrared radiation was applicable to the clouds and water vapor. In comparison, the involvement of CO2 was only 0.04%, making it too minuscule to measure reliably.

CONTINUOUS THERMODYNAMICS FOR POLYMER SOLUTIONS II . LATTICE FLUID MODEL

Using lattice-fluid model, a continuous thermodynamic framework is presented for phase-equilibrium calculations for binary solutions with a polydisperse polymer solute. A two-step process is designed to form a real polymer solution containing a solvent and a polydisperse polymer solute occupying a volume at fixed temperature and pressure. In the first step, close-packed pure components including solvent and polymers with different molar masses or different chain lengths are mixed to form a closed-packed polymer solution. In the second step, the close-packed mixture, considered to be a pseudo-pure substance is mixed with holes to form a real polymer solution with a volume dependent on temperature and pressure. Revised Freed's model developed previously is adopted for both steps. Besides pure-component parameters, a binary size parameter cr and a binary energy parameter e12 are used. They are all temperature dependent. The discrete-multicomponent approach is adopted to derive expressions for chemical potentials, spinodals and critical points. The continuous distribution function is then used in calculations of moments occurring in those expressions. Computation procedures are established for cloud-point-curve, shadow-curve, spinodal and critical-point calculations using standard distribution or arbitrary distribution on molar mass or on chain length. Illustrative examples are also presented.

A Maxwell Demon Model Connecting Information and Thermodynamics

In the past decades several theoretical Maxwell＇s demon models have been proposed to exhibit effects such as refrigerating, doing work at the cost of information, and some experiments have been carried out to realize these effects. We propose a model with a two-level demon, information represented by a sequence of bits, and two heat reservoirs. The reservoir that the demon is interacting with depends on the bit. When the temperature difference between the two heat reservoirs is large enough, the information can be erased. On the other hand, when the information is pure enough, heat transfer from one reservoir to the other can happen, resulting in the effect of refrigeration. Genuine examples of such a system are discussed.

Phonon Dispersion and Thermodynamics Properties of CaF_2 via Shell Model Molecular Dynamics Simulations

The phonon and thermodynamics properties of face-centered cubic CaF2 at high pressure and high temperature are investigated by using the shell model interatomic pair potential within General Utility Lattice Program （GULP）. The phonon dispersion curves and the corresponding density of state （PDOS） in this work are consistent with the experimental data and other theoretical results. The transverse optical （TO） and longitudinal optical （LO） mode splitting as well as heat capacity at constant volume Cv and entropy S versus pressure and temperature are also obtained.

Thermodynamics of 1D N-Component Bariev Model Under Open Boundary Conditions

The thermodynamic Bethe ansatz equations and free energy for 1D N-component Bariev model under open boundary conditions are derived based on the string hypothesis for both, a repulsive and an attractive interaction. These equations are discussed in some limiting cases, such as the ground state, weak and strong couplings.

Coherent Application of a Contact Structure to Formulate Classical Non-Equilibrium Thermodynamics

This contribution presents an outline of a new mathematical formulation for Classical Non-Equilibrium Thermodynamics (CNET) based on a contact structure in differential geometry. First a non-equilibrium state space is introduced as the third key element besides the first and second law of thermodynamics. This state space provides the mathematical structure to generalize the Gibbs fundamental relation to non-equilibrium thermodynamics. A unique formulation for the second law of thermodynamics is postulated and it showed how the complying concept for non-equilibrium entropy is retrieved. The foundation of this formulation is a physical quantity, which is in non-equilibrium thermodynamics nowhere equal to zero. This is another perspective compared to the inequality, which is used in most other formulations in the literature. Based on this mathematical framework, it is proven that the thermodynamic potential is defined by the Gibbs free energy. The set of conjugated coordinates in the mathematical structure for the Gibbs fundamental relation will be identified for single component, closed systems. Only in the final section of this contribution will the equilibrium constraint be introduced and applied to obtain some familiar formulations for classical (equilibrium) thermodynamics.

A New Class of Simple,General and Efficient Finite Volume Schemes for Overdetermined Thermodynamically Compatible Hyperbolic Systems

In this paper,a new efficient,and at the same time,very simple and general class of thermodynamically compatiblefinite volume schemes is introduced for the discretization of nonlinear,overdetermined,and thermodynamically compatiblefirst-order hyperbolic systems.By construction,the proposed semi-discrete method satisfies an entropy inequality and is nonlinearly stable in the energy norm.A very peculiar feature of our approach is that entropy is discretized directly,while total energy conservation is achieved as a mere consequence of the thermodynamically compatible discretization.The new schemes can be applied to a very general class of nonlinear systems of hyperbolic PDEs,including both,conservative and non-conservative products,as well as potentially stiff algebraic relaxation source terms,provided that the underlying system is overdetermined and therefore satisfies an additional extra conservation law,such as the conservation of total energy density.The proposed family offinite volume schemes is based on the seminal work of Abgrall[1],where for thefirst time a completely general methodology for the design of thermodynamically compatible numerical methods for overdetermined hyperbolic PDE was presented.We apply our new approach to three particular thermodynamically compatible systems:the equations of ideal magnetohydrodynamics(MHD)with thermodynamically compatible generalized Lagrangian multiplier(GLM)divergence cleaning,the unifiedfirst-order hyperbolic model of continuum mechanics proposed by Godunov,Peshkov,and Romenski(GPR model)and thefirst-order hyperbolic model for turbulent shallow waterflows of Gavrilyuk et al.In addition to formal mathematical proofs of the properties of our newfinite volume schemes,we also present a large set of numerical results in order to show their potential,efficiency,and practical applicability.