Dialectical Thermodynamics’Solution to the Conceptual Imbroglio That Is the Reversible Path

According to the second law of thermodynamics, as currently understood, any given transit of a system along the reversible path proceeds with a total entropy change equal to zero. The fact that this condition is also the identifier of thermodynamic equilibrium, makes each and every point along the reversible path a state of equilibrium, and the reversible path, as expressed by a noted thermodynamic author, “a dense succession of equilibrium states”. The difficulties with these notions are plural. The fact, for example, that systems need to be forced out of equilibrium via the expenditure of work, would make any spontaneous reversible process a consumer of work, this in opposition to common thermodynamic wisdom that makes spontaneous reversible processes the most efficient transformers of work-producing-potential into actual work. The solution to this and other related impasses is provided by Dialectical Thermodynamics via its previously proved notion assigning a negative entropy change to the energy upgrading process represented by the transformation of heat into work. The said solution is here exemplified with the ideal-gas phase isomerization of butane into isobutane.

View of thermodynamic phase transition of the charged Gauss-Bonnet AdS black hole via the shadow

We examine thermodynamic phase transition(PT)of the charged Gauss-Bonnet Ad S black hole(BH)by utilizing the shadow radius.In this system,we rescale the corresponding Gauss-Bonnet coefficientαby a factor of 1/(D-4),and ensure thatαis positive to avoid any singularity problems.The equation derived for the shadow radius indicates that it increases as the event horizon radius increases,making it an independent variable for determining BH temperature.By investigating the PT curve in relation to shadows,we can observe that the shadow radius can be used as an alternative to the event horizon radius in explaining the phenomenon of BH PT.Furthermore,the results indicate that an increase in the parameterαcorresponds to a decrease in the temperature of the BH.By utilizing the relationship between the temperature and the shadow radius,it is possible to obtain the thermal profile of the Gauss-Bonnet AdS BH.It is evident that there is an N-type variation in temperature for pressures P<P_(c).Additionally,as the parameterαincreases,the region covered by shadow expands while the temperature decreases.The utilization of BH shadows as a probe holds immense significance in gaining a deeper understanding of BH thermodynamic behavior.

TP-PROFILE: Monitoring the Thermodynamic Structure of the Troposphere over the Third Pole

Ground-based microwave radiometers(MWRs)operating in the K-and V-bands(20–60 GHz)can help us obtain temperature and humidity profiles in the troposphere.Aside from some soundings from local meteorological observatories,the tropospheric atmosphere over the Tibetan Plateau(TP)has never been continuously observed.As part of the Chinese Second Tibetan Plateau Scientific Expedition and Research Program(STEP),the Tibetan Plateau Atmospheric Profile(TPPROFILE)project aims to construct a comprehensive MWR troposphere observation network to study the synoptic processes and environmental changes on the TP.This initiative has collected three years of data from the MWR network.This paper introduces the data information,the data quality,and data downloading.Some applications of the data obtained from these MWRs were also demonstrated.Our comparisons of MWR against the nearest radiosonde observation demonstrate that the TP-PROFILE MWR system is adequate for monitoring the thermal and moisture variability of the troposphere over the TP.The continuous temperature and moisture profiles derived from the MWR data provide a unique perspective on the evolution of the thermodynamic structure associated with the heating of the TP.The TP-PROFILE project reveals that the low-temporal resolution instruments are prone to large uncertainties in their vapor estimation in the mountain valleys on the TP.

Thermodynamic model for deoxidation of liquid steel considering strong metal-oxygen interaction in the quasichemical model framework

Herein,a thermodynamic model aimed at describing deoxidation equilibria in liquid steel was developed.The model provides explicit forms of the activity coefficient of solutes in liquid steel,eliminating the need for the minimization of internal Gibbs energy preliminarily when solving deoxidation equilibria.The elimination of internal Gibbs energy minimization is particularly advantageous during the coupling of deoxidation equilibrium calculations with computationally intensive approaches,such as computational fluid dynamics.The model enables efficient calculations through direct embedment of the explicit forms of activity coefficient in the computing code.The proposed thermodynamic model was developed using a quasichemical approach with two key approximations:random mixing of metallic elements(Fe and oxidizing metal) and strong nonrandom pairing of metal and oxygen as nearest neighbors.Through these approximations,the quasichemical approach yielded the activity coefficients of solutes as explicit functions of composition and temperature without requiring the minimization of internal Gibbs energy or the coupling of separate programs.The model was successfully applied in the calculation of deoxidation equilibria of various elements(Al,B,C,Ca,Ce,Cr,La,Mg,Mn,Nb,Si,Ti,V,and Zr).The limitations of the model arising from these assumptions were also discussed.

Composition optimization and performance prediction for ultra-stable water-based aerosol based on thermodynamic entropy theory

Water-based aerosol is widely used as an effective strategy in electro-optical countermeasure on the battlefield used to the preponderance of high efficiency,low cost and eco-friendly.Unfortunately,the stability of the water-based aerosol is always unsatisfactory due to the rapid evaporation and sedimentation of the aerosol droplets.Great efforts have been devoted to improve the stability of water-based aerosol by using additives with different composition and proportion.However,the lack of the criterion and principle for screening the effective additives results in excessive experimental time consumption and cost.And the stabilization time of the aerosol is still only 30 min,which could not meet the requirements of the perdurable interference.Herein,to improve the stability of water-based aerosol and optimize the complex formulation efficiently,a theoretical calculation method based on thermodynamic entropy theory is proposed.All the factors that influence the shielding effect,including polyol,stabilizer,propellant,water and cosolvent,are considered within calculation.An ultra-stable water-based aerosol with long duration over 120 min is obtained with the optimal fogging agent composition,providing enough time for fighting the electro-optic weapon.Theoretical design guideline for choosing the additives with high phase transition temperature and low phase transition enthalpy is also proposed,which greatly improves the total entropy change and reduce the absolute entropy change of the aerosol cooling process,and gives rise to an enhanced stability of the water-based aerosol.The theoretical calculation methodology contributes to an abstemious time and space for sieving the water-based aerosol with desirable performance and stability,and provides the powerful guarantee to the homeland security.

Improving hydrogen storage thermodynamics and kinetics of Ce-Mg-Ni-based alloy by mechanical milling with TiF_(3)

Mg-based hydrides are too stable and the kinetics of hydrogen absorption and desorption is not satisfactory.An efficient way to improve these shortcomings is to employ reactive ball milling to synthesize the nanocomposite materials of Mg and additives.In this experiment,TiF_(3)was selected as an additive,and the mechanical milling method was employed to prepare the experimental alloys.The alloys used in this experiment were the as-cast Ce_(5)Mg_(85)Ni_(10),as-milled Ce_(5)Mg_(85)Ni_(10)and Ce_(5)Mg_(85)Ni_(10)+3 wt.%TiF3.The phase transformation,structural evolution,isothermal and non-isothermal hydrogenation and dehydrogenation performances of the alloys were inspected by XRD,SEM,TEM,Sievert apparatus,DSC and TGA.It revealed that nanocrystalline appeared in the as-milled samples.Compared with the as-cast alloy,ball milling made the particle dimension and grain size decrease dramatically and the defect density increase significantly.The addition of TiF_(3)made the surface of ball milling alloy particles markedly coarser and more irregular.Ball milling and adding TiF_(3)distinctly improved the activation and kinetics of the alloys.Moreover,ball milling along with TiF_(3)can decrease the onset dehydrogenation temperature of Mg-based hydrides and slightly ameliorate their thermodynamics.

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.

Thermodynamics in a quantum corrected Reissner-Nordstr?m-AdS black hole and its GUP-corrections

We calculate the thermodynamic quantities in the quantum corrected Reissner-Nordstr?m-AdS(RN-AdS)black hole,and examine their quantum corrections.By analyzing the mass and heat capacity,we give the critical state and the remnant state,respectively,and discuss their consistency.Then,we investigate the quantum tunneling from the event horizon of massless scalar particle by using the null geodesic method,and charged massive boson W^(±)and fermions by using the Hamilton-Jacob method.It is shown that the same Hawking temperature can be obtained from these tunneling processes of different particles and methods.Next,by using the generalized uncertainty principle(GUP),we study the quantum corrections to the tunneling and the temperature.Then the logarithmic correction to the black hole entropy is obtained.

Comparative analysis of thermodynamic and mechanical responses between underground hydrogen storage and compressed air energy storage in lined rock caverns

Underground hydrogen storage(UHS)and compressed air energy storage(CAES)are two viable largescale energy storage technologies for mitigating the intermittency of wind and solar power.Therefore,it is meaningful to compare the properties of hydrogen and air with typical thermodynamic storage processes.This study employs a multi-physical coupling model to compare the operations of CAES and UHS,integrating gas thermodynamics within caverns,thermal conduction,and mechanical deformation around rock caverns.Gas thermodynamic responses are validated using additional simulations and the field test data.Temperature and pressure variations of air and hydrogen within rock caverns exhibit similarities under both adiabatic and diabatic simulation modes.Hydrogen reaches higher temperature and pressure following gas charging stage compared to air,and the ideal gas assumption may lead to overestimation of gas temperature and pressure.Unlike steel lining of CAES,the sealing layer(fibre-reinforced plastic FRP)in UHS is prone to deformation but can effectively mitigates stress in the sealing layer.In CAES,the first principal stress on the surface of the sealing layer and concrete lining is tensile stress,whereas UHS exhibits compressive stress in the same areas.Our present research can provide references for the selection of energy storage methods.

Recent progress in thermodynamic and kinetics modification of magnesium hydride hydrogen storage materials

Hydrogen energy has emerged as a pivotal solution to address the global energy crisis and pave the way for a cleaner,low-carbon,secure,and efficient modern energy system.A key imperative in the utilization of hydrogen energy lies in the development of high-performance hydrogen storage materials.Magnesium-based hydrogen storage materials exhibit remarkable advantages,including high hydrogen storage density,cost-effectiveness,and abundant magnesium resources,making them highly promising for the hydrogen energy sector.Nonetheless,practical applications of magnesium hydride for hydrogen storage face significant challenges,primarily due to their slow kinetics and stable thermodynamic properties.Herein,we briefly summarize the thermodynamic and kinetic properties of MgH2,encompassing strategies such as alloying,nanoscaling,catalyst doping,and composite system construction to enhance its hydrogen storage performance.Notably,nanoscaling and catalyst doping have emerged as more effective modification strategies.The discussion focuses on the thermodynamic changes induced by nanoscaling and the kinetic enhancements resulting from catalyst doping.Particular emphasis lies in the synergistic improvement strategy of incorporating nanocatalysts with confinement materials,and we revisit typical works on the multi-strategy optimization of MgH2.In conclusion,we conduct an analysis of outstanding challenges and issues,followed by presenting future research and development prospects for MgH2 as hydrogen storage materials.

Crystal structure,phase transitions,and thermodynamic properties of magnesium metavanadate(MgV_(2)O_(6))

As a promising anode material for magnesium ion rechargeable batteries,magnesium metavanadate(MgV_(2)O_(6))has attracted considerable research interest in recent years.A MgV_(2)O_(6)sample was synthesized via a facile solid-state reaction by multistep-firing stoichiometric mixtures of MgO and V2O5 powder under an air atmosphere.The solid-state phase transition fromα-MgV_(2)O_(6)toβ-MgV_(2)O_(6)occurred at 841 K and the enthalpy change was 4.37±0.04 kJ/mol.The endothermic effect at 1014 K and the enthalpy change was 26.54±0.26 kJ/mol,which is related to the incongruent melting ofβ-MgV_(2)O_(6).In situ XRD was performed to investigate phase transition of the as-prepared MgV_(2)O_(6)at high temperatures.The cell parameters obtained by Rietveld refinement indicated that it crystallizes in a monoclinic system with the C2/m space group,and the lattice parameters of a=9.280 A°,b=3.501 A°,c=6.731 A°,β=111.76°.The solid-state phase transition fromα-MgV_(2)O_(6)toβ-MgV_(2)O_(6)was further studied by thermal kinetics,indicating that this process is controlled first by a fibril-like mechanism and then by a spherulitic-type mechanism with an increasing heating rate.Additionally,the enthalpy change of MgV_(2)O_(6)at high temperatures was measured utilizing the drop calorimetry,heat capacity was calculated and given as:Cp=208.3+0.03583T-4809000T^(−2)(298-923 K)(J mol^(−1)K^(−1)),the high-temperature heat capacity can be used to calculate Gibbs free energy of MgV_(2)O_(6)at high temperatures.

Thermodynamic theory of flotation for a complex multiphase solid -liquid system and high-entropy flotation

The flotation of complex solid–liquid multiphase systems involve interactions among multiple components,the core problem facing flotation theory.Meanwhile,the combined use of multicomponent flotation reagents to improve mineral flotation has become an important issue in studies on the efficient use of refractory mineral resources.However,studying the flotation of complex solid–liquid systems is extremely difficult,and no systematic theory has been developed to date.In addition,the physical mechanism associated with combining reagents to improve the flotation effect has not been unified,which limits the development of flotation theory and the progress of flotation technology.In this study,we applied theoretical thermodynamics to a solid–liquid flotation system and used changes in the entropy and Gibbs free energy of the reagents adsorbed on the mineral surface to establish thermodynamic equilibrium equations that de-scribe interactions among various material components while also introducing adsorption equilibrium constants for the flotation reagents adsorbed on the mineral surface.The homogenization effect on the mineral surface in pulp solution was determined using the chemical potentials of the material components of the various mineral surfaces required to maintain balance.The flotation effect can be improved through synergy among multicomponent flotation reagents;its physical essence is the thermodynamic law that as the number of compon-ents of flotation reagents on the mineral surface increases,the surface adsorption entropy change increases,and the Gibbs free energy change of adsorption decreases.According to the results obtained using flotation thermodynamics theory,we established high-entropy flotation theory and a technical method in which increasing the types of flotation reagents adsorbed on the mineral surface,increasing the adsorption entropy change of the flotation reagents,decreasing the Gibbs free energy change,and improving the adsorption efficiency and stability of the flotation reagents improves refractory mineral flotation.

Two innovative equivalent statements of the third law of thermodynamics

It is found from textbooks and literature that there are three different statements for the third law of thermodynamics,i.e., the Nernst theorem, the unattainability statement of absolute zero temperature, and the heat capacity statement. It is pointed out that such three statements correspond to three thermodynamic parameters, which are, respectively, the entropy,temperature, and heat capacity, and can be obtained by extrapolating the experimental results of different parameters at ultralow temperatures to absolute zero. It is expounded that because there is no need for additional assumptions in the derivation of the Nernst equation, the Nernst theorem should be renamed as the Nernst statement. Moreover, it is proved that both the Nernst statement and the heat capacity statement are mutually deducible and equivalent, while the unattainability of absolute zero temperature is only a corollary of the Nernst statement or the heat capacity statement so that it is unsuitably referred to as one statement of the third law of thermodynamics. The conclusion is that the Nernst statement and the heat capacity statement are two equivalent statements of the third law of thermodynamics.

Rigidity Symmetry Line for Thermodynamic Fluid Equations-of-State

We report progress towards a modern scientific description of thermodynamic properties of fluids following the discovery (in 2012) of a coexisting critical density hiatus and a supercritical mesophase defined by percolation transitions. The state functions density ρ(p,T), and Gibbs energy G(p,T), of fluids, e.g. CO2, H2O and argon exhibit a symmetry characterised by the rigidity, ω = (dp/dρ)T, between gaseous and liquid states along any isotherm from critical (Tc) to Boyle (TB) temperatures, on either side of the supercritical mesophase. Here, using experimental data for fluid argon, we investigate the low-density cluster physics description of an ideal dilute gas that obeys Dalton’s partial pressure law. Cluster expansions in powers of density relate to a supercritical liquid-phase rigidity symmetry (RS) line (ω = ρrs(T) = RT) to gas phase virial coefficients. We show that it is continuous in all derivatives, linear within stable fluid phase, and relates analytically to the Boyle-work line (BW) (w = (p/ρ)T = RT), and to percolation lines of gas (PB) and liquid (PA) phases by: ρBW(T) = 2ρPA(T) = 3ρPB(T) = 3ρRS(T)/2 for T TB. These simple relationships arise, because the higher virial coefficients (bn, n ≥ 4) cancel due to clustering equilibria, or become negligible at all temperatures (0 T TB) within the gas phase. The Boyle-work line (p/ρBW)T is related exactly at lower densities as T → TB, and accurately for liquid densities, by ρBW(T) = −(b2/b3)T. The RS line, ω(T) = RT, defines a new liquid-density ground-state physical constant (ρRS(0) = (2/3)ρBW(0) for argon). Given the gas-liquid rigidity symmetry, the entire thermodynamic state functions below TB are obtainable from b2(T). A BW-line ground-state crystal density ρBW(0) can be defined by the pair potential minimum. The Ar2 pair potential, ∅ij(rij) determines b2(T) analytically for all T. This report, therefore, advances the salient objective of liquid-state theory: an argon p(ρ,T) Equation-of-state is obtained from ∅ij(rij) for all fluid states, without any adjustable parameters.

Finite-Time Thermodynamic Simulation of Circulating Direct Condensation Heat Recovery on Chillers

A time series model is used in this paper to describe the progress of circulating direct condensation heat recovery of the compound condensing process (CCP) which is made of two water cooling condensing processes in series for a centrifugal chiller in the paper. A finite-time thermodynamics method is used to set up the time series simulation model. As a result, an upper bound of recoverable condensation heat for the compound condensing process is obtained which is in good agreement with experimental result. And the result is valuable and useful to optimization design of condensing heat recovery.

A Number Theoretic Analysis of the Enthalpy, Enthalpy Energy Density, Thermodynamic Volume, and the Equation of State of a Modified White Hole, and the Implications to the Quantum Vacuum Spacetime, Matter Creation and the Planck Frequency

In this paper, we analyze the enthalpy, enthalpy energy density, thermodynamic volume, and the equation of state of a modified white hole. We obtain new possible mathematical connections with some sectors of Number Theory, Ramanujan Recurring Numbers, DN Constant and String Theory, that enable us to extract the quantum geometrical properties of these thermodynamic equations and the implication to the quantum vacuum spacetime geometry of our early universe as they act as the constraints to the nature of quantum gravity of the universe.

Removal of Organochlorine from Model Oil Using Mg-Modified ZSM-5 Zeolite:Dechlorination Performance,Regeneration,and Thermodynamics

Various metal-modified ZSM-5 zeolite adsorbents prepared by the impregnation method were applied to the removal of organic chlorides from model naphtha.The adsorption performance and regeneration stability were investigated by static adsorption experiments.The morphologies,structural features,and physicochemical properties of the adsorbents were characterized by X-ray diffraction,Brunauer-Emmett-Teller analysis,NH3 temperature-programmed desorption,scanning electron microscopy,transmission electron microscopy,and pyridine adsorption infrared spectroscopy.The Mg/ZSM-5 zeolite adsorbent possessed a relatively high specific surface area and good metal dispersion and exhibited the best dechlorination and regeneration performance.The characterization results revealed that introduction of the metal exerted a significant influence on the acidic properties of the catalyst surface.A decrease in the ratio of Brønsted acidic sites to Lewis acidic sites and an increase in the amount of moderately acidic sites were confirmed to be responsible for the excellent adsorption performance of the Mg-modified ZSM-5 zeolite.Furthermore,the Langmuir adsorption isotherm model was applied to study the adsorption equilibrium and thermodynamics of the Mg/ZSM-5 adsorbent under mild conditions.The results revealed that the removal of 1,2-dichloroethane by the Mg/ZSM-5 adsorbent was endothermic,spontaneous,disordered,and primarily involved physical adsorption.

Solubility measurement,correlation and thermodynamic properties of 2,3,4-trichloro-1,5-dinitrobenzene in fifteen mono-solvents at temperatures from 278.15 to 323.15 K

The solubility of 2,3,4-trichloro-1,5-dinitrobenzene(TCDNB) was measured by a laser dynamic method over the temperature range from 278.15 K to 323.15 K under 0.1 MPa in fifteen mono-solvents(methanol,ethanol,isopropanol,n-butanol,toluene,dichloromethane,chloroform,tetrachloromethane,1,2-dichloroethane,acetone,ethyl acetate,acetonitrile,N-methylpyrrolidone(NMP),N,Ndimethylformamide dimethyl sulfoxide(DMF),dimethyl sulfoxide(DMSO).The solubility of TCDNB could be increased with increasing temperature in fifteen mono-solvents.TCDNB solubility is in the following order at 298.15 K:NMP>DMF>DMSO>toluene>acetone>ethyl acetate>dichloromethane>1,2-dich loroethane>chloroform>acetonitrile>tetrachloromethane>methanol>ethanol>n-butanol>isopropanol.The KAT-LSER model was used to investigate the solvent effect,which revealed that the hydrogen bond acidity of solvents has a greater effect on TCDNB solubility.The van't Hoff model,the modified Apelblat model,theλh model,and the non-random two liquid(NRTL)model were used to correlate the solubility of TCDNB.The calculated solubility data agreed well with the experimental data,and the modified Apelblat model fit best.Furthermore,the van't Hoff and Gibbs equations were also used to calculate the dissolution thermodynamic properties of TCDNB in various solvents.TCDNB dissolution could be an enthalpy-driven,non-spontaneous,and endothermic process in fifteen mono-solvents.The determination and fitting solubility of TCDNB,as well as the calculation of its thermodynamic properties,would be critical in the purification and crystallization of its preparation process research.

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.

Contribution of biodiversity to ecosystem functioning:a non-equilibrium thermodynamic perspective

Ecosystem stays far from thermodynamic equilibrium. Through the interactions among biotic and abiotic components, and encompassing physical environments, ecosystem forms a dissipative struc- ture that allows it to dissipate energy continuously and thereby remains functional over time. Biotic regulation of energy and material fluxes in and out of the ecosystem allows it to maintain a homeostatic state which corresponds to a self-organized state emerged in a non-equilibrium thermodynamic system. While the associated self-organizational processes approach to homeostatic state, entropy （a measure of irre- versibility） degrades and dissipation of energy increases. We propose here that at a homeostatic state of ecosystem, biodiversity which includes both phenotypic and functional diversity, attains optimal values. As long as biodiversity remains within its optimal range, the corresponding homeostatic state is maintained. However, while embedded environmental conditions fluctuate along the gradient of accelerating changes, phenotypic diversity and functional diversity contribute inversely to the associated self-organizing proc- esses. Furthermore, an increase or decrease in biodiversity outside of its optimal range makes the eco- system vulnerable to transition into a different state.