A principle was proposed for designing a method to seal anodized aluminum used in semiconductor processing apparatuses.Thermodynamic calculations and Fick’s second law were used to reveal trends in the metal ion depo...A principle was proposed for designing a method to seal anodized aluminum used in semiconductor processing apparatuses.Thermodynamic calculations and Fick’s second law were used to reveal trends in the metal ion deposition,deposition product stability,vapor pressures of halides for selected metal ions,the holding temperature,and time.Interactions between ion concentrations and the sealing temperature were also revealed.According to the design principles,anodized aluminum dipped in 1 mM Cr^(3+)ion solution and steam-sealed for 18 h exhibited the highest corrosion resistance when exposed to 5 wt.%HCl solution and HCl gas,verifying the designed results.展开更多
We modify the method to generate the exact solutions of the Einstein equations basing on the laws of thermodynamics. Firstly, the Komar mass is used to take the place of the Misner-Sharp energy, which is used in the o...We modify the method to generate the exact solutions of the Einstein equations basing on the laws of thermodynamics. Firstly, the Komar mass is used to take the place of the Misner-Sharp energy, which is used in the original methods, and then several exact solutions of Einstein equations are obtained, including the black hole solution which is surrounded by quintessence. Moreover, the geometry surface gravity defined by Komar mass is also constructed.Secondly, we use both the Komar mass and the ADM mass to modify such method, and the similar results are obtained.Moreover, with some generalize addition to the definition of the ADM mass, our method can be generalized to global monopole spacetime.展开更多
The structure and behaviour of LiF-KF solution,as a typical common-anion system,has been simulated by Monte Carlo method.The calculation of partial radial distribution function of ions,heat of mixing and potential ene...The structure and behaviour of LiF-KF solution,as a typical common-anion system,has been simulated by Monte Carlo method.The calculation of partial radial distribution function of ions,heat of mixing and potential energy distribution shows that the average distance be- tween Li^+ and F^- ions will significantly narrow after mixing of molten LiF and KF.This is very similar to the lean-on-one-side effect in molten LiF-KCl solution.The calculated heat of mixing is in fair agreement with the measured one.The dominant source of the energy of mixing may be that the decrease of the repulsion energy between cations,the decrease of the attraction energy between cations and anions,and the decrease of the repulsion energy be- tween anions.展开更多
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...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.展开更多
The world's first full Experimental Advanced Superconducting Tokamak(EAST) is designed with the auxiliary heating method of neutral beam injection(NBI)system. Beam collimators are arranged on both sides of the bea...The world's first full Experimental Advanced Superconducting Tokamak(EAST) is designed with the auxiliary heating method of neutral beam injection(NBI)system. Beam collimators are arranged on both sides of the beam channel for absorbing the divergence beam during the beam transmission process in the EAST-NBI system.The gas baffle entrance collimator(GBEC) is a typical high-heat-flux component located at the entrance of gas baffle. An efficient and accurate analysis of its thermodynamic performance is of great significance to explore the working limit and to ensure safe operation of the system under a high-parameter steady-state condition. Based on the thermo-fluid coupled method, thermodynamic analysis and simulation of GBEC is performed to get the working states and corresponding operating limits at different beam extraction conditions. This study provides a theoretical guidance for the next step to achieve long pulse with highpower experimental operation and has an important reference to ensure the safe operation of the system.展开更多
Catalytic conversion of COinto chemicals and fuels is an alternative to alleviate climate change and ocean acidification.The catalytic reduction of COby Hcan lead to the formation of various products:carbon monoxide,c...Catalytic conversion of COinto chemicals and fuels is an alternative to alleviate climate change and ocean acidification.The catalytic reduction of COby Hcan lead to the formation of various products:carbon monoxide,carboxylic acids,aldehydes,alcohols and hydrocarbons.In this paper,a comprehensive thermodynamics analysis of COhydrogenation is conducted using the Gibbs free energy minimization method.The results show that COreduction to CO needs a high temperature and H/COratio to achieve a high COconversion.However,synthesis of methanol from COneeds a relatively high pressure and low temperature to minimize the reverse water-gas shift reaction.Direct COhydrogenation to formic acid or formaldehyde is thermodynamically limited.On the contrary,production of CHfrom COhydrogenation is the thermodynamically easiest reaction with nearly 100%CH4 yield at moderate conditions.In addition,complex reactions with more than one product are also calculated in this work.Among the considered carboxylic acids（HCOOH,CHCOOH and CHCOOH）,propionic acid dominates in the product stream（selectivity above 90%）.The same trend can also be found in the hydrogenation of COto aldehydes and alcohols with the major product of propionaldehyde and butanol,respectively.In the process of COhydrogenation to alkenes,low temperature,high pressure,and high Hpartial pressure favor the COconversion.CHis the most thermodynamically favorable among all considered alkynes under different temperatures and pressures.The thermodynamic calculations are validated with experimental results,suggesting that the Gibbs free energy minimization method is effective for thermodynamically understanding the reaction network involved in the COhydrogenation process,which is helpful for the development of high-performance catalysts.展开更多
Mg-based materials are one of the most promising hydrogen storage candidates due to their high hydrogen storage capacity,environmental benignity,and high Clarke number characteristics.However,the limited thermodynamic...Mg-based materials are one of the most promising hydrogen storage candidates due to their high hydrogen storage capacity,environmental benignity,and high Clarke number characteristics.However,the limited thermodynamics and kinetic properties pose major challenges for their engineering applications.Herein,we review the recent progress in improving their thermodynamics and kinetics,with an emphasis on the models and the influence of various parameters in the calculated models.Subsequently,the impact of alloying,composite,and nanocrystallization on both thermodynamics and dynamics are discussed in detail.In particular,the correlation between various modification strategies and the hydrogen capacity,dehydrogenation enthalpy and temperature,hydriding/dehydriding rates are summarized.In addition,the mechanism of hydrogen storage processes of Mg-based materials is discussed from the aspect of classical kinetic theories and microscope hydrogen transferring behavior.This review concludes with an outlook on the remaining challenge issues and prospects.展开更多
Thermodynamic analysis was applied to study combined partial oxidation and carbon dioxide reforming of methane in view of carbon formation. The equilibrium calculations employing the Gibbs energy minimization were per...Thermodynamic analysis was applied to study combined partial oxidation and carbon dioxide reforming of methane in view of carbon formation. The equilibrium calculations employing the Gibbs energy minimization were performed upon wide ranges of pressure （1-25 atm）, temperature （600-1300 K）, carbon dioxide to methane ratio （0-2） and oxygen to methane ratio （0-1）. The thermodynamic results were compared with the results obtained over a Ru supported catalyst. The results revealed that by increasing the reaction pressure methane conversion decreased. Also it was found that the atmospheric pressure is the preferable pressure for both dry reforming and partial oxidation of methane and increasing the temperature caused increases in both activity of carbon and conversion of methane. The results clearly showed that the addition of O2 to the feed mixture could lead to a reduction of carbon deposition.展开更多
An effective relativistic continuum massive Proca Lagrangian action is used to account for the Lorentzvector condensation effects on the equation of state of the strongly interacting fermions system.The interior quant...An effective relativistic continuum massive Proca Lagrangian action is used to account for the Lorentzvector condensation effects on the equation of state of the strongly interacting fermions system.The interior quantumfluctuation effects are incorporated as an external field approximation indirectly through a fictive generalized ThomsonProblem counterterm background.The general analytical formulas for the d-dimensional thermodynamics are given nearthe unitary limit region,In the non-relativistic limit for d=3,the universal dimensionless coefficientε=4/9 andenergy gap △/ε_f=5/18 are reasonably consistent with the existing theoretical and experimental results.In the unitarylimit for d=2 and T=0,the universal coefficient can even approach the extreme occasion ξ=0 corresponding to theinfinite effective fermion mass m~*=∞,which can be mapped to the strongly coupled two-dimensional electrons and isquite similar to the three-dimensional Bose-Einstein condensation of ideal boson gas.Instead,for d=1,the universalcoefficient ξ is negative,implying the non-existence of phase transition from superfluidity to normal state.The solutionsmanifest the quantum Ising universal class characteristic of the strongly coupled unitary fermions gas.展开更多
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 dis...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.展开更多
A matrix eigenvalue method is applied to analyse the thermodynamic stability of two-component interacting fermions. The non-relativistic and ultra-relativistic d = 1, 2, 3 dimensions have been discussed in detail, res...A matrix eigenvalue method is applied to analyse the thermodynamic stability of two-component interacting fermions. The non-relativistic and ultra-relativistic d = 1, 2, 3 dimensions have been discussed in detail, respectively. The corresponding stability region has been given according to the two-body interaction strength and the particle number density ratio.展开更多
Non-equilibrium thermodynamics theory is used to analyze the transmembrane heat and moisture transfer process,which can be observed in a membrane-type total heat exchanger(THX).A theoretical model is developed to simu...Non-equilibrium thermodynamics theory is used to analyze the transmembrane heat and moisture transfer process,which can be observed in a membrane-type total heat exchanger(THX).A theoretical model is developed to simulate the coupled heat and mass transfer across a membrane,total coupling equations and the expressions for the four characteristic parameters including the heat transfer coefficient,molardriven heat transfer coefficient,thermal-driven mass transfer coefficient,and mass transfer coefficient are derived and provided,with the Onsager’s reciprocal relation being confirmed to verify the rationality of the model.Calculations are conducted to investigate the effects of the membrane property and air state on the coupling transport process.The results show that the four characteristic parameters directly affect the transmembrane heat and mass fluxes:the heat and mass transfer coefficients are both positive,meaning that the temperature difference has a positive contribution to the heat transfer and the humidity ratio difference has a positive contribution to the mass transfer.The molar-driven heat transfer and thermal-driven mass transfer coefficients are both negative,implying that the humidity ratio difference acts to reduce the heat transfer and the temperature difference works to diminish the mass transfer.The mass transfer affects the heat transfer by 1%–2%while the heat transfer influences the mass transfer by7%–14%.The entropy generation caused by the temperature difference-induced heat transfer is much larger than that by the humidity difference-induced mass transfer.展开更多
Nanofiltration of aqueous NaNO3 solution with a dynamically formed Zr(IV) hydrousoxide-PAA membrane is presented. The practical transpoft coefficients Lp, σ, ω were obtainedusing relationships of the non-equilibrium...Nanofiltration of aqueous NaNO3 solution with a dynamically formed Zr(IV) hydrousoxide-PAA membrane is presented. The practical transpoft coefficients Lp, σ, ω were obtainedusing relationships of the non-equilibrium thermodynamics and were used to calculate thefrictional coefficients of a friction model.展开更多
Schiff<sup> </sup>base synthesis is usually acid catalyzed and it usually requires refluxing the mixture of aldehydes and amine in ethanolic solution. Synthesis and characterization of Schiff base ligands ...Schiff<sup> </sup>base synthesis is usually acid catalyzed and it usually requires refluxing the mixture of aldehydes and amine in ethanolic solution. Synthesis and characterization of Schiff base ligands derived from substituted amine and salicylaldehyde and their complexes (Cu<sup>2+</sup>, Co<sup>2+</sup>) are reported. The ligands and ligand-complexes were characterized by melting point, FTIR, CHN-elemental analysis and UV-Visible analysis. The UV-Visible and elemental analysis of complexes established (1:2) mole ratio (M:L). The stability constant and thermodynamic parameters (K, ΔG, ΔH, ΔS) were determined at different temperature (30 - 40)°C which established that the metal-complexes were very stable. The review describes the promising biological<sup> </sup>activities of Schiff base and their metal complexes.展开更多
The Gibbs-Bogoliubov （GB） inequality is applied to investigate the thermodynamic properties of some equiatomic noble metal alloys in liquid phase such as Au-Cu, Ag-Cu, and Ag-Au using well recognized pseudopotential...The Gibbs-Bogoliubov （GB） inequality is applied to investigate the thermodynamic properties of some equiatomic noble metal alloys in liquid phase such as Au-Cu, Ag-Cu, and Ag-Au using well recognized pseudopotential formalism. For description of the structure, well known Percus-Yevick （PY） hard sphere model is used as a reference system. By applying a variation method the best hard core diameters have been found which correspond to minimum free energy. With this procedure the thermodynamic properties such as entropy and heat of mixing have been computed. The influence of local field correction function viz; Hartree （H）, Taylor （T）, lehimaru-Utsumi （IU）, Farid et al. （F）, and Sarkar et al. （S） is also investigated. The computed results of the excess entropy compares favourably in the case of liquid alloys while the agreement with experiment is poor in the case of heats of mixing. This may be due to the sensitivity of the heats of mixing with the potential parameters and the dielectric function.展开更多
A Discrete Boltzmann Method(DBM)with a Maxwell-type boundary condition is constructed to investigate the influence of rarefaction on laminar Shock Wave/Boundary Layer Interaction(SWBLI).Due to the complexity of compre...A Discrete Boltzmann Method(DBM)with a Maxwell-type boundary condition is constructed to investigate the influence of rarefaction on laminar Shock Wave/Boundary Layer Interaction(SWBLI).Due to the complexity of compressible flow,a Knudsen number vector Kn,whose components include the local Knudsen numbers such as Kn_(ρ)and Kn_(U),is introduced to characterize the local structures,where Kn_(ρ)and Kn_(U)are Knudsen numbers defined in terms of the density and velocity interfaces,respectively.Since first focusing on the steady state of SWBLI,the DBM considers up to the second-order Kn_(ρ)(rarefaction/non-equilibrium)effects.The model is validated using Mach number 2 SWBLI and the necessity of using DBM with sufficient physical accuracy is confirmed by the shock collision problem.Key findings include the following:the leading-edge shock wave increases the local density Knudsen number Kn_(ρ)and eventually leads to the failure of linear constitutive relations in the Navier-Stokes(N-S)model and surely also in the lower-order DBM;the non-equilibrium effect differences in regions behind the leading-edge shock wave are primarily correlated with Kn_(ρ),while in the separation region are primarily correlated with Kn_(U);the non-equilibrium quantities D_(2)and D_(4,2),as well as the viscous entropy production rate S_(NOMF)can be used to identify the separation zone.The findings clarify various effects and main mechanisms in different regions associated with SWBLI,which are concealed in N-S model.展开更多
The Richtmyer–Meshkov(RM)instability plays an important role in various natural and engineering fields such as inertial confinement fusion.In this study,the effect of relaxation time on the RM instability under resho...The Richtmyer–Meshkov(RM)instability plays an important role in various natural and engineering fields such as inertial confinement fusion.In this study,the effect of relaxation time on the RM instability under reshock impact is investigated using a two-component discrete Boltzmann method.The hydrodynamic and thermodynamic characteristics of the fluid system are comprehensively analyzed from the perspectives of the density gradient,vorticity,kinetic energy,mixing degree,mixing width and non-equilibrium intensity.Simulation results indicate that for longer relaxation time,the diffusion and dissipation are enhanced,the physical gradients decrease,and the growth of the interface is suppressed.Furthermore,the non-equilibrium manifestations show complex patterns,driven by the competitive physical mechanisms of the diffusion,dissipation,shock wave,rarefaction wave,transverse wave and fluid instabilities.These findings provide valuable insight into the fundamental mechanism of compressible fluid flows.展开更多
In this study,a powerful thermo-hydro-mechanical(THM)coupling solution scheme for saturated poroelastic media involving brittle fracturing is developed.Under the local thermal non-equilibrium(LTNE)assumption,this sche...In this study,a powerful thermo-hydro-mechanical(THM)coupling solution scheme for saturated poroelastic media involving brittle fracturing is developed.Under the local thermal non-equilibrium(LTNE)assumption,this scheme seamlessly combines the material point method(MPM)for accurately tracking solid-phase deformation and heat transport,and the Eulerian finite element method(FEM)for effectively capturing fluid flow and heat advection-diffusion behavior.The proposed approach circumvents the substantial challenges posed by large nonlinear equation systems with the monolithic solution scheme.The staggered solution process strategically separates each physical field through explicit or implicit integration.The characteristic-based method is used to stabilize advection-dominated heat flows for efficient numerical implementation.Furthermore,a fractional step approach is employed to decompose fluid velocity and pressure,thereby suppressing pore pressure oscillation on the linear background grid.The fracturing initiation and propagation are simulated by a rate-dependent phase field model.Through a series of quasi-static and transient simulations,the exceptional performance and promising potential of the proposed model in addressing THM fracturing problems in poro-elastic media is demonstrated.展开更多
The thermodynamic re-assessment of Au-Pt binary system was carried out by using the Calphad method and based on the recent experimental data. The Gibbs energies of face-centred cubic and liquid phases were described b...The thermodynamic re-assessment of Au-Pt binary system was carried out by using the Calphad method and based on the recent experimental data. The Gibbs energies of face-centred cubic and liquid phases were described by a sub-regular solution model with the Redlich-Kister equation. Much effort was taken to reproduce the phase equilibrium results and thermodynamic properties of the solid phase, including the activity and mixing enthalpy. The constraint of the third law of thermodynamics was also considered in the assessment. According to the presently assessed results, the miscibility gap region in the Au-Pt system slightly shifts to the Au-rich side, and the critical !0oint of the miscibility gap is about 1200 ℃ and Au-56% Pt.展开更多
In this paper, the methodology of non-equilibrium thermodynamics is introduced for kinetics research of CO2 capture by ionic liquids, and the following three key scientific problems are proposed to apply the methodolo...In this paper, the methodology of non-equilibrium thermodynamics is introduced for kinetics research of CO2 capture by ionic liquids, and the following three key scientific problems are proposed to apply the methodology in kinetics research of CO2 capture by ionic liquids: reliable thermodynamic models, interfacial transport rate description and accurate experimental flux. The obtaining of accurate experimental flux requires reliable experimental kinetics data and the effective transport area in the CO2 capture process by ionic liquids. Research advances in the three key scientific problems are reviewed systematically and further work is analyzed. Finally, perspectives of non-equilibrium thermodynamic research of the kinetics of CO2 capture by ionic liquids are proposed.展开更多
基金supported by the Program of the National Natural Science Foundation of China(Grant No.52371055)the Young Elite Scientist Sponsorship Program Cast(Grant No.YESS20200139)+1 种基金the Basic Scientific Research Project of Liaoning Provincial Department of Education(Grant No.JYTMS20230618)Special thanks are due to the instrumental analysis from the Analytical and Testing Centre,Northeastern University.
文摘A principle was proposed for designing a method to seal anodized aluminum used in semiconductor processing apparatuses.Thermodynamic calculations and Fick’s second law were used to reveal trends in the metal ion deposition,deposition product stability,vapor pressures of halides for selected metal ions,the holding temperature,and time.Interactions between ion concentrations and the sealing temperature were also revealed.According to the design principles,anodized aluminum dipped in 1 mM Cr^(3+)ion solution and steam-sealed for 18 h exhibited the highest corrosion resistance when exposed to 5 wt.%HCl solution and HCl gas,verifying the designed results.
基金Supported by the National Natural Science Foundation of China under Grant Nos.11273009 and 11303006
文摘We modify the method to generate the exact solutions of the Einstein equations basing on the laws of thermodynamics. Firstly, the Komar mass is used to take the place of the Misner-Sharp energy, which is used in the original methods, and then several exact solutions of Einstein equations are obtained, including the black hole solution which is surrounded by quintessence. Moreover, the geometry surface gravity defined by Komar mass is also constructed.Secondly, we use both the Komar mass and the ADM mass to modify such method, and the similar results are obtained.Moreover, with some generalize addition to the definition of the ADM mass, our method can be generalized to global monopole spacetime.
文摘The structure and behaviour of LiF-KF solution,as a typical common-anion system,has been simulated by Monte Carlo method.The calculation of partial radial distribution function of ions,heat of mixing and potential energy distribution shows that the average distance be- tween Li^+ and F^- ions will significantly narrow after mixing of molten LiF and KF.This is very similar to the lean-on-one-side effect in molten LiF-KCl solution.The calculated heat of mixing is in fair agreement with the measured one.The dominant source of the energy of mixing may be that the decrease of the repulsion energy between cations,the decrease of the attraction energy between cations and anions,and the decrease of the repulsion energy be- tween anions.
文摘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.
基金supported by the National Natural Science Foundation of China(No.11605234)the Foundation of ASIPP(No.DSJJ-15-GC02)
文摘The world's first full Experimental Advanced Superconducting Tokamak(EAST) is designed with the auxiliary heating method of neutral beam injection(NBI)system. Beam collimators are arranged on both sides of the beam channel for absorbing the divergence beam during the beam transmission process in the EAST-NBI system.The gas baffle entrance collimator(GBEC) is a typical high-heat-flux component located at the entrance of gas baffle. An efficient and accurate analysis of its thermodynamic performance is of great significance to explore the working limit and to ensure safe operation of the system under a high-parameter steady-state condition. Based on the thermo-fluid coupled method, thermodynamic analysis and simulation of GBEC is performed to get the working states and corresponding operating limits at different beam extraction conditions. This study provides a theoretical guidance for the next step to achieve long pulse with highpower experimental operation and has an important reference to ensure the safe operation of the system.
基金funded by the National Research Foundation(NRF)Prime Minister’s Office,Singapore under its Campus for Research Excellence and Technological Enterprise(CREATE)Program
文摘Catalytic conversion of COinto chemicals and fuels is an alternative to alleviate climate change and ocean acidification.The catalytic reduction of COby Hcan lead to the formation of various products:carbon monoxide,carboxylic acids,aldehydes,alcohols and hydrocarbons.In this paper,a comprehensive thermodynamics analysis of COhydrogenation is conducted using the Gibbs free energy minimization method.The results show that COreduction to CO needs a high temperature and H/COratio to achieve a high COconversion.However,synthesis of methanol from COneeds a relatively high pressure and low temperature to minimize the reverse water-gas shift reaction.Direct COhydrogenation to formic acid or formaldehyde is thermodynamically limited.On the contrary,production of CHfrom COhydrogenation is the thermodynamically easiest reaction with nearly 100%CH4 yield at moderate conditions.In addition,complex reactions with more than one product are also calculated in this work.Among the considered carboxylic acids（HCOOH,CHCOOH and CHCOOH）,propionic acid dominates in the product stream（selectivity above 90%）.The same trend can also be found in the hydrogenation of COto aldehydes and alcohols with the major product of propionaldehyde and butanol,respectively.In the process of COhydrogenation to alkenes,low temperature,high pressure,and high Hpartial pressure favor the COconversion.CHis the most thermodynamically favorable among all considered alkynes under different temperatures and pressures.The thermodynamic calculations are validated with experimental results,suggesting that the Gibbs free energy minimization method is effective for thermodynamically understanding the reaction network involved in the COhydrogenation process,which is helpful for the development of high-performance catalysts.
基金supported by the Chongqing Special Key Project of Technology Innovation and Application Development,China(cstc2019jscx-dxwt B0029)the National Natural Science Foundation of China(51871143)+5 种基金the Science and Technology Committee of Shanghai(19010500400)the Shanghai Rising-Star Program(21QA1403200)Chongqing Research Program of Basic Research and Frontier Technology(No.cstc2019jcyj-msxm X0306)the Start-up Funds of Chongqing University(02110011044171)the Senior Talent Start-up Funds of Jiangsu University(4111310024)the Independent Research Project of State Key Laboratory of Mechanical Transmissions(SKLMT-ZZKT-2021M11)
文摘Mg-based materials are one of the most promising hydrogen storage candidates due to their high hydrogen storage capacity,environmental benignity,and high Clarke number characteristics.However,the limited thermodynamics and kinetic properties pose major challenges for their engineering applications.Herein,we review the recent progress in improving their thermodynamics and kinetics,with an emphasis on the models and the influence of various parameters in the calculated models.Subsequently,the impact of alloying,composite,and nanocrystallization on both thermodynamics and dynamics are discussed in detail.In particular,the correlation between various modification strategies and the hydrogen capacity,dehydrogenation enthalpy and temperature,hydriding/dehydriding rates are summarized.In addition,the mechanism of hydrogen storage processes of Mg-based materials is discussed from the aspect of classical kinetic theories and microscope hydrogen transferring behavior.This review concludes with an outlook on the remaining challenge issues and prospects.
基金supported by University of Kashan(Grant No.158426/5)
文摘Thermodynamic analysis was applied to study combined partial oxidation and carbon dioxide reforming of methane in view of carbon formation. The equilibrium calculations employing the Gibbs energy minimization were performed upon wide ranges of pressure （1-25 atm）, temperature （600-1300 K）, carbon dioxide to methane ratio （0-2） and oxygen to methane ratio （0-1）. The thermodynamic results were compared with the results obtained over a Ru supported catalyst. The results revealed that by increasing the reaction pressure methane conversion decreased. Also it was found that the atmospheric pressure is the preferable pressure for both dry reforming and partial oxidation of methane and increasing the temperature caused increases in both activity of carbon and conversion of methane. The results clearly showed that the addition of O2 to the feed mixture could lead to a reduction of carbon deposition.
基金the Scientific Starting Research Fund of Central China Normal UniversityNational Natural Science Foundation of China under Grant No.10675052
文摘An effective relativistic continuum massive Proca Lagrangian action is used to account for the Lorentzvector condensation effects on the equation of state of the strongly interacting fermions system.The interior quantumfluctuation effects are incorporated as an external field approximation indirectly through a fictive generalized ThomsonProblem counterterm background.The general analytical formulas for the d-dimensional thermodynamics are given nearthe unitary limit region,In the non-relativistic limit for d=3,the universal dimensionless coefficientε=4/9 andenergy gap △/ε_f=5/18 are reasonably consistent with the existing theoretical and experimental results.In the unitarylimit for d=2 and T=0,the universal coefficient can even approach the extreme occasion ξ=0 corresponding to theinfinite effective fermion mass m~*=∞,which can be mapped to the strongly coupled two-dimensional electrons and isquite similar to the three-dimensional Bose-Einstein condensation of ideal boson gas.Instead,for d=1,the universalcoefficient ξ is negative,implying the non-existence of phase transition from superfluidity to normal state.The solutionsmanifest the quantum Ising universal class characteristic of the strongly coupled unitary fermions gas.
基金supported by the U.S. National Science Foundation's Biocomplexity Program (DEB-0421530)Long-Term Ecological Research Program (Sevilleta LTER,DEB-0620482)
文摘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.
基金Project supported by the Scientific Starting Research Fund of Central China Normal University of Chinathe National Natural Science Foundation of China (Grant Nos 10675052 and 10875050)Ministry of Education of China (Grant No IRT0624)
文摘A matrix eigenvalue method is applied to analyse the thermodynamic stability of two-component interacting fermions. The non-relativistic and ultra-relativistic d = 1, 2, 3 dimensions have been discussed in detail, respectively. The corresponding stability region has been given according to the two-body interaction strength and the particle number density ratio.
基金funded by Beijing Natural Science Foundation(3182015)。
文摘Non-equilibrium thermodynamics theory is used to analyze the transmembrane heat and moisture transfer process,which can be observed in a membrane-type total heat exchanger(THX).A theoretical model is developed to simulate the coupled heat and mass transfer across a membrane,total coupling equations and the expressions for the four characteristic parameters including the heat transfer coefficient,molardriven heat transfer coefficient,thermal-driven mass transfer coefficient,and mass transfer coefficient are derived and provided,with the Onsager’s reciprocal relation being confirmed to verify the rationality of the model.Calculations are conducted to investigate the effects of the membrane property and air state on the coupling transport process.The results show that the four characteristic parameters directly affect the transmembrane heat and mass fluxes:the heat and mass transfer coefficients are both positive,meaning that the temperature difference has a positive contribution to the heat transfer and the humidity ratio difference has a positive contribution to the mass transfer.The molar-driven heat transfer and thermal-driven mass transfer coefficients are both negative,implying that the humidity ratio difference acts to reduce the heat transfer and the temperature difference works to diminish the mass transfer.The mass transfer affects the heat transfer by 1%–2%while the heat transfer influences the mass transfer by7%–14%.The entropy generation caused by the temperature difference-induced heat transfer is much larger than that by the humidity difference-induced mass transfer.
文摘Nanofiltration of aqueous NaNO3 solution with a dynamically formed Zr(IV) hydrousoxide-PAA membrane is presented. The practical transpoft coefficients Lp, σ, ω were obtainedusing relationships of the non-equilibrium thermodynamics and were used to calculate thefrictional coefficients of a friction model.
文摘Schiff<sup> </sup>base synthesis is usually acid catalyzed and it usually requires refluxing the mixture of aldehydes and amine in ethanolic solution. Synthesis and characterization of Schiff base ligands derived from substituted amine and salicylaldehyde and their complexes (Cu<sup>2+</sup>, Co<sup>2+</sup>) are reported. The ligands and ligand-complexes were characterized by melting point, FTIR, CHN-elemental analysis and UV-Visible analysis. The UV-Visible and elemental analysis of complexes established (1:2) mole ratio (M:L). The stability constant and thermodynamic parameters (K, ΔG, ΔH, ΔS) were determined at different temperature (30 - 40)°C which established that the metal-complexes were very stable. The review describes the promising biological<sup> </sup>activities of Schiff base and their metal complexes.
文摘The Gibbs-Bogoliubov （GB） inequality is applied to investigate the thermodynamic properties of some equiatomic noble metal alloys in liquid phase such as Au-Cu, Ag-Cu, and Ag-Au using well recognized pseudopotential formalism. For description of the structure, well known Percus-Yevick （PY） hard sphere model is used as a reference system. By applying a variation method the best hard core diameters have been found which correspond to minimum free energy. With this procedure the thermodynamic properties such as entropy and heat of mixing have been computed. The influence of local field correction function viz; Hartree （H）, Taylor （T）, lehimaru-Utsumi （IU）, Farid et al. （F）, and Sarkar et al. （S） is also investigated. The computed results of the excess entropy compares favourably in the case of liquid alloys while the agreement with experiment is poor in the case of heats of mixing. This may be due to the sensitivity of the heats of mixing with the potential parameters and the dielectric function.
基金support from the National Key R&D Program of China(No.2020YFC2201100)the Foundation of National Key Laboratory of Shock Wave and Detonation Physics,China(No.JCKYS2023212003)+1 种基金the National Natural Science Foundation of China(No.12172061)the Opening Project of State Key Laboratory of Explosion Science and Safety Protection(Beijing Institute of Technology)(No.KFJJ25-02M).
文摘A Discrete Boltzmann Method(DBM)with a Maxwell-type boundary condition is constructed to investigate the influence of rarefaction on laminar Shock Wave/Boundary Layer Interaction(SWBLI).Due to the complexity of compressible flow,a Knudsen number vector Kn,whose components include the local Knudsen numbers such as Kn_(ρ)and Kn_(U),is introduced to characterize the local structures,where Kn_(ρ)and Kn_(U)are Knudsen numbers defined in terms of the density and velocity interfaces,respectively.Since first focusing on the steady state of SWBLI,the DBM considers up to the second-order Kn_(ρ)(rarefaction/non-equilibrium)effects.The model is validated using Mach number 2 SWBLI and the necessity of using DBM with sufficient physical accuracy is confirmed by the shock collision problem.Key findings include the following:the leading-edge shock wave increases the local density Knudsen number Kn_(ρ)and eventually leads to the failure of linear constitutive relations in the Navier-Stokes(N-S)model and surely also in the lower-order DBM;the non-equilibrium effect differences in regions behind the leading-edge shock wave are primarily correlated with Kn_(ρ),while in the separation region are primarily correlated with Kn_(U);the non-equilibrium quantities D_(2)and D_(4,2),as well as the viscous entropy production rate S_(NOMF)can be used to identify the separation zone.The findings clarify various effects and main mechanisms in different regions associated with SWBLI,which are concealed in N-S model.
基金supported by the National Natural Science Foundation of China(Grant No.U2242214)the Guangdong Basic and Applied Basic Research Foundation(Grant No.2024A1515010927)+3 种基金the Humanities and Social Science Foundation of the Ministry of Education in China(Grant No.24YJCZH163)the Fujian Provincial Units Special Funds for Education and Research(Grant No.2022639)Fundamental Research Funds for the Central Universities,Sun Yatsen University(Grant No.24qnpy044)partly supported by the Open Research Fund of Key Laboratory of Analytical Mathematics and Applications(Fujian Normal University),Ministry of Education,P.R.China(Grant No.JAM2405)。
文摘The Richtmyer–Meshkov(RM)instability plays an important role in various natural and engineering fields such as inertial confinement fusion.In this study,the effect of relaxation time on the RM instability under reshock impact is investigated using a two-component discrete Boltzmann method.The hydrodynamic and thermodynamic characteristics of the fluid system are comprehensively analyzed from the perspectives of the density gradient,vorticity,kinetic energy,mixing degree,mixing width and non-equilibrium intensity.Simulation results indicate that for longer relaxation time,the diffusion and dissipation are enhanced,the physical gradients decrease,and the growth of the interface is suppressed.Furthermore,the non-equilibrium manifestations show complex patterns,driven by the competitive physical mechanisms of the diffusion,dissipation,shock wave,rarefaction wave,transverse wave and fluid instabilities.These findings provide valuable insight into the fundamental mechanism of compressible fluid flows.
基金supported by National Natural Science Foundation of China(Grant No.42377149)the Research Grants Council of Hong Kong(General Research Fund Project No.17202423).
文摘In this study,a powerful thermo-hydro-mechanical(THM)coupling solution scheme for saturated poroelastic media involving brittle fracturing is developed.Under the local thermal non-equilibrium(LTNE)assumption,this scheme seamlessly combines the material point method(MPM)for accurately tracking solid-phase deformation and heat transport,and the Eulerian finite element method(FEM)for effectively capturing fluid flow and heat advection-diffusion behavior.The proposed approach circumvents the substantial challenges posed by large nonlinear equation systems with the monolithic solution scheme.The staggered solution process strategically separates each physical field through explicit or implicit integration.The characteristic-based method is used to stabilize advection-dominated heat flows for efficient numerical implementation.Furthermore,a fractional step approach is employed to decompose fluid velocity and pressure,thereby suppressing pore pressure oscillation on the linear background grid.The fracturing initiation and propagation are simulated by a rate-dependent phase field model.Through a series of quasi-static and transient simulations,the exceptional performance and promising potential of the proposed model in addressing THM fracturing problems in poro-elastic media is demonstrated.
基金Project (50871028) supported by the National Natural Science Foundation of ChinaProjects (N100702001,N090502002) supported by the Fundamental Research Funds for the Central Universities,China+1 种基金Project (NCET-09-0272) supported by the Program for New Century Excellent Talents in University of Ministry of Education, ChinaProject (200803) supported by Northeastern University Research Foundation for Doctor Candidates,China
文摘The thermodynamic re-assessment of Au-Pt binary system was carried out by using the Calphad method and based on the recent experimental data. The Gibbs energies of face-centred cubic and liquid phases were described by a sub-regular solution model with the Redlich-Kister equation. Much effort was taken to reproduce the phase equilibrium results and thermodynamic properties of the solid phase, including the activity and mixing enthalpy. The constraint of the third law of thermodynamics was also considered in the assessment. According to the presently assessed results, the miscibility gap region in the Au-Pt system slightly shifts to the Au-rich side, and the critical !0oint of the miscibility gap is about 1200 ℃ and Au-56% Pt.
基金supported by the National Basic Research Program of China (2009CB226103, 2009CB219902)Swedish Research Councilgrateful to the support by the 363rd Session of Xiangshan Science Conferences, "Scientific Issues of Energy Conservation Mechanism for Waste-decreasing Process"
文摘In this paper, the methodology of non-equilibrium thermodynamics is introduced for kinetics research of CO2 capture by ionic liquids, and the following three key scientific problems are proposed to apply the methodology in kinetics research of CO2 capture by ionic liquids: reliable thermodynamic models, interfacial transport rate description and accurate experimental flux. The obtaining of accurate experimental flux requires reliable experimental kinetics data and the effective transport area in the CO2 capture process by ionic liquids. Research advances in the three key scientific problems are reviewed systematically and further work is analyzed. Finally, perspectives of non-equilibrium thermodynamic research of the kinetics of CO2 capture by ionic liquids are proposed.
