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
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
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 formalism realised according to the Generalised Approach to Electrolytic Systems (GATES) is presented and applied to typical redox systems known from the laboratory practice. In any redox system, the Generalized E...The formalism realised according to the Generalised Approach to Electrolytic Systems (GATES) is presented and applied to typical redox systems known from the laboratory practice. In any redox system, the Generalized Electron Balance (GEB), perceived as the law of the matter conservation, is derivable from linear combination 2·f(O) – f(H) of elemental balances: f(O) for oxygen and f(H) for hydrogen. It is an equation linearly independent from other (charge and concentration) balances referred to an electrolytic redox system (aqueous media) of any degree of complexity, and named as the primary form of GEB and then denoted as pr-GEB. A compact equation for GEB is obtained from linear combination of 2·f(O) – f(H) with other (charge and concentration) balances. For a non-redox electrolytic system, of any degree of complexity, the balance 2·f(O) – f(H) is not an independent equation. In the derivation of GEB, all known components (species) of the system tested, taken in their real (i.e., hydrated) form, are involved in the balances, and none simplifying assumptions are needed. The redox systems are simulated with use of an iterative computer program.展开更多
The response of ecosystems to perturbations is considered from a thermodynamic perspective by acknowl-edging that, as for all macroscopic systems and processes, the dynamics and stability of ecosystems is sub-ject to ...The response of ecosystems to perturbations is considered from a thermodynamic perspective by acknowl-edging that, as for all macroscopic systems and processes, the dynamics and stability of ecosystems is sub-ject to definite thermodynamic law. For open ecosystems, exchanging energy, work, and mass with the en-vironment, the thermodynamic criteria come from non-equilibrium or irreversible thermodynamics. For ecosystems during periods in which the boundary conditions may be considered as being constant, it is shown that criteria from irreversible thermodynamic theory are sufficient to permit a quantitative prediction of ecosystem response to perturbation. This framework is shown to provide a new perspective on the popula-tion dynamics of real ecosystems.展开更多
Calorimetric Titrations in anhydrous acetonitrile at 298.15K have been performed to give the complex stability constants and thermodynamic properties for the complexation reactions of sodium thiocyanate and potassium ...Calorimetric Titrations in anhydrous acetonitrile at 298.15K have been performed to give the complex stability constants and thermodynamic properties for the complexation reactions of sodium thiocyanate and potassium thiocyanate with dibenzo-18-crown-6(Ⅰ), dibenzo-20-crown-6 (Ⅱ) and dibenzo-22-crown-6(Ⅲ ). The complex stability constanta, reaction enthalpies and (entropies were calculated directly by using calorimeter connected to an CA-033 Ancrocomputer. Data analyses assuming 1:1 stoichiometry were sussessfully applied to all of the crown ether-cation combinations employed. The thermodynamic parameters obtained and examination of CPK molecular models reveal that the less-symmetrical arrangement of donor oxygen induced by increasing methylene in dibenzo-18-crown-6 molecule and lead to an unfavorable conformation for complexation compared with parent crown ether. The complex stability constants are lower than those of dibenzo-18-crown-6(Ⅰ) for the ligands (Ⅱ ) and (Ⅲ) with Na+ and K+ but the relative cation selectivity for K+/Na+ are increased respectively. The effects of molecular structure of benzo crown ether and cation diameter upon complex stability are discussed from a viewpoint of thermodynamics.展开更多
The reactions between sodium iodide, potassium iodide and a series of N-(parasubstituted phenyl) nitrogen-hetero-15-crown-5 were studied by titration calorimetry at 25 ℃ in ethanol. It was found that the aza-crown et...The reactions between sodium iodide, potassium iodide and a series of N-(parasubstituted phenyl) nitrogen-hetero-15-crown-5 were studied by titration calorimetry at 25 ℃ in ethanol. It was found that the aza-crown ethers and the alkali metal ions form 1:1complexes. The electron-donating substituent on the phenyl ring may enhance the ligation ability of the macrocyclic ligand. It was found that linear thermodynamic function relationships exist in the systems studied.展开更多
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.
文摘The formalism realised according to the Generalised Approach to Electrolytic Systems (GATES) is presented and applied to typical redox systems known from the laboratory practice. In any redox system, the Generalized Electron Balance (GEB), perceived as the law of the matter conservation, is derivable from linear combination 2·f(O) – f(H) of elemental balances: f(O) for oxygen and f(H) for hydrogen. It is an equation linearly independent from other (charge and concentration) balances referred to an electrolytic redox system (aqueous media) of any degree of complexity, and named as the primary form of GEB and then denoted as pr-GEB. A compact equation for GEB is obtained from linear combination of 2·f(O) – f(H) with other (charge and concentration) balances. For a non-redox electrolytic system, of any degree of complexity, the balance 2·f(O) – f(H) is not an independent equation. In the derivation of GEB, all known components (species) of the system tested, taken in their real (i.e., hydrated) form, are involved in the balances, and none simplifying assumptions are needed. The redox systems are simulated with use of an iterative computer program.
文摘The response of ecosystems to perturbations is considered from a thermodynamic perspective by acknowl-edging that, as for all macroscopic systems and processes, the dynamics and stability of ecosystems is sub-ject to definite thermodynamic law. For open ecosystems, exchanging energy, work, and mass with the en-vironment, the thermodynamic criteria come from non-equilibrium or irreversible thermodynamics. For ecosystems during periods in which the boundary conditions may be considered as being constant, it is shown that criteria from irreversible thermodynamic theory are sufficient to permit a quantitative prediction of ecosystem response to perturbation. This framework is shown to provide a new perspective on the popula-tion dynamics of real ecosystems.
文摘Calorimetric Titrations in anhydrous acetonitrile at 298.15K have been performed to give the complex stability constants and thermodynamic properties for the complexation reactions of sodium thiocyanate and potassium thiocyanate with dibenzo-18-crown-6(Ⅰ), dibenzo-20-crown-6 (Ⅱ) and dibenzo-22-crown-6(Ⅲ ). The complex stability constanta, reaction enthalpies and (entropies were calculated directly by using calorimeter connected to an CA-033 Ancrocomputer. Data analyses assuming 1:1 stoichiometry were sussessfully applied to all of the crown ether-cation combinations employed. The thermodynamic parameters obtained and examination of CPK molecular models reveal that the less-symmetrical arrangement of donor oxygen induced by increasing methylene in dibenzo-18-crown-6 molecule and lead to an unfavorable conformation for complexation compared with parent crown ether. The complex stability constants are lower than those of dibenzo-18-crown-6(Ⅰ) for the ligands (Ⅱ ) and (Ⅲ) with Na+ and K+ but the relative cation selectivity for K+/Na+ are increased respectively. The effects of molecular structure of benzo crown ether and cation diameter upon complex stability are discussed from a viewpoint of thermodynamics.
文摘The reactions between sodium iodide, potassium iodide and a series of N-(parasubstituted phenyl) nitrogen-hetero-15-crown-5 were studied by titration calorimetry at 25 ℃ in ethanol. It was found that the aza-crown ethers and the alkali metal ions form 1:1complexes. The electron-donating substituent on the phenyl ring may enhance the ligation ability of the macrocyclic ligand. It was found that linear thermodynamic function relationships exist in the systems studied.