The use of supercritical-fluid chromatography for determining partial molar volumes of ethyl esters of cis-5,8,11,14,17-eicosapentaenoic acid (EPA) and cis -4,7,10,13,16,19- docosa-hexaenoic acid (DHA) in supercritica...The use of supercritical-fluid chromatography for determining partial molar volumes of ethyl esters of cis-5,8,11,14,17-eicosapentaenoic acid (EPA) and cis -4,7,10,13,16,19- docosa-hexaenoic acid (DHA) in supercritical carbon dioxide is presented and discussed. Partial molar volumes of EPA and DHA esters are obtained from the variation of the retention properties with the density of mobile phase at 313.15 K, 323.15 K, 333.15 K and in the pressure range from 9 MPa to 21 MPa.展开更多
The densities of supercritical CO2-tetrahydrofuran (cosolvent) binary mixture weremeasured at temperatures in range of 308.15 to 323.15 K and at pressure up to 16.5 MPa.The concentrations of tetrahydrofuran were from ...The densities of supercritical CO2-tetrahydrofuran (cosolvent) binary mixture weremeasured at temperatures in range of 308.15 to 323.15 K and at pressure up to 16.5 MPa.The concentrations of tetrahydrofuran were from 0 to 0.57 mol/L.The partial molar volume of tetrahydrofuran was calculated based on the relationship between the density of the mixture and the concentration of the cosolvent.It is observed that the partial molar volume of the cosolvent is negative and the absolute value decreases with increasing pressure and the concentration of the cosolvent.展开更多
The thermodynamical properties of MgCl_2 in KCI-MgCl_2-LiCl molten electrolytes containing MgCl_2 below 0.5 (mole fraction, the same below) have been determined from the interchange energies of two binary systems KCI...The thermodynamical properties of MgCl_2 in KCI-MgCl_2-LiCl molten electrolytes containing MgCl_2 below 0.5 (mole fraction, the same below) have been determined from the interchange energies of two binary systems KCI-MgCl_2 and LiCI-MgCl_2, by means of a model on the assumptions that the electrolytes in the solution are treated as independent particles instead of their ion forms and the interchange energy between the component pair KCI-LiCl is ignored when compared with those of component pairs KCl-MgCl_2 and MgCl_2-LiCl. The interchange energies, wKCl-MgCl_2 and wMgcCl_2-Licl, are obtained as-70000 and -13800 J.mol-1, from the corresponding binary solutions, respectively.展开更多
There are at least two valid approaches to the thermodynamics of electrons in metals. One takes a microscopic view, based on models of electrons in metals and superconductor and uses statistical mechanics to calculate...There are at least two valid approaches to the thermodynamics of electrons in metals. One takes a microscopic view, based on models of electrons in metals and superconductor and uses statistical mechanics to calculate the total thermodynamic functions for the model-based system. Another uses partial molar quantities, which is a rigorous thermodynamic method to analyze systems with components that can cross phase boundaries and is particularly useful when applied to a system composed of interacting components. Partial molar quantities have not been widely used in the field of solid state physics. The present paper will explore the application of partial molar electronic entropy and partial molar electronic heat capacity to electrons in metals and superconductors. This provides information that is complementary information from other approaches to the thermodynamics of electrons in metals and superconductors and can provide additional insight into the properties of those materials. Furthermore, the application of partial molar quantities to electrons in metals and superconductors has direct relevance to long-standing problems in other fields, such as the thermodynamics of ions in solution and the thermodynamics of biological energy transformations. A unifying principle between reversible and irreversible thermodynamics is also discussed, including how this relates to the completeness of thermodynamic theory.展开更多
Vapor-liquid phase equilibrium data of tertpentanol in carbon dioxide were measured at temperatures of 313.4, 323.4, 333.5 and 343.5 K and in the pressure range of 4.56--11.44 MPa. The phase equilibium apparatus used ...Vapor-liquid phase equilibrium data of tertpentanol in carbon dioxide were measured at temperatures of 313.4, 323.4, 333.5 and 343.5 K and in the pressure range of 4.56--11.44 MPa. The phase equilibium apparatus used in the work was a variable-volume high-pressure cell. The experimental data were reasonably correlated with Peng-Robinson equation of state(PR-EOS) together with van der Waals-2 two-parameter mixing rules. Henry's Law constants and partial molar volumes of CO2 at infinite dilution were estimated with Krichevsky-Kasarnovsky equa- tion, and Henry's Law constants increase with increasing temperature, however, partial molar volumes of CO2 at infinite dilution are negative whose magnitudes decrease with temperature. Partial molar volumes of CO2 and tertpentanol in liquid phase at equilibrium were calculated.展开更多
The relaxation time of several ferrocene derivatives was measured, and the internal rotation was discussed. For almost all the derivatives, the degree of the internal rotation was constant in spite of the different mo...The relaxation time of several ferrocene derivatives was measured, and the internal rotation was discussed. For almost all the derivatives, the degree of the internal rotation was constant in spite of the different molecular weights. However, for (triphenylmethyl)ferrocene, the rotation of the unsubstituted ring would be slower due to the bulkiness of the substituent. Furthermore, the derivatives that have a hydroxyl- or acetyl group on the substituent were also discussed. Their rotation would be influenced by the location of these substituents.展开更多
Nine functions of atomic volume interaction have been established. The values of average atomic volumes and lattice constants of Ag-Cu alloys obtained from each V-function are, respectively, equal to each other and in...Nine functions of atomic volume interaction have been established. The values of average atomic volumes and lattice constants of Ag-Cu alloys obtained from each V-function are, respectively, equal to each other and in good agreement with experimental values. But the average atomic volumes of components and the volumes of characteristic atoms obtained from each V-function are different from each other. Only after the correlative study of energy, volume and electronic structure is carried out, can the V-function be correctly chosen, can a knowledge system about the alloys be established, thus providing the base for scientific design of new alloys. The relationships between lattice parameters of metastable phases of Ag-Cu alloys and composition and between average properties and partial molar properties of components are discussed.展开更多
文摘The use of supercritical-fluid chromatography for determining partial molar volumes of ethyl esters of cis-5,8,11,14,17-eicosapentaenoic acid (EPA) and cis -4,7,10,13,16,19- docosa-hexaenoic acid (DHA) in supercritical carbon dioxide is presented and discussed. Partial molar volumes of EPA and DHA esters are obtained from the variation of the retention properties with the density of mobile phase at 313.15 K, 323.15 K, 333.15 K and in the pressure range from 9 MPa to 21 MPa.
基金Project (No. 29633020) supported by the National Natural Sceience Foundation of China
文摘The densities of supercritical CO2-tetrahydrofuran (cosolvent) binary mixture weremeasured at temperatures in range of 308.15 to 323.15 K and at pressure up to 16.5 MPa.The concentrations of tetrahydrofuran were from 0 to 0.57 mol/L.The partial molar volume of tetrahydrofuran was calculated based on the relationship between the density of the mixture and the concentration of the cosolvent.It is observed that the partial molar volume of the cosolvent is negative and the absolute value decreases with increasing pressure and the concentration of the cosolvent.
基金National Natural Science Foundation of China!No.59774028
文摘The thermodynamical properties of MgCl_2 in KCI-MgCl_2-LiCl molten electrolytes containing MgCl_2 below 0.5 (mole fraction, the same below) have been determined from the interchange energies of two binary systems KCI-MgCl_2 and LiCI-MgCl_2, by means of a model on the assumptions that the electrolytes in the solution are treated as independent particles instead of their ion forms and the interchange energy between the component pair KCI-LiCl is ignored when compared with those of component pairs KCl-MgCl_2 and MgCl_2-LiCl. The interchange energies, wKCl-MgCl_2 and wMgcCl_2-Licl, are obtained as-70000 and -13800 J.mol-1, from the corresponding binary solutions, respectively.
文摘There are at least two valid approaches to the thermodynamics of electrons in metals. One takes a microscopic view, based on models of electrons in metals and superconductor and uses statistical mechanics to calculate the total thermodynamic functions for the model-based system. Another uses partial molar quantities, which is a rigorous thermodynamic method to analyze systems with components that can cross phase boundaries and is particularly useful when applied to a system composed of interacting components. Partial molar quantities have not been widely used in the field of solid state physics. The present paper will explore the application of partial molar electronic entropy and partial molar electronic heat capacity to electrons in metals and superconductors. This provides information that is complementary information from other approaches to the thermodynamics of electrons in metals and superconductors and can provide additional insight into the properties of those materials. Furthermore, the application of partial molar quantities to electrons in metals and superconductors has direct relevance to long-standing problems in other fields, such as the thermodynamics of ions in solution and the thermodynamics of biological energy transformations. A unifying principle between reversible and irreversible thermodynamics is also discussed, including how this relates to the completeness of thermodynamic theory.
基金Supported by the Youth Key Teacher Foundation of Henan Educational Committee,China(No.2010GGJS-162)
文摘Vapor-liquid phase equilibrium data of tertpentanol in carbon dioxide were measured at temperatures of 313.4, 323.4, 333.5 and 343.5 K and in the pressure range of 4.56--11.44 MPa. The phase equilibium apparatus used in the work was a variable-volume high-pressure cell. The experimental data were reasonably correlated with Peng-Robinson equation of state(PR-EOS) together with van der Waals-2 two-parameter mixing rules. Henry's Law constants and partial molar volumes of CO2 at infinite dilution were estimated with Krichevsky-Kasarnovsky equa- tion, and Henry's Law constants increase with increasing temperature, however, partial molar volumes of CO2 at infinite dilution are negative whose magnitudes decrease with temperature. Partial molar volumes of CO2 and tertpentanol in liquid phase at equilibrium were calculated.
文摘The relaxation time of several ferrocene derivatives was measured, and the internal rotation was discussed. For almost all the derivatives, the degree of the internal rotation was constant in spite of the different molecular weights. However, for (triphenylmethyl)ferrocene, the rotation of the unsubstituted ring would be slower due to the bulkiness of the substituent. Furthermore, the derivatives that have a hydroxyl- or acetyl group on the substituent were also discussed. Their rotation would be influenced by the location of these substituents.
基金Project supported by the Na tional Na tu ral Science Foundation of Chim(Grant No.59371029).
文摘Nine functions of atomic volume interaction have been established. The values of average atomic volumes and lattice constants of Ag-Cu alloys obtained from each V-function are, respectively, equal to each other and in good agreement with experimental values. But the average atomic volumes of components and the volumes of characteristic atoms obtained from each V-function are different from each other. Only after the correlative study of energy, volume and electronic structure is carried out, can the V-function be correctly chosen, can a knowledge system about the alloys be established, thus providing the base for scientific design of new alloys. The relationships between lattice parameters of metastable phases of Ag-Cu alloys and composition and between average properties and partial molar properties of components are discussed.