An idea on interfacial equilibrium-potential differences () which are generated for the extraction of univalent metal picrate (MPic) and divalent ones (MPic2) by crown ethers (L) into high-polar diluents was improved....An idea on interfacial equilibrium-potential differences () which are generated for the extraction of univalent metal picrate (MPic) and divalent ones (MPic2) by crown ethers (L) into high-polar diluents was improved. These potentials were clarified with some experimental extraction-data reported before on the M = Ag(I), Ca(II), Sr(II) and Ba(II) extraction with 18-crown-6 ether (18C6) and benzo-18C6 into 1,2-dichloroethane (DCE) and nitrobenzene (NB). Consequently, it was demonstrated that the? values from the extraction-experimentally obtained logKD,Pic ones are in agreement with or close to those calculated from charge balance equations in many cases, where the symbol, KD,Pic, denotes an individual distribution constant of Pic﹣ into the DCE or NB phase. Also, it was experimentally shown that extraction constants based on the overall extraction equilibria do not virtually contain the? terms in their functional expressions.展开更多
This paper stuides the elastic constants and some thermodynamic properties of Mg2SixSn1-x （x = 0, 0.25, 0.5, 0.75, 1） compounds by first-principles total energy calculations using the pseudo-potential plane-waves ap...This paper stuides the elastic constants and some thermodynamic properties of Mg2SixSn1-x （x = 0, 0.25, 0.5, 0.75, 1） compounds by first-principles total energy calculations using the pseudo-potential plane-waves approach based on density functional theory, within the generalized gradient approximation for the exchange and correlation potential. The elastic constants of Mg2SixSn1-x were calculated. It shows that, at 273 K, the elastic constants of Mg2Si and Mg2Sn are well consistent with previous experimental data. The isotropy decreases with increasing Sn content. The dependences of the elastic constants, the bulk modulus, the shear modulus and the Debye temperatures of Mg2Si and Mg2Si0.5Sn0.5 on pressure were discussed. Through the quasi-harmonic Debye model, in which phononic effects were considered, the specific heat capacities of Mg2SixSn1-x at constant volume and constant pressure were calculated. The calculated specific heat capacities are well consistent with the previous experimental data.展开更多
The unifiedΩ-series of the Gauss and Bailey2F1(1/2)-sums will be investigated by utilizing asymptotic methods and the modified Abel lemma on summation by parts.Several remarkable transformation theorems for theΩ-ser...The unifiedΩ-series of the Gauss and Bailey2F1(1/2)-sums will be investigated by utilizing asymptotic methods and the modified Abel lemma on summation by parts.Several remarkable transformation theorems for theΩ-series will be proved whose particular cases turn out to be strange evaluations of nonterminating hypergeometric series and infinite series identities of Ramanujan-type,including a couple of beautiful expressions forπand the Catalan constant discovered by Guillera(2008).展开更多
AgGa1-xInxSe2 polycrystals were synthesized by the method of mechanical oscillation and temperature oscillation. X-ray diffraction spectra of polycrystal powder are conformable with the JCPDS cards. Lattice constants ...AgGa1-xInxSe2 polycrystals were synthesized by the method of mechanical oscillation and temperature oscillation. X-ray diffraction spectra of polycrystal powder are conformable with the JCPDS cards. Lattice constants a and c calculated from the XRD were found to obey Vegard's law. The melting point of AgGa0.8In0.2Se2 obtained by means of differential scanning calorimetry (DSC) is 796.53 ℃. The DSC curve also show that there are no other transformation points below the melting point. The results indicate that polycrystalline materials synthesized by the method mentioned above are high-quality and can be used to grow single crystals by the vertical Bridgman technology.展开更多
Values of the second thermodynamic dissociation constant pK2 of the protonated form of monosodium 1,4-piperazinediethanesulfonate (PIPES) have been determined at twelve different temperatures in the temperature range ...Values of the second thermodynamic dissociation constant pK2 of the protonated form of monosodium 1,4-piperazinediethanesulfonate (PIPES) have been determined at twelve different temperatures in the temperature range from (278.15 to 328.15) K including the body temperature 310.15 K by measurement of the electromotive-force for cells without liquid junction of the type: Pt (s), H2 (g), 101.325 kPa|Na-PIPES (m1) + Na 2-PIPES (m2) + NaCl (m3)|AgCl (s), Ag (s), where m1, m2 and m3 indicate the molalities of the corresponding species at 1 atm = 101.325 kPa in SI units. The pK2 values for the dissociation of Na-PIPES are represented by the equation: pK2 = -1303.76/T + 48.369 - 6.46889 lnT with an uncertainty of ± 0.001. The values of pK2 for Na-PIPES were found to be 7.1399 ± 0.0004 at 298.15 K and 7.0512 ± 0.0004 at 310.15 K, respectively, and indicate that this buffer would be useful as pH standard in the range of physiological application. Standard thermodynamic quantities for the acidic dissociation process of Na-PIPES have been derived from the temperature coefficients of the pK2. These values are compared with those of structurally related N-substituted PIPERAZINE and TAURINE at 298.15 K.展开更多
The structural, elastic, and thermodynamic properties of cubic-Fe2TiA1 under high temperatures and pressures are investigated by performing ab initio calculation and using the quasi-harmonic Debye model. Some ground s...The structural, elastic, and thermodynamic properties of cubic-Fe2TiA1 under high temperatures and pressures are investigated by performing ab initio calculation and using the quasi-harmonic Debye model. Some ground state properties such as lattice constant, bulk modulus, pressure derivative of the bulk modulus, and elastic constants are in good agreement with the available experimental results and theoretical data. The thermodynamic properties of Fe2TiA1 such as thermal expansion coefficient, Debye temperature, and heat capacity in ranges of 0 K-1200 K and 0 GPa-250 GPa are also obtained. The calculation results indicate that the heat capacities at different pressures all increase with temperature increasing and are close to the Dulong-Petit limit at higher temperatures, Debye temperature decreases with temperature increasing, and increases with pressure rising. The cubic-FezTiA1 is stable mechanically under 250 GPa. Moreover, under lower pressure, thermal expansion coefficient rises rapidly with temperature increasing, and the increasing rate becomes slow at higher pressure.展开更多
Ab initio electronic structure calculations at 6 31G ** level were performed to determine the mechanism of the isomerization reaction from 1,2 butadiene to 1,3 butadiene. The MP2 method was used to improve the barrier...Ab initio electronic structure calculations at 6 31G ** level were performed to determine the mechanism of the isomerization reaction from 1,2 butadiene to 1,3 butadiene. The MP2 method was used to improve the barrier energies of the reaction. The calculation results show that the reaction is a stepwise process via a radical INT; the barrier energies determined for TS1 and TS2 at UMP2/6 31G ** //UHF/6 31G ** +ZPE level are 64 95×4.184 and 64.10×4.184 kJ/mol, respectively. Based on the unified statistical theory, the thermal rate constants for the present complex reaction mechanism were computed over the termperature range 1 100\1 600 K. The computed thermal rate constants for the reaction are well represented by the following Arrhenius expression: k（T）=2.4×10 13 exp （-62 8 kJ/RT） s -1 . The theoretical investigations are found to be in quantitative agreement with the experimental results.展开更多
文摘An idea on interfacial equilibrium-potential differences () which are generated for the extraction of univalent metal picrate (MPic) and divalent ones (MPic2) by crown ethers (L) into high-polar diluents was improved. These potentials were clarified with some experimental extraction-data reported before on the M = Ag(I), Ca(II), Sr(II) and Ba(II) extraction with 18-crown-6 ether (18C6) and benzo-18C6 into 1,2-dichloroethane (DCE) and nitrobenzene (NB). Consequently, it was demonstrated that the? values from the extraction-experimentally obtained logKD,Pic ones are in agreement with or close to those calculated from charge balance equations in many cases, where the symbol, KD,Pic, denotes an individual distribution constant of Pic﹣ into the DCE or NB phase. Also, it was experimentally shown that extraction constants based on the overall extraction equilibria do not virtually contain the? terms in their functional expressions.
基金supported by the National Natural Science Foundation of China(Grant No 50504002)China Postdoctoral Science Foundation(Grant No 20060390030)the Scientific Research Foundation for the Returned Overseas Chinese Scholars,State Education Ministry,China
文摘This paper stuides the elastic constants and some thermodynamic properties of Mg2SixSn1-x （x = 0, 0.25, 0.5, 0.75, 1） compounds by first-principles total energy calculations using the pseudo-potential plane-waves approach based on density functional theory, within the generalized gradient approximation for the exchange and correlation potential. The elastic constants of Mg2SixSn1-x were calculated. It shows that, at 273 K, the elastic constants of Mg2Si and Mg2Sn are well consistent with previous experimental data. The isotropy decreases with increasing Sn content. The dependences of the elastic constants, the bulk modulus, the shear modulus and the Debye temperatures of Mg2Si and Mg2Si0.5Sn0.5 on pressure were discussed. Through the quasi-harmonic Debye model, in which phononic effects were considered, the specific heat capacities of Mg2SixSn1-x at constant volume and constant pressure were calculated. The calculated specific heat capacities are well consistent with the previous experimental data.
文摘The unifiedΩ-series of the Gauss and Bailey2F1(1/2)-sums will be investigated by utilizing asymptotic methods and the modified Abel lemma on summation by parts.Several remarkable transformation theorems for theΩ-series will be proved whose particular cases turn out to be strange evaluations of nonterminating hypergeometric series and infinite series identities of Ramanujan-type,including a couple of beautiful expressions forπand the Catalan constant discovered by Guillera(2008).
文摘AgGa1-xInxSe2 polycrystals were synthesized by the method of mechanical oscillation and temperature oscillation. X-ray diffraction spectra of polycrystal powder are conformable with the JCPDS cards. Lattice constants a and c calculated from the XRD were found to obey Vegard's law. The melting point of AgGa0.8In0.2Se2 obtained by means of differential scanning calorimetry (DSC) is 796.53 ℃. The DSC curve also show that there are no other transformation points below the melting point. The results indicate that polycrystalline materials synthesized by the method mentioned above are high-quality and can be used to grow single crystals by the vertical Bridgman technology.
文摘Values of the second thermodynamic dissociation constant pK2 of the protonated form of monosodium 1,4-piperazinediethanesulfonate (PIPES) have been determined at twelve different temperatures in the temperature range from (278.15 to 328.15) K including the body temperature 310.15 K by measurement of the electromotive-force for cells without liquid junction of the type: Pt (s), H2 (g), 101.325 kPa|Na-PIPES (m1) + Na 2-PIPES (m2) + NaCl (m3)|AgCl (s), Ag (s), where m1, m2 and m3 indicate the molalities of the corresponding species at 1 atm = 101.325 kPa in SI units. The pK2 values for the dissociation of Na-PIPES are represented by the equation: pK2 = -1303.76/T + 48.369 - 6.46889 lnT with an uncertainty of ± 0.001. The values of pK2 for Na-PIPES were found to be 7.1399 ± 0.0004 at 298.15 K and 7.0512 ± 0.0004 at 310.15 K, respectively, and indicate that this buffer would be useful as pH standard in the range of physiological application. Standard thermodynamic quantities for the acidic dissociation process of Na-PIPES have been derived from the temperature coefficients of the pK2. These values are compared with those of structurally related N-substituted PIPERAZINE and TAURINE at 298.15 K.
基金supported by the Advanced Research Foundation,China(Grant No.20100210)
文摘The structural, elastic, and thermodynamic properties of cubic-Fe2TiA1 under high temperatures and pressures are investigated by performing ab initio calculation and using the quasi-harmonic Debye model. Some ground state properties such as lattice constant, bulk modulus, pressure derivative of the bulk modulus, and elastic constants are in good agreement with the available experimental results and theoretical data. The thermodynamic properties of Fe2TiA1 such as thermal expansion coefficient, Debye temperature, and heat capacity in ranges of 0 K-1200 K and 0 GPa-250 GPa are also obtained. The calculation results indicate that the heat capacities at different pressures all increase with temperature increasing and are close to the Dulong-Petit limit at higher temperatures, Debye temperature decreases with temperature increasing, and increases with pressure rising. The cubic-FezTiA1 is stable mechanically under 250 GPa. Moreover, under lower pressure, thermal expansion coefficient rises rapidly with temperature increasing, and the increasing rate becomes slow at higher pressure.
文摘Ab initio electronic structure calculations at 6 31G ** level were performed to determine the mechanism of the isomerization reaction from 1,2 butadiene to 1,3 butadiene. The MP2 method was used to improve the barrier energies of the reaction. The calculation results show that the reaction is a stepwise process via a radical INT; the barrier energies determined for TS1 and TS2 at UMP2/6 31G ** //UHF/6 31G ** +ZPE level are 64 95×4.184 and 64.10×4.184 kJ/mol, respectively. Based on the unified statistical theory, the thermal rate constants for the present complex reaction mechanism were computed over the termperature range 1 100\1 600 K. The computed thermal rate constants for the reaction are well represented by the following Arrhenius expression: k（T）=2.4×10 13 exp （-62 8 kJ/RT） s -1 . The theoretical investigations are found to be in quantitative agreement with the experimental results.
