Densities and excess molar volumes for binary mixtures of N,N-dimethylformamide+ 1,2-dimethoxyethane

Densities are reported for N,N-dimethylformamide and 1,2-dimethoxyethane binary mixtures at different mole fractions covering the whole miscibility range and at 19 temperatures ranging from –10 to 80°C. The experimental density data have been fitted by empirical relations and the excess volumes by a Redlich-Kister equation. The 11 N,N-dimethylformamide and 1,2-dimethoxyethane adduct appears to be stable throughout the temperature range. A comparison with other DMF containing mixtures is made.     

Densities, refractive indices and speeds of sound of the ternary mixtures (dimethyl carbonate + methanol + ethanol) and (dimethyl carbonate + methanol + 1-propanol) at T=298.15 K

Density, refractive index and speed of sound at T=298.15 K and atmospheric pressure have been measured over the entire composition range for (dimethyl carbonate (DMC) + methanol + ethanol) and (DMC + methanol + 1-propanol). Excess molar volumes, changes of refractive index on mixing and deviations in isentropic compressibility for the above systems have been calculated. The calculated quantities are further fitted to the Cibulka equation to estimate the ternary fitting parameters. Standard deviations from the regression lines are shown.     

Refractive Indices, Densities and Excess Molar Volumes of Monoalcohols + Water

The refractive index, n _D , and density, ρ, of binary mixtures of monoalcohols + water, have been measured at a temperature of 298.15,K and atmospheric pressure. The variation of the refractive indices of these solutions has also been determined with temperature in the range T = (278.15 to 338.15) K and atmospheric pressure. A comparative study has been made of the refractive indices obtained experimentally and those calculated by means of the Lorentz-Lorenz [Theory of Electrons, Dover Phoenix (1952)] and Gladstone-Dale relations [Trans. R. Soc. London 148:887–902 (1858)]; in all cases, the Gladstone–Dale equation was seen to afford values similar to those obtained experimentally. Calculations have been made of the excess molar volumes, V ^E, and the molar refraction deviations, ΔR, of these mixtures and the differences between the experimental values for refractive index and those obtained by means of the Gladstone–Dale equation. Values of V ^E were compared with others in the literature. In all cases the V ^E values were negative, and in all cases, except in the methanol + water, ΔR showed a maximum for x = 0.8.     

Atomistic Modeling of Silica Based Sol-Gel Processes

Density Functional Theory is used to study water, methanol, ethanol, TMOS, and TEOS molecules and the most important silica clusters participating in sol-gel processes. Calculated bond lengths, bond angles and electric dipole moments compare well with experimental data. The energy of these molecules is reported and used to discuss the energetics of the hydrolysis and condensation reactions. Molecular Dynamics is employed to simulate liquid water, methanol, ethanol, TMOS, TEOS and experimental sol-gel solutions. Calculated densities and enthalpies of vaporisation compare well with experimental data. Preliminary results are presented for MD simulations of sol-gel solutions.     

低温加氢催化剂的设计: 理论与实践

简要总结了我们在C=C及C=O双键低温加氢双金属催化剂方面的最新研究成果. 首先, 我们以环己烯加氢为探针反应, 证明了平行使用多种研究手段的重要性, 包括单晶表面的基础研究与DFT计算, 多晶表面的合成与表征, 负载型催化剂的制备与性能测试等. 其次, 总结了双金属催化剂在其他加氢反应, 如丙烯醛C=O双键的选择性加氢, 苯的低温加氢, 以及乙炔的选择性加氢等反应中的应用. 最后, 讨论了利用金属碳化物代替贵金属Pt以减少双金属催化剂中Pt用量的可能性.     

氢甲酰化反应溶剂效应的量子化学研究

在B3LYP/6-31G(d, p)(Rh和P采用LANL2DZ + Polar)水平下,利用自洽反应场（SCRF）的Onsager模型,系统研究了C6H12、C6H6、THF、CH2Cl2、CH3OH和H2O（相对介电常数ε分别为2.02、2.25、7.58、8.93、32.63和78.39）六种溶剂对乙烯氢甲酰化反应中各驻点的结构和反应机理的影响.分别在上述溶剂中优化了反应物、产物、中间体和过渡态的结构,并计算了自由能和活化自由能.计算结果表明,不同溶剂对反应势能面上各驻点的结构和能量均有一定的影响,而且随着相对介电常数ε的增加,反应的活化自由能下降.水是以上六种溶剂中最佳的溶剂,这与大量的实验研究结果一致.     

Origin of the Landau-Lifshitz hydrodynamic fluctuations in nonequilibrium systems and a new method for reducing the Boltzmann equation

The Landau-Lifshitz fluctuating fluxes in fluctuating hydrodynamics are derived from the deterministic Boltzmann equation with the aid of a reduction method developed by Fujisaka and Mori. Thus it is shown that the hydrodynamic fluctuations innonequilibrium systems are generated by the reduction of variables from the-space distribution function to its five momentum moments, i.e., the hydrodynamic variables. This differs from the Bixon-Zwanzig and Fox-Uhlenbeck theories, in which the Landau-Lifshitz fluctuating fluxes are derived from the molecular fluctuating force in thestochastic Boltzmann-Langevin equation, which is, however, negligible in nonequilibrium systems. Thus the present method improves the Chapman-Enskog reduction method so as to include the hydrodynamic fluctuations generated by the reduction of variables.Supported in part by the Scientific Research Fund of the Ministry of Education.     

On fluctuations in μ-space

A master equation is derived microscopically to describe the fluctuating motion of the particle density in . space. This equation accounts for the drift motion of particles and is valid for any inhomogeneous gas. The Boltzmann equation is obtained from the first moment of this equation by neglecting the second cumulant (the pair correlation function). The successive moments form coarse-grained BBGKY-like hierarchy equations, in which small spatial regions with r_ij < the force range are smeared out. These hierarchy equations are convenient for investigating the nonequilibrium long-range pair correlation function, which arises mainly from sequences of isolated binary collisions and gives rise to the much-discussed long-time tail and the logarithmic term in the density expansion of transport coefficients. It is shown to have a spatial long tail, like the Coulombic potential, in a steady laminar flow. The stochastic nature of the nonlinear Boltzmann-Langevin equation is also investigated; the random source term is found to be expressed as a linear superposition of Poisson random variables and to become Gaussian in special cases.     

A DFT analysis of the vibrational spectra of nitrobenzene

Raman and FTIR, spectra of nitrobenzene, nb, and its isotopomers, nb-¹⁵N, nb-¹³C₆ and nb-d₅, were obtained and the fundamental vibrational modes assigned with the aid of a B3LYP/6-311+G** calculation, without the need for scaling of the force constants. The changes in vibrational coupling between the nitro and benzene groups upon certain isotopic substitutions are well modelled by the calculation, which is able to reproduce the isotopic shifts in frequencies for the nitro vibrations, as well as changes in IR intensities.     

Dimeric water embedded within a hydrophobic cavity of tetra-(p-tert-butyl)thiacalix[4]arene

X-ray crystallographic analysis and density functional B3LYP/6-31G(d) calculation confirm that dimeric water is embedded within a hydrophobic cavity of tetra-(p-tert-butyl)thiacalix[4]arene and stabilized by hydrogen bondings of aromatic π?H₂O(1) and methyl?H₂O(2) in the dimeric water inclusion complex with binding energies of 1.4 and 0.9 kcal mol⁻¹ respectively, and by hydrogen bonding formed between H₂O(2) and four phenolic OH groups from an adjacent tetra-(p-tert-butyl)thiacalix[4]arene, with binding energy of 3.8-4.2 kcal mol⁻¹.