一种确定氧化数的新方法

氧化数是元素的重要性质,在无机化学中应用广泛。长期以来,确定元素氧化数主要根据桐山良一和鲍林等建立的规则,这些规则对于氧化数概念在化学中的推广普及起了很大的作用,但在遇到结构复杂或未知化合物时有时仍然会出现问题。本文根据IUPAC的氧化数定义提出,氧化数完全取决于成键两原子之间的电子供需关系,元素的最高正氧化数受到其原子价层电子数的限制,而元素的最低负氧化数受到同周期稀有气体元素外层电子数与其价层电子数差值的限制,据此建立了确定元素氧化数的新方法,该方法既不需要考虑分子结构,也不依赖元素氧化数的习惯规定,符合氧化数概念提出的初衷,简便易行,例外情况少,不仅适合大学化学教学,也适合中学化学教学。     

Calculations of Two and Three-Body Correlation Entropies at the Freezing Points of Soft-Core Fluids: Effect of the Softness on the Correlation Entropy

Two and three-body correlation entropies of model fluids, in which particles interact each other through the 4th, 6th, 9th and 12th-inverse-power potentials, were calculated from their atomic configurations obtained by molecular dynamics simulations at their freezing points. Besides the soft-core fluid model with the inverse-power potentials, hard-sphere and classical one-component plasma models were employed to provide a comparison with the entropies of the soft-core model. The correlation entropies were plotted as a function of the softness of the potential. These values were also compared with the excess entropies of the hard-sphere and the one-component plasma models at their freezing points.     

Statistical Spectral Analysis of liquid X-ray Diffraction Data

Abstract

The experimental procedure of determining the structure of a liquid by diffraction techniques is reformulated herein as a stochastic experiment subject to the data analysis formalism of statistical spectral analysis. Observed in such an experiment are averaged local microscopic fluctuations from the bulk density. The intensity function then represents a stochastic spectrum and it becomes necessary to statistically estimate a minimum bias, minimum variance covariance function which is the net radial distribution function. A low-pass tapered data window produces such an optimum estimate.     

Microscopic calculation of the magnetic field of neutron stars

Based on the Dirac equation describing an electron moving in a uniform and cylindrically symmetric magnetic field which may be the result of the self-consistent mean field of the electrons themselves in a neutron star, we have obtained the eigen solutions and the orbital magnetic moments of electrons in which each eigen orbital can be calculated. From the eigen energy spectrum we find that the lowest energy level is the highly degenerate orbitals with the quantum numbers pZ=0, n=0, and m≥0. At the ground state, the electrons fill the lowest eigen states to form many Landau magnetic cells and each cell is a circular disk with the radius λfree and the thickness λe, where λfree is the electron mean free path determined by Coulomb cross section and electron density and λe is the electron Compton wavelength. The magnetic moment of each cell and the number of cells in the neutron star are calculated, from which the total magnetic moment and magnetic field of the neutron star can be calculated. The results are compared with the observational data and the agreement is reasonable.     

Excess Molar Enthalpies for Isomeric Chlorobutanes with Isomeric Butanols

Abstract

Excess molar enthalpies for mixtures of each of the isomers of chlorobutane with each of the isomers of butanol were determined at the temperature 298.15 K and atmospheric pressure. Excess molar enthalpies are positive for all the mixtures. The results are discussed in terms of molecular interactions.     

Densities and viscosities of propylene carbonate with aromatic hydrocarbons (benzene, 1,4-dimethylbenzene and ethylbenzene) at 288.15, 298.15 and 308.15 K

Densities and viscosities of the binary mixtures of propylene carbonate with benzene, 1,4-dimethylbenzene and ethylbenzene were measured over the entire mole fraction range at 288.15, 298.15 and 308.15?K. Using the experimental values of densities and viscosities the excess molar volumes and viscosity deviations were calculated. The results were fitted by Redlich–Kister equation. The results were discussed in terms of intermolecular interactions.     

Phase equilibria and excess properties for binary systems in reactive distillation processes Part I. Methyl acetate synthesis

Isothermal vapor–liquid equilibrium (VLE) and excess enthalpy (H^E) data were measured for binary systems required for the design of reactive distillation processes for the methyl acetate production. The isothermal P–x data were measured with the help of a computer-operated static apparatus. A commercial isothermal flow calorimeter was used for the determination of the heats of mixing. Temperature-dependent interaction parameters for the UNIQUAC model were fitted simultaneously to the experimental data from this work and other authors.     

Density functional study of structural and electronic properties of Al<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>P (2 ≤ <Emphasis Type="Italic">n</Emphasis> ≤ 12) clusters

Low-lying equilibrium geometric structures of Phosphorus-doped aluminum cluster Al _n P (n = 2–12) clusters obtained by an all-electron linear combination of atomic orbital approach, within spin-polarized density functional theory, are reported. The binding energy, dissociation energy, and stability of these clusters are studied within the local spin density approximation (LSDA) and the three-parameter hybrid generalized gradient approximation (GGA) due to Becke-Lee-Yang-Parr (B3LYP). Ionization potentials, electron affinities, hardness, and static polarizabilities are calculated for the ground-state structures within the GGA. It is observed that symmetric structures with the P atom occupying a peripheral position are lowest-energy geometries of Al _n P (n = 2, 4–11), while the P impurities of Al₃P and Al₁₂P prefer to occupy internal sites in the aluminum clusters. Generalized gradient approximation extends bond lengths as compared to the LSDA lengths. The odd-even oscillations in the dissociation energy, the second differences in energy, the HOMO–LUMO gaps, the ionization potential, the electron affinity, and the hardness are more pronounced within both GGA and LSDA. The stability analysis based on the energies clearly shows the clusters with an even number of valence electrons are more stable than clusters with odd number of valence electrons.     

On Quantum Phase Transition. II. The Falicov–Kimball Model

The Falicov–Kimball (FK) model⁽¹⁾ involves two types of interacting particles: first the itinerant spinless electrons are quantum particles, secondly the static ions are classical particles. It is striking to see that, despite the simplicity of its hamiltonian, the phase diagram of the FK model is highly sophisticated, moreover it remains in great part conjectural. An antiferromagnetic phase transition was proven for the FK model on a square lattice in the seminal paper of T. Kennedy and E. Lieb.⁽²⁾ This result was extended by Lebowitz and Macris⁽³⁾ to small magnetic field. Then the same result was obtained by using a new method.⁽⁴⁾ The main results of this paper concerns the two dimensional FK model on a square lattice, for which we apply the general results contained in ref. 5. First there exists an effective hamiltonian which is a long range many body Ising model, and which governs the behaviour of the ions. Secondly we compute explicitly the truncated effective hamiltonian up to the fourth order w.r.t. a small parameter (the inverse of the on site energy). Finally we use the classical Pirogov–Sinai theory, to get the hierarchy of the phase diagrams up to the fourth order. More precisely, we show that, when the chemical potential varies, the FK model exhibits, at low temperature, a sequence of phase transitions: first between phases of period two, then of period three, then of period four, and finally of period five. In each case the completeness of the phase diagram is proved. This paper supports the conjecture that the phase diagram of the FK model contains periodic phases outside of a Cantor set.