Thermodynamic properties of germanium and lead tellurites

The temperature dependence of the molar heat capacities of the tellurites PbTeO₃, Pb₂Te₃O₈ and Ge(TeO₃)₂ are determined. By statistical manipulation of the values obtained, the parameters in the equations for the corresponding compounds showing this dependence are determined using the least-squares method. These equations and the standard molar entropies are used to determine the thermodynamic functions Δ₀ ^T S _m ⁰ , Δ_T ^T H _m ⁰ and (Φ_m ⁰+Δ₀ ^T H _m ⁰/T) for T'=298.15 K.     

Vibrational properties of sodium microclusters

The structural and vibrational properties of Na_n (n=2–8) microclusters at very low temperature (T≈0.1 K) are analyzed by tight-binding molecular dynamics simulations. By using the Fourier transform of the velocity autocorrelation function from the trajectories of tight-binding molecular dynamics, the present model is successful in predicting some of the experimental, far infrared spectra and agrees very well with a standard finite difference harmonic method and some other more sophisticated calculations.     

Thermodynamic and transport properties of argon/carbon and helium/carbon mixtures in fullerene synthesis

The equilibrium composition and thermodynamic and transport properties of argon; carbon and helium/carbon mixtures are calculated in the temperature range 300–20,000 K. The curves for the composition of mixtures of 50%, carbon in argon or helium are shown fir a pressure of 1.33 × 10⁴ Pa. The calculations for the heat capacity at constant pressure (C_p) and transport coefficients are validated with other studies, for the cases or pure argon and pure helium at a pressure of 10⁵ Pa. The properties of mixtures with various proportions of carbon in argon and helium are calculated. Results are presented at pressures of 105 and 1.33 × 10⁴ Pa, typical of reactors for the synthesis of fullerenes and nanotubes. It is observed that the properties of carbon and mixtures of carbon with a buffer gas (argon or helium) are very different from those of the buffer gas, thus the need to consider this effect in simulations. In general, the mixtures follow trends intermediate to those of the pure gases from which they are composed except for the thermal conductivity which shows a deviation from this tendency in the region between 11,500 and 19,000 K for argon/carbon mixtures and between 8,000 and 12,000 K for helium/carbon mixtures. Also, the electrical conductivity of mixtures of low carbon concentration is very close to that ofpure carbon. A datafile containing the transport properties of mixtures for pressures between 10⁴ and 10⁵ Pa is available free of charge from the authors.     

Evolution of bulk-like properties in mercury microclusters

The transition from non-metallic to metallic behavior of mercury microclusters, Hg _n , withn ranging from 2 to 79, is investigated using first principles tight-binding linear muffin-tin orbital method. Then dependence of the ionization potential, the cohesive energy, the energy gap, and the nature of the bonding indicates metallic behavior for Hg _n withn≧80. The average bond length of Hg clusters is found to be larger than that of the bulk. Our results are in good agreement with experiments.     

Structural and dynamical properties of magnesium microclusters

We present systematic Density Functional Theory-Local Density Approximation computations for neutral Magnesium clusters Mg _n withn≤13. For the smaller sizes the ground state structure is optimized starting from selected symmetries and allowing for relaxation, Jahn-Teller distorsion and spin polarization. For the larger sizes we perform a simulated annealing based on the ab-initio Molecular Dynamics. By the same method, we study the thermal and dynamical properties of Mg₁₀ and Mg₁₆. The general picture emerging from these computations shows that already atn ≈10 these clusters have acquired many characteristic features of metallic Magnesium.     

多体展开势能函数在碳族元素原子簇研究中的应用III. 锗原子族的结构和相对稳定性

基于从晶体锗确立的多体展开势能函数, 本文通过坐标完全优化, 发现小的锗原子簇分子(Ge~2~Ge~14)倾向于形成密堆积结构, 表面原子分布以蝶形四元环(D~2d)为主; 常见立方晶体“微观晶体碎片”的分层优化结果表明, 在Ge~15~Ge~100范围内, 多数壳层的原子到分子中心的距离均受到压缩, 且以畸变的简单立方、面心立方及体心立方较为稳定; 在这些畸变密堆积结构中, 表面原子向内压缩最为严重, 使整个分子趋于球形化。较为开放的金刚石类层状原子族只有当所含原子数达数百以上时才可能相对更为稳定。     

Thermodynamic properties of liquid mixtures of carbon monoxide and methane

The equations of state of liquid methane at 125.00 K and of six liquid mixtures of carbon monoxide and methane at 116.30, 120.00 and 125.00 K have been measured from just above the saturation vapour pressure to the freezing pressure of methane. The results show that the excess volume V^E is large and negative at low pressures but becomes less negative as the pressure is increased, being almost zero at the highest pressures. The curve of V^E against the mole fraction x is very asymmetrical at low pressures, but becomes more symmetrical with rising pressure.The effect of pressure on the excess functions G^E, H^E and T·S^E has been calculated. H^E and T·S^E prove to be much more sensitive to pressure than G^E.Conformal solution theory, in the van der Waals one-fluid form, reproduces the experimental results very successfully.     

Thermodynamic and physical properties of carbon tetrachloride + sulfolane mixtures

The solid + liquid phase diagram, drawn from thermal and dielectric measurements, is presented. It exibits a miscibility gap at 0.08 ≤ χ₂ ≤ 0.58, and two eutectics. The occurrence of a (likely 1:1) intermediate compound, which decomposes on melting into two immiscible liquids, is postulated. Mixed crystals are observed in the sulfolane richer region.Deviations of the liquid mixtures from ideality, positive in the case of viscosity and negative in the case of dielectric constants, are evidenced.     

Thermodynamic and transport properties of carbon dioxide from molecular simulation

Monte Carlo and molecular dynamics simulations have been used in order to test the ability of a three center intermolecular potential for carbon dioxide to reproduce literature experimental thermophysical values. In particular, both the shear viscosity under supercritical conditions and along the phase coexistence line, as well as the thermal conductivity under supercritical conditions, have been calculated. Together with the already reported excellent agreement for the phase coexistence densities, the authors find that the agreement with experimental values is, in general, good, except for the thermal conductivity at low density. Although extended versions of the model were employed, which include an explicit account of bending and vibrational degrees of freedom, a significant difference was still found with respect to the reported experimental value.     

Thermodynamic properties of dilute solutions of carbon monoxide in a hydrocarbon

Partial molar volumes, enthalpies, entropies, and energies have been obtained for dilute solutions of carbon monoxide in liquid benzene and in liquid n-octane up to 523 K and 15 MPa. As for (hydrogen + a hydrocarbon), the ratio $\text{a}{}_{12}\text{a}{}_{11}$ of the cohesive energy densities is independent of hydrocarbon type.     

Thermodynamic properties of carbon dioxide derived from the speed of sound

Thermodynamic properties of CO₂ are derived from speed of sound in the temperature range 300 to 360 K (from 0 to 6 MPa), and 300 to 220 K (from 0 to 90% of the saturation pressure). The density, the specific heat capacity at constant pressure, and the specific heat capacity at constant volume are obtained by numerical integration of differential equations connecting the speed of sound with other thermodynamic properties. The set of differential equations is solved as the initial value problem, with the initial values specified along the isotherm at 300 K in terms of several accurate values of the density and the specific heat capacity at constant pressure. The density, the specific heat capacity at constant pressure and the specific heat capacity at constant volume are derived with the absolute average deviations of 0.018%, 0.19%, and 0.18%, respectively. The results of numerical integration are extrapolated to the saturation line for ρ, c _p , and c _v with the absolute average deviations of 0.056%, 2.31%, and 1.32%, respectively.     

Melting of gold microclusters

The transition from solid-like to liquid-like behavior in Au _n ,n=6, 7, 13, clusters is studied using molecular dynamics simulations. A Gupta-type potential with all-neighbour interactions is employed to incorporaten-body effects. The melting-like transition is described in terms of short-time averages of the kinetic energy per particle, root-mean-square bond length fluctuations and mean square displacements. A comparison between melting temperatures of Au _n and Ni _n clusters is presented.     

Thermodynamic functions of gaseous beryllium,titanium and germanium organometallic molecules

The thermal functions S⁰_T, -(G⁰_T-H⁰_O)/T and (H⁰_T-H⁰_O) have been calculated from structural and spectroscopic data for the gaseous organometallics C₅H₅BeX (X = Cl, Br and BH₄), C₅H₅MX₃ (M = Ti and Ge; X = Cl, Br and I) and CH₃TiX₃ (X = Cl, Br and I). The rotational barriers of the C₅H₅ and CH₃ groups have been evaluated and discussed.     

Thermodynamic properties of hexacosane

The heat capacity of a purified sample of hexacosane, n-C₂₆H₅₄, has been measured from 13 to 358 K. The enthalpies of transition near 325.5 K and fusion at 329.25 K, and the purity of the sample have been determined; the accuracy of the results is influenced by the closeness in temperature, and overlap, of the crystal-to-crystal and crystal-to-liquid phase transitions. Thermodynamic properties have been calculated from the heat capacities and enthalpies.     

Thermodynamic properties of methylvinylsulphide

Enthalpies of the overall decomposition reactions MX₂L₂(c) → MX₂(c) + 2L(g) and of the intermediate stepwise loss of ligand, L, where X is Cl or Br; L is 3-chloropyridine, 3-bromopyridine, 2-chloropyridine, 2-bromopyridine, or 2-methoxypyridine; and M is Mn, Ni, Cu, or Cd have been measured by use of a differential scanning calorimeter. Enthalpies of sublimation of NiCl₂(3-chloropyridine)₂, NiCl₂(3-bromopyridine)₂ and CuCl₂(3-bromopyridine)₂ have been determined. Values of the metal—nitrogen bond dissociation energies in these compounds have been calculated. A value for the specific heat of CuCl₂(2-chloropyridine)₂ is reported.     

Thermodynamic properties of chloropinnoite

The molar enthalpies of solution of 2MgO · 2B₂O₃ · MgCl₂ · 14H₂O in approximately 1 mol · dm⁻³ aqueous hydrochloric acid (HCl) and of MgCl₂ · 6H₂O(s) in aqueous (approximately 1 mol · dm⁻³ HCl + MgCl₂ + H₃BO₃) at T=298.15 K were determined. From a combination of these results with measured enthalpies of solution of boric acid (H₃BO₃) in HCl(aq) and of magnesium oxide (MgO) in aqueous (HCl + H₃BO₃) solution, together with the standard molar enthalpies of formation of MgO(s), H₃BO₃(s), MgCl₂ · 6H₂O(s) and H₂O(l), the standard molar enthalpy of formation of −(8812 ± 3) kJ · mol⁻¹ of 2MgO · 2B₂O₃ · MgCl₂ · 14H₂O was obtained. Thermodynamic properties of this compound were also calculated by group contribution method.     

Thermodynamic properties of tetrachlorocyclopropene

A facility is described which incorporates the use of electronic microbalances to follow gravimetric changes due to the formation or spallation of surface oxides on metals or alloys during high temperature oxidation. The outputs from the balances are fed into a data acquisition system which allows easy collection and analysis of the data from more than one microbalance.The sensitivity of the technique is illustrated by reference to the measurements of oxidation and spallation on a 20Cr/25Ni/Nb stabilised stainless steel oxidised in flowing CO₂ based gas at 1 atmosphere pressure and 850°C.     

Temperature-induced structural transitions and vibrational properties of microclusters: ab-initio molecular dynamics studies

We present the results of ab-initio molecular dynamics studies of selected microclusters of sodium, silicon and magnesium at finite temperatures, and especially discuss those obtained around room temperature. In particular, from the analysis of the atomic trajectories we can identify in some cases the existence of different isomers and the isomerization pathways. We have also calculated vibrational spectra at low temperatures and find that they can be used as a very sensitive structural probe also in sodium clusters, where the electronic properties are quite insensitive to the geometry.