Existence of Gibbs measures for countable Markov shifts

We prove that a potential with summable variations and finite pressure on a topologically mixing countable Markov shift has a Gibbs measure iff the transition matrix satisfies the big images and preimages property. This strengthens a result of D. Mauldin and M. Urbanski (2001) who showed that this condition is sufficient.

     

Thermodynamic properties of liquid magnesium-nickel alloys

Summary Magnesium vapor pressures were determined over liquid Mg-Ni alloys for compositionsx _Mg>0.65 using an isopiestic method. Data points between 760 and 890°C were evaluated to derive corresponding partial thermodynamic properties. The composition dependence of the magnesium activities in liquid alloys is shown for a temperature of 1073 K. Additionally, it is possible to obtain the shape of the liquidus curve between about 60 and 70 at% Mg from the results of the isopiestic measurements.

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Thermodynamische Eigenschaften flüssiger Mg-Ni Legierungen

Zusammenfassung Magnesiumdampfdrücke wurden mit Hilfe einer isopiestischen Methode über flüssigen Mg-Ni-Legierungen mit einer Zusammensetzungx _Mg>0.65 bestimmt. Aus experimentellen Punkten zwischen 760 und 890°C wurden die entsprechenden partiellen thermodynamischen Eigenschaften abgeleitet. Es wird die Konzentrationsabhängigkeit der Magnesiumaktivitäten in flüssigen Legierungen bei 1073 K gezeigt. Zusätzlich kann aus dem Ergebnis der isopiestischen Messungen der Verlauf der Liquiduskurve zwischen etwa 60 und 70 At% Mg ermittelt werden.

     

HCFC133a的热力学性质的实验研究

l引言替代工质和替代技术的研究，都离不开工质准确而可靠的热物性数据。HFC134a是目前国际上公认的制冷剂CFC12的替代物之一，而HCFC133a是合成替代工质HFC134a过程中的中间产物。为了提纯HFC134a，需要设计分离装置，这就必需知道HCFC133a的热力学性质。但是，目前公开发表的HCFC133a的热力学性质数据很少。本研究的目的就是测量HCFC133a的热力学性质，为HFC134a的合成工艺设计和其它工业应用提供基础的物性数据。2实验装置、实验方法及其可靠性检验本研究工作是在我室于1985年建成，并经过多次改进的定容法PVTX试验台上进…     

ESR study of kinetic acidity of 6-tert-butyl-2-hydroxy-4-triphenylmethylphenoxyl

Thermodynamic and kinetic acidities of 6-tert-butyl-2-hydroxy-4-triphenylmethylphenoxyl during its interaction with triethylamine in toluene have been studied by ESR. It has been shown that the protolysis of this radical is a two-pathway process, since tautomeric transitions, i.e. ammonium ion migration between oxygen atoms of the semiquinone radical anion, have been detected in the reaction products, that is, in contact ion pairs of the corresponding semiquinone radicals.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No 1, pp. 81–84, January, 1993.     

Thermodynamic consistency of data banks

Data sets originated from different sources are typically used simultaneously either in data banks or in data bases of flowsheeting programs. If these data sets concern different kinds of data, they ought to be in accordance with the laws of thermodynamics. This is not assured, however, and in many cases it is not even checked. Methods used for data compilation rely on approximate models, which may bias the residuals.

Two model-free methods are proposed, where the residuals of the thermodynamic differential equations are investigated.

The first method is a χ² test based on a quadratic form of the f residuals, involving variances of the elementary measurements, if they are available.

The second method is a rather sensitive trend/shift analysis of residuals, which does not require the knowledge of error variances.

The examples are the Clausius-Clapeyron equation, a binary vapor-liquid equilibrium data set and a simultaneous treatment of PVT and caloric data.     

Metastable effects on martensitic transformation in SMA (I) recoverable effects by the action of thermodynamic forces in parent phase

Summary The applicability of SMA requires a matching of the properties with the technological needs. The metastability effects and the phase coexistence can produce, via atomic diffusion, some changes in the expected properties against time. The careful analysis of the external thermodynamic forces (stress) on the parent phase of a Cu-Al-Zn single crystal alloy establishes a proportional minor change in critical transformation stress (near 1 per cent of the external stress). Via the Clausius-Clapeyron coefficient, the stress effects show a similar behaviour but faster than the room temperature effects on the transformation temperature M_S. In parent phase, the effect of the thermodynamic force regarded as an M_S shift lies between 10 to 15 percent of temperature change.     

The Influence of the Addition of Nuts on the Thermal and Rheological Properties of Wheat Flour

The aim of the study was to assess the influence of replacing wheat flour with hazelnuts or walnuts, in various amounts, on the thermal and rheological properties of the obtained systems. The research material were systems in which wheat flour was replaced with ground hazelnuts (H) or walnuts (W) in the amount of 5%, 10%, and 15%. The parameters of the thermodynamic gelatinization characteristics were determined by the differential scanning calorimetry method. In addition, the pasting characteristics were determined with the use of a viscosity analyzer and the viscoelastic properties were assessed. Sweep frequency and creep and recovery tests were used to assess the viscoelastic properties of the tested gels. It was found that replacing wheat flour with nuts increased the values of gelatinization temperature, gelatinization, and retrogradation enthalpy, and the degree of retrogradation. The highest viscosity was characteristic of the control sample (2039 mPa·s), and the lowest for the paste with 15% addition of walnuts (1120 mPa·s). Replacing the flour with nuts resulted in a very visible reduction in the viscosity of such systems. In addition, gels based on the systems with the addition of H and W were weak gels (tan δ = G″/G′ > 0.1), and the values of G′ and G″ parameters decreased with the increased share of nuts in the systems. Creep and recovery analysis indicated that the systems in which wheat flour was replaced with hazelnuts were less susceptible to deformation compared to the systems with the addition of W.     

Efficiency of alchemical free energy simulations. II. Improvements for thermodynamic integration

We attempt to optimize the efficiency of thermodynamic integration, as defined by the minimal number of unphysical intermediate states required for the computation of accurate and precise free energy differences. The suitability of various numerical quadrature methods is tested. In particular, we compare the trapezoidal rule, Simpson's rule, Gauss-Legendre, Gauss-Kronrod-Patterson, and Clenshaw-Curtis integration, as well as integration based on a cubic spline approximation of the integrand. We find that Simpson's rule and spline integration are already significantly more efficient that the trapezoidal rule, i.e., correct free energy differences can be obtained using fewer λ-states. We demonstrate that Simpson's rule can be used advantageously with nonequidistant values of the abscissa, which increases the flexibility of the method. Efficiency is enhanced even further if higher order methods, such as Gauss-Legendre, Gauss-Kronrod-Patterson, or Clenshaw-Curtis integration, are used; no more than seven λ-states, which in the case of Clenshaw-Curtis integration include the physical end states, were required for accurate results in all test problems studied. Thus, the performance of thermodynamic integration can equal that of Bennett's acceptance ratio method. We also show, however, that the high efficiency found here relies on the particular functional form of the soft-core potential used; overall, thermodynamic integration is more susceptible to the details of the hybrid Hamiltonian used than Bennett's acceptance ratio method. Therefore, we recommend Bennett's acceptance ratio method as the most robust method to compute alchemical free energy differences; nevertheless, scenarios when thermodynamic integration may be preferable are discussed.     

Soft-core potentials in thermodynamic integration: comparing one- and two-step transformations

Molecular dynamics-based free energy calculations allow the determination of a variety of thermodynamic quantities from computer simulations of small molecules. Thermodynamic integration (TI) calculations can suffer from instabilities during the creation or annihilation of particles. This "singularity" problem can be addressed with "soft-core" potential functions which keep pairwise interaction energies finite for all configurations and provide smooth free energy curves. "One-step" transformations, in which electrostatic and van der Waals forces are simultaneously modified, can be simpler and less expensive than "two-step" transformations in which these properties are changed in separate calculations. Here, we study solvation free energies for molecules of different hydrophobicity using both models. We provide recommended values for the two parameters α(LJ) and β(C) controlling the behavior of the soft-core Lennard-Jones and Coulomb potentials and compare one- and two-step transformations with regard to their suitability for numerical integration. For many types of transformations, the one-step procedure offers a convenient and accurate approach to free energy estimates.     

Theoretical Studies on the Molecular Structures and Thermodynamic Properties of Polychlorinated Acenaphthylenes

Geometric structures of 135 polychlorinated acenaphthylene (PCAC) molecules were optimized using density functional theory (DFT) at the B3LYP/6-311G** level and some thermodynamic properties of them in the ideal gas state were calculated. The relations of these thermodynamic properties with the number and position of chlorine atoms were also explored, from which the relative stability of PCAC congeners was theoretically proposed according to the magnitude of the relative standard Gibbs free energy of formation (△r,fGθ). The results show that all PCAC isomers have planar geometric configuration. There exists intramolecular Cl···Cl weak interaction in some PCAC molecules. The change of △fHθ and fGθ of most stable PCAC isomers with increasing the number of chlorine atoms is different from that in the least stable PCAC congeners. The values of fHθ and fGθ for PCAC isomers with the same number of chlorine atoms show a strong dependence on the position of chlorine atoms and the relative stability of PCAC congeners has close relation with the intramolecular Cl···Cl nuclear repulsive interaction.