Comparative thermodynamic study of GaSb-Sn system

The results of comparative thermodynamic study of GaSb-Sn system are presented in this paper. Calorimetric measurements according to Oelsen's method and EMF measurements with zirconia as solid electrolyte were used for experimental investigation, while Chou's general solution model, Toop, Kohler and Muggianu methods were used for predicting thermodynamic characteristics in this system. Also, phase diagram of this quasibinary system, determined by DTA and optical microscopy, is presented. This revised version was published online in July 2006 with corrections to the Cover Date.     

Comparative thermodynamic analysis of the Pb-Au0.7Sn0.3 section in the Pb-Au-Sn ternary system

The results of comparative thermodynamic analysis of Pb-Au_0.7Sn_0.3 section in Pb-Au-Sn system are presented in this paper. Investigation was done comparatively by calorimetric measurements and thermodynamic calculation according to the general solution model. Thermodynamic parameters, such as partial and integral molar quantities, were determined at different temperatures. The comparison between experimental and calculated results showed mutual agreement. Demixing tendency of lead, presented in the positive deviation from ideal behavior, was confirmed through the study of concentration fluctuation in the long-wavelength limit. Also, chosen alloys in the investigated section were characterized using SEM-EDX analysis.     

Comparative thermodynamic investigation of binary Ga-Bi system; Experimental determination of enthalpies of mixing and activity estimation for liquid Ga-Bi alloys

The results of experimental and analytical thermodynamic investigation of binary Ga-Bi system are presented in this paper. Integral molar enthalpies of mixing for liquid Ga-Bi alloys were obtained using quantitative differential thermal analysis. Activities of bismuth in the entire composition range and temperature interval 573-1073 K, were calculated by Zhang-Chous method for binary systems having two liquid or solid coexisting phases in combination with other Chous method developed for simple eutectic systems. Activities of gallium were derived from Gibbs-Duhem equation. Comparison between experimental, calculated values and existing literature data shows good agreement.     

Phase diagram investigation and thermodynamic study of Os-B system

The constitution of the Os-B system was investigated in this work. The phase regions were determined by metallographic investigations. The existence of the following borides was confirmed: OsB_1.1 (hex.), Os₂B₃ (hex.) and OsB₂ (orthorh.), while the new high temperature Os₂B₃ compound with a not yet identified structure was observed. OsB_1.1 melts congruently at 1820±15°C and OsB₂ at 1870±15°C, while the solid solubility of B in Os was found to be less than 0.5 at%B. Considering thermodynamic study of this system, the activities and activity coefficients for osmium and boron were determined in temperature interval 3300-3500 K, based on the known liquidus and solidus lines from phase diagram, according to calculation procedure given by Rao and Belton. This revised version was published online in July 2006 with corrections to the Cover Date.     

Surface composition of PdCuAu ternary alloys: a combined LEIS and XPS study

PdCuAu ternary alloy samples with different composition were synthesized on top of ZrO₂‐modified porous stainless steel disks by the sequential electroless deposition technique. The structure, morphology and bulk composition of the samples were characterized by X‐ray diffraction (XRD), scanning electron microscopy and energy dispersive X‐ray spectroscopy (EDX). Complete alloy formation with a pure fcc phase for the Pd₇₁Cu₂₆Au₃, Pd₇₀Cu₂₅Au₅ and Pd₆₇Cu₂₄Au₉ samples and a bcc structure for the Pd₆₂Cu₃₆Au₂ and Pd₆₀Cu₃₇Au₃ samples were obtained upon annealing at 500 °C for 120 h as revealed by XRD. A combination of low‐energy ion scattering (LEIS) and X‐ray photoelectron spectroscopy (XPS) was used to investigate the surface properties of the PdCuAu alloys. XPS results confirmed alloy formation under the annealing conditions. XPS analysis also revealed that the near‐surface regions of the alloys became enriched in Pd with respect to the bulk composition determined by EDX. In contrast, LEIS and angle‐resolved XPS analyses showed that the top‐most surface layers in all samples were copper‐rich compared with the bulk composition. This high Cu surface concentration could impart resistance to bulk sulfide formation to the PdCuAu alloy membranes. Copyright © 2015 John Wiley & Sons, Ltd.     

Thermodynamics of liquid Fe-Si and Fe-Ge alloys

The enthalpies of mixing of liquid binary Fe-Ge (1765±5 K) and Fe-Si (1750±5 K) alloys were determined using a high-temperature isoperibolic calorimeter. The thermodynamic properties of Fe-Ge melts were also studied by electromotive force method in the temperature range of 1250-1580 K. The comparison of our measurement results with literature data has been performed. The extreme negative values of integral enthalpy of mixing and alternating-sign deviations from Raoult's low for germanium can be explained by the influence of binary clusters formation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermodynamic properties of liquid Al-Si and Al-Cu alloys

The partial and integral enthalpies of mixing in liquid Al-Si and Al-Cu alloys were determined by high-temperature isoperibolic calorimetry at 1750±5 and 1590±5, respectively. The thermodynamic properties of Al-Si melts were also studied by electromotive force method in temperature range 950-1270 K. The partial and integral excess Gibbs free energies of mixing in liquid Al-Si and Al-Cu alloys were also calculated from literature data on thermodynamic activity of aluminium. The comparison of our experimental results with literature data has been performed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Correlation of thermodynamic modeling and molecular simulations for liquid-liquid equilibrium of ternary polymer mixtures based on a phenomenological scaling method

In our previous study [S.Y. Oh, Y.C. Bae, J. Phys. Chem. B 114 (2010) 8948-8953], we presented a new method to predict liquid-liquid equilibria in ternary simple liquid mixtures by using a combination of a thermodynamic model and molecular simulations. As a continuation of that effort, we extend our previously developed method to ternary polymer systems. In the simulations, we used the dummy atoms to calculate the pair interaction energy values between the polymer segments and the solvent molecules. Furthermore, a thermodynamic model scaling concept is introduced to consider the chain length dependence of the energy parameters. This method was applied to ternary mixtures incorporating low to high molecular weight polymers. The method presented here well described the experimental observations using one or no adjustable parameters.     

Experimental and theoretical study of thermodynamic properties of levoglucosan

The heat capacity of levoglucosan was measured over the temperature range (5 to 370) K by adiabatic calorimetry. The temperatures and enthalpies of a solid-phase transition and fusion for the compound were found by DSC. The obtained results allowed us to calculate thermodynamic properties of crystalline levoglucosan in the temperature range (0 to 384) K. The enthalpy of sublimation for the low-temperature crystal phase was found from the temperature-dependent saturated vapor pressures determined by the Knudsen effusion method. The thermodynamic properties of gaseous levoglucosan were calculated by methods of statistical thermodynamics using the molecular parameters from quantum chemical calculations. The enthalpy of formation of the crystalline compound was found from the experiments in a combustion calorimeter. The gas-phase enthalpy of formation was also obtained at the G4 level of theory. The thermodynamic analysis of equilibria of levoglucosan formation from cellulose, starch, and glucose was conducted.     

Crystal structure,thermodynamic properties and detonation characterization of bis(5‐amino‐1,2,4‐triazol‐3‐yl)methane

Bis(5‐amino‐1,2,4‐triazol‐3‐yl)methane (BATZM, C₅H₈N₈) was synthesized and its crystal structure characterized by single‐crystal X‐ray diffraction; it belongs to the space group Fdd2 (orthorhombic) with Z = 8. The structure of BATZM can be described as a V‐shaped molecule with reasonable chemical geometry and no disorder. The specific molar heat capacity (C_p,m) of BATZM was determined using the continuous C_p mode of a microcalorimeter and theoretical calculations, and the C_p,m value is 211.19 J K^?1 mol^?1 at 298.15 K. The relative deviations between the theoretical and experimental values of C_p,m, H_T – H_298.15K and S_T – S_298.15K of BATZM are almost equivalent at each temperature. The detonation velocity (D) and detonation pressure (P) of BATZM were estimated using the nitrogen equivalent equation according to the experimental density; BATZM has a higher detonation velocity (7954.87 ± 3.29 m s^?1) and detonation pressure (25.72 ± 0.03 GPa) than TNT.     

Calorimetric study of liquid gadolinium-based alloys

The enthalpies of mixing of liquid Gd-Si (1770±5 K) and Al-Gd (1760±5 K) alloys have been measured by high-temperature isoperibolic calorimetry. The calorimetric study of the gadolinium-based liquid alloys demonstrates the great negative enthalpies of mixing, which is associated with the contribution of GdSi and GdAl₂ intermetallides into the liquid-state thermodynamics. The comparison of obtained results with literature data has been performed. This revised version was published online in August 2006 with corrections to the Cover Date.     

A study of the thermodynamic properties and dehydration reaction kinetics of some salt-hydrates

Correlations were determined between heat capacity and temperature and phase change enthalpy of Ba(OH)₂·8H₂O. The phase diagram and DSC curve of the binary system Na₂CO₃·10H₂O?Na₂HPO₄·12H₂O were determined The kinetics of the dehydrating reaction of Ba(OH)₂·8H₂O, Na₂CO₃·10H₂O and Na₂HPO₄·12H₂O were measured and theoretically analyzed by TG.     

Strong and selective binding of amiloride to an abasic site in RNA duplexes: thermodynamic characterization and microRNA detection

Firmly tied: The binding affinity of amiloride for an abasic (AP) site-containing RNA duplex is two orders of magnitude superior to the affinity of the corresponding AP site-containing DNA duplex. The observed high binding affinity for the RNA duplex arises from a favorable enthalpy gain. The binding-induced fluorescence response of amiloride is applicable to microRNA detection.     

Surface characterization and heats of adsorption of chromatographic alumina gel

The porous nature of chromatographic alumina gel has been investigated by adsorption/condensation processes and electron microscopy. Having 63% porosity, the gel is very porous. Total pore volume as determined by the fluid-displacement method is 0.497 cm³ g^–1. Its specific surface area, as determined by water vapor adsorption, is 225 m² g^–1. Micropore volume, as determined by utilizing Gurwitsch's rule, turns out to be 0.262 cm³ g^–1. The greater portion of the surface area and pore volume occurs in small and transitional pores, with average pore radii (hydraulic) less than 2.1 nm.Organic vapors, such as methyl ethyl ketone, acetone, methyl acetate, and methyl alcohol, were adsorbed on the gel between 0 and 36°C under vacuum, and the data were recorded on a Cahn-1000 electrobalance device. Isosteric heats of adsorption were calculated by applying the Clausius Clapeyron equation to the adsorption isosters at different surface coverages. Two types of adsorption processes, one with low activation energy and other with high activation energy can be distinguished. The increase in values ofq _st indicates that increasing temperature changes physical adsorption into chemisorption.     

三聚氰胺结构和热力学性质的密度泛函理论研究

采用Materials Studio 软件中的DMol~3模块对三聚氰胺的结构和性质进行了理论研究.得到了分子的几何构型、振动频率、各原子上的电荷分布、热力学、以及Fukui指数和前线分子轨道.计算结果表明:三聚氰胺分子中的C原子易得电子,是亲核试剂进攻点,而胺基上的N原子因含孤对电子是亲电反应中心.     

Comparative Thermodynamic Analysis of Ga-GeSb0.855 Section in the Ternary System Ga-Ge-Sb

Thermodynamic investigations of Ga-GeSb_0.855 section in the ternary system Ga-Ge-Sb, which is of a practical importance in electric-industry, are presented in this paper. Results of a comparative thermodynamic analysis at 1273 K obtained by Oelsen calorimetry and predicting methods - general solution model and Hajra's method are also given. This revised version was published online in August 2006 with corrections to the Cover Date.     

DSC calibration in the study of shape memory alloys

The unusual mechanical properties (i.e. shape memory effect and superelasticity) of shape memory alloys (SMA) rely on the thermoelastic martensitic transformation (TMT) which is a first-order solid-solid, non-diffusive phase transition, athermal in character. Differential scanning calorimetry (DSC) is often used as a convenient method of investigating the thermal properties ofSMAs. The common practice of standard temperature calibration, required for a correct instrument performance, is here critically discussed in relation to the study of both the direct exothermic transformation on cooling, and the reverse endothermic transformation on heating in a NiTiSMA. The DSC results show that, with the standard temperature calibration, the instrument is calibrated on heating but un-calibrated on cooling. A general method is advanced to overcome this problem, intrinsically related to the dynamic character of DSC.     

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.

     

The estimation of the thermodynamic properties of ternary alloys from binary data using the shortest distance composition path

A new composition path, X_i-X_j=constant, is suggested for the semi-empirical calculation of the thermodynamic properties of ternary ‘substitutional’ solutions from binary data, when the binary systems show deviations from the regular solution model. A comparison is made between the results obtained for integral and partial properties using this composition path and those calculated employing other composition paths suggested in literature. It appears that the best estimate of the ternary properties is obtained when binary data at compositions closest to the ternary composition are used.