Analysis of P-V-T relationships and thermodynamic properties for some alkali halides

In this paper, Pandey approximation for the volume dependence of Anderson-Grüneisen parameter at fixed pressure, Anderson approximation for the temperature dependence of thermal expansivity, the equations of thermal expansivity along isobars derived by Shanker et al., and the presented approximation for the volume dependence of Anderson-Grüneisen parameter along isobars, have been used to study and predict the pressure-volume-temperature (P-V-T) data and the variations of the volume expansion coefficient and isothermal bulk modulus with temperature and pressure for NaCl, CsCl, LiF, NaF crystals, up to 30 GPa and in the temperature range 298-1073 K. The calculated values are compared with each other. It is found that these equations-of-state are valid and present good agreement with the available experimental data.     

Analysis of thermoelastic behaviour of MgO at high temperatures and high pressures

The thermoelastic behaviour of MgO has been studied for the temperature range (300-3000 K) under different compressions down to V/V₀=0.3. It has been shown that a comprehensive study of the thermoelastic properties of MgO can be made with the help of the Anderson-Isaak equation for thermal expansivity and the Vinet equation of state taken together. We have estimated the values of thermal expansivity α, isothermal bulk modulus K_T, their variations with pressure and temperature, the Anderson-Gruneisen parameter and the change in entropy with compression for MgO along isotherms at different temperatures. The results have been discussed and compared with the corresponding values reported in the recent literature.     

Analysis of equation of state and thermodynamic functions for trans-decahydronaphthalene up to 200~MPa and 446~K

This paper develops a modified Tait equation of state(EOS) for trans-decahydronaphthalene with four parameters A,B,V0 and P0 being treated as linear functions of temperature.The coefficients contained in these functions are determined through fitting the experimental compression data in the literature between 293 K and 446 K and at pressures from 10 to 200 MPa.Expressions for the thermal expansivity,isothermal compressibility and thermodynamic quantities are deduced and the numerical results are analytically derived.The numerical results show that the precision of the modified Tait EOS developed in this paper is superior to the EOS in the literature.     

Simulated equation of state of CaF2 with fluorite-type structure at high temperature and high pressure

The pressure-volume-temperature (P-V-T) equation of state (EOS), isothermal bulk modulus, and thermal expansivity of CaF₂ with cubic fluorite-type structure are investigated using the constant temperature and pressure shell model molecular dynamics (MD) method with effective pair potentials which consist of the Coulomb, dispersion, and repulsion interaction. It was shown that MD simulation is very successful in accurately reproducing the measured volumes of the CaF₂ over a wide range of pressures. The simulated P-V data matched X-ray diffraction experimental results up to 9.5 GPa at 300 K. In addition, volume thermal-expansion coefficient and isothermal bulk modulus were also calculated and compared with available experimental data and the latest theoretical results at ambient condition. At extended temperature and pressure ranges, The P-V EOS under different isotherms at selected temperatures, T-V EOS under different isobars at selected pressures, thermal expansivity, and isothermal bulk modulus were predicted up to 1500 K and 10 GPa. The detailed knowledge of thermodynamic behavior and EOS at extreme conditions are of fundamental importance to the understanding of the physical properties of CaF₂.     

Thermal expansion coefficient of ternary liquid mixture using hard sphere models and Flory’s statistical theory

The coefficients of thermal expansion (α) of ternary liquid mixtures of heterocyclic compounds viz., pyridine/quinoline with phenol in benzene have been evaluated at 308.15, 318.15 and 328.15 K, respectively. A comparative study of thermal expansivity using different models for hard sphere equation of state and Flory’s statistical theory has been made. The computed values of thermal expansivity are compared with the experimental results. The excess values of thermal expansivity have also been computed and utilized to discuss the existence and strength of intermolecular interactions in the ternary liquid system under investigation.     

Ab-initio theoretical analysis of thermal expansivity,thermal vibrations and melting of thorium

The thermal expansivity and mean-square thermal vibrational amplitudes were determined as a function of temperature for thorium from first principles total energy calculations using the full potential linearized augmented plane wave (FP-LAPW) method. The coefficient of thermal expansion determined from variation of theoretical potential energy with interatomic separation is ～1.427 × 10^?5 K^?1 as compared to an experimental value of 1.23 × 10^?5 K^?1. The mean-square thermal vibrational amplitudes determined as a function of temperature from the theoretically calculated volume-dependent Debye temperature agree well with experimental data derived form neutron diffraction measurements. The melting temperature of thorium, determined theoretically from the mean-square thermal vibrations and the Lindemann rule for melting, is 2234 K, as compared to the reported experimental value of 2021 K.     

Isochoric temperature coefficient of surface tension andS o-parameter of quasi-spherical molecular liquids

The Sharma parameterS _o which is characteristic of molten alkali halides and polymers has also been shown to be characteristic of a wide variety of liquids. Calculated data using the volume expansivity of the liquid establish the constancy of theS _o-parameter which retains, on an average, a constant value of 1·11 for quasi-spherical molecular liquids. It is shown thatS _o-parameter is also related to volume expansivity of the surface layer of the liquid, temperature coefficient of surface tension of liquids and describes the temperature and volume or pressure dependence of thermodynamic Grüneisen parameter and isochoric heat capacity with significant contribution for influencing the thermoacoustic and surface tension properties of liquids.     

氮化硅α，β和γ相的解析状态方程和热物理性质

对固体通用状态方程考虑热效应的Einstein模型进行修正，提出一种利用参考温度下的实验数据计算绝对零度下物质参数的方法，并用于Baonza方程以考虑热效应.结果表明，对于Baonza方程，零温下的参数可以解析地求解出来，常用的热物理量也可以推出解析表达式.将得出的公式用于研究氮化硅α，β和γ相的热物理性质.通过对文献的分析确定了这三种相的方程参数，计算的体积随压强变化和热膨胀系数随温度变化的结果与实验数据符合很好.     

X-ray reflectivity studies on glass transition of free standing polystyrene thin films

We have studied thermal expansion of free standing polystyrene thin films using X-ray reflectivity to elucidate the glass transition temperature and the thermal expansivity. We found that the glass transition temperature T_g decreased with the film thickness, depending on molecular weight. The reduction in the free standing films is much larger than in the supported films on Si substrate, suggesting that some segmental motions are activated due to free surfaces on both sides in the free standing films. We also found that the thermal expansivity in the glass and the melt decreased with the film thickness. This decrease must be attributable to chain confinement effects.     

Analysis of thermal expansivity and isothermal compressibility of liquid hexane and chloroform

In the present paper, we have analysed the pressure dependences of thermal expansivity (α _p ) and isothermal compressibility (K _T ) for the liquid hexane and chloroform. We have used the formulae based on the pseudospinodal model and the Sanchez et al [1,2] equation of state obtained from the Pade approximation. The thermal expansion coefficient and isothermal compressibility follow a power law function of pressures. It is found that the quantities, α _p as well as K _T decreases with the increasing pressure. The isothermal compressibility decreases more rapidly in comparison to thermal expansivity. The pressure at which the spinodal condition is satisfied, i.e. α _p and K _T both tend to infinity, has been found to be a characteristic property of the liquid hexane and chloroform.     

Analysis of thermal expansivity of iron (Fe) metal at ultra high temperature and pressure

In the present investigation we have explained the thermal and compression properties of HCP iron (Fe) at high pressure with variable temperature (isobars) and at high temperature with variable pressure (isotherm). The usual Tait equation of state is modified by incorporating the effect of thermal pressure. The calculated values of pressure for different isotherms and isochors and thermal expansivity (α) as a function of both temperature and pressure have been compared with those values obtained by Isaak et al and Wasserman et al.      

Elastic constants for NaCl and KCl solids at high temperatures

In the present study we derive new relationships to predict the temperature dependence of elastic constants. Proposed relationships are applied to study elastic constants of NaCl and KCl. A linear relationship between thermal expansivity and elastic constants at high temperatures is found to exhibit for solids. The extrapolated data on elastic constants in very high temperature region obtained in the present study are useful to understand the thermoelastic properties of NaCl and KCl. A close agreement between theory and experiment reveals the validity of the formulations used.     

Heat capacity and lattice dynamics of yttrium diboride in the temperature range 5–300 K

This paper reports an experimental study of the heat capacity and crystal lattice parameters of a polycrystalline sample of yttrium diboride prepared by high-temperature synthesis from elements. The electronic and lattice contributions to the heat capacity are isolated. The temperature dependences of the characteristic temperature, the linear thermal expansion coefficients α_a(T) and α _c (T), the bulk thermal expansion coefficient β(T), and the Grüneisen coefficient are calculated. A region of negative values of α _c (T) and β(T) is revealed. Anharmonicity is found to exert only a minor effect on the YB₂ lattice dynamics over a larger part of the temperature range covered.     

Ferromagnetic order in silicon-manganese alloys with phase separation

A phenomenological model of high-temperature ferromagnetism in silicon-manganese alloys has been proposed taking into account phase separation in these alloys, where manganese-rich particles of the secondary phase (precipitate MnSi_{2 − z} with z ≈ 0.25–0.30) are formed inside a manganese-depleted matrix of almost pure silicon. Precipitate MnSi_{2 − z} is considered as the silicide MnSi_1.7 containing a certain number of magnetic defects whose origin is due to the presence of weakly hybridized 3d orbitals of manganese. The silicide MnSi_1.7 is a weak band ferromagnet in which strong fluctuations of the spin density (paramagnons) are present at a temperature much higher than its Curie temperature. It has been shown that the ferromagnetic exchange interactions between the magnetic moments of defects in precipitate exists due to thermal excitations of the spin density and the ferromagnetic order can appear at a temperature much higher than the Curie temperature of the silicide. The spatial structures and characteristics of this order have been described in the framework of the proposed approach for both homogeneous bulk precipitate and precipitate particles of various shapes and sizes. The short-range magnetic order near the bulk phase transition has been analyzed taking into account inhomogeneities in the distribution of magnetic defects in precipitate. The experimental data on the magnetic properties of silicon-manganese alloys have been interpreted in terms of the theoretical results obtained in this work.     

Analysis of temperature dependence of thermal pressure of solids

Various models for determination of the temperature dependence of thermal pressure are critically examined in the light of experimental data. We have considered Mg₂SiO₄, Olivine, MgAl₂O₄, Pyrope rich garnet, Fe₂SiO₄, Grossular garnet, MnO, NaCl and KCl. The superiority of one model over others is discussed. The model is extended to study the compression behaviour at different temperatures, and the combined effect of pressure and temperature on thermal pressure of San Carlo Olivine. A good agreement obtained between theory and experiment demonstrates the validity of the present approach.     

Temperature invariance ofS 0-parameter of polymers

The parameterS ₀ which is characteristic of molten alkali halides and liquids has also been shown to be characteristic of a wide variety of polymers. Calculated data using the volume expansivity of the polymer establish the temperature invariance and constancy of theS ₀-parameter which retains, on an average, a constant value of 1.11 for polymers. Further understanding of the significance of fractional free volume andS ₀-parameter in describing various thermoacoustic properties and the anharmonic behaviour in polymers, has been developed.     

A model for compression dependence of thermal expansivity

In the present study, we propose a suitable model to compute volume dependence of thermal expansivity which is applicable up to infinite pressure or compression. The newly developed model satisfies the constraints of infinite pressure as suggested by high-pressure thermodynamics. The compression dependence of thermal expansivity for lower mantle of the Earth is evaluated with the help of the proposed model. A close agreement between theory and the results predicted with the seismic data is found, which in turn reveals the validity of the present work.     

Experimental and modeling study of the low to high-temperature oxidation of the methyl isopropyl ketone in O2/N2/Ar and O2/CO2/Ar atmospheres

Few studies on the low-temperature combustion behavior of MIPK, being a promising fuel additive, have been conducted. In this work, ignition delay times (IDTs) of MIPK were measured in the temperatures ranging between 780–910 K and pressures of 20 and 25 bar using a rapid compression machine (RCM). Oxy-fuel combustion combined with biofuel could remove CO₂ from the atmosphere. The IDTs of MIPK were measured in the temperatures ranging between 1125–1600 K under the O₂/CO₂ atmosphere at the pressures of 1 and 10 bar using a shock tube. A low to high-temperature MIPK kinetic model (HUST-MIPK model) was proposed, in which the low-temperature sub-model consists of 19 low-temperature reaction classes and was constructed by analogy-based method, the high-temperature sub-model was adapted from the works of Cheng et al.. The predictions of HUST-MIPK model are in good agreement with the present low-temperature IDTs, high-temperature O₂/CO₂ atmosphere IDTs, and the literature experimental data. The negative temperature coefficient (NTC) behavior was not observed in the temperature range from 790 to 910 K in the present RCM experiments, but was observed for methyl propyl ketone (MPK) and diethyl ketone (DEK) under similar conditions. The low-temperature chemistry of three pentanone isomers (MIPK, MPK, and DEK) was compared using the flux and sensitivity analysis. The comparison of the experimental high-temperature IDTs between O₂/CO₂ and O₂/Ar atmospheres indicates the IDTs of MIPK under O₂/CO₂ atmosphere are longer than those under O₂/Ar atmosphere at 1 bar, and the effects of CO₂ are almost independent of the pressure. The physical and chemical effects of CO₂ on the ignition were studied in detail.     

Isochoric measurement of the equation of state of solid argon at high pressure

Isochoric P-T traces have been measured for solid argon at eight different molar volumes by using a capacitance technique which records the radial expansion of the vessel due to pressure. These measurements extend from melting curve temperatures down to 4 °K at pressures ranging up to 7 kbar.Analysis of the data indicates that, for the high temperature region (above 80 °K) the thermodynamic derivative ?P/?T_r is independent of both temperature and density to within experimental errors. Using the fact that ?P/?T_r is constant, it is possible to generate PVT and isothermal bulk modulus data at high temperatures. These data are compared with X-ray diffraction measurements and piston displacement data and are found to be in good agreement with both. The data also agree quite well with current theoretical predictions. The high-temperature bulk modulus data were found to have a simple exponential dependence on the molar volume, prividing another convenient representation of the high-temperature equation-of-state data.