Thermodynamic properties of the mixtures of some ionic liquids with alcohols using a simple equation of state

In the present work, we have used a simple equation of state called the GMA EoS to calculate the density of three ionic liquid mixtures including 1-butyl-3-methylimidazolum hexafluorophosphate, [BMIM] [PF₆] + methanol, 1-butyl-3-methylimidazolum tetrafluoroborate, [BMIM] [BF₄] + methanol, and [BMIM] [BF₄] + ethanol at different temperatures, pressures, and compositions. The isothermal compressibility, excess molar volumes, and excess Gibbs molar energy of these mixtures have been computed using this equation of state. The values of statistical parameters show that the GMA EoS can predict these thermodynamic properties very well within the experimental errors. The results show that isothermal compressibility of ionic liquids is lower than alcohols and the effect of temperature and pressure on the isothermal compressibility of ionic liquids is lower than alcohols. The excess molar volumes and excess molar Gibbs energy for these ionic liquid mixtures with alcohols are all negative at various temperatures and pressures over the whole composition range. The results have been interpreted in terms of intermolecular interactions and structural factors of the ionic liquids and alcohols.     

高温高压下闪锌矿相GaN结构和热力学特性的分子动力学研究

利用分子动力学方法和Buckingham经验势模型对重要半导体材料GaN立方闪锌矿相的晶格常数、相变压力(从闪锌矿到岩盐结构)、热膨胀、等温体模量、定压热容等结构和热力学特性在300—3000K的温度范围和0—65GPa的压力范围内进行了研究.研究表明，闪锌矿相GaN常态下的结构和热力学参数的模拟结果与实验数据及其他理论结果相符.同时在所选作用势模型可靠性检验的基础上，对等温体模量、定压热容诸非谐性参量在高温高压下的热力学行为进行了预测.所得结果在材料科学等领域的研究中具有一定的应用背景和参考价值. 关键词： GaN Buckingham势 分子动力学模拟 高温高压     

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.     

Ultrasonic study of the phase diagram of methanol

The phase diagram of methanol is studied by an ultrasonic technique over the temperature range 90–290 K at pressures up to 1.2 GPa. The pressure and temperature dependence of the velocity of longitudinal ultrasonic waves and the density of crystalline and liquid phases has been determined. Weak anomalies in the velocity of ultrasound in the liquid phase of methanol and the corresponding anomalous additional compression of the liquid at 230–250 K and 0.2–0.6 GPa have been found, and they are likely attributable to structural changes in the liquid phase.     

Thermal conductivity and thermal diffusivity of the R134a refrigerant in the liquid state

Thermal conductivity and thermal diffusivity of “ozone-safe” refrigerant R134a in liquid state within the range of temperatures 295.9–354.9 K and pressures from the liquid — vapor equilibrium line up to 4.08 MPa have been studied by high-frequency thermal-wave method. The experimental uncertainties of the temperature, pressure, thermal conductivity and thermal diffusivity measurement errors were estimated to be 0.1 K, 3 kPa, 1.5 and 2.5 %, respectively. Values of thermal conductivity and thermal diffusivity of liquid R134a on saturated line have been calculated. Approximation dependences for thermal conductivity and thermal diffusivity within the whole studied range of temperatures and pressures as well as on the saturated line have been obtained. The work was financially supported by the Russian Foundation for Basic Research (grant No. 07-08-00295-a).     

Loci of extrema of thermodynamic response functions for the Lennard–Jones fluid

Lines of extrema along isotherms and isobars for the residual isochoric heat capacity, the residual isobaric heat capacity, the isobaric thermal expansivity, and the isothermal compressibility of the Lennard–Jones fluid have been studied from popular equations of state due to Johnson et al. [Mol. Phys. 78, 591 (1993)], Kolafa and Nezbeda [Fluid Phase Equilib. 100, 1 (1994)], and Mecke et al. [Int. J. Thermophys. 17, 391 (1996)]. On depicting such loci in the pressure–temperature plane, the characteristic behaviour of thermodynamic response functions in the ideal-gas limit (at high enough temperatures or low enough pressures), the close-packed-fluid limit (at low enough temperatures or high enough pressures) as well as in the liquid, critical, and supercritical regions is identified. The present analysis is informative itself, but it also stimulates further work in order to tackle more complicated cases of study including associated fluids.     

Acoustic cavitation in 1-butyl-3-methylimidazolium bis(triflluoromethyl-sulfonyl)imide based ionic liquid

In this work, a comparison between the temperatures/pressures within acoustic cavitation bubble in an imidazolium-based room-temperature ionic liquid (RTIL), 1-butyl-3-methylimidazolium bis(triflluoromethyl-sulfonyl)imide ([BMIM][NTf₂]), and in water has been made for a wide range of cavitation parameters including frequency (140–1000 kHz), acoustic intensity (0.5–1 W cm⁻²), liquid temperature (20–50 °C) and external static pressure (0.7–1.5 atm). The used cavitation model takes into account the liquid compressibility as well as the surface tension and the viscosity of the medium. It was found that the bubble temperatures and pressures were always much higher in the ionic liquid compared to those predicted in water. The valuable effect of [BMIM][NTf₂] on the bubble temperature was more pronounced at higher acoustic intensity and liquid temperature and lower frequency and external static pressure. However, confrontation between the predicted and the experimental estimated temperatures in ionic liquids showed an opposite trend as the temperatures measured in some pure ionic liquids are of the same order as those observed in water. The injection of liquid droplets into cavitation bubbles, the pyrolysis of ionic liquids at the bubble-solution interface as well as the lower number of collapsing bubbles in the ionic liquid may be the responsible for the lower measured bubble temperatures in ionic liquids, as compared with water.     

U_(1-x)Pu_xO_2热膨胀性质分子动力学模拟研究

基于部分离子势函数的分子动力学方法,研究了U_(1-x)Pu_xO_2(x=0.07,0.15,0.25和0.5)在300—3000 K温度范围和0—1.5 GPa下的热力学性质,研究发现,在等压和不同温度下,随着钚(Pu)比率的增加,U_(1-x)Pu_xO_2的晶格常数线性减小,线性膨胀系数有所增大,等温压缩系数减小,通过拟合得到了零压下U_(1-x)Pu_xO_2晶格常数和线膨胀系数随Pu比率变化的经验表达式。     

Thermodynamic and magnetic properties of LaSn3

Thermal expansion coefficient between 77 and 900K, isothermal compressibility in the 0–80 Kbar pressure range, magnetic susceptibility between 77 and 1300 K and heat capacity at constant pressure in the 20–300 K temperature range were determined for the LaSn₃ compound. From the experimental data, the specific heat at constant volume was calculated and the thermal dependence of the Debye's parameter θ_D was obtained. The electron contribution to the heat capacity was also determined from the high temperature data. The magnetic properties confirm that there is no evidence of the existence of a magnetic moment localized on La atoms, in contrast with a previous report and in agreement with the general assumptions. A little anomaly found in the expansion coefficient, in the isothermal compressibility and in the specific heat is discussed in terms of a lattice order-disorder phenomenon.     

The Kirkwood correlation factor of dense methanol as a function of temperature and pressure under isochoric conditions and its statistical mechanical treatment

Experimental data of dielectric susceptibilities of methanol available in the literature over a wide range of temperature and pressure have been used for constructing a state function of the Kirkwood correlation factor g _K of methanol applicable in the homogeneous fluid region between 298 and 580?K and up to 350?MPa. Results of three isochores at 786.32, 820 and 850 kg m^?3 of this state function have been compared with predictions made by a statistical mechanical theory developed in previous work. The theory is based on an association model of alcohols accounting for the correlation of effective dipole moments of chains of all length as well as ringlike cluster formations. Most of the parameters such as association constants and association enthalpies have been obtained from quantum mechanical ab initio calculations of methanol clusters up to six members, reducing the numbers of adjustable parameters to three association constants and an averaged value of the angle between dipoles. The theory which has turned out to provide excellent results for alcohol + hydrocarbon and alcohol +?CCl₄ liquid mixtures at ambient pressure is also able to predict isochoric values of pure methanol up to a pressure of 350?MPa and temperatures of 570?K without adjusting further parameters in satisfying agreement with experimental data.     

Some aspects of the design of sonochemical reactors

The magnitudes of collapse pressures and temperatures as well as the number of free radicals generated at the end of cavitation events are strongly dependent on the operating parameters of the equipment namely, intensity and frequency of irradiation along with the geometrical arrangement of the transducers and the liquid phase physicochemical properties, which affect the initial size of the nuclei and the nucleation process. In the present work, the effect of these parameters on the collapse pressure generated and the maximum size of the cavity during the cavitation phenomena have been studied using the bubble dynamics equation, which considers the compressibility of the medium and a single bubble in isolation. The different liquid phase properties considered include, liquid vapor pressure, viscosity, bulk liquid temperature, surface tension and nature of dissolved gases (polytropic constant of the gas). The theoretical predictions have been also compared with the experimental results observed in the literature qualitatively and some recommendations have been made for the selection of the operating parameters so as to achieve maximum benefits. The work presented here is novel in sense that no earlier studies have considered the compressibility of the liquid medium and tried to evaluate the effect of all the operating parameters on the cavitational activity.     

Synchrotron X-ray diffraction study of phenacite at high pressure

We report the results of a natural phenacite from 0 to 30.9 GPa using in situ angle-dispersive X-ray diffraction and a diamond anvil cell at the National Synchrotron Light Source, Brookhaven National Laboratory. Over this pressure range, no phase change or disproportionation has been observed. The isothermal equation of state was determined. The values of V₀, K₀, and K₀′ refined with a third-order Birch-Murnaghan equation of state are V₀=1116.1±1.2 ų, K₀=223±9 GPa, and K₀′=5.5±0.8. Furthermore, we confirm that the linear compressibilities (β) along a and c directions of phenacite are elastically isotropic (β_a=1.50×10^-3 and β_c=1.34×10^-3 GPa^-1). Consequently, it can be concluded that the compressibility of phenacite under high pressures has been accurately constrained.     

Isothermal bulk modulus of solid xenon for zero pressure at 4.2 K, 65 K and 77 K

An interferometric method has been used to measure the isothermal bulk modulus (the reciprocal of the compressibility) of solid xenon at zero pressure for several temperatures. It is the first time that an elastic constant of this substance has been measured at a temperature below 10 K. The smoothed results are (37.9 ± 0.5) kbars at 4.2 K, (29.6 ± 0.5) kbars at 65.6 K, and (28.2 ± 0.5) kbars at 77 K.     

Speeds of sound and isothermal compressibility of ternary liquid systems: Application of Flory’s statistical theory and hard sphere models

Speeds of sound and densities of three ternary liquid systems namely, toluene + n-heptane + n-hexane (I), cyclohexane + n-heptane + n-hexane (II) and n-hexane + n-heptane + n-decane (III) have been measured as a function of the composition at 298.15 K at atmospheric pressure. The experimental isothermal compressibility has been evaluated from measured values of speeds of sound and density. The isothermal compressibility of these mixtures has also been computed theoretically using different models for hard sphere equations of state and Flory’s statistical theory. Computed values of isothermal compressibility have been compared with experimental findings. A satisfactory agreement has been observed. The superiority of Flory’s statistical theory has been established quite reasonably over hard sphere models.      

Thermal expansivity and bulk modulus of ZnO with NaCl-type cubic structure at high pressures and temperatures

The thermal expansivity and bulk modulus of ZnO with NaCl-type cubic structure were estimated by using the constant temperature and pressure molecular dynamics technique with effective pair potentials which consist of the Coulomb, dispersion, and repulsion interaction at high pressures and temperatures. It is shown that the calculated thermodynamic parameters including linear thermal expansion coefficient, isothermal bulk modulus and its pressure derivative are in good agreement with the available experimental data and the latest theoretical results. At an extended pressure and temperature ranges, linear thermal expansion coefficient and isothermal bulk modus have also been predicted. The thermodynamic properties of ZnO with NaCl-type cubic structure are summarized in the pressure 0–150 GPa ranges and the temperature up to 3000 K.     

Study of electrical resistivity of semiconductor SmS in the absence of a metallic phase on the surface

The temperature dependences of the electrical resistivity of samarium monosulfide single-crystal samples subjected to chemical treatment to remove a metallic phase from their surfaces have been measured in the range of 1.5–400 K at atmospheric pressure and at a pressure of 0.3 GPa. The temperature dependences of the activation energy of conduction electrons at these pressures and the piezoresistance coefficient of uniform compression have been calculated. It has been shown that the known model of the structure of the impurity-level spectrum in SmS remains partially valid at temperatures higher than 15 K. At lower temperatures, the existence of shallow donor centers in SmS and the hopping conduction over them should be taken into account.     

Melting of cubic boron nitride at extreme pressures

Due to its large pressure range of stability and inert nature, cubic boron nitride has been proposed as a potential pressure standard for high pressure experiments. It is extremely refractive upon compression, although its melting temperature is not known beyond 10 GPa. We apply first-principles molecular dynamics to evaluate the thermodynamics of zincblende structured (cubic) and liquid boron nitride at extreme temperatures and pressures, and compute the melting curve up to 1 TPa by integration of the Clapeyron equation. The resulting equations of state reveal that liquid boron nitride becomes denser than the solid phase at pressures of around 0.5 TPa. This is expressed as a turnover in the melting curve, which reaches a maximum at 510 GPa and 6550 ± 700 K. The origin of this density crossover is explained in terms of the underlying liquid structure, which diverges from that of the zincblende structured solid as the phases are compressed.     

Melting Curve of Iron: The Never-Ending Story?

For the better general understanding of melting behavior at high pressure, we investigated the influence of both crystallographic and electronic structure, and compressibility on melting temperatures for a large class of materials. In particular, we have established a large data base for melting of transition metals to megabar pressures. In general, bcc metals ( e.g. W, Ta, Mo, V, Cr) have very flat melting curves, and the initially steeper melting curves of fcc metals (Fe, Co, Ni) flatten significantly at high pressure. We also observed this trend for the more complicated alkaline earth, and rare earth metals. The flattening of the melting curves is due to the similarity of the solid and liquid structures and volumes. For iron there may exist an additional complication which may explain the reported results on both melting temperatures and structures. Due to the similarity in the free energies of its high pressure structures, these may coexist over a large pressure range. This phenomenon has been recently documented for noble gases with similar structures.