流体的格鲁尼森数及其对状态方程的检验

格鲁尼森数是一个无量纲的热力学参数,通常被用来描述固体的热力学性质.由于其对流体的临界点不敏感,它对于检验非理想流体的热力学性质也有指导意义.本文通过计算多种流体在不同温度和压力下的格鲁尼森数,发现其数值在宽广区域里变化稳定,进而论述了格鲁尼森数与其他热力学参数的关系.以PR方程和BWR方程为例,阐述了格鲁尼森数对于检验状态方程完善性的标尺性作用.     

固液黏着功的Berthelot平均规则的推广及应用

以固液黏着功的Berthelot几何平均规则及其推广为基础的Zisman方程、Fowkes方程和Owens-Wendt方程是固体表面张力测定的基础.对Berthelot几何平均规则进行了进一步的推广,并以此为基础,对Zisman方程中的参数给出了推广的表示式,并对Fowkes方程和Owens-Wendt方程进行了进一步的推广. 关键词： 接触角 Berthelot规则 Fowkes方程 Owens-Wendt方程     

理想气体热容的声学测试技术研究

根据热力学基本定律导出的一些热力学关系式,确定了各种热力学参数之间的普遍关联.只要知道了流体在理想气体状态下热容随温度的函数关系以及流体的状态方程,就能确定出该流体的内能、焓、熵、自由能、自由焓、(火用)以及逸度系数等热力学参数.此外,理想气体状态下的热容数据,还可用以反推分子结构与分子间相互作用的微观特性.因此,用实验方法确定工质在理想气体状态下的热容,对于流体工质热物性的研究具有十分重要的意义和作用.     

用形状因子法对应状态原理研究流体的热力学性质

形状因子法对应态原理是一种普遍化计算方法,有其严密的分子热力学依据。本文用此方法预测了气体的压缩因子和亨利常数,与实验值相比较均取得较好的结果。此方法还能用来计算迁移性质。 一、方法的分子热力学依据 用对应状态原理预测流体的热力学性质必须选择一参考流体“0”,当所研究流体“α”     

磁场中非广延相对论费米系统的统计性质

基于广义外势中的非广延统计理论,运用理论解析与数值模拟方法,研究磁场中非广延极端相对论费米气体的热力学性质,给出总能、热容量、化学势的解析式,分析非广延参数、极端相对论效应、磁场及温度对系统热力学性质的影响机理.研究显示,非广延参数不仅对热力学性质有直接的影响,而且也影响着磁场的物理效应. 随温度的升高,非广延参数及磁场对热力学性质的影响均被放大.极端相对论效应对化学势及热容量有特别显著的影响.     

微细尺度对流体饱和性质影响的MonteCarlo模拟定

本文采用ＭｏｎｔｅＣａｒｌｏ方法研究了纳米石墨管中流体氩的热力学性质。模拟表明在纳米石墨管中,流体的饱和性质与大尺度条件下相比可以有很大差别,同时空间尺度、固体壁面势能和流体密度的大小都对流体的饱和性质有明显的影响．本文的研究结果对微尺度条件下流体相交换热现象的研究有重要意义．     

具有长程相互作用S-1/2 XY链的研究

采用平均场Jordan-Wigner变换分析方法,研究了外场中且具有Z方向均匀长程相互作用自旋-1/2 XY链的热力学性质,得到了系统格点的亥姆赫兹自由能、内能、比热、磁化强度、磁化率等热力学量的解析表达式及其数值解,讨论了系统的一级和两级相变,数值结果在退化条件下与其他文献的结果符合很好.     

空分流体的临界热力学性质研究

论述了主要空分流体的临界区热力学性质,总结了这些流体目前最为准确的临界参数、临界指数及临界系数实验数据,并与多种模型的计算结果进行了比较.在整合多种流体临界区饱和密度实验数据的基础上,利用幂定律拟合方法得到了统一的临界指数β.该结果与实验数据及重正化群理论计算结果吻合良好.     

弱磁场中弱相互作用费米气体的热力学性质

根据赝势法和系综理论导出弱磁场中弱相互作用费米气体的内能、化学势和热容量的小参数r的解析式.在此基础上给出高温和低温两种情况下弱磁场中弱相互作用费米气体的热力学性质,探讨磁场及粒子间相互作用对热力学性质的影响,分析磁场与三维谐振势两种约束对系统性质影响的不同及其原因. 关键词： 赝势法 费米气体 相互作用 热力学性质     

临界点附近流体比热计算方法

一、引 言 临界点是气液相变的终点.在该点附近流体显示出奇异特性.奇异特性使得临界点附近流体热力学性质的实验测量与理论计算变得非常困难. 为了更好地表示临界点附近的热力学性质,状态方程应能表达流体在临界点的奇异性.Schofield首先提出能满足上述要求的参数标度状态方程——线性模型与立方模型两种.该方程用两个参变数R,θ表示.可以证明:在限定立方模型中,等温压缩率KT仅与R有关,与θ无关,所以R是KT大小的直接度量.KT具有强烈发散性,且又与密度涨落相关.从而,KT更能表征流体的临界特性.可见,从理论上讲,限定立方模型能更好地表…     

Thermodynamic modeling of oxide phases in the Fe–Mn–O system

A critical evaluation and thermodynamic modeling for thermodynamic properties of all oxide phases and phase diagrams in the Fe–Mn–O system are presented. Optimized Gibbs energy parameters for the thermodynamic models of the oxide phases were obtained which reproduce all available and reliable experimental data within error limits from 298 K to above the liquidus temperatures at all compositions covering from known oxide phases, and oxygen partial pressure from metal saturation to 0.21 bar. The optimized thermodynamic properties and phase diagrams are believed to be the best estimates presently available. Two spinel phases (cubic and tetragonal) were modeled using Compound Energy Formalism (CEF) with the use of physically meaningful parameters. The present Fe–Mn spinel solutions can be integrated into a larger spinel solution database, which has been already developed. The database of the model parameters can be used along with a software for Gibbs energy minimization in order to calculate any type of phase diagram section and thermodynamic properties.     

Perturbation theory for non-axial molecular fluids

The thermodynamic perturbation theory in which all angle-dependent interactions are considered as a perturbation of the central potential is applied to study the equilibrium properties of a fluid composed of non-axial molecules. The influence of a large number of anisotropic pair and three-body non-additive interactions have been taken into account. Using the same set of force parameters the calculation is made for gaseous pressure second and third virial coefficients and liquid phase thermodynamic properties (Helmholtz free-energy, configurational energy, pressure and entropy). It is shown that the non-axial approximation is an improvement over the axial one. Excellent agreement between theory and experiment is obtained for ethylene.     

Simulation of phase equilibria and interfacial properties of binary mixtures on the liquid-vapour interface using lattice sums

Molecular dynamics simulations of Lennard-Jones binary mixtures were performed to obtain phase equilibria and thermodynamic properties for the liquid—vapour interface. The dispersion interactions were handled using the lattice sum method where the full interaction is obtained and there is no requirement for any long range correction to the properties. The application of the method using the Lorentz—Berthelot combining rule for unlike interactions is discussed. The coexisting densities, adsorption of molecules at the interface and surface tension are the main results of this work. Coexisting properties were compared with Gibbs ensemble Monte Carlo results and with those of the grand canonical Monte Carlo method combined with the histogram reweighting technique, and good agreement was found. The lattice sum method results were compared with those of the spherically truncated and shifted potential to analyse the truncation effect. The adsorption of molecules at the interface and surface tension increase with interaction.     

Phase separation of highly dissymmetric binary ionic mixtures

We study the phase separation of binary ionic mixtures involving two species of classical point ions in a rigid uniform neutralizing background of degenerate electrons. The thermodynamic properties of the ionic fluid are calculated on the basis of the HNC integral equation for the three partial pair distribution functions. We develop a systematic technique which allows the properties of mixtures of arbitrary composition to be expressed in terms of infinitely dilute solutions. Phase diagrams and critical parameters are determined for 12 different binary systems involving ionic charge ratios between 2 and 8. The dependence of the critical temperature on the ionic charges, on the pressure and an ionic quantum corrections is examined in detail.     

Composition and thermodynamic properties of thermal plasma with condensed phases

The initial relations of a method for calculating the composition and thermodynamic properties of a closed heterogeneous system in thermodynamic equilibrium at constant pressure and temperature are given. The gaseous phase is always present in the system, and substances in the condensed state can also be present, which are divided into several condensed phases. The essence of the method consists in the minimizing the Gibbs energy of a system in ideal state. The application possibilities of the method described are discussed in detail. The main aim of the article is to provide solutions to problems arising in the calculations of composition and thermodynamic properties. These problems are not only of physico-chemical nature but they also relate to the numerical calculations and stability. The nature of the problems is general and independent of computation method.     

Thermodynamic properties and phase equilibria of charged hard sphere chain model for polyelectrolyte solutions

A recent thermodynamic perturbation theory for flexible polyelectrolyte solutions is extended to study thermodynamic properties and phase equilibria for polyelectrolyte solutions with different polyion, chain lengths. Osmotic pressure, activity coefficient of an individual ion (polyion or counterion) and average activity coefficient are calculated. Except for the activity coefficient of the polyion, the chain length dependence of the properties is small. Also presented are vapour-liquid equilibrium coexisting curves, vapour pressures and critical points. As the polyion chain length approaches infinity the critical properties (temperature, pressure and density) become constants.     

流体混合物热力学性质计算的混合法则新进展

回顾近期关于流体混合物热物性混合法则的研究新进展,特别是余吉布斯自由能(GE)和余亥姆霍兹自由能(AE)型混合法则的拓展及应用,重点介绍一种基于AE,仅通过偏微分方程便可计算混合物所有热力学性质的混合法则。可为发展未知流体混合物热物性计算方法以及各种常见混合物热物性的工程应用提供参考和依据。     

Exact viscous fluid FRW cosmologies: The case of general k

Exact solutions of the Einstein field equations for a viscous fluid in which the geometrical part is identical to that of the FRW dust models with k = 0, ±1 is presented. The solutions have a radially flowing fluid, all necessary energy and thermodynamic conditions are satisfied, and all physical quantities are well behaved everywhere in space-time if the model is expanding.     

Analytic equation of state for solids with multi-exponential potential based on analytic mean field potential approach and applied to the epsilon phase of solid oxygen

The thermodynamic properties of the ε phase of solid oxygen are studied by using the analytic mean field approach （AMFP）. Analytic expressions for the Helmholtz free energy, internal energy and equation of state of solid oxygen have been derived based on the multi-exponential potential. The formulism for the case of double-exponential （DE） model is applied to the ε phase of solid oxygen. Its four potential parameters are determined through fitting the experimental compression data of the ε phase of solid oxygen. Numerical results of the pressure dependence of the volume calculated by using the AMFP are in good agreement with the original experimental data. This suggests that the AMFP is a useful approach to study the thermodynamic properties of the ε phase of solid oxygen. Furthermore, we predict the variation of the volume, lattice parameters and intermolecular distances with pressure, and some thermodynamic quantities versus volume, at several higher temperatures.     

Critical evaluation and thermodynamic modeling of the Mn–Cr–O system for the oxidation of SOFC interconnect

A complete critical evaluation and thermodynamic modeling of the phase diagrams and thermodynamic properties of the Mn–Cr–O system at 1 bar total pressure are presented. Optimized equations for the thermodynamic properties of all phases are obtained, which reproduce all available and reliable thermodynamic and phase equilibrium data within experimental error limits from 25 °C to above the liquidus temperatures at all compositions and oxygen partial pressures. As results of optimization, the Gibbs energy function of MnCr₂O₄ is for the first time properly estimated and the discrepancies of the phase diagram experiments of the Mn–Cr–O system are resolved. In particular, unexplored phase diagrams and thermodynamic properties of the Mn–Cr–O system of importance for the oxidation of SOFC interconnect are predicted on the basis of the optimized model parameters. The database of the model parameters can be used along with software for Gibbs energy minimization in order to calculate any type of phase diagram sections and thermodynamic properties.