液体混合物导热率的测量及导热率数据的理论预测

液体混合物导热率的测量及导热率数据的理论预测童景山，唐建，高光华，梁燕波（清华大学化学工程系北京１０００８４）关键词导热率，液体混合物，测量仪，预计法１测量原理与测量装置本文报道的这种仪器，它不仅可用来测量有机化合物的液相导热率，而且也可测量高导热率...     

凝聚态物质状态方程的一个数值模型

建立了凝聚态物质的一个三项式状态方程：以Faussurier平均原子模型为基础计算电子热压和电子热能;以Cowan模型为基础计算离子热压和离子热能;用基于实验数据的半经验拟合公式计算物质的冷压和冷能。用实验数据检验了用平均原子模型计算的平均电离度。将状态方程与Hugoniot关系式相结合,计算了Be和Al的冲击绝热曲线,结果充分地展现出电子在高温、高密度条件下的壳层结构效应。     

比较实验结果时应注意的问题

通常我们在实验结束后,常要查表将其测得值与表中值加以比较,并以此为根据来判断实验结果的正确与否或进行误差分析。但表中的值也是实验测得的,既然是实验测得也就有其测量时特定的各种条件与因素。在实验结果与之比较时,要根据自己实验的具体情况和条件,加以具体分析,不能盲目拿来比较。例如在测定物质的导热系数时,由于导热率受温度影响很大,相同物质温度不同,则导热率不同。纯金属和大多数液体(水例外)的导热率随温度的升高而降低,而非金属和气体的导热率随温度升高而增大,计算时应取用物质平均温度下的数值。     

近固体表面拟有序液体边界层的导热研究

本文用分子动力学模拟方法研究了近固体壁面拟有序液体边界层及其导热特性。得出分子密度沿垂直壁面方向呈衰减分布,且拟有序层内的分子运动方式接近于晶体分子。结合径向分布函数定量分析得出拟有序层的有序程度随固液耦合作用加强而增加。用G-K公式计算了拟有序层的导热系数,发现其与物件尺度、边界条件有密切关系。但在相同的边界条件下,导热系数随有序程度的增加而增加。     

绝缘液体中空间电荷的扩散和介电谱

用微分时域谱方法，研究了苯和正烷烃中空间电荷的存在和运动规律．理论分析表明，高绝缘体中空间电荷位移的等效扩散运动导致慢极化效应；其响应时间与电极距离的平方成比例，实验证实了理论结果．在苯和正烷烃中都观察到一个快极化和两个慢极化分量．其强度和响应时间随温度的变化给出分子运动与链长关系的信息．微分时域介电谱方法对高绝缘液体中的极微量杂质十分灵敏 关键词：     

制冷剂二元混合物液体粘度预测方程

针对目前较缺乏适用性强的预测液体混合物输运物性的方法的现状,本文作者通过对大量实验数据的分析和规律研究,提出了一种新的预测直链烷烃和直链烷烃的卤代物类物质液体二元混合物粘度的方程。该方程形式简单,精度可以满足工程应用需要,且具有较广的适用性。     

液体理论极限过热度的确定

本文利用统计热力学涨落理论提出一个新的假说，并由此建立了确定液体极限过热度的新方法。用导出的公式对18种液体物质极限过热度的计算结果表明，与其他作者提供的实验数据比较，其平均偏差小于0．67％，最大偏差不超过2.65％。本文给出的表达式具有普适性，可以对任何液体物质进行极限过热度预测。因此，这种新的方法在理论和应用上的价值都是显见的。     

应用胞腔理论计算纯物质的汽化热

1引言胞腔模型或称自由体积模型早在本世纪30年代就已经提出［’－‘］，但由于该模型的重要参数，即自由体积一直无法予以确定，以至于就无法用该模型来计算物质的一系列性质、作者曾于1985年利用胞腔型状态方程导出两个物质特性参数一内压因子和构形因子问，本文根据上述状态方程和两个特性参数导出了计算物质的自由体积公式。从此即可应用自由体积参数计算物质的热力学性质。本文是介绍应用自由体积参数计算纯物质的汽化热的方法。2自由体积模型的液体理论和自由体积的计算自由体积理论最早由Lennard－Jones和Devon－shire用来将液体的…     

一种适用于烷烃高压液相黏度的推算模型

本文基于绝对速率理论和SRK状态方程,建立了一种可以精确计算烷烃高压液相黏度的推算模型。选取10种正构烷烃(C_1-C_(10))的液相黏度作为研究对象,温度范围为90~448 K,压力范围为0.01~254.4 MPa,利用本文所提出的黏度模型对其进行了计算。计算结果表明:本文的黏度推算模型对这10种烷烃黏度的计算值与实验值之间的平均绝对偏差小于3%,验证了模型的精确性。     

纳米流体导热系数的分子动力学模拟

纳米流体的导热系数相对于基础流体而言有了显著提高,然而这种现象却无法用现有理论进行解释。应用平衡分子动力学方法对纳米流体的导热系数进行了模拟,并研究了纳米颗粒表面类似于固体的液体吸附层的存在和特性以及其对纳米流体导热能力的影响,在此基础上进一步对纳米流体导热性能显著提高的微观机理进行了探讨。模拟结果表明由于固体分子较强的吸引力,一部分液体分子被吸附在固体颗粒表面形成一个薄层,薄层内分子的排列结构不同于纯液体的分子排列结构,导热性能也优于基础流体,从而使得纳米流体的导热系数有了显著提高。最后对纳米颗粒表面液体薄层的厚度进行了定量计算。     

The thermal conductivity of mixtures of methane with argon and neon

The paper reports new measurements of the thermal conductivity of mixtures of neon and argon with methane at a temperature of 27.5°C. The measurements have been performed with a transient hot-wire instrument within the pressure range 1 to 22 MPa and the results have an estimated uncertainty of ±0.3%.The thermal conductivity data for the mixtures in the limit of zero density can be represented with the aid of the best available kinetic theory formulae, but not within their experimental uncertainty. The density dependence of the thermal conductivity of the mixtures is adequately described by a semi-empirical correlation scheme based on the modified Enskog theory.     

The corrected Enskog theory and the transport properties of molecular liquids

Analytical expressions for the transport coefficients of liquids based on the corrected Enskog theory have been used in order to determine the self-diffusion coefficient (D) for molecular liquids as a function of density and temperature. The liquids considered are those composed of linear molecules and NH₃. The calculated D values agree with the experimental ones for those molecular liquids for which experimental self-diffusion data are available. The translational part of the thermal conductivity (λ_trans) has also been calculated and compared with the experimental thermal conductivity (λ). It turns out that λ_trans for diatomic molecular liquids practically represents the whole of λ in a substantial fraction of the liquid range, indicating that the internal degrees of freedom hardly contribute to the thermal conductivity in these dense liquids. A comparison is made with recently published results based on the modified Enskog theory.     

Hydrodynamic correlation functions of hard-sphere fluids at short times

The short-time behavior of the coherent intermediate scattering function for a fluid of hard-sphere particles is calculated exactly through ordert ⁴, and the other hydrodynamic correlation functions are calculated exactly through ordert ². It is shown that for all of the correlation functions considered the Enskog theory gives a fair approximation. Also, the initial time behavior of various Green-Kubo integrands is studied. For the shear-viscosity integrand it is found that at densityn³=0.837 the prediction of the Enskog theory is 32% too low. The initial value of the bulk viscosity integrand is nonzero, in contrast to the Enskog result. The initial value of the thermal conductivity integrand at high densities is predicted well by Enskog theory.     

Chapman–Enskog solutions to arbitrary order in Sonine polynomials I: Simple,rigid-sphere gas

The Chapman–Enskog solutions of the Boltzmann equations provide a basis for the computation of important transport coefficients for both simple gases and gas mixtures. These coefficients include the viscosities, the thermal conductivities, and diffusion coefficients. The Chapman–Enskog solutions are also useful for computation of the associated slip and jump coefficients near surfaces. Generally, these solutions are expressed in terms of Sonine polynomial expansions. While it has been found that relatively, low-order expansions (of order 4) can provide reasonable precision in the computation of the transport coefficients (to about 1 part in 1000), the adequacy of the low-order expansions for computation of the slip and jump coefficients still needs to be explored. Also of importance is the fact that such low-order expansions do not provide good convergence (in velocity space) for the actual Chapman–Enskog solutions even though the transport coefficients derived from these solutions appear to be reasonable. Thus, it is of some interest to explore Sonine polynomial expansions to higher orders. It is our purpose in this paper to report the results of our investigation of high-order, standard, Sonine polynomial expansions for the viscosity and the thermal conductivity related Chapman–Enskog solutions for a simple, rigid-sphere gas where we have carried out our calculations using expansions to order 150 and where our reported values for the transport coefficients have been demonstrated to converge to at least 25 significant digits. We note that, for a rigid-sphere gas, all of the relevant integrals needed for these solutions are evaluated analytically as pure fractions and, thus, results to any desired precision may be obtained. This work also indicates how results may be obtained in a similar fashion for realistic intermolecular potential models, and how gas-mixture problems may also be addressed with some additional effort.     

A simultaneous electronic transition of the oxygen-naphthalene complex

Thorne's extension of the Enskog theory to thermal conductivity and viscosity of binary hard sphere fluid mixtures is examined. It is shown that for molecules of the same size and different mass the expression for the thermal conductivity of such a mixture obtained by Longuet-Higgins, Pople and Valleau is identical to the collisional term in Thorne's equation arising from the locally maxwellian velocity distribution. Thorne's equations are evaluated by using the Percus-Yevick approximation for the contact radial distribution functions obtained by Lebowitz. The variations of the transport coefficients are examined as functions of pressure, composition and ratios of diameters and masses of the two species. Some comparison is made with experimental results.     

The thermal conductivities of some low melting materials relevant to energy storage

The thermal conductivities of seven candidate materials for solar-energy storage were measured as a function of temperature in the solid and liquid states. A drop in thermal conductivity was observed near the melting point. It was shown that the ratio of thermal conductivities in the liquid and solid phases depended on the structure of the material investigated. The vibrational conductivity contribution was calculated and compared with the experimental values for the thermal conductivities.     

基于团聚理论的纳米制冷剂导热系数预测方法

纳米流体中纳米颗粒以团聚体的形式存在.为预测纳米流体的导热系数,模拟了流体中纳米颗粒团聚体的三维空间结构并用热阻网络法计算了团聚体的导热系数.在得到团聚体的导热系数与考虑液体分子吸附层后团聚体的体积分数后,预测纳米流体的导热系数.用实验数据验证了该预测方法并运用该方法预测了铜-R22纳米制冷剂的导热系数.     

Different effects of grain boundary scattering on chargeand heat transport in polycrystalline platinum and goldnanofilms

The in-plane electrical and thermal conductivities of several polycrystalline platinum and gold nanofilms with different thicknesses are measured in a temperature range between the boiling point of liquid nitrogen (77K) and room temperature by using the direct current heating method. The result shows that both the electrical and thermal conductivities of the nanofilms reduce greatly compared with their corresponding bulk values. However, the electrical conductivity drop is considerably greater than the thermal conductivity drop, which indicates that the influence of the internal grain boundary on heat transport is different from that of charge transport, hence leading to the violation of the Wiedemann--Franz law. We build an electron relaxation model based on Matthiessen's rule to analyse the thermal conductivity and employ the Mayadas & Shatzkes theory to analyse the electrical conductivity. Moreover, a modified Wiedemann--Franz law is provided in this paper, the obtained results from which are in good agreement with the experimental data.     

Transport Coefficients in Some Stochastic Models of the Revised Enskog Equation

A stochastic model of the revised Enskog equation is considered. A choice of the smearing function suggested by the work of Leegwater is used to apply the model to the repulsive part of the Lennard-Jones potential and the inverse-power soft-sphere potential. The virial coefficients obtained from the equilibrium properties of the models are in excellent agreement with the known exact coefficients for these models. The transport coefficients for the repulsive Lennard-Jones (RLP) model are also computed and appear to be of comparable accuracy to the Enskog-theory coefficients applied directly to a hard-sphere system, although exact results for the RLP with which to make an extensive comparison are not yet available. The pressure and the transport coefficients obtained from the model (shear viscosity, thermal conductivity, and self-diffusion) are compared with the pressure and the corresponding transport coefficients predicted by the Enskog and square-well kinetic theories.     

Quantum liquids of particles with generalized statistics

We propose a phenomenological approach to quantum liquids of particles obeying generalized statistics of a fermionic type, in the spirit of the Landau Fermi liquid theory. The approach is developed for fractional exclusion statistics. We discuss both equilibrium (specific heat, compressibility, and Pauli spin susceptibility) and nonequilibrium (current and thermal conductivities, thermopower) properties. Low-temperature quantities have the same temperature dependences as for the Fermi liquid, with the coefficients depending on the statistics parameter. The novel quantum liquids provide an explicit realization of systems with a non-Fermi liquid Lorentz ratio in two and more dimensions. Consistency of the theory is verified by deriving the compressibility and f-sum rules.