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基于Roth, Evans和Dietrich有关耗尽势的密度泛函理论研究了Lennard-Jones (L-J)流体中胶体粒子间的耗尽势. 通过计算胶体稀溶液中两个胶体粒子在不同条件下的耗尽势, 进一步分析了L-J流体的相关因素对耗尽势的影响. 结果表明, L-J流体分子的体积分数、胶体粒子与溶剂分子的尺寸比率、L-J流体分子间的相互作用以及胶体粒子与流体分子之间的弱相互作用等因素均可对胶体粒子间耗尽势产生显著影响. 研究结果可为实验上调控胶体粒子间的相互作用提供可能的线索. 相似文献
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为了了解简单流体混合物在微孔介质中的流动和传递性质,对微孔中氩和氪流体混合物的扩散系数进行了计算机模拟和关联模型研究.运用平衡分子动力学方法模拟了宏量条件下饱和氩流体的扩散系数和恒温氪流体的扩散系数,模拟值与文献实验值符合良好,从而程序的正确性得到验证.然后,采用类似Bitsanis等人的方法模拟了平板湿壁微孔中氩和氪等摩尔流体混合物在不同对比温度、不同对比密度以及不同对比孔径条件下的扩散系数,发现孔径很小的时候扩散系数会急剧的增大.同时基于这些模拟值,参考CE理论和Heyes关系式,以对比温度、对比密度以及对比孔径为变量,关联出两个简单流体等摩尔混合物在微孔中扩散系数的计算模型.模型的计算结果与计算机模拟值能够较好地吻合. 相似文献
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建立了基于反相液相制备色谱和超临界流体制备色谱的组合方法,用于分离纯化醇提水沉后石油醚层中的海风藤。首先以甲醇作为改性剂,采用醇提水沉法去除海风藤甲醇提取物中的叶绿素,加入硅藻土后用石油醚回流富集目标成分。选用反相C18制备色谱柱将其分为18个组分,然后将组分在SFC模式下进行制备。选用酰胺色谱柱,以甲醇为改性剂,在柱温30℃、背压15.0 MPa的条件下进行分离。基于反相色谱和超临界流体色谱不同的分离选择性,最后分离得到6个高纯度化合物。该法展示了反相制备色谱和超临界流体制备色谱在海风藤分离纯化方面的优势,特别是超临界流体色谱在天然产物的分析和制备方面的巨大潜力。 相似文献
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采用分子动力学模拟(MD)方法对甲醇和乙醇在超临界二氧化碳中的无限稀释扩散系数进行了模拟计算, 并应用泰勒分散理论, 采用超临界色谱仪对模拟结果进行了实验验证. 模拟计算值与实验值较吻合, 且变化规律基本一致, 表明采用这种新方法可以准确有效地预测超临界体系的扩散性质, 能够方便地应用于工程设计. 相似文献
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固体溶质在超临界三元系统中的溶解度 总被引:1,自引:0,他引:1
溶质在超临界流体中的溶解度数据是研究超临界流体技术的基础.本文对纯组分固体溶质有夹带剂存在的超临界流体三元系统中,夹带剂增大溶质溶解度的作用进行了总结,述评了夹带剂增大溶质溶解度的机理和常用的计算模型.此外,针对两种固体混合溶质共存于超临界流体中的三元系统,讨论了混合溶质共存对彼此溶解度的影响及其相关的理论假说和计算模型. 相似文献
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The self- and mutual diffusion coefficients for binary mixtures of Ar-Kr both in the bulk and in the nanopores were studied by molecular dynamics simulations. The composition dependences and the relationships between the self- and the mutual diffusion coefficients both in the bulk and in the nanopores were further discussed. It was found that the simulation results (D(c.m.)) are close to the calculated ones (D(s)) for the Ar-Kr system. Both self- and mutual diffusion coefficients in nanopores are much lower than that of the bulk, and they ever decrease as the pore width decreases. Nevertheless, the self- and mutual diffusion coefficients increase as the mole fraction of Ar increases, and as expected, increase as the temperature increases. The self-diffusion coefficients of mixtures both in the bulk and in the nanopores are predicted by the Carman model and by the molecular cluster model. 相似文献
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《Physics and Chemistry of Liquids》2012,50(2):206-218
Molecular dynamic computer simulations are performed to study the mass dependence of mutual diffusion coefficient in an isotopic, equimolar binary system. The particles of the system are assumed to be interacting via Lennard-Jones potential. The self- and mutual diffusion coefficients are calculated from the time dependence of the mean square displacement and from the velocity correlation function using the Green–Kubo formula. The study has been carried out at different densities and temperatures. Like the self-diffusion coefficient, the mutual diffusion coefficient is also found to be weakly dependent on the mass ratio. Our study also shows that the temperature of the system has a negligible effect on the mass dependence of the diffusion coefficients. 相似文献
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Wyn Brown Peter Stilbs Robert M. Johnsen 《Journal of Polymer Science.Polymer Physics》1983,21(7):1029-1039
The concentration dependences of the friction coefficient(s) for poly(ethylene oxide) have been determined on well-defined fractions in dilute aqueous solution. Three independent techniques have been used: FT-pulsed field gradient NMR (self-diffusion), photon correlation spectrosccpy (mutual diffusion), and velocity sedimentation, in the concentration range 1-25 kg m?3. The results establish that, at a given concentration, the friction coefficient in self-diffusion is appreciably smaller than that operating in mutual diffusion and sedimentation; the friction coefficient in the latter processes are identical within experimental error. 相似文献
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分子动力学模拟苯和萘在超临界二氧化碳中的无限稀释扩散系数 总被引:5,自引:1,他引:4
采用球型模型和点位-点位模型对超临界二氧化碳的自扩散系数及苯或萘在超临界二氧化碳中的无限稀释扩散系数进行了分子动力学模拟。结果表明,球型模型及点位-点位模型均可较准确地预测二氧化碳的自扩散系数,球型模型因形式简单,准确度相对较差;点位-点位模型准确度虽高,但需较长的模拟机时。两种位能模型所获得的准确度相当,但点位-点位模型可以更精细地反映体系的微观结构。 相似文献
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Pair correlation functions and the self-diffusion coefficient of Lennard-Jones liquid in the modified free volume theory of diffusion 总被引:1,自引:0,他引:1
In this paper, we apply the Matteoli-Mansoori empirical formula for the pair correlation function of simple fluids obeying the Lennard-Jones potential to calculate reduced self-diffusion coefficients on the basis of the modified free volume theory. The self-diffusion coefficient thus computed as functions of temperature and density is compared with the molecular dynamics simulation data and the self-diffusion coefficient obtained by the modified free volume theory implemented with the Monte Carlo simulation method for the pair correlation function. We show that the Matteoli-Mansoori empirical formula yields sufficiently accurate self-diffusion coefficients in the supercritical regime, provided that the minimum free volume activating diffusion is estimated with the classical turning point of binary collision at the mean relative kinetic energy 3k(B)T/2, where k(B) is the Boltzmann constant and T is the temperature. In the subcritical regime, the empirical formula yields qualitatively correct, but lower values for the self-diffusion coefficients compared with computer simulation values and those from the modified free volume theory implemented with the Monte Carlo simulations for the pair correlation function. However, with a slightly modified critical free volume, the results can be made quite acceptable. 相似文献
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Most of the models proposed in literature for binary diffusion coefficients of solids in supercritical fluids are restricted to infinite dilution; this can be explained by the fact that most of experimental data are performed in the dilute range. However some industrial processes, such as supercritical fluid separation, operate at finite concentration for complex mixtures. In this case, the concentration dependence of diffusion coefficients must be considered, especially near the upper critical endpoint (UCEP) where a strong decrease of diffusion coefficients was experimentally observed. In order to represent this slowing down, a modified version of the Darken equation was proposed in literature for naphthalene in supercritical carbon dioxide. In this paper, the conditions of application of such a modelling are investigated. In particular, we focus on the order of magnitude of the solubility of the solid and on the vicinity of the critical endpoint. Various equations proposed in literature for the modelling of the infinite dilution diffusion coefficients of the solutes are also compared. Ten binary mixtures of solids with supercritical carbon dioxide were considered for this purpose. 相似文献
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Nanopore diffusion in multicomponent adsorption is described using different macroscopic theories: Onsager irreversible thermodynamics, Maxwell-Stefan, and Fickian approaches. A new equivalence between Fickian and Maxwell-Stefan formulations is described by [D]=[n(s)][B](-1)[Gamma][n(s)](-1). The elements of D and B are explicitly related to the Fickian and Maxwell-Stefan diffusivities, respectively. Only when the saturation loadings ni(s) for different components are the same can the matrix be reduced to the generally accepted equation [D]=[B](-1)[Gamma]. On the basis of the relationship between the irreversible thermodynamics and Maxwell-Stefan approaches, an equation is derived for a binary system with the symmetric form (1/Eth1 + theta2/Eth12)(1/Eth2 + theta1/ Eth21)=(L11L22)/(L12L21)(theta1theta2)/(Eth12Eth21) The Maxwell-Stefan binary exchange coefficients Ethij are shown to depend not only on the Maxwell-Stefan diffusivities, Ethi, but also on the Onsager coefficients. For a strong molecular interaction, that is, Ethi>Ethij , the ratio of Onsager coefficients will approach unity, giving the commonly used relation L12=square root L11L22 . In addition, the Maxwell-Stefan diffusivities, Ethi, are shown to depend on the interaction effects in mixtures, and Ethi in mixtures will not generally be equal to pure component values evaluated at the same total fractional loading. 相似文献
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Ar—Kr溶液扩散系数的分子动力学模拟及其与温度的关系 总被引:2,自引:1,他引:2
用分子动力学模拟方法研究确定Ar-Kr溶液的自扩散系数D1、D2和互扩散系数D12以及它们随温度变化的规律。结果表明,分别用Green-Kubo法和Einstein法得到的扩散系数在数值上一致;该溶液的3种扩散系数均满足D=D0e^E/RT关系。 相似文献
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Structural and thermodynamic properties as well as diffusion coefficients of binary fluid mixtures with asymmetry in mass, size, charge and their combinations have been studied using classical molecular dynamics simulations. The fluid mixture is modelled as spherical particles interacting via the Weeks–Chandler–Andersen and Coulomb potential. The diameter, charge and mass of the fluid particles are in the range 6–60 Å, 1–10e and 1—500 amu, respectively. Systematic variations in pair-correlation functions, thermodynamic properties as well as the self-diffusion coefficient are found with the size, charge and mass ratio of the particles. The self-diffusion coefficient for systems having more than one type of asymmetry is calculated and expressed in terms of diffusion coefficients of systems with only one type of asymmetry. 相似文献
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Nieto-Draghi C Bonet Avalos J Contreras O Ungerer P Ridard J 《The Journal of chemical physics》2004,121(21):10566-10576
We have employed an anisotropic united atom model of benzene (R. O. Contreras, Ph.D. thesis, Universitat Rovira i Virgili 2002) that reproduces the quadrupolar moment of this molecule through the inclusion of seven point charges. We show that this kind of interaction is required to reproduce the solvation of these molecules in supercritical water. We have computed self-diffusion coefficient and Maxwell-Stefan coefficients as well as the shear viscosity for the mixture water-benzene at supercritical conditions. A strong density and composition dependence of these properties is observed. In addition, our simulations are in qualitative agreement with the experimental evidence that, at medium densities (0.6 g/cm(3) and 673 K), almost half of the benzene molecules have one hydrogen bond with water molecules. We also observe that these bonds are longer lived than the corresponding hydrogen bonds between water molecules. Similarly, we obtain an important reduction of the dielectric constant of the mixture with the increment of the amount of benzene molecules at medium and high densities. 相似文献