Self-diffusion,mass transfer,and viscosity coefficients for a binary mixture in narrow slit-like pores

The concentration dependences of the dynamic characteristics of a binary mixture in narrow slit-shaped pores of different widths are considered. The local and mean partial self-diffusion, label transfer, mass transfer (mutual diffusion), and shear viscosity coefficients for binary mixtures of various compositions were calculated. The calculation was based on the lattice-gas model in the quasichemical approximation for spherical components with approximately the same size. The calculation of dynamic characteristics took into account collisions between the molecules that determine the direction of their motion. All the kinetic coefficients depend substantially on the mixture density, the direction of motion, and the distance to the pore wall. The effect of the pore width on the calculated dynamic characteristics is considered. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1726—1735, August, 2005.     

Molecular grounds of the calculation of equilibrium and transport characteristics of inert gases and liquids in complex narrow-pore systems

A self-consistent approach to the calculation of equilibrium and transport characteristics of inert gases and liquids in complex narrow-pore systems based on the lattice-gas model is proposed. A supramolecular structure for fine-grained solids was constructed and the adsorbate distribution within the pore volume is described. The supramolecular structure is simulated using slit-shaped, cylindrical, spherical, and globular segments. Additionally, junctions of pore systems with different structures are included, and the heterogeneity of their walls and the presence of structural defects in the pore segments are taken into account. The distributions of molecules are described in the quasi-chemical approximation to take into account intermolecular interactions using calibration functions to correct this approximation in the near-critical area. Expressions for local and integrated flow transfer coefficients are constructed, in particular, self-diffusion, shear viscosity and heat conductivity. The contributions of the near-wall areas and the core parts of pores to the general form of phase diagrams, the effect of the pore size on the conditions of capillary condensation, and the role of surface mobility of molecules are discussed.     

Calculations of the distribution of trace impurities in cylindrical pores

The equilibrium distribution of a trace impurity and the self-diffusion coefficients of molecules of the base component and the trace impurity in narrow cylindrical pores were calculated using the lattice-gas model. Two types of lattice structures with six and eight closest neighbors were considered. The sizes of the base component and impurity molecules were taken to be identical. Lateral interactions were taken into account in the quasi-chemical approximation. The equilibrium distributions of the trace impurity across a pore section in the gas and liquid phases of the base component and at the interface for the case of capillary condensation were considered. The probability of existence of isolated dimeric clusters was estimated and the self-diffusion coefficients of the base component and trace impurity for a single-phase distribution of the base component were calculated. The effects of the energy of interaction of impurities with the pore walls and the concentration of the base component on the diffusion mobility of the impurities were analyzed. The concentration dependences of the partition coefficient for the trace impurity between the pore center and the pore wall and the concentration dependences of the self-diffusion coefficients for the trace impurity molecules become nonmonotonic with an increase in the base component concentration. These effects are due to the displacement of the impurity from the near-surface area to the bulk of a pore following an increase in the pore coverage by the base component and to higher mobility of the impurity in the free bulk of the pore. Further filling of the pore bulk reduces the mobility of all molecules. The energetics of intermolecular interactions also plays a certain role. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 605–615, April, 2000.     

Self-Diffusion Coefficients for Pure and Mixed Adsorbate Fluids in Narrow Pores

The equilibrium distribution and the concentration dependence of the local and average self-diffusion coefficients for pure fluid and binary mixture components in narrow slitlike pores were analyzed. The coefficients were calculated using the lattice gas model in the quasi-chemical approximation on the assumption of a spherical shape and approximately equal sizes of the components. For the pure adsorbate, these calculations were compared with molecular dynamics simulations. Both methods gave similar concentration profile changes and dynamic characteristics of interlayer particle redistributions in strong nonuniform adsorption fields for dense fluids. A satisfactory agreement was obtained for the temperature dependences of the self-diffusion coefficients along the pore axis. The influence of the molecule–wall potential and of intermolecular interaction were considered. The self-diffusion coefficients of the adsorbate were shown to strongly depend on the density of the mixture and the distance from pore walls.     

Spherical particles in small porous sphero-cylindrical systems: phase diagrams and transfer coefficients

The equilibrium and transport characteristics of spherical particles in sphero-cylindrical porous systems were studied in terms of the lattice-gas model. The supramolecular structure of these systems is modeled by segments with a simple regular geometry (cylindrical and spherical) with additional inclusion of the interconnecting areas between different pore segments. Thus, one can model various types of porous systems ranging from zeolite cavities to stackings of long cylindrical sections in new mesoporous materials such as MCM-41 and MCM-49. The distribution of molecules is described in the quasichemical approximation with allowance for intermolecular interactions. The concentration dependences for local self-diffusion and shear viscosity coefficients were calculated. The contributions of the near-wall regions caused by the molecule—wall potential to the general pattern of phase diagrams, the effect of the pore size on the capillary condensation conditions, and the role of the molecular mobility on pore walls were discussed.     

Thermal diffusion and partial molar enthalpy variations of n-butane in silicalite-1

We report for the first time the heat of transfer and the Soret coefficient for n-butane in silicalite-1. The heat of transfer was typically 10 kJ/mol. The Soret coefficient was typically 0.006 K(-1) at 360 K. Both varied with the temperature and the concentration. The thermal conductivity of the crystal with butane adsorbed was 1.46 +/- 0.07 W/m K. Literature values of the isosteric enthalpy of adsorption, the concentration at saturation, and the diffusion coefficients were reproduced. Nonequilibrium molecular dynamics simulations were used to find these results, and a modified heat-exchange algorithm, Soft-HEX, was developed for the purpose. Enthalpies of butane were also determined. We use these results to give numerical proof for a recently proposed relation, that the heat of transfer plus the partial molar enthalpy of butane is constant at a given temperature. The proof is offered for a regime where the partial molar enthalpy can be approximated by the molar internal energy. This result may add to the understanding of the sign of the Soret coefficient. The technical importance of the heat of transfer is discussed.     

Colloido-chemical characteristics of porous glasses with different compositions in KNO3 solutions. 1. Structural and electrokinetic characteristics of membranes

The structural (specific surface area, liquid-filtration coefficient, average pore radius, volume porosity, and structural-resistance coefficient) and electrokinetic (counterion transport numbers, specific electrical conductivity, and electrokinetic potential) characteristics of porous glasses with different compositions have been determined in potassium nitrate solutions with concentrations of 10^?3–10^?1 M. All the membranes under investigation have been shown to exhibit the dependences of efficiency coefficients and counterion transport numbers on electrolyte concentration and pore size that are predicted by the theory of an electrical double layer. It has been established that, at a constant electrolyte concentration, the absolute values of electrokinetic potential increase with the average pore radius because of variations in the slipping-plane position.     

Study on radiative heat transfer property of fiber assemblies using FTIR

Radiative heat transfer could be a significant contribution to the total heat transfer within the highly porous materials. This article reports on the use of a conventional instrument, viz. Fourier transform infrared (FTIR) spectroscopy, for the characterization of radiative heat properties of fiber assemblies with low bulk densities. Experimental measurements on spectral transmission with FTIR were performed on five types of fiber assemblies commonly used for insulating materials. From the measurements, radiative heat conductivity was determined by calculating extinction coefficient using Beer’s Law and applying the diffusion approximation approach. Bulk density, fiber arrangement, and temperature influences to radiative heat transfer were discussed. Results show that radiative heat conductivity decreases with bulk density and that of the random arranged fiber assemblies shows lower radiative heat conductivity than the random ball and parallel arranged fiber assemblies. Radiative heat conductivity is proportional to the cubic temperature. The existing theoretical model was modified by comparing theoretical and experimental radiative heat conductivity results.     

Temperature and Concentration Dependence of the Electrical Conductance,Diffusion, and Kinetics Parameters of the Ions in Aqueous Solutions of Sulfuric Acid,Selenic Acid,and Potassium Tellurate

The temperature and concentration dependences of the electrical conductance of aqueous solutions of sulfuric acid, selenic acid, and potassium tellurate were studied. The coefficients of the corresponding empirical equations were determined, and the values of equivalent conductances of the anions were evaluated at infinite dilution at the experimental temperatures. The values of the coefficients in the Fuoss and Onsager equation were evaluated for the three electrolytes at 298 K. The values of the molecular and ionic coefficients of self-diffusion at infinite dilution were calculated in the temperature range 288–318 K. The change of the translational energy Δ E∘_tr. of water molecules in the ionic hydration sphere was determined. The number of water molecules participating in the ionic hydration sphere at 298 K and the changes of Gibbs free energy, enthalpy, and entropy of activation of ionic conductance were calculated. The results obtained were interpreted according to the Samoylov’s theory of positive and negative hydration of ions. The differences observed in the temperature dependences of the mentioned parameters were explained in terms of the different radii and hydration numbers of the ions.     

Influence of the counterion and co-ion diffusion coefficient values on some dielectric and electrokinetic properties of colloidal suspensions

The dependences of the conductivity increment, the electrophoretic mobility, and the permittivity increment on the counterion diffusion coefficient value were numerically determined. The use of the network simulation method made it possible to solve the governing equations for the whole range of counterion and co-ion diffusion coefficients and for very low frequencies, despite the far-reaching field-induced charge density outside the double layer. Calculations performed for different zeta potential and electrolyte concentration values show that increasing the counterion mobility, while keeping constant the electrolyte solution conductivity and the kappa a values, strongly increases the conductivity increment, barely affects the electrophoretic mobility, and strongly decreases the permittivity increment. The numerical results are discussed and compared to analytical predictions derived from the Shilov-Dukhin model, which generally leads to a good agreement, at least for high kappa a and moderate zeta.     

Prediction of thermodynamic derivative properties of natural condensate gases at high pressure by Monte Carlo simulation

We have employed Monte Carlo simulation in the isobaric–isothermal ensemble to determine thermodynamic derivative properties of naturally occurring hydrocarbon gas mixtures. Thermal expansivity, isothermal compressibility, heat capacity and Joule–Thomson coefficient have been obtained from a fluctuation method detailed in our previous work [Phys. Chem. Chem. Phys. 3 (2001) 4333]. We have investigated two natural gases using an original method to model hydrocarbon distribution in a representative way with a limited number of linear, branched and cyclic hydrocarbon molecules. The composition used in Monte Carlo simulations was represented by 500 molecules of 20 different types with up to 35 carbon atoms. The two condensate gases are composed of rigid and flexible molecules for which intermolecular potentials have been used without fitting any parameters. Predictions are in good agreement with respect to available molar volumes at high pressure. Joule–Thomson coefficients and the other thermodynamic derivative properties have been then predicted at pressures up to 110 MPa at reservoir temperature, showing a consistent behaviour compared with light hydrocarbon gases. Inversion pressure of the Joule–Thomson effect is obtained within 1.2% compared to experimental value from volumetric measurements.     

Concentration dependences of the transport coefficients of rod-like molecules in narrow slit-shaped pores

The concentration dependences of the label transport and shear viscosity coefficients for rod-like molecules in slit-shaped pores were studied. The calculations were carried out using the lattice gas model, which describes a broad range of fluid concentrations (from the gaseous to the liquid state) and temperatures (including the critical region). In the calculation of the local distributions of mixture components in the equilibrium states, lateral interactions were taken into account. The translational and rotational motions of molecules were described in terms of the transition state theory for nonideal reaction systems, which took into account the influence of neighboring molecules on the height of the activation barrier. The model equations reflect the pronounced anisotropy of the distribution of system components along the normal to the pore wall surface and ordering effects of molecules along various directions. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1485–1494, September, 2006.     

Properties of an aqueous solution of ionic liquid [Emim][Cl] at standard atmospheric pressure

The density, viscosity, electric conductivity, volumetric thermal expansion coefficient, melting point, and refractive index of an aqueous solution of the [Emim][Cl] ionic liquid are measured over wide ranges of temperature and concentrations at standard atmospheric pressure. Analytical dependences of the investigated properties on the concentration and temperature are suggested.     

Transport properties of Mie(14,7) fluids: molecular dynamics simulation and theory

An extensive computer simulation study is presented for the self-diffusion coefficient, the shear viscosity, and the thermal conductivity of Mie(14,7) fluids. The time-correlation function formalism of Green-Kubo is utilized in conjunction with molecular dynamics (MD) simulations. In addition to molecular simulations, the results of a recent study [A. Eskandari Nasrabad, J. Chem. Phys. 128, 154514 (2008)] for the mean free volume are applied to calculate the self-diffusion coefficients within a free volume theory framework. A detailed comparison between the MD simulation and free volume theory results for the diffusion coefficient is given. The density fluctuation theory of shear viscosity is used to compute the shear viscosity and the results are compared to those from MD simulations. The density and temperature dependences of different time-correlation functions and transport coefficients are studied and discussed.     

Phenomenological study on heat and mass coupling mechanism of waxy crude oil pipeline transport process

Based on the phase equilibrium model of the paraffin wax precipitation in the process of oil pipeline transportation, theory and method of non-equilibrium thermodynamics were applied to obtain the linear phenomenological equations for the cross-interaction of heat and mass transfer during pipeline transport, which were derived from the irreversible entropy production rate equation. Then, the analysis of the irreversible heat flow and the mass flow were carried out, and the mathematical expressions of the phenomenological coefficient of liquid phase, the phenomenological coefficient of solid phase flow, and the heat flow phenomenological coefficient were obtained. Taking a waxy crude oil transportation pipeline in Daqing Oilfield as an example, based on the analysis of liquid–solid phase equilibrium, the irreversible linear phenomenological mechanism of heat and mass coupling in waxy crude oil pipeline transportation was analyzed in detail from three levels: phenomenological coefficients which reflect characteristic of the effect of force on flow in heat and mass transfer; thermodynamic forces which trigger heat and mass transfer; transmitted heat and mass flow density, providing a theoretical basis for the further study of the wax deposition in the process of pipeline transportation.     

Approximation of contacts for calculating the velocity of the thermal motion of rodlike molecules in narrow slitlike pores

Expressions for calculating the thermal velocities of the motion of rodlike molecules in slitlike pores were obtained within the framework of a lattice gas model valid over a wide range of fluid densities (from rarefied gases to liquids) and temperatures, including the critical region. The translational and rotational motion of molecules was described using the transition-state theory for nonideal reaction systems, which takes into account the effect of the neighboring molecules on the activation barrier height. The local distributions of the components of the mixture under equilibrium conditions were calculated by describing lateral interactions in the approximation of isolated contacts. The equations of the model reflect the fact that the distributions of the components in the direction perpendicular to the pore walls (due to the effect of adsorption forces) and along the pore axis (if capillary condensation occurs) exhibit a strong anisotropy.     

Evaporation of Lennard-Jones fluids

Evaporation and condensation at a liquid/vapor interface are ubiquitous interphase mass and energy transfer phenomena that are still not well understood. We have carried out large scale molecular dynamics simulations of Lennard-Jones (LJ) fluids composed of monomers, dimers, or trimers to investigate these processes with molecular detail. For LJ monomers in contact with a vacuum, the evaporation rate is found to be very high with significant evaporative cooling and an accompanying density gradient in the liquid domain near the liquid/vapor interface. Increasing the chain length to just dimers significantly reduces the evaporation rate. We confirm that mechanical equilibrium plays a key role in determining the evaporation rate and the density and temperature profiles across the liquid/vapor interface. The velocity distributions of evaporated molecules and the evaporation and condensation coefficients are measured and compared to the predictions of an existing model based on kinetic theory of gases. Our results indicate that for both monatomic and polyatomic molecules, the evaporation and condensation coefficients are equal when systems are not far from equilibrium and smaller than one, and decrease with increasing temperature. For the same reduced temperature T/T(c), where T(c) is the critical temperature, these two coefficients are higher for LJ dimers and trimers than for monomers, in contrast to the traditional viewpoint that they are close to unity for monatomic molecules and decrease for polyatomic molecules. Furthermore, data for the two coefficients collapse onto a master curve when plotted against a translational length ratio between the liquid and vapor phase.     

Heat conduction in chain polymer liquids: molecular dynamics study on the contributions of inter- and intramolecular energy transfer

In this paper, the molecular mechanisms which determine the thermal conductivity of long chain polymer liquids are discussed, based on the results observed in molecular dynamics simulations. Linear n-alkanes, which are typical polymer molecules, were chosen as the target of our studies. Non-equilibrium molecular dynamics simulations of bulk liquid n-alkanes under a constant temperature gradient were performed. Saturated liquids of n-alkanes with six different chain lengths were examined at the same reduced temperature (0.7T(c)), and the contributions of inter- and intramolecular energy transfer to heat conduction flux, which were identified as components of heat flux by the authors' previous study [J. Chem. Phys. 128, 044504 (2008)], were observed. The present study compared n-alkane liquids with various molecular lengths at the same reduced temperature and corresponding saturated densities, and found that the contribution of intramolecular energy transfer to the total heat flux, relative to that of intermolecular energy transfer, increased with the molecular length. The study revealed that in long chain polymer liquids, thermal energy is mainly transferred in the space along the stiff intramolecular bonds. This finding implies a connection between anisotropic thermal conductivity and the orientation of molecules in various organized structures with long polymer molecules aligned in a certain direction, which includes confined polymer liquids and self-organized structures such as membranes of amphiphilic molecules in water.     

氢在沸石上的吸附行为

应用基于Ono-Kondo格子理论得到的通用吸附等温方程, 通过分析氢在不同温度下, 在沸石NaX、CaA、NaA和ZSM-5上的吸附数据, 确定了氢的最大单层吸附容量. 并引入维里吸附方程, 由第二维里吸附系数和圆柱孔的Lennard-Jones(12-6)势模型计算了氢与沸石微孔壁面的作用势. 结果表明, 通用吸附等温方程可较好地描述氢在沸石上的超临界吸附行为, 拟合所得的氢在沸石上的最大单层吸附容量与吸附剂相关, 而与吸附温度无关. 圆柱孔作用势模型计算所得的氢分子在沸石上的吸附作用势与吸附热相近. 氢分子间的作用力表现为吸引力.     

Molecular Dynamics Simulation of Diffusion of Vitamin C in Water Solution

Under different temperatures and concentrations, the diffusion of Vitamin C (VC) in water solution was examined by molecular dynamics simulation. The diffusion coefficients were calculated based on the Einstein equation. The influences of temperature, concentration, and simulation time on the diffusion coefficient were discussed. The results showed that at higher temperature and lower concentration the normal diffusions appear relatively late, but the linear range of mean square displacement curves continues longer than that at lower temperature and higher concentration. At the same temperature, the normal diffusion time increases and the diffusion coefficient decreases as the simulation concentration increases. These simulation results are in good agreement with experiments. Analyses of the pair correlation functions of the simulation systems showed that hydrogen bonds are mainly formed between the hydrogen atoms of VC molecules and oxygen atoms of H₂O molecules, rather than between the O atoms of VC molecules and H atoms of H₂O molecules. The diffusion coefficient is higher as the interaction between water molecules and VC molecules is stronger when VC concentration is lower. The water in the model systems affects the diffusion of VC molecules by the short‐range repulsion of O(H₂O)‐O(H₂O) pairs and the non‐bond interaction of H(H₂O)‐H(H₂O) pairs. The short‐range repulsion of O(H₂O)‐O(H₂O) pairs is greater when VC concentration is higher, the diffusion of VC is weaker. The greater the non‐bond interaction of H(H₂O)‐H(H₂O) pairs is, the higher the VC diffusion is. It is expected that this study can provide a theoretical direction for the experiments on the mass transfer of VC in water solution.