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Byung Chan Eu

Publications and source records attributed to Byung Chan Eu.

15 recordsLinked to original sources
PubMed2006

Relative Boltzmann entropy, evolution equations for fluctuations of thermodynamic intensive variables, and a statistical mechanical representation of the zeroth law of thermodynamics.

Generalized thermodynamics or extended irreversible thermodynamics presumes the existence of thermodynamic intensive variables (e.g., temperature, pressure, chemical potentials, generalized potentials) even if the system is removed from equilibrium. It is necessary to properly understand the nature of such intensive variables and, in particular, of their fluctuations, that is, their deviations from those defined in the extended irreversible thermodynamic sense. The meaning of temperature is examined by means of a kinetic theory of macroscopic irreversible processes to assess the validity of the generalized (or extended) thermodynamic method applied to nonequilibrium phenomena. The Boltzmann equation is used for the purpose. Since the relative Boltzmann entropy has been known to be intimately related to the evolution of the aforementioned fluctuations in the intensive thermodynamic variables, we derive the evolution equations for such fluctuations of intensive variables to lay the foundation for investigating the physical implications and evolution of the relative Boltzmann entropy, so that the range of validity of the thermodynamic theory of irreversible processes can be elucidated. Within the framework of this work, we examine a special case of the evolution equations for the aforementioned fluctuations of intensive variables, which also facilitate investigation of the molecular theory meaning of the zeroth law of thermodynamics. We derive an evolution equation describing the relaxation of temperature fluctuations from its local value and present a formula for the temperature relaxation time.

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PubMed2006

Excluded volume in the generic van der Waals equation of state and the self-diffusion coefficient of the Lennard-Jones fluid.

In the previous papers applying the generic van der Waals equation of state the mean excluded volume was defined with the contact diameter of particles at which the potential energy is equal to zero-the size parameter in the case of the Lennard-Jones potential. This parameter appears as the upper limit of the integral for the generic van der Waals parameter B (mean excluded volume divided by the density) in the generic van der Waals equation of state. Since the choice is not unique, in this paper we reexamine the manner of defining the upper limit and propose another choice for the upper limit. We also propose an interpretation of the free volume overlap factor alpha appearing in the free volume theory of diffusion and a method of estimating it in terms of the intermolecular potential energy only. It is shown that with the so-estimated free volume overlap factor and the new choice of the upper limit of the integral for B the self-diffusion coefficient in the modified free volume theory of diffusion not only acquires a better accuracy than before, but also becomes calculable in terms of only the intermolecular interaction potential without an adjustable parameter. We also assess some of effective diameters of molecules proposed in the literature for their ability to predict the self-diffusion coefficient within the framework of the modified free volume theory of diffusion.

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PubMed2006

Molecular theory of thermal conductivity of the Lennard-Jones fluid.

In this paper the thermal conductivity of the Lennard-Jones fluid is calculated by applying the combination of the density-fluctuation theory, the modified free volume theory of diffusion, and the generic van der Waals equation of state. A Monte Carlo simulation method is used to compute the equilibrium pair-correlation function necessary for computing the mean free volume and the coefficient in the potential-energy and virial contributions to the thermal conductivity. The theoretical results are compared with our own molecular dynamics simulation results and with those reported in the literature. They agree in good accuracy over wide ranges of density and temperature examined in molecular dynamics simulations. Thus the combined theory represents a molecular theory of thermal conductivity of the Lennard-Jones fluid and by extension simple fluids, which enables us to compute the nonequilibrium quantity by means of the Monte Carlo simulations for the equilibrium pair-correlation function.

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PubMed2006

Relations between transport coefficients and their density and temperature dependence.

Nonequilibrium statistical mechanics via density fluctuation theory predicts relations between the bulk and shear viscosity, thermal conductivity, and self-diffusion coefficient of a fluid. In this Feature Article, we discuss such relations holding for fluids over wide ranges of density and temperature experimentally studied in the laboratory. It is discussed how such relations can be used to successfully compute the density and temperature dependence on the basis of intermolecular interaction potential models with the help of the modified free volume theory and the generic van der Waals equation of state once the parameters in them are determined at a low density or at a subcritical temperature. Although some approximations have been made to derive them, they represent a reliable molecular theory of transport coefficients over the entire density and temperature ranges of fluids--namely, gases and liquids--a theory hitherto unavailable in the kinetic theory of liquids and dense gases.

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PubMed2005

Statistical-mechanical theory of rheology: Lennard-Jones fluids.

The generalized Boltzmann equation for simple dense fluids gives rise to the stress tensor evolution equation as a constitutive equation of generalized hydrodynamics for fluids far removed from equilibrium. It is possible to derive a formula for the non-Newtonian shear viscosity of the simple fluid from the stress tensor evolution equation in a suitable flow configuration. The non-Newtonian viscosity formula derived is applied to calculate the non-Newtonian viscosity as a function of the shear rate by means of statistical mechanics in the case of the Lennard-Jones fluid. For that purpose we have used the density-fluctuation theory for the Newtonian viscosity, the modified free volume theory for the self-diffusion coefficient, and the generic van der Waals equation of state to compute the mean free volume appearing in the modified free volume theory. Monte Carlo simulations are used to calculate the pair-correlation function appearing in the generic van der Waals equation of state and shear viscosity formula. To validate the Newtonian viscosity formula obtained we first have examined the density and temperature dependences of the shear viscosity in both subcritical and supercritical regions and compared them with molecular-dynamic simulation results. With the Newtonian shear viscosity and thermodynamic quantities so computed we then have calculated the shear rate dependence of the non-Newtonian shear viscosity and compared it with molecular-dynamics simulation results. The non-Newtonian viscosity formula is a universal function of the product of reduced shear rate (gamma*) times reduced relaxation time (taue*) that is independent of the material parameters, suggesting a possibility of the existence of rheological corresponding states of reduced density, temperature, and shear rate. When the simulation data are reduced appropriately and plotted against taue*gamma* they are found clustered around the reduced (universal) non-Newtonian viscosity formula. Thus we now have a molecular theory of non-Newtonian shear viscosity for the Lennard-Jones fluid, which can be implemented with a Monte Carlo simulation method for the pair-correlation function.

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PubMed2005

Pair correlation functions and the self-diffusion coefficient of Lennard-Jones liquid in the modified free volume theory of diffusion.

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.

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PubMed2005

Modified free volume theory of self-diffusion and molecular theory of shear viscosity of liquid carbon dioxide.

In previous work on the density fluctuation theory of transport coefficients of liquids, it was necessary to use empirical self-diffusion coefficients to calculate the transport coefficients (e.g., shear viscosity of carbon dioxide). In this work, the necessity of empirical input of the self-diffusion coefficients in the calculation of shear viscosity is removed, and the theory is thus made a self-contained molecular theory of transport coefficients of liquids, albeit it contains an empirical parameter in the subcritical regime. The required self-diffusion coefficients of liquid carbon dioxide are calculated by using the modified free volume theory for which the generic van der Waals equation of state and Monte Carlo simulations are combined to accurately compute the mean free volume by means of statistical mechanics. They have been computed as a function of density along four different isotherms and isobars. A Lennard-Jones site-site interaction potential was used to model the molecular carbon dioxide interaction. The density and temperature dependence of the theoretical self-diffusion coefficients are shown to be in excellent agreement with experimental data when the minimum critical free volume is identified with the molecular volume. The self-diffusion coefficients thus computed are then used to compute the density and temperature dependence of the shear viscosity of liquid carbon dioxide by employing the density fluctuation theory formula for shear viscosity as reported in an earlier paper (J. Chem. Phys. 2000, 112, 7118). The theoretical shear viscosity is shown to be robust and yields excellent density and temperature dependence for carbon dioxide. The pair correlation function appearing in the theory has been computed by Monte Carlo simulations.

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PubMed2005

Generic van der Waals equation of state, modified free volume theory of diffusion, and viscosity of simple liquids.

The shear viscosity formula derived by the density fluctuation theory in previous papers is computed for argon, krypton, and methane by using the self-diffusion coefficients derived in the modified free volume theory with the help of the generic van der Waals equation of state. In the temperature regime near or above the critical temperature, the density dependence of the shear viscosity can be accounted for by ab initio calculations with the self-diffusion coefficients provided by the modified free volume theory if the minimum (critical) free volume is set equal to the molecular volume and the volume overlap parameter (alpha) is taken about unity in the expression for the self-diffusion coefficient. In the subcritical temperature regime, if the density fluctuation range parameter is chosen appropriately at a temperature, then the resulting expression for the shear viscosity can well account for its density and temperature dependence over the ranges of density and temperature experimentally studied. In the sense that once the density fluctuation range is fixed at a temperature, the theory can account for the experimental data at other subcritical temperatures on the basis of the intermolecular force only; the theory is predictive even in the subcritical regime of temperature. Theory is successfully tested in comparison with experimental data for self-diffusion coefficients and shear viscosity for argon, krypton, and methane.

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PubMed2004

Generalized hydrodynamics in the transient regime and irreversible thermodynamics.

In this article the thermodynamically consistent formulation of generalized hydrodynamics is reviewed and applications to shock-wave structures, ultrasonic wave absorption and dispersion and microchannel flows of the generalized hydrodynamics so formulated are discussed. The kinematic terms of the constitutive equations in the generalized hydrodynamic equations for liquids, which have been calculated by means of non-equilibrium grand canonical ensemble, are also presented.

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PubMed2004

Generalized hydrodynamics and microflows.

In this paper, a mathematical model within the framework of generalized hydrodynamics is developed for the description of flows in microsystems where the Knudsen number is large and the aspect ratio [(width)/(length)] is not so small. The model is based on a set of empirical generalized hydrodynamic equations, which are fashioned from the steady-state generalized hydrodynamic equations derived from the Boltzmann equation in a manner consistent with the laws of thermodynamics. The constitutive equations used for the model are highly nonlinear, unlike the Newtonian law of viscosity and the Fourier law of heat conduction, but they are thermodynamically consistent. In the absence of heat conduction, the model yields exact solutions for the velocity components and a nonlinear differential equation for the pressure distribution in the rectangular microchannel. The Langmuir adsorption model for surface-gas interaction is used for boundary conditions for the velocity. The calculated flow rate exhibits a Knudsen minimum with respect to the Knudsen number. The longitudinal velocity profile is also non-Poiseuille. The differential equation for pressure distribution is also solved approximately in order to obtain an analytic formula for the flow rate, which exhibits a Knudsen minimum. The formula, although approximate, provides considerable insights into the Knudsen flow phenomena in microchannels.

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PubMed2003

Theory of the viscosity of supercooled liquids and the glass transition: fragile liquids.

A statistical mechanical theory is presented for viscosity of relatively low molecular weight organic liquids which are supercooled down to the glass transition temperature. In this theory a relation resembling the Stokes-Einstein relation between the viscosity and self-diffusion coefficient of supercooled liquids and an expression for the self-diffusion coefficient are augmented by a suitably constructed semiempirical generic van der Waals equation of state that makes it possible to calculate the free volume. The theory accounts in excellent accuracy for viscosities and self-diffusion coefficients of fragile liquids over the entire range of temperature experimentally investigated. According to the theory, vitrification occurs when the free volume available for translational molecular motion falls below a critical value.

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PubMed2002

Nonlinear viscosity derived by means of Grad's moment method.

In this paper we examine the stress tensor component evolution equations recently derived by Uribe and Garcia-Colin [Phys. Rev. E 60, 4052 (1999)] for unidirectional flow at uniform temperature under the assumption/approximation of vanishing transversal velocity gradients. By removing this assumption/approximation we derive the stress tensor evolution equation from the Boltzmann equation within the framework of the Grad moment expansion for the case of uniform temperature (the same condition as theirs). Specializing the evolution equation to the case of steady unidirectional flow in a square channel, we obtain a set of steady state evolution equations for the components of the stress tensor. Because the transversal velocity gradients are not assumed to vanish in this paper in contrast to their paper, the present result is more general than theirs. Its special case corresponding to the one-dimensional flow considered by Uribe and Garcia-Colin is at variance with theirs because of a missing term in their stress evolution equation for the xy component. The nonlinear viscosity formulas are also different. A general remark is given with regard to the relation of dimensionalities of hydrodynamic equations and the kinetic equation underlying the former. They are not necessarily the same.

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PubMed2002

Free volume and density and temperature dependence of diffusion coefficients of liquid mixtures.

A simple formula for the diffusion coefficient of liquid mixtures, expressed in terms of the work necessary to create a characteristic free volume in the liquid, is presented in the spirit of the Arrhenius activation theory and tested in comparison with available experimental data. If use is made of the generic van der Waals equation of state, the free volume appearing in the formula for the diffusion coefficient can be expressed in terms of the equilibrium pair correlation functions. The theoretical values for diffusion coefficients agree excellently with experimental values with regard to the density and temperature dependence of the diffusion coefficients of argon and krypton.

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