Structure of ternary additive hard-sphere fluid mixtures

Monte Carlo simulations on the structural properties of ternary fluid mixtures of additive hard spheres are reported. The results are compared with those obtained from a recent analytical approximation [S. B. Yuste, A. Santos, and M. Lopez de Haro, J. Chem. Phys. 108, 3683 (1998)] to the radial distribution functions of hard-sphere mixtures and with the results derived from the solution of the Ornstein-Zernike integral equation with both the Martynov-Sarkisov and the Percus-Yevick closures. Very good agreement between the results of the first two approaches and simulation is observed, with a noticeable improvement over the Percus-Yevick predictions especially near contact.Comment: 11 pages, including 8 figures; A minor change; accepted for publication in PR

Diffusion of impurities in a granular gas

Diffusion of impurities in a granular gas undergoing homogeneous cooling state is studied. The results are obtained by solving the Boltzmann--Lorentz equation by means of the Chapman--Enskog method. In the first order in the density gradient of impurities, the diffusion coefficient $D$ is determined as the solution of a linear integral equation which is approximately solved by making an expansion in Sonine polynomials. In this paper, we evaluate $D$ up to the second order in the Sonine expansion and get explicit expressions for $D$ in terms of the restitution coefficients for the impurity--gas and gas--gas collisions as well as the ratios of mass and particle sizes. To check the reliability of the Sonine polynomial solution, analytical results are compared with those obtained from numerical solutions of the Boltzmann equation by means of the direct simulation Monte Carlo (DSMC) method. In the simulations, the diffusion coefficient is measured via the mean square displacement of impurities. The comparison between theory and simulation shows in general an excellent agreement, except for the cases in which the gas particles are much heavier and/or much larger than impurities. In theses cases, the second Sonine approximation to $D$ improves significantly the qualitative predictions made from the first Sonine approximation. A discussion on the convergence of the Sonine polynomial expansion is also carried out.Comment: 9 figures. to appear in Phys. Rev.

Predicting diffusivities in dense fluid mixtures

In this work the Enskog solution of the Boltzmann equation, as corrected by Speedy, together with the Weeks-Chandler-Andersen (WCA) perturbation theory of liquids is employed in correlating and predicting self-diffusivities of dense fluids. Afterwards this theory is used to estimate mutual diffusion coefficients of solutes at infinite dilution in sub and supercritical solvents. We have also investigated the behavior of Fick diffusion coefficients in the proximity of a binary vapor-liquid critical point since this subject is of great interest for extraction purposes. The approach presented here, which makes use of a density and temperature dependent hard-sphere diameter, is shown to be excellent for predicting diffusivities in dense pure fluids and fluid mixtures. The calculations involved highly nonideal mixtures as well as systems with high molecular asymmetry. The predicted diffusivities are in good agreement with the experimental data for the pure and binary systems. The methodology proposed here makes only use of pure component information and density of mixtures. The simple algebraic relations are proposed without any binary adjustable parameters and can be readily used for estimating diffusivities in multicomponent mixtures

Alternative Approaches to the Equilibrium Properties of Hard-Sphere Liquids

An overview of some analytical approaches to the computation of the structural and thermodynamic properties of single component and multicomponent hard-sphere fluids is provided. For the structural properties, they yield a thermodynamically consistent formulation, thus improving and extending the known analytical results of the Percus–Yevick theory. Approximate expressions for the contact values of the radial distribution functions and the corresponding analytical equations of state are also discussed. Extensions of this methodology to related systems, such as sticky hard spheres and squarewell fluids, as well as its use in connection with the perturbation theory of fluids are briefly addressed.