Small hard spheres binary mixtures

Binary Mixtures of Large and Small Hard Spheres. 167... 

For a binary mixture, if experimental diffusivities do not exist over the whole range of concentration, an interpolation of the diffusivities at infinite dilution D k] J is used. In calculating the diffusivities at infinite dilution by the Stokes-Einstein relation, we consider small isolated hard spheres, submerged in a liquid, that are subjected to Brownian motion The friction of the spheres in the liquid is given by the Stokes law Einstein used the Stokes law to calculate the mean-square displacement of a particle. The displacement increases linearly with time, and the proportionality constant is the Stokes-Einstein diffusivity... 

The possibility of entropy-driven phase separation in purely hard-core fluids has been of considerable recent interest experimentally, theoretically, and via computer simulations. Systems studied include binary mixtures of spheres (or colloids) of different diameters, mixtures of large colloidal spheres and flexible polymers, mixtures of colloidal spheres and rods," and a polymer/small molecule solvent mixture under infinite dilution conditions (here an athermal conformational coil-to-globule transition can occur)." For the latter three problems, PRISM theory could be applied, but to the best of our knowledge has not. The first problem is an old one solved analytically using PY integral equation theory by Lebowitz and Rowlinson." No liquid-liquid phase separation... 

Both SAFT and PC-SAFT contain pure component parameters the energy parameter or u, the hard-sphere diameter a, or the hard-sphere volume and the number of segments m per molecule. For small (solvent) molecules these parameters are obtained from a fit of vapor pressure data and saturated liquid volume data. Since they do not have a vapor pressure, this fit is not possible for polymers, and the pure component polymer parameters are obtained from a fit to PVT data of the molten polymer or from a fit to PVT data and binary phase equilibrium data. For the description of a mixture one needs one binary interaction parameter ky per binary, which has to be fitted to phase equilibrium data. If necessary, ky can be made temperature-dependent. In general, phase equilibria are very sensitive to the kij value. 

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