THE WERTHEIM INTEGRAL EQUATION THEORY WITH THE IDEAL CHAIN APPROXIMATION AND A DIMER EQUATION OF STATE - GENERALIZATION TO MIXTURES OF HARD-SPHERE CHAIN FLUIDS

摘要

We have extended the Wertheim integral equation theory to mixtures of hard spheres with two attraction sites in order to model homonuclear hard-sphere chain fluids, and then solved these equations with the polymer-Percus-Yevick closure and the ideal chain approximation to obtain the average intermolecular and overall radial distribution functions. We obtain explicit expressions for the contact values of these distribution functions and a set of one-dimensional integral equations from which the distribution functions can be calculated without iteration or numerical Fourier transformation. We compare the resulting predictions for the distribution functions with Monte Carlo simulation results we report here for five selected binary mixtures. It is found that the accuracy of the prediction of the structure is the best for dimer mixtures and declines with increasing chain length and chain-length asymmetry. For the equation of state, we have extended the dimer version of the thermodynamic perturbation theory to the hard-sphere chain mixture by introducing the dimer mixture as an intermediate reference system. The Helmholtz free energy of chain fluids is then expressed in terms of the free energy of the hard-sphere mixture and the contact values of the correlation functions of monomer and dimer mixtures. We compared with the simulation results, the resulting equation of state is found to be the most accurate among existing theories with a relative average error of 1.79% for 4-mer/8-mer mixtures, which is the worst case studied in this work. (C) 1995 American Institute of Physics. [References: 72]