An Equation of State for the Hard-Sphere Chain Fluid Based on the Thermodynamic Perturbation Theory of Sequential Polymerization

New equations of state for freely joiInted hard-sphere chain fluids are developed. The equations of state are based on the thermodynamic perturbation theory. The new equations of state use the contact values of the radial distribution function (RDF) for monomer–dimer mixtures, which is derived from the multidensity Ornstein–Zernike theory. These RDFs are composed of a monomer reference term, the Carnahan–Starling or the Percus–Yevick expression, and an additional bond contribution. These equations of state are then extended to real fluids. To calculate the phase equilibrium properties of nonassociating chain fluids, a dispersion contribution is added to the repulsive hard-chain reference term. With the new equations of state of chain fluids supplemeInted with the dispersion term, the vapor pressures and the coexisting densities of several real fluids are calculated.