Abstract
A closed-form statistical mechanical based equation of state for associating chain fluids is presented. A Lennard-Jones chain is used as a reference to account for the repulsive, dispersive and anisotropic (size) contributions, while the short-range directional attraction is treated as a perturbation expansion based on Wertheim's first-order theory of associating fluids. A model fluid composed of a chain of tangently bonded Lennard-Jones spheres with an associating square-well site at one of the end spheres is studied. Isobaric-isothermal Monte Carlo simulations were performed for this model at subcritical and supercritical temperatures at a association strength typical of hydrogen-bonding systems. The theory is seen accurately to predict the simulation results subject to the limitations of the equation of state of the reference fluid. The system studied has some of the main complexities found in associating chain molecules such as organic acids, alkanols, and primary amines.
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Müller, E.A., Vega, L.F. & Gubbin, K.E. Molecular simulation and theory of associating chain molecules. Int J Thermophys 16, 705–713 (1995). https://doi.org/10.1007/BF01438855
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DOI: https://doi.org/10.1007/BF01438855