Print Email Facebook Twitter Generic low-density corrections to the equation of state of chain molecules with repulsive intermolecular forces Title Generic low-density corrections to the equation of state of chain molecules with repulsive intermolecular forces Author van Westen, Thijs (University of Stuttgart) Rehner, Philipp (ETH Zürich) Vlugt, T.J.H. (TU Delft Engineering Thermodynamics) Gross, Joachim (University of Stuttgart) Date 2024 Abstract Molecular-based equations of state for describing the thermodynamics of chain molecules are often based on mean-field like arguments that reduce the problem of describing the interactions between chains to a simpler one involving only nonbonded monomers. While for dense liquids such arguments are known to work well, at low density they are typically less appropriate due to an incomplete description of the effect of chain connectivity on the local environment of the chains’ monomer segments. To address this issue, we develop three semi-empirical approaches that significantly improve the thermodynamic description of chain molecules at low density. The approaches are developed for chain molecules with repulsive intermolecular forces; therefore, they could be used as reference models for developing equations of the state of real fluids based on perturbation theory. All three approaches are extensions of Wertheim’s first-order thermodynamic perturbation theory (TPT1) for polymerization. The first model, referred to as TPT1-v, incorporates a second-virial correction that is scaled to zero at liquid-like densities. The second model, referred to as TPT1-y, introduces a Helmholtz-energy contribution to account for correlations between next-nearest-neighbor segments within chain molecules. The third approach, called TPT-E, directly modifies TPT1 without utilizing an additional Helmholtz energy contribution. By employing TPT1 at the core of these approaches, we ensure an accurate description of mixtures and enable a seamless extension from chains of tangentially bonded hard-sphere segments of equal size to hetero-segmented chains, fused chains, and chains of soft repulsive segments (which are influenced by temperature). The low-density corrections implemented in TPT1 are designed to preserve these good characteristics, as confirmed through comparisons with novel molecular simulation results for the pressure of various chain fluids. TPT1-v exhibits excellent transferability across different chain types, but it relies on knowing the second virial coefficient of the chain molecules, which is non-trivial to obtain and determined here using Monte Carlo simulation. The TPT1-y model, on the other hand, achieves comparable accuracy to TPT1-v while being fully predictive, requiring no input besides the geometry of the chain molecules. To reference this document use: http://resolver.tudelft.nl/uuid:e5f96899-72d8-43a7-a6c4-bbdfad6172d0 DOI https://doi.org/10.1063/5.0197910 Embargo date 2024-11-01 ISSN 0021-9606 Source Journal of Chemical Physics, 160 (17) Bibliographical note Green Open Access added to TU Delft Institutional Repository 'You share, we take care!' - Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public. Part of collection Institutional Repository Document type journal article Rights © 2024 Thijs van Westen, Philipp Rehner, T.J.H. Vlugt, Joachim Gross Files file embargo until 2024-11-01