Print Email Facebook Twitter Scaling towards the critical point in the combined reaction/Gibbs ensemble Title Scaling towards the critical point in the combined reaction/Gibbs ensemble Author Polat, H.M. (TU Delft Engineering Thermodynamics) Lasala, Silvia (Laboratoire Réactions et Génie des Procédés (LRGP)) De Meyer, Frédérick (TotalEnergies; Center for Thermodynamics of Processes (CTP)) Houriez, Céline (Center for Thermodynamics of Processes (CTP)) Moultos, O. (TU Delft Engineering Thermodynamics) Vlugt, T.J.H. (TU Delft Engineering Thermodynamics) Date 2024 Abstract We explore the impact of force field parameters and reaction equilibrium on the scaling behavior towards the critical point in reactive binary systems, focusing on NO 2/N 2O 4. This system can be considered as a special single-component system since NO 2 and N 2O 4 are in chemical equilibrium via the chemical reaction 2NO 2⇌N 2O 4. We simplify the system by representing both components as single LJ particles, achieving excellent agreement with densities computed using molecular simulations in which all-atom force fields were used. We investigate the effect of force field parameters (ɛ and σ) on phase behavior and show that the critical exponent β remains constant, which means that intermolecular interactions do not affect the scaling to the critical point when the chemical reaction takes place. We also investigate the sensitivity of the reaction equilibrium constant and show that even small changes in isolated molecule partition functions lead to large differences in chemical equilibria. We show that the critical exponent β is different for systems with different reaction equilibrium constants, so a careful parameterization of β is needed for an accurate computation of critical temperatures of reactive mixtures. We perform a screening of reactive binary mixtures for a wide range of ideal gas reaction equilibrium constants, revealing key insights into the thermodynamic behavior and critical properties. Thereby we facilitate the efficient screening of reactive binary mixtures for various applications. Our results emphasize the importance of accurately parameterizing β and provide valuable insights into the critical scaling behavior of complex reactive systems. Subject Gibbs ensembleReaction ensembleMonte Carlo simulationsCritical temperatureCritical densityReactive mixtures To reference this document use: http://resolver.tudelft.nl/uuid:576d1052-37ed-4375-85fe-65ce1b68aac2 DOI https://doi.org/10.1016/j.fluid.2024.114084 ISSN 0378-3812 Source Fluid Phase Equilibria, 582 Part of collection Institutional Repository Document type journal article Rights © 2024 H.M. Polat, Silvia Lasala, Frédérick De Meyer, Céline Houriez, O. Moultos, T.J.H. Vlugt Files PDF 1-s2.0-S037838122400061X-main.pdf 1.1 MB Close viewer /islandora/object/uuid:576d1052-37ed-4375-85fe-65ce1b68aac2/datastream/OBJ/view