Intramolecular bonding in a statistical associating fluid theory of ring aggregates

Febra, Sara; Aasen, Ailo; Adjiman, Claire S.; Jackson, George; Galindo, Amparo

doi:10.1080/00268976.2019.1671619

Cited by 9 publications

(3 citation statements)

References 79 publications

(180 reference statements)

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“…Since then, the theory has been successfully applied to a variety of fluid mixtures such as electrolyte solutions, polymer mixtures, mixtures of cyclic and ring-forming compounds, and much more. [24][25][26][27] However, the present work is the first time the theory is used to describe mixtures of quantum-corrected Mie fluids. The hard-sphere contribution turns out to be especially important for these fluids, since their interaction potentials have shallower attractive tails and harder repulsive cores than classical Mie fluids.…”

Section: Introductionmentioning

confidence: 98%

Equation of state and force fields for Feynman–Hibbs-corrected Mie fluids. II. Application to mixtures of helium, neon, hydrogen, and deuterium

Aasen

Hammer

Müller

et al. 2020

The Journal of Chemical Physics

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We extend the SAFT-VRQ Mie equation of state, previously developed for pure fluids [Aasen et al., J. Chem. Phys. 151, 064508 (2019)], to fluid mixtures of particles interacting via Mie potentials with Feynman-Hibbs quantum corrections of first (Mie-FH1) or second order (Mie-FH2). This is done using a third-order Barker-Henderson expansion of the Helmholtz energy from a non-additive hard-sphere reference system. We survey existing experimental measurements and ab initio calculations of thermodynamic properties of mixtures of neon, helium, deuterium and hydrogen, and use them to optimize the Mie-FH1 and Mie-FH2 force fields for binary interactions. Simulations employing the optimized force fields are shown to follow the experimental results closely over the entire phase envelopes. SAFT-VRQ Mie reproduces results from simulations employing these force fields, with the exception of near-critical states for mixtures containing helium. This breakdown is explained in terms of the extremely low dispersive energy of helium, and the challenges inherent in current implementations of the Barker-Henderson expansion for mixtures. The interaction parameters of two cubic equations of state (SRK, PR) are also fitted to experiments, and used as performance benchmarks. There are large gaps in the ranges and properties that have been experimentally measured for these systems, making the force fields presented especially useful.

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Section: Introductionmentioning

confidence: 98%

Equation of state and force fields for Feynman–Hibbs-corrected Mie fluids. II. Application to mixtures of helium, neon, hydrogen, and deuterium

Aasen

Hammer

Müller

et al. 2020

The Journal of Chemical Physics

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“…Although neglecting Δ c p , i ( T i fus , P ) can significantly affect the solubility prediction, − depending on the mixture and the temperature, experimental values for Δ c p , i ( T i fus , P ) are unknown for most of the molecules considered in our work. Hence, we do not take this contribution into account in our current calculations.…”

Section: Methodsmentioning

confidence: 99%

Modeling the Thermodynamic Properties of Saturated Lactones in Nonideal Mixtures with the SAFT-γ Mie Approach

Bernet,

Wehbe,

Febra

et al. 2023

J. Chem. Eng. Data

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The prediction of the thermodynamic properties of lactones is an important challenge in the flavor, fragrance, and pharmaceutical industries. Here, we develop a predictive model of the phase behavior of binary mixtures of lactones with hydrocarbons, alcohols, ketones, esters, aromatic compounds, water, and carbon dioxide. We extend the group-parameter matrix of the statistical associating fluid theory SAFT-γ Mie group-contribution method by defining a new cyclic ester group, denoted cCOO. The group is composed of two spherical Mie segments and two association electron-donating sites of type e 1 that can interact with association electron-accepting sites of type H in other molecules. The model parameters of the new cCOO group interactions (1 like interaction and 17 unlike interactions) are characterized to represent target experimental data of physical properties of pure fluids (vapor pressure, single-phase density, and vaporization enthalpy) and mixtures (vapor−liquid equilibria, liquid−liquid equilibria, solid−liquid equilibria, density, and excess enthalpy). The robustness of the model is assessed by comparing theoretical predictions with experimental data, mainly for oxolan-2-one, 5-methyloxolan-2-one, and oxepan-2-one (also referred to as γ-butyrolactone, γvalerolactone, and ε-caprolactone, respectively). The calculations are found to be in very good quantitative agreement with experiments. The proposed model allows for accurate predictions of the thermodynamic properties and highly nonideal phase behavior of the systems of interest, such as azeotrope compositions. It can be used to support the development of novel molecules and manufacturing processes.

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“…Current SAFT models do not explicitly account for intramolecular association. Most current SAFT models do not explicitly account for intramolecular association or ring formation, but extensions to include intramolecular association or ring formation are available. ,− …”

Section: Activity Coefficients At Low Concentrations and Idacsmentioning

confidence: 99%

Wertheim’s Association Theory for Phase Equilibrium Modeling in Chemical Engineering Practice

Lira

Elliott

Gupta

et al. 2022

Ind. Eng. Chem. Res.

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Association and complex formation are the most important contributors to nonidealities in modeling phase equilibria. Models based on Wertheim's association theory are reviewed in the context of current industrial practice, showing great promise in resolving many of the shortcomings of the currently available models. Several pitfalls of common models are highlighted, showing the advantages of association theory. Infinite dilution activity coefficients can provide valuable insights into the liquid phase nonidealities. Trends for various mixture classifications are tabulated and explained simply in terms of "differences in molecular association". The need for a systematic procedure to characterize association parameters is cited as the most important barrier to broader implementation of these models. Improper characterizations can undermine the advantages of association theory, possibly confusing whether it offers any advantage. Resolving these issues will improve traditional small molecule phase equilibrium modeling and many other applications as well.

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Intramolecular bonding in a statistical associating fluid theory of ring aggregates

Cited by 9 publications

References 79 publications

Equation of state and force fields for Feynman–Hibbs-corrected Mie fluids. II. Application to mixtures of helium, neon, hydrogen, and deuterium

Equation of state and force fields for Feynman–Hibbs-corrected Mie fluids. II. Application to mixtures of helium, neon, hydrogen, and deuterium

Modeling the Thermodynamic Properties of Saturated Lactones in Nonideal Mixtures with the SAFT-γ Mie Approach

Wertheim’s Association Theory for Phase Equilibrium Modeling in Chemical Engineering Practice

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