Modeling the thermodynamic properties of saturated lactones in nonideal mixtures with the SAFT-γ Mie approach
Author(s)
Type
Journal Article
Abstract
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 e1 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, γ-valerolactone, 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.
Date Issued
2024-02-08
Date Acceptance
2023-08-30
Citation
Journal of Chemical and Engineering Data, 2024, 69 (2), pp.650-678
ISSN
0021-9568
Publisher
American Chemical Society
Start Page
650
End Page
678
Journal / Book Title
Journal of Chemical and Engineering Data
Volume
69
Issue
2
Copyright Statement
© 2023 The Authors. Published by American Chemical Society. This publication is licensed under CC-BY 4.0 .
License URL
Identifier
https://www.ncbi.nlm.nih.gov/pubmed/38352073
Subjects
ASSOCIATING FLUIDS
BINARY-SYSTEMS
CHAIN MOLECULES
Chemistry
Chemistry, Multidisciplinary
Engineering
Engineering, Chemical
EQUATION-OF-STATE
EXCESS-ENTHALPIES
INTERMOLECULAR INTERACTIONS
PHASE-EQUILIBRIA
Physical Sciences
RELATIVE PERMITTIVITIES
Science & Technology
Technology
Thermodynamics
THERMOPHYSICAL PROPERTIES
VAPOR-LIQUID-EQUILIBRIA
Publication Status
Published
Coverage Spatial
United States
Date Publish Online
2023-11-10