Modeling the thermodynamic properties of cyclic alcohols with the SAFT-γ Mie approach: application to cyclohexanol and menthol systems
Author(s)
Type
Journal Article
Abstract
Cyclic alcohols are commonly found in natural and synthetic products and are involved in many biological processes. An ability to model their thermodynamic properties is of interest in food, flavouring, and pharmaceutical manufacturing, particularly for mixtures for which available experimental data are limited. Good examples are mixtures including menthol, a naturally occurring cyclic alcohol widely used in the food and pharmaceutical industries, well-known for its cooling-sensation properties and its role in the discovery of the TRPM8 receptor. Here, we extend the SAFT-γ Mie group-contribution method to model cyclic alcohols, by introducing a new cCHOH group (c for cyclic) composed of two identical Mie segments. Three association sites (two electronic sites of type e and one hydrogen site of type H) are also included to mediate hydrogen bonding. New parameters that characterise the group interactions (one new like interaction and 26 new unlike interactions) are developed and are employed to determine the thermophysical properties (vapour pressure, saturation density, vaporisation enthalpy, and second-order thermodynamic derivative properties) of pure cyclic alcohols, and mixture properties (vapour–liquid equilibria, liquid–liquid equilibria, solid–liquid equilibria, density, and excess enthalpy) of cyclic alcohols in several solvents. The quality of the model is evaluated by comparing predictive calculations with experimental data of 76 systems: six pure fluids and 70 binary mixtures, selected from a large range of solvent families: cyclic, linear, and branched alkanes, 1-alcohols, 2-alcohols, 2-ketones, esters, aromatic compounds, water, and carbon dioxide. Very good overall agreement is found, including for the prediction of solid–liquid solubility, which confirms the transferability of the new group parameters. Together with previously developed parameters, these open the way for the prediction of the thermodynamic properties of further complex mixtures.
Date Issued
2024-11-01
Date Acceptance
2024-08-08
Citation
Molecular Physics, 2024, 122 (21-22)
ISSN
0026-8976
Publisher
Taylor and Francis Group
Journal / Book Title
Molecular Physics
Volume
122
Issue
21-22
Copyright Statement
© 2024 The Author(s). Published by Informa UK Limited, trading as Taylor & Francis Group.This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use,distribution, and reproduction in any medium, provided the original work is properly cited. The terms on which this article has been published allow the posting of the AcceptedManuscript in a repository by the author(s) or with their consent.
License URL
Subjects
ALKANOL PLUS CYCLOALKANE
BINARY-MIXTURES
BUTANE-CARBON-DIOXIDE
Chemistry
Chemistry, Physical
EQUATION-OF-STATE
EXCESS MOLAR ENTHALPIES
group contribution
ISENTROPIC COMPRESSIBILITIES
menthol
METHYLCYCLOHEXANE PLUS
phase equilibria
PHASE PROPERTIES
Physical Sciences
Physics
Physics, Atomic, Molecular & Chemical
Science & Technology
Statistical associating fluid theory (SAFT)
TERNARY MIXTURES
thermodynamic properties
VAPOR-LIQUID-EQUILIBRIA
Publication Status
Published
Article Number
e2394132
Date Publish Online
2024-09-12