Extending the SAFT-γ Mie group-contribution approach to model cyclic ketones: application to monoterpenoids
File(s)
Published version (ahead of print)
Author(s)
Type
Journal Article
Abstract
Monoterpenoids such as menthone are essential in organic synthesis, pharmaceuticals, and the fragrance industry for their versatile roles in developing complex molecules, flavours, and therapeutic agents. We extend the capability of the SAFT-γ Mie group-contribution equation of state by developing a new cyclic-ketone group, denoted as cCO, featuring two electron lone-pair sites that can interact with electropositive hydrogen sites in other associating compounds. The model parameters of the new cCO group are refined to represent target experimental thermophysical data of pure cyclic ketones, including the vapour pressure, single-phase density, heat capacity, and vaporisation enthalpy, as well as mixture data including the excess enthalpy, liquid density, vapour–liquid, liquid–liquid, and solid–liquid equilibria. New parameters that characterise the group interactions (one like interaction and 16 unlike interactions) are developed and used to calculate these thermophysical properties. We evaluate the robustness of the newly developed group and its transferability to other compounds, focussing on pure cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, and cyclooctanone, and their mixtures with hydrocarbons, alcohols, ketones, esters, aromatic compounds, and water. The theoretical calculations and found to be in good agreement with experiment, and the final model allows for accurate predictions of thermodynamic properties and complex phase behaviour, including azeotrope compositions. Morever, we transfer the parameters developed for the cyclic ketone group to predict the properties of pure 3-methylcyclohexanone and menthone, as well as the phase behaviour of binary mixtures of menthone with menthol and water, finding good agreement with available experimental data.
Date Issued
2025-05-11
Date Acceptance
2025-04-10
Citation
Molecular Physics, 2025, 123 (21-22)
ISSN
0026-8976
Publisher
Taylor and Francis Group
Journal / Book Title
Molecular Physics
Volume
123
Issue
21-22
Copyright Statement
© 2025 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 Accepted Manuscript in a repository by the author(s) or with their consent.
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Subjects
ACTIVITY-COEFFICIENTS
BINARY-MIXTURES
CHEMICAL CONSTITUTION
Chemistry
Chemistry, Physical
cyclic ketones
equation of state
EQUATION-OF-STATE
EXCESS MOLAR ENTHALPIES
HEAT-CAPACITIES
ISENTROPIC COMPRESSIBILITIES
monoterpenoids
ORGANIC-COMPOUNDS
phase behaviour
Physical Sciences
Physics
Physics, Atomic, Molecular & Chemical
SAFT-<italic>gamma</italic> Mie
Science & Technology
THERMODYNAMIC PROPERTIES
VAPOR-LIQUID-EQUILIBRIA
Publication Status
Published
Article Number
e2493320
Date Publish Online
2025-05-11