Modeling the Thermodynamic Properties of Saturated Lactones in Nonideal Mixtures with the SAFT-? Mie Approach
Modeling the Thermodynamic Properties of Saturated Lactones in Nonideal Mixtures with the SAFT-? Mie Approach
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使用 SAFT-? 模拟非理想混合物中饱和内酯的热力学性质
DOI：
10.1021/acs.jced.3c00358
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发表时间：
2023
影响因子：
--
通讯作者：
Bernet T
中科院分区：
文献类型：
--
作者：
Bernet T
预测内酯的热力学性质在香料、香料和制药工业中是一个重要的挑战。在这里，我们开发了内酯与碳氢化合物、醇、酮、酯、芳香化合物、水和二氧化碳的二元混合物的相行为的预测模型。通过定义一个新的环酯基团，扩展了统计缔合流体理论SAFT-γMie基团贡献方法的基团参数矩阵。该基团由两个球形Mie链段和两个e1型缔合给电子点组成，它们可以与其他分子中的H型缔合电子接受点相互作用。新的CCOO基团相互作用的模型参数(1个类似相互作用和17个不同相互作用)被表征为代表纯流体(蒸汽压、单相密度和汽化热)和混合物(汽液平衡、液-液平衡、固-液平衡、密度和过量热)的物理性质的目标实验数据。通过将理论预测与实验数据进行比较，评估了模型的稳健性，主要是氧杂环己烷-2-酮、5-甲基-氧杂环己烷-2-酮和氧杂环己酮-2-酮(也分别称为γ-丁内酯、γ-戊内酯和ε-己内酯)。计算结果与实验符合得很好。所提出的模型可以准确地预测感兴趣的体系的热力学性质和高度非理想的相行为，如共沸物组成。它可用于支持新分子和制造工艺的开发。
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 e1that 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.