Simultaneous Predictions of Chemical and Phase Equilibria in Systems with an Esterification Reaction Using PC-SAFT

Self Cite

State of the art thermodynamic models, such as the Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT), require a thorough parametrization (three pure-component parameters for nonassociating molecules) of the molecules considered. In our previous work (J. Habicht, C. Brandenbusch, G. Sadowski, Fluid Phase Equilibria, 2023, 565, 113657), we introduced a Machine Learning approach for a predictive parametrization of nonassociating components. Within this approach, training is performed using a Huber-loss function, comparing the ML-predicted parameter set with the original one, e.g., from literature. However, often multiple pure-component parameter sets exist for one molecule. This fact makes the training to only one "true" parameter set questionable. Within this work, we thus performed a detailed analysis on the fact of multiparameter set existence. We further expanded our ML-approach by developing a choice of two physics-informed loss functions that allow for the consideration of multiple "true" parameter sets during training. Results indicate that reliable pure-component parameters have a certain orientation when plotted in the three-dimensional parameter space. The results of this work will lead to a more reliable ML-based parametrization and ensure the prediction of optimized purecomponent parameters for a given molecule.

Section: Methodsmentioning

confidence: 99%

Fitting Error vs Parameter Performance─How to Choose Reliable PC-SAFT Pure-Component Parameters by Physics-Informed Machine Learning

Habicht,

Sadowski,

Brandenbusch

2023

Self Cite

“…These data were obtained in our previous work, 19 during which we encountered certain difficulties in capturing the heterogeneous chemical equilibrium state for the region of the low values of the α 2 : the chemical equilibrium was established extremely slowly, the continuous "drift" of the composition was observed which was caused, in particular, by the simultaneous phase transition "inhibiting" the reaction. Consequently, the application of the α-variables and PC-SAFT calculation 20 might be useful for the additional correlation of the simultaneous chemical and phase equilibria data.…”

Section: Chemical Equilibrium Surfacementioning

confidence: 99%

“…This can be done through an experimental investigation of vapor–liquid equilibria, , using several modeling approaches, e.g. UNIFAC, UNIQUAC, NRTL, SAFT, − and with quantum chemical calculations . In particular, recently, Ascani et al have studied the ability of PC-SAFT to predict simultaneously chemical and phase equilibria in systems with an esterification reaction including the system under consideration in our work.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Chemical Equilibrium in the System Acetic acid–n-Amyl Alcohol–n-Amyl Acetate–Water at 323.15 K and Atmospheric Pressure: Experimental Data and Equilibrium Constant Estimation

Misikov,

Zolotovsky,

Samarov

et al. 2024

In this work, the results of the experimental study of the chemical equilibrium in both homogeneous and heterogeneous areas for the system acetic acid− n-amyl alcohol−n-amyl acetate−water at 323.15 K and atmospheric pressure are presented. The chemical equilibrium compositions and compositions of coexisting liquid phases were determined by gas chromatography. The obtained compositions were plotted in a composition tetrahedron for better clarity. The tie-lines of the heterogeneous chemical equilibrium were presented in transformed variables (the α-variables). The peculiarities of the surface of the chemical equilibrium are discussed. The obtained data are compared with the literature information at 318.15 K. The value of the thermodynamic constant of the chemical equilibrium was estimated using three approaches: an empirical equation, the UNIFAC model, and the quantum chemical calculation.

“…Chemical engineering requires precise thermodynamic data and calculations for different purposes such as process design, and it means using the equation of state as one of the most important tools in thermodynamic would be necessary for calculations and modeling. − Accordingly, selecting the proper equation of state is crucial for chemical engineering purposes between the numerous models. − On the other hand, statistical mechanics includes equation of states that uses microscopic information from quantum mechanics of a certain system, processes it, and calculates macroscopic measurable variables. − One of the most successful equations of states is Perturbation chain- statistical associated fluid theory (PC-SAFT) that has been applied for modeling of the mixture’s thermodynamic properties. − A molecule is assumed as a hard chain consisting of hard spheres in PC-SAFT by imposing first- and second-order thermodynamic perturbations. , Also, different terms have been added to extend the model for different varieties of the molecules. − …”

Section: Introductionmentioning

confidence: 99%

Thermodynamic Properties of Binary Mixtures Containing Ionic Liquid 1-Butyl-3-methylimidazolium Thiocyanate and Ethanolamines at Different Temperatures: Measurement and PC-SAFT Modeling

Gharehzadeh Shirazi,

Shahabadi,

Shekaari

et al. 2023

Thermodynamic properties of liquid absorbents are important for industrial applications. Ionic liquids (ILs) are more efficient alternatives to organic solvents that are used for CO2 absorption and storage. The IL, 1-butyl-3-methylimidazolium thiocyanate ([BMIM] [SCN]) with ethanolamines are considered as an efficient material for gas absorption. The density and speed of sound for a full-range concentration of binary ([BMIM] [SCN] + ethanolamine (MEA)/diethanolamine (DEA)/triethanolamine (TEA)) systems have been measured at (288.15 – 318.15) K, and excess molar properties as nonideality of the mixtures has been calculated. The conductor-like screening model (COSMO) as a microscopic approach has been used to calculate the PC-SAFT equation of state parameters, prediction the density of the studied mixtures, and compare the experimentally obtained parameters of PC-SAFT. The excess molar volumes for systems containing IL + monoethanolamine are positive while negative for DEA and TEA. Also, the excess isentropic compressibilities for the studied mixtures are negative at all temperatures. The PC-SAFT equation of state as a microscopic approach for interpreting the molecular interactions is an efficient model in predicting thermodynamic properties. The results indicate that increasing OH groups of ethanolamines enhances their interactions with IL molecules.