Experimental Data of Fluid Phase Equilibria- Correlation and Prediction Models: A Review

Domańska, Urszula

doi:10.3390/pr7050277

Cited by 22 publications

(15 citation statements)

References 133 publications

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“…The excess enthalpy is theoretically expressed in terms of mole fraction and the activity coefficient, γ, of species i (=1 or 2) where R denotes the gas constant. The activity coefficient as a function of composition (or temperature) can be estimated, empirically or theoretically, by activity coefficient models, , of which the simplest one is the empirical one-parameter Margules model Here, A 12 is a constant that indicates the strength of the specific interactions. Equation results in a correction similar to the Braun–Kovacs equation (eq ).…”

Section: Methodsmentioning

confidence: 99%

Prediction of the Synergistic Glass Transition Temperature of Coamorphous Molecular Glasses Using Activity Coefficient Models

et al. 2021

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The glass transition temperature (T g) of a binary miscible mixture of molecular glasses, termed a coamorphous glass, is often synergistically increased over that expected for an athermal mixture due to the strong interactions between the two components. This synergistic interaction is particularly important for the formulation of coamorphous pharmaceuticals since the molecular interactions and resulting T g strongly impact stability against crystallization, dissolution kinetics, and bioavailability. Current models that describe the composition dependence of T g for binary systems, including the Gordon–Taylor, Fox, Kwei, and Braun–Kovacs equations, fail to describe the behavior of coamorphous pharmaceuticals using parameters consistent with experimental ΔC P and Δα. Here, we develop a robust thermodynamic approach extending the Couchman and Karasz method through the use of activity coefficient models, including the two-parameter Margules, non-random-two-liquid (NRTL), and three-suffix Redlich–Kister models. We find that the models, using experimental values of ΔC P and fitting parameters related to the binary interactions, successfully describe observed synergistic elevations and inflections in the T g versus composition response of coamorphous pharmaceuticals. Moreover, the predictions from the NRTL model are improved when the association-NRTL version of that model is used. Results are reported and discussed for four different coamorphous systems: indomethacin–glibenclamide, indomethacin–arginine, acetaminophen–indomethacin, and fenretinide–cholic acid.

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Section: Methodsmentioning

confidence: 99%

Prediction of the Synergistic Glass Transition Temperature of Coamorphous Molecular Glasses Using Activity Coefficient Models

et al. 2021

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“…To provide further insight into the potential utility of electronic structure calculations with SMx universal solvent models to predict ln γ ∞ i,j , the top performing SM12 was compared to two well-known methods, the Universal Quasichemical Functional-group Activity Coefficients (UNIFAC) method [15,16,71] and the Modified Separation of Cohesive Energy Density (MOSCED) model [19,20,72]. UNIFAC was selected as a comparative method because it is perhaps the most common predictive excess Gibbs free energy method [73].…”

Section: Reference Calculationsmentioning

confidence: 99%

Assessment of the SM12, SM8, and SMD Solvation Models for Predicting Limiting Activity Coefficients at 298.15 K

et al. 2020

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The SMx (x = 12, 8, or D) universal solvent models are implicit solvent models which using electronic structure calculations can compute solvation free energies at 298.15 K. While solvation free energy is an important thermophysical property, within the thermodynamic modeling of phase equilibrium, limiting (or infinite dilution) activity coefficients are preferred since they may be used to parameterize excess Gibbs free energy models to model phase equilibrium. Conveniently, the two quantities are related. Therefore the present study was performed to assess the ability to use the SMx universal solvent models to predict limiting activity coefficients. Two methods of calculating the limiting activity coefficient where compared: (1) the solvation free energy and self-solvation free energy were both predicted and (2) the self-solvation free energy was computed using readily available vapor pressure data. Overall the first method is preferred as it results in a cancellation of errors, specifically for the case in which water is a solute. The SM12 model was compared to both the Universal Quasichemical Functional-group Activity Coefficients (UNIFAC) and modified separation of cohesive energy density (MOSCED) models. MOSCED was the highest performer, yet had the smallest available compound inventory. UNIFAC and SM12 exhibited comparable performance. Therefore further exploration and research should be conducted into the viability of using the SMx models for phase equilibrium calculations.

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“…Therefore, moving forward the selected method for calculating ln γ ∞ i,j will be to compute ∆G solv i,j and ∆G self i,i consistently; put differently, both ∆G solv i,j and ∆G self i,i will be predicted. To provide further insight into the potential utility of electronic structure calculations with SMx universal solvent models to predict ln γ ∞ i,j , the top performing SM12 was compared to two well-known methods, the Universal Quasichemical Functional-group Activity Coefficients (UNIFAC) method [15,16,70] and the Modified Separation of Cohesive Energy Density (MOSCED) model [19,20,71]. UNIFAC was selected as a comparative method because it is perhaps the most common predictive excess Gibbs free energy method [72].…”

Section: Reference Calculationsmentioning

confidence: 99%

Assessment of the SM12, SM8, and SMD Solvation Models for Predicting Limiting Activity Coefficients at 298.15 K

Roese¹,

Heintz²,

Uzat³

et al. 2020

Preprint

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The SMx (x= 12, 8, or D) universal solvent models are implicit solvent models which using electronic structure calculations can compute solvation free energies at 298.15 K. While solvation free energy is an important thermophysical property, within the thermodynamic modeling of phase equilibrium, limiting (or infinite dilution) activity coefficients are preferred since they may be used to parameterize excess Gibbs free energy models to model phase equilibrium. Conveniently, the two quantities are related. Therefore the present study was performed to assess the ability to use the SMx universal solvent models to predict limiting activity coefficients. Two methods of calculating the limiting activity coefficient where compared: 1) The solvation free energy and self-solvation free energy were both predicted and 2) the self-solvation free energy was computed using readily available vapor pressure data. Overall the first method is preferred as it results in a cancellation of errors, specifically for the case in which water is a solute. The SM12 model was compared to both UNIFAC and MOSCED. MOSCED was the highest performer, yet had the smallest available compound inventory. UNIFAC and SM12 exhibited comparable performance. Therefore further exploration and research should be conducted into the viability of using the SMx models for phase equilibrium calculations.

show abstract

Experimental Data of Fluid Phase Equilibria- Correlation and Prediction Models: A Review

Cited by 22 publications

References 133 publications

Prediction of the Synergistic Glass Transition Temperature of Coamorphous Molecular Glasses Using Activity Coefficient Models

Prediction of the Synergistic Glass Transition Temperature of Coamorphous Molecular Glasses Using Activity Coefficient Models

Assessment of the SM12, SM8, and SMD Solvation Models for Predicting Limiting Activity Coefficients at 298.15 K

Assessment of the SM12, SM8, and SMD Solvation Models for Predicting Limiting Activity Coefficients at 298.15 K

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