Evaluating the Performance of the PC-SAFT and CPA Equations of State on Anomalous Properties of Water

Kontogeorgis, Georgios M.

doi:10.1021/acs.jced.0c00689

Cited by 17 publications

(11 citation statements)

References 64 publications

(189 reference statements)

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“…PC‐SAFT and CPA are not able to predict the density anomaly. In fact, these two models are not able to predict any of water's anomalies 3 . On the other hand, TIP4P/2005 69 and iAMOEBA 55 are able to predict a density maximum and they predict water's density almost perfectly.…”

Section: Resultsmentioning

confidence: 87%

Multiple insights call for revision of modern thermodynamic models to account for structural fluctuations in water

2022

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Modern thermodynamic models incorporate the concept of association (hydrogen bonding) and they can describe very satisfactorily many properties of water containing mixtures. They have not been successful in representing water's anomalous properties and this work provides a possible explanation. We have analyzed and interpreted recent experimental data, molecular simulation results, and two‐state theory approaches and compared against the predictions from thermodynamic models. We show that the dominance of the tetrahedral structure implemented in modern thermodynamic models may be the reason for their failure for describing water systems. While this study does not prove the two‐state theories for water, it indicates that a high level of tetrahedral structure of water is not in agreement with water's anomalous properties when used in thermodynamic models.

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Section: Resultsmentioning

confidence: 87%

Multiple insights call for revision of modern thermodynamic models to account for structural fluctuations in water

2022

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“…ADPC‐SAFT represents a vast improvement over standard applications of PC‐SAFT. Tsochantaris et al 8 recently published an extensive review of PC‐SAFT parameter sets for water. The percentage deviations of ADPC‐SAFT are generally 1–2 orders of magnitude lower than those observed for a wide range of PC‐SAFT models 8 …”

Section: Summary and Discussionmentioning

confidence: 99%

“…PC‐SAFT has been extensively 7,8 applied to the pure component thermodynamic and phase behavior of water. Tsochantaris et al 8 recently published a detailed study examining the accuracy of several literature PC‐SAFT parameter sets for the description of pure water. The results clearly demonstrate that PC‐SAFT is inadequate as an equation of state for the prediction of pure water properties.…”

Section: Introductionmentioning

confidence: 99%

A modified perturbed chain‐statistical associating fluid theory equation of state for water which includes an association dependent hard sphere diameter

Marshall

2021

AIChE Journal

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The concept of an association dependent hard sphere diameter is introduced as a means to obtain an accurate perturbed chain‐statistical associating fluid theory (PC‐SAFT) equation of state model for water. The new approach is demonstrated to be a step change in accuracy for the representation of pure water properties as compared with standard PC‐SAFT applications. Extension of the approach to mixtures is discussed.

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“…It was illustrated elsewhere that the SAFT-type models for pure water are generally inaccurate, because they cannot incorporate the complex structural features present in the water liquid phase. 45,145,146 Surprisingly, Figure 7 shows that both PC-SAFT and COSMO-RS did not provide the worst total RMSLD for aqueous systems. For PC-SAFT, however, there is a large outlier in terms of RMSLD constituted by the aqueous solubility of GSF (see Figure 6), but this can be attributed to the description of GSF itself and its HB acceptor behavior, as discussed in the previous section.…”

Section: Performance With Respect To Individual Solvents and Their Fa...mentioning

confidence: 93%

Purely Predicting the Pharmaceutical Solubility: What to Expect from PC-SAFT and COSMO-RS?

Klajmon

2022

Mol. Pharmaceutics

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A pair of popular thermodynamic models for pharmaceutical applications, namely, the perturbed-chain statistical associating fluid theory (PC-SAFT) equation of state and the conductor-like screening model for real solvents (COSMO-RS), are thoroughly benchmarked for their performance in predicting the solubility of active pharmaceutical ingredients (APIs) in pure solvents. The ultimate goal is to provide an illustration of what to expect from these progressive frameworks when applied to the thermodynamic solubility of APIs based on activity coefficients in a purely predictive regime without specific experimental solubility data (the fusion properties of pure APIs were taken from experiments). While this kind of prediction represents the typical modus operandi of the first-principles-aided COSMO-RS, PC-SAFT is a relatively highly parametrized model that relies on experimental data, against which its pure-substance and binary interaction parameters (kij) are fitted. Therefore, to make this benchmark as fair as possible, we omitted any binary parameters of PC-SAFT (that is, kij = 0 in all cases) and preferred pure-substance parameter sets for APIs not trained to experimental solubility data. This computational approach, together with a detailed assessment of the obtained solubility predictions against a large experimental data set, revealed that COSMO-RS convincingly outperformed PC-SAFT both qualitatively (that is, COSMO-RS was better in solvent ranking) and quantitatively, even though the former is independent of both substance-and mixture-specific experimental data. Regarding quantitative comparison, COSMO-RS outperformed PC-SAFT for nine of the ten APIs and for 63 % of the API-solvent systems, with root-mean-square deviations of the predicted data from the entire experimental data set being 0.82 and 1.44 log units, respectively.The results were further analyzed to expand the picture of the performance of both models with respect to the individual APIs and solvents. Interestingly, in many cases, both models were found to qualitatively incorrectly predict the direction of deviations from ideality. Furthermore, we examined how the solubility predictions from both models are sensitive to different API parametrizations.

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Evaluating the Performance of the PC-SAFT and CPA Equations of State on Anomalous Properties of Water

Cited by 17 publications

References 64 publications

Multiple insights call for revision of modern thermodynamic models to account for structural fluctuations in water

Multiple insights call for revision of modern thermodynamic models to account for structural fluctuations in water

A modified perturbed chain‐statistical associating fluid theory equation of state for water which includes an association dependent hard sphere diameter

Purely Predicting the Pharmaceutical Solubility: What to Expect from PC-SAFT and COSMO-RS?

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