eCPA: An ion-specific approach to parametrization

Schlaikjer, Anders; Thomsen, Kaj; Kontogeorgis, Georgios M.

doi:10.1016/j.fluid.2017.12.008

Cited by 31 publications

(43 citation statements)

References 36 publications

(76 reference statements)

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“…In this way, DHFULL still presents a thermodynamically consistent approach, and it can be integrated into a thermodynamic model, for example, an equation of state, 29 with other molecular interactions considered. The integrated model shall then offer the capability to describe various experimental data over a wide range of temperature, pressure and concentration 30,38,49,51,69,70 . It also provides the flexibility to adjust the size parameters together with other model parameters to the experimental data if this becomes necessary.…”

Section: Resultsmentioning

confidence: 99%

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Predicting activity coefficients with the Debye–Hückel theory using concentration dependent static permittivity

et al. 2020

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In order to investigate the impacts of a concentration dependent static permittivity in the Debye-Hückel theory, two electrostatic Helmholtz free energy models and four activity coefficient models, with the ion-solvent interactions naturally included, are derived under different assumptions. The effects of static permittivity and model parameters are analyzed by predicting the mean ionic activity coefficients. It is found out that it is reasonable to assume a constant static permittivity in deriving the electrostatic Helmholtz free energy model but it is highly recommended to take the concentration dependence of static permittivity into account in subsequent calculations of thermodynamic properties. The activity coefficient model derived in this way accurately predicts the mean ionic activity coefficients of the investigated systems up to 0.1 mol/kg H 2 O, which indicates that the size parameters in the Debye-Hückel theory might be determined in advance before it is integrated into a more complete thermodynamic model.

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Section: Resultsmentioning

confidence: 99%

“…There are discussions which size parameter shall be used in the Debye–Hückel theory and the Born equation 37,45,49,50 . The same parameter was used in both contributions in some studies, 22,35 and different size parameters were used in some other cases 29,45,51 …”

Section: Introductionmentioning

confidence: 99%

Predicting activity coefficients with the Debye–Hückel theory using concentration dependent static permittivity

et al. 2020

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“…As Schlaikjer et al 2017 50,52 have noticed satisfactory correlation of both activity coefficients and salt solubilities required that both data are included in a simultaneous parameter estimation of the model parameters (e-CPA in that case). We suspect that a similar approach may be needed for most models and thus models (e-EoS) with parameters estimated by ignoring salt solubilities may not perform satisfactory for SLE.…”

Section: Should We Convert Between Lewis-randall and Mcmillan-mayer Fmentioning

confidence: 99%

The Debye-Hückel theory and its importance in modeling electrolyte solutions

Kontogeorgis

Maribo-Mogensen

Thomsen

2018

Fluid Phase Equilibria

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“…a res ¼ a hard chain þ a dispersion þ a association (11) Interactions are considered caused by the repulsion of the molecules (hard chain), unspecific attractive forces (dispersion) as well as for hydrogen-bonding interactions (association). The single independent terms require pure-component parameters.…”

Section: Thermodynamic Modelling With Pc-saftmentioning

confidence: 99%

Extremely Low Vapor‐Pressure Data as Access to PC‐SAFT Parameter Estimation for Ionic Liquids and Modeling of Precursor Solubility in Ionic Liquids

et al. 2021

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Precursor solubility is a crucial factor in industrial applications, dominating the outcome of reactions and purification steps. The outcome and success of thermodynamic modelling of this industrially important property with equations of states, such as Perturbed‐Chain Statistical Associating Fluid Theory (PC‐SAFT), vastly depends on the quality of the pure‐component parameters. The pure‐component parameters for low‐volatile compounds such as ionic liquids (ILs) have been commonly estimated using mixture properties, e. g. the osmotic pressure of aqueous solutions. This leads to parameters that depend on the solvent, and transferability to other mixtures often causes poor modeling results. Mixture‐independent experimental properties would be a more suitable basis for the parameter estimation offering a way to universal parameter sets. Model parameters for ILs are available in the literature [10.1016/j.fluid.2012.05.029], but they were estimated using pure‐IL density data. The present work focuses on a step towards a more universal estimation strategy that includes new experimental vapor‐pressure data of the pure IL. ILs exhibit an almost negligible vapor pressure in magnitude of usually 10−5 Pa even at elevated temperatures. In this work, such vapor‐pressure data of a series of 1‐ethyl‐3‐methyl‐imidazolium‐based [C2mim]‐ILs with various IL‐anions (e. g. tetrafluoroborate [BF4]−, hexafluorophosphate [PF6]−, bis(trifluoromethylsulfonyl)imide [NTf2]−) were experimentally determined and subsequently used for PC‐SAFT parameter estimation. The so‐determined parameters were used to predict experimental molecular precursor solubility in ILs and infinitely diluted activity coefficients of various solvents in ILs. The parameters were further compared to modeling results using classical parametrization methods (use of liquid‐density data only for the molecular PC‐SAFT and the ion‐based electrolyte PC‐SAFT). As a result, the modeled precursor solubilities using the new approach are much more precise than using the classical parametrization methods, and required binary parameters were found to be much smaller (if needed). In sum, including the pure‐component vapor‐pressure data of ILs opens the door towards parameter estimation that is not biased by mixture data. This procedure might be suitable also for polymers and for all kind of ionic species but needs extension to ion‐specific parametrization in the long term.

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eCPA: An ion-specific approach to parametrization

Cited by 31 publications

References 36 publications

Predicting activity coefficients with the Debye–Hückel theory using concentration dependent static permittivity

Predicting activity coefficients with the Debye–Hückel theory using concentration dependent static permittivity

The Debye-Hückel theory and its importance in modeling electrolyte solutions

Extremely Low Vapor‐Pressure Data as Access to PC‐SAFT Parameter Estimation for Ionic Liquids and Modeling of Precursor Solubility in Ionic Liquids

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