Comparison of activity coefficient models for electrolyte systems

Lin, Yi; Kate, Antoon ten; Mooijer, Miranda; Delgado, J.; Fosbøl, Philip Loldrup; Thomsen, Kaj

doi:10.1002/aic.12040

Cited by 44 publications

(38 citation statements)

References 40 publications

(51 reference statements)

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“…Capabilities and limitations of these models are described in the literature 2,3,17 and Lin et al 18 recently presented a comparison of some of the most popular approaches. In this comparison of the Electrolyte NRTL (Aspen), Mixed-Solvent Electrolyte (OLI), and Extended UNIQUAC (CERE) 10 different test systems were modelled and while all models predicted VLE quite well, SLE calculations sometimes lead to incorrect speciation and solid phases.…”

Section: Thermodynamic Modeling Of Electrolyte-containing Systemsmentioning

confidence: 99%

“…The research community is divided quite sharply into two groups with limited interaction; those advocating the non-primitive approach [22][23][24][25] , fig.6-right, where water (solvent) is treated as a (dipolar) molecule interacting directly with ions, and the -currently-many more who support the primitive approach, with water being a dielectric continuum, fig.6-left 2,12,[18][19][20][21][26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44]46 where the solvent (e.g. water) is considered to be a dielectric continuum characterized by its static permittivity (relative static permittivity) r ε .…”

Section: Accepted Manuscriptmentioning

confidence: 99%

“…Another problem with the formulation in terms of molality is that it requires that the solvent is present in large quantities since the molality is defined as Equation 22can be derived from eq. (18) by assuming that all ions have the same limit i l . This is not necessarily a reasonable assumption, as there can be large differences in the sizes between e.g.…”

Section: Accepted Manuscriptmentioning

confidence: 99%

See 2 more Smart Citations

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

Kontogeorgis

Maribo-Mogensen

Thomsen

2018

Fluid Phase Equilibria

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160

127

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Section: Thermodynamic Modeling Of Electrolyte-containing Systemsmentioning

confidence: 99%

Section: Accepted Manuscriptmentioning

confidence: 99%

Section: Accepted Manuscriptmentioning

confidence: 99%

See 1 more Smart Citation

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

Kontogeorgis

Maribo-Mogensen

Thomsen

2018

Fluid Phase Equilibria

Self Cite

160

127

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“…The temptation to improve the fitting of thermodynamic property models by repeatedly introducing new variants with systemspecific basis functions and additional adjustable parameters is not confined to the Pitzer equations (e.g., see Partanen, 2012). It is important to remember that these other theoretical approaches have so far only been tested in rather narrow ways (Lin et al, 2010) compared to the multicomponent modelling applications which have been based on the Pitzer framework.…”

Section: Discussionmentioning

confidence: 99%

Aqueous electrolyte solution modelling: Some limitations of the Pitzer equations

Rowland

Königsberger

Hefter

et al. 2015

Applied Geochemistry

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Despite intense efforts, general thermodynamic modelling of aqueous electrolyte solutions still presents a difficult challenge, with no obvious method of choice. Even though the Pitzer equations seemingly provide a well-established theoretical framework applicable to many chemical systems over a wide range of temperatures and pressures, they are not as widely adopted as their early promise might have suggested. This is strikingly illustrated by the simultaneous appearance in the literature of numerous, different (and potentially incompatible) Pitzer models alongside a proliferation of alternative theoretical approaches with inferior capabilities.To better understand this problem, the ability of the Pitzer equations to represent the physicochemical properties of aqueous solutions has been systematically investigated for exemplar electrolyte systems. Pitzer ion-interaction parameters have been calculated for selected systems by least-squares regression analysis of published solution data for activity coefficients, osmotic coefficients, relative enthalpies, heat capacities, volumes and densities to high temperatures and pressures. Although satisfactory fits can be achieved when the ranges of conditions are carefully chosen and when sufficient data are available to constrain the regression, the fits obtained tend otherwise to be unsatisfactory. The Pitzer equations do not cope well with gaps and other deficiencies in the regressed data. Profound difficulties, poorly recognized hitherto, can also arise because of variation in the sensitivity of the Pitzer functions to values for different physicochemical properties when these are combined. Given the dimensionality of numerous related thermodynamic properties, all changing as functions of composition, temperature and pressure, these problems are difficult to detect, let alone address, especially in multicomponent systems. The growing practice of improving fits simply by adding basis functions (thereby increasing the number of adjustable parameters) should be deprecated because it increases the likelihood of error propagation, introduces subjectivity, makes independent verification difficult and has deleterious implications for both automated data processing and for consistency between thermodynamic models.

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“…The models most often used in industry [31] are based on activity coefficients (the most known ones are Pitzer [32], modified e-NRTL [26][27][28] and e-UNIQUAC [29], as well as MSE [33,34]). In addition to their low pressure limitation, these models rely on adjusting many interaction parameters against the available experimental data.…”

Section: Activity Coefficients Vs Equation Of Statementioning

confidence: 99%

Modeling of mixed-solvent electrolyte systems

Ahmed

Ferrando

Hemptinne

et al. 2018

Fluid Phase Equilibria

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Models for mixed-solvent strong electrolytes, using an equation of state (EoS) are reviewed in this work. Through the example of ePPC-SAFT (that includes a Born term and ionic association), the meaning and the effect of each contribution to the solvation energy and the mean ionic activity coefficient are investigated. The importance of the dielectric constant is critically reviewed, with a focus on the use of a salt-concentration dependent function. The parameterization is performed using two adjustable parameters for each ion: a minimum approach distance () and an association energy (). These two parameters are optimized by fitting experimental activity coefficient and liquid density data, for all alkali halide salts simultaneously, in the range 298K to 423K. The model is subsequently tested on a large number of available experimental data, including salting out of Methane/Ethane/CO 2 /H 2 S. In all cases the deviations in bubble pressures were below 20% AADP. Predictions of vapor-liquid equilibrium of mixed solvent electrolyte systems containing methanol, ethanol are also made where deviations in bubble pressures were found to be below 10% (AADP).

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Comparison of activity coefficient models for electrolyte systems

Cited by 44 publications

References 40 publications

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

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

Aqueous electrolyte solution modelling: Some limitations of the Pitzer equations

Modeling of mixed-solvent electrolyte systems

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