A Review of Electrolyte Equations of State with Emphasis on Those Based on Cubic and Cubic-Plus-Association (CPA) Models

Kontogeorgis, Georgios M.; Schlaikjer, Anders; Olsen, Martin Due; Maribo-Mogensen, Bjørn; Thomsen, Kaj; Solms, Nicolas von; Liang, Xiaodong

doi:10.1007/s10765-022-02976-4

Cited by 33 publications

(24 citation statements)

References 96 publications

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“…Modeling electrolyte systems is a challenging endeavor because of the strong long-range ionic interactions, which make the solutions highly nonideal. ,− Electrolyte solutions are commonly modeled using semiempirical equations of state and molecular based simulations. ,− Semiempirical equations provide a rapid and convenient method for the prediction of thermophysical properties . The quality of these equations depends on the availability of accurate experimental and simulation data. − For aqueous alkaline solutions, experimental data for self-diffusivities and solubilities of H 2 and O 2 at high concentrations (above 4 mol/kg), temperatures (323–373 K), and pressures (above 50 bar) is lacking, especially in the case of aqueous NaOH solutions. , These temperatures (ca.…”

Section: Introductionmentioning

confidence: 99%

A New Force Field for OH^– for Computing Thermodynamic and Transport Properties of H₂ and O₂ in Aqueous NaOH and KOH Solutions

et al. 2022

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The thermophysical properties of aqueous electrolyte solutions are of interest for applications such as water electrolyzers and fuel cells. Molecular dynamics (MD) and continuous fractional component Monte Carlo (CFCMC) simulations are used to calculate densities, transport properties (i.e., self-diffusivities and dynamic viscosities), and solubilities of H2 and O2 in aqueous sodium and potassium hydroxide (NaOH and KOH) solutions for a wide electrolyte concentration range (0–8 mol/kg). Simulations are carried out for a temperature and pressure range of 298–353 K and 1–100 bar, respectively. The TIP4P/2005 water model is used in combination with a newly parametrized OH– force field for NaOH and KOH. The computed dynamic viscosities at 298 K for NaOH and KOH solutions are within 5% from the reported experimental data up to an electrolyte concentration of 6 mol/kg. For most of the thermodynamic conditions (especially at high concentrations, pressures, and temperatures) experimental data are largely lacking. We present an extensive collection of new data and engineering equations for H2 and O2 self-diffusivities and solubilities in NaOH and KOH solutions, which can be used for process design and optimization of efficient alkaline electrolyzers and fuel cells.

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Section: Introductionmentioning

confidence: 99%

A New Force Field for OH^– for Computing Thermodynamic and Transport Properties of H₂ and O₂ in Aqueous NaOH and KOH Solutions

et al. 2022

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“…Notable examples are the Pitzer model, − the electrolyte versions of the Nonrandom Two-Liquid (eNRTL) model, , the electrolyte Universal Quasichemical (UNIQUAC) model, and a hybrid model of Pitzer and UNIQUAC called the mixed-solvent electrolyte (MSE) model by OLI . The strengths and weaknesses of these models have been extensively reviewed in the literature. , There are also recent efforts to develop electrolyte models based on equations of state, such as PC-SAFT and CPA EoS …”

Section: Introductionmentioning

confidence: 99%

“…9,10 There are also recent efforts to develop electrolyte models based on equations of state, such as PC-SAFT and CPA EoS. 11 The purpose of this work is to present the electrolyte thermodynamic modeling methodology to address the solution chemistry together with the two electrolyte thermodynamic models, Pitzer and eNRTL, implemented in Aspen process simulators, namely, Aspen Properties. Also covered are an experimental data compilation, best practice in data regression, and successful industrial applications for various electrolyte systems.…”

Section: Introductionmentioning

confidence: 99%

Electrolyte Thermodynamic Models in Aspen Process Simulators and Their Applications

Wang

Song

Zhang

et al. 2022

Ind. Eng. Chem. Res.

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Electrolyte systems are becoming increasingly important as the process industries transition to better address environmental sustainability and climate change. Industrial processes such as carbon capture and sequestration, brine water treatment, lithium refining, and many others require accurate and rigorous electrolyte thermodynamic models to support process simulation and design of chemical processes involving electrolyte systems. Distinctly different from nonelectrolyte systems, the solution nonideality of electrolyte systems is primarily characterized by the electrolyte solution chemistry and secondly impacted by the subsequent physical interactions and associations of true species in solutions. This Article presents the methodology in Aspen process simulators to address the solution chemistry with true species and apparent component approaches together with the two electrolyte thermodynamic models, Pitzer and Electrolyte Nonrandom Two-Liquid equations. Also covered are experimental data compilation, best practice in data regression, and industrial applications highlighted with CO 2 capture with amine solutions and high salinity brine solutions. We further present our perspectives in current challenges and emerging opportunities with thermodynamic modeling for electrolyte systems with high charge density ions, transport property estimation, and systematic data collection and verification.

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“…Numerous versions of them have already been derived and discussed in the literature. , The great success of these models both in literature and in practical applications is undeniable. Many electrolyte equations of state − still rely on DH equations to represent ion–ion interactions in electrolyte solutions. However, there is still a lack of understanding of what we lose when giving up the higher-order electrostatic terms present in the Poisson–Boltzmann equation when deriving these models.…”

Section: Introductionmentioning

confidence: 99%

Investigation of the Limits of the Linearized Poisson–Boltzmann Equation

Silva

Kontogeorgis

2022

J. Phys. Chem. B

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This work presents a comparison between a numerical solution of the Poisson–Boltzmann equation and the analytical solution of its linearized version through the Debye–Hückel equations considering both size-dissimilar and common ion diameters approaches. In order to verify the limits in which the linearized Poisson–Boltzmann equation is capable to satisfactorily reproduce the nonlinear version of Poisson–Boltzmann, we calculate mean ionic activity coefficients for different types of electrolytes as various temperatures. The divergence between the linearized and full Poisson–Boltzmann equations is higher for lower molalities, and both solutions tend to converge toward higher molalities. For electrolytes of lower valencies (1:1, 1:2, 2:1, and 1:3) and higher distances of closest approach, the full version of the Debye–Hückel equation is capable of representing the activity coefficients with a low divergence from the nonlinear Poisson–Boltzmann. The size-dissimilar full version of Debye–Hückel represents a clear improvement over the extended version that uses only common ion diameters when compared to the numerical solution of the Poisson–Boltzmann equation. We have derived a salt-specific index (Θ) to gradually classify electrolytes in order of increasing influence of nonlinear ion–ion interactions, which differentiate the Debye–Hückel equations from the nonlinear Poisson–Boltzmann equation.

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A Review of Electrolyte Equations of State with Emphasis on Those Based on Cubic and Cubic-Plus-Association (CPA) Models

Cited by 33 publications

References 96 publications

A New Force Field for OH^– for Computing Thermodynamic and Transport Properties of H₂ and O₂ in Aqueous NaOH and KOH Solutions

A New Force Field for OH^– for Computing Thermodynamic and Transport Properties of H₂ and O₂ in Aqueous NaOH and KOH Solutions

Electrolyte Thermodynamic Models in Aspen Process Simulators and Their Applications

Investigation of the Limits of the Linearized Poisson–Boltzmann Equation

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A Review of Electrolyte Equations of State with Emphasis on Those Based on Cubic and Cubic-Plus-Association (CPA) Models

Cited by 33 publications

References 96 publications

A New Force Field for OH– for Computing Thermodynamic and Transport Properties of H2 and O2 in Aqueous NaOH and KOH Solutions

A New Force Field for OH– for Computing Thermodynamic and Transport Properties of H2 and O2 in Aqueous NaOH and KOH Solutions

Electrolyte Thermodynamic Models in Aspen Process Simulators and Their Applications

Investigation of the Limits of the Linearized Poisson–Boltzmann Equation

Contact Info

Product

Resources

About

A New Force Field for OH^– for Computing Thermodynamic and Transport Properties of H₂ and O₂ in Aqueous NaOH and KOH Solutions

A New Force Field for OH^– for Computing Thermodynamic and Transport Properties of H₂ and O₂ in Aqueous NaOH and KOH Solutions