Predictive models for the phase behaviour and solution properties of weak electrolytes: nitric, sulphuric, and carbonic acids

Kohns, Maximilian; Lazarou, Georgia; Kournopoulos, Spiros; Forte, Esther; Perdomo, Felipe A.; Jackson, George; Adjiman, Claire S.; Galindo, Amparo

doi:10.1039/c9cp06795g

Cited by 18 publications

(18 citation statements)

References 145 publications

(197 reference statements)

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“…8,9 The necessity of modeling the relative permittivity accurately has recently been stressed in different applications, for example, when using ePC-SAFT for describing aqueous solutions of ionic liquids 10 or when applying SAFT-VRE Mie to aqueous solutions of weak electrolytes. 11 Another important aspect is the availability of experimental data for the relative permittivity. The relative permittivity of water, being the most important solvent, is well-known, and correlations to experimental data are available over wide ranges of temperature and pressure.…”

Section: ■ Introductionmentioning

confidence: 99%

Relative Permittivity of Stockmayer-Type Model Fluids from MD Simulations and COFFEE

2020

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The relative permittivity is a property that depends on the orientation structure of a fluid. Thus, using state-of-the-art equations of state it can be modeled only when using high level techniques, such as nonprimitive models. This is a drawback, especially when electrolytes are present: when using a primitive model, an auxiliary model for the relative permittivity must be introduced. Here, we pursue a different approach to predict the relative permittivity. The recently developed 'Co-Oriented Fluid Functional Equation for Electrostatic Interactions' (COFFEE) framework considers the mutual orientation of molecular dipole moments. It thereby enables a prediction of the relative permittivity when combined with Kirkwood's theory. To assess these predictions obtained from COFFEE, we present a comprehensive set of molecular simulation data for the relative permittivity of Stockmayer-type model fluids at wide ranges of temperature and density. Continuing a previous work, we extend the range of states considered to the homogeneous vapor, liquid, and supercritical regions. We find that when plotting the relative permittivity as a function of the ratio of density and temperature, all data points for a certain fluid collapse onto a single master curve. To a good approximation, the same holds for experimental data of the relative permittivity of water. By comparing the molecular simulation results with COFFEE, a good overall agreement is observed. Both data sets follow the same qualitative trends. Also reasonable quantitative agreement is found for many state points, the only exception being dense states at low temperatures.

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Section: ■ Introductionmentioning

confidence: 99%

Relative Permittivity of Stockmayer-Type Model Fluids from MD Simulations and COFFEE

2020

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“…The latest developments in the SAFT-γ approach ,,, also incorporate charged groups in the formalism. The free-energy contributions related to the Coulombic and solvent–ion polar interactions, for the case of spherical ions, are accounted for in the A ion and A Born terms discussed earlier.…”

Section: Illustration Of Performancementioning

confidence: 99%

“…The free-energy contributions related to the Coulombic and solvent–ion polar interactions, for the case of spherical ions, are accounted for in the A ion and A Born terms discussed earlier. Examples of the description of charged systems have been published for strong electrolytes, , weak acids, and deep eutectic solvents …”

Section: Illustration Of Performancementioning

confidence: 99%

“…The free-energy contributions related to the Coulombic and solvent−ion polar interactions, for the case of spherical ions, are accounted for in the A ion and A Born terms discussed earlier. Examples of the description of charged systems have been published for strong electrolytes, 43,214 weak acids, 156 and deep eutectic solvents. 124 In Figure 7 we exemplify the performance of SAFT-γ Mie in modeling electrolyte systems, presenting osmotic coefficients (in Figure 7a) and mean ionic activity coefficients (in Figure 7b) of sodium halide salts, both calculated as a function of the molality, m, of the salt, at T = 298.15 K and P = 0.101 MPa.…”

Section: Illustration Of Performancementioning

confidence: 99%

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Expanding the Applications of the SAFT-γ Mie Group-Contribution Equation of State: Prediction of Thermodynamic Properties and Phase Behavior of Mixtures

et al. 2020

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We present the latest developments in thermodynamic modeling using the SAFT-γ Mie group-contribution equation of state. The group database is updated, featuring now 58 groups; this expanded database incorporates new parameters for interactions between both like and unlike groups. This provides the capability to treat mixtures including alcohols, ethers, ketones, carboxylic acids, and acetates, amines, aromatic and cyclic compounds, electrolytes, inorganic acids, and some common solvents, such as water and acetone. A discussion is provided relating to the assignment of the groups, including some secondary groups that are introduced for multifunctional molecules to capture the influence of molecular polarization effects on the thermodynamic properties. Performance of the SAFT-γ Mie approach is illustrated for a wide variety of systems, highlighting its use in describing solid−liquid as well as vapor−liquid and liquid−liquid equilibria.

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“…However, such information is important for chemical engineering, e.g. for electrolyte solutions with mixed solvents [61] or solutions of weak electrolytes [43]. On the molecular scale, the relative permittivity is directly related to the mutual orientation of the molecular dipoles via Kirkwood's theory [40].…”

Section: Relative Permittivity Of Mixturesmentioning

confidence: 99%

Molecular Modeling and Simulation: Model Development, Thermodynamic Properties, Scaling Behavior and Data Management

Heinen

Chatwell

Homes

et al. 2021

High Performance Computing in Science and Engineering '20

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We are outlining our most recent findings, covering: 1) A comparison of a micro-and macroscopic solution of a two-phase Riemann problem obtained from molecular dynamics simulations and finite volume schemes; 2) A novel equation of state for the bulk viscosity of liquid noble gases based on a multi-mode relaxation ansatz; 3) A detailed analysis of the evaporation process of simple fluids; 4) Diffusion coefficients of quaternary liquid mixtures obtained by the Green-Kubo formalism; 5) An analysis of the solid/fluid phase transition for the face centered cubic (fcc) lattice; 6) The relative permittivity of mixtures of water and acetone; 7) An assessment of the reliability and reproducibility of molecular simulation results; 8) Techniques for the data management in simulation workflows, including annotations of simulation outcomes with appropriate metadata standardized by an ontology.

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Predictive models for the phase behaviour and solution properties of weak electrolytes: nitric, sulphuric, and carbonic acids

Abstract:
SAFT-VRE Mie allows for elucidating association and ion pairing in weak electrolyte systems.

Cited by 18 publications

References 145 publications

Relative Permittivity of Stockmayer-Type Model Fluids from MD Simulations and COFFEE

Relative Permittivity of Stockmayer-Type Model Fluids from MD Simulations and COFFEE

Expanding the Applications of the SAFT-γ Mie Group-Contribution Equation of State: Prediction of Thermodynamic Properties and Phase Behavior of Mixtures

Molecular Modeling and Simulation: Model Development, Thermodynamic Properties, Scaling Behavior and Data Management

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Predictive models for the phase behaviour and solution properties of weak electrolytes: nitric, sulphuric, and carbonic acids

Abstract: SAFT-VRE Mie allows for elucidating association and ion pairing in weak electrolyte systems.

Cited by 18 publications

References 145 publications

Relative Permittivity of Stockmayer-Type Model Fluids from MD Simulations and COFFEE

Relative Permittivity of Stockmayer-Type Model Fluids from MD Simulations and COFFEE

Expanding the Applications of the SAFT-γ Mie Group-Contribution Equation of State: Prediction of Thermodynamic Properties and Phase Behavior of Mixtures

Molecular Modeling and Simulation: Model Development, Thermodynamic Properties, Scaling Behavior and Data Management

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Product

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Abstract:
SAFT-VRE Mie allows for elucidating association and ion pairing in weak electrolyte systems.