The simultaneous representation of dielectric constant, volume and activity coefficients using an electrolyte equation of state

Inchekel, Radia; Hemptinne, Jean-Charles de; Fürst, Walter

doi:10.1016/j.fluid.2008.06.013

Cited by 68 publications

(92 citation statements)

References 37 publications

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“…, and γ i, m is the molal-based activity coefficient given by Equation (27). The chemical potential of ion i at the reference state of unit molality corresponds to the molar Gibbs free energy of formation G f i (aq) of 1 mol kg −1 of the solvated ion.…”

Section:  Solid-liquid Phase Equilibriamentioning

confidence: 99%

“…A simple treatment to account for the introduction of a charged species in a dielectric medium was provided by Born [25]. The Born contribution has now been incorporated within cubic and CPA EOSs [26,27], and, more recently, within the ePPC-SAFT [20] and SAFT-VRE [21] approaches. A non-primitive treatment that incorporates a polar solvent within a SAFT formalism has also been presented [17,[28][29][30].…”

Section: Introductionmentioning

confidence: 99%

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Development of intermolecular potential models for electrolyte solutions using an electrolyte SAFT-VR Mie equation of state

et al. 2016

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We present a theoretical framework and parameterisation of intermolecular potentials for aqueous electrolyte solutions using the statistical associating fluid theory based on the Mie interaction potential (SAFT-VR Mie), coupled with the primitive, non-restricted mean-spherical approximation (MSA) for electrolytes. In common with other SAFT approaches, water is modelled as a spherical molecule with four off-centre association sites to represent the hydrogen-bonding interactions; the repulsive and dispersive interactions between the molecular cores are represented with a potential of the Mie (generalised Lennard-Jones) form. The ionic species are modelled as fully dissociated, and each ion is treated as spherical: Coulombic ion-ion interactions are included at the centre of a Mie core; the ion-water interactions are also modelled with a Mie potential without an explicit treatment of iondipole interaction. A Born contribution to the Helmholtz free energy of the system is included to account for the process of charging the ions in the aqueous dielectric medium. The parameterisation of the ion potential models is simplified by representing the ion-ion dispersive interaction energies with a modified version of the London theory for the unlike attractions. By combining the Shannon estimates of the size of the ionic species with the Born cavity size reported by Rashin and Honig, the parameterisation of the model is reduced to the determination of a single ion-solvent attractive interaction parameter. The resulting SAFT-VRE Mie parameter sets allow one to accurately reproduce the densities, vapour pressures, and osmotic coefficients for a broad variety of aqueous electrolyte solutions; the activity coefficients of the ions, which are not used in the parameterisation of the models, are also found to be in good agreement with the experimental data. The models are shown to be reliable beyond the molality range considered during parameter estimation. The inclusion of the Born free-energy contribution, together with appropriate estimates for the size of the ionic cavity, allows for accurate predictions of the Gibbs free energy of solvation of the ionic species considered. The solubility limits are also predicted for a number of salts; in cases where reliable reference data are available the predictions are in good agreement with experiment.

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Section:  Solid-liquid Phase Equilibriamentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Development of intermolecular potential models for electrolyte solutions using an electrolyte SAFT-VR Mie equation of state

et al. 2016

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“…Held et al (2008) extended the work done by Cameretti et al correlating densities and mean ionic activity coefficients at 298.15 K and predicting vapor pressures. Inchekel et al (2008) proposed an extension of the Cubic Plus Association (CPA) equation along with Born and MSA terms, in order to calculate the apparent molar volume, mean ionic activity coefficient and osmotic coefficient for 10 aqueous electrolyte solutions considering three ion-specific parameters. Held et al (2008) studied the behavior of systems containing weak electrolytes, correlating densities and mean ionic activity coefficients, using ion-pairing parameters.…”

Section: List Of Symbolsmentioning

confidence: 99%

Thermodynamic Properties of 1:1 Salt Aqueous Solutions with the Electrolattice Equation of State

Zuber

Checoni

Mathew

et al. 2013

Oil Gas Sci. Technol. – Rev. IFP Energies nouvelles

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Re´sume´-Proprie´te´s thermophysiques des solutions aqueuses de sels 1:1 avec l'e´quation d'e´tat de re´seau pour e´lectrolytes -L'e´quation d'e´tat, dite e´lectrolattice, est un mode`le qui e´tend l'e´quation d'e´tat de Mattedi-Tavares-Castier a`des syste`mes avec e´lectrolytes. Ce mode`le prend en compte l'effet de trois termes. Le premier terme est base´sur les trous dans le re´seau en conside´rant les effets de la composition locale, e´tude effectue´e dans le cadre de la the´orie ge´ne´ralise´e de Van der Waals : l'e´quation d'e´tat de Mattedi-Tavares-Castier a e´te´choisie pour ce premier terme. Les deuxie`me et troisie`me termes sont les contributions de Born et du MSA. Ils tiennent compte du chargement et du de´chargement des ions, et des interactions ioniques al ongue distance, respectivement. Le mode`le n'ayant besoin que de deux parame`tres d'interaction e´nerge´tique, il mode´lise de manie`re satisfaisante la pression de vapeur et le coefficient d'activiteí onique moyenne pour des solutions aqueuses simples contenant du LiCl, LiBr, LiI, NaCl, NaBr, NaI, KCl, KBr, KI, CsCl, CsBr, CsI, ou du RbCl. Deux me´thodes pour obtenir les parame`tres du mode`le sont pre´sente´es et mises en contraste : une me´thode spe´cifique pour le sel en question et une autre base´e sur les ions. Par conse´quent, l'objectif de ce travail est de calculer les proprie´te´s thermophysiques qui sont largement utilise´es pour la conception, l'exploitation et l'optimisation de nombreux proce´de´s industriels, parmi eux le dessalement de l'eau.Abstract -Thermodynamic Properties of 1:1 Salt Aqueous Solutions with the Electrolattice Equation of State -The electrolattice Equation of State (EOS) is a model that extends the MattediTavares-Castier EOS (MTC EOS) to systems with electrolytes. This model considers the effect of three terms. The first one is based on a lattice-hole model that considers local composition effects derived in the context of the generalized Van der Waals theory: the MTC EOS was chosen for this term. The second and the third terms are the Born and the MSA contributions, which take into account ion charging and discharging and long-range ionic interactions, respectively. Depending only on two energy interaction parameters, the model represents satisfactorily the vapor pressure and the mean ionic activity coefficient data of single aqueous solutions containing LiCl, LiBr, LiI, NaCl, NaBr, NaI, KCl, KBr, KI, CsCl, CsBr, CsI, or RbCl. Two methods are presented and contrasted: the salt-specific and the ion-specific approaches. Therefore, the aim of this work is to calculate thermodynamic properties that are extensively used to design, operate and optimize many industrial processes, including water desalination.

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“…Finally, the capability of the models was depicted to confirm the experimental data. Additionally, Inchekel et al [21] proposed an extension of CPA EOS for electrolyte solutions. They used a simplified MSA theory, and interpreted the Born term as a Gibbs free energy for short-range interactions of ion-solvent.…”

Section: Introductionmentioning

confidence: 99%

Application of ion-based ePC-SAFT in prediction of density of aqueous electrolyte solutions

Shadloo

Abolala

Peyvandi

2016

Journal of Molecular Liquids

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The simultaneous representation of dielectric constant, volume and activity coefficients using an electrolyte equation of state

Cited by 68 publications

References 37 publications

Development of intermolecular potential models for electrolyte solutions using an electrolyte SAFT-VR Mie equation of state

Development of intermolecular potential models for electrolyte solutions using an electrolyte SAFT-VR Mie equation of state

Thermodynamic Properties of 1:1 Salt Aqueous Solutions with the Electrolattice Equation of State

Application of ion-based ePC-SAFT in prediction of density of aqueous electrolyte solutions

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