Prediction of binary intermolecular potential parameters for use in modelling fluid mixtures

Haslam, Andrew J.; Galindo, Amparo; Jackson, George

doi:10.1016/j.fluid.2008.02.004

Cited by 134 publications

(106 citation statements)

References 88 publications

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“…Importantly, the ion potential models obtained are seen to be physically realistic. This is achieved by introducing experimental information for a number of the model parameters; experimentally derived quantities such as the ionic and Born diameters are used directly, while experimental ionisation potentials, polarisabilities, and electron affinities inform ion-ion energetic parameters through the use of a theoretical relation developed in previous work [66]. The number of adjustable parameters has therefore been reduced, compared with the previous formulation of SAFT-VRE SW [21].…”

Section: Discussionmentioning

confidence: 99%

“…The dispersion energy ε ii between two identical ions or ε i j between any two unlike is obtained by analogy to the work of Hudson and McCoubrey [21,65,66]. In order to obtain the dispersion energy between two ions, we relate the London [67] dispersion interaction potential to the Mie intermolecular potential model given by Equation (3).…”

Section: Ion-ion Interactionsmentioning

confidence: 99%

“…In order to obtain the dispersion energy between two ions, we relate the London [67] dispersion interaction potential to the Mie intermolecular potential model given by Equation (3). The London interaction potential can be expressed as a function of ionisation potentials as [66] …”

Section: Ion-ion Interactionsmentioning

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: Discussionmentioning

confidence: 99%

Section: Ion-ion Interactionsmentioning

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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“…Equation 28, may be obtained through a procedure given by Hudson and McCoubrey [117] as detailed in reference [118].…”

Section: Combining Rulesmentioning

confidence: 99%

Interfacial tensions of systems comprising water, carbon dioxide and diluent gases at high pressures: Experimental measurements and modelling with SAFT-VR Mie and square-gradient theory

Chow

Eriksen

Galindo

et al. 2016

Fluid Phase Equilibria

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“…58 including interactions such as dipole-dipole and dipole-induce dipole, as well those arising from the permanent quadrupole moment of the molecules. In the absence of dipole and hydrogenbonding terms the k ij is given by 58…”

Section: Mixturesmentioning

confidence: 99%

Experimental and Molecular Modeling Study of the Three-Phase Behavior of (n-Decane + Carbon Dioxide + Water) at Reservoir Conditions

2011

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Knowledge of the phase behaviour of mixtures of oil with carbon dioxide and water is essential for reservoir engineering, especially in the processes of enhanced oil recovery and geological storage of carbon dioxide. However, for a comprehensive understanding, the study of simpler systems needs to be completed. In this work the system (n-decane + carbon dioxide + water) was studied as a model (oil + carbon dioxide + water) mixture. To accomplish our aim, a new analytical apparatus to measure phase equilibria at high pressure was designed with maximum operating temperature and pressure of 423 K and 45 MPa, respectively. The equipment relies on recirculation of two coexisting phases using a two-channel magnetically operated micro-pump designed during this work, with sampling and on-line compositional analysis by gas chromatography. The apparatus has been validated by comparison with published isothermal vapour-liquid equilibrium data for the binary system (n-decane + carbon dioxide). New experimental data have been measured for the system (n-decane + carbon dioxide + water) under conditions of three-phase equilibria. Data for the three coexisting phases have been obtained on five isotherms at temperatures from (323 to 413) K and at pressures up to the point at which two of the phases become critical. The experimental work is 1 complemented here with a theoretical effort in which we developed models for these molecules within the framework of the statistical associating fluid theory for potentials of variable range (SAFT-VR). The phase behaviour of the three binary subsystems was calculated using this theory and, where applicable, a modification of the Hudson and McCoubrey combining rules was used to treat the systems predictively. The experimental data obtained for the ternary mixture are compared to the predictions of the theory. Furthermore, a detailed analysis of the ternary mixture is carried out based on comparison with available data for the constituent binary subsystems. In this way, we analysed the observed effects on the solubility when the third component was added.

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Prediction of binary intermolecular potential parameters for use in modelling fluid mixtures

Cited by 134 publications

References 88 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

Interfacial tensions of systems comprising water, carbon dioxide and diluent gases at high pressures: Experimental measurements and modelling with SAFT-VR Mie and square-gradient theory

Experimental and Molecular Modeling Study of the Three-Phase Behavior of (n-Decane + Carbon Dioxide + Water) at Reservoir Conditions

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