An equation‐of‐state contribution for polar components: Dipolar molecules

Groß, Joachim; Vrabec, Jadran

doi:10.1002/aic.10683

Cited by 329 publications

(429 citation statements)

References 53 publications

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“…The change in free energy due to short-range directional association between molecules follows the TPT1 formulation [35,[38][39][40][41]56] of Wertheim (the latest formalism for associating Mie fluids is employed in our current work [107]):…”

Section: Free-energy Termsmentioning

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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Section: Free-energy Termsmentioning

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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“…The two parameters, the dipole moment D and the quadrupole moment Q, can suitably be approximated from quantum chemical calculations or from experiments. [44][45][46] Although the vacuum values do not do justice to the higher effective dipole moment in a dense fluid phase, the vacuum values can ͑at least for purposes of correlations͒ be used. This can be attributed to the observation that induced dipolar interactions can for pure fluids be well "hidden" as quasidispersive attractions.…”

Section: Molecular Model and Bulk Equation Of Statementioning

confidence: 99%

“…The equation-of-state expressions are based on a third-order perturbation theory that was parametrized to comprehensive molecular simulation data for two-center Lennard-Jones fluids. [44][45][46] For molecular elongations up to two segments, the molecular model is well defined and the multipole moments ͑dipole and quadrupole moment͒ are assumed to be aligned along the molecular axis. 44 For molecules with more than two segments the multipolar interactions are assumed to only stretch between two segments.…”

Section: Molecular Model and Bulk Equation Of Statementioning

confidence: 99%

A density functional theory for vapor-liquid interfaces using the PCP-SAFT equation of state

Groß

2009

The Journal of Chemical Physics

Self Cite

104

110

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A Helmholtz energy functional for inhomogeneous fluid phases based on the perturbed-chain polar statistical associating fluid theory ͑PCP-SAFT͒ equation of state is proposed. The model is supplemented with a capillary wave contribution to the surface tension to account for long-wavelength fluctuations of a vapor-liquid interface. The functional for the dispersive attraction is based on a nonlocal perturbation theory for chain fluids and the difference of the perturbation theory to the dispersion term of the PCP-SAFT equation of state is treated with a local density approximation. This approach suggested by Gloor et al. ͓Fluid Phase Equilib. 194, 521 ͑2002͔͒ leads to full compatibility with the PCP-SAFT equation of state. Several levels of approximation are compared for the nonlocal functional of the dispersive attractions. A first-order non-mean-field description is found to be superior to a mean-field treatment, whereas the inclusion of a second-order perturbation term does not contribute significantly to the results. The proposed functional gives excellent results for the surface tension of nonpolar or only moderately polar fluids, such as alkanes, aromatic substances, ethers, and ethanoates. A local density approximation for the polar interactions is sufficient for carbon dioxide as a strongly quadrupolar compound. The surface tension of acetone, as an archetype dipolar fluid, is overestimated, suggesting that a nonisotropic orientational distribution function across an interface should for strong dipolar substances be accounted for.

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“…Also, we note that the axially symmetric case studied in the paper is probably the most difficult case to study theoretically due to the fact that, in this case, association induces long range order of the clusters. Possible extensions of this work include incorporation of the results of this letter with a bulk equation of state for dipolar molecular fluids 31 allowing for the study of the effect of electric fields on phase equilibria. Also, using the multi -density approach of Kalyuzhnyi and Stell 11 , Kalyuzhnyi et al 13 developed an equation of state for dipolar hard spheres.…”

Section:    mentioning

confidence: 99%

Classical density functional theory for associating fluids in orienting external fields

2013

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We develop a classical density functional theory (DFT) for two site associating fluids in spatially homogeneous external fields which exhibit orientational inhomogeneities. The Helmholtz free energy functional is obtained using Wertheim's thermodynamic perturbation theory and the orientational distribution function is obtained using DFT in the canonical ensemble. It is shown that an orientating field significantly enhances association by ordering the molecules thereby reducing the entropic penalty of association. It is also shown that association enhances the orientational order for fixed field strength.The statistical mechanics of associating fluids has been the focus of much development for many decades. In the 1980's the search for primitive models of the hydrogen bond was the catalyst for advancement. Development of a theory for hydrogen bonding had to account for both the anisotropic nature of the pair potential as well as bond saturation. In a series of four classic papers 1-4 Wertheim developed a multi -density cluster expansion incorporating these basic features of the hydrogen bond. Since its development, Wertheim's theory has been widely applied in the modeling of homogeneous hydrogen bonding fluids 5-8 and, more recently, to study the self assembly and phase behavior of patchy colloid fluids 9, 10 . A similar multi -density approach for associating fluids with spherically symmetric attractions 11 has had application to highly asymmetric electrolyte solutions 12 as well as equations of state for dipolar fluids 13Patchy colloids are colloids with discrete attractive patches giving orientation dependant potentials with limited valence. 9 Recently, a number of synthetic methods [14][15][16] have been developed to produce patchy colloids. This gives researchers the ability to program the self assembly of these colloids into colloidal molecules 16 , Kagome lattices 17 and network fluid

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An equation‐of‐state contribution for polar components: Dipolar molecules

Cited by 329 publications

References 53 publications

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

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

A density functional theory for vapor-liquid interfaces using the PCP-SAFT equation of state

Classical density functional theory for associating fluids in orienting external fields

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