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American Chemical Society, Journal of Physical Chemistry B (Soft Condensed Matter and Biophysical Chemistry), 27(117), p. 8159-8171, 2013

DOI: 10.1021/jp401307t

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Free-Volume Theory Coupled with Soft-SAFT for Viscosity Calculations: Comparison with Molecular Simulation and Experimental Data

Journal article published in 2013 by Fèlix Llovell ORCID, Rosa M. Marcos, Lourdes F. Vega
This paper is available in a repository.
This paper is available in a repository.

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Abstract

The evaluation of phase equilibria and solubility properties through theoretical approaches is a well-known field, where a significant amount of models are able to describe those properties with a good degree of accuracy. However, the simultaneous calculation of transport properties together with these phase properties still remains a challenge, due to the difficulties in describing the behavior of properties like the viscosity of fluids with the same approach. In this work, the Free-Volume Theory (FVT) has been coupled with the soft-SAFT equation for the first time to extend the capabilities of the equation to the calculation of transport properties. The theory has been first tested using simulation data of the viscosity of the Lennard-Jones (LJ) fluid and LJ chains over a wide range of temperature and pressure. Good agreement has been found at all chain lengths, except for some deviations at near-zero density values. Several trends of the viscosity parameters with the length of the chain are identified, allowing the prediction of other chain fluids. Finally, the new equation has been applied to the n-alkanes family, where viscosity is a key property, and results compared with experimental data. The three viscosity parameters were fitted to viscosity data of the pure fluid at several isotherms or isobars, while the density and pressure were taken from the soft-SAFT output. Again, the effect of these parameters on the viscosity has been investigated and compared with results obtained for the LJ chains. The new equation performs very well in all cases, with a global Average Absolute Deviation of 1.85%, and shows predictive capabilities for heavier compounds. This empowers soft-SAFT with new capabilities, allowing the equation to calculate phase, interfacial and transport properties with the same model and degree of accuracy.