Unlike Lennard-Jones Parameters for Vapor-Liquid Equilibria

TL;DR

This study examines how unlike Lennard-Jones parameters affect vapor-liquid equilibria and evaluates the predictive accuracy of eleven combining rules, concluding that direct adjustment to experimental data is necessary for accurate mixture modeling.

Contribution

It systematically analyzes the influence of unlike LJ parameters on vapor-liquid properties and assesses the performance of multiple combining rules, highlighting the need for experimental data fitting.

Findings

Vapor pressure depends strongly on both size and energy LJ parameters.

Bubble density is mainly influenced by the size parameter.

None of the eleven combining rules consistently predicts accurate unlike LJ parameters.

Abstract

The influence of the unlike Lennard-Jones (LJ) parameters on vapor-liquid equilibria of mixtures is investigated and the performance of eleven combining rules is assessed. In the first part of the work, the influence of the unlike LJ size and energy parameter on vapor pressure, bubble density and dew point composition is systematically studied for the mixtures CO+$\rm C_2H_6$ and $\rm N_2$ + $\rm C_3H_6$, respectively. It is found that mixture vapor pressure depends strongly both on the size and the energy parameter whereas the bubble density depends mostly on the size parameter and the dew point composition is rather insensitive to both parameters. In preceding work, unlike LJ parameters were adjusted to experimental binary vapor-liquid equilibria for 44 real mixtures. On the basis of these results, in the second part of the work eleven combining rules are assessed regarding their predictive power. A comparison with the adjusted unlike LJ parameters determined from the fit shows that none of the eleven combining rules yields appropriate parameters in general. To obtain an accurate mixture model, the unlike dispersive interaction should therefore be adjusted to experimental binary data. The results from the present work indicate that it is sufficient to use the Lorenz rule for the unlike LJ size parameter and to fit the unlike LJ energy parameter to the vapor pressure.