Non Random Two Liquid Model

Presented By Nahid Arefin

Introduction

The non-random two-liquid model (short NRTL equation) is an activity coefficient model that correlates the activity coefficients i of a compound i with its mole fractions xi in the liquid phase concerned. It is frequently applied in the field of chemical engineering to calculate phase equilibria. The concept of NRTL is based on the hypothesis of Wilson that the local concentration around a molecule is different from the bulk concentration. This difference is due to a difference between the interaction energy of the central molecule with the molecules of its own kind Uii and that with the molecules of the other kind Uij.

Dan F. Smith Department of Chemical Engineering, Lamar University

Introduction
The energy difference also introduces a non-randomness at the local molecular level. The NRTL model belongs to the so-called localcomposition models. Other models of this type are the Wilson model, the UNIQUAC model, and the group contribution model UNIFAC. These local-composition models are not thermodynamically consistent due to the assumption that the local composition around molecule i is independent of the local composition around molecule j. This assumption is not true, as was shown by Flemmer in 1976.

Dan F. Smith Department of Chemical Engineering, Lamar University

Equations for a binary mixture

For a binary mixture the following equations are used:

Dan F. Smith Department of Chemical Engineering, Lamar University

Equations for a binary mixture

In here 12 and 21 are the dimensionless interaction parameters, which are related to the interaction energy parameters g12 and g21 by:

Here R is the gas constant and T the absolute temperature, and Uij is the energy between molecular surface i and j. Uii is the energy of evaporation. Here Uij has to be equal to Uji, but gij is not necessary equal to gji.

Dan F. Smith Department of Chemical Engineering, Lamar University

Equations for a binary mixture

The parameters 12 and 21 are the so-called non-randomness parameter, for which usually 12 is set equal to 21. For a liquid, in which the local distribution is random around the center molecule, the parameter 12 = 0.

Dan F. Smith Department of Chemical Engineering, Lamar University

Equations for a binary mixture

In practice, 12 is set to 0.2, 0.3 or 0.48. The latter value is frequently used for aqueous systems. The high value reflects the ordered structure caused by hydrogen bonds. However in the description of liquid-liquid equilibria the non-randomness parameter is set to 0.2 to avoid wrong liquid-liquid description

In some cases a better phase equilibria description is obtained by setting 12 = 1. However this mathematical solution is impossible from a physical point of view, since no system can be more random than random (12 =0). In general NRTL offers more flexibility in the description of phase equilibria than other activity models due to the extra non-randomness parameters. However in practice this flexibility is reduced in order to avoid wrong equilibrium description outside the range of regressed data.

Dan F. Smith Department of Chemical Engineering, Lamar University

Equations for a binary mixture

The limiting activity coefficients, aka the activity coefficients at infinite dilution, are calculated by:

The expressions show that at 12 = 0 the limiting activity coefficients are equal. This situation that occurs for molecules of equal size, but of different polarities. It also shows, since three parameters are available, that multiple sets of solutions are possible.

Dan F. Smith Department of Chemical Engineering, Lamar University

General equations
The general equation for ln(i) for species i in a mixture of n components is

With

There are several different equations forms for ij and ij, the most general of which are shown above.
Dan F. Smith Department of Chemical Engineering, Lamar University

Temperature dependent parameters

To describe phase equilibria over a large temperature regime, i.e. larger than 50 K, the interaction parameter has to be made temperature dependent. Two formats are frequently used. The extended Antoine Equation format:

Here the logarithmic term is mainly used in the description of liquidliquid equilibria. The other format is a third-order polynomial format:

Dan F. Smith Department of Chemical Engineering, Lamar University

Example
Equilibrium for n-Butanol - water - n-Butyl-acetate A water rich stream is removed at the top of the column and the organic phase is refluxed back to the column. The NRTL binary parameters are given in the following table.

Dan F. Smith Department of Chemical Engineering, Lamar University

Example
These parameters are temperature independent. So there is no need to consider a vapor phase. The problem was solved for the conditions in the top phase separator and the corresponding feed charge is as shown in the following table.

Dan F. Smith Department of Chemical Engineering, Lamar University

Example
is defined the objective function that was minimized and The global solution for the feed charge under consideration is supplied in the above table. The water rich phase composes 52% of the top phase separator exit stream. The algorithm tool 105 iterations and a total time of 2.01 cpu sec to obtain this solution. The fathoming rate was 67%.

Dan F. Smith Department of Chemical Engineering, Lamar University

Conclusion

Dan F. Smith Department of Chemical Engineering, Lamar University

Questions??

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Dan F. Smith Department of Chemical Engineering, Lamar University