CHE 624 – ENCH 633 Assignment Series 5

Due date is November 30th 2009.

The Problem
NRTL is a common activity coefficient method used to simulate the behavior of highly
non-ideal systems with considerable success. Nevertheless, NRTL is known to predict
incorrect phase behavior, including the prediction of multiple liquid when only one or
two actually exist in reality as shown by Heidemann and Mandhane (1973).

Using Heidemann and Mandhane’s paper as a reference, focus on the n-Butyl Acetate /
Water system using the interaction parameters shown in equation 18.

1. Calculate the Gibbs free energy of this system and compare to the results shown
in figure 2.

This part is trivial, you just have to calculate the Gibbs free energy using activity
coefficients:

2. Using the tangent plane criteria determine the approximate liquid phase
compositions at equilibrium when the bulk composition is equal to 0.2 n-Butyl
Acetate graphically.
3. Using the tangent plane criteria determine the approximate liquid phase
compositions at equilibrium when the bulk composition is equal to 0.8 n-Butyl
Acetate graphically.
4. The mutual solubility of n-Butyl Acetate in water at 363.65 K is 0.824 n-Butyl
Acetate in the organic phase and 0.0009 n-Butyl Acetate in the aqueous phase
(Gomis et al, 2000). Using the Gibbs free energy diagram you calculated in (1)
determine the composition of phases at equilibrium for a bulk feed phase with 0.4
mole fraction n-Butyl Acetate graphically.
 5. Comment on the applicability of NRTL as a thermodynamic model for this
system.

The model is incorrect since there should be a constant composition for the water rich
phase and the n-Butyl Acetate rich phase if feed is between approximately 0.0009 and
0.824 n-Butyl Acetate mole fraction. This is an issue with activity coefficient models
particularly with NRTL. This issue is not limited to activity coefficient models but also
appears when you have activity coefficient models integrated with an equation of state
using Gibbs free energy matching (e.g. Huron-Vidal) or composition dependent mixing
rules such as Stryjek-Vera and Schwartzengruber and Renon.

References
Gomis, V.; Ruiz, F.; Asensi, J. C.; Fluid Phase Equilib., 2000, 172, 245.
Heidemann, R.E. and Mandhane, J.M.; Chemical Engineering Science. 1973, Vol. 28. pp.
1213-1221.