T-xy & P-xy Diagram

The following graph is a Txy, which represents the binary interaction of water with ethanol,
using the Ideal model:

The following graph is a Pxy, which represents the binary interaction of water with ethanol,
using the Ideal model:

The Wilson model.

The Wilson model is frequently used to study vapor-liquid equilibria. Based on the
molecular considerations the equation for the Wilson model presents the following
expression for the excess Gibbs energy of a binary solution (Wilson, NRTL and UNIQUAC
Equations, s.f.):

In the next graphic we can see the Wilson Txy for the binary system: water-ethanol.

As we can see, it is very different from the Txy ideal graphic, and maybe the strongest
reason is because the wilson model takes into account activity coefficients from the
system. (Wilson, NRTL and UNIQUAC Equations, s.f.):

And also has two adjustable parameters: 12, 21, these are related to the purecomponent molar volumes and to characteristic energy differences by:

In the next graphic we can see how is the deviation from the ideal model to the wilson
model comparing the two models in one graphic, in which the wilson model is in pink color
and the ideal model is in green and blue:

However the wilson model has two main disadvantages for the modeling of the vaporliquid equilibria: the first one is that the equations for the activity coefficients derived from
this formula are not useful when the logarithms of the activity coefficients, when plotted
against x, exhibit maxima or minima. Although these systems are not common. The
second one and most important is that when Wilson's equation is used for a binary system
with thermodynamic stability, no parameters are found for 12, 21 that indicates the
existence of two stable liquid phases (Suppes, s.f.).
The NRTL Model.
Renon als Wilson used the concept of local composition for the non random, two liquid
model (NRTL model), however this model is applicable to partially miscible or full miscible
systems (where the Wilson model fails). (Wilson, NRTL and UNIQUAC Equations, s.f.).
The model presents the following expression for the excess Gibbs energy of a binary
solution:

In the next graphic we can see the NRTL Txy for the binary system: water-ethanol.

As we can see the Txy graphic from NRTL model is similar to the Txy Graphic from Wilson
model, that can be because the energy parameter (gij) from NRT model is similar to the
characteristic energy parameter from Wilsons model (ij). (Wilson, NRTL and UNIQUAC
Equations, s.f.). These parameter measure the i-j interactions. This can be demonstrated
in the following graphic which compares NRTL vs Ideal vs Wilson:

UNIQUAC Model
The UNIQUAC model is an extension of the quasi-chemical theory for non-random
mixtures containing components of different size (Rlvia, 2009). This model is a derivation
of the NRTL equation, however it is more suitable for than (Wilson, NRTL and
UNIQUAC Equations, s.f.). This model for the excess Gibbs energy, consists in two parts:
a combinatorial part which describes the dominant entropic contribution, and a residual
part responsible for the enthalpy of mixing. The combinatorial part is determined by the

size and shapes of the molecules. On the other side, the residual part depends on
intermolecular forces (Rlvia, 2009).
The UNIQUAC equation is:

and for binary mixtures are:

In the following graph, it is represented the interaction of water and ethanol using
UNIQUAC model.

As said before, the UNIQUAC model is a deviation from the NRT model and therefore
their graphics are very similar. However, they both have a small deviation from Wilsons
model. This comparison can be observed in the following graphic in which the 4 models
are included:

Choosing one model

As seen in the previous graphs, the four models are very similar and they could all be
used to demonstrate the water-ethanol interactions. But according to the usage of each
model UNIQUAC and Wilson would be the best options for this.
UNIQUAC is derived from NRT model, but it considers the size and shape of the
molecules. Therefore, in this case, in which both molecules are of different size, it has a
better modeling of the reality of the interactions. However, in order to make the next
analysis we decided to use the Wilson model, because according to Galen J. Suppes the
Wilson model is the best choice for vapor-liquid equilibria for alcohols and phenols, and
as our binary system is composed by water and ethanol, we have one alcohol in the
system. Also the NRTL is more advisable for the liquid-liquid equilibria.
Maximum X achievable.
The maximum X achievable is calculated using the wilson graph from Aspen Plus, as we
approximate to the point at which the two graphics, X and Y join together. The following
graph shows that point and the value of the maximum X achievable(0.780061):

Calculating the theoretical plates for the distillation column

In order to calculate the theoretical plates for the distillation column, we use the level rule,
starting at a concentration of 0.05. The following graph shows the application of the level
rule. We consider that 3 plates for the column are enough, since the X achieved is 0.70,
other plate, would be an additional cost and it only increase the separation in 0.08.

Relation of the component structure with intermolecular forces

As it can be seen in the previous graphics, were Wilson, NRTL and UNIQUAC models
were compared against the Ideal one, all three have a completely different graphic than
the Ideal one. This is because the Ideal model does not considers at all intermolecular
interactions and on the other side, the other three models consider them and have other
properties to correct their possible deviations.
In case of water-ethanol solutions, there can be formed strong O-H and O-O bondings,
and therefore this strong interactions must be considered in the Model used to represent
the solution (Kholmurodov, 2011).
References
Kholmurodov, K.; Dushanov, E.; Yasuoka, K.; et.al. (2011). Molecular dynamics simulation
of the interaction of ethanol-water mixture with a Pt surface. Retrieved on 23 november 2015
from:
https://www.google.com.mx/url?sa=t&rct=j&q=&esrc=s&source=web&cd=6&cad=rja&uact=8&ve
d=0ahUKEwiftbS1nKnJAhUBwiYKHR2XAPkQFghQMAU&url=http%3A%2F%2Fwww.scirp.org
%2Fjournal%2FPaperDownload.aspx%3FpaperID%3D9240&usg=AFQjCNFMZEr1n3LJdVjdJ0
PiKiGMBqGt7Q&sig2=tai7yAW9JVZRV0GrImtBkQ&bvm=bv.108194040,d.eWE
Rlvia, S.; Geormenny, R.; Aznar, M. (2009). UNIQUAC correlation of liquidliquid
equilibrium in systems involving ionic liquids: The DFTPCM approach. Retrieved on 23
november 2015 from: http://www.sarec-fiq.edu.ni/pmciq/che570/pdf/articulo.pdf
Suppes J. (s.f.) Selecting thermodynamic models for Process simulation of Organic VLE
and LLE systems. Retrieved from: http://people.clarkson.edu/~wwilcox/Design/
Wilson, NRTL and UNIQUAC Equations. (s.f) Retreived on 23 november 2015 from:
http://webpages.sdsmt.edu/~ddixon/prausnitz_activcoeff.pdf