How to Model Vapor-Liquid Equilibria (VLE) Data with ChemSep

Here we will explain you how you make your comparisons with VLE data with activity coefficient models using
ChemSep (LITE) (available free from www.chemsep.com).
We will illustrate by trying to model the VLE of a mixture of acetone and benzene.
Selecting the components
When we want to compare the VLE data to predicted values by thermodynamic models we need to define the
components as well as make a model selection and provide the interaction parameters for the models. Select
"Components" in the tree of the input navigator on the left hand side. This will open a pane where we can select
the compounds. ChemSep shows the compounds in the default component library (a "PCD" file) and you can
select any of these by double-clicking a compound. Typing a (part of a ) name in the "find" box will narrow down
the list of components to only those with the particular string in the name (clicking the "advanced" checkbox
allows for more sophisticated searched). We add the components in the order of their boiling point, first acetone
and then benzene:
Selecting the thermodynamic model(s)
Next we click on the "properties" in the input navigation tree to select the thermodynamic models. For nonideal
systems such as the system at hand an activity coefficient model is needed to represent the non-ideality of the
liquid mixture. The resulting model for the K-values is called the DECHEMA model, since it is also used in the
DECHEMA data book series. As activity model we will first select a predictive model, UNIFAC, which will require
no further input. As vapor pressure model we select the Antoine model.
Specifying units of measure
To display our calculations in the same units of measure, select "units" in the navigator. Our experimental data
was in degrees Celcius and torr (mm Hg). Since torr is not part of the standard list of pressure units you must
type it in the edit box. ChemSep allows you to do so and thus compose all kinds of personal units of measure.
ChemSep knows most chemical engineering units and all the prefixes to scale them.

Now save the file under a descriptive name, for example "bvle_acetone_benzene_t25.sep".
VLE model predictions
Then go to Analysis - Phase diagrams - Binary menu option. This opens a window to generate our pxy diagram.
Select the type of diagram (pxy) and phase equilibrium (VLE) as well the condition (temperature = 25C) and click
on calculate to generate the phase diagram:
VLE Data
Binary VLE data for Acetone and Benzene was published by A. Tasic, B. Djordjevic, D. Grozdanic, N. Afgan, D.
Malic, in Chem. Eng. Sci. (1978), 33, pp. 189-197. We created a text file that contains their data as shown
below:
# file=bvle_acetone_benzene_t25.txt
# ref=ces33p189
# title=P-xy data for acetone (1051) / benzene (501) at 25 C in torr
# fullref=A.Tasic, B.Djordjevic, D.Grozdanic, N.Afgan, D.Malic, Chem.Eng.Sci. (1978), 33, pp. 189-197
p x y
95.05 0 0
116.65 0.082 0.248
137.2 0.185 0.416
156.3 0.307 0.55
169.3 0.401 0.632
182.1 0.505 0.703
191.2 0.59 0.755
203.2 0.704 0.824
213.4 0.8055 0.882
220.95 0.8955 0.936
222.35 0.909 0.944
225.05 0.932 0.958
230.4 1 1

Since acetone boils at a lower temperature than benzene it comes first. As a last part of the file we add a
comment line that specifies the conditions at which the measurements were taken; here at constant temperature
of 25 C and the units for pressure.
It is important to note that pressure must be identified by a lower-case p.
Note that the numerical values in the table are separated by tabs. ChemSep's import option for binary VLE data
also allows spaces, comma's, or semicolons as separators. It is important that you include a line describing the
type of data in each column. With the "Copy data" button you can copy the data to the clipboard and from there
to a sep file or a text file. Be sure to always include the complete reference to the original article and a
descriptive title. Use specific set of journal abbreviations and refer to the volume and first page of the publication
so that will be easy to find the original source at some point in the future; in this case "ces33p189". The title and
reference are put on lines that start with a "#" to indicate the line does not contain data. You can have as many
lines with “comments as needed as long as each of them starts with the “#”. You MUST have at least one
comment line.
Adding the data to ChemSep
Copy the data file above into the space for Comments on the Title panel as shown below.
Comparing experimental data with the selected model predictions
Now we want to make a comparison of the model predictions with the experimental data. For this we must load
the data either from a file or from the comments section. For both methods you must click the "file open" icon
next to data. In our case we must click Yes when asked to Load data from comments field. This loads the
information from the comments page onto the data line (all in one line) – as shown below:
pxy;
p=95.05,x=0,y=0;
p=116.65,x=0.082,y=0.248;
p=137.2,x=0.185,y=0.416;
p=156.3,x=0.307,y=0.55;
p=169.3,x=0.401,y=0.632;
p=182.1,x=0.505,y=0.703;
p=191.2,x=0.59,y=0.755;
p=203.2,x=0.704,y=0.824;
p=213.4,x=0.8055,y=0.882;
p=220.95,x=0.8955,y=0.936;
p=222.35,x=0.909,y=0.944;
p=225.05,x=0.932,y=0.958;
p=230.4,x=1,y=1;

We see the data is processed: the pxy identifier is repeated and then used for identifying each data item,
separated by comma's. The data points themselves are separated by semicolons. Note that the original data did
not have units, so no conversions are done. The diagram now has the points shown as entered:
Calculating standard deviations in y and p
To quantify the deviations between the model and the experimental points we can compute the standard
deviations by clicking the "Data Dev." button. This computes for each point the pressure p and vapor fraction z
that is in equilibrium with the measured liquid composition x and the specified temperature 25 oC. ChemSep adds
these to the the data line:
pxy;
p=95.05,x=0,y=0;
p=116.65,x=0.082,y=0.248,q=116.8901,z=0.231314;
p=137.2,x=0.185,y=0.416,q=137.7293,z=0.414939;
p=156.3,x=0.307,y=0.55,q=158.3805,z=0.557008;
p=169.3,x=0.401,y=0.632,q=171.8393,z=0.636984;
p=182.1,x=0.505,y=0.703,q=184.7208,z=0.708714;
p=191.2,x=0.59,y=0.755,q=193.9699,z=0.759586;
p=203.2,x=0.704,y=0.824,q=204.9321,z=0.822478;
p=213.4,x=0.8055,y=0.882,q=213.554,z=0.877809;
p=220.95,x=0.8955,y=0.936,q=220.3915,z=0.930066;
p=222.35,x=0.909,y=0.944,q=221.3489,z=0.938402;
p=225.05,x=0.932,y=0.958,q=222.9353,z=0.95301;
p=230.4,x=1,y=1;

It also computes the relative standard deviations (only for the binary points) and adds them to the title of the
diagram: sy is the standard deviation in the vapor composition and sp is the standard deviation in pressure.
In this case most of the deviation in the pxy diagram is caused by the Antoine model not being good enough in
this case at predicting the pure component vapor pressures.
Selecting the UNIQUAC activity coefficient model and interaction parameters
We now return to the thermodynamic model selections and select the UNIQUAC model and load the parameters
from the library:
UNIQUAC fit of the VLE data
When we return to the phase diagrams panel and redraw the diagram we will obtain a fit that is less good -
deviations in pressure increase by more than a factor two - but the curvature of the dew and bubble point lines is
correct:

Thus, lower relative deviations of pressure and mole fractions aren't necessarily indicative for a qualitative better
description of the binary VLE. This is due to the errors in the pure component vapour pressures. Errors over half
of the concentration range are introduced when a pure component bubble point temperature is off by just one or
two degrees! We leave it to the reader as an exercise to select different models for the vapor pressure to see
how the predictions can vary.