Paulina Monroy Escobedo

Chemical Engineering
Problem definition
Liquids and gases formed by several components usually undergo changes in composition,
which are due to mixing processes. Thecalculation of mixture equilibria from pure
component data often gives a deviation for the actual system. This test will look for r program
an algorithm in Excel to predict a binary mixture azeotropic (T etrachloride carbon (1)- T
richloroethylene (2) at 20 ° C), using the model of thermodynamic activity of Margules for
the free energy of Gibbs. The Margules model is used to describe the Gibss free energy of a
binary system by an analytical equation defined in the range 0 to 1. The thermodynamic
model for calculating mixture equilibria is particularly important in process design for
industrial applications.

Objectives
General objective:
• Generate an algorithm in Excel that helps us to the thermodynamic characterization
of a binary mixture, with respect to the Gibbs free energy related to the composition
of the mixture (Carbon tetrachloride (1)- Trichloroethylene (2))). This through the
determination of the influence of temperature on the parameters of the Margules
function.

Specific objective:

• Find the parameters of Margules that is, to be able to 𝐴12 𝑦 21obtain the compositions
x1, y1 and P calculated. This will allow us to validate if our generated algorithm is
correct.

Research and methodology

The experimental values (activity coefficients) of y1 and y2 are obtained, which are:

𝑦1∗𝑃
𝑦1 𝑒𝑥𝑝 = 𝑥1∗𝑃𝑠𝑎𝑡 [Equation No.1]

The residual Gibbs energy is defined as the sum of the multiplications of the mole fractions
with the natural logarithm of the activity coefficients.

𝐺𝐸
= 𝑥1 ∗ ln(𝑦1) + 𝑥2 ∗ ln(𝑦2) [Equation No.2]
𝑅𝑇
Paulina Monroy Escobedo
Chemical Engineering
In order to get our values right 𝐴12 𝑦 21 we have two options. Una modifying the equation
𝐺𝐸
of𝑅𝑇 . Or two, using Excel's solver function.

𝐺𝐸 1 𝐺𝐸
To modify the equation , multiply both sides by the equation and 2 yields =
𝑅𝑇 𝑥1𝑥2 𝑅𝑇𝑥1𝑥2
𝑥1∗ln(𝑦1)+𝑥2∗ln (𝑦2)
. Now, the Margules model can be approximated by means of the equation:
𝑥1∗𝑥2

𝐺𝐸
= 𝐴12 ∗ 𝑥2 + 𝐴21 ∗ 𝑥1. [Equation No. 3]
𝑅𝑇𝑥1𝑥2

Where A12 and A21 are confirmations to be found.

𝐺𝐸
Once we have we𝑅𝑇𝑥1𝑥2 can obtain the values of ln y1 and ln y2. Through the equations:

ln 𝑦1 = [𝐴12 + 2(𝐴21 − 𝐴12 ) ∗ 𝑥1] ∗ 𝑥22 [Equation No.4]

ln 𝑦2 = [𝐴21 + 2(𝐴12 − 𝐴21 ) ∗ 𝑥2] ∗ 𝑥12 [Equation No.5]

Where Y are adjustable parameters 𝐴21 𝐴12 forthe binary mixture. These can be determined
as:

𝐴12 = 𝐿𝑛𝑦1∞ ]𝑥1=0 [Equation No.6]

𝐴21 = 𝐿𝑛𝑦2∞ ]𝑥1=1 [Equation No.7]

With the values of 𝐴12 𝑦 21 , we obtain P, X and Y calculated. Through the equations:

𝑥1∗𝑦1∗𝑃1
𝑦1𝑐𝑎𝑙 = [Equation No.8]
𝑃𝑐𝑎𝑙

𝑦1∗𝑃 𝑐𝑎𝑙
𝑥1𝑐𝑎𝑙 = 𝑦1𝑐𝑎𝑙 ∗𝑃1 [Equation No.9]

𝑃𝑐𝑎𝑙 = 𝑥1 ∗ 𝑦1 ∗ 𝑃1 + 𝑥2 ∗ 𝑦2 ∗ 𝑃2 [Equation No.10]

The methodology used was obtained from the book Smith J.M [5] and the article
"Estimación de las constants de Margules y Van laar para sistemas binarios por correlation"
[4]. As well as other sources of information for your understanding [3], [6].

Application of specific knowledge

Paulina Monroy Escobedo
Chemical Engineering
Our algorithm starts by obtaining x2 and y2, lors which are proportional, which is understood
to only subtract from 1.

To obtain the 𝐴12 𝑦 21 , we reuse the Gibbs free energy equation (equation 2). For this method,
the saturation pressure is found in our experimental data. Whenx or y have a value of zero
in their compositions, the first pressure given to us becomes the pressure for component two.
For pressure 1 , the lowest is taken when x and y are equal to 1.

Use equation 1 to get gamma1 and gamma 2. Then we getthe 𝐿𝑛(𝑦1) 𝑦 𝐿𝑛(𝑦2), to finally
replace these new values in equation 2. Once solved we graph the values reached ofl Ln
(y1) and Ln (y2), with respect to the methodology described in equations 6 and 7. With the
graph we obtain the values close to once with these 𝐴12 𝑦 21 we canfind two different ones,
𝐺𝐸 𝐺𝐸
one with equation 𝑅𝑇2 (exp𝑅𝑇erimental) and other with equation 3. The first will handle it
𝐺𝐸
as the experimental one and the one obtained with equation 3 (supposed)𝑅𝑇. Once we had
𝐺𝐸
our two𝑅𝑇, we took out their mistake. To obtain the error we will use:𝐴𝑏𝑠 =
𝐺𝐸 𝐺𝐸
(𝑅𝑇 − 𝑅𝑇 )2 , having its errors, we calculate the total sum of these. Within Excel in the
𝑐𝑎𝑙 𝑒𝑥𝑝

'data' section, click on the solver function. Within solver it will ask us to select "set goal"
and "changing variable cells". In 'set objectivev' we select the cell where the sum of our
error is located, and give it a value of zero, for the section 'changing the variable cells', we
select our two cells𝐴12 𝑦 21 . We click on accept, and solver will provide us with our correct
values of 𝐴12 𝑦 21 . Once with our results of , 𝐴12 𝑦 21 we can determine P, X and Y calculated
with equations 8, 9 and 10.

Resolution of the problem.

We were provided with data for the mole fractions (x1 and y1) in the liquid and vapor phases
as follows:

Table No.1. Experimental data for the Carbon tetrachloride (1)-Trichloroethylene (2)
system
Paulina Monroy Escobedo
Chemical Engineering
x1 Y1 P (mmHg) P (kpa)
0 0 72.8 9.70424
0.05 0.111 75 9.9975
0.1 0.195 78.3 10.43739
0.15 0.254 80.1 10.67733
0.2 0.297 81.2 10.82396
0.25 0.324 81.7 10.89061
0.3 0.343 81.9 10.91727
0.35 0.361 82 10.9306
0.4 0.378 82 10.9306
0.45 0.391 81.8 10.90394
0.5 0.4 81.5 10.86395
0.55 0.401 81.1 10.81063
0.6 0.408 80.3 10.70399
0.65 0.433 79 10.5307
0.7 0.458 77.4 10.31742
0.75 0.472 75.9 10.11747
0.8 0.505 75.3 10.03749
0.85 0.581 68.5 9.13105
0.9 0.689 61.9 8.25127
0.95 0.829 53.6 7.14488
1 1 43.6 5.81188

The values of the experimental compositions x2 and y2, y1 and y2 (equation 1), Ln y1 and
Lny2 were found, hausingthe methodology.

𝐺𝐸
Table 2. Previous results to be able to obtain 𝑅𝑇 experimental and supposed.

X2 Y2 y1 exp y2 exp Ln y1 Ln y2
1 1 0 1 0 0
0.95 0.889 3.81880734 0.96406883 1.33993816 -0.03659259
0.9 0.805 3.50194954 0.96201923 1.25331983 -0.03872084
0.85 0.746 3.11091743 0.96565288 1.13491768 -0.03495085
0.8 0.703 2.7656422 0.98014423 1.01727287 -0.02005554
0.75 0.676 2.42851376 1.01152381 0.88727945 0.01145792
0.7 0.657 2.14768349 1.05589286 0.76438981 0.05438672
0.65 0.639 1.93984273 1.10731192 0.6626069 0.10193538
0.6 0.622 1.77729358 1.16767399 0.57509175 0.15501373
0.55 0.609 1.6301631 1.24416084 0.48868007 0.21846128
0.5 0.6 1.49541284 1.34340659 0.40240232 0.29520862
0.45 0.599 1.35617598 1.48287241 0.30466896 0.39398102
0.4 0.592 1.25238532 1.63247253 0.22504999 0.49009575
0.35 0.567 1.20702188 1.75796703 0.18815607 0.56415805
0.3 0.542 1.16150721 1.92082418 0.14971848 0.65275435
0.25 0.528 1.09555963 2.20193407 0.09126531 0.7893361
0.2 0.495 1.06125287 2.49199863 0.05945016 0.91308505
0.15 0.419 1.07389369 2.62834249 0.071291 0.96635342
0.1 0.311 1.08687819 2.6443544 0.08330954 0.97242695
0.05 0.171 1.07277644 2.51802198 0.07025009 0.92347366
0 0 1 0 0 0

Inequations 6 and 7, we are told that𝐴12 it is defined as Ln(y1) evaluated in x1 which is

equal to zero and in as Ln𝐴21 (y2) which seeks to be equal to one. When observing our
results we agree with this methodology, understanding that the procedure is in the right
direction.

Counting on the logarithms, it was possible to proceed to graph and find the values close or
'supposed' to 𝐴12 𝑦 21 .

Graph 1. Ln(y1) vs Ln(y2).

Paulina Monroy Escobedo
Chemical Engineering

1.5

1
Ln y1
0.5
Ln y2
0
0 0.5 1 1.5
-0.5

With respect to the graph we can deduce that our assumed value of is 𝐴12 equal to 0.9 and
𝐴21 is 1.3.

Up to this point, and with regard to the methodology within equations 6 and 7, every mark
that our graph is represented in the correct way,

Without proper analysis of the 'assumed' values it would be more difficult to have an exact
approximation of the real values of .𝐴12 𝑦 21

𝐺𝐸
Table 3. Results of 𝑅𝑇 experimental and calculated, together with the sum of its error.

Ge/rt exp Ge/RT cal Delta Ge/RT

0 0 0
0.03223395 0.05243266 0.00040799
0.09048323 0.10192895 0.000131
0.14052943 0.1480584 5.6685E-05
0.18741014 0.19039051 8.8826E-06
0.2304133 0.22849483 3.6805E-06
0.26738765 0.26194088 2.9667E-05
0.29817041 0.29029817 6.1972E-05
0.32304494 0.31313623 9.8182E-05
0.34005973 0.33002459 0.0001007
0.34880547 0.34053277 6.8438E-05
0.34485939 0.3442303 3.9575E-07
0.3310683 0.34068669 9.2514E-05
0.31975676 0.32947148 9.4376E-05
0.30062924 0.31015418 9.0725E-05
0.26578301 0.28230433 0.00027295
0.23017714 0.24549144 0.00023453
0.20555036 0.19928503 3.9254E-05
0.17222128 0.14325464 0.00083907
0.11291127 0.07696979 0.00129179
0 0 0
suma 0.00392281

Table 4. Exact values 𝐴12 𝑦 21 .

A21 1.64911505
A12 1.07514713
Paulina Monroy Escobedo
Chemical Engineering
Results and analysis
Following our methodology, using equations 4, 5, 8.9 and 10, we obtain our final results.

Table 5. Final results.

LN Y1 LN Y2 Y1 Y2 Pcal (mmhg) y1 cal x1 cal
1.075 0 2.9299929 1 72.8 0 0
1.021991 0.001396 2.77872169 1.00139697 75.3142281 0.08043119 0.06900308
0.963738 0.006158 2.62147726 1.006177 77.3543579 0.14775691 0.13197352
0.901102 0.015147 2.46231509 1.0152623 78.9279716 0.20402831 0.18673879
0.834944 0.029224 2.30468498 1.02965521 80.0639726 0.25100994 0.23664401
0.766125 0.04925 2.15141335 1.05048294 80.806774 0.29020346 0.27911452
0.695506 0.076086 2.00472321 1.07905537 81.2104412 0.3228868 0.31868754
0.623948 0.110593 1.8662816 1.11694022 81.3330684 0.3501584 0.36083669
0.552312 0.153632 1.73726493 1.1660617 81.2314754 0.37298227 0.40538119
0.481459 0.206064 1.61843398 1.22883185 80.9561017 0.39223325 0.44858513
0.41225 0.26875 1.51021194 1.30832802 80.5457602 0.4087443 0.48930346
0.345546 0.342551 1.41276108 1.40853619 80.0216561 0.42336053 0.52095079
0.282208 0.428328 1.32605451 1.53468938 79.3797406 0.43700805 0.56017274
0.223097 0.526942 1.24994181 1.69374491 78.5799712 0.45079364 0.62434333
0.169074 0.639254 1.18420777 1.89506663 77.5302763 0.46616655 0.68773704
0.121 0.766125 1.12862491 2.15141335 76.0617577 0.48521144 0.72957885
0.079736 0.908416 1.08300112 2.48039048 73.8895644 0.511237 0.79024015
0.046143 1.066988 1.04722415 2.90661159 70.5503257 0.55010557 0.89773677
0.021082 1.242702 1.0213058 3.46496316 65.3009712 0.61371276 1.01040754
0.005414 1.436419 1.00542868 4.20560854 56.9532711 0.73121096 1.07704895
0 1.649 1 5.20177545 43.6 1 1

Graph 2. Experimental vs calculated data.

85
75 exp
65
exp
55
cal
45
35 cal
0 0.5 1 1.5

In our method equations 8, 9 and 10 were found, to solve the compositions and the calculated
pressure. One of the key points when obtaining the graph is that thanks to this we can observe
if our results coincide with those provided by the problem or that they change so much.

If we analyze our table 5 from bottom to top in x 1 cal, we can notice that in terms s 2 and 3,
values above1 are presented, which means that they are erroneous because they are outside
the expected range. With our methodology regarding equations 6, 7, and the experimental
data provided, we understand that compositions should be in a parameter of 1 to 0.

According to what we discussed above and reaching one of the objectives about calculating
the parameters of Margules, our final values will depend n on the most exact value we find
for 𝐴12 𝑦 21 . Following the methodology mentioned at the beginning, we realize that our
Paulina Monroy Escobedo
Chemical Engineering
values of 𝐴12 𝑦 21 assumptions vs. those calculated through our algorithm do not tend to be
very different. With the obtaining of the "𝐴12 𝑦 21 supposed" we were looking for a value to
approach our real results of 𝐴12 𝑦 21 . Since if we wanted to get a real value from the 𝐴12 𝑦 21
graphs we would be very far from reaching it, since the percentage of error between the
𝐴12 𝑦 21 supposed and the real ones is 18.73%. Dwithin our algorithm the results of these
parameters were the closest we found and without instead, they were not very variable
because the pressure difference was only 1.39%, and for y1cal 4.87%. For these results to
be closer to those providedby the problem, the results would have to continue to be
modified; however, it would already be interfering with the algorithm. 𝐴12 𝑦 21

Very close values could be found between the Pcal and the Ycal, which indicates that the
procedure is still correct. Finally, the objectives of generating an algorithm that would serve
to determine a binary mixture, with respect to the Gibbs free energy, were achieved. As well
as the parameters of the Margules function (𝐴12 𝑦 21 ), to obtain our calculated data x1, y1
and P. Which allowed the validation of our algorithm.

Self-reflection
(a) Gaps and/or the weaknesses.

The project was not shown as an easy task, because although it already had previous
knowledge, regarding the compositions and the constants of temperature and pressure, the
method of obtaining it remained different. The first gap I found was the methodology,
because it is often difficult and takes time to understand the information we are given. As
well as the fact of looking for different sources and not knowing which one to work with,
since based on the method I would find if my algorithm would work or not. Anothergap that
was to obtain the 𝐴12 𝑦 21 pues within the research I found different ways of finding, some
with more precise methods than others. However, the one I put into practice within this
project, turned out to be the closest and with more sense, because it supported the
methodology that I analyze. As a mencione, I found a deficit in the understanding of the
methodology specifically in the formulas, since these are derived from mathematical proofs,
which at first cost me; There isno doubt that improving in this area would be very useful
for the development of new projects and understanding future problems.
Paulina Monroy Escobedo
Chemical Engineering
(b) Growth awareness

Within our energy balances course, we have learned to identify different methodologies, for
the understanding of bubble graphs, spray, as well as the use of Raoult's law.
Thisinformation acquired, helpedor to understand the development of the problem, because
finally we continued to make an analysis of the experimental values against the calculated,
which facilitated the understanding of these. The fact of having already worked with the dew
and bubble graphs, within Raoult's law provided me with the skills, to identify if my result
was right, because the most important parameter to point out was that the graph of the
experimental values coincided against the calculated which is pude obtain. At the same time
I can highlight that there was a growth in the way of understanding the function of Margules
and its parameters, since they all go hand in hand, and follow a line with which I have
worked. Once I hadto understand the concepts, the theory and the equences that allowed me
to obtain the algorithm, the resolution of the problem was easier, because it finally goes in
the direction of the information I acquired during the semester.

References

[1] Basic Engineering. "Exercise Obtaining the Parameters of the Margules Equation | L-V

equilibrium." Www.youtube.com, 2021, www.youtube.com/watch?v=mxl-

KmmctxY. Accessed 20 Oct. 2022.

[2] Engineering and Easy Chemistry. "How to Calculate Margules Solution Model

Parameters Using Excel." Www.youtube.com, 2018,

www.youtube.com/watch?v=M9Fi3DY2WpQ . Accessed 2 2 Oct. 2022.

[3] Jung, S. C., Jeon, M. J., & Jeon, Y. W. (2020). Adsorption of binary hydrocarbon gas

mixtures on activated carbon: Theoretical prediction of the binary equilibrium data.

Energy Reports, 6, 515–520. https://doi.org/10.1016/j.egyr.2019.09.017

Paulina Monroy Escobedo
Chemical Engineering
[4] Lainfiesta López, D. (2017). ESTIMATION OF THE CONSTANTS OF MARGULES

AND VAN LAAR FOR BINARY SYSTEMS BY LINEAR CORRELATION. Rafael

Landívar University.

[5] Smith, J.M, et al. Introduction to thermodynamics in chemical engineering. Translated

by Efrén Alatorre Miguel et al., edited by McGraw Hill, 7th ed., McGraw Hill,

2007, pp. 338–358.

[6] Stanley, I. (2015, June 3). Molar Excess Gibbs Free Energy - an overview |

ScienceDirect Topics. Www.sciencedirect.com.

https://www.sciencedirect.com/topics/chemistry/molar-excess-gibbs-free-energy