VAPOR-LIQUID EQUILIBRIUM EXPERIMENT

Written Report

Tuesday – Group 8

Gabriella Bergeron – Group Leader

Mae Anne Mangaoil – Written Reporter

Jason Tullos – Oral Reporter

Faculty Advisor: Ye Xu

Date of Submission: 4/24/18

1
EXECUTIVE SUMMARY

This experiment focuses on studying the Vapor-Liquid Equilibrium (VLE) of the binary
ethanol-water system using an Othmer Still, determining the exact location of the
azeotrope in terms of temperature and molar fraction for ethanol-water, and using this
data to determine the Three-suffix Margules parameters – A and B. Then the
experimentally measured ethanol-water VLE data will be compared to the results
obtained. Finally, the significance of the parameters, deviations, and errors will be further
discussed.

BACKGROUND

An extensive knowledge of the Vapor-Liquid Equilibrium is very useful to chemical

engineers especially when working with fractional distillation, where components in a
chemical mixture are separated into different fractions according to their different boiling
points [5].

In addition, a common kind of fractional distillation unit is a crude distillation column,

which is used in petrochemicals. Refer to Figure 1 for a visual.

Figure 1: Diagram of the Main Fractions from Crude Oil and their Uses

2
In a crude distillation column, the crude oil is evaporated and its vapors condense at
different temperatures in the column. The substances with high boiling points condense
at the bottom, while the substances with low boiling points condense at the top. This
results to gases condensing at the top, the liquids in the middle and the solids at the
bottom of the distillation column [1]. Then the product, which is the liquid, is removed from
the middle of the column by trays that collect the condensate.

Furthermore, having an extensive knowledge of VLE becomes useful in optimizing the

fractional distillation column and adjusting the temperatures within the column to get the
desired fraction(s). This include refinery gases, gasoline, naphtha, kerosene, diesel oil,
fuel oil and residue (the main ones), as shown in Figure 1. Additionally, most of these
fractions are used as fuels, while some are used for other purposes such as making
chemicals and are key components in roads and roofs [1].

THEORY

Within the Vapor-Liquid Equilibrium, the fugacities of a species in both the liquid and the
vapor phase are equal.

"f#$ = f"#& (Equation 1)

The fugacities of the liquid and vapor phases can be further expanded to:

"f#$ = y# φ
) $# P (Equation 2)

"f#& = x# γ&# f#- (Equation 3)

Where y represents the vapor mole fraction, x represents the liquid mole fraction, P
represents pressure, φ
) represents the fugacity coefficient, and γ represents the activity
coefficient.

In cases where the system has a low pressure and has similar intermolecular forces, it
can be assumed that both the vapor and liquid are ideal. When it is an ideal gas and an
) = γ = 1 and f#- = P#/01 . This results to Raoult’s Law:
ideal solution, φ

3
 y# P = x# P#/01 (Equation 4)

Since the experiment deals with ethanol-water, which is chemically dissimilar species,
Raoult’s Law will no longer be valid to model the VLE. The liquid is no longer ideal so γ
is not equal to 1. The equation that would be used to accurately model the VLE of the
system is

y# P = x# γ# P#/01 (Equation 5)

Furthermore, the rest of the ethanol-water VLE will be modeled by calculating the excess
Gibbs energy. The three models that calculate the excess Gibbs energy include the Two-
suffix Margules, Three-suffix Margules, and van Laar. The Three-Suffix Margules will be
used since it can accurately model asymmetric binary systems, which will accurately
model the VLE of the ethanol-water mixture. The Three-suffix Margules equation for
excess Gibbs is shown below:

g 3 = x0 x4 [A + B(x0 − x4 )] (Equation 6)

Where gE represents excess Gibbs energy, xa represents the liquid composition of

species a, xb represents the liquid composition of species b, and A and B represents the
Three-suffix Margules parameters.

EQUIPMENT

In the experiment, Othmer Still and gas chromatography (GC) were used. The binary
mixture of ethanol-water was poured unto the Othmer still, which was on top of a hot
plate. The mixture was then heated. The vapor was condensed and returned back to the
mixture. When the temperature stabilized, indicating thermal equilibrium, a sample of both
the liquid and vapor were taken and analyzed [5]. The sample from the bottom
represented the composition of the liquid phase while the sample from the condenser
represented the composition of the vapor phase.

4
The samples were then run through the GC, which detected the compositions of ethanol
and water in both the liquid and vapor phases. The GC determined the compositions by
first vaporizing some liquid sample and injecting it to the head of the chromatographic
column. The vapor then traveled through the stationary phases then over liquid stationary
phases, which were normally a polymer. The compounds within the mixture were then
separated based on the different strengths of interaction of the compounds with the
stationary phases. The stronger the interaction was, or if the interactions were “like,” the
longer the compound interacted with the stationary phases; therefore, it took more time
to move through the column. However, when the compound exhibited “unlike”
interactions, it moved through the column much quicker. This helped the GC determine
the percentage of each compound in the mixture [2].

RESULTS
Before any experiments were conducted, a calibration test was run through the GC in
order to create a calibration curve. Then different percent compositions of ethanol (90%,
92%, 94%, 96% and 98%), and water were poured through the Othmer Still and heated.
It was a closed system and pressure was assumed almost equal to atmospheric pressure
(1 atm). The samples were then taken from the bottom and the condenser once thermal
equilibrium was reached for each trial. These samples were then analyzed in the GC to
determine the compositions of the liquid and vapor phases.

During Day 1 and 2, the calibration test was conducted, and samples were run through
the GC machine; however, only the samples from the bottom were analyzed, so the trials
were repeated. On Day 3, the different trials were conducted with different percent
compositions of ethanol (90%, 92%, 94%, 96% and 98%) and water, and this time, both
the samples from the condenser and bottom were taken and analyzed.

These data were used to determine the azeotrope, which is where the composition of a
mixture in the vapor phase is equal to the composition of a mixture in the liquid phase.
Refer to Figure 2 for the graph of the molar fraction of ethanol in the liquid phase vs. molar
fraction of ethanol in the vapor phase:

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 Vapor-Liquid Equlibrium
Ethanol-Water
1.200

1.000

0.800
ethanol molar fraction
0.600 in the liquid phase
ethanol molar fraction
0.400
in the vapor phase

0.200

0.000
0.010
0.070
0.130
0.190
0.250
0.310
0.370
0.430
0.490
0.550
0.610
0.670
0.730
0.790
0.850
0.910
0.970
Figure 2: Diagram of the VLE of the Ethanol-Water Mixture

Three-suffix Margules parameters calculated and averaged from the calibrated data:
A= 3844.028 J/mol and B= -1690.7746 J/mol

Three-suffix Margules parameters calculated and averaged from the non-calibrated data:

A= 3647.216 J/mol and B= -1395.2972J/mol

DISCUSSION

According to the results from the GC and the calculations that were done, it has been
determined that the azeotrope of ethanol-water mixture occurs at 78.5 C with 73% ethanol
and 27% water by composition. This is not close to the accepted value of 95.6% ethanol
and 4.4% water by composition at 78.2C [4]. The disparity in the results was caused by
the calibration errors between the actual composition and the composition reported by
the GC conducted before the experiments. It can also be due to the fact that the pressure
and temperature were not being monitored and properly maintained throughout the
experiment.

6
In addition, the Three-suffix Margules parameters that were calculated based on
calibrated data were A= 3844.028 J/mol and B= -1690.7746 J/mol. Since there was an
error between the experimental and actual composition of where the azeotrope occurs,
then it was a given that the parameters calculated is also far from the actual values.

STATISTICAL ANALYSIS

A calibration test was conducted in order to account for the difference in the actual
composition of ethanol and the composition of ethanol reported by the GC. This was done
by running mixtures with known concentrations through the GC machine. This error
largely affected the results taken from the GC machine and were considered when
constructing the VLE and other calculations. The actual composition and the GC reported
composition is shown in Figure 3:

Figure 3: Difference Between Actual Composition and GC Reported Composition of

Ethanol

In addition, the data collected throughout the experiment is used to determine the
azeotrope and the Three-Suffix Margules. A plot of the actual composition vs. reported
composition from the GC is shown in Figure 4.

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 Reported Composition
100
Reported Composition

y = 0.8906x + 4.3029
80

60

40

20

0
0 20 40 60 80 100 120
Actual Composition

Figure 4: Actual Composition vs. Reported Composition

CONCLUSIONS

Based on the experiments that were conducted and the compositions of the vapor and
liquid phases determined from the GC, the VLE graph of ethanol-water mixture was
constructed and the temperature and the compositions of where the azeotrope occurred
were determined, which was at 78.5 C with 73% ethanol and 27% water by composition.
From these data, the Three-Suffix Margules parameters where calculated to be A=
3844.028 J/mol and B= -1690.7746 J/mol. Since a calibration test showed a discrepancy
between the actual composition and the composition reported by the GC, the results from
the calculations of the azeotrope and the Three-Suffix Margules parameters where
different from the actual values.

REFERENCES

1. “GCSE Bitesize: Fractional Distillation.” BBC, BBC,

www.bbc.co.uk/schools/gcsebitesize/science/aqa_pre_2011/rocks/fuelsrev3.sht
ml.

8
 2. “Gas Chromatography.” Gas Chromatography Theory, UCLA, 1 Apr. 2016,
www.chem.ucla.edu/~bacher/General/30BL/gc/theory.html.
3. Helmenstine, Anne Marie. “What You Need to Know About Fractional
Distillation.” ThoughtCo, 11 Sept. 2017, www.thoughtco.com/definition-of-
fractional-distillation-604421.
4. Libretexts. “Azeotopes.” Chemistrt LibreTexts,Libretexts, 21 July 2016,
chem.libretexts.org/Core/Physical_and_Theoretical_Chemistry/Physical_Properti
es_of_Matter/Solutions_and Mixtures/Nonideal_Solutions/Azeotropes.
5. Libretexts. “Fractional Distillation of Non-Ideal Mixtures (Azeotropes).” Chemistry
LibreTexts, Libretexts, 24 Jan. 2018,
chem.libretexts.org/Core/Physical_and_Theoretical_Chemistry/Equilibria/Physica
l_Equilibria/Fractional_Distillation_of_Non-ideal_Mixtures_(Azeotropes).

APPENDICES

Data (without Calibration)

Calibration Data:

wt % etOH etOH water soln goal actual true wt % slot GC EtOH GC H20
0 0.00 15 15.00 15 0.00 1 0.23 99.77
20 -4.54 4.31 -0.23 5.39 0.20 2 31.05 68.95
40 -3.99 3.89 -0.10 6.51 0.40 3 42.27 57.73
60 -2.30 2.26 -0.04 5.66 0.60 4 48.77 51.23
80 -1.48 1.46 -0.02 7.34 0.80 5 71.1 28.9
100 15.00 0 0.00 0 1.00 6 99.59 0.41

Error theoretical-experimental stdev of difference

0 -0.23 8.057989203
55.25 -11.05
5.675 -2.27
-18.7167 11.23
-11.125 8.9
-0.41 0.41

Experimental Data:

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 Initial'wt%'ethanol' Temp'C Temp'K Liquid'wt%'ethanol Liquid'wt%'water' Vapor'wt%'ethanol Vapor'wt%'water
0.94 78.6 315.75 77.9 17.92 82.5 13
0.95 78.5 315.65 84.83 15.17 86.11 13.89
0.96 78.5 315.65 78.83 16.58 81.75 14.49
0.97 78.6 315.75 88.68 11.32 88.9 11.1
0.98 78.3 315.45 84.31 12.24 85.88 11.25

y"ethanol y"water" x"ethanol x"water Psat"ethanol"bar Psat"Water"bar gamma"ethanol gamma"water

0.71283 0.28717 0.6296764 0.3703236 1.016576935 0.447475479 1.128353007 1.755920532
0.708018 0.291982 0.686250911 0.313749089 1.012556774 0.445650243 1.032424984 2.115905582
0.688159 0.311841 0.650313328 0.349686672 1.012556774 0.445650243 1.058920811 2.027572275
0.758026 0.241974 0.753948572 0.246051428 1.016576935 0.447475479 1.002117693 2.226846162
0.749116 0.250884 0.729307404 0.270692596 1.004556371 0.442018526 1.036050072 2.124578315
1.012564758 0.445653994

Solving for Three-Suffix Margules Parameters:

x"ethanol x"water gamma"ethanol gamma"water

0.6296764 0.3703236 1.128353007 1.755920532
0.686250911 0.313749089 1.032424984 2.115905582
0.650313328 0.349686672 1.058920811 2.027572275
0.753948572 0.246051428 1.002117693 2.226846162
0.729307404 0.270692596 1.036050072 2.124578315

L"eq"1 xb2 xb3 L"eq"2 xa2 xa3 A B

317.0101 0.13714 0.050786019 1477.939168 0.396492369 0.249661887 3386.79 5707.976
83.74288 0.098438 0.030884987 1966.878521 0.470940313 0.323183219 3752.46 51662.88
150.2427 0.122281 0.042759955 1854.967958 0.422907424 0.275022335 3756.69 51578.78
5.553374 0.060541 0.014896275 2101.655542 0.568438448 0.428573356 3725.72 51802.78
92.88244 0.073274 0.01983486 1976.360107 0.53188929 0.387910797 3614.42 51224.07
average 3647.216 51395.2972
average"(w/o) 3712.3225 51567.1275

Prediction (not throwing out outlier):

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 % x#ethanol x#water gamma#ethanol gamma#water y#ethanol y#water
1 0.01 0.99 6.44 1.00 0.06 0.94
2 0.02 0.98 6.08 1.00 0.12 0.88
3 0.03 0.97 5.74 1.00 0.17 0.83
4 0.04 0.96 5.43 1.00 0.22 0.78
5 0.05 0.95 5.15 1.01 0.26 0.74
6 0.06 0.94 4.88 1.01 0.29 0.71
7 0.07 0.93 4.63 1.01 0.32 0.68
8 0.08 0.92 4.40 1.02 0.35 0.65
9 0.09 0.91 4.19 1.02 0.38 0.62
10 0.10 0.90 3.99 1.03 0.40 0.60
11 0.11 0.89 3.81 1.03 0.42 0.58
12 0.12 0.88 3.63 1.04 0.44 0.56
13 0.13 0.87 3.47 1.05 0.45 0.55
14 0.14 0.86 3.32 1.05 0.47 0.53
15 0.15 0.85 3.18 1.06 0.48 0.52
16 0.16 0.84 3.05 1.07 0.49 0.51
17 0.17 0.83 2.93 1.08 0.50 0.50
18 0.18 0.82 2.81 1.09 0.51 0.49
19 0.19 0.81 2.71 1.10 0.51 0.49
20 0.20 0.80 2.61 1.11 0.52 0.48
21 0.21 0.79 2.51 1.12 0.53 0.47
22 0.22 0.78 2.42 1.13 0.53 0.47
23 0.23 0.77 2.34 1.14 0.54 0.46
24 0.24 0.76 2.26 1.15 0.54 0.46
25 0.25 0.75 2.19 1.17 0.55 0.45
26 0.26 0.74 2.12 1.18 0.55 0.45
27 0.27 0.73 2.05 1.19 0.55 0.45
28 0.28 0.72 1.99 1.21 0.56 0.44
29 0.29 0.71 1.93 1.22 0.56 0.44
30 0.30 0.70 1.88 1.24 0.56 0.44
31 0.31 0.69 1.82 1.25 0.57 0.43
32 0.32 0.68 1.78 1.27 0.57 0.43
33 0.33 0.67 1.73 1.28 0.57 0.43
34 0.34 0.66 1.69 1.30 0.57 0.43
35 0.35 0.65 1.64 1.32 0.58 0.42
36 0.36 0.64 1.61 1.33 0.58 0.42
37 0.37 0.63 1.57 1.35 0.58 0.42
38 0.38 0.62 1.53 1.37 0.58 0.42
39 0.39 0.61 1.50 1.39 0.59 0.41
40 0.40 0.60 1.47 1.41 0.59 0.41
41 0.41 0.59 1.44 1.43 0.59 0.41
42 0.42 0.58 1.41 1.45 0.59 0.41
43 0.43 0.57 1.39 1.47 0.60 0.40
44 0.44 0.56 1.36 1.49 0.60 0.40
45 0.45 0.55 1.34 1.51 0.60 0.40
46 0.46 0.54 1.32 1.53 0.61 0.39
47 0.47 0.53 1.30 1.55 0.61 0.39
48 0.48 0.52 1.28 1.57 0.61 0.39
49 0.49 0.51 1.26 1.59 0.62 0.38
50 0.50 0.50 1.24 1.62 0.62 0.38

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 51 0.51 0.49 1.22 1.64 0.62 0.38
52 0.52 0.48 1.21 1.66 0.63 0.37
53 0.53 0.47 1.19 1.69 0.63 0.37
54 0.54 0.46 1.18 1.71 0.64 0.36
55 0.55 0.45 1.16 1.73 0.64 0.36
56 0.56 0.44 1.15 1.76 0.64 0.36
57 0.57 0.43 1.14 1.78 0.65 0.35
58 0.58 0.42 1.13 1.80 0.65 0.35
59 0.59 0.41 1.12 1.83 0.66 0.34
60 0.60 0.40 1.11 1.85 0.66 0.34
61 0.61 0.39 1.10 1.87 0.67 0.33
62 0.62 0.38 1.09 1.90 0.68 0.32
63 0.63 0.37 1.08 1.92 0.68 0.32
64 0.64 0.36 1.08 1.95 0.69 0.31
65 0.65 0.35 1.07 1.97 0.69 0.31
66 0.66 0.34 1.06 1.99 0.70 0.30
67 0.67 0.33 1.06 2.01 0.71 0.29
68 0.68 0.32 1.05 2.04 0.71 0.29
69 0.69 0.31 1.04 2.06 0.72 0.28
70 0.70 0.30 1.04 2.08 0.73 0.27
71 0.71 0.29 1.04 2.10 0.73 0.27
72 0.72 0.28 1.03 2.13 0.74 0.26
73 0.73 0.27 1.03 2.15 0.75 0.25
74 0.74 0.26 1.02 2.17 0.76 0.24
75 0.75 0.25 1.02 2.19 0.76 0.24
76 0.76 0.24 1.02 2.21 0.77 0.23
77 0.77 0.23 1.02 2.22 0.78 0.22
78 0.78 0.22 1.01 2.24 0.79 0.21
79 0.79 0.21 1.01 2.26 0.80 0.20
80 0.80 0.20 1.01 2.27 0.81 0.19
81 0.81 0.19 1.01 2.29 0.82 0.18
82 0.82 0.18 1.01 2.30 0.82 0.18
83 0.83 0.17 1.00 2.32 0.83 0.17
84 0.84 0.16 1.00 2.33 0.84 0.16
85 0.85 0.15 1.00 2.34 0.85 0.15
86 0.86 0.14 1.00 2.35 0.86 0.14
87 0.87 0.13 1.00 2.36 0.87 0.13
88 0.88 0.12 1.00 2.37 0.88 0.12
89 0.89 0.11 1.00 2.38 0.89 0.11
90 0.90 0.10 1.00 2.38 0.90 0.10
91 0.91 0.09 1.00 2.39 0.91 0.09
92 0.92 0.08 1.00 2.39 0.92 0.08
93 0.93 0.07 1.00 2.39 0.93 0.07
94 0.94 0.06 1.00 2.39 0.94 0.06
95 0.95 0.05 1.00 2.39 0.95 0.05
96 0.96 0.04 1.00 2.39 0.96 0.04
97 0.97 0.03 1.00 2.38 0.97 0.03
98 0.98 0.02 1.00 2.38 0.98 0.02
99 0.99 0.01 1.00 2.37 0.99 0.01
100 1.00 0.00 1.00 2.36 1.00 0.00

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Prediction (throwing out outlier):
% x#ethanol x#water gamma#ethanol gamma#water y#ethanol y#water
1 0.010 0.990 7.019 1.000 0.070 0.930
2 0.020 0.980 6.596 1.001 0.132 0.868
3 0.030 0.970 6.207 1.003 0.186 0.814
4 0.040 0.960 5.849 1.005 0.234 0.766
5 0.050 0.950 5.518 1.008 0.276 0.724
6 0.060 0.940 5.213 1.011 0.313 0.687
7 0.070 0.930 4.931 1.015 0.345 0.655
8 0.080 0.920 4.670 1.019 0.373 0.627
9 0.090 0.910 4.429 1.025 0.398 0.602
10 0.100 0.900 4.205 1.030 0.420 0.580
11 0.110 0.890 3.997 1.036 0.439 0.561
12 0.120 0.880 3.804 1.043 0.456 0.544
13 0.130 0.870 3.625 1.050 0.471 0.529
14 0.140 0.860 3.458 1.058 0.484 0.516
15 0.150 0.850 3.303 1.066 0.495 0.505
16 0.160 0.840 3.158 1.075 0.505 0.495
17 0.170 0.830 3.023 1.084 0.514 0.486
18 0.180 0.820 2.897 1.094 0.521 0.479
19 0.190 0.810 2.780 1.105 0.528 0.472
20 0.200 0.800 2.670 1.115 0.534 0.466
21 0.210 0.790 2.567 1.127 0.539 0.461
22 0.220 0.780 2.470 1.139 0.543 0.457
23 0.230 0.770 2.380 1.151 0.547 0.453
24 0.240 0.760 2.296 1.164 0.551 0.449
25 0.250 0.750 2.216 1.177 0.554 0.446
26 0.260 0.740 2.142 1.191 0.557 0.443
27 0.270 0.730 2.072 1.205 0.559 0.441
28 0.280 0.720 2.006 1.220 0.561 0.439
29 0.290 0.710 1.945 1.235 0.564 0.436
30 0.300 0.700 1.887 1.251 0.566 0.434
31 0.310 0.690 1.832 1.268 0.568 0.432
32 0.320 0.680 1.780 1.284 0.569 0.431
33 0.330 0.670 1.732 1.301 0.571 0.429
34 0.340 0.660 1.686 1.319 0.573 0.427
35 0.350 0.650 1.643 1.337 0.575 0.425
36 0.360 0.640 1.603 1.356 0.577 0.423
37 0.370 0.630 1.565 1.374 0.579 0.421
38 0.380 0.620 1.529 1.394 0.581 0.419
39 0.390 0.610 1.495 1.414 0.583 0.417
40 0.400 0.600 1.463 1.434 0.585 0.415
41 0.410 0.590 1.433 1.454 0.587 0.413
42 0.420 0.580 1.404 1.475 0.589 0.411
43 0.430 0.570 1.377 1.496 0.592 0.408
44 0.440 0.560 1.352 1.518 0.594 0.406
45 0.450 0.550 1.328 1.540 0.597 0.403
46 0.460 0.540 1.305 1.562 0.600 0.400
47 0.470 0.530 1.284 1.585 0.603 0.397
48 0.480 0.520 1.264 1.608 0.606 0.394
49 0.490 0.510 1.245 1.631 0.609 0.391
50 0.500 0.500 1.227 1.654 0.613 0.387

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 51 0.510 0.490 1.210 1.677 0.617 0.383
52 0.520 0.480 1.194 1.701 0.620 0.380
53 0.530 0.470 1.179 1.725 0.625 0.375
54 0.540 0.460 1.165 1.749 0.629 0.371
55 0.550 0.450 1.152 1.773 0.633 0.367
56 0.560 0.440 1.139 1.797 0.638 0.362
57 0.570 0.430 1.128 1.821 0.642 0.358
58 0.580 0.420 1.117 1.846 0.647 0.353
59 0.590 0.410 1.107 1.870 0.652 0.348
60 0.600 0.400 1.097 1.894 0.658 0.342
61 0.610 0.390 1.088 1.918 0.663 0.337
62 0.620 0.380 1.080 1.941 0.669 0.331
63 0.630 0.370 1.072 1.965 0.675 0.325
64 0.640 0.360 1.065 1.988 0.681 0.319
65 0.650 0.350 1.058 2.012 0.687 0.313
66 0.660 0.340 1.052 2.034 0.694 0.306
67 0.670 0.330 1.046 2.057 0.700 0.300
68 0.680 0.320 1.040 2.079 0.707 0.293
69 0.690 0.310 1.036 2.100 0.714 0.286
70 0.700 0.300 1.031 2.121 0.721 0.279
71 0.710 0.290 1.027 2.142 0.729 0.271
72 0.720 0.280 1.023 2.162 0.736 0.264
73 0.730 0.270 1.020 2.181 0.744 0.256
74 0.740 0.260 1.017 2.199 0.752 0.248
75 0.750 0.250 1.014 2.217 0.760 0.240
76 0.760 0.240 1.011 2.234 0.768 0.232
77 0.770 0.230 1.009 2.250 0.777 0.223
78 0.780 0.220 1.007 2.265 0.785 0.215
79 0.790 0.210 1.006 2.279 0.794 0.206
80 0.800 0.200 1.004 2.292 0.803 0.197
81 0.810 0.190 1.003 2.304 0.812 0.188
82 0.820 0.180 1.002 2.314 0.821 0.179
83 0.830 0.170 1.001 2.324 0.830 0.170
84 0.840 0.160 1.000 2.332 0.840 0.160
85 0.850 0.150 1.000 2.339 0.849 0.151
86 0.860 0.140 0.999 2.345 0.859 0.141
87 0.870 0.130 0.999 2.349 0.868 0.132
88 0.880 0.120 0.999 2.352 0.878 0.122
89 0.890 0.110 0.999 2.354 0.888 0.112
90 0.900 0.100 0.999 2.354 0.898 0.102
91 0.910 0.090 0.999 2.352 0.908 0.092
92 0.920 0.080 0.999 2.349 0.918 0.082
93 0.930 0.070 0.999 2.344 0.928 0.072
94 0.940 0.060 0.999 2.338 0.939 0.061
95 0.950 0.050 0.999 2.330 0.949 0.051
96 0.960 0.040 1.000 2.321 0.959 0.041
97 0.970 0.030 1.000 2.309 0.969 0.031
98 0.980 0.020 1.000 2.296 0.979 0.021
99 0.990 0.010 1.000 2.282 0.989 0.011
100 1.000 0.000 1.000 2.266 0.999 0.001

14
Data (with Calibration):

Experimental Data:

Initial wt% ethanol Temp C Temp K Liquid wt% ethanol Liquid wt% water Vapor wt% ethanol Vapor wt% water
0.94 78.6 315.75 77.9 17.92 82.5 13
0.95 78.5 315.65 84.83 15.17 86.11 13.89
0.96 78.5 315.65 78.83 16.58 81.75 14.49
0.97 78.6 315.75 88.68 11.32 88.9 11.1
0.98 78.3 315.45 84.31 12.24 85.88 11.25

Calibrated L ethanol Calibrated l water Calibrated v ethanol Calibrated v water y ethanol y water
73.68064 20.262452 77.7774 15.8807 0.657025479 0.342974521
79.852498 17.813302 80.992466 16.673334 0.655175091 0.344824909
74.508898 19.069048 77.10945 17.207694 0.636727724 0.363272276
83.281308 14.384492 83.47724 14.18856 0.697085669 0.302914331
79.389386 15.203844 80.787628 14.32215 0.688118299 0.311881701

x ethanol x water Psat ethanol bar Psat Water bar gamma ethanol gamma water
0.58717299 0.412827 1.016576935 0.447475479 1.115302056 1.881226657
0.63681248 0.363188 1.012556774 0.445650243 1.029539562 2.158689502
0.60448122 0.395519 1.012556774 0.445650243 1.054066902 2.088274617
0.69368282 0.306317 1.016576935 0.447475479 1.001616746 2.239215208
0.671314566 0.328685 1.004556371 0.442018526 1.033901908 2.175131795
1.012564758 0.445653994

Solving for Three-Suffix Margules Parameters:

To solve for A&B

x ethanol x water gamma ethanol gamma water
0.657025479 0.342974521 1.115302056 1.881226657
0.655175091 0.344824909 1.029539562 2.158689502
0.636727724 0.363272276 1.054066902 2.088274617
0.697085669 0.302914331 1.001616746 2.239215208
0.688118299 0.311881701 1.033901908 2.175131795

L eq 1 xb2 xb3 L eq 2 xa2 xa3 A B

286.4697 0.117631522 0.040344615 1658.892553 0.43168248 0.283626389 3581.12 -703.773
76.39818 0.118904218 0.041001136 2019.413178 0.429254399 0.28123679 3934.12 -2030.98
138.1857 0.131966746 0.04793986 1932.382676 0.405422195 0.258143551 3923.78 -1859.61
4.240766 0.091757092 0.027794538 2116.196599 0.485928431 0.338733745 3898.43 -2156.91
87.43894 0.097270195 0.030336794 2038.034153 0.473506794 0.32582869 3882.69 -1702.6
average 3844.028 -1690.7746
average (w/o) 3909.755 -1937.525

15
Prediction (not throwing out outlier):

% x ethanol x water gamma ethanol gamma water y ethanol y water

1 0.010 0.990 7.707105351 1.000337399 0.077019 0.922981068
2 0.020 0.980 7.21629251 1.001339954 0.144228 0.855771755
3 0.030 0.970 6.766350734 1.002994147 0.202853 0.797146757
4 0.040 0.960 6.353392844 1.005287652 0.253964 0.746036153
5 0.050 0.950 5.973942307 1.008209244 0.298495 0.701504888
6 0.060 0.940 5.624886104 1.011748715 0.337265 0.662735074
7 0.070 0.930 5.303433407 1.01589679 0.370989 0.629010724
8 0.080 0.920 5.007079287 1.020645057 0.400295 0.599704553
9 0.090 0.910 4.733572817 1.025985892 0.425733 0.574266557
10 0.100 0.900 4.480888992 1.031912388 0.447786 0.552214135
11 0.110 0.890 4.247203989 1.038418293 0.466876 0.533123515
12 0.120 0.880 4.030873338 1.045497942 0.483378 0.51662232
13 0.130 0.870 3.830412648 1.053146197 0.497617 0.502383113
14 0.140 0.860 3.644480555 1.061358388 0.509882 0.49011778
15 0.150 0.850 3.471863636 1.070130253 0.520427 0.479572648
16 0.160 0.840 3.311463035 1.07945788 0.529476 0.470524231
17 0.170 0.830 3.162282598 1.089337655 0.537224 0.462775519
18 0.180 0.820 3.023418338 1.099766201 0.543847 0.456152742
19 0.190 0.810 2.894049062 1.110740325 0.549497 0.450502545
20 0.200 0.800 2.773428032 1.122256966 0.55431 0.445689517
21 0.210 0.790 2.66087554 1.134313138 0.558406 0.441594032
22 0.220 0.780 2.555772273 1.146905877 0.56189 0.438110353
23 0.230 0.770 2.4575534 1.160032184 0.564855 0.435144977
24 0.240 0.760 2.365703282 1.173688974 0.567385 0.432615184
25 0.250 0.750 2.279750737 1.187873021 0.569552 0.430447754
26 0.260 0.740 2.199264804 1.202580901 0.571422 0.428577855
27 0.270 0.730 2.123850946 1.217808935 0.573052 0.426948051
28 0.280 0.720 2.053147633 1.233553138 0.574493 0.425507444
29 0.290 0.710 1.986823285 1.249809157 0.575789 0.424210906
30 0.300 0.700 1.924573516 1.266572217 0.576982 0.423018411
31 0.310 0.690 1.866118655 1.283837063 0.578106 0.421894444
32 0.320 0.680 1.811201514 1.301597899 0.579193 0.420807478
33 0.330 0.670 1.759585373 1.319848335 0.58027 0.419729519
34 0.340 0.660 1.711052165 1.338581319 0.581364 0.418635696
35 0.350 0.650 1.665400829 1.357789086 0.582496 0.417503908
36 0.360 0.640 1.622445834 1.377463092 0.583685 0.416314503
37 0.370 0.630 1.582015826 1.397593959 0.58495 0.415050003
38 0.380 0.620 1.543952416 1.41817141 0.586305 0.413694858
39 0.390 0.610 1.508109076 1.43918421 0.587765 0.412235224
40 0.400 0.600 1.474350134 1.460620109 0.589341 0.410658777
41 0.410 0.590 1.442549867 1.48246578 0.591045 0.408954538
42 0.420 0.580 1.412591674 1.50470676 0.592887 0.407112727
43 0.430 0.570 1.384367317 1.527327396 0.594875 0.405124629
44 0.440 0.560 1.357776244 1.550310784 0.597018 0.402982478
45 0.450 0.550 1.332724956 1.573638716 0.599321 0.400679353
46 0.460 0.540 1.309126441 1.597291627 0.601791 0.398209093
47 0.470 0.530 1.286899648 1.621248544 0.604434 0.39556621
48 0.480 0.520 1.265969016 1.645487037 0.607254 0.392745825
49 0.490 0.510 1.246264034 1.669983175 0.610256 0.389743608
50 0.500 0.500 1.227718843 1.694711479 0.613444 0.38655572

16
 51 0.510 0.490 1.210271869 1.71964489 0.616821 0.383178774
52 0.520 0.480 1.193865489 1.744754729 0.62039 0.379609788
53 0.530 0.470 1.178445717 1.770010671 0.624154 0.375846159
54 0.540 0.460 1.163961929 1.795380717 0.628114 0.371885628
55 0.550 0.450 1.150366594 1.820831178 0.632274 0.367726258
56 0.560 0.440 1.137615035 1.846326659 0.636634 0.363366415
57 0.570 0.430 1.125665212 1.871830052 0.641195 0.358804751
58 0.580 0.420 1.114477512 1.897302539 0.64596 0.354040189
59 0.590 0.410 1.104014562 1.922703599 0.650928 0.349071917
60 0.600 0.400 1.094241054 1.947991022 0.656101 0.343899377
61 0.610 0.390 1.085123582 1.973120935 0.661478 0.338522263
62 0.620 0.380 1.076630494 1.998047836 0.667059 0.332940519
63 0.630 0.370 1.068731754 2.022724634 0.672846 0.327154336
64 0.640 0.360 1.061398806 2.047102704 0.678836 0.321164159
65 0.650 0.350 1.054604464 2.07113195 0.685029 0.314970684
66 0.660 0.340 1.048322793 2.094760877 0.691425 0.308574871
67 0.670 0.330 1.042529008 2.117936675 0.698022 0.301977944
68 0.680 0.320 1.037199376 2.140605318 0.704819 0.295181403
69 0.690 0.310 1.032311128 2.162711667 0.711813 0.288187033
70 0.700 0.300 1.027842375 2.184199593 0.719003 0.280996915
71 0.710 0.290 1.023772026 2.205012102 0.726387 0.273613436
72 0.720 0.280 1.020079718 2.225091483 0.733961 0.266039303
73 0.730 0.270 1.016745748 2.24437946 0.741722 0.258277556
74 0.740 0.260 1.013751008 2.262817356 0.749668 0.250331584
75 0.750 0.250 1.011076923 2.280346271 0.757795 0.242205137
76 0.760 0.240 1.0087054 2.296907272 0.766098 0.233902344
77 0.770 0.230 1.006618775 2.312441591 0.774572 0.225427727
78 0.780 0.220 1.00479976 2.326890832 0.783214 0.216786218
79 0.790 0.210 1.003231405 2.340197194 0.792017 0.207983178
80 0.800 0.200 1.001897052 2.352303693 0.800976 0.19902441
81 0.810 0.190 1.000780294 2.363154405 0.810084 0.189916177
82 0.820 0.180 0.999864945 2.372694702 0.819335 0.180665221
83 0.830 0.170 0.999135003 2.380871505 0.828721 0.171278775
84 0.840 0.160 0.99857462 2.387633539 0.838235 0.161764586
85 0.850 0.150 0.998168073 2.392931586 0.847869 0.152130924
86 0.860 0.140 0.997899743 2.396718749 0.857613 0.142386601
87 0.870 0.130 0.997754088 2.398950714 0.867459 0.132540987
88 0.880 0.120 0.997715625 2.399586004 0.877396 0.122604018
89 0.890 0.110 0.997768909 2.398586246 0.887414 0.112586218
90 0.900 0.100 0.997898525 2.395916418 0.897501 0.102498702
91 0.910 0.090 0.998089065 2.391545099 0.907647 0.092353191
92 0.920 0.080 0.998325125 2.385444712 0.917838 0.082162022
93 0.930 0.070 0.998591294 2.377591753 0.928062 0.071938152
94 0.940 0.060 0.998872149 2.36796701 0.938305 0.061695167
95 0.950 0.050 0.99915225 2.356555773 0.948553 0.051447285
96 0.960 0.040 0.999416141 2.343348021 0.958791 0.041209356
97 0.970 0.030 0.999648348 2.328338601 0.969003 0.030996865
98 0.980 0.020 0.999833386 2.311527379 0.979174 0.020825927
99 0.990 0.010 0.999955767 2.292919378 0.989287 0.01071328
100 1.000 0.000 1 2.272524887 0.999324 0.000676281

17
Prediction (throwing out outlier):

% x ethanol x water gamma ethanol gamma water y ethanol y water

1 0.010 0.990 8.62940073 1.00036776 0.086236 0.913764
2 0.020 0.980 8.032446316 1.001460018 0.16054 0.83946
3 0.030 0.970 7.488697685 1.003261359 0.224509 0.775491
4 0.040 0.960 6.992755469 1.005757777 0.279521 0.720479
5 0.050 0.950 6.539827059 1.008936556 0.32677 0.67323
6 0.060 0.940 6.125652679 1.012786167 0.367291 0.632709
7 0.070 0.930 5.746441108 1.017296173 0.401979 0.598021
8 0.080 0.920 5.398813699 1.022457131 0.431613 0.568387
9 0.090 0.910 5.079755572 1.028260501 0.456869 0.543131
10 0.100 0.900 4.786572994 1.034698569 0.478334 0.521666
11 0.110 0.890 4.516856123 1.041764356 0.496518 0.503482
12 0.120 0.880 4.268446392 1.049451543 0.511867 0.488133
13 0.130 0.870 4.039407922 1.057754398 0.524768 0.475232
14 0.140 0.860 3.828002429 1.066667695 0.535558 0.464442
15 0.150 0.850 3.632667181 1.076186647 0.544532 0.455468
16 0.160 0.840 3.4519956 1.086306834 0.551946 0.448054
17 0.170 0.830 3.28472017 1.097024131 0.558025 0.441975
18 0.180 0.820 3.129697373 1.108334641 0.562965 0.437035
19 0.190 0.810 2.985894379 1.120234626 0.566936 0.433064
20 0.200 0.800 2.852377278 1.132720439 0.57009 0.42991
21 0.210 0.790 2.72830067 1.145788456 0.572556 0.427444
22 0.220 0.780 2.612898439 1.159435007 0.574449 0.425551
23 0.230 0.770 2.505475559 1.17365631 0.57587 0.42413
24 0.240 0.760 2.405400831 1.188448402 0.576906 0.423094
25 0.250 0.750 2.312100413 1.203807067 0.577634 0.422366
26 0.260 0.740 2.225052066 1.21972777 0.578122 0.421878
27 0.270 0.730 2.143780023 1.236205585 0.578429 0.421571
28 0.280 0.720 2.067850419 1.253235126 0.578607 0.421393
29 0.290 0.710 1.996867198 1.270810472 0.5787 0.4213
30 0.300 0.700 1.930468465 1.288925099 0.578749 0.421251
31 0.310 0.690 1.868323211 1.307571804 0.578789 0.421211
32 0.320 0.680 1.810128389 1.326742634 0.578849 0.421151
33 0.330 0.670 1.755606282 1.346428811 0.578958 0.421042
34 0.340 0.660 1.704502145 1.366620656 0.579139 0.420861
35 0.350 0.650 1.656582087 1.387307519 0.579412 0.420588
36 0.360 0.640 1.611631162 1.4084777 0.579795 0.420205
37 0.370 0.630 1.569451652 1.430118376 0.580304 0.419696
38 0.380 0.620 1.529861516 1.45221553 0.580954 0.419046
39 0.390 0.610 1.492692997 1.474753873 0.581757 0.418243
40 0.400 0.600 1.457791357 1.497716774 0.582722 0.417278
41 0.410 0.590 1.425013735 1.521086189 0.583861 0.416139
42 0.420 0.580 1.394228117 1.54484259 0.58518 0.41482
43 0.430 0.570 1.365312398 1.568964901 0.586687 0.413313
44 0.440 0.560 1.338153533 1.593430427 0.588389 0.411611
45 0.450 0.550 1.312646768 1.6182148 0.590292 0.409708
46 0.460 0.540 1.28869494 1.643291911 0.592399 0.407601
47 0.470 0.530 1.266207837 1.668633864 0.594715 0.405285
48 0.480 0.520 1.245101623 1.69421092 0.597245 0.402755
49 0.490 0.510 1.225298304 1.719991454 0.59999 0.40001
50 0.500 0.500 1.206725251 1.745941917 0.602955 0.397045

18
 51 0.510 0.490 1.189314755 1.772026797 0.60614 0.39386
52 0.520 0.480 1.173003626 1.798208601 0.609549 0.390451
53 0.530 0.470 1.157732828 1.82444783 0.613183 0.386817
54 0.540 0.460 1.143447132 1.850702969 0.617044 0.382956
55 0.550 0.450 1.130094818 1.87693049 0.621132 0.378868
56 0.560 0.440 1.11762738 1.903084855 0.625448 0.374552
57 0.570 0.430 1.105999272 1.929118536 0.629993 0.370007
58 0.580 0.420 1.095167663 1.954982044 0.634768 0.365232
59 0.590 0.410 1.085092217 1.98062397 0.639771 0.360229
60 0.600 0.400 1.07573489 2.00599104 0.645004 0.354996
61 0.610 0.390 1.067059737 2.031028175 0.650466 0.349534
62 0.620 0.380 1.059032744 2.055678575 0.656156 0.343844
63 0.630 0.370 1.05162166 2.079883809 0.662074 0.337926
64 0.640 0.360 1.044795854 2.103583922 0.668217 0.331783
65 0.650 0.350 1.03852617 2.126717559 0.674585 0.325415
66 0.660 0.340 1.032784804 2.149222097 0.681177 0.318823
67 0.670 0.330 1.027545182 2.171033798 0.68799 0.31201
68 0.680 0.320 1.02278185 2.192087977 0.695021 0.304979
69 0.690 0.310 1.018470368 2.212319183 0.702269 0.297731
70 0.700 0.300 1.014587219 2.231661392 0.709731 0.290269
71 0.710 0.290 1.011109716 2.250048227 0.717402 0.282598
72 0.720 0.280 1.00801592 2.267413173 0.725281 0.274719
73 0.730 0.270 1.005284561 2.283689829 0.733361 0.266639
74 0.740 0.260 1.002894967 2.298812151 0.74164 0.25836
75 0.750 0.250 1.000826998 2.312714727 0.750113 0.249887
76 0.760 0.240 0.99906098 2.325333049 0.758773 0.241227
77 0.770 0.230 0.99757765 2.336603805 0.767615 0.232385
78 0.780 0.220 0.996358098 2.346465177 0.776634 0.223366
79 0.790 0.210 0.995383723 2.354857148 0.785821 0.214179
80 0.800 0.200 0.99463618 2.361721812 0.795171 0.204829
81 0.810 0.190 0.994097342 2.367003694 0.804674 0.195326
82 0.820 0.180 0.993749259 2.370650073 0.814323 0.185677
83 0.830 0.170 0.993574122 2.3726113 0.824109 0.175891
84 0.840 0.160 0.993554233 2.372841122 0.834021 0.165979
85 0.850 0.150 0.993671971 2.371296997 0.84405 0.15595
86 0.860 0.140 0.993909773 2.367940409 0.854184 0.145816
87 0.870 0.130 0.994250103 2.362737172 0.864413 0.135587
88 0.880 0.120 0.994675439 2.355657723 0.874722 0.125278
89 0.890 0.110 0.995168254 2.346677401 0.885101 0.114899
90 0.900 0.100 0.995711001 2.335776715 0.895534 0.104466
91 0.910 0.090 0.996286107 2.322941592 0.906007 0.093993
92 0.920 0.080 0.996875959 2.308163601 0.916506 0.083494
93 0.930 0.070 0.997462907 2.291440157 0.927013 0.072987
94 0.940 0.060 0.998029257 2.272774698 0.937513 0.062487
95 0.950 0.050 0.998557279 2.252176839 0.947988 0.052012
96 0.960 0.040 0.999029205 2.229662483 0.958419 0.041581
97 0.970 0.030 0.999427244 2.205253919 0.968789 0.031211
98 0.980 0.020 0.99973359 2.178979867 0.979076 0.020924
99 0.990 0.010 0.999930437 2.150875498 0.989262 0.010738
100 1.000 0.000 1 2.120982414 0.999324 0.000676

19