CENG3950 VLE Lab Report – Group 3 Kwok Tsz Lun (20736021)

VLE Lab Report

1. Plot the Abbe refractometer calibration curves with line equations (refractive
index vs mass fraction) for the ethanol/water system.

11 samples with different concentration of ethanol were prepared for plotting the
calibration curve. Refractive index can be measured by Abbe refractometer.

Table 1 Composition and refractive index of 11 samples

Sample Volume of ethanol (ml) Volume of water (ml) Refractive index

1 0 2.0 1.3325
2 0.2 1.8 1.3370
3 0.4 1.6 1.3435
4 0.6 1.4 1.3490
5 0.8 1.2 1.3540
6 1.0 1.0 1.3585
7 1.2 0.8 1.3605
8 1.4 0.6 1.3635
9 1.6 0.4 1.3640
10 1.7 0.3 1.3645
11 1.8 0.2 1.3640
12 2.0 0 1.3610

Table 2 Information about ethanol and water

Component Density 𝜌 Molar mass

Ethanol 0.789 g/ml 46 g/mol
Water 1 g/ml 18 g/mol

Mass fraction of ethanol can be calculated from Table 1 and 2.

Equation of calculating mass is shown below:

𝑚 =𝜌×𝑉

Equation of calculating mass fraction of ethanol is shown below:

𝜌!"#$%&' × 𝑉!"#$%&'
𝑀𝑎𝑠𝑠 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑒𝑡ℎ𝑎𝑛𝑜𝑙 =
𝜌!"#$%&' × 𝑉!"#$%&' + 𝜌($"!) × 𝑉($"!)
CENG3950 VLE Lab Report – Group 3 Kwok Tsz Lun (20736021)

With the above equations, we can calculate mass fraction of ethanol.

Table 3 Mass fraction of ethanol according to its water-ethanol ratio

Sample Vethanol Vwater Mass fraction Mass fraction Refractive

(ml) (ml) of ethanol of water index
1 0 2.0 0 1 1.3325
2 0.2 1.8 0.08060 0.919399 1.3370
3 0.4 1.6 0.16475 0.835247 1.3435
4 0.6 1.4 0.25269 0.747304 1.3490
5 0.8 1.2 0.34469 0.655308 1.3540
6 1.0 1.0 0.44102 0.558971 1.3585
7 1.2 0.8 0.54201 0.45798 1.3605
8 1.4 0.6 0.64801 0.351989 1.3635
9 1.6 0.4 0.75938 0.240616 1.3640
10 1.7 0.3 0.81722 0.182782 1.3645
11 1.8 0.2 0.87655 0.123442 1.3640
12 2.0 0 1 0 1.3610

Abbe refractometer calibration curve can be plotted using data from Table 3.

Calibration curve of water-ethanol

1.3700
1.3650
1.3600
Retractive index

1.3550
y = -0.0536x2 + 0.0836x + 1.3315
1.3500 R² = 0.9976
1.3450
1.3400
1.3350
1.3300
1.3250
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mass fraction of ethanol

Figure 1 Calibration curve of refractive index vs mass fraction of ethanol

CENG3950 VLE Lab Report – Group 3 Kwok Tsz Lun (20736021)

Calibration curve of water-ethanol

1.3700
1.3650
1.3600
Refractive index

1.3550 y = -0.0536x2 + 0.0836x + 1.3315

R² = 0.9976
1.3500
1.3450
1.3400
1.3350
1.3300
1.3250
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mass fraction of water

Figure 2 Calibration curve of refractive index vs mass fraction of water

2. Construct the T-x-y diagram (mole fraction) using experimental data with clear
labeling. Then, determine the position of the azeotrope.

(Construction of a proper T-x-y diagram requires the use of mole fractions for
composition, not mass fraction. However, you may find that the calibration curve
is easier to be read if it is constructed using mass fraction data.)

During the experiment, total 18 samples were taken. Data shown below are the
experimental data.

Table 4 Experimental data of VLE with refractive index

Volume of Sample Temperature RI of RI of still-pot

water added T1 (°C) distillate
to still-pot
(ml)
0 0 77.2 1.3610 1.3610
10 1 77.1 1.3619 1.3620
10 2 77.2 1.3629 1.3629
10 3 77.2 1.3630 1.3629
10 4 77.5 1.3635 1.3635
10 5 78.2 1.3640 1.3639
30 6 79 1.3640 1.3640
30 7 79.7 1.3640 1.3620
CENG3950 VLE Lab Report – Group 3 Kwok Tsz Lun (20736021)

30 8 80.4 1.3640 1.3600

30 9 81.2 1.3645 1.3571
30 10 82.3 1.3645 1.3539
30 11 83.4 1.3649 1.3500
30 12 85.9 1.3640 1.3450
30 13 87.8 1.3635 1.3410
30 14 91 1.3620 1.3375
30 15 94.1 1.3580 1.3350
30 16 96.5 1.3496 1.3337
30 17 98.1 1.3390 1.3329

Mass fraction of ethanol in distillate and still-pot can be calculated from

calibration curve in Figure 1 by using quadratic formula.

𝐶𝑎𝑙𝑖𝑏𝑟𝑎𝑡𝑖𝑜𝑛 𝑐𝑢𝑟𝑣𝑒: 𝑦 = −0.0536𝑥 * + 0.0836𝑥 + 1.3315

−𝑏 ± √𝑏* − 4𝑎𝑐
𝑄𝑢𝑎𝑑𝑟𝑎𝑡𝑖𝑐 𝑓𝑜𝑟𝑚𝑢𝑙𝑎: 𝑥 =
2𝑎

Mass fraction of ethanol is x-value in the equation of calibration curve. To obtain

the mass fraction, the corresponding refractive index (y-value) should be moved
to right hand side of the equation of calibration curve.

−0.0836 ± J0.0836* − 4 × (−0.0536) × (1.3315 − 𝑟𝑒𝑓𝑟𝑎𝑐𝑡𝑖𝑣𝑒 𝑖𝑛𝑑𝑒𝑥)

𝑀𝑎𝑠𝑠 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 =
2 × (−0.0536)

Calculated mass fraction of ethanol in distillate and still-pot are shown below:

Table 5 Mass fraction of ethanol in distillate

Sample Mass fraction of ethanol (+) Mass fraction of ethanol (-)

0 0.539446811 1.020254682
1 0.577358753 0.98234274
2 0.630363988 0.929337505
3 0.636740232 0.922961261
4 0.67424648 0.885455013
5 0.73714357 0.822557922
6 0.73714357 0.822557922
7 0.73714357 0.822557922
CENG3950 VLE Lab Report – Group 3 Kwok Tsz Lun (20736021)

8 0.73714357 0.822557922
9 #NUM! #NUM!
10 #NUM! #NUM!
11 #NUM! #NUM!
12 0.73714357 0.822557922
13 0.67424648 0.885455013
14 0.582019162 0.97768233
15 0.442561254 1.117140238
16 0.259773233 1.299928259
17 0.095568777 1.464132715

Table 6 Mass fraction of ethanol in still-pot

Sample Mass fraction of ethanol (+) Mass fraction of ethanol (-)

0 0.539446811 1.020254682
1 0.582019162 0.97768233
2 0.630363988 0.929337505
3 0.630363988 0.929337505
4 0.67424648 0.885455013
5 0.719108878 0.840592614
6 0.73714357 0.822557922
7 0.582019162 0.97768233
8 0.503353425 1.056348067
9 0.418526451 1.141175041
10 0.343666452 1.216035041
11 0.266998006 1.292703486
12 0.182940774 1.376760718
13 0.123399392 1.436302101
14 0.075417011 1.484284482
15 0.04305452 1.516646973
16 0.026775444 1.532926048
17 0.016930185 1.542771308

Mass fraction of ethanol should be decreased gradually during the process. Since
there are two answers for mass fraction of ethanol by using the quadratic
equation, the one which reflected the decreasing mass fraction should be chosen
as the correct answer. Also, sample 9, 10, and 11 shows no solution since they
did not lie on the calibration curve. Therefore, data of sample 9, 10, and 11 would
CENG3950 VLE Lab Report – Group 3 Kwok Tsz Lun (20736021)

be omitted. Moreover, we assume that the numbers of mass fraction which are
greater than 1 are equal to 1 due to experimental errors. By considering the
decreasing trend of mass fraction and omitted data, the shaded number would be
chosen to be the mass fraction of their corresponding temperature.

To obtain the T-x-y diagram of experimental data, mole fraction of ethanol

should be calculated from mass fraction and molar mass. The equation of
calculating the mole fraction is shown below:

𝑀𝑎𝑠𝑠 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑒𝑡ℎ𝑎𝑛𝑜𝑙

𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑒𝑡ℎ𝑎𝑛𝑜𝑙
𝑀𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑒𝑡ℎ𝑎𝑛𝑜𝑙 =
𝑀𝑎𝑠𝑠 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝑀𝑎𝑠𝑠 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟
𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑒𝑡ℎ𝑎𝑛𝑜𝑙 + 𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟

Table 7 Mole fraction of ethanol in distillate and still-pot with temperature

Temperature (T1) Mole fraction of ethanol Mole fraction of ethanol

Sample
(°C) in distillate in still-pot
0 77.2 1 1
1 77.1 0.956082174 0.944879538
2 77.2 0.837301766 0.837301766
3 77.2 0.824191739 0.837301766
4 77.5 0.75154407 0.75154407
5 78.2 0.644627256 0.673569561
6 79 0.644627256 0.523209571
7 79.7 0.523209571 0.352697756
8 80.4 0.523209571 0.283969538
12 85.9 0.523209571 0.080555836
13 87.8 0.447490599 0.052208217
14 91 0.352697756 0.030930919
15 94.1 0.237027941 0.017300825
16 96.5 0.12074255 0.010650938
17 98.1 0.039706284 0.006693837

T-x-y can be plotted using data in Table 7. The shade regions of Table 7 show the
location of azeotropes since there is same composition in liquid and vapor phase
due to the property of non-ideal mixture. Since there may be experimental errors,
there is two azeotropes in the experiment. Therefore, I decide to choose Sample 2
as the azeotrope which appears when the mole fraction of ethanol becomes
0.8373 at 77.2°C. Due to the non-ideal binary mixture, there is azeotrope in the
CENG3950 VLE Lab Report – Group 3 Kwok Tsz Lun (20736021)

T-x-y diagram. In Figure 2, the azeotrope appeared when mole fraction of ethanol
became 0.8373 at 77.2°C. It can be shown on the intersection of dew point curve
and bubble point curve in Figure 2 and Table 7.

T-x-y diagram of experimental data

97
Temperature (°C)

92

87
(0.8373, 77.2°C)
82

77
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mole fraction of ethanol

Dew point curve Bubble point curve

Figure 3 T-x-y diagram of experimental data for water-ethanol

3. Propose a 2-parameter Margules model for the vapor liquid equilibrium of

ethanol/water system. Assume the experiment was done under atmospheric
pressure. You may calculate the Margules parameters using the Antoine equation
for vapor pressures and the azeotrope data.

Antoine equation parameters (P = bar, T = K): Ethanol: A = 5.24677, B =

1598.673, C = -46.424 Water: A = 4.6543, B = 1435.264, C = -64.848

(NIST Chemistry WebBook)

Antoine equation is shown below:

𝐵
𝑙𝑜𝑔𝑃 = 𝐴 −
𝐶+𝑇

Azeotrope is located at 350.35K.

Vapor pressure of ethanol and water at azeotrope are calculated below:

-$"
1598.673
𝑙𝑜𝑔𝑃!,$, = 5.24677 −
−46.424 + 350.35𝐾
CENG3950 VLE Lab Report – Group 3 Kwok Tsz Lun (20736021)

-$"
𝑃!,$, = 0.9698 𝑏𝑎𝑟

-$"
1435.264
𝑙𝑜𝑔𝑃(,$, = 4.6543 −
−64.848 + 350.35𝐾

-$"
𝑃(,$, = 0.4238 𝑏𝑎𝑟

Modified Raoult’s Law is shown below:

𝑦. 𝑃 = 𝑥. 𝛾. 𝑃.-$"

𝑦. 𝑃
𝛾. =
𝑥. 𝑃.-$"

For azeotrope, mole fraction of ethanol and water can be omitted. We assume P =
1.01325 bar. Therefore, activity coefficient of ethanol and water at azeotrope can
be calculated below:

𝑃 1.01325 𝑏𝑎𝑟
𝛾!,$, = -$"
= = 1.0448
𝑃!,$, 0.9698 𝑏𝑎𝑟

𝑃 1.01325 𝑏𝑎𝑟
𝛾(,$, = -$"
= = 2.3910
𝑃(,$, 0.4238 𝑏𝑎𝑟

Two parameters Margules equation is shown below:

𝑙𝑛𝛾!,$, = 𝑥(,$, * [𝐴!( + 2(𝐴(! − 𝐴!( )𝑥!,$, ]

𝑙𝑛𝛾(,$, = 𝑥!,$, * [𝐴(! + 2(𝐴!( − 𝐴(! )𝑥(,$, ]

Rearrange,

1 𝑙𝑛𝛾!,$% 2𝑙𝑛𝛾",$% 1 𝑙𝑛1.0448 2𝑙𝑛2.3910

𝐴!" = #2 − (# (+# ( = -2 − 2- 2+- 2 = 0.9660
𝑥",$% 𝑥",$% 𝑥!,$% 0.1627 0.1627 0.8373

1 𝑙𝑛𝛾",$% 2𝑙𝑛𝛾!,$% 1 𝑙𝑛2.3910 2𝑙𝑛1.0448

𝐴"! = #2 − (# (+# ( = -2 − 2- 2+- 2 = 1.3771
𝑥!,$% 𝑥!,$% 𝑥",$% 0.8373 0.8373 0.1627

2-parameter Margules model for VLE of water-ethanol system is shown below:

𝑙𝑛𝛾! = 𝑥( * [0.9660 + 2(1.3771 − 0.9660)𝑥! ] = 𝑥( * [0.9660 − 0.8222𝑥! ]

CENG3950 VLE Lab Report – Group 3 Kwok Tsz Lun (20736021)

𝑙𝑛𝛾( = 𝑥! * [1.3771 + 2(0.9660 − 1.3771)𝑥( ] = 𝑥! * [1.3771 + 0.8222𝑥( ]

4. Construct a T-x-y plot of the results calculated from i) Raoult’s Law (Appendix
II) and ii) your Margules model (Appendix III).

Compare to your experimental data and comment on the performance on each

method.

i) Assume it works under P=1.01325 bar. By using the method in Appendix II,
T-x-y diagram of Raoult’s Law is constructed.

Table 8 Data of constructing bubble point curve of Raoult’s Law

x_e x_w T_bubble P_e P_w SP

0 1 373.600898 2.29353345 1.013246923 9.22351E-12
0.1 0.9 370.200585 2.03793044 0.899394192 4.64027E-12
0.2 0.8 367.214927 1.83330368 0.808234646 2.33109E-12
0.3 0.7 364.558042 1.66576831 0.733597973 8.34223E-13
0.4 0.6 362.167906 1.52607156 0.671368453 9.04826E-14
0.5 0.5 359.998279 1.40780514 0.618693471 4.71896E-13
0.6 0.4 358.013855 1.30639173 0.5735342 1.59906E-12
0.7 0.3 356.187112 1.21847479 0.534394821 6.20627E-13
0.8 0.2 354.495985 1.14152672 0.500148484 1.12106E-12
0.9 0.1 352.922786 1.07361973 0.469935449 1.6451E-12
1 0 351.452938 1.01324962 0.443084724 1.38312E-13
RMS 1.43703E-06

Table 9 Data of constructing dew point curve of Raoult’s Law

y_e y_w T_dew P_e P_w SP

0 1 373.60074 2.29352097 1.013241366 7.26182E-11
0.1 0.9 371.951886 2.16647132 0.956653025 2.22058E-10
0.2 0.8 370.220263 2.03933898 0.900021654 2.38141E-10
0.3 0.7 368.395637 1.91209582 0.843336613 8.19424E-11
0.4 0.6 366.465313 1.7846858 0.786575227 4.14115E-11
0.5 0.5 364.413939 1.65705663 0.729717057 1.9145E-10
0.6 0.4 362.223181 1.52918882 0.672756982 1.01806E-10
0.7 0.3 359.868821 1.40099596 0.615661037 5.94138E-12
0.8 0.2 357.319278 1.27236244 0.55838359 2.6818E-11
CENG3950 VLE Lab Report – Group 3 Kwok Tsz Lun (20736021)

0.9 0.1 354.533369 1.14318287 0.500885451 1.47894E-12

1 0 351.452468 1.01323078 0.443076347 3.5964E-10
RMS 1.10507E-05

T-x-y diagram of Raoult's Law

375

370
Temperature (K)

365

360

355

350
0 0.2 0.4 0.6 0.8 1
Mole fraction of ethanol

Bubble point curve Dew point curve

Figure 4 T-x-y diagram of Raoult’s Law

ii) Assume it works under P=1.01325 bar. By using the method in Appendix III,
T-x-y diagram of Margules model is constructed.

2-parameter Margules model for VLE of water-ethanol system which

calculated in Q3 is shown below:

𝑙𝑛𝛾! = 𝑥( * [0.9660 − 0.8222𝑥! ]

𝑙𝑛𝛾( = 𝑥! * [1.3771 + 0.8222𝑥( ]

Activity coefficient for each composition can be calculated using the above
equation.

Vapor pressure and mole fraction of liquid phase of each composition can be
calculated using Antoine equation and modified Raoult’s Law respectively.

Based on the above calculation methods, we can get the data below:
CENG3950 VLE Lab Report – Group 3 Kwok Tsz Lun (20736021)

Figure 5 Data of constructing T-x-y diagram of Margules model

T-x-y diagram of Margule model

375

370
Temperature (K)

365

360

355

350

345
0 0.2 0.4 0.6 0.8 1
Mole fraction of ethanol

Bubble point curve Dew point curve

Figure 6 T-x-y diagram of Margules model

Compare experimental data with Raoult’s Law method and Margules model,
Margules model is most similar with the experimental data.

Compare Raoult’s Law method and Margules model, both Figure 4 and
Figure 6 show negative relationship between temperature and mole fraction
of ethanol. However, Figure 4 did not show the location of azeotrope since
Raoult’s Law shows ideal mixture. Figure 6 shows the location of azeotrope
since it considered the mixture as non-ideal mixture. In equation of Margules
model, there is activity coefficient for non-ideal mixture. Therefore,
Margules model can demonstrate the condition of the water-ethanol mixture
more accurately in real condition.
CENG3950 VLE Lab Report – Group 3 Kwok Tsz Lun (20736021)

Compare experimental data and Raoult’s Law method, both Figure 3 and
Figure 4 show negative relationship between temperature and mole fraction
of ethanol. However, Figure 4 did not show the location of azeotrope since
Raoult’s Law shows ideal mixture while Figure 3 shows location of
azeotrope since it is a non-ideal mixture under reality.

Compare experimental data and Margules model, both Figure 3 and Figure 6
show negative relationship between temperature and mole fraction of
ethanol. Also, both figures locate the azeotrope since both demonstrate the
behaviour of non-ideal mixture. Additionally, the location of azeotrope in
Figure 3 is similar to that in Figure 6. Besides, bubble point curve and dew
point curve show overlapping after the location of azeotrope on both figures.
Therefore, Margules model is very similar to the experimental data.

To conclude, Raoult’s Law only demonstrate behaviour of ideal mixture, so

it is inaccurate compare with experimental data. Margules model considers
activity coefficient, so it can demonstrate behaviour of non-ideal mixture.
Hence, it is more accurate to predict the behaviour of experimental data.
However, the T-x-y diagram from experimental data may not be absolutely
accurate since there may be experimental errors.