BACHELOR OF ENGINEERING (HONOURS) CHEMICAL ENGINEERING

UEMK2113 CHEMICAL ENGINEERING THERMODYNAMICS

LECTURER: DR. CHONG WOON CHAN, DR. PANG YEAN LING

GROUP 3

SUBMISSION DATE: 21 APRIL 2023

Name Student ID Tutorial Contribution Signature

Group
Lim Meng Hong 2102345 T2 100%

Chin Kwang Yaw 2202200 T2 100%

Lui Xu Yuan 2103227 T2 100%

Wong Jing Xiang 2103353 T2 100%

Damon Lim Ching 2202843 T3 50%

Ann

1
 Executive Summary

This report focuses on investigating the vapor-liquid equilibrium (VLE) behaviour of the
acetone-chloroform system using experimental data obtained from literature and Aspen Plus
process simulator. The report is divided into several parts, including a comparison of
experimental VLE data with data from the National Institute of Standards and Technology
(NIST) database using Aspen Plus, estimation of specific volumes and fugacity coefficients
using the Peng-Robinson equation of state (EOS), fitting of adjustable parameters for activity
models, and comparison of predicted equilibrium vapor mole fractions with experimental data.

The experimental VLE data for acetone-chloroform system is searched from literature
and compared with NIST database using Aspen Plus. Tabulation of the respective data were
made for the ease of comparison. Using the same set of data from the literature, specific volumes
is first estimated for a set of equilibrium compositions using the Peng-Robinson EOS. This is
accomplished by tabulating data and using the respective equations from the Peng-Robinson
EOS to find the components such as critical temperature, critical pressure, attraction and
repulsion forces, etc. Then, the specific volume can be calculated along with these components
through Excel’s goal-seek function. After selecting the most suitable value for the specific
volume of each state, the data can be used to calculate the fugacity coefficient and vapour mole
fraction.

The adjustable parameters for three-suffix Margules, van Laar, and Wilson activity
models are fitted using the Antoine equation’s help to calculate the saturated pressure. Applying
their respective relevant equations to obtain the required parameters of each model. Then, the
equilibrium vapor mole fractions predicted using the activity models are compared with
experimental data. Upon with the tabulation and graphing the data, the most suitable model is
analysing VLE systems can be deduced through the comparison of data and the percentage
difference.

Aspen Plus process simulator is used to generate VLE data for the acetone-chloroform
system based on the UNIQUAC activity model for this report. The ability to shift the VLE curve
or azeotropic compositions at different pressures in a pressure-swing distillation is also
demonstrated. Besides that, the Aspen Plus process simulator is also used to demonstrate the
suitability of dimethyl sulfoxide (DMSO) and ethylene glycol (EG) as solvents in an extractive
distillation for the acetone-chloroform system based on their VLE behaviour.

2
3
 Table of Content

Section Title Page

Executive Summary 2
1.0 Introduction 4
1.1 Background 4
1.2 Objectives 4
2.0 Question 1 5-30
2.1 VLE data comparison 5-8
2.2 Specific volume and fugacity coefficients 9-14
2.2.1 Vapour mole fraction 14-16
2.3 Adjustable parameters 17
2.3.1 Three-suffix Margules 18-19
2.3.2 Van Laar Model 19-20
2.3.3 Wilson Model 20-21
2.4 Vapour mole fraction comparison 22-30
3.0 Question 2 31-38
3.1 VLE Data for Acetone-Chloroform System from UNIQUAC 31
Activity Model
3.1.1 Generation of VLE Data based on UNIQUAC Activity 31-34
Model
3.2 Demonstration of DMSO and EG used as Solvents based on 35-38
their VLE in the System
4.0 Conclusion 39
5.0 Reference 40

4
1.0 Introduction

1.1 Background

In thermodynamics, a pure substance or mixture that is in mechanical and thermal

equilibrium and in which there is no net mass transfer between the two phases is said to be in
vapor-liquid equilibrium (VLE). For Peng-Robinson equation of state (EOS), it is used to
estimate the specific volumes of vapor and liquid for a set of equilibrium compositions. Activity
models that are being used to calculate the activity coefficient of acetone and chloroform
including three-suffix Margules, Van Laar, and Wilson models. Aspen Plus based on UNIQUAC
activity model can be used to obtain the liquid mole fraction, x and vapour mole fraction, y for
acetone and chloroform at specific pressures.

1.2 Objective

The objectives of this report are to

 identify the fugacity coefficients by fitting the equation of state against a sample of
representative experimental data.
 identify the adjustable parameters of activity models by applying them to a sample of
representative experimental data.
 elect the most appropriate thermodynamic model(s) to portray the system.
 acquire and produce the VLE curve using process simulator.
 picture how extractive distillation and pressure-swing distillation changed the VLE of
acetone-chloroform system.

5
2.0 Acetone-chloroform system

2.1 Data comparison

Experimental Data  
T(K) x1 y1
335.75 0.098 0.06
336.65 0.186 0.143
337.25 0.266 0.23
337.55 0.36 0.36
336.95 0.468 0.514
335.85 0.578 0.646
334.65 0.673 0.751
333.45 0.755 0.83
332.15 0.827 0.89
331.05 0.892 0.939
330.15 0.949 0.975
Table 1.1 VLE data from literature (DDBST GmbH, 2022)

Graph of T-xy for Acetone-Chloroform

340

338

336
Temperature, K

334
x1
332 y1

330

328

326
0 0.2 0.4 0.6 0.8 1 1.2
Liquid/vapour mole fraction

Figure 1.1 Graph of T-xy for Acetone-Chloroform from literature

6
 Aspen Plus Data  
T(K) x1 y1
334.624 0 0
0.097
335.724 6 0.0598
0.185
336.624 9 0.1428
0.266
337.224 2 0.2302
0.360
337.524 2 0.3602
0.468
336.924 3 0.5143
0.578
335.824 1 0.6457
0.672
334.624 7 0.7512
0.755
333.424 1 0.8302
332.124 0.827
3 5 0.8903
331.024 0.891
6 6 0.9394
330.124 0.948
9 7 0.975
329.325
1 1 1
Table 1.2 VLE data from NIST Aspen Plus

7
 T-xy for Acetone-chloroform
340

338

336
Temperature, K
334
x1
y1
332

330

328

326
0 0.2 0.4 0.6 0.8 1 1.2
Liquid/vapour mole fraction

Figure 1.2 Graph of T-xy for Acetone-Chloroform from

8
 Consider:

x 1=Liquid mole fraction of acetone

y 1=Vapour mole fraction of acetone

x 2=Liquid mole fraction of chloroform

y 2=Vapour mole fraction of chloroform

Table 1.1 and Table 1.2 has shown 2 set of isobaric VLE data for acetone-chloroform
system. Table 1.1 is the experiment data that is obtained from online resources while Table 1.2 is
the Aspen Plus data that is obtained from National Institute of Standards and Technology (NIST)
database by using Aspen Plus simulator. Data with colour highlighted are the selected data to be
used for the following questions.

Percentage Difference between

experiment data and Aspen Plus
Experimental Data Aspen Plus Data data
T(K) x1 y1 T(K) x1 y1 T(K) x1 y1
0.00774445
335.75 0.098 0.06 335.724 0.0976 0.0598 7 0.0004 0.33444816
0.00772375
336.65 0.186 0.143 336.624 0.1859 0.1428 1 1E-04 0.14005602
0.00771000
337.25 0.266 0.23 337.224 0.2662 0.2302 9 0.0002 0.08688097
0.00770315
337.55 0.36 0.36 337.524 0.3602 0.3602 6 0.0002 0.05552471
0.00771687
336.95 0.468 0.514 336.924 0.4683 0.5143 4 0.0003 0.05833171
0.00774215
335.85 0.578 0.646 335.824 0.5781 0.6457 1 1E-04 0.0464612
0.00776991
334.65 0.673 0.751 334.624 0.6727 0.7512 5 0.0003 0.02662407
0.00779787
333.45 0.755 0.83 333.424 0.7551 0.8302 9 1E-04 0.02409058

9
 0.00773806
332.15 0.827 0.89 332.1243 0.8275 0.8903 7 0.0005 0.03369651
0.00767314
331.05 0.892 0.939 331.0246 0.8916 0.9394 6 0.0004 0.04258037
0.00760318
330.15 0.949 0.975 330.1249 0.9487 0.975 3 0.0003 0
Table 1.3 Selected data set that has percentage difference less than 1

Table 1.3 has shown the selected data with percentage differences that will be used for
the following questions. From table 1.2, 11 group of data from the Aspen Plus data has been
selected and tabulated in Table 1.3. The percentage differences thar are found to be less than 1%
are calculated and tabulated by using the formula below:

Percentage Difference= |ExperimentAspen

Data− Aspen Plus Data
Plus Data |×100 %

10
2.2 Specific volume and fugacity coefficients

The Peng-Robinson equation of state (EOS) is used to estimate specific volumes of

vapour and liquid for a set of equilibrium compositions, and the fugacity coefficients of acetone
and chloroform for both vapour and liquid phases are calculated.

Let:

x 1= Acetone liquid mole fraction

x 2= Chloroform liquid mole fraction

y 1= Acetone vapour mole fraction

y 2= Chloroform vapour mole fraction

First, the critical temperature (T c), critical pressure ( Pc ) and acentric factor (ω) can be
found from Appendix A and tabulated in Table 1.4:

  Acetone Chloroform
T c (K) 508.1 536.4
Pc (bar) 47.01 54.72
ω 0.309 0.216
Table 1.4 Critical temperature, critical pressure, and acentric factor from Appendix A

Attraction and repulsion parameter which include a , b can be defined by the equations
stated below:

2 2
0.45724 R T c
a=
Pc

0.07780 R T c
b=
Pc

11
By using these equations, the parameters of acetone and chloroform can be calculated and
tabulated:

Acetone Chloroform
3
Jm
a( 2)
mol 1.7128673 1.64
m3
b( )
mol 6.90254e-05 6.26026e-05
Table 1.5 Parameters a and b of acetone and chloroform

Moving on, the reduced temperature, T r is calculated to obtained polarizability, a by using the
equation stated, and the values are tabulated in Table 1.6.

T
T r=
Tc

2 0.5 2
∝=[1+(0.37464+1.54226 ω−0.26992 ω )(1−T r )]

T [K] T r1 T r2 α1 α2
335.7 0.6607 0.6259 1.3327 1.3114
5 95 32 21 21
336.6 0.6625 0.6276 1.3306 1.3097
5 66 1 47 34
337.2 0.6637 0.6287 1.3292 1.3086
5 47 29 67 12
337.5 0.6643 0.6292 1.3285 1.3080
5 38 88 77 51
336.9 0.6631 0.6281 1.3299 1.3091
5 57 69 57 73
335.8 0.6609 0.6261 1.3324 1.3112
5 92 19 91 33
334.6 0.6586 0.6238 1.3352 1.3134
5 3 81 62 87
333.4 0.6562 0.6216 1.3380 1.3157

12
 5 68 44 42 46
332.1 0.6537 0.6192 1.3410 1.3182
5 1 21 62 01
331.0 0.6515 0.6171 1.3436 1.3202
5 45 7 25 83
330.1 0.6497 0.6154 1.3457 1.3219
5 74 92 26 91
Table 1.6 Calculated T r and for acetone and chloroform.

13
In the next step, the equations below are used to calculate aα and b mix to proceed to the following
steps. The values calculated is tabulated in Table 1.7:

(a) Liquid phase

·
a ∝=x 1 ( a ∝)1 +2 x1 x 2 √ ( a ∝ )1 ( a ∝ )2 + x2 ( a ∝ )2
2 2

2 2
a mix=x 1 a1 +2 x 1 x2 a12 + x 2 a 2

b mix=x 1 b1+ x2 b2

(b) Vapor Phase

a ∝= y 21 ( a ∝ )1+2 y 1 y 2 √ ( a ∝ )1 ( a ∝ )2+ y 22 ( a ∝ )2

2 2
a mix= y 1 a1 +2 y 1 y 2 a12 + y 2 a2

b mix= y 1 b1 + y 2 b2

T [K] x1 y1 x2 y2
335.75 0.098 0.06 0.902 0.94
336.65 0.186 0.143 0.814 0.857
337.25 0.266 0.23 0.734 0.77
337.55 0.36 0.36 0.64 0.64
336.95 0.468 0.514 0.532 0.486
335.85 0.578 0.646 0.422 0.354
334.65 0.673 0.751 0.327 0.249
333.45 0.755 0.83 0.245 0.17
332.15 0.827 0.89 0.173 0.11
331.05 0.892 0.939 0.108 0.061
330.15 0.949 0.975 0.051 0.025
α1 α2 a mix b mix( x) b mix( y)
1.33272
1 1.311421 1.669029 6.4E-05 6.21E-06
1.33064
7 1.309734 1.675475 6.46E-05 1.18E-05
1.32926 1.308612 1.681346 6.51E-05 1.69E-05
14
 7
1.32857
7 1.308051 1.688257 6.57E-05 2.28E-05
1.32995
7 1.309173 1.696216 6.65E-05 2.97E-05
1.33249
1 1.311233 1.704341 6.72E-05 3.66E-05
1.33526
2 1.313487 1.711373 6.78E-05 4.27E-05
1.33804
2 1.315746 1.717455 6.83E-05 4.79E-05
1.34106
2 1.318201 1.722804 6.88E-05 5.24E-05
1.34362
5 1.320283 1.72764 6.92E-05 5.66E-05
1.34572
6 1.321991 1.731887 6.96E-05 6.02E-05
Table 1.7 Calculated aa , a mix , bmix

To calculate a mix and b mix , the component mole fraction, z is involved and calculated by the
equation stated below:

RT
z=
Pv

Derivation of Peng-Robinson equation:

RT am
P= − 2
V −bm V + 2b m V −b m2

RT ( v 2+ 2b mix v−b2mix ) −a ∝(v−bmix )

P= 2 2
(v −bmix )( v + 2b mix v−bmix )

RT v 2 +2 RT b2mix v−RT b2mix −va∝+b mix ∝

P=
v 3 +2 b2mix −v b2mix−v 2 b mix−2 b2mix v +b3mix

15
P v + v (−RT + P b mix ) + v ( −3 P b mix +2 RT b mix −a ∝) + (−RT b mix +b mix a ∝+ P bmix )=0
3 2 2 2 3

16
By using the equation derived above, the specific volume, v can be obtained by utilising the goal
seek function in Microsoft Excel. The results are tabulated in Table 1.8:

T [K] x1 y1 x2 y2 V(x) V(y)

0.02838 0.02838
335.75 0.098 0.06 0.902 0.94 8 8
0.02846 0.02846
336.65 0.186 0.143 0.814 0.857 3 3
0.02851 0.02851
337.25 0.266 0.23 0.734 0.77 3 3
337.55 0.36 0.36 0.64 0.64 0.02854 0.02854
0.02849 0.02849
336.95 0.468 0.514 0.532 0.486 7 7
0.02841 0.02841
335.85 0.578 0.646 0.422 0.354 5 5
0.02832 0.02832
334.65 0.673 0.751 0.327 0.249 5 5
0.02823 0.02823
333.45 0.755 0.83 0.245 0.17 4 4
0.02813 0.02813
332.15 0.827 0.89 0.173 0.11 5 5
0.02805 0.02805
331.05 0.892 0.939 0.108 0.061 2 2
0.02798 0.02798
330.15 0.949 0.975 0.051 0.025 3 3
Table 1.8 Calculated specific volume, v by using goal seek function

For liquid phase, the largest specific volume value, which is v(x)=0.027983 is selected to
further calculate the fugacity coefficient of liquid phase, φ x . This is due to the reason that the
specific volume of a liquid causes higher intermolecular interactions between its components.
This indicates that for liquids with smaller specific volumes, the departure from optimal
behaviour is larger. In order to account for the impact of these interactions, it is crucial to utilise
a smaller specific volume when computing the fugacity coefficient of a liquid phase.

17
 For vapor phase, the smallest specific volume, which is v(y)=0.02854 is selected to
calculate the fugacity coefficient of vapor phase, φ y. This is because when calculating the
fugacity coefficient of a vapor phase, it is important to consider the effect of intermolecular
interactions between molecules in the vapor. The specific volume of a vapor is larger than that of
a liquid at the same temperature and pressure, as the molecules in a vapor are more spread out
and have less opportunity to interact with each other. The relationship between specific volume
and fugacity coefficient can be complex, but in general, a larger specific volume is associated
with a larger fugacity coefficient.

18
 Lastly, by using the equation,

b1 aα b1 2 v + ( 1+ √ 2 ) b
lnφ= ( z−1 ) −ln ((v−b)¿¿¿ RT ) + ( − ( y 1 ( aα )1 ¿ +¿ y 2 ( aα )2 ) )ln
b 2 √2 bRT b aα v+ ( 1−√ 2 ) b

We can obtain the fugacity coefficient, φ:

Phase T [K] φx 1 φx 2 φy1 φy2

Liquid 1.03136
330.15 1.025264 9 - -
Vapor 337.55 - - 1.02893 1.027417
Table 1.9 Calculated fugacity coefficient of selected group of data of acetone and
chloroform in liquid and vapor phase

2.2.1 Vapour mole fraction

Phase T [K] x1 y1 x2 y2 φx 1 φx 2 φy1 φy2

Liquid 1.02526
330.15 0.949 0.975 0.051 0.025 4 1.031369 - -
Vapor 337.55 0.36 0.36 0.64 0.64 - - 1.02893 1.027417
Table 1.10 Data of result

To calculate the vapor mole fraction, the equation is shown as follow:

L V
μi =μ i

L V
f i =f i

L V
P φi xi =P φi y i

( )
L
φi
y i= V
xi
φi

19
 y1
L V
Percentage
T [K] φ1 φ1 calculate
Difference
x1 y1 d
335.75 0.098 0.06 1.025264 1.02893 0.097651 62.75145
336.65 0.186 0.143 1.025264 1.02893 0.185337 29.60655
337.25 0.266 0.23 1.025264 1.02893 0.265052 15.24016
337.55 0.36 0.36 1.025264 1.02893 0.358717 0.356254
336.95 0.468 0.514 1.025264 1.02893 0.466333 9.273788
335.85 0.578 0.646 1.025264 1.02893 0.575941 10.84507
334.65 0.673 0.751 1.025264 1.02893 0.670602 10.7054
333.45 0.755 0.83 1.025264 1.02893 0.75231 9.360207
332.15 0.827 0.89 1.025264 1.02893 0.824054 7.409688
331.05 0.892 0.939 1.025264 1.02893 0.888822 5.343747
330.15 0.949 0.975 1.025264 1.02893 0.945619 3.01342
Table 1.11 Calculated vapor mole fraction, y 1 of acetone in liquid and vapor phase

y2 Percentag
T [K] x2 y2 φ L2 φ v2 calculate e
d Difference
335.75 0.902 0.94 1.031369 1.027417 0.90547 3.673418
336.65 0.814 0.857 1.031369 1.027417 0.817131 4.652118
337.25 0.734 0.77 1.031369 1.027417 0.736824 4.308624
337.55 0.64 0.64 1.031369 1.027417 0.642462 0.384686
336.95 0.532 0.486 1.031369 1.027417 0.534047 9.886117
335.85 0.422 0.354 1.031369 1.027417 0.423623 19.66762
334.65 0.327 0.249 1.031369 1.027417 0.328258 31.83049
333.45 0.245 0.17 1.031369 1.027417 0.245942 44.67205
332.15 0.173 0.11 1.031369 1.027417 0.173666 57.87773
331.05 0.108 0.061 1.031369 1.027417 0.108415 77.73026
330.15 0.051 0.025 1.031369 1.027417 0.051196 104.7848
Table 1.12 Calculated vapor mole fraction, y 2 of chloroform in liquid and vapor phase

20
 A component's fugacity coefficient, which indicates how far from ideal behaviour the
component deviates in a combination, is a dimensionless quantity. The ideal behaviour
corresponds to the fugacity coefficient of a component being less than or equal to one. The
fugacity coefficient of a component in a mixture, on the other hand, can occasionally be more
than one, indicating that the component is acting more like an ideal gas than it would in pure
form.

The Peng-Robinson equation of state may not be appropriate for a given acetone-
chloroform system. This is due to the reason that the fugacity coefficient obtained is greater
than 1. This is so that non-ideal behaviour brought on by interactions between molecules,
which are not taken into account by the Peng-Robinson equation of state, which assumes that
each molecule in the mixture behaves independently (Kumar and Sandler, 2007).

The other activity models such as Three-suffix margules, van Laar and Wilson, which
takes into account molecular interactions and can provide more precise predictions for the
fugacity coefficients of acetone-chloroform system with non-ideal behaviour, may be more
appropriate in such circumstances (Sui et al., 2013).

21
2.3 Adjustable parameters

The value of A, B and C can be found from Appendix A.1.1 and A.1.2 as tabulated in Table
1.13 to obtain saturated pressure, psat by using the Antoine equation as shown below:

B
ln psat =A−
T ( K ) +C

  A B C
10.031 2940.4
Acetone 1 6 -35.93
Chlorofor 9.353 2696.7
m 9 -46.16
Table 1.13 Parameter A, B and C obtained.

Saturated pressures, psat calculated by using Antoine equation which are in unit of bar is then
converted to unit of pascal by using the formula below and the calculated psat is tabulated in
Table 1.14:

psat ( Pa )= psat ¿

y1 x2 P(sat) P(sat)
T [K] x 1 acetone
acetone chloroform acetone chloroform
335.75 0.098 0.06 0.902 125067.4 104139.2
336.65 0.186 0.143 0.814 128792.7 107187.6
337.25 0.266 0.23 0.734 131324.9 109258.4
337.55 0.36 0.36 0.64 132605.8 110305.5
336.95 0.468 0.514 0.532 130053.9 108219.1
335.85 0.578 0.646 0.422 125477 104474.5
334.65 0.673 0.751 0.327 120631.2 100506.3
333.45 0.755 0.83 0.245 115935.7 96657.56
332.15 0.827 0.89 0.173 111014.6 92619.97
331.05 0.892 0.939 0.108 106982.2 89308.4
22
 330.15 0.949 0.975 0.051 103770.7 86669.01
Table 1.14 Saturated Pressure, psat calculated in Pascal

2.3.1 Three-suffix Margules

In order to calculate the parameters of Three-suffix Margules, two equations as stated

below is used:

2 3
RT ln γ a= ( A+ 3 B ) x b−4 B x b
2 3
RT ln γ b= ( A+ 3 B ) x a−4 B x a

By using these equations, the activity coefficient of acetone and chloroform, γ 1 & γ 2 can be
obtained and tabulated in Table 1.15. With the aids of objective functions and solver function
in Excel, the parameters of A and B can be obtained and shown below:

A=−1724.356371

B=146.237923

The calculated pressure, pcalculated and objective function are calculated by using the equation
below:

pcalculated =x 1 γ 1 p sat 1+ x 2 γ 2 psat 2

2
Objective Function=(p experiment − p calculated )

γa γb Pressure Objective
(acetone) (Chloroform) (calculated) Function

0.589485 0.99278129 100480.6 721537.5

0.658971 0.9749278 100849.1 231299.6
0.719262 0.95060339 101359.9 892.4142
0.784834 0.91377904 101975.2 416287.9
0.851013 0.86267827 101463.7 17884.02
0.906886 0.80384309 101212.5 13796.47
23
 0.94482 0.74973065 101345.3 233.9084
0.969534 0.70190948 101486.7 24562.97
0.985082 0.65973992 101010.6 102001.5
0.9943 0.62221235 100885.6 197486.2
0.998754 0.59003428 100963.8 134114.8
1860097
Table 1.15 Calculated activity coefficient of acetone and chloroform for Three-suffix
Margules

2.3.2 Van Laar Model

In order to obtain parameters of van Laar models, two equations stated below are used:

2
B xb
RT ln γ a= A ( )
A x a + B xb

2
A xa
RT ln γ b=B( )
A x a +B x b

Similar as Three-suffix Margules, activity coefficient of acetone and chloroform, γ 1 & γ 2 is

calculated and tabulated in Table 1.6. Parameter of A and B can be obtained by utilizing the
objective function and solver function from Microsoft Excel.

A=−1872.450312

B=−1593.690947

The calculated pressure, Psat and objective function is calculated with the same equation
stated in 2.3.1 and tabulated in Table 1.16.

γa γb Pressure Objecti
(Aceton (Chlorofor (calculate ve
e) m) d) Functio

24
 n
720654.
0.59007 0.9927106 100481.1 2
0.65982 221048.
7 0.97481638 100859.8 6
0.72000 2840.75
1 0.95057392 101383.3 4
0.78515 458237.
9 0.91400889 102006.9 9
0.85075 24260.1
8 0.86333098 101485.8 1
0.90619
8 0.80484824 101207 15135
0.94402 236.611
5 0.75075966 101314.6 4
0.96886 13029.3
1 0.70260242 101444.1 6
0.98463 129698.
1 0.65978051 100969.9 7
224614.
0.99408 0.62133003 100856.1 7
0.99869 144936.
6 0.5880593 100949.3 5
1954692
Table 1.16 Calculated activity coefficient of acetone and chloroform for van Laar model

2.3.3 Wilson Model

Two equations used to calculate the parameters of Wilson model:

⋀ ba ⋀ ab
RT ln γ a=−RT [ln ( x a+ ⋀ ab x b ) + x b ( − )]
x b+ ⋀ ba x a x a + ⋀ab x b

⋀ ab ⋀ ba
RT ln γ b=−RT [ln ( x b+ ⋀ ba x a ) + x a ( − )]
x a+ ⋀ ab x b x b + ⋀ba x a

25
By utilizing the equations above, the activity coefficient of acetone and chloroform, γ 1 & γ 2 is
calculated and tabulated in Table 1.7 with the aids of objective function and solver function
in Microsoft Excel.

⋀ ab =0.023129362

⋀ ba =4.359879573

The equation used to calculate the calculated pressure and objective function is stated in 2.3.1

γa γb Pressure Objecti
(Aceton (Chlorofor (calculate ve
e) m) d) Functio
n
0.52039 438723.
2 1.01789103 101992.4 7
0.60257 83475.9
6 0.99261234 101041.1 2
0.69247 481845.
4 0.95324401 100635.8 7
0.78506 74009.5
2 0.90063193 101058 8
0.86700 36396.0
7 0.84013374 101139.2 5
0.92557 88043.0
9 0.78248717 101626.7 5
0.95962
1 0.73694863 102126.9 634982
0.97920
5 0.700874 102308.7 957828
0.99037
3 0.67155399 101685.7 126538
0.99648 0.64685561 101331.9 3.78905

26
 7 2
24125.8
0.99926 0.62648805 101174.7 2
294597
      2
Table 1.17 Calculated activity coefficient of acetone and chloroform for Wilson model

27
2.4 Vapour mole fraction comparison

In this part, we need to compare the suitability of 3 activity models which are Three Suffix
Margules, Van Laar and Wilson model through the y-x plotting with the equilibrium vapour
mole fraction.

In the graph of y-x plot for 3 different activity models, x-axis is related to the liquid
mole fraction for acetone, x1 while y-axis related to the vapour mole fraction for acetone, y1.
For each plotting of graph for equilibrium mole fraction, there will be a trendline which
indicate the experiment data that we are referring.

For the plotting of the graph, we need the calculated value for vapour mole fraction, y-
1 from each activity model where the mole fraction for the vapour is obtained through
equation as shown as below,

Hence, for the calculation of vapour mole fraction of acetone, we need to refer the
information in part D such as saturated pressure for both acetone and chloroform,
experimental liquid and vapour mole fraction for acetone and chloroform and this
information is summarize in the table form.

Table 1.18: Data obtained form question 1 (d)

T (K) x1 y1 x2 y2 Psat1 (Pa) P sat2(Pa) P (Pa)

335.75 0.098 0.06 0.902 0.94 125067.3 104139.2 101330

512
336.65 0.186 0.143 0.814 0.857 128792.7 107187.6 101330
098
337.25 0.266 0.23 0.734 0.77 131324.9 109258.4 101330
351
337.55 0.36 0.36 0.64 0.64 132605.8 110305.5 101330
05
336.95 0.468 0.514 0.532 0.486 130053.9 108219.1 101330
214
335.85 0.578 0.646 0.422 0.354 125476.9 104474.5 101330

28
 923
334.65 0.673 0.751 0.327 0.249 120631.1 100506.3 101330
787
333.45 0.755 0.83 0.245 0.17 115935.6 96657.56 101330
674
332.15 0.827 0.89 0.173 0.11 111014.5 92619.97 101330
845
331.05 0.892 0.939 0.108 0.061 106982.1 89308.4 101330
675
330.15 0.949 0.975 0.051 0.025 103770.7 86669.01 101330
488

Another than that, we also calculate the percentage difference for the value of 2 set
data from the experiment. One set of data is taken from the literature and another set of data
was obtain from the calculation from the part above. Percentage difference is used instead of
percentage error because there is no accurate value of an experimental value that we need in
the percentage error.

Calculation of vapour mole fraction and percentage difference for both acetone and
chloroform are tabulated as shown below.

Table 1.19: Calculated vapour mole fraction and the percentage difference between the
calculated data and experimental data in Three-suffix Margules model
ϒ1 (calc) ϒ2 (calc) P(calc) (Pa) y1 calc y2 calc Percentage Percentage
difference difference
of y1 (%) of y2 (%)
0.58948546 0.99278129 100480.5664 0.07190532 0.928094674 0.144986858 0.012745955
5 5
0.65897088 0.974927798 100849.0639 0.15653035 0.84346964 0.029447814 0.015913674

29
 7 9
0.71926248 0.950603393 101359.8733 0.24788496 0.75211504 0.000153146 0.023500142
1
0.78483403 0.913779042 101975.2038 0.36740772 0.632592277 0.058139864 0.011641943
3
0.85101333 0.862678269 101463.7311 0.51049893 0.489501063 0.071261136 0.007177979
8 8
0.90688558 0.803843087 101212.5416 0.64984548 0.350154513 0.025783855 0.010922282
7 7
0.94481959 0.749730646 101345.2941 0.75686764 0.243132357 0.016095318 0.023845794
3 3
0.96953444 0.701909479 101486.7258 0.83621512 0.163784876 0.056198948 0.037240295
1 4
0.98508187 0.659739916 101010.6233 0.89534584 0.104654152 0.092643136 0.049808937
3 8
0.99430024 0.622212352 100885.6058 0.94051253 0.059487469 0.123344454 0.025106859
2
0.99875425 0.590034283 100963.7831 0.97416873 0.025831263 0.151521649 0.032706766
7

Table 1.20: Calculated vapour mole fraction and the percentage difference between the
calculated data and experimental data in Van Laar model

ϒ1 (calc) ϒ2 (calc) P(calc) (Pa) y1 calc y2 calc Percentage Percentage

difference difference
of y1 (%) of y2 (%)
0.520392 1.017891 101992.3622 0.071976217 0.937463585 0.041398555 0.002701959

0.602576 0.992612 101041.078 0.156716878 0.857137648 0.000963033 0.000160603

0.692474 0.953244 100635.8489 0.248082058 0.759630414 0.04409123 0.01355829

30
0.785062 0.900632 101057.953 0.367445417 0.629149876 0.029691789 0.017098254

0.867007 0.840134 101139.2225 0.510234891 0.478238381 0.01498727 0.016098963

0.925579 0.782487 101626.7205 0.64938836 0.339462725 0.022253136 0.041926624

0.959621 0.736949 102126.8576 0.756460225 0.2371583 0.015644567 0.048715409

0.979205 0.700874 102308.6869 0.835984618 0.162229328 0.009318634 0.046778963

0.990373 0.671554 101685.7219 0.895297157 0.105820963 0.004684549 0.038726883

0.996487 0.646856 101331.9465 0.940579487 0.061571117 0.000608404 0.009318952

0.99926 0.626488 101174.6751 0.974251505 0.027370012 0.002433739 0.09051026

Table 1.21: Calculated vapour mole fraction and the percentage difference between the
calculated data and experimental data in Wilson model

ϒ1 (calc) ϒ2 (calc) P(calc) (Pa) y1 calc y2 calc Percentage Percentage

difference difference of
of y1 (%) y2 (%)
0.520392 1.017891 101992.3622 0.062536415 0.937463585 0.041398555 0.002701959

0.602576 0.992612 101041.078 0.142862353 0.857137648 0.000963033 0.000160603

0.692474 0.953244 100635.8489 0.240369587 0.759630414 0.04409123 0.01355829

0.785062 0.900632 101057.953 0.370850124 0.629149876 0.029691789 0.017098254

0.867007 0.840134 101139.2225 0.52176162 0.478238381 0.01498727 0.016098963

0.925579 0.782487 101626.7205 0.660537276 0.339462725 0.022253136 0.041926624

0.959621 0.736949 102126.8576 0.762841699 0.2371583 0.015644567 0.048715409

0.979205 0.700874 102308.6869 0.837770672 0.162229328 0.009318634 0.046778963

31
0.990373 0.671554 101685.7219 0.894179037 0.105820963 0.004684549 0.038726883

0.996487 0.646856 101331.9465 0.938428883 0.061571117 0.000608404 0.009318952

0.99926 0.626488 101174.6751 0.972629988 0.027370012 0.002433739 0.09051026

With the result for calculation vapour mole fraction for acetone and chloroform in 3
activity models, the graph of y-x plot for 3 different activity models, x-axis is related to the
liquid mole fraction for acetone, x1 while y-axis related to the vapour mole fraction for
acetone, y1 is then plotted with Excel.

Graph of Vapour mole fraction, y1 against Liquid mole

fraction, x1
1.2

1 1
Vapour mole fraction, y1

0.8

0.6

0.4

0.2

00
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.65 0.7 0.75 0.8 0.85 0.9 0.95 1 1.05
Liquid mole fraction,x1
Three-Suffix Margules Model Experimental Value
y=x

Figure 1.3 Graph of Vapour mole fraction, y1 against Liquid mole fraction, x1 for Three-
suffix Margules model

32
 Graph of Vapour mole fraction, y1 against Liquid mole
fraction, x1
1.05
1
0.95
0.9
0.85
0.8
0.75
Vapour mole fraction, y1

0.7
0.65
0.6
0.55
0.5
0.45
0.4
0.35
0.3
0.25
0.2
0.15
0.1
0.05
0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.65 0.7 0.75 0.8 0.85 0.9 0.95 1 1.05

Liquid mole fraction, x1

Van-Laar Model Experimental Value y=x

Figure 1.4 Graph of Vapour mole fraction, y1 against Liquid mole fraction, x1 for Van
Laar Model

33
 Graph of Vapour mole fraction, y1 against Liquid mole
fraction, x1
1.05
1
0.95
0.9
0.85
0.8
0.75
Vapour mole fraction, y1

0.7
0.65
0.6
0.55
0.5
0.45
0.4
0.35
0.3
0.25
0.2
0.15
0.1
0.05
0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.65 0.7 0.75 0.8 0.85 0.9 0.95 1 1.05

Liquid mole fraction, x1

Wilson Model Experimental Value y=x

Figure 1.5 Graph of Vapour mole fraction, y1 against Liquid mole fraction, x1 for
Wilson Model

34
 1.05 Graph of Vapour mole fraction, y1 against Liquid mole
1 fraction, x1
0.95
0.9
0.85
0.8
0.75
0.7
Vapour mole fraction, y1

0.65
0.6
0.55
0.5
0.45
0.4
0.35
0.3
0.25
0.2
0.15 Experimental Value Three-suffix Margules Model
0.1 Van Laar Model Wilson model
0.05 y=x
0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.65 0.7 0.75 0.8 0.85 0.9 0.95 1 1.05

Liquid mole fraction, x1

Figure 1.6 Graph of comparison of Vapour mole fraction, y1 against Liquid mole
fraction, x1 for Three-suffix Margules model, Van Laar model and Wilson model.

From the result of percentage difference of vapour mole fraction for acetone and
chloroform also the graph of comparison of vapour mole fraction, y1 against liquid mole
fraction x1 in three-suffix margules model, Van Laar model and Wilson model, the most
suitable activity model among this 3-activity model is Three-suffix Margules. It is due to it
overlapping the vapour mole fraction is most fit with the experimental value. Another than
that, Three-suffix Margules coefficient will having the most consistent percentage difference
which avoid large different value for the experiment.

This model is particularly useful for estimating fugacity coefficients because it

accounts for mixture non-idealities and interactions between molecules in the mixture where
the activity coefficient smaller than one (Dave Waters, 2004). The Margules activity model

35
assumes that the activity coefficients of a component in a mixture are related to the
component's mole fraction and its binary interaction parameter. The three-suffixed Margules
activity model goes a step further by including an additional interaction parameter that
describes the interaction between the three different components in the mixture.

Fugacity coefficients are related to activity coefficients using the Gibbs-Duhem equation.
This equation relates changes in the chemical potential of one component to changes in the
chemical potential of other components in the mixture. The three-suffixed Margules activity
model is particularly useful for estimating fugacity coefficients because it can more
accurately describe the interactions between components in a mixture than a simpler model
such as B. An ideal solution model or a normal solution model.

In summary, the three-suffix Margules activity model is suitable for estimating fugacity
coefficients because it takes into account mixture non-idealities and interactions between
molecules within mixtures, which are important factors affecting fugacity coefficients.
model. 

36
3.0 Question 2

3.1 VLE Data for Acetone-Chloroform System from UNIQUAC Activity Model

3.1.1 Generation of VLE Data based on UNIQUAC Activity Model

By using the Aspen Plus process simulator, two sets of VLE data for the acetone-
chloroform system based on the UNIQUAC activity model with different pressure, which are
1 atm and 10 atm. The difference in pressure is used to demonstrate that the VLE curve or the
azeotropic compositions can be shifted at different pressure in pressure-swing distillation.

The liquid mole fraction, x and vapour mole fraction, y for acetone (1) and chloroform
(2) at pressure of 1 atm and 10 atm are generated by Aspen Plus based on UNIQUAC activity
model and the data is tabulated in Table 3.1.1 and Table 3.1.2 respectively.

Table 3.1.1: Vapor mole fraction and liquid mole fraction of acetone and chloroform at
pressure = 1 atm
Pressure(atm) x1 y1 x2 y2
1 0 0 1 1
1 0.1 0.0641545 0.9 0.935845
1 0.2 0.161778 0.8 0.838222
1 0.3 0.28573 0.7 0.71427
1 0.4 0.423149 0.6 0.576851
1 0.5 0.56 0.5 0.440001
1 0.6 0.685116 0.4 0.314884
1 0.7 0.792125 0.3 0.207875
1 0.8 0.879191 0.2 0.120809
1 0.9 0.947561 0.1 0.052439
1 1 1 0 0

37
Table 2.1: Vapor mole fraction and liquid mole fraction of acetone and chloroform at
pressure= 10 atm

Pressure(atm) x1 y1 x2 y2
10 0 0 1 1
10 0.1 0.0824088 0.9 0.917591
10 0.2 0.184473 0.8 0.815527
10 0.3 0.301742 0.7 0.698258
10 0.4 0.42742 0.6 0.57258
10 0.5 0.553524 0.5 0.446476
10 0.6 0.672482 0.4 0.327518
10 0.7 0.778566 0.3 0.221434
10 0.8 0.8688645 0.2 0.131355
10 0.9 0.942073 0.1 0.0579274
10 1 1 0 0

The way to prove the separation has occurred is to compare the mole fractions of
acetone and chloroform in the initial mixture to the mole fractions in the vapor and liquid
phases after distillation process. In table 3.0.1, the vapor and liquid mole fraction of acetone
are 0 but the vapor and liquid mole fraction of chloroform are 1 at 1 atm. After that, the
vapour and liquid mole fraction of acetone increased until 1 at the constant pressure. At the
same time, the vapour and liquid mole fraction of chloroform decreased until 0 at constant
pressure. Since the mole fraction of acetone is increasing when the mole fraction of
chloroform is decreasing, this has indicated the separation of the binary mixture has been
successful.

The separation of binary mixture acetone-chloroform occurs due to the selective

vaporization of the more volatile component, which is acetone. At the beginning of the
distillation process, there is an equilibrium and same composition for both liquid and vapour
phases. During the distillation process, the mole fraction of acetone increased due to the
selectivity vaporized as acetone is more volatile while the mole fraction of chloroform will
decrease.

38
 Figure 2.1: Graph of y-x for Acetone-Chloroform system at 1 atm and 10 atm

With these two sets of VLE data, a y-x plot has been plotted to demonstrate that the
azeotrope composition or the VLE curve can be shifted at different pressure in pressure-
swing distillation.
To show the different, another set of data at 10 atm has obtained. Since the mole
faction of acetone also increased while the mole fraction of the chloroform decreased during
distillation, the binary mixture has separated successfully. This showed that it can be shifted
at different pressure in pressure-swing distillation.

39
 Figure 2.2: Graph of T-xy for Acetone-Chloroform system at 1 atm and 10 atm

The graph of T-xy for acetone-chloroform system showed the mole fraction of vapor
and liquid phases for acetone under the pressure of 1 atm and 10 atm. The gradient of vapor
and liquid mole fraction of acetone is higher when the pressure is at 10 atm. There are many
azeotrope positions in the graph. This also proved that the VLE curve can be shifted at
different pressure in a pressure-swing distillation.

40
3.2 Demonstration of DMSO and EG used as Solvents based on their VLE in the System

Figure 2.2: Graph of T-xy for Acetone-DMSO system at 1 atm

Figure 2.3: Graph of T-xy for Acetone-EG system at 1 atm

41
 Figure 2.4: Graph of T-xy for Chloroform-DMSO system at 1 atm

Figure 2.5: Graph of T-xy for Chloroform-EG system at 1 atm

Based on the four T-xy phase diagrams, dimethyl sulfoxide (DMSO) and ethylene
glycol (EG) are shown that they are suitable to be used as solvents. This is because there is
not any azeotrope or knowns as zeotropic behaviour in the system for acetone and chloroform
with DMSO and EG. Besides that, fractional distillation also can used to separate the liquid
mixture into respective two components. The below diagram is the example of zeotropic.

42
Figure 2.6: Binary zeotropic mixture diagram phase (Ciro, 2002)

Figure 2.7: Residue curve for acetone-chloroform with EG

43
 Figure 2.8: Residue curve for acetone-chloroform with DMSO

Based on the analysis of figures 3.2.6, 3.2.7, and 3.2.8, it can be concluded that there
are no unstable or stable nodes in the residue curve, indicating that the system is not
azeotropic. In an azeotropic system, there should be an unstable node with lines pointing
towards a stable node, and a saddle point where the lines move towards and away from it.
However, this is not observed in the residue curve of DMSO and EG mixture, which
confirms that they can be used as solvents to modify the vapour-liquid equilibrium without
forming an azeotrope with other components in the mixture.

Figure 2.9: Diagram of typical homogeneous mixtures with maximum boiling azeotrope
(W.Shen, H. Benyounes, J. Song, 2015)

44
4.0 Conclusion

In conclusion, the vapor-liquid equilibrium (VLE) behaviour of the acetone-

chloroform system can be observed through experimental data obtained from literature and
Aspen Plus process simulator. The experimental data is compared with data from the
National Institute of Standards and Technology (NIST) database using Aspen Plus, and
specific volumes and fugacity coefficients are estimated using the Peng-Robinson equation of
state (EOS). While the sources of these data may be different, it is found that we can
determine the fugacity coefficients both by using EOS or through experimental data as the
resulting percentage different is found to be less than 1%.

Besides that, the adjustable parameters for three-suffix Margules, van Laar, and
Wilson activity models are fitted using the Antoine equation, and the equilibrium vapor mole
fractions predicted using the activity models are compared with experimental data. Through
the further comparison between the different models through the values of the data obtained,
the graph performance suggests that the Wilson equation from the Wilson model is the most
suitable for analyzing the Vapor-Liquid Equilibrium (VLE) system among the other activity
models used. This is because the Wilson equation considers the possibility of local
composition differing from bulk composition in various liquids. On the other hand, the Three
Suffix Margules equation is only used to obtain activity coefficients (γ1) from ideal solubility
in a liquid. However, it should be noted that the Wilson equation is restricted to completely
miscible mixtures, such as activity coefficients in the liquid-liquid equilibrium (LLE). It may
not be suitable for systems where complete miscibility is not observed.

Aspen Plus is also used to generate VLE data for the acetone-chloroform system
based on the UNIQUAC activity model, and the suitability of dimethyl sulfoxide (DMSO)
and ethylene glycol (EG) as solvents in an extractive distillation for the acetone-chloroform
system is demonstrated. Based on the analysis of the residue curve for the DMSO and EG
mixture, it can be determined that the system is not azeotropic. This is evident from the
absence of unstable or stable nodes in the residue curve, as well as the lack of a saddle point
where lines move towards and away from it. In an azeotropic system, these features would
typically be observed. Therefore, it can be inferred that DMSO and EG can be used as
solvents to modify the vapor-liquid equilibrium without forming an azeotrope with other
components in the mixture.

45
5.0 References

An experimental evaluation of the vapour compression plant performances in presence of

R407C leaks using an electronic expansion valve - Scientific Figure on ResearchGate.
Available from: https://www.researchgate.net/figure/Binary-zeotropic-mixture-diagram-
phase_fig2_245212989 [Accessed: 19 Apr, 2023]

Dave Waters, U.of O. (2004) Practical aspects of mineral thermobarometry, Practical

DDBST GmbH (2022). Vapor-Liquid Equilibrium Data of Acetone + Chloroform from

Dortmund Data Bank. [online] Ddbst.com.
Available at: http://www.ddbst.com/en/EED/VLE/VLE%20Acetone%3BChloroform.php.
[Accessed: 3 Apr, 2023]

Introducing Aspen Plus. (2016). Aspen Plus®, pp.1–47. doi:

https://doi.org/10.1002/9781119293644.ch1. [Accessed: 20 Apr 2023]

Kumar, R., & Sandler, S. I. (1997). Fugacity coefficient models for associating fluids. AIChE
Journal, 43(8), 2039-2051. [Accessed: 20 Apr 2023]

Shen, Weifeng, Hassiba Benyounes and J. Song. “THERMODYNAMIC TOPOLOGICAL

ANALYSIS OF EXTRACTIVE DISTILLATION OF MAXIMUM BOILING
AZEOTROPES.” Brazilian Journal of Chemical Engineering 32 (2015): 957-966. [Accessed:
20 Apr 2023]

Sui, Z., Zhang, X., & Wu, J. (2013). Investigation of carbon dioxide-rich phases in carbon
dioxide-ionic liquid systems using a thermodynamic model. Fluid Phase Equilibria, 355, 53-
62. [Accessed: 20 Apr 2023]

Thermobarometer Part 3 : Solid Solutions - non-ideal mixing.

Available at https://www.earth.ox.ac.uk/~davewa/pt/pt03_nonid.html [Accessed: April 20,
2023].

46