Agung Ari Wibowo, S.T, M.

Sc

THERMODYNAMICS MODEL
 THERMODYNAMICS MODEL

For the description of phase equilibria today

modern thermodynamic models are available.
For vapor-liquid equilibria it can
bedistinguished between two different
methods. One method only requires fugacity
coefficients φi and the other require
coefficient activity (ɣ) for the liquid (L) and the
vapor (V) phase:

Or
 Coefficient Activity Model
Thermodynamic model for the excess Gibbs free energy of a liquid mixture
Abrams D.S., Prausnitz J.M., “Statistical
Published by Grant M. Wilson as Thermodynamics of Liquid Mixtures: A New
Introduced in 1895 "Vapor-Liquid Equilibrium. XI. A New Expression for the Excess Gibbs Energy of Partly
by Max Margules Expression for the Excess Free Energy or Completely Miscible Systems”, AIChE J., 21(1),
of Mixing" 1964. 116–128, 1975

Margules Van Laar Wilson NRTL UNIQUAC

Developed by Johannes Renon H., Prausnitz J. M., "Local

van Laar in 1910-1913. The Compositions in Thermodynamic
equation was derived from Excess Functions for Liquid Mixtures",
the Van der Waals . AIChE J., 14(1), S.135–144, 1968
 Coefficient Activity Model
Both methods mentioned above have different advantages
and disadvantages. They have in common that phase
equilibria of multicomponent mixtures can be calculated
using binary data alone. This is most important since nearly
no data are available for multicomponent systems. But for
fitting the required binary parameters reliable phase
equilibrium information for the whole concentration and a
large temperature range is required.

For actual problems often at least a part of the required

binary data is missing. This means that in many cases the
methods mentioned above cannot directly be applied

Kuswandi, K., Winarsih, W., Hartanto, D. dan Wibowo, A. A. (2011) “Pengukuran Kesetimbangan Uap-Cair Sistem Biner Etanol Etil Asetat dan Etanol Isoamil Alkohol Pada Tekanan 101,33 79,99
dan 26,67 kPa,” in Prosiding Seminar Nasional Fundamental dan Aplikasi Teknik Kimia 2011. Surabaya: Jurusan Teknik Kimia - ITS, hal. 1–6.
 Coefficient Activity Model
Margules Model

Roult Modification

The activity coefficient of component i is found by differentiation of the excess Gibbs energy towards xi

In here A12 and A21 are binary interaction parameter

 Coefficient Activity Model

Kuswandi, K., Winarsih, W., Hartanto, D. dan Wibowo, A. A. (2011) “Pengukuran Kesetimbangan Uap-Cair Sistem Biner Etanol Etil Asetat dan Etanol Isoamil Alkohol Pada Tekanan 101,33 79,99
dan 26,67 kPa,” in Prosiding Seminar Nasional Fundamental dan Aplikasi Teknik Kimia 2011. Surabaya: Jurusan Teknik Kimia - ITS, hal. 1–6.
 Data Fitting to get binary interaction parameter

VLE data of Etanol + Isoamil Alkohol at

101,33 kPa
How to perform data fitting?
• Calculate 𝑃 𝑠𝑎𝑡 of each component at given experimental T, using
Antoine Equation
• Calculate γ1 𝑎𝑛𝑑 γ2 𝑜𝑓 𝑒𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡𝑎𝑙 𝑑𝑎𝑡𝑎 𝑢𝑠𝑖𝑛𝑔 𝑅𝑜𝑢𝑙𝑡 𝑀𝑜𝑑𝑖𝑓𝑖𝑒𝑑
Equation
• Calculate γ1 𝑎𝑛𝑑 γ2 using Margules Model, by Guessing any Value
of A12 and A21
• Evaluate the new value of P total using
• P = x1* γ1 * 𝑃1𝑠𝑎𝑡 + x2* γ2 * 𝑃2𝑠𝑎𝑡
• Calculate ΔP = abs (P exp – P calc)
• Sum all ΔP and perform minimization of total ΔP using “Solver” by
changing the value of A12 and A21

Kuswandi, K., Winarsih, W., Hartanto, D. dan Wibowo, A. A. (2011) “Pengukuran Kesetimbangan Uap-Cair Sistem Biner Etanol Etil Asetat dan Etanol Isoamil Alkohol Pada Tekanan 101,33 79,99
dan 26,67 kPa,” in Prosiding Seminar Nasional Fundamental dan Aplikasi Teknik Kimia 2011. Surabaya: Jurusan Teknik Kimia - ITS, hal. 1–6.
 Coefficient Activity Model
Antoine Etanol Iso amyl
A 8.204 7.334
B 1642.890 1353.300 Before Optimization
C 230.300 172.190

𝐵
log 𝑃 𝑠𝑎𝑡 = 𝐴 +
𝐶 + 𝑇/℃

A12 0.5
A21 0.21
P 101.3 kPa
Fraksi etanol
No x1 x2 y1 y2 T Exp P1 sat (kPa) P2 sat (kPa) gamma 1 exp gamma 2 exp gamma 1 cal gamma 2 cal P cal delta P
1 1.0000 0.0000 1.0000 0.0000 78.3000 101.2228 11.3785 1.0008 1.0000 1.2337 101.2228 0.0772
2 0.9513 0.0487 0.9955 0.0045 79.3000 105.3110 11.9555 1.0066 0.7833 0.9999 1.2687 100.9115 0.3885
3 0.8751 0.1249 0.9918 0.0082 81.2000 113.4594 13.1195 1.0119 0.5082 0.9999 1.3248 101.4482 0.1482
4 0.6169 0.3831 0.9412 0.0588 88.4000 149.2769 18.4281 1.0352 0.8444 1.0211 1.5020 104.6381 3.3381
5 0.4716 0.5284 0.8518 0.1482 93.4000 179.3157 23.0806 1.0203 1.2311 1.0653 1.5409 108.8791 7.5791
6 0.3896 0.6104 0.8319 0.1681 96.7000 201.7611 26.6553 1.0721 1.0467 1.1075 1.5762 112.6967 11.3967
7 0.2619 0.7381 0.6855 0.3145 105.2000 270.4739 38.0194 0.9804 1.1352 1.2088 1.5086 127.9590 26.6590
8 0.0967 0.9033 0.3964 0.6036 122.3000 467.3119 72.9951 0.8889 0.9273 1.4366 1.3395 153.2211 51.9211
9 0.0215 0.9785 0.1479 0.8521 127.4000 544.5513 87.4022 1.2784 1.0094 1.5948 1.2491 125.5093 24.2093
10 0.0000 1.0000 0.0000 1.0000 131.7000 617.4413 101.2604 1.0004 1.6487 1.2337 124.9228 23.6228
OF (ΣΔP) 149.3399

Kuswandi, K., Winarsih, W., Hartanto, D. dan Wibowo, A. A. (2011) “Pengukuran Kesetimbangan Uap-Cair Sistem Biner Etanol Etil Asetat dan Etanol Isoamil Alkohol Pada Tekanan 101,33 79,99
dan 26,67 kPa,” in Prosiding Seminar Nasional Fundamental dan Aplikasi Teknik Kimia 2011. Surabaya: Jurusan Teknik Kimia - ITS, hal. 1–6.
 Coefficient Activity Model
Antoine Etanol Iso amyl
A 8.204 7.334
B 1642.890 1353.300 After Optimization
C 230.300 172.190
𝐵
log 𝑃 𝑠𝑎𝑡 = 𝐴 +
𝐶 + 𝑇/℃

A12 0.029962097
A21 0.043072889
P 101.3 kPa
Fraksi etanol
No x1 x2 y1 y2 T Exp P1 sat (kPa) P2 sat (kPa) gamma 1 exp gamma 2 exp gamma 1 cal gamma 2 cal P cal delta P
1 1.0000 0.0000 1.0000 0.0000 78.3000 101.2228 11.3785 1.0008 1.0000 1.0440 101.2228 0.0772
2 0.9513 0.0487 0.9955 0.0045 79.3000 105.3110 11.9555 1.0066 0.7833 1.0001 1.0427 100.8053 0.4947
3 0.8751 0.1249 0.9918 0.0082 81.2000 113.4594 13.1195 1.0119 0.5082 1.0008 1.0407 101.0763 0.2237
4 0.6169 0.3831 0.9412 0.0588 88.4000 149.2769 18.4281 1.0352 0.8444 1.0068 1.0348 100.0238 1.2762
5 0.4716 0.5284 0.8518 0.1482 93.4000 179.3157 23.0806 1.0203 1.2311 1.0119 1.0336 98.1779 3.1221
6 0.3896 0.6104 0.8319 0.1681 96.7000 201.7611 26.6553 1.0721 1.0467 1.0151 1.0325 96.5855 4.7145
7 0.2619 0.7381 0.6855 0.3145 105.2000 270.4739 38.0194 0.9804 1.1352 1.0203 1.0346 101.2997 0.0003
8 0.0967 0.9033 0.3964 0.6036 122.3000 467.3119 72.9951 0.8889 0.9273 1.0269 1.0401 114.9717 13.6717
9 0.0215 0.9785 0.1479 0.8521 127.4000 544.5513 87.4022 1.2784 1.0094 1.0297 1.0434 101.2998 0.0002
10 0.0000 1.0000 0.0000 1.0000 131.7000 617.4413 101.2604 1.0004 1.0304 1.0440 105.7173 4.4173
OF (ΣΔP) 27.9980

Kuswandi, K., Winarsih, W., Hartanto, D. dan Wibowo, A. A. (2011) “Pengukuran Kesetimbangan Uap-Cair Sistem Biner Etanol Etil Asetat dan Etanol Isoamil Alkohol Pada Tekanan 101,33 79,99
dan 26,67 kPa,” in Prosiding Seminar Nasional Fundamental dan Aplikasi Teknik Kimia 2011. Surabaya: Jurusan Teknik Kimia - ITS, hal. 1–6.
 Coefficient Activity Model

No x1 y1-exp y 1 -calc
1 1.000 1.000 1.001
2 0.951 0.996 1.000
Calculate y1 using Parameter
3 0.875 0.992 0.994 obtained by Margules Minimization
4 0.617 0.941 0.953
5 0.472 0.852 0.879
6 0.390 0.832 0.872
7 0.262 0.686 0.686
8 0.097 0.396 0.349
9 0.022 0.148 0.148
10 0.000 0.000 0.000

Kuswandi, K., Winarsih, W., Hartanto, D. dan Wibowo, A. A. (2011) “Pengukuran Kesetimbangan Uap-Cair Sistem Biner Etanol Etil Asetat dan Etanol Isoamil Alkohol Pada Tekanan 101,33 79,99
dan 26,67 kPa,” in Prosiding Seminar Nasional Fundamental dan Aplikasi Teknik Kimia 2011. Surabaya: Jurusan Teknik Kimia - ITS, hal. 1–6.
 Coefficient Activity Model
VLE data of Etanol + Isoamyl Alcohol at 101,33 kPa
140

130
x
120 y- exp

110
y- calc
T/°C

100

90

80

70
0.0 0.2 0.4 0.6 0.8 1.0
x1 (etanol mol fraction)

Kuswandi, K., Winarsih, W., Hartanto, D. dan Wibowo, A. A. (2011) “Pengukuran Kesetimbangan Uap-Cair Sistem Biner Etanol Etil Asetat dan Etanol Isoamil Alkohol Pada Tekanan 101,33 79,99
dan 26,67 kPa,” in Prosiding Seminar Nasional Fundamental dan Aplikasi Teknik Kimia 2011. Surabaya: Jurusan Teknik Kimia - ITS, hal. 1–6.