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Identification of Best Model for Equilibrium

Data of Ethanol-Water Mixture

Article · July 2010

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June 2010, Volume 4, No.6 (Serial No.31)
Journal of Chemistry and Chemical Engineering, ISSN 1934-7375, USA

Identification of Best Model for Equilibrium Data of

Ethanol-Water Mixture

Bilel Hadrich and Nabil Kechaou

Process Engineering Group Agri-food Research Unit and Applied Fluid Mechanics Modeling, National Engineering School of Sfax,
Sfax 3038, Tunisia

Received: January 18, 2010 / Accepted: February 1, 2010 / Published: June 30, 2010.

Abstract: Four empirical models are tested for fitting the T-y-x equilibrium data of ethanol-water mixture by minimizing the Root
Mean Square (RMS) between equilibrium data and theoretical points. The total pressure of the correspondent data is 101.3 kPa. All
models parameters are also identified. The study suggests that NRTL model fits the equilibrium data best with RMS = 0.4 %.

Key words: Equilibrium datas, models, ethanol-water mixture.

used for identification of those activity coefficients [1,

1. Introduction
2]. Each of them presents some particularities in their
The bioethanol is considered as a very important expressions.
renewable energy in this decade. It could be produced The aim of this work is the identification of the best
from natural sources (wheat, sugar cane, sugar beet, mathematical model fitting the T-y-x equilibrium data
corn, etc.) by fermentation and purified by distillation. of ethanol-water mixture.
The calculation of distillation column (continuous and
2. Mathematical models
batch processes) is based on determination of its
equilibrium-stage. This step could be obtained by 2.1 Thermodynamic Data
graphic methods (McCabe and Thiele or Ponchon-
The relative volatility of an ideal binary system is
Savarait) basing on equilibrium curve and operating
defined by:
lines. Usually, the equilibrium curve is presented in
Pi0
literature as equilibrium point. Its fitting by D ij (1)
Pj0
mathematical models is a very important step for Where Pi0 is the vapour pressure of the component i
programming the graphic methods. The equilibrium in the mixture. It could be determined by Antoine
liquid-vapour of ethanol-water mixture presents some equation [1].
particularity. In fact, it’s considered as a non-ideal In the whole manuscript, the index 1 is relative to
mixture and it presents an azeotrope in mole fraction of ethanol and the index 2 is relative to water.
89% [1]. In this case, the identification of the activity For the non-ideal system, relation 1 became:
coefficients of ethanol and water is a very important J i ˜ Pi0
D ij (2)
step in fitting equilibrium data. Wilson, NRTL, Van J j ˜ P j0
Laar and Margules are among the most empiric models Where Ji is the activity coefficient of the
component i.
Corresponding author: Bilel Hadrich, Ph.D. student,
research field: bioethanol production. E-mail:
Those parameters could be obtained by identificat-
bilelhadrich@yahoo.fr.
 Identification of Best Model for Equilibrium Data of Ethanol-Water Mixture 47

ion, by using a number of mathematical models for The activity coefficients are presented by the follow-
different binary or complex systems. The ing relations [1]:
determination of those parameters allows to fit the ln J1  A12  2 ˜ A 21  A12  ˜ x1  ˜ x 22 (9)
equilibrium data. ln J 2  A 21  2 ˜ A12  A 21  ˜ x 2  ˜ x12
(10)
Aij is the adjustable parameters of Margules model.
2.2 Wilson Model

The Wilson model presents the activity coefficients

3. Statistical Analysis
for binary system with the following relations [1]: The models parameters were determined by
§ /12 / 21 ·
ln J1   ln x1  /12 ˜ x 2   x 2 ˜ ¨¨  ¸
¸
(3) minimizing the Root Mean Square (RMS) which
© x1  /12 ˜ x 2 x 2  / 21 ˜ x1 ¹
expresses the difference between equilibrium and
§ /12 / 21 ·
lnJ 2   lnx 2  / 21 ˜ x1   x1 ˜ ¨¨  ¸
¸
(4)
© x1  /12 ˜ x 2 x 2  / 21 ˜ x1 ¹
predicted equilibrium curves. The root mean square
vj § O ij  O ii · was calculated as following:
Wher / ij ˜ exp¨¨  ¸ ; O ij is interaction
vi RT ¸ N 2
§ y i,cal  y i,eq · §T  Ti,eq ·
2
© ¹
¦ ¨¨© y i,cal
¸  ¨ i,cal
¸ ¨ T
¸
¸ (11)
energy between components i and j, Ȝij = Ȝji ; vi is molar RMS i 1 ¹ © i , cal ¹
100 N 1
volume of pure-liquid component I, in J/mol;
Where yi,eq and yi,cal were equilibrium and predicted
A 12 O 12  O 11 and A 21 O 21  O 22 are the adjustable
ethanol mole fraction in vapour, respectively; Ti,eq and
model parameters.
Ti,cal were equilibrium and predicted temperature
2.3 NRTL Model saturation, respectively and N is the number of points.
The model which gives the minimum RMS will be
In this case, the activity coefficients are presented by
considered as the best one and fitting the equilibrium
relations 5 and 6:
data best. The tolerance is fixed at 10-4.
§ § ·
2 ·
¨ ¸
ln J1 
G 21 G12
x 22 ˜ ¨ W21 ˜ ¨¨ ¸  W12 ˜
¸ ¸
(5) A program was carried out with Matlab®, to
¨
© © x1  x 2 ˜ G 21 ¹ x 2  x1 ˜ G12 2 ¸
¹ optimize and to determinate the models parameters.
§ § ·
2 ·
¨ ¸
lnJ 2 
G12 G 21
x12 ˜ ¨ W12 ˜ ¨¨ ¸  W21 ˜
¸ ¸
(6) 4. Results and Discussion
¨
© © 2
x  x1 ˜ G12 ¹ x1  x 2 ˜ G 
21 ¸¹
2

Where G ij  
exp  0,3 ˜ W ij , Wij
A ij
RT
.
Table 1 shows the predicted parameters and the
RMS values for all tested models.
The binary interaction parameters to determinate are
It’s clear that the NRTL and Van Laar models show
A12 and A21. They are different to zero but A12 = A21 =
fit best. Having the smallest RMS, the NRTL model is
0. So, A12 and A21 must be optimized to fit the
retained to fit the T-y-x equilibrium data of
equilibrium data.
ethanol-water mixture.
2.4 Van Laar Model It is important to remark that all activity coefficients
are very comparable for all models. So it could be
Relations 7 and 8 present the activity coefficients as
considered that the suggested program was validated
follows [1]:
2 and it’s very important to optimize this type of model.
§ A 21 ˜ x 2 ·
lnJ1  A12 ˜ ¨¨ ¸¸ (7) Fig. 1 shows the quality of fitting equilibrium data
© 12 x 1  A 21 ˜ x 2
A ˜ ¹
§ A12 ˜ x1 ·
2 (at atmospheric pressure) by NRTL model.
lnJ 2  A 21 ˜ ¨¨ ¸¸ (8)
© A12 ˜ x 1  A 21 ˜ x 2 ¹ 5. Conclusions
Aij is the adjustable parameters of Van Laar model.
The fitting of liquid-vapour equilibrium of
2.5 Margules Model ethanol-water mixture at atmospheric pressure was in-
 48 Identification of Best Model for Equilibrium Data of Ethanol-Water Mixture

Table 1 Parameters and RMS values obtained for the tested models.
Parameters’ model Activity coefficient
Model RMS (%)
A12 A21 J1 J2
Wilson 1242.5 4096.8 1.0085 2.3933 1.323
NRTL -633 5823.1 1 2.4090 0.403
Van Laar 1.6939 0.9076 1.0060 2.2315 0.745
Margules 1.6432 0.6923 0.9994 2.0431 1.246

the best one fitting equilibrium data. It’s important to

say that this work is very important step to program the
graphic methods valid for calculation of distillation
column (batch and continuous).

References
[1] J.D. Seader, J.J. Siirola, S.D. Bernicki, Perry’s Chemical
Engineers’ Handbook, 7th ed., chapter 13, Distillation, pp.
13-1-13-108. The McGraw-Hill Companies, Inc., 1997.
[2] J.L. Humphrey, G.E. Keller II, Separation Processes:
techniques, selection, dimensionnement, Dunod, 2001.

Fig. 1 Equilibrium and predicted (by NRTL model)
equilibrium liquid-vapour of ethanol-water mixture at
atmospheric pressure.
vestigated. Four models were tested. NRTL model is
Nomenclature
R ideal gas constant [J/(mol K)]
T absolute temperature (K)
X ethanol mole fraction in liquid (-)
y ethanol mole fraction in vapour (-)
J activity coefficient (-)

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