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Liquid-Liquid Equilibrium and Extraction using Mathematica

Article  in  Computers in Education Journal · September 2005

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 LIQUID-LIQUID EQUILIBRIUM AND EXTRACTION USING
MATHEMATICA

Housam Binous
National Institute of Applied Sciences and Technology
BP 676 Centre Urbain Nord, 1080 Tunis, Tunisia

Abstract obtain anhydrous ethanol using benzene as an

entrainer (e.g. the three column Kubierschky
In the present paper, we show a new approach, system). This ternary system is of a Type I with
based on the utilization of Mathematicato a plait point separating the raffinate phase and
solve liquid-liquid extraction problems. Since the extract phase. In order to take into account
liquid-liquid equilibrium data are primordial for liquid demixtion, we will use the liquid phase
the design of extraction columns, we start with activity coefficients from the NRTL model[5]
the calculation of such data for a multi- given by equation (1):
component mixture using the NRTL model. We
will consider a ternary mixture of benzene - C
  C

ethanol - water at 25°C. The built-in  ji G ji x j C  xG    kj G kj x k 
(1)
ln  i 
j 1
  C
j ij   k 1 
®
Mathematica function, FindRoot, is used to C
  ij C 
solve a system of nonlinear algebraic equations G ki xk j 1
  G kj x k 

 G kj x k 

k 1  k 1 k 1

traducing the equilibrium relation between the

two liquid phases. We also study the where xi is the mole fraction of a component and
separation[1] of acetic acid from water using
Gij and  ij are written as follows,
isopropyl ether for each of the following cases:
single-feed countercurrent extractor and two-
( g ij  g jj )
G ji  exp  ji ji   ij 
feed extraction column. We use the graphical
method derived by Hunter and Nash[2] and later (2)
RT
by Kinney[3] to obtain for both cases the
number of equilibrium stages required to The energy parameters (expressed in
achieve a particular raffinate specification. kcal/kmol), g ij , and the nonrandomness
Finally, we use the McCabe-Thiele diagram to
obtain the same value of the number of parameters,  ij , are given in Tables 1 and 2.
equilibrium stages. The notebooks are available
from the author upon request or at Wolfram g ij Benzene Ethanol Water
Research[4]. Benzene 0 334.1524 3719.395
Ethanol 991.5067 0 1332.312
Key words: Liquid-liquid extraction, tie-lines,
Water 4843.376 -109.6339 0
NRTL model, Hunter-Nash diagram, McCabe-
Thiele method
Table 1 - Energy parameters.
Liquid-Liquid Equilibrium Diagram of
A Ternary Mixture  ij Benzene Ethanol Water
Benzene 0 0.291099 0.20
We present in this section, the computation of Ethanol 0.291099 0 0.303099
equilibrium data for the ternary system: benzene Water 0.20 0.303099 0
- ethanol - water at a temperature of 25°C.
Application of such equilibrium diagram Table 2 - Nonrandomness parameters.
include heterogeneous azeotropic distillation to

78 COMPUTERS IN EDUCATION JOURNAL

 The condition of equilibrium states that the Extraction of Acetic Acid from Water
activities in the two liquid phases must be equal: Using Isopropyl Ether

xi1 i1  xi2 i2 i  1,2,3 (3) We will now study the separation of acetic
acid from water using isopropyl ether as a
We also have additional relations such as the solvent. This separation is usually difficult to
summation rules and material balances: realize with distillation due to the presence of a
severe tangent pinch at high compositions of
water which prevent the distillate from being
 
i 3 1 i 3
x  1 and
i 1 i i 1
xi2  1 (4) acid-free. A graphical solution performed by
hand calculation has been presented by
L1  L2  1 and L1 xi1  L2 xi2  X i i  1,2 (5) Wankat[1]. We will show how one can use
Mathematica to solve this problem more
Equations 1-5 can be solved simultaneously easily and accurately using the graphical
using the built-in Mathematica approach of Hunter and Nash[2] as well as the
function, McCabe-Thiele diagram. Equilibrium data, at 1
FindRoot, in order to get the eight unknown, atm and 25°C, are given by Wankat[1], they can
xi1 , xi2 , L1 and L2 , which are the mole fractions be used to plot the following diagram where the
tie lines has been drawn (see Figure 2). Note
in both liquid phase for the three components that the conjugate line can be easily constructed
and the total number of moles in the two liquid using the equilibrium points.
phase in equilibrium. If we solve this system of
equations for different values of X 1 and X 2 , we
wt. frac . acetic acid
get Figure 1. Tie lines are obtained by joining 100
with lines the equilibrium points, the extract and
raffinate curves are also plotted. The system
80
considered in this study is a Type I where the a
plait point is marked as a bold dot in the figure.
60

Ethanol
1 40

0.8 20

0.6
wt. frac . water
20 40 60 80 100

0.4

0.2
Figure 2 - Equilibrium data for the ternary
system.

-0.2 0.2 0.4 0.6 0.8 1 1-Single feed countercurrent extractor

Water Benzene
-0.2
The feed is 1000 kg/hr of a solution composed
of 35 wt % acetic acid and 65 wt % water. The
Figure 1 - Liquid-liquid equilibrium diagram for solvent used to perform the extraction is pure
a ternary system. isopropyl ether with a flow rate equal to 1475
kg/hr. We require that the raffinate composition

COMPUTERS IN EDUCATION JOURNAL 79

in acid do not exceed 10 wt %. First, we locate Using the triangular diagram (see Figure 3)
the mixing point and the difference point. Then, and the procedure described by Wankat[1], we
we step off stages using alternatively the tie can get the McCabe-Thiele diagram shown in
lines and the operating lines until we reach a Figure 4. We draw steps between the
raffinate composition lower than 10 wt %. The equilibrium and operating lines to get the total
method is illustrated in Figure 3. We find that number of equilibrium stages which will
5.35 equilibrium stages are required to achieved achieve the raffinate specification. We find that
10 wt % of acid in the raffinate. both methods are in agreement.

2- Two-feed extraction system

wt. frac . acetic acid
Pure isopropyl ether with a flow rate of 1800
40
kg/hr is used to extract acetic acid from water.
Two feeds composed of water and acid are used
in this case; the first feed rate and acid
30
composition are, 600 kg/hr and 35 wt. %
respectively, while the second feed has the
20
following characteristics: feed flow rate of 400
kg/hr and weight fraction of acid equal to 20 wt.
10
%. As in the previous case, we would like to
achieve a raffinate purity of 10 wt. % in acetic
wt. frac . water acid. We find the mixing point and the two
-50 -25 25 50 75 100
difference points,  1 and  2 ,as described by
Wankat[1] using Mathematica. We start by
Figure 3 - Hunter and Nash diagram for the stepping off the stages using the first difference
single feed case. point until a tie line intersect the line joining the
two difference points and the second feed point
F2 . Finally, we step off the stages using the
second difference point until we reach the
raffinate specifications. Figure 5, obtained with
extract wt. frac Mathematica, shows the entire graphical
35 procedure. We find a total of 2.89 stages as well
30 as the location of the optimum feed stage which
for this particular case turns out to be stage
25
number 2.
20

15

10

raffinate wt. frac

10 20 30 40

Figure 4 - McCabe-Thiele diagram for the

single feed case.

80 COMPUTERS IN EDUCATION JOURNAL

 References
wt. frac acetic acid
100 1. P. C. Wankat, Equilibrium Stages
Separations, Prentice Hall, Englewood
80 Cliffs, 1988 (example 18-2, page 595 and
example 18-3, page 609).
60
2. T. G. Hunter and A. W. Nash, J. Soc. Chem.
Ind., (53) 95T-102T, 1934.
40
3. G. F. Kinney, Ind. Eng. Chem., (34) 1102-
20 1104, 1942.

4 http://library.wolfram.com/infocenter/search
wt. frac water
-50 -25 25 50 75 100 /?search_results=1;search_person_id=1536 .

5. J. M. Prausnitz, R. N. Lichtenthaler and E.

Figure 5 - Hunter and Nash diagram for the G. deAzevedo, Molecular Thermodynamics
two feed case. of Fluid-Phase Equilibria, Prentice-Hall,
Englewood Cliffs, NJ, 3rd ed., 1998.
Conclusion

In this study, we showed how simple Biographical Information

Mathematica commands can be used to solve
problems that required in the past tedious Dr. Housam Binous is a full time faculty
numerical and graphical techniques. We present member at the National Institute of Applied
the computation of the equilibrium diagram of a Sciences and Technology in Tunis. He earned a
the ternary mixture (benzene - ethanol - water). Diplôme d'ingénieur in Biotechnology from the
We also solve two problems proposed by Ecole des Mines de Paris and a Ph.D. in
Professor Wankat[1]. These problems concern Chemical Engineering from the University of
the extraction of acetic acid from water using California at Davis. His research interests
isopropyl ether. The graphical method, derived include the applications of computers in
by Hunter and Nash, is used to obtain the Chemical Engineering.
number of equilibrium stages for a specific
raffinate purity. Finally, the McCabe-Thiele
method is employed to give the same result.
These classic problems are junior and senior
level study material at the National Institute of
Applied Sciences in Tunis. The students excel in
these type of problems despite the fact that they
do not have prior knowledge of Mathematica.

COMPUTERS IN EDUCATION JOURNAL 81

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