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Estimation of Activity Coefficients for binary mixture VLE Data using

MATLAB

Article · October 2007

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 IARJSET ISSN (Online) 2393-8021
ISSN (Print) 2394-1588

International Advanced Research Journal in Science, Engineering and Technology

ISO 3297:2007 Certified
Vol. 3, Issue 10, October 2016

Estimation of Activity Coefficients for binary

mixture VLE Data using MATLAB
Tarun Jain1, Parminder Singh2
Student, Department of Chemical Engineering, Thapar University Patiala, India1
Assistant Professor, Department of Chemical Engineering, Thapar University Patiala, India2

Abstract: Vapor- liquid equilibrium data for three strongly associated binary systems was taken for estimation of
parameters of four different thermodynamic models by developing a general code using optimization techniques in
MATLAB software. Isobaric vapor-liquid equilibrium measurements are considered in this work for three binary
systems methanol-ethanoic acid, methanol-water and water-ethanoic acid at 101.325 kpa. None of the systems form an
azeotrope. The activity coefficient has been calculated taking into consideration the non-ideality of the mixture. The
experimental T, x, y data are used to estimate nonrandom two-liquid (NRTL), Wilson, Margules and VanLaar model
parameters, and these parameters in turn are used to calculate vapor phase compositions. The activity coefficients of the
solution were correlated with NRTL, Wilson, Margules, and VanLaar models through fitting by least-squares method.
The VLE data of binary system were well predicted from these binary interaction parameters of NRTL, Wilson,
Margules, and VanLaar model parameters without any additional adjustment to build the thermodynamic model of
VLE for binary system and obtain the vapor-pressure compositions and the calculated bubble points.

Keywords: Binary mixture, Vapor liquid equilibrium, Wilson, Margules, VanLaar, NRTL.

1. INTRODUCTION 2. RESULTS AND DISCUSSION

Mass transfer operations such as distillation are 2.1 Calculation of vapor-phase Mole Fraction y for
extensively used for separation or extraction of large Binary Systems from Model
number of liquid mixtures. Due to this, the knowledge of There are several methods concerning the correlation and
Vapor liquid equilibrium data is of great importance when predicting VLE data. VLE data can also be predicted and
it comes to accurate designing of required equipment. correlated using model-free approach. It was suggested by
Nonideality plays a very important role in industrial Wisniak’s group that novel model-free computation
processes and equipment design calculations. techniques and limiting conditions have been applied for
When VLE data is generated and phases are analyzed azeotropic systems [3]. But Segura and coworkers stated
using samples. While sampling the compositions of both that model-free approach dealt with VLE data in
liquid and gaseous phase change and accordingly behavior application of ternary systems [4, 5]. In this paper, for all
of system also changes. This decreases the possibility of three binary systems, activity coefficients were correlated
highly accurate VLE data. with Wilson [6], Margules [7], NRTL [8] and Van-Laar
This fact points towards the necessity for much analytical [9] equations. The Interaction parameters were computed
work which leads to enhance an interest in exploring new by minimizing the objective function using fitting by least-
methods for determination of equilibrium data that do not squares method.
involve sampling and analysis of vapor phase components.
Several methods have been suggested for determination of 2.2 Equations and models used for calculations are-
accurate data. Van Ness and coworkers classified these 1. Wilson Model
methods in two categories, direct and indirect methods [1]. One limitation of Wilson’s equation is that it is unable to
Direct method contains calculation of vapor compositions model liquid-liquid equilibria, but it is reasonably accurate
by integration of coexistence equation which was derived for modeling the liquid phase when correlating the vapor-
from Gibbs-Duhem equation [2]. Indirect methods involve liquid equilibria of many mixtures. Wilson equation
ascertaining which of the selected solution equations to the should be used only for liquid systems that are completely
Gibbs-Duhem equation which lead to best fit to the miscible or else for those limited regions of partially
experimental data, and determination of parametric values limited systems where only one liquid phase is present.
Λ12 Λ21
producing the best fit. This paper reports novel correlation lnγ1= -ln(x1+Λ12x2) + x2( − )
x1+Λ12x2 x2+Λ21x1
and prediction of VLE data for these isobaric binary Λ12 Λ21
systems at 101.25 kpa. Non ideality of mixture was lnγ2= -ln(x2+Λ21x1) + x1(x1+Λ12x2 − x2+Λ21x1)
corrected by the calculation of its activity coefficient,
which was obtained based on NRTL, Wilson, Margules 2. Van-Laar Model
and VanLaar models as function of T,x,y through non- The Van-Laar equation was derived from Van der Waals
linear fit of least squares method. equation. The original van der Waals parameters didn't

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give good description of vapor-liquid phase equilibria, concentration around a molecule is different from the bulk
which forced the user to fit the parameters to experimental concentration.
results. Because of this, the model lost the connection to G21 G12
lnγ1=x22[τ21( )2 + τ12 ]
x1+x2G21 (x2+x1G12)2
molecular properties, and therefore it has to be regarded as G12 G21
an empirical model to correlate experimental results. lnγ2=x1 [τ12(x2+x1G12 ) + τ21(x1+x2G21)2]
2 2

A21x2
lnγ1=A12 ( ) 2
lnG12= -α12τ12
A12x1+A21x2
A21x1 lnG21= -α21τ21
lnγ1=A21 (A12x1+A21x2) 2
Objective function in our work was taken as –
3. Margules Model N
γi,cal − γi,exp 2
The Margules activity model is a simple thermodynamic Objective function =
model for the excess Gibbs free energy of a liquid mixture 2
i=1
introduced in 1895 by Max Margules. In chemical
engineering the Margules Gibbs free energy model for Where N is the number of experimental points, γi,calc ,
liquid mixtures is better known as the Margules activity or γi,exp are activity coefficients of component i calculated
activity coefficient model. Although the model is old it has and experimental values from measured data, respectively.
the characteristic feature to describe extrema in the The method of least squares is a standard approach
activity coefficient which other models cannot. in regression analysis to the approximate solution
lnγ1= [A12+2(A21-A12)x1]x22 of overdetermined systems, i.e., sets of equations in which
lnγ2= [A21+2(A12-A21)x2]x12 there are more equations than unknowns. "Least squares"
means that the overall solution minimizes the(6)sum of the
4. NRTL (Non-Random Two-Liquid) Model squares of the errors made in the results of every single
The Non-random two-liquid model is an activity equation. The most important application is in data fitting.
coefficient model that correlates the activity coefficients of The best fit in the least-squares sense minimizes the sum
a compound i with its mole fractions in the liquid phase of squared residuals, a residual being the difference
concerned. It is frequently applied in the field of chemical between an observed value and the fitted value provided
engineering to calculate phase equilibria. The concept of by a model.
NRTL is based on the hypothesis of Wilson that the local

Table 1: Antoine coefficients of the compounds

Compound Ai Bi Ci
Methanol 7.19736 1574.99 -34.29
Water 7.07404 1657.46 -46.13
Ethanoic acid 6.42452 1479.02 -56.34

Table 2: Correlation parameters of activity coefficient

Equation Parameters Methanol(1)+water(2) Methanol(1)+ Ethanoic Water(1)+Ethanoic acid

acid (2) (2)
Van-Laar A12 0.8407 - 0.2777
A21 0.5386 - 0.4607
Fmin 0.0075 - 0.0421
Margules Λ12 0.8256 -0.335 0.2416
Λ21 0.4791 0.0219 0.4632
Fmin 0.0080 0.0599 0.0360
Wilson A12 0.4139 0.5307 1.2795
A21 1.0354 1.8843 0.4759
Fmin 0.0074 0.0784 0.0423
NRTL G12 -0.2831 2.7759 1.0233
G21 1.1457 -1.5237 -0.4846
Fmin 0.0075 0.0390 0.0405

Table 3: Experimental data for Methanol (1) + Water (2) System at 101.25 kpa

x1 y1 Texp γ1exp γ2exp

0.0484 0.2704 365.54 2.1436 1.0034
0.0539 0.3009 364.88 2.1147 1.0042

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0.0607 0.3213 364.12 2.0799 1.0053

0.0696 0.3492 363.19 2.0358 1.0069
0.0806 0.3866 362.13 1.9835 1.0092
0.0911 0.4126 361.21 1.9360 1.0117
0.1056 0.4492 360.05 1.8739 1.0155
0.1197 0.4762 359.04 1.8172 1.0197
0.1354 0.4885 358.02 1.7584 1.0248
0.1436 0.5047 357.53 1.7293 1.0277
0.1586 0.5323 356.70 1.6788 1.0334
0.1815 0.5677 355.56 1.6083 1.0428
0.2092 0.5969 354.35 1.5325 1.0555
0.2202 0.6031 353.91 1.5049 1.0609
0.2380 0.6237 353.24 1.4633 1.0701
0.2648 0.6519 352.32 1.4066 1.0847
0.2918 0.6681 351.48 1.3561 1.1005
0.3166 0.6923 350.76 1.3148 1.1157
0.3442 0.7197 350.02 1.2740 1.1336
0.4015 0.7431 348.61 1.2038 1.1730
0.4282 0.7443 348.00 1.1767 1.1924
0.4644 0.7613 347.21 1.1449 1.2194
0.5240 0.7860 345.98 1.1026 1.2656
0.6091 0.8231 344.33 1.0595 1.3338
0.6899 0.8633 342.85 1.0325 1.3995
0.8213 0.9221 340.56 1.0086 1.5038

Table 4: Experimental data for Methanol (1) + Ethanoic acid (2) System at 101.25 kpa

𝐱𝟏 𝐲𝟏 𝐓𝐞𝐱𝐩 𝛄𝟏𝐞𝐱𝐩 𝛄𝟐𝐞𝐱𝐩

0.0359 0.1574 386.23 0.9388 0.9999
0.0410 0.1664 385.56 0.9393 0.9999
0.0648 0.2719 382.68 0.9419 0.9997
0.0741 0.3133 381.90 0.9428 0.9996
0.0859 0.3333 380.60 0.9441 0.9995
0.1040 0.3830 379.06 0.9460 0.9992
0.1280 0.4602 377.35 0.9485 0.9988
0.1629 0.5213 374.70 0.9521 0.9981
0.1919 0.5873 372.43 0.9551 0.9973
0.2510 0.6495 368.44 0.9609 0.9954
0.3391 0.7538 363.56 0.9692 0.9916
0.4401 0.8232 357.71 0.9776 0.9857
0.5829 0.8999 350.75 0.9874 0.9748
0.7050 0.9389 346.39 0.9936 0.9633
0.7509 0.9533 344.06 0.9955 0.9583
0.8109 0.9693 342.35 0.9974 0.9515
0.8711 0.9766 340.75 0.9988 0.9442
0.9161 0.9850 340.00 0.9995 0.9384

Table 5: Experimental data for Water (1) + Ethanoic acid (2) System at 101.25 kpa

𝐱𝟏 𝐲𝟏 𝐓𝐞𝐱𝐩 𝛄𝟏𝐞𝐱𝐩 𝛄𝟐𝐞𝐱𝐩

0.0665 0.1140 387.22 1.4161 1.0025
0.0749 0.1288 387.00 1.4046 1.0031
0.0855 0.1603 386.48 1.3903 1.0040
0.0995 0.1938 385.86 1.3117 1.0054
0.1507 0.2802 384.16 1.2888 1.0121
0.1722 0.3155 383.44 1.2684 1.0156
0.2168 0.3676 382.39 1.2171 1.0242

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0.2502 0.4101 381.53 1.1838 1.0316

0.2936 0.4407 380.94 1.1589 1.0425
0.3303 0.4815 380.20 1.1318 1.0528
0.3756 0.5253 379.40 1.0965 1.0666
0.4465 0.5890 378.27 1.0768 1.0908
0.4946 0.6274 377.61 1.0543 1.1087
0.5615 0.6777 376.80 1.0427 1.1355
0.6036 0.7137 376.24 1.0315 1.1533
0.6517 0.7546 375.59 1.0213 1.1746
0.7067 0.7849 375.11 1.0217 1.1998
0.7045 0.7848 375.11 1.0148 1.1988
0.7507 0.8173 374.71 1.0091 1.2207
0.8008 0.8501 374.31 1.0035 1.2451
0.8723 0.9011 373.80 1.0016 1.2809
0.9116 0.9315 373.54 1.0004 1.3009

Figure 1- T-xy diagram of Methanol (1) +Water(2) System at 101.25 kpa

Figure 2- Plot of γ1 and γ2 vs x1 of Methanol(1)+Water(2) System at 101.25 kpa

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Figure 3- γcalc and γexp vs x1 of Methanol(1)+Water(2) System at 101.25 kpa

Figure 4- T-xy diagram of Methanol(1)+Ethanoic acid(2) System at 101.25 kpa

Figure 5- Plot of γ1 and γ2 vs x1 of Methanol(1)+Ethanoic acid(2) System at 101.25 kpa

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Figure 6- T-xy diagram of Water(1)+Ethanoic acid(2) System at 101.25 kpa

Figure 7- Plot of γ1 and γ2 vs x1 of Water(1)+Ethanoic acid(2) System at 101.25 kpa

3. MATLAB CODE

3.1 Code for determining activity coefficients of binary y2=1-y1;

Methanol(1)+Water(2) System using various models. p1= 10.^(a1 - b1./(T+c1));
%-----------------------Methanol(1)+Water(2) SYSTEM----- p2= 10.^(a2 - b2./(T+c2));
-----% gamma1_exp=(y1.*P)./(p1.*x1);
gamma2_exp=(y2.*P)./(p2.*x2);
P=101.325; gamma1_calc=
a1=7.19736;b1=1574.99;c1=-34.29; @(c)exp(c(1).*(((c(2).*x2)./(c(1).*x1+c(2).*x2)).^2));
a2=7.07404;b2=1657.46;c2=-46.13; gamma2_calc=
%-------------------VAN LAAR--------------------% @(c)exp(c(2).*(((c(1).*x1)./(c(1).*x1+c(2).*x2)).^2));
x1=[0.0484 0.0539 0.0607 0.0696 0.0806 0.0911 0.1056 ini_guess = [1,1];
0.1197 0.1354 0.1436 0.1586 0.1815 0.2092 0.2202 U=@(c)(0.5*(sum(((gamma1_calc(c)-
0.2380 0.2648 0.2918 0.3166 0.3442 0.4015 0.4282 gamma1_exp)+(gamma2_calc(c)-gamma2_exp)).^2)));
0.4644 0.5240 0.6091 0.6899 0.8213 ]; display 'Vanlaar model activity coeffcients'
y1=[0.2704 0.3009 0.3213 0.3492 0.3866 0.4126 0.4492 [c,fmin] = fminsearch(U,ini_guess)
0.4762 0.4885 0.5047 0.5323 0.5677 0.5969 0.6031 gamma1_calcvalue=exp(c(1).*(((c(2).*x2)./(c(1).*x1+c(2)
0.6237 0.6519 0.6681 0.6923 0.7197 0.7431 0.7443 .*x2)).^2));
0.7613 0.7860 0.8231 0.8633 0.9221 ]; gamma2_calcvalue=exp(c(2).*(((c(1).*x1)./(c(1).*x1+c(2)
T=[366.00 365.05 364.40 363.50 362.25 361.35 360.05 .*x2)).^2));
359.09 358.60 358.00 356.95 355.55 354.35 354.10 %---------Graphs----------%
353.25 352.05 351.35 350.30 349.05 347.95 347.90 subplot(3,3,1),plot(x1,T,'*',y1,T,'-*'),xlabel('x1(*),y1(-
347.20 346.20 344.80 343.31 341.20 ]; )'),ylabel('T'),title('Methanol-Water
Tsat1 = 338.1; Tsat2 = 373.16; system'),subplot(3,3,2),plot(x1,gamma1_calcvalue,x2,gam
x2=1-x1; ma2_calcvalue),xlabel('xi'),ylabel('gammai'),title('Van

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Vol. 3, Issue 10, October 2016

Laar model'),
,subplot(3,3,6),plot(x1,gamma1_exp,x1,gamma1_calcvalu
e),xlabel('xi'),ylabel('gamma_exp &
gamma_calc'),title('Van Laar model');

4. CONCLUSION

The experimental data of three binary mixture i.e.

methanol + water, methanol + ethanoic acid and water +
ethanoic acid at 101.325 kpa was correlated using the
NRTL, Wilson, Margules, and van Laar equations. The
vapor liquid equilibrium data of these binary mixture was
available in literature. So activity coefficients of these
systems were determined using MATLAB. It was shown
that the deviations of NRTL, Wilson, Margules, and van
Laar equations are reasonably small. The calculated
bubble points accorded well with the experimental data.
The results show that the calculated bubble point is well
fitted by the models, which satisfy the need for the design
and operation of separation process in chemical industry.
Moreover, the method will provide theoretical guidance
for the research of VLE data of strongly associating
system of vapor and liquid phase in non-ideal behavior.

REFERENCES

[1] J.J.Ljunglin and H.C. van Ness, “Calculation of vapor-liquid

equilibria from vapor pressure data,” Chemical Engineering
Science, vol.17, no. 7, pp.531-539, 1962.
[2] E.Hala, J.Pick, V.Fried, and O. Vilim, Vapor-Liquid Equilibrium,
Pergamon, New York, NY, USA, 1958.
[3] J.Wisniak,A.Apelblat, and H.Segura, “Application of model-free
computation techniques and limiting conditions for azeotropy. An
additional assessment of experimental data,” Chemical Engineering
Science, vol. 52, no. 23, pp. 4393-4402, 1997.
[4] E. Lam, A. Mejia, H. Segura, J. Wisniak, and S. Loras, “A model-
free approach data treatment of vapor-liquid equilibrium data in
ternary systems. . 1. Theory and numerical procedures,” Industrial
and Engineering Chemistry Research, vol. 40, no. 9, pp.2134-2148,
2001.
[5] E. Lam, A. Mejia, H. Segura, J. Wisniak, and S. Loras, “A model-
free approach data treatment of vapor-liquid equilibrium data in
ternary systems.2.Application”. Industrial and Engineering
Chemistry Research, vol. 40, no. 9, pp.2149-2159, 2001.
[6] G.M. Wilson, “Vapor-liquid equilibrium. A new expression for the
excess free energy of mixing,” Journal of American Chemical
Society, vol. 86, no. 2, pp.127-130, 1964.
[7] M.S. Margules, “On the composition of saturated vapors of
mixtures,” Akademie der Wissenschaften in Wien, Mathematisch-
Naturwissenschaftliche Klasse Abteilung 2, vol. 104, pp.1234-
1239, 1895.
[8] H. Renon and J.M. Prausnitz, “Estimation of parameters for the
NRTL equation for excess gibbs energies of strongly non-ideal
liquid mixtures,” Industrial & Engineering Chemistry Process
Design and Development, vol. 8, no. 3, pp. 413-419, 1969.
[9] J.J. Van Laar, “The vapor pressure of binary mixtures,” Zeitschrift
fur Physikalische Chemie, vol. 72, pp.723-751, 1910.

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