CHE513 –Advanced Chemical Engineering Thermodynamics - Term Project – Sem.

181

Equilibrium calculations for mixtures of n-Hexane and Benzene using

Extended Van Laar model

Syed Samsamuddin g201803440, Hassam Mazhar g201803660

Department of Chemical Engineering, King Fahd University of Petroleum & Minerals (KFUPM), Dhahran, Saudi Arabia

Abstract – Vapor-Liquid Equilibrium calculations are presented for a different binary and ternary
mixtures. Extended Van Laar model which accounts for temperature dependence of the energy
parameter as proposed by Y. Peng was used to calculate the activity coefficient and some of the
results were reproduced. Systems which illustrated azeotropic behavior were added with suitable
solvent to enhance the separation process. The recommended solvent for n-hexane – benzene is
ethylenediamine (EDA) as suggested by C. Cumming et. al. Due to limited availability of experiment
data to estimate the binary interaction parameters of n-hexane-benzene-EDA mixture, a different
ternary mixture of n-hexane – benzene- cyclohexane was used to verify the calculation approach
and to validate the robustness of the Extended Van Laar model for multicomponent systems. The
predicted bubble temperatures were then compared to the available experimental data. The results
showed good agreement of the predicted bubble temperatures and the vapor-liquid mole fractions
with the experiment values. Copyright © 2018

Keywords: VLE, LLE, Benzene, Hexane, Cyclohexane, Sulfolane, Binary, Ternary, EDA

Nomenclature
VLE Vapor Liquid Equilibrium
LLE Liquid-Liquid Equilibrium
NRTL Non-Random Two Liquid
EDA Ethylene Diamine
I. Objectives
The objectives of this work are to:
1. Reproduce VLE (Vapor-Liquid-Equilibrium)
data for different binary mixtures viz. n-
hexane – benzene, benzene, – n-heptane,
benzene – cyclohexane and hexane –
cyclohexane using Extended Van Laar Models
for activity coefficient as presented by Ding-
Yu Peng [1].
2. Perform VLE calculations for ternary mixture
n-hexane, benzene, and the selected solvent.
3. Adjust the operating conditions to get LLE
(Liquid-Liquid-Equilibrium) for ternary
mixture n-hexane, benzene, and solvent and
perform LLE calculations to analyze this
separation process based on extraction.
4. To replace the solvent with a salt to carry the
LLE calculations.
II. Introduction
Vapor-Liquid Equilibrium is very important, in
particular for chemical engineers because of its wide
applications such as for the design of distillation
columns and other related separation processes. It
also renders a scope for improving the separation
processes based on the phase behavior. The accuracy
of the VLE calculations is based on the ideality of the
mixture in vapor as well as in the liquid phase.
Selection of appropriate models to account for the
non-ideality will help improve the VLE calculations.
The non-ideality of the mixture is characterized by
the activity coefficient of the mixture in modified
Rault’s Law. There are several models available to
calculate the activity coefficient such as NRTL,
Wilson, Margules, and Van Laar etc.
In this project, a model proposed by Ding-Yu Peng
called Extended Van Laar model was used to
perform the VLE calculations for different binary
and ternary mixtures. In comparison to the original
Van Laar model, the Extended Van Laar model
accounts for the temperature dependence of the
energy parameter (a) as opposed to Van Der Waal’s
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 CHE513 –Advanced Chemical Engineering Thermodynamics - Term Project – Sem. 181
approach which considers the energy parameter as a
constant for any given system thus making the
Extended Van Laar model applicable for systems
exhibiting both positive and negative deviations
from Raoult's Law.
The vapor-liquid equilibrium for the selected
binary system n-hexane (1) and benzene (2) was
studied. To this system, a solvent was introduced to
analyze the system behavior for ternary VLE. By
adjusting the temperature and pressure, LLE
calculations were performed for the same ternary
system to analyze this separation process based on
extraction. Furthermore, the ternary LLE
calculations can be extended by replacing the solvent
with a suitable ionic liquid to enhance the separation.
III. Literature Review
VLE calculations for non-ideal systems require the
use of robust models to account for the non-ideality.
There are several models available throughout the
literature. Of them, the most common are Van Laar
[2], Margules [3], Wilson [4], NRTL [5] etc. These
models relate the Excess Gibb’s Free Energy to
activity coefficient as a function of liquid mole
fractions. P. Colburn et. al. [6] offered ways to
evaluate the experimental data to Vapor-Liquid
Equilibrium. The Extended Van Laar model as
proposed by Ding-Yu Peng provides a reliable model
for systems showing deviation from Raoult's law
while accounting for the temperature dependence of
energy parameter used in the Van Der Waal’s
equation of state. Ding-Yu Peng’s work provides
experimental evidence for the accuracy of this
model. It was also extended to ternary &
multicomponent systems and compared to
experimental data. His model requires the knowledge
of the interaction parameter between binary pairs of
molecules for accurate results to calculate the excess
Gibb’s free energy.
There have been several works done for the VLE
calculations of the selected system of n-hexane and
benzene [7] [8] [9]. S. Govindaswami et. al used
Wilson models for estimating the activity coefficient
for the binary and ternary system. A. Harris et. al.
used NRTL model for the activity coefficient of Four
Binary Systems at 363.15 K. S. Nebig et. al. used the
UNIFAQ models to estimate the activity coefficient
and perform VLE calculations for binary systems.
Liquid-Liquid-Extraction becomes more important
for systems in which vapor-liquid equilibrium
separation is difficult because of azeotrope formation
for systems with very close boiling points i.e. relative
volatility becomes 1 at certain saturation
temperatures. J. Chen et. al. [10] presented Liquid-
liquid equilibrium of multi-component systems. The
equilibrium calculations were performed using
NRTL models. A. Kareem et. al. [11] studied the
LLE for a ternary system of n-hexane, benzene with
phosphonium based deep eutectic solvent.
Ionic liquids may be used for liquid-liquid
extraction as an alternative to routine solvents. Ionic
liquids are the subject of recent studies because the
use of ionic liquids provides alternative methods of
separations which may be more economical
providing ease of recovery from the extract [12] [13].
In this work, a binary mixture of n-hexane and
benzene was selected to perform VLE calculations
using Extended Van Laar model. Bubble T
calculations were performed at atmospheric
pressure. A solvent was introduced to this binary
mixture and ternary calculations were performed at
the same operating pressure. For this ternary mixture,
the operating conditions were changed to perform the
LLE calculations.
IV. Methodology
The modified Raoult's Law for calculations of liquid
(x) and vapor (y) compositions is given by:
𝑦𝑖 𝑃 = 𝑥𝑖 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡 (1)
where 𝛾𝑖 is the activity coefficient of the species (i),
P and 𝑃𝑖𝑠𝑎𝑡 are the operating and saturation pressures
respectively.
The Excess Gibbs Energy for the binary system is
extended to the multicomponent system as suggested
by Y. Peng is given by:
𝐺 𝐸 ∑𝑁−1 𝑁
𝑖=1 ∑𝑗=𝑖+1 𝑥𝑖 𝑥𝑗 𝑏𝑖 𝑏𝑗 𝜀𝑖𝑗
=
𝑅𝑇 ∑𝑁𝑖=1 𝑥𝑖 𝑏𝑖
Where 𝜀𝑖𝑗 is the interaction parameter between
component i and j and b is the size parameter
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 CHE513 –Advanced Chemical Engineering Thermodynamics - Term Project – Sem. 181

calculated from the Peng-Robinson equation of state was found that our T-x-y calculations were in good
given by: agreement with the first four plots reported by Y.
0.07796 𝑅𝑇𝑐 Peng.
𝑏=
𝑃𝑐
Where 𝑇𝑐 and 𝑃𝑐 are critical temperature and pressure
respectively.

And the activity coefficient is given by:

𝑁
𝑏𝑘 𝐺𝐸
𝑙𝑛𝛾𝑘 = 𝑁 (∑ 𝑥𝑖 𝑏𝑖 𝜀𝑖𝑘 − )
∑𝑖=1 𝑥𝑖 𝑏𝑖 𝑅𝑇
𝑖=1
𝑖≠𝑘

The value of the interaction parameters at 101.3 kPa

reported by Y. Peng is given in below table:

TABLE I
INTERACTION PARAMETERS Figure 1: T-x1-y1 for Benzene (1) and n-Heptane (2) at
Component Component 53.33kPa
102 𝜀12
1 2
n-Hexane Benzene 0.4909
n-Heptane Benzene 0.4962
Cyclohexane Benzene 0.4283
Cyclohexane n-Hexane 0.0265

𝑁
𝑡𝑖𝑠𝑎𝑡 𝑇𝑒𝑠𝑡𝑖𝑚𝑎𝑡𝑒 = ∑ 𝑥𝑖 𝑡𝑖𝑠𝑎𝑡
From Antoine eqn. 𝑖=1

𝑃𝑖𝑠𝑎𝑡
Calculate 𝛾𝑖 , 𝑃𝑖𝑠𝑎𝑡 𝛼=
𝑃𝑗𝑎𝑠𝑡

Figure 2: T-x1-y1 for Benzene (1) and Cyclohexane (2) at

𝑃 101.33kPa
Calculate New T 𝑁𝑒𝑤 𝑃1𝑠𝑎𝑡 = 𝑥2 𝛾2
Until T converges 𝑥1 𝛾1 +
𝛼

Algorithm for Bubble Temperature calculation

V. Results and Discussions

V.1. VLE Binary Mixtures

The Extended Van Laar models were tested for
different binary mixtures by reproducing VLE
plots of T-x-y for Benzene – n-heptane, Benzene-
cyclohexane, n-hexane - cyclohexane and n-
hexane – benzene. The binary interaction
parameters used were presented by Y. Peng which Figure 3: T-x1-y1 for Hexane (1) and Cyclohexane (2) at
101.33kPa
were calculated using Barker’s method [13]. It

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 CHE513 –Advanced Chemical Engineering Thermodynamics - Term Project – Sem. 181
Figure 4: T-x1-y1 for Hexane (1) and Benzene (2) at
101.33kPa
The reliability of our VLE calculations was verified
with the experimental data. For Benzene – n-Heptane
the source of the experimental data was Nielsen et.
al. [14], for benzene-cyclohexane was Richards et.
al. [15], for Hexane – Cyclohexane was Ridgway et
al. [16].
The system of our interest is Hexane (1) and
Benzene (2). The VLE calculations were performed
for this system and then compared to the
experimental data as reported by Ridgway et al. It
can be observed from the plotted figures that the
calculations are accurate. The VLE binary figures
were reproduced using the new Matlab code which
was developed as per the Bubble T calculation
algorithm. The Matlab code is attached at the end of
this paper. The error tolerance for the iterations was
set to be less than 0.0001 before the desired bubble
temperature is converged.
V.2. VLE Ternary Mixtures
The VLE calculation for the binary mixture Hexane
(1) and Benzene (2) was extended to ternary systems.
Initially, a Matlab program was developed to
perform the calculations. The Extended Van Laar
model in ternary form was used to calculate the
activity coefficient. The suggested solvent for
Ternary VLE of Hexane and Benzene mixture is
Ethylene-diamine as recommended by C. Cumming
[17]. Due to unavailability of literature for the above
solvent, the calculations were tested for the different
ternary system. In order to validate our calculation
approach, a different ternary system was selected to
perform the Ternary VLE calculations.
The algorithm for the calculations is similar to a
binary system as mentioned in the previous section.
The Matlab code used for the calculations is attached
at the end of this paper. The Matlab code is a
combination of a function file & main file. The
function file called ‘vlet’ consists of the iterative
loops. The function consists of inter loops which
perform the bubble temperature calculations for
every possible combination of component liquid
mole fractions, i.e. x1, x2 and x3. The generated data
was exported to Excel for data analysis. The data was
filtered to remove the redundant and physically
unrealizable combinations of the liquid mole
fractions. The resultant data provided the range of
Bubble Temperatures for the ternary mixture of
Hexane, Benzene, and Cyclohexane. The calculated
bubble temperatures were verified against
experimental data as reported by Li et. al [18] as
depicted in figure 5.
■ - Tcalc
Figure 5: VLE - Ternary Bubble T calculations for
Hexane-Benzene-Cyclohexane
V.3. LLE Ternary Mixtures (Solvent Extraction)
Ethylenediamine (EDA) is miscible with benzene
while immiscible in hexane. It is a potential solvent
for Benzene – Hexane separation. The saturation
temperature at atmospheric pressure is 117 degC.
The VLE operating conditions of the Hexane –
Benzene – EDA ternary system can be changed to get
LLE by changing the temperature to be well below
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 CHE513 –Advanced Chemical Engineering Thermodynamics - Term Project – Sem. 181
the lowest saturation temperature of the VLE. So far
in the literature, there seems to be limited evidence
reported about the research done on LLE using this
ternary system.
VI. Conclusions & Recommendations
The Extended Van Laar model was reproduce the
VLE T-x-y curves for n-hexane – benzene, benzene,
– n-heptane, benzene – cyclohexane and hexane –
cyclohexane and compared to the experimental
values. The Extended Van Laar model was found be
in good approximation with the experimental results.
Furthermore, predicted VLE data of ternary
system of n-hexane, benzene and cyclohexane was
compared to experimental data reported by Li et. al.
The predicted bubble temperatures were in very good
agreement with the experimental values.
The LLE and ternary VLE and calculations of the
proposed system n-hexane, benzene and
ethylenediamine (solvent) can be produced using the
same approach provided in the Matlab program upon
availability of the experimental data to estimate the
binary interaction parameters, as required by the
Extended Van Laar model.
REFERENCES
[1] Peng, D.-Y. (2010). Extending the Van Laar Model to
Multicomponent Systems. The Open Thermodynamics
Journal, 129-140.
[2] J. J. van Laar, “Über Dampfspannungen von binären
Gemischen (The vapor pressure of binary mixtures)”, Z.
Physik. Chem., vol. 72, pp. 723-751, May 1910.
[3] M. Margules, “Über die Zusammensetzung der
gesättigten Dämpfe von Mischungen”, Sitzungsber Akad.
Wiss. Wien, Math. Naturw. Klasse, II, vol. 104, pp.
1243-1278, 1895
[4] G. M. Wilson, “Vapor-liquid equilibrium. XI. A new
expression for the excess free energy of mixing”, J. Am.
Chem. Soc., vol. 86, pp.127-130, January 1964
[5] H. Renon and J. M. Prausnitz, “Local compositions in
thermodynamic excess functions for liquid mixtures”,
AIChE J., vol. 14, pp. 135-144, January 1968
[6] H. C. Carlson and A. P. Colburn, “Vapor-liquid
equilibria of nonideal solutions. Utilization of theoretical
methods to extend data”, Ind. Eng. Chem., vol. 34,
pp.581-589, May 1942
[7] Roger A. Harris‡, Roland Wittig, “Vapor-Liquid
Equilibria for Four Binary Systems”, J. Chem. Eng. Data,
2003, 48 (2), pp 341–343.
[8] S. Govindaswamy, AN. Andlappan, “Vapor-Liquid
Equilibrium Data at Atmospheric Pressure for the
Ternary”, Department of Technology, Annamalai
University, Annamalainagar-608101
[9] Silke Nebig, Rainer Bölts, “Measurement of vapor–
liquid equilibria (VLE) and excess enthalpies (HE) of
binary systems”, Fluid Phase Equilibria Volume 258,
Issue 2, 15 September 2007, Pages 168-178
[10] Jian Chen, Li-PingDuan, “Liquid–liquid equilibria
of multi-component systems”, Fluid Phase Equilibria
Volume 173, Issue 1, 5 August 2000, Pages 109-119
[11] A. Kareema,∗, Farouq S. Mjalli, “iquid–liquid
equilibria for the ternary system”, J. Chem. Eng. Data,
2018, 63 (3), pp 613–624.
[12] Alberto Arce a, Martyn J. Earle, “Separation of
aromatic hydrocarbons from alkanes using the ionic
liquid 1-ethyl-3-methylimidazoliumbis{(trifluoromethyl)
sulfonyl}amide” Green Chem., 2007, 9, 70-74.
[13] Ionic Liquids in Synthesis, ed. P. Wasserscheid and
T. Welton, Wiley-VCH, Weinheim, 2003 [13]
J. A. Barker, “Determination of activity coefficients from
total pressure measurements”, Aust. J. Chem., vol. 6, pp.
207-210, August 1953.
[14] R. L. Nielsen and J. H. Weber, “Vapor-liquid
equilibria at subatmospheric
pressures. Binary and ternary systems containing ethyl
alcohol, benzene, and n-heptane”, J. Chem. Eng. Data,
vol. 4, pp. 145-151, April 1959
[15] A. R. Richards and E. Hargreaves, “Vapor-liquid
equilibria of close-boiling binary hydrocarbon mixtures”,
Ind. Eng. Chem., vol. 36, pp. 805-808, September 1944
[16] K. Ridgway and P. A. Butler, “Some physical
properties of the ternary system benzene-cyclohexane-n-
hexane”, J. Chem. Eng. Data, vol. 12, pp. 509-515,
October 1967
[17] C. Cumming F. Morton, “Separation of benzene
and n‐hexane by means of ethylenediamine as a solvent:
Molar solutropy” Volume3, Issue8, August 1953 Pg.
358-366
[18] I. P.-C. Li, J. Polak, and B. C.-Y. Lu, “Ternary
vapor-liquid equilibria for n-hexane + cyclohexane +
benzene”, J. Chem. Thermodynamics, vol. 5, pp. 417-
424, May 1974
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 CHE513 –Advanced Chemical Engineering Thermodynamics - Term Project – Sem. 181

Matlab Codes:

VLE Binary Calculations Matlab Code:

Main File:
clc
clear

%Hexane, Benzene:
[T11,X11,Y11] = vleb(1.0132,0.004909, 507.6,30.25, 13.8193, 2696.04, 224.317,562.2, 48.8,
13.7819, 2726.81, 217.572);
subplot(2,2,1)
plot(X11,T11)
hold on
plot(Y11,T11);
hold on

TexpHBK = [353.25 350.75 348.25 344.05 342.55 341.95 341.95];

TexpHB = TexpHBK-273.15;
x1expHB = [0 0.073 0.172 0.4620 0.692 0.962 1];
y1expHB = [0 0.14 0.268 0.54 0.725 0.964 1];

plot(x1expHB,TexpHB,'*', y1expHB, TexpHB,'*')

%Hexane, Cyclo-hexane:
[T12,X12,Y12] = vleb(1.0132,0.000265, 507.6,30.25, 13.8193, 2696.04, 224.317,553.6,
40.73, 13.6568, 2723.44,220.618);
subplot(2,2,2)
plot(X12,T12)
hold on
plot(Y12,T12);
hold on

TexpHCK = [353.87 352.65 351.35 347.85 346.85 343.20 341.85];

TexpHC = TexpHCK-273.15;
x1expHC = [0.00 0.082 0.167 0.438 0.523 0.877 1];
y1expHC = [0 0.121 0.226 0.523 0.602 0.904 1];

plot(x1expHC,TexpHC,'*', y1expHC, TexpHC,'*')

hold on

%Benzene, Cyclo-hexane:
[T13,X13,Y13] = vleb(1.0132,0.004283, 562.2, 48.8, 13.7819, 2726.81, 217.572,553.6,
40.73, 13.6568, 2723.44,220.618);
subplot(2,2,3)
plot(X13,T13)
hold on
plot(Y13,T13);
hold on

TexpBCK = [353.85 352.65 352.05 350.65 350.55 352.45 353.25];

TexpBC = TexpBCK-273.15;
x1expBC = [0 0.101 0.171 0.428 0.571 0.945 1];
y1expBC = [0 0.131 0.211 0.445 0.564 0.926 1];

plot(x1expBC,TexpBC,'*', y1expBC, TexpBC,'*')

hold on

%Benzene, Heptane:
[T14,X14,Y14] = vleb(0.5333,0.004962, 562.2, 48.8, 13.7819, 2726.81, 217.572,540.2,
27.40, 13.8622, 2910.26, 216.432);
subplot(2,2,4)
plot(X14,T14)
hold on
plot(Y14,T14);
hold on

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 CHE513 –Advanced Chemical Engineering Thermodynamics - Term Project – Sem. 181

TexpBH = [77.9 73.9 70.6 64.4 63.3 60.8 60.3];

x1expBH = [0 0.1 0.2 0.5 0.6 0.9 1];
y1expBH = [0 0.218 0.373 0.66 0.727 0.916 1];

plot(x1expBH,TexpBH,'*', y1expBH, TexpBH,'*')

hold on

Fuction File:
function [T1,X1,Y1] = vleb(P,e12,Tc1,Pc1,A1,B1,C1,Tc2,Pc2,A2,B2,C2)

%Temperature are in K, Pressure are in bar, Antoine Constants for deg C & kPA

Pkpa = P*100;%Kpa
Pc2kpa = Pc2*100;
Pc1kpa = Pc1*100;
R = 8310;
%Initial Guess for Saturation Temperatures in deg C:

t1sat = ((B1/(A1-log(Pkpa)))-C1);
t2sat = ((B2/(A2-log(Pkpa)))-C2);

% Peng Robinson Constants for the size terms:

b1 = (0.07780*R*Tc1)/Pc1kpa;
b2 = (0.07780*R*Tc2)/Pc2kpa;

x1= 0; % initial value for x1 calculations will be repeated until x1 = 1;

cx = 0;
output = zeros(100,3);

while x1<=1;
cx=cx+1;
T = zeros(100,1);%Changing T to vector;
c = 0; % counter;
tol = 1;
%initial guess for temperature
T(1) = (x1*t1sat) + ((1-x1)*t2sat);

while tol>0.0001;% accuracy of the iteration

c=c+1;

GeRT = (x1*(1-x1)*b1*b2*e12)/(x1*b1+((1-x1)*b2));
gamma1 = exp((b1/((x1*b1)+((1-x1)*b2)))*(((1-x1)*b2*e12)-GeRT));
gamma2 = exp((b2/((x1*b1)+((1-x1)*b2)))*((x1*b1*e12)-GeRT));

P1sat = exp(A1-(B1/(T(c)+C1)));
P2sat = exp(A2-(B2/(T(c)+C2)));

Alpha = P1sat/P2sat;

P1sat1 = Pkpa/(x1*gamma1+(((1-x1)*gamma2)/Alpha));
T(c+1) = (B1/(A1-log(P1sat1))-C1); % in degree C
tol = abs(T(c)-T(c+1));
end
y1 = (x1*gamma1*P1sat1)/Pkpa;
output(cx,1) = T(c+1);
output(cx,2) = x1;
output(cx,3) = y1;
x1=x1+0.01;
end

T1 = output(:,1);
X1 = output(:,2);
Y1 = output(:,3);

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 CHE513 –Advanced Chemical Engineering Thermodynamics - Term Project – Sem. 181

VLE Ternary Matlab Code:

Main File:

clc
clear

%Hexane, Benzene, Cyclohexane:

[T11, X11, Y11, X22, Y22, X33,Y33] = vlet2(1.0132,0.004909,0.000265,0.004283,507.6,30.25,
13.8193, 2696.04, 224.317,562.2, 48.8, 13.7819, 2726.81, 217.572,553.6, 40.73, 13.6568,
2723.44,220.618 );

O = [T11 X11 X22 X33 Y11 Y22 Y33];

Function File:

function [T1,X1,Y1,X2,Y2,X3,Y3] =
vlet(P,e12,e13,e23,Tc1,Pc1,A1,B1,C1,Tc2,Pc2,A2,B2,C2,Tc3,Pc3,A3,B3,C3)

%Temperature are in K, Pressure are in bar, Antoine Constants for deg C & kPA
Pkpa = P*100;%Kpa
Pc2kpa = Pc2*100;
Pc1kpa = Pc1*100;
Pc3kpa = Pc3*100;
R = 8310;

%Initial Guess for Saturation Temperatures in deg C:

t1sat = ((B1/(A1-log(Pkpa)))-C1);
t2sat = ((B2/(A2-log(Pkpa)))-C2);
t3sat = ((B3/(A3-log(Pkpa)))-C3);

% Peng Robinson Constants for the size terms:

b1 = (0.07780*R*Tc1)/Pc1kpa;
b2 = (0.07780*R*Tc2)/Pc2kpa;
b3 = (0.07780*R*Tc3)/Pc3kpa;

x1= 0; % initial value for x1 calculations will be repeated until x1 = 1;

output = zeros(1000000,7);

cx1=0;
while x1<=1;
x2 = 0;
cx1=cx1+1;

while x2<=1

x3=abs(1-x1-x2);
cx=cx1;
while x3<=1;
T = zeros(1000000,1);%Changing T to vector;
cx=cx+1;
tol = 1;
%initial guess for temperature
T(1) = (x1*t1sat) + (x2*t2sat)+(x3*t3sat);
c = cx; % counter;
while tol>0.0001;% accuracy of the iteration
c=c+1;

GeRT =
((x1*x2*b1*b2*e12)+(x2*x3*b2*b3*e23)+(x1*x3*b1*b3*e13))/((x1*b1)+(x2*b2)+(x3*b3));
gamma1 = exp((b1/((x1*b1)+(x2*b2)+(x3*b3)))*((x2*b2*e12)+(x3*b3*e13)-
GeRT));
gamma2 = exp((b2/((x1*b1)+(x2*b2)+(x3*b3)))*((x1*b1*e12)+(x3*b3*e23)-
GeRT));

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 CHE513 –Advanced Chemical Engineering Thermodynamics - Term Project – Sem. 181

gamma3 = exp((b3/((x1*b1)+(x2*b2)+(x3*b3)))*((x1*b1*e13)+(x2*b2*e23)-
GeRT));

P1sat = exp(A1-(B1/(T(c)+C1)));
P2sat = exp(A2-(B2/(T(c)+C2)));
P3sat = exp(A3-(B3/(T(c)+C3)));

Alpha12 = P1sat/P2sat;
Alpha13 = P1sat/P3sat;

P1sat1 = Pkpa/((x1*gamma1)+((x2*gamma2)/Alpha12)+((x3*gamma3)/Alpha13));
T(c+1) = (B1/(A1-log(P1sat1))-C1); % in degree C
tol = abs(T(c)-T(c+1));
end

y1 = (x1*gamma1*P1sat1)/Pkpa;
y2 =(x2*gamma2*P2sat)/Pkpa;
y3 = 1-y2-y1;

output(c,1) = T(c+1);
output(c,2) = x1;
output(c,3) = y1;
output(c,4) = x2;
output(c,5) = y2;
output(c,6) = x3;
output(c,7) = y3;
format shortg
A = [T(c+1) x1 x2 x3 y1 y2 y3]
x3 = x3+0.01;
end
x2 = x2+0.01;
end
x1=x1+0.01;
end
T1 = output(:,1);
X1 = output(:,2);
Y1 = output(:,3);
X2 = output(:,4);
Y2 = output(:,5);
X3 = output(:,6);
Y3 = output(:,7);