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Vapor-liquid equilibrium

2089

Tilman Knorr1
Eberhard Aust2

Research Article

Karl-Heinz Jacob2

Calculation of Vapor-Liquid Equilibrium Data


of Binary Mixtures Using Vapor Pressure
Data*

University of ErlangenNrnberg, Institute of


Chemical Reaction
Engineering, Erlangen,
Germany.
Georg-Simon-Ohm
Hochschule, Department of
Applied Chemistry, Nrnberg,
Germany.

The design of plants or unit operations requires the knowledge of data for multicomponent systems. An approach is presented for the regression of binary interaction parameters required for the calculation of activity coefficients. Binary
vapor pressure data are used to correlate these parameters for calculation of
vapour/liquid equilibrium data. The advantage of the approach is the fact that
only easily measured vapor pressure data are required. The procedure is demonstrated by means of two binary mixtures. Parameter regression, prediction of
vapour/liquid equilibrium data as well as their experimental verification are
demonstrated.
Keywords: Binary interaction parameter, NRTL equation, Vapor-liquid equilibrium,
Vapor pressure
Received: August 17, 2010; accepted: August 17, 2010
DOI: 10.1002/ceat.201000356

Introduction

A number of problems in safety engineering and the design of


plants or unit operations in chemical industries require the
knowledge of data for multicomponent systems. Without
knowledge of phase equilibria, the design of separation processes such as distillation, rectification, or extraction would
not be possible with scale-up factors as they are achieved
nowadays. Examples are vapor pressures of mixtures, the phase
behavior of liquid/liquid biphasic systems, and others. In the
petrochemical industry and automobile sector biofuels like,
e.g., ethanol or FAME (fatty acid methyl ester = biodiesel) as
well as blend components like ethers are getting more and
more in the focus. The strongly nonideal behavior of these
polar substances in a fuel consisting of unpolar alkanes, olefins, and aromatics requires several experimental data to fit
parameters for calculation of phase equilibria. For multicomponent systems in general only few experimental data are
available which leads to the necessity of mathematical prediction of these data. Several equations have been developed to
describe the phase behavior of multicomponent systems [1].

Correspondence: Prof. Dr.-Ing. E. Aust (eberhard.aust@ohmhochschule.de), Georg-Simon-Ohm Hochschule, Department of Applied Chemistry, Prinzregentenufer 47, 90489 Nrnberg, Germany.

* English version of: Chem. Ing. Tech. 2009, 81 (12), 1999.


DOI: 10.1002/cite.200900058

Chem. Eng. Technol. 2010, 33, No. 12, 20892094

Basically these complex systems are split into a number of


binary systems. In general, as fundamental equation for calculation of vapor-liquid equilibria (VLEs) Eq. (1) is used:


vi p pi
yi pui xi ci ui pi exp
RT

(1)

The exponential term in Eq. (1) is the Poynting factor which


could be neglected for low total pressure p. With this simplification Eq. (1) becomes:
yi pui xi ci pi

(2)

The variables left in Eq. (2) are the vapor pressure pi* of the
pure substance, the activity coefficient ci, and the fugacity
coefficient ji for the correction of real gas behavior. The vapor
pressure can be calculated with, e.g., the Antoine equation.
The fugacity coefficient is accessible from an equation of state
such as the Soave, Redlich, and Kwong (SRK) equation [1].
For the activity coefficient generally expressions for the free
excess enthalpy (gE) are used such as the Wilson equation,
NRTL (Non-Random-Two-Liquid Model) equation, or the
UNIQUAC (Universal Quasiemical) equation. Among these
equations the NRTL equation (and its modifications) is most
widely used [2]. All these approaches require two or three
binary interaction parameters (BIPs) to describe a binary mixture. The interaction parameters are generated with experimental data or can be predicted by the group contribution
method UNIFAC (Universal Quasichemical Functional Group
Activity Coefficients).

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T. Knorr et al.

Calculation of Interaction Parameters

Gij exp

State-of-the-art and established without doubt is the adjustment to VLE data (Tpxy data) [3, 4]. Furthermore, the use of
enthalpies of mixtures (hE), activity coefficients for infinite
dilution (c), or liquid/liquid equilibria data (LLE data) is
reported [3]. Recently, a method for determination of VLE
data using differential scanning calorimetry (DSC) coupled
with a flame ionization detector (FID) for analysis of the gas
phase was published [5]. This method leads to traditional VLE
data which could be used to adjust binary interaction parameters.
Barker demonstrated the regression of interaction parameters from vapor pressure data [6]. However, this method
requires vapor pressure data of binary mixtures with different
compositions but for the same temperature and no vapor pressure curves over a certain range of temperature. The RedlichKister equation was used in combination with a virial equation
of state for the gas phase correction. The adjustment of the
interaction parameters is done at a fixed temperature. Unfortunately, the experimental effort for this method is considerable, and the data obtained are valid only for a certain temperature. A method requiring only few data leading to parameters
valid for a wide range of temperature would be preferable. In
another work, published in 1962, the method of Barker was
used for some systems [7]. Furthermore, the use of vapor pressure data is mentioned in connection with the calculation of
VLE data but no system for the regression of interaction
parameters out of these data is presented.
The determination of binary interaction parameters from
VLE data requires access to these equilibrium data. For measurement of phase equilibria several strategies have been developed but most of these methods require a lot of experimental
work. On the other hand, this work is required to obtain reasonable data for a set of interaction parameters one can trust.
The classical methods use a variety of different equilibrium
stills to take samples from the liquid and the condensed vapor
phase at a certain temperature and pressure [5, 9, 10]. These
samples have to be analyzed by gas chromatography or other
methods to determine the compositions.

New Method for Determination of Binary


Interaction Parameters

3.1

Idea

Since a lot of effort has to be put into the generation of VLE


data, it would be desirable to use more accessible experimental
data for adjustment of the parameters. For this purpose an
approach using binary vapor pressure data is characterized.
This method allows calculation of the parameters for a certain
range of temperature. The NRTL equation was used to calculate the liquid phase activity coefficient.
sij Gji
sij Gji
gE
xi xj

RT
xi xj Gji xj xi Gij

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aij sji

Gji exp


(4)

aij aji
sij

gij

gji

sij

RT

Aij gij

gji

gji

gij

(5)

RT

Aji gji

gij

(6)

The nomenclature Aij and Aji for the binary interaction


parameters was chosen according to the Vapor-Liquid Equilibrium Data Collection published by the DECHEMA, Germany
[11]. In the NRTL equation, the parameters gij and gji are interpreted as a number for the interaction between the two species
i and j, and aij represents the nonideal behavior of the mixture.
However, this study is based on the parameters A which can be
calculated from the g-values according to Eq. (6).
To calculate a binary VLE, the solution of a system of two
equations is required. For both components the distribution
between gas and liquid phase is given by Eq. (1). In this study,
the simplified version of Eq. (1), namely Eq. (2), was used.
yi pui xi ci pi

(7)

yj puj xj cj pj

(8)

The solution of the system of equations given above is possible if values for the coefficients c and j as well as for the vapor
pressure p* are known. In the following study the fugacity
coefficient j was calculated according to the SRK equation of
state [12]. The vapor pressure was calculated using the Antoine
equation, and the activity coefficient was obtained from the
NRTL equation as already mentioned. From the solution of
Eqs. (7) and (8) the total pressure of the system can be calculated as the sum of all partial pressures using Daltons law.
pi yi p

pi

(9)

This total pressure over the mixture of two species is equal


to the vapor pressure of the liquid phase. With given values Aij
and Aji for the binary interaction parameters, the vapor pressure can be calculated over a liquid phase with known composition and at a certain temperature. If the procedure is repeated, the vapor pressure for a defined range of temperature
can be calculated as a function of the given values for the interaction parameters Aij and Aji. These calculated vapor pressure
curve can now be compared to the measured data for the same
interval of temperature and the same composition of the liquid
phase. The differences between measured and calculated pressures lead to the sum of squares, again as a function of the given values for the interaction parameters according to Eq. (10).
Sum of squares

X
i

(3)

aji sij

pmeasured pcalculated
pmeasured

2 !
(10)

For a simple visualization of the method, the third parameter in the NRTL equation, aij, was kept constant for a certain

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Chem. Eng. Technol. 2010, 33, No. 12, 20892094

Vapor-liquid equilibrium

binary system. Hence, the number of variables is set to two


and the sum of squares could be displayed easily in a Cartesian
coordinate system on the Z-axis while Aij and Aji are on the
X-axis and the Y-axis, respectively, as shown in Fig. 1.
As a first indication for the value of aij, the commendations
of Renon and Prausnitz are used [2]. However, the group contribution method UNIFAC will provide useful values as well.
Besides the NRTL equation, other approaches for activity coefficients can be treated in a similar way.

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Table 1. Compositions of n-pentane/o-xylene mixtures.


Molar fractions
Composition

xn-pentane

xo-xylene

0.59

0.41

0.19

0.81

Table 2. Compositions of n-hexane/ethanol mixtures.

3.2 Validation

Molar fractions
Composition

For verification of the method two binary systems have been


chosen. The first system is a rather ideal one, while the second
system shows an azeotrope and thus exhibits strong nonideal
characteristics. The system n-pentane/o-xylene is known as an
almost ideal system. The mixture n-hexane/ethanol shows an
azeotrope and is well-known from literature [1315]. For the
regression of the interaction parameters of both systems vapor
pressure curves for different mixtures have been measured (see
Tabs. 1 and 2). For the vapor pressures an equipment developed for precise measurement was available and used in the
present work [16]. The accessible temperature range is
approximately from 30 C to 200 C. For the measurements
of vapor pressures the above-mentioned substances (from
E. Merck, Germany) were used. The purities of all chemicals
were either for synthesis or for spectroscopy: n-pentane
> 99 %, o-xylene > 98 %, n-hexane > 99 %, ethanol > 99.9 %.
The purities have been controlled by gas chromatography. For
the pure substances vapor pressure curves have been determined, being in good agreement with the ones calculated by
the Antoine equation (using the process simulator ChemCAD) [17].

Figure 1. Scheme of calculation of the sum of squares.

Chem. Eng. Technol. 2010, 33, No. 12, 20892094

xn-hexane

xethanol

0.91

0.09

0.50

0.50

0.09

0.91

3.3

Computation

Based on the process simulator Chem-CAD (version 6.0.2)


[17] in combination with Excel/VBA (Visual Basic for Application, version 2003), regression of the interaction parameters
was carried out using measured vapor pressure data as described in Section 3.1. For a reasonable number of supporting
points the sum of squares for the measured and calculated
vapor pressures was calculated. The scheme of the regression
procedure using Excel/VBA and Chem-CAD is illustrated in
Fig. 2.
When plotted for all studied parameters Aij and Aji as
described in Section 3.1, a clear connection between both
interaction parameters and the sum of squares is displayed
in Fig. 3. The results for the first mixture (see Tab. 1) of
the system n-pentane/o-xylene are demonstrated.
The parameters have been varied in the
range of 0 to 1000 and 500 to 400, respectively. Fig. 3 shows that many pairs of Aij
and Aji can be given describing the chosen
vapor pressure data quite similarly. For all
mixtures of all systems similar results are
obtained. The sets of possible parameters
represent a line in the plot of the sum of
squares, a line of minima. If one compares
the trends for the minimum sum of
squares for both mixtures in the system
n-pentane/o-xylene, a clear intersection
point is found as shown in Fig. 4.
It is obvious to choose the parameters at
the intersection point as solution for the
interaction parameters since this is the
only set of values describing both vapor
pressure curves with good accuracy. Also
for the system n-hexane/ethanol a similar
correlation was found. Due to the strongly
nonideal behavior of the system a third
composition was added (see Tab. 2). Even

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T. Knorr et al.

for the nonideal system with azeotrope a similar trend for the
minimum sum of squares was found, as can be seen in Fig. 5.
All three curves intersect in a small area.

Figure 2. Scheme of the regression of interaction parameters


using Excel and Chem-CAD.
Figure 5. Trends for the minimal sum of squares for the three
compositions given in Tab. 2 for the system n-hexane/ethanol.

Figure 3. 3D plot of the sum of squares for a mixture of n-pentane and o-xylene as a function of the two binary interaction
parameters of the NRTL equation.

Figure 4. Trends for the minimal sum of squares for the two
compositions given in Tab. 1 for the system n-pentane/o-xylene.

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Validation of Results and Discussion

For validation of the interaction parameters obtained from the


procedures described above for both systems, VLE data have
been calculated using the found parameters. The calculated
data were compared to measured data. For this purpose, an
isobaric VLE was measured for the system n-pentane/o-xylene
using the equilibrium still of Rck and Sieg manufactured by
the NORMAG AG Company, Germany [18]. Comparing both
experimental and calculated data, one can see a good agreement in Fig. 6. Again, as done for regression, the gas phase
behavior was corrected by the SRK equation.
For the system n-hexane/ethanol two different VLEs, an isothermal and an isobaric one, were calculated and compared to
literature data [13, 14] (see Figs. 7 and 8). These plots point
out that the method presented in this work is able to lead to

Figure 6. Isobaric vapor-liquid equilibrium for n-heptane/o-xylene at 940 mbar. The calculation was done using the NRTL
equation in combination with the SRK equation of state for gas
phase correction. The data have been measured at the
Hochschule Nrnberg.

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Chem. Eng. Technol. 2010, 33, No. 12, 20892094

Vapor-liquid equilibrium

Figure 7. Isobaric vapor-liquid equilibrium for n-hexane/ethanol


at 1013 mbar. The calculation was done using the NRTL equation in combination with the SRK equation of state for gas phase
correction. Measured data from [10].

2093

Figure 9. Isothermal vapor-liquid equilibrium for n-hexane/ethanol at 318.15 K. The curves Parameter I to Parameter IV represent
the sets of BIPs indicated in Fig. 5. Calculation was done using
the NRTL and SRK equations. Measured data from [11].

interaction parameters should be valid for the total range of


concentration, the regression using vapor pressure data has to
be done with at least two curves for different liquid phase
compositions.

Figure 8. Isothermal vapor-liquid equilibrium for n-hexane/ethanol at 318.15 K. The calculation was done using the NRTL equation in combination with the SRK equation of state for gas phase
correction. Measured data from [11].

parameters even for strongly nonideal mixtures like azeotropes. Only minor deviations between measurement and calculation could be observed.
However, Fig. 5 illustrates that several sets of parameters are
able to describe the measured vapor pressure curves with sufficient precision. In the following, a sensitivity study proves that
only the set of parameters at the intersection point of the
curves will also describe VLE data properly. The sets of parameters, indicated in Fig. 5 by the numbers I to IV, reproduce the
vapor pressure curve used for their calculation with good accuracy. Obviously the results are different when these sets of
parameters are used to calculate VLE data. In Fig. 9 the calculated isothermal VLE data were compared to those of the literature [12]. The azeotropic point, the dew point line, and the
bubble point line vary with the set of parameters.
These sets of parameters were generated from composition 1
(see Tab. 2) with 9 mol.-% of ethanol. This explains why all the
curves almost look the same for low ethanol concentration
and vary strongly for higher ethanol concentrations. Since

Chem. Eng. Technol. 2010, 33, No. 12, 20892094

Conclusions

Calculation of phase equilibria requires accurate interaction


parameters of the equation used to calculate activity coefficients. As an alternative to the regression from VLE data it is
also possible to use vapor pressure curves of binary mixtures
for the fit of the parameters. Here, the parameters are fitted
until the calculated data are in good agreement with the experimental curves using the least square method. To achieve
parameters for the full range of concentration, at least two
vapor pressure curves of binary mixtures with different concentrations are required. The method was demonstrated for
two different binary mixtures. Even for a strongly nonideal
system, namely n-hexane/ethanol with an azeotropic point,
good agreement between calculated and experimental data was
found. Since conventional VLEs require a lot of samples to be
analyzed (e.g., GC or refraction index), this method demands
simply the measurement of the pressure over the liquid phase
as well as the composition of the liquid phase.
The authors have declared no conflict of interest.

Symbols used
Aij

[cal mol1]

gE
hE
p
pi
pi*
R

[J mol1]
[J mol1]
[Pa]
[Pa]
[Pa]
[J mol1K1]

interaction parameter of NRTL


equation
free excess enthalpy
enthalpy of mixing
pressure
partial pressure
vapor pressure
universal gas constant

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T. Knorr et al.

T
vi
xi
yi
ui
aij

[K]
[m3mol]
[moli mol1]
[moli mol1]
[]
[]

ci

[]

temperature
molar volume of liquid phase
molar fraction in liquid phase
molar fraction in gas phase
fugacity coefficient
interaction parameter of NRTL
equation
activity coefficient

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[5] I. von Buchholz, K. Schnitzlein, Chem. Ing. Tech. 2008, 80
(10), 1557.

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Chem. Eng. Technol. 2010, 33, No. 12, 20892094