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Uni Cuac
Uni Cuac
Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44, 01-224 Warszawa, Poland
Received 16 March 2000; accepted 28 November 2000
Abstract
The UNIQUAC equation was modied by introduction of a linear temperature dependence of the volume and
surface area parameters, r
i
and q
i
. The slope of r
i
and q
i
functions were found to be the same for hydrocarbons
and pyridine. The modied equation was used for prediction of vaporliquid equilibria (VLE) in binary mixtures
of hydrocarbons and pyridine with hydrocarbons as well as for the prediction of the excess enthalpy (H
E
) in
binary mixtures formed by pyridine with aliphatic alkanes. The results obtained were compared with predictions by
UNIFAC and further with UNIQUAC equation and its modication involving temperature dependant coordination
number z. The proposed temperature dependence of the r
i
and q
i
parameters enables prediction of the VLE at
various temperatures and leads to reasonable values of H
E
. The necessary input reduces to one set of isothermal
VLE data. One set of UNIQUAC interaction parameters u
ij
is sufcient for representation of VLE in a wide range
of temperature and to obtain a reasonable prediction of H
E
. 2001 Published by Elsevier Science B.V.
Keywords: Vaporliquid equilibria; Excess enthalpy; Activity coefcient; Correlation; Prediction
1. Introduction
Knowledge of the vaporliquid equilibriumdata (VLE) is necessary to design and optimize distillation,
which is one of the most frequently used separation methods. To minimize design cost, tedious and expen-
sive VLE measurements are avoided and prediction and correlation methods are used instead. The most
difcult problem is to obtain accurate information on the temperature dependence of activity coefcients.
Knowledge of this dependence is important for systems formed by pyridines with hydrocarbons. The
UNIQUAC equation [1] represents the activity coefcients as a function of concentration for systems
formed by pyridine with aliphatic alkanes very well.
The main aim of the present work was to modify the UNIQUAC equation in such a way that it would
be possible to predict, with high accuracy, the activity coefcients and VLE of these systems as function
i
and q
i
at standard temperature T
i
+a(T T
) (1)
q
i
= q
i
+b(T T
) (2)
Reduction of literature data [4] available for two binary systems: pyridine +n-heptane and benzene +
cyclohexane leads to the following values:
a = 0.015 and b = 0.010
The reference values of r
i
and q
i
at temperature T
1
N
N
i=1
P
exp.
i
P
cal.
i
P
exp.
i
1/2
(3)
where P
exp.
i
is the experimental vapor pressure, P
cal.
i
the corresponding calculated vapor pressure, and N
the number of data points.
The average relative standard deviations of equilibrium pressures RMSD(P) for each investigated
isotherm are shown in Table 1. For binary mixtures formed by pyridine and aliphatic alkanes the average
relative standard deviation of equilibrium pressures RMSD(P) are also plotted in Figs. 14.
The values of r
i
and q
i
used in the UNIQUACequation are shown in Table 2. The values of the interac-
tion parameters u
ij
in the original UNIQUAC equation and in the UNIQUAC equation with temperature
dependent coordination number z (obtained by data reduction at the reference temperature T
) are shown
in Table 3.
A computation of the excess enthalpy (H
E
) is the most sensitive method to check the reliability of
equations representing the temperature dependence of phase equilibrium parameters for mixtures. For
binary systems formed by pyridine and aliphatic alkanes a comparison of H
E
computed from various
Fig. 1. The average relative standard deviation of equilibrium pressures, RMSD(P), for each isotherm T for the binary mixture
pyridine + n-heptane: () prediction using UNIQUAC with r, q = f (T T
i
and surface area q
i
parameters
Substance r
i
q
i
Benzene 3.1878 2.400
Carbon tetrachloride 3.3900 2.910
Cyclohexane 4.0464 3.240
n-Decane 7.1974 6.016
Ethylbenzene 4.5972 3.508
n-Hexane 4.4998 3.856
n-Heptane 5.1742 4.396
iso-Propylbenzene 5.2708 4.044
Methylbenzene 3.9228 2.968
Methylcyclohexane 4.7200 3.776
n-Octane 5.8486 4.936
n-Nonane 6.5230 5.476
Pyridine 2.9993 2.113
versions of UNIQUACequation with experimental data [8] was made. The excess enthalpy was calculated
by equation
H
E
= RT
2
(G
E
/T )
T
p,x
(4)
The excess Gibbs energy (G
E
) and the excess enthalpy H
E
were calculated using the UNIQUAC equa-
tion:
Table 3
The interaction parameters u
ij
in original UNIQUAC equation and in UNIQUAC equation with temperature dependent coordi-
nation number z obtained by data reduction at temperature T
System T