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Fluid Phase Equilibria, 1 (1977) 3-l 1 3

o Elsevier Scientific Publishing Company, Amsterdam - Printed in The Netherlands

AN EXTENSION OF BARKER’S METHOD FOR REDUCTION OF VLE


DATA

M.M. ABBOTT and H.C. VAN NESS


Department of Chemical and Environmental Engineering, Rensselaer Polytechnic Institute,
Troy, New York 12181 (U.S.A.)
(Received October 25th, 1976)

ABSTRACT

Abbott, M.M. and Van Ness, H.C., 1977. An extension of Barker’s method for reduction
of VLE data. Fluid Phase Equilibria, 1: 3-11

A set of P VS. x data for vapor-liquid equilibrium properly contains the pure-component
vapor pressures. These values are as uncertain as the values for other measured pressures,
and data reduction should yield smoothed values for these as well as for the other pressures.
However, the vapor pressures also appear as constants in the reducing equation; here they
must have assigned values. This paper shows how the results of data reduction are influenced
by different treatments of the vapor pressure.

INTRODUCTION

We have earlier demonstrated (Abbott and Van Ness, 1975) the general
applicability and advantages of the method proposed by Barker (1953) for
the reduction of isothermal vapor/liquid equilibrium data at low pressures.
The method requires no more than a set of P vs. x data, and is based on the
equation:
P = C (Xj yi P;sat/@i) (1)
i

The activity coefficients yi are replaced in eqn. (1) by the equations which
relate them to the excess Gibbs function GE of the liquid phase. The compo-
sition dependence of GE is then expressed by an equation of suitable form,
and values of the undetermined parameters in this equation are found by a
regression procedure that yields a best fit of the P vs. x data. The @i in eqn.
(1) account primarily for vapor-phase nonidealities and depend on the yi;
since these are not initially known, an iterative procedure is required. The
final result is an expression for the composition dependence of GE from
which correlated values of P and y can be calculated at any value of 3~.
The vapor pressures Pisat of the pure components appear explicitly on the
right side of eqn. (1) as physical constants, presumed fixed and known for
4

data taken at constant temperature. On the other hand, values for Prt are
properly measured as part of the P vs. x data set to which eqn. (1) is applied,
and they should be treated in the regression procedure exactly as all other
data points. As limiting values of P for Xi = 1.0, the P,@ values are no more
significant than other values of P and are equally subject to experimental
error and to smoothing during data reduction. Their special significance
enters only through the terms on the right of eqn. (1); here they interact
with all data points of the regression set. We propose to accommodate this
dual role of the Pyt values in Barker’s method by treating them both as data
points and as adjustable parameters; thus measured values of P for xi = 1.0
are included in the data set, but are not initially identified with Pisat. Rather,
the values of Psat are determined by regression along with the parameters in
the equation which expresses the composition dependence of GE. These
values of PFat of course become the smoothed values of P for x; = 1.0 in any
comparison of correlated results with experimental data.
Fabries and Renon (1975) suggested that the Prt be treated as adjustable
parameters “when no vapor pressure is given or when values appear to be in
error”, but they provided no examples. Other precedents may exist, but we
are not aware of any study which provides a critical examination of the
method in comparison with the conventional Barker method or with other
variants of it. That is the purpose of this paper.
We will compare results determined by three methods: the conventional
Barker method, called the CB method; the extended Barker method as
described here and called the EB method; and the method suggested by
Fabries and Renon, denoted the EB’ method. In applying the three methods,
we will adopt the conventional practice of assigning equal weights to all data
points.
In the CB method the eat are assigned their experimental values. Since
these are fixed prior to regression, the values of P for Xi = 1.0 can have no
separate identity, and are not part of the data set. The EB’ method differs
from the EB method in that, although the Pi”t are determined by regression,
values of P for 3ti = 1.0 are not included in the data set for lack of experimen-
tal values. This regrettably is a rather common circumstance.

Example 1

We deal first with the set of P--x1 data for a binary system given in Table 1.
The x1 values come from a table of random numbers. The P values are gener-
ated by eqn. (1) for arbitrarily chosen values of P,“t and Pzsat and for y1 and
yz values consistent with the equation:
GE/RT = 0.40000 xlxz
The vapor phase is taken to be an ideal gas and the liquid-phase properties are
considered independent of pressure; the 4ji values are therefore unity. The
values of pressure so computed are designated by the symbol P*, and repre-
TABLE1

Artificial
P-x data forExample 1

Xl P*(mmHg) J'(mmHg)

0.0000 397.22 396.90


0.0220 408.06 408.26
0.0521 422.07 421.90
0.0838 435.86 435.89
0.1293 454.08 454.47
0.1677 468.15 467.90
0.2256 487.36 487.79
0.2753 502.14 502.06
0.3382 518.89 518.41
0.3909 531.42 531.28
0.4484 543.74 543.59
0.4810 550.14 550.93
0.5335 559.64 559.55
0.5914 569.04 569.41
0.6591 578.69 578.28
0.7083 584.81 584.21
0.7647 590.93 591.09
0.8030 594.51 594.73
0.8532 598.49 598.35
0.8965 601.21 601.09
0.9439 603.40 603.62
0.9808 604.46 604.28
1.0000 604.78 605.14

sent “true” or perfect values. We have added to P* random errors of magni-


tude less than 0.8 mm Hg and of average absolute value equal to 0.27 mm Hg,
thus providing pressures P which simulate experimental values. This model
data set is reduced by each of the three Barker methods to yield the psram-
eter A in the equation:
GE/RT = Ax1 x1 (2)
Results for all methods appear in Table 2, and pressure residuals, AP =
P talc-P exp, are plotted for the CB and EB methods in Fig. 1. Since the
pressure residuals for the EB and EB’ methods follow almost the same pat-
tern, the latter are not shown.
All three methods yield satisfactory correlations, as might be expected for
a data set of reasonable extent and containing only random error. However,
the pressure residuals for the CB method clearly show the effect of an assign-
ment of fixed, but slightly wrong, values for Pyt. Although the errors assigned
to the values of P at xi = 1.0 are “random” errors within the context of the
whole P vs. x data set, they are in no sense random with respect to Pyt and
Psat.
2 They are simply errors which affect all calculated values in a systematic
way, and cause the bias seen in the results represented by the open triangles
6

I .o

I
AP
a
(mmHg)

0
,

0 I
XI
Fig. 1. Pressure residuals for Example 1. a Conventional Barker method (CB method);
l Extended Barker method (EB method).

TABLE 2

Results for Example 1

“True” values CB method EB method EB’ method

A 0.40000 0.39995 0.39988 0.39971


Ps”t 604.78 605.14 t 604.81+ 604.74’
Pmt 397.22 396.90 + 397.21’ 397.31+
$MS AP (mmHg) - 0.40 0.33 0.32
Max IAPI (mmHg) 0.79 0.80 0.80

+ Fixed at “experimental” value.


+ By regression.

of Fig. 1. Calculated values of vapor compositions also reflect this bias. On


the other hand, the EB and EB’ methods yield values of Pfat and Pzsatclose
to the “true” values, and therefore produce virtually unbiased results.

Example 2

We turn now to several sets of real data of good precision. The system is
l-propanol(l)-n-heptane(2), for which Peloquin (1965) measured P-x, data
at 30, 40, 50, and 60°C. These data sets include values for P at Xi = 1.0, and
are appropriate for reduction by the EB method. However, the composition
dependence of GE is complex, and the EB method is not suitable except with
an equation that is known capable of providing an excellent fit of the data.
7

TABLE 3

Results for 1 -propanol( 1 bn-heptane( 2) at constant 2’

T(“C)

30 40 50 60

A*, 2.0346 2.0064 1.9797 1.9388


A,, 3.8241 3.6263 3.2504 2.9568
B,, 22.2921 18.8469 11.1700 6.9903
B*, 2.1701 2.0098 1.7192 1.4495
C 6.0720 5.3554 3.8467 2.1594
RMS AP (mmHg) 0.08 0.11 0.21 0.31
Max IAPI (mmHg) 0.17 0.24 0.46 0.60
Pyt (mmHg) 29.43 52.99 91.58 152.52
(Exp. value) (29.44) (53.04) (91.65) (152.46)
Pyt (mmHg) 58.74 92.79 142.07 210.86
(Exp. value) (58.75) (92.79) (142.08) (211.00)

Thus all preliminary data fits designed to test the suitability of the correlating
equation must be carried out by the CB method. Once the suitability of an
equation is demonstrated, then the final values for Ppt and the fitting param-
eters are determined by data reduction with the EB method. This two-step
procedure minimizes the possibility that the Pyt may act as primary fitting
parameters in the EB method.
For the propanol-heptane data considered here application of the CB
method demonstrated the suitability of a B-parameter modification of the
Margules equation (Abbott and Van Ness, 1975):

1
GE &~BZIXIG
jyj_=vz A12x2 - - (3)
3312x1 + B2lx.2 + (31x2

Detailed final results of the data-reduction process by the EB method are


published elsewhere (Van Ness and Abbott, 1976); Table 3 presents a summary.
Excellent correlations are obtained for all data sets: the pressure residuals are
small; the fitting parameters vary regularly with temperature; and the values
of Pzvt obtained by regression agree well with experimental values, indicating
excellent internal agreement of the measured Pisat values with other members
of the p-3c1 data sets and demonstrating that the Pyt do not act as primary
fitting parameters.
This example serves as an illustration of the proper application of the EB
method to complete sets of good quality P-x data.

Example 3

Van Ness et al. (1973) presented an analysis of a set of P-xl-y1 data pub-
lished by Fried et al. (1967) for the pyridine(l)-tetrachloroethylene(2) sys-
8

tern at 60°C. In this example we apply all three Barker methods to the reduc-
tion of this same data set, representing the composition dependence of GE,
as in all previous work, by the 3-parameter Margules equation:
GE
- =xlxZIAzlxl +Alzx,- Dx~x~]
RT
The reported data set does not include experimental values for Pyt; rather,
the authors cite Antoine equations in the literature for required values. Thus
for the CB method we have calculated values for Pyt and Piat from the cited
equations, For the EB method we have included these same values with the
data set so as to provide data points at Xi = 1.0. The EB’ method requires
only the reported data set of 17 points for values of x1 from 0.0652 to 0.9525.
Results for the three methods are summarized in Table 4.
The CB and EB methods yield comparable results, which indicates that the
P vs. x1 data are smooth and that the foreign values for Prt are compatible
with the data set. The EB’ method, which makes no use of the foreign vapor
pressures, produces an excellent correlation, but surprisingly the correlating
expression for GE requires just a single parameter. That is, eqn. (4) reduces
to the special case represented by eqn. (2). The considerable difference in
results between the EB and EB’ methods is illustrated by the plot of
GE/xl xy2RT vs. x1 shown in Fig. 2. Although the pressure residuals shown in
Fig. 3 for the two methods are not strikingly different, the values for Pyt
and Plat produced by the EB’ method are significantly higher than either the
literature values or those found by the EB method. This suggests that in this
particular application of the EB’ method the Pyt are playing the role of
primary curve-fitting parameters, even to the extent of affecting the nature
of the correlating expression for G E. This is not the proper function of the
PSat in either of the extended Barker methods, wherein they are unconstrain-
ei so that as data points they may be treated on the same basis as the other

TABLE 4

Results for pyridine( l)-tetrachloroethylene(2) at 60°C

CB method EB method EB’ method

A21 0.8469 0.8391


} 0.7459*
A.. 0.8859 0.8780
D’_ 0.2964 0.2765 -
RMS AP (mmHg) 0.20 0.19 0.16
Max lAPi (mmHg) 0.37 0.38 0.32
Pyt (mmHg) 110.95 + 111.02+ 111.76+
Pyt (mmHg) 94.88 + 94.97 r 96.53’

*A,, =A,,=A.
+ Fixed at value given by Antoine equation
’ By regression.
9

Fig. 2. Correlations of G” for Example 3. Curve A: EB method; Curve B: EB’ method.

0 5 I

Fig. 3. Pressure residuals for Example 3. a EB method; l EB’ method.

pressure measurements, not so that they may preempt the role assigned the
parameters in the expression for GE. Whenever the Pyt act as primary curve-
fitting parameters, incorrect results are obtained, and they must be rejected.
Thus we cannot accept the results of the EB’ method in the example treated
here.
This conclusion is reinforced by consideration of additional data published
by Fried et al. (1967 and 1968) for this same system at 50, 80, and 100°C.
Analysis of these data by whatever method shows that a 3-parameter Margules
equation is required. Moreover, cross correlations with respect to temperature
indicate that the values of GE produced by the EB’ method applied to the
data for 60°C are too low.
10

CONCLUSIONS

The extended Barker (EB) method can be recommended as an appropriate


procedure for the reduction of complete sets of good quality P vs. x data.
The method is also in principle certainly applicable to data for multicompo-
nent systems. We cannot, however, recommend application of this method as
a means of correctin for the neglect of experimentalists to provide careful
measurements of q $ values, taken in the same apparatus and with the same
lots of materials as all other reported P vs.x data. These values are critical to
the determination of correct expressions for the composition dependence of
GE. In the extended Barker method they are necessary for the determination
that the Pyt do not act as primary fitting parameters.

ACKNOWLEDGMENT

We appreciate the financial support provided for this work by National


Science Foundation Grant No. ENG75-17367. This paper was presented at
the 69th Annual AIChE Meeting, Chicago, Illinois (November 30,1976).

NOTATION

A An, A21 = Parameters in eqns. (2), (3), (4)


B12, B219 C = Parameters in eqn. (3)
D = Parameter in eqn. (4)
GE = Excess Gibbs free energy
P = Pressure
psat = Saturation vapor pressure of pure i
R’ = Universal gas constant
T = Absolute temperature
xi = Mole fraction of species i in liquid phase
Yi = Mole fraction of species i in vapor phase
= Activity coefficient for species i in liquid phase
lpli = Correction factor in eqn. (1)

REFERENCES

Abbott, M.M. and Van Ness, H.C., 1975. Vapor-liquid equilibrium: Part III. Data reduction
with precise expressions for GE. AIChE J., 21: 62.
Barker, J.A., 1953. Determination of activity coefficients from total pressure measure-
ments. Aust. J. Chem., 6: 207.
Fabries, J.-F. and Renon, H., 1975. Method of evaluation and reduction of vapor-liquid
equilibrium data of binary mixtures. AIChE J., 21: 735.
Fried, V., Gallant, P. and Schneier, G.B., 1967. Vapor-liquid equilibrium in the system
pyridine-tetrachloroethylene. J. Chem. Eng. Data, 12: 504.
11

Fried, V., Franceschetti, D.R. and Schneier, G.B., 1968. Excess free energies of the sys-
tems carbon tetrachloride-pyridine and pyridine-tetrachloroethylene. J. Chem. Eng.
Data, 13: 415.
Peloquin, G., 1965. Vapor-liquid equilibrium for the system n-propyl alcohol-n-heptane.
M.Ch.E. Thesis, Rensselaer Polytechnic Institute, August, 1965.
Van Ness, H.C. and Abbott, M.M., 1976. Int. DATA Ser., Selec. Data Mixtures, Ser. A,
1-42 (in press).
Van Ness, H.C., Byer, S.M. and Gibbs, R.E., 1973. Vapor-liquid equilibrium: Part I. An
appraisal of data reduction methods. AIChE J., 19: 238.