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.

© All Rights Reserved

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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.

© All Rights Reserved

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DATA

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)

0.0220 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

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

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

+ By regression.

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

T(“C)

30 40 50 60

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

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

} 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

0 5 I

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

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

Science Foundation Grant No. ENG75-17367. This paper was presented at

the 69th Annual AIChE Meeting, Chicago, Illinois (November 30,1976).

NOTATION

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.

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