Fluid Phase Equilibria, 14 (1983) 383-392 383

Elsevier Science Publishers B.V., Amsterdam - Printed in Tbe Netherlands

THERMODYNAMIC CONSISTENCY TESTING OF PTx-DATA VIA THE GIBBS-HELMHOLTZ EQUATION

JAMES D. OLSON
Union Carbide Corporation, Research and Development Department, P. 0. Box 8361,

South Charleston, West Virginia 25303 (U.S.A.)

ABSTRACT
Although the Gibbs-Duhem slope and area consistency tests cannot be used on
PTx vapor-liquid equilibrium data, the Gibbs-Helmholtz equation can be used to
test the consistency of PTx data measured at several temperatures. This is
done by comparison to calorimetrically-determined excess enthalpy (HE) data.
Results are presented for Gibbs-Helmholtz tests on ebulliometrically-determined
PTx data for the systems acetone + methyl acetate, propylene glycol + ethylene
glycol and ethanol + water. In addition, results on the effect of random
errors on Gibbs-Helmholtz testing of computer-generated PTx data are given.
These studies on actual and simulated PTx data indicate that, on the one hand,
random errors in pressure measurement usually claimed (0.01 to 0.1 kPa) should
not cause the Gibbs-Helmholtz test to fail, and, on the other hand, random
errors in pressure measurement large enough to give Gibbs-Helmholtz inconsis-
tency may not be large enough to cause unacceptable errors in the calculated
vapor compositions. This indicates that the Gibbs-Helmholtz test is stringent
and data that fail may still have practical value for chemical process design.

INTRODUCTION
PTxy (pressure-temperature-liquid mole fraction-vapor mole fraction) vapor-
liquid equilibrium data are redundant according to the phase rule. Hence,
differential and integral thermodynamic consistency tests can be constructed
from the Gibbs-Duhem equation (Prausnitz, 1969). More recently, a PTxy
consistency test has been developed in which y(exper) vs. y(calc) are examined
for systematic errors (Van Ness et al., 1973). In contrast, Px or TX (PTx)
data are the minimum necessary to specify VLE so that the Gibbs-Duhem tests are
not possible. However, GE data derived from PTx data measured at several

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384

temperatures can be compared to calorimetric HE data with the Gibbs-Helmholtz

equation,

-RT+ (GE/~~)/2 T], = HE (1)

This comparison can be used as a thermodynamic consistency test for PTx data.
Examples have appeared (Harris and Prausnitz, 1968; Bae et al., 1980; Van Ness
and Smith, 1981; Olson, 1981; Rubio et al., 1982). The discussion here is
limited to low-pressure VLE (up to ~1.5 MPa) where volumetric effects can
usually be neglected.
The principal objective of thermodynamic consistency tests is to show the
likely absence of systematic errors. The practical uses are (i) to referee
between different data sets on the same system, (ii) to justify confidence in
the chemical process equipment designed from the data, and (iii) to ensure
data of the highest quality for experimental standards and for testing and
extension of theory. The failure of PTx data to pass the Gibbs-Helmholtz test
is indirect evidence that the experimental measurements and/or the details of
the data reduction procedure contain systematic errors. This also suggests
that the vapor compositions calculated from the PTx data contain systematic
errors.
The purpose of this paper is to discuss “how bad” PTx data have to be to
fail the Gibbs-Helmholtz test and whether y values predicted from PTx data
that fail can still have any practical value for design. This is done by
examining Gibbs-Helmholtz tests on three systems measured at Union Carbide and
on computer-generated data that contain successively larger random errors in
pressure.

01 SCUSSION
Gibbs-Helmholtz tests on measured PTx data
Experimental PTx data suitable for Gibbs-Helmholtz testing have been
determined at Union Carbide for three systems: acetone + methyl acetate,
propylene glycol + ethylene glycol, and ethanol + water. These PTx data were
measured by ebulliometry (Olson, 1982) and GE data were derived by Barker’s
method (for a discussion of PTx data reduction methods, see Van Ness and
Abbott, 1982, Chapter 6). The GE model fitted to the PTx data was the
Redlich-Kister equation. The vapor-phase fugacity coefficients were
calculated from the pressure-explicit second virial equation except for
propylene glycol + ethylene glycol where the ideal gas model was found to be
sufficient. Equimolar GE/RT data were plotted against temperature to obtain
 385

an equimolar HE(PTx) from a graphical slope. This HE(PTx) was then

compared to an equimolar HE(exper) value from heat-of-mixing experiments to

perform the Gibbs-Helmholtz test. In addition, plots of GE, HE, and TSE
vs. composition were constructed from the equation:

GE= HE- TSE (2)

TABLE 1
Comparison of calorimetric equimolar HE(exper) with equimolar HE(PTx) derived
from Gibbs-Helmholtz analysis of PTx data

System HE T;;oPyr) "5 F'F'y)

(KT) 5 5 4 ErrSr p

Acetone (1) + 323. 5 86.5a a8b 1.7 0.05-0.07

Methyl Acetate (2)

Propylene Glycol (1) + 408.

Ethylene Glycol (2)

Ethanol (1) + 323. -175d 42 0.05-0.12

Water (2) 343. 5" -g: 118d 11

aH. C. Van Ness and M. M. Abbott, personal communication, 1980.

bOlson, 1981.
cJ. J. Christensen, personal communication, 1980.
dUnpublished Union Carbide data.
ePemberton and Mash, 1978.
HE(exper) = HE measured directly by calorimetry.
HE(PTx) = HE derived from Gibbs-Helmholtz analysis of PTx data.
Error P = Standard deviation in pressure from Barker's method fit.

Table 1 gives a summary of the Gibbs-Helmholtz tests. If we use the

criterion,

0.5 HE(exper)sHE(PTx)s1.5 HE[exper), x1=x2=0.5 (3)

the systems acetone + methyl acetate and ethanol + water pass the Gibbs-
Helmholtz test while the system propylene glycol + ethylene glycol fails. Note
that the level of pressure uncertainty in these data is low (0.05 to 0.22% in
pressure equal to absolute errors of 0.01 to 0.08 kPa).
Acetone (1) + methyl acetate (2). The experimental data for this system
have been published (Olson, 1981). Figure l(a) indicates the high degree of
Gibbs-Helmholtz consistency shown by the derived GE for this nearly ideal
system.
 (b)

L . 1 . ’ * ’ ’ ’ .
290 300 310 320 330 0 0.2 0.4 0.6 0.6
TEMPERATURE 1 K I Xl

Fig. 1.Gibbs-Helmholtz analysis of PTx data for acetone (1) + methyl acetate
Equimolar GF/RT vs. temperature. Points (0) and ( -_) derived
!',b, P!Z) data; (------) is the sl ope at 323.15 K calculated from calorimetric
equimolar . HE. (b) Excess thermodynamic functions at 323.15 K. Curves:
(-)I derived from PTx data; (------) derived from calorimetric HE.

In the published analysis, the degree of agreement of HE(PTx) and HE(exper) was
shown to be sensitive to the method of estimating virial coefficients for
calculation of vapor-phase fugacity coefficients. Use of a different method

gave a 323.15 K value of the equimolar HE(PTx) = 0.0 and hence Gibbs-
Helmholtz inconsistency. This shows that Gibbs-Helmholtz testing is sensitive

not only to the experimental data but also to the details of data reduction.
However, values of calculated vapor composition differed <0.0002 between the

two methods because of cancellation between changes in the fugacity

coefficients and changes in the activity coefficients. This sensitivity of

HE(PTx) to fugacity coefficients is found only in nearly ideal systems where

the activity coefficients and fugacity coefficients have similar magnitudes.
Figure l(b) indicates that, although the magnitude of HE(PTx) vs. x is

correct, the second-order skewness is not. This suggests a composition-

dependent systematic error.

Propylene qlycol (1) + ethylene glycol (2). Figure 2(a) shows that the

derived equimolar GE data have only qualitatively correct temperature

dependence; the equimolar HE(PTx) value is more than seven times too large.
 387

(a) (b)

-250 -
I , I I . I .

390 400 410 420

TEMPERATURE ( K 1 Xl

Fig. 2. Gibbs-Helmholtz
analysis of PTx data for propylene glycol (1) +
~thyle;ed~;~;~; I;;, Pi;?) Equimolar GE/RT vs. temperature. Points (0) and
data* (------) is the slope at 408.15 K calculated
from calorimetric equimolar Ht. (b) Excess thermodynamic functions at
408.15 K. Curves: (- ) derived from PTx data; (------) derived from
calorimetric HE.

Data for this system were not determined directly on isotherms as were data
for the other systems. Instead, isobaric data at 6.67, 13.33 and 26.66 kPa
were measured and isotherms were constructed by interpolation. Note also that
the slope disagreement in Fig. Z(a) is worse at lower temperatures (if we
assume dHE/dT to be small). This suggests a temperature-dependent
systematic error in the measurement. For example, hydrogen-bonding materials
boil differently and less consistently at lower pressures. Finally,
relative-volatility data derived from these PTx measurements agree well with a
previous PTxy study (Sokolov et al., 1972) when actually measured vapor
pressures are used to analyze the 1972 data.
Figure Z(b) shows that the HE and TSE functions obtained from HE(exper)
are of the same magnitude as GE.
Ethanol (1) + water (2). This system is an excellent choice for testing
VLE measurement methods because of the extensive and consistent data published
by Larkin and Pemberton (1976) and Pemberton and Mash (1978). Figure 3(a)
shows that the sign reversal in the equimolar HE is correctly predicted and
that Gibbs-Helmholtz consistency is achieved at the +10-40X error level in
equimolar HE(PTx).
388

(a) (b)

306
600
;i
d
“Cd
:: 305
?s.
0
8
-

F” 304
yi -400
(r
\ E
% -600

-600
I . 4 , I
303
320 330 340 350 0 0.2 0.4 0.6 0.6 I.0

TEMPERATURE (K 1

fig. 3. Gibbs-Helmholtz analysis of PTx data for ethanol (1) + water (2).
(a) Equimol ar Gk/RT vs. temperature. Points (0) and (- ) derived from PTx
data; (---- --) is the slope calculated at 323.15 K and at 343.15 K from
calorimetric equimolar HF. (b) Excess thermodynamic functions at 343.15 K.
Curves: (-) derived from PTx data; (------) excess functions from
Pemberton and Mash (1978).

It is significant that again the slope disagreement is worse at lower

temperatures which suggests that the ethanol + water system boils more smoothly
and consistently at higher pressures. Absence of this type of systematic
dependence on temperature can be used as a criterion of the suitability of
ebulliometry as a route to VLE data.
For this system, we can compare all three excess functions with an
independent study. Figure 3(b) shows that the GE function at 343.15 K
agrees with the NPL study well within experimental error. Hence, the derived
vapor compositions would be more than sufficiently accurate for design
purposes (error in yCO.0005 mole fraction). There is a systematic deviation
between HE(PTx) and HE(exper) in the ethanol-rich mixtures which again
suggests small composition-dependent changes in the boiling characteristics of
the system.

Gibbs-Helmholtz tests on simulated PTx data

It appears from the ethanol + water data discussed in the preceding section
that even if the level of random errors in the measured PTx data is low (0.05
to 0.12% scatter in the Barker's method pressure residuals), errors in
HE(PTx) can be much larger, say 10 to 50%. This is due to the temperature
 389

differentiation of the GE data which magnifies experimental errors. As

noted in the case of propylene glycol + ethylene glycol and ethanol + water, a
particular level of random error may be large enough to cause Gibbs-Helmholtz
inconsistency but not large enough to introduce significant errors into the
calculated vapor compositions. This can also be true of certain types of
systematic errors as was discussed for acetone + methyl acetate in relation to
the effect of fugacity-coefficient calculation method. Hence, data that fail
the Gibbs-Helmholtz test could still be used for chemical process design.
To investigate further, Gibbs-Helmholtz testing was done on computer-
generated PTx data to which known levels of random errors in pressure were
added. Details on the simulation are given in Table 2.

TABLE 2
Details on simulation of PTx data for Gibbs-Helmholtz testing shown in Table 3

Antoine Constants (LogTO, Wa. K) Component 1 Component 2

A 7.242673 6.173133

: 1580.92
-53.54 1294.40
-72.15

Temperatures (K) = 303.15, 308.15, 313.15, 318.45, 323.15, 328.15, 333.15,

338.15, 343.15

$(T) = (GE(323.15K)/323.15 + HE((323.15-T)/(T*323.,5)))(T)

GE l-5 GE(323'~~Kki
1 AxTx2 = Ax,2/RT Py = t .P.sati j = 1 2

J i ix11 3 9
Data were generated for xl = 0.0, 0.05, 0.10, 0.15, 0.2, 0.3, 0.4, 0.5
0.6, 0.7, 0.8, 0.85, 0.9, 0.95, 1.0

The derived HE(PTx) is from a least-squares fit of Barker-method derived

equimolar GE:

GE/RT = HE/RT - SE R
Fit parameters = H L and SE

The equimolar GE values were obtained from a Barker's method fit of the
corrupted PTx data. A one-parameter Redlich-Kister equation and ideal-gas
vapor phase were used in the data generation and fitting. Three levels of
nonideality were studied: equimolar GE(323.15K) values of 100, 500, and
1000 J/mol. Results of the Gibb-Helmholtz tests are shown in Table 3.
The results in Table 3 show that while the actual estimate'of equimolar
HE(PTx) fluctuates widely as the error in pressure increases, the uncertainty
in the estimated HE(PTx) increases monotonically. Hence, the level of
390

scatter in HE(PTx), which leads to Gibbs-Helmholtz inconsistency, increases

with the level of random error in pressure as expected.

TABLE 3
Effect of random errors in pressure on equimolar HE derived from simulated
PTx data via the Gibbs-Helmholtz equation

x1 = x2 = 0.5

GE(323.15K) HE Error P HE (PTx) Error HE <IY-YcalcI>

W;;;Tx))
J/mol J/mol % J/mol % mol %

100 150 0.01 150.2 0.8 0.13 0.0011

0.05 151 5.6 0.7 0.0081
0.25 148 15 1.3 0.024
0.50 183 32 22 0.056
1.00 205 37 0.12
1.00 410 1:: 170 0.22
1.75 -374 150 350 0.39
2.50 188 200 25 0.29
5.00 -790 380 630 0.66

500 750 0.5 743 30 0.9 0.056

1.o 853 65 14 0.13
2.5 738 200 .2 0.30
5.0 606 260 19 0.47
7.5 433 420 42 0.96

1000 1500 1.0 1428 5 0.073

5.0
10.0
2005
743
23240
436
33
50
0.52
1.2

HE(PTx) = Equimolar excess enthalpy from least-squares fit of GE/RT vs. T

SD = Standard deviation estimate from least-squares fit
Error P = Level of random error in pressure added to simulated data
Error HE = (/HE-HE(PTx)l/HE) x 100
<(y-ycalcI>= Average mean deviation of vapor composition for liquid
compositions 0.055x10.40

For the case where the equimolar GE(323.15K) value is 100 J/mol, a random
error level in pressure of 0.50 to 1.00% leads to Gibbs-Helmholtz inconsistency
as defined by eqn. (3). However, this level of random error introduces
uncertainties only of 0.0006 to 0.0012 into the calculated vapor mole
fractions. PTxy data thus derived could be used for chemical process design.
Results for the more non-ideal systems, equimolar GE(323.15K) values at 500
and 1000 J/mol, show that although higher levels of random errors in pressure
could be tolerated before Gibbs-Helmholtz inconsistency occurred, the effect
on derived vapor compositions remained constant.
 391

Two final notes on this analysis of simulated data: (i) Any number of
artificial systems could have been studied although the present constraint
that equimolar HE = 1.5 GE(323.15K) increases the level of random pressure
errors that are needed to produce Gibbs-Helmholtz inconsistency and thus-
represents a conservative case. (ii) More often in practice, it is systematic
data errors that are important and no consistency test can "undo" systematic
measurement errors (Van Ness and Abbott, 1982, pp. 326-327). However, these
simulated data tests indicate that a modest level of random error may vitiate
the Gibbs-Helmholtz consistency test before it can be used to detect
systematic errors, particularly for nearly ideal systems.

CONCLUSIONS
The Gibbs-Helmholtz thermodynamic consistency test should be used to judge
the overall integrity of PTx data measured at several temperatures rather than
to test whether derived vapor compositions are suitable for chemical process
design. The weakest link in producing accurate vapor compositions from PTx
data often is the vapor-phase fugacity model (Abbott, 1977). The Gibbs-
Helmholtz analysis tests primarily for correct temperature dependence, usually
a second-order effect in VLE for chemical process design.
Data of the highest quality should pass the Gibbs-Helmholtz test; therefore,
it should be used to analyze measurements reported as reference data. In this
context, equimolar HE(PTx) values within +30% of HE(exper) can be regarded
as thermodynamically consistent. Failure to pass the Gibbs-Helmholtz test
suggests the presence of:
levels of random error higher than can be tolerated in reference
data (for example,>O.Ol to 0.13 kPa errors in pressure),
temperature-dependent systematic errors related to the experimental

apparatus or procedure,
systematic errors in either the data-reduction process or in
the required ancillary thermophysical property data.

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