Fluid Phase Equilibria, 14 (1983) 383-392 Elsevier Science Publishers B.V.

, Amsterdam

383 - Printed in Tbe Netherlands

THERMODYNAMIC

CONSISTENCY

TESTING

OF PTx-DATA

VIA THE GIBBS-HELMHOLTZ

EQUATION

JAMES

D. OLSON Corporation, Research and Development (U.S.A.) Department, P. 0. Box 8361,

Union Carbide

South Charleston,

West Virginia

25303

ABSTRACT Although the Gibbs-Duhem equilibrium slope data, and area consistency the Gibbs-Helmholtz at several tests cannot equation be used on

PTx vapor-liquid

can be used to This is

test the consistency done by comparison Results

of PTx data measured

temperatures. enthalpy

to calorimetrically-determined for Gibbs-Helmholtz acetone + methyl tests

excess

(HE) data.

are presented

on ebulliometrically-determined propylene glycol + ethylene

PTx data for the systems glycol errors These random and ethanol

acetate, results

+ water.

In addition,

on the effect

of random

on Gibbs-Helmholtz studies errors on actual

testing

of computer-generated PTx data usually indicate claimed

PTx data are given. that, on the one hand,

and simulated measurement

in pressure

(0.01 to 0.1 kPa) should hand, random inconsis-

not cause errors

the Gibbs-Helmholtz measurement

test to fail, large enough to cause

and, on the other

in pressure

to give Gibbs-Helmholtz errors

tency may

not be large enough This

unacceptable

in the calculated test is stringent design.

vapor compositions.

indicates

that the Gibbs-Helmholtz

and data that fail may still

have practical

value for chemical

process

INTRODUCTION PTxy (pressure-temperature-liquid data are redundant thermodynamic mole fraction-vapor mole fraction) vapor-

liquid equilibrium differential

according

to the phase rule. tests

Hence,

and integral

consistency 1969).

can be constructed a PTxy are examined

from the Gibbs-Duhem consistency

equation

(Prausnitz,

More

recently, vs. y(calc)

test has been developed errors

in which

y(exper)

for systematic

(Van Ness et al., necessary

1973).

In contrast,

Px or TX (PTx) tests are

data are the minimum not possible.

to specify

VLE so that the Gibbs-Duhem

However,

GE data derived

from PTx data measured

at several

0378-3812/83/$03.00

@ 1983

Elsevier Science Publishers B.V.

384 temperatures equation,

(GE/~~)/2

can be compared

to

calorimetric

HE data

with

the

Gibbs-Helmholtz

-RT+

T],

= HE

(1)
as a thermodynamic and Prausnitz, Rubio to et ~1.5 al., consistency 1968; 1982). Bae et test al., for 1980; PTx data. Van Ness is can

This

comparison have

can be used appeared Olson, (Harris 1981;

Examples and Smith, limited usually

1981;

The discussion volumetric

here

to

low-pressure

VLE (up

MPa) where

effects

be neglected. objective of systematic data sets of thermodynamic errors. on the consistency uses (ii) data, to tests are justify and (iii) is (i) to to show the referee in

The principal likely between the data absence different

The practical same system, from the

confidence to testing ensure and

chemical of the of

process highest theory. evidence

equipment quality for

designed

experimental of PTx data

standards to pass

and for the

extension is the that errors. indirect data the

The failure that procedure the

Gibbs-Helmholtz the also details suggests systematic

test of

experimental contain

measurements errors. PTx data

and/or This contain

reduction vapor

systematic from the

compositions

calculated

The purpose fail that the fail

of

this

paper test any

is

to

discuss

how bad PTx data y values for predicted design. measured larger This at

have from is Union random

to

be to

Gibbs-Helmholtz can still have

and whether practical on three contain

PTx data done by and in

value

examining

Gibbs-Helmholtz data

tests that

systems successively

Carbide errors

on computer-generated pressure.

01 SCUSSION Gibbs-Helmholtz Experimental determined propylene measured method Abbott, (for 1982, at glycol tests on measured suitable for PTx data for three Gibbs-Helmholtz systems: and ethanol 1982) reduction fitted acetone + water. were methods, to virial ideal the testing have been

PTx data Union

Carbide

+ methyl These derived

acetate, PTx data by Barker s were

+ ethylene of 6).

glycol, (Olson, PTx data

by ebulliometry a discussion Chapter equation. from glycol the

and GE data

see Van Ness and PTx data was the were except for to be was found to

The GE model The vapor-phase glycol where were

Redlich-Kister calculated propylene sufficient.

fugacity the

coefficients equation gas model

pressure-explicit

second

+ ethylene

Equimolar

GE/RT data

plotted

against

temperature

obtain

385 an equimolar compared perform HE(PTx) from a graphical HE(exper) test. slope. This HE(PTx) was then experiments to

to an equimolar

value

from heat-of-mixing

the Gibbs-Helmholtz

In addition, from

plots of GE, HE, and TSE

vs. composition

were constructed

the equation:

GE= HETABLE 1

TSE

(2)

Comparison

of calorimetric

equimolar

HE(exper)

with

equimolar

HE(PTx)

derived

from Gibbs-Helmholtz

analysis

of PTx data

System

(KT) 323. 5

HE T;;oPyr) 5

"5 F'F'y) 5

ErrSr p

Acetone (1) + Methyl Acetate

(2)

86.5a

a8b

1.7

0.05-0.07

Propylene Glycol (1) + Ethylene Glycol (2) Ethanol Water (1) + (2)

408.

323. 343. 5"

-g:

-175d
118d

42 11

0.05-0.12

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 criterion,

gives

a summary

of the Gibbs-Helmholtz

tests.

If we use the

0.5 HE(exper)sHE(PTx)s1.5

HE[exper),

x1=x2=0.5

(3) + water pass the Gibbsglycol fails. Note in

the systems Helmholtz

acetone

+ methyl

acetate

and ethanol

test while

the system

propylene

glycol + ethylene

that the level of pressure pressure equal to absolute

uncertainty errors

in these data is low (0.05 to 0.22% to 0.08 kPa). data for this system the high degree ideal

of 0.01

Acetone

(1) + methyl

acetate

(2).

The experimental Figure

have been published Gibbs-Helmholtz system.

(Olson,

1981).

l(a) indicates

of

consistency

shown by the derived

GE for this nearly

(b)

L
290

1 300

310

320 1 K I

330

0.2

0.4

0.6

0.6

TEMPERATURE

Xl

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

In

the

published to be

analysis,

the

degree

of

agreement

of HE(PTx) virial Use

and

HE(exper) for method

was

shown

sensitive

to the method fugacity the

of estimating coefficients. HE(PTx) that also

coefficients

calculation gave a 323.15

of vapor-phase K value of

of a different hence Gibbs-

equimolar shows but

= 0.0

and

Helmholtz not only

inconsistency. to the values

This

Gibbs-Helmholtz to the details

testing of data <0.0002 fugacity

is sensitive reduction. between the

experimental of calculated

data

However,

vapor

composition between

differed

two methods coefficients HE(PTx) the

because

of cancellation in the

changes

in the

and changes

activity is found

coefficients. only in nearly have

This

sensitivity systems

of where

to fugacity

coefficients and that,

ideal similar

activity Figure

coefficients indicates

fugacity although

coefficients the magnitude This

magnitudes. vs. x is

l(b) the

of HE(PTx)

correct, dependent

second-order error.

skewness

is not.

suggests

a composition-

systematic qlycol GE

Propylene derived

(1) + ethylene data have only

glycol

(2).

Figure

2(a)

shows

that

the

equimolar the

qualitatively is more

correct than seven

temperature times too large.

dependence;

equimolar

HE(PTx)

value

387

(a)

(b)

-250 -

390

400

410

420 ( K 1

TEMPERATURE

Xl

analysis of PTx data for propylene glycol (1) + Points (0) and I;;, Pi;?) Equimolar GE/RT vs. temperature. 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. ~thyle;ed~;~;~; Data for this system for the other were measured were not determined Instead, were isobaric directly on isotherms as were data

Fig. 2.

Gibbs-Helmholtz

systems.

data at 6.67,

13.33 and 26.66 kPa Note also that (if we

and isotherms

constructed is worse

by interpolation.

the slope disagreement assume dHE/dT

in Fig. Z(a) This

at lower temperatures

to be small).

suggests

a temperature-dependent hydrogen-bonding Finally, agree well with vapor a materials

systematic

error

in the measurement. and less consistently data derived (Sokolov

For example,

boil differently

at lower pressures.

relative-volatility previous pressures Figure PTxy study

from these PTx measurements actually

et al., 1972) when the 1972 data.

measured

are used to analyze Z(b) shows

that the HE and TSE functions as GE. This system

obtained

from HE(exper)

are of the same magnitude Ethanol (1) + water methods

(2).

is an excellent

choice

for testing data published Figure 3(a) and

VLE measurement by Larkin shows

because

of the extensive

and consistent (1978).

and Pemberton

(1976) and Pemberton in the equimolar is achieved

and Mash

that the sign reversal

HE is correctly at the +10-40X

predicted

that Gibbs-Helmholtz equimolar HE(PTx).

consistency

error

level in

388

(a)

(b)

306 600 ;i d Cd :: ?s. 0 8 F (r \ %

I .

305

304

yi -400 E -600 -600

4 , I

303 320

330 TEMPERATURE

340 (K 1

350

0.2

0.4

0.6

0.6

I.0

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 temperatures and which

that

again

the that

slope the

disagreement + water

is worse system type

at

lower more smoothly

suggests

ethanol Absence

boils

consistently

at higher

pressures. can be used

of this

of systematic suitability of

dependence ebulliometry For this

on temperature as a route system, study. the NPL we

as a criterion

of the

to VLE data. can compare 3(b) well all three that excess functions with an K derived

independent agrees vapor with

Figure study would

shows within than

the

GE function error. accurate

at 343.15 Hence, for the

experimental sufficiently There

compositions (error HE(PTx) small

be more mole

design deviation

purposes between suggests the

in yCO.0005 and HE(exper)

fraction).

is a systematic which

in the

ethanol-rich changes

mixtures

again of

composition-dependent

in the boiling

characteristics

system.

Gibbs-Helmholtz It appears that even

tests from the

on simulated ethanol

PTx

data data discussed in the PTx preceding data is low in section (0.05

+ water errors method

if the scatter

level in the

of random Barker's say

in the measured pressure This

to 0.12% HE(PTx)

residuals), is due

errors

can

be much

larger,

10 to 50%.

to the

temperature

389 differentiation noted of the GE data which magnifies glycol experimental glycol errors. As + water, a

in the case of propylene level of random

+ ethylene

and ethanol

particular

error may be large enough to introduce

to cause Gibbs-Helmholtz errors into the

inconsistency calculated systematic the effect

but not large enough

significant

vapor compositions. errors

This can also be true of certain for acetone calculation + methyl method. acetate Hence,

types of in relation to

as was discussed

of fugacity-coefficient

data that fail design.

the Gibbs-Helmholtz To investigate generated added.

test could still be used for chemical further, Gibbs-Helmholtz

process

testing was done on computererrors in pressure were

PTx data to which known on the simulation

levels of random are given

Details

in Table 2.

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

Antoine

Constants A :

(LogTO,

Wa.

K)

Component

Component

7.242673 1580.92 -53.54 308.15, 343.15 313.15, 318.45, 323.15, 328.15,

6.173133 1294.40 -72.15 333.15,

Temperatures

(K) = 303.15, 338.15,

$(T) GE

= (GE(323.15K)/323.15 l-5 GE(323'~~Kki 1 AxTx2 generated

+ HE((323.15-T)/(T*323.,5)))(T) Py i = t .P.sati ix11 3

j = 1

= Ax,2/RT J

Data were

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 is from a least-squares fit of Barker-method derived

The derived HE(PTx) equimolar GE:

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

The equimolar corrupted vapor

GE values

were obtained

from

a Barker's

method

fit of the and ideal-gas levels of

PTx data.

A one-parameter

Redlich-Kister

equation

phase were were

used in the data generation studied: equimolar

and fitting. values

Three

nonideality 1000 J/mol.

GE(323.15K) tests

of 100, 500, and 3.

Results

of the Gibb-Helmholtz 3 show that while as the error increases

are shown in Table estimate'of

The results HE(PTx)

in Table

the actual

equimolar

fluctuates

widely

in pressure

increases, Hence,

the uncertainty

in the estimated

HE(PTx)

monotonically.

the level of

390 scatter with the in HE(PTx), level which leads error to Gibbs-Helmholtz in pressure inconsistency, increases

of random

as expected.

TABLE Effect PTx

3 of random via the errors in pressure on equimolar HE derived from simulated

data

Gibbs-Helmholtz

equation

x1 = x2 = 0.5 GE(323.15K) J/mol HE J/mol Error % P HE (PTx) J/mol W;;;Tx)) Error HE % <IY-YcalcI> mol %

100

150

0.01 0.05 0.25 0.50 1.00 1.00 1.75 2.50 5.00 0.5

150.2 151 148 183 205 410 -374 188 -790 743 853 738 606 433 1428 2005 743

0.8 5.6 15 32 1:: 150 200

380

0.13 0.7 1.3 22 37 170 350 25 630 0.9 14 .2 19 42 5 33 50

0.0011 0.0081 0.024 0.056 0.12 0.22 0.39 0.29 0.66 0.056 0.13 0.30 0.47 0.96 0.073 0.52 1.2

500

750

1.o
2.5 5.0 7.5

30 65 200 260 420

1000

1500

1.0 5.0 10.0

436

23240

HE(PTx) SD Error P Error HE <(y-ycalcI>=

= = = =

Equimolar excess enthalpy from least-squares fit of GE/RT Standard deviation estimate from least-squares fit Level of random error in pressure added to simulated data (/HE-HE(PTx)l/HE) x 100 Average mean deviation of vapor composition for liquid compositions 0.055x10.40

vs.

For error

the level

case

where

the

equimolar to

GE(323.15K) 1.00% this leads

value

is

100 J/mol,

a random inconsistency

in pressure by eqn. only PTxy (3).

of 0.50 However,

to Gibbs-Helmholtz error

as defined

level into be

of random the used

introduces mole design. at 500

uncertainties fractions. Results and 1000 for

of 0.0006 thus

to 0.0012 derived

calculated for

vapor

data

could

chemical

process values

the more show

non-ideal that

systems,

equimolar levels

GE(323.15K) of random

J/mol,

although

higher

errors

in pressure the effect

could

be tolerated vapor

before

Gibbs-Helmholtz remained

inconsistency constant.

occurred,

on derived

compositions

391 Two final artificial notes on this could analysis of simulated data: (i) Any number of

systems

have been studied

although

the present

constraint pressure

that equimolar errors

HE = 1.5 GE(323.15K) to produce case.

increases

the level of random inconsistency in practice,

that are needed

Gibbs-Helmholtz (ii) More often

and thusit is systematic systematic these

represents data errors measurement simulated

a conservative

that are important errors

and no consistency

test can "undo"

(Van Ness and Abbott, indicate consistency particularly

1982, pp. 326-327). level of random

However,

data tests

that a modest test before for nearly

error may vitiate

the Gibbs-Helmholtz systematic errors,

it can be used to detect ideal systems.

CONCLUSIONS The Gibbs-Helmholtz the overall integrity thermodynamic consistency test should be used to judge rather than

of PTx data measured vapor compositions

at several

temperatures

to test whether design.

derived

are suitable

for chemical

process

The weakest

link in producing fugacity

accurate model

vapor compositions 1977).

from PTx

data often Helmholtz

is the vapor-phase analysis tests

(Abbott,

The Gibbsusually

primarily

for correct

temperature design.

dependence,

a second-order

effect

in VLE for chemical quality should pass

process

Data of the highest it should context,

the Gibbs-Helmholtz reported as reference

test; data.

therefore, In this

be used to analyze equimolar HE(PTx)

measurements

values

within +30% Failure

of HE(exper)

can be regarded test

as thermodynamically suggests the presence

consistent. of: error

to pass the Gibbs-Helmholtz

levels data

of random

higher

than can be tolerated

in reference

(for example,>O.Ol

to 0.13 kPa errors systematic errors

in pressure), to the experimental

temperature-dependent apparatus systematic or procedure, errors

related

in either

the data-reduction property

process data.

or in

the required

ancillary

thermophysical

REFERENCES Abbott, M. M., 1977. Measurement of vapor-liquid equilibrium. In: S. I. Sandler and T. S. Storvick (Editors), Phase Equilibria and Fluid Properties in the Chemical Industry ACS Symp. Ser. No. 60, pp. 87-98. Bae, K. H., Nagahama, K. ani Hirata, M., 1980. Evaluation and correlation of vapor-liquid equilibria in the ternary system nitrogen-argon-oxygen, Fluid Phase Equilibria, 4: 45-60.

392 Harris, H. G. and Prausnitz, J. M., 1968. Thermodynamic properties of binary mixtures of 1-hexyne and polar organic solvents. 14: AIChE Journal, 737-740. Larkin, J. A. and Pemberton, R. C., 1976. Thermodynamic properties of mixtures of water + ethanol between 298.15 and 383.15 K, NPL Report Chem. 43, National Physical Laboratory, Division of Chemical Standards, Teddington, UK. Ebulliometric determination of PTx data and GE for Olson, J. D., 1981. acetone + methyl acetate from 20 to 60C, J. Chem. Eng. Data, 1981, 26: 58-64. Ebulliometry as a route to mixture thermodynamic data: Olson, J. D., 1982. J. V. Sengers (Editor), Proceedings of the Eighth PTx, GE, 'boo. In: Symposium on Thermophysical Properties. Volume I: Thermophysical Properties of Fluids. ASME, New York, pps. 343-348. Pemberton, R. C. and Mash, C. J., 1978. Thermodynamic properties of aqueous non-electrolyte mixtures II. Vapor pressures and excess Gibbs energies for water + ethanol at 303.15 to 363.15 K determined by an accurate static method. J. Chem. Thermodynamics, 10: 867-888. Prausnitz, J. M., 1969. Molecular Thermodynamics of Fluid-Phase Equilibria, Prentice-Hall, Englewood Cliffs, New Jersey, pps. 212-220. Rubio, R. G., Renuncio, J. A. R., and Diaz Pena, M., 1982. Excess Gibbs energies of (benzene + n-pentadecane) at 298.15 and 323.15 K. J. Chem. Thermodynamics, 14: 983-989. Sokolov, N. M., Tsygankova, L. N., Shtrom, M. I. and Zhavoronkov, N. M., 1972. Vapor-liquid equilibrium of 1,2-propylene glycol-ethylene glycol. Khim. Prom. 48: 499-501 (in Russian). Van Ness, H. C. and Abbott, M. M., 1982. Classical Thermodynamics of Nonelectrolyte Solutions with Applications to Phase Equilibria, McGraw-Hill, New York. Van Ness, H. C. and Smith, B. D., 1981. 4a. Excess Gibbs energy: aniline (1) + 1-pentene (2). Int. DATA Ser., Ser. A, Selec. Data Mixtures, No. 2: 87. Van Ness, H. C., Byer, S. M. and Gibbs, R. E., 1973. Vapor-liquid equilibrium: Part 1. An appraisal of data reduction methods. AIChE Journal, 19: 238-244.