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[LUIDPHASE

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ELSEVIER Fluid Phase Equilibria 137 (1997) 149-162

Vapour-liquid equilibria. XII. The ternary system


methanol-chloroform-acetone at 303.15 K
P. O r a c z , S. W a r y c h a *
Warsaw University, Department of Chemistry, Pasteura 1, 02-093 Warsaw, Poland
Received 20 January 1997; accepted 15 April 1997

Abstract

Total vapour pressure measurements made by the modified static method for the ternary system methanol-
chloroform-acetone and the constituent binary system chloroform-acetone at 303.15 K are presented. Different
expressions for G E suitable for correlation of these data are tested. The prediction of ternary VLE from
constituent binaries is studied. Accuracy of prediction of H E from general parameters fitted to several (4)
isotherms is studied for binary system. The possibility of predicting the ternary H e from VLE isotherms is also
studied. Our results are compared with literature data. © 1997 Elsevier Science B.V.

Keywords: Data; Vapour-liquid equilibria; Correlation; Acetone; Chloroform; Methanol

1. Introduction

The m e t h a n o l - c h l o r o f o r m - a c e t o n e system at 313.15 and 323,15 K was investigated in our


laboratory [1] within project on measurements, correlation and prediction of the ternary V L E systems
of non-electrolytes. In this paper we report the results of total vapour pressure measurements at
303.15 K for the ternary system and the binary c h l o r o f o r m - a c e t o n e ones. The remaining constituent
binaries were investigated and published previously [2,3].

2. Materials

The chemicals used were of the highest purity available from the suppliers. Chloroform (analytical
reagent grade, POCh) was prepared just before measurement to avoid its decomposition. The small

* Corresponding author.

0378-3812/97/$17.00 © 1997 ElsevierScienceB.V. All rights reserved.


PII S0378-3812(97)00101-5
150 P. Oracz, S. Wao:cha / Fluid Phase Equilibria 137 (1997) 149-162

Table 1
Vapour pressures P and second virial coefficients /3~,,, of pure substances used
Compound P(303.15 K)(kPa) -/3~ (303.15 K)
This work Literature ( d m 3 m o l - t)
Methanol 21.913 21.860 _+0.012 ~ 1.833 d
21.887 b
Chloroform 32.351 32.330 + 0.013 ~ 1.234 ~
32.331 b
Acetone 37.977 38.008 -+-0.012 ~' 1.906 ~
38.009 _+0.02Y ~
38.000 b

~Calculated according to Boublik et al. [46].;


bCalculated according to Dykyj and Repa~ [47] and Dykyj et al. [48].;
CCalculated according to Dymond et al. [49] with parameters fitted to recommended data of Dymond and Smith [50].
dCalculated with Tsonopoulos parameters fitted to recommended data of Dymond [51]. (Note: molar liquid volumes were
calculated according to Yen and Woods [52].)

quantity of ethanol (about 0.8%), which is added for stabilization, and possible trace amounts of water
were removed with 5A molecular sieves. Methanol (analytical reagent grade, POCh) was fractionated
on an efficient column having 80 theoretical plates and stored over 3A sieves. Acetone (analytical
reagent grade, POCh) was purified as a sodium iodide addition compound, in accordance with the
recommendations of Vogel [4]. The product obtained was then rectified on an efficient column and
dried by the 3A molecular sieves. It is very important to use neither basic nor acidic dehydrated
reagents due to formation of the enol form of acetone.
Impurities were determined chromatographically. Water content was checked using Fischer's
reagent and was on the limit of detectability. All the substances had purity not less than 99.95 mole
per cent. Table 1 gives the vapour pressures of the pure substances, measured both in our laboratory
and reported in the literature, along with second virial coefficients.

3. Method

The vapour pressures of the mixtures were determined by a modified static method. The apparatus
and experimental procedure have been described previously [5]. During our measurements the
temperature was constant to within 0.004 K and was controlled up to 0.001 K; the absolute deviation
is estimated to be equal to + 0.02 K (ITS-90). The cathetometer readings contribute less than 0.004
kPa to the error of a single pressure measurement. This is a major part of the error in pressure if both
errors in temperature and pressure are treated separately. The errors in the mole fractions were not
higher than 0.0005. The ternary samples were prepared from mixtures of chloroform with methanol,
to which acetone was added.

4. Results and discussion

The results of total vapour pressure measurements are given in Table 2 for binary (chloroform-
acetone) system and in Table 3 for ternary one.
P. Oracz., S. Warycha / Fluid Phase Equilibria 137 (l 997) 149-162 151

Table 2
Liquid mole fraction x,,, calculated vapour mole fractions Ya, total vapour pressures P and deviations d P for the
chloroform-acetone system at 303.15 K; ( d P = P - Pcalc and y,, calculated with Eq. (1))
x. Ya P (kPa) d P (kPa) x~, y~, P (kPa) d P (kPa)
0.0000 0.0000 37.977 0.000 0.5562 0.5246 27.148 0.002
0.0322 0.0140 37.274 0.027 0.6062 0.6041 26.991 - 0.005
0.0797 0.0366 36.182 0.018 0.6582 0.6844 27.127 0.009
0.1414 0.0701 34.749 -0.000 0.7366 0.7927 27.786 -0.015
0.2076 0.1128 33.212 -0.013 0.7989 0.8631 28.690 0.002
0.2855 0.1752 31.453 - 0.005 0.8650 0.9216 29.828 -0.006
0.3527 0.2423 30.018 -0.001 0.9355 0.9681 31.176 0.026
0.4254 0.3305 28.668 0.008 1.0000 1.0000 32.351 0.000
0.4551 0.3712 28.192 -0.001

The binary systems were correlated by various equations such as: Redlich and Kister [6], Van Laar
extended by Van Ness [7], Myers and Scott [8], Marsh [9], SSF (Rogalski and Malanowski, [10]),
Wilson [11], the 3 parameter Wilson (Novak et al., [12]), Wilson as modified by Tsuboka and
Katayama [13], NRTL (Renon and Prausnitz, [14]), UNIQUAC (Anderson and Prausnitz, [15]), Abott
and Van Ness [16], Ortega [17] and pseudo-volume-fraction Redlich-Kister (as suggested by
Scatchard and Hamer [18] and Asmanova and G6ral [19]). For the methanol containing systems the
Wilson and NRTL equations were also used with additional term accounting, for association of
methanol; the Kretschmer-Wiebe model was used [20]. The association constants, used in this model,
were adopted from works of Nagata and treated as non-adjustable parameters. Unfortunately,
equations with the Kretschmer-Wiebe term described experimental data much worse than original
one and were rejected from consideration. Coefficients of these equations were obtained by a
modified Barker's method [21-23]. The values of second virial coefficients for the pure substances
were calculated using literature data (cf. Table 1) and for the mixtures were calculated according to
Tsonopoulos [24]. Table 4 shows the efficiency of these equations applied to our data. We assumed
that the maximum number of the coefficients used should not exceed six.
The presented results as well as those reported previously [1] demonstrate that the expressions for
G E based on the local composition concept do not provide a sufficiently accurate description of
systems with an extremum on the activity coefficient versus mole fraction (methanol-chloroform) as
well as complex curves of activity coefficients in chloroform-acetone system. The moderate
non-ideal system methanol-acetone can be described by any equation with approximately the same
accuracy.
For correlation of our binary measurements we chose the Redlich-Kister equation

GE/RT=x,,(1 --Xa) ~ Ki(Zx o - 1) i (1)


i=0

Values of the K i coefficients in Eq. (1) together with their standard errors o-( K i) and the correlation
coefficients qo for pairs (K i, Kj) are given in Table 5 for all the binary systems. The qij values
together with the standard errors o-(Ki) allow, if necessary, the estimation of standard errors of all
values, which depend on K.
The chloroform-acetone system was measured at 303.15 K by Schulze [25], Schmidt [26], R~3ck
152 P. Oracz, S. War3'cha/ Fluid Phase Equilibria 137 (1997) 149-162

Table 3
Ternary system methanol (a)-chloroform (b)-acetone (c) at 303.15 K: experimental liquid mole fractions x a, x b and total
pressure P; vapour mole fractions Ya, Yb and deviations d P (d P = P - P~-alc) calculated with Eq. (3) and (4) having three
ternary parameters fitted to the data
Xa "X'b Ya Yb P (kPa) d P (kPa)
0.8655 0.0673 0.7133 0.1421 27.136 0.010
0.7941 0.0617 0.6264 0,1002 29.099 0.073
0.7083 0.0550 0.5398 0.0683 31.121 0.044
0.6276 0.0488 0.4718 0.0491 32.813 0.068
0.5398 0.0419 0,4075 0.0348 34.312 0.031
0.3438 0.0267 0.2807 0.0162 36.808 0.021
0.1921 0,0149 0.1778 0.0076 37.926 0.005
0.6742 0.2537 0.4927 0.4308 32.383 - 0.151
0.6174 0.2323 0.4873 0.3392 31.704 -0.095
0.5469 0.2058 0.4558 0.2453 31,915 -0.008
0.4337 0.1632 0.3773 0.1422 33.353 0.027
0.2676 0.1007 0.2498 0.0613 35,802 - 0.017
0.4844 0.4644 0.3627 0.6100 36.897 - 0.033
0.4505 0.4320 0.3791 0.5440 34.925 -0.069
0.4139 0.3969 0.3845 0.4670 33.405 - 0.107
0.3565 0.3418 0.3657 0.3470 32.481 0.001
0,3237 0,3103 0.3428 0.2854 32.593 0.115
0.2489 0.2386 0.2730 0.1741 33.424 -0.003
0.2153 0.2064 0.2384 0.1367 34.048 -0.022
0.1344 0,1289 0.1526 0,0699 35.624 -0.072
0.0771 0.0740 0.0895 0.0358 36.737 - 0.019
0.2821 0.6692 0.2887 0.6939 38.369 - 0,011
0.2683 0.6365 0.2935 0,6659 36.957 -0.012
0.2456 0.5827 0.2969 0.6076 34.784 - 0.020
0.2282 0.5413 0.2940 0.5529 33.461 0.022
0.1939 0.4599 0.2710 0.4295 31.904 0.066
0.1749 0.4150 0.2492 0.3601 31.651 0,061
0.1271 0.3016 0.1794 0.2092 32.429 -0.023
0.0670 0.1591 0.0887 0.0845 34.850 -0.066
0.1738 0.7770 0.2489 0.7346 38.213 0.031
0.1649 0.7370 0.2459 0.7149 36.728 0.045
0.1510 0.6750 0.2399 0.6695 34.465 0.023
0.1427 0.6378 0.2346 0.6333 33.291 0.036
0.1233 0.5514 0.2140 0.5262 31,329 0.060
0.1007 0.4501 0.1758 0.3814 30.605 0.031
0.0812 0.3632 0.1362 0.2665 31.145 -0.037
0.0739 0,3304 0.1212 0.2286 31.564 -0,050
0.0850 0.8602 0.1954 0.7848 37.048 0.179
0.0806 0,8160 0.1849 0.7714 35.368 0.049
0.0739 0,7477 0.1703 0.7337 33.048 - 0.050
0.0652 0,6604 0,1510 0.6533 30.767 -0.060
0.0505 0.5115 0.1114 0.4545 29.222 - 0.054
0.0412 0,4169 0.0838 0.3236 29,787 -0.056
P. Oracz, S. Wa~cha / Fluid Phase Equilibria 137 (1997) 149-162 153

and Schr6der [27], and Hopkins et al. [28]. We compared the experimental pressure of our data and
their data to the same reference line P + = f ( x a, K~ . . . . . Kn). The reference total pressure P+ was
calculated with Eq. (1) and parameters from Table 5. The same virial coefficients were used in all
cases. The pure component vapour pressures were those reported with the given set of data. Results
are presented in Fig. 1. As can be seen, literature data differ significantly from ours; the systematic
differences are up to 1.330 kPa (4.8%). For the more recent data differences are lower and have not
exceeded 1%. R6ck and Schr6der reported vapour phase compositions but a strict thermodynamic
consistency test of their data cannot be performed because pure component vapour pressures have not
been reported.
The binary systems under consideration have been investigated by other authors, who have
measured VLE under isobaric or isothermal conditions as well as molar enthalpy of mixing, H E.
Therefore it is possible to compare, simultaneously, various VLE and H e sets of data. In a previous
paper [29] we have presented different tests comparing our data for the chloroform-methanol system
with literature one including GE/RT vs. 1 / T test and comparison of azeotropic compositions at
different temperatures. For these tests data at 303.15 K were also used. The GE/RT vs. 1 / T test is
based on the following idea: each VLE data set under comparison may be represented by the value of
GE/RT at, for example, mole fraction equal to 0.5, henceforth denoted Qo.5. The Q0.5 values
calculated from various data sets were plotted against 1 / T . From the Gibbs-Helmholtz equation, the
slope of the resulting line should be equal to H~.5/R. Resulting plot for methanol-chloroform system,
not presented here, shows excellent consistency between our data at four temperatures and agreement
with those published in the literature as well as their consistency with the chosen values of H E.
Similar comparisons for the methanol-acetone and chloroform-acetone systems were presented
already in our previous paper [ 1]. Completing of these comparisons with corresponding data at 303.15
K shows excellent agreement with previous figures.
It is also possible to compare our values for the azeotropic point with those calculated from the
literature VLE data. For the methanol-chloroform and methanol-acetone systems such comparisons
are presented in our papers [29,3], respectively. For the chloroform-acetone system the mole fraction
of chloroform can be expressed as a function of temperature using the polynomial Xaz----0.2567--
1.165" 10 -3 T, with standard error o - ( x a z ) = 0.023, in the temperature range 273-363 K. For this
calculation 49 experimental data sets were used, the remaining literature data, evidently inconsistent,
were rejected. The accepted 49 data still exhibit great scatter. The subset including data of RiSck and
Schr6der [27], Abbott et al. [30], G6ral et al. [1] and data of this work, totally 11 points, can be
represented using equation Xa: = 0.3814 + 7.45 • 1 0 - 4 T with standard deviation cr(Xaz) = 0.0044,
whereas our data alone can be expressed as Xa~ = 0.3978 + 7 • 1 0 - 4 T with o-(xaz) = 1 • 1 0 - 1 2
According to suggestions of Malesifiski [31] we have used Antoine equation l n ( P a J k P a ) = A +
B/(T,~ + C) for fitting experimental azeotropic pressure data versus temperature; the resulting
equation l n ( P ~ J k P a ) = 1 4 . 8 6 2 6 - 3 1 1 1 . 8 8 / ( T ~ z - 3 3 . 8 4 8 ) represents 49 data, in the temperature
range 273-363 K, with standard deviation o - ( P / k P a ) = 0.41. All the above results indicate excellent
internal consistency of our data.
Calculated limiting activity coefficients at 303.15 K (this work), 313.15 and 323.15 K (our data
[1]), and 329.25 K or 334.35 K [32] may be used in test of agreement with corresponding limiting
partial molar enthalpy of acetone in chloroform, HaEcetone, a n d chloroform in acetone, OEloroform . T o
this end the relation [Olnyi/O(1/T)]e, x = HiE/R is used, where HiE is the partial molar enthalpy of
mixing of component i. The calculated value o f HaEccetoneat infinite dilution, equal to - 7.4 kJ m o l - 1,
154 P. Oracz, S. Warvcha/ Fluid Phase Equilibria 137 (1997) 149-162

Table 4
Comparison of the efficiency of different equations for binary systems at 303.15 K (number of parameters n, average
standard error of the total vapour pressure o-(P) ~')
Equation n cr (P)(kPa) Number of Calculated
sign changes b azeotropic point
x ~z P,z (kPa)
Methanol(a) + chloroform(b)
Pseudovolume
Redlich-Kister 6 0.032 7 0.278 39.84
Redlich-Kister 5 0.032 7 0.278 39.84
Van Laar-Van Ness 4 0,035 6 0.279 39.85
Myers-Scott 6 0.032 8 0.278 39.84
Marsh 2+ 3 0.034 8 0.279 39.87
Abbott-Van Ness 5 0.035 7 0.278 39.85
Ortega (k = 0.55) 4 0.035 6 0.278 39.85
SSF 6 0.043 14 0.280 39.87
Wilson 2 0.397 4 0.265 39.72
(4 isotherms) 4 0.413 2 0.268 39.81
(Novak et al.) 3 0.409 2 0.266 39.76
(Tsuboka-Katayama) 2 1.006 2 0.238 39.42
NRTE (ce = 0.2) 2 0.171 3 0.278 39.94
3 0.158 3 0.282 39.96
(4 isotherms, ce = 0.2) 4 0.173 3 0.279 39.93
UNIQUAC 2 0.342 2 0.266 39.75
(4 parameters) 4 0.345 2 0.268 39.78
Athermal Mecke-Kempter c 2 0.423 2 0.263 39.71

Methanol(a) + acetone(b)
Pseudovolume
Redlich-Kister 3 0.011 5 0.130 38.36
Redlich-Kister 3 0.010 7 0.114 38.37
Van Laar-Van Ness 3 0.010 7 0.114 38.37
Myers-Scott 3 0.029 4 0.114 38.33
Marsh 2+2 0.010 8 0.115 38.36
Abbott-Van Ness 4 0.010 8 0.115 38.36
Ortega (k = 0.90) 3 0.009 8 0.115 38.36
SSF 4 0.010 8 0.115 38.36
Wilson 2 0.019 4 0.114 38.35
(4 isotherms) 4 0.024 2 0.113 38.34
(Novak et al.) 3 0.018 3 0.112 38.37
(Tsuboka-Katayama) 2 0.012 5 0.114 38.36
NRTL (c~ = 0.3) 2 0.028 2 0.114 38.34
3 0.010 7 0.114 38.37
(4 isotherms, o~ = 0.3) 4 0.036 2 0.112 38.31
UNIQUAC 2 0.023 4 0.114 38.34
(4 isotherms) 4 0.032 4 0.112 38.32
Athermal Mecke-Kempter c 2 0.014 5 0.117 38.36

Chloroform(a)-acetone(b)
Pseudovolume
Redlich-Kister 4 0.012 8 0.644 21.05
Redlich- Kister 4 0.015 I0 0.610 26.99
P. Oracz., S. Warycha / Fluid Phase Equilibria 137 (1997) 149-162 155

Table 4 (continued)
Equation n cr(P)(kPa) Number of Calculated
sign changesb azeotropic point
x~ P~(kPa)
Van Laar-Van Ness 3 0.018 4 0.609 27.00
Myers- Scott 3 0.013 8 0.611 27.00
Marsh 2+ 2 0.015 8 0.611 27.00
Abbott-Van Ness 4 0.013 8 0.611 27.00
Ortega (k = 1.2) 4 0.013 8 0.611 27.00
SSF 4 0.041 3 0.617 26.99
Wilson 2 0.185 2 0.625 27.19
(4 isotherms) 4 0.182 2 0.625 27.17
(Novak et al.) 3 0.066 3 0.609 27.07
(Tsuboka-Katayama) 2 0.179 2 0.625 27.18
NRTL ( el = 0.3) 2 0.167 2 0.624 27.16
3 0.060 3 0.609 27.07
(4 isotherms, c~ = 0.05) 4 0.093 4 0.605 27.03
(4 isotherms, c~ = 0.3) 4 0.167 2 0.625 27.09
UNIQUAC 2 0.173 2 0.625 27.09
(4 isotherms) 4 0.169 2 0.624 27.16
Association modeld 2 0.055 2 0.615 27.07

ao"(P)= ['~(Pexp.- Pcalc.)2/(m- n)]°5, where m = number of points.


blf two neighbouring points lie on opposite sides of an approximation curve then one speaks of a sign change of their
deviations. The points should be scattered randomly in respect to the correlating curve. Easy measure of the randomness is
number of sign changes, which should be roughly equal to m/2_+(m/2) °5.
CAthernal Mecke-Kempter model according to Kehiaian and Treszczanowicz [20].
dldeal Association model with two postulated complexes, AB and AB 2, where A stands for acetone and B for chloroform,
respectively; cf. e.g. [53].

agrees with the corresponding value, - 8 . 1 +_ 0.2 kJ mol ~, obtained from experimental H e data of
Nagata et al. [33] at 298.15 K. For the Hjhlorofo~, e corresponding values are - 5 . 1 4 kJ mol-~ and
- 5 . 1 3 + 0.1 kJ m o l - ~ ; this is an excellent agreement. The above test can be performed, of course,
for any mole fraction but the limiting concentration activity coefficients best reflected all inaccuracies
in V L E data.
Use o f a local composition model with temperature dependent parameters for several isotherms
a n d / o r isobars results in 'general' parameters. Such parameters are built-in in process simulators data
bases. W e have performed such calculations using Wilson, N R T L and U N I Q U A C equations. For
a c e t o n e - m e t h a n o l system general parameters were used previously for comparison of experimental
and predicted enthalpy of mixing by Oracz et al. [3]. For m e t h a n o l - c h l o r o f o r m we have used 4
isotherms, measured in our laboratory, at 293.15 K [29], 303.15 K [2], 313.15 and 323.15 K [1], with
resulting standard error for Wilson equation 0.377 kPa (1.00%). For c h l o r o f o r m - a c e t o n e system we
have used also our 4 isotherms (303.15 K, this work; 313.15 and 323.15 K [1], and 293.17 K [34])
obtaining for Wilson equation standard error of 0.251 kPa (0.50%). Use o f N R T L equation with 4
adjustable parameters (with predefined c~ parameter) gives the lowest standard error, cr(kPa) = 0.146
(0.30%), but N R T L a-parameter has unusually low value of 0.05. A b o v e standard errors are of one
order higher than the corresponding values for m e t h a n o l - a c e t o n e system but comparable with values
156 P. Oracz, S. Wao, cha / Fluid Phase Equilibria 137 (1997) 149-162

Table 5
Parameters K s o f Eq. (1) with their standard errors ~r(Ks), correlation coefficients qij, and cross second virial coefficients
/ ~ a b a t 303.15 K

Methanol ( a ) - c h l o r o f o r m (b)
~ a b = - - 0.924 d m 3 mol i
i 0 1 2 3 4
Ks 1.28534 -0.55006 0.06808 -0.17218 0.14810
~K i 0.00117 0.00305 0.00800 0.00762 0.01534
qli - 0.0434
qzi -0.5967 - 0.1020
q3i 0.3041 -0.6824 - 0.0033
q4s 0.4816 0.2483 -0.8710 - 0.0354
Methanol ( a ) - acetone (b)
~ab = -- 1.357 d m 3 mol ]
i 0 1 2
K i 0.71070 0.00252 0.02018
~K s 0.00041 0.00090 0.00182
qli --0.0540
q2i - 0.4799
- - 0.2081
Chloroform ( a ) - a c e t o n e ( b )
~ a b = - - 1.953 d m 3 mol J
i 0 1 2 3
Ki - 0.97311 -0.19914 0.11907 0.06432
~K i 0.00109 0.00311 0.00363 0.00678
qli 0.1993
q2i - 0.6521
- - 0.0725
q3i -0.2112 -0.8281 0.1969

, , , , , , , , ,

1.2 A

a8 z~
g_
A
[]
L []
Qt.
0h A
[]

[] % @ • 1
o.o I I ~ l ~ , m ~ C ~ . - - - .-. _-~-a/

. . . . ~ . . . . I
0.5 1
Xch

Fig. 1. Chloroform-acetone. C o m p a r i s o n b e t w e e n literature and experimental data c o m p a r e d with the same reference line:
[3, Schulze [25]; A, S c h m i d t [26]; Q~, RiSck and SchfiSder [27]; O , Hopkins et al. [28]; • this work.
P. Oracz, S. Wa~cha / Fluid Phase Equilibria 137 (1997) 149-162 157

obtained in a single set correlation. These calculations also confirm internal consistency of our data.
The general parameters may be used for both inter- and extrapolation, and prediction of enthalpy of
mixing.
Having two sets of VLE data, at 303,15 (this work) and 313.15 K [1], we can calculate, using the
Gibbs-Helmholtz equation, the molar enthalpy of mixing, H e. Such calculations could be treated as a
consistency test of our data and a test of practical possibility of prediction of H e from narrow
temperature range VLE data. To this end we have rewritten the Gibbs-Helmholtz equation to the
form
Q(313.15 K) - Q(303.15 K)
He(3OS.15K)=R (2)
1/313.15- 1/303.15

Fig. 2 shows the comparison of the H e values calculated with Eq. (2), to the corresponding
experimental data, at 308.15 K, for chloroform-acetone systems. The experimental H e data at 308.32
and 308.15 K were taken from Marsh and Mgczyfiski [35]. The root mean square deviation, rmsd,
defined as [ ~ ( H i , E e x p t l - HiEcalc)2/m] °5, for both data sets treated simultaneously, is equal to 190 J
mol-~. For the proper understanding of Fig. 2 one should realize that each inaccuracy in the
difference Q(313.15 K) - Q(303.15 K) is reflected about 79000 times in H e value. To account for
random errors in total vapour pressure we plot on Fig. 2 boundaries (dashed lines) estimated for
relative standard error in pressure equal to 0.001. The boundaries were calculated at a confidence
level equal to 0.95. The dash-dotted line in Fig. 2 represents the H e values calculated from Wilson
equation with general, temperature dependent parameters. The root mean square deviations for
general parameters are 129 J mo1-1 for Wilson, 122 J m o l - ' for UNIQUAC and 126 J mo1-1 for

, , , , , , , , ,

-500

k', \
#
5"
"~ -I 000
E
', ~ \ //.'/
, \ ,\ \ / //,
I \OxXx, "_~ //0'
-I 500
/ " °">'-'/-'/
\ 0 (I)o/
-2 000 J l i l L ~1 ~l i i i

0 0.5
XCh
Fig. 2. Chloroform-acetone. Comparison of calculated enthalpy of mixing with experimental data: @, Onken [54]; ©,
Staveley et al. [55]. ( - - ) represents H E curve calculated using Eq. (2) with our VLE data. (---) mark the range
calculated with the assumption that relative standard error of single pressure measurement is equal to 0.001. ( - . - )
represents H E curve calculated using Wilson equation with general parameters. All the literature H E data were taken from
Marsh and Mgczyfiski [35].
158 P. Oracz, S. Warycha / Fluid Phase Equilibria 137 (1997) 149-162

NRTL. The use of local composition equations with general parameters results in better agreement
with experimental H e data than use of Eq. (2) with, better fitted to experimental VLE data,
Redlich-Kister one. According to the criteria discussed by Olson [36] the results shown in Fig. 2 can
be regarded as thermodynamically consistent. The same conclusion follows from comparison of
experimental and predicted values with statistical boundaries.
The ternary system was correlated by Eq. (3) and (4) using polynomial equations as well as the
Wilson, NRTL and UNIQUAC models. Eq. (3) is the one discussed previously by Oracz [37], to
which ternary terms were added. The equation has the form
2 3
GElRT= E E (xi + a p ,2+~,-.E,
u i j t x i, ) / R T + G e ( t e r ) / R T (3)
i=1 j - i + l

where xi* = x s / ( x i + xj). G~ is any equation suitable for the correlation of a binary mixture (i + j ) .
For this reason, Eq. (3) is much more general than any other proposed in the literature. Parameter/3 is
adjustable. In this work we used /3 = 1. This value is suitable for systems with saddle shaped
Ge-surface [1]. If /3 = 0 then Eq. (3) is equivalent to Kohler's equation. For the ternary contribution
Ge(ter) the following equation was used

O e ( t e r ) / R T = x , x t , x,. [ C 1 + C=(3x,,- 1) + C3(3xt, - 1)] (4)


Table 6 shows the efficiency of various equations applied to the ternary data. Use of ternary terms
results, in all cases, in better fits. Therefore, we have decided to use the Redlich-Kister equation with
3 adjustable parameters ternary term given by Eq. (4). Table 7 reports values of parameters in Eq. (4)

Table 6
Comparison of different equations for the ternary system methanol (a) - chloroform (b) - acetone (c) at 303.15 K (average
standard error of the total vapour pressure, cr ( P ) , relative standard error of the total vapour pressure, cr (d P / P ) a
Equation Number of parameters s ( P ) (kPa) cr(d P ~ P ) (%)
Binary b Ternary
Eq. (3),(4) with /3 = 0 (Kohler) using
Redlich-Kister 5/3/4 0 0.831 2.562
5 0.059 0.183
Eq. (3),(4) with /3 = 1 using
Redlich-Kister 5/3/4 0 0.211 0.633
3 0.063 0.188
Wilson 3/2/2 0 0.434 1.361
(4 isotherms) 4/4/4 0 0.643 1.982
NRTL 3/3/3 0 0.816 2.519
(4 isotherms) 4/4/4 0 2.691 8.312
(4 isotherms) 4/4/4 0 0.726 2.240
UNIQUAC 2/2/2 0 0.391 1.226
(4 isotherms) 4/4/4 0 0.342 1.07 |

ao-(P) = [X(Pex p - Pcalc)2/(m -- rt)] 05 (1/ = number of parameters, m = number of points); o-(dP/P)=[X(l-
Pcalc/Pexp)2/(m -- n)]° 5;
bthis column should be read: number of adjustable parameters for the mixture a + b / f o r the mixture a + c / f o r the mixture
b + c. The parameters are those fitted to the binary data (cf. Table 4)
P. Oracz, S. Warycha / Fluid Phase Equilibria 137 (1997) 149-162 159

Table 7
Coefficients C i o f Eq. (4) f o r the t e r n a r y p a r t o f the e x c e s s G i b b s e n e r g y , t h e i r s t a n d a r d e r r o r s cr(Ci), c o r r e l a t i o n
coefficients qij a n d c a l c u l a t e d p a r a m e t e r s o f the a z e o t r o p i c p o i n t f o r the t e r n a r y s y s t e m m e t h a n o l (a) - c h l o r o f o r m (b) -
a c e t o n e (c) at 3 0 3 . 1 5 K
i=1 2 3

C i = 0.0824 - 0.4221 - 0.5703


~ ( C i) = 0 . 0 1 4 4 0.0357 0.0278
q2i = 0 . 2 0 8 4
q3i = - 0 . 1 4 5 4 0.3912
azeotropic point: x a = 0.371; x b = 0.312; P/kPa = 32.45

with their standard errors and correlation parameters as well as calculated parameters of ternary
azeotropic point.
The ternary system was measured by Abbott et al. [30] at 323.15 K, Tamir et al. [38] at 298.15 K,
Shishkin et al. [39], Willock and Van Winkle [40], Tochigi et al. [41], Hiaki et al. [32] at 101.325 kPa
but these data cannot be compared directly with ours. We have found ternary enthalpy of mixing data
measured at 298.15 K [42] and 323.15 K [43]. Having VLE data at two temperatures, T 1 and T2, we
can predict values of enthalpy of mixing at temperature T = (TI + Tz)/2 (cf. Eq. (2)). Using Eq. (3)
and (4), with parameters fitted to ternary VLE data at 303.15 K and those at 313.15 K taken from our
previous paper [1], we have predicted ternary H E data. These predicted values were compared to
corresponding experimental one reported by Nagata and Tamura [42] at 298.15 K. The root mean
square deviation, rmsd, is equal to 299 J mol -I. The distribution of H E deviations between the
experimental and the predicted values exhibits systematic shift to positive deviations. This can be
explained by two factors. First, we have used data at 298.15 K instead of 308.15 K. All constituent
binary systems have positive molar excess heat capacities (at constant pressure) C~, so H E data at
308.15 K are higher than those at 298.15 K. The use of H E data at 308.15 K should result in shift of
the distribution of H E deviations to more negative deviations. The crude estimates for C~ enable
recalculation of H E data from 298.15 to 308.15 K; the rmsd for recalculated data is about 190 J
mol -~ The second factor we must take into account in such comparison is related to error
propagation; we must realize that any difference in Q(313.15 K ) - Q(303.15 K) is reflected about
79000 times in H E value. Taking into account the above factors one should state good internal
agreement of our VLE data with HE data of Nagata and Tamura.
Ternary azeotropic data were reported by Tochigi et al. [41], Hiaki et al. [32], Tamir et al. [38],
Ewell and Welch [44], and Horsley [45] at the pressure of 101.325 kPa. Abbott et al. [30] reported
azeotropic pressure at 323.15 K. Using data of Abbott et al. we have estimated compositions of
azeotropic point as being equal to Xmethanol= 0.4303, Xchloroform= 0.2611. From binary and ternary
data of Tamir et al. [38] we have calculated parameters of the ternary azeotropic point at 298.15 K
which differ sufficiently from original estimates of the authors. The literature azeotropic pressures,
together with values calculated from our present and previous ([1]) VLE data, were fitted to Antoine
equation, ln(P,z/kPa) = 14.0449-2420.47/(Taz - 74.116), with the standard deviation o- ( P / k P a ) ---
0.28. The azeotropic mole fraction of methanol can be expressed as a linear function of temperature,
xaz = -0.5361 - 0.003 • T, with standard error O'(Xaz) = 0.003, in the temperature range 298-331 K.
For the chloroform mole fraction the corresponding formula, xa~-- 1 . 1 2 9 3 - 0.0027. T, represents
160 P. Oracz, S. Wao'cha/Fluid Phase Equilibria 137 (1997) 149-162

data with standard deviation o-(xaz) = 0.004. In both above fittings the corresponding data of Tamir
et al. were neglected.

5. List of symbols

Ci coefficients in Eq. (4)


Ce molar excess heat capacity at constant pressure
GP~ excess Gibbs energy
excess Gibbs energy for the binary mixture i + j
Hk molar enthalpy of mixing
H 0.5
E molar enthalpy of mixing at mole fraction 0.5
Hi E partial molar enthalpy of mixing of component i
k selectable parameter in Ortega equation
Ki parameters in Eq. (1)
m number of experimental points
n number of adjustable parameters
P vapour pressure (kPa)
Q value of G E / R T
QO.5 value of G E / R T at mole fraction 0.5
qij correlation coefficients between parameter pairs ( K i, Ky) or (C i, Cy)
R gas constant
T temperature (K)
x mole fraction in liquid
x mole fraction in liquid in Eq. (3)
Y mole fraction in vapour

5.1. Greek letters

NRTL parameter
exponent in Eq. (3)
~aa' J~bb, J~ab second virial coefficients
Yi activity coefficient of component i
or standard error

Acknowledgements

This work was partially supported by KBN funds through the Department of Chemistry, University
of Warsaw within the project BST 5 3 2 / 1 6 / 9 6 .

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