452 K.-D. Kassmann and H. Knapp: Vapor-Liquid Equilibria for Binary and Ternary Mixtures etc.

~ _ _ _

as we have already done [I31 with measurements on low-
molecular weight DNA solutions.
Here, @ ( 4 ) is the counterion-counterion interaction ener-
gy in the Debye-Huckel approximation.
If the average number of counterions no is assumed to be
From the results presented here, we have deduced some
informations on the effects of strongly interacting counter-
ions on the conformation of linear, rod-like polyelectrolytes
in solutions with excess salt. Our results lead additional
I support to the continuum counterion distribution model of

equal to f of the Mandel model and estimated from the
degree of substitution, the average distance bo between two
charged groups may be calculated.
In the present case, for all the polyion concentrations
examined b,, assumes unrealistic high values so that the poly-
ion length L = Nbo would exceed the effective length of the
full extended macromolecular chain.
As has been done previously [I], a dependence of the
dielectric increment on a power of the macroion concentra-
tion must be supposed.
On the contrary, as might be expected from the similarity
of the dielectric profiles between monovalent and divalent
counterions, the dependence on frequency may be correctly
described adjusting the values of the C and W parameters.
Their values are found of the order of magnitude of lo6+lo7
sec-’ and lo3+ lo4 sec-’ respectively.
This model is rather successful in explaining, even quan-
titatively [14], the dielectric dispersions of many polyelec-
trolyte systems, but althought proposed for one dimensional
lattice structure, probably it fails at low ionic concentration
where electrostatic interactions will lead to a considerable
extension of the macromolecular chain.
It should also be noted that, since the static dielectric
constant of the solutions depends little on the ionic species,
the influence of the adjustable parameters is so predominant
that a quantitative comparison between the effect of different
counterions may be meaningless.
Mandel and co-workers and offer credibility to the hypo-
thesis of the polyion configuration as a sequence of rod-like
subunits.
References
F. Bordi and C. Cametti, Ber. Bunsenges. Phys. Chem. 89,
747 (1985).
W. E. Davis and J. H. Elliott, in: “High Polymers - Cellulose
and Cellulose derivatives”, eds. N. M. Bikales and L. Segal,
Vol. V, Part. 111, Wiley-Interscience.
R. J. Molinari, R. H. Cole, and J. H. Gibbs, Biopolymers 20,
977 (1981).
T. Vreugdenhil, F. van der Touw, and M. Mandel, Biophys.
Chem. 10, 67 (1979).
F. van der Touw and M. Mandel, Biophys. Chem. 2, 231
(1974).
F. van der Touw and M. Mandel, Biophys. Chem. 2, 218
(1974).
J. F. Thibault and M. Rinaudo, Biopolymers 24, 2131 (1985).
K. Ward Jr. and P. A. Seib, in: “The carbohydrates, chemistry
and biochemistry”, eds. W. Pigman and D. Horton, Academic
Press 1970.
R. Ullman, Macromolecules 2, 27 (1969).
W. van Dijk, F. van der Touw, and M. Mandel, Macromo-
lecules 14, 792 (1981).
W. van Dijk, F. van der Touw, and M. Mandel, Macromo-
lecules 14, 1554 (1981).
[12] A. Minakata, Ann. N.Y. Acad. Sci. 303, 107 (1977).
I131 A Bonincontro, C. Cametti, A. Di Biasio, and F. Pedone,
Biophys. J. 45, 495 (1984).
[14] A. Minakata and N. Imai, Biopolymers 11, 329 (1972).
(Eingegangen am 2. Januar 1986) E 6181

Vapor-Liquid Equilibria for Binary and Ternary Mixtures of Benzene, Toluene

and n-Butyraldehyde
K.-D. Kassmann and H. Knapp
Institut fur Thermodynamik und Anlagentechnik, Technische Universitat Berlin (West)

Fluid Phase Equilibrium / Liquid Mixtures f Materials Properties Thermodynamics

Isothermal vapor-liquid equilibria were investigated in a pressure controlled, dynamic still with vapor and liquid recirculation. The
temperature, the pressure and the compositions of the vapor and the liquid phase were determined for benzene/toluene at 313.15 K and
334.15 K, n-butyraldehyde/benzene at 313.15 K and 343.15 K, n-butyraldehyde/toluene at 313.15 K and 333.15 K and for the ternary
mixture at 313.15 K. - The experimental binary VLE-data were reduced: a point-to-point consistency test was performed, with a
maximum likelihood method binary parameters were fitted for five popular activity coefficient models. The experimental ternary
VLE-data could be used to check the adequacy of gE-models.

1. Introduction data can be used to find optimum values of binary para-

Experimental VLE-data are the indispensable basis for
the thermodynamic design of separation processes on the
one hand and for the understanding of the conditions in
liquid mixtures and for the improvement of molecular the-
ories on the other hand. In want of an exact theory, imper-
fect but. yseful‘models are suggested and experimental VLE-
meters in appropriate correlations including predictive cor-
relations based on group interaction models.
In this study isothermal measurements were made in an
equilibrium apparatus for systems containing benzene, tol-
uene and n-butyraldehyde. Relatively few VLE-data have
been reported for mixtures containing aldehydes since al-

3er. Bunsenges. Phys. Chem. 90, 452-458 (1986) - 0VCH Verlagsgesellschaft mbH, D-6940 Weinheim, 1986.
0005 - 9021/86/0505 -0452 $ 02.50/0
 K.-D. Kassmann and H. Knapp: Vapor-Liquid Eauilibria for Binarv and Ternarv Mixtures etc.
dehydes will react chemically under the presence of air and
therefore require special care and attention.
The results of the measurements can be used for the es-
timation of UNIFAC parameters for aldehyde/aromatic hy-
drocarbon functional-group interactions which are unavail-
able.
14
13
I gas chromatograph Hewlett Packard 5830 A equipped with a ther-
I"S.Ch, 1
10 U
Fig. 1
Overall setup of the apparatus
(1) Schuberth still; (2) cold trap; (3) manostat; (4) solenoid valve;
(5) bypass; (6) vacuum pump; (7) buffer tank; (8) closed ended
manometer; (9) nitrogen supply; (10) Teflon 3-way valves; (11) ma-
nometer
Fig. 2
Detailed diagram of Schuberth still
(1) reboiler; (2) thermostated jacket; (3) exchangable Cottrell pump;
(4) equilibrium chamber; ( 5 ) thermometer; (6)condensers; (7) funnel;
(8) cooler; (9) preheater; (10) magnetic stirrer; (11) Teflon valve; (12)
sample flask; (13) heater; (14) filling spout; (15) jacket thermometer
2. Experimental
2.1. Vapor-Liquid Equilibrium Apparatus
A schematic flow diagram of the equipment is shown in Fig. 1
with details of the all-glass still in Fig. 2. The still was constructed
by Schuberth [l], following a design of Kortiim [2], and was modi-
fied by the authors.
Vapor generated in the reboiler by an electric heater carries liquid
through a vertical Cottrell-pump into the equilibrium chamber. The
liquid returns through the annular downpipe into the reboiler, the
vapor is condensed and recirculated into the reboiler. The core of
453
the equilibrium cell is surrounded by a jacket through which ther-
mostated liquid is circulated by a Haake F 3 C thermostat. Tem-
perature fluctuations are less than kO.01 K.
Samples for analysis can be taken without interrupting the op-
eration. A sample of the condensed vapor phase is filled in the
sample holder through a funnel which can be moved by a magnet.
A liquid sample can be withdrawn from the reboiler into the de-
pressurized sample flask. Samples are taken after steady state con-
ditions are established. The samples are transferred in chilled sam-
ple flasks to the analysing lab.
A small bleedstreem of high purity nitrogen is constantly added
in order to avoid exposure to moisture and oxygen and to actuate
the pressure controller.
2.2. Instrumentation
In the beginning the temperature was read at high precision mer-
cury thermometers with a resolution of 0.01 K. Later a platinum
resistance thermometer PT 100 in combination with a 7 1/2 digit
multimeter was used with a resolution of 0.00025 K. Both ther-
mometers were calibrated by comparison with a Rosemount PT 25
standard resistance thermometer.
The pressure in the system was regulated with a highly sensitive
two liquid manostat shown in Fig. 1. Pressure fluctuations were
dampened by a 50 liter buffer volume to less than 5 Pa. The pressure
was determined with a U-tube mercury manometer corrected for
temperature changes.
The composition of the samples was determined by means of a
mal conductivity detector and 1.8 m stainless steel columns packed
with Apiezon M on 80 mesh Chromosorb. Reference samples were
prepared gravimetrically on an electrical high precision balance
with a resolution of 0.1 mg. Each sample was analysed at least three
times.
The sensitivity of the instruments, the inaccuracy of the readings
and the uncertainty of a T-p-x-y point are given in Table 1.
Table 1
Sensitivity and accuracy of instruments or systems and uncertainty of meas-
urements
S A U
T [K]") 0.01 0.02 -
T [K] b, 0.00025 0.01 -
P Wal 0.05 0.25 -
x [mol/mol] 0.m1 0.001 -
y [mol/mol] o.oooo1 0.001 -
T , P , x , Y[%I - - 0.3
S = Sensitivity of instruments or system.
A = Accuracy of the system, limited by calibration, fluctuations, sample
handling etc.
(I = Uncertainty of experimental point.
a) = Mercury thermometers.
b, = Platinum resistance thermometer PT 100.
2.3. Pure Substances
Benzene could be purchased at very high purity and no further
purification was required. Toluene and the aldehyde were distilled
in columns of approximately 1 m height, one of 0.03 m inside di-
ameter and packed with 2 mm glass spiral packing and the other
operated with a spinning band of PTFE. The distillation was carried
out under nitrogen atmosphere specifically to avoid oxidation of
the aldehyde. Also small amounts of hydrochinone were added into
the reboiler.
The purity of the substances was checked by measuring ther-
mophysical properties such as density, refractive index and normal
boiling point and by comparing the values with Refs. [3,5, 12- 141.
454 K.-D. Kassmann and H. Knapp: Vapor-Liquid Equilibria for Binary and Ternary Mixtures etc.

Table 2 Deviations between experimental and correlated values are an in-

Properties of pure compounds dication of the scattering, that means the inaccuracy of the meas-
urements, and an indication for the reproducibility especially if the
No. 1 2 3 vapor pressures are taken with rising and falling temperatures.
name n-butyraldehyde benzene toluene In Table 3 the Antoine constants A, B and C fitted with a maxi-
formula C4HsO C6H8 C7H8 mum likelihood method are listed together with integrated devia-
producer Fluka AG Fluka AG Merck
registry. no. 123-72-8 71-43-2 108-88-3 tions between experimental pressures and pressures calculated with
the Antoine equation either with our own constants or with con-
M Cg/moO 72.108 78.114 92.141
P= [bar] 40.52 48.98 41.14 Table 3
Tc CK1 524.00 562.09 591.72 Antoine constants for pure liquids
zc [-I 0.260 0.271 0.264
w [-I 0.352 0.212 0.257
Comp. A B C u(P-P+) u(T-T+)
R D CAI 3.0540 3.0040 3.4431
~~ ~

P CDebyesl 2.6 0.0 0.4

R4 [-I 3.248 3.188 3.923 C,HsO 13.297 2392.002 72.371 0.78 0.03 a)
Qz [-I 2.876 2.400 2.968 14.419 2986.798 43.150 2.698 - (11)
13.950 2720.988 56.360 2.902 - (15)
d2' [g/cm3] 0.8016 (3) 0.87901 (3) 0.86696 (3) 14.152 2839.087 50.150 2.458 - (3)
0.8020 (5) - 0.876 (5) 12.688 2103.619 87.667 4.172 - (4)
0.8010 (12) - 0.8665 (12)
- 0.8785 (13) - C6H6 13.901 2797.600 51.889 0.15 0.005 a'
- 0.8765 (14) 0.8669 (14) 13.886 2788.510 52.360 0.29 - (3)
0.801596a' 0.878903a' 0.866911 13.857 2771.930 53.230 0.24 - (4)

ng [-I 1.3791 (3) 1.50112 (3) 1.49693 (3) C A 13.710 2925.416 62.106 0.25 0.014
1.38 (12) - 1.497 (12) 13.999 3096.516 53.668 0.32 - (3)
1.3843 (14) 1.5011 (14) 1.4961 (14) 13.949 3075.178 54.397 1.49 - (4)
1.37915a) 1.5011a) 1.4969"'
a) = This work.
Tnh C"c1 74.8 (3) 80.10 (3) 110.625 (3)
74.85 (5) 80.15 (5) 110.65 (5)
74-75 (12) - -
Table 4
- 80.1 (14) 110.6 (14) Vapor liquid equilibrium data for benzene (l)/toluene (2)
74.84a' 80.1 15") 110.69"'
.
No. PWal
~~

4 - - This work. x1 Yl a

The results of the purity test are shown in Table 2 which also gives T = 313.15 K
information about the substances. Finally the substances were ana- 1 78.72 O.oo00 O.oo00 -
lysed in the gas chromatograph: no impurities could be detected. 2 85.38 0.0401 0.1128 3.04
The purified substances were stored under a nitrogen atmosphere 3 95.17 0.0992 0.2514 3.05
at -20-c. 4 119.73 0.2484 0.5020 3.05
5 130.85 0.3094 0.5839 3.13
2.4. Experimental Program 6 133.47 0.3315 0.6012 3.04
A summary of the experimental program is given in the following 7 143.06 0.3854 0.6599 3.09
table (N: number of experimental points): 8 156.08 0.4673 0.7273 3.04
9 167.83 0.5398 0.7801 3.02
10 181.19 0.6209 0.8312 3.01
Comp. 1 Comp. 2 Comp. 3 T Pmrn Pmar
N 0.8797 3.03
11 196.20 0.7068
(K) @Pa) 0.7899 0.9181 2.98
12 208.90
13 220.80 0.8616 0.9490 2.99
benzene - - 303 - 353 160 1016 15 14 232.77 0.9352 0.9773 2.98
- n-butanal - 305 - 345 240 1013 20 1s 243.89 1.oooo 1 .oooo
.~ - toluene 305 - 384 54 1013 25
benzene - toluene 313.15 79 244 15 T = 334.15 K
benzene - toluene 334.15 193 541 16
1 192.90 O.oo00 O.oo00 -
benzene n-butanal - 313.15 244 286 17
benzene n-butanal 2 215.72 0.0622 0.1535 2.73
- 343.15 734 865 17
n-butanal toluene 3 233.29 0.1140 0.2589 2.12
- 313.15 79 286 15
n-butanal toluene 4 251.69 0.1680 0.3516 2.69
- 333.15 355 619 16
benzene n-butanal toluene 5 275.21 0.2334 0.4519 2.71
313.15 109 244 15
6 299.36 0.3003 0.5390 2.72
7 312.10 0.3368 0.5802 2.72
3. Results 8 343.26 0.4288 0.6683 2.68
3.1. Vapor Pressure of Pure Liquids 9 362.04 0.4799 0.7128 2.69
10 399.92 0.5873 0.7949 2.72
The vapor pressures of the pure substances were measured as a
11 423.28 0.6571 0.8372 2.68
function of temperature for several reasons: 12 469.17 0.7891 2.67
0.9091
If accurate vapor pressure data are reported in literature a com- 13 485.57 0.8374 0.9332 2.71
parison can be made. 14 506.45 0.9574 2.55
0.8981
The experimental points can be interpolated by a suitable vapor 15 523.49 0.9478 2.84
0.9810
pressure formula, for instance the Antoine equation: 16 540.59 1.m 1.oooO -
In p F P a = A - B/(T/K - C ) (SI-Units) . (1) ~
 K.-D. Kassmann and H. Knapp: Vapor-Liquid Equilibria for Binary and Ternary Mixtures etc. 455

Table 5 Table 6 (Continued)

Vapor liquid equilibrium data for n-butyraldehyde (l)/benzene (2)
No. P ChPal XI Y1 U
No. PWal x1 Y1 U

T = 333.15 K
T = 313.15 K 1 185.39 O.oo00 O.oo00 -
1 243.63 O.oo00 O.oo00 - 2 203.90 0.0327 0.1146 3.83
2 246.05 0.0235 0.0321 1.39 3 235.36 0.0920 0.2718 3.68
3 249.02 0.0582 0.0767 1.34 4 261.22 0.1436 0.3781 3.63
4 252.54 0.1037 0.1301 1.29 5 294.75 0.2123 0.4856 3.50
5 255.80 0.1516 0.1823 1.25 6 323.09 0.2729 0.5640 3.45
6 258.68 0.2036 0.2380 1.22 7 354.60 0.3432 0.6367 3.35
7 261.41 0.2573 0.2946 1.21 8 355.39 0.3459 0.6381 3.33
8 264.15 0.3154 0.3532 1.19 9 405.86 0.4691 0.7343 3.13
9 264.45 0.3212 0.3600 1.19 10 444.24 0.5656 0.7990 3.05
10 267.61 0.3904 0.4286 1.17 11 479.90 0.6531 0.8489 2.98
11 270.89 0.4677 0.5026 1.15 12 523.60 0.7596 0.9001 2.85
12 273.94 0.5493 0.5790 1.13 13 560.03 0.8491 0.9400 2.78
13 276.88 0.6321 0.6568 1.11 14 582.10 0.9051 0.9629 2.72
14 279.11 0.7080 0.7292 1.11 15 604.38 0.9614 0.9854 2.71
15 282.91 0.8512 0.8615 1.09 16 619.20 1.oooO 1.m -

16 284.90 0.9364 0.9406 1.08

17 286.40 1.m 1.m -
Table 7
Vapor-liquid equilibrium data for n-butyraldehyde (l)/benzene (2)/toluene(3)
T = 343.15 K at 313.15 K
1 734.27 O.oo00 O.oo00 -
2 740.81 0.0228 0.031 1 1.38 No. p [hPa] x1 x2 x3 Yl Y2 Y3

3 749.68 0.0575 0.0754 1.34

4 758.24 0.0955 0.1205 1.30 1 109.19 O.oo00 0.1853 0.8147 O.oo00 0.4110 0.5890
5 768.04 0.1423 0.1745 1.27 2 122.27 0.0565 0.1717 0.7718 0.1574 0.3448 0.4978
6 777.63 0.1912 0.2284 1.25 3 134.62 0.1227 0.1883 0.7190 0.2891 0.2862 0.4247
7 786.57 0.2436 0.2836 1.23 4 150.63 0.2112 0.1404 0.6484 0.4251 0.2275 0.3474
8 805.75 0.3781 0.4177 1.18 5 168.22 0.3182 0.1195 0.5623 0.5512 0.1733 0.2755
9 811.30 0.4206 0.4585 1.17 6 186.22 0.4316 0.0958 0.4726 0.6573 0.1265 0.2162
10 821.24 0.4980 0.5312 1.14 7 210.73 0.5812 0.0705 0.3483 0.7694 0.0835 0.1471
11 830.41 0.5787 0.6078 1.13 8 195.04 O.oo00 0.7033 0.2967 O.oo00 0.8783 0.1217
12 840.17 0.6761 0.6979 1.11 9 204.14 0.0726 0.6508 0.2766 0.1135 0.7766 0.1099
13 850.15 0.7803 0.7947 1.09 10 213.95 0.1643 0.5847 0.2610 0.2343 0.6701 0.0956
14 855.18 0.8580 0.8670 1.08 11 222.16 0.2548 0.5193 0.2259 0.3401 0.5762 0.0837
15 860.28 0.9271 0.9315 1.07 12 228.59 0.3365 0.4620 0.2015 0.4243 0.5012 0.0745
16 863.54 0.9757 0.9771 1.06 13 234.49 0.4048 0.4134 0.1818 0.4936 0.4405 0.0659
17 865.20 1.m 1.m - 14 238.52 0.4599 0.3742 0.1659 0.5470 0.3933 0.0597
~ 15 244.42 0.5349 0.3217 0.1434 0.6161 0.3328 0.0511

stants taken from the Refs. [4,5]. There is very good agreement for
benzene and toluene and some moderate disagreement for n-bu-
Table 6 t yraldehyde.
Vapor liquid equilibrium data for n-butyraldehyde (l)/toluene (2)
3.2. Vapor Liquid Equilibria
Experimental T-p-x-y and GI values are presented for the three
binary mixtures and one ternary mixture in Tables 4 to 7. Experi-
mental points are presented in Figs. 4 to 6. The diagrams show also
T = 313.15 K
curves calculated with g" models after data reduction.
1 78.78 O.oo00 O.oo00 -
2 93.64 0.0542 0.1924 4.16 4. Data Reduction
3 105.80 0.1016 0.3163 4.10
4 116.38 0.1438 0.4053 4.06 4.1. Consistency Test
5 153.40 0.3112 0.6286 3.75 If T, p , x and y are measured in an isothermal experiment
6 169.34 0.3915 0.7007 3.64
0.7440 3.54
and if an equation of state is known for the gas phase the
7 179.81 0.4508
8 191.49 0.5103 0.7836 3.47 Gibbs-Duhem equation allows a test of thermodynamic
9 208.95 0.5991 0.8358 3.41 consistency of the experimental data. A method suggested
10 228.42 0.6967 0.8839 3.31 by Van Ness [6] or Fredenslund [7] was applied. The fu-
11 242.76 0.7692 0.9144 3.21
gacity coefficients in the gas phase were calculated with a
12 256.29 0.8424 0.9442 3.17
13 268.14 0.9038 0.9670 3.12 volume explicit virial equation of state, terminated after the
14 278.37 0.9543 0.9847 3.08 second term. The virial coefficients were estimated by the
15 287.63 1.m 1.m - method of Hayden-OConnell [S].
456 K.-D. Kassmann and H. Knapp: Vapor-Liquid Equilibria for Binary and Ternary Mixtures etc.

70 60

KO
50

50

40

L 40
/
d I
d
m.
a
1

/
a 7’ ,s/ a
m 30
3

30 d
*.- P’ 3

0
a a

2G

20

10

0 c
0.0 0.2 0.4 0.6 0.8 1.0 0.2 0.4 0.6 0.8 1.0
cancentiat,on X I or yi . mol/mal cancentiatlon x, or yi . mol/rnol

C7H812 I C,H83 I I I C7H8[21 CeHSi II

TOLUENE BUIRNRL TOLUENE BENZENE
Fig. 5
Fig. 3 p-x-y phase equilibrium diagram for n-butyraldehyde (1) and tol-
p-x-y phase equilibrium diagram for benzene (1) and toluene (2) at uene (2) at 313.15 K ([3) and 333.15 K ( 0 ) .Legend as in Fig. 3
313.15 K (FJ) and 334.15 K ( 0 ) .The lines are the results from the a. 1
UNIQUAC equation fit of the data 2 1
T i 313.i5 x

MOLE FRACTION C,Hp

Fig. 6
x-y phase equilibrium diagram for n-butyraldehyde (I), benzene (2)
and toluene (3) at 313.15 K. The dashed lines are the results of a
bubble-point calculation using the UNIQUAC equation fit of the
binary data

The consistency can be checked either overall by calcu-

lating the D A A y of all points along one isotherm or by cal-
culating the point by point deviation. The deviations be-
tween experimental and calculated points should be less
20
0.0
‘ 0.2 0.4 0.6 0.8
than the experimental uncertainty of a T-p-y point. Table 8
shows the results of the overall and the point by point test.
cancentratlo” XI or y, . rnol/mol

CsHs121 C,H& [ II 4.2. Models for the Excess Gibbs Energy

BENZENE BUTANRL
Based on the experimental data activity coefficients can
Fig. 4 be calculated.
p-x-y phase equilibrium diagram for n-butyraldehyde (1) and ben-
zene (2) at 313.15 K (m)
and 343.15 K (0). Legend as in Fig. 3 Yi = ( Y I V Y p I X i f l ) (2)
 K.-D. Kassmann and H. Knapp: Vapor-Liquid Equilibria for Binary and Ternary Mixtures etc. 451

where The so called binary interaction coefficients of five gE

models were then fitted using the maximum likelihood
IncpV = P/RT(CC y j y k ~ 2 1 -
3 1~3~~ ~ 1 ) (3)
j k . method and the objective function proposed by Prausnitz
and and Anderson [lo]. The results of the parameter optirni-
sation are given in Table 9. Fig. 7 shows experimental gE
f p = PoiL V (poiL V exp [uki ( P - pkY)/R 7 7 . (4) points calculated with the experimentally determined activ-
ity coefficients and gE curves calculated with the g E models.
The virial coefficients in (3) were estimated as mentioned The maximum value of gE is less than 200 J/mol and the
above, the volume of the pure liquid was estimated by the maximum value for y m is less than 1.3 - indicating almost
correlation of Hankinson [9]. ideal behaviour of the mixtures.

Table 8
Results of the point-to-point consistency test

System T DAA~ DAAP consistency Yeconsistency

Vapor
CKI [mol %] ChPal overall point-to-point

benzene/toluene 313 real 0.16 0.27 + 69

334 real 0.54 0.40 + 35
butanal/benzene 313 real 0.04 0.12 + 80
343 real 0.30 0.12 + 93
butanal/toluene 313 real 0.40 0.30 + 62
333 real 0.34 0.10 + 29

Table 9
Estimated parameters from data correlation

T Parameters")
System Model
CKI A12 ,421

benzene/toluene 313 Margules 0.0092 -0.0090 0.27 0.29

Van Laar 198.16 0.0139 0.13 0.61
Wilson - 112.36 108.01 0.32 1.17
NRTL - 1302.9 1564.9 0.27 0.30
UNIQUA'C -715.65 865.01 0.27 0.29
334 Margules 0.0229 0.0048 0.45 0.99
Van Laar 25.674 0.0164 0.13 1.50
Wilson - 540.93 851.01 0.45 0.94
NRTL 1431.8 - 1185.0 0.45 0.97
UNIQUAC 722.34 -598.10 0.45 0.94
butanal/benzene 313 Margules 0.1214 -0.0437 0.14 0.33
Van Laar 0.1884 0.0869 0.1 1 0.24
Wilson 1831.7 - 1089.9 0.1 1 0.25
NRTL - 1564.5 2328.2 0.12 0.28
UNIQUAC - 1530.2 2104.9 0.10 0.16
343 Margules 0.1343 -0.0281 0.17 0.53
Van Laar 0.1712 0.1091 0.14 0.43
Wilson 1394.8 -782.67 0.14 0.44
NRTL - 1245.8 1897.3 0.15 0.47
UNIQUAC - 1429.2 1862.9 0.1 1 0.28
butanal/toluene 313 Margules 0.2085 -0.0721 0.26 0.35
Van Laar 0.3226 0.1512 0.22 0.28
Wilson 2578.4 - 1495.7 0.23 0.28
NRTL - 1606.7 2714.3 0.24 0.31
UNIQUAC -1481.2 2161.5 0.21 0.27
333 Margules 0.2249 -0.0475 0.39 0.18
Van Laar 0.2950 0.1805 0.35 0.16
Wilson 2127.4 - 1197.0 0.35 0.16
NRTL - 1235.3 2199.4 0.37 0.14
UNIQUAC - 1393.4 1964.3 0.33 0.15

a) NRTL and UNIQUAC parameters in J/mol.

Third NRTL parameter fixed to 0.3.
458
__
K.-D. Kassmann and H. Knapp: Vapor-Liquid Equilibria for Binary and Ternary Mixtures etc.

Especially in the benzene/toluene case where the g E’sare total pressure, hPa
in the order of magnitude of the experimental error it can vapor pressure of pure liquid, hPa
be seen that the VLE-data were obtained with very good critical pressure, bar
area parameter in the Uniquac equation
accuracy. gas constant, 8.31441 J/mol K
volume parameter in the Uniquac equation
radius of gyration, 8,
temperature, K
critical temperature, K
molar volume of pure liquid, cm3/mol
liquid phase mole fraction
vapor phase mole fraction
critical compressibility factor
relative volatility
activity coefficient
dipole moment, Debyes
standard deviation
fugacity Coefficient
acentric factor

Subscripts
i, j , k component i , j , k
min minimum
max maximum
oi pure component

Supercripts
E excess
LV equilibrium liquid/vapor
V vapor
0 standard state
+ calculated value

Excess Gibbs energy in J/mol as a function of composition for
benzene (1) and toluene (2) at 313.15 K ([I])and 334.15 K (O),for
n-butyraldehyde (1) and benzene (2) at 313.15 (A) and 343.15 K
(+) and for n-butyraldehyde (1) and toluene (2) at 313.15 K ( x )
and 333.15 K (0).Legend as in Fig. 3
4.3. Prediction of Ternary VLE
After the binary parameters were fitted with the experi-
mental binary VLE points ternary VLE were calculated with
the UNIQUAC equation. With the temperature and liquid
composition of the experiment the vapor pressure and the
vapor composition was calculated with a bubble-point pro-
cedure. For all data points the D A A y , is 0.01 mol/mol, the
D A A y 2 is 0.005 mol/mol and the D A A p is 2.5 hPa.
The authors are grateful for the financial assistance by DFG
(Deutsche Forschungsgemeinschaft). The assistance given by Mr.
Weber in the experimental work is appreciated.
Symbols
A . B, C constants in the Antoine vapor pressure equation
DAA absolute average deviation
B second virial coefficient, J/mol
dZo density at 20”C, g/cm3
f;” standard-state fugacity of liquid, hPa
Yf: excess Gibbs energy, J/mol
ng refractive index at 20°C
Tn h normal boiling point, ‘C
M molecular weight, g/mol
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