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www.elsevier.nlrlocaterfluid
Institute of Physical Chemistry, Applied Thermodynamics, UniÕersity of Heidelberg, Im Neuenheiner Feld 253,
69120 Heidelberg, Germany
Received 7 July 1999; accepted 27 October 1999
Abstract
Experimental data are reported of excess molar volumes V E of binary and of excess molar enthalpies H E of
ternary mixtures of methanol, tert-amyl methyl ether ŽTAME. and n-heptane or 2,2,4-trimethylpentane
Ž iso-octane. as well as isothermal vapor–liquid equilibrium ŽVLE. data of binary and ternary mixtures
containing these components. The experimental data are used to test the applicability of the ERAS and the
UNIQUAC model to describe the various excess properties. In particular, the possibility is tested to predict
ternary data using only binary model parameters. q 2000 Elsevier Science B.V. All rights reserved.
Keywords: H E ; V E ; VLE; TAME; Methanol; Alkane; Mixtures; Thermodynamics; ERAS model; UNIQUAC model
1. Introduction
Substituting tetraethyl–lead as gasoline additive, methyl tert-butyl ether ŽMTBE., ethyl tert-butyl
ether ŽETBE. and tert-amyl methyl ether ŽTAME. have become important because of their good
™
anti-knocking properties. These ethers can be synthesized by the simple reaction: alcoholq isoolefine
ether. For a complete conversion of the olefine, it is necessary to add the alcohol in surplus. To
purify the ether and to recycle the nonreacted alcohol, various separation processes are applied. In
order to design these separation processes properly, phase behavior and thermodynamic properties of
the fluid mixtures involved have to be known. Corresponding data are necessary also for estimating
)
Corresponding author. Tel.: q49-6221545204; fax: q49-6221544255; e-mail: r.lichtenthaler@urz.uni-heidelberg.de
0378-3812r00r$ - see front matter q 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 8 - 3 8 1 2 Ž 9 9 . 0 0 3 1 5 - 5
224 K. Kammerer et al.r Fluid Phase Equilibria 167 (2000) 223–241
the phase behavior of gasoline mixtures containing the ethers because complete miscibility has to be
guaranteed at any state condition occurring in practical use.
In previous papers, experimental H E of binary and ternary mixtures containing MTBE w1,2x, ETBE
w3x or TAME w4,5x as well as experimental V E and excess heat capacities CPE of binary, ternary and
quaternary mixtures containing ETBE w6–8x and vapor–liquid equilibria Ž VLE. of mixtures containing
ETBE w5x have been published. The ERAS ŽExtended Real Associated Solution. model, developed for
calculating thermodynamic properties of mixtures containing associating components, has been
applied successfully for the simultaneous description of H E , V E and CPE w8x. Continuing these
investigations in this paper, experimental results of V E are reported for the binary mixtures of TAME
with methanol, n-heptane and 2,2,4-trimethylpentane Ž iso-octane.. Furthermore, excess enthalpies H E
are presented for the ternary mixtures of methanol, TAME and n-heptane or iso-octane, respectively,
as well as isothermal VLE for these two ternaries and of all of the corresponding binary mixtures.
VLE of the binary mixtures containing methanol and the three branched ethers have been discussed
and compared to literature data available w5x. The experimental data and already published data of H E
w4x are used to test the applicability of the ERAS model for describing all the various properties with
the same set of system-specific model parameters. In particular, the possibility to predict ternary data
using only binary model parameters has been investigated. Analogously, the UNIQUAC model has
been tested for describing the VLE-data. The benefits and the drawbacks of both models are
discussed.
Table 1
Experimental results of the molar excess volumes V E for the binary mixtures of TAME with methanol, n-heptane and
iso-octane at 298.15 and 313.15 K
Methanol ŽA.qTAME ŽB. TAME ŽB.q n-heptane ŽC. TAMEŽB.q iso-octane ŽC.
E 3 E 3
xA V Žcm rmol. xB V Žcm rmol. xB V E Žcm3rmol.
298.15 K
0.8993 y0.164 0.0990 0.128 0.1000 0.092
0.8002 y0.284 0.1895 0.193 0.2003 0.138
0.7013 y0.371 0.3010 0.276 0.3006 0.178
0.6011 y0.425 0.3996 0.317 0.4040 0.210
0.5003 y0.454 0.5009 0.337 0.5014 0.218
0.4011 y0.452 0.6003 0.313 0.6012 0.207
0.3032 y0.416 0.7002 0.273 0.7008 0.187
0.1983 y0.330 0.8001 0.219 0.1820 0.134
0.0939 y0.187 0.9008 0.123 0.9430 0.073
313.15 K
0.8993 y0.163 0.0990 0.143 0.1000 0.083
0.8002 y0.286 0.1895 0.246 0.2003 0.136
0.7013 y0.375 0.3010 0.291 0.3006 0.174
0.6011 y0.434 0.3996 0.331 0.4040 0.192
0.5003 y0.461 0.5009 0.341 0.5014 0.120
0.4011 y0.458 0.6003 0.323 0.6012 0.190
0.3032 y0.417 0.7002 0.282 0.7008 0.172
0.1983 y0.331 0.8001 0.224 0.8120 0.131
0.0939 y0.189 0.9008 0.128 0.9430 0.071
K. Kammerer et al.r Fluid Phase Equilibria 167 (2000) 223–241 225
2. Experimental
2.1. Materials
The substances were obtained from standard laboratory sources and were used without further
purification. The purities were 99.5% for methanol Ž Merck. , ) 97% for TAME ŽFLUKA. , which was
further purified by fractional distillation up to 99.9% ŽGC. , 99.5% for n-heptane ŽMerck. and 99.5%
for iso-octane ŽMerck. . All substances were carefully degassed and dried with molecular sieves.
2.2. Apparatus and procedure
Excess molar volumes were measured using an Anton Paar DMA 60 vibrating-tube densitometer
with a DMA 602 HT measuring cell. The densities of the pure components and the binary mixtures
are measured with high accuracy Ž D r - 10y5 g P cmy3 .. From these data, molar excess volumes can
be determined according to the following relation:
Ý x i Mi Mi
E i
V s yÝ xi Ž1.
rM i ri
where r i is the density and Mi is the molar mass of pure component iŽ i s A,B. and x i is the mole
fraction. r M is the density of the mixture. V E data are obtained with an accuracy "0.2% of the
Table 2
Experimental results of the molar excess enthalpies H E for the ternary mixture x A s Ž1y x B y x C . methanolq x B
TAMEq x C n-heptane at 298.15 K a
xA xB xC H E ŽJrmol. xA xB xC H E ŽJrmol.
x B r x C s 0.8r 0.2 x B r x C s 0.4r 0.6
0.000 0.800 0.200 193.4 0.000 0.400 0.600 280.3
0.094 0.725 0.181 415.3 0.094 0.403 0.504 449.6
0.194 0.644 0.161 480.8 0.194 0.358 0.448 528.7
0.295 0.564 0.141 520.1 0.295 0.314 0.392 552.4
0.392 0.486 0.122 505.1 0.392 0.270 0.338 546.4
0.496 0.403 0.101 480.3 0.496 0.224 0.280 516.0
0.605 0.316 0.079 450.6 0.605 0.176 0.220 478.9
0.707 0.234 0.059 390.4 0.707 0.130 0.163 424.4
0.795 0.164 0.041 300.3 0.795 0.091 0.114 343.1
0.900 0.080 0.020 180.7 0.900 0.044 0.056 363.1
maximum of the V E curve describing the dependence on composition and the error of the mole
fraction is - "0.0001.
Molar excess enthalpies were measured using a modified TRONAC 1250 calorimeter. This
quasi-isothermal flow calorimeter and its operating procedure have been described elsewhere w9x in
detail. In order to obtain H E of binary mixtures, two pure liquid components are mixed together; in
the case of ternary mixtures, a binary liquid mixture of known composition is mixed with a third pure
component and the resulting heat effect is measured directly. The errors of H E and the mole fraction
x are estimated to be - "0.01 H E Žbut at least "1 Jrmol. and - "0.0005 Ži.e., x is accurate in
the third decimal place., respectively.
VLE data have been measured using a VLE apparatus Ž analytical method. described in detail
elsewhere w10x. Phase equilibrium is established after intensively mixing the two phases in a
thermostated equilibrium cell. The experimental setup allows the simultaneous measurement of
temperature, pressure, liquid-phase and vapor-phase compositions. Temperature is measured directly
in the equilibrium cell using a PT 100 digital thermometer within "0.01 K. Pressure is recorded
using an MKS Baratron pressure sensor attached to the top of the cell with a relative error estimated
"D PrP s 0.1%. The liquid phase is circulated and passes through a liquid-sampling valve with
which samples can be drawn and analyzed automatically by a gas chromatograph Ž Sichromat 1–4,
Table 3
Experimental results of the molar excess enthalpies H E for the ternary mixture x A s Ž1y x B y x C . methanolq x B
TAMEq x C iso-octane at 298.15 K a
xA xB xC H E ŽJrmol. xA xB xC H E ŽJrmol.
x B r x C s 0.8r 0.2 x B r x C s 0.4r 0.6
0.000 0.800 0.200 177.6 0.000 0.400 0.600 256.8
0.098 0.722 0.180 395.2 0.098 0.361 0.541 424.2
0.201 0.639 0.160 452.8 0.201 0.320 0.479 498.3
0.297 0.562 0.141 487.6 0.297 0.281 0.422 531.5
0.389 0.489 0.122 485.6 0.389 0.244 0.367 521.3
0.495 0.404 0.101 466.3 0.495 0.202 0.303 506.2
0.601 0.319 0.080 428.5 0.601 0.160 0.239 464.9
0.711 0.231 0.058 362.5 0.711 0.116 0.173 409.2
0.803 0.158 0.039 264.2 0.803 0.079 0.118 301.7
0.895 0.084 0.021 160.1 0.895 0.042 0.063 207.3
Siemens.. Samples of the gaseous phase are drawn using a special six port valve Ž VALCO, VICI,
Switzerland.. Liquid and gaseous phases are analyzed almost simultaneously each one with an error
of "0.15% in mole fraction. Quantitative analysis of the gas chromatographic peaks of both phases
and measurement of pressure and temperature recordings provide complete information of the phase
equilibrium of the system. From these data, activity coefficients and G E values of the liquid phase are
calculated.
3. Experimental results
The molar excess volumes V E of the binary mixtures at 298.15 and 313.15 K are listed in Table 1.
The excess volumes of the system methanolq TAME are negative, whereas the excess volumes for
the TAMEq alkane systems are slightly positive. The values for methanolq TAME at 298.15 K are
in very good agreement with the data reported by Letcher and Govender w11x. The temperature
dependence of V E is not very pronounced for all systems. The excess volumes are becoming slightly
more negative with increasing temperature for the system methanolq TAME and slightly more
Table 4
Isothermal vapor–liquid equilibrium data for methanol ŽA.qTAME ŽB., methanol ŽA. q n-heptane ŽC. and methanol
ŽA.q iso-octane ŽC. at 313.15 K
Methanol ŽA.q n-heptane ŽC. Methanol ŽA.q iso-octane ŽC. Methanol ŽA.qTAME ŽB.
PrkPa xA yA PrkPa xA yA PrkPa xA yA
12.40 0.000 0.000 13.31 0.000 0.000 19.80 0.000 0.000
24.20 0.011 0.465 32.87 0.022 0.599 24.67 0.043 0.227
36.55 0.033 0.657 42.67 0.083 0.706 26.51 0.063 0.295
40.37 0.054 0.701 44.65 0.134 0.724 30.03 0.115 0.405
42.88 0.074 0.716 45.89 0.221 0.732 32.20 0.159 0.463
43.21 0.091 0.725 46.09 0.254 0.732 32.87 0.178 0.481
44.41 0.124 0.730 46.25 0.291 0.733 35.67 0.264 0.548
45.27 0.168 0.740 46.35 0.336 0.733 37.11 0.331 0.583
45.55 0.194 0.743 46.49 0.813 0.733 38.09 0.392 0.609
45.80 0.228 0.743 46.47 0.841 0.733 38.81 0.450 0.630
45.89 0.249 0.743 46.28 0.883 0.734 39.33 0.498 0.647
45.98 0.857 0.744 45.94 0.917 0.741 39.85 0.559 0.667
45.93 0.871 0.744 45.49 0.935 0.753 40.13 0.611 0.684
45.88 0.883 0.744 44.52 0.954 0.777 40.45 0.683 0.708
45.83 0.893 0.745 42.75 0.972 0.819 40.53 0.724 0.723
45.59 0.914 0.747 39.90 0.988 0.889 40.54 0.772 0.742
44.55 0.945 0.772 44.55 0.945 0.772 40.56 0.784 0.748
42.73 0.968 0.816 42.73 0.968 0.816 40.47 0.791 0.751
40.55 0.983 0.868 40.55 0.983 0.868 40.42 0.815 0.765
39.07 0.989 0.907 39.07 0.989 0.907 39.97 0.861 0.796
37.37 0.995 0.952 37.37 0.995 0.952 38.44 0.944 0.885
35.80 1.000 1.000 35.80 1.000 1.000 37.01 0.981 0.951
– – – – – – 35.80 1.000 1.000
228 K. Kammerer et al.r Fluid Phase Equilibria 167 (2000) 223–241
Table 5
Isothermal vapor–liquid equilibrium data for TAME ŽB.q n-heptane ŽC. and TAME ŽB.q iso-octane ŽC. at 313.15 K
TAME ŽB.q iso-octane ŽC. TAME ŽB.q n-heptane ŽC.
PrkPa xB yB PrkPa xB yBa
13.11 0.000 0.000 12.40 0.000 0.00
13.67 0.058 0.096 13.07 0.051 0.09
14.16 0.109 0.170 13.58 0.101 0.18
14.73 0.174 0.259 14.22 0.166 0.27
15.33 0.244 0.347 14.61 0.209 0.33
15.77 0.302 0.411 15.10 0.265 0.39
16.38 0.391 0.503 15.35 0.296 0.43
16.81 0.455 0.565 15.77 0.348 0.48
17.18 0.515 0.618 16.08 0.389 0.52
17.19 0.522 0.628 16.44 0.438 0.57
17.61 0.595 0.689 16.59 0.461 0.59
18.07 0.672 0.752 16.91 0.502 0.62
18.51 0.754 0.815 17.13 0.541 0.66
18.85 0.820 0.866 17.53 0.602 0.71
19.23 0.896 0.922 17.72 0.635 0.73
19.49 0.948 0.961 18.09 0.698 0.78
19.80 1.000 1.000 18.40 0.751 0.82
– – – 18.59 0.787 0.85
– – – 18.90 0.843 0.89
– – – 19.09 0.880 0.91
– – – 19.43 0.943 0.96
– – – 19.61 0.982 0.99
– – – 19.80 1.000 1.00
a
Due to experimental difficulties, the error is "0.01 in vapor mole fraction.
positive for the system TAMEq n-heptane. The behavior of the system TAMEq iso-octane is vice
versa, that is, the excess volume is becoming less positive with increasing temperature.
The experimental values for the molar excess enthalpies at 298.15 K of the two ternary systems
methanolq TAMEq n-heptane and methanolq TAMEq iso-octane are listed in Tables 2 and 3,
respectively. For both mixtures, the excess enthalpies are positive over the whole composition range.
The VLE at 313.15 K, that is, vapor pressure and liquid and vapor phase equilibrium compositions
of the binary mixtures investigated are listed in Tables 4 and 5 and the experimental results for the
two ternary systems are given in Tables 6 and 7. VLE of the binary mixture methanolq TAME
already have been discussed and compared to literature data available w5x. Data at 311.15 K reported
by Antosik and Sandler w12x for the binary TAMEq iso-octane are in good agreement with those in
Table 5 taking into account the difference in temperature. The results for methanolq n-heptane and
those for methanolq iso-octane agree within experimental error with literature data, for example,
those of Hongo et al. w13x and Yasuda et al. w14x, respectively. From these data, the activity
coefficients g i were calculated according to the formula
Pyi w i
gi s Ž i s A, B,C . Ž2.
x i Pi0 w i0
K. Kammerer et al.r Fluid Phase Equilibria 167 (2000) 223–241 229
Table 6
Isothermal vapor–liquid equilibrium data for the ternary system methanol ŽA.qTAME ŽB.q n-heptane ŽC. at 313.15 K
PrkPa xA yA xC yC PrkPa xA yA xC yC
a b
x A r x B s 0.214r 0.786 x B r x C s 0.815r 0.185
34.01 0.214 0.509 0.000 0.000 18.86 0.000 0.000 0.185 0.158
34.73 0.183 0.539 0.180 0.088 35.97 0.233 0.555 0.142 0.081
34.97 0.156 0.556 0.307 0.136 39.57 0.422 0.632 0.107 0.075
35.05 0.133 0.570 0.411 0.173 41.35 0.604 0.682 0.073 0.077
35.03 0.123 0.575 0.451 0.186 41.91 0.734 0.710 0.049 0.081
34.97 0.113 0.580 0.502 0.202 41.97 0.783 0.733 0.040 0.080
34.83 0.095 0.588 0.580 0.227 41.10 0.901 0.799 0.018 0.074
34.61 0.080 0.594 0.650 0.250 – – – – –
34.35 0.069 0.597 0.700 0.267 – – – – –
34.27 0.066 0.598 0.715 0.273 – – – – –
where w i is the fugacity coefficient of component i in the gaseous mixture and w i0 is the fugacity
coefficient of the pure component. w i and w i0 are determined using second virial coefficients
230 K. Kammerer et al.r Fluid Phase Equilibria 167 (2000) 223–241
Table 7
Isothermal vapor–liquid equilibrium data or the ternary system methanol ŽA.qTAME ŽB.q iso-octane ŽC. at 313.15 K
PrkPa xA yA xC yC PrkPa xA yA xC yC
a b
x B r x C s 0.799r 0.201 x A r x B s 0.246r 0.754
18.74 0.000 0.000 0.201 0.157 35.02 0.246 0.535 0.000 0.000
36.35 0.231 0.559 0.157 0.084 35.59 0.230 0.552 0.096 0.052
40.14 0.434 0.644 0.116 0.081 35.87 0.206 0.562 0.192 0.097
41.50 0.587 0.681 0.085 0.083 36.05 0.182 0.573 0.288 0.135
42.08 0.694 0.707 0.063 0.086 36.16 0.150 0.585 0.414 0.179
42.19 0.822 0.749 0.036 0.089 36.14 0.131 0.592 0.493 0.205
41.40 0.901 0.802 0.020 0.081 35.85 0.098 0.601 0.624 0.247
– – – – – 35.53 0.079 0.604 0.700 0.273
according to the method of Tsonopoulos w15–17x in order to account for real gas behavior. Because of
the low pressures, the values of the fugacity coefficients differ by less than 0.2% from unity. Since the
experimental error for g i is much larger Ž"2.5%., gas phase corrections have no influence on the
K. Kammerer et al.r Fluid Phase Equilibria 167 (2000) 223–241 231
results and can therefore be neglected. In order to check the consistency of the phase-equilibrium
data, two different tests have been applied. The Herington–Redlich–Kister area test w18,19x and the
point test according to Van Ness w20,21x both confirmed consistency within experimental error.
Table 8
Parameters of the pure substances and the binary mixtures used in ERAS calculations
Pure component T Vmol PU VU TU s
ŽK. Žcm3rmol. ŽJrcm3 . Žcm3rmol. ŽK. Žnmy1 .
Methanola 298.15 40.73 422.3 32.15 4980 16.49
313.15 41.47 412.1 32.4 5077
TAME 298.15 133.23 469.3 102.7 4661 14.05
313.15 135.84 457.9 103.4 4727
n-Heptane 298.15 147.42 432.2 113.7 4663 14.00
313.15 150.28 424.5 114.2 4713
iso-Octane 298.15 166.08 378.1 129.1 4760 14.12
313.15 168.99 374.3 129.3 4794
exhibit cross-association. Therefore, the only binary parameters adjustable from V E and H E of these
systems are the interaction parameters X AC and X BC , respectively, which account for the difference in
intermolecular interaction between the different types of molecules Ž see Appendix A. . For the system
methanolq TAME, it is necessary to take cross-association into account, that is, hydrogen bonding
between the alcohol and the ether. The adjustable binary parameters for this system are X A B , K A B ,
D hUA B and DÕAUB , where K A B is the equilibrium constant of cross-association and D hUA B and DÕAUB are
the association energy and the ‘‘reaction’’ volume due to the formation of 1 mole of hydrogen bonds,
respectively. These parameters were fitted simultaneously to experimental H E and V E data using
least-square analysis. As can be seen from Eq. Ž15. in Appendix A, an additional entropy parameter
Q A B is introduced for the description of the excess Gibbs energy which is the binary parameter to be
adjusted using VLE data. The properties and parameters of the pure substances used in the model
calculations and the adjusted binary parameters are listed in Table 8. The calculated data for the
Fig. 1. Experimental V E and H E Žfrom Ref. w4x. and ERAS model calculations for the binary systems methanolqTAME Ža.
and TAMEq n-heptane Žb.. Experiment: ` 298.15 K, v 313.15 K; ERAS model: - - - 298.15 K, 313.15 K.
K. Kammerer et al.r Fluid Phase Equilibria 167 (2000) 223–241 233
ternary systems were predicted using only the adjusted parameters of the corresponding binary
systems.
As shown in Fig. 1, the model description for H E and V E of the binary systems is good;
especially, the temperature dependence of these properties is described very well. The prediction of
ternary H E using only binary model parameters also agrees pretty good with the experimental data as
shown in Fig. 2.
In Fig. 3, the model representation of binary VLE is compared with experimental results. The
agreement is very good for the nearly ideal system TAMEq n-heptane, but the model fails to
describe satisfactorily the systems methanolq TAME with an azeotrope and methanolq n-heptane
with a liquid–liquid mixing gap. Therefore, it is not surprising that the prediction of ternary VLE as
Fig. 2. Experimental H E and ERAS model calculations for the ternary system methanolqTAMEq n-heptane at various
compositions at 298.15 K. Experiment: ` obtained by adding methanol to mixtures with fixed composition ratios of
TAMEr n-heptane; v measured by mixing n-heptane with a 50:50 mixture of methanolrTAME; ERAS model.
234 K. Kammerer et al.r Fluid Phase Equilibria 167 (2000) 223–241
Fig. 3. ERAS model calculations for VLE of the binary mixtures TAMEq n-heptane Ža., methanolqTAME Žb. and
methanolq n-heptane Žc. at 313.15 K. Experiment: ` liquid phase, I vapor; ERAS model.
shown in Fig. 4 does not yield good results with the ERAS model. As shown by Coto et al. w26,27x, it
is possible to describe VLE of binary strongly nonideal systems with the ERAS model, but only at the
expense of a worser description of H E and V E.
4.2. UNIQUAC model
The UNIQUAC model w28x was also used to correlate the VLE data and a very good description is
¨
achieved for all binary systems. As reported by Mossner et al. w29x for methanolq TAME, the
K. Kammerer et al.r Fluid Phase Equilibria 167 (2000) 223–241 235
Fig. 4. Comparison between experimental values and ERAS model calculations for VLE of the ternary mixture methanol
ŽA.qTAME ŽB.q n-heptane ŽC. at 313.15 K of four different fixed mole fraction ratios of TAME ŽB.q n-heptane ŽC.
using only binary parameters. Experiment: ` x B r x C s 0.80r0.20, I x B r x C s 0.55r0.45, e x B r x C s 0.45r0.55, ^
x B r x C s 0.20r0.80; ERAS model.
Table 9
UNIQUAC parameters
Binary system a i j,1 wKx a i j,2 wyx a ji,1 wKx a ji,2 wyx
a
MethanolqTAME y63.86 0.0283 454.4 0.2641
a i j wKx b a ji wKx b
Methanolq n-heptane 11.05 1342
Methanolq iso-octane y6.93 1430
TAMEq n-heptane y82.18 111.9
TAMEq iso-octane y82.21 108.5
Pure component r q qX
Methanol 1.4311 1.432 0.960
TAME 4.7422 4.172 4.172
n-Heptane 5.1742 4.396 4.396
iso-Octane 5.8463 5.008 5.008
a
Kammerer et al. w5x; temperature dependence according to Eq. Ž3. with T0 s 298.15 K for the range 288–345 K.
b
At 3.13.15 K.
236 K. Kammerer et al.r Fluid Phase Equilibria 167 (2000) 223–241
Fig. 5. Comparison between experimental values and UNIQUAC model calculations for VLE of the ternary mixture
methanol ŽA.qTAME ŽB.q n-heptane ŽC. at 313.15 K of four different fixed mole fraction ratios of TAME ŽB.q n-heptane
ŽC. using only binary parameters. Experiment: ` x B r x C s 0.815r0.185, I x B r x C s 0.545r0.455, e x B r x C s
0.447r0.553, ^ x B r x C s 0.187r0.813; UNIQUAC model.
other systems, the parameters were determined only at 313.15 K. All binary parameters are listed in
Table 9. The parameters for the system TAMEq n-heptane agree very well with those determined by
¨
Mossner et al. w30x from VLE at different temperatures.
The results of the UNIQUAC calculations for the ternary system methanolq TAMEq n-heptane
using these binary parameters are shown in Fig. 5. It is obvious that the agreement between model
calculations and the experimental data is very good. For the second ternary mixture methanolq
TAMEq iso-octane, the agreement is equally good.
5. Conclusion
Excess volumes for three binary systems have been reported as well as excess enthalpies and
vapor-equilibrium data for two ternary systems containing methanol, TAME and an alkane. Two
models have been applied for the description of the data.
The ERAS model represents V E and H E of the binary systems very well and even the prediction
of ternary H E works reasonably well using only binary parameters. However, the ERAS model fails
to describe VLE of strongly nonideal mixtures with the system-specific parameters determined from
V E and H E.
K. Kammerer et al.r Fluid Phase Equilibria 167 (2000) 223–241 237
The UNIQUAC model is able to describe VLE of all binary systems almost quantitatively and even
the prediction of ternary VLE data using only binary model parameters is very good. However,
UNIQUAC, which is a rigid lattice model, is restricted to the description of VLE because it does not
give reliable H E and cannot give V E at all.
List of symbols
AEchem chemical contribution of excess property
AEphys physical contribution of excess property
a i j , a ji UNIQUAC parameters wKx
D hUA ; D hUB self-association enthalpies of components A and B wkJ moly1 x
D hUA B association enthalpy of component A with component B wkJ moly1 x
K A, K B self-association constants of components A and B
K AB association constant of component A with component B
P pressure wkPAx
Pio vapor pressure of pure component i wkPax
PiU reduction parameter of component i for pressure wJ cmy3 x
QAB entropic contribution to nonpolar intramolecular interactions between components
A and B wJ cmy1 Ky1 x
q, qX external surface areas, corrected external surface areas Ž UNIQUAC.
R universal gas constant wJ Ky1 moly1 x
r molecular size Ž UNIQUAC.
si surface-to-volume ratio of a molecule i wnmy1 x
T˜ reduced temperature
TiU reduction parameter of the temperature for pure component i wKx
T temperature wKx
DÕAU , DÕBU self-association volumes of components A and B wcm3 moly1 x
DÕAUB cross-association volume of component A with component B wcm3 moly1 x
Ṽ reduced volume
ViU molar hard core volume of component i wcm3 moly1 x
Vmol molar volume wcm3 moly1 x
XA B nonpolar van der Waals interaction parameter of component A with component
B wJ cmy3 x
xi mole fraction of component i in the liquid phase
yi mole fraction of component i in the vapor phase
Greek letters
gi activity coefficient of component i
F iU segment fraction of component i ŽUNIQUAC.
u i , u iX surface fraction and corrected surface fraction of component i ŽUNIQUAC.
Fi hard core volume fraction of component i in the mixture
fA1 , f B1 hard core volume fractions of the monomer molecules A and B
fA18, f B18 monomer hard core volume fractions of A and B in the pure liquid state
w i8 fugacity coefficient of pure component i
wi fugacity coefficient of component i in the mixture
qi surface fraction of component i
238 K. Kammerer et al.r Fluid Phase Equilibria 167 (2000) 223–241
Acknowledgements
The authors are grateful to the Deutsche Forschungsgemeinschaft for financial support Ž DFG Li
197r20-1 and 20-2..
Appendix A
The equations for the molar excess enthalpy H E and the molar excess volume V E of ternary
mixtures Ž A q B q C . with A s alkanol, B s ether and C s alkane are:
H E s Hchem
E E
q Hphys Ž4.
E
Hchem s x A D hUA K A Ž fA1 y fA1
0
. q x B D hUB K B Ž fB1 y fB10 .
f B1 Ž 1 y K A fA1 . PMU Vchem
E
q x A D hUA B K A B y Ž5.
Ž VBmolrVAmol . Ž1 y K B fB1 . q K A B fB1 V˜M2
FA PAU F B PBU F C PCU PMU
E
Hphys s Ž x AVAU q x B VBU q x C VCU . ½ V˜A
q
V˜B
q
V˜C
y
V˜M 5 Ž6.
V E s Vchem
E E
q Vphys Ž7.
E
Vchem ½
s V˜M x A DÕAU K A Ž fA1 y fA1
0
. q x B DÕBU K B Ž fB1 y fB10 .
f B1 Ž 1 y K A fA1 .
qx A DÕAUB K A B
Ž VBmolrVAmol . Ž1 y K B fB1 . q K A B fB1 5 Ž8.
E
Vphys s Ž x AVAU q x B VBU q x C VCU . V˜M y FAV˜A y F B V˜B y F C V˜C
ž / Ž9.
The equation for the molar excess Gibbs energy G E of a ternary mixture is:
with
1 fA1 f B1 K A B fA1 f B1 FC
s q q q Ž 12.
V VAU Ž 1 y K A fA1 . VBU Ž 1 y K B f B1 . VBU Ž 1 y K A fA1 .Ž 1 y K B f B1 . VCU
K. Kammerer et al.r Fluid Phase Equilibria 167 (2000) 223–241 239
and
0
1 f B1
s Ž i s A, B . Ž 13.
ViU ViU Ž 1 y K i f i1
U
.
1 1
s Ž 14.
VC8 VCU
The physical contribution to the activity coefficient of component A in a ternary mixture is given
by
PAU VAU V˜A1r3 y 1 1 1
ln gA,phys s
RT ½ ž3T˜A ln
VM1r3 y 1 / q
V˜A
q
V˜M 5
VAU XA B
q
RT
qB Ž 1 y qA . ½ V˜M
y T P QAB 5
VAU X AC
q
RT
qC Ž 1 y qA . ½ V˜M
y T P Q AC 5
VBU SA X BC
y
RT ž /½SB V˜M
y T P Q BC qBqC 5 Ž 15.
The expression for ln g B,phys and ln gC,phys is obtained by exchanging A by B and A by C in the
equation above. The parameter Q A B appears only in the expression for G E representing the entropic
contribution to nonpolar intramolecular interactions.
The physical contribution to the excess properties is derived from Flory’s equation of state, which
holds not only for pure components Žindex A, B or C ., but also for mixtures Žindex M .:
VMU and also VM need not be known explicitly because in order to use Eqs. Ž5., Ž6., Ž8., Ž9. and Ž15.,
only V˜M has to be known which is obtained from Eq. Ž 16. with P˜M and T˜M following from the
mixing rules for PMU and TMU.
q B is the surface fraction of the component B in the mixture, defined as:
siF i
qi s Ž 20.
Ý s jF j
j
si values can be estimated using Bondi’s method w31x. X i j in Eq. Ž18. is the energetic interaction
parameter characterizing the differences of dispersive intermolecular interactions between molecules i
and j in the mixture and in the pure components. X i j is the only adjustable parameter of the physical
part for H E and V E.
The chemical contribution to the excess properties arises from chemical interactions between the
molecules, in particular, hydrogen bonding. It is assumed that there is an equilibrium of linear chain
association of the components A and B and the possibility of cross-association:
lA
Ai q A
KA
iq1 Ž 21.
B qB l B
KB
i iq1 Ž 22.
A qB l A B
K AB
i j i j Ž 23.
The association constants K i are assumed to be independent from chain length i and their
temperature dependence is given by the following equation:
D hUi 1 1
K i s K i0 exp y ½ R ž T
y
T0 /5 i s Ž A, B, AB . Ž 24.
where D hUi is the association energy and c i the molar concentration of the i-mer. The reaction
volume DÕiU is related to the formation of the linear chain. f i1 and f i10 Ž i s A, B . are the volume
fractions of the monomeric species A1 Žalkanol. and B1 Žether. in the mixture and in the pure
0
components, respectively. To determine fA1 and fA1 , the following two equations have to be solved:
fA1 VAmol K A B f B1
FA s
Ž 1 y K A fA1 .
2 ½ 1q
VBmol Ž 1 y K B f B1 . 5 Ž 25.
f B1 K A B f B1
FB s
Ž 1 y K B f B1 .
2 ½ 1q
Ž 1 y K A fA1 . 5 Ž 26.
References