J. Chem.

Thermodynamics 37 (2005) 249–257

www.elsevier.com/locate/jct

VLE of the binary systems (dimethyl carbonate

with 2-propanol or 2-butanol) and (diethyl carbonate
with methylcyclohexane) at 101.3 kPa
A.B. Pereiro, A. Rodrı́guez, J. Canosa, J. Tojo *

Chemical Engineering Department, Vigo University, Lagoas-Marconende, s/n Apartado 874, 36200 Vigo, Spain

Received 9 February 2004; received in revised form 3 September 2004; accepted 16 September 2004
Available online 28 October 2004

Abstract

Isobaric vapour + liquid equilibria (VLE) have been experimentally determined for the binary systems (2-propanol + dimethyl
carbonate (DMC), dimethyl carbonate + 2-butanol, and methylcyclohexane + diethyl carbonate (DEC)) at 101.3 kPa. The activity
coefficients were calculated to be thermodynamically consistent and were correlated with the Wilson, NRTL, and UNIQUAC equa-
tions. ASOG and UNIFAC group contribution methods will be employed to predict these binary systems. Densities at T = (293.15,
298.15, 303.15, 308.15, and 313.15) K and atmospheric pressure have been measured over the whole composition range for
(DEC + methylcyclohexane). Excess molar volumes have been calculated for each temperatures. A polynomial equation has been
used to estimate the binary fitting parameters as a function of mole fraction and temperature. Standard deviations from the regres-
sion lines are shown for the binary mixture.
Ó 2004 Elsevier Ltd. All rights reserved.

Keywords: Density; VLE; Diethyl carbonate; Dimethyl carbonate; 2-Propanol; 2-Butanol; Methylcyclohexane; UNIFAC; ASOG; Correlation
equation

1. Introduction
This paper is a continuation of the thermodynamic
study of esters of carbonic acid with alkanes and alcoh-
ols [1,2], which is arousing an increasing interest due to
dimethyl carbonate (DMC) is considered an option for
meeting the oxygenated specifications on gasoline and
as a means of converting natural gas to a liquid trans-
portation fuel [3].
In this work, the densities of the binary mixture
(diethyl carbonate (DEC) + methylcyclohexane) at
T = (293.15, 298.15, 303.15, 308.15, and 318.15) K and
atmospheric pressure have been measured. The excess
*
Correponding author. Tel.: +34 986 812287; fax: +34 986 812382.
E-mail address: jtojo@uvigo.es (J. Tojo).
molar volumes have been calculated over the entire mole
fraction range for this mixture.
A modified polynomial equation [4] has been used to
correlate the excess quantities as a function of mole frac-
tion and temperature. The standard deviations between
experimental and calculated values are shown. No
experimental data corresponding to density have been
found in the literature on the binary mixtures.
Experimental data of isobaric vapor + liquid equili-
bria for the binary systems (2-propanol + DEC,
DMC + 2-butanol, and methylcyclohexane + DEC) at
101.3 kPa have been determined. In this case, there have
no been found data in the literature, either. The experi-
mental results will be compared with those correlated
through the equation of Wilson [5], NRTL [6], and
UNIQUAC [7]. Predictive methods [8,9], based on con-
tribution groups, have been used to predict the
experimental VLE data. The interaction parameters of

0021-9614/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jct.2004.09.009
250 A.B. Pereiro et al. / J. Chem. Thermodynamics 37 (2005) 249–257

TABLE 1 TABLE 2
Comparison of data with literature data for pure liquids at T = 298.15 K Density q, and excess molar volume V Em for (diethyl carbonate + meth-
Component q/(g Æ cm
3) Tbp/(K) ylcyclohexane) at several temperatures

Experiment Literature Experiment Literature x1 q V Em x1 q V Em

DEC 0.96924 0.96926a 399.32 399.32e g Æ cm
3 cm3 Æ mol
1 g Æ cm
3 cm3 Æ mol
1
0.96924b T = 293.15 K T = 298.15 K
DMC 1.06336 1.0632c 363.46 363.50j 0 0.76930 0 0 0.76498 0
1.0635d,e 0.0473 0.77744 0.182 0.0473 0.77305 0.187
2-propanol 0.78087 0.78094f 355.61 355.55k 0.0978 0.78643 0.331 0.0978 0.78197 0.338
0.7809g 0.1985 0.80496 0.544 0.1985 0.80036 0.558
2-butanol 0.80240 0.80239h 372.34 372.34l 0.2968 0.82373 0.666 0.2968 0.81899 0.684
0.80241a 0.3924 0.84256 0.722 0.3924 0.83770 0.740
Methylcyclohexane 0.76498 0.76506e 374.07 374.09l 0.4993 0.86426 0.719 0.4993 0.85923 0.742
0.7651i
0.5999 0.88533 0.657 0.5999 0.88020 0.674
a
Reference [12]. 0.6985 0.90648 0.559 0.6985 0.90124 0.573
b
Reference [13]. 0.7988 0.92864 0.409 0.7988 0.92328 0.419
c
Reference [14]. 0.8996 0.95153 0.215 0.8996 0.94606 0.220
d
Reference [15]. 0.9509 0.96341 0.103 0.9509 0.95786 0.107
e
Reference [16]. 1 0.97483 0 1 0.96924 0
f
Reference [17].
g
Reference [1]. T = 303.15 K T = 308.15 K
h
Reference [18]. 0 0.76065 0 0 0.75629 0
i
Reference [19]. 0.0473 0.76864 0.191 0.0473 0.76422 0.196
j
Reference [20]. 0.0978 0.77750 0.346 0.0978 0.77300 0.354
k
Reference [21]. 0.1985 0.79573 0.572 0.1985 0.79109 0.587
l
Reference [22]. 0.2968 0.81423 0.702 0.2968 0.80944 0.721
0.3924 0.83280 0.760 0.3924 0.82788 0.781
0.4993 0.85418 0.764 0.4993 0.84914 0.783
0.5999 0.87504 0.693 0.5999 0.86985 0.712
0.6985 0.89595 0.589 0.6985 0.89065 0.605
0.7988 0.91788 0.429 0.7988 0.91246 0.441
1.0 0.8996 0.94054 0.226 0.8996 0.93501 0.232
0.9509 0.95229 0.110 0.9509 0.94670 0.113
1 0.96361 0 1 0.95796 0
0.8
T = 313.15 K
0 0.75193 0
0.0473 0.75978 0.200
VE/(cm ·mol )
-1

0.6
0.0978 0.76848 0.363
0.82
0.1985 0.78642 0.603
3

0.80
0.2968 0.80460 0.746
VE/(cm3·mol-1)

0.4 0.78
0.3924 0.82290 0.810
0.76
0.4993 0.84404 0.807
0.74
0.5999 0.86464 0.733
0.2 0.72
0.6985 0.88531 0.623
0.70
290 295 300 305 310 315 0.7988 0.90702 0.453
T/(K) 0.8996 0.92944 0.238
0.0
0.0 0.5 1.0
0.9509 0.94108 0.116
x1 1 0.95229 0

FIGURE 1. Plot of excess molar volumes versus mole fraction for

diethyl carbonate + methylcyclohexane at: s, T = 293.15 K; n,
the functional group (OCOO) with (CH2), (ArCH) and
T = 298.15 K; h, T = 303.15 K; ,, T = 308.15 K; }, T = 313.15 K.
Internal figure: excess molar volumes at equimolar composition versus with (OH) in ASOG method and (OCOO) with (CH2)
temperature from T = 293.15 K to T = 313.15 K for diethyl and with (CH3OH) and (OH) in UNIFAC method have
carbonate + methylcyclohexane. been determined [10,11]; using previous experimental

TABLE 3
Parameters and standard deviations r for the system (diethyl carbonate + methylcyclohexane)
A11 A12 A21 A22 r
E
3
1
V m =ðcm  mol Þ 12.96 ± 0.10 0.069 ± 0.012
10.61 ± 0.11
0.055 ± 0.013 0.005
 A.B. Pereiro et al. / J. Chem. Thermodynamics 37 (2005) 249–257 251

TABLE 4 TABLE 5
Experimental vapor pressures values and boiling temperatures of pure Antoine coefficients
components
Component A B C DT/K
T/K P i =ðkPaÞ T/K P i =ðkPaÞ
2-Propanol 7.4859 1203.78 178.81 345.46–385.42
2-Propanol 2-Butanol 7.2649 1199.40 174.40 355.98–405.32
345.46 66.64 179.94 Methylcyclohexane 7.1443 1494.59 249.71 352.46–409.98
347.71 73.31 371.81 186.61
349.79 79.97 372.80 193.27
351.72 86.64 373.76 199.93
353.54 93.30 374.69 206.60
354.01 95.04 375.57 213.26 isobaric VLE data. Comparison between experimental
355.25 99.97 376.46 219.93 and predictive VLE data have been made.
355.61 101.30 377.29 226.59
356.27 103.97 378.13 233.26
356.90 106.63 378.93 239.92
358.45 113.30 379.71 246.59 2. Experimental
359.91 119.96 380.45 253.25
361.29 126.63 381.17 259.91 The pure components were supplied by Merck ex-
362.65 133.29 381.89 266.58
363.94 139.95 382.80 273.24
cept DMC by Fluka. They were degassed ultrasoni-
365.20 146.62 383.48 279.91 cally, and dried over molecular sieves type 0.3 and
366.38 153.28 384.11 286.57 0.4 nm (supplied by Aldrich) and kept in an inert ar-
367.56 159.95 384.79 293.24 gon atmosphere. Chromatographic testing of the rea-
368.65 166.61 385.42 299.90 gents showed purities, which fulfilled purchaser
369.76 173.28
specifications. Their mass fraction purities were more
2-Butanol than 0.99 for DMC, 0.995 for diethyl carbonate,
355.98 53.32 387.69 173.28
0.999 for 2-propanol, 0.995 for 2-butanol, and more
358.80 59.98 388.83 179.94
361.41 66.64 389.94 186.61 than 0.99 for methylcyclohexane. The maximum water
363.82 73.31 391.00 193.27 contents of the liquids were determined using a Metr-
366.02 79.97 392.05 199.93 ohm 737 KF coulometer. The corresponding obtained
368.13 86.64 393.07 206.60 values were 6 Æ 10
4 for 2-propanol, 1.5 Æ 10
3 for 2-
370.09 93.30 394.07 213.26
butanol, 1.1 Æ 10
3 for methylcyclohexane mass per
370.83 95.97 395.06 219.93
371.54 98.63 396.01 226.59 cent, and inappreciable quantities for carbonates.
372.34 101.30 396.94 233.26 The components purities were compared with recent
373.09 103.97 397.86 239.92 published values in table 1.
373.79 106.63 398.76 246.59 The mixtures were prepared by adding known
375.46 113.30 399.64 253.25
masses of the pure liquids into stoppered bottles with
377.04 119.96 400.48 259.91
378.57 126.63 401.34 266.58 a syringe to prevent preferential evaporation and to re-
380.02 133.29 402.19 273.24 duce possible errors in mole fraction calculations, using
381.42 139.95 402.98 279.91 a Mettler AX-205 Delta Range balance with a preci-
382.76 146.62 403.77 286.57 sion of ±10
5 g.
384.06 153.28 404.56 293.24
The density of the pure liquids and mixtures were
385.31 159.95 405.32 299.90
386.52 166.61 measured with an Anton Paar DSA-5000 digital vibrat-
ing tube densimeter. This densimeter was calibrated
Methylcyclohexane
periodically with Millipote quality water, following the
352.46 53.32 387.59 146.62
356.26 59.98 389.36 153.28 purchasers specifications. The precision for the density
359.62 66.64 391.04 159.95 measurements is ±1 Æ 10
5 g Æ cm
3.
362.83 73.31 392.80 166.61 A glass Fischer LABODEST VLE apparatus model
365.81 79.97 394.38 173.28 602/D, manufactured by Fischer Labor und Verfah-
368.47 86.64 395.87 179.94
renstechnik (Germany), was used in the equilibrium
370.99 93.30 397.33 186.61
371.98 95.97 398.76 193.27 determinations. The equilibrium vessel was a dynamic
373.08 98.63 400.12 199.93 recirculating still, equipped with a Cottrell circulation
374.07 101.30 401.45 206.60 pump. This pump ensures that both liquid and vapor
374.95 103.97 402.80 213.26 phases are in intimate contact during boiling and also
375.86 106.63 404.10 219.93
in contact with the temperature sensing element. The
378.04 113.30 405.35 226.59
380.12 119.96 406.56 233.26 equilibrium temperature was measured with a digital
382.12 126.63 407.66 239.92 Yokogawa model 7563 thermometer with an accuracy
384.05 133.29 408.90 246.59 of ±0.01 K. The apparatus is equipped with a glass
385.89 139.95 409.98 253.25 temperature probe PT 100 with an accuracy of
252 A.B. Pereiro et al. / J. Chem. Thermodynamics 37 (2005) 249–257

350 350

300 300

250 250

200 200
Pi0 /(KPa)

Pi0 /(KPa)
150 150

100 100

50 50

0 0
310 320 330 340 350 360 370 380 390 320 340 360 380 400 420
(a) T/(K) (b) T/(K)

300

250

200
Pi0 /(KPa)

150

100

50

0
280 300 320 340 360 380 400 420

(c) T/(K)

FIGURE 2. Plot of experimental data with their fitted curves — and comparative vapour pressure values of: (a) 2-propanol; (b) 2-butanol; (c)
methylcyclohexane, as a function of the temperature: s, this work; n, from [24]; h, from [25]; $, from [26]; }, from [27].

±0.01 K. For the pressure measurement, digital pres- 3. Results and discussion
sure controller Ruska model 7218 with an accuracy of
±0.001 kPa was used. Equilibrium conditions were as- Density and excess molar volume for the binary mix-
sumed when constant temperature and pressure were ture (DEC + methylcyclohexane) at T = (293. 15,
obtained for 30 min or longer. Then, samples of liq- 298.15, 303.15, 308.15, and 318.15) K are reported in ta-
uid and condense were taken for analysis. The com- ble 2. Excess molar quantities, for the binary mixtures,
position analysis of both samples were determined were derived, respectively, from:
using the abovementioned digital vibrating tube dens-
imeter. The concentration of the liquid and vapor X
N

phases at equilibrium were determined on the basis V Em ¼ xi M i ðq
1
qi
1 Þ: ð1Þ

i¼1
of density-composition curves obtained previously
for each of the binary mixtures. The root-mean- In this equation, q is the density of the mixture and qi is
square deviation in the mole fraction was usually the density of pure components. The binary excess prop-
<0.001. erties were fitted to a polynomial equation:
 A.B. Pereiro et al. / J. Chem. Thermodynamics 37 (2005) 249–257 253

TABLE 6 TABLE 7
(Vapor + liquid) equilibrium data for (2-propanol + DEC) at 101.3 (Vapor + liquid) equilibrium data for (DMC + 2-butanol) at 101.3 kPa
kPa
T/(K) x y c1 c2
T/(K) x y c1 c2
371.33 0.0320 0.0842 2.0887 0.9801
361.68 0.0246 0.0939 3.0655 0.9726 369.99 0.0745 0.1617 1.7887 0.9844
360.09 0.0630 0.1646 2.2248 0.9814 368.15 0.1356 0.2677 1.7140 0.9845
359.69 0.0780 0.1950 2.1604 0.9734 366.57 0.1994 0.3507 1.5982 0.9993
358.28 0.1226 0.2611 1.9401 0.9823 366.55 0.2022 0.3511 1.5788 1.0030
357.07 0.1582 0.3118 1.8797 0.9917 366.06 0.2252 0.3788 1.5513 1.0070
355.48 0.2217 0.3882 1.7748 1.0046 365.77 0.2434 0.3966 1.5155 1.0127
354.18 0.3041 0.4597 1.6113 1.0362 365.59 0.2517 0.4068 1.5111 1.0135
353.77 0.3368 0.4844 1.5577 1.0520 365.14 0.2795 0.4315 1.4626 1.0262
353.67 0.3553 0.4883 1.4944 1.0776 364.75 0.2975 0.4532 1.4598 1.0275
353.29 0.3839 0.5103 1.4670 1.0930 364.41 0.3328 0.4760 1.3843 1.0505
353.01 0.4136 0.5299 1.4296 1.1130 363.98 0.3649 0.5042 1.354 1.062
352.82 0.4483 0.5459 1.369 1.150 363.59 0.4066 0.5328 1.299 1.087
352.72 0.4782 0.5562 1.313 1.193 363.30 0.4418 0.5545 1.255 1.115
352.57 0.5102 0.5721 1.273 1.231 363.02 0.4741 0.5749 1.223 1.142
352.46 0.5419 0.5877 1.236 1.273 362.72 0.5109 0.5973 1.189 1.177
352.35 0.5789 0.6051 1.197 1.332 362.70 0.5357 0.6104 1.160 1.201
352.28 0.6086 0.6235 1.176 1.370 362.51 0.5623 0.6286 1.144 1.224
352.27 0.6382 0.6422 1.155 1.409 362.37 0.5940 0.6473 1.120 1.260
352.25 0.6854 0.6622 1.110 1.531 362.23 0.6038 0.6567 1.122 1.264
352.29 0.7177 0.6813 1.089 1.608 362.14 0.6242 0.6702 1.111 1.285
352.36 0.7507 0.7084 1.079 1.663 362.09 0.6474 0.6831 1.093 1.319
352.50 0.7829 0.7256 1.054 1.789 362.01 0.6717 0.6978 1.079 1.356
352.66 0.8117 0.7458 1.038 1.901 361.98 0.6940 0.7131 1.068 1.383
352.75 0.8277 0.7613 1.035 1.946 361.95 0.7138 0.7254 1.057 1.418
352.93 0.8478 0.7826 1.032 1.995 361.93 0.7412 0.7449 1.046 1.459
353.15 0.8696 0.8002 1.019 2.124 361.95 0.7693 0.7648 1.033 1.509
353.36 0.8908 0.8223 1.014 2.241 362.04 0.8009 0.7893 1.021 1.562
353.66 0.9111 0.8498 1.012 2.305 362.19 0.8372 0.8193 1.009 1.631
353.96 0.9352 0.8774 1.006 2.556 362.35 0.8741 0.8529 1.001 1.708
354.46 0.9585 0.9157 1.005 2.701 362.60 0.9158 0.8944 0.994 1.819
354.97 0.9769 0.9556 1.008 2.515 362.97 0.9548 0.9413 0.992 1.861
355.05 0.9791 0.9596 1.007 2.523

2 X
X 2
j
1 Vapor pressure of DEC and DMC were determined
V Em ¼ xð1
xÞ Aij xi=8 ðT
T 0 Þ ; ð2Þ
experimentally, by us, and were presented in previous
i¼1 j¼1
papers [10,11]. Experimental vapor pressures for 2-pro-
where T0 is 298.15 K, x is the mole fraction and Aij is the panol, 2-butanol, and methylcyclohexane have been cal-
fitting parameter. The degree of this equation was culated and listed in table 4. Figure 2 shows the
optimized by applying the F test [23]. The correlation experimental vapor pressure data for the pure compo-
parameters are listed in table 3, together with the stand- nents and the comparison with the literature data. The
ard deviations (r). This deviation is calculated by apply- Antoine parameters of the pure components are listed
ing the following expression: in table 5, together with the temperature interval in
which they have been determined.
!1=2 Experimental isobaric VLE data, corresponding to
nX
DAT
2
r¼ zexp
zpred =nDAT ; ð3Þ the temperature, T, and the liquid-phase and vapor-
i phase mole fractions, x and y, for the binary systems
(2-propanol + DEC, DMC + 2-butanol, and methylcy-
where property values and the number of experimental clohexane + DEC) at 101.3 kPa are presented in tables
data are represented by z and nDAT, respectively. 6–8. The activity coefficients, ci, that were calculated
Figure 1 shows the excess molar volumes and the cor- from the equation,
responding fitted curves for the binary mixture at the


studied interval temperatures. Excess molar volumes yiP Bii
V Li P
P i P X n X n
ln ci ¼ ln  þ þ yy 
are positive in the entire composition range. In figure xi P i RT 2RT j¼1 k¼1 i k
1, the variation of the excess molar volumes with the

2dji
djk ; ; ð4Þ
temperature is also exhibited, when the composition is
equimolar. where dji and djk are defined by,
254 A.B. Pereiro et al. / J. Chem. Thermodynamics 37 (2005) 249–257

TABLE 8 dji ¼ 2Bji
Bjj
Bii ; ð5Þ

(Vapor + liquid) equilibrium data for (methylcyclohexane + DEC) at
101.3 kPa djk ¼ 2Bjk
Bjj
Bkk ; ð6Þ
T/K x y c1 c2
where, T and P, are the boiling point and the total pres-
398.09 0.0079 0.0223 1.5684 1.0118
sure, respectively, V Li , is the molar liquid volume of
396.87 0.0296 0.1002 1.9322 0.9846
392.92 0.0696 0.2058 1.8488 1.0129 component i, Bii and Bjj, are the second virial coefficients
391.10 0.0963 0.2651 1.7962 1.0168 of the pure gases, P i , is the saturation pressure, and dij,
389.74 0.1263 0.3325 1.7734 0.9940 is related to the cross second virial coefficient. The molar
387.31 0.1796 0.4123 1.6392 1.0014 virial coefficients, Bii and Bij, were estimated by the
385.47 0.2246 0.4702 1.5634 1.0095
method of Hayden and O
Connell [28] using the molec-
383.50 0.2532 0.5036 1.5597 1.0426
382.24 0.2973 0.5496 1.4958 1.0454 ular parameters suggested by Prausnitz et al. [29]. Crit-
381.19 0.3227 0.5736 1.4768 1.0609 ical properties of all components were taken from
380.18 0.3614 0.6123 1.4440 1.0562 DIPPR [30]. The activity coefficients are listed in the last
379.44 0.3958 0.6352 1.394 1.075 columns of tables 6–8.
378.10 0.4659 0.6712 1.295 1.144
The results reported in these tables indicate that the
377.92 0.4925 0.6932 1.271 1.130
377.92 0.5162 0.7063 1.235 1.135 binary systems 2-propanol + DEC and DMC + 2-buta-
377.13 0.5523 0.7256 1.211 1.176 nol exhibit a minimum boiling azeotrope. Azeotropic
376.22 0.6123 0.7569 1.166 1.239 compositions have been obtained by determining the
376.04 0.6478 0.7736 1.132 1.278 x1 values that make the function (x1
y1) = f(x1)
375.60 0.6785 0.7953 1.124 1.285
equal to zero. The corresponding azeotropic tempera-
375.38 0.7122 0.8025 1.087 1.395
375.02 0.7479 0.8186 1.066 1.480 tures were computed from a cubic polynomial equa-
374.66 0.7839 0.8365 1.049 1.575 tion T = f(x1), whose coefficients were obtained by
374.50 0.8226 0.8563 1.027 1.695 fitting the experimental results around the azeotropic
374.21 0.8635 0.8879 1.023 1.736 point, using the x1 values determined previously. The
374.05 0.9057 0.9159 1.010 1.897
liquid composition and boiling temperature of the aze-
373.98 0.9523 0.9535 1.002 2.080
otropes for the binary mixtures 2-propanol + DEC
and DMC + 2-butanol are 0.645 and 352.27 and
0.754 and 361.94, respectively. The azeotropes can
be due to a somewhat hydrogen-bonding character
TABLE 9 of 2-propanol and 2-butanol, which means that their
Consistency test for the binary mixtures mixtures with DMC may have strong intermolecular
System DP/(mm Hg) Dy interactions or not, depending upon the composition
2-Propanol + DMC 0.002 0.007 range.
DMC + 2-butanol 0.003 0.007 The VLE data were found to be thermodynamically
Methylcyclohexane + DEC 0.006 0.008 consistent by the point-to-point method of Van Ness
DP, deviation between Pexp and Pcalc; Dy, deviation between yexp and et al. [31] and modified by Fredenslund et al. [32] and
ycalc. the results are reported in table 9.

TABLE 10
Parameters and standard deviations between experimental and calculated values for the binary systems at 101.3 kPa
Model Parameters DT/K Dy
2-Propanol (1) + DMC (2)
Wilson k11
k12 1439.9 k21
k22 1844.3 0.435 0.0094
NRTL g11
g12 2038.9 g21
g22 1726.8 a 0.827 0.410 0.0089
UNIQUAC u11
u12 244.11 u21
u22 585.26 0.437 0.0091
DMC (1) + 2-butanol (2)
Wilson k11
k12 1434.8 k21
k22 906.42 0.296 0.0067
NRTL g11
g12 1329.1 g21
g22 1302.1 a 0.925 0.301 0.0076
UNIQUAC u11
u12 514.35 u21
u22 191.62 0.296 0.0065
Methylcyclohexane (1) + DEC (2)
Wilson k11
k12
227.49 k21
k22 3059.3 0.526 0.0099
NRTL g11
g12
630.43 g21
g22 2694.1 a
0.228 0.399 0.0105
UNIQUAC u11
u12
109.20 u21
u22 1050.2 0.484 0.0100
k11
k12, g11
g12 and u11
u12 are in units of J Æ mol
1.
 A.B. Pereiro et al. / J. Chem. Thermodynamics 37 (2005) 249–257 255

1 365

0.8

360
0.6

T/(K)
y1
0.4
355

0.2

0 350
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
(a) x1 (a) x1, y1
1 375

0.8

370
0.6
T/(K)

y
1
0.4
365

0.2

0 360
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
(b) x1 (b) x1, y1
405
1

400
0.8
395

0.6 390
T/(K)

y1 385
0.4

380

0.2
375

0 370
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
(c) (c) x1, y1
x1
FIGURE 3. Plot of experimental x–y data for the binary systems at FIGURE 4. Plot of boiling temperature diagram (T) for the binary
101.3 kPa: s, experimental data; — the best correlated model; systems at 101.3kPa: s, experimental data; — the best correlated
(a) 2-propanol (1) + DMC (2), NRTL; (b) DMC (1) + 2-butanol model; (a) 2-propanol (1) + DMC (2), NRTL; (b) DMC (1) + 2-
(2), UNIQUAC; and (c) methylcyclohexane (1) + DEC (2), butanol (2), UNIQUAC; and (c) methylcyclohexane (1) + DEC (2),
UNIQUAC. UNIQUAC.
256 A.B. Pereiro et al. / J. Chem. Thermodynamics 37 (2005) 249–257

The correlated equations of Wilson, NRTL, and Group contribution methods have been employed to
UNIQUAC have been used. The parameters were predict the VLE of the binary systems under study.
optimized by minimizing the objective function, Figure 5 displays the comparison of the calculated and
" exp #2 the experimental activity coefficients for the binary sys-
X np Xnc
cij
ccal
ij tems with a good agreement achieved. Table 11 presents
O:F: ¼ : ð7Þ
j¼1 i¼1
cexp
ij TABLE 11
Standard deviations of boiling points r(T), and vapor-phase mole
Table 10 gives the correlating parameters and the fraction r(y) resulting by the prediction of VLE using ASOG and
standard deviations for all methods, the boiling point UNIFAC method
and the vapor-phase mole fraction. Inspection of the re- Method r(y) r(T)/K
sults shows that all models are suitable to correlate the 2-Propanol (1) + DMC (2)
binary data. Figures 3 and 4 show the temperature, ASOG 0.0087 0.3129
the liquid-phase and vapor-phase mole fractions, and UNIFAC 0.0181 0.6082
the correlated line corresponding to the best model for DMC (1) + 2-butanol (2)
each binary system. ASOG 0.0140 1.4434
ASOG and UNIFAC group contribution methods UNIFAC 0.0110 0.3411
have been employed to predict the VLE of the binary Methylcyclohexane (1) + DEC (2)
systems. The volume Rk and surface area Qk parame- ASOG 0.0198 1.4895
UNIFAC 0.0155 1.2015
ters were obtained from the literature [30,33].

3.0 3.0

2.5 2.5

2.0 2.0
γ1
γ1

1.5 1.5

1.0 1.0

0.0 0.5 1.0 0.0 0.5 1.0

(a) x1 (b) x1
3.0

2.5

2.0
γ1

1.5

1.0

0.0 0.5 1.0

(c) x1

FIGURE 5. Plot of activity coefficient (c) for the binary systems at 101.3kPa: s, experimental data; – fitting curves using the ASOG and – UNIFAC
methods for the binary systems: (a) 2-propanol (1) + DMC (2); (b) DMC (1) + 2-butanol (2); and (c) methylcyclohexane (1) + DEC (2).
 A.B. Pereiro et al. / J. Chem. Thermodynamics 37 (2005) 249–257
the standard deviation between experimental and pre-
dicted values of the boiling points and the vapor-phase
mole fractions for the binary systems. The standard
deviations of the temperature and the composition of
the vapor phase indicate that ASOG and UNIFAC
methods give better predictions for alcohols with car-
bonates than methylalkane with DEC. The intermolecu-
lar interactions between methylcyclohexane, a non-polar
component, and DEC, a slightly polar liquid can explain
large positive values of de excess molar volume and of
large positive activity coefficients for this mixture, this
may be the reason to explain the difficulty of the predic-
tion methods applied to this mixture.
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JCT 04-38