Fluid Phase Equilibria 169 2000. 8599 www.elsevier.

nlrlocaterfluid

Vapourliquid equilibria XIV. The ternary system cyclohexanemethanolhexane at 293.15 K

M. Goral ) , P. Oracz, S. Warycha
Department of Chemistry, Warsaw Uniersity, Pasteura 1, 02-093 Warsaw, Poland Received 5 October 1999; accepted 11 January 2000

Abstract The total vapour pressure for the ternary mixture cyclohexanemethanolhexane and constituent binary systems methanolhexane and cyclohexanehexane were measured at 293.15 K with a modified static method. Different expressions for G E suitable for the correlation of these data as well as an equation of state incorporating an association term are tested. The possibility to predict ternary VLE from constituent binary data and the simultaneous correlation of VLE and LLE data at 293.15, 303.15 and 313.15 K is investigated. q 2000 Elsevier Science B.V. All rights reserved.
Keywords: Data; Vapourliquid equilibria; Correlation; Prediction; Association; Cyclohexane; Hexane; Methanol

1. Introduction The system cyclohexanemethanolhexane at 303.15 and 313.15 K was investigated in our laboratory w1,2x within a project on the measurement, correlation and prediction of the VLE of ternary systems of non-electrolytes. In this paper, we report the results of total vapour pressure measurements at 293.15 K for this ternary system and the two constituent binaries methanolhexane and cyclohexanehexane. The results for the remaining binary, i.e., cyclohexanemethanol, were published previously w3x. 2. Materials The chemicals used were of the highest purity available commercially. Cyclohexane and hexane both analytical reagent grade, POCh. were crystallized threefold, fractionated on an 80 TP column
)

Corresponding author. E-mail address: mgoral@chem.uw.edu.pl M. Goral ..

0378-3812r00r$ - see front matter q 2000 Elsevier Science B.V. All rights reserved. PII: S 0 3 7 8 - 3 8 1 2 0 0 . 0 0 3 0 6 - X

86

M. Goral et al. r Fluid Phase Equilibria 169 (2000) 8599

Table 1 Vapour pressures P and second virial coefficients bii of pure substances used at 293.15 K Molar liquid volumes used in the correlation of VLE were calculated according to Yen and Woods w40x. Compound Cyclohexane Methanol Hexane P 293.15 K. kPa. This work 10.336 13.004 16.159 Literature 10.336"0.005a 10.338 c 12.995"0.012 a 13.021c 16.166"0.012 a 16.173 c 16.160"0.005e 1.905 b 2.339 d 2.054 b y bii 293.15 K. dm3 moly 1 .

Calculated according to Boublik et al. w35x. Calculated with Tsonopoulos parameters fitted to recommended data of Dymond and Smith w37x. c Calculated according to Dykyj et al. w36a,36bx. d Calculated with Tsonopoulos parameters fitted to recommended data of Dymond w38x. e Calculated according to Wieczorek and Stecki w39x.
b

and stored over 4A sieves. Methanol analytical reagent grade, POCh. was fractionated on an efficient column having 80 theoretical plates and stored over 3A sieves. Impurities were determined chromatographically. The water content was checked using Fischers reagent and was found to be on the limit of detectability. All the substances had a purity not less than 99.95 mol%. 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 for the pure substances.

3. Method The vapour pressures of the mixtures were determined with an apparatus differing from a static one by some modifications concerning degassing of the sample and working without null manometer. The apparatus and experimental procedure have been described previously w4x. During 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 pressure was measured with a cathetometer. 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 cyclohexane with hexane, to which methanol was added.

4. Results and discussion The results of total vapour pressure measurements are given in Table 2 for the binary systems and in Table 3 for the ternary system. Our previous results for the binary systems as well as the binary data presented in this paper were tested in Refs. w1,3,57x.

M. Goral et al. r Fluid Phase Equilibria 169 (2000) 8599

87

Table 2 Liquid mole fraction x b , total vapour pressures P ; vapour mole fractions y b and deviations d P d P s P y Pcalc . calculated with EoSC xb yb P kPa. d P kPa.
y1

xb ; D b b s 1.8 cm 0.95540 0.96600 0.97200 0.97730 0.98240 0.98393 0.98666 0.98710 0.98989 0.99150 0.99268 0.99430 0.99488 0.99670 0.99713 0.99750 0.99848 0.99850 0.99895 0.99920 0.99930 0.99962 1.00000 xa 0.6032 0.7059 0.8101 0.8996 1.0000
3

yb 0.5424 0.5821 0.6131 0.6481 0.6912 0.7065 0.7372 0.7426 0.7805 0.8056 0.8258 0.8563 0.8682 0.9088 0.9193 0.9287 0.9547 0.9553 0.9681 0.9754 0.9784 0.9881 1.0000 ya 0.4889 0.5945 0.7162 0.8372 1.0000

P kPa. 23.47 21.94 20.87 19.76 18.52 18.34 17.56 17.25 16.59 15.96 15.68 15.02 14.92 14.27 13.87 13.93 13.52 13.58 13.35 13.31 13.21 13.16 13.00 P kPa. 13.071 12.459 11.775 11.154 10.336

d P kPa. 0.11 0.05 0.02 y0.03 y0.09 0.11 0.06 y0.12 0.03 y0.10 0.00 y0.11 y0.01 y0.01 y0.25 y0.05 y0.08 y0.02 y0.07 y0.02 y0.08 0.00 0.00 d P kPa. y0.014 0.000 0.002 0.023 0.000

Methanol b. hexane c. Q bc s 0.0521; K bb s 1.381 MPa 0.00000 0.0000 16.16 0.00 0.00002 0.0021 16.18 y0.01 0.00003 0.0031 16.19 y0.02 0.00027 0.0263 16.34 y0.25 0.00076 0.0667 16.59 y0.73 0.00188 0.1353 17.53 y1.15 0.00233 0.1563 17.94 y1.20 0.00609 0.2606 21.08 y0.73 0.00829 0.2927 22.37 y0.42 0.02319 0.3753 25.40 y0.28 0.02443 0.3783 25.53 y0.27 0.04142 0.4032 26.51 y0.29 0.07120 0.4199 27.42 y0.05 0.08599 0.4240 27.50 y0.13 0.10228 0.4273 27.65 y0.11 0.14830 0.4325 27.97 0.03 0.85920 0.4440 27.87 0.10 0.90070 0.4608 27.17 0.21 0.93490 0.4964 25.46 0.16 0.93970 0.5047 25.08 0.14 0.94420 0.5136 24.68 0.14 0.95020 0.5277 24.07 0.11 0.95400 0.5382 23.86 0.33 xa ya P kPa. d P kPa.

Cyclohexane a. hexane c. Qac sy0.0017 0.0000 0.0000 16.159 0.000 0.2031 0.1501 15.213 0.007 0.3099 0.2332 14.684 0.007 0.4054 0.3111 14.178 y0.006 0.5072 0.3992 13.618 y0.015

For methanolcyclohexane system test of Q0.5 vs. 1rT , test of infinite dilution activity coefficients as well as comparisons of azeotropic point parameters were performed w5x. Methanolcyclohexane data at 293.15 and 303.15 K were used in Ref. w3x to predict the molar enthalpy of mixing at 298.15 K. For the methanolhexane system, the infinite dilution activity coefficient for methanol at 293.15 K has been estimated to be 65.1 " 9. This value together with corresponding values measured at 303.15 and 313.15 K were used in Ref. w1x to test with the partial molar enthalpy of mixing of methanol at infinite dilution. In Ref. w6x the Q0.5 vs. 1rT test has been presented and in Ref. w1x parameters of the azeotropic point has been discussed and relevant equations were reported.

88

M. Goral et al. r Fluid Phase Equilibria 169 (2000) 8599

Table 3 Ternary system cyclohexane a. methanol b. hexane c. at 293.15 K: experimental liquid mole fractions x a , x b and total pressure P ; vapour mole fractions ya , y b and deviations d P d P s P y Pcalc . calculated with EoSC xa 0.7627 0.7178 0.6832 0.6526 0.2120 0.1651 0.1344 0.1032 0.0547 0.5953 0.5452 0.5190 0.1669 0.1293 0.1217 0.0992 0.0846 0.0459 0.0982 0.0705 0.0383 0.4550 0.4313 0.4144 0.1192 0.1005 0.0573 0.3186 0.3072 0.2940 0.0723 0.0641 0.0453 0.0242 0.0246 0.1922 0.1817 0.1793 0.0314 0.0259 0.0138 xb 0.0575 0.1130 0.1557 0.1935 0.7380 0.7960 0.8339 0.8711 0.9316 0.0825 0.1597 0.2001 0.7427 0.8007 0.8129 0.8471 0.8700 0.9294 0.8128 0.8656 0.9269 0.0795 0.1274 0.1617 0.7589 0.7967 0.8841 0.0938 0.1262 0.1638 0.7944 0.8157 0.8698 0.9304 0.9313 0.0797 0.1297 0.1412 0.8496 0.8707 0.9313 ya 0.3624 0.3532 0.3509 0.3500 0.3591 0.3582 0.3550 0.3432 0.3062 0.2793 0.2747 0.2740 0.2778 0.2762 0.2763 0.2720 0.2688 0.2416 0.2170 0.2113 0.1906 0.2105 0.2076 0.2067 0.2055 0.2042 0.1943 0.1482 0.1470 0.1462 0.1418 0.1392 0.1347 0.1204 0.1238 0.0886 0.0873 0.0871 0.0802 0.0755 0.0673 yb 0.4909 0.5046 0.5082 0.5098 0.5023 0.5034 0.5073 0.5156 0.5651 0.4759 0.4854 0.4872 0.4822 0.4837 0.4848 0.4896 0.4962 0.5421 0.4713 0.4808 0.5236 0.4574 0.4653 0.4679 0.4661 0.4672 0.4848 0.4472 0.4518 0.4548 0.4542 0.4553 0.4651 0.5099 0.5123 0.4327 0.4409 0.4420 0.4485 0.4530 0.4973 P kPa. 23.065 23.509 23.625 23.651 23.666 23.661 23.635 23.410 21.794 24.238 24.550 24.614 24.667 24.678 24.658 24.542 24.315 22.695 25.378 25.079 23.483 25.011 25.358 25.451 25.451 25.565 25.003 25.851 26.105 26.171 26.334 26.375 26.017 24.195 24.131 26.424 26.803 26.859 26.879 26.758 24.854 d P kPa. 0.084 0.004 y0.003 y0.024 y0.045 y0.021 0.066 0.093 0.142 y0.026 y0.047 y0.033 y0.059 y0.007 0.013 0.054 0.067 0.125 y0.005 0.046 0.124 y0.061 y0.002 0.004 y0.169 y0.025 0.084 y0.068 0.020 y0.012 y0.031 0.038 0.078 0.151 0.191 y0.067 0.009 0.030 0.013 0.080 0.169

For the cyclohexanehexane system, a critically evaluated selection of VLE data is published w8x. From all available literature data, six data sets have been selected in the range 283354 K and 6101

M. Goral et al. r Fluid Phase Equilibria 169 (2000) 8599

89

kPa. These data were fitted with the two parameter Wilson equation with standard deviation s PrkPa. s 0.076. Our data were not included in these calculations. Results of prediction of our VLE data using these parameters as well as performance of other correlating equations are given in Table 4. Similar results can be obtained with NRTL and UNIQUAC. For the cyclohexanehexane system Q0.5 vs. 1rT test is presented in Ref. w7x. All these tests show excellent internal consistency of our data and agreement with good literature data. The binary VLE data were correlated with the following equations for the excess Gibbs energy: Redlich and Kister w9x, Van Laar extended by Van Ness w10x, Myers and Scott w11x, Marsh w12x, SSF Rogalski and Malanowski w13x., Wilson w14x, the three parameter Wilson Novak et al. w15x., Wilson as modified by Tsuboka and Katayama w16x, NRTL Renon and Prausnitz w17x. , UNIQUAC Anderson and Prausnitz w18x., Abbott and Van Ness w19x and Ortega et al. w20x. For the methanol-containing systems, the Wilson and NRTL equations were also applied with an additional term accounting for the association of methanol according to the KretschmerWiebe model w21x. The association constant used in this model was adopted from works of Nagata and treated as a non-adjustable parameter. Addition of the association term does not result in a significantly better description of the data and therefore this term was neglected in further considerations. The coefficients of the G E-equations were obtained using a modified Barkers method w2224x. In the case of multi-parameter equations, the number of the parameters is limited to six. The values of second virial coefficients for the pure substances were calculated using literature data cf. Table 1. and for the mixtures, they were calculated according to Tsonopoulos w25x. The results of the correlations are presented in Table 4. Table 4 also contains experimental and predicted liquidliquid equilibrium LLE. data in binary systems containing methanol. It was observed that the parameters of the G E-equations depend on the second virial coefficients used in the fit of VLE data, which influence the predicted LLE compositions. Therefore, special care was taken to select the most reliable values. The presented results demonstrate that the polynomial expressions for G E and the expressions based on the local composition concept do not provide sufficiently accurate simultaneous description of vapourliquid and liquidliquid equilibrium data for both systems containing methanol. This conclusion agrees with literature cf. e.g., Refs. w27,28x.. The near ideal system cyclohexanehexane can be described by any equation with approximately the same accuracy. In addition to the methods using activity coefficients, an equation of state proposed by Goral w26x, suitable for systems with associated compounds, was used. This equation, denoted further as EoSC, uses one adjustable parameter per binary in the classical mixing rule for an energetic parameter, and, in the chemical part, one self-association constant for methanol. This constant is assumed to be independent of any other compound in the mixture. The experimental values of pressure in the ternary system were compared with values predicted by EoSC, Wilson, NRTL and UNIQUAC equations using parameters adjusted to the constituent binary mixtures. Results are given in Table 5. It shows that EoSC predicts the pressure of the ternary system much better than the other investigated equations. The polynomial equation of Marsh was applied to the ternary system using Eq. 1. as discussed previously by Oracz w33x, to which ternary terms were added. The equation has the form G E s x i q x j .
2q b E GiEj xU i . q G ter .

1.

90

M. Goral et al. r Fluid Phase Equilibria 169 (2000) 8599

Table 4 Efficiency of different equations for binary systems at 293.15 K number of parameters n, number of experimental binary points m, standard deviation of the total vapour pressure s P . a , deviations of predicted mole fractions of methanol in liquid phases at equilibrium D xX , D xY Equation n s P . kPa. Number of sign changesb Calculated azeotropic point x az Paz kPa. Deviations of predicted phase split D xXa D xY a xY s 0.842 0.005 0.009 y0.014 y0.008 y0.013 y0.012 two regions. 0.009 y0.017 y0.005 y0.012 two regions. 0.010 y0.046 not applicable not applicable 0.060 y0.331 y0.067 y0.010 unstable. y0.063 0.001 2 regions. y0.074 y0.445 0.003 0.007 y0.010 0.001 0.024 y0.020 y0.054 0.006

Methanol a.qcyclohexane b., EoSC RedlichKister Van LaarVan Ness MyersScott Marsh AbbottVan Ness Ortega k s 0.3. SSF Wilson three isotherms. Novak et al.. TsubokaKatayama. NRTL a s 0.45. a s 0.4. three isotherms, a s 0.45. LLE. d UNIQUAC three isotherms. Athermal MeckeKempter e

m s 26; Paz s 22.31 kPa; experimental LLE datac : xX s 0.103; 2 0.178 4 0.546 22.34 6 0.363 9 0.458 28.19 6 0.212 7 0.484 24.01 5 0.128 4 0.544 22.24 2q3 0.129 6 0.543 22.41 5 0.132 5 0.536 22.57 6 0.149 9 0.602 21.48 6 0.128 5 0.545 22.35 2 0.309 7 0.543 22.24 2 0.443 6 0.540 22.04 3 0.307 8 0.543 22.29 2 0.475 4 0.536 22.59 2 1.041 6 0.555 21.56 2 1.635 4 0.544 22.15 3 1.039 6 0.561 21.26 2 1.040 6 0.546 21.54 6. 3.275 0 0.535 22.19 2 0.194 6 0.542 22.50 2 0.369 15 0.561 36.05 2 0.542 4 0.540 22.21

Cyclohexane a.qhexane b., m s 10 zeotropic. homogeneous. RedlichKwong EoS 1 0.013 1 RedlichKwong EoS 0 0.077 0 RedlichKister 2 0.014 2 Van LaarVan Ness 2 0.012 2 Ortega k s 4. 3 0.008 4 SSF 2 0.013 2 Wilson 2 0.013 2 three isotherms. 2 0.072 0 six data sets. f 2 0.035 0 TsubokaKatayama. 2 0.012 2 2 0.013 2 NRTL a s 0.3. three isotherms. 2 0.073 0 UNIQUAC 2 0.012 2 three isotherms. 4 0.026 0 Methanol a.qhexane b., m s 20; experimental LLE datac xX s 0.210; xY s 0.820 EoSC 2 0.328 4 0.437 28.60 RedlichKister 6 0.223 14 0.438 28.06 Van LaarVan Ness 6 0.163 13 0.438 28.08 MyersScott 6 0.152 13 0.438 28.08 0.012 y0.072 y0.049 y0.052 0.016 0.027 0.017 y0.099

M. Goral et al. r Fluid Phase Equilibria 169 (2000) 8599

91

Table 4 continued . Equation n s P . kPa. Number of sign changesb Calculated azeotropic point x az Paz kPa. Deviations of predicted phase split D xXa D xY a

Methanol a.qhexane b., m s 20; experimental LLE datac xX s 0.210; xY s 0.820 Marsh 3q3 0.156 13 0.438 28.07 AbbottVan Ness 5 0.152 13 0.438 28.07 Ortega k s 0.3. 6 0.177 11 0.417 26.99 SSF 6 0.152 11 0.438 28.08 Wilson 2 0.369 4 0.433 27.88 three isotherms. 2 0.395 4 0.433 27.94 Novak et al.. 3 0.310 4 0.435 28.09 TsubokaKatayama. 2 0.691 8 0.438 28.09 2 0.525 5 0.420 27.29 NRTL a s 0.45. a s 0.4. 2 0.872 4 0.440 28.03 three isotherms, a s 0.4. 4 0.918 4 0.437 28.05 qKretschmerWiebe 2 1.236 6 0.440 27.85 LLE. d 6. 2.380 0 0.449 26.69 UNIQUAC 2 0.172 7 0.442 28.01 three isotherms. 2 0.316 8 0.438 27.99 Athermal MeckeKempter e 2 0.535 8 0.437 28.12
a b

y0.001 0.026 y0.027 0.022 two regions. y0.028 0.007 not applicable not applicable y0.112 y0.052 y0.155 0.077 y0.172 y0.423 y0.156 0.068 y0.165 0.058 y0.151 0.181 0.000 0.000 y0.043 0.039 y0.015 0.028 y0.143 0.076

s P . s w S P y Pcalc . 2 r m y n.x0.5. If 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 with respect to the correlating curve. Easy measure of the randomness is the number of sign changes, which should be roughly equal to m r2" m r2. 0.5. c Solubilities of methanol according to the experimental data reported in Refs. w27,32x. d Parameters fitted to experimental LLE data. according to Ref. w27x. e Mecke-Kempter model according to Kehiaian and Treszczanowicz w21x. f Parameters fitted to selected experimental VLE data taken from Ref. w8x.

E . where xU i s x ir x i q x j and Gi j is any equation suitable for the correlation of a binary mixture i q j .. For this reason, Eq. 1. is much more general than any other equation proposed in the literature. b is a selectable parameter. In this work we used b s y0.1. This value is suitable for systems with high positive deviations. If b s 0 then Eq. 1. is equivalent to Kohlers equation. For the ternary contribution, G E ter., the following equation was used 2 2 G E ter . s x a x b x c C 0 q C 1 f a q C 2 f b q C 3 f a qC4f b q C5faf b

2.

where fa s 3 x a y 1 . f b s 3 x b y 1. The subscripts a, b and c denote cyclohexane, methanol and hexane, correspondingly.

92

M. Goral et al. r Fluid Phase Equilibria 169 (2000) 8599

Table 5 Comparison of different equations for the ternary system cyclohexane a. methanol b. hexane c. at 293.15 K average standard error of the total vapour pressure, s P ., relative standard error of the total vapour pressure, s d P r P . a . Equation Number of parameters Binary
b

s P . kPa.
Ternary 0 0 0 0 0 0 6 0 6 0.08 0.37 1.23 1.68 0.20 1.44 0.09 1.46 0.09

s d P r P . %.
0.32 1.47 4.91 6.76 0.78 5.81 0.38 5.91 0.36

EoSC 1r0r1q3 Wilson 2r2r2 NRTL 2r2r2 LLE. c 6r6r6. UNIQUAC 2r2r2 Eqs. 1 and 2 with b s 0 Kohler. using Marsh 2r3q3r3q2 Eqs. 1 and 2 with b s 0 Kohler. using Marsh 2r3q3r3q2
a

s P . s w S Pexp y Pcalc . 2 r m y n.x0.5 n s number of parameters, m s number of points.; s d P r P . s w S1y Pcalc r Pexp . 2 r m y n.x 0.5. b This column should be read: number of adjustable parameters for the mixture a,b.rfor the mixture a,c.rfor the mixture b,c.. The parameters are those fitted to the binary data cf. Table 4.. c Parameters fitted to experimental LLE data. according to Ref. w27x.

Table 5 demonstrates that the polynomial equation used in Eq. 1. predicts ternary data in the investigated system very badly. The correlation with Eq. 2. using six adjustable constants give the same result as EoSC, which does not use any ternary parameter. We did not find ternary enthalpy of mixing data for the ternary system w30x.. The data published by Rant et al. w31x for the similar system methylcyclohexanemethanol hexane at 303.15 agree qualitatively with the enthalpy calculated from our VLE data at the three temperatures. The investigated ternary system contains a two-liquid-phase region of type 2 cf. e.g., Refs. w27,32x.. The upper critical solution point, UCST, for the cyclohexanemethanol system is 318.9 " 0.3 K w27x, and for methanolhexane system 307.7 " 0.15 K w32x. According to Hradetzky and Lempe w27x, at 305.7 K there exists a double plait point in the ternary system and at 306.15 K two separate plait points. Below 305.7 K, the two-liquid-phase region is of type 2 according to Srensen and Arlt w29x. The system cyclohexanehexane is nearly ideal and both methanol-containing systems exhibit high positive and nearly equal deviations from ideal behaviour. The vicinity of the UCST and the flat shape of the G x .-surface makes the prediction of the liquid-phase split difficult. Any small error in G E results in significant shift of the predicted liquidliquid equilibria. All equations, reported in Table 5, predict a ternary phase split of type 2 except for the Wilson equation, which is not applicable for liquid phase split prediction. Among the extensions of the Wilson equation, the TsubokaKatayama modification reproduces the methanol-rich phase but unacceptably overestimates the concentration of hydrocarbon-rich phase. The extension of the Wilson equation due to Novak et al. predicts, in contrary with experiment, LLE of type 1. NRTL overestimates the phase split when parameters were fitted to binary VLE data. Parameters fitted to

M. Goral et al. r Fluid Phase Equilibria 169 (2000) 8599

93

Fig. 1. Methanolqcyclohexane at 293.15, 303.15 and 313.15 K. Experimental total vapour pressure P . vs. liquid mole fraction of methanol correlated with EoSC.

ternary LLE data taken from Ref. w27x. correctly reproduce the phase split but very poorly predict binary and ternary vapourliquid equilibria. UNIQUAC predicts much broader phase split than experimentally observed, mainly in the hexane rich area. The use of six adjustable ternary parameters for the Marsh equation, the best from the point of view of ternary VLE data, result in a worse agreement of the predicted liquid-phase split. Taking into account the results of the test calculations, we have chosen EoSC for simultaneous description of the VLE and LLE data presented below in Figs. 16. The EoSC gives the best results using the less adjustable parameters than the other investigated equations. In the physical part of the EoSC, one temperature-dependent parameter Q i j is used for each binary mixture. In the system cyclohexane a. methanol b. hexane c. , this parameter was approximated with:

Qab s 0.0588 y 18.0 1rT y 1r313.15 . Q bc s 0.0554 y 15.3 1rT y 1r313.15 . Qac s 0.0

3a . 3b. 3c .

94

M. Goral et al. r Fluid Phase Equilibria 169 (2000) 8599

Fig. 2. Methanolqhexane at 293.15, 303.15 and 313.15 K. Experimental total vapour pressure P . vs. liquid mole fraction of methanol correlated with EoSC.

Fig. 3. Ternary system cyclohexaneqmethanolqhexane at 293.15 triangles., 303.15 circles. and 313.15 squares.. Relative differences in %. between experimental vapour pressure and the pressure predicted with EoSC 100 D P r P . vs. liquid mole fraction of methanol.

M. Goral et al. r Fluid Phase Equilibria 169 (2000) 8599

95

Fig. 4. Methanolqcyclohexane. Experimental LLE data correlated with EoSC. Temperature T . vs. mole fraction of methanol.

The chemical part of the EoSC uses one constant of self-association for methanol, K . The temperature dependence of K was approximated with vant Hoffs equation: K T . rMPay1 s 0.855 exp 2200 1rT y 1r313.15 .

4.

The excluded volume b . used in the chemical part of the EoSC is shifted by D b with respect to the value of b used in the physical part. The D b for a given component is treated as an adjustable, temperature-independent parameter. The following values of D b were used:

D ba s y4.8 cm3 D b b s 1.8 cm3 D bc s 0

5a . 5b. 5c .

where indices a, b, c denote cyclohexane, methanol and hexane, respectively. The parameters for methanol used for calculation of K T . with Eq. 4. as well as of D b b have the same values as those used in Vols. 3 and 4 of the data selection of Goral et al. w34x. They were adjusted to verified VLE literature data of methanol with hydrocarbons in temperature range 293348 K. Eq. 3a. and D ba were adjusted only to our binary VLE data at the three temperatures because we did not find literature data for this system. Afterwards, the obtained values were slightly refitted to LLE data investigated in this paper. Parameters in Eq. 3b. were adjusted to our VLE data as well as to literature VLE data selected in . They cover the temperature range 293348 K. Altogether, Eqs. 3a5c contain eight constants, which were used in the EoSC method for the description of the VLE and LLE investigated in this paper. The figures below show VLE data

96

M. Goral et al. r Fluid Phase Equilibria 169 (2000) 8599

Fig. 5. Methanolqhexane. Experimental LLE data correlated with EoSC. Temperature T . vs. mole fraction of methanol.

presented in this paper and two isotherms published previously w1,2x. The LLE data are taken from Refs. w27,32x. They were checked in comparison with other available literature data.

Fig. 6. Ternary LLE data at 293.15, 303.15 and 313.15 K correlated with EoSC. Normalised mole fraction of hexane Z . defined with Eq. 6. vs. mole fraction of methanol. Triangles and solid lines 293.15 K; circles and dashed lines 303.15 K; squares and dotted line 313.15 K.

M. Goral et al. r Fluid Phase Equilibria 169 (2000) 8599

97

Figs. 1 and 2 show the results of the correlation of binary, methanol-containing, VLE data at temperatures 293.15, 303.15 and 313.15 K. The P x curves are very steep at the ends of the composition range. Therefore, a small error in mole fraction results in a big error in the corresponding vapour pressure. Nevertheless, the experimental points are very well approximated with the EoSC. For the ternary systems at the three temperatures, the deviations between measured and predicted pressure in %. are shown in Fig. 3. The magnitude of the deviations is comparable with the experimental error. The relative standard deviations at 293.15, 303.15 and 313.15 K are 0.32%, 0.41% and 0.33%, respectively. Figs. 4 and 5 show the correlation of binary LLE data taken from Refs. w27,32x The results are quite good especially when compared with results for the other equations discussed above. Fig. 6 shows the correlation of the ternary LLE data at 293.15, 303.15 and 313.15 K, respectively. The data are taken from Ref. w27x. In these figures, the X-axis corresponds to the mole fraction of methanol, whereas on the Y-axis the normalised mole fraction of hexane Z . is plotted. Z is defined by equation: Z s x cr x c q x a .

6.

where x c and x a are mole fractions of hexane and cyclohexane, respectively. In this plot, the conodes of the investigated system were practically horizontal and therefore were not plotted. At 306.15 K, the EoSC gives two separate plait points in accordance with the experiment. The results presented above show that the EoSC enables accurate prediction of ternary VLE from constituent binaries and simultaneous correlation of VLE and LLE data using less adjustable parameters than the other equations studied in this paper. List of symbols a, b energetic parameter and excluded volume in equation of state Ci coefficients in Eq. 2. E G molar excess Gibbs energy molar excess Gibbs energy for the binary mixture i q j GiEj K constant of self association of methanol m number of experimental points n number of adjustable parameters P vapour pressure kPa. Q0.5 equimolar value of G ErRT R gas constant T temperature K. x mole fraction in liquid xU mole fraction in liquid in Eq. 1. mole fractions in coexisting liquid phases xX , xY y mole fraction in vapour Z mole fraction of hexane normalised according to Eq. 6. Greek letters a NRTL parameter b exponent in Eq. 1.

98

M. Goral et al. r Fluid Phase Equilibria 169 (2000) 8599

bii Db s Q

second virial coefficient dm3 moly 1 . difference between b in physical and chemical parts of EoSC, respectively standard deviation adjustable binary parameter in equation of state

Acknowledgements This work was partially supported by KBN funds through the Department of Chemistry, University of Warsaw within the project BST 592r16r98.

References
w1x w2x w3x w4x w5x w6x w7x w8x w9x w10x w11x w12x w13x w14x w15x w16x w17x w18x w19x w20x w21x w22x w23x w24x w25x w26x w27x w28x w29x w30x w31x M. Goral, P. Oracz, S. Warycha, Fluid Phase Equilib. 152 1998. 109120. M. Goral, P. Oracz, S. Warycha, Fluid Phase Equilib. 129 1997. 223233. P. Oracz, M. Goral, G. Wilczek-Vera, S. Warycha, Fluid Phase Equilib. 126 1996. 7192. B. Janaszewski, P. Oracz, M. Goral, S. Warycha, Fluid Phase Equilib. 9 1982. 295310. P. Oracz, M. Goral, G. Wilczek-Vera, S. Warycha, Fluid Phase Equilib. 112 1995. 291306. P. Oracz, S. Warycha, Fluid Phase Equilib. 108 1995. 199211. M. Goral, P. Oracz, S. Warycha, Fluid Phase Equilib. 81 1992. 261272. A. Ma czynski, A. Bok, P. Oracz, A. Skrzecz, VaporLiquid Equilibria: Vol. 1. Hydrocarbons: Part 1. Binary systems of C 5 and C 6 with C 5 to C 20 hydrocarbons, Thermodynamics Data Center, Warsaw, Poland, 1997. O. Redlich, A.T. Kister, Ind. Eng. Chem. 40 1948. 345348. H.C. Van Ness, Classical Thermodynamics of Nonelectrolyte Solutions, Pergamon, London, 1964. D.B. Myers, R.L. Scott, Ind. Eng. Chem. 55 1963. 4346. K.N. Marsh, J. Chem. Thermodyn. 9 1977. 719724. M. Rogalski, S. Malanowski, Fluid Phase Equilib. 1 1977. 137152. G.M. Wilson, J. Am. Chem. Soc. 86 1964. 127130. J.P. Novak, P. Vonka, J. Suska, J. Pick, Coll. Czech. Chem. Commun. 39 1974. 35933598. T. Tsuboka, T. Katayama, J. Chem. Eng. Jpn. 8 1975. 181187. H. Renon, J.M. Prausnitz, AIChE J. 14 1968. 135144. T.F. Anderson, J.M. Prausnitz, Ind. Eng. Chem. Process Des. Dev. 17 1978. 552561. M.M. Abbott, H.C. Van Ness, AIChE J. 21 1975. 6271. J. Ortega, J.A. Pena, C. de Alfonso, J. Chem. Eng. Data 31 1986. 339342. H. Kehiaian, A. Treszczanowicz, Bull. Acad. Polon. Sci., Ser. Sci. Chim. 18 1970. 693. M. Goral, Z. Phys. Chem. Leipzig. 258 1977. 10401044. M. Goral, B. Janaszewski, Z. Phys. Chem. Leipzig. 258 1977. 417425. G. Kolasinska, P. Oracz, Z. Phys. Chem. Leipzig. 260 1979. 169173. C. Tsonopoulos, AIChE J. 20 1974. 263272. M. Goral, Fluid Phase Equilib. 118 1996. 2759. G. Hradetzky, D.A. Lempe, Fluid Phase Equilib. 69 1991. 285301. J.P. Novak, J. Matous, J. Pick, LiquidLiquid Equilibria, Academia, Prague, 1987. J.M. Srensen, W. Arlt, LiquidLiquid Equilibrium Data Collection. Ternary Systems. Chemistry Data Series, Vol. V, Part 2, Dechema, 1980. czynski, Floppy Book on Heat of Mixing. Version 1993-1.1., Thermodynamic Research Center, The K.N. Marsh, A. Ma Texas Engineering Experimental Station, The Institute of Coal Chemistry of the Polish Academy of Sciences, 1993. D. Rant, B. Nietzschmann, G. Werner, H. Schuberth, Z. Phys. Chem. Leipzig. 244 1970. 387400.

M. Goral et al. r Fluid Phase Equilibria 169 (2000) 8599

99

w32x G. Hradetzky, H.-J. Bittrich, Int. Data Series 3., 216. w33x P. Oracz, in: The third CODATA Symposium on Critical Evaluation and Prediction of Phase Equilibria in Multicomponent Systems, Budapest, 68 Sept., 1987. w34x M. Goral, czynski, A. Bok, P. Oracz, A. Skrzecz, VaporLiquid Equilibria: Vol. 3. Alcoholsqaliphatic A. Ma hydrocarbons. Vol. 4. Alcoholsqnon-aliphatic hydrocarbons, Thermodynamics Data Center, Warsaw, Poland, 1998. w35x T. Boublik, V. Fried, E. Hala, The Vapour Pressures of Pure Liquids, Elsevier, Amsterdam, 1973. w36ax J. Dykyj, M. Repas, Tlak Nasytenej Pary Organickych Zlucenin, Veda, Bratislava, 1979. w36bx J. Dykyj, M. Repas, J. Svoboda, Tlak Nasytenej Pary Organickych Zlucenin, Veda, Bratislava, 1984. w37x J.H. Dymond, E.B. Smith, The Virial Coefficients of Pure Gases and Mixtures, Clarendon Press, Oxford, 1980. w38x J.H. Dymond, in: The Second International IUPAC Workshop on VaporLiquid Equilibria in 1-Alkanolq n-Alkane Mixtures, Paris, 57 September, 1985. w39x S.A. Wieczorek, J. Stecki, J. Chem. Thermodyn. 10 1978. 117186. w40x L.C. Yen, S.S Woods, AIChE J. 12 1966. 9599.