Fluid Phase Equilibria 248 (2006) 197205

Vaporliquid equilibria for binary and ternary mixtures of diisopropyl ether, ethanol, and 2,2,4-trimethylpentane at 101.3 kPa
Hsu-Chen Ku a , Chein-Hsiun Tu b,
a

Department of Nursing, Cardinal Tien College of Nursing, Hsintien, Taipei 23148, Taiwan b Department of Applied Chemistry, Providence University, Taichung 43301, Taiwan

Received 24 February 2006; received in revised form 26 July 2006; accepted 7 August 2006 Available online 14 August 2006

Abstract Vaporliquid equilibrium (VLE) at 101.3 kPa has been determined for diisopropyl ether + ethanol + 2,2,4-trimethylpentane ternary system, as well as for diisopropyl ether + ethanol and diisopropyl ether + 2,2,4-trimethylpentane (isooctane) binary systems. A minimum boiling azeotrope was found in the diisopropyl ether + ethanol system, while no azeotrope was observed in the diisopropyl ether + 2,2,4-trimethylpentane system or in the ternary system. Calculations of nonideality of the vapor-phase were made with SoaveRedlichKwong equation of state. The thermodynamic consistency of the binary VLE data was examined by both the direct test of Van Ness and the method of Kojima et al. The VLE data of the ternary system passed the thermodynamic consistency test of the McDermottEllis method as modied by Wisniak and Tamir. The activity coefcients of the binary mixtures were satisfactorily correlated as a function of mole fraction with the Wilson, NRTL, and UNIQUAC models. The models with their best-tted binary parameters were used to predict the phase equilibrium behavior of the ternary system. 2006 Elsevier B.V. All rights reserved.
Keywords: Experiments; Isobaric VLE; Diisopropyl ether; Ethanol; 2,2,4-Trimethylpentane

1. Introduction The reformulation of gasoline includes certain oxygenated compounds such as alcohols and ethers. These oxygenated compounds are added to improve the octane rating and pollutionreducing capability of gasoline. This work has been carried out as a part of the project to investigate the thermophysical behavior of the oxygenated compounds containing mixtures. The main purpose of the present paper is to investigate the vaporliquid equilibrium (VLE) for the liquid mixtures formed by two oxygenated compounds, such as ethanol and diisopropyl ether, as well as 2,2,4-trimethylpentane (isooctane), a component that generally appears in gasoline. In this work, we undertake to obtain the isobaric VLE data for a ternary mixture (diisopropyl ether + ethanol + 2,2,4trimethylpentane) and two constituent binary mixtures (diisopropyl ether + ethanol and diisopropyl ether + 2,2,4trimethylpentane) at 101.3 kPa. In a previous work, we reported

the VLE data for the binary system of ethanol + 2,2,4trimethylpentane at 101.3 kPa [1]. A recent literature survey only revealed the isobaric VLE data of the diisopropyl ether + ethanol system at 684.00 mmHg from Vijayaraghavan et al. [2]. No isobaric data in literature are available for diisopropyl ether + 2,2,4-trimethylpentane or diisopropyl ether + ethanol + 2,2,4-trimethylpentane system. 2. Experimental 2.1. Chemicals The chemicals used were of analytical grade. Diisopropyl ether (>99.0 mass%) and 2,2,4-trimethylpentane (>99.5 mass%) were obtained from Tedia (USA). Ethanol (>99.9 mass%) was obtained from Merck (Germany). All chemicals were used without further purication after gas chromatography failed to show any signicant impurities. Before measurements the liquids were dried over molecular sieves (Merck, type 0.3 nm pellets). The purity of components was further ascertained by comparing their normal boiling points, densities, and refractive indices with the corresponding literature values [3] as shown

Corresponding author. E-mail address: chtu@pu.edu.tw (C.-H. Tu).

0378-3812/$ see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.uid.2006.08.004

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Table 1 Comparison of measured boiling points T, densities , and refractive indices nD with literature values [3] Component T (101.3 kPa) (K) This work Diisopropyl ether Ethanol 2,2,4-Trimethylpentane 341.53 351.44 372.33 Literature 341.66 351.443 372.388 (298.15 K) (kg m3 ) This work 718.37 785.09 687.72 Literature 718.54 784.93 687.81 nD (298.15 K) This work 1.36512 1.35926 1.38887 Literature 1.3655 1.35941 1.38898

in Table 1. The density, , of each pure component was measured at (298.15 0.01) K using a vibrating-tube densimeter (Model: DMA-58, Anton-Paar, Austria) with an uncertainty of 0.02 kg m3 . The refractive index, nD , of each pure component was measured at (298.15 0.05) K by an Abbe refractometer (Model: RX-5000, Atago, Tokyo) with an uncertainty of 0.00002. 2.2. Apparatus and procedure The apparatus to measure VLE was all-glass equilibrium still (NGW, Wertheim, Germany) with provisions for both vapor and liquid recirculation as described by Hunsmann [4]. The equilibrium still has a total volumetric capacity of about 100 cm3 . The charge for experimental runs was prepared by mixing known masses of the three components. Equilibrium conditions were indicated by constant boiling temperatures in the liquid and vapor-phases inside the still with the difference in temperature being within 0.02 K. The system was maintained at an equilibrium state at least 30 min before samples were taken. The equilibrium boiling temperature was measured using a standard platinum resistance thermometer connected to a digital multi-meter (Model: 1560/2560, Hart Scientic, USA) with an uncertainty of 0.02 K. The system pressure was regulated using a manostat as that described by Fowler and Hunt [5]. The system pressure could then be controlled at 101.3 kPa under the ow of high-purity nitrogen gas. The constant pressure at 101.3 kPa was determine, with an uncertainty of 0.1 kPa, via the boiling temperature of a reference substance, pure water, etosawski ebulliometer [6] connected to the measured in a Swi system. During each experimental run, the system was maintained at the pressure when the temperature reading on the ebulliometer was 373.15 K with an uncertainty of 0.02 K. The uncertainty of measurement in the boiling temperature is estimated to be 0.05 K. The equilibrium compositions of the liquid and condensed vapor were analyzed by a Perkin-Elmer Autosystem gas chromatograph (GC). A ame ionization detector along with a (60 m long, 0.25 mm i.d., 0.5 m lm) capillary column packed with Petrocol DH (SUPELCO, USA) was used. The GC response peaks were integrated using a Perkin-Elmer Turbochrom software. Calibration analyses by using gravimetrically prepared standard solutions were carried out to convert the peak area ratio to mole fraction of the sample. The pertinent polynomial ts had a correlation coefcient R2 better than 0.99. The uncertainty of composition analysis is estimated to be 0.003 in mole fraction.

3. Results and discussion The VLE data for two binary systems of diisopropyl ether + ethanol and diisopropyl ether + 2,2,4-trimethylpentane at 101.3 kPa are presented in Tables 2 and 3, respectively. The activity coefcient of pure liquid i was calculated from the equation: i = i Pyi o s o Pi xi i exp[vL i (P Pi )/RT ] (1)

s , and vL are the liquid mole fracwhere xi , yi , Pio , i , i i tion, vapor mole fraction, vapor pressure, vapor-phase fugacity coefcient, vapor-phase fugacity coefcient at saturation, and liquid molar volume for component i, respectively. Vapors , were calculated from the phase fugacity coefcients, i and i SoaveRedlichKwong (SRK) equation of state [7], where the binary interaction parameter, kij , was set to 0. The temperature dependence of the pure component vapor pressure Pio was obtained from the equation:

ln Pio (Pa) = a +

b + c ln T + d T e T

(2)

where a , b , c , d , and e are component specic coefcients for vapor pressure and T is the temperature in Kelvin. The liquid
Table 2 Experimental VLE data for diisopropyl ether (1) + ethanol (2) system at 101.3 kPa T (K) 348.29 345.76 343.73 342.15 341.00 340.08 339.34 338.80 338.34 337.97 337.67 337.47 337.35 337.31 337.37 337.58 337.97 338.73 339.92 x1 0.044 0.089 0.143 0.193 0.240 0.287 0.338 0.389 0.440 0.489 0.537 0.598 0.649 0.705 0.757 0.809 0.859 0.907 0.954 y1 0.154 0.256 0.339 0.403 0.452 0.490 0.523 0.552 0.578 0.604 0.631 0.651 0.675 0.703 0.730 0.760 0.795 0.848 0.915 1 2.868 2.539 2.223 2.055 1.920 1.790 1.660 1.549 1.454 1.384 1.329 1.239 1.188 1.140 1.101 1.065 1.036 1.022 1.010 2 1.001 1.021 1.047 1.072 1.095 1.129 1.173 1.221 1.280 1.337 1.393 1.531 1.641 1.787 1.968 2.206 2.511 2.734 2.941 gE /RT 0.047 0.102 0.154 0.195 0.226 0.254 0.277 0.292 0.303 0.307 0.306 0.299 0.286 0.264 0.237 0.202 0.160 0.113 0.059

H.-C. Ku, C.-H. Tu / Fluid Phase Equilibria 248 (2006) 197205 Table 3 Experimental VLE data for diisopropyl ether (1) + 2,2,4-trimethylpentane (3) system at 101.3 kPa T (K) 368.15 366.30 363.99 362.04 360.37 358.57 356.67 355.32 353.86 352.21 350.82 349.49 348.18 346.88 345.82 344.59 343.57 342.57 x1 0.084 0.125 0.179 0.228 0.273 0.325 0.384 0.427 0.476 0.534 0.585 0.637 0.690 0.744 0.790 0.849 0.898 0.950 y1 0.179 0.254 0.343 0.415 0.474 0.535 0.597 0.640 0.684 0.732 0.771 0.807 0.841 0.874 0.900 0.930 0.954 0.977 1 1.015 1.014 1.015 1.015 1.012 1.007 1.002 1.003 1.002 1.001 1.002 1.000 1.000 1.001 1.002 1.000 1.000 0.998 2 1.000 1.001 1.003 1.005 1.007 1.011 1.016 1.016 1.020 1.024 1.026 1.030 1.036 1.037 1.038 1.052 1.059 1.116 gE /RT 0.001 0.003 0.005 0.007 0.008 0.010 0.011 0.010 0.011 0.012 0.012 0.011 0.011 0.010 0.009 0.008 0.006 0.004

199

molar volume (vL ) for pure component was evaluated from the equation as vL (m3 kmol1 ) = b1+(1(T/c)) a
d

Fig. 1. Experimental Tx1 y1 diagram for diisopropyl ether (1) + ethanol (2) system at 101.3 kPa: ( : liquid-phase and : vapor-phase) this work (: liquidphase and : vapor-phase) literature values at 648 mmHg [2], and () Wilson equation.

(3)

where a, b, c, and d are component specic coefcients for liquid molar volume. The reduced excess molar Gibbs energy (gE /RT) was calculated according to the denition: gE = RT
N

xi ln i
i=1

(4)

where N is the number of components. Table 4 presents the parameters of the pure components pertaining to this investigation (CHEMCAD Data Bank [8]). This table includes the values

of the corresponding parameters for determining vapor pressures and liquid molar volumes, critical properties, acentric factors, and UNIQUAC parameters for pure components. Figs. 1 and 2 are the temperature-composition phase diagrams for the binary systems of diisopropyl ether + ethanol and diisopropyl ether + 2,2,4-trimethylpentane, respectively. Fig. 3 plots the gE /RT as a function of liquid composition for these two systems. A positive deviation from ideal behavior was observed for entire systems. Fig. 1 contains our experimental Txy values with those from Vijayaraghavan et al. [2] for diisopropyl ether + ethanol system. It is noted that our isobaric condition (101.3 kPa) is different from theirs (684.00 mmHg).

Table 4 Critical properties and the parameters of vapor pressure, liquid molar volume, and UNIQUAC equation for pure components used in this study Parameters Tc (K) Pc (bar) Vc (cm3 mol1 ) Po (Pa) a b c d e v (m3 kmol1 ) a b c d UNIQUAC q UNIQUAC r Diisopropyl ether 500.05 28.80 386 0.3387 114.74 7130.0 15.184 1.7234 102 1 0.6921 0.2697 500.05 0.28570 4.088 4.7421 Ethanol 513.92 61.48 167 0.6452 74.475 7164.3 7.3270 3.134 106 2 1.6480 0.27627 513.92 0.23310 1.972 2.1054 2,2,4-Trimethylpentane 543.96 25.68 468 0.3031 120.81 7550.0 16.111 1.710 102 1 0.5886 0.27373 543.96 0.28460 5.0079 5.8463

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Fig. 2. Experimental Tx1 y1 diagram for diisopropyl ether (1) + 2,2,4trimethylpentane (3) system at 101.3 kPa: ( : liquid-phase and : vapor-phase) this work and () Wilson equation.

Fig. 3. Experimental gE /RT vs. x1 diagram at 101.3 kPa for systems: ( ) diisopropyl ether (1) + ethanol (2) and () diisopropyl ether (1) + 2,2,4trimethylpentane (3); () Wilson equation. Table 5 Results of the thermodynamic consistency tests for two binary systems studied Systems i + j Direct test of Van Ness Consistency index 1 + 2c 1 + 3e
a b c d e f

The system of diisopropyl ether + ethanol shows a minimum boiling azeotrope, but there is no azeotrope observed for the system of diisopropyl ether + 2,2,4-trimethylpentane. Azeotropic composition for diisopropyl ether (1) + ethanol (2) system was obtained by determining the x1 values that make the function ((x1 y1 ) = f(x1 )) zero. A quadratic polynomial equation was assumed for f(x1 ). The corresponding azeotropic temperature was computed from the experimental result around the azeotropic point, using the x1 value previously determined. Thus, the azeotropic composition was found at x1 = 0.700 and the corresponding azeotropic temperature was obtained at T = 337.30 K. The thermodynamic consistency of binary systems was treated using the direct test proposed by Van Ness [9]. According to the Van Nesss method, a consistency index associated with the test characterizes the degree of departure of a data set from consistency. For this method, the values of gE /RT were calculated from experimental activity coefcients and were correlated with a three-parameter RedlichKister equation [10]. The quadratic polynomial dependence in temperature was assumed for each parameter. With constants from this t, residuals in the logarithm of the activity-coefcient ratio ln( i / j ) were calculated; where two sets of activity coefcients come from the experimental data and from the correlation. Table 5 shows the result of the thermodynamic consistency test. The value of the consistency index for diisopropyl ether + ethanol system was found to be 4, suggesting that the VLE data are of acceptable quality. However, the diisopropyl ether + 2,2,4-trimethylpentane system has the consistency index of 10, and the quality of the VLE data was considered to be poor. The thermodynamic consistency of binary systems was also examined by the point, area, and innite dilution tests using the analysis of Kojima and co-workers [11]. According to the Kojimas method, the experimental data are considered thermodynamically consistent if < 5 for the point, A < 3 for the area, and I1 and I2 < 30 for the innite dilution tests. In this method, the gE /RT was correlated with a three-constant RedlichKister equation and the ln( 1 / 2 ) was represented with a four-constant equation as described by Kojima et al. The result of the thermodynamic consistency test is also shown in Table 5. The diisopropyl ether + ethanol system successfully passed the three tests. The diisopropyl ether + 2,2,4-trimethylpentane system passed

Method of Kojima et al.a RMSD 0.087 0.657 ln( i / j )b 4.8 (+)d 0.9 (+) A 1.7 (+) 2.1 (+) I1 13.2 (+) 32.5 ()f I2 10.8 (+) 44.9 ()

4 10

Criteria for passing the thermodynamic consistency tests: < 5, A < 3, I1 < 30, I2 < 30. RMSD ln(i /j ) = (
n expt [(ln(i /j ))k k =1

(ln(i /j ))calc k ] )/n.

1 + 2: diisopropyl ether + ethanol. (+): passes the consistency test. 1 + 3: diisopropyl ether + 2,2,4-trimethylpentane. (): fails to pass the consistency test.

H.-C. Ku, C.-H. Tu / Fluid Phase Equilibria 248 (2006) 197205 Table 6 Experimental VLE data reduction with the Wilson, NRTL, and UNIQUAC models Model System i + j Aij a (K) Aji a (K) RMSDb T (K) Wilson 1 + 2c 1 + 3d 2 + 3e NRTL 1+2 1+3 2+3 1+2 1+3 2+3 180.67 266.05 1804.70 125.23 18.52 185.53 709.93 2.28 179.13 1126.40 216.69 317.18 98.91 8.33 239.83 192.20 17.20 1085.80 0.321 0.300 0.254 0.38 0.07 0.80 0.34 0.11 0.67 0.35 0.47 0.68 y1 0.0056 0.0042

201

y2

0.012 0.0072 0.0048 0.012 0.0079 0.0081 0.013

UNIQUAC

a The binary adjustable parameters for Wilson: A = ( )/R, A = ( )/R; NRTL: A = (g g )/R, A = (g g )/R; UNIQUAC: A = (U U )/R, ij ij ii ji ji jj ij ij ii ji ji jj ij ij ii Aji = (Uji Ujj )/R. b c d e

RMSD: root mean square deviation, dened as RMSD T =

n expt (T k =1 k

calc Tk ) )/n; RMSD yi =

n expt (y k=1 i,k

calc yi,k ) )/n.

1 + 2: diisopropyl ether + ethanol. 1 + 3: diisopropyl ether + 2,2,4-trimethylpentane. 2 + 3: ethanol + 2,2,4-trimethylpentane from the previous paper [1].

the point and area tests, but it failed to pass the innite dilution test. The VLE experimental data of two binary systems were then calculated with the various activity-coefcient models, including the Wilson, the NRTL, and the UNIQUAC equations [1214] by a bubble temperature calculation procedure [15]. Estimation of energy parameters of the models studied was based on the simplex method [16] by minimization of the following objective function (OF) in terms of calculated and experimental values: 2 n 2 expt calc i i OF = (5) expt i k=1 i=1
k

where n is number of data points. The tted parameters for the Wilson, NRTL, and UNIQUAC equations along with the results of data reduction are shown in Table 6. As can be seen, all the activity-coefcient models are generally satisfactory in representation for the investigated binary systems, while the Wilson equation seems to give a slightly better result. The equilibrium phase compositions were also measured for the ternary system of diisopropyl ether + ethanol + 2,2,4trimethylpentane at 101.3 kPa, and the results are presented in Table 7. Similarly, Eq. (1) was applied to calculate the activity coefcients for each component. Fig. 4 shows the experimental tie-lines between the saturated vapor and liquid-phases, indicating the absence of a ternary azeotrope. This can be further conrmed by the azeotropic rule (Doherty and Perkines [17]) for ternary systems: 2(N3 S3 ) + N2 S2 + N1 = 2 (6)

that N1 = 2. Also, the system of diisopropyl ether + ethanol exists with a lowest binary azeotrope and this binary azeotropic point is an unstable node, leading to N2 = 1. The binary azeotropic point of ethanol + 2,2,4-trimethylpentane as obtained from the previous paper [1] is a saddle point, leading to S2 = 1. Under the above situation, the azeotropic rule is fullled if and only if N3 = S3 . However, still there is no experimental evidence of more than one ternary azeotropic point in a ternary system (Gmehling and M ollman [18]). It implies that N3 = 0 and S3 = 0 in consistency with the experimental observation of the present study. The thermodynamic consistency of diisopropyl ether + ethanol + 2,2,4-trimethylpentane ternary system was tested using the McDermottEllis method [19] as modied by Wisniak and Tamir [20]. According to this method, two experimental points a and b are considered to be thermodynamically consistent if D < Dmax where D is a local deviation and Dmax is a maximum deviation, both related to the equilibrium data a and b. In the present study, the errors in the measurements were set to 0.1 kPa for pressure, 0.05 K for boiling temperature, and 0.003 for liquid and vapor compositions. The values of calculated Dmax D were greater than zero for all experimental points with a mean value of 0.087, which indicates that the system is thermodynamically consistent. Furthermore, the Wilson, NRTL, and UNIQUAC models with the determined binary interaction parameters in Table 6 were utilized to predict the bubble points of the ternary system. The results are given in Table 8, indicating that the Wilson model yields the best prediction. The deviation in the boiling temperature, TE , for mixture is dened in terms of the boiling temperature of pure component as
N

where N1 is the number of nodes among the pure components, N2 the number of nodes among the binary azeotropes, S2 the number of saddle points among the binary azeotropes, and N3 and S3 are the numbers of ternary nodes and saddles, respectively. The experimental results show that the corners of 2,2,4-trimethylpentane and ethanol are stable nodes, resulting

TE = T
i=1

xi Ti

(7)

where T and Ti are the boiling temperatures of mixtures and pure component i, respectively. The mixing functions gE /RT and TE for binary mixtures were then represented mathematically by the

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Table 7 Experimental VLE data for diisopropyl ether (1) + ethanol (2) + 2,2,4-trimethylpentane (3) system at 101.3 kPa T (K) 337.98 337.98 338.38 338.64 339.04 339.28 339.34 339.78 340.11 340.36 340.54 340.62 340.64 340.78 341.18 341.28 341.63 341.68 341.74 341.94 342.03 342.34 342.41 342.45 342.93 343.04 343.15 343.21 343.41 343.83 343.88 343.89 344.07 344.07 344.16 344.17 344.32 344.49 344.50 344.57 345.29 345.64 345.86 345.89 346.17 346.88 347.04 347.75 348.41 350.79 352.28 352.83 355.27 358.25 360.38 x1 0.600 0.705 0.489 0.808 0.385 0.605 0.498 0.394 0.284 0.704 0.286 0.901 0.396 0.504 0.296 0.606 0.192 0.193 0.404 0.299 0.193 0.798 0.194 0.503 0.302 0.195 0.096 0.096 0.097 0.050 0.050 0.098 0.051 0.701 0.095 0.049 0.098 0.197 0.051 0.406 0.051 0.303 0.047 0.099 0.597 0.050 0.196 0.098 0.501 0.403 0.049 0.301 0.194 0.096 0.047 x2 0.350 0.245 0.464 0.140 0.567 0.240 0.353 0.456 0.670 0.142 0.567 0.049 0.353 0.246 0.457 0.143 0.760 0.663 0.237 0.347 0.561 0.048 0.460 0.136 0.240 0.363 0.655 0.757 0.555 0.702 0.596 0.459 0.494 0.046 0.860 0.806 0.351 0.229 0.394 0.143 0.288 0.149 0.911 0.257 0.048 0.178 0.144 0.133 0.047 0.045 0.070 0.043 0.046 0.048 0.028 y1 0.627 0.685 0.567 0.761 0.509 0.599 0.527 0.451 0.445 0.692 0.386 0.883 0.424 0.502 0.344 0.602 0.356 0.291 0.407 0.320 0.251 0.821 0.227 0.517 0.315 0.211 0.141 0.169 0.115 0.075 0.064 0.106 0.059 0.755 0.221 0.091 0.106 0.210 0.056 0.427 0.055 0.329 0.132 0.110 0.682 0.056 0.224 0.112 0.604 0.517 0.066 0.411 0.294 0.149 0.080 y2 0.341 0.287 0.396 0.214 0.446 0.320 0.382 0.440 0.500 0.230 0.487 0.093 0.424 0.357 0.479 0.267 0.568 0.549 0.406 0.465 0.539 0.104 0.530 0.308 0.441 0.512 0.603 0.624 0.587 0.633 0.612 0.570 0.599 0.118 0.678 0.669 0.555 0.483 0.582 0.331 0.563 0.376 0.775 0.544 0.130 0.530 0.423 0.479 0.140 0.151 0.412 0.185 0.216 0.249 0.253 1 1.170 1.088 1.282 1.033 1.432 1.064 1.135 1.211 1.641 1.021 1.395 1.010 1.103 1.021 1.177 1.003 1.853 1.504 1.003 1.059 1.284 1.005 1.141 1.001 1.001 1.035 1.401 1.676 1.122 1.402 1.194 1.009 1.073 0.999 2.153 1.718 0.996 0.976 1.005 0.961 0.964 0.960 2.471 0.976 0.995 0.955 0.970 0.950 0.982 0.976 0.982 0.980 1.015 0.958 0.992 2 1.681 2.022 1.448 2.566 1.297 2.178 1.763 1.543 1.177 2.530 1.330 2.934 1.853 2.227 1.581 2.807 1.106 1.223 2.526 1.960 1.399 3.120 1.652 3.245 2.580 1.971 1.281 1.144 1.456 1.220 1.387 1.677 1.625 3.443 1.052 1.107 2.098 2.780 1.946 3.042 2.494 3.177 1.060 2.637 3.341 3.566 3.497 4.169 3.363 3.454 5.717 4.096 4.078 4.036 6.509 3 1.817 1.590 2.206 1.334 2.569 1.419 1.655 1.941 3.160 1.325 2.249 1.244 1.570 1.455 1.825 1.324 3.977 2.784 1.301 1.508 2.114 1.191 1.717 1.182 1.279 1.500 2.453 3.354 2.025 2.747 2.131 1.702 1.739 1.159 5.186 3.820 1.411 1.220 1.488 1.220 1.284 1.182 4.844 1.171 1.142 1.131 1.122 1.091 1.136 1.119 1.053 1.075 1.045 1.042 1.003 gE /RT 0.306 0.255 0.330 0.173 0.331 0.279 0.338 0.373 0.303 0.190 0.376 0.073 0.370 0.301 0.406 0.220 0.261 0.360 0.315 0.396 0.421 0.086 0.444 0.221 0.340 0.432 0.418 0.329 0.465 0.407 0.472 0.474 0.495 0.094 0.191 0.303 0.449 0.343 0.483 0.233 0.427 0.251 0.162 0.348 0.102 0.319 0.250 0.252 0.106 0.108 0.167 0.102 0.101 0.098 0.055

following type of the RedlichKister equation for correlating the data:

m

Qij = xi xj
k=0

ak (xi xj )k

(8)

where Qij refers to gE /RT or TE (K) for each component i + j pair. xi and xj are the liquid mole fractions of pure component i and j, respectively. The values of the coefcients ak for each binary system were determined by a nonlinear regression analysis based on the least-squares method. The results are given in Table 9 and

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203

Fig. 4. Tie-lines for diisopropyl ether (1) + ethanol (2) + 2,2,4-trimethylpentane (3) system at 101.3 kPa: () liquid-phase mole fraction and ( ) vapor-phase mole fraction. Table 8 VLE prediction for diisopropyl ether (1) + ethanol (2) + 2,2,4-trimethylpentane (3) ternary system from the determined binary parameters of Table 6 Model RMSD T (K) Wilson NRTL UNIQUAC 0.75 0.75 0.79 y1 0.006 0.006 0.006 y2 0.019 0.022 0.022 y3 0.017 0.019 0.020

Fig. 5. The isoclines of boiling temperature, T (K), for diisopropyl ether (1) + ethanol (2) + 2,2,4-trimethylpentane (3) system at 101.3 kPa.

ethanol + 2,2,4-trimethylpentane system with 0.13 K for TE and 0.0052 for gE /RT. The derived properties, gE /RT and TE (K), for diisopropyl ether (1) + ethanol (2) + 2,2,4-trimethylpentane (3) ternary system were correlated using the equation: Q123 = Q12 + Q13 + Q23 + x1 x2 x3 C123 (10)

the standard deviation, , is dened by 1/2 n [(Qexpt ) (Qcalc ) ]2 ij ij k k = np

k=1

(9)

where Q123 refers to gE /RT or TE (K) for ternary mixtures, x3 = 1 x1 x2 , and Qij is the binary contribution of component i + j pair to the gE /RT or TE (K) given by Eq. (8). The ternary contribution term C123 was correlated using the expression suggested by Cibulka [21]: C123 = C0 x1 + C1 x2 + C2 x3 (11)

where n is the number of experimental points and p is the number of parameters. The largest standard deviations occurred in the

The ternary parameters C0 , C1 , and C2 were obtained with the optimization algorithm similar to that used for determining the

Table 9 Coefcients of RedlichKister equation and standard deviations for gE /RT and TE for mixtures Function a0 a1 0.028 7.885 a2 0.194 18.142 0.001 3.848 0.306 41.482 C1 3.409 5.145 a3 0.051 0.606 0.038 0.925 0.489 30.637 C2 0.250 277.287 a4 0.166 10.198 a5 0.0014 0.05 0.0005 0.02 0.087 110.694 0.0096 0.44 0.0052 0.13

Diisopropyl ether (1) + ethanol (2) gE /RT 1.228 34.351 TE (K)

Diisopropyl ether (1) + 2,2,4-trimethylpentane (3) gE /RT 0.046 0.004 TE (K) 14.990 4.714 Ethanol (2) + 2,2,4-trimethylpentane (3)a gE /RT 2.134 TE (K) 69.481 Function C0 0.007 37.100

3.334 0.412 164.194

Diisopropyl ether (1) + ethanol (2) + 2,2,4-trimethylpentane (3) gE /RT 1.056 TE (K) 106.749
a

The constants of the system were obtained from the previous VLE data [1].

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the binary VLE data using the Wilson, NRTL, and UNIQUAC models showed that all three models were generally satisfactory, while the Wilson equation gave a slightly better result. Based on the information of the constituent binaries, the Wilson model yielded the best prediction for the ternary equilibrium. List of symbols a, b, c, d coefcients of the liquid molar volume equation ak coefcients of the RedlichKister equation a , b , c , d , e coefcients of the vapor pressure equation A used in the area test of Kojima et al. Aij , Aji binary parameters for liquid activity-coefcient models C0 , C1 , C2 coefcients of the Cibulka equation C123 ternary contribution used in the Cibulka equation D local deviation in the method of McDermottEllis Dmax maximum deviation used by Wisniak and Tamir gij , gjj NRTL parameters excess molar Gibbs energy gE I1 , I2 used in the innite dilution test of Kojima et al. n number of experimental data nD refractive index N number of components OF objective function p number of parameters of tted equations P system pressure Po vapor pressure of pure component q surface area parameter of the UNIQUAC model Qij gE /RT or TE (K) for binary i + j pair gE /RT or TE (K) for the ternary mixture Q123 r volume parameter of the UNIQUAC model R universal gas constant RMSD root mean squared deviation T boiling temperature in K Uij , Ujj UNIQUAC parameters VLE vaporliquid equilibrium xi mole fraction of component i in liquid-phase yi mole fraction of component i in vapor-phase summation Greek letters NRTL parameter liquid-phase activity coefcient used in the point test of Kojima et al. deviation between experimental and calculated value ij , ii Wilson parameters density standard deviation vapor-phase fugacity coefcient Subscripts c critical max maximum value 1, 2, 3, i, j components 123 ternary mixture Superscripts calc calculated value

Fig. 6. The isoclines of the liquid-phase gE /RT for diisopropyl ether (1) + ethanol (2) + 2,2,4-trimethylpentane (3) system at 101.3 kPa.

binary parameters. The corresponding standard deviations were 0.43 K in boiling temperature and 0.0096 in gE /RT. The results of the correlation are given in Table 9. The isoclines of boiling temperature and the gE /RT of liquid-phase for the ternary mixtures were plotted in Figs. 5 and 6, respectively, using Eqs. (10) and (11) with the parameters reported in Table 9. As can be expected from the behavior of binary mixtures, a positive deviation from ideal behavior was observed. The maximum gE /RT value was found in the system of ethanol + 2,2,4-trimethylpentane near x = 0.5. 4. Conclusion Isobaric VLE data were determined experimentally for diisopropyl ether + ethanol + 2,2,4-trimethylpentane ternary system and two constituent binary systems of diisopropyl ether + ethanol and diisopropyl ether + 2,2,4-trimethylpentane at 101.3 kPa. The entire systems exhibited a positive deviation from ideal behavior. A minimum boiling azeotrope occurred in the diisopropyl ether + ethanol system. Azeotropic behavior was not found for the ternary system and this was conrmed by the azeotropic rule of Doherty and Perkines. The vapor-phase fugacity coefcients were calculated from the SoaveRedlichKwong equation of state with its binary interaction parameter being set to 0. All the new VLE data were examined by the thermodynamic consistency tests. By the analysis of the direct test of Van Ness, the VLE data of diisopropyl ether + ethanol system were of acceptable quality, while those of diisopropyl ether + 2,2,4trimethylpentane system were poor. According to the point, area, and innite dilution tests of Kojima et al., the diisopropyl ether + ethanol system successfully passed all three tests, but the diisopropyl ether + 2,2,4-trimethylpentane system failed to pass the innite dilution test. Using the test of McDermottEllis as modied by Wisniak and Tamir for ternary VLE data, the diisopropyl ether + ethanol + 2,2,4-trimethylpentane system adequately fullled the criterion of consistency. Reduction of

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expt E L o s

experimental value excess value liquid state pure component at saturation

Acknowledgement The authors wish to extend their deep gratitude for the support by the National Science Council of Republic of China under grant NSC 91-2214-E126-001. References
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