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Vapor−Liquid Equilibrium, Densities, and Interfacial Tensions of the System Ethanol + Tetrahydro-2H-pyran
Andrés Mejía,*,† Hugo Segura,*,† Marcela Cartes,† and J. Ricardo Pérez-Correa‡
† ‡

Departamento de Ingeniería Química, Universidad de Concepción, P. O. Box 160-C, Correo 3, Concepción, Chile Department of Chemical and Bioprocesses Engineering, Pontificia Universidad Católica de Chile, Avenida Vicuña Mackenna 4860, Santiago, Chile
S * Supporting Information

ABSTRACT: Isobaric vapor−liquid equilibrium (VLE) data have been measured for the binary system ethanol + tetrahydro-2H-pyran at (50, 75, and 94) kPa and over the temperature range (331 to 358) K using a vapor−liquid equilibrium still with circulation of both phases. Mixing volumes were also determined at 298.15 K and atmospheric pressure with a vibrating tube densimeter, while a maximum differential bubble pressure tensiometer was used to measure atmospheric interfacial tensions at 303.15 K. According to experimental results, the mixture exhibits positive deviation from ideal behavior, and minimum boiling point azeotropy is present at mid-range concentrations (0.55 < x1Az < 0.67). VLE measurements show also that the azeotropic mole fraction impoverishes in ethanol as pressure (or temperature) increases. The mixing volumes of the mixture evolve from positive to negative deviations as the concentration of ethanol increases. Finally, it is experimentally observed that the interfacial tensions exhibit positive deviations from the linear behavior. The VLE data of the binary mixture satisfy Fredenlund's consistency test and were well-correlated by the Wohl, nonrandom two-liquid (NRTL), Wilson, and universal quasichemical (UNIQUAC) equations for all of the measured isobars. The mixing volumes and interfacial tensions, in turn, were satisfactorily correlated using the Redlich−Kister equation.

INTRODUCTION Ethers (branched and cyclic) are considered some of the most important chemicals in the industry. Particularly, branched ethers (such as 2-methoxy-2-methylpropane or MTBE, 2ethoxy-2-methyl-propane or ETBE, 2,2′-oxybis[propane] or DIPE, and 2-methoxy-2-methylbutane or TAME) have extensively been used as oxygenates in gasoline production. Cyclic ethers, in turn (e.g., tetrahydrofuran or THF, 1,4dioxane, and tetrahydro-2H-pyran or THP), are frequently used as solvents in chemical and electrochemical processes, as well as basic reagents (i.e., monomer) for ring-opening polymerization, and for the production of other chemical intermediaries. Recently, industrial interest in using THP as a potentially attractive cyclic ether has increased due to new and economic production routes.1−4 Thermophysical properties of THP-based mixtures are useful for exploring their potential in the formulation of new alternatives for commercial fuels. In fact, detailed vapor−liquid equilibrium (VLE) data are needed for rationalizing the production of THP1 at industrial scale, and additionally, they may provide useful information for characterizing the distillation curve (fuel concentration during vaporization) and the Reid vapor pressures (volatility indicator) for possible gasoline blending applications. Density data, in turn, are required for designing engine injection systems and for adequate vessels for fuel storage and transportation. Interfacial tension (IFT) data are needed to characterize the formation
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and ignition kinetics of fuel drops. Finally, VLE, density, and IFT data are important for assessing the environmental impact of organic mixtures in air, ground, and aquifers. In fact, IFTs define the wettability patterns of fluid systems in aquifers and soils, thus providing a route to rationalize environmental remediation methods. In spite of their potential relevance, and compared to the case of more traditional cyclic ethers,5−7 few experimental works have been devoted to characterize the thermophysical properties of THP mixtures. In general, we have observed that available data for THP + n-alkane and + alcohol mixtures are scarce and incomplete. Only Uno et al.8 have reported boiling temperatures and liquid phase mole fractions from (40 to 98) kPa for ethanol + THP. According to that data, the mixture exhibits positive deviation from ideal behavior, and additionally, an azeotrope is present. To the best of our knowledge, neither mixing volumes (or excess volumes, VE) nor IFT data have been previously reported for THP-based mixtures. This contribution is undertaken to experimentally determine new and accurate data for the phase equilibrium, mixing densities, and atmospheric interfacial tensions of ethanol + THP, thus contributing to the thermophysical characterization of THP + polar solvents.
Received: October 25, 2011 Accepted: December 14, 2011 Published: December 29, 2011
561
dx.doi.org/10.1021/je201140q | J. Chem. Eng.Data 2012, 57, 561−567

the liquid xi.528 0.896 1.052 1.31d lit. and Bij were estimated by the method of Hayden and O'Connell23 using the molecular and solvation parameters η suggested by Prausnitz et al.60 332.937 1. Table 1 reports the purity of the components (as determined by gas chromatography.768 0.020 1.306 0.52 331.77 333.11 dGill et al.064 1.075 1.9 bRiddick et al.20 ■ Daubert and Danner.200 0.18 whereas maximum differential bubble pressure technique have been described by Adamson and Gast19 and Rusanov and Prokhorov.33 exp. Vapor−Liquid Equilibrium. and the temperature was kept constant to within ± 0.000 0.74 331. the liquid molar volumes of pure components are incompressible over the pressure range under consideration.770 1. γi are the activity coefficients of component i.1021/je201140q | J. Additional details concerning to the VLE technique have been extensively described by Raal and Mühlbauer. the refractive indexes (nD) at 298.148 1.251 0. Equation 1 is valid from low to moderate pressures.114 0.15.452 0.10 cGiner et al.000 0.824 0.029 1.01 K. Eng.832 0.636 0.05.57 a −Bij/cm3·mol−1 x1 0.org/10.45 361. conditions in which interfacial tension measurements were accurate within ± 0. molecular parameters and physical properties were also taken from ref 10. Bij is the cross second virial coefficient. Refractive Index (nD) at Na D line.36068 1.7 27.78589 0. and Bij are the molar virial coefficients. 561−567 .602 0. Specific details concerning the experimental procedures have been described in depth in recent works.275 0.229 0. conditions in which concentration measurement accuracies were better than ± 0.939 1.574 1.786 1. and the interfacial tensions (σ) of pure fluids at 303.100 1.092 0. VLE data were determined by using an all-glass VLE cell model 601 (Fischer Labor and Verfahrenstechnik).293 1.391 0.999) THP (0. The reported values are also compared with those reported in the literature.138 1.354 0.82 333.40 331.998 1.565 1.001 1.130 0. 1.65 334.375 0. a exp. without considering additional purification.42000 lit.77 331.423 0. the mass densities (ρ).414 1. and detector.007 1. respectively. and 94) kPa are reported in Tables 2 to 4 and illustrated in Figure 1 (solid symbols).106 1.288 1. additionally. The accuracy of density measurements was 5·10−6 g·cm−3.43 331.728 0.99 332.15 exp.10 The molar virial coefficients Bii.55 331.68a 26.72 333.49 334.540 0. 57.354 1. and vapor-phase yi mole fractions of component i at P = (50. 21. Tables 2 to 4 also include the activity coefficients (γi).095 1.44 361. xi and yi are mole fractions in liquid and vapor phases of component i.36 21.493 1. Gas Chromatography (GC) Purities (Mass Fraction).675 1. where the virial equation of state truncated after the second term is adequate for describing the vapor phase of the pure components and their mixtures and.432 0. injector. whereas the pressure was measured with an estimated accuracy of ± 0.33 337.40 331. Normal Boiling Points (Tb). Temperature conditions in gas chromatography were (373.12 eInterpolated data from Villares et al. THP's solvation parameter η was estimated by smoothing experimental data of second virial coefficients reported in ref 25.66e 0. Experimental VLE Data for Ethanol (1) + THP (2) at P = 50. Densities were measured using a Anton Paar DMA 5000 vibrating U-tube densimeter. Liquid molar volumes were estimated from the correlation proposed by Rackett.346 2. and Interfacial Tensions (σ) of Pure Components nD T/K = 298.11 332. which are displayed in Figures S1 to S3 in the Supporting Information and were calculated from the following equation:21 ■ RESULTS AND DISCUSSION δijP yP (B − ViL)(P − Pi0) ln γi = ln i 0 + ii + yj 2 RT RT xiPi (1) 562 where P is the total pressure and Pi0 is the pure component vapor pressure.9−13 Apparatus and Procedure. For the case of THP.15 K.doi. ViL is the liquid molar volume of component i. The temperature accuracy was ± 0. GC).41950b lit.01 K using a Julabo thermostatic bath. thus yielding the value η = 0.578 0.998) a ρ/g·cm−3 T/K = 298.1 EXPERIMENTAL SECTION Chemicals.15 K. we constrain our description to key operating parameters. The refractive indexes were measured using a multiscale automatic refractometer RFM 81 (Bellingham and Stanley). and the mixing rule of second virial coefficients (δij) is given by δij = 2Bij − Bjj − Bii.02 K.002 1.000 γ2 1.15. and the temperature of the apparatus was maintained constant to within ± 0.15) K for column.24 for ethanol.15 component (purity/mass fraction) ethanol (0. together with the normal boiling points of the pure fluids (Tb).678 0.069 11 1170 1196 1212 1229 1241 1250 1257 1265 1270 1271 1272 1272 1271 1269 1266 1261 1255 1246 1234 1214 22 1258 1279 1295 1305 1315 1322 1328 1332 1337 1340 1341 1341 1341 1341 1340 1337 1335 1331 1326 1318 12 710 718 723 728 732 734 737 739 740 741 741 741 741 740 739 738 736 733 730 T is the equilibrium temperature.658 1. Densities (ρ).000 γ1 2.001 in mole fraction.233 1. dx.200 1.479 0. Chem. The temperature of the sample in the vessel was kept constant to within ± 0.044 1. and 493.181 1. 351.78509 0.87880c lit.03 kPa.324 0.032 1. 1.87903 351.01 mN·m−1.Data 2012.571 0.044 0. respectively. 75.717 0. 393.00 kPaa T K 339. R is the universal gas constant.35940 1.675 0.19 331.458 1. Bjj. 0.000 y1 0. Interfacial tensions were measured using a Sensadyne maximum differential bubble pressure tensiometer model PC500-LV.22 Critical properties were taken from Riddick et al. Pure component and cross virial coefficients are reported in Tables 2 to 4.01 K.15 exp. Ethanol (Merck) and tetrahydro-2H-pyran (Aldrich) were used as received.000 0.Journal of Chemical & Engineering Data Article Table 1.181 0.13 Table 2.19 335. Bii and Bjj are the second virial coefficients of the pure gases.14−17 so briefly.371 1. a σ/mN·m−1 T/K = 303.011 1. The uncertainties in measurements are ± 10−5.922 2.512 0.779 0.883 0. The boiling temperature T.242 1.484 0.31 332.627 0.45 331. a Tb/K p/kPa = 101.

272 1.259 0.374 0.638 0.70 336.105 1.00 a x1Az 0. 53.811 1.0 kPa.103 1.65 341.786 0.056 1. 79.090 0.26 347.56 a −Bij/cm3·mol−1 x1 0.33 kPa.00 kPaa T K 351.102 0.40 339.60 347.00 kPaa T K 358.000 γ1 2.470 0.430 0.20 347.526 1.447 1.526 0.984 11 913 934 949 965 976 985 994 1002 1007 1011 1013 1015 1015 1015 1015 1013 1011 1006 1000 990 22 1085 1108 1123 1133 1145 1153 1159 1165 1171 1174 1176 1178 1179 1179 1179 1179 1178 1176 1173 1169 12 621 629 635 641 645 648 651 654 656 657 658 658 659 659 658 658 657 655 653 Table 6.414 0.000 1.53 349.737 1.60624 − 1010.038 0. 75.284 1.594 0.67 341.0 87.92 342.70 341.391 1.626 0. Experimental VLE Data for Ethanol (1) + THP (2) at P = 94.138 1.92 342.001 1.936 1. 94. and Bij are the molar virial coefficients.200 0.12 344.696 0.676 0.676 0.0 kPa.576 0.576 0. xi and yi are mole fractions in liquid and vapor phases of component i.33 347.75 349.735 1.0 45. γi are the activity coefficients of component i.051 1. 93. .904 1.61 356.doi.459 1.272 0. Table 5 reports 563 Equation 2 correlates Pi0 data of THP from (321. ⧫.0 73.546 0.737 0.323 0.13 344.0 51.171 1.225 0.000 0.1 312.262 0. x1Az is the azeotropic mole fraction.97 354.625 0.49 342.613 1.629 0. respectively.004 1.365 0.00 75. predicted from the two-parameter Legendre polynomial used in consistency analysis.000 y1 0.000 0.828 0.882 1.14 343.96 348.04 341.01 24.010 1.778 0.002 1. 561−567 .28 348.225 0.429 1.357 1.534 0.000 0.34 342.0 kPa.631 1.000 y1 0.659 0. and TAz is the azeotropic temperature.02 a Article −Bij/cm3·mol−1 x1 0. azeotropic line.360 1.403 0. whose dependence on temperature can be accurately correlated by using the Antoine equation: log(Pi0/kPa) = 5.612 1.203 0.29 358.053 1.60 347.009 1.793 0.318 0.479 0.372 0.322 0.428 0.128 0.727 0.754 1.727 0.0 94. Table 5.009 1.010 1.55 Table 4. 57. ···. . and Bij are the molar virial coefficients. Estimated Azeotropic Coordinates for the System Ethanol (1) + THP (2)a P/kPa 50.000 1.526 0.283 1.374 1.85 355.665 TAz/K 331.01 38.519 1.260 1.851 1.833 0.439 1.139 1.16 342.086 1.036 1.Journal of Chemical & Engineering Data Table 3..000 γ1 2.222 1. Experimental Vapor Pressures (P) as a Function of Temperature (T) for THP T/K P/kPa 18.56 P is the pressure of the system.063 1.0 80.79 347.org/10.519 1.52 343.59 347. Experimental data at ●.091 1.74 353.182 1.58 348.838 0. respectively.000 1.001 1.77 341. □.176 0.28 346.577 0.36 331.327 1.018 1.088 0.000 γ2 1.181 1.0 102.020 1. ■.64 350.180 1. γi are the activity coefficients of component i.625 0.97 344.64 341.00 94.91 351.26 348.004 1. Experimental data reported by Uno et al.122 0.326 0.98 344.32 kPa.91 349.314 1.670 0.506 0. Chem.708 0. Isobaric phase diagram for the system ethanol (1) + THP (2).3546/[(T /K) − 80.84 341.37 341.518 0.000 0.936 1.Data 2012.178 0.881 0.846 0.971 1.607 0. Eng.000 γ2 1.477 0.570 0.075 1.1021/je201140q | J. xi and yi are mole fractions in liquid and vapor phases of component i.01 30.213 1.992 1. T is the equilibrium temperature.033 1.8 at ○. Experimental VLE Data for Ethanol (1) + THP (2) at P = 75.62 325.441 0.011 11 993 1020 1035 1051 1063 1072 1081 1089 1094 1097 1099 1100 1100 1099 1098 1095 1092 1087 1078 1065 22 1145 1164 1182 1193 1203 1211 1217 1223 1228 1231 1233 1234 1235 1235 1235 1234 1232 1230 1226 1221 12 651 660 665 671 675 678 681 684 685 686 687 687 687 687 687 686 685 683 680 Figure 1.0 66.451 0.629 1.272 0.032 1.17 352.023 1.778 0. predicted from the Wohl model with the parameters indicated in Table 8.126 0.77 347.541 1.7458] (2) The vapor pressures of pure components were experimentally determined as a function of temperature using the same equipment as that for obtaining the VLE data.563 0.66 347.231 1. T is the equilibrium temperature.074 1.190 1.700 1.476 0. the experimental values obtained for the vapor pressures of THP.99 kPa.58 350.046 0.866 2.039 1.65 347.882 0.123 1.59 319.65 349.97 347.-.019 1.908 1.59 to 360) K with an average of the absolute percentage deviation (AAPD) dx.748 0.81 361.0 59. 50.139 1.369 0.133 1.228 1. ◊.

nonrandom two-liquid (NRTL). From Figure 1 we can conclude a good coherency between the present VLE data and those reported by Uno et al. together with the relative Table 8.52 −506.79860 0.85954 0.1 dew-point pressures ΔP (%)b 0. Chem.2 0.97 3231.8 Azeotropic concentrations of the measured binary were estimated by fitting the empirical function ⎛ y − x⎞ ⎟ f (x) = 100⎜ ⎝ x ⎠ (4) where x and y have been taken from the experimental data.1 NRTL Wilsonf UNIQUACg a A12 and A21 are the GE model parameters in J·mol−1.3 0.3 kPa ρ x1 0.0 94.41 A21 0.1021/je201140q | J.9400. N is the number of data points.890] (3) 0.299 0.81 −739.115 0.87903 0.3 0.doi.86685 0.3 0. are indicated in Table 6. 564 dx.3 0.2 0.799 0.5 %.27 as modified by Fredenslund et al.3 0.959 1.1 0.2 0.14 and their temperature dependence was obtained from:14 log(Pi0/kPa) = 7.781 0. 57.95 1705.1 0.85 2130.735 1915.84401 0.9720. Eng. The parameters of the different activity coefficient models are reported in Table 8.193 0.1 0.6159.2 100 Δyic 0.568d 0.63 2143.3 0. Densities (ρ) and Excess Volumes (VE) as a Function of the Liquid Mole Fraction (x1) for the Binary System Ethanol (1) + THP (2) at 298.80 837.38 3056.2 0.2 0.1 0. experimental vapor pressures have been previously reported.3 0.2 0.3 0.496 0.00 a Article L1a 0. Pertinent consistency statistics and Legendre polynomial parameters are presented in Table 7. r2 = 3.82274 0. Azeotropic concentrations. the reported azeotropic coordinates are in good agreement with results presented by Uno et al. eα12 parameter for the NRTL model.8044 0.2 0.030 0.1 0.Journal of Chemical & Engineering Data Table 7.0 94. The reliability of eq 2 for predicting vapor pressures of THP has been successfully tested against the data reported by Miyano et al.2 0. For the case of ethanol. Statistical analysis30 reveals that a two-parameter Legendre polynomial is adequate for fitting the equilibrium vapor pressure in each case.80 −458.0 50.000 g·cm 3 103·VE cm3·mol−1 0 19 41 45 40 24 14 0 −11 −15 −12 −6 0 Parameters for the Legendre polynomial28 used for consistency.910 0. where it is concluded that the mole fraction of the azeotrope impoverishes in ethanol as pressure (or temperature) increases. the superscript exp stands for experimental data.2 0.000 0.0 75.2 0.0 75.org/10.448d 1. the consistency criterion (Δy < 0.00 75.91 −764.2 0.9 %.911 0. cΔδ = 1/N∑iN|δiexp − δical| with δ = y or x. Consistency Test Statistics for the Binary System Ethanol (1) + THP (2) P/kPa 50. and universal quasichemical (UNIQUAC) equations.Data 2012.40 3097.3 0.0 50.3 0. while cal means calculated quantity.0 A12 0.2 Table 9. Wilson.30 1753.400e 0.0 94.91 −455.81313 0.0 50.2 0.1 0.83465 0.516d 1.28 For each isobaric condition.400e 0.3 0.2 0.30 %.3 0.00 94.22 gThe molecular parameters r and q are those reported in DECHEMA:5 r1 = 2. q2 = 2. as determined by solving f(x) = 0.2 0.716 0.2 0.3 0.8442 0. fLiquid molar volumes have been estimated from the Rackett equation.0 75.15 K and 101.8 The VLE data reported in Tables 2 to 4 were found to be thermodynamically consistent by the point-to-point method of Van Ness et al.1 0.3 100 Δxic 0.06 820.31 whose adjustable parameters were obtained by minimizing the following objective function (OF): OF = ∑ (|Piexp − Pical|/Piexp + |yiexp − yical |)2 i=1 N (5) In eq 5.3 0. cAverage absolute N deviation in vapor pressure δP = (1/N)∑i=1 |Piexp − Pical|.3 0.12 2224.0425 −0. The activity coefficients presented in Tables 2 and 4 are estimated to be accurate to within 0.1 0. 561−567 .1055. bΔP = (100/N)∑iN|Piexp − Pical|/Piexp.752 0. q1 = 1. as it is shown in Figure 1.6973/[(T /K) − 50.79141 0.0201 −0.0 94. The VLE data reported in Tables 2 to 4 were correlated with the Wohl.804 732.7858 L2a −0.16178 − 1549.78511 The experimental data reported in Tables 2 to 4 allow the conclusion that the binary mixture exhibits positive deviation from ideal behavior and azeotropic behavior is present for each isobar. b Average absolute deviation in vapor-phase mole fractions Δy = (1/ N N)∑i=1 |yiexp − yical| (N: number of data points).2 0.3 0.02 α12 1.0 75.599 0.400e ΔP (%)b 0.84989 0.426 0.87714 0.1 0.3 0.0105 100 Δyb 0.87186 0.3 δPc/kPa 0.837 0.3 0.2 0.01) was met by fitting the equilibrium vapor pressure according to Barker's29 reduction method. dq parameter for the Wohl model.1 0. Parameters and Prediction Statistics for Different Gibbs Excess (GE) Models in Ethanol (1) + THP (2)a bubble-point pressures model Wohl P/kPa 50.3 0.2 0.26 with an AAPD of 0.41 −743. As it was observed with the general trend of the VLE data.2 0. of 0.

To assess the coherency of their trend.Data 2012.420 0.320883(x2 − x1) + 0. Interfacial Tension Data..657 0.org/10. Chem. .0·10−6 cm3·mol−1.64 23. ρ is the mass density of the mixture. The interfacial tension measurements for the mixture and its pure constituents at T = 303. VE data have been correlated by using a three-parameter Redlich−Kister expansion:32 (V E/cm3·mol−1) = x1x2[0.Journal of Chemical & Engineering Data Article Figure 2.76 26.-.70 Figure 3.0·10−6 cm3·mol−1.50 25.323 0. .223 0. .15 K and P = 101.722 0.90 24. 57.3 kPa. experimental data. Table 9 reports the experimental density data for the mixture and its pure constituents at T = 298. As it is illustrated in Figure 1.707 0.01 22. the quoted Wohl's parameters predict with fair accuracy the isobaric (T.122 0.000 mN·m−1 27. ●. smoothed by the three-parameter Redlich− Kister expansion (see eq 7).91 26.15 K and P = 101. Experimental data were correlated using a three-parameter Redlich−Kister expansion:33 dx. Excess Volume Data. Excess volumes (VE) as a function of the liquid phase (x1) for the system ethanol (1) + THP (2) at 298. x) data reported by Uno et al.604 0. showing a sharp change from a slight positive to negative deviation as the concentration of ethanol increases. we have used the best-ranked model (Wohl's model) to predict available VLE data.and liquid-phase mole fractions. Eng. According to the previous results.0·10−5 cm3·mol−1. The capability of simultaneously predicting the bubbleand dew-point pressures and the vapor. These density data allow calculating the excess volumes (VE) of the mixture according to VE = x1M1 + x2M2 M M − x1 1 − x2 2 ρ ρ1 ρ2 (6) deviation for the case of bubble. Interfacial tension (σ) as a function of the liquid mole fraction (x1) for the system ethanol (1) + THP (2) at 303.052384 + 0. it is possible to conclude that the excess volumes of the system are almost negligible. According to the results presented in Table 9 and Figure 2. it is possible to conclude that all of the fitted models gave a reasonable correlation of the binary system and that the best fit is obtained with the Wohl model. Interfacial Tensions (σ) as a Function of the Liquid Mole Fraction (x1) for the Binary System Ethanol (1) + THP (2) at 303.1021/je201140q | J.81 23.3 kPa σ x1 0.35 24.15 K and 101. ●.3 kPa.821 0.918 0. while ρi corresponds to the mass density of the pure components (that have been reported in Table 1) and Mi is the molecular weight of the constituents that were taken from refs 9 and 10.34 24.3 kPa are reported in Table 10 and in Figure 3. Experimental data.15 K and 101. smoothed by the three-parameter Redlich−Kister expansion (see eq 8).13493(x2 − x1)2 ] (7) The model reported in eq 7 is characterized by a maximum deviation of 3. From the results presented in Table 8. an average deviation of 4.07 23.24 24.and dew-point pressures. respectively.doi.963 1.068 0.00 21.622 0. linear behavior (x1σ1 + x2σ2).15 K and 101.520 0. to accurately and consistently predict the VLE of the binary system.000 0. has been used as the ranking factor. and a standard deviation of 8. Table 10. we can conclude that the Gibbs excess (GE) parameters reported in this work can be used 565 In eq 6. 561−567 .8 (open symbols).10 26.98 25.42 22. The calculated V E are estimated accurate to within ± 10−3 cm3·mol−1.3 kPa. To establish the coherency of the present binary data and to test the predictive capability of the parameters reported in Table 8.

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Fluid Phase Equilib. Ed. Data 2008. The mole fraction of the azeotrope decreases in ethanol as the pressure (or temperature) increases. Tetrahydrofuran. Rasmussen. A. Computer Calculations for Multicomponent Vapor−Liquid and Liquid−Liquid Equilibria. Process Des. 278. 1973. (21) Van Ness. O'Connell. Chem. In Physical Properties and Methods of Purification. Fluid Phase Equilib. J. 1395−1400.. (2) Karas. 53.cl and hsegura@udec. 43. (19) Adamson. J. K. E. 561−567 . Data 2008. Phase Equilibria: Measurement and Computation. 514−517. Eng.Journal of Chemical & Engineering Data Article (σ/mN· m−1) = x1x2[2. Eng. H. (23) Hayden.. A. Wiley Interscience: New York. H. Montano.ac. Eng. Interfacial Tensiometry. Prentice Hall: New York. Kato. R. J. 15. Numerical Data and Functional Relationships in Science and Technology. S. Chem. Kurihara. National Institute of Standards and Technology: Gaithersburg.. (8) Uno. 2010. (14) Mejía. 2009. Danner. Study of the Surface Tension of Chlorocyclohexane or Bromocyclohexane with Some Cyclic Ethers. Vapor−liquid equilibria and interfacial tensions of the system ethanol + 2-methoxy-2-methylbutane. (13) Villares.. Strehlke. 1334−1337. 1982. B. A.. Germany. Data 2011. Bunger. Eng. trans-2-Butene. 1997.. (5) DECHEMA Database. Data 2007. John Wiley & Sons. Cartes. Cartes. S. Vol. H.. Measurement and theoretical prediction of the vapor−liquid equibrium. 1975.uk/detherm/ (retrieved Nov 2010). 428−434. S. M.. Cartes. 57. Chem. cis-2-Butene. (26) Miyano. II. Eng. A. 2008. Ullmann’s Encyclopedia of Industrial Chemistry. E. Data 2010. Henry's Law Constants and Infinite Dilution Activity Coefficients of Propane.. Chem. J. 209−216. (20) Rusanov. Funding This work was financed by FONDECYT. A. 1-Butene. CONCLUSIONS Isobaric VLE data at (50. 53. Byer. K.. 566 (7) Wohlfarth... Lechner. H. Mensing. J..0. Ch. it is possible to conclude that the interfacial tensions of the mixture ethanol + THP exhibit positive deviations from the lineal behavior (x1σ1 + x2σ2). 3142−3148. (9) Daubert. (16) Mejía.org/10. M. Physical Chemistry of Surfaces. and 94. PA. Yasuda. W. From Figure 3. 55.. 50.acs.. M.. 2010. Springer Verlag: Berlin.. M.. 1997.... W. P. K. A. Wohlfarth.. A generalized method for predicting second virial coefficients. J. H. 2041− 2043. 2-Methylpropane. Grens. I. Chem. Tochigi... Wilson. V.. 75. M. Eckert. 1997. H.. The activity coefficients and boiling points of ethanol + THP were well-correlated with the liquid-phase mole fraction using the Wohl. Miyano. densities and interfacial tensions of the system hexane + 2-methoxy-2-methylbutane.. Rattan. A. Santiago. Eng. This material is available free of charge via the Internet at http://pubs. J. In Kirk-Othmer Encyclopedia of Chemical Technology.1-Difluoroethane.. respectively. J.. R.org. 4rd ed. Interfacial tensions of binary mixtures of ethanol with octane.. Eng. C. Data 1970. Ch. 2004. H. A. dodecane and tetradecane. 56. Lechner. S. 2010.. J.

M.. Eng. D. Chem. N.Data 2012. NJ. Phys. 57. Determination of Activity Coefficients from total pressure measurements. 3rd ed. R. 40. 1−58. L. 341−345. 6. O. Scott. B.. J. 561−567 . 1948. Chem Liq. 1953.. Aust. Segura. Chem. Kister. Molecular Thermodynamics of Fluid-Phase Equilibria. Ind. A. Gomes de Azevedo. 35.. PrenticeHall: Upper Saddle River. (32) Redlich. Lichtenthaler. J. An Assessment of Thermodynamic Consistency Tests for Vapor-Liquid Equilibrium Data. Eng. Apelblat. Eng. 43−46.x-y-t relations in a binary system. Chem. A.. Chem. (31) Prausnitz.org/10. 1997.. 207−210. R. Thermodynamic functions for nonelectrolyte solutions. (33) Myers. 55. Thermodynamics of nonelectrolyte solutions .. 1999. E. A. H. J. Article 567 dx. T.1021/je201140q | J.. J. Ind. (30) Wisniak.Journal of Chemical & Engineering Data (29) Barker. 1963.doi.

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