VaporâLiquid Equilibrium of Binary Mixtures Containing Isopropyl

Article pubs.acs.org/jced

Vapor−Liquid Equilibrium of Binary Mixtures Containing Isopropyl Acetate and Alkanols at 101.32 kPa Filipa M. Casimiro,† Dânia S. M. Constantino,‡ Carla S. M. Pereira,‡ Olga Ferreira,*,† Alírio E. Rodrigues,‡ and Simaõ . P. Pinho† †

Laboratory of Separation and Reaction Engineering, Associate Laboratory LSRE/LCM, Instituto Politécnico de Bragança, Campus de Santa Apolónia, 5301-857 Bragança, Portugal ‡ Laboratory of Separation and Reaction Engineering, Associate Laboratory LSRE/LCM, Faculdade de Engenharia, Universidade do Porto, Rua Doutor Roberto Frias, 4200-465 Porto, Portugal ABSTRACT: Isobaric vapor−liquid equilibria of binary mixtures of isopropyl acetate plus an alkanol (1-propanol, 2-propanol, 1-butanol, or 2butanol) were measured at 101.32 kPa, using a dynamic recirculating still. An azeotropic behavior was observed only in the mixtures of isopropyl acetate + 2-propanol and isopropyl acetate + 1-propanol. The application of four thermodynamic consistency tests (the Herington test, the Van Ness test, the infinite dilution test, and the pure component test) showed the high quality of the experimental data. Finally, both NRTL and UNIQUAC activity coefficient models were successfully applied in the correlation of the measured data, with the average absolute deviations in vapor phase composition and temperature of 0.01 and 0.16 K, respectively. propanol9−13 and also more specific information about azeotropic data at 101.32 kPa.9,12,14−17 For the isopropyl acetate + 1-propanol, three azeotropic data points are available at 26.37 kPa, 101.50 kPa, and 281.18 kPa.18 To the best of our knowledge, none of the remaining two binary systems has been described yet in literature.

1. INTRODUCTION The design of separation processes in second generation biorefineries requires the knowledge of phase equilibria data of a wide range of oxygenated organic compounds such as alcohols, esters, carboxylic acids, among others.1 In particular, not only esters and alcohols are common solvents and reactants widely used in the chemical industry,2 but most solvents obtained from renewable feedstock, being proposed as alternative for current volatile organic compounds, have the alcohol, ester or ether functional groups.3 The phase behavior of those mixtures is influenced by the presence of association and solvation effects, and new experimental data are fundamental to develop more robust thermodynamic models.1 In this context, more recently, several authors have presented new information regarding low pressure vapor−liquid equilibria of mixtures containing esters and alcohols, such as methyl acetate + methanol or ethanol;4 isobutyl acetate with ethanol, 1-propanol or 2-propanol;2 methyl acetate or ethyl acetate with 2-propanol;5 isoamyl alcohol and isoamyl propionate;6 2-butanol with ethyl acetate or butyl acetate.7 Aiming at obtaining additional experimental data, in this work, a dynamic recirculating still (VLE 100D), manufactured by Fischer (Germany),8 was used for the experimental measurement of low pressure vapor−liquid equilibrium of binary mixtures of isopropyl acetate plus an alkanol (1propanol, 2-propanol, 1-butanol, or 2-butanol). Within those mixtures, the information available in the literature is scarce. A few sets of low pressure vapor−liquid equilibrium (VLE) data can be found for the binary system isopropyl acetate + 2© XXXX American Chemical Society

2. MATERIALS AND METHODS 2.1. Chemicals. The source and purity of the chemical compounds used are given in Table 1. All chemicals were used without any further purification. 2.2. Experimental Method. The VLE experiments were performed by using an all-glass dynamic recirculating still, apparatus model VLE 100D, manufactured by Fischer Company (Germany). The equipment and the experimental method were already described in detail, in a previous work.8 Table 1. Specifications of the Chemicals Used

a

chemical name

supplier

minimum mass fraction puritya

isopropyl acetate (±)-2-butanol 1-propanol 2-propanol 1-butanol

Sigma-Aldrich Sigma-Aldrich Fisher Company Fisher Company Fisher Company

0.995 0.995 0.9997 0.9997 0.9992

Declared by the supplier.

Received: April 22, 2015 Accepted: October 26, 2015

A

DOI: 10.1021/acs.jced.5b00360 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

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Table 2. Experimental Vapor Pressures Psat of 1-Propanol, 2-Propanol, 1-Butanol, 2-Butanol, and Isopropyl Acetate As a Function of Temperature Ta 1-propanol

a

2-propanol

T

P

sat

K 370.10 376.30 381.50 385.89 389.89 393.59 396.19

1-butanol

T

sat

P

kPa

K

100.51 125.86 151.03 176.20 201.37 226.54 251.71

355.41 361.21 366.10 370.40 374.20 377.60 380.80

2-butanol

T

sat

P

kPa

K

101.54 127.12 152.55 177.97 203.40 228.82 254.25

390.69 397.19 402.79 407.58 411.88 415.88

isopropyl acetate

T

P

sat

T

Psat

kPa

K

kPa

K

kPa

101.47 127.02 152.42 177.83 203.23 228.64

372.30 378.60 383.89 388.59 392.79 396.69 400.09

100.57 125.86 151.03 176.20 201.37 226.54 251.71

361.41 368.80 375.00 380.40 385.39 389.89 393.99

100.54 125.86 151.03 176.20 201.37 226.54 251.71

Standard uncertainties u are u(T) = 0.15 K, u(Psat) = 1.4 kPa.

Table 3. Coefficients Used to Calculate Pisat, in Pa, of Pure Components Using Aspen Plus V8.6 Software and Relative Deviations coefficients used on eq 1 component

T range

isopropyl acetate 1-propanol 2-propanol 1-butanol 2-butanol

199.75−532.00 146.95−536.80 185.26−508.30 183.85−563.10 158.45−535.90

A

B

C

D

E

average |ΔP|/P

6.00 6.00 2.00 6.00 6.00

0.012 0.006 0.010 0.006 0.010

K 4.9754 8.4664 1.1072 1.0629 1.2255

× × × × ×

101 101 102 102 102

−5.5639 −8.3072 −9.0400 −9.8664 −1.0236

× × × × ×

103 103 103 103 104

× × × × ×

10−18 10−18 10−6 10−17 10−17

Figure 1. Percentage relative deviations of the vapor pressure of: ×,isopropyl acetate; □, 1-propanol; △, 2-propanol; +, 1-butanol; and ○, 2-butanol.

3. RESULTS AND DISCUSSION 3.1. Pure Components. First, the vapor pressures of the pure compounds isopropyl acetate, 1-propanol, 2-propanol, 1butanol, and 2-butanol were measured. The experimental values are presented in Table 2. A comparison was made with the vapor pressure (Psat i ) calculated using the following extended Antoine equation B + C ln T + DT E T

2.4755 7.5091 5.5380 1.0832 2.3559

Software, 2014) as well as the average relative deviations. Those are lower than 1.2 %, showing very good agreement between the experimental and calculated values. As can be seen in Figure 1, the percentage relative deviation for each experimental point

Briefly, the device is equipped with a Cottrell circulation pump, a vacuum pump, and an electrovalve activated by an on−off controller in order to minimize the pressure deviations from the setting. Temperature was measured using Pt-100 class A sensors with the standard uncertainty of 0.15 K and pressure by a vacuum (0 mbar to 1000 mbar absolute range) or a pressure (0 mbar to 4000 mbar relative range) sensor, both presenting the standard uncertainty of 0.35 % full scale output and a standard uncertainty of 1.4 kPa. 2.3. Analytical Method. All collected samples were analyzed in a Shimadzu GC 2010 Plus gas chromatograph equipped with flame ionization detector. The compounds were separated using a silica capillary column (CP-WAX 57CB 25 m × 0.53 mm ID, film thickness of 2.0 μm). Helium N50 was used as the carrier gas at a flow rate of 30.0 mL·min−1. The temperature of the injector and of the detector was set to 523.15 K and 573.15 K, respectively. For the analysis of each binary mixture, appropriate temperature programs were selected for the column, within the range of 323.15 K to 413.15 K. In this way, the standard uncertainty of the measured mole fractions was 0.005.

ln Pisat = A +

−3.8789 −8.5767 −1.2676 × 101 −1.1655 × 101 −1.4125 × 101

varied between −2.3 % and 1.6 %. The highest deviation was found for isopropyl acetate, for which only 77 vapor pressure data points are available, according to the Dortmund Data Bank.19 This value is quite low when compared to the information available for 1-propanol, 2-propanol, 1-butanol, and 2-butanol which have 1405, 1137, 1583, and 1007 data points, respectively, already reported in the literature.19 3.2. Binary Systems. The VLE data for the 2-propanol (1) and isopropyl acetate (2) binary system were first measured at 101.32 kPa to further evaluate the performance of the equipment. The experimental data are presented in Table 4, where xi is the mole fraction of component i in the liquid phase,

(1)

where T is the absolute temperature. Table 3 presents the coefficients A, B, C, D, and E found in the Aspen Physical Property System Pure Component Databank (Aspen Plus V8.6 B



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Table 4. Isobaric VLE Data for Isopropyl Acetate (1) and 2-Propanol (2) System at 101.32 kPaa T

x1

y1

γ1

γ2

T

K 355.21 354.01 353.81 353.61 353.61 353.51 353.61 353.81 353.91 354.11 354.41 354.81 355.11 355.61 356.11 a

x1

y1

γ1

γ2

0.8190 0.8442 0.8789 0.8969 0.9278 0.9503 0.9599 0.9679 0.9749 0.9792 0.9841 0.9884 0.9907 0.9932

0.7175 0.7446 0.7748 0.7956 0.8596 0.8891 0.9086 0.9240 0.9448 0.9550 0.9645 0.9712 0.9775 0.9832

1.022 1.012 0.995 0.985 1.006 0.993 0.998 0.994 1.003 1.002 1.004 1.003 1.001 1.001

1.458 1.502 1.671 1.748 1.667 1.863 1.887 1.932 1.777 1.740 1.789 1.982 1.920 1.943

K 0.0009 0.1031 0.1654 0.2278 0.2673 0.3117 0.3890 0.4315 0.4876 0.5453 0.5945 0.6412 0.6925 0.7314 0.7708

0.0012 0.1131 0.2108 0.2580 0.2913 0.3316 0.3888 0.4130 0.4532 0.4949 0.5299 0.5625 0.6048 0.6360 0.6732

1.579 1.409 1.648 1.475 1.419 1.390 1.301 1.238 1.198 1.162 1.130 1.097 1.082 1.059 1.046

0.999 1.037 1.000 1.024 1.031 1.039 1.066 1.092 1.124 1.160 1.196 1.238 1.290 1.333 1.375

356.91 357.41 357.91 358.41 359.11 359.81 360.01 360.41 360.61 360.81 360.91 361.01 361.21 361.31

Standard uncertainties u are u(T) = 0.15 K, u(P) = 1.4 kPa, u(x1) = u(y1) = 0.005.

yi is the mole fraction of component i in the vapor phase and γi is the activity coefficient of component i calculated in accordance to eq 2: yP γi = i sat xiPi (2)

Table 5. Azeotropic Data for the System Isopropyl Acetate (1) and 2-Propanol (2) System at 101.32 kPa T

x1

reference

0.3369 0.3100 0.3493 0.3074 0.3447 0.3500 0.3100

this work 12 14 15 16 17 9

K 353.59 354.05 353.25 354.15 353.25 354.05 353.67

where P is the system’s total pressure. For this system, VLE data measured by other authors at 101.32 kPa can be found.9,10,12,13 All sets of data are in satisfactory agreement, showing a minimum boiling point azeotrope. For simplicity, the VLE data determined in this work is compared graphically, in Figure 2, only with the data

point test was not used as it is not applicable to isobaric data sets. For each test, a quality factor Ftest was calculated. The maximum value is 1.0 for the pure component test and 0.25 for the remaining three tests. Then, for each VLE data set, an overall quality factor (QVLE) can be calculated as follows:20 Q VLE = [Fpure component·(FHerington + FVan Ness + Finfinite dilution)]/0.75

(3)

For this system QVLE is 0.94, close to the maximum value, showing the good quality of the data. Afterward, the VLE data of the three remaining systems were measured at 101.32 kPa. Tables 6, 7, and 8 present the experimental data collected as well as the experimental activity coefficients of both components for the binary systems isopropyl acetate + 1-propanol, isopropyl acetate + 1-butanol, and isopropyl acetate + 2-butanol, respectively. A minimum boiling point azeotrope was also observed in the mixture of isopropyl acetate + 1-propanol. For the systems isopropyl acetate + 1-butanol or isopropyl acetate + 2-butanol, no azeotrope was identified. A moderate positive deviation from ideal behavior was observed for all systems, as already found for similar alcohol + ester binary systems.2,4−6 Though esters are not able to selfassociate, cross-association between the ester and the hydroxyl groups exists, in agreement with the moderate magnitude of the activity coefficients in the highly diluted regions of composition.

Figure 2. VLE for isopropyl acetate (1) and 2-propanol (2) system at 101.32 kPa: ○, experimental data (this work); +, experimental data;9 − −−− NRTL model; − − − UNIQUAC model.

obtained more recently by Andreatta et al.9 The azeotropic data were estimated in this work at T = 353.59 K and x1 = 0.3369 (liquid mole fraction of isopropyl acetate), using either the NRTL or the UNIQUAC models, as described in more detail below. As can be seen in Table 5, our data satisfactorily agree with the information already available in the literature. The quality of the experimental data was further analyzed by applying a quality assessment algorithm for vapor−liquid equilibrium data proposed by Kang et al.20 Four consistency tests were combined: the Herington test, the Van Ness test, the infinite dilution test, and the pure component test.20−24 The C



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Table 6. Isobaric VLE Data for Isopropyl Acetate (1) and 1-Propanol (2) System at 101.32 kPaa T

x1

y1

γ1

γ2

T

K 369.90 369.60 369.40 369.00 368.60 368.20 367.60 367.40 366.60 366.10 365.50 364.90 364.30 363.80 a

x1

y1

γ1

γ2

0.3392 0.3832 0.4355 0.5128 0.5798 0.6688 0.7354 0.7554 0.8222 0.8653 0.9248 0.9380 0.9764

0.4587 0.4969 0.5395 0.5901 0.6468 0.7004 0.7469 0.7634 0.8181 0.8501 0.9110 0.9279 0.9688

1.284 1.251 1.210 1.149 1.128 1.073 1.041 1.039 1.023 1.007 1.003 1.004 1.004

1.076 1.092 1.110 1.177 1.195 1.306 1.382 1.403 1.484 1.608 1.698 1.662 1.875

K 0.0133 0.0219 0.0304 0.0428 0.0562 0.0717 0.0891 0.0972 0.1458 0.1745 0.2052 0.2314 0.2865 0.3052

0.0333 0.0512 0.0696 0.0944 0.1173 0.1463 0.1709 0.2033 0.2510 0.2867 0.3199 0.3466 0.4011 0.4202

1.936 1.829 1.796 1.753 1.683 1.665 1.592 1.748 1.475 1.429 1.381 1.352 1.288 1.287

0.996 0.998 0.995 0.996 0.999 0.998 1.011 0.987 1.012 1.017 1.030 1.048 1.060 1.074

363.30 362.81 362.41 361.71 361.31 360.91 360.91 360.81 360.81 360.91 361.11 361.21 361.31


Table 7. Isobaric VLE Data for Isopropyl Acetate (1) and 1-Butanol (2) System at 101.32 kPaa T

x1

y1

γ1

γ2

T

K 390.49 390.39 390.09 389.89 389.49 389.09 388.59 388.09 387.19 385.09 383.19 381.90 a

x1

y1

γ1

γ2

0.2183 0.2802 0.3235 0.3542 0.4542 0.6240 0.6791 0.7577 0.8353 0.9239 0.9766

0.4764 0.5488 0.6016 0.6218 0.7026 0.8128 0.8545 0.9005 0.9254 0.9700 0.9889

1.245 1.190 1.191 1.151 1.075 1.030 1.052 1.040 1.013 1.013 1.005

0.988 1.006 1.014 1.041 1.048 1.140 1.119 1.079 1.265 1.182 1.479

K 0.0060 0.0082 0.0114 0.0155 0.0208 0.0292 0.0390 0.0504 0.0533 0.1051 0.1479 0.1813

0.0207 0.0281 0.0393 0.0552 0.0786 0.1025 0.1292 0.1584 0.2000 0.3149 0.3783 0.4224

1.490 1.484 1.504 1.564 1.670 1.574 1.505 1.445 1.768 1.495 1.346 1.271

1.000 0.998 1.000 0.995 0.989 0.986 0.984 0.980 0.965 0.944 0.965 0.980

380.30 378.10 376.30 375.50 373.50 369.20 367.40 365.90 364.50 362.81 361.91


Table 8. Isobaric VLE Data for Isopropyl Acetate (1) and 2-Butanol (2) System at 101.32 kPaa T

x1

y1

γ1

γ2

T

K 372.40 372.20 372.10 371.80 371.40 371.20 370.90 370.60 370.10 369.60 369.30 368.80 368.40 367.60 367.30 a

x1

y1

γ1

γ2

0.3534 0.4168 0.4415 0.4808 0.5158 0.5555 0.6195 0.6898 0.7668 0.8195 0.8867 0.9336 0.9663 0.9901

0.4780 0.5379 0.5619 0.5973 0.6160 0.6583 0.7057 0.7543 0.8119 0.8556 0.9047 0.9445 0.9725 0.9906

1.151 1.133 1.128 1.118 1.082 1.087 1.061 1.035 1.021 1.020 1.006 1.004 1.002 0.996

1.017 1.037 1.039 1.047 1.079 1.063 1.090 1.139 1.187 1.196 1.273 1.275 1.251 1.454

K 0.0203 0.0258 0.0340 0.0473 0.0582 0.0744 0.0885 0.1071 0.1278 0.1563 0.1733 0.1996 0.2319 0.2764 0.3028

0.0367 0.0485 0.0640 0.0885 0.1108 0.1362 0.1577 0.1857 0.2178 0.2571 0.2799 0.3153 0.3503 0.4021 0.4321

1.298 1.362 1.361 1.368 1.410 1.364 1.338 1.315 1.311 1.285 1.273 1.265 1.224 1.208 1.196

1.002 1.003 0.999 0.997 0.999 0.995 0.996 0.994 0.996 0.997 0.997 0.998 1.002 1.009 1.006

366.80 365.80 365.50 365.00 364.80 364.40 363.90 363.40 362.81 362.41 362.11 361.91 361.81 361.81


the remaining systems, the overall quality factors are 0.86 and 0.98 for isopropyl acetate + 1-butanol and isopropyl acetate + 2-butanol, respectively, values that are reasonably close to the maximum.

Once more, the above-mentioned thermodynamic consistency tests were applied to these mixtures. The results can be found in Table 9. The quality factor attained the maximum value for the isopropyl acetate + 1-propanol binary mixture. For D



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Table 9. Overall Quality Factor for the Thermodynamic Consistency Check binary system isopropyl isopropyl isopropyl isopropyl

acetate acetate acetate acetate

+ + + +

2-propanol 1-propanol 1-butanol 2-butanol

FHerington

FVan Ness

Finfinite dilution

Fpure component

QVLE

0.25 0.25 0.23 0.25

0.25 0.25 0.20 0.25

0.21 0.25 0.21 0.24

1.00 1.00 1.00 1.00

0.94 1.00 0.86 0.98

Table 10. Binary Interaction Parameters, in J·mol−1, and Deviations of Temperature and Isopropyl Acetate Vapor Phase Composition binary system

models

δT

parameters

δy1

K isopropyl acetate (1) + 1-propanol (2) isopropyl acetate (1) + 2-propanol (2) isopropyl acetate (1) + 1-butanol (2) isopropyl acetate (1) + 2-butanol (2)

NRTL (α = UNIQUAC NRTL (α = UNIQUAC NRTL (α = UNIQUAC NRTL (α = UNIQUAC

Δg12 = 471.54 Δu12 = −1166.72 Δg1 = 1180.45 Δu12 = −1516.02 Δg12 = 2585.49 Δu12 = −1870.20 Δg12 = 1644.15 Δu12 = −605.58

0.3) 0.3) 0.3) 0.3)

Δg21 = 1481.72 Δu21 = 368.72 Δg21 = 667.78 Δu21 = 661.06 Δg21 = −1190.90 Δu21 = 1175.53 Δg21 = −512.94 Δu21 = 278.52

0.160 0.160 0.088 0.090 0.309 0.311 0.092 0.061

0.005 0.005 0.008 0.008 0.018 0.018 0.008 0.009

Finally, the experimental data were correlated using the NRTL25 and the UNIQUAC26 activity coefficient models. The vapor phase fugacity coefficients were calculated using the virial equation of state truncated at the second term, and the second virial coefficients (Bii, Bij) were obtained by applying the Hayden and O’Connell method.27 The data regression was performed by Aspen Plus V8.6 software. The binary interaction parameters of both models were determined by the leastsquares method by minimizing the following objective function Fobj: 2 ⎧⎡ calc ⎡ P calc − P exp ⎤2 ⎪ T j − T jexp ⎤ j ⎥ +⎢ j ⎥ Fobj = ∑ ⎨⎢ ⎢ ⎥ ⎢ ⎥⎦ σ σ ⎪ T P ⎦ ⎣ j=1 ⎣ ⎩ N

2 ⎡ x calc − x exp ⎤2 ⎡ y calc − y exp ⎤ ⎫ j j j j ⎥⎪ ⎥ +⎢ ⎬ +⎢ ⎢ ⎥⎪ ⎢⎣ ⎥⎦ σx σy ⎣ ⎦⎭

Figure 3. VLE for isopropyl acetate (1) and 1-propanol (2) system at 101.32 kPa: ○, experimental data; − −−−, NRTL model; − − −, UNIQUAC model.

(4)

where N is the number of experimental points and σ is the standard deviation of the measured variables: temperature T (0.1 K), pressure P (0.2 kPa), liquid composition x (0.005), and vapor composition y (0.005). The superscripts “calc” and “exp” represent calculated and experimental values, respectively. The minimization of the objective function is subject to the constraints of phase equilibrium that is the “calc” quantities in eq 4 are constrained by the two equality of fugacity equations. Table 10 presents the binary interaction parameters obtained for both models, as well as the average absolute deviations in temperature and vapor phase composition. The small deviations show that all systems are almost equally well represented by both models, as can be also seen by the corresponding overlapping curves represented in Figures 2 to 5. Finally, using the thermodynamic models described above, the azeotropic data for the isopropyl acetate + 1-propanol system was estimated at T = 360.86 K and x1 = 0.7832, using either the UNIQUAC or NRTL models. This result satisfactorily agrees with the experimental data available at a close pressure of 101.50 kPa (T = 361.05 K and x1 = 0.7744).18

Figure 4. VLE for isopropyl acetate (1) and 1-butanol (2) system at 101.32 kPa: ○, experimental data; − −−−, NRTL model; − − −, UNIQUAC model.

4. CONCLUSIONS Isobaric vapor−liquid equilibria diagrams of the binary mixtures containing isopropyl acetate and an alkanol (1-propanol, 2propanol, 1-butanol, or 2-butanol) were obtained at 101.32 kPa. Both isopropyl acetate + 2-propanol and isopropyl acetate + 1-propanol systems presented a minimum boiling point E



Article

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Figure 5. VLE for isopropyl acetate (1) and 2-butanol (2) system at 101.32 kPa: ○, experimental data; − −−−, NRTL model; − − −, UNIQUAC model.

azeotrope. The consistency of the experimental data was assessed by applying the Herington test, the Van Ness test, the infinite dilution test, and the pure component test, indicating the high quality of the measured data. Finally, both NRTL and UNIQUAC activity coefficient models were able to successfully correlate the measured data, with similar accuracy.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Tel.: +351 273 303 087. Fax: +351 273 313 051. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was cofinanced by FCT/MEC and FEDER under Programe PT2020 (Project UID/EQU/50020/2013) and also by QREN, ON2 and FEDER (Project NORTE-07-0162FEDER-000050). C.S.M.P. acknowledges also Fundo Social Europeu and POPH-Programa Operacional Potencial Humano (FCT Investigator-IF/01486/2013). The authors thank DDBST, Dortmund Data Bank Software & Separation Technology GmbH, namely Dr. Wilfried Cordes, for supplying relevant sets of phase equilibria data.

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REFERENCES

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