Vapor–Liquid Equilibria for Ternary Mixtures of Isopropyl Alcohol

Tianjin United Environmental Engineering Design Company Limited, Tianjin 300191, China. ∥ School of ... Publication Date (Web): August 5, 2016. Copy...
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Vapor−Liquid Equilibria for Ternary Mixtures of Isopropyl Alcohol, Isopropyl Acetate, and DMSO at 101.3 kPa Hui Ding,† Yujie Gao,*,‡,§ Jiaqi Li,∥ Jinlong Qi,∥ Hang Zhou,∥ Shejiang Liu,† and Xu Han† †

School of Environmental Science and Engineering, Tianjin University, Tianjin 300072, China Tianjin Academy of Environmental Sciences, Tianjin 300191, China § Tianjin United Environmental Engineering Design Company Limited, Tianjin 300191, China ∥ School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China ‡

S Supporting Information *

ABSTRACT: The vapor−liquid equilibrium (VLE) data for the binary system isopropyl alcohol + dimethyl sulfoxide (DMSO), isopropyl acetate + DMSO, and ternary system isopropyl alcohol + isopropyl acetate + DMSO were measured with a VLE modified Othmer still at 101.3 kPa. The experimental data were proved to be thermodynamically consistent when the point-to-point consistency test of Van Ness test was applied. The binary experimental data were correlated with the nonrandom two-liquid (NRTL), Wilson, and universal quasichemical (UNIQUAC) activity coefficient models. Then, the ternary VLE data were predicted with the obtained binary interaction parameters. The results indicate that the values of equilibrium temperature and vapor mole fraction calculated by the NRTL, Wilson, and UNIQUAC models are in good agreement with the experimental data. When the mole ratio of the binary azeotrope to DMSO was 1:1.5, the binary azeotrope of isopropyl alcohol and isopropyl acetate was eliminated. Therefore, DMSO is a potential extractive agent to separate the azeotrope by extractive distillation.

1. INTRODUCTION Isopropyl alcohol is an important industrial raw material, which is widely applied in pesticide, medicine, electronics, daily chemical, fuel additives, and so forth.1−4 Isopropyl acetate, an important raw material of synthetic resin and surface coating, has received increasing attention for its application as solvent, dehydrating agent, and medicine extraction agent, fiber derivative, oil fat, and so forth.5,6 In industry, the catalytic hydrogenation of isopropyl acetate can be used to synthesize high added value products of ethanol and isopropyl alcohol, both of which have high theoretical research and practical application value. Isopropyl alcohol and acetic acid are used to generate isopropyl acetate,7−9 and in this industrial process, isopropyl alcohol and isopropyl acetate are mixed together. Therefore, the separation of the two substances is necessary for the purity of materials in industry to be guaranteed. The mixture of isopropyl acetate and isopropyl alcohol is a minimum-boiling azeotrope. Therefore, they cannot be separated by common distillation.10 Extractive distillation, a special rectification process, is widely used in the separation of azeotropic systems. The selection of solvents is the key point to ensure a cost-effective process.11 Previous literature12,13 reports that the isopropyl alcohol and the isopropyl acetate binary azeotropic mixture can be separated by the solvent of ionic © XXXX American Chemical Society

liquids, but most of the ionic liquids have the property of high viscosity, which may cause a large amount of loss in the experiment and industry. In addition, the high cost restricts the large-scale application in the industry.14 With low viscosity and cost, dimethyl sulfoxide, a versatile solvent, can dissolve most organic and inorganic substance, which also possesses the properties of high polarity, high boiling point, and thermal stability.15,16 In previous literature, DMSO can effectively break the azeotrope system of alcohol and ester.17,18 Therefore, DMSO was selected as the extracting agent to change the relative volatility of azeotrope in our study. The VLE data for the ternary system of isopropyl alcohol (1) + isopropyl acetate (2) + DMSO (3) and its constituent binary systems are essential to design an extractive distillation process. So far, no VLE data except those for isopropyl alcohol (1) + isopropyl acetate (2)12,19−21 has been reported in open literature. In this work, some thermodynamic studies on the ternary system of isopropyl alcohol (1) + isopropyl acetate (2) + DMSO (3) and the corresponding binary systems were carried out. The VLE data for the binary and ternary system were determined with a modified Othmer still. The reliability of the experimental Received: January 14, 2016 Accepted: July 27, 2016

A

DOI: 10.1021/acs.jced.6b00040 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 1. Experimental Reagents Description molecular formula

CAS RN

supplier

purity (mass %)

analysis method

purification method

Tb(K) (101.3 kPa) this work

Tb(K) (101.3 kPa) literature

isopropyl alcohol

C3H8O

67-63-0

Kewei, China

⩾99.7%

GCa, KFb

none

355.35

isopropyl acetate

C5H10O2

108-21-4

TCI, China

>99.8%

GCa, KFb

none

361.45

dimethyl sulfoxide

C2H6SO

67-68-5

Aladdin, China

>99.8%

GCa, KFb

none

463.38

355.35c 355.30d 361.45e 361.65c,d 463.15f 464d

chemical name

a f

Gas chromatography. bKarl Fischer titration. cTaken from ref 23. dTaken from Aspen Plus physical properties databanks. eTaken from ref 13. Taken from ref 24.

first-order raising speed was 40 K/min. Standard solutions prepared gravimetrically by an electronic balance (FA2004N, uncertainty of ±0.0001 g) were used to calibrate the GC. The accuracy of the analytical method was tested by known samples of mixtures, and the maximum relative error did not exceed 0.5%.

data was examined and verified with the Van Ness test.22 Then, the binary VLE data were correlated by the NRTL, Wilson, and UNIQUAC models to acquire the binary parameters, and the ternary VLE data were predicted by these models with the parameters.

2. EXPERIMENTAL SECTION 2.1. Materials. The materials isopropyl alcohol, isopropyl acetate, and DMSO were used in this work. Information about the molecular formula, CAS Registry Number (CASRN), purity levels, sources, and the measured boiling points of pure compounds at 101.3 kPa as well as the values reported in the literature is listed in Table 1, respectively. Purities of the reagents were determined by a gas chromatography (GC 2060, China) equipped with a flame ionization detector. In addition, the water contents were measured by Karl Fischer titration, and no appreciable water was detected. All of the materials were used without further purification. 2.2. Apparatus and Procedure. The isobaric VLE data were determined with a modified circulation still,25 which includes an equilibrium chamber, gas phase sampling port, liquid phase sampling port, heating rods, and condenser. A precision thermometer with the accuracy of ±0.05 K was used to measure the temperature. A Fisher M101 pressure control system was employed to control and detect the pressure. During the experiment, the pressures in the VLE experiment were kept at 101.3 ± 0.1 kPa. In each measurement of the VLE data, 40 mL mixtures of the different ratio liquid were added into the chamber and then heated at 101.3 kPa. The vapor was condensed in the condensing coil and immediately returned to the equilibrium chamber through the vapor-phase sampling port. The temperature was maintained at the boiling point for 0.5−1.0 h to ensure that equilibrium was established. After that, the samples of liquid and vapor phase were carefully taken at least three times for the composition analysis. The mean value was recorded when the deviation of the measuring values was less than 0.5%. More detailed information about the device can be found in our previous work.26 2.3. Analysis. The liquid samples and vapor samples were simultaneously withdrawn to be analyzed by GC with flame ionization detector (FID) and FFAP column (30 m × 0.45 mm × 2.55 μm). The response of the GC was handled with N-2000 chromatography station. Nitrogen was used as carrier gas, and the flow rate was constant at 1 mL/min. Temperatures of the detector and the injector were kept at 473.15 K. The programmed temperature gas chromatography was adopted to detect the composition of isopropyl alcohol and isopropyl acetate. The specific condition is that the programmed temperature of the oven started from 313.15 to 413.15 K, and the

3. RESULTS AND DISCUSSION 3.1. Isobaric VLE Data. The VLE data for the ternary system of isopropyl alcohol (1) + isopropyl acetate (2) + DMSO (3) and its constituent binary systems were determined at 101.3 kPa. The tabulated activity coefficient (γi) was calculated by the equation as follows27,28 ⎛ V L(P − P s) ⎞ i ⎟ φiPyi = γixiPisφis exp⎜ i RT ⎝ ⎠

(1)

where yi and xi are the mole fractions of component i in the vapor and liquid phase, respectively. γi is the activity coefficient of component i. R is the gas constant, and VLi is the molar volume of pure liquid i. Psi is the saturation vapor pressure of component i, which was obtained by the following extended Antoine equation:29,30 ln(Pis/KPa) = C1, i + C2, i /[(T /K) + C3, i] + C4, i(T /K) + C5, i(ln T /K) + C6, i(T /K)C7,i

(2)

Table 2. Value of Constants C1, i−C7, i, Tmin, and Tmax for Pure Componentsa

a

component

isopropyl alcohol

isopropyl acetate

DMSO

C1 C2 C5 C6 C7 Tmin (K) Tmax (K)

103.8122 −9040.00 −12.6760 5.5380 × 10−6 2.00 185.26 508.30

42.8462 −5563.90 −3.8789 2.4755 × 10−18 6.00 199.75 532.00

49.3652 −7620.60 −4.6279 4.3819 × 10−7 2.00 291.67 729.00

Taken from Aspen Plus physical properties databanks.

Table 3. Physical Properties of the Componentsa

a

B

component

isopropyl alcohol

isopropyl acetate

DMSO

M/g·mol−1 Tc/K Pc/kPa ω Zc Vc/cum·kmol−1

60.0959 508.30 4765.00 0.6630 0.250 0.222

102.1332 532.00 3290.00 0.3678 0.250 0.336

78.1350 729.00 5650.00 0.2806 0.212 0.227

Taken from Aspen Plus physical properties databanks. DOI: 10.1021/acs.jced.6b00040 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 4. Experimental VLE Data, Activity Coefficients γi, and Fugacity Coefficients φi for the Binary System of Isopropyl Alcohol (1) + DMSO (3) at Temperature T, Liquid Mole Fractions xi, Gas Mole Fractions yi, and Pressure p = 101.3 kPaa

For the three substances, C3 = C4 = 0. Therefore, eq 2 can be simplified as ln(Pis/KPa) = C1, i + C2, i/(T /K) + C5, i(ln T /K) + C6, i(T /K)C7,i

(3)

where the temperature ranges from Tmin to Tmax. In the range of Tmin to Tmax, the Antoine equation can be used. The values of constants C1,i−C7,i, Tmin, and Tmax for the pure components are listed in Table 2. φsi and φi are the fugacity coefficients of pure vapor i and component i in the mixture vapor phase, respectively, which were calculated by the Soave−Redlich−Kwong (SRK) equation.31 The physical properties of the pure components, which were used to calculate the φi and φsi , including molecular weight M, critical temperature Tc, critical pressure Pc, acentric factor ω, critical compression factor Zc, and critical volume Vc were listed in Table 3.

(

V L(P − P s)

)

The Poynting factor exp i RT i is approximately equal to 1 at low or moderate pressure. Therefore, eq 1 can be simplified as φiPyi = γixiPisφis

(4)

The VLE data of the ternary system isopropyl alcohol (1) + isopropyl acetate (2) + DMSO (3) and the binary systems isopropyl alcohol (1) + DMSO (3) and isopropyl acetate (2) + DMSO (3) were listed in Table 4−6. Thus, the γi listed in Table 4 and Table 5 can be obtained by eq 4. 3.2. Thermodynamic Consistency Test. The Herington area32 test method is used to check the thermodynamic consistency of the binary VLE data. The test can be described by the following equations. x=1

D = 100 ×

1

y1

γ1

1.0000 0.9983 0.9972 0.9961 0.9925 0.9869 0.9776 0.9726 0.9623 0.9483 0.9371 0.9015 0.8675 0.8045 0.6991 0.6560 0.5481 0.4695 0.3120 0.0000

1.0000 1.0110 1.0111 1.0017 0.9803 0.9752 0.9414 0.9312 0.9295 0.9078 0.9088 0.8683 0.8674 0.8554 0.8389 0.8323 0.8232 0.8258 0.8110

γ3

φ1

φ3

0.6903 0.6718 0.6774 0.7301 0.8035 0.8798 0.8945 0.9062 0.9179 0.9409 0.9496 0.9488 0.9761 0.9778 0.9812 0.9852 1.0023 1.0052 1.0000

0.9747 0.9751 0.9754 0.9763 0.9771 0.9782 0.9787 0.9795 0.9807 0.9809 0.9826 0.9833 0.9845 0.9860 0.9864 0.9877 0.9880 0.9890

0.9532 0.9538 0.9543 0.9556 0.9569 0.9586 0.9593 0.9606 0.9620 0.9628 0.9650 0.9664 0.9683 0.9704 0.9711 0.9724 0.9731 0.9743

The standard uncertainty is u(T) = 0.05 K, u(P) = 0.3 kPa, and u(y1) = u(x1) = 0.004.

Table 5. Experimental VLE Data, Activity Coefficients γi, and Fugacity Coefficients φi for the Binary System of Isopropyl Acetate (2) + DMSO (3) at Temperature T, Liquid Mole Fractions xi, Gas Mole Fractions yi, and Pressure p = 101.3 kPaa

γ

2

γ1

∫x = 0 ln γ dx1 1

x1 1.0000 0.9032 0.8481 0.8051 0.7091 0.6138 0.5225 0.4832 0.4149 0.3561 0.3207 0.2491 0.2009 0.1512 0.1022 0.0890 0.0635 0.0496 0.0286 0.0000

a

∫x = 0 1 ln γ1 dx1 x1= 1

T/K 355.33 357.51 359.14 360.75 364.71 368.77 374.24 376.78 381.24 386.47 389.52 398.61 405.21 414.02 425.63 429.39 437.48 441.94 450.41 463.38

2

T − Tmin J = 150 × max Tmin

(5)

(6)

where Tmax and Tmin are the maximum and minimum boiling temperatures in the studied system, respectively. The isobaric VLE was considered as thermodynamically consistent if (D − J) < 10. The results of the consistency test are listed in Table 7, indicating that all of the VLE data pass the thermodynamic consistency tests. 3.3. Data Regression. The NRTL, Wilson, and UNIQUAC models were employed by Aspen Plus33 to correlate the isobaric VLE data in this work. The maximum likelihood objective function taken from Aspen Plus was adopted in the regression of the binary VLE data, which is expressed as ⎡ exp cal 2 ⎛ T exp − T cal ⎞2 ⎢⎛ P − Pi ⎞ i ⎟⎟ + ⎜⎜ i ⎟⎟ F = ∑ ⎢⎜⎜ i σ σ ⎝ ⎠ ⎝ ⎠ P T i=1 ⎢ ⎣ N

2 ⎛ x exp − x cal ⎞2 ⎛ y exp − y cal ⎞ ⎤ 1, i 1, i 1, i 1, i ⎟⎥ ⎟ +⎜ + ⎜⎜ ⎟ ⎜ ⎟⎥ σx σy ⎝ ⎠ ⎝ ⎠ ⎥⎦

T/K

x2

y2

γ2

361.45 363.59 366.56 369.36 370.72 374.06 376.18 377.74 381.61 383.18 384.96 386.62 388.17 392.92 400.53 413.46 425.98 444.02 456.01 463.38

1.0000 0.9207 0.8012 0.6769 0.6144 0.4838 0.4237 0.3817 0.3019 0.2720 0.2541 0.2341 0.2199 0.1791 0.1341 0.0859 0.0551 0.0266 0.0098 0.0000

1.0000 0.9935 0.9849 0.9776 0.9769 0.9648 0.9577 0.9560 0.9432 0.9412 0.9355 0.9301 0.9254 0.9062 0.8705 0.7871 0.6715 0.4241 0.1891 0.0000

1.0000 1.0172 1.0600 1.1470 1.2140 1.3843 1.4787 1.5695 1.7629 1.8733 1.9015 1.9661 2.0006 2.1349 2.2806 2.4089 2.4781 2.3211 2.2994

γ3

φ2

φ3

2.4356 1.9781 1.5979 1.3022 1.2863 1.2673 1.1520 1.1256 1.0494 1.0471 1.0356 1.0219 1.0191 1.0088 1.0045 1.0025 1.0014 1.0006 1.0000

0.9645 0.9653 0.9661 0.9664 0.9673 0.9678 0.9682 0.9692 0.9698 0.9699 0.9706 0.9707 0.9717 0.9733 0.9757 0.9781 0.9804 0.9819

0.9534 0.9544 0.9553 0.9558 0.9568 0.9575 0.9579 0.9591 0.9595 0.9600 0.9605 0.9609 0.9622 0.9641 0.9671 0.9697 0.9731 0.9750

a The standard uncertainty is u(T) = 0.05 K, u(P) = 0.3 kPa, and u(y1) = u(x1) = 0.004.

(7)

liquid composition σx, and vapor composition σy used in this VLE data correlation are 0.1013 kPa, 0.1 K, 0.001, and 0.001, respectively.

where σ is the standard deviation of the corresponding parameters. The standard deviations of pressure σP, temperature σT, C

DOI: 10.1021/acs.jced.6b00040 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 6. Experimental VLE Data for Ternary System of Isopropyl Alcohol (1) + Isopropyl Acetate (2) + DMSO (3) at Temperature T, Liquid Mole Fractions xi, Normalization Liquid Mole Fractions xi′, Gas Mole Fractions yi, Normalization Gas Mole Fractions yi′, and Pressure p = 101.3 kPaa

a

T/K

x1

x2

x3

x1′b

x2′b

y1

y2

y3

y1′c

y2′c

377.52 377.82 378.22 378.50 378.70 379.09 378.99 379.25 379.82 379.93 380.32 381.19 381.82 382.21 382.24 382.16 382.59 382.87 383.34 383.63 383.70

0.0191 0.0376 0.0554 0.0751 0.0974 0.1150 0.1254 0.1385 0.1531 0.1755 0.1924 0.2080 0.2244 0.2463 0.2674 0.2928 0.3159 0.3264 0.3462 0.3564 0.3744

0.3664 0.3437 0.3240 0.3074 0.2941 0.2721 0.2657 0.2521 0.2332 0.2151 0.1972 0.1716 0.1528 0.1342 0.1172 0.0994 0.0773 0.0595 0.0398 0.0201 0.0111

0.6145 0.6187 0.6206 0.6175 0.6085 0.6129 0.6089 0.6094 0.6137 0.6094 0.6104 0.6204 0.6228 0.6195 0.6154 0.6078 0.6068 0.6141 0.6140 0.6235 0.6145

0.0495 0.0986 0.1460 0.1963 0.2488 0.2971 0.3206 0.3546 0.3963 0.4493 0.4938 0.5479 0.5949 0.6473 0.6953 0.7466 0.8034 0.8458 0.8969 0.9466 0.9712

0.9505 0.9014 0.8540 0.8037 0.7512 0.7029 0.6794 0.6454 0.6037 0.5507 0.5062 0.4521 0.4051 0.3527 0.3047 0.2534 0.1966 0.1542 0.1031 0.0534 0.0288

0.0254 0.0479 0.0769 0.1089 0.1428 0.1783 0.1961 0.2198 0.2543 0.3022 0.3452 0.3928 0.4388 0.4942 0.5495 0.6131 0.6862 0.7393 0.8103 0.8762 0.9153

0.9335 0.9102 0.8810 0.8496 0.8164 0.7797 0.7628 0.7393 0.7036 0.6567 0.6125 0.5632 0.5161 0.4619 0.4058 0.3436 0.2719 0.2174 0.1475 0.0795 0.0426

0.0411 0.0419 0.0421 0.0415 0.0408 0.0420 0.0411 0.0409 0.0421 0.0411 0.0423 0.0440 0.0451 0.0439 0.0447 0.0433 0.0419 0.0433 0.0422 0.0443 0.0421

0.0265 0.0500 0.0803 0.1136 0.1489 0.1861 0.2045 0.2292 0.2655 0.3152 0.3604 0.4109 0.4595 0.5169 0.5752 0.6408 0.7162 0.7728 0.8460 0.9168 0.9555

0.9735 0.9500 0.9197 0.8864 0.8511 0.8139 0.7955 0.7708 0.7345 0.6848 0.6396 0.5891 0.5405 0.4831 0.4248 0.3592 0.2838 0.2272 0.1540 0.0832 0.0445

The standard uncertainty is u(T) = 0.05 K, u(P) = 0.3 kPa, and u(yi) = u(xi) = 0.004. bxi′ = xi/(x1 + x2). cyi′ = yi/(y1 + y2).

Table 7. Herington Area Test Results for the Binary Systems of Isopropyl Alcohol (1) + DMSO (3) and Isopropyl Acetate (2) + DMSO (3) Herington system

D

isopropyl alcohol (1) + DMSO (3) 54.0166 isopropyl acetate (2) + DMSO (3) 9.7412

J

D−J

results

45.6125 42.3005

8.4041 −32.5593

passed passed

Figure 2. T vs x1, y1 diagram for the isopropyl alcohol + DMSO system at 101.3 kPa (△, experimental data; ---, calculated with the NRTL model; ···, calculated with the Wilson model; , calculated with the UNIQUAC model).

mole fraction. The binary VLE data of isopropyl alcohol and isopropyl acetate were taken from ref 12. The modeling results show that there are some deviations between calculated and experimental data, which demonstrate that the model temperature dependence is not sufficient, while this is a common deficiency of the general models. Broad application of these general models often leads to poor pertinence. 3.4. Data Prediction. The VLE data of the ternary system isopropyl alcohol + isopropyl acetate + DMSO were predicted by the NRTL, Wilson, and UNIQUAC models with the obtained binary parameters. Table 9 shows the maximum and mean absolute deviations of vapor mole fraction and equilibrium temperature between experimental and calculated

Figure 1. T vs x1, y1 diagram for the isopropyl alcohol + isopropyl acetate system at 101.3 kPa (△, literature data;12 ---, calculated with the NRTL model; ···, calculated with the Wilson model; , calculated with the UNIQUAC model).

The comparisons between calculated and experimental data are presented in Figure 1, Figure 2, Figure 3, and Table S1 in the Supporting Information. The correlated binary parameters of the NRTL, Wilson, and UNIQUAC models from experimental data are shown in Table 8, together with the root-mean-square deviations (RMSD) in temperature, pressure, vapor, and liquid D

DOI: 10.1021/acs.jced.6b00040 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Figure 5 shows the isobaric VLE data of the system isopropyl alcohol + isopropyl acetate with and without DMSO, from which one can note that the azeotropic phenomenon is eliminated when the mole ratio of the binary azeotrope and DMSO is 1:1.5. With the data in Table 6 and the VLE data without DMSO compared, it can be concluded that the DMSO shows better selectivity analyzing with a smaller proportion of alcohol. It also can be speculated that the attraction of DMSO for alcohols is larger than that for esters. The same rule can be also draw in the open literature.18,36 Therefore, DMSO can change the relative volatility of azeotrope in our work, which demonstrates that DMSO is a potential extraction agent for this system.

4. CONCLUSIONS The isobaric VLE data of the binary systems isopropyl alcohol + DMSO, isopropyl acetate + DMSO, and the ternary system isopropyl alcohol + isopropyl acetate + DMSO at 101.3 kPa have been measured. The experimental data are thermodynamically consistent as checked by the Van Ness test. The NRTL, Wilson, and UNIQUAC models were employed to correlate the binary VLE data. The results show that these models match well with the experimental data. The obtained binary interaction parameters were used to predict the ternary VLE data, and the results show that all of these models can provide a satisfactory prediction. The azeotrope system is broken when the mole ratio of the azeotrope mixture to DMSO is 1:1.5. The experimental and modeling results demonstrate that DMSO is an extractive agent with great promise for the separation of isopropyl alcohol and isopropyl acetate by extractive distillation.

Figure 3. T vs x1, y1 diagram for the isopropyl acetate + DMSO system at 101.3 kPa (△, experimental data; ---, calculated with the NRTL model; ···, calculated with the Wilson model; , calculated with the UNIQUAC model).

values. The results show that some errors appear between calculated and measured results, since the general models have a common deficiency. The residue curves of the ternary system calculated by the Wilson model were shown in Figure 4. The connecting lines of the vapor phase points and liquid phase points are tangent well with the predict residue curves at the liquid phase points, indicating that the residue curves are in good agreement with the experimental data.34,35

Table 8. Correlated Parameters and RMSD for Systems of Isopropyl Alcohol (1) + Isopropyl Acetate (2), Isopropyl Alcohol (1) + DMSO (3), and Isopropyl Acetate (2) + DMSO (3) correlation parameters model

aij

aji

NRTLe Wilsonf UNIQUACg

−6.3761 −4.3709 3.4186

4.3534 6.9760 −3.8933

NRTLe Wilsonf UNIQUACg

3.3041 −1.6656 3.2563

−5.4220 1.0551 −0.7736

NRTLe Wilsonf UNIQUACg

−1.0165 3.1440 3.1036

−0.7025 −4.8432 −1.9080

N

a

RMSD

bij

δT/Ka

bji

Isopropyl Alcohol (1) + Isopropyl Acetate (2) 2374.47 −1447.04 0.08 1445.25 −2586.15 0.08 −1146.49 1221.97 0.08 Isopropyl Alcohol (1) + DMSO (3) −1680.18 2473.13 0.22 559.96 −206.68 0.25 −1731.62 623.59 0.25 Isopropyl Acetate (2) + DMSO (3) 587.72 541.82 0.25 −1403.22 1539.26 0.23 −1411.75 773.32 0.23

δP/kPab

δx1c

δy1d

0.0239 0.0243 0.0238

0.0000 0.0000 0.0000

0.0036 0.0035 0.0037

0.0729 0.0856 0.0876

0.0003 0.0003 0.0003

0.0025 0.0042 0.0020

0.1148 0.0963 0.0987

0.0002 0.0002 0.0002

0.0054 0.0043 0.0037 N

N

N

δT = (1/N × ∑i = 1 (Tiexp − Tical)2 )1/2 . bδP = (1/N × ∑i = 1 (Piexp − Pical)2 )1/2 . cδxi = (1/N × ∑i = 1 (xiexp − xical)2 )1/2 . dδyi = (1/N × ∑i = 1 (yiexp − yical )2 )1/2 .

NRTL, τij = aij + bij/T, the value of αij was fixed at 0.3. Wilson, ln Aij = aij + bij/T. UNIQUAC, τij = exp(aij + bij/T). f

e

g

Table 9. Maximum and Mean Absolute Deviations of the Vapor-Phase Mole Fraction and Equilibrium Temperature for the System of Isopropyl Alcohol + Isopropyl Acetate + DMSO maximum absolute deviations

a

model

ΔmaxT /K

Δmax y1b

NRTL Wilson UNIQUAC

1.28 0.77 1.52

0.0136 0.0052 0.0146

a

mean absolute deviations

Δmaxy2b

Δmaxy3b

c

δT /K

δy1d

δy2d

δy3d

0.0152 0.0049 0.0166

0.0033 0.0022 0.0040

0.85 0.43 0.98

0.0075 0.0026 0.0073

0.0088 0.0028 0.0095

0.0016 0.0011 0.0028

N

N exp b c exp − Tical)2 )1/2 . dδyi = (1/N × ∑i = 1 (yiexp − yical )2 )1/2 . ΔmaxT = max|Texp − Tcal − ycal i i |. Δmaxyi = |yi i |. δT = (1/ N × ∑i = 1 (Ti

E

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Figure 5. y1 − x1 vs x1 diagram for contrast of VLE behavior for the system isopropyl alcohol + isopropyl acetate with and without DMSO (●, , experimental VLE data with DMSO; ○, , experimental VLE data without DMSO).

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.6b00040. Comparison of experimental data and calculated data in Wilson, NRTL, and UNIQUAC models (PDF)

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REFERENCES

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Figure 4. Residue curves of the ternary system isopropyl alcohol + isopropyl acetate + DMSO (●, experimental liquid phase composition; ○, experimental vapor phase composition; , pairs of VLE data; ···, residue curves).

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AUTHOR INFORMATION

Corresponding Author

*Tel.: +86-87671944. Fax: +86-87671963. E-mail: wsgmdzs@ 163.com. Funding

This work was supported by the National Natural Science Foundation of China (Grant No. 21376166). Notes

The authors declare no competing financial interest. F

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