Isobaric Vapor–Liquid Equilibrium for Binary Systems of Allyl Alcohol

Article pubs.acs.org/jced

Isobaric Vapor−Liquid Equilibrium for Binary Systems of Allyl Alcohol with Water, Methanol, and Ethanol at 101.3 kPa Lianzheng Zhang,† Yangchen Gao,‡ Dongmei Xu,† Zhishan Zhang,† Jun Gao,*,† and Dhakal Pratik† †

College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266590, China College of Material and Chemical Engineering, Hainan University, Haikou, 570228, China

‡

ABSTRACT: Isobaric vapor−liquid equilibrium (VLE) data for three binary systems of (allyl alcohol + water), (allyl alcohol + methanol), and (allyl alcohol + ethanol) were measured at atmospheric pressure of 101.3 kPa by a modified Rose vapor recirculating type equilibrium still. The thermodynamic consistency test for the experimental data of the three binary systems containing allyl alcohol were checked by Herington method and van Ness test, respectively. Meanwhile, the measured VLE data were correlated by three activity coefficient models of Wilson, nonrandom two-liquid (NRTL), and universal quasichemical (UNIQUAC), for which all of the calculated results showed good consistency. The binary interaction parameters of the models were also regressed. The azeotropic behavior could not be observed in (allyl alcohol + methanol) and (allyl alcohol + ethanol) systems, but for (allyl alcohol + water) system, the azeotropic behavior was found, and it had the minimum azeotropic point.

1. INTRODUCTION Trimethylolpropane diallyl ether is known as resin air drying agent, which is widely used in the coating industry. Because of the air drying property of the resin can be improved obviously due to the air-dried group. So trimethylolpropane diallyl ether has an extensively used in produce the air-drying resin of unsaturated polyester,1 oil-free alkyd resin, UV cured resin,2 and so forth. Few works have been presented regarding the process on the synthesis trimethylolpropane diallyl ether in the form of patent.3,4 Considering trimethylolpropane is solid, alcohols are chosen as the reaction solvent due to its good ability in dissolving trimethylolpropane. During the general synthesis, allyl alcohol can be produced as a byproduct in the aqueous solution. Therefore, the vapor−liquid equilibrium data for allyl alcohol is needed which can be used for its separation. Thus, the vapor−liquid equilibrium behavior for the three systems of (allyl alcohol + water), (allyl alcohol + methanol), and (allyl alcohol + ethanol) were measured at pressure of 101.3 kPa by a modified Rose type still. In previous works, the VLE behavior of systems containing allyl alcohol has been investigated by some researchers. The binary systems of allyl alcohol + benzene, cyclohexane,5 and 1-propanol6 were reported by Lubomska. Kumar measured the isobaric VLE behavior for mixtures of allyl alcohol + 1,2-dichloroethane,7 1,1,2,2-tetrachloroethane,8 and 1,1,1-trichloroethane,9 respectively. Meanwhile, isobaric binary VLE behavior for systems allyl alcohol with toluene10 and isopropylbenzene11 were determined by Rao and Kumar, respectively. However, the VLE behavior for systems of allyl alcohol with methanol and ethanol have not been found in the NIST and the DDB (Dortmund Data Bank). Grabner12 determined the isobaric VLE data of allyl alcohol + water at 101.3 kPa, and the other researchers reported the VLE data of allyl alcohol + water at different pressures or salt effect to the VLE of allyl alcohol + water system.13−16 Although the binary system of allyl alcohol + water © XXXX American Chemical Society

has already been studied, the system was also studied to test and verify the apparatus. The isobaric vapor−liquid equilibrium for (allyl alcohol + water), (allyl alcohol + methanol), and (allyl alcohol + ethanol) systems were measured at pressure of 101.3 kPa. The vapor− liquid equilibrium data were determined by a modified Rose type still, and all of the obtained data were checked by the thermodynamic consistency test method of Herington17 and van Ness. All of the experimental data were correlated by Wilson,18 NRTL,19,20 and UNIQUAC21 models, respectively, which the binary interaction parameters were also regressed. The main objective of the presented work was to explore the phase behavior of those three binary systems. Moreover, it also can provide some basic data for the separation process optimization and design.

2. EXPERIMENTAL SECTION 2.1. Chemicals. All chemicals were obtained commercially, and all of them were analytical pure reagents, which the purities of those reagents were checked and confirmed by GC, and no impurity peak was emerged. Thus, the reagents were used without purification. Ultrapure water was used during all the experiments. The relevant detailed information about the chemical reagents used in this work are shown in Table 1. The physical properties of density and refractive index were further ascertained for all reagents. The density was measured at 293.15 K by using the Dahometer DH-120N densimeter (Beijing Yitenuo Electronic Technology Co., Ltd.), which the accuracy was 0.0005 g cm−3. The refractive index was measured by the 2AWJ refractometer (Shanghai Experimental Instrument Co., Ltd.) at Received: December 10, 2015 Accepted: May 11, 2016

A

DOI: 10.1021/acs.jced.5b01048 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 1. Suppliers and Mass Fractions of the Chemical Reagent component

CAS

suppliers

allyl alcohol

107-18-6

methanol

67-56-1

ethanol

64-17-5

Chengdu Kelong Chemical Co., Ltd. Tianjin Fuyu Fine Chemical Co., Ltd. Tianjin Fuyu Fine Chemical Co., Ltd.

a

Table 3. Analysis Conditions for the Gas Chromatography name

mass fraction

purification method

analysis method

≥0.99

none

GCa

0.995

none

GCa

0.997

none

GCa

column

carrier gas

injector

Gas chromatograph. detector

293.15 K for which the measurement range was 1.3000−1.7000 with an accuracy of 0.0002. Both the measured and the literature values are presented in Table 2. 2.2. Apparatus and Procedures. A modified Rose type recirculating equilibrium still was used to measure the VLE data which was presented in detail in the previous work.22,23 The reliability of the equipment was checked. And the temperature was determined by an accurate mercury thermometer (Tianjin Glass Instrument Factory). The pressure was maintained with a manometer (Nanjing Hengyuan Automatic Gauge Co., Ltd.) and because of the two-step automatic control scheme, the pressure fluctuation was controlled within 0.03 kPa. The uncertainties of pressure and temperature are 0.1 kPa and 0.02 K. To reach the equilibrium state as soon as possible, both of the liquid phase and the condensed vapor phase were consecutively recirculated which would present close touch of the phases. During the measurement, the equilibrium state was obtained after maintained a constant temperature of vapor phase for at the least of 50 min. Then both the vapor and the liquid samples were withdrawn into a gas chromatograph vials immediately for analysis. The gas chromatograph vial was filled as much as possible to avoid any loss of the volatile component. 2.3. Analysis. The compositions of liquid phase and condensed vapor phase were all determined by GC (SP 6890) which were equipped with a capillary column and a thermal conductivity detector (Shandong Lunan Ruihong Chemical Instruments Co., Ltd.). The samples of the two phases were checked three times, and the mean value was adopted. The detailed analysis conditions of the gas chromatography are presented in Table 3. For each sample analysis, the peak area of GC was calibrated by five different standard samples that covered the whole composition range. The standard samples were prepared gravimetrically, and the gravimetrical weighed uncertainty was 0.0001 g. Each standard sample was checked four times to make sure that a high accuracy of the VLE measurement could be obtained. With the N2000 workstation software developed by Zhejiang University, the compositions of all samples were obtained. Then the mole compositions were compared with those obtained by mass. The uncertainty of mole fraction was 0.001.

characteristic

description

type packing temperature type flow rate pressure injection volume split ratio temperature type current temperature

20 m × 6 mm Porapak Q-S 80/100 453.15 K hydrogen 30 mL min−1 0.3 MPa 1 μL 5:1 473.15 K thermal conductivity detector (TCD) 100 mA 473.15 K

3. RESULTS AND DISCUSSION 3.1. Experimental Data. The vapor−liquid equilibrium data for allyl alcohol with water, methanol, and ethanol systems were determined at pressure of 101.3 kPa, which were all expressed in mole fraction and shown in Table 4, and the equilibrium phase diagrams of those VLE data are presented in Figures 1−4, respectively. The azeotropic behavior was found for the allyl alcohol + water system as reported by Grabner,12 but for the other two systems of allyl alcohol with methanol and ethanol, the azeotropic behavior could not be observed. 3.2. VLE Calculation. The VLE relationship is usually expressed as follows: ⎛ V l(P − P S) ⎞ i S S ⎜⎜ i yi φi V P = xiγφ P exp ⎟⎟ i i i RT ⎠ ⎝

(1)

φSi

Since the pressure was 101.3 kPa, the Poynting factor, and φVi associated with nonideality were all close to 1. Considering the nonidealities of the liquid phase, γi for the three systems can be calculated by eq 2, and all results are presented in Table 4: Py γi = S i Pi xi (2) where xi presents mole fraction of component i in vapor phase and yi presents mole fraction of component i in liquid phase; P is the system pressure, 101.3 kPa, and PSi is the saturation pressure of pure component i, which was obtained by the extended Antoine expression. The extended Antoine expression is shown as follows: ln(PiS/kPa) = C1i + + C6iT C7i

C 2i + C4iT + C5i ln T T + C 3i

for C8i ≤ T ≤ C9i

(3)

The constant values for all components were obtained directly from the Aspen databank24 and presented in Table 5.

Table 2. Molecular Weights (M), Boiling Temperatures (Tb), Density (ρ), and Refractive Index (n) at 293.15 K under Pressure P = 101.3 kPaa ρ/g·cm−3

a

−1

component

M/g mol

allyl alcohol methanol ethanol water

58.08 32.04 46.07 18.02

n

Tb/K

exp.

lit.

exp.

lit.

369.7529 337.8529 351.5529 373.1529

0.8540 0.7922 0.7900 0.9984

0.8573b,29 0.791030 0.788231 0.998233

1.4119 1.3276 1.3616 1.3328

1.413529 1.328430 1.361632 1.333033

The uncertainty of u is u(ρ) = 0.0005 g cm−3, u(n) = 0.0002, u(T) = 0.02 K, and u(P) = 1 kPa. bDetermined at 15 °C. B

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Table 4. Isobaric Experimental VLE Data of Liquid Phase (Mole Fraction), x1, Vapor Phase (Mole Fraction), y1, Activity Coefficient, γ1, and the Absolute Deviation between the Experimental and Calculated Values of Temperature, ΔT, Mole Fractions of the Vapor Phase, Δy, Results for the Three Binary Systems at P = 101.3 kPaa Wilson no.

a

T/K

x1

y1

γ1

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

372.95 372.08 371.21 370.13 369.04 367.79 366.88 364.90 363.83 362.88 362.41 362.68 363.66 364.93 366.07 367.13 368.04 368.70 369.23 369.80

0.001 0.004 0.008 0.013 0.020 0.032 0.043 0.085 0.129 0.272 0.401 0.535 0.736 0.821 0.875 0.913 0.944 0.963 0.978 0.995

0.008 0.043 0.075 0.115 0.155 0.199 0.233 0.305 0.347 0.404 0.459 0.502 0.612 0.696 0.764 0.827 0.879 0.919 0.951 0.987

0.980 0.978 0.979 0.979 0.980 0.984 0.986 1.006 1.034 1.171 1.315 1.543 2.040 2.248 2.394 2.424 2.547 2.519 2.514 2.874

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

368.20 366.33 365.08 363.52 360.76 359.42 356.69 352.37 348.47 347.68 345.86 343.81 341.97 339.19 338.82

0.967 0.937 0.907 0.874 0.811 0.775 0.707 0.575 0.455 0.419 0.355 0.280 0.197 0.078 0.057

0.903 0.815 0.754 0.685 0.568 0.512 0.435 0.305 0.211 0.186 0.144 0.095 0.060 0.019 0.012

1.027 1.025 1.025 1.025 1.017 1.011 1.046 1.073 1.101 1.093 1.076 0.979 0.963 0.876 0.777

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

370.11 369.50 367.14 366.08 364.45 363.53 362.01 361.55 360.94 359.58 358.54 357.71 356.86 356.01 354.50 352.92

0.993 0.973 0.886 0.843 0.776 0.738 0.664 0.640 0.609 0.545 0.488 0.436 0.383 0.333 0.240 0.129

0.987 0.953 0.799 0.735 0.642 0.588 0.500 0.473 0.443 0.375 0.325 0.280 0.241 0.195 0.130 0.063

1.020 1.027 1.031 1.036 1.045 1.042 1.043 1.041 1.050 1.046 1.054 1.050 1.065 1.023 1.008 0.966

γ2

ΔT/K

Allyl Alcohol (1) + Water (2) 9.043 0.01 10.45 0.05 9.619 0.06 8.933 0.04 8.143 0.01 7.029 0.12 6.327 0.16 4.472 0.13 3.477 0.03 1.990 0.14 1.561 0.05 1.267 0.25 1.082 0.05 1.052 0.03 1.038 0.00 1.036 0.08 1.030 0.07 1.030 0.10 1.030 0.09 1.029 0.02 Allyl Alcohol (1) + Methanol (2) 0.973 0.08 1.035 0.06 0.974 0.28 0.968 0.35 0.972 0.31 0.963 0.35 0.944 0.03 0.931 0.04 0.949 0.35 0.945 0.13 0.958 0.19 0.981 0.25 0.978 0.04 0.990 0.09 0.989 0.01 Allyl Alcohol (1) + Ethanol (2) 0.914 0.27 0.875 0.11 0.959 0.07 0.959 0.06 0.960 0.02 0.978 0.04 0.978 0.06 0.979 0.09 0.973 0.09 0.988 0.07 0.986 0.13 0.985 0.12 0.980 0.14 0.994 0.23 0.998 0.36 0.998 0.35

NRTL

UNIQUAC

Δy1

ΔT/K

Δy1

ΔT/K

Δy1

0.001 0.003 0.002 0.002 0.001 0.002 0.001 0.004 0.013 0.014 0.025 0.012 0.004 0.003 0.003 0.003 0.000 0.003 0.002 0.001

0.02 0.07 0.08 0.11 0.11 0.03 0.02 0.17 0.11 0.15 0.05 0.13 0.16 0.12 0.07 0.05 0.06 0.09 0.09 0.01

0.001 0.003 0.003 0.004 0.004 0.000 0.000 0.005 0.002 0.005 0.026 0.019 0.000 0.001 0.002 0.003 0.000 0.003 0.003 0.001

0.01 0.06 0.06 0.05 0.02 0.04 0.05 0.02 0.12 0.02 0.18 0.08 0.04 0.15 0.15 0.16 0.08 0.07 0.06 0.02

0.001 0.003 0.002 0.002 0.001 0.002 0.001 0.001 0.002 0.001 0.013 0.006 0.001 0.003 0.003 0.006 0.001 0.002 0.001 0.001

0.001 0.008 0.000 0.001 0.013 0.016 0.008 0.003 0.010 0.011 0.009 0.000 0.002 0.000 0.001

0.08 0.12 0.19 0.25 0.29 0.39 0.12 0.02 0.45 0.25 0.34 0.40 0.15 0.13 0.04

0.000 0.009 0.000 0.000 0.007 0.009 0.002 0.002 0.005 0.006 0.005 0.003 0.001 0.000 0.001

0.08 0.13 0.16 0.22 0.26 0.37 0.13 0.01 0.44 0.26 0.37 0.44 0.20 0.15 0.05

0.000 0.009 0.000 0.000 0.006 0.007 0.002 0.005 0.006 0.006 0.004 0.003 0.001 0.000 0.001

0.000 0.001 0.001 0.002 0.008 0.005 0.005 0.006 0.008 0.002 0.003 0.003 0.006 0.003 0.002 0.002

0.27 0.11 0.07 0.05 0.01 0.04 0.06 0.08 0.08 0.08 0.14 0.12 0.14 0.23 0.36 0.35

0.000 0.001 0.001 0.003 0.009 0.005 0.006 0.005 0.008 0.002 0.004 0.003 0.005 0.003 0.003 0.002

0.27 0.12 0.07 0.07 0.02 0.05 0.06 0.09 0.09 0.07 0.13 0.11 0.14 0.23 0.36 0.36

0.000 0.001 0.001 0.002 0.008 0.005 0.006 0.005 0.008 0.003 0.004 0.003 0.006 0.003 0.003 0.002

Standard uncertainties u of temperature T, composition x1, y1, and pressure P are u(T) = 0.02 K, u(x1) = u(y1) = 0.001, and u(P) = 0.1 kPa.

C

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Figure 1. Equilibrium diagram for the binary system allyl alcohol (1) + water (2) at 101.3 kPa: ■, T−x for experimental data; ●, T−y for experimental data; □, T−x for literature data, ○, T−y for literature data;12 - - -, Wilson; •••, NRTL; , UNIQUAC.

Figure 3. Equilibrium diagram for the binary system allyl alcohol (1) + methanol (2) at 101.3 kPa: ●, T−x for experimental data; ○, T−y for experimental data; - - -, Wilson; •••, NRTL; , UNIQUAC.

Figure 2. Equilibrium diagram for the binary system allyl alcohol (1) + methanol (2) at 101.3 kPa: ▲, T−x for experimental data; △, T−y for experimental data; - - -, Wilson; •••, NRTL; , UNIQUAC.

Figure 4. Experimental and calculated y1−x1 diagram for the binary system allyl alcohol (1) + water (2) at 101.3 kPa: ■, experimental data; ○, literature data;12 - - -, Wilson; •••, NRTL; , UNIQUAC.

3.3. Consistency Check of the Experimental Data. The consistencies of experimental data for the three binary systems were checked by Herington area method,17,25 which was a semiempirical method used to confirm the reliability of the measurement. With the method, the experimental data would pass the test, if the values of |D-J| was smaller than 10.26 D and J are defined as follows:

Besides the Herington check, the measured data also passed the van Ness test,27,28 which was applied to confirm the reliability of VLE data. This check requires that Δy should be less than 1, which means that the measured point was reliable. Δy was the mean absolute deviation between the experimental mole fractions and the calculated results of the component i in the vapor phase. The criterion is presented as follows:

D = 100

J = 150

A−B A+B

ΔTmax Tmin

Δy =

(4)

1 N

N

∑ 100|yiexp − yical | i=1

(6)

where N is the experimental point number; exp stands for measured data, and cal stands for the calculated results by the NRTL model. The mean absolute deviation for the binary systems (allyl alcohol + water), (allyl alcohol + methanol), and (allyl alcohol + ethanol) were 0.419, 0.343, and 0.372, respectively, and all of them were less than 1, which confirmed that the measured data were reliable, which indicates that all the measured VLE data passed the thermodynamic consistency test.

(5)

where A is the area above the zero line on the diagram of ln(γ1/γ2) vs x, B is the area under the zero line on this diagram; ΔTmax = Tmax − Tmin (K), Tmin and Tmax are the lowest and the highest boiling temperature, respectively. The values of |D−J| for (allyl alcohol + water), (allyl alcohol + methanol), and (allyl alcohol + ethanol) systems were 0.010, 9.668, and 4.671, respectively. D

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Table 5. Parameters of the Extended Antoine Equationa

a

compound

C1i

C2i

C3i

C4i

C5i

C6i (× 106)

C7i

C8i/K

C9i/K

allyl alcohol methanol ethanol water

77.83 75.81 66.40 66.74

−8057.60 −6904.50 −7122.30 −7258.20

0 0 0 0

0 0 0 0

−8.71 −8.86 −7.14 −7.30

1.66 × 10−11 7.47 2.89 4.17

6.00 2.00 2.00 2.00

144.15 175.47 159.05 273.16

545.10 512.50 514.00 647.10

Taken from Aspen property databank.

Table 6. Binary Interaction Parameters, the Root-Mean-Square Deviation (RMSD) and the Average Absolute Deviations (AAD) for the Equilibrium Temperature (T) and Mole Fractions of the Vapor Phase (y1) of the Wilson, NRTL, and UNIQUAC Activity Coefficient Models binary interaction parameters model

aij

Wilson NRTL UNIQUAC

1.26 8.30 −25.87

4.45 1.77 22.70

Wilson NRTL UNIQUAC

−3.15 −12.92 7.13

21.20 3.87 −2.54

Wilson NRTL UNIQUAC

−21.30 −26.62 14.25

20.72 26.09 −14.4

aji

bij/K

RMSD bji/K

Allyl Alcohol (1) + Water (2) −512.61 −2470.58 −2187.23 −707.69 0.3 9385.22 −8394.46 Allyl Alcohol (1) + Methanol (2) 1461.93 −8278.20 5269.95 −1802.39 0.3 −2935.72 1145.90 Allyl Alcohol (1) + Ethanol (2) 7668.27 −7467.49 9618.36 −9418.73 0.3 −5138.09 5170.24

j

where ln Aij = aij +

∑ j

bij T

∑j xjτjiGji ∑k xkGki

∑ j

⎛ ∑ x τ G ⎞ ⎜⎜τij − m m mj mj ⎟⎟ ∑k xkGkj ⎠ ∑k xkGkj ⎝ xjGij

(8)

where τij = aij +

bij T

Gij = exp( −αijτij).

;

UNIQUAC: ln γi = ln

Φi θ z + qi ln i − qit ln tit − xi 2 Φi

+ qit −

(

Φi xi

where τij = exp aij +

∑j θjtτij t qi t jt

bij T

0.008 0.008 0.004

0.10 0.10 0.09

0.005 0.004 0.003

0.08 0.09 0.07

0.008 0.005 0.004

0.21 0.25 0.25

0.006 0.003 0.003

0.17 0.21 0.22

0.004 0.004 0.004

0.17 0.17 0.17

0.003 0.003 0.004

0.14 0.14 0.14

(10)

+ li

ΔTi = |Ti ,exp − Ti ,cal|

(11)

Δyi = |yi ,exp − yi ,cal |

(12)

∑ xjlj

N

(9)

j

δ(T)

where N presents experimental data number; σ presents the standard deviation; x, y, T, and P are mole fractions in liquid phase and vapor phase, equilibrium temperature, and pressure, respectively; and superscripts of cal and exp presents the calculated results and experimental data, respectively. The regressed interaction parameters of the three models are given in Table 6. The absolute deviation between the experimental and calculated values were presented in Table 4, and the root-mean-square deviation (RMSD) and the average absolute deviation (AAD) for the temperature (T) and the mole fraction of the vapor phase (y1) for the three models given in Table 6, are expressed as follows:

(7)

.

+

δ(y1)

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

NRTL: ln γi =

T/K

N

Aji xj ∑k Ajk xk

AAD

y1

⎡⎛ exp cal ⎞2 ⎛ P exp − P cal ⎞2 ⎢⎜ Ti − Ti ⎟ i i ⎟⎟ OF = ∑ ⎢⎜ ⎟ + ⎜⎜ P T σ σ ⎝ ⎠ ⎝ ⎠ i=1 ⎣

3.4. VLE Data Correlation. The VLE data of (allyl alcohol + water), (allyl alcohol + methanol), and (allyl alcohol + ethanol) at 101.3 kPa were correlated by the Wilson,18 NRTL,19,20 and UNIQUAC21 models as follows. Wilson: ln γi = 1 − ln(∑ Aij xj) −

α

RMSD(y) =

∑ i=1

)

(yical − yiexp )2 N

(13)

. N

The interaction parameters of the models were obtained by minimizing the following objective equation according to the maximum likelihood method:

RMSD(T ) =

∑ i=1

E

(Tical − Tiexp)2 N

(14)

DOI: 10.1021/acs.jced.5b01048 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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δ(T ) =

1 n 1 n

■

n

∑ |y1cal

− y1exp |

1

(15)

1

aij, bij parameters of the NRTL model Aij parameters of the Wilson model AAD average absolute deviation C1i, C2i, ..., C9i coefficients of the extended Antoine equation D, J variables used in Herington consistency test M mole weights MAD maximum absolute deviation n refractive index N number of data points OF objective function P pressure (kPa) q van der Waals surface area of molacular r van der Waals volume of molecular R gas constant (J mol−1 K−1) RMSD root-mean-square deviation T absolute temperature (K) Tb boiling temperature u standard uncertainties V molar volume x mole fraction in the liquid phase y mole fraction in the vapor phase Z coordination number

(16)

For the three binary systems of (allyl alcohol + water), (allyl alcohol + methanol), and (allyl alcohol + ethanol), the calculated results and the determined data are compared graphically in Figures 1−4, respectively. It is obviously to be seen that, in Table 6, the AAD of the vapor compositions, the equilibrium temperatures between the calculated results and the experimental data are less than 0.006 and 0.22, respectively. The previous VLE data reported by Grabner12 for the binary system of allyl alcohol + water was presented in Figures 1 and 4. As can be seen from Figures 1 and 4, the determined VLE data are close to the reported literature data. Meanwhile, it revealed the azeotropic behavior of this binary system, and the azeotropic point was found to be x1 = 0.452 and T = 362.49 K compared with those values x1 = 0.447 and T = 362.05 K in the literature.29 The two binary systems of allyl alcohol with methanol and ethanol are plotted in Figures 2 and 3, which indicates that the regressed values agreed well with the experimental data. Therefore, the Wilson, NRTL, and UNIQUAC models were all suitable for the investigated binary systems.

Greek Letter

α nonrandomness parameter of the NRTL model γi activity coefficient ρ density (g cm−3) σ standard deviation τij parameters of the UNIQUAC model φ fugacity coffieients

4. CONCLUSIONS The isobaric vapor−liquid equilibrium data for the three binary systems of allyl alcohol with water, methanol, and ethanol were determined at pressure of 101.3 kPa by a modified Rose type still. The Herington area test and van Ness point to point test method were used to check the thermodynamic consistency of the experimental VLE data. |D − J| and Δy for the three systems were 0.010, 9.668, 4.671, and 0.419, 0.343, 0.372, respectively. Meanwhile, the minimum azeotropic point was found in the (allyl alcohol + water) binary system which the azeotropic composition and temperature were x1 = 0.452 and T = 362.49 K, respectively. On the contrary, there is no azeotropic point observed in the other two systems. The Wilson, NRTL, and UNIQUAC models were applied to correlate the measured VLE data for the three binary systems, which the calculated results were in good agreement with the experimental data. Meanwhile the corresponding interaction parameters were also regressed. All of the three models can give good performance in correlating the experimental data for the systems. Furthermore, the determined vapor−liquid equilibrium data and the regressed parameters provided the basis for the design and simulation of the distillation process.

■

NOMENCLATURE

List of Symbols

n

∑ |T1cal − T1exp|

Article

Superscripts and Subscripts

■

b normal boiling cal calculated values exp experimental data i, j components i and j ij pair interaction k data number l liquid phase v vapor phase S saturation state

REFERENCES

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Telephone: +86 532 8605 7798. Funding

This work was supported by the Project of Shandong Province Higher Educational Science and Technology Program (Project J13LD16). The authors are grateful for the financial support. Notes

The authors declare no competing financial interest. F

DOI: 10.1021/acs.jced.5b01048 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

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DOI: 10.1021/acs.jced.5b01048 J. Chem. Eng. Data XXXX, XXX, XXX−XXX