Measurement and Correlation of Isobaric Vapor–Liquid Equilibrium for

Article pubs.acs.org/jced

Measurement and Correlation of Isobaric Vapor−Liquid Equilibrium for Binary Systems of 1‑(Ethoxymethoxy)-2-methyl-propane with Isobutyl Alcohol or 1‑Butanol at 101.33 kPa Yu-He Song,*,†,‡ Shu-E Wang,§ Hui Hua,⊥ Juan Song,†,‡ Ping-He Wei,†,‡ and Cun-Fu Li†,‡ †

Jiangsu Key Laboratory of Chiral Pharmaceuticals Biosynthesis, and ‡Separation Engineering Research Group, College of Pharmacy and Chemistry & Chemical Engineering, Taizhou University, Taizhou 225300, P. R. China § Weifang College of Engineering Technician, Zhucheng City, Shandong 262200, China ⊥ Zhejiang Pharmaceutical College, Ningbo City, Zhejiang 315100, China S Supporting Information *

ABSTRACT: Experimental vapor−liquid equilibrium (VLE) data for binary systems of 1-(ethoxymethoxy)-2-methylpropane (EMMP) with isobutyl alcohol and 1-butanol at 101.33 kPa was measured. The measurements of saturated vapor pressure for EMMP were also measured. The experiment was performed by an improved Rose still. A minimum boiling azeotrope was found about the binary system containing 1-butanol for which the azeotropic temperature and composition are 389.64 K and 75.92 mol% (1-butanol) at 101.33 kPa. The VLE measurements were correlated by the Wilson, nonrandom two-liquid, and universal quasichemical models for which the results showed that the measurements had a good correlation by using three models about two binary systems, respectively. The thermodynamic consistency of the VLE measurements was checked by the traditional area test and the direct test methods.

1. INTRODUCTION

2. EXPERIMENTAL 2.1. Chemicals and Analysis. Ethanol and isobutyl alcohol were supplied from the Sinopharm Chemical Reagent. The EMMP (molecular structure in Figure 1) was synthesized by

Oxygenated compounds such as 1-(methoxymethoxy)-2methyl-propane (MMMP) and 1-(ethoxymethoxy)-2-methylpropane (EMMP) can be used as additives of gasoline or diesel. They can reduce soot formation and increase the combustion efficiency during combustion and can be synthesized from formaldehyde, methanol, ethanol, and isobutyl alcohol.1−3 However, before developing the separation technology of EMMP, the measurements of the vapor−liquid equilibrium (VLE) and the azeotropic state with alcohols (as the raw material) mixture must be clarified. The data of VLE and the azeotropic state are always required for engineering use such as in the design of a distillation process. Here, we have measured the isobaric VLE measurements at 101.33 kPa for binary mixtures composed of EMMP with isobutyl alcohol or 1butanol and the vapor pressure measurements of EMMP in this study to provide a reference for the development of distillation technology in the process of purifying the EMMP. In addition, the thermodynamics consistency of these VLE measurements was checked in the help of the traditional area test and direct test methods. These VLE data have been compared with the results correlated by the Wilson,4 nonrandom two-liquid (NRTL),5 and universal quasichemcial (UNIQUAC)6 models. © 2017 American Chemical Society

Figure 1. Molecular structure of EMMP.

using ethanol, isobutyl alcohol, and formaldehyde7 under 383.15 K and 1.0 MPa with the help of the acid catalyst, and purified by a complicated separation process that contains an alkali wash and reduced pressure distillation technology. An alkaline hydrogen peroxide solution was used in the process of washing, and the reduced-pressure distillation process was operated at 20 ± 1 kPa and 314 ± 2 K before removing water. The boiling portion of 332−402.5 K which separated at 101.0− 101.8 kPa was conveyed to the rectification under vacuum, and Received: April 22, 2017 Accepted: July 14, 2017 Published: July 27, 2017 2443

DOI: 10.1021/acs.jced.7b00377 J. Chem. Eng. Data 2017, 62, 2443−2449

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Table 1. Comparison of Density (ρ) at 293.15 K, Refractive Index (nD) at 298.15 K and the Boiling Points (Tb) at 101.33 kPa of the Pure Components with Literature Data ρ (293.15 K)(kg/m3)b

Tb (K)a

nD (298.15 K)b

component

this work

lit.

this work

lit.

this work

lit.

isobutyl alcohol

381.08

801.8

390.90

801.8d 802.0f 809.7f 809.5j

1.3939

1-butanol

381.04c 381.15f 390.81h 390.90f

1.3939e 1.3937g 1.3971i 1.3974k

EMMP

401.87

809.5

1.3971

823.8

1.3873

a

Standard uncertainties u are u(T) = 0.05 K, u(P) = 0.15 kPa. bStandard uncertainties u are u(T) = 0.2 K, u(P) = 0.3 kPa, u(ρ) = 0.0001 kg/m3, u(nD) = 0.0001. cStandard literature.8 dStandard literature.9 eStandard literature.10 fStandard literature.11 gStandard literature.12 hStandard literature.13 iStandard literature.14 jStandard literature.15 kStandard literature.16

the distillate of 401.8 K at 101.33 kPa was collected upon secondary rectification as the experimental chemical of EMMP. The rectification was operated by a rectifying tower whose theoretical plate number is 12 under the condition of reflux ratio at 3:1.

Table 2. Materials Description chemical name source molecular formula CASRN suppliers’ purity (wt %) purification method final purity (wt %) water content (wt %) analysis method

CH3CH 2OH + (CH 2O)n + (CH3)2 CHCH 2OH → CH3CH 2OCH 2OCH 2CH(CH3)2

(1)

The isobutyl alcohol and 1-butanol were purified by a separation process of the secondary rectification. The chemicals were tested by the Agilent gas chromatograph (GC) 7890B with a thermal conductivity detector (TCD). The type of chromatographic column used is porapak N (Hangzhou Kexiao Chemical Instrument Company, China), and the system used a flame ionization detector (FID) and a KB-5 capillary column (Kromat corporation, America) which failed to show any significant impurities. The results showed the purities of isobutyl alcohol, 1-butanol, and EMMP were ≥99.9 wt %. The temperature of detector, injector, and column box was set at 483.15 K and 393.15 to 453.15 K (programmed temperature, heating rate of 10 K/min). Quantitative results were acquired by the area normalization method in the process of analysis. The water content was ≤0.03 wt % of three chemicals and was analyzed by the GC7890B with TCD and porapak N. The detection limit of this GC for the water content in organic compounds is 0.001 wt %. The synthesized compounds in which the purity of EMMP is about 99.5 wt% was analyzed by NMR and GC−MS/MS. As additional purity checks, we tested the normal boiling points, densities (ρ), and refractive indices (nD) of three pure chemicals and compared these measurements to the literature values8−16 presented in Table 1. The methods of measurement and calculation for three physical property parameters have been described in our previous paper.17 The results showed that these measurements were basically consistent with literature data. We analyzed the compositions of vapor and liquid samples of the equilibrium state by the same GC. The operating condition has also been introduced.17 The sources and purity of the reagents are listed in Table 2. 2.2. Apparatus and Procedure. Similar to our previous work, the VLE measurements of two binary mixtures above at 101.33 kPa and the vapor pressure measurements of pure component EMMP were measured by a dynamic modified Rose still1 which is a typical experiment apparatus, and its total capacity is 150 mL. A detailed description about operation and veracity of the apparatus in measuring the VLE and vapor pressure value has been reported.3,17

isobutyl alcohol Sinopharm, China C4H10O 78-83-1 99.8

1-butanol

EMMP

Sinopharm, China C4H10O 71-36-3 99.8

homemade

distillation

distillation

99.9 0.03

99.9 0.02

distillation and dehydration 99.9 0.02

GC

GC

GC

C7H16O2 121601-45-4

First, EMMP was injected into the kettle, and the content of another compound in the kettle was increased to 100% at intervals. In experiment, we measured the temperature by using a precise standard mercury thermometer (Beijing Glass Research Institute Co., first-class) with an error range of less than 0.05 K. The apparatus must remain sealed throughout the experiment. The pressure was measured by a digital display vacuum measuring instrument (Taizhou Aide Mechanical and Electrical Technology Co., VR-208C-510A) with an error range of less than 0.02 kPa, which was controlled and adjusted to the setting value by two bottles (the volume is 5 L) of buffer and a sealed rubber tube (its length and inner diameter are 1 m and 0.8 cm, respectively) with a moving clip. The sealed apparatus was kept at 101.33 ± 0.02 kPa by the pressure control system. In the process of experiment, sufficient equilibrium could be established by continuous circulation of the liquid and vapor phase when the temperature remains constant for 60 min. Two samples of vapor and liquid (the volume is 2 mL, respectively) were withdrawn rapidly and simultaneously for anlaysis when sufficient equilibrium was obtained. The measurements of vapor pressure for pure component EMMP were also measured by the dynamic modified Rose still above. This operation method was similar to the description above. The difference is that the compound is only pure component EMMP in the still kettle. The temperature at the setting pressure was recorded as the vapor pressure measurements of pure component EMMP.

3. RESULTS AND DISCUSSION 3.1. Experimental Results. The isobaric VLE measurements for two binary mixtures composed of EMMP with isobutyl alcohol or 1-butanol at 101.33 kPa are listed in Tables 2444

DOI: 10.1021/acs.jced.7b00377 J. Chem. Eng. Data 2017, 62, 2443−2449

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Table 3. Experiment Data and Deviations Correlated of Isobutyl Alcohol (1) + EMMP (2) System by Wilson, NRTL, and UNIQUAC at 101.33 kPa Wilson x1expa

y1expa

γ1

γ2

α12b

1 401.87 0.0000 2 400.95 0.0180 3 396.31 0.0896 4 393.03 0.1604 5 389.98 0.2326 6 388.27 0.2981 7 386.68 0.3686 8 385.40 0.4480 9 384.59 0.5065 10 383.82 0.5712 11 383.10 0.6352 12 382.57 0.6951 13 382.09 0.7455 14 381.81 0.7902 15 381.64 0.8290 16 381.57 0.8450 17 381.48 0.8684 18 381.38 0.8910 19 381.26 0.9216 20 381.15 0.9556 21 381.10 0.9907 22 381.08 1.0000 maximum deviation average absolute deviation

0.0000 0.0546 0.2142 0.3334 0.4269 0.4919 0.5554 0.6154 0.6576 0.6960 0.7353 0.7719 0.8041 0.8306 0.8578 0.8692 0.8866 0.9034 0.9280 0.9581 0.9909 1.0000

1.5477 1.4161 1.3723 1.3440 1.2819 1.2370 1.1799 1.1474 1.1070 1.0792 1.0552 1.0428 1.0267 1.0167 1.0134 1.0092 1.0059 1.0031 1.0028 1.0023

0.9886 1.0068 1.0157 1.0432 1.0632 1.0842 1.1147 1.1374 1.1899 1.2450 1.3048 1.3621 1.4414 1.4920 1.5170 1.5530 1.6032 1.6664 1.7181 1.7780

3.1508 2.7697 2.6180 2.4576 2.2795 2.1399 1.9716 1.8713 1.7187 1.5953 1.4844 1.4013 1.3018 1.2443 1.2190 1.1848 1.1441 1.0965 1.0624 1.0222

no.

Texp (K)a

NRTL

UNIQUAC

ΔTc

Δy1c

ΔTc

Δy1c

ΔTc

Δy1c

−0.16 −0.57 −0.37 −0.34 0.13 0.04 0.04 −0.11 −0.18 −0.23 −0.20 −0.23 −0.16 −0.18 −0.25 −0.26 −0.28 −0.28 −0.27 −0.25 −0.25 −0.25 −0.57 0.23

0.0000 0.0000 0.0101 0.0106 0.0099 0.0127 0.0106 0.0098 0.0069 0.0091 0.0085 0.0077 0.0059 0.0074 0.0056 0.0050 0.0040 0.0038 0.0027 0.0009 0.0000 0.0000 0.0127 0.0060

−0.16 −0.56 −0.36 −0.33 0.14 0.03 0.03 −0.12 −0.19 −0.23 −0.21 −0.23 −0.16 −0.18 −0.25 −0.26 −0.28 −0.27 −0.27 −0.25 −0.25 −0.25 −0.56 0.23

0.0000 −0.0002 0.0098 0.0106 0.0102 0.0131 0.0111 0.0102 0.0072 0.0092 0.0085 0.0075 0.0057 0.0072 0.0054 0.0049 0.0039 0.0037 0.0027 0.0009 0.0001 0.0000 0.0131 0.0060

−0.16 −0.49 −0.20 −0.21 0.20 0.07 0.05 −0.11 −0.18 −0.23 −0.21 −0.23 −0.16 −0.18 −0.24 −0.25 −0.27 −0.26 −0.26 −0.24 −0.25 −0.25 −0.49 0.21

0.0000 −0.0025 0.0044 0.0042 0.0026 0.0041 0.0008 −0.0009 −0.0040 −0.0016 −0.0014 −0.0009 −0.0011 0.0019 0.0016 0.0017 0.0016 0.0022 0.0021 0.0010 0.0002 0.0000 0.0044 0.0019

a

Standard uncertainties u are u(T) = 0.05 K, u(P) = 0.15 kPa, and u(x1) = u(y1) = 0.0020. bRepresents the relative volatility. The antoine equation used is αij = yi /yj /xi/xj . cΔT = (Tcal − Texp), Δy1 = (y1cal − y1exp).

Table 4. Experiment Data and Deviations Correlated of 1-Butanol(1) + EMMP (2) System by Wilson, NRTL, and UNIQUAC at 101.33 kPa Wilson x1expa

y1expa

γ1

γ2

α12b

1 401.87 0.0000 2 400.79 0.0233 3 397.45 0.1127 4 394.96 0.1926 5 393.43 0.2630 6 392.28 0.3350 7 391.25 0.4248 8 390.35 0.5169 9 389.98 0.5830 10 389.79 0.6448 11 389.69 0.6944 12 389.67 0.7424 13 389.74 0.7946 14 389.82 0.8358 15 389.94 0.8792 16 390.11 0.9259 17 390.20 0.9403 18 390.43 0.9648 19 390.72 0.9905 20 390.90 1.0000 maximum deviation average absolute deviation

0.0000 0.0542 0.2078 0.3138 0.3918 0.4557 0.5256 0.5890 0.6360 0.6763 0.7106 0.7453 0.7856 0.8208 0.8610 0.9074 0.9245 0.9533 0.9870 1.0000

1.6504 1.4651 1.4106 1.3601 1.2935 1.2201 1.1606 1.1259 1.0901 1.0672 1.0477 1.0292 1.0192 1.0120 1.0068 1.0067 1.0033 1.0015

0.9987 1.0089 1.0295 1.0437 1.0700 1.1101 1.1757 1.2192 1.2800 1.3344 1.3938 1.4685 1.5323 1.6094 1.7401 1.7557 1.8290 1.8713

2.4022 2.0652 1.9171 1.8052 1.6619 1.5002 1.3394 1.2498 1.1509 1.0806 1.0153 0.9472 0.8999 0.8511 0.7842 0.7774 0.7448 0.7282

no.

Texp (K)a

NRTL

UNIQUAC

ΔTc

Δy1c

ΔTc

Δy1c

ΔTc

Δy1c

−0.16 −0.23 −0.33 −0.04 0.05 0.08 0.06 0.19 0.18 0.13 0.10 0.06 0.01 0.00 0.02 0.11 0.12 0.09 0.07 0.00 −0.57 0.23

0.0000 −0.0003 0.0079 0.0075 0.0042 0.0050 0.0049 0.0058 0.0028 0.0035 0.0030 0.0023 0.0016 0.0004 −0.0006 0.0005 −0.0005 −0.0001 −0.0003 0.0000 0.0127 0.0060

−0.16 −0.22 −0.32 −0.03 0.05 0.07 0.05 0.18 0.17 0.12 0.10 0.06 0.00 0.00 0.02 0.11 0.12 0.09 0.07 0.00 −0.56 0.23

0.0000 −0.0005 0.0077 0.0077 0.0047 0.0055 0.0054 0.0061 0.0028 0.0033 0.0027 0.0020 0.0013 0.0001 −0.0008 0.0005 −0.0005 −0.0001 −0.0002 0.0000 0.33 0.10

−0.16 −0.19 −0.26 0.00 0.04 0.04 −0.01 0.11 0.09 0.05 0.03 0.00 −0.04 −0.03 0.01 0.11 0.13 0.10 0.07 0.00 0.0079 0.0026

0.0000 −0.0016 0.0054 0.0054 0.0023 0.0031 0.0028 0.0033 0.0000 0.0005 0.0000 −0.0005 −0.0008 −0.0015 −0.0017 0.0004 −0.0004 0.0003 0.0000 0.0000 0.32 0.10

a Standard uncertainties u are u(T) = 0.05 K, u(P) = 0.15 kPa, and u(x1) = u(y1) = 0.0020. bRepresent the relative volatility. The antoine equation used is αij = yi /yj /xi/xj . cΔT = (Tcal − Texp), Δy1 = (y1cal − y1exp).

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Table 5. Experimental Saturated Vapor Pressure Data and Relative Derivations (Δ) from eq 6 for EMMP at Different Temperaturesa

a

no.

Tb (K)

P (kPa)

Δb

no.

Tb (K)

P (kPa)

Δb

1 2 3 4 5 6 7

320.54 335.10 344.53 351.76 359.38 370.93 379.83

5.00 10.00 15.00 20.02 26.67 39.90 53.33

0.0000 0.0003 −0.0007 −0.0001 0.0003 0.0016 −0.0002

8 9 10 11 12 13

386.16 393.18 397.46 401.87 405.77 410.02

64.80 79.60 89.90 101.33 112.00 125.00

−0.0009 −0.0013 −0.0026 −0.0019 0.0015 0.0016

Standard uncertainties u are u(T) = 0.05 K and u(P)/kPa = 0.02 + 0.0015(p/kPa). bΔ = (Pcal − Pexp)·Pcal.

Table 6. Parameters in the Antoine Equation and Structure Parameters in the UNIQUAC Equation component c

isobutyl alcohol 1-butanold EMMPe

A

B (K)

C (K)

T range (K)a

RAD%

lb

qb

14.8538 22.10877 19.55511

−2874.72 −3137.02 −2397.51821

−100.30 −94.43 −103.33159

293.00−405.00 288.00−404.00 315.00−410.00

0.070

3.45353 3.45419 5.71918

3.048 3.048 4.984

0.100

a

Standard uncertainties u are u(T) = 0.05 K and u(P)/kPa = 0.02 + 0.0015(p/kPa). bThe structure parameters used in the UNIQUAC equation are from the APV80 VLE-IG database of Aspen plus. cStandard literature.20 The antoine equation used is

ln pis (kPa) = A +

B T (K) + C

d Standard literature.21 The Antoine equation used is eq 6. eParameters of 1-(ethoxymethoxy)-2-methyl-propane were correlated using the saturated vapor pressure data shown in Table 5 according to eq 6.

psi represents the vapor pressure of pure component i under the different equilibrium temperature, which is calculated by eq 6, and these Antoine parameters are listed in Table 6. B ln pis (Pa) = A + T (K) + C (6)

3 and 4. The measurements of vapor pressure of pure component EMMP are listed in Table 5. 3.2. Thermodynamic Consistency. The thermodynamic consistency for VLE measurements of two binary systems was checked by using the Herington semiempirical method, under normal conditions the value of D − J must be less than 10; the D and J values are calculated by the following Eq. 2 and (3):18,19 D=

|I | × 100 ∑

The results of thermodynamic consistency for VLE measurements are listed in Table 7 and Figures 2 and 3, which indicate Table 7. Thermodynamic Consistency Test of VLE Data

(2) system

θ J = 150 × Tmin ∫ 10ln(γ1/γ2) dx1,

isobutyl alcohol(1) + EMMP 1-butanol(1) + EMMP

(3)

I= ∑= θ = Tmax − Tmin. The Tmin and Tmax are the lowest and the highest boiling point (K) in two binary systems measurements, respectively. The equilibrium relationship about the liquid and vapor phase is expressed by the following eq 4: V

yi φi p =

s s xiγφ p i i i

Tmin (K)

D

J

D−J

401.87

381.08

11.024

8.176

2.848

401.87

389.65

6.536

4.705

1.831

∫ 10|ln(γ1/γ2)| dx1,

⎛ V l(p − ps ) ⎞ i i ⎟ exp⎜⎜ ⎟ RT ⎝ ⎠

that our experimental data have passed the consistency test of thermodynamics. The relative absolute deviations (RAD) between the experimental and calculated vapor pressures are shown in Table 5 and Figure 4, calculated in accordance to eq 7, which indicates that their Antoine equation parameters were able to predict the vapor pressure of the studied components with high reliability under the entire experimental data set.

(4)

In the above equation, P and T are the total pressure and equilibrium temperature. φVi represents the fugacity coefficient of component i in the vapor mixture. φSi represents the fugacity coefficient of pure vapor i at the state of equilibrium. As is well known, eq 5 is modified Raoult’s law. Considering the experimental operation at 101.33 kPa and assuming the vapor phase as an ideal gas, we neglect the pressure effect of the liquid phase fugacity in the eq 5: yp = xiγipis i

Tmax (K)

RAD% =

∑ |Pcal ‐Pexp| /Pexp N

·100

(7)

3.3. Correlations for VLE. The isobaric VLE measurements for two binary mixtures composed of EMMP with isobutyl alcohol or 1-butanol at 101.33 kPa were correlated by the Wilson, NRTL, and UNIQUAC models with the maximum-likelihood method. The binary interaction parameters α, aij, bij, the average absolute deviations about the equilibrium temperature, and vapor phase mole fraction of two VLE systems above were listed in Table 8. These binary

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Figure 2. Diagram of ln(γ1/γ2) to x1 for the isobutyl alcohol(1) and EMMP(2) system.

Figure 4. Relative deviations ΔP/P between calculated and experimental values for EMMP.

The γi can be calculated as follows: Wilson: ln γi = 1 − ln(∑ Aij xj) − j

∑ j

Aji xj ∑k Ajk xk

(11)

NRTL: γi =

∑j xjτjiGji ∑k xkGki

+

∑ j

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

(12)

UNIQUAC: ln γi = ln

ϕi xi

+ 5qi ln

− q′i ∑ Figure 3. Diagram of ln(γ1/γ2) to x1 for the 1-butanol(1) and EMMP(2) system.

j

Wilson:

(8)

NRTL: τij = aij +

bij T

(9)

UNIQUAC: ⎛ bij ⎞ τij = exp⎜aij + ⎟ T⎠ ⎝

θ′ j τij ∑k θ′k τkj

+ li + q′i −

ϕi xi

∑ xjlj j

(13)

The equilibrium temperature and vapor phase composition of each binary system can be predicted by using the binary interaction energy parameters. The t−x−y diagrams about binary mixtures composed of EMMP with isobutyl alcohol or 1butanol at 101.33 kPa are depicted in Figures 5 and 6. By comparing, it is very significant that these calculated values obtained by Wilson, NRTL, and UNIQUAC models can be correlated with a good degree of accuracy with these measurements. 3.4. Correlations for Azeotropic Data. The azeotropic data of the binary system about EMMP + 1-butanol were estimated based on the T−x−y diagram which was described by using calculated data correlated by the NRTL model for EMMP + the 1-butanol system. The azeotropic state is 389.64 K and 75.92 mol % (1-butanol). In addition, the azeotropic data were measured by a rectifying process using the rectifying column. the theoretical plate number of the column is 25 under the conditions of total reflux where the composition of the binary

interaction energy parameters can be obtained by three following equations: ⎛ bij ⎞ Aij = exp⎜aij + ⎟ T⎠ ⎝

θi − q′i ln ∑ θ′k τki ϕi k

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Table 8. Wilson, NRTL, and UNIQUAC Equations Parameters and Mean Absolute Deviations of the Binary Systems model parameters model

aij

aji

Wilson NRTL UNIQ

0 0 4.65960285

0 0 −5.7863343

Wilson NRTL UNIQ

0 0 5.35119753

0 0 −6.33123597

average absolute deviation

bij (K)

bji (K)

Isobutyl Alcohol(1) + EMMP(2) −19.6529224 −209.979707 265.521339 −36.2760758 −1665.71455 1988.37076 1-Butanol(1) + EMMP (2) −45.7629999 −215.325964 263.252986 −5.84095213 −2015.52891 2304.386

αija

|ΔT|b

|Δy1|c

0 0.3 0

0.23 0.23 0.21

0.0060 0.0060 0.0019

0 0.3 0

0.10 0.10 0.07

0.0026 0.0026 0.0015

a The parameter of NRTL is set to 0.3 when the mixture contains a polar component. b|ΔT| = ∑ |Tcal − Texp|/k. c|Δy1| = ∑ |ycal − yexp|/k, where k is the number of data points.

Figure 5. T−x−y diagram for the isobutyl alcohol(1) and EMMP(2) system at 101.33 kPa.

Figure 6. T−x−y diagram for the 1-butanol(1) and EMMP(2) system at 101.33 kPa.

system mixture is 50 mol % (EMMP) + 50 mol % (1-butanol) in the kettle. These azeotropic data are 389.70 K and 75.85 mol % (1-butanol).

the measurements can be applied to design separation technologies for the purification of EMMP.

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ASSOCIATED CONTENT

S Supporting Information *

4. CONCLUSIONS In this work, the VLE measurements for two binary mixtures composed of EMMP with isobutyl alcohol or 1-butanol at 101.33 kPa and the saturated vapor pressure measurements of pure component for EMMP at different temperature were measured by a dynamic modified Rose still. The t−x−y diagram of EMMP + 1-butanol system at 101.33 kPa shows a minimum boiling azeotrope. The azeotropic state is 389.64 K and 75.92 mol % (1-butanol) for EMMP + 1-butanol mixture. The Antoine equation parameters of EMMP were correlated by measurements presented in this paper. Our VLE measurements passed the thermodynamic consistency test with the help of the Herington semiempirical method. They were correlated by using the Wilson, NRTL, and UNIQUAC models for which the binary interaction energy parameters were obtained, and there is a good correlation under the three models. The average absolute deviations (ΔT/Δy) correlated under the Wilson, NRTL, and UNIQUAC models were less than 0.23 K and 0.0060, respectively. Therefore, there is reason to believe that

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.7b00377. GC−MS/MS and 1H NMR results (PDF)

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AUTHOR INFORMATION

Corresponding Author

*Tel.: +86 181 3694 7270. E-mail [email protected]. ORCID

Yu-He Song: 0000-0002-2366-5481 Funding

The authors thank the Project of Natural Science Research of Higher Education Institutions of Jiangsu Province (No. 15KJD530001) and the Taizhou University research project (No. TZXY2015QDXM025) for financial support for this work. Notes

The authors declare no competing financial interest. 2448

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ACKNOWLEDGMENTS We wish to thank Prof. Joshua Qingsong Li at China University of Petroleum−East China for his valuable support with the calculations.

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ABBREVIATIONS AND SYMBOL LIST A, B, C = parameters of the Antoine equation Aij, Aji = binary energy interaction parameters of Wilson model Gij = binary energy interaction parameters of NRTL model Øi, θi = binary energy interaction parameters of UNIQUAC model T = absolute temperature Tb = boiling temperature Vil = the molar volume of pure liquid p = pressure ps = saturated pressure aij, bij = binary interaction parameters τij = temperature dependent parameter of NRTL model x = mole fraction in liquid y = mole fraction in vapor nD = refractive index c = average concentration of the analyte

Greek Letters

α = NRTL nonrandomness parameter γ = activity coefficient ρ = density Δ = standard deviation Subscripts

cal = calculated value exp = experimental value i, j = component k = data number

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DOI: 10.1021/acs.jced.7b00377 J. Chem. Eng. Data 2017, 62, 2443−2449