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Isobaric vapor–liquid equilibrium at 101.3 kPa and excess properties at 298.15 K for binary mixtures of methyl phenyl carbonate with methanol or dimethyl carbonate
Fluid Phase Equilibria 360 (2013) 260–264
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Isobaric vapor–liquid equilibrium at 101.3 kPa and excess properties at 298.15 K for binary mixtures of methyl phenyl carbonate with methanol or dimethyl carbonate In-Chan Hwang, Sang-Hong Shin, In-Yong Jeong, Yeong-Hwan Jeon, So-Jin Park ∗ Department of Chemical Engineering, Chungnam National University, 99 Daehak-Ro, Yuseong-Gu, Daejeon 305-764, Republic of Korea
a r t i c l e
i n f o
Article history: Received 26 March 2013 Received in revised form 6 September 2013 Accepted 11 September 2013 Available online 19 September 2013 Keywords: Vapor pressure Vapor–liquid equilibrium Methyl phenyl carbonate Dimethyl carbonate Methanol
a b s t r a c t The vapor pressure of the pure component of methyl phenyl carbonate (MPC) was measured at temperatures ranging from 378 K to 488 K. The experimental vapor pressures could be fit well with a three-parameter Antoine equation. Isobaric vapor–liquid equilibria for binary systems (MPC + methanol and MPC + dimethyl carbonate) were determined using a dynamic method at 101.3 kPa. They were correlated with Wilson, NRTL and UNIQUAC models. In addition, excess molar volumes (VE ) and deviations in molar refractivity (R) at 298.15 K were recorded for the same binary systems using a digital vibrating tube densitometer and a precision digital refractometer. The VE and R data were in good agreement with the predictions of the Redlich–Kister equation. © 2013 Elsevier B.V. All rights reserved.
1. Introduction Currently, polycarbonates are widely used for engineering plastic. They have beneficial features, such as transparency, impact resistance, thermal stability, dimensional stability, and flame resistance. Polycarbonates have also been widely applied in pharmaceuticals, cosmetics, electronic appliances, automobiles, mobile phones, and natural and synthetic resins [1–3]. Diphenyl carbonate (DPC), one of the alkyl carbonates, is a very useful chemical intermediate in the synthesis of aromatic and aliphatic polycarbonates and other important industrial polymers. DPC is generally produced via the phosgene process, which uses carbon monoxide and chloride as raw materials. However, this phosgene process has several environmental drawbacks [4,5]. Transesterification of dimethyl carbonate (DMC) with phenol is another method for synthesizing DPC. In this process, DMC reacts with phenol and bisphenol A by transesterification, and methyl phenyl carbonate (MPC), DPC, anisole and methanol are produced. This newly developed DPC synthetic process is also considered to be a “green process” because it does not use toxic phosgene. Thus, mutual separation of the reaction products is very important to increase the yield of pure DPC in this synthetic process.
∗ Corresponding author. Tel.: +82 42 821 5684; fax: +82 42 823 6414. E-mail address: [email protected] (S.-J. Park). 0378-3812/$ – see front matter © 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.fluid.2013.09.030
This work reports vapor pressures for the pure component of MPC, as well as isobaric vapor–liquid equilibria (VLE) for binary systems of MPC + methanol and MPC + DMC at 101.3 kPa. The Antoine constants were determined using the measured vapor pressures for MPC because these pressures were not available in the literature. The experimental VLE data for the binary systems were correlated with three activity coefficient models: the Wilson [6], NRTL [7] and UNIQUAC [8] models. Additionally, we report the mixture properties, excess molar volumes (VE ) and deviations in molar refractivity (R) at 298.15 K for the binary systems, as measured by a digital vibrating tube densitometer and a precision digital refractometer. These data were well correlated with the predictions of the Redlich–Kister polynomial [9]. 2. Experimental 2.1. Materials Commercial grade analytical chemicals were used in this investigation. Methanol (CH4 O, M = 32.04 g mol−1 , CAS-RN 67-56-1, 99.9 wt%) was provided by J.T. Baker Chemical Co. DMC (C3 H6 O3 , M = 90.08 g mol−1 , CAS-RN 616-38-6, 99.9 wt%) was obtained from Aldrich Co. MPC (C8 H8 O3 , M =152.15 g mol−1 , CAS-RN13509-27-8. 38 wt%) was obtained from Samsung Cheil Ind. (Korea) as a mixture of MPC, DMC and phenol. The phenol and DMC were then evaporated from the mixture in a 1 m glass distillation column at 500 mbar. After the removal of DMC and phenol, the purity of the
I.-C. Hwang et al. / Fluid Phase Equilibria 360 (2013) 260–264
List of symbols A, B, C Ai Aij , Aji gij Mi n nD N R VE Vi xi yi uij
Antoine constant adjustable parameter for the Redlich–Kister equation parameters used in the Wilson, NRTL and UNIQUAC equations interaction energy in the NRTL equation (J mol−1 ) molar mass of pure component i (g mol−1 ) number of fitted parameters for the Antoine equation refractive index number of experimental data points deviations in molar refractivity (cm3 mol−1 ) excess molar volume (cm3 mol−1 ) molar volume of pure component i liquid-phase mole fraction of component i vapor-phase mole fraction of component i interaction energy in the UNIQUAC equation (J mol−1 )
Greek letters parameter in the NRTL equation ˛ i activity coefficient of component i density of component i (g cm−3 ) i m density of the mixture (g cm−3 ) standard deviation st i volume fraction of pure component i ij interaction energy in the Wilson equation (J mol−1 ) Subscripts i, k component; i, k experimental value exp cal calculated value
MPC was determined to be better than 99.5 wt% by mass using gas chromatographic analysis. All chemicals were dried over molecular sieves with a pore diameter of 0.4 nm, except methanol, which was dried using a 0.3 nm molecular sieve before the experiment. The water content of the chemicals, determined by a Karl-Fischer titrator (Metrohm 684 KF-Coulometer), was less than 1 × 10−5 g/g. The uncertainty of the Karl-Fischer titrations was estimated to be less than ±5 g. The mass %, densities and refractivities of the chemicals are listed in Table 1, together with reported values from the literature [10–12]. 2.2. Apparatus and procedure For determinations of vapor pressure and isobaric VLE, Dr. Sieg & Röck type recirculating glass still was used. Details about this
261
apparatus were described previously [13]. For both measurements, approximately 250 mL of pure component or liquid mixture was introduced to the still, and the pressure of the still was regulated using a Baratron pressure regulating system with an accuracy of ±0.1 kPa. In addition, the pressure inside the equilibrium cell was observed using a Wallace & Tiernan precision mercury manometer throughout the measurement period. When the desired equilibrium pressure was reached, the liquid phase was heated until rigorously boiling. With the temperature of the liquid phase held constant, the liquid and vapor phases were kept circulating in the still for more than 2 h. Then, the equilibrium temperature was checked with an A A F250 temperature probe, and samples of both phases were carefully taken while regulating the internal pressure of the still. The temperature of the equilibrium vessel was regulated by a thermostat to within ±0.02 K. Liquid and vapor samples were analyzed using a gas chromatograph (HP 6890N) equipped with an HP-FFAP (polyethylene glycol TPA, 25 m × 0.20 mm × 0.30 m) capillary column and a thermal conductivity detector. An injection volume of 1 L was used for gas chromatography, with a split ratio of 50:1. The injector and detector temperature were set to 503.15 K and 523.15 K, respectively. The oven temperature was maintained at 333.15 K for 4 min, then increased at a rate of 50 ◦ C min−1 to a final temperature of 503.15 K, which was maintained for 8 min. The carrier gas was high-purity helium at a total flow rate of 2.0 mL s−1 through the column. The uncertainty of the calculated mole fractions was estimated to be less than ±1 × 10−4 . The experimental procedure is described in detail elsewhere [14]. The densities were measured by a digital vibrating glass tube densitometer (Anton Paar, model DMA 5000, Graz, Austria). The densitometer was automatically calibrated with distilled water and dried air. The uncertainty of the densitometer is 5 × 10−6 g cm−3 in the density range of 0–3 g cm−3 , as stated by the manufacturer. The temperature was controlled to within ±0.01 K. The details of the operating procedures have been described elsewhere [15,16]. The refractive indices (nD ) of the pure components and mixtures were measured by a digital precision refractometer (KEM, model RA520N, Kyoto, Japan). The refractometer was calibrated with distilled water; the uncertainty of this refractometer is ±5 × 10−5 within the range of 1.32–1.40 and ±1 × 10−4 within the range of 1.40–1.58. The experimental procedure is described in detail elsewhere [17]. The accuracies of the densitometer and refractometer were tested periodically with doubly distilled water (298.15K = 0.997045 g cm−3 ) under atmospheric conditions. The margins of uncertainty for and nD in this test were estimated to be less than 1 × 10−5 g cm−3 and 1 × 10−4 , respectively. An approximately 3 ml sample mixture was prepared using a microbalance (OHAUS, model DV215CD, USA) with a precision of 1 × 10−5 g. The heavier component was charged first to minimize vaporization. The experimental systematic uncertainty was estimated to be less than 1 × 10−4 as a mole fraction. To achieve a constant temperature and stable oscillation, the time interval of the and nD measurement was chosen to be 15 min.
Table 1 Purities, densities, refractive indices and Antoine constants of pure components. Chemicals
MPC Methanol DMC
GC analysis (wt%)
>99.53 >99.99 >99.99
Water content (wt%)
<0.001 <0.001 <0.001
at 298.15 K
nD at 298.15 K a
Present study
Literature value
Present study
Literature value
1.14363 0.78669 1.06326
– 0.78660a 1.06328a
1.4948 1.3267 1.3666
– 1.32676b 1.36670c
The uncertainty of the measured water content was less than ±5 g. The uncertainty of the densitometer was less than ±1 × 10−5 g cm−3 and the accuracy of the temperature was ± 0.01 K. The uncertainty of the refractometer was less than ±1 × 10−4 and the accuracy of the temperature was ±0.05 K. a Ref. [10]. b Ref. [11]. c Ref. [12].
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I.-C. Hwang et al. / Fluid Phase Equilibria 360 (2013) 260–264 Table 4 Isobaric VLE for the binary systems of MPC with methanol and DMC at 101.3 kPa.
Table 2 Vapor pressures for the pure components of MPC. Psat (kPa)
T (K)
Psat (kPa)
T (K)
T (K)
3.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0 50.0 55.0
378.81 391.17 409.87 421.56 430.23 437.25 443.16 448.12 452.73 456.91 460.67 464.09
60.0 65.0 70.0 75.0 80.0 85.0 90.0 95.0 100.0 101.3 102.1
467.21 470.26 473.02 475.46 477.91 480.35 482.69 484.85 486.71 487.48 487.66
{MPC (1) + methanol (2)} 338.12 0.0000 338.58 0.2912 340.99 0.5483 0.6616 345.80 352.23 0.7393 0.7956 358.20 0.8499 365.27 375.12 0.8901 0.9105 383.33 0.9312 391.76 0.9492 401.65 {MPC (1) + DMC (2)} 0.0000 363.25 0.1596 366.04 0.3091 370.38 0.3756 373.86 380.92 0.5229 388.27 0.6097 0.6821 394.42 404.66 0.7539 0.8054 412.45 0.8515 421.48 0.8825 430.55
The uncertainty of the measured pressure was estimated as ±0.1 kPa and the accuracy of the temperature was ±0.02 K.
x1
y1
T (K)
x1
y1
0.0000 0.0028 0.0092 0.0125 0.0132 0.0147 0.0178 0.0277 0.0346 0.0465 0.0711
409.31 422.19 431.33 438.89 445.02 451.10 457.42 465.10 473.70 481.70 487.48
0.9587 0.9736 0.9788 0.9819 0.9876 0.9911 0.9932 0.9952 0.9976 0.9990 1.0000
0.0934 0.1494 0.2039 0.2618 0.3214 0.3850 0.4609 0.5612 0.7065 0.8687 1.0000
0.0000 0.0050 0.0095 0.0098 0.0177 0.0328 0.0494 0.0720 0.0989 0.1471 0.1978
437.50 443.09 449.36 455.87 462.06 467.02 471.54 475.80 480.55 484.12 487.48
0.9079 0.9212 0.9325 0.9451 0.9591 0.9688 0.9775 0.9858 0.9905 0.9963 1.0000
0.2438 0.2995 0.3611 0.4368 0.5117 0.5831 0.6541 0.7406 0.8207 0.8987 1.0000
The uncertainty of the calculated mole fractions to be less than 1 × 10−4 . The uncertainty of the measured pressure was estimated as ±0.1 kPa and the accuracy of the temperature was ±0.02 K.
Table 5 The GE model parameters and mean deviation between the calculated and experimental equilibrium temperature (T) and vapor-phase mole fraction (y1 ) for the binary systems of MPC, methanol and DMC at 101.3 kPa. Model equation
{MPC (1) + methanol (2)} Wilson 72153.71 NRTL −1767.48 UNIQUAC 2144.66 {MPC (1) + DMC (2)} Wilson 8201.73 NRTL −1720.12 −2376.69 UNIQUAC
Fig. 1. Vapor pressures of MPC: (䊉), experimental data point. Solid curve was calculated from Antoine equation.
a
3. Results and discussion
The vapor pressure for MPC was determined by boiling point measurements at 23 different arbitrarily assigned pressures. The ranges of temperature and pressure for vapor pressure measurements were T = (335–463) K and P = (3–102.1) kPa, respectively. The results are listed and plotted in Table 2 and Fig. 1, respectively. The experimental vapor pressure data were fit to the Antoine equation (Eq. (1)). The correlation coefficient (r2 ) of the determined Antoine constants for each pure component was 0.9999. The Antoine constants and standard deviations of recalculated vapor pressures derived from the Antoine constants are provided
Table 3 Antoine constantsa and standard deviationsb (SD) for the vapor pressures of MPC.
b
Component
A
B
C
SD (KPa)
MPC
7.54048
2778.727
14.953
0.0025
log P
sat
/kPa = A −
SD (KPa) =
B C+T/K
.
sat ) (P sat −Pexp cal
N−n
2
RMSD M =
1/NP
NP k=1
Aji (J mol−1 )
˛
T (K)a
y1 a
3628.80 10256.12 1075.24
– 0.2529 –
0.24 0.18 0.25
0.0233 0.0141 0.0249
−1037.27 6291.39 4718.44
– 0.5626 –
0.07 0.08 0.08
0.0126 0.0127 0.0138
exp
Mkcal − Mk
2 1/2
, where Np is the number of data
points and M represents T or y1 .
3.1. Vapor pressures and isobaric vapor–liquid equilibrium (VLE)
a
Aij (J mol−1 )
1/2 .
in Table 3. In Fig. 1, the solid line illustrates the calculated values and their associated Antoine constants. log P sat (kPa) = A −
B C + T/K
(1)
Isobaric VLE data for the binary systems (MPC + methanol and MPC + DMC) were measured at 101.3 kPa. The simplified VLE relation (modified Raoult’s law, Eq. (2)) was used for the calculation of VLE behavior. yi P = xi i Pisat
(2)
The equilibrium compositions and temperatures at 101.3 kPa are listed in Table 4 and plotted in Fig. 2. As shown in Fig. 2, the binary systems were zeotropic systems. The experimental binary VLE data were correlated with three common GE models: the Wilson, NRTL and UNIQUAC models [6–8]. The adjustable binary parameters of the GE model correlation are listed in Table 5, together with the mean deviations. The binary interaction parameters (Aij ) in the activity coefficient () expression for the Wilson, NRTL and UNIQUAC models are as follows: Aij = (ij − ii )(J mol−1 )
(Wilson)
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263
Table 6 Densities, excess molar volumes, refractive indices and deviations in molar refractivity for the binary systems {MPC (1) + methanol (2)} and {MPC (1) + DMC (2)} at 298.15 K. (g cm−3 )
x1
Fig. 2. Isobaric VLE for binary systems of MPC with methanol or DMC at 101.3 kPa: filled symbols, vapor phase; open symbols, liquid phase; (䊉), {MPC (1) + methanol (2)}; (), {MPC (1) + DMC (2)}; solid curves were calculated from best fitted GE model parameters.
Aij = (g ij − g ii )(J mol−1 )
Rm =
(UNIQUAC)
With these parameters, correlations with the experimental data were calculated, and deviations from experimental values for equilibrium composition and temperature at equilibrium pressure were calculated. The results are satisfactory, with small deviations in temperature (T) and vapor-phase mole fraction (y1 ) between the experimental and calculated data. The deviations were less than T = 0.17 K and y1 = 0.015, respectively. 3.2. Excess molar volumes and deviations in molar refractivity The VE values for the binary mixtures were calculated from the measured densities of pure substances and mixtures by Eq. (3):
xM i i i
m
−
x M i i i
(3)
i
where xi , Mi , i and m are the mole fraction, molar mass, pure component density and mixture density, respectively. The R value was calculated from the molar refractivity (Rm ) data for the pure components and the mixtures, which are derived from the measured densities and refractive indices by using Eq. (4) through (7) [18,19]: R (cm3 mol−1 ) = Rm −
i
i Ri
(4)
nD
R (cm3 mol−1 )
−0.1587 −0.2676 −0.3798 −0.4127 −0.4041 −0.3751 −0.3392 −0.2818 −0.2025 −0.1151 −0.0585
1.3647 1.3885 1.4283 1.4500 1.4670 1.4748 1.4801 1.4848 1.4877 1.4915 1.4929
−3.4059 −5.9916 −8.8643 −10.1078 −10.0743 −9.4711 −8.3004 −6.6673 −4.7622 −2.4595 −1.3585
−0.0400 −0.0746 −0.1252 −0.1570 −0.1695 −0.1663 −0.1515 −0.1217 −0.0890 −0.0495 −0.0263
1.3764 1.3863 1.4038 1.4190 1.4336 1.4463 1.4575 1.4680 1.4774 1.4853 1.4901
−0.6317 −1.1361 −1.9221 −2.4236 −2.6143 −2.6010 −2.4168 −2.0284 −1.5073 −0.8977 −0.4675
The uncertainty of the calculated mole fractions to be less than 1 × 10−4 . The uncertainty of the densitometer was estimated less than 1 × 10−5 g cm−3 and the accuracy of the temperature was ±0.01 K. The uncertainty of the refractometer was estimated less than 1 × 10−4 .
(NRTL)
Aij = (uij − uii )(J mol−1 )
V E (cm3 mol−1 ) =
{MPC (1) + methanol (2)} 0.0501 0.84207 0.88648 0.1001 0.95327 0.2002 1.00092 0.3002 0.4003 1.03671 0.5000 1.06449 0.6013 1.08716 0.7008 1.10528 1.12025 0.8003 1.13312 0.9015 0.9471 1.13814 {MPC (1) + DMC (2)} 1.06988 0.0499 1.07610 0.1000 0.2001 1.08737 1.09732 0.2999 1.10617 0.4000 0.5002 1.11408 1.12117 0.6000 1.12760 0.7007 1.13342 0.8003 0.8991 1.13871 0.9493 1.14122
VE (cm3 mol−1 )
Ri =
nD 2 − 1 nD 2 + 1
nD,i 2 − 1 nD,i 2 + 1
xM i i i
(5)
m
Mi i
(6)
and i =
x Vi
i
(7)
xV j j j
where i , nD , nD,i and Vi are the volume fraction of the pure components in the mixture, the refractive index of the mixture, and the refractive index and molar volume of pure component i, respectively. The experimental densities, VE values, refractive indices and R values for the binary systems (MPC + methanol and MPC + DMC) at 298.15 K are listed in Table 6. The binary VE and R data were determined by correlation with the Redlich–Kister polynomial, Eq. (8) [9]. The number of parameters (Ai ) was empirically fixed as 4 because standard deviation has the smallest value when using the 4 parameters. The regressed 4 parameters are listed in Table 7 with standard deviations. E V12 or R (cm3 mol−1 ) = x1 x2
4 i=1
Ai (x1 − x2 )i−1
(8)
Table 7 Fitted parameters for the Redlich–Kister equation and standard deviations for VE and R for the binary systems {MPC (1) + methanol (2)} and {MPC (1) + DMC (2)} at 298.15 K. Systems E
V
R
{MPC (1) + methanol (2)} {MPC (1) + DMC (2)} {MPC (1) + methanol (2)} {MPC (1) + DMC (2)}
A1
A2
A3
A4
st (cm3 mol−1)
−1.5059 −0.6646 −37.7602 −10.4130
0.6767 0.2079 18.6533 2.3611
−0.9274 −0.0238 −14.0419 −1.1514
0.6246 −0.0498 8.1307 −0.7433
0.0031 0.0010 0.0459 0.0173
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I.-C. Hwang et al. / Fluid Phase Equilibria 360 (2013) 260–264
entire composition range. This outcome may be attributable to the polarity of carbonate and alcohol. The large size effect causes other interactions. The two C-O bonds of carbonate are slightly negative, and methanol is a typical polar molecule. Therefore, the MPC + methanol mixture showed a greater negative deviation compared to the MPC + DMC mixture. The binary VE data were correlated with the Redlich–Kister polynomial, and the recalculated values from the correlated parameters were in good agreement with experimental data, as shown in Fig. 3 with solid curves. The standard deviations of the differences between experimental and calculated VE values were 0.0031 and 0.0010 cm3 mol−1 for the MPC + methanol and MPC + DMC systems, respectively. Additionally, as shown in Fig. 4, the R values of the same binary systems had negative deviations. The binary R values also correlated well with the Redlich–Kister polynomial, as shown in Fig. 4. The standard deviations of the differences between experimental and calculated R values were 0.0459 and 0.0173 cm3 mol−1 for the MPC + methanol and MPC + DMC systems, respectively. 4. Conclusions
Fig. 3. VE (cm3 mol−1 ) for binary systems at 298.15 K: (䊉), {MPC (1) + methanol (2)}; (), {MPC (1) + DMC (2)}; solid curves were calculated from Redlich–Kister parameters.
New Antoine coefficients for MPC are reported for pressures from 3 to 102.1 kPa. Isobaric VLE data for the binary systems MPC + methanol and MPC + DMC were measured at 101.3 kPa. Experimental VLE data sets came from zeotropic systems and correlated well with the Wilson, NRTL and UNIQUAC models. The experimental VE and R data for the same binary systems showed negative deviations from ideal behavior because of the polarity of the components. The VE and R data were correlated well with the Redlich–Kister polynomial. Acknowledgment This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (Grant No: 2012R1A1A2008315). References
Fig. 4. R (cm3 mol−1 ) for binary systems at 298.15 K: (䊉), {MPC (1) + methanol (2)}; (), {MPC (1) + DMC (2)}; solid curves were calculated from Redlich–Kister parameters.
The standard deviation of the fits st , is defined as follows:
3
st (cm mol
−1
)=
i
2
((V E or R)cal − (V E orR)exp )i (N − 4)
1/2
(9)
where N is the number of experimental data points, and four is the number of fitted parameters. The calculated VE and R values are plotted in Figs. 3 and 4, respectively. The VE values of MPC + methanol and MPC + DMC at 298.15 K showed negative deviations from ideal behavior over the
[1] K. Othmer, Encyclopedia of Chemical Technology, 4th ed., John Wiley and Sons, New York, 1993. [2] J. Haubrock, M. Raspe, G.F. Versteeg, H.A. Kooijman, R. Taylor, J.A. Hogendoorn, Ind. Eng. Chem. Res. 47 (2008) 9854–9861. [3] J. Gong, X. Ma, S. Wang, Appl. Catal. A 316 (2007) 1–21. [4] S. Fukuoka, M. Kawamura, K. Komiya, M. Tojo, H. Hachiya, K. Hasegawa, M. Aminaka, H. Okamoto, I. Fukawa, S. Konno, Green Chem. 5 (2003) 497–507. [5] Y. Ono, Appl. Catal. A 155 (1997) 133–166. [6] G.M. Wilson, C.H. Deal, Ind. Chem. Fundam. 1 (1962) 20–23. [7] H. Renon, J.M. Prausnitz, AIChE J. 14 (1968) 135–144. [8] D.S. Abrams, J.M. Prausnitz, AIChE J. 21 (1975) 116–128. [9] O. Redlich, A.T. Kister, Ind. Eng. Chem. 40 (1948) 345–348. [10] Dortmund Data Bank Software Package (DDBSP), Version 2006 Professional, Software and Separation Technology GmbH (http://www.ddbst.de). [11] M. Iglesias, B. Orge, J. Tojo, Fluid Phase Equilib. 126 (1996) 203–223. [12] I.G. Fuente, J.A. Gonztilez, J.C. Cobos, C. Casanova, J. Chem. Eng. Data 37 (1992) 535–537. [13] S.J. Park, K.J. Han, J. Gmehling, Fluid Phase Equilib. 200 (2002) 399–409. [14] K.J. Han, I.C. Hwang, S.J. Park, M.J. Choi, S.B. Lee, J.S. Han, Fluid Phase Equilib. 249 (2006) 187–191. [15] J.H. Oh, S.J. Park, J. Chem. Eng. Data 43 (1998) 1009–1013. [16] S.J. Park, H.H. Kim, K.J. Han, D.B. Won, S.B. Lee, M.J. Choi, Fluid Phase Equilib. 180 (2001) 361–373. [17] K.J. Han, J.H. Oh, S.J. Park, J. Ind. Eng. Chem. 13 (2007) 360–366. [18] T.M. Aminabhavi, B. Golalakrishina, J. Chem. Eng. Data 40 (1995) 856–861. [19] A.H. Al-Dujaili, A.A. Yassen, A.M. Awwad, J. Chem. Eng. Data 45 (2000) 647–649.
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Isobaric vapor–liquid equilibrium at 101.3 kPa and excess properties at 298.15 K for binary mixtures of methyl phenyl carbonate with methanol or dimethyl carbonate In-Chan Hwang, Sang-Hong Shin, In-Yong Jeong, Yeong-Hwan Jeon, So-Jin Park ∗ Department of Chemical Engineering, Chungnam National University, 99 Daehak-Ro, Yuseong-Gu, Daejeon 305-764, Republic of Korea
a r t i c l e
i n f o
Article history: Received 26 March 2013 Received in revised form 6 September 2013 Accepted 11 September 2013 Available online 19 September 2013 Keywords: Vapor pressure Vapor–liquid equilibrium Methyl phenyl carbonate Dimethyl carbonate Methanol
a b s t r a c t The vapor pressure of the pure component of methyl phenyl carbonate (MPC) was measured at temperatures ranging from 378 K to 488 K. The experimental vapor pressures could be fit well with a three-parameter Antoine equation. Isobaric vapor–liquid equilibria for binary systems (MPC + methanol and MPC + dimethyl carbonate) were determined using a dynamic method at 101.3 kPa. They were correlated with Wilson, NRTL and UNIQUAC models. In addition, excess molar volumes (VE ) and deviations in molar refractivity (R) at 298.15 K were recorded for the same binary systems using a digital vibrating tube densitometer and a precision digital refractometer. The VE and R data were in good agreement with the predictions of the Redlich–Kister equation. © 2013 Elsevier B.V. All rights reserved.
1. Introduction Currently, polycarbonates are widely used for engineering plastic. They have beneficial features, such as transparency, impact resistance, thermal stability, dimensional stability, and flame resistance. Polycarbonates have also been widely applied in pharmaceuticals, cosmetics, electronic appliances, automobiles, mobile phones, and natural and synthetic resins [1–3]. Diphenyl carbonate (DPC), one of the alkyl carbonates, is a very useful chemical intermediate in the synthesis of aromatic and aliphatic polycarbonates and other important industrial polymers. DPC is generally produced via the phosgene process, which uses carbon monoxide and chloride as raw materials. However, this phosgene process has several environmental drawbacks [4,5]. Transesterification of dimethyl carbonate (DMC) with phenol is another method for synthesizing DPC. In this process, DMC reacts with phenol and bisphenol A by transesterification, and methyl phenyl carbonate (MPC), DPC, anisole and methanol are produced. This newly developed DPC synthetic process is also considered to be a “green process” because it does not use toxic phosgene. Thus, mutual separation of the reaction products is very important to increase the yield of pure DPC in this synthetic process.
∗ Corresponding author. Tel.: +82 42 821 5684; fax: +82 42 823 6414. E-mail address: [email protected] (S.-J. Park). 0378-3812/$ – see front matter © 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.fluid.2013.09.030
This work reports vapor pressures for the pure component of MPC, as well as isobaric vapor–liquid equilibria (VLE) for binary systems of MPC + methanol and MPC + DMC at 101.3 kPa. The Antoine constants were determined using the measured vapor pressures for MPC because these pressures were not available in the literature. The experimental VLE data for the binary systems were correlated with three activity coefficient models: the Wilson [6], NRTL [7] and UNIQUAC [8] models. Additionally, we report the mixture properties, excess molar volumes (VE ) and deviations in molar refractivity (R) at 298.15 K for the binary systems, as measured by a digital vibrating tube densitometer and a precision digital refractometer. These data were well correlated with the predictions of the Redlich–Kister polynomial [9]. 2. Experimental 2.1. Materials Commercial grade analytical chemicals were used in this investigation. Methanol (CH4 O, M = 32.04 g mol−1 , CAS-RN 67-56-1, 99.9 wt%) was provided by J.T. Baker Chemical Co. DMC (C3 H6 O3 , M = 90.08 g mol−1 , CAS-RN 616-38-6, 99.9 wt%) was obtained from Aldrich Co. MPC (C8 H8 O3 , M =152.15 g mol−1 , CAS-RN13509-27-8. 38 wt%) was obtained from Samsung Cheil Ind. (Korea) as a mixture of MPC, DMC and phenol. The phenol and DMC were then evaporated from the mixture in a 1 m glass distillation column at 500 mbar. After the removal of DMC and phenol, the purity of the
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List of symbols A, B, C Ai Aij , Aji gij Mi n nD N R VE Vi xi yi uij
Antoine constant adjustable parameter for the Redlich–Kister equation parameters used in the Wilson, NRTL and UNIQUAC equations interaction energy in the NRTL equation (J mol−1 ) molar mass of pure component i (g mol−1 ) number of fitted parameters for the Antoine equation refractive index number of experimental data points deviations in molar refractivity (cm3 mol−1 ) excess molar volume (cm3 mol−1 ) molar volume of pure component i liquid-phase mole fraction of component i vapor-phase mole fraction of component i interaction energy in the UNIQUAC equation (J mol−1 )
Greek letters parameter in the NRTL equation ˛ i activity coefficient of component i density of component i (g cm−3 ) i m density of the mixture (g cm−3 ) standard deviation st i volume fraction of pure component i ij interaction energy in the Wilson equation (J mol−1 ) Subscripts i, k component; i, k experimental value exp cal calculated value
MPC was determined to be better than 99.5 wt% by mass using gas chromatographic analysis. All chemicals were dried over molecular sieves with a pore diameter of 0.4 nm, except methanol, which was dried using a 0.3 nm molecular sieve before the experiment. The water content of the chemicals, determined by a Karl-Fischer titrator (Metrohm 684 KF-Coulometer), was less than 1 × 10−5 g/g. The uncertainty of the Karl-Fischer titrations was estimated to be less than ±5 g. The mass %, densities and refractivities of the chemicals are listed in Table 1, together with reported values from the literature [10–12]. 2.2. Apparatus and procedure For determinations of vapor pressure and isobaric VLE, Dr. Sieg & Röck type recirculating glass still was used. Details about this
261
apparatus were described previously [13]. For both measurements, approximately 250 mL of pure component or liquid mixture was introduced to the still, and the pressure of the still was regulated using a Baratron pressure regulating system with an accuracy of ±0.1 kPa. In addition, the pressure inside the equilibrium cell was observed using a Wallace & Tiernan precision mercury manometer throughout the measurement period. When the desired equilibrium pressure was reached, the liquid phase was heated until rigorously boiling. With the temperature of the liquid phase held constant, the liquid and vapor phases were kept circulating in the still for more than 2 h. Then, the equilibrium temperature was checked with an A A F250 temperature probe, and samples of both phases were carefully taken while regulating the internal pressure of the still. The temperature of the equilibrium vessel was regulated by a thermostat to within ±0.02 K. Liquid and vapor samples were analyzed using a gas chromatograph (HP 6890N) equipped with an HP-FFAP (polyethylene glycol TPA, 25 m × 0.20 mm × 0.30 m) capillary column and a thermal conductivity detector. An injection volume of 1 L was used for gas chromatography, with a split ratio of 50:1. The injector and detector temperature were set to 503.15 K and 523.15 K, respectively. The oven temperature was maintained at 333.15 K for 4 min, then increased at a rate of 50 ◦ C min−1 to a final temperature of 503.15 K, which was maintained for 8 min. The carrier gas was high-purity helium at a total flow rate of 2.0 mL s−1 through the column. The uncertainty of the calculated mole fractions was estimated to be less than ±1 × 10−4 . The experimental procedure is described in detail elsewhere [14]. The densities were measured by a digital vibrating glass tube densitometer (Anton Paar, model DMA 5000, Graz, Austria). The densitometer was automatically calibrated with distilled water and dried air. The uncertainty of the densitometer is 5 × 10−6 g cm−3 in the density range of 0–3 g cm−3 , as stated by the manufacturer. The temperature was controlled to within ±0.01 K. The details of the operating procedures have been described elsewhere [15,16]. The refractive indices (nD ) of the pure components and mixtures were measured by a digital precision refractometer (KEM, model RA520N, Kyoto, Japan). The refractometer was calibrated with distilled water; the uncertainty of this refractometer is ±5 × 10−5 within the range of 1.32–1.40 and ±1 × 10−4 within the range of 1.40–1.58. The experimental procedure is described in detail elsewhere [17]. The accuracies of the densitometer and refractometer were tested periodically with doubly distilled water (298.15K = 0.997045 g cm−3 ) under atmospheric conditions. The margins of uncertainty for and nD in this test were estimated to be less than 1 × 10−5 g cm−3 and 1 × 10−4 , respectively. An approximately 3 ml sample mixture was prepared using a microbalance (OHAUS, model DV215CD, USA) with a precision of 1 × 10−5 g. The heavier component was charged first to minimize vaporization. The experimental systematic uncertainty was estimated to be less than 1 × 10−4 as a mole fraction. To achieve a constant temperature and stable oscillation, the time interval of the and nD measurement was chosen to be 15 min.
Table 1 Purities, densities, refractive indices and Antoine constants of pure components. Chemicals
MPC Methanol DMC
GC analysis (wt%)
>99.53 >99.99 >99.99
Water content (wt%)
<0.001 <0.001 <0.001
at 298.15 K
nD at 298.15 K a
Present study
Literature value
Present study
Literature value
1.14363 0.78669 1.06326
– 0.78660a 1.06328a
1.4948 1.3267 1.3666
– 1.32676b 1.36670c
The uncertainty of the measured water content was less than ±5 g. The uncertainty of the densitometer was less than ±1 × 10−5 g cm−3 and the accuracy of the temperature was ± 0.01 K. The uncertainty of the refractometer was less than ±1 × 10−4 and the accuracy of the temperature was ±0.05 K. a Ref. [10]. b Ref. [11]. c Ref. [12].
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I.-C. Hwang et al. / Fluid Phase Equilibria 360 (2013) 260–264 Table 4 Isobaric VLE for the binary systems of MPC with methanol and DMC at 101.3 kPa.
Table 2 Vapor pressures for the pure components of MPC. Psat (kPa)
T (K)
Psat (kPa)
T (K)
T (K)
3.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0 50.0 55.0
378.81 391.17 409.87 421.56 430.23 437.25 443.16 448.12 452.73 456.91 460.67 464.09
60.0 65.0 70.0 75.0 80.0 85.0 90.0 95.0 100.0 101.3 102.1
467.21 470.26 473.02 475.46 477.91 480.35 482.69 484.85 486.71 487.48 487.66
{MPC (1) + methanol (2)} 338.12 0.0000 338.58 0.2912 340.99 0.5483 0.6616 345.80 352.23 0.7393 0.7956 358.20 0.8499 365.27 375.12 0.8901 0.9105 383.33 0.9312 391.76 0.9492 401.65 {MPC (1) + DMC (2)} 0.0000 363.25 0.1596 366.04 0.3091 370.38 0.3756 373.86 380.92 0.5229 388.27 0.6097 0.6821 394.42 404.66 0.7539 0.8054 412.45 0.8515 421.48 0.8825 430.55
The uncertainty of the measured pressure was estimated as ±0.1 kPa and the accuracy of the temperature was ±0.02 K.
x1
y1
T (K)
x1
y1
0.0000 0.0028 0.0092 0.0125 0.0132 0.0147 0.0178 0.0277 0.0346 0.0465 0.0711
409.31 422.19 431.33 438.89 445.02 451.10 457.42 465.10 473.70 481.70 487.48
0.9587 0.9736 0.9788 0.9819 0.9876 0.9911 0.9932 0.9952 0.9976 0.9990 1.0000
0.0934 0.1494 0.2039 0.2618 0.3214 0.3850 0.4609 0.5612 0.7065 0.8687 1.0000
0.0000 0.0050 0.0095 0.0098 0.0177 0.0328 0.0494 0.0720 0.0989 0.1471 0.1978
437.50 443.09 449.36 455.87 462.06 467.02 471.54 475.80 480.55 484.12 487.48
0.9079 0.9212 0.9325 0.9451 0.9591 0.9688 0.9775 0.9858 0.9905 0.9963 1.0000
0.2438 0.2995 0.3611 0.4368 0.5117 0.5831 0.6541 0.7406 0.8207 0.8987 1.0000
The uncertainty of the calculated mole fractions to be less than 1 × 10−4 . The uncertainty of the measured pressure was estimated as ±0.1 kPa and the accuracy of the temperature was ±0.02 K.
Table 5 The GE model parameters and mean deviation between the calculated and experimental equilibrium temperature (T) and vapor-phase mole fraction (y1 ) for the binary systems of MPC, methanol and DMC at 101.3 kPa. Model equation
{MPC (1) + methanol (2)} Wilson 72153.71 NRTL −1767.48 UNIQUAC 2144.66 {MPC (1) + DMC (2)} Wilson 8201.73 NRTL −1720.12 −2376.69 UNIQUAC
Fig. 1. Vapor pressures of MPC: (䊉), experimental data point. Solid curve was calculated from Antoine equation.
a
3. Results and discussion
The vapor pressure for MPC was determined by boiling point measurements at 23 different arbitrarily assigned pressures. The ranges of temperature and pressure for vapor pressure measurements were T = (335–463) K and P = (3–102.1) kPa, respectively. The results are listed and plotted in Table 2 and Fig. 1, respectively. The experimental vapor pressure data were fit to the Antoine equation (Eq. (1)). The correlation coefficient (r2 ) of the determined Antoine constants for each pure component was 0.9999. The Antoine constants and standard deviations of recalculated vapor pressures derived from the Antoine constants are provided
Table 3 Antoine constantsa and standard deviationsb (SD) for the vapor pressures of MPC.
b
Component
A
B
C
SD (KPa)
MPC
7.54048
2778.727
14.953
0.0025
log P
sat
/kPa = A −
SD (KPa) =
B C+T/K
.
sat ) (P sat −Pexp cal
N−n
2
RMSD M =
1/NP
NP k=1
Aji (J mol−1 )
˛
T (K)a
y1 a
3628.80 10256.12 1075.24
– 0.2529 –
0.24 0.18 0.25
0.0233 0.0141 0.0249
−1037.27 6291.39 4718.44
– 0.5626 –
0.07 0.08 0.08
0.0126 0.0127 0.0138
exp
Mkcal − Mk
2 1/2
, where Np is the number of data
points and M represents T or y1 .
3.1. Vapor pressures and isobaric vapor–liquid equilibrium (VLE)
a
Aij (J mol−1 )
1/2 .
in Table 3. In Fig. 1, the solid line illustrates the calculated values and their associated Antoine constants. log P sat (kPa) = A −
B C + T/K
(1)
Isobaric VLE data for the binary systems (MPC + methanol and MPC + DMC) were measured at 101.3 kPa. The simplified VLE relation (modified Raoult’s law, Eq. (2)) was used for the calculation of VLE behavior. yi P = xi i Pisat
(2)
The equilibrium compositions and temperatures at 101.3 kPa are listed in Table 4 and plotted in Fig. 2. As shown in Fig. 2, the binary systems were zeotropic systems. The experimental binary VLE data were correlated with three common GE models: the Wilson, NRTL and UNIQUAC models [6–8]. The adjustable binary parameters of the GE model correlation are listed in Table 5, together with the mean deviations. The binary interaction parameters (Aij ) in the activity coefficient () expression for the Wilson, NRTL and UNIQUAC models are as follows: Aij = (ij − ii )(J mol−1 )
(Wilson)
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263
Table 6 Densities, excess molar volumes, refractive indices and deviations in molar refractivity for the binary systems {MPC (1) + methanol (2)} and {MPC (1) + DMC (2)} at 298.15 K. (g cm−3 )
x1
Fig. 2. Isobaric VLE for binary systems of MPC with methanol or DMC at 101.3 kPa: filled symbols, vapor phase; open symbols, liquid phase; (䊉), {MPC (1) + methanol (2)}; (), {MPC (1) + DMC (2)}; solid curves were calculated from best fitted GE model parameters.
Aij = (g ij − g ii )(J mol−1 )
Rm =
(UNIQUAC)
With these parameters, correlations with the experimental data were calculated, and deviations from experimental values for equilibrium composition and temperature at equilibrium pressure were calculated. The results are satisfactory, with small deviations in temperature (T) and vapor-phase mole fraction (y1 ) between the experimental and calculated data. The deviations were less than T = 0.17 K and y1 = 0.015, respectively. 3.2. Excess molar volumes and deviations in molar refractivity The VE values for the binary mixtures were calculated from the measured densities of pure substances and mixtures by Eq. (3):
xM i i i
m
−
x M i i i
(3)
i
where xi , Mi , i and m are the mole fraction, molar mass, pure component density and mixture density, respectively. The R value was calculated from the molar refractivity (Rm ) data for the pure components and the mixtures, which are derived from the measured densities and refractive indices by using Eq. (4) through (7) [18,19]: R (cm3 mol−1 ) = Rm −
i
i Ri
(4)
nD
R (cm3 mol−1 )
−0.1587 −0.2676 −0.3798 −0.4127 −0.4041 −0.3751 −0.3392 −0.2818 −0.2025 −0.1151 −0.0585
1.3647 1.3885 1.4283 1.4500 1.4670 1.4748 1.4801 1.4848 1.4877 1.4915 1.4929
−3.4059 −5.9916 −8.8643 −10.1078 −10.0743 −9.4711 −8.3004 −6.6673 −4.7622 −2.4595 −1.3585
−0.0400 −0.0746 −0.1252 −0.1570 −0.1695 −0.1663 −0.1515 −0.1217 −0.0890 −0.0495 −0.0263
1.3764 1.3863 1.4038 1.4190 1.4336 1.4463 1.4575 1.4680 1.4774 1.4853 1.4901
−0.6317 −1.1361 −1.9221 −2.4236 −2.6143 −2.6010 −2.4168 −2.0284 −1.5073 −0.8977 −0.4675
The uncertainty of the calculated mole fractions to be less than 1 × 10−4 . The uncertainty of the densitometer was estimated less than 1 × 10−5 g cm−3 and the accuracy of the temperature was ±0.01 K. The uncertainty of the refractometer was estimated less than 1 × 10−4 .
(NRTL)
Aij = (uij − uii )(J mol−1 )
V E (cm3 mol−1 ) =
{MPC (1) + methanol (2)} 0.0501 0.84207 0.88648 0.1001 0.95327 0.2002 1.00092 0.3002 0.4003 1.03671 0.5000 1.06449 0.6013 1.08716 0.7008 1.10528 1.12025 0.8003 1.13312 0.9015 0.9471 1.13814 {MPC (1) + DMC (2)} 1.06988 0.0499 1.07610 0.1000 0.2001 1.08737 1.09732 0.2999 1.10617 0.4000 0.5002 1.11408 1.12117 0.6000 1.12760 0.7007 1.13342 0.8003 0.8991 1.13871 0.9493 1.14122
VE (cm3 mol−1 )
Ri =
nD 2 − 1 nD 2 + 1
nD,i 2 − 1 nD,i 2 + 1
xM i i i
(5)
m
Mi i
(6)
and i =
x Vi
i
(7)
xV j j j
where i , nD , nD,i and Vi are the volume fraction of the pure components in the mixture, the refractive index of the mixture, and the refractive index and molar volume of pure component i, respectively. The experimental densities, VE values, refractive indices and R values for the binary systems (MPC + methanol and MPC + DMC) at 298.15 K are listed in Table 6. The binary VE and R data were determined by correlation with the Redlich–Kister polynomial, Eq. (8) [9]. The number of parameters (Ai ) was empirically fixed as 4 because standard deviation has the smallest value when using the 4 parameters. The regressed 4 parameters are listed in Table 7 with standard deviations. E V12 or R (cm3 mol−1 ) = x1 x2
4 i=1
Ai (x1 − x2 )i−1
(8)
Table 7 Fitted parameters for the Redlich–Kister equation and standard deviations for VE and R for the binary systems {MPC (1) + methanol (2)} and {MPC (1) + DMC (2)} at 298.15 K. Systems E
V
R
{MPC (1) + methanol (2)} {MPC (1) + DMC (2)} {MPC (1) + methanol (2)} {MPC (1) + DMC (2)}
A1
A2
A3
A4
st (cm3 mol−1)
−1.5059 −0.6646 −37.7602 −10.4130
0.6767 0.2079 18.6533 2.3611
−0.9274 −0.0238 −14.0419 −1.1514
0.6246 −0.0498 8.1307 −0.7433
0.0031 0.0010 0.0459 0.0173
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I.-C. Hwang et al. / Fluid Phase Equilibria 360 (2013) 260–264
entire composition range. This outcome may be attributable to the polarity of carbonate and alcohol. The large size effect causes other interactions. The two C-O bonds of carbonate are slightly negative, and methanol is a typical polar molecule. Therefore, the MPC + methanol mixture showed a greater negative deviation compared to the MPC + DMC mixture. The binary VE data were correlated with the Redlich–Kister polynomial, and the recalculated values from the correlated parameters were in good agreement with experimental data, as shown in Fig. 3 with solid curves. The standard deviations of the differences between experimental and calculated VE values were 0.0031 and 0.0010 cm3 mol−1 for the MPC + methanol and MPC + DMC systems, respectively. Additionally, as shown in Fig. 4, the R values of the same binary systems had negative deviations. The binary R values also correlated well with the Redlich–Kister polynomial, as shown in Fig. 4. The standard deviations of the differences between experimental and calculated R values were 0.0459 and 0.0173 cm3 mol−1 for the MPC + methanol and MPC + DMC systems, respectively. 4. Conclusions
Fig. 3. VE (cm3 mol−1 ) for binary systems at 298.15 K: (䊉), {MPC (1) + methanol (2)}; (), {MPC (1) + DMC (2)}; solid curves were calculated from Redlich–Kister parameters.
New Antoine coefficients for MPC are reported for pressures from 3 to 102.1 kPa. Isobaric VLE data for the binary systems MPC + methanol and MPC + DMC were measured at 101.3 kPa. Experimental VLE data sets came from zeotropic systems and correlated well with the Wilson, NRTL and UNIQUAC models. The experimental VE and R data for the same binary systems showed negative deviations from ideal behavior because of the polarity of the components. The VE and R data were correlated well with the Redlich–Kister polynomial. Acknowledgment This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (Grant No: 2012R1A1A2008315). References
Fig. 4. R (cm3 mol−1 ) for binary systems at 298.15 K: (䊉), {MPC (1) + methanol (2)}; (), {MPC (1) + DMC (2)}; solid curves were calculated from Redlich–Kister parameters.
The standard deviation of the fits st , is defined as follows:
3
st (cm mol
−1
)=
i
2
((V E or R)cal − (V E orR)exp )i (N − 4)
1/2
(9)
where N is the number of experimental data points, and four is the number of fitted parameters. The calculated VE and R values are plotted in Figs. 3 and 4, respectively. The VE values of MPC + methanol and MPC + DMC at 298.15 K showed negative deviations from ideal behavior over the
[1] K. Othmer, Encyclopedia of Chemical Technology, 4th ed., John Wiley and Sons, New York, 1993. [2] J. Haubrock, M. Raspe, G.F. Versteeg, H.A. Kooijman, R. Taylor, J.A. Hogendoorn, Ind. Eng. Chem. Res. 47 (2008) 9854–9861. [3] J. Gong, X. Ma, S. Wang, Appl. Catal. A 316 (2007) 1–21. [4] S. Fukuoka, M. Kawamura, K. Komiya, M. Tojo, H. Hachiya, K. Hasegawa, M. Aminaka, H. Okamoto, I. Fukawa, S. Konno, Green Chem. 5 (2003) 497–507. [5] Y. Ono, Appl. Catal. A 155 (1997) 133–166. [6] G.M. Wilson, C.H. Deal, Ind. Chem. Fundam. 1 (1962) 20–23. [7] H. Renon, J.M. Prausnitz, AIChE J. 14 (1968) 135–144. [8] D.S. Abrams, J.M. Prausnitz, AIChE J. 21 (1975) 116–128. [9] O. Redlich, A.T. Kister, Ind. Eng. Chem. 40 (1948) 345–348. [10] Dortmund Data Bank Software Package (DDBSP), Version 2006 Professional, Software and Separation Technology GmbH (http://www.ddbst.de). [11] M. Iglesias, B. Orge, J. Tojo, Fluid Phase Equilib. 126 (1996) 203–223. [12] I.G. Fuente, J.A. Gonztilez, J.C. Cobos, C. Casanova, J. Chem. Eng. Data 37 (1992) 535–537. [13] S.J. Park, K.J. Han, J. Gmehling, Fluid Phase Equilib. 200 (2002) 399–409. [14] K.J. Han, I.C. Hwang, S.J. Park, M.J. Choi, S.B. Lee, J.S. Han, Fluid Phase Equilib. 249 (2006) 187–191. [15] J.H. Oh, S.J. Park, J. Chem. Eng. Data 43 (1998) 1009–1013. [16] S.J. Park, H.H. Kim, K.J. Han, D.B. Won, S.B. Lee, M.J. Choi, Fluid Phase Equilib. 180 (2001) 361–373. [17] K.J. Han, J.H. Oh, S.J. Park, J. Ind. Eng. Chem. 13 (2007) 360–366. [18] T.M. Aminabhavi, B. Golalakrishina, J. Chem. Eng. Data 40 (1995) 856–861. [19] A.H. Al-Dujaili, A.A. Yassen, A.M. Awwad, J. Chem. Eng. Data 45 (2000) 647–649.