VaporâLiquid Equilibrium for Several Compounds Relevant to the

Article pubs.acs.org/jced

Vapor−Liquid Equilibrium for Several Compounds Relevant to the Biofuels Industry Modeled with the Wilson Equation Rubin J. McDougal,* Louis V. Jasperson, and Grant M. Wilson Wiltec Research Company, 488 S 500 W, Provo, Utah 84601, United States ABSTRACT: Vapor−liquid equilibrium (VLE) measurements have been performed on several binary systems incorporating chemicals of interest to the biofuels industry. Systems were chosen based on two criteria: (1) similarity to measurement requests received by Wiltec and (2) suitability of using the Wilson Equation to model the activity coefficients for the VLE data. The Wilson Equation is a good choice for modeling fully miscible solutions of moderately polar compounds. With these two ideas in mind, systems were chosen incorporating the following compounds: 1-methoxy-2-propanol, 2-furaldehyde, allyl alcohol, butyl acetate, carbon dioxide, carbon disulfide, carbonyl sulfide, ethanolamine, ethyl acetate, n-butanol, pentane, and tert-butanol. Measurement temperatures ranged from −25 °C to +200 °C.

■

INTRODUCTION

Vapor−liquid equilibrium (VLE) measurements have been performed on several binary systems incorporating chemicals of interest to the biofuels industry. Systems were chosen based on two criteria: (1) similarity to measurement requests received by Wiltec and (2) suitability of using the Wilson Equation to model the activity coefficients for the VLE data. The Wilson Equation is a good choice for modeling fully miscible solutions of moderately polar compounds. With these two ideas in mind, systems were chosen incorporating the following compounds: 1-methoxy-2-propanol, 2-furaldehyde, allyl alcohol, butyl acetate, carbon dioxide, carbon disulfide, carbonyl sulfide, ethanolamine, ethyl acetate, n-butanol, pentane, and tert-butanol. Measurement temperatures ranged from −25 °C to +200 °C.

■

APPARATUS AND PROCEDURES The reported VLE data have been measured using the total pressure method (PTx), where total pressure is a function of charge composition at a constant temperature. The experimental apparatus is shown in Figure 1. This apparatus consisted of a 300 cm3 stainless steel cylinder immersed in a constant temperature oil bath. Stainless steel tubing was connected to the cell for adding material, degassing, and measuring the pressure. The pressure was measured using a pressure transducer to an accuracy of ± 0.5 kPa. A thermowell extended through the top of the cell and into the liquid phase. Platinum resistance thermometers were used to measure the temperature in the cell and in the bath. These thermometers were calibrated using ice and steam points and then referenced to a NIST traceable standard resistance thermometer. Temperatures were measured to an accuracy of ± 0.025 °C. A PTx run was initiated by evacuating the cell and then charging it gravimetrically with a known mass of one of the compounds, accurate to ± 0.001 g. The cell was submerged in an isothermal bath and the cell contents were vigorously shaken until equilibrium was established at the desired temperature. The cell contents were then degassed by withdrawing the vapor into a weighed receiver. Degassing was done to remove any © 2014 American Chemical Society

Figure 1. Stainless steel cell used for vapor−liquid equilibrium measurements.

compounds from the cell that were lighter than the compounds of interest. These light compounds can cause errors in the total pressure measurements. The vapor pressure of the pure compound was then read. The cell contents were again degassed, and the pressure was again recorded. This procedure was repeated until a stable vapor pressure was obtained. Weighed increments of the second compound were then added to the cell. After each addition, the cell contents were Special Issue: In Honor of Grant Wilson Received: October 7, 2013 Accepted: March 13, 2014 Published: March 25, 2014 1069

dx.doi.org/10.1021/je400885z | J. Chem. Eng. Data 2014, 59, 1069−1085

Journal of Chemical & Engineering Data

Article

Table 1. Physical Properties, Sources, and Purities of Chemicals MW

Tc

Pc

chemical name

formula

g mol−1

K

kPa

Zc

ω

CAS No.

vendor

purity

1-methoxy-2-propanol 2-furaldehyde allyl alcohol butyl acetate carbon dioxide carbon disulfide carbonyl sulfide ethanolamine ethyl acetate n-butanol pentane tert-butanol

C4H10O2 C5H4O2 C3H6O C6H12O2 CO2 CS2 COS C2H7NO C4H8O2 C4H10O C5H12 C4H10O

90.12 96.09 58.08 116.16 44.01 76.14 60.08 61.08 88.11 74.12 72.15 74.12

553.00 670.15 545.10 575.40 304.19 552.00 378.80 678.20 523.30 563.05 469.70 506.21

4340 5660 5620 3090 7382 7900 6349 7124 3880 4423 3370 3973

0.278 0.256 0.258 0.251 0.274 0.275 0.272 0.284 0.255 0.260 0.270 0.260

0.7219 0.3678 0.5697 0.4394 0.2276 0.1107 0.0970 0.4467 0.3664 0.5935 0.2515 0.6115

107-98-2 98-01-1 107-18-6 123-86-4 124-38-9 75-15-0 463-58-1 141-43-5 141-78-6 71-36-3 109-66-0 75-65-0

Aldrich Aldrich Aldrich Aldrich Praxair Aldrich Praxair Aldrich Aldrich Aldrich Aldrich Aldrich

98+ % 99 % 99+ % 99.5 % 99.99 % 99.9+ % 99 % 99+ % 99.8 % 99.5+ % 99+ % 99.5+ %

Table 2. VLE Measurement Summary component 1

component 2

T/°C

Λ12

Λ21

γ12∞

γ21∞

deviation

carbonyl sulfide carbonyl sulfide carbon disulfide carbon disulfide n-butanol n-butanol ethanolamine ethanolamine ethanolamine ethanolamine ethanolamine ethanolamine 1-methoxy-2-propanol 1-methoxy-2-propanol 2-furaldehyde 2-furaldehyde 2-furaldehyde 2-furaldehyde butyl acetate butyl acetate butyl acetate butyl acetate butyl acetate butyl acetate

carbon dioxide carbon dioxide carbonyl sulfide carbonyl sulfide pentane pentane allyl alcohol allyl alcohol tert-butanol tert-butanol 1-methoxy-2-propanol 1-methoxy-2-propanol ethyl acetate ethyl acetate allyl alcohol allyl alcohol 1-methoxy-2-propanol 1-methoxy-2-propanol allyl alcohol allyl alcohol tert-butanol tert-butanol 1-methoxy-2-propanol 1-methoxy-2-propanol

−25 0 −25 0 60 120 100 150 100 150 100 150 100 150 100 150 100 150 100 150 100 150 150 200

0.6600 0.8529 0.4805 0.5135 0.0975 0.2722 0.4542 0.6094 1.0498 0.7643 0.3259 1.0220 0.6232 0.6571 0.3359 0.4062 0.4821 0.6872 0.3040 0.3571 0.5915 0.6876 0.5162 0.5891

0.6555 0.5941 0.8710 0.9908 0.6118 0.6306 2.2020 1.6400 0.4128 0.5837 1.4249 0.6276 1.0459 1.1283 1.0558 1.2463 0.9417 0.9080 1.4707 1.6087 1.1845 1.2767 1.2885 1.3080

2.138 1.759 2.368 1.965 15.126 5.316 0.662 0.865 1.714 1.984 2.006 1.420 1.533 1.338 2.815 1.924 2.199 1.595 2.054 1.523 1.406 1.103 1.452 1.247

2.143 1.950 1.930 1.642 4.031 3.283 0.784 0.901 2.305 2.168 1.377 1.559 1.394 1.249 1.840 1.453 1.782 1.506 1.364 1.182 1.270 1.071 1.259 1.153

positive positive positive positive positive positive negative negative positive positive positive positive positive positive positive positive positive positive positive positive positive nearly ideal positive positive

comments

pinch pinch

pinch pinch pinch

azeotrope azeotrope

To derive equilibrium phase compositions from PTx data, an iterative procedure is used to solve the basic equation of vapor− liquid equilibrium, given as follows:

brought to equilibrium at the desired temperature and degassed. The pressure was then measured and recorded. This procedure was repeated until over half of the entire composition range had been traversed. The other half of the composition range was covered by repeating the same procedure starting with the second compound and adding increments of the first compound. Table 1 lists the source, purity, and critical constants of the compounds used in this study.

⎡ V (P − Pio) ⎤ Pyiϕi = xiγiPioϕio exp⎢ i ⎥ ⎣ ⎦ RT

(1)

where P is the total pressure, yi is the vapor mole fraction of component i, ϕi is the fugacity coefficient of component i, xi is the liquid mole fraction of component i, γi is the activity coefficient of component i, Poi is the vapor pressure of component i at system temperature, ϕoi is the fugacity coefficient of component i at system temperature and corresponding vapor pressure of component i, and the exponential term is the Poynting correction where Vi is the molar volume of component i, R is the gas constant, and T is the absolute temperature. In the above expression, it is assumed that the molar volume of component i is equal to the partial molar volume of component

■

DATA REDUCTION PROCEDURE The results of the PTx measurements were reduced to equilibrium phase compositions and activity and fugacity coefficients. The Soave equation of state1 was used to represent the vapor phase, while the Wilson activity coefficient equation2 was used to represent the liquid phase nonidealities in the data reduction procedure. The Soave binary interaction parameters used in the data reduction procedure were assumed to be zero. 1070



Article

Figure 2. Px plot for two systems with carbonyl sulfide.

Figure 4. Px plot for three systems with butyl acetate.

Figure 3. Px plot for three systems with allyl alcohol.

Figure 5. Px plot for three systems with n- or tert-butanol.

i at these conditions. Pure component molar volumes were calculated from correlations of density data. These correlations and critical constants used in the data reduction procedure were taken from Rowley et al.3 Critical constants are reported in Table 1. The data reduction procedure consists of fitting the pressure data to eq 1 across the entire composition range by adjusting the parameters of the activity coefficient model. The Wilson activity coefficient equation was used in the data reduction procedure. This equation is shown below:

Wilson Equation: ⎞ ⎛ Λ12 Λ 21 ln γ1 = −ln(x1 + Λ12x 2) + x 2⎜ − ⎟ Λ 21x1 + x 2 ⎠ ⎝ x1 + Λ12x 2 (2)

⎞ ⎛ Λ 21 Λ12 ln γ2 = −ln(x 2 + Λ 21x1) − x1⎜ − ⎟ Λ 21x1 + x 2 ⎠ ⎝ x1 + Λ12x 2 (3) 1071



Article

Table 3. Carbonyl Sulfide (1) + Carbon Dioxide (2) PTx Measurements at −25 °C and 0 °C with Calculated Vapor Phase Composition, Activity Coefficients, Fugacity Coefficients, and Relative Volatilitya mole fraction (1) run

charge

liquid

pressure/kPa vapor

meas

calc

activity coefficient

fugacity coefficient

(1)

(1)

(2)

(2)/(1)

0.950 0.940 0.930 0.920 0.911 0.895 0.882 0.869 0.854 0.844 0.834 0.824 0.815 0.815 0.808 0.807 0.800 0.799 0.792 0.785 0.777 0.770 0.764 0.756 0.752 0.749 0.747 0.745 0.743 0.741

0.980 0.974 0.969 0.963 0.958 0.949 0.941 0.933 0.925 0.919 0.913 0.908 0.902 0.902 0.898 0.897 0.893 0.893 0.888 0.884 0.879 0.875 0.871 0.865 0.863 0.861 0.860 0.858 0.857 0.856

10.78 10.37 9.967 9.540 9.152 8.447 7.847 7.222 6.564 6.076 5.618 5.143 4.747 4.739 4.398 4.363 4.070 4.029 3.747 3.458 3.188 2.942 2.727 2.485 2.395 2.292 2.251 2.185 2.128 2.085

0.913 0.900 0.888 0.875 0.863 0.842 0.824 0.804 0.784 0.768 0.753 0.736 0.721 0.721 0.708 0.707 0.696 0.693 0.682 0.669 0.657 0.644 0.632 0.618 0.612 0.606

0.969 0.961 0.954 0.947 0.940 0.928 0.918 0.907 0.895 0.886 0.877 0.868 0.859 0.859 0.852 0.851 0.844 0.843 0.836 0.828 0.820 0.812 0.804 0.795 0.791 0.786

8.038 7.732 7.432 7.114 6.826 6.303 5.861 5.402 4.923 4.570 4.243 3.907 3.625 3.619 3.388 3.365 3.173 3.137 2.962 2.774 2.597 2.437 2.296 2.138 2.079 2.011

(2)

Carbonyl Sulfide (1) + Carbon Dioxide (2) at −25 °C 1 1 1 1 1 1 1 1 1 1 1 1 2 1 2 1 2 1 2 2 2 2 2 2 2 2 2 2 2 2

1.0000 0.9758 0.9513 0.9245 0.8991 0.8507 0.8063 0.7566 0.6993 0.6529 0.6058 0.5525 0.5072 0.5029 0.4575 0.4525 0.4075 0.4039 0.3543 0.3033 0.2524 0.2028 0.1567 0.1014 0.0796 0.0542 0.0437 0.0268 0.0115 0.0000

1.0000 0.9790 0.9573 0.9330 0.9096 0.8638 0.8209 0.7716 0.7138 0.6664 0.6178 0.5625 0.5121 0.5110 0.4636 0.4586 0.4146 0.4082 0.3621 0.3114 0.2602 0.2100 0.1629 0.1060 0.0833 0.0568 0.0459 0.0281 0.0121 0.0000

1.0000 0.8180 0.6920 0.5933 0.5238 0.4289 0.3687 0.3187 0.2754 0.2474 0.2235 0.2000 0.1810 0.1806 0.1643 0.1626 0.1482 0.1462 0.1316 0.1157 0.0994 0.0829 0.0666 0.0455 0.0366 0.0256 0.0209 0.0131 0.0057 0.0000

282.15 340.21 394.78 462.16 515.73 613.55 696.20 782.76 875.57 944.79 1008.5 1079.2 1125.0 1141.8 1180.5 1205.0 1234.4 1254.8 1291.7 1344.3 1397.8 1451.2 1501.5 1562.7 1584.9 1619.2 1629.8 1648.8 1666.3 1672.6

282.15 342.04 400.51 462.00 517.49 617.38 701.53 788.53 879.76 947.63 1011.7 1079.5 1137.5 1138.7 1190.6 1196.0 1242.5 1249.2 1296.7 1348.3 1400.1 1451.1 1499.5 1558.9 1582.8 1611.1 1622.9 1642.0 1659.4 1672.6

1.000 1.000 1.001 1.004 1.006 1.015 1.025 1.041 1.065 1.089 1.117 1.156 1.196 1.197 1.241 1.246 1.293 1.300 1.356 1.426 1.506 1.596 1.692 1.826 1.885 1.959 1.991 2.046 2.098 2.138

relative volatility

b

2.143 2.073 2.004 1.933 1.868 1.753 1.658 1.562 1.464 1.393 1.330 1.267 1.217 1.216 1.175 1.171 1.138 1.134 1.104 1.077 1.053 1.035 1.021 1.009 1.005 1.003 1.002 1.001 1.000 1.000

Carbonyl Sulfide (1) + Carbon Dioxide (2) at 0 °Cc 1 1 1 1 1 1 1 1 1 1 1 1 1 2 2 1 2 1 2 2 2 2 2 2 2 2

1.0000 0.9758 0.9513 0.9245 0.8991 0.8507 0.8063 0.7566 0.6993 0.6529 0.6058 0.5525 0.5029 0.5072 0.4575 0.4525 0.4075 0.4039 0.3543 0.3033 0.2524 0.2028 0.1567 0.1014 0.0796 0.0542

1.0000 0.9803 0.9598 0.9367 0.9144 0.8701 0.8281 0.7793 0.7215 0.6736 0.6244 0.5680 0.5152 0.5140 0.4666 0.4615 0.4185 0.4099 0.3669 0.3167 0.2658 0.2155 0.1679 0.1098 0.0866 0.0592

1.0000 0.8657 0.7627 0.6755 0.6101 0.5152 0.4511 0.3953 0.3448 0.3111 0.2815 0.2517 0.2267 0.2261 0.2052 0.2030 0.1849 0.1813 0.1636 0.1432 0.1224 0.1013 0.0808 0.0546 0.0436 0.0303

638.23 728.70 816.82 929.52 1018.9 1187.5 1338.8 1501.9 1680.7 1821.8 1957.7 2106.9 2239.8 2207.6 2315.5 2373.5 2431.2 2497.7 2558.2 2677.1 2801.8 2926.5 3042.6 3203.7 3265.3 3348.9

638.23 735.12 831.12 933.69 1027.8 1201.3 1352.2 1513.2 1688.5 1823.8 1955.8 2100.1 2230.2 2233.3 2347.6 2359.7 2462.1 2482.5 2584.4 2703.3 2824.7 2946.0 3062.2 3206.3 3264.7 3334.0 1072

1.000 1.000 1.001 1.003 1.006 1.013 1.022 1.036 1.057 1.078 1.102 1.134 1.168 1.169 1.203 1.206 1.241 1.248 1.286 1.334 1.387 1.445 1.505 1.585 1.619 1.661

1.950 1.889 1.830 1.768 1.712 1.613 1.531 1.448 1.365 1.306 1.253 1.201 1.160 1.159 1.128 1.124 1.100 1.096 1.075 1.055 1.038 1.024 1.015 1.006 1.004 1.002



Article

Table 3. continued mole fraction (1) run 2 2 2 2

charge 0.0437 0.0268 0.0115 0.0000

liquid 0.0478 0.0294 0.0127 0.0000

pressure/kPa vapor 0.0247 0.0153 0.0067 0.0000

meas

calc



(1)

(1)

(2)

(2)/(1)

0.603 0.599 0.595 0.592

0.784 0.781 0.778 0.776

1.984 1.941 1.904 1.876

(2)

Carbonyl Sulfide (1) + Carbon Dioxide (2) at 0 °Cc 3372.7 3362.8 1.679 1.001 3420.9 3409.9 1.709 1.000 3462.3 3452.6 1.738 1.000 3485.1 3485.1 1.759 1.000

relative volatility

a c

Standard uncertainties u are u(T) = 0.025 K, u(P) = 0.5 kPa, and u(x) = 0.0001. bWilson Equation parameters are Λ12 = 0.6600 and Λ21 = 0.6555. Wilson Equation parameters are Λ12 = 0.8529 and Λ21 = 0.5941.

Figure 6. Px plot for three systems with ethanolamine.

Figure 7. Px plot for two systems with 2-furaldehyde.

As a beginning point, the ideal-solution parameters of the activity coefficient model are selected. Then, assuming the fugacity coefficients are unity, eq 1 is solved for the product Pyi for each component. The calculated pressure is then the sum of these products:

are adjusted to improve the fit of the total pressure data, and the entire procedure is repeated until the best fit of the measured total pressure curve is obtained.

Pcalc =

∑ (Pyi)

■

RESULTS AND DISCUSSION The results of the PTx measurements are reported in Tables 3 to 13. These tables show the run number, the measured molar charge (z) compositions, the calculated molar liquid (x) and vapor (y) compositions, the measured and correlated total pressure (P), the calculated activity (γ) and fugacity (ϕ) coefficients, and the resulting relative volatility (α) for the binary system. Wilson Equation parameters (Λ) were used to correlate the measured data and are shown at the bottom of each table. Error in calculated activity coefficients is ±3 %. A summary of the systems is contained in Table 2. This table compiles the results for each system and lists the compounds, measurement temperatures, Wilson Equation parameters, infinite dilution activity coefficients, descriptions of the deviation from ideality, and other noteworthy comments. Figures 2 to 8 show plots of the total pressure versus composition for several of the binary isotherms studied. In these plots, open symbols represent the measured Px data while the long dashed lines represent the correlations of the Px data.

(4)

The vapor mole fraction for each component is then determined: Py yi = i Pcalc (5) With values for the vapor-phase composition, the fugacity coefficients can be calculated from the equation of state. The next step is to correct the liquid composition for the amounts of each component in the vapor, return to the step in which the activity coefficients are calculated, and continue iterating until the calculated pressure converges. As part of each iteration step, the amount of material removed from the cell as degas is subtracted from the total charge at the calculated vapor composition. This procedure is performed for each measured point across the composition range. The calculated pressures are compared with the measured pressures. The activity coefficient parameters 1073



Article

Table 4. Carbon Disulfide (1) + Carbonyl Sulfide (2) PTx Measurements at −25 °C and 0 °C with Calculated Vapor Phase Composition, Activity Coefficients, Fugacity Coefficients, and Relative Volatilitya mole fraction (1) run

charge

liquid

pressure/kPa vapor

meas

calc

activity coefficient

fugacity coefficient

(1)

(1)

(2)

(2)/(1)

0.998 0.994 0.989 0.985 0.981 0.973 0.967 0.961 0.955 0.951 0.946 0.946 0.942 0.938 0.938 0.935 0.931 0.928 0.924 0.921 0.917 0.914 0.911 0.909 0.907 0.905

0.999 0.997 0.994 0.992 0.990 0.986 0.983 0.980 0.977 0.974 0.972 0.972 0.970 0.968 0.968 0.966 0.964 0.962 0.960 0.958 0.956 0.954 0.953 0.952 0.951 0.950

116.1 112.5 108.9 105.8 102.6 95.52 89.00 83.29 77.34 72.18 67.42 66.80 62.23 57.75 57.66 53.47 49.34 45.33 41.51 37.78 34.15 30.87 29.07 27.36 25.81 24.21

0.995 0.988 0.982 0.976 0.970 0.958 0.947 0.937 0.927 0.919 0.911 0.910 0.904 0.903 0.896 0.896 0.889 0.882 0.876 0.869 0.863 0.855 0.849 0.844 0.840 0.836 0.832

0.998 0.994 0.991 0.988 0.985 0.979 0.973 0.968 0.963 0.958 0.954 0.953 0.950 0.950 0.946 0.946 0.942 0.939 0.935 0.932 0.928 0.924 0.921 0.919 0.916 0.914 0.912

55.58 54.28 52.99 51.85 50.63 47.94 45.39 43.10 40.65 38.47 36.42 36.10 34.51 34.12 32.15 32.09 30.23 28.33 26.46 24.63 22.80 20.98 19.30 18.36 17.45 16.62 15.75

(2)

Carbon Disulfide (1) + Carbonyl Sulfide (2) at −25 °C 1 1 1 1 1 1 1 1 1 1 1 2 2 2 1 2 2 2 2 2 2 2 2 2 2 2

1.0000 0.9713 0.9429 0.9175 0.8904 0.8303 0.7726 0.7200 0.6631 0.6119 0.5628 0.5579 0.5078 0.4569 0.4562 0.4065 0.3562 0.3054 0.2552 0.2043 0.1529 0.1045 0.0771 0.0506 0.0260 0.0000

1.0000 0.9724 0.9450 0.9203 0.8938 0.8346 0.7772 0.7246 0.6675 0.6158 0.5663 0.5597 0.5100 0.4595 0.4585 0.4094 0.3592 0.3085 0.2582 0.2071 0.1552 0.1064 0.0786 0.0516 0.0265 0.0000

1.0000 0.2388 0.1363 0.0983 0.0758 0.0502 0.0377 0.0306 0.0253 0.0217 0.0190 0.0187 0.0165 0.0145 0.0145 0.0128 0.0112 0.0097 0.0083 0.0069 0.0054 0.0038 0.0029 0.0020 0.0011 0.0000

4.50 19.18 32.03 42.78 53.61 76.24 97.50 114.28 131.34 146.95 162.97 161.49 172.75 184.23 188.64 195.02 206.46 216.76 226.40 240.15 251.27 263.30 270.58 277.26 283.84 287.13

4.50 18.44 31.59 42.89 54.40 78.14 98.84 116.03 133.07 147.21 159.80 161.41 173.15 184.46 184.68 195.18 205.59 215.95 226.23 236.86 248.06 259.26 266.01 272.86 279.60 287.13

1.000 1.000 1.002 1.003 1.006 1.015 1.029 1.045 1.068 1.094 1.124 1.128 1.165 1.210 1.211 1.262 1.325 1.400 1.489 1.599 1.734 1.890 1.994 2.107 2.226 2.368

relative volatility

b

1.930 1.875 1.822 1.776 1.730 1.632 1.546 1.474 1.403 1.344 1.293 1.286 1.240 1.197 1.196 1.158 1.124 1.093 1.067 1.044 1.026 1.012 1.007 1.003 1.001 1.000

Carbon Disulfide (1) + Carbonyl Sulfide (2) at 0 °Cc 1 1 1 1 1 1 1 1 1 1 1 2 1 2 2 1 2 2 2 2 2 2 2 2 2 2 2

1.0000 0.9713 0.9429 0.9175 0.8904 0.8303 0.7726 0.7200 0.6631 0.6119 0.5628 0.5579 0.5161 0.5078 0.4569 0.4562 0.4065 0.3562 0.3054 0.2552 0.2043 0.1529 0.1045 0.0771 0.0506 0.0260 0.0000

1.0000 0.9731 0.9464 0.9221 0.8961 0.8377 0.7807 0.7283 0.6711 0.6192 0.5692 0.5612 0.5216 0.5120 0.4618 0.4604 0.4120 0.3621 0.3115 0.2612 0.2100 0.1578 0.1083 0.0801 0.0527 0.0271 0.0000

1.0000 0.4004 0.2498 0.1859 0.1455 0.0972 0.0727 0.0585 0.0478 0.0405 0.0350 0.0342 0.0306 0.0298 0.0260 0.0259 0.0227 0.0196 0.0168 0.0142 0.0115 0.0088 0.0063 0.0047 0.0032 0.0017 0.0000

17.30 43.06 67.04 88.45 110.30 155.79 198.63 233.59 269.52 302.46 337.50 348.36 365.73 375.10 401.48 394.26 426.58 453.14 477.63 502.33 529.45 559.53 586.91 603.70 621.84 638.15 651.42

17.30 42.38 66.59 87.85 109.98 157.13 200.09 237.15 275.19 307.75 337.52 342.19 364.72 370.10 397.47 398.22 423.83 449.70 475.62 501.38 528.00 555.94 583.62 600.18 616.92 633.25 651.42

1.000 1.000 1.001 1.002 1.004 1.011 1.020 1.032 1.049 1.068 1.090 1.094 1.115 1.121 1.153 1.154 1.191 1.237 1.291 1.355 1.433 1.528 1.637 1.709 1.788 1.869 1.965

1.642 1.609 1.577 1.549 1.520 1.458 1.401 1.353 1.303 1.262 1.224 1.219 1.191 1.185 1.153 1.152 1.124 1.098 1.075 1.054 1.036 1.021 1.010 1.006 1.003 1.001 1.000

a c

Standard uncertainties u are u(T) = 0.025 K, u(P) = 0.5 kPa, and u(x) = 0.0001. bWilson Equation parameters are Λ12 = 0.4805 and Λ21 = 0.8710. Wilson Equation parameters are Λ12 = 0.5135 and Λ21 = 0.9908. 1074



Article

Table 5. Ethanolamine (1) + Allyl Alcohol (2) PTx Measurements at 100 °C and 150 °C with Calculated Vapor Phase Composition, Activity Coefficients, Fugacity Coefficients, and Relative Volatilitya mole fraction (1) run

charge

liquid

pressure/kPa vapor

1 1 1 1 1 1 1 1 1 1 1 2 1 2 1 2 1 2 2 2 2 2 2 2 2 2 2 2

1.0000 0.9754 0.9520 0.9283 0.9055 0.8579 0.8091 0.7595 0.7111 0.6602 0.6100 0.5702 0.5587 0.5186 0.5084 0.4673 0.4569 0.4153 0.3639 0.3118 0.2597 0.2065 0.1540 0.1026 0.0770 0.0510 0.0256 0.0000

1.0000 0.9755 0.9522 0.9286 0.9059 0.8584 0.8097 0.7601 0.7117 0.6609 0.6107 0.5705 0.5593 0.5191 0.5089 0.4679 0.4573 0.4159 0.3646 0.3126 0.2605 0.2073 0.1547 0.1032 0.0774 0.0513 0.0258 0.0000

1.0000 0.7382 0.5837 0.4762 0.4005 0.2928 0.2222 0.1728 0.1376 0.1097 0.0884 0.0745 0.0710 0.0599 0.0573 0.0480 0.0458 0.0381 0.0299 0.0230 0.0172 0.0122 0.0082 0.0049 0.0035 0.0022 0.0010 0.0000

1 1 1 1 1 1 1 1 1 1 1 2 1 2 1 2 1 2 2 2 2 2 2 2 2 2 2 2

1.0000 0.9754 0.9520 0.9283 0.9055 0.8579 0.8091 0.7595 0.7111 0.6602 0.6100 0.5702 0.5587 0.5186 0.5084 0.4673 0.4569 0.4153 0.3639 0.3118 0.2597 0.2065 0.1540 0.1026 0.0770 0.0510 0.0256 0.0000

1.0000 0.9758 0.9528 0.9295 0.9071 0.8600 0.8116 0.7622 0.7138 0.6629 0.6125 0.5715 0.5609 0.5204 0.5102 0.4695 0.4583 0.4178 0.3667 0.3148 0.2628 0.2095 0.1566 0.1047 0.0786 0.0522 0.0263 0.0000

1.0000 0.8256 0.7026 0.6060 0.5315 0.4148 0.3305 0.2670 0.2196 0.1803 0.1491 0.1279 0.1229 0.1056 0.1017 0.0870 0.0833 0.0710 0.0574 0.0456 0.0353 0.0261 0.0181 0.0113 0.0082 0.0053 0.0026 0.0000

meas

calc



(1)

(1)

(2)

(2)/(1)

0.998 0.997 0.997 0.996 0.996 0.994 0.993 0.992 0.990 0.989 0.987 0.986 0.986 0.984 0.984 0.983 0.982 0.981 0.979 0.977 0.975 0.973 0.971 0.969 0.968 0.967 0.966 0.966

0.999 0.998 0.998 0.997 0.997 0.996 0.995 0.994 0.993 0.992 0.990 0.989 0.989 0.988 0.988 0.987 0.987 0.985 0.984 0.983 0.981 0.980 0.978 0.977 0.976 0.975 0.975 0.974

14.00 14.10 14.20 14.31 14.41 14.64 14.90 15.18 15.47 15.81 16.18 16.50 16.59 16.95 17.04 17.44 17.55 18.00 18.62 19.34 20.15 21.10 22.21 23.47 24.19 24.98 25.83 26.78

0.989 0.987 0.985 0.983 0.981 0.977 0.973 0.968 0.964 0.959 0.954 0.950 0.949 0.945 0.944 0.940 0.939 0.935 0.930 0.924 0.919 0.913 0.907 0.901 0.898 0.896 0.893 0.890

0.992 0.991 0.989 0.988 0.987 0.984 0.981 0.977 0.974 0.971 0.967 0.964 0.963 0.960 0.960 0.957 0.956 0.953 0.949 0.945 0.941 0.937 0.932 0.928 0.926 0.924 0.922 0.920

8.497 8.524 8.551 8.578 8.605 8.664 8.727 8.795 8.865 8.943 9.025 9.095 9.113 9.187 9.206 9.284 9.307 9.390 9.502 9.624 9.755 9.899 10.05 10.22 10.31 10.40 10.50 10.60

(2)

Ethanolamine (1) + Allyl Alcohol (2) at 100 °Cb 6.16 6.16 1.000 0.784 8.17 8.14 1.000 0.790 10.24 10.06 1.000 0.795 12.34 12.03 0.999 0.801 14.00 13.95 0.999 0.806 18.23 18.07 0.997 0.818 22.67 22.43 0.994 0.830 26.98 27.01 0.990 0.842 31.55 31.63 0.985 0.855 37.10 36.64 0.978 0.868 42.17 41.75 0.970 0.881 44.73 45.96 0.962 0.891 47.48 47.15 0.959 0.894 49.54 51.49 0.950 0.904 52.89 52.60 0.947 0.907 56.02 57.15 0.936 0.917 59.16 58.35 0.933 0.920 61.90 63.07 0.919 0.930 67.49 69.06 0.900 0.943 74.40 75.27 0.878 0.955 81.08 81.59 0.852 0.967 88.06 88.12 0.822 0.977 95.59 94.62 0.788 0.986 102.47 100.94 0.751 0.993 105.82 104.06 0.730 0.996 109.24 107.17 0.708 0.998 112.18 110.16 0.686 1.000 113.10 113.10 0.662 1.000 Ethanolamine (1) + Allyl Alcohol (2) at 150 °Cc 50.62 50.62 1.000 0.901 59.82 59.96 1.000 0.904 70.54 68.93 1.000 0.908 77.80 78.12 1.000 0.911 87.66 87.08 0.999 0.914 108.22 106.15 0.998 0.920 128.21 126.18 0.997 0.927 148.41 147.09 0.995 0.933 169.45 167.98 0.993 0.939 192.07 190.44 0.990 0.946 214.96 213.17 0.986 0.952 225.31 232.04 0.982 0.957 239.03 236.95 0.981 0.958 249.11 255.96 0.977 0.963 262.69 260.75 0.976 0.964 273.06 280.23 0.971 0.969 288.59 285.65 0.970 0.970 299.05 305.38 0.964 0.974 324.77 330.65 0.957 0.980 351.06 356.76 0.948 0.984 379.51 383.29 0.938 0.989 409.11 410.81 0.926 0.992 438.75 438.40 0.913 0.996 468.37 465.66 0.899 0.998 483.19 479.36 0.891 0.999 498.02 493.27 0.883 0.999 513.42 506.90 0.874 1.000 520.67 520.67 0.865 1.000

relative volatility

a c




Article

Table 6. Ethanolamine (1) + tert-Butanol (2) PTx Measurements at 100 °C and 150 °C with Calculated Vapor Phase Composition, Activity Coefficients, Fugacity Coefficients, and Relative Volatilitya mole fraction (1) run

charge

liquid

pressure/kPa vapor

1 1 1 1 1 1 1 1 1 1 1 2 1 2 1 2 1 2 2 2 2 2 2 2 2 2 2 2

1.0000 0.9777 0.9555 0.9358 0.9140 0.8644 0.8150 0.7689 0.7184 0.6682 0.6179 0.5723 0.5652 0.5203 0.5133 0.4696 0.4606 0.4175 0.3646 0.3123 0.2592 0.2072 0.1541 0.1044 0.0813 0.0616 0.0419 0.0000

1.0000 0.9784 0.9568 0.9375 0.9160 0.8669 0.8178 0.7717 0.7211 0.6707 0.6201 0.5735 0.5670 0.5218 0.5148 0.4712 0.4617 0.4193 0.3664 0.3142 0.2611 0.2089 0.1556 0.1055 0.0822 0.0623 0.0424 0.0000

1.0000 0.4140 0.2673 0.2057 0.1655 0.1166 0.0913 0.0761 0.0644 0.0555 0.0483 0.0427 0.0419 0.0372 0.0366 0.0325 0.0317 0.0281 0.0239 0.0201 0.0164 0.0129 0.0094 0.0063 0.0049 0.0037 0.0025 0.0000

1 1 1 1 1 1 1 1 1 1 1 2 1 2 1 2 1 2 2 2 2 2 2 2 2 2 2 2

1.0000 0.9777 0.9555 0.9358 0.9140 0.8644 0.8150 0.7689 0.7184 0.6682 0.6179 0.5723 0.5652 0.5203 0.5133 0.4696 0.4606 0.4175 0.3646 0.3123 0.2592 0.2072 0.1541 0.1044 0.0813 0.0616 0.0419 0.0000

1.0000 0.9798 0.9593 0.9410 0.9204 0.8728 0.8246 0.7787 0.7280 0.6771 0.6258 0.5763 0.5717 0.5252 0.5185 0.4752 0.4643 0.4238 0.3712 0.3190 0.2658 0.2133 0.1594 0.1084 0.0846 0.0642 0.0437 0.0000

1.0000 0.6376 0.4708 0.3833 0.3188 0.2318 0.1833 0.1534 0.1301 0.1126 0.0987 0.0875 0.0865 0.0775 0.0763 0.0688 0.0670 0.0606 0.0528 0.0454 0.0380 0.0308 0.0233 0.0161 0.0127 0.0097 0.0067 0.0000

meas

calc



(1)

(1)

(2)

(2)/(1)

0.998 0.995 0.993 0.991 0.989 0.985 0.982 0.979 0.976 0.974 0.971 0.969 0.969 0.967 0.967 0.965 0.964 0.962 0.960 0.957 0.955 0.952 0.949 0.947 0.945 0.944 0.943 0.941

0.998 0.996 0.994 0.993 0.991 0.988 0.985 0.983 0.981 0.979 0.977 0.975 0.975 0.973 0.973 0.971 0.971 0.969 0.967 0.965 0.963 0.961 0.959 0.956 0.955 0.954 0.953 0.951

68.02 64.18 60.70 57.88 55.01 49.35 44.69 41.01 37.59 34.69 32.19 30.17 29.91 28.21 27.96 26.52 26.22 24.98 23.59 22.37 21.25 20.25 19.33 18.54 18.20 17.91 17.64 17.08

0.989 0.982 0.976 0.971 0.966 0.955 0.945 0.936 0.928 0.920 0.912 0.906 0.905 0.899 0.898 0.893 0.891 0.886 0.879 0.873 0.866 0.858 0.851 0.843 0.839 0.836 0.832 0.825

0.991 0.987 0.982 0.978 0.974 0.965 0.958 0.951 0.944 0.938 0.933 0.927 0.927 0.922 0.922 0.917 0.916 0.912 0.907 0.902 0.897 0.891 0.885 0.879 0.876 0.874 0.871 0.865

28.61 27.54 26.52 25.65 24.72 22.74 20.94 19.42 17.90 16.53 15.28 14.19 14.09 13.17 13.04 12.25 12.06 11.39 10.59 9.854 9.166 8.538 7.944 7.424 7.193 7.001 6.814 6.431

(2)

Ethanolamine (1) + tert-Butanol (2) at 100 °Cb 6.17 6.17 1.000 2.305 13.75 14.64 1.001 2.177 22.11 22.28 1.002 2.063 29.11 28.48 1.005 1.973 36.16 34.80 1.009 1.882 48.60 47.50 1.020 1.709 58.39 58.34 1.036 1.573 67.40 67.37 1.055 1.470 73.75 76.36 1.078 1.378 85.58 84.68 1.105 1.303 92.48 92.60 1.134 1.242 99.56 99.67 1.164 1.195 101.12 100.64 1.168 1.189 107.09 107.37 1.200 1.152 108.69 108.40 1.205 1.147 114.26 114.85 1.238 1.117 116.04 116.26 1.245 1.111 122.38 122.55 1.279 1.088 129.72 130.50 1.324 1.064 135.54 138.51 1.371 1.045 144.90 146.87 1.422 1.030 154.76 155.34 1.474 1.018 163.52 164.29 1.531 1.010 173.14 173.00 1.587 1.004 177.13 177.16 1.614 1.003 181.01 180.77 1.637 1.001 185.36 184.45 1.661 1.001 192.46 192.46 1.714 1.000 Ethanolamine (1) + tert-Butanol (2) at 150 °Cc 52.71 52.71 1.000 2.168 79.21 81.59 1.000 2.091 105.91 109.02 1.001 2.017 132.56 132.31 1.003 1.956 159.74 156.93 1.006 1.891 211.99 208.97 1.014 1.758 258.65 255.70 1.027 1.642 297.64 295.63 1.042 1.547 338.10 335.75 1.062 1.457 374.24 372.71 1.087 1.379 408.93 407.42 1.117 1.312 432.11 439.11 1.150 1.256 443.46 442.00 1.153 1.251 463.89 470.57 1.188 1.206 476.70 474.66 1.194 1.200 494.48 500.60 1.231 1.164 508.80 507.12 1.241 1.156 525.54 531.13 1.280 1.127 559.51 562.38 1.337 1.095 591.77 593.80 1.400 1.069 626.39 626.73 1.472 1.047 662.39 660.48 1.552 1.030 701.12 696.75 1.643 1.017 739.46 732.95 1.739 1.008 759.47 750.65 1.788 1.005 776.76 766.21 1.832 1.003 793.62 782.29 1.878 1.001 818.16 818.16 1.984 1.000

relative volatility

a c




Article

Table 7. Ethanolamine (1) + 1-Methoxy-2-propanol (2) PTx Measurements at 100 °C and 150 °C with Calculated Vapor Phase Composition, Activity Coefficients, Fugacity Coefficients, and Relative Volatilitya mole fraction (1) run

charge

liquid

pressure/kPa vapor

1 1 1 1 1 1 1 1 1 1 1 2 1 2 1 2 1 2 2 2 2 2 2 2 2 2 2 2

1.0000 0.9754 0.9499 0.9268 0.9035 0.8559 0.8072 0.7584 0.7083 0.6576 0.6068 0.5698 0.5570 0.5200 0.5067 0.4688 0.4555 0.4177 0.3656 0.3144 0.2625 0.2105 0.1579 0.1056 0.0789 0.0531 0.0272 0.0000

1.0000 0.9755 0.9501 0.9271 0.9039 0.8564 0.8077 0.7590 0.7089 0.6581 0.6073 0.5700 0.5575 0.5203 0.5071 0.4692 0.4557 0.4181 0.3661 0.3148 0.2629 0.2109 0.1582 0.1058 0.0791 0.0532 0.0273 0.0000

1.0000 0.7960 0.6527 0.5582 0.4852 0.3780 0.3038 0.2504 0.2092 0.1767 0.1508 0.1348 0.1299 0.1165 0.1121 0.1005 0.0967 0.0867 0.0742 0.0632 0.0529 0.0432 0.0335 0.0236 0.0183 0.0128 0.0069 0.0000

1 1 1 1 1 1 1 1 1 1 1 2 1 2 1 2 1 2 2 2 2 2 2 2 2 2 2 2

1.0000 0.9754 0.9499 0.9268 0.9035 0.8559 0.8072 0.7584 0.7083 0.6576 0.6068 0.5698 0.5570 0.5200 0.5067 0.4688 0.4555 0.4177 0.3656 0.3144 0.2625 0.2105 0.1579 0.1056 0.0789 0.0531 0.0272 0.0000

1.0000 0.9759 0.9508 0.9280 0.9050 0.8577 0.8092 0.7605 0.7103 0.6594 0.6084 0.5706 0.5584 0.5209 0.5078 0.4699 0.4562 0.4189 0.3670 0.3157 0.2638 0.2117 0.1589 0.1064 0.0795 0.0535 0.0275 0.0000

1.0000 0.8618 0.7536 0.6764 0.6129 0.5126 0.4370 0.3783 0.3297 0.2888 0.2538 0.2308 0.2238 0.2034 0.1966 0.1779 0.1715 0.1545 0.1323 0.1117 0.0918 0.0727 0.0539 0.0357 0.0266 0.0178 0.0091 0.0000

meas

calc



(1)

(1)

(2)

(2)/(1)

0.998 0.997 0.997 0.997 0.996 0.995 0.994 0.994 0.993 0.992 0.991 0.991 0.991 0.990 0.990 0.989 0.989 0.989 0.988 0.988 0.987 0.987 0.986 0.985 0.985 0.985 0.985 0.984

0.998 0.997 0.997 0.996 0.996 0.995 0.994 0.993 0.993 0.992 0.991 0.991 0.990 0.990 0.990 0.989 0.989 0.988 0.988 0.987 0.987 0.986 0.986 0.985 0.985 0.984 0.984 0.984

10.30 10.22 10.14 10.06 9.984 9.813 9.627 9.427 9.208 8.968 8.711 8.511 8.441 8.226 8.147 7.911 7.825 7.573 7.203 6.811 6.384 5.924 5.426 4.897 4.614 4.332 4.043 3.730

0.989 0.987 0.986 0.984 0.983 0.981 0.978 0.976 0.974 0.972 0.970 0.969 0.969 0.967 0.967 0.965 0.965 0.964 0.962 0.960 0.958 0.957 0.955 0.953 0.952 0.951 0.950 0.949

0.989 0.987 0.986 0.985 0.984 0.981 0.979 0.977 0.975 0.973 0.971 0.970 0.969 0.968 0.968 0.966 0.966 0.965 0.963 0.961 0.960 0.958 0.956 0.954 0.953 0.953 0.952 0.951

6.675 6.496 6.318 6.165 6.017 5.732 5.464 5.218 4.985 4.767 4.567 4.428 4.385 4.258 4.215 4.095 4.054 3.944 3.801 3.669 3.544 3.427 3.316 3.212 3.161 3.114 3.068 3.020

(2)

Ethanolamine (1) + 1-Methoxy-2-propanol (2) at 100 °Cb 6.64 6.64 1.000 1.377 7.72 8.15 1.000 1.367 9.41 9.68 1.000 1.357 10.59 11.06 1.001 1.347 12.81 12.42 1.002 1.337 15.55 15.15 1.004 1.317 18.12 17.85 1.007 1.296 20.32 20.46 1.011 1.275 23.04 23.04 1.018 1.253 25.49 25.55 1.026 1.231 27.78 27.96 1.037 1.208 30.32 29.66 1.047 1.192 30.24 30.22 1.051 1.186 32.20 31.83 1.064 1.170 32.85 32.39 1.069 1.164 33.95 33.96 1.085 1.147 34.90 34.50 1.092 1.142 35.76 35.99 1.112 1.125 37.51 37.95 1.146 1.104 39.17 39.80 1.190 1.083 40.93 41.59 1.246 1.063 42.72 43.33 1.319 1.044 44.70 45.06 1.417 1.027 46.67 46.77 1.549 1.014 47.77 47.66 1.635 1.008 48.49 48.54 1.734 1.004 50.07 49.45 1.853 1.001 50.45 50.45 2.006 1.000 Ethanolamine (1) + 1-Methoxy-2-propanol (2) at 150 °Cc 51.97 51.97 1.000 1.559 58.49 58.97 1.000 1.517 66.05 65.88 1.001 1.477 72.22 71.84 1.003 1.444 78.71 77.59 1.005 1.412 90.05 88.66 1.011 1.352 97.46 99.17 1.019 1.299 107.11 108.99 1.029 1.253 117.09 118.49 1.041 1.212 127.24 127.64 1.056 1.175 136.45 136.41 1.073 1.144 141.03 142.71 1.087 1.123 146.10 144.71 1.091 1.117 152.74 150.78 1.106 1.099 153.12 152.89 1.112 1.093 160.70 158.90 1.128 1.078 162.07 161.05 1.134 1.073 167.43 166.88 1.152 1.060 174.10 174.95 1.178 1.045 182.52 182.87 1.206 1.032 191.31 190.90 1.236 1.022 198.86 199.00 1.268 1.014 207.68 207.28 1.303 1.008 215.96 215.63 1.339 1.003 221.36 219.94 1.359 1.002 225.12 224.15 1.378 1.001 229.28 228.40 1.398 1.000 232.93 232.93 1.420 1.000

relative volatility

a c




Article

Table 8. 1-Methoxy-2-propanol (1) + Ethyl Acetate (2) PTx Measurements at 100 °C and 150 °C with Calculated Vapor Phase Composition, Activity Coefficients, Fugacity Coefficients, and Relative Volatilitya mole fraction (1) run

charge

liquid

pressure/kPa vapor

1 1 1 1 1 1 1 1 1 1 1 2 1 2 1 2 1 2 2 2 2 2 2 2 2 2 2 2

1.0000 0.9816 0.9540 0.9269 0.9037 0.8545 0.8056 0.7537 0.7048 0.6541 0.6047 0.5727 0.5538 0.5222 0.5020 0.4703 0.4521 0.4187 0.3660 0.3143 0.2613 0.2087 0.1564 0.1034 0.0773 0.0520 0.0265 0.0000

1.0000 0.9819 0.9546 0.9278 0.9049 0.8560 0.8072 0.7554 0.7065 0.6556 0.6061 0.5739 0.5549 0.5237 0.5029 0.4721 0.4527 0.4207 0.3681 0.3164 0.2634 0.2106 0.1580 0.1046 0.0782 0.0527 0.0268 0.0000

1.0000 0.9082 0.7958 0.7072 0.6441 0.5375 0.4572 0.3905 0.3399 0.2961 0.2600 0.2393 0.2278 0.2101 0.1990 0.1834 0.1741 0.1594 0.1369 0.1162 0.0961 0.0768 0.0579 0.0388 0.0292 0.0199 0.0102 0.0000

1 1 1 1 1 1 1 1 1 1 1 2 1 2 1 2 1 2 2 2 2 2 2 2 2 2 2 2

1.0000 0.9816 0.9540 0.9269 0.9037 0.8545 0.8056 0.7537 0.7048 0.6541 0.6047 0.5727 0.5538 0.5222 0.5020 0.4703 0.4521 0.4187 0.3660 0.3143 0.2613 0.2087 0.1564 0.1034 0.0773 0.0520 0.0265 0.0000

1.0000 0.9822 0.9553 0.9288 0.9061 0.8576 0.8091 0.7573 0.7084 0.6574 0.6076 0.5753 0.5561 0.5256 0.5038 0.4744 0.4532 0.4234 0.3711 0.3196 0.2665 0.2136 0.1606 0.1065 0.0797 0.0538 0.0274 0.0000

1.0000 0.9442 0.8690 0.8034 0.7528 0.6592 0.5810 0.5102 0.4528 0.4003 0.3551 0.3284 0.3132 0.2904 0.2748 0.2548 0.2408 0.2220 0.1908 0.1619 0.1335 0.1063 0.0797 0.0531 0.0398 0.0270 0.0138 0.0000

meas

calc



(1)

(1)

(2)

(2)/(1)

0.985 0.983 0.981 0.980 0.978 0.975 0.972 0.969 0.966 0.964 0.961 0.960 0.959 0.957 0.956 0.955 0.954 0.953 0.950 0.948 0.946 0.944 0.942 0.940 0.938 0.937 0.936 0.935

0.984 0.983 0.981 0.979 0.978 0.975 0.972 0.969 0.966 0.963 0.961 0.959 0.958 0.957 0.956 0.955 0.954 0.952 0.950 0.948 0.946 0.943 0.941 0.939 0.938 0.937 0.936 0.935

5.533 5.480 5.401 5.323 5.256 5.114 4.971 4.818 4.675 4.524 4.378 4.283 4.226 4.134 4.072 3.981 3.923 3.828 3.673 3.519 3.362 3.207 3.052 2.895 2.818 2.744 2.669 2.591

0.951 0.949 0.946 0.943 0.940 0.935 0.930 0.924 0.919 0.914 0.909 0.906 0.904 0.901 0.899 0.897 0.895 0.892 0.887 0.883 0.878 0.873 0.869 0.864 0.862 0.859 0.857 0.855

0.949 0.947 0.943 0.940 0.937 0.932 0.926 0.921 0.915 0.910 0.905 0.902 0.900 0.897 0.895 0.892 0.890 0.887 0.882 0.877 0.872 0.867 0.862 0.857 0.855 0.852 0.850 0.847

3.273 3.253 3.224 3.194 3.168 3.113 3.057 2.995 2.937 2.874 2.812 2.771 2.747 2.707 2.679 2.641 2.613 2.573 2.503 2.432 2.358 2.283 2.207 2.129 2.089 2.051 2.011 1.970

(2)

1-Methoxy-2-propanol (1) + Ethyl Acetate (2) at 100 °Cb 48.26 48.26 1.000 1.394 51.68 52.26 1.000 1.381 58.01 58.13 1.001 1.361 63.45 63.76 1.001 1.343 67.89 68.47 1.002 1.327 77.81 78.14 1.006 1.295 87.48 87.33 1.011 1.265 96.61 96.66 1.018 1.235 105.76 105.05 1.026 1.208 114.41 113.40 1.037 1.181 122.43 121.20 1.049 1.157 127.65 126.09 1.059 1.142 128.44 128.94 1.065 1.134 132.24 133.51 1.076 1.120 136.67 136.50 1.084 1.111 139.93 140.86 1.096 1.099 145.28 143.57 1.105 1.092 147.19 147.97 1.120 1.080 154.78 155.03 1.149 1.063 161.22 161.83 1.182 1.047 168.82 168.71 1.221 1.034 175.68 175.47 1.266 1.022 182.91 182.22 1.318 1.013 189.53 189.10 1.379 1.006 193.64 192.53 1.414 1.003 197.19 195.88 1.450 1.001 201.06 199.31 1.489 1.000 202.90 202.90 1.533 1.000 1-Methoxy-2-propanol (1) + Ethyl Acetate (2) at 150 °Cc 230.60 230.60 1.000 1.249 237.77 240.48 1.000 1.241 253.31 255.21 1.000 1.230 268.87 269.53 1.001 1.219 281.52 281.66 1.002 1.210 307.91 307.10 1.004 1.191 333.81 331.92 1.007 1.173 359.60 357.74 1.011 1.154 383.36 381.54 1.017 1.137 408.58 405.81 1.024 1.120 431.36 428.91 1.032 1.105 439.48 443.63 1.038 1.095 455.85 452.31 1.043 1.089 461.45 465.95 1.050 1.081 478.01 475.58 1.055 1.075 484.04 488.44 1.063 1.067 500.47 497.66 1.069 1.062 506.37 510.50 1.078 1.055 529.03 532.76 1.097 1.043 551.32 554.40 1.118 1.033 573.97 576.51 1.143 1.023 597.93 598.43 1.171 1.015 620.58 620.35 1.204 1.009 644.89 642.75 1.243 1.004 656.59 653.92 1.265 1.002 668.62 664.79 1.287 1.001 680.44 675.90 1.311 1.000 687.53 687.53 1.338 1.000

relative volatility

a c




Article

Table 9. 2-Furaldehyde (1) + Allyl Alcohol (2) PTx Measurements at 100 °C and 150 °C with Calculated Vapor Phase Composition, Activity Coefficients, Fugacity Coefficients, and Relative Volatilitya mole fraction (1) run

charge

liquid

pressure/kPa vapor

1 1 1 1 1 1 1 1 1 1 1 2 1 2 1 2 1 2 2 2 2 2 2 2 2 2 2 2

1.0000 0.9756 0.9522 0.9283 0.9052 0.8569 0.8085 0.7587 0.7084 0.6585 0.6086 0.5675 0.5580 0.5163 0.5069 0.4643 0.4564 0.4075 0.3564 0.3049 0.2531 0.2005 0.1507 0.0975 0.0766 0.0506 0.0295 0.0000

1.0000 0.9759 0.9527 0.9289 0.9060 0.8580 0.8097 0.7600 0.7096 0.6597 0.6096 0.5681 0.5588 0.5170 0.5076 0.4651 0.4569 0.4084 0.3573 0.3059 0.2540 0.2014 0.1514 0.0980 0.0769 0.0508 0.0296 0.0000

1.0000 0.7537 0.6081 0.5068 0.4359 0.3359 0.2715 0.2255 0.1915 0.1656 0.1450 0.1307 0.1278 0.1157 0.1132 0.1027 0.1008 0.0901 0.0799 0.0703 0.0608 0.0511 0.0413 0.0295 0.0242 0.0170 0.0105 0.0000

1 1 1 1 1 1 1 1 1 1 1 2 1 2 1 2 1 2 2 2 2 2 2 2 2 2 2 2

1.0000 0.9756 0.9522 0.9283 0.9052 0.8569 0.8085 0.7587 0.7084 0.6585 0.6086 0.5675 0.5580 0.5163 0.5069 0.4643 0.4564 0.4075 0.3564 0.3049 0.2531 0.2005 0.1507 0.0975 0.0766 0.0506 0.0295 0.0000

1.0000 0.9764 0.9537 0.9303 0.9077 0.8602 0.8123 0.7627 0.7124 0.6623 0.6120 0.5693 0.5609 0.5188 0.5093 0.4673 0.4582 0.4109 0.3600 0.3087 0.2568 0.2039 0.1535 0.0996 0.0782 0.0517 0.0301 0.0000

1.0000 0.8239 0.7018 0.6071 0.5354 0.4256 0.3489 0.2911 0.2465 0.2115 0.1830 0.1627 0.1590 0.1420 0.1384 0.1237 0.1207 0.1061 0.0919 0.0787 0.0660 0.0535 0.0416 0.0283 0.0228 0.0156 0.0094 0.0000

meas

calc



(1)

(1)

(2)

(2)/(1)

0.995 0.993 0.992 0.990 0.989 0.987 0.984 0.982 0.980 0.978 0.976 0.975 0.975 0.973 0.973 0.972 0.972 0.971 0.969 0.968 0.967 0.966 0.965 0.964 0.964 0.963 0.963 0.962

0.997 0.996 0.995 0.994 0.993 0.991 0.990 0.988 0.987 0.986 0.984 0.983 0.983 0.982 0.982 0.982 0.981 0.981 0.980 0.979 0.978 0.978 0.977 0.976 0.976 0.975 0.975 0.975

13.49 13.23 12.98 12.72 12.47 11.95 11.42 10.87 10.32 9.764 9.209 8.747 8.644 8.179 8.074 7.601 7.510 6.970 6.402 5.832 5.261 4.685 4.145 3.579 3.358 3.089 2.872 2.576

0.980 0.977 0.973 0.970 0.966 0.960 0.953 0.947 0.941 0.935 0.930 0.925 0.924 0.920 0.919 0.915 0.914 0.910 0.905 0.901 0.897 0.892 0.888 0.884 0.882 0.880 0.878 0.876

0.989 0.987 0.984 0.982 0.980 0.975 0.971 0.967 0.963 0.959 0.956 0.953 0.952 0.949 0.949 0.946 0.946 0.943 0.940 0.937 0.934 0.931 0.929 0.926 0.925 0.923 0.922 0.920

8.952 8.846 8.743 8.636 8.531 8.307 8.076 7.830 7.573 7.310 7.039 6.803 6.756 6.516 6.461 6.214 6.160 5.874 5.558 5.229 4.887 4.529 4.180 3.797 3.643 3.450 3.292 3.070

(2)

2-Furaldehyde (1) + Allyl Alcohol (2) at 100 °Cb 14.62 14.62 1.000 1.840 17.83 18.97 1.000 1.806 22.27 23.00 1.001 1.773 26.63 26.99 1.002 1.741 30.63 30.69 1.004 1.710 38.08 38.02 1.009 1.648 45.13 44.84 1.016 1.588 51.49 51.31 1.027 1.529 57.79 57.33 1.041 1.472 62.78 62.82 1.059 1.418 67.56 67.87 1.082 1.367 73.19 71.75 1.105 1.327 72.98 72.58 1.110 1.318 76.54 76.16 1.139 1.279 77.50 76.93 1.146 1.271 79.57 80.29 1.182 1.235 82.23 80.90 1.189 1.228 83.30 84.43 1.241 1.189 85.98 87.89 1.307 1.151 89.25 91.17 1.391 1.116 92.50 94.33 1.498 1.085 95.98 97.45 1.638 1.057 98.96 100.39 1.811 1.034 103.28 103.59 2.059 1.015 104.92 104.89 2.182 1.010 107.04 106.55 2.359 1.005 108.74 107.94 2.529 1.002 109.94 109.94 2.815 1.000 2-Furaldehyde (1) + Allyl Alcohol (2) at 150 °Cc 77.51 77.51 1.000 1.453 87.27 92.26 1.000 1.438 100.85 106.23 1.000 1.423 115.73 120.35 1.001 1.409 132.21 133.76 1.002 1.395 157.63 161.17 1.005 1.365 185.59 187.81 1.009 1.336 212.77 214.24 1.015 1.307 239.23 239.96 1.023 1.277 264.90 264.44 1.034 1.249 285.61 287.93 1.048 1.221 307.98 307.00 1.061 1.198 310.07 310.71 1.065 1.193 326.03 328.69 1.082 1.171 331.67 332.65 1.086 1.166 343.97 349.79 1.107 1.145 352.60 353.41 1.112 1.141 363.40 371.83 1.141 1.118 380.73 390.89 1.179 1.096 399.84 409.46 1.226 1.074 424.50 427.72 1.286 1.054 439.35 445.99 1.361 1.037 459.14 463.29 1.452 1.022 480.74 482.04 1.577 1.010 490.57 489.62 1.637 1.006 500.84 499.19 1.720 1.003 509.29 507.17 1.798 1.001 518.64 518.64 1.924 1.000

relative volatility

a c




Article

Table 10. 2-Furaldehyde (1) + 1-Methoxy-2-propanol (2) PTx Measurements at 100 °C and 150 °C with Calculated Vapor Phase Composition, Activity Coefficients, Fugacity Coefficients, and Relative Volatilitya mole fraction (1) run

charge

liquid

pressure/kPa vapor

1 1 1 1 1 1 1 1 1 1 1 1 2 1 2 2 2 2 2 2 2 2 2 2 2 2

1.0000 0.9749 0.9506 0.9260 0.9020 0.8522 0.8016 0.7521 0.7015 0.6509 0.6006 0.5492 0.5121 0.4993 0.4609 0.4098 0.3587 0.3072 0.2549 0.2043 0.1515 0.1010 0.0751 0.0529 0.0319 0.0000

1.0000 0.9751 0.9509 0.9264 0.9024 0.8527 0.8022 0.7528 0.7022 0.6514 0.6011 0.5496 0.5124 0.4996 0.4612 0.4102 0.3590 0.3075 0.2553 0.2046 0.1517 0.1011 0.0753 0.0529 0.0320 0.0000

1.0000 0.8728 0.7762 0.6975 0.6342 0.5325 0.4562 0.3985 0.3512 0.3121 0.2793 0.2503 0.2314 0.2252 0.2076 0.1857 0.1649 0.1446 0.1241 0.1037 0.0812 0.0576 0.0445 0.0324 0.0203 0.0000

1 1 1 1 1 1 1 1 1 1 1 2 1 2 1 2 1 2 2 2 2 2 2 2 2 2 2 2

1.0000 0.9749 0.9506 0.9260 0.9020 0.8522 0.8016 0.7521 0.7015 0.6509 0.6006 0.5631 0.5492 0.5121 0.4993 0.4609 0.4484 0.4098 0.3587 0.3072 0.2549 0.2043 0.1515 0.1010 0.0751 0.0529 0.0319 0.0000

1.0000 0.9754 0.9515 0.9272 0.9034 0.8540 0.8037 0.7542 0.7036 0.6527 0.6022 0.5639 0.5506 0.5131 0.5004 0.4620 0.4491 0.4111 0.3600 0.3085 0.2562 0.2055 0.1525 0.1017 0.0757 0.0532 0.0322 0.0000

1.0000 0.9015 0.8216 0.7529 0.6951 0.5968 0.5185 0.4563 0.4033 0.3581 0.3190 0.2924 0.2836 0.2602 0.2526 0.2305 0.2234 0.2031 0.1770 0.1517 0.1267 0.1027 0.0774 0.0527 0.0397 0.0282 0.0173 0.0000

meas

calc



(1)

(1)

(2)

(2)/(1)

0.995 0.994 0.994 0.993 0.992 0.991 0.990 0.990 0.989 0.988 0.988 0.987 0.987 0.986 0.986 0.986 0.985 0.985 0.984 0.984 0.984 0.983 0.983 0.983 0.983 0.983

0.995 0.995 0.994 0.994 0.993 0.992 0.992 0.991 0.990 0.989 0.989 0.988 0.988 0.988 0.988 0.987 0.987 0.986 0.986 0.986 0.985 0.985 0.985 0.985 0.985 0.984

5.834 5.705 5.580 5.455 5.334 5.085 4.836 4.596 4.355 4.118 3.887 3.655 3.491 3.434 3.268 3.050 2.837 2.628 2.420 2.224 2.025 1.840 1.747 1.669 1.596 1.487

0.981 0.979 0.978 0.976 0.975 0.972 0.969 0.967 0.965 0.962 0.960 0.959 0.958 0.957 0.957 0.955 0.955 0.954 0.952 0.950 0.949 0.947 0.946 0.944 0.944 0.943 0.942 0.942

0.984 0.983 0.981 0.980 0.979 0.977 0.974 0.972 0.970 0.969 0.967 0.966 0.965 0.964 0.964 0.963 0.962 0.961 0.960 0.958 0.957 0.956 0.954 0.953 0.953 0.952 0.952 0.951

4.413 4.333 4.256 4.179 4.105 3.953 3.802 3.657 3.512 3.369 3.232 3.129 3.094 2.997 2.964 2.866 2.834 2.740 2.616 2.494 2.373 2.259 2.143 2.035 1.981 1.935 1.892 1.827

(2)

2-Furaldehyde (1) + 1-Methoxy-2-propanol (2) at 100 °Cb 14.65 14.65 1.000 1.782 16.15 16.38 1.000 1.743 17.99 17.99 1.001 1.707 19.47 19.54 1.002 1.671 20.99 20.99 1.004 1.637 23.70 23.79 1.010 1.570 26.30 26.38 1.019 1.506 28.39 28.68 1.031 1.448 30.63 30.83 1.046 1.392 32.65 32.80 1.065 1.341 34.54 34.57 1.088 1.293 36.53 36.24 1.117 1.248 38.62 37.36 1.141 1.218 38.51 37.73 1.151 1.208 39.40 38.80 1.181 1.180 40.07 40.13 1.227 1.145 40.79 41.38 1.283 1.113 41.85 42.56 1.351 1.085 42.79 43.69 1.433 1.060 44.06 44.74 1.529 1.040 45.13 45.80 1.652 1.023 46.30 46.76 1.796 1.011 47.02 47.24 1.883 1.006 47.43 47.64 1.966 1.003 48.22 48.01 2.051 1.001 48.55 48.55 2.199 1.000 2-Furaldehyde (1) + 1-Methoxy-2-propanol (2) at 150 °Cc 76.13 76.13 1.000 1.506 80.88 82.54 1.000 1.479 84.63 88.55 1.001 1.454 94.29 94.43 1.002 1.430 102.14 99.98 1.003 1.407 111.63 110.92 1.008 1.361 119.25 121.30 1.015 1.318 130.12 130.82 1.023 1.279 138.40 139.94 1.035 1.242 147.30 148.54 1.048 1.208 155.79 156.58 1.065 1.177 163.61 162.40 1.079 1.156 163.59 164.36 1.084 1.148 172.27 169.75 1.101 1.129 171.78 171.55 1.107 1.123 176.45 176.82 1.126 1.105 179.57 178.55 1.133 1.099 184.75 183.56 1.155 1.083 188.06 190.08 1.188 1.064 193.56 196.45 1.226 1.048 200.78 202.74 1.270 1.033 206.34 208.72 1.319 1.022 212.74 214.86 1.377 1.012 220.39 220.67 1.441 1.005 222.71 223.62 1.476 1.003 225.60 226.15 1.509 1.002 228.83 228.52 1.542 1.001 232.13 232.13 1.595 1.000

relative volatility

a c


1080



Article

Table 11. Butyl Acetate (1) + Allyl Alcohol (2) PTx Measurements at 100 °C and 150 °C with Calculated Vapor Phase Composition, Activity Coefficients, Fugacity Coefficients, and Relative Volatilitya mole fraction (1) run

charge

liquid

pressure/kPa vapor

1 1 1 1 1 1 1 1 1 1 1 1 1 2 1 2 2 2 2 2 2 2 2 2 2 2

1.0000 0.9746 0.9489 0.9229 0.8991 0.8502 0.8007 0.7423 0.7000 0.6510 0.6004 0.5496 0.4989 0.4710 0.4492 0.4185 0.3670 0.3136 0.2611 0.2081 0.1550 0.1038 0.0776 0.0526 0.0264 0.0000

1.0000 0.9748 0.9493 0.9235 0.8999 0.8512 0.8018 0.7435 0.7012 0.6521 0.6014 0.5505 0.4997 0.4720 0.4498 0.4196 0.3681 0.3147 0.2621 0.2089 0.1556 0.1042 0.0779 0.0527 0.0264 0.0000

1.0000 0.9222 0.8523 0.7895 0.7377 0.6455 0.5676 0.4907 0.4431 0.3945 0.3504 0.3113 0.2764 0.2588 0.2453 0.2278 0.1998 0.1726 0.1471 0.1219 0.0960 0.0694 0.0545 0.0390 0.0209 0.0000

1 1 1 1 1 1 1 1 1 1 1 2 1 2 1 2 1 2 2 2 2 2 2 2 2 2 2 2

1.0000 0.9746 0.9489 0.9229 0.8991 0.8502 0.8007 0.7423 0.7000 0.6510 0.6004 0.5732 0.5496 0.5226 0.4989 0.4710 0.4492 0.4185 0.3670 0.3136 0.2611 0.2081 0.1550 0.1038 0.0776 0.0526 0.0264 0.0000

1.0000 0.9754 0.9504 0.9250 0.9017 0.8536 0.8047 0.7465 0.7043 0.6552 0.6042 0.5760 0.5530 0.5260 0.5018 0.4750 0.4516 0.4228 0.3715 0.3182 0.2654 0.2120 0.1581 0.1061 0.0793 0.0537 0.0269 0.0000

1.0000 0.9313 0.8679 0.8095 0.7605 0.6707 0.5925 0.5132 0.4629 0.4108 0.3629 0.3386 0.3198 0.2988 0.2810 0.2621 0.2464 0.2279 0.1969 0.1669 0.1390 0.1119 0.0852 0.0590 0.0452 0.0314 0.0163 0.0000

meas

calc



(1)

(1)

(2)

(2)/(1)

0.982 0.981 0.980 0.979 0.978 0.977 0.975 0.973 0.972 0.970 0.969 0.968 0.966 0.966 0.965 0.965 0.964 0.963 0.962 0.961 0.960 0.960 0.960 0.960 0.959 0.959

0.991 0.990 0.989 0.989 0.988 0.987 0.986 0.984 0.984 0.983 0.982 0.981 0.980 0.979 0.979 0.979 0.978 0.977 0.977 0.976 0.976 0.975 0.975 0.975 0.975 0.975

3.294 3.270 3.245 3.219 3.194 3.141 3.082 3.008 2.950 2.877 2.797 2.709 2.615 2.560 2.515 2.450 2.333 2.200 2.058 1.903 1.735 1.559 1.465 1.371 1.271 1.167

0.947 0.944 0.942 0.939 0.937 0.932 0.927 0.921 0.918 0.913 0.909 0.907 0.905 0.903 0.901 0.899 0.897 0.895 0.891 0.888 0.884 0.881 0.878 0.875 0.874 0.873 0.872 0.871

0.974 0.972 0.970 0.968 0.967 0.963 0.960 0.956 0.953 0.950 0.947 0.946 0.945 0.943 0.942 0.940 0.939 0.938 0.935 0.933 0.930 0.928 0.926 0.924 0.923 0.922 0.921 0.920

2.937 2.925 2.913 2.901 2.889 2.862 2.833 2.794 2.764 2.725 2.681 2.654 2.632 2.604 2.578 2.547 2.519 2.482 2.411 2.329 2.238 2.135 2.018 1.891 1.820 1.748 1.669 1.585

(2)

Butyl Acetate (1) + Allyl Alcohol (2) at 100 °Cb 44.71 44.71 1.000 1.364 46.42 47.32 1.000 1.355 49.15 49.93 1.000 1.345 51.69 52.52 1.001 1.335 53.96 54.86 1.002 1.326 58.96 59.54 1.004 1.308 63.77 64.10 1.007 1.288 69.27 69.27 1.012 1.265 72.99 72.85 1.018 1.247 76.99 76.81 1.026 1.227 80.67 80.71 1.036 1.206 84.41 84.40 1.050 1.184 88.26 87.86 1.068 1.163 91.11 89.65 1.079 1.151 91.71 91.04 1.090 1.141 93.27 92.86 1.106 1.129 95.81 95.78 1.139 1.107 98.25 98.57 1.184 1.086 100.46 101.08 1.241 1.065 102.39 103.39 1.317 1.046 104.77 105.48 1.421 1.028 106.88 107.26 1.559 1.014 107.83 108.08 1.650 1.008 108.86 108.79 1.755 1.004 109.47 109.44 1.888 1.001 109.95 109.95 2.054 1.000 Butyl Acetate (1) + Allyl Alcohol (2) at 150 °Cc 195.63 195.63 1.000 1.182 201.76 205.54 1.000 1.179 211.77 215.57 1.000 1.175 222.49 225.69 1.000 1.172 231.83 234.92 1.001 1.168 252.88 253.81 1.002 1.160 270.74 272.77 1.003 1.152 295.15 294.89 1.006 1.142 310.13 310.65 1.008 1.134 328.42 328.63 1.012 1.124 343.55 346.83 1.018 1.114 357.84 356.69 1.022 1.108 361.98 364.63 1.025 1.103 373.71 373.79 1.030 1.097 379.37 381.87 1.034 1.092 389.11 390.69 1.040 1.086 395.91 398.25 1.046 1.081 403.63 407.34 1.054 1.074 418.72 423.09 1.072 1.063 433.25 438.79 1.096 1.051 447.77 453.59 1.126 1.039 462.50 467.90 1.166 1.028 477.27 481.60 1.220 1.017 491.21 494.24 1.290 1.009 497.99 500.50 1.335 1.005 505.66 506.34 1.386 1.003 513.29 512.30 1.448 1.001 518.11 518.11 1.523 1.000

relative volatility

a c




Article

Table 12. Butyl Acetate (1) + tert-Butanol (2) PTx Measurements at 100 °C and 150 °C with Calculated Vapor Phase Composition, Activity Coefficients, Fugacity Coefficients, and Relative Volatilitya mole fraction (1) run

charge

liquid

pressure/kPa vapor

1 1 1 1 1 1 1 1 1 1 1 1 1 2 1 2 2 2 2 2 2 2 2 2 2 2

1.0000 0.9764 0.9511 0.9261 0.9015 0.8532 0.8036 0.7533 0.7033 0.6524 0.6026 0.5523 0.5016 0.4768 0.4508 0.4233 0.3699 0.3176 0.2586 0.2043 0.1562 0.1038 0.0770 0.0511 0.0253 0.0000

1.0000 0.9769 0.9521 0.9275 0.9033 0.8555 0.8062 0.7561 0.7061 0.6552 0.6052 0.5545 0.5035 0.4793 0.4524 0.4259 0.3726 0.3204 0.2612 0.2067 0.1582 0.1053 0.0781 0.0519 0.0257 0.0000

1.0000 0.8865 0.7876 0.7065 0.6395 0.5340 0.4512 0.3850 0.3317 0.2867 0.2495 0.2170 0.1884 0.1760 0.1630 0.1508 0.1282 0.1077 0.0862 0.0675 0.0515 0.0343 0.0255 0.0170 0.0085 0.0000

1 1 1 1 1 1 1 1 1 1 1 2 1 2 1 2 1 2 2 2 2 2 2 2 2 2 2 2

1.0000 0.9764 0.9511 0.9261 0.9015 0.8532 0.8036 0.7533 0.7033 0.6524 0.6026 0.5812 0.5523 0.5295 0.5016 0.4768 0.4508 0.4233 0.3699 0.3176 0.2586 0.2043 0.1562 0.1038 0.0770 0.0511 0.0253 0.0000

1.0000 0.9777 0.9538 0.9299 0.9063 0.8596 0.8111 0.7615 0.7118 0.6608 0.6105 0.5868 0.5593 0.5364 0.5076 0.4849 0.4557 0.4323 0.3796 0.3277 0.2686 0.2136 0.1643 0.1100 0.0819 0.0545 0.0271 0.0000

1.0000 0.9161 0.8373 0.7686 0.7086 0.6079 0.5229 0.4511 0.3907 0.3380 0.2931 0.2741 0.2533 0.2371 0.2179 0.2036 0.1862 0.1730 0.1454 0.1207 0.0950 0.0731 0.0547 0.0357 0.0262 0.0173 0.0085 0.0000

meas

calc



(1)

(1)

(2)

(2)/(1)

0.983 0.981 0.980 0.978 0.976 0.973 0.970 0.966 0.963 0.960 0.958 0.955 0.952 0.951 0.950 0.948 0.946 0.943 0.940 0.938 0.935 0.933 0.932 0.930 0.929 0.928

0.990 0.989 0.988 0.986 0.985 0.983 0.981 0.978 0.976 0.974 0.972 0.970 0.969 0.968 0.967 0.966 0.964 0.962 0.960 0.959 0.957 0.955 0.954 0.954 0.953 0.952

5.458 5.412 5.363 5.313 5.263 5.164 5.060 4.952 4.842 4.727 4.611 4.492 4.369 4.310 4.243 4.177 4.041 3.905 3.747 3.598 3.463 3.312 3.234 3.157 3.080 3.004

0.949 0.945 0.941 0.937 0.934 0.926 0.919 0.911 0.903 0.895 0.888 0.884 0.880 0.877 0.872 0.869 0.864 0.861 0.853 0.845 0.836 0.827 0.820 0.811 0.806 0.802 0.798 0.793

0.972 0.969 0.966 0.964 0.961 0.956 0.951 0.946 0.941 0.935 0.930 0.928 0.925 0.922 0.919 0.917 0.914 0.912 0.906 0.901 0.895 0.889 0.883 0.878 0.874 0.871 0.868 0.865

4.035 4.022 4.008 3.993 3.979 3.949 3.918 3.885 3.851 3.815 3.779 3.761 3.741 3.723 3.701 3.683 3.659 3.640 3.596 3.550 3.497 3.445 3.397 3.342 3.312 3.283 3.253 3.223

(2)

Butyl Acetate (1) + tert-Butanol (2) at 100 °Cb 42.55 42.55 1.000 1.270 46.24 46.99 1.000 1.260 50.95 51.67 1.000 1.250 55.84 56.24 1.001 1.240 60.97 60.67 1.002 1.230 69.86 69.21 1.004 1.210 78.05 77.73 1.007 1.191 86.31 86.12 1.012 1.172 94.64 94.21 1.018 1.154 102.39 102.21 1.025 1.136 110.10 109.82 1.034 1.119 117.93 117.29 1.045 1.102 125.28 124.61 1.059 1.087 127.13 128.02 1.066 1.080 133.15 131.75 1.074 1.072 134.05 135.38 1.084 1.065 141.36 142.56 1.105 1.051 148.18 149.46 1.129 1.039 156.25 157.16 1.162 1.027 163.15 164.19 1.198 1.018 168.62 170.43 1.235 1.011 175.97 177.26 1.283 1.005 179.22 180.80 1.311 1.003 184.75 184.25 1.340 1.001 188.70 187.73 1.372 1.000 191.18 191.18 1.406 1.000 Butyl Acetate (1) + tert-Butanol (2) at 150 °Cc 188.81 188.81 1.000 1.071 199.48 202.38 1.000 1.068 213.90 216.97 1.000 1.066 228.60 231.53 1.000 1.064 242.64 245.89 1.000 1.061 271.54 274.40 1.001 1.057 302.28 303.99 1.002 1.052 333.22 334.29 1.003 1.047 365.64 364.72 1.005 1.042 397.06 395.96 1.007 1.038 430.18 426.82 1.009 1.033 444.87 441.36 1.011 1.031 462.12 458.27 1.012 1.029 473.01 472.41 1.014 1.027 494.86 490.13 1.016 1.025 504.07 504.21 1.018 1.023 526.64 522.26 1.020 1.021 535.34 536.82 1.023 1.019 568.61 569.68 1.028 1.015 600.31 602.19 1.035 1.012 638.99 639.60 1.043 1.008 674.38 674.73 1.052 1.005 707.68 706.59 1.062 1.003 745.37 742.16 1.073 1.002 764.67 760.87 1.080 1.001 784.35 779.22 1.087 1.000 804.00 797.81 1.095 1.000 816.37 816.37 1.103 1.000

relative volatility

a c




Article

Table 13. Butyl Acetate (1) + 1-Methoxy-2-propanol (2) PTx Measurements at 150 °C and 200 °C with Calculated Vapor Phase Composition, Activity Coefficients, Fugacity Coefficients, and Relative Volatilitya mole fraction (1) run

charge

liquid

pressure/kPa vapor

1 1 1 1 1 1 1 1 1 1 1 1 2 1 2 1 2 2 2 2 2 2 2 2 2 2 2

1.0000 0.9692 0.9412 0.9132 0.8871 0.8607 0.8039 0.7514 0.6939 0.6432 0.5949 0.5432 0.5093 0.4917 0.4594 0.4411 0.4082 0.3564 0.3024 0.2512 0.2019 0.1531 0.1049 0.0781 0.0476 0.0189 0.0000

1.0000 0.9694 0.9416 0.9138 0.8878 0.8615 0.8048 0.7523 0.6947 0.6439 0.5955 0.5437 0.5097 0.4921 0.4599 0.4413 0.4086 0.3568 0.3027 0.2514 0.2019 0.1530 0.1048 0.0779 0.0474 0.0188 0.0000

1.0000 0.9550 0.9158 0.8782 0.8444 0.8115 0.7443 0.6862 0.6265 0.5767 0.5314 0.4849 0.4553 0.4402 0.4130 0.3975 0.3705 0.3281 0.2840 0.2417 0.2000 0.1571 0.1122 0.0858 0.0540 0.0223 0.0000

1 1 1 1 1 1 1 1 1 1 1 2 1 2 2 2 2 2 2 2 2 2 2 2 2 2

1.0000 0.9728 0.9476 0.9234 0.8989 0.8476 0.7960 0.7451 0.6923 0.6412 0.5894 0.5715 0.5370 0.5213 0.4693 0.4181 0.3650 0.3136 0.2597 0.2074 0.1536 0.1018 0.0760 0.0498 0.0244 0.0000

1.0000 0.9734 0.9487 0.9249 0.9007 0.8500 0.7986 0.7478 0.6949 0.6436 0.5914 0.5726 0.5387 0.5227 0.4709 0.4198 0.3668 0.3152 0.2610 0.2084 0.1543 0.1021 0.0762 0.0499 0.0244 0.0000

1.0000 0.9629 0.9296 0.8983 0.8675 0.8051 0.7454 0.6890 0.6331 0.5811 0.5303 0.5125 0.4808 0.4661 0.4193 0.3741 0.3281 0.2838 0.2375 0.1923 0.1450 0.0981 0.0742 0.0493 0.0245 0.0000

meas

calc



(1)

(1)

(2)

(2)/(1)

0.948 0.947 0.946 0.946 0.945 0.944 0.943 0.942 0.941 0.940 0.939 0.939 0.938 0.938 0.938 0.938 0.937 0.937 0.937 0.937 0.937 0.937 0.937 0.937 0.938 0.938 0.938

0.960 0.960 0.959 0.958 0.958 0.957 0.956 0.955 0.954 0.954 0.953 0.952 0.952 0.952 0.951 0.951 0.951 0.951 0.950 0.950 0.950 0.950 0.950 0.950 0.950 0.951 0.951

1.509 1.495 1.483 1.470 1.457 1.445 1.416 1.388 1.357 1.327 1.298 1.266 1.244 1.232 1.210 1.197 1.174 1.136 1.094 1.053 1.012 0.969 0.925 0.900 0.871 0.844 0.825

0.889 0.888 0.886 0.885 0.884 0.882 0.879 0.877 0.875 0.873 0.871 0.871 0.870 0.869 0.868 0.867 0.866 0.865 0.864 0.863 0.863 0.863 0.863 0.863 0.863 0.863

0.920 0.918 0.917 0.916 0.915 0.913 0.911 0.909 0.907 0.906 0.904 0.903 0.902 0.902 0.901 0.899 0.898 0.897 0.896 0.896 0.895 0.895 0.895 0.895 0.895 0.895

1.415 1.407 1.400 1.394 1.386 1.371 1.355 1.338 1.320 1.301 1.282 1.275 1.261 1.255 1.233 1.211 1.186 1.161 1.134 1.106 1.075 1.045 1.029 1.013 0.996 0.980

(2)

Butyl Acetate (1) + 1-Methoxy-2-propanol (2) at 150 °Cb 191.33 191.33 1.000 1.259 193.81 194.45 1.000 1.248 195.37 197.20 1.001 1.238 198.87 199.87 1.001 1.228 201.06 202.27 1.002 1.219 204.14 204.62 1.003 1.210 208.57 209.42 1.006 1.190 213.12 213.53 1.011 1.172 217.87 217.67 1.017 1.153 221.00 220.98 1.024 1.136 223.73 223.87 1.033 1.121 226.11 226.64 1.044 1.105 228.79 228.27 1.053 1.095 228.62 229.07 1.058 1.089 231.60 230.42 1.068 1.080 231.39 231.14 1.074 1.075 233.18 232.30 1.087 1.066 234.28 233.86 1.109 1.053 235.24 235.09 1.137 1.040 236.06 235.86 1.169 1.029 236.53 236.20 1.206 1.020 236.09 236.09 1.250 1.012 235.79 235.49 1.301 1.006 234.74 234.91 1.334 1.003 234.14 234.00 1.376 1.001 233.33 232.87 1.420 1.000 231.95 231.95 1.452 1.000 Butyl Acetate (1) + 1-Methoxy-2-propanol (2) at 200 °Cc 583.23 583.23 1.000 1.153 589.50 590.73 1.000 1.147 596.47 597.54 1.000 1.142 604.12 604.00 1.001 1.137 609.08 610.41 1.001 1.132 625.35 623.47 1.002 1.122 638.18 636.08 1.004 1.111 650.93 647.96 1.007 1.101 662.66 659.66 1.011 1.091 672.38 670.36 1.015 1.081 683.27 680.56 1.021 1.071 684.93 684.06 1.024 1.067 693.13 690.17 1.028 1.061 692.30 692.93 1.031 1.058 700.71 701.44 1.040 1.049 707.06 709.11 1.050 1.041 713.47 716.31 1.063 1.032 718.92 722.51 1.078 1.025 724.85 728.14 1.097 1.018 729.53 732.68 1.118 1.012 734.08 736.33 1.144 1.007 736.50 738.75 1.173 1.003 739.12 739.51 1.190 1.002 738.57 739.96 1.208 1.001 739.81 740.06 1.227 1.000 739.81 739.81 1.247 1.000

relative volatility

a c


1083



Article

Table 14. n-Butanol (1) + Pentane (2) PTx Measurements at 60 °C and 120 °C with Calculated Vapor Phase Composition, Activity Coefficients, Fugacity Coefficients, and Relative Volatilitya mole fraction (1) run

charge

liquid

pressure/kPa vapor

meas

calc



(1)

(2)

(1)

(2)

(2)/(1)

4.031 3.822 3.649 3.482 3.317 3.022 2.765 2.527 2.316 2.134 1.963 1.868 1.825 1.729 1.690 1.607 1.572 1.499 1.402 1.314 1.237 1.168 1.108 1.057 1.056 1.044 1.034 1.025 1.017 1.010 1.005 1.001 1.000

0.996 0.988 0.982 0.976 0.970 0.960 0.952 0.944 0.938 0.933 0.929 0.927 0.926 0.924 0.923 0.921 0.920 0.919 0.917 0.916 0.915 0.914 0.913 0.912 0.912 0.911 0.911 0.911 0.910 0.910 0.909 0.909 0.909

0.998 0.992 0.988 0.984 0.980 0.973 0.967 0.962 0.958 0.955 0.952 0.950 0.950 0.948 0.948 0.947 0.946 0.945 0.944 0.943 0.942 0.942 0.941 0.940 0.940 0.940 0.940 0.939 0.939 0.939 0.939 0.938 0.938

96.30 91.04 86.62 82.26 77.89 69.91 62.72 55.85 49.54 43.93 38.52 35.42 33.99 30.80 29.47 26.60 25.37 22.76 19.24 15.93 12.92 10.16 7.628 5.338 5.243 4.673 4.163 3.665 3.191 2.734 2.301 1.913 1.536

3.283 3.157 3.042 2.930 2.823 2.614 2.409 2.224 2.051 1.896 1.753 1.626 1.609 1.508 1.496 1.419 1.402 1.338 1.265 1.200 1.144 1.095

0.970 0.959 0.948 0.937 0.928 0.909 0.890 0.874 0.859 0.846 0.834 0.824 0.823 0.815 0.814 0.809 0.807 0.802 0.797 0.791 0.786 0.781

0.981 0.973 0.966 0.959 0.952 0.939 0.926 0.915 0.905 0.896 0.888 0.881 0.880 0.875 0.874 0.870 0.869 0.866 0.862 0.858 0.855 0.851

22.54 21.59 20.72 19.86 19.03 17.37 15.71 14.16 12.68 11.31 10.01 8.819 8.654 7.677 7.559 6.783 6.604 5.938 5.144 4.414 3.743 3.103

n-Butanol (1) + Pentane (2) at 60 °C 1 1 1 1 1 1 1 1 1 1 1 2 1 2 1 2 1 2 2 2 2 2 2 2 3 3 3 3 3 3 3 3 3

1.0000 0.9744 0.9520 0.9289 0.9046 0.8571 0.8101 0.7608 0.7109 0.6621 0.6102 0.5794 0.5626 0.5262 0.5104 0.4734 0.4586 0.4208 0.3683 0.3147 0.2617 0.2089 0.1564 0.1042 0.1030 0.0890 0.0760 0.0629 0.0501 0.0371 0.0244 0.0124 0.0000

1.0000 0.9762 0.9549 0.9328 0.9094 0.8630 0.8165 0.7671 0.7168 0.6673 0.6145 0.5819 0.5661 0.5291 0.5131 0.4767 0.4604 0.4242 0.3718 0.3180 0.2648 0.2116 0.1585 0.1057 0.1034 0.0893 0.0762 0.0631 0.0502 0.0372 0.0245 0.0124 0.0000

1.0000 0.3101 0.1965 0.1445 0.1142 0.0827 0.0662 0.0557 0.0486 0.0437 0.0397 0.0378 0.0370 0.0352 0.0345 0.0331 0.0325 0.0314 0.0298 0.0284 0.0271 0.0257 0.0241 0.0217 0.0215 0.0205 0.0194 0.0181 0.0163 0.0140 0.0108 0.0065 0.0000

8.39 24.62 40.81 58.61 71.93 94.64 113.67 130.08 145.09 155.61 164.90 172.69 172.34 178.66 178.55 184.72 184.40 189.32 193.21 197.04 200.69 202.71 206.26 210.17 209.66 210.55 211.17 211.59 212.46 213.23 214.55 214.65 215.21

8.39 26.65 41.51 55.67 69.39 93.12 112.90 130.26 144.79 156.52 166.74 172.08 174.41 179.36 181.29 185.25 186.84 190.03 193.95 197.26 200.04 202.50 204.88 207.48 207.60 208.40 209.19 210.06 210.99 212.00 213.08 214.14 215.21

relative volatility

b

1.000 1.001 1.002 1.005 1.009 1.021 1.039 1.064 1.097 1.137 1.192 1.232 1.254 1.311 1.339 1.409 1.445 1.535 1.698 1.921 2.228 2.676 3.378 4.606 4.681 5.193 5.773 6.498 7.405 8.586 10.145 12.159 15.126

n-Butanol (1) + Pentane (2) at 120 °Cc 1 1 1 1 1 1 1 1 1 1 1 1 2 2 1 2 1 2 2 2 2 2

1.0000 0.9771 0.9555 0.9337 0.9123 0.8678 0.8201 0.7729 0.7240 0.6747 0.6237 0.5723 0.5701 0.5187 0.5117 0.4677 0.4606 0.4155 0.3625 0.3097 0.2572 0.2028

1.0000 0.9811 0.9629 0.9440 0.9251 0.8844 0.8392 0.7928 0.7434 0.6927 0.6394 0.5852 0.5772 0.5275 0.5211 0.4777 0.4672 0.4263 0.3734 0.3203 0.2668 0.2109

1.0000 0.7057 0.5557 0.4589 0.3935 0.3057 0.2494 0.2127 0.1860 0.1662 0.1505 0.1379 0.1363 0.1269 0.1259 0.1188 0.1172 0.1112 0.1038 0.0964 0.0886 0.0793

110.26 151.40 193.56 236.37 275.62 350.33 422.89 485.71 543.21 593.62 637.92 675.28 681.64 710.62 713.40 736.53 741.86 761.51 783.47 804.63 824.77 844.78

110.26 155.48 196.42 236.50 274.21 348.12 419.70 483.07 540.97 591.74 637.06 676.23 681.46 711.67 715.23 738.15 743.33 762.37 784.77 805.48 825.24 845.44 1084

1.000 1.000 1.001 1.003 1.006 1.014 1.027 1.046 1.072 1.106 1.150 1.206 1.215 1.281 1.290 1.360 1.379 1.461 1.591 1.755 1.969 2.268



Article

Table 14. continued mole fraction (1) run 2 2 2 2 2 2

charge 0.1513 0.1026 0.0781 0.0521 0.0258 0.0000

liquid 0.1574 0.1066 0.0808 0.0538 0.0264 0.0000

pressure/kPa vapor 0.0683 0.0546 0.0457 0.0340 0.0190 0.0000

meas

calc



(1)

(2)

(1)

(2)

(2)/(1)

1.056 1.028 1.017 1.008 1.002 1.000

0.776 0.772 0.770 0.767 0.765 0.764

0.848 0.844 0.843 0.841 0.840 0.838

2.546 2.064 1.838 1.612 1.397 1.202

n-Butanol (1) + Pentane (2) at 120 °C 863.52 864.85 2.662 882.78 883.49 3.188 892.24 892.85 3.539 901.62 902.37 3.997 912.50 911.10 4.584 917.75 917.75 5.316

relative volatility

c

a c


■

REFERENCES

(1) Soave, G. Equilibrium Constants from a Modified Redlich−Kwong Equation of State. Chem. Eng. Sci. 1972, 27, 1197−1203. (2) Wilson, G. Vapor−Liquid Equilibrium. XI. A New Expression for the Excess Free Energy of Mixing. J. Am. Chem. Soc. 1964, 86, 127−130. (3) Rowley, R.; Wilding, W.; Oscarson, J.; Yang, Y.; Zundel, N. DIPPR Data Compilation of Pure Chemical Properties. Design Institute for Physical Properties; AIChE: New York, 2008. (4) Ronc, M.; Ratcliff, G. A. Measurement of Vapor−Liquid Equilibria Using a Semi-continuous Total Pressure Static Equilibrium Still. Can. J. Chem. Eng. 1976, 54, 326−332. (5) Kim, Y.; Bae, W.; Kim, H. Isothermal Vapor−Liquid Equilibria for the n-Pentane + 1-Butanol Systems near the Critical Region of the Mixtures. J. Chem. Eng. Data 2005, 50, 1520−1524. (6) Sunder, M. S.; Prasad, D. H. L. Vapor−Liquid Equilibrium and Excess Gibbs Energies of Hexane + N,N-Dimethyl Formamide, 2Methylpropan-2-ol + 2-Aminophenol, N,N-Dimethyl Formamide, and 2-Propanol + Diisopropyl Amine at 94.4 kPa. J. Chem. Eng. Data 2007, 52, 2050−2052.

Figure 8. Px plot for four systems with 1-methoxy-2-propanol.

The measured data for the n-butanol + pentane system are in good agreement with the low temperature data reported by Ronc and Ratcliff4 and the high temperature data reported by Kim et al.5 Together these data sets provide a thorough examination of this system over the range 30 °C to 240 °C. The measured data for the tert-butanol + ethanolamine system have fair agreement with the isobaric data reported by Sunder and Prasad,6 with the activity coefficients reported in this work lower in value than those calculated using their reported correlation.

■

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.

■

ACKNOWLEDGMENTS The authors also wish to thank their co-workers who helped measure the data with precision and meticulous effort; special thanks to Ammon Avans, Lane Gardner, and Gabriel Kelly. 1085


VaporâLiquid Equilibrium for Several Compounds Relevant to the

Recommend Documents

VaporâLiquid Equilibrium for Several Compounds Relevant to the