benzene chlorobenzene vle data

100 J. Chem. fng. Data 1983, 28, 100-107

Total-Pressure Vapor-Liquid Equilibrium Data for Binary Systems of Chlorobenzene with Nitromethane, Ethanol, Benzene, and 1 -Chlorobutane

Jagjit R. Khurma, 01 Muthu, Sarat MunJal, and Buford D. Smith

Thermodynamics Research Laboratory, Washington University, St. Louis, Missouri 63 130

Total-pressure vapor-llquld equlllbrlum (VLE) data are reported at approxlmately 298, 348, and 398 K for each of four chlorobenzene binaries with nltromethane, ethanol, benzene, and I-chlorobutane as the other components. The experimental PTx data were reduced to y,, y,, and GE values by both the Ylxon-Gumowskl-Carpenter and the Barker methods, but only the Mlxon et al. resuits are reported In their entirety. SIX GE correlatlons were tested In the Barker data reductlon; the five-constant Redllch-Klster equatlon gave the best results. Various equatlons of state were used to estlmate vapor-phase fugacity coeff lclents. the Peng-Roblnson equatlon of state was used for the reported data for the nitromethane and 1-chlorobutane systems. The vlrlal equation through the second term, with the coefflclents predicted by the Hayden-OConnell correlation, was used for the data reported for the ethanol and benzene systems.

I ntroductlon

This is the second paper reporting totalpressure vapor-liquid equilibrium (VLE) data on binary systems containing chlorobenzene. The first paper ( I ) used acetone, acetonitrile, ethyl acetate, ethylbenzene, methanol, and 1-pentene as the other component. This paper reports data for nitromethane, ethanol, benzene, and I-chlorobutane.

The apparatus and techniques for the experimental measurements have been described in detail in a previous paper ( Z ) , along with the defining equation for the activity coefficient and the definition of the standard states used.

Chemlcats Used

The sources and purities of the chemicals used are listed in Table I . Activated molecular sieves (either 3A or 4A) were put into the chemical containers as they were received. Just prior to being loaded in the VLE cells, the chemicals were poured into distillation flasks and distilled through a Vigreux column (25 0.d. and 470 mm long). The first and last portions of the distillate were discarded. The retained samples were back-flushed with dry nitrogen and put into amber glass bottles for transfer to the cell-loading operation. The stated purities of the chemicals were verified chromatographically at this point.

None of the compounds exhibited any degradation during the VLE measurements. The cell pressures were stable with re- spect to time, and all liquids were still perfectly clear when removed from the cells at the end of the last isotherm.

Experimental Data

Tables 11-V present the experimental PTx data. The smooth pressure values reported there are from the least- squares cubic splined fits used to provide the evenly spaced

Table 1. Chemicals Used stated

component vendor purity, 70

ethanol U.S. Industrial Chemicals 200 proof chlorobenzene Burdick and Jackson 99.9+ 1-chlorobutane Burdick and Jackson 99.9+ benzene Burdick and Jackson 99.9+

0 0

W f

0 0

O f

a e Y

. a w o a 3 % m m W e e o 0 2 - c U - L o , 0 . LD -

0 0

m

0 0

0

N I T R B M E T H R N E ( 1 1 + CHLOROBENZENE [21 R 2 9 8 . 1 5 K

C 399.26 K E 3 ~ 8 . 1 7 K

IO 0 . 2 0 0 . 4 0 0.60 0.80

X I

00

Flgure 1. Deviation from Raoults law for the nitromethane (1) + chlorobenzene (2) system.

values required by the finitedifference Mixon-Gumowski-Car- penter method (3) for reduction of PTx data.

Figures 1-4 show the experimental data in terms of the pressure deviation P , from Raoults law

P, = P - [P* + x , (P , - P*)] where P is the experimental mixture pressure and the P,values are the pure-component vapor pressures. The deviation pressure plot emphasizes the scatter more than a P vs. x , plot but has the disadvantage of not indicating whether an azeotrope exists.

The point symbols in Figure 1-4 denote the experimental data points. The curves approximate-sometimes not very

0021-9568/83/1728-0100$01.50/0 0 1983 American Chemical Society

Journal of Chemical and Engineering Data, Vol. 28, No. 1, 1983 101

Table 11. Experimental P vs. x , Values for the Nitromethane (1) + Chlorobenzene (2) System

,000i) e0474 0962 1650 2297 3106

a 5 1 3 3 -6113 7522

e7926 ,0965 ,9173 ,9596 1,0000

.4 lac)

1.629 2 409 2.973 3.544 3.915 4.217 4 491 4 660 4.790 4 e931 9.937 4.954 4.939 4.782 4.8ae

.oooo 04 7 4 0961 1649 2296 : it15 e5132 61 13 7521 7926 8965

,9178 9596

1.0000

I - - - - - - - - - - - - - -

16.35 1 21 543 2 5 . 5 5 7 29.84 32 79 35.61 38.26 39.98 41 30 42.71 42.94 43.24 43.18 42.90 42.21

.-------- it: 325 2 5 . 5 4 3 29.83 32.83 35.58 38.27 39.97 41.30 42.70 42.96 4 3 . 2 2 43.18 42.91 42.21

Table 111. Experimental P vs. x. Values for the Ethanol (1) + Chlorobenzene ( 2 ) System

---------- .oooo .0472 0959 1646

-2292 :Mi 8 51 30 e61 11 7520 7926 8965 -9178 -9596 1.0000

0000 1.644 1.643 .oooo 23.322 23.321 .oooo 85.51 85.51 ,0614 5 305 5.324 00610 43.09 43.16 -0599 169.39

190.04 241 e55

0795 5.612 5.591 ,0791 47.99 47.86 1233 6 109 6.097 1289 56.79 56.89 e1276 242.18 1816 6.418 6.438 .le11 62.45 62.30 -1797 282.3 282.6

,2926 6 794 6.793 -2921 69.69 69.74 2906 338.0 372.9 397.6

.3954 7.024 7.011 395 1 73 . 94 73.98 - 4 0 7 0 7.191 7.191 4867 76.89 76.78 ,4856 397.9 . 5 839 7 356 7 e369 ,5837 79.61 79.57 ,5825 420.0 420.0 e6751 I . 559 7.562 6950 82 59 82.69 e6942 443.7 443.9 ,7814 7.710 7.706 .la14 84.85 84 96 e 7 8 0 8 461.5 461.7 8519 7.832 7.821 -8519 86.72 86.68 -8517 475.9 475.9 9059 7.897 7.901 9058 88.00 87.88 e9056 486.8 486.6 -9631 7.929 7.937 09631 89.16 89.05 09630 498.1 497.8 1.0000 7.914 7.310 1.0000 89.59 89.73 3.0000 504.7 505.0

,0784 t$8:2 e3936 !$J:o"

. 0000 1 635 1 e635 .oooo 16.333 16.338 .0000 85.38 8 5 . 4 8 , 0 4 3 2 2 146 2.147 ,0431 19.449 19.436 04 30 96.28 96.22 ,0958 2 739 2.743 ,0957 23.155 23.159 ,0956 109.38 109.33 1348 3.184 3.179 1347 25 887 25.892 -1345 119.03 119.06 1929 3.831 3.828 1927 29.33 29.93 ,1924 133.59 133.54

2765 154 64 .3700 \?'a:!'; 78: 16 0 4 7 7 1 205.20

a2771 't 768 4 e768 . 2 7 7 0 35.81 370 7 5 e 807 5 309 0 3704 4 2 . 3 3

a5772 230.00 $!8:'BJ ,4 779 6 993 7.000 4777 49.82 49.82 ,5780 d . 107 8.110 05778 56.84 56.84 258.58 e6858 9 s 327 9 301 6855 64.42 64.40 e6851 258.68

a7890 285.6 285.6 ,8302 296.3 296.4 e9179 319.6 319.5

,7095 10 e433 10.444 ,7893 71.67 3306 13 886 10.897 8304 7 4 . 5 7 9 182 11.862 11.859 a9181 80.80 00 .78 ,9583 12 304 12.299 9582 83.67 83.62 e9582 330.3 330.2

1.0000 12 755 12.757 1.0000 86.54 86.57 1.OOOC 341.3 341.4

:;:!I$

;::I8

Table V. Experimental P vs. x Values for the l-Chlorobutane (1) t Chlorobenzene (2) System

16.278 16.299 . 0000 -0434 . 418 19.949 .208 32 78

38.79 38.77 46.66 46.66 53.69 60.89 68.15 78.27 80.61 05.57 88.33 88.31 1.21 91.22

.p33

.2ssl

.597! 2a:as 85 :3 :!?If

1:%88&

23::s' : -6860 $!: :# -8237

-----------. 84 .f3 97.17 109.54 t $42: St

269.27 306.3 315.0 333.4 343.5 354.4

102 Journal of Chemical and Engineering Data, Vol. 28, No. 1, 1983

Table VI. Calculated Data for the Nitromethane ( 1 ) t Chlorobenzene (2) System at 298.15, 348.17, and 398.26 K Obtained with the Mixon et ai. Method and the Peng-Robinson Equation of State

L I Q U I D MDLAd VOLUMES, CC/YOL: V L ( 1 ) f 53.942

x 1 .oooo . l o o 0 ,2000 ,3390 m 4000 -5000 6000 ,7000 .8000 9300

1.0000

TiITAL PRESSURE, KPA EXPTL CALC

1.629 1,623 3.012 3.013 3.761 3.761 4.453 4.453 4.641 4.641 6.776 4. 776 4.383 4,893 4 .949 4.949 4.949 4.9 (13 4.782 4. 782

4 . 1 9 3 4.1 a3

M IXTURE F UC A C I T Y COtFF I C I E N J S

,9494 ,9589 .99as . 9 w o ,9984 ,9976 ,9983 ,9973 ,9981 ,9970 eY980 e9970 ,9980 e9969 ,9979 e9969 ,9979 ,9969 e9980 ,9970

.9982 .3971

L I # U i O M O L A R VOLUMES, CC/'lOL: V L ( 1 ) 57.211

FUGACITY C I E N I S

x 1 .oooo ,1000 2000 ,3000 4000 5000 a6000 ,7090 8300 9000

1.0000

T O T A L PRE EXPTL. 16.350 25.J21 31,562 35.273 37.372 39.760

42.263 42.996 43.212 42.209

41.163

SSUi


Table VII. Calculated Data for the Ethanol ( 1 ) + Chlorobenzene (2) System at 298.15, 348.35, and 398.66 K Obtained with the Mixon et al. Method and the Virial Equation of State through Bij

L I Q U I D POL46 VOLUMES, CC/MOL: VL(1) * 59.821 V L ( 2 ) t 102.280 V I R I A L COEFFICIENTS, CC/fOL: B ( l , l ) = -2169.9 8 ( 1 , 2 ) = -1185.0 B (2 ,2 ) -3127.6

x 1 .oooo . l o o 3 ,2300

3000 4300 5000

e 6 0 0 0 7300

.0000 9000

1.0300

TOTAL PRESSURE, K P A EXPTL. C A L C .

1.643 1.643 5.125 5.824 6.523 6.523 6.309 6.809 7.020 7.020 7.216 7.216 7.398 7.398 7 . i 7 0 7.573 7.736 7.736 7.393 7.893 7.410 7.9 10

MIXTURE FUGACITY COCFF ICIENX S

1 Oh05 ,9954 ,9947 ,9944 - 7 9 4 2

9 9 4 0 . 9 9 3 8 0 9 9 3 6

9 9 3 4 9932 9 9 3 1

e9679 9 9 6 3 9 9 6 3 9 9 6 3

e 9 9 6 4 ,9964

9 9 6 5 9 9 6 7

e 9 9 7 1 ,9979 e 9 9 9 4

Y 1 .oooo ,7317

7 6 6 8 e7810

7928 e8054 ,8199 .a384

8 6 6 3 e9187

1 .oooo

ACTIVlTY COEFFIC/ENTS

15.&072 5.4006 3.1670 2.2441 l e 7 6 1 0 1 4707 1.2789 1 1 4 6 8 l e 0 5 9 4 1 e0187 1 .oooo

f 1.0000 1.0545 1.2930 1 1549 1.4728 1 e 7059 2.0232 2.4779 3.1425 3.9024 5.6941

EXCESS CIBBS J/MOLE

FUNCTION, 0.00

536.46 957e09

1048.08 1136.98 1140.09 1064.71

912.55 682.14 378.84 0.00

L I Q U I D KOLAR VCLUMES, CCIMOL: V L ( 1 ) = 63.708 V L ( 2 ) = 107.690 V I R I A L COEFFICIENTS, CC/POL: 8 ( 1 , 1 ) = -976.6 8 (1 ,2 ) 1 -785.8 8 I 2 r 2 ) * -1857.1

EXCESS MIXTURE FUGACITY CIBBS

A C T I V I T Y COEFFICIENTS FUNCTION, x1 EXPTL. CILC. 2 Y 1 J/MOLE 0.00 2

1.0000 1

4.3344 1 .oooo

1.0144 398.88 23.321 23.321 1.0025 ,9850 695.98 883.01

3*4852 1.0790 .5878

.0300 52.270 - 9 3 6 3 e9744

2.4535 52.272

6 8 0 3 1300

63.919 63.917 ,9813 09719 70.129 - 7 2 2 2 1 8 9 9 9 1.1741 1.3048 .2000

978.03 3300 l e 5 6 0 7 7496 988.59

,9770 ,9706 1.4799

74 .141 74.141 4000 921.99

- 9 7 5 7 ,9706 7726 e1932 1.7004

77.161 .7985

e5500 77.161 a9744 .9709

784.87 00.041

1.9827 e 6 3 0 0 80.041 1 e0983

e0299 580.56

e 9 7 3 1 ,9717 2.3516

0 2 . a ~ ~ 82.829 1 e0375

7000 313.16

. 9 7 i a .9734 e 8 6 9 8 2.7827

0 5 . 4 3 0 1 e0064

05.430 e9252

.8JOO e9706 e9765

3.1027 0.00 07.759 07.759

1 .oooo e9000 1 .0000 89.726 89.726 - 3 6 9 7 ,9816 1.0000

COEFFICIENTS TOTAL PRESSURE K P A

.37a7 . w i o 70.128 1 e3373

L I Q U I D HOLdR VOLUMES, CC/HOLI VL(1) f 70.160 V L ( 2 ) 113.961

V I R I A L COEFFICIENTS, CC/tOL: 8 ( 1 , 1 ) = -560.4 B ( 1 9 2 ) = -563.8 8 ( 2 , 2 ) -1260.6

x 1 .oooo ,1300 .2000 -3000 4000

g5000 6000 7000

,8000 ,9300

1 e 0000

TOTAL PRE EXPTL.

85.509 2 14.384 2 95.332 341.575

374. i iOl 4 0 1 - 1 5 2 423.788 445.088 465.567 485.463 505.016

SSURE, KPA CALC. 85.509

214.379 295.320 3 4 1.574 374. bC1 401.152 423.787

465.567

505.0 16

445. 088

405.463

MIXTURE COCFF

l e o b 4 1 9703

- 9 5 9 2 ,9454 e 9392 e9342 s 9 2 9 9 - 9 2 5 8 0 9 2 1 9 ,9180 e9144

FUGACITY ICIENXS . 9L675

e 9 3 6 0 e 92 1 9 s 9 1 4 7 0 9 1 0 1 s 9 0 6 9

9 0 4 8 9 0 3 6 90 3 6

e 9 0 5 9 , 9 1 3 3

closely-the cubic splined fits of those data points. Interpo- lated values (at 0.025 increments in x l) from the splined fis are fed to the plotting software which then makes its own fit of the input values. Those fits are often not very good if the curve is irregularly shaped. Nevertheless, the curves do help illustrate the scatter and the general behavior of the experimental points. For an accurate determination of how closely the splined fits represent the experimental points, Tables 11-V must be used.

The nitromethane and ethanol systems show positive deviations from Raoults law at all three temperatures. The nitromethane forms an azeotrope at all three temperatures. No azeotropes are formed with ethanol.

The benzene and I-chlorobutane systems change their mind as the temperature increases (mixed deviation systems). Both systems are almost ideal with small positive deviations at room temperature. At 348 K, the benzene system is still almost ideal but the deviation at high x values has become negative despite the fact that the positive deviation at low xi values has increased. The positive deviation in the 1-chlorobutane system increased across the composition range at 348 K but the slight sag at the higher x , values is a portent of the behavior at 398 K. At the highest temperature, the positive deviation of the 1-chlorobutane system at low x values has increased further but the deviation is definitely negative at the high x , values. The

Y 1 e 0000 6 2 2 0 74 19

e7887 0 8 1 0 5 .a418 0 8 6 2 9 e 0 8 5 2 -9111 .9454

1.0000

ACTIV lTY COEFFIC!ENTS

3.4133 1. 0000 2.8189 1.0143 2.2737 1.0543

1 1 3 0 2 1.8440 1.5641

1.2294 1.5704 1.1299 1 8374 1.0594 2.2315 1.0142 2 e8634 1.0000 3.6278

1.3693 1 :$+:$

EXCESS CIBBS JIHOLE

FUNCTION e

0.00 385.82 684.65 892.85

101 2.58 1050.71 1009.19

888.31 685.10 390.78

0.00

benzene system has become a negative deviation system at all compositions, and the system has become more nonideal. Neither the benzene nor the I-chlorobutane system forms an azeotrope at any of the three temperatures.

Reduced Data

The y,, y,, and GE values selected for publication are in Tables VI-IX. Those values were obtained with the Mixon et al. data reduction method (3). The Peng-Robinson equation of state (4) was used for the nitromethane and I-chlorobutane systems to estimate the vapor-phase fugacity coefficients. The virial equation truncated after the second term was used for the ethanol and benzene systems. The Hayden-OConnell (5) correlation was used to estimate the 4, and Si! values. The equation of state parameters are listed in Tables X and XI .

The experimental pressure values tabulated in Tables VI- I X are actually interpolated values from the cubic splined fits of the experimental P vs. x values. (The fidelity with which the splined f is represent the actual experimental P values is shown in Tables 11-V.) The calculated pressure values are from the Mixon et al. data reduction method and show how well that method can reproduce the original pressure data.

The calculated activity coefficient curves are shown in Figure

104 Journal of Chemical and Engineering Data, Val. 28, No. 1, 1983

m 0

R 2 9 9 1 7 6

C 399 P I K a 3 q 9 17 K

ETHRNOL (11 T C H l O R O B E N Z E N t (21 A A 2 9 8 . 1 5 K + E 3 4 8 . 3 5 K x C 3 9 8 . 6 6 K

g i , I I

I I I I I i 0.00 0.20 0.110 0.60 o . a o 1.00

X.

0 I I I I

Flgure 4. Deviation from Raoult's law for the 1-chlorobutane (1) + chlorobenzene (2) system.

1 N I T S O M E T H R N E ( 1 1 * CHLOROBENZENE [21 r? 2 9 8 . L5 K

C 3 9 8 . 2 6 K E 3 4 8 . 1 7 K

0 1 I I I I 0.00 0.20 0.40 0.60 0.80 DO

Figure 5. Activity coefficients for the nitromethane (1) + chlorobenzene (2) system. Curves are from Barker results; points are from Mixon et al. method.

Figure 6. Activity coefflcients for the ethanol (1) + chlorobenzene (2) system. Curves are from the Barker results: points are from Mixon et al. method.

I

31

I

N I

8 E N t E N E 1 1 1 + CHLOROBENZENE 123 A R 2 3 8 . 2 0 6 + B 3 u a . 1 6 6 x c 3 9 8 . ~ 6 K

Flgure 7. Activity coefficients for the benzene (1) + chlorobenzene (2) system. Curves are from Barker results; points are from Mixon et al. method. Move decimal point one place to left in ordinate scale values.


Table VIII. Calculated Data for the Benzene ( 1 ) + Chlorobenzene (2) System at 298.20, 348.16, and 398.66 K Obtained with the Mixon et al. Method and the Virial Equation through B"

L I Q U I D M O L A R ' V O L U M E S , C C / M O L : V L ( 1 ) = 09,409 V I R I A L C O E F F I C I E N T S t C C / M O L : 0(1,1) -1509.1

V L ( 2 ) = 102.290 e(1,2) = -2060.1 8(2,2) = -3125.7

M I X T U R E F U G A C I T Y T O T A L P R E S S U R E K P A C O E F F I C I E N T S

x1 E X P T L C l L C . 1 2 ,0000 1.635 1.635 .9993 .9979 ,1300 2.789 2.789 e9905 -9066 .zoo0 3.307 3.907 ,9977 .9954 a3000 5.023 5.023 ,9970 -9743 e4000 6.136 6.136 ,9963 ,9931 ,5000 7.246 7.246 e9956 ,3920 6000 8.353 8.353 a9949 ,9909 e7000 9.450 9.458 .'?'I42 ,9890 . 8000 10.560 10.560 a9936 ,9807 .9000 1 1 -660 11.660 e9929 ,9876

1.0300 12.757 12.757 a9922 ,9065 L I Q U I D MOLAR V O L U M E S , C C / M O L : V L ( 1 ) = 95.342 V I R I A L C O E F F I C I E N T S , C C / M O L : B(1,lJ = -988.1

M I X T U R E F U G A C I T Y T O T A L P R E S S U R E K P A C O E F F I C I E N T S

x 1 E x r T L . C l L C , 1 2 ,0303 16.338 16.338 09958 ,9895 .loo0 23.458 23.457 a9728 ,9852 .2000 30.442 30.441 e9901 ,9813 3503 37.413 37.412 .9875 ,9775

e 4000 44.395 44.394 ,9850 ,9738 ,5000 51.380 51.307 e9826 ,9701 6300 5d.394 58.393 e9801 19665 700J 65.?14 65.413 -3777 ,9620 .oooo 72.949 72.443 e9753 e9592 e9000 79.502 79.502 09729 ,9556

1 .oooo 86.574 86.5 74 ,9704 ,9519 L I Q U I O KOLAR V C L U M E S , C C / M O L : V L ( 1 ) = 102,570 V I R I A L C O E F F I C I E N T S , CC/!'OL: B(l,l) = -710.7

T O T A L P R E S S U R E K P A

85.402 8 5 . 4 8 2 E X P T L C l L C .

110.435 110.431 135.r141 135.436 160.535 160.528 105.748 105.742 211.115 211.113 236.668 236.664 262.440 262.430 288.165 2 0 0 . 4 6 4 314.776 314. 776 341.406 341.406

M I X T U R E F U G A C I T Y C O $ F F I C I E N I S

a9656 .'It75 ,9789 ,9584 ,9726 e9499 a9667 ,9417 e9609 ,9337 a9552 e9257 ,9495 ,9177 ,9438 ,9098 e3324 ,8939 e9266 e8058 ,9381 .?ole

I - C H L 3 R O B U T A N E ( 1 1 + C H L O R O B E N Z E N E (21 A R 2 9 8 . 1 7 K

0 3118.17 K x c 3 9 8 . 2 1 K

N

m - L -

0.00 0.20 0.110 0.60 0.BO

X l

10

Flgure 8. Activity coefficients for the 1-chlorobutane (1) + chlorobenzene (2) system. Curves are from Barker results; points are from Mixon et al. method. Move decimal point one place to left in ordinate scale values.

A C T I V ! T Y C O E F F I C I E N T S 1 L

1 0962 1 .oooo 1.0357

1 1 e 0 0 4 8 0025 1.0155 1.0120 1 ,0085 1.0093 1.0107 1.0070 1.0135

1.0173 1 e0050 1.0031 1.0231 1.0014 1.0333 1 .oooo 1.0799

1.0211 1 e0066

::CeLiss F U N C T I O N ,

J / M O L E 0.00 14.28 19-87 22.87 24.63 23.60 21.39 17.48 11.27 0.00

24.37

V L ( 2 ) 107.690 8(1,2) = -13CO.O B(2.2) * -1860.2

E X C E S S c1ee5

Y 1 1. 2 J / M O L E 0.00 .oooo 1.0443

m3697 1 e0269 1.0008 9.80 ,5657 1.0165 1 0026 15.43 6690 1.0117 1.0041 18.42 7741 1 e0007 1 e0057 19.90 ,8364 1.0065 1 e0075 20.19 e0041 1.0047 1 0097 19.35 e9219 1 0032 1.0125 17.32 ,9526 1.0019 1.0165 13.92 a9702 1 .0000 1.0232 0.72

1.0000 1.0000 1.0472 0.00

A C T I V I T Y C O E F F I C I E N T S F U N C T I O N ,

1 .oooo

V L ( 2 ) * 113.961 0(1,2) = -912.1 8(212) -1260.6

E X C E S S C I B B S

Y l 1 2 J / H O L E .oooo 1.0228 1.0000 0.00 e2960 1.0107 1.0002 6.76 . 4 a 4 4 1.0150 1 0009 12.11 ,6153 1.0117 1.0019 16.05

1 m 0089 10.56 19.62 19.19

1.0064 /:!8% e7119 ,7863 e0457 1 e0044 1.0080

17.22 1.0111 ,8943 1.0027 ,9350 1.0014 1.0151 13.60 ,9698 1 e 0 0 0 5 1 e0205 0.12

1.0000 1.0000 1.0323 0.00

A C T I V I T Y C O E F F I C I E N T S F U N C T I O N ,

1 E T H R N O L 1 1 ' + C H L O P S E E N Z E N E ( 2 1

% I 01

2 9 E . 1 5 K a M I X O N * a i l a K E R

+

-- 1

A

- I

I +

A

A

+ +

+

x + 0 m

D 1 I I 1

0 . 6 0 0.80 0.20 0.40 0 . 0 0

X l

.a0

Flgure 9. Comparison of the Barker and Mixon et ai. results on the resolution error plot for ethanol (1) + chlorobenzene (2) at 348.35 K. Move decimal pont one place to left in ordinate scale values.

106 Journal of Chemical and Engineering Data, Vol. 28, No. 1, 1983

Table IX. Calculated Data for the 1-Chlorobutane (1) + Chlorobenzene (2) System at 298.17, 348.17, and 398.21 K Obtained with the Mixon et al. Method and the Peng-Robinson Equation of State

L I Q U I D HOLAR VOLUMES, CC/YOL: V L ( 1 ) 105.126 VL(2) a 102.282

TOTAL PRESSURE KPA

1.641 2.959 4.187 4 s 187

5.398 5.398 6.598 6.598 7 . 787 7.787 8.967 6.967

10.141 10.141 11s 313 11.313 12.485 12.485 13.654 13.654

EXPTL. C lLC.

2:854'9

MIXTURE FUGACITY COCFFICI E N I S

.9d9l ,9589 e9984 e9981 .9978 ,9973 e9971 a9965 e9965 e9957 ,9959 ,9949 -9952 ,9942 a9946 a9934 e9940 ,9927 ,9934 e9919 ,9927 ,9911

4 C T IV!TY CflEFF l C I F N T 5 : : i $ s b I 1.0000 s i 0 3 3 1.0532 1.0087 1.0379 1.01 35

1.0141 1.0327 1.0422 1.0091 1.0546 1.0952

1.0022

k"Oil'3 l : 8 M

1.0000 \:!:E

L I Q C I O MOLAR VOLUHES, CC/MOL: V L I I ) 8 112.244 V L ( 2 ) 1C7.690

TOTAL PRESSURE, KP4 EXPTL. CAL C.

4:: f193 5'41:m

16 -299 24.413 32 m092 32.091 39.631 39.630 47.072 5 4 . 4 4 8 61 791 61 790 69.126 69s 126 76.473 76.479 R3.870 83.870 91.216 91.216

HIXTURE FUGACITY COfFFICIEN!S

L I C U I D POLAR VOLUMES, CC/MOL: V L ( 1 ) 121.271

TOTAL PRESSURE KP4

84.573 84.573 112.856 112.853 140.171 140.167 15? e 0 6 1 167.058 13 3.665 246.519 246.518 273.053 273,052 299.863 299.863 327.089 327.089 354.376 354.376

EXPTL. C l L C .

220.107 $%:(1%

HIXTURE FUGACITY CO$FFICIENSS

Table X. Parameters for Peng-Robinson Equation (4)a component T c , K P,, MPa L

nitromethane 588.0 6.313 0.3460 1-chlorobutane 542.0 3.688 0.2180 chlorobenzene 632.4 4.520 0.2490

a Binary interaction constant was set at 0.0 for all systems.

Table XI. Virial Coefficient Values (5)

system T, K B , , B , , B?2 ethanol (1) + 298.15 2169 1186 3128

chlorobenzene (2) 348.35 977 -786 1857 398.66 560 564 - 1261

benzene (1) t 298.20 1509 2068 -3126 chlorobenzene (2 ) 348.16 988 1300 -1860

398.66 711 912 1261

5-8 for both the Mixon et ai. and the Barker (6) data reduction methods. The Barker results shown used the five-constant Redlich-Kister equation to represent GE and used the same equations of state as the Mixon et al. calculation (see Tables X and XIj .

V L I 2 ) =

Y l 0000

03177 ,505 2 06314

723 1 .7933 .9494 895 7

e9351 ,9694

1.0000

ACT I V ? T Y COEFF I CjFNTS 1.i401 1. '0000 I OR69 1.0589 1.0430 I e O l l A 1.0314 1.0179 1.0222 1.0253 1 e 0 1 51 1.0341 1 e0095 1.0448 1 0854 1.0571 1.0026 1.0750 1 0000 1 e 1726

113.906

A C T I v y T Y CflEFF I C fENTS 1; 5000

001 6 1 sO6S2 1.0051 1.0495 1.0101 1.0361 1.0168 1.0260 1.0254 1.0173 1.0362

le0492 1 e0105 10 064 7 1.0836 1 s 1731 1.0000

t : % $

FXCFSS C198S

J / Y M F FUHCTICN*

0. a0 28. 26 42.89 51.02 55.97 55.55 52.74 46.51 36.59 22.33

0 . 0 0

FXCESS C I R P S

FUh CT 1 PN J/HOC F

0.00 30.27 4R. 79 40.37 66.63 6 R s 06 64.91 57.23 44.92 ?7.56

0 . 0 0

E XCES S C 19RS

J/MrlLE FUNCTT CN

0.00 32.42 5 5 . 3 6 71 26 90.79 fl4.11 91. 16 71 s 89 56.22 33.97 0 . 0 0

Table XII. Comparison of the Barker and Mixon et al. Results max % dev in Pa rms for 96 devb

temp, K Barker Mixon Barker Mixon

Nitromethane (1) i Chlorobenzene (2), Peng-Robinson 298.15 0.285 0.190 0.140 0.079 348.17 0.072 0.106 0.040 0.045 398.26 0.059 0.055 0.030 0.024

E.thano1 (1 ) + Chlorobenzene (2), Virial, Hayden-O'Connell 298.15 0.490 0.360 0.243 0.181 348.35 0.786 0.266 0.297 0.133 398.16 0.544 0.261 0.186 0.109

Benzene (1 ) + Chlorobenzene (2), Virial, Hayden-O'Connell 298.20 0.316 0.276 0.123 0.107 348.16 0.099 0.066 0.036 0.033 398.66 0.051 0.122 0.024 0.044

1-Chlorobutane (1) t Chlorobenzene (2), PenpRobinson 298.17 0.449 0.428 0.164 0.163 348.17 0.335 0.349 0.106 0.115 398.21 0.158 0.144 0.585 0.049


Table Xlll . Effect of Calculation Method on yi- Values for the Ethanol (1) + Chlorobenzene (2) Systema calcd yj'" values accuracy of P fits,

max % dev/rmsd component 1 component 2 calculation method 298.15 K 348.35 K 398.16 K 298.15 K 348.35 K 398.16 K 298.15 K 348.35 K 398.16 K -

Mixon et al. 0.4/0.2 0.3/0.1 Barker:

absolute Van Laar 5.712.6 1.313.8 Wilson 0.9/0.4 2.410.9 NRTL 1.4/0.7 1.1/0.4 modified Margules O.liO.0 1.7/0.6 UNIQUAC 4.712.3 1.210.4 Redlich-Kister, five constants 0.5/0.2 0,SiO.S

splined fits Gautreaux-Coa tes :

PJJlx,x, plots a Virial equation, Tsonopoulous correlation (7).

Table XIV. Effect of Equation of State Choice on yi- Values Obtained with Mixon et al. Method for Ethanol (1) + Chlorobenzene (2) at 398.16 K

eq of state used

ideal gas virial through E i j :

Tsonopolous (7) Hayden-O'Connell (5)

Redlich-Kwong, Lu modification ( I 1 )

3.6839 3.6369

3.8218 3.1537 3.9133 3.6278 3.7938 3.3872

The points in Figures 5-8 are the evenly spaced Mixon et al. values while the curves represent the Barker results. (As in the case of the P, curves in Figures 1-4, the curves plotted are approximations by the plotting software of the Barker input values: hence, small irregularities in the shapes of the curves are usually the fault of the plotting program rather than the Barker fit.) Both methods agreed very well for the nitromethane data sets but not so well for the other systems.

As shown in Table XII, the two methods reproduced the experimental P values at about the same level of accuracy for all systems but the ethanol system. A further comparison for that system is shown in Table XIII. Of the six GE correlations tried with the Barker method, only the five-constant Redlich- Kister equation reproduced the experimental P values at a level close to that of the Mixon et al. results. (The maximum percent deviation and root-mean-squared deviation (rmsd) values tabulated were calculated as shown at the bottom of Table XII.) However, as shown in the resolution error band plot in Figure 9, some of the Barker points fell outside the error band even with the Redlich-Kister equation. The zero line in Figure 9 represents the experimental P values. The boundaries formed by the large X's represent the maximum plus or minus experimental errors which could result due to the resolution lim- itations of the devices used to measure the pressure, temperature, and mole fraction values. The formula used to cal- culate the maximum possible resolution errors has been given in a previous paper (8). The resolution error does not include errors such as operator error, inadequate degassing, chemical reactions, etc. (Note that the 10-1 multiplier on the ordinate scale in Figure 9 means that the decimal point is to be moved one place to the left in the ordinate scale values.)

As shown in the Table XIII, the ethanol 4- chlorobenzene system is a difficult one for the popular GE correlations. Note the variation in the y im values, particularly at 298.15 K. The Redlich-Kister equation gives y im values which agree fairly well with the Mixon et al. results but even that equation has trouble

0.3/0.1 15.562

0.8i0.4 10.959 1.5/0.6 17.270 0.9/0.4 14.636 2.0/0.7 20.079 0.9/0.4 11.602 0.5/0.2 15.809

15.519

4.271

5.135 5.651 5.092 4.825 5.150 4.916

4.228 4.453

3.822

3.565 3.735 3.610 3.459 3.588 3.317

3.843 3.450

5.566

4.330 5.3 75 5.776 5.236 4.422 5.594

5.547 5.323

2.905

3.144 3.345 3.118 3.017 3.106 2.930

2.903 3.090

3.154

3.302 3.46 8 3.348 3.549 3.316 3.268

3.135 3.276

with the 298.15 K data set as shown in Figures 6 and 9. The use of the P,lxlx, plots along with the Gautreaux-

Coates equations (9) to obtain ylm values has been discussed previously (70). The (dPldxl)," values needed by the Gau- treaux-Coates equation were obtained both from the cubic splined fits and from extrapolation of the PDlx ,x, plots. The PD/XlX, plot could not be extrapolated with any certainty at 298.15 K for the ethanol + chlorobenzene system but other- wise the Gautreaux-Coates results support the general validity of the ylm values from the Mixon et al. method for that system.

The Mixon et al. "curves" in Figure 7 for the benzene + chlorobenzene system are very nicely spaced and are probably more reliable than the Barker results.

The activity coefficients for the 1-chlorobutane 4- chlorobenzene system do not vary much with temperature (see Figure 8). When the curves lie so close together, it is difficult to avoid crossing even when such crossing should not occur. From the shapes of the PD curves for this system (see Figure 4), crossing of the activity coefficient curves was not unexpected. The Barker and Mixon et al. results agreed reasonably well except for the intercepts at x , = 1.0.

Besides depending upon the data reduction method used, the calculated yi, y i , and GE values depend upon the equation of state used for the vapor-phase fugacity coefficients. An indi- cation of the magnitude of the effect on the y, values is given in Table XIV. The pressure for the ethanol + chlorobenzene system at 298.16 K ranged from 85.5 to 504.7 kPa.

Reglstry No. Chlorobenzene, 10&9&7; nitromethane, 75-52-5; ethanol, 64-17-5; 1-chiorobutane, 109-69-3; benzene, 7 1-43-2.

Literature Clted

(1) Maher, P. J.; Smith, 8. D. J. C h m . Eng. Data 1979, 2 4 , 363. (2) Maher, P. J.; Smith, 8. D. J. Chem. Eng. Data 1979, 2 4 , 16. (3) Mixon, F. 0.; Gumowski, B.; Carpenter, B. H. Ind. Eng. Chem. Fun-

dam. 1965, 4 , 455. (4) Peng, D.-Y.; Robinson, D. B. Ind. Eng. Chem. Fundam. 1976, 4,

455. (5) Hayden, J. G.; O'Conneli, J. P. Ind. Eng. Chem. Process Des. Dev.

1975, 14, 209. (6) Barker, J. A. Aust. J. Chem. 1953, 6, 207. (7) Tsonopoulos, C. AIChE J. 1974, 2 0 , 263. (8) Muthu, 0.; Maher, P. J.; Smith, B. D. J. Chem. Eng. Data 1980, 2 5 ,

163. (9) Gautreaux. M. F.; Coates, J. AIChE d . 1955, I , 496.

(IO) Maher, P. J.; Smith, B. D. Ind. Eng. Chem. Fundam. 1979, 18, 354. (11) Hamam, S. E. M.; Chung, W. K.; Elshayal, I. M.; Lu, B. C. Y. I d . Eng.

Chem. Process Des. Dev. 1977, "3, 51.

Received for review July 22, 1962. Accepted September 24, 1962. We gratefully acknowledge the financial support received from the National Sci- ence Foundation @ant CPE-80000534 and from the Industrlal Participants in the Thermodynamics Research Laboratory.

benzene chlorobenzene vle data

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