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
Table 1. Chemicals Used
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 G E 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. t h e 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-O’Connell correlation, was used for the data reported for the ethanol and benzene systems.
stated purity, 70
component
vendor
ethanol chlorobenzene 1-chlorobutane benzene
U.S. Industrial Chemicals Burdick and Jackson Burdick and Jackson Burdick and Jackson
NITRBMETHRNE (11
200 proof 99.9+ 99.9+ 99.9+
+ CHLOROBENZENE R 298.15 K E 3 ~ 8 . 1 7K
[21
C 399.26 K
0 f W
0 f O
a e Y
. a w o
I ntroductlon
a
3
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.
m
‘
%
m W
e e
o 0
-L o , 2
’
c U
0
-
LD.
0 0
m
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 respect to time, and all liquids were still perfectly clear when removed from the cells at the end of the last isotherm.
0 0
IO
0.20
0.40
0.60
00
0.80
XI
Flgure 1. Deviation from Raoult’s law for the nitromethane (1) chlorobenzene (2) system.
values required by the finitedifference Mixon-Gumowski-Carpenter method (3) for reduction of PTx data. Figures 1-4 show the experimental data in terms of the pressure deviation P , from Raoult’s 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
,
Experimental Data Tables 11-V present the experimental PTx data. The “smooth” pressure values reported there are from the leastsquares cubic splined fits used to provide the evenly spaced
+
0021-9568/83/1728-0100$01.50/00 1983 American Chemical Society
Journal of Chemical and Engineering Data, Vol. 28, No. 1, 1983 101
Table 11. Experimental P vs. x , Values for the Nitromethane (1)
+ Chlorobenzene (2) System
.--------
I--------------
,000i) e0474 0962 1650 2297 3106 .4 lac) a5133 -6113 7522 e7926 ,0965 ,9173 ,9596 1,0000
.oooo
1.629 2.973 3.544 3.915 4.217 4 491 4 660 4.790 4 e931 9.937 4.954 4.939 4.8ae 4.782 2 409
04 7 4
0961 1649 2296
:e5132 it15
61 13 7521 7926 8965 ,9178 9596 1.0000
Table 111. Experimental P vs. x . Values for the Ethanol (1)
0000
,0614 0795 1233 1816 ,2926 .3954 -4070 . 5 839 e6751 ,7814 8519 9059 -9631 1.0000
.0000
,0432
,0958 1348 1929 a2771 370 7 ,4 779 ,5780 e6858 ,7095 3306 9 182 ,9583 1.0000
1.644 5 305 5.612 6 109 6.418 6 794 7.024 7.191 7 356 I . 559 7.710 7.832 7.897 7.929 7.914
1.643 5.324 5.591 6.097 6.438 6.793 7.011 7.191 7 e369 7.562 7.706 7.821 7.901 7.937 7.310
1 635 2 146 2 739 3.184 3.831 't 768 5 e 807 6 993 d . 107 9 s 327 10 e433 13 886 11.862 12 304 12 755
1 e635 2.147 2.743 3.179 3.828 4 e768 5 309 7.000 8.110 9 301 10.444 10.897 11.859 12.299 12.757
.oooo
00610 ,0791 1289 .le11 -2921 395 1 4867 ,5837 6950 .la14 -8519 9058 09631 1.0000
.oooo
,0431 ,0957 1347 1927 .27 70 0 3704 4777 05778 6855 ,7893 8304 a9181 9582 1.0000
16.35 1 21 543 25.557 29.84 32 79 35.61 38.26 39.98 41 30 42.71 42.94 43.24 43.18 42.90 42.21
it: 325 25.543
---------.oooo
29.83
32.83 35.58 38.27 39.97 41.30 42.70 42.96 43.22 43.18 42.91 42.21
.0472 0959 1646 -2292
:Mi 51 30 8
e61 11 7520 7926 8965 -9178 -9596 1.0000
+ Chlorobenzene ( 2 ) System
23.322 43.09 47.99 56.79 62.45 69.69 73 94 76.89 79.61 82 59 84.85 86.72 88.00 89.16 89.59
23.321 43.16 47.86 56.89 62.30 69.74 73.98 76.78 79.57 82.69 84 96 86.68 87.88 89.05 89.73
16.333 19.449 23.155 25 887 29.33 35.81 42.33 49.82 56.84 64.42 71.67
16.338 19.436 23.159 25.892 29.93
.
74.57
80.80
83.67 86.54
: ;:!I$ 49.82 64.40 56.84
;::I8
00.78
83.62 86.57
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-0599 ,0784 e1276 -1797 2906 e3936 ,4856 ,5825 e6942 e7808 -8517 e9056 09630 3.0000
.0000 04 30
,0956 -1345 ,1924 2765 .3700 04771
a5772 e6851 a7890 ,8302 e9179 e9582 1.OOOC
85.51
t$8:2 242.18 282.3 !$J:o" 397.9 420.0 443.7
461.5 475.9 486.8 498.1 504.7
85.38 96.28 109.38 119.03 133.59
\205.20 ?'a:!';
230.00 258.68 285.6 296.3 319.6 330.3 341.3
85.51 169.39 190.04 241 e55 282.6 338.0 372.9 397.6 420.0 443.9 461.7 475.9 486.6 497.8 505.0
85.48
96.22 109.33 119.06 133.54 154 6 4 78: 16
$!8:'BJ
258.58 285.6 296.4 319.5 330.2 341.4
Table V. Experimental P vs. x Values for the l-Chlorobutane (1) t Chlorobenzene (2) System
16.278 19.949
23:s' 32
78 38.79 46.66 53.69 60.89 68.15 78.27 80.61 05.57 88.33 1.21
16.299
38.77 46.66
.
0000 -0434 .p33 418 .208 .2ssl
.
:.597! 2a:as $!: :# -6860 -8237 85:3 :!?If 88.31 91.22
1:%88&
-----------. 84 .f3 97.17 109.54
t $42: St 269.27 306.3 333.4
315.0
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,
x1
.oooo
.loo0 ,2000
,3390 4000 -5000 6000 ,7000
m
.8000
9300
1.0000
CC/YOL:
TiITAL PRESSURE, KPA EXPTL CALC
1.629 3.012 3.761 4.193 4.453 4.641 6.776 4.383
1,623 3.013 3.761 4 . 1 a3 4.453 4.641 4. 776 4,893 4.949 4.9 (13 4. 782
4.949
4.949 4.782
L I # U i O M O L A R VOLUMES,
x1
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,1000 2000 ,3000 4000 5000 a6000 ,7090 8300 9000 1.0000
CC/'lOL:
T O T A L PRE SSUi
