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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 stated
reported at approxlmately 298, 348, and 398 K for each component vendor purity, 70
of four chlorobenzene binaries with nltromethane, ethanol,
ethanol U.S. Industrial Chemicals 200 proof
benzene, and I-chlorobutane as the other components. chlorobenzene Burdick and Jackson 99.9+
The experimental PTx data were reduced to y,, y,, and 1-chlorobutane Burdick and Jackson 99.9+
GE values by both the Ylxon-Gumowskl-Carpenter and benzene Burdick and Jackson 99.9+
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 NITRBMETHRNE (11 + CHLOROBENZENE [21
R 298.15 K
equatlons of state were used to estlmate vapor-phase E 3 ~ 8 . 1 7K
C 399.26 K
fugacity coeff lclents. t h e Peng-Roblnson equatlon of 0

state was used for the reported data for the nitromethane W
f

and 1-chlorobutane systems. The vlrlal equation through


the second term, with the coefflclents predicted by the
0
Hayden-O’Connell correlation, was used for the data
O
f
reported for the ethanol and benzene systems. a
e
Y
. a
I ntroductlon w o
a ‘
3 %
m
This is the second paper reporting totalpressure vapor-liquid m
W
equilibrium (VLE) data on binary systems containing chloro- e
e o
0
benzene. The first paper ( I ) used acetone, acetonitrile, ethyl
acetate, ethylbenzene, methanol, and 1-pentene as the other -
2 ’

component. This paper reports data for nitromethane, ethanol,


benzene, and I-chlorobutane.
-L o ,
c
U

The apparatus and techniques for the experimental mea-


surements have been described in detail in a previous paper
0
-
LD.

( Z ) ,along with the defining equation for the activity coefficient


and the definition of the standard states used.
0
0

m
Chemlcats Used

The sources and purities of the chemicals used are listed in 0


Table I . Activated molecular sieves (either 3A or 4A) were 0
put into the chemical containers as they were received. Just IO 0.20 0.40 0.60 0.80 00
prior to being loaded in the VLE cells, the chemicals were XI
poured into distillation flasks and distilled through a Vigreux
column (25” 0.d. and 470 mm long). The first and last Flgure 1. Deviation from Raoult’s law for the nitromethane (1) +
portions of the distillate were discarded. The retained samples chlorobenzene (2) system.
were back-flushed with dry nitrogen and put into amber glass
bottles for transfer to the cell-loading operation. The stated values required by the finitedifference Mixon-Gumowski-Car-
purities of the chemicals were verified chromatographically at penter method (3) for reduction of PTx data.
this point. Figures 1-4 show the experimental data in terms of the
None of the compounds exhibited any degradation during the pressure deviation P , from Raoult’s law
VLE measurements. The cell pressures were stable with re-
spect to time, and all liquids were still perfectly clear when
P, = P - [ P * ‘ + x , ( P , ’ - P*’)]
removed from the cells at the end of the last isotherm. where P is the experimental mixture pressure and the P,’values
are the pure-component vapor pressures. The deviation
Experimental Data pressure plot emphasizes the scatter more than a P vs. x plot ,
but has the disadvantage of not indicating whether an azeotrope
Tables 11-V present the experimental PTx data. The exists.
“smooth” pressure values reported there are from the least- The point symbols in Figure 1-4 denote the experimental
squares cubic splined fits used to provide the evenly spaced data points. The curves approximate-sometimes not very

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

1.629 .oooo
I--------------

16.35 1
.-------- ----------
.oooo
,000i)
e0474
0962
2 409
2.973
04 7 4
0961
21 543
25.557
it: 325
25.543
.0472
0959
1650 3.544 1649 29.84 29.83 1646
2297 3.915 2296 32 79 32.83 -2292
3106
.4 lac)
a5133
4.217
4 491
4 660
:e5132
it15 35.61
38.26
39.98
35.58
38.27
39.97
:Mi
851 30
-6113 4.790 61 13 41 30 41.30 e61 11
7522 4 e931 7521 42.71 42.70 7520
e7926 9.937 7926 42.94 42.96 7926
,0965 4.954 8965 43.24 43.22 8965
,9173 4.939 ,9178 43.18 43.18 -9178
,9596 4.8ae 9596 42.90 42.91 -9596
1,0000 4.782 1.0000 42.21 42.21 1.0000

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

0000 1.644 1.643 .oooo 23.322 23.321 .oooo 85.51 85.51


,0614
0795
1233
5 305
5.612
6 109
5.324
5.591
6.097
00610
,0791
1289
43.09
47.99
56.79
43.16
47.86
56.89
-0599
,0784
e1276
t$8:2
242.18
169.39
190.04
241 e55
1816
,2926
.3954
-4070
. 5 839
6.418
6 794
7.024
7.191
7 356
6.438
6.793
7.011
7.191
7 e369
.le11
-2921
395 1
4867
,5837
62.45
69.69
73 94
76.89
79.61
. 62.30
69.74
73.98
76.78
79.57
-1797
2906
e3936
,4856
,5825
282.3
!$J:o"
397.9
420.0
282.6
338.0
372.9
397.6
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 e7808 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

.0000 1 635 1 e635 .oooo 16.333 16.338 .0000 85.38 85.48


,0432 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
.27 70
a2771
370 7
,4 779
't 768
5 e 807
6 993
4 e768
5 309
7.000
0 3704
4777
35.81
42.33
49.82
:;:!I$
49.82
2765
.3700
04771
\205.20
?'a:!'; 154 6 4
78: 16
,5780
e6858
d . 107
9 s 327
8.110
9 301
05778
6855
56.84
64.42 64.40
56.84
a5772
e6851
230.00
258.68
$!8:'BJ
258.58
,7095
3306
9 182
10 e433
13 886
11.862
10.444
10.897
11.859
,7893
8304
a9181
71.67
74.57
80.80
;::I8
00.78
a7890
,8302
e9179
285.6
296.3
319.6
285.6
296.4
319.5
,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

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

16.278 16.299 .0000


-----------.
84 .f3
19.949
23:s'
32
38.79
78
38.77
.
-0434
.p33
418
.208
.2ssl
97.17
109.54
t $42: St
46.66
53.69
60.89
46.66
2a:as :.597!
68.15
78.27
80.61
$!: :# -6860
-8237
269.27
306.3
05.57
88.33
85:3
88.31
:!?If 315.0
333.4
343.5
1.21 91.22 1:%88& 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: VL(1) f 53.942 VL(2) = 102.280

M IXTURE F UC A C I T Y
TiITAL PRESSURE, KPA COtFF I C I E N J S ACT I V! T Y COEFF I C EN15
x1 EXPTL CALC Y1
.oooo 1.629 1,623 ,9494 ,9589 .oooo
.loo0 3.012 3.013 .99as .9wo 5045
,2000 3.761 3.761 ,9984 ,9976 ,6314
,3390 4.193 4 . 1 a3 ,9983 ,9973 6886
m4000 4.453 4.453 .9982 .3971 ,7247
-5000 4.641 4.641 ,9981 ,9970 ,7521
6000 6.776 4. 776 eY980 e9970 -7762
,7000 4.383 4,893 ,9980 e9969 -8028
.8000 4.949 4.949 ,9979 e9969 ,8327
9300 4.949 4.9 (13 ,9979 ,9969 8883
1.0000 4.782 4. 782 e9980 ,9970 1.0000
L I # U i O M O L A R VOLUMES, CC/'lOL: VL(1) 57.211 VL(2) = 107 691

M I X TURE FUGACITY
T O T A L PRE SSUi<E, KPA COEFF C I E N I S A C T I V ~ T YCOEFFIC!ENTS
x1 EXPTL. CALC L Y1
.oooo 16.350 16.353 9928 .oooo 3.a207 1,booo
,1000 25.J21 25.222 9887 e4193 2.5785 1.0144
2000 31,562 31.96'1 .9863 e5613 2.1058 1 e0510
,3000 35.273 35. 274 .9847 ,6358 1.7751 1.1126
4000 37.372 37.872 9836 6859 1.5407 102006
5000 39.760 39.763 YO29 7245 1.3663 lo3247
a6000 41.163 41.152 9823 .7588 1.2337 1 e5010
107482
,7090 42.263 42.252 e9819 .7947 1.1367 2.1412
8300 42.996 42.994 9016 s8351 1.0632
9000 43.212 43.212 9816 8967 1.0197 2,6979
1.0000 42.209 42.209 9822 1.0000 1 .oooo 4.0137
L i U U I O HJLA3 VOLUMES, CC/HOL: VL(1) 0 61.120 VL(2) ' 113.907

tl I X 1URE FUC A C I T Y
TUTAL PRE ss U7E U P 4 C0:FF ICIENSS A C T I V ! T Y COEFF I CIENT S
X I EXPTL. CALC. Y1 I L
.0000 84.d05 84.835 .9h51 .9?36 .oooo 2.6586 1 .oooo
.loo0 121.200 121.2dB e3775 e9625 -3560 2.1798 1.0406
1.0105
.2090 145.445 115.449 e3727 ,9554 5042 1.6413
e 3000 162. 710 162. 7 13 ,9692 ,9504 ,5918 1.6054 1.0894
e4000 175.533 175.535 eV667 ,9467 ,6533 1.4298 1 1594
,5009 185 183 I 85. I a4 e7649 a9440 73 17 1.2934 1.2588
6000 17i.soo 1'12*61)1 e9633 a9420 ,7447 1.1877 1 e3971
.7300
,8300
,9000
198.544
202.147
204.Z63
198,544
20:. 747
204.5JL
,7621
,9612
,9608
-9404
,9394
,9392
7892
.a379
,9919
1.1106
1.0525
1.0158
!:z!$g
2 ,2726
1.0000 201.114 2310 714 ,9613 09407 1.0000 1.0000 3.1401

I
I
ETHRNBL [ I I + C H L D R B B E N Z E N E I21
A z 9 a . i ~K
BEhZEkE [I 1 t CHLOROBENZENE [ E l
P 298.20 K
8 3'48.35 K 3'48. 16 K
C 398.66 K 3 9 8 66 K

0 0

0.00 0.20 0.40 0.60 0.80


I
0.00
I
0.20
I
0.uo
I
0.60 0.80
I
. 00
XI XI
Figure 2. Deviation from Raoult's law for the ethanol (1) chloro- +-
benzene (2)system. Decimal point must be moved one place to right Figure 3. Deviation from Raoult's law for the benzene (1) 4- chloro-
in ordinate scale values. benzene (2) system.
Journal of Chemical and Engineering Data, Vol. 28, No. 1, 1983 103

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 VL(2) t 102.280


V I R I A L COEFFICIENTS, CC/f‘OL: B(l,l) = -2169.9 8(1,2) = -1185.0 B(2,2) -3127.6
EXCESS
MIXTURE FUGACITY CIBBS
TOTAL PRESSURE, K P A COCFF ICIENX S ACTIVlTY COEFFIC/ENTS FUNCTION,
x1 EXPTL. CALC. Y1 f J/MOLE
.oooo 1.643 1.643 1 Oh05 e9679 .oooo 15.&072 1.0000 0.00
.loo3 5.’125 5.824 ,9954 9963 ,7317 5.4006 1.0545 536.46
,2300 6.523 6.523 ,9947 9963 7668 3.1670 1 1549
1.2930 957e09
3000 6.309 6.809 ,9944 9963 e7810 2.2441 1048.08
4‘300
5000
e 6000
7300
.0000
7.020
7.216
7.398
7.i70
7.736
7.020
7.216
7.398
7.573
7.736
.
-7942
9940
9938
0 9936
9934
e 9964
,9964
9965
9967
e9971
7928
e8054
,8199
.a384
8663
le7610
1 4707
1.2789
1 1468
le0594
1.4728
1e 7 0 5 9
2.0232
2.4779
3.1425
1136.98
1140.09
1064.71
912.55
682.14
9000 7.393 7.893 9932 ,9979 e9187 1e0187 3.9024 378.84
1.0300 7.410 7.9 10 9931 e 9994 1.oooo 1.oooo 5.6941 0.00

L I Q U I D KOLAR VCLUMES, CCIMOL: V L ( 1 ) = 63.708 VL(2) = 107.690


V I R I A L COEFFICIENTS, CC/POL: 8(1,1) = -976.6 8(1,2) 1 -785.8 8I2r2) * -1857.1
EXCESS
MIXTURE FUGACITY CIBBS
TOTAL PRESSURE K P A COEFFICIENTS A C T I V I T Y COEFFICIENTS FUNCTION,
x1 EXPTL. CILC. 1 2 Y1 1 2 J/MOLE
0.00
.0300 23.321 23.321 1.0025 ,9850 .oooo 4.3344 1.0000
1‘300 52.272 52.270 -9363 e9744 .5878 1.0144 398.88
.2000 63.919 63.917 ,9813 09719 6803 2.4535
3*4852 1.0790 695.98
70.129 70.128 .37a7 .wio -7222 1 8999 1.1741
1.3048 883.01
3300 7496 le5607 978.03
4000
e5500
e6300
74.141
77.161
80.041
74.141
77.161
00.041
,9770
-9757
a9744
,9706
,9706
.9709
7726
.7985
1 e3373
e1932
1e0983
1.4799
1.7004
988.59
921.99
7000 0 2 . a ~ ~ 82.829 e9731 ,9717 e0299 1.9827 784.87
.8JOO 05.430 05.430 .97ia .9734 e 8698 1e0375 2.3516 580.56
e9000 07.759 07.759 e9706 e9765 e9252 1e0064 2.7827 313.16
1.0000 89.726 89.726 -3697 ,9816 1.0000 1.oooo 3.1027 0.00

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


V I R I A L COEFFICIENTS, CC/t‘OL: 8(1,1) = -560.4 B(192) = -563.8 8(2,2) -1260.6

EXCESS
MIXTURE FUGACITY CIBBS
x1
.oooo
,1300
.2000
TOTAL PRE SSURE, KPA
EXPTL.
85.509
2 14.384
2 95.332
CALC.
85.509
214.379
295.320
COCFF ICIENXS
leob41
9703
-9592
.
e
e
9L675
9360
92 19
Y1
e 0000
6220
7 4 19
A C T I V l T Y COEFFIC!ENTS
3.4133
2.8189
2.2737
1. ‘0000
1.0143
1.0543
FUNCTION e
JIHOLE
0.00
385.82
684.65
892.85
-3000 341.575 3 4 1.574 ,9454 s9147 e7887 1.8440 1 1302
4000
g5000
6000
’374.iiOl
401- 152
423.788
374. bC1
401.152
423.787
e 9392
e9342
s 9299
09101
s9069
9048
08105
.a418
08629
1.5641
1.3693
1.2294
11.5704
:$+:$ 1012.58
1050.71
1009.19
7000 445.088 445. 0 8 8 -9258 9036 e 0852 1.1299 1 8374 888.31
,8000 465.567 465.567 09219 90 3 6 -9111 1.0594 2.2315 685.10
390.78
,9300 485.463 405.463 ,9180 e 9059 .9454 1.0142 2 e8634
1e 0000 505.016 505.0 16 e9144 ,9133 1.0000 1.0000 3.6278 0.00

closely-the cubic splined fits of those data points. Interpo- benzene system has become a negative deviation system at
lated values (at 0.025 increments in x l) from the splined fis are all compositions, and the system has become more nonideal.
fed to the plotting software which then makes its own fit of the Neither the benzene nor the I-chlorobutane system forms an
input values. Those fits are often not very good if the curve azeotrope at any of the three temperatures.
is irregularly shaped. Nevertheless, the curves do help illustrate
the scatter and the general behavior of the experimental points. Reduced Data
For an accurate determination of how closely the splined fits
represent the experimental points, Tables 11-V must be used. The y,, y,, and GE values selected for publication are in
The nitromethane and ethanol systems show positive devia- Tables VI-IX. Those values were obtained with the Mixon et
tions from Raoult’s law at all three temperatures. The nitro- al. data reduction method (3).The Peng-Robinson equation of
methane forms an azeotrope at all three temperatures. No state (4) was used for the nitromethane and I-chlorobutane
azeotropes are formed with ethanol. systems to estimate the vapor-phase fugacity coefficients. The
The benzene and I-chlorobutanesystems change their mind virial equation truncated after the second term was used for the
as the temperature increases (mixed deviation systems). Both ethanol and benzene systems. The Hayden-O’Connell (5)
systems are almost ideal with small positive deviations at room correlation was used to estimate the 4, and Si! values. The
temperature. At 348 K, the benzene system is still almost ideal equation of state parameters are listed in Tables X and X I .
but the deviation at high x values has become negative despite The “experimental” pressure values tabulated in Tables VI-
the fact that the positive deviation at low xi values has in- I X are actually interpolated values from the cubic splined fits
creased. The positive deviation in the 1-chlorobutane system of the experimental P vs. x values. (The fidelity with which the
increased across the composition range at 348 K but the slight splined f i s represent the actual experimental P values is shown
sag at the higher x , values is a portent of the behavior at 398 in Tables 11-V.) The “calculated” pressure values are from the
K. At the highest temperature, the positive deviation of the Mixon et al. data reduction method and show how well that
1-chlorobutane system at low x values has increased further method can reproduce the original pressure data.
,
but the deviation is definitely negative at the high x values. The The calculated activity coefficient curves are shown in Figure
104 Journal of Chemical and Engineering Data, Val. 28, No. 1, 1983

E T H R N O L ( 1 1 T C H l O R O B E N Z E N t (21
R 299 1 7 6 A A 298.15 K
a 3 q 9 17 K + E 348.35 K
C 399 PI K m x C 398.66 K
0

g i
, I
I
I I I I I i 0 I I I I
0.00 0.20 0.110 0.60 o.ao 1.00
X.

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


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

1 NITSOMETHRNE (11 * C H L O R O B E N Z E N E [21


I 8ENtENE 111 + CHLOROBENZENE 123
r? 2 9 8 . L5 K
I A R 238.20 6
E 348.17 K + B 3ua. 16 6
C 398.26 K 31
N I
x c 3 9 8 . ~ 6K

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

+
Flgure 7. Activity coefficients for the benzene (1) chlorobenzene
Figure 5. Activity coefficients for the nitromethane (1) chloro- + (2) system. Curves are from Barker results; points are from Mixon et
benzene (2) system. Curves are from Barker results; points are from al. method. Move decimal point one place to left in ordinate scale
Mixon et al. method. values.
Journal of Chemical and Engineering Data, Vol. 28, No. 1, 1983 105

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 MOLAR'VOLUMES, CC/MOL: VL(1) = 09,409 VL(2) = 102.290
V I R I A L C O E F F I C I E N T S t CC/MOL: 0(1,1) -1509.1 e(1,2) = -2060.1 8(2,2) = -3125.7

T O T A L P R E S S U R E KPA
MIXTURE FUGACITY
COEFF I C I E N T S ACTIV!TY COEFFICIENTS
:CeLiss
FUNCTION,
x1 EXPTL ClLC. 1 2 1 L J/MOLE
,0000 1.635 1.635 .9993 .9979 1 0962 1 .oooo 0.00
,1300 2.789 2.789 e9905 -9066 1.0357 14.28
.zoo0 3.307 3.907 ,9977 .9954 1.0211 0 0 24 58
1 ee0066 19-87
a3000 5.023 5.023 ,9970 -9743 1.0155 22.87
e4000 6.136 6.136 ,9963 ,9931 1.0120 1 ,0085 24.37
,5000 7.246 7.246 e9956 ,3920 1.0093 1.0107 24.63

.
6000
e7000
8000
.9000
1.0300
8.353
9.450
10.560
1 1 -660
12.757
8.353
9.458
10.560
11.660
12.757
a9949
.'?'I42
a9936
e9929
a9922
,9909
,9890
,9807
,9876
,9065
1.0070
1 e0050
1.0031
1.0014
1 .oooo
1.0135
1.0173
1.0231
1.0333
1.0799
23.60
21.39
17.48
11.27
0.00
L I Q U I D MOLAR V O L U M E S , C C / M O L : V L ( 1 ) = 95.342 VL(2) 107.690
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 8(1,2) = -13CO.O B(2.2) * -1860.2
MIXTURE FUGACITY EXCESS
TOTAL PRESSURE KPA COEFFICIENTS
c1ee5
ACTIVITY COEFFICIENTS FUNCTION,
x1 ExrTL. ClLC, 1 2 Y1 1. 2 J/MOLE
,0303 16.338 16.338
09958 ,9895 .oooo 1.0443 1 .oooo 0.00
.loo0 23.458 23.457
a9728 ,9852 m3697 1 e0269 1.0008 9.80
.2000 30.442 30.441
e9901 ,9813 ,5657 1.0165 1 0026 15.43
3503 37.413 37.412
.9875 ,9775 6690 1.0117 1.0041 18.42
e 4000 44.395 44.394
,9850 ,9738 7741 1 e0007 1 e0057 19.90
,5000 51.380 51.307
e9826 ,9701 ,8364 1.0065 1 e0075 20.19
6300 5d.394 58.393
e9801 19665 e0041 1.0047 1 0097 19.35
700J 65.?14 65.413
-3777 ,9620 e9219 1 0032 1.0125 17.32
.oooo 72.949 72.443
e9753 e9592 ,9526 1.0019 1.0165 13.92
e9000 79.502 79.502
09729 ,9556 a9702 1 .0000 1.0232 0.72
1 .oooo 86.574 86.5 74
,9704 ,9519 1.0000 1.0000 1.0472 0.00
L I Q U I O KOLAR V C L U M E S , C C / M O L : V L ( 1 ) = 102,570 VL(2) * 113.961
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 0(1,2) = -912.1 8(212) -1260.6
EXCESS
MIXTURE FUGACITY CIBBS
TOTAL PRESSURE KPA CO$FF I C I E N I S ACTIVITY COEFFICIENTS FUNCTION,
EXPTL ClLC. Yl 1 2 J/HOLE
85.402 85.482 a9656 .'It75 .oooo 1.0228 1.0000 0.00
110.435 110.431 ,9789 ,9584 e2960 1.0107 1.0002 6.76
135.r141 135.436 ,9726 e9499 .4a44 1.0150 1 0009 12.11
160.535 160.528 a9667 ,9417 ,6153 1.0117 1.0019 16.05
105.748 105.742 e9609 ,9337 e7119
211.115
236.668
211.113
236.664
a9552
,9495
e9257
,9177
,7863
e0457
1 m 0089
1.0064
1 e0044
/1.0080
:!8% 10.56
19.62
19.19
262.440 262.430 ,9438 ,9098 ,8943 1.0027 1.0111 17.22
288.165 200.464 ,9381 .?ole ,9350 1.0014 1.0151 13.60
314.776 314. 776 e3324 ,8939 ,9698 1 e0005 1 e0205 0.12
341.406 341.406 e9266 e8058 1.0000 1.0000 1.0323 0.00
1
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 ETHRNOL 11' + CHLOPSEENZENE( 2 1
A R 298.17 K 29E.15 K
0 3118.17 K
x c 398.21 K a MIXON

N %I * ailaKER

01
+

m -
L -
-- 1
A

- I

+ + +
I +
A

x +
m
0

D
I I 1 1
0.00 0.20 0.110 0.60 0.BO 10 0.00 0.20 0.40 0.60 0.80 .a0

Xl Xl

Flgure 8. Activity coefficients for the 1-chlorobutane (1) chloro- +


benzene (2) system. Curves are from Barker results; points are from Flgure 9. Comparison of the Barker and Mixon et ai. results on the
Mixon et al. method. Move decimal point one place to left in ordinate +
resolution error plot for ethanol (1) chlorobenzene(2) at 348.35 K.
scale values. 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: VL(1) 105.126 VL(2) a 102.282

FXCFSS
MIXTURE FUGACITY C198S
TOTAL PRESSURE KPA COCFFICI E N I S 4 C T IV!TY CflEFF l C I F N T 5 FUHCTICN*
EXPTL.
2:854'9
ClLC.
1.641
2.959
.9d9l
e9984
,9589
e9981
::i$sb I1.0000
si033
J/YM F
0. a 0
28. 26
4 s187 4.187 .9978 ,9973 1.0532 1.0087 42.89

.
5.398
6.598
7 787
8.967
10.141
5.398
6.598
7.787
6.967
10.141
e9971
e9965
,9959
-9952
a9946
a9965
e9957
,9949
,9942
a9934
1.0379
k"Oil'
1.0141
1.0091
3
1.01 35
l:8M
1.0327
1.0422
51.02
55.97
55.55
52.74
46.51
11s 313 11.313 e9940 ,9927 1.0952 1.0546 36.59
12.485 12.485 ,9934 e9919 1.0022
13.654 13.654 ,9927 ,9911 1.0000 \:!:E 22.33
0.00

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

FXCESS
HIXTURE FUGACITY CIRPS
TOTAL PRESSURE, KP4 COfFFICIEN!S ACT I V ? T Y COEFF I CjFNTS FUh CT 1PN
EXPTL. CAL C. J/HOC F
16 -299
24.413
32 m092
:432.091
f193 1.i401
I OR69
1.0589
1. '0000 0.00
30.27
4R. 79
39.631 39.630 1.0430 IeOllA 40.37
47.072
54.448
6 1 791
69.126
5'41:m
61 790
69s 126
1.0314
1.0222
1e 0 1 51
1 e0095
1.0179
1.0253
1.0341
1.0448
66.63
6 R s 06
64.91
57.23
76.473 76.479 1 0854 1.0571 44.92
R3.870 83.870 1.0026 1.0750 ?7.56
91.216 91.216 1 0000 1 e 1726 0.00

L I C U I D POLAR VOLUMES, CC/MOL: VL(1) 121.271 VLI2) = 113.906

E XCES S
HIXTURE FUGACITY C 19RS
TOTAL PRESSURE KP4 CO$FFICIENSS A C T I v y T Y CflEFF I C fENTS FUNCTT CN
EXPTL. ClLC. Yl
84.573
112.856
84.573
112.853
0000
03177
1; 5000
001 6
J/MrlLE
0.00
32.42
140.171 140.167 ,505 2 1 sO6S2 1.0051 55.36
1 5 ?e 0 6 1 167.058 06314 1.0495 1.0101 71 26
13 3.665 723 1 1.0361 1.0168 90.79
220.107
246.519
$%:(1%
246.518
.7933 1.0260 1.0254 fl4.11
.9494 1.0173 1.0362 91. 16
273.053 273,052 895 7 1 e0105 le0492 71 s 89
299.863 299.863
327.089
354.376
327.089
354.376
e9351
,9694
1.0000
t:%$
1.0000
10064 7
1.0836
1 s 1731
56.22
33.97
0.00

Table X. Parameters for Peng-Robinson Equation (4)a Table XII. Comparison of the Barker and Mixon et al. Results
component Tc, K P,, MPa L max % dev in Pa rms for 96 devb
nitromethane 588.0 6.313 0.3460 temp, K Barker Mixon Barker Mixon
1-chlorobutane 542.0 3.688 0.2180
chlorobenzene 632.4 Nitromethane (1) iChlorobenzene (2), Peng-Robinson
4.520 0.2490
298.15 0.285 0.190 0.140 0.079
a Binary interaction constant was set at 0.0 for all systems. 348.17 0.072 0.106 0.040 0.045
398.26 0.059 0.055 0.030 0.024
Table XI. Virial Coefficient Values (5) E.thano1 (1) + Chlorobenzene (2), Virial, Hayden-O'Connell
298.15 0.490 0.360 0.243 0.181
system T, K B,, B,, B?2
348.35 0.786 0.266 0.297 0.133
ethanol (1) + 298.15 2169 1186 3128 398.16 0.544 0.261 0.186 0.109
chlorobenzene (2) 348.35 977 -786 1857 Benzene (1) + Chlorobenzene (2), Virial, Hayden-O'Connell
398.66 560 564 - 1261
298.20 0.316 0.276 0.123 0.107
benzene (1) t 298.20 1509 2068 -3126 348.16 0.099 0.066 0.036 0.033
chlorobenzene ( 2 ) 348.16 988 1300 -1860 398.66 0.051 0.122 0.024 0.044
398.66 711 912 1261
1-Chlorobutane (1) t Chlorobenzene (2), PenpRobinson
5-8 for both the Mixon et ai. and the Barker (6) data reduction 298.17 0.449 0.428 0.164 0.163
348.17 0.335 0.349 0.106 0.115
methods. The Barker results shown used the five-constant 398.21 0.158 0.144 0.585 0.049
Redlich-Kister equation to represent GE and used the same
equations of state as the Mixon et al. calculation (see Tables
X and X I j .
Journal of Chemical and Engineering Data, Vol. 28, No. 1, 1983 107

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 0.3/0.1 15.562 4.271 3.822 5.566 2.905 3.154
Barker:
absolute Van Laar 5.712.6 1.313.8 0.8i0.4 10.959 5.135 3.565 4.330 3.144 3.302
Wilson 0.9/0.4 2.410.9 1.5/0.6 17.270 5.651 3.735 5.3 75 3.345 3.46 8
NRTL 1.4/0.7 1.1/0.4 0.9/0.4 14.636 5.092 3.610 5.776 3.118 3.348
modified Margules O.liO.0 1.7/0.6 2.0/0.7 20.079 4.825 3.459 5.236 3.017 3.549
UNIQUAC 4.712.3 1.210.4 0.9/0.4 11.602 5.150 3.588 4.422 3.106 3.316
Redlich-Kister, five constants 0.5/0.2 0,SiO.S 0.5/0.2 15.809 4.916 3.317 5.594 2.930 3.268
Gautreaux-Coa tes :
splined fits 15.519 4.228 3.843 5.547 2.903 3.135
PJJlx,x, plots 4.453 3.450 5.323 3.090 3.276
a Virial equation, Tsonopoulous correlation (7).

Table XIV. Effect of Equation of State Choice on yi- Values with the 298.15 K data set as shown in Figures 6 and 9.
Obtained with Mixon et al. Method for Ethanol (1) + The use of the P,lxlx, plots along with the Gautreaux-
Chlorobenzene (2) at 398.16 K
Coates equations (9) to obtain ylmvalues has been discussed
previously (70). The (dPldxl)," values needed by the Gau-
eq of state used treaux-Coates equation were obtained both from the cubic
splined fits and from extrapolation of the PDlx,x, plots. The
ideal gas 3.6839 3.6369 PD/XlX, plot could not be extrapolated with any certainty at
virial through E i j :
Tsonopolous (7) 3.8218 3.1537
+
298.15 K for the ethanol chlorobenzene system but other-
Hayden-O'Connell (5) 3.9133 3.6278 wise the Gautreaux-Coates results support the general validity
Redlich-Kwong, Lu 3.7938 3.3872 of the ylmvalues from the Mixon et al. method for that system.
modification ( I 1 ) The Mixon et al. "curves" in Figure 7 for the benzene +
chlorobenzene system are very nicely spaced and are probably
The points in Figures 5-8 are the evenly spaced Mixon et al. more reliable than the Barker results.
values while the curves represent the Barker results. (As in the The activity coefficients for the 1-chlorobutane 4- chloro-
case of the P, curves in Figures 1-4, the curves plotted are benzene system do not vary much with temperature (seeFigure
approximations by the plotting software of the Barker input 8). When the curves lie so close together, it is difficult to avoid
values: hence, small irregularities in the shapes of the curves crossing even when such crossing should not occur. From the
are usually the fault of the plotting program rather than the shapes of the PD curves for this system (see Figure 4), crossing
Barker fit.) Both methods agreed very well for the nitromethane of the activity coefficient curves was not unexpected. The
data sets but not so well for the other systems. Barker and Mixon et al. results agreed reasonably well except
As shown in Table XII, the two methods reproduced the for the intercepts at x , = 1.0.
experimental P values at about the same level of accuracy for Besides depending upon the data reduction method used, the
all systems but the ethanol system. A further comparison for calculated yi, y i , and GE values depend upon the equation of
that system is shown in Table XIII. Of the six GEcorrelations state used for the vapor-phase fugacity coefficients. An indi-
tried with the Barker method, only the five-constant Redlich- cation of the magnitude of the effect on the y, values is given
Kister equation reproduced the experimental P values at a level +
in Table XIV. The pressure for the ethanol chlorobenzene
close to that of the Mixon et al. results. (The maximum percent system at 298.16 K ranged from 85.5 to 504.7 kPa.
deviation and root-mean-squared deviation (rmsd) values tabu-
lated were calculated as shown at the bottom of Table XII.) Reglstry No. Chlorobenzene, 10&9&7; nitromethane, 75-52-5; ethanol,
64-17-5; 1-chiorobutane, 109-69-3; benzene, 7 1-43-2.
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 Literature Clted
represents the experimental P values. The boundaries formed
(1) Maher, P. J.; Smith, 8. D. J. C h m . Eng. Data 1979, 2 4 , 363.
by the large X's represent the maximum plus or minus ex- (2) Maher, P. J.; Smith, 8. D. J. Chem. Eng. Data 1979, 2 4 , 16.
perimental errors which could result due to the resolution lim- (3) Mixon, F. 0.; Gumowski, B.; Carpenter, B. H. Ind. Eng. Chem. Fun-
dam. 1965, 4 , 455.
itations of the devices used to measure the pressure, tem- (4) Peng, D.-Y.; Robinson, D. B. Ind. Eng. Chem. Fundam. 1976, 4,
perature, and mole fraction values. The formula used to cal- 455.
culate the maximum possible resolution errors has been given (5) Hayden, J. G.; O'Conneli, J. P. Ind. Eng. Chem. Process Des. Dev.
1975, 14, 209.
in a previous paper (8). The resolution error does not include (6) Barker, J. A. Aust. J. Chem. 1953, 6, 207.
errors such as operator error, inadequate degassing, chemical (7) Tsonopoulos, C. AIChE J. 1974, 2 0 , 263.
reactions, etc. (Note that the 10-1 multiplier on the ordinate (8) Muthu, 0.; Maher, P. J.; Smith, B. D. J. Chem. Eng. Data 1980, 2 5 ,
163.
scale in Figure 9 means that the decimal point is to be moved (9) Gautreaux. M. F.; Coates, J. AIChE d . 1955, I , 496.
one place to the left in the ordinate scale values.) (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.
As shown in the Table XIII, the ethanol 4-chlorobenzene Chem. Process Des. D e v . 1977, "3, 51.
system is a difficult one for the popular GE correlations. Note
the variation in the y i mvalues, particularly at 298.15 K. The Received for review July 22, 1962. Accepted September 24, 1962. We
gratefully acknowledge the financial support received from the National Sci-
Redlich-Kister equation gives y i mvalues which agree fairly well ence Foundation @ant CPE-80000534 and from the Industrlal Participants in
with the Mixon et al. results but even that equation has trouble the Thermodynamics Research Laboratory.