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-OConnell 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

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
W

e
e

o
0

-L o ,
2

c
U

LD.

0
0

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 Raoults 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 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

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

.oooo

-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

.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

.oooo

,1000
2000
,3000
4000
5000
a6000
,7090
8300
9000
1.0000

CC/'lOL:

T O T A L PRE SSUi<E, KPA

CALC
EXPTL.

16.353
25.222
31.96'1
35. 274
37.872
39.763

16.350
25.J21
31,562
35.273
37.372
39.760
41.163
42.263
42.996
43.212
42.209

.loo0
.2090
e

3000

e4000

,5009
6000
.7300
,8300
,9000

1.0000

121.200
145.445
162. 710
175.533
185 183
17i.soo
198.544

CC/HOL:

121.2dB
115.449
162. 7 13
175.535
I 85. I a4
1'12*61)1
198,544
20:. 747

202.147

204.5JL
2310 714

204.Z63

201.114
ETHRNBL [ I I

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

,9494
.99as
,9984
,9983
.9982
,9981
eY980
,9980
,9979
,9979
e9980

,9589
.9wo
,9976
,9973
.3971
,9970
e9970
e9969
e9969
,9969
,9970

VL(1)

57.211

M I X TURE FUGACITY
COEFF C I E N I S
L

41.152

TUTAL PRE ss U7E U P 4

CALC.
EXPTL.
84.835
84.d05

53.942

42.252
42.994
43.212
42.209

L i U U I O HJLA3 VOLUMES,

X I
.0000

VL(1)

VL(1)

9928
9887
.9863
.9847
9836
YO29
9823
e9819
9016
9816
9822
61.120

VL(2) =

ACT I V! T Y COEFF I C EN15

Y1

.oooo

5045
,6314
6886
,7247
,7521
-7762
-8028
,8327
8883
1.0000
VL(2) =

ICIENSS

.9h51
e3775
e3727
,9692
eV667
e7649
e9633
,7621
,9612
,9608
,9613

.9?36
e9625
,9554
,9504
,9467
a9440
a9420
-9404
,9394
,9392
09407

107 691
A C T I V ~ T YCOEFFIC!ENTS

Y1

.oooo

1.0000
VL(2)

113.907
A C T I V ! T Y COEFF I CIENT S
I
L

1 .oooo

2.6586
2.1798
1.6413
1.6054
1.4298
1.2934
1.1877
1.1106
1.0525
1.0158
1.0000

-3560
5042
,5918
,6533
73 17

,7447

7892
.a379
,9919
1.0000

C H L D R B B E N Z E N E I21

1.0144
1 e0510
1.1126
102006
lo3247
1
107482
e5010
2.1412
2,6979
4.0137

1 .oooo

'

Y1

.oooo

1,booo

3.a207
2.5785
2.1058
1.7751
1.5407
1.3663
1.2337
1.1367
1.0632
1.0197

e4193
e5613
,6358
6859
7245
.7588
.7947
s8351
8967

tl I X 1URE FUC A C I T Y
C0:FF

102.280

BEhZEkE

A z 9 a . i ~K
8 3'48.35 K
C 398.66 K

1.0105
1.0406
1.0894
1 1594
1.2588
1 e3971

!:z!$g

2 ,2726
3.1401

[I 1

CHLOROBENZENE [ E l

P 298.20 K
3'48. 16 K
3 9 8 66 K

0.00

0.20

0.60

0.40
XI

0.80

0.00

+-

Figure 2. Deviation from Raoult's law for the ethanol (1) chlorobenzene (2)system. Decimal point must be moved one place to right
in ordinate scale values.

0.20

0.60

0.uo

0.80

. 00

XI

Figure 3. Deviation from Raoult's law for the benzene (1) 4- chlorobenzene (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:

V I R I A L COEFFICIENTS, CC/fOL:

x1

.oooo

.loo3
,2300
3000
4300
5000
e 6000
7300
.0000

9000

1.0300

TOTAL PRESSURE, K P A
EXPTL.
CALC.
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.i70
7.573
7.736
7.736
7.393
7.893
7.410
7.9 10

L I Q U I D KOLAR VCLUMES,
V I R I A L COEFFICIENTS,

x1

.0300
1300
.2000
3300
4000
e5500
e6300
7000
.8JOO
e9000
1.0000

V I R I A L COEFFICIENTS,

x1

.oooo

,1300
.2000
-3000

4000

g5000
6000

7000
,9300
,8000

1e 0000

59.821
-2169.9

MIXTURE FUGACITY
COCFF ICIENX S
e9679
9963
9963
9963
e 9964
,9964
9965
9967
e9971
,9979
e 9994

1 Oh05
,9954
,9947
,9944
-7942
9940
9938
0 9936
9934
9932
9931

CCIMOL: V L ( 1 ) =
CC/POL:

TOTAL PRESSURE K P A
EXPTL.
CILC.
23.321
23.321
52.270
52.272
63.919
63.917
70.129
70.128
74.141
74.141
77.161
77.161
00.041
80.041
0 2 . a ~ ~
82.829
05.430
05.430
07.759
07.759
89.726
89.726

L I Q U I D HOLdR VOLUMES,

VL(1) *
B(l,l)

CC/HOLI
CC/tOL:

TOTAL PRE SSURE, KPA

CALC.
EXPTL.
85.509
85.509
214.379
2 14.384
295.320
2 95.332
3 4 1.574
341.575
374. bC1
374.iiOl
401.152
401- 152
423.787
423.788
445. 0 8 8
445.088
465.567
465.567
405.463
485.463
505.0 16
505.016

8(1,1)

VL(1)

-1185.0

B(2,2)

-3127.6

ACTIVlTY COEFFIC/ENTS

Y1

.oooo

15.&072
5.4006
3.1670
2.2441
le7610
1 4707
1.2789
1 1468
le0594
1e0187
1.oooo

,7317
7668
e7810
7928

e8054
,8199
.a384

8663
e9187
1.oooo

-976.6

8(1,2)

1.0000
1.0545
1.2930
1 1549
1.4728
1e 7 0 5 9
2.0232
2.4779
3.1425
3.9024
5.6941

107.690
-785.8

8I2r2) *

-1857.1
EXCESS

.5878
6803
-7222
7496
7726
.7985
e0299
e 8698
e9252
1.0000

70.160

VL(2)

113.961

-560.4

B(192) =

9L675
9360
92 19
s9147
09101
s9069
9048
9036
90 3 6
e 9059
,9133

e
e

CIBBS

FUNCTION,
J/MOLE
0.00
536.46
957e09
1048.08
1136.98
1140.09
1064.71
912.55
682.14
378.84

0.00

A C T I V I T Y COEFFICIENTS
2
1
4.3344
1.0000
1.0144
2.4535
3*4852
1.0790
1 8999
1.1741
1.3048
le5607
1.4799
e3373
e1932
1.7004
1e0983
1.9827
2.3516
1e0375
2.7827
1e0064
3.1027
1.oooo

closely-the cubic splined fits of those data points. Interpolated 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-chlorobutanesystems 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

EXCESS

VL(2) =

MIXTURE FUGACITY
COCFF ICIENXS
leob41
9703
-9592
,9454
e 9392
e9342
s 9299
-9258
09219
,9180
e9144

102.280

8(1,2)

63.708

MIXTURE FUGACITY
COEFFICIENTS
2
1
1.0025
,9850
-9363
e9744
,9813
09719
.37a7
.wio
,9770
,9706
-9757
,9706
a9744
.9709
e9731
,9717
.97ia
.9734
e9706
e9765
-3697
,9816

8(1,1)

VL(2)

Y1

.oooo

CIBBS

FUNCTION,
J/MOLE
0.00
398.88
695.98
883.01
978.03
988.59
921.99
784.87
580.56
313.16
0.00

-563.8

8(2,2)

-1260.6
EXCESS

Y1
e 0000
6220
7 4 19
e7887
08105
.a418
08629
e 0852
-9111
.9454

A C T I V l T Y COEFFIC!ENTS

1.0000

3.4133
2.8189
2.2737
1.8440
1.5641
1.3693
1.2294
1.1299
1.0594
1.0142
1.0000

1. 0000
1.0143
1.0543
1 1302

11.5704
:$+:$

1 8374
2.2315
2 e8634
3.6278

CIBBS

FUNCTION e
JIHOLE
0.00
385.82
684.65
892.85
1012.58
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 X I .
The experimental pressure values tabulated in Tables VII X are actually interpolated values from the cubic splined fits
of the experimental P vs. x values. (The fidelity with which the
splined f i s 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
E T H R N O L ( 1 1 T C H l O R O B E N Z E N t (21
A A 298.15 K
+ E 348.35 K
x C 398.66 K

R 299 1 7 6

3 q 9 17 K

C 399

PI

m
0

g 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) system.

NITSOMETHRNE (11

8ENtENE 111

31

C H L O R O B E N Z E N E [21

r? 2 9 8 . L5 K
E 348.17 K
C 398.26 K

0 1

0.00

0.20

0.40

0.60

chlorobenzene(2)
system. Curves are from the Barker results: points are from Mixon
et al. method.

Figure 6. Activity coefflcients for the ethanol (1)

CHLOROBENZENE 123

R 238.20 6
B 3ua. 16 6

3 9 8 . ~ 6K

DO

0.80

Figure 5. Activity coefficients for the nitromethane (1)

chlorobenzene (2) system. Curves are from Barker results; points are from
Mixon et al. method.

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.

Journal of Chemical and Engineering Data, Vol. 28, No. 1, 1983 105

Table VIII. Calculated Data for the Benzene (1)

et al. Method and the Virial Equation through B"
L I Q U I D MOLAR'VOLUMES, CC/MOL:
V I R I A L C O E F F I C I E N T S t CC/MOL:
T O T A L P R E S S U R E KPA
EXPTL
ClLC.

+ Chlorobenzene (2) System at 298.20, 348.16, and 398.66 K Obtained with the Mixon
=

VL(1)

0(1,1)

x1

TOTAL PRESSURE KPA

ExrTL.
ClLC,

16.338
23.458
30.442
37.413
44.395
51.380
5d.394
65.?14
72.949
79.502
86.574

16.338
23.457
30.441
37.412
44.394
51.307
58.393
65.413
72.443
79.502
86.5 74

TOTAL PRESSURE KPA

EXPTL
ClLC.
85.402
85.482

110.435
135.r141
160.535
105.748
211.115
236.668
262.440
288.165
314.776
341.406

110.431
135.436
160.528
105.742
211.113
236.664
262.430
200.464
314. 776
341.406

2
.9979
-9066
.9954
-9743
,9931
,3920
,9909
,9890
,9807
,9876
,9065
95.342
-988.1

MIXTURE FUGACITY
COEFFICIENTS
1
2

09958
a9728
e9901
.9875
,9850
e9826
e9801
-3777
e9753
09729
1 .oooo
,9704
L I Q U I O KOLAR V C L U M E S , C C / M O L : V L ( 1 ) =
V I R I A L C O E F F I C I E N T S , CC/!'OL:
B(l,l) =
,0303

.loo0
.2000
3503
e 4000
,5000
6300
700J
.oooo
e9000

VL(2) =

e(1,2) =

MIXTURE FUGACITY
COEFF I C I E N T S

1
,0000
1.635
1.635
.9993
,1300
2.789
2.789
e9905
3.307
3.907
,9977
.zoo0
a3000
5.023
5.023
,9970
e4000
6.136
6.136
,9963
7.246
e9956
,5000
7.246
6000
8.353
8.353
a9949
e7000
9.450
9.458
.'?'I42
10.560
a9936
8000
10.560
.9000
1 1 -660
e9929
11.660
1.0300
12.757
12.757
a9922
L I Q U I D MOLAR V O L U M E S , C C / M O L : V L ( 1 ) =
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 =
x1

09,409
-1509.1

,9895
,9852
,9813
,9775
,9738
,9701
19665
,9620
e9592
,9556
,9519
102,570
-710.7

MIXTURE FUGACITY
CO$FF I C I E N I S

a9656
,9789
,9726
a9667
e9609
a9552
,9495
,9438
,9381
e3324
e9266

.'It75
,9584
e9499
,9417
,9337
e9257
,9177
,9098
.?ole
,8939
e8058

102.290
-2060.1
ACTIV!TY
1

8(2,2) =

-3125.7

COEFFICIENTS
L

:CeLiss

FUNCTION,
J/MOLE

1 0962
1 .oooo
1.0357
0 0 24 58
1.0211
1 ee0066
1.0155
1.0120
1 ,0085
1.0093
1.0107
1.0070
1.0135
1 e0050
1.0173
1.0031
1.0231
1.0014
1.0333
1 .oooo
1.0799
VL(2)
107.690
8(1,2) = -13CO.O
B(2.2) * -1860.2
ACTIVITY COEFFICIENTS

0.00
14.28
19-87
22.87
24.37
24.63
23.60
21.39
17.48
11.27
0.00

EXCESS
c1ee5
FUNCTION,
J/MOLE

Y1
1.
2
.oooo
1.0443
1 .oooo
1 e0269
1.0008
m3697
,5657
1.0165
1 0026
6690
1.0117
1.0041
7741
1 e0007
1 e0057
,8364
1.0065
1 e0075
e0041
1.0047
1 0097
e9219
1 0032
1.0125
,9526
1.0019
1.0165
a9702
1 .0000
1.0232
1.0000
1.0000
1.0472
VL(2) *
113.961
0(1,2) =
-912.1 8(212)
-1260.6

0.00
9.80
15.43
18.42
19.90
20.19
19.35
17.32
13.92
0.72
0.00

EXCESS
ACTIVITY COEFFICIENTS

Yl
.oooo
e2960
.4a44
,6153
e7119
,7863
e0457
,8943
,9350
,9698
1.0000

1
1.0228
1.0107
1.0150
1.0117
1 m 0089
1.0064
1 e0044
1.0027
1.0014
1 e0005
1.0000

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 298.17 K

1.0000
1.0002
1 0009
1.0019

0 3118.17 K
398.21 K

%I
01

0.00
6.76
12.11
16.05
10.56
19.62
19.19
17.22
13.60
0.12
0.00

/1.0080
:!8%

1.0111
1.0151
1 e0205
1.0323

ETHRNOL 11'

x c

CIBBS

FUNCTION,
J/HOLE

CHLOPSEENZENE( 2 1

29E.15 K
MIXON
*
ailaKER

-- 1

m L -

A
-

+ +

+
x

m
0
D

0.00

0.20

0.110

0.60
Xl

10

0.BO

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.

0.00

0.20

0.60

0.40

0.80

.a0

Xl

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:

TOTAL PRESSURE KPA

EXPTL.
ClLC.

2:854'
9
187
4 s

5.398
6.598
7 787
8.967
10.141
11s 313
12.485
13.654

16 -299
24.413
32 m092
39.631
47.072
54.448
6 1 791
69.126
76.473
R3.870
91.216

.9d9l
e9984
.9978
e9971
e9965
,9959
-9952
a9946
e9940
,9934
,9927

CC/MOL:

TOTAL PRESSURE, KP4

EXPTL.
CAL C.

VLII)

112.244

HIXTURE FUGACITY
CO$FFICIENSS

84.573
112.853
140.167
167.058

VLI2)

Yl
0000

03177
,505 2
06314
723 1
.7933
.9494
895 7
e9351
,9694
1.0000

$%:(1%
246.518

273,052
299.863
327.089
354.376

55.97

0.00

1. '0000

IeOllA
1.0179
1.0253

1.0341
1.0448

1.0571
1.0750
1 e 1726

FXCESS
CIRPS
FUh CT 1PN
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
0.00

113.906

A C T I v y T Y CflEFF I C fENTS

1; 5000
001 6

1.0051
1.0101
1.0168
1.0254
1.0362
le0492
10064 7
1.0836
1 s 1731

1 sO6S2
1.0495
1.0361
1.0260
1.0173
1 e0105

t:%$

1.0000

E XCES S
C 19RS
FUNCTT CN
J/MrlLE

0.00
32.42

55.36

71 26
90.79
fl4.11
91. 16
71 s 89
56.22
33.97
0.00

Table XII. Comparison of the Barker and Mixon et al. Results

max % dev in Pa

Tc, K

P,, MPa

nitromethane
1-chlorobutane
chlorobenzene

588.0
542.0
632.4

6.313
3.688
4.520

0.3460
0.2180
0.2490

Binary interaction constant was set at 0.0 for all systems.

Table XI. Virial Coefficient Values (5)

B,,
1186
-786
564
2068
1300
912

55.55
52.74
46.51
36.59
22.33

ACT I V ? T Y COEFF I CjFNTS

61 790
69s 126
76.479
83.870
91.216

121.271

1.0327
1.0422
1.0546

1C7.690

VL(2)

1.i401

VL(1)

28. 26
42.89
51.02

\:!:E

1.0000

1.0589
1.0430
1.0314
1.0222
1e 0 1 51
1 e0095
1 0854
1.0026
1 0000

component

benzene (1) t
chlorobenzene ( 2 )

1.0091
1.0952
1.0022

FXCFSS
C198S
FUHCTICN*
J/YM F
0. a 0

1.0087
1.01 35

l:8M

k"Oil'
3
1.0141

5'41:m

B,,
2169
977
560
1509
988
711

I1.0000
si033

1.0532
1.0379

39.630

T, K
298.15
348.35
398.66
298.20
348.16
398.66

CflEFF l C I F N T 5

I OR69

Table X. Parameters for Peng-Robinson Equation (4)a

system
ethanol (1) +
chlorobenzene (2)

::i$sb

,9589
e9981
,9973
a9965
e9957
,9949
,9942
a9934
,9927
e9919
,9911

102.282

4 C T IV!TY

:432.091
f193

TOTAL PRESSURE KP4

EXPTL.
ClLC.

HIXTURE FUGACITY
COfFFICIEN!S

L I C U I D POLAR VOLUMES, CC/MOL:

84.573
112.856
140.171
1 5 ?e 0 6 1
13 3.665
220.107
246.519
273.053
299.863
327.089
354.376

VL(2)

MIXTURE FUGACITY
COCFFICI E N I S

1.641
2.959
4.187
5.398
6.598
7.787
6.967
10.141
11.313
12.485
13.654

L I Q C I O MOLAR VOLUHES,

105.126

VL(1)

B?2

3128
1857
- 1261
-3126
-1860
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 X I j .

temp, K

Barker

Mixon

rms for 96 devb

Barker

Mixon

Nitromethane (1) iChlorobenzene (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)
298.15
348.35
398.16

+ Chlorobenzene (2), Virial, Hayden-O'Connell

Benzene (1)
298.20
348.16
398.66

+ Chlorobenzene (2), Virial, Hayden-O'Connell

0.490
0.786
0.544
0.316
0.099
0.051

0.360
0.266
0.261
0.276
0.066
0.122

0.243
0.297
0.186
0.123
0.036
0.024

0.181
0.133
0.109
0.107
0.033
0.044

1-Chlorobutane (1) t Chlorobenzene (2), PenpRobinson

298.17
0.449
0.428
0.164
0.163
0.115
348.17
0.335
0.349
0.106
398.21
0.158
0.144
0.585
0.049

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
calculation method
Mixon et al.
Barker:
absolute Van Laar
Wilson
NRTL
modified Margules
UNIQUAC
Redlich-Kister, five constants
Gautreaux-Coa tes :
splined fits
PJJlx,x, plots
a

component 1

component 2

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

0.4/0.2

0.3/0.1

0.3/0.1

15.562

4.271

3.822

5.566

2.905

3.154

5.712.6
0.9/0.4
1.4/0.7
O.liO.0
4.712.3
0.5/0.2

1.313.8
2.410.9
1.1/0.4
1.7/0.6
1.210.4
0,SiO.S

0.8i0.4
1.5/0.6
0.9/0.4
2.0/0.7
0.9/0.4
0.5/0.2

10.959
17.270
14.636
20.079
11.602
15.809

5.135
5.651
5.092
4.825
5.150
4.916

3.565
3.735
3.610
3.459
3.588
3.317

4.330
5.3 75
5.776
5.236
4.422
5.594

3.144
3.345
3.118
3.017
3.106
2.930

3.302
3.46 8
3.348
3.549
3.316
3.268

15.519

4.228
4.453

3.843
3.450

5.547
5.323

2.903
3.090

3.135
3.276

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
3.9133
3.7938

3.1537
3.6278
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 GEcorrelations
tried with the Barker method, only the five-constant RedlichKister 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 limitations of the devices used to measure the pressure, temperature, and mole fraction values. The formula used to calculate 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 i mvalues, particularly at 298.15 K. The
Redlich-Kister equation gives y i mvalues which agree fairly well
with the Mixon et al. results but even that equation has trouble

with the 298.15 K data set as shown in Figures 6 and 9.

The use of the P,lxlx,
plots along with the GautreauxCoates equations (9) to obtain ylmvalues has been discussed
previously (70). The (dPldxl)," values needed by the Gautreaux-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 otherwise the Gautreaux-Coates results support the general validity
of the ylmvalues 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 (seeFigure
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 indication 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. Fundam. 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.
Maher, P. J.; Smith, B. D. J. Chem. Eng. Data 1980, 2 5 ,
(8) Muthu, 0.;
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. D e v . 1977, "3, 51.

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