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204
1, Kalamazoo, M I 49002.
0021-9568/86/1731-0204$01.50/0
I.
The solutes to be studied were selected such that each was
either a simple polycyclic hydrocarbon or a monofunctional
derivative of one. As noted above, we wished to examine how
the addition of a specific chemical group to a hydrocarbon
skeleton affected that molecule's solubility in various supercritical fluids. Most of the solutes were derivatives of naphthalene, but, for practical reasons, a few of the solutes were
derivatives of either anthracene or benzene.
The principal solutes, along with several of their pertinent
physical properties, are listed in Table 11, Vapor pressures
for all of the solutes were found in the literature with the exception of 2-aminofluorene. The sublimation vapor pressures
of this compound were determined as a function of temperature
with a Knudsen sublimation apparatus in our laboratory (6).
Experimental Procedure
A schematic diagram of the experimental apparatus is shown
in Figure 1. I t is similar to several described before (2, 72).
To expedite data collection, two extraction columns (C1 and C2)
were run in parallel. These could be operated at different
temperatures, but the pressures in each column were identical
since they were fed from a common compressor and surge
tank (a 2 1 autoclave). The system pressure was held to within
f0.3 bar at pressures up to 150 bar and was maintained to
within *I bar at the highest pressures used (360 bar). Temperatures in the bath@)were maintained within fO.l OC and
the supercritical fluid from both extraction vessels passed
through lines traced with flowing water at the same temperature
as in the constant temperature bath. This precaution was
necessary to prevent solid precipitation in an exit line since the
solubility of solutes in supercritical fluids may either increase or
decrease with temperature depending upon the specific temperature and pressure employed. The precipitated solid was
subsequently weighed and analyzed. The operation of the unit
is similar to that described earlier (2).
Preliminary extraction experiments were made with solid
naphthalene and supercritical carbon dioxide. The results over
a temperature range of 35-45 OC and a pressure range of
MW
T,,OC
P., bar
44.01
30.07
104.46
70.01
31.1
32.2
28.8
26.1
73.8
48.8
39.2
49.5
p,,
mol/cm3
0.0106
0.0067
0.0055
0.0075
0.225
0.098
0.180
0.272
formula
structure
T,,"C
V,m3/mol
naphthalene
80.1
1.10 X
biphenyl
69.2
lo4
vapor press.
B
supplier, purity
13.583
3733.9
Baker, >98%
1.32
14.804
4367.4
Aldrich, 98%
phenanthrene
100
1.51
13.545
4567.7
Aldrich, -98%
anthracene
218
1.42
14.755
5313.7
Aldrich, >99.5%
benzoic acid
1,4-naphthoquinone
uCozH
0
122
0.965
14.408
4618.1
Baker, 99%
126
1.11
14.735
4739.4
Aldrich, >97%
107-109
1.78
13.721
4740.1
Fluka, 98%
s-3)
O
acridine
2-naphthol
2-aminofluorene
moH
mNHz
122
1.18
14.815
4923.9
Aldrich, 99%
131
1.53
14.865
5469
Aldrich, 98%
OVapor pressure constants in the equation log P a p (Pa) = A - BIT. For use in the range 35-70 OC, except naphthalene 35-55 "C. Vapor
biphenyl (IO), anthracene (8),benzoic acid (8),
pressure references: naphthalene (7), phenanthrene (8),1,4-naphthoquinone (9),acridine (8),
2-naphthol (11).
R
DT
RV
r0tam.t.r
dry t e s t meter
maina*t.r
pres8ure regulator
fli-Jr-?+
_____
1 .______.
SUPPLY COMPRESSOR
TANK
AUTOCLAVE
always operating in a sufficiently low flow regime that equllibrium was attained between the solid and the exit fluid (6).
Expertmental Results
206
temp,
O C
35.1
35.1
35.1
35.0
35.0
34.9
35.0
35.0
35.0
35.0
34.9
35.1
35.1
34.9
35.0
45.0
45.0
45.1
45.0
45.0
45.0
45.1
44.9
44.9
45.0
45.1
45.0
55.0
55.0
55.0
55.1
54.9
54.9
55.1
55.0
55.0
55.0
55.0
55.0
55.0
55.0
press.
P9
(abs), bar mol/cm3
pr
Solubility of Naphthalene
50.9
0.00630 0.926
0.009 28 1.373
55.6
0.01001 1.482
60.1
0.010 55 1.559
65.5
0.01084 1.604
69.1
0.011 79 1.742
91.5
0.012 03 1.780
99.4
0.012 51 1.848
120.5
0.01284 1.897
131.0
0.012 98 1.921
150.8
0.013 36 1.975
181.0
0.013 59 2.009
198.7
0.014 08 2.081
250.0
0.014 51 2.144
301.7
0.014 86 2.196
362.0
0.003 50 0.517
51.0
0.004 48 0.663
55.5
0.007 63 1.127
65.5
0.008 62 1.276
69.1
0.010 72 1.584
91.5
0.011 78 1.741
120.5
0.01200 1.773
131.0
0.012 47 1.845
150.7
0.013 18 1.951
199.0
0.013 72 2.030
250.0
0.014 14 2.090
301.7
0.014 58 2.151
364.0
0.003 57 0.528
56.3
0.004 25 0.625
61.3
0.006 49 0.960
71.5
0.008 10 1.199
80.2
0.009 66 1.431
100.8
0.01090 1.613
100.8
0.011 91 1.760
164.0
0.012 24 1.809
175.0
0.012 67 1.872
202.0
0.012 72 1.879
206.0
0.012 98 1.918
225.0
0.013 26 1.959
251.0
0.013 73 2.029
302.0
0.014 20 2.098
364.0
mole
fraction
in Ethane
0.25 X lo-'
1.12
1.29
1.42
1.54
1.97
2.08
2.30
2.54
2.56
2.78
3.02
3.24
3.19
3.48
0.06 x 10-2
0.15
1.36
1.40
2.67
3.46
3.86
4.08
4.74
5.25
5.42
5.85
0.12 x 10-2
0.19
1.14
2.09
4.37
6.48
10.7
11.1
13.7
13.0
13.6
12.9
13.6
13.4
enhance.
factor"
temp,
"C
660
2 090
2 600
3 180
3 600
6 200
6 980
9 450
11400
13100
17 200
20 000
27 600
32 700
42 900
43
118
1260
1380
3 470
5 940
7 130
8 750
13400
18 600
23 000
29 900
41
72
503
1020
2 750
4 920
10 900
1 2 100
17 400
17 000
19 100
20 100
25 900
30 400
35.1
35.1
34.9
35.0
35.0
35.1
45.1
45.1
44.9
45.0
44.9
45.0
55.0
55.1
55.0
55.0
55.1
54.9
press.
P,
(abs), bar mol/cm3
pr
Solubility of Naphthalene in
60.5
0.006809 0.9029
0.009 532 1.264
73.3
0.011 298 1.498
96.1
0.013 027 1.727
141.3
0.014 68
221.0
1.947
0.016 25
351.3
2.155
0.004 422 0.5864
60.5
73.3
96.1
141.3
221.0
351.3
66.0
82.8
123.0
171.0
240.8
351.4
0.006 920
0.009 704
0.011 988
0.013 95
0.015 71
0.004 300
0.006 547
0.010 043
0.011 970
0.013 59
0.015 17
0.9176
1.287
1.590
1.850
2.083
0.5702
0.8681
1.332
1.587
1.802
2.012
~~~
mole
fraction
Fluoroform
2.46
~. X
4.24
6.06
7.49
8.71
9.18
0.857 X
10-3
3.30
7.04
10.09
12.3
13.4
1.24 X
4.21
11.1
14.4
18.4
18.5
~
enhance.
factor"
500
..
1050
1990
3 600
6 500
10 800
72
338
962
2 000
3 870
6 620
50
214
850
1530
2 730
4 050
Correlatlon
The solubilities of solkJs in supercritical solvents are usually
correlated with eq 1. As written, we have assumed that the
Solubility
45.0
45.0
45.0
45.0
55.0
55.0
55.0
55.0
REDUCED DENSITY
of Phenanthrene in
0.00807
75.5
0.00960
108.0
0.01126
180.0
0.0127
301.0
0.00686
75.5
0.00880
108.0
0.0107
180.0
0.0124
301.0
enhance.
factor
18500
47 800
131400
375 000
832 000
1392 000
3400
10 900
46 000
168000
402 500
674 000
7 690
32 900
116 700
302 500
1860
1 2 500
55 900
148 100
Monochlorotrifluoromethane
11650
1.455 2.38 X
29 500
1.730 4.21
76 200
2.028 6.52
170 300
2.290 8.73
4075
1.237 2.31 X
12 200
1.587 4.78
38 500
1.933 9.02
78 200
2.221 11.0
A
O'
0.8
1.0
1.2
1.4
1.6
1.8
2.0
R E D U C E D DENSITY
Flgure 3.
and pressure, one must know the pure solute vapor pressure
(P;P), the molar volume of the solute (V;), and the fugacity
coefficient of the solute in the supercritical phase (4
I t is
the last that concerns us here as we assume P 2q and V,S are
available from independent measurements or from literature
data.
of BiDhenvl in Ethane
P,
mol/.Cm3
0.0109
0.0116
0.0124
0.0134
0.0143
0.00891
0.0106
0.0116
0.0129
0.0136
pr
1.603
1.706
1.824
1.971
2.103
1.310
1.559
1.700
1.903
2.051
mole
fraction
1.24 X
1.54
1.89
2.66
3.09
1.01 X
1.77
2.66
4.81
6.22
enhance.
factor
20600
30 200
49 000
109 800
198 900
5970
12 500
25 400
72 600
143 700
No. 2, 7986
::;:
42 = ( b , / b ) ( Z -
1)
- In
[P(V- b)/RT]
[ a / 8 1 2 ~ ~ b l ~ [ 2 ( a+
l gal g 2 ) / a 1 - b 2 / b ) x
In [( V
2.4146)/( V - 0.414b)I (2)
(4)
Journal of Chemical and Engineering Data, Vol. 31, No. 2, 1986 209
I
400
450
IO2
P
a
8 10.~
z
W
0
c
u
a
rx
II.
10-4
2
0700
k,,=-O.0094
I0-5
50
0.8
1.0
1.2
1.4
1.6
REDUCED D E N S I T Y
1.8
150
200 250
300
350
PRESSURE ( E A R )
2.0
35.1
35.0
35.0
35.0
35.0
35.0
35.0
45.1
45.0
45.1
45.0
Solubility of 2-Naphthol
61.0
0.01010 1.495
73.5
0.0111
1.643
92.5
0.0118
1.746
130.5
0.0127
1.880
187
0.0134
1.983
277
0.0143
2.116
363
0.0149
2.205
61.0
0.00606 0.897
73.5
0.00855
1.265
92.5
0.01080
1.598
130.5
0.0120
1.776
in Ethane
0.134 X 10"'
0.80
1.15
1.47
1.77
2.12
2.34
0.28 X 10"'
0.84
1.51
2.22
100
16500
35 000
93 500
154000
260 000
380 000
4 700
12 800
31 500
62 700
95 200
158000
1300
1900
3 500
10 100
24 800
52 200
78 300
209
365
558
2 100
6 600
15 700
25 000
2 960
8 410
15 100
27 300
47 300
83 500
121 000
773
2 770
6 210
13020
~~
press.
(abs). bar
mol/cm3
D.
..
mole
fraction
45.0
45.0
45.0
55.1
55.2
55.1
55.1
55.1
55.0
55.0
70.1
70.0
70.0
70.0
70.0
70.0
70.0
187
277
363
66.0
76.0
93.0
131.5
192
280
364
66.0
76.0
93.0
131.5
192
280
364
0.0130
0.0139
0.0146
0.00529
0.00741
0.00939
0.01125
0.0125
0.0135
0.0142
0.00379
0.00508
0.00730
0.00995
0.01165
0.01286
0.01366
1.924
2.057
2.161
0.783
1.097
1.390
1.665
1.850
1.998
2.102
0.561
0.752
1.080
1.473
1.724
1.903
2.022
2.86
3.55
4.61
0.26 X
0.79
1.79
3.15
4.44
5.49
6.28
0.30 X 10"'
0.63
1.95
5.04
7.85
11.3
11.8
55.0
55.0
55.0
55.0
55.0
70.1
70.1
70.0
70.0
70.0
Solubility of 2-Naphthol in
79.0
0.00603 0.800
95.0
0.00797 1.057
135.5
0.0107
1.415
241.0
0.0136
1.803
364.0
0.0153
2.030
79.0
0.00464 0.615
95.0
0.00613 0.812
135.5
0.00906 1.202
241.0
0.0125
1.665
364.0
0.0145
1.925
P>
Solubility of 2-Naphthol in
55.0
73.0
0.00662
55.0
101.5
0.00853
55.0
151.0
0.0101
54.9
259.0
0.0119
55.0
364.0
0.0129
70.0
73.0
0.00503
70.0
101.5
0.00726
70.0
151.0
0.00922
69.9
259.0
0.0113
69.9
364.0
0.0124
Fluoroform
0.53 X
1.51
3.27
5.72
7.28
0.51 X
1.38
4.65
10.4
13.9
enhance.
factor
24 000
44
100
.._._
75 100
262
896
2 500
6 200
12 800
23 300
34 700
66
161
608
2 200
5 060
10 600
12 022
657
2 220
6 870
21 300
41 000
137
445
2 150
8 540
17 260
Monochlorotrifluoromei;hane
1.193
0.49 X
556
1.536
0.76
1190
1.824
1.14
2 660
2.141
1.55
6 270
2.320
1.91
10 800
0.907
0.52 X
130
1.308
1.37
470
1.661
2.52
1300
2.023
3.52
3 150
2.230
4.31
5 420
a 12 = (a la 2)12
a = (a112yl
(5)
+ a212y2)2
b = bIY1 + b2y2
(7)
( b 2 / b l ) ( Z 1- 1) - In [ P ( V l
- b,)/RT] -
(a,/812RTb,)[2(a2/al)12
- (b2/b1)1 In [ ( V l
42 = 42mexp(-W2)
(9)
Journal of Chemical and Engineering Data, Vol. 31, No. 2, 1986 211
Pt
mol/cm3
0.0108
0.0121
0.0128
0.0138
0.0145
0.00526
0.00741
0.00962
0.0114
0.0124
0.0133
0.0142
0.00383
0.00524
0.00745
0.0102
0.0115
0.0127
0.0137
pr
1.599
1.797
1.908
2.041
2.145
0.778
1.096
1.423
1.686
1.834
1.967
2.101
0.567
0.775
1.102
1.509
1.701
1.879
2.027
mole
fraction
5.98
9.19
11.1
15.2
18.6
0.35 X
2.09
5.90
12.3
18.6
21.8
34.5
0.37 X
1.09
5.32
8.78
29.0
43.5
61.3
of 2-Aminofluorene in Fluoroform
0.00758 1.006
3.38 X
0.0107
1.418
11.8
1.801
25.1
0.0136
2.030
31.5
0.0153
0.00578 0.7672
2.27 X
0.00909 1.206
16.1
1.662
43.1
0.0125
60.3
0.0145
1.925
enhance.
fractor
121500
265 000
426 800
841 000
1423 000
1480
10 200
35 800
106 700
215 200
361 700
793 900
290
1000
5 980
14 400
62 400
133 800
264 000
19 600
102 000
383 000
729 000
2 450
25 900
122 400
259 700
212 Journal of Chemical and Engineering Data, Vol. 31, No. 2, 1986
T a b l e XIII. Regressed S o l u t e P a r a m e t e r s a and
b 2 in Eq 2
solvent
solute
naphthalene
phenanthrene
anthracene
biphenyl
benzoic acid
1,4-naphthoquinone
acridine
2-naphthol
2-aminofluorene
6.25
13.2
11.6
9.40
9.23
9.90
13.2
9.90
11.2
123
194
174
169
136
145
190
155
142
7.18
13.9
12.8
10.5
9.00
9.21
15.1
9.00
13.7
129
183
172
174
126
155
217
145
177
7.03
12.9
12.0
145
191
190
7.00
13.4
145
200
10.0
12.2
15.5
10.5
17.8
157
175
225
169
231
8.58
9.00
14.1
8.0
14.2
133
157
215
144
195
sion (eq 8) to model the solubilities with nearly the same accuracy as is achieved by using eq 2. The error introduced by
using eq 8 over eq 2 was typically less than 5% for solutes of
low and medium volatility, but rose to approximately 40 % error
when highly soluble solutes such as naphthalene were modeled.
However, when the experimental solubilities of naphthalene
were regressed by using the simplified form of the fugacity
coefficient, a different set of a , and b 2 parameters were obtained which did improve the correlation considerably.
Finally, it can be seen from Table XI11 that the a , and b ,
solute parameters are not actually constants for a given solute, but do vary somewhat depending on the solvent used. I t
is hoped that a method of correlating the constants for use in
an a priori predictive method will be found.
Greek Letters
fugacity coefficient
acentric factor
Subscripts
1
2
12
r
Superscripts
solid solute
vapor pressure
infinite dilution
S
VP
m
Concluslons
The solubilities of the model solutes were found to be dependent on the choice of the supercritical solvent used to di+
solve the compound. Carbon dioxide was a very encompassing
solvent, performing especially well with polar compounds, while
ethane was better for simple aromatic hydrocarbons. Fluoroform was a poor solvent for hydrocarbons, but a good solvent
for those molecules containing potential hydrogen-bondlng sites,
such as C=O, NH, and to a lesser extent -N=.
Chlorotrifluoromethane was consistently the poorest of the four solvents.
A modified Peng-Robinson equation of state, in which two parameters are required to fit experimental data, was used to
correlate solubilities over a wide range of supercritical pressures. The model correlates the solubilities better than the
classical Peng-Robinson equation and alleviates some of the
problems associated with application of equations of state to
solid-fluid equilibria.
This study has shown that chemical effects are important in
determining the solubility of solutes in supercrltbl fluids. I n the
same way as one searches for appropriate liquid solvents,
employing the broad concepts of polar-nonpolar, hydrogenbonding-non-hydrogen bonding, acid-base, etc., one can apparently use the same rules in choosing appropriate supercritical fluid sotvents to affect desired separations and to maximize
yields.
Glossary
a
b
K
P
R
T
Y
Reglstry No. CO, 124-38-9; CHF,, 75-46-7; CCIF,, 75-72-9; naphthalene, 91-20-3; biphenyl, 92-52-4; phenanthrene, 85-01-8 anthracene,
120-12-7; benzoic acM, 65-85-0 1,4-naphthoquinone, 130-15-4; acrkiine,
260-94-6; 2-naphthol, 135-19-3; 2-aminofiuorene, 153-78-6; ethane, 7484-0.
Llterature Cited
(1) Johnston, K. P.; Ziger. D. H.; Eckert, C. A. Ind. Eng. Chem. Fundam.
(2) Kurnik, R. T.; Holla, S.;ReM. R. C. J. Chem. Eng. Data 1981. 26, 47.
(3) McHugh, M. A.; Paulaitis, M. E. J. Chem. Eng. Data 1980, 25,326.
(4) Stahl, E.;Willig. E. Mlkrochim. Acta 1980, 2,465.
(5) Chrastil, J. J. Phys. Chem. 1982. 86,3016.
(6) Schmitt, W. J. Ph.D. Dissertation, Department of Chemical Engineering, Massachusetts Institute of Technology. Cambrklge, MA, 1984.
(7) Fowler, L.; Trump, W.; Vogler, C. J . Chem. Eng. Data 1988, 13,209.
(8)de Kruif, C. G.; van Ginkel, C. H. D.; Voogel, J. Torsion-Effusbn Vapor Pressure Measurements of Organic Compounds, Quatrieme Conference Internationale de Thermodynamique Chemique, Aout, Montpellier, France, 1975.
(9) de Kruif, C. G. Smit, E. J.; Govers, H. A. J. J . Chem. Phys. 1981, 74,
5838.
(IO) Bradley, R. S.;Cleasby, T. G. J. Chem. SOC.(London) 1953, 1690.
(11) Colomina, M.; Roux, M. V.; Turrion, C. J. Chem. Thennodyn. 1974, 6 ,
571.