M-2467

.I. Chem. Thermodvnamics 1990, 22, 335-353

Fluid

mixtures

IX. Phase
phenomena
mixtures
ERWIN

at high

pressures

separation
and critical
in 23 (n-alkane
+ water)

BRUNNER

BASF Aktiengesellschaft, D-6700 Ludwigshqfen,

Federal Republic qf Germany
(Received 11 January 1990)

The p(T) projections of the critical curves and of the (liquid + liquid + gas) (Ilg) three-phase
curves for 23 binary mixtures of (an n-alkane + water) with alkane-carbon numbers i = 1 to 12
and i = 14, 16, 18, 20, 24, 25, 26, 28, 30, 32, and 36 were measured. The shape of the critical
curves of the mixtures changes systematically with i. All critical curves are interrupted and show
(gas + gas) equilibria of the second kind. The Ilg curves are at higher pressures than the vapour
pressures of the pure substances, and all end in a (liquid + gas) upper critical end point
(Ig-UCEP). Up to the mixtures i = 25, along the p(T) projection of the Ilg lines up to the
Ig-UCEP, the alkane-rich liquid phase is lighter than the water-rich liquid phase. The
consequence is that the critical curve starting from the Ig-UCEP ends in the critical point of the
alkane. As from i = 28, a barotropic phase reversal of the two liquid phases occurs on the Ilg
curve before the UCEP is reached, so that, at the UCEP, the now lighter water-rich liquid
phase becomes identical with the gas phase and the critical curve starting from the UCEP runs
to the critical point of water. For a defined pseudo-binary mixture of (alkane mixture + water)
with a fictitious alkane-carbon number between i = 26 and i = 28, this barotropic effect must
occur directly at the UCEP. This means that all three phases here become simultaneously
identical at the UCEP and the llg curve thus ends in a tricritical end point TCEP, a phase
behaviour which has hitherto not been known. The three branches of the critical curve, oiz. the
high-pressure branch I,& and the two branches I,g and lag, which start from the critical point
of water or the alkane mixture, respectively, end in this tricritical end point TCEP. At TCEP
the three-phase line and the three branches of the critical curve (l,l,, lig, and lag) have the same
slope. The TCEP occurs in the border-line case between the two sub-classes a and b of phasebehaviour type III (classification according to van Konynenburg and Scott). In sub-class IIIa
the critical curve starting at the UCEP ends at the critical point of the n-alkane and in sub-class
IIIb at the critical point of water. For mixtures with i = 1 to i = 26, the high-pressure branch of
the critical curve starting from the critical point of water runs first to lower temperatures and,
with increasing pressures, oia a temperature minimum back to higher temperatures. For all
mixtures with i = 7 to i = 26 this branch of the critical curve additionally also passes through a
pressure minimum between the critical point of water and the temperature minimum. All
mixtures with i 2 28 have a high-pressure high-temperature branch of the critical curve which,
starting from the critical point of the alkane, first runs via a pressure maximum and pressure
minimum to lower temperatures and finally, after passing through a temperature minimum,
rises again. The phenomenological relations in phase behaviour on transition from type II to
type III and from type IIIa to type IIIb with the characteristic intermediate stages are presented
schematically with the aid of the p(T) projections of their critical curves.
CO21-9614/90/040335 + 19 $02.00/0

0 1990 Academic Press Limited

336

E. BRUNNER

1. ~ntr~u~tio~
In connection with our investigations on phase separation and critical phenomena at
high pressures in binary mixtures containing polar substances, ) we measured p(T)
values of the critical curves and the (liquid + liquid + gas) (Ilg) three-phase lines for
23 mixtures of (an n-alkane + water) with alkane-carbon numbers of i = 1 to 12 and
i = 14, 16, 18, 20, 24, 25, 26, 28, 30, 32, and 36.
At temperatures near the critical temperature of water, fluid-phase equilibria of (an
n-alkane -i- water) with i = 1 to 7 had been measured already; all these show (gas +
gas) equilibria of the second type: (methane + water),8~9 (ethane + water),. I)
(propane + water), 9 13) (butane + water),iO~ i . i4) (pentane + water), 5, (hexane
+ water),41 and (heptane + water). ( I The low-tem~rature
branch of the
interrupted critical curve of (hexane + water) had been measured by Scheffero8 A
brief summary of the classification of phase behaviour and critical phenomena
according to Scott and van Konynenburg
l) was given in part VI of this series of
publications.@

2. Experimental
The apparatus and measuring method for the present study were largely the same as
those previously described by Brunner et uL(~~)and used for parts I to VII in this
series of papers on fluid mixtures at high pressures.-) All measurements were
performed in a 30 cm3 cylindrical high-pressure optical cell. The high-pressure cell
previously used was fitted with a heating jacket which was connected to a thermostat
circulation, so that its maximum operating temperature was limited to 600 K. To
enable the measuring range to be extended to higher temperatures, a high-pressure
cell fitted with bayonet heaters was built according to the same principle of
construction (figure 1). The characteristics of the high-pressure optical cell are:
30 cm3 capacity; maximum
operating pressure: 200 MPa at 750 K; material:
Nimonic 90, a heat-resistant N&based alloy (equivalent to German standard 2.4969);
eight electric heating cartridges of 500 W each; graphite as a high-pressure seal.
The precision and repeatability with which the appearance or disappearance of a
phase boundary was observable is in general Ap/p < 10d3 and AT < 0.2 K. The
pressures were measured by means of strain-gauge pressure transducers, which were
cahbrated against a free-piston gauge before and after each series of measurements. If
it is assumed that any impurities in the test substances and their thermal
decomposition have no significant effect on the position of the critical or llg threephase loci, the total error was estimated to be Ap/p < 0.004. The temperature was
measured inside the cell by a 1 mm steel-sheathed thermocouple, which was checked
several times over the entire temperature range of the particular tests against a
calibrated platinum resistance the~ometer
using a the~ostatically
controlled oil
and salt bath, and by measuring the vapour-pressure curve of water in the optical
high-pressure cell,up to the critical point. The resolution of the device for measuring
the temperature was 0.02 K, and the absolute accuracy of the temperature
measurements is estimated to be as follows: 60.2 K below 373 K, ~0.3 K between

23 (n-ALKANE

+ WATER) MIXTURES

331

A-A

-3

50 mm

FIGURE 1. High-pressure optical cell, 30 cm3, 200 MPa, 750 K. 1, pressure-distributing ring (17-4 PH);
2, pressure screw (Nimonic 90); 3, eight bayonet heaters of 500 W each; 4, high-pressure seal ring
(graphite); 5, pressure ring (Nimonic 90); 6, window (sapphire); 7, pressure vessel (Nimonic 90).
TABLE 1. Mole-fraction purity x, supplier of the test substances used, and selected literature values of the
critical temperature T, and the critical pressure pEof the pure substances
Substance
H,O
CH,
CA,
Ws
W-I,,
GH,,
Cd,,
WI,,
GH,,
GH,,
CIOHH
C,,H,,
C,,H,,
Cd,,
C,,H,,
C,&JS
GA,
Cd-ho
C,J,,
G,H,a
G.sH,s
Go%
C,,H,,
Cd,,

0.9995
0.9995
0.9995
0.9995
0.9987
0.9954
0.9967
0.9962
0.9997
0.9982
0.9945
0.9976
0.9974
0.983 *
0.9922
0.9970
0.997
0.994
0.996
0.998
0.980
0.987
0.990

Supplier
Merck
Messer-Griesheim
Messer-Griesheim
Messer-Griesheim
Messer-Griesheim
Merck
Merck
Merck
Fluka
Ventron
Merck
Merck
Ventron
Fluka
Fluka
Fluka
Aldrich
Fluka
Fluka
Fluka
Fluka
Fluka
Fhtka
Ventron

T,IK

p,lMPa

Ref.

647.14
190.555
305.33
369.85
425.25
469.80
507.90
540.15
568.95
594.65
617.65
638.85
658.65
693.15
722
749
771
809
818
827
843
857
871
894

22&x6
4.595
4.8714
4.2470
3.791
3.375
3.030
2.736
2.488
2.281
2.103
1.953
1.835
1.622
1.444
1.290
1.200
1.020
0.98
0.95
0.89
0.83
0.79
0.71

23
24
24
24
24
24
24
24
25
25
26
26
26
26
26
26
26
26
c
c
c
c
c
c

a Pro analysi, conductivity 5 uS m-r as guaranteed by the supplier.

*The impurities are isomers with nearly the same vapour pressure: x(C15H3J = 0.0012, x(C, ,Hs6) =
0.0005.
Critical quantities estimated according to reference 47.
Own measurement: pE= (22.060~0.010) MPa. The recommended value of 22.115 MPa from reference
27 is too high. Experimental values from Blank..(*s) TE= (674.14kO.03) K (corrected from IPTS-49 to
IPTS-68) pc = (22.045 &0.003) MPa.

E. BRUNNER

338

TABLE 2. Experimental points on the llg three-phase lines and the two branches of the interrupted critical
p(T) curves of 23 (n-alkane + water) mixtures with n-alkane numbers i = 1 to 12, and i = 14, 16, 18, 20,
24, 25, 26, 28, 30, 32, and 36: temperature T, pressure p; llg, (liquid + liquid + gas) three-phase point;
lg, (liquid + gas) critical point; UCEP, upper critical end point; cpl, critical point of water; cp2, critical
point of the alkane
T/K

p/MPa

T/K

p/MPa

T/K

T/K

p/MPa

28.65
31.70
34.50

Methane + water
636.4 38.40
634.8 41.80
633.2 45.20

631.8

49.80

Ethane + water
628.5 35.00
624.9 39.80
622.3 44.90

621 .l

49.80

24.88
26.20
27.70
29.80
31.40
34.40

623.2
621.9
621.9

37.60
43.90
48.60

23.31
23.70
24.27
24.98
26.15
27.80
29.80

623.9
623.4
623.3
623.8
624.5
626.2

33.10
36.90
38.70
42.00
45.00
49.80

625.3
626.4
628.1
630.1

34.80
38.20
42.60
47.30

629.8
632.2
634.3
636.2

36.60
40.80
43.90
47.30

647.14 22.064
646.0 23.65
644.3 26.05

cpl
lg

642.4
640.3
638.6

647.14 22.064
642.9 23.90
641.0 24.80

cpl
k

639.3
635.6
631.4

25.80
28.30
31.70

Propane
4.2470 cp2
22.064 cpl
22.39 lg
22.65
23.45
24.05

+ water
638.5
635.5
632.3
628.9
627.2
624.7

312.4
336.8
342.2
352.7
361.5
369.7

1.360 lb
2.322
2.583
3.170
3.729
4.260 UCEP

369.85
647.14
645.8
644.9
642.5
640.8

325.5
347.9
363.4
382.9
401.3
411.5
414.7

0.545 lk
0.945
1.335
1.985
2.820
3.400
3.600

417.8
3.800
422.1
4.110
424.1
4.260
425.25 3.791
647.14 22.064
645.3 22.38
643.0 22.83

377.5
395.6
410.6
426.6
441.2
455.1
462.2

0.810
1.210
1.680
2.296
3.032
3.915
4.452

463.8
464.7
465.7
467.5
468.6
469.4
469.80

419.0
436.1
456.3
476.8
485.6
493.5
496.4

1.125
1.645
2.490
3.750
4.363
5.020
5.282 UCEP

499.0
4.980
501.6
4.525
504.4
3.995
506.4
3.460
507.90 3.030
647.14 22.064
642.2 22.52

Hexane + water
lg
640.0
636.7
633.7
631.4
cp2
629.9
cpl
627.9
Ig
627.6

414.7
429.5
444.5
459.1

0.713 Ilg
1.028
1.450
1.988

473.8
489.7
504.4
516.9

Heptane + water
520.0
523.8
526.7
529.7

Butane + water
640.7
639.0
UCEP 636.8
cp2
634.4
cpl
631.4
Ig
628.4
626.0

Pentane
4.577 UCEP
4.365 lg
4.220
3.878
3.608
3.440
3.375 cp2

2.688
3.659
4.792
5.995

+ water
647.14
641.6
636.6
630.6
627.4
626.2
625.3

p/MPa

22.064
22.79
23.65
25.32
27.20
28.50
31.00

cpl
lg

22.76
23.20
23.82
24.59
25.35
27.78
31.50
6.320 UCEP
5.89 lg
5.45
4.96

533.1
535.5
537.7
540.15

4.36
3.895
3.400
2.736 cp2

23 @-ALKANE

+ WATER)

TABLE
T/K

p/MPa

647.14
645.2
643.2
641.7
639.9

22.064
22.13
22.20
22.27
22.36

418.3
443.0
464.3
484.4
503.8
524.0
535.1
540.0
544.8

339

MIXTURES

2-c~~ti~~~

T/K

PlMPa

T/K

p/MPa

T/K

PIMPa

cpl
Ii

637.7
635.9
633.7
631.5
629.7

22.52
22.67
22.97
23.42
24.04

628.3
628.7
429.2
632.5
636.0

25.00
27.4
29.8
35.6
40.4

639.8
642.7

45.6
49.9

0.583
1.087
1.755
2.668
3.868
5.552
6.750
7.410
6.970

llg

548.6
552.0
556.6
550.0
562.9
568.95
647.14
646.1
645.0

6.525
6.030
5.250
4.663
4.112
2.488
22.064
22.09
22.10

22.10
22.13
22.19
22.30
22.53
22.78
23.15
23.85
24.6

630.3
631.6
635.8
637.0
639.7
644.2

27.2
29.7
35.3
36.8
40.4
45.6

447.9
457.7
468.8
479.2
488.8
509.6
523.5
539.0
545.4
548.7
553.3

1.081
1.350
1.745
2.181
2.652
3.960
5.105
6.670
7.418
7.833
8.452

llg

3.345
2.830
2.281
22.064
22.05
22.03
22.02
22.01
22.04
22.07
22.24

632.4
631.1
632.2
634.8
638.8
644.7
648.6
653.7

22.85
25.15
27.05
30.6
35.2
41.3
45.3
SO.8

465.8
494.0
523.3
543.2
562.8
567.6
569.4

1.473
2.686
4.630
6.495
9.000
9.655
9.600

Ilg

633.3
632.0
634.8
438.7
642.9
649.1

22.44
23.14
28.28
32.18
36.10
42.07

475.8
495.2
510.5
522.3
534.4
544.5
552.2
558.2
563.0
566.8
569.8

1.760
2.597
3.470
4.305
5.310
6.300
7.150
7.873
8.500
9.040
9.476

639.0
637.6
636.2
634.5
633.4
633.3
634.2
635.7
638.4
642.9

21.73
21.73
21.78
21.94
22.45
23.70
25.05
26.60
29.15
33.25

Octane

UCEP
lg

554.0
558.9
562.8
566.9
570.8
574.2
577.4
580.3
583.3
586.0
588.0

8.540
8.26
7.91
7.45
6.95
6.44
5.88
5.40
4.850
4.245
3.800

574.8
580.2
585.2
590.6
596.1
600.9
605.9

9.330
8.880
8.300
7.580
6.790
5.970
4.945

572.9
575.5
577.8
581.9
586.7
591.0
595.8
600.8
605.5
610.1
615.1

9.953
10.38
10.75
10.67
10.45
10.20
9.780
9.280
8.690
8.070
7.310

CQ2
CQl
k

Nonane

+ water
590.3
592.4
594.65
647.14
646.1
643.8
642.5
640.3
638.8
636.0
634.1

UCEP
Ig

cp2
cp1
le
-

+ water
610.4
613.6
617.65
647.14
644.5
643.2
641.0

Undecane
Ilg

643.8
641.6
639.3
637.1
634.9
633.4
632.1
630.7
630.2

UCEP
fg

Decane

UCEP
lg

+ water

3.923
3.224
2.103
22.064
22.00
21.95
21.90

CQ2
co1
1g

+ water
623.1
626.9
629.8
633.0
638.85
647.14
645.8
644.4
643.0
642.2
640.8

5.890
5.120
4.420
3.590
1.953
22.064
22.03
21.95
21.87
21.84
21.78

cp2
CQl

lg

340

E. BRUNNER
TABLE

T/K

p/MPa

519.4
534.8
546.1
554.6
561.3
565.4
568.2
571.3
574.4
577.3

4.06
5.27
6.42
1.27
8.06
8.60
9.01
9.43
9.86
10.35

Ilg
-

446.9
477.5
508.3
539.0
558.4
566.9
572.9
578.5
582.7
587.7
592.7
594.8

0.88
1.72
3.15
5.37
7.32
8.34
9.13
9.94
10.57
11.37
12.23
12.63

456.3
486.9
517.9
548.4
578.4
589.6
593.3
596.8
599.9
603.2

1.10
2.08
3.72
6.14
9.65
11.34
11.95
12.56
13.12
13.17

lb

439.4
469.1
499.1
528.9
549.1
569.1
589.4
599.3
608.4
612.8

0.730
1.442
2.623
4.437
6.160
8.307
10.96
12.55
14.27
15.18

llg

421.8
451.6
479.9

0.454
0.945
1.77

llg

T/K

p/MPa

580.4
583.1
584.8
594.3
597.8
608.5
617.9
629.0
638.8
646.6

10.88
11.34
11.66
11.55
11.36
10.58
9.560
7.850
6.185
4.580

597.3
598.7
599.1
604.6
608.7
616.4
625.9
633.8
641.9
648.7
653.7
659.7

13.12
13.41
13.48
13.43
13.40
13.18
12.61
11.93
10.98
10.10
9.33
8.28

605.6
608.3
623.6
632.0
641.6
651.8
660.6
670.4
679.9
689.1

14.27
14.87
15.300
15.235
14.880
14.065
12.97
11.47
9.880
7.990

615.0
615.9
616.5
618.4
620.9
625.2
632.4
639.7
647.2
654.9

15.72
15.93
16.07
16.30
16.44
16.62
16.76
16.72
16.54
16.13

509.7
540.5
570.2

3.15
5.27
8.27

2-continued
T/K

Dodecane

UCEP
le
-

Tetradecane
-

UCEP
lg

Hexadecane
UCEP
Ig

Octadecane

UCEP
lg

Eicosane

elMPa

p/MPa

+ water
654.2
658.65
647.14
646.3
645.1
644.0
642.9
641.8
640.7
639.4

2.805
1.835
22.064
22.01
21.93
21.84
21.77
21.72
21.68
21.63

cp2
cpl
In
-

638.0
636.3
635.0
634.4
634.5
635.4
636.5
639.9
643.9
647.0

21.61
21.68
21.93
22.35
22.90
24.38
25.54
28.56
31.56
34.01

636.6
635.6
636.4
639.1
642.3
645.9
649.2
652.5
655.8

21.53
22.30
23.45
25.30
27.75
30.10
32.20
34.10
36.30

637.3
636.3
636.6
637.7
638.8
640.8
643.3
646.3
650.7

21.26
21.60
21.95
23.05
23.85
25.08
26.55
28.50
31.10

640.6
639.1
638.5
637.6
637.2
637.8
639.2
640.8
643.0
651.1

21.32
21.22
21.14
21.18
21.63
22.15
22.97
23.98
25.10
29.55

613.4
617.9
622.1

14.98
15.96
17.08

+ water
664.5
667.9
671.1
693.15
647.14
646.7
644.8
643.6
642.2
641.4
640.0
638.1

7.41
6.66
6.01
1.622
22.064
22.03
21.90
21.80
21.70
21.63
21.54
21.47

cp2
cpl
Ii

+ water
722
647.14
646.2
645.3
644.5
643.9
642.6
641.0
639.8
638.2

1.444
22.064
21.98
21.88
21.78
21.70
21.56
21.42
21.30
21.24

cp2
cpl
Ig

+ water
662.9
670.2
678.6
686.4
749
647.14
645.3
643.9
643.0
642.1

15.56
14.92
14.05
13.19
1.290
22.064
21.85
21.68
21.57
21.46

cp2
cpl
Ig

+ water
598.5
603.7
608.3

12.27
13.19
14.00

UCEP

23 @-ALKANE

+ WATER)

TABLE
T/K

p/MPa

630.8
639.0
649.0
659.1
669.0
678.9

17.86
17.99
17.91
17.45
16.82
16.05

Ig

455.7
484.4
513.0
533.8
554.6
573.1
594.2
612.3

1.066
1.960
3.345
4.750
6.570
8.630
Il.68
14.83

Ilg

451.4
480.7
510.7
539.7
570.7
599.4
613.3
620.8
626.9
627.3
630.3
631.9

0.970
1.825
3.233
5.265
8.385
12.38
14.78
16.24
17.56
17.67
18.36
18.77

llg

487.5
510.1
540.6
569.0
589.3
604.7
619.3
627.4
630.3
632.2
635.5

2.10
3.21
5.34
8.16
10.80
13.22
15.90
17.58
18.27
18.70
19.58

llg

533.8
4.75
564.1
7.57
584.3
10.07
603.6
13.03
624.0
16.93
633.9
19.23
637.3
20.19
638.1 a 20.44
639.4
20.77
640.2
21.04

&3

T/K

p/MPa

689.1
771
647.14
645.5
643.8
641.0

14.95
1.200
22.064
21.85
21.62
21.33

632.7
651.7
662.7
472.8
682.7
692.6
809
647.14

19.40
20.98
21.40
21.30
20.57
19.60
1.020
22.064

632.9
634.9
636.0
636.4
436.9
637.4
638.1
639.4
641.9
646.7
650.4
654.4

19.02
19.62
20.06
20.22
20.15
20.11
20.15
20.27
20.53
20.95
21.25
21.55

637.9
639.5
640.4
640
641.2
647.9
651.3
655.4
659.4
663.1
666.7

20.25
20.89
21.16

641.2
641.0
641.1
641.6
642.0
643.0
644.7
645.5
647.14
843

21.44
21.35
21.29
21.23
21.28
21.41
21.66
21.80
22.064
0.89

2-continued

cp2
cpl
Ig

Tetracosane
UCEP
Ig

cp2
cpl
Pentacosane

UCEP
Ig

Hexacosane

21.44
21.45
21.71
22.00
22.25
22.41
22.57

UCEP
lg

Oetaeosane
UCEP
lg

CD1

ep2

341

MIXTURES

T/K

p/MPa

T/K

PFrPa

639.7
638.6
638.3
638.5
638.8
640.5

21.19
21.18
21.34
21.86
22.07
23.00

642.3
644.6
648.4
654.8

23.85
24.87
26.98
30.38

640.1
640.4
640.5
641.9
645.6
651.6
659.0

21.13
21.43
21.54
22.24
23.71
26.13
29.35

644.3
644.6*
645.0
646.1
650.2
653.9
658.0
662.3
666.4

22.83
23.20
23.60
25.15
26.70
28.35
30.10
32.05

640.6
640.6
640.8
641.4
642.2
642.8
643.5
651.2
655.7
662.1

21.18
21.28
21.41
21.64
22.00
22.22
22.46
25.50
27.30
29.90

644.3
644.1
645.3
647.9
648.5
650.8
652.4
656.f

22.05
22.34
22.98
24.02
24.25
25.14
25.80
27.30

+ water
646.2
645.8
645.3
644.6
643.8
642.7
641.7
640.9

21.95
21.90
21.82
21.71
21.58
21.41
21.27
21.17

fg
-

+ water
658.0
818
647.14
646.5
645.2
643.8
643.1
642.3
641.8
641.0
641.9
643.0

21.75
0.98
22.064
21.93
21.75
21.53
21.42
21.32
21.23
21.16
21.96
22.38

cP2
cpl
Ig

+ water
669.3
672.1
675.0
827
647.14
646.2
645.5
644.5
644.0
643.0
642.4

22.67
22.78
22.88
0.95
22.064
21.96
21.85
21.69
21.61
21.45
21.37

CP2
cpl
Ig

+ water
672.2
669.0
664.9
661.9
658.4
655.4
652.2
649.2
647.6
646.0

23.78
23.63
23.44
23.25
23.05
22.84
22.60
22.35
22.22
22.12

Ig

E. BRUNNER

342

TABLE 2-continued

T/K

p/MPa

T/K

502.5
532.1
562.0
590.2
609.9
629.9
635.3
635.9
636.7

2.76
4.62
7.36
11.02
14.32
18.30
19.46
19.63
19.80

Hg

499.3
429.4
560.0
590.8
608.9
617.6
629.2
633.5

2.612
4.450
7.163
11.00
13.95
15.56
17.95
18.97

llg

549.3
570.3
591.4
611.9
633
634.2
636.7

6.09
8.30
11.08
14.40
19.00
19.62

Ilg

637.9
638.5
639.8
641.1
641.6
641.7
642.1
642.6
643.f

PIMPa

T/K
Tricontane + water
643.9
644.8
645.6
646.3
UCEP 646.7
Ig
647.14
8.57
670.8
661.4

20.09
20.27
20.63
21.03
21.35
21.30
21.37
21.43
21.50

pIMPa
21.63
21.73
21.87
21.96
22.03
22.064
0.83
24.90
24.27

CPl
CP2
k

Dotricontane + water
646.2 21.95
646.6 22.02
647.14 22.064
UCEP 871
0.79
Ig
673.3 25.85
671.1 25.68
668.6 25.53
666.2 25.35

CPl
CP2
43

Hexatricontane + water
646.3 21.95
647.14 22.064
UCEP 895
0.71
lg
684.2 28.00
680.3 27.60
677.0 27.27
612.7 27.00

CPf
CP2
k

635
637.2
640.1
642.1
643.4
644.3
644.9
645.5

19.87
20.63
21.20
21.45
21.60
21.71
21.82

639.4
641.6
642.4
644.5
644.7
645.1
645.8

20.28
21.83
21.49
21.64
21.70
21.77
21.88

T/K

p/MPa

655.6
653.0
654.5
657.8
662.1
665.3

23.95
24.13
25.25
26.85
28.75
30.20

663.7
661.0
660.0
661.7
664.8
669.1
671.9

25.22
25.28
25.66
26.85
28.55
31.02
32.45

670.5
664.6
667.6
671.3
675.0
679.5
682.9

26.87
26.55
29.00
31.46
33.50
36.05
38.05

Barotropic reversal of the two liquid phases on the Ilg three-phase line.
bBarotropic reversal of the two fluid phases on the Ig-critical curve.

373 and 473 K; and ~0.5 K above 473 K. The main error in the temperature
measurement by the calibrated thermocouples is to be ascribed to a time drift of the
electromotive force E(t). However, this error can be significantly reduced by
prolonged
tempering
and repeated calibration
of the therm~ouples.
The
thermocouple was checked additionally by measuring the critical temperature for the
pure substances and relating it to the critical temperature T, quoted in table 1. As a
result, the relative accuracy in the vicinity of the critical temperature for both pure
substances of the corresponding binary mixture has been increased to AT < 0.2 K.
Systematic drifts of the measured values of pressure and temperature were observed,
above all with higher alkanes, whenever the test substances were heated for a
considerable time to temperatures above about 600 K. To reduce these measurement
errors, which are difficult to estimate, the residence times of the test substances at
high temperatures were shortened as far as possible. As a rule, these were not more
than 2 to 4 h. The maximum measurement errors due to the thermal degradation of

23 @-ALKANE

343

+ WATER) MIXTURES

the alkanes above 600 K would in general probably not exceed values of AT = 1 K
and Apfp = 0.005.
The mole-fraction purities of the substances and the suppliers are summarized in
table 1, which also contains selected literature values of the critical tem~ratures and
pressures of the pure substances. The purities quoted for water, methane, ethane,
propane, and butane are guaranteed by the supplier. Those for alkanes with a carbon
number of 4 < i < 20 were determined by capillary g.c. with different capillaries. The
25 m fused capillaries used for i > 4 were SE 54 (methylsilicone rubber with 5 per
cent of phenyl and 1 per cent of vinyl) and SE 31 (methylsilicone rubber with 1 per
cent of chemically bonded vinyl). A 50 m capillary with squalane was additionally
used for i = 5 to 9. The alkanes for i > 19 were assayed by d.s.c. The alkanes with
i > 4 and water were carefully degassed in a separate apparatus. All those having a
melting temperature higher than 280 K were introduced by means of a heated screw
press and heated feed lines. The substances investigated were not further purified
except for hexane, which was obtained by rectification of 99 moles per cent hexane in
a 50-plate column at a high reflux ratio.

TABLE 3. Prominent vatues of the Ilg three-phase line and the critical phenomena of (n-afkane + water):
i, carbon number of the n-alkane; p, pressure; T, tem~ratme; ~p/~T, gradient of the critieai curve at the
critical point of water, 1, upper critical end point, UCEP; 2, temperature minimum of the high-pressure
branch of the critical curves; 3, pressure minimum of the high-pressure branch of the critical curve;
4, pressure maximum of the low-pressure branch of the critical curve; 5, barotropic reversal of the two
liquid phases on the Ilg three-phase line

%PT

MPa.K-

T,lK

-1.39

-0.43
-0.24
-0.17
-0.13
-0.090

369.1
424.1
463.8
496.4

- 0.036
- 0.020
0.010
0.025
0.040
0.055
0.070
0.090
0.11
0.12
0.12
0.14
0.12
0.15
0.12
0.12
0.13

520.0
540.0
554.0
561.6
577.8
584.8
598.7
608.3
616.5
622.7
632.7
636.4
641.2
641.2
641.6
642.1
642.4

- -----__I
I
2
3
4
5
6
1
8
9

10
11
12
14
16
18
20
24
25
26
28
30
32
36

4.260
4.260
4.577
5.282
6,320
7.410
8.540
9.655
10.75
11.66
13.41
14.87
16.07
17.08
19.40
20.22
21.44
21.44
21.35
21.20
21.49

621.7
623.0
625.1
626.4
628.6
630.1
631.0
631.9
633.2
634.4
635.5
636.3
637.1
638.2
640.0
640.4
640.6
644.1
653.0
660.0
664.2

_46.3
38.0
32.5
29.7
27.0
26.0
25.0
24.0
23.0
22.5
22.1
21.6
21.4

21.5
21.2
21.2
21.2
22.2
24.2
25.6
26.8

640
638
638
638.0
638.0
638.0
638.2
639.0
640.2
640.6
640.8
645.5
653.8
662.5
665.0

_-.

22.00
21.90
21.70
21.60
21.46
21.23
21.13
21.13
21.10
21.13
21.1s
22.0s
23.90
25.20
26.55

623.0
634.0
640

667

15.33
16.78

18.00
21.42

640
638.1
635.9
635
633

344

E. BRUNNER

T/K
FIGURE 2. Survey of the p(T) proj~tjons of the llg three-phase fines and of the two branches of the
inte~upted lg-critical curves of (n-alkane f water). indicated numbers are carbon numbers of the
n-alkane; -0,
vapour pressure and critical point of water; - - - 0, vapour pressure and critical
point of the n-alkane; -0,
llg three-phase line and Ig-UCEP. To allow easier review, only the highpressure branches of the Ig-critical curve for the eight mixtures with i = 1, 3, 6, 12, 18, 24, 30, and 36, are
plotted. So as not to complicate the curves, measured p(T) points have not been indicated besides the
Ig-UCEPs.

3. Results aad discussion

All (n-alkane -I- water) mixtures investigated have an interrupted critical curve of
type III according to the classification of Scott and Konynenburg(9-21) and, with the
exception of (methane + water), an llg three-phase line that terminates at an
lg-UCEP. For {methane + water) there is no common range of temperature in which
both pure substances in the mixture are liquid; this means that the llg three-phase
line and the lg-UCEP do not exist. The experimental p(T) values on the llg threephase lines and on both branches of the critical curves for 23 (n-alkane f water)
mixtures with carbon numbers of the n-alkanes of i = 1 to 12 and i = 14, 16, l&20,
24,25,26,28,30,
32, and 36 have been compiled in table 2. Prominent values on the
critical curves are summarized in table 3. They include the slope i3pjaT of the critical
curves at the critical point of water, the p(T) values of the UCEP, of the temperature
minima, and of the pressure minima and maxima of the critical curves, and also of
the barotropic reversal of the two liquid phases on the Ilg three-phase line. The shape

23 @-ALKANE

+ WATER) MIXTURES

5\

o-

E
r

s-

oi

630

640

650

660

670

680

TIK
FIGURE 3. Larger-scale section of the high-pressures branches of the critical p(T) curves for eight
(n-alkane + water) mixtures with carbon numbers i = 1, 3. 6, 12, 18, 24, 30, and 36. -0,
Vapour
pressure and critical point of water. So as not to complicate the curves, the measured p(r) points have not
been indicated.

of the llg three-phase lines and of the critical curves of the mixtures changes
systematically with the carbon number i and, because of the very large differences in
the polarity of alkane and water, these mixtures show a very characteristic phase
behaviour.
A general review of the phase behaviour of the (n-alkane + water) family is given
in figure 2. To allow easier review on the phase behaviour of the (n-alkane + water)
family only for the eight mixtures with i = 1, 3, 6, 12, 18, 24, 30, and 36, the highpressure branches of the critical curves are plotted in this figure. These high-pressure
branches are presented in an enlarged scale in figure 3. To allow the shape of the
high-pressure branches of critical p(T) curves to be recognized more clearly all 23
curves are plotted in figures 4a, 4b, and 4c also in an enlarged scale. In contrast to
the already investigated families of (an n-alkane + pyridinef5) or acetic acid() or
methanol6* I or ammoniat7) or tetrafluoromethane30* 31) or carbon dioxide(32* 33)
or ethane34) and of (methane + a mixture of alkanes),35* 36) where a change of the
phase behaviour from type II to type III always takes place at a corresponding
change in the carbon number of the alkane, all 23 (n-alkane + water) mixtures have
an interrupted critical curve with an lg-UCEP, at which the gas phase and the liquid
phase of the lower density become identical. Because of the wide range of the critical
temperatures, which is covered by the alkanes: T,(CH,) = 190.6 K to K(C36H74) =
894 K, the investigations cover regions of temperature, where the non-polar alkanes

E. BRUNNER

346

25

25

620

I
630

640

650

660

670

680

FIGURE 4. Larger-scale section of the high-pressure branches of the critical p(T) curves for all 23
(n-alkane + water) mixtures investigated. Indicated numbers are the carbon numbers of the n-alkane.
-0,
Vapour pressure and critical point of water. So as not to complicate the curves, the measured
p(T) points have not been plotted.

have a higher volatility than water, and also regions where their volatility is lower
than that of water. With increasing carbon number i, the decreasing volatility of the
n-alkanes leads to the following characteristic changes in the phase behaviour of the
binary mixtures. At i = 2 to i = 26, the dT) projection of the llg three-phase lines
runs to an lg-UCEP. Since the water-rich liquid phase on the llg three-phase line
always has a higher density than the alkane-rich liquid phase at all temperatures, the
gas phase becomes identical with the alkane-rich liquid phase at the lg-UCEP. At the
same time, this has the consequence that the critical curve starting from this

23 (n-ALKANE

+ WATER) MIXTURES

341

FIGURE 5. Dependence of the critical temperatures T(lg-UCEP) and of the temperatures Tb of the
barotropic reversal of the two liquid phases of (an n-alkane + water) on the n-alkane carbon number i.
0, 1%UCEP; - - -, critical temperature of water; 0, temperatures Tb of the barotropic reversal of the
two liquid phases on the Ilg three-phase lines.

lg-UCEP ends at the critical point of the corresponding alkane. With increasing
carbon number of the alkane, this branch of the interrupted critical curve sweeps
increasingly large temperature ranges and, for i = 26, reaches the extraordinarily
high value of AT = 186 K. The second branch of the interrupted critical curve of the
mixtures with i = 1 to i = 26, which starts from the critical point of water, initially
passes through a temperature minimum, and rises steeply to high pressures as the
temperatures rise again. For all mixtures with i = 7 to i = 26 this branch of the
critical curve additionally
also passes through a pressure minimum between the
critical point of water and the temperature minimum.
With the carbon number i of the alkanes rising further, the temperature of the
lg-UCEP rises further. Because of the very wide (liquid + liquid) miscibility gap,
however, no 11-UCEP occurs with any of the mixtures. In contrast to some mixtures
of (an aromatic compound + water) where, for example, an infinite miscibility was
found for (naphthalene
+ water),37) (diphenyl
+ water),
and (1,2,3,4tetrahydronaphthalene
+ water). (45*46)the lg-critical curves remain interrupted even
at high carbon numbers. When the lg-UCEP then reaches, with increasing carbon
number i, temperatures which are in the range of the critical temperature of water,
T,(H,O) = 647.14 K, a very characteristic change takes place in the phase behaviour,
such as has hitherto not yet been found with other homologous mixtures. In the
temperature region immediately below the critical temperature of water, the density

E. BRUNNER

348

(e)

(f) i = 32

i = 30

25-

TIK

TIK

FIGURE 6. Section of the Ilg three-phase lines and the two branches of the critical p(T) curves for
(n-alkane + water) with the carbon numbers i = 20,24,26,28, and 30 in the region of the critical point of
water. -0,
Vapour pressure and critical point of water; - - - 0, Ilg three-phase line and lg-UCEP.

of the water-rich liquid phase 1, on the three-phase line decreases substantially faster
with rising temperatures than that of the alkane-rich liquid phase 1, until finally the
water-rich phase 1, has the lower density before the UCEP is reached. A barotropic
effect with reversal of theliquid
phases occurs on the l,l,g three-phase line; the
consequence is that the water-rich liquid phase 1, becomes identical with the gas
phase at the Ilg-UCEP. This also means that the l,g-critical curve which starts from
the l,g-UCEP, now no longer ends at the critical point of the alkane cp2 but at the
critical point of water cpl. The dependence of the critical temperature T(lg-UCEP)
on the carbon number i together with the temperature Tb of the barotropic reversal
of the two liquid phases on the 1,12g three-phase lines for i = 28, 30, 32, and 36 have
been plotted in figure 5. The larger-scale section of figure 5 shows clearly the decrease
of the temperature difference AT = (T(lg-UCEP)Tb) with decreasing carbon
number i. The barotropic effect was found with all mixtures with i > 28, whereas

23 @-ALKANE+

WATER) MIXTURES

349

T/K
FIGURE 7. Larger-scale section of the llg three-phase line and the critical p(r) curves for (n-alkane -t
water) with i = 24, 25, 26, and 28. To have a better review the critical p(T) curves extending from the
critical point of water for the mixtures with i = 24, 25, and 26 have been omitted. -0,
Vapour
pressure and critical point of water; - - - 0, llg-three-phase line and lg-UCEP. So as not to complicate
the curves, the measured p(T) points have not been indicated.

with all mixtures with i < 26 no barotropic effect exists on the I,l,g three-phase line.
With a defined quasi-binary (n-alkane + water) mixture, whose effective carbon
number i lies approximately at i = 26 or a little above, AT becomes zero and the
tem~rature
of the UCEP and of the barotropic reversal of the two liquid phases
must collapse in a (liquid 1 + liquid 2 + gas) tricritical end point l,f,g-TCEP where
all three phases become simultaneously identical. When the temperature of the llg
three-phase mixture with i = 26 is increased slowly, the beginning of the barotropic
phase reversal of the two liquid phases makes itself conspicuous by a strong spherical
rising in some parts of the interface of the two liquids shortly before the UCEP is
reached.
Because the tricritical point of a ternary mixture is an invariant that exists only at
a unique set of physical quantities Cp, T, x1, x2) it cannot be measured directly. For
the defined quasi-binary (n-alkane + water) mixture with i x 26 this tricritical point
is the end point of the three-phase line and of the three branches of the critical curve,
(a) l,g, which starts from the critical point of water, (b) 12g, which starts from the
critical point of the alkane mixture, and (c) 1,12, which is the ~ntinuation
of the l,l,g
three-phase line and which rises with increasing temperature up to high pressures. At

350

E. BRUNNER

the tricritical end point TCEP the three-phase line and the three branches of the
critical curve possess the same slope. There has so far been no other example in the
literature of the type of a tricritical point such as was found in the (n-alkane + water)
family, where the tricritical point simultaneously is the end point of an llg threephase line and of three branches l,l,, l,g, and 1,g of the critical curve. Tricritical
points are of great thermodynamic
interest, and numerous theoretical and
experimental
investigations
have dealt
with
this
interesting
phase
hhaviour (38-40,489
49)
To show the systematic changes and the characteristic differences in phase
behaviour between mixtures with i < 26 and i 2 28 sections of the llg three-phase
lines and the critical p(T) curves in the region of the critical point of water are
summarized for the mixtures with i = 20,24,25,26,28,
and 30 in figures 6a to 6f. To
give a better idea of the shape of the different curves these figures have also been
simplified by omitting all measured p(T) points with the exception of those that are
prominent. A larger-scale section of the region of the critical point of water for the
mixtures with i = 24,25,26, and 28 is plotted in figure 7 to show in more detail these
systematic changes in phase behaviour.
A further characteristic very typical of (an n-alkane + water) is the very low
mutual solubility of alkane and water. (42) A consequence of this is the fact that, in the
llg three-phase region, the total pressure of the mixtures is sometimes significantly
higher than the sum of the vapour pressures of the individual components. This
remarkable effect has already been found by Scheffer and confirmed by Roof(43
and by Tsonopoulos and Wilson. (44) It is not possible to predict quantitatively this
enhancement of the vapour pressures and the effect of gas-phase non-ideality
because of the inability to calculate fungacities in gaseous (alkane + water) mixtures.
This is due to insufficient knowledge about intermolecular forces and volumetric
properties of the mixed fluids.

4. On the topology of tricritical points

To demonstrate how tricritical points of quasi-binary mixtures occur, the two basic
types of tricritical point which have so far been found in real mixtures are compared
below and presented schematically in figures 8a to e and 9a to e.
TYPE II-TO-TYPE

III TRANSITION

Figure 8 (a) to (f) shows in schematic p(T) projections the typical intermediate stages
and border-line cases for the transition from type II to type III, as has for instance
been found in (n-alkane + ammonia). () Type II (figure 8a) possesses an l,l,g
three-phase line, an l,l,-UCEP,
and an uninterrupted critical curve designated (1,g
+ l,g), to underline the connection with the other phase diagrams of figure 8. Index
1 refers to the more volatile component and index 2 to the less volatile component.
As the carbon number of the alkane rises, the (1,g + 1,g) critical curve begins to
bifurcate into the two branches 1,g and 1,g. The border-line case type II/IV

73 (rr-ALKANE+

351

WATER) MIXTURES

FIGURE 8. The transition of the phase behaviour of binary mixtures from type II to type III shown as
p(r) projections of the critical loci and the Ilg three-phase lines due to increasing molecular dissimilarities
between the components 1 and 2, according to the classification of Scott and van Konynenburg. U, upper
critical end point; L, lower critical end point; 1,12, I,g, 1~ branches of the critical curves; (l,g + t,g),
uninterrupted critical curve; (I,& + llg), high-pr~sure branch of the interrupted critical curve, which
starts from the critical point of component 2; p, pressure; T, temperature.

(figure 8b) is designated by the tricritical point l,l,g-TCP

on the (I,g + 1,g)
uninterrupted critical curve; 1,g and 1,g have the same slope at 1,&g-TCP.
Type IV (figure SC) is characterized by the interrupted three-phase line with the
three critical end points Iii,-UCEP,
LCEP, and l,g-UCEP
and the three critical
curves lil,, l,g, and 1,g.
As the carbon number of the alkane increases further and as the miscibility of the
alkane and ammonia decreases, the branch of the three-phase line between LCEP
and l,g-UCEP gets bigger and the gap between l,l,-UCEP
and LCEP smaller, until
in the border-line case of type IV/III (figure Sd) I,l,-UCEP
and LCEP unite and a
double-critical point DCP occurs on the three-phase line. The now united branches
1,12 and 1,g form the critical curve (lil, + l,g), which tangentially touches the
three-phase line at the double-critical point.
As the miscibility of the components decreases further as a result of the increase in
carbon number of the alkane, the critical curve separates from the three-phase line
and phase behaviour of type III (figure 8e) is obtained with the two branches (l,l, +
1,g) and 1,g of the interrupted critical curve and an uninterrupted three-phase line
with an l,g-UCEP.
The special case of the tricritical point (figure 80, in which no type IV behaviour
occurs on transition from type If to type III, in other words, where the three-phase
line and the (1,12 + 1,g) critical curve touch tangentialiy at l,g-UCEP, and thus the
double-critical point, the tricritical end point, and the UCEP unite at a tricritical end

352

E. BRUNNER
(4

(b)

Cc)
412
hg / CD1

TCEP

9. The transition of the phase behaviour of binary mixtures from type IIIa to type IIIb with
the border-line case type IIIa/IIIb. (l,l, + I,g), high-pressure branch of the interrupted critical curve,
which starts from the critical point of component 1. The meaning of the other symbols is the same as in
figure 8.
FIGURE

point l,l,g-TCEP,
has so far not been found for any real fluid mixture. However, this
in the realm of real probability.
TYPE IIIa-TO-TYPE

IIIb TRANSITION

Figure 9 (a) to (c) shows schematically the phase behaviour of a mixture family in
which only type III with an interrupted critical curve occurs as was found for the first
time in (an n-alkane + water). At low alkane carbon numbers, the critical curve
which starts at l,g-UCEP runs to the critical point of the n-alkane (component 2); by
contrast, at high carbon numbers, it runs from lrg-UCEP to the critical point of
water (component 1). The two types of phase behaviour are designated type IIIa and
type IIIb, respectively.
In the border-line case IIIa/IIIb
(figure 9b) the two branches of the critical curve
touch the three-phase line tangentially at lg-UCEP and possess here a tricritical end
point l,l,g-TCEP.
The two branches 1,g and (l,l, + 1,g) which exist at low carbon
numbers become the two branches 1,g and (l,l, + 1,g) which exist at high carbon
numbers. A transition from type IIIa oia type IV to type IIIb analogous to the
transition from type II via type IV to type III does in all probability not occur in real
fluid mixtures.
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