Fluid Phase Equilibria, 57 (1990) 1-33 1

Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

Review

HIGH PRESSURE FLUID PHASE EQUILIBRIA: EXPERIMENTAL

METHODS AND SYSTEMS INVESTIGATED (1978-1987)

ROSA E. FORNARI
Planta Pilot0 de Ingenieria Quimica, UNS-CONICET, CC 717, 8000 Bahia Blanca (Argentina)

PAOLO ALESSI and IRENE0 KIKIC

Istituto di Chimica Applicata e Industriale, Via A. Valerio, 2, Universita di Trieste,
3412 7 Trieste (Italy)
(Received April 25, 1989)

ABSTRACT

Fornari, R.E., Alessi, P. and Kikic, I., 1990. High pressure fluid phase equilibria: experimen-
tal methods and systems investigated (1978-1987). Fluid Phase Equilibria, 57: l-33.

The phase behaviour of fluid mixtures at high pressure has received great attention over
the past decade. This upsurge of interest has been occasioned by the importance that high
pressure fluid phase equilibria has now assumed in some industrial areas.
This work reviews and classifies recently developed experimental methods for investigating
high pressure fluid phase equilibria. A review of the systems studied in the last 10 years is
also given.

INTRODUCTION

The growing motivation for studying equilibria of several coexisting

phases at elevated pressures arose from the need to describe such phase
behaviour for fluid mixtures of interest in supercritical fluid extraction
(SCFE). In recent times, a large number of applications of this technology
have been proposed covering the food, pharmaceuticals, chemical, coal and
oil processing and producing industries. A complete review of the potential
applications of SCFE processes is given by Brignole (1986).
High pressure multiphase behaviour is also important in the development,
often at cryoscopic temperatures, of new and highly efficient separation
techniques in the natural gas, oil and petrochemical industries.
The development of high pressure technology led to systematic studies of
the effects of high pressure on phase equilibria in fluid systems. Experiments

0378-3812/90/$03.50 0 1990 - Elsevier Science Publishers B.V.

2

in the critical region, even in two-component mixtures of relatively simple

molecules, showed phase relationships of surprising complexity and variety.
Continuous transitions between liquid-gas, liquid-liquid and gas-gas equi-
libria in the P-T-x space occur. Discussions of this behaviour are given by
Rowlinson (1982), Schneider (1976), Wichterle (1977, 1978) and Streett
(1983). The understanding of these phenomena has great importance in
experimental work.
In the last few years different techniques for experimental investigation of
high pressure phase equilibria have been proposed. A review covering the
1970s is given by Eubank et al. (1980). This work presents an actual review
and a classification of the experimental methods. The systems studied in the
last 10 years are also presented.

BIBLIOGRAPHY INFORMATION

Taking into consideration the review done by Hiza et al. (1974) and this
work, there are approximately 600 papers which provide high pressure fluid
phase equilibrium data.
The growth of interest started in the 60s and almost one third of the data
have been found in the last decade.
A selection of data is also published by Hicks (1978) and by Knapp et al.
(1981) in DECHEMA Data Series, covering the period 1900-1980.
This review covers only the last 10 years for the journals listed in Table 1.
It can be seen that more than 80% of the information is published in the
Journal of Chemical Engineering Data and in Fluid Phase Equilibria.

TABLE 1
Bibliographic information

Journal Number of papers

(1978-1987)
J. Chem. Eng. Data 92
Fluid Phase Equilibria a 69
Ind. Eng. Chem. 15
Ber. Bunsenges. Phys. Chem. 9
AIChE J. 5
J. Phys. Chem. 3
Can. J. Chem. Eng. 3
Chem. Eng. Sci. 2
J. Chem. Sot. Faraday Trans. I 1
a Covered from the first issue (1977).
 3

TABLE 2
Classification of experimental methods in high pressure fluid phase equilibria
constant-volume static cell (CVSC)
Static
Analytical or C variable-volume static cell (WSC)
direct sampling
methods
(DSMs)
pure gas circulation (PGC)
gas phase recirculation (GPR)
liquid phase recirculation (LPR)
gas and liquid phase recirculation (GLPR)
continuous flow (CF)
Synthetic or
indirect methods
(IMs)

EXPERIMENTAL METHODS

The experimental techniques used to investigate multiphase equilibria can

be classified by the method employed to determine compositions: analytical
or direct sampling methods (DSMs) and synthetic or indirect methods (IM),
also called stoichiometric determinations.
DSMs require composition analysis following the attainment of equi-
librium. They can be subdivided by considering the techniques used to
achieve equilibrium conditions: static, continuous flow (CF) and circulation
methods. CF and circulation methods are dynamic methods.
IMs involve an indirect determination of equilibrium compositions without
sampling.
Table 2 gives the classification of experimental methods in high pressure
fluid phase equilibria and Table 3 shows the papers which provide informa-
tion about the equipment and instrumentation for the different experimental
techniques.
In the last few years both methods were used incorporating the capacity
for visual observations of the phase behaviour. The advantage of an equi-
librium cell with visual capabilities is that phase separation can be observed
directly. This eliminates the possibility of missing an additional equilibrium
phase. Taking into account the behaviour of high pressure mixtures, the
visual cell must always be considered.

Analytical or DSMs

At high pressure, the main experimental difficulty is sampling. Near

critical conditions large disturbances to equilibrium can occur when
withdrawing samples from the cell. Working at elevated pressures also
4

TABLE 3
Papers which provide information about equipment and instrumentation in the different
experimental techniques a

Constant-volume static cell (CVSC)

Ng, H-J. and Robinson, D.B., 1978, 1979; Vera, J.H. and Orbey, H., 1984; Lhotak, V. and
Wichterle, I., 1981; Richon, D. and Renon, H., 1983; Ng, H-J. et al., 1985; Melpolder, F.W.,
1986; Deiters, U.K. and Schneider, G.M., 1986; Dohrn, R. and Brunner, G., 1986; Wagner,
Z. and Wichterle, I., 1987; Nakayama, T. et al., 1987; Guillevic, J-L. et al., 1983; Japas, M.L.
and Franck, E.U., 1985; Gomez-Nieto, M. and Thodos, G., 1978a; Figuiere, P. et al., 1980;
Legret, D. et al., 1981.
Variable volume static cell (WSC)
Kaira, H.K. et al., 1978; Li, Y-H. et al., 1981; Meskel-Lesavre, M. et al., 1982; Huang, S.S.S.
et al., 1985; Dingrani, J.G. and Thodos, G., 1978; Gomez-Nieto, M. and Thodos, G., 1978b;
FontaIba, F. et al., 1982; Fontalba, F. et al., 1984.
Pure gas circulation (PGC)
Garber, J.D. and Ziegler, W.T., 1979
Gas phase recirculation (GPR)
Mraw, S.C. et al., 1978; Somait, F.A. and Kidnay, A.J., 1978; Tsang, C.Y. and Streett, W.B.,
1981; Chang, E. et al., 1982; Nasir, P. et al., 1980/81; Kubic, W.L., Jr. and Stein, F. P.,
1980/81; Dorau, W. et al., 1983; Weber, W. et al., 1984; Chang, T. and Rousseau, R.W.,
1985;. Charoensombut-Amon, T. et al., 1986; Freitag, N.P. and Robinson, D.B., 1986; Pozo
de Femandez, M.E. et al., 1987; Al-Sahhaf, T.A., et al. (1983).
Liquid phase recirculation (LPR)
Kir’n, C-k. et al., 1986.
Gas and liquid phase recirculation (GLPR)
Parrish, W.R. and Sitton, D.M., 1982; Behrens, P.K. and Sandler, S.I., 1983; Morris, W.O.
and Donohue, M.D., 1985; Radosz, M., 1986; Rizvi, S.S.H. and Heidemann, R.A., 1987; D.
Souza, R. and Teja, A.S., 1988 (161); Ramanujam, S., et al., 1985; Radosz, M., 1984; Kuk,
M.S. and Montagna, J.C., 1983; Panagiotopoulos, A.Z. and Reid, R.C., 1986.
Continuous flow (CF)
Thies, M.C. and Paula&is, M.E., 1984; Gilbert, M.L. and Paulaitis, M.E., 1986; Inomata, H.
et al., 1986 (139); Niesen, V. et al., 1986; Briones, J.A. et al., 1987; Lin, H-M. et al., 1985;
Simnick, J.J. et al., 1977; Radosz, M., 1985.
Indirect method (IM)
Fall, D.J. et al., 1985 (63); De Loos, T.W. et al., 1986; Rousseaux, P. et al., 1983; Richon, D.
and Renon, H., 1983; Enick, R. et al., 1985; Occhiogrosso, R.N. et al., 1986; Deite.rs, U.K.
and Schneider, G.M., 1986; Peters, C.J. et al., 1987; Meskel-Lesavre, M. et al., 1981;
DiAndreth, J.R. et al., 1987; Japas, M.L. and Franck, E.U., 1985; Gehrig, M. et al., 1986;
Francesconi, A.Z. et al., 1981.

a Papers followed by a number in parentheses are to be found under that number in the Data
References list.
 5

presents the possibility of preferentially sampling the more volatile mixture

constituents. This shows that analytical methods work well far away from
critical points, where the equilibrium is disturbed by sampling, and baro-
tropic points, where the phases do not separate (Deiters and Schneider,
1986).

Static methods

The gas-liquid mixture is simply stirred in a closed cell until pressure and
temperature reach equilibrium values, then samples of both phases are
withdrawn and analysed. If sampling can be achieved in a simple and
reproducible way, static methods allow the use of the least expensive,
accurate laboratory apparatus (Legret et al., 1981; Fontalba et al., 1982,
1984).
In previous works, static cells used mercury injection in order to keep the
pressure constant during the sampling process. More recently the pressure
drop while sampling has been avoided by trying to reduce the amount
withdrawn; in this manner the equilibrium in the cell is disturbed only
slightly and does not affect the results at all. This can be done with
capillaries (Wagner and Wichterle, 1987), fast-acting pneumatic or electro-
magnetic valves (Figuier et al., 1980) or detachable sampling microcells
(Legret et al., 1981).
Static methods use constant or variable volume cells and hence can be
classified as constant-volume static cells (CVSCs) and variable-volume static
cells (WSCs).
In WSCs the pressure of the system can be increased or decreased
alternately by the movement of a piston in the cell (Huang et al., 1985). This
adds flexibility to the operation. Extension of the application of WSCs to
solutions containing polymers has been proposed by Rousseaux et al. (1985)
where ethene-polyethylene mixtures were investigated up to 26.1 MPa.

CF methods

The flow cell concept of phase equilibrium measurements was pioneered

by Simnick and co-workers (1977).
Figure 1 shows a simplified diagram of a continuous flow apparatus.
Upstream of the cell, two high pressure metering pumps feed the con-
densable components to a mixer. The mixer provides the mechanical energy
needed to promote mass transfer. The feed streams are also heated to the
desired operating temperature. Downstream of the cell, two low pressure
separators, one for each of the phases, separate the depressurized effluents
into vapour and liquid. Four samples are generated; vapour and liquid from
6

Fig. 1. Continuous flow apparatus.

each of the equilibrium phases. The equilibrium phase compositions are

calculated from the material balance based on the measured vapour and
liquid weight (Radosz, 1985).
The time needed to reach a steady state with constant effluent stream
compositions depends on the system.
This technique presents some advantages; residence time of the sample in
the high temperature zone is reduced and the thermal decomposition of
temperature sensitive substances is thereby minimized, mixing and subse-
quent sampling are facilitated, heavy compounds can be handled and large
samples can be generated.
In the last few years this method has frequently been used. A complete
description can be found in the literature given by different authors (see
Table 3).
A modification of continuous flow apparatus was proposed by Legret et
al. (1983), who applied the dilutor technique to high pressure. In this case
the mixture is contained in the equilibrium cell and an inert gas strips the
gas phase in equilibrium.

Circulation methods

One circulation method is the single-pass flow design; the more volatile
component in the gaseous state is passed through a liquid mixture at
measured temperature and pressure (pure gas circulation, PGC). The ef-
fluent gaseous phase is sampled and analysed, as is the residual liquid phase
(or phases). Such an apparatus is particularly useful for studying mixtures
containing high concentrations of the volatile component and the major
uncertainty is the possible lack of attainment of equilibrium within the
liquid sample (Garber and Ziegler, 1979).
Fig. 2. Gas phase recirculation apparatus.

This uncertainty is greatly reduced in the other circulation methods which

use recirculation loops to achieve equilibrium conditions. They can be
subdivided into gas phase recirculation (GPR), liquid phase recirculation
(LPR) and gas and liquid phase recirculation (GLPR) methods.
Figure 2 is a simplified diagram of a GPR apparatus. The vapour phase is
recirculated around the loop by the action of a magnetic pump and it must
pass completely through the liquid in a short period of time to ensure a
rapid approach to equilibrium (Tsang and Streett, 1981).

AL

AL

lo-

I L _tl I

Fig. 3. Gas and liquid phase recirculation apparatus with sampling loops.
8

_--- --
r
-em-,
I

Fig. 4. Gas and liquid phase recirculation apparatus with static sampling ports and variable
volume cylinder.

GLPR methods were also used by many authors in the last few years. The
techniques present some differences: Kuk and Montagna (1983) employed
recirculation-sampling loops for the gas phase and the dense liquid phase
and an additional sampling port for the third phase of intermediate density.
A diagram of this apparatus is shown in Fig. 3.
In other works, recirculation is used as a means of internal mixing only,
the sampling being accomplished through static sampling ports (Behrens and
Sandler, 1983; Ng and Robinson, 1979; Radosz, 1986). In this case a serious
difficulty which must be avoided is the drop in pressure while sampling. To
solve this problem, Radosz (1986, 1984) added a variable-volume cylinder to
the top-phase recirculation loop. A simplified diagram of the variable-volume
circulation apparatus is given in Fig. 4.
Some apparata present the possibility of choosing the phase (gas or
liquid) to be recycled (Hsu et al., 1985).

Synthetic or IA4

In this method no sampling is necessary, so the difficulties related to

sampling process are avoided, and measurements can be made near critical
conditions.
Stoichiometric techniques have been used to measure phase boundaries in
the critical region (Jockers and Schneider, 1978). The experimental proce-
dure is at follows. Known amounts of the components are placed into the
variable-volume pressure cell. The temperature and pressure are then ad-
justed so that the contents of the pressure vessel form a homogeneous phase;
mole fractions can be calculated from the amounts of substances initially
 9

transferred into the cell. The pressure or the temperature are varied until the
formation of a new separation is observed. The pressure and the temperature
at which this phase separation starts and the mole fractions, define a point
of the phase envelope. This technique applied to multicomponent mixtures
yields the P, T, x envelopes, but not the tie lines.
Hottovy and co-workers (1981) have applied a synthetic method to
liquid-liquid-gas equilibrium for binary and ternary mixtures characteristic
of liquified natural gas and CO, reservoir fluid systems. A view cell is
loaded with a mixture of known overall composition such that one liquid
phase is present in excess. After equilibration, the temperature, pressure and
phase volumes are measured, and the liquid phase compositions are related
directly to the known overall composition with the assumption that the gas
phase consists only of the most volatile constituent. For liquid-liquid-gas
equilibrium, the cell loadings must result in gas phase and one liquid phase
present in relatively small quantities.
Di Andreth and co-workers (1987) presented a stoichiometric technique
for determining equilibrium compositions and molar volumes of multiple
coexisting fluid phases for binary and ternary mixtures. This technique
represents an improvement over other stoichiometric techniques (Hottovy et
al., 1981) because the data analysis does not require simplifying assumptions
about the compositions of any of the phases, and the variable-volume
apparatus used with this technique adds considerable flexibility to the
experimental method. It can be applied to investigation of multicomponent
mixtures and multiple phases in equilibrium, so long as the number of
phases is greater than or equal to the number of mixture constituents. This
means that the degrees of freedom must be less than or equal to two. Fixing
temperature, pressure or both, the compositions in the different phases are
constant. Different cell loads will give different phase volumes which are
measured. The compositions are then determined from the material balance.
The technique is well suited for measurements of phase equilibria at
elevated pressure, at conditions near the critical region, and for complex
multiphase equilibria.

SYSTEM INVESTIGATED

Tables 4a to 4r give information about the systems studied in the last 10

years. For each system, pressure and temperature ranges, the experimental
method employed and references are provided. The reader interested in
comparing the different techniques can easily find many systems investi-
gated at the same temperature and pressure ranges with different apparatus
and procedure, so that an analysis of the performance can be realized.
10

TABLE 4a
Binary system: Hydrogen-X

X Refer- Experi- T(=‘C) P (MPa)

ences a mental
method
Argon (99) GPR - 190- - 132 up to 52.0
Carbon monoxide (107) GPR - 203- - 148 up to 53.0
Carbon dioxide (198) GPR -53- 17 up to 172.0
Methane (33) GPR -165- -90 up to 28.0
Ethane (48) GPR -210- 7 up to 560.0
Pentane (145) GPR o- 100 up to 27.6
2,2,4-Trimethylpentane (26) cvsc 226- 260 3.0- 18.7
Decane (19) CF 189- 310 2.0- 25.0
Hexadecane (25) CF 190- 391 2.0- 25.0
Ethene (178) GPR -159- -26 4.0-600.0
1,1-Bicyclohexyl (4) CF 190- 430 2.0- 25.0
Toluene (26) cvsc 269- 295 3.5- 30.8
1-Methylnaphthakne (95j CF 190- 430 2.0- 25.0
Diphenyhnethane (162) CF 190- 430 2.0- 25.3
Tetrahydronaphthalene (103) GPR 150- 349 2.0- 27.3
(186) CF 189- 389 20.0-250.0
QuinoIine (8) CF 190- 430 2.0- 25.0
9,lO Dihydrophenanthrene (17) CF 188- 430 2.0- 25.0
Thionaphthene (195) CF 190- 430 up to 25.3
Tetrafluoromethane (23) PGC - 178- - 108 2.0- 12.0
Chlorotrifluoromethane (23) PGC -138- -53 2.0- 12.0
a Numbers refer to Data reference list at end of papers.

TABLE 4b
Binary system: Water-X

X References Experimental T(OC) P (MPa)

method
Ammonia (71) cvsc 130-230 0.8- 7.2
(84) GLPR 33-345 up to 22.0
Nitrogen (182) IM 250-400 20.0-270.0
cvsc
Oxygen (183) IM 227-387 20.0-280.0
cvsc
Carbon dioxide (158) CF 50 6.8- 17.7
Pentane (113) IM 327-402 15.0-170.0
Heptane (113) IM 327-402 15.0-170.0
Ethanol (146) CF 150-250 0.7- 7.1
Dimethylether (119) GPR 50-220 up to 50.0
l,l-Difluoroethane (160) cvsc 50 0.6- 10.1
Fluorobenzene (177) IM 280-420 up to 360.0
l&Difluorobenzene (177) IM 280-420 up to 360.0
 11

TABLE 4c
Binary system: hydrogen sulfide-X

X References Experimental T(“C) P (MPa)

method
Heptane (18) wsc 38-204 0.1-9.5
Methylcyclohexane WV cvsc 37-205 0.3-9.5
Benzene (116) IM 157-280 5.6-8.3
Toluene (18) wsc 38-204 0.2-11.6
Ethylcyclohexane (64) cvsc 40-100 0.1-13.0
1,3-Dimethylbenzene (122) cvsc 37-205 0.2-13.1
Propylcyclohexane (64) cvsc 40-100 0.1-13.0
1,3,5-Trimethylbenzene (122) cvsc 37-205 0.2-13.8
Triethyleneglycol (157) GPR 25-125 up to 6.5
Methanethiol (2) GPR 38- 42 2.4-2.6

TABLE 4d
Binary system: Nitrogen-X

X References Experimental T(‘C) P (MPa)

method
Water (182) IM 250- 400 20.0-270.0
cvsc
Carbon dioxide (7) GPR -3 3.0- 12.0
(65) wsc 0- 25 4.0- 8.0
(165) GPR -53- -33 0.6- 16.7
Ethane (27) GPR -13- 7 1.7- 9.9
(72) IM -155--140 2.1- 4.1
(93) GPR -73- 17 0.2- 13.2
(181) IM -185- 40 up to 200.0
Propane (56) IM -go- 70 O.l- 5.7
(72) IM -156--146 2.2- 3.5
(93) GPR -43- 17 0.4- 21.9
Butane (56) IM -5o- 40 O.l- 6.7
Isobutane (10) wsc -18- 121 0.2- 21.0
cvsc
(56) IM -5o- 80 O.l- 5.5
Pentane (181) IM -185- 40 up to 200.0
Heptane (188) cvsc 180- 224 up to 30.0
(189) cvsc 32 9.1- 99.9
Hexadecane (109) CF 190- 430 2.0- 25.5
Ethene (93) GPR -73- -13 0.4- 11.0
(105) GPR -153- -73 up to 9.3
(132) GPR -33- -13 1.8- 9.1
Propene (93) GPR -13- 17 0.4- 21.4
1-Methylnaphthalene (112) CF 189- 430 2.0- 25.0
Methanol (123) GPR -48- 27 2.1- 17.9
(131) GPR -33- -13 l.O- 7.5
1-Dodecanol (152) cvsc 119 9.0- 33.0
3-Hydroxytoluene (51) CF 190- 390 2.0- 25.0
Quinoline (43) CF 189- 431 2.0- 25.0
Tetrahydronaphthalene (51) CF 190- 390 2.0- 25.0
12

TABLE 4e
Binary system: carbon dioxide-X

X References Experimental T(OC) P (MPa)

method
Hydrogen (198) GPR -53 - 17 up to 172.0
Water (158) CF 50 6.8-17.7
Nitrogen (7) GPR -3 3.0-12.0
(65) wsc o.o- 25 4.0- 8.0
(165) GPR -53 --33 0.6-16.7
Methane (3) GPR -120 --54 0.6- 6.0
(7) GPR -3 3.0- 8.0
(165) GPR -54 - -3 0.6- 8.5
Ethane (94) cvsc 10 - 25 3.0- 6.4
Propane (58) IM -60 - 0.0 o.o- 2.0
Butane (73) GorLPR 46 - 105 2.2- 8.1
(91) wsc 95 - 145 1.4- 7.9
2-Methylpropane (91) wsc .llO - 125 2.5- 6.0
Pentane (92) wsc 135 - 190 1.2- 9.0
2-Methylbutane (92) wsc 135 - 180 1.5- 8.3
Hexane (32) wsc 40 - 120 0.7-11.6
(148) IM 0 - 30 l.O- 6.0
(151) cvsc 30 - 50 2.0- 8.5
Heptane (9) wsc 37 - 204 0.2-13.3
(139) CF 121 up to 14.0
Decane (20) CF 190 - 310 2.0- 5.0
(78) GorLPR 70 - 110 6.0-17.0
(139) CF 138 up to 20.0
(201) CF 137.8 3.4-10.3
Dodecane (37) IM -19 - -6 2.0- 2.9
Tridecane (37) IM -18- 6 2.1- 3.9
(68) IM 38 - 41 8.1- 8.7
(127) IM 27 - 42 7.0- 9.5
Tetradecane (37) IM -4 - 38 3.1- 8.3
Pentadecane (37) IM -3 - 36 3.2- 8.0
Hexadecane (20) CF 190 - 390 2.0- 5.0
(144) GPR 35 - 70 0.7-26.0
Nonadecane (63) IM 19 - 60 0.9- 8.0
Heneicosane (63) IM 30 - 65 0.9- 8.0
Docosane (60) IM 50 - 100 l.l- 7.2
Octacosane (167) CF 35 - 52 8.1-32.9
wsc
Dotriacontane (60) IM 75 - 125 0.9- 7.2
Ethene (40) cvsc -10 - 25 2.5- 6.6
Propene (111) cvsc 10 - 25 0.9- 6.0
l-Butene (49) GLPR 37 - 45 0.5- 7.3
1-Hexene (54) cvsc 30 - 70 l.O- 3.4
(151) cvsc 30 - 50 2.1- 8.5
 13

TABLE 4e (continued)

X References Experimental T(“C) P (MPa)

method
2-Methyl-1-pentene (54) cvsc 30 - 70 l.O- 3.4
l-Heptene (54) cvsc 30 - 70 l.O- 3.7
Cyclopentane (75) GLPR 38 - 60 0.2- 8.3
Cyclohexane (88) GorLPR 71.1 6.9-11.0
(148) IM o.o- 30 0.7- 6.0
Methylcyclohexane (100) cvsc 37 - 205 0.4-14.9
Transdecahydro-
naphthalene (1) IM 0 - 75 l.O- 7.0
(139) CF 72 - 251 4.7-22.1
(174) IM 40 8.2
Tetrahydronaphthalene (101) CF 190 - 390 2.0- 5.0
Benzene (41) wsc 40 - 120 0.1-13.3
(88) GorLPR 71.1 6.9-11.0
(116) IM 31 - 289 4.9-13.4
(147) LPR 40 - 120 2.1- 6.3
(148) IM o.o- 30 l.O- 6.0
(156) CF 70 - 141 2.3-15.4
Toluene (11) cvsc 38 - 204 0.3-15.3
(24) CF 120 - 270 l.O- 5.1
(67) GLPR 80 - 140 0.2-13.2
(147) LPR 80 - 120 0.5- 6.5
Ethylbenzene (150) CF 39 - 93 2.4-14.2
1,2_Dimethylbenzene (150) CF 39 - 93 1.5-14.9
1,3-Dimethylbenzene (24) CF 190 - 310 2.1- 5.2
(42) cvsc 38 - 205 0.3-17.0
(54) cvsc 30 - 70 0.7- 2.7
(150) CF 39 - 93 1.3-15.4
1,4-Dimethylbenzene (147) LPR 80 - 120 0.5- 6.1
(150) CF 39 - 93 1.2-14.2
1,3,5_Trimethylbenzene (196) cvsc 38 - 205 0.2-17.6
Isopropylbenzene (133) IM 26 - 110 0.7-17.5
Butylbenzene (1) IM 0 - 20 l.O- 5.0
Hexylbenzene (137) IM -56 --18 0.5- 2.0
(154) IM 15 - 45 0.7- 9.2
Heptylbenzene (137) IM -54 - 39 0.6- 8.5
(154) IM -5 - 45 l.O- 9.2
Octylbenzene (137) IM -49 - 37 0.7- 8.2
(154) IM 15 - 45 0.9- 8.3
Nonylbenzene (129) IM -45 - 35 0.8- 7.9
Pentadecylbenzene (129) IM 2 - 31 3.7- 7.5
Diphenylmethane (21) CF 189 - 430 2.0- 5.0
1-Methylnaphthalene (21) CF 189 - 430 2.0- 5.0
(67) GLPR 80 - 140 1.8-14.4
14

TABLE 4e (continued)

x References Experimental T(OC) P (MPa)

method
Methanol (123) GPR -4o- 25 0.3- 5.1
(128) GPR -3o- 25 up to 5.5
Ethanol (202) GLPR 35- 65 up to 11.0
2-Hydroxypropane (76) GLPR 44- 121 5.9-12.1
(180) GLPR 62 5.8- 9.3
I-Dodecanol (152) cvsc 119 9.0-37.0
Triethyleneglycol (157) GPR 25- 125 up to 20.3
Dimethylether (35) GPR o- 113 0.3- 7.9
Butylether (150) CF 39- 93 1.2-14.2
Acetone (202) GLPR 40- 60 up to 10.0
Acetic Acid (158) CF 50 5.6- 8.4
3-Hydroxytoluene (31) CF 189- 392 2.0- 5.0
Quinoline (31) CF 188- 430 2.0- 5.0
(139) CF 70- 268 4.5-22.5

It should be mentioned that the methods more often used are IM, GPR,
CF, and CVSC.
Tables 4a to 4p correspond to binary systems, Table 4q to ternary systems
and Table 4r to multicomponent systems.
The high number of systems with CO, can be noted: this can be justified
by the increasing interest in employing CO, as a solvent in supercritical
fluid extraction.
 15

TABLE 4f
Binary system: methane-X

X References Experimental T ( o C) P (MPa)

method
Hydrogen (33) GPR -165 --90 up to 28.0
Krypton (199) GPR -113 --69 l.l- 5.3
Carbonyl sulfide (15) wsc 25 - 100 2.5-10.7
Carbon dioxide (3) GPR -120 --54 0.6- 6.0
(7) GPR -3 3.0- 8.0
(165) GPR -54 - -3 0.6- 8.5
Ethane (27) GPR -13- 7 1.7- 7.1
Nonane (115) wsc 50 - 150 2.0-25.6
Deeane (12) CF 150 - 310 3.0-18.0
Hexadecane (25) CF 190 - 430 2.0-25.0
Benzene (12) CF 150 - 230 2.0-24.0
(45) cvsc 40.0 3.7-37.4
Toluene (6) GPR -84- 4 0.3-48.7
(12) CF 150 - 270 2.0-25.0
(45) cvsc 40 10.1-42.4
1,3_Dimethylbenzene (42) cvsc 38 - 205 0.4-14.0
(45) cvsc 40 5.1-46.5
(98) CF 190 - 310 2.0-25.0
1,3,5-Trimethylbenzene (45) cvsc 40 10.2-51.9
(196) cvsc 30 - 205 0.3-14.6
Diphenylmethane (13) CF 190 - 430 2.0-25.0
1-Methylnaphthalene (13) CF 190 - 430 2.0-25.0
Methanol (159) GPR -73 - 57 0.7-41.4
(191) IM 69 - 240 up to 300.0
Triethyleneglycol (157) GPR 25 - 125 up to 20.2
Dimethylether (86) cvsc 9 - 71 2.0-10.7
Diethylether (86) cvsc 9 - 71 2.0-17.1
Quinoline (14) CF 189 - 430 2.0-25.0
Tetrahydronaphthalene (13) CF 190 - 390 2.0-25.0
9,10-Dihydrophenanthrene (30) CF 190 - 430 2.0-25.0
Methylal (87) cvsc 0 - 159 1.0-20.2
IM
3-Hydroxytoluene (98) CF 190 - 390 2.0-25.0
Acetone (66) GLPR 25 - 50 1.0-12.0
Chlorodifluoromethane (65) wsc -10 - 25 l.O- 9.0
Dichlorodifluoromethane (65) wsc -10 - 25 l.O- 8.0
16

TABLE 4g
Binary system: ethane-X

X References Experimental T(“C) P (MPa)

method
Hydrogen (48) GPR -210- 7 up to 560
Nitrogen (27) GPR -13- 7 1.7- 9.9
(72) IM - 155- - 140 2.1- 4.1
(93) GPR -73- 17 0.2-13.2
(181) IM -185- 40 up to 200.0
Xenon (192) GPR -63- 31 up to 5.2
Carbon dioxide (94) cvsc lo- 25 3.0- 6.4
Butane (106) cvsc 30- 90 0.4- 5.3
2-Methylpropane (77) IM 38- 129 up to 5.5
Dodecane (163) IM 25- 100 0.3- 5.9
(164) IM 35- 100 0.4- 5.3
Eicosane (153) IM -3- 177 up to 18.0
Docosane (85) IM 28- 35 4.5- 5.1
Tricosane (85) IM 25- 34 4.1- 5.1
Tetracosane (85) IM 28- 34 4.5- 5.0
Propene (111) cvsc lo- 25 0.9- 4.1
Methanol (131) GPR -33- 25 0.4- 4.2
Triethyleneglycol (157) GPR 25- 125 up to 20.5
2-Aminopropane (89) IM 5- 95 0.2- 6.9

TABLE 4h
Binary system: propane-X

X References Experimental T(‘C) P (MPa)

method
Nitrogen (56) IM -98- 70 O.l- 6.7
(72) IM - 156- - 146 2.2- 3.5
(93) GPR -43- 17 0.4-21.9
Carbon dioxide (58) IM -6O- 0 o.o- 2.0
Octane (166) cvsc 154- 250 2.2- 5.1
Ethanol (187) cvsc 52- 152 0.6- 5.6
Triethyleneglycol (157) GPR 25- 125 up to 6.5
Acetone (197) wsc 52- 152 up to 4.7
 17

TABLE 4i
Binary system: Ethene-X

X References Experimental T(OC) P (MPa)

method
Helium (16) PGC - 143- -57 2.3- 12.0
Hydrogen (178) GPR -159--26 4.0-600.0
Nitrogen (93) GPR -73--13 0.4- 11.0
(105) GPR - 153- -73 up to 9.3
(132) GPR -33--13 1.8- 9.1
Carbon dioxide (40) cvsc -lo- 25 2.5- 6.6
Xenon (193) GPR -7o- 14 up to 5.7
Eicosane (28) IM 50 l.O- 15.0
(179) IM 50- 150 0.5- 24.4
Tetracontane (179) IM loo- 175 0.9- 40.6
Hexacosane (179) IM 75- 175 0.8- 30.2
Triacontane (140) IM 75- 175 l.O- 33.4
2,6,10,15,19,23-hexa-
methyltetracosane (140) IM 75- 175 0.8- 29.0
Dotriacontane (28) IM 75 l.O- 29.0
Propene (111) cvsc lo- 25 LO- 5.4
Methanol (132) GPR -33- 25 0.4- 6.0
Acetone (66) GLPR 25- 50 l.O- 8.0

TABLE 4j
Binary system: methanol-X

X References Experimental T(‘C) P (MPa)

method
Nitrogen (123) GPR -48- 27 2.1- 17.9
(131) GPR -33--13 l.O- 7.5
Carbon dioxide (123) GPR -4O- 25 0.3- 5.1
(128) GPR -3O- 25 up to 5.5
Methane (159) GPR -73- 57 0.7- 41.1
(191) IM 69- 240 up to 300.0
Ethane (131) GPR -33- 25 0.4- 4.2
Propane (136) cvsc 40- 100 0.4- 4.3
IM
Hexane (135) IM 19- 67 1.0-150.0
Nonane (135) IM 75- 114 1.0-150.0
Decane (135) IM 86- 117 1.0-100.0
Ethene (132) GPR -33- 25 0.4- 6.0
Naphthalene (74) CF 248- 306 1.5- 12.1
1-Methylnaphthalene (61) CF 246- 297 1.3- 12.1
Ethanol (146) CF lO@- 140 0.2- 1.1
Dimethylether (46) GPR 0- 180 up to 6.7
Quinoline (79) CF 248- 307 l.l- 12.5
1-Naphthol (74) CF 248- 306 Ll- 13.7
Tetrahydronaphthalene (79) CF 248- 307 1.6- 11.3
18

TABLE 4k
Binary system: isopropyl fluoride-X
X References Experimental T(OC) P (MPa)
method
Propane (47) GLPR 30-50 0.4-1.4
Butane (47) GLPR 30-50 0.4-0.7
2-Methylpropane (47) GLPR 30-50 0.4-0.8
Propene (47) GLPR 30-50 0.4-1.4

TABLE 41
Binary system: tetrafluoromethane-X

X Refer- Experi- T(‘C) P (MPa)

ences mental
method
Hydrogen (23) PGC - 178- - 108 2.0- 12.0
Heptane (126) IM 40- 119 20.3-350.0
Dodecane (126) IM 145- 206 39.8-221.0
cis-Decahydronaphthalene (126) IM 188 291 35.0-260.0
Tetrahydronaphthalene (126) IM 245- 324 39.0-270.0
2,6,10,15,19,23-hexa- (126) IM 271- 359 54.0-270.0
methyltetracosane
Chlorotrifluoromethane (104) GPR -74- 16 O.l- 4.3

TABLE 4m
Binary system: trifluoromethane-X

X Refer- Experimental T(“C) P (MPa)

ences method
Hexane (126) IM 2- 96 2.7-234.0
Octane (126) IM 36-151 9.2-235.0
Decane (126) IM 77-159 18.2-239.0
cis-Decahydronaphthalene (126) IM 128-254 27.0-245.0
Tetrahydronaphthalene (126) IM 67-178 29.0-255.0
1-Dodecanol (152) cvsc 119 9.0- 33.0
Trichlorotrifluoroethane (90) wsc 25-100 l.O- 8.0
 19

TABLE 4n
Binary system: chlorotrifluoromethane-X

X References Experimental T(“C) P (MPa)

method
Hydrogen (23) PGC -138--53 2.0-12.0
Tetrafhioromethane (104) GPR -74- 16 O.l- 4.3
1-Dodecanol (152) cvsc 119 9.0-37.0
1,1,2-TrichIorotri-
fluoroethane (44) IM 25- 100 LO- 5.0

TABLE 4o
Binary system: perfluoromethylcyclohexane-X

X References Experimental T(“C) P (MPa)

method
Hexane (29) IM 110-230 0.3-3.0
3-Methylpentane (29) IM 110-230 0.3-3.0
2-Methylpentane (29) IM 110-230 0.3-3.0
2,3-Dimethylbutane (29) IM 110-230 0.3-3.0
2,ZDimethylbutane (29) IM 110-230 0.3-3.0

TABLE 4p
Other binary systems

X Refer- Experimental T(“C) P (MPa)

ences method
He-Propene (16) PGC -98 --33 2.3-12.0
Pentane-Pentene (52) IM 70 - 90 0.3- 3.3
Difluoroethane-Trichlo-
rotrifluoroethane (90) wsc 25 - 100 0.3- 3.0
Chlorodifluoromethane-
Trichlorofluoromethane (110) IM 25 - 100 0.3- 4.0
Acetone-Pentane (130) IM 170 - 227 3.0- 4.6
Butane-ZMethyl-
2-Propanol (134) cvsc 60 - 160 0.2- 4.3
Benzene-Tetrabydro-
naphthalene (139) CF 336.2 1.9- 3.0
Benzene-Quinolme (139) CF 296 - 437 up to 6.5
Dimethylether-1-Butene (155) GPR 20 - 96 0.2- 3.0
20

TABLE 4q
Ternary systems
System Refer- Experi- T(OC) P (MPa)
ences mental
method
Carbon dioxide- truns-deca- (5) IM 12 - 38 4.5- 8.0
hydronaphthalene-Eicosane
Carbon dioxide- trans- (5) IM -5- 41 2.5- 9.0
decahydronaphthalene-
2-Methylnaphthalene
Carbon dioxide-Nitrogen- (7) GPR -3 4.0- 11.0
Methane
(165) GPR -53 - -33 6.1- 12.2
Carbon dioxide-Nitrogen- (81) IM 21 - 28 5.8- 9.0
Nonadecane
Carbon dioxide-Hydrogen- (38) CF 270 - 390 5.0- 25.0
Tetrahydronaphthalene
Carbon dioxide-Hydrogen- (39) CF 270 - 430 5.0- 25.0
Quinoline
Carbon dioxide-Methane- (50) IM -87 - -69 3.9- 5.8
Hexane
Carbon dioxide-water- (53) GPR 24 - 49 2.5- 8.0
Diethyleneglycol
Carbon dioxide-water- (53) GPR 24 - 49 2.5- 8.0
Triethyleneglycol
Carbon dioxide-Propane- (81) IM 24 - 36 5.3- 7.3
Nonadecane
Carbon dioxide-Butane- (62) IM 71 9.6
Decane
Carbon dioxide-Butane- (62) IM 71 9.6
Butylcyclohexane
Carbon dioxide-Butane- (62) IM 71 9.6
Butylbenzene
Carbon dioxide-Toluene- (67) GLPR 80 - 140 2.1- 13.1
l-Methylnaphthalene
Carbon dioxide-water- (80) CF 35 - 65 10.2- 17.0
Ethanol (200) GLPR 40- 60 7.6- 20.7
Carbon dioxide-Hydrogen- (108) CF 270 - 431 5.0- 25.0
l-Methylnaphthalene
Carbon dioxide-Nitrogen- (123) GPR -5o- 0 5.0- 12.5
Methanol
Carbon dioxide-Methane- (125) cvsc -83 - 29 up to 13.0
Hydrogensulfide
Carbon dioxide-water- (128) GPR -30 - 25 up to 5.5
Methanol
Carbon dioxide-Propane- (136) cvsc 40- 70 0.5- 3.2
Methanol IM
 21

TABLE 4q (continued)

System Refer- Experi- T(“C) P (MPa)

ences mental
method
Carbon dioxide-water- (142) GLPR 40- 60 2.0- 15.0
Butanol
Carbon dioxide-Methane- (145) GPR -46 - -15 6.9- 27.6
Hydrogen
Carbon dioxide-Hydrogen- (145) GPR o- 50 6.9- 27.6
Pentane
Carbon dioxide-water- (149) IM 40- 60 7.8- 12.2
2-Hydroxypropane (141) GLPR 60 9.0- 13.9
(174) IM 60 ll.l- 12.2
(180) GLPR 60 - 61 10.4- 12.2
Carbon dioxide- (150) CF 39 - 93 5.7- 14.2
1,4-Dimethylbenzene-
1,2-Dimethylbenzene
Carbon dioxide-Hexane- (151) cvsc 30 - 50 2.0- 8.6
1-Hexene
Carbon dioxide-1-Dodecanol- (152) cvsc 119 9.0- 35.0
Chlorotrifluoromethane
Carbon dioxide-1-Dodecanol- (152) cvsc 119 9.0- 33.0
Nitrogen
Carbon dioxide-1-Dodecanol- (152) cvsc 119 9.0- 33.0
Trifluoromethane
Carbon dioxide-Benzene- (156) CG 143 - 247 5.0- 14.8
Tetrahydronaphthalene
Carbon dioxide-Decane- (156) CF 70 - 247 5.0- 12.1
TetrahydronaphthaIene
Carbon dioxide-water- (158) CF 40- so 7.3- 13.9
Acetic acid
Carbon dioxide-water- (202) GLPR 40- 60 2.9- 15.0
Acetone
Carbon dioxide-Biphenyl- (176) wsc 54 - 98 10.6- 19.1
Dodecane
Carbon dioxide-water- (184) IM 135 - 520 3.0-300.0
Sodium chloride
Methane-Hydrogen- (22) CF 189 - 390 5.0- 25.0
TetrahydronaphthaIene
Methane-Nitrogen-Ethane (27) GPR -13- 7 5.0- 8.5
(83) IM -148 --129 2.7- 5.1
Methane-Ethane-Propane (98) IM -130 - 30 0.6- 4.6
Methane-Ethane-Pentane (172) GPR -20 - -20 0.6- 5.0
Methane-Ethane-Hexane (82) IM -79 - -70 4.8- 5.9
Methane-Ethane-Heptane (82) IM - 105 - -65 2.1- 6.1
Methane-Ethane-Octane (34) IM -75 - -54 4.0- 7.0
Methane-Ethane-Decane (190) CF 21 0.5- 9.5
Methane-Propane-Decane (190) CF 21 0.5- 9.5
22

TABLE 4q (continued)

System Refer- Experi- T(=‘C) P (MPa)

ewes mental
method
Methane-Butane-Decane (190) CF 71 OS- 5.6
Methane-Pentane-Dee (1%) CF 71 0.5- 10.1
Methane-Pentane-Octane (50) IM -81 - -73 4.2- 5.8
Methane-Hexane-Octane (50) IM -91 - -79 2.9 5.0
Methane-Nitrogen-Hexane (55) IM -109 - -83 2.2- 5.2
Methane-Nitrogen-Pentane (55) IM -141 - -93 1.2- 5.8
Methane-Nitrogen-Propane (83) IM -156 --113 1.4- 6.1
Methane-Hydrogen- (102) CF 269 - 431 5.0- 25.0
1-Methylnaphthalene
Methane-Hydrogen- (114) GPR - 133 5.0
Carbon monoxide (117) GPR -153 --133 2.9- 5.0
Methane-Nitrogen- (117) GPR -193 --129 3.4- 10.0
Hydrogen
Methane-Nitrogen- (117) GPR -153 --133 1.5- 4.0
Carbon monoxide
Methane-Water- (185) IM 365 - 526 40.0-263.0
Sodium chloride
Methane-Water- (185) IM 379 - 444 67.0-265.0
Calcium chloride
Hydrogen-Water-Quinoline (69) CF 189 - 349 5.0- 20.0
Hydrogen-Water- (70) CF 189 - 347 5.0- 20.0
3-Hydroxytoluene
Hydrogen-Water- (143) cvsc 200 - 350 lO.O- 30.0
Hexadecane
Hydrogen-Water-Benzene (143) cvsc 300 lO.O- 30.0
Hydrogen-Benzene- (143) cvsc 300 20.0
Hexadecane
Hydrogen-Tetrahydro- (96) CF 190 - 430 2.0- 25.0
naphthalene-
Diphenylmethane
Hydrogen-Tetrahydro- (96) CF 190 - 310 2.0- 25.0
naphthakne-
1,3-Dimethylbenzene
Ethene-Nitrogen-Methanol (132) GPR -33 - -13 4.0- 10.0
Ethane-Nitrogen-Methanol (131) GPR -33 - -13 1.5- 7.5
Ethane-Propane-Butane (118) cvsc 31 - 33 .0.6- 4.9
(121) cvsc 31- 34 4.3- 4.9
Water-Ethanol- (160) cvsc 50 1.3- 10.1
l,l-Difluoroethane
2-Butanol-Water-Butane (141) GLPR 43 - 175 0.5- 6.9
Ammonia-Biphenyl- (176) wsc 156.5 14.1
Dodecane
Ethane-Butane-Hexane (194) wsc 48 - 144 up to 7.6
 23

TABLE 4q (continued)

System Refer- Experi- T(“C) P (MPa)

ences mental
method
Ethane-Biphenyl-Dodeane (176) wsc 77 - 126 8.8- 12.8
1,2,3,4_Tetrahydro (177) IM 280 - 420 up to 360.0
naphthalene-
Decahydronaphthalene-
(trans)-Water
Difluoroethane- (90) wsc 25 - loo 0.3- 2.7
DichlorodifIuoromethane-
Trichlorotrifluoroethane

TABLE 4r
Multicomponent systems

System Refer- Experi- T(=‘C) P (MPa)

ences mental
method
Methane-Carbon dioxide- (124) wsc 37- 204 0.4-18.5
Hydrogen sulfide-Water
Nitrogen-Methane- (97) cvsc -lOO--40 2.0- 8.0
Carbon dioxide-
Hydrogen sulfide-
Ethane-Propane
Hydrogen-Water-Benzene- (143) cvsc 300 20.0
Hexadecane
Methane-Ethane- (36) wsc 104- 204 1.4-14.0
Propane-Toluene-
l-Methyhraphthalene
Glucose-Fructose-Water- (161) GLPR 45- 80 8.0-17.0
Ethanol-Carbon dioxide
Methane-Aromatic w-9 GLPR 130- 277 2.0-11.1
oil mixture
Hydrogen-Aromatic (170) GLPR 154- 268 2.4-10.5
oil mixture
Carbon dioxide- (171) GPR -2o- 20 0.7- 4.5
Rich gas mixture
Methane-Carbon dioxide- (173) GPR -3o- 10 0.7- 5.4
Rich gas mixture
Propane-Saturates rich oil (175) CF lOl- 140 3.1- 5.5
Propane-Aromatics rich oil (175) CF 120- 140 3.1- 5.5
24

DATA REFERENCES FOR TABLES 4a-4r

(1) Tiffin, D.L., DeVera, A.L., Luks, K.D. and Kohn, J.P., 1978. J. Chem. Eng. Data, 23,
45.
(2) Lee, J.I., Mather, A.E. and Otto, F.D., 1978. J. Chem. Eng. Data, 23, 78.
(3) Mraw, S.C., Hwang S.C. and Kobayashi, R., 1978. J. Chem. Eng. Data, 23, 135.
(4) Sebastian, H.M., Yao, J., Lin, H.M. and Chao, K.C., 1978. J. Chem. Eng. Data, 23,
167.
(5) Tiffin, D.L., Guzman, G., Luks, K.D. and Kohn, J.P., 1978. J. Chem. Eng. Data, 23,
203.
(6) Lin, Y.N., Hwang, S.C. and Kobayashi, R., 1978. J. Chem. Eng. Data, 23, 231.
(7) Somait, F.A. and Kidnay, A.J., 1978. J. Chem. Eng. Data, 23, 301.
(8) Sebastian, H.M., Simmick, J.J., Lin, H.M. and Chao, KC., 1978. J. Chem. Eng. Data,
23, 305.
(9) Kaira, H., Kubota, H., Robinson, D.B. and Ng, H-J., 1978. J. Chem. Eng. Data, 23,
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(10) Kaira, H., Ng, H-J., Miranda, R.D. and Robinson, D.B., 1978. J. Chem. Eng. Data, 23,
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(11) Ng, H-J. and Robinson, D.B., 1978. J. Chem. Eng. Data, 23, 326.
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24,146.
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24, 149.
(14) Simmick, J.J., Sebastian, H.M., Lin, H.M. and Chao, K.C., 1979. J. Chem. Eng. Data,
24, 239.
(15) Senturk, N.H., Kaira, H. and Robinson, D.B., 1979. J. Chem. Eng. Data, 24, 311.
(16) Garber, J.D. and Ziegler, W.T., 1979. J. Chem. Eng. Data, 24, 330.
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(18) Ng, H-J., Kaira, H., Robinson, D.B. and Kubota, H., 1980. J. Chem. Eng. Data, 25, 51.
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(23) Shiau, J.F. and Ziegler, W.T., 1980. J. Chem. Eng. Data, 25, 239.
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25, 246.
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 25

DATA REFERENCES FOR TABLES 4a-4r (continued)

(31) Sebastian, H.M., Lin, H.M. and Chao, K.C., 1980. J. Chem. Eng. Data, 25, 381.
(32) Li, Y.H., Dillard, K.H. and Robinson, R.L., Jr., 1981. J. Chem. Eng. Data, 26, 53.
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26

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 27

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28

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 29

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ACKNOWLEDGMENT

The authors thank C.N.R. Progetto Finalizzato Energetica for financial

support. In addition, R.E. Fomari gratefully acknowledges the award of a
fellowship from the Italian Government.
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32

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