Sei sulla pagina 1di 70

ELSEVIER

Fluid Phase Equilibria 106 (1995) 213-282

PJI

rligh-Prm Flaid-Ph Equilibri . ental MethodsandSystemsInmtigated(19m1-1993)

Rltlf Dohnla'b and C.~rd Brunnera

aTheaTnische Veffahrenstechnik, 772 Hamburg-Harbueg, 21071Hambmg, Germany

bcnrrent address: Bayer AG, ZF-TI47 5, 51368 Leverknsen,

Germany; coeresponding author

Received28 December1994;acceptedin finalform4 February1995

Mmraet

Experimental methods for the investigation of high-pressure phase equilibria are classified

and described. A

published between 1988 and 1993 is given. Vapor-liquid equilibria (VIE), liquid-liquid equili- bria 0.,LE), vapor-liquid-liquid equilibria (VLLE), the solubility of high-boiling substances in

supercritical fluids and the solubilityof gases in liquids are included.For the systems inve- stigated, the reference,the temperature and pressure range of the data, and the experimental method used for the measurementsis given in 28 tabhs.

Keywords: experiments,data, method,VLE highpressure, hydrocarbons,non-hydrocarbons

review of systems for which high-pressure phase-equilibrium data have been

1. Inn-oduction For many chemical processes and separation operations that are conducted at high pressures, knowledge of the phase behavior is of special interest. Other examples for the need of high-pressure phase equilibrium data are the simulation of petroleum reservoirs, enhanced oil recovery, the transportation and storage of natural gas, and the study of geological processes. In particular, the interest in supercritical-fluid extraction proces- ses has lead to an increase in the number of publications concerning high-pressure phase-equilibrium data. Fundamentals and applications of supercritical-fluid technology have been described in several monographs, e.g., McHugh and Krukonis 0994) and Brunner (1994). There are many ways to obtain information about the phase behavior of fluid mixtures. The direct measurement of phase-equilibrium data remains an important source of information, though it is difficult and expensive to take precise experimental data. There are several review articles about techniques for experimental investigation, e.g., by Tsiklis (1968), Schneider (1975), Eubank et al. (1980), Deiters and Schneider (1986) and by Fornari et al. (1990). Information about experimental equilibrium data is important, even when thermodynamic models are used to calculate the phase behavior of a mixture. Thermodynamic models can help to re- duce the number of experimental data points needed for a special design problem. But very often, at least some experimental data points are

0378-3812/95/$09.50 © 1995- ElsevierScienceB.V. All rights reserved SSDI0378-3812 (95) 02703-3

214 R. Dohrn, G. Brunner / Fluid Phase Equilibria 106 (1995) 213-282

needed to adjust interaction parameters of the model (Dohm, 1994). Reviews of high-pressure phase-equilibrium data in the literature have been published by several authors, e.g., by Hicks (1978), Knapp et al. (1981), covering the period from 1900 to 1980, and by Fornari et al. (1990), covering 1978 to 1987. This work gives an overview about systems for which high-pressure phase equilibrium data have been published from 1988 to 1993, including vapor-liquid equilibria (VLE), liquid-liquid equilibria (LLE), vapor-liquid-liquid equilibria (VLLE), the solubility of high-boiling substances in supercritical fluids, and the solubility of gases in liquids. This survey covers readily accessible journals, as listed in Table 1, as well as proceedings of meetings concerning phase equilibria and supercritical fluids. Of course, the expression high pressure is relative; we chose 1 MPa as the lower limit: a paper was considered to contain high-pressure data if at least one data point was measured at a pressure of 1 MPa or higher.

Table 1

Bibliographic Information

Journal

Number of papers

1978 - 19870

1988 - 19932)

Fluid Phase Equilibria

69

158

Journal of Chemical Engineering Data

92

115

Journal

of Supercritical

Fluids0

0

43

Industrial

and Engineering Chemistry Research

15

18

Journal of Chemical Engineering of Japana)

0

14

Canadian Journal of Chemical Engineering

3

13

Berichte der Bunsengesellschaft, Physical Chemistry

9

7

AIChE Journal

5

5

Journal of Physical Chemistry

3

5

Chemical Engineering Science

2

1

Journal of the Chemical Society / Faraday Transactions

1

1

1) Fornari et al. (1990); 2) This work; a) Not covered by Fornari et al. (1990) 4) The first issue of the Journal of Supercfifical Fluids appeared in 1988.

The interest in high-pressure phase equilibria, which started in the 1960s, is still increasing. In Table 1 the number of papers published from 1978 to 1987 (Fornari et al., 1990) is compared with the number published from 1988 to 1993. While in the first period each year about 20 publications containing phase-equilibrium data appeared, three times as many articles were published in the second period. With 158 publications from 1988 to 1993, Plum Phase Equilibria has become the leading journal of high- pressure phase-equilibrium data. More than 80~ of the information was

published in l;quid Phase Equih'bria, the Journal of Chemical Engineering Data, and the Journal of Supercritical Fluids.

R. Dohrn, G. Brunner / Fluid Phase Equilibria 106 (1995) 213-282

215

Experimental methods for the investigation of high-pressure phase equilibria can be divided into two classes, depending on how the composi- tion is determined: analytical methods (or direct sampling methods) and synthetic methods (or indirect methods).

2.1 An

ieatl m

hocls

Analytical methods involve the determination of the compositions of the coexisting phases. This can be done by taking samples from each phase and analyzing them outside the equilibrium cell at normal pressure or by using physicochemical methods of analysis inside the equilibrium cell under pressure, e.g., spectroscopic methods (designated by "$1~¢" in Tables 2 - 29) (e.g., Kaiser et al., 1992). Withdrawing a large sample from an autoclave causes a considerable pressure drop, which disturbs the phase equilibrium significantly. This pressure drop can be avoided by using a variable-volume cell ('Nrm°') (e.g., Staby and MoUerup, 1991) or by blocking off ("ltlo") a sampling cell from the equilibrium cell before pressure reduction (e.g., Dohrn et al., 1993). If only a small sample is withdrawn or if a relatively large equilibrium cell is used, the slight pressure drop does not affect the phase compositions significantly. Small samples can be withdrawn using capillaries ("Cap") (e.g., Matos et al., 1989) or special sampling valves ('%ral"), e.g., using HPLC-valves or fast-acting pneumatic valves (Lauret et al., 1994). Often sampling valves are directly coupled to analytical equipment, e.g., to a gas chromatograph (e.g., Danesh and Todd, 1990). A simple method to reduce the pressure drop during sampling by using a second autoclave has been proposed by Brunner et al. (1993). Depending on the attainment of equilibrium, analytical methods ("An") can be classified as constant-temperature methods ("ANT'), constant- pressure-and-temperature methods ("~') and constant-pressure methods

2.1.1 Constant-temperature

An equilibrium cell is charged with the substances of interest. After

the

constant temperature. At the beginning of the experiment, the pressure is

adjusted above or below the desired equilibrium value, depending on how equilibration will change the pressure. By stirring the mixture or by rocking the autoclave or by recirculating one or more phases, time for

pressure

equilibration

a

methods ("ANT')

has

been

desired

temperature

reached,

the

mixture

is

kept

at

of

the

phases

is

reduced.

After

some

time,

the

reaches

a

plateau.

The

pressure

can

be

readjusted,

by

adding

or

with-

drawing material

or

by

changing

the

volume

of

the

equilibrium cell.

Usually, the equilibration is continued for at least 30 minutes after the

216 R. Dohrn, G. Brunner / Fluid Phase Equilibria 106 (1995) 213-282

pressure plateau is sufficiently close to the desired value. Before analyzing the compositions of the coexisting phases, the mixture is given some time without stirring, rocking or recircuiation for the separation of the phases (e.g., W'aterling et al., 1991). Constant-temperature methods that use stirring or rocking to ensure a rapid approach to equilibrium are often called analytical-static methods. As opposed to recirculating methods, the mixture does not leave the equi- librium cell during the experiment. But, since the expressions "static cell" and "static method" are used by some authors for other experimental me- thods (e.g. for a synthetic method in a view cell or for a synthetic method using the material balance to determine solubilities of gases in liquids), we avoid the expression "static" in our classification. Recirculation of one or more phases has the advantage that the sampl- ing volume (e.g., the loop of a six-port valve) is fiUed isobarically. In this way problems are avoided which can be encountered when samples of light and heavy components are taken through capillaries (Renon et al., 1989; Brunner et al., 1994). When only the vapor phase is recirculated ("Vt~'), the vapor phase is withdrawn continually and passed back into the equilibrium cell through the liquid phase by the action of a magnetic pump (e.g., Knapp et al., 1990). Samples can be withdrawn by placing a sampling valve (e.g., Hart et al., 1992) or a sampling autoclave (e.g., Dohrn et al., 1993) in the recircu- lation loop. The liquid phase is usually analyzed by taking samples through capillaries. Recirculation of both the vapor and the liquid phase ('~'Ld~') has the advantage that sampling from both phases is possible without using capillaries (e.g., Kim et al., 1989). If a vibrating-tube densi- meter is installed in a recirculation loop, the density of the circulated phase can be determined easily. The pump should be turned off during density measurement to avoid errors due to pulsation (Wendland et al., 1993). Sometimes only the liquid phase is circulated ("Lgi~'), e.g., for the measurement of solubilities of gases in liquids (Chang, 1992) or for the measurement of liquid-liquid equilibria (Hooper et al., 1988). Constant-temperature methods need relatively simple and inexpensive laboratory equipment. If carried out carefully they can produce very reliable results.

2.1.2 Constant-pressure-and-temperature methods ("AnP~) In constant-pressure-and-temperature methods, often called dynamic methods, one or more fluid streams are pumped continuously into a thermostated equilibrium cell. The pressure is kept constant during the experiment by controlling an effluent stream, usually of the vapor phase.

R. Dohrn, G. Brunner / Fluid Phase Equilibria 106 (1995) 213-282

217

2.1.2.1 Continuous-flow methods (~~')

In a typical design of a continuous-flow method, high-pressure meter- ing pumps feed the preheated components into a mixer (often a static mixer) where the desired temperature is attained. The feed stream from the mixer is separated in an equilibrium cell into a vapor and a liquid phase. Effluents from both phases are withdrawn continually, depres- surized, accumulated and analyzed, usually after the experiment. The pressure is adjusted by controlling the effluent stream of the top phase. The interface level between the fluid phases in the equilibrium cell can be adjusted with the bottom-phase expansion valve. Although the interface level is usually determined visually, nonvisual methods were successfully used, e.g., with an AC impedance bridge technique (Hochgeschurtz et al.,

1993).

Continuous-flow methods have the advantage that sampling does not disturb the equilibrium. If larger samples are needed for analyses, the run time of the experiment can be extended to accumulate more material. Measurements at higher temperatures are possible without chemical cracking or polymerization reactions due to the short residence time of the components in the apparatus (Hutchenson et al., 1990). Continuous-flow methods can be used only for systems where the time needed to attain phase equilibrium is sufficiently short.

2.1.2.2 Semi-flow methods ('l~lPTSem')

only one phase is flowing while the other phase

stays in an equilibrium cell. Semi-flow methods are sometimes called single-pass flow methods or pure-gas circulation methods. For the mea- surement of vapor-liquid equilibria, a gas stream from a high-pressure cylinder is passed through two cells in series containing the liquid. The

In semi-flow methods,

first cell serves as a presaturator

and

the

second

cell

is

the

equilibrium

cell. Upon equilibration,

the

effluent

of

the

vapor

phase

is

reduced

in

pressure and directed to a trap where the condensed liquid is collected.

The

metrically with a wet test meter. Sarnples from the liquid phase are with- drawn through tubing, depressurized, and analyzed (Lee and Chao, 1988).

The major uncertainty is the possible lack of attainment of equilibrium.

quantity of the

gas coming

out

of the

trap

can be

determined

volu-

Semi-flow methods

can be also used to measure

the solubility of a gas

in

one for measuring vapor-liquid equilibria, but there is no need to deter- mine the composition of the effluent from the vapor phase (e.g., Huang et

al., 1988c). Many investigators

determine the solubility of a low-boiling (liquid or solid) substance in a supercritical gas (e.g., Di Giacomo et al., 1989). Only the composition of the vapor-phase effluent is analyzed, e.g., by using a multi-port sampling

a

liquid.

The

experimental

procedure

use

a

(nAI~T~I~')

method

is similar

("~~")

to

the

to

semi-flow

218 R. Dohrn, G. Brunner / Fluid Phase Equilibria 106 (1995) 213-282

valve (Sako et al., 1991b) or after expansion to atmospheric pressure. No samples from the condensed phase are taken.

2.1.3 Constant-pressure

An

alternative

to

methods ("AnF')

direct

measurements

of

pressure-temperature-liquid

mole fraction-vapor mole fraction (PTxy) data is the measurement of PTx data followed by a thermodynamic analysis. A fast and simple way to measure PTx data is the use of an ebulliometer, which is a one-stage total-reflux boiler equipped with a vapor-lift pump to spray slugs of equlibrated liquid and vapor onto a thermometer well (Olson, 1989). A mixture of known composition is brought to boil at a controlled pressure. The compositions of the liquid and the vapor phase change with time and reach a steady state which should differ insignificantly from the true equilibrium value. A thermodynamic analysis yields the phase composi- tions. Usually ebulliometry is used to measure low-pressure data. Recently, ebulliometers have been proposed (Olson, 1989; Wlsniewska et al., 1993) which can be used for pressures up to 3 MPa.

2a

m

.xts Cs

')

The idea of synthetic methods is to prepare a mixture of known com- position and then observe the phase behavior in an equilibrium cell. No sampling is necessary. The problem of analyzing fluid mixtures is replaced by the problem of "synthesizing" them (Deiters and Schneider, 1986). After known amounts of the components have been placed into an equili- brium cell, values of temperature and pressure are adjusted so that the mixture is homogeneous. Then the temperature or pressure is varied until the formation of a new phase is observed (Suppes and McHugh, 1989). Each experiment yields one point of the P-T-x phase envelope. Synthetic methods can be used where analytical methods fail, i.e., when a phase separation is difficult due to similar densities of the coexisting phases, e.g. near or even at critical points and in barotropic systems, where at certain conditions the coexisting phases have the same density. Because no sampling is necessary the experimental equipment can be rather inexpensive. Often, the experimental procedure is easy and quick (Schneider, 1975). For multicomponent systems, experiments with synthetic methods yield less information than with analytical methods, because the tie lines cannot be determined without additional experiments, e.g., refrac- tive index measurements (Bolz and Stephan, 1991).

2.2.1 Visual synthetic methods ("$yn~ff')

The

appearance

of

a

new phase

is usually detected

by visual

observa-

tion

of

the

resulting

turbidity

or

meniscus

in

a

view

cell.

The visual

synthetic

method

can

be

used

not

only

for

the

determination

of simple

R. Dohrn, G. Brunner / Fluid Phase Equilibria 106 (1995) 213-282

219

vapor-liquid equilibria, but also to study complicated phase behavior, e.g., multiphase equilibria (Jangkamolkulchai and Luks, 1989), to measure the solubitity of gases in electrolyte solutions (Rumpf and Maurer, 1993a), or for solid-liquid and solid-fluid equilibria (Hammam and Sivik, 1993). For isooptic systems where the coexisting phases have approximately the same refractive index, visual observation is impossible.

2.2.2 Non-visual

As an alternative to visual observation, other physical properties can be monitored to detect phase transitions. If the total volume of a variable-volume cell can be measured accurately, the appearance of a new phase can be obtained from the abrupt change in slope on the pressure- volume plot more accurately than by visual observation (Japas et al., 1992). Fogh et al. (1989) used a microwave technique to detect phase transitions.

synthetic methods ("$NnNon~)

2.2.3 Synthetic methods using the material balance ("$ynMat")

For systems with two degrees of freedom (e.g., binary two-phase equili- bria or ternary three-phase equilibria), the compositions are fixed when temperature and pressure are given. Tanaka et al. 0993) measured the phase densities and the total volume for different cell loads to calculate the phase compositions using the material balance.

2.1 Other Methods

Experimental methods for the investigation of phase equilibria that do not fall into the classification as described above shall be designated as other methods ("Oth"). One example is the chromatographic technique used by Bartle et al. (1990) to measure the solubility of polycyclic aromatic hydrocarbons in carbon dioxide.

3. smm

In

Tables

2

-

29,

the

following

information

about the systems

investigated is given: the reference, the temperature and pressure range of

the data and the experimental method used for the measurements.

abbreviations used to designate the experimental method have been

explained in the text above or are explained in the list of symbols.

e.g., for

the pressure drop during sampling or for the amount of substances needed, the volume of the equilibrium cell is also given. Tables 2 - 23 cover binary systems and Tables 24 - 28 cover ternary systems. Multicom- ponent systems are listed in Table 29.

The

Because the size of the equilibrium

cell can be of importance,

220 R. Dohrn, G. Brunner / Fluid Phase Equilibria 106 (1995) 213-282

Table 2

Binary systems: carbon dioxide + X

X

acetic acid

acetone

acetophenone

5-aminoindoh

2-amino-2-methyl-

1-propanol(AMP)

anisole

~-apo-8"-carotenal

arachidic acid

arachidyl alcohol

barium hexafluoro-

acetylacetonate

benzaldehyde

benzonitrile

benzophenone

benzylalcohol

bibenzyl

biphenyl

bixin

n-butane

1-butanol

2-butoxyethanol

bromobenzene

caffeine

caproic acid

capsaicin

Reference

 

Exp. Method and

Temp.

Pressure

 

Call Volume

(cms)

(K)

(MPa)

Laugier et al., 1990

 

AnTVal

Var

293-333

0.6-7.4

Gurdial et al., 1993

SynVis

n.a.

304-323

7.4-9

Traub & Stephan, 1990

AnTVal

68

308-333

0-6

Kato et al.,

1991

 

SynVisVLcirVar 100

298

0.5-6

Weng & Lee, 1992d

AnPTSem

300

313-348

2-16_5

Nakatani et al., 1989

AnTValY

n.a.

308

8.2-18.4

Ohgaki et al., 1988b

AnTVaIY

n.a.

308

8-17.5

Teng & Mather, 1989

AnTVcir

75

323.5

0-5

Kim et M., 1989

AnTVLcirVal

150

343-372

2.4-16.8

Park & Kim, 1991

AnTVLcirVal

50

333-398

4.1-18.3

Jay et

al.,

1991

 

AnTSpecY

12

288-323

5-50

Yau et al.,

1992

1993a

AnPTGon

n.a.

373-473

1-5.1

Iwai et al.,

AnPTSemY

315

308

8.9-23.7

M'Hamdi et al., 1992

AnPTSemY

130

423-443

12-22

Kim et al.,

1989

 

AnTVLcirVal

150

343-372

2.8-18.3

Walther & Maurer,

1992

AnPTGon

40

313-393

6.1-22.3

Walther & Maurer, 1993

AnPTCon

40

313-393

6.1-18.3

Walther & Maurer, 1993

AnPTCon

40

313-393

6-18

Graaf et al., 1992

SynNonY

508

421-565

1.9-3.1

Walther & Maurer, 1993

AnPTCon

40

313-393

6-20

Chung & Shing, 1992

AnTVal

n.a.

308-328

8.4-27.6

Chung & Shing, 1992

AnTVal

n.a.

308-328

7.9-27.1

Jan & Tsai,

1991

 

AnPTSemY

n.a.

373-573

1-5

Zhang et al., 1991

SynVis

n.a.

333-343

5.4-46.3

Jay et al., 1991

AnTSpecY

12

288-323

10-70

P.de Fernandez et al., 1989 AnTVcir n.a. 277-418

0.1-8.2

Shibata & Sandler, 1989a

AnTVLcirVal

100

310-410

0.3-8

Traub & Stephan, 1990

AnTVal

68

310

0-8

Weber, 1989a

AnTVLcir

65

309-394

0_3-5.7

Brown et al., 1989b

AnTVcir

n.a.

250-270

0-2.8

Jennings et al., 1992c

AnPTCon

40

314-337

4.5-12

Jennings et al., 1991

AnPTCon

40

314-337

4.6-11.7

Chang, 1992

AnTLcirX

58~

298

0.1-62

Gurdial et al., 1993

SynVis

n.a.

305-329

7.5-10.8

Wmkler & Stephan, 1991

AnTCap

n.a.

313

1-8

Chai Kao et al., 1993

AnTX

n.a.

321-337

0.4-9

Walther & Maurer, 1992

AnIrrC,on

40

313-393

6.1-16.3

Li

et aL,

1991

AnPTSemSpecYn.a.

313-368

8-29~

Li

& Hartland,

1992

AnPTSemSpecYn.a.

313-368

8-30

Bharath et al.,

1993

 

AnTVcir

n.a.

313-353

2.7-15.9

Knez, 1992

AnTVal

500

298-333

5-40

R. Dohrn, G. Brunner / Fluid Phase Equilibria 106 (1995) 213-282

Table 2 (matiamd)

Binary systems: carbon dioxide + X

221

X

Reference

Exp. Method and

Temp.

Pressure

 

Cell Volume (cm3)

(K)

(MPa)

capsanthin

Jay et

al.,

1991

AnTSpecY

12

288-323

5-50

carbon disulfide

Rdff et al.,

1992

AnTCap

n.a.

273-473

0.4-15.8

~carotene

Cygnarowicz et al., 1990

AnTVcirY

n.a.

313-343

21.2-43.9

Jay & Steytler, 1992

AnTSpecY

12

288-328

5-50

Jay et

al.,

1991

AnTSpecY

12

288-323

5-80

SMralrl, 1992

AnP~emValY

n.a.

308-323

9.8-29.8

catechol

Yau & Tsai, 1992a

AnPTSem

n.a.

398-473

1-5.1

cetyl alcohol

Iwai et al.,

1991

AnPTSemY

315

308

8.9-21.8

2-chloro-l-methyl-

bengcne

Walther & Maurer, 1992

AnPTCon

40

313-393

6.1-17.3

chlorobenzene

Walther & Maurer, 1992

AnPTCon

40

313-393

6.1-16.3

chlorodifluoromethane Roth et

al., 1992

AnTCap

n.a.

273-353

0.7-5.4

 

Wang et al., 1991

AnTVdrVal

13

263-283

0.3-5

cholesterol

Tun et al.,

1991

2MxPTCon

n.a.

313-333

10-25

cineole

Matos & Azevedo, 1989

AnTVal

30

318-323

7.8-9.8

Azevedo et al., 1988

AnTCap

30

313

7.1-8_3

cis-verbenol

Richter & Sovov~, 1993

AnPTSemY

12

313-328

5.09,9.8

citral

Di Giacomo et al., 1989

AnFlX3emY

200

308-323

3-11

copper acetylacetonate M'Hamdi

et M., 1992

An_WISemY

130

423-443

12-22

m-cresol

Lee & Chao, 1988

AnPTSem

300

308-328

2-24

cummin

Jay et al.,

1991

AnTSpecY

12

288-323

20-50

cyclohexane

Shibata & Sandler, 1989b

AnTVLdrVal

100

366-410

0.1-14.5

cyclohexanone

Chang, 1992

AnTLcirX

58.8

298

0.1-5.5

cyclopentane

Marathe & Sandier, 1991

AnTVLcirVal

100

366-412

3.6-11.9

Shah et al., 1991

AnTVcirVal

n.a.

276-493

0-12-9

n-decane

Adams et al., 1988

AnTVLdrVal

n.a.

313

1.4-7.8

Han et al.,

1992

AnTVcirVal

400

310

2-8

Chen et al., 1993b

AnTValVar

17

344444

0-20

Gurdial et al., 1993

SynVis

n.a.

306-324

7.7-10

1-decanol

Lain et al., 1990a

SynVis

9

270-307

3.2-7.6

dibenzothiophene

Mitra et al., 1988

AnPTSemY

n.a.

309-328

7.6-27.6

dichlorobenzene

Walther & Maurer, 1992

AnPTCon

40

313-393

6.3-18.3

dichloroethane

Sengupta et al., 1993

AnPTCon

30

313-323

6.2-7.6

diethylene glycol

Jou

et al.,

1989

AnTVcirBlo

150

313-333

3.4-14.1

diethylether

Wu, G.-W. et al., 1988

AnTVcir

n.a.

313

1.5-7

dilaurin

Ashour & Hammam, 1993 AnTValY

7.5

313-318

15-40

Hammam & Sivik, 1993

SynVis

1.62

303-333

0-20

2,6-dimethyl-

naphthalene

Iwai et al., 1993b

AnlY[SemY

120

308-328

7.9-14.6

2,7-dimethyl-

naphthalene

Iwai et al., 1993b

AnPTSemY

120

308-328

8.8-24.9

2,2-dimethylpropane

Leu & Robinson, 1988

AnTVal

Vat

313-423

0.3-8.3

Shah et al., 1990

AnTVcirVal

n.a.

261-423

0-8_3

diphenyl methane

Chung & Shing, 1992

AnTVal

n.a.

308-328

7.9-26.7

222 R. Dohrn, G. Brunner / Fluid Phase Equilibria 106 (1995)213-282

Table 2 (~

Binary systems: carbon dioxide + X

X

Reference

Exp. Method and Cell Volume (cmS)

1-dodecanol

Kordikowski&Schneider1993 AnT

n.0,.

H~Ischer et al., 1989

AnTCap

100

Spee & Schneider, 1991 AnT

1"1.0

dotriacontane

Spee &

Schneider, 1991

AnT

n.0,.

n-dotriacontane

Tsai & Yau, 1990

AnPTSemX

n.a.

Yau & Tsai, 1993

AnTValY

n.a.

n-eicosane

Kordikowski&Schneider 1993 AnT

n.0,.

Feng & Mather, 1992

AnTVdrX

1"1.0,.

Huang et al., 1988a

AnPTSemY

n.a.

ethane

Brown et al., 1988

AnTVdrVal

n.a.

ethanol

Jennings et al., 1992c

AnPTCon

4O

Jennings et al., 1991

AnPTCon

4O

Gurdial et al., 1993

SynVis

1"1.0,.

Suzuki et al., 1990a

AnTVLcirVal

n.a.

Suzuki et al., 1991

AnPTSemY

3OO

Hirohama&Takatsuka,1993aAnTVal

Yoon et al.,

Inomata et al.,

Feng et al.,

1993a

1989b

1988

AnTVLcirVal

AnPTCon

AnTVLcirVal

n.0,.

5O

n.0,.

IO0

M.

de la Ossa

et al.,

1990

AntrISemY

1"1.0,.

Nagahama

et al.,

1988

AnTVal

n.0,.

2-ethoxyethanol

Hiflscheret al.,1989

AnTCap

IO0

ethylbenzene Tan et al., 1991

AnTVcirCap

n.0,.

ethyl stearate (C18:0) Bharath et al., 1989

AnTVdr

500

ethyl oleate (G18:1)

Bharath et al., 1989

AnTVdr

500

Liong et al., 1992

AnPTSemV'mY

n.0,.

ethyl linoleate (C18:2) Bharath et al., 1989

AnTVdr

500

ethyl ester (C20:3)

Liong et al., 1992

AnPTSemVisY

1'1.0,.

ethyl ester (C20:4)

Liong et al., 1992

AnPTSemV-mY

n.a,.

ethyl ester (C20:5)

Bharath et al., 1989

AnTVdr

500

ethyl ester (C22:6)

Liong et al., 1991

SynVis

n.0,.

Liong et al., 1992

AnPTSemV'mY

n.a.

Bharath et al., 1989

AnTVcir

500

ethylene glycol

Jou

et al., 1990a

AnTVdr

n.0,.

Jou et al.,

1989

AnTVdrBlo

150

n-formyl morpholine Jou et al., 1989

AnTVcirVal

n.a.

fluorene Battle et al., 1990 fluorinated metal di-

OthY

.008

ethyldithiocarbamatesLaintz et al., 1991

AnTSpec

14.8

furfural Sako et al., 1991b

~emYCal

500

henelcosafluor-

n-dcosane

Wikramanayake&Enick,1991SynVis

Vat

n-heptane

Gurdial et al.,

1993

SynVis

n.a.

hexachlorobenzene

Madras et al., 1993

AnPTSemValX n.a.

Temp.

CK)

Pressure

O~P0,)

353

10-252

333

0-30

293-393

10-27.5

393

10-63

373-573

10-50

318-338

4.7-20.6

353-393

10-32

322-423

0.4-7.7

373-573

0.9-5

207-270

0.%32

314-337

4-11

314-337

5-5-10.8

305-325

7.6-9.7

313-333

0.5-10.8

313-333

1.1-10.2

283-308

1.1-7.1

313

0.6-7.5

290-5O4

2-6-3

304-308

3.3-72

313

2-8

312-313

0.5-10.7

393

14-18

308-328

1.3-8.4

313-333

1.5-18-3

313-333

1.1-18.6

313-373

10-25

313-333

2-17

313-373

10-25

313-373

10-25

313-333

2-20

304

7.4-75

313-373

10-25

313-333

1.9-21

298-398

0.1-20.3

313-333

2.4-15.1

298-403

0.5-7.1

308-323

8.3-20.7

323

102

343-421

2-243

296

3.5-62

305-323

7.5-9.2

298-318

11.5

 

R. Dohrn, G. Brunner / Fluid Phase Equilibria 106 (1995) 213-282

 

223

Table 2 (ameamd} Binary systems: carbon dioxide + X

 

X

Reference

 

Exp. Method and

Temp.

Fressure

 

Call Volume

(cm3)

(K)

(MPa)

n-hexadecane

D'Souza et al., 1988

 

AnTVLcirVal

100

314-353

7.7-16.1

Hiflscher et al., 1989

AnTCap

100

333-393

10-25

Kordikowski&Schneider1993

AnT

n.a.

353

10-252

Spee & Schneider, 1991

AnT

n.a.

294-413

10.1-25.6

van

der

Steen et al., 1989

Syr~on

n.a.

283-306

4.4-7.5

Tanaka et al.,

1993

 

SynMatX

100

313

1.7-6.4

1-hexadecanol

Kramer & Thodos,

1988

AnPTSemY

n.a.

318-338

14.2.-41.5

Yau & Tsai,

1992b

AnIrrSemY

n.a.

308-328

5-20-3

Htilscher et al., 1989

AnTCap

100

333

0-30

n-hexane

Gurdial et al., 1993

SynVis

n.a.

305-322

7.5-8.9

Koelliker & Thies, 1993

AnTCap

2500

293-473

1.3-22.3

1-he~anol

Gurdial et al.,

1993

 

SynVis

n.a.

306-312

7.7-8.4

Lain et al., 1990a

SynVis

9

217-312

0.5-8.4

n-hexatriacontane

Hong & Luks,

1991

SynVis

9

342-348

0.1-7.9

Yau & Tsai,

1993

AnTVaIY

n.a.

318-338

3-20.7

1-hexene

Jennings & Te~a, 1989

AnTVLcir

40

309-332

1.6-93

1-hexyne

Jenninge & Teja, 1989

AnTVLcir

40

309-332

2.1-8.4

hydrogen sulfide

Morris & Byers, 1990

AnTVcirVal

300

283

2-4

5-hydroxyindde

Nakatani

et al.,

1989

AnTValY

n.a.

308

9-19~

Ohgaki et al., 1988b

 

AnTValY

n.a.

308

7-17.5

indoh

OhgakJ et al., 1988b

AnTValY

n.a.

308

7-20

Sako et al.,

1988

Antr~emValY

100

308

5.4-20.4

Yamamoto, S. et al.,

1989

SynVis

100

302-319

1.6-24.4

indohacetic acid

Ohgaki et al., 1988b

AnTValY

n.a.

308

9-19.5

indoh-3-aldehyde

Nakatani et al., 1989

AnTValY

n.a.

308

7.9-15.8

Ohgaki et al., 1988b

AnTVaIY

n.a.

308

5-19

indole-3-

Ohgaki et al., 1988b

AnTValY

n.a.

308

7.5-19.5

carboxylic acid

Nakatani et al., 1989

AnTValY

n.a.

308

9.2-19.4

lauric acid

Bamberger et al., 1988

Anl~Con

69

313

7.7-24.8

Bharath et al., 1993

AnTVcir

n.a.

313-353

2.6-27.6

Maheshwari et al., 1992

An_WlX3emY

n.a.

308-318

13.9-20.7

Yau et al., 1992

An_WI'Con

n.a.

313-473

1-5.1

limonene

Matos & Azevedo,1989

AnTVal

30

318-323

8.5-9~

Di Giacomo et al., 1989

AnPTSemY

200

308-323

3-10

Azevedo et al.,

1988

 

AnTCap

30

313

7.1-8.3

linohic acid

Zou et al.,

1990a

AnTVLcirVal

n.a.

313-333

6.3-27.1

Maheshwari et al.,

1992

AntrI~emY

n.a.

313-333

13~-27.6

luthein

Jay et al., 1991

AnTSpecY

12

288-323

5-65

methane

Adisasmito et al.,

1991

AnTVal

150

273-287

1.4-10.9

Xu

et al.,

1992

AnTCap

500

288-293

5.1-8.1

Morris & Byers, 1991

AnTVcirVal

300

270-288

3-7.5

methanol

Roskar et al., 1992

SynVis

Vat

323-338

5.5-31.9

Gurdial et al., 1993

SynVis

n.a.

305-320

7.6-9.3

Hong & Kobayashi, 1988

AnTVcir

n.a.

230-330

0.7-10.6

Schlichting et al., 1993

AnFISemBlo

n.a.

241-282

0.4-2.6

Suzuki et al., 1990a

AnTVLcirVal

n.a.

313

0.6-7.7

Yoon et al., 1993a

AnTVLcirVal

50

313

0.7-6.8

Lemert & Johnston, 1989

SynVis

n.a.

380-384

8.2-21.1

224 R. Dohrn, G. Brunner / Fluid Phase Equilibria 106 (1995) 213-282

Table 2 (maiau~

Binary systems: carbon dioxide + X

X

Reference

 

Exp. Method and

Temp.

Pressure

 

Call Volume

(cm3)

(g)

(MPa)

methoxybenzene

Walther & Maurer, 1993

AnPTCon

40

313-393 5.6-16~5

5-methoxyindole

Ohgaki et al., 1988b

AnTValY

n.a.

308

8-17

Salm,

S.

et

al.,

1989

AnPTSemValY 100

308

7.1-19

2-methyl anisole

Park

&

Kim, 1991

AnTVLcirVal

50

333-393 6.4-192

3-methyl anisole

Park

&

Ydm, 1991

AnTVLcirVal

50

333-393 6-1.89

4-methyl anisole

Park

&

Kim,

1991

AnTVLcirVal

50

333-393 6.3-18.7

methylbenzoate

Weng & Lee,

1992c

AnPTSem

300

313-348 3-13.5

methyl diethyl- dithiocarbamates

Laintz et al., 1991

AnTSpec

14.8

323

102

2-methyl butane

Bian et al., 1993

AnTVal

500

377

2-9.3

methyl ester (DHA)

Liong et

al., 1991

SynVis

n.a.

304

7.4-7.5

methyl ester (EPA)

Liong et

al., 1991

SynVis

n.a.

304

7.4-7.5

methyl laurate

Wu, A.H.

et al., 1988

~n

7.1

313,333

8-14

methyl linoleate

Wu, A.H. et al., 1988

~n

7.1

313,333

8-20

Zou et al., 1990a

AnTVLcirVal

n.a.

313-333 3.8-20.3

Adams et al., 1988

AnTVLcirVal

n.a.

313-343 4.8-12.8

methyl myristate

Inomata et al., 1989a

AnTVcirVal

500

313-333 1.2-16

Wu, AJ-I. et al., 1988

AnPTCon

7.1

313, 333

1-14

1-methyl naphthalene

Chung & Shing, 1992

AnTVa]

n.a.

308-328 7.7-27.8

Kim et al., 1989

AnTVLcirVal

150

372

3.7-20.6

Lee & Chao, 1988

AnPTSem

300

308-328 2-24

2-methyl naphthalene

(::hung & Shing, 1992

AnTVaJ

n.a.

308-328 7.7-27.8

Yanagiuchi et al., 1991

AnTVcirVar

1000

394-435 3.7-16.6

Jan & Tsai, 1991

AnPTSemY

n.a.

373-423 1-5

methyl oleate

Yu et al.,

1992a

et al., 1988

1990a

AnTVLcirVal

n.a.

313-333 2.9-13.7

Wu, AM.

An]riW~n

7.1

313,333

8-15

Zou et al.,

AnTVLcirVal

n.a.

313-333 4-18~

Inomata et al., 1989a

AnTVcirVal

500

313-343 1.8-20

methyl palmitate

Inomata et al., 1989a

AnTVcirVal

500

313-343 1-18.3

2-methylpropane

Weber, 1989a

AnTVLdr

65

310-394 0.5-4.4

n-methylpyrrolidone

Mm~ieta-Guevara etal.,1988 SymMatX

n.a.

298-373 0,2-1.4

methyl stearate

Inomata et al., 1989a

AnTVdrVal

500

313-343 2.1-20.4

Wu, AM. et al., 1988

~n

7.1

313,333

1-20

methyl tert-butylether Wu, G.-W. et al., 1988 molybdenum hexa-

AnTVcir

n.a.

310-338

0.5-9.1

carbonyl

Warzinski et al., 1992

SynVisY

Vat

313-333 6.2-11.8

monoethano|amine

Shen & Li, 1992

AnTValX

n.a.

313-373 0.2-32

monolaurin

Ashour ~

Hammam, 1993

AnTValY

7.5

313-318 15-40

Hammam & Sivik, 1993

SynVls

1.62

298-323 0-20

myristic acid

Bamberger et al., 1988

AnPT~n

69

313

8~-24.9

Bmnetti et al., 1989

AnIYISemY

n.a.

313-323

20

Iwai et al., 1991

AnPTSemY

315

308

8.1-22~

Maheshwari et al., 1992

AnPTSemY

n.a.

308-333 13.9-41.9

naphthalene

Battle et al., 1990

OthY

.008

308-318 7-25

Jan & Tsai, 1991

AnPTSemY

n.a.

373-473

1-5

 

R. Dohrn, G. Brunner / Fluid Phase Equilibria 106 (1995) 213-282

 

225

Table

2 (mufimmi) Binary

systems:

carbon

dioxide

+

X

X

Reference

Exp. Method and

Temp.

Pressure

 

Cell Volume

(cms)

('K.)

(MPa)

 

1992

An'Wal

n.a.

308-338

6.2-26.4

Chung & Shing, Hong & Luks,

1992

 

SynVis

9

339-353

0.1-7.2

Iwai et al.,

1991

AnPTSemY

315

308

8.5-23.8

Madras et al.,

1993

AnPTSemValX

n.a.

308-328

10.6-10.8

Hansen & Bruno,

1993

AnTValX

n.a.

328

6.5-10.2

Mitra et al.,

1988

AnFTSemY

n.a.

30%328

7.7-27.6

Reverchon et a]., 1993b

AnPTSemY

50

308

9,14

Richter & Sovova, 1993

AnPTSemY

12

308

6.5-12

White & Lira,

1991

 

AnTVal

n.a.

332-340

6.9-24.9

Sako et a].,

1988

AnPTSemValY

100

308

12.2-20.4

Han

et al.,

1992

AnTVdrVal

400

318-328

8-30

Yanagiuchi et al.,

1991

AnTVcirVar

1000

394-435

3.7-16.6

Lemert & Johnston,

1989

SynVis

n.a.

325-338

10-27.5

1-naphthol

Jan & Tsai,

1991

AnYISemY

n.a.

393-473

1-5

2-naphthol

Lemert & Johnston,

1989

SynVis

n.a.

313-393

9-21

 

Jan & Tsai,

1991

1993

AnFTSemY

n.a.

413-473

1-5

naproxen

"ling et al.,

AnPTCon

n.a.

313-333

8.9-19.31

nitrogen

Xu

et al.,

1992

AnTCap

500

288-293

5.1-9.7

Brown et al., 1989a

AnTVcir

n.a.

220-270

0.5-13

Brown

et

al.,

1989b

AnTVcir

n.a.

250-270

1.8-14.1

n-nonadecane

Korcllknwski&Schndder1993 AnT

 

n.a.

303-393

10-30.3

n-nonacosane

AnPTSemY

n.a.

308-318

6.5-16.7

n-nonane

Moradinia & Teja, 1988 Gurdial et al., 1993

SynVis

n.a.

307-317

7.6-8.7

n-octacosane

AnPTSemY

50

308-318

8-15

 

Reverchon et al., 1993b Yau & Tsai, 1993

AnTValY

n.a.

308-328

4.8-20.5

Huang et al., 1988a

AnP'ISemY

n.a.

373-573

1-5

n-octane

Gurdial et al., 1993

SynVis

n.a.

307-325

7.6-9.4

 

AnlYPSem

300

313-348

1.5-11.3

1,8-octanediol

n-octadecane

Weng & Lee, 1992a Spee & Schneider, 1991

AnT

n.a.

393.2

10-98

Graaf et al., 1992

SynNonY

n.a.

421-565

19.5-30

1-octadecanol

Kramer & Thodos,

1989

AnP~emY

n.a.

318.338

13.9-45.5

 

Yau & Tsai,

1992b

AnlrPSemY

n.a.

302-338

4.8-20.4

1-octanol

Weng & Lee, 1992b

AnlYFSem

300

313-348

4-19

Lam et al.,

1990a

SynVis

9

250-309

1.8-8

oleic acid

Bharath et al., 1992

AnTVcir

n.a.

313-353

10-30

Brunetti et al., 1989

AnPTSemY

n.a.

313-333

20-30

Foster et al.,

1991

 

~emY

n.a.

308-318

9.6-20

Yu et

aL,

1992a

AnTVLcirVal

n.a.

313-333

3.4-31.1

Zou

et

al.,

1990a

AnTVLcirVal

n.a.

313-333

7.1-28.8

Maheshwari et al., 1992

AnF~em¥

n.a.

313-333

13.8-27.6

oxindole

Nakatani et al., 1989

AnTValY

n.a.

308

8.5-18.9

Ohgaki et al., 1988b

AnTValY

n.a.

308

9-18

palmitic acid

An_PTCon

69

313

8-24.8

 

Bamberger et al., 1988 Bharath et al., 1993

AnTVcir

n.a.

353-373

13.6-30.5

Brunetti et al., 1989

An_PTSem¥

n.a.

308-323

20-30

Iwai et al., 1991

AnPTSemY

315

308

9.9-23

Maheshwafi et al., 1992

AnPTSem¥

n.a.

308-328

13.9-41.2

Kramer & Thodos, 1988

AnPTSemY

n.a.

318-338

14.2-57-5

226 R. Dohrn, G. Brunner / Fluid Phase Equilibria 106 (1995) 213-282

Table 2 (cffi~mKl)

Binary systems: carbon dioxide + X

X

Reference

 

Exp. Method and

Temp.

Pressure

 

Cell Volume

(cma)

(K)

(MPa)

 

Ohgaki et al., 1989

AnTLcirY

200

298-313

7.9-18.7

Yau et al.,

1992

An_PTSem

n.a.

373-473

1-5.1

pedagonic acid

Peter & Jacob, 1991

AnTVal

n.a.

333

2-12

Schiemann et al.,

1993

AnTVLcir

2500

313-393

0.1-23

penicillin V

Ko et

al.,

1990

AnTSpec

n.a.

313-334

7.9-28

pentachlorophenol

Madras et al., 1993

AnPTSemValX n.a.

298-318

11~5

pentacosafluor-

n-eicosane

grlkramanayake&Enick, 1991 SynVis

Vat

296

4.6-6.2

pentacosafluor-

n-tetracosane

W'dcramanayake&Enick, 1991 SynVis

Vat

296

5.8-6.3

n-pentadecane

van der Steen et al., 1989 SynNon

n.a.

273-308

3.5-7.8

Tanaka et al., 1993

SynMatX

100

313

1.7-6.4

n-pentane

Cheng et al., 1989

AnTVcirVal

n.a.

252-458

0.2-9.6

Wu, G.-W. et al., 1988

AnTVcir

n.a.

311,329

1-9

Lemert & Johnston, 1989

SynVis

n.a.

333-337

8.8-26.3

Xu

et al.,

1991

AnTCap

500

343

0.6-9.1

Gurdial et al., 1993

SynVis

n.a.

306-322

7.4-8.1

1-pentanol

Gurdial et al., 1993

SynVis

n.a.

307-318

7.6-9.1

Jennings et al., 1992a

Anl~Con

40

314-337

5.2-11.9

Stab}, & Mollerup, 1993 AnTCap

Vat

283-373

2-17.3

pentene

Wu, G.-W. et al., 1988

AnTVcir

n.a.

303-329

1A-8A

phenanthrene

Battle et al., 1990

OthY

.008

308-328

10-24

Zhang et al., 1988

SynVis

40

353-365

3.8-24.1

Yau &Tsai,

1992c

 

AnPTSem.X

n.a.

423-523

1-5.1

phenol

Yau & Tsai, 1992a

An_W~em

n.a.

348-423

1-5.1

phenylacetic acid

Wells et al., 1990

AnPTSemY

n.a.

308-318

8.3-19.1

pheophyfin a

Jay et

al.,

1991

AnTSpecY

12

288-323

5-65

ot-pinene

Richter & Sovov~, 1993

AnIrlSemY

12

295-335

3.2-9~

poly(ethylene glycol)co0Daneshvat

et al., 1990

AnTVLcirVal

n.a.

323

1.4-26.4

poly(ethylene glycol)6mDaneshvar et al., 1990

AnTVLcirVal

n.a.

313-323

1.1-29

poly(ethylene glycol)m0Daneshvar et

al., 1990

AnTVLcirVal

n.a.

323

1.7-26.3

1-pmpanol

Suzuki et al., 1990a

AnTVLcirVal

n.a.

313-333

0.5-10.8

Suzuki et al.,

1991

AnPTSemY

300

313-333

1.4-10.5

Gurdial et al., 1993

SynVis

n.a.

307-320

7.5-9

2-pmpanol

Suzuki et al., 1991

AnIrP3emY

300

313-333

1.3-10.1

Gurdial et al., 1993

SynVis

n.a.

304-322

7.5-9.1

n-propylbenzene

Renon et al., 1989

 

AnTVal

n.a.

393-473

1.2-19.4

Renon et al.,

1989

AnTBlo

n.a.

313

1.1-6.9

Renon et al., 1989

AnTCap

n.a.

313

0.5-77

Renon et al., 1989

AnT

Vat

313-393

1.1-17.3

n-propylcyclohexane

Richon et al., 1992

AnTBlo

n.a.

313

1-7.8

Richon et al., 1992

AnTVal

n.a.

391-472

2-18.4

pmpylene carbonate

Murrieta-Guevara et al,1988AnT

n.a.

298-373

0-2.2

pyrazine