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Fluid Phase Equilibria

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / f l u i d

High-pressure fluid-phase equilibria: Experimental methods and systemsinvestigated (20002004)

Ralf Dohrn a,, Stephanie Peper b, Jos M.S. Fonseca c

a Bayer Technology Services GmbH, Fluid Properties & Thermodynamics, Geb. B310, D 51368 Leverkusen, Germanyb Helmut-Schmidt-University/University of the Federal Armed Forces Hamburg, Institute of Thermodynamics, D 22043 Hamburg, Germanyc Technical University of Denmark, Department of Chemical and Biochemical Engineering, DK-2800 Kgs. Lyngby, Denmark

a r t i c l e i n f o

Article history:Received 26 June 2009Received in revised form 12 August 2009Accepted 13 August 2009Available online 20 August 2009

Keywords:

ExperimentDataMethodVLE high pressureHydrocarbonsNon-hydrocarbons

a b s t r a c t

As a part of a series of reviews, a compilation of systems for which high-pressure phase-equilibriumdata were published between 2000 and 2004 is given. Vaporliquid equilibria, liquidliquid equilibria,vaporliquidliquid equilibria,solidliquid equilibria,solidvapor equilibria,solidvaporliquidequilib-ria, critical points, the solubility of high-boiling substances in supercritical fluids, the solubility of gasesin liquids and the solubility (sorption) of volatile components in polymers are included. For the systemsinvestigated, the reference,the temperature andpressure rangeof the data, andthe experimental methodused for the measurements are given in 54 tables. Most of experimental data in the literature have beengiven for binary systems. Of the 1204 binary systems, 681 (57%) have carbon dioxide as one of the com-ponents. Information on 156 pure components, 451 ternary systems of which 267 (62%) contain carbondioxide, 150multicomponentand complex systems, and129 systems with hydrates is given.Experimen-tal methods for the investigation of high-pressure phase equilibria are classified and described. Work onthe continuation of the review series is under way, covering the period between 2005 and 2008, andwillbe published in 2010.

2009 Elsevier B.V. All rights reserved.

1. Introduction

For the design and optimization of high-pressure chemical pro-cesses and separation operations, information on high-pressurephase equilibria and solubilities is essential. The simulation ofpetroleum reservoirs, enhanced oil recovery, carbon capture andstorage, the transportation and storage of natural gas, refrigerationand heat-pump cycles, and the study of geological processes areother examples for the need of high-pressure phase-equilibriumdata. The interest in old and new applications of supercritical fluids[13], like extraction,particle formation, impregnation and dyeing,cleaning, reaction, chromatography, injection molding and extru-sion, and electronic chip manufacturing, as well as the interest

in ionic liquids and green solvents, led to a continuation of theincrease in the number of publications concerning high-pressurephase-equilibrium data.

There are many ways to obtain information about the phasebehavior of fluid mixtures, but the direct measurement of phase-equilibrium data remains an important source of information,though it is difficult and expensive to take precise experimentaldata. Onthe other hand, for a company, it is very oftenmore expen-

Corresponding author. Fax: +49 214 30 81554.E-mail address:[email protected](R. Dohrn).

sive to use imprecise data or to estimate data a couple of timesover the years, if experimental data are not available. There areseveral review articles about techniques for experimental investi-gations[414].Information about experimental equilibrium datais important, even when thermodynamic models are used to calcu-late the phase behavior of a mixture. Thermodynamic models canhelp to reduce the number of experimental data points needed fora special design problem, but very often, at least some experimen-tal data points are needed to adjust interaction parameters of themodel[15].

Reviews of high-pressure phase-equilibrium data in the litera-ture have been published by several authors [8,10,13,14,1624].Some reviews cover a specific topic, like the solubility of cer-

tain substances in supercritical carbon dioxide, e.g., Bartle et al.[14]for solids and liquids, Gcli-stndag and Temelli[19,23,24]for lipids, and Higashi et al. [21] for high-boiling compounds,or for a specific binary system, like Diamond and Akenfiev [22]on carbon dioxide + water. Other reviews cover high-pressurefluid-phase-equilibria data that have been published in a spe-cific periods, e.g., Knapp et al. [17]covering 19001980, Fornariet al.[8] covering 19781987, Dohrn and Brunner[10]covering19881993, andChristov and Dohrn [13] covering 19941999. Thiswork gives an overview about systems for which high-pressurephase-equilibrium data have been published from 2000 to 2004,including vaporliquid equilibria (VLE), liquidliquid equilibria

0378-3812/$ see front matter 2009 Elsevier B.V. All rights reserved.

doi:10.1016/j.fluid.2009.08.008
http://www.sciencedirect.com/science/journal/03783812http://www.elsevier.com/locate/fluidmailto:[email protected]://localhost/var/www/apps/conversion/tmp/scratch_1/dx.doi.org/10.1016/j.fluid.2009.08.008http://localhost/var/www/apps/conversion/tmp/scratch_1/dx.doi.org/10.1016/j.fluid.2009.08.008mailto:[email protected]://www.elsevier.com/locate/fluidhttp://www.sciencedirect.com/science/journal/03783812


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(LLE), vaporliquidliquid equilibria (VLLE), the solubility of high-boiling substancesin supercritical fluids, and the solubility of gasesin liquids (GLE). Work on the continuation of the review series isunder way, covering the period between 2005 and 2008, and willbe published in 2010.

2. Literature search and evaluation

This survey covers the most important journals in the field ofhigh-pressure phase equilibria, as listed inTable 1;abbreviationof journal titles were used according to ISO 4 [25].To find can-didates for articles that are of interest for this review we used athree-stage search strategy. In Stage 1 we systematically searchedthe table of contents of all volumes that appeared between 2000and 2004 of the journals ofTable 1,checked in cases of doubt theabstracts and downloaded the article. Stage 1 yielded more than95% of the articles of interest. In Stage 2 we used the online searchfunction of the journals to search for certain keywords, like high-pressure, phase equilibrium or gas solubility. Stage 3 was onlystarted after the evaluation process of the articles of interest wasalmost finished. We identified important authors in the field ofhigh-pressure phase-equilibrium measurements and searched forother papers of these authors that might have been overlooked inStages 1 and 2. During the evaluation process of more than 700articles of interest, about 10% of the papers were found to be irrel-evant for this review, since they contain neither new experimentaldata nor the description of a new experimental apparatus, or themeasured data were not high pressure. Of course, the expressionhigh pressure is relative; we chose 1 MPa as the lower limit: apaper was considered to contain high-pressure data if at least onedata point was measured at a pressure of 1 MPa or higher.

The increase of interest in high-pressure phase equilibria con-tinues.Fig. 1shows an almost linear increase of articles publishedper year during the last 25 years. While in the early 1980s about20 articles on high-pressure phase equilibria were published eachyear, this number increases by 67 each year, so that in 2004 morethan 7 times as many articles appeared as in 1982. InTable 1,the

Table 1

Bibliographic information.

Journal Number of articles

19781987a 19881993b 19941999c 20002004d

J. Chem. Eng. Data 92 115 214 231Fluid Phase Equilibr. 69 158 182 206

J. Supercrit. Fluidse 0 43 73 115Ind. Eng. Chem. Res. 15 18 30 58

J. Chem. Thermodyn. 30 26Int. J. Thermophys. 23Phys. Chem. Chem.

Phys.f10 8 6 13

AIChE J. 5 5 1 10

J. Phys. Chem. B 3 5 1 4Chem. Eng. Sci. 2 1 4 4Can. J. Chem. Eng. 3 13 8 1Green Chemistryg 0 0 0 1

J. Chem. Eng. Jpn. 14 4 0Other journals 16 5

Total 199 380 569 697

Abbreviation of journal titles according to ISO 4[25]. (): not covered in the reviewof the period.

a Fornari et al.[8].b Dohrn and Brunner[10].c Christov and Dohrn[13].d This work.e The first issue ofThe Journal of Supercritical Fluidsappeared in 1988.f Before 1999: Berichte der Bunsengesellschaft fr Physikalische Chemie and J.

Chem./Faraday Trans.g

The first issue ofThe Green Chemistry

appeared in 1999.

Fig.1. Increasein thenumberof articles publishedper yearduringthe last25 years.

numberof paperspublished in differentjournals from 1978to 1987

[8]is compared with the number published from 1988 to 1993[10],from 1994 to 1999[13],and from 2000 to 2004 (this work).Authors tend to submit their publications on high-pressure phase-equilibrium data to a rather limited number of mostly specialized

journals. More than 80% of the information was published in thethree major journals of high-pressure phase equilibria: the Journalof Chemical Engineering Data,Fluid-Phase Equilibria, andThe Journalof Supercritical Fluids. As compared to our previous reviews [10,13],we no longer coverZeitschrift fr Physikalische Chemie since no rele-vantarticleswerefoundinthisjournalfortheperiodbetween2000and 2004, and ELDATA (International Electronic Journal of Physico-Chemical Data), which had 13 relevant articles in the previousperiod (19941999), but ceased to appear in 1999. We includedInternational Journal of Thermophysics asa new journal.And we alsoincludedGreen Chemistry, which first appeared in 1999 and showsrising coverage of high-pressure phase equilibria due to increas-ing interest in the solubility of volatile components in ionic liquids,particularly in the period of the coming review that will cover 2005and 2008.

3. Experimental methods

Particularly at high pressures, the measurement of phase equi-libriais the most suitable method to determine the phase behavior,which often is far more complex than at ambient and moderatepressures. Due to large deviations from ideal behavior, the pre-diction of high-pressure phase equilibria is less accurate than atlower pressures. Another difficulty of using predictive methods is

the fact that molecules of interest for high-pressure applications,particularly supercritical fluid extraction, can be large and containseveral functional groups. Many differentmethods areusedto mea-sure high-pressure phase equilibria. The reason is that not a singlemethod is suitable to determine all different phenomena. To thereader the variety of experimental methods is even more confusingsince different authors use different names for the same experi-mental method. Expressions like static or dynamic are used inconnection with many different methods.

Therefore, an overview and a classification of experimentalmethods for the determination of high-pressure phase equilibriaare given in this chapter. The classification includes a unique nameand an abbreviation of the name for each method. InTables 356,listing the investigated systems, information on the experimental

method used to determine the data is included.


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R. Dohrn et al. / Fluid Phase Equilibria 288 (2010) 154 3

Fig. 2. Classification of experimental methods for high-pressure phase equilibria.

The classification of experimental methods for the investiga-tion of high-pressure phase equilibria that has been used in theprevious reviews[10,13]has been further refined for this work(Fig. 2).There are two main classes, depending on how the com-positions of the equilibrium phases are determined (analytically ornot) and whether the mixture to be investigated has been prepared(synthesized) with precisely known composition or not: analyticalmethods and synthetic methods.

3.1. Analytical methods (An)

Analytical methods (designated with An) involve the analyticaldetermination of the compositions of the coexisting phases. Whenthe equilibrium cell is filled with the components at the beginningof the experiment, the overall composition of the mixture is notprecisely known, only so far that the mixture under desired con-ditions (Pand T) separates into two or more phases that are tobe investigated, e.g., into a liquid and a vapor phase when VLE isto be measured. The composition of the phases is analyzed eitherwith sampling and analysis under ambient pressure or withoutsampling by using physicochemical methods of analysis inside theequilibrium cell under pressure.

Analytical methods with samplingcan be classified, depend-ing on the attainment of equilibrium, into isothermal methods

(AnT), isobaricisothermal methods (AnPT) and isobaric methods(AnP). Withdrawing a large sample from an autoclave causes aconsiderable pressure drop, which disturbs the phase equilibriumsignificantly. This pressure drop can be avoided by a variable-volume cell (Var)[26],by using a buffer autoclave in combinationwith a syringe pump[27],or by blocking off (Blo) the samplingvolume from the remaining content of the equilibrium cell beforepressure reduction [2830]. Sane et al. [31] use an electronicsyringe pump to keep the pressure in a variable-volume cell con-stant during sampling. If only a small sample is withdrawn or ifa relatively large equilibrium cell is used, the slight pressure dropdoes not affect the phase compositions significantly. The largestequilibriumcell(volumeof9dm3)usedinthearticlesofthisreviewwas used by the late Danesh and co-workers [32] to measure phase

equilibria in gas condensate systems.

Small samples can be withdrawn using capillaries (Cap)[33]orspecial sampling valves (Val), e.g., using HPLC-valves[34]or fast-acting pneumatic valves, like the rapid on-line sampler-injector ofRichon [35]. Oftensamplingvalvesaredirectlycoupledtoanalyticalequipment, e.g., to a gas chromatograph[36],a high-performanceliquid chromatograph[37],or a supercritical fluid chromatograph[34].For sampling from multiphase systems (e.g., VLLE) a movablesampling needle[38]can be used.

The smallest equilibrium cell of all articles from this reviewusing an analytical method with sampling was used by Bahramifaret al.[39]:only 0.5 cm3 volume with a sampling loop of 23mm3.

The largest relative sample (14%) from a constant volume cell wastaken by Garmroodi et al. [40]:a 143mm3 sample from a 1cm3

equilibrium cell.Sometimes, equilibrium cells used for analytical methods are

equipped with one or more windows for visual observation of thecell content (Vis). Secuianu et al. [41]use a variable-volume cellwith two sapphire windows where one of the windows acts as apiston.

Analytical methods without samplinguse a physicochemicalmethod of analysis inside the equilibrium cell under pressure.These are mainly spectroscopic methods (AnSpec), e.g., Andersenet al.[42],gravimetric methods (AnGrav), e.g., Sato et al. [43],orother methods (AnOth), e.g., Boudouris et al.[44].These methodsavoid the problems related to sampling from a high-pressure cell.

The main advantage of analytical methods is that they can beused for systemswith more than 2 components without significantcomplications. When the compositions of all phases are analyzed,each experiment yields complete information on the tie-line(s).

3.1.1. Analytical isothermal methods (AnT)

Characteristic for isothermal methods is that the temperatureof the system stays constant during the equilibration process, e.g.,when the system is in contact with a heat reservoir. The other equi-librium properties, like the pressure and the composition of thephases, reach equilibrium values, depending on other variables,like mole numbers and volume. At the beginning of an experiment,an equilibrium cell is charged with the substances of interest. Thepressure is adjusted above or below the desired equilibrium value,

depending on how equilibration will change the pressure. After


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the desired temperature has been reached, the mixture is kept ata constant temperature. By stirring the mixture or by rocking theautoclaveor by recirculating oneor more phases, time forequilibra-tion of the phases is reduced.After some time, the pressure reachesa plateau.The pressurecan be readjusted, by addingor withdrawingmaterial or by changing the volume of the equilibrium cell. Usually,the equilibration is continued for at least 30min after the pressureplateau is sufficiently close to the desired value. Before taking sam-ples from the coexisting phases, the mixture is given sufficient timewithout stirring, rocking or recirculation for the separation of thephases[41].Otherwise the sample might not be homogeneous butcontain material from anotherphase, e.g., droplets, bubbles or solidparticles.

For the measurement of solidliquid equilibria in wax systems,Pauly et al. [45] used an isobaric and isothermal filtration stepto ensure that the liquid phase to be sampled is free of solidparticles. This was performed in an equilibrium cell with twovariable-volume chambers connected via a filtration system (a discof sintered steel with 3m of porosity).

Isothermalmethodsthatusestirringorrockingtoensurearapidapproach to equilibrium are often called analytical-static methods.As opposed to recirculatingmethods,the mixture does notleavetheequilibrium cell during the experiment. But, since the expressions

static cell and static method are used by some authors for otherexperimental methods (e.g., for a synthetic method in a view cellor for a synthetic method using the material balance to determinesolubilities of gases in liquids), we avoid the expression static inour classification.

Sampling through capillaries can lead to differential vaporiza-tion and scattering results, especially for mixtures containing lightand heavy components when no precautions have been taken toprevent a pressure drop all along the capillary[46].Differentialvaporization can be avoided with an experimental design thatensures that most of the pressure drop occurs at the end of thecapillary close to the chromatographic circuit, e.g., Richon and co-workers [47] used a micro-stem ending with a nose entering insidethe capillary to reduce the cross-sectional area at the end of the

capillary. Another possibility to reduce sampling problems is therecirculation of one or more phases, having the advantage thatthe sampling volume (e.g., the loop of a six-port valve) is filledisobarically.Disadvantagesofarecirculationaretheneedforawell-working pump with only little pressure drop and the need for auniform temperature field to avoid partial condensation or vapor-ization in the recirculation line. Therefore, recirculation methodsare not suitable in the region close to thecritical point where smallchanges in temperature and pressure have a strong influence onthe phase behavior[11].

When only thevaporphaseis recirculated(Vcir), it is withdrawncontinually and passed back into the equilibrium cell through theliquid phase by the action of a pump, e.g., Mather and co-worker[48].Samples can be withdrawn by placing a sampling valve in the

recirculation loop[37]or by blocking off a volume between twovalves in the recirculation loop[49].The liquid phase is usuallyanalyzed by taking samples through capillaries. Laursen et al.[50]proposed a simple VLE equipment with vapor-phase recirculationthat allows liquid phase sampling to measure the gas solubility insubstances with high stickiness and viscosity, like wood resins.

Recirculation of both the vapor and the liquid phase (VLcir) hasthe advantage that sampling from both phases is possible withoutusing capillaries[51,52]. If a vibrating-tube densimeter is installedin a recirculation loop, the density of the circulated phase can bedetermined easily. The pump should be turned off during densitymeasurementtoavoiderrorsduetopulsation[52]. Sometimesonlythe liquid phase is circulated (Lcir), e.g., for mixing, for blockingoff a large liquid phase volume from the equilibrium cell before

pressure reduction [53], for the measurementof liquidliquid equi-

libria or for the measurement of solubilities of gases in liquids[54].

In a special kind of blocking off a part of the equilibrium cellthe sampling volume is within the equilibrium cell. We call thismethod in situ sampling (AnTIns). It can be used for the mea-surement of the solubility of solids in supercritical fluids. Shermanet al.[55]put an excess amount of solute in a glass vial, cappedwith coarse filter paper, in the equilibrium cell. After equilibrationand careful depressurization, the vial is removed and weighed. Thesolubility can be calculated from the difference of the initial andfinal mass of the solute in the vial and the difference of the volumeof the equilibrium cell and the vial. As modification, Galia et al.[56] used three vials, of which only one was initially filled with thesolute.

Nikitin et al. [57,58] used an alternative technique which avoidssampling from a high-pressure cell, for sorption measurementsof carbon dioxide in polystyrene. Equilibration, the absorption ofvolatile component in the polymer, might take several hours. Then,a fast depressurization procedure (


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and salt nucleation studies in near-critical aqueous solutions. Thecrystalline phases were observed using Raman spectroscopy.

Continuous-flow methods can be used only for systems wherethe time needed to attain phase equilibrium is sufficiently short.

3.1.2.2. Semi-flow methods (AnPTSem). In semi-flow methods, onlyone phase is flowing while the other phase stays in an equilib-rium cell. Semi-flow methods are sometimes called single-passflow methods, gas-saturation methods or pure-gas circulationmethods. A gas stream from a high-pressure cylinder is passedthroughtwocellsinseriescontainingtheliquid.Thefirstcellservesas a presaturator and the second cell as equilibrium cell. Uponequilibration, the effluent of the vapor phase is reduced in pres-sure and directed to a trap where thecondensed liquid is collected.The quantity of the gas coming out of the trap can be determinedvolumetrically, e.g., with a wet test meter.

Most often, only the composition of the vapor phase is ana-lyzed (AnPTSemY), for example to determine the solubility of alow-boiling (liquid or solid) substance in a supercritical gas [65].The composition of the vapor-phase effluent can be determined inmany different ways, e.g., by using a spectroscopic method [66],by using a multi-port sampling valve and subsequent HPLC anal-ysis or after expansion to atmospheric pressure using cold traps,

an absorption bath, or a chromatography column filled with anappropriate adsorbent for the solute studied[67]. Forthesekindsofmeasurements (AnPTSemY), no samples from the condensed phaseare taken.

When a semi-flow method is used for the measurement ofvaporliquid equilibria AnPTSemXY, the composition of the liquidphase needs to be determined. Therefore, a sample from the liquidphase is withdrawn through tubing, depressurized, and analyzed[68]. Semi-flow methods can also be used to measure the solubilityof a gas in a liquid, e.g., Tan et al. [69].The experimental proce-dure (AnPTSemX) is similar to the one for measuring vaporliquidequilibria, but there is no need to determine the composition of theeffluent from the vapor phase.

Tuma et al.[70]used a modified supercritical fluid chromato-

graph (SFC) to measure the solubility of dyesin carbon dioxide. Thecolumn was filled with finely pulverized dyestuff. Analysis of thevapor-phase stream is done by VIS-spectroscopy (AnPTSemYSpec).

The major uncertainty of all flow methods is thepossible lack ofattainment of equilibrium. Sauceau et al. [71]used an equilibriumcell with three compartments, which is equivalent to three cells inseries. Another difficulty is the partial condensation of the solutefrom the saturated vapor stream in the tubing, particularly in andafter the expansion valve. This undesired variable hold-up of thesolute can lead to scattering results in the order of 10%[72].Tocollect precipitated solute at the end of an experiment from thetubing and from the expansion valve, Takeshita and Sato [73] use astream of carbon dioxide after having blocked off the equilibriumcell.

Ferri et al.[74]describe an experimental technique that allowsto measure high concentrations of dyestuff in a supercritical fluid.They use a second pumpto stabilize the flow rate ofthe fluidin theextractor, damping the pulses of the first pump. Glass wool beforeand after the packed bed guarantees a uniform flow distributionand prevents particle entrainment. A line by-passing the extractorallows solubility measurements at high concentrations. It dilutesthe saturated fluid stream with clean carbon dioxide and reducesthe risk of valve clogging and flow rate instability.

To overcome the problems connected to depressurization,Pauchon et al. [75] developed a semi-flow method that workswithout pressure reduction. The effluent vapor-phase flows intothe top part of an autoclave which is filled with mercury. Theuse of mercury, acting as a piston, allows obtaining a precise

adjustment of the vapor flow and avoids pressure changes that

produce solute precipitation.Sampling at isobaricconditionsis per-formed with a six-port valve. Special attention must be taken intoaccount during the regeneration of mercury and cleaning of theapparatus.

3.1.2.3. Chromatographic methods (AnPTChro).Chromatographicmethods measure solute retention in a chromatographic columnand connect it with the Gibbs energy of solute transfer betweenthe stationary and the mobile phase. Roth[76]gives a review onapplications of SFC for the determination of the relative values ofsolute solubilities in supercritical fluids, and on the determinationof solute partition coefficients between a supercritical fluid andthe stationary phase. In SFC, the thermodynamic analysis of soluteretention is more difficult than in GC because the uptake of themobile phase fluid by the stationary phase is no longer negligi-ble. Chromatographic methods have as advantage the possibilityto determine equilibrium properties and diffusion coefficients inone experiment[77].

Sato et al.[78]used a chromatographic method (AnPTChro) tomeasure the vaporliquid equilibrium ratio of n-hexane at infinitedilution in propylene + impact polypropylene copolymer, while todetermine the solubility of propylene in the polymer they used thesynthetic isothermal method (SynT).

Chester[79]reviewed a chromatographic technique, which hecalls flow injection peak-shape method that allows to deter-mine thepTcoordinates of the vaporliquid critical locus of binarysystems. It can be implemented using open-tubular SFC instru-mentation by replacing the SFC column with several meters offused-silica tube. This tube may be deactivated but is not coatedwith a stationary phase. The procedure to map a critical locusinvolves selecting a temperature, then making injections at variouspressures while looking for the pressure where the peaks changefrom their rectangular appearance (=liquid+vapor phase in thecolumn) to distorted Gaussian (=homogeneous phase in the col-umn). This transition pressure provides an estimate of the mixturecritical pressure corresponding to the oven temperature.

3.1.3. Analytical isobaric methods (AnP)The boiling temperature of a mixture is measured at isobaric

conditions and phase compositions are determined after samplingand analysis. Typically, isobaric experiments are performed in anebulliometer (from latin ebullioto boil, to bubble up), which isa one-stage total-reflux boiler equipped with a vapor-lift pump tospray slugs of equilibrated liquid and vapor onto a thermometerwell. As opposed to the more frequently used synthetic isobaricmethod (SynP), vapor and liquid streams are separated, collectedand can be sampled and analyzed. The compositions of the liquidand the vapor phase change with time and reach a steady statewhich should differinsignificantly from the true equilibrium value.Usually, the analytical isobaric method is used to measure low-pressure data. Then, it is often called the dynamic VLE method.

3.1.4. Analytical spectroscopic methods (AnSpec)

Spectroscopic methods allow analyzing the compositionof the phases at high pressures without having to take sam-ples, e.g., by using near infrared spectroscopy [42]. CruzFrancisco et al. [80] investigated the phase behavior oflecithin + water + hydrocarbon + carbon dioxide mixtures usinga2H NMR technique in combination with light microscopy.

Aizawa et al.[81]developed a high-pressure optical cell for theinvestigation of absorption and fluorescence phenomena using atotsu (denoting the shape) type window. The protruding part ofthe window acts as a light-guide and enhances the laser powerimparted onto the sample in the monitoring light.

Shieh et al. [82] studied theeffect of carbon dioxideon the mor-

phological structure of compatible crystalline/amorphous polymer


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blends by means of small angle X-ray scattering (SAXS) with themeasurement of absolute scattering intensity.

The advantage of avoiding the trouble with taking samples isoften overcompensatedby the need of time consumingcalibrationsat high pressures. Only 1.5% of all systems covered in this reviewhave been investigated with a spectroscopic method.

3.1.5. Analytical gravimetric methods (AnGrav)

With gravimetric methods the mass of a condensed phase (e.g.,a polymer[43]or an ionic liquid[83])in phase equilibrium witha fluid phase is measured. Using additional information, like thephase densities, the phase compositions can be determined. Pala-mara et al.[84]placed the entire high-pressure cell on a balanceand performed the equilibration under isobaric conditions. Theweight of the cell and attached valve is critical because commer-cially available analytical balances sensitive enough to performthese measurements have low maximum load capacities. In thestudy of Palamara et al.[84]the cell and attached valve weighedapproximately 190 g.

Cutugno et al.[85]placed a quartz spring balance and Mooreand Wanke [86]placed an electro microbalance within a high-pressure cell to measure sorption of gases in polymers. Kleinrahmand Wagner [87] developed a unique balance, so-called a magnetic

suspension balance, for accurate measurements of fluid densities.It has the main advantage that the sample and the balance are iso-lated. An electronically controlled magnetic suspension coupling isused to transmit the measured force from the sample enclosed in apressure vessel to a microbalance. The suspension magnet, whichis used for transmitting the force, consists of a permanent mag-net, a sensor core and a device for decoupling the measuring-load.An electromagnet, which is attached at the underfloor weighinghook of a balance, maintains the freely suspended state of the sus-pension magnet via an electronic control unit. Using this magneticsuspension coupling, the measuring force is transmitted contact-lessly from the measuring chamber to the microbalance, whichis located outside the chamber under ambient atmospheric con-ditions. Several investigators used a magnetic suspension balance

to measure the solubility and diffusivity of volatile components inpolymers, e.g., Sato et al.[88].

Gravimetric methods need corrections for buoyancy. Therefore,particularly at high pressures, exact information on the density ofthe fluid phase and on the density and volume of the condensedphase is essential.

3.1.6. Other analytical methods (AnOth)

Like in gravimetric methods, quartz crystal microbalances canbe usedto determine the solubility ofa gas in a polymer by measur-ing the mass of the polymer in equilibrium with the gas. From thebasic principle, it is not a gravimetric measurement, so that buoy-ancy effects play a different role. Quartz crystal microbalances arebased on the piezoelectric effect observed in a AT-cut quartz crys-

tal. Thecrystal under the influence of an applied alternating electricvoltage undergoes a shear deformation which becomes maximumat a certain frequency called theresonance frequency[44]. This res-onance frequency depends on the mass, and thus any mass changewill result in a respective frequency shift. The sorption experi-mentinvolvesmeasurement of theresonance frequency of thebare(clean) crystal, of the same crystal coated with polymer, and of thecoated crystal after the polymer reaches equilibrium with a gas, allat the same controlled temperature. Concurrently, the resonancefrequency of a reference crystal is also measured under the sameconditions in order to compensate any temperature or pressureeffects.Parketal. [89] examinedtheeffectoftemperaturedeviationand pressure change on the frequency shift by measuring the fre-quency change of an uncoated crystal under high-pressure carbon

dioxide.

Guigard et al. [90]further developed the quartz crystal tech-nique to measure low solubilities of metal chelates in supercriticalfluids. A small mass of solute was deposited on the crystal and sol-ubility was measured by observing the crystals frequency changeas this solute dissolves in the supercritical fluid.

Mohammadi et al. [91] used a quartz crystal balance as anextremely sensitive detector for the appearance of hydrates. 1 ngmass change results in a 1Hz frequency change. Concerning theclassification of methods this is not an analytical method (AnOth),but a non-visual synthetic method (SynNon).

As compared to conventional methods, such as gravimetric(AnGrav) or pressure decay (SynT), a much higher sensitivity forthe determination of mass changes can be achieved with a quartzmicrobalance. Therefore, smaller samples are needed and phaseequilibrium is attained much faster[92],since equilibration timeis inversely proportional to the square of the film thickness. Errorsrise with temperature and pressure, due to dampening and viscousdissipation[89].

Another analytical method was used by Morris et al. [93]tomeasure low gas solubilities, e.g., of hydrogen in water. A palla-dium/hydrogen electrical resistance sensor was used to determinethe hydrogen content in the liquid phase.

Abbott et al. [94]proposed a capacitative method (dielectric

constant method) to measure the solubility of low-volatile sub-stances in supercritical gases. They used a 25cm3 high-pressurecell, lined with a layer of Teflon. A capacitor consisting of two par-allel rectangular stainless steel plates (area of 6.6cm2, held 1mmapart by Teflon spacers) was placed in the vapor phase. The dielec-tric constant ofthe saturatedvaporphase wasmeasured at differentpressures. To calculate the concentration of the solute in the vaporphase from the dielectric constant, information on the permanentdipole moments and the molecular polarizabilites of the compo-nents of the mixture needs to be known.

3.2. Synthetic methods (Syn)

The idea of synthetic methods is to prepare a mixture of pre-

cisely known composition and then observe the phase behaviorin an equilibrium cell and measure properties in the equilibriumstate, like pressure and temperature. No sampling is necessary. Theproblem of analyzing fluid mixtures is replaced by the problem ofsynthesizing them[7].Synthetic methods can be applied with orwithout a phase transition. In both cases,first a mixture of preciselyknown composition is prepared.

In synthetic methodswith a phase transitionvalues of tempera-ture andpressure areadjusted so that the mixture is homogeneous,a single phase exists. Then the temperature or pressure is varieduntil the beginning of the formation of a new, a second phase isobserved. The composition of thefirst, large phase can be set to theknown overall composition. The composition of the second, smallphase is not known. Each experiment yields one point of thepTx

phase envelope.Insteadofavariationoftemperatureorpressuretocauseaphasetransition theoverall concentration canbe changed. Wubbolts et al.[95]use this approach, designated with vanishing-point methodor clear-point method, for SLE measurements. A clear solution ofa given solute concentration is added to a known amount of anti-solvent until the last crystal disappears. The composition of themixture at this vanishing point equals the solubility of the mix-ture. When the procedure is repeated with a solution of a differentconcentration another point of the curve is found.

Depending on how the phase transition is detected, syntheticmethodswitha phase transitionscan be divided into visual(SynVis)and non-visual synthetic methods (SynNon).

In synthetic methods without a phase transition, equilibrium

properties like pressure, temperature, phase volumes and densi-


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ties are measured and phase compositions are calculated using thematerial balance. Synthetic methodswithout a phasetransitioncanbe divided into isothermal (SynT), isobaric (SynP) and other (Syn-Oth) synthetic methods. During the period covered in this review(20002004) synthetic methods with a phase transition have beenused about 5 times more often than synthetic methods without aphase transition.

Synthetic methods can be used where analytical methods fail,i.e., when phase separation is difficult due to similar densitiesof the coexisting phases, e.g., near or even at critical points andin barotropic systems, where at certain conditions the coexistingphases have the same density. Often, the experimental procedureis easy and quick[5].Because no sampling is necessary the experi-mentalequipment canconcentrateon fewcomponents andthe vol-ume of the equilibrium cell can be small. Therefore, the apparatuscan be rather inexpensive. On the other hand,it can be designed forextreme conditions concerning temperatures and pressures[96].Cohen-Adad[97]describes a diamond anvil cell that can be usedfor pressures up to 135GPa. The experimental data at the highestpressures of all articles covered in this review were taken by Fanget al. [98], also with a diamond anvil cell, at pressures up to 2.6 GPa.

For multicomponent systems, experiments with syntheticmethods yield less information than with analytical methods,

because the tie-lines cannot be determined without additionalexperiments. Therefore, synthetic methods are less often used forsystems containing more than 2 components.

3.2.1. Visual synthetic methods (SynVis)

The appearance of a new phase is usually detected by visualobservation of the resulting turbidity or meniscus in a view cell.For isooptic systems where the coexisting phases have approxi-mately the same refractive index, visual observation is impossible.Thevisualsyntheticmethodcanbeusednotonlyforthedetermina-tionofsimplevaporliquidequilibria,butalsotostudycomplicatedphase behavior, e.g., multiphase equilibria[99],solidliquid equi-libria [100], critical curves of mixtures [101], gas hydrate formation[102], cloud-point determination [103] and phase equilibria in

polymersolvent systems[104].The Cailletet apparatus of TU Delft[105]is the most frequently

used type of apparatus according to the synthetic visual method. Itconsists of a thick-walled Pyrex glass tube (50cm long, 3 mm innerdiameter) with the open end placed in an autoclave and immersedinmercury.ThemercuryconfinesthesampleintheCailletettube.Astainlesssteelballdrivenbyreciprocatingmagnetsstirsthesample.

Daridon et al. [106]used a very small cell with a volume of0.03cm3 for the visual observation of synthetic waxes at highpressures. The cell is placed within a polarizing microscope. Theapparatus allows the visual observation of crystals of 2m.

When only small quantities of a sample shall be used in theexperiment,e.g., to observe solidliquidgas equilibria,a glasscap-illary can be placed inside the high-pressure view cell[107,108].

To improve the detection of phase transitions, some authors uselaser light scattering techniques[103,109].Jager and Sloan[110]use Raman spectroscopy to detect hydrates. Dong et al.[111]useadditional SAXS measurements to determine the median micellesize of the water-in-carbon dioxide microemulsions.

Veiga et al.[112]used glass capillary helixes not only to inves-tigate the high pressure behavior of pure compounds but also atnegative pressures as far down as 20.8MPa.

With 36.4% of all systems investigated in this review, syntheticvisual methods were the most frequently used type of method.

3.2.2. Non-visual synthetic methods (SynNon)

As an alternative to visual observation, other physical proper-ties can be monitored to detect phase transitions. Minicucci et al.

[113]made use of transmitted X-rays instead of visible light, as

the basis of phase detection, while Drozd-Rzoska et al.[114]usedmeasurements of the relative dielectric permittivity for LLE mea-surements at high, low and negative pressures. If the total volumeof a variable-volume cell can be measured accurately, the appear-ance of a new phase can be obtained from the abrupt change inslope on the pressurevolume plot more accurately than by visualobservation [115,116]. As an alternativepVTmeasurements can beperformed and the intersection of isochors can be used to deter-mine points on the coexistence curve. A sharp change in the slope(dp/dT), occurs at the phase boundary.

Mayetal. [117] useda microwavere-entrant resonatorto detectthe appearance of dew and bubble points in hydrocarbon sys-tems.Takagi et al. [118] measured bubble point pressures using anultrasonic speed apparatus. Since the acoustic wave excited in thesamplefor the speed of sound measurement wasstrongly absorbedin the gas phase as compared to the absorption in the liquid phase,the appearance of the gas phase was detected by the change ofthe acoustic echo signal. For searching critical points of pure fluids,acoustic methods have the advantage that even for temperaturesseveral degrees above the critical point, the sound velocity exhibitsa minimum when measured isothermally as a function of pressure[119].

To measure the critical temperature of thermally unstable sub-

stance, the pulse-heating method, as described by Nikitin et al.[120],can be used. It is based on measuring the pressure depen-dence of the temperature of the attainable superheat (spontaneousboiling-up) of a liquid with the help of a thin wire probe heatedby pulses of electric current. When the pressure in the liquidapproaches the critical pressure, the temperature of the attainablesuperheat approaches the critical temperature.

A synthetic non-visual method that looks at first sight likean analytical continuous-flow method (AnPTCon) was used byVonNiederhausern et al.[121]to determine the critical points ofthermally unstable or reactive components. To achieve very shortresidence times, a sample of precisely known composition is con-tinuouslydisplacedandheatedinacapillarytube.Noanalysisofthesamples takes place. To determine the critical point, several tem-

perature scans must be made in the vicinity of the critical point.Below thecritical point, thetemperature scan will show a flat, hor-izontal region indicative of isothermal boiling. Above the criticalpoint, the transition region is no longer flat and horizontal. Thecritical point is inferred by the temperature and pressure whereisothermal boiling is no longer observed.

Valyashko et al.[122]used jumps of the isochoric heat capacityto detect the appearance of a vapor phase or a second liquid phase.Wurflinger and Urban[123]studied the phase behavior of liquidcrystals with high-pressure differential thermal analysis (DTA).

The experiments at the highest temperatures of all articles cov-ered in this review were performed by Manara et al. [96].Theyinvestigated the melting point of uranium dioxide at high pres-sures. Temperatures of almost 3200K were needed. Such high

temperatures canbe measured optically by pyrometry. Two pulsedNdYAG laser beams were mixed through a suitable optical sys-tem in the same fiber and then focused onto the sample surface.The pulse with the higher power peak was used to heat the sampleabove themelting point; the otherone,lesspowerful, but of longerduration, was used to control the cooling rate on the sample sur-face. This lead to a much better definition of the freezing plateau.Pressure was applied by using helium.

Diamond anvilcells are particularly suitable fornon-visualmea-surements at very high pressures[97].The selective transparencyof diamond for IR to X-ray and gamma-ray radiations permits insitumeasurements during experiments.

Ngo et al.[124]used the synthetic non-visual method to mea-sure the solubility of solids in carbon dioxide. First the cell was

charged with the solid. Then it was pressurized with carbon diox-


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ideand stirred constantly. Equilibrium of themixture wasobservedin situby periodically taking spectra (UV absorbance) of the solu-tion. The pressure was raised stepwise until no further significantincrease in the peak absorbance was observed. This meant that allsolids had been dissolved in the fluid phase.

Randzio[125]used a new transitiometric method for investi-gation of the solid phase behavior in asymmetric binary systems.Transitiometry is based on a simultaneous recording of bothmechanical and thermal variables of a thermodynamic transitioninduced by scanning one independent variable (p, Tor V) whilethe other independent variable is being kept constant. Takingthe (tetracosane+methane) binary system as a test example, thethree-phase curve (solid+ liquid+ vapor) hasbeen determined. Theapparatus (transitiometer) consists of a calorimeter equippedwith high-pressure vessels, and apVTsystem. During the isobarictemperature scans both the heat flux and the volume variationswere recorded.

For measurements of solidliquid equilibria at high pressures,the dead-volume of the apparatus can have a very negative influ-ence [97]. The volatility of constituents changes the nominalcomposition of a sample and can induce an incorrect apparentretrograde solubility curve.

To investigate the phase behavior in porous media, non-visual

methodsare particularly advantageous. Zatsepina and Buffett [126]used electrical resistance measurements to monitor the appear-ance and growth of CO2hydrate crystals in the pore fluid. Omi etal.[127]used a high-pressure NMR probe to investigate the pres-sure and pore size dependence of the critical behavior of xenon inmesopores.

Ivanic et al.[128]monitored the pressure and temperature ina hydrate-bearing system and identified equilibrium at the condi-tions where the last hydrate crystal in thesystem dissociatesat thecross-point of thepTcurves from cooling and from heating.

Oag et al. [119]describe an apparatus where the determina-tion of phase transitions and critical points can be carried out withdifferent methods: visually, by measuring the laser reflectance ofthe fluid, which is at its maximum at the critical point, the sound

velocity and by using vibrating shear mode sensors.

3.2.3. Synthetic isothermal methods (SynT)

Synthetic isothermal methods are performedwithout a phasetransition, where the pressure of a synthesized multiphase mix-ture is measured at isothermal conditions and phase compositionsare calculated using the material balance. At the beginning of anexperiment, an equilibrium cell is charged with a known amountof the first component, evacuated and thermostated to a giventemperature. Then a known amount of the second component isadded whereby the pressure increases. The second componentdissolves into the liquid phase, which leads to a decay of the pres-sure in the equilibrium cell. Therefore, this method is also calledpressure-decay method, especially when a polymer is used as the

first component. After equilibration pressure and temperature areregistered. No samples are taken. The composition of the vaporphase is calculated using a phase equilibrium model or assumedas just containing the pure gas, if we consider solubility in poly-mers for example, or other compounds with negligible volatility.The composition of the liquid phase is calculated using the mate-rial balance from the known total composition, the compositionof the vapor phase and the phase densities and volumes [129].By repeating the addition of the second component into the cell,several points along the boiling point line can be measured.

At lower pressures, were they are often designated as staticmethod or isothermalpTx method, synthetic isothermal meth-ods are very commonly used[130,131].Examples for the use ofthe synthetic isothermal methods at high pressures are the deter-

mination of the solubility of low-boiling substances in polymers

[132] orthesolubilityofgasesinionicliquids [133] or in electrolytesolutions, e.g., by Gmehling and co-workers[134].

When used for a pure component, the synthetic isothermalmethod delivers the vapor pressure, e.g., Funke et al. [135]. Then, itis often called the static vapor-pressure method.

Often in synthetic isothermal methods, a view cell is used asequilibrium cell. This has the advantages that unusual behavior,like foaming, can be seen, that the volumes of the liquid and thevaporphasecanbedeterminedvisuallyandthatthecellcanbeusedalso according to the synthetic visual method. For example, Fukn-Kokot et al.[107]measured solidliquidgas equilibria using thesynthetic isothermal method to determine the CO2content in theliquid phase and the synthetic visual method to detect solid forma-tion.

Krger et al.[136]compared results of the isothermal methodfor VLE of the n-pentane+poly(dimethylsiloxane) system withresults of the gravimetric sorption method (AnGrav) and withinverse gas chromatography. These methods differ in the under-lying experimental principles as well as in the complexity of dataanalysis. Despite of these differences, the agreement of the mea-sured VLE data is excellent.

3.2.4. Synthetic isobaric methods (SynP)

Theboiling temperature of a synthesized mixture is measured atisobaricconditionsandphasecompositionsarecalculatedusingthematerial balance. As opposed to analytical isobaric methods (AnP),no sampling or analysis is performed. Just as synthetic isothermalmethods (SynT), synthetic isobaric methods (SynP) are performedwithout a phase transition. When used for a pure component the composition is given anyway the synthetic isobaric methoddelivers the vapor pressure, e.g., Weber et al. [137]. Then, it is oftencalled the dynamic vapor-pressure method. Typically, isobaricexperiments are performed in an ebulliometer as described in Sec-tion 3.1.3 (AnP). An ebulliometer was first used to determine themolecular weights of substances, by measuring the changes of theboiling point of water caused by the presence of the unknown sub-stance. Twin ebulliometry can be used to determine the activity

coefficient at infinite dilution. The temperaturedifference betweenan ebulliometer filled with the first (pure) component and a sec-ond ebulliometer (under the same pressure) filled with the firstcomponent and with a small amount of a second component(diluted solution) is measured. From the difference of the boilingtemperatures, the activity coefficient at infinite dilution can be cal-culated. Usually synthetic isobaric methods are used to measurelow-pressure data.

Ewing and Ochoa[138]used comparative ebulliometry to pre-cisely determine the vapor pressure of pure components at highpressures. The sample and a reference fluid are boiled in separateebulliometers under a common pressure of gas such as helium ornitrogen, and the condensation temperatures of the sample and ofthe reference fluid are measured. The common pressure is calcu-

lated from the known vapor pressure of the reference fluid. Themethod has many advantages: direct measurement of pressure isavoided, the fluids are degassed by boiling, and the ebulliome-ters act as heat pipes to provide high-performance thermostats.The corresponding disadvantages are the considerable demandsonthermometry, the solubility of the buffer gas at high pressures, andthermal gradients due to pressure heads. But the greatest advan-tage is speed of measurement; typically, a pressuretemperaturepoint can be obtained in an hour.

3.2.5. Other synthetic methods (SynOth)

Properties measured in the homogenous or heterogeneousregion are used to calculate the phase boundaries.

Abdulagatov et al. [139] used two-phase isochoric heat capacity

measurements to determine the values of the critical pressure and


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slope of the vapor-pressure curve at the critical point of 18 purecomponents.

Forsystems with twodegrees offreedom (e.g.,binary two-phaseequilibria or ternary three-phase equilibria), the compositionsare fixed when temperature and pressure are given. Luks andco-worker[140]took phase volume and overall composition rawdata for a set of three experimental runs at the same temperatureand pressure; in each run a different phase is caused to be volu-metrically dominant relative to the other two phases. With the useof mass balance, the compositions and molar volumes of the threephases were determined from the three conjugate measurements[141].

Di Nicola et al.[142]used isochoric pvTx measurements in thesingle phase region (remark: otherwise it would be SynT) to fitthe binary interaction parameters of an equation of state. Then,the compositions of the coexisting phases are calculated using theequation of state model.

4. Systems investigated

Almost 700 articles with experimental data on high-pressurephase equilibria were found [143745]. More than 2000 sys-tems have been investigated, from pure components, binarysystems up to complex mixtures with many components. InTables 356,the following information about the systems inves-tigated is given: the reference, the temperature and pressurerange of the data and the experimental method used for the mea-surements. The abbreviations used to designate the experimentalmethod have been explained in the text above or are explainedinTable 2.

Because the size of the equilibrium cell can be of importance,e.g., for the pressure drop during sampling or for the amount ofsubstances needed, the volume of the equilibrium cell is also givenin the tables.

Information on pure-component systems is given in Table 3.Most of experimental phase equilibrium data were on binary sys-tems: 1204 systems investigated have been divided into 28 tables(Tables 431), withTable 4 (carbon dioxide + X) containing 681binary system being by far the largest one. Many data have beenmeasured for binary systems containing water, propane, difluo-romethane (HFC-32), and methane. Information on the tables andtheir order can be found in the list of tables.

The additional components X are listed in alphabetic sequence.The results of 434 ternary systems are given in 17 tables(Tables 3248), e.g., 76 ternary systems of thetype CO2 +water+X.The order of the tables is analog to the order of the binary systems.Information on 134 multicomponent systems (410 components)is listed inTables 4952.Results for complex systems with manycomponents, like gas condensate reservoirs, are listed inTable 53.

Special tables have been generated for systems containinghydrates (Tables 5456).Overall, 129 systems with hydrates werefound.

To provide the reader with information on articles with cor-

rections and discussions on published experimental high-pressuredata, we prepared a compilation (Table 57).We give the originalarticle and the articles with corrigenda, comments or rebuttals tocomments when at least one of them falls in the period of thereview.

Work on the continuation of the review series is under way,covering the period between 2005 and 2008,and will be publishedin 2010.

Table 2

Experimental methods: abbreviations and frequency of use in review period.

46.7% Analytical methods, total composition is not exactly known, analysis of phases in equilibriumAnalytical methods with sampling:

27.6% AnT Analytical method: isothermal methodBlo Blocking off a large sampling volume from the equilibrium cellCap Sampling through capillariesIns In situsampling: a sampling vial is in the equilibrium cell, careful depressurization, removal of vialLcir Liquid-phase recirculationMla Material loss analysis: sampling after depressurization, weight loss of sample due to desorption is

investigatedVal Sampling using a special valveVar Variable-volume cellVcir Vapor-phase recirculationVLcir Recirculation of the vapor and the liquid phase

0.0% AnP Analytical isobaric method, ebulliometry with phase analysis15.4% AnPT Analytical isobaric-isothermal method

Con Continuous-flow methodSemX Semi-flow method used to measure the solubility of a gas in a liquidSemY Semi-flow method used to measure the solubility of substance in a gas (or supercritical fluid)Chro Chromatographic method, e.g. inverse SFC, inverse HPLC

Analytical methods without sampling:1.5% AnSpec Spectroscopic analysis

1.1% AnGrav Gravimetric determination of phase composition: suspension balance or microbalance or quartzspring balance

1.1% AnOth Other determination of phase composition, e.g. by resonance in a Quartz Crystal Microbalance

53.3% Synthetic methods, total composition is exactly known, no analysis of phases in equilibriumSynthetic methods with a phase transition:

36.4% SynVis Visual detection of phase transitions8.4% SynNon Non-visual detection of phase transitions

Synthetic methods without a phase transition:6.1% SynT Isothermal, at least 2 phases, total pressure measured, often for pure-component vapor pressures;

mixtures: y calculated0.2% SynP Isobaric, at least two phases, ebulliometry, often for pure-component vapor pressures, mixtures:

differential ebulliometry2.2% SynOth Measured properties in the homogenous or heterogenous region are used to calculate the phase

boundaries

Additional remarks for all methods: Var, variable-volume cell; Vis, view cell, visual observation; Spec, spectroscopic method to get information; Pc, the critical pressure hasbeen measured; Tc, the critical temperature has been measured; X, only the composition of the liquid phase is determined; Y, only the composition of the vapor phase is

determined.


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Table 3

Pure-component systems: X.

X Reference T(K) P(MPa) V(cm3) Method

1,1,1,2,2,3,3,4,4-Nonafluorohexan-5-one Otake et al.[553] 332498 02.2 16 SynVisVarPcTc1,1,1,2,2,3,3-Heptafluoropentan-4-one Otake et al.[553] 302476 02.5 16 SynVisVarPcTc1,1,1,2,2-Pentafluoro-3-(1,1,2,2-tetrafluoroethoxy)-propane Yasumoto et al.[731] 299473 02.2 16 SynVisVarPcTc1,1,1,2,2-Pentafluoro-3-butanone Sako et al.[596] 453453 2.92.9 5.3 SynVisPcTc

Sako et al.[597] 453453 2.92.9 5.3 SynVisPcTc1,1,1,2,2-Pentafluoroethane (HFC-125) Lee et al.[439] 293313 1.22 80 SynT

Lim et al.[463] 283293 0.91.2 85 SynVisPitschmann and Straub[564] 303339 1.53.6 n.a. SynVisPcTc1,1,1,2,2-Pentafluoropentan-3-one Otake et al.[553] 299475 02.6 16 SynVisVarPcTc1,1,1,2,3,3,3-Heptafluoropropane (HFC-227ea) Di Nicola[264] 235365 02.4 254.8 SynT

Gruzdev et al.[342] 272373 0.12.8 439 SynTHu et al.[363] 233375 02.9 13 SynVisLee et al.[439] 303323 0.50.9 80 SynTPark et al.[555] 283323 0.20.9 85 SynVisValtz et al.[685] 293353 0.31.8 n.a. SynVisValtz et al.[689] 276375 0.22.9 n.a. SynVisWang and Duan[701] 253373 02.8 200 SynT

1,1,1,2,3,3-Hexafluoro-3-(2,2,2-trifluoroethoxy)propane Yasumoto et al.[731] 302475 02.2 16 SynVisVarPcTc1,1,1,2,3,3-Hexafluoro-3-(2,2,3,3,3-pentafluoropropoxy)-propane Yasumoto et al.[731] 312486 01.9 16 SynVisVarPcTc1,1,1,2,3,3-Hexafluoro-3-(2,2,3,3-tetrafluoropropoxy)-propane Yasumoto et al.[731] 285516 02.1 16 SynVisVarPcTc1,1,1,2,3,3-Hexafluoropropane (HFC-236ea) Di Nicola and Giuliani[260] 255363 01.2 254.8 SynT1,1,1,2,4,4,4-Heptafluoroisobutyltrifluoromethyl ether

Sako et al.[596] 447447 2.12.1 5.3 SynVisPcTcSako et al.[597] 447447 2.12.1 5.3 SynVisPcTc

1,1,1,2-Tetrafluoro-2-difluoro-methoxyethyldifluoromethyl ether


1,1,1,2-Tetrafluoro-2-trifluoromethyl-3-butanone


1,1,1,2-Tetrafluoroethane (HFC-134a) Ho et al.[353] 273313 0.21 85 SynVisLim et al.[466] 273313 0.61.8 85 SynVisPark et al.[555] 303323 0.71.3 85 SynVisYasumoto et al.[731] 374374 44 16 SynVisVarPcTc

1,1,1,3,3,3-Hexafluoropropane (HFC-236fa) Duan et al.[274] 253396 03 200 SynT1,1,1,3,3-Pentafluoropropane (HFC-245fa) Wang and Duan[701] 255393 01.9 200 SynT1,1,1-Trifluoro-2-(2,2,2-trifluoroethoxy)ethane Yasumoto et al.[731] 293476 02.7 16 SynVisVarPcTc1,1,1-Trifluoroethane (HFC-143a) Duan et al.[274] 251343 0.23.5 200 SynT

Lim et al.[462] 323333 2.32.8 85 SynTLim et al.[465] 283293 0.81.1 85 SynTLim et al.[466] 273313 0.21 85 SynVisPitschmann and Straub[564] 316345 23.7 n.a. SynVisPcTcWidiatmo et al.[705] 300345 1.33.7 139 SynT

1,1,2,2-Tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane Yasumoto et al.[731] 297463 02.7 16 SynVisVarPcTc

1,1,2,2-Tetrafluoro-2-(2,2-difluoroethoxy)ethane Yasumoto et al.[731] 300501 03.1 16 SynVisVarPcTc1,1,2,2-Tetrafluoro-3-(1,1,2,2-tetrafluoroethoxy)propane Yasumoto et al.[731] 322510 02.5 16 SynVisVarPcTc1,1,2,2-Tetrafluorobutan-3-one1,1-Difluoroethane (HFC-152a)

Otake et al.[553] 297500 03.6 16 SynVisVarPcTcLim et al.[463] 293293 0.50.5 85 SynVisLim et al.[465] 283293 0.30.5 85 SynTLim et al.[466] 273313 0.20.9 85 SynVisPark et al.[555] 283303 0.30.6 85 SynVisTakagi et al.[661] 243333 01.4 60 SynNon

1,2-Ethanediol VonNiederhausern et al.[693] 719719 8.28.2 n.a. SynNonConPcTc1,2-Propanediol VonNiederhausern et al.[693] 676676 5.95.9 n.a. SynNonConPcTc1,3-Propanediol VonNiederhausern et al.[693] 722722 6.36.3 n.a. SynNonConPcTc

Wilson et al.[708] 718718 6.56.5 n.a. SynNonConPcTc1,4-Butanediol Wilson et al.[708] 723723 5.55.5 n.a. SynNonConPcTc1-Butanol Abdulagatov et al.[139] 530563 4.84.8 n.a. SynOthPcTc1-Chloro-1,1-difluoroethane Yasumoto et al.[731] 410410 44 16 SynVisVarPcTc1-Docosanol Nikitin et al.[537] 827827 11 n.a. SynNonPcTc

Nikitin et al.[538] 827827 11 n.a. SynNonPcTc

1-Eicosanol Nikitin et al.[537] 808808 1.11.1 n.a. SynNonPcTcNikitin et al.[538] 808808 1.11.1 n.a. SynNonPcTc1-Heptadecanol Nikitin et al.[537] 780780 1.31.3 n.a. SynNonPcTc

Nikitin et al.[538] 780780 1.31.3 n.a. SynNonPcTc1-Hexadecanol Nikitin et al.[537] 770770 1.41.4 n.a. SynNonPcTc

Nikitin et al.[538] 770770 1.41.4 n.a. SynNonPcTc1-n-Butoxy-2-propanol VonNiederhausern et al.[693] 624624 2.72.7 n.a. SynNonConPcTc1-n-Propoxy-2-propanol VonNiederhausern et al.[693] 605605 33 n.a. SynNonConPcTc1-Octadecanol Nikitin et al.[537] 790790 1.21.2 n.a. SynNonPcTc

Nikitin et al.[538] 790790 1.21.2 n.a. SynNonPcTc1-Octanol Yang et al.[100] 263293 24.8183.6 n.a. SynVis

Yang et al.[728] 263293 24.8183.6 n.a. SynVis1-Pentadecanol Nikitin et al.[537] 757757 1.61.6 n.a. SynNonPcTc

Nikitin et al.[538] 757757 1.61.6 n.a. SynNonPcTc1-Phenylethanol VonNiederhausern et al.[693] 699699 3.73.7 n.a. SynNonConPcTc1-Propanol Abdulagatov et al.[139] 403536 10.110.1 n.a. SynOthPcTc1-Tetradecanol Nikitin et al.[537] 743743 1.61.6 n.a. SynNonPcTc

Nikitin et al.[538] 743743 1.61.6 n.a. SynNonPcTc


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Table 3 (Continued )


1-Tridecanol Nikitin et al.[537] 732732 1.71.7 n.a. SynNonPcTcNikitin et al.[538] 732732 1.71.7 n.a. SynNonPcTc

2-(2-Aminoethylamino)ethanol Wilson et al.[708] 739739 4.64.6 n.a. SynNonConPcTc2-(2-Butoxyethoxy)ethyl acetate Wilson et al.[708] 693693 2.12.1 n.a. SynNonConPcTc2-(2-Ethoxyethoxy)ethyl acetate Wilson et al.[708] 673673 2.52.5 n.a. SynNonConPcTc2,2-Difluoroethylbis(trifluoromethyl)amine Otake et al.[553] 293460 02.6 16 SynVisVarPcTc2,3,3,5,5,6,6-Heptafluoro-1,4-dioxane Sako et al.[596] 452452 2.82.8 5.3 SynVisPcTc

Sako et al.[597] 452452 2.82.8 5.3 SynVisPcTc2-Butanol Abdulagatov et al.[139] 519546 4.64.6 n.a. SynOthPcTc2-Difluoromethoxy-1,1,1-trifluoroethane Yasumoto et al.[731] 294444 03.4 16 SynVisVarPcTc2-Methyl-1,3-propanediol Wilson et al.[708] 708708 5.35.3 n.a. SynNonConPcTc2-Methylpropane (isobutane) Galicia-Luna et al.[47] 317406 0.53.5 40 SynT

Glos et al.[331] 115340 01 n.a. SynTGlos et al.[332] 115340 01 n.a. SynTLee et al.[439] 293323 0.30.6 80 SynTMiyamoto et al.[517] 310407 0.53.6 1125 SynTVar

2-Propanol (isopropanol) Abdulagatov et al.[139] 473508 5.15.1 n.a. SynOthPcTc2-Trifluoromethyl-4,4,5,5-tetrafluoro-1,3-dioxolane


3-Difluoromethoxy-1,1,1,2,2-pentafluoropropane Yasumoto et al.[731] 298455 02.7 16 SynVisVarPcTc3-Methoxy-1,1,2,2,3,3-hexafluoropropane Yasumoto et al.[731] 301487 03.1 16 SynVisVarPcTc3-Methoxy-1,1,2,2-tetrafluoropropane Yasumoto et al.[731] 342505 03.2 16 SynVisVarPcTc4-Ethoxy-1,1,1,2,2,3,3,4,4-nonafluorobutane Yasumoto et al.[731] 309482 01.9 16 SynVisVarPcTc

Yasumoto et al.[731] 473482 1.71.9 16 SynVisVarPcTc4-Methoxy-1,1,1,2,2,3,3-heptafluorobutane Yasumoto et al.[731] 291481 02.3 16 SynVisVarPcTc

5-Methoxy-1,1,2,2,3,3,4,4-octafluoropentane Yasumoto et al.[731] 301546 02.5 16 SynVisVarPcTc5-n-Decyl-2-(4 -isothiocyanato-phenyl)-1,3-dioxane Wuerflinger and Urban[123] 317395 0.1200 n.a. SynNon5-n-Hexyl-2-(4-isothiocyanato-phenyl)-1,3-dioxane Wuerflinger and Urban[123] 308395 0.1200 n.a. SynNon5-n-Octyl-2-(4-isothiocyanato-phenyl)-1,3-dioxane Wuerflinger and Urban[123] 319395 0.1200 n.a. SynNonAcetonitrile (ethanenitrile) Ewing and Ochoa[138] 277535 04.1 605 SynPVcir

VonNiederhausern et al.[693] 545545 4.84.8 n.a. SynNonConPcTcAdamantane Poot et al.[565] 546639 3.467.2 n.a. SynVisAmmonia Brandt et al.[187] 342405 3.211.3 n.a. SynVisVarArgon Abdulagatov et al.[139] 83149 4.84.8 n.a. SynOthPcTcBenzene Wang et al.[698] 562562 4.84.8 18 SynVisPcTcBis(2-aminoethyl)amine VonNiederhausern et al.[693] 709709 4.34.3 n.a. SynNonConPcTc

Wilson et al.[708] 709709 4.34.3 n.a. SynNonConPcTcButanedioic acid Nikitin et al.[541] 851851 6.46.4 n.a. SynNonPcTcButylbenzene Nikitin et al.[120] 660660 2.92.9 n.a. SynNonPcTcButylcyclohexane Nikitin et al.[540] 650650 2.52.5 n.a. SynNonPcTcCarbon dioxide Abdulagatov et al.[139] 278304 7.37.3 n.a. SynOthPcTc

Horstmann et al.[358] 304304 7.37.3 10 SynVisTc

May et al.[117] 295295 66 185 SynNonVcirVarStuart et al.[654] 299300 6.67 28 SynVisVarChlorodifluoromethane (HCFC-22) He et al.[351] 310345 1.43.1 25 SynTChlorotrifluoromethane (CFC-13) Magee et al.[491] 250301 13.8 28.8 SynTCumene Wang et al.[698] 631631 3.33.3 18 SynVisPcTcCyclohexane Domanska and Morawski[269] 293353 23.3153.1 n.a. SynNonVar

Ewing and Ochoa[287] 281552 04 605 SynPVcirNikitin et al.[540] 551551 44 n.a. SynNonPcTc

Decanedioic acid Nikitin et al.[541] 845845 2.52.5 n.a. SynNonPcTcDeuterium oxide Abdulagatov et al.[139] 605643 21.621.6 n.a. SynOthPcTc

Veiga et al.[112] 258333 -20.88.2 0.004 SynVisDiamantane Poot et al.[565] 523655 4.1115.2 n.a. SynVisDiethyl sulfide VonNiederhausern et al.[693] 557557 3.83.8 n.a. SynNonConPcTcDifluoromethane (HFC-32) Coquelet et al.[26] 283343 1.14.8 n.a. SynVis

Lee et al.[440] 268318 0.62.7 85 SynVisLim et al.[463] 283293 1.11.4 85 SynVisPark et al.[555] 283303 1.11.9 85 SynVisPitschmann and Straub[564] 318351 2.85.7 n.a. SynVisPcTc

Dimethyl ether Wu et al.[710] 233400 05.3 11.3 SynTVisDocosanoic acid Nikitin et al.[539] 837837 1.11.1 n.a. SynNonPcTcDodecanedioic acid Nikitin et al.[541] 859859 2.12.1 n.a. SynNonPcTcDodecanoic acid Nikitin et al.[539] 743743 1.91.9 n.a. SynNonPcTcEicosane Domanska and Morawski[269] 313353 16.2225 n.a. SynNonVarEicosanoic acid Nikitin et al.[539] 820820 1.21.2 n.a. SynNonPcTcEthane Funke et al.[311] 91305 04.8 n.a. SynTPcTc

Horstmann et al.[358] 305305 4.84.8 10 SynVisTcEthanoic acid Nikitin et al.[539] 590590 5.85.8 n.a. SynNonPcTcEthylbenzene Nikitin et al.[120] 614614 3.63.6 n.a. SynNonPcTc

VonNiederhausern et al.[121] 492618 0.63.6 0.1 SynNonConPcTcEthylcyclohexane Nikitin et al.[540] 604604 3.23.2 n.a. SynNonPcTcGallium Veiga et al.[112] 302303 -818 0.004 SynVisHeptadecanoic acid Nikitin et al.[539] 792792 1.31.3 n.a. SynNonPcTcHeptanedioic acid Nikitin et al.[541] 842842 3.23.2 n.a. SynNonPcTcHexadecanoic acid Nikitin et al.[539] 785785 1.41.4 n.a. SynNonPcTcHexafluoroethane (pfc-116) Kao and Miller[405] 177291 02.9 30 SynT

Hexanedioic acid Nikitin et al.[541] 841841 3.83.8 n.a. SynNonPcTc


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Hexanoic acid Nikitin et al.[539] 652652 3.33.3 n.a. SynNonPcTcHexylbenzene Nikitin et al.[120] 695695 2.32.3 n.a. SynNonPcTcMethane Abdulagatov et al.[139] 105190 4.64.6 n.a. SynOthPcTcMethanol Veiga et al.[112] 298329 3.823.8 0.004 SynVisMethylbenzene Nikitin et al.[120] 588588 44 n.a. SynNonPcTcMethylcyclohexane Nikitin et al.[540] 569569 3.43.4 n.a. SynNonPcTcMobil eal arctic 22 oil Skripov et al.[645] 825825 0.60.6 n.a. SynNonPcTcn-Butane Glos et al.[331] 135340 00.7 n.a. SynT

Glos et al.[332] 135340 00.7 n.a. SynTn-Decane Abdulagatov et al.[139] 453617 2.12.1 n.a. SynOthPcTcn-Dodecane Yang et al.[728] 268293 27.4160.3 n.a. SynVisn-Heptane Abdulagatov et al.[139] 373540 2.72.7 n.a. SynOthPcTc

Weber[137] 335479 01 n.a. SynPVcirn-Hexadecane Domanska and Morawski[269] 293353 9.2309.7 n.a. SynNonVar

Skripov et al.[645] 720720 1.41.4 n.a. SynNonPcTcYang et al.[100] 293323 8.1144.6 n.a. SynVis

n-Hexane Abdulagatov et al.[139] 343507 33 n.a. SynOthPcTcNitrogen tetraoxide Abdulagatov et al.[139] 313431 4.44.4 n.a. SynOthPcTcNitrous oxide Di Nicola et al.[265] 219273 0.53.1 273.5 SynOthn-Nonane Abdulagatov et al.[139] 383594 2.22.2 n.a. SynOthPcTcn-Octadecane Domanska and Morawski[269] 303353 11.2259.9 n.a. SynNonVarn-Octane Abdulagatov et al.[139] 373569 2.42.4 n.a. SynOthPcTc

Ewing and Ochoa[288] 323563 02.3 605 SynPVcirNonanedioic acid Nikitin et al.[541] 844844 2.72.7 n.a. SynNonPcTcn-Pentane Abdulagatov et al.[139] 313470 3.43.4 n.a. SynOthPcTc

Pfohl et al.[132] 308423 01.5 345 SynTVisn-Tetradecane Yang et al.[100] 283318 16183.1 n.a. SynVisn-Tridecane Daridon et al.[106] 267287 0.198.3 0.03 SynVis

Domanska and Morawski[269] 293353 134.3582 n.a. SynNonVarOctadecanoic acid Nikitin et al.[539] 803803 1.31.3 n.a. SynNonPcTcOctafluorocyclobutane Kao and Miller[405] 234387 02.6 85 SynTOctanedioic acid Nikitin et al.[541] 843843 2.92.9 n.a. SynNonPcTcOctanoic acid Nikitin et al.[539] 690690 2.82.8 n.a. SynNonPcTcPentadecanoic acid Nikitin et al.[539] 777777 1.51.5 n.a. SynNonPcTcPentafluoroethyl methyl ether (HFC245mc) Kayukawa et al.[409] 240380 01.7 n.a. SynT

Widiatmo et al.[705] 310406 0.32.8 139 SynTPentanedioic acid Nikitin et al.[541] 840840 4.24.2 n.a. SynNonPcTcPentylbenzene Nikitin et al.[120] 675675 2.52.5 n.a. SynNonPcTcPhenyl acetate Wilson et al.[708] 685685 3.53.5 n.a. SynNonConPcTcPhenyldecane Nikitin et al.[120] 752752 1.71.7 n.a. SynNonPcTcPhenylheptane Nikitin et al.[120] 708708 2.12.1 n.a. SynNonPcTcPhenyloctane Nikitin et al.[120] 725725 1.91.9 n.a. SynNonPcTc

Phenyltridecane Nikitin et al.[120] 790790 1.51.5 n.a. SynNonPcTcPhenylundecane Nikitin et al.[120] 763763 1.61.6 n.a. SynNonPcTcPoly(ethylene) (MDPE) Grolier et al.[341] 380460 50200 36.3 SynNonPropane Abdulagatov et al.[139] 292369 4.24.2 n.a. SynOthPcTc

Coquelet et al.[26] 277353 0.53.1 n.a. SynVisGlos et al.[331] 90340 02.4 n.a. SynTGlos et al.[332] 90340 02.4 n.a. SynTHorstmann et al.[358] 369369 4.24.2 10 SynVisTcLee et al.[440] 268318 0.41.5 85 SynVis

Propene Glos et al.[331] 95340 02.9 n.a. SynTGlos et al.[332] 95340 02.9 n.a. SynTHo et al.[353] 273313 0.51.6 85 SynVisWang et al.[698] 364364 4.64.6 18 SynVisPcTc

Propylcyclohexane Nikitin et al.[540] 624624 2.82.8 n.a. SynNonPcTcPropylene carbonate Wilson et al.[708] 762762 4.14.1 n.a. SynNonConPcTcStyrene VonNiederhausern et al.[121] 473635 0.33.8 0.1 SynNonConPcTcSulfur dioxide Valtz et al.[35] 288403 0.24.9 n.a. SynVis

Valtz et al.[689] 288403 0.23.3 n.a. SynVisSulfur hexafluoride Horstmann et al.[358] 318318 3.73.7 10 SynVisTc

Hurly et al.[368] 278313 1.43.3 27 SynTSulphur hexafluoride Funke et al.[135] 224318 0.23.7 n.a. SynTPcTcSynthethic natural gas Jarne et al.[380] 213261 0.18.1 n.a. SynVisTert-perfluorobutyl methyl ether Sako et al.[596] 462462 2.32.3 5.3 SynVisPcTc

Sako et al.[597] 462462 2.32.3 5.3 SynVisPcTcTetradecanedioic acid Nikitin et al.[541] 862862 1.91.9 n.a. SynNonPcTcTetradecanoic acid Nikitin et al.[539] 763763 1.61.6 n.a. SynNonPcTcToluene Abdulagatov et al.[139] 562593 4.24.2 n.a. SynOthPcTc

Bazaev et al.[164] 591673 435.5 n.a. SynOthPcTcVonNiederhausern et al.[121] 586591 3.94.1 0.1 SynNonConPcTc

Trifluoromethane (HFC-23) Lim et al.[462] 283293 3.24.2 85 SynTLim et al.[463] 283293 3.24.1 85 SynVisLim et al.[465] 283293 3.24.2 85 SynT

Trifluoromethyl methyl ether Kayukawa et al.[409] 300375 0.63.4 n.a. SynNonUndecanoic acid Nikitin et al.[539] 728728 2.12.1 n.a. SynNonPcTcUranium dioxide Manara et al.[96] 31353180 10250 n.a. SynNonVis

Uranium dioxide (non-stoichiometric) Manara et al.[496] 24003150 100100 n.a. SynNonVis


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Water Abdulagatov et al.[139] 573646 2222 n.a. SynOthPcTcVeiga et al.[112] 253333 15.519.5 0.004 SynVis

Xenon Omi et al.[127] 291323 010 n.a. SynNonTcXMPA refrigeration oil Skripov et al.[645] 890890 2.52.5 n.a. SynNonPcTc

Table 4

Binary systems: carbon dioxide + X.


(S)-Boc-piperazine Uchida et al.[679] 308328 920.5 240 AnPTSemY 1-((4-Nitrophenyl)azo)-2-naphthalenol (Para Red) Fasihi et al.[290] 308348 12.235.5 1 AnTValY 1,1,1,2,2-Pentafluoroethane (HFC-125) Di Nicola et al.[263] 284304 1.63.3 254.8 SynT1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea) Valtz et al.[687] 276367 0.27.1 n.a. AnTValVis1,1,1,2,3,4,4,5,5,5-Decafluoropentane Kho et al.[413] 298298 0.76.3 130 AnTVisVar1,1,1,2-Tetrafluoroethane (HFC-134a) Duran-Valencia et al.[276] 252292 0.12 50 AnTVal

Silva-Oliver et al.[641] 329354 1.97.3 40 AnTValVis1,10-Phenanthroline Shamsipur et al.[621] 308348 10.135.5 1 AnTValY 1,2-Limoneneoxide Corazza et al.[236] 313343 8.213.8 25 SynVisVar1,4-Bis-(1-methylethylamino)-9,10-anthraquinone (AQiso03) Tuma et al.[70] 299346 7 20 n.a. AnPTSemYSpec1,4-Bis-(butylamino)-9,10-anthraquinone (AQ04) Tuma et al .[70] 299346 7 20 n.a. AnPTSemYSpec1,4-Bis-(ethylamino)-9,10-anthraquinone (AQ02) Tuma et al .[70] 299346 7 20 n.a. AnPTSemYSpec1,4-Bis-(methylamino)-9,10-anthraquinone (AQ01) Tuma et al .[70] 299346 7 20 n.a. AnPTSemYSpec1,4-Bis-(octadecylamino)-9,10-anthraquinone (AQ18) Tuma et al.[678] 330400 17180 n.a. SynVisSpec1,4-Bis-(octylamino)-9,10-anthraquinone (AQ08) Kraska et al.[430] 310340 919.9 n.a. AnPTSemYSpec

Tuma et al.[70] 299346 7 20 n.a. AnPTSemYSpec1,4-Bis-(pentylamino)-9,10-anthraquinone (AQ05) Tuma et al .[70] 299346 7 20 n.a. AnPTSemYSpec1,4-Bis-(propylamino)-9,10-anthraquinone (AQ03) Kraska et al.[430] 305340 7.818.9 n.a. AnPTSemYSpec

Tuma et al.[70] 299346 7 20 n.a. AnPTSemYSpec1,4-Diamino-2-methoxy-9,10-anthraquinone (C.I. Disperse Red 11) Tuma et al.[678] 300340 10140 n.a. SynVisSpec1,4-Dihydroxy-3-methylthioxanthone Shamsipur et al.[619] 308348 12.135.4 1 AnTValY 1,4-Dimethoxybenzene Lee et al.[447] 313328 2028 5 0 AnPTSemY 1,4-Naphthoquinone Ngo et al.[124] 313313 8.412.3 n.a. SynNonSpec1,8-Cineole Cruz Francisco and Sivik[239] 313333 825 30 AnPTSemY 1,8-Dihydroxy-2-(prop-2-enyl)-9-anthrone Karami et al.[406] 308348 10.132.9 1 AnTValY 1,8-Dihydroxy-9-anthrone Karami et al.[406] 308348 10.135.5 1 AnTValY 1,8-Dihydroxyanthraquinone Galia et al.[56] 327357 6.920.1 85.3 AnTIns1-Amino-2,3-dimethyl-9,10-anthraquinone Shamsipur et al.[618] 308358 12.235.5 1 AnTValY 1-Amino-2,4-dimethyl-9,10-anthraquinone Shamsipur et al.[618] 308358 12.235.5 1 AnTValY 1-Amino-2-ethyl-9,10-nthraquinone Shamsipur et al.[618] 308358 12.235.5 1 AnTValY 1-Amino-2-methyl-9,10-anthraquinone Shamsipur et al.[618] 308358 12.235.5 1 AnTValY 1-Amino-4-hydroxy-2-phenoxy-9,10-anthraquinone (C.I. Disperse Red 60) Kraska et al.[430] 303322 7.297.6 n.a. AnSpecVis

Tuma et al.[678] 310310 7130 n.a. SynVisSpec

1-Butanol Chen et al.[224] 333353 512 100 AnTVcirVisSecuianu et al.[607] 293324 0.510 2560 AnTVisVarSilva-Oliver and Galicia-Luna[640] 324426 9.617 40 AnTValVisPcYeo et al.[732] 303428 717.4 26.71 SynVisVar

1-Butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) Wu et al.[711] 313313 1515 55 AnPTSemYVis1-Butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]) Wu et al.[711] 313313 1515 55 AnPTSemYVis1-Butyne Bardas et al.[163] 303333 0.28.4 200 AnTVLcirVis1-Decanol Scheidgen and Schneider[601] 393393 01000 80 AnT1-Ethyl-2-pyrrolidinone Lee et al.[441] 313393 1.723.1 28 SynVisVarPc1-Ethyl-3-methylimidazolium ethyl sulfate [emim][EtSO4] Blanchard et al.[133] 313333 09.4 10 SynT1-Ethyl-3-methylimidazolium hexafluorophosphate Shariati and Peters[624] 308366 1.497.1 3.5 SynVisVar1H,1H,9H,9H-perfluoro-1,9-nonanediol Mesiano et al.[512] 323323 3035 n.a. SynVisVar1-Heptanol Elizalde-Solis et al.[283] 293431 421.5 100 AnTValVisPc

Scheidgen and Schneider[601] 393393 01000 80 AnTScheidgen and Schneider[601] 393393 01000 80 AnT

1-Hexanol Beier et al.[168] 303313 0.59.8 5 0 AnTVLcirVisElizalde-Solis et al.[283] 324432 2.220.1 100 AnTValVisPc

1-Hexyl-3-methylimidazolium hexafluorophosphate Shariati and Peters[623] 298363 0.694.6 3.5 SynVisVar1-Hydroxy-2-(1-propoxymethyl)-9,10-anthraquinone Shamsipur et al.[620] 308348 12.235.5 1 AnTValY 1-Hydroxy-2-(butoxymethyl)-9,10-anthraquinone Shamsipur et al.[620] 308348 12.235.5 1 AnTValY 1-Hydroxy-2-(ethoxymethyl)-9,10-anthraquinone Shamsipur et al.[620] 308348 12.235.5 1 AnTValY 1-Hydroxy-2-(methoxymethyl)-9,10-anthraquinone Shamsipur et al.[620] 308348 12.235.5 1 AnTValY 1-Hydroxy-2-(n-amyloxymethyl)-9,10-anthraquinone Shamsipur et al.[620] 308348 12.235.5 1 AnTValY 1-Hydroxy-2,4-dimethyl-9-anthrone Karami et al.[406] 308348 10.135.5 1 AnTValY 1-Hydroxy-2-ethyl-9-anthrone Karami et al.[406] 308348 10.135.5 1 AnTValY 1-Hydroxy-2-methyl-9,10-anthraquinone Shamsipur et al.[620] 308348 12.235.5 1 AnTValY 1-Hydroxy-2-methyl-9-anthrone Karami et al.[406] 308348 10.135.5 1 AnTValY 1-Hydroxy-3-methylthioxanthone Shamsipur et al.[619] 308348 12.135.4 1 AnTValY 1-Hydroxy-9,10-anthraquinone Shamsipur et al.[620] 308348 12.235.5 1 AnTValY 1-Hydroxythioxanthane Shamsipur et al.[619] 308348 12.135.4 1 AnTValY 1-Methyl-2-pyrrolidinone Lee et al.[441] 318398 4.824.9 28 SynVisVarPc1-Methylnaphthalene Gutirrez and Luks[346] 219308 0.57.9 79 SynOthVis1-N-Butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) Kamps et al.[403] 293393 0.19.6 3 0 SynVis

Kumelan et al.[433] 293395 0.19.6 29.2 SynVis1-n-Butyl-3-methylimidazolium hexafluorophosphate [bmim][PF6] Anthony et al.[83] 283323 01.3 n .a. AnGrav


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Blanchard et al.[133] 313313 13.713.7 n.a. AnPTSemY Blanchard et al.[133] 313333 09.5 10 SynT

1-n-Butyl-3-methylimidazolium methyl sulfate([bmim][CH3SO4])

Kumean et al.[433] 293413 0.99.8 29.2 SynVis

1-n-Butyl-3-methylimidazolium nitrate [bmim][NO3] Blanchard et al.[133] 313333 09.3 10 SynT1-n-Octyl-3-methylimidazolium hexafluorophosphate

[C8mim][PF6]Blanchard et al.[133] 313333 09.2 10 SynT

1-n-Octyl-3-methylimidazolium tetrafluoroborate[C8mim][BF4]

Blanchard et al.[133] 313333 09.3 10 SynT

1-Octanol Feng et al.[291] 328328 313.3 300 AnPTSemXY Hwu et al.[369] 328328 313.3 300 AnPTSemXY Scheidgen and Schneider[601] 393393 01000 80 AnT

1-Pentanol Laursen et al.[50] 313343 1.910.3 90 AnTVcirXSilva-Oliver and Galicia-Luna[642] 333426 3.518.6 40 AnTValVisPc

1-Phenylethanol Gamse and Marr[317] 303323 3.59 140 AnTVcirVal1-Propanol Laursen and Andersen[435] 308318 0.48.3 570 AnTVis

Yeo et al.[732] 298425 6.216 26.71 SynVisVar2,2 ,3,3,4,4-Hexafluoro-1,5-pentanediol Mesiano et al.[512] 323323 2335 n.a. SynVisVar2,2,3,3-Tetrafluoro-1,4-butanediol Mesiano et al.[512] 323323 3035 n.a. SynVisVar2,3-Dimethylanilin Medina and Bueno[511] 313333 820 15.7 AnPTSemY 2,3-Dimethylhexane Lee et al.[448] 318328 1224 50 AnPTSemY 2,4-Dinitrophenol Shamsipur et al.[617] 308348 12.448.6 1 AnTValY 2,5-Dinitrophenol Shamsipur et al.[617] 308348 12.448.6 1 AnTValY 2,Chloroethyl sulfide Shen et al.[627] 294377 2.317.6 30 SynVis2-Butanol Chen et al.[225] 331351 4.912 n.a. AnTVcirVisVar

Silva-Oliver sand Galicia-Luna[640] 335431 8.514.5 40 AnTValVisPc2-Chloroethyl methyl sulfide Garach-Domech et al.[321] 308348 1.913.5 30 SynVisVar2-Ethoxyethanol Joung et al.[394] 323344 7.312.4 50 AnTVLcirValVisPc2-Ethyl hexanoic acid Ghaziaskar et al.[329] 313323 6.818 10 AnPTSemY 2-Ethyl-1-hexanol Ghaziaskar et al.[329] 313323 6.818 10 AnPTSemY 2-Ethyl-hexyl-2-ethyl hexanoate Ghasziaskar and Daneshfar[327] 313353 1325.3 10 AnPTSemY 2-Methoxyethanol Joung et al.[394] 322343 5.212.4 50 AnTVLcirValVisPc2-Methyl-1-propanol (isobutanol) Chen et al.[225] 331351 512 n.a. AnTVcirVisVar

da Silva and Barbosa[247] 288313 1.58.2 23 AnTVis2-Methyl-2-butanol Heo et al.[352] 313353 3.612.9 33 SynVisVar2-Methyl-2-propanol Heo et al.[352] 313353 4.612.1 33 SynVisVar2-Methylanthracene Yamini et al.[725] 308348 12.235.5 0.5 AnTValY 2-Methylpentan-2,4-diol Petrova et al.[562] 313333 3.216 4.014.0 SynVisVar2-Naphthol Li et al.[459] 308328 1030 377 AnPTSemY

Ngo et al.[124] 313313 8.818 n.a. SynNonSpec2-Nitroanisole Medina and Bueno[509] 313333 820 20 AnPTSemY 2-Octanol Gamse and Marr[317] 303323 2.27.2 140 AnTVcirVal

2-Pentanol Silva-Oliver and Galicia-Luna[642] 332431 2.115.7 40 AnTValVisPc2-Phenyl-1-propanol Medina and Bueno[509] 313333 820 20 AnPTSemY 2-Phenylethanol Lopes et al.[484] 313323 8.224.4 35 AnTValVis2-Propanol (isopropanol) Bamberger and Maurer[160] 293333 1.18.1 38 AnPTConVis

Galicia-Luna et al.[47] 324348 110.4 40 AnTCapValVisSecuianu et al.[41] 293323 0.68.6 2560 AnTVisVar

3,3,4,4,5,5,6,6-Octafluorooctan-1,8-diol Mesiano et al.[512] 323323 918 n.a. SynVisVar3,3,4,5,7-Pentahydroxyflavone (quercetin) Matsuyama et al.[506] 308318 10.125.3 210 AnPTSemY 3-Methoxybenzamide Bristow et al.[189] 343363 912 n.a. AnPTSemYSpec3-Methyl-1-butanol (isopentanol) da Silva and Barbosa[247] 288313 1.28.1 23 AnTVis

Lee et al.[442] 313313 28.3 n.a. AnTVLcirValPcLopes et al.[484] 313323 5.29.4 35 AnTValVis

3-Methyl-2-butanol Lee et al.[442] 313313 28.2 n.a. AnTVLcirValPc3-Nitrotoluol Medina and Bueno[511] 313333 820 15.7 AnPTSemY 4-(N,N-Diethylamino)-4-nitroazobenzene Fasihi et al.[290] 308348 12.235.5 1 AnTValY 4-(N,N-Dimethylamino)-4-nitroazobenzene Fasihi et al.[290] 308348 12.235.5 1 AnTValY 4-Methoxybenzamide Bristow et al.[189] 343363 914 n.a. AnPTSemYSpec4-Methoxyphenylacetic acid Lee and McHugh[451] 308367 13.489.2 n.a. SynVisVar4-Phenyl-toluene Leeke et al.[453] 353383 9.430.7 25 SynVis4-Vinylbenzyl acetylacetone Powell et al.[572] 273333 1025.6 n.a. SynVisVar5,10,15,20-

Tetrakis(3,5bis(trifluoromethyl)phenyl)porphyrinSane et al.[31] 313373 10.332.4 45 AnTVisVarVal

5,10,15,20-Tetrakis(pentafluorophenyl)porphyrin Sato et al.[598] 313333 10.325.2 40 AnTVcirSpec5-Fluorouracil Guney and Akgerman[344] 308328 1121 n.a. AnPTSemY 7,8-Dihydroxyflavone Matsuyama et al.[506] 308318 9.125.3 210 AnPTSemY 8-Hydroxyquinoline Shamsipur et al.[621] 308338 10.135.5 1 AnTValY 9-nitroanthracene Yamini et al.[725] 308348 12.235.5 0.5 AnTValY -Asarone Chen et al.[228] 308322 918 1500 AnPTSemY Acenaphthene Yamini and Bahramifar[722] 308348 12.135.4 1 AnTValY Acetaminophen Bristow et al.[189] 313353 825 n.a. AnPTSemYSpecAcetic acid (ethanoic acid) Bamberger et al.[61] 313353 1.111.1 38 AnPTCon

Byun et al.[195] 313393 2.716.5 28 SynVisVarAcetoacetate Powell et al.[572] 273333 7.231.7 n.a. SynVisVarAcetoacetate fluoroacrylate polymer Powell et al.[572] 293293 9.511 n.a. SynVisVarAcetone Bamberger and Maurer[160] 303333 1.18.1 38 AnPTConVis


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Chen et al.[226] 323336 8.99.9 2050 SynVisVarPcTcWu et al.[709] 322363 9.211 14 SynVis

Acetonitrile (ethanenitrile) Corazza et al.[236] 313343 4.811.7 25 SynVisVar-Cyclodextrin octadecaacetate Potluri et al.[569] 298298 2047 100 SynVisVar-Methylstyrene Phiong and Lucien[563] 308323 2.99.1 70 AnTLcirVisAmical-48 (diiodomethyl p-tolyl sulfone) Sahle-Demessie et al.[595] 318338 1030 43.92 AnPTSemYVis-Naphthol Abaroudi et al.[143] 308318 10.616.2 n.a. AnPTSemY Anthracene Goodarznia and Esmaeilzadeh[334] 308308 10.218.1 n.a. AnPTSemY

Li et al.[459] 308328 1030 377 AnPTSemY Ngo et al.[124] 313313 720.8 n.a. SynNonSpecShinoda and Tamura[635] 323323 1030 2.3 AnPTSemY

Anth

dohrn et al

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