High-Pressure Uid-Phase Equilibria: Experimental Methods and Systems Investigated (2005-2008)

Fluid Phase Equilibria 300 (2011) 1–69
Contents lists available at ScienceDirect
Fluid Phase Equilibria

journal homepage: www.elsevier.com/locate/fluid
Review
High-pressure fluid-phase equilibria: Experimental methods and systems

investigated (2005–2008)
José M.S. Fonseca a , Ralf Dohrn b,∗ , Stephanie Peper c
a
Technical University of Denmark, Department of Chemical and Biochemical Engineering, DK-2800 Kgs. Lyngby, Denmark
b
Bayer Technology Services GmbH, Fluid Properties & Thermodynamics, Geb. B310, D-51368 Leverkusen, Germany
c
Helmut-Schmidt-University/University of the Federal Armed Forces Hamburg, Institute of Thermodynamics, D-22043 Hamburg, Germany
a r t i c l e i n f o a b s t r a c t
Article history: A review of systems is given, for which experimental high-pressure phase-equilibrium data were pub-
Received 11 August 2010 lished in the period between 2005 and 2008, continuing a series of reviews. To find candidates for articles
Received in revised form 3 September 2010 that are of interest for this survey a three-stage search strategy was used including a systematic search of
Accepted 7 September 2010
the contents of the 17 most important journals of the field. Experimental methods for the investigation
Available online 25 September 2010
of high-pressure phase equilibria were classified, described and illustrated using examples from arti-
cles of the period between 2005 and 2008. For the systems investigated, the reference, the temperature
Keywords:
and pressure range of the data, and the experimental method used for the measurements is given in 54
Experimental equipment
Data
tables. Vapor–liquid equilibria, liquid–liquid equilibria, vapor–liquid–liquid equilibria, solid–liquid equi-
Method libria, solid–vapor equilibria, solid–vapor–liquid equilibria, critical points, the solubility of high-boiling
High pressure VLE review substances in supercritical fluids, the solubility of gases in liquids and the solubility (sorption) of volatile
Hydrocarbons components in polymers are included. Most of experimental data in the literature has been given for
Non-hydrocarbons binary systems. Of the 1469 binary systems, 796 (54%) have carbon dioxide as one of the components.
Information on 206 pure components, 535 ternary systems of which 355 (66%) contain carbon dioxide,
163 multicomponent and complex systems, and 207 systems with hydrates is given. A continuation of
the review series is planned, covering the years from 2009 to 2011.
© 2010 Elsevier B.V. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Literature search and evaluation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. Experimental methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.1. Analytical methods (An) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.1.1. Analytical isothermal methods (AnT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.1.2. Analytical isobaric–isothermal methods (AnPT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
3.1.3. Analytical isobaric methods (AnP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
3.1.4. Analytical spectroscopic methods (AnSpec) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
3.1.5. Analytical gravimetric methods (AnGrav) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3.1.6. Other analytical methods (AnOth) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
3.2. Synthetic methods (Syn) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.2.1. Synthetic-visual methods (SynVis) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
3.2.2. Synthetic-non-visual methods (SynNon) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
3.2.3. Synthetic-isothermal methods (SynT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
3.2.4. Synthetic-isobaric methods (SynP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
3.2.5. Other synthetic methods (SynOth) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
∗ Corresponding author at: Bayer Technology Services GmbH, Fluid Properties & Thermodynamics, BTS-PT-RPT-KPM, Geb. B310 Room 609, D-51368 Leverkusen,
Germany. Tel.: +49 214 30 21787; fax: +49 214 30 81554.
E-mail address: ralf.dohrn@bayer.com (R. Dohrn).
0378-3812/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2010.09.017
2 J.M.S. Fonseca et al. / Fluid Phase Equilibria 300 (2011) 1–69
3.3. Important points for experimental methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60

3.3.1.1. Charging of the cell – synthesis of the mixture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
3.3.1.2. Equilibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
3.3.1.3. Analysis and determination of a phase transition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
4. Systems investigated . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
1. Introduction like Schwarz et al. [17] for ethane + n-alkane systems, or for a spe-
cific substance, like Abdulagatov et al. [18] for methanol or Loerting
Knowledge of high-pressure phase equilibria is important for et al. [19] for phase transitions of ice. Other reviews cover high-
the understanding of technical and natural processes that occur pressure fluid-phase equilibria data that have been published in
at high pressures. It is essential for the design and optimization of specific periods, e.g. Knapp et al. [20] covering 1900–1980, Fornari
high-pressure chemical processes and separation operations. Other et al. [21] covering 1978–1987, Dohrn and Brunner [22] cover-
examples for the need of high-pressure phase equilibrium data are ing 1988–1993, Christov and Dohrn [23] covering 1994–1999, and
the simulation of petroleum reservoirs, enhanced oil recovery, car- Dohrn et al. [6] covering 2000–2004. This work gives an overview
bon capture and storage, the transportation and storage of natural about systems for which high-pressure phase equilibrium data
gas, refrigeration and heat-pump cycles, and the study of geologi- have been published from 2005 to 2008, including vapor–liquid
cal processes. There are several established and new applications of equilibria (VLE), liquid–liquid equilibria (LLE), vapor–liquid–liquid
supercritical fluids [1,2], like extraction, particle formation, impreg- equilibria (VLLE), the solubility of high-boiling substances in super-
nation (wood preservation, polymers, catalysts, textiles), leather, critical fluids, and the solubility of gases in liquids (GLE). Work on
paper and textile treatment, dyeing, cleaning, reaction, chromatog- the continuation of the review series is under way, covering the
raphy, drying of aerogel, injection molding and extrusion, and period between 2009 and 2011.
electronic chip manufacturing. Examples of new applications are
given in the recent review of Brunner [3]. A critical review of the 2. Literature search and evaluation
present state and future directions of supercritical fluid science and
technology is given in the 20th anniversary special issue of The To find the articles that are of interest for this review, a three-
Journal of Supercritical Fluids [4]. stage search strategy was applied. A detailed description of this
Although the patent review on supercritical fluid technology strategy can be found in our previous review [6]. The main source
of Schütz [5] showed that the number of patents applications on of information were the most important journals in the field of
supercritical fluids reached a maximum in 2002, the number of high-pressure phase equilibria, as listed in Table 1; abbreviation of
publications in this field is still increasing, e.g. the total number of journal titles were used according to ISO 4 [24]. In addition to the 13
publications in The Journal of Supercritical Fluids. Other reasons for journals that were systematically covered in our previous review,
the high number of publications on high-pressure phase equilibria we added 4 journals: Thermochimica Acta, International Journal of
are a rising interest in ionic liquid applications at high pressures, Refrigeration, Journal of Cellular Plastics and Separation Science and
in hydrate formation and in polymer foaming processes. Gas solu- Technology. The latter journal yielded only one relevant article and
bility in the polymer plays a significant role in almost all stages of will not be continued in the future review, planned to cover the
the foaming process including the gas dissolution at compounding period 2009–2011. The table of contents of the journals of Table 1
temperatures and pressures, bubble nucleation, and growth and were systematically searched. Conference proceedings were not
partitioning between cells and matrix for cell structure stabiliza- considered, but articles from other journals that came to our knowl-
tion. The search for new solvents for carbon dioxide (CO2 ) capture edge were included. During the evaluation process of more than
also increased the number of publications on high-pressure phase 800 articles of interest, about 5% of the papers were found to be
equilibria. irrelevant for this review, since they contain neither new experi-
There are many ways to obtain information about the phase mental data nor the description of a new experimental apparatus, or
behavior of fluid mixtures, but the direct measurement of phase- the measured data were not “high pressure”. Of course, the expres-
equilibrium data remains an important source of information, sion “high pressure” is relative; we chose 1 MPa as the lower limit:
though it is difficult and expensive to take precise experimental a paper was considered to contain high-pressure data if at least one
data. On the other hand, for a company, it is very often more expen- data point was measured at a pressure of 1 MPa or higher.
sive to use imprecise data or to estimate data a couple of times over The increase of interest in high-pressure phase equilibria con-
the years, if experimental data are not available. tinued from 2005 to 2008 but first signs of a slowing down of this
An overview on review articles about techniques for exper- process can be seen. In Table 1 the number of papers published
imental investigations and about reviews on high-pressure in different journals from 1978 to 1987 [21] is compared with the
phase-equilibrium data in the literature has been given in the pre- number published from 1988 to 1993 [22], from 1994 to 1999 [23],
vious article of this series [6]. From the reviews on experimental from 2000 to 2004 [6] and from 2005 to 2008 (this work). While in
methods that appeared after 2004 the articles of Knox [2], Richon the early 1980s about 20 articles on high-pressure phase equilib-
[7], Smith and Fang [8], and Dohrn et al. [6] shall be mentioned. ria were published each year, this number increases by 6–7 each
Some reviews on experimental data in the literature cover a year, so that in 2008 more than 10 times as many articles appeared
specific topic, such as the phase behavior of ionic liquids with super- as in 1982. Fig. 1 shows an almost linear increase of articles on
critical fluids, e.g. Keskin et al. [9], the critical properties of elements high-pressure phase equilibria published per year during the last
and compounds, e.g. Marsh et al. [10,11], the solubility of certain 30 years.
substances in supercritical CO2 , e.g. Gücli-Üstündag and Temelli Authors tend to submit their publications on high-pressure
[12,13] for lipids, Su and Chen [14] for pharmaceutical compounds, phase equilibrium data to a rather limited number of mostly spe-
or the solubility of inorganic and organic compounds in liquids at cialized journals. More than 80% of the information was published
high pressures, e.g. Sawamura [15], for high-pressure gas hydrates, in the three major journals of high-pressure phase equilibria: Jour-
e.g. Loveday and Nelmes [16], for a certain class of binary systems, nal of Chemical Engineering Data, Fluid Phase Equilibria, and The
J.M.S. Fonseca et al. / Fluid Phase Equilibria 300 (2011) 1–69 3
225 fluid extraction, can be large and contain several functional groups.
Therefore, the experimental investigation is often the only suitable
200
method to precisely determine the high-pressure phase behav-
175 ior. Many different methods are used to measure high-pressure
Number of articles/year
phase equilibria. The reason is that no single method is suitable

150 to determine all different phenomena. To the reader the variety
125 of experimental methods is even more confusing since different
authors use different names for the same experimental method.
100 Expressions like ‘static’ or ‘dynamic’ are used in connection with
many different methods.
75
Therefore, an overview of experimental methods for the deter-
50 mination of high-pressure phase equilibria is given in this section.
The methods are described, their advantages and disadvantages are
25
discussed and many examples of their application are given citing
0 articles of the period of this review. At the end of Section 3 some
1981 1984 1987 1990 1993 1996 1999 2002 2005 2008 guidelines for the design of the apparatus and the experimental
year procedure to measure high-pressure phase equilibria are given.
The used classification of experimental methods for the investi-
Fig. 1. Number of articles published per year during the last 30 years.
gation of high-pressure phase equilibria is described in detail in our
previous review [6]. There are two main classes, depending on how
Journal of Supercritical Fluids. From 1996 to 2008 between 12 and the compositions of the equilibrium phases are determined (ana-
18% of all articles in these journals were on high-pressure phase lytically or not) and whether the mixture to be investigated has
equilibria. During the last 10 years the average percentage stayed been prepared (synthesized) with precisely known composition or
more or less constant at 15%, meaning that the increase of the not: analytical methods and synthetic methods. The classification
number of articles on high-pressure phase equilibria can be partly includes a unique name and an abbreviation of the name for each
explained by the general increase of published articles in these method as given in Table 2.
journals, particularly in The Journal of Supercritical Fluids. The frequency of the use of a method gives an indication on
its importance; it is given in Table 2 as well. 62.4% of all systems
3. Experimental methods of the period of this review have been measured with a synthetic
method, while 37.6% have been investigated with an analytical
High-pressure phase behavior is often complex and difficult to method. When these numbers are compared with the values of
predict. At high pressures deviations from ideal behavior become the period of our earlier review [6] (2000–2004) it can be seen
much larger than at ambient or moderate pressures. Another dif- that there is a tendency towards synthetic methods. Particularly,
ficulty of using predictive methods is the fact that molecules of non-visual synthetic methods and the synthetic isothermal method
interest for high-pressure applications, particularly supercritical have been used more frequently than in the past. Since commer-
Table 1
Bibliographic information.
Journal Number of articles on high-pressure phase equilibria
1978–1987a 1988–1993b 1994–1999c 2000–2004d 2005–2008e
J. Chem. Eng. Data 92 115 214 231 283

Fluid Phase Equilib. 69 158 182 206 169
J. Supercrit. Fluidsf 0 43 73 115 143
J. Chem. Thermodyn. – – 30 26 48
Ind. Eng. Chem. Res. 15 18 30 58 44
Int. J. Thermophys. – – – 23 14
J. Phys. Chem. B 3 5 1 4 14
Chem. Eng. Sci. 2 1 4 4 13
Thermochim. Acta – – – – 12
Green Chemistryg 0 0 0 1 10
AIChE J. 5 5 1 10 8
Int. J. Refrig. – – – – 4
J. Cell. Plast. – – – – 3
Can. J. Chem. Eng. 3 13 8 1 3
Phys. Chem. Chem. Phys.h 10 8 6 13 2
J. Chem. Eng. Jpn. – 14 4 0 2
Sep. Sci. Technol. – – – – 1
Other journals – – 16 5 18
Total 199 380 569 697 791
Abbreviation of journal titles according to ISO 4 [24], (–): not covered in the review of the period.
a
Fornari et al. [21].
b
Dohrn and Brunner [22].
c
Christov and Dohrn [23].
d
Dohrn et al. [6].
e
This work.
f
The first issue of The Journal of Supercritical Fluids appeared in 1988.
g
The first issue of Green Chemistry appeared in 1999.
h
Before 1999: Berichte der Bunsengesellschaft für Physikalische Chemie and J. of the Chemical Society/Faraday Transactions.
Table 2
Experimental methods: abbreviations and frequency of use in review period.
Experimental method Systems measured with method
2000–2004 2005–2008 Trend
Analytical methods 46.7% 37.6%

Total composition not exactly known, analysis of phases
Analytical methods with sampling
AnT Analytical isothermal method 27.6% 19.7%
Cap Sampling through capillaries
Val Sampling using a special valve
Blo Blocking off a large sampling volume from the equil. cell
Vcir Vapor-phase recirculation
Lcir Liquid-phase recirculation
VLcir Recirculation of the vapor and the liquid phase
Ins In situ sampling
Mla Material loss analysis
AnP Analytical isobaric method 0.0% 0.0% –
AnPT Analytical isobaric–isothermal method 15.4% 11.2%
Con Continuous-flow method
SemX Semi-flow method (gas solubility in liquid phase)
SemY Semi-flow method (solubility in vapor phase)
Chro Chromatographic method, e.g. Inverse SFC
Analytical methods without sampling
AnSpec Analytical spectroscopic method 1.5% 1.1% –
AnGrav Analytical gravimetric method 1.1% 5.0%
AnOth Other analytical method 1.1% 0.6% –
Synthetic methods 53.3% 62.4%
Total composition exactly known, no analysis of phases
Synthetic methods with a phase transition
SynVis Synthetic-visual method 36.4% 36.0% –
SynNon Synthetic-nonvisual method 8.4% 13.4%
Synthetic methods without a phase transition
SynT Synthetic-isothermal method 6.1% 11.8%
SynP Synthetic-isobaric method 0.2% 0.5% –
SynOth Other synthetic method 2.2% 0.7%
Additional information for all methods
Var Variable-volume cell
Vis Visual observation is possible
Spec Spectroscopic method to get information
Pc Critical pressure has been measured
Tc 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
cially available electrobalances became more prevalent, analytical significantly. This pressure drop can be avoided by different mea-
gravimetic methods have been used significantly more frequently sures, e.g by decreasing the cell volume during sampling by using a
(5.0% of all systems) as compared to the period 2000–2004 (1.1% of variable-volume cell (Var) like in the new VLE apparatus of Raal
all systems), being the only analytical method whose usage did not and coworkers [25], or by blocking off (Blo) the sampling vol-
decline. ume from the remaining content of the equilibrium cell before
In Tables 3–56, listing the investigated systems, information on pressure reduction [26,27]. If only a small sample is withdrawn
the experimental method used to determine the data is included. or if a relatively large equilibrium cell is used, the slight pres-
sure drop does not affect the phase compositions significantly.
The largest equilibrium cell described in an article within this
3.1. Analytical methods (An) review had a volume of 40 dm3 . It was used by van der Kraan
et al. [28] for the measurement of the partitioning of C.I. Disperse
Analytical methods (designated with An) involve the analyti- Orange 3 between CO2 and poly(ethylene terephtalate) textile
cal determination of the compositions of the coexisting phases. cloth.
When the equilibrium cell is filled with the components at the Small samples can be withdrawn using capillaries (Cap) or
beginning of the experiment, the overall composition of the mix- special sampling valves (Val), e.g. using HPLC-valves, or fast-
ture does not need to be precisely known, only so far that the acting electromagnetic or pneumatic valves, like the rapid on-line
mixture under desired conditions (p and T) separates into two sampler-injector of Richon and coworkers [29]. Often sampling
or more phases that are to be investigated, e.g. into a liquid valves are directly coupled to analytical equipment, in most cases
and a vapor phase when VLE is to be measured. The composi- to a gas chromatograph [30], but also to a high-performance liquid
tion of the phases is analyzed either with sampling and analysis chromatograph, or a supercritical fluid chromatograph.
under ambient pressure or without sampling by using physico- The smallest equilibrium cell described in an article within this
chemical methods of analysis inside the equilibrium cell under review had a volume of only 1 cm3 and was used by Yamini and
pressure. coworkers [31,32]. From this cell they took a sample-volume of
Analytical methods with sampling can be classified, depend- 102 mm3 which is the largest relative sample (10%) from a constant
ing on the attainment of equilibrium, into isothermal methods volume cell [32].
(AnT), isobaric–isothermal methods (AnPT) and isobaric methods Sometimes, equilibrium cells used for analytical methods are
(AnP). Withdrawing a large sample from an autoclave causes a equipped with one or more windows for visual observation of the
considerable pressure drop, which disturbs the phase equilibrium
Table 3
Pure-component systems: X.
X Reference T (K) P (MPa) V (cm3 ) Method
1,1,1,2,3,3,3-Heptafluoropropane (HFC-227ea) Lim et al. [507] 273–323 0.1–0.9 85 SynT

Yun et al. [786] 288–363 0.3–2.2 200 SynT
1,1,1,2,3,3-Hexafluoropropane (HFC-236ea) Gruzdev et al. [329] 293–412 0.1–3.3 439 SynT
1,1,1,2-Tetrafluoroethane (HFC-134a) Cui et al. [240] 263–283 0.2–0.4 n.a. SynTVis
Fedele et al. [296] 253–293 0.1–0.6 50 SynT
Hong et al. [352] 295–304 0.6–0.7 329 SynT
Marcelino Neto and Barbosa [538] 283–313 0.4–1 4000 SynT
Saleh and Wendland [627] 253–363 0.1–3.2 200 AnGrav
Valtz et al. [731] 277–360 0.3–3 n.a. SynTVis
1,1,1,3,3-Pentafluoropropane (HFC-245fa) Pan et al. [589] 253–403 0–2.3 11.3 SynVis
1,10-Diaminodecane Nikitin et al. [574] 736–736 2.4–2.4 n.a. SynNonPcTc
1,12-Diaminododecane Nikitin et al. [574] 767–767 2–2 n.a. SynNonPcTc
1,1-Difluoroethane (HFC-152a) Lim et al. [504] 273–323 0.2–1.1 85 SynT
Madani et al. [532] 253–348 0.1–2.1 n.a. AnTCapValVis
1,1-Ethanediol diacetate VonNiederhausern et al. [748] 461–618 0.1–2.9 n.a. SynNonConPcTc
1,2,2,2-Tetrafluoroethyl trifluoromethyl ether Yasumoto et al. [777] 377–377 3.6–3.6 16 SynVisVarPcTc
(HFE-227me)
1,2-Benzenediol VonNiederhausern et al. [749] 511–754 0–3.9 n.a. SynNonCon
1,2-Bis-(4-n-dodecyloxybenzoyl)hydrazine Maeda and Yokoyama [534] 405–465 0.1–89 n.a. SynNon
1,2-Bis-(4-n-octyloxybenzoyl)hydrazine Maeda and Yokoyama [534] 407–467 0.1–83 n.a. SynNon
1,2-Diaminoethane Nikitin et al. [574] 614–614 6.6–6.6 n.a. SynNonPcTc
1,2-Epoxy-2-methylpropane VonNiederhausern et al. [748] 320–499 0–4.3 n.a. SynNonConPcTc
1,3-Benzenediol VonNiederhausern et al. [749] 546–836 0–6.2 n.a. SynNonConPcTc
1,3-Butanediol VonNiederhausern et al. [748] 481–692 0.1–5.1 n.a. SynNonConPcTc
1,3-Diaminopropane Nikitin et al. [574] 632–632 5.5–5.5 n.a. SynNonPcTc
1,4-Diaminobutane Nikitin et al. [574] 651–651 4.5–4.5 n.a. SynNonPcTc
1,5-Hexadiene Giles and Wilson [316] 333–373 0.1–0.3 n.a. SynT
1,6-Diaminohexane Nikitin et al. [574] 685–685 3.5–3.5 n.a. SynNonPcTc
1,6-Hexanediol VonNiederhausern et al. [749] 523–740 0–4 n.a. SynNonConPcTc
1,8-Diaminooctane Nikitin et al. [574] 712–712 2.8–2.8 n.a. SynNonPcTc
1,9-Diaminononane Nikitin et al. [574] 726–726 2.6–2.6 n.a. SynNonPcTc
1-Butanol Dell’Era et al. [254] 364–364 0–0 n.a. SynT
Gil et al. [115] 563–563 4.4–4.4 4 SynVisConPcTc
1-Butene Ihmels et al. [365] 289–419 0.2–4 n.a. SynVisVarPcTc
Visuri et al. [743] 364–364 1.5–1.5 113 SynT
1-Dodecanethiol VonNiederhausern et al. [131] 544–733 0–1.8 n.a. SynNonConPcTc
1-Heptanol Gil et al. [115] 632–632 3–3 4 SynVisConPcTc
1-n-Butyl-3-methylimidazolium hexafluorophosphate Gomes de Azevedo et al. [119] 285–303 0.1–88.9 0.8 SynNon
[bmim] [PF6 ]
1-Phenyldodecane Milhet et al. [547] 269–292 0.1–100 0.03 SynVis
1-Phenylheptadecane Milhet et al. [547] 292–292 0.1–0.1 0.03 SynVis
1-Phenylhexadecane Milhet et al. [547] 299–320 0.1–100 0.03 SynVis
1-Phenylnonadecane Milhet et al. [547] 302–322 0.1–100 0.03 SynVis
1-Phenyloctadecane Milhet et al. [547] 309–329 0.1–100 0.03 SynVis
1-Phenylpentadecane Milhet et al. [547] 285–306 0.1–100 0.03 SynVis
1-Phenyltetradecane Milhet et al. [547] 289–309 0.1–100 0.03 SynVis
1-Phenyltridecane Milhet et al. [547] 272–293 0.1–100 0.03 SynVis
1-Phenylundecane Milhet et al. [547] 256–277 0.1–100 0.03 SynVis
1-Propanol Gil et al. [115] 537–537 5.1–5.1 4 SynVisConPcTc
Roininen et al. [620] 364–364 0.1–0.1 113 SynT
Visuri et al. [743] 364–364 0.1–0.1 113 SynT
1-Tert-butoxy-2-propanol VonNiederhausern et al. [131] 450–600 0.2–2.7 n.a. SynNonConPcTc
2-(2-Aminoethoxy)-ethanol VonNiederhausern et al. [748] 500–721 0.1–4.8 n.a. SynNonConPcTc
2-Butanol Dell’Era et al. [254] 364–364 0.1–0.1 n.a. SynT
Laavi et al. [475] 364–364 0.1–0.1 113 SynT
Visuri et al. [743] 364–364 0.1–0.1 113 SynT
Wierink et al. [765] 364–364 0.1–0.1 113 SynT
2-Methyl-2-propanol Dell’Era et al. [254] 364–364 0.1–0.1 n.a. SynT
Laavi et al. [475] 364–364 0.1–0.1 113 SynT
Visuri et al. [743] 364–364 0.1–0.1 112.7 SynT
Wierink et al. [765] 364–364 0.1–0.1 112.7 SynT
2-Methylpropane (isobutane) Chen et al. [219] 272–313 0.1–0.5 31.7 SynT
Giles and Wilson [316] 298–248 0.3–1.2 n.a. SynT
Glos et al. [318] 115–340 0–1 n.a. SynT
Masui et al. [111] 310–407 0.4–3.6 18 SynVisVarPcTc
Yasumoto et al. [776] 407–407 3.6–3.6 16 SynVisVarPcTc
2-Phenyl-1-ethanol Nikitin et al. [130] 720–720 3.8–3.8 n.a. SynNonPcTc
2-Phenylacetic acid (phenylethanoic acid) Nikitin et al. [576] 766–766 3.9–3.9 n.a. SynNonPcTc
2-Phenylethanol VonNiederhausern et al. [131] 488–723 0–3.9 n.a. SynNonConPcTc
2-Propanol (isopropanol) Dell’Era et al. [254] 364–364 0.1–0.1 n.a. SynT
Laavi et al. [475] 364–364 0.1–0.1 113 SynT
Visuri et al. [743] 364–364 0.1–0.1 113 SynT
Table 3 (Continued)
2-Propene-1-ol VonNiederhausern et al. [131] 438–547 0.7–5.6 n.a. SynNonConPcTc

3-(3 -Chloro-)(4 -n- Maeda et al. [533] 408–491 0.1–300 n.a. SynNon
octyloxybenzoyloxyphenyliminomethyl)
phenyl-4 -n-octyloxy biphenylcarboxylate
3-(4 -n-octyloxybenzoyloxyphenyliminomethyl) Maeda et al. [533] 405–506 0.1–300 n.a. SynNon
phenyl-4 -n-octyloxy biphenylcarboxylate
3,3 -Diamino-4,4 -azofurazan (DAAzF) Sinditskii et al. [683] 873–1028 1–5 50 SynNon
3-Phenyl-1-propanol Nikitin et al. [130] 732–732 3.4–3.4 n.a. SynNonPcTc
3-Phenylpropanoic acid Nikitin et al. [576] 776–776 3.4–3.4 n.a. SynNonPcTc
4-(Ethylpentoxy)-anilinebenzylidenen-4 -carboxylic Maeda et al. [124] 423–518 0.1–300 n.a. SynNon
acid
4-Formylmorpholine VonNiederhausern et al. [748] 507–779 0–5 n.a. SynNonConPcTc
4-Hexyloxybenzoloxy-4 -cyanoazobenzene Sandhya et al. [629] 399–448 0.1–150 n.a. SynNon
4-Octyloxybenzoloxy-4 -cyanoazobenzene Sandhya et al. [629] 368–413 0.1–120 n.a. SynNon
4-Phenyl-1-butanol Nikitin et al. [130] 746–746 3–3 n.a. SynNonPcTc
4-Phenylbutanoic acid Nikitin et al. [576] 783–783 3.2–3.2 n.a. SynNonPcTc
5-Phenylpentanoic acid Nikitin et al. [576] 790–790 2.9–2.9 n.a. SynNonPcTc
6-Phenylhexanoic acid Nikitin et al. [576] 794–794 2.6–2.6 n.a. SynNonPcTc
7-Phenylheptanoic acid Nikitin et al. [576] 798–798 2.4–2.4 n.a. SynNonPcTc
Acetonitrile (ethanenitrile) Giles and Wilson [316] 393–453 0.2–1 n.a. SynT
Allyl chloride Giles and Wilson [316] 333–373 0.1–0.4 n.a. SynT
Ammonia Gil et al. [115] 405–405 11.3–11.3 4 SynVisConPcTc
Martin et al. [96] 403–404 11.1–11.1 27 SynVisPcTc
Sato et al. [631] 310–405 1.4–11.3 n.a. SynVisVarPcTc
Tomida et al. [718] 303–373 1.1–6.2 65.2 SynT
Wu et al. [768] 286–324 0.7–2 769 SynT
Anhydrous caffeine Deiters and Randzio [252] 410–560 0–200 n.a. SynNon
Benzene Xu et al. [772] 306–663 100–3000 94 SynNonVar
Bis(2-ethylhexyl) phthalate Nikitin et al. [575] 835–835 1–1 n.a. SynNonPcTc
Bromobenzene Xu et al. [772] 259–587 100–3500 94 SynNonVar
Butyl benzoate Nikitin et al. [577] 725–725 2.4–2.4 n.a. SynNonPcTc
Carbon dioxide Gil et al. [115] 304–304 7.3–7.3 4 SynVisConPcTc
Kim and Kim [423] 253–303 1.9–7.2 150 SynTVis
Ravipaty et al. [612] 308–328 10.1–28 1.6 AnPTSemYVal
Saleh and Wendland [627] 233–293 1–5.7 200 AnGrav
Shariati et al. [659] 293–304 5.7–7.3 n.a. SynT
Vyhmeister et al. [751] 304–305 3.3–7.6 n.a. SynVisVarPcTc
Ceramide 3A (N-linoeoyl-phytosphingosine, 97%) Vezzu et al. [742] 397–397 0.1–0.1 n.a. SynNon
Chlorobenzene Xu et al. [772] 246–530 100–3500 94 SynNonVar
Chloromethane (HCC-40) Giles and Wilson [316] 273–313 0.2–0.8 n.a. SynT
Cholesterol Vezzu et al. [742] 420–420 0.1–0.1 n.a. SynNon
Cis-2-Butene Ihmels et al. [365] 290–435 0.1–4.2 n.a. SynVisVarPcTc
Cyclohexane Gil et al. [115] 553–553 4–4 4 SynVisConPcTc
Cyclopropane Fedele et al. [296] 253–293 0.1–0.5 50 SynT
Decylcyclohexane Milhet et al. [546] 271–293 0.1–100.1 0.03 SynVis
Dipropylene glycol VonNiederhausern et al. [748] 505–705 0.1–3.3 n.a. SynNonConPcTc
Dibutyl phthalate Nikitin et al. [575] 797–797 1.6–1.6 n.a. SynNonPcTc
Didecyl phthalate Nikitin et al. [575] 870–870 0.9–0.9 n.a. SynNonPcTc
Diethyl oxalate VonNiederhausern et al. [748] 454–645 0.1–3 n.a. SynNonConPcTc
Diethyl phthalate Nikitin et al. [575] 776–776 2.2–2.2 n.a. SynNonPcTc
Diheptyl phthalate Nikitin et al. [575] 830–830 1.2–1.2 n.a. SynNonPcTc
Dihexyl phthalate Nikitin et al. [575] 817–817 1.3–1.3 n.a. SynNonPcTc
Dimethoxymethane Pan et al. [589] 283–398 0–0.9 11.3 SynVis
Dimethyl adipate Verevkin et al. [741] 692–692 2.5–2.5 n.a. SynNonPcTc
Dimethyl disulfide VonNiederhausern et al. [748] 466–607 0.6–5 n.a. SynNonConPcTc
Dimethyl ether Corvaro et al. [233] 219–361 0–2.6 273.5 SynT
Giles and Wilson [317] 253–293 0.1–0.5 n.a. SynT
Ihmels and Lemmon [366] 264–400 0.1–5.3 n.a. SynVisVarPcTc
Valtz et al. [731] 278–360 0.3–2.5 n.a. SynTVis
Wu and Yin [767] 213–393 0–4.7 11.3 SynTVis
Dimethyl glutarate Verevkin et al. [741] 682–682 2.7–2.7 n.a. SynNonPcTc
Dimethyl malonate Verevkin et al. [741] 649–649 3.5–3.5 n.a. SynNonPcTc
Dimethyl oxalate Verevkin et al. [741] 639–639 4–4 n.a. SynNonPcTc
Dimethyl phthalate Nikitin et al. [575] 772–772 2.7–2.7 n.a. SynNonPcTc
Dimethyl pimelate Verevkin et al. [741] 711–711 2.3–2.3 n.a. SynNonPcTc
Dimethyl sebacate Verevkin et al. [741] 742–742 2–2 n.a. SynNonPcTc
Dimethyl suberate Verevkin et al. [741] 723–723 2.3–2.3 n.a. SynNonPcTc
Dimethyl succinate Verevkin et al. [741] 662–662 3–3 n.a. SynNonPcTc
Di-n-butyl disulfide VonNiederhausern et al. [748] 504–614 0.1–0.7 n.a. SynNonCon
Dinonyl phthalate Nikitin et al. [575] 858–858 1–1 n.a. SynNonPcTc
Dioctyl phthalate Nikitin et al. [575] 840–840 1–1 n.a. SynNonPcTc
Dipentyl phthalate Nikitin et al. [575] 811–811 1.4–1.4 n.a. SynNonPcTc
Table 3 (Continued)
Dipropyl phthalate Nikitin et al. [575] 784–784 1.9–1.9 n.a. SynNonPcTc

Diundecyl phthalate Nikitin et al. [575] 886–886 0.8–0.8 n.a. SynNonPcTc
Dodecylcyclohexane Milhet et al. [546] 285–308 0.1–100.1 0.03 SynVis
Eicosane Machado et al. [138] 318–344 33.5–150 n.a. SynNon
Ethane Gil et al. [115] 305–305 4.8–4.8 4 SynVisConPcTc
Zhang et al. [806] 188–243 0.1–1 300 AnTVcir
Zhu et al. [815] 179–210 0.1–0.3 300 AnTVcir
Ethanol Bazaev et al. [184] 373–513 0.2–6 32 SynT
Gil et al. [115] 514–514 6.1–6.1 4 SynVisConPcTc
Ethyl benzoate Nikitin et al. [577] 700–700 3–3 n.a. SynNonPcTc
Ethyl fluoride Chen et al. [220] 235–372 0.1–4.7 141 SynT
Ethylene oxide Giles and Wilson [316] 298–248 0.1–0.7 n.a. SynT
Fluoroethane (HFC-161) Cui et al. [240] 253–323 0.2–1.7 n.a. SynTVis
Freon R-404a Gruzdev et al. [330] 298–330 1.2–2.6 438 SynT
␥-Butyrolactone VonNiederhausern et al. [748] 474–732 0.1–5.1 n.a. SynNonConPcTc
Heavy fraction of Kumkolsk oil Kutcherov and Chernoutsan [125] 275–320 0.1–500 n.a. SynNon
Kutcherov and Chernoutsan [125] 275–320 0.1–500 n.a. SynNon
Hexafluoroethane (PFC-116) Madani et al. [530] 253–292 1–2.9 n.a. SynT
Valtz et al. [734] 244–292 0.7–2.9 28 SynT
Hexyl benzoate Nikitin et al. [577] 748–748 1.9–1.9 n.a. SynNonPcTc
Hydrogen sulfide Théveneau et al. [713] 223–373 0.1–8.9 n.a. SynVis
Hyperstoichiometric uranium dioxide (UO2.01) Manara et al. [134] 3071–3135 100–150 n.a. SynNon
Hyperstoichiometric uranium dioxide (UO2.66–U3O8) Manara et al. [134] 2010–2010 100–100 n.a. SynNon
Indium Ledru et al. [482] 434–444 64–403 n.a. SynNon
Isobutane (2-methylpropane) Laavi et al. [475] 364–364 1.6–1.6 113 SynT
Isobutene Ihmels et al. [365] 285–418 0.2–4 n.a. SynVisVarPcTc
Yun et al. [786] 288–363 0.2–1.5 200 SynT
Isopropyl acetate Giles and Wilson [316] 393–453 0.2–0.9 n.a. SynT
Komsomolsk oil Kutcherov and Chernoutsan [125] 249–373 0.1–500 n.a. SynNon
Linear polyethylene (LPE) Sato et al. [632] 394–454 0.1–200 n.a. SynNonVar
Mercury Dan and Grolier [242] 234–238 15–90 18 SynNonVar
Grolier and Dan [328] 234–238 15–90 18 SynNonVar
Methane Zhu et al. [816] 159–178 1.5–3.1 300 SynT
Methanol Bazaev et al. [158] 423–653 1.4–40 32 SynOthPcTc
Dell’Era et al. [254] 364–364 0.2–0.2 n.a. SynT
Gil et al. [115] 512–512 8–8 4 SynVisConPcTc
Laavi et al. [475] 364–364 0.2–0.2 113 SynT
Visuri et al. [743] 364–364 0.2–0.2 113 SynT
Methyl benzoate Nikitin et al. [577] 695–695 3.4–3.4 n.a. SynNonPcTc
Methylpentafluoroethylether (HFE-245mc) Yasumoto et al. [777] 406–406 2.8–2.8 16 SynVisVarPcTc
Model oil Kutcherov and Chernoutsan [125] 275–320 0.1–500 n.a. SynNon
Naphthalene VonNiederhausern et al. [131] 502–750 0.1–4.1 n.a. SynNonConPcTc
n-Butane Dell’Era et al. [254] 364–364 1.2–1.2 n.a. SynT
Glos et al. [318] 135–340 0–0.7 n.a. SynT
Lim et al. [504] 273–323 0.1–0.4 85 SynT
Miyamoto [549] 280–424 0.1–3.7 25 SynTVar
n-Butyl acrylate VonNiederhausern et al. [748] 441–601 0.1–2.8 n.a. SynNonConPcTc
n-Heptane Ewing and Ochoa [153] 372–537 0.1–2.6 605 SynPVcir
n-Hexadecane Milhet et al. [103] 291–313 0.1–100 0.03 SynVis
n-Hexane Ewing and Ochoa [154] 315–504 0–2.8 605 SynPVcir
Gil et al. [115] 507–507 3–3 4 SynVisConPcTc
Nitrobenzene Xu et al. [772] 299–614 100–3000 94 SynNonVar
N-Methyldiethanolamine (MDEA) VonNiederhausern et al. [748] 519–741 0.1–4.1 n.a. SynNonConPcTc
Nonadecylcyclohexane Milhet et al. [546] 315–333 0.1–100.1 0.03 SynVis
n-Pentadecane Milhet et al. [103] 283–303 0.1–100 0.03 SynVis
n-Pentane Ewing and Ochoa [286] 309–456 0–2.7 605 SynPVcir
n-Tetradecane Milhet et al. [103] 279–302 0.1–100 0.03 SynVis
Octadecylcyclohexane Milhet et al. [546] 314–328 0.1–100.1 0.03 SynVis
Oxazole VonNiederhausern et al. [748] 479–550 2.4–6.7 n.a. SynNonConPcTc
p-Diisopropyl benzene VonNiederhausern et al. [748] 518–676 0.2–2.3 n.a. SynNonConPcTc
Pentadecylcyclohexane Milhet et al. [546] 298–320 0.1–100.1 0.03 SynVis
Pentafluoroethane (HFC-125) Chen et al. [219] 272–313 0.6–2 31.7 SynT
Table 3 (Continued)
Fedele et al. [296] 253–293 0.3–1.2 50 SynT

Pentyl benzoate Nikitin et al. [577] 736–736 2.1–2.1 n.a. SynNonPcTc
Petroleum product FR 353–383 K of catalytic cracking Ovchinnikov et al. [586] 393–522 3–24.6 n.a. AnT
Petroleum product FR 383–413 K of catalytic cracking Ovchinnikov et al. [586] 445–558 2.6–17.9 n.a. AnT
Petroleum product FR 413–443 K of catalytic cracking Ovchinnikov et al. [586] 443–579 1.2–13 n.a. AnT
Petroleum product FR 443–473 K of catalytic cracking Ovchinnikov et al. [586] 472–593 1.3–10.4 n.a. AnT
Petroleum wax from Kumkolsk oil Kutcherov and Chernoutsan [125] 275–320 0.1–500 n.a. SynNon
Phenol Nikitin et al. [130] 695–695 5.6–5.6 n.a. SynNonPcTc
Phenyl isocyanate VonNiederhausern et al. [748] 479–656 0.2–4 n.a. SynNonConPcTc
Piperazine VonNiederhausern et al. [749] 445–656 0.1–5.4 n.a. SynNonConPcTc
Poly(ethylene-co-1-butene) (EB) Sato et al. [632] 354–394 0.1–200 n.a. SynNonVar
Poly(ethylene-co-1-hexene) (EH) Sato et al. [632] 394–454 0.1–200 n.a. SynNonVar
Poly(ethylene-co-1-octene) (EO) Sato et al. [632] 354–414 0.1–200 n.a. SynNonVar
Poly(ethylene-co-propylene) (EP) Sato et al. [632] 314–354 0.1–200 n.a. SynNonVar
Propane Gil et al. [115] 369–369 4.2–4.2 4 SynVisConPcTc
Glos et al. [318] 90–340 0–2.4 n.a. SynT
Ho et al. [41] 273–313 0.4–1.3 85 SynTVis
Honda et al. [351] 320–370 1.6–4.2 18 SynVisVarPcTc
Kim and Kim [423] 253–323 0.2–1.7 150 SynTVis
Lim et al. [507] 273–323 0.4–1.7 85 SynT
May et al. [543] 260–293 0.3–0.8 1000 SynT
Miyamoto and Uematsu [548] 280–369 0.5–4.1 25 SynTVar
Propene Giles and Wilson [317] 253–293 0.3–1 n.a. SynT
Glos et al. [318] 95–340 0–2.9 n.a. SynT
Ho et al. [41] 273–313 0.5–1.6 85 SynTVis
Propyl benzoate Nikitin et al. [577] 710–710 2.6–2.6 n.a. SynNonPcTc
Sulfolane VonNiederhausern et al. [748] 560–829 0.1–4.1 n.a. SynNonCon
Tert-butyl acetate VonNiederhausern et al. [748] 472–541 1–3 n.a. SynNonConPcTc
Tetrabutoxysilane Nikitin et al. [578] 682–682 1.1–1.1 n.a. SynNonPcTc
Tetracontane Machado et al. [138] 351–385 10–130 n.a. SynNon
Tetracosane Deiters and Randzio [252] 320–353 0–130 n.a. SynNon
Machado et al. [138] 326–357 10–150 n.a. SynNon
Tetradecylcyclohexane Milhet et al. [546] 297–320 0.1–100.1 0.03 SynVis
Tetradexoxysilane Nikitin et al. [578] 849–849 0.6–0.6 n.a. SynNonPcTc
Tetraethoxysilane Nikitin et al. [578] 587–587 2–2 n.a. SynNonPcTc
Tetrafluoromethane (CFC-14) Zhu et al. [815] 179–210 0.6–2.1 300 AnTVcir
Zhu et al. [816] 159–178 0.2–0.6 300 SynT
Tetraheptoxysilane Nikitin et al. [578] 778–778 0.7–0.7 n.a. SynNonPcTc
Tetrahexoxysilane Nikitin et al. [578] 757–757 0.7–0.7 n.a. SynNonPcTc
Tetramethoxysilane Nikitin et al. [578] 558–558 2.8–2.8 n.a. SynNonPcTc
Tetramethyl orthosilicate Anderson [149] 334–522 0–1.4 5.6 SynT
Tetranonoxysilane Nikitin et al. [578] 830–830 0.6–0.6 n.a. SynNonPcTc
Tetraoctoxysilane Nikitin et al. [578] 812–812 0.6–0.6 n.a. SynNonPcTc
Tetrapentoxysilane Nikitin et al. [578] 714–714 0.8–0.8 n.a. SynNonPcTc
Tetrapropoxysilane Nikitin et al. [578] 649–649 1.3–1.3 n.a. SynNonPcTc
Thioanisole VonNiederhausern et al. [131] 436–705 0.1–4 n.a. SynNonConPcTc
Tin Ledru et al. [482] 508–511 64–370 n.a. SynNon
Trans-2-butene Ihmels et al. [365] 274–428 0.1–4 n.a. SynVisVarPcTc
Triacontane Machado et al. [138] 338–372 10–150 n.a. SynNon
VonNiederhausern et al. [131] 713–809 0.1–0.4 n.a. SynNonCon
Tridecylcyclohexane Milhet et al. [546] 286–309 0.1–100.1 0.03 SynVis
Trifluoromethane (HFC-23) Shariati et al. [659] 288–298 3.6–4.7 n.a. SynT
Zhang et al. [806] 188–243 0.1–1 300 AnTVcir
Trifluoromethoxymethane (HFE-143m) Yasumoto et al. [777] 377–377 2.6–2.6 16 SynVisVarPcTc
Undecylcyclohexane Milhet et al. [546] 272–293 0.1–100.1 0.03 SynVis
Uranium dioxide (UO2 ) Manara et al. [134] 3147–3147 100–100 n.a. SynNon
Vinyl chloride Giles and Wilson [316] 273–313 0.1–0.6 n.a. SynT
Vulcanized rubber Grolier and Dan [328] 225–240 10–90 18 SynNonVar
Water Salzmann [628] 77–170 200–1900 3.8 SynNon
cell content (Vis). Secuianu et al. [33] used a variable volume cell The main advantage of analytical methods is that they can be
with two sapphire windows where one of the windows acts as a used for systems with more than two components without sig-
piston. nificant complications. When the compositions of all phases are
Analytical methods without sampling can be realized using a analyzed, each experiment yields complete information on the tie-
physicochemical method of analysis inside the equilibrium cell line(s).
under pressure. This can be spectroscopic methods (AnSpec), e.g.
Koglbauer and Wendland [34], gravimetric methods (AnGrav), e.g. 3.1.1. Analytical isothermal methods (AnT)
C.B. Li et al. [35], or other methods (AnOth), e.g. Hussain et al. [36] Characteristic for isothermal methods is that the temperature
who used a quartz crystal microbalance. These methods avoid the of the system stays constant during the equilibration process, e.g.
problems related to sampling from a high-pressure cell. when the system is in contact with a heat reservoir. The other equi-
Table 4
Binary systems: carbon dioxide + X.
(1-Methylimidazole)(triethylamine)boronium bis Muldoon et al. [84] 298–298 0.1–1.3 n.a. AnGrav

(trifluoromethylsulfonyl)imide [Et3NBH2mim] [Tf2N]
(1S,2R)-1-Hydroxy-N,N,N-trimethyl-1-phenylpropan-2- Scurto et al. [648] 364–364 15–15 n.a. SynVis
ammonium triflate [EP]
[Tfo]
(Acetylacetonato)(1,5-cyclooctadiene)rhodium(I) Aschenbrenner et al. 333–333 10–30 10 AnPTSemY
[177]
(R)-1-Methoxy-N,N,N-trimethylbutan-2-ammonium Scurto et al. [648] 272–272 2–2 n.a. SynVis
bis(trifyl)imide [IHETMAm] [Tf2N]
(S)-(+)-Ibuprofen Suleiman et al. [68] 313–313 14–22 n.a. AnPTChro
Suleiman et al. [68] 313–313 20–20 n.a. AnPTSemY
(S)-(+)-Naproxen Suleiman et al. [68] 313–313 14–28 n.a. AnPTChro
(S)-N-(1-Hydroxybutan-2-yl)-N,N-dimethylbutan-1- Scurto et al. [648] 333–340 15–35 n.a. SynVis
ammonium + mentholsulfate [MTOA] [+MS]
1-(1-Hydroxypropyl)-methylimidazolium nitrate [hopmim] [NO3 ] Bermejo et al. [105] 303–353 0.8–11.6 n.a. SynVisVar
1-(Prop-2c-enyloxy)-9,10-anthraquinone Shamsipur et al. 308–348 15.2–35.5 1 AnTValY
[657]
1,1,1,2-Tetrafluoroethane (HFC-134a) Lim et al. [508] 323–343 1.6–7.1 50 AnTVLcirValVis
1,1,3,3-Tetramethylguanidium lactate Zhang et al. [798] 308–327 0.4–10.1 n.a. SynTVis
1,1-Difluoroethane (HFC-152a) Di Nicola et al. [260] 223–343 0–3.8 273.5 SynNon
1,2-Butanediol Inomata et al. [377] 313–333 4.4–13.9 n.a. AnPTCon
1,2-Epoxycyclohexane van Schilt et al. [736] 353–423 1.5–13.6 n.a. SynVisVar
1,3,5-Tri-tert-butylbenzene Dilek et al. [93] 298–328 2.1–19.4 60 SynNonVisVar
Dilek et al. [93] 298–328 2.1–19.4 60 SynVisVar
1,3-Butanediol Inomata et al. [377] 313–333 3.9–13.9 n.a. AnPTCon
1,4-Bis(1-methylethylamino)-9,10-anthraquinone Kautz et al. [54] 305–340 7.9–17.7 0.63 AnPTSemYSpec
1,4-Bis(butylamino)-9,10-anthraquinone Kautz et al. [54] 305–340 7.6–19 0.63 AnPTSemYSpec
1,4-Bis(ethylamino)-9,10-anthraquinone Kautz et al. [54] 299–346 7.6–18.6 0.63 AnPTSemYSpec
1,4-Bis(methylamino)-9,10-anthraquinone Kautz et al. [54] 299–345 6.7–18.8 0.63 AnPTSemYSpec
1,4-Bis(octylamino)-9,10-anthraquinone Kautz et al. [54] 310–340 9–19.9 0.63 AnPTSemYSpec
1,4-Bis(pentylamino)-9,10-anthraquinone Kautz et al. [54] 299–340 6.5–18.7 0.63 AnPTSemYSpec
1,4-Dihydroxy-2-(prop-2-enyl)-9,10-anthraquinone Shamsipur et al. 308–348 15.2–35.5 1 AnTValY
[657]
1,4-Dihydroxy-9,10-anthraquinone Shamsipur et al. 308–348 15.2–35.5 1 AnTValY
[657]
1,4-Dimethoxy-9,10-anthraquinone Shamsipur et al. 308–348 15.2–35.5 1 AnTValY
[657]
1,5-Naphthalenediamine Khimeche et al. [421] 313–333 11–20 n.a. AnPTSemY
15-Crown-5 (1,4,7,10,13-pentaoxacyclopentadecane) Kong et al. [440] 308–313 7.9–30 3.14 AnPTChro
1-Butanol Elizalde-Solis et al. 354–430 2–16.1 100 AnTCapValVis
[281]
Ghaziaskar et al. 323–323 8.5–14 16 AnPTSemY
[314]
Najdanovic-Visak 313–333 5.7–10.7 24 SynVisVar
et al. [570]
1-Chloro-1,2,2,2-tetrafluoroethane (HCFC-124) Jeong et al. [387] 313–333 0.5–7.7 320 AnTVLcirValVis
1-Decanol Ghaziaskar et al. 323–323 10–18 16 AnPTSemY
[314]
1-Ethyl-3-methylimidazolium 2-(2-methoxyethoxy) ethylsulfate Soriano et al. [82] 303–343 0.8–6.7 n.a. AnGrav
[Emim] [MDEGSO4 ]
1-Ethyl-3-methylimidazolium acetate [emim] [Ac] Yokozeki et al. [780] 298–298 0–1,9 n.a. AnGrav
1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide Kim et al. [147] 298–298 0.2–0.9 n.a. SynT
([emim] [Tf2N])
1-Ethyl-3methylimidazolium bis(trifluoromethylsulfonyl)imide Yokozeki et al. [780] 298–298 0–1,9 n.a. AnGrav
[emim] [Tf2N]
1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide Shin et al. [671] 292–344 1.2–43.2 31 SynVisVar
[emim] [Tf2N]
1-Ethyl-3-methylimidazolium ethyl sulfate [emim] [EtSO4 ] Petermann et al. [79] 298–298 0.1–6 n.a. AnGrav
1-Ethyl-3-methylimidazolium hexafluorophosphate Shariati and Peters 310–370 1–99 3.5 SynVisVar
[658]
1-Ethyl-3-methylimidazolium tetrafluoroborate ([emim] [BF4 ]) Kim et al. [147] 298–298 0.2–0.8 n.a. SynT
1-Ethyl-3-methylimidazolium tetrafluoroborate [Emim] [BF4 ] Soriano et al. [688] 303–343 0.4–4.3 n.a. AnGrav
1-Ethyl-3-methylimidazolium trifluoroacetate [emim] [TFA] Yokozeki et al. [780] 298–298 0–1.9 n.a. AnGrav
1-Ethyl-3-methylimidazolium trifluoromethanesulfonate [C2mim] Shin and Lee [672] 303–344 0.8–37.8 31 SynVisVar
[TfO]
1-Heptanol Secuianu et al. [33] 284–310 4.4–8 60 SynVisVar
Secuianu et al. [33] 289–353 0.5–14 60 AnTVisVar
Secuianu et al. [649] 298–316 0.6–11.4 60 AnTVisVar
1-Hexadecylpyrdinium chloride [HDPy] [Cl] Scurto et al. [648] 344–348 15–15 n.a. SynVis
1-Hydroxy-4-(prop-2-enyloxy)-9,10-anthraquinone Shamsipur et al. 308–348 15.2–35.5 1 AnTValY
[657]
1-Hydroxy-9,10-anthraquinone Shamsipur et al. 308–348 15.2–35.5 1 AnTValY
[657]
Table 4 (Continued)
1-Methyl-3-(3,3,4,4,5,5,6,6,6-nonafluorohexyl)imidazolium Muldoon et al. [84] 298–333 0.1–1.3 n.a. AnGrav

bis(trifluoromethylsulfonyl)imide [C6 H4 F9 mim] [Tf2N]
Muldoon et al. [84] 298–333 1.3–9 n.a. SynT
1-Methyl-3-(3,3,4,4,5,5,6,6,7,7,8,8,8- Muldoon et al. [84] 298–298 0.1–1.3 n.a. AnGrav
tridecafluorooctyl)imidazolium
bis(trifluoromethylsulfonyl)imide [C8 H4 F13 mim] [Tf2N]
1-n-Butyl-1-methylpyrrolidinium Zhang et al. [802] 283–323 0–1.8 n.a. AnGrav
Tris(pentafluoroethyl)trifluorophosphate ([bmpyrr] [FEP])
1-n-Butyl-3-methyl imidazolium tetrafluoroborate ([bmim] [BF4 ]) Chen et al. [221] 307–322 1–9 n.a. SynVis
1-n-Butyl-3-methylimidazoium hexyfluorophosphate [bmim] Shariati et al. [659] 293–363 0.5–73.5 n.a. SynVisVar
[PF6 ]
1-n-Butyl-3-methylimidazolium 2-(2-methoxyethoxy)ethylsulfate Muldoon et al. [84] 333–333 0.1–1.3 n.a. AnGrav
(Ecoeng 41 M)
1-n-Butyl-3-methylimidazolium acetate ([bmim] [Ac]) Shiflett and Yokozeki 281–292 4.5–5.6 1.2 SynOthVis
[667]
Shiflett and Yokozeki 283–348 0–1.9 n.a. AnGrav
[667]
1-n-Butyl-3-methylimidazolium acetate [bmim][Ac] Yokozeki et al. [780] 298–298 0–1.9 n.a. AnGrav
1-n-Butyl-3-methylimidazolium Anthony et al. [74] 283–323 0–1.3 n.a. AnGrav
bis(trifluoromethylsulfonyl)imide ([bmim] [Tf2N])
1-n-Butyl-3-methylimidazolium Lee and Outcalt [483] 279–339 0.2–4.7 35.9 SynTVis
bis(trifluoromethylsulfonyl)imide [bmim] [Tf2N]
Shin et al. [671] 293–344 1–42.8 31 SynVisVar
1-n-Butyl-3-methyl-imidazolium chloride [C4MIm] [Cl] Scurto et al. [648] 332–332 15–15 n.a. SynVis
1-n-Butyl-3-methylimidazolium hexafluorophosphate Shariati and Peters 290–365 1–86 3.5 SynVisVar
[658]
1-n-Butyl-3-methyl-imidazolium hexafluorophosphate Zhang et al. [808] 313–313 1–16 50 AnTVisVar
1-n-Butyl-3-methylimidazolium hexafluorophosphate ([bmim] Kim et al. [147] 298–298 0.5–0.6 n.a. SynT
[PF6 ])
1-n-Butyl-3-methylimidazolium hexafluorophosphate [bmim] Kumełan et al. [461] 293–395 0.1–9.6 29.2 SynVis
[PF6 ]
Shiflett and Yokozeki 283–348 0–2 n.a. AnGrav
[81]
Yokozeki et al. [780] 298–298 0–1.9 n.a. AnGrav
Zhang et al. [798] 297–322 0.7–8 n.a. SynTVis
1-n-Butyl-3-methylimidazolium iminoacetric acid acetate [bmim] Yokozeki et al. [780] 298–298 0–1.9 n.a. AnGrav
[IAAc]
1-n-Butyl-3-methylimidazolium isobutyrate [bmim] [ISB] Yokozeki et al. [780] 298–298 0–1.9 n.a. AnGrav
1-n-Butyl-3-methylimidazolium levulinate [bmim] [LEV] Yokozeki et al. [780] 298–298 0–1.9 n.a. AnGrav
1-n-Butyl-3-methylimidazolium methyl sulfate [bmim] [CH3 SO4 ] Kumełan et al. [461] 293–413 0.9–9.8 29.2 SynVis
1-n-Butyl-3-methylimidazolium nitrate [bmim] [NO3 ] Bermejo et al. [105] 292–368 0.3–12.8 n.a. SynVisVar
1-n-Butyl-3-methylimidazolium pentadecafluorooctanoate Muldoon et al. [84] 333–333 0.1–1.3 n.a. AnGrav
[bmim] [C7 F15 CO2 ]
1-n-Butyl-3-methylimidazolium propionate [bmim] [PRO] Yokozeki et al. [780] 298–298 0–1.9 n.a. AnGrav
1-n-Butyl-3-methylimidazolium succinamate [bmim] [SUC] Yokozeki et al. [780] 298–298 0–1.9 n.a. AnGrav
1-n-Butyl-3-methylimidazolium tetrafluoroborate ([bmim] [BF4 ]) Anthony et al. [74] 283–323 0–1.3 n.a. AnGrav
1-n-Butyl-3-methylimidazolium tetrafluoroborate [bmim] [BF4 ] Shiflett and Yokozeki 282–348 0–2 n.a. AnGrav
[81]
Yokozeki et al. [780] 298–298 0–2 n.a. AnGrav
1-n-Butyl-3-methylimidazolium tetrafluoroethanesulfonate Yokozeki et al. [780] 298–298 0–1.9 n.a. AnGrav
[bmim] [TFES]
1-n-Butyl-3-methylimidazolium trifluoroacetate [bmim] [TFA] Muldoon et al. [84] 333–333 0.1–1.3 n.a. AnGrav
1-n-Butyl-3-methylimidazolium trifluoromethanesulfonate Shin and Lee [672] 303–344 0.8–37.5 31 SynVisVar
[C2mim] [TfO]
1-n-Butyl-3-methylimidazolium trimethylacetate [bmim] [TMA] Yokozeki et al. [780] 298–298 0–1.9 n.a. AnGrav
1-n-Butyl-3-methylimidazolium Muldoon et al. [84] 333–333 0.1–1.3 n.a. AnGrav
tris(trifluoromethylsulfonyl)methide [bmim] [methide]
1-n-Butyl-nicotinic acid butyl ester Muldoon et al. [84] 333–333 0.1–1.3 n.a. AnGrav
bis(trifluoromethylsulfonyl)imide [b2-Nic] [Tf2N]
1-n-Hexyl-3-methyl imidazolium tetrafluoroborate ([hmim] [BF4 ]) Chen et al. [221] 307–322 1–9 n.a. SynVis
1-n-Hexyl-3-methylimidazolim Shiflett and Yokozeki 282–348 0–1.9 n.a. AnGrav
bis(trifluoromethylsulfonyl)-imide [hmim] [Tf2N] [665]
1-n-Hexyl-3-methylimidazolium acesulfamate [hmim] [ACE] Muldoon et al. [84] 333–333 0.1–1.3 n.a. AnGrav
1-n-Hexyl-3-methylimidazolium Kumelan et al. [463] 293–413 0.6–9.9 30 SynVis
bis(trifluoromethylsulfonyl)imide [C6-mim] [Tf2N]
Shin et al. [671] 303–344 1.4–39 31 SynVisVar
1-n-Hexyl-3-methylimidazolium Muldoon et al. [84] 298–298 0.1–1.3 n.a. AnGrav
bis(trifluoromethylsulfonyl)imide [hmim] [Tf2N]
1-n-Hexyl-3-methyl-imidazolium bis(trifyl)imide Ren and Scurto [141] 333–333 2.4–12.2 5.72 SynTVis
Ren and Scurto [141] 333–333 2.4–12.2 5.72 SynTVis
Table 4 (Continued)
1-n-Hexyl-3-methylimidazolium hexafluorophosphate Shariati and Peters 295–365 1–93 3.5 SynVisVar

[658]
1-n-Hexyl-3-methylimidazolium hexafluorophosphate ([C6mim] Kim et al. [147] 298–298 0.2–0.9 n.a. SynT
[PF6 ])
1-n-Hexyl-3-methylimidazolium saccarinate [hmim] SAC] Muldoon et al. [84] 333–333 0.1–1.3 n.a. AnGrav
1-n-Hexyl-3-methylimidazolium tetrafluoroborate ([C6mim] Kim et al. [147] 298–298 0.3–0.8 n.a. SynT
[BF4 ])
1-n-Hexyl-3-methylimidazolium tetrafluoroborate [C6-mim] [BF4 ] Costantini et al. [236] 278–368 0.5–10.1 3.5 SynVisVar
Costantini et al. [236] 303–362 4.8–86.6 n.a. SynVis
Kroon et al. [448] 278–362 2.9–67.6 n.a. SynVis
Kroon et al. [448] 278–368 0.5–12.8 3.5 SynVisVar
1-n-Hexyl-3-methylimidazolium Kim et al. [147] 298–298 0.1–0.8 n.a. SynT
tri(bisfluoromethylsulfonyl)imide [C6mim] [Tf2N]
Kim et al. [425] 298–298 0.1–0.8 n.a. AnTVcirVal
1-n-Hexyl-3-methylimidazolium trifluoromethanesulfonate Shin and Lee [672] 303–344 1.2–36.3 31 SynVisVar
[C2mim] [TfO]
tris(heptafluoropropyl)trifluorophosphate [hmim] [pFAP]
1-n-Hexyl-3-methylimidazolium Zhang et al. [802] 283–323 0–1.7 n.a. AnGrav
Tris(pentafluoroethyl)trifluorophosphate ([hmim] [FEP])
tris(pentafluoroethyl)trifluorophosphate [hmim] [eFAP]
1-n-Hexyl-3-methylimidazolium Yokozeki et al. [780] 298–298 0–1.9 n.a. AnGrav
tris(pentafluoroethyl)trifluorophosphate [hmim] [FAP]
1-n-Hexyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide Muldoon et al. [84] 298–298 0.1–1.3 n.a. AnGrav
[hmpy] [Tf2N]
1-n-Octyl-3-methyl imidazolium tetrtafluoroborate ([omim] [BF4 ]) Chen et al. [221] 307–322 1–9 n.a. SynVis
1-n-Octyl-3-methylimidazolium Shin et al. [671] 301–344 0.6–34.8 31 SynVisVar
bis(trifluoromethylsulfonyl)imide [C8-mim] [Tf2N]
1-n-Octyl-3-methylimidazolium tetrafluoroborate [C8mim] [BF4 ] Gutkowski et al. 293–363 0.1–100 3.5 SynVisVar
[332]
1-n-Octyl-3-methylimidazolium trifluoromethanesulfonate Shin and Lee [672] 303–344 0.6–34 31 SynVisVar
[C2mim] [TfO]
1-n-Pentyl-3-methylimidazolium Muldoon et al. [84] 298–333 0.1–1.3 n.a. AnGrav
tris(nonafluorobutyl)trifluorophosphate [p5mim] [bFAP]
1-Octanol Chiu et al. [224] 313–348 3.2–18.2 60 SynVisVar
Fourie et al. [819] 308–348 6.8–17.9 80 SynVisVar
Hou et al. [356] 303–323 1–8 50 AnTBloVisVar
Ke et al. [140] 300–333 6.5–22.9 320 SynNonPcTc
1-Pentanol Hou et al. [356] 303–323 1–8.1 50 AnTBloVisVar
1-Propanol Elizalde-Solis et al. 344–426 10.6–15.7 100 AnTCapValVis
[281]
Secuianu et al. [651] 293–353 0.6–12.6 60 AnTVisVar
Schilderman et al. 312–450 0.6–14.4 3.5 SynVisVar
[638]
2-(2-Hydroxy ethoxy)-ammonium acetate (HEAA) Yuan et al. [783] 303–323 0.7–7.6 n.a. SynT
2-(2-Hydroxy ethoxy)-ammonium formate (HEAF) Yuan et al. [783] 303–323 0.6–8.5 n.a. SynT
2-(2-Hydroxy ethoxy)-ammonium lactate (HEAL) Yuan et al. [783] 303–323 1.2–8.5 n.a. SynT
2,2,2-Trifluoroethanol Lazzaroni et al. [479] 298–313 1.1–7.7 150 SynTVis
2,2,2-Trifluoroethyl methacrylate Kwon et al. [474] 323–353 2.3–11.7 n.a. SynVisVar
2,2,4-Trimethylpentane (isooctane) Mutelet et al. [564] 278–393 1.2–11.1 1.7–12.4 SynVisVar
Zhang et al. [790] 270–282 1.4–3,6 474 AnT
2,2,6,6-Tetramethyl-3,5-heptanedionato potassium Aschenbrenner et al. 333–333 10–30 10 AnPTSemY
[177]
2,2,6,6-Tetramethyl-3,5-heptanedionato rubidium Aschenbrenner et al. 333–333 10–30 10 AnPTSemY
[177]
2,2,6,6-Tetramethyl-3,5-heptanedionato silver(I) Aschenbrenner et al. 333–333 10–30 10 AnPTSemY
[177]
2,2-Bipyridine Bai et al. [179] 313–323 8.1–11.4 7.11 SynVis
2,2-Dichloro-1,1,1-trifluoroethane (HCFC-123) Jeong et al. [387] 313–333 0.8–8 320 AnTVLcirValVis
2,2-Dimethyl-1,3-propanediol Park et al. [593] 352–403 18.9–166 n.a. SynVisVar
2,2 -Oxybis(N,N-dibutylacetamide) Liu et al. [512] 313–333 8.8–13.1 7.11 SynVis
2,2 -Oxybis(N,N-diethylacetamide) Liu et al. [512] 313–333 8.7–13.3 7.11 SynVis
2,2 -Oxybis(N,N-dihexylacetamide) Liu et al. [512] 313–333 9–16.4 7.11 SynVis
2,3,5,6,-Tetramethylpyrazine Sun et al. [704] 318–338 10–30 10 AnPTSemY
2,3,5-Trimethyl phenol Ravipaty et al. [611] 308–308 10.1–28 1.6 AnPTSemYVal
2,3-Dimethyl phenol Ravipaty et al. [611] 308–308 10.1–28 1.6 AnPTSemYVal
2,3-Dimethylpyrazine Shen et al. [661] 294–381 2.1–34.9 15 SynVisVar
2,5-Dimethyl phenol Ravipaty et al. [611] 308–308 10.1–28 1.6 AnPTSemYVal
2,5-Dimethylhexane Mutelet et al. [564] 278–413 2.5–12.5 12.4 SynVisVar
2-Acetylpyrazine Shen et al. [661] 295–371 2.1–19.7 15 SynVisVar
2-Ethoxyethanol Missopolinou et al. 313–328 1.4–9.8 202.1 AnTVLcirValVis
[43]
Table 4 (Continued)
2-Ethyl-1-hexanol Ghaziaskar et al. 313–313 9.9–9.9 16 AnPTSemY

[314]
2-Ethylhexanoic acid Ghaziaskar et al. 313–313 9.9–9.9 16 AnPTSemY
[314]
2-Ethylhexyl methacrylate Liu et al. [519] 313–393 3.2–15.4 28 SynVisVar
2-Hydroxy ethylammonium acetate (HEA) Yuan et al. [783] 303–323 0.8–10.9 n.a. SynT
2-Hydroxy ethylammonium formate (HEF) Yuan et al. [783] 303–323 0.4–10 n.a. SynT
2-Hydroxy ethylammonium lactate (HEL) Yuan et al. [783] 303–323 0.7–10 n.a. SynT
2-Hydroxyethyl methacrylate Soares da Silva et al. 313–338 2.8–21 n.a. SynVisVar
[686]
2-Hydroxyethyl methacrylate (HEMA) Byun and Choi [207] 313–393 5.3–26.8 28 SynVisVarPc
2-Hydroxypropyl acrylate (HPA) Byun and Choi [207] 313–393 5.2–25.9 28 SynVisVarPc
2-Hydroxypropyl methacrylate (HPMA) Byun and Choi [207] 313–393 5.3–23.6 28 SynVisVarPc
2-Methoxypyrazine Shen et al. [661] 294–372 0.7–16.6 15 SynVisVar
2-Methyl-1-propanol (isobutanol) Inomata et al. [377] 313–313 4.1–6.9 n.a. AnPTCon
2-Methylbutanol Inomata et al. [377] 313–333 3.9–9.8 n.a. AnPTCon
2-Methylbutyric ester oil Bobbo et al. [191] 283–283 0–4.5 180 SynVis
2-Methylhexanoic ester oil Bobbo et al. [191] 283–283 0–4.5 180 SynVis
2-Methyl-N-phenylacetamide Huang et al. [357] 308–328 12.1–22.5 300 AnPTSemY
2-Methylpropane (isobutane) Li et al. [496] 304–409 3.6–7.5 18 SynVisPcTc
2-Methylpyrazine Shen et al. [661] 294–387 1.9–28.4 15 SynVisVar
2-Methylvaleric ester oil Bobbo et al. [191] 283–283 0–4.5 180 SynVis
2-Octanol Fourie et al. [819] 308–348 6.7–14.9 80 SynVisVar
Ke et al. [140] 297–334 6–12.5 320 SynNonPcTc
2-Phenyl-4H-1,3-benzoxazin-4-one Suleiman et al. [68] 318–328 10–30 n.a. AnPTChro
2-Propanol (isopropanol) Elizalde-Solis et al. 334–443 9.1–13.7 100 AnTCapValVis
[281]
Khalil et al. [420] 308–348 1.7–11.3 n.a. SynNon
Lazzaroni et al. [479] 313–313 0.7–7.5 150 SynTVis
Lim et al. [506] 323–353 1–10.7 50 AnTVLcirValVis
Zevnik and Levec 298–313 5.2–7.4 300 AnTX
[788]
2-Sulfosalicylic acid Tian et al. [715] 308–328 8–21 100 AnPTSemY
2-Trifluoromethylbenzoic acid Higashi et al. [347] 308–323 9.3–22.6 220 AnPTSemY
3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-Heptadecafluoro-1-decanol Shin et al. [674] 313–363 2.9–14.3 25 SynVisVar
3-Methyl-1-butanol (isopentanol) Inomata et al. [377] 313–333 3.8–10.7 n.a. AnPTCon
3-Methylpentane Mutelet et al. [564] 293–383 2.8–11.1 12.4 SynVisVar
3-Trifluoromethylbenzoic acid Higashi et al. [347] 308–323 9.4–22.5 315 AnPTSemY
Higashi et al. [347] 308–323 9.6–22.4 220 AnPTSemY
4,4 -Diaminodiphenylmethane Khimeche et al. [421] 313–333 11–20 n.a. AnPTSemY
4,4-Dimethyl-2,2-bipyridine Bai et al. [179] 308–318 9.6–25.9 7.11 SynVis
4-Methyl-N-phenylacetamide Huang et al. [357] 308–328 12.1–22.5 300 AnPTSemY
4-Phenyl phenol Ravipaty et al. [611] 308–308 10.1–28 1.6 AnPTSemYVal
4-Phenyltoluene Leeke et al. [487] 353–383 10.2–29.2 100 SynNonVis
4-Tert-butyl phenol Ravipaty et al. [611] 308–308 10.1–28 1.6 AnPTSemYVal
5-Fluorouracil Suleiman et al. [68] 318–328 12–25 n.a. AnPTChro
Acetic acid (ethanoic acid) Calvo and de Loos 283–303 2.9–5.1 n.a. SynVis
[208]
Acetic anhydride Calvo and de Loos 283–363 0.4–14.8 n.a. SynVisPcTc
[208]
Acetone Chiu et al. [225] 291–131 0.7–7.9 n.a. SynVisVar
Han et al. [333] 333–393 2.3–11.7 n.a. AnTVisVar
Stievano and 291–323 0.7–4 60 SynNonLCirVisVar
Elvassore [122]
Wu et al. [133] 333–482 6.7–11.7 n.a. SynNonCon
Acetonitrile (ethanenitrile) Lazzaroni et al. [479] 313–313 0.2–7.2 150 SynTVis
Acetylsalicylic acid Ravipaty et al. [612] 308–328 15.1–28 1.6 AnPTSemYVal
Acrylonitrile Favareto et al. [292] 303–333 4.7–9.9 25 SynVisVar
␣-d-Glucopyranose pentaacetate Haines et al. [70] 313–313 3.9–10 15 AnSpec
␣-Methylbenzyl acetate Calvo and de Loos 283–363 0.4–14.6 n.a. SynVis
[208]
␣-Methylbenzyl alcohol Calvo and de Loos 283–363 0.6–13.9 n.a. SynVis
[208]
Anhydrous caffeine Deiters and Randzio 365–560 0–200 n.a. SynNon
[252]
Anthracene Esmaeilzadeh and 318–318 10.1–20.1 n.a. AnPTSemY
Goodarznia [283]
Argon Coquelet et al. [232] 233–299 1.5–14 28 AnTCapValVis
Artemisinin (artemisia annua L.) Coimbra et al. [227] 308–328 10.4–25.2 30 AnTValVis
Astaxanthin de la Fuente et al. 313–333 9.4–40 50 AnTValVis
[247]
␣-Tocopherol succinate Hybertson [363] 313–323 15–30 7.5 AnPTSemYVal
Table 4 (Continued)
Atorvastatin Hojjati et al. [32] 308–348 12.1–35.4 1 AnTValY

Azelaic acid Sparks et al. [689] 313–333 10–30 100 AnPTSemY
Azo dye 2-[6-((E)-2-[4-(diethylamino)-2-methylphenyl]-1- Hojjati et al. [350] 308–348 12.2–35.5 1 AnTValY
diazenyl)-1,3-dioxo-1H-benzol[de]isoquinolin-2(3H)-yl]acetate
Azo dye 6-((E)-2-[4-(diethylamino)phenyl]-1-diazenyl)-2-propyl- Hojjati et al. [350] 308–348 12.2–35.5 1 AnTValY
1H-benzo[de]isoquinoline-1,3(2H)-dione
Azo dye ethyl 2-[6-((E)-2-3-hydroxy-2-naphthyl-1-diazenyl)-1,3- Hojjati et al. [350] 308–348 12.2–35.5 1 AnTValY
dioxo-1H-benzo[de]isoquinolin-2(3H)-yl]acetate
Azodicarbonamide Suleiman et al. [68] 318–328 10–30 n.a. AnPTChro
Babassu fat Soares et al. [687] 313–353 20–35 100 AnTY
␤-Carotene Saldana et al. [87] 313–323 12–20 n.a. AnOth
␤-d-Galactose pentaacetate Dilek et al. [263] 308–323 9.9–15.4 60 SynNonVisVar
Dilek et al. [263] 308–323 9–15.6 60 SynVisVar
␤-d-Glucopyranose penta(isobutyrate) Haines et al. [70] 313–313 3.9–21 15 AnSpec
␤-d-Glucopyranose penta(trimethylacetate) Haines et al. [70] 313–313 3.9–10 15 AnSpec
␤-d-Glucopyranose pentaacetate Haines et al. [70] 313–313 3.9–10 15 AnSpec
␤-d-Glucopyranose pentabutyrate Haines et al. [70] 313–313 3.9–20 15 AnSpec
␤-d-Glucopyranose pentapropionate Haines et al. [70] 313–313 3.9–21 15 AnSpec
␤-d-Maltose octaacetate Hong et al. [353] 253–323 2.3–19 120 SynVis
Beclomethasone dipropionate Vatanara et al. [737] 338–358 21.3–38.5 1 AnT
Benzene Lay et al. [478] 293–308 1.7–7.3 130 AnTVisVar
Benzoic acid Bertakis et al. [189] 370–391 1.9–20.6 50 SynVisVar
Harris et al. [339] 403–458 0–20.7 112.8 SynT
Uchida et al. [727] 371–395 0.1–22.7 35 SynVis
Wang et al. [754] 313–313 12.1–12.1 n.a. SynVis
Benzyl acrylate Liu et al. [520] 313–393 5.9–24.4 28 SynVisVar
Benzyl methacrylate Liu et al. [520] 313–393 5.7–24.4 28 SynVisVar
Benzyldodecyldimethylammonium bromide [BDMDDAm] Br] Scurto et al. [648] 295–300 5–5 n.a. SynVis
Bertholletia excelsa oil (Brazil nut oil) Rodrigues et al. [618] 323–343 15–30 1000 AnTCap
Beta-sitosterol Dohrn et al. [95] 374–401 0.1–13.8 250 SynVisVar
Biphenyl Leeke et al. [487] 353–383 10.1–29.5 100 SynNonVis
Bis(1-butyl-3-methylimidazolium iminodiacetate [bmim]2[IDA] Yokozeki et al. [780] 298–298 0–1.9 n.a. AnGrav
Bis(2,2,6,6-tetramethyl-3,5-heptanedionato)(1,5- Aschenbrenner et al. 333–333 10–25 10 AnPTSemY
cyclooctadiene)ruthenium(II) [177]
Bis(2,2,6,6-tetramethyl-3,5-heptanedionato)copper(II) Aschenbrenner et al. 333–333 10–30 10 AnPTSemY
[177]
Bis(2,2,6,6-tetramethyl-3,5-heptanedionato)nickel(II) Aschenbrenner et al. 333–333 10–30 10 AnPTSemY
[177]
Bis(2,2,6,6-tetramethyl-3,5-heptanedionato)zinc Aschenbrenner et al. 333–333 10–30 10 AnPTSemY
[177]
Bis(2-cyclohexylethyl)-1,4-dihydro-2,6-dimethyl-4-(1-methyl-5- Khajeh et al. [31] 338–358 12.2–35.5 1 AnTValY
nitro-imidazol-2-yl)-3,5-pyridinedicarboxylates
Bis(3-cyclohexylpropyl)-1,4-dihydro-2,6-dimethyl-4-(1-methyl- Khajeh et al. [31] 338–358 12.2–35.5 1 AnTValY
5-nitro-imidazol-2-yl)-3,5-pyridinedicarboxylates
Bis(4-cyclohexylbutyl)-1,4-dihydro-2,6-dimethyl-4-(1-methyl-5- Khajeh et al. [31] 338–358 12.2–35.5 1 AnTValY
Bis(cyclohexyl)-1,4-dihydro-2,6-dimethyl-4-(1-methyl-5-nitro- Khajeh et al. [31] 328–348 12.2–35.5 1 AnTValY
imidazol-2-yl)-3,5-pyridinedicarboxylates
Bis(cyclohexylmethyl)-1,4-dihydro-2,6-dimethyl-4-(1-methyl-5- Khajeh et al. [31] 328–348 12.2–35.5 1 AnTValY
Bis(cyclopentadienyl)chromium Aschenbrenner et al. 333–333 10–17.5 10 AnPTSemY
[177]
Bis(cyclopentadienyl)cobalt(II) Aschenbrenner et al. 333–333 10–17.5 10 AnPTSemY
[177]
Bis(cyclopentadienyl)iron Aschenbrenner et al. 333–333 10–17.5 10 AnPTSemY
[177]
Bis(cyclopentadienyl)manganese Aschenbrenner et al. 333–333 10–30 10 AnPTSemY
[177]
Bis(cyclopentadienyl)nickel Aschenbrenner et al. 333–333 10–30 10 AnPTSemY
[177]
Bis(cyclopentadienyl)osmium Aschenbrenner et al. 333–333 10–30 10 AnPTSemY
[177]
Bis(cyclopentadienyl)ruthenium Aschenbrenner et al. 333–333 10–30 10 AnPTSemY
[177]
Bis(p-tolyl)hexafluoropropane (BTHFP) Liu et al. [515] 293–382 5.6–25.1 30 SynVisVar
Bis(p-tolyl)propane (BTP) Liu et al. [515] 295–373 5.8–71.1 30 SynVisVar
Bisphenol A Margon et al. [39] 403–473 30–30 65 AnTY
Margon et al. [39] 403–473 2.4–9.5 3.5 SynVisVar
Bisphenol A diglycidyl ether Medina-Gonzalez 318–318 14.5–14.5 10 AnT
et al. [544]
Bisphenol AF (2,2-bis(4-hydroxyphenyl)hexafluoropropane) Liu et al. [516] 297–408 3–20 30 SynVisVar
Bisphenol-A polysulfone Blasig et al. [75] 298–348 0.1–1 n.a. AnGrav
Boldine [(S)-2,9-dihydroxi-1,10-dimethoxiaporphine] de la Fuente et al. 298–333 8.6–40.9 50 AnTValVis
[245]
Budesonide Vatanara et al. [737] 338–358 21.3–38.5 1 AnT
Butyl acetate Byun et al. [200] 313–373 2–14.4 25 SynVisVar
Table 4 (Continued)
Butyl methacrylate Husain et al. [361] 323–333 1.9–10 70 AnTLcirVis

Butyl-methyl pyrrolidinium bis(trifluoromethylsulfonyl) imide Anthony et al. [74] 283–323 0–1.3 n.a. AnGrav
([MeBuPyrr] [Tf2N])
C.I. Disperse Blue 79 Banchero et al. [59] 353–393 15.9–24 32 AnPTSemY
Banchero et al. [64] 353–393 18–30 32 AnPTSemY
C.I. Disperse Orange 3 Banchero et al. [59] 353–393 15.9–28 32 AnPTSemY
C.I. Disperse Orange 30 Özcan and Özcan [63] 353–373 20–30 10.4 AnPTSemY
C.I. Disperse Red 60 Bao and Dai [181] 353–393 11–23 60 AnPTSemY
(1-amino-4-hydroxy-2-phenoxy-9.10-anthraquinone)
Kim et al. [424] 333–393 10–30 n.a. SynVis
C.I. disperse Violet 1 Tsai et al. [721] 353–393 15–30 n.a. AnPTSemY
C.I. Disperse Yellow 54 Kim et al. [424] 333–393 10–30 n.a. SynVis
Caffeine Iwai et al. [379] 313–313 15–15 26.5 AnSpecVcir
Camphor Carvalho et al. [210] 304–354 3.4–15.7 25 SynVisVar
Candeia oil (Eremanthus erythropappus) de Souza et al. [251] 313–333 6.1–24.6 25 SynVisVar
Capsaicin de la Fuente et al. 298–318 6–40 30 AnTVal
[244]
Elizalde-Solis and 312–332 10.4–22.9 10 SynVisVar
Galicia-Luna [280]
Carbazole Esmaeilzadeh and 318–318 10.1–20.1 n.a. AnPTSemY
Goodarznia [283]
Carbonylhydridotris(triphenylphosphine)-rhodium Shimoyama et al. 333–333 10–17 26.5 AnSpecVcir
[670]
Carbonylhydridotris(tris(p-trifluoromethylphenyl)-phosphine)- Shimoyama et al. 320–333 9–15.3 26.5 AnSpecVcir
rhodium [670]
Castor oil Ndiaye et al. [572] 308–343 2.1–26 n.a. SynVisVar
Ceramide 3A (N-linoeoyl-phytosphingosine. 97%) Vezzu et al. [742] 390–397 0.1–6 n.a. SynNon
Chlorobenzene Wang et al. [753] 323–333 8.5–10.6 n.a. SynVisVar
Chlorobutane Wang et al. [753] 323–333 7.9–9.7 n.a. SynVisVar
Chloroform Favareto et al. [292] 303–333 3.9–9.3 25 SynVisVar
Cholesterol Vezzu et al. [742] 409–420 0.1–6 n.a. SynNon
Choline bis(trifluoromethylsulfonyl)imide [choline] [Tf2N] Muldoon et al. [84] 333–333 0.1–1.3 n.a. AnGrav
Cis-Decalin Vitu et al. [745] 292–373 1.5–49 n.a. SynVisVar
Citric acid Wang et al. [754] 313–313 12.1–12.1 n.a. SynVis
Cocoa butter Venter et al. [738] 295–306 0.1–15 25 SynVis
Venter et al. [738] 313–373 2–35 500 AnT
Coenzyme Q10 (ubiquinone) Li et al. [494] 305–322 0.1–19.2 25 SynVisVar
Pecar and Dolecek 306–323 0.1–40 14 SynVis
[598]
Compritol 888 ATO de Sousa et al. [250] 339–345 0.1–22.7 4 SynVis
de Sousa et al. [250] 340–348 10.1–19.5 60 AnT
Copper(II) acetylacetonatea Aschenbrenner et al. 333–333 10–30 10 AnPTSemY
[177]
Corn oil Soares et al. [687] 313–353 20–35 100 AnTY
Coumarin Rodrigues et al. [619] 308–328 11–24 300 AnPTSemY
Crude oil Nobakht et al. [580] 300–300 2.5–6 41 SynT
Cyclohexane Esmelindro et al. 293–333 3.9–9.7 27 SynVisVar
[284]
Zhang et al. [797] 304–556 4.2–14.1 18 SynVisPcTc
Cyclohexanol Esmelindro et al. 303–343 5.3–26.9 27 SynVisVar
[284]
Cyclohexanone Esmelindro et al. 293–333 3.5–10.8 27 SynVisVar
[284]
Cyclohexyl acrylate Byun [199] 313–393 1.6–19.9 28 SynVisVarPc
Cyclohexyl methacrylate Byun [199] 313–393 2–20.5 28 SynVisVarPc
Decyl acrylate Byun and Lee [201] 326–429 11.7–29.5 28 SynVisVar
Decyl methacrylate Byun and Lee [201] 313–393 3–20 28 SynVisVar
Dialkyl Khajeh et al. [31] 338–358 12.2–35.5 1 AnTValY
1,4-dihydro-2,6-dimethyl-4-(1-methyl-5-nitro-imidazol-2-yl)-
3,5-pyridinedicarboxylates derivative 1
Table 4 (Continued)
Diallylsulfide Andreatta et al. [172] 275–370 1.7–14 3.5 SynVisVar

Dibenzo-24-crown-8 (2,3,14,15-dibenzo-1,4,7,10,13,16,19,22- Kong et al. [440] 308–313 15–35 3.14 AnPTChro
octaoxacyclotetracosa-2,14-diene)
dibenzofuran Perez et al. [600] 301–338 5.7–27.5 15 SynVisVar
Dichloromethane (HCC-30) Shin et al. [680] 308–328 1.7–8.9 25 SynVisVar
Kalogiannis and 308–328 4–8 26.75 SynVisVar
Panayiotou [403]
Stievano and 291–311 1.9–5.9 60 SynNonLCirVisVar
Elvassore [122]
Dicofol Kotnik et al. [446] 293–313 10.9–26.2 120 AnT
Kotnik et al. [446] 319–344 1–29.9 35 SynVis
Diethyl carbonate Cheng and Chen 308–318 4.3–8.2 320 AnTLcirValVis
[159]
Lu et al. [528] 273–293 0.5–3.8 100 AnTCapVisVar
Diethyldichlorosilane Vyhmeister et al. 308–337 7.3–12.2 n.a. SynVisVarPc
[751]
Diflunisal Coimbra et al. [229] 308–328 9.3–24.4 30 AnTValVis
Diisobutyl adipate Liu et al. [514] 294–424 2.4–26.6 30 SynVisVar
Diisopropoxititanium bis(acetylacetonate) Montequi et al. [559] 353–473 10–20 110 AnPTSemY
Diisopropyl ether Matsuda et al. [156] 298–308 5–7.5 n.a. SynOth
Zhu et al. [814] 265–333 0.5–2.5 120 AnTValVis
Dimethyl carbonate Lu et al. [528] 273–293 0.6–4.1 100 AnTCapVisVar
Dimethyl sulfoxide Andreatta et al. [173] 278–368 0.5–13.1 3.5 SynVisVar
Chiu et al. [224] 313–348 3.9–17.6 60 SynVisVar
Dimethyl(1,5-cyclooctadiene)platinum(II) Aschenbrenner et al. 333–333 10–30 10 AnPTSemY
[177]
Dimethyldichlorosilane Vyhmeister et al. 307–348 6.6–11 n.a. SynVisVarPc
[751]
Diphenyl carbonate Margon et al. [39] 353–453 30–30 65 AnTY
Diphenyl(4-phenyl)phenylphosphine Filardo et al. [48] 313–313 35.2–35.2 23.35 AnTIns
Diphenyl-aryl peracetylated sugar phosphine Ablan et al. [164] 296–296 6.8–11.5 n.a. SynVisVar
Disperse yellow 54 Tsai et al. [720] 353–393 15–30 33 AnPTSemY
Docosahexaenoic acid ethyl ester Chang et al. [215] 313–333 4.2–23.5 n.a. SynTVLcirVis
Dodecafluoro-2-methylpentan-3-one (NOVEC1230) Jeong et al. [386] 313–343 1.6–8.7 320 AnTVLcirValVis
Dodecanoic acid Garlapati and Madras 308–308 9.9–22.6 n.a. AnPTSemY
[310]
Dodecylpolyoxyethylene polyoxypropylene ether nonionic Su et al. [693] 308–328 13.6–35 10.15 SynVisVar
surfactant A(EO)9(PO)2
Dodecylpolyoxyethylene polyoxypropylene ether nonionic Su et al. [693] 308–328 16–32 10.15 SynVisVar
surfactant A(EO)9(PO)3
d-Pinitol Chafer et al. [213] 313–333 10–40 10 AnPTSemY
Eicosapentaenoic acid ethyl ester Chang et al. [215] 313–333 2.8–20.7 n.a. SynTVLcirVis
Ethane Gil et al. [115] 291–304 5–7.1 4 SynVisConPcTc
Ethanol Chiu et al. [225] 291–313 2.4–8.1 n.a. SynVisVar
Elizalde-Solis and 333–333 3–10.4 100 AnTCapValVisPc
Galicia-Luna [277]
Knez et al. [430] 313–353 1.3–13.9 500 AnTVLcirVis
Kodama and Kato 291–291 2–5.4 320 AnTVLcir
[433]
Stievano and 291–323 3.3–8.1 60 SynNonLCirVisVar
Elvassore [122]
Ethene–octene-copolymer Li et al. [78] 433–473 3.5–28 n.a. AnGrav
Ethoxylated nonyl phenol Koh et al. [101] 313–313 8–10 22.4 SynVisVar
Ethyl acetate Borges et al. [195] 303–343 2.5–10.1 27 SynVisVar
Byun et al. [200] 313–373 1.7–11.6 25 SynVisVar
Kato et al. [413] 313–313 0.6–7.7 134 SynNonVisVar
Ethyl butyrate Cheng and Chen 308–318 4.5–8.9 320 AnTLcirValVis
[159]
Ethyl methacrylate Wang et al. [753] 323–333 8.9–10.3 n.a. SynVisVar
Ethyl p-aminobenzoate Li et al. [498] 308–328 8–21 100 AnPTSemY
Ethyl p-hydroxybenzoate Li et al. [498] 308–328 8–21 100 AnPTSemY
Ethylbenzene Zhang et al. [792] 303–335 6.4–10.8 50 SynVisVarPcTc
Ethylvanillin Skerget et al. [684] 313–353 8.1–30.1 120 AnT
Skerget et al. [684] 350–330 0–44 74 SynVis
Fatty acid ethyl esters from castor oil Ndiaye et al. [572] 294–343 1.7–25.4 n.a. SynVisVar
Fatty acid ethyl esters from soybean oil Ndiaye et al. [572] 313–343 1.3–6 n.a. SynVisVar
Felodipine Weinstein et al. [762] 298–318 8–25 30 SynVisVar
Weinstein et al. [762] 298–318 8–25 2.7 AnSpec
Fennel extract Moura et al. [563] 303–333 4.7–22 25 SynVisVar
Ferulic acid (3-(4-hydroxy-3-methoxyphenyl)-2-propenoic acid) Sun et al. [704] 308–338 10–35 10 AnPTSemY
Fish oil Darvarnejad et al. 313–343 13.6–27.2 n.a. AnPTSemY
[243]
Fluoromethane (HFC-41) Di Nicola et al. [256] 217–292 0.3–4.3 273.5 SynT
Table 4 (Continued)
Fluvastatin Hojjati et al. [32] 308–348 12.1–35.4 1 AnTValY

Gelucire 43-01 de Sousa et al. [250] 308–321 0.1–15.1 4 SynVis
de Sousa et al. [250] 310–326 10–19 60 AnT
Glycidyl methacrylate Franceschi et al. 303–343 2–13.1 25 SynVisVar
[301]
Hardened rapeseed oil Rp70 Münüklü et al. [565] 333–367 3.1–30.7 3.5 SynVisVar
Hexadecanoic acid Garlapati and Madras 308–318 12.8–22.6 n.a. AnPTSemY
[311]
Hexafluoroethane (PFC-116) Di Nicola et al. [256] 214–269 0.3–3.3 273.5 SynT
Valtz et al. [734] 253–296 1–6.4 28 AnTCapValVis
Hexanal Seredynska et al. [30] 323–383 2.3–15.2 87 AnTCapValVisVar
Hexyl acetate Byun et al. [200] 313–373 3–16.4 25 SynVisVar
Hydrogen Ke et al. [139] 292–304 8.4–13.4 320 SynNonPcTc
Zevnik and Levec 298–298 0.9–6 300 AnTX
[788]
Hydrogen sulfide Rivollet et al. [617] 254–303 1.4–4.7 n.a. SynNon
Hydrogenated castor oil Münüklü et al. [565] 353–403 4.2–32.2 3.5 SynVisVar
Hydrogen-containing silicone oil SiH Li et al. [497] 308–328 10–14.5 50 SynVis
hydroxyl-ended silicone oil SiOH (Mw 400) Li et al. [497] 308–328 8–10 50 SynVis
Iodobenzene Leeke et al. [487] 353–383 10.1–24.8 100 SynNonVis
Iodopropynyl butylcarbamate Shin and Kim [679] 313–333 8.7–34.1 25 SynVisVar
Irgacure® 2959 photoinitiator Coimbra et al. [228] 308–328 10–26 30 AnTValVis
Isoamyl acetate Kwon et al. [472] 313–333 1.5–8.8 150 AnTVLcirVal
Isobutoxyethanol (iC4E1) Sam et al. [678] 313–333 0.3–8.8 320 AnTVLcirValVis
Isobutyl acetate Kwon et al. [472] 313–333 1.3–8.5 150 AnTVLcirVal
Isobutyl acrylate Byun and Lee [204] 313–393 2.4–14.7 28 SynVisVar
Isobutyl methacrylate Byun and Lee [204] 313–393 4.5–15.9 28 SynVisVar
isopropoxyethanol (iC3E1) Sam et al. [678] 313–333 0.4–9.9 320 AnTVLcirValVis
Isopropyl acetate Cheng and Chen 308–318 3–7.8 320 AnTLcirValVis
[159]
Kwon et al. [472] 313–333 1.6–8.7 150 AnTVLcirVal
Isopropyl acrylate Byun and Lee [203] 313–393 2.6–13.6 28 SynVisVarPc
Byun and McHugh 313–473 2.6–12.6 28 SynVisVar
[206]
Isopropyl ethanoate Kodama et al. [160] 313–313 3–6.1 320 AnTVLcirValVis
Kodama et al. [160] 313–313 0.4–7.1 299 SynNonVisVar
Isopropyl methacrylate Byun and Lee [203] 313–393 2.4–14.2 28 SynVisVarPc
Byun and McHugh 313–473 2.4–14.2 28 SynVisVar
[206]
Isopropylcyclohexane Vitu et al. [746] 292–373 1–16.9 30 SynVisVar
Krytox Aguiar-Ricardo et al. 304–304 7.4–7.5 5 SynNonVisPcTc
[167]
Lactic acid Wang et al. [754] 313–313 12.1–12.1 n.a. SynVis
Linoleic acid methyl ester Chang et al. [215] 313–333 2.8–18 n.a. SynTVLcirVis
Lithium bis(trifluoroethyl)dithiocarbamate Weinstein et al. [761] 298–318 9.9–24.9 30 SynVisVar
Lithium dibutyldithiocarbamate Weinstein et al. [761] 298–318 8–24.9 30 SynVisVar
Lithium diethyldithiocarbamate Weinstein et al. [761] 298–318 8.5–25 30 SynVisVar
Lithium dipropyldithiocarbamate Weinstein et al. [761] 298–318 10–25 30 SynVisVar
l-Lactide Gregorowicz [325] 275–355 7.6–80.5 n.a. SynVisVar
Lovastatin Hojjati et al. [32] 308–348 12.1–35.4 1 AnTValY
Lycopene de la Fuente et al. 313–333 19.4–41.8 50 AnTValVis
[247]
Menthol Sovová et al. [58] 303–333 6.6–9.3 12 AnPTSemY
Sovová et al. [58] 276–313 0.8–9 10 SynVis
Methane Le and Trebble [481] 168–187 0.9–3 n.a. SynVis
Methanol Ke et al. [139] 304–328 7.3–10.4 80–320 SynNonPcTc
Naidoo et al. [25] 263–373 0.7–12 200 AnTValVisVar
Schwinghammer 303–303 0.8–5.4 140 AnTVcirVis
et al. [646]
Xie et al. [770] 313–313 0.9–7.9 5–20 SynVisVar
Methyl acetate Byun et al. [200] 313–373 1.3–11.3 25 SynVisVar
Kato et al. [414] 313–313 0.6–7.8 299 SynNonVLcirVarVis
Schwinghammer 308–328 1–8.8 140 AnTVcirVis
et al. [646]
Methyl methacrylate Soares da Silva et al. 313–338 6.3–10.4 n.a. SynVisVar
[686]
Uzun et al. [729] 323–353 6.2–12.2 115 AnTBlo
Zwolak et al. [818] 308–333 1–8.3 70 AnTLcirVis
Zwolak et al. [818] 308–333 1–8.3 70 AnTLcirVis
Methyl salycilate Ismadji [378] 343–423 9–31 n.a. AnTBlo
Methylcyclopentane Vitu et al. [746] 292–373 1.1–13.7 30 SynVisVar
Methyl-tri-butylammonium bis(trifluoromethylsulfonyl)imide Anthony et al. [74] 298–298 0–1.3 n.a. AnGrav
([MeBu3N] [Tf2N])
Methyl-tributylphosphonium triflate [TBMP] [Tfo] Scurto et al. [648] 306–392 0.1–35 n.a. SynVis
Scurto et al. [648] 392–392 15–15 n.a. SynVis
Methyltrichlorosilane Vyhmeister et al. 307–347 6.6–10.7 n.a. SynVisVarPc
[751]
Table 4 (Continued)
Methyltrioctylammonium bromide [MTOAm] [Br] Scurto et al. [648] 292–292 4–4 n.a. SynVis
Methyltrioctylammonium triflate [MTOAm] [Tfo] Scurto et al. [648] 296–296 3.5–3.5 n.a. SynVis
Methyl-tris(2-methyl-propyl)ammonium triflate [TiBMAm] [Tfo] Scurto et al. [648] 327–327 15–15 n.a. SynVis
Modified phosphines DPPE Li et al. [497] 323–323 16.9–16.9 50 SynVis
Modified poly(propylene oxide) Ac–PPO Li et al. [497] 308–328 8.1–13.7 50 SynVis
Modified poly(propylene oxide) Ac–PPO–Ac Li et al. [497] 308–328 7.5–12.8 50 SynVis
Modified poly(propylene oxide) TMS–PPO (Mw 1000) Li et al. [497] 308–328 16–18 50 SynVis
Modified poly(propylene oxide) TMS–PPO (Mw 2000) Li et al. [497] 308–328 20–23 50 SynVis
Modified poly(propylene oxide) TMS–PPO (Mw 400) Li et al. [497] 308–328 7.6–12.4 50 SynVis
Modified poly(propylene oxide) TMS–PPO–Ac Li et al. [497] 308–328 7.7–12.5 50 SynVis
Modified poly(propylene oxide) TMS–PPO–TMS Li et al. [497] 308–328 7.6–12.3 50 SynVis
m-Xylene Knez et al. [430] 313–353 0.7–10.3 500 AnTVLcirVis
N,N,N ,N -Teraethyl-3-oxapentanediamide Koh et al. [435] 313–313 9.3–11.8 22.4 SynVisVar
N,N,N ,N -Tetra-n-butyl-3-oxapentanediamide Koh et al. [435] 313–313 9.3–11.5 22.4 SynVisVar
N,N,N ,N -Tetra-n-butyl-3-oxapentanediamide/nitric acid/Uranium Koh et al. [435] 293–313 7–35 22.4 SynVisVar
Komplex
N,N,N ,N -Tetra-n-butyl-3-oxapentanediamide/nitric acid Komplex Koh et al. [435] 293–313 7–35 22.4 SynVisVar
N,N,N ,N -Tetrahexyl-3-osxapentanediamide Koh et al. [435] 313–313 11.2–12.8 22.4 SynVisVar
N,N,N ,N -Tetraoctyl-3-oxapentanediamide Koh et al. [435] 313–313 11.5–13.6 22.4 SynVisVar
N,N,N-Trimethylbutylammonium Muldoon et al. [84] 333–333 0.1–1.3 n.a. AnGrav
bis(trifluoromethylsulfonyl)imide [N4111] [Tf2N]
N,N-Dimethylacrylamide Santos et al. [630] 303–358 5–16.5 28 SynVisVar
Nabumetone Su and Chen [696] 308–328 10–22 150 AnPTSemY
N-Acetyl-l-phenylalanine (AP) Freitag et al. [304] 308–308 7.8–23.5 10 AnPTSemY
N-Acetyl-l-phenylalanine ethyl ester (APEE) Freitag et al. [304] 308–328 7.8–23.5 10 AnPTSemY
N-Acetyl-l-tyrosine (AT) Freitag et al. [304] 308–308 7.8–23.5 10 AnPTSemY
N-Acetyl-l-tyrosine ethyl ester (ATEE) Freitag et al. [304] 308–308 7.8–23.5 10 AnPTSemY
Naphthalene Bertakis et al. [189] 333–353 0.1–23.1 50 SynVisVar
Dahmen et al. [241] 328–328 10–12 10 AnPTSemY
Fu et al. [307] 313–333 8–10 n.a. AnTVal
Harris et al. [339] 372–430 0–20.8 112.82 SynT
Harris et al. [339] 372–430 18.5–23.4 112.82 SynVis
Khimeche et al. [421] 308–333 10–19.6 n.a. AnPTSemY
Perez et al. [600] 308–328 5–25 15 SynVisVar
Ravipaty et al. [611] 308–308 9.8–19.9 1.6 AnPTSemYVal
Scurto et al. [648] 328–353 0.1–22.2 n.a. SynVisVar
Suleiman et al. [68] 308–308 12–28 n.a. AnPTChro
Vyhmeister et al. 307–307 8.8–8.8 n.a. SynVisVarPc
[751]
Zúñiga-Moreno et al. 313–328 8.7–20.5 n.a. SynVisVar
[817]
N-CBZ-l-phenylalanine(CBZ-P) Freitag et al. [304] 308–308 7.8–23.5 10 AnPTSemY
N-CBZ-l-tyrosine (CBZ-T) Freitag et al. [304] 308–308 7.8–23.5 10 AnPTSemY
n-Decane Ayirala and Rao [129] 310–310 0.1–8 n.a. SynNon
Jiménez-Gallegos 319–372 3.4–16 40 AnTCapValVis
et al. [391]
Polikhronidi et al. 377–460 16.2–18.2 n.a. SynOthPcTc
[155]
n-Heptane Ke et al. [140] 300–338 6.3–10.3 320 SynNonPcTc
Mutelet et al. [564] 310–413 2.3–13.4 12.4 SynVisVar
n-Hexadecane Venter et al. [738] 313–333 2–22 500 AnT
n-Hexane Lay et al. [478] 293–308 1.7–7.3 130 AnTVisVar
Wang et al. [753] 323–333 7.2–9.2 n.a. SynVisVar
Nickel(II) acetylacetonatea Aschenbrenner et al. 333–333 10–30 10 AnPTSemY
[177]
Nitrendipine Weinstein et al. [762] 298–318 8–25.1 30 SynVisVar
Weinstein et al. [762] 298–318 8–25.1 2.7 AnSpec
Nitromethane Lazzaroni et al. [479] 298–313 0.5–7.1 150 SynTVis
Nitrous oxide Di Nicola et al. [258] 214–281 0.4–4.1 273.5 SynT
N-Methyl caprolactam Kwon et al. [473] 323–353 5.6–19.6 25 SynVisVar
N-Methyl-2-pyrrolidone Lazzaroni et al. [479] 313–313 0.7–7.7 150 SynTVis
n-Nonane Camacho-Camacho 315–418 2–16.7 100 AnTCapValVis
et al. [209]
n-Octane Jiménez-Gallegos 322–372 2–13.7 40 AnTCapValVis
et al. [391]
Yu et al. [781] 313–393 1.1–14.4 100 AnTCapVisVarPcTc
Nonanoic acid (pelargonic acid) Sparks et al. [690] 313–333 10–30 100 AnPTSemY
n-Pentadecane Secuianu et al. [649] 298–316 0.5–12.7 60 AnTVisVar
N-Phenylacetamide Huang et al. [357] 308–328 10.4–22.5 300 AnPTSemY
n-Undecane Camacho-Camacho 314–418 2–20 100 AnTCapValVis
et al. [209]
N-Vinyl caprolactam Kwon et al. [473] 323–353 3.8–20.6 25 SynVisVar
Table 4 (Continued)
Octadecanoic acid Garlapati and Madras 308–318 12.8–22.6 n.a. AnPTSemY

[311]
Octyl acrylate Byun and Yoo [99] 313–473 4.5–20.1 28 SynVisVar
Octyl benzoate head–head dimer (HC8 H–H) Shen et al. [660] 294–375 6–69.3 15 SynVisVar
Octyl benzoate tail–tail dimer (HC8 T–T) Shen et al. [660] 294–372 6.1–148 15 SynVisVar
Octyl methacrylate Byun and Yoo [99] 313–473 4–20.8 28 SynVisVar
o-Ethylvanillin Skerget et al. [684] 311–339 0–34.3 74 SynVis
Skerget et al. [684] 313–353 10.3–30.2 120 AnT
Oleic acid methyl ester Chang et al. [215] 313–333 2.8–18 n.a. SynTVLcirVis
Oligo (dimethylsiloxane)-substituted gem-diphosphate 1 Dzielawa et al. [275] 313–313 3–9.1 10 SynPVis
Oligo (dimethylsiloxane)-substituted gem-diphosphate 2 Dzielawa et al. [275] 313–313 3.3–8.8 10 SynPVis
Oligo (dimethylsiloxane)-substituted gem-diphosphate 5 Dzielawa et al. [275] 313–313 4–8.8 10 SynPVis
Olive husk oil de Lucas et al. [249] 333–353 15–35 75 AnPTSemY
o-Phthalic acid Tian et al. [716] 308–328 8–21 377 AnPTSemY
o-Vanillin Skerget et al. [684] 294–316 0–5.5 74 SynVis
Skerget et al. [684] 313–353 7.8–30.3 120 AnT
o-Xylene Knez et al. [430] 313–353 0.7–14.8 500 AnTVLcirVis
Oxymatrine Su et al. [694] 308–328 11–21 2.5 AnPTSemYSpec
Paclitaxel Suleiman et al. [68] 318–328 10–28 n.a. AnPTChro
Palladium(II) acetylacetonate Yoda et al. [778] 313–313 10–30 1 AnTVcirVal
Palladium(II) acetylacetonateb Aschenbrenner et al. 333–333 10–30 10 AnPTSemY
[177]
Palmitic acid Bertakis et al. [189] 319–335 0.1–30 50 SynVisVar
p-Aminobenzoic acid Tian et al. [716] 308–328 8–21 377 AnPTSemY
Patchoulol Hybertson [57] 313–323 10–25 7.5 AnPTSemYVal
p-Bromobenzaldehyde Favareto et al. [292] 303–333 9–11.7 25 SynVisVar
PEG-5 cocomonium nethylsulfate (Ecoeng 500) Muldoon et al. [84] 333–333 0.1–1.3 n.a. AnGrav
Pentaerythritol tetra(2-ethylhexanoate) Fandino et al. [287] 283–333 0.3–6.3 23 SynT
Pentaerythritol tetrahexanoate Bobbo et al. [192] 243–343 0.1–9.8 180 SynT
Pentaerythritol tetrapentanoate Fandino et al. [287] 283–333 0.7–6.3 23 SynT
Pentafluoroethane (HFC-125) Jeong et al. [386] 313–333 2–6.4 320 AnTVLcirValVis
Pentyl acetate Byun et al. [200] 313–373 2.4–15.5 25 SynVisVar
Pentyl acrylate Byun and Yoo [205] 313–393 2.2–16.8 28 SynVisVarPc
Pentyl methacrylate Byun and Yoo [205] 313–393 2.5–17.4 28 SynVisVarPc
Perfluorobenzene Dias et al. [262] 293–353 0.6–11.5 30 SynVisVar
Perfluorodecalin Dias et al. [262] 293–353 0.7–12.6 30 SynVisVar
Perfluorohexane (PFC-72) Lazzaroni et al. [479] 313–313 0.6–6.4 150 SynTVis
Perfluoromethylcyclohexane Dias et al. [262] 293–353 0.7–10.4 30 SynVisVar
Perfluoro-n-octane Dias et al. [262] 293–353 0.5–10.6 30 SynVisVar
Perfluorotoluene Dias et al. [262] 293–353 0.6–12 30 SynVisVar
Permethrin Kotnik et al. [446] 293–313 11.6–26.9 120 AnT
Kotnik et al. [446] 313–319 0.2–21.8 35 SynVis
Phenanthrene Bertakis et al. [189] 354–368 1.4–28 50 SynVisVar
Dohrn et al. [95] 357–371 0.1–9.7 250 SynVisVar
Esmaeilzadeh and 318–318 11.7–20.1 n.a. AnPTSemY
Goodarznia [283]
Shin and Kim [679] 308–308 11.3–33.2 25 SynVisVar
Suleiman et al. [68] 318–318 16–28 n.a. AnPTChro
Phenylboric acid Leeke et al. [487] 353–383 9.9–30 100 SynNonVis
Phenylbutazone Su and Chen [696] 308–328 10–22 150 AnPTSemY
Phosphine Ph3P Li et al. [497] 323–323 12.5–12.5 50 SynVis
Pindolol Weinstein et al. [760] 298–318 8–27.5 30 SynVisVar
Platinum(II) acetylacetonate Yoda et al. [778] 313–313 10–30 1 AnTVcirVal
p-Methylbenzen sulfonic acid Zhang et al. [807] 308–328 8–21 100 AnPTSemY
p-Nitrobenzoic acid Tian et al. [714] 308–328 8–21 377 AnPTSemY
Poly([2-(methacryloyloxy)ethyl] trimethyl ammonium Blasig et al. [75] 298–348 0.1–1.5 n.a. AnGrav
tetrafluoroborate) P[MATMA] [BF4 ]
Poly(1-(p-vinylbenzyl)-3-methyl-imidazolium tetrafluoroborate) Blasig et al. [190] 298–348 0.1–18 n.a. AnGrav
(P[VBMI] [BF4 ])
Poly(1,1,2,2-tetrahydroperfluorodecyl acrylate) André et al. [171] 297–331 8.5–18 n.a. SynVisVar
Poly(1,1-dihydroperfluorooctyl methacrylate-r-2- Hussain et al. [36] 308–338 0.1–10.5 25 AnOth
tetrahydropyranylmethacrylate) (poly(FOMA-r-THPMA))
Poly(1-O-(vinyloxy) Tapriyal et al. [712] 298–298 35–77 n.a. SynVisVar
ethyl-2,3,4,6-tetra-O-acetyl-␤-d-glucopyranoside)
Poly(2,2,2-trifluoroethyl methacrylate) Kwon et al. [474] 316–451 26.3–59.6 n.a. SynVisVar
Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Cravo et al. [237] 308–313 10–15 n.a. AnTMla
Poly(butylene succinate) Lian et al. [501] 374–391 0.1–20.7 3 SynVis
Poly(cylclohexene carbonate) van Schilt et al. [735] 455–479 254–335 n.a. SynVisVar
Table 4 (Continued)
Poly(␧-caprolactone) Byun et al. [202] 458–502 252.2–283.2 28 SynVisVar

Poly(ethylen glycol) (PEG 1500) Aionicesei et al. [168] 298–323 5.6–25.4 n.a. AnGrav
Poly(ethylen glycol) (PEG 4000) Aionicesei et al. [168] 298–323 5.6–24.6 n.a. AnGrav
Poly(ethylene adipate) Lian et al. [501] 306–306 27.6–27.6 3 SynVis
Poly(ethylene glycol) 1500 Pasquali et al. [71] 308–328 3–19.5 n.a. AnSpec
Poly(ethylene glycol) 400 Matsuyama and 313–313 13.5–18.9 150 SynVisVar
Mishima [541]
Poly(ethylene glycol)200 Hou et al. [356] 303–323 1–8.1 50 AnTBloVisVar
Poly(ethylene oxide) (PEG) (Mw 400) Li et al. [497] 308–328 22–22 50 SynVis
Poly(ethylene) Grolier [327] 333–353 0.1–43 n.a. SynT
Poly(heptadecafluorodecyl acrylate) Shin et al. [673] 303–364 8.1–30.5 25 SynVisVar
Poly(heptadecafluorodecyl methacrylate (poly(HDFDMA)) Shin et al. [677] 303–364 9.1–29.2 25 SynVisVar
Poly(heptadecafluorodecyl methacrylate) Shin et al. [676] 303–365 10–35 25 SynVisVar
Poly(heptadecafluorodecyl methacrylate-co-methyl methacrylate) Shin et al. [676] 303–365 10–35 25 SynVisVar
Poly(isopropyl acrylate) Byun and McHugh 406–485 135.2–268.5 28 SynVisVar
[206]
Poly(lactic acid) Kasturirangan et al. 313–344 0.8–7.8 25 AnOth
[412]
Tapriyal et al. [712] 298–298 120–142 40 SynVisVar
Poly(lactic-co-glycolic acid) Elvassore et al. [282] 313–313 0.6–4 42 SynT
Poly(lactide) 100DL Liu and Tomasko 303–333 0.1–10 n.a. SynT
[145]
Poly(lactide-co-glycolide) Kasturirangan et al. 313–344 1.3–8.1 25 AnOth
[412]
Poly(lactide-co-glycolide) 5050 Aionicesei et al. [77] 308–323 10–30 n.a. AnGrav
Liu and Tomasko 303–333 0.1–10 n.a. SynT
[145]
Poly(lactide-co-glycolide) 7525 Liu and Tomasko 303–333 0.1–10 n.a. SynT
[145]
Poly(l-lactide) Aionicesei et al. [77] 308–323 10–30 n.a. AnGrav
Lian et al. [501] 393–393 27.6–27.6 3 SynVis
Poly(methyl methacrylate) Kasturirangan et al. 313–313 2–8 25 AnOth
[412]
Pantoula et al. [85] 308–354 0.1–6 n.a. AnOth
Pantoula and 308–405 3–40 n.a. AnTMla
Panayiotou [86]
Pantoula and 324–354 1.5–36.9 n.a. AnGrav
Panayiotou [86]
Rajendran et al. [610] 323–353 5–23.8 n.a. AnGrav
Poly(methylmethacrylate-co-ethylhexyacrylate-co- Duarte et al. [270] 300–313 4.9–10.3 n.a. AnSpec
ethyleneglycoldimethacrylate)
Duarte et al. [49] 313–313 4.9–10.3 n.a. AnTMla
Poly(methymethacrylate-co-ethylhexylacrylate-co- Duarte et al. [49] 308–323 10–20 n.a. AnTMla
ethyleneglycoldimethacrylate)
Poly(octyl acrylate) Byun and Yoo [99] 425–493 126.9–266.3 28 SynVisVar
Poly(p-perfluorooctyl-ethylene sulfonylmethyl styrene) Shin et al. [675] 350–453 55.6–132.5 28 SynVisVar
Poly(p-perfluorooctyl-ethyleneoxymethyl styrene) Shin et al. [675] 331–452 23.9–48.1 28 SynVisVar
Poly(p-perfluorooctyl-ethylenethiomethyl styrene) Shin et al. [675] 333–453 25.6–47.7 28 SynVisVar
Poly(propylene glycol)monobutyl ether (PPG-MBE, MW 340, 1000, Hong et al. [354] 298–298 6.4–42.2 120 SynVis
1200)
Poly(propylene oxide) PPO (Mw 400) Li et al. [497] 308–328 8.2–12.6 50 SynVis
Poly(propylene) Lei et al. [83] 313–483 2–10 n.a. AnGrav
Li et al. [78] 453–493 3.5–28 n.a. AnGrav
Poly(propylene) branched Li et al. [493] 453–493 3–28 n.a. AnGrav
Poly(propylene) linear Li et al. [492] 453–493 3.4–31 n.a. AnGrav
Li et al. [493] 453–493 3–28 n.a. AnGrav
Poly(p-vinylbenzyltrimethyl ammonium tetrafluoroborate) Blasig et al. [190] 298–348 0.1–18 n.a. AnGrav
(P[VBTMA] [BF4 ])
Poly(p-vinylbenzyltrimethyl ammonium tetrafluoroborate) Blasig et al. [75] 298–348 0.1–1.5 n.a. AnGrav
P[VBTMA] [BF4 ]
Poly(vinylidene fluoride) Grolier [327] 391–391 0.1–43 n.a. SynT
von Solms et al. [80] 353–393 1.8–3.8 n.a. AnGrav
Polyalkylene glycol lubricant oil Garcia et al. [309] 253–333 0.7–11.5 314 SynT
Polyamide (PA-11) von Solms et al. [747] 323–363 2–4.2 n.a. AnGrav
Polycaprolactone Lian et al. [501] 307–332 0.1–27.6 3 SynVis
Polycaprolactone (CAPA 6800) Leeke et al. [488] 313–333 8–20 100 AnTVal
Polyethylene oxide-2,6,8-trimethyl-4-nonyl ethers (TMN) Haruki et al. [340] 308–343 19.8–32.8 15 SynNonVisVar
Polyethylene terephthalate Faridi and Todd [50] 373–448 6–11 45 AnTMla
Polyisoprene rubber Kojima et al. [436] 323–323 6–18 n.a. AnGrav
Polylactide Li et al. [35] 453–473 3.4–27.8 n.a. AnGrav
Polymethylmethacrylate Üzer et al. [730] 308–318 8–15 60 AnTVis
Polystyrene Pantoula et al. [85] 308–324 0.1–6 n.a. AnOth
Pantoula and 308–405 3–42 n.a. AnTMla
Panayiotou [86]
Pantoula and 324–405 1.5–44.6 n.a. AnGrav
Panayiotou [86]
Table 4 (Continued)
Polystyrene-␤-poly(1,1,2,2-tetrahydroperfluorodecyl acrylate) André et al. [171] 297–331 12–23 n.a. SynVisVar

block copolymer
Polyvinyl acetate Tapriyal et al. [712] 298–298 40–60 120 SynVis
Precirol Calderone [94] 323–336 0.1–30 4 SynVis
Calderone [94] 323–333 10–20 60 AnT
Precirol ATO5 de Sousa et al. [250] 323–333 10–19.7 60 AnT
de Sousa et al. [250] 323–336 0.1–15.1 4 SynVis
Progesterone Favareto et al. [291] 283–301 4.2–9.3 25 SynVIsVar
Propyl acetate Byun et al. [200] 313–373 1.7–12.6 25 SynVisVar
Propyl p-hydroxybenzoate Jin et al. [392] 308–328 8–23 377 AnPTSemY
Propylene glycol monomethyl ether acetate Chiu et al. [224] 318–358 1.7–13.3 60 SynVisVar
p-Xylene Knez et al. [430] 313–353 0.6–12.3 500 AnTVLcirVis
Pyrazine Shen et al. [661] 294–366 4.7–20.7 15 SynVisVarPc
Pyrrole Kulik et al. [455] 313–343 7–17 4–14 SynVisVar
Quinoline Chiu et al. [224] 308–333 3.4–27.7 60 SynVisVar
Racemic trans-4-(4 -fluorophenyl)-3-hydroxymethyl-1-methyl- Bao et al. [182] 308–328 8.8–24.2 0.83 AnPTSemYSpec
piperidine
Rhodium(III) acetylacetonate Yoda et al. [778] 313–313 10–30 1 AnTVcirVal
Rosuvastatin Hojjati et al. [32] 308–348 12.1–35.4 1 AnTValY
RS-(+-)-ibuprofen Uchida et al. [727] 320–349 0.1–25.9 35 SynVis
Ruthenium(III) acetylacetonate Yoda et al. [778] 313–313 10–30 1 AnTVcirVal
S-(+)-Ibuprofen Uchida et al. [727] 293–324 0.1–4.7 35 SynVis
Salicylamide Su and Chen [696] 308–328 10–22 150 AnPTSemY
Salicylic acid Lin et al. [509] 318–328 11–14.6 25 SynVisVar
Ravipaty et al. [612] 308–328 12–28 1.6 AnPTSemYVal
Seawater Zhang et al. [803] 276–278 3.5–21.6 100 SynT
Semifluorinated octyl benzoate head–head dimer (FC8 H–H) Shen et al. [660] 294–371 4.8–21.4 15 SynVisVar
Semifluorinated octyl benzoate tail–tail dimer (FC8 T–T) Shen et al. [660] 294–369 5.8–24.3 15 SynVisVar
S-ethyl-N,N,N ,N -tetramethylthiouronium Zhang et al. [802] 283–323 0–1.7 n.a. AnGrav
Tris(pentafluoroethyl)trifluorophosphate ([ETT] FEP])
Silicone with pendant phosphine ligands Ph2P-DB570-sioh (1:3) Li et al. [497] 308–323 16.5–20.1 50 SynVis
Silicone with pendant phosphine ligands Ph2P-DB570-sioh/PEG Li et al. [497] 308–328 10.4–17.8 50 SynVis
(2:1)
Silicone with pendant phosphine ligands Ph2P-HDDA-sih (1:10) Li et al. [497] 308–328 7.8–13.9 50 SynVis
Silicone with pendant phosphine ligands Ph2P-HDDA-sih (1:5) Li et al. [497] 308–328 7.4–14.9 50 SynVis
Silicone with pendant phosphine ligands Ph2P-NPGDA-sih (1:10) Li et al. [497] 308–328 7.7–13.7 50 SynVis
Silicone with pendant phosphine ligands Ph2P-NPGDA-sih (1:5) Li et al. [497] 308–328 8.1–13.8 50 SynVis
Silver(I) acetylacetonate Yoda et al. [778] 313–313 10–30 1 AnTVcirVal
Simvastatin Hojjati et al. [32] 308–348 12.1–35.4 1 AnTValY
Sodium bis-(2,2,3,3,4,4,5,5-octafluoro-1-pentyl)-2-sulfosuccinate Koh et al. [101] 313–313 0.1–12.5 22.4 SynVisVar
Sodium dibutyl sulfosuccinate Liu et al. [47] 308–338 10–30 48 AnTIns
Sodium dihexyl sulfosuccinate Liu et al. [47] 308–338 10–30 48 AnTIns
Sodium dioctyl sulfosuccinate Liu et al. [47] 318–318 30–30 48 AnTIns
Sodium dipentyl sulfosuccinate Liu et al. [47] 318–318 30–30 48 AnTIns
Sodium salt of dipentyl-2-sulfosuccinate Liu et al. [521] 308–338 15–35 48 AnTIns
Solvent brown 1 Banchero et al. [59] 353–393 18–30.1 32 AnPTSemY
Soybean oil Ndiaye et al. [572] 276–343 3.7–26.4 n.a. SynVisVar
Spiroindolinonaphthoxazine photochromic dye (1,3-dihydro-3, Coimbra et al. [226] 308–328 10–26 30 AnTValVis
3-dimethyl-1-isopropyl-6-(2,3)-(dihydroindole-1-yl)spiro
[2H-indole-2,3 -3H-naphtho[2,1-b] [1,4] oxazine]
Stearic acid Bertakis et al. [189] 325–342 0–30 50 SynVisVar
Styrene Wang et al. [753] 323–333 8.7–10.8 n.a. SynVisVar
Zhang et al. [792] 303–333 6.3–10.7 50 SynVisVarPcTc
Substituted bis(acetylacetone)ethylenediimine (R4BAE, where Dunbar et al. [273] 303–332 7–21 n.a. SynVisVar
R = CH3 or CF3 )
Sunflower oil Hegel et al. [345] 288–308 3.4–7.5 80 AnTCapVis
Soares et al. [687] 313–353 20–35 100 AnTY
Surfynol-420 (S20) Akutsu et al. [98] 318–318 11–17.5 61.6 SynVisVar
Tert-butyl acrylate Byun and Lee [204] 313–393 4.2–13.9 28 SynVisVar
Tert-butyl methacrylate Byun and Lee [204] 313–393 3.2–14.7 28 SynVisVar
Tetra-n-butylammonium bromide [tbam] [Br] Scurto et al. [648] 353–353 15–15 n.a. SynVis
Tetra-n-butylammonium docusate [N4444] [docusate] Muldoon et al. [84] 333–333 0.1–1.3 n.a. AnGrav
Tetra-n-butylammonium tetrafluoroborate [tbam] [BF4 ] Scurto et al. [648] 300–429 0.1–33.5 n.a. SynVis
Scurto et al. [648] 301–433 0.1–10.2 n.a. SynVisVar
Tetra-n-butylammonium tosylate [tbam] [Tosyl] Scurto et al. [648] 311–311 15–15 n.a. SynVis
Tetra-n-butylammonium trifluorotris(perfluoroethyl)phosphate Scurto et al. [648] 290–290 3.4–3.4 n.a. SynVis
[tbam] [TFEPF3]
Tetra-n-butylphosphonium bromide [TBP] [Br] Scurto et al. [648] 333–333 15–15 n.a. SynVis
Tetradecanoic acid Garlapati and Madras 308–318 9.9–22.6 n.a. AnPTSemY
[310]
Tetraethyl orthosilicate Jammaer et al. [381] 306–343 7.2–11.9 66 SynVisVar
Tetraethylammonium bis(trifyl)imide [team] [Tf2N] Scurto et al. [648] 294–294 1.5–1.5 n.a. SynVis
Table 4 (Continued)
Tetraheptylammonium bromide [thepam] [Br] Scurto et al. [648] 321–321 15–15 n.a. SynVis
Tetrahexylammonium bromide [thexam] [Br] Scurto et al. [648] 373–307 0.1–23.1 n.a. SynVisVar
Tetrahydrofuran Knez et al. [430] 313–353 0.4–10.2 500 AnTVLcirVis
Li [495] 313–333 6–10 25 SynVisVar
Tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionato)zirconium(IV) Aschenbrenner et al. 333–333 10–17.5 10 AnPTSemY
[177]
Tetra-n-butylphosphonium formate [TBP] [FOR] Yokozeki et al. [780] 298–298 0–1.9 n.a. AnGrav
Tetraoctylammonium bromide [toam] [Br] Scurto et al. [648] 332–370 1–35 n.a. SynVis
Tetrapentylammonium bromide [tpam] [Br] Scurto et al. [648] 354–354 15–15 n.a. SynVis
Thiophene Elizalde-Solis and 314–383 2–14.4 100 AnTCapValVisPc
Galicia-Luna [277]
Serrano-Cocoletzi 314–363 2–12.9 100 AnTValVis
[656]
Thymidine Suleiman et al. [68] 318–328 10–30 n.a. AnPTChro
Toluene Kwon et al. [472] 323–323 1.8–8.7 150 AnTVLcirVal
Lay et al. [478] 293–308 1.7–7.3 130 AnTVisVar
Lee et al. [484] 352–352 0.1–2.9 n.a. SynT
Lee [485] 352–352 0.2–3 n.a. SynT
Naidoo et al. [25] 283–391 0.4–12.1 200 AnTValVisVar
Trans-Co2 (CO)6 [3,5-bis(CF3 )C6 H3 P(i-C3 H7 )2 ] Dahmen et al. [241] 313–343 10–26 10 AnPTSemY
Tri(2-furyl)phosphine Ablan et al. [164] 296–296 12.4–23.3 n.a. SynVisVar
Tri-(2-hydroxy ethyl)-ammonium acetate (THEAA) Yuan et al. [783] 303–323 1–10.1 n.a. SynT
Tri-(2-hydroxy ethyl)-ammonium lactate (THEAL) Yuan et al. [783] 303–323 0.9–8.4 n.a. SynT
Tridodecylamine Kaboudvand 308–328 8–40 n.a. AnPTSemY
Ghaziaskar [401]
Kaboudvand 308–328 8–40 n.a. AnPTSemY
Ghaziaskar [402]
Trifluoroethyl acrylate Wang et al. [753] 323–333 8–10 n.a. SynVisVar
Trifluoromethane (HFC-23) Nasrifar [571] 263–302 1.9–7 3.5 SynVisVar
Triglycidyl p-aminophenol Medina-Gonzalez 318–318 14.5–14.5 10 AnT
et al. [544]
Trihexyl (tetradecyl) phosphonium dodecylbenzenesulfonates Zhang [799] 307–322 4.6–8.9 n.a. SynTVis
[P6,6,6,14] [c12h25phso3]
Trihexyl (tetradecyl) phosphonium mesylate [P6,6,6,14] [meso3] Zhang [799] 307–322 4.4–8.7 n.a. SynTVis
Trihexyltetradecylphoshonium chloride Hutchings [362] 292–343 5.8–11 n.a. SynVisVar
Tri-isobutyl-methyl phosphonium p-toluenesulfonate ([ibu3mep] Anthony et al. [74] 323–323 0–1.3 n.a. AnGrav
[TOS])
Trimethylchlorosilane Vyhmeister et al. 308–343 7.1–10 n.a. SynVisVarPc
[751]
Tri-n-butyl phosphate Koh et al. [435] 313–313 8.7–9 22.4 SynVisVar
Trioctylamine Ghaziaskar [315] 308–338 8–40 12.8 AnPTSemY
Trioxane Tanaka and Ogino 323–393 7.9–11.6 50 AnTY
[710]
Tripalmitin Li et al. [494] 322–337 0.1–19.6 25 SynVisVar
Münüklü et al. [565] 336–363 3.2–24.7 3.5 SynVisVar
Triphenylphosphine Shimoyama et al. 320–333 9–16 26.5 AnSpecVcir
[670]
Tris(2,2,6,6-tetramethyl-3,5-heptanedionato)chromium(III) Aschenbrenner et al. 333–333 10–30 10 AnPTSemY
[177]
Tris(2,2,6,6-tetramethyl-3,5-heptanedionato)cobalt(III) Aschenbrenner et al. 333–333 10–30 10 AnPTSemY
[177]
Tris(2,2,6,6-tetramethyl-3,5-heptanedionato)iron(III) Aschenbrenner et al. 333–333 10–30 10 AnPTSemY
[177]
Tris(2,2,6,6-tetramethyl-3,5-heptanedionato)manganese(III) Aschenbrenner et al. 333–333 10–30 10 AnPTSemY
[177]
Tris(2,2,6,6-tetramethyl-3,5-heptanedionato)ruthenium(III) Aschenbrenner et al. 333–333 10–30 10 AnPTSemY
[177]
Tris(2,2,6,6-tetramethyl-3,5-heptanedionato)titanium(iii) Aschenbrenner et al. 333–333 10–30 10 AnPTSemY
[177]
Tris(p-trifluoromethylphenyl)-phosphine Shimoyama et al. 320–333 9–14 26.5 AnSpecVcir
[670]
Tristearin Spilimbergo [123] 308–325 1–5.8 n.a. SynNon
Tri-tert-butylphenol Hong [106] 301–343 6.8–66.8 n.a. SynVisVar
Ucuuba fat Soares et al. [687] 313–353 20–35 100 AnTY
Uracil Zhou [812] 308–338 15–40 10 AnPTSemY
Uranium dioxide(acetylacetonate)2dimethylsulfoxide Tsukahara [724] 313–313 10–25 216 AnSpec
Uranium dioxide(hexafluoroacetylacetonate)2dimethylsulfoxide Tsukahara [724] 313–313 10–25 216 AnSpec
Uranium dioxide(trifluoroacetylacetonate)2dimethylsulfoxide Tsukahara [724] 313–313 10–25 216 AnSpec
Urea Catchpole [211] 313–353 0.1–30 500 AnPTSemY
Vanillin Hybertson [57] 318–318 10–20 7.5 AnPTSemYVal
Liu [513] 305–408 6.1–135.7 30 SynVis
Skerget et al. [684] 313–353 8–27.6 120 AnT
Skerget et al. [684] 338–354 0.1–48.3 74 SynVis
Table 4 (Continued)
Vetiver grass extract Takeuchi [706] 303–333 6–32 25 SynVisVar

Vitamin K1 (2-methyl-3-phytyl-1,4-naphthoquinone) Kong et al. [440] 313–313 10–30 3.14 AnPTChro
Water Bermejo et al. [187] 296–369 1.5–8.3 n.a. SynVis
Kang et al. [128] 270–282 1–4 350 SynNon
Kim et al. [426] 279–280 10.1–20.1 n.a. SynVisVar
Kiyono et al. [428] 257–283 1.6–4.4 191.5 SynNon
Koglbauer and 293–373 0.1–5.5 49 AnSpec
Wendland [434]
Koschel et al. [443] 323–373 2–20.2 22 SynOth
Qin et al. [605] 323–375 30.1–49.9 200 AnT
Yasuda and Ohmura 244–275 0.3–1.6 200 SynNon
[775]
Zhang et al. [803] 274–281 1.8–23.5 100 SynT
Xanthene Huang et al. [358] 308–328 12–30 20 AnPTSemY
Huang et al. [360] 308–328 8–24 20 AnPTSemY
Xanthone Huang et al. [358] 308–328 8–30 20 AnPTSemY
Huang et al. [360] 308–328 12–30 20 AnPTSemY
librium properties, like the pressure and the composition of the were as follows: empty bags 4.1 g, CO2 collected 2.5–6.5 g, solids
phases, reach equilibrium values, depending on other variables, 0.006–0.6 g. The solids were washed out of the collection bag with
like mole numbers and volume. At the beginning of an experi- a solvent and transferred to NMR tubes.
ment, an equilibrium cell is charged with the substances of interest. Another possibility to reduce sampling problems is the recir-
The pressure is adjusted above or below the desired equilibrium culation of one or more phases, having the advantage that the
value, depending on whether the pressure will rise or fall during sampling volume (e.g., the loop of a six-port valve) is filled iso-
equilibration. After the desired temperature has been reached, the barically. Disadvantages of a recirculation are the need for a
mixture is kept under isothermal conditions. By stirring the mixture well-working pump with only little pressure drop and the need for a
or by rocking the autoclave or by recirculating one or more phases, uniform temperature field to avoid partial condensation or vapor-
time for equilibration of the phases is reduced. After some time, ization in the recirculation line. Therefore, recirculation methods
the pressure reaches a plateau. The pressure can be readjusted, are not suitable in the region close to the critical point where small
by adding or withdrawing material or by changing the volume of changes in temperature and pressure have a strong influence on
the equilibrium cell. Usually, the equilibration is continued for at the phase behavior.
least 30 min after the pressure plateau is sufficiently close to the When only the vapor phase is recirculated (Vcir), it is withdrawn
desired value. Before taking samples from the coexisting phases, continually and passed back into the equilibrium cell through the
the mixture is given sufficient time without stirring, rocking or liquid phase by the action of a pump, e.g. Kato and Nishiumi [40].
recirculation for the separation of the phases. Otherwise the sam- Samples can be withdrawn by placing a sampling valve in the recir-
ple might not be homogeneous but contain material from another culation loop [27] or by blocking off a volume between two valves
phase, e.g. droplets, bubbles or solid particles. in the recirculation loop. The liquid phase is usually analyzed by
Isothermal methods that use stirring or rocking to ensure a rapid taking samples through capillaries.
approach to equilibrium are often called static analytical methods. Seredynska et al. [30] developed an apparatus that consists of
As opposed to recirculating methods, the mixture does not leave the two equilibrium cells that are run parallel at identical tempera-
equilibrium cell during the experiment. But, since the expressions tures and similar pressures. One autoclave was used for sampling
“static cell” and “static method” are used by some authors for other the liquid phase and the other for sampling the vapor phase, each
experimental methods (e.g., for a synthetic method in a view cell via a capillary that is connected to a pneumatic sampling valve. For
or for a synthetic method using the material balance to determine binary systems, it does not matter that slightly different equilib-
solubilities of gases in liquids), we avoid the expression “static” in rium pressures are reached in the autoclaves.
our classification. Recirculation of both the vapor and the liquid phase (VLcir) has
Sampling through capillaries can lead to differential vaporiza- the advantage that sampling from both phases is possible without
tion and scattering results, especially for mixtures containing light using capillaries [41,42]. If a vibrating-tube densimeter is installed
and heavy components when no precautions have been taken to in a recirculation loop, the density of the circulated phase can be
prevent a pressure drop all along the capillary [37]. Differential determined [43]. The pump should be turned off during density
vaporization can be avoided with an experimental design that measurement to avoid errors due to pulsation [42].
ensures that most of the pressure drop occurs at the end of the capil- Ruffine et al. [27] developed an apparatus with vapor-phase cir-
lary close to the chromatographic circuit, e.g. Richon and coworkers culation and a special liquid-phase sampling technique to measure
[38] used a micro-stem ending with a nose entering inside the VLE and VLLE. The liquid phase is transferred from the equilibrium
capillary to reduce the cross-sectional area at the end of the cell to a buffer cell at isobaric conditions by means of two volumet-
capillary. ric pumps. Then the sample is completely vaporized by flash within
Margon et al. [39] investigated VLE of binary, ternary and qua- a vaporization loop and the thermostatic air bath temperature of
ternary systems of phenol, diphenyl carbonate, Bisphenol A and the sampling system is increased up to 373 K. The vaporized sample
CO2 . To determine the solubility of these high-boiling substances is injected into a gas chromatograph. The same procedure is used
in CO2 , an unusual sampling technique was used: a sample of the for each liquid phase.
vapor-phase was trapped into a polyethylene sample bag by quickly Sometimes only the liquid phase is circulated (Lcir), e.g. for
opening and closing the outlet valve to let a part of the vapor-phase mixing, for blocking off a large liquid phase volume from the equi-
out of the autoclave. The amounts of solids and CO2 in the sam- librium cell before pressure reduction [44], for the measurement
ple bags were determined by weighing, while correcting for the of liquid–liquid equilibria or for the measurement of solubilities of
buoyancy effect due to the air displaced by CO2 . Typical weights gases in liquids [45].
Table 5
Binary systems: water + X.
1,2-Benzanthracene Karásek et al. [409] 313–423 4.9–5.2 1.4 AnPTSemY

1,2-Diphenylethane Brunner et al. [197] 476–733 1.6–22 30 SynVis
1,3,5-Trimethylbenzene Brunner et al. [197] 412–647 3.9–22 30 SynVis
1,4-Diphenylbenzene Brunner et al. [197] 511–926 3.2–28.5 30 SynVis
1-Chloronaphthalene Brunner et al. [197] 500–715 2.7–22 30 SynVis
1-Methylnaphthalene Brunner et al. [197] 458–771 1.1–22 30 SynVis
2-butanol Shimoyama et al. [668] 523–573 4.8–11.1 31 AnPTConVis
2-Methylanthracene Karásek et al. [410] 313–453 5–6.4 1.4 AnPTSemY
2-Methylpentane (isohexane) Neely et al. [573] 298–491 0.1–7.2 120 AnPTCon
2-Pentanol Shimoyama et al. [668] 523–523 3.3–4.9 31 AnPTConVis
2-Propanol (isopropanol) Bermejo et al. [188] 400–459 0.4–1.7 n.a. SynVis
Shimoyama et al. [668] 548–573 6.4–11.4 31 AnPTConVis
4,6-Dimethyldibenzothiophene Karásek et al. [55] 313–423 5–5 1.4 AnPTSemY
9,10-Dimethylanthracene Karásek et al. [410] 313–448 5–5.3 1.4 AnPTSemY
9-Phenylanthracene Karásek et al. [410] 313–423 5–5.1 1.4 AnPTSemY
Acenaphthene Andersson et al. [170] 523–523 5–5 11 AnPTSemY
Brunner et al. [197] 470–803 1.4–22 30 SynVis
Acetic acid (ethanoic acid) Richardson et al. [615] 160–300 0.5–7.4 2000 AnT
Acridine Karásek et al. [55] 313–363 5–5 1.4 AnPTSemY
Adamantane Karásek et al. [411] 313–493 5–5.2 1.4 AnPTSemY
Ammonia Sakabe et al. [624] 436–503 14.1–18.6 18 SynVisVarPcTc
Anthracene Andersson et al. [170] 373–473 5–5 3 AnPTSemY
Andersson et al. [170] 523–573 5–10 11 AnPTSemY
Brunner et al. [197] 521–869 3.9–27.1 30 SynVis
Karásek et al. [409] 313–483 3.9–7.7 1.4 AnPTSemY
Argon Koglbauer and Wendland [434] 293–373 0.1–25 49 AnSpec
Benzene Neely et al. [573] 299–490 0.1–6.8 120 AnPTCon
Benzil (1,2-diphenylethane-1,2-dione) Brunner et al. [197] 473–559 1.6–7.2 30 SynVis
Benzophenone Brunner et al. [197] 473–747 1.5–27.5 30 SynVis
Calcium bromide Gruszkiewicz and Simonson [148] 413–523 0.1–3.3 n.a. SynT
Calcium chloride Gruszkiewicz and Simonson [148] 413–523 0.1–3.3 n.a. SynT
Carbazole Karásek et al. [55] 313–433 5–5 1.4 AnPTSemY
Carbon dioxide Kang et al. [128] 270–282 1–4 350 SynNon
Bermejo et al. [187] 296–369 1.5–8.3 n.a. SynVis
Koglbauer and Wendland [434] 293–373 0.1–5.5 49 AnSpec
Koschel et al. [443] 323–373 2–20.2 22 SynOth
Qin et al. [605] 323–375 30.1–49.9 200 AnT
Yasuda and Ohmura [775] 244–275 0.3–1.6 200 SynNon
Zhang et al. [803] 274–281 1.8–23.5 100 SynT
Cyclopentane Brunner et al. [197] 460–647 3.5–32.5 30 SynVis
Diamantane Karásek et al. [411] 313–493 4.8–5.3 1.4 AnPTSemY
Dibenzofuran Karásek et al. [55] 313–353 5–5 1.4 AnPTSemY
Dibenzothiophene Karásek et al. [55] 313–363 5–5 1.4 AnPTSemY
Difluoromethane (hfc-32) Imai et al. [374] 278–290 0.2–1 70 SynNon
Dimethyl ether Park et al. [594] 323–323 0–1.1 n.a. SynT
Diphenyl Brunner et al. [197] 526–789 4.3–30.3 30 SynVis
Diphenylether Brunner et al. [197] 518–766 1.3–30.3 30 SynVis
Diphenylmethane Brunner et al. [197] 526–770 4.3–30.6 30 SynVis
Ethane Kim et al. [426] 277–280 10.1–15.1 n.a. SynVisVar
Mohammadi et al. [556] 275–282 0.6–1.4 58 SynNon
Mokraoui et al. [558] 288–303 3.4–3.4 34 AnTCapVal
Yarrison et al. [774] 314–466 3.4–110.3 1300 AnPTSemY
Ethanol Bazaev et al. [183] 456–598 2.1–15,5 32.56 SynOthPcTc
Bazaev et al. [185] 456–598 2.1–15.5 32.56 SynOthPcTc
Ethylbenzene Coquelet et al. [231] 297–402 0–0.3 n.a. SynTVis
Fluoranthene Karásek et al. [408] 313–378 5–5 1.4 AnPTSemY
Fluorene Brunner et al. [197] 474–747 1.6–23.6 30 SynVis
Karásek [408] 313–383 5–5 1.4 AnPTSemY
Hydrogen sulfide Koschel et al.[444] 323–393 1.6–30.8 n.a. SynOth
Indene Brunner et al. [197] 472–695 1.6–22 30 SynVis
Isobutane (2-methylpropane) Mokraoui et al. [558] 293–353 0.3–1.3 34 AnTCapVal
Krypton Sugahara et al.[699] 274–320 1.6–445 0.2 SynVisSpec
Methane Kang et al. [128] 271–284 2–10 350 SynNon
Abdi et al. [163] 324–324 10–40 n.a. AnT
Chapoy et al. [216] 283–293 10–35 34 AnTCapVal
Chapoy et al. [216] 283–318 0.9–34.6 34 AnTCapVal
Gayet et al. [313] 275–300 3.1–55 250 SynNonVis
Lee et al. [486] 276–281 3.6–6 474 SynNon
Qin et al. [605] 324–375 30.1–49.9 200 AnT
Turner et al. [726] 273–285 2.5–9 n.a. SynNon
Table 5 (Continued)
Voronov et al. [750] 270–285 2.1–9.1 n.a. SynNon

Folas et al. [65] 253–293 1.5–18 300 AnPTSemY
Chapoy et al. [217] 277–297 0.4–4.3 20 AnTCapValVis
Methylfluoride Takeya et al. [708] 273–296 0.2–3.5 202 SynNon
Naphthalene Brunner et al. [197] 470–647 1.7–22 30 SynVis
Karásek et al. [409] 313–348 5–5.1 1.4 AnPTSemY
n-Butane Mokraoui et al. [558] 293–353 0.2–1 34 AnTCapVal
n-Hexane Mokraoui et al. [558] 298–353 0.4–0.5 34 AnTCapVal
Nitrogen Koglbauer and Wendland [434] 293–373 0.1–25 49 AnSpec
Mohammadi et al. [550] 282–363 0.4–4.9 28 AnTCapValVis
n-Pentane Mokraoui et al. [558] 293–353 0–0.4 34 AnTCapVal
o-Xylene Brunner et al. [197] 434–647 0.8–22 30 SynVis
Phenanthrene Karásek et al. [55] 313–363 5–5 1.4 AnPTSemY
Phenanthridine Karásek et al. [55] 313–363 5–5 1.4 AnPTSemY
Phenazine Karásek et al. [55] 313–433 5–5 1.4 AnPTSemY
Phenol Brunner et al. [197] 633–694 5.9–22 30 SynVis
Phenothiazine Karásek et al. [55] 313–453 5–5 1.4 AnPTSemY
Phenoxathiin Karásek et al. [55] 313–328 5–5 1.4 AnPTSemY
Phenoxazine Karásek et al. [55] 313–413 5–5 1.4 AnPTSemY
Potassium chloride Higashi et al. [348] 623–673 9–12 11 AnPTSemY
Propane Gaudette and Servio [312] 274–276 0.1–0.3 n.a. AnT
Yasuda and Ohmura [775] 245–275 0–0.2 200 SynNon
Melnikov et al. [113] 257–275 0.1–0.3 100 SynVis
p-Terphenyl Karásek et al. [409] 333–483 4.9–6.7 1.4 AnPTSemY
p-Xylene Brunner et al. [197] 420–647 0.5–22 30 SynVis
Pyrene Andersson et al. [170] 323–413 5–5 3 AnPTSemY
Andersson et al. [170] 473–573 5–10 11 AnPTSemY
Quinacridone Sue et al. [698] 453–592 24–24 470 AnPTSemY
Sodium chloride Sawamura et al. [634] 263–313 0.1–300 n.a. AnTVar
Higashi et al. [348] 623–673 9–12 11 AnPTSemY
Sulfur hexafluoride (SF6) Sugahara et al. [700] 274–313 0.1–155 5 SynVis
Sugahara et al. [700] 274–313 0.1–155 1 SynVisSpec
Sugahara et al. [700] 274–313 0.1–155 0.2 SynVisSpec
Tetrabutyl ammonium bromide Arjmandi et al. [176] 280–279 3.6–20.9 2400 SynNon
Tetradecyl-trimethylammonium bromide (TTAB) Haramagatti et al. [116] 277–313 0.1–270 0.196 SynNon
Tetrafluoromethane (CFC-14) Mooijer-van den Heuvel [560] 273–281 3.4–12.9 3.5 SynVisVar
Tetrahydrofuran Riesco et al. [616] 345–405 0.4–6 0.035 SynVisCon
Tetralin Brunner et al. [197] 459–719 1.1–22 30 SynVis
Thianthrene Karásek et al. [55] 313–423 5–5 1.4 AnPTSemY
Toluene Neely et al. [573] 297–490 0.1–3.8 120 AnPTCon
Valtz et al. [733] 299–402 0–0.4 n.a. SynTVis
Trans-decalin Brunner et al. [197] 499–687 2.8–32.5 30 SynVis
Trifluoromethane (HFC-23) Mooijer-van den Heuvel [560] 282–293 0.9–4.1 3.5 SynVisVar
Triphenylene Karásek et al. [409] 313–468 5–6.4 1.4 AnPTSemY
Triptycene Karásek et al. [410] 313–513 5–5.2 1.4 AnPTSemY
Wheat starch Randzio et al. [137] 317–321 10–100 n.a. SynNon
Xenon Sugahara et al. [699] 324–345 106–440 0.2 SynVisSpec
Xylene Coquelet et al. [231] 292–402 0–0.3 n.a. SynTVis
Sherman et al. [46] developed a method in which the sampled less steel cylindrical container that was fixed to the head of the
volume stays within the equilibrium cell until depressurization is equilibrium cell. This upper cylindrical container was equipped
finished. We call this method “in situ sampling” (AnTIns). It can with a small magnetic stir bar and communicates with the external
be used for the measurement of the solubility of solids in super- chamber through two slits opened in its uppermost part.
critical fluids. An excess amount of solute is put into a glass vial, In the material-loss-analysis method (AnTMla) the sample is
capped with coarse filter paper, into the equilibrium cell. With two taken out of the equilibrium cell an analyzed after depressuriza-
magnetic stir bars in the equilibrium cell of which one is placed tion. It is used to determine the solubility and diffusivity of volatile
into the vial a faster equilibration can be achieved. After the phase components (often CO2 ) in polymers. After equilibration a fast
equilibrium has been attained, the high-pressure cell is carefully depressurization procedure and a quick transport of the sample
depressurized, and the vial is removed and weighed. The solubility (loaded polymer) to an analytical balance are performed. The mass
can be calculated from the difference of the initial and final mass of decrease of the polymer sample due to desorption of the volatile
the solute in the vial and the difference of the volume of the equilib- component is recorded and analyzed. The initial value of sorbate
rium cell and the vial. Liu et al. [47] used in situ sampling to measure mass can be determined by extrapolation of the desorption curve
the solubility of surfactants in CO2 and in 1,1,1,2-tetrafluoroethane to the beginning of depressurization. Duarte et al. [49] used a quick
(HFC-134a). Instead of a glass vial Filardo et al. [48] used a stain- opening cell. They established a compromise between the veloc-
Table 6
Binary systems: ammonia + X.
1-n-Butyl-3-methylimidazolium Yokozeki and Shiflett [779] 283–355 0.1–2.3 15.3 SynT

hexyfluorophosphate [bmim] PF6 ]
1-n-Butyl-3-methylimidazolium Yokozeki and Shiflett [779] 282–355 0–2.5 15.3 SynT
tetrafluoroborate [bmim] [BF4 ]
1-Dodecene Martin et al. [96] 404–443 11.3–15.8 27 SynVisPcTc
1-Ethyl-3-methylimidazolium Yokozeki and Shiflett [779] 283–347 0.1–2.8 15.3 SynT
bis(trifluoromethylsulfonyl)imide
[emim] [Tf2N]
1-Hexyl-3-methylimidazolium Yokozeki and Shiflett [779] 283–347 0–2.4 15.3 SynT
chloride [hmim] [Cl]
1-Octene Martin et al. [96] 409–434 11.2–12.3 27 SynVisPcTc
1-Pentene Martin et al. [96] 397–401 9.2–9.6 27 SynVisPcTc
Ammonium chloride Tomida et al. [718] 303–373 1–6.2 65.2 SynT
Caesium iodide Sciaini et al. [647] 418–418 8.1–12.8 3 AnSpec
Lithium nitrate Libotean et al. [502] 293–353 0–1.9 166 SynT
Methanol Schäfer et al. [636] 313–395 0.1–4.2 30 SynVis
Schäfer et al. [636] 353–393 0.1–1.6 1600 AnT
Potassium iodide Sciaini et al. [647] 419–426 9.7–14.4 3 AnSpec
Sodium iodide Sciaini et al. [647] 419–426 9.7–14.4 3 AnSpec
Water Sakabe et al. [624] 436–503 14.1–18.6 18 SynVisVarPcTc
Table 7
Binary systems: hydrogen sulfide + X.
1-n-Butyl-3-methylimidazolium Jou and Mather [399] 298–403 0–9.6 n.a. AnTVcir

hexafluorophosphate ([bmim] PF6 ])
Carbon dioxide Rivollet et al. [617] 254–303 1.4–4.7 n.a. SynNon
Carbon disulfide Guilbot et al. [331] 273–348 0–5.8 30 AnTCapValVis
Dimethylsulfide Guilbot et al. [331] 278–293 0–1.5 30 SynTVis
Guilbot et al. [331] 293–333 0.3–4 30 AnTCapValVis
Ethylmethylsulfide Guilbot et al. [331] 293–313 0–2.5 30 SynTVis
n-Heptane Théveneau et al. [713] 293–373 0.3–6.8 n.a. AnTCapValVis
Water Koschel et al. [444] 323–393 1.6–30.8 n.a. SynOth
ity of depressurization and opening of the cell, so that CO2 would that the volume of the cell plays an important role, but they do
not freeze inside. The volume of the cell plays an important role in not give information on the volume of their new cell. They only
preventing the CO2 to freeze; this becomes more evident for the say that it should be as small as possible to prevent freezing of the
experiments with lower time of exposure. The authors point out CO2 .
Table 8
Binary systems: hydrogen + X.
1,1,3,3-Tetramethylguanidium lactate Yuan et al. [782] 308–328 1.2–9.9 n.a. SynT

1,2-Butylene carbonate Kumelan et al. [468] 283–323 1.4–9.2 30 SynVis
1-Hexadecanol Rovetto et al. [621] 371–450 4.1–14.1 3.5 SynVisVar
Rovetto et al. [622] 370–450 4–15 3.5 SynVisVar
1-n-Butyl-3-methylimidazolium Kumelan et al. [460] 313–373 1–9.1 29.5 SynVis
hexafluorophosphate [bmim] [PF6 ]
1-n-Butyl-3-methylimidazolium Kumelan et al. [465] 293–413 1.1–8.9 29.2 SynTVis
methyl sulfate ([bmim] [CH3 SO4 ])
1-n-Hexyl-3-methylimidazolium Kumelan et al. [462] 293–413 1.4–9.8 29.5 SynVis
bis(trifluoromethylsulfonyl)imide
[C6-mim] [Tf2N]
Benzene Tsuji et al. [722] 303–303 0.9–4.6 37 SynVis
Zhou et al. [813] 298–323 1.6–4.6 600 SynT
Carbon dioxide Ke et al. [139] 292–304 8.4–13.4 320 SynNonPcTc
Zevnik and Levec [788] 298–298 0.9–6 300 AnTX
Cis-Decahydronaphthalene Tsuji et al. [723] 303–303 1.7–4.4 37 SynVis
Cyclohexane Tsuji et al. [722] 303–303 0.8–4.7 37 SynVis
Methanol Descamps et al. [255] 248–308 0–3.4 30 AnTCapValVis
Descamps et al. [255] 278–278 0–0.3 30 SynTVis
Methylcyclohexane Tsuji et al. [722] 303–303 1.2–4.3 37 SynVis
Methylpalmitate Rovetto et al. [622] 360–450 3–15 3.5 SynVisVar
Propane Zevnik and Levec [788] 333–333 1.4–7.1 300 AnTX
Propylene carbonate Shaharun et al. [146] 298–343 0.1–1.5 300 SynT
Pyrolysis gasoline (pygas) Zhou et al. [813] 298–343 0.5–5.5 600 SynT
Toluene Tsuji et al. [722] 303–303 1.2–4.4 37 SynVis
Yin [62] 305–343 1.4–7.1 177 AnPTSemX
Zhou et al. [813] 298–343 1.6–7 600 SynT
Trans-decahydronaphthalene Tsuji et al. [723] 303–303 1.7–4.2 37 SynVis
Table 9
Binary systems: nitrogen + X.

1-Hexene Jabloniec et al. [380] 302–363 0–3.2 n.a. SynT
2,2,4-Trimethylpentane (isooctane) Zhang et al. [790] 269–282 2.7–9.4 474 AnT
2-Butanol Weng et al. [764] 333–393 20–100 300 AnPTSemXY
2-Heptanol Weng et al. [763] 333–393 2–10 300 AnPTSemXY
2-Hexanol Weng et al. [763] 333–393 2–10 300 AnPTSemXY
2-Octanol Weng et al. [763] 333–393 2–10 300 AnPTSemXY
2-Pentanol Weng et al. [764] 333–393 20–100 300 AnPTSemXY
2-Propanol (isopropanol) Weng et al. [764] 333–393 20–100 300 AnPTSemXY
Acetate Jabloniec et al. [380] 303–363 0–2.8 n.a. SynT
Acetone Jabloniec et al. [380] 303–363 0–2.9 n.a. SynT
Acetonitrile Jabloniec et al. [380] 303–363 0–3.1 n.a. SynT
Aniline Jabloniec et al. [380] 303–363 0–3.5 n.a. SynT
Benzene Jabloniec et al. [380] 303–363 0–3.6 n.a. SynT
Diethylamine Jabloniec et al. [380] 303–363 0–2.9 n.a. SynT
Diethylene glycol monobutyl ether Weng et al. [61] 323–393 3–10 600 AnPTSemY
Dimethyl sulfoxide Weng [60] 323–393 3–10 600 AnPTSemXY
Dipropylamine Jabloniec et al. [380] 303–363 0–2.8 n.a. SynT
Ethane Janisch et al. [382] 149–269 1.5–8 n.a. AnTLcirBlo
Ethene–octene-copolymer Li et al. [78] 433–473 3.5–28 n.a. AnGrav
Ethyl formate Jabloniec et al. [380] 303–363 0–2.9 n.a. SynT
Methane Janisch et al. [382] 130–179 0.5–5 n.a. AnTLcirBlo
Methyl formate Jabloniec et al. [380] 303–303 0–2.9 n.a. SynT
n-Butyl acetate Jabloniec et al. [380] 303–363 0–2.9 n.a. SynT
n-Butylamine Jabloniec et al. [380] 303–363 0–3 n.a. SynT
n-Heptane Garcia-Sánchez et al. [308] 313–523 1.9–50.1 100 AnTCapValVis
n-Hexane Eliosa-Jiménez et al. [276] 344–488 0.9–51.4 100 AnTCapValVis
Jabloniec et al. [380] 303–393 0–3.4 n.a. SynT
n-Methyl-2-pyrrolidone Weng [60] 323–393 3–10 600 AnPTSemY
n-Nonane Silva-Oliver [682] 344–543 1.9–49.7 100 AnTValVis
n-Pentane Silva-Oliver [681] 344–447 1.6–35.4 100 AnTCapValVis
Poly(propylene) Li et al. [78] 453–493 3.5–28 n.a. AnGrav
Poly(propylene) branched Li et al. [493] 453–493 3–28 n.a. AnGrav
Poly(propylene) linear Li et al. [493] 453–493 3–28 n.a. AnGrav
Polyethylene terephthalate Faridi and Todd [50] 323–353 5–14 45 AnTMla
Polylactide Li et al. [35] 453–473 3.4–27.8 n.a. AnGrav
Propionic aldehyde Jabloniec et al. [380] 303–363 0–2.8 n.a. SynT
Pyridine Jabloniec et al. [380] 303–363 0–3.3 n.a. SynT
Toluene Jabloniec et al. [380] 303–363 0–2.9 n.a. SynT
Triethylamin Jabloniec et al. [380] 303–363 0–2.7 n.a. SynT
Trioxane Tanaka and Ogino [710] 323–373 7.6–11.9 50 AnTY
Water Koglbauer and Wendland [434] 293–373 0.1–25 49 AnSpec
Mohammadi [550] 282–363 0.4–4.9 28 AnTCapValVis
Table 10
Binary systems: oxygen + X.

1-n-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([bmim] [Tf2N]) Anthony et al. [74] 283–323 0–1.3 n.a. AnGrav
1-N-Butyl-3-methylimidazolium hexafluorophosphate [bmim] [PF6 ] Kumelan et al. [458] 293–373 1.2–9.1 30 SynVis
Kumelan et al. [464] 293–373 1.2–9.1 30 SynVis
Butyl-methyl pyrrolidinium bis(trifluoromethylsulfonyl) imide ([MeBuPyrr] [Tf2N]) Anthony et al. [74] 283–323 0–1.3 n.a. AnGrav
Dimethyl carbonate Hongling et al. [355] 293–373 2–12 100 AnTVarVis
Methyl-tri-butylammonium bis(trifluoromethylsulfonyl)imide ([mebu3n] [Tf2N]) Anthony et al. [74] 298–298 0–1.3 n.a. AnGrav
Nitrogen Baidakov et al. [180] 80–132 0–3 n.a. SynVis
Toluene Li et al. [490] 283–393 0.2–0.9 218.5 SynT
Tri-isobutyl-methyl phosphonium p-toluenesulfonate ([ibu3mep] [TOS]) Anthony et al. [74] 323–323 0–1.3 n.a. AnGrav
Table 11
Binary systems: carbon monoxide + X.
1-n-Butyl-3-methylimidazolium Kumelan et al. [459] 293–373 0.7–9.1 29.5 SynVis

hexafluorophosphate [bmim] PF6 ]
1-n-Butyl-3-methylimidazolium methyl Kumelan et al. [465] 293–413 1.2–9.3 29.2 SynTVis
sulfate ([bmim] CH3 SO4 ])
Acetone Lopez-Castillo et al. [526] 313–313 1.7–8.4 n.a. AnTVarVis
Acetonitrile (ethanenitrile) Lopez-Castillo et al. [526] 298–313 1.3–6.8 n.a. AnTVarVis
Dimethyl carbonate Hongling et al. [355] 293–373 2–12 100 AnTVarVis
Propane Kim and Kim [423] 253–323 0.2–7.2 150 AnTVcirVis
Propylene carbonate Shaharun et al. [146] 298–343 0.1–1.5 300 SynT
Table 12
Binary systems: nitrous oxide + X.
1,1,1,2,2-Pentafluoroethane (HFC-125) Di Nicola et al. [259] 217–293 0.1–1.3 273.5 SynT

1-n-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([bmim] [Tf2N]) Anthony et al. [74] 283–323 0–1.3 n.a. AnGrav
Carbon dioxide Di Nicola et al. [258] 214–281 0.4–4.1 273.5 SynT
Difluoromethane (HFC-32) Di Nicola et al. [257] 227–303 0.2–2.7 273.5 SynT
Ethane Corvaro et al. [234] 215–282 0.4–3.8 273.5 SynT
Fluoromethane (HFC-41) Di Nicola et al. [257] 213–282 0.2–3.8 273.5 SynT
Trifluoromethane (HFC-23) Di Nicola et al. [257] 214–263 0.3–2.3 273.5 SynT
Faridi and Todd [50] used a very “basic” form of material loss be easily extended. If carried out carefully they can produce very
analysis to measure the solubility of blowing agents in polyethylene reliable results.
terephthalate: they perform a fast depressurization and sampling, 19.7% of all systems investigated of this review have been mea-
weigh the polymer sample just once and assume that this is the sured with an analytical isothermal method.
equilibrium value. No corrections for weight loss during depres-
surization and sampling were taken into account. 3.1.2. Analytical isobaric–isothermal methods (AnPT)
As compared to analytical isobaric–isothermal methods isother- In isobaric–isothermal methods, often called dynamic methods,
mal methods have the advantage that time for equilibration can one or more fluid streams are pumped continuously into a ther-
Table 13
Binary systems: methane + X.
1,1,3,3-Tetramethylguanidium lactate Yuan et al. [782] 308–328 1–10.3 n.a. SynT

1-Ethyl-3-methylimidazolium ethyl sulfate Petermann et al. [79] 298–298 0.1–6 n.a. AnGrav
[emim] EtSO4 ]
1-n-Butyl-3-methylimidazolium methyl Kumelan et al. [467] 293–413 1.3–8.8 30 SynVis
sulfate [bmim] CH3 SO4 ]
1-n-Hexyl-3-methylimidazolium Kumelan et al. [466] 293–413 0.8–9.3 30 SynVis
bis(trifluoromethylsulfonyl)amide [hmim]
Tf2N]
2-Methylpropane (isobutane) Li et al. [496] 190–409 3.6–11.6 18 SynVisPcTc
Aniline Ventura et al. [739] 302–370 6.7–74.4 30 SynVisVar
Carbon dioxide Le [481] 168–187 0.9–3 n.a. SynVis
Dimethylsulfide Guilbot et al. [331] 252–313 0–10.3 30 SynTVis
Guilbot et al. [331] 313–313 0.3–12 30 AnTCapValVis
Ethane Janisch et al. [382] 139–270 0.4–6.6 n.a. AnTLcirBlo
Ethylene glycol Abdi et al. [163] 298–298 5.9–20.3 n.a. AnT
Ethylene glycol (MEG) Folas et al. [299] 278–323 5–20 450 AnTVar
Ethylmercaptan Guilbot et al. [331] 272–313 0–10.7 30 SynTVis
Ethylmethylsulfide Guilbot et al. [331] 247–313 0–11.6 30 SynTVis
Methyldiethanolamine Schmidt et al. [640] 298–423 0–20 n.a. AnTVcir
Methylmercaptan Guilbot et al. [331] 243–298 0–8.1 30 SynTVis
n-Butane Gozalpour et al. [321] 310–310 10.8–12.8 400 AnTVcirValVis
n-Decane Gozalpour et al. [321] 310–310 10.3–34.4 400 AnTVcirValVis
n-Heptadecane Pauly [597] 283–374 0.1–99.3 30 SynVisVar
n-Hexane Luo et al. [45] 298–298 2–8.1 360 AnTLcirBloVar
Nitrogen Janisch et al. [382] 130–179 0.5–5 n.a. AnTLcirBlo
N-Methyldiethanolamine (MDEA) Jou and Mather [397] 298–403 0.1–20.3 n.a. AnTVcir
Perfluoromethylcyclohexane Gozalpour et al. [320] 373–373 4.9–16.7 400 AnTVcirValVis
Poly(vinylidene fluoride) von Solms [80] 353–393 5–15.8 n.a. AnGrav
Polyamide (PA-11) von Solms [747] 323–363 5.1–15.8 n.a. AnGrav
Propane Kandil et al. [117] 315–340 2.8–6.8 60 SynNon
Reis [613] 305–329 8.5–9.4 5 SynNonPcTc
Tetracosane Deiters and Randzio [252] 318–332 0–180 n.a. SynNon
Tetrafluoromethane (CFC-14) Zhu et al. [816] 159–178 0.2–3.1 300 AnTVcir
Triethylene glycol Jerinic et al. [388] 298–316 1.6–8.6 1000 AnT
Water Abdi et al. [163] 324–324 10–40 n.a. AnT
Chapoy et al. [216] 283–293 10–35 34 AnTCapVal
Chapoy et al. [216] 283–318 0.9–34.6 34 AnTCapVal
Chapoy et al. [217] 277–297 0.4–4.3 20 AnTCapValVis
Kang et al. [128] 271–284 2–10 350 SynNon
Lee [486] 276–281 3.6–6 474 SynNon
Qin et al. [605] 324–375 30.1–49.9 200 AnT
Turner et al. [726] 273–285 2.5–9 n.a. SynNon
Table 14
Binary systems: ethane + X.
1-Ethyl-3-methylimidazolium ethyl sulfate [emim] Petermann et al. [79] 298–298 0.1–6 n.a. AnGrav
EtSO4 ]
1-n-Butyl-3-methylimidazolium Anthony et al. [74] 283–323 0–1.3 n.a. AnGrav
bis(trifluoromethylsulfonyl)imide ([bmim] Tf2N])
1-n-Hexyl-3-methylimidazolium Florusse et al. [298] 298–360 0.3–13 3.5 SynVisVar
bis(trifluoromethylsulfonyl)imide [hmim] Tf2N]
1-Propanol Jiménez-Gallegos et al. [390] 313–348 0.8–9.4 40 AnTCapValVisPc
Carbon dioxide Gil et al. [115] 291–304 5–7.1 4 SynVisConPcTc
Diamantane Poot and de Loos [604] 290–512 0.8–197.9 n.a. SynVis
Diethylene glycol (DEG) Jou et al. [395] 298–398 0–20.4 n.a. AnTVcir
Ethylene glycol Jou et al. [398] 298–398 0–20.3 n.a. AnTVcir
Hexafluoroethane (PFC-116) Zhang et al. [804] 199–242 0.1–1.2 300 AnTVcirCap
Zhang et al. [805] 189–252 0–1.6 300 AnTVcir
Methane Janisch et al. [382] 139–270 0.4–6.6 n.a. AnTLcirBlo
Methanol Ruffine et al. [27] 193–309 0.1–5.1 100 AnTVcirBloValVis
n-Decane Schwarz et al. [17] 310–360 4.6–9.3 40 SynVisVar
n-Eicosane Schwarz et al. [17] 310–360 5.7–12.7 40 SynVisVar
n-Hexadecane Schwarz et al. [17] 310–360 5.2–9.5 40 SynVisVar
n-Hexatriacontane Schwarz et al. [17] 350–366 13.4–22.4 40 SynVisVar
Nitrogen Janisch et al. [382] 149–269 1.5–8 n.a. AnTLcirBlo
Nitrous oxide Corvaro et al. [234] 215–282 0.4–3.8 273.5 SynT
n-Octacosane Schwarz et al. [17] 330–360 9.1–13 40 SynVisVar
n-Tetracontane Gregorowicz [324] 360–423 0.1–160 n.a. SynVisVar
Poly(ethylene) 23,625 Gregorowicz [324] 360–423 0.1–160 n.a. SynVisVar
Poly(ethylene) 7000 Gregorowicz [324] 360–423 0.1–160 n.a. SynVisVar
Poly(ethylene-co-20,2 mol%-1-butene) (PEB10) Kostko et al. [445] 368–424 111.6–128.4 15 SynVisVar
Tetrafluoromethane (CFC-14) Zhu et al. [815] 179–210 0–2.1 300 AnTVcir
Trifluoromethane (HFC-23) Zhang et al. [806] 188–243 0–1.6 300 AnTVcir
Water Kim et al. [426] 277–280 10.1–15.1 n.a. SynVisVar
mostated equilibrium cell. The pressure is kept constant during the 3.1.2.2. Semi-flow methods (AnPTSem). In semi-flow methods, only
experiment by controlling an effluent stream, usually of the vapor one phase is flowing while the other phase stays in an equilib-
phase. rium cell. Semi-flow methods are sometimes called “single-pass
flow methods”, “gas-saturation methods” or “pure-gas circulation
methods”. A fluid stream from a high-pressure reservoir is passed
3.1.2.1. Continuous-flow methods (AnPTCon). In a typical design of a
through two cells in series containing the solute, either a liquid or
continuous-flow method, high-pressure metering pumps feed the
a solid. The first cell serves as a presaturator and the second cell
preheated components into a mixer, where the desired tempera-
as equilibrium cell. Often, a syringe pump is used since it operates
ture and phase equilibrium is attained. Often, static mixers are used
at constant pressure and enables a pulse-free constant fluid flow
[51]. The feed stream from the mixer is separated in an equilibrium
[54]. Usually, the effluent is a supercritical fluid and the method is
cell into a vapor and a liquid phase. Effluents from both phases are
used to determine the solubility of a liquid or solid in the super-
withdrawn continually, depressurized, accumulated and analyzed,
critical fluid. Roth and coworkers [55] used a semi-flow method to
usually after the experiment. The pressure in the equilibrium cell
determine the solubility of solids in hot pressurized water. Upon
is adjusted by controlling the effluent stream of the top phase. The
equilibration, the effluent is reduced in pressure and directed to a
interface level between the fluid phases in the equilibrium cell can
trap where the condensed solute is collected. The quantity of the
be adjusted with the bottom-phase expansion valve, whereby the
gas coming out of the trap can be determined volumetrically, e.g.
interface level is usually determined visually, e.g. Shimoyama et al.
with a wet test meter.
[52].
Most often, only the composition of the effluent phase (vapor
Continuous-flow methods have the advantage that sampling
or liquid) is analyzed (AnPTSemY), for example to determine the
does not disturb the equilibrium. If larger samples are needed for
solubility of a low-boiling (liquid or solid) substance in a supercrit-
analyses, the run time of the experiment can be extended to accu-
ical fluid [56]. The composition of the vapor-phase effluent can be
mulate more material. Measurements at higher temperatures are
determined in many different ways, e.g. by using a spectroscopic
possible without thermal decomposition or polymerization reac-
method [54], by using a multi-port sampling valve and subsequent
tions due to the short residence time of the components in the
HPLC analysis [57] or after expansion to atmospheric pressure using
apparatus. Therefore, continous-flow methods should be preferred
a cold trap [58], an absorption bath [59], or a short column filled
when working with temperature-sensitive compounds. Using a
with an appropriate adsorbent that captures the solute from the
continuous-flow method, Fang et al. [53] measured phase equilibria
effluent stream [60].
for methanol + methyl-esterified deodorizer destillate of soybean
Kautz et al. [54] used a modified supercritical fluid chromato-
oil at temperatures up to 598 K.
graph to measure the solubility of dyes in CO2 . The column was
Continuous-flow methods can be used only for systems where
filled with finely pulverized dyestuff. Analysis of the vapor-phase
the time needed to attain phase equilibrium is sufficiently
stream is done by VIS-spectroscopy (AnPTSemYSpec).
short.
Table 15
Binary systems: propane + X.
1,1,1,2,3,3,3-Heptafluoropropane (HFC-227ea) Lim et al. [507] 273–323 0.1–1.8 85 AnTVLcirValVis

1,1,1,2-Tetrafluoroethane (HFC-134a) Lim et al. [503] 273–323 0.2–2.1 85 AnTVLcirValVis
1,1,1-Trifluoroethane (HFC-143a) Im et al. [368] 313–363 1.3–4.4 320 AnTVLcirValVis
Lim et al. [503] 268–318 0.4–2.3 85 AnTVLcirValVis
1,1-Difluoroethane (HFC-152a) Park et al. [595] 273–313 0.2–1.5 128 AnTVcir
1-Decanol Schwarz and Knoetze [644] 378–408 3.7–6.7 40 SynVisVar
1-Docosanol (behenyl alcohol) Schwarz and Knoetze [644] 378–408 4.1–8.3 40 SynVisVar
1-Dodecanol (lauryl alcohol) Schwarz and Knoetze [644] 378–408 3.5–6.8 40 SynVisVar
1-Hexadecanol Rovetto et al. [621] 312–450 1.3–10.1 3.5 SynVisVar
1-Hexadecanol (cetyl alcohol, palmityl alcohol) Schwarz and Knoetze [644] 378–408 4–7.5 40 SynVisVar
1-n-Butyl-3-methylimidazolium Lee and Outcalt [483] 279–339 0–1 35.9 SynTVis
bis(trifluoromethylsulfonyl)imide [bmim] Tf2N]
1-n-Hexyl-3-methylimidazolium Kim et al. [425] 298–298 0.3–0.7 n.a. AnTVcirVal
tri(bisfluoromethylsulfonyl)imide [C6mim]
Tf2N]
1-Octadecanol (stearyl alcohol) Schwarz and Knoetze [644] 378–408 3.9–7.6 40 SynVisVar
1-Propanol Jiménez-Gallegos et al. [390] 318–348 0.5–2.6 40 AnTCapValVisPc
2-Methylpropane (isobutane) Kayukawa et al. [415] 240–380 0–3.3 n.a. SynNonVar
Kayukawa et al. [416] 260–320 0.1–1.3 n.a. AnTVLcirVal
2-Propanol (isopropanol) Zevnik and Levec [788] 333–393 5.2–7.4 300 AnTX
Alkane C102 wax Schwarz et al. [643] 408–408 5–20 40 SynVisVar
AOT surfactant Benazzi [186] 298–343 0.9–2.7 27 SynVisVar
Camphor Carvalho et al. [210] 304–384 1–4.8 25 SynVisVar
Carbon monoxide Kim and Kim [423] 253–323 0.2–7.2 150 AnTVcirVis
Castor oil Lanza et al. [477] 303–343 1.8–21.8 n.a. SynVisVar
Diamantane Poot and de Loos [604] 398–512 3.7–13.2 n.a. SynVis
Dimethyl ether Yasumoto et al. [776] 369–399 4.2–5.2 16 SynVisVarPcTc
Ethyl tetradecanoate (ethyl myristate) Schwarz et al. [645] 378–408 3.4–6.8 40 SynVisVar
Ethylvanillin Knez et al. [102] 345–347 0.9–29.2 74 SynVis
Glycidyl methacrylate Franceschi et al. [301] 313–343 1.3–2.3 25 SynVisVar
Hardened rapeseed oil Rp70 Münüklü et al. [565] 328–363 0.9–7.1 3.5 SynVisVar
Hydrogen Zevnik and Levec [788] 333–333 1.4–7.1 300 AnTX
Hydrogen chloride Llovell et al. [524] 273–369 0.4–8.2 n.a. SynVisVar
Methane Kandil et al. [117] 315–340 2.8–6.8 60 SynNon
Reis et al. [613] 305–329 8.5–9.4 5 SynNonPcTc
Methyl tetradecanoate (methyl myristate) Schwarz et al. [645] 378–408 3.4–6.8 40 SynVisVar
n-Butane Kayukawa et al. [415] 240–380 0–3.1 n.a. SynNonVar
Seong et al. [655] 273–323 0.1–1.7 85 AnTVLcirValVis
Gregorowicz [324] 360–423 0.1–160 n.a. SynVisVar
n-Tetradecane Schwarz et al. [645] 378–408 2.9–6.4 40 SynVisVar
o-Ethylvanillin Knez et al. [102] 330–337 0.2–28 74 SynVis
o-Vanillin Knez et al. [102] 311–315 0.9–29.3 74 SynVis
Parafint C80 wax Schwarz et al. [642] 378–408 3.9–9.6 40 SynVisVar
Poly(2-ethylhexyl acrylate) Liu et al. [519] 354–452 13.6–27.4 28 SynVisVar
Poly(2-ethylhexyl methacrylate) Liu et al. [519] 335–454 14.3–30.1 28 SynVisVar
Poly(decyl acrylate) Byun and Lee [201] 332–453 16.9–28.5 28 SynVisVar
Poly(isopropyl acrylate) Byun and McHugh [206] 437–475 92.9–277.1 28 SynVisVar
Propene Ho et al. [41] 273–313 0.4–1.6 85 AnTVLcirVis
Squalane Hong et al. [352] 324–400 0–1.2 329.2 SynTVcir
Sulfolane Schmidt [639] 298–403 0.1–17.6 150 AnTVcirX
Tetracontane Gregorowicz [104] 322–338 2.4–106.1 n.a. SynVisVar
Tetradecanoic acid (myristic acid) Schwarz et al. [645] 378–408 3.8–8.4 40 SynVisVar
Unilin 550 Schwarz et al. [641] 378–408 3.4–13..8 40 SynVisVar
Unithox 550 Schwarz et al. [641] 378–408 4.4–26.8 40 SynVisVar
Vanillin Knez et al. [102] 352–353 0.8–27 74 SynVis
Water Gaudette and Servio [312] 274–276 0.1–0.3 n.a. AnT
Melnikov et al. [113] 257–275 0.1–0.3 100 SynVis
When a semi-flow method is used for the measurement of analyzed, e.g. Weng et al. [61]. Semi-flow methods can also be
vapor–liquid equilibria AnPTSemXY, the composition of the liq- used to measure the solubility of a gas in a liquid, e.g. Yin and
uid phase needs to be determined. Therefore, a sample from the Tan [62]. The experimental procedure (AnPTSemX) is similar to
liquid phase is withdrawn through tubing, depressurized, and the one for measuring vapor–liquid equilibria, but there is no
Table 16
Binary systems: n-butane + X.
1,1,1,2,2-Pentafluoroethane (HFC-125) Fedele et al. [294] 278–298 0.1–1.3 50 AnTVcirVis

Im et al. [367] 313–333 0.3–3.1 320 AnTVLcirValVis
1,1,1,2,3,3,3-Heptafluoropropane (HFC-227ea) Seong et al. [653] 273–323 0.1–0.9 85 AnTVLcirValVis
1,1,1,2-Tetrafluoroethane (HFC-134a) Im et al. [367] 313–333 0.3–1.7 320 AnTVLcirValVis
Lim et al. [505] 273–323 0.1–1.3 85 AnTVLcirValVis
1,1,1-Trifluoroethane (HFC-143a) Im et al. [373] 313–363 0.3–3.7 320 AnTVLcirValVis
1,1-Difluoroethane (HFC-152a) Im et al. [371] 313–363 0.3–2.9 320 AnTVLcirValVis
Lim et al. [504] 273–323 0.1–1.2 85 AnTVLcirVis
1-Butanol Dell’Era et al. [254] 364–364 0–1.2 n.a. SynT
1-n-Butyl-3-methylimidazolium Lee and Outcalt [483] 280–340 0–0.3 35.9 SynTVis
2-Butanol Dell’Era et al. [254] 364–364 0–1.2 n.a. SynT
2-Methyl-2-propanol Dell’Era et al. [254] 364–364 0.1–1.2 n.a. SynT
2-Methylpropane (isobutane) Kayukawa et al. [415] 240–380 0–2.1 n.a. SynNonVar
2-Propanol (isopropanol) Dell’Era et al. [254] 364–364 0.1–1.2 n.a. SynT
2-Propanone Pasanen et al. [596] 364–364 0.2–1.2 113.1 SynT
Castor oil Lanza et al. [477] 303–423 0.4–23.8 n.a. SynVisVar
Difluoromethane (HFC-32) Fedele et al. [295] 263–293 0–1.4 50 AnTVcirVis
Dimethyl ether Yasumoto et al. [776] 399–5 3.7–5.2 16 SynVisVarPcTc
Methane Gozalpour et al. [321] 310–310 10.8–12.8 400 AnTVcirValVis
Methanol Dell’Era et al. [254] 364–364 0.2–1.4 n.a. SynT
Poly(ethylene) (LDPE) Wang et al. [757] 383–473 0.3–3.4 42 SynT
Propane Kayukawa et al. [415] 240–380 0–3.1 n.a. SynNonVar
Water Mokraoui et al. [558] 293–353 0.2–1 34 AnTCapVal
need to determine the composition of the effluent from the vapor a supercritical fluid. Glass wool before and after the packed
phase. bed guarantees a uniform flow distribution and prevents parti-
The major uncertainty of all flow methods is the possible cle entrainment. A line by-passing the extractor allows solubility
lack of attainment of equilibrium. Another difficulty is the par- measurements at high concentrations. It dilutes the saturated fluid
tial condensation of the solute from the saturated vapor stream stream with clean CO2 and reduces the risk of valve clogging and
in the tubing, particularly in and after the expansion valve. flow rate instability.
This undesired variable hold-up of the solute leads to scattering Folas et al. [65] used a semiflow method to determine the sol-
results. After having blocked off the equilibrium cell at the end ubility of water in nitrogen, methane and a synthetic natural gas.
of an experiment, a stream of CO2 can be used to collect pre- Instead of a presaturator they used a “supersaturator” consisting
cipitated solute from the tubing and from the expansion valve. of two cylinders in series that dissolves water in the gas stream
To avoid unwanted precipitation after the restrictor, Özcan and at a higher temperature than the desired equilibrium tempera-
Özcan [63] added a flow of 0.1 ml methanol/min between the ture. Then the saturated gas stream flows through a condenser
restrictor and the back pressure regulator to the CO2 stream of that is thermostated at the desired equilibrium temperature. A
1 ml/min. part of the dissolved water is precipitated in the condenser which
Banchero et al. [64] used an experimental technique that consists of three cylinders in series. A high pressure dew point mir-
allowed the measurement of high concentrations of dyestuff in ror is used to determine when stable conditions are reached in
Table 17
Binary systems: n-hexane + X.
Carbon dioxide Lay et al. [478] 293–308 1.7–7.3 130 AnTVisVar

Wang et al. [753] 323–333 7.2–9.2 n.a. SynVisVar
Ethene Nagy et al. [567] 390–495 1.5–9 n.a. SynVisPcTc
Methane Luo et al. [45] 298–298 2–8.1 360 AnTLcirBloVar
n-Hexadecane Morawski et al. [561] 293–343 9.2–1045 n.a. SynNonVar
Nitrogen Eliosa-Jiménez et al. [276] 344–488 0.9–51.4 100 AnTCapValVis
Jabloniec et al. [380] 303–393 0–3.4 n.a. SynT
n-Octadecane Morawski et al. [561] 293–343 8.8–677.4 n.a. SynNonVar
n-Tridecane Morawski et al. [561] 293–343 133–1163.7 n.a. SynNonVar
Perfluoro-n-octane Pratas de Melo et al. [110] 310–394 0.1–143 1 SynVis
Pratas de Melo et al. [110] 310–394 0.1–143 1.6 SynVis
Poly(ethylene) (LLDPE) Nagy et al. [568] 410–495 0.6–9.6 3.5 SynVisVar
Poly(ethylene) 108,000 Haruki et al. [100] 373–473 0.1–8.5 20 SynVisVar
Water Mokraoui et al. [558] 298–353 0.4–0.5 34 AnTCapVal
Table 18
Binary systems: ethene + X.
Eicosane Gregorowicz [104] 290–348 5.5–50.2 n.a. SynVisVar

n-Tetracontane Gregorowicz [324] 360–423 0.1–160 n.a. SynVisVar
Methanol Haneda et al. [337] 278–283 2–5.9 320 AnTVLcir
Poly(ethene-co-methacrylic acid) Kleiner et al. [429] 520–535 220–275 16 SynVisVar
Ethanol Kodama et al. [431] 283–283 1.2–5.2 320 AnTVLcir
2-Propanol (isopropanol) Kodama et al. [432] 283–283 2.2–5 320 AnTVLcir
Toluene Lee et al. [484] 323–423 0.4–2.8 n.a. SynT
n-Hexane Nagy et al. [567] 390–495 1.5–9 n.a. SynVisPcTc
Trioxane Tanaka and Ogino [710] 323–373 9.9–9.9 50.0 AnTY
Poly(ethylene-co-methyl acrylate-co-vinyl Tumakaka et al. [725] 373–503 132–212 65 SynVisVar
acetate)
Poly(ethylene-co-butyl Tumakaka et al. [725] 373–528 103–265 65 SynVisVar
methacrylate-co-methacrylic acid)
Table 19
Binary systems: propene + X.

bis(trifluoromethylsulfonyl)imide [bmim] Tf2N]
2-Propanol (isopropanol) Stringari et al. [691] 300–350 0.5–2.6 n.a. SynNon
Difluoromethane (HFC-32) Ho et al. [349] 273–313 0.5–2.8 85 AnTVLcirVis
Dimethyl ether Giles and Wilson [317] 253–293 0.1–1 n.a. SynT
Poly(2-ethylhexyl acrylate) Liu et al. [519] 373–453 17–28.7 28 SynVisVar
Propane Ho et al. [41] 273–313 0.4–1.6 85 AnTVLcirVis
the experimental equipment. During measurements the gas flow In SFC, the thermodynamic analysis of solute retention is more
bypasses the mirror. Both saturation and condensation are done difficult than in GC because the uptake of the mobile phase fluid
at the same pressure. A Karl Fischer (KF) coulometric titrator from by the stationary phase is no longer negligible. Chromatographic
Metrohm is used to measure the water content in the gas from the methods have as advantage the possibility to determine equi-
condenser. librium properties and diffusion coefficients in one experiment
[67].
3.1.2.3. Chromatographic methods (AnPTChro). Chromatographic Suleiman et al. [68] combined a supercritical fluid chro-
methods measure solute retention in a chromatographic column matographic technique (AnPTChro) in combination with the
and connect it with the Gibbs energy of solute transfer between semi-flow method (AnPTSemY) to determine the solubility of
the stationary and the mobile phase. Roth [66] gives a review anti-inflammatory, anti-cancer, and anti-HIV drugs in supercrit-
on applications of supercritical fluid chromatography (SFC) for ical CO2 . The chromatographic method provided the retention
the determination of the relative values of solute solubilities in times of the solutes of interest and those of an un-retained
supercritical fluids, and on the determination of solute partition substance, which were used to obtain equilibrium partition coeffi-
coefficients between a supercritical fluid and the stationary phase. cients. The partition coefficients were subsequently used to obtain
Table 20
Binary systems: 1-butene + X.

1-Propanol Visuri et al. [743] 364–364 0–1.5 113 SynT
2-Butanol Visuri et al. [743] 364–364 0–1.5 113 SynT
2-Methyl-2-propanol Visuri et al. [743] 364–364 0.1–1.5 113 SynT
2-Methylpropane Li et al. [496] 409–421 3.6–4 18 SynVisPcTc
2-Propanol (isopropanol) Visuri et al. [743] 364–364 0.1–1.5 113 SynT
2-Propanone Pasanen et al. [596] 364–364 0.2–1.5 113.1 SynT
Methanol Visuri et al. [743] 364–364 0.2–1.6 112.7 SynT
Poly(2-ethylhexyl methacrylate) Liu et al. [519] 374–455 2.9–15 28 SynVisVar
Poly(␧-caprolactone) Byun et al. [202] 425–484 161–283.6 28 SynVisVar
Poly(isopropyl acrylate) Byun and McHugh [206] 350–474 34–2347 28 SynVisVar
Table 21
Binary systems: methanol + X.
1-Butene Visuri et al. [743] 364–364 0.2–1.6 112.7 SynT

2-Methylpropene Hynynen et al. [364] 364–364 0.2–1.6 n.a. SynT
Ammonia Schäfer et al. [636] 313–395 0.1–4.2 30 SynVis
Schäfer et al. [636] 353–393 0.1–1.6 1600 AnT
␣-Tocopherol Fang et al. [290] 523–573 3.3–15 31 AnPTConVis
C18 methyl esters Fang et al. [290] 523–573 2.4–11.4 31 AnPTConVis
Carbon dioxide Ke et al. [139] 304–328 7.3–10.4 320 SynNonPcTc
Schwinghammer et al. [646] 303–303 0.8–5.4 140 AnTVcirVis
Xie et al. [770] 313–313 0.9–7.9 20 SynVisVar
Cis-2-Butene Wierink et al. [765] 364–364 0.2–1.3 112.7 SynT
Dimethyl carbonate Yunhai et al. [787] 337–428 0–1.5 138.11 SynTVis
Ethane Ruffine [27] 193–309 0.1–5.1 100 AnTVcirBloValVis
Ethene Haneda et al. [337] 278–283 2–5..9 320 AnTVLcir
Hydrogen Descamps et al. [255] 248–308 0–3.4 30 AnTCapValVis
Descamps et al. [255] 278–278 0–0.3 30 SynTVis
Isobutane (2-methylpropane) Laavi et al. [475] 364–364 0.2–1.8 113 SynT
Methyl laurate Shimoyama [669] 493–543 2.1–8.4 31 AnPTConVis
Methyl myristate Shimoyama [669] 493–543 2.4–8.4 31 AnPTConVis
Methyl-esterified deodorizer destillate of soybean Fang et al. [53] 523–598 8.2–24.5 31 AnPTConVis
oil (squalene, tocopherols, sterols, FAME)
N-Butane Dell’Era et al. [254] 364–364 0.2–1.4 n.a. SynT
Trans-2-butene Roininen et al. [620] 364–364 0.2–1.3 113 SynT
Triolein Tang et al. [711] 353–463 6–10 50 AnTVisVar
solubilities at various temperatures and pressures. A few experi- 3.1.4. Analytical spectroscopic methods (AnSpec)
mental solubility data obtained with the semi-flow method were Using spectroscopic methods, the composition of the phases is
used to provide a calibration parameter for the chromatographic analyzed at high pressures without having to take samples. Often,
method. infrared techniques are used. Koglbauer and Wendland [34] devel-
Machida et al. [69] used an inverse supercritical-fluid chromato- oped an apparatus where a high-pressure view cell was placed in
graphic method to measure infinite dilution partition coefficients the sample compartment of an Fourier transform infrared (FTIR)
of aromatic compounds between an ionic liquid and CO2 . spectrometer to measure the solubility of water in compressed
synthetic air. The IR light absorbance could be measured in situ
in the gas phase, which was inside the view cell in equilibrium
3.1.3. Analytical isobaric methods (AnP) with the relatively thin liquid phase. The IR light absorbance in
The boiling temperature of a mixture is measured at isobaric compressed air is related to that in saturated pure water vapor. An
conditions and phase compositions are determined after sampling additional calibration in a homogeneous compressed air sample
and analysis. Typically, isobaric experiments are performed in an with known humidity content is needed to correct for the effect of
ebulliometer (from latin ebullio “to boil, to bubble up”), which is the gas density on the FTIR spectra.
a one-stage total-reflux boiler equipped with a vapor-lift pump to Haines et al. [70] applied near infrared (NIR) spectroscopy to
spray slugs of equilibrated liquid and vapor onto a thermometer determine the solubility of surfactants in CO2 . Pasquali et al. [71]
well. As opposed to the more frequently used synthetic-isobaric used attenuated total reflection infrared (ATR-IR) spectroscopy to
method (SynP), vapor and liquid streams are separated, collected simultaneously measure the sorption of CO2 in polyethylene glycol
and can be sampled and analyzed. The compositions of the liq- (PEG) and the polymer swelling.
uid and the vapor phase change with time and reach a steady Rondinone et al. [72] developed a single-crystal sapphire cell
state which should not differ significantly from the true equi- that allows unobstructed spectroscopic access to the cell for per-
librium value. Usually, analytical isobaric methods are used to forming neutron-scattering experiments on gas hydrates. Since
measure low-pressure data. Then, it is often called the “dynamic” sapphire contains only aluminum and oxygen, it possesses a low
VLE method. incoherent neutron scattering and absorption cross-section and
Table 22
Binary systems: ethanol + X.
1,1,1,2,3,3,3-Heptafluoropropane (HFC-227ea) Gordon et al. [319] 283–343 0–1.4 75 SynNon

Carbon dioxide Chiu et al. [225] 291–313 2.4–8.1 n.a. SynVisVar
Elizalde-Solis and Galicia-Luna [277] 333–333 3–10.4 100 AnTCapValVisPc
Knez et al. [430] 313–353 1.3–13.9 500 AnTVLcirVis
Kodama and Kato [433] 291–291 2–5.4 320 AnTVLcir
Stievano and Elvassore [122] 291–323 3.3–8.1 60 SynNonLCirVisVar
Ethene Kodama et al. [431] 283–283 1.2–5.2 320 AnTVLcir
Ethyl laurate Shimoyama [52] 493–543 2.2–7 31 AnPTConVis
Ethyl myristate Shimoyama [52] 493–543 2.1–6.9 31 AnPTConVis
Poly(methyl methacrylate) Matsuyama [542] 338–357 0–15 150 SynVisVar
Water Bazaev et al. [183] 456–598 2.1–15.5 32.56 SynOthPcTc
Bazaev et al. [185] 456–598 2.1–15.5 32.56 SynOthPcTc
Table 23
Binary systems: dimethyl ether + X.
1,1,1,2,2-Pentafluoroethane (HFC-125) Im et al. [370] 313–363 0.8–3.9 320 AnTVLcirVis

1,1,1,2-Tetrafluoroethane (HFC-134a) Im et al. [369] 313–343 8.6–21 320 AnTVLcirValVis
Valtz et al. [731] 293–358 0.4–2.8 n.a. AnTCapValVis
1-Octene Park et al. [594] 323–323 0–1.1 n.a. SynT
2-Methylpropane (isobutane) Yasumoto et al. [776] 399–407 3.6–5.2 16 SynVisVarPcTc
Benzene Park et al. [594] 323–323 0–1.1 n.a. SynT
Difluoromethane (HFC-32) Coquelet et al. [230] 283–363 0.4–5.5 n.a. AnTCapValVis
Fedele et al. [293] 258–293 0.1–1.4 50 AnTVcirVis
Dimethyl carbonate Hongling et al. [355] 293–373 0–3.2 100 AnTVarVis
n-Butane Yasumoto et al. [776] 399–5 3.7–5.2 16 SynVisVarPcTc
n-Decane Park et al. [594] 323–323 0–1.1 n.a. SynT
n-Dodecane Park et al. [594] 323–323 0–1.1 n.a. SynT
Park et al. [590] 312–413 13.1–35.5 n.a. SynVisVar
Poly(l-lactide) Park et al. [590] 331–412 3.1–24.9 n.a. SynVisVar
Poly(p-decyloxymethyl styrene) Shin et al. [675] 372–452 5–19.1 28 SynVisVar
Poly(p-decylsulfonylmethyl styrene) Shin et al. [675] 325–452 11–31.5 28 SynVisVar
Poly(p-decylthiomethyl styrene) Shin et al. [675] 330–453 1.7–25.8 28 SynVisVar
Poly(p-perfluorooctyl-ethylene sulfonylmethyl styrene) Shin et al. [675] 414–473 11.3–18.7 28 SynVisVar
Poly(p-perfluorooctyl-ethyleneoxymethyl styrene) Shin et al. [675] 394–452 6.7–13.9 28 SynVisVar
Poly(p-perfluorooctyl-ethylenethiomethyl styrene) Shin et al. [675] 410–452 6.7–11.2 28 SynVisVar
Polystyrene Park et al. [591] 300–408 25.2–44 n.a. SynVisVar
Park [592] 300–408 25.2–44 n.a. SynVisVar
Propane Yasumoto et al. [776] 369–399 4.2–5.2 16 SynVisVarPcTc
Propene Giles and Wilson [317] 253–293 0.1–1 n.a. SynT
Toluene Park et al. [594] 323–323 0–1.1 n.a. SynT
Water Park et al. [594] 323–323 0–1.1 n.a. SynT
Table 24
Binary systems: chlorodifluoromethane (HCFC-22) + X.
Dimethylether of tetraethyleneglycol (DMETEG) Jelinek et al. [384] 298–393 0–1.9 n.a. SynNon
N,N-Dimethylformamide (DMF) He et al. [344] 283–363 0–1.9 80 SynTVcirVis
Tristearin Spilimbergo et al. [123] 309–324 0.1–0.7 n.a. SynNon
Table 25
Binary systems: trifluoromethane (HFC-23) + X.
1,1,1,2-Tetrafluoroethane (HFC-134a) Cui et al. [238] 258–293 0.2–3.4 80 AnTLcirVis

1-n-Butyl-3-methylimidazoium hexyfluorophosphate [bmim] [PF6 ] Shariati et al. [659] 303–363 0.5–41 n.a. SynVisVar
Shiflett and Yokozeki [662] 282–348 0–2 n.a. AnGrav
Carbon dioxide Nasrifar et al. [571] 263–302 1.9–7 3.5 SynVisVar
Ethane Zhang et al. [806] 188–243 0–1.6 300 AnTVcir
Ethylvanillin Knez et al. [102] 313–333 3.2–24.7 120 AnT
Knez et al. [102] 337–347 0.2–31 74 SynVis
o-Ethylvanillin Knez et al. [102] 313–333 4.3–20 120 AnT
Knez et al. [102] 315–336 0.2–24.7 74 SynVis
Knez et al. [102] 313–333 2.4–25.2 120 AnT
Poly(l-lactide) Park et al. [591] 333–415 93.1–116 n.a. SynVisVar
Park et al. [592] 333–415 93.1–116 n.a. SynVisVar
Vanillin Knez et al. [102] 313–333 3.1–20.2 120 AnT
Knez et al. [102] 347–354 0.1–30.6 74 SynVis
Water Mooijer-van den Heuvel et al. [560] 282–293 0.9–4.1 3.5 SynVisVar
Table 26
Binary systems: difluoromethane (HFC-32) + X.
1,1,1,2-Tetrafluoroethane (HFC-134a) Cui et al. [239] 258–343 0.1–4.8 80 AnTVcirVis

Kato and Nishiumi [40] 323–350 1.1–4.8 1200 AnTLcirVisVar
Kato and Nishiumi [40] 354–368 4.5–5.6 1200 SynVisVarPcTc
1,2-Dimethyl-3-propylimidazolium Shiflett et al. [663] 298–298 0–1 n.a. AnGrav
bis(trifluoromethylsulfonyl)-imide [dmpim] [BMeI]
1,2-Dimethyl-3-propylimidazolium Shiflett et al. [663] 283–348 0–1 n.a. AnGrav
tris(trifluoromethylsulfonyl)-methide [dmpim]
[TMeM]
1-Ethyl-3-methylimidazolium Shiflett et al. [663] 298–298 0–1 n.a. AnGrav
1,1,2,2-tetrafluoroethanesulfonate [emim] [TFES]
bis(pentafluoroethylsulfonyl)imide [emim] [BEI]
bis(trifluoromethylsulfonyl)imide [emim] [BMeI]
1-Heptyl-3-methylimidazolium Shiflett et al. [663] 298–298 0–0.9 n.a. AnGrav
1,1,2,2-tetrafluoroethanesulfonate [C7-mim] [TFES]
1-n-Butyl-3-methylimidazoium hexyfluorophosphate Shiflett and Yokozeki [662] 283–348 0–0.9 n.a. AnGrav
[bmim] [PF6 ]
1-n-Butyl-3-methylimidazoium tetrafluoroborate Shiflett and Yokozeki [662] 283–348 0–0.9 n.a. AnGrav
[bmim] [BF4 ]
1-n-Butyl-3-methylimidazolium Shiflett et al. [663] 298–298 0–0.9 n.a. AnGrav
1,1,2,2-tetrafluoroethanesulfonate [bmim] [TFES]
1-n-Butyl-3-methylimidazolium Shiflett et al. [663] 298–298 0–1 n.a. AnGrav
1,1,2,3,3,3-hexafluoropropanesulfonate [bmim] [HFPS]
1-n-Butyl-3-methylimidazolium 1,1,2-trifluoro- Shiflett et al. [663] 298–298 0–0.9 n.a. AnGrav
2-(perfluoroethoxy)ethanesulfonate [bmim] [TPES]
1-n-Butyl-3-methylimidazolium 1,1,2-trifluoro- Shiflett et al. [663] 298–298 0–0.9 n.a. AnGrav
2-(trifluoromethoxy)-ethanesulfonate [bmim] [TTES]
1-n-Butyl-3-methylimidazolium 2-(1,2,2,2- Shiflett et al. [663] 298–298 0–1 n.a. AnGrav
tetrafluoroethoxy)-1,1,2,2-tetrafluoroethanesulfonate
[bmim] [FS]
1-n-Butyl-3-methylimidazolium acetate [bmim] [Ac] Shiflett et al. [663] 298–298 0–1 n.a. AnGrav
1-n-Butyl-3-methylimidazolium methyl sulfate Shiflett et al. [663] 298–298 0–1 n.a. AnGrav
[bmim]-[MeSO4 ]
1-n-Butyl-3-methylimidazolium thiocyanate Shiflett et al. [663] 298–298 0–0.9 n.a. AnGrav
[bmim]-[SCN]
1-n-Butyl-3-methylpyridinium Shiflett et al. [663] 298–298 0–1 n.a. AnGrav
bis(trifluoromethylsulfonyl)imide [C4-py] [BMeI]
1-n-Dodecyl-3-methylimidazolium Shiflett et al. [663] 298–298 0–1 n.a. AnGrav
1,1,2,2-tetrafluoroethanesulfonate [C12-mim] [TFES]
1-Propyl-3-methylpyridinium Shiflett et al. [663] 283–348 0–1 n.a. AnGrav
bis(trifluoromethylsulfonyl)imide [pmpy] [BMeI]
2-Methylpropane (isobutane) Akasaka et al. [169] 260–321 0.1–2.6 n.a. AnTVLcirVal
Dimethyl ether Coquelet et al. [230] 283–363 0.4–5.5 n.a. AnTCapValVis
Fedele et al. [293] 258–293 0.1–1.4 50 AnTVcirVis
n-Butane Fedele et al. [295] 263–293 0–1.4 50 AnTVcirVis
Pentafluoroethane (HFC-125) Han et al. [335] 265–303 0.5–1.9 80 AnTVcirVis
Han et al. [336] 265–303 0.5–1.9 80 AnTVcirVis
Poly(l-lactide) Park et al. [591] 334–416 77–111.3 n.a. SynVisVar
Park et al. [592] 334–416 77–111.3 n.a. SynVisVar
Propene Ho et al. [349] 273–313 0.5–2.8 85 AnTVLcirVis
Water Imai et al. [374] 278–290 0.2–1 70 SynNon
Table 27
Binary systems: 1,1,1,2,2-pentafluoroethane (HFC-125) + X.
1,1,1,2-Tetrafluoroethane (HFC-134a) Kato and Nishiumi [40] 303–363 0.9–3.9 1200 AnTLcirVisVar
1-Ethyl-3-methylimidazolium Shiflett et al. [666] 283–348 0–0.9 n.a. AnGrav
bis(trifluoromethylsulfonyl)imide [emim] [Tf2N]
1-n-Butyl-3-methylimidazoium Shiflett and Yokozeki [662] 283–348 0–0.9 n.a. AnGrav
hexyfluorophosphate [bmim] [PF6 ]
1-n-Butyl-3-methylimidazolium Shiflett and Yokozeki [157] 271–313 0.6–2 1.2 SynOthVis
hexafluorophosphate ([bmim] [PF6 ])
2-Methylpropane (isobutane) Chen et al. [219] 243–333 0–3.1 31.7 SynT
Cyclopropane Fedele et al. [296] 253–293 0.1–1.2 50 AnTVcirVis
Dimethyl ether Im et al. [370] 313–363 0.8–3.9 320 AnTVLcirVis
Fluoroethane (HFC-161) Han et al. [334] 265–313 0.3–2 80 AnTLcirVis
n-Butane Fedele et al. [294] 278–298 0.1–1.3 50 AnTVcirVis
Table 28
Binary systems: 1,1,1,2-tetrafluoroethane (HFC-134a) + X.
1,1,1,2,2-Pentafluoroethane (HFC-125) Kato and Nishiumi [40] 303–363 0.9–3.9 1200 AnTLcirVisVar
1-n-Butyl-3-methylimidazolium Shiflett and Yokozeki [664] 318–355 0.7–2.7 1.2 SynOthVis
6-Methoxy-1-tetralone Abbott et al. [89] 378–378 7–19 25 AnOth
Carbon dioxide Lim et al. [508] 323–343 1.6–7.1 50 AnTVLcirValVis
Crotonic acid Abbott et al. [89] 378–378 5–15 25 AnOth
Cyclopropane Fedele et al. [296] 253–293 0.1–0.6 50 AnTVcirVis
Difluoromethane (HFC-32) Cui et al. [239] 258–343 0.1–4.8 80 AnTVcirVis
Kato and Nishiumi [40] 323–350 1.1–4.8 1200 AnTLcirVisVar
Dimethyl ether Im et al. [369] 313–343 8.6–21 320 AnTVLcirValVis
Valtz et al. [731] 293–358 0.4–2.8 n.a. AnTCapValVis
Ethylene-glycol dimethylether Chaudhari et al. [218] 283–353 0–2.6 48.26 SynT
Ethylvanillin Knez et al. [102] 313–333 6–29 120 AnT
Knez et al. [102] 337–343 0.9–31 74 SynVis
Fluoroethane (HFC-161) Dong et al. [268] 253–292 0.1–0.8 300 AnTVcir
Hexafluoroethane (PFC-116) Madani et al. [530] 263–353 0.1–4.1 n.a. AnTCapValVis
Itaconic acid Abbott et al. [89] 378–393 5–20.5 25 AnOth
Methylsuccinic acid Abbott et al. [89] 378–383 5–20 25 AnOth
n- Im et al. [367] 313–333 0.3–1.7 320 AnTVLcirValVis
Butane Lim et al. [505] 273–323 0.1–1.3 85 AnTVLcirValVis
o-Ethylvanillin Knez et al. [102] 313–333 4.7–26 120 AnT
Knez et al. [102] 313–333 5.2–24.6 120 AnT
Poly(ethylene) (LDPE) Wang et al. [757] 383–473 0.3–2.2 42 SynT
Polystyrene (PS) Li et al. [73] 403–463 1.3–5.5 n.a. AnGrav
Propane Lim et al. [503] 273–323 0.2–2.1 85 AnTVLcirValVis
Sodium dibutyl sulfosuccinate Liu et al. [47] 308–338 10–30 48 AnTIns
Sodium dihexyl sulfosuccinate Liu et al. [47] 308–338 10–30 48 AnTIns
Sodium dioctyl sulfosuccinate Liu et al. [47] 318–318 30–30 48 AnTIns
Sodium dipentyl sulfosuccinate Liu et al. [47] 318–318 30–30 48 AnTIns
Sodium salt of dibutyl-2-sulfosuccinate Liu et al. [521] 318–318 25–25 48 AnTIns
Sodium salt of dihexyl-2-sulfosuccinate Liu et al. [521] 318–318 25–25 48 AnTIns
Sodium salt of dioctyl-2-sulfosuccinate Liu et al. [521] 318–318 25–25 48 AnTIns
Sodium salt of dipentyl-2-sulfosuccinate Liu et al. [521] 308–338 15–35 48 AnTIns
Squalane Hong et al. [352] 324–400 0–0.6 329.2 SynTVcir
Triethylene glycol dimethyl ether Marchi et al. [539] 282–322 0.2–1.3 n.a. SynNon
Trifluoromethane (HFC-23) Cui et al. [238] 258–293 0.2–3.4 80 AnTLcirVis
Tristearin Spilimbergo et al. [123] 313–326 0.1–0.4 n.a. SynNon
Knez et al. [102] 346–352 0.6–30.4 74 SynVis
␣-Acetamidocinnamic acid Abbott et al. [89] 378–378 4–20 25 AnOth
thus has a low contribution to the background. The cell is a hollow 3.1.5. Analytical gravimetric methods (AnGrav)
cylinder with flanges on each end as support surfaces for sealing With gravimetric methods the mass of a condensed phase (e.g.,
endcaps. No bolts run along the outside of the cell. No other exter- a polymer [73], an ionic liquid [74], or an polymerized ionic liquid
nal supports are needed. The cell has an internal volume of 7.8 cm3 [75]) in phase equilibrium with a fluid phase is measured. Using
and can be operated at pressures up to 35 MPa and temperatures addtional information, like the phase densities, the phase compo-
between 10 and 300 K. sitions can be determined.
In the analytical spectroscopic methods, the advantage of avoid- While quartz spring balances are less and less used, commer-
ing the trouble with taking samples is often overcompensated by cially available electrobalances become more widespread. Almost
the need of time consuming calibrations at high pressures. Only 25 years ago Kleinrahm and Wagner [76] from Ruhr-Universität
1.5% of all systems covered in this review have been investigated Bochum proposed a unique balance, the so-called magnetic suspen-
with a spectroscopic method. sion balance, which they further developed and commercialized.
Table 29
Binary systems: 1,1,1-trifluoroethane (HFC-143a) + X.
1-n-Butyl-3-methylimidazoium Shiflett and Yokozeki [662] 284–348 0–1 n.a. AnGrav

Shiflett and Yokozeki [664] 291–338 1.1–3.2 1.2 SynOthVis
Dimethyl ether (DME) Im et al. [372] 313–363 0.8–4.2 320 AnTVLcirValVis
Isobutene Yun et al. [784] 273–348 0.1–3.6 200 AnTVLcirValVis
n-Butane Seong et al. [654] 273–323 0.1–2.2 85 AnTVLcirValVis
Propane Lim et al. [503] 268–318 0.4–2.3 85 AnTVLcirValVis
Table 30
Binary systems: 1,1-difluoroethane (HFC-152a) + X.
1-n-Butyl-3-methylimidazolium Shiflett and Yokozeki [664] 318–354 0.7–2.4 1.2 SynOthVis

Bisphenol A (2,2-bis(4-hydroxyphenyl) Liu et al. [516] 383–451 17.5–60 30 SynVisVar
propane)
Bisphenol AF (2,2-bis(4-hydroxyphenyl) Liu et al. [516] 348–453 2–15 30 SynVisVar
hexafluoropropane)
Carbon dioxide Di Nicola et al. [260] 223–343 0–3.8 273.5 SynNon
Isobutene Yun et al. [785] 273–348 0.1–2.1 200 AnTVLcirValVis
n-Butane Im et al. [371] 313–363 0.3–2.9 320 AnTVLcirValVis
Lim et al. [504] 273–323 0.1–1.2 85 AnTVLcirVis
Polyethylene terephthalate Faridi and Todd [50] 353–373 0.4–3.5 45 AnTMla
Polystyrene (PS) Li et al. [73] 403–463 1.3–5.6 n.a. AnGrav
Propane Park et al. [595] 273–313 0.2–1.5 128 AnTVcir
Originally, it was intended for accurate measurements of fluid den- They used the analytical gravimetric method (AnGrav) only at
sities, but other applications were found, particularly to measure pressures up to 1.3 MPa. At higher pressures they measured the
the solubility and diffusivity of volatile components in polymers, same systems using the synthetic-isothermal method (SynT). Pan-
e.g. Aionicesei et al. [77] or Li et al. [78]. It has the main advan- toula et al. combined magnetic-suspension-balance experiments
tage that the equilibrium cell and the balance are separate units. (AnGrav) with the material-loss-analysis method (AnTMla). This
An electronically controlled magnetic suspension coupling is used combination allows the determination of sorption and swelling at
to transmit the measured force from the sample enclosed in a pres- high pressures and temperatures where optical methods are diffi-
sure vessel to a microbalance. The suspension magnet, which is cult to use.
used for transmitting the force, consists of a permanent magnet,
a sensor core and a device for decoupling the measuring-load. An 3.1.6. Other analytical methods (AnOth)
electromagnet, which is attached at the underfloor weighing hook Quartz crystal microbalances can be used to determine the solu-
of a balance, maintains the freely suspended state of the suspen- bility of a gas in a polymer by measuring the mass of the polymer in
sion magnet via an electronic control unit. Using this magnetic equilibrium with the gas. From the basic principle, it is not a gravi-
suspension coupling, the measuring force is transmitted contact- metric measurement, so that buoyancy effects play a different role.
lessly from the measuring chamber to the microbalance, which is Quartz crystal microbalances are based on the piezoelectric effect
located outside the chamber under ambient atmospheric condi- observed in a AT-cut quartz crystal. The crystal under the influence
tions. Petermann et al. [79] used a magnetic suspension balance of an applied alternating electric voltage undergoes a shear defor-
with which additional to the sample a sinker (titanium or silicon) mation which becomes maximum at a certain frequency called the
can be weighed. This allows a highly accurate determination of the resonance frequency [86]. This resonance frequency depends on
sorptiv gas density surrounding the sample. the mass, and thus any mass change will result in a respective fre-
Von Solms et al. [80] used a purpose-built high-pressure quency shift. The sorption experiment involves measurement of the
microbalance to determine solubility and diffusivity of gases in resonance frequency of the bare (clean) crystal, of the same crystal
polymers intended for use in offshore oil and gas applications. The coated with polymer, and of the coated crystal after the polymer
polymer sample is placed on one arm of a microbalance, with quartz reaches equilibrium with a gas, all at the same controlled temper-
spheres placed on the other as counterweights. Gas is admitted ature. Concurrently, the resonance frequency of a reference crystal
rapidly to the whole balance at the pressure of interest (or evac- is also measured under the same conditions in order to compensate
uated rapidly in the case of an evacuation run), after the whole any temperature or pressure effects.
apparatus, including the sample, has been at the temperature of Saldana et al. [87] further developed the quartz crystal tech-
interest for at least 24 h. The difference in the reading on the balance nique to measure low solubilities of ␤-carotene in supercritical
before and after a run, is the amount of gas adsorbed or desorbed. fluids. ␤-Carotene was dissolved in chloroform, an aliquot was
The diffusion coefficient can also be obtained by studying the time- placed on the quartz crystal electrode area. The solvent was slowly
dependent behavior of the adsorbed/desorbed mass of gas. evaporated under gentle nitrogen flow. The solubility was mea-
Shiflett and Yokozeki [81] used a gravimetric microbalance sured by observing the crystal’s frequency change as this solute
to measure solubility and diffusivity of CO2 in ionic liquids. The dissolves in the supercritical fluid.
microbalance consists of an electrobalance with sample and coun- As compared to conventional methods, such as analytical gravi-
terweight components inside a stainless steel pressure-vessel. It metric (AnGrav) or synthetic-isothermal (SynT, pressure decay), a
has a weighing range of 0–100 mg with a resolution of 0.1 ␮g. Sori- much higher sensitivity for the determination of mass changes can
ano et al. [82] used a gravimetric microbalance with a weighing be achieved with a quartz crystal microbalance. Therefore, smaller
range of up to 100 g with a readability of 1 ␮g. samples are needed and phase equilibrium is attained much faster,
Gravimetric methods need corrections for buoyancy, which since equilibration time is inversely proportional to the square of
can be higher than the uncorrected solubility [83]. Therefore, the film thickness. Pantoula and Panayiotou [86] report an equi-
particularly at high pressures, exact information on the density librium time of 30 min for CO2 in PMMA or polystyrene at a film
of the fluid phase and on the density and volume of the con- thickness of 1–3 ␮m on the crystal. However, the quartz crystal
densed phase is essential [81]. Owing to this problem often the microbalance technique also has some drawbacks: the preparation
analytical gravimetric method is combined with other methods and loading of the sample onto the crystal can be very challenging
as described, e.g. by Muldoon et al. [84] or Pantoula et al. [85]. in addition to the system being highly sensitive to small changes in
Muldoon et al. measured the solubility of CO2 in ionic liquids. electrical current, any air flow or motion in the surroundings and
Table 31
Binary systems: X + Y.
X Y Reference T (K) P (MPa) V (cm3 ) Method
1,1,1,2,3,3,3-Heptafluoropropane (HFC-227ea) Isobutene Yun et al. [786] 288–363 0.2–2.4 200 AnTVLcirVal
1,1,1,3,3,3-Hexafluoropropane (HFC-236fa) Ethylvanillin Knez et al. [102] 313–333 5.7–26.6 120 AnT
Knez et al. [102] 342–347 1.3–29.2 74 SynVis
Ortho-ethylvanillin Knez et al. [102] 313–333 4.2–27 120 AnT
Ortho-vanillin Knez et al. [102] 299–302 1.1–3.6 74 SynVis
Knez et al. [102] 313–333 7.9–26.3 120 AnT
1,1,1,3,3,3-Hexafluoropropane (HFC-236fa) Vanillin Knez et al. [102] 350–355 1.3–28.3 74 SynVis
1,1,1,3,3-Pentafluorobutane (HFC-365mfc) Galden HAT 55 Fröba et al. [305] 304–448 0–2.7 10 SynTVis
1,2,2,2-Tetrafluoroethyl trifluoromethyl ether (HFE-227me) Methylpentafluoroethylether (HFE-245mc) Yasumoto et al. [777] 401–382 2.8–2.6 16 SynVisVarPcTc
Trifluoromethoxymethane (HFE-143m) Yasumoto et al. [777] 377–376 2.8–3.4 16 SynVisVarPcTc
1,5-Hexadiene Allyl chloride Giles and Wilson [316] 333–373 0.1–0.4 n.a. SynT
1-Butanol 1-n-Hexyl-3-methylimidazolium Łachwa et al. [476] 268–269 10.1–50.2 0.5 SynVis
bis(trifluoromethylsulfonyl)amide [C6-mim] [Tf2N]
1-Chloro-1,1-difluoroethane (HCFC-142b) (HCFC-142b) Polystyrene Choudhary et al. [114] 423–460 1.4–10 n.a. SynVisCon
1H,1H,2H,2H-tridecafluorooctanol 1-n-Decyl-3-methylimidazolium Ferreira et al. [297] 275–277 0.1–4.2 1 SynVis
bis-[(trifluoromethyl)sulfonyl]imide [C10-mim] [Tf2N]
J.M.S. Fonseca et al. / Fluid Phase Equilibria 300 (2011) 1–69

1-n-Dodecyl-3-methylimidazolium Ferreira et al. [297] 268–269 0.1–5 1 SynVis
1-n-Dodecyl-3-methylpyridinium Ferreira et al. [297] 283–285 0.1–5 1 SynVis
bis-[(trifluoromethyl)sulfonyl]imide [C10-py] [Tf2N]
1-n-Octyl-3-methylimidazolium Ferreira et al. [297] 285–288 0.1–4 1 SynVis
1H,1H,7H-perfluoroheptan-1-ol Perfluoro-n-heptane Trindade et al. [719] 291–292 0.5–4.4 1 SynVis
Perfluoro-n-hexane Trindade et al. [719] 288–288 0.5–4.2 1 SynVis
Perfluoro-n-nonane Trindade et al. [719] 307–308 0.2–4.4 1 SynVis
Perfluoro-n-octane Trindade et al. [719] 301–302 0.1–4.4 1 SynVis
1-Hexanol 1-n-Hexyl-3-methylimidazolium Łachwa et al. [476] 306–307 10–55 0.5 SynVis
1-Nitropropane n-Decane Losada-Pérez [109] 281–282 0.3–4.2 1 SynVis
n-Dodecane Losada-Pérez [109] 292–292 0.3–4.4 1 SynVis
n-Tetradecane Losada-Pérez [109] 300–301 0.4–4.6 1 SynVis
n-Tridecane Losada-Pérez [109] 296–296 0.3–4.8 1 SynVis
1-Octanol Cyclohexyl carboxylic acid (CCA) Domanska et al. [267] 303–353 0.8–729 n.a. SynNonVar
1-Pentanol 1-n-Hexyl-3-methylimidazolium Łachwa et al. [476] 288–289 10.1–50.1 0.5 SynVis
2,2,4-Trimethylpentane (isooctane) 2-Methylpropane Li et al. [496] 409–544 2.5–4.2 18 SynVisPcTc
2,2-Dimethylpropane (neopentane) Deuterated poly(ethylene-co-20.2 mol%-1-butene) (PEB10) Kostko et al. [445] 285–461 19.4–196.2 15 SynVisVar
2,3-Pentanedione Cyclohexane Domanska et al. [266] 293–343 23.3–1549.2 n.a. SynNonVar
n-Tridecane Domanska et al. [266] 293–343 132.3–1549.2 n.a. SynNonVar
2-Methylbutane (isopentane) Deuterated poly(ethylene-co-20,2 mol%-1-butene) (PEB10) Kostko et al. [445] 281–448 1.5–165.3 15 SynVisVar
2-Methylpentane (isohexane) Poly(ethylene) (LDPE) Nagy et al. [569] 380–500 0.7–12 3.5 SynVisVar
2-Methylpropane (isobutane) 2-Butanol Laavi et al. [475] 364–364 0–1.6 113 SynT
2-Methyl-2-propanol Laavi et al. [475] 364–364 0.1–1.6 113 SynT
2-Propanol (isopropanol) Laavi et al. [475] 364–364 0.1–1.6 113 SynT
Ethylvanillin Knez et al. [102] 341–347 1–31.5 74 SynVis
o-Ethylvanillin Knez et al. [102] 331–336 0.8–30.8 74 SynVis
POE ISO 7 lubricant oil Marcelino Neto and Barbosa [538] 283–333 0–0.8 4000 AnTLcirBlo
Vanillin Knez et al. [102] 350–356 1.2–30.6 74 SynVis
2-Methylpropene 1-Propanol Hynynen et al. [364] 364–364 0–1.5 n.a. SynT
2-Butanol Hynynen et al. [364] 364–364 0–1.5 n.a. SynT
2-Methyl-2-propanol Hynynen et al. [364] 364–364 0.1–1.5 n.a. SynT
2-Propanol (isopropanol) Hynynen et al. [364] 364–364 0.1–1.5 n.a. SynT
2-Propanone 2-Methylpropane (isobutane) Pasanen et al. [596] 364–364 0.2–1.6 113.1 SynT
2-Methylpropene Pasanen et al. [596] 364–364 0.2–1.5 113.1 SynT
Cis-2-Butene Pasanen et al. [596] 365–365 0.3–1.2 113.1 SynT
37
38
Table 31 (Continued)
2-Propanone Trans-2-butene Pasanen et al. [596] 364–364 0.2–1.2 113.1 SynT

Argon Polyethylene terephthalate Faridi and Todd [50] 323–373 6–12 45 AnTMla
Benzene 1-n-Butyl-3-methylimidazolium tetrafluoroborate ([bmim] Anthony et al. [74] 283–323 0–0 n.a. AnGrav
[BF4 ])
Boron Boron (III) oxide Solozhenko [92] 300–2750 5000–5000 n.a. SynNon
Caprylic acid (C8:0) Myristic acid (C14:0) Costa et al. [235] 285–348 0.1–90 0.03 SynVis
Cholesterol Ceramide 3A (N-linoeoyl-phytosphingosine, 97%) Vezzu et al. [742] 378–420 0.1–0.1 n.a. SynNon
Cis-2-Butene 2-Butanol Wierink et al. [765] 364–364 0–1.1 112.7 SynT
2-Methyl-2-propanol Wierink et al. [765] 364–364 0.1–1.1 112.7 SynT
2-Propanol (isopropanol) Wierink et al. [765] 364–364 0.1–1.1 112.7 SynT
Cyclopentane Polyethylene terephthalate Faridi and Todd [50] 373–448 0.1–1.8 45 AnTMla
d-Ethane Poly(ethylene-co-20, 2 mol%-1-butene) (PEB10) Kostko et al. [445] 368–428 103.3–117 15 SynVisVar
Deuterium Heavy water Efimchenko et al. [151] 233–278 20–180 n.a. SynT / SynNon
Difluoromethoxy trifluoromethane (HFE-125) 1-Ethyl-3-methylimidazolium Shiflett et al. [666] 283–348 0–0.4 n.a. AnGrav
bis(trifluoromethylsulfonyl)imide [emim] [Tf2N]
Ethylene oxide 2-Methylpropane (isobutane) Giles and Wilson [316] 298–348 0.1–1.3 n.a. SynT
Fluoroethane (HFC-161) 1-n-Butyl-3-methylimidazolium hexafluorophosphate [bmim] Shiflett and Yokozeki [664] 243–338 0.1–2.4 1.2 SynOthVis

[PF6 ]
Fluoromethane (HFC-41) 1-n-Butyl-3-methylimidazolium hexafluorophosphate [bmim] Shiflett and Yokozeki [664] 243–294 0.8–3.5 1.2 SynOthVis
[PF6 ]
Hydrogen chloride n-Dodecane Llovell et al. [524] 258–368 0.7–12.1 n.a. SynVisVar
Isopropyl acetate Acetonitrile (ethanenitrile) Giles and Wilson [316] 393–453 0.2–1.1 n.a. SynT
lauric acid (C12:0) Myristic acid (C14:0) Costa et al. [235] 308–348 0.1–90 0.03 SynVis
n-Hexadecane 2,2-Dimethylbutane Domanska and Morawski [264] 293–343 9.2–648.3 n.a. SynNonVar
3-Methylpentane Domanska and Morawski [264] 293–343 9.2–684.1 n.a. SynNonVar
Benzene Domanska and Morawski [264] 293–343 9.2–418.6 n.a. SynNonVar
N-Methyl-2-pyrrolidone 1,4-Benzenedicarboxylic acid Wang et al. [758] 343–468 1.6–1.6 800 AnT
4-Carboxybenzaldehyde Wang et al. [758] 353–421 1.6–1.6 800 AnT
n-Octadecane 2,2-Dimethylbutane Domanska and Morawski [264] 303–353 8.8–578.6 n.a. SynNonVar
3-Methylpentane Domanska and Morawski [264] 303–353 8.8–894.6 n.a. SynNonVar
n-Pentane 1-Butanol Kim et al. [427] 468–513 0.8–4.1 100 AnTVLcirValVisPc
1-Propanol Jung et al. [400] 468–513 1.5–4.8 100 AnTVLcirValVisPc
2-Butanol Kim et al. [427] 468–513 1.3–4 100 AnTVLcirValVisPc
2-Methyl-1-propanol Jung et al. [400] 468–513 1.1–4.1 100 AnTVLcirValVisPc
Deuterated poly(ethylene-co-20,2 mol%-1-butene) (PEB10) Kostko et al. [445] 283–408 1.8–220.6 15 SynVisVar
Isotactic poly(4-methyl-1-pentene) Fang and Kiran [288] 297–337 10.7–44.5 n.a. SynVisVar
Poly(ethylene) Zhang and Kiran [800] 360–378 10–52 n.a. SynVisVar
Polyethylene terephthalate Faridi and Todd [50] 373–448 0.2–2.4 45 AnTMla
n-Tetradecane n-Hexadecane Milhet et al. [103] 279–313 0.1–100 0.03 SynVis
n-Pentadecane Milhet et al. [103] 275–303 0.1–100 0.03 SynVis
n-Tridecane 1-Hexyne Domanska and Morawski [265] 293–343 133–969.2 n.a. SynNonVar
2,2-Dimethylbutane Domanska and Morawski [265] 293–343 133–1100.6 n.a. SynNonVar
3-Methylpentane Domanska and Morawski [265] 293–343 133–1436.5 n.a. SynNonVar
Perfluoromethylcyclohexane n-Decane Gozalpour et al. [320] 373–373 0.2–0.3 400 AnTVcirValVis
Perfluoro-n-octane n-Heptane Pratas de Melo et al. [110] 330–334 0.1–4.4 1 SynVis
n-Nonane Pratas de Melo et al. [110] 344–347 0.1–4.4 1 SynVis
n-Octane Pratas de Melo et al. [110] 330–353 0.1–4.4 1 SynVis
Poly(ethylene) (LDPE) 1-Chloro-1,1-difluoroethane (HCFC-142b) Wang et al. [757] 383–473 0.2–2.9 42 SynT
2-Methylpropane (isobutane) Wang et al. [757] 383–473 0.3–3 42 SynT
Sulfur hexafluoride (SF6) Ethylvanillin Knez et al. [102] 351–356 3.4–30.1 74 SynVis
o-Ethylvanillin Knez et al. [102] 340–346 4.9–31.9 74 SynVis
Vanillin Knez et al. [102] 357–362 5.2–31 74 SynVis
Tetrafluoroethane (HCF-134a) Bisphenol AF (2,2-bis(4-hydroxyphenyl)hexafluoropropane) Liu et al. [516] 396–453 12.5–20 30 SynVisVar
any other interference occurring in the same room or even next
Method
SynVis
SynVis
SynVis
door [87]. Errors rise with temperature and pressure, due to damp-
SynT
SynT
SynT
SynT
SynT
ening and viscous dissipation upon entering the glass transition
and rubbery state [86].
Another analytical method was used by Giraudeau et al. [88]
V (cm3 )
to measure low gas solubilities, e.g. of hydrogen in water. A palla-
29.7
113
113
113
113
n.a.
dium/hydrogen electrical resistance sensor was used to determine
30
30
the hydrogen content in aqueous electrolyte solutions.
A capacitative method (relative-permittivity method) was used
by Abbott et al. [89] to measure the solubility of unsaturated
1.1–11.2
carboxylic acids in supercritical HFC 134a. Experiments were per-
0–1.2
0–1.2
0.1–1.2
0.1–1.2
0.1–0.8
1.1–9
0.1–2
formed in a 25 cm3 high-pressure cell, lined with a layer of Teflon.
P (MPa)
A capacitor consisting of two parallel rectangular stainless steel

plates (area of 6.6 cm2 , held 1 mm apart by Teflon spacers) was
placed in the vapor-phase. The dielectric constant of the saturated
vapor phase was measured at different pressures. To calculate the
293–413
364–364
364–364
364–364
364–364
273–313
293–413
293–413
concentration of the solute in the vapor phase from the dielectric

T (K)
constant, information on the permanent dipole moments and the

molecular polarizabilities of the components of the mixture needs
to be known.
Giles and Wilson [316]
Roininen et al. [620]
Kumelan et al. [469]
3.2. Synthetic methods (Syn)
The basic principle of synthetic methods is to prepare a mix-

Reference
ture of precisely known composition and then to observe the

phase behavior in an equilibrium cell and to measure proper-
ties in the equilibrium state, like pressure and temperature. No
sampling is necessary. The problem of analyzing fluid mixtures is
replaced by the problem of “synthesizing” them. Synthetic meth-
ods can be applied with or without a phase transition. In both
cases, first a mixture of precisely known composition is pre-
1-n-Butyl-3-methylimidazolium methyl sulfate [bmim]
pared.
In synthetic methods with a phase transition values of tempera-
bis(trifluoromethylsulfonyl)amide [hmim] [Tf2N]
bis(trifluoromethylsulfonyl)amide [hmim] [Tf2N]
ture and pressure are adjusted so that the mixture is homogeneous,

a single phase exists. Then the temperature or pressure is varied
until the beginning of the formation of a new phase is observed.
The composition of the first, large phase can be set to the known
1-n-Hexyl-3-methylimidazolium
1-n-Hexyl-3-methylimidazolium
overall composition. The composition of the second, small phase

is not known. Each experiment yields one point of the pTx phase
envelope.
Chloromethane (HCC-40)
2-Propanol (isopropanol)
Instead of a variation of temperature or pressure to cause a

2-Methyl-2-propanol
phase transition the overall concentration can be changed. Munto

et al. [90,91] used this approach, designated with “vanishing-point
method” or “clear-point method”, for SLE measurements. A clear
1-Propanol
2-Butanol
[CH3 SO4 ]
solution of a given solute concentration is added to a known amount

of anti-solvent until the last crystal disappears. The composition of
the mixture at this vanishing point equals the solubility of the mix-
Y
ture. When the procedure is repeated with a solution of a different

concentration another point of the curve is found.
Depending on how the phase transition is detected, synthetic
methods with a phase transition can be divided into visual (SynVis)
and non-visual methods (SynNon).
In synthetic methods without a phase transition, equilibrium
properties like pressure, temperature, phase volumes and densi-
ties are measured and phase compositions are calculated using the
material balance. Synthetic methods without a phase transition can
be divided into isothermal (SynT), isobaric (SynP) and other (Syn-
Tetrafluoromethane (CFC-14)
Oth) synthetic methods. During the period covered in this review

(2005–2008) synthetic methods with a phase transition have been
used more often (49.4% of all systems) than synthetic methods
without a phase transition (13% of all systems).

Trans-2-butene
Vinyl chloride
Synthetic methods can be used where analytical methods fail,

i.e., when phase separation is difficult due to similar densities
of the coexisting phases, e.g. near or even at critical points and
Xenon
in barotropic systems, where at certain conditions the coexisting

X
phases have the same density. Often, the experimental procedure

Table 32
Ternary systems: carbon dioxide + water + X.
1-(1-Hydroxypropyl)-methylimidazolium nitrate Bermejo et al. [105] 303–353 0.8–11.3 n.a. SynVisVar

[hopmim][NO3 ]
1,4-Dioxane Seo et al. [652] 274–280 1–3.7 50 SynVis
1-Butanol Najdanovic-Visak et al. [570] 297–297 5.9–64.1 24 SynVisVar
1-n-Butyl-3-methylimidazolium Fu et al. [306] 313–333 1–25 n.a. SynTVis
hexafluorophosphate [bmim][PF6 ]
1-n-Butyl-3-methylimidazolium nitrate Bermejo et al. [105] 293–368 0.8–9.4 n.a. SynVisVar
[bmim][NO3 ]
2-Amino-2-methyl-1-propanol Arcis et al. [174] 322–322 0.2–5.2 22 SynOth
3-Methylpentaethyleneglycol-2-(2-ethylhexyl)-1- Sawada et al. [633] 318–328 20–30 4.6 SynVis
(2-ethylhexylglycerol)
3-Methylpentaethyleneglycol-2-(2-ethylhexyl)-1- Sawada et al. [633] 318–328 20–30 4.6 SynVis
octhylglycerol
3-Methylpentaethyleneglycol-2-octyl-1-n- Sawada et al. [633] 318–328 20–30 4.6 SynVis
pentylglycerol
3-Methylpentaethyleneglycol-2-pentyl-1-n- Sawada et al. [633] 318–328 20–30 4.6 SynVis
octylglycerol
Acetone Jödecke et al. [393] 313–395 0.1–9.6 30 SynVis
Seo et al. [652] 270–279 0.8–3.5 50 SynVis
Bis(2,2,3,3,3-pentatfluoropropyl)2-sulfosuccinate Liu et al. [523] 307–337 12–25 n.a. SynVisVar
Bis(2,2,3,4,4,4-hexafluorobutyl)2-sulfosuccinate Liu et al. [523] 312–337 18–22.5 n.a. SynVisVar
Calcium chloride Mohammadi et al. [554] 270–274 2.1–3.6 57.5 SynNonVis
Diethylene glycol Afzal et al. [166] 272–281 1.4–3.7 n.a. SynNon
Dimethyl sulfoxide Andreatta et al. [173] 278–370 1.2–11.5 3.5 SynVisVar
Dimethylsulfoxide Perez de Diego et al. [599] 273–363 1.8–8.2 30 SynVisVar
Ethanol de la Fuente et al. [248] 313–343 10.1–18.6 300 SynVisVar
Durling et al. [274] 313–313 10–30 n.a. AnPTCon
Ethoxylated nonyl phenol Koh et al. [101] 313–313 10–24 22.4 SynVisVar
Ethylene glycol Abdi et al. [163] 273–303 1–3.4 n.a. AnT
Glycerol Mohammadi et al. [555] 264–279 1.2–3.3 58 SynNon
Hydrogen Kumar et al. [456] 273–281 1.5–10.7 n.a. AnTVis
Linga et al. [511] 273–273 1–8.5 323 AnTVis
Sugahara et al. [701] 274–281 1.4–9.1 150 AnTVis
Sugahara et al. [701] 274–274 15.2–15.2 0.2 SynVisSpec
Methane Beltrán and Servio [97] 275–285 1.9–7.4 150 SynVisVar
Qin et al. [605] 324–375 10.7–49.9 200 AnT
Methanol Levitin et al. [489] 342–343 11.9–20 20 SynVisVar
Methyldiethanolamine (MDEA) Arcis et al. [175] 322–322 0.5–5.1 22 SynOth
Nitrogen Bruusgaard et al. [198] 275–283 1.6–22.4 150 SynVisVar
Linga et al. [511] 273–273 1–11 323 AnTVis
Polyethylene oxide-2,6,8-trimethyl-4-nonyl ethers Haruki et al. [340] 308–343 16.8–38.7 15 SynNonVisVar
(TMN)
Potassium carbonate Kamps et al. [407] 313–393 0.3–8.9 30 SynVis
Potassium chloride Kamps et al. [407] 315–433 0.3–9.1 30 SynVis
Mohammadi et al. [554] 273–278 2–3.3 57.5 SynNonVis
Propylene oxide Seo et al. [652] 271–281 0.3–3.3 50 SynVis
Sodium Koh et al. [101] 313–313 12.5–25 22.4 SynVisVar
bis-(2,2,3,3,4,4,5,5-octafluoro-1-n-pentyl)-2-
sulfosuccinate
Sodium bis(2,2,3,3,3-pentafluoro-1- Liu et al. [522] 303–333 11–30 60 SynVis
propanol)sulfosuccinate
Sodium bis(2,2,3,3-tetrafluoro-1- Liu et al. [522] 303–333 11–30 60 SynVis
propanol)sulfosuccinate
Sodium bis(2,2,3,4,4,4-hexafluoro-1- Liu et al. [522] 303–333 11–30 60 SynVis
butanol)sulfosuccinate
Sodium bis(3,3,4,4,5,5,6,6,6-nonafluoro-1- Liu et al. [522] 303–333 6–16 60 SynVis
hexanol)sulfosuccinate
Sodium chloride Kim et al. [426] 278–280 10.1–20.1 n.a. SynVisVar
Mohammadi et al. [554] 271–280 1.3–3.7 57.5 SynNonVis
Sodium dodecyl sulfate Zhang et al. [789] 270–281 1.3–3.1 474 AnTVis
Sodium salt of bis(2,2,3,3,4,4,5,5-octafluoro- Park et al. [590] 308–368 14–97.3 n.a. SynVisVar
1-pentanol) sulfosuccinate
Sodium sulfate Bermejo et al. [187] 286–368 1.9–13.1 n.a. SynVis
Soduim chloride Koschel et al. [443] 323–373 5–20.2 22 SynOth
Tetrabutyl ammonium bromide Arjmandi et al. [176] 285–291 1.4–4 2400 SynNon
Tetrahydrofuran Delahaye et al. [253] 278–290 0.1–3.5 46 SynNon
Delahaye et al. [253] 278–290 0.1–3.5 n.a. SynNon
Seo et al. [652] 272–291 0.2–4 50 SynVis
Martinéz et al. [540] 278–290 0.2–2 n.a. SynNon
Tetra-n-butylammonium bromide Lin et al. [510] 279–288 0.3–2.2 46 SynNonVis
Lin et al. [510] 283–283 0.4–2.2 46 SynT
Triethylene glycol Afzal et al. [165] 264–282 0.6–4.2 58 SynNon
Trifluoromethane (HFC-23) Mooijer-van den Heuvel et al. [560] 280–303 1.4–9.9 3.5 SynVisVar
Tri-iso-butyl(methyl)phosphonium tosylate Ventura et al. [740] 276–369 0.8–99.7 n.a. SynVisVar
[iBu3MeP][TOS]
Table 33
Ternary systems: carbon dioxide + methanol + X.
Aspirin Huang et al. [359] 318–328 10–20 20 AnPTSemY

Atenol Kikic et al. [422] 313–323 7.9–9.8 72.32 SynVisVar
C.I. Acid Red 57–dodecyltrimethylammonium Özcan and Özcan [587] 318–373 25–32.5 10.4 AnPTSemY
C.I. acid red 57-hexadecyltrimethylammonium bromide Özcan and Özcan [63] 308–348 25–32.5 10.4 AnPTSemY
Carbon monoxide Lopez-Castillo et al. [526] 298–298 4.1–4.1 n.a. AnTVarVis
Cyclohexane Saito [623] 276–316 0.2–1.9 22 SynVis
Dibenzofuran Perez [601] 318–338 9.3–20.6 15 SynVisVar
Dimethyl carbonate Pinero [602] 320–455 8–15 n.a. SynNonCon
Hydrogen Lopez-Castillo [527] 313–313 2.5–9 n.a. AnTVisVar
n-Decane Saito [623] 318–361 0.4–2.2 22 SynVis
n-Hexane Saito [623] 275–299 0.4–1.3 22 SynVis
n-Octane Saito [623] 275–337 0.4–2.1 22 SynVis
Oxygen Lopez-Castillo et al. [526] 313–313 1.5–5.3 n.a. AnTValVis
Perfluorohexane (PFC-72) Draucker et al. [269] 313–313 2.1–5.5 103 SynTVisVar
Poly(ethylene glycol) Kong et al. [439] 313–313 9.5–9.5 3.3 AnPTChro
Water Levitin et al. [489] 342–343 11.9–20 20 SynVisVar
is easy and quick. Because no sampling is necessary the experimen- extreme conditions concerning temperatures and pressures. Smith
tal equipment can concentrate on few components and the volume and Fang [8] give examples of the use of diamond anvil cells at very
of the equilibrium cell can be small. Therefore, the apparatus can high pressures. The experimental data at the highest pressures of
be rather inexpensive. On the other hand it can be designed for all articles covered in this review were taken by Solozhenko et al.
Table 34
Ternary systems: carbon dioxide + ethanol + X.
(R,S)-(+-)-Ibuprofen Munto et al. [90] 298–298 10–10 75 SynVisVarVcir

(S)-Naproxen Munto et al. [90] 298–298 10–10 75 SynVisVarVcir
Acetazolamide Duarte et al. [271] 313–323 15–20.1 30 AnTCapValVis
Aspirin Huang et al. [359] 318–328 10–20 20 AnPTSemY
Atenol Kikic et al. [422] 313–323 7.6–9.1 72.3 SynVisVar
␤-Carotene Borges et al. [195] 303–343 3.1–11.4 27 SynVisVar
C.I. Disperse violet 1 Tsai et al. [721] 353–393 15–30 n.a. AnPTSemY
C.I. Disperse yellow 54 Tsai et al. [720] 353–393 15–30 33 AnPTSemY
Kopcak and Mohamed [442] 323–343 15.2–30 300 AnPTSemY
Carnosic acid Chafer et al. [212] 313–333 28–40 10 AnPTSemY
Dichloromethane (HCC-30) Franceschi et al. [302] 303–343 3–10.6 27.0 SynVIsVar
Subra et al. [697] 309–333 5–11 n.a. SynVisVar
Wang et al. [752] 308–328 6.2–9.2 50 SynVisVarPc
Dodecanoic acid Garlapati and Madras [310] 308–308 9.9–22.6 n.a. AnPTSemY
Ethyl acetate Cheng and Chen [223] 303–312 4.1–7 320 AnTLcirValVis
Gallic acid Chafer et al. [214] 313–333 10–40 n.a. AnPTSemY
Hexadecanoic acid Garlapati and Madras [311] 308–318 12.8–22.6 n.a. AnPTSemY
Limonene Iwai et al. [44] 313–313 6.9–6.9 n.a. AnTLcirBlo
Iwai et al. [44] 313–313 6.9–6.9 n.a. AnPTSemY
Linalool Iwai et al. [44] 313–333 6.9–10 n.a. AnTLcirBlo
Iwai et al. [44] 313–333 6.9–10 n.a. AnPTSemY
Octadecanoic acid Garlapati and Madras [311] 308–318 12.8–22.6 n.a. AnPTSemY
p-Methylbenzen sulfonic acid Zhang et al. [807] 308–308 8–21 100 AnPTSemY
Poly(ethylene glycol) Kong et al. [439] 313–313 9.5–9.5 3.3 AnPTChro
Poly(ethylene glycol) 1000 Matsuyama and Mishima [541] 313–313 15–15 150 SynVisVar
Poly(ethylene glycol) 20,000 Matsuyama and Mishima [541] 313–313 15–15 150 SynVisVar
Poly(ethylene glycol) 6000 Matsuyama and Mishima [541] 300–324 8.2–20 150 SynVisVar
Poly(methyl methacrylate) Matsuyama and Mishima [542] 293–359 2–14.1 150 SynVisVar
Polyoxyalkylene block co-polymer Munto et al. [91] 298–298 10–10 75 SynVisVarVcir
surfactant (poloxamer F-127)
Puerarin Wang and Cheng [756] 308–328 0–20 1000 AnT
Salicylic acid Lin et al. [509] 318–328 9.8–12.3 6–25 SynVisVar
Sodium bis(2-ethylhexyl) Liu et al. [517] 311–311 10–33 10 SynVis
sulfosuccinate
Sunflower oil Hernández et al. [346] 313–333 13–20 120 AnTVarVis
Tetradecanoic acid Garlapati and Madras [310] 308–318 9.9–22.6 n.a. AnPTSemY
Theophylline Subra et al. [697] 309–309 11–11 n.a. SynVisVar
Thiophene Serrano-Cocoletzi et al. [656] 333–363 2–11.3 100 AnTValVis
Urea Catchpole et al. [211] 313–333 15–30 500 AnPTSemY
Water de la Fuente et al. [248] 313–343 10.1–18.6 300 SynVisVar
Durling et al. [274] 313–313 10–30 n.a. AnPTCon
Table 35
Ternary systems: carbon dioxide + tetrahydrofuran + X.
Polystyrene Xu et al. [771] 393–393 6.5–18 21 SynVis

Polysulfone Zhang and Kiran [801] 296–426 13.8–54.9 24.8 SynVisVar
Water Delahaye et al. [253] 278–290 0.1–3.5 46 SynNon
Martinéz et a. [540] 278–290 0.2–2 n.a. SynNon
Seo et al. [652] 272–291 0.2–4 50 SynVis
Table 36
Ternary systems: carbon dioxide + dimethyl ether + X.

Poly(␧-caprolactone) Byun et al. [202] 327–483 115–236 28 SynVisVar
Poly(octyl acrylate) Byun and Yoo [99] 323–454 2.5–201.5 28 SynVisVar
Poly(p-decyloxymethyl styrene) Shin et al. [675] 353–454 2.5–21.5 28 SynVisVar
Poly(p-decylsulfonylmethyl styrene) Shin et al. [675] 327–453 12.9–212.5 28 SynVisVar
Poly(p-decylthiomethyl styrene) Shin et al. [675] 333–452 8.7–31.3 28 SynVisVar
Table 37
Ternary systems: carbon dioxide + acetone + X.
(R,S)-(+-)-Ibuprofen Munto et al. [90] 298–298 10–10 75 SynVisVarVcir

(S)-Naproxen Munto et al. [90] 298–298 10–10 75 SynVisVarVcir
1-n-Butyl-3-methyl-imidazolium Zhang et al. [808] 313–313 3–15 50 AnTVisVar
hexafluorophosphate
Carbon monoxide Lopez-Castillo et al. [526] 313–313 9–9 n.a. AnTVarVis
Hydrogen Lopez-Castillo et al. [527] 313–313 2.5–9 n.a. AnTVisVar
Oxygen Lopez-Castillo et al. [526] 313–313 1.4–5.2 n.a. AnTValVis
Perfluorohexane (PFC-72) Draucker et al. [269] 313–313 1.2–2 103 SynTVisVar
Phenanthrene de la Fuente et al. [246] 295–347 1.3–11.9 3.5 SynVisVar
Polycaprolactone Liu and Kiran [518] 340–375 18–27 45.3 SynVisVar
Potassium aurocyanide Rajasingam et al. [609] 308–308 1.5–5 150 AnT
Propyl p-hydroxybenzoate Jin [392] 308–308 8–23 377 AnPTSemY
Salicylic acid Lin et al. [509] 318–328 10.6–25.2 25 SynVisVar
Water Jödecke [393] 313–395 0.1–9.6 30 SynVis
Seo [652] 270–279 0.8–3.5 50 SynVis
[92] who studied the phase behavior of boron + boron(III) oxide at 3.2.1. Synthetic-visual methods (SynVis)
5 GPa. The appearance of a new phase is usually detected by visual
For multicomponent systems, experiments with synthetic observation of the resulting turbidity or meniscus in a view cell. For
methods yield less information than with analytical methods, isooptic systems where the coexisting phases have approximately
because the tie lines cannot be determined without additional the same refractive index, visual observation is impossible. The
experiments. Therefore, synthetic methods are mainly used for synthetic-visual method can be used not only for the determina-
binary or pseudo-binary systems. In latter systems at least one of tion of simple vapor–liquid equilibria, but also to study complicated
the components is a pseudocomponent which is grouped of com- phase behavior, e.g. multiphase equilibria [93,94], solid–liquid
ponents with similar properties. An example for a pseudo-binary equilibria [95], critical curves of mixtures [96], gas hydrate for-
system is CO2 + seawater. mation [97], cloud-point determination [98] and phase equilibria
Table 38
Ternary systems: carbon dioxide + hydrogen + X.
2-Propanol (isopropanol) Zevnik and Levec [788] 298–313 0.6–5 300 AnTX
Acetone Lopez-Castillo et al. [527] 313–313 2.5–9 n.a. AnTVisVar
Acetonitrile Lopez-Castillo et al. [527] 313–313 2.5–9 n.a. AnTVisVar
Limonene Bogel-Lukasik et al. [193] 323–323 11–13 n.a. AnTVarVis
Methanol Lopez-Castillo et al. [527] 313–313 2.5–9 n.a. AnTVisVar
Toluene Yin and Tan [62] 305–343 1.2–10.3 177 AnPTSemX
Water Kumar et al. [456] 273–281 1.5–10.7 n.a. AnTVis
Table 39
Ternary systems: carbon dioxide + X + Y.
(R,S)-1-Phenylethanol Vinyl acetate Paiva et al. [588] 323–343 7–12 160 AnTVisVar
(S)-Naproxen 1-n-Butyl-3-methylimidazolium tetrafluoroborate Kuehne et al. [450] 310–370 1–14 3.5 SynVisVar
[bmim][BF4 ]
1-(4-Isobutylphenyl)-ethanol 1-n-Butyl-3-methylimidazolium tetrafluoroborate Kuehne et al. [453] 278–368 0.7–14 3.5 SynVisVar
[bmim][BF4 ]
1,1,1-Trifluoroethane (HFC-143a) 1,1,1,2,2-Pentafluoroethane (HFC-125) Esperança et al. [120] 305–344 3.7–7.3 5 SynNonPcTc
1-Butanol 2-Ethylhexanoic acid Ghaziaskar et al. [314] 323–323 10–18 16 AnPTSemY
1-Butene 2-Methylpropane (isobutane) Li et al. [496] 376–345 6.4–7.4 18 SynVisPcTc
Poly(octyl acrylate) Byun et al. [99] 393–452 4.6–13.2 28 SynVisVar
1-Decanol 2-Ethylhexanoic acid Ghaziaskar et al. [314] 323–323 10–18 16 AnPTSemY
1-Heptanol n-Pentadecane Secuianu et al. [649] 298–316 4.7–8.5 60 AnTVisVar
1-Methyl-3-octylimidazolium dicyanamide 2-Octanol Bogel-Lukasik et al. [194] 308–308 5–11 42.5 AnTValVis
[omim][N(CN)2 ]
4-(Octan-2-yloxy)-4-oxobutanoic acid Bogel-Lukasik et al. [194] 308–308 5–11 42.5 AnTValVis
Dioctan-2-yl succinate Bogel-Lukasik et al. [194] 308–308 5–11 42.5 AnTValVis
1-Methyl-3-octylimidazolium hexafluorophosphate 2-Octanol Bogel-Lukasik et al. [194] 308–308 5–11 42.5 AnTValVis

[omim][PF6 ]
4-(Octan-2-yloxy)-4-oxobutanoic acid Bogel-Lukasik et al. [194] 308–308 5–11 42.5 AnTValVis
1-Methyl-3-octylimidazolium hexafluorophosphate Dioctan-2-yl succinate Bogel-Lukasik et al. [194] 308–308 5–11 42.5 AnTValVis
[omim][PF6 ]
1-n-Butyl-3-methylimidazolium hexafluorophosphate Naphthalene Fu et al. [307] 313–333 8–20 n.a. AnTVal
([bmim][PF6 ])
1-n-Butyl-3-methylimidazolium tetrafluoroborate 1-Methyl-3-phenylpiperazine Kuehne et al. [449] 343–443 2–12 3.5 SynVisVar
[bmim][BF4 ]
2-(4-Methyl-2-phenyl-1-piperazinyl)-3- Kuehne et al. [449] 343–443 1–14 3.5 SynVisVar
pyridinecarbonitrile
2-Chloro-nicotinonitrile Kuehne et al. [449] 343–443 1–14 3.5 SynVisVar
1-n-Hexyl-3-methylimidazolium Nitrogen Kim et al. [425] 298–298 0.4–0.9 n.a. AnTVcirVal
tri(bisfluoromethylsulfonyl)imide [C6mim][Tf2N]
Propane Kim et al. [425] 298–298 0.3–0.8 n.a. AnTVcirVal
1-Octene Polyethylene glycol Li et al. [500] 308–328 1–9.8 50 AnTVarVis
1-Pentanol 2-Ethylhexanoic acid Ghaziaskar et al. [314] 323–323 10–18 16 AnPTSemY
Sodium bis(2-ethylhexyl)sulfosuccinate Liu et al. [517] 311–311 10–38 10 SynVis
1-Phenylethanol 1-n-Butyl-3-methylimidazolium tetrafluoroborate Kuehne et al. [452] 279–367 0.7–13 3.5 SynVisVar
[bmim][BF4 ]
1-Propanol Poly(ethylene glycol) Kong et al. [439] 313–313 9.5–9.5 3.3 AnPTChro
Propyl acetate Cheng et al. [222] 308–318 3.9–10 320 AnTLcirValVis
2,2,3,3,4,4,5,5-Octafluoro-1-pentanol Sodium bis(2-ethylhexyl)sulfosuccinate Liu et al. [517] 311–325 11–30 10 SynVis
2,2,4-Trimethylpentane (isooctane) 2-Methylpropane (isobutane) Li et al. [496] 342–405 6.8–8.8 18 SynVisPcTc
2-Ethyl-1-hexanol 2-Ethylhexanoic acid Ghaziaskar et al. [314] 313–313 9.9–18 16 AnPTSemY
2-Propanol (isopropanol) Atenol Kikic et al. [422] 313–323 7.2–9.1 72.32 SynVisVar
Caffeine Kopcak et al. [442] 323–343 15.2–30 300 AnPTSemY
2-Sulfosalicylic acid p-Aminobenzoic acid Tian et al. [715] 308–328 8–21 100 AnPTSemY
3-Methyl-1-butanol Dodecanoic acid Garlapati et al. [310] 308–308 9.9–22.6 n.a. AnPTSemY
Hexadecanoic acid Garlapati et al. [311] 308–318 12.8–22.6 n.a. AnPTSemY
Octadecanoic acid Garlapati et al. [311] 308–318 12.8–22.6 n.a. AnPTSemY
Tetradecanoic acid Garlapati et al. [310] 308–318 9.9–22.6 n.a. AnPTSemY
2-Phenylethanol Lopes et al. [525] 287–315 7–15 35 AnTVal
4-Isobutylacetophenone 1-n-Butyl-3-methylimidazolium tetrafluoroborate Kuehne et al. [451] 310–370 1.7–12.5 3.5 SynVisVar
[bmim][BF4 ]
Kuehne et al. [454] 278–368 0.5–14 3.5 SynVisVar
4-Phenyl phenol 2,3,5-Trimethyl phenol Ravipaty et al. [611] 308–308 10.1–28 1.6 AnPTSemYVal
Acetic anhydride ␣-Methylbenzyl alcohol Calvo et al. [208] 283–363 1.4–10.5 n.a. SynVis
Acetophenone 1-n-Butyl-3-methylimidazolium tetrafluoroborate Kuehne et al. [452] 278–368 0.5–13 3.5 SynVisVar
[bmim][BF4 ]
43
44
Acetylsalicylic acid Benzoic acid Ravipaty et al. [612] 308–328 10.1–28 1.6 AnPTSemYVal
Salicylic acid Ravipaty et al. [612] 308–328 10.1–28 1.6 AnPTSemYVal
␣-Methylbenzyl acetate Acetic acid (ethanoic acid) Calvo et al. [208] 282–363 1.2–5.9 n.a. SynVis
␣-Phellandrene Polystyrene Xu et al. [771] 393–393 6.5–18 21 SynVis
Argon 2-Propanol (isopropanol) Lazzaroni et al. [480] 313–313 6.9–15 103 SynTVisVar
␤-Carotene Freeze dried carrots Saldana et al. [87] 313–323 12–20 n.a. AnPTSemY
Benzene 1-n-Butyl-3-methylimidazolium hexafluorophosphate Machida et al. [69] 313–333 5.4–14.8 n.a. AnPTChro
[bmim][PF6 ]
Benzil (1,2-diphenylethane-1,2-dione) 1-n-Butyl-3-methylimidazolium hexafluorophosphate Sakellarios et al. [626] 308–308 6.5–10.5 n.a. SynTVisSpec
[bmim][PF6 ]
Benzoic acid Poly(ethylene glycol) Kong et al. [439] 313–313 9.5–9.5 3.3 AnPTChro
Kong et al. [439] 313–313 9.5–9.5 3.3 AnPTChro
Bisphenol A Diphenylcarbonate Margon et al. [39] 403–453 30–30 65 AnTY
C.I. Disperse Blue 79 Poly(ethylene) terephthalate Banchero et al. [64] 353–393 18–24 1000 AnT
Ferri et al. [820] 353–393 18–24 1000 AnT
C.I. Disperse Orange 13 Poly(ethylene terephtalate) van der Kraan et al. [28] 368–388 16.5–26.4 40,000 AnT

C.I. Disperse Orange 3 Poly(ethylene terephtalate) van der Kraan et al. [28] 358–398 16.5–28.7 40,000 AnT
Poly(ethylene) terephthalate Ferri et al. [820] 353–393 16–24 1000 AnT
C.I. Disperse yellow 55 Dimethyl sulfoxide Tsai et al. [720] 353–353 20–30 33 AnPTSemY
Carbon monoxide Acetonitrile (ethanenitrile) Lopez-Castillo et al. [526] 298–313 4.1–9 n.a. AnTVarVis
Ceramide 3A (N-linoeoyl-phytosphingosine, 97%) Cholesterol Vezzù et al. [742] 370–413 3.6–6 n.a. SynNon
Chlorobenzene 1-n-Butyl-3-methylimidazolium hexafluorophosphate Machida et al. [69] 313–333 5.1–14.6 n.a. AnPTChro
[bmim][PF6 ]
Chlorodifluoromethane (HCFC-22) Poly(␧-caprolactone) Byun et al. [202] 322–496 59.1–276 28 SynVisVar
Cholesteryl benzoate (CBE) Cholesteryl butyrate (CBU) Huang et al. [56] 308–328 12–24 377 AnPTSemY
Choline chloride Urea Li et al. [499] 313–333 0.8–12.7 50 AnTVarVis
Cyclohexane Cyclohexanol Esmelindro et al. [284] 293–343 4.4–14.2 27 SynVisVar
Cyclohexanone Esmelindro et al. [284] 293–343 4.1–11.5 27 SynVisVar
Cyclohexanone Cyclohexanol Esmelindro et al. [284] 293–343 5.1–13.6 27 SynVisVar
Cyclohexene oxide Poly(cylclohexene carbonate) van Schilt et al. [735] 367–464 115–363 n.a. SynVisVar
Cyclohexylbenzene Polystyrene Xu et al. [771] 393–393 6.5–18 21 SynVis
Decahdydronaphthalene Polystyrene Xu et al. [771] 313–453 6.5–18 21 SynVis
Decahydroquinoline Polystyrene Xu et al. [771] 393–393 6.5–18 21 SynVis
Decyl acrylate Poly(decyl acrylate) Byun et al. [201] 321–479 15.9–209.6 28 SynVisVar
Decyl methacrylate Poly(decyl methacrylate) Byun et al. [201] 314–458 22.1–233.2 28 SynVisVar
Dibenzofuran Acetic acid Perez et al. [601] 318–338 10.3–20.5 15 SynVisVar
Dichloromethane (HCC-30) Lovastatin Oh et al. [582] 303–333 8.8–40.7 31 SynVisVar
Poly(vinyl pyrrolidone) Shin et al. [680] 313–363 3.2–25.5 25 SynVisVar
Simvastatin Oh et al. [582] 303–333 6.4–39.4 31 SynVisVar
Dicyclohexyl Polystyrene Xu et al. [771] 393–393 6.5–18 21 SynVis
Difluoromethane (HFC-32) 1,1,1,2,2-Pentafluoroethane (HFC-125) Ribeiro et al. [614] 306–344 4.9–7.3 5 SynNonPcTc
Dimethyl sulfoxide C.I. Disperse Violet 1 Tsai et al. [721] 353–353 20–30 n.a. AnPTSemY
Dimethylsulfoxide Dextran Perez de Diego et al. [599] 282–363 1.2–12 30 SynVisVar
Diphenyl(4-phenyl)phenylphosphine Peracetylated ␤-cyclodextrin Filardo et al. [48] 313–313 35.2–35.2 23.4 AnTIns
Ethane 1-Ethyl-3-methylimidazolium ethyl sulfate Petermann et al. [79] 298–298 2–4 n.a. AnGravSynT
[emim][EtSO4 ]
Ethyl acetate ␤-Carotene Borges et al. [195] 303–343 2.5–10.1 27 SynVisVar
Ethyl heptanoate Bisphenol A diglycidyl ether Medina-Gonzalez et al. [544] 318–318 14.5–14.5 10 AnT
Triglycidyl p-aminophenol Medina-Gonzalez et al. [544] 318–318 14.5–14.5 10 AnT
Ethyl lactate Sclareol Tombokan et al. [717] 308–308 1.3–13.7 24 SynVis
Ethyl nonanoate Bisphenol A diglycidyl ether Medina-Gonzalez et al. [544] 318–318 14.5–14.5 10 AnT
Ethyl nonanoate Triglycidyl p-aminophenol Medina-Gonzalez et al. [544] 318–318 14.5–14.5 10 AnT
Ethyl oleate Bisphenol A diglycidyl ether Medina-Gonzalez et al. [544] 318–318 14.5–14.5 10 AnT
Ethyl p-hydroxybenzoate Ethyl p-aminobenzoate Li [498] 308–328 8–21 100 AnPTSemY
Ethyl undecanoate Bisphenol A diglycidyl ether Medina-Gonzalez et al. [544] 318–318 14.5–14.5 10 AnT
Ethylbenzene Styrene Zhang et al. [792] 303–341 6.3–11.7 50 SynVisVarPcTc
Ethylcyclohexane Polystyrene Xu et al. [771] 393–393 6.5–18 21 SynVis
Ethylene carbonate Bisphenol A diglycidyl ether Medina-Gonzalez et al. [544] 318–318 14.5–14.5 10 AnT
␥-Linolenic acid Poly(ethylene glycol) Kong et al. [67] 308–343 9–30 3.3 AnPTChro
␥-Linolenic acid ethyl ester Poly(ethylene glycol) Kong et al. [67] 313–343 9–16 3.3 AnPTChro
␥-Linolenic acid methyl ester Poly(ethylene glycol) Kong et al. [67] 313–343 8–16 3.3 AnPTChro
Glycerol carbonate Bisphenol A diglycidyl ether Medina-Gonzalez et al. [544] 318–318 14.5–14.5 10 AnT
Glycerol carbonate acetate Bisphenol a diglycidyl ether Medina-Gonzalez [544] 318–318 14.5–14.5 10 AnT
Glycidyl methacrylate Propane Franceschi et al. [301] 303–343 1.8–7..2 25 SynVisVar
Heptadecafluorodecyl methacrylate Poly(heptadecafluorodecyl acrylate) Shin et al. [673] 303–363 6.7–25.2 25 SynVisVar

Heptadecafluorodecyl methacrylate (HDFDMA) Poly(heptadecafluorodecyl methacrylate Shin et al. [677] 303–363 6.5–26.3 25 SynVisVar
(poly(HDFDMA))
Isobutyl acrylate Poly(isobutyl acrylate) Byun et al. [204] 303–428 7–182.2 28 SynVisVar
Isobutyl methacrylate Poly(isobutyl methacrylate) Byun et al. [204] 316–435 23.4–204.6 28 SynVisVar
Isopropyl acrylate Poly(isopropyl acrylate) Byun et al. [206] 377–455 69.3–242.9 28 SynVisVar
Isopropyl benzoate Polystyrene Xu et al. [771] 393–393 6.5–18 21 SynVis
Isopropyl methacrylate Poly(isopropyl methacrylate) Byun et al. [206] 314–443 6.6–221.6 28 SynVisVar
Limonene Linalool Raeissi et al. [607] 293–349 5–14 3.5 SynVisVar
Methane 1-Ethyl-3-methylimidazolium ethyl sulfate Petermann et al. [79] 298–298 2–4 n.a. AnGravSynT
[emim][EtSO4 ]
Ethane Le et al. [481] 173–183 1.2–2.2 n.a. SynVis
Nitrogen Le et al. [481] 173–183 1.2–2.2 n.a. SynVis
Methyl caprylate Bisphenol A diglycidyl ether Medina-Gonzalez et al. [544] 318–318 14.5–14.5 10 AnT
Methyl laurate Bisphenol A diglycidyl ether Medina-Gonzalez [544] 318–318 14.5–14.5 10 AnT
Methyl linoleate Bisphenol A diglycidyl ether Medina-Gonzalez et al. [544] 318–318 14.5–14.5 10 AnT
Methyl methacrylate Poly(methyl methacrylate) Görnert et al. [322] 338–338 10–15 200 AnTSpec
Görnert et al. [322] 338–353 10–15 60 SynVisVar
Methyl myristate Bisphenol A diglycidyl ether Medina-Gonzalez et al. [544] 318–318 14.5–14.5 10 AnT
Methyl oleate Bisphenol A diglycidyl ether Medina-Gonzalez et al. [544] 318–318 14.5–14.5 10 AnT
Tocopherol Fang et al. [289] 313–353 10–29 30 AnTValVis
Methyl palmitate Bisphenol A diglycidyl ether Medina-Gonzalez et al. [544] 318–318 14.5–14..5 10 AnT
Methyl stearate Bisphenol A diglycidyl ether Medina-Gonzalez [544] 318–318 14.5–14.5 10 AnT
Methylcyclohexane Polystyrene Xu et al. [771] 393–393 6.5–18 21 SynVis
N,N-Dimethylacrylamide C.I. Disperse Blue 79 Santos et al. [630] 308–358 7–15.7 28 SynVisVar
C.I. Disperse Red 60 Santos et al. [630] 308–358 7–16.3 28 SynVisVar
(1-amino-4-hydroxy-2-phenoxy-9,10-anthraquinone)
Naphthalene 1-n-butyl-3-methylimidazolium hexafluorophosphate Machida et al. [69] 313–353 5.1–14.6 n.a. AnPTChro
[bmim][PF6 ]
Phenanthrene Tian et al. [716] 308–308 8–20 377 AnPTSemY
Polymethylmethacrylate Üzer et al. [730] 308–318 8–15 60 AnTVis
n-Butane Poly(octyl acrylate) Byun et al. [99] 373–453 2.9–13.9 28 SynVisVar
n-Hexane Naphthalene AlNashef et al. [108] 313–353 2–8.9 100 SynVisVar
45
n-Hexylcyclohexane Polystyrene Xu et al. [771] 393–393 6.5–18 21 SynVis
46
Nitrogen 2,2,4-Trimethylpentane (isooctane) Zhang et al. [790] 273–273 3.7–3.9 474 AnT
Polyethylene terephthalate Faridi et al. [50] 323–373 5–12 45 AnTMla
N-Methyl-2-pyrrolidone Potassium aurocyanide Rajasingam et al. [609] 308–308 5–11.8 150 AnT
N-Methyldiethanolamine (MDEA) N-Methylpyrrolidone Jou et al. [394] 273–423 0.1–19 n.a. AnT
n-Octane Thiophene Elizalde-Solis et al. [279] 334–383 3–14 100 AnTCapValVis
n-Pentane Isotactic poly(4-methyl-1-pentene) Fang et al. [288] 297–360 10.7–44.5 n.a. SynVisVar
Thiophene Elizalde-Solis et al. [279] 333–383 3–10.4 100 AnTCapValVis
n-Tetradecane Polystyrene Xu et al. [771] 393–393 6.5–18 21 SynVis
Octyl acrylate Poly(octyl acrylate) Byun et al. [99] 308–454 7–213.9 28 SynVisVar
Octyl methacrylate Poly(octyl acrylate) Byun et al. [99] 305–472 6.3–222.5 28 SynVisVar
o-Hydroxybenzoic acid Poly(methyl methacrylate) Diankov et al. [261] 313–313 12–20 100 AnT
Oleic acid Squalene Ruivo et al. [51] 313–333 14–22 n.a. AnPTcon
Oxygen Acetonitrile (ethanenitrile) Lopez-Castillo et al. [526] 313–313 0.6–8.2 n.a. AnTValVis
p-Aminobenzoic acid o-Phthalic acid Tian [716] 308–328 8–21 377 AnPTSemY
Perfluorohexane (PFC-72) Toluene Draucker et al. [269] 313–313 1.1–3.5 103 SynTVisVar
Perhydrofluorene Polystyrene Xu et al. [771] 393–393 6.5–18 21 SynVis

Phenol Bisphenol A Margon et al. [39] 403–453 30–30 65 AnTY
Diphenylcarbonate Margon et al. [39] 353–453 30–30 65 AnTY
Margon [39] 353–453 4.8–9.8 3.5 SynVisVar
p-Methylbenzen sulfonic acid Ethyl acetate Zhang et al. [807] 308–308 8–21 100 AnPTSemY
p-Nitrobenzoic acid Cyclohexane Tian et al. [714] 308–308 8–21 377 AnPTSemY
Poly(2-ethylhexyl acrylate) 2-Ethylhexyl acrylate Liu et al. [519] 303–454 7.7–248.4 28 SynVisVar
Poly(2-ethylhexyl methacrylate) 2-Ethylhexyl methacrylate Liu et al. [519] 314–477 9.6–247 28 SynVisVar
Poly(␧-caprolactone) (Mw = 124 200) Dichloromethane (HCC-30) Kalogiannis et al. [404] 308–373 3.4–19.7 26.75 SynVisVar
Trichloromethane (HCC-20) Kalogiannis et al. [404] 308–373 4.1–20.8 26.75 SynVisVar
Poly(ethylene glycol)200 1-Octanol Hou et al. [356] 303–323 0.9–8.2 50 AnTBloVisVar
1-Pentanol Hou et al. [356] 303–323 1–8.2 50 AnTBloVisVar
Poly(l-lactic acid) (MW = 189 000) Dichloromethane (HCC-30) Kalogiannis et al. [403] 308–373 3.4–24 26.75 SynVisVar
Poly(methyl methacrylate) Yao et al. [773] 298–298 0.3–5.5 n.a. AnGrav
Propane Camphor Carvalho et al. [210] 304–354 2.4–15 25.0 SynVisVar
Poly(octyl acrylate) Byun et al. [99] 326–453 10.5–27.7 28 SynVisVar
Sunflower oil Hegel et al. [345] 308–308 2.8–6.2 80 AnTCapVis
Propene Poly(octyl acrylate) Byun et al. [99] 334–453 11.5–28.1 28 SynVisVar
Propyl p-hydroxybenzoate Cyclohexane Jin et al. [392] 308–308 8–23 377 AnPTSemY
Propylene carbonate Bisphenol A diglycidyl ether Medina-Gonzalez et al. [544] 318–318 14.5–14.5 10 AnT
Salicylic acid Benzoic acid Ravipaty et al. [612] 308–328 10.1–28 1.6 AnPTSemYVal
Solvent brown 1 Poly(ethylene) terephthalate Ferri et al. [820] 353–393 14–24 1000 AnT
Tert-butyl acrylate Poly(tert-butyl acrylate) Byun et al. [204] 319–457 20.2–206.3 28 SynVisVar
Tert-butyl methacrylate Poly(tert-butyl methacrylate) Byun et al. [204] 314–463 6.2–257.5 28 SynVisVar
Tetrhydronaphthalene Polystyrene Xu et al. [771] 393–393 6.5–18 21 SynVis
Thiophene 1-Propanol Elizalde-Solis et al. [277] 314–363 1.8–12.5 100 AnTCapValVisPc
n-Decane Elizalde-Solis et al. [278] 334–383 2.5–15..3 100 AnTCapValVis
n-Nonane Elizalde-Solis et al. [278] 334–383 1.9–15.1 100 AnTCapValVis
Toluene 1-n-Butyl-3-methylimidazolium hexafluorophosphate Machida et al. [69] 313–333 5.3–14.8 n.a. AnPTChro
[bmim][PF6 ]
Triarachidonin Poly(ethylene glycol) Kong et al. [437] 313–313 9.9–30.2 3.19 AnPTChro
Kong et al. [438] 313–313 9.9–30.2 3.19 AnPTChro
Trierucin Poly(ethylene glycol) Kong et al. [437] 308–323 8.2–30 3.19 AnPTChro
Kong et al. [437] 308–323 8.2–30 3.19 AnPTChro
Tri-n-butylphosphate Benzoic acid Wang et al. [754] 313–313 12.1–12.1 n.a. SynVis
Trinervonin Poly(ethylene glycol) Kong et al. [437] 308–323 9–30 3.19 AnPTChro
Kong et al. [438] 308–323 9–30 3.19 AnPTChro
Weyburn oilfield light crude oil Asphaltene Nobakht et al. [579] 300–300 4.8–4.8 310 SynVis
Table 40
Ternary systems: water + methane + X.
1,1-Dimethylcyclohexane Hara et al. [338] 274–289 1–6.7 150 SynNon

1-Propanol Maekawa [536] 274–286 2.6–11 1000 SynNon
Mohammadi and Richon [553] 273–279 2.4–5.1 n.a. SynNon
2,2-Dimethylbutane Ohmura et al. [583] 254–272 0.5–1 200 SynNon
2,2-Dimethylpentane Kozaki et al. [447] 273–279 2.4–4.8 236 SynNon
2-Methyltetrahydrofuran Ohmura et al. [584] 273–285 2.5–9.6 200 SynNon
2-Propanol (isopropanol) Maekawa [536] 274–287 2.2–11 1000 SynNon
3-Methyltetrahydropyran Ohmura et al. [584] 273–282 1.2–3.8 200 SynNon
Aniline Ventura et al. [739] 303–369 9.1–73.9 30 SynVisVar
Calcium chloride Atik et al. [178] 265–282 3–22.9 n.a. SynNon
Mohammadi et al. [554] 268–283 2.8–9 57.5 SynNonVis
Carbon dioxide Beltrán and Servio [97] 275–285 1.9–7.4 150 SynVisVar
Qin et al. [605] 324–375 10.7–49.9 200 AnT
Cyclopropane Makino et al. [537] 291–291 0.9–18.7 n.a. AnTVis
Makino et al. [537] 291–291 1–15.1 n.a. SynVisSpec
Diethylene glycol Afzal et al. [166] 274–282 5–8 n.a. SynNon
Ethane Kumar et al. [457] 273–273 1.4–1.4 n.a. SynNon
Wu and Englezos [766] 276–279 1.9–2.7 21.6 AnTVis
Ethanol Mohammadi et al. [556] 271–280 2.9–7.4 58 SynNon
Ethene Zhang et al. [793] 273–278 2.5–5.5 256 AnTVis
Ethylbenzene Coquelet et al. [231] 297–393 0.5–6.8 n.a. AnTCapValVis
Ethylene glycol Abdi et al. [163] 263–283 15–30 n.a. AnT
Ethylene glycol (MEG) Folas et al. [299] 278–298 5–20 451 AnTVar
Hydrogen Ma et al. [529] 274–274 3.8–5.5 256 AnT
Hydrogen Skiba et al. [685] 266–313 0.1–250 n.a. SynNon
Magnesium chloride Atik et al. [178] 270–292 3.4–22.6 n.a. SynNon
Methylcyclohexane Ohmura et al. [583] 251–272 0.5–1.2 200 SynNon
Susilo et al. [705] 275–275 0.1–2 n.a. AnTVis
Neohexane Susilo et al. [705] 275–275 0.1–2 n.a. AnTVis
n-Heptane Susilo et al. [705] 275–275 0.1–2 n.a. AnTVis
n-Propanol Chapoy et al. [126] 276–293 3.5–37.6 500 SynNon
p-toluene sulfonic acid Rovetto et al. [127] 277–280 4–5 200 SynNon
Potassium chloride Mohammadi et al. [554] 270–283 2.7–8.8 57.5 SynNonVis
Propane Kumar et al. [457] 273–273 0.5–0.5 n.a. SynNon
Sodium dodecyl sulfate Gayet et al. [313] 275–300 3.1–55 250 SynNonVis
Lee et al. [486] 276–281 3.7–5.9 474 SynNon
Watanabe et al. [759] 275–293 0.1–3.9 19.6 SynNon
Tert-butyl methyl ether Ohmura et al. [583] 252–270 0.6–1.2 200 SynNon
Susilo et al. [705] 275–275 0.1–2 n.a. AnTVis
Tetrafluoromethane (CF4) Kunita et al. [470] 291–291 18.5–90 0.2 SynVisSpec
Tetrafluoromethane (CFC-14) Mooijer-van den Heuvel et al. [560] 272–289 2–14 3.5 SynVisVar
Tetra-n-butyl ammonium bromide Li et al. [491] 281–295 0.4–10.2 n.a. SynVisVar
Toluene Valtz et al. [733] 297–392 0.5–10.7 n.a. AnTCapValVis
Triethylene glycol Afzal et al. [165] 264–275 3–5.1 58 SynNon
Trifluoromethane (HFC-23) Mooijer-van den Heuvel et al. [560] 274–303 1–14 3.5 SynVisVar
Xylene Coquelet et al. [231] 298–393 0.5–0.5 n.a. AnTCapValVis
Table 41
Ternary systems: water + ethane + X.
2-Propanol (isopropanol) Mohammadi and Richon [553] 277–281 0.6–1.1 n.a. SynNon
Argon Maekawa [535] 273–276 0.4–1 700 AnTVis
Diethanolamine (DEA) Jou and Mather [396] 298–398 0–13.2 n.a. AnTVcir
Ethylene glycol Mohammadi et al. [557] 269–281 0.4–1.7 58 SynNon
Krypton Maekawa [535] 273–276 0.4–1 700 AnTVis
Methane Kumar et al. [457] 273–273 1.4–1.4 n.a. SynNon
Methanol Mohammadi et al. [557] 268–280 0.5–2.6 58 SynNon
Monoethanolamine (MEA) Jou and Mather [396] 298–398 0–13.1 n.a. AnTVcir
Triethylene glycol Mohammadi et al. [557] 274–281 0.5–1.7 58 SynNon
Xenon Maekawa [535] 276–278 0.2–0.8 700 AnTVis
Table 42
Ternary systems: water + propane + X.
2-Propanol (isopropanol) Mohammadi and Richon [553] 274–278 0.1–0.3 n.a. SynNon
Argon Maekawa [535] 273–276 0.1–0.7 700 AnTVis
Calcium chloride Mohammadi et al. [554] 271–276 0.1–0.4 58 SynNonVis
Krypton Maekawa [535] 273–278 0.1–0.5 700 AnTVis
Methane Kumar et al. [457] 273–273 0.5–0.5 n.a. SynNon
Sodium chloride Mohammadi et al. [554] 271–275 0.2–0.4 57.5 SynNonVis
Sodium dodecyl sulfate Zhang et al. [789] 270–278 0.4–0.5 474 AnTVis
Table 43
Ternary systems: water + hydrogen + X.
Carbon dioxide Kumar et al. [456] 273–281 1.5–10.7 n.a. AnTVis

Dimethylcyclohexane Duarte et al. [272] 274–279 60.1–95 n.a. SynVis
Methane Ma et al. [529] 274–274 3.8–5.5 256 AnT
Skiba et al. [685] 266–313 0.1–250 n.a. SynNon
Methyl tert-butyl ether Duarte et al. [272] 269–272 70.1–100.1 n.a. SynVis
Methylcyclohexane Duarte et al. [272] 274–275 83.1–100.1 n.a. SynVis
Tetrabutyl ammonium bromide Arjmandi et al. [176] 280–288 4.2–23 2400 SynNon
Tetrahydrofuran Hashimoto et al. [112] 277–281 0.1–13.3 150 SynVisSpec
Hashimoto et al. [342] 273–280 0–13.8 150 SynVisSpec
Nagai et al. [566] 269–275 3.6–8.4 130 SynTVis
Ogata et al. [150] 277–277 0.1–72 10.0 SynT
Tetra-n-butyl ammonium bromide Hashimoto et al. [112] 277–281 0.1–13.3 150 SynVisSpec
Hashimoto et al. [343] 279–285 0.5–12.7 150 SynNonVis
Tetra-n-butyl ammonium fluoride Sakamoto et al. [625] 298–302 0.2–37.6 150 SynNonVis
Tetra-n-butyl ammonium bromide Strobel et al. [692] 279–279 13.8–13.8 20 AnT
in polymer–solvent systems [99,100]. Koh et al. [101] used the mental apparatus is built around an autoclave cell, made of stainless
synthetic-visual method to study acid-in-CO2 emulsions for super- steel and equipped with two sapphire windows through which
critical fluid surface decontamination (SFSD) of radioactive metal the studied sample can be observed with the help of a polarizing
wastes. microscope coupled with a video camera. This technique allows the
Concerning the design of the view cell either an autoclave with detection of very small crystals, up to 2 ␮m in length, even when
one or more windows is used or a tube made from a transparent their concentration is too low for other approaches.
material (e.g., pyrex glass). Most equilibrium cells are made of stainless steel or Nickel based
When only small quantities of a sample shall be used for an high-performance alloys, like Hastelloy C4, e.g. [95]. Gregorow-
experiment in a rather larger high-pressure view cell, e.g. to observe icz [104] selected titanium as material for his variable volume
solid–liquid–gas equilibria, a glass capillary can be placed inside a view-cell. As the reason he gives the comparatively low weight,
high-pressure view cell [95,102]. unfortunately, without reporting the actual weight of the cell.
Milhet et al. [103] used a very small cell with a volume The Cailletet apparatus of TU Delft [105] is the most frequently
of 0.03 cm3 for the visual observation of melting points and used type of apparatus for high-pressure phase equilibrium mea-
solid–liquid equilibria on n-alkanes at high pressures. The experi- surements. It consists of a thick-walled Pyrex glass tube (50 cm
Table 44
Ternary systems: water + krypton + X.

2-Methyl-2-propanol Imai et al. [376] 266–293 0.1–4.7 70.7 SynNon
2-Propanol (isopropanol) Imai et al. [376] 267–289 0.3–4.9 70.7 SynNon
2-Propanone Imai et al. [376] 268–291 0.1–4.9 70.7 SynNon
Cyclopentane Takeya and Ohmura [707] 283–308 0.1–7.6 200 SynNon
Cyclopentene Takeya and Ohmura [707] 280–297 0.1–2 200 SynNon
Ethane Maekawa [535] 273–276 0.4–1 700 AnTVis
Fluorocyclopentane Imai et al. [375] 286–308 0.1–4.8 70.7 SynNon
Propane Maekawa [535] 273–278 0.1–0.5 700 AnTVis
Tetrahydropyran Takeya and Ohmura [707] 278–296 0.1–2 200 SynNon
Table 45
Ternary systems: water + X + Y.
1,1,1,2-Tetrafluoroethanie (HFC-134a) Bis(2,2,3,3,3-pentatfluoropropyl)2- Liu et al. [523] 303–332 0.1–38 n.a. SynVisVar
sulfosuccinate
Bis(2,2,3,4,4,4-hexafluorobutyl)2- Liu et al. [523] 307–337 0.2–38 n.a. SynVisVar
sulfosuccinate
1-Butanol 1-n-Butyl-3-methylimidazolium Najdanovic-Visak 254–346 0.1–4.2 24 SynVisVar
bis(trifluoromethanesulfonyl)imide et al. [570]
2-Propanol (isopropanol) Sodium acetate Bermejo et al. [188] 396–459 0.4–1.8 n.a. SynVis
Sodium oleate Bermejo et al. [188] 400–459 0.4–1.6 n.a. SynVis
Ammonia Lithium bromide Wu et al. [768] 287–356 0–2.6 769 AnT
Lithium nitrate Libotean et al. [502] 293–353 0–2 166 SynT
Methanol Schäfer et al. [635] 313–393 0–1.5 1600 AnT
Decalin Tetralin Brunner et al. [197] 524–664 4.4–28.5 30 SynVis
Difluoromethane (HFC-32) 2-Methyl-2-propanol Imai et al. [376] 268–287 0.1–1.1 70.7 SynNon
2-Propanone Imai et al. [376] 268–284 0–0.7 70.7 SynNon
Cyclopentane Imai et al. [374] 280–299 0–1.5 70 SynNon
Fluorocyclopentane Imai et al. [375] 288–299 0.1–1 70.7 SynNon
Tetra-n-butylammonium bromide Imai et al. [374] 286–289 0.1–1.2 70 SynNon
Diglycolamine (DGA) Benzene Valtz et al. [732] 292–393 0–0.4 n.a. SynTVis
Ethylbenzene Diglycolamine (DGA) Coquelet et al. [231] 294–394 0–0.3 n.a. SynTVis
Methyldiethanolamine (MDEA) Benzene Valtz et al. [732] 291–402 0–0.6 n.a. SynTVis
Methylfluoride Cyclopentane Takeya et al. [709] 287–305 0.1–2.9 138.2 SynNon
Cyclopentene Takeya et al. [709] 283–300 0.1–1.9 138.2 SynNon
Fluorocyclopentane Takeya et al. [709] 290–307 0.1–2.5 138.2 SynNon
Methylcyclohexane Takeya and Ohmura 273–294 0.1–2.7 202 SynNon
[708]
Tetrahydrofuran Takeya et al. [709] 284–301 0.1–1.8 138.2 SynNon
Natural gas n-Propanol Chapoy et al. [126] 289–290 9.9–10 500 SynNon
Nitrogen Ethylene glycol Abdi et al. [163] 263–283 15–20 n.a. AnT
Propene 2-Propanol (isopropanol) Grigiante et al. [326] 313–313 1.3–1.6 80 AnTCapValVis
Synthetic natural gas p-Toluene sulfonic acid Rovetto et al. [127] 285–3 285–3 200 SynNon
Toluene Diglycolamine Valtz et al. [733] 292–394 0–0.3 n.a. SynTVis
Methyldiethanolamine Valtz et al. [733] 295–392 0–0.3 n.a. SynTVis
Trans-decalin Cis-Decalin Brunner et al. [197] 521–647 4.2–22 30 SynVis
Xenon 1,1-Dimethylcyclohexane Sugahara et al. [702] 274–301 0.1–2.7 10 SynVis
Cis-1,2-Dimethylcyclohexane Sugahara et al. [702] 274–283 0.1–0.4 10 SynVis
Trans-1,2-dimethylcyclohexane Sugahara et al. [702] 274–283 0.1–2.7 10 SynVis
Table 46
Ternary systems: methane + X + Y.
1-Butene 2-Methylpropane (isobutane) Li et al. [496] 336–380 6.5–10 18 SynVisPcTc

2,2,4-Trimethylpentane (isooctane) 2-Methylpropane (isobutane) Li et al. [496] 344–417 7.2–11.4 18 SynVisPcTc
Ethanol Tetrahydrofuran Luo et al. [45] 274–300 2.7–9.4 360 AnTLcirBloVar
Methanol Benzene Xia et al. [769] 288–303 1.9–12 30 SynVisVar
Cyclohexane Xia et al. [769] 303–303 2–11.9 30 SynVisVar
Methylbenzene Xia et al. [769] 288–303 2–12 30 SynVisVar
n-Heptane Xia et al. [769] 303–303 1.9–12 30 SynVisVar
n-Hexane Xia et al. [769] 303–303 2–12 30 SynVisVar
n-Decane Perfluoromethylcyclohexane Gozalpour et al. [320] 373–373 4.5–23 400 AnTVcirValVis
n-Hexane n-Decane Uribe-Vargas and Trejo [728] 258–298 0.9–18.8 n.a. AnTVal
long, 3 mm inner diameter) with the open end placed in an auto- be placed into a high-pressure vessel. An example is the apparatus
clave and immersed in mercury. The mercury confines the sample of Hong et al. [106] who used a thick-walled quartz tube containing
in the Cailletet tube. the sample that has a floating piston and is positioned in a win-
Transparent tubes are limited concerning their maximum pres- dowed, agitated, invertible, high-pressure cell. The floating piston
sures before they crack or burst. For higher pressures, the tube can separates the sample volume from a transparent overburden fluid.
Table 47
Ternary systems: ethene + X + Y.
n-Hexane Poly(ethylene) 150,00 Haruki et al. [100] 373–473 0.6–15.9 20 SynVisVar

Poly(ethylene) (LLDPE) Nagy et al. [568] 410–495 1.3–13.3 3.5 SynVisVar
Vinyl Poly(ethylene-co-methyl acrylate) Tumakaka et al. [725] 373–493 108–127.7 65 SynVisVar
acetate Poly(ethylene-co-methyl acrylate-co-vinyl acetate) Tumakaka et al. [725] 373–503 115–178 65 SynVisVar
50
Table 48
Ternary systems: X + Y + Z.
X Y Z Reference T (K) P (MPa) V (cm3 ) Method
1,1,1,2-Tetrafluoroethane (HFC-134a) 1,1-Difluoroethane (HFC-152a) Polystyrene Li et al. [73] 403–463 1.2–5.6 n.a. AnGrav
Ethanol Polystyrene Choudhary et al. [114] 423–460 1.3–9 n.a. SynVisCon
Methylsuccinic acid Itaconic acid Abbott et al. [89] 383–383 5–20.5 25 AnOth

1-Butene Chlorodifluoromethane (HCFC-22) Poly(␧-caprolactone) Byun et al. [202] 323–474 84.9–263.2 28 SynVisVar
Dimethyl ether Poly(␧-caprolactone) Byun et al. [202] 321–473 32.5–253.7 28 SynVisVar
Carbon monoxide Propylene carbonate n-Dodecane Shaharun et al. [146] 298–343 0.1–1.5 300 SynT
Difluoromethane (HFC-32) 1,1,1,2,2-Pentafluoroethane (HFC-125) 1,1,1,2-Tetrafluoroethane (HFC-134a) Kato and Nishiumi [40] 333–363 3.6–4.4 1200 AnTLcirVisVar
1,1,1,2-Tetrafluoroethane (HFC-134a) Kato and Nishiumi [40] 348–363 3.8–4.4 1200 SynVisVarPcTc
2-Methylpropane (isobutane) Propane Akasaka et al. [169] 260–290 0.1–1.2 n.a. AnTVLcirVal
Ethane Limonene Linalool Raeissi and Peters [608] 284–368 3–9.1 3.5 SynVis
Hydrogen Benzene Cyclohexane Tsuji et al. [722] 303–303 0.8–4.8 37 SynVis
Methylcyclohexane Tsuji et al. [107] 303–303 1.3–3.9 37 SynVis
Toluene Tsuji et al. [107] 303–303 1.5–4.2 37 SynVis
Cis-Decahydronaphthalene Naphthalene Tsuji et al. [723] 303–303 1.8–4.2 37 SynVis
Cyclohexane Methylcyclohexane Tsuji et al. [107] 303–303 1.2–4.2 37 SynVis
Cyclohexane Toluene Tsuji et al. [107] 303–303 1.2–3.9 37 SynVis
Methylcyclohexane Toluene Tsuji et al. [722] 303–303 1.3–4.4 37 SynVis
Propane 1-Hexadecanol Rovetto et al. [621] 303–450 2.9–14.3 3.5 SynVisVar
Propane 1-Hexadecanol Rovetto et al. [622] 310–450 7–14.7 3.5 SynVisVar
Propane 2-Propanol (isopropanol) Zevnik and Levec [788] 333–393 0.3–6.7 300 AnTX
Propane Methyl palmitate Rovetto et al. [622] 360–450 5–11.5 3.5 SynVisVar
Propylene carbonate n-Dodecane Shaharun et al. [146] 298–343 0.1–1.5 300 SynT
Trans-decahydronaphthalene Cis-Decahydronaphthalene Tsuji et al. [723] 303–303 1.8–4.3 37 SynVis
Trans-decahydronaphthalene Naphthalene Tsuji et al. [723] 303–303 1.9–4.2 37 SynVis
Propane 1-Hexadecanol Methyl palmitate Rovetto et al. [621] 341–450 2.2–9.9 3.5 SynVisVar
AOT surfactant Glycerol Benazzi et al. [186] 298–343 1.1–29.4 27 SynVisVar
Methanol 1-Hexadecanol Rovetto et al. [621] 351–450 2.9–10.5 3.5 SynVisVar
n-Butane 2-Methylpropane (isobutane) Kayukawa et al. [415] 240–380 0–3.5 n.a. SynNonVar
Chlorodifluoromethane (HCFC-22) Poly(␧-caprolactone) Byun et al. [202] 323–475 60.8–256.3 28 SynVisVar
Dimethyl ether Poly(␧-caprolactone) Byun et al. [202] 322–474 92.5–266.3 28 SynVisVar
Table 49
Multicomponent systems: carbon dioxide + water + X + Y (+. . .).
X(+Y +. . .) Reference T (K) P (MPa) V (cm3 ) Method
1-Butanol + 1-n-butyl-3-methylimidazolium Najdanovic-Visak et al. 295–333 6.8–96.5 24 SynVisVar

bis(trifluoromethanesulfonyl)imide [570]
2,2,3,3,4,4,5,5-Octafluoro-1-pentanol + sodium Liu et al. [517] 311–325 15.4–33.7 10 SynVis
bis(2-ethylhexyl)sulfosuccinate
2-Propanol (isopropanol) + argon + acetone Lazzaroni et al. [480] 313–313 6.9–15.1 103 SynTVisVar
3-Methylpentaethyleneglycol-2-octyl-1-n-pentylglycerol + 1,2- Sawada et al. [633] 318–318 20–20 4.6 SynVis
dihydroxyanthoraquinone
3-Methylpentaethyleneglycol-2-octyl-1-n-pentylglycerol + 3,4- Sawada et al. [633] 318–318 20–20 4.6 SynVis
dihydroxy-9,10-dioxo-2-anthoraquinonesulfonic acid sodium
salt
Ammonium carboxylate perfluoropolyether + oxymatrine Su et al. [695] 308–328 14.9–22.8 39.7 AnTCap
AOT surfactant + ethanol Wang and Wai [755] 308–318 16–19.5 20 SynVis
AOT surfactant + n-heptane + cobalt(II) chloride Wang and Wai [755] 323–323 18–20 20 SynVis
AOT surfactant + n-heptane + potassium permanganate Wang and Wai [755] 323–323 12.5–20 20 SynVis
AOT surfactant + n-octanol Wang and Wai [755] 308–318 18–25 20 SynVis
Ethanol + boldine de la Fuente et al. [248] 313–343 3.7–16.8 300 SynVisVar
Ethanol + boldine + catechin de la Fuente et al. [248] 313–343 3.6–16.6 300 SynVisVar
Ethanol + boldo leaf tincture de la Fuente et al. [248] 313–343 4.8–17.3 300 SynVisVar
Ethanol + caffeine Iwai et al. [379] 313–313 15–15 26.5 AnSpecVcir
Ethanol + catechin de la Fuente et al. [248] 313–343 3.5–16.6 300 SynVisVar
Nunes et al. [581] 313–313 15–19 30 AnTCapValVis
Ethanol + p-coumaric acid Nunes et al. [581] 313–313 15–19 30 AnTCapValVis
Ethoxylated nonyl phenol + nitric acid Koh et al. [101] 313–313 14–35 22.4 SynVisVar
Hydrogen + propane Kumar et al. [456] 274–282 2.5–9.7 n.a. AnTVis
Hydrogen + tetrahydrofuran Hashimoto et al. [341] 280–280 0.2–3.6 150 AnTVis
Methane + neohexane Beltrán and Servio [97] 275–285 1.3–6.1 150 SynVisVar
Methanol + sodium cloride Kamps et al. [406] 313–395 0.1–9.4 30 SynVis
Methanol + sodium sulfate Kamps et al. [405] 313–395 0.2–9.6 30 SynVis
Methanol + tetramethylammonium bicarbonate Levitin et al. [489] 298–343 1.5–27.1 20 SynVisVar
Nitrogen + cyclohexanol + cyclohexanone + cyclohexane Zhang et al. [797] 388–511 15.9–22.5 18 SynVisPcTc
Nitrogen + methane + ethane + propane + 2-methyl propane + Arjmandi et al. [176] 280–292 0.9–9.5 2400 SynNon
n-butane + 2-methyl butane + tetrabutyl ammonium bromide
nitrogen + tetrahydrofuran Linga et al. [511] 273–273 1.5–1.5 323 AnTVis
N-methyldiethanolamine (MDEA) + piperazine Jenab et al. [385] 313–343 0–3.9 1000 AnT
N-methyldiethanolamine (MDEA) + tetramethylensulfone Jenab et al. [385] 313–343 0–3.1 1000 AnT
N-methyldiethanolamine Jenab et al. [385] 313–343 0–3.1 1000 AnT
(MDEA) + tetramethylensulfone + piperazine
Quercetin-3-glucoside + ethanol Nunes et al. [581] 313–313 15–19 30 AnTCapValVis
Resveratrol + ethanol Nunes et al. [581] 313–313 15–19 30 AnTCapValVis
Sodium bis-(2,2,3,3,4,4,5,5-octafluoro-1-n-pentyl)-2- Koh et al. [101] 313–313 13–35 22.4 SynVisVar
sulfosuccinate + nitric
acid
Sodium bis(3,3,4,4,5,5,6,6,6-nonafluoro-1-hexanol) Liu et al. [522] 303–328 11–20 60 SynVis
sulfosuccinate + cadnium nitrate
Tri-n-butylphosphate + citric acid Wang et al. [754] 313–313 12–12.1 n.a. SynVis
Tri-n-butylphosphate + lactic acid Wang et al. [754] 313–313 12.1–12.1 n.a. SynVis
Trioxane + formaldehyde Tanaka and Ogino [710] 323–393 9.6–19.1 200 AnTY
To reduce time for equilibration most frequently magnetic stir- Using the synthetic-visual method (V = 100 cm3 ) Melnikov
rer bars are used, usually to agitate the liquid phase. Tsuji et al. et al. [113] reliably recorded for the first time the formation
[107] used a magnetic stirrer bar that is positioned in the top part of metastable (supercooled) water upon dissociation of propane
of their view cell, a pyrex glass tube. The Cailletet tubes of TU Delft hydrates in the temperature range 257–270 K.
[105] are agitated with a stainless steel ball driven by reciprocat- To measure the solubilities of gases or blowing agents in vis-
ing magnets. Visual cells equipped with a rocking mechanism to cous polymer melt systems the synthetic-visual method can be
facilitate the attainment of equilibrium are only rarely used, e.g. by used with a continous feed of the components by means of a foam-
AlNashef et al. [108]. ing extruder [114]. The solid polymer is melted in the extruder
To improve the detection of phase transitions, some authors (twin screw or single screw) and saturated with a gas or a blowing
used laser light scattering techniques [109,110]. Masui et al. [111] agent. An optical flow cell and a manually controlled valve were
introduced image analysis for the determination of the critical installed at the end of the extruder. Solubility data are generated
parameters of n-butane. Pictures taken from the variable-volume by observing/recording the onset of bubble formation/dissolution
view cell by a CCD camera were cut to the region where the phase in the gas-laden melt through the window using a microscope-CCD
behavior is observed best. The color image was then transformed camera-monitor/recorder system.
into a monochromatic image for determination of relative bright- Equivalent to analytical continous flow methods, continous-
ness (LR) of each picture. Using this method the existence of a feed synthetic-visual methods have the advantage of that the
meniscus can be detected in a reliable way. substances are kept only for a short time at the desired temper-
Some authors used spectroscopic methods to get additional ature, so that thermal degradation can be reduced when critical
information, e.g. Hashimoto et al. [112] confirmed by use of Raman points are measured at high temperatures. Gil et al. [115] describe
spectroscopy that H2 is enclathrated in the hydrate cages by a flow apparatus (SynVisConPcTc) that is suitable for the measure-
adding a small amount of tetrahydrofuran or tetra-n-butyl ammo- ment of critical points of pure components and of binary mixtures.
nium. The loading section consists of two thermostatic chromatography
Table 50
Multicomponent systems: carbon dioxide + X + Y (+. . .).
1,1,1-Trifluoroethane (HFC-143a) + 1,1,1,2,2-pentafluoroethane Esperança et al. [285] 305–344 3.7–7.2 5 SynNonPcTc

(HFC-125) + 1,1,1,2-tetrafluoroethane (HFC-134a)
1-Methyl-3-octylimidazolium dicyanamide[omim] Bogel-Lukasik et al. [194] 308–308 9–11 42.5 AnTValVis
N(CN)2] + 2-octanol + 4-(octan-2-yloxy)-4-oxobutanoic
acid + dioctan-2-yl succinate
1-Methyl-3-octylimidazolium hexafluorophosphate [omim] Bogel-Lukasik et al. [194] 308–308 9–11 42.5 AnTValVis
[PF6 ] + 2-octanol +4-(octan-2-yloxy)-4-oxobutanoic
acid + dioctan-2-yl succinate
4-Cyano-4 -n-pentyl-1,1 -biphenyl + 4-cyano-4 -n-heptyl-1,1 - Brás et al. [196] 313–333 8.8–18.6 35 AnTValVis
biphenyl + 4-cyano-4 -n-octyloxy-1,1 -biphenyl + 4-cyano-4 -n-
pentyl-1,1 ,1 -terphenyl
␣-Methylbenzyl acetate + ␣-methylbenzyl alcohol + acetic Calvo and de Loos [208] 283–363 2.3–7.1 n.a. SynVis
anhydride + acetic acid (ethanoic acid)
Anisole + acetic anhydride + p-methoxyacetophenone + acetic acid Ji et al. [389] 374–530 16.1–22.2 18 SynVisPcTc
(ethanoic acid)
Cyclohexane + cyclohexanone + cyclohexanol Esmelindro [284] 293–343 4.4–12.2 27 SynVisVar
Ethanol + dichloromethane (HCC-30) + theophylline Franceschi et al. [302] 303–343 5.8–10.4 27 SynVIsVar
Subra et al. [697] 309–309 11–11 n.a. SynVisVar
Ethanol + limonene + linalool Iwai et al. [44] 313–313 6.9–6.9 n.a. AnTLcirBlo
Iwai et al. [44] 313–313 6.9–6.9 n.a. AnPTSemY
Methane + ethane + 1-ethyl-3-methylimidazolium ethyl sulfate [emim] Petermann et al. [79] 298–298 2–4 n.a. AnTYGrav
[EtSO4 ]
Methane + ethane + propane + n-butane + methanol Ruffine et al. [27] 243–273 2–5 100 AnTVcirBloValVis
Methane + n-butane + n-decane Ayirala and Rao [129] 344–344 0.1–12.2 n.a. SynNon
Methane + neohexane + water Beltrán and Servio [97] 275–285 1.3–6.1 150 SynVisVar
n-Butane + n-pentane + n-hexane + n-heptane Qiu et al. [606] 310–473 3.9–10.6 39 SynVisPcTc
Nitrogen + methane + ethane + propane + 2-methylpropane Zhou et al. [811] 231–340 3.1–19.6 70 SynNon
(isobutane) + n-butane + 2-methylbutane (isopentane) + n-pentane
n-Octane + n-hexadecane + methylcyclohexane + cis- Vitu et al. [744] 292–373 1.9–16.5 30 SynVisVar
decalin + methylbenzene
Phenanthrene + anthracene + carbazole Esmaeilzadeh and 318–318 11.1–20.1 n.a. AnPTSemY
Goodarznia [283]
Phenol + bisphenol A + diphenylcarbonate Margon et al. [39] 343–473 30–30 65 AnTY
Phenol + bisphenol A + diphenylcarbonate Margon et al. [39] 343–473 3.2–11.2 3.5 SynVisVar
p-Methylbenzen sulfonic acid + ethyl acetate + ethanol Zhang et al. [807] 308–308 8–21 100 AnPTSemY
p-Nitrobenzoic acid + cyclohexane + acetone Tian et al. [714] 308–308 8–21 377 AnPTSemY
Propyl p-hydroxybenzoate + cyclohexane +acetone Jin et al. [392] 308–308 8–23 377 AnPTSemY
Tristearin + phosphatidylcholine + dioctyl sulfosuccinate Spilimbergo et al. [123] 308–326 1–5.8 n.a. SynNon
Water + 1-butanol + 1-n-butyl-3- Najdanovic-Visak et al. 295–333 6.8–96.5 24 SynVisVar
methylimidazoliumbis(trifluoromethanesulfonyl)imide [570]
Table 51
Multicomponent systems: methane + X + Y (+. . .).
Diglycolamine (DGA) + benzene + water Valtz et al. [732] 298–393 0.5–5 n.a. AnTCapValVis
Ethane + propane + 2-methylpropane(isobutane) + Mørch et al. [562] 236–278 0.3–9.4 n.a. SynVis
n-butane + n-pentane
Ethane + propane + water Kumar et al. [457] 273–273 0.7–0.7 n.a. SynNon
Ethane + water + glycerol Wu and Englezos [766] 274–281 2.1–4.7 21.6 AnTVis
Ethane + water + n-butane Mohammadi et al. [551] 277–292 0.5–3.2 34 AnTValVis
Ethane + water + p-toluene sulfonic acid Rovetto et al. [127] 284–284 3.5–3.5 200 SynNon
Ethane + water + triethylene glycol Wu and Englezos [766] 272–282 1.5–4.5 21.6 AnTVis
Ethene + water + tetrahydrofuran Ma et al. [529] 274–274 1.1–1.8 256 AnT
Ma et al. [529] 277–288 0.1–2.4 60 SynVisVar
Zhang et al. [794] 273–282 2–4.5 256 AnT
Zhang et al. [795] 277–288 0.1–4 60 SynVisVar
Ethylbenzene + diglycolamine (DGA) + water Coquelet et al. [231] 298–393 0.5–5 n.a. AnTCapValVis
Ethylbenzene + methyldiethanolamine (MDEA) + water Coquelet et al. [231] 333–333 0.5–0.5 n.a. AnTCapValVis
Hydrogen + nitrogen + tetrahydrofuran + water Ma et al. [529] 274–274 6–7.4 256 AnT
Hydrogen + water + tetrahydrofuran Ma et al. [529] 278–278 1.4–6.2 256 AnT
Zhang et al. [796] 277–285 0.1–8.8 60 SynVisVar
n-Hexane + nitrogen + n-decane Uribe-Vargas and Trejo [728] 258–258 3.4–11.9 n.a. AnTVal
Propane + water + glycerol Wu and Englezos [766] 274–281 0.8–1.9 21.6 AnTVis
Propane + water + triethylene glycol Wu and Englezos [766] 273–281 0.7–2.2 21.6 AnTVis
Water + diethanolamine (DEA) + toluene Valtz et al. [733] 298–353 0.5–0.5 n.a. AnTCapValVis
Water + diglycolamine (DGA) + toluene Valtz et al. [733] 298–393 0.4–5 n.a. AnTCapValVis
Water + ethane + magnesium chloride + sodium chloride Atik et al. [178] 278–286 6.1–18.6 n.a. SynNon
Water + ethane + n-butane Chapoy et al. [217] 303–361 0.5–4.9 20 AnTCapValVis
Water + ethane + propane + 2-methylpropane Folas et al. [65] 263–293 1.5–6 300 AnPTSemY
(isobutane) + n-butane
Water + ethene + sodium dodecyl sulfate Zhang et al. [793] 273–278 2.5–5.5 256 AnTVis
Water + methyldiethanolamine (MDEA) + benzene Valtz et al. [732] 298–393 0.4–8.1 n.a. AnTCapValVis
Water + methyldiethanolamine (MDEA) +toluene Valtz et al. [733] 298–393 0.4–8.1 n.a. AnTCapValVis
Water + monoethanolamine (MEA) + toluene Valtz et al. [733] 298–353 0.5–0.5 n.a. AnTCapValVis
Table 52
Multicomponent systems: X + Y (+. . .).
X(+Y + . . .) Reference T (K) P (MPa) V (cm3 ) Method
1,1,1,2-Tetrafluoroethane Spilimbergo et al. [123] 318–326 0.1–0.4 n.a. SynNon

(HFC-134a) + tristearin + phosphatidylcholine + dioctyl sulfosuccinate
Ammonia + methanol + water + sodium chloride Schäfer et al. [637] 353–393 0.1–0.9 1600 AnT
Ammonia + methanol + water + sodium sulfate Schäfer et al. [637] 353–393 0–0.6 1600 AnT
Carbon monoxide + propylene carbonate + 1-4-dioxane + n-dodecane Shaharun et al. [146] 298–343 0.1–1.5 300 SynT
Chlorodifluoromethane Spilimbergo et al. [123] 311–324 0.1–0.7 n.a. SynNon
(HCFC-22) + tristearin + phosphatidylcholine + dioctyl sulfosuccinate
Ethene + water + 2-propanol (isopropanol) + 2,5-hexanediol Freitag et al. [42] 293–333 7.4–16.6 30 AnTVLcirVisVal
Ethene + water + 2-propanol (isopropanol) + 2,5-hexanedione Freitag et al. [42] 293–333 7.4–16.6 30 AnTVLcirVisVal
Ethene + water + 2-propanol (isopropanol) + d-phenylalanine Freitag et al. [303] 293–333 7.4–16.6 30 AnTVLcirVisVal
Ethene + water + 2-propanol (isopropanol) + l-phenylalanine Freitag et al. [303] 293–333 7.4–16.6 30 AnTVLcirVisVal
Ethene + water + 2-propanol (isopropanol) + N-acetyl-d-glucosamine Freitag et al. [303] 293–333 7.4–16.6 30 AnTVLcirVisVal
Ethene + water + 2-propanol (isopropanol) + N-acetyl-d-mannosamine Freitag et al. [303] 293–333 7.4–16.6 30 AnTVLcirVisVal
Glycerol + olive oil + propane + AOT surfactant Benazzi et al. [186] 298–373 0.9–29.5 27 SynVisVar
Hydrogen + benzene + toluene + cyclohexane + methylcyclohexane Tsuji et al. [107] 303–303 1–4.5 37 SynVis
Hydrogen + benzene + toluene + xylene + styrene Zhou et al. [813] 298–343 1.6–5.8 600 SynT
Hydrogen + carbon monoxide + ammonia + 1-octene Martin et al. [96] 396–416 20.9–21.8 27 SynVisPcTc
Hydrogen + carbon monoxide + ammonia + 1-octene +water Martin et al. [96] 393–448 19–21.8 27 SynVisPcTc
Hydrogen + carbon monoxide + ammonia + 1-pentene Martin et al. [96] 389–393 17.3–19.5 27 SynVisPcTc
Hydrogen + carbon monoxide + ammonia + nonylamine + water + dioxane Martin et al. [96] 393–431 19–23 27 SynVisPcTc
Hydrogen + carbon monoxide + ammonia + nonylamine + water + methanol Martin et al. [96] 393–433 19–24 27 SynVisPcTc
Hydrogen + carbon Martin et al. [96] 393–431 19–23 27 SynVisPcTc
monoxide + ammonia + nonylamine + water + methyl-tert-butyl ether
Hydrogen + carbon Martin et al. [96] 393–431 19–23 27 SynVisPcTc
monoxide + ammonia + nonylamine + water + tetrahydrofuran
Hydrogen + carbon monoxide + ammonia + nonylamine + water + toluene Martin et al. [96] 393–431 19–23 27 SynVisPcTc
Hydrogen + propylene carbonate + 1-4-dioxane + n-dodecane Shaharun et al. [146] 298–343 0.1–1.5 300 SynT
Hydrogen + water + lithium + boron Giraudeau et al. [88] 491–582 13.8–13.8 n.a. AnOth
Nitrogen + oxygen + argon + water Koglbauer Wendland [34] 293–413 0.1–25 49 AnSpec
n-Octane + sodium dodecylsulfate + 1-pentanol + water Polikhronidi et al. [603] 289–520 0–5.8 105.4 SynNon
Propane + anisole + acetic anhydride + p-methoxyacetophenone + acetic Ji et al. [389] 416–596 5.4–11.8 18 SynVisPcTc
acid (ethanoic acid)
Sulfur dioxide + ammonia + water + ammonium sulfate Meyer et al. [545] 313–373 6.7–12.4 30 SynVis
Sulfur dioxide + ammonia + water + sodium sulfate Meyer et al. [545] 313–373 5.7–9.1 30 SynVis
syringe pumps in which the pure substances (liquids or lique- method to determine the pT melting curve of ionic liquids. Search-
fied gases) are stored and that provide a flow of defined constant ing critical points with an acoustic method, e.g. Esperança et al.
composition (=synthetic method). The measuring part includes a [120], has the advantage that even for temperatures several degrees
transparent cell (a sapphire tube pressed between two Titanium above the critical point, the sound velocity exhibits a minimum
flanges) placed in an air thermostatic bath. The internal volume when measured isothermally as a function of pressure.
of the cell is approximately 4 cm3 . Pressure and temperature are If the total volume of a variable-volume cell can be measured
adjusted until critical opalescence is observed. accurately, the appearance of a new phase can be obtained from
With 36.0% of all systems investigated in this review, synthetic- the abrupt change in slope on the pressure–volume plot more
visual methods were the most frequently used type of method. accurately than by visual observation, e.g. Kodama et al. [121].
As an alternative pVT measurements can be performed and the
3.2.2. Synthetic-non-visual methods (SynNon) intersection of isochors can be used to determine points on the
As an alternative to visual observation, other physical proper- coexistence curve. A sharp change in the slope, (dp/dT), occurs at
ties can be monitored to detect phase transitions. Haramagatti et al. the phase boundary. Stievano and Elvassore [122] measured the
[116] made use of small angle neutron scattering in combination liquid density in a liquid recirculation loop of a variable-volume
with optical Raman spectroscopy instead of visible light, as the cell while the volume was slowly expanded. Because vapor and
basis of phase detection, while Kandil et al. [117] used a microwave liquid phases have different compressibilities, the slope of curves
re-entrant resonator to detect the appearance of dew and bubble changes at the VLE equilibrium point. The equilibrium point can
points in hydrocarbon systems. be evaluated intersecting two gas-like and liquid-like correlations
Eckert and coworkers [118] proposed a synthetic-non-visual obtained for either density–pressure or window (=movable piston)
method to measure the solubility of solids in CO2 . First the cell is displacement–pressure profiles. The authors confirmed the results
charged with the solid. Then it is pressurized with CO2 and stirred by visual observation of small vapor bubble formation in the VLE
constantly. Equilibrium of the mixture is observed in situ by period- cell at equilibrium conditions.
ically taking spectra (UV absorbance) of the solution. The pressure Spilimbergo et al. [123] used high-pressure differential scan-
is raised stepwise until no further significant increase in the peak ning calorimetry (DSC) to study solid–liquid–vapor equilibria of
absorbance is observed. This means that all solids had been dis- high-pressure gases with solid lipids. Maeda et al. [124] studied
solved in the fluid phase, the phase change has been detected. solid–solid phase transitions of a thermotropic cubic mesogen (=the
Phase changes can be detemined using sound of speed measure- fundamental unit of a liquid crystal that induces structural order in
ments. Since the acoustic wave excited in a sample for the speed of the crystals) with high-pressure differential thermal analysis (DTA)
sound measurement is strongly absorbed in the gas phase as com- at pressures up to 300 MPa.
pared to the absorption in the liquid phase, the appearance of the Kutcherov and Chernoutsan [125] investigated two sequential
gas phase can be detected by the change of the acoustic echo sig- phase transitions, a wide range crystallization and glass transi-
nal. Speed of sound measurements can be also used for solid–liquid tion, of different crude oils and their fractions at high pressures by
phase changes, e.g. Gomes de Azevedo et al. [119] used an acoustic measuring the thermal conductivity using the transient hot-wire
54
Table 53
Complex systems X + Y (+. . .).
V W X Y Z Reference T (K) P (MPa) V (cm3 ) Method
Heavy fractions of Kumkolsk oil Kutcherov [471] 275–320 0.1–1000 n.a. SynNon
Heavy fractions of Usinsk oil Kutcherov [471] 275–320 0.1–1000 n.a. SynNon
Kalchinsk oil Kutcherov [471] 275–320 0.1–1000 n.a. SynNon
Komsomolsk oil Kutcherov [471] 275–320 0.1–1000 n.a. SynNon
Kumkolsk oil Kutcherov [471] 275–320 0.1–1000 n.a. SynNon
Shtokman condensate Kutcherov [471] 275–320 0.1–1000 n.a. SynNon
Usinsk oil Kutcherov [471] 275–320 0.1–1000 n.a. SynNon
Verhozimsk oil Kutcherov [471] 275–320 0.1–1000 n.a. SynNon
Vostochno-Gorinsk oil Kutcherov [471] 275–320 0.1–1000 n.a. SynNon
1,1,1,3,3-Pentafluoropropane Synthetic polyester compressor Zhelezny et al. [810] 333–424 0.3–3.4 191 SynT
(HFC-245fa) oil Planetelf ACD 100FY
2-Methylpropane (isobutane) Mineral compressor oil Azmol Zhelezny et al. [809] 303–363 0.2–1.4 14 SynTVis

Carbon dioxide China reservoir crude oil Sun and Chen [703] 339–339 11.7–25 n.a. SynT
Rainbow Keg River reservoir fluid Ayirala and Rao [129] 360–360 0.1–17.5 n.a. SynNon
Terra Nova reservoir fluid Ayirala and Rao [129] 369–369 0.1–38 n.a. SynNon
Methane Water Conroe crude oil Greaves et al. [323] 277–298 1–7.6 1890 SynVis
Synthetic natural gas Synthetic sea water Gas condensate (Frigg Field) Kelland et al. [418] 277–293 0.2–9.2 22.8 SynVis
Gas condensate (Exxsol D60) FX-OTMAA Kelland et al. [417] 277–293 0.2–8.5 22.8 SynVis
FX-DPCEDA Kelland et al. [417] 277–293 0.2–8.5 22.8 SynVis
Gas condensate (Frigg Field) FX-OTMAA Kelland et al. [417] 277–293 0.2–12.3 22.8 SynVis
FX-DTMAA Kelland et al. [417] 277–293 0.2–9.2 22.8 SynVis
FX-LTMAA Kelland et al. [417] 277–293 0.2–9.2 22.8 SynVis
FX-DPCEOA Kelland et al. [417] 277–293 0.2–9.2 22.8 SynVis
FX-DPCEDA Kelland et al. [417] 277–293 0.2–12.2 22.8 SynVis
FX-DIPCECA Kelland et al. [417] 277–293 0.2–9 22.8 SynVis
FX-ACAA-IPO Kelland et al. [417] 277–293 0.2–9.2 22.8 SynVis
FX-ACAA-IPD Kelland et al. [417] 277–293 0.2–9.2 22.8 SynVis
FX-BETA-ADS Kelland et al. [418] 277–293 0.2–9.2 22.8 SynVis
FX-BETA-CDS Kelland et al. [418] 277–293 0.2–9.2 22.8 SynVis
FX-BETA-PDS Kelland et al. [418] 277–293 0.2–9.2 22.8 SynVis
FX-BETA-EDS Kelland et al. [418] 277–293 0.2–9.2 22.8 SynVis
FX-BETA-EOS Kelland et al. [418] 277–293 0.2–9.2 22.8 SynVis
Polyvinylcaprolactam Kelland et al. [418] 277–293 0.2–9.2 22.8 SynVis
ACER 96S35 Kelland et al. [418] 277–293 0.2–20 22.8 SynVis
FX-BETA-PDS Kelland et al. [418] 277–293 0.2–8.5 22.8 SynVis
FX-BETA-EDS Kelland et al. [418] 277–293 0.2–8.5 22.8 SynVis
Gas condensate (Exxsol D60) FX-OTMAA FX-LTMAA Kelland [417] 277–293 0.2–18.8 22.8 SynVis
Gas condensate (Frigg Field) FX-OTMAA FX-LTMAA Kelland [417] 277–293 0.2–20 22.8 SynVis
FX-ACAA-IPC FX-ACAA-IPO Kelland et al. [417] 277–293 0.2–9.2 22.8 SynVis
FX-BETA-PDS Imidazoline corrosion Kelland et al. [418] 274–293 0.2–8.5 22.8 SynVis
inhibitor
Polyvinylcaprolactam Tetrabutylammonium Kelland et al. [418] 277–293 0.2–9.2 22.8 SynVis
bromide
Polyvinylcaprolactam FX-BETA-P Kelland et al. [418] 277–293 0.2–9.2 22.8 SynVis
(3-[N,N-dibutyl-N-(2-
hydroxypropyl)
ammonio]propanoate)
Table 54
Binary systems with hydrates: water + X.
Carbon dioxide Kang et al. [128] 270–282 1–4 350 SynNon

Zhang et al. [803] 274–281 1.8–23.5 100 SynT
Carbon dioxide (+seawater) Zhang et al. [803] 276–278 3.5–21.6 100 SynT
Deuterium (+heavy water) Efimchenko et al. [151] 233–278 20–180 n.a. SynT/SynNon
Difluoromethane (HFC-32) Imai et al. [374] 278–290 0.2–1 70 SynNon
Ethane Kim et al. [426] 277–280 10.1–15.1 n.a. SynVisVar
Krypton Sugahara et al. [699] 274–320 1.6–445 0.2 SynVisSpec
Methane Chapoy et al. [216] 283–293 10–35 34 AnTCapVal
Kang et al. [128] 271–284 2–10 350 SynNon
Lee et al. [486] 276–281 3.6–6 474 SynNon
Methylfluoride Takeya and Ohmura [708] 273–296 0.2–3.5 202 SynNon
Propane Gaudette and Servio [312] 274–276 0.1–0.3 n.a. AnT
Melnkov et al. [113] 257–275 0.1–0.3 100 SynVis
Sulfur hexafluoride (SF6) Sugahara et al. [700] 274–313 0.1–155 5 SynVis
Sugahara et al. [700] 274–313 0.1–155 1 SynVisSpec
Sugahara et al. [700] 274–313 0.1–155 0.2 SynVisSpec
Tetra-n-butyl ammonium bromide Arjmandi et al. [176] 280–279 3.6–20.9 2400 SynNon
Tetrafluoromethane (CFC-14) Mooijer-van den Heuvel et al. [560] 273–281 3.4–12.9 3.5 SynVisVar
Trifluoromethane (HFC-23) Mooijer-van den Heuvel et al. [560] 282–293 0.9–4.1 4 SynVisVar
Xenon Sugahara et al. [699] 324–345 106–440 0.2 SynVisSpec
method as well as the isochoric heat capacity by using differential To investigate the phase behavior in porous media, non-visual
scanning calorimetry. The range of pressures was from atmospheric methods are particularly advantageous. Kang et al. [128] used
to 1.2 GPa. the isochoric temperature cycle method to investigate the phase
Tohidi and coworkers [126] and Sloan and coworkers [127] used behavior of methane and CO2 hydrates in meso- and macro-sized
a synthetic-non-visual method to determine pressure and temper- porous media. To identify the crystalline structure of the gas
ature at which hydrates form in a certain mixture by performing hydrates formed in the silica gel pores and to compare them with
an isochoric temperature cycle. Once the cell is charged with the those of the bulk state hydrate, an NMR spectrometer was used.
desired components, the mixing is started and the temperature of Ayirala and Rao [129] developed a technique to determine the
the cell is lowered, a linear decrease in pressure is observed, reflect- miscibility of gas–oil systems, which they call “VIT – vanishing
ing the isochoric cooling of the sample. This pressure–temperature interfacial tension”. This method is based on the concept that, at
response is called ‘the pT cooling curve’. Hydrate formation initi- miscibility, the value of interfacial tension between the two phases
ates after sub-cooling the sample (usually more than 4 K below the is zero. The interfacial tension between the injected gas and crude
estimated equilibrium temperature). This process can be identi- oil at reservoir temperature is measured in a capillary in a high-
fied by a sudden drop in pressure (due to gas consumption as the pressure view cell at varying pressures. The miscibility conditions
gas is enclathrated into the hydrate lattice), together with a tem- are then determined by extrapolating the plot between interfacial
perature increase of the sample (due to the exothermic hydrate tension against pressure to zero interfacial tension.
crystallization process). The bath temperature is then kept con- To measure the critical temperature of thermally unstable sub-
stant to allow further hydrate formation to proceed, until no further stance, the pulse-heating method, as described by Nikitin and
decrease in pressure is observed. This process typically requires coworkers [130], can be used. It is based on measuring the pres-
more than 8 h to be completed [127]. The temperature is then sure dependence of the temperature of the attainable superheat
increased stepwise, hydrates dissociate, causing an increase in the (spontaneous boiling-up) of a liquid with the help of a thin wire
pressure of the cell. This pressure temperature dependence is called probe heated by pulses of electric current. When the pressure in
the “pT heating curve”. Rovetto et al. [127] obtained the heating the liquid approaches the critical pressure, the temperature of the
curve by increasing the temperature of the sample in steps of 1 K attainable superheat approaches the critical temperature.
with intervals of at least 8 h between each step, in order to ensure A continous-feed synthetic-non-visual method (SynNonCon)
that the system had achieved thermodynamic equilibrium at each that looks at first sight like an analytical continous-flow method
temperature step. Outside the hydrate region, only a small pres- (AnPTCon) was used by VonNiederhausern et al. [131] to determine
sure increase is seen, due to thermal expansion, and heating curve the critical points of thermally unstable or reactive components. To
and cooling curve coincide. The hydrate dissociation point for each achieve very short residence times, a sample of precisely known
experiment is determined from the intersection of both (cooling composition is continuously displaced and heated in a capillary
and heating) curves. This point represents the equilibrium transi- tube. No analyis of the samples takes place. To determine the crit-
tion hydrate + liquid + gas → liquid + gas. The procedure is repeated ical point, several temperature scans must be made in the vicinity
at different pressures in order to determine the hydrate phase of the critical point. Below the critical point, the temperature scan
boundaries over a wide temperature range making it a very time will show a flat, horizontal region indicative of isothermal boiling.
consuming method. Above the critical point, the transition region is no longer flat and
Table 55
Ternary systems with hydrates: water + X + Y.
X Y Reference T (K) P (MPa) V (cm3 )Method
Argon Ethane Maekawa [535] 273–276 0.4–1 700 AnTVis

Carbon dioxide 1,4-Dioxane Seo et al. [652] 274–280 1–3.7 50 SynVis
Acetone Seo et al. [652] 270–279 0.8–3.5 50 SynVis
Hydrogen Kumar et al. [456] 273–281 1.5–10.7 n.a. AnTVis
Sugahara et al. [701] 274–27415.2–15.2 0.2 SynVisSpec
Methane Beltrán and Servio [97] 275–285 1.9–7.4 150 SynVisVar
Nitrogen Bruusgaard et al. [198] 275–283 1.6–22.4 150 SynVisVar
Linga et al. [511] 273–273 1–11 323 AnTVis
Potassium chloride Mohammadi et al. [554] 273–278 2–3.3 57.5 SynNonVis
Propylene oxide Seo et al. [652] 271–281 0.3–3.3 50 SynVis
Sodium chloride Kim et al. [426] 278–28010.1–20.1 n.a. SynVisVar
Tetra-n-butylammonium bromide Arjmandi et al. [176] 285–291 1.4–4 2400 SynNon
tetrahydrofuran Delahaye et al. [253] 278–290 0.1–3.5 46 SynNon
Martinéz et al. [540] 278–290 0.2–2 n.a. SynNon
Seo et al. [652] 272–291 0.2–4 50 SynVis
Tetra-n-butylammonium bromide Lin et al. [510] 279–288 0.3–2.2 46 SynNonVis
Triethylene glycol Afzal et al. [165] 264–282 0.6–4.2 58 SynNon
Trifluoromethane (HFC-23) Mooijer-van den Heuvel et al. [560]280–303 1.4–9.9 3.5 SynVisVar
Difluoromethane (HFC-32) 2-Methyl-2-propanol Imai et al. [376] 268–287 0.1–1.1 70.7 SynNon
2-Propanone Imai et al. [376] 268–284 0–0.7 70.7 SynNon
Cyclopentane Imai et al. [374] 280–299 0–1.5 70 SynNon
Fluorocyclopentane Imai et al. [375] 288–299 0.1–1 70.7 SynNon
Tetra-n-butylammonium bromide Imai et al. [374] 286–289 0.1–1.2 70 SynNon
Ethane 2-Propanol (isopropanol) Mohammadi and Richon [553] 277–281 0.6–1.1 n.a. SynNon
Sodium chloride Kim et al. [426] 278–28110.1–15.1 n.a. SynVisVar
Hydrogen Dimethylcyclohexane Duarte et al. [272] 274–27960.1–95 n.a. SynVis
Methane Skiba et al. [685] 266–313 0.1–250 n.a. SynNon
Methyl tert-butyl ether Duarte et al. [272] 269–27270.1–100.1n.a. SynVis
Methylcyclohexane Duarte et al. [272] 274–27583.1–100.1n.a. SynVis
Tetra-n-butylammonium bromide Arjmandi et al. [176] 280–288 4.2–23 2400 SynNon
Tetrahydrofuran Hashimoto et al. [112] 277–281 0.1–13.3 150 SynVisSpec
Hashimoto et al. [342] 273–280 0–13.8 150 SynVisSpec
Nagai et al. [566] 269–275 3.6–8.4 129.8 SynTVis
Ogata et al. [150] 277–277 0.1–72.0 10 SynT
Tetra-n-butylammonium bromide Hashimoto et al. [112] 277–281 0.1–13.3 150 SynVisSpec
Hashimoto et al. [343] 279–285 0.5–12.7 150 SynNonVis
Strobel et al. [692] 279–27913.8–13.8 20 AnT
Tetra-n-butylammonium fluoride Sakamoto et al. [625] 298–302 0.2–37.6 150 SynNonVis
Krypton 2,2-Dimethylbutane Ohmura et al. [585] 273–285 0.4–2 200 SynNon
2-Methyl-2-propanol Imai et al. [376] 266–293 0.1–4.7 70.7 SynNon
2-Propanone Imai et al. [376] 268–291 0.1–4.9 70.7 SynNon
Cyclopentane Takeya and Ohmura [707] 283–308 0.1–7.6 200 SynNon
Cyclopentene Takeya and Ohmura [707] 280–297 0.1–2 200 SynNon
Ethane Maekawa [535] 273–276 0.4–1 700 AnTVis
Fluorocyclopentane Imai et al. [375] 286–308 0.1–4.8 70.7 SynNon
Tetrahydropyran Takeya and Ohmura [707] 278–296 0.1–2 200 SynNon
Methane 1,1-Dimethylcyclohexane Hara et al. [338] 274–289 1–6.7 150 SynNon
1-Propanol Maekawa [536] 274–286 2.6–11 1000 SynNon
2,2-Dimethylpentane Kozaki et al. [447] 273–279 2.4–4.8 236 SynNon
2-Methyltetrahydrofuran Ohmura et al. [584] 273–285 2.5–9.6 200 SynNon
2-Propanol (isopropanol) Maekawa [536] 274–287 2.2–11 1000 SynNon
3-Methyltetrahydropyran Ohmura et al. [584] 273–282 1.2–3.8 200 SynNon

Calcium chloride Atik et al. [178] 265–282 3–22.9 n.a. SynNon
Mohammadi et al. [554] 268–283 2.8–9 57.5 SynNonVis
Cyclopropane Makino et al. [537] 291–291 0.9–18.7 n.a. AnTVis
Makino et al. [537] 291–291 1–15.1 n.a. SynVisSpec
Diethylene glycol Afzal et al. [166] 274–282 5–8 n.a. SynNon
Ethane Kumar et al. [457] 273–273 1.4–1.4 n.a. SynNon
Ethene Zhang et al. [793] 273–278 2.5–5.5 256 AnTVis
Hydrogen Ma et al. [529] 274–274 3.8–5.5 256 AnT
Magnesium chloride Atik et al. [178] 270–292 3.4–22.6 n.a. SynNon
Methylcyclohexane Ohmura et al. [583] 251–272 0.5–1.2 200 SynNon
n-Propanol Chapoy et al. [126] 276–293 3.5–37.6 500 SynNon
p-Toluene sulfonic acid Rovetto et al. [127] 277–280 4–5 200 SynNon
Propane Kumar et al. [457] 273–273 0.5–0.5 n.a. SynNon
Sodium dodecyl sulfate Gayet et al. [313] 275–300 3.1–55 250 SynNonVis
Lee et al. [486] 276–281 3.7–5.9 474 SynNon
Tert-butyl methyl ether Ohmura et al. [583] 252–270 0.6–1.2 200 SynNon
Tetra-n-butylammonium bromide Arjmandi et al. [176] 287–298 1.4–41.3 2400 SynNon
Tetrafluoromethane (CF4) Kunita et al. [470] 291–291 18.5–90 0.2 SynVisSpec
Tetrafluoromethane (CFC-14) Mooijer-van den Heuvel et al. [560] 272–289 2–14 3.5 SynVisVar
Tetra-n-butylammonium bromide Li et al. [491] 281–295 0.4–10.2 n.a. SynVisVar
Triethylene glycol Afzal et al. [165] 264–275 3–5.1 58 SynNon
Trifluoromethane (HFC-23) Mooijer-van den Heuvel et al. [560] 274–303 1–14 3.5 SynVisVar
Methylfluoride Cyclopentane Takeya et al. [709] 287–305 0.1–2.9 138.2 SynNon
Cyclopentene Takeya et al. [709] 283–300 0.1–1.9 138.2 SynNon
Fluorocyclopentane Takeya et al. [709] 290–307 0.1–2.5 138.2 SynNon
Methylcyclohexane Takeya and Ohmura [708] 273–294 0.1–2.7 202 SynNon
Tetrahydrofuran Takeya et al. [709] 284–301 0.1–1.8 138.2 SynNon
Natural gas n-Propanol Chapoy et al. [126] 289–290 9.9–10 500 SynNon
Nitrogen Tetra-n-butylammonium bromide Arjmandi et al. [176] 285–292 4.6–33.5 2400 SynNon
Propane 2-Propanol (isopropanol) Mohammadi and Richon [553] 274–278 0.1–0.3 n.a. SynNon
Synthetic natural gas p-Toluene sulfonic acid Rovetto et al. [127] 285–3 285–3 200 SynNon
Xenon 1,1-Dimethylcyclohexane Sugahara et al. [702] 274–301 0.1–2.7 10 SynVis
Trans-1,2-dimethylcyclohexane Sugahara et al. [702] 274–283 0.1–2.7 10 SynVis
horizontal. The critical point is inferred by the temperature and dioxide UO2+x at high pressures. The determination of the phase-
pressure where isothermal boiling is no longer observed. transition boundaries for the uranium–oxygen system is of great
Poliakoff and coworkers [132,133] developed a fibre optic reflec- importance in the nuclear industry. Knowledge about the melting
tometer (FOR) technique to monitor refractive index and density transition in the nuclear fuel is particularly important in the analy-
changes in gases, liquids and supercritical fluids. The key oper- sis of hypothetical meltdown accidents, as it defines the structural
ating principle is the measurement of the intensity of light from limit of a combustible element. Temperatures of almost 3200 K
a light emitting diode (LED) which is reflected from the end of were needed. Such high temperatures can be measured optically by
a fibre immersed in the medium. The amount of reflected light pyrometry. Two pulsed Nd-YAG laser beams were mixed through a
depends on the difference between the refractive indices of the suitable optical system in the same fibre and then focused onto the
fibre and the medium. The refractive index of the medium is related sample surface. The pulse with the higher power peak was used to
in turn to its density. The FOR is particularly sensitive to phase sep- heat the sample above the melting point; the other one, less pow-
aration, because of the density discontinuity which accompanies erful, but of longer duration, was used to control the cooling rate
the separation. Wu et al. [133] used FOR to detect phase changes on the sample surface. This lead to a much better definition of the
in a continous-feed synthetic-non-visual method (SynNonCon) to freezing plateau. Pressure was applied by using helium.
determine the phase boundaries of CO2 + solvent systems. Diamond anvil cells are particularly suitable for non-visual mea-
The experiments at the highest temperatures of all articles surements at very high pressures [8]. The selective transparency of
covered in this review were performed by Manara et al. [134]. diamond from IR to X-ray and gamma-ray radiations permits in situ
They investigated the melting point of hyperstochiometric uranium measurements during experiments.
Table 56
Multicomponent and complex systems with hydrates: water + X + Y (+. . .).
Carbon dioxide + methane + neohexane Beltrán and Servio [97] 275–285 1.3–6.1 150 SynVisVar
Methane + ethane + p-toluene sulfonic acid Rovetto et al. [127] 284–284 3.5–3.5 200 SynNon
Carbon dioxide + hydrogen + tetrahydrofuran Hashimoto et al. [341] 280–280 0.2–3.6 150 AnTVis
Carbon dioxide + hydrogen + propane Kumar et al. [456] 274–282 2.5–9.7 n.a. AnTVis
Methane + ethane + propane Kumar et al. [457] 273–273 0.7–0.7 n.a. SynNon
Carbon dioxide + nitrogen + tetrahydrofuran Lingaet al. [511] 273–273 1.5–1.5 323 AnTVis
Methane + ethene + tetrahydrofuran Ma et al. [529] 274–274 1.1–1.8 256 AnT
Ma et al. [529] 277–288 0.1–2.4 60 SynVisVar
Methane + hydrogen + tetrahydrofuran Ma et al. [529] 278–278 1.4–6.2 256 AnT
Methane + ethane + triethylene glycol Wu and Englezos [766] 272–282 1.5–4.5 21.6 AnTVis
Methane + propane + triethylene glycol Wu and Englezos [766] 273–281 0.7–2.2 21.6 AnTVis
Methane + ethane + glycerol Wu and Englezos [766] 274–281 2.1–4.7 21.6 AnTVis
Methane + propane + glycerol Wu and Englezos [766] 274–281 0.8–1.9 21.6 AnTVis
Methane + ethene + sodium dodecyl sulfate Zhang et al. [793] 273–278 2.5–5.5 256 AnTVis
Methane + ethene + tetrahydrofuran Zhang et al. [794] 273–282 2–4.5 256 AnT
Zhang et al. [795] 277–288 0.1–4 60 SynVisVar
Hydrogen + methane + tetrahydrofuran Zhang et al. [796] 277–285 0.1–8.8 60 SynVisVar
Methane + ethane + magnesium chloride + sodium Atik et al. [178] 278–286 6.1–18.6 n.a. SynNon
chloride
Methane + hydrogen + nitrogen + tetrahydrofuran Ma et al. [529] 274–274 6–7.4 256 AnT
Carbon dioxide + nitrogen + methane + ethane + Arjmandi et al. [176] 280–292 0.9–9.5 2400 SynNon
propane + 2-methyl propane + n-butane +
2-methyl butane + tetra-n-butylammonium
bromide
Using a multi-anvil cell and energy-dispersive X-ray diffraction thermodynamic derivatives, one is always thermal and the other
with synchroton radiation, Solozhenko et al. [92] studied the phase mechanical. During an isobaric temperature scan both the heat flux
behavior of boron + boron(III) oxide at 5 GPa and temperatures up and the volume variations are recorded. The transitiometer consists
to 2750 K. Solozhenko described the apparatus in an earlier publi- of a calorimeter equipped with high-pressure vessels, and a pVT
cation [135]. A boron-epoxy gasket was used as the compressing system. Machado et al. [138] used the transitiometric method to
medium between the conical tungsten carbide anvils. The sample measure solid–solid transition and melting temperatures for long
volume is only 7 mm3 , the smallest volume of all articles covered n-alkanes at high pressures.
in the period of this review. A new approach to locating the dew points, bubble points and
Randzio developed and described [136,137] the transitiomet- critical points of fluid mixtures was developed by Poliakoff and
ric method for the investigation of phase transitions. Scanning coworkers [139,140] utilizing a shear mode piezoelectric sensor.
transitiometry is based on a simultaneous recording of both This technique employs a single piece of quartz crystal that is
mechanical and thermal variables of a thermodynamic transition installed at the bottom of a strongly stirred high-pressure ves-
induced by scanning one independent variable (p, T or V) while sel. The sensor response indicates whether liquid or gas is in
the other independent variables are kept constant. The appara- contact with its surfaces. Thus, the sensor is able to identify
tus (“transitiometer”) permits to determine simultaneously two vapor–liquid phase separation by registering a discontinuity in
Table 57
Articles containing corrigenda, comments, or rebuttals to comments.
Original article Year Content Article with corrigendum or comment
Chapoy et al. [821] 2003 Methane, water Chapoy et al. [216] 2005 Corrigendum
Kamps et al. [823] 2003 CO2 , [bmim] [PF6 ] Kumelan et al. [461] 2006 Corrigendum
Zhang and Kiran [825] 2003 CO2 , tetrahydrofuran, polysulfone Zhang and Kiran [801] 2006 Corrigendum
Glos et al. [822] 2004 Propane Glos et al. [218] 2006 Corrigendum
Levitin et al. [824] 2004 CO2 , methanol, water, tetramethylammonium Levitin et al. [489] 2005 Corrigendum
bicarbonate
Kong et al. [437] 2005 CO2 , trinervonin, triarachidonin Kong et al. [438] 2005 Corrigendum
Kumelan et al. [458] 2005 CO2 , 1-N-butyl-3-methylimidazolium Kumelan et al. [464] 2007 Corrigendum
hexafluorophosphate ([bmim] [PF6 ])
Park et al. [592] 2006 CO2 , dimethyl ether, HFCFC-22, HFC-23, HFC152a, Park et al. [591] 2006 Corrigendum + Addition
poly(␧-caprolactone), poly(l-lactide), polystyrene
Yarrison et al. [774] 2006 Water, methane, ethane Kontogeorgis and Yan [441] 2007 Comment
Bazaev et al. [183] 2007 CO2 , ethanol Bazaev et al. [185] 2008 Corrigendum
Folas et al. [299] 2007 Water, methane, ethylene glycol Mohammadi and Richon [552] 2007 Comment
Folas et al. [300] 2007 Reply to Comments
Han et al. [335] 2007 Difluoromethane (HFC-32), pentafluoroethane Han et al. [336] 2008 Corrigendum
(HFC-125)
Ren and Scurto [141] 2007 CO2 , 1-n-hexyl-3-methyl-imidazolium Ren and Scurto [826] 2008 Publisher’s Note
bis(trifyl)imide, n-decane
Madani et al. [530] 2008 Hexafluoroethane (PFC-116), Mandani et al. [531] 2008 Corrigendum
1,1,1,2-tetrafluoroethane (HFC-134a)
Kaboudvand and 2008 CO2 , tridodecylamine Kaboudvand and Ghaziaskar [402] 2008 Corrigendum
Ghaziaskar [401]
Zhang et al. [790] 2008 CO2 , 2,2,4-trimethylpentane (isooctane) Jaubert and Vitu [383] 2008 Comment
Zhang et al. [791] 2008 Reply to Comments
the impedance minimum of the sensor as a function of pres- and with inverse gas chromatography (AnPTChro). These meth-
sure. ods differ in the underlying experimental principles as well as in
the complexity of data analysis. Despite of these differences, the
3.2.3. Synthetic-isothermal methods (SynT) agreement of the measured VLE data is excellent.
Synthetic-isothermal methods are performed without a phase
transition, where the pressure of a synthesized multi-phase mix- 3.2.4. Synthetic-isobaric methods (SynP)
ture is measured at isothermal conditions and phase compositions The boiling temperature of a synthesized mixture is measured
are calculated using the material balance. Prior to an experiment, at isobaric conditions and phase compositions are calculated using
all substances have to be carefully degassed. An equilibrium cell the material balance. As opposed to analytical isobaric methods
is charged with a known amount of the first component and ther- (AnP), no sampling or analysis is performed. Just as synthetic-
mostated to a given temperature. Then, a known amount of the isothermal methods (SynT), synthetic-isobaric methods (SynP) are
second component is added whereby the pressure increases. The performed without a phase transition. When used for a pure com-
second component dissolves into the liquid phase, which leads to a ponent – the composition is given anyway – the synthetic-isobaric
decay of the pressure in the equilibrium cell. Therefore, this method method delivers the vapor pressure, e.g. Ewing and Ochoa [153].
is also called pressure-decay method, especially when a polymer is Then, it is often called the “dynamic” vapor–pressure method. Typ-
used as the first component. After equilibration pressure and tem- ically, isobaric experiments are performed in an ebulliometer as
perature are registered. No samples are taken. The composition of described in Section 3.1.3 (AnP). An ebulliometer was first used to
the vapor phase is calculated using a phase equilibrium model or determine the molecular weights of substances, by measuring the
assumed as just containing the pure gas, as it is feasible for example changes of the boiling point of water caused by the presence of
when the solubility in polymers or in other compounds with negli- the unknown substance. Twin ebulliometry can be used to deter-
gible volatility is considered. The composition of the liquid phase is mine the activity coefficient at infinite dilution. The temperature
calculated using the material balance from the known total compo- difference between an ebulliometer filled with the first (pure) com-
sition, the composition of the vapor phase and the phase densities ponent and a second ebulliometer (under the same pressure) filled
and volumes, e.g. using the equations given by Ren and Scurto [141]. with the first component and with a small amount of a second
By repeating the addition of the second component into the cell, component (diluted solution) is measured. From the difference of
several points along the boiling-point line can be measured. To get the boiling temperatures, the activity coefficient at infinite dilution
a complete boiling-point line, the isothermal experiment has to be can be calculated. Usually synthetic-isobaric methods are used to
performed again, this time starting with the second component and measure low-pressure data.
adding the first. Ewing and Ochoa [154] used comparative ebulliometry to pre-
At lower pressures synthetic-isothermal methods are very cisely determine the vapor pressure of pure components at high
commonly used [142–144]. They are often designated as “static pressures. The sample and a reference fluid are boiled in separate
method” or “isothermal pTx method”. Examples for the applica- ebulliometers under a common pressure of gas such as helium or
tion of the synthetic-isothermal methods at high pressures are nitrogen, and the condensation temperatures of the sample and of
given by Liu and Tomasko [145] who determinded the solubility the reference fluid are measured. The common pressure is calcu-
of low-boiling substances in polymers, or by Shaharun et al. [146], lated from the known vapor pressure of the reference fluid. The
Kim et al. [147], and Gruszkiewicz and Simonson [148] who deter- method has many advantages: direct measurement of pressure is
mined the solubility of gases in organic solvents, ionic liquids, or avoided, the fluids are degassed by boiling, and the ebulliome-
electrolyte solutions. ters act as heat pipes to provide high-performance thermostats.
When used for a pure component, the synthetic-isothermal The corresponding disadvantages are the considerable demands on
method delivers the vapor pressure, e.g. Anderson et al. [149]. Then, thermometry, the solubility of the buffer gas at high pressures, and
it is often called the “static” vapor–pressure method. thermal gradients due to pressure heads. But the greatest advan-
Ogata et al. [150] used the synthetic-isothermal method to mea- tage is speed of measurement; typically, a pressure–temperature
sure the absorption of hydrogen in tetrahydrofuran hydrates. For point can be obtained in an hour.
a given temperature, they determined the storage capacity of the
hydrate as a function of pressure. 3.2.5. Other synthetic methods (SynOth)
The synthetic-isothermal method can be used in combination Properties measured in the homogenous or heterogeneous
with other methods, often in the same apparatus. For exam- region are used to calculate the phase boundaries.
ple, when gas-solubilities are measured with synthetic-isothermal Polikhronidi et al. [155] used one-phase and two-phase iso-
method in a view cell, the formation of solids could be determined choric heat capacity measurements to determine the values of the
with the synthetic-visual (SynVis) method. Efimchenko et al. [151] temperatures and densities at saturation and of the critical param-
combined the synthetic-isothermal method with the synthetic- eters (TC , pC , C ) for the CO2 + n-decane system. They call their
non-visual method to measure the deuterium solubility in heavy method quasi-static thermogram technique. Matsuda et al. [156]
water and the formation of high-pressure cubic clathrate ice. measured excess molar enthalpies hE of the CO2 + diisopropyl ether
Petermann et al. [79] presented a new experimental technique system using a flow-type isothermal microcalorimeter both in the
to measure directly the selective sorption of gas mixtures up to homogeneous liquid region and in the two-phase region. The liquid
high pressures. They combine an analytical gravimetric method composition of CO2 at the phase boundary for a certain temperature
(AnGrav) with a synthetic-isothermal method (SynT), which they and pressure was determined from the intersection of the hE -curves
call “gravimetric-volumetric method”. By combining both mea- in the homogeneous liquid region and in the two-phase region.
suring effects (mass increase measured with magnetic suspension For systems with two degrees of freedom (e.g., binary two-phase
balance and pressure drop from the volumetric measurement) the equilibria or ternary three-phase equilibria), the compositions
co-adsorption equilibrium of binary gas or vapor mixtures can be are fixed when temperature and pressure are given. Shiflett and
measured. To measure the sorption of three gases, samples from Yokozeki [157] investigated the phase behavior of a univariant
the vapor phase have to taken and analyzed (AnTYGrav). system: VLLE in a binary system. If the system temperature T
Krüger et al. [152] compared results of the synthetic-isothermal is fixed, then all other thermodynamic intensive variables (pres-
method (SynT) for VLE of the n-pentane + poly(dimethylsiloxane) sure, compositions, and molar volumes in each phase) are uniquely
system with results of the gravimetric sorption method (AnGrav) determined, regardless of any given overall-feed composition. The
overall feed composition merely changes the physical volume in In the following, we summarize some points that are important
each liquid phase and gas phase, but the composition and molar vol- for experimental methods for phase equilbrium measurement.
ume in each phase remain constant as long as the three phases exist
at the fixed T. They prepared a set of VLLE solutions with three dif- 3.3.1.1. Charging of the cell – synthesis of the mixture
ferent feed compositions in three sample containers (alternatively, 1. All parts of the apparatus need to be clean at the beginning of the
the same equilibrium cell could be used in three experimental runs) experiment. The possibility of dirty corners or parts of the appa-
and measured the volume of each phase at constant T. With the use ratus which are difficult to clean should be minimized already
of the mass balance, the compositions and molar volumes of the during the design of the apparatus (important for all methods).
three phases were calculated. 2. Pure and degassed substances should be used (even more impor-
Bazaev et al. [158] used isochoric pvTx measurements in the sin- tant for synthetic methods).
gle phase region (remark: otherwise it would be SynT) to derive 3. The mixture must be prepared very precisely (essential for syn-
equilibrium properties. Saturated liquid and vapor densities were thetic methods).
derived by extrapolation of measured pVT data to the saturation 4. It has to be ensured that the investigated components are stable
pressure. The values of the saturated properties (saturated tem- during the entire time of experiment especially during long-time
peratures and vapor–pressures) for measured isochors were also experiments at higher temperatures.
derived by using the isochoric and isothermal break-point tech-
niques.
3.3.1.2. Equilibration
3.3. Important points for experimental methods 1. The involved phases should be sufficiently mixed to ensure an
efficient equilibration (important for all methods).
Even though most of the experimental methods have been used 2. It has to be ensured, that the time for equilibration is sufficiently
for decades, the knowledge of how to get precise results with a long (important for all methods). In case of using continuous
certain method and how to avoid mistakes is not generally known. flow methods (AnPT) the flow rates need to be sufficiently
Good measurements are not easy to perform, many mistakes can low.
be made. Experience is very important. In many cases, the quality 3. The conditions (temperature, composition) should be constant
of the personnel performing and supervising the experiment has everywhere in the equilibrium cell. Leaks are unacceptable.
a higher impact on the results than details of the equipment. This Dead spots which are not at the conditions of the desired
shall be illustrated by the following example. phase equilibrium have to be avoided (important for all meth-
In 2005 Cheng and Chen [159] from National Taiwan Univer- ods).
sity (Taipeh) measured the CO2 + isopropyl acetate system using 4. The conditions (temperature and pressure) should be
an analytical isothermal method with liquid phase recirculation measured precisely which implies the calibration of the
and online sampling (AnTLcirValVis, V = 320 cm3 , GC analysis). pressure and temperature sensors. Thereby it should
Cheng and Chen estimated the accuracy of their measured equilib- be ensured, that the calibration is always done for the
rium compositions as ±0.2 mol%. Three years later Kodama et al. entire range of measurement. Furthermore it should be
[160] from Nihon University (Fukushima, Japan) measured the kept in mind that the relative error of pressure measure-
same system using a synthetic-non-visual method, determining the ments is higher at lower pressures and dependent on the
boiling-point pressure for a given mixture from the abrupt change maximum pressure of the transducer (important for all
in slope on the pressure–volume plot (SynNonVisVar). Since they methods).
measured a significantly higher CO2 solubility in the liquid phase, 5. It has to be considered that a small change of pres-
by a factor of 30 outside of the range of accuracy given by Cheng and sure or temperature leads to a phase split, e.g. par-
Chen, they measured the system again using an analytical isother- tial condensation. This is particularly important if a satu-
mal method with recirculation of both phases and online sampling rated phase is flowing, e.g. in circulation lines (e.g. AnTV-
(AnTVLcirValVis, V = 320 cm3 , GC analysis). The results showed that cir).
both data sets of Kodama et al. measured with different methods 6. It must be also considered that temperature might change
agreed well within 0.9 mol%, while the two data sets measured with a measuring signal, e.g. the signal of a pressure trans-
the analytical isothermal method by different authors differed by ducer.
7.9 mol%.
Such significant discrepancies between phase equilibria data 3.3.1.3. Analysis and determination of a phase transition
determined by different authors has not only been observed in 1. Pressure loss during sampling disturbs the phase equilibrium
this particular case, but similar observations concerning deviations which results in a (significant) loss of accuracy of the measured
have been found for other systems in the literature, e.g. by Peper data points (essential for AnT). This disturbance can be avoided
et al. [161]. e.g. by pressure compensation or by sampling of only small vol-
It is astonishing why the real accuracy of published experimen- umes from a large equilibrium cell.
tal data is much lower than the accuracy given by the authors. Often 2. Samples must be representative of the studied phases. Besides
this can be explained by the fact that less experienced personnel the disturbance of the equilibrium state in the cell the pressure
has overlooked sources of errors of the experimental procedure and reduction changes the sample itself (phase split). Therefore, it
deficiencies of the apparatus. has to be ensured that the sample will be completely withdrawn
Experimental difficulties and errors are rarely published, though from the equilibrium cell and the sampling system, respectively
they are an important part of the know-how for measuring high- (AnT, AnPT).
quality data. This knowledge can be developed and maintained 3. Special care must be taken in order to avoid adsorption inside
within the research group, if a certain level of ongoing experimen- transfer lines, samplers, columns, etc. This is even more impor-
tal activity exists. A survey of the European Federation of Chemical tant when working in the trace region of many compounds, like
Engineering on industrial needs for thermodynamics and transport water, hydrogen sulfide, methanol, etc. (AnT, AnPT).
properties [162] showed that there is a clear need for qualified 4. Concerning the analysis of the samples, it is very important to
laboratories with experienced staff to provide experimental mea- carefully calibrate all instruments used and to give calibration
surements. results (AnT, AnPT).
5. Pressure induced changes of measuring signal, e.g. absorption To provide the reader with information on articles with cor-
units (AnSpec) or buoyancy (AnGrav) have to be considered. rections and discussions on published experimental high-pressure
6. For the determination of phase changes it must be taken into data, we prepared a compilation (Table 57). We give the original
account that the change of the volume will lead to a change articles and the articles with corrigenda, comments, rebuttals to
of the temperature, e.g. due to compression work (SynVis, comments or publisher’s notes, when at least one of them falls in
SynNon). the period of the review. Most of the corrigenda are concerning
minor corrections, but they can be very substantial, e.g. Han et al.
[827] corrected a substance investigated that was originally given
4. Systems investigated repeatedly wrong in the title, the abstract and the text of the article.
Work on the continuation of the review series is under way,
Almost 800 articles with experimental data on high pres- covering the period between 2009 and 2011, and will be published
sure phase equilibria were found [163–818]. More than 2400 in 2012. We are also working on a supplemental edition of this
systems have been investigated, from pure-components, binary review series, containing data that have not been included in one
systems up to complex mixtures with many components. In of the earlier reviews, e.g. because they were published in journals
Tables 3–56, the following information about the systems inves- that are not or were not yet searched systematically, or because
tigated is given: the reference, the temperature and pressure they were overlooked. We appreciate suggestions by the authors.
range of the data and the experimental method used for the The supplemental edition will be published in 2013.
measurements.
Because the size of the equilibrium cell can be of importance, References
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High-Pressure Uid-Phase Equilibria: Experimental Methods and Systems Investigated (2005-2008)

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High-Pressure Uid-Phase Equilibria: Experimental Methods and Systems Investigated (2005-2008)

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Fluid Phase Equilibria 300 (2011) 1–69

Contents lists available at ScienceDirect

Fluid Phase Equilibria

High-pressure ﬂuid-phase equilibria: Experimental methods and systems

3.3. Important points for experimental methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60

phase equilibria. The reason is that no single method is suitable

Journal Number of articles on high-pressure phase equilibria

1978–1987a 1988–1993b 1994–1999c 2000–2004d 2005–2008e

J. Chem. Eng. Data 92 115 214 231 283

Total 199 380 569 697 791

Experimental method Systems measured with method

2000–2004 2005–2008 Trend

Analytical methods 46.7% 37.6%

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

1,1,1,2,3,3,3-Heptaﬂuoropropane (HFC-227ea) Lim et al. [507] 273–323 0.1–0.9 85 SynT

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

2-Propene-1-ol VonNiederhausern et al. [131] 438–547 0.7–5.6 n.a. SynNonConPcTc

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

Dipropyl phthalate Nikitin et al. [575] 784–784 1.9–1.9 n.a. SynNonPcTc

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

Fedele et al. [296] 253–293 0.3–1.2 50 SynT

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

(1-Methylimidazole)(triethylamine)boronium bis Muldoon et al. [84] 298–298 0.1–1.3 n.a. AnGrav

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

1-Methyl-3-(3,3,4,4,5,5,6,6,6-nonaﬂuorohexyl)imidazolium Muldoon et al. [84] 298–333 0.1–1.3 n.a. AnGrav

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

1-n-Hexyl-3-methylimidazolium hexaﬂuorophosphate Shariati and Peters 295–365 1–93 3.5 SynVisVar

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

2-Ethyl-1-hexanol Ghaziaskar et al. 313–313 9.9–9.9 16 AnPTSemY

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

Atorvastatin Hojjati et al. [32] 308–348 12.1–35.4 1 AnTValY

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

Butyl methacrylate Husain et al. [361] 323–333 1.9–10 70 AnTLcirVis

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

Diallylsulﬁde Andreatta et al. [172] 275–370 1.7–14 3.5 SynVisVar

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

Fluvastatin Hojjati et al. [32] 308–348 12.1–35.4 1 AnTValY

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

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

Octadecanoic acid Garlapati and Madras 308–318 12.8–22.6 n.a. AnPTSemY

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

Poly(␧-caprolactone) Byun et al. [202] 458–502 252.2–283.2 28 SynVisVar

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

Polystyrene-␤-poly(1,1,2,2-tetrahydroperﬂuorodecyl acrylate) André et al. [171] 297–331 12–23 n.a. SynVisVar

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

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

Vetiver grass extract Takeuchi [706] 303–333 6–32 25 SynVisVar

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

1,2-Benzanthracene Karásek et al. [409] 313–423 4.9–5.2 1.4 AnPTSemY

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

Voronov et al. [750] 270–285 2.1–9.1 n.a. SynNon

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

1-n-Butyl-3-methylimidazolium Yokozeki and Shiﬂett [779] 283–355 0.1–2.3 15.3 SynT

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

1-n-Butyl-3-methylimidazolium Jou and Mather [399] 298–403 0–9.6 n.a. AnTVcir

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

1,1,3,3-Tetramethylguanidium lactate Yuan et al. [782] 308–328 1.2–9.9 n.a. SynT

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

1,1,3,3-Tetramethylguanidium lactate Yuan et al. [782] 308–328 2.1–8.7 n.a. SynT

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

1,1,3,3-Tetramethylguanidium lactate Yuan et al. [782] 308–328 1.1–9.7 n.a. SynT

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

1-n-Butyl-3-methylimidazolium Kumelan et al. [459] 293–373 0.7–9.1 29.5 SynVis