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Article history: As a part of a series of reviews, a compilation of systems for which high-pressure phase-equilibrium
Received 26 June 2009 data were published between 2000 and 2004 is given. Vapor–liquid equilibria, liquid–liquid equilibria,
Received in revised form 12 August 2009 vapor–liquid–liquid equilibria, solid–liquid equilibria, solid–vapor equilibria, solid–vapor–liquid equilib-
Accepted 13 August 2009
ria, critical points, the solubility of high-boiling substances in supercritical fluids, the solubility of gases
Available online 20 August 2009
in liquids and the solubility (sorption) of volatile components in polymers are included. For the systems
investigated, the reference, the temperature and pressure range of the data, and the experimental method
Keywords:
used for the measurements are given in 54 tables. Most of experimental data in the literature have been
Experiment
Data
given for binary systems. Of the 1204 binary systems, 681 (57%) have carbon dioxide as one of the com-
Method ponents. Information on 156 pure components, 451 ternary systems of which 267 (62%) contain carbon
VLE high pressure dioxide, 150 multicomponent and complex systems, and 129 systems with hydrates is given. Experimen-
Hydrocarbons tal methods for the investigation of high-pressure phase equilibria are classified and described. Work on
Non-hydrocarbons the continuation of the review series is under way, covering the period between 2005 and 2008, and will
be published in 2010.
© 2009 Elsevier B.V. All rights reserved.
0378-3812/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2009.08.008
2 R. Dohrn et al. / Fluid Phase Equilibria 288 (2010) 1–54
The classification of experimental methods for the investiga- Small samples can be withdrawn using capillaries (Cap) [33] or
tion of high-pressure phase equilibria that has been used in the special sampling valves (Val), e.g., using HPLC-valves [34] or fast-
previous reviews [10,13] has been further refined for this work acting pneumatic valves, like the rapid on-line sampler-injector of
(Fig. 2). There are two main classes, depending on how the com- Richon [35]. Often sampling valves are directly coupled to analytical
positions of the equilibrium phases are determined (analytically or equipment, e.g., to a gas chromatograph [36], a high-performance
not) and whether the mixture to be investigated has been prepared liquid chromatograph [37], or a supercritical fluid chromatograph
(synthesized) with precisely known composition or not: analytical [34]. For sampling from multiphase systems (e.g., VLLE) a movable
methods and synthetic methods. sampling needle [38] can be used.
The smallest equilibrium cell of all articles from this review
using an analytical method with sampling was used by Bahramifar
3.1. Analytical methods (An) et al. [39]: only 0.5 cm3 volume with a sampling loop of 23 mm3 .
The largest relative sample (14%) from a constant volume cell was
Analytical methods (designated with An) involve the analytical taken by Garmroodi et al. [40]: a 143 mm3 sample from a 1 cm3
determination of the compositions of the coexisting phases. When equilibrium cell.
the equilibrium cell is filled with the components at the beginning Sometimes, equilibrium cells used for analytical methods are
of the experiment, the overall composition of the mixture is not equipped with one or more windows for visual observation of the
precisely known, only so far that the mixture under desired con- cell content (Vis). Secuianu et al. [41] use a variable-volume cell
ditions (P and T) separates into two or more phases that are to with two sapphire windows where one of the windows acts as a
be investigated, e.g., into a liquid and a vapor phase when VLE is piston.
to be measured. The composition of the phases is analyzed either Analytical methods without sampling use a physicochemical
with sampling and analysis under ambient pressure or without method of analysis inside the equilibrium cell under pressure.
sampling by using physicochemical methods of analysis inside the These are mainly spectroscopic methods (AnSpec), e.g., Andersen
equilibrium cell under pressure. et al. [42], gravimetric methods (AnGrav), e.g., Sato et al. [43], or
Analytical methods with sampling can be classified, depend- other methods (AnOth), e.g., Boudouris et al. [44]. These methods
ing on the attainment of equilibrium, into isothermal methods avoid the problems related to sampling from a high-pressure cell.
(AnT), isobaric–isothermal methods (AnPT) and isobaric methods The main advantage of analytical methods is that they can be
(AnP). Withdrawing a large sample from an autoclave causes a used for systems with more than 2 components without significant
considerable pressure drop, which disturbs the phase equilibrium complications. When the compositions of all phases are analyzed,
significantly. This pressure drop can be avoided by a variable- each experiment yields complete information on the tie-line(s).
volume cell (Var) [26], by using a buffer autoclave in combination
with a syringe pump [27], or by blocking off (Blo) the sampling 3.1.1. Analytical isothermal methods (AnT)
volume from the remaining content of the equilibrium cell before Characteristic for isothermal methods is that the temperature
pressure reduction [28–30]. Sane et al. [31] use an electronic of the system stays constant during the equilibration process, e.g.,
syringe pump to keep the pressure in a variable-volume cell con- when the system is in contact with a heat reservoir. The other equi-
stant during sampling. If only a small sample is withdrawn or if librium properties, like the pressure and the composition of the
a relatively large equilibrium cell is used, the slight pressure drop phases, reach equilibrium values, depending on other variables,
does not affect the phase compositions significantly. The largest like mole numbers and volume. At the beginning of an experiment,
equilibrium cell (volume of 9 dm3 ) used in the articles of this review an equilibrium cell is charged with the substances of interest. The
was used by the late Danesh and co-workers [32] to measure phase pressure is adjusted above or below the desired equilibrium value,
equilibria in gas condensate systems. depending on how equilibration will change the pressure. After
4 R. Dohrn et al. / Fluid Phase Equilibria 288 (2010) 1–54
the desired temperature has been reached, the mixture is kept at libria or for the measurement of solubilities of gases in liquids
a constant temperature. By stirring the mixture or by rocking the [54].
autoclave or by recirculating one or more phases, time for equilibra- In a special kind of blocking off a part of the equilibrium cell
tion of the phases is reduced. After some time, the pressure reaches the sampling volume is within the equilibrium cell. We call this
a plateau. The pressure can be readjusted, by adding or withdrawing method “in situ sampling” (AnTIns). It can be used for the mea-
material or by changing the volume of the equilibrium cell. Usually, surement of the solubility of solids in supercritical fluids. Sherman
the equilibration is continued for at least 30 min after the pressure et al. [55] put an excess amount of solute in a glass vial, capped
plateau is sufficiently close to the desired value. Before taking sam- with coarse filter paper, in the equilibrium cell. After equilibration
ples from the coexisting phases, the mixture is given sufficient time and careful depressurization, the vial is removed and weighed. The
without stirring, rocking or recirculation for the separation of the solubility can be calculated from the difference of the initial and
phases [41]. Otherwise the sample might not be homogeneous but final mass of the solute in the vial and the difference of the volume
contain material from another phase, e.g., droplets, bubbles or solid of the equilibrium cell and the vial. As modification, Galia et al.
particles. [56] used three vials, of which only one was initially filled with the
For the measurement of solid–liquid equilibria in wax systems, solute.
Pauly et al. [45] used an isobaric and isothermal filtration step Nikitin et al. [57,58] used an alternative technique which avoids
to ensure that the liquid phase to be sampled is free of solid sampling from a high-pressure cell, for sorption measurements
particles. This was performed in an equilibrium cell with two of carbon dioxide in polystyrene. Equilibration, the absorption of
variable-volume chambers connected via a filtration system (a disc volatile component in the polymer, might take several hours. Then,
of sintered steel with 3 m of porosity). a fast depressurization procedure (<10 s) followed by a quick trans-
Isothermal methods that use stirring or rocking to ensure a rapid port of the sample to an analytical balance (<5 s) is performed. The
approach to equilibrium are often called analytical-static methods. mass decrease of the polymer sample due to desorption of car-
As opposed to recirculating methods, the mixture does not leave the bon dioxide is recorded and analyzed. The initial value of sorbate
equilibrium cell during the experiment. But, since the expressions mass can be determined by extrapolation of the desorption curve
“static cell” and “static method” are used by some authors for other to the beginning of depressurization. We designate this sampling
experimental methods (e.g., for a synthetic method in a view cell and analytical method with “material loss analysis” (AnTMla).
or for a synthetic method using the material balance to determine As compared to analytical isobaric–isothermal methods,
solubilities of gases in liquids), we avoid the expression “static” in isothermal methods have the advantage that time for equilibration
our classification. can be easily extended. If carried out carefully they can produce
Sampling through capillaries can lead to differential vaporiza- very reliable results.
tion and scattering results, especially for mixtures containing light 27.6% of all systems investigated of this review have been mea-
and heavy components when no precautions have been taken to sured with an analytical isothermal method.
prevent a pressure drop all along the capillary [46]. Differential
vaporization can be avoided with an experimental design that 3.1.2. Analytical isobaric–isothermal methods (AnPT)
ensures that most of the pressure drop occurs at the end of the In isobaric–isothermal methods, often called dynamic methods,
capillary close to the chromatographic circuit, e.g., Richon and co- one or more fluid streams are pumped continuously into a ther-
workers [47] used a micro-stem ending with a nose entering inside mostated equilibrium cell. The pressure is kept constant during the
the capillary to reduce the cross-sectional area at the end of the experiment by controlling an effluent stream, usually of the vapor
capillary. Another possibility to reduce sampling problems is the phase.
recirculation of one or more phases, having the advantage that
the sampling volume (e.g., the loop of a six-port valve) is filled 3.1.2.1. Continuous-flow methods (AnPTCon). In a typical design of a
isobarically. Disadvantages of a recirculation are the need for a well- continuous-flow method, high-pressure metering pumps feed the
working pump with only little pressure drop and the need for a preheated components into a mixer, where the desired temper-
uniform temperature field to avoid partial condensation or vapor- ature and phase equilibrium is attained. Often, static mixers are
ization in the recirculation line. Therefore, recirculation methods used [59,60]. The feed stream from the mixer is separated in an
are not suitable in the region close to the critical point where small equilibrium cell into a vapor and a liquid phase. To facilitate phase
changes in temperature and pressure have a strong influence on separation, a cyclone separator was used by Fonseca et al. [59].
the phase behavior [11]. Effluents from both phases are withdrawn continually, depressur-
When only the vapor phase is recirculated (Vcir), it is withdrawn ized, accumulated and analyzed, usually after the experiment. The
continually and passed back into the equilibrium cell through the pressure is adjusted by controlling the effluent stream of the top
liquid phase by the action of a pump, e.g., Mather and co-worker phase. The interface level between the fluid phases in the equilib-
[48]. Samples can be withdrawn by placing a sampling valve in the rium cell can be adjusted with the bottom-phase expansion valve,
recirculation loop [37] or by blocking off a volume between two whereby the interface level is usually determined visually [61].
valves in the recirculation loop [49]. The liquid phase is usually Continuous-flow methods have the advantage that sampling
analyzed by taking samples through capillaries. Laursen et al. [50] does not disturb the equilibrium. If larger samples are needed for
proposed a simple VLE equipment with vapor-phase recirculation analyses, the run time of the experiment can be extended to accu-
that allows liquid phase sampling to measure the gas solubility in mulate more material. Measurements at higher temperatures are
substances with high stickiness and viscosity, like wood resins. possible without thermal decomposition or polymerization reac-
Recirculation of both the vapor and the liquid phase (VLcir) has tions due to the short residence time of the components in the
the advantage that sampling from both phases is possible without apparatus [62]. Using a continuous-flow method, Haruki et al. [63]
using capillaries [51,52]. If a vibrating-tube densimeter is installed measured phase equilibria for water + hydrocarbon systems near
in a recirculation loop, the density of the circulated phase can be the critical point of water.
determined easily. The pump should be turned off during density Hurst et al. [64] describe a continuous-flow cell with large
measurement to avoid errors due to pulsation [52]. Sometimes only diameter optical ports suitable for visual observation and Raman
the liquid phase is circulated (Lcir), e.g., for mixing, for blocking spectroscopic studies of aqueous solutions at temperatures up to
off a large liquid phase volume from the equilibrium cell before 500 ◦ C. The cell was instrumented with a heated cylindrical insert
pressure reduction [53], for the measurement of liquid–liquid equi- (‘hot finger’) that was employed for salt solubility, salt deposition
R. Dohrn et al. / Fluid Phase Equilibria 288 (2010) 1–54 5
and salt nucleation studies in near-critical aqueous solutions. The produce solute precipitation. Sampling at isobaric conditions is per-
crystalline phases were observed using Raman spectroscopy. formed with a six-port valve. Special attention must be taken into
Continuous-flow methods can be used only for systems where account during the regeneration of mercury and cleaning of the
the time needed to attain phase equilibrium is sufficiently short. apparatus.
3.1.2.2. Semi-flow methods (AnPTSem). In semi-flow methods, only 3.1.2.3. Chromatographic methods (AnPTChro). Chromatographic
one phase is flowing while the other phase stays in an equilib- methods measure solute retention in a chromatographic column
rium cell. Semi-flow methods are sometimes called “single-pass and connect it with the Gibbs energy of solute transfer between
flow methods”, “gas-saturation methods” or “pure-gas circulation the stationary and the mobile phase. Roth [76] gives a review on
methods”. A gas stream from a high-pressure cylinder is passed applications of SFC for the determination of the relative values of
through two cells in series containing the liquid. The first cell serves solute solubilities in supercritical fluids, and on the determination
as a presaturator and the second cell as equilibrium cell. Upon of solute partition coefficients between a supercritical fluid and
equilibration, the effluent of the vapor phase is reduced in pres- the stationary phase. In SFC, the thermodynamic analysis of solute
sure and directed to a trap where the condensed liquid is collected. retention is more difficult than in GC because the uptake of the
The quantity of the gas coming out of the trap can be determined mobile phase fluid by the stationary phase is no longer negligi-
volumetrically, e.g., with a wet test meter. ble. Chromatographic methods have as advantage the possibility
Most often, only the composition of the vapor phase is ana- to determine equilibrium properties and diffusion coefficients in
lyzed (AnPTSemY), for example to determine the solubility of a one experiment [77].
low-boiling (liquid or solid) substance in a supercritical gas [65]. Sato et al. [78] used a chromatographic method (AnPTChro) to
The composition of the vapor-phase effluent can be determined in measure the vapor–liquid equilibrium ratio of n-hexane at infinite
many different ways, e.g., by using a spectroscopic method [66], dilution in propylene + impact polypropylene copolymer, while to
by using a multi-port sampling valve and subsequent HPLC anal- determine the solubility of propylene in the polymer they used the
ysis or after expansion to atmospheric pressure using cold traps, synthetic isothermal method (SynT).
an absorption bath, or a chromatography column filled with an Chester [79] reviewed a chromatographic technique, which he
appropriate adsorbent for the solute studied [67]. For these kinds of calls “flow injection peak-shape method” that allows to deter-
measurements (AnPTSemY), no samples from the condensed phase mine the pT coordinates of the vapor–liquid critical locus of binary
are taken. systems. It can be implemented using open-tubular SFC instru-
When a semi-flow method is used for the measurement of mentation by replacing the SFC column with several meters of
vapor–liquid equilibria AnPTSemXY, the composition of the liquid fused-silica tube. This tube may be deactivated but is not coated
phase needs to be determined. Therefore, a sample from the liquid with a stationary phase. The procedure to map a critical locus
phase is withdrawn through tubing, depressurized, and analyzed involves selecting a temperature, then making injections at various
[68]. Semi-flow methods can also be used to measure the solubility pressures while looking for the pressure where the peaks change
of a gas in a liquid, e.g., Tan et al. [69]. The experimental proce- from their rectangular appearance ( = liquid + vapor phase in the
dure (AnPTSemX) is similar to the one for measuring vapor–liquid column) to distorted Gaussian (= homogeneous phase in the col-
equilibria, but there is no need to determine the composition of the umn). This transition pressure provides an estimate of the mixture
effluent from the vapor phase. critical pressure corresponding to the oven temperature.
Tuma et al. [70] used a modified supercritical fluid chromato-
graph (SFC) to measure the solubility of dyes in carbon dioxide. The 3.1.3. Analytical isobaric methods (AnP)
column was filled with finely pulverized dyestuff. Analysis of the The boiling temperature of a mixture is measured at isobaric
vapor-phase stream is done by VIS-spectroscopy (AnPTSemYSpec). conditions and phase compositions are determined after sampling
The major uncertainty of all flow methods is the possible lack of and analysis. Typically, isobaric experiments are performed in an
attainment of equilibrium. Sauceau et al. [71] used an equilibrium ebulliometer (from latin ebullio “to boil, to bubble up”), which is
cell with three compartments, which is equivalent to three cells in a one-stage total-reflux boiler equipped with a vapor-lift pump to
series. Another difficulty is the partial condensation of the solute spray slugs of equilibrated liquid and vapor onto a thermometer
from the saturated vapor stream in the tubing, particularly in and well. As opposed to the more frequently used synthetic isobaric
after the expansion valve. This undesired variable hold-up of the method (SynP), vapor and liquid streams are separated, collected
solute can lead to scattering results in the order of 10% [72]. To and can be sampled and analyzed. The compositions of the liquid
collect precipitated solute at the end of an experiment from the and the vapor phase change with time and reach a steady state
tubing and from the expansion valve, Takeshita and Sato [73] use a which should differ insignificantly from the true equilibrium value.
stream of carbon dioxide after having blocked off the equilibrium Usually, the analytical isobaric method is used to measure low-
cell. pressure data. Then, it is often called the “dynamic” VLE method.
Ferri et al. [74] describe an experimental technique that allows
to measure high concentrations of dyestuff in a supercritical fluid. 3.1.4. Analytical spectroscopic methods (AnSpec)
They use a second pump to stabilize the flow rate of the fluid in the Spectroscopic methods allow analyzing the composition
extractor, damping the pulses of the first pump. Glass wool before of the phases at high pressures without having to take sam-
and after the packed bed guarantees a uniform flow distribution ples, e.g., by using near infrared spectroscopy [42]. Cruz
and prevents particle entrainment. A line by-passing the extractor Francisco et al. [80] investigated the phase behavior of
allows solubility measurements at high concentrations. It dilutes lecithin + water + hydrocarbon + carbon dioxide mixtures using
the saturated fluid stream with clean carbon dioxide and reduces a 2 H NMR technique in combination with light microscopy.
the risk of valve clogging and flow rate instability. Aizawa et al. [81] developed a high-pressure optical cell for the
To overcome the problems connected to depressurization, investigation of absorption and fluorescence phenomena using a
Pauchon et al. [75] developed a semi-flow method that works “totsu” (denoting the shape) type window. The protruding part of
without pressure reduction. The effluent vapor-phase flows into the window acts as a light-guide and enhances the laser power
the top part of an autoclave which is filled with mercury. The imparted onto the sample in the monitoring light.
use of mercury, acting as a piston, allows obtaining a precise Shieh et al. [82] studied the effect of carbon dioxide on the mor-
adjustment of the vapor flow and avoids pressure changes that phological structure of compatible crystalline/amorphous polymer
6 R. Dohrn et al. / Fluid Phase Equilibria 288 (2010) 1–54
blends by means of small angle X-ray scattering (SAXS) with the Guigard et al. [90] further developed the quartz crystal tech-
measurement of absolute scattering intensity. nique to measure low solubilities of metal chelates in supercritical
The advantage of avoiding the trouble with taking samples is fluids. A small mass of solute was deposited on the crystal and sol-
often overcompensated by the need of time consuming calibrations ubility was measured by observing the crystal’s frequency change
at high pressures. Only 1.5% of all systems covered in this review as this solute dissolves in the supercritical fluid.
have been investigated with a spectroscopic method. Mohammadi et al. [91] used a quartz crystal balance as an
extremely sensitive detector for the appearance of hydrates. 1 ng
3.1.5. Analytical gravimetric methods (AnGrav) mass change results in a 1 Hz frequency change. Concerning the
With gravimetric methods the mass of a condensed phase (e.g., classification of methods this is not an analytical method (AnOth),
a polymer [43] or an ionic liquid [83]) in phase equilibrium with but a non-visual synthetic method (SynNon).
a fluid phase is measured. Using additional information, like the As compared to conventional methods, such as gravimetric
phase densities, the phase compositions can be determined. Pala- (AnGrav) or pressure decay (SynT), a much higher sensitivity for
mara et al. [84] placed the entire high-pressure cell on a balance the determination of mass changes can be achieved with a quartz
and performed the equilibration under isobaric conditions. The microbalance. Therefore, smaller samples are needed and phase
weight of the cell and attached valve is critical because commer- equilibrium is attained much faster [92], since equilibration time
cially available analytical balances sensitive enough to perform is inversely proportional to the square of the film thickness. Errors
these measurements have low maximum load capacities. In the rise with temperature and pressure, due to dampening and viscous
study of Palamara et al. [84] the cell and attached valve weighed dissipation [89].
approximately 190 g. Another analytical method was used by Morris et al. [93] to
Cutugno et al. [85] placed a quartz spring balance and Moore measure low gas solubilities, e.g., of hydrogen in water. A palla-
and Wanke [86] placed an electro microbalance within a high- dium/hydrogen electrical resistance sensor was used to determine
pressure cell to measure sorption of gases in polymers. Kleinrahm the hydrogen content in the liquid phase.
and Wagner [87] developed a unique balance, so-called a magnetic Abbott et al. [94] proposed a capacitative method (dielectric
suspension balance, for accurate measurements of fluid densities. constant method) to measure the solubility of low-volatile sub-
It has the main advantage that the sample and the balance are iso- stances in supercritical gases. They used a 25 cm3 high-pressure
lated. An electronically controlled magnetic suspension coupling is cell, lined with a layer of Teflon. A capacitor consisting of two par-
used to transmit the measured force from the sample enclosed in a allel rectangular stainless steel plates (area of 6.6 cm2 , held 1 mm
pressure vessel to a microbalance. The suspension magnet, which apart by Teflon spacers) was placed in the vapor phase. The dielec-
is used for transmitting the force, consists of a permanent mag- tric constant of the saturated vapor phase was measured at different
net, a sensor core and a device for decoupling the measuring-load. pressures. To calculate the concentration of the solute in the vapor
An electromagnet, which is attached at the underfloor weighing phase from the dielectric constant, information on the permanent
hook of a balance, maintains the freely suspended state of the sus- dipole moments and the molecular polarizabilites of the compo-
pension magnet via an electronic control unit. Using this magnetic nents of the mixture needs to be known.
suspension coupling, the measuring force is transmitted contact-
lessly from the measuring chamber to the microbalance, which 3.2. Synthetic methods (Syn)
is located outside the chamber under ambient atmospheric con-
ditions. Several investigators used a magnetic suspension balance The idea of synthetic methods is to prepare a mixture of pre-
to measure the solubility and diffusivity of volatile components in cisely known composition and then observe the phase behavior
polymers, e.g., Sato et al. [88]. in an equilibrium cell and measure properties in the equilibrium
Gravimetric methods need corrections for buoyancy. Therefore, state, like pressure and temperature. No sampling is necessary. The
particularly at high pressures, exact information on the density of problem of analyzing fluid mixtures is replaced by the problem of
the fluid phase and on the density and volume of the condensed “synthesizing” them [7]. Synthetic methods can be applied with or
phase is essential. without a phase transition. In both cases, first a mixture of precisely
known composition is prepared.
3.1.6. Other analytical methods (AnOth) In synthetic methods with a phase transition values of tempera-
Like in gravimetric methods, quartz crystal microbalances can ture and pressure are adjusted so that the mixture is homogeneous,
be used to determine the solubility of a gas in a polymer by measur- a single phase exists. Then the temperature or pressure is varied
ing the mass of the polymer in equilibrium with the gas. From the until the beginning of the formation of a new, a second phase is
basic principle, it is not a gravimetric measurement, so that buoy- observed. The composition of the first, large phase can be set to the
ancy effects play a different role. Quartz crystal microbalances are known overall composition. The composition of the second, small
based on the piezoelectric effect observed in a AT-cut quartz crys- phase is not known. Each experiment yields one point of the pTx
tal. The crystal under the influence of an applied alternating electric phase envelope.
voltage undergoes a shear deformation which becomes maximum Instead of a variation of temperature or pressure to cause a phase
at a certain frequency called the resonance frequency [44]. This res- transition the overall concentration can be changed. Wubbolts et al.
onance frequency depends on the mass, and thus any mass change [95] use this approach, designated with “vanishing-point method”
will result in a respective frequency shift. The sorption experi- or “clear-point method”, for SLE measurements. A clear solution of
ment involves measurement of the resonance frequency of the bare a given solute concentration is added to a known amount of anti-
(clean) crystal, of the same crystal coated with polymer, and of the solvent until the last crystal disappears. The composition of the
coated crystal after the polymer reaches equilibrium with a gas, all mixture at this vanishing point equals the solubility of the mix-
at the same controlled temperature. Concurrently, the resonance ture. When the procedure is repeated with a solution of a different
frequency of a reference crystal is also measured under the same concentration another point of the curve is found.
conditions in order to compensate any temperature or pressure Depending on how the phase transition is detected, synthetic
effects. Park et al. [89] examined the effect of temperature deviation methods with a phase transitions can be divided into visual (SynVis)
and pressure change on the frequency shift by measuring the fre- and non-visual synthetic methods (SynNon).
quency change of an uncoated crystal under high-pressure carbon In synthetic methods without a phase transition, equilibrium
dioxide. properties like pressure, temperature, phase volumes and densi-
R. Dohrn et al. / Fluid Phase Equilibria 288 (2010) 1–54 7
ties are measured and phase compositions are calculated using the the basis of phase detection, while Drozd-Rzoska et al. [114] used
material balance. Synthetic methods without a phase transition can measurements of the relative dielectric permittivity for LLE mea-
be divided into isothermal (SynT), isobaric (SynP) and other (Syn- surements at high, low and negative pressures. If the total volume
Oth) synthetic methods. During the period covered in this review of a variable-volume cell can be measured accurately, the appear-
(2000–2004) synthetic methods with a phase transition have been ance of a new phase can be obtained from the abrupt change in
used about 5 times more often than synthetic methods without a slope on the pressure–volume plot more accurately than by visual
phase transition. observation [115,116]. As an alternative pVT measurements can be
Synthetic methods can be used where analytical methods fail, performed and the intersection of isochors can be used to deter-
i.e., when phase separation is difficult due to similar densities mine points on the coexistence curve. A sharp change in the slope
of the coexisting phases, e.g., near or even at critical points and (dp/dT), occurs at the phase boundary.
in barotropic systems, where at certain conditions the coexisting May et al. [117] used a microwave re-entrant resonator to detect
phases have the same density. Often, the experimental procedure the appearance of dew and bubble points in hydrocarbon sys-
is easy and quick [5]. Because no sampling is necessary the experi- tems. Takagi et al. [118] measured bubble point pressures using an
mental equipment can concentrate on few components and the vol- ultrasonic speed apparatus. Since the acoustic wave excited in the
ume of the equilibrium cell can be small. Therefore, the apparatus sample for the speed of sound measurement was strongly absorbed
can be rather inexpensive. On the other hand, it can be designed for in the gas phase as compared to the absorption in the liquid phase,
extreme conditions concerning temperatures and pressures [96]. the appearance of the gas phase was detected by the change of
Cohen-Adad [97] describes a diamond anvil cell that can be used the acoustic echo signal. For searching critical points of pure fluids,
for pressures up to 135 GPa. The experimental data at the highest acoustic methods have the advantage that even for temperatures
pressures of all articles covered in this review were taken by Fang several degrees above the critical point, the sound velocity exhibits
et al. [98], also with a diamond anvil cell, at pressures up to 2.6 GPa. a minimum when measured isothermally as a function of pressure
For multicomponent systems, experiments with synthetic [119].
methods yield less information than with analytical methods, To measure the critical temperature of thermally unstable sub-
because the tie-lines cannot be determined without additional stance, the pulse-heating method, as described by Nikitin et al.
experiments. Therefore, synthetic methods are less often used for [120], can be used. It is based on measuring the pressure depen-
systems containing more than 2 components. dence of the temperature of the attainable superheat (spontaneous
boiling-up) of a liquid with the help of a thin wire probe heated
3.2.1. Visual synthetic methods (SynVis) by pulses of electric current. When the pressure in the liquid
The appearance of a new phase is usually detected by visual approaches the critical pressure, the temperature of the attainable
observation of the resulting turbidity or meniscus in a view cell. superheat approaches the critical temperature.
For isooptic systems where the coexisting phases have approxi- A synthetic non-visual method that looks at first sight like
mately the same refractive index, visual observation is impossible. an analytical continuous-flow method (AnPTCon) was used by
The visual synthetic method can be used not only for the determina- VonNiederhausern et al. [121] to determine the critical points of
tion of simple vapor–liquid equilibria, but also to study complicated thermally unstable or reactive components. To achieve very short
phase behavior, e.g., multiphase equilibria [99], solid–liquid equi- residence times, a sample of precisely known composition is con-
libria [100], critical curves of mixtures [101], gas hydrate formation tinuously displaced and heated in a capillary tube. No analysis of the
[102], cloud-point determination [103] and phase equilibria in samples takes place. To determine the critical point, several tem-
polymer–solvent systems [104]. perature scans must be made in the vicinity of the critical point.
The Cailletet apparatus of TU Delft [105] is the most frequently Below the critical point, the temperature scan will show a flat, hor-
used type of apparatus according to the synthetic visual method. It izontal region indicative of isothermal boiling. Above the critical
consists of a thick-walled Pyrex glass tube (50 cm long, 3 mm inner point, the transition region is no longer flat and horizontal. The
diameter) with the open end placed in an autoclave and immersed critical point is inferred by the temperature and pressure where
in mercury. The mercury confines the sample in the Cailletet tube. A isothermal boiling is no longer observed.
stainless steel ball driven by reciprocating magnets stirs the sample. Valyashko et al. [122] used jumps of the isochoric heat capacity
Daridon et al. [106] used a very small cell with a volume of to detect the appearance of a vapor phase or a second liquid phase.
0.03 cm3 for the visual observation of synthetic waxes at high Wurflinger and Urban [123] studied the phase behavior of liquid
pressures. The cell is placed within a polarizing microscope. The crystals with high-pressure differential thermal analysis (DTA).
apparatus allows the visual observation of crystals of 2 m. The experiments at the highest temperatures of all articles cov-
When only small quantities of a sample shall be used in the ered in this review were performed by Manara et al. [96]. They
experiment, e.g., to observe solid–liquid–gas equilibria, a glass cap- investigated the melting point of uranium dioxide at high pres-
illary can be placed inside the high-pressure view cell [107,108]. sures. Temperatures of almost 3200 K were needed. Such high
To improve the detection of phase transitions, some authors use temperatures can be measured optically by pyrometry. Two pulsed
laser light scattering techniques [103,109]. Jager and Sloan [110] Nd–YAG laser beams were mixed through a suitable optical sys-
use Raman spectroscopy to detect hydrates. Dong et al. [111] use tem in the same fiber and then focused onto the sample surface.
additional SAXS measurements to determine the median micelle The pulse with the higher power peak was used to heat the sample
size of the water-in-carbon dioxide microemulsions. above the melting point; the other one, less powerful, but of longer
Veiga et al. [112] used glass capillary helixes not only to inves- duration, was used to control the cooling rate on the sample sur-
tigate the high pressure behavior of pure compounds but also at face. This lead to a much better definition of the freezing plateau.
negative pressures as far down as −20.8 MPa. Pressure was applied by using helium.
With 36.4% of all systems investigated in this review, synthetic Diamond anvil cells are particularly suitable for non-visual mea-
visual methods were the most frequently used type of method. surements at very high pressures [97]. The selective transparency
of diamond for IR to X-ray and gamma-ray radiations permits in
3.2.2. Non-visual synthetic methods (SynNon) situ measurements during experiments.
As an alternative to visual observation, other physical proper- Ngo et al. [124] used the synthetic non-visual method to mea-
ties can be monitored to detect phase transitions. Minicucci et al. sure the solubility of solids in carbon dioxide. First the cell was
[113] made use of transmitted X-rays instead of visible light, as charged with the solid. Then it was pressurized with carbon diox-
8 R. Dohrn et al. / Fluid Phase Equilibria 288 (2010) 1–54
ide and stirred constantly. Equilibrium of the mixture was observed [132] or the solubility of gases in ionic liquids [133] or in electrolyte
in situ by periodically taking spectra (UV absorbance) of the solu- solutions, e.g., by Gmehling and co-workers [134].
tion. The pressure was raised stepwise until no further significant When used for a pure component, the synthetic isothermal
increase in the peak absorbance was observed. This meant that all method delivers the vapor pressure, e.g., Funke et al. [135]. Then, it
solids had been dissolved in the fluid phase. is often called the “static” vapor-pressure method.
Randzio [125] used a new transitiometric method for investi- Often in synthetic isothermal methods, a view cell is used as
gation of the solid phase behavior in asymmetric binary systems. equilibrium cell. This has the advantages that unusual behavior,
Transitiometry is based on a simultaneous recording of both like foaming, can be seen, that the volumes of the liquid and the
mechanical and thermal variables of a thermodynamic transition vapor phase can be determined visually and that the cell can be used
induced by scanning one independent variable (p, T or V) while also according to the synthetic visual method. For example, Fukné-
the other independent variable is being kept constant. Taking Kokot et al. [107] measured solid–liquid–gas equilibria using the
the (tetracosane + methane) binary system as a test example, the synthetic isothermal method to determine the CO2 content in the
three-phase curve (solid + liquid + vapor) has been determined. The liquid phase and the synthetic visual method to detect solid forma-
apparatus (“transitiometer”) consists of a calorimeter equipped tion.
with high-pressure vessels, and a pVT system. During the isobaric Krüger et al. [136] compared results of the isothermal method
temperature scans both the heat flux and the volume variations for VLE of the n-pentane + poly(dimethylsiloxane) system with
were recorded. results of the gravimetric sorption method (AnGrav) and with
For measurements of solid–liquid equilibria at high pressures, inverse gas chromatography. These methods differ in the under-
the dead-volume of the apparatus can have a very negative influ- lying experimental principles as well as in the complexity of data
ence [97]. The volatility of constituents changes the nominal analysis. Despite of these differences, the agreement of the mea-
composition of a sample and can induce an incorrect apparent sured VLE data is excellent.
retrograde solubility curve.
To investigate the phase behavior in porous media, non-visual 3.2.4. Synthetic isobaric methods (SynP)
methods are particularly advantageous. Zatsepina and Buffett [126] The boiling temperature of a synthesized mixture is measured at
used electrical resistance measurements to monitor the appear- isobaric conditions and phase compositions are calculated using the
ance and growth of CO2 –hydrate crystals in the pore fluid. Omi et material balance. As opposed to analytical isobaric methods (AnP),
al. [127] used a high-pressure NMR probe to investigate the pres- no sampling or analysis is performed. Just as synthetic isothermal
sure and pore size dependence of the critical behavior of xenon in methods (SynT), synthetic isobaric methods (SynP) are performed
mesopores. without a phase transition. When used for a pure component –
Ivanic et al. [128] monitored the pressure and temperature in the composition is given anyway – the synthetic isobaric method
a hydrate-bearing system and identified equilibrium at the condi- delivers the vapor pressure, e.g., Weber et al. [137]. Then, it is often
tions where the last hydrate crystal in the system dissociates at the called the “dynamic” vapor-pressure method. Typically, isobaric
cross-point of the pT curves from cooling and from heating. experiments are performed in an ebulliometer as described in Sec-
Oag et al. [119] describe an apparatus where the determina- tion 3.1.3 (AnP). An ebulliometer was first used to determine the
tion of phase transitions and critical points can be carried out with molecular weights of substances, by measuring the changes of the
different methods: visually, by measuring the laser reflectance of boiling point of water caused by the presence of the unknown sub-
the fluid, which is at its maximum at the critical point, the sound stance. Twin ebulliometry can be used to determine the activity
velocity and by using vibrating shear mode sensors. coefficient at infinite dilution. The temperature difference between
an ebulliometer filled with the first (pure) component and a sec-
3.2.3. Synthetic isothermal methods (SynT) ond ebulliometer (under the same pressure) filled with the first
Synthetic isothermal methods are performed without a phase component and with a small amount of a second component
transition, where the pressure of a synthesized multiphase mix- (diluted solution) is measured. From the difference of the boiling
ture is measured at isothermal conditions and phase compositions temperatures, the activity coefficient at infinite dilution can be cal-
are calculated using the material balance. At the beginning of an culated. Usually synthetic isobaric methods are used to measure
experiment, an equilibrium cell is charged with a known amount low-pressure data.
of the first component, evacuated and thermostated to a given Ewing and Ochoa [138] used comparative ebulliometry to pre-
temperature. Then a known amount of the second component is cisely determine the vapor pressure of pure components at high
added whereby the pressure increases. The second component pressures. The sample and a reference fluid are boiled in separate
dissolves into the liquid phase, which leads to a decay of the pres- ebulliometers under a common pressure of gas such as helium or
sure in the equilibrium cell. Therefore, this method is also called nitrogen, and the condensation temperatures of the sample and of
pressure-decay method, especially when a polymer is used as the the reference fluid are measured. The common pressure is calcu-
first component. After equilibration pressure and temperature are lated from the known vapor pressure of the reference fluid. The
registered. No samples are taken. The composition of the vapor method has many advantages: direct measurement of pressure is
phase is calculated using a phase equilibrium model or assumed avoided, the fluids are degassed by boiling, and the ebulliome-
as just containing the pure gas, if we consider solubility in poly- ters act as heat pipes to provide high-performance thermostats.
mers for example, or other compounds with negligible volatility. The corresponding disadvantages are the considerable demands on
The composition of the liquid phase is calculated using the mate- thermometry, the solubility of the buffer gas at high pressures, and
rial balance from the known total composition, the composition thermal gradients due to pressure heads. But the greatest advan-
of the vapor phase and the phase densities and volumes [129]. tage is speed of measurement; typically, a pressure–temperature
By repeating the addition of the second component into the cell, point can be obtained in an hour.
several points along the boiling point line can be measured.
At lower pressures, were they are often designated as “static 3.2.5. Other synthetic methods (SynOth)
method” or “isothermal pTx method”, synthetic isothermal meth- Properties measured in the homogenous or heterogeneous
ods are very commonly used [130,131]. Examples for the use of region are used to calculate the phase boundaries.
the synthetic isothermal methods at high pressures are the deter- Abdulagatov et al. [139] used two-phase isochoric heat capacity
mination of the solubility of low-boiling substances in polymers measurements to determine the values of the critical pressure and
R. Dohrn et al. / Fluid Phase Equilibria 288 (2010) 1–54 9
slope of the vapor-pressure curve at the critical point of 18 pure Because the size of the equilibrium cell can be of importance,
components. e.g., for the pressure drop during sampling or for the amount of
For systems with two degrees of freedom (e.g., binary two-phase substances needed, the volume of the equilibrium cell is also given
equilibria or ternary three-phase equilibria), the compositions in the tables.
are fixed when temperature and pressure are given. Luks and Information on pure-component systems is given in Table 3.
co-worker [140] took phase volume and overall composition raw Most of experimental phase equilibrium data were on binary sys-
data for a set of three experimental runs at the same temperature tems: 1204 systems investigated have been divided into 28 tables
and pressure; in each run a different phase is caused to be volu- (Tables 4–31), with Table 4 (carbon dioxide + X) containing 681
metrically dominant relative to the other two phases. With the use binary system being by far the largest one. Many data have been
of mass balance, the compositions and molar volumes of the three measured for binary systems containing water, propane, difluo-
phases were determined from the three conjugate measurements romethane (HFC-32), and methane. Information on the tables and
[141]. their order can be found in the list of tables.
Di Nicola et al. [142] used isochoric pvTx measurements in the The additional components X are listed in alphabetic sequence.
single phase region (remark: otherwise it would be SynT) to fit The results of 434 ternary systems are given in 17 tables
the binary interaction parameters of an equation of state. Then, (Tables 32–48), e.g., 76 ternary systems of the type CO2 + water + X.
the compositions of the coexisting phases are calculated using the The order of the tables is analog to the order of the binary systems.
equation of state model. Information on 134 multicomponent systems (4–10 components)
is listed in Tables 49–52. Results for complex systems with many
components, like gas condensate reservoirs, are listed in Table 53.
4. Systems investigated Special tables have been generated for systems containing
hydrates (Tables 54–56). Overall, 129 systems with hydrates were
Almost 700 articles with experimental data on high-pressure found.
phase equilibria were found [143–745]. More than 2000 sys- To provide the reader with information on articles with cor-
tems have been investigated, from pure components, binary rections and discussions on published experimental high-pressure
systems up to complex mixtures with many components. In data, we prepared a compilation (Table 57). We give the original
Tables 3–56, the following information about the systems inves- article and the articles with corrigenda, comments or rebuttals to
tigated is given: the reference, the temperature and pressure comments when at least one of them falls in the period of the
range of the data and the experimental method used for the mea- review.
surements. The abbreviations used to designate the experimental Work on the continuation of the review series is under way,
method have been explained in the text above or are explained covering the period between 2005 and 2008, and will be published
in Table 2. in 2010.
Table 2
Experimental methods: abbreviations and frequency of use in review period.
46.7% Analytical methods, total composition is not exactly known, analysis of phases in equilibrium
Analytical methods with sampling:
27.6% AnT Analytical method: isothermal method
Blo Blocking off a large sampling volume from the equilibrium cell
Cap Sampling through capillaries
Ins In situ sampling: a sampling vial is in the equilibrium cell, careful depressurization, removal of vial
Lcir Liquid-phase recirculation
Mla Material loss analysis: sampling after depressurization, weight loss of sample due to desorption is
investigated
Val Sampling using a special valve
Var Variable-volume cell
Vcir Vapor-phase recirculation
VLcir Recirculation of the vapor and the liquid phase
0.0% AnP Analytical isobaric method, ebulliometry with phase analysis
15.4% AnPT Analytical isobaric-isothermal method
Con Continuous-flow method
SemX Semi-flow method used to measure the solubility of a gas in a liquid
SemY Semi-flow method used to measure the solubility of substance in a gas (or supercritical fluid)
Chro Chromatographic method, e.g. inverse SFC, inverse HPLC
Analytical methods without sampling:
1.5% AnSpec Spectroscopic analysis
1.1% AnGrav Gravimetric determination of phase composition: suspension balance or microbalance or quartz
spring balance
1.1% AnOth Other determination of phase composition, e.g. by resonance in a Quartz Crystal Microbalance
53.3% Synthetic methods, total composition is exactly known, no analysis of phases in equilibrium
Synthetic methods with a phase transition:
36.4% SynVis Visual detection of phase transitions
8.4% SynNon Non-visual detection of phase transitions
Synthetic methods without a phase transition:
6.1% SynT Isothermal, at least 2 phases, total pressure measured, often for pure-component vapor pressures;
mixtures: y calculated
0.2% SynP Isobaric, at least two phases, ebulliometry, often for pure-component vapor pressures, mixtures:
differential ebulliometry
2.2% SynOth Measured properties in the homogenous or heterogenous region are used to calculate the phase
boundaries
Additional remarks for all methods: Var, variable-volume cell; Vis, view cell, visual observation; Spec, spectroscopic method to get information; Pc, the critical pressure has
been measured; Tc, the critical temperature has been measured; X, only the composition of the liquid phase is determined; Y, only the composition of the vapor phase is
determined.
10 R. Dohrn et al. / Fluid Phase Equilibria 288 (2010) 1–54
Table 3
Pure-component systems: X.
Table 3 (Continued )
Table 3 (Continued )
Table 3 (Continued )
Table 4
Binary systems: carbon dioxide + X.
Table 4 (Continued )
Table 4 (Continued )
Table 4 (Continued )
Table 4 (Continued )
Table 4 (Continued )
Table 4 (Continued )
Table 4 (Continued )
Table 4 (Continued )
Table 4 (Continued )
Uranyl-thenoyltrifluoroaceton-water (UO2(TTA) * Wai and Waller [696] 313–313 10–32 3.5 or 15 AnTVal
2H2O)
Valeric acid Byun et al. [195] 313–393 2.5–20.7 28 SynVisVar
Vanillic acid Murga et al. [529] 313–333 8.5–50 4.4 AnPTSemY
Stassi et al. [652] 313–328 8.6–25 125 AnPTSemY
Vanillin Fukné-Kokot et al. [107] 343–353 0.1–19.7 14 SynVis
Fukné-Kokot et al. [107] 343–353 0.1–17.4 20 SynTVis
Fukné-Kokot et al. [304] 343–353 0.1–17.4 20 SynTVis
Vinyl acetate Byun and Shin [200] 313–393 2.4–12.6 28 SynVisVarPc
Vinyl acrylate Byun and Shin [200] 318–398 4.6–13.8 28 SynVisVarPc
Vitamin D2 Knez and Skerget [425] 303–353 7.9–30.2 120 AnT
Knez and Skerget [425] 336–382 0.2–27.2 14 SynVis
Vitamin D3 Knez and Skerget [425] 313–353 9.7–29.8 120 AnT
Knez and Skerget [425] 411–352 0.3–30.1 14 SynVis
Vitamin K3 Knez and Skerget [425] 313–353 8.1–30.7 120 AnT
Knez and Skerget [425] 347–379 0.2–31.7 14 SynVis
Water Addicks et al. [147] 293–293 1–2.5 450 AnTVarVis
Anderson [151] 274–288 0–2.1 1119 SynT
Bamberger et al. [61] 323–351 4–14.1 38 AnPTCon
Chapoy et al. [217] 274–351 0.1–9.3 n.a. SynNonVar
Jarne et al. [381] 251–288 0.1–4.1 n.a. AnPTSemY
Jarne et al. [381] 251–288 0.1–4.1 n.a. SynVis
Kiepe et al. [134] 313–393 0–9.2 n.a. SynT
Li et al. [461] 332–332 3.3–19.8 500 AnTVar
Mooijer-van den Heuvel et al. [521] 276–286 1.8–7.3 n.a. SynVis
Servio and Englezos [614] 273–283 2–6 n.a. AnTVis
Valtz et al. [688] 278–318 0.4–7.9 28 AnTValVis
Yang et al. [729] 277–280 4.9–14.2 n.a. AnTVcirVisVar
Zatsepina and Buffett [126] 271–281 2.8–3 n.a. SynNon
Weyburn formation brine Li et al. [461] 332–332 1.7–20.8 500 AnTVar
Xenon Ribeiro et al. [585] 282–299 5.9–7.2 5 SynNonPcTc
XMPA refrigeration oil Skripov et al. [645] 890–890 7–7 n.a. SynNonPcTc
Zopiclone Medina and Bueno [510] 313–333 10–25 15 AnPTSemY
Table 5
Binary systems: water + X.
1,8-Cineol (1,8-epoxy-p-menthane or eucalyptol) Miller and Hawthorne [513] 298–473 6.4–6.8 10.4 AnPTSemY
1-Octanol Brown et al. [190] 354–542 6.8–6.8 20 SynVisVar
2,2,4-Trimethylpentane Miller and Hawthorne [514] 298–473 6.5–6.5 10.4 AnPTSemY
2-Methylpropane (isobutane) Tian et al. [669] 625–695 25.7–306 60.1 SynVis
Acetophenone Brown et al. [190] 339–502 6.8–6.8 20 SynVisVar
Air Mohammadi et al. [91] 274–283 17–45.1 150 SynNon
Ammonia Munakata et al. [526] 310–400 0.5–4.5 n.a. SynNonVar
Anisole Brown et al. [190] 344–551 6.8–8.1 20 SynVisVar
Benzene Jou and Mather [392] 279–453 0–2 n.a. AnTLcirVis
Marche et al. [497] 343–424 1.7–1.7 530 AnT
Mathis et al. [502] 298–473 5–5 10 AnT
Miller and Hawthorne [514] 298–473 0.1–40 10.4 AnPTSemY
Black oil A—Westport Technology Center Ivanic et al. [128] 287–293 6.6–16.8 300 SynNon
Black oil B—Westport Technology Center Ivanic et al. [128] 279–284 3–7.8 300 SynNon
Black oil C—Westport Technology Center Ivanic et al. [128] 282–286 4.6–16.3 300 SynNon
Carbon dioxide Addicks et al. [147] 293–293 1–2.5 450 AnTVarVis
Anderson [151] 274–288 0–2.1 1119 SynT
Bamberger et al. [61] 323–351 4–14.1 38 AnPTCon
Chapoy et al. [217] 274–351 0.1–9.3 n.a. SynNonVar
Jarne et al. [381] 251–288 0.1–4.1 n.a. AnPTSemY
Jarne et al. [381] 251–288 0.1–4.1 n.a. SynVis
Kiepe et al. [134] 313–393 0–9.2 n.a. SynT
Li et al. [461] 332–332 3.3–19.8 500 AnTVar
Mooijer-van den Heuvel et al. [521] 276–286 1.8–7.3 n.a. SynVis
Servio and Englezos [614] 273–283 2–6 n.a. AnTVis
Valtz et al. [688] 278–318 0.4–7.9 28 AnTValVis
Yang et al. [729] 277–280 4.9–14.2 n.a. AnTVcirVisVar
Zatsepina and Buffett [126] 271–281 2.8–3 n.a. SynNon
Carvone (p-mentha-6,8-dien-2-one) Miller and Hawthorne [513] 298–473 6.1–6.5 10.4 AnPTSemY
Cesium chloride Matsuo et al. [504] 273–313 0.1–400 n.a. AnTVar
Copoly(PNIPAAM/VS) Azevedo et al. [156] 310–319 0.1–40 n.a. SynVis
Cyclohexane Marche et al. [497] 343–424 1.7–1.7 530 AnT
Deuterium oxide Bazaev et al. [165] 517–680 3.5–37.4 n.a. SynOthPcTc
d-Limonene ((R)-p-mentha-1,8,diene) Miller and Hawthorne [513] 298–473 6.9–7.2 10.4 AnPTSemY
Ethane Chapoy et al. [215] 278–303 0.3–4.6 34 AnTVal
Kim et al. [422] 277–298 1.4–20.1 n.a. SynVisVar
Mohammadi et al. [518] 274–343 0.3–4.9 34 AnTValVis
R. Dohrn et al. / Fluid Phase Equilibria 288 (2010) 1–54 23
Table 5 (Continued )
Table 6
Binary systems: ammonia + X.
Table 7
Binary systems: hydrogen sulfide + X.
Table 8
Binary systems: hydrogen + X.
Table 9
Binary systems: nitrogen + X.
1-n-Butyl-3-methylimidazolium hexafluorophosphate [bmim][PF6] Anthony et al. [83] 298–298 0–1.3 n.a. AnGrav
2-Methyltetrahydrofuran Fischer and Wilken [129] 311–311 0–9 n.a. SynT
␣-Pinene Laursen et al. [50] 298–318 3.1–14.5 90 AnTVcirX
Dimethyl ether Laursen et al. [38] 298–318 0.6–10.3 570 AnTValVis
Teodorescu Rasmussen [666] 278–318 0.4–8.4 700 AnTVal
Dimethylether Wallbruch et al. [697] 160–276 20.4–200 n.a. SynVisVar
Ethane Raabe et al. [53] 209–270 1.1–9 n.a. AnTLcirBlo
Raabe and Köhler [573] 114–138 0.7–3.2 n.a. AnTLcirBlo
Ethanol Fischer and Wilken [129] 298–398 0–9.2 n.a. SynT
Methanol Laursen and Andersen [434] 298–318 0.6–3 570 AnTValVis
1-Propanol Fischer and Wilken [129] 298–398 0–9.9 n.a. SynT
Oleic acid Laursen et al. [50] 298–318 3.2–14.6 90 AnTVcirX
Poly(ethylene glycol) 1500 Wiesmet et al. [33] 323–373 4.9–19.2 1000 AnTCap
Poly(ethylene glycol) 4000 Wiesmet et al. [33] 338–373 6.2–20 1000 AnTCap
Poly(ethylene glycol) 8000 Wiesmet et al. [33] 353–393 5.8–17.8 1000 AnTCap
Poly(ethylene) (LDPE) Davis et al. [252] 423–423 0.6–6.5 72 SynT
Polyvinylidene fluoride Grolier et al. [341] 411–436 0.1–190 36.3 SynNon
Vitamin K3 Knez and Skerget [425] 377–383 0.6–27.6 14 SynVis
Water Chapoy et al. [216] 274–363 0.9–7.1 28 AnTValVis
Mohammadi et al. [91] 274–283 19–45.3 150 SynNon
R. Dohrn et al. / Fluid Phase Equilibria 288 (2010) 1–54 25
Table 10
Binary systems: oxygen + X.
1-n-Butyl-3-methylimidazolium hexafluorophosphate [bmim][PF6] Anthony et al. [83] 298–298 0–1.3 n.a. AnGrav
Acetonitrile (ethanenitrile) Horstmann et al. [362] 305–353 0–2.6 n.a. SynT
Dibutyl ether Fischer and Wilken [129] 298–298 0–2.1 n.a. SynT
Methanol Fischer and Wilken [129] 298–348 0–9.1 n.a. SynT
n-Octane Fischer and Wilken [129] 298–348 0–8.9 n.a. SynT
1-Propanol Fischer and Wilken [129] 298–348 0–9.2 n.a. SynT
Toluene Fischer and Wilken [129] 298–348 0–9 n.a. SynT
Water Mohammadi et al. [91] 273–284 13.5–43.7 150 SynNon
Tan et al. [69] 300–300 1–10 500 AnPTSemX
Table 11
Binary systems: carbon monoxide + X.
1-n-Butyl-3-methylimidazolium hexafluorophosphate [bmim][PF6] Anthony et al. [83] 298–298 0–1.3 n.a. AnGrav
Carbon dioxide Ke et al. [411] 280–298 8.1–9.9 n.a. SynNonPcTc
Cyclohexane Gao et al. [319] 344–410 1.5–5.1 25 SynT
Dichloromethane (HCC-30) Jónasson et al. [386] 303–363 0.4–7 700 AnTVal
n-Hexane Gao et al. [318] 501–505 3–3.3 50 SynVisVarPcTc
Table 12
Binary systems: nitrous oxide + X.
Table 13
Binary systems: methane + X.
1-n-Butyl-3-methylimidazolium hexafluorophosphate [bmim][PF6] Anthony et al. [83] 298–298 0–1.3 n.a. AnGrav
2-Ethyl-hexyl-C8C10 Bureau et al. [193] 363–423 30–60 n.a. AnTVar
2-Ethyl-hexyl-oleate Bureau et al. [193] 363–423 35–70 n.a. AnTVar
Bureau et al. [193] 363–423 70–100 220 AnTVisVar
Acenaphthene Tobaly et al. [672] 398–453 4.6–144.1 2.4–9.3 AnSpecVar
Carbon dioxide Webster and Kidney [703] 230–270 0.8–8.4 n.a. AnTVcir
cis-Decahydronaphthaline (decalin) Tohidi et al. [674] 323–423 34.6–66.1 1 SynVis
Decalin Tobaly et al. [672] 294–423 0.1–76.7 2.4–9.3 AnSpecVar
Ethane Raabe et al. [53] 239–270 1.5–6.6 n.a. AnTLcirBlo
Ethanol Ukai et al. [681] 280–280 1.5–5.6 134 SynOthX
Isobutyl-C12C14 Bureau et al. [193] 363–423 30–60 n.a. AnTVar
Methanol Ukai et al. [681] 280–280 2.1–6 134 SynOthX
Xia et al. [719] 298–298 5.4–12 200–360 AnTLcirVar
n-Butane Dandekar and Stenby [250] 311–344 11.5–12.6 80 SynVisVar
n-Hexane Cebola et al. [206] 348–383 2.3–19.6 n.a. AnTVLcirPc
Chylinski et al. [51] 348–348 2.2–11.6 650 AnTVLcirValVis
Uribe-Vargas and Trejo [682] 338–338 0.3–10.3 n.a. AnTVal
Xia et al. [719] 310–310 2.1–6 200–360 AnTLcirVar
Propane May et al. [507] 290–293 5.3–8.6 n.a. SynNonVcirVar
Webster and Kidney [703] 230–270 0–9.2 n.a. AnTVcir
Tetracosane Randzio et al. [125] 317–322 30–103.8 n.a. SynNon
Triacontane Machado and de Loos [488] 337–472 1.6–193.1 n.a. SynVisPcTc
Water Addicks et al. [147] 298–298 7.3–17.8 450 AnTVarVis
Chapoy et al. [214] 283–318 0.9–34.6 34 AnTVal
Chapoy et al. [214] 283–293 10–35 34 AnTVal
26 R. Dohrn et al. / Fluid Phase Equilibria 288 (2010) 1–54
Table 13 (Continued )
Table 14
Binary systems: ethane + X.
Table 15
Binary systems: propane + X.
Table 16
Binary systems: n-butane + X.
1,1-Difluoroethane (HFC-152a) Shimawaki and Fujii [632] 283–313 0.1–2.4 163 AnTVLcirValVis
Adamantane Poot et al. [565] 285–493 0.2–5.7 n.a. SynVisVar
Diamantane Poot et al. [565] 343–523 0.8–6.9 n.a. SynVisVar
Ethane Horstmann et al. [357] 305–424 3.7–5.8 10 SynVisTc
Ethyl mercaptan Giles and Wilson [330] 323–373 0.1–1.5 300 SynT
Methane Dandekar and Stenby [250] 311–344 11.5–12.6 80 SynVisVar
Poly(propylene) Oliveira et al. [549] 358–423 1.2–11.4 28 SynVisVar
Poly(propylene) (metallocene) Ndiaye et al. [534] 358–423 1.7–11 27 SynVisVar
Poly(propylene) (Ziegler Natta) Ndiaye et al. [534] 358–423 1.7–11 27 SynVisVar
Water Tian et al. [669] 622–695 23.2–306 60.13 SynVis
Table 17
Binary systems: n-hexane + X.
Table 18
Binary systems: ethene + X.
Table 19
Binary systems: propene + X.
Table 20
Binary systems: 1-butene + X.
Table 21
Binary systems: methanol + X.
Table 22
Binary systems: ethanol + X.
Table 23
Binary systems: dimethyl ether + X.
Table 24
Binary systems: chlorodifluoromethane (HCFC-22) + X.
Table 25
Binary systems: trifluoromethane (HFC-23) + X.
Table 26
Binary systems: difluoromethane (HFC-32) + X.
Table 27
Binary systems: 1,1,1,2,2-pentafluoroethane (HFC-125) + X.
Table 28
Binary systems: 1,1,1,2-tetrafluoroethane (HFC-134a) + X.
Table 29
Binary systems: 1,1,1-trifluoroethane (HFC-143a) + X.
Table 30
Binary systems: 1,1-difluoroethane (HFC-152a) + X.
Table 31
Binary systems: X + Y.
Table 32
Ternary systems: carbon dioxide + water + X.
Table 33
Ternary systems: carbon dioxide + methanol + X.
Table 34
Ternary systems: carbon dioxide + ethanol + X.
Table 35
Ternary systems: carbon dioxide + ethyl acetate + X.
Table 36
Ternary systems: carbon dioxide + dimethyl ether + X.
Table 37
Ternary systems: carbon dioxide + acetone + X.
Table 38
Ternary systems: carbon dioxide + limonene + X.
Table 39
Ternary systems: carbon dioxide + X + Y.
1,1,1,2-Tetrafluoroethane (HFC-134a) Salicylic acid Abbott et al. [144] 323–343 12.1–29 n.a. AnOth
1,8-Cineole ␣-Pinene Cruz Francisco and Sivik 313–333 8–25 30 AnPTSemY
[239]
1-Butyl-3-methylimidazolium Acetonitrile (ethanenitrile) Wu et al. [711] 313–313 15–15 55 AnPTSemYVis
hexafluorophosphate ([bmim][PF6])
1-Decanol n-Tetradecane Scheidgen and Schneider 393–393 0–1000 80 AnT
[601]
Scheidgen and Schneider 280–316 5–61 80 AnT
[602]
1-Heptanol n-Pentadecane Scheidgen and Schneider 393–393 0–1000 80 AnT
[601]
Scheidgen and Schneider 281–384 5–95 80 AnT
[602]
1-Hexanol 1-Heptanol Scheidgen and Schneider 393–393 0–1000 80 AnT
[601]
n-Pentadecane Scheidgen and Schneider 272–297 5–90 80 AnT
[602]
n-Tetradecane Scheidgen and Schneider 393–393 0–1000 80 AnT
[601]
1-Hexene Carbon monoxide Ke et al. [410] 308–316 8–10.2 4 SynNonPcTc
1-n-Hexene Hydrogen Ke et al. [410] 312–320 8.8–10.9 4 SynNonPcTc
1-Octanol n-Hexadecane Scheidgen and Schneider 393–393 0–1000 80 AnT
[601]
1-Propanol Salicylic acid Shariati and Peters [105] 273–367 1–13.9 3.5 SynVisVar
2-Ethyl-1-hexanol 2-Ethyl hexanoic acid Ghaziaskar et al. [329] 313–343 13.8–13.8 10 AnPTSemY
2-Naphthol Cyclohexane Li et al. [459] 308–328 10–30 377 AnPTSemY
3,3,4,4,5,5,6,6-Octafluorooctan-1,8-diol Divinyl adipate Mesiano et al. [512] 323–323 9–15 n.a. SynVisVar
9-Nitroanthracene 2-Methylanthracene Yamini et al. [725] 308–348 12.2–35.5 0.5 AnTValY
␣-Linolenic acid Poly(ethylene glycol) Funazukuri et al. [308] 308–343 8.5–30.1 3.3 AnPTChro
Anthracene Cyclohexane Li et al. [459] 308–328 10–30 377 AnPTSemY
␣-Pinene Pinane Chouchi et al. [232] 323–323 9.3–9.3 50 SynVis
Arachidonic acid Poly(ethylene glycol) Funazukuri et al. [307] 308–343 9.5–30.2 3.3 AnPTChro
␣-Tocopherol Poly(ethylene glycol) Funazukuri et al. [77] 313–323 12.1–22 3.3 AnPTChro
Funazukuri et al. [306] 308–333 8.5–30.3 3.3 AnPTChro
-Carotene Grape seed oil Sovova et al. [649] 313–333 19–28.3 12 AnPTSemY
Poly(ethylene glycol) Funazukuri et al. [77] 313–323 12.1–23 3.3 AnPTChro
Funazukuri et al. [306] 308–333 9.1–30.2 3.3 AnPTChro
Funazukuri et al. [309] 313–313 16.1–16.1 3.2 AnPTChro
Butyl methacrylate Poly(butylmethacrylate) Byun and McHugh [104] 298–503 6–210 28 SynVisVar
C,I, Disperse Blue 134 C.I. Disperse Yellow 16 Tamura and Shinoda [662] 323–383 10–25 n.a. AnPTSemY
C,I, Disperse Orange 25 Poly(methyl methacrylate) Ngo et al. [535] 313–313 8.8–9.5 n.a. SynNonSpec
Carbon monoxide Hydrogen Ke et al. [411] 281–302 8.3–13.7 n.a. SynNonPcTc
Chlorodifluoromethane (HCFC-22) Poly(l-lactide) Lee et al. [444] 302–393 3.6–71.4 31 SynVisVar
Poly(l-lactide) 100 000 Lee et al. [438] 303–373 3.6–68.5 31 SynVisVar
Poly(l-lactide) 2000 Lee et al. [438] 302–372 3.6–71.4 31 SynVisVar
Poly(l-lactide) 50 000 Lee et al. [438] 303–373 4–64 31 SynVisVar
Clove oil Cellulosic structure Rodrigues et al. [588] 283–308 6.6–10 500 AnPTSemY
Coenzyme Q10 (ubiquinone) Poly(ethylene glycol) Funazukuri et al. [305] 308–328 8.5–30.1 3.3 AnPTChro
Cyclohexane Polybutadiene Joung et al. [395] 353–473 0.5–21.5 33 SynVisVar
Decanoic acid 1-Dodecanol Scheidgen and Schneider 273–393 0–100 80 AnT
[603]
n-Tetradecane Scheidgen and Schneider 273–393 0–100 80 AnT
[603]
Dichloromethane (HCC-30) Poly(l-lactide) Lee ad Kuk [437] 304–375 4.8–84.7 31 SynVisVar
Diethyl ether Cholesterol Wubbolts et al. [95] 292–314 7–10 30 SynVisVar
Dimethylsulfoxide Eflucimibe Sauceau et al. [600] 308–318 12.2–29.1 n.a. AnPTSemY
Diolein Poly(ethylene glycol) Funazukuri et al. [310] 313–313 10–25 3.2 AnPTChro
Docoahexaenoic acid Poly(ethylene glycol) Funazukuri et al. [308] 308–343 9.2–30.1 3.3 AnPTChro
Eicosapentaenoic acid Poly(ethylene glycol) Funazukuri et al. [308] 308–343 8.6–30.1 3.3 AnPTChro
Ethene Poly(ethylene-co-1-hexene) Dörr et al. [270] 393–493 118.6–168.3 14.5–19.0 SynVisVar
copolymer
Poly(ethylene-co-propylene) de Vries et al. [257] 312–342 171.8–213.2 n.a. SynVis
Poly(ethylene-co-vinyl Kinzl et al. [423] 393–493 108.3–130.3 14.5–19.0 SynVisVar
acetate) copolymer
Ethyl methacrylate Poly(ethylmethacrylate) Byun and McHugh [104] 298–488 25–100 28 SynVisVar
Eucalyptus oil Cellulosic structure Rodrigues et al. [588] 283–288 6.6–7.8 500 AnPTSemY
Ginger oil Cellulosic structure Rodrigues et al. [588] 293–313 15–30 500 AnPTSemY
Hexyl acrylate Poly(hexyl acrylate) Byun et al. [201] 303–435 6.7–255.3 28 SynVisVar
Hexyl methacrylate Poly(hexyl methacrylate) Byun et al. [201] 313–472 6.7–220.8 29 SynVisVar
Hydrogen Methylcyclohexane Zhang et al. [736] 304–326 7.3–14 20–50 SynVisVarPc
Toluene Zhang et al. [735] 307–313 8.3–11.3 20–50 SynVisVarTc
Hydroquinone (1,4-dihydroxybenzene) p-Quinone Deiters [259] Comments
(1.4-benzoquinone)
García-González et al. [323] 333–363 10–35 50 AnTVcirVal
38 R. Dohrn et al. / Fluid Phase Equilibria 288 (2010) 1–54
Table 39 (Continued )
Ligand bis-(2,4,4-trimethyl ion Ag(I) in solid matrix Pourmortazavi [570] 308–328 10–30 1 AnPTSemY
pentyl)-dithiophosphinic acid (cyanex
301)
Ion Au(III) in solid matrix Pourmortazavi [570] 308–328 10–30 1 AnPTSemY
Ion Bi(III) in solid matrix Pourmortazavi [570] 308–328 10–30 1 AnPTSemY
Ion In(III) in solid matrix Pourmortazavi [570] 308–328 10–30 1 AnPTSemY
Ion Mn(II) in solid matrix Pourmortazavi [570] 308–328 10–30 1 AnPTSemY
Ion Pd(II) in solid matrix Pourmortazavi [570] 308–328 10–30 1 AnPTSemY
Linoleic acid Poly(ethylene glycol) Funazukuri et al. [307] 308–343 8.5–30.3 3.3 AnPTChro
Low MW poly(2,6-dimethyl-1,4-phenylene Polystyrene Sato et al. [599] 373–473 2.1–20.1 n.a. AnGrav
ether) (PPO)(L)
Ls-54 surfactant 1-Pentanol Liu et al. [475] 308–308 14.8–16.1 40 SynVis
1-Propanol Liu et al. [475] 308–308 14.3–15.7 40 SynVis
Benzyl alcohol Liu et al. [475] 308–308 21.8–21.8 40 SynVis
n-Heptanol Liu et al. [475] 308–323 15.5–22.1 40 SynVis
Medroxyprogesterone Cyproterone acetate Asghari-Khiavi et al. [154] 308–348 12.2–35.5 1 AnTValY
Methane Propane Webster and Kidney [703] 230–270 0.8–8 n.a. AnTVcir
Microalga Haematococcus pluvialis Astaxantine Valderrama et al. [684] 333–333 30–30 450 AnPTSemY
Microalga Spirulina maxima Phycocyanine Valderrama et al. [684] 333–333 30–30 450 AnPTSemY
Monoolein Poly(ethylene glycol) Funazukuri et al. [310] 313–313 10–25 3.2 AnPTChro
n-Heptane Poly(ethylene) Joung et al. [395] 383–503 0.6–33.5 33 SynVisVar
Polyisobutylene Joung et al. [395] 323–493 0.4–23.7 33 SynVisVar
Nitrogen Oleic acid Laursen et al. [50] 298–318 2.5–14.6 90 AnTVcirX
N-methyldiethanolamine (MDEA) Sodium sulfate Kamps et al. [401] 313–413 3.8–4.5 30 SynVis
Sulfuric acid Kamps et al. [401] 313–413 7.8–10.6 30 SynVis
n-Vinyl-2-pyrrolidone Poly(vinyl pyrrolidone) Bae et al. [158] 321–458 18.4–212 25 SynVisVar
Oleic acid Poly(ethylene glycol) Funazukuri et al. [310] 313–313 9.4–30.1 3.2 AnPTChro
Oleic acid ethyl ester Poly(ethylene glycol) Funazukuri et al. [310] 313–313 8.6–11 3.2 AnPTChro
Oleic acid methyl ester Poly(ethylene glycol) Funazukuri et al. [310] 313–313 8–11 3.2 AnPTChro
Phenol Poly(ethylene glycol) Funazukuri et al. [77] 308–328 8.7–30.2 3.3 AnPTChro
Funazukuri et al. [309] 313–313 17.8–17.8 3.2 AnPTChro
Poly(ethylene oxide) Poly(methyl methacrylate) Shieh et al. [82] 305–305 35–35 10 AnSpec
Poly(l-lactide) 110 000 1,1-Difluoroethane Lim et al. [469] 352–415 54.3–61.3 n.a. SynVisVar
(HFC-152a)
Chlorodifluoromethane Lim et al. [469] 333–410 3.7–26.1 n.a. SynVisVar
(HCFC-22)
Difluoromethane (HFC-32) Lim et al. [469] 342–416 77.3–93.6 n.a. SynVisVar
Trifluoromethane (HFC-23) Lim et al. [469] 333–414 94.1–115.1 n.a. SynVisVar
Poly(l-lactide) 2000 Chlorodifluoromethane Lim et al. [469] 314–395 3.6–44.1 n.a. SynVisVar
(HCFC-22)
Poly(l-lactide) 230 000 1,1-Difluoroethane Lim et al. [469] 354–414 56.8–64.2 n.a. SynVisVar
(HFC-152a)
Chlorodifluoromethane Lim et al. [469] 332–409 3.6–26.1 n.a. SynVisVar
(HCFC-22)
Difluoromethane (HFC-32) Lim et al. [469] 334–413 81.4–111.3 n.a. SynVisVar
Trifluoromethane (HFC-23) Lim et al. [469] 333–413 96.1–116 n.a. SynVisVar
Poly(l-lactide) 80 000 1,1-Difluoroethane Lim et al. [469] 354–413 53.2–59.5 n.a. SynVisVar
(HFC-152a)
Chlorodifluoromethane Lim et al. [469] 334–408 3.6–25.2 n.a. SynVisVar
(HCFC-22)
Difluoromethane (HFC-32) Lim et al. [469] 344–412 77–91.6 n.a. SynVisVar
Trifluoromethane (HFC-23) Lim et al. [469] 333–415 93.1–112.1 n.a. SynVisVar
Polychlorinated biphenyl St. Lawrence River sediments Zhou et al. [744] 313–333 6.5–27 50 AnTVcirVal
Propane Tripalmitin Rovetto et al. [592] 317–451 1.4–14.5 3.5 SynVis
Propene Carbon monoxide Ke et al. [410] 299–303 7.5–7.9 4 SynNonPcTc
Hydrogen Ke et al. [410] 305–305 8.3–9 4 SynNonPcTc
Squalene Methyl oleate Ruivo et al. [60] 313–343 11–21 n.a. AnPTCon
Sulfur hexafluoride SF6 Ethane Horstmann et al. [358] 292–304 4.4–6.2 10 SynVisTc
Tetraethylene glycol n-laurel ether (C12E4) n-Pentane Liu et al. [474] 313–323 8.8–19.6 40 SynVis
Tetrahydrofuran Polysulfone Zhang and Kiran [740] 296–426 13.8–54.9 24.8 SynVisVar
Zhang and Kiran [741] 296–426 13.8–54.9 24.8 SynVisVar
Toluene Polybutadiene Joung et al. [395] 323–473 1.9–23.7 33 SynVisVar
Trichloromethane (HCC-20) Iron Roggeman et al. [589] 333–333 13.7–27.5 50 AnTVal
tris(pentane-2.4-dionate)
Trifluoromethane (HFC-23) Naphthalene Diefenbacher and Türk 335–338 7.8–29.6 1310 SynVis
[267]
Triolein Poly(ethylene glycol) Funazukuri et al. [310] 313–313 9.1–14 3.2 AnPTChro
Undecanoic acid n-Hexadecane Scheidgen and Schneider 273–393 0–100 80 AnT
[603]
R. Dohrn et al. / Fluid Phase Equilibria 288 (2010) 1–54 39
Table 40
Ternary systems: water + methane + X.
Table 41
Ternary systems: water + ethane + X.
Diethylene glycol (DEG) Mahmoodaghdam and Bishnoi [492] 274–282 0.6–2.2 n.a. SynVisVar
Ethylene glycol Majumdar et al. [493] 271–282 0.5–2.6 n.a. SynVisVar
Wang et al. [700] 283–303 0.5–4 600 AnTVal
Helium Maekawa [490] 273–287 0.7–4 500 SynVis
Methane Wang et al. [700] 275–283 1–4 540 AnTVLcirVar
Zhang et al. [738] 274–274 2.5–4 60 AnTVarVis
Methanol Wang et al. [700] 283–303 0.5–4 600 AnTVal
Propane Ballard et al. [159] 276–279 0.5–2 3 SynVis
Ballard et al. [159] 277–282 0.5–2.5 n.a. SynVis
40 R. Dohrn et al. / Fluid Phase Equilibria 288 (2010) 1–54
Table 42
Ternary systems: water + propane + X.
Table 43
Ternary systems: water + nitrogen + X.
Table 44
Ternary systems: water + hydrogen sulfide + X.
Table 45
Ternary systems: water + X + Y.
Ammonia Potassium hydroxide Brass et al. [188] 303–318 0.1–1.1 n.a. AnTLcirVis
Sodium hydroxide Brass et al. [188] 303–318 0.1–1.3 n.a. AnTLcirVis
Chlorodifluoromethane Ethanol Elbaccouch and Elliot [279] 351–371 0.6–3.7 40 AnTVLcirVal
(HCFC-22)
Dimethyl ether 2-Propanol (isopropanol) Elbaccouch and Elliot [281] 323–373 0.1–2.4 40 AnTVLcirVal
Ethanol Elbaccouch et al. [280] 333–373 0.2–2.5 40 AnTVLcirVal
Ethanethiol Tetraethylene glycol Jou et al. [389] 298–403 0–1 n.a. AnTVcir
Ethene 1-Propanol Freitag et al. [52] 287–352 3.5–21.6 30 AnTVLcirVisVal
2-Propanol (isopropanol) Freitag et al. [52] 288–353 6.1–17.9 30 AnTVLcirVisVal
Methanol Natural near critical reservoir fluid (C1-C20+) Ostergaard et al. [551] 276–283 5.3–24.2 540 SynVis
n-Decane 2-Butanol Shimoyama et al. [634] 573–573 20–20 31 AnPTConVis
2-Propanol (isopropanol) Shimoyama et al. [634] 573–593 15–20 31 AnPTConVis
n-Hexane 2-Propanol (isopropanol) Shimoyama et al. [634] 573–573 20–20 31 AnPTConVis
n-Hexadecane Shimoyama et al. [633] 573–573 20–20 31 AnPTConVis
Oxygen Sodium carbonate Tan et al. [69] 300–300 0.7–10 500 AnPTSemX
Propene Diethanolamine (dea) Jou and Mather [393] 313–373 1.7–20.6 250 AnTVcirVar
Di-isopropanolamine Jou and Mather [393] 313–333 1.7–2.7 250 AnTVcirVar
Monoethanolamine (mea) Jou and Mather [393] 280–373 0.1–5.5 250 AnTVcirVar
N-methyldiethanolamine (MDEA) Jou and Mather [393] 313–333 1.7–2.7 250 AnTVcirVar
Synthethic natural gas Methanol Jarne et al. [380] 247–288 0.1–2 n.a. SynVis
Toluene Ethylbenzene Shimoyama et al. [633] 553–553 20–20 31 AnPTConVis
n-Decane Shimoyama et al. [633] 553–573 20–20 31 AnPTConVis
R. Dohrn et al. / Fluid Phase Equilibria 288 (2010) 1–54 41
Table 46
Ternary systems: methane + X + Y.
Table 47
Ternary systems: ethene + X + Y.
1-Hexene Poly(ethylene-co-1-hexene) copolymer Dörr et al. [270] 393–493 25.6–156 14.5–19.0 SynVisVar
2,6-Di-tertbutyl-4-methylphenol Ethylene–butyl acrylate copolymers Becker et al. [167] 354–530 95.3–114.4 n.a. SynVisVar
Ethylene–ethyl acrylate copolymers Becker et al. [167] 353–533 98.2–163.1 n.a. SynVisVar
Ethylene–methyl acrylate copolymers Becker et al. [167] 373–493 124.4–211.5 n.a. SynVisVar
Ethylene–methyl methacrylate copolymers Becker et al. [167] 353–528 103.9–185.5 n.a. SynVisVar
Ethylene–propyl acrylate copolymers Becker et al. [167] 353–532 97.8–152.7 n.a. SynVisVar
Ethylene-butyl methacrylate copolymers Becker et al. [167] 353–533 81.3–138 n.a. SynVisVar
Poly(ethyl acrylate) Becker et al. [167] 354–533 101–161.3 n.a. SynVisVar
Poly(ethylene) (ldpe) Becker et al. [167] 403–521 120.4–163.7 n.a. SynVisVar
Poly(propyl acrylate) Becker et al. [167] 352–531 87.4–109.3 n.a. SynVisVar
Benzene Ethylbenzene Liu et al. [477] 282–572 5–11.9 n.a. SynVisPcTc
Ethane Poly(ethylene-co-1-hexene) copolymer Dörr et al. [270] 393–493 112–156 14.5–19.0 SynVisVar
Poly(ethylene-co-vinyl acetate) copolymer Kinzl et al. [423] 393–493 107.5–126 14.5–19.0 SynVisVar
Helium Poly(ethylene-co-1-hexene) copolymer Dörr et al. [270] 393–493 118.6–214.6 14.5–19.0 SynVisVar
Poly(ethylene-co-vinyl acetate) copolymer Kinzl et al. [423] 393–493 108.3–209.4 14.5–19.0 SynVisVar
n-Butane Poly(ethylene-co-1-hexene) copolymer Dörr et al. [270] 393–493 101–156 14.5–19.0 SynVisVar
Poly(ethylene-co-vinyl acetate) copolymer Kinzl et al. [423] 393–493 94.3–125.9 14.5–19.0 SynVisVar
n-Hexane Impact poly(propylene) copolymer (icp–pp) Sato et al. [78] 323–363 0.6–2.4 n.a. AnPTChro
Poly(ethylene) (ldpe) Chen et al. [229] 393–473 0.6–15.7 6–20 SynVisVar
Poly(ethylene) 108k Chen et al. [229] 373–473 0.4–17 6–20 SynVisVar
Poly(ethylene) 15k Chen et al. [229] 373–473 0.4–20.9 6–20 SynVisVar
Propane Poly(ethylene-co-1-hexene) copolymer Dörr et al. [270] 393–493 106.6–156 14.5–19.0 SynVisVar
Poly(ethylene-co-vinyl acetate) copolymer Kinzl et al. [423] 393–493 98–125.9 14.5–19.0 SynVisVar
Table 48
Ternary systems: X + Y + Z.
Table 48 (Continued )
Nitrogen Cyclohexane Polystyrene ter Horst et al. 437–513 7.5–16 3.5 SynVis
[667]
Dimethyl ether Methanol Teodorescu 288–313 0.1–9.2 700 AnTVal
Rasmussen [666]
n-Hexane n-Decane Uribe-Vargas and 258–298 1.4–20.1 n.a. AnTVal
Trejo [682]
n-Tridecane n-Tetradecane n-Pentadecane Daridon et al. [106] 273–293 0.1–100 0.03 SynVis
Propane cyclohexane Polystyrene ter Horst et al. 438–513 2.5–12.4 3.5 SynVis
[667]
Propene 2,6-Di-tertbutyl-4- Poly(methyl acrylate) Becker et al. [167] 473–531 139.9–275 n.a. SynVisVar
methylphenol
2,6-Di-tertbutyl-4- Poly(methyl methacrylate) Becker et al. [167] 427–532 107.8–270 n.a. SynVisVar
methylphenol
Vinyl acetate Ethene Poly(ethylene-co-vinyl acetate) Kinzl et al. [423] 393–493 4.8–125.9 14.5–19.0 SynVisVar
copolymer
Table 49
Multicomponent systems: carbon dioxide + water + X (+Y + . . .).
1,8-Cineole + lecithin Cruz Francisco et al. [80] 308–353 15–15 n.a. AnSpecVis
1,8-Cineole + monoolein Cruz Francisco et al. [240] 308–353 15–15 n.a. AnSpecVis
1-Octene + tetrahydrofuran Lazzaroni et al. [436] 298–298 0.2–25.6 350 AnTValVis
1-Pentanol + fluorosurfactant F-53B Gao et al. [320] 290–334 7.5–13.5 n.a. SynVisVar
1-Propanol + adenine Adrian et al. [148] 313–333 7.1–16.1 30 AnTVcirLcir
1-Propanol + anthranilate Adrian et al. [148] 313–333 7.1–16.1 30 AnTVcirLcir
1-Propanol + caffeine Adrian et al. [148] 313–333 7.1–16.1 30 AnTVcirLcir
1-Propanol + fluorosurfactant F-53B Gao et al. [320] 308–334 12–14.5 n.a. SynVisVar
1-Propanol + l-phenylalanine Adrian et al. [148] 313–333 7.1–16.1 30 AnTVcirLcir
1-Propanol + salicyclic alcohol Adrian et al. [148] 313–333 7–16.1 30 AnTVcirLcir
1-Propanol + vanillin Adrian et al. [148] 313–333 7.1–16.1 30 AnTVcirLcir
Acetic acid (ethanoic acid) + sodium acetate Sieder and Maurer [639] 313–353 6–16.1 38 AnPTCon
Acetic acid (ethanoic acid) + sodium chloride Sieder and Maurer [639] 313–353 6.1–16.3 38 AnPTCon
Diethanolamine (DEA) + N-methyldiethanolamine (MDEA) Sidi-Boumedine et al. [637] 298–348 0–4.5 n.a. SynT
Ethanol + capsaicin Duarte et al. [34] 313–323 12–14 36 AnTCapVal
Ethanol + dimethyl ether Laursen and Andersen [435] 298–318 0.5–4.2 570 AnTVis
Ethanol + fluorosurfactant F-53B Gao et al. [320] 308–334 8–24.5 n.a. SynVisVar
Ethylene glycol + sodium cloride Majumdar et al. [493] 264–272 1.3–3.1 n.a. SynVisVar
Fluorosurfactant F-53B + butanol Gao et al. [320] 308–334 12–14.5 n.a. SynVisVar
Fluorosurfactant F-53B + heptanol Gao et al. [320] 308–334 12–14.5 n.a. SynVisVar
Fluorosurfactant F-53B + hexanol Gao et al. [320] 308–334 8.5–15.5 n.a. SynVisVar
Fluorosurfactant F-53B + octyl alcohol Gao et al. [320] 308–334 15–17 n.a. SynVisVar
Methane + hydrogen sulfide Sun et al. [658] 274–299 0.5–8.6 60 SynVisVar
Methane + methanol Jarne et al. [379] 241–288 0.1–5.9 n.a. SynVis
Methane + N-methyldiethanolamine (MDEA) Addicks et al. [147] 313–353 10–20 450 AnTVarVis
Methanol + dimethyl ether Laursen et al. [38] 298–318 0.4–5.5 570 AnTValVis
Methanol + tetramethylammonium bicarbonate Levitin et al. [454] 298–343 1.5–27.1 5–20 SynVisVar
Methanol + tetramethylammonium bicarbonate Levitin et al. [455] 298–343 1.5–27.1 5–20 SynVisVar
Nitric acid + tri-n-butyl phosphate Enokida et al. [285] 313–333 7–16.5 n.a. SynVis
Nitrogen + tetrahydrofuran Kang et al. [404] 274–295 0.2–12.9 70 AnTValVis
N-methyldiethanolamine (MDEA) + diethanolamine (DEA) Rebolledo-Libreros and Trejo [582] 313–393 0–1.9 320 AnTVcir
Phenol + potassium chloride Wagner et al. [694] 313–313 22–22 200 AnTVLcirVis
Phenol + sodium bromide Wagner et al. [694] 313–313 22–22 200 AnTVLcirVis
Phenol + sodium chloride Wagner et al. [694] 313–313 8–30 200 AnTVLcirVis
Phenol + tetramethylammonium bromide Wagner et al. [694] 313–313 8–30 200 AnTVLcirVis
Piperazine + N-methyldiethanolamine (MDEA) Kamps et al. [402] 353–353 0.1–6.4 30 SynVis
2,2,3,3,4,4,5,5-Octafluoro-1-pentanol + sodium Liu et al. [476] 311–311 34.5–34.5 2.2 AnSpec
bis(2-ethylhexyl)sulfosuccinate + dimidium bromice
2,2,3,3,4,4,5,5-Octafluoro-1-pentanol + sodium Liu et al. [476] 311–311 34.5–34.5 2.2 AnSpec
bis(2-ethylhexyl)sulfosuccinate + methyl orange
2,2,3,3,4,4,5,5-Octafluoro-1-pentanol + sodium Liu et al. [476] 311–311 34.5–34.5 2.2 AnSpec
bis(2-ethylhexyl)sulfosuccinate + thymol blue
Ethanol + didecyldimethylammonium chloride + soysolv Elbaccouch et al. [282] 298–333 0.2–8.7 9.5 SynTVis
Methane + diethanolamine (DEA) + ethanethiol Jou and Mather [387] 313–343 6.8–6.8 n.a. AnTVcir
Methane + diethanolamine (DEA) + methanethiol Jou and Mather [387] 313–343 6.8–6.8 n.a. AnTVcir
Methane + toluene + N-methyldiethanolamine (MDEA) Valtz et al. [686] 333–333 0.5–0.5 n.a. AnTValVis
Nitrogen + dimethyl ether + methanol Laursen et al. [38] 298–318 0.4–9.9 570 AnTValVis
N-methyldiethanolamine (MDEA) + diethanolamine Rebolledo-Libreros and Trejo [582] 313–393 0–1.9 320 AnTVcir
(DEA) + 2-amino-2-methyl-1-propanol
Methane + diethanolamine (DEA) + hydrogen Jou and Mather [387] 313–343 6.8–6.8 n.a. AnTVcir
sulfide + ethanethiol
Methane + diethanolamine (DEA) + hydrogen Jou and Mather [387] 313–343 6.8–6.8 n.a. AnTVcir
sulfide + methanethiol
R. Dohrn et al. / Fluid Phase Equilibria 288 (2010) 1–54 43
Table 50
Multicomponent systems: carbon dioxide + X + Y (+ . . .).
Table 51
Multicomponent systems: methane + X + Y (+. . .).
Diglycolamine (DGA) + ethylbenzene + water Valtz et al. [686] 298–393 0.5–5 n.a. AnTValVis
Ethane + water + ethylene glycol Wang et al. [700] 275–283 0.5–40 540 AnTVLcirVar
Ethane + water + methanol Wang et al. [700] 275–283 1.3–40 540 AnTVLcirVar
Ethane + water + n-butane Blanco et al. [175] 250–288 0.4–9.9 n.a. SynVisCon
Chapoy et al. [218] 278–313 0.9–14.4 34 AnTVal
Ethane + water + tetrahydrofuran Zhang et al. [738] 274–284 2–3 60 AnTVarVis
Ethylene glycol + water + sodium chloride Eichholz et al. [278] 262–281 2.1–9.5 64–74 SynVisVar
n-Butane + n-heptane + n-hexadecane Fenghour et al. [293] 340–372 4.8–3.6 207 SynNon
n-Hexane + n-decane + n-tetradecane Chylinski et al. [51] 296–296 5.8–5.8 650 AnTVLcirValVis
Nitrogen + water + 2,2-dimethylpentane Ostergaard et al. [550] 276–286 6.2–22.6 540 SynVis
Nitrogen + water + 2-methylbutane (isopentane) Ostergaard et al. [550] 276–284 5.1–15.4 540 SynVis
Water + benzene + diglycolamine (DGA) Valtz et al. [686] 298–393 0.5–5 n.a. AnTValVis
Water + ethane + propane Ostergaard et al. [552] 276–290 1.4–7.9 540 SynVis
Water + hydrogen + propane Zhang et al. [739] 274–280 0.6–4.9 60 SynVisVar
Water + methanethiol + diethanolamine (DEA) Jou and Mather [387] 313–343 6.8–6.8 n.a. AnTVcir
Water + methanol + sodium chloride Jager et al. [377] 249–281 2–16 n.a. SynVis
Jager et al. [377] 260–292 7.4–73.2 1 SynVisSpec
Water + sodium chloride + magnesium chloride Link et al. [102] 269–293 7.9–9.6 40 SynVis
Water + toluene + diglycolamine (DGA) Valtz et al. [686] 298–393 0.5–5 n.a. AnTValVis
Water + toluene + N-methyldiethanolamine (MDEA) Valtz et al. [686] 298–393 0.4–8.1 n.a. AnTValVis
n-Pentane + 2-methylbutane Jensen et al. [383] 277–410 11.7–40 150 SynVisVar
(isopentane) + n-hexane + naphthalene
n-Pentane + 2-methylbutane Jensen et al. [383] 279–413 9.8–39.5 150 SynVisVar
(isopentane) + n-hexane + n-tetracosane
44 R. Dohrn et al. / Fluid Phase Equilibria 288 (2010) 1–54
Table 51 (Continued )
Propane + n-pentane + n-decane + n- Gozalpour et al. [32] 303–353 19.4–30.4 9000 AnTValVisVar
hexadecane Gozalpour et al. [337] 278–383 10.4–41.4 9000 SynVisVar
Gozalpour et al. [338] 278–383 10.4–41.4 9000 SynVisVar
Water + ethane + cyclohexane + propane Sun et al. [659] 273–289 0.6–6.2 n.a. SynVisVar
Water + ethane + propane + 2-methylbutane Ostergaard et al. [552] 275–282 2–5.1 540 SynVis
(isopentane)
Water + ethane + propane + methylcyclohexane Sun et al. [660] 273–288 0.9–6.1 n.a. SynVisVar
Ostergaard et al. [552] 280–288 2.6–8.1 540 SynVis
Water + ethane + propane + methylcyclopentane Ostergaard et al. [552] 278–288 2–7.7 540 SynVis
Water + ethylene glycol + potassium chloride + sodium Masoudi et al. [501] 259–283 3.9–46.6 n.a. SynNon
chloride
Water + hydrogen + ethane + propane Zhang et al. [739] 274–279 1.1–7 60 SynVisVar
Water + methanethiol + diethanolamine Jou and Mather [387] 313–343 6.8–6.8 n.a. AnTVcir
(DEA) + hydrogen sulfide
n-Pentane + 2-methylbutane (isopentane) + n- Jensen et al. [383] 278–419 8.9–40 150 SynVisVar
hexane + n-tetracosane + naphthalene
Water + benzene + N-methyldiethanolamine Valtz et al. [686] 333–333 0.5–0.5 n.a. AnTValVis
(MDEA) + ethylbenzene + toluene
Water + ethane + propane + n-pentane + n-decane Ostergaard et al. [552] 279–286 1.2–3.8 540 SynVis
Ethane + propane + 2-methylpropane Dandekar and Stenby [250] 298–298 7.4–7.4 80 SynVisVar
(isobutane) + n-butane + 2-methylbutane
(isopentane) + n-pentane
Water + ethane + propane + n-pentane + n-decane + 2,2- Ostergaard et al. [552] 278–286 0.9–3.4 540 SynVis
dimethylpropane
(neopentane)
Water + ethane + propane + n-pentane + n- Ostergaard et al. [552] 276–284 0.8–3.1 540 SynVis
decane + cyclohexane
Water + ethane + propane + n-pentane + n- Ostergaard et al. [552] 278–287 0.2–4.2 540 SynVis
decane + cyclopentane
Water + ethane + propane + n-pentane + n- Ostergaard et al. [552] 278–288 0.4–2.6 540 SynVis
decane + cyclopentane + 2,2-dimethylpropane
(neopentane)
Table 52
Multicomponent systems: X + Y (+ . . .).
Benzene + water + deuterium oxide + deuterium protium oxide Furutaka and Ikawa [312] 473–648 10–35 n.a. AnSpecVis
Ethene + n-hexane + poly(ethylene) 15k + poly(ethylene) 108k Chen et al. [229] 443–473 2.8–14.8 6–20 SynVisVar
Ethene + toluene + norbornene + cyclic olefin copolymer Lee et al. [449] 323–423 0.5–2.5 n.a. AnT
Ethylbenzene + water + deuterium oxide + deuterium protium Furutaka and Ikawa [313] 473–623 10–35 n.a. AnSpecVis
oxide
Hydrogen + carbon monoxide + methanol + n-hexane Gao et al. [318] 504–506 3–3.3 50 SynVisVarPcTc
Hydrogen sulfide + N-methyldiethanolamine Rebolledo-Libreros and Trejo [583] 313–393 0–1 320 AnTVcir
(MDEA) + diethanolamine (DEA) + water
Hydrogen sulfide + N-methyldiethanolamine Sidi-Boumedine et al. [638] 313–373 0–1.1 n.a. SynT
(MDEA) + water + diethanolamine (DEA)
Hydrogen sulfide + water + ethylene glycol + sodium cloride Majumdar et al. [493] 273–289 0.2–1.4 n.a. SynVisVar
Hydrogen Xia et al. [717] 353–353 0.1–6.2 30 SynVis
sulfide + water + piperazine + N-methyldiethanolamine
(MDEA)
Nitrogen + dimethyl ether + water + methanol Laursen et al. [38] 298–318 0.4–10.2 570 AnTValVis
Nitrogen + ethanol + water + dimethyl ether Laursen and Andersen [435] 298–318 0.4–10.2 570 AnTVis
Nitrogen + ethene + 1-hexene + poly(ethylene-co-1-hexene) Dörr et al. [270] 393–493 12.7–206.5 14.5–19.0 SynVisVar
copolymer
Nitrogen + oleic acid + ␣-pinene + abietic acid Laursen et al. [50] 298–318 3.7–14.7 90 AnTVcirX
Nitrogen + vinyl acetate + ethene + poly(ethylene-co-vinyl Kinzl et al. [423] 393–493 26.7–193 14.5–19.0 SynVisVar
acetate) copolymer
n-Tridecane + n-tetradecane + n-pentadecane + n-hexadecane Daridon et al. [106] 277–296 0.1–100.3 0.03 SynVis
Hydrogen sulfide + N-methyldiethanolamine Rebolledo-Libreros and Trejo [583] 313–393 0–1 320 AnTVcir
(MDEA) + diethanolamine
(DEA) + 2-amino-2-methyl-1-propanol + water
n-Tridecane + n-tetradecane + n-pentadecane + n- Daridon et al. [106] 279–298 0.1–100.3 0.03 SynVis
hexadecane + n-heptadecane
Toluene + water + deuterium oxide + deuterium protium Furutaka and Ikawa [313] 473–623 10–35 n.a. AnSpecVis
oxide +
n-Tridecane + n-tetradecane + n-pentadecane + n- Daridon et al. [106] 283–302 0.1–100 0.03 SynVis
hexadecane + n-heptadecane + n-octadecane
n-Tridecane + n-tetradecane + n-pentadecane + n- Daridon et al. [106] 286–305 0.1–98 0.03 SynVis
hexadecane + n-heptadecane + n-octadecane + n-nonadecane
n-Tridecane + n-tetradecane + n-pentadecane + n- Daridon et al. [106] 289–309 0.1–100 0.03 SynVis
hexadecane + n-heptadecane + n-octadecane + n-
nonadecane + n-eicosane
n-Tridecane + n-tetradecane + n-pentadecane + n- Daridon et al. [106] 295–315 0.1–100 0.03 SynVis
hexadecane + n-heptadecane + n-octadecane + n-
nonadecane + n-eicosane + n-heneicosane + n-docosane
R. Dohrn et al. / Fluid Phase Equilibria 288 (2010) 1–54 45
Table 53
Complex systems: X + Y (+ . . .).
Table 54
Binary systems with hydrates: water + X.
Table 55
Ternary systems with hydrates: water + X + Y.
Carbon Copper(II) sulfate Clarke et al. [233] 273–286 0.7–4.3 n.a. SynVisVar
dioxide Cyclobutanone Mooijer-van den Heuvel et al. [521] 279–315 0.3–11.9 n.a. SynVis
Cyclohexane Mooijer-van den Heuvel et al. [521] 274–288 0.9–10.4 n.a. SynVis
Ethylene glycol Majumdar et al. [493] 264–276 1.2–3.1 n.a. SynVisVar
Magnesium sulfate (1:1) Clarke et al. [233] 275–280 1.8–3.8 n.a. SynVisVar
Methane Seo et al. [612] 273–285 1.5–6.7 50 AnTValVis
Methylcyclohexane Mooijer-van den Heuvel et al. [521] 277–280 1.8–11.3 n.a. SynVis
Nitrogen Kang et al. [404] 272–284 1.3–32.3 70 AnTValVis
Potassium nitrate Clarke et al. [233] 275–278 1.8–3.5 n.a. SynVisVar
Tetrahydropyran Mooijer-van den Heuvel et al. [521] 280–291 0.4–4.2 n.a. SynVis
Ethane Diethylene glycol (DEG) Mahmoodaghdam and Bishnoi [492] 274–282 0.6–2.2 n.a. SynVisVar
Ethylene glycol Majumdar et al. [493] 271–282 0.5–2.6 n.a. SynVisVar
Helium Maekawa [490] 273–287 0.7–4 500 SynVis
Propane Ballard et al. [159] 276–279 0.5–2 3 SynVis
Ballard et al. [159] 277–282 0.5–2.5 n.a. SynVis
Hydrogen Propane Zhang et al. [739] 274–278 0.8–4 60 SynVisVar
Hydrogen sulfide Ethylene glycol Majumdar et al. [493] 272–295 0.2–1.5 n.a. SynVisVar
Methane 1,3-Dioxolane De Deugd et al. [253] 282–299 2–14 n.a. SynVis
1,4-Dioxane Seo et al. [613] 280–292 1.7–8.9 50 SynVis
2,2-Dimethylpentane Ostergaard et al. [550] 274–285 2.6–9.8 540 SynVis
2-Methylbutane (isopentane) Ostergaard et al. [550] 277–287 3.7–12 540 SynVis
2-Methylcyclohexanone Ohmura et al. [547] 273–280 1.4–3.2 201 SynNon
3,3-Dimethyl-2-butanol (pinacolyl alcohol) Ohmura et al. [546] 273–280 1.5–3.4 200 SynNon
3,3-Dimethyl-2-butanone (pinacolone) Ohmura et al. [546] 273–280 1.1–2.8 200 SynNon
3-Methyl-1-butanol (isopentanol) Ohmura et al. [548] 273–281 2.2–6.1 200 SynNon
3-Methylcyclohexanone Ohmura et al. [547] 273–279 1.6–3.4 201 SynNon
4-Methylcyclohexanone Ohmura et al. [547] 237–280 1.5–3.3 201 SynNon
Acetone Seo et al. [613] 279–288 1.9–7.6 50 SynVis
Calcium chloride Kharrat and Dalmazzone [412] 260–284 4.9–10.3 n.a. SynNon
cis-1,4-Dimethylcyclohexane Nakamura et al. [531] 274–287 1.6–9.1 150 SynVis
Cyclobutanone Mooijer-van et al. [520] 293–301 3.8–12.7 n.a. SynVis
Cyclohexane Sun et al. [659] 273–291 0.6–9.4 n.a. SynVisVar
Cyclooctane Makino et al. [494] 274–288 1.6–9.3 150 SynVis
Cyclopentane Sun et al. [659] 282–301 0.1–7.3 n.a. SynVisVar
Ethane Zhang et al. [738] 274–274 2.5–4 60 AnTVarVis
Ethene Ma et al. [486] 273–287 0.6–6 60 SynVis
Sugahara et al. [656] 284–293 1.9–19 100 AnTVis
Sugahara et al. [656] 293–293 8.5–20.8 0.1 SynVisSpec
Ethylene glycol Mahmoodaghdam and Bishnoi [492] 267–277 2–4.4 n.a. SynVisVar
Helium Maekawa [490] 273–284 3.4–10.2 500 SynVis
Hydrogen Zhang et al. [739] 274–278 3.7–6.6 60 SynVisVar
Methylcyclohexane Mooijer-van et al. [520] 279–288 2.6–9.1 n.a. SynVis
Ohmura et al. [547] 275–281 1.5–3.3 201 SynNon
Sun et al. [660] 273–290 1.3–11.9 n.a. SynVisVar
Methylcyclopentane Makino et al. [494] 274–287 1.7–9.3 150 SynVis
Neohexane Ohmura et al. [546] 274–280 1.3–2.7 200 SynNon
Propene Ma et al. [486] 273–283 0.5–6.5 60 SynVis
Propylene oxide Seo et al. [613] 283–294 1.9–8.7 50 SynVis
Sodium chloride Jager and Sloan [110] 270–303 6.6–72.2 1 SynVisSpec
Kharrat and Dalmazzone [412] 269–278 4.2–8.6 n.a. SynNon
Sodium dodecyl sulfate Link et al. [102] 276–293 3.9–9.6 40 SynVis
Tetrafluoromethane (CFC-14) Mooijer-van et al. [520] 273–290 3.4–12.9 n.a. SynVis
Tetrahydrofuran De Deugd et al. [253] 289–306 2–14 n.a. SynVis
Tetrahydrofuran (THF) Seo et al. [613] 292–302 2–8.9 50 SynVis
Tetrahydropyran De Deugd et al. [253] 288–302 2–14 n.a. SynVis
Mooijer-van et al. [520] 293–303 3.4–13.5 n.a. SynVis
Trifluoromethane (HFC-23) Mooijer-van et al. [520] 282–297 0.9–12.9 n.a. SynVis
Methanol Natural near critical reservoir fluid (C1−C20+) Ostergaard et al. [551] 276–283 5.3–24.2 540 SynVis
Nitrogen 1,4-Dioxane Seo et al. [613] 275–283 3.7–11.8 50 SynVis
2,2-Dimethylpentane Ostergaard et al. [550] 275–280 15–26.4 540 SynVis
2-Methylbutane (isopentane) Ostergaard et al. [550] 276–282 14.9–30.2 540 SynVis
Acetone Seo et al. [613] 274–280 4.4–11.3 50 SynVis
Propylene oxide Seo et al. [613] 279–285 4–11.7 50 SynVis
Tetrahydrofuran (THF) Seo et al. [613] 287–293 4.3–10.8 50 SynVis
Propane Cyclobutanone Mooijer-van et al. [522] 276–277 0.2–12.8 n.a. SynVis
Cyclohexane Mooijer-van et al. [522] 274–276 0.1–9.9 n.a. SynVis
Methylcyclohexane Mooijer-van et al. [522] 274–277 0.1–7.8 n.a. SynVis
Tetrahydropyran Mooijer-van et al. [522] 274–276 0.1–4.8 n.a. SynVis
R. Dohrn et al. / Fluid Phase Equilibria 288 (2010) 1–54 47
Table 56
Multicomponent and complex systems with hydrates: water + X + Y (+. . .).
Carbon dioxide + ethylene glycol + sodium cloride Majumdar et al. [493] 264–272 1.3–3.1 n.a. SynVisVar
Carbon dioxide + methane + hydrogen sulfide Sun et al. [658] 274–299 0.5–8.6 60 SynVisVar
Carbon dioxide + nitrogen + tetrahydrofuran Kang et al. [404] 274–295 0.2–12.9 70 AnTValVis
Hydrogen + methane + propane Zhang et al. [739] 274–280 0.6–4.9 60 SynVisVar
Hydrogen sulfide + ethylene glycol + sodium cloride Majumdar et al. [493] 273–289 0.2–1.4 n.a. SynVisVar
Methane + ethane + propane Ostergaard et al. [552] 276–290 1.4–7.9 540 SynVis
Methane + ethane + tetrahydrofuran Zhang et al. [738] 274–284 2–3 60 AnTVarVis
Methane + ethylene glycol + sodium chloride Eichholz et al. [278] 262–281 2.1–9.5 64–74 SynVisVar
Methane + magnesium chloride + sodium chloride Link et al. [102] 269–293 7.9–9.6 40 SynVis
Methane + methanol + sodium chloride Jager et al. [377] 249–281 2–16 n.a. SynVis
Jager et al. [377] 260–292 7.4–73.2 1 SynVisSpec
Methane + nitrogen + 2,2-dimethylpentane Ostergaard et al. [550] 276–286 6.2–22.6 540 SynVis
Methane + nitrogen + 2-methylbutane (isopentane) Ostergaard et al. [550] 276–284 5.1–15.4 540 SynVis
Hydrogen + methane + ethane + propane Zhang et al. [739] 274–279 1.1–7 60 SynVisVar
Methane + ethane + cyclohexane + propane Sun et al. [659] 273–289 0.6–6.2 n.a. SynVisVar
Methane + ethane + propane + methylcyclohexane Ostergaard et al. [552] 280–288 2.6–8.1 540 SynVis
Methane + ethane + propane + methylcyclopentane Ostergaard et al. [552] 278–288 2–7.7 540 SynVis
Methane + ethane + propane + 2-methylbutane (isopentane) Ostergaard et al. [552] 275–282 2–5.1 540 SynVis
Methane + ethane + propane + methylcyclohexane Sun et al. [660] 273–288 0.9–6.1 n.a. SynVisVar
Methane + ethylene glycol + potassium chloride + sodium chloride Masoudi et al. [501] 259–283 3.9–46.6 n.a. SynNon
Methane + ethane + propane + n-pentane + n-decane Ostergaard et al. [552] 279–286 1.2–3.8 540 SynVis
Methane + ethane + propane + n-pentane + n-decane + cyclohexane Ostergaard et al. [552] 276–284 0.8–3.1 540 SynVis
Methane + ethane + propane + n-pentane + n-decane + cyclopentane Ostergaard et al. [552] 278–287 0.2–4.2 540 SynVis
Methane + ethane + propane + n-pentane + n-decane + 2,2- Ostergaard et al. [552] 278–286 0.9–3.4 540 SynVis
dimethylpropane
(neopentane)
Methane + ethane + propane + n-pentane + n- Ostergaard et al. [552] 278–288 0.4–2.6 540 SynVis
decane + cyclopentane + 2,2-dimethylpropane
(neopentane)
Synthethic natural gas Ostergaard et al. [552] 276–290 1.2–7.6 540 SynVis
Natural gas—Alinta Gas Ltd., Perth, Australia + para-toluene sulfonic Gnanendran and Amin [333] 285–293 1.4–8 700 SynNonVisVar
acid
Synthethic natural gas + cyclohexane Ostergaard et al. [552] 277–292 1.1–9.6 540 SynVis
Synthethic natural gas + cyclopentane Ostergaard et al. [552] 283–288 1.2–3.1 540 SynVis
Synthethic natural gas + methylcyclopentane Ostergaard et al. [552] 278–289 1.7–7 540 SynVis
Table 57
Articles containing corrigenda, comments or rebuttals to comments.
Nikitin et al. [537] 1998 1-Alkanols (C13–C22) Nikitin et al. [538] 2000 Corrigendum
Xia et al. [712] 1999 CO2 , water, sodium acetate, Xia et al. [713] 2000 Corrigendum
ammonium acetate
Bobbo et al. [177] 2000 HFC-125, HFC-236ea, HFC-32 Deiters [258] 2001 Comments
da Silva and Barbosa [243] 2000 CO2 , n-butanal Coquelet et al. [234] 2002 Comments
da Silva and Barbosa [246] 2002 Rebuttal to Comments
Lee et al. [445] 2000 CO2 , C.I. Disperse Blue 3, C.I. Lee et al. [446] 2001 Corrigendum
Disperse Blue 79
Sako et al. [596] 2001 5 fluorinated ethers and 2 Sako et al. [597] 2002 Corrigendum
fluorinated ketones
García-González et al. [323] 2002 CO2 , hydroquinone, p-quinone Deiters [259] 2003 Comments
Kato et al. [407] 2002 HFC-32, HFC-125 Kato et al. [408] 2004 Corrigendum
Zhang and Kiran [740] 2003 CO2 , tetrahydrofuran, polysulfone Zhang and Kiran [741] 2006 Corrigendum
Gozalpour et al. [337] 2003 Methane, propane, n-pentane, Gozalpour et al. [338] 2003 Corrigendum
n-decane, n-hexadecane
Chapoy et al. [214] 2003 Methane, water, methane hydrate Chapoy et al. [220] 2005 Corrigendum
Kamps et al. [403] 2003 CO2 , [bmim][PF6] Kumelan et al. [433] 2006 Corrigendum
Kiepe et al. [415] 2003 Methane, water, lithium bromide Kiepe et al. [417] 2004 Corrigendum
Nikitin et al. [57] 2003 CO2 , polystyrene Nikitin et al. [58] 2003 Corrigendum
Glos et al. [331] 2004 Propane, 2-methylpopane, Glos et al. [332] 2006 Corrigendum
n-butane, propylene
Levitin et al. [454] 2004 CO2 , methanol, water, Levitin et al. [455] 2005 Corrigendum
tetramethylammonium
bicarbonate
48 R. Dohrn et al. / Fluid Phase Equilibria 288 (2010) 1–54
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1–12. (2002) 29–47.
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(2003) 53–67. [716] J. Xia, B. Rumpf, G. Maurer, Fluid Phase Equilibr. 168 (2000) 283–284.
[688] A. Valtz, A. Chapoy, C. Coquelet, P. Paricaud, D. Richon, Fluid Phase Equilibr. [717] J. Xia, Á.P.-S. Kamps, G. Maurer, Fluid Phase Equilibr. 207 (2003) 23–34.
226 (2004) 333–344. [718] J. Xia, M. Jodecke, Á.P.-S. Kamps, G. Maurer, J. Chem. Eng. Data 49 (2004)
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[690] A. van Miltenburg, W. Poot, T.W. de Loos, J. Chem. Eng. Data 45 (2000) [719] S. Xia, P. Ma, Y. Guo, C. Hua, J. Chem. Eng. Data 49 (2004) 479–482.
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761–764. [740] W. Zhang, E. Kiran, J. Chem. Thermodyn. 35 (2003) 605–624.
[709] J. Wu, Q. Pan, G.L. Rempel, J. Chem. Eng. Data 49 (2004) 976–979. [741] W. Zhang, E. Kiran, J. Chem. Thermodyn. 38 (2006) 504.
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194–201.