FluidPhaseEquilibria,

29(1986)145-160 145
Elsevier Science Publishers B.V.. Amsterdam - Printed in The Netherlands

HIGH PRESSURE PHASE EQUILIBRIA: EXPERIMENTALMETHODS

U.K. DEITERS and G.M. SCHNEIDER

Lehrstuhl fiirPhysikalischeChemie II
Ruhr-UniversitatBochum
D-4630 Bochum 1, Federal Republic of Germany

ABSTRACT
The experimental investigationof high pressure phase equilibria, especially
the measurement of properties of coexisting phases, is not only of fundamental
scientific interest, but is also an intriguing and fascinating technical prob-
lem. This work reviews some recently developed experimental methods and clas-
sifies them with respect to the observed thermodynamicproperties. Several de-
vices and experimental procedures for the determinationof phase equilibria are
briefly explained. The advantages and limitations of these different methods
are discussed.

INTRODUCTION
Among the many thermodynamic properties of fluid mixtures the phase equili-
brium properties are especially important for several reasons: Many separation
processes in the chemical industry utilize phase equilibria so that understand-
ing the phase behaviour of mixtures is of considerable economic interest. On
the other hand, many theoretical studies of the thermodynamicsof mixtures have
shown that the phase behaviour of mixtures is quite sensitive to intermolecular
forces. In particular the calculation of phase equilibria at high pressures is
a very severe test for the theoretical concepts involved (equations of state,
pair potentials, mixing rules, etc.). Therefore experimental methods for the
determination of phase equilibria are not only immediately valuable to the
chemical engineer (by providing him with data on which his designs may be
based), but they are also very important to the theoretician.

0378-3812/86/$03.50 0 1986 Elsevier Science Publishers B.V.

146

EXPERIMENTAL METHODS
In mixture thermodynamics it is often practical to distinguish between SO-
called density and field variables (Griffiths and Wheeler, 1970). "Fields" are
variables which have'the same values in coexisting phases (e.g., temperature,
pressure), whereas "densities" are usually different (e.g., mole fractions,
molar volumes). The experimental determination of the field variables, although
an art in itself, is usually rather straightforward. The central problem of a
phase equilibrium experiment is the determination of the density variables. It
is more the exception than the rule that in a given experiment more than one
pair of 'idensities"is observed directly. Therefore it seems permissible to
classify the different experimental methods according to the "densities" which
are primarily observed.
The following descriptions of experimental methods do not constitute a com-
plete catalogue of modern techniques, but are meant to explain the underlying
principles. For older reviews see Schneider (1975) or Young (1978).

Determination of mole fractions

Synthetic method. This is probably one of the oldest methods of investi-
gating phase equilibria, but it is still used rather often. The idea is to pre-
pare a mixture of known composition and then to observe its behaviour so that
the problem of analyzing fluid mixtures is replaced by the problem of "synthe-
sizing" them.
Figure 1 shows an apparatus using this principle, which has been developed
recently (Matzik and Schneider, 1985; Ott, Holscher, and Schneider, 1986). The
pressure cell shown in figure 1 is fitted with a pair of sapphire windows so
that its contents can be observed during the experiment. The volume of the
pressure cell is variable; in this case the pressure is generated by a piston.
The experimental procedure is as follows: Known amounts of the components
are placed into the pressure vessel. Then the temperature and the pressure are
adjusted so that the contents of the pressure cell form one homogeneous phase;
its mole fractions can be calculated from the amounts of substances transferred
into the cell at the beginning. During the experiment the pressure or the tem-
perature is varied until the formation of a new phase is observed. Then the
pressure and the temperature, at which this phase separation starts, and the
mole fractions define a point of the phase envelope.
The typical results of synthetic experiments are sets of isopleths (phase
boundaries at constant composition), from which the P-x and T-x diagrams must
be obtained by cross-plotting.
As an example for a "synthetic" experiment, we present some recent phase
equilibrium data for the methanol/hexane system (Holscher, Schneider, and Ott,
 147

Fig. 1. Synthetic pressure cell

(Matzik and Schneider, 1985).
l-3: pressure cell, 4: magnetic
wire, 5: O-ring seals, 6: thermo-
couple, 7-8: windows, 9: heaters,
10: magnetic stirrer;
max. pressure 2000 bar, temperature
range 0 - 170°C.

Fig. 2. Isobaric phase diagram of

the methanol/hexanesystem (Holscher,
Schneider, and Ott, 1986).
symbols: experimental data, -:
empirical fitting functions.
Reproduced with permission from
Holscher et al. (1986); copyright
1986, Elsevier, Amsterdam.

0.0 0.2 0.4 0.6

- x Methanol
148

1986) in figure 2. The experimental isobars have a very broad, flat top. Here,
even slight disturbanceswould lead to large fluctuations of the phase composi-
tions, and so the application of the analytic method (see below) is not recom-
mended, whereas the synthetic method encounters no problems. On the other hand,
the synthetic method is less accurate on the steep parts of the isobars because
here a slight error in the overall compositionwould lead to a large deviation
of the temperature.
If the motions of the pressure-transferringelement (piston or bellows) can
be recorded with sufficient precision, it is also possible to obtain PVT data
and even orthobaric densities from a synthetic experiment, An example of such
an application has been published by Meskel-Lesavre, Richon, and Renon (1981).
Because of the high resolution of the volume measurements, the formation of a
new phase is detected not visually, but from the appearance of discontinuities
in pressure vs. volume curves.
Synthetic experiments with visual observation of the phase separation have
also been carried out at high temperatures,e.g. with mixtures containing long-
chain alkanes (de Loos, Poot, Perbal, and Lichtenthaler,1985) or mixtures con-
taining water in the vicinity of its critical point (Japas and Franck, 1985;
de Loos, Wijen, and Diepen, 1980).

Analytic method. In contrast to the synthetic method, analytical methods

do not have to rely on a precise knowledge of the overall concentration. Here
temperature and pressure are adjusted to bring about a phase separation (pre-
ferably with large amounts of both phases). Then samples are taken from the
phases and analyzed by appropriate methods. Most analytical methods require
that the sample is in a well defined state; e.g. gas chromatographyor mass
spectrometryrequire gases at low pressure. But if high pressure phase equili-
bria are studied, the equilibrium state may be quite different from the "input"
state of the analytical device; in fact, a change of temperature or pressure
may lead to a partial separation of components. Therefore the problem of the
analytical methods is not so much the determination of compositions from a
sample, but the preparation and handling of the sample.
The apparatus shown in figure 3 combines some features of the synthetic and
the analytic method (Wisotzki, 1984). Its centerpiece is a pressure cell equip-
ped with sapphire windows. The investigatedmixture and the pressure fluid are
separated by bellows; since the position of the bellows can be read precisely
(There is a magnetic wire attached to the bellows, which glides in the main
high pressure capillary; its position is detected by means of a high frequency
differential transformer), it is possible to gain some informationabout densi-
ties, too. The mixture is stirred vigorously with a magnetic stirrer. The appa-
 149

Fig. 3. Analytic/syntheticapparatus
(Wisotzki, 1984).
a) pressure cell
This view shows the Bridgman piston with
the bellows attached to it, the magnetic
stirrer, a sapphire window, and the two
sampling capillaries;
max. pressure 3000 bar, temperature range
80 - 373 K.

b) general assembly without pressure

generation and filling devices.
FV: sampling valves, PS: sample
loops, KK: coolant, DR: electromag-
netic valve, WT, MWT: Pt resistance
thermometers,HP: electrical heaters,
DMD A: pressure cell, KH: jacket, WA:
lzX==== differential transformer, DMD:
pressure transducer, SI,S2: recor-

m ders for temperature, pressure, and

_a
WA

I
~____________-____

bellows position.

51

._
-I BZ

d
PS
FV
He
---_____ C-V
GC

I
150

ratus can be used according to the synthetic method as described above; for
mole fractions far away from the critical point it is operated in the analyti-
cal mode: Samples of the liquid or the vapour phase are transferred into sample
loops connected to six-way valves. From there the samples are flushed into a
gas chromatographby flowing helium gas.
This apparatus has been designed for cryogenic applications. The pressure
cell is cooled with liquid nitrogen or with methanol from a cryostat. As long
as all components of the mixture under investigationhave high vapour pressures
at ambient temperature, no components of the samples are lost through condensa-
tion in the sampling capillaries, and so the compositions of the phases within
the pressure cell agree - at least after thorough flushing - with the input
compositionsto the gas chromatograph.
A typical result from this apparatus is shown in figure 4, which contains an
isothermal phase diagram of the nitrogen/ethanesystem. At the lowest tempera-
ture shown, a liquid-liquid immiscibility and the melting phase transition
"overlap" so that a solid-liquid-liquidthree-phase state occurs at about 1600
bar. At the higher temperatures the liquid-liquid immiscibilityregion remains
undisturbed (Wisotzkiand Schneider, 1985).

The apparatus shown in figure 5 is suitable for mixtures of supercritical

gases with low-volatile compounds. Again there are two capillaries for the
withdrawal of liquid and vapour samples. Because of the height of the pressure
vessel, a powerful magnetic stirrer had to be designed. In contrast to the ana-
lytic apparatus described above, the samples are not introduced into the gas
chromatograph immediately because condensation of the low-volatilecomponents
cannot be avoided when the pressure is reduced to the operating pressure of the
gas chromatograph. Instead, the samples are analyzed in two steps: First, the
samples are expanded into evacuated glass vessels. The supercritical component
is then in a gas state at low pressure; its amount is calculated from the re-
sulting total pressure. Second, the low-volatile components are flushed out
with an organic solvent, a calibration standard is added, and the solution is
analyzed by gas chromatography (Konrad, 1982; Konrad, Swaid, and Schneider,
1983).
Figure 6 shows the isothermal phase diagram of the system carbon dioxide/
tridecane/hexadecanolas obtained with this apparatus (Konrad, 1982). The ter-
nary critical line, which joins the critical points of the binaries (at con-
stant temperature), is not a straight line, but quite evidently curved in a
concave way. This indicates that the range of complete miscibility in this
system is larger than one might conclude from a linear interpolationbetween
the binary systems. It should be noted that not only the phase envelopes but
 151

p/MPa

150

100

sl

2 phases
.

0.2 Ok 0.6 OB
X

Fig. 4. Isothermal phase equilibria in the nitrogen/

ethane system at low temperatures and high pressures
(Wisotzki and Schneider, 1985).
o, q, o, 0: experimental data, -: interpolating
curves, -.-: three-phase line liquid-liquid-solid.
Reproduced with permission from Wisotzki et al. (1985);
copyright 1985, VCH Verlag, Weinheim.
152

Fig. 5. Analytic apparatus

(Konrad, 1982).
a) pressure vessel
l-4: Bridgman piston, 5-6: sampling
capillaries, 7: thermocouple, 8-9:
magnetic stirrer, 10: sapphire
window;
max. pressure 2000 bar, temperature
range 20 - 200°C.
The heating jacket, the compressor,
and the stirrer coils are not shown.

b) sample preparation
l-2 sampling valves, 14:
separator funnel, 15: orga-
nic solvent reservoir, 16:
calibration volume, 17:
manometer, 20: vacuum pump,
21: helium reservoir, 22:
carbon dioxide reservoir.
For further details see the
original literature.
 153

Fig. 6. Isothermal phase equilibria in the system

CO,/tridecane/hexadecanol (Konrad, Swaid, and
Schneider, 1983) at 423.4 K.
The compositions are represented by weight fractions.
0: exp. data, -: exp. tie-lines, -: binary phase
envelopes, ---: ternary critical line.
Reproduced with permission from Konrad et al. (1983);
copyright 1983, Elsevier, Amsterdam.
154

also the tie lines have been obtained, and so it is possible to study enhance-
ment factors or K-values with this apparatus.

It is not possible to give a complete explanation of all known sampling

techniques in this paper. In order to withdraw a sample without affecting its
overall compositionand without disturbing the equilibrium in the pressure cell
too much, the following principal techniques have been used:
- expansion into a sample loop, from there (through a six-way valve) evapora-
tion and transfer to a gas chromatograph;
- fast expansion directly into a gas flow leading to a gas chromatograph or
other analytical device, accomplished by means of fast-acting (pneumatic or
electromagnetic)valves (Figuiere, Horn,Laugier, Renon, Richon, and Szwarc,
1980; HUbner, 1983);
- expansion into a gas chromatographor other analyticaldevice through narrow
capillaries (Heintz and Streett, 1983; Radosz, 1984) or micro-bores (Maier
and Stephan, 1984);
- detachable sampling vessels; if their volume is known, it is possible to de-
termine orthobaric densities (Legret, Richon, and Renon, 1981);
- recirculationmethods, where the coexistingphases are continuallywithdrawn,
heated to a homogeneous vapour state (from where transfer to a gas chromato-
graph is easier), cooled by heat exchangers,and passed back into the equili-
brium cell (Dorau, Kremer, and Knapp, 1983; Weber, Zeck, and Knapp, 1984).
Analysis by gas chromatographyseems to be the most versatile method, espe-
cially for multicomponentmixtures, and is preferred by many authors. For bina-
ry mixtures of volatile compounds it is possible to determine compositionsfrom
heat conductivity (Streett and Calado, 1978; Heintz and Streett, 1983). Espe-
cially if one of the components of the mixture is hydrogen or helium, very pre-
cise mole fraction readings can be obtained.
Direct coupling of high pressure experiments and mass spectrometry is rather
difficult, but possible in principle, and has been demonstratedsuccessfullyin
connectionwith supercriticalfluid chromatography(Yonker, Wright, Udseth, and
Smith, 1984).

Determinationof concentrations
Spectroscopyor photometry usually belong to this class of methods, because
they make use of Beer's law (proportionalitybetween concentration (amount of
substance per volume) and absorbance). The difficulty with these methods is
that the extinction coefficientshave to be determined by extensive calibration
procedures. In some recent publicationsnear infrared (NIR) (Swaid, Nickel, and
Schneider, 1985) or ultraviolet (RiiBlingand Franck, 1983; Ebeling and Franck,
 155

1984) spectra have been utilized. The application of ultraviolet and visual
light spectroscopy is more or less restricted to aromatic or coloured com-
pounds. With infrared spectroscopy it is easier to find strong absorption
bands; unfortunately,the probability is quite high that absorption bands of
different compounds are overlapping. The use of larger wavelengths (fundamental
range) cannot be recommended for high pressure applications, because the ex-
tinction coefficients of fundamental bands are so large that rather small op-
tical pathlengths are required; these are difficult to keep constant when the
pressure is varied.
Instead of infrared absorption, Raman scattering can be used for the deter-
mination of compositions (e.g. Diller and Chang, 1980). Except for the fact
that Raman spectroscopycalls for a different pressure cell design from infra-
red spectroscopy,applicabilityand experimentalprocedure remain similar.
Figure 7 shows a schematic diagram of a phase equilibrium apparatus with
near-infraredspectroscopicdeterminationof phase concentrations.The pressure
vessel is equipped with two pairs of windows. It can be moved with respect to
the spectrometer so that the infrared sample beam may pass either through the
lower or through the upper phase. A piston is used to build up the pressure and
to control the volume of the pressure cell. The position of the piston, to
which a magnetic wire is attached, can be sensed by means of a high frequency
differential transformer. Further details of the high pressure cell have been
described elsewhere (Swaid, 1984). The infrared light intensitiesare digitized
and passed to a microcomputer, which records the data and performs baseline
corrections,smoothing, integrations,and other services required to obtain the
desired concentrationdata.
In analogy to the synthetic method described above, at the beginning of an
experimentalrun known amounts of the components of the mixture are transferred
into the pressure cell and brought to a homogeneous state. Since the volume of
the cell is known from previous calibrations, it is possible to calculate the
overall concentrationand to determine the extinction coefficients. Then the
pressure or the temperature is changed to bring about a phase separation. The
previously determined extinction coefficients are then used to calculate the
concentrationsof the coexisting phases.
With infrared spectra of hydrocarbons dissolved in supercritical gases, it
has been observed that the shapes and positions of the absorption bands depend
on pressure, temperature,and the solvent gas used; fortunately,the integrated
extinction coefficients show little dependence on pressure, temperature, or
compositionso that they can be used to calculate the concentrations.
The spectroscopic method is also applicable to high-pressure equilibria
involvingsolid phases. As a typical example for such a system, figure 8 shows
156

Fig. 7. Apparatus for investiga-

tion of phase equilibria by near-
infrared spectroscopy (Swaid,
Nickel, and Schneider, 1985).
a) pressure vessel
8- 14: moving piston, 6: magnetic
wire attached to it, 15: magnetic
stirrer, 16- 20: sapphire window
assembly;
max. pressure 2000 bar, tempera-
ture range 20- 18O'C.

b) general assembly
SG: stirrer driver, SPl, SP2:
stirrer coils, TE: thermocouple,
TM: thermostat iacket.MMS:micro-
meter screw, INF,TFM:-high fre-
quency bridge for determining
position of piston, SP: screw
press, A/O: sample and reference
beam analog/digital converters;
spectrometer: Cary 17H.
For further details see the ori-
ginal literature.
Reproduced with permission from
Konrad et al. (1983); copyright
1983, Elsevier, Amsterdam.
 157

the phase behaviour of the carbon dioxide/adamantane system (Swaid, Nickel, and
Schneider, 1985). The solubility of adamantane, which is solid at the tempera-
ture shown, in supercritical carbon dioxide is almost negligible at pressures
below some 100 bar, but increases very much in the pressure range 100 - 200
bar. Beyond 500 bar the solubility declines slightly. It is interesting to see
that the differences between two proposed calculation methods (based on the
Redlich-Kwong equation (1949) and our own equation of state (Deiters and Swaid,
1984)) become evident at high pressures only. This stresses the importance of
high pressure experiments for the development and testing of better computa-
tional methods.

Determination of volumes
A very interesting method, which avoids the complications of withdrawing
samples from a high pressure vessel, is based on in situ determinations of
fluid volumes. The idea is that at fixed pressure and temperature the composi-
tions and densities of coexisting phases of a binary system are also fixed; the
amounts of the coexisting phases, however, are not fixed, but depend on the
overall composition within the pressure vessel. If the same equilibrium state
(phase separation at the same temperature and pressure) can be reached with
different overall compositions, and if the volumes of the coexistingphases can
be measured, it is possible to calculate the orthobaric densities as well as
the mole fractions from a set of linear balance equations.
There are different technical realizationsof this experimentalprinciple.
Specovius, Leiva, Scott, and Knobler (1981) have used a glass apparatus and ob-

P/MPa
' 80
70
60
50
40
0 343.15 K
30 0 383.15 K
20 4 363.15 K
10 v 403.15 K
I
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 C 6
ci/mol*dm-'

Fig. 8. Isothermal phase equilibria of the carbon dioxide/adamantane system -

pressure vs. adamantane vapour phase concentration (Deiters and Swaid, 1984).
Adamantane is solid at the temperatures shown.
0, 0, A, V: experimental data, --- calculated with Redlich-Kwong equation of
state, - calculated with non-cubic equation of state.
158

served the position of the meniscus with a cathetometer. Fontalba, Richon, and
Renon (1984) have used a steel cell, where the position of the meniscus is
sensed by a movable thermistor.
It must be noted that this experimental principle requires an excellent re-
producibility of pressure and temperature in the autoclave. Furthermore, the
set of balance equations, which has to be solved for the phase compositions and
densities, is not always well-conditioned. It is necessary to observe the phase
volumes quite precisely.
The connection between total composition, total volume, phase compositions,
and phase densities can also be used to obtain the orthobaric densities from
mole fractions (by means of the analytic method described above; HUbner, 1983).

DISCUSSION
The rather large number of experimental methods and devices for the determi-
nation of phase equilibria in fluid mixtures under high pressure indicates that
there is no "perfect" method yet. Each method has its drawbacks and advantages,
and it is quite important to be aware of them.
The synthetic method does not require complicated analytical devices and so
it is relatively inexpensive. Furthermore, since there is no need to wait for
equilibration of phase compositions, the synthetic method is able to give much
information in a short time.
It is important to realize that the synthetic method does not observe the
phase boundary itself, but the formation of a new phase. Since a certain amount
of this new phase is necessary in order to be visible, the recorded pressure-
temperature state is never on, but always within, the phase envelope. As long
as the slopes of the phase boundary lines (e.g., dew point lines) vs. composi-
tion are small, the deviations will be negligible, but for mole fractions far
away from the critical this may not be so. Furthermore, if during a dew point
experiment the liquid phase does not condense as a mist, but as a thin film
on a wall of the pressure cell, the dew point may easily be overlooked. In
addition, the synthetic method cannot be applied when the coexisting phases
have similar refractive indices. On the other hand, the synthetic method does
not disturb the equilibrium very much so that it is reliable and especially
useful in the vicinity of critical points.
If the synthetic method is applied to multicomponent mixtures, it yields the
P-T-x envelopes only, but not the tie lines, so that its usefulness is much re-
duced in this case.
Analytic methods are generally slower and more expensive to use than syn-
thetic devices, but they are not restricted to binary systems. Furthermore,the
analytic method works well far away from critical points. It cannot be applied,
 159

however, in the vicinity of critical points, where the equilibrium is disturbed

by sampling, and of barotropic points, where the phases do not separate. This
shows that the analytic method is recommended when the synthetic method is
not, and vice versa.
For a severe and thorough test of theoretical methods it is necessary to
have not only the phase compositions, but densities and other thermodynamical
properties, too. It is very pleasing that the number of experimental methods
which produce orthobaric densities is increasing. For the future it is to be
hoped that the tendency to higher precision will continue.

ACKNOWLEDGMENTS
Financial support by the Deutsche Forschungsgemeinschaft,the Minister filr
Wissenschaftund Forschung NRW, and the Fonds der Chemischen Industriee.V. for
the experimentalwork performed at Bochum is gratefully acknowledged.

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