Fluid Phase Equilibria, 2 (1979) 297-309 297

0 Elsevier Scientific Publishing Company, Amsterdam - Printed in The Netherlands

Review Series

LIQUID-LIQUID EQUILIBRIUM DATA: THEIR RETRIEVAL,

CORRELATION AND PREDICTION

PART I: RETRIEVAL

JENS M. S6RENSEN l, THOMAS MAGNUSSEN 2, PETER RASMUSSEN

and AAGE FREDENSLUND l*
1 Znstituttet for Kemiteknik, Danmarks Tekniske Hdjskole, DK-2800 Lyngby (Denmark)
2 DECHEMA, Postfach 970146, D-6000 Frankfurt (Main) 97 (G.F.R.)
(Received July 4rd, 1978; in revised form October ZOth, 1978)

ABSTRACT

SQrensen, J.M., Magnussen, T., Rasmussen, P. and Fredenslund, A., 1979. Liquid-liquid
equilibrium data: their retrieval, correlation and prediction. Part I: Retrieval. Fluid
Phase Equilibria, 2: 297-308.

Part one of this series of articles contains a status report covering the published
liquid-liquid equilibrium data for binary and multicomponent mixtures with organic
components. Different methods of measuring liquid-liquid equilibrium data are briefly
mentioned, and a new, computerized data bank for storage and retrieval of the data is
described.
This part will be followed by articles on the correlation and prediction of liquid-
liquid equilibria.

INTRODUCTION

Solvent extraction is a major unit operation based entirely on limited

liquid miscibility and the distribution of solutes between two liquid phases.
In azeotropic distillation, the separation of the entrainer (the added compo-
nent) from the overhead product is often enhanced by the formation of two
liquid phases after the condenser. In the design of such processes - and
indeed whenever solvents are used in chemical technology - it is uncondi-
tionally necessary to know, from data or from calculations, the compositions
of the two phases in equilibrium.
Limited miscibility is also of interest in another context. The unexpected
presence of two liquid phases can be a serious problem in, for example,
distillation and pumping. Hence one must be able to determine, by experi-
ment or by calculation, whether one or two (or more) liquid phases are pre-
sent.

l To whom correspondence should be addressed.

298

In spite of its practical importance, liquid-liquid equilibria has not

received nearly as much attention in the literature as vapor-liquid equilibria.
There are several reasons for this: (1) the experimental determination of
liquid-liquid equilibrium compositions can often be carried out on an ad
hoc basis which reduces the incentive for correlation and publication; (2)
the correlation of liquid-liquid equilibrium data can be, from a numerical
point of view, much more difficult than the correlation of vapor-liquid
equilibria; (3) temperature-effects are more pronounced for liquid-liquid
equilibria than for vapor-liquid equilibria; (4) economically speaking, distil-
lation plays a bigger role in industry than does extraction. Nevertheless,
many references -. especially to experimental work - do exist for liquid-
liquid equilibria.
The latest comprehensive lists of references to liquid-liquid equilibrium
data are quite old. Some of them are: Francis (1963, 1972), Stephen and
Stephen (1963), Seidel et al. (1941, 1952), and Landolt-Bornstein (1959).
Valuable information is also given in Fortschritte der Verfahrenstechnik,
1952-, which contains yearly citations of liquid-liquid equilibrium data.
We have, in collaboration with the University of Dortmund and DECHEMA
(Deutsche Gesellschaft fiir chemisches Apparatewesen), begun systematically
to collect, to correlate, and to predict all published liquid-liquid equilibrium
data within the range of components, temperature, and pressure given at the
end of this section. The aim of this effort is: to establish a comprehensive,
computerized data bank for liquid-liquid equilibrium data; to correlate
these data and report the results in the DECHEMA Chemistry Data Seires
(Stirensen and Arlt, 1979) and to estabhsh a group-contribution method
similar to UNIFAC (Fredenslund et al., 1977) for liquid-liquid equilibria.
The purpose of this series of articles is to report our major conclusions
from this work.
In Part I we give a status report on the published liquid-liquid equilib-
rium data for binary and multicomponent mixtures. Different methods of
measuring liquid-liquid equilibrium data are discussed, and the new data
bank described. Part II will be on the correlation of and Part III on the pre-
diction of liquid-liquid equilibrium data.
The kinds of mixtures considered in this series are the same as those
included in the data bank (S$rensen and Arlt, 1979). That is, the compo-
nents are water and organic, non-polymeric compounds. The components
must contain two or more of the following atoms: C, H, 0, N, F, Cl, Br and
S. All components have a normal boiling point above 0C; the temperature
range is roughly O-150 C; and the pressure range is up to approximately
20 atm. These are the kinds of mixtures that are of interest in the petro-
chemical and related industry.
LIQUID-LIQUID EQUILIBRIUM DATA
Binary, ternary, and quaternary liquid-liquid equilibrium data have been
reported in the literature.
 299

Francis (1963) gives a thorough discussion of the different liquid-liquid

equilibrium phase diagrams encountered. In this section, we show the differ-
ent types found in the data bank by Srjrensen and Arlt (1979), and we indi-
cate the approximate frequency by which each type of phase diagram is
encountered. This does not exhaust the many different liquid-liquid equilib-
rium diagrams found in general (see for example Francis, 1963). Phase dia-
grams different from those shown in this section may be formed when com-
ponents such as inorganic salts or volatile gases are present. As already
stated, such mixtures are not covered in this work. At the time of writing
this article, we estimate that 75% of the possible literature data are included
in the data bank.
Binary liquid-liquid equilibrium data may be presented as T-x diagrams
giving the mutual solubilities (xi) as functions of temperature (T). Note that
the concentration unit, xi, throughout this work is mole fraction. The differ-
ent types of T--x diagrams which can be constructed from the data in the
data bank are shown in Fig. 1. The relative frequency of encountering each
type of diagram among the binary mixtures with a total of five or more data
points is given. The information for such a mixture is constructed from all
available equilibrium data. For example, all published equilibrium data for
benzene-water belong to only one mixture, even if the data are taken from
different publications. The total number of such mixtures is now 382.
In Fig. 1, the curves separating the two-phase region from the one-phase
region are termed binodal curues. A horizontal line -termed a tie line -
intersects the binodal at two points which give the compositions of the two
liquid phases in equilibrium at the given temperature.
From a theoretical point of view, the most general T-~E diagram is that
shown in Fig. la, which exhibits both a lower and upper critical solution
temperature. Below the LCST and above the UCST there is only one liquid
phase. The LCST and UCST are also referred to as, respectively, the lower
and upper consolute temperatures.
If the region with two liquid phases intersects the mixture freezing-point
curve, the LCST does not exist. In this case -.- and when the LCST simply
lies below the temperature range in which data are recorded - a phase dia-
gram similar to Fig. lb results.
If the region with two liquid phases intersects the vapor-liquid equilib-
rium curve, the UCST does not exist. In this case - and when the UCST lies
above the temperature range of the data - a phase diagram similar to Fig. 1~
results.
When both the LCST and the UCST are missing a phase diagram similar to
Fig. Id results.
It is worthwhile to note that among the binary mixtures included in the
data bank, 94% of the mixtures are covered by phase diagrams of the types
shown in Figs. Id and lb.
Examples of binary mixtures shown in Fig. 1 are:
Figure la: Furan, tetrahydro-Water
Nicotine-Water
300

UCST UCST

Two phases

Two phases

LCST

0. 1
Xl
1 a: Lower (LCST) and lb: Upper critical solution
upper (UCST) critical temperature

n
solution temperature Frequency: 41%
Frequency: 4%

\./
Two phases

T T TWO phases

LCST

0.
Xl
1. 0.
Xl 1.

lc: Lower critical solution Id : Two-phase region in the

temperature whole temperature range
Frequency: 2% Frequency: 53%
Fig. 1. Types of binary liquid-liquid equilibria,

Figure lb: 1-Butanol-Water

Aniline-Hexane
Figure lc: Amine, dipropyl-Water
Pyridine, 2,4-dimethyl-Water
Figure Id: Benzene-Water
Methane, tetrachloro-Water
Ternary liquid--liquid equilibrium data are usually recorded at constant
temperature. The data may be portrayed in triangular diagrams as shown in
Fig. 2. Each vertex represents one of the pure components. The concentra-
tion units are mole percent. The binodal curve separates the one-phase region
from the two-phase region, and a tie line (the dotted line in Fig. 2) connects
two points corresponding to the compositions of the two liquid phases in
equilibrium. As the plait point (P) is approached, the tie lines become
 301

Fig. 2. Triangular diagram for ternary liquid-liquid equilibria.

shorter and shorter, and finally at the plait point only one liquid phase exists.
The different types of ternary diagrams found in the data bank are shown
in Fig. 3, which also gives the relative frequency of encountering each type
of diagram among the ternary mixtures with a total of five or more tie lines.
At the present, the data bank contains 405 such mixtures. The components
are ordered such that the tie lines nearly always slope towards the corner
representing pure component 3 (negative slopes). In many applications, com-
ponents 1 and 3 are considered solvents, and component 2 is solute.
The most common ternary diagram is that corresponding to Fig. 3a. The
1-3 binary shows immiscibility, and the l-2 and 2-3 binaries are completely
miscible. All tie lines have negative slopes. This is termed a type one diagram.
The two-phase region may look different from the one shown in Fig. 3a. It
may be narrow and deep, but this is unusual. Slightly more frequently the
curve is more shallow than Fig. 3a.
Figure 3c corresponds to another frequently encountered ternary phase
diagram, a type two diagram. Here both binaries l-3 and 2-3 exhibit immisci-
bility while binary 1-2 is completely miscible. There is no plait point, and
the tie lines near the edge of the graph are almost parallel with the sides
of the triangle. Figure 3b is a transient between Figs. 3a and 3c. If Figs. 3a,
3b, and 3c apply to the same mixture at different temperatures, T, is typi-
cally the highest temperature and T, the lowest. This applies when the tie lines
for the binary 2-3 are in the area of the TXX diagrams towards the UCST.
Figure 3d is quite similar to Fig. 3a, except that two of the binaries are
immiscible. Fig. 3d is a type two diagram with two separate two-phase
regions. It contains in reality two small type one diagrams. Fig. 3e corre-
sponds to Fig. 3d, but the temperature is different.
Island curves similar to Fig. 3f can often be explained in terms of the
formation of a fourth component, for example the formation of a salt from
the simultaneous presence of a weak acid and a weak base. In this case the
mixture is not truly a three-component system, and we do not include these
in the data bank.
However, there still are some systems which we consider three-component
mixtures in the data bank and which exhibit island curve behavior (see
302

2 2 2

/qA
1 3 1 3 1
A 3

3a: Type one 3b : Type two (Tranm 3c : Type two

Frequency: 75% sient between Frequency: 20%
type one and two)
Frequency: 2%
2

A -ZZ--
1 3 1 3

3d: Type two (Con- 3e: Type two (The

structured from two two curves from
type one diagrams) 3d have merged)
Frequency: < 1% Frequency: < 1%
2 2

1 3 I 3

3f: Island curve 3g: Type one (Evolved

Frequency : < 1% from 3f by a temper-
ature change)
Frequency: < 1%
2

1 3 1 3

3h: Type one (Tie 3i: Three coexist-

lines with ing liquid
negative slopes) phases (a, b
Frequency: C 1% and c)
Frequency: < 1%

Fig. 3. Types of ternary liquid-liquid equilibria.

 303

below). Note that there are two plait points in an island curve. In these cases,
the temperature is above the UCST or below the LCST for the binary 1-3,
but the ternary still has a two-phase region. If we are above the UCST of a
binary and the temperature is raised, the two-phase region becomes smaller
and smaller; as the temperature is lowered, one may get below the UCST of
one or more of the binaries, and a phase diagram as shown in Fig. 3g results.
In some cases the tie lines in a diagram similar to Fig. 3a do change from
having negative to having positive slopes. One tie line is parallel with the base
line, and this tie line is called a solutrope. There are even diagrams with two
solutropes, i.e. the slopes of the tie lines are reversed twice. An example of
this is indicated in Fig. 3h.
Finally, a system with three coexisting liquid phases is indicated in Fig. 3i.
The concentrations of the three phases are given by the points a, b and c.
Note that among the ternary mixtures included in the data bank, more
than 95% are covered by phase diagrams similar to Figs. 3a, 3b, and 3c. ,
Examples of ternary phase diagrams are:
Figure 3a: Water-Ethanol-Benzene
Ether, diisopropyl-2-Propanol-Water
Figure 3b: Phenol-Acetic acid, butyl ester-Water
Figure 3c: Heptane-Cyclohexane, methyl-Aniline
Cyclohexane-Benzene-Water
Figure 3d: 2-Butanol--2.Butanone-Water
Nicotine-2-Butanone-Water
Figure 3e: 2-Butanol--2.Butanone-Water
Nicotine-2.Butanone-Water
Figure 3f: Phenol--2.Propanol-Water
Water-Sulfoxide, dimethyl-Furan, tetrahydro
Figure 3g: Phenol--2.Propanol-Water
Figure 3h: Water-l-Propanol-Heptane
Water-1-Propanol-Ether, diphenyl
Figure 3i: Aniline-Water-Heptane
1-Dodecanol-Methane, nitro-1,2-Ethanediol
Only 23 quaternary mixtures have been found for the data bank. Data of
this type are of some practical interest, e.g. in solvent extraction processes
with two solvents. Some of the mixtures studied in detail are: water-acetic
acid-acetone--chloroform and benzene-hexane-N,N-dimethylformamide-
water. A detailed discussion and classification of the quaternary mixtures
will not be attempted here.

MEASUREMENT OF LIQUID-LIQUID EQUILIBRIA

In this section we briefly describe the major methods used for measuring
liquid-liquid equilibria.
The easiest way of measuring the solubility of a solute in a solvent is to
place a known amount of solvent in an open vessel and, while agitating, add
304

the solute by titration until the binary mixture becomes turbid. A similar
experiment may be carried out in a closed vessel, from which air has been
evacuated. In this case, the system will contain two liquid phases and one
vapor phase in equilibrium.
In a binary system with two liquid phases and one vapor phase, there is
only one degree of freedom according to the phase rule. If we want to estab-
lish a T-x diagram, we may fix T and measure x or vice versa. The pressure
will vary with T and X. In experiments carried out in the open vessel, the
pressure is constant. This is, of course, not in disagreement with the phase
rule; the two liquid phases are not in equilibrium with the vapor phase and
the presence of air gives rise to additional components in the system.
For the mixtures and range of pressures (up to 20 atm) considered in this
work, the effect of pressure on the liquid solubility is negligible. This holds
for both binary and multicomponent systems. In many references, the pres-
sure is not even recorded, and in the following the system pressure can safely
be omitted from the discussion.
Ternary liquid-liquid equilibrium data are usually determined in one of
two ways: the method of analysis or the method of titration (Alders,
1959). Both of the methods are carried out at constant temperature.
The method of analysis simply consists of letting a ternary mixture
separate into two liquid phases and determining the compositions of the two
phases in equilibrium by analyzing for each component. Obviously, the
method of analysis gives the tie lines directly.
In the method of titration, the binodal curve is first established. Figure 4
shows how part of a type one binodal curve is found. Component 3 is first
added to a known mixture of component 1 and 2 from a burette, until the
mixture becomes turbid. This establishes one point on the binodal, point A.
Then a known amount of component 2 is added, until an arbitrary point B
in the miscible region is reached. Then component 3 is again added to the
mixture, etc. The composition of the mixture is always known, as the
amounts of the three components added are known. The tie lines need still
to be determined. However, once the binodal curve is known, the concentra-
tion of only one of the components in each phase is sufficient information

A
I
I
II

,?
I,

El/ \\
-. . . . .
A--__ -__..\.
.I
-*
1 3

Fig. 4. Determination of binodal curve by titration.

 305

to determine a tie line. This may be a component, whose concentration is

easily determined, e.g. an acid.
Many investigators report their results from experiments using the method
of titration in two separate tables; one table gives the concentrations on the
binodal, and one gives the concentration of one component in each of the
two phases. In those cases it is necessary to combine the information in the
two tables in order to obtain tie line concentrations.

THE LIQUID-LIQUID EQUILIBRIUM DATA BANK

The purpose of the data bank (S$rensen and Arlt, 1979) is to make avail-
able all published, experimental liquid-liquid equilibrium data within the
limits given below. The data are stored on a computer and can be readily
retrieved. As described in Part II of this series, we use the data bank in the
study of mathematical models for representing and predicting liquid-liquid
equilibria. Other potential uses of the data bank include guidance in
choosing mixtures to study experimentally, direct use of the experimental
data in extraction process design, and others.
The data bank contains experimental binary, ternary, and quaternary
liquid-liquid equilibrium data giving the compositions in each of the
coexisting liquid phases. Whenever this information is not given directly by
the investigator - for example in some cases when the method of titration is
used - we have performed the necessary manipulations in order to obtain
the concentrations of all the components at each end of a tie line. Ternary
and quaternary data giving distribution ratios or critical solution tempera-
tures only have not been included in the data bank since tie line information
cannot be determined from such data.
The types of components (organic and water) found in the data bank are
those which can be constructed from two or more of the atoms: C, H, 0, N,
F, Cl, Br and S. Except for the lower fatty acids, phenol, amines and similar
components, electrolytes are not included. Polymers are not included. The
normal boiling point must be above 0C. The temperature range is 0-15OC,
but in a certain few cases data beyond this range are included. Finally, the
data bank contains only low-pressure data, i.e. below approximately 20 atm.
(For reasons explained in the previous section, the pressure is not recorded
in the data bank.) Data which are obviously erroneous - for example if the
concentrations do not add up to 100% - are excluded. (As explained in Part
II of this series, a consistency test is not available for liquid-liquid equilib-
ria.)
The data are arranged in data sets. For binary data, a data set consists of
the solubility of a component in a solvent (mole percent) as a function of
temperature. Data from both equilibrium phases (see Fig. 1) may be
included in a data set, but then the data must be from the same reference.
For ternary and quaternary data, a data set means a set of isothermal tie
line data.
306

---233 data sets

-- 121 data sets

1 5 10 15 20 25 1 k lb 1'5
Number of data points Number of tie lines in
in binary data sets ternary data sets

Fig. 5. Distribution of data sets with respect to number of data points or tie lines.

TABLE 1
Frequency with which the most common components appear in binary and ternary mix-
tures
(Only mixtures with a total of five or more data points/tie lines are included)

Component Frequency in binary Frequency in ternary

mixtures, % of total mixtures, % of total

Water 55.5 78.0

Methane, nitro 10.2
Glycerol 3.9
Heptane 3.9 9.6
Furfural 3.4 9.4
Hexane 3.4
Methanol 3.4 7.9
Benzene 2.6 10.9
Cyclohexane 2.6
Isocyanic acid, methyl ester 2.4
Pentane, 2,2,4-trimethyl 2.4
Acetic acid 9.4
Ethanol 7.9
2-Propanone 6.7
ZPropanol 4.9
Toluene 4.7
Total number of mixtures 382 405
with a total of five or
more data points/tie
lines
 307

At present we estimate that the data bank is 75% complete. It contains

884 binary, 772 ternary, and 23 quaternary data sets. Figure 5 indicates the
distribution of the binary and ternary data sets with respect to the number
of data points or tie lines they contain. It is seen that for binary mixtures,
many data sets contain only one data point. These may still be valuable,
since several data sets may pertain to the same mixture. For ternary data
sets, there is a maximum at 4-6 tie lines per data set.
Table 1 shows how frequently the most commonly encountered compo-
nents appear in a mixture. It is striking that water appears in 55% of the
binary and 78% of the ternary mixtures.
Table 2 shows which mixtures have been reported most extensively in the
literature.
The distribution of data points or tie lines with respect to temperature is
given in Fig. 6. The important feature is that 75% of the ternary data are
within 10 C of room temperature.

TABLE 2
Mixtures with most data points/tie lines
(The number in parentheses refers to the number of publications from which the mixture
information is taken)

Binary mixture Number of data points

(publications)

Benzene-Water 150 (30)

Phenol-Water 123 (11)
1-Butanol-Water 117 (8)
2-Butanone-Water 105 (10)
l-Propanol, 2-methyl-Water 105 (5)
Ether, diethyl-Water 34 (7)
Acetic acid, ethyl ester--Water 67 (3)
Phenol, 4-nitro-Water 52 (3)
Cyclohexane-Methanol 46 (3)
Phenol, 3-nitro-Water 44 (2)

Ternary mixture Number of tie lines

(publications)

Benzene-2-Propanol-Water 91 (4)
WaterEthanol-Benzene 73 (3)
Propenoic acid, nitrile-Acetic acid, nitrile-Water 75 (3)
2-Butanol-2-Butanone-Water 74 (1)
Water-Acetic acid-Benzene 60 (4)
Water-Acetic acid-Toluene 56 (2)
Nicotine-2-Butanoneater 52 (1)
Aniline-Phenol-Water 51(l)
1-Butanol-Methanol-Water 50 (2)
Acetic acid, propyl ester-l-Propanol-Water 47 (3)
Benzene-l-Propanol-Water 47 (3)
308

--- 27.1%

LI
m,
0. IO. 30. 120.
Temperature

Binary data
160.
C
0. 20.

Ternary
40.
Temperatura

data
60.

Fig. 6. Distribution of data points/tie lines with respect to temperature.

with a total of five or more data points/tie lines are included.)
C

(Only mixtures

The data bank does not contain information regarding the purity of the
components used in the experimental investigation. This is not feasible, since
many authors do not give this information, and when the information is
given, it is often not stated in easily convertible units. Often there is rela-
tively large disagreement between solubility data reported by different
authors for the same system. The reason for this may well be the presence of
small amounts of impurities.

CONCLUSIONS

The data bank described in the previous section brings together a vast
amount of information on liquid-liquid equilibria. The information may in
some cases be contradictory, in other cases doubtful. Nevertheless, it has
now become very easy to establish whether data exist for a given mixture,
and where new experimental work should be carried out. And more impor-
tantly, a systematic study of the correlation of liquid-liquid equilibrium
data is now within reach. We have selected for closer study a number of
binary and ternary data sets exemplifying the different types of phase behay-
ior (Figs. 1 and 31, and we have correlated these data in different ways using
various models. Part II of this series contains our conclusions from this work
and a review of how liquid-liquid equilibrium data have been correlated in
the past.
ACKNOWLEDGEMENTS

The authors are indebted to Mr. W. Arlt, Dr. J. Gmehling, and Professor
U. Onken, The University of Dortmund, for their collaboration. This work
was supported by Bundesministerium fi.ir Forschung und Technologie and
Statens teknisk-videnskabelige Forskningsrsd

REFERENCES

Alders, L., 1959. Liquid-Liquid Extraction, 2nd edn. Elsevier, Amsterdam.

Francis, A.W., 1963. Liquid-Liquid Equilibrium, Interscience, New York.
Francis, A.W., 1972. Handbook for Components in Solvent Extraction. Gordon and
Breach, New York.
Fredenslund, Aa., Gmehling, J., Michelsen, M.L., Rasmussen, P. and Prausnitz, J.M.,
1977. Computerized design of multicomponent distillationcolumns using the UNIFAC
group-contribution method for calculation of activity coefficients. Ind. Eng. Chem.,
Process Des. Dev., 16 (1977) 450. See also: Fredenslund, A., Gmehling, J. and Ras-
mussen, P., 1977. Vapor-Liquid Equilibria using UNIFAC. Elsevier, Amsterdam.
Landolt-Bornstein, 1959. Zahlenwerte und Funktionen, Zweiter Band. Springer-Verlag,
Berlin.
Seidel, A., 1941. Solubilities of Organic Compounds, 3rd edn. Van Nostrand, Princeton,
New Jersey, 1941; Supplement (with W.F. Linke), ibid., 1952.
Stephen, H. and Stephen, T., 1963. The Solubilities of Inorganic and Organic Com-
pounds, Pergamon Press, Oxford.
S$rensen, J.M. and Arlt, W., 1979. Liquid-Liquid Equilibrium Data Collection.
DECHEMA Chemistry Data Series, Frankfurt, in preparation.