Alfred w.

%rancisl
Mobil Oil Coroorotion I
Paulsboro, N e w Jersey
and Norman O. Smith I Ternmy Liquid Systems
Fordham University
N e w York, N e w York 10458
I
O v e r the past thirty years an extensive extent. (Such interaction does not destroy the ternary
body of data on ternary liquid systems has been pub- character of the system as long as the composition of all
lished. A survey of these data and, in particular, the phases a t thermodynamic equilibrium can still he
considerable experimental work of one of us (AWF) expressed in terms of the original three components.
with such systems have revealed certain features of I n general, a quadrangle is needed to represent the
phase diagrams found only in monographs or research isothermal behavior of truly reciprocal ternary systems
papers but which are not general knowledge. The but, with the example mentioned, the composition
frequency with which some of the features have heen range studied is confined to a triangle, thus making the
observed suggests that there are guiding principles to be latter an adequate means of representation.) It is
followed, and that textbooks are frequently in error in clear, however, that a concavity cannot occur at the
certain matters. I n most cases apparent exceptions to plait point for then the tie lines immediately adjacent to
these principles have been found to be the result of it would have to cross the one-phase area and so result
known or probable impurities. This paper is an attempt in a contradiction. A symmetrical hinodal curve, with
to summarize what generalizations have been observed a plait point near the apex of the triangle is rare, but
and to draw attention to some examples of novel and observed in the system water-acetone-carbon disulfide
fascinating behavior which add interest to a classical at 20-21C (5) when compositions are plotted in
subject. It is hoped, at the same time, that it will weight per cent. This system also possesses an isopyc-
help to discourage the drawing of unrealistic phase n i e a phenomenon to he discussed below.
diagrams for instructional purposes. Except where The tie lines, when produced, intersect the side of the
stated, it is understood that ternary systems are being triangle on which the binodal curve is based only when
discussed, so that the presence of a fourth substance that side is also extended, as shown in Figure 1. Al-
(especially water), even in small amounts as an im- leged examples of tie lines intersecting the unextended
purity, is excluded. side have, in several cases tested, been shown to be the
result of impurities (4).Similarly, a tangent to the curve
Two Coexisting Phases at the plait point does not intersect the unextended
The most familiar phase behavior is that in which side. Alternatively, if straight lines be drawn from
two of the three liquid components are immiscible or the plait point to all three corners of the triangle, only
partially miscible, but each is miscible with the thud. one of these fails to cross the corresponding two-liquid
Addition of a sufficient quantity of the latter increases region. Meeting this restriction which, so far a3 is
the mutual solubility of the other two to the point where known, has no thermodynamic proof, requires con-
complete miscibility is attained, as shown in Figure 1 siderable care in the construction of figures with two or
(1) for the system acetic acid-isopropyl ether-water a t three plait points. Such systems will be discussed
23-24C. The binodal curve or "bite," XPY, separ- below. I n these the reverse relation also probably
ating the one-phase and two-phase areas, is the locus of holds, viz., only one plait point can be reached by a
the ends of the tie lines. At P, the plait point, the tie straight line from any one corner without crossing its
lines have shrunk to a point. As applied to isothermal
ACETIC ACIDO
extraction for an unusually favorable situation, B is the
original solvent for the solute A, and C is the extracting
solvent. The extract lies on Y P and the residual solu-
tion (raffinate) on XP. For a more common, hut less
favorable, situation the meanings of B and C are re-
versed. If the two-phase area is small then it is
usually also shallow. Othmer and coworkers (1)
observed that the plait point is located at a flatter por-
tion of the binodal curve. While the curve is generally
convex, a concavity can occur, as in the system water-
sulfuric acid-diethyl ether ($) at 25'C, where chemical
interaction between components takes place to some
Presented before the Division of Chemical Education of the
American Chemical Society, Minneapolis, Minnesota, April 1969.
Present Address: Apt. 12A-3, Redfield Village, Metuchen, Figure 1. The system acetic ocid(A1-iropropyl other(B1-water(C1 at
New Jersey 08840. 23-24'C.

Volume 46, Number 12, December 1969 / 81 5

own hinodal curve. This correspondence of compo- !BON DIOXIDE
nents (corners) with plait points suggests that more
than three plait points are impossible. The slope of the
tie lines usually changes steadily with increase in the
quantity of distributed component (A). This is to be
expected, at least for small additions of A, from the
distribution law. In many systems the direction of
change of slope reverses as the amount of distributed
component increases (6); in a few systems, e.g., water-
propionic acid-benzene a t 40C (6) there are at least
two reversals. (It is worth observing, however, that
changing from weight per cent to mole per cent com-
position coordinates not only changes the slopes of the
tie lines but may even change their sign.) METHYL PHTHALATE wHEPTANE
I n many two-phase areas there is, at a given tempera-
Figure 3. Tho ryrtem carbon dioxide(1)-methyl phfhdote-n-heptone a t
ture, one tie line connecting phases of equal density 21-26'C lunder prcsrurel.
(an isopycnic). Total compositions anywhere on such
a line have the same overall density as that of the
phases. It may he noted that isopycnics are to he ing effect if not too much is added; continued addition,
avoided in extraction processes, since settling of the however, can cause two liquid phases to reappear if the
layers is prevented. (An interesting lecture demon- composition of the original mixture lies in a suitable
stration can he arranged by adding traces of colored range. Three separate hinodal curves are also common
substances to an isopycnic system in order to make if one is not limited to ambient pressures. To show the
the two phases readily distinguishable (7).) The phenomenon at atmospheric pressure, however, com-
system water-o-toluidine-propionic acid at 20C (7) ponents must be chosen so that the three binary
has two isopycnics such that the addition of propionic critical solution temperatures are near together-a rare
acid to the immiscible water-o-toluidinc system causes combination. The system ethylene glycol-nitro-
the water-rich and o-toluidine-rich layers to change methane-lanryl alcohol at 29C (10) is representative
places twice before complete homogenization is attained. (see Fig. 10a, to he discussed later).
By analogy with isopycnics there are also iso-optics- When a single two-phase region extends from one
unique tie lines which join phase compositions that have binary system to another, either as a result of the merg-
the same refractive index for a given wave length of ing of two bites or, more commonly, from the enlarge-
light. Such two-phase systems are usually colored. ment of one bite until it reaches the other side of the
There may he a set of such iso-optics adjacent to each triangle, a hand results as in Figure 4 for the system
other, all giving differently colored pairs of layers. furfural-water-ethyl acetate at 25'C (11). This situa-
Figure 2 (8)shows a binodal area in the system benzene- tion is quite common. The short side of the band is
nitromethane-n-heptane at 25C to be covered with often slightly concave. The slope of the tie lines
"colored" tie lines. Thus the complete tie line pattern crossing the band, although usually changing steadily
can he observed colorimetrically. The colors are also as the triangle is crossed, can somewhat rarely reverse
temperature-sensitive. the direction of change, as in the system water-hydrogen
The above description applies, in general, to systems bromide-n-heptane at 25C (If?).
which show two or even three separate binodal areas. There are also "island curves," hinodal areas com-
I n Figure 3 (9) for the system carbon dioxide(1)- pletely surrounded by a one-phase area. These curves
methyl phthalate-n-heptane at 21-26'C under pressure, are smooth in their entirety, although occasionally
which is typical of many systems, the addition of the drawn erroneously with discontinuities in slope. The
third component to the other two exerts an homogeniz- three components, taken in pairs, may or may not he

BENZENE

A
FURFURAL

NITROMETHANE n-HEKANE

Figure 2. The system benzene-nitmmefhone-n-heptane a t 25'C rhowing

rtruclurol o%rr: a, light blue; b, indigo; c, purple; d, lilac; e, magenta; Figure 4. The ryrtem furfurol-voter-ethyl acetate a t 25'C. The dashed
f, brick red; g, amber; h, amber yellow; i, yellow. line is on bopycnic.

8 16 / Journol o f Chemicol Education

 miscible. The island area will have two plait points. The coexistence of three liquid phases is illustrated
The phenomenon is often associated with the reversibIe by Figure 6 for the system carbon dioxide@-water-
formation of a soluble product of chemical reaction phenol a t 25-C (under pressure) (9),simplified for the
between two of the components. I n the system water- present purpose by omitting the equilibria involving
acetone-phenol between 66' and 92'C (IS) there is an solid phenol. (Inclusion of the latter would have
island curve, but complete miscibility in all three required a region for liquid saturated with solid phenol
binaries. The same is true for propionic acid-hydrogen which would have interrupted, and reduced the size of,
bromide-n-heptane a t 0C (14). Here the island is the miscibility gap based on the carbon dioxide-phenol
almost triangular and nearly fills the entire diagram. side of the triangle.) Similar three-liquid regions are
I n the system hydrogen chloride-water-dioxane at 20C evident in Figures l o b and l l b described below.
under pressure (14) there is an island near the dioxane The manner in which the borders of two areas, each
corner of the diagram and a small bite on the opposite denoting two-phase equilibria, make contact with a
side near the hydrogen chloride corner as in Figure 6. three-phase area is governed by the Schreinemakers
The tie lines shown in t,his figure, and those in T'g
4 1 ures rule (16) according to which the tangents of ac and be
8, 9, 10, and 11 are speculative, but have been included s t c in Figure 6, for example, must both lie within or
for emphasis. I t seems improbable that more than one both lie without the three-phase regions. The same must
island curve can exist in a genuinely ternary system: he true at the other corners of the internal triangle.
although two islands have been reported in the system This rule is valid regardless of the state of aggregation
aniline acetic acid-isooctane at 51C (15) it would ap- of the various phases. (Thus it applies to the well
pear that the formation of aniline acetate is not rapid or known isothermal solubility curves in ternary systems
reversible enough to maintain the true ternary quality of two salts with a commou ion and water at the point
of the system. representing simultaneous saturation of liquid with two
solids.) A proof of the rule is given by Schreinemakers
Three Coexisting Phases
(16) and by Williamson and Morey (17). Figure 7
illustrates an erroneous disposition of the isothermal
At constant temperature and pressure three coexisting solubility curvecfor two salts (B and C) with a common
phases (three liquids, two liquids and one solid, one ion and water (A). The reader may wish also to exam-
liquid and two solids, etc.) are represented by the ine Figures 8, lob, and l l b for conformity with the
corners of a scalene "internal triangle." Only the Schreinemakers rule.
first two possibilities are pertinent to this discussion. Examples in which the three coexistiug phases are

Figure 5. The ryrtem hydrogen chloride.woter-dioxane a t 20'C. Figure 7. System of two ralh with o common ion and wafer showing
ermneour dirporition of isothermal solubility curves.

POTASSIUM CARBONATE

Figure 6. The system carbon dioxide-water-phenol a t 25'C (under prel- Figure 8. The ryrtem potosium carbonate-water-methml at 25'C. H
sure). ?ha equilibria inrdving d i d phenol ore omiwed. represents the hydrate 2KzCOs .3Hz0.

Volume 46, Number 12, December 1969 / 817

two liquids and one solid are common, and arise, for tinguished: (1) external contact of two binodal
example, when the components are two miscible or curves rut a "col," (2) external contact of two binodal
partially miscible liquids, and a solid which is soluble in curves a t a "subcol," and (3) eruption of one two-
both of them as in the system aniline-isooctane-naph- phase area from within another.
thalene at 20C (18). Systems in these categories also The first of these modes arises when the two binodal
arise in connection with the process of salting-out, as areas first make contact at their plait points. This is
with potassium carbonate-water-methanol a t 25%, illustrated in Figure 9a,b,c representing schematically
shown schematically in Figure 8 (19). the relations of the system nitrobenzene-methanol-
The manner in which a change in temperature can isooctane at 15.0, 14.1 and 14.0C (to). Points PI
cause two-phase regions to interact with each other has and P, are the plait points. The name col or saddle
been a matter of speculation for some time. It is only point, found at 14.1C, derives from the appearance of
recently that sufficient experimental data have been the solid model obtained when a temperature axis is
available to provide examples in support of the specula- erected on the composition triangle. Careful experi-
tion. Three such types of interaction may now be dis- mental study has shown that a t the col temperature the
two curves which have just made contact, Figure 9b,

A
NlTR BENZENE do not have a common tangent as sometimes postulated,
but appear as two nearly straight lines intersecting a t a
finite angle. Thereafter, the borders of the resulting
band are highly concave but have no cusps, Figure
9c.
The second mode of contact arises when two binodal
areas make contact involving only one of the two plait
points. Figures 10a and lob show schematically the
sequence of events in the system nitromethane-eth-
ylene glycol-lauryl alcohol at temperatures just above
and just below the subcol temperature, 28.5"C, respec-
tively (10). The subcol tie line ab, Figure 10a, splits
to form the internal triangle a'af'b of Figure lob. It is
to be noted that one of the contacting curves-the one
the plait point of which is not involved in the coutact-

Figure 10. a, b. The system nitmmethme-ethylene glycol-lauryl alcohol

Figure 9. o, b, r The system nitrobenzene-methonoI.i~oocttne a t 15.0.' l u a above and /"st below the subcol temperoture, 28.5'C, respestiveiy.
'
14.1 and 1 4.0C, respectively. The subcol tie line is ab.

818 I Journal of Chemicol Education

 A
NlTR ETHANE and water are partially miscible and that the addition
of sufficient acid produces homogeneity, just as the
addition of A in Figure 1 makes the partially miscible
system B-C homogeneous. When the water is replaced
by salt solution the triangular diagram is still adequate
for expressing all compositions if the salt solution,
alcohol, and acid are mixed in proportions such as to
give a single liquid phase. When, however, the pro-
portions are such as to give more than one phase (the
only situation of interest in heterogeneous equilibrium)
it is not, in general, possible t,o describe all the phase
compositions in terms only of the three variables salt
solution, alcohol, and acid, and therefore not possible to
represent them by a point within the triangle--unless
the salt/water ratio is the same in every phase as it is in
the original solution represented by the corner of the

Figure 1 1 . a, b. T h e system nitroethane-ethylene glycol-lauryl alcohol Figwe 12. The 3ystem toluene-97% acetic acid-n-heptone ot 2SPC
lust above a n d lust below 16..SC. The equilibria involving d i d loury1 ghoxing phore boundory cunrer.
olcohol ore omitted.

must be concave at the point where the merger occurs, triangle. The latter event is unlikely since the salt
in order not to contravene the Schreinemakers rule would tend to enter the water-rich layer to a greater
given above. extent than the alcohol-rich layer.
The t,hird
~-~ kind of behavior is shown in F i ~ u r e sl l a
~~
In spite of the inability to represent even two-phase
and l l b which illustrate schematically the system equilibria, one can still plot "phase boundary curves"
nitroethane-ethylene glycol-lauryl alcohol (10) a t tem- on triangular diagrams in such cases. These are
peratures just above and just below the temperature at curves resembling XPY of Figure 1. Total composi-
which the new binodal area erupts from within the old, tions lying outside of the "bite" area give a single phase
also a subcol temperature, 16.5"C. (The phase re- of the same composition; total compositions lying within
lationships are actually slightly more complex than the area give more than one phase, but the compositions
shown, because of the presence of solid lauryl alcohol, of these phases cannot be accurately represented since
m.p. 22.7'C. The equilibria involving this solid have such phases are not ternary. As they cannot be
been omit,ted from the diagram for simplicity, but the plotted they do not necessarily lie on the phase bound-
omission does not affect the liquid-liquid equilibria ary curve and, strictly, tie lines cannot be drawn across
features under consideration.) the area. The curve is not, therefore, a binodal curve,
and the comments made earlier concerning the shape of
Presence of a Fourth Substance binodal curves are not applicable to it. Nevertheless,
The presence of small amounts of a fourth substance it is possible to plot a plait point under these circum-
can exert a profound influence on the phase behavior of stances, since it, too, lies on the edge of an area of
the other t,hree. The location of plait points, for homogeneity.
example, is very sensitive to impurities. The fourt,h Phase boundary curves frequently consist of reverse
substance is sometimes deliberately introduced in curves with concavities, as shown by Figure 12 for the
appreciable quant,it,iesby, for example, replacing one of system toluene-aqueous acetic acid-n-heptane at 25'C
the component,^ of a ternary system by a solution of the (81). When anhydrous acetic acid is used, the three
fourth substance in that component. The system is components, acetic acid, toluene, and n-heptane, are
now quaternary (21), but certain features of ternary miscible in all proportions, so the phase diagrams con-
systems may be retained under these circumstances. sist of an empty triangle. When 98% acetic acid
Consider, for example, the use of an aqueous salt (in water) is used, however, partial miscibility develops
solution in place of pure water in the ternary system between the aqueous acid and the heptane. When
wat,er-alcohol-acid. Let us suppose that the alcohol 97% acetic acid is used partial miscibility also develops
Volume 46, Number 12, December 1969 / 819
between the aqueous acid and the toluene, a seen in (11) TRIMBLF. F.. A N D DUNLOP. A. P.. Ind. EW. chsm.. ~ n a l ~. d . 12,
. 721
(1940).
Figure 12. By regarding water as an impurity in this ( 1 2 ) F m m r a . A. w.. A N D KING.
W. H., "chemistry of P ~ nydro- ~ ~
svstem one can readily
" auureciate the drastic influence
.A

on liquid-liquid equilibria of the presence of soluble

.,..,-,
.a=.
".
- "A*(Editor: Rnooxs. B. T.. etol.) ~ e i n h d dN, ~ ~Wo r k vol.
oarbone."
r.",..
( 1 3 ) S o n n e m ~ u ~ x e aF.s . A. H.. Z.Phyaik. Chem.. 33, 79 (1900).
, I,

(14) F n ~ ~ c lA. s ,W.. J . Phya. Cham.. 6 2 , 579 (1958).

impurities. (15) R e f . ( 4 ) p. 88. 9. Z~unAvbev.E. F.. A N D V o ~ n o v .A. A,. Imesl.
Vysshikh Uchob. Zovdenii Khim. i Khim. Tekhnol 3.427 (1960).
(16) S c ~ = m ~ n r ~ F. m ~A.s .H., "Die Heterogsnen Gleiohgewiohte Vom
Standpunkte Der Phssenlehre," (Editor: B ~ a m o sRoozsaoow.
Literature Cited H . W.) Braunschweig, Vol. 111, Part 1. 1913, pp. 71-74, 260-270.
(17) W r ~ ~ ~ ~ r sEo. rD.. i , h m Monzr, G. W.. J . Am. Chcm. Soc.. 40, 49
( 1 ) O T R ~ RD. . F.. WBITE. R. E., A N D T R U ~ ~E.. ~ R , Enp. Chem..
Ind. ,.-.",.
,<",a,
33, 1241 (1941). E... A N D ZINC*, 8.. Bull. Slcl. Sci. Acod. Roumoinc. 24,
(18) A x o e ~ ~ s c u
( 2 ) Trrrr, A,. Bull. Soc. C h m . Fmnce, 13,583 (1946). 7-" \."-",.
**a ,>o*.,,
( 3 ) LEIKO~A E.,, Suomen. Kem., 13B,13 (1940). See ~ 1 8 0Ref. (22). p. 845. (19) FRANKFOATER, G . B., ANDFRART, F. C., J.Phya. Chem., 17,402 (1913).
( 4 ) F n ~ ~ o xA.s , W., "Liquid-Liquid Equilibriums." Intemoiencs (division (201 FRANOIS. A. W.. J . Am. Chcm. Sor.. 7 6 , 393 (1954).
of John Wiiey &Sons, Ine.). New York. 1963, P. 36. (21) For detailed studies of quaternary liquid systems as such, see, for
( 5 ) S M I T ~J., C., STIBOLT, V. C.. A N D D A Y . R. W.. Ind. Ens. Cham., 43, example. Bnmonm, A. V., H U N T ~ RT,. G., A N D NASH.A. W.. J .
.n,, ,.r".,.
,.,,K,,
Phys. Chem.. 44, 683 (1940) and P n o m o ~C. , F., W*Lsn, T. J., A N D
(6) BIANCANI. M.. A N D DEFILIPPO, D.. G ~ u .Chim. I t d . . 88, 1202 (1958). ~ , M., Ind. Eno. Chsm., 42, 1210 (1950).
D E S A A.
(7) F n * ~ c ~ A.
s , W.. Ind. Eno. Cham.. 45, 2789 (1953). (22) FRANCIS. A. W.."Tern&w Systems Separating into T w o Liquid Layers,"
(8) F n ~ ~ mA. s , W.. J . Phys. Chcm.. 56, 510 (1952). Solubilities of Inorganic and Organio Compounda. Supplement to
(9) F R A N CA. ~ .W.. J . Phya. Cham.. 58, 1099 (1954). 3rd ed.. (Editor*: SELDELL,A , . A N D LINKE,W. P.) Vsn Noatr*.~.d.
(10) FRANCIS, A. W., J . Phya. Chem., 60, 20 (1956). N e w York. 1952, 8. 1077.

820 1 lournal of Chemical Education