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1969 - Ternary Liquid Systems
1969 - Ternary Liquid Systems
1969 - Ternary Liquid Systems
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Figure 1.
23-24'C.
81 5
own hinodal curve. This correspondence of components (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., waterpropionic 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 composition coordinates not only changes the slopes of the
tie lines but may even change their sign.)
I n many two-phase areas there is, at a given temperature, one tie line connecting phases of equal density
(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
avoided in extraction processes, since settling of the
layers is prevented. (An interesting lecture demonstration can he arranged by adding traces of colored
substances to an isopycnic system in order to make
the two phases readily distinguishable (7).) The
system water-o-toluidine-propionic acid at 20C (7)
has two isopycnics such that the addition of propionic
acid to the immiscible water-o-toluidinc system causes
the water-rich and o-toluidine-rich layers to change
places twice before complete homogenization is attained.
By analogy with isopycnics there are also iso-opticsunique tie lines which join phase compositions that have
the same refractive index for a given wave length of
light. Such two-phase systems are usually colored.
There may he a set of such iso-optics adjacent to each
other, all giving differently colored pairs of layers.
Figure 2 (8)shows a binodal area in the system benzenenitromethane-n-heptane at 25C to be covered with
"colored" tie lines. Thus the complete tie line pattern
can he observed colorimetrically. The colors are also
temperature-sensitive.
The above description applies, in general, to systems
which show two or even three separate binodal areas.
I n Figure 3 (9) for the system carbon dioxide(1)methyl phthalate-n-heptane at 21-26'C under pressure,
which is typical of many systems, the addition of the
third component to the other two exerts an homogeniz-
!BON DIOXIDE
METHYL PHTHALATE
wHEPTANE
BENZENE
FURFURAL
h
NITROMETHANE
n-HEKANE
8 16
The dashed
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?ha equilibria inrdving d i d phenol ore omiwed.
sure).
817
two liquids and one solid are common, and arise, for
example, when the components are two miscible or
partially miscible liquids, and a solid which is soluble in
both of them as in the system aniline-isooctane-naphthalene at 20C (18). Systems in these categories also
arise in connection with the process of salting-out, as
with potassium carbonate-water-methanol a t 25%,
shown schematically in Figure 8 (19).
The manner in which a change in temperature can
cause two-phase regions to interact with each other has
been a matter of speculation for some time. It is only
recently that sufficient experimental data have been
available to provide examples in support of the speculation. Three such types of interaction may now be dis-
NlTR BENZENE
'
818
NlTR ETHANE
~~
819
Literature Cited
( 1 ) O T R ~ RD.
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~ R
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( 3 ) LEIKO~A
( 4 ) F n ~ ~ o xA.
s , W., "Liquid-Liquid Equilibriums." Intemoiencs (division
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V. C.. A N D D A Y . R. W.. Ind. Ens. Cham., 43,
.n,,
(6)
(7)
(8)
(9)
(10)
,.r".,.
,.,,K,,
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820
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~ nydro- ~
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.a=.
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,
I,
.,..,-,
".
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r.",..
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Vysshikh Uchob. Zovdenii Khim. i Khim. Tekhnol 3.427 (1960).
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(17) W r ~ ~ ~ ~ r sEo. rD..
i , h m Monzr, G. W.. J . Am. Chcm. Soc.. 40, 49
,.-.",.
,<",a,
(18) A x o e ~ ~ s c u
E... A N D ZINC*, 8.. Bull. Slcl. Sci. Acod. Roumoinc. 24,
\."-",.
**a ,>o*.,,
7-"
(19) FRANKFOATER,
G . B., ANDFRART,
F. C., J.Phya. Chem., 17,402 (1913).
(201 FRANOIS.
A. W.. J . Am. Chcm. Sor.. 7 6 , 393 (1954).
(21) For detailed studies of quaternary liquid systems as such, see, for
example. Bnmonm, A. V., H U N T ~ RT,. G., A N D NASH.A. W.. J .
, F., W*Lsn, T. J., A N D
Phys. Chem.. 44, 683 (1940) and P n o m o ~C.
D E S A A.
~ , M., Ind. Eno. Chsm., 42, 1210 (1950).
(22) FRANCIS.
A. W.."Tern&w Systems Separating into T w o Liquid Layers,"
Solubilities of Inorganic and Organio Compounda. Supplement to
3rd ed.. (Editor*: SELDELL,A , . A N D LINKE,W. P.) Vsn Noatr*.~.d.
N e w York. 1952, 8. 1077.