1

Determination of Liquid-Liquid Equilibria in Ternary Systems

Ternary diagrams
You will use triangular diagrams to depict your results. Only composition will be
changed, as you will work at constant pressure and temperature (25
o
C). The vertices denote
pure A, B and C liquids. All binary compositions are at AB, BC and AC sides.



E. g. in our figure the numbers are mole or weight (our case) or volume fractions of one
component. Point at BC side denoted 0.25 means a binary mixture of 25% B and 75% C,
point at AB side denoted 0.75 means a binary mixture of 25% B and 75% A. Mention that all
25% B mixtures lie on the connecting line of both points. Therefore, the point inside the
triangle lying on the connecting line represents a mixture of 25% B, 25% C and 50% A.
Determine composition at point M and put it down!



Determination of binodal curve by titration method
Binodal curve is the equilibrium curve separating the two-phase region from the
homogeneous region. About 75% of the measured ternary systems have only one
heterogeneous binary system; this is also our case. If A stands for water, B and C following
the number of your table are unknown liquids, then A and C is the heterogeneous binary
system. There are two binodal curves in the following figure. Curve I is very high and close to
the A, C vertices and may be very close to one side, too. The second one is rather flat and the
immiscibility region of AC binary is narrower. Above the binodal curve is a homogeneous
region, under it a heterogeneous one. Let us imagine that we prepared (by weighing) sample
BC given by point N. Adding water to the sample we shall move along a straight line
connecting N and A. Touching binodal curve the heterogeneous mixture springs up. Knowing
the B and C weights and amount of water added (1 ml = 1 g as density of water is 1 g/cm
3
,
0.25 0.50 0.75
0.25
0.50
0.75 0.25
0.50
0.75
M



C A
B
2


approximately), you will thus obtain an experimental point (R). It can happen for the flatter
binodal curve that we will not touch it. Starting from mixtures rich in C and having the higher
curve several not very interesting experimental points practically lying on CB side could be
obtained.
Recommendation: start with pure C.
If C is practically immiscible in A the second point could be about 1:1 B and C. The result
will tell you where to design next mixture. What must be the initial composition of BC
mixture to get point O?

If A and C are partly miscible you will obtain point P. The second point ought to be rich
in C to be sure to get to heterogeneous region.



PROCEDURE
Weight about 25 g of C (first point) or mixture of B and C to a dry Erlenmayer flask.
Put it into a thermostat for about 10-min. Flask with distilled water will be also thermostated.
After 10 min. fill your burette with the water and start to titrate mixture in the second flask.
Mix the content after every drop of water. You are in a homogeneous region till the mixture
wets uniformly walls of the flask. First droplets of the second liquid phase still visible after
same more mixing indicate the end of titration. You read the water consumption and plot it
into a diagram.
In some cases (e.g. to get to S point) it is better to weight B add A (water) from burette
and than add C drop by drop from a pipette. Weight the flask after titration is over. There is
now sense to use burette for density of C is unknown. You are ready when you are able to
draw the whole heterogeneous region.
0.2 0.4 0.6 0.8
0.2
0.4
0.6
0.8 0.2
0.4
0.6
0.8
S
R
N
O
P
II
I
B
C A