Three Component Systems

The mutual solubility of a pair of partially miscible liquids may be altered by the
addition of a third component.

If the third component is soluble in one only of the two other components, the
mutual solubility of the two liquids decreases.

If the third component dissolved readily in each of the two other components, the
mutual solubility of the latter two components increases until a point is reached at
which the mixture becomes homogeneous.

With a system of three components, four variables are possible; the pressure,
temperature and two concentration terms (the concentration of the third component
will be automatically fixed).
In a system of three components the variance

F=CP+2

F= 3 P+ 2 = 5 - P
So, when they form one phase F = 4 then 4 intensive variables are required to
describe the system. These are temperature, pressure, X1 and X2 where X is the % of
composition of each component.
To simplify the study of the phase properties, the system is treated as a condensed one
at a constant temperature, in which case the pressure and temperature as variables, are
dispensed with. The phase rule expression reduces hence to
F = C P

at constant temperature and pressure

So, when the three components form one phase, F = 2 and when they form 2 phases
F = 1. These variables are composition variables X1, X2 and X3 related by
X1 + X2 + X3 = 100 %
Specifying any two of them fixes the value of the third.
The phase properties are best defined by using the graphical method of Gibbs and
Roozeboom equilateral triangle. Fig. 1 illustrates the principle of the method.
1) The points A, B and C at the apices of the triangle represent 100 % of component
A, 100 % of B and 100 % of C.
2) The lines parallel to AB represent the various percentages of component C.

3) Any point on the line AB represents a system containing 0 % C; any point on xy

represents a system containing 10 % C, etc. Point P represents a system containing
30 % C.
4) The length perpendicular to a given side of the triangle represents the percent of
the component at the vertex opposite to that side. Thus the length PM represents the
percent of C, the length PN represents the percent of A, and the length PL represents
the percent of B.
5) The sum of the lengths of these perpendiculars is always equal to the length of the
side of the triangle which is taken as 100 %.
By this method any composition of a three component system can be represented by a
point within the triangle.

Fig. 1 The triangular diagram

If components A, B and C are completely miscible with each other at all proportions,
then any point inside the triangle represents a system of three components and one
phase, therefore F, the number of degrees of freedom, is 2, which means that the
concentrations of any two components can be varied with respect to one another
while that of the third component is maintained constant.

If components B and C form a pair of partially miscible liquids, a mixture of the two
of composition X (Fig. 2) will separate into two layers having the composition
determined by points b and a (compare the phenol-water system). If component A is
gradually added to the above mixture, the composition will vary following points on
the line AX. If A is completely miscible with both B and C, it will distribute itself
between the two layers and eventually a composition corresponding to point M is
reached where complete miscibility is observed.

Fig. 2. A system of three components A, B and C

Similarly, for any other mixture of A and B of composition between a and b, a point is
reached where there is complete miscibility. The line connecting the various points is
the binodal curve b M a. Within this curve (immiscibility region) any point
represents a system with C = 3 and P = 2, therefore F = 1, which means that changing
the concentration of one component, the concentrations of both other components
must change. Outside the curve, is the region of complete miscibility and is treated as
explained before.
Experiment:
Construct the binodal curve for the system Ethyl acetate-Ethanol-Water.
Procedure:
1) Into five clean and dry stopper bottles introduce the following volumes of ethyl
acetate and water. (Using pipette for ethyl acetate and burette for water)

Bottle
1
2
Ethyl acetate, ml
10
8
Water, ml
2
4
The mixtures will appear turbid.

3
6
6

4
4
8

5
2
10

2) Thermostat the bottles at 25C.

3) From a burette, run ethanol drop by drop into each of the bottles in turn. Shake
well after each addition.
4) Continue addition of ethanol till turbidity just disappears on shaking.
5) Record the volume of ethanol used.
Calculations:
1) Calculate the percentage composition by mass of each mixture at the stage when
turbidity just disappears.
Densities at 25C are
Ethyl acetate = 0.902 g/ml
Ethanol

= 0.786 g/ml

Water

= 0.997 g/ml

2) Tabulate your results and plot them on a triangular diagram. Join the points by a
smooth curve to obtain the binodal curve.
Helpful questions for the discussion:
1) What is the effect of the third component on the solubility of a mixture of two
partially miscible liquids? And mention what is happen in your experiment.
2) Explain all the points, lines and areas in the Roozeboom equilateral triangle and
define them by the phase rule (C, P and F).