Ternary Phase Diagram

Objectives:
(1) To construct the ternary phase diagram for the Acetic acid- Chloroform- Water
system at 25°C and barometric pressure.
(2) To determine the bimodal curve and the tie line.

Theory:
In this experiment, we are going to study a ternary system containing two partially miscible
liquids (water and chloroform) in addition to a third liquid (acetic acid) which is completely
miscible with the other two liquids. The later (acetic acid) is called co-solvent, where its
addition will increase the miscibility of the other two components.

The Phase Rule:

The number of independent variables (degrees of freedom) required to completely describe
the state of system at equilibrium is given by a simple rule (“Gibb’s phase rule”)

F=C–P+2 (1)
F= number of independent variables called degrees of freedom.

C= number of components.

P= number of phases present in the system.

*Degrees of freedom: the number of intensive variables such as temperature, pressure and
composition, etc.

Example: For pure gas (e.g. one component system) c = 1 (pure gas; only one component) and
p = 1 (only one phase; the gas phase) and by Eq. (1) we have f = 2. This means that two
variables are required for complete description of pure gas (i.e., any two of the three variables
P, V or T).
Example: Consider water with the phase diagram shown in Fig. 1

Figure 1: A schematic drawing of the phase diagram for water.

For pure phases (solid, liquid or vapor) f = 2. When two phases are present simultaneously
(e.g. the point resides on the lines separating the phases in Fig. 1), only P or T can be varied
independently and the phase rule gives f = 1. When all three phases are present (H2O (gas),
H2O (liquid), and H2O (solid, ice)) (triple point), all variables must be fixed and the phase rule
says that f = 0. So we are not talking about the chemical state of the system but rather it
physical state. This version of the Gibbs phase rule is only valid for non-reacting systems.
For the system of interest in this experiment (Acetic acid- Chloroform- Water system), the
three components will form regions, in terms of mutual solubility, on their phase diagram
depending of course on the relative amount of each component. One region is called the one
phase region where the three components are completely miscible in each other and in this
case the Gibb’s phase rule becomes:

F=3-1+2=4
Thus, for the system of three components, four variables would have to be plotted against
each other to fully describe the physical state of the system such are: two for describing the
relative composition (mole fractions) and one of the pairs (P, V ), (P, T), or (T, V ). Note that if
only two mole fractions x1 and x2, are given, the third can be obtained by x3 = 1 − x2 − x1.
Since plots of four variables are difficult to construct and visualize, the usual procedure is to
hold one or more of these variables constant and plot the remaining variable against each
other. For a ternary system the temperature and pressure are commonly held constant and
the composition variables are plotted against each other.
The other region is called the two phase region, where the amounts of acetic acid added is
not enough to cause completely miscibility of water and chloroform. In this case the Gibb’s
phase rule is:

F=3-2+2=3
The two regions are shown in fig 2 below:

Point at which the Bimodal Curve

solution will begin
to appear turbid as
the two phase
region begins

Figure 2: A ternary phase diagram of Acetic acid- Chloroform- water system showing the two region
mentioned in the text above. Also shown the bimodal curve rounding the miscibility gab of water and
chloroform systems. The point marked in the diagram (•) represents 30% water, 10% chloroform and
60% acetic acid. The point marked ( ) represent a point where the two phase region is crossed upon
adding water to an acetic acid-chloroform system.

The pure components are located at the corners of the triangle as shown in fig 2. The set of
lines parallel to a triangle edge opposite one of the corners, give the total percentages in the
system of the component located at that corner. When a pure component is added to the
system, say e.g. water, the overall composition of the system moves along the line connecting
the original system composition and the corner of the triangle where the pure component is
located.

In the case where the three pure components are liquids, as is the case in our experiment, at
the temperature and pressure at which the diagram is constructed, there may be system
compositions where two immiscible liquid phase form. The two phases will be acetic
acid/water phase and acetic acid/chloroform phase. If we start with a system where only one
phase is present and add a component that will move the overall system composition into
region where two phases are stable, the point at which the phase boundary is crossed and a
second phase begins to form can be recognized by a cloudiness or turbid appearance in the
system when it is shaken. This is demonstrated in fig 2 above.
If the three components are mixed to give an overall system composition that falls in the two
phase region, the system will separate into two phases. A phase rich in water and the other
is rich in chloroform. The compositions of the phases that form will be given by the
intersections of a tie line with the phase boundary as shown in fig 3 below. The tie line must
also contain the point describing the overall system. The location of the tie line must be
determined experimentally.

Figure 3: Drawing of a tie line in a triangular phase diagram that gives the composition, A, of a phase
rich in water and the composition of a phase, C, rich in chloroform that form when the overall
composition is a point B.

Procedure, Materials, and Chemicals:

First meeting: Among other materials you need for this experiment such as conical flasks
(Erlenmeyer flasks), beakers.
Two burettes in the fume hood (the fume hood should be switched on) one is filled with acetic
acid and the other is filled with chloroform. Both of these burettes are labelled with the
appropriate name of the materials present. Do not take these burettes out of the fume hood.
A third burette can be put on a stand on the bench in the front of each group and should filled
with distilled water.

Second meeting: Chloroform, Acetic acid, Distilled water, Phenolphthalein indicator, 0.1 M
Sodium hydroxide, Potassium hydrogen phthalate (KHP), Separatory funnel, 200 ml
volumetric flask, Beakers, Burettes.
Experimental Part:
Part one: Construction of the bimodal curve
You will prepare the following solutions of chloroform and acetic acid in cleaned and tried
125 ml conical flasks in order to experimentally determine the necessary points to draw the
bimodal curve:
Table 1:

Chloroform 1 ml 2 ml 3 ml 4 ml 5 ml 6 ml 7 ml 8 ml 9 ml
Acetic acid 9 ml 8 ml 7 ml 6 ml 5 ml 4 ml 3 ml 2 ml 1 ml

You will start with a clear transparent solution with on layer and then add water to the
chloroform-acetic acid solution drop by drop with continuous stirring until the turbidity
appears and remains for at least 2 min. Record the amount of water required.

Results and Calculations:

After obtaining the densities of acetic acid and chloroform you should make calculation of
the mole fraction of the components present as follows:
Table 2:

Chloroform Acetic acid Water

V m n Mole V m n Mole V (ml) m n Mole
(ml) (g) (mol) fraction (ml) (g) (mol) fraction (g) (mol) fraction
(X) (X) (X)
1 9
2 8
3 7
4 6
5 5
6 4
7 3
8 2
9 1

- Density (water) = 1g/ml, Molar mass (water) = 18g/mol, Density (acetic acid) =1.049g/ml,
Molar mass (acetic acid) =60 g/mol, Density (chloroform) = 1.492g/ml, Molar mass
(chloroform) =119.48 g/mol.
- Use the well-known relation density = mass/ volume to get the masses of the components.
- After you determine the mole fraction for each component you should plot these points on
a ternary phase diagram.
- Mole Fraction X ……….XA = nA/ ntotal = moles of solute A/ total moles in solution
And if mixture of multiple components A, B, C,.…
Then…. 1= XA + XB + XC + …

How to plot the mole fractions on the phase diagram?

As an example take the point x acetic acid =0.6, x water=0.2 and x chloroform=0.2.

In order to plot this point, you should go clockwise following the long arrows. Determine the
mole fraction of acetic acid along the right side of the triangle. So 0.6 acetic acid will be at the
solid pentagon shaped point. Then determine the mole fraction of water along the base of
the triangle. The point 0.2 water will be at the solid multisided star and finally the mole
fraction of chloroform along the left side of the triangle and so 0.2 chloroform will at the solid
circle. From the acetic acid point (0.6) draw a line parallel to the base of the triangle, from the
water point a line parallel to the acetic acid-chloroform side and finally from the chloroform
point (0.2) draw a line parallel to the acetic acid-water side as shown in figure 4. The three
lines should meet (intersect) at the solid five star point ( ).

Figure 4: Plotting the point 0.6, 0.2 and 0.2 of the mole fraction of acetic acid, water and chloroform
respectively
Part two: Determination of the tie line
Aim: To find out the amount of each phase in the two phase region.
1. In a clean try separatory funnel take 4 ml acetic acid, 5 ml water and 7 ml chloroform.
Close the funnel tightly and then shake it rigorously for few seconds. Leave it on a
stand to settle down. The solution will separate into two layers. The acetic acid will
partition itself into:
 An organic layer that consists of acetic acid and chloroform (organic layer)
 An aqueous layer that contains water and acetic acid. The organic layer will be
below because of its higher density.
2. Separate the aqueous layer from the organic one by pouring it in clean dry conical
flask.
3. Dilute the aqueous layer by adding water to 200 ml volumetric flask.
4. Take 25 ml of the solution and titrate with standardized (0.1 M) NaOH using two drops
of the indicator phenolphthalein (end points is indicated by the appearance of pink
color)
 Note that the standardization of NaOH must be done during the period of titration
that is done since the NaOH concentration changes rapidly when carbon dioxide is
absorbed from the atmosphere.
 Use potassium hydrogen phthalate (KHP; M.W. 204.23 g mol−1) for
standardization. Use the same indicator for standardization.

Calculation:
From the calculated moles of NaOH, the moles of acetic acid in the aqueous layer will be
determined. (Hint: Don’t forget that the amount of acetic acid is diluted to 200ml). The moles
of acetic acid in the organic layer can be determined by subtracting the determined moles
from the original total amount mixed.
To plot the tie line see figure 5 below: from the moles of acetic acid in the aqueous layer the
mole of fraction of it will be determined and plotted in acetic acid-water side of the phase
diagram. The determined mole fraction of the acetic acid in the organic will be plotted at the
acetic acid-chloroform side of the phase diagram. The extra lines between the open circles in
figure 5 and the bimodal curve should be eliminated and then the tie line will be determined.
Figure 5: Drawing of the tie line across the two phase region