PHASE DIAGRAM OF

THREE-COMPONENT
LIQUID SYSYTEM

ABSTRACT:

I. INTRODUCTION

A phase diagram shows the phases

existing in equilibrium at any given
condition. According to the Phase Rule, a
maximum of four intensive variables
(intensive properties) must be specified to
completely define the state of a three-
component system. In this system, there are
Figure 1: Triangular diagram of a
3 components but only 1 phase exists. Thus, three component system
by using the phase rule, we can find out that In the diagram shown above, every corner of
the degree of freedom is 4 which are the triangle represents a pure component,
temperature, pressure, and concentrations of which are 100% A, 100% B and 100% C.
the two of the three components. The Each side represents one binary mixture and
composition of a ternary system can be area in this triangular diagram represents
presented in the form of triangular ternary components. Rules Relating to
coordinates at constant temperature and Triangular Diagrams are as below:
pressure.
1. Each of three corners or apexes of the
triangle represent 100% by weight of one
component (A, B, or C). As a result, that
same apex will represent 0% of the other
two components.
2. The three lines joining the corner points
represent two-component mixtures of the
three possible combinations of A, B and C.
Thus the lines AB, BC and CA are used for
two-component mixtures of A and B, B and
C, and C and A, respectively
3. The area within the triangle represents
all the possible combinations of A, B, and C
to give three-component systems
4. If a line is drawn through any apex to a
point on the opposite side (e.g. line DC in
Diagram 1) then all systems represented by
points on such a line have a constant ratio of
two components, in this case A and B
5. Any line drawn parallel to one side of
the triangle, for example, line HI , represents
ternary systems in which the proportion (or
percent by weight) of one component is
constant. In this instance, all systems
prepared along HI will contain 20% of C
and varying concentrations of A and B
Addition of the third component
into one pair of miscible liquids can change
their solubility. If this third component is
more soluble in either one from the two
components, the solubility of both
components will reduce. But if the third
component is soluble in both components at
the same time, the solubility increases. Thus,
when ethanol is added into a mixture of
benzene and water, the solubility of these
two components will increase until a point is
reached, where the mixture become
homogenous. This study can be applied in
the case of preparing pharmaceutical
formulation as it often involve the mixing of
more than one components while the
resulting formulation need to be in
homogeneous form. By knowing the exact
ratio of each component needed to be mixed
and take into consideration the temperature
and pressure of the surrounding then this
requirements can be made possible.
In this experiment to be conducted,
Acetic acid, Chloroform and Water are the
three components that will be involved. At
equilibrium, a homogenous solution can be
formed in mixture of acetic acid and water
with chloroform in suitable proportion.
Behind these phenomena, the solutions are
said to be homogeneous considering that
throughout the solution the ratio of solute to
solvent remains the same regardless of its
homogenization with multiple sources.
Moreover, solubility since the solute will not
settle out after any period of time, and it
cannot be removed by a filter or centrifuge.
Thus, one phase exists in three components.
This study was aimed to:
a.) determine the phase diagram for three-
component liquid system consisting
of Acetic acid, Chloroform and Water.
MATERIALS AND METHODS
A. Solubility curve
A mixture of H2O and CHCl3 was prepared
containing the following percentages: 10%,
20%, 30%, 40%, 50%, 60%, 70%, 80%, and
90%. 20mL of mixtures was prepared by
filling a certain volumes using buret. Each
mixture was titrated with acetic acid until
the solution no longer turns cloudy, due to
the existence of the second phase. Then,
record the volume of each liquid, calculate
the weight and % weight of each liquid.
Then, plot the composition of the mixture on
a Stokes and Rozeboom diagram.
If no layers formed, increased the amount of
water until a second layer can be observed.
Then transfer each mixture into a separatory
funnel, shake well for 2 minutes allow the
layers to separate. And pipet 5mL of each
aqueous layer, then weight the Erlenmeyer
flasks, and weight again. And add 50mL of
distilled water and titrate to the
phenolphthalein endpoint with 0.5M NaOH.
And then, pipet 5mL of each CHCl3 layer
and weight the Erlenmeyer flasks and weigh
again. Add 50mL water and titrate to the
phenolphthalein endpoint with 0.25MNaOH.
And calculate the % by weight acetic acid
in each layer, then locate the points on the
solubility curve and construct the tie lines by
connecting compositions. And lastly,
determine the plait point of the system.
Table 1. Volume liquid of water, chloroform, and
acetic acid in each One-phase mixture

B. Connection of the tie lines Volume of

liquid
A 20mL mixture was prepared with Mixture
the following composition (% by volume). no. H2O CHCl3 HOAc
1 9mL 1mL 3mL
2 8mL 2mL 9.2mL
Mixture 1-15% HOAC,25%CHCl3,60%H20
3 7mL 3mL 9.3mL
4 6mL 4mL 10mL
Mixture2-30%HOAC,25%CHCl3, 45%H20 5 5mL 5mL 10.7mL
6 4mL 6mL 9.6mL
Mixture3-45%HOAC, 25%CHCl3,30%H2O 7 3mL 7mL 9mL
8 2mL 8mL 7.7mL
Mixture 4-60%HOAC, 25%CHCl3,15%H2O 9 1mL 9mL 5.5mL
 Table 2. Weights of water, chloroform, and
Table 4. Composition of aqueous and
acetic acid in each One-phase mixture
chloroform layers in each Two-phase
mixture
Weight of liquid Mixture
(g) no 1 2 3 4
H2O HOAc CHCl3
1.00 8.34 13.3 Weight(g) 5 5 5 5
1.99 9.59 11.83 Aqueous V of
layer NaOH(mL) 50.2 60.8 138 52.5
2.99 9.69 12.35
3.99 10.42 8.87 %HOAc
4.99 11.39 7.39
5.98 12.01 5.92 weight
V of
6.98 13.27 4.44
CHCl3 NaOH(mL) 53 117.8 93.5 115
7.98 10.45 2.96
8.97 7.42 1.48 %HOAc
Thus, regarding to this issue, phase rule is
Table 4. Percent Weight of water, chloroform, formulated by J. Willard Gibbs. Phase rule
and acetic acid in each One-phase mixture
is used to relate the effect of the minimal
%Weight number of independent variables upon the
H20 CHCl3 HOAc various phases that can exist in an
4.42 58.76 36.82
equilibrium system that containing a given
8.50 50.53 40.97
11.95 49.34 38.71 number of components. The phase rule is
17.14 38.10 44.76 expressed as follows:
20.99 31.09 47.92
25.01 24.76 50.23 F=C–P+2
28.33 18.02 53.86
37.78 14.02 49.48 where,
50.20 8.28 41.52 F = Number of degree of freedom
Phase diagram is a diagram representing the P = Number of phases
limits of stability of the various phases in a C= Number of components
chemical system at equilibrium, with respect By using phase rule equation in this
to variables of parameters such as experiment, the number of degree of
concentration and temperature. Therefore, to freedom, F can be determined. In this
define the state of each phase, knowledge of experiment, we use three components as
several variables is needed and essential each components are composed of different
elements. At the beginning of the
experiment, we mixed toluene and ethanol
which eventually resulting only one liquid
phase (homogenous solution). Thus the F
obtain in this experiment is 4 (as F = 3-1+2)
for a non-condensed system. The degree of
freedom at the beginning of the experiment
is comprised of temperature, pressure and
the each of the concentration of the
components. As water is added to the
system, F will be reduced to 2 (as F= 3-3+2)
for a condensed system as the number of
phases are increased from one liquid phase
to two liquid phase and addition of one
vapour phase. As the number of components
increase, the number of degree of freedom
also will be increased. However, as F is
increased, the system will become more
complex, it becomes necessary to fix more
variable to define the system. Thus, the
greater the number of phases in equilibrium,
the fewer the degrees of freedom.
In this experiment, we are using three
different components, which are acetic acid,
water, and chloroform. It is important to
know the properties of water and chloroform
solubility in water. Both water and
chloroform have different properties in
water. Chloroform is soluble in water and
acetic acid is extremely soluble in water. At
the beginning of the experiment, we mixed
an amount of water and Chloroform
together. Both are forming a clear mutual
miscible solution and forming homogenous
solution (one liquid phase). But after adding
an amount of acetic acid, the solubility of
the will be no longer cloudy. The cloudy
solution turns clear which indicates the
solution miscible to each other and starts to
form two layer (two liquid phase) as
resulting from the different degrees of
solubility of water and chloroform in acetic
acid.
The addition of acetic acid (third
component) to miscible liquids, which is
water and chloroform can change their
mutual solubility. Acetic acid is more
soluble in water compared to chloroform,
the mutual solubility of chloroform and
water is decreased. However, if acetic acid
is soluble in both of the liquids, the mutual
solubility will be increased. Thus, when
acetic acid is added to the mixture of water
and chloroform, the mutual solubility
increased until it reached a point where the
mixture becomes homogenous solution. This
is proved in the experiment, as more amount
of acetic acid is needed to turn the cloudy
miscible solution into clear solution. In
addition, all of the component in this
experiment can be a miscible solution when
they are mixed together if and only if correct
proportions of each component are
determined.
Based on this experiment, we are
discussing about the phase diagram for
ternary systems as we are dealing with three
component systems. Thus, it is more
convenient for us to use triangular
coordinate graph paper. In this ternary
system, only liquid phases are involved
either it will form one phase or two phase.
By using a triangular coordinate graph
paper, there are certain rules that relate to
the use if triangular coordinates. The
concentrations of the two component used in
this experiment must be expressed on
weight-weight basis. This is because in
pharmaceutical interest, it will be an
efficient method of preparing dispersions
and allows the concentration to be expressed
as mole fraction or molality. Based on the
Figure 3.1, each of three corners or apexes
of the triangle represent 100% by weight (in
this experiment we use volume of the
component) of one component (A: water, B:
chloroform or C: acetic acid). As a result,
the same apex will represent 0 % of the
other two components. For instance, the top
corner point in Figure 3.1 represents 100%
A. The three lines joining of the corner
points (referred to point AB, BC and CA)
represent two-component mixtures of three
possible combinations of A, B and C. Thus,
lines AB, BC and CA are used for two-
component mixtures of A and B, B and C
and C and A, respectively.
By dividing each line into 100 equal
units, location of point along the line
(referred to line AB, BC and CA) can
directly related to the percentage
concentration of one component in two-
component system as the third component of
the system is equal to 0. On the hand, the
area within the triangle represents all the
possible combinations of A, B and C to give
three-component systems. For example,
based on Figure 3.1, the line parallel to CB
that cuts point D is equivalent to 85.31% A ,
resulting the system to contains 85.31% of A
and 14.69% of B and C together. Applying
similar arguments to the other two
components in the system, we can say that
along the line AB, C= 0. As we proceed
from line AC towards B, the concentration
of B is elevated until the apex, B=100%.
The point D lies on the line parallel to line
AC is equivalent to 5.21% of B. Thus, to
find the concentration of C, we use 100% -
(A+B) % = 100% - 90.25% = 9.48%. This is
confirmed in the Figure 3.1 as the line AB
towards apex C, the point D lies on the line
is equivalent to 9.48% of C. This is applied
to all points that lies within the line in the 2. http://chemed.chem.purdue.edu/genchem/
triangle. topicreview/bp/ch14/phase.php
3. https://www.csun.edu/~jeloranta/CHEM3
CONCLUSION 55L/experiment5.pdf

In conducting the experiment of phase

equilibrium in three-component systems, it
is important to define the number of degree
of freedom to find out the least number of
variables that needs to be fixed in order to
describe the system completely. This is
important as it will affect the data obtained
to plot the complete binomial curve.
Besides, in this experiment also, all the three
component can achieve a homogenous
solution (one liquid phase) if the correct
proportions of each component is mixed
together. The mixture of water, chloroform
and acetic acid become more homogenous
when decreasing amount of chloroform and
increasing amount of water is used in the
system. If the proportion of the three
components is not correct in order to
achieve a clear miscible solution, two liquid
phases will be form which is indicates by the
appearing of the cloudiness of the mixed
solution.

REFERENCES

1.http://chemhail.wordpress.com/2009/07/05
/application-of-phase-rule-to-three-
component-systems/