ADAMSON UNIVERSITY

College of Engineering
Chemical Engineering Department
M a n il a

Experiment no. 5

PHASE DIAGRAM OF A
THREE-COMPONENT LIQUID SYSTEM

Researchers:
Baldovino, Shiela Marie G.
Cabotaje, Amiel Clark G.
Carlos, Fauline Deune G.

Date performed: January 30, 2016

Reporter: Cabotaje, Amiel Clark G.

ABSTRACT:
The phase diagram of a ternary system of water acetic acid chloroform mixture was created. Different
concentrations of water and chloroform were prepared. Each solution was titrated with glacial acetic acid until the solution no
longer turns cloudy when shaken vigorously. The tie lines and the phase diagram were created using the three different mixtures
with different concentrations. The point on the solubility curve was located and the tie lines were constructed by connecting the
compositions of the complimentary layers with straight line. The plaint point of the system was determined. After performing the
experiment, it was found out that as the addition of water as the third component to a pair of miscible liquids of acetic acid and
chloroform can change their mutual solubility. If the third component is more soluble in one of the two different component
mixtures the mutual solubility of the liquid pair is decreased and thus, two phases of liquids will appear. The possible sources of
errors are human errors and systematic errors.

INTRODUCTION:
A ternary system is one with three components.

We can independently vary the

temperature, the pressure, and two independent composition variables for the system as a whole.
A two-dimensional phase diagram for a ternary system is usually drawn for conditions of
constant T and p.

Figure 1: Representing the composition of a ternary system by a point in an equilateral triangle.

Although we could draw a two-dimensional phase diagram with Cartesian coordinates to
express the mole fractions of two of the components, there are advantages in using instead the
triangular coordinates shown in Fig. 1. Each vertex of the equilateral triangle represents one of
the pure components A, B, or C. A point on the side of the triangle opposite a vertex represents a

binary system of the other two components, and a point within the triangle represents a ternary
system with all three components.
To determine the mole fraction Za of component A in the system as a whole represented
by a point within the triangle, we measure the distance to the point from the side of the triangle
that is opposite the vertex for pure A, then express this distance as a fraction of the height of the
triangle. We follow the same procedure to determine Zb and Zc. The concept is shown in Fig.
1(a).
As an aid for the conversion between the position of a point and the overall composition,
we can draw equally-spaced lines within the triangle parallel to the sides as shown in Fig. 1(b).
One of these lines, being at a constant distance from one side of the triangle, represents a
constant mole fraction of one component. In the figure, the lines divide the distance from each
side to the opposite vertex into ten equal parts; thus, adjacent parallel lines represent a difference
of 0.1 in the mole fraction of a component, starting with 0 at the side of the triangle and ending
with 11 at the vertex. Using the lines, we see that the filled circle in the figure represents the
overall composition Za=0.20, Zb=0.30, and Zc=0.50.
The sum of Za, Zb, and Zc must be 1. The method of representing composition with a
point in an equilateral triangle works because the sum of the lines drawn from the point to the
three sides, perpendicular to the sides, equals the height of the triangle.
Two useful properties of this way of representing a ternary composition are as follows:
1. Points on a line parallel to a side of the triangle represent systems in which one of the
mole fractions remains constant.
2. Points on a line passing through a vertex represent systems in which the ratio of two of
the mole fractions remains constant.

REVIEW OF RELATED LITERATURE:

The determination of plait point coordinates from the experimental conjugated

compositions is recognized to be very important from both practical and theoretical sides. In
fact: i) its position on the binodal curve, being correlated to the derivatives of the free energy of
mixing, can provide information about the intermolecular interactions existing among the three
components; ii) its position is fundamental for studying critical dynamics of fluids and
mixtures and ; iii) it can be used to check for the reliability of theoretical expressions used in the
description of multicomponent solutions, such as Wilson, NRTL, and UNIQUAC excess
functions ; iv) it is also useful in evaluating, by using appropriate models, the spinodal curve. At
this aim, very recently some of us have proposed, by using the Wheeler-Widom model, a
calculation procedure using the plait point position for obtaining the spinodal curve from the
knowledge of the binodal one.
Whereas a direct experimental determination of the plait point is only rarely performed,
the most used procedures involve tie line correlations and/or graphical plots with subsequent
extrapolation that can be performed with a much better accuracy. At this aim, different
approaches have been proposed in the literature. Coolidge has suggested a graphical method
consisting in building up, on each experimental tie line, a virtual triangle with the other two sides
parallel to those oblique of the Roozeboom triangle: a smooth curve joining the apices of all the
virtual triangles drawn crosses the binodal curve at the plait point. This method makes use of
points some of which are external to the triangle delimiting the region of physical compositions
0 xi 1. A modification of the Coolidge procedure, adopted by Sherwood, uses virtual triangles
with at least one horizontal side.
Brancker has proposed a different graphic method to evaluate the plait point, whose
position is subsequently used to correlate and interpolate tie lines: the proposed procedure is
based on variably dimensioned concentration scale, such to make linear the relationship existing
between conjugate solution concentrations. Bachman has recognized the considerable plotting
efforts necessary for analyzing ternary systems with Brancker's procedure and has introduced an
empirical linear equation correlating conjugate solution concentrations: this equation works well

when the immiscibility between the two solvents is almost complete. Othmer and Tobias, in their
well-known paper, have analyzed the Bachman equation providing an extension to systems with
partial miscibility between the solvents and showing the consistency of an equation due to Hand.
Fleming and Vinatieri have proposed a different approach based on equations derived from a
theory of critical phenomena: they are able to determine the composition of the plait point from
the experimental knowledge of tie lines. Nevertheless, the approach proposed is quite tricky and
works well only if tie lines selected for the fitting procedure are close to the plait point. Very
recently, Goutaudier and Bahramian have presented two new approaches for the determination of
the plait point coordinates. While Goutadier uses the barycentric weighting of the binodal points,
the rectilinear diameter method, and the tie line modulus, the approach of Bahramian is based
on the assumption that the composition of the interfacial phase between two bulky liquid phases
is independent of the compositions of these latter and is identical to the plait point composition.
This supposition has been proved only for binary regular solutions and has been extended for
generic multicomponent systems.
Most of the investigations performed by the authors mentioned, have the aim to propose
linear relations between the concentrations of conjugate solutions. However, the equations
proposed have to be intended as empirical attempts to correlate tie line data, since no theoretical
background is offered. Indeed, Carniti has analyzed the Hand and OthmerTobias equations on
83 aqueous and 26 non-aqueous ternary systems, concluding that both of them are not suitable as
a check of experimental data reliability. The Hand equation may be used only for locating
approximately the position of plait point.
Whereas Hand, Bahramian, and OthmerTobias approaches are easy to implement from a
numerical point of view, on the other hand they are based on empirical equations and can lead to
uncorrected results. On the contrary, Coolidge, Sherwood and Branker's methods are exact, but
they require considerable plot efforts, especially when performed in a Roozeboom diagram
representation. Regarding the recent paper of Goutaudier, it is to be noted that the idea to use the
tie line length variation for determining the plait point position is correct; the same idea is used
here, but the research of the independent parameter to use in this analysis is unnecessarily
complicated. In this paper we propose three methods for evaluating the composition of the plait
point that are in between the two principal approaches existing in the literature: they are based on

numerical methods very straightforward to implement and, at the same time, they use an exact
procedure. Furthermore, we show how, by using the Cartesian coordinate system (X,Y) described
and with a suitable choice of the experimental data to be used, the plait point determination can
be carried out in a very accurate way.

METHODOLOGY:
A. Preparation of Solubility Curve:
First, 10-ml mixtures of H2O and CHCl containing the following % by volume
of water in 125-ml Erlenmeyer flasks: 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% and
90% were prepared. The volume of each liquid was measured accurately using burets.
Next, each solution was titrated with glacial acetic acid until the solution no longer turns
cloudy when shaken vigorously. The volume of each liquid was recorded. Afterwards, the
weight of each liquid in each solution was calculated. Finally, the composition of the
mixture was plotted on a Stokes and Roozeboom diagram and the points were connected
to construct a solubility curve. The curve was extrapolated to zero on both ends.
B. Construction of Tie Lines:
First, 20-ml mixtures of the three liquids with different composition (% by
volume) were prepared. If no layers were formed, the amount of water was increased
until a considerable amount of the second layer can be observed. Then, each mixture was
transferred into the separatory funnel, and was shook well for 2 minutes and the layers
were allowed to separate. Next, 5.0 mL of each aqueous layer was pipetted into
previously weighted 250-mL Erlenmeyer flasks, and was weighed again. 50-mL of
distilled water was added and was titrated to the phenolphthalein end point with 0.5M
NaOH. Afterwards, 5.0 mL of each CHCl 3 layer was pipetted into previously weighted
250-mL Erlenmeyer flasks, and was weighed again. 50 mL of water was added and it was
titrated to the phenolphthalein end point with 0.25M NaOH. The percent by weight of the
acetic acid in each layer was calculated. Finally, the point on the solubility curve was

located and the tie lines were constructed by connecting the compositions of the
complimentary layers with straight line. The plaint point of the system was determined.
RESULTS:
Table 1. Composition of Mixtures
MIXTUR

Volume of Liquid (mL)

H2O
HOAc CHCl3
E NO.
1
9
20.5
1
2
8
22.5
2
3
7
24.4
3
4
6
40
4
5
5
25
5
6
4
19.6
6
7
3
11.3
7
8
2
3.2
8
9
1
1.6
9
Density of H2O
Density of HOAc
Density of CHCl3

Weight of Liquid (g)

% by Weight
H2O
HOAc CHCl3
H2O
HOAc CHCl3
9
20.5
1.474
29.06
66.18
4.76
8
22.5
2.948
24.13
66.97
8.89
7
24.4
4.422
19.54
68.11
12.34
6
40
5.896
6.53
43.53
6.42
5
25
7.37
13.38
66.90
19.72
4
19.6
8.844
12.33
60.41
27.26
3
11.3
10.318 12.19
45.90
41.90
2
3.2
11.792 11.77
18.83
69.40
1
1.6
13.266
6.30
10.08
83.61
0.999 g/mL
1.000 g/mL
1.474 g/mL

Table 2. Tie Lines

MIXTURE
Weight
AQUEOUS
V of NaOH
LAYER
% HOAc
Weight
CHCl3
V of NaOH
LAYER
% HOAc

1
4.98
4.3
15
2.2
0.1
15

2
5.9
1.7
30
1.4
0.15
30

3
6.6
4.2
45
1.24
0.2
45

4
6.94
5.5
60
0.43
0.23
60

Figure 2. Ternary Phase Diagram of Water Acetic Acid Chloroform System

DISCUSSION:
Ternary phase diagram contains three components which are water, acetic acid and
chloroform. From figure 2, each of the three corners or apexes of triangle represents 100% by
volume of one component (water, acetic acid and chloroform). As a result, that same apex will
represent 0% of another two components. When the percentages of acetic acid increases in the
mixture, the volume of water need to be titrated until the mixture turn cloudiness also increases.
The addition of water as the third component to a pair of miscible liquids of acetic acid and
chloroform can change their mutual solubility. If the third component is more soluble in one of
the two different component mixtures the mutual solubility of the liquid pair is decreased and
thus two phases of liquids will appear.

During the experiment there are some errors that may happen. While taking the
measurements of the liquids, the eyes do not perpendicularly on the scale of the measuring
cylinder. Hence, the eyes must be perpendicular to the scale of the mixture to prevent the false
measurement of the liquids. Other than that, when undergoing the shaking process during
titrating to make the mixture completely miscible, the shaking process does not undergo gently
and it may affect the person to take the actual amount of water needed to make the mixture
cloudiness and hence while titrating, the shaking process must undergo gently and the actual
volume of water can be recorded.
Other than that, the errors are the degree of cloudiness. We do not have a specific range
of degree of cloudiness in each of the experiment. This might affect the volume of water added
to the solution. It may be less or more than the actual one. This has greatly affected the
percentage by volume and the curve as well.
Besides, room temperature in the laboratory is not constant during the experiment and
could be another source of error. Room temperature is one of the significant factors that will
change the graph or curve pattern and this might be the cause of incomplete binomial curve.

CONCLUSION AND RECOMMENDATION:

Based from the data obtained by the researchers, it was found out that as the addition of
water as the third component to a pair of miscible liquids of acetic acid and chloroform can
change their mutual solubility. If the third component is more soluble in one of the two different
component mixtures the mutual solubility of the liquid pair is decreased and thus, two phases of
liquids will appear.
The researchers would recommend the use of a larger amount for each of the component
of the mixture of ternary system in order to obtain a more accurate and more precise data.

APPENDIX:
SAMPLE CALCULATIONS:
volume of liquiddensity of liquid=mass of liquid
9 mL

g
=9 g water
( 0.999
mL )

20.5 mL 1.000

1 mL 1.474

g
=20.5 g acetic acid
mL

g
=1.474 g chloroform
mL

total weight=9 g +20.5 g +1.474 g=30.974 g

9g
( 30.974
)100 =29.06

weight of water =

weight of acetic acid=

20.5 g
( 30.974
)100 =66.18

g
100 =4.76
( 1.474
30.974 )

weight of water =

REFERENCES:
http://www.ijesit.com/Volume%203/Issue%205/IJESIT201405_03.pdf
http://onlinelibrary.wiley.com/doi/10.1002/cjce.5450380204/pdf
www.sciencedirect.com/article/pii/S0378381215301229

http://chemwiki.ucdavis.edu/Textbook_Maps/Physical_Chemistry_Textbook_Maps/DeVoe's_
%22Thermodynamics_and_Chemistry
%22/13%3A_The_Phase_Rule_and_Phase_Diagrams/13.3_Phase_Diagrams%3A_Ternary_Systems
http://petrowiki.org/Ternary_phase_diagrams
http://homepage.univie.ac.at/herbert.ipser/Lehre/Phase_Diagrams_Ternary_Systems.pdf