ADAMSON UNIVERSITY

College of Engineering
Chemical Engineering Department
M a ni l a

Experiment no. 5

PHASE DIAGRAM OF A

THREE-COMPONENT LIQUID SYSTEM

Submitted by:

Group 7

Manalili, Francis Kent A. 201411493

Peñarubia, Chester James P. 201611024

Piliin, Ryan Karlo F. 201520251

Submitted to:

Engr. Jarlie Rosario Clemeña

Date performed: January 18, 2018

Date submitted: January 25, 2018

 ABSTRACT
The ternary phase diagram of partially miscible liquids: water – acetic acid – chloroform was
constructed and examined. Water and chloroform are immiscible liquids. Addition of acetic acid
increases the mutual solubility of these two liquids. The solubility curve generated in the ternary
phase diagram shows the transition of the system from a one phase to a two phase system. A tie
line in a ternary phase diagram connects the two phases existing in equilibrium. All points along
a tie line have the same ration of water and chloroform. The length of a tie line decreases as it
approaches the plait point or the point at which three phases exist in equilibrium.

INTRODUCTION
Mutual solubility between component liquids of a particular mixture is an essential knowledge
applicable in many fields of science including metallurgy, petrology, mineralogy, pharmaceuticals,
and etc. For example in making a pharmaceutical formulation, multiple components are needed to
be mixed in homogeneous form. This can be done by knowing the exact ratio of each component
to be mixed in accordance to conditions (i.e. temperature, pressure and composition) such that the
resulting formulation is homogenous (Sinko and Singh, 2006). In this experiment, the three
component mixture of water – acetic acid – chloroform will be examined.

According to the Gibbs phase rule, information regarding phase equilibria can be predicted as
follows:

𝑓 =𝑐−𝑝+2

where f is the variance or the number of variables needed to be specified to describe a particular
system, c is the number of components and p is the number of phases. The number 2 represents
the variables temperature and pressure. At constant temperature and pressure,

𝑓 =𝑐−𝑝

In a three component system at constant temperature and pressure,

𝑓 =3−𝑝

Where the phase can be 1 if all components are completely miscible with one another and 2 if only
2 of the 3 components are completely miscible with each other and other component is only
partially miscible with either of the two components. If the phase is 1, then the variance is 2 which
represent the compositions of the two components needed to describe the system. Consequently,
if there 2 phases present in the system then the variance would result to 1 which indicates the
composition of one of the components needed to describe the system. This information can be
obtained from a phase diagram of a three component system or ternary system (Atkins, 2010).
The main purpose of this experiment is to construct a ternary phase diagram including the
solubility curve for the water – acetic acid – chloroform system. This experiment has four main
objectives: (1) to construct the solubility curve by preparing mixtures of different compositions
and titrating them with water or chloroform; (2) to draw the anticipated tie lines inside the
solubility curve and to select points on the tie lines that correspond to the mixtures; (3) to prepare
these mixtures and determine each of their compositions; (4) to determine the experimental tie
lines and plait point.

THEORETICAL BACKGROUND
The phase diagram for ternary systems is represented using an equilateral triangle. The
compositions of the three components are showed in this diagram such that each apex represents
100% of each of the component in the system. These diagrams are based on the three properties of
equilateral triangles: (1) the sum of the perpendicular distances from any point to each side of the
diagram is a constant equal to the length of any of the sides; (2) mixtures lying on any line
connecting a corner with the opposite side contain a constant ratio of the components at the ends
of the side; (3) mixtures of any two compositions lie on a straight line connecting the two points
on the ternary diagram. Compositions represented on a ternary diagram are usually expressed in
mole fraction, mass fraction and weight or volume percentages (Reamer, et. al, 1949).

One of the features of a ternary phase diagram is a solubility curve. When a system contains two
immiscible components, the third component, which is miscible with all the other components,
increases the mutual solubility of the two immiscible components. A solubility curve is the point
of transition from a two-phase to a one-phase system. A tie line is the line connecting the points
signifying solutions of two different phases existing in equilibrium with each other. These
solutions are called as conjugate solutions. As the amount of the third miscible component
increases in the system, the tie lines becomes shorter and shorter until it approaches a critical point
on the curve called the plait point. At this point, the conjugate solutions are of identical
composition and the tie line appears to be a point in the boundary of the solubility curve (Chua, et.
al., 1996).

PROCEDURE
A. Preparation of Solubility Curves

In this experiment, CHCl3, glacial acetic acid and water were used to construct a ternary phase
diagram system. First, 10-mL mixtures of water and chloroform containing 10%, 20%, 30%, 40%,
50%, 60%, 70%, 80% and 90% by volume of water was prepared in a 125-ml Erlenmeyer flask.
Eaxh solution was then titrated with glacial acetic acid until the solution will no longer turn cloudy
upon shaking. The volume was then recorded and the weight of each liquid was also calculated.
The composition of the mixture was then plotted on a Stokes and Roozeboom diagram.

B. Construction of Tie-Lines

Next, 20-mL mixtures of the three liquids with different percent composition were
prepared. The mixtures were then transferred into a separatory funnel and were shook for 2 minutes
until the layers separated. 5ml of each aqueous layer was pipetted into an Erlenmeyer flask and
was weighed. 50ml of distilled water was added and was titrated to the phenolphthalein endpoint
with 0.5M NaOH. The percent weight of the acetic acid was then calculated and the point on the
solubility curve was located. Tie lines were constructed by connecting the compositions of the
complementary layers with a straight line.

RESULTS
A. Preparation of Solubility Curves

MIXTURE Volume of Liquid (mL) Weight of Liquid (g) % by Weight

NO. H2 O HOAc CHCl3 H2 O HOAc CHCl3 H2 O HOAc CHCl3
1 1 5.3 9 1 5.73 13.48 4.95 28.35 66.70
2 2 7.45 8 2 8.06 11.98 9.07 36.57 54.36
3 3 7.95 7 3 8.60 10.49 13.58 38.93 47.49
4 4 10.05 6 4 10.87 8.99 16.76 45.56 37.68
5 5 10.30 5 5 11.14 7.49 21.16 47.14 31.70
6 6 10.65 4 6 11.52 5.99 25.52 49.00 25.48
7 7 10.90 3 7 11.79 4.49 30.07 50.64 19.29
8 8 11.35 2 8 12.28 3.00 34.36 52.75 12.89
9 9 11.55 1 9 12.50 1.50 39.13 54.35 6.52

Sample Computations:
𝑚 = 𝜌𝑉
 𝑔
𝑤𝑡. 𝐻2 𝑂 = 1𝑚𝐿 (1 ) = 1 𝑔 𝐻2 𝑂
𝑚𝐿
𝑔
𝑤𝑡. 𝐻𝑂𝐴𝑐 = 5.3 𝑚𝐿 (1.08 ) = 5.73 𝑔 𝐻𝑂𝐴𝑐
𝑚𝐿
𝑔
𝑤𝑡. 𝐶𝐻𝐶𝑙3 = 9 𝑚𝐿 (1.50 ) = 13.48𝑔 𝑐ℎ𝑙𝑜𝑟𝑜𝑓𝑜𝑟𝑚
𝑚𝐿

1
% 𝑤𝑡. 𝐻2 𝑂 = ( ) × 100 = 4.95
1 + 5.73 + 13.48

5.73
% 𝑤𝑡. 𝐻𝑂𝐴𝑐 = ( ) × 100 = 28.35
1 + 5.73 + 13.48

13.48
%𝑤𝑡. 𝐶𝐻𝐶𝑙3 = ( ) × 100 = 66.70
1 + 5.73 + 13.48

B. Construction of Tie-Lines

Mixture No. 1 2 3 4

Aqueous Weight ___6.04____ ___6.09____ ____5.79____ ___5.74___

Layer V of ___21.23___ ___35.2____ ___72.8_____ ___41.2___
NaOH
% HOAc ____15___ ____30____ ____45____ ____60____

CHCl3 Layer Weight ___3.2____ ___3.4____ ____3.24___ ___1.43____

V of ___10____ ____15____ ___20____ ___23____
NaOH
% HOAc __15____ ____30____ ___45____ ___60_____

DISCUSSION OF RESULTS
The system of water – acetic acid – chloroform involves partially miscible liquids. Water and
chloroform are almost completely immiscible with each other at room temperature. When mixed,
these two components form two layers: an aqueous layer containing small portions of chloroform
and a chloroform layer containing small portions of water. Acetic acid, on the other hand, is
miscible with water and chloroform. The addition of acetic acid to a heterogeneous mixture of
water and chloroform will increase the mutual solubility of water and chloroform such that the
aqueous layer will contain more of chloroform and the chloroform layer will contain more of water.

This behavior can be explained by the fact that acetic acid behaves as an amphiphilic solvent. The
molecules of acetic acid contain a hydrophilic moiety, the carboxylic group, –COOH, and the
alcoholic one, –OH, and a hydrophobic one, the CH3– and the CH3CH2– one. Acetic acid can
interact with water through its hydrophilic constituents, and also with chloroform through its
hydrophobic constituents. This results to a mutual solubility of water and chloroform (de Moura
et. al., 2013).

The tie lines drawn connect two compositions in each phase of the system existing in equilibrium.
The relative amounts of the two phases can be estimated by using the lever rule. It is shown that
the tie lines decrease in length as it approaches the plait point. However, it should be noted that
these values are “anticipated” values and yet to be verified experimentally. This was done by taking
account the fact that all points lying in a tie line correspond to chloroform and water present in the
same ratio. In order to determine the composition of each phase connecting a tie line, a mixture
which corresponds to a point from the “anticipated” tie line was prepared. Since this mixture was
taken from a point below the solubility curve, the mixture prepared will be of two phases. These
phases are let to separate from each other: the lower layer contains more of the chloroform because
it is denser than water; the upper layer contains more of water. The acetic acid compositions of
each of the layers were determined to know the composition of the two phases in equilibrium and
thus constructing a tie line. Take note that only the composition of the acetic acid is needed to
define the system because the phase below the solubility curve is 2 and therefore the variance or
degrees of freedom according to the Gibbs phase rule is 1.

Few observations pertaining to the acetic compositions can be deduced. (1) The amount of acetic
acid is not the same in the two phases. This means that the tie lines are not straight lines parallel
to one another. (2) The composition of acetic acid in the lower and upper layer increases as it
approaches the anticipated plait point. (3) The upper and lower layers of mixture 4 have almost
the same composition of acetic acid. This signifies that the experimental plait point has a
composition near to the composition of that of mixture 4. Take note that when the acetic acid
composition of the two layers will be equal, that mixture corresponds to the mixture at the plait
point where the three phases are present in equilibrium. The plait point is also the boundary point
between the two phases of the solubility curve. The left side of the solubility curve corresponds
to the upper layer phase which is abundant in water and the right side is of the lower layer phase
which is abundant in chloroform.

CONCLUSION AND RECOMMENDATIONS

The ternary phase diagram the ternary system of water – acetic acid – chloroform was constructed
and examined. Water and chloroform are immiscible liquids. The mutual solubility of these two
liquids is increased by adding a third component, acetic acid which is soluble in both liquids. In
the experiment, the solubility curve of this system was constructed by sets of mixtures, mixture of
water and chloroform. The mixtures were then titrated against acetic acid. Plotting these
compositions in a triangular diagram will give the solubility curve of the system. The solubility
curve acts as the boundary between regions where the system exists in two phases and one phase.
Below the solubility curve, the system exists in two phases. Consequently, outside the curve means
that the system exists only in one phase.

Another features of a ternary phase diagram are the tie lines and plait point. Tie lines are the lines
connecting the composition of the two phases existing in equilibrium. The relative amounts of the
phases in a tie line can be determined using the lever rule. All the points on a tie line correspond
to chloroform and water present in the same ratio. Plait point, on the other hand, is the point at
which three phases exists in equilibrium. This is also the point that margins the left and right curves
that represent the two phases existing in equilibrium. Tie lines and the plait point can be determined
experimentally by preparing mixtures that correspond to the midpoint of the anticipated tie line
drawn inside the solubility curve. It is observed that the length of the tie line decreases as it
approaches the tie line. These mixtures were let to separate into layers: lower layer rich in
chloroform and an upper layer rich in water. Since these mixtures are all present in two phases,
only one composition is needed to describe the system. The acetic acid compositions of each of
the layers were determined.

REFERENCES
 Atkins, P.; de Paula, J. Physical Chemistry Ninth Edition; Oxford University Press: Great

Britain, 2010; pp. 176-181.

 Chua et. al. Energetics of Aerobic and Anaerobic Reactions. In Experiments in Physical

Chemistry Part One. Institute of Chemistry: University of the Philippines-Diliman, 1996;

pp. 55-59.

 De Moura, S. L., dos Santos, J. A. V., da Silva, F. C. M. Thermodynamic study of the

liquid- liquid equilibrium water – chloroform – acetic acid. American Journal of Physical

Chemistry. November 2013; 2(6): 17-121.