Exercise No.

2
Ternary Systems

Charles Michael B. Umerez, Cherrylene M. Bolante, Bernadette P. Cabaccang, Omhar DC. Maravillas,
and Heidi Rose B. del Rosario

Date Performed: February 6, 2019; Date Submitted: February 20, 2019; Lab Section:3L; Instructor:
Eljezwyne Clomer Barcellano

Abstract

A ternary system has three components whose solubility can be represented

by Gibbs-Roozeboom diagram. The exercise determined the Gibbs-
Roozeboom diagram of CH3COOH-H2O-CHCl3 mixture. Data for the
construction of binodal curve was determined via turbidimetric titration.
Construction of tie lines was done by titrating the conjugate phases whose
compositions were found in the two-phase region. Delta point was
determined by extending the tie lines until intersection. Delta point was
needed to determine the plait point, where the components at each phase
is identical. The composition of the plait point is 30% CH3COOH, 4% H2O, and
66% CHCl3.

I. Introduction

In a three-component system, the

system requires four dimensions
representing T, P, and two mole fractions.
Gibbs’ phase rule predicts four degrees of
freedom for a three-component system. At
a fixed pressure, a temperature composition
phase diagram is obtained with three
dimensions. At a fixed temperature and
pressure, a composition–composition phase
diagram with two independent mole
fractions and one dependent mole fraction is
obtained (Mortimer, 2008). This system
reduces the number of degrees of freedom
to two is a single phase is present, and an
equilateral triangle is customarily used to
plot the mole fractions. This method is called
Figure 2.1 Gibbs- Roozeboom Diagram
the Gibbs-Roozebom method, where an
equilateral triangle is used for graphic In an equilateral triangle, the sum of the
representation. Figure 2.1 shows the Gibbs- perpendiculars from a given point to the
Roozeboom diagram. three sides is a constant. The points A, B, and
 C at the apices of the triangle contains 100%
of A, 100% of B and 100% of C. The lines
parallel to AB represent the different
percentages of C. Any point on the line AB
represents a system containing 0% C
(Castellan, 1983). There is a one-phase
region of complete miscibility and a two-
phase region containing tie lines,
representing the compositions of two liquid
phases that coexist at equilibrium
(Mortimer, 2008).
II. Methodology
Turbidimetric Titration
The data points for the binodal curve was
determined using turbidimetric titration at
constant temperature and pressure.
Five 25.0 mL solutions containing CH3COOH-
H2O (A-B) at varying concentrations of 20, 30, 40,
60, and 70% v/v CH3COOH were prepared. Each
of the solution was titration with CHCl3 (C) until
turbid solution was observed. The 60% solution
was titrated first for familiarization of the
desired end point.
The steps above were repeated but using
another five 25.0 mL solutions of CH3COOH-
Determination of %w/w CH3COOH in each
conjugate phase.
The density of the conjugate phases was
measured using a pycnometer. A 5.00 mL aliquot
of each phases was obtained using a pipette and
was placed into a 250-mL E. flask. The aliquot
was titrated with 1.0 M NaOH until the
phenolphthalein end point.
In this exercise, a Gibbs-Roozeboom
diagram representing a three-component
system was constructed; and the behavior
of the system in terms of the various
molecular interactions present was
explained.
CHCl3 (A-C) at varying concentrations of 20, 30,
40, 60, and 70% v/v CH3COOH. The solutions
were titrated with H2O (B).
Preparation of conjugate phases
Four 50 g mixtures containing CH3COOH –
H2O – CHCl3 whose compositions were found
within the two-phase regions of the diagram
were prepared. The compositions of the
mixtures were chosen in such a way that they
gave approximately equal volumes of the
conjugate phases. Each mixture was equilibrated
in a 250-mL separatory funnel at 25°C. The
conjugate phases were separated and
transferred into 125-mL Erlenmeyer flasks. The
mixtures were covered and labeled properly.
III. Results and Discussion
The first part of the experiment is the
turbidimetric titration to determine the
binodal curve. The Gibbs-Roozeboom
diagram for the three-system component
consisting CH3COOH, H2O, and CHCl3 was
made. The Gibbs-Roozeboom diagram of
the three-system component is shown in
figure 2.2.
 Figure 2.2 Gibbs-Roozeboom diagram of the ternary system composed of CH3COOH, H2O, and CHCl3
The pairs chloroform-acetic acid and
water-acetic acid are completely miscible
while the pair chloroform-water is not. This
resulted to the diagram obtain in figure 2.2.
Acetic acid and water are miscible with each
other due to hydrogen bonding while acetic
acid and chloroform are partially miscible
due to hydrophobic interaction. Water and
chloroform are immiscible in water due to
infinite repulsions between the molecules of
the solutes (Buzato, 2008). Also, chloroform
is nonpolar while water is polar, so there is a
difference between their polarity that
causes the immiscibility.
Table 2.1 Average %mass of A, B, and C from the titration of A-B with C.
Component Mass at 20% A Mass at 30% A
A (CH3COOH) 19.9662 29.22751
B (H2O) 75.83656 64.75777
C (CHCl3) 4.197241 6.01472
The tie lines were determined by
preparing the conjugated phases whose
compositions are found within the two-
phase region of the diagram. The tie lines
represent the compositions of two liquid
phases that coexist at equilibrium
(Mortimer, 2008). When the compositions of
B-rich and C-rich phases become nearly the
The binodal curve is the curve line within
the triangle. The binodal curve is the region
of immiscibility, which divides a region of
component concentrations that will form
two immiscible aqueous phases (i.e., above
the curve) from those that will form one
phase (Kaul, 2000). Turbidimetric titration
was used to obtain the data for the
construction of the binodal curve. This
indicates the limit or extent when it comes
to percent composition of each component
to form a solution. The calculated percent
mass of each component after titration is
showed in table 2.1
Mass at 40% A Mass at 60% A Mass at 70% A
36.21539 51.00604 46.79663
51.58313 32.28893 19.04413
12.20148 16.70503 34.15924
same, the tie lines get shorter. Two
conjugate phases were obtained, the upper
layer and lower layer. The densities of the
conjugate phases were determined using
pycnometer in order to obtain the mass of
the aliquot. The aliquots of the conjugated
phases were titrated with standardized
NaOH to determine the %CH3COOH present.
 The points where the tie lines intersect are phase is the water rich while the lower layer
determine the composition of the conjugate is the chloroform rich, since water and
phases. The upper layer of the conjugate chloroform are only partially miscible.

Table 2.2 Average %mass of A, B, and C from the titration of A-C with B.

Component Mass at 20% A Mass at 30% A Mass at 40% A Mass at 60% A Mass at 70% A
A (CH3COOH) 14.945 22.7161 30.34324 43.54094 48.10236
B (H2O) 1.135296 2.876046 5.762557 15.71027 22.95769
C (CHCl3) 83.91971 74.40785 63.8942 40.74879 28.9399

Table 2.3 Data on the density of the phases

Mixture Phase Density

1 U 1.024639478
L 1.447850031
2 U 1.037440117
L 1.426597627
3 U 1.042765012
L 1.410228759
4 U 1.042765012
L 1.374618365

Table 2.4 Calculated %w/w CH3COOH from titration of conjugated phases.

Mixture Phases Mass CH3COOH, g Mass of sample, g %w/w CH- Average %w/w
3COOH CH3COOH
1 U I 1.005275174 5.123197388 19.62202698 19.62202698
II 1.005275174 5.123197388 19.62202698
L I 0.242448718 7.239250156 3.349086068 5.673705767
II 0.277929019 3.474840075 7.998325467
2 U I 1.36599156 5.187200586 26.33388737 26.33388737
II 1.36599156 5.187200586 26.33388737
L I 0.405066761 7.132988135 5.678780808 5.699506285
II 0.408023453 7.132988135 5.720231763
3 U I 1.986896814 5.213825058 38.10823709 37.6545676
II 1.939589747 5.213825058 37.20089811
L I 0.579511571 7.051143796 8.218688876 7.967096359
II 0.544031271 7.051143796 7.715503843
4 U I 2.341699817 5.213825058 44.91327942 44.68644468
II 2.318046283 5.213825058 44.45960993
L I 1.147196375 6.873091826 16.69112539 17.80960286
II 0.780566606 4.123855096 18.92808034
 The obtained density of the mixtures
and the %CH3COOH of the upper and lower
phases of the mixtures are shown in table 2.3
and table 2.4. The tie lines can be extended
outside the triangle until they intersect at one
point. This point is called the delta point. The
delta point helps in determining the plait point,
which is the point where it is tangent with the
delta point. The plait point is where the two
conjugate phase solutions have the same
composition (Castellan, 1983). From figure 2.2,
the plait point of the ternary system is at 30%
CH3COOH, 4% H2O, and 66% CHCl3.
One of the errors committed in the
experiment is determining the end point during
turbidimetric titration. The end point was not
clear so there were cases of inaccurate
determination or overrun of the end point. Also,
contamination of the samples or reagent might
cause errors in the data.
Ternary system has an application in
specific cosmetic formulation. A study
conducted by Comelles et al (1988) uses ternary
system to understand the physico-chemical
aspect and contribution of the different
components to develop a cosmetic formulation.
Another use of ternary system is the proper
flux/ore combinations to ensure the correct flux
is chosen for a specific ore. It is to ensure that the
flux supplied reacts with the ore or concentrate
to form a liquid slag at the furnace operating
temperature (Twidwell, 2016). Another example
of ternary system application is on stainless steel
(Fe-Ni-Cr). Ternary phase diagrams are needed
so that the three components can be compared
at once. To view all three compositions at the
same time, a triangular plot is set up with an
element at each of the vertexes with the
temperature and pressure stated (Yeakle, 1996).
Another method for constructing a
ternary diagram is the cloud-point method which
follows the same principle with turbidimetric
titration. A concentrated stock of component 1
(e.g., dextran or phosphate) is added drop-wise
to a known amount of a concentrated stock of
component 2 (e.g., PEG). At a critical point—the
cloud point—the mixture will become turbid and
is indicative of two-phase formation. The
composition, just prior to two-phase formation,
is calculated and provides a point on the binodal.
The mixture is then diluted to below the cloud
point and the procedure is repeated (Kaul, 2000).
Cloud-point method is relatively inaccurate
when using polymers that are polydisperse. Such
polymers produce a gradual decrease or increase
in turbidity rather than a sharp change, making
the point of transition awkward to calculate.
IV. Conclusion
The Gibbs-Roozeboom diagram for the
ternary system composed of CH3COOH, H2O,
and CHCl3 was constructed in the
experiment using turbidimetry titration.
Turbidimetry titration was done in order to
obtain the data points for the construction of
the binodal curve or the region of
immiscibility. The tie lines, delta point and
plait point were determined by titrating the
conjugate phases obtained. Tie lines were
made by connecting a line between the
composition of acetic acid in the upper layer
and lower layer. Delta point was determined
by extending the tie lines until they intersect
in one point. Plait point was determined by
constructing a line from the delta point to a
point tangent to the binodal curve. Based on
the Gibbs-Roozeboom diagram, the
composition of the plait point is 30%
CH3COOH, 4% H2O, and 66% CHCl3.
Errors in the experiment include
inaccurate determination of the end point
and possible contamination of the reagents.
 V. References MORTIMER, R.G. 2008. Physical Chemistry. 3rd
ed. Canada: Elsevier Academic Press. p. 290.
Buzatu, F.D., Lungu, R.P., Buzatu,D., Sartorio, R.,
and Paduano L. (2008). Spinodal Composition of Twindell, L.G. (2016). Application of Binary and
the System Water + Chloroform + Acetic Acid at Ternary Phase Diagramsto Fire Assaying.
25 °C. J Solution Chem (2009) 38: 403–415
YEAKLE, J. (1996). Ternary Phase Diagrams.
CASTELLAN, G.W. 1983. Physical Chemistry. 3rd Retrieved on February 19, 2019 at
ed. New York: Addison Wesley. p. 337-339. http://sv.rkriz.net/classes/MSE2094_NoteBo
ok/96ClassProj/experimental/ternary2.html
Comelles, F.,Megias, V., Sanchez, J., Parra, J.L.,
Coll, J., Balaguer, F.,and Pelejero, C.
(1989).Applications of Ternary Systems in
Specific Cosmetic Formulation. International
Journal of Cosmetic Science, 11(1), 5-19

DANIELS, F., et al., 1970. Experimental Physical

Chemistry. New Hill-Hill Book Co., Inc. p. 105-
108

Kaul, Anita. (2000). Phase Diagram. Retrieved

on February 19, 2019

VI. Sample Caculations