Exercise No.

2
Ternary Systems

Gerry Mark S. Gubantes, John Patricia Mae Centeno, Joshua P. Movilla, Jo Darryl Fillaro, Jose Carmelo
P. Tinio, Alyssa Zen Aguillana
Date Performed: February 07, 2018; Date Submitted: February 14, 2018; 2L; Sir King Bryan Gabog

Abstract

In this exercise, a Gibbs-Roozeboom diagram was constructed representing

CH3COOH-H2O-CHCl3 mixture. A system of acetic acid-water-chloroform
forms two separate layers since two of the components: water-acetic acid and
acetic acid-chloroform are completely miscible, while one pair is partially
immiscible (water-chloroform). The binodal curve was generated
experimentally via turbidimetric titration of known amounts of each component.
Mixtures outside the binodal curve are homogeneous whereas mixtures within
the binodal curve are heterogeneous in nature. Also, tie lines, plait point and
delta point were determined and located in the diagram. The plait point was
determined to be 37% Acetic acid, 5% water, and 58% chloroform.

I. Introduction third. The distance from each apex to the

Gibb’s phase rule describes the relationship
among the number of degrees of freedom (F),
the number of components (C), and the
number of phases (P) at equilibrium:
F=C–P+2 Equation 2.1
For a ternary component (three-component)
system in one phase, Gibbs’ phase rule
predicts four degrees of freedom.
center of the opposite side of the equilateral
triangle is divided into 100 parts,
corresponding to weight percentage
composition. The composition corresponding
to a given point is readily obtained by
measuring the perpendicular distance to the
three sides. By this method, any composition
of a three-component system can be
represented by a point within the triangle.
Refer to Figure 2.1 (Castellan, 1983).

F= 3 – 1 + 2
F=4

However, a system of four variables cannot be

graphically represented on paper, thus, study
of ternary systems are carried out at constant
temperature and pressure. By doing this, the
degrees of freedom will be reduced to two
(F=2). This can then be represented using
Gibbs and Roozeboom method (Levine,
2002).
Figure 2.1. Gibbs-Roozeboom diagram.
The Gibbs-Roozeboom method is done by
plotting the molar fraction of each component When three components are mixed in certain
of a ternary system in the triangular ratios, two separate layers result if two of the
coordinates with equal sides. Knowing the liquids are completely miscible and one pair is
weight fractions of two components fixes the partially miscible. When a sufficient number of
data points representing the two separate
layers are plotted on the Gibbs-Roozeboom The solutions were then titrated with H2O (B)
diagram, a binodal curve which encloses the until the desired end point. Solution 4 was
“region of immiscibility” can be constructed titrated first.
(Davidson et al., 1941).
Three 50 g mixtures containing all three
components (CH3COOH-H2O-CHCl3) were
This specific exercise aims to construct a
prepared such that the compositions were
Gibbs-Roozeboom diagram representing a
found within the two-phase region of the
three-component system and to explain the
diagram. Proportion of each component
behavior of the system in terms of various
indicated in Table 2.3 was specifically
molecular interactions present.
followed.
II. Methodology Table 2.3. Preparation of mixtures for
determination of tie lines.
Five 25.0-mL solutions, each containing point vol. A, mL vol. B, mL vol. C, mL
CH3COOH-H2O (A-B) at carrying 1 4.76 15.58 18.66
concentrations 20, 30, 40, 60, and 70 %v/v 2 7.15 15.07 18.66
CH3COOH were prepared by following the 3 9.53 12.56 18.66
proportions indicated on Table 2.1. 4 11.91 10.05 18.66
Table 2.1. Preparation of CH3COOH-H2O (A- Each mixture was allowed to equilibrate in a
B) mixture.
250-mL separatory funnel at 25 °C. The
sol’n no. %A (v/v) vol. A, mL vol. B, mL
conjugate phases were separated and were
1 20 2.5 10
transferred into 125-mL Erlenmeyer flasks.
2 30 3.75 8.75
3 40 5 7.5 1 M stock NaOH solution was standardized by
4 60 7.5 5 weighing 0.25 g KHP and dissolving in water.
5 70 8.75 3.75 Two-three drops of phenolphthalein indicator
was added to the solution and was then
Each solution was titrated (2 trials) with CHCl3 titrated to phenolphthalein end point.
(C) until the first sign of turbidity was observed,
i.e., appearance of a second phase. Solution Densities of the conjugate phases were
no. 4 was first titrated to familiarize with the measure using pycnometer. Whereas the %
desired end point. w/w CH3COOH in each conjugate phases
were determined by titration with the
Another five 25.0-mL solutions were of, this standardized NaOH. Using a pipette, 5.00 mL
time, CH3COOH-CHCl3 (A-C) were prepared of aliquot of each phase were placed in a
by following the proportions indicated on Table 250—mL E-flask. Two-three drops of
2.2. phenolphthalein indicator were added to the
analyte and the sample was titrated (2 trials)
Table 2.2. Preparation of CH3COOH-CHCl3 (A-C) with the standardized NaOH to the
mixture. phenolphthalein end point.
sol’n no. %A (v/v) vol. A, mL vol. C, mL
1 20 2.5 10 III. Results and Discussion
2 30 3.75 8.75
3 40 5 7.5 There are several types of ternary systems
4 60 7.5 5 depending on the miscibility of the
5 70 8.75 3.75 components with each other. For system
A:B:C, wherein A is completely miscible with B
and C, and B:C are partially miscible with each
other, it results to the following general ternary
phase diagram:
Figure 2.2. A ternary phase diagram for system A:B:C.
In Figure 2.2, the vertices of the triangle show
pure substances A, B and C. The curve line
within the triangle is called the binodal curve.
As previously discussed, this binodal curve
encloses the region of immiscibility. This
indicates the limit or extent when it comes to
percent composition of each component to
form a solution. When B and C are mixed with
amounts included in this region, the resulting
mixture has two phases and B and C are now
immiscible (Castellan, 1983).
Another part of the Gibbs-Roozeboom
diagram is the tie line. Significantly, tie line
refers to the isothermal line connecting the
composition of the two phases in a two phase
field. It is used to determine the composition of
the phases in the two-phase field. Delta point,
on the other hand, is where all the tie lines
meet or the intersection of the tie lines. This
delta point is important in order to locate the
plait point. The plait point is the isothermal
critical point in a ternary phase diagram. At the
plait point, it is easy to locate which region is
A-rich and which is B-rich. Also, at the plait
point, the composition of A,B and C at phase
1 is identical to the composition of A,B and C
at phase 2 (Levine, 2002).
In the experiment, acetic acid (A), water (B),
and chloroform (C) were used as the ternary
system. This exercise aimed to explain the
behavior of the system in terms of the various
molecular interactions present.
In essence, acetic acid and chloroform are
completely miscible as well as acetic acid and
water. Since acetic acid can interact with both
water and chloroform, it should be placed at
the center of the diagram.
The interaction between acetic acid and water
is governed by hydrogen bonding, making
them miscible with each other. However,
chloroform and water are only slightly soluble
in one another.
For chloroform and acetic acid, there exists a
significant dipole-dipole interaction which
causes them to be completely miscible. This
can be supported by the close values of their
dielectric polarization which are 4.8 and 6.2,
respectively. The dielectric polarization is a
measure of polarity. Compounds with low
dielectric polarization values are relatively
nonpolar, while those with higher values are
polar, and the latter includes water whose
dielectric polarization constant is 80.4. Due to
the large difference in the dielectric constants
of water and chloroform, which renders
chloroform as weakly polar while water as
strongly polar, plus the absence of H-bonding,
water’s dipole-dipole interaction with
chloroform is weak resulting to partial
miscibility (Solomons, 2011).
In the construction of the Gibbs-Roozeboom
diagram, turbidimetric titration was first
performed to obtain the necessary data for the
construction of the binodal curve. The volume
where the first sign of turbidity appeared was
recorded for both water-acetic acid and acetic
acid- chloroform mixtures with chloroform and
water as titrants, respectively.
Initially, acetic acid - water was titrated with
chloroform. The two components are miscible
and addition of chloroform forms
homogeneous solution still. However,
saturation was reached when chloroform was
further added, resulting to turbidity. As the
amount of chloroform was increased, the
miscibility of acetic acid with water decreased
due to the dipole-dipole interaction between
acetic acid and chloroform molecules.
Eventually, when enough chloroform had been
added, the mixture separated into two layers –
the water-rich phase and the chloroform-rich
phase – since water and chloroform are only
partially miscible with each other (Rogers,
2011).
The same phenomena happened when acetic
acid - chloroform mixture was titrated with
water. As water was added to the system, the
miscibility of acetic acid with chloroform
decreased due to the hydrogen bonding
between the acetic acid and water molecules.
Eventually, when enough amount of water has
been added, the mixture separated into two
layers.
The amounts of titrants used were recorded
and were used to compute the %w/w of the
three components at the end point or at which
the second phase of the mixture/turbidity was
observed. Table 2.4 and 2.5 shows the
experimental and derived data.

Table 2.4. Data on the titration of mixture A-B with C.

Trial Prescribed Volume Mass %Weight
% v/v
A B C A B C A B C
1 20 5 20 0.2 5.25 19.9408 0.2948 20.59987 78.2434 1.156732
30 7.5 17.5 0.7 7.875 17.4482 1.0318 29.88048 66.20452 3.915007
40 10 15 2.2 10.5 14.9556 3.2428 36.58741 52.11301 11.29958
60 15 10 3.9 15.75 9.9704 5.7486 50.04925 31.68324 18.2675
70 17.5 7.5 9.7 18.375 7.4778 15.477 44.45945 18.093 37.44756
2 20 5 20 0.8 5.25 19.9408 1.1792 19.90899 75.61926 4.471748
30 7.5 17.5 1 7.875 17.4482 1.474 29.3874 65.11203 5.500575
40 10 15 2.2 10.5 14.9556 3.2428 36.58741 52.11301 11.29958
60 15 10 3 15.75 9.9704 4.422 52.25198 33.07766 14.67036
70 17.5 7.5 10 18.375 7.4778 14.74 45.26665 18.42149 36.31186

Table 2.5. Data on the titration of mixture A-C with B.

Trial Prescribed Volume Mass %Weight
% v/v
A B C A B C A B C
1 20 5 3 20 5.25 2.99112 29.48 13.91793 7.929563 78.1525
30 7.5 1 17.5 7.875 0.99704 25.795 22.7161 2.876046 74.40785
40 10 2.1 15 10.5 2.093784 22.11 30.25607 6.033302 63.71063
60 15 6.4 10 15.75 6.381056 14.74 42.71643 17.30641 39.97716
70 17.5 8.6 7.5 18.375 8.574544 11.055 48.34948 22.56189 29.08863
2 20 5 0.4 20 5.25 0.398816 29.48 14.945 1.135296 83.91971
30 7.5 1 17.5 7.875 0.99704 25.795 22.7161 2.876046 74.40785
40 10 2 15 10.5 1.99408 22.11 30.34324 5.762557 63.8942
60 15 5.4 10 15.75 5.384016 14.74 43.90364 15.00812 41.08824
 70 17.5 8 7.5 18.375 7.97632 11.055 49.12272 21.32346 29.55383

The mass for each component at varying
concentrations of % v/v CH3COOH were
computed given the density and the volume
used of the titrant for each component. Adding
the mass of CH3COOH, H2O, and CHCl3 gives
the total mass. The mass of each component
divided by the total mass gave the % w/w of
CH3COOH. The % w/w of CH3COOH for each
component both in H2OCH3COOH titrated
with CHCl3 and CH3COOHCHCl3 titrated with
H2O were recorded and used to form a binodal
curve. See Figure 2.3.
After the binodal curve was constructed, the
tie lines were then plotted. The values to be
plotted were obtained by preparing the ternary
mixtures whose compositions were located
within the two-phased region of the diagram.
The phases were separated and from each
phase (upper and lower), aliquots were
obtained and titrated using the standardized
sodium hydroxide, NaOH solution. The
standard used was KHP.
From the prepared mixtures containing
CH3COOHH2OCHCl3, its compositions are
found within the two-phase region of the
diagram. The conjugate phases were
separated and their density was computed
using the pycnometer. From the density of
each conjugate phase and given the volume of
aliquot, the mass of the aliquot were
computed. From this the mass of CH3COOH is
computed given the molarity and volume used
of NaOH for standardization multiplied by the
molar mass of CH3COOH. Finally the % w/w
of CH3COOH is computed from mass of
CH3COOH divided by mass of aliquot
multiplied this quantity by 100. Table 2.6, 2.7
and 2.8 summarizes the experimental and
derived data.

Table 2.6. Data for the density of conjugate phases at room temperature.
mass pyc. mass pyc. w/ mass pyc. mass pyc. density lower, density upper,
Mixture
empty,g water,g w/ lower,g w/upper, g g/mL g/mL
1 16.028 26.2843 30.8904 26.5743 1.444810243 1.025231609
2 16.028 26.2843 30.6631 26.6788 1.422713854 1.03539031
3 17.6083 27.7399 31.9028 28.2209 1.40670657 1.044374699
4 17.6083 27.7399 31.626 28.2974 1.379466975 1.051902983

Table 2.7. Standardization of NaOH.

Parameter Trial 1 Trial 2
mass KHP, g 0.254 0.247
volume used, ml 1.4 1.1
molarity of NaOH, M 0.923374 1.0995272
average molarity, M 1.066766587

Table 2.8. Data on the titration of conjugate phases.

vol. NaOH used,
mass A, g Average
Phase mass aliquot, g mL
%w/w, A
trial 1 trial 2 trial 1 trial 2
U1 5.126158 16.5 20.8 1.057014 1.332479 23.30686
L1 7.224051 4.2 4 0.269058 0.256246 3.635799
U2 5.176952 25.4 24 1.627161 1.537475 30.56467
 L2 7.113569 7.5 7.4 0.480461 0.474055 6.70912
U3 5.221873 32.4 32 2.075592 2.049967 39.50267
L3 7.033533 18 11.2 1.153106 0.717488 13.29769
U4 5.259515 39.6 37.4 2.536834 2.395899 46.89342
L4 6.897335 18.2 17 1.165919 1.089045 16.34663

The computed % w/w of CH3COOH for each
conjugate phases, upper layer (B-rich) and
lower layer (C-rich), were the two points
connected with a straight line (tie lines). When
the compositions of B-rich and C-rich phases
become nearly the same, the tie lines get
shorter. Extending the tie lines, the delta point
is obtained and a line tangent to the binodal
curve was drawn to locate the plait point
wherein the two phases finally become
identical.
It can be seen from the ternary diagram that
the addition of acetic acid to the water and
chloroform mixture increases the miscibility of
the two liquids. Addition of acetic acid results
to further mixing of water and chloroform until
it reaches a point with composition outside the
binodal curve where only one phase exist
(Rogers, 2011).
In Figure 2.3, the Gibbs-Roozeboom
method’s plait point is at, 37% acetic acid,
5% water and 58% chloroform.
system which has shaped memory properties.
Of these, ‘Spangold’, which has the nominal
stoichiometry Au7Cu5Al4, has received some
attention for jewelry applications, while the
edge compound Cu3Al is a well-known shape
memory composition with corresponding
specialized industrial uses (Bhadia et al.,
2007). Another application is the production of
amorphous alloys in ternary systems Zr-(Pd,
Ru, Mo)-(Si, Bi). The synthesis of zirconium
alloys can make use of the ternary system
since the alloys are expected to lie near the
eutectic ranges.
Lastly, stainless steel (Fe-Ni-Cr) is another
common example of a metal alloy that is
represented by a ternary phase diagram. It
has iron, nickel, and chromium compositions.
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. See figure below for
better illustration (Yeakle, 1996).

The properties of many systems are

conveniently described with the help of
triangular graphs. The increase in mutual
solubility of two liquids, owing to the addition
of a third, is a practical as well as theoretical
importance. This is important in deciding in
which solvent to use in dissolving a specific
solute. It will be a great help in choosing the
right solvent to use in the extraction method.
Likewise, ternary system is very useful in the
field of Petrology and Geology as in the study
of basalts, studies concerning minerals and
metals. Also, symbolic ternary system models
are used in the formal verifications of digital
circuits.
Figure 2.4. Stainless steel phase diagram.
Specifically, one of the important applications
of ternary system is the Al-Au-Cu ternary
Errors may be accounted to the limitations of
the instruments used, like the defective buret.
Also, it may also be due to the experimenters,
such as overruns. Another factor that may
alter the gathered data is contamination of the
sample.
On the other hand, Salih (2017) uses a liquid-
liquid extraction to contruct a ternary phase
diagram. It utilizes a liquid-liquid extractor
design in which a liquid solution (the feed) is
IV. Conclusion
The Gibbs- Roozeboom diagram of the acetic
acid-water- CHCl3 system was constructed in
this experiment. Since the predicted degrees
of freedom of the Gibbs phase rule cannot be
represented graphically, the temperature and
pressure were held constant. To be able to
graphically represent the ternary system, the
Gibbs- Roozeboom diagram was used. This
makes use of an equilateral triangle.
V. References
BHADIA, V.K., LEVEY, F.C., KEALLEY, C.S.,
DOWD, A., and CORTIE, M.B. 2007. The
aluminum-copper-gold ternary system.
Australia: Institute for Nanoscale Technology.
CASTELLAN, G.W. 1983. Physical
Chemistry. 3rd ed. Massachusetts: Addison-
Wesley Publishing Company.
DAVIDSON, A.W., H.K. VAN KLOOSTER,
and W.H. BAUI. 1941. Laboratory Manual of
Physical Chemistry USA: Parallex Binding,
Sieves Mechanical Binding Co.
LEVINE, I. N. 2002. Physical Chemistry, 6 th
Ed. New York: McGraw-Hill.
contacted with an immiscible or nearly
immiscible liquid (solvent) that exhibits
preferential affinity or selectivity towards one
or more of the components in the feed. This
type of method is more efficient than the
turbidimetric method because it does not rely
upon human judgement to determine
immisicibility (Salih, 2017).
Mixtures of the acetic acid-water- CHCl3
system whose composition lies under the
binodal curve were prepared to be able to
obtain the conjugate phases. From this data,
the tie lines were constructed. The delta and
plait points were also located. Extending the
tie lines does this and the point of intersection
is the delta point. The plait point is the point
where the line extended from the delta point
and the curve meets. Consequently, the plait
point is at, 37% acetic acid, 05% water and
58% chloroform.
ROGERS, D.W. 2011. Concise Physical
Chemistry. New Jersey: John Wiley & Sons,
Inc.
SALIH, M. 2017. Liquid-liquid equilibrium
for the design of extraction column.
European Journal of Engineering and
Technology. Vol. 5 No. 4
SOLOMONS, T.W.G. 2011. Organic
Chemistry. 10th ed. USA: John Wiley and
Sons, Inc.
YEAKLE, J. Ternary Phase Diagrams.
Retrieved from:
<http://www.sv.vt.edu/classes/MSE2094_Not
eBook/96ClassProj/experimental/ternary2.ht
ml> on December 2, 2013.
VI. Calculations

Construction of binodal curve massA = (MV)NaOH ∙ MMA

massphase = ρphase (Vphase ) massA

g
g = (1.0114506 M)(0.01619 mL) (60.052 )
massA = 1.05 (5 mL) = 5.25 g mol
mL = 0.9833746 g

massB = 19.94 g

massC 0.737 g %A in aliquot

massA
total weight = ∑ massphase mass fractionA = × 100
massaliquot
total weight = 5.25 g A + 19.94 g B + 0.737 g C 0.9833746 g
= 25.9278 g mass fractionA = × 100 = 19.1929%
5.1236 g
massphase
% w⁄w phase = × 100
total weight

5.25 g A
% w ⁄w A = × 100 = 20.25%
25.9278 g

Density of conjugate phases

massphase+pyc − masspyc
ρphase = ρ
massH2O+pyc − masspyc H2O

31.702 g − 16.722 g g
ρlower layer = × 0.99704
27.085 g − 16.722 g mL
= 1.44 g/mL

Standardization of NaOH

(mass⁄MM)KHP
MNaOH =
VNaOH

0.254g
( ⁄204.22 g/mol)
MNaOH =
0.0014 L
= 1.066766587 M

Mass of aliquot

massaliquot = ρphase (Valiquot )

g
massaliquot = 1.0247 (5.00 mL) = 5.1236 g
mL

Mass of A in aliquot