American Journal of Physical Chemistry

2013; 2(6): 117-121

Published online November 30, 2013 (http://www.sciencepublishinggroup.com/j/ajpc)
doi: 10.11648/j.ajpc.20130206.11

Thermodynamic study of the liquid-liquid equilibrium

water-chloroform-acetic acid
Silio Lima de Moura, José Aroldo Viana dos Santos, Francisco Carlos Marques da Silva
Bioelectrochemistry Laboratory, Federal University of Piauí, Teresina 64 049 550, Brazil

Email address:
siliosilicio@hotmail.com(S. L. Moura)

Tocite thisarticle:
Silio Lima de Moura, José Aroldo Viana dos Santos, Francisco Carlos Marques da Silva. Thermodynamic Study of the Liquid-Liquid
Equilibrium Water-Chloroform-Acetic Acid. American Journal of Physical Chemistry. Vol. 2, No. 6, 2013, pp. 117-121.
doi: 10.11648/j.ajpc.20130206.11

Abstract: Experimental liquid-liquid equilibria of the water-chloroform-acetic acid system were studied at temperature of
298.15 K. Complete phase diagrams were obtained by determining solubility and tie-line data. Data for the construction of
ties-lines were determined by preparing mixtures of known mole fraction of components in the region of formation of two
phases. Separation factors were evaluated for the immiscibility region.

Keywords: Liquid-Liquid Equilibrium, Microstructure, Ternary System

within this system is a open homogeneous system in the

1. Introduction
Recovery of organic acids from dilute solutions resulting
from fermentation processes is important, and many
solvents have been tried in attempts to improve recovery
[1-19].
Pure liquids when mixed in appropriate proportions at
certain temperatures and pressures, do not form only one
homogeneous liquid phase, but two liquid phases with
different compositions. This fact is due to the two-phase
state to be more stable than the monophasic state. If these
phases are in equilibrium, then the phenomenon is called
liquid-liquid equilibrium (LLE) [20].
All systems seek thermodynamic equilibrium. The
thermodynamic stability criterion provides that must be
satisfied by providing that at a constant temperature and
pressure, a steady state is that in which present a minimum
of the Gibbs free energy (Equation 1) [21,22]:
, 0
When two or more substances are mixed, dGis defined as
the difference between the Gibbs free energy of the solution
and the pure compounds. If dG ≤ 0, forms a stable single
phase solution, but if dG ≥ 0, the homogeneous solution is
unstable and the system is forced to split into two or more
phases in order to minimize the Gibbs free energy. This way
or two-phase systems are formed by multiphasic.
System comprising two or more phases, thus a
heterogeneous system is a closed system and each phase
closed total system. Such system, in which no chemical
reaction occurs, will be in equilibrium in relation to the
process of heat transfer, displacement of the border and mass
transfer.
The mechanical and thermal equilibrium, it’s necessary
that the pressure and temperature within the system are
uniform throughout all phases π, to achieve the mechanical
and thermal equilibrium. If µi is the chemical potential, it is
also expected to have a uniform value across all phases
composing the heterogeneous system. This was proved by
Gibbs in 1875, and the results for a closed heterogeneous
system in equilibrium without chemical reaction with
respect to the processes mentioned are [21, 22]:
.………… (2)
.………… (3)
.…………
(1)
.………… (4)
where the superscripts represent the phases and the
subscripts represent the components.
The status of each phase of a steady state can be
characterized with n+2 variables: pressure, temperature, and
chemical potential of each of the n components in phase.
However, not all of these variables are independent, however,
the Gibbs-Duhem equation (Equation 5) shows how these
variables are related [22]:
118 Silio Lima de Moura et al.: Thermodynamic Study of the Liquid-Liquid Equilibrium Water-Chloroform-Acetic Acid
∑ 0 (5)
This equation introduces a restriction on simultaneous
variation of T, P and chemical potential µi for a single phase.
Thus, the n+2 variables that can be used to characterize a
phase, only n+1 are independent. The limitation introduced
by the equation of Gibbs-Duhem causes one of the variables
is dependent. Therefore, it is said that a phase has n+1
degrees of freedom.
Thus, if each step of the system is in equilibrium, the total
number of independent variables is p(n+1). If the
heterogeneous system as a whole is in equilibrium, then
there are (p-1)(n +2) equilibrium relationships between the
p(n+1) variables given by the equations (2), (3) and (4).
Then the number of degrees of freedom, which is the
number of intensive variables minus the number of relations
or constraints are [22]:
1 1 2 (6)
This equation is the Gibbs phase rule.
In this paper, we evaluate acetic acid as an agent for the
extraction of chloroform from dilute aqueous solutions, we
herein report liquid-liquid equilibrium results at
temperatures of 298.15 K for the ternary system of
water-chloroform-acetic acid.
2. Experimental
2.1. Materials
Acetic acid and butyl acetate with purities of 99.98 %
(W/W) and 99.50 % (W/W), respectively, were purchased
from Merck. Acetic acid and butyl acetate were used without
further purification. Deionized water was further distilled
before use. Densities were measured with an Anton
Paardensimeter (model 4500), along with some values from
the literature (Weast, 1990).
Table 1. Mole fraction of each substance.
Tube
1 2 3 4
Substance
H2O 0.12 0.26 0.36 0.43
CHCl3 0.54 0.36 0.26 0.20
H3CCOOH 0.37 0.39 0.37 0.36
Figure 2 illustrates the composition of each component of
Table 1. One observation is that there is a decrease of the
molar fractions of chloroform and acetic acid, with the
increase of the molar fraction of water. However, an
important data shows that for the composition
chloroform-water, the acetic acid addition a slight increase
and then immediately decrease more and more, meaning that
the system reaches equilibrium liquid-liquid with greater
ease with lower amount of solvent (acetic acid).The amount
of acetic acid is lower at the beginning in relation the amount
of chloroform, but this phenomenon is reversed immediately,
2.2. Procedure
The binodal curve for the water-chloroform-acetic acid
ternary system was determined by the solubility method.
Binary mixtures of known compositions were shaken in a
glass erlenmeyer (Figure 1) equipped with a microburet with
an accuracy of 0.005 cm3. The third component (acetic
acid)was progressively added until the transition point was
reached. The end point was determined by observing the
transition from a heterogeneous to homogenous a mixture
until a permanent homogenous could be observed. Ternary
mixtures of known overall compositions lying within the
two phase region were prepared shaken thoroughly and then
allowed to reach equilibrium. Samples were carefully taken
from each phase and analyzed to obtain the tie lines. An
electronic balance, accurate to ±0.1 mg, was used during the
experiments.
Figure1. Scheme of chloroform-water mixtures prepared for the
determination of the phase diagram.
3. Results and Discussion
Table 1 shows the mole fractions of all components
obtained from the experiments for he acetic acid solvent at
298.15 K. All points shown are the results of measurements
obtained in duplicates.
5 6 7 8 9
0.49 0.53 0.59 0.62 0.74
0.14 0.11 0.08 0.05 0.02
0.37 0.36 0.34 0.32 0.24
staying always above the composition of chloroform in the
system.
Figure 3 shows the increasing of chloroform composition
but a much larger statement of the composition of acetic acid,
confirmed Figure 2. This can be explained by the fact that
acetic acid having a different interaction with chloroform,
and this is more effective interaction with water,
remembering that this type of analysis same evaluating the
behavior of the two components in the system there is the
other component water.
 American Journal of Physical Chemistry 2013; 2(6): 117-121
Figure2. Curves of the composition of chloroform and acetic acid vs. water
composition obtained for the system water-chloroform-acetic acid at
298.15 K.
Figure3. Binodal curve of system chloroform vs. acetic acid (Mole fraction)
obtained for the system water-chloroform-acetic acid at 298.15 K.
Figure4. Liquid-Liquid equilibria (Mole fraction) for system
water-chloroform vs acetic acid at 298.15 K. (■) solubility (binodal curve)
data for water and (●) chloroform.
In the ternary diagram of Figure 5, the part that lies inside
the solubility curve is the region where two phases in
equilibrium has a microstructure rich in water (blue balls)
but also contains minor amounts of microstructures in other
dissolved components and other microstructure rich in
chloroform (green balls) microstructures which also
contains small amounts of other dissolved. This is because
119
water and chloroform form microstructures partially
miscible, whereas acetic acid (white balls) forms a
microstructure completely miscible in each of them in any
proportion.
Figure5. Ternary diagram with binodal curve and ties-lines (a, b, c) for the
system water-chloroform-acetic acid at 298.15K.
The overall composition of the system with the addition
of acetic acid is shown in Figure 4. This graph depicts in a
partial diagram of the ternary system, because it can identify
nearby where the mole fraction of acetic acid tends to zero,
the composition of the other components (water and
chloroform) are distant or nearly pure as well as in vertices
of the ternary diagram.
Above the solubility line has become a single phase
region, where the three components form a microstructure
completely miscible. The point c'' is defined as the critical
point, ie, where the two curve segments finds itself. At this
point formed two liquid phases with the same composition
and density.
The points a and b represent the combined liquid layers in
the absence of acetic acid. The total composition of the
system is c, so that the lever rule, there is a greater amount
than the layer b of the layer. Adding a small amount of acetic
acid to the system, the composition varies along the line that
joins the vertex c corresponds to acetic acid, the new
composition is represented by c'.The addition of acetic acid
alters the composition of the two layers for the data values a'
and b'. Note that the acetic acid will preferably for the layer
b' rich in water, so that the correlation line between the two
solutions combined a' and b' does not remain parallel to
ab.The relative amounts of a' and b' are given by the lever
rule, that is, the ratio of the correlation line segments a'b',
this segment is referred ties-line or mooring line. With
addition of more acid, the composition varies along the
broken line cC; layer rich in water increases in quantity,
while the other rich in chloroform decreases.
As the correlation lines are not parallel , the point at which
the two solutions combined have the same composition is
not located on top of the binodal curve but is on one side at
the point c'', called lattice point. If the system have the
120 Silio Lima de Moura et al.: Thermodynamic Study of the Liquid-Liquid Equilibrium Water-Chloroform-Acetic Acid
composition initial C and will add acetic acid, the
composition will vary over cc'', immediately below of c'' the
two layers are present in comparable amounts; in c'' the
separation surface between the two layers disappears such as
the solution becomes homogeneous. If we increase the
temperature, the shape and size of the two-phase region will
change.
4. Conclusion
The study ternary system, water-chloroform-acetic acid at
temperature of 298.15 K, may be characterized by an
increase in solubility of a solvent in which was obtained a
microstructure of liquid-liquid equilibrium. In the study of
these microstructures, it can be concluded that the
performance of acetic acid specifically in the binodal curve
presented points of solubilizing effects which according to
the theory of Gibbs are thermodynamically favorable. In the
extreme case of ternary diagram, the substances are arranged
in a microstructure almost pure, that is, without the
formation of a microstructure with another liquid system.
These studies on the microstructures formed in liquid-liquid
equilibrium are important because through these, we can
obtained separation methods increasingly effective.
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