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Silio Lima de Moura, Jos 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
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]:
,
(1)
(2)
(3)
.
.
(4)
118
Silio Lima de Moura et al.: Thermodynamic Study of the Liquid-Liquid Equilibrium Water-Chloroform-Acetic Acid
(5)
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.
(6)
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).
0.12
0.54
0.37
0.26
0.36
0.39
0.36
0.26
0.37
0.43
0.20
0.36
0.49
0.14
0.37
0.53
0.11
0.36
0.59
0.08
0.34
0.62
0.05
0.32
0.74
0.02
0.24
119
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.
Figure5. Ternary diagram with binodal curve and ties-lines (a, b, c) for the
system water-chloroform-acetic acid at 298.15K.
Figure3. Binodal curve of system chloroform vs. acetic acid (Mole fraction)
obtained for the system water-chloroform-acetic acid at 298.15 K.
120
Silio Lima de Moura et al.: Thermodynamic Study of the Liquid-Liquid Equilibrium Water-Chloroform-Acetic Acid
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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