American Journal of Physical Chemistry

2013; 2(6): 117-121
Published online November 30, 2013 (
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: 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

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
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]:



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

within this system is a open homogeneous system in the
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
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]:




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]:

05 0. the acetic acid addition a slight increase and then immediately decrease more and more. . if each step of the system is in equilibrium.1 mg. Thus.98 % (W/W) and 99. 1990). Mole fraction of each substance. An electronic balance. an important data shows that for the composition chloroform-water. Figure 3 shows the increasing of chloroform composition but a much larger statement of the composition of acetic acid. (6) 2 This equation is the Gibbs phase rule. remembering that this type of analysis same evaluating the behavior of the two components in the system there is the other component water.24 Figure 2 illustrates the composition of each component of Table 1. This can be explained by the fact that acetic acid having a different interaction with chloroform. The limitation introduced by the equation of Gibbs-Duhem causes one of the variables is dependent. and this is more effective interaction with water.36 0. Acetic acid and butyl acetate were used without further purification.36 0.08 0. P and chemical potential µi for a single phase.37 0.005 cm3.53 0. Scheme of chloroform-water mixtures prepared for the determination of the phase diagram. One observation is that there is a decrease of the molar fractions of chloroform and acetic acid. only n+1 are independent. Table 1. staying always above the composition of chloroform in the system. Results and Discussion Table 1 shows the mole fractions of all components obtained from the experiments for he acetic acid solvent at 298. Therefore.36 0. 3.26 0. accurate to ±0.50 % (W/W). Samples were carefully taken from each phase and analyzed to obtain the tie lines. All points shown are the results of measurements obtained in duplicates.62 0.14 0.: Thermodynamic Study of the Liquid-Liquid Equilibrium Water-Chloroform-Acetic Acid ∑ (5) 0 This equation introduces a restriction on simultaneous variation of T. meaning that the system reaches equilibrium liquid-liquid with greater ease with lower amount of solvent (acetic acid). (3) and (4). were purchased from Merck. Ternary mixtures of known overall compositions lying within the two phase region were prepared shaken thoroughly and then allowed to reach equilibrium.32 0. Deionized water was further distilled before use.37 0. The end point was determined by observing the transition from a heterogeneous to homogenous a mixture until a permanent homogenous could be observed. but this phenomenon is reversed immediately. Figure1.20 0. In this paper. 2. Then the number of degrees of freedom.12 0. If the heterogeneous system as a whole is in equilibrium. However. Tube Substance H2O CHCl3 H3CCOOH 1 2 3 4 5 6 7 8 9 0.54 0.43 0. the total number of independent variables is p(n+1). we herein report liquid-liquid equilibrium results at temperatures of 298. it is said that a phase has n+1 degrees of freedom. was used during the experiments. Materials Acetic acid and butyl acetate with purities of 99.49 0. which is the number of intensive variables minus the number of relations or constraints are [22]: 1 1 2.39 0. Binary mixtures of known compositions were shaken in a glass erlenmeyer (Figure 1) equipped with a microburet with an accuracy of 0.The amount of acetic acid is lower at the beginning in relation the amount of chloroform. Procedure The binodal curve for the water-chloroform-acetic acid ternary system was determined by the solubility method. then there are (p-1)(n +2) equilibrium relationships between the p(n+1) variables given by the equations (2).02 0.118 Silio Lima de Moura et al. Experimental 2.26 0.2.34 0.1. Densities were measured with an Anton Paardensimeter (model 4500).11 0. respectively. The third component (acetic acid)was progressively added until the transition point was reached. the n+2 variables that can be used to characterize a phase.59 0.74 0. with the increase of the molar fraction of water.15 K.37 0.36 0. we evaluate acetic acid as an agent for the extraction of chloroform from dilute aqueous solutions. along with some values from the literature (Weast. confirmed Figure 2.15 K for the ternary system of water-chloroform-acetic acid. Thus.

The addition of acetic acid alters the composition of the two layers for the data values a' and b'. (■) solubility (binodal curve) data for water and (●) chloroform. while the other rich in chloroform decreases. the ratio of the correlation line segments a'b'. Figure5. the new composition is represented by c'. This graph depicts in a partial diagram of the ternary system. 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''. Binodal curve of system chloroform vs. that is. ie. this segment is referred ties-line or mooring line.The relative amounts of a' and b' are given by the lever rule. acetic acid (Mole fraction) obtained for the system water-chloroform-acetic acid at 298. Figure4. c) for the system water-chloroform-acetic acid at 298. water composition obtained for the system water-chloroform-acetic acid at 298. 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. The point c'' is defined as the critical point. because it can identify nearby where the mole fraction of acetic acid tends to zero. Curves of the composition of chloroform and acetic acid vs. whereas acetic acid (white balls) forms a microstructure completely miscible in each of them in any proportion. the composition of the other components (water and chloroform) are distant or nearly pure as well as in vertices of the ternary diagram. With addition of more acid. b. 2(6): 117-121 119 water and chloroform form microstructures partially miscible.15K. so that the lever rule. The points a and b represent the combined liquid layers in the absence of acetic acid. At this point formed two liquid phases with the same composition and density.15 K.American Journal of Physical Chemistry 2013. Figure2. Above the solubility line has become a single phase region.15 K. The total composition of the system is c. there is a greater amount than the layer b of the layer. where the two curve segments finds itself. where the three components form a microstructure completely miscible. called lattice point. This is because The overall composition of the system with the addition of acetic acid is shown in Figure 4. layer rich in water increases in quantity. If the system have the . Figure3. In the ternary diagram of Figure 5. the composition varies along the broken line cC. the composition varies along the line that joins the vertex c corresponds to acetic acid. As the correlation lines are not parallel . Liquid-Liquid equilibria (Mole fraction) for system water-chloroform vs acetic acid at 298. Note that the acetic acid will preferably for the layer b' rich in water.15 K. Adding a small amount of acetic acid to the system. Ternary diagram with binodal curve and ties-lines (a. so that the correlation line between the two solutions combined a' and b' does not remain parallel to ab.

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