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Liquid-Liquid Equilibrium in 2-Components Systems.

Determination of the
Solubility Curves (at Equilibrium) of the Phenol-Water System

Theoretical aspects
It was established experimentally that some liquids dont form, on mixing a
homogenous system (one phase).The system has 2 phases and the study of it is
based on the thermodynamic model of the liquid (L1)-liquid(L2) equilibrium.
In the case of a 2 components system, the two phases contain both
components, but in different proportions. In order to describe these systems we
introduce the notion of partial miscibility (solubility).A limit case is the one when
each phase, L1 and L2, contains practically only one of the components, these
being immiscible.
The thermodynamic conditions are:
T L1 TL2

PL1 PL2

1L (T , P, xi' ) 2L (T , P, xi'' );
1

i 1,2

, which means that the temperature and pressure are constant and the chemical
potential are equal in the 2 phases. The 4 variables which characterize the
equilibrium state are: T, P , xi, xi.
The phase law is: l = C-F+2, l=number of degrees of freedom
F=number of phases
C=number of components
For the type of system studied in this experiment l=2. So, if the 2 variables
are fixed (for example T and P) the others will depend on these. So a variation of
the temperature at constant pressure will imply a variation in the composition of
the phases. Several systems have been studied and it was observed that an increase
of temperature determines the decrease of the difference between the compositions
of the 2 phases until it becomes 0 (the corresponding temperature is called T c,
(critical temperature), meaning that the system is reduced to a single phase.
The graphical representation of the phase composition for different
temperatures is represented by an equilibrium curve (also, solubility curve) of the
system, characterized by a maximum .There exist systems with a maximum critical
temperature of dissolution, systems with an inferior critical temperature of
dissolution and also systems which present a closed solubility curve (having 2
critical temperature: a maximum and a minimum one).
A simple model that describes the behavior of systems with a maximum
critical temperature is the model of the ideal solutions, whose activity coefficients
of the components are:

1E R T ln 1 (1 x1 ) 2
2E R T ln 2 x12

, represents a constant.

The chemical potentials are given by the following relations:


1 10 (T , P ) R T ln x1 (1 x1 ) 2

2 20 (T , P ) R T ln(1 x1 ) x12

10 , 20 are the standard chemical potentials of the pure components

By introducing eq. 2,5 in the equilibrium conditions (1), we obtain:


R T ln x1' (1 x1' ) 2 R T ln x1'' (1 x1'' ) 2
R T ln(1 x1' ) ( x1' ) 2 R T ln(1 x1'' ) ( x1'' ) 2

In the case of the symmetrical curves: x 1=1-x1. Putting this condition in


eq.6 we obtain:
R T ln x1' (1 x1' ) 2 R T ln(1 x1' ) ( x1' ) 2
or : T

1 2 x1'

R ln[(1 x1' ) / x1' ]

The critical point is when:


1

x 2

and

2 1

x 2
2

0
c

So: (x1)c= 0.5 and Tc= /2R


Eq.9 can be written in the following form:
1 2 x1'
T 2Tc
ln[(1 x1' ) / x1' ]
and represents the solubility curve for the model of ideal solutions. The theoretical
results are not very close to the experimental ones and so more complex models
were proposed (Laar , NRTL, UNIQUAC equations etc).
As an empirical rule, it was established that the mean average of the
compositions of the 2 phases in equilibrium is a linear function of temperature and
that the intersection between the line obtained from these mean values with the
solubility curve corresponds to the critical temperature of dissolution (the rule of
the linear diameter).This rule is better reflected when mass fractions are employed.
Working procedure

We introduce in a test tube E a mixture of 5g of phenol and a known


volume (2, 4, 6, 10, 14, 20, 25, 30, 35) of water.
Heat the water bath. By increasing the temperatures, the 2 phases which
form an emulsion, pass from a single homogenous liquid phase, at a certain
temperature marked by the disappearing of the opalescence. This temperature is
written down.
Cool the system and write down the temperature at which the second phase
appears again. Take the average of the experimental values in order to determine
the dissolution temperature of the mixture. Proceed in the same manner for the
following compositions of the mixture.

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