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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.
2 20 (T , P ) R T ln(1 x1 ) x12
1 2 x1'
x 2
and
2 1
x 2
2
0
c