Physical Chemistry

Practical Solutions Chemistry and Chemical

Department of Chemistry
Second year

Aveen AL-Saka
 Determination of phase diagram
for water phenol binary system
(mutual solubility)

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Liquids which are partially miscible, form solutions which
considerably deviate from ideal behavior. Partially miscible
liquid pairs dissolve in each other only in certain limits. Thus
in the case of system water and phenol which are only
partially miscible , phenol will completely dissolve in a
large quantity of water to form a solution of phenol in
.water
If the quantity of phenol is gradually increased, a stage is
reached when a saturated solution of phenol in water is
formed. Further addition of phenol to water will result in
the formation of two liquid layers, one a saturated solution
of phenol in water and the other a saturated solution of
water in phenol
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. Similarly, water will completely dissolve in a large
quantity of phenol to form a solution of water in
phenol.
Thus with high proportions of one of the two liquids,
it is possible to have a completely miscible solution.
But if the proportions taken exceed the saturation
limits, two liquid layers are formed.

The two liquid layers in equilibrium are known as

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It has been observed that at constant
pressure, the mutual solubility of two liquids
. changes with temperature
The four types of liquid pairs. which are
:obtained in actual practice are
.with increasing mutual solubility -1
.with decreasing mutual solubility-2
.with closed mutual solubility-3
4- Type without critical solution temperature.

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 :Type with increasing mutual solubility.1
The two liquids are partially miscible and form two liquid
layers when their proportions are taken outside the
saturation limits (inside the dome shape). For water-phenol
system the lower will consist of a small amount of water
dissolved in phenol and the upper layer will consist of a small
amount of phenol in water. At a given temperature, the
compositions of the two layers in equilibrium with each other
.are definite and can be determined experimentally
As long as two layers are present together and temperature
is constant, there will be no change in the compositions of
.the two layers
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The addition of small amounts of either phenol or water will
merely change the relative volumes of the two layers and not
their compositions. On increasing the temperature, the
mutual solubility of two liquids in the two layers, increases
until at a certain temperature, the composition of the two
layers become the same. Beyond this temperature, the two
.liquids are completely miscible
This temperature, at which the two partially miscible
liquids first become completely miscible, is known as the
critical solution temperature (CST) or consolute
temperature of the system. The composition corresponding
to (CST) is known as critical composition. Above this
temperature, the two liquids are miscible in all proportions
.and thus one layer is possible
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 The variation of mutual solubility of water and phenol with
:temperature is shown in the figure

One phase region

C
⁰C 68.9

T A x
● B

Two phase region

0.0 n m
100
Water Wt%phenol phenol
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At any definite temperature the compositions of the
conjugate solution are given by points on opposite branches
of parabola. This at temperature T, the tie line AB gives the
.composition of the conjugate solutions
point (n) represents composition of water rich layer and
point (m) represent the composition of phenol rich layer.
Between A and B. all mixture yield two layers of
.compositions (n) and (m)
if X represents a system of two layer whose relative
composition are given by (n) and (m). respectively, the
relative weights of the two layers is given by the lever rule
.according to which
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As the temperature is raised the compositions of the two
conjugate solutions gradually approach each other. This is
due to the fact that the mutual solubility of the two liquids
increased with rise of temperature. at the critical solution
temperature (point C which is maximum of the curve), the
two compositions become identical and the two layers
merge into a single layer. This within the parabola, the
system is heterogeneous and represents the range of
.existence of two liquid layers
Outside this parabola the system is homogeneous and
. there is only a single liquid phase

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Type with decreasing mutual solubility -2
There is certain system in which the mutual solubility
decreases with increasing temperature. For such system
the shape of the curve is reversed to type (1) and a lower
critical solution temperature is observed.
As the curve indicates the mutual solubility of water and
triethylamine increases with decrease of temperature. At a
temperature of 18.5C (lower consolute temperature) and
below, the two liquids are completely miscible. The
composition corresponding to the (CST) is found to be 30%
by weight of triethylamine.

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Type with closed mutual solubility -3
In some system both upper and lower critical solution
temperature are exhibited. For such a system there is a
closed solubility curve. For the system water-nicotine,
which belong to this class, the upper (CST) is 208 ºC and
:the lower (CST) is 60.8 ºC. As shown from diagram
Within these two temperatures in the closed area, the two
liquids are partially miscible but outside them they are
completely miscible. It was also found that the
compositions corresponding to the two critical solution
.temperature are same (34% by weight of nicotine)

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:Type without critical solution temperature -4
There are some systems which do not exhibit either an upper
critical solution or lower critical solution temperature. an example
of such a system is ethyl ether-water. These two liquids are
.therefore, partially miscible at all temperature

:Effect of pressure on critical solution temperature

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Effect of impurities on critical solution
:temperature
The impurities have a marked effect on the critical solution
temperature. the effect of impurities on (CST) was first observed by
.Crismer
It was found that
if a substance dissolves in one of the two liquids the upper (CST)
rises and the lower (CST) decreases further.
If a substance dissolves in both the liquids, the upper (CST) will be
.lowered and the lower (CST) will rise
the (CST) is so sensitive to minute traces of impurities that is can be
used as a criterion of purity. Actually (CST) is a linear function of the
.concentration of impurities

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 -:Procedure

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