Experiment 6: Solubility Diagram of two Partially Miscible Liquids

Determination of critical solution temperature of water-phenol system.

Abstract
When a small quantity of phenol is mixed with water and shaken, the phenol undergoes
dissolution, resulting in a single layer. When larger phenol quantities are added, there are two
layers of liquids formed. The lower layer is made of small amounts of water dissolved in
phenol and the upper layer consists of phenol dissolved in water. Two partially miscible
liquids may become completely miscible at a higher temperature since solubility increases
with temperature generally. This miscibility temperature is different for different
compositions of the mixture. The highest miscibility temperature is called the critical solution
temperature or CST. Above this temperature, all compositions of this mixture are completely
miscible.
Introduction
To determine the conditions existing in a system of two liquids that are partially miscible, the
physical properties of the solutions on both sides of the solubility curve were measures. This
was done over the whole range of concentrations at a series of temperatures up to and above
the critical solution temperature. The water-phenol system was used in the experiment, and
the densities of the solutions of phenol in water and water in phenol were determined every 10
degrees between 20 degrees and 70 degrees. The densities of the conjugate solutions were
measures frequently near the critical solution temperature.
Procedure:
1. In a clean dry test tube (phenol tube) weigh accurately about 1 g phenol.
2. From a burette, add 0.5 ml of distilled water. Cover the tube with a cork stopper carrying a
thermometer and a stirrer, and then place in a beaker containing water to serve as bath.
3. Heat (or cool) gradually while the mixture is constantly stirred until the two layers
disappear forming one homogeneous layer. The two temperatures (T1 and T2), at which
this occurs on passing from a lower (T1) to a higher (T2) temperature and the reverse, are
recorded. These two temperatures should be nearly the same, and their mean gives the
miscibility temperature of the mixture used.
4. To the same mixture add the necessary volumes of water (0.5, 1, 1.5,…) and heat
gradually, then determine the miscibility temperature of the new mixture as described
above.
Calculations:
1. Record the volume of water used for each composition.
2. Plot miscibility temperature against percentage water or phenol for the various mixtures.
3. From the curve obtained find out the critical solution temperature and the corresponding
composition.
Results and Discussion
For a binary mixture of two partially miscible liquids e-g phenol and water the ‘certain
condition’ heterogeneous phase is formed under it studied by continuous adding of water in
phenol until a saturated solution of water in phenol obtained. Thus continuous adding of water
in phenol results saturated solution of phenol in water after a certain time. So two phases
form. On increase in volume of water first phase ( i.e water in phenol) decreases and second
phase ( i.e phenol in water) increases. Here component 2, phase 2, so degrees of freedom
(F)=2-2+2=2 i.e Bivariant . In this experiment if pressure remain constant then, F=2-2+1=1 i.e
univarient system. With increase in temperature mutual solubility increases . At a certain
temperature the mutual solubility curve attain maximum, this temperature is called critical
solution temperature (CST)or consolute temperature (CT) and corresponding composition is
called consolute composition . Under a constant pressure above the CST the homogeneous
phase is obtained. For phenol water system the critical solution temperature is 65.9℃ and
consolute composition is 34% The expected mutual solubility curve is as follows

Phase 1 is heterogeneous phase consisting of binary mixture of phenol and water. Phase 2 is
homogeneous phase. The composition can be calculated by drawing tie line in the curve
‘between A and A’. In the point A and A’, no of phase two, component 2 so degrees of
freedom F=C-P+1 = 2-2+1= 1 i.e univarient so this expressed as line. In the phase 2, no of
phase (p) = 1 component 2, so F=2-1+1=2 i.e bivarient so it is expressed by area. In the point
x’ i.e critical solution temperature, F=0 i.e invariant so this expressed as point. Under constant
pressure, we carry out the experiment by adding water in phenol and for each solubility
temperature will be noted. Then the temperature vs. Weight percentage of phenol will be
plotted. From the graph, obtained maximum solubility temp and its corresponding
composition; those will be critical solution temperature(CST) and con solute composition of
phenol respectively. And this will be studied using the law of rectilinear motion.