Group Leader: Jean Criste T.

Cainila Date Performed:

August 25, 2009
Group No.3 Date Submitted: September
2, 2009
4ChE-B Professor: Philipina A.
Marcelo,Ph.D.

Experiment 2:
Partially Miscible Liquids:
Determination of Mutual Solubility

I. Introduction

The objective of the experiment is to determine the solubility of two partially miscible
liquids, construct the mutual solubility curve for the pair and determine their critical solution
temperature.

Miscibility means how completely two or more liquids dissolve in each other. It is a
qualitative rather than quantitative observation—miscible, partially miscible, not miscible.

Like any other solubility phenomenon, miscibility depends on the forces of attraction
between the molecules of the different liquids. The rule of thumb "like dissolves like" means
that liquids with similar molecular structures, in particular similar polarity, will likely dissolve
in each other. (Polarity means the extent to which partial positive and negative charges
appear on a molecule, because of the type and arrangement of its component atoms.)
However there are some substances with varying polarity like water which will play a vital
issue on how solute will dissolve in it.

Volume vs Solute

The above diagram shows the solubility trend mostly occuring in solid-liquid
solutions. The level of concentration of the dissolved solute can be classified as saturated,
supersaturated and unsaturated solution. Saturated solution is attained when the maximum
amount of solute a solvent can dissolve has already been reached. The saturation point of
a solution is represented graphically by points along the straight line. On the other hand,
unsaturated solutions are those when the maximum amount of solute dissolved is not yet
reached by the solvent. The unsaturated region is represented by the lower region of the
graph(below the line).Lastly, a supersaturated solution is attained when the maximum
amount of solute is exceeded and precipitation are evident. The supersaturated solution
takes the section above the saturation line. This however can be altered depending on the
temperature on which dissolving takes place. For solubility depends highly on temperature.

For a liquid-liquid solution, it is but normal for components to be immiscible at the

moment they are introduced to one another however they will be miscible once stirred or
mixed. In some cases some liquiid-liquid solutions can be completely immiscible even if
 stirring and mixing and other alteration has already been made. Liquid systems that can
break up into two liquid phases are the simplest of two-component phase diagrams. Such
systems are usually treated at some constant pressure high enough to ensure that no vapor
can occur in equilibrium with the liquid phases and over a range of temperatures high
enough to ensure that no solid phase appear. The region of the components signifies that
there are regions of pure component A and B but there is also a region where in a part of A
is dissolved in B and vice-versa. This is now characterized as the partial miscibility of a
certain liquid-liquid solution. Such solutions are heated and cooled to attain at constant
pressure to attain the complete homogeneity of the solution or complete miscibility. The
graph below shows the trend for partially immiscible liquids that are either heated or cooled.

Partial Miscibility Plot

From the figure above it is noticeable that a peak or maximum temperature is

reached by the solution but it the maximum temperature of the solution differs into some
extent to the critical temperature of a solution. The critical temperature of a solution marks
the point wherein the solution will be completely miscible either if the temperature is lowered
or increased. More of critical temperature will be discussed on the latter part of the analysis

As been stated ealier miscibility is a solubility phenomenon, thus, it can also be

affected by factors which plays an important role in a substance solubility. The factors are as
follows: (1) nature of solute/solvent, (2) temperature and (3) pressure. For liquid and solid
solution pressure does not affect much of their solubility. Temperature on the other hand will
depend whether the reaction results to an endothermic or exothermic process, if
endothermic the solubility of the solution will increase with an increase in temperature. For
an exothermic process, solubility will increase with a decrease in temperature. The nature of
solvent and solute also take part in its solubility, such nature involves polarity and molecular
size. Polarity was discussed earlier stating that “likes dissolves like”. While larger molecules
are less soluble than that of the smaller ones.

If the phase rule is applied in this two-phase mixture, two variables are needed to be
specified to describe the system completely. The phase rule calculation is shown below.
P=c–p+2
=2–2+2
=2

At constant pressure, the remaining significant variables are temperature and

composition. The composition is uttered in percent by weight. Usually, both liquids become
more soluble as the temperature is increased, and eventually a critical solution temperature
is reached above which the two liquids are completely miscible. An upper critical solution
temperature will be observable, the highest temperature at which phase separation occurs.
On the other hand, some systems show a lower critical solution temperature below which
the components mix in all proportions and above which the components form two phases.

II. Methodology
 Preliminary procedures were done before the actual experiment. The density of
phenol was obtained from literature and the amount of water required to prepare 5% to 95%
phenol at 5% increment, starting with 10 mL phenol in each proportion, was calculated.
95% phenol-5% water by weight mixture was prepared based on 10 mL phenol. The
mixture was heated with mild stirring until the cloudiness disappeared, the temperature of
which was recorded. The mixture was then cooled with mild stirring until the cloudiness
reappeared, the temperature of which was recorded. The process was repeated until fairly
constant readings were observed. Water was added to make 90% phenol and 10% water.
The procedure was repeated until 55% phenol. For 5% to 50%, 5 mL phenol was initially
used.
III.Discussion of Results

Different changes were observed and noted in the experiment. After the 95% phenol-
5% water by weight solution was prepared, the mixture was heated in a water bath with mild
stirring and recorded its constant temperature until the cloudiness of the solution
disappeared and cooled instantly until the cloudiness reappeared. It is observed that the
turbidity, which signifies the partial immiscibility of the liquids, is highly dependent on
concentration of mixture and temperature. If the mixture is highly concentrated to either
water or phenol, after the mild stirring in room temperature there would be no visible
cloudiness observed. It is seen in the 5% and 95% phenol-water solution that no cloudiness
appeared because both exhibits almost a pure compound. In the 80, 85, and 90% it is noted
that there was cloudiness before heating the mixture and required a certain heating
temperature to make the mixture miscible. In the cooling process, however, it is observed
that no cloudiness reappeared. The reason for this is that just a certain small amount of heat
can make the solute and solvent miscible but once the equilibrium is established, the
mixture is hard to separate into two components. An account to the said results is seen on
Table I.
Table I: Values of the temperature for each increment

HEATING COOLING
% by Weight
Temperat Temperat
Phenol-Water
ure ure
Solution
(ºC) (ºC)
5 No change No change
10 40 38
15 58 56
20 65 63
25 66 64
30 66 65
35 66 65
40 66 65
45 66 66
50 66 64
55 64 58
60 63 58
65 55 54
 70 45 42
75 41 30
80 34 No change
85 30 No change
90 29 No change
95 No change No change

The heating and cooling temperatures gradually increase but as it reached a certain
constant high temperature, it gradually decreases. It is seen on the 45% mixture that the
heating and cooling temperature is the same. It is where, after heating the solution and
putting in the ice bath, the cloudiness immediately reappears.
The temperature versus percentage by weight phenol mixture was plotted in order to
determine the critical solution temperature of the mixture and is seen in Graph 1.

Graph 1

Critical solution temperature is the temperature at which a mixture of two liquids

immiscible at ordinary temperatures, cease to separate into two distinct phases. The red
line symbolizes the temperature reading of phenol mixture in the hot water bath while the
blue line is the temperature reading of phenol mixture in the cold water bath.

To clearly see the single and double-phase regions, the lines were set to polynomial
trend line forming smooth curves. The dotted lines represent the temperature at which the
cloudiness of the mixture disappeared in the heating step and said to be the state where the
mixture is single-phase. The dashed lines represent the temperature at which the cloudiness
reappeared in the cooling step and said to be the point in which the mixture began to
separate and became double-phase. It is seen in the graph that there would be a region
created in the intersection of the dotted and dashed line. This region is a single-phase
region in which the phenol and water are miscible. Beyond this region would be a double-
phase in which the mixture is said to be partially miscible or immiscible.

Critical solution temperature is the temperature which will lead to separation of the
mixture into two distinct liquid phases. This is denoted by the intersection of the polynomial
trend line of the heating and cooling temperature. The critical temperatures at which the
lines intersect are 63ºC and 66ºC.
IV.Answers to Questions

1. Two types of liquid-liquid critical points are the upper critical solution temperature, or,
which denotes the warmest point at which cooling will induce phase separation, and
the lower critical solution temperature, which denotes the coolest point at which
heating will induce phase separation. Based on Graph 1, the maximum temperature
is 66ºC and the minimum critical solution temperature is 63ºC.

2. The different temperature readings have very small differences. Thus, the
temperature readings were constant.
 3. The high phenol concentration of percentage of phenol-water mixture solidifies
during cooling process mainly because of phenol’s freezing point. At 41˚C, phenol
forms into a solid that can be liquefied by a very small amount of water. Thus, a high
concentration solution of phenol with water would solidify on lower temperatures.

4. Given an unknown solution of the components, its concentration will be known by the
use of the mutual solubility plot/graph. The composition of a layer can be determined
by getting the critical solution temperature experimentally and plotting the point on
the graph. The weight percentage could be obtained at the point where in the
temperature intersects the curve.
I. Conclusions

In this experiment, it is concluded that the solubility of two partially

miscible liquids could be determined by constructing a mutual solubility curve for the pair of
liquids. Turbidity of the mixture signified two-phase mixture and the cloudiness could
disappear and reappear depending on the heating and cooling temperature at which the
mixture became one-phase. The heating and cooling temperatures gradually increased but
as it reached a certain constant high temperature, it gradually decreased.

It is also concluded that in the plot of the mutual solubility curve, a region was
enclosed and signified the single-phase stage of the mixture. Beyond that region, the
mixture is of double-phase. The intersection of the trend lines for heating and cooling would
be the critical solution temperature of the mixture and was found to be approximately 63ºC
and 66ºC.

II. References

[1] Atkins, Peter & De Paula, Julio. Atkins’ Physical Chemistry, 7th ed. (Oxford University
Press Inc., New York, 2002.)

[2] Barrow, Gordon M. Physical Chemistry, 6th ed. (The McGraw-Hill Companies Inc., USA,
1995) pp. 327-330

[3] Daniels, Farrigton and Alberty, Robert. Physical Chemistry, 2nd ed. (John Wiley & Sons,
Inc., USA, 1961) pp. 241-243

[5] http://science.jrank.org/pages/4382/Miscibility.html

[4] http://www.citycollegiate.com/chapter3d.htm

[6] http://www.sciencebyjones.com/solubility.htm