ADAMSON UNIVERSITY

College of Engineering

Chemical Engineering Department

Manila

Experiment no. 3

SOLUBILITY DIAGRAM OF A

PARTIALLY MISCIBLE LIQUID SYSTEM

Aquino, Kathrine Faye M.

Section: 51018

Schedule: Friday, 10:30-1:30, OZ 403

BS Chemical Engineering, 3rd year

Date performed: January 22, 2016

Date submitted: January 29, 2016

ABSTRACT:

The purpose of this experiment is to determine the solubility diagram for a system that is made up
of two partially miscible liquid components A and B which is phenol and water. This solubility diagram is
an equilibrium composition of solution as a function of temperature and pressure. In the experiment, 80%
phenol solution was prepared. Using a burette, distilled water was added to the phenol solution. The tube
was placed in the water bath and the water in the hot bath was heated with continuous stirring using the
copper stirrer until a clear solution formed. After that, the solution was subjected to air bath with
continuous stirring until the solution became cloudy. The clouding and clearing temperatures were
recorded. The results showed that the increase in water content of the solution decreases the %wt phenol.
The different volume ratios of mixtures prepared were subjected to constant heating and cooling in order
to gather the needed temperature necessary for the construction of the solubility curve of Phenol-Water
solution.

INTRODUCTION:

The mutual solubility or miscibility of two liquids is a function of temperature and

composition. When two liquids (A and B) are partially soluble in each other, two liquid phases
can be observed. At equilibrium, each phase contains A and B in amounts that reflect their
mutual solubility. Some systems are totally miscible (i.e. they form a one-phase liquid) at high
temperatures, but separate into two liquid phases at lower temperatures. These systems have an
upper consolute temperature, T in a plot of temperature versus mole fraction. Other systems are
totally miscible at low temperatures but separate into two phases at higher temperatures giving
rise to a lower consolute temperature, T.

A mixture of liquids is a homogeneous distribution of two or more substances, whereby

all components have a definite vapour pressure. Two liquids may either be completely miscible
or only partly miscible. When the van der Waal forces between the two components are smaller
than those between molecules of the same type, then an increase in the vapour pressure results.
The molecules can leave their arrangement more easily than with equally large attractive forces.
With sufficiently high deviation from Raoult’s law: where

𝑃𝑎 = 𝑃𝑎∗ . 𝑋𝑎
Where:
𝑃𝑎 - Vapour pressure of pure substance A
𝑃𝑎∗ - Partial vapour pressure of substance A in solution
𝑋𝑎 - Molar fraction of substance A

The components of a binary system no longer continuously mix, but instead have the
tendency to again unmixed. A miscibility gap can be observed. This is a range of concentrations
in which the two liquids form two phases. The molar mixing enthalpy is positive. Unmixing
means in this case the transition to a lower energy condition.
Systems with limited miscibility can be presented as isobars in temperature/ mass content
and temperature/ quantity diagrams. In these separation curves, the compositions of the two
coexisting liquid phases, which form from the homogeneous mixture when a certain temperature
has been reached, are plotted as functions of temperature. The coexisting liquid phases are
described as conjugated solutions. They are saturated solutions of the one component in the
other. The line connecting the coexisting liquids is designated as the tie line. Normally the
mutual solubility of liquid components increases with increasing temperature. The coexisting
solutions are identical at a critical dissolving temperature. Above the critical dissolving
temperature the components are miscible with one another in any ratio. The compositions of the
coexisting solutions at certain temperature are constant and independent of the mass ratios or the
two components.

REVIEW OF RELATED LITERATURE:

The solubility diagram is a graph of the equilibrium composition of a mixture as function

of temperature. A solubility diagram for a system made up of two partially miscible liquid
components can be made. Miscible liquid mixtures are being studied in recent researches
(Califano et. al., 2014). A simple phenol-water system can be examined and used in
constructring a solubility diagram.

Solubility and phase diagrams for complex mixtures of soluble and membrane proteins
are being examined in recent studies (Talreja, 2010). Solubility diagrams have many applications
and uses. Analysis of solubility diagrams are made on some important pharmaceutical drugs like
diazepam and nitrazepam (Hadziabdic, 2012). Solubility and phase diagrams for fatty acids are
also being examined in some researches (Tzocheva, 2011).

Heats of mixing of polymers with each other have been measured, the behavior of the
mixtures of solutions of various polymers has been studied, and the dependence of mechanical
properties of polymer mixtures on the ratio of components has been investigated. It has been
shown that mixing of polymers with each other is usually an endothermic process and, therefore,
leads to formation of macroscopically homogenous, but actually microheterogenous, systems
with an extremely high degree of dispersion. These microheterogenous polymer mixtures are
formed because of the enormous viscosity of polymer mixtures, which prevents macroscopic
separation into phases but does not hinder the considerable mobility of the segments of flexible
chain molecules. (Slonimski, 1998)

The terms, miscibility and solubility, are widely used in phase behavior studies of
multicomponent hydrocarbon systems. The distinction between these two terms appears to be
still hazy, leading to their synonymous use in some quarters. (Ayiralam and Rao, 2006)

The phenol-water system is the mixture used in this experiment. Other studies examine
phase and solubility of other systems. For example, in a certain study the liquid-liquid equibria
of the water-acetic acid-butyl acetate system was investigated. (Ince, 2002). Studies are also
made about the equilibria of mixtures involving water -phenol and another third component like
carbon dioxide. (Yoon, 2004)

The study of phenol-water system has many industrial applications. It can be applied to
cases that involve extraction of phenol from industrial water (Jabrou, 2012). It can also be
applied to phenol removal from water in some recent study (Zhang, 2013). Another research
probed the degradation of phenol in water solution by photo catalysis (Laoufi, 2008). A recent
study quantified phenol in surface water by gas chromatography and mass spectroscopy.
(Hossain, 2009)
METHODOLOGY:

Eighty percent of phenol solution was prepared. This was done by using graduated
cylinder. About twenty ml of melted phenol was put in the graduated cylinder and distilled water
was added which was equivalent to one-fourth the weight of the phenol using burette.

The weight of the phenol was recorded. The phenol was transferred to the 50-ml test tube
that is covered with a cork fitted with a thermometer and a copper wire stirrer. Using acid
burette, distilled water was added to phenol solution. Stirred continuously until the solution
turned cloudy. The volume of the phenol solution was recorded.

The test tube was placed in a water bath and stirred until a clear solution was formed. The
temperature of the clear solution was recorded. The tube was removed from water bath and
continuously stirred the solution until the solution turned cloudy. The clouding temperature was
recorded. An additional 1-ml of distilled water was added from the burette and the previous step
was repeated. This was done nine times.

Finally, all the data was recorded in the table. The % weight of pure phenol in all solution
was computed and the density of the eighty percent of phenol solution used is 1.05 g/mL. The
data of the temperature versus the percent weight of phenol was graphed.

RESULTS:

Water add to phenol

Run No. 1 2 3 4 5 6 7 8 9 10
Clearing
70 67 66 64 62 61 60 58 58 56
temperature
(oC)
Clouding
59 60 60 59 59 57 50 53 50 51
temperature
(oC)
Average
64.5 63.5 63 61.5 60.5 59 55 55.5 54 53.5
temperature
(oC)
Volume of
10 10 10 10 10 10 10 10 10 10
phenol
solution
 Weight of
10.5 10.5 10.5 10.5 10.5 10.5 10.5 10.5 10.5 10.5
the phenol
solution
(W1)
Weight of
8.4 8.4 8.4 8.4 8.4 8.4 8.4 8.4 8.4 8.4
pure phenol
Weight of
water added
1 2 3 4 5 6 7 8 9 10
to phenol
(W2)
Total weight
9.4 10.4 11.4 12.4 13.4 14.4 15.4 16.4 17.4 19.4
of solution
(WT)
Weight %
89.36 80.77 73.68 67.74 62.69 58.33 54.55 51.22 48.28 43.30
phenol

GRAPH:

Solubility Curve
70

60

50
Temperature

40

30

20

10

0
0 20 40 60 80 100
%Weight of Phenol
DISCUSSION:

Phenol and water are partially miscible at normal temperatures though the solubility of
both liquids increases with the increasing temperature until the critical solution temperature is
attained and the liquids become completely miscible above this point. Water becomes more
soluble in phenol. In this experiment mixtures of known composition are heated until they
dissolve completely. This is easily recognized by the disappearance of cloudiness due to two
phases.

On the water added to phenol the results showed that as the number of runs increases, the
weight% of the phenol decreases. For the clearing temperature, as the runs increases, the
temperature decreases. On the other hand, in the clouding temperature, as the runs continue, the
temperature becomes unsteady.

If a small amount of water is added to a large quantity of liquid phenol, it gives a single
phase system, which means the solution of water in phenol. When water and liquid phenol are
mixed in ‘comparable’ proportion, a two phase system results in one phase. The solubility of
partially miscible liquids rises with temperature. In this case, the solubility curve exhibits a
maximum temperature of 70°C. The critical solution temperature didn’t attained because as the
%weight of phenol decreases as the temperature decreases.

The possible sources of error are personal errors. Personal errors may appear from the
fault of determining the correct temperature and fault in giving an accurate volume reading.

CONCLUSION AND RECOMMENDATION:

From the water added to phenol, as the volume of water increases, the weight percent of
phenol decreases. Partially miscible liquids become more soluble in each other with increasing
temperature but the critical solution temperature didn’t reached. As the %weight of phenol
decreases, the temperature decreases.

The researchers recommend avoiding any solution of phenol. Also avoid spilling and
clean up immediately with large amounts of water, and to never pipette by mouth.
APPENDIX:

Sample computations:

𝑐𝑙𝑜𝑢𝑑𝑖𝑛𝑔 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 + 𝑐𝑙𝑒𝑎𝑟𝑖𝑛𝑔 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒

𝐴𝑣𝑒. 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 =
2

59 + 70
𝐴𝑣𝑒. 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 = = 64.5℃
2

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑝ℎ𝑒𝑛𝑜𝑙 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑝ℎ𝑒𝑛𝑜𝑙 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 =
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑝ℎ𝑒𝑛𝑜𝑙 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

𝑔
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑝ℎ𝑒𝑛𝑜𝑙 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 1.05 ∗ 10𝑚𝑙 = 10.5𝑔
𝑚𝑙

𝑡𝑜𝑡𝑎𝑙 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑝𝑢𝑟𝑒 𝑝ℎ𝑒𝑛𝑜𝑙 + 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟

𝑡𝑜𝑡𝑎𝑙 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 8.4𝑔 + 1𝑔 = 9.4𝑔

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑝ℎ𝑒𝑛𝑜𝑙
𝑤𝑒𝑖𝑔ℎ𝑡% 𝑜𝑓 𝑝ℎ𝑒𝑛𝑜𝑙 = 𝑥100%
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

8.4
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑝ℎ𝑒𝑛𝑜𝑙 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 𝑥100% = 89.36%
9.4

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