BINARY LIQUID-VAPOR EQUILIBRIUM OF AN AZEOTROPIC MIXTURE

Faybelle Ayuban October 5, 2018

Abstract

Phase diagrams offer much more information about a system than the phases that exist
on a particular system given a specific temperature and composition. An azeotrope is defined as
the point where the liquid and vapor phase contain equal amounts of each composition. An
azeotrope temperature can be determined from phase diagrams. The system under study is an
isopropanol-water where the experimental azeotropic temperature is found to be at 75.5℃.

I. Introduction
The main purpose of phase diagrams is to offer empirical information about the
physical changes mixtures can undergo under different conditions. Phase diagrams can
be in the form where with temperature or pressure is in the y-axis and composition in
the x-axis. A temperature-composition is the form of phase diagram used since it is
generally more feasible to study varying temperature conditions than it us to studying
varying pressure conditions. In liquid-liquid systems, a phase diagram can be mapped
out while the liquids are considered as partially miscible. The degree of freedom would
be one, implying that one variable, pressure, is held constant. In increasing the
temperature, the partially miscible substances tend to avoid each other, forming an
azeotrope. It is defined as a mixture that boils without changing its composition. As a
distillation progresses for low boiling azeotrope, shows a minimum, implying that the
interactions between two substances are unfavorable and they would repel each other
instead. [1]
The objectives of the experiment are as follows:
1. Plot a phase diagram from the data gathered.
2. Determine the experimental azeotropic temperature.
II. Experimental Method
Location and Duration
The experiment was conducted on October 1, 2018 at Central Mindanao University,
Musuan, Maramag, Bukidnon.

Chemicals, Apparatuses, Equipment

The following are chemicals and equipment used during the experiment: analytical
balance, distilling flask, hot plate, condenser, rubber tubing, adapter, Erlenmeyer flask,
vials, pipette, rubber aspirator, fume hood.
 General Experimental Approach
Solutions were prepared to mole fractions of 0, 0.1, 0.3, 0.5 and 1.0 isopropyl
alcohol to water. Each solution was then distilled, where the second drop of distillate
was collected and its density was determined using weighed vials.

III. Results and Discussion

From the calibration curve, density of each solution with differing mole fraction was
obtained to create an equation of the line. From the equation of the line, the density of the
liquid and vapor compositions were substituted as y to obtain their respective compositions, in
the form of x. The results are summarized on the Table 1 below. From the table given, a phase
diagram can be constructed, given in Figure 1.

Table 1. Table of treated data and results

Composition Composition
Temperature
in Liquid in Vapor
°C
xPrOH yPrOH
1.1543 1.3646 74.0
1.0543 1.3282 76.5
1.0761 0.9516 75.5
1.000 1.0000 82.6
0.1519 0.1810 94.0
0.0000 0.0000 100.0

100
Azeotropic
temperature
Temperature, °C

0 1
Composition, xPrOH
Figure 1. Isopropanol-water binary system phase diagram
 As observed in the graph, the experiment was not in all an accurate one since the
appearance of the graph deviates significantly from ideal graphs. The orange curve presents the
vapor phase composition while the blue curve presents the composition in liquid phase. The
vapor ideally must contain more alcohol since it is more volatile, it would escape from the liquid
phase and into the vapor phase, saturating the vapor phase. A distillate produced from this
fractional distillation, called as such because sets of distillates may be collected leading to a
pure distillate and that the difference in their boiling points are not too large, is a mixture of
both the vapor and liquid compositions saturated with the more volatile component.

The graph is a plot of the boiling points in particular compositions. The ideal graph for
this has a curve with a generally downward slope, which is due to the decrease in the boiling
point of the less volatile component. The system in the experiment is an obvious deviation from
this ideal behavior. Despite of that, the phase diagram still successfully portrayed how liquid
mixtures are affected in the presence of each other.

The experiment studies a system of isopropanol-water in different mole fractions. Since

isopropanol is an alcohol, it has a polar hydroxyl and a nonpolar methyl group while water is
polar, one might lead to believe that the interaction between two substances, due their
polarities, would be favorable. This is accepted only for ideal solutions where interactions
between molecules are negligible. However, it is not an ideal solution and therefore would
deviate from its expected behavior. The presence of the bulky methyl group hinders hydrogen
bonding. This accounts for the ideal appearance of a minimum azeotrope phase diagram; where
the components of the system repel each other. The azeotrope is seen to form in the straight
line region of the graph which implies that the mixture has its lowest boiling point in those
conditions. According to literature, the composition of the azeotrope for this system is around
0.6 to 0.8 at a temperature below the boiling point of the more volatile component, which is the
isopropanol at 82.6 ℃. The experimental azeotropic temperature is found to be 75.5℃.

The sources of errors include high temperature setting on the hot plate used to boil the
mixture. The effect of this was the azeotropic temperature cannot be properly observed since
the temperature set, 300℃, is far too high from the azeotrope’s boiling point, which becomes
easily bypassed. The introduction of high temperature to the mixture directs the system to a
more abrupt molecular change. The presence of inorganic ions in the water, for example, leads
to the water having a higher boiling point than normal. The same event happens to the system
studied. Since the values used were obtained from literature, the effects are cancelled.

IV. Conclusion
The azeotropic temperature is experimentally 75.5℃, determined from the phase
diagram.
V. References

Atkins, P. & de Paula, J. (2014). Physical chemistry thermodynamics, structure, and change.
10th Ed; W.H. Freeman and Company, NY.