Lab 6 Liquid-Vapour Equilibrium Azeotropic Mixtures

Performed on November 3, 2015, November 10, 2015, and November 17,

2015
By Amanda Grennan
Partners: Justin Williams and Alisha Marks
Submitted to: David Duncan
On November 24, 2015

Objective

To determine and construct a temperature-composition diagram for a twocomponent liquid system with a minimum or maximum boiling mixture.
Procedure
David H. Duncan (2015). Physical Chemistry Laboratory Manual Fall 2015. P.
22-24.
Observations
Isopropyl alcohol
Lot# KNG221
Exp 07/22/17
Company: VWR
Modification: 160mL solutions were made not 500mL.
It is assumed that the solution of water and isopropyl alcohol is completely
miscible because no layers formed when the two liquids were mixed together
in the round-bottom flask. Each solution was clear and colourless. Each gave
off a pungent alcohol odour except for pure water. The round bottom flask
was thoroughly cleaned and was rinsed with a small amount of acetone in
between each distillation.
Table 1: Week
Hot or Cold
Bath
Ice bath
Boiling water
bath

1 Temperature Readings
RBF
Distillate
Thermometer Thermometer
5.0C
6.0C
100C
100C

Table 2: Week 1 Results

Mixture
Boiling
temperature
in RBF
Pure
90C
isopropyl
Pure
90C
isopropyl
redo

Temperature
of distillate

Digital
Time
Thermometer
10:40am
5.6C
10:35am
102C

81C

Refractive
index of RBF
liquid
1.5640

Refractive
Index of
distillate
1.3180

82C

1.3770

1.3770

Table 3: Week
Hot or Cold
Bath
Ice bath
Boiling water
bath

2 Temperature Readings
RBF
Distillate
Thermometer Thermometer
5.0C
5.0C
100C
100C

Table 4: Week 2 Results

Mixture
Boiling
temperature
in RBF
Pure water
103C
25% water
83C
Table 5: Week
Hot or Cold
Bath
Ice bath
Boiling water
bath

Temperature
of distillate
91C
72C

3 Temperature Readings
RBF
Distillate
Thermometer Thermometer
1C
3C
95C
102C

Table 6: Week 3 Results

Mixture
Boiling
temperature
in RBF
75% water
81C
50% water
81C
40% water
80C

Temperature
of distillate
79C
81C
80C

Digital
Time
Thermometer
10:20am
4.5C
10:30am
100C

Refractive
index of RBF
liquid
1.3330
1.3730

Refractive
Index of
distillate
1.3335
1.3735

Digital
Time
Thermometer
10:15am
1.7C
10:20am
100.2C

Refractive
index of RBF
liquid
1.3450
1.3620
1.3670

Refractive
Index of
distillate
1.3730
1.3735
1.3745

Mole fraction calculation example:

25% water:
Density of water: 0.9970g/mL
Density of isopropyl: 0.786g/mL
Mass of water = D x V = (0.9970g/mL) x (40mL) = 39.88g H2O
Mass is isopropyl = D x V = (0.786g/mL) x (120mL) = 94.32g C3H8O
39.88g H2O / 18.02g/mol = 2.213 moles H2O
94.32g C3H8O / 60.1g/mol = 1.569 moles C3H8O

Mole fraction water =

2.213moles water
2.213 moles water +1.569 moles isopropyl

= 0.585

Graph 1: Mole Fraction of Water vs Temperature

Graph 2: Mole Fraction of Water vs Indices of Refraction

Graph 3: Thermometer Reading vs Expected Reading

102
100

5
0

Discussion
Two curved lines are shown in Graph 1 comparing the mole fraction of water
vs temperature readings. Below the lower curved line, only liquid exists, and
above the upper curved line, only vapour exists. The area between the two
curved lines both phases coexist. An azeotrope is a liquid solution that boils
at a constant temperature at a certain composition. When this occurs, the
solution behaves as if it is one component with one constant boiling point.
When a liquid boils at its azeotropic composition it produces a vapour of
exactly the same composition as the liquid. This liquid does not change its
composition as it vapourizes. Since the vapour and liquid have the same
concentration, its components are unable to separate by distillation
depending on their volatility. By referring to Graph 1, the results obtained
from the experiment demonstrate an azeotropic point of about 0.77 mole
fraction of water (40% water by volume) at about 81C. This point was
determined by referring to Graph 1 where the two lines intersect, indicating
that there is a constant temperature. Graph 2 demonstrates the relationship
of the mole fraction of water and the indices of refraction of both the
distillate and the mixture remaining in the RBF. The RI of the distillate
showed a different pattern than the RI of the liquid remaining in the RBF. The
RI of the distillate remained constant until the pure water sample. The reason
for the distillate RI to remain constant is because it contained only isopropyl
alcohol due to the fact that is it more volatile than water. Isopropyl alcohol
has a boiling point of 82.6C whereas water has a boiling point of 100C;
therefore the distillate would contain isopropyl resulting in the RI to remain

constant for every mixture except for pure water. The refractive indices of
the pure samples were the same, which was also expected.
The theoretical azeotropic point of an isopropyl alcohol/water mixture is
isopropyl alcohol is 87.9% by weight isopropyl and 12.1% by weight water.
Assume 100g:
87.9g C3H8O / 60.1g/mol = 1.463mol C3H8O
12.1g H2O / 18.02g/mol = 0.314mol H2O
0.314 mol
Mol fraction water =
= 0.314
(0.314 mol +1.463 mol)
Therefore, the theoretical azeotropic point of an isopropyl alcohol/water
solution is 0.314 mole fraction of water, which is roughly about 15% water by
volume. This indicates that the experimental results have an error of about
30%.
There are numerous possible sources of error in this experiment. A significant
source was the error associated with the thermometer readings. Prior to each
distillation performed, the thermometers were calibrated to determine the
+/- error that could occur from each temperature reading during the
distillation. By referring to Graph 3, it can be seen that the temperature
readings of both thermometers were slightly higher than expected
temperatures (thermometer temperature is orange; expected temperature is
green). Both thermometers read ice baths to be within +5C of the expected
temperature of 0C. Both thermometers read boiling water baths to be within
+/- 5C from the expected temperature of 100C. This allows for a great
amount of error to occur because during the distillation a thermometer could
give a temperature reading that is possibly off by 5C. If both thermometers
are off by 5C it would cause a very significant change to the results. This
could explain why pure isopropyl and pure water did not have consistent
temperature readings when theoretically they should have. This would also
explain why the temperature reading of boiling water was 103C which is not
possible. Another possible error could be that the RBF was heated too rapidly.
It is important that the RBF is heated at a slow constant pace to ensure that
the most accurate temperature readings are taken. The distillate will also
start dripping too fast if the RBF is heated and boiled too quickly which could
potentially affect its refractive index. The theoretical azeotropic point for
water/isopropyl is 0.314 mole fraction of water; however, this mixture was
not tested in the lab. This lab could have been performed better if the
theoretical azeotropic mixture components were calculated prior to
completing the experiment, to ensure that the mixture would have been
tested.
Questions

1. Index of refraction, also called the refractive index, measures the

bending of a ray of light when it passes from one medium to another. It
is the measure of difficulty for light to travel through a media. It is a
ratio of the velocity of light in a vacuum to its speed in that substance.
Because it is a ratio, it is unitless.
2. The index of refraction of a solution can be used to determine the
solution composition if the components are known by finding the
refractive index of the known components and do a ratio calculation to
determine the mole fraction of each component.
3. Yes, a tie-line can be used to determine compositions of a mixture at a
given temperature with an azeotropic curve. A tie-line is a horizontal
line that is drawn through a system point when the two phases are at
equilibrium and this line intersects the curve of each phase at the
equilibrium composition. The mole fraction can be calculated by using
the lever rule.
Conclusion
A temperature-composition diagram was constructed for the two-component
liquid system of water and isopropyl alcohol and the experimental results
were that the azeotropic mixture was 0.77 water by mole fraction.

References
Dow Chemical Company. (2012). Technical Data Sheet. Retrieved on
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http://msdssearch.dow.com/PublishedLiteratureDOWCOM/dh_08ac/0901b803
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David H. Duncan (2015). Physical Chemistry Laboratory Manual Fall 2015. P.
22-24.
University of Virginia. (n.d.). Binary Phase Diagrams. Retrieved on November
23, 2015 from http://people.virginia.edu/~lz2n/mse305/notes/PD-Binary.pdf
Science Direct. (February 2005). Tie-Lines. Retrieved on November 24, 2015
from
http://www.sciencedirect.com/science/article/pii/S0005273604002950
Chemfield Sdn Bhd. (2011). Isopropyl alcohol. Retrieved on November 23,
2015 from
http://www.chemfield.com.my/isopropyl-alcohol

Separation Processes. (n.d.). Azeotrope/Azeotropic Mixtures. Retrieved on

November 23, 2015 from
http://www.separationprocesses.com/Distillation/DT_Chp01f.htm
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from
http://chemwiki.ucdavis.edu/Physical_Chemistry/Physical_Properties_of_Matte
r/Solutions_and_Mixtures/Nonideal_Solutions/Azeotropes
Wikipedia. (n.d.). Isopropyl Alcohol. Retrieved on November 24, 2015 from
https://en.wikipedia.org/wiki/Isopropyl_alcohol
EveryScience. (2004). Temperature Composition Diagrams. Retrieved on
November 24, 2015 from
http://www.everyscience.com/Chemistry/Physical/Mixtures/f.1270.php