Fractional distillation of an unknown mixture

Xiaohan Zhang (1717717)

Introduction
Each pure liquid substance has a fixed boiling point under a certain pressure. When the
liquid organic substance is heated, the vapor pressure increases, as the vapor pressure
reaches atmospheric pressure or a given pressure, the liquid boils, and the temperature
at this time is called liquid boiling point. The boiling point is related to the temperature
when the vapor pressure is equal to the ambient pressure, that is, the boiling point is
related to the air pressure. Usually the boiling point we call is measured at standard
atmospheric pressure.1

Distillation is perhaps the most common laboratory technique used by chemists to

purify organic liquids. After carefully distilling of the mixture, the compounds with
different boiling points are separated into separate components. Ordinary distillation
can only separate and purifiy substances with large differences of boiling points, When
the boiling points of two compounds differ by less than 40oC, they cannot be separated
by simple distillation. Although many times of repeating distillation can achieve a better
separation effeciency, but the operation is more troublesome, the loss is also very large.
In that case, fractionation must be used, and the method has an effect that can exceed
simple distillation. In fractional distillation, a mixture of liquids is boiled and the
resulting vapors travel up a glass tube called a "fractionating column" and separate.

Principles
The boiling point composition curve can be used to predict the number of theoretical
towers required to achieve the required separation. The curve data is obtained by
obtaining the different mixtures, heating them to boiling point, recording the
temperature and analyzing the vapor composition above each mixture. The lower curve
represents the liquid composition, and the upper curve represents the vapor composition.
Fractional distillation is basically a sequential number of many simple distillations, the
number of which is determined by the theoretical tower plate. The boiling point
composition curve can be used to determine the number of theoretical towers required
to obtain a certain degree of separation. Take the 1:1 mixture of Toluene and
cyclohexane as an example, the third theoretical tower plate will produce about 99% of
the pure cyclohexane distillate. More theoretical towers are needed to obtain pure
cyclohexane, but the efficiency of the fractionation tower is limited, so it can no longer
provide the required separation, resulting in more contamination in the distillate.

Fractional distillation is the use of fractionation columns to achieve this "repeated"

distillation process. When the vapor of the mixture enters the fractional column, due to
the heat exchange with the air outside the column, the components of the higher boiling
point in the vapor are easily condensed, so the condensate contains more component
with higher boiling point, and the composition of the low boiling point in the vapor is
relatively increased. When the condensate flows down, it comes into contact with the
rising vapor, and the heat exchange is carried out which made the substance with higher
boiling point in the rising vapor to be condensed while the substance at the low boiling
point is still vaporized. In the condensate, the substance at the low boiling point is
vaporized. Such a number of times the heat exchange between the liquid phase and the
gas phase, the low boiling point of the substance rising and finally distilled, high boiling
point substance of the mixture is constantly flowing back into the flask, thus the boiling
point of different substances separated. 2

Equipments
Stands with Clamps
Heating plate with oil bath
Magnetic stir bar
Fractionating column
distillation adaptor
Thermometer
100-mL round bottom flask
Liebig Condenser
Conical flask
25-mL graduated cylinders

Materials
Unknown mixture 1
Unknown mixture 2

Procedures
(1) Simple distillation of the unknown mixture 1
Gather all of the equipment needed to assemble the normal distillation apparatus and
place them in a fume hood. After the installation of the instrument, check that the
various grinding ports are closely connected to prevent air leakage. Add 50 cm3 of
unknown mixture 1 into a 100 cm3 round bottom flask. Let the cool water flow from
the condenser then start the heating plate. Record the temperature of two fractions.

The heating speed should be fast at beginning and then slow down, and when the liquid
starts to boil, you can see the vapor slowly rising and the liquid flowing back. When
the top of the vapor to reach the mercury dome, the temperature rises sharply, then more
attention should be paid to control the heating temperature, so that the lower end of the
thermometer at all times to maintain a water drop of condensation, at this time, the
liquid and steam remain balanced, the temperature displayed by the thermometer is the
real liquid boiling point.

(2) Fractional distillation of the unknown mixture 1

Assemble the equipment of fractional distillation. Add 50 cm3 of unknown mixture 1
into a 100 cm3 round bottom flask. Record the temperature after the first drop is
collected and again after every 2 ml of distillate is collected.

(3) Fractional distillation of the unknown mixture 2

Assemble the equipment of fractional distillation. Add 50 cm3 of unknown mixture 2
into a 100 cm3 round bottom flask. Record the temperature after the first drop is
collected and again after every 2 ml of distillate is collected.

Results
Simple distillation of unknown mixture 1
Temperature (oC) Approx. Volume (cm3)
Fraction 1 63 oC 0-5 cm3
Fraction 2 71 oC 5-44 cm3

Curve of fractional distillation of unknown mixture 1

Curve of fractional distillation of unknown mixture 1
74

72

70
Temp (oC)

68

66

64

62

60
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44
volume (cm3)

Component of mixture1: hexane and benzene

Component of mixture2: tetrahydrofuran (THF) and Ethyl Acecate

Discussion
Azeotrope or a constant boiling point mixture refers to the phenomenon of a liquid
mixture consisting of two components or components at a specific proportion, boiling
at a constant pressure, and its vapor composition is the same as that of a solution
Equipment and materials. Azeotrope could not possible to separate by conventional
distillation or fractionation.

Literature review gives the theorical boiling point of the substances:

Experiment 1
Substances Boiling Point oC
Benzene 80
hexane 69

Benzene（5.2%） and hexane（94.8%） azeotrope 67.85

Water with hexane(22.1%) Azeotrope 61.6

Water (8.9%) with hexane(91.1%) 69.40

According to Sadighi et el, Benzene and n-hexane make azeotropic mixture and their
separation by distillation method at normal atmospheric pressure is impossible. By
using suitable solvent like N-methyl pyrrolidone (NMP) the relative volatility of
components could be modified and enhanced to some extent.2
The temperature when each millimeter of mixture was collected is shown on the figure
and the relation between them is shown on figure 1. The expected temperature range
was 61.6oC (Benzene and hexane azeotrope), 67.85 oC (Benzene and hexane
azeotrope) and 69.70 oC(Water with hexane azeotrope) In additionally, the relation
between the temperature and volume was more similar to the simple distallation rather
than the fractional distallation. According to the distillation curve, the unknown mixture
1 contains about 23% benzene, 72% hexane and about 5% water. It can be confirmed
that the mixture contains moisture, which may be caused by inadequate water out when
the solution is configured, or by the mixture absorbing water vapor in the air. In addition,
the first two co-boiling mixtures flowed out without an effective distinction, possibly
because of the excessive rate of heating.3

Experiment 2
Substances Boiling Point
THF 66
Ethyl acatate 77.2

THF（95.3%） and water（6.7%） 64.8

azeotrope

Ethyl acetate（84.5%） and water 70.4

（15.5%） azeotrope

THF would not form any azeotrope with ethyl acetate. The first distillation is divided
into THF, more likely the THF and water co-boiling, so we can observe that there are
two stages of the previous THF heating process, one of which may be co-boiling. The
second distillation is divided into ethyl acetate, which is also possibly a co-boiling of
ethyl acetate and water. The most possible reason was that the heating rate was set too
high so that the thermometer had a delay of showing temperature. It means that the
actual temperature of the vapor was higher than the reading temperature on the
thermometer.4
Qusetions
1. One mole of compound A, with vapor pressure 400 mmHg at 50 °C, mixed with 3
moles of compound B, with vapor pressure 480 mmHg at 50 °C to form a homogeneous
solution. What is the vapor pressure of mixture at 50 °C?
460mmHg

2. Why should a distilling flask be filled not less than 1/3 filled or more than 2/3 full?

If the flask is more than half full bumping occurs and the condenser as well as the
distillate will be contaminated with undistilled liquid. If the flask is too big for the
amount of liquid,a lot of heat loss occurs from the flask and the rate of distillation is
hence lowered.

3. A 50% aqueous solution of ethanol (50 ml total) is distilled and collected in 10ml
fractions. Predict the boiling range of each fraction.
fractions vol. collected(ml) temp. °C (predicted)
1 10
78.13℃

2 20
78.13℃

3 20-26.3
78.13℃

4 26.3-30
100℃

5 30-40
100℃

6 40-50
100℃

Explain: Ethanol forms azeotrope with water at 78oC (95:5), so the first fraction is a
little bit more than water fractions.

4 What is the mole fraction of each component if 3.9 g of benzene (C6H6) is dissolved
in 4.6 g of toluene (C7H8)

Benzene：C6H6 =0.05 mol

Toluene：C7H8 =0.05 mol

the mole fraction of each is 0.050/0.100 = 0.5

Applications and conclusion

Distillation accounts for about 95% of all industrial separation processes today. The
main difference between distillation on laboratory scale and distillation on an industrial
scale is that the former is usually done in batches, while the latter is usually carried out
continuously. In continuous distillation, the starting mixture, vapor and distillation are
maintained in a constant composition by carefully replenishing the gaze material and
removing the fractions from the vapors and liquids in the system. The most extensive
industrial applications for continuous fractionation are in refineries and natural gas
processing facilities.

REFERENCE LIST

1 J. P. Garcia Villaluenga and A. Tabe-Mohammadi, J. Membr. Sci., 2000, 169, 159–

174.
2 R. F. Marschner and W. P. Cropper, Ind. Eng. Chem., 1946, 38, 262–268.
3 S. Maghsoudi, A. Sadighi, F. Feyzi and H. Shahraki, アジア・太平洋化学工学会

議発表論文要旨集, 2004, 2004, 243–243.

4 Azeotropic Data of Ethyl acetate + Tetrahydrofuran from Dortmund Data Bank,

http://www.ddbst.com/en/EED/AZD/AZD%20Ethyl%20acetate%3BTetrahydrofura
n.php, (accessed 18 October 2019).