Chapter 3

Fractional
Distillation

In this experiment, you will separate (to some

extent) a mixture of isopropyl acetate and toluene
by one method of fractional distillation, collecting
the initial fractions from your Hickman still, then
redistilling them.

Background
Gas Chromatography
Chromatography is the separation of compounds by repeated
partitioning between a stationary and a mobile phase. In this course
you will carry out column and thin layer chromatography (solidliquid
partitioning) and gas chromatography (gasliquid partitioning). In gas
chromatography using a packed column, a volatile sample is
introduced in a flow of gas to a heated large diameter column, which
is packed with beads coated with a non-volatile liquid (usually a
silicone oil).
Figure 3.1 Schematic of a gas chromatogram and
column.
In capillary gas chromatography the sample passes through a heated
small diameter column whose interior surface is coated with the non-
volatile liquid phase (compare Figures 3.1a and 3.1b). In either case,
the partitioning is between the sample choosing to be in the mobile
gas expressed as a partition coecient. A compound which spends
relatively more time in the mobile gas phase will be swept along faster
and will elute earlier than a component which spends relatively more
time in the stationary liquid phase. A significant part of a mixtures
ability to be resolved depends on you can, in part, view the gas
chromatographic column as a giant distillation column with many
theoretical distillation plates. Other factors are also important, such as
the polarity of the compounds being separated (which influences how
much they want to dissolve in the liquid phase). As the components
come o the column, they pass through a detector. The resolution
using capillary gas chromatography is much higher than with packed
columns. We will be using a Hewlett-Packard Gas Chromatograph
equipped with a capillary column coated with a phenyl methyl silicone
polymer, and our carrier gas is helium. Our detector is a Thermal
Conductivity Detector (TCD), which is a hot conducting wire over
which the eluent gas passes. As compounds pass over the wire, its
electrical resistance changes due to dierent heat transfer properties
of pure helium versus helium with some organic compound in it. The
change in resistance is measured and sent to the plotter which plots
the chromatograph (see Figure: 3.1c for a sketch of a gas
chromatogram).
27
Gas chromatograms contain three types of informationthe number compounds you would need to standardize the areas by measuring
of peaks, the retention time of the compounds (how long it takes for the relative areas produced by a known ratio of compounds.)
each compound to pass through the column), and the size of the
peak. The number of peaks indicates the number of compounds in the
injected sample. The length of time a compound spends in the column
is the retention time. The retention time depends on the compounds Figure 3.2 Gas chromatogram of a mixture of isopropyl
partition coecient (a function mainly of volatility) and can be used to acetate and toluene.
identify the compound when compared to the retention times of
known reference compounds. For example, Figure 3.2 shows the gas
chromatogram of a mixture of isopropyl acetate and toluene.

We can identify the compound giving rise to either peak by injecting

pure isopropyl acetate or toluene and noting the retention time of the
peaks in those known, pure samples. As shown in Figure 3.3,
isopropyl acetate has a retention time of about 1.67 min, while that for
toluene is about 1.91 min. Given a limitation of choices to these
compounds, we can conclusively assign the peaks in Figure 3.2 based
on their retention time. The size of the peak depends on how much
concentration of sample in the helium flow results in a larger peak. The
area of the peak can be given either by the electronic integration
provided by the computer, or you can measure it manually by using
the formula for the area in a triangle (area = 1/2 base height). This
area is a measure of how much compound is passing over the
detector wire and is a measure of the concentration of compound in
the sample. The more sample, the bigger the peak. (It is important to
note that not all compounds interact with the detector in the same
way. While you can use the raw area data to get a good idea about the
proportions of the compounds in a mixture, to get an exact ratio of

28
 spectra for isopropyl acetate, toluene, and a mixture of the two are
Background: Procedures in Lab
given at the end of this experiment. Please review these spectra. We
By collecting the distillate in an initial distillation of a mixture of
will cover NMR spectroscopy in greater depth later in the term and will
isopropyl acetate and toluene and redistilling the distillate, you are
at that time refer back to these spectra.
acting as a manual theoretical plate. You should notice that the

Pre-Lab Preparation
Figure 3.3 Pure samples of Toluene and isopropyl acetate. Readings in Manual

Read the background on the theory for this experiment and the
experimental procedure. Review the distillation background in
chapter 3. You should be familiar with the dierence between simple
and fractional distillation and with the concepts of theoretical plates
and liquid-vapor phase diagrams. Gas chromatography (GC) is the
first of several chromatographic techniques to which you will be
exposed. The background of this technique is covered in the
background section and will be covered in the lab lecture. You should
be able to describe the various components of the gas chromatograph
(injection port, column, detector). You should be able to describe how
separations are achieved by this technique, including the eects of
column liquid phase and temperature. You should know how to use
GC to qualitatively identify compounds and quantitatively determine
how much of each component you have in a mixture. You should be
able to draw the correct chemical structure of compounds used in this
redistilled distillate is quite pure in ethyl acetate. By redistilling the pot,
experiment when given their name.
you should remove most of the lower boiling component, leaving fairly
pure, less volatile toluene in the pot. The gas chromatogram will give
you a very good idea about how well your distillations separated the
components. Another way to analyze the outcome of this experiment
would be to record the NMR spectra of the fractions. The 1H NMR

29
Reading from Padas place the thermometer in the heating block, but it should be moved
Distillation, Gas Chromatography into the Hickman still once the temperature of the heating block is
near the listed temperature, as shown in Figure 3.4b.
Reading from OChem.net
Distillation, Gas Chromatography, Isopropyl Acetate, Toluene 2. Stir the solution slowly (rapid stirring can cause splashing of
undistilled material into the still). Turn on the hot plate and slowly (5
Physical Data Table C/min) raise the temperature of the heating block to 8090 C. Do
Isopropyl Acetate (MSDS), Toluene (MSDS) not raise the temperature too rapidly. You should see a condensate
collecting in your stillhead. Periodically tighten the connector
between your flask and the Hickman still, as it often becomes loose
Compound Physical Molecular
Density Amount during heating. If your solution is boiling and no distillate is
/Formula Properties Weight
condensing, ask your TA for help (your seals may be bad). Also
Isopropyl colorless note that you should judge the temperature range of the heating
acetate liquid 102.1 g/mol 0.88 g/mL 1.5 mL
block for yourself. The range of correct temperatures can vary
C5H10O2 bp 89 C
widely depending on the placement of the flask and thermometer. If
Colorless
Toluene the distillate seems to be coming over too slowly or too quickly,
liquid 92.15 g/mol 0.87 g/mL 1.5 mL
C 7H 8 raise or lower the setting on the hot plate.
bp 111 C

Procedure
This experiment will be completed in two lab periods. In the first lab
period you will carry out an initial distillation. In the second period, you
will redistill either the initial distillate or the distillation pot.
1. Using a calibrated Pasteur pipette, add a mixture of 1:1 isopropyl
acetate/toluene (3.0 mL) to your 5 mL conical vial. Add a spin vane
and assemble the Hickman still and heating block as in Figure 3.4a.
Wrap the connector and lower portion of the Hickman still with
aluminum foil to help contain the heat during the distillation. Also
loosely cover the top of the Hickman still with aluminum foil. Initially
3. Using the bent pipette that your TA will provide to you, keep
removing the distillate and placing it into a 0.5 dram vial labeled
Fraction 1 until you have collected about 1.2 mL (you can gauge
this amount by using your calibrated 1 mL Pasteur pipette to
temporarily draw up the liquid from the vial).
4. After about 1.2 mL of the distillate is collected, raise the heating
block temperature to about 105115 C (or about 2030 C higher
than in step 2), collect and place the next approximately 0.6 mL in a
0.5 dram vial labeled Fraction 2.

30
5. Remove the distillation apparatus from the heating block and allow
it to cool. You should have about 1.2 mL of liquid left in your
distillation conical vial (the pot). Transfer this liquid from the pot to
a vial labeled Fraction 3.

6. After removing some of these samples for gas chromatographic Figure 3.4 Experimental setup, Hickman still.
analysis (see
you step 7), cap and save Fractions 1 and 3 for the
should
redistillation
following lab step.
period. You may dispose of the intermediate Fraction
2 in the liquid waste after the GC analysis is completed.

Note: The GC sampler may not contain any water droplets (e.g., from
7. Follow the GC analysis procedure to acquire GC of Fractions 1, 2 and 3.
incorrect cleaning). Water will ruin the column.
8. From the chromatograms the retention times of peaks are used to identify
the compounds
Note: and the
Save the bent relative
pipette for areas
Day 2.of peaks are used to measure the
amount of isopropyl acetate and toluene in the fractions.

Redistillation
9. You will work with another group for the redistillation. Combine both
Fraction 1s and both Fraction 3s ( the " pots"). You will redistill one of the
combined fractions while the other group redistill the other.

10. Set up a Hickman still as in Figure 3.4a with a spin vane and either the
combined Fraction 1 or combined Fraction 3.
Figure 3.4a: Initial thermometer setup.
11. Raise the temperature of the heating block to about 80-90 C if you are
redistilling Fractions 1. Collect about 1.0 mL of the distillate.

12. Raise the temperature of the heating block to about 105-115 C if you are
redistilling Fraction 3. Discard the first few drops of distillate as it may
contain isopropyl acetate. Collect about 1.0 ml of distillate.

13. Run GC for your distillate and share the results with your partner group.

31



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32
Experimental Write-Up
Follow the Guidelines for Laboratory Notebook. Include an Build your reaction vessel!
interpretation of retention times and areas of each peak on your gas
chromatographs. Discuss the composition of each fraction and the
eciency of the separation. Comment on your results in comparison
to the labs results. Include your labeled chromatographs with your lab
report as an appendix.

Interactive 3.1
calculator App.

Check Answer

33
Question 1 of 4
Distillation is a process that utilizes heat to sepa-
rate a component of a mixture. What intrinsic
property does distillation utilize to separate two
liquids?

A. Boiling point

B. Melting point

C. Density

D. Specific heat

Check Answer

34