Experiment: Distillation

Distillation is the most commonly used technique for purifying an organic liquid or for
separating two or more organic liquids from each other. The technique consists of heating the
liquid being distilled in a flask until it starts to boil. The resulting vapor rises up a vertical tube,
called a distillation column, attached to the flask. At the top of the tube, the vapor enters another
tube called a condenser, where it is cooled and condensed, forming a liquid that is collected in a
container called a receiver. Mechanically, this technique is rather straightforward, boiling a
liquid, transporting the resulting vapor to a location where it is condensed and collected. How
distillation brings about the separation of two or more compounds with close boiling points is a
more complex issue. Such a distillation is called fractional distillation.

 Simple Distillation

A simple distillation is one in which only a short, unpacked distillation column is used. It is
effective for separating volatile organic liquids from non-volatile ones or from solids. In
addition, when the boiling point difference between two liquids in the sample is 80 °C or more,
separation by simple distillation is very effective. (Note: Some sources state that simple
distillation can be used in cases where the boiling point differences between the liquids in the
solution are at least 25 °C apar, but In practice, this boiling point difference is too small for use
in simple distillation.)

 Fractional Distillation

Fractional distillation is used to separate organic liquids with boiling points closer than 80 °C to
each other. How does fractional distillation work? Manipulation of Raoult’s and Dalton’s laws
leads to the conclusion that in any mixture of liquids, the vapor pressure will have a higher
percentage of the more volatile (lower boiling) liquid than the liquid phase. Said another way,
the vapor phase in equilibrium with the liquid phase will be richer in the more volatile
component than the liquid phase.

Consider a solution of two organic liquids, X and Y, where X is the more volatile component. The
solution mixture consists of 50% X and 50% Y by volume. When heat is applied to this mixture,
the vapor in equilibrium with the remaining liquid will be richer in the more volatile X than the
liquid will. Let’s say that this vapor is now 60% X and 40% Y. If this vapor condenses at some
point up the distillation column, the condensed liquid will now have a composition of 60% X and
40% Y. As more heat is applied, this liquid too will partially vaporize and again the vapor formed
from it will be richer in X than the liquid left behind, let’s say 70% X and 30% Y. As this vapor
travels up the distillation column, it too condenses, forming a 70% X and 30% Y liquid. This
vaporization–condensation process continues, each time enriching the vapor phase in the more
volatile component X. If the distillation column is long enough and if it contains enough sites
where these vaporization–condensation steps can take place, by the time the vapor reaches the
condenser, it will be 100% X. The pure X will condense and flow through the condenser and into
the receiver, and the distillation will have been successful in separating X and Y.
Fractionation columns, as these distilling columns are called, may be long or short. They contain
sites where condensation of the vapor can occur. These sites may be built into the column as
with the glass prongs (alembics) of a Vigreux column, or they may be introduced to the column
in the form of pieces of steel scrubbing sponge or glass helices. The closer together the boiling
points of the solution components are, the longer and/or more fully packed the distillation
column must be to bring about a good separation.

As you distill a mixture with different boiling points, you will be able to track quality of
separation by monitoring the temperature. Again, considering liquids X and Y, assuming X boils
at 40 °C and Y boils at 150 °C, in a perfect separation you would first collect pure X while your
thermometer steadily reads 40 °C. Once all of the X has distilled out, the temperature on the
thermometer will drop for a time while no vapor is contacting the tip of the thermometer. Then,
as soon as enough heat has been put into the flask, compound Y will begin to vaporize, rise up
the column and begin containing the thermometer tip. At this point you would have a new flask
ready to collect pure Y at a steady temperature of 150 °C. In reality, however, separations are
rarely perfect and, therefore, you will instead observe a gradual increase in temperature as you
transition from compound X to compound Y. The more gradual the increase, the poorer the
separation.

In the experiment below, you will not actually be separating the two compounds. Instead, in this
study of distillation techniques, you will track temperature and volume data while collecting all
of the distillate in one graduated cylinder. The goal is to graph temperature volume data from
your distillation and two other types of distillation data from your peers. Using this data, you
should be able to determine which type of distillation gave the best separation of ethyl acetate
and butyl acetate.

 Pre-lab Preparation

1. Describe how a distillation column is able to separate a mixture of ethyl acetate and butyl
acetate. Your description must describe the effect of repeated evaporation-condensation
steps on the composition of the vapor rising through the column.

2. Look up the physical constants (bp, RI and density) of ethyl acetate and butyl acetate.
Write these constants in a table format in your notebook along with the chemical
structure for each.

3. Based on your data above, which compound will you collect first in your distillation?
Explain briefly why this compound will distill first.

4. The procedure requires that you distill until you have collected 4 – 5 mL of butyl acetate.
How will you know when this has occurred?
 Experimental Procedure

! Safety Considerations

! Ethyl and butyl acetate are not dangerous compounds but it is a good idea to keep from
breathing large quantities of organic vapors. Keep containers stoppered until you are ready to
use them, and when you are finished with them, dispose of them properly according to your
instructor's directions. As you are distilling, check to be certain that your ground glass joints are
tightly sealed so that hot vapors don't escape into the lab.
! Use boiling stones.
! Don’t plug sand baths directly into the wall; use Variac controllers.
! Never distill to dryness.

In this lab, you will do a distillation of a mixture of ethyl acetate and butyl acetate. You will be
told to do this distillation in one of three ways listed below:

1. Simple distillation with no column

2. Fractional distillation with Vigreux column
3. Fractional distillation with steel sponge column

You will compare the results of your distillation with those of students using a different
distillation column, in an effort to determine which column was most effective for separation of
the mixture.

1. Setting up the Distillation Apparatus

After you are assigned a particular type of distillation, assemble a distillation apparatus as shown
in the diagrams below. For safety, be certain to clamp the distilling round bottom flask. You
should also adjust the height on the monkey bars in the hood to allow easy raising and lowering
of heat and easy emptying of the receiver. Note: In the event of an emergency, your distillation
apparatus should be stable if you lower the heating mantle.

Pay close attention to the following details.

If it is difficult to insert the temperature probe, use glycerol to lubricate the rubber adapter.
Position the thermometer so that the tip of the metal probe is approximately one inch (2.5 cm)
below the bottom of the side arm of the distilling head. This is critical. If the vapor does not
come in contact with this much of the probe, you will have an erroneous reading.
Check to make sure you have all of the clamps and water hoses connected as shown.
Verify that your water hoses are securely attached and turn the water on slowly to prevent
pressure surges from popping off the hoses and drenching your area. Remember, water always
goes in through the lower side of the condenser and out through the higher side.
 After you have set up your own apparatus, do not turn on the heat to your heating mantle until
your instructor has checked your apparatus. However, you may put the solution to be distilled
into the distilling flask along with 3-4 boiling stones before your set-up is cleared for work.

Simple Distillation
condenser
(water out)

condenser
(water in)
distillation
head
vacuum take-off
(used only for
50 mL r.b. flask can be vacuum distillations)
heated with a sand-bath or
small heating mantle
receiver
(graduated tube)

Keck clips indicated by this

Clamp style of arrow:

Note: Always use a clamp for the hot distilling flask. Keck clips are insufficient.
Fractional Distillation

condenser
(water out)

condenser
distillation (water in)
head

vacuum take-off
fractionating (used only for
column vacuum distillations)

receiver
(graduated tube
50 mL r.b. flask with or r.b. flask)
heating mantle
Keck clips indicated by
this style of arrow:

If you are assigned a simple distillation, there will be no fractionating column present (see
previous photo). If you are doing fractional distillation, you will be assigned a column, either a
steel sponge column or a Vigreux column. For the steel sponge column, you will need to insert
the steel into the column using a long deflagrating spoon to push the steel into the column to
achieve a uniform packing in the column. See the photo below to guide you on the amount of
steel to use. Too little and you will have insufficient surface area for condensation to occur. Too
much and the vapor will not be able to progress up the column. When the lab is complete, push
the steel sponge out of the column and discard in the trash.

Too Little Correct Too Much

With your set-up, either simple or fractional, you will distill a mixture of ethyl acetate and butyl
acetate. As the experiment progresses, you will collect temperature - volume data every 1 mL.
Collect your distillate in a 50-mL graduated cylinder. The temperature will change as you
collect distillate. You will plot this temperature-volume data to see how well each of the
columns separates the mixture.

 It is important to remember that distillation is used to separate two liquids, so in a normal

distillation, you would be trying to separate ethyl acetate from butyl acetate. You would
collect a fraction of material boiling from 76 °C to 80 °C, consisting mostly of ethyl
acetate, a hopefully small fraction boiling between 80 °C to 120 °C, and a third fraction
boiling from 120 °C to 126 °C consisting mostly of butyl acetate. In this case, we are
collecting all of the distillate in one graduated cylinder to determine from the
temperature-volume data which distillation apparatus works best. This will probably be
the last time you ever collect distillate in a graduated cylinder. In the future you will
collect it in flasks, one for each boiling point fraction.

2. Distillation

Into the 50-mL round bottom flask pour 25.0 mL of the ethy1 acetate and buty1 acetate solution
(already prepared for you). Add two or three boiling stones, and connect the flask to the rest of
the apparatus. After your instructor has checked your apparatus, verify that the condenser water
is flowing. Set the Variac to begin controlling the current into the 50-mL heating mantle. You
should start an intermediate setting and gradually increase the current as needed to vaporize the
two components.

Distill the liquid, collecting temperature-volume data every one milliliter of distillate collected.
Once it is clear you have collected 4-5 mL of only butyl acetate (based on temperature), you may
stop the distillation by lowering the heating mantle until it is a few inches below the round
bottom flask. (Note: If the temperature drops in the middle of your distillation, do not record
that value, as this indicates that insufficient vapor is present. Instead, turn up the Variac and
record when the temperature rises again.)

After the distillation apparatus has cooled to room temperature, take it down carefully. Return
both the distillate you collected and remaining liquid in your distillation flask to the labeled
container. (This liquid is re-used each semester, so do not dispose of any of your liquids into the
sink or general waste.) Leave all glassware to evaporate. Do NOT wash with water or
acetone. As always, make sure to turn off your thermometer before returning it.

The Excel file for graphing the data can be found here: Science Learning Center [licensed for
non-commercial use only] / CHEM203_Distillation.xlsx Using the computer at the front of the
room, add your data and the data from the two other types of distillation to the Excel file. Once
you have all three sets of data, print copies of the graph to use for post-lab analysis.
  Post-Lab and Report Requirements

1. Tables of temperature-volume data for the Vigreux column distillation, the steel
sponge column distillation, and the "no column" distillation.

2. On a computer, make a graph with temperature on the vertical axis and the volume of
distillate collected on the horizontal axis. Use the Excel spreadsheet available on the
Science Learning Center website. Go to the Montgomery College Homepage and
scroll to the very bottom. On the right, under “Counseling and Advising” select
“Learning Centers” (tiny font at the very bottom right of the page). Select the
“Germantown Campus Science Learning Center. From the left column, select
“Online Study Materials”. Select CH203 and then scroll down to open “Excel Graph
Distillation Template”. Type the temperature data into the correct columns and print.
Compare the curves for the three distillation columns. A “perfect” distillation would
give a curve like the one shown below.

126° C
Temp

77° C

At ~12.5 mL (all ethyl acetate should be gone)

Volume of Distillate

3. A student from another college (MC students would never do this) is distilling their
sample of butyl acetate and is unable to reach the required distillation temperature for this
substance of 126oC. The highest temperature he recorded was only 118ºC. What possible
things could they have done wrong with their distillation?
4. Which of the distillation columns separates the ethyl acetate from butyl acetate best?
Discuss all three methods and explain how you decided which is best.
5. What would be the impact of the following factors on the quality of separation of two
components in a fractional distillation?
a. Heating the distilling mixture more rapidly.
b. Using a longer distilling column.
c. Using a column with better packing.
Explain why you answered as you did. Your explanation should relate to the number of
evaporation-condensation steps that take place in the distillation.
6. What would be the impact of the above factors on the speed with which the distillation
could be carried out? Explain your answer.
7. Explain how your answers to 5 and 6 above relate to your decision about how to carry out
an effective distillation in a reasonable amount of time. Is fractional distillation always
the best choice?

8. An organic liquid decomposes at 240 °C, before its boiling point can be reached. What
steps can be taken to distill this liquid to separate it from some solid impurities dissolved
in it?

As always, write a concise summary/conclusion for your work done in this lab.