SIMPLE & FRACTIONAL

DISTILLATION
Chemistry 315
 Simple vs. Fractional
■ Simple Distillation
– Relatively pure substances can be separated from a
mixture if the b.pts. of the components differ by
>100oC or if impurities in mixture are <10%.
– Often used as a purification step or to determine
b.pt. as done in the Identification of an Unknown.
■ Fractional Distillation
– Separates components in the liquid mixture by
distilling them through a longer path with more
vaporization-condensation cycles (just like re-
distilling over and over again).
 Terminology
■ Superheating – When a liquid temperature exceed a
normal BP, due to increased atmospheric pressure or
surface tension, and the bubbles are unable to form.
Sudden popping may occur once this surface tension is
broken.
■ Condensate – the liquid that drips into the receiving
flask (lower, cooler) from the initial distilling flask
(higher, warmer)
■ Reflux – the vaporization and subsequent condensation
of a liquid such that it returns to its original position.
– In distillation, it will stack reflux events such that
theoretical plates (discussed later) are formed.
– The highest theoretical plate should contain a larger
proportion of the lower boiling point compound
relative to the overall composition of the solution.
 Simple Distillation
■ Distillation is the process of vaporizing a liquid
in a container, condensing the vapor, and
collecting the condensate in another container.
■ Simple distillation may be used to:
– Purify a liquid from a minor amount of impurity,
either solid or liquid;
– Separate liquids with different boiling points (~80-
100°);
– Obtain an approximate boiling point.
 In Lab
■ The distillation glassware, particularly the
fractionating column, is expensive –
please be careful when handling it!
■ Have a picture of the glassware setup
available so you can refer to it while you
work.
 Simple Distillation Set-up

Instructor For purifications only!

must approve Not for this week!

your
distillation set- distilling head

up before you water condenser

begin heating take-off adaptor

your flask. distilling flask

water out
WATER OUT
water in
WATER IN
receiving flask
immersed in ice-water bath
 Simple Distillation Set-up

Instructor For this week!

must approve
your
distillation
set-up before
you begin
heating your
flask.
 In Lab
■ Distillation (separation) of a mixture of ethyl acetate
and butyl acetate by simple distillation.

■ You will discuss the efficiency of fractional distillation.

• “Efficiency” is determined by how well the mixture is

separated into its components (similar to “resolution”
in chromatography).

• The closeness of your calculated mole %

composition by distillation to the actual composition
will be the measure of efficiency.
Fractional Distillation Apparatus
A simple distillation
apparatus becomes a
fractional distillation
apparatus by placing a
column between the
distilling flask and the
condenser.

The fractionating
column allows many
vaporization-
condensation cycles to
take place, which
effectively separates the
components of the
mixture.
Fractional Distillation Concept:
■ More vaporization/condensation cycles are able to take place in
the longer column with increased surface area, like the
vigreux column (A)

■ Column efficiency is determined by theoretical plates

– A theoretical plate for distillation is one cycle of
evaporation and condensation.
– Fractional distillation has many theoretical plates
(6-8 on average, column dependent)
■ Rate of heating needs to be increased gradually as the
distillation proceeds
– Too fast: the number of cycles are not allowed to occur
for good separation
– Too low: column may lose heat faster than it can be
warmed by the vapor and vapor may not reach the top of
the column
■ Allows for the head-gas to be composed of only one pure
compound.
 In Lab
■ Distillation (separation) of a mixture of n-butanol and
n-propanol by fractional distillation.

■ You will discuss the efficiency of fractional distillation

for this separation as well.
 Experimental Procedure
■ Put boiling stones (2) and the
mixture in the distilling flask first.
(Use a glass funnel for liquid.)
■ Clamp flask securely to ring stand.
Use a lab jack to support a hot
plate and sand bath or Al block.
■ Insert the Vigreux column between
the distilling flask and the distilling
head for the fractional distillation.
■ Position thermometer correctly. If
you do not position it correctly,
your temperature readings will
5 6 5 6
4 7 4 7

3 8 3 8

2 9 2 9
1 1 01 1 10

be incorrect!
■ Use a water pump to circulate
cooling water through the
condenser.
 Experimental Procedure
■ You will collect “fractions” of distillate in test
tubes.
■ Have a test tube rack ready in which to
place test tubes containing the fractions.
■ THE INSTRUCTOR WILL CHECK YOUR SET-UP
BEFORE YOU HEAT.

■ Conduct distillation slowly but steadily after

initial rapid heating.
■ The liquid that distills over a ~5-deg.(or
less) interval is collected in one test tube.
3
4
5 6
7
8 3
4
5 6
7
8
■ It may be a large or small volume of liquid. It doesn’t
2 9 2 9

matter.
1 1 01 1 10

■ If you accidently mess up an interval, write down the

actual temperature interval and then proceed with a
new 5-deg. interval.

■ Continue to collect fractions until there is

only about 1 mL liquid in the distilling flask
(small puddle about the boiling chips)
 Experimental Procedure
■ Measure the volume of
each fraction with a small
graduated cylinder. Discard
material into a beaker.
■ DO Not distill to dryness!
■ Leave a few drops of liquid
in the distilling flask.
■ When you are finished,
remove the heat source by
4
5 6
7 4
5 6
7
lowering the lab jack.
3 8 3 8

2 9 2 9
1 1 01 1 10

■ Allow the apparatus to cool.

■ Put distillation waste in
marked jar in Hood.
 Distillation Notes
■ Distilling flask must be securely attached by
a metal clamp (if lab jack is lowered, the
clamp must support the entire apparatus!).
■ Use a glass funnel when pouring liquid into
distilling flask. Avoid contaminating flask neck
or sample may leak out or worse.
■ After putting liquid unknown in distilling flask,
cap the vial and return to the waste area. Do
not rinse the vial.
 Distillation Notes
■ Thermometer must be properly placed in the
distilling head to record an accurate temperature.
The Bulb should sit below the bend in the
distillation joint.
■ Distillate is to be collected in a round bottom
flask for the fractional distillation.
■ Please have your apparatus completely
assembled, with water tubing properly attached,
before asking the instructor to approve your set-
up.
 Procedure Notes:
 Measure volume of unknown mixture with
graduated cylinder 20.0 mL ±1.0 mL

 Wrap fractionating column with Aluminum

foil
 Wrap the whole RBF for simple
 Wrap the RBF and some of the column,
but make sure not to melt the Keck clip

 Control distillation rate (~ 1 drop/2-3 sec)

by moving heating mantle up and down
with the lab jack– don’t try to control by
changing dial.
 Distillation of a Mixture
■ Put your mixtures in distilling flask with boiling
stones
– Don’t forget the boiling stones before assembling the
apparatus!!
– We will need these to reduce surface tension and improve
resolution
■ Conduct distillation slowly but steadily
– Rate of distillation should be ~1 drop/2-3 seconds
at the distillation head
■ Collect fractions in test tubes.
– The liquid that distills over a 5-deg. interval is
collected in one test tube.
– It may be a large or small volume of liquid; it
doesn’t matter.
■ Measure the volume of each fraction after the
distillation completes; keep the samples in order!
 Distillation Notes,
continued:

■Do NOT distill to

dryness!!!!!
■ Why? Dangerous peroxides may form in the pot
residue that are explosive.
■ In general, you should never distill to dryness…

Pay CLOSE attention!

 Example: Distillation
 Results
Simple Distillation 3

of a mixture where
components have

Fraction Volume
2

similar boiling
points 1
Graphs of Volume of distillate vs.
Temperature
0
55 65 75 85 95 105 115 125
Temperature

12
10
8
 Simple Distillation 6
of a mixture where 4
boiling points are 2
0
very different or a
55 65 75 85 95 105 115 125
Fractional
temperature
Distillation
 Distillation Analysis
 You will be graphing “Volume of
Fraction vs. Temperature” for each
distillation method
 Expect to collect the most volume at
the temperature(s) nearest the boiling
point
 Ethyl Acetate, Butyl Acetate, n-
butanol, and n-propanol literature
boiling points should be retrieved
from the CRC Handbook of
Chemistry and Physics!
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