Distillation 64
Chem 355 Jasperse DISTILLATION
Background Distillation is a widely used technique for purifying liquids. The basic distillation process involves
heating a liquid such that liquid molecules vaporize. The vapors produced are subsequently passed through a
water-cooled condenser. Upon cooling, the vapor returns to it’s liquid phase. The liquid can then be collected.
The ability to separate mixtures of liquids depends on differences in volatility (the ability to vaporize).
For separation to occur, the vapor that is condensed and collected must be more pure than the original liquid mix.
Distillation can be used to remove a volatile solvent from a nonvolatile product; to separate a volatile product
from nonvolatile impurities; or to separate two or more volatile products that have sufficiently different boiling
points.
Vaporization and Boiling When a liquid is placed in a closed container, some of the molecules evaporate
into any unoccupied space in the container. Evaporation, which occurs at temperatures below the boiling point
of a compound, involves the transition from liquid to vapor of only those molecules at the liquid surface.
Evaporation continues until an equilibrium is reached between molecules entering and leaving the liquid and
vapor states. The pressure exerted by these gaseous molecules on the walls of the container is the equilibrium
vapor pressure. The magnitude of this vapor pressure depends on the physical characteristics of the compound
and increases as temperature increases. In an open container, equilibrium is never established, the vapor can
simply leave, and the liquid eventually disappears. But whether in an open or closed situation, evaporation
occurs only from the surface of the liquid.
If a liquid is heated to its boiling point, quite a different phenomenon occurs. The boiling point is the
temperature at which the vapor pressure of a liquid is equal to the external pressure applied to the surface of the
liquid. This external pressure is commonly atmospheric pressure. At the boiling point, bubbles of vapor are
produced throughout the liquid, not just at the surface, and the vapor pressure inside the bubbles is sufficiently
high to allow them to grow in size. The escape of these bubbles results in the characteristic chaotic motion of the
liquid identified as boiling.
When a pure liquid boils, liquid is converted to vapor rapidly. Even if the heating rate increases, the
temperature of the boiling liquid doesn’t change, only the rate of vaporization. The energy supplied by heating is
used by the liquid-vapor phase change.
Mixtures When a mixture of liquids is heated, the vapor pressure above the mixture equals the sum of the
vapor pressures of the individual compounds. When their combined vapor pressures equal the external pressure,
then boiling ensues just as for a pure liquid. However, the vapor above a mixture always has a different
composition than the liquid mixture itself. The vapor above a liquid is always enriched in the more volatile
component.
The table on the right shows the difference in composition Cyclohexane/ Cyclohexane/
between liquid and vapor for mixtures of cyclohexane (bp 80ºC) and Toluene Temp Toluene
toluene (bp 110ºC). Notice that a 50/50 liquid mix is 80/20 in the Liquid ºC Vapor
vapor, and a 75/25 liquid mixture provides vapor that is 90% 100/0 80º 100/0
cyclohexane. In all cases, the vapor is significantly enriched in the 85/15 82º 95/5
lower boiling cyclohexane. 75/25 84º 90/10
The temperature column in the middle gives the boiling 65/35 86º 88/12
points for the liquid mixtures. Notice that the top is pure 58/42 88º 84/16
cyclohexane, and the bottom pure toluene. But for any mixture of the 50/50 90º 80/20
two, the boiling point is somewhere in between that of pure 44/56 92º 70/30
cyclohexane and pure toluene. 38/62 94º 64/36
That the vapor is enriched in the more volatile component is 32/68 96º 52/48
the key to separating mixtures. In a distillation, liquid is vaporized,
25/75 98º 46/54
then the vapor is condensed. If the vapor above a mixture is pure,
21/79 100º 41/59
then a single vaporization/condensation provides pure product. This
is often true, one component of the mixture is nonvolatile, or is very 18/82 102º 37/63
much less volatile than the other. For a single simple distillation to 12/88 104º 30/70
provide good separation, two liquids in a mixture should differ in 7/93 106º 20/80
boiling points by at least 100ºC. But if you vaporize 50/50 3/97 108º 12/88
cyclohexane/toluene and then condense the vapor, the condensate will 0/100 110º 0/100
still not be fully pure; it will be only 80% cyclohexane. Simple
distillation would enrich cyclohexane, but would not provide pure
cyclohexane.
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Distillation 66
Fractional Distillation But consider what might happen if you did a series of vaporization-
concentration cycles on a cyclohexane/toluene mixture. If you start with a 50/50 liquid mix, the vapor will
be 80/20. If you condense some of that 80/20 vapor, the vapor above an 80/20 liquid mix would in turn be
over 90% pure. If you condense that vapor, you will have 93/7 liquid. But the vapor above that liquid will
in turn be >98/2 pure in cyclohexane. If you then condense that vapor, the resulting condensate will be quite
pure in cyclohexane. Thus by doing four distillations, you could have relatively pure cyclohexane.
This kind of sequence of multiple distillations is involved in a process called “fractional
distillation”. A fractional distillation apparatus includes a column placed in between the boiling pot and
the condenser. The fractionating column is filled with packing material with high surface area (typically
glass beats or metal wire.) The vapors generated in the pot rise up the fractionating column and encounter
cooler surfaces, upon which they condense. The condensed liquid is then reheated by rising hot vapors and
revaporize. This process of condensation and revaporization may occur again and again as the vapors rise
up the column. These composition changes are reflected by a decrease in boiling temperature as the
mixture moves up the fractioning column. If the condensation-revaporization is repeated a sufficient
number of times, the vapors of the more volatile compound reach the top of the column in a pure form. As
these vapors move into the condenser, the compound condenses and is collected as a purified liquid. SLOW
DISTILLATION IS KEY!
Purification of the high-boiling component: As the more volatile component is being selectively
removed, the residual liquid is increasingly enriched in the less volatile component. Thus, a separation of
the two compounds is achieved.
However, as the more volatile compound is removed, and the composition of the residual liquid
becomes enriched in the less volatile compound, the boiling temperature of the residual liquid also creeps
up. If a cyclohexane/toluene mixture is originally 50/50, then the liquid boils at 91ºC. But as the
cyclohexane is removed, the boiling temperature of the liquid gets higher and higher. (And it gets harder to
purify the lower-boiling fraction.) After a while, all of the low-boiling material is removed. At this point,
the only material that can climb all the way up the fractionating column is the low boiling component, and
you can distill it over as well. By changing collectors, you can thus isolate both the more volatile and less
volatile components in reasonable purity. SLOW DISTILLATION IS KEY!
Technical Aspects for Fractional Distillation: SLOW DISTILLATION IS KEY!
• The fractionating column must be positioned vertically so that condensed liquid can percolate down
through the rising hot vapors. This percolation promotes equilibration/heat exchange between the
liquid and vapor phases, a condition that allows the column to operate at maximum efficiency and
provide an optimum separation.
• A crucial factor is the distillation rate. In order to get the maximum number of
vaporization/condensation cycles and maximum purification, fractional distillation must be
conducted slowly. A one mL per minute rate (or slower) is recommended for best results in a
fractional distillation; simple can go faster. Slow, gradual distillation essentially allows the best
equilibration and heat transfer. If you heat too fast, vapors may not condense as quickly as desired,
and may waste some of the column.
• Packing material is also crucial. High surface area packing material provides surface on which
condensation can occur. The more easily vapor can condense, the more distillation cycles you get.
Miscellaneous SLOW DISTILLATION IS KEY!
• At reduced pressure, liquids boil at lower temperatures. (The external pressure is less, so it’s easier
to build up enough vapor pressure to escape.) High-boiling liquids are often distilled under vacuum.
• Simple distillation is useful when there are large differences in boiling point (>100ºC.) Often
organic solvents will be much more volatile than the target samples, so simple distillation is useful
for rapid removal of the solvent. Simple distillation is faster than fractional. But fractional is much
more powerful for more difficult separations.
• The temperature of the vapor is a direct reflection of it’s composition.
• When the temperature of the vapor is changing, it’s because the composition of the vapor is
changing.
• The vapor temperature and composition of the vapor is almost constantly changing because the
composition of the residual liquid is continuously getting depleted in the more volatile component.
• In a distillation curve, there will always be middle portion reflecting mixtures. For a typical
purification, three separate collections would be made: the initial relatively horizontal portion
(reflecting relatively pure volatile component); a middle portion which would be thrown away
(reflecting mixtures not worth saving); and a subsequent relatively high-boiling horizontal portion
(reflecting relatively pure less volatile component.)
Distillation 67
Part I: Simple Distillation of Cyclohexane/Toluene
Setup:
1. Securely clamp a 100-mL round-bottomed flask to one of the vertical rods way at the left extreme of
your hood. (Find flask in your kit).
• The neck of the flask has a “lip”.
• If you have a 3-fingered clamp, try to have all three fingers of the clamp completely below this
fat lip, so that the “lip” has no chance of slipping through.
2. Add a 3-way connector (#10 in your kit map).
3. To the almost horizontal branch of the connector, attach a condensing tube (#12 in your kit map).
• Use a blue Keck clip to hold the joints snug between the connector and the condensing tube.
• Note: you do not need a Keck clip to connect the bottom flask to the 3-way connector; gravity
will naturally hold the connector into the flask.
a. But, gravity will NOT naturally connect the condensing tube onto the connector!
b. In general, Keck clips are ONLY used when an attachment is angling downward and
gravity might otherwise cause it to fall.
• You don’t need the metal clamp on the condenser that’s shown in the picture. Skip it.
4. Set your hot plate on a jack, and place the jack and hotplate underneath your round-bottomed flask.
5. Plug the hot plate into one of the top two outlets.
• Don’t use either of the bottom two outlets.
6. Get out a 100-mL graduated cylinder, and place a liquid funnel into the top.
7. Raise the entire array high enough so
that the 100-mL graduated cylinder fits
underneath the end of the condensing
tube to collect the distillate. Again,
make sure your 100-mL flask, on which
the rest of the array rests, is very
securely clamped! It should be able to
hold everything up even without the
support of the hotplate.
8. Note: The picture shown isn’t perfect.
You don’t need the ring underneath;
your Keck clips will be blue, not
yellow; and you don’t need the extra
clamp to secure the condensing tube.
9. Use rubber tubing to connect the a
water tap (lowest green outlet at back of
hood) to the lower end of condenser); a
second hose should run from the higher
of your condense and feed into drain in
your hood.
• MAKE SURE THE SECOND HOSE IS FEEDING INTO THE DRAIN, AND IS NOT
HOOKED UP TO THE VACUUM OR TO ANOTHER TAP OF ANY KIND. HAVE
INSTRUCTOR DOUBLE-CHECK!
10. Add 60 mL of 50/50 cyclohexane/toluene and 2-3 boiling chips to your flask. You can just drop in
the chips, but you may wish to use your long-stemmed funnel to pour in the liquid.
11. To the open tube on top, add a thermometer. (There will probably be a setup display on a table.)
12. Adjust the position of the thermometer so that the alcohol liquid is just below the branch point of
your array.
13. Try to have a lab instructor check your setup to make sure everything is good!
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Doing the Distillation SLOW HEATING IS NOT CRUCIAL FOR SIMPLE DISTILLATION
1. Turn the condenser water on, but do so only very gently. All you need is enough flow to keep
the water circulating and keep the condenser cold. You do not need to turn it on full blast like
when you use the aspirator. Again, make sure this is draining into a sink!
2. Turn your hotplate setting to 10 to warm up the solution to the boiling point as fast as possible.
Since this is a simple distillation anyway, you may as well distill it over pretty quickly.
3. Record your thermometer temperatures (which reflect the composition of the vapor that is
actually distilling over at any point in time) at 2 mL intervals.
4. Continue the distillation until you have collected at least 50 mL of liquid..
5. Turn off the heater and lower the heating mantel away from the flask to allow cooling. Allow
the flask to cool for a few minutes.
Part II: Fractional Distillation of Cyclohexane/Toluene
Setup
6. Pour the liquid that you collected in Part I back into the round-bottomed flask.
7. Your setup for the fractional distillation will be very similar to what you did previously, except
for the following changes:
• You will insert a steel-wool packed distilling column (#13 in your kit map) in between your
flask and your three-way connecting tube. (You do not need to clean out your condensing
tube, you can use the exact same “top half” glassware from your previous setup, even if it is
slightly contaminated by a little distillate. The only difference is that the steel-wool column
in now added in.)
• Because of the height of the fractionating column, you can probably rest your heating mantle
on the bench top, or close to it, and still have enough height to fit your graduated cylinder to
collect drops
Doing the Distillation. SLOW AND STEADY IS CRUCIAL
8. Proceed as above, with the following adjustments:
a. Set your hotplate power to ~7.5. (This may not be perfect for everybody, but is a good
first guess.)
b. An ideal drop rate is one drop per second, and ≤1 mL per minute. If you are collecting
more than 1 mL per minute, you’re going too fast. It’s especially important that the
solution climb through the packing relatively slowly at the beginning.
c. This time record temperatures at 1-mL increments, beginning at 1-mL.
d. As the cyclohexane distills away, the composition in the residue will be continuously
changing, and getting harder to boil. As a result, you may need to raise the setting on
your hotplate to sustain a reasonable distillation rate, particularly as you approach 30 mL
of collected liquid..
e. Continue the distillation until you have collected at least 40mL of product and the
temperature has stabilized. (Discuss with instructor.)
Distillation 69
Name:
Distillation Lab Report
1. Plot your temperature (y-axis) versus mL collected (x-axis). Plot both distillations on the same graph.
Since little of the action takes place near room temperature, have the low end of your y-axis be 80ºC, with
a high end of your y-axis 112ºC. You may prepare your graph on computer with Excel, but I will also
accept hand-drawn graphs or other graph procedures. (Graphing difficulty isn’t the goal!). Either staple your
graph to this sheet or else generate your graph on the other side of this sheet for handing in your lab report.
2. Why is the vertical change in the fractional distillation so much sharper than in the simple distillation? (In
other words, why does it jump from say 85ºC to 105ºC over such a smaller number of mL with fractional
than with simple distillation? And why does it wait longer to creep up over, say, 90ºC?)
3. Give a brief discussion of how simple and fractional distillation differ. What is the difference? Why? When
and why would you choose fractional distillation? Would there be any circumstances in which you’d choose
simple distillation?
4. For the simple distillation, compare your vapor temperatures at 2 mL, 16 mL, and 30 mL. Why is the
temperature different at these different times? Does the temperature also change like that in the fractional
distillation?
5. Why is better separation of two liquids achieved by slow rather than fast distillation? (Particularly in the case
of fractional distillation?)
6. Explain why a lot of packing material with a lot of surface area is helpful for an effective fractionating column?
In our case, you had steel wool in your column. What would be worse if you didn’t have the steel wool present?
7. What effect does doing a distillation under reduced pressure have? For a particular sample, will the boiling point
be unchanged, go up, or go down if you try to distill it under a reduced pressure/vacuum type situation?
8. If you wanted to collect material that was >90% pure cyclohexane from your fractional distillation, which
section would you save? (For example, the first 5 mL? First 10?) How about 95% or 80%? (Looking at the
chart on the first page of the prelab is relevant!)
a. >90% pure:
b. >95% pure?
c. >80% pure?
