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Experiment 2
Experiment 2
Experiment 2
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Ptotal = PA + PB
where PA and PB are the partial pressures of components A and B respectively. Remember that
partial pressures increase as the temperature of the liquid reaches its boiling point. You can see
water begin to steam shortly before it boils. In a mixture of miscible substances, the partial
pressure of a component depends on the vapor pressure of the pure component and the relative
amount of the component in the mixture. This relationship is stated as Raoults lawthe
partial pressure of a component in an ideal solution is equal to the vapor pressure of the pure
component multiplied by its mole fraction:
PA = PAo X A
XA =
number of moles of A
total number of moles in mixture
For a mixture containing only two components, A and B, the mole fraction is:
XA =
number of moles of A
number of moles of A + number of moles of B
Combining Daltons law of partial pressures and Raoults law to a mixture of A and B, the
vapor pressure of the mixture is:
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boiling component and higher boiling component. If the difference in the boiling points of the
two components is large, a careful distillation can separate the mixture into its two components.
In the figure below two curves representing the temperature of the distilling vapor as a
function of the volume of distillate. The black curve represents an ideal distillation in which
the lower boiling component distills completely and then the higher boiling component distills.
The gray curve is a more empirical plot in which the distillate at the beginning of the
distillation is enriched in the amount of the lower boiling component and the distillate at the
later stages of the distillation is enriched in the higher boiling component. You will be making
a curve like this one for your lab report.
Temperature C
80
70
60
50
40
30
20
10
0
0
10
20
30
40
Volume of Distillate (mL)
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distillation rate. Sophisticated fractionating columns have regulated heating coils built into
them.
Increasing the surface area over which the vapor must travel increases the purity of the
distillate because the number of times that the liquid is distilled is effectively increased. As
the vapor travels up the column it condenses on the surface and then re-evaporates. Every time
this happens, the vapor becomes more pure. The units for measuring how many times the
vapor goes through this cycle of condensation and re-evaporation are called Theoretical
Plates. This term comes from the very old distillation columns that had actual plates in the
column for the vapor to condense and evaporate from.
Techniques:
Distillation Apparatus - Fractional Distillation
Thermometer
Adapter (check for O-Ring!)
Distilling
Adapter
Water Out
Water in
Open to the Air
Air Condenser
Acts as Fractionating
Column
Water Condenser
Distillation Flask
Recieving Flask
Collect Fractions Here
Boiling Chips
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to form. An alternative method for promoting even boiling is to agitate the liquid with a
magnetic stirrer as it is being heated. CAUTION: Never add boiling chips or a stir bar to a
hot liquid. This can cause a seemingly calm liquid to boil suddenly and violently.
Distilling adapter: The adapter connects the distillation flask, the condenser, and the
thermometer. This type of adapter is often referred to as a distillation head. The ground glass
joints must be lined up and connected tightly to avoid leakage of the vaporized liquid. Seal the
joints with a little bit of grease. More grease does not make a better seal, use just enought to
coat the joint. Leakage will result in loss of some (or all!) of the vapor and will pollute the
laboratory environment. The position of the thermometer is adjusted so the bulb is below the
adapter sidearm connected to the condenser. (See the diagram) In order to get reliable readings
on the thermometer during the distillation, the vapors of the heated liquid must totally surround
and contact the thermometer bulb.
Condenser. The condenser cools the vapor to a liquid and directs this condensate to the
receiving flask. The most common type of condenser is the water-jacketed type shown in the
diagram above. The water supply is connected to the condenser with rubber hoses. The water
flows in the lower hose connection (most remote from the distillation flask) and out the upper
hose connection. Remember: With condensers, the water should flow up-hill. Before turning
the water flow on, check the hose connections carefully to ensure that they are secure and will
not pop off. An extra margin of security can be gained by twisting wire around the hose
connections. The water flow is adjusted so there is a slow, constant flow of cold water to the
condenser. You really only need a trickle, more than that will cause the hoses to pop off, spray
your neighbors, and cause a flood.
The receiving flask. The container to collect the condensed vapor is called the receiver.
It may be a round-bottom flask, an Erlenmeyer flask, a bottle, or a graduated cylinder. Use
your graduated reaction vial as the reciever to help you monitor the volume of your fractions.
In the diagram, an adapter leads from the end of the condenser into a small graduated container.
In this case the sole purpose of the adapter in this case is to direct the condensate from the
condenser to the receiver. One important feature of the setup should be noted at this pointthe
system is open to the atmosphere. This apparatus is being heated, and you should never heat a
closed system. If the liquid being collected has a low boiling point, it is good practice to cool
the receiving flask with a cold water bath.
Heat is slowly applied to the distillation flask. The amount of heat to apply is
determined by the rate of distillation. The liquid should gently bubble and vaporize. As vapor
rises from the liquid, it moves up the apparatus raising the temperature of the apparatus. The
vapor will fill the distillation flask and most of the distillation head. The thermometer bulb
should be completely surrounded by the vapor. If vapor creeps past the thermometer bulb
without contacting it, the measured boiling point will be low. The vapor condenses in the
condenser and drips into the receiving flask. Typically, the liquid should drip into the receiving
flask at a rate of about 10 drops per minute. If the rate of distillation is too rapid, the heat
applied to the distillation flask must be decreased. With too rapid a rate, the measured boiling
point is likely to be inaccurate and the purity of the distilled liquid will be compromised.
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The first material that distills before the temperature stabilizes is called the forerun. The
forerun will contain any low boiling impurities and is usually discarded after checking its purity.
The material collected after the temperature stabilizes is the purified substance. Usually the
temperature stabilizes slightly below the literature value for the boiling point and then slowly
creeps up. When the temperature begins to drop, the distillation is halted by removing the heat
from the distillation flask. As a safety precaution, distillations are never carried out to dryness.
The residual liquid plus the liquid from the take-up volume is the price one pays for purity. The
boiling point of the collected material is actually a range rather than a point.
Note: A technique called Steam Distillation is often used to purify high boiling organic
compounds by distilling an immiscible mixture of the impure compound and water. For
example, the perfume industry uses this technique to purify many essential oils.
Heating
Many of the experiments in this course require heating. Although there are numerous
methods available, reaction conditions and chemical and physical properties of the materials
make certain heating methods preferable to others. Since most organic compounds,
especially the commonly used solvents such as hexane and ether, are flammable, a flameless
method is generally preferred. In these laboratories, you will usually use either a steam bath
or a sand bath.
Steam Bath: A steam bath, illustrated below, is often used to heat solutions that boil
below about 90C, or to heat a mixture to approximately 100C. The laboratories are
supplied with steam from a central boiler.
Before connecting the steam line to the bath, drain the water out of the steam pipes.
Turn the steam on with caution, the knobs are usually quite hot and some hot water will
come out before the steam does. Turn it on slowly, its quite normal for the pipes to make
some odd noises before the steam starts to come out. When youve got mostly steam, rather
than mostly hot water, connect the steam line to the top inlet on the bath. The bottom inlet
is attached to a hose, which drains into the sink. Any water that condenses in the bath while
youre using it will drain out. Think of the top of the steam bath like a stove burner, the
whole metal surface will be hot. You usually wont need to turn the steam up very far to
keep the steam bath hot. Having the steam turned up higher than necessarly just makes
noise and an odd smelling, jungle-style atmosphere. Moisture is the enemy of many
reactions and the lab should be kept as dry as possible. Usually, steam baths have concentric
rings as covers which should be in your lab drawer. You can control the size of the bath by
adding or removing rings.
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Sand baths or Heating Mantles: A useful source of heat for reactions, especially
where controlled temperatures over 100C are required, is the heating mantle( illustrated in
the figure below). The heating mantle used in these laboratories consists of a ceramic shell
with embedded electric heating coils. The ceramic bowl will accommodate flasks with
volume capacities up to 250 mL. With flasks smaller than 250 mL, the mantle can be used as
an air bath or a sand bath, usually the latter. A small layer of sand in the bowl will serve as
a medium for conducting heat to the reaction flask. Add just enough sand to nestle your flask
into. A depth of about 1 cm should be plenty. Large amounts of sand act more as an
insulator than a conductor. If you use more sand than just a thin layer, you will find that the
reaction will take a longer time to heat up.
The heating mantle is saferr, because it does not produce flames. However, there are
still precautions to be taken. Heating mantles must be used with variable transformers.
ALWAYS PLUG THE HEATING MANTLE INTO THE VARIAC. NEVER PLUG IT
DIRECTLY INTO THE WALL. If a heating mantle is plugged directly into the wall outlet,
it will become extremely hot. This is extremely hazardous as it can cause fires and burns and
can also cause the heating mantle to burn out. Avoid spilling chemicals into the heating
mantle.
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Procedure:
Miscible liquids such as a mixture of organic solvents with similar polarities (miscible
mixtures) with boiling point differences of at least 10oC can be separated by fractional
distillation. In this experiment, you will be given a mixture of two hydrocarbons included in the
list given below. You will be distilling this mixture and collecting fractions appropriately.
Using the boiling point data, the bromine test for unsaturation, and a test for aromaticity
(which will be done in Experiment 3) and spectroscopic data (NMR) you will be able to
identify the components of the mixture.
bp = 63
bp = 84
bp = 123
bp = 146
Aromatics
Toluene
bp = 111
Ethylbenzene
bp = 136
1,3,5-trimethylbenzene
bp = 165
Procedure
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Let your TA check your setup before you start distilling. Distill the mixture slowly
to obtain the best result, increase the temperature very gradually. The key to a good separation
is to establish liquid-vapor equilibria throughout the column. Too vigorous heating will flood
the column.
Think about it: Even though your heating mantle is heating, the temperature that the
thermometer displays doesnt change much until after the liquid boils. Why?
Collect the distillate in a receiver with volumetric graduations, your reaction vial with
the conical bottom is good for this. Save fractions about every 2 mL in labeled vials. Cap the
vials immediately. You may need an extra pair of hands to help you transfer liquid into the
vials, now is the time to make friends with the person down the bench from you! If the
boiling point changes or there is any change in the appearance of the distillate start a new
fraction immediately.
Think about it: Which fractions are the most pure samples of your low boiling
substance? Which fractions are the most pure samples of your high boiling substance? Is
more fractions better than less? Why?
While youre collecting fractions, you should also be recording temperature vs.
volume data so that you can create a graph like the one shown below. As the distillation
proceeds, record the temperature and the total volume of the distillate collected in your
laboratory notebook. Plot the data on graph paper or using a computer, the volume of distillate
on the horizontal(X) axis and the temperature on the vertical(Y) axis . Note on the graph the
positions that correspond to the collected fractions. In an ideal fractional distillation with
complete separation of the components, the first substance would distill at its boiling point until
there was none of it left in the mixture. Then, the temperature of the distilling vapor would rise
to the boiling point of the second substance and all of it would distill at its boiling point. In
practice, the behavior will depend on the fractionating column, the difference in boiling points,
and the rate of distillation.
Think about it: You may have observed a drop in temperature in the m iddle of the
distillation, in between the low and high boiling substances. Why might this have happened?
What does this say about the quality of your separation?
After the distillation is complete, use your temperature vs volume data to determine
which fractions are likely to contain the most pure samples of the two different hydrocarbons in
your unknown mixture. Make NMR samples of the two most pure fractions, noting which
sample is high boiling and which sample is low boiling. Save these fractions (at least two) to
check for the purity by gas chromatography and for chemical test for unsaturation and
aromaticity which will be done as part of Experiment 3. Wrap the vials containing the
collected fractions and your pre-distilled mixture with parafilm and store them in the
refrigerator (this will prevent evaporation of the samples). Make sure to label the vials with
your name and section number.
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