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Chapter the Eleventh

BP: Boiling Point Elevation by a Solid

11.1 INTRODUCTION

A colligative property is a physical property that depends solely on the number of


particles of solute present and not on their nature (big, small, ionic, light, heavy,
etc.). This experiment studies one of the four colligative properties of dilute systems:
boiling point elevation, that is, the increase in the boiling point of some volatile
material as small amounts of nonvolatile solute are added. Boiling point elevation
data can be used to calculate the molecular weight of the added solute; however, this
requires an extremely accurate measurement of the temperature change. We use a
special thermometer for this purpose. In addition, we have to take steps to avoid the
effects of superheating on our measurement of the boiling point. The technique of
determining molecular weight by boiling point elevation is called ebullioscopy.

Figure 11.1 Experimental Setup

147
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148 Hooked on PChem Lab

It is important to remember that boiling point elevation is dependent on the


number of solute particles. An interesting application of this experiment is to study
solutions in which the number of solute particles is not necessarily the number pre-
dicted solely from the number of moles of solute in the solution. For example, an
ionic solid in an aqueous solution will dissociate, resulting in an increased number
of particles in solution. In this experiment, you will investigate the alternative sit-
uation where a solute dimerizes, decreasing the number of particles in solution.

11.2 TEXTBOOK REFERENCES

Daniels, F.; Alberty, R. A.; Williams, J. W.; Cornwell, C. D.; Bender, P.; Harriman,
J. E. Experimental Physical Chemistry; McGraw-Hill: New York, 1970; p. 86.
(available in the library in the pchem reference folder, and through E-Reserves)

11.3 CHEMICALS

Above your bench

Benzoic acid

Chloroform

Naphthalene

11.4 EQUIPMENT

Refer to Sections 4.2, Analytical Balance, 4.10, Pellet Press, 4.11.2, Thermistor
and 4.14, Volumetric Pipette.

Stockroom In the experiment drawer

Condenser Two beakers (one large, one


medium)

Cottrell flask Heat-protecting gloves

Glass pumping mechanism Boiling chips

50 mL volumetric pipette Hot/Stir plate

Digital thermometer Magnetic stir bar

Thermistor probe with digital readout Pipette bulb

One one-holed rubber stopper Two spatulas

Supply bench Large tweezers

Analytical balance Hoses and hose clamps

Pellet press Lab stand and clamps


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Chapter 11 BP: Boiling Point Elevation by a Solid 149

11.5 SAFETY

Physical Hazards Health Hazards

Benzoic acid None Severe irritant, sensitizer

Chloroform None Highly toxic, carcinogenic, mutagenic

Naphthalene Flammable Toxic, irritant, sensitizer, carcinogenic

Wear gloves and use a fume hood while measuring these chemicals. Keep the con-
denser pointing toward the back of the bench at all times. (The boiling solution can
‘bump’, blowing the hot solution out of the condenser with considerable force.)

11.6 PROCEDURE

The boiling point elevation experiment is the most sensitive experiment in this lab.
Pay attention to the hints in the procedure warning you of potential problem areas.
A small experimental error will result in a large error in your final results.

Thermistor

Condenser

Rubber
stopper

Cottrell
Flask

Glass
Pumping
Mechanism

Figure 11.2 Boiling Point Elevation Apparatus


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11.6.1 Setup

1. The glassware supplied by the stockroom will be clean. Thoroughly clean and
dry the probe of the thermistor. Assemble the flask and condenser. (Do not
use grease for the ground glass joint, unless you are interested in the boiling
point elevation of a solution of vacuum grease in chloroform.)
2. Set up a 500 mL beaker on the hot plate to be used as a water bath. Position
one clamp to hold the Cottrell flask so that the water bath can be used to heat
the contents of the flask, positioning the clamp as high up the flask body as
safely possible (to maximize the length of flask able to be in the water bath,
minimizing the amount of water needed in the water bath, and thus minimiz-
ing the amount of time needed to heat the water bath). Attach the condenser,
taking care to point the condenser away from you and toward the back of the
bench. (This is important. We’ve had several instances where boiling liquid has
bumped out of the condenser, for reasons that we think we understand and are
avoiding now.) Make sure that it is possible to disconnect the flask from the
condenser, so that you can change flasks later in the experiment. (Note that the
pumping mechanism should not yet be in the flask.)
3. When you are satisfied that all parts of your apparatus are securely positioned
and clamped, connect the hoses to and from the condenser, making sure to
use hose clamps, and ensure that there are no leaks. Add enough warm water
to your water bath to immerse the bottom inch of the Cottrell flask. Set up the
small digital thermometer to monitor the bath temperature. Use a stir bar to
distribute the heat throughout the bath, making sure the stir bar rotates with-
out bumping the flask or the thermometer. Start heating the water.

11.6.2 Boiling Point of the Pure Liquid

4. Add enough chloroform to the flask to submerge the bottom 1 cm of the ther-
mistor probe. Place the pumping mechanism in the flask. Add three or four
large boiling chips. (Too many, or too small, boiling chips will prevent the
pumping mechanism from functioning properly. You do not want to use boil-
ing chips that are small enough to fit inside the main arm of the pumping
mechanism, to prevent possible bumping hazards.) Use the rubber stopper to
position the tip of the thermistor probe inside the flask about 1 cm below the
liquid surface. Make sure there is a good seal between the thermistor and the
stopper, so that no vapour escapes. Make sure the level of liquid in the water
bath is slightly higher than that of the liquid in the flask. (Lowering the flask
into the bath, rather than increasing the volume of water, will reduce the time
you will spend waiting for the bath to heat up.) Plug the thermistor probe cable
into the digital thermometer readout, and keep it away from the hot plate. Press
the upper half of the rubber rocker switch marked On/Off to turn the unit on.
A second press will turn the unit off. Note that the thermometer will shut it-
self off after 10 minutes of operation. Make sure the thermometer is working
in degrees C . To toggle between °C and °F, press the lower half of the rubber
rocker switch down for ,4 seconds, while the HOLD indicator flashes, and
then the units indicator will switch to show which units are now in use.
5. Heat the water bath up to its boiling point. As heat transfers from the bath to
the chloroform, the chloroform will begin to boil and reflux in the condenser.
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Chapter 11 BP: Boiling Point Elevation by a Solid 151

(You will see liquid drops forming inside the condenser. If this is occurring too
close to the exit end of the condenser, increase the water flow to the condenser
water jacket, or reduce the heat of the water bath, so that you don’t lose your
chloroform out the end of your condenser and gas your neighbours.)
6. Wait until the chloroform has established a good rolling boil. You should
clearly see reflux in the condenser, and the liquid surface should be agitated,
not just an occasional bubble rising to the surface. Record the temperature
reading on the thermistor at regular intervals. The resolution of the thermis-
tor probe is very sensitive (60.01K at this temperature range), so the temper-
ature reading will not remain stationary but will vary around some average
position, due to temperature and pressure fluctuations in the laboratory.
7. The temperature of the refluxing liquid will approach a constant value as the
system approaches equilibrium. Wait long enough to be satisfied that it has
equilibrated. (A perfectly constant boiling point cannot be expected, but at
equilibrium the observed temperature will vary slightly around a mean value.)
When your system has reached equilibrium, record your estimated average
temperature of the refluxing liquid. (Care must be exercised in all temperature
readings, since a small error here will lead to large errors in your data
analysis.) Because boiling point is sensitive to changes in pressure, record the
barometric pressure of the room just after taking your final temperature
reading.

11.6.3 Boiling Point of the Calibration Solution

8. While you are waiting for the chloroform to boil, weigh , 5 g of naphtha-
lene. Use the pellet press to compact the naphthalene into several tablets. Ac-
curately record the total weight of your tablets. (Making a pellet makes it
easier not to lose some of your sample when adding it to the flask. Naphtha-
lene flakes easily stick to the sides of the flask.)
9. After recording the boiling point of pure chloroform, turn the heating plate
off. Remove the thermistor probe. Carefully, using protective gloves, discon-
nect the flask from the condenser and clamps. Pour the hot chloroform into a
beaker in the hood, and leave it to cool.
10. DO NOT leave the beaker of waste chloroform/benzoic acid/naphthalene in
the beaker in the hood. Dispose of it appropriately, clean the beaker, and re-
turn it to your drawer.
11. You do not have to clean the flask. Simply put two or three large boiling chips
and your naphthalene tablets into the bottom of the flask, followed by the
pumping mechanism. Connect the flask to the condenser and clamp it into
place.
12. Use the volumetric pipette to add 50.0 mL of chloroform to the flask. Use the
rubber stopper to position the thermistor probe inside the flask so that the end
of the probe falls between the arms of the pumping mechanism and down
about 3/4 of their length. Make sure there is a good seal between the thermis-
tor and the stopper so that no vapour escapes and so the level of liquid in the
water bath is slightly higher than that of the liquid in the flask.
13. Heat the mixture, dissolving the naphthalene. Do not leave your experiment
unattended. Check periodically to ensure that no boiling chips have become
lodged up the main arm of the pumping mechanism. This is potentially
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152 Hooked on PChem Lab

dangerous, because if pressure that is built up behind the boiling chip is sud-
denly released, hot liquid can bump out the end of the condenser. If you see
such a situation developing, stop the experiment and remove that boiling chip
from your system. As the solution boils, it will start bubbling up through the
arms of the pumping mechanism and spraying out over the thermistor probe.
(If the liquid does not flow steadily through the pumping mechanism, adjust
the water bath heat. Do not allow the liquid to get hot enough to bubble up over
the pumping mechanism. You may have to reposition things so that the boil-
ing chips are beneath the pumping mechanism.) Record the temperature read-
ing on the thermistor at regular intervals. Wait until the temperature has
finished rising and is relatively stable. Wait longer because you probably
haven’t waited long enough. When your system has reached equilibrium,
record your estimated average boiling point of the chloroform/naphthalene
mixture as read by the thermistor. The difference between this reading and
that taken for the pure chloroform is the boiling point elevation for this
solution.
14. While you are waiting for the naphthalene/chloroform solution to boil, weigh
, 5 g of benzoic acid. Use the pellet press to compact this into several tablets,
and accurately record the total weight of your tablets.
15. After recording the boiling point of the naphthalene/chloroform solution, add
the hot solution to the beaker in the hood to cool and thoroughly clean and
dry the flask and the lower portion of the thermistor probe. (You don’t want
to study a benzoic acid/naphthalene/chloroform mixture.)

11.6.4 Boiling Point of the Benzoic Acid Solution

16. Repeat the experiment, investigating a benzoic acid/chloroform solution. It is


unnecessary to again measure the boiling point of chloroform.

Table 11.1 Waste Disposal

Waste Chemicals Waste Container

Excess solid naphthalene, benzoic acid Solid waste

Chloroform-containing waste Organic halogenated

11.7 WASTE DISPOSAL

Do not pour hot chloroform into the waste bottle. Wait until it has cooled. Speed up
cooling by placing the beaker in a bucket of ice water.

11.8 SHUT DOWN

1. Turn off water to the condenser. Turn off the hot plate/magnetic stirrer.
2. Make sure the pellet press/balance area is clean and that you have returned your
chemicals to where they belong.
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Chapter 11 BP: Boiling Point Elevation by a Solid 153

3. Put all waste, including the chloroform you left in the hood to cool, in the ap-
propriate waste containers. Clear up any spills that have occurred. Clean and dry
all glassware. Put away all equipment used. Return appropriate items to the
stockroom.
4. Ask your TA to check and sign for your equipment drawer, initial your lab book
and fill in the appropriate Report Summary Sheet.

11.9 LITERATURE VALUES

Chloroform: Boiling point 5 334.8 K


Density 5 1.4832 g cm23
Kb 5 3.63 K kg mol21

11.10 DATA ANALYSIS

11.10.1 Boiling Point of the Calibration Solution

1. Calculate the molality of your solution of naphthalene in chloroform.

# of moles of solute
molality 5 (11.1)
mass of solvent in kg

2. For dilute solutions, the size of the boiling point elevation depends upon the
solute concentration:

DTb 5 Kb m (11.2)

where DTb is the elevation of the boiling point (in Kelvin) for a solution of mo-
lality m over that of the pure solvent and Kb is a constant characteristic of the
solvent called the boiling point constant, or the molal elevation of the boiling
point. Find the experimental Kb for chloroform from your observed boiling
point elevation. Compare to the supplied literature value.

11.10.2 Boiling Point of the Benzoic Acid Solution

3. Equation 11.2 can be converted to calculate the molecular weight of the solute
M in g mol21, where g grams of solute dissolved in G grams of solvent of
boiling point constant Kb gives a boiling point elevation DTb:

1000[g ? kg21]Kbg
M5 (11.3)
GDTb

Using your experimentally determined Kb for chloroform, your observed boil-


ing point elevation for the benzoic acid/chloroform mixture, and your masses
of solute (benzoic acid) and solvent (chloroform), calculate the apparent mo-
lecular weight of benzoic acid for your solution.
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4. Compare your apparent molecular weight to the actual molecular weight of


benzoic acid. Benzoic acid forms dimers in chloroform solutions,2 (i.e., the
number of particles in solution is decreased).

2(Benzoic acid)S(Benzoic acid)2 (11.4)

In this solution, the apparent molecular weight calculated using equation 11.3
is an average of the molecular weights of the components of the solution. You
should have gotten an apparent molecular weight that is higher than the molec-
ular weight of benzoic acid but lower than the molecular weight of a benzoic
acid dimer. (If you were way off, try recalculating your apparent molecular
weight using the literature value of Kb. If this doesn’t help, either do the calcu-
lations anyway with your data, or ask your TA for some sample data, and then
comment on the experimental problems that may have specifically led to your
bad data. Suggest how you would avoid them in future.)
5. For the monomer/dimer equilibrium, the experimentally determined apparent
molecular weight M is:

M 5 Xdimer Mdimer 1 Xmonomer Mmonomer (11.5)

where X are the solute mole fractions and M are the actual molecular weights.
Solute mole fractions are based on solute only (i.e., neglect solvent), thus:

Xmonomer 1 Xdimer 5 1 (11.6)

Substituting (6) into (5):

M 5 (1 2 Xmonomer) Mdimer 1 Xmonomer Mmonomer (11.7)

Assume that benzoic acid in a chloroform solution exists in an equilibrium such


as described by equation 11.4. Using the known molecular weights of benzoic
acid monomer and dimer and your experimental apparent molecular weight,
calculate the mole fractions of monomer and dimer at equilibrium by solving
equations 11.6 and 11.7 simultaneously.
6. We can define Nr as the number of moles of benzoic acid that has reacted to
make dimer. The number of moles of benzoic acid monomer and benzoic acid
dimer in the final solution is given by:

Final number of moles Benzoic acid monomer 5 (11.8)


Initial moles of benzoic acid 2 Nr
Nr
Final number of moles Benzoic acid dimmer 5 (11.9)
2

Express the mole fraction of benzoic acid monomer in terms of the final number
of moles of monomer and dimer in solution, and therefore solve for Nr and hence
calculate the final number of moles of monomer and dimer in the solution.
7. Calculate the corresponding molarities of the monomer and dimer, assuming
that the density of the solution at its boiling point is 1.55 g>cm3. Don’t forget
to use the total mass of the solution, including the mass of the chloroform and
the mass of the benzoic acid.
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Chapter 11 BP: Boiling Point Elevation by a Solid 155

8. Use these molarities to calculate the equilibrium constant of the dimerization


reaction.

11.11 DISCUSSION QUESTIONS

1. What is superheating, and what causes it? How do we compensate for this ef-
fect in our experiment?
2. Explain why your experimentally determined molecular weight from the ben-
zoic acid solution is not equal to the molecular weight of benzoic acid. Draw
the structure of a benzoic acid dimer, taking note of equation 11.4. Why didn’t
we worry about the formation of naphthalene dimers?
3. The thermistor you used can be read to within 60.01K . Do a test calculation
to determine how a small discrepancy in your temperature measurement can
create a large change in your predicted molecular weight. We formerly used a
Beckmann thermometer in this experiment that could be read at a higher reso-
lution than the thermistor. (We stopped using the Beckmann thermometer be-
cause it is extremely expensive, easily breakable, and difficult to calibrate.) Is
our current thermistor sensitive enough, or should we use a more sensitive ther-
mometer for this experiment?
4. What would you observe if you measured the boiling point elevation of benzoic
acid dissolved in ethanol? You should address intermolecular forces in your
answer.

11.12 CONCLUSIONS

As part of your conclusions for this experiment, compare your equilibrium con-
stant to its literature value.1

1
Tanaka, H.; Yamamoto, Y., Chuman, H. Determination of the distribution coefficients of phenol de-
rivatives and others based on a volume ratiometry coupled with a shake-flask method. Analytical Sci-
ences 2002, 18, 485. This paper did not measure Keq ; however they state it clearly on page 486. They
used a mathematical manipulation of data from another paper (Davies, M. and Griffiths, D. M. L. In-
tramolecular hydrogen bonds and the association and solubilities of substituted benzoic acids J. Chem.
Soc. 1955, 132.) to arrive at this value. (Keq 5 1/104K12/104) 5 1/210 3 1024 5 48 L mol21).
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