EXPERIMENT 8

Colligative Properties;
Determination of Molecular Weight
by Freezing-Point Depression

Whenever a substance is dissolved in a solvent, the vapor pressure of the solvent is lowered.
As a result, the boiling point, freezing point, and osmotic pressure are changed. The mag-
nitude of these changes depends on the number of solute particles in a mass of the solvent.
Properties of the solvent that depend only on the number of solute particles dissolved and
are independent of the nature of the particles are called COLLIGATIVE PROPERTIES. If a non-
volatile substance is the solute, the freezing point of the solution is lowered and the boiling
point is raised. Some common uses of these colligative properties are the addition of anti-
freeze to automobile cooling water to lower its freezing temperature, and the sprinkling
of salt on icy sidewalks to melt the ice by lowering its freezing temperature.
CoIIigative properties are very useful for determining molecular weights of unknown com-
pounds and the degree of dissociation of known compounds in solution.
The relation between the molecular weight of an unknown solute and the freezing-point
depression of a solvent is given by
tr (pure solvent) - tr (solution) = Krm
where
tr = freezing temperature
Kr = freezing-point constant for the solvent
m = molality of solute in the solvent
Molality of solute is defined as
moles of solute g of solute/molecular wt of solute
m = kg of solvent = kg of solvent
To determine molecular weights by the freezing-point depression of a solvent, you first
calibrate the solvent by dissolving a measured amount of a known compound into it. It is
important that the solute does not dissociate so that the number of particles of solute in
solution is equal to the number of molecules added. The freezing-point depression is
measured and the freezing-point constant is determined. The freezing-point constant is
equal to the number of Celsius degrees that the freezing-point of the solvent is lowered when
1 mole of solute particles is present in 1000 g of solvent. Some freezing-point constants of
common solvents are given in Table 8.1.
In this experiment you will use paradichlorobenzene (PDB)O as the solvent. Because your

o Naphthalene may be used instead. Its freezing point and K. value are compatible with the procedure de-
scribed here.

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EXPERIMENT 8: COLLIGATIVE PROPERTIES; MW BY FREEZING-POINT DEPRESSION

Table 8.1

Solvent Freezing point (0C) Kr (OC kg solvent/moles solute)

Water 0.0 1.86

Naphthalene 80.2 6.9
Benzene 5.5 5.1
Camphor 17.8 37.7
Paradichlorobenzene 53.1 7.10
(PDB)

thermometer is not precisely calibrated you cannot assume that it would indicate the exact
freezing point of PDB, but you are only interested in the temperature change anyway. So
you must first determine the freezing point of PDB as measured with your equipment.
To do this, you will have to measure the rate at which the liquid and solid PDB cools. This
is necessary because the freezing temperature is often difficult to determine by simple visual ob-
servation, due to undercooling and the fact that solidification of solutions often takes place over
a broad temperature range. Therefore, it is necessary to construct time-temperature graphs
called cooling curves, as in Fig. 8.1, so that you can determine the freezing point by extrap-
olation. You will do this first for pure PDB, to calibrate your thermometer, and then for
a solution of an unknown solute in PDB. The figure shows how the freezing point of a
solution must be determined by extrapolation of the cooling curve. Extrapolation is neces-
sary because when a solution freezes, the solid that forms has a different composition from
the liquid. Usually the solid is pure or nearly pure solvent, and therefore the remaining
liquid becomes increasingly more concentrated in solute as solidification progresses. The
change in solute concentration continues to lower the freezing point during crystallization

Pure liquid Pure liquid Pure solid

is cooling is freezing is cooling
I
Freezing I
Pure substance
point of I
Solution pure substance
/ / i Estimated freezing
/ I point of solution
I

t / I
- - - - - - - --I-,...""T""------.I..
I -....... Undercoollng
.
-1---- -
- ~--- :::-
(supercooling)

Variation in
observed freezi ng
point depends
on how much
undercooling
takes place

Time -----
Fig. 8.1. Cooling curves for pure and impure substances

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 EXPERIMENT 8: COLLIGATIVE PROPERTIES; MW BY FREEZING-POINT DEPRESSION

and produces the sloping cooling curve that follows the start of crystallization, as shown in
Fig. 8.1. Clearly, undercooling produces an ambiguity in the freezing point and should be
minimized. Sometimes "seeding" the mixture by dropping a small crystal of the solute into
it at the expected freezing point will reduce the amount of undercooling. Stirring the solution
also helps. Usually, you still have to extrapolate the "liquid freezing" line back to the
"liquid cooling" line of the solution, as in Fig. 8.1, to estimate the freezing point.

Procedure

A. Calibration of Thermometer with Pure Paradichlorobenzene

Weigh a large test tube on a triple beam balance to 0.01 g.

Add about 25 g of paradichlorobenzene (PDB) and weigh again.
Fill your 600-ml beaker nearly full of water and heat it to about 75°C. Clamp the test tube
(I

in the water bath as shown in Fig. 8.2.

Wire stirrer Thermometer

Testtube

Water bath

PDB in test tube

Fig. 8.2. Apparatus for measuring cooling curves.

(I If naphthalene is used, heat the water to 85°C.

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EXPERIMENT 8: COLLIGATIVE PROPERTIES; MW BY FREEZING-POINT DEPRESSION

When most of the PDB has melted, insert your thermometer and stirrer into the test tube.
Have the loop of the stirrer circled around the bulb of the thermometer and be sure the bulb
is well covered with liquid PDB.
When all of the PDB has melted, stop heating, empty the water bath beaker, and dry the
outside of the test tube with a towel.
Place the test tube in an empty wide mouth bottle to let it cool. Stir the liquid continuously
as it cools, to minimize the undercooling and maintain a uniform temperature. Take tem-
perature readings every 30 seconds.
When the freezing point of PDB is reached, crystals will start to form and the temperature
will remain constant. Shortly after this, the PDB will have solidified to the point where you
can no longer stir it.
Your cooling curve should resemble the "pure substance" curve in Fig. 8.1. Repeat this
cooling curve and take the average of your two freezing points.

B. Determination of the Molecular Weight of an Unknown Compound

Weigh your unknown in its container to 0.01 g.

Add about 3 g of unknown to the test tube containing the PDB on which you have just run
a cooling curve.
Reweigh the sample container to obtain the solute weight by difference.
Heat the test tube in a water bath as before until all the solid material is melted.
Then discard the water, dry the tube, and allow the solution to air cool as before. Record
the temperature every 30 seconds. The cooling curve should be similar to the "solution"
curve in Fig. 8.1. Repeat the cooling-curve measurements so you have two estimated freezing
points to average. Calculate the molecular weight of your unknown.
Dispose of the PDB solution by melting it in the hot water bath and pouring it into the dis-
posal jar provided for that purpose. Most of the remaining PDB can be scraped out of the
test tube with a dry brush.
DO NOT DISCARD poe IN THE SINK.

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NAME . _ GRADE .... _. ... __... .. ..

CHEMISTRY CLASS . _ INSTRUCTOR'S INITIALS _

DATE . _

Experiment 8: DATA

(Indicate units)

Unknown No _ _ _._ __ .

Determination
1 2
Freezing point of solvent
Freezing point of solution
Depression of freezing point
Weight of solvent
Weight of solute
Molecular weight of unknown
Relative average deviation

Calculations: (Graph paper for your cooling curve plots is provided in the back of the book.)

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EXPERIMENT 8: COLLIGATIVE PROPERTIES; MW BY FREEZING-POINT DEPRESSION

Experiment 8: ANSWER SHEET

1. Expain how the following errors would affect your calculated value of the molecular weight.
(a) Some solvent is lost by volatilization.

(b) Some unknown is lost during transfer to solvent.

(c) Thermometer reads 1° too low in range from 0° to lOO°C..

2. What is the advantage of placing the tube in a bottle during cooling, rather than leaving it in the
open air?

3. What relative error is introduced in the molecular weight of the unknown if 1.0% of the solid does
not dissolve? Will the error be positive or negative?

4. Is it necessary for the solvent to be free of impurities? Explain your answer.

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