EXPERIMENT 15

FREEZING POINT: A COLLIGATIVE

PROPERTY OF SOLUTIONS
INTRODUCTION
Scientists seldom work alone today. Instead they work in teams on projects, sharing the labor of carrying out
the experiments and of interpreting the results. In this experiment, your lab group will work together to collect and
analyze data to determine the freezing points of a number of liquids, both pure solvent and solutions made from the
solvent and several solutes. The freezing point data you and your lab partner collect will be combined with the data
for your entire lab group, and your instructor will lead a discussion of what conclusions can be drawn from the data.
Following this you will measure the freezing point of a solution containing an unknown solid. Using the
information gathered above, you will determine the molar mass of the unknown solid.

TECHNIQUE
Determination of Freezing Points Using Cooling Curves
A cooling curve for a liquid shows graphically how the temperature varies with time as the liquid is cooled in a
constant-temperature bath. The liquid is contained in a test tube and is stirred continuously to maintain thermal
homogeneity. The rate of cooling is determined mainly by two factors. The first is the difference in temperature
between the liquid and the bath. This factor causes the cooling curve to become gradually less steep (smaller
negative slope) as the liquid temperature approaches that of the bath, eventually becoming zero, yielding a
horizontal line at the bath temperature. The second factor is the extent to which the liquid is insulated from the bath.
This factor does not control the overall shape of the cooling curve, but it does affect how long the experiment takes.
If the freezing point of the liquid is above the bath temperature, the cooling curve will not proceed in a smooth
curve all the way to the bath temperature. It will instead show a discontinuity, i.e., a sudden decrease in slope, at the
freezing point of the liquid. This slowing of the cooling occurs because the heat of fusion of the liquid is released as
the liquid freezes, at least partially compensating for the heat being lost to the bath. It is occasionally observed that
freezing does not begin immediately at the freezing point, but that supercooling occurs. When freezing does begin,
the heat released will raise the temperature to the level that would have been observed in the absence of
supercooling. Should supercooling occur in any of your samples, it will be obvious from the sudden, small rise in
temperature after the supercooling “dip” in the cooling curve.
Cooling curves for pure liquids differ from those for solutions. The temperature remains constant as a pure
liquid freezes, so a flat, horizontal region is expected in the cooling curve. If the cooling is continued until all of the
liquid has frozen, the temperature will then decrease further as the solid is cooled, until it finally reaches the
temperature of the bath. For a solution, on the other hand, the temperature continues to decrease as freezing occurs,
although at a lower rate. This occurs because it is pure solvent that is freezing out of the solution, leaving the liquid
solution more and more concentrated, continually decreasing the freezing point. If cooling is continued until all of
the solution has frozen, the cooling curve will become steeper again, since no more heat of fusion is being released.
It is important to note that it is the temperature at which the solution begins to freeze that is desired, since it is only
there that the concentration is known.
An experimental cooling curve for a pure liquid is shown in FIGURE 15-1 and for a solution in FIGURE 15-2.
Careful examination shows that a small supercooling “dip” occurred in both curves. It is also apparent that the

Tf = 6.52C

Tf = 3.35C

Figure 15-1. Cooling curve of a pure liquid. Figure 15-2. Cooling curve of a solution.

region after the onset of freezing in FIGURE 15-1 isn’t quite horizontal. The temperature continued to decrease
slightly as the solvent froze. This could mean that the solvent wasn’t 100% pure. It might, however, be due simply
to a cooling rate that was too high. The temperature remains constant as a pure liquid freezes only if the solid and
liquid are always essentially in equilibrium with each other. This may not be the case if the cooling is too rapid or if
the stirring is not adequate. The solvent must freeze rapidly enough to produce heat (heat of fusion) at the rate at
which heat is lost to the bath, and the stirring must be rapid and thorough enough to keep the temperature uniform
throughout the sample.
The cooling curve in FIGURE 15-1 was followed much longer than necessary after the onset of freezing, in
order to illustrate how the temperature drops quickly again after all of the liquid has frozen. Note how the freezing
point, Tf, is determined in each case. A line is drawn to extrapolate the behavior just after freezing began back
through the supercooling “dip” to the curve just before freezing began. The intersection of the extrapolated line
with this curve is taken as the freezing point. If supercooling were not observed, the freezing point would be taken
to be the point where the slope changes abruptly.
OBJECTIVES
 to determine the freezing points of several liquids
 to combine and discuss your data with the other students on your network
 to prepare a solution of an unknown solute and measure its freezing point
 to determine the molar mass of the unknown solute from the freezing point

EQUIPMENT NEEDED
beakers (150 mL and 800 mL) medium test tube
ring stand and clamp glass stirring rod
Styrofoam cups (2) temperature probe
Kimwipe tissues smaller test tube (supplied by stockroom)

CHEMICALS NEEDED
Note: Concentrations of solutions are expressed in units of molality.
cyclohexane, C6H12
naphthalene in cyclohexane (0.040 m, 0.080 m, 0.120 m, 0.160 m)
biphenyl in cyclohexane (0.040 m, 0.080 m, 0.120 m, 0.160 m)

PROCEDURE
A. Freezing Point Determination of Known Solutions and/or Pure Solvents
Each pair of students will be assigned at least three test liquids from the front of the lab room. Your instructor
will give you an assignment sheet. One of the liquids you will investigate will be pure solvent (cyclohexane); the
others will be solutions of a solute dissolved in cyclohexane. You will determine the freezing point of each of the
liquids you have been assigned.

Calibration of the Temperature Probe and Setup of Workstation Display

Press MAIN MENU on the workstation, press the function key for TEMPERATURE, and then the function
key for TEMPERATURE V TIME. Fill your 800-mL beaker with ice. Fill a Styrofoam cup approximately three-
quarters full with ice and add enough distilled water to barely cover the ice. This ice/water mixture will be at 0.0°C.
Press CALIBRATE and place the temperature probe in the ice water, using the temperature probe to continuously
stir the ice water for at least two minutes. Follow the instructions on the display for the calibration of the
temperature probe. Since data from all of the students on your network will be combined in this exercise, it is
particularly important to do a good job calibrating the temperature probe. Calibration errors will lead
directly to disagreement among the values obtained by various group members. When you have finished
calibrating the temperature probe, remove it from the ice bath and carefully dry it. This is necessary in order to
avoid contaminating one of the liquids to be studied by introducing water.
Press SETUP and set the graph limits for your workstation display. Set the minimum and maximum
temperatures at 0°C and 10°C, respectively, and set the maximum time at 900 seconds. Press DISPLAY to accept
the graph limits and begin monitoring the temperature.
Cooling Curve Measurements
Measuring a cooling curve experimentally would seem to be a very simple matter. However, in order to achieve
results of comparable quality to those in FIGURES 15-1 and 15-2, you must pay surprisingly close attention to
various details. Lack of careful technique in following the instructions below will be immediately apparent in your
cooling curves.
Place the Styrofoam cup you used in the temperature probe calibration inside another Styrofoam cup. Use this
nested pair of cups as the constant-temperature bath for each cooling curve measurement. Before each experiment
fill the cup to the top with ice and add (or pour out) just enough water to bring its level to within a centimeter or so
of the top. You need to have ice all the way to the bottom of the cup. Be sure to stir the ice-water bath
thoroughly before each experiment.
Perform the cooling curve experiment on the pure solvent first. Attach the clamp to the ring stand and clamp a
medium (18 mm  150 mm) test tube near its open end. Obtain a KimWipe, tear~ ¼ of it off, roll the smaller piece
into a ball, and place it in the medium test tube. To a smaller (15 mm x 125 mm) test tube (not in your drawer—
obtain from the back bench), add a small amount of cyclohexane (just enough to fill the curved bottom of the test
tube) and tilt the test tube so that the inner walls are rinsed, then pour the cyclohexane into the organic waste
container Now fill the test tube ~1/4 full (no more!) with cyclohexane and place it inside the medium test tube. The
KimWipe will hold the smaller test tube in the center of the larger one in such a way that they do not actually touch.
The reason for this rather strange-sounding arrangement is that it conveniently limits the rate at which heat can be
transferred from the smaller test tube to the bath around the larger one. If the cooling occurs too quickly, in addition
to the resulting problems discussed above, the temperature probe may not be able to “keep up” and accurately show
what is happening. The result would be a smearing out of the details around the onset of freezing, and that would
make it difficult or impossible to determine just where freezing begins.
Loosen the clamp on the ring stand and slide it down to lower the test tubes into the ice bath in the Styrofoam
cups. Wiggle the cups around as you insert the tube until it rests on the bottom. Do not press down too hard,
though, or you will break through the bottom of the cup. Insert the temperature probe into the liquid in the
smaller test tube and begin stirring the liquid. The best stirring technique is a regular, but gentle, up-and-down
motion, about twice per second, in which the probe is raised about two centimeters and then returned to the bottom
of the tube. It is important that you keep stirring smoothly throughout the course of the measurements in
order to maintain temperature homogeneity. While you stir, monitor the temperature on the workstation screen.
When it reaches 10°C, press START/STOP to begin collecting data. Continue stirring and monitor the plot of
temperature vs. time on the workstation screen. After freezing begins, as seen in the a change in slope on the plot or
from the numbers themselves, continue collecting data for about a minute more, then remove the smaller test tube
from the larger test tube (do not press START/STOP yet). When the liquid in the test tube has warmed up to
~10ºC, place it back in the larger test tube and allow the liquid to cool down to its freezing point. In this manner,
you will have two cooling curve experiments plotted on the workstation screen. When the second experiment is
complete, press START/STOP to stop collecting data. Remove the smaller test tube from the ice bath (you can
leave the larger one in the ice bath), remove the probe from the test tube, and wipe it off. (If the probe becomes
stuck in the frozen liquid, warm the tube with your hand until the liquid melts and you can remove the probe.)
Dispose of the liquid in the non-halogenated liquid organic waste container.
 Print your temperature versus time plot. To do this, press FILE OPTIONS, press the function key for PRINT
standard, and enter the number of copies to print, probably 2—one for you and one for your lab partner. As soon
as you obtain your printout, label the plot with the name of the liquid being investigated (in this case, cyclohexane)
. Show the printout to your instructor to make sure it is acceptable. To summarize, in order to obtain good-quality
cooling curves, you must (1) keep the ice bath filled to the bottom with ice, (2) use a tissue to properly position the
test tubes, (3) use the correct amount of liquid (no more than ¼ test tube full), and (4) stir smoothly and
continuously as data are collected.
Press DISPLAY twice after printing your data to clear the plot on the workstation screen. Repeat the above
procedure to obtain a cooling curve for each of your assigned solutions, adding more ice to the ice bath before the
experiment if necessary. As you print out each plot, be sure to label it completely for later identification.

DATA ANALYSIS
Analyze your cooling curves as illustrated in FIGURES 15-1 and 15-2 to determine the freezing points. If your
freezing point curve for the pure solvent does not have a horizontal portion (indicating too-rapid cooling or the
presence of an impurity in the solvent), analyze the curve as if it were for a solution. If the freezing points of your
two trials differ, record the average of the two trials. Before proceeding to the next step, have your instructor verify
that you are analyzing the data correctly.
Go to the computer connected to your network, be sure the program entitled “Freezing Point Plot” is running
and visible, (select it from the task bar at the bottom of the computer screen if it is not), enter your data, and update
the group plot.
When everyone has finished this part of the experiment, the freezing point data will be compiled into a single
plot of freezing point vs. concentration. Your instructor will print and distribute this plot and lead a discussion of
the results. In order to have this discussion in a timely fashion, you must have all of your freezing point data entered
into the computer by the time announced. After the discussion, you may proceed to Part B.

B. Molar Mass Determination of an Unknown Solute

Weigh out ~0.10 to 0.15 g of your unknown solute on an analytical balance into a 150-mL beaker, recording
the mass to the nearest 0.0001 g. Its molar mass is in the range from 100 to 200 g/mol. Be sure to record the
unknown number! Measure out 10 mL of cyclohexane from a buret into the beaker. It is not important that you
measure exactly 10 mL. However, you should record the actual volume you use to the nearest 0.01 mL. After
the solute is completely dissolved in the cyclohexane, measure the freezing point of the solution by performing the
cooling curve experiment as described in Part A.
Look up and record the density of cyclohexane, which will be used to calculate the mass of cyclohexane used.

Waste Disposal
Any unused solution should be poured into the Liquid Organic Waste container.
RESULTS
Part A. Freezing Points of Known Solutions
1. Include in your report the printouts of your cooling curves, showing how you determined the freezing points,
and the group freezing point vs. concentration plot. Make sure all graphs are given appropriate titles.
2. Fill out the report sheet table summarizing the results of your freezing point measurements.
Part B. Molar Mass of Unknown Solute
1. Determine the freezing point, Tf, from the cooling curve of the solution containing your unknown solute. Show
how you determined the freezing point, and be sure the graph is given an appropriate title.
2. Use the freezing point of your unknown solution and the equation of the best fit line drawn through the group
plot data to determine the molality of your solution. Show how you obtained this value.
3. Calculate the mass of cyclohexane used in the experiment. Use the mass of cyclohexane and the solution
molality determined above to calculate the molar mass of your unknown solute. Recall that molality is
calculated by:
moles solute
molality = (15-1)
kg of solvent
Record this information on the REPORT SHEET. Show all calculations.

DISCUSSION
Write a paragraph or two briefly describing the results and conclusions of the group experiment involving the
freezing points of the known solutions. Be sure to cover the following topics:
1. How is the freezing point determined from a cooling curve graph?
2. What is the effect of the concentration of solute (expressed in molality, m) on the freezing point of the solution?
3. What is the effect of the chemical identity of the solute on the slope of the concentration vs. freezing point
curve?
4. Explain how the data support the assertion that freezing point depression is a colligative property.
 EXPERIMENT 15
REPORT SHEET
Name: _______________________________________ Date:__________

Partner:______________________________________

PART A. FREEZING POINTS OF KNOWN SOLUTIONS

concentration solute freezing point

_________________________________________ ________ ________

_________________________________________ ________ ________

_________________________________________ ________ ________

_________________________________________ ________ ________

PART B. MOLAR MASS OF UNKNOWN SOLUTE

Unknown Number of Solute _______

Mass of Solute ______________________________________

Volume of Cyclohexane_______________________________

Density of Cyclohexane _______________________________

Mass of Cyclohexane, kg ______________________________

calculation:
Freezing Point of Solution ________________________________

Concentration of Solution ________________________________

(from freezing point curve)

Moles of Solute ________________________________________

calculation:

Molar Mass of Unknown _________________________________

calculation:
 Lab Notes
Experiment 15
Freezing Point: A Colligative Property of Solutions

Procedure considerations
 Part A: You should perform three freezing point experiments: one with a pure solvent,
two with solutions. Your assigned liquids are listed on the last page. Measure the
freezing point of the pure liquid first.
 You should be able to do two cooling curve trials for a liquid without having to reset the
workstation screen. Do not press 'Start/Stop' until after the second time the liquid has
frozen.
 You will be following a timetable during this experiment in order to have a group
discussion of the Part A data. The timetable will be as follows:
First two hours Collect freezing point data for Part A; analyze curves; enter data
on computer
At 2 hour mark TA leads group discussion of compiled data
After discussion Complete Part B
 Be sure to take notes during this discussion! There will be topics discussed that will
need to be included in your lab report.
 If you have completed Part A before the discussion you may begin Part B by preparing
your unknown solution. You may perform the cooling curve trials for Part B if you are
ready do so before the discussion; however, you should stop what you are doing when it
is time for the group discussion.

Helpful Hints:
The two most important points to remember in this experiment are stir the solution or
solvent continually and make sure the ice bath is sufficiently cold. The ice bath should be at
least 3/4 filed with ice for each trial. Stir the ice water briefly before each trial to ensure
that the temperature of the ice bath is relatively uniform. Submerge the test tube in the ice
bath as far as possible.
 Freezing Point Liquid Assignments

Station # Liquid Assignment Station # Liquid Assignment

1, 9 1) Cyclohexane 5 1) Cyclohexane
2) 0.04 m biphenyl in cyclohexane 2) 0.04 m biphenyl in cyclohexane
3) 0.16 m naphthalene in cyclohexane 3) 0.16 m naphthalene in cyclohexane

2, 10 1) Cyclohexane 6 1) Cyclohexane
2) 0.08 m biphenyl in cyclohexane 2) 0.08 m biphenyl in cyclohexane
3) 0.12 m naphthalene in cyclohexane 3) 0.12 m naphthalene in cyclohexane

3, 11 1) Cyclohexane 7 1) Cyclohexane
2) 0.12 m biphenyl in cyclohexane 2) 0.12 m biphenyl in cyclohexane
3) 0.08 m naphthalene in cyclohexane 3) 0.08 m naphthalene in cyclohexane

4, 12 1) Cyclohexane 8 1) Cyclohexane
2) 0.16 m biphenyl in cyclohexane 2) 0.16 m biphenyl in cyclohexane
3) 0.04 m naphthalene in cyclohexane 3) 0.04 m naphthalene in cyclohexane