Freezing Point Depression

Introduction

Solutions that contain nonvolatile solutes have a higher boiling point and a lower freezing
point than the initial pure solvent. These colligative properties result from the fact that the vapor
pressure of a solution with a nonvolatile solute is lower than the vapor pressure of the pure solvent.
Remember that a colligative property is a physical property of a solution that depends on the
number, but not the kind, of solute particles in a given amount of solvent.
The vapor pressure of a liquid is determined by the ability of particles at the liquids surface
to escape into the vapor phase. When we add solute to a pure solvent some of the spaces at the
surface of the liquid will be occupied by the nonvolatile solute. Since some of the spaces are taken
by the solute fewer solvent particles are in a position to escape into the gas phase. This means that
the solutions vapor pressure is lower than the pure solvent’s vapor pressure at all temperatures.
The boiling point of a substance is when the vapor pressure is equal to the atmospheric pressure.
Since the solute decreases the vapor pressure of the solvent, more heat needs to be added for the
vapor pressure of the solution to be equal to the atmospheric pressure. This is why solutions with a
nonvolatile solute have higher boiling points than the pure solvent.
Vapor pressure lowering also causes freezing point depression (see Figure 1). The
freezing point of a substance is the temperature at which its solid and liquid phases coexist in
equilibrium. The freezing point depression of a solution is the decrease in the freezing point of a
solvent caused by the presence of a solute. Another way to state this is that the freezing point of a
solution is the temperature at which the solvent in a solution and the pure solid solvent have the
same vapor pressure. Vapor pressure lowering results in freezing point depression provided that the
solution does not freeze as a solid solution. The solid that forms must be the pure solvent.

Figure 1: Vapor Pressure Diagram for Water and an Aqueous Solution

Wate
rSolutio
n
Liquid
Solven
Pressure, atm

Solid
Solven t
t
Dtb

Dtf

Temperature
 We can relate the freezing point depression of a pure solvent, Dtf, to the molality of the solution (m),
as seen in Equation 1 and 2.

(1) Dtf = tsolvent – tsolution

(2) Dtf = Kf m

Where tsolvent is the freezing point of the pure solvent, tsolution is the freezing point of the solvent from
the solution, and Kf is the molal freezing point depression constant, which is a property of the solvent.
Kf for water is 1.86°C/m. The molality of a solution is defined as the number of moles of solute per
kilogram of solvent (Equation 3).

(3)
moles solute
m=
kg solvent

Expressing the number of moles of solute in terms of its mass and its molar mass, we can rewrite
Equation 3 as in Equation 4.

(4) (mass of solute, g) (1 mole solute/molar mass of solute, g/mol)

m=
mass of solvent, kg

Determining the Molar Mass of an Unknown Solute

Equation 2 reveals that by measuring the freezing point depression of a solution you can
determine the solution molality. Knowing this experimentally determined molality and knowing how
the solution was prepared (what mass of solute was combined with what mass of solvent) you can
obtain the molar mass of the solute. A scheme for obtaining the molar mass can be seen in Equations
5-7.
ΔT f
(5) mExperimental = (6) (mexperimental) (kg solvent) = moles solute
Kf
mass solute (g)
(7) Molar Mass of solute =
( moles solute)
Graphing the temperature vs. the time for a pure solvent and a Solution we can see their respective
freezing points. See Figure 2 A and B.

Figure 2: Cooling Curves for A (water) and B (Solution)

Temperature

Temperature

Tf
Tf

(2A) Time (2B) Time

Materials:
1. Apparatus: Sketch the apparatus used for the freezing point depression lab.
a. Figure 3: Apparatus for Freezing Point Determination.

Thermometer attached to
LabQuest

Stoppe

Freezing Point Depression

Cla Test Tube

Support
Ring
600 mL Beaker
with
Ice/Water/Rock
Salt Bath

Ring
Water or Solution
Stand
 2. Chemicals:
a. Sodium Chloride
b. Water

Procedure

1. Go to Beyond Labz and login. Select Calorimetry followed by presets, and then select
Freezing Point Depression of NaCl from the list of assignments. The lab will open in the
Calorimetry laboratory with a beaker containing 45.00 g of ice and a coffee cup
calorimeter on the lab bench. A sample of sodium chloride (NaCl) will also be on the
balance.
2. Click on the Lab Book to open it. Record the mass of the sodium chloride in the data
table. If it is too small to read, click on the Balance area to zoom in, record the mass, and
then return to the laboratory.
3. 100 mL of water is already in the calorimeter. Use the density of water at 25oC (0.998
g/mL) to determine the mass from the volume and record it in the data table. Make
certain the stirrer is On (you should be able to see the shaft rotating). In the
thermometer window, click Save to begin recording data in the lab book. Allow 20-30
seconds to obtain a baseline temperature of the water. Click the clock on the wall
labeled Accelerate to accelerate the laboratory time if necessary.
4. Drag the beaker of ice (45.0 g)until it snaps into place above the calorimeter and then
pour the ice into the calorimeter. Click the thermometer and graph windows to bring
them to the front and observe the change in temperature in the graph window until it
reaches zero. Drag the weigh paper from the balance to the calorimeter and then pour it
into the calorimeter. Observe the change in temperature until it reaches a stable
minimum and click Stop in the temperature window. A data link icon will appear in the
lab book. Click the data link icon and record the lowest temperature after adding the
salt in the data table. (Remember that the water may have begun to warm back up.)
5. If you want to repeat the experiment, click on the red disposal bucket to clear the lab,
click on the Stockroom, click on the clipboard, and select Preset Experiment #1, Freezing
Point Depression –NaCl.

Data Table

Mass of NaCl
Mass of Water
Mass of Ice
Mass of Water + Ice
Minimum Temperature
 6. The freezing point depression can be predicted using the equation DT = Kf x m x i ,
where DT is the change in freezing point, i is the number of ions in the solution per mole
of dissolved NaCl (i = 2), m is the molality of the solution, and Kf is the molal freezing
point constant for water which is 1.86 oC/m.

7. The change in freezing point must be subtracted from the freezing point of pure water,
which is 0.0 0C, in order to compare the predicted freezing point with the actual freezing
point.

Q7a: What is the calculated freezing point of the solution? Compare this to the actual freezing
point.
Pre-Lab Questions

1. Why is it important to keep stirring the solution while performing a freezing point determination?

2. Explain why there is a constant temperature plateau in the cooling curve in Figure 2A but not in
Figure 2B.

3. A mixture of 2.05 g of unknown plus 123.10 g of water had the following cooling behavior:

Time, min Temp., °C Time, min Temp., °C

1.0 10 10.5 -0.50
2.0 9 11 -0.75
3.0 8 11.5 -0.10
4.0 7 12.5 -0.10
5.0 5 13 -1.00
6.0 4 14 -2.00
7.0 3 15 -3.00
8.0 2 16 -4.00
9.0 1
10.0 0

Using Excel, prepare a graph showing the temperature on the y-axis and the time on the x-axis. Label
both axes, include a title for the graph, and label the freezing point. Attach plot to the report.
Post-Lab Questions

1. Calculate the molar mass of a molecular unknown if a solution containing 35.6 g of unknown in
165.2 g of water froze at –4.77°C

2. Pure substance “A” freezes at 78.2°C. A solution of 1.786 g of “B” (“B” molar mass = 153.80
g/mol) and 34.28 g of “A” froze at 68.1°C. Calculate Kf of “A”