1

Freezing Point Depression

1


Freezing point depression is an example of a colligative property, along with vapor
pressure lowering, boiling point elevation, and osmotic pressure. These are
characteristics of solutions that depend only on the identity of the solvent and the
concentration of the solute, but not on the solutes identity. These properties depend on
the entropy (lack of order) of the solutions involved. More solute increases entropy, i.e.
it increases the disorder of the arrangement of solvent molecules, which 1) makes it more
difficult to freeze; 2) gives it less driving force to vaporize, which in turn 3) makes it
more difficult to boil; and 4) gives pure solvent a greater tendency to enter a solution to
dilute it. [Look in Chapter 11 of the text for more thorough explanations.]

The following equations describe the colligative properties of dilute solutions:

T
f
= k
f
m where T
f
is the decrease in freezing point of a solution of molal
concentration m relative to the pure solvent, and k
f
is the
proportionality constant specific to a given solvent.

P = P
o
x
2
where P is the difference in vapor pressures between the pure
solvent and a solution with a mole fraction of a nonvolatile solute
x
2
, and P
o
is the vapor pressure of the pure solvent.

T
b
= k
b
m where T
b
is the increase in boiling point from the pure solvent
for a solution of molal concentration m, and k
b
is the
proportionality constant specific to a given solvent.

= M RT where is the pressure needed to stop the flow of solvent from the
less-concentrated to the more-concentrated sides of a
semipermiable membrane. M is the molar concentration
difference. R is the gas constant, and T is the absolute temperature.

Notice how none of the equations have any terms that depend on the identity of the
solute. They have terms that depend on the concentration of the solute, but that is a
reflection of the number of moles, not their chemical identity. Consequently, these
properties are often used where a knowledge of a number of moles is useful; for
instance, in determining a MW. A measured mass of an unknown can be dissolved in a
particular solvent, and by looking at the freezing point depression or boiling point
elevation or osmotic pressure, one can tell how many moles of solute there must have
been, and consequently determine the molecular weight.

If we are to believe the Freezing Point Depression equation T
f
= k
f
m, it should be the
case that when making solutions of two substances with different freezing points, we
should not see the freezing point simply increase from that of the lower freezing
substance to the higher freezing substance. Rather, the freezing points of solutions close
in composition to either pure substance should be lower than the freezing points of the
pure substances. This is what we are going to try to demonstrate today. We will make
2
solutions of two fatty acids covering the complete range of possible compositions and
measure their freezing points. A plot of Freezing Point vs mole fraction will
demonstrate whether or not there is any merit to this Freezing Point Depression
stuff or not. And we should also be able to use the equation T
f
= k
f
m and a plot of
T
f
vs m to determine the freezing point depression constant, k
f
for both of the fatty
acids.
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Some Comments about the Concentrations used in this Experiment:

The molality of a solution is defined as the number of moles of solute per kg of solvent.
It commonly shows up in thermodynamic formulas since it is basically a ratio of
quantities of two substances and doesnt depend on more complicated properties such as
volume which can change with temperature.

The mole fraction is the ratio of the moles of one on the components in a solution to the
total number of moles (solvent + solute).

To do the necessary calculations in the lab today, you will need to know the molar
masses of the fatty acids used:
Stearic acid C
18
H
36
O
2
284.48 g/mole
Lauric acid C
12
H
24
O
2
200.32 g/mole

Calculate the mole fraction of stearic acid as follows:

|
|
.
|

\
|
+

=
g
Acid Lauric mole
Acid Lauric g
g
Acid Stearic mole
d StearicAci g
g
Acid Stearic mole
d StearicAci g
fraction mole
32 . 200
1
48 . 284
1
48 . 284
1


Furthermore, if one has a solution of 2 acids, the molality of the solute (the one in lesser
amount) may be calculated as follows:

acid solvent kg
acid solute moles
molality solute =

For example, if you used 4.000 g of Stearic acid and 0.1000 g of Lauric acid, perform the
following calculation:


g
kg
Acid Stearic g
g
Acid Lauric mole
Acid Lauric g
molality acid lauric
1000
1
000 . 4
32 . 200
1
1000 . 0

=
3

Recognize that to determine k
f
for Stearic Acid, one needs to plot T
f
vs molality of
Lauric acid in Stearic acid, and to determine k
f
for Lauric acid, one needs to plot T
f
vs
molality of Stearic acid in Lauric acid.


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A Consideration Concerning the Plot of T vs Concentration:

One aspect of colligative properties we may see in todays experiment is that the stated
equations work best with very dilute solutions. Consequently in order to define the k
f

we to define the slop with the most dilute solutions call it the limiting slope. When
we determine k
f
by finding the slope of T
f
vs concentration, we should only use the
experimental points that define the limiting slope. In the case plotted below, for instance,
the trendline is appropriate for determining k
f
. It was obtained by defining an additional
series in the EXCEL plot which included only the first four points of the data series; and
that series was used to define the trendline.






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4
Today you will be making temperature measurements using one of the Pasport Chemistry
Sensors. The device will be tied to your computer, and the computer will control it using
the DataStudio software which should have been part of the standard load that came with
your computer.
_________________________________________________________________
Making measurements with Pasport Chemistry Sensors and DataStudio:

The Pasport Chemistry sensors in conjunction with the Pasport interface and the
DataStudio software allow you to measure, temperature, pressure, pH, or voltage as a
function of time and store the measurements on your computer.

Before starting the program, connect the probe to your computer through a USB port as
shown in the figure in the Procedure section below.

To start the program click on

StartPrograms-WFU Academic ToolsScientific ToolsData Studio 1.9.8r7.
Then click on Create an experiment, and close the Digits 1 window.
Double click on any Display you want to see in the DISPLAYS window. You will
probably want to see the measured value and a graph of the values, so you double click
on 3.14Digits and Graph. In each case select the Temperature Data Source.

If you are running a Table, you will not want to be storing data very rapidly. Click on the
Setup button and set the sampling rate suitably low (say 1 seconds).

When you are ready to start measuring, click the Start button, and when you are ready
to stop, click Stop

To save the data for later work, click on File Export Data, then give it a location to put
a text file version of your data. You can control the number of decimal places in the
exported values by double-clicking on the Run# in the Data window and selecting the
Numeric tab.

The exported text file can be opened in EXCEL, but you have to make EXCEL look for
.txt files in the OPEN window. The files are TAB delimited, and only one run is kept in
each file. When you save the EXCEL file, save it as a regular .xls or .xlsx file.

_________________________________________________________________
5
Procedure:
You will be working in pairs today.

Prepare a hot water bath by putting about 100mL of water in a 250mL beaker and
bringing it to a boil on a hotplate.

Prepare a holder in which to carry out the cooling curves. Clamp your largest test
tube to a ring stand, and put a small wad of paper towel in the bottom. You will put a 20
x 150mm test tube containing the sample inside this clamped tube. The clamped tube
will isolate the sample tube from the surroundings to minimize the occurrence of regions
that will cool faster.

Assemble the Pasport Chemistry Sensor with the temperature probe





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Determine freezing point of your pure solvent acid:
- Transfer about 4 g (weigh accurately) of your solvent acid (Room 101 Stearic Acid, and
Room 105 Lauric Acid) to a large test tube. The large test tube, 20x150, is the one that
fits into the jumbo clamped test tube).

- Heat in hot water above 85
o
C. All should be melted.
- Remove from the hot water bath and quickly insert the temperature probe. Put the test
tube in the clamped insulating tube.
- Start the readings in Data Studio (take data at least as often as once every second).
- Continue taking readings while stirring until formation of solid prevents stirring.
- Repeat the melting and cooling process until you get two freezing points that agree
within 0.25
o
C.

Freezing point determination from cooling curve of pure acid.



Determine freezing points of an acid solution:
In addition to the pure acid freezing point determined above, you will make a solution
with your solute acid and determine the freezing point. Each group should prepare a
slightly different mixture as follows.

If you are in Room 101, accurately weigh the desired mass of lauric acid and add it to
your stearic acid. The mass should be between 0.05 and 0.4 g, but different from the
other groups in your room. In Room 105, do the same, but add 0.05-0.4 g of stearic acid
to your lauric acid. (Be careful not to lose sample when taking the temperature probe out
of the test tube.)

- Repeat the melting and freezing steps as above, being certain to mix the solute well
while collecting the cooling curve.

- Repeat the melting and cooling process until you get two freezing points that agree
within 0.25
o
C. If you expand the scale, you should be able to identify the freezing
point by eye in Data Studio.


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Freezing point determination from cooling curve of solution



Data Analysis:

Accurately determine the freezing point of each sample you worked with. This may be
done in Excel by performing a linear fit on the two ends of the curve, and setting the
resulting equations equal to one another. For easiest analysis, copy two selected portions
of the data into new columns, and perform the linear fits separately.

For each sample, calculate the mole fraction of stearic acid and the molality of your
solute acid (see equations above). Submit your concentration and T
f
results to the
website.

Collect the classs results and plot T
f
vs mole fraction. What does this plot say about the
notion of Freezing Point Depression? Plot T
f
(T
f
for the pure acid T
f
for the solution;
it should be a positive number) vs molality for your solvent acid, find the limiting slope,
and determine k
f
for that acid.

Be sure your lab report includes

plots of temperature vs time for the pure fatty acid you used, and one of your solutions.
Clearly identify the freezing points.

a plot of T
f
vs mole fraction of the appropriate fatty acid (listen in pre-Lab or to your
TA to figure this one out) using the complete set of the data from the class.

a plot of T
f
vs molality for your solute/solvent combination. Include pertinent class
data for this. Clearly identify the limiting slope.

a determination of k
f
for your fatty acid.

answers to the questions asked through the procedure.

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See also, McCarthy and Gordon-Wylie, J.Chem.Ed, 82, 2005, p116-119.