Freezing Point Depression
Freezing Point Depression
Freezing Point Depression
Experiment 1
MOLAR MASS DETERMINATION BY FREEZING POINT DEPRESSION
Whenever a substance is dissolved in a solvent, the vapor pressure of the solvent is lowered. As a result
of the decrease in the vapor pressure, the boiling point, freezing point, and osmotic pressure of the solvent are
changed. The magnitude of these changes depends on the number of solute particles dissolved in a given mass
of solvent. At low solute concentrations, the changes in the vapor pressure, boiling point, freezing point, and
osmotic pressure of a solution are all proportional to the amount of solute that is dissolved in the solvent. These
four properties of solutions are collectively known as colligative properties .
The colligative properties of a solution depend only on the number of solute particles present in a given
amount of solvent and are independent of the nature of the particles dissolved. If the solute is a nonvolatile
substance, the vapor pressure and the freezing point of the solution is lower than that of the pure solvent and the
boiling point is higher. Some common uses of colligative properties are the addition of "antifreeze" to automobile
radiators to lower the freezing point of water and the sprinkling of salt on icy sidewalks to melt the ice by lowering its
freezing point.
Colligative properties are useful for determining molar masses of unknown compounds and the degree of
dissociation in solution of known compounds. For low concentrations of a nonvolatile solute, the freezing-point
depression of a solvent is given by the relationship:
Tf = Kf m ,
(1)
where Tf = Tf (solvent) - Tf (solution), Tf is the freezing temperature, Kf is the molal freezing point depression
constant for the solvent (which is simply a proportionality constant characteristic of the solvent used), and m is the
molality of the solution. Molality is a unit of concentration that is defined as:
m = mol(solute) .
kg(solvent)
(2)
In order to determine the molar mass of an unknown compound by measuring the freezing point
depression of a solvent, the molal freezing point depression constant for the solvent must be known. The value
of Kf is determined by dissolving a measured amount of a known compound into a given amount of solvent and
then measuring the depression of the freezing point. The value of Kf 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
(i.e., the difference in the freezing point of the pure solvent and a 1 molal solution). NOTE: It is important when
determining the value of K f for a solvent that the solute does not dissociate when it dissolves so that the number
of particles of solute in solution is equal to the number of molecules added. The freezing points and molal
freezing point depression constants of some common solvents are listed in Table 1.
Table 1. Freezing points and molal freezing point depression constants of some common solvents.
Solvent
acetic acid
16.6
3.90
5.5
5.12
benzene
camphor
K f (C m-1)
179
cyclohexane
6.47
formic acid
8.40
39.7
20.0
2.76
naphthalene
80.2
6.9
paradichlorobenzene
53.0
7.10
tert -butanol
25.5
9.1
water
0.00
1.86
To experimentally determine the molar mass of an unknown substance by the freezing point depression
method, a solution is prepared by adding a measured mass of sample (i.e., the solute) into a known amount of
solvent. From the observed freezing point depression (T), the molal concentration of the unknown substance in
the solution can be calculated rearranging Equation (1):
m = T .
Kf
(3)
Rearranging the definition of molality [Equation (2)] and using the mass of solvent (in kg), the number of moles of
unknown substance can be determined from the relationship:
mol (solute) = m x kg (solvent) .
(4)
The molar mass (MM) of a compound is defined as the number of grams per mole. Therefore, from the definition of
molar mass, the molar mass of the unknown sample can be determined by dividing the number of grams of solute
by the number of moles of solute:
MM =
g (solute)
.
moles(solute)
(5)
Example :
A solution containing 15.00 g of glucose in 100.0 g of water is found to freeze at -1.53C. What is
the molar mass of glucose? NOTE: The solvent is water since it is present in excess.
Answer :
From Table 1, Kf for water is 1.86C m-1 and the freezing point of water is 0.00C. From the data
given:
Tf = Tf (solvent) - Tf (solution) = 0.00 - (-1.53) = 1.53C.
From the freezing point depression and the molal freezing point depression constant, the molality
of the solute can be determined from Equation (3):
molality = 1.53C = 0.823m
1.86 C
m
Using the molality and the number of kilograms of solvent, the number of moles of solute can be
determined using Equation (4):
mol= 0.823 mol x 0.1000kg=0.0823mol
kg
NOTE: In order for the units to cancel, the mass of solvent, which was given in grams, must be
converted into kilograms (100.0 g = 0.1000 kg).
From the number of grams of solute and the number of moles of solute, the molar mass can be
determined from Equation (5):
MM =
15.00g
g
= 182
.
0.0823mol
mol
The true molar mass of glucose (C6H12O6), determined from its formula, is 180.15 g mol-1. The
percent error, which is a comparison of a measured value with its actual or true value, is given by
the relationship:
actual - experimental
percenterror =
actual
x100% .
percenterror =
180.15- 182
180.15
x100%=1% .
(6)
In this experiment, the molar mass of an unknown compound will be determined by the freezing point
depression method using cyclohexane (C6H12) as the solvent. Cyclohexane is used as the solvent because it has
a convenient melting point (6.47C) and a relatively large value for Kf (20.0). All other things being equal, the larger
the value of Kf , the larger will be the change in the freezing point for the same molality of solute. Thus the larger
the value of Kf , the more sensitive the solvent is for determining molar masses by the freezing point depression
method.
Because most thermometers are not precisely calibrated, it cannot be assumed that a thermometer would
indicate the correct freezing point of cyclohexane. Thus the freezing point of cyclohexane, as measured with
each thermometer, must first be determined. The freezing point will be obtained by studying the rate at which
liquid cyclohexane cools in an ice-water bath. This procedure is necessary because the temperature at which a
liquid freezes is often difficult to determine by simple visual observation, due to supercooling and because the
solidification of solutions takes place over a range of temperatures. Therefore, temperature-time graphs called
cooling curves , as shown in Figure 1, will be constructed.
Temperature
Time
Figure 1. Cooling curve for a pure substance.
Because the melting point of cyclohexane is 6.47C, it is a liquid at room temperature. If a test tube
containing cyclohexane is cooled by immersing it in an ice-water bath at 0C, the temperature of the sample will
vary with time, as shown in Figure 1. Initially, the temperature will fall quite rapidly. When the freezing point is
reached, solid cyclohexane will begin to form, and the temperature will remain constant until the sample
completely solidifies. The freezing point of a pure liquid is the constant temperature observed while the liquid is
freezing to a solid.
The cooling behavior of a solution is somewhat different from that of a pure liquid and is shown in Figure 2.
The temperature at which the solution begins to freeze is lower than for the pure solvent. In addition, there is a
slow gradual fall in temperature as freezing proceeds. Clearly, the drop in temperature as the solution freezes
makes determining the 'freezing point' somewhat ambiguous. However, the 'best' value for the freezing point of a
solution is obtained by drawing two straight lines connecting the points on the cooling curve. The first line
connects points where the solution is all liquid (i.e., the "liquid cooling" line). The second line connects points
where solid and liquid coexist (i.e., the "liquid freezing" line). The temperature at which the two lines intersect is
the freezing point of the solution. Extrapolation is necessary 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 concentrated in solute as solidification progresses. The increase in
solute concentration continues to lower the freezing point during solidification and produces the sloping "liquidfreezing" line in the cooling curve that follows the start of solidification. The extrapolation technique allows the
easy and accurate determination of the 'initial' freezing point of a solution.
Temperature
Freezing point
Supercooling
Solidification begins
Time
the freezing point and should be minimized. Gentle stirring of the solution as it cools will reduce the amount of
supercooling. However, in order to establish the proper straight line in the solid-liquid region, it is necessary to
record the temperature until the trend with time is smooth and definitely established.
EXPERIMENTAL PROCEDURE
A. Determination of the Freezing Point of Cyclohexane
CAUTION: Vapors of organic compounds are always potentially hazardous. Avoid breathing cyclohexane vapor
unnecessarily. Cyclohexane is flammable, be sure to avoid any ignition source. There should be no flames in lab!
Obtain a sample of an unknown solid from the instructor. Be sure to record the unknown number on the
preliminary data sheet. Check out a digital thermometer from the stockroom. NOTE: The digital thermometers
used in this experiment are both fragile and expensive (approximately $20.00), so handle them with care. Obtain
from the cart in the front of the laboratory a #4 2-hole rubber stopper (with Teflon sleeves), a universal clamp, a
wide-mouth test tube, a stirrer made of stainless steel, a short piece of tygon tubing, and a ruler.
Record the mass of the clean, dry wide-mouth test tube1 placed inside a 250 mL beaker, as shown in
Figure 3, to a precision of 0.001 g on the preliminary data sheet. As demonstrated by the instructor, using the
repipet, deliver 20.0 mL of cyclohexane into the wide-mouth test tube. Place the test tube containing the
cyclohexane back into the 250 mL beaker and obtain the mass to the same precision as before. Record the mass
of the test tube containing the cyclohexane in the 250 mL beaker on the preliminary data sheet. The difference
between these two masses is the mass of the cyclohexane. [NOTE: Since the density of cyclohexane is
0.7781 g mL -1, the mass of cyclohexane should be ~15.5 g.]
250 mL Beaker
Pack a 400 mL beaker with crushed ice. Add enough water to bring the level of the ice-water slurry to
about 350 mL. Place the 400 mL beaker into a 600 mL beaker. The 600 mL beaker serves to trap air and help
insulate the ice-water bath so that the ice will not melt as rapidly. Insert the short piece of tygon tubing onto the
thermometer and slide it up as far as it will go and then insert the thermometer into the center hole of the two-hole
rubber stopper. The tygon tubing should position the thermometer so that it will nearly reach the bottom when
inserted into the wide-mouth test tube. Insert the stirrer through the outside hole of the rubber stopper (from the
bottom) and assemble the apparatus as shown in Figure 4. NOTE: Ring stands are in the large cabinets in the lab
benches. The tip of the thermometer should be well covered by cyclohexane. Attach the wide-mouth test tube to
the ring stand using a universal clamp. The test tube should be clamped so that the level of the cyclohexane is
below the level of the ice-water bath in the beaker. Be sure that the loop of the stirrer circles around the
thermometer and slides easily.
Digital thermometer
Ring stand
Tygon tubing
Stirrer
Rubber stopper
Wide-mouth test tube
Universal clamp
600 mL Beaker
Ice-water bath
400 mL Beaker
cooling proceeds until the solution may solidify to the point where it can no longer be stirred. Keeping recording
data until the temperature remains constant (0.1C for 4 minutes). When plotted, the cooling curve should
resemble the cooling curve for a pure substance shown in Figure 1. The horizontal portion of the graph indicates
the freezing point of the cyclohexane as measured by your thermometer.
10
To dispose of the cyclohexane-unknown solution, allow the solution to warm to room temperature and
pour the liquid into the disposal jars provided in the hoods for that purpose. Do NOT pour the solution into the
sink! To remove the solid, which solidifies on the test tube and the thermometer, use a 5 mL portion of acetone to
dissolve solids remaining in the test tube or on the thermometer. Pour the acetone rinsings into the same
cyclohexane-unknown waste container. As before, do NOT pour the acetone rinse into the sink! If necessary,
repeat the rinsing procedure with up to 2 additional portions of acetone. Do not use more than a total of 15 mL of
acetone. If any solid still remains on the sides of the test tube, wash with Alconox solution and vigorous scrubbing
and then rinse with hot water. The rinsings with water may be disposed of in the sink.
Return the equipment to the cart upon completion of the experiment and return the ring stand to the large
cabinet in the lab bench. Also, be sure to turn the thermometer off (to help extend the life of the battery) and
return it to the stockroom. Return the vial, which contained the unknown to the instructor.
Before leaving the laboratory, transfer all of the necessary information from the
preliminary data sheet onto the laboratory report and enter the data into the computer. Be
sure to turn in the preliminary data sheet with the laboratory report .
NOTES:
1
If the wide-mouth test tube has any residual solids on the inside, it must be cleaned and dried before being
used in this experiment. The test tube may be cleaned by rinsing it with a 5 mL portion of acetone to dissolve
solids remaining in the test tube. Pour the acetone rinsings into the disposal jars provided in the hoods for
that purpose. Do NOT pour the acetone rinse into the sink! If necessary, repeat the rinsing procedure with
up to 2 additional portions of acetone. Do not use more than a total of 15 mL of acetone. If any solid still
remains on the sides of the test tube, wash with Alconox solution and vigorous scrubbing with a test tube
brush and then rinse with hot water. The rinsings with water may be disposed of in the sink. The test tube
must be dry before being used in this experiment. If water was used to clean the test tube, rinse the test tube
with a final 5 mL rinse of acetone and, as before, pour the acetone containing rinse into the waste container
and then dry the test tube by placing it over the dryers in the hood as demonstrated by your instructor. If it was
not necessary to use water to clean the test tube, the test tube may be dried after the final acetone rinse as
described above.
Plot your data while waiting for the solution to warm and the unknown to dissolve.
11
Exp. 1
Drawer _______
58.5
57.0
55.3
53.9
52.6
51.4
50.0
48.9
49.1
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
49.2
49.1
49.0
48.9
48.8
48.7
48.6
48.5
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
Temperature (C)
56
55
54
53
52
51
50
49
48
4
Time (minutes)
FP = ___________ C
12
3. From other data, the freezing point of PDB was found to be 53.1C. What is the freezing point depression,
Tf ? (Show all work!)
T = ___________ C
4. Using Equation (1), what is the molality of the camphor?
mol = ___________
6. From the definition of molar mass (i.e., MM = grams per mole), knowing the number of grams and
moles of camphor, calculate its molar mass.
MM = ___________ g mol-1
7. If the molecular formula of camphor is C10H16O, what is the percent error in the determination of its molar mass?
9. Would you expect the unknowns used in this experiment most likely to be molecular or ionic compounds?
Explain.
10. Pure cyclohexane and the cyclohexane solutions may supercool at their freezing points. Define supercooling
and explain how we attempt to minimize supercooling in this experiment.
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Exp. 1
Drawer _______
___________
Mass of wide-mouth test tube plus cyclohexane [in 250 mL beaker] (g)
___________
___________
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___________
___________
Temperature-time Readings:
Temperature (C)
Time (min)
0.00
0.25
0.50
0.75
1.00
1.25
1.50
1.75
2.00
2.25
2.50
2.75
3.00
3.25
3.50
3.75
4.00
4.25
4.50
4.75
5.00
5.25
5.50
5.75
6.00
6.25
6.50
6.75
7.00
7.25
7.50
7.75
8.00
8.25
8.50
8.75
9.00
9.25
9.50
9.75
10.00
Cyclohexane
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Solution 1
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Solution 2
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Solution 3
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14
Plot the temperature-time data for pure cyclohexane and for each of the three solutions. To avoid
overlapping the graphs, add 6 minutes to all observed times in making the graph of the cooling curve for pure
cyclohexane. Add 4 minutes to all times for Solution 1. Add 2 minutes to all times for Solution 2. Use times as
observed for Solution 3.
12
11
10
9
Temperature (C)
8
7
6
5
4
3
2
1
0
7
8
9
Time (minutes)
10
11
12
13
14
15
16
15
Exp. 1
Drawer _______
___________
Mass of wide-mouth test tube plus cyclohexane [in 250 mL beaker] (g)
___________
___________
___________
___________
___________
Solution 1 = ________C
Solution 2 = ________C
Solution 3 = ________C
CALCULATIONS
(Show all work!)
Solution 1
Solution 2
Solution 3
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QUESTIONS
1. How would the following errors affect the calculated value of the molar mass (high, low, or no effect), if you
were not aware that they had occurred? Explain your answers.
a. A small amount of unknown adheres to the inside of test tube and did not get dissolved in the
cyclohexane.
c.
The thermometer used in this experiment was miscalibrated to read 0.5C lower than the actual
temperature over its entire scale.
16