EXERCISE 4: COOLING CURVE

I. Introduction

In principle, substances can be classified and can exist in three different phases namely liquid,
solid and gas (Wysession, Frank, & Yancopoulus, 2014). Solid has definite volume and shape,
unlike liquid which only has definite volume. Gas, on the other hand, has neither definite shape
and volume, it only assumes the volume and shape of its container (Zumdahl, 2007). The
temperature is one of the factors which plays a huge role in the transition between these states.

Phase change usually occurs when heat is added or removed from a substance which causes
it to transform from one phase to another. The physical appearance of the substance has
something to do with its molecular order—molecules in solid state have the most order while those
in gas state have the least (Chang, 2008). The temperature and kinetic energy stay constant
during a phase change while the heat energy either increases or decreases.

Cooling curve displays a graphical representation about what happens to a substance as the
temperature decreases. It helps in determining the temperature where the freezing point and
condensation point occurs (Wysession, Frank, & Yancopoulus, 2014). Cooling curve also shows
that the temperature and time is inversely proportional to each other and that the freezing point
of a particular substance can be obtained by searching for the value of temperature which remains
constant for a period of time.

In a solution, there are properties such as vapor-pressure lowering, boiling-point elevation,

freezing-point depression, and osmotic pressure which are affected by the number of solute
particles in a solution. These are called “colligative properties” or collective properties for the
reason that they are bound together by a common origin (Chang, 2008). Freezing point
depression occurs when solute is introduced to a solution, take for example, using salt in thawing
icy roads in other countries. The salt helps in depressing the freezing point of water since a
solution has greater disorder than pure solvent. Greater disorder in its compositions means that
it needs more energy to be removed from it in order to create order (Chang, 2008). This shows
that a solution has lower freezing point than that of a pure liquid. Its freezing point is the
temperature at which the first crystals of pure solvent begin to form in equilibrium with the solution
(Brown, LeMay, Bursten, Murphy, Woodward, 2009). The freezing point depression can be
computed using the equation:

ΔTf = Tf (solvent)−Tf (solution)= kfm

Where:
Tf = freezing point
kf = freezing point depression constant of the solvent
m = molality of a solution

The objective for this exercise is to examine and plot the cooling curves of the given unknown
solvent and solution, and then determine their freezing point. This exercise also aims to identify
the possible identity of the unknown compound using the obtained freezing point from the
experiment, describe the computed freezing point depression, compute for the molality of the
solution and then the molecular mass of the unknown solute.
II. Materials
A. Reagents
 Unknown Solvent for Part A
Mass: 2.06 g
 Unknown Solvent for Part B
Mass: 2.02 g
 Unknown Solute for Part B
Mass: 0.35 g

B. Apparatus and Equipment

 Beaker: 250-mL
 Bunsen burner
 Iron ring
 Iron clamp
 Iron stand
 Wire gauze pad
 Stirring rod
 Thermometer
 Small test tubes: 186.30 g; 157.70 g

III. Procedure
A. Freezing point of a pure compound
In a clean dry test tube, two grams of the assigned solvent was first weighed. The
test tube was then placed in a water bath so that the sample level in the test tube is
below the water level of the bath and that the test tube didn’t touch the bottom and
sides of the beaker used. The water bath was heated until the sample melted. A tissue
paper was also used to loosely plug the test tube to prevent the foul smell from
escaping the container. While heating the water bath, a stirring rod was used to stir it,
this is to make sure that the heat was evenly distributed. When the sample melted, a
thermometer was inserted into the test tube while it was heated continuously for two
more minutes. After putting off the flame, the temperature was recorded at 15-second
intervals, making sure that the water bath was still continuously stirred. The physical
state or the appearance of the sample was then observed while cooling.
The temperature was recorded in Table 4.1 until the sample in the test tube
completely solidified and the cooling curve of the unknown solvent was plotted.

B. Freezing point of a solution

For the freezing point of the unknown solution, 0.20 grams was weighed in a clean
dry test tube and then it was mixed with the two grams of unknown solvent. Following
the steps from part A of the experiment, the appearance of the sample while cooling
 was also observed. The cooling curve of a pure substance and a solution was then
compared.

C. Waste Management

Lard was poured into the solidified sample. It was then heated gently and stirred
until the sample completely melted back into its liquid state. The mixture was poured
in the waste bottle with the label “Lard Containing Wastes” while it was still warm.

IV. Data/Observation

For the Part A of the experiment, the measured mass of the unknown solvent sample is 2.06g
while its container is 186.30g. Their combined mass is 188.36g. The weighed mass in Part B for
the unknown solvent is 2.02g with a container measuring 157.70g. Adding their mass will result
to 159.72g. For the unknown solute sample, the weighed mass is 0.35g with a 157.70g container,
while their combined mass is 158.05g. The obtained data and observations on cooling of unknown
solvent and mixture at 15-second intervals is shown in Table 4.1 and Table 4.2 respectively.

The list of physical properties of some compounds is shown in Table 4.4 and the list of
probable identity of the solute is shown in Table 4.5. The observed value, based from the cooling
curved displayed in Figure 4.1, for the freezing point of the unknown solvent is 77°C which is
closest to Napthalene’s freezing point (80.2°C). The solvent was identified as Napthalene. Its
freezing point depression constant is 6.9°C/m.

Based from the graph shown in 4.2, the freezing point of the solution might be at 72°C, while
its computed molality and molecular mass are 1.463x10^-3mol/kg and 239.1g/mol respectively.

Cooling Curve of the Solvent

100

80
TEMPERATURE (°C)

60

40

20

0
0 30 60 90 120 150 180 210 240 270 300 330 360 390 420 450 480 510 540 570 600 630 660
TIME (sec)

Figure 4.1. Graph of Cooling Curve of the Solvent

 Cooling Curve of the Solution
TEMPERATURE (°C) 100

80

60

40

20

0
0 30 60 90 120 150 180 210 240 270 300 330 360 390 420 450 480 510 540 570 600
TIME (sec)

Figure 4.1. Graph of Cooling Curve of the Solution

V. Discussion

The unknown solvent and unknown solution were observed gradually turning transparent
before completely melting at 90°C and 85°C respectively. The samples started to solidify again at
75°C and 72°C respectively and they slowly turned back to their original color. This is because in
solid form, the crystallites in the samples scattered light which resulted to higher opacity, but when
they were exposed to high temperature, these crystallites melted leaving the liquid with clear
appearance. At 70°C and 68.8°C respectively, the samples completely turned opaque and solid.

Figure 4.1 shows a gradual decreasing trend which means that as the samples cooled down,
the temperature decreases. The curved graph shows the declining of the difference between the
temperature of the substance and the environment. It also displays the state of the substance—
whether they’re undergoing phase change or not. Based on the data recorded, the temperature
of the unknown samples in the test tube kept decreasing until it reached a certain value where it
remained constant for a few seconds before it continued to fall again. This point shows that the
temperature wasn’t changing because the kinetic energy wasn’t changing as well (according to
Charles’ Law), unlike the potential energy which was altering during this point. The figure also
showed the freezing points of the unknown solvent and solution which were 77°C and 72°C
respectively. Their temperature remained constant for more than one 15-second interval as it was
undergoing phase change (liquid to solid).

The freezing point depression can be obtained by multiplying the molality of the solution and
the freezing point depression constant of the solvent. The freezing point depression of the solution
is lower than that of a pure solvent because it is a colligative property of the solution. This means
that it is dependent on the number of the dissolved particles in it and they are directly proportional
to each other. Its application can be seen when people put salt on ice roads to prevent the melting
ice from freezing back. Salt can also be used to make the ice colder when the two of them are
put together in a container. Another practical use of this is the mixture of ethylene glycol and water
which makes up the radiator fluid of an automobile. This helps in keeping the radiators from
freezing during winter. The introduction of solute to the solvent also makes the freezing point of
the mixture lower than the freezing point of a pure substance because the solute concentration
increases as the solvent freezes.

The cooling curves show the freezing point of the solvent and solution which are 77°C and
72°C respectively. By comparing the freezing point of the unknown solvent to the given freezing
points of other substances, it was found out that the experimental freezing point of the unknown
solvent was closest to that of Napthalene’s which is 80°C as shown in Table 4.4, hence, it is
identified as Napthalene. Its cooling curve is shown in Figure 4.1.

The equation for the freezing point depression will be used in order to identify the unknown
solute:

ΔTf = Tf (solvent)−Tf (solution)= kfm

Where:

ΔTf = freezing point depression

Tf = freezing point

kf = freezing point depression constant of the solvent

m = molality of the solution

Deriving the formula for the molality of the solution from this and plugging in the values will
give us the equation and answer:
(𝚫𝐓𝐟 )
𝒎=
𝐤𝐟
|(𝟖𝟎−𝟕𝟐)| 𝒎𝒐𝒍
𝒎= 𝒎 = 𝟏. 𝟏𝟔
𝟔.𝟗 𝒌𝒈

The theoretical freezing point of the solvent was used in the equation above which is 80°C
while the freezing point depression (kf) was given in Table 4.4. The molecular mass of the solute
can now be computed using this value of molality with the given data from Table 4.3.
𝒎𝒐𝒍 (𝒎𝒐𝒍𝒔𝒐𝒍𝒖𝒕𝒆 )
𝟏. 𝟏𝟔 =
𝒌𝒈 𝒌𝒈𝒔𝒐𝒍𝒗𝒆𝒏𝒕
𝒎𝒐𝒍 (𝒎𝒐𝒍𝒔𝒐𝒍𝒖𝒕𝒆 )
𝟏. 𝟏𝟔 =
𝒌𝒈 𝟐. 𝟎𝟐𝒙𝟏𝟎^ − 𝟑 𝒌𝒈

molsolute = (1.16 mol/kg) (𝟐. 𝟎𝟐𝒙𝟏𝟎^ − 𝟑 kg) = 2.34x10^-3 mol

MM = g/mol = 0.35 g / 2.34x10^-3 mol = 149.37g/mol

Now that the molecuar mass of the unknown solute is computed, it can be compared to the
list of probable identity of the solute shown in Table 4.5 to find out what it is. The closest molecular
mass to this is the molecular mass of Benzoic acid which is 122.12 g/mol. The unknown solvent
can now be identified as Benzoic acid whose cooling curve is shown in Figure 4.2.
 To compute for the value of the freezing point depression of this experiment, the obtained
values from the previous calculation are substituted into the equation:

ΔTf = kfm

Hence, the answer will be:

8.004°C = (6.9)(1.16 mol/kg)

For the computation for the % error of the freezing point and molecular mass the equation
below will be used:

% error = |accepted – experimental| x 100

accepted

Plugging in the obtained values will result to the % error of the freezing point:

3.75% = |80 – 77| x 100

80

While substituting the obtained values for computing the % error of molecular mass will give
the answer:

22.31% = |122.12 – 149.37| x 100

122.12

Table 4.4 shows that the experimental freezing point of Napthalene which is 77°C is different
from its expected freezing point which is 80.2°C. One of the reasons for this difference could be
the inconsistent stirring of the water bath which was supposed to distribute the heat evenly
throughout the bottom of the beaker. This could have caused the temperature to decrease more
slowly. The recorded 15-second interval time recorded from the stopwatch could have also
affected the results of the experiment as well as the air-conditioned room where this experiment
took place. If the temperature was also recorded more often rather than by 15-second interval
only, the data obtained would’ve been more precise. Another possible source of error is the
inaccurate reading of the thermometer during the heating of the samples.

As stated above, reading the temperature of the sample more often can help in obtaining more
precise values and decreasing the percent error of the experiment. Making sure that the stirring
bath is continuously stirred during the heating process will also give better results.
V. Conclusion

From the conducted experiment, the following conclusions were made:

 The plotted cooling curves showed a decreasing trend which means that the
temperature (°C) of the samples is inversely proportional to the time (sec). The observed
states in the cooling curves were liquid, semi-solid, and solid states.
 It was also found out that the solution has lower experimental freezing point than the
solvent—72°C and 77°C respectively. The difference between the freezing point in 5°C.
This proves that the properties of a solution indeed differ from its components which are
the solute and solvent.
 From the obtained data, we have proved that the presence of the particles of a solute
decreases its freezing point and changes its molecular order.
 Freezing point depression was observed in the difference between the freezing point of
the pure solvent which is greater than the freezing point of the solution. The computed
freezing point depression is 8.004°C.
 The unknown solvent was identified as Napthalene with a freezing point of 80°C and the
unknown solute was identified as Benzoic Acid with a molecular mass of 149.45 g/mol,
while the computed molality of the solution is 1.16 mol/kg.
VI. Literature Cited/Bibliography

Brown, T., LeMay, H., Bursten, B., Murphy, C., & Woodward, P. (2009). Chemistry: The

Central Science (11th ed.). Singapore: Pearson Education South Asia.

Chang, R. (2008). General Chemistry: The Essential Concepts (5th ed.). New York:

McGraw-Hill.

Wysession, M., Frank, D., & Yancopoulos, S. (2004). Physical Science: Concepts in Action

with Earth and Space Science. New Jersey: Pearson Prentice Hall.

Zumdahl, S. S., & Zumdahl, S. A. (2007). Chemistry (7th ed.). U.S.A.: Houghton Mifflin

Company.
Appendices

Table 4.1. Data and observations on cooling of unknown solvent at 15-second intervals.

Time Temperature Appearance Time Temperature Appearance

(sec) (°C) (sec) (°C)
0 90°C Liquid 345 78°C Liquid
15 91°C Liquid 360 77.5°C Liquid
30 92°C Liquid 375 77°C Liquid
45 92.1°C Liquid 390 76.5°C Liquid
60 92.5°C Liquid 405 76°C Liquid
75 92°C Liquid 420 77°C Liquid
90 91°C Liquid 435 77°C Liquid
105 90.5°C Liquid 450 77°C Liquid
120 90°C Liquid 465 76.5°C Liquid
135 89°C Liquid 480 76°C Liquid
150 88°C Liquid 495 75.8°C Liquid
165 87°C Liquid 510 75°C Liquid
180 86°C Liquid 525 75°C Solidifying
195 85°C Liquid 540 74.5°C Semi-solid
210 84.5°C Liquid 555 74°C Semi-solid
225 84°C Liquid 570 73.5°C Semi-solid
240 83°C Liquid 585 73°C Semi-solid
255 82°C Liquid 600 72°C Semi-solid
270 81.5°C Liquid 615 72°C Semi-solid
285 81°C Liquid 630 71.5°C Semi-solid
300 80.5°C Liquid 645 71°C Semi-solid
315 80°C Liquid 660 70°C Solid
330 79°C Liquid

Table 4.2. Data and observations on cooling of unknown mixture at 15-second intervals.

Time Temperature Appearance Time Temperature Appearance

(sec) (°C) (sec) (°C)
0 85°C Liquid 315 75.5°C Liquid
15 89°C Liquid 330 74°C Liquid
30 90°C Liquid 345 73.5°C Liquid
45 90°C Liquid 360 73°C Liquid
60 89°C Liquid 375 72.5°C Liquid
75 88.5°C Liquid 390 72°C Solidifying
90 88.5°C Liquid 405 72°C Semi-solid
105 88°C Liquid 420 72°C Semi-solid
120 87°C Liquid 435 72°C Semi-solid
135 86°C Liquid 450 72°C Semi-solid
 150 85°C Liquid 465 71.5°C Semi-solid
165 84°C Liquid 480 71°C Semi-solid
180 83°C Liquid 495 71°C Semi-solid
195 82°C Liquid 510 70.8°C Semi-solid
210 80.5°C Liquid 525 70.5°C Semi-solid
225 80°C Liquid 540 70°C Semi-solid
240 79°C Liquid 555 69.9°C Semi-solid
255 78°C Liquid 570 69.5°C Semi-solid
270 77.5°C Liquid 585 69°C Semi-solid
285 77°C Liquid 600 68.8°C solid
300 76°C Liquid

Table 4.3. Data obtained on the determination of the molecular mass of the unknown solute.

Parameter Value
Unknown Solvent Solvent 1 Solvent 2
Mass of container + sample, g 188.36 g 159.72 g
Mass of container, g 186.30 g 157.70 g
Mass of sample, g 2.06 g 2.02 g
Freezing point, °C 77°C 77°C
Freezing point depression constant, °C/m 6.9°C/m
Unknown Solute
Mass of container + sample, g 158.05 g
Mass of container, g 157.70 g
Mass of sample, g 0.35 g
Freezing point of solution, °C 72 °C
Molality of solution, mol/kg 0.7246 mol/kg
Molecular mass of unknown solute, g/mol 239.1g/mol

Table 4.4. Physical properties of some compounds.

Compound Freezing Point, °C Freezing point depression

constant, °C-kg/mol
Benzophenone 49 9.8
Stearic acid 69.4 4.27
Napthalene 80 6.9
Table 4.5. Probable Identity of the Solute.

Name Chemical Formula Molar Mass

Caffeine C8H10N4O2 194.19 g/mol
Sodium Chloride NaCl 58.44 g/mol
Benzoic Acid C7H7O2 122.12 g/mol

Table 4.6. % Error of Freezing Point and Molecular Mass.

Accepted Value Experimental Value % Error

Freezing Point 80°C 77°C 3.75%
Molecular Mass 122.12 g/mol 146.47 g/mol 19.94%