Title: Determination of the molar entropy of fusion of camphor.

Objectives:

1. To study the molar entropy of fusion of camphor.

2. To determine the molar entropy of fusion (∆Sr) of camphor.

Introduction:

The molar entropy fusion (∆Sr) of camphor can be determined cryoscopically. The technique for
determining the molecular weight of a substance by dissolving it and measuring the freezing
point of the solution is called cryoscopic method. For dilute solutions of naphthalene in camphor

∆T = KfX

Where ∆T = depression of freezing point of the mixture in K

Kf = cryoscopic constant

and X = mole fraction of naphthalene in the mixture

The limit of Kf as X approaches zero i.e.

lim K f = RT02 / ∆Hf

X→0

Where R (the gas constant) = 8.314 JK-1mol-1

T0 is the freezing point of pure camphor in K and ∆Hf is the molar enthalpy of fusion of camphor
in J.

Since, ∆Sr = ∆Hf / T0

Thus, lim K f = RT02 / ∆Hf

X→0

= RT0 / ∆Sr
Materials and Apparatus:

On the test tube, 250cm3 beaker, Bunsen burner, 0-200˚C thermometer, tripod and gauge, retort
stand, clamp and boss head, camphor (M=152 g/mol) and naphthalene (M=128 g/mol).

Experimental Procedure:

2g of camphor was melted and stirred in a test tube, then clamped in an air jacket (a large beaker)
and it was allowed to solidify. The air jacket was removed and the test tube was heated gently
until melting commenced. The contents were stirred with a thermometer and the temperature at
which the last crystal disappeared was noted. That was the freezing point of camphor. 0.05g of
naphthalene was added to this test tube and the process was repeated. The procedure was
repeated for further 0.05g additions of naphthalene up to a total weight of 0.20g of naphthalene.

Results and Calculations:

Weight of No. of moles

No. of moles Weight of Freezing
naphthalene of camphor X (x 10-2) ∆T
of naphthalene camphor (g) point (K)
(g) (x 10-2)
0.0000 0.0000 2.0143 1.325 0.0000 401 0
0.0503 3.9300 x10-4 2.0143 1.325 2.8806 383 18
0.0998 7.7969 x10-4 2.0143 1.325 5.5574 337 64
0.1543 1.2055 x10-3 2.0143 1.325 8.3394 325 76
0.2075 1.6211 x10-3 2.0143 1.325 10.9010 314 87
∆T = KfX

Kf = ∆T / X

X (x 10-2) ∆T Kf
0.0000 0 0
2.8806 18 625
5.5574 64 1152
8.3394 76 911
10.9010 87 798
lim K f = RT0 / ∆Sr
X→0

1530 = [(8.314)(401)] / ∆Sr

∆Sr = 2.1790 J / K . mol

∆Hf = ∆Sr T0

= (2.1790 J K-1 mol-1) (401 K)

= 873.779 J / mol

Discussion:

The molar entropy of the camphor was obtained as 2.1790 J / K . mol in this experiment. The
change of temperature, when different amounts of naphthalene was added was measured before
the entropy was obtained. With these values, the cryoscopic constant, Kf was also calculated as
shown in Table 2. The values obtained were used to plot a graph of Kf against the mole constant
of naphthalene, X was plotted. The y-intercept from the graph was supposed to be the cryoscopic
constant for pure camphor. In this experiment, there were particular errors that led to the failure
of being able to obtain a straight line graph and hence, it was not possible to obtain the
cryoscopic constant value for pure camphor. The error that occurred was due to the breakage of
the of the test tube while heating the camphor with the naphthalene. Then, the mixture of
camphor and naphthalene was also sticking to the thermometer which gave an inaccurate
temperature reading.

The Second Law of Thermodynamics states that, the entropy of a substance is the measure of
the degree of disorder in a particular system (Kessel, Hans Van and Frank Jenkins , 2012). The
measure of the disorder in arrangements of the particles of the distribution of an atom or a
molecule in a thermodynamic system is given by the value of entropy. The entropy of the
substance can be determined by its physical state. The degree of disorder is the least in solid state
followed by the liquid state and then followed by the gaseous state. This means that a substance
will have its highest entropy when it is in gaseous state compared to solid or liquid state. This is
also the reason why the molar entropy of fusion of camphor which is denoted by Sf, increased
when the pure camphor melted.

As the pure camphor acted as the controlling variable in the experiment, different amounts of
naphthalene were added to it. As more naphthalene was added into the same amount of camphor,
the freezing point of the camphor eventually decreased. Since the system of the camphor was
being disturbed by the addition of naphthalene, the more naphthalene added, the more the
freezing point dropped. Due to he formation of bonds between camphor and naphthalene, the
naphthalene molecules were rearranged with the camphor molecules. A cluster begins to form
between the molecules of both the substances for conversion to solid state to occur in order to
freeze a substance which is in liquid state. The molecules prefer slower movement, because high
speed movement has high kinetic energy which inhibits cluster formation whereas slow
movement will reduce the kinetic energy. As the temperature of the mixture drops, the kinetic
energy is released as heat energy to the surroundings. Hence, pure camphor has higher freezing
point compared to camphor mixed with naphthalene.

Conclusion:

The molar entropy of fusion of camphor was studied. However, the due to the failure in the
experiment, the molar entropy of fusion of pure camphor was not able to be determined.

References

Kessel, Hans Van and Frank Jenkins . (2002). Nelson Chemistry 12 (12th ed.). Nelson Education
Limited.