Experiment 13: Determination of the molar entropy of fusion of camphor

Objective

1. To study the molar entropy of fusion of camphor

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

Introduction
Camphor, C10H16O is an aromatic crystalline compound which is obtained from naturally from the wood
or leaves of the camphor tree or synthesized. The camphor is used in this experiment to determine its
molar entropy of fusion. Molar entropy of fusion is denoted as (∆Sf), which represents the entropy
increases when a particular substance is melting. The entropy is always depends on the state of the
substance. The disorder in entropy of a substance is the lowest in solid state, whereas liquid is more
disorder and followed by gas state with highest disorder in entropy. In another words, the degree of
disorder increases in the transition from a closely packed molecule arrangement solid to the disorganized
molecules arrangement of liquid state. But, in this experiment, the entropy of camphor is the energy
absorbed by the camphor is disturbed by the adding of naphthalene in the system.
The molar entropy of fusion (∆Sf) of camphor can be determined cryoscopically. Entropy, S is a
thermodynamic quantity that is a measure of how dispersed the energy of a system is among the
different possible ways that system can contain energy. When the energy of a thermodynamic system is
concentrated in a relatively few energy states, the entropy of the system is low. When the same energy is
dispersed or spread out over a great many energy states, the entropy of the system is high. Cryoscopy is
a technique used for determining the molecular weight of a solute by dissolving a known quantity of the
solute into a solvent and records the drops of freezing point of the solvent. For dilute solutions of
naphthalene in camphor is described as below.
∆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 Kf = RT02/∆Hf
X0
Where R (the gas constant) = 8.314 Jk-1 mol-1
T0 is the freezing point of pure camphor in K and ∆Hf is molar enthalpy of fusion of camphor in J

Since ∆Sf = ∆Hf/T0

Thus Lim Kf = RT02/∆Hf
Colligative properties are defined as those properties of solutions that depend on the number of
dissolved particles in solution, but not on the natures of the solutes. The freezing point and boiling point
of the particular solutions will be affected. This is because a liquid solution containing a solvent with an
impurity is more disordered than a pure solvent. Therefore more energy must be removed to take the
solution from its highly disordered liquid state to its ordered solid state than to do the same for a pure
solvent. Hence, solutions of solvents with impurities freeze at a lower temperature than pure solvents
due to colligative effect. In this experiment, colligative property is related to the freezing point
depression and molality of a liquid.
The molality of a liquid is calculated by using the number of mole of solute is divided by the mass of
solvent used in kg

Molarity = moles of solute/kilograms of solvent

Apparatus
Test tube, beaker (250cm3), Bunsen burner, thermometer (0-200)

Materials
Camphor (M=152g/mol), naphthalene (M=128g/mol)

Procedure
2g of camphor is being melted and stirred in a test tube. The test tube in an air jacket and is allowed it to
solidify. The air jacket is removed and the test tube is heated gently until melting commerce. The
content is stirred with the thermometer and the temperature at the last crystal just disappears. Then,
0.05g of naphthalene is added into this test tube and the process is repeated. The procedure is repeated
for further 0.05g of naphthalene up to a total weight of 0.20g of naphthalene.
 Results and calculations
Weight of naphthalene (g) 0 0.0518 0.1030 0.1537 0.2050
Number of moles of naphthalene (mol×10-4) 0 4.05 8.04 12.00 16.01
Weight of camphor (g) 2.0016 2.0016 2.0016 2.0016 2.0016
Number of moles of camphor (mol) 0.0132 0.0132 0.0132 0.0132 0.0132
X 0 0.0298 0.0574 0.0833 0.1082
Freezing point (K) 413 373 343 333 328
∆ T (K) 0 40 70 80 85
Kf 0 1342 1220 960 786
*Molecular mass of naphthalene and camphor are 128.06 g/mol and 152.13g/mol
ΔT= depression of freezing point of the mixture in K
Kfp= freezing point depression constant (Kfp of camphor= 37.7 /m)
m = molality of the solute = No. of solute mole (mol)/ mass of solvent (kg)

∆T = Kf X
= 40/0.0298
= 1342
= 70/0.0574
=1220
= 80/0.0833
= 960
= 85/0.1082
= 786

Since

Lim Kf = RT02/ ∆Hf Equation 1

∆Sf = ∆Hf / T0 Equation 2
Thus substitute Equation 2 Equation 1
Lim Kf = RT0/ ∆Sf

From the graph plotted,

Lim Kf = RT0/ ∆Sf
X=0
RT0/ ∆Sf = 1550
1550 = 8.314 x (413) / ∆Sf
∆Sf = 2.216 J K--1 mol-1

∆Sf = ∆Hf / T0
∆Hf = 2.216 J K--1 mol-1 x 413 K
= 0.9149 kJ mol-1

Discussion
In this experiment, the molar entropy, Sf of the camphor is obtained which has the value of 15 J/mol.
Before obtain the molar entropy, we have to measure the temperatures change in each of the different
amount of naphthalene added into the camphor. After the temperature changes are obtained, the
cryoscopic constant for each amount of naphthalene added are calculated, the value of cryoscopic
constant for each are shown in table. By using the value obtained, a graph of cryoscopic constant against
mole fraction of naphthalene in the mixture is plotted and the y-intercept represents the cryoscopic
constant of pure camphor which is 246.5.
According to the Thermodynamics Second Law, the entropy of a substance is the measure of the degree
of disorder in a particular system. The value of the entropy of a distribution of atoms and molecules in a
thermodynamic system is a measure of the disorder in the arrangements of its particles. State of the
substance can determine the entropy of its substance. The degree of disorder is increase from solid state
to liquid state and finally to gaseous state. In another word, the entropy of the same substance has higher
entropy when it is in gaseous state compared with solid or liquid state. Molar entropy of fusion of
camphor is denoted as (∆Sf), which represents the entropy increases when a pure camphor is melting.
The different amounts of naphthalene are added into camphor as the pure camphor act as the control
experiment. The pure freezing point of camphor is 140 in this experiment. After added the naphthalene,
the freezing temperature are decrease as more amount of naphthalene is added into the same amount of
camphor. The more the naphthalene added, the lower the freezing temperature of the particular mixture.
This is showed that the system of camphor is being disturbed by naphthalene. The naphthalene
molecules are rearranged with the camphor naphthalene in order to form bond in between each other.
For a substance in liquid state to freeze, the naphthalene and camphor molecules begin to form cluster of
molecules to convert to solid state. The molecule moves in high speed are not able to form a cluster of
molecule with each other, so the molecules prefer move slower by reducing their kinetic energy. The
kinetic energy is converted into heat energy that is being released to the surrounding as the temperature
of the mixture decrease. Thus, the freezing point of the solvent with different solute is lower than the
freezing temperature of pure solvent.
Precaution steps
In this experiment, there is some precaution steps should be taken. Firstly, the zero error should be
avoided when measuring the weight of naphthalene and camphor. This can be avoided by press the tare
button when use it. Secondly, the reading of temperature on thermometer should be taken parallel to the
eyes to avoid parallax error.

References
Cann, P. a. H. P., 2015. Cambridge International AS and A Level Chemistry. s.l.:Hodder Education.
Silberberg, M., 2009. Principles of General Chemistry. s.l.:s.n.