Experiment #5: Melting Point and Boiling Point Determination

Dela Cruz, Renzxymon L.; Gabriel, Ezekiel M

Chem 31.1, HEJ, Ms. Kristine Tolentino
October 16, 2014
I. Abstract
Boiling point and melting point are two of the physical properties of organic compounds that are
determined by intermolecular forces. The experiment made use of quantitative methods to determine
such properties. Samples in test tubes attached in a thermometer were placed in an oil bath to break the
bonds between molecules. It was observed that pure benzoic acid has a higher melting point as
compared to benzoic acid mixed with urea, thus impurities in a compound lowers its melting point due to
the disruption in the packing of benzoic acid. The distillate obtained through simple distillation was found
to have a higher boiling point as compared to the distillate obtained through fractional distillation because
the first distillate contains more water and was able to increase hydrogen-bond strength between its
molecules. The objectives of the experiment are to understand the factors affecting physical properties
and to use these understanding in the industrial level to estimate purity and identify compounds.
II. Keywords
Melting Point, Boiling Point, Intermolecular Forces
III. Introduction
The physical properties according to
Klein (2012) of a compound are determined by
the attractive forces between the individual
molecules, called intermolecular forces. Boiling
point and melting point are physical properties
exhibited by liquid and solid chemical
substances respectively and in this case,
organic compounds. Chang (2010) defines the
boiling point of a substance as the temperature
at which the vapor pressure of a liquid is equal
to the external pressure. The normal boiling
point of a liquid is the temperature at which it
boils when the external pressure is 1 atm. The
melting point of a solid is the temperature at
which solid and liquid phases coexist in
equilibrium. The normal melting point of a
substance is the temperature at which a
substance melts at 1 atm pressure.
In order for a compound to boil or melt,
the forces that hold the individual molecules
together must be broken. This means that the
boiling point and melting point of a compound
depends on the strength of the attractive forces
between the individual molecules. If the
molecules are held together by stronger forces,
more energy will be needed to pull the
molecules away from each other and the
compound will have a higher boiling point and
melting point. In contrast, if the molecules are
held together by weaker forces, fewer amount of
energy will be needed to pull the molecules
away from each other and the compound will
have a lower boiling point.
It is difficult to predict the boiling point or
melting point of a compound based only on its

Chem 31.1

structure but there are certain trends that can be

observed which make it easier to compare
compounds and predict which would have a
higher boiling point or melting point. These
trends are the size and weight of the molecule,
branching, polarity, the symmetry of the
molecule, and the presence of intramolecular
hydrogen bonding within the molecule.
The Boiling Point and Melting Point may
also be affected by pressure and the presence
of impurities within a substance. The purity of an
impure substance can therefore be measured
using the boiling point or melting point given that
the boiling point or melting point of the pure
substance is known. An impure substance will
tend to boil or melt over wider range of
temperature as compared to that of pure
substances. Since most organic compounds
have varying boiling points and melting points,
we can then use these properties in order to test
and identify unknown organic substances.
This experiment seeks to develop the ability
to determine the melting point and boiling point
of substances. It also develops the skill to
determine the purity of a compound using its
intensive properties such as melting and boiling
points. It also provides an understanding on how
structural features of a compound affect its
melting point or boiling point.
The significance of this experiment lies on
the practical and industrial application of the
concepts governing melting and boiling points.
These physical properties can be used to
estimate the purity and determine the identity of
an unknown solid or liquid compound.

Melting Point and Boiling Point Determination

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IV. Experimental

B. Boiling Point Determination.

A. Melting Point Determination of Benzoic

Acid and Benzoic Acid-Urea Mixture
In this experiment, the melting point of pure
benzoic acid and benzoic acid-urea mixture
were determined by placing 0.5g of their
respective ground sample in two different
capillaries sealed in one end occupying 1cm.
Each sample was powdered using different
mortar and pestle. These capillaries were then
attached to a thermometer using a rubber band.
The thermometer was then place in a beaker
containing enough oil to submerge the 1cm
sample. It was then heated and the
temperatures at which the sample starts to
liquefy and the temperature at which the solid
has completely melted were recorded as their
respective ranges of melting point.
B. Boiling Point Determination of Distillate and
Hexane
st

The boiling points of hexane, 1 distillate

nd
and 2 distillate were determined by introducing
10 drops of each sample into a 5mL test tube
attached to a thermometer by a rubber band.
Capillaries sealed at one end were place in the
test tube such that the open end is immersed in
the sample being tested. This was then
subjected in an oil bath raising the temperature
until a continuous stream of bubbles is
observed. The bath was allowed to cool and the
temperature was noted as the instant bubbles
cease to come out of the capillary and just
before the liquid sample enters the capillary
tube. Their respective boiling points were then
determined.
V. Results
A. Melting Point Determination
Table 1. The table shows the ranges of melting point of
benzoic acid and benzoic acid-urea sample.

Sample

Melting Point Range

o
( C)

Benzoic Acid

110 - 120

Benzoic AcidUrea Mixture

79 - 85

The samples were placed in capillaries and

were placed in an oil bath. The following
experimental melting points of each sample
yielded. The melting point of pure benzoic acid
is greater than the melting point of benzoic acid
with urea as an impurity to the sample. .

Chem 31.1

Table 2. The table shows the different experimental

boiling points of each sample.
o

Sample

Boiling Point ( C)

Hexane

69.5

Distillate 1
(from simple
92
distillation)
Distillate 2
(from fractional
86
distillation)
The solutions were again placed in an oil
bath to determine their respective boiling
points. The boiling point of hexane is closed to
o
the theoretical value which is 68 C. The first
distillate has a higher boiling point than the
second and these values were compared to
the results of the previous experiment. Their
boiling points have deviated from the
temperature from which the distillate was
extracted.
VI. Discussion
Melting point and boiling point determination
involves the breaking of bonds so different
attractive forces in the molecule must be
considered. Ionic compounds tend to have
higher boiling and melting points due to the ionic
interactions between particles which exhibits the
strongest attractive force. However, organic
compounds are covalently bonded so dipole
forces, hydrogen bonding, and London
dispersion forces (which are exhibited by all
molecules) only affect the physical properties of
the compounds. Of the three forces, hydrogen
bonding is the strongest since it is a special type
of dipole-dipole forces involving hydrogen
covalently bonded with a very electronegative
atom such as oxygen, nitrogen, and fluorine
while the weakest is the London dispersion
forces.
Factors affecting the boiling point and
melting point of a compound are molecular
weight, branching, polarity, intramolecular Hbonding and molecular symmetry.
Larger
hydrocarbon
chains
and
compounds with higher molecular weight have
larger surface area meaning that they
experience stronger London dispersion forces
and this result in the compounds having higher
boiling points and melting points.

Melting Point and Boiling Point Determination

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The more branched a molecule is, the

more sphere-like it becomes and this in turn,
reduces the surface area in which the molecule
could interact which causes a decrease in the
boiling point and melting point of a compound.
The more rod-like a compound, the easier for it
to line up together and interact which gives the
compound a higher boiling point and melting
point.
More polar compounds have stronger
dipole-dipole interaction and thus increase the
boiling point and melting point of the compound.
Symmetrical molecules have a lower
boiling point than asymmetrical molecules
because the dipole moments cancel out and the
molecule becomes non-polar and would
therefore have less interaction. The melting
point of symmetrical molecules is influenced by
packing in its crystal lattice and so tighter fit
compounds would require more energy to break
the lattice thus increasing its melting point.
Presence of Intramolecular hydrogen
bonding within a compound decreases the
boiling point and melting point of the compound
because it reduces the interaction between
molecules as the polar groups are prevented
from interacting.
Part A of the experiment was focused on
determining and comparing the melting points of
a pure benzoic acid and benzoic acid-urea
mixture. Conceptually, the amount of sample
placed in the capillaries does not matter
because melting point is an intensive property
which means that melting point does not depend
on the amount of matter.
Enough heat was applied to break the
attractive forces interacting between the
molecules of both samples. As expected, pure
benzoic acid has a very high melting point. This
is because carboxylic acids have the ability to
from two hydrogen bonds per pair of molecule
consequently requiring huge amount of energy
to melt the compound. The benzoic acid-urea
mixture has a lower melting point than the pure
compound because the urea acts as an impurity.
Impurities in compounds disrupt the packing of
the crystal making it disorganize. This
disorganization of molecules weakens the
attractive forces present in the compound and
so less energy is required to break these forces
and lower energy requirement means lower
melting point. Thus, the purer the compound the
sharper and the higher its melting point. Same
compounds have the same melting point but the
melting point of a mixture of different
compounds (initially having identical melting

Chem 31.1

point) will be lower as compared to the melting

points of the compounds taken separately
because both compounds will act toward each
other as impurities.
In Part B of the experiment, determination
and analysis of the boiling points of hexane,
distillate 1 (from simple distillation), and distillate
2 (from fractional distillation) were performed.
The rationale in setting up the method for
determining the boiling point of each sample is
the relationship of atmospheric pressure, vapor
pressure, and temperature. During the initial
heating, the air trapped in the capillary tube
expands and leaves the tube and vapor from the
sample also enters the capillary tube. This gives
rise to the initial stream of bubbles. When the
temperature reaches the boiling point, the
atmospheric pressure equals the vapor pressure
inside the tube. As the temperature rises just
above the boiling point, vapor pressure will start
to escape and this accounts for the second set
of bubbles. Once, the heating is stopped, its
vapor pressure will decrease and when the
vapor pressure drops below the atmospheric
pressure, the liquid will be drawn to the capillary
tube forced by the atmospheric pressure and so
the temperature before the sample went up the
tube was recorded as the samples boiling point.
The result for the boiling point of hexane
o
which is 69.5 C was close to the theoretical
o
value of 68 C giving us 2.21% error. The boiling
st
point of the 1 distillate (from simple distillation)
nd
is greater than the boiling point of the 2
distillate (from fractional distillation). As the
previous
experiment
implies,
fractional
distillation is more efficient as it greatly extract
the ethanol from water (leaving 95% Ethanol
and 5% water in the distillate) than simple
st
distillation. Hence, the 1 distillate contains more
water than the second distillate. The boiling
st
point elevation of the 1 distillate is due to the
formation of hydrogen bonds between ethanol
and water. The greater the strength of this force
means the higher the boiling point. As compared
nd
to the 2 distillate which has purer ethanol, then
it can be expected that its boiling point will be
st
lower than the boiling point of the 1 distillate.
The experiment also wants to confirm the
boiling point of the distillates via comparing it
from the temperature from which these distillates
were extracted from the previous experiment.
From experiment 4, the temperature from which
o
distillate 1 was extracted is 84 C while distillate
o
2 is 74 C. The deviation of the results from
experiment 4 and the results from this
experiment is may be due to different

Melting Point and Boiling Point Determination

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atmospheric
pressure
from
which
the
experiments were performed because it affects
the boiling point of a substance.

impurity. Impurities change the crystal

lattice of a pure compound thereby
making it poorly arranged or organized.
This poor stacking of molecules such that
in benzoic acid-urea mixture will be
needing lesser amount of energy to
break the existing bonds between
molecules than a well organized structure
as in the pure benzoic acid. Less energy
means lower melting point while higher
energy requirement to break such bonds
means higher melting point.

VII. Conclusions and Recommendations

In this experiment, melting and boiling points
of different samples were determined. These
physical properties are affected by different
factors such as intermolecular forces of
attraction, molecular weight, polarity, branching
and molecular symmetry.
It was noted that impurities in a compound
lowers its melting point and that this physical
property can be used to determine the identity of
a compound. The determination of the boiling
points of the two distillates was performed to
confirm that compounds can be extracted via
distillation by using the knowledge of boiling
points.
It is recommended that during the procedure,
the temperature of the oil bath must be lowered
significantly before heating the capillary tubes
containing the samples. This is because heating
the capillary tube in an oil bath with a high initial
temperature would cause an immediate
boiling/melting of the sample, resulting in the
inaccuracy of temperature reading.
VIII. References
Brown, W.H., Foote, C.S., Iverson, B.L., &
Anslyn, E.V. (2012).Organic
th
Chemistry (6 Ed.).Belmont, CA:
Brooks/Cole Cengage Learning.
Brown, W.H. & Poon, T. (2000).Introduction
th
To Organic Chemistry (5 ed.). New
York, NY: John Wiley & Sons.
th
Chang, R. (2010). Chemistry (10 ed.). New
York, NY: McGraw-Hill Companies,
Inc.
Klein, D.R. (2012). Organic Chemistry. New
York, NY: John Wiley & Sons

IX. Guide Questions

1. Give an explanation of the observed melting
points.
- The melting point of benzoic acid-urea
mixture is lower than the melting point of
pure benzoic acid because urea is an

Chem 31.1

2. Give an explanation of the observed boiling

points of the two distillates.
st
- The boiling point of the 1 distillate is
nd
higher than the 2
because simple
distillation was used to extract ethanol
from water. Simple distillation is not that
efficient as compared to fractional
distillation so the distillate coming from
the simple distillation has more water
st
than the second. Since the 1 distillate is
o
mostly water (BP = 100 C), it elevates
the boiling point of pure ethanol alone
o
(BP = 78.37 C) due to hydrogen bonding
between ethanol and water. Distillate 2
has a lower boiling point because it has
purer ethanol.
3. What effect would poor circulation of the
melting point bath liquid have on the observed
melting point?
Poor circulation may cause uneven
heating of the sample. This may lead to
inaccurate results because the observe
melting point will be a little higher than
the actual value of the melting point of
the substance being observe.
4. What effect would incomplete drying of a
sample have on the melting point?
Incomplete drying of sample may
decrease its observe melting point
because incomplete drying may cause
some impurties to mix with the pure
compound. Any impurity in the compound
lowers its boiling point due to the
unorganized stacking of the molecues.
5. Three test tubes, labeled A, B, and C, contain
substances with approximately the same melting
points. How could you prove the test tubes
contain three different chemical compounds?
- Combine A and B, B and C, and A and C
in separate test tubes. Test for the

Melting Point and Boiling Point Determination

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melting points of the mixtures and

supposing that the three substances are
different chemical compounds, then one
of the compounds will act as an impurity
to the other compound within each of the
test tubes and so the melting point would
be different than previously observed.
6. Which would be expected to have higher
boiling point t-butyl alcohol or n-butyl alcohol?
Explain.
- n-butyl is expected to have higher boiling
point than t-butyl. T-butyl is more
branched and spherical so it lessens
the intermolecular forces of attraction
(London dispersion force) between its
molecules.
The surface area for
interaction gets shorter and the molecule
cannot get close enough for stronger
interaction. The weaker the IFA the lower
the energy required to break the
attractive forces, thus lower boiling point
as compared to n-butyl which is linear
that exhibits higher IFA and therefore will
have a higher boiling point.
7. Calculate the vapor pressure of a solution
containing 30 mol% hexane and 70 mol%
o
octane at 90 C assuming Roults Law is obeyed.
(Given vapor pressure of the pure compounds at
o
90 C: hexane = 1330 torr; octane = 253 torr).
o
o
PTotal = XhexP hex + XoctP oct
Xhex = 0.3; Xoct = 0.7 : P
o
P oct= 253torr

hex =

1330 torr;

PTotal = (0.3)(1330torr) + (0.7)(253 torr)

PTotal = 399 torr + 177.1 torr
PTotal = 576.1 torr

We hereby certify that we have given substantial

contribution to this report

__________________
Dela Cruz, Renzxymon L.

Chem 31.1

_______________
Gabriel, Ezekiel M.

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