CHM145L Organic Chemistry 1 Laboratory

1st Quarter, S.Y. 2015-2016

Melting Point and Boiling Point of Organic Compounds

Castro, Ethan Zachary G., Pasia, Abraham Paul L., Pulido, Froileth S.1
1

Professor Oliver Villaflores, School of Chemical Engineering, Chemistry, Biological Engineering and Materials

Science Engineering, Mapa Institute of Technology; 2Castro, Ethan Zachary G., Pasia, Abraham Paul L., Pulido,
Froileth S., CHM145L-C11, School of Chemical Engineering, Chemistry, Biological Engineering and Materials
Science Engineering, Mapa Institute of Technology

ABSTRACT
The Structural Theory of Organic Chemistry implies that the chemical structures of compounds, most
especially organic compounds, greatly influence their physical and chemical properties. Two of the essential physical
properties of organic compounds are their boiling point and melting point, or the temperature where the organic
substance shall begin to boil and melt, respectively. The experiment primarily aims to validate the effect of the chemical
structure of various organic compounds to their two aforementioned physical properties by comparing the boiling point
and melting points of various organic compounds with various chemical structures. Chemical structure primarily refers
to the intermolecular forces of attraction occurring within the molecules of an organic compound, and geometric
isomerism, or the variety of molecular geometries or arrangements that molecules of a certain organic compound may
be arranged. To address the primary objective of the experiment, a variety of solid organic compounds, including
naphthalene, benzoic acid, salicylic acid, benzoin, and urea were heated to determine their melting point range
experimentally, using the Thomas-Hoover Apparatus. Further, to test the effect of geometric isomerism, finely ground
maleic (cis) and fumaric (trans) acids, which are isomers of each other, were tested in the same manner. Moreover, to
test the effect of purity of substances on the melting point, pure and impure samples of urea were tested in the same
way. In addition, various types of liquid organic substances were tested in terms of their boiling points by applying heat
using a hot plate. Among these include n-Butanol, 2-Butanone, n-Hexane, n-Heptane, and propanoic acid. Finally, the
effect of more branched molecular structures on the boiling point was tested by treating n-butyl alcohol, sec-butyl
alcohol, and tert-butyl alcohol in the same manner. Doing these, the researchers were able to validate the effects of
various chemical structures on the melting and boiling points of organic substances. It was proven that as the
intermolecular forces occurring within an organic compound are stronger, its boiling point and melting point is higher
than those with weak intermolecular forces. On the other hand, the trans isomers, such as fumaric acid, have higher
melting points than those of the cis isomers, like the maleic acid. Finally, as branching within an organic compound
increases, its boiling point decreases due to the increase in the surface area of the compound.
Keywords: structural theory, organic compounds, intermolecular forces, geometric isomerism, branching

INTRODUCTION
The melting point of a solid substance is
the point at which the solid state changes into
liquid state at an atmospheric pressure; at this
point, the solid and liquid phases exist in an
equilibrium. On the other hand, the boiling point of
a substance is the temperature in which the vapor
pressure of the liquid is the same with the

Experiment 1 | Group 4 | October 13, 2015

pressure of the surrounding liquid, at this point, the

liquid changes into vapor or gas.
The melting point and boiling point of
organic substances are being affected by several
factors: the relative strength of the four
intermolecular forces, the number of carbons
present in the compound or the molar mass of the
compound, the branching of the structures, the
geometric isomers and purity.
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For a solid to liquefy or liquid to vaporize,

the molecules of the substances should have an
attraction to one another. As a process that gas to
liquid to solid is involved, the molecules of the
compound that undergoes that process are turned
more ordered and arranged in a closer proximity.
The attractions are often in the form of charge or
partial charge and these attractions are coined
forces that define and describe the physical and
chemical properties of molecules.

lastly, Van der Waals forces, in this order the

strength of the forces of attraction decreases
therefore, the melting point and boiling point of the
compound decreases as well.

Figure 2. Summarized description of some forces of

attraction.

Figure 1. Certain compounds with different forces of

attraction but with equal molecular weight

As mentioned before, the intermolecular

force of a compound affects the melting point and
boiling point of the organic compound.
Compounds which has an ion-ion force of
attraction have greater melting and boiling point.
The ion-ion force is the strongest of the other three
forces of attraction because of the attraction
having at least a whole positive charge or full
negative charge. A recall in General Chemistry,
fully charged compounds are attracted to each
other very much, they tend to get close and form
extensive ion networks. Highly ordered tightly
packed networks of ions, which ion-ion forces
exhibit, are very hard to break therefore, a greater
amount of energy is needed to break these bonds
or forces. That being said, as the forces get
weaker, the melting point and boiling point of the
compound lower. Second to ion-ion forces, dipoledipole forces follows, then Hydrogen bonding and
Experiment 11 | Group 4 | October 13, 2015

Second, as the molecular weight of the

compound increases, the melting point and boiling
point also increases. When the molecular weight
of the compound increases, the length of the chain
also increases which is proportional to the surface
area, and by increasing the surface area, the
ability of the individual molecule to attract each
other strengthens and increases, which will now
go under the first discussed condition.

Figure 3. Few examples where as the string increases, the

boiling point increases.

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The branching of a compound decreases

the boiling point of a substance. As the chain of
the molecule branches, the structure of the
molecule becomes more compact and makes the
surface area decrease. In relation with the first and
second discussed conditions, the intermolecular
attractive forces that depends upon the surface
area, turns small in magnitude on account of
branching. Therefore proving the relationship of
branching to the melting and boiling point of a
compound.

Figure 4. Example of Branching

Isomers are molecules which has the

same molecular formula, but a different
arrangement of the atoms in space can be viewed
from them. This is one of the factors that can affect
the melting point of an organic compound. Two
common example of isomers are cis and trans
isomers. Cis isomers display two chlorine atoms
which are locked on the same side of the double
bond, and Trans isomers display chlorine atoms
that are locked on the opposite sides of the double
bond. By applying the first condition alone, we can
say that cis isomers will display higher melting
point, but that is not the case, it is important for the
intermolecular attractive forces to have a molecule
which is tightly packed together in solid efficiently.
With that being mentioned, the cis isomers fall
behind trans isomers because the U shape of the
cis isomer does not pack as well as the straighter
shape of the trans isomer. The poorer packing of
the cis isomer will display a lesser effectivity of the
intermolecular forces of attraction compared to
trans isomers. Therefore, cis isomers will have a
lower melting point compared to the trans isomers.

Experiment 11 | Group 4 | October 13, 2015

Lastly, the purity of organic compounds

can also affect the melting point range of an
organic substance. Considering a pure organic
substance, all of the molecules in this compound
are the same, hence, they are perfectly packed
together in a very orderly array. In this condition,
the intermolecular attractive forces between the
molecules are maximized. On the other hand, an
impure organic compound or an organic
compound which contains two or more different
organic molecules, they will not fit perfectly
together and would not make an orderly array.
Therefore, pure organic compounds have narrow
melting point range while, an impure organic
compound will have a broader melting point range.
Again, the melting point and boiling point
of a particular organic substance may increase or
decrease depending on the condition or factor that
it undergoes. If it is of strong intermolecular
attractive force, it is expected to have a high
melting point and boiling point, otherwise, lower
melting point and boiling point will be observed.
Second, organic compounds with greater
molecular weight and has lesser branches will
display high melting point and boiling point. The
last two conditions also affects the melting point
and boiling point of the organic compounds, but
they are easy to comprehend since the first three
conditions applies to the last two conditions.

METHODOLOGY
The experiment is divided into two parts
which are melting point and boiling point. It is
subdivided into a single part: structural effect,
which is still subdivided into few parts, for melting
point, intermolecular forces of attraction,
geometric isomers and effect of purity on melting
point range; for boiling point: intermolecular forces
of attraction and branching.
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In the melting point part, the researchers

must obtain a capillary tube, where one end of this
tube will be sealed by heat so this tube can be
used as a sample holder. After this procedure,
obtain a small amount of the solid sample and
push it into the open mouth of the tube until
enough samples are contained. Tap the tube
(close end) on the table to move the sample to the
bottom. If it still remained on the upper portion of
the tube, drop the capillary tube inside a one meter
glass tubing where one end of the tubing is placed
on the floor. The sample should be at least 5-6 mm
in height which must be tightly-packed. In order to
know the melting point of the sample, place the
capillary tube inside the sample holder of the
Thomas Hoover Apparatus.

In the second part of the experiment,

boiling point, a different procedure will be followed.
Acquire a Thiele tube and fill up the tube
with glycerol slightly above its arm. Again, obtain
a capillary tube and heat it at the middle until it
becomes completely twisted. Place the processes
capillary tube inside a micro test tube containing
two to three drops of the test compounds or
mixtures. Place the micro test tube containing the
sample and the capillary tube in the Thiele tube,
use a 2-mm wide rubber tubing to hold the
capillary tube. Immerse the thermometer, along
with the micro test-tube, in the Thiele tube. Note
that the rubber tubing must not be in contact with
the glycerol. Then, heat the oil bath until bubbles
are visible. As bubbles can be observed, remove
the flame and allow the oil to cool. As the
temperature decreases, the bubbling will slowly
stop and the liquid will start to enter the tube, in
this process, record this temperature as the boiling
point of the compound. To acquire the boiling point
range, reheat the oil slowly and take note of the
temperature when the liquid comes out of the
capillary tube. The initial temperature recorded,
and the final recorded temperature will serve as
the boiling point range.

RESULTS AND DISCUSSION

Figure 5. Thomas Hoover Apparatus

After which, switch the apparatus on,

adjust the temperature and turn the stirrer on.
Record the temperatures at which the compound
starts to turn to liquid and when it has completely
turn to liquid, this will serve as the melting point
range.

For the first part of the experiment, Table

1 shows the data obtained in testing the given
samples in the Thomas-Hoover Melting Point
Apparatus for the effect of the intermolecular
forces of attraction on the compounds melting
point.

For the other sub-parts of melting point,

the procedures will be the same.
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TABLE 1
Compound
Benzoic
Acid
Benzoin
Naphthalene
Salicylic
Acid
Urea

Melting
Point

True
Value

112 123

118

122.41

130 138
74 86

134
80

132
80.26

151 157

154

159

127 135

131

133

T1

T2

From these data, it can be inferred that

naphthalene has the lowest melting point while
salicylic acid has the highest. By observing these
two species, the researchers observed the
polarity. Salicylic acid, also known as 2hydroxybenzoic acid and 2-carboxypheno,
contains a carboxylic group and a hydroxyl group
which is asymmetric with each other. These
asymmetric groups give salicylic acid a net dipole
moment making it a polar molecule. On the other
hand, naphthalene, being a hydrocarbon is a
non-polar molecule. Hence, it can be observed
that for a compound that sticks closer together or
is held by a stronger intermolecular forces of
attraction, like dipole-dipole for some polar
compounds and hydrogen bond, the melting
point is higher because it requires more energy
for it to change from solid to liquid. Thus, salicylic
acid being a polar compound has a high melting
point because of the hydrogen bonding it
displays while naphthalene has a lower melting
point because it only exhibits London dispersion
force.
On the next part of the experiment where
the effect of geometric isomerism on the melting
point of the two samples, Fumaric and Maleic
acid, was investigated. Geometric Isomerism or
Cis-Trans Isomerism is a form of
stereoisomerism where the atoms making up the
isomers are joined in the same order but still
manage to have different spatial arrangement.
Experiment 11 | Group 4 | October 13, 2015

The words cis and trans are of Latin origin

which means on the side and on the other
side or across. These words tells us which side
of the double bond the similar atoms are found.
Theoretically, Fumaric acid, a Trans-isomer, and
Maleic acid, a Cis-isomer, both have
intermolecular forces, but intermolecular forces
work well when the molecules are held efficiently
in the solid. Trans-isomer are held better than
cis-isomer. The U-shape of the Cis-isomer is not
that efficient in packing together the structure and
molecules compared to a straighter shape of a
trans-isomer, making the intermolecular forces in
the cis-isomer less effective then, requiring less
energy to melt itself. This concept is also
supported by the data that we have gathered in
the laboratory summarized below in Table 2
TABLE 2
Compound
Fumaric
Acid
Maleic Acid

T1

T2

Melting
Point

True
Value

300

304

302

287

127

132

130

135

Purity has also an effect on the melting

point range of the substance. In fact, melting
points are even used in some experiment to
determine impurities. In this part, the researchers
observed the melting points of a pure and impure
sample of urea. From Table 3 below, we can see
that impure urea has lower melting point
compared to urea. This is because of the effects
of the impurities on the forces of attraction in the
molecule. From general chemistry, solids are
classified into two, crystalline and amorphous
solids. The most common type are the crystalline
solids. Inside these type of solids are molecules
or repeating cluster of ions arranged in a regular
tightly packed repeating crystal lattice which are
held by different intermolecular forces of
attraction. The pattern of these forces are
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disordered when a substance melts. But when

interferences such as impurities disrupt the
pattern of forces it will result to a lesser
requirement of energy input to melt the
substance because the intermolecular forces of
the compound are already disrupted. That is why
the average melting point of impure urea sample,
as seen on Table 3 is lower compared to that of
the pure urea.
TABLE 3
Compound
Impure Urea
Pure Urea

T1
120
127

T2
129
135

Melting point
125
131

Melting point is not only the physical

property of matter which is important in studying
chemistry and is affected by the factors
considered in this experiment. One of these
many physical properties is the boiling point.
Boiling point is the temperature at which the
vapor pressure of the liquid is equal to the
pressure of the surrounding. It is also the point
where the gas and liquid phases are in
equilibrium. The only factor considered in this
experiment is the structural effect, specifically the
effects of intermolecular forces of attraction and
branching. Like what the researchers discovered
in the effect of intermolecular forces on the
substances melting point, boiling point also
increases as the strength of the intermolecular
forces increases. Considering the data below in
Table 4, n-Butanol is an isomer of Butanol. It
exhibits limited miscibility in water due to the
carbon chains of alcohol that resists being
miscible to this solvent and the hydroxyl group
which makes it a polar substance with a high
boiling point.
2-Butanone is also a polar compound.
The oxygen which carries a partially negative
charge and carbon which is partially positive
creates a strong dipole-dipole which in turn will
Experiment 11 | Group 4 | October 13, 2015

require greater energy to break the bonds

resulting to a high boiling point. Heptane on the
other hand is a non-polar compound but its
boiling point is still high because it has seven
carbon atoms. For alkanes, both boiling and
melting points increases as the number of carbon
atoms increases because it also increases the
molecular weight and an increase in molecular
weight will also increase the magnitude of the
van der Waals force of attraction. n-Hexane is
also a non-polar compound, the bonds with its
hydrogen and carbon are very symmetric and
uniform that there is no net dipole formed. The
last one is the Propanoic acid with the highest
boiling point. Propanoic acid is a carboxylic acid
which is generally polar hence, it showed a high
boiling point.
TABLE 4
Compound

T1

T2

n-Butanol 115 119

2-Butanone 77 82
Heptane
97 103
Propanoic
138 144
Acid
n-Hexane
69 71

Boiling
Point
117
80
100

True
Value
117.4
79.64
98.42

141

141.2

70

68

The last part is about the effect of

branching. Branched compounds have lower
boiling point compared to straight chain isomer.
This is because of the weak intermolecular forces
of attraction are most likely formed in straight
chain producing stronger intermolecular forces
and requiring great amount of energy to break
the bonds. Among the three, tert-butyl is the
compound has more branching, which explains
the low boiling point observed in the experiment
while n-butyl is just linear.

CONCLUSION AND RECOMMENDATIONS

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The first part of the experiment exhibited

the effects of intermolecular forces of attraction
and geometric isomerism on the melting points of
compounds. In the case of naphthalene, benzoic
acid, salicylic acid, benzoin and urea, their
difference in intermolecular force is the cause of
the different melting points. When determined,
salicylic acid had the highest melting point then
followed by urea, benzoin, benzoic acid and
finally naphthalene. Salicylic acid had the highest
melting point due to the intermolecular forces of
attraction found in the compound, hydrogen
bonding and its 2 hydroxyl groups. Benzoin also
benefits from hydrogen bonding but does not
require as high of a melting point as salicylic acid
due to it having only 1 hydroxyl group. This is
then followed by urea containing 2 amine groups
which are capable of hydrogen bonding and then
benzoic acid, also capable of hydrogen bonding
using the hydrogen in its carboxylic group. And
finally for naphthalene, its main intermolecular
force of attraction is the London Dispersion
forces and considering this is the weakest
intermolecular force and being the easiest to
break, it results in this compound having the
lowest melting point in all the organic substances
analyzed.
In the case of the Maleic acid and
Fumaric acid, both having C4H4O4 as their
molecular formula, their melting point is affected
by the fact that they are stereoisomers. The
arrangement affects the melting points of these
compounds. Fumaric acid showed a much higher
melting point than maleic acid due to the fact that
Fumaric acid is a trans-isomer and Maleic acid is
a cis-isomer. The fumaric acid contains stronger
intermolecular force because of the two
carboxylic groups that are on opposite sides of
the double bond in the compound, making the
compound more compact. This makes the
compound require a higher temperature in order
to achieve its melting point. This is in opposition
Experiment 11 | Group 4 | October 13, 2015

to maleic acid being a cis-isomer meaning that its

two carboxylic groups are found on only one side
of the double bond in the compound and thus not
having as strong of an intermolecular force of an
attraction as the fumaric acid.
In terms of purity, pure urea melted at a
more tapered down melting point range. With
pure urea being a homogenous substance, the
needed temperature for it to melt would be a
more narrowed down value. This is as opposed
to the impure urea that can easily affect the
melting point range because of the different
constituents that may raise or lower the melting
point of the substance. The melting point range is
then widened and thus becomes harder to
precisely determine the actual melting point of
urea.
The second part of the experiment
exhibited the effects of intermolecular forces of
attraction on the boiling points of different organic
compounds. The test compounds were nButanol, 2-Butanone, n-Hexane, Heptane, and
Propanoic acid. The compound that contained
the highest boiling point was Propanoic acid,
followed by n-Butanol, Heptane, 2-Butanone, and
finally n-Hexane. This is due to Propanoic acid
containing a hydrogen bond as opposed to nHexane mainly having its forces be the London
Dispersion forces, the weakest and easiest to
break forces.
Lastly, branching resulted in a decrease
of boiling point of the compound butyl alcohol.
Thus, n-butyl alcohol had the highest boiling
point and tert-butyl alcohol had the lowest boiling
point. Branched molecules result in weaker
dispersion forces; thus requiring less temperature
needed in order to break the bonds between
molecules.
In the melting point of organic
compounds, there were three trends that showed
an effect on the test compounds. The
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intermolecular forces of attraction, the greater the

attraction the greater the temperature needed to
break the bond. The geometric isomers of a
compound, having the same molecular weight
but differ in geometry and thus affecting the
melting point. And lastly, the purity and the
melting point range, the more pure the
substance, the narrower the melting point range.
In the boiling point of organic
compounds, the trends were intermolecular
forces and branching. Intermolecular forces
affected the compound in the way that it needed
higher temperature levels in order to break the
stronger intermolecular forces and lower
temperature levels for the weaker intermolecular
forces. Branching, however, due to it resulting in
weaker dispersion forces and making the bonds
easier to break, required lower temperature
levels.
It is recommended for other researchers
to analyze more organic compounds in order to
clearly see the differences that the trends make
in consideration to their melting points and boiling
points. It is also recommended to confirm
findings and try to replicate gathered results.

References
Brittain, C. G. (2009, May 18). Using Melting Point to
Determine Purity of Crystalline Solids.
Retrieved from The University of Rhode
Island:
http://www.chm.uri.edu/mmcgregor/chm228/
use_of_melting_point_apparatus.pdf
Clark, J. (2012). STEROISOMERISM - GEOMETRIC
ISOMERISM. Retrieved from Chemguide:
http://www.chemguide.co.uk/basicorg/isomer
ism/geometric.html
Feynman, M. (2014). Why do branched chain
compounds have lower boiling points than
the corresponding straight chain isomers?
Retrieved from Chemistry StackExchange:
http://chemistry.stackexchange.com/questio
ns/6944/why-do-branched-chaincompounds-have-lower-boiling-points-thanthe-corresponding
Master Organic Chemistry. (2015). 3 Trends That
Affect Boiling Points. Retrieved from Master
Organic Chemistry:
http://www.masterorganicchemistry.com/201
0/10/25/3-trends-that-affect-boiling-points/
Shimizu, K. (2015). HOW TO: PREDICT BOILING
POINT AND MELTING POINT TRENDS.
Retrieved from Organic Chemistry FAQ:
http://www.chem.sc.edu/faculty/shimizu/333/
Chem_333/2b.i.html

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