CM134-1L: ORGANIC CHEMISTRY (LABORATORY)

1ST Quarter SY 2019-2020

Experiment 1
MELTING POINT, BOILING POINT AND SOLUBILITY OF ORGANIC COMPOUNDS
Bares, Ma. Ella Glyze B. / Group No. 1
August 22, 2019

INTRODUCTION
Pure substances are made up of only one type of atom or molecule. They exhibit very well-defined
physical properties that are not connected with the substance’s ability to combine with different substances.
Purity has an important impact on the chemical properties of a substance and these chemical properties
largely influence the behavior and properties of organic compounds. Pure substances have the potential to
form predictable products from chemical reactions. This reliability is because of the absence of foreign
substances or impurities that might interfere with the reaction. To measure the purity of a substance or
compound, numerous ways can be utilized: physical comparison with pure standard, boiling point and melting
point determination, colorimetric methods, analytical methods. Among the methods mentioned above,
determination of boiling and melting point range was chosen to be the medium in this experiment.
The melting point is the temperature at which the solid and liquid phase forms a pure substance that
exists in equilibrium at specific pressure. As heat is applied to the compound in solid phase, its temperature
increases until it meets the melting point. More heat then will turn solid into liquid by breaking up the
intermolecular forces that bind the organic compounds in a pack or solid state, additional heat then will raise
the temperature of the liquid as those broken up forces are freer to move in the liquid state. The amount of
heat or energy required depends on the strength of intermolecular forces that glues the intermolecular forces
together a pack or solid. Most mixtures and amorphous solids melt over a range of temperatures.
Most of the pure organic compounds have sharp melting point while others melt reproducibly over a
narrow range of temperatures, usually 1°C-2°C difference unless there is a presence of impurity in the
compound or error in the process that will yield a very significant difference or range of temperature. Melting
point determination--- to test the purity of an organic compound is done in a micro scale using less than a
gram of the test sample. A special equipment, apparatus in specific, will be used and utilized in this
experiment. We determine melting points for three reasons. Firstly, melting point helps in characterizing the
sample if ever the test sample is known. Secondly, melting point allows future characterization of organic
compounds that are yet to be tested. Lastly, the melting point range indicates whether the compound tested
is pure or not. Wide range of temperatures determine that the organic compound is impure while narrow-
range determines that it is pure.
The boiling point, on the other hand, is the temperature at which the vapor pressure of a liquid equals
the pressure surrounding the liquid and the liquid changes into a vapor. The boiling point varies depending
upon the surrounding environmental pressure. The atmospheric boiling point is the temperature at which the
vapor pressure of a liquid equals the defined atmospheric pressure at sea level, 1 atm. Standard boiling point
is the temperature at which boiling occurs at a pressure of 1 bar. At these boiling point temperatures, the
vapor pressure of the liquid becomes sufficient to overcome the pressure and allow bubbles of vapor to form
inside the bulk of the liquid. Heat of vaporization is the energy required to make the transition of phases
possible.
Boiling point determination is used to characterize new organic liquids. Boiling point is a type of
physical property which can be used for comparison of different organic liquids, as in the process of identifying
an unknown organic substance. Boiling point determination is much more complex than melting point
determination as it requires more material and is less affected by impurities. Boiling point, however, is not a
good indicator of purity because it mostly works on few micro liters of liquid but on small scale like this
experiment, it is very challenging to determine the range. In a homologous series of molecules, boiling point
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 CM134-1L: ORGANIC CHEMISTRY (LABORATORY)
1ST Quarter SY 2019-2020

increases in a regular manner. In fact, the normal saturated hydrocarbons’ boiling point ranges from 162°C
for methane and 330°C for n-C19H40. Heating must be slowed down to have narrow-boiling point range.
MATERIALS AND METHODS
Equipment and Glassware
Thiele tubes, Micro test tubes, Capillary tubes, Thermometer, Hot plate or Bunsen burner, Thomas-Hoover
Melting Point Apparatus
Test Compounds for Melting Point Determination
Naphthalene, Benzoic acid, Salicylic acid, Benzoin, Urea (pure and impure), Maleic acid, Fumaric acid
Test Compounds for Boiling Point Determination
n-Butanol, 2-Butanone, n-Hexane, n-Pentane, Propanoic acid, sec-Butanol, Glycerol, tert-Butanol
Methodology
a. Melting Point Determination
Capillary tubes were provided by the laboratory assistant, we sealed one end of the tubes using heat
from the Bunsen burner. We have gotten about a half an inch of each test sample, pressed it in the open end
of the capillary tube and dropped the tube in a one-meter glass tubing to transfer the test samples in the open
end to the sealed end and got it ready for melting point determination using Thomas-Hoover Melting Point
Apparatus. To operate the apparatus, we first placed the capillary tube in the sample holder, switched the
apparatus on, adjusted the heat and turned on the stirrer. We recorded the temperature at which the
compound started to liquefy and when it was completely liquefied to get the melting point range.
This process was repeated for all samples to determine the structural effects of intermolecular forces,
geometric isomers and the effect of purity on melting point range.
b. Boiling Point Determination
We filled the Thiele tube with glycerol up to the level slightly above its arm and clamped it to the iron
stand. We were instructed to make the three drops (as indicated from the laboratory manual) of test samples
to six for faster reaction, we put it in the micro test tube and placed a capillary tube in it. We tied the micro
test tube with thermometer using a rubber and submerged them in the glycerol. We clamped the thermometer
and micro test tube in the iron stand for support. We heated the oil bath using a Bunsen burner instead of hot
plate to get faster reaction. As instructed and clarified by the professor, T1 would be the temperature at which
there was a flow of bubbles coming out of the capillary tube and T 2 would be the temperature at which the
liquid started to enter the tube as it cools down. We were no longer asked to reheat the oil.
This process was repeated for all samples to determine the structural effects of intermolecular forces
and branching on boiling point range.
RESULTS AND DISCUSSION
A. Melting Point Determination
Organic Compound Melting Point Obtained Theoretical Melting Point Solubility in Water
Salicylic acid 158°C 158.6°C Less Soluble
Urea 132.2°C 133°C-135°C Soluble
Benzoin 134.4°C 134°C -136°C Slightly Soluble
Benzoic acid 121.35°C 122.4°C Poorly Soluble
Naphthalene 81°C 80.6°C Insoluble
Table 1. Structural Effect of Intermolecular Forces of Attraction
Intermolecular forces mediate reaction between molecules, including forces of attraction or repulsion
which act between molecules and other types of neighboring molecules. Intermolecular forces are weak
relative to intramolecular forces which are forces that hold a molecule together. Intermolecular forces are
simply indicators that there is existence and action of forces in the molecule. Intermolecular forces determine
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 CM134-1L: ORGANIC CHEMISTRY (LABORATORY)
1ST Quarter SY 2019-2020

bulk properties such as melting point and boiling point. The strongest of all intermolecular forces is hydrogen
bonding, followed by dipole-dipole interaction and then London dispersion of forces, this is in decreasing in
terms of strength manner. All matter experiences London dispersion of forces. Salicylic acid,
C6H4(OH)COOH, got the highest melting point among the five test samples for intermolecular forces. Salicylic
acid is a monohydroxy benzoic acid and undergoes dipole-dipole interaction and capable of hydrogen
bonding. The electrostatic bonds between the constituents of molecules of salicylic acid are increasing over
time through series of additions of heat compared to others. As the crystal lattice forms stronger bonds
between the molecules, it needs more heat or energy to melt. Given that salicylic acid is lipophilic in nature,
meaning “fat-friendly”, its solubility in water is very poor. The temperature at which salicylic acid started to
liquefy was at 153°C and the temperature at which it was completely liquefied was at 163°C, getting the
average yields our calculation 158°C which is slightly below but relatively close to the theoretical melting
point of the compound which is 158.6°C. The reason as to why the melting point calculated was slightly
behind or above the theoretical temperature was because our group was not the first to operate the Thomas-
Hoover Apparatus, meaning, as we had our turn to use the equipment, it was already preheated, thus, giving
us such values for melting point, however, despite the slight increase and decrease in temperature, it can be
observed that the experimental data obtained are close to the theoretical and accepted melting point of each
organic compound. Comes on the second highest is urea which is soluble in water; just like salicylic acid, it
also undergoes dipole moment or interaction and hydrogen bonding, however, it is smaller in molecule size
compared to salicylic acid; molecule size, aside from intermolecular forces, is also a basis or a factor in
determining the melting point of a compound. The experimental melting point obtained for urea was 132.2°C
which is also slightly behind the accepted range. Benzoin comes third, it is actually comparable to benzoic
acid, however, its structure made it outstand the latter because of its size, it undergoes dipole-dipole
interaction and capable of hydrogen bonding, too. Benzoin is slightly soluble in water, the melting point
obtained from the experiment was 134.4°C, this is within the accepted range of melting point of the
compound. Benzoic acid comes fourth and it is poorly soluble in water. Benzoic acid’s calculated melting
point is 121.35° which is short by 1.05°C to get the theoretical melting point, however, the difference is still
tolerable and negligible. Lastly, naphthalene with a calculated melting point of 81°C, it us a polar compound
with no hydrogen bonds or other polar groups at all, meaning, unlike the first-mentioned organic compounds,
naphthalene is not capable of hydrogen bonding and is not soluble in water. It can be observed that it is
slightly higher than its theoretical melting point. These small errors are given by the operation in the
equipment, however, these are relatively small and small differences are tolerable.
Organic Compound Melting Point Obtained Theoretical Melting Point Solubility in Water
Fumaric acid 298.65°C 298°C-300°C Less Soluble
Maleic acid 138.3°C 137°C-140°C Soluble
Table 2. Structural Effects of Geometric Isomers or Substituents
Intermolecular forces of attraction has been the sole and initial basis in ranking and comparing organic
compounds in the previous part of this experiment. However, attraction of intermolecular forces is not the
only factor that affects the melting point of the substance, the size of the molecule, too. If the melting point of
two pure samples shows significant and clear difference, it says that the two samples have different structural
arrangements to begin with, and this is the case for maleic acid and fumaric acid. Maleic acid and fumaric
acid are both stereoisomers, cis-trans in particular. When we say that two compounds are cis-trans isomers,
they have the same formula but differs on the rotation of their functional groups when put in a three-
dimensional space. Maleic acid is the cis isomer and fumaric acid is the trans isomer. Since they have
different structural arrangement, it is expected that they also yield different physical properties. The molar
mass of maleic acid is 134.087 g/mol and fumaric acid’s molar mass is 116.072 g/mol. Maleic acid has a
dipole-dipole interaction and hydrogen bonding, it got the moderate in strength and the strongest
intermolecular forces; maleic acid is a polar molecule because of dipole-dipole interaction. Fumaric acid, on
the other hand, only have London Dispersion of forces, a weak type of intermolecular force, this also explains
why trans isomers are always non-polar or less polar most of the time. At this point alone, it can be concluded
that maleic will have a higher melting point compared to fumaric acid, but no. Fumaric acid yields a higher
melting point and it can be justified by its orientation alone. Trans isomers have more symmetry than cis
isomers, meaning, their bonds are harder to break as compared to the latter. In order for intermolecular forces
to work well, the molecules must be able to pack together efficiently in the solid and trans isomers pack better
than cis isomers. Poor packing in cis isomers mean that the intermolecular forces are not as effective and
efficient as they should be and so less energy is needed to melt the molecule. Fumaric acid has many London
Dispersion forces and it has efficient packing structure which requires more energy to break the bonds. The
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 CM134-1L: ORGANIC CHEMISTRY (LABORATORY)
1ST Quarter SY 2019-2020

melting point of maleic acid obtained from the experiment was 138.3°C, this is within the range of accepted
melting point of maleic acid which is 137°C-140°C. The melting point of fumaric acid that was obtained from
the experiment was 298.65°C which is also within the accepted range of 298°C-300°C.
Organic Compound Melting Point
Pure Urea 133°C
Impure Urea 131.05°C
Table 3. Effect of Purity on Melting Point Range
Purity has always been the core of this experiment, such melting and boiling point determination
characterizes the purity of an organic compound. On this particular part of the experiment, melting point is a
useful indicator of purity as there is general lowering and broadening of the melting range as impurities
increase. Presence of foreign particles in a crystalline solid disrupts the repeating pattern of forces that hold
the solid together, thus, requiring lower or smaller amount of energy to melt the part of the solid surrounding
the impurity. An impure solid is typically heterogenous on the microscopic level, with pure regions of each
component distributed through the bulk solid. When an impure solid is warmed, microscopic melting first
occurs in a pure region by the component with the lower melting point, this is not visible to the eye. The more
impure the solid is, the more structure is disrupted and the greater variation in intermolecular forces in
different areas of the solid; the more impure the solid is, the lower its melting point will be since impurity and
melting point are inversely proportional to each other. The melting of pure substance or compound that occurs
at higher temperature than that of impure compound is called melting point depression, in here, significant
melting point range can be observed. In this experiment, pure and impure urea were put into test. The melting
point obtained for pure urea was 133°C while the melting point for impure urea was 131.05°C. The accepted
melting point range of urea is 133°C-135°C. It can be observed that the melting point for pure compound,
specifically urea was within the accepted range, however, for the case of impure urea, it was behind the
accepted melting point range which clearly shows that it has undergone melting point depression due to the
impure substances mixed with compound. When it comes solubility, urea dissolves in its own weight in water
but becomes increasingly difficult to dissolve as the concentration increases but generally, urea is soluble, in
fact, it is very soluble in water.
B. Boiling Point Determination
Organic Compound Boiling Point Obtained Theoretical Boiling Point Solubility in Water
Propanoic acid 142.5°C 141.2°C Insoluble
n-Butanol 118.5°C 117.7°C Soluble
2-Butanone 81°C 79.64°C Soluble
n-Hexane 70°C 68°C Insoluble
n-Pentane 37°C 36.1°C Insoluble
Table 4. Structural Effects of Intermolecular Forces of Attraction
There are three important trends to consider that affect the boiling point of the compound:
intermolecular forces, number of carbons and branching. The greater the number of carbons present in the
compound are, the greater the intermolecular forces will be, because more carbon atoms naturally means a
straight chain and a straight chain means greater surface area in contact with the molecules; the greater the
intermolecular forces are, the higher the boiling point is; the greater the boiling point is, the greater the polarity
is; they are all directly proportional. However, if the organic compound is branched, boiling point decreases
because it makes the molecule more compact and more compressed and thereby decreasing the surface
area. For propanoic acid, it undergoes extensive hydrogen bonding, the strongest of all intermolecular forces.
It contains polar and nonpolar end and is essentially insoluble. The boiling point obtained from the experiment
for propanoic acid was 142.5°C. For n-butanol, the extent of hydrogen bonding is not that prominent that is
why propanoic acid has the highest boiling point and it only came second. It is a polar molecule and is soluble
in water, the calculated boiling point for n-Butanol was 118.5°C. For 2-Butanone, it undergoes dipole-dipole
forces between molecules which are stronger than the London dispersion forces of n-Hexane and n-Pentane.
2-Butanone’s molecules tend to stick together more tightly that is why the boiling point is higher as compared
to the two. It is also a polar aprotic solvent and is soluble in water. The calculated boiling point for 2-Butanone
was 81°C. n-Hexane and n-Pentane were the bottom two on this lineup. They both have relatively small
boiling points because they are hydrocarbons. Due to the number of carbons they have, n-Pentane was
officially placed last for having only 5 carbons, whereas n-Hexane contains 6 carbons. n-Hexane has
obviously larger surface area compared to n-Pentane. They are both nonpolar and insoluble in water. the
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 CM134-1L: ORGANIC CHEMISTRY (LABORATORY)
1ST Quarter SY 2019-2020

obtained boiling point for n-Hexane was 70°C and 37°C for n-Pentane. It can be observed that all the boiling
point values gathered for the test samples are slightly higher or above the theoretical boiling point values. In
this experiment, the Bunsen burner was utilized instead of a hot plate. Knowing that naturally, Bunsen burner
heats stuff way faster than hot plate and as clarified by the professor, we chose this medium. It is also
instructed in the methodology to heat the oil bath rapidly and we wanted faster reaction. Slowing down the
heat will only mean narrow range of temperature, however, we are not even sure if the test samples are all
pure in the first place that was why we neglected it. Slight difference from theoretical values are caused of
errors from heating the oil bath rapidly.
Organic Compound Boiling Point Obtained Theoretical Boiling Point Solubility in Water
n-butyl alcohol 118.5°C 117.7°C Soluble
sec-butyl alcohol 101.5°C 100°C Insoluble
tert-butyl alcohol 84°C 82.4°C Soluble
Table 5. Structural Effects of Geometric Isomers or Substituents
Temperatures at which boiling point is reached for geometric isomers or branched compounds are
expected to be low because of their compact structure which yields a lower or smaller surface area which
means low polarizability and boiling points. For organic compounds with the same molecular weight and
functional group attached, the extent to which the individual molecules attract each other would be the factor
of justifying the obtained boiling points of the test sample in this experiment. The boiling point of butyl alcohols
decrease regularly, same trend exists also in their solubility. For n-butyl, the molecules have efficient packing
and can bind with each other so it resulted to have the highest boiling point among the three, this is because
it is capable of hydrogen bonding. The boiling point obtained for this compound was 118.5°C which may be
higher but is relatively close to its theoretical boiling point of 117.7°C. Increase in boiling point was because
of the uncontrolled heat of the Bunsen burner which was utilized in this activity. For the case of sec-butyl and
tert-butyl, their alkyl chains interact through OH groups through hydrogen bonding. To distinguish which will
have a higher boiling point between the two, we will have to look upon their parent chain. sec-butyl’s parent
chain is butane, it has 4 carbons, while tert-butyl’s is propane, it only has 3 carbons, from this point alone,
we can conclude that sec-butyl must have a higher boiling point than tert-butyl and this conclusion satisfied
the results. The calculated boiling point for sec-butyl was 101.5°C which is higher than its theoretical boiling
point by 1.5°C and for tert-butyl, the temperature calculated was 84°C which is 1.6°C higher than its
theoretical boiling point
CONCLUSION
In this experiment, the melting and boiling points were utilized as reagents to determine the purity of
the test samples or organic compounds. We have learned that melting point characterizes the sample, it is a
good indicator of purity, too. It can be learned that narrow range of melting point temperatures categorize the
compound as pure while the otherwise categorizes the compound as impure. As observed in the experiment
and as stated on literature, melting point of compounds vary on their structures and in their purity. Straight
chains or a compound bearing many carbons tend to have higher melting point because of its large surface
area and size, this concept was satisfied by salicylic acid having the highest melting point, followed by urea,
benzoin, benzoic acid and naphthalene in decreasing of melting point manner based on intermolecular forces
of attraction. Intermolecular forces still are the biggest determinants of melting and boiling point. However,
this is not always the case, just like what happened with fumaric and maleic acid which are cis-trans isomers.
Trans isomers, as learned from this experiment tends to have higher melting point because it is more
symmetrical than cis isomers, making it difficult for its bonds to break. However, the structure of maleic acid
and fumaric acid themselves seemed inversely proportional with their intermolecular forces. At first, we
assumed that maleic acid will have higher melting point because it undergoes two intermolecular forces of
attraction, however, these two, namely hydrogen bonding and dipole-dipole interaction are not sufficient,
efficient and effective enough to hold the bonds together tightly. Fumaric acid only undergoes London
dispersion of forces but there is too many of them and they are efficiently packed which will obviously be
requiring more energy to break the bond. From the experiment, we also realized that when there is a presence
of foreign substances in the molecule or compound, the compound melts faster than its pure form as the pure
region of the compound melts first yielding us lower melting point recorded for the sample which is impure
urea. This is because impurities disrupt the crystalline patterns of the compound. This lowered temperature,
in significant values, from the accepted or melting point of the pure substance is called melting point
depression. Clearly, the factors that affect the melting point of an organic compound are the following: the
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 CM134-1L: ORGANIC CHEMISTRY (LABORATORY)
1ST Quarter SY 2019-2020

structure itself, its orientation and all, its molecule size, the intermolecular forces it undergo, and its purity. It
can be observed from the obtained data that they are above and beneath the accepted range of melting
point, however, looking at the bright side, they are also relatively close to those accepted and theoretical
values making us realize and acknowledge the presence of error in the experiment. There will always be
errors in an experiment. The possible root of error in melting point determination could be the fact the there
is only one Thomas-Hoover Apparatus where we had to wait to get our turn, due to running time we may
have forgotten to make sure that the silicone fluid in the apparatus cooled down properly before we started
operating the apparatus itself.
Boiling point is a poor indicator of purity, however, high boiling point means high polarizability; high
polarizability means large number of carbon atoms and strong intermolecular forces of attraction which will
lead as to reasons as to why and how melting point became a good indicator of purity. Presence of dipole
moment means polarizability in an organic compound. Comparing polarizability to solubility is like comparing
oranges and apples, they have nothing to do with each other. Just like in melting point determination, straight-
chained compounds still have higher boiling point than branched ones because of surface area. Molecule
size also matters and must be taken to consideration because it is a huge factor, a tie breaker, when
comparing and ranking hydrocarbons. The experiment shows that propanoic acid has the highest boiling
point because it undergoes the strongest intermolecular force and that is hydrogen bonding. Followed by n-
Butanol, 2-Butanone, n-Hexane and n-Pentane. For branched compounds, their boiling points are expected
to be low from the very start because compactness and compression decreases the surface area of their
molecule. Although in this experiment, the branched compounds have the same molecular weight and
functional group attached, their intermolecular forces of attraction are different from one another and that
justifies the decreasing trend in their boiling points. Efficient packing of the molecule and hydrogen bonding
will always be the determinant of which among the test samples will yield the highest boiling point. The factors
that affect the boiling point of a substance is the same as determination of melting point except that
polarizability is a factor in determining the boiling point of a substance. It can be observed that the boiling
point temperatures our group gathered or obtained are slightly above the theoretical or accepted range of
boiling point temperatures, this is because we chose to use Bunsen burner instead of a hot plate to satisfy
the procedure in the manual that says we have to bathe the oil rapidly. Since heat from Bunsen burner is
very uncontrollable, it became a source in this experiment. However, the gap or difference between the
gathered values from the accepted range are relatively close to each other.
Melting point and boiling point can truly characterize and determine the purity of a compound. At the
end of the experiment, we were able to discern and justify the factors that affect the melting point and boiling
point of a certain compound. We were also able to understand intermolecular forces more, that it is not always
about undergoing the strongest intermolecular force but the efficient packing of the molecules in the
compound. I, personally, initially thought that impure urea will have the higher melting point than that of the
pure urea because of the presence of extra or foreign bodies but the result made me think twice and corrected
this thought, it was supported by research which clarifies that the pure region melts first, it is like neglecting
the impurities thereby obtaining lower melting point. This experiment made me look carefully upon the parent
chain, it does not matter how many alkyl groups, branches or substituents a compound have, the carbons,
the parent chain, the surface area will get to determine which among the experimental compounds will yield
a higher boiling point.
REFERENCES
Retrieved from https://phs.psdr3.org/science/chemistry1/MatterNotes.htm
Retrieved from https://www.ausetute.com.au/puresubs.html
Retrieved from https://www.wiredchemist.com/chemistry/instructional/laboratory-tutorials/determination-of-
melting-point
Retrieved from https://socratic.org/questions/how-can-melting-point-determinations-be-used-in-identifying-
and-or-characterizin
Retrieved from https://en.m.wikipedia.org/wiki/Intermolecular_force
Retrieved from http://www.hmdb.ca/metabolites/HMDB0000176

Experiment 01 │ A10 │ Group No. 2 │ August 22, 2019