You are on page 1of 7

Experiment 5: Boiling Point and Melting Point Determination

Cailao, Ma. Victoria T.


Masigan, Maureen Margaret R.
Group 5, Chem 31.1, AB2, Ms. Denise Arganda
April 30, 2009
I. Abstract
Two of the more important physical properties of pure substances are the boiling point and the melting point.
They can be used to characterize organic and inorganic substances and are also an indicative of the purity of a
substance. The boiling point of a liquid is the temperature at which that liquid is converted to a gaseous state. It
is formally defined as the temperature at which the vapor pressure of the liquid becomes equal to the pressure
at the surface of the liquid. The melting point is the temperature at which a solid is converted to liquid. In this
experiment, melting and boiling points were determined by conducting a setup consisting of capillary tubes,
thermometer, and oil bath.
II. Keywords: boiling point, melting point, benzoic acid, urea, hexane, distillate
III. Introduction
the liquid phase in less than 1 atmosphere of
pressure. The melting point is one physical property
Boiling point refers to the temperature at
of a substance that is useful for characterizing
which the vapor pressure of a liquid slightly
(describing) and identifying the substance. To
exceeds the pressure of the atmosphere above the
measure the melting point of a substance, it is
liquid. At temperatures below the boiling point (b.p.),
necessary to gradually heat a small sample of the
evaporation takes place only from the surface of the
substance while monitoring its temperature with a
liquid; during boiling, vapor forms within the body of
thermometer. The temperature at which it begins to
the liquid; and as the vapor bubbles rise through the
liquify is the lowest end of the melting point range and
liquid, they cause the turbulence and seething
the temperature at which the last solid disappears is
associated with boiling. If the liquid is a single
the highest end. A pure substance normally has a
substance or an azeotropic solution (a mixture that
melting point range no larger than 1-1.5 C.
has a constant b.p.), it will continue to boil as heat
Although
many
substances
melted,
is added without any rise in temperature; that is,
crystallized, and melted again repeatedly without
boiling occurs at constant temperature regardless of
chemical
decomposition,
others
chemically
the amount of heat applied to the liquid.
decompose before they melt, forming substances of
When the pressure on a liquid is increased,
lower molecular weight. The temperature of
the b.p. goes up. Water at 1 atmosphere pressure
decomposition is just as useful as the melting point in
(760 torr, or about 14.7 lb/sq in) boils at 100 C
physically characterizing a substance. Decomposition
(212 F), but when the pressure is 218
is usually signaled by a color change; for example,
atmospheres (165,000 torr, or 3200 lb/sq in), the
white substances invariably start to turn brown near
b.p. reaches its maximum, 374 C (705 F). Above
the decomposition temperature. The temperature, at
this temperature (the critical temperature of water),
which the color change is first observed, signals that
liquid water is identical to saturated steam.
the substance is approaching the decomposition
If the pressure on a liquid is reduced, the
temperature. At a higher temperature, liquid may
b.p. is lowered. At higher elevations, where air
form. At this temperature or at an even higher
pressure is less, water boils below 100 C. In
temperature, gas bubbles may be seen if gaseous
Denver, Colorado, which is 1.6 km (1 mi) above sea
decomposition products are formed. All of these
level, the b.p. of water averages 94 C (201 F).
temperatures aid in characterizing a substance, so all
When the pressure on a sample of water falls to
should be noted and reported.
4.55 torr (0.088 lb/sq in), boiling occurs at 0 C (32
The objectives of the experiment are the
F), which is the normal freezing point.
determination of the melting point of benzoic acid and
Boiling points cover a wide temperature
benzoic acid-urea mixture; and the boiling point of
range. The lowest b.p. is that of helium, -268.9 C (hexane and the distillates. It also aims to teach
452 F). The highest is probably that of tungsten,
students the proper laboratory techniques in
about 5900 C (10,650 F). The boiling points given
determining the said physical properties.
in the separate articles on the various elements and
compounds apply at normal pressure unless
specifically stated otherwise.
The melting point of a substance is the
IV. Experimental
temperature at which the solid phase converts to
Chem 31.1 Boiling Point and Melting Point Determination

Page 1 of 7

A. Melting Point Determination of Benzoic Acid


and Benzoic Acid-Urea Mixture
Two capillaries (1 mm in diameter and 6 cm
in length) were prepared, one end of each capillary
sealed. Approximately 0.5 g benzoic acid was
obtained and powdered using mortar and pestle.
The powdered sample was introduced into the first
capillary tube until it occupied about 1 cm in height.
This was done by pushing the open end of the
capillary into the powder and tapping the closed
end on the table top. Another 0.5 g of benzoic acid
was obtained; a pinch of urea added to the sample.
The mixture was powdered using mortar and pestle,
and then introduced to the second capillary tube.
The two capillaries were attached to the
thermometer.
Figure 2: Boiling Point Apparatus

The capillary tube was introduced into the test


tube with the open end immersed in the liquid sample.
The temperature of the oil bath was raised until a
rapid and continuous stream of bubbles was
observed. The flame was removed and the bath was
allowed to cool. The temperature reading was taken
as the instant bubbles ceased to come out of the
capillary tube and just before the liquid sample enters
the capillary tube. The respective boiling points of the
two distillates (obtained in Experiment #4) were
determined using the same procedure.
V. Results
A. Melting Point Determination
Sample

Figure 1: Melting Point Apparatus

10 mL of cooking oil was introduced in a


20-mL test tube. The thermometer, along with the
capillaries, were immersed in the oil bath and
heated over a hot plate. The temperature at which
the sample starts to liquefy and the temperature at
which the solid has completely liquefied were
recorded.
B. Boiling Point Determination of Distillate and
Hexane
Three capillaries were prepared, one end of
each capillary sealed. 10 drops of hexane was
introduced into the 5-mL test tube. Attach this to the
thermometer as shown in the figure below.

Benzoic Acid
Benzoic AcidUrea Mixture

Melting Point Range ( )


Experimental
Theoretical
115
121-122
85

--

Table 1. Experimental and Theoretical Melting Points of the


Samples Used

B. Boiling Point Determination


Sample
Hexane
Distillate 1 (from
simple
distillation)
Distillate 2 (from
fractional
distillation)

Boiling Point ( )
Experimental
Theoretical
68

69

82

78.3

105

78.15

Table 2. Experimental and Theoretical Boiling Points of the


Samples Utilized

Chem 31.1 Boiling Point and Melting Point Determination

Page 2 of 7

VI. Discussion
Boiling Point
The boiling point of a compound is the
temperature at which it changes from a liquid to a
gas. This is a physical property often used to
identify substances or to check the purity of the
compound. It is difficult, though, to find a boiling
point. Usually, chemists can only obtain a boiling
range of a 2 - 3C accuracy. This is usually
sufficient for most uses of the boiling point.
A liquid boiling point is the temperature
when its vapor pressure is equal to the atmospheric
pressure. Normally, the boiling point is measured at
one atmosphere (101 kPa or 760 mmHg or 760
torr). Like melting points, boiling points are
characteristic properties of pure materials. Boiling
points are approximately related to their molecular
weight, the higher the molecular weight, the higher
the boiling point.
Boiling point is the temperature at which the
vapor pressure of the liquid exactly equals the
pressure exerted on it, causing the liquid to "boil" or
change to the gas phase. For purposes of this
laboratory experiment, the boiling point of an
organic liquid is the temperature range over which
the state of the organic compound changes from
the liquid phase to the gas phase at 760mm of
pressure. While the boiling point is a characteristic
physical property of a compound, many compounds
may have the same boiling point.
The molecules of compounds that exist in
the liquid state are relatively close together,
compared with molecules of gaseous compounds.
The close proximity of molecules in the liquid state
allow these molecules to interact via non-covalent
interactions (dipole-dipole, H-bonding, van der
Waals forces). In general, these interactions are
favorable and help to hold the molecules together in
a defined volume, but still allow free motion or
"flow". Conversely, molecules of a gaseous
compound are much farther away from each other
and are not confined to a specific volume by noncovalent interactions. If enough energy (often in the
form of heat) is provided to the liquid, the molecules
begin to move away from each other by "breaking"
the non-covalent forces that hold the compound in
the liquid state.
Structural features of a compound influence
the boiling point by increasing or decreasing the
molecules' ability to establish and maintain noncovalent interactions that hold the molecules close
together in the liquid state. The structural features
of a compound that influence boiling point are:
(a) Polarity - Increased H-bonds, polar covalent
bonds or formal charges in a molecule tend to
increase the boiling point. More polar elements in a
Chem 31.1 Boiling Point and Melting Point Determination

molecule increase the total number of dipole-dipole,


ion-dipole and/or H-bonding interactions. More energy
(higher boiling point temperature) is necessary to
break these interactions and allow the molecules to
move away from each other into a gaseous state.
(b) Molecular Weight - Increased molecular weight
increases boiling point. A higher molecular weight
compound has more atoms that can be involved in
non-covalent interactions. The greater the number of
non-covalent interactions, the more energy (higher
boiling point temperature) that is necessary to break
the non-covalent interactions to transform the
compound from the liquid phase to the gas phase.
(c) Branching - Branching decreases boiling point. It
blocks molecules from packing together too closely.
The closer molecules are, the stronger the noncovalent interactions. Thus, molecules that are forced
to be farther away from each other due to branching
have weaker non-covalent interactions. Less energy
(lower temperatures) is needed to induce a phase
change from the liquid phase to the gas for branched
compounds relative to straight chain compounds.
Melting Point
The melting point of a crystalline compound is
best defined as the temperature at which the solid
phase is in equilibrium with the liquid phase. At the
melting point, sufficient heat has been applied so that
thermal vibrations of the molecules in the crystal
lattice are great enough to overcome the electrostatic,
dipole, and van der Waals cohesive forces, allowing
the molecules to take on the more random and mobile
arrangement of the liquid state. The freezing point, or
the temperature observed as the liquid form cools and
solidifies, is the same temperature as the melting
point.
Melting points are readily obtained with great
precision using simple apparatus. It is the most widely
determined and useful physical constants of organic
compounds. Melting points are used both as criteria
of purity and as a clue to the identification of organic
compounds. A narrow melting point range is indicative
of a pure substance. It is a good generalization that,
as a compound is purified, the melting points become
sharper (range narrower) and higher. Since hundreds
of organic compounds may have similar melting
points, exact identities are difficult and risky, based
only on simple melting point determinations; but at
least the number of possibilities can be narrowed
from the millions of known organic compounds.
Observed melting points are generally
recorded as a range of temperatures because of the
rather large quantities of compounds used and the
difficulty in controlling the experimental variables in
the usual methods for determining melting points.
Only when one or two crystals of an extremely pure
Page 3 of 7

compound are melted on specially controlled hot


stages and observations conducted with the aid of
high-powered magnifiers and/or polarized light are
then, melting points observed as single
temperatures. The temperatures recorded as the
observed melting point range are the temperature
at which there is a definite sign of liquid in the
sample and the temperature at which there is
nothing but liquid in the sample, e.g. 123.5-125.0
C. An apparent shrinking, slumping, or softening is
often the first indication that something is about to
happen as the melting point is approached but
these changes should not be mistaken for the first
signs of liquid in the sample.
The melting point range (the interval
between the beginning of liquefaction and complete
liquefaction) is a valuable inaction of the purity of
the substance. A pure crystalline organic compound
generally possesses a sharp melting point range,
usually 2.The melting point range is influenced not
merely by the purity of the material but also by
factors such as the size of the crystals, the amount
of material, rate of heating, determination method,
experimenter, etc.
In the most common methods of melting
point determination, a small amount of finely
powdered crystals is placed in a thin-walled
capillary tube. The tube is placed in very close
proximity to a thermometer and the capillary tube is
heated in a small electric block or oven or in a wellstirred oil bath. A finite time is necessary for the
transfer of heat from the hot block or bath through
the walls of the capillary tube and throughout the
mass of the sample. If the block or bath is heated
too rapidly, the temperature of the block or bath will
rise several degrees. This time lag required for the
melting process makes the observed melting point
range larger than the theoretical one. Likewise, too
rapid heating will cause the thermometer reading to
be lower than the actual block or bath temperature,
because of the time required for heat transfer to the
mercury. Consequently, the observed melting point
range will generally be broader and lower than the
actual melting point range if too rapid heating
occurs.
Satisfactory results are obtainable if a
uniform rate of heating of no more than 1 or 2 rise
per minute is employed in the vicinity of the melting
point. The temperature may normally be raised
rapidly until 10 or 15 below the melting point with
the rate of heating then being adjusted to the
uniform rise of 1 to 2 per minute.
To minimize the lag in the melting process
and heat transfer the compound should be finely
ground and packed densely to a height of 2-5 mm
in a fine capillary tube having a small diameter and
very thin walls. Two other sources of error in melting
point determinations are incorrect calibration of the
Chem 31.1 Boiling Point and Melting Point Determination

thermometer scale (this can be eliminated by


standardizing the thermometer with a set of melting
point standards) and stem exposure of the
thermometer.
The surrounding atmosphere cools that
portion of the mercury column that is exposed above
the surface of the heating bath of block. The
registered temperature is, therefore, below the true
temperature of the mercury in the bulb of the
thermometer and of the sample in the capillary tube.
For temperatures below 100 C, this cooling effect
does not cause any considerable error, but for high
temperatures the observed reading maybe several
degrees lower than the true temperature.
Systematic variations of melting point with
changes in structure are not as obvious or predictable
as are the variations in boiling point.
(a) Molecular Weight - Although melting points do
generally increase with increasing molecular weight,
the first members of homologous series (compounds
differing by only a CH2) often have melting points that
are considerably different from what would be
expected on the basis of the behavior of the higher
homology In some homologous series of straightchain aliphatic compounds, melting points alternate:
the melting point of successive members of the series
is higher or lower than that of the previous member,
depending on whether the number of carbon atoms is
even or odd. Sometimes, as with the normal alkanes,
the melting points of successive members of the
series always increase, but by a larger or smaller
amount, depending upon whether the number of
carbons is even or odd.
(b) Polarity - As with boiling points, compounds with
polar functional groups generally have higher melting
points than compounds with nonpolar functional
groups.
(c) Branching - In contrast to the case with boiling
points, highly branched or cyclic molecules (relatively
symmetrical molecules) tend to have higher melting
points than their straight-chain isomers. The
combined effects of branching or the presence of
rings, then, are to reduce the range of temperature
over which the liquid can exist at a vapor pressure of
less than 760 torr. In extreme cases, a liquid range
does not exist at a vapor pressure of less than 760
torr; at atmospheric pressure, the substance will
sublime without melting. Hexachloroethane and
perfluoro-cyclohexane behave in this way.
Melting points of organic compounds are
usually markedly influenced by the presence of even
small amounts of miscible or even partially miscible
impurities. These impurities normally depress the
melting point and broaden the range. This lowering
Page 4 of 7

and broadening of the melting point range is


presumably caused by the molecules of the impurity
interrupting and weakening the uniform structure of
the crystal lattice of the organic compound. These
facts may be used to establish the identity of
organic compounds by determining the melting
points or mixtures, a method commonly referred to
as mixed melting points.
Mixed Melting Points
Two sample of the same compound, having
the same melting point separately, should have the
same melting point when they are mixed together.
Also, in general, sample of two different compounds
having the same or similar melting points
separately, will act towards each other as impurities
when they are mixed together; hence, such
mixtures will have broadened and depressed
melting point ranges. Identification of a solid
unknown by mixed melting points is remarkably
reliable when an authentic specimen is available.
A broadened melting point range may be
due not only to impurities present in the original
sample but also may result from the pure substance
undergoing some decomposition before or during
the melting. In some instances the material
undergoes a slight softening or contraction
(sintering) at a temperature below the true melting
point; in others, the material may become
discolored slightly; and in still others, the substance
may decompose completely and turn black so that
a definite melting point cannot be ascertained. The
behavior of substance on melting should be
observed closely and recorded in the lab-book.
Each time a melting point is determined or
rechecked a fresh sample should be placed in a
new capillary since even slight, undetected
decomposition may cause a false reading if the old
sample is melted again. Broadened and depressed
melting point ranges are also frequently obtained if
the sample is not completely dry. It is because the
sample is wet with water or some other solvent
used in the purification of the compound. Instead of
melting, wet compounds merely dissolve in the
solvent present as heat is applied. If the compound
dances around or there are bubbles when melting,
a wet compound should be suspected.
Experimentally observed melting points will
normally match literature melting points within two
degrees, with the observed melting points generally
on the low side since literature melting points as a
rule are reported on compounds of very high purity.
Variations in literature melting points from one
reference to another for the same compound are
encountered frequently. It is due to differences in
purity of the samples.

1. Give an explanation of the observed boiling points.


The benzoic acid-urea mixture has a melting
point range lower and larger in the range of values
than the benzoic acid alone. This is brought about by
the impurity of the mixture. Impurities change the
crystal lattice of a pure compound, making it
asymmetrical or poorly organized. Since melting point
is dependent on the high symmetry and organization
of molecular structures, any change on the latter will
cause the deviation of the former.
2. Give an explanation of the observed boiling points
of the two distillates.
Whatever method of preparation is used, the
ethanol is initially obtained in admixture with water.
Although the boiling point of ethanol, 78.3C, is
significantly lower than the boiling point of water, 100
C, these materials cannot be separated completely
by distillation. Instead, an azeotropic mixture (i.e. a
mixture of 95% ethanol and 5% water) is obtained,
and the boiling point of the azeotrope is 78.15C. In a
distillation, the most volatile material (i.e. the material
that has the lowest boiling point) is the first material to
distill from the distillation flask, and this material is the
azeotrope of 95% ethanol which has the lowest
boiling point. If an efficient fractionating column is
used, there is obtained first 95% alcohol, then a small
intermediate fraction of lower concentration, and then
water. But no matter how efficient the fractionating
column used, 95% alcohol cannot be further
concentrated by distillation.
The separation of a mixture by fractional
distillation occurs because the vapour has a different
composition from the liquid from which it distils (i.e.
the vapour is richer in the more volatile component).
We cannot separate 95% alcohol into its components
by distillation, because here the vapour has exactly
the same composition as the liquid; towards
distillation, then, 95% alcohol behaves exactly like a
pure compound.
3. What effect would poor circulation of the melting
point bath liquid have on the observed melting point?
Poor circulation can cause uneven heating of
a sample. This may lead to inaccurate results.
Observed melting point may be unusually higher than
the actual.

VII. Guide Questions and Answers


Chem 31.1 Boiling Point and Melting Point Determination

Page 5 of 7

4. What effect would the incomplete drying of a


sample have on the melting point?
Incomplete drying of a sample may cause
some depression of the melting point. This is
caused by the impurities that are left in the sample.
Any impurity of a substance lowers its melting point.
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 compounds?
First, determine the respective melting
points of the unknown compounds. If they are
approximately the same, mix the substances in test
tubes A, B, and C. Determine the melting point
exhibited once again. If the melting point of the
mixture depresses from the individual melting points
of the substances, therefore, the unknown
compounds are different.
6. Which would be expected to have a higher
boiling point t-butyl alcohol or n-butyl alcohol?
Explain.
n-butyl alcohol is expected to have a higher
boiling point than t-butyl alcohol because the
previous has a more linear structure compared to
tert-butyl alcohol which exhibits branching. This
decreases the strength of the intermolecular forces,
thus, also reduces the boiling point.
7. Calculate the vapor pressure of a solution
containing 30mol % hexane and 70mol % octane at
90C assuming Raoults Law is obeyed. (Given:
vapor pressure of the pure compounds at C:
hexane=1330 torr; octane=253 torr).
Phexane=PhexaneXhexane = (1330 torr)(0.3)
= 399 torr
Poctane=PoctaneXoctane = (253 torr)(0.7)
= 177.1 torr
Ptotal=Phexane + Poctane =399 + 177.1 = 576.1 torr
VIII. Conclusion and Recommendations
A simple and widely used method for
determining the identity of an unknown liquid is by
measuring the temperature at which it boils. This
temperature, called the boiling point, is a physical
property. It can be used to identify liquids much like

Chem 31.1 Boiling Point and Melting Point Determination

solids can be identified by melting points. The


apparatus to be used is a simple distillation set-up.
The normal melting point of a solid is defined
as the temperature at which the solid and liquid are in
equilibrium at a total pressure of 1 atmosphere. In
contrast to the volume change that accompanies the
vaporization of a liquid, the change in volume that
takes place upon the melting of a solid is very small.
This makes the melting point of a solid, unlike the
boiling point of a liquid, practically independent of any
ordinary pressure change. Since the melting point of
a solid can be easily and accurately determined with
small amounts of material, it is the physical property
that has most often been used for the identification
and characterization of solids.
A dilute solution of a liquid begins to freeze at
a temperature somewhat lower than the freezing point
of the pure liquid. The presence of an impurity causes
a reduction of the freezing point of the sample. As the
pure solvent crystallizes from solution, the
concentration of the impurity must increase and the
freezing point of the solution must fall. Thus, a sharp
melting point (actually, a melting range of less than
about 1C) is often taken as evidence that the sample
is fairly pure, and a wide melting range is evidence
that it is not pure.
If two samples have different melting points,
their molecules must differ either in structure or in
configuration. They must be either structural isomers
or diastereomers. If the melting points of two samples
are the same, the structures of their molecules must
be the same, although they might have enantiomeric
configurations. These statements apply only to pure
substances, and do not take into account the fact that
some substances can exist in different crystalline
forms that have different melting points.
Mixtures of different substances generally
melt over a range of temperatures, and melting is
usually complete at a temperature that is below the
melting point of at least one of the components. Thus,
the nonidentity of two substances of the same melting
point can often be established by determining that the
melting point of a mixtures of the two is depressed. If
each individual sample melts "sharply" (and at the
same temperature, of course), and if an intimate
mixture of the two, made by rubbing approximately
equal amounts together, melts over a wide range, the
two substances are not the same.
Usually, however, in establishing the identity
rather than the nonidentity of two samples, it is
unfortunate that the converse is not always true: the
absence of a depression of the melting point or of a
wide melting range of the mixture is not certain
evidence that the two substances are identical in
molecular structure and configuration.
Boiling a liquid and melting a solid involve the
same process that is, breaking away from the
attractive forces that hold particles together. Thus, the
Page 6 of 7

strength of the interparticle forces of attraction


(IPFA) is the principal factor that determines boiling
point and melting point. Moreover, the factors
affecting boiling point and melting point are:
molecular size, branching, polarity, molecular
symmetry and intramolecular H-bonding.
IX. References
Brown, T. L., Lemay Jr., H. E., Bursten, B.
E. Chemistry: The Central Science (9th ed.).
Singapore: Pearson Education (Asia) Pte
Ltd.
Committee on General Chemistry (2006).
Laboratory manual in general chemistry
(2006 ed.). Manila, Philippines: University
of the Philippines Manila
Microsoft Encarta 2007. 1993-2006
Microsoft Corporation. All rights reserved.
Sackheim, G. I, Lehman, D,D. (2002)
Chemistry for the Health Sciences (8th ed.)
Upper Saddle River, New Jersey: Pearson
Education Asia Pte. Ltd.
Whitten, K. W, Davis, R. E, Peck, M. L,
(2005) General Chemistry (7th ed.).
Singapore: Thompson Learning Asia Pte.
Ltd.

I hereby certify that I have given substantial


contribution to this report.

Cailao, Ma. Victoria T.

Masigan, Maureen Margaret R.

Chem 31.1 Boiling Point and Melting Point Determination

Page 7 of 7