Experiment 1

DETERMINATION OF MELTING POINT

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 Melting Point
Physical properties are often utilized by chemists in identifying an organic
compound. These physical properties include :
color, odor, physical state, melting point (M.P.), boiling point (B.P.), index of
refraction(n),density (d), infrared (IR) spectrum, nuclear magnetic spectrum
(NMR) ,specific rotation ([_]),solubility and ultraviolet (UV) spectrum.

As long as the physical constants are determined under standard conditions

(temperature, pressure, etc.), they are invariant and, therefore, useful in helping
to determine the identity of unknown substances.

Chemists regard a table of physical properties and physical constants to be

extremely helpful in identifying unknown compounds. There are a number of
reference books that contain tables of physical properties and physical
constants of compounds.

One of the most common is the Handbook of Chemistry and Physics. If the
physical properties of an unknown compound are identical to the physical
properties of a compound listed in the tables, the two compounds are probably
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Definitions:
The melting point of a solid is defined as the temperature at which the liquid
and solid phases are in equilibrium.
The freezing point of a liquid is the same temperature as the melting point
of its solid. However, freezing points are rarely measured in practice because
they are more difficult to determine. One reason for this is that solidification
may not occur at the correct temperature due to the phenomenon of
supercooling(Super-cooling occurs when a liquid is cooled below its freezing point and
does not solidify).
Determination of the temperature at which the solid and liquid phases of a
substance are in equilibrium is tedious and time consuming; it is also quite
difficult with a small amount of sample.

Thus, in practice, most melting points are determined as capillary melting

points, which can be done quickly with a small amount of sample in a capillary
tube.
A capillary melting point is defined as the temperature range over which a
small amount of solid in a thin walled capillary tube first visibly softens (first
drop of liquid) and then completely liquefies.
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 Melting Points and Mixed Melting points

Melting points are determined for three reasons.

1. If the compound is a known one, the melting point will help to characterize
the sample in hand.
2. If the compound is new then the melting point is recorded in order to allow
future characterization by others.
3. If the range of the melting point is indicative of the purity of the
compound; an impure compound will melt over a wide range of temperatures.
Pure organic compounds generally have sharp melting points. An impurity
lowers the melting point and widens the range.

A technique for proving the identity of an unknown compound is the mixed

melting point. Advantage is taken of the depression of melting points of
mixtures to prove whether two compounds having the same melting points are
identical.
If X and Y are identical, then a mixture of the two will have the same
melting point; but if X and Y are not identical, then a small amount of X in Y
or of Y in X will cause the melting point to be lowered.
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 Eutectic Mixtures

Eutectic mixture is defined as a mixture of two or

more components which usually do not interact
to form a new chemical compound but, which at
certain ratios(e.g. 60%x +40%y), inhibit the
crystallization process of one another resulting in
a system having a lower melting point than
either of the components x and y

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 Eutectic Mixtures

The melting point behavior of impure compounds is best understood

by consideration of a simple binary mixture of compounds X and Y (Fig. 1).

This melting point-composition diagram shows the melting point behavior

as a function of composition. The melting point of a pure compound is the
temperature at which the vapor pressures of the solid and liquid are equal.

But in dealing with a mixture the situation is different. Consider the case of a
mixture of 75% X and 25% Y.
At a temperature below ET, the eutectic temperature, the mixture is solid Y and
solid X.
At the eutectic temperature the solid begins to melt. The melt is a solution of Y
dissolved in liquid X. The vapor pressure of the solution of X and Y together is
less than that of pure X at the melting point; therefore, the temperature at which
X will melt is lower when mixed with Y.

As the temperature is raised, more and more of solid X melts until it is all gone
at point M (temperature m). The melting point range is thus from ET to m.
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 Eutectic Mixtures

Temp Liquid X + Y

MpY

Mp X M

m
Liquid + solid Y

liquid
+solid X
ET

Eutectic Point
Solid X + Y

Mole% X 100 75 0
Mole% Y 0 25 100
Fig (1)
The minimum freezing point attainable corresponding to the eutectic mixture
is known as “Eutectic Point”(which means lowest melting point).
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 The Thiele apparatus and heating set-up

Thiele tube apparatus achieves stirring and uniform heat

distribution by convection. It is filled to the base of the neck
with silicone oil (the oil expands on heating) and the
thermometer can be held by an adapter and a clamp.
The tube is heated at the base of the bend. The bulb of the
thermometer should be halfway down the tube to assure uniform
heating.

A small
beaker
containing
silicone oil
 Thiele tube
→

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 The Thiele apparatus and heating set-up

Melting points are also easily determined in a small beaker.

A small beaker containing silicone oil can be used as
alternative set-up through which heat distribution will be done
by convection .The beaker can be heated on a hot plate or
a Bunsen burner.
Important safety alert:
• Do not discard the silicone oil used in any apparatus because it will be
necessary to determine a number of melting points in future experiments.
• Silicone oils may be heated to about 300 °C without danger (Mineral oil is a
mixture of high-boiling hydrocarbons and should not be heated above 200
°C .because of the possibility of spontaneous ignition, particularly when a
burner is used for heating).
• The silicone oil should never be heated if they are contaminated with few
drops of water because heating above 100 °C may produce splattering of
hot silicone oil as the water turns to steam (Never cool the heating bath
with water).

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Filling Melting Point Capillaries
The dry sample is ground to a fine powder on a watch glass or a piece of
paper on a hard surface using the flat portion of a spatula or a glass rod.
It is formed into a small pile and the melting point capillary forced down into the
pile.
The sample is shaken into the closed end of the capillary by rapping sharply on
a hard surface or by dropping it down a 2-ft length of glass tubing onto a hard
surface. The height of the sample in the capillary should be no more
than2-3 mm.

Determining the Melting Point

The accuracy of the melting point depends on the accuracy of the thermometer,
so the first exercise in this experiment will be to calibrate the thermometer.
Melting points of pure, known compounds will be determined and deviations
recorded so that a correction can be applied to future melting points.
The most critical factor in determining an accurate melting point is the
rate of heating. At the melting point the temperature rise should not be
greater than 1-2°C per minute. This may seem extraordinarily slow, but it
is necessary in order that heat from the bath be transferred equally to the
sample and to the glass and mercury of the thermometer.
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 Calibration of the Thermometer
Calibration over a range of temperatures is necessary because the error is likely to vary at
different temperatures.
Determine the melting point of standard substances (Table 1) over the temperature range of
interest.
The thermometer correction is the difference between the true(literature) and the
observed temperature measurement, and this provides a correction that must be
applied to the observed reading.
Include both temperatures(when starts melting until complete melting occurs) making up the
melting point range. Use your data to graph a correction curve for your thermometer(as shown in
Fig 2).
Table (1) Melting point of samples might be used for calibration.
Thermometer
Observed Literature
Compound Average correction
m.p. Range m.p.
necessary
1,4- 52-54 oC
Dichlorobenzene

Acetanilide 114-115 oC
Benzamide 125-127oC
Urea 132oC
Salicylic Acid 159-160oC
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Calibration of the Thermometer

Calibration of the Thermometer

Fig (2)

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 Melting Points of Mixtures

Determine the melting point of the following mixtures including the range(the
mixed samples have no literature m.p. values).
Plot a melting point /composition diagram of urea and benzamide using the
average temperature.
From the line connecting the points, estimate the eutectic point. This is the
lowest point on the curve and it occurs at the greatest melting point depression.

Table (2) Melting point of samples to determine the eutectic point .

Compound Melting Literature
point m.p.
pure urea
pure benzamide
75%urea, 25% benzamide ---------------
50%urea, 50% benzamide ---------------
25%urea, 75% benzamide ---------------
Eutectic melting point of
urea-benzamide

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 Melting Points of Unknown
Determine the melting point of an unknown provided by your instructor.
The unknown is expected to be one of the 7 compounds listed in table (3)

Table (3) Compounds available for the experiment

Compound Literature m.p.

1,4-dichlorobenzene
1 52-54 oC

Acetanilide
2 114-115 oC

Salcylic acid
3 159-160oC

Urea
4 132oC

Benzamide
5 125-127oC

Benzanilide
6 161oC

Benzoic acid
7 122-124oC

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 Melting Points of Unknown
1. Prepare two capillaries of the unknown.
2. Run a very fast determination on the first sample to ascertain the
approximate melting point .
3. Cool the melting point bath to just below the melting point and make
a slow, careful determination of the melting point using the other
capillary.
4. Mix equal amounts of the unknown and the suspected compound
(Mixed technique) and prepare a capillary of the mixture and a
second capillary of the pure sample of the unknown.
5.Attach the two capillaries to the same thermometer using the same
rubber band.
6. Run a slow, careful determination of the melting point of the two
attached capillaries under the same conditions(same rate of heating in
the same heating bath).
7.Record your observation (you might need mixing with a different pure
compound).

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