Basra University College of science and Technology

Pharmacy department

ORGANIC CHEMISTRY LABORATORY

Title of Report :-
Determination of Mealting Point

Students Names :
‫علي مكي عبدالحسن عبدعلي‬

Supervised by:
Dr. Ahmed Makki

Submission date:
14 / 5 / 2021
Contents

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Apparatus: ........................................................................................... 4

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Melting point: it is the temperature at which the solid and liquid forms of a pure
substance can exist in equilibrium. As heat is applied to a solid, its temperature
will increase until the melting point is reached. More heat then will convert the
solid into a liquid with no temperature change. When all the solid has melted,
additional heat will raise the temperature of the liquid. The melting temperature of
crystalline solids is a characteristic figure and is used to identify pure compounds
and elements. Most mixtures and amorphous solids melt over a range of
temperatures. The melting point of a substance (the temperature at which a
substance melts) is a physical property that can be used for its identification. It is a
measure of the amount of kinetic energy (heat) that must be supplied to the
particles of the substance in order to overcome the intermolecular forces (such as
Van der Waals, dipole-dipole, and Hbonding) that confine them to the solid state.
The determination of melting points is particularly important to organic chemists,
since they often work with solid molecular compounds that have low melting
points (below 300°C) and which can be conveniently measured. Organic
compounds are used in this experiment for the same reasons.

Measuring of melting point:

There are a few ways in which you can setup an experiment with the capillary
method. The first is a manual apparatus setup with the aim of heating up a sample
inside a capillary tube whilst visually looking for when the sample has melted. The
concept involves placing a small amount of the substance in a capillary tube and
joining this to a thermometer. The capillary tube is then placed into a heating bath
and the experiment is conducted. If you don’t have a heating bath, you can use
Mineral Oil in a Thiele Tube and heat the tube with a Bunsen Burner. It is

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important to heat the sample slowly using this method so that a thermal
equilibrium can be established.

A more modern way of using the capillary method is to use a device called a
Melting Point Apparatus. This device uses the same concept of heating a sample in
a capillary tube but makes the process far simpler and quicker. There are many
different types of Melting Point Apparatus machines and they range in
functionality and accuracy. At a basic level, the machine is designed so that a
capillary tube with the sample can be inserted into the device and rapidly heated to
a set temperature. Generally, you will heat the capillary tube to near melting point
and then decrease the speed of the temperature increase so that you can observe
when the sample melts. Observation is generally conducted through a viewing
eyepiece. A Melting Point Apparatus will more than likely have the temperature
displayed in digital format for easy recording of data.

The melting point is practically unaffected by changes in external pressure, making

it a convenient physical constant for the identification of solids. Many organic
compounds are solids at room temperature as a result of strong intermolecular
forces which hold the individual molecules together in a crystal lattice. The nature
and strength of these intermolecular forces are responsible for the observed
differences in melting point. In general, if the forces are strong, the melting point
will be high, and if they are relatively weak, the melting point will be low. A pure
solid has a sharp melting point and will melt within a narrow range of (1-2) C°.
Soluble impurities affect the melting point of a solid in the following manner:

a) Lower the melting point of the substance. with the upper limit considerably
below the true melting point. The presence of an impurity in the molten
compound, reduces its vapor pressure thus lowering the melting point of the
compound.

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b) Broaden the melting point range. Depending on the amount of impurity, the
melting process may extend over a range of 2-20 C° or more. The lattice energy
and consequently Melting point depends on: 1- Molecular weight. 2- Symmetry
of the molecules. 3- Polarity of the molecules. 4- The type of bonding.

The purpose of this laboratory exercise is to identify and assess the purity of an
unknown solid organic compound by determining its melting point and comparing
this number to a list of possible compounds.

heater thermometer – Oil bath (paraffin– sulfuric acid -) _capillary tube – rubber
band – the materials to be measured for melting point

Apparatus:
A simple device for determining melting points is shown in Figure (1). It consists
of a thermometer fitted through a cork and suspended into a long-necked flask
which is three quarters filled with a high boiling and stable liquid like paraffin oil.
The thermometer bulb should be about (1) cm above the bottom of the flask. The
sample in the capillary tube is fastened to the thermometer with a rubber band
placed above the level of the oil. The capillary tube should be close to and on a
level with the thermometer bulb.

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Capillary melting point tubes are about (6-7) cm in length and (1) mm in diameter.
They are sealed by rotating one end of the capillary tube in the edge of a small hot
flame Figure (2).

Figure (2): Sealing the end of the capillary tube

The dry solid is ground to a fine powder on a piece of paper with a spatula. The
open end of the capillary is then pushed into the powder which is forced down the
capillary tube by gently tapping the closed end on the bench top Figure (3). This is
repeated several times until the solid is densely packed at the bottom of the tube to
a height of 2-3 mm

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To determine the melting point of a solid, a small amount of the powdered
substance is introduced into a capillary tube which is then attached to a
thermometer and placed in the oil bath.

A. If we have a known organic compound: The bath is heated rapidly to within

(20) C° of the expected melting point then slowly, and at a constant rate of (2-
3) degrees per minute, close to the melting point. The temperature at which the
solid begins to melt, and that at which it is completely liquid, is recorded as the
melting point range of that substance.

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B. If we have an unknown organic compound:

1. Obtain approximately 0.01 g of the chemical to be tested in a plastic tray.

Using a mortar and pestle, grind the sample into a fine powder.
2. It is suggested that a rough and quick trial run is completed to get an
approximate melting point for your unknown. Once a rough melting point is
determined, allow the machine to cool to at least 15°C below the bottom
temperature of the rough melting point.
3. After the rough trial, head the machine very slowly through the melting point.
The slower it heats through the melting point, the more accurate the melting
points.
4. Record the temperature at which the first liquid droplets appear.
5. Record the temperature at which the last solid particles liquefy.
6. Average the two temperatures to get the experimental melting point of the
solid.

The melting point range is affected by a number of factors in addition to that of

purity. Particle size, amount of material used, density of packing in the capillary
tube, thickness of the capillary tube and the rate of heating of the liquid bath, are
all factors that should be carefully considered to ensure an accurate melting point.
The rate of heating is the most critical factor affecting experimental results, and
should be carefully monitored, particularly close to the expected melting point.

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Liquid paraffin is used in determination of melting point for the following reasons:

❖ Melting point of a substance is the temperature at which it changes state from

solid to liquid.
❖ Boiling point of paraffin is > 370 °C.
❖ Due to its higher boiling point, liquid paraffin it easily reaches desired
temperature (200-250 °C) without boiling.
❖ Therefore, liquid paraffin is used in melting point determination.

There are 3 important trends to consider that affects the boiling point in organic
chemistry:

(1) The relative strength of the four intermolecular forces is: Ionic > Hydrogen
bonding > dipole dipole > Van der Waals dispersion forces. The influence of each
of these attractive forces will depend on the functional groups present.

Compare the different butane alcohol derivatives shown below. Molecules of

diethyl ether, C4H10 O, are held together by dipole-dipole interactions which arise
due to the polarized C-O bonds. Compare its boiling point of (35 °C) with that of
Its isomer butanol (117 °C). The greatly increased boiling point is due to the fact
that butanol contains a hydroxyl group, which is capable of hydrogen bonding.
Still, the attractive forces in butanol pale in comparison to those of the salt sodium
butoxide, which melts at an extremely high temperature (well above 260 °C) and
actually decomposes before it can turn into a liquid.

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Then think about butane, C4H10, which contains no polar functional groups. The
only attractive forces between individual butane molecules are the relatively weak
Van der Waals dispersion forces. The result is that butane boils at the temperature
at which water freezes (0° C), far below even that of diethyl ether.

Moral of the story: among molecules with roughly similar molecular weights, the
boiling points will be determined by the functional groups present.

(2) For molecules with a given functional group, boiling point increases with
molecular weight.

(3) The Role of Symmetry (or lack thereof) On Melting and Boiling Points

This is another byproduct of the surface-area dependence of Van der Waals

dispersion forces – the more rod-like the molecules are, the better able they will be
to line up and bond. To take another intuitive pasta example, what sticks together
more: spaghetti or macaroni? The more spherelike the molecule, the lower its
surface area will be and the fewer intermolecular Van der Waals interactions will

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operate. Compare the boiling points of pentane (36°C) and 2,2-dimethyl propane (9
°C).

Factors that affect boiling point:

Impurities in the solution increase the boiling point. This is

because impurities decrease the water molecules available for vaporization
during boiling. A greater amount of heat is needed to make the same amount of
impure solution to vaporize than the heat that is required to make a pure solution
vaporize

There is molecular size. Large molecules have more electrons and nuclei that
create van der Waals attractive forces, so their compounds usually have higher
boiling points than similar compounds made up of smaller molecules.

[1] Goldberg, David E. (1988). 3,000 Solved Problems in Chemistry (1st ed.).
McGraw-Hill. section 17.43, p. 321. ISBN 0-07-023684-4.
[2] Wohler’s Outlines of Organic Chemistry – page 275.
[3] Theodore, Louis; Dupont, R. Ryan; Ganesan, Kumar, eds. (1999). Pollution
Prevention: The Waste Management Approach to the 21st Century. CRC
Press. section 27, p. 15. ISBN 1-56670-495-2.
[4] General Chemistry Glossary Purdue University website page
[5] Perry, R.H.; Green, D.W., eds. (1997). Perry's Chemical Engineers'
Handbook (7th ed.). McGraw-Hill. ISBN 0-07-049841-5.
[6] The London, Edinburgh and Dublin Philosophical Magazine and Journal of
Science.
[7] DeVoe, Howard (2000). Thermodynamics and Chemistry (1st ed.). Prentice-
Hall. ISBN 0-02-328741-1.

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