Melting Point Determination

Pre-requisite: https://www.youtube.com/watch?v=Oh6o-2Pp_Ik
https://www.youtube.com/watch?v=TGR4IZFh4cA

Background

The melting point of a solid can be easily and accurately determined with only small amounts of
material and, in combination with other measurements, can provide rapid confirmation of identity.
The most accurate method of determination is to record a cooling curve of temperature versus
time. However, this approach requires quite large amounts of material and has been exclusively
replaced by the capillary method.
Capillary Melting Point Determination
The method involves placing a little of the sample in the bottom of a narrow capillary tube. The
determination is made using a Melting Point Apparatus that heats automatically the sample tube.
The temperature range, over which the sample is observed to melt, is recorded. Some pure
materials have a very narrow melting range, perhaps as little as 0.5–1.0 °C, while more typically
a 2–3 °C range is observed. Data is typically recorded as, for example, melting point 232–234 °C.
Though formally denoting the melting range, this piece of data is almost universally referred to as
a melting point (mp).
Although a pure solid might be expected to have a single, sharp melting point, most samples are
observed to melt over a narrow range of a few degrees Celsius. The observation of a melting range
may be a result of the heating process involved in capillary measurements (mentioned above), may
reveal the presence of inhomogeneity in the macroscopic nature of the solid sample, or may
indicate the presence of other substances in the sample (contaminants or by–products of the
method used to prepare the materials).
An impure solid melt at a lower temperature and over a wider range. Thus, a solid's melting point
is useful not only as an aid in identification but also as an indication of purity. Suppose two
compounds X and Y have identical melting points of 131- 132 o C and appear to be identical. We
can easily determine whether or not X and Y really are the same compound by mixing a small
amount of Y with X (or vice versa) and taking the melting point of the mixture. (The melting point
of a mixture is called the mixture melting point). If X and Y are the same compound, the mixture
melting point will be the same as the melting point of pure X or pure Y. If X and Y are not the
same compound, one will act as an impurity in the other and the mixture melting point will be
lower and more spread out (wide range 120-125 o C in this case) than the individual melting points
of pure X or pure Y.

Melting Points as Criteria of Purity

Thermodynamics tells us that the melting point of a pure material decreases as the amount of
an impurity is increased. The presence of an impurity in a sample will both lower the observed
melting point, and cause melting to occur over a broader range of temperatures. Generally, a
melting temperature range of 0.5–1.0 °C is indicative of a relatively high level of purity. It follows
that for a material whose identity is known, an estimate of the degree of purity can be made by
comparing melting characteristics with those of a pure sample.

Melting Points as a Means of Identification and Characterization

For pure samples a clear difference of melting point between two materials reveals that they must
possess different arrangements of atoms, or configurations. If two materials are found to have the
same melting point then they may, but not necessarily, have the same structure. Clearly, the
recording of a melting point is a desirable check of purity and identity but must be combined with
measurements from other analytical techniques in order to unambiguously identify a material and
assess the purity. Part of the need for additional verification derives from the subjective nature of
capillary melting point determination. Even when heating is very finely controlled, to ensure
consistency of sample and thermometer temperature, the human element of visual inspection of
the melting point introduces significant variation.

Melting Points and Molecular Structure

Melting points are notoriously difficult to predict with any accuracy or confidence. Systematic
variations of melting point with variation in structure are not as obvious or predictable as with
boiling points. However, the sometimes surprising variations are often only highlighted in very
closely related molecules and the obvious general rule can be applied: melting points do generally
increase with increasing molecular weight. The difficulties involved in predicting melting points
are a result of the problems associated with predicting molecular packing in crystals. Many,
potentially conflicting, factors play a role in determining melting points including molecular shape,
interactions between groups within the molecule, and the degrees of freedom the molecule
possesses within the crystal.

What are the factors that affect the melting point?

1. Size of the molecule
Melting point is used for the identification and characterization of a compound. The observable
melting and boiling points of different organic molecules provides an additional illustration of the
effects of noncovalent interactions. The main principle involved is simple: how well can a
compound bind to itself? Melting and boiling are processes in which noncovalent interactions
between identical molecules in a pure sample are disrupted. The stronger the noncovalent
interactions, the more energy that is required, in the form of heat, to break them apart.

As a rule, larger molecules have higher boiling (and melting) points. Consider the boiling points
of increasingly larger hydrocarbons (shown below). More carbons and hydrogens means a greater
surface area possible for van der Waals interaction, and thus higher boiling points.

2. Force of attraction between the molecules

The force of attraction between the molecules affects the melting point of a compound. Stronger
intermolecular interactions result in higher melting points. Ionic compounds usually have high
melting points because the electrostatic forces holding the ions (ion-ion interaction) are much
stronger. In organic compounds the presence of polarity, or especially hydrogen bonding,
generally leads to higher melting point. Consider the following examples.
The only force of attraction between butane molecules is weak Van der Waals force of attraction,
so it has very low melting point. But in the case of methyl propionate, because of the presence of
polar C – O group, the molecules are held together by dipole-dipole interaction. Therefore, its
melting point is greater than that of butane. In the case of butyric acid, the molecules are held
together by hydrogen bonding, so it has a higher melting point. The melting point of sodium
butanoate is higher than that of butyric acid because the attractive force in sodium butanoate is
strong ionic interaction.

Glassware and Equipment:

- Melting point apparatus (Stuart SMP 10)

- Capillary melting point tubes (sealed at one side)
- Watch glass
- Test Tube
Chemicals:

Chemical Chemical Special Waste

Hazards
Name Formula Precautions Management
Eye: Causes severe eye irritation, redness
and pain.

Skin: Causes skin irritation. Harmful and

may cause sensitization by skin contact.

Ingestion: Harmful if swallowed and may Solid Waste

Benzoic C6H5COOH -
cause irritation of the digestive tract. Container
Acid
Inhalation: Causes respiratory tract
irritation. May be harmful if inhaled and
causes respiratory sensitization.

Eye: Causes severe eye irritation. May

result in corneal injury.

Skin: Contact with skin causes irritation

and possible burns, especially if the skin is
wet or moist. If absorbed, may cause
symptoms similar to those for ingestion.
May cause skin rash and eruptions.

Solid Waste
Ingestion: Causes gastrointestinal irritation -
Salicylic C7H6O3 Container
Acid with nausea, vomiting and diarrhea. May
cause "salicylism"; characterized by
headache, dizziness, ringing in the ears,
hearing difficulty, visual disturbances,
mental confusion, drowsiness, sweating and
thirst.

Inhalation: Causes irritation of the mucous

membrane and upper respiratory tract.

Eyes: Dust or powder may irritate eye

Solid Waste
Sucrose C12H22O11 tissue. Irritation might be transient. -
Container
 Skin: Health injuries are not known or
expected under normal use.

Inhalation: Health injuries are not

Known or expected under normal use.

Ingestion: Expected to be a low ingestion

hazard.

Inhalation: Causes irritation to the

respiratory tract.

Ingestion: Causes irritation to the Solid Waste

-
Urea CH4N2O gastrointestinal tract. Container

Skin: Causes irritation to the skin.

Eyes: Causes irritation to the eyes.

Experimental Procedure:

For the melting point determinations you will use the melting point instruments housed in the
laboratory.
1. Obtain a capillary melting point tube (sealed at one end).
2. Place a small amount of the compound on a clean and dry watch glass.
3. Using the test tube, grind the sample into fine powder.
4. To pack the tube, press gently the open end of the tube into a small amount of the fine
powdered sample.

5. Once a 2–3 mm depth of powder has been introduced, transfer the sample from the open
end to the bottom of the tube by tapping the bottom gently on a hard surface (bench top)
until the sample rests evenly at the bottom.
 6. Place the capillary tube in the melting point apparatus, measure the melting point of the
given unknown compounds. NOTE: the sample should be observed continuously, so that
the melting point of the sample is not missed.

The unknown compound will be one of the solids listed in the table below.

Compound Theoretical Melting point (o C)

Benzoic acid 122
Salicylic acid 159
Sucrose 186
Urea 132

Carefully record the melting point range, which begins when the sample first starts to melt
and ends when the sample is completely melted, for the requested compound and determine
the unknown. Also pay attention to any changes in appearance at or near the melting
temperature range.