Laboratory Experiments for

organic chemistry (81113)

EXP 2: Melting point- identification of organic compound
Sahar Dowek
PURPOSE
• 1. Determine the purity of an organic compound using melting point
as physical property.
• 2. Identify an unknown substance using its melting point.
• 3. Identify an unknown substance using mixture melting point.
• 4.Learn how to obtain an accurate melting point using a Mel-Temp
apparatus.
Thomas
Hoover
UniMelt)
Introduction
• Physical properties :
• 1. melting point
• 2. boiling point.
• 3. Index of refraction
• 4.Density
• 5. Specific rotation
• 6. Solubility.
INTRODUCTION
• The melting point :of a solid organic compound is the temperature at
which the solid Phase is in equilibrium with the liquid phase. A solid
compound changes to a liquid When the molecules acquire enough
energy to overcome the forces holding them together in the
crystalline form. Generally, in most organic substances, the
intermolecular forces are relatively weak.
• The melting point range: is defined as the temperature at which the
crystals begin to liquefy to the point at which the entire sample is
liquid.
• The difference between temperatures is that material starts to melt
and completely melt.
Factors affecting on melting point
• 1. molecular weight or size of molecule .( )
• 2. impurities.( )
• 3. branching ( )
• 4. intermolecular interaction ( )
• Most pure organic compounds melt over a narrow temperature range
of 1-2°C
• (1- 3°C)range: we consider the melting point is sharp and the solid is
pure.
• The range upper 3 we consider the melting point is broad and the
compound is not pure.
•
• The development manufacturing of pure chemicals requires that
close attention be paid to purity, quality, stability, and safety to
ensure that the final product performed as intended.
• The presence of impurities in organic compound will:
• 1. Decrease in the melting point.
• 2. broadening of the melting point range.
• WHY?
Melting Point Diagrams of pure compound
Melting Point Diagrams of mixture compound
Melting Point of mixture compound
* both compounds have sharp melting points.
• 150°C : melting point of pure X
• 148°C: melting point of pure Y
point C:
• When we mix (20X:80Y) mass ratio
•Melting point decrease along curve C-B
(142°C)until minimum temp. of (130°C)
Is obtained.
Point A:
• We mix (80X:20Y) mass ratio.
• the melting point decrease along curve A-B
to (146°C) until minimum temp. of (130°C)
Is obtained.
130°C :eutectic tempreture
Is the minimum melting point for a mixture
of X and Y.
Heating mixture then the tempreture rise to
eutectic tempreture (130°C).
 The Melting Point of a Mixture of Two Compounds

• * (20 mg X: 80 mg Y)
X acts as an impurity in Y the eutectic
point is D at temp. 130°C.
at this temp X and Y start to melt
Together.
• * (40 mg X: 60 mg Y)
the eutictic point 130°C piont B.

* (80 mg X: 20 mg Y)
• Y acts as an impurity in X the eutectic
point is E at temp. 130°C.
• at this temp X and Y start to melt
together
• (40 mg X: 60 mg Y)
• The tempreture remains constant at 130°C until all 20mg X melts at
the eutectic point
• X and Y will melt in the ratio of 40 parts X to 60 parts Y.
• If 20 mg of X melts, then 30 mg of Y also melts
• (20 mg X x 60/40 = 30 mg Y).
• At this point, the remaining 50 mg of solid Y is
in equilibrium with a molten mixture of
the eutectic composition
• more heat is applied to the mixture
• the remaining Y begins to melt.
• shown by curve B-C At 142°C
• point C (20X:80Y) liquid composition of X and Y),
• all of Y is melted. At temperatures higher than 142°C, liquid X and
liquid Y exist together with a composition at which the entire mixture
liquefies is 142°C, 6 degrees lower than the melting point of pure Y.
Also, the melting point range 130-142°C is quite broad.
• If a mixture has exactly the eutectic composition of 40 mass percent X
and 60 mass percent Y, the mixture exhibits a sharp melting point at
130°C, this melting point could lead to the false conclusion that the
mixture is a pure compound. Addition of either pure X or pure Y to
the mixture causes an increase in the melting point, as indicated by
curve B-A or B-C, respectively. Observing this melting point increase
indicates that the original sample is not pure.
Identification of Unknown Compound
• The melting point can be used to identity of an unknown compound.
• A mixed melting Point can be useful in identifying the identity of an
unknown compound.
• Experimentally, A small portion of a known compound, whose
melting point is known from the chemical literature, is mixed with the
unknown compound. If the melting point of the mixture is the same
as that of the known compound, then the known and the unknown
compounds may be identical. A decrease in the melting point of the
mixture and a broadening of the melting point range indicates that
the compounds are likely to be different
Assessment of a Compound Purity
• In general, a melting point range of 5°C or more indicates that a
compound is impure. Purification of the compound causes the
melting point range to narrow and the melting point to increase.
Repeated purification may be necessary before the melting point
range narrows to 1-2°C and reaches its maximum value, indicating
that the compound is pure.
Capillary Melting Point Determination
• The method involves placing a little of the sample in the bottom of a
narrow capillary tube that has been sealed at one end. The
determination is made using a Melting Point Apparatus that
simultaneously heats both the sample tube and a thermometer. 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, mp 232–234°C. Though
formally denoting the melting range, this piece of data is almost
universally referred to as a melting point
• The rate of heating, controlled by a dial, should be kept relatively low,
especially for samples with a low melting point, to ensure that the
thermometer reading represents, as accurately as possible, the true
temperature experienced by the sample tube (since the transfer of
heat within the apparatus is relatively slow). With this fact in mind, it
is sensible when recording a melting point of an unknown material to
perform a trial run where the temperature is increased relatively
rapidly in order to ascertain a rough melting range.
• The determination is then repeated by heating rapidly to within
around twenty degrees of the expected melting point and then very
carefully (slowly) increasing the temperature the remaining few
degrees until the melting point is reached. Of course, if the melting
point of the material is known with some confidence, for instance if
the determination is being made to confirm identity, then the trial run
is unnecessary
• 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 in
homogeneities 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).
Melting Points and Molecular Structure
• 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 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 :
1. molecular shape, 2. interactions between groups within the molecule,
and the 3. degrees of freedom the molecule possesses within the crystal.
THE END