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CHM compound


									CHM138                                                                                       Lab 7
                                      Melting Points


Identifying an unknown compound requires a chemist to measure several physical properties1
and to observe a few chemical properties2 of the compound. Even though it is quite possible
for two different compounds to have a few physical and chemical properties in common, it is
much less likely that the two different compounds will have many identical physical and
chemical properties3.

Useful physical properties that are utilized by chemists in identifying an organic compound
include the compound’s: color, odor, physical state, melting point (mp), boiling point (bp),
density (d), refractive index (nD). infrared (IR) spectrum, ultraviolet (UV) spectrum and nuclear
magnetic resonance (NMR) spectrum4.

A physical constant is a numerical value measured at the time certain physical properties are
observed. As long as the physical constants of compounds are measured under standard
conditions (temperature, pressure, etc.), the values are invariant and are, therefore, useful in
determining 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 references that contain extensive
tables of physical properties and physical constants of compounds. Two of the more commonly
used references are the CRC Handbook of Chemistry and Physics, published by the Chemical
Rubber Company, and The Merck Index, by Merck & Co., Inc. If the physical properties of an
unknown substance are identical to the physical properties of a compound listed in the tables,
the two compounds are probably the same. Thus, a colorless liquid with a mp of 5.5°C, a bp of
80.1°C, and nD = 1.5011 at 20°C is very likely to be benzene, although we might want to make
a few more observations to be certain.

It must be pointed out, however, that it is not possible to accurately predict the physical
properties of newly synthesized and isolated compounds. Therefore, tables of physical
properties are only useful for identifying previously discovered compounds. However, useful
information as to the compound's identity and purity can often be obtained by the
measurement of its melting point.

Crystalline solids are composed of atoms, ions, or molecules in a highly ordered geometric
pattern (the crystal lattice). These atoms, ions or molecules are held in their positions by
electrostatic, dipole and/or London (van der Waals) forces. When a pure crystalline solid is
heated, the atoms, ions, or molecules begin to vibrate more and more rapidly until at a definite
temperature the thermal motion of the particles is great enough to overcome the forces of
attraction. Then they enter a more random and mobile state, the liquid state. The melting point
of a solid is defined as the temperature at which the solid and liquid phases of a substance are
in equilibrium5. 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 solidification may not
occur at the correct temperature due to the phenomenon of supercooling6.
Determination of the temperature at which the solid and its liquid phases of a substance are in
equilibrium is tedious and time consuming; it is also quite difficult to do if there is only a small
amount of sample available. Thus, in practice, most melting points are determined as capillary
melting points, which can be done quickly with a small amount of sample. A capillary melting
point is the temperature range over which a small amount of solid in a thin-walled capillary
tube begins to visibly soften (first drop of liquid)7 and then completely liquefies. Melting points
recorded in chemical references are capillary melting points unless otherwise stated.

A solid is said to melt SHARPLY if the melting point range is 1-2°C. A pure solid will generally
melt sharply because the forces of attraction between its particles are the same. However, the
presence of a foreign particle interrupts its uniform structure and the attractive forces are
weakened. An impure solid melts at a lower temperature and over a wider range than a pure
solid. Thus, the melting point of a solid not only helps to identify the compound but also gives
an indication of purity.

Suppose that two unknown compounds A and B have identical melting points and appear to be
identical. One can easily determine whether or not A and B are really the same compound by
determining the melting point of a mixture of A and B. (The melting point of a mixture is called
a mixture melting point). If A and B are the same substance, the mixture melting point will be
same. However, if they are different, one compound will act as an impurity in the other and the
mixture melting point will be lower and wider than the melting point of pure A or pure B.

It should be noted, however, that there is one unique mixture of two compounds A and B that
has a lower melting point than the mixture of any composition of the two. That particular
mixture is called the eutectic mixture. The melting point of the eutectic mixture is called the
eutectic point. A mixture whose composition corresponds exactly to its eutectic mixture will
have a relatively sharp melting point. Thus, there is a possibility that an eutectic mixture could
be mistaken for a pure compound. However, if a small amount of either A or B is added to the
mixture (assuming they are both known), the melting point of the resulting mixture will be
higher and more spread out than the melting point of the eutectic mixture.

Some solids pass directly from the solid state to the gaseous state without first liquefying. The
phenomenon is called sublimation. The temperature at which sublimation occurs is called the
sublimation point. Other solids decompose rather than melt. The temperature at which a solid
decomposes is called the decomposition point. While both sublimation points and
decomposition points are useful helping to identify compounds, neither is helpful in
establishing the purity of the compound.
  Physical properties are those properties that can be observed or measured without changing the composition of
the substance.
  Chemical properties are those properties observed only as a substance is changed chemically into another
  An exception would occur if the two compounds were enantiomers.
  Spectra (NMR, IR, UV, etc.) are graphs of absorption intensity vs. wavelength or frequency as electromagnetic
radiation of the proper wavelength is passed through a sample.
  A system is at equilibrium when two opposing processes (for example, melting and solidification) occur at the
same rate.
  Supercooling occurs when a liquid, cooled below its freezing point, does not solidify.
  Some solids begin to "sweat" a few degrees below their true melting points. Other solids suddenly shrink Just
before melting. Such shrinkage of a solid being heated is called sintering. Neither phenomenon is melting.

A. Preparing the Sample

Place a "pea-sized" mound of one of the "known" or "standard" compounds on a clean piece of
paper and grind it to a fine powder using a spatula. Use the spatula to push a small amount of
the solid into the opening of a capillary tube. Tap the capillary tube gently on the tabletop to
cause the solid to fall to the bottom. Repeat the process until you have accumulated a sample
1-2 mm high in the bottom of the tube. You should try to tap the sample tightly together to
remove air pockets since heat will transfer more consistently through a tightly packed sample.

B. Determining the Melting Point of two known samples

Select two known samples with similar or identical melting points from the “List of Melting Points
for Standard Compounds” given below, and prepare the capillary tubes for both of the samples.

A Mel-Temp apparatus will be used for the melting point measurements. Allow the temperature
to rise rapidly at first (a setting of 3 or 4). When the temperature is about 20°C below the
expected melting points of the compounds, slow down the heating by turning the dial down so
that temperature rises at a rate of no more than 2-3°C/min. just before, during and after the
solid melts. For each compound record the name and the range of temperature over which a
solid first shows a definite drop of liquid to the temperature at which the entire sample is liquid.

C. Mixture Melting Point

Take approximately equal amounts of the two compounds for which you already have the
melting points in B; grind and mix them together thoroughly. Prepare a third capillary tube
containing a sample of this mixture. Determine the melting point of this mixture. Be aware that
some mixtures do not lower and spread the melting point very much; However, other mixtures
have very low and very wide melting points. In other words, one must cool the Mel-Temp down
to about room temperature before attempting to determine the melting point of the mixture.

D. Determining the identity of an Unknown

Obtain an unknown solid. Your unknown sample is one of the compounds listed below.
Prepare two capillary tubes containing the unknown. The first sample is heated rapidly to
determine the approximate melting point. Then let the Mel-Temp cool to at least 20°C below
this approximate melting point and use the second tube to obtain an accurate melting point
with a heating rate of no more than 3°C per minute.

From the melting point you determined for your unknown, decide which of the listed
compounds it might possibly be. There may be more than one reasonable possibility. Prepare
a 50:50 mixture of your unknown and the compound that is the most likely of the possible
choices. Determine the melting point of this mixture. If the melting point of the mixture is the
same as that of the pure unknown, it is likely that your unknown and the compound with which
you mixed it are the same. If the melting point of the mixture is lower and wider than that of the
unknown, you should prepare a new mixture of your unknown with the second most likely
choice of known substance. You should continue to experiment until you identify a substance
that does not lower the melting point of your unknown. When you have thus confirmed the
identity of your unknown, report your findings to your instructor.

The data can be listed in a table as follows:

                          Name of               Exp. mp (°C)    Lit. mp (°C)
                         Benzoic acid                -             122.4
                         2-Naphthol                  -            121-123
                      Mixture of Benzoic
                           acid and                  -

Data Tables

Standard Compounds       Lit. mp. °C       Name of Test Compounds       Exp mp (oC)   Lit. mp (oC)
Resorcinol                 109-111
Acetanilide                113-115
d,l-Mandelic Acid             119
Benzoic Acid                 122.4
2-Naphthol                 121-123
Urea                         132.7
trans-Cinnamic Acid           133
Benzoin                    134-136
Maleic Acid                138-139         Unknown #
Anthranilic Acid           144-146
Cholesterol                  148.5         Mixed melting points with:
Adipic Acid                   152
Citric Acid                   153
Salicyllic Acid            157-159
Benzanilide                   163
Itaconic Acid              162-164

Unknown #______             Identity___________________________

Lab Exercises
1. List four (4) physical properties of organic compounds that are often measured by organic
chemists in attempting to identify a compound.

2. List two ways in which the melting point of a solid organic compound is useful to organic

3. Define the following terms.

a. melting point

b. eutectic mixture

c. eutectic point

d. sintering

4. What is the effect of a small amount of impurity on the melting point of an organic

5. Why does a sample in the melting point capillary tube have to be packed tightly?

6. Why are sublimation points and decomposition points less useful to a chemist than a melting
7. How is it possible that a mixture could fool a chemist into believing that the mixture was a
pure compound?

8. The freezing point of a substance has the same numerical value as its melting point, yet
melting points are routinely measured whereas freezing points are not. Why?

9. Which of the following temperature is the most likely to be the correct melting point range of
a mixture of urea (132-3°C) and trans-cinnamic acid (mp=132-3°C)?

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