Melting Point Experiment

Introduction
The melting point of a solid is defined as the temperature at which the solid and liquid phase
of the compound are in equilibrium. The melting point is a physical characteristic of solid
crystalline organic compounds.

The melting point can be determined on a small sample of the compound. We will use the
melting point of an organic compound:
1. To identify the compound.
2. As a measure of the purity of the compound.

A pure organic compound, whatever its source, will melt at the characteristic melting point
of that compound. Melting points of pure organic compounds are listed in handbooks, and
can be obtained from reliable online sources, such as NIST, Sigma-Aldrich, Fisher Scientific,
and many others.

An impure organic compound will melt lower than characteristic melting point of that
compound and have a wide melting point range.

Determination of the Melting Point (Melting Point Range):

The melting point range is determined using a hot block melting point apparatus called
DigiMelt as shown below.

A capillary tube is a thin and hollow glass tube has opening on one side and sealed on the
other side. A small quantity of the compound is placed in a capillary tube by gently tap the
opening side of the capillary tube on the compound. Then insert the sealed side of the
capillary tube into the chassis holes near the Tube Tapper button. Press the gray Tube
Tapper button to pack down the compound into the capillary tube. Carefully sets the Start
Temp, End Temp, and Ramp Rate (instruction given in class), and push the Start/Stop button
to preheat the block to the starting temperature. The Preheat LED will light (red). When the
Ready LED becomes lit (green), the metal block is holding at the start temperature. Next, the
capillary tube is placed into the metal block, and push Start/Stop button again to begin
 Melting Point Experiment
ramping the temperature at the preset ramp rate (°C per min). The Melt LED will light (red).
The metal block is then slowly heated by electrical resistance which is controlled by a
variable transformer. The compound is observed via the magnifying lens. When the
compound in the capillary tube starts to melt, record the digital output to the nearest 0.1°C.
When the compound finishes melting the temperature is also recorded to the nearest 0.1°C.
Push Start/Stop button to stop the measurement or simply wait until the metal block
reaches the preset End Temp. The Cooling LED will light (red). This is called the melting point
range of the compound and it is reported as a range. We want a narrow melting point range
of 3.0°C or less.

The Onset Point is generally considered the “official” start of the melt: liquid clearly appears
for the first time as a separate phase in coexistence with the crystals. It’s also called collapse
point as “the temperature at which the column of the substance under test is observed to
collapse definitely against the side of the tube”. The onset point corresponds to the lower
temperature recorded in the Melting Point Range of a substance.

The Meniscus Point corresponds to the stage of the melt when the meniscus of the liquid
becomes visible: there is a solid phase at the bottom and a clear liquid phase on top with a
well-defined visible meniscus. This point is readily detectable except occasionally when air
bubbles from the bottom push unmelted solid to the surface.

The Clear Point corresponds to the stage of the melt at which the substance becomes
completely liquid – no more solid is left (i.e. the last crystals are melted). The clear point
corresponds to the high temperature record in the Melting Point Range of a substance, and
is most often the single temperature listed in melting point tables.

Example of the melting point range of a pure compound:

mp 101.0 – 102.5°C This is a 1.5°C range.
 Melting Point Experiment

In order to get a narrow melting point range (a range of 3.0°C or less), you must use a small
sample of fine powdered crystal tightly packed in the capillary tube and the melting point
apparatus must be heated slowly.

Compounds that are impure will show a melting point lowering and a wide melting point
range.

Example of the melting point range of an impure compound:

mp 75.5 – 92.0°C (for the same compound above)
This is a wide, 16.5°C mp range and well below the reported mp of the compound.

Mixed Melting Point

If samples of two different compounds are mixed together, the mixture is an impure
compound. This impure compound (the mixture) will melt below the characteristic melting
point of either pure compound.

If samples of the same pure compound are mixed together, the result mixture is still the
same pure compound. This mixture (a pure compound) will melt at the characteristic melting
point of the pure compound.

Procedure
Part I Measure Known Compounds Melting Point
1. Obtain four capillary tubes from your instructor and pack two melting point samples
for each of the pure compounds.
2. Preset DigiMelt apparatus. For pure compounds, set the Start Temp 10°C below the
literature value; and set the End Temp 5°C above the literature value. Set the Ramp
Rate at 5°C per minute.
3. Once the DigiMelt reaches the preset temperature, insert one sample capillary tube
and measure the melting point. Do one sample at time. Record the melting point
RANGE to the nearest 0.1°C in Data Table 1.
Tips: Sometimes a student heats a sample too fast in the melting point apparatus, or
looks away just as the sample melts. In most cases, the sample could simply be
cooled and re-melted, without preparing a new sample.
4. Repeat the procedure for trial 2 of the same pure compound.
5. Repeat the procedure for the second pure sample. This time, practice to take two
trials of melting point at the same time.
6. On a watch glass, use a metal spatula mix a small and equal amount (eyeball it) of
urea and t-cinnamic acid. Be sure to mix them well.
7. Pack two melting point samples of this 1:1 mixture and obtain their melting points.
Record it in Data Table 1.
 Melting Point Experiment
Tips: This is a mixture, how do you like to preset your DigiMelt? Consult with your
instructor.

Part II Measure Unknown Compounds Melting Point

8. Sign out an unknown compound from your lab instructor, and record the unknown
number in Data Table 2. Pack two melting point samples of the unknown.
9. The unknown compound is from the following list: acetanilide, benzoic acid,
t-cinnamic acid, salicylic acid and urea. Use the Table of Reagents and Products in
your prelab to reference the literature melting points of each compound.
10. Preset DigiMelt apparatus. Set the Start Temp 10°C below the lowest melting points
of the five compounds above; and set the End Temp 5°C above the highest melting
points of the five compounds above. Set the Ramp Rate at 5°C per minute.
Determine the melting point range of your unknown compound and record it in Data
Table 2.
11. Compare your experimentally determined melting point of your unknown with the
literature values of list of unknown compounds. Tentatively identify your unknown
from this information.
12. Obtain an authentic sample of your tentatively identified compound and perform a
mixed melting point. Refer to Part I Step 6 for sample preparation. The result must
agree with the reported melting point to prove the identity of your unknown
compound.
13. Record the mixed melting point range and identify your unknown in Data Table 2.
14. Confirm the identity with your lab instructor.
15. Cleanup. Dispose the mixed sample to the hazardous solid waste container in the
chemical fume hoods. Dispose the capillary tubes in the broken glass containers.
Rinse the glassware with small quantity of acetone into the hazardous liquid waste
containers in the chemical fume hoods. Then, use soapy water to wash the glass with
a scrub brush. Finally, wipe down your workstation with acetone to remove any
organic residues and wipe it again with water.
 Melting Point Experiment

Data and Conclusion

Table 1. Melting Point of Known Compounds
Compound Literature MP (°C) Experimental MP (°C)

Trial 1 Trial 2

Urea

t-Cinnamic acid

1:1 Mixture n/a

Table 2. Melting Point of Unknown Compounds

Unknown Number

Trial 1 Trial 2

Unknown Melting Point (°C)

Mixed MP of unknown and authentic sample (°C)

Identity of unknown