38 Experimental Organic Chemistry ■ Gilbert and Martin

pour the solid directly from the original bottle, because spills are more likely.
Carefully transfer the solid to your reaction flask or other container. You may also
weigh the solid directly into the reaction vessel by first taring the flask or conical vial.
Clean any spills promptly.

2.7 M E L T I N G - P O I N T M E T H O D S A N D A P P A R A T U S
The laboratory practices and apparatus used to determine melting points of solids
are discussed in this section, and the theory and use of melting points are described
w in Section 3.3. The task of determining the melting point of a compound simply
See video on Melting
Point Methods involves heating a small amount of a solid and determining the temperature at
which it melts. Many different types of heating devices can be used, but most uti-
lize a capillary tube to contain the sample so that only a small amount of the sam-
ple is required.

Capillary Tubes and The first step in determining a melting point is transferring the sample into a melting-
Sample Preparation point capillary tube. Such tubes have one sealed end and are commercially avail-
able. The proper method for loading the sample into the capillary tube is as follows.
Place a small amount of the solid on a clean watchglass and press the open end of
the tube into the solid to force a small amount of solid (about 2–3 mm in height)
into the tube (Fig. 2.16a); this operation should not be performed on filter paper,
because fibers of paper as well as the solid may be forced into the tube. Then take a
piece of 6–8-mm tubing about 1 m long, hold it vertically on a hard surface such as
the bench top or floor, and drop the capillary tube down the larger tubing several
times with the sealed end down (Fig. 2.16b). This packs the solid sample at the
closed end of the capillary tube.

Melting-Point The melting point of the crystalline solid is determined by heating the packed cap-
Determination illary tube until the solid melts. Some representative devices for measuring melting
points are presented in Figures 2.17–2.19. The most reproducible and accurate
results are obtained by heating the sample at the rate of about 1–2 °C/min to ensure
that heat is transferred to the sample at the same rate as the temperature increases
and that the mercury in the thermometer and the sample in the capillary tube are
in thermal equilibrium.
Many organic compounds undergo a change in crystalline structure just before
melting, perhaps as a consequence of release of the solvent of crystallization. The
solid takes on a softer, “wet” appearance, which may also be accompanied by
shrinkage of the sample in the capillary tube. These changes in the sample should
not be interpreted as the beginning of the melting process. Wait for the first tiny
drop of liquid to appear.
Melting usually occurs over a range of a degree, perhaps slightly more. Accord-
ingly, a melting-point range of a compound is typically reported with the lower
temperature being that at which the first tiny drop of liquid appears and the higher
temperature is that at which the solid has completely melted.

Melting-Point Apparatus A simple type of melting-point apparatus is the Thiele tube, shown in Figure 2.17a.
This tube is shaped such that the heat applied to a heating liquid in the sidearm by
a burner is distributed evenly to all parts of the vessel by convection currents, so
 Chapter 2 ■ Techniques and Apparatus 39

Open end

Sample Melting-point
capillary tube

Melting-point
capillary tube
Packing tube
Sample
Watchglass

Figure 2.16
(a) Filling a melting-point
capillary tube. (b) Packing
the sample at the bottom
of the tube. (a) (b)

Thermometer

Cork notched Thermometer

to permit
escape of air
Slice of
rubber
Rubber band or slice of
tubing
rubber tubing
Level of heating
fluid at 200 °C Melting-
Heating fluid point
Level of heating
capillary
fluid of room
tube
temperature
Figure 2.17
(a) Thiele melting-point Melting-point
capillary tube Sample
apparatus. (b) Arrangement
of sample and thermometer for Thiele tube
Microburner
determining melting point. (a) (b)

stirring is not required. Temperature control is accomplished by adjusting the flame

produced by the microburner; this may seem difficult at first but can be mastered
with practice.
Proper use of the Thiele tube is required to obtain reliable melting points.
Secure the capillary tube to the thermometer at the position indicated in Figure 2.17b
using either a rubber band or a small segment of rubber tubing. Be sure that the
40 Experimental Organic Chemistry ■ Gilbert and Martin

Thermometer

Thermometer

Melting-point Melting-
capillary tube point
capillary
View tube

Magnifying View Temperature

glass control
Light
source
Temperature
control

Figure 2.18
Thomas-Hoover© melting-point Figure 2.19
apparatus (courtesy of Arthur H. Mel-Temp© melting-point apparatus
Thomas Company). (courtesy of Laboratory Devices).

band holding the capillary tube on the thermometer is as close to the top of the
tube as possible. Now support the thermometer and the attached capillary tube
containing the sample in the apparatus either with a rubber stopper cork, as
shown in Figure 2.17a, or by carefully clamping the thermometer so that it is
immersed in the oil. The thermometer and capillary tube must not contact the glass
of the Thiele tube. Since the oil will expand on heating, make sure that the height
of the heating fluid is approximately at the level indicated in Figure 2.17a and that
the rubber band is in the position indicated. Otherwise, the hot oil will come in
contact with the rubber, causing the band to expand and loosen; the sample tube
may then fall into the oil. Heat the Thiele tube at the rate of 1–2 °C/min in order to
determine the melting point. The maximum temperature to which the apparatus
can be heated is dictated by the nature of the heating fluid, a topic that is discussed
in Section 2.9.
The Thiele tube has been replaced in modern laboratories by various electric
melting-point devices, which are much more convenient to use. One common type
of electric melting-point apparatus is the Thomas-Hoover melting-point unit
shown in Figure 2.18. This particular unit has a built-in vibrating device to pack
the sample in the capillary tube, and it also allows for the determination of the
melting points of up to five samples simultaneously. The oil bath in this unit is elec-
trically heated and stirred. An electrical resistance heater is immersed in a con-
tainer of silicone oil. The voltage across the heating element is varied by turning
the large knob in the front of the apparatus so that the oil is heated at a slow, con-
trolled rate. A motor drives a stirrer in the oil bath to ensure even heating; the rate
of stirring is controlled by a knob at the bottom of the unit. Some models are
equipped with a movable magnifying lens system that gives the user a better view of
 Chapter 2 ■ Techniques and Apparatus 41

the thermometer and the sample in the capillary tube. The capillary tube containing
the sample is inserted into the apparatus as illustrated in Figure 2.18.
The Mel-Temp® apparatus shown in Figure 2.19 is another electrical unit that
utilizes a heated metal block rather than a liquid for transferring the heat to the
capillary tube. A thermometer is inserted into a hole bored into the block, and the
thermometer gives the temperature of the block and the capillary tube. Heating is
accomplished by controlling the voltage applied to the heating element contained
within the block.

2.8 B O I L I N G - P O I N T M E T H O D S A N D A P P A R A T U S
There are several techniques that may be used to determine the boiling point of a
liquid, depending upon the amount of material available. When multigram quanti-
ties are available, the boiling point is typically determined by reading the ther-
mometer during a simple distillation, which is described in Section 2.13. However,
for smaller amounts of liquid there is sometimes not enough sample to distill, so
other techniques have been developed. Two of these are described here.

Miniscale Method An accurate boiling point may be determined with as little as 0.5–1.0 mL of liquid
using the method illustrated in Figure 2.20. Working at a hood, place the liquid in a
long, narrow Pyrex® test tube, and add a small, black carborundum boiling stone;
do not use a white marble chip, as bumping is more likely. Clamp the test tube and
position the thermometer about 2 cm above the level of the liquid using a second
clamp. Bring the liquid rapidly to a vigorous boil using a suitable heating device
suggested by your instructor. You should see a reflux ring move up the test tube,
and drops of the liquid should condense on the walls of the test tube. Control the
amount of heating so the liquid does not boil out of the test tube. Be sure the bulb
of the thermometer is fully immersed in the vapor of the boiling liquid long enough
to allow the equilibration required for a good temperature reading to be obtained.

Figure 2.20
Refluxing vapor
Miniscale technique to
determine the boiling point
Boiling liquid
of a liquid. Boiling stone