BIO 105L LABORATORY MODULE

CHAPTER 6
MELTING POINT DETERMINATION

INTRODUCTION

Molecules in a crystal are arranged in a regular pattern. Melting occurs when the fixed
array of molecules in the crystalline solid rearranges to a more random, freely moving liquid
state. The transition from solid to liquid requires energy in the form of heat to break down the
crystal lattice. The solid's melting point is the temperature at which this transition occurs, an
important physical property of any solid compound. The melting point of a compound is useful in
establishing its identity and as a criterion of its purity. Until the advent of modern chromatography
and spectroscopy, the melting point was the primary index of purity for an organic solid. Melting
points are still used as a preliminary indication of purity.

INTENDED LEARNING OUTCOMES

At the end of this course, the students must be able to:

1. Determine the melting point range of a solid substance accurately
2. Determine the purity of the extracted compound.

GENERAL CONCEPT

Melting Point Theory

The melting point, or more correctly, the melting range, of a crystalline organic compound is
determined by the strength of the intermolecular forces between the molecules-hydrogen bonds,
dipole-dipole interactions, and van der Waals interactions. These forces hold the molecules
together in an orderly crystalline array and must be overcome for the molecules to enter the less
orderly liquid phase. Large molecular surface area and high molecular symmetry are associated
with greater intermolecular forces and higher melting points.

Melting Behavior

The melting point is generally reproducible for a pure compound. Relatively pure compounds
normally melt over a narrow temperature range of 0.5°C – 1.5°C, whereas impure substances
often melt over a much larger range. However, even small amounts of impurities usually depress
the melting point a few degrees and cause melting over a relatively wide temperature range.
Adding greater amounts of an impurity generally causes a greater decrease in the melting point.

Apparatus for Determining Melting Ranges

Two types of electrically heated melting-point devices are commonly used in introductory organic
chemistry laboratories-the Mel-Temp apparatus and the Fisher-Johns hot-stage apparatus.

A Mel-Temp apparatus is shown in Figure 14.2. The heating block with sample chambers and a
thermometer well are located within the surrounding safety shield. A thin-walled glass capillary

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tube holds the sample. The capillary tube fits into one of these sample chambers in the heating
block, multiple chambers allow simultaneous determinations of three melting points. A cylindrical
cavity in the top of the heating block holds the thermometer, a light illuminates the sample chamber,
and an eyepiece containing a small magnifying lens facilitates observation of the sample. A digital
thermometer can also be used with a Mel-Temp apparatus.

A rheostat controls the rate of heating by allowing continuous adjustment of the voltage. The
higher the rheostat setting, the faster the rate of heating. However, the rate of heating at any
particular setting increases more rapidly at the start and then shows as the temperature increases.
The decreasing rate of heating at the higher temperatures allows for the slower heating needed in
the melting point is approached.

The Fisher-Johns hot-state apparatus is another device for the determination of melting points
(Figure 14.3). The crushed sample is placed between thin, circular, microscope coverslips rather
than in a capillary tube. The coverslips fit in a depression in the metal block surface. A rheostat
controls the rate of heating, and the lighted sample area is viewed through a small magnifying
glass.

DETERMINING MELTING RANGES

The melting range of an organic solid can be determined by introducing a small amount of the
substance between two coverslips or into a capillary tube with one sealed end. Such capillary tubes,
which are approximately I mm in diameter, are commercially available.

Filling a capillary tube. Place a few milligrams of the dry solid in a piece of smooth-surfaced
paper and crush it to a fine powder by rubbing a spatula over the solid while pressing down.
Introduce the solid into the capillary tube by tapping the open end of the tube in the powdered
substance. A small amount of material will stick in the open end. Invert the capillary tube so that
the sealed end is down, and holding it very near the sealed end, tap it lightly with quick motions

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against the bench top. (Care must be taken while tapping the capillary tube against the bench top,
the tube could break and cause a cut).

The solid will fall to the bottom of the tube. Repeat this operation until the amount of solid in the
tube is 1-2 mm in height. A small sample is essential for accurate melting points. Melting-point
determinations made with too much sample lead to a broad melting range because more time is
required to melt the complete sample and the temperature continues to rise while the sample melts.

An alternative method for getting the solid to the bottom of a capillary tube is to drop the tube
down a piece of glass tubing about 1m in length or down the inside tube of a condenser, the bottom
end of which is resting on the lab bench. After a few trips down the glass tubing, the solid will
usually have fallen to the bottom of the capillary tube.

Wet Samples. If a solid is still wet from recrystallization, it will not fall to the bottom of a capillary
tube but will stick to the capillary wall. This failure to behave properly is probably a good thing,
because melting points of wet solids are usually low and thus nearly worthless. If your sample is
still wet, allow it to dry completely before continuing with the melting-range determination

Heating the sample to the Melting Point

The melting point apparatus can be heated rapidly until the temperature is about 20°C below the
expected melting point. Then decrease the rate of heating so that the temperature rises only 1°- 2°
per minute and the sample has time to melt before the temperature rises above the true melting
point. When you are raking successive melting points, remember that the apparatus needs to cool
to at least 20° below the expected melting point before it can be used for the next determination.

Approximate melting point. If you do not know the melting point of a solid sample, you can make
a quick preliminary determination by heating the sample rapidly and watching for the temperature
at which melting begins. In a more accurate second determinations, you can then carefully control
the temperature rise to 1°- 2° per minute when you get within 15°- 20° of the expected melting
point.

Use a fresh sample for each determination. Always prepare a fresh sample for each melting-point
determination; many organic compounds decompose at the melting point, making reuse of the
solidified sample a poor idea. Moreover, many low-melting compounds (mp 30°- 80°C) do not
easily resolidify with cooling.

Digital thermometers. Digital thermometers have a metal probe that responds more rapidly than a
mercury-filled glass thermometer to temperature changes. The role of heating near the melting
point must be 1°- 2° per minute or else the observed melting point range will be probable be above
the true melting point.

Reporting the Melting Point

Unless you have an extraordinary pure compound in hand, you will always observe and report a
melting range – from the temperature at which the first drop of liquid appears to the temperature
at which the solid is completely melted and only a clear liquid is present. This melting range is
usually 1°- 2° or slightly more. For example, salicylic acid usually gives a melting range of 157°-
159°C. An extremely pure sample of salicylic acid, however, melts over less than a 1° range (for

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example, 160°- 160.5°C) and it may have 160°C listed as its melting point. Published melting
points are usually the highest value obtained after several recrystallization; the values you observe
will probably be slightly lower.

LEARNING ACTIVITY

1. Watch the video clip below:

Capillary tube melting point: https://www.youtube.com/watch?v=zMjl9MzpySU
2. Based on the video clip, determine the melting point range of benzoic acid sample.
3. Compare the obtained melting point range of benzoic acid to the melting point of benzoic
acid
4. Determine the level of purity of the benzoic acid sample.
5. Prepare a laboratory report following the prescribed format.

REFERENCES:

Techniques in Organic Chemistry by Jerry R. Mohrig, Christina Noring Hammond, Paul F.

Schatz (z-lib.org)

https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Book%3A_Organic_Chemistry_
Lab_Techniques_(Nichols)/06%3A_Miscellaneous_Techniques/6.01%3A_Melting_Point/6.1
C%3A Melting_Point_Theory

https://www.slideserve.com/shae/theory-of-melting-point

http://amrita.olabs.edu.in/?sub=73&brch=7&sim=33&cnt=1