ChE 314L: Instrumental Methods of Chemical Analysis

Melting Point

Solids are similar to liquids in that both are condensed states, with particles that are far closer together than those of a gas.
However, while liquids are fluid, solids are not. The particles of most solids are packed tightly together in an orderly arrangement.
The motion of individual atoms, ions, or molecules in a solid is restricted to vibrational motion about a fixed point. Solids are almost
completely incompressible and are the densest of the three states of matter.

As a solid is heated, its particles vibrate more rapidly as the solid absorbs kinetic energy. Eventually, the organization of the particles
within the solid structure begins to break down and the solid starts to melt. The melting point is the temperature at which a solid
changes into a liquid. At its melting point, the disruptive vibrations of the particles of the solid overcome the attractive forces
operating within the solid. As with boiling points, the melting point of a solid is dependent on the strength of those attractive forces.
Sodium chloride (NaCl)(NaCl) is an ionic compound that consists of a multitude of strong ionic bonds. Sodium chloride melts
at 801oC801oC. Ice (solid H2OH2O) is a molecular compound whose molecules are held together by hydrogen bonds. Though
hydrogen bonds are the strongest of the intermolecular forces, the strength of hydrogen bonds is much less than that of ionic bonds.
The melting point of ice is 0⁰C.

The melting point of a solid is the same as the freezing point of the liquid. At that temperature, the solid and liquid states of the
substance are in equilibrium. For water, this equilibrium occurs at 0⁰C

H2O(s)⇌H2O(l) H2O(s)⇌H2O(l)

We tend to think of solids as those materials that are solid at room temperature. However, all materials have melting points of some
sort. Gases become solids at extremely low temperatures, and liquids will also become solid if the temperature is low enough.

What is the importance of knowing the melting point of organic compounds?

The melting point is an important physical property of a compound. The melting point can be used to identify a substance and as an
indication of its purity. The melting point of solid is defined as the temperature at which the solid exists in equilibrium with its liquid
under an external pressure of one atmosphere.
A pure crystalline compound usually possesses a sharp melting point and it melts completely over a narrow range of temperature of
o
not more that 0.5-1 C. The presence of even small amount of impurities usually produces a depression in the freezing points and
o
shows a marked increase in the width of the melting point range. The melting point range of > 5 C indicates that the substance is
impure. For a material whose identity is known, an estimate of degree of purity can be made by comparing its melting point with
that of a pure sample.

What are the factors that affect the melting point?

1. Size of the molecule

Melting point is also used for the identification and characterisation of a compound. If
the melting point of two pure samples shows a clear difference in melting points, it
indicates that the two compounds must have different structural arrangements. or
they must have different arrangements of atoms or configurations. If two materials
have the same melting point, then they may (not necessarily) have the same
structure.
Consider the isomers n-butanol and t-butanol. Both have the same molecular formula
(C4 H10O), but differ in their structure.

2. Force of attraction between the molecules

The force of attraction between the molecules affects the melting point of a compound. Stronger intermolecular interactions result
in higher melting points. Ionic compounds usually have high melting points because the electrostatic forces holding the ions (ion-ion

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ChE 314L: Instrumental Methods of Chemical Analysis
interaction) are much stronger. In organic compounds the presence of polarity, or especially hydrogen bonding, generally leads to
higher melting point.
Consider the following examples.

The only force of

attraction between
butane molecules is weak
Van der Waals force of
attraction, so it has very
low melting point. But in
the case of methyl
propionate, because of
the presence of polar C –
O group, the molecules
are held together by
dipole-dipole interaction.
Therefore, its melting
point is greater than that
of butane. In the case of
butyric acid, the
molecules are held together by hydrogen bonding, so it has a higher melting point. The melting point of sodium butanoate is higher
than that of butyric acid because the attractive force in sodium butanoate is strong ionic interation.

Melting point of some common organic compounds

o o
Compound Melting Point ( C) Compound Melting Point ( C)
Phenol 42 α-Naphthylamine 50
α-Naphthol 96 Acetamide 82
β-Naphthol 123 Benzamide 128
Oxalic Acid 101 Urea 132
Benzoic Acid 122 Fructose 103
Cinnamic Acid 133 Glucose 146
p-Toludine 43 Sucrose 186
Naththalene 80 Acetanilide 114.3

Experimental Determination of the Melting Point

There are several methods by which melting points can be determined, and the choice of method depends mainly upon
how much material is available.

Melting Points from Cooling Curves

If large amounts of the solid are available (a gram or so), the most accurate method for determining the melting point is
to heat the sample until it is melted and then allow it to cool slowly for crystallization. Keep track of the temperature of the
sample as a function of time by means of an immersed thermometer or thermistor. At first, the temperature falls as the liquid loses
heat to the surroundings. When crystallization begins, however, the heat evolved during this process (-∆Ηf, the heat of
fusion) will maintain the temperature at a constant value until crystallization is complete. At this point, the temperature will again
fall as the solid loses heat to the surroundings. If the material is pure, the temperature of the sample remains constant during the
entire process of solidification; this temperature is the melting point.
This procedure is the one that should be used for calibrating a thermometer or checking the calibration of a thermometer
by using solids of known melting point. In this case, any disagreement between the reading of the thermometer and the true
melting point is attributed to an error in the calibration of the thermometer.

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ChE 314L: Instrumental Methods of Chemical Analysis

Capillary Melting Points

Capillary melting points, either in an oil bath or a melting-point apparatus, are most often used for the determination of
the melting point of a solid. A few crystals of the compound are placed in a thinwalled capillary tube 10-15 cm long, about 1 mm in
inside diameter, and closed at one end. The capillary, which contains the sample, and a thermometer are then suspended so they
can be heated slowly and evenly. The temperature range over which the sample is observed to melt is taken as the melting point.
The thermometer and sample must be at the same temperature while the sample melts, so the rate of heating must be
slow as the melting point is approached (about 1 degree per minute). Otherwise, the temperature of the thermometer bulb and
the temperature of the crystals in the capillary may not be the same. The transfer of heat energy by conduction takes place
rather slowly.
If the approximate temperature at which the sample will melt is not known, determine a preliminary
melting point determination by allowing the temperature of the sample to rise quickly. Then carry out a more accurate
determination, with a low rate of heating near the melting point.

Filling a Capillary Tube

Usually, the melting point capillary can be filled by pressing the open end into a small heap of the crystals of the substance,
turning the capillary open end up, and vibrating it by drawing a file across the side to rattle the crystals down into the bottom. If
filing does not work, drop the tube, open end up, down a length of glass tubing about 1 cm in diameter (or a long condenser)
onto a hard surface such as a porcelain sink, stone desk top, or the iron base of a ring stand. The solid should be tightly packed
to a depth of 2-3 mm.
A variety of oil baths can be used in a melting point determination, as well as in a boiling point
determination. The simplest use a burner flame and depend upon convection for mixing; the more elaborate and accurate use an
electric immersion heater and are stirred. It is easy to heat at a low and steady rate with an electric heater, but almost impossible
with a flame. When an oil bath is used, the capillary can be fastened to the thermometer by means of a small slice of rubber
tubing used as a rubber band (see Figure below).
There is also a type of melting point apparatus in which the sample and
thermometer are both supported in an electrically heated metal block and the sample in
the capillary can be observed through a magnifying glass. Usually you can heat the block
rapidly when the temperature is well below the melting point, and slowly as the melting
point is approached.
If a compound begins to decompose near the melting point, the capillary with
the sample should be
placed in the bath after the temperature has been raised to within 6 or 10 degrees of the
expected melting point, so as to minimize the length of time that the sample is heated.
Capillary melting points are properly compared with one another, but
occasionally they are
considerably different from melting points determined from cooling curves.
Micro Hot-Stage Melting Points
A quick and easy method to determine the melting point of a solid is to heat a few crystals of the
sample between a pair of microscope cover glasses on an electrically heated metal block while observing the crystals with the
aid of a magnifying glass. This method requires as little as a single crystal and it is very convenient.
Unfortunately, hot stage melting points are inherently too high. Complete thermal equilibrium between the sample,
block, and thermometer is not possible, since the thermometer is inside the block and the sample is on the surface, exposed
to the cooler atmosphere. For this reason, observed block melting points often appear to be higher than capillary melting points;
the higher the melting point, the greater the difference. However, a melting point quickly determined on a block can serve as an
approximate melting point for the determination of a capillary melting point.
Melting Ranges

Although there should be a single temperature at which a pure solid and a liquid are in equilibrium, most samples
appear to melt over a small temperature range. This happens because, with capillary or block melting points, the temperature of
the bath or block rises a little during the time it takes the sample to melt. The presence of impurities in the sample can also cause
the sample to melt over a range of temperatures. Thus, the “melting point” will usually be reported as a melting range, the
temperatures between which the sample melted.

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ChE 314L: Instrumental Methods of Chemical Analysis

The Melting Point as a Criterion of Purity

A dilute solution of a liquid begins to freeze at a temperature somewhat lower than the freezing point of the pure
liquid. The presence of an impurity causes a reduction of the freezing point of the sample. As the pure solvent crystallizes from
solution, the concentration of the impurity must increase and the freezing point of the solution must fall. Thus, a sharp melting
point (actually, a melting range of less than about 1°C) is often taken as evidence that the sample is fairly pure, and a wide melting
range is evidence that it is not pure.

The Melting Point as a Means of Identification and Characterization

If two samples have different melting points, their molecules must differ either in structure or in configuration. They must
be either structural isomers or diastereomers. If the melting points of two samples are the same, the structures of their molecules
must be the same, although they might have enantiomeric configurations. These statements apply only to pure substances, and do
not take into account the fact that some substances can exist in different crystalline forms that have different melting points.
Mixture Melting Points
Mixtures of different substances generally melt over a range of temperatures, and melting is usually complete at a
temperature that is below the melting point of at least one of the components. Thus, the nonidentity of two substances of the
same melting point can often be established by determining that the melting point of a mixtures of the two is depressed. If each
individual sample melts "sharply" (and at the same temperature, of course), and if an intimate mixture of the two, made by rubbing
approximately equal amounts together, melts over a wide range, the two substances are not the same.
Usually, however, you wish to establish the identity rather than the nonidentity of two samples, so it is unfortunate that
the converse is not always true: the absence of a depression of the melting point or of a wide melting range of the mixture is
not certain evidence that the two substances are identical in molecular structure and configuration.

Melting Point and Molecular Structure

Systematic variations of melting point with changes in structure are not as obvious or predictable as are the variations in boiling
point.

Molecular Weight
Although melting points do generally increase with increasing molecular weight, the first members of homologous series
(compounds differing by only a CH2) often have melting points that are considerably different from what would be expected on the
basis of the behavior of the higher homology In some homologous series of straight-chain aliphatic compounds, melting points
alternate: the melting point of successive members of the series is higher or lower than that of the previous member,
depending on whether the number of carbon atoms is even or odd. Sometimes, as with the normal alkanes, the melting points of
successive members of the series always increase, but by a larger or smaller amount, depending upon whether the number of
carbons is even or odd.

Polarity
As with boiling points, compounds with polar functional groups generally have higher melting points than compounds with
nonpolar functional groups. In contrast to the case with boiling points, highly branched or cyclic molecules (relatively
symmetrical molecules) tend to have higher melting points than their straight-chain isomers. The combined effects of branching or
the presence of rings, then, are to reduce the range of temperature over which the liquid can exist at a vapor pressure of less
than 760 Torr. In extreme cases, a liquid range does not exist at a vapor pressure of less than 760 Torr; at atmospheric pressure,
the substance will sublime without melting. Hexachloroethane and perfluoro-cyclohexane behave in this way.

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ChE 314L: Instrumental Methods of Chemical Analysis

Thomas-Hoover “Uni-Melt” Melting Point Apparatus

Thomas-Hoover Apparatus

Developed by Dr. John R. E. Hoover, of Philadelphia, for determining with ease and accuracy capillary
melting points in accordance with official U .S.P. and other methods.
Consisting of oil bath with electric stirrer, lightweight heating element controlled by autotransformer, built-in
capillary vibrator, etc .. combined in a single sturdy unit.
The lightweight heating coil offers the advantage of rapid response to changes in input voltage. This
permits heating the bath rapidly to within a Iow degrees of the anticipated mel ting point and then
quickly reducing the beating rate to raise slowly the temperature until melting occurs. The bath may
then be cooled rapidly for the next determination by attaching the laboratory compressed air line to
the fitting provided.
A standard 100 ml beaker of borosilicate glass is used as the melting point bath eliminating
replacement of costly custom glassware in the event of breakage.
The bath is protected from dust and air currents by being completely contained within the instrument
case.
Observation of the melting point is facilitated by the magnifier and adjustable, self-contained lighting.
Oil hath is stirred by an electrically driven stirrer with speed controlled from instrument panel.
Provision is made for running as many as five samples simultaneously.
A unique feature of the apparatus is a built-in capillary vibrator which permits the capillaries to be
shaken violently and uniformly, thereby insur ing uniform packing of sample in the capillary.
Instrument is housed in a gray metal case, with thermometer protected by metal guard. For
ease in replacing or changing the bath liquid, bath assemblv, including stirrer arid thermometer,
can be tilted out o r t he cabinet.

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ChE 314L: Instrumental Methods of Chemical Analysis

Thiele-Tube Apparatus
The Thiele tube, named after the German chemist Johannes Thiele, is a laboratory glassware designed to contain and heat an oil
bath. Such a setup is commonly used in the determination of the melting point of a substance. The apparatus itself resembles a
glass test tube with an attached handle.

Oil is poured into the tube, and then the "handle" is heated, either by a small flame or some other heating element. The shape of the
Thiele tube allows for formation of convection currents in the oil when it is heated. These currents maintain a fairly uniform
temperature distribution throughout the oil in the tube. The side arm of the tube is designed to generate these convection currents
and thus transfer the heat from the flame evenly and rapidly throughout the heating oil.

The sample, packed in a capillary tube, is attached to the thermometer, and held by means of a rubber band or a small slice o f
rubber tubing. The Thiele tube is usually heated using a microburner with a small flame.

A sample in a sealed capillary, attached to a thermometer with a rubber band, is immersed in the tube. Heating is commenced, and
the temperature ranges at which the sample melts can then be observed. During heating, the point at which melting is observed and
the temperature constant is the melting point of the sample.

A more modern method uses dedicated equipment, known as

a melting point apparatus. A slow heating rate at the melting point is
needed in order to get an accurate measurement. Record the
temperature on the thermometer when the sample starts to melt
and record the temperature again when all of the sample has melted
(this gives you the melting point range, which is what is usually
quoted in chemical literature

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ChE 314L: Instrumental Methods of Chemical Analysis

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