First Lab Session

Bring the following Lab Dress Code

1. Face shield (optional in case you do not

want to borrow safety glasses from the lab). 1. Wear pants (make sure they are
2. Lab coat (long sleeved and to the not torn. (Shorts, skirts, and
knees). anything that exposes the feet are
3. Box of gloves. not allowed).
4. Towel (quantity=2, size=small). 2. Wear closed shoes (open
5. Sponge. shoes such as sandals, ballerinas,
ballerinas with socks.. are not
6. Detergent.
allowed).
7. Lab manual (hard copy)
3. Long hair must be tied in a bun.
8. Calculator

If you do not abide by the safety rules

➢ you will NOT be allowed to enter the lab
➢ you will get a zero on the experiment
 Experiment I Melting Points
Lecture Outline

1. Purpose of the Experiment

2. Melting Point
▪ Definition
▪ Melting point Range
3. Purity of Compounds
▪ Effect of Impurities
4. Identification of Compounds
▪ Mixed Melting Point Technique
5. Procedure
 Purpose:

1. To learn the technique of melting point

determination.
2. To determine the melting points of three
known organic compounds.
3. To determine the melting point of an
unknown organic compound.
4. To identify an unknown organic
compound by mixed melting point
technique.
 Melting Points
Definitions:

Melting point: is the temperature at which the

solid and liquid phases exist in equilibrium.

Normal melting point: is the temperature at which

a substance melts at a pressure of 1 atm.

➢In general, melting points are unaffected by

changes in pressure or other external factors.

➢Most organic compounds are molecular

substances that have melting points below 300oC.
Molecules in a crystal are arranged in a regular pattern.

➢ Melting occurs when this fixed array of molecules rearranges

to the more random, freely moving liquid state.

➢ Such a transition requires energy in the form of heat to break

down the crystal lattice and to overcome the intermolecular
forces of attraction between molecules.

➢ The melting point is the temperature at which this transition

occurs
Melting points are determined for three reasons:
1. To identify unknown compounds
2. To determine the purity of a compound
3. To characterize new compounds
 Melting Point Range
The melting point of a solid compound is a
physical property that can be measured as a
method for identification.
The melting point of a solid is usually reported
as a melting point range (t1-t2)
➢ t1: the temperature at which the first drop of
liquid appears
➢ t2: the temperature at which the entire solid
sample is liquid.
 Purity of Compounds
The measured melting point gives a rough
indication of its purity.
➢ Pure substances have sharp melting points
(0.5-1.0oC)
➢ The purer the compound, the higher its melting
point and the narrower its melting point range.
➢ Melting a solid requires energy to overcome the
crystal lattice energy.
➢ Impurities disrupt the crystal lattice and, so less
energy is required to break the intermolecular
attractions.
 Effect of Impurities
➢ A Soluble impurity Y will lower the melting point of
compound X and broaden the melting point range
➢ The decrease in melting point is proportional to the
amount of impurity present.
➢ A limiting situation is reached when the amount of the
soluble impurity Y saturates the liquid X compound.
➢ The temperature at which this occurs is called the
eutectic temperature TE and the composition is called
eutectic composition.
➢ A mixture of X & Y cannot exist as a liquid at atmospheric
pressure below TE
➢ A eutectic composition behaves like a pure compound
exhibiting a sharp melting point
➢ Insoluble impurities have no effect on the melting point.
 Generalized Vapor Pressure-Temperature Diagram

Melting point
of x with
Eutectic Impurity y

Melting point
of pure x

Brewster, R. Q. ; Vanderwerf, C. A.; McEwen, W. E. In Unitized Experiments in Organic Chemistry, 5th Edition, 1977
• The eutectic mixture is the of at least two solid
components that produces a change of phase to
liquid at a certain temperature.
• This temperature receives the name of eutectic
point temperature and corresponds to the
minimum melting temperature of the different
possible compositions.
• Thus, the melting point of pure components (A
or B) is higher than that of the eutectic mixture
The melting point of a compound is used as an
index of its purity

➢A pure substance shows a sharp melting

point i.e. a narrow range (0.5-1.0oC) with t2
very close to the true or reported m.p.

➢An impure substance shows a broad m.p.

range with t2 well below the true m.p.

➢Note: A sharp melting point may also be

obtained if the compound and impurity form a
eutectic composition.
Some compounds decompose upon heating
➢ decomposition usually involves changes such
as darkening or evolution of a gas
➢ decomposition can occur below or at the
melting point, in such cases the exposure to high
temperatures should be limited.

Some compounds sublime upon heating

➢ Such compounds have fairly high vapor pressures
and can change directly from the solid to the gas
phases without passing through the liquid phase
this is called sublimation
➢ the melting point is determined in a sealed capillary
tube.
 Identification of Compounds
The melting point is used for identification of
compounds.
Use “mixed melting point technique”.
Equal amounts of two solids are crushed and
mixed together.
1. If the substances are identical,
⇒ the mixture has the same m.p. as either of
the two solids
2. If the substances are different,
⇒ the m.p. will be lower and the range will be
wider
i.e. one substance will act as an impurity.
 Melting Point Apparatus
➢ The sample is placed in
a capillary tube sealed
at one end.
➢ The tube is then placed
in the sample holder.
➢ Up to three samples
can be run at the same
time.
➢ The sample is
observed with the aid
of a magnifier.
➢ The melting points are
recorded with a touch
of a button.
 Experimental procedure
Determination of the melting point of 3 known compounds:

1. Fill a capillary with around 3 mm height of sample 1.

2. Place the prepared sample in the sample holder of the melting
point instrument.
3. Heat rapidly until the temperature is within 10oC of the reported
m.p. of the sample.
4. Continue heating slowly at a rate of 2oC per minute.
5. Observe the sample through the magnifying glass as it melts
6. Record the melting point as the temperature from the start of
melting (first drop of liquid), this may be preceded by a visible
softening and shrinking of the sample, until it becomes a clear
liquid.
7. When the sample has melted turn off the melting point
apparatus.
 Actual mp (oC) Compound name
1 115 Acetanilide

2 122 Benzoic acid

3 128 Benzamide

4 133 Trans-cinnamic acid

5 133 Benzoin

6 135 Phenacetin

7 140 o-Chlorobenzoic acid

8 152 Adipic Acid

9 158 Salicylic acid

II. Determination of the melting point of an
unknown solid:
➢ Prepare the sample
➢ Heat rapidly to get a rough estimation of
the melting point.
➢ Follow steps 1-7 as before to determine
the m.p.
III. Identification of the unknown compound:
1. The unknown sample may be identified by
comparing its m.p. with the m.p. of the compounds
listed in the manual.
2. Select all compounds whose m.p. are within 5oC of
that observed for the unknown
3. Perform a mixed melting point determination:
➢ Mix equal amounts of the unknown and the
suspected compound and determine the m.p. of the
mixture.
➢ If the compounds are identical , the melting point of
the unknown will be unchanged
➢ If the compounds are different, the known
compound will act as an impurity and will result in a
lower m.p. and broader range.
Basic melting point tips:
➢ Take at least two m.p. measurements:
– one fast, to get a rough idea of the melting point range
– one slow, an accurate m.p. can only be obtained if the
temperature is allowed to rise slowly.
➢ Use a small amount of sample
- if too large a sample is used the time required for complete
melting is longer and the temperature range larger.

➢ Technique affects range

- if you heat too fast, an inaccurate m.p is obtained (lower or
higher values depending on the type of thermometer).