Basra University College of science and Technology

Pharmacy department

ORGANIC CHEMISTRY LABORATORY

Title of Report :-
Determination of Boiling Point
Student Name :

‫علي مكي عبد الحسن‬

Supervised by:

Dr: Ahmed makki

Theory:
Boiling point, temperature at which the pressure exerted by the
surroundings upon a liquid is equaled by the pressure exerted by the vapour
of the liquid; under this condition, addition of heat results in the
transformation of the liquid into its vapour without raising the temperature.
At any temperature a liquid partly vaporizes into the space above it until the
pressure exerted by the vapour reaches a characteristic value called the
vapour pressure of the liquid at that temperature. As the temperature is
increased, the vapour pressure increases; at the boiling point, bubbles of
vapour form within the liquid and rise to the surface.
The normal boiling point of a compound is an indicator of the volatility of
that compound. The higher the boiling point, the less volatile is the
compound. Conversely, the lower the boiling point, the more highly volatile
is the compound. At a given temperature, if a compound’s normal boiling
point is lower, then that compound will generally exist as a gas at
atmospheric pressure. If the boiling point of the compound is higher, it then
exists as a liquid or a solid
A liquid's boiling point can be determined using the capillary method, where
an inverted capillary is placed in the liquid of interest and the liquid is
heated. As the temperature increases, the air in the capillary escapes and is
replaced by the vapor of the liquid. The vapor pressure in the capillary
increases with temperature. Once it exceeds the atmospheric pressure, the
vapor escapes the capillary in a stream of bubbles. When the heat is
removed, the liquid cools, and the vapor pressure in the capillary decreases.
When the vapor pressure reaches the atmospheric pressure, the liquid begins
to fill the capillary. The temperature at which this occurs is the boiling point.
the boiling point is considered as a criterion of purity of a compound and is
useful for identification of organic compounds. Similar to the melting point
the boiling point may be sharp or may vary over a temperature range. Pure
liquids have sharp boiling points while mixtures show a boiling point range.
The atmospheric pressure plays an important role in determination of the
boiling point correctly. Reduction of the pressure leads to a decrease or a
depression in the boiling point and vice versa.
The purpose of this experiment is to determine the boiling points of
various organic compounds and to use these to identify unknowns
The boiling point of an organic substance is directly related to its structure,
where stronger intramolecular forces result in a higher boiling point as
molecules are able to hold onto each other and remain in the liquid phase
longer. The higher boiling point for ethanol is observed due to the OH
structure that causes hydrogen bonding between the molecules. Acetone has
a polar CO double bond, which results in dipole-dipole forces. Since
hydrogen bonding is stronger than dipole-dipole forces, ethanol has a higher
boiling point.
Additionally, ethanol has a lower molecular weight than acetone. However,
molecular weight has less of an impact on the boiling point than the
molecular structure. For example, butane is a gas at room temperature and
pressure, as it has a boiling point lower than 25°C. Ethanol has a slightly
lower molecular mass than butane, but it is liquid at room temperature and,
therefore, has a boiling point higher than room temperature. This is due to
the hydrogen bonding between the ethanol molecules, which is stronger than
the van der Waals forces between the butane molecules.
Material & Tools:

❖ Ethanol
❖ Test tube
❖ Capillary tube
❖ Water bath
❖ Thermometer
❖ Stand and clamp
Procedure:

1- Obtain a liquid unknown from your instructor. Record the sample

number.

2- Attach a clean and empty test tube to a thermometer with sewing

thread. Put an empty capillary tube in the test tube so that the open
end of capillary is down.

3- Ensure that the temperature of the paraffin oil is below 50 °C. Place
2‐3 mL of sample in the test tube.

4- Turn on the hot plate and use a clean glass rod to stir the paraffin oil
to ensure a uniform heat distribution.

5- Record the temperature when rapid air bubbles come out from the
capillary. At this stage, the vapor pressure of the unknown inside the
capillary is higher than the atmospheric pressure.

6- Turn off the hot plate and carefully insert a ceramic tile between the
beaker and the hotplate. Alternatively, you may replace the hot plate
with the one that has not been used. However, the thermometer bulb
and the content in the test tube should be submerged in the paraffin oil
at all times.

7- As the temperature decreases, air bubbling will gradually slow down.

Record the temperature when you see the last bubble come out and
some liquid goes into the capillary.
general trends that affect the boiling point:

1. Strength of intermolecular forces

The relative strength of intermolecular forces such as ionic, hydrogen

bonding, dipole-dipole interaction and Vander Waals dispersion force affects
the boiling point of a compound. The influence of these forces depends on the
functional group present. We can explain the effect of these forces on the
boiling point of compounds with the help of some examples.
Consider butane and its
three derivatives such as
diethyl ether, n- butanol
and sodium n-
butoxide. n-butane
(C4H10) contains no polar
functional group. The
only attraction between
the butane molecules is
weak Vander Waals
dispersion forces. The
result is that butane boils
at a temperature at which water freezes, and is much lower than diethyl ether.
In the case of diethyl ether, the molecules are held together by dipole-dipole
interaction which arises due to the polarized C-O bond. Its boiling point is
35oC. Compare its boiling point with that of n-butanol. The boiling point of
n-butanol is 117oC. The greatly increased boiling point is due to the fact that
butanol contains hydroxyl group, which is capable of hydrogen bonding. But
the boiling point of sodium butoxide is higher than that of butanol because the
attractive force in sodium butoxide is very strong ionic bond. The
intermolecular forces go in the order Ionic > Hydrogen Bonding > Dipole-
Dipole > Van der Waals dispersion force.
2. Length of carbon-carbon chain

As the number of carbon atoms increases

or the length of carbon-carbon chain
increases, the boiling point also increases.
This is because the force of attraction
between the molecules increases as the
molecule gets longer and has more
electrons. It takes more energy to
overcome the force of attraction, and so the boiling point rises.

3. Branching decreases the boiling point

As the length of carbon chain increases, the surface area of the compound will
also increase. Van der Waals dispersion force is proportional to the surface
area. So, the increase of surface area increases the ability of individual
molecules to attract each other. Branching in molecules decreases the surface
area thereby decreasing the attractive force between individual molecules. As
a result, the boiling point decreases.
Consider the boiling point of n-pentane and neo-pentane (2,2-dimethyl
propane). These are isomers having the same molecular formula (C5H12), but
differ in their structures.
4. Polarity
Polarity of the molecule determines the force of attraction between the
molecules in the liquid state. In polar compounds, the positive end of one
molecule is attracted by the negative end of another molecule. That means
polar molecules are attracted by opposite charge effect. The polarity of a
molecule is determined by its functional group. The greater the polarity, the
higher is the boiling point.
Water baths, heated on a hotplate, are most commonly used to heat solutions
to 100 C. They may also be used to heat to lower temperatures, although it
can be difficult to maintain a constant temperature. Water baths can be
covered with aluminum foil to prevent excessive evaporation, or to prevent
excess moisture from entering open vessels. Cold water baths can also be used
to cool apparatuses in a quick manner.
Oil baths are much like water baths, but use silicone or mineral oils in order
to enable temperatures hotter than the boiling point of water (> 100oC100oC).
Silicone oil baths can be heated to 250oC, while mineral oil baths can be
heated to 300oC.77 Mineral oil is composed of mixtures of long-chain
alkanes, and so is combustible. Direct contact with open flames should
therefore be avoided.
Oil baths can be heated in a Pyrex crystallizing dish atop a hotplate. It is also
quite common for the oil to be electrically heated, through immersion of a
coiled wire connected to a "Variac". A Variac connects to the outlet and can
deliver variable voltage through the wire. A Variac set to "100" would be
equivalent to plugging the system directly into the wall (100%), while a
setting of "50" means the delivered voltage is halved (50%). By controlling
the delivered voltage, Variacs are used to regulate the temperature of the oil.
If you have previous experience using a Variac with heating mantles, the
settings will not translate to the oil bath as oil bath wires heat more rapidly
than a heating mantle's wires. A paper clip can also be used in an oil bath and
stirred with a stirring plate in order to dissipate heat. This allows for the
temperature of an oil bath to quickly respond to adjustments up or down.

References:

❖ Safety Glossary: Boiling Point, Physical and Theoretical Chemistry

Laboratory, Oxford University.
❖ The Clausius-Clapeyron Equation, Professor Chung Chieh,
University of Waterloo, Canada.
❖ Editors: R.H. Perry and D.W. Green (1997), Perry's Chemical
Engineers' Handbook, 7th Edition
❖ Standard Pressure IUPAC defines the "standard pressure" as being
105 Pa (which amounts to 1 bar).
❖ DeVoe, Howard (2000). Thermodynamics and Chemistry (1st ed.).
Prentice-Hall. ISBN 0-02-328741-1.