Unit 6B

Heating under reflux:

It is used when the reaction is slow and one of the reactants is volatile.
The organic vapours that boil off as the reaction mixture is heated are condensed and
flow back into the reaction vessel.
As most organic compounds are flammable, it is safer to heat the mixture using an
electric heater or a water bath rather than direct heating.

Distillation:

This is used to remove a volatile substance from a mixture containing non-volatile

inorganic species, such as acid or alkali.
This can also be carried out to separate two volatile organic substances present in a
homogeneous mixture only when there is a large enough difference in the boiling
temperature of the organic substances.
The product must not decompose at the boiling temperature
The mixture is carefully heated and the vapour that comes over at 2C of the boiling
temperature (obtained from a data booklet) of the particular substance is condensed
and collected.

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Steam Distillation:

It is used to extract a volatile substance that is insoluble in water from a reaction

mixture that contains an immiscible liquid as well as a solution.
it is particularly useful for obtaining a substance that would decompose at its boiling
point.

Safety Precautions:

Distillation (simple or steam) and heating under reflux must be carried out in a fume
cupboard if the vapour of one of the reactants or products is harmful, poisonous
(toxic) or irritant.
The thermometer bulb must be placed adjacent to the mouth of the joint at the neck
of round bottom flask.
If the mixture is being heated under reflux or distilled, there must be some outlet to
the air. If there is not, pressure will build up in the apparatus, which will then fly
apart, spraying hot, flammable, and often corrosive, liquid around.
Gloves must be worn when corrosive substances are used. Such substances are must
always be handled with care.
The flask should never be heated with a naked flame. This is because almost all
organic substances are flammable and if the liquid being heated were to spill over or
the flask to crack, a fire would result.

Solvent Extraction:

An organic product can often be separated from inorganic substances by solvent

extraction.
This is useful when the components of a mixture have similar boiling temperatures and
fractional distillation is not possible.
The organic compound is separated by adding a suitable organic solvent which
dissolves the organic compound but not the inorganic one. The organic compound and

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Unit 6B
the solvent should have a large enough difference in boiling temperature so that they
can be later separated by distillation.

Purification of a liquid that is insoluble in water:

The product is distilled out of the reaction mixture and the following processes are carried
out:
The distillate is washed with sodium carbonate or sodium hydrogen carbonate solution
in a separating funnel. This removes any acidic impurities. The pressure must be
released from time to time to let out the carbon dioxide. This washing is repeated
until no more fizzing is seen.
CO32-(aq) + 2H+(aq) CO2(g) + H2O(l)
HCO3-(aq) + H+(aq) CO2(g) + H2O(l)
The aqueous layer is discarded and the organic layer is washed with water. This
removes any unreacted sodium salts and any soluble organic substances, such as
ethanol.

Less dense liquid

More dense liquid

The aqueous layer is discarded and the organic layer is dried, usually with lumps of
anhydrous calcium chloride or calcium oxide or silica gel. Solid potassium hydroxide is
used to dry amines and alcohols as they forms complex ions with calcium chloride

Purification of a solid by Recrystallisation:

The solid is filtered off from the reaction mixture and purified by recrystallisation.
A suitable solvent is chosen in which the solid is soluble when hot and almost insoluble
at room temperature.
The solid is dissolved in minimum amount of hot solvent. Minimum volume is used to
get a saturated solution.
The solution is filtered through a pre-heated glass filter funnel fitted with a fluted
paper. This removes any insoluble impurities.

The filtrate is allowed to cool and the crystals of the pure solid appears.

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Unit 6B

Then filtration is carried out again using a Buchner funnel under reduced pressure.
This removes any soluble impurities.

The solid is washed with a little cold solvent in order to remove any remaining
insoluble impurities.
The solid is then dried either between packs of filter paper or else a vacuum
desiccator or an electric oven. Using filter papers will reduce the yield as some of the
solids will get stick to the papers.

Melting Point Determination:

Method 1:

Some of the pure solid is inserted into a capillary tube and then the tube is attached
open end upwards to a thermometer with a rubber band.
The thermometer is placed into a bath of liquid. The liquid must boil at a higher
temperature than the melting temperature of the solid being tested.
Slowly the liquid bath is heated with constant stirring and solid in the capillary tube is
observed. The temperature is noted when the solid melts.

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Method 2:

The solid is placed in a boiling tube.

The boiling tube is heated in a beaker of hot liquid (water if the solid melts below
100C)
When the solid melts, a thermometer and a stirrer are placed in the molten solid and
boiling tube is removed from the liquid bath.
The molten substance is allowed to cool, stirring the whole time, and the temperature
is recorded when the first crystal of solid appears.
The melting temperature is the mean of these two values.

Method 3:

The sample is placed in a capillary tube, and the temperature increased slowly until it
melts. The melting temperature is then recorded.

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Unit 6B
Boiling Point Determination:

A small amount of the test liquid is placed in an ignition tube and it is attached to a
thermometer using a rubber band.
An empty capillary tube is placed in the liquid, with its open end below the surface.
The thermometer is clamped in the beaker of water.
The water is heated slowly, stirring all the time. When the stream of bubbles coming
out of the capillary tube is rapid and continuous, the temperature of the water bath is
noted and the heating process is stopped.
The beaker of water is allowed to cool, stirring continuously. The temperature of the
water bath is noted when bubbles stop coming out of the capillary tube and liquid
begins to suck back to the capillary tube.
The average of these two temperatures is the boiling of the liquid.
Both temperatures are slightly inaccurate because there is a time lag before the
thermometer can register the boiling temperature. Averaging these two temperatures
cancels out this error

Note:
Melting and boiling point determinations are used to identify a substance. The melting
and boiling point are determined and checked with a data booklet.
There are many problems with the boiling temperature method:
1. The boiling points of similar substances are often quite close together and can
differ by less than the experimental errors.
2. Impurities and variation in atmospheric pressure, alter the boiling point.
3. It is difficult to judge the flow of bubbles.
4. Water is a poor conductor of heat, so temperature of liquid is different from
that recorded in the thermometer. Oil can be used, but there will be rapid rise
and fall in temperature. Sufficient time is needed to be allowed, in case of
water to distribute heat equally and reach equilibrium temperature.

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5. Heating is too rapid, so it is difficult to control the rise of temperature. For

this reason, the intensity of flame of Bunsen burner can be lowered or spirit
lamp can be used so heating can be slowed down.
6. Stirring is not enough for equal heat distribution. Automatic magnetic stirrer
can be used for uniform heat distribution.
The measurement of boiling point is not very reliable compared to melting point.
Disadvantages and improvements of melting point determination:
1. Solid may be damped or impure.
Solid can be dried by heating inside oven and purified.
2. Insufficient stirring.
Automatic magnetic stirrers can be used.
3. Heating is too rapid.
Spirit lamp can be used or the intensity of Bunsen burner flame can be
lowered.
4. Water is a poor conductor, so temperature of solid is different to that on the
thermometer.
Oil can be used as a medium.
5. It is difficult to see solid and thermometer together.
The experiment should be repeated until consistent values are obtained.

Freezing Point Determination:

Two beakers are filled with water. One beaker is arranged on a tripod and gauze. The
boiling tube containing the test sample is placed in this beaker. The second beaker is
left alone on the bench.
The water in the beaker on the tripod and gauze is heated. When the solid begins to
melt the thermometer is placed in the tube. The water bath continued is heating, and
the melted solid is stirred.
When the solid completely melts, heating is stopped.
The boiling tube containing the test sample is transferred to the second beaker
containing cold water. Immediately the test sample is stirred with thermometer and a
stop watch is turned on. The temperature is recorded at regular intervals of time
(every 30 seconds interval for 7 minutes).
A graph is plotted temperature against time. This is called the cooling curve.

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Note:

The method may not be accurate due to rapid cooling.

Improvements:
1. Slowly cooling in air instead of water.
2. More accurate thermometer can be used.

Hazards and Risks:

Hazard is the potential of a substance or activity to do harm.

Risk is the chance that a substance or activity will cause harm.

Types of Hazards:

Toxicity
Absorption through the skin
Irritation if inhaled
Corrosive compounds
High flammability
Carcinogenic compounds

Risks can be reduced by:

Using less material the reaction is easier to contain and to control, and the risk of
spillage is reduced.
Using lower concentrations of solutions diluted corrosive solutions can become
irritants, still a hazard but a much reduced one.
Using specific protective clothing e.g. gloves when handling corrosive liquids.
Doing a reaction in a fume cupboard thus removing harmful vapours from the work
area.
Reducing the temperature at which the procedure is carried out thus slowing the
reaction and reducing the risk of overheating and too many fumes being produced.
Changing the materials used less hazardous material may not react as quickly or give
as much as product, but they will allow the same reaction to be studied.

Yield:
Yields are less than 100 percent because of:
Competing / side reactions.
Handling losses during transfer and purification.

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