EXPERIMENTAL PROCEDURES - AS CHEMISTRY

Heating under reflux (synthesis of an organic product) :

If a reaction that involves heating requires an organic volatile liquid, heating under reflux is used.
The method boils a liquid and has a vertically mounted condenser with a pear-shaped flask so any
volatile /evaporating liquids will condense and return to the reaction mixture. This prevents
escape of substances and promotes further reaction if possible.
1. Reactants are added to a pear shaped flask with a few anti-bumping granules.
2. The flask is not stoppered as this would build up pressure and could cause the glassware to
crack.
3. Attach the condenser vertically to the flask so that the water flows in thought he condenser
bottom and out the top. This ensures all internal surfaces of the condenser are cooled; all
parts are filled with cold water.
4. Heat the reaction mixture gently with a Bunsen burner or a heating mantle. Indirect heating
(heating a beaker of water below the pear-shaped flask) is a safe method.

If the organic product needs distilling to prevent further reaction then non-reflux heating is used.
In his case, quick fit distillation apparatus may be used during synthesis. Non-reflux is shown on
the right.
 Simple distillation (separating miscible liquids)
A mixture of substances will separate off into fractions when heated as each substance will have a
different boiling point. By heating the mixture, each pure component is vaporised, condensed and
collected. A thermometer is used to keep track of the range at which a substance can be distilled off
at.

The substance with the lowest boiling point will evaporate off first. Quick fit glassware is commonly
used. Grease/Vaseline is used to seal joints to prevent loss of reagents.

1. Put the mixture into a pear-shaped flask and add a few anti-
bumping granules. Set up the distillation apparatus as shown
below.
2. Gently heat the mixture with a heating mantle or a Bunsen flame
(maybe indirectly by heating a beaker of water below which the
pear-shaped flask is submerged in).
Heating mantles are safer than Bunsen burners for organic liquids;
they do not have a naked flame.
3. When the thermometer reads 20C below the boiling point of the
liquid you are about to collect, put the beaker in place. Collecting
the distilled liquid until the temperature rises above (+0.50C) of the
liquid you are collecting. Stop heating.
4. The process can be repeated for another compound of a higher
boiling point following on from step 3. A clean beaker must be
used.
Purifying an organic liquid (separating immiscible liquids):
Synthesised organic liquids are usually crude and contain a mixture of reactants, solvents or impurities of
side reactions.

1. The organic product is mixed with another immiscible liquid (usually aqueous liquid i.e. water). This
mixture is placed in a separating funnel. The liquids separate into two layers with the denser forming at
the bottom. Run off and dispose of the aqueous layer. Run the organic product layer into a clean
conical flask.
2.
a. If acidic purities are present then some sodium hydrogen carbonate solution is added to remove
them. A stopper is added to the funnel and the mixture must be well shaken. Gas will be produced so
pressure inside the separating funnel must periodically be released. Repeat this step until no
effervescing is observed.

b. If the crude product is alkaline and needs neutralising then add dilute acid until the mixture is
neutral. Testing regularly with damp universal litmus paper.

3. Dry the crude product by adding anhydrous sodium sulfate ( a common drying agent) and swirling the
mixture. Other anhydrous (group 1 / 2) salts like calcium chloride (or magnesium sulfate) could be
used instead.

4. The product is then separated by distillation.

The aqueous layer in the separating funnel can be detected by simply adding more water.
The larger layer will then clearly be the aqueous one. Most organic solvents float on top of an aqueous
phase, though important exceptions are most halogenated solvents
Vacuum filtration:
Vacuum filtration is used to separate a solid from a filtrate/solution rapidly.

1- Connect a conical flask to a pump via the side arm.

2- Dampen a piece of filter paper with distilled water and place in the Buchner funnel
3- Switch the vacuum pump on and carefully pour in the mixture to be filtered. Cover the top of the
Buchner funnel with the palm of your hand and press down gently.
4- The pump will create a partial vacuum so that the filtrate gets pulled through quicker.
5- Disconnect the flask from the vacuum pump before turning the pump off to prevent `suck back’.
6- If necessary, wash the filtered solid with distilled water to remove excess soluble impurities, then
allow solid to dry.
Recrystallisation:
Recrystallisation is used to purify solid crude organic compounds with small amounts of impurities
(both soluble/insoluble). A suitable hot solvent (e.g. ethanol) is chosen based on the desired
product.

1. Select a suitable solvent which the desired substance is very soluble at high temperatures
and insoluble, or nearly so, at lower temperatures.
2. Dissolve the crude mixture in a minimum amount of the hot solvent (less solvent equates to
higher yields).
3. Any insoluble impurities are then filtered off and the filtrate (solution) is retained. It is best
to preheat the funnel and conical flask to prevent any solids crystallising out at this stage.
4. The filtrate/flask is then cooled (sometimes in an ice bath) until crystals begin to form. These
are filtered off using suction filtration (to remove soluble impurities).
5. A very small amount of hot solvent may be dropped over the crystals while the filtrate is
removed to removed excess impurities.
6. The crystals are left to dry (covered by an inverted funnel).

Melting point determination:

Measuring melting pints is a good method to determine if a solid organic
compound is pure. Impurities will lower a substance’s melting point.

If the compound melts at or just above (+/- 0.50C) the published melting
point of the compound, it is pure. If the compound melts over a range of
temperatures (typically lower) than the published melting point of the
substance, it contains impurities.

1. Seal the end of a glass melting point tube by heating it to melt in a Bunsen
flame and stretching it apart in the centre.
2. Tap the open end into the solid so it is picked up and then tap it again
inverted so a small amount falls into the bottom of the sealed end.
3. Fix the tube in the melting point apparatus with the thermometer in line
with the sample (a rubber band may be used). Heat the surrounding liquid
(oil) gently, stirring to ensure even heating throughout. Temperature
should rise slowly.
4. Record the temperature which the solid begins and finished melting at to
obtain melting range.
Thin layer chromatography (TLC) / paper chromatography:
Two techniques that can be used to separate small quantities of
organic compounds, purify organic substances or follow the progress of
reaction over time.

Chromatography relies on the fact that different substances have

different affinities (or solubilities) with a particular solvents are carried
through the chromatography medium at different rates.

• Paper chromatography: Uses paper as the medium/stationary

phase
• TLC: Uses a silica plate as the medium/stationary phase.

1. Place a pencil line across the chromatography paper 1cm form its base. Spot a sample of the
test mixture on the pencil line, using a capillary tube or dropper pipette. Pencil will not mix
with the solvent (ink will).
2. Repeat this along different points across this line with the reference samples.
3. Place the plate in a beaker of solvent so the solvent is just below the pencil line. Cover the
beaker with a lid to create a saturated environment and allow the solvent to rise up through
the chromatography plate.
4. Remove the plate when the solvent front is near the top. Mark the solvent front with
another pencil line. Allow the plate to then dry in a fume cupboard.
5. Place the plate in a beaker with iodine granules and shake. This will ease identification of the
spots for each sample. Ultraviolet light (from UV lamp) can also be used to identify spots.
6. Match the heights reached, or Rf values, with known compounds using the
same chromatography solvent mix.

Enthalpy change for combustion:

1. Place the fuel in a spirit burner and weight with the lid on (using a top pan balance)
2. Fill a calorimeter can with a known volume of water (measured with a measuring cylinder) and
clamp it, using a clamp stand, clamp and boss, so it is directly above the spirit burner.
3. Surround the setup with a draught excluder to help reduce energy losses.
4. Place a thermometer into the water recording the initial temperature. Add a lid with a hole for the
thermometer, this will reduce heat loss by evaporation.
5. Ignite the spirit burner and so heat the water for a given time period
6. Measure the final temperature of the water and put out the spirit burner by placing the lid back on.
Reweigh the burner.
7. Mass of fuel burnt, m = Final mass – Initial mass (of the burner). Weigh with lid on burner in both
cases so the fuel does not evaporate.
8. Temperature change ΔT = Final temperature – Initial temperature (of the water) This is measured
using a thermometer.
9. Energy (KJ) = ( mass of water X C (=4.18) *ΔT ) / 1000
10. Scale up for one mole of fuel burnt using the calculation: Energy / (Mass of fuel/Mr)
= (-) ΔH (KJmol-1)
 Reasons why the experimental value may be
lower than the published standard enthalpy
change of combustion
1. Heat loss to the surroundings/air molecules.
2. Heat loss through evaporation of the water.
3. Evaporation of the fuel form the wick of the spirt
burner.
4. Incomplete combustion.
5. Energy goes into heating the calorimeter not just
the water.
6. Standard conditions may not have been used in
the reaction.

How to improve the accuracy of the enthalpy

change result:
Use a bomb calorimeter, this has a number of
features that improve accuracy:
1. Fuel is ignited electronically (combustion of
another material like a wooden splint will not
interfere).
2. Fuel is combusted under plentiful supply of compressed oxygen to ensure complete combustion.
3. The reaction vessel is well insulated in a thermostatted tank.
4. A platinum resistance thermometer is used to increase the accuracy of the temperature
measurements.
However, the combustion occurs at a constant volume in a closed container and with a constant
pressure. The results must be modified accordingly as these are not standard conditions.

Hess’ Law states that the enthalpy change of any chemical reaction is independent of the
intermediate stages so long as the initial and final conditions are the same for each route.

The enthalpy change for combustion is the enthalpy change that occurs when one mole of fuel is
completely combusted in oxygen under standard conditions ( with elements in standard states).

NOTE: This is not experimentally possible as the exothermic reaction means H2O formed will be a
vapour (steam) and not in its standard state.