- Place 35 cm3 of concentrated nitric acid in a 500 cm3
round bottomed flask, and add slowly 40 cm3 of concentrated
sulphuric acid, keeping the mixture cool during the addition by
immersing the flask in cold water.
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- Why does the mixture of acids become warm?
- The reaction between the acids is:
HNO3 + 2H2SO4 → NO2+
+ H3O+ + 2HSO4-
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The nitric acid contains about 30% water, and the
hydration of the proton released by the sulphuric acid gives out heat. |
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- Place a thermometer in this nitrating mixture, and then add very
slowly 29 cm3 of benzene. This should be added about 3 cm3
at a time, and the contents of the flask thoroughly mixed
after each addition. The temperature of the mixture must not be allowed
to rise above 50oC, and should be kept under control if
necessary by immersing the flask in cold water.
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- Why must the benzene be added slowly?
- The nitration is exothermic, and the temperature must not rise too
much.
- Explain the need to mix the ingredients thoroughly.
- The nitrating mixture and benzene are nearly immiscible, so the
mixture must be agitated vigorously so that the two phases are broken
into small drops to maximise the surface area of the two phases in
contact. That is where reaction occurs.
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- When all the benzene has been added, fit a reflux water condenser to
the flask, and place the latter in a water bath, which is then
maintained at 60oC for 45 minutes. During this period the
flask should be withdrawn from the bath from time to time and vigorously
shaken in order to break up the nitrobenzene layer which would otherwise
float on the dense acid layer below.
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- Why is the mixture then heated for 45 minutes?
- This increases the yield by allowing time for the rather slow
reaction to occur.
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- After completion of heating pour the contents of the flask into a
large excess of cold water (about 300 cm3) in which the
nitrobenzene sinks to the bottom. Stir the mixture as vigorously as
possible. Decant off as much as possible of the supernatant aqueous
layer, and transfer the residual liquid to a separating funnel. Run off
and retain the lower nitrobenzene layer, and discard the upper aqueous
layer. Return the nitrobenzene to the funnel, and shake it vigorously
with an equal volume of cold water. Allow the nitrobenzene to separate
and run it off as before. Return it to the funnel, and wash with an
equal volume of dilute sodium carbonate solution, releasing the pressure
as necessary. Repeat the washing with fresh sodium carbonate solution
until there is no evolution of carbon dioxide.
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- What is the function of the cold water?
- The acids are diluted and the reaction stopped.
- What is the reason for the vigorous stirring?
- The acids are to some extent soluble in nitrobenzene, so vigorous
stirring removes as much of this into the aqueous layer as is possible.
- Why is the nitrobenzene washed with sodium carbonate solution?
- This reacts with and removes in the aqueous layer any residual acid
dissolved in the nitrobenzene.
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- Separate the nitrobenzene from the sodium carbonate solution a
completely as possible (see below), transfer it to a small flask, and
add some anhydrous granular calcium chloride. Shake until the liquid is
completely clear.
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- What is the function of the calcium chloride?
- It is a drying agent.
- What is the significance of the liquid becoming clear?
- The organic layer is then dry; wet organic compounds that are nearly
immiscible with water look hazy.
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- Filter the nitrobenzene through a fluted paper directly into a 60cm3
distilling flask fitted with an air condenser. Distil the nitrobenzene
carefully, collecting the fraction that boils between 207oC
and 211oC.
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- Why is a fluted filter paper used?
- Fluted papers enable faster filtering.
- What is an air condenser?
- A glass tube that is cooled by the surrounding air rather than by a
water jacket.
- Why is such a condenser used?
- The boiling temperature of nitrobenzene is sufficiently high to make
an air condenser efficient for condensing the vapour.
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Note: after washing with sodium carbonate solution it would be usual to
wash with water to remove any traces of sodium carbonate. However
nitrobenzene tends to produce an emulsion if this is done, which takes a
long time to separate, so the step is best omitted. |
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