Experiment No.

03

Objective:

To prepare NITRO-BENZENE in the laboratory.

Apparatus:

i. Bolt head flask
ii. Reflux water condenser
iii. Dropping funnel
iv. Measuring cylinder
v. Wooden cork
vi. Thermometer
vii. Burner
viii. Water bath
ix. Ice jacket

Chemicals used:

i. Benzene
ii. Sulfuric acid
iii. Nitric acid
iv. Water

Principle:

Nitrobenzene is prepared by nitration of benzene with a mixture of concentrated sulfuric
acid, water, and nitric acid. This mixture is sometimes called "mixed acid". The nitration
reaction is carried out by following aromatic electrophilic subtitiution reaction. The reaction is
highly exotheremic and quite dangerous and hence special care has been taken while performing
the experiment.
Theory:

Nitrobenzene - is an organic compound with the chemical formula C6H5NO2. It is a water-
insoluble pale yellow oil with an almond-like odor. It freezes to give greenish-yellow crystals. It
is produced on a large scale from benzene as a precursor to aniline. In the laboratory, it is
occasionally used as a solvent, especially for electrophilic reagents.

Benzene - is an important organic chemical compound with the chemical formula C6H6 The
benzene molecule is composed of 6 carbon atoms joined in a ring with 1 hydrogen atom attached
to each. Because it contains only carbon and hydrogen atoms, benzene is classed as
a hydrocarbon. Benzene is a natural constituent of crude oil and is one of the
elementary petrochemicals. Because of the cyclic continuous pi bond between the carbon atoms,
benzene is classed as an aromatic hydrocarbon. It is a colorless and highly flammable liquid with
a sweet smell. It is used primarily as a precursor to the manufacture of chemicals.

Nitration - is a general class of chemical process for the introduction of a nitro group into an
organic chemical compound. The process involves a nitrating agent mostly nitric acid HNO3 or
NO2.

Aromatic nitration – synthesis of nitrobenzene undergoes aromatic nitration using mixture of
sulfuric acid and nitric acid (mixed acid) as a nitrating agent. Sulfuric acid which is a strong acid
is used as a catalyst for reaction. The process involves aromatic electrophilic substitution
reaction because of the delocalization of the pi-electrons and to retain the aromaticity of the
benzene ring.

The electrophile (nitronium ion NO2+) can be generated by the following reaction of the mixture
of acids:

The electrophile then attack on nucleophilic benzene ring to substitute hydrogen giving off nitrobenzene
as follows:
This nitration reaction is highly exothermic. The temperature should not exceeds 50oC and is
maintained in between 50oC & 60oC as the nitration process is highly dependent on the
temperature and hence influencing the extent of nitration which ultimately determines the
number of nitro groups attached to the benzene ring.

Moreover, special care should be taken while preparing the mixture of acid as great amount of
heat is released as nitric acid contains water and hence due to the hydration of the proton
released by the sulfuric acid. i.e.

HNO3 + 2H2SO4 → NO2+ + H3O+ + 2HSO4-

Also benzene is also smoothly and very slowly added in the acid mixture in order to avoid rise in
temperature due to exothermic nature of the reaction. Ice bath must be used during the addition.

The reaction mixture must be heated for 40 to 45 minutes in order to increase the yield.

Mechanism of reaction:

The simplified reaction is:

Step 1:
Step 2:

Step 3:

The above intermediate is sigma complex (arenium ion) and is resonance stabilized.

Step 4:

The sulfuric acid acting as a catalyst is recovered in last step.
Properties of NITRO-BENZENE:

Chemical formula C6H5NO2

Molar mass 123.06 g/mol

Appearance Yellowish oily liquid

Density 1.99 g/cm3

Odor Pungent like paste shoe polish

Boiling point 210.9oC

Nitrobenzene is a greenish-yellow crystalline solid or colorless to pale yellow, oily liquid with an
almond oil odor. Nitrobenzene is soluble in about 500 parts water and freely soluble in alcohol,
benzene, ether, acetone, and oils. It is also combustible with steam. It is very important
component of the explosives. Nitrobenzene exists in the atmosphere in the gas phase. The
dominant chemical loss process for nitrobenzene in the troposphere is expected to be by reaction
with the hydroxyl (OH) radical, although photolysis may be important. The calculated half-life
and lifetime of nitrobenzene due to reaction with the OH radical are 2 months and 3 months,
respectively.

Health effects - Nitrobenzene causes methemoglobinemia, headache, cyanosis, weakness, and
gastrointestinal upset. It may cause skin sensitization. It is also carcinogenic in nature and cause
cancer.

Applications:

i. Approximately 97% of nitrobenzene is consumed in the production of aniline, which is a
precursor to rubber chemicals, pesticides, dyes (particularly azo dyes), explosives,
and pharmaceuticals.
ii. Nitrobenzene is also used to mask unpleasant odors in shoe and floor polishes, leather
dressings, paint solvents, and other materials.
iii. Redistilled, as oil of mirbane, nitrobenzene has been used as an inexpensive perfume
for soaps.
iv.

Procedure:

i. Take 35 ml of nitric acid and pour it into bolt head flask.
ii. Take 40 ml of sulfuric acid and add it into the dropping funnel and drop wise add it to the
flask and shaking. The temperature should not exceed 50oC and is maintained using an
ice bath.
iii. Now take 29 ml of benzene and add it in the dropping funnel. Then add it drop wise in
the acid mixture present in the flask. It will take approximately 20 to 30 minutes.
At this stage the desired electrophilic substitution reaction takes place.
iv. Now, take vertical condenser and attach it to the middle neck of the flask.
v. Now gently heat the mixture for 45 minutes and make sure that the necks are closed and
temperature should maintain at 60oC using water bath.
vi. After 45 minutes two layers are formed. One layer is of nitrobenzene and other is acid
layer.
vii. Chill the mixture using water and then add to the dropping funnel. The above layer is of
nitrobenzene.

Precautions:

i. Safely and necessarily follow the instructions described in the procedure.
ii. Special care should be taken while adding sulfuric acid and benzene.
iii. Maintain the temperature and avoid heating of system by the usage of ice bath, water bath
and porcelain.
iv. Nitrobenzene is carcinogenic and toxic or corrosive to skin so, special care should be
taken while handling.
v. Reflux water condenser should be used in order to avoid loss of reaction mixture.

Observations & calculations:

Molar mass of benzene = 78 g/g mol

Molar mass of nitrobenzene = 123 g/g mol
Density of benzene = 0.8737 g/ml

Density of nitrobenzene = 1.204 g/ml

Volume of benzene taken = 29 ml

Mass of benzene taken = 29 x 0.8737
= 25.3373 g

According to balanced chemical reaction;

1 mole of benzene will give 1 mole of nitrobenzene

And hence,

78 g of benzene will give 123 g of nitrobenzene

25.373 g of benzene will give nitrobenzene = 39.95 g

So, volume of nitrobenzene obtained = 39.954 / 1.204
= 33.185 ml

Theoretical yield = 33.185 ml

Actual yield = 8 ml

%age conversion = % yield = actual yield / theoretical yield x 100

= 8 / 33.185 x 100
= 24.107 %

Results:

Nitrobenzene is prepared in the laboratory and the % yield was found to be 24.107 %.