Name: Dina L.

Lacson

Date Performed: 09/20/16

BS Chemistry III

Date Submitted: 09/30/16

Experiment No. 4
SYNTHESIS OF NITROBENZENE FROM BENZENE

I.

DISUSSION
Benzene (C6H6) is a colorless liquid. It is carcinogenic, highly flammable and toxic

and exposure to it may cause serious health effects. Nitrobenzene on the other hand, is the
simplest aromatic nitro compound, having the molecular formula C6H5NO2 and is used in the
manufacture of aniline, benzidine, and other organic chemicals. It has a colorless to pale
yellow, oily, highly toxic liquid with the odor of bitter almonds undergoing nitration,
halogenation, and sulfonation much more slowly than does benzene. Nitrobenzene is highly
toxic and is readily absorbed through the skin so prolonged exposure may cause serious
damage to the central nervous system, impair vision, cause liver or kidney damage, anemia
and lung irritation. Inhalation and ingestion of this chemical compound can also have
dangerous effects. It may be reduced to a variety of compounds, depending on the reaction
conditions. Most nitrobenzene produced is reduced to aniline while smaller amounts are
converted to azobenzene, hydrazobenzene, and phenylhydroxylamine.
Nitrobenzene has been extensively used for making the shoe polishes as it dissolves
dyes and penetrate the leather well. It is used as a scent for cheap soaps. It has also been used
for making the floor polishes and also been used as an oxidizing agents in organic synthesis.
The reaction of alkenes with nitric acid is not a generally useful reaction. Addition of nitric
acid to the double bond is accompanied by more or less oxidation. However, benzene is quite
stable to most oxidizing agents and its reaction with nitric acid is not a generally useful
reaction. Addition of nitric acid to the double bond is accompanied by more or less oxidation.
However, benzene is quite stable to most oxidizing agents, and its reaction with nitric acid is
an important organic reaction.

O
+

HNO3

H2SO4

H2O

The acid mixture was added in portions so that the temperature does not exceed 50
C. Sulfuric acid is a catalyst, allowing nitration to occur more rapidly and at lower
temperatures. After all of the acid has been added, the reaction mixture is cooled and the oily
nitrobenzene separated, washed and distilled. Selection of the appropriate nitrating agent and
the conditions of reaction is based upon factors such as reactivity of the compound to be
nitrated, its solubility in the nitrating medium, and the ease of isolation and purification of
the product.
The nitro group is an important functional group in aromatic chemistry because it
may be converted into many other functional groups. The nitration reaction thus provides a
route to many substituted aromatic compounds. Many properties of the nitro group can be
interpreted on the basis of a resonance hybrid of two Lewis structures:

In these structures, the ONO system is seen to have an allylic anion type of
system. In a mixture of nitric acid and sulfuric acids, an equilibrium is established in which
many species are present. One of these species is the nitronium ion, NO 2+, which has been
detected by spectroscopic methods. In the mixture of acids, it is produced by a process in
which sulfuric acid functions as an acid and nitric acid functions as a base.

(1)

H2SO4

(2)

H2O ONO 2

2 H 2SO4

+
+
+

HONO 2

H2O NO 2

H2SO4

H 3O

HONO 2

H 3O

+
+

HSO 4
NO 2

NO 2

+
+ 2 HSO 4
HSO 4

The mechanism is similar to other sulfuric acid catalyzed dehydrations. Sulfuric acid
protonates the hydroxyl group of nitric acid, allowing it to leave as water. The structure of
nitronium ion is known from spectroscopic measurements. It is related to the isoelectric
compound, carbon dioxide. The molecule is linear, and is a powerful electrophilic reagent.
O

O
N
O

H2SO 4
O

H
O

H2 O

It reacts directly with benzene to give a pentadienyl cation intermediate. The

nitronium ion reacts with benzene to form a sigma complex. Loss of a proton from the sigma
complex gives the nitrobenzene.
O

benzene

H SO

O
O

sigma complex

nitronium ion

H2SO 4

nitrobenzene

(resonance-delocalized)

It can be noted that the reaction occurs on nitrogen rather than oxygen. Reaction at
oxygen gives a nitrite compound, RONO. Nitrites are unstable under such strongly
acidic conditions and decompose to products containing CO bond. These oxidation
products react further to give highly colored polymeric compounds. The formation of more
or less tarry byproducts is usual side reaction in most aromatic nitration reactions.
The final product produced after distillation was a pale yellow oil which have the
characteristic odor of almonds. The boiling point of nitrobenzene is 210- 211 C.
C6 H6

NO 2

HSO 4

C6H5NO 2

H2SO4

Due to several errors and some factors such as the temperature, a final product of
nitrobenzene was not synthesized. The hot plate used for the experiment has not reached a
temperature of 210C, thus a nitrobenzene product was not obtained. The loss of yield might
also because of incomplete reactions due to certain factors such as the temperature, or when

the reactants have not completely come into contact with each other, or when the experiment
was done without waiting for the mixture to complete its reaction.
During isolation and purification process a lot of product was most probably lost
especially when washing the nitrobenzene with Na 2CO3 which was done 5 times before the
nitrobenzene was neutral in the litmus test. Some of the sample was probably discarded with
the Na2CO3. During distillation the mixture was not distilled to dryness, which might have
also account for loss of product. There is also the possibility of loss due to nitrobenzene
further nitrating to m-dinitrobenzene. If a residue remains in the distilling flask it is probably
m-dinitrobenzene which is formed when the temperature of nitration is not carefully
controlled. Water is added during the first part to prevent the mixture from nitrating further
into m-dinitrobenzene.

II.

CONCLUSION
This experiment generally aims to synthesize nitrobenzene from benzene.

Nitrobenzene (C6H5NO2) is the simplest aromatic nitro compound used in the manufacture of
aniline, benzidine, and other organic chemicals. Benzene showed neither the typical
reactivity nor the usual addition reaction of alkenes. Addition of nitric acid to the double
bond is accompanied by more or less oxidation. However benzene is quite stable to most
oxidizing agents and its reaction with nitric acid is an important organic reaction. The
reaction used for this synthesis was therefore an electrophilic aromatic substitution reaction
using an appropriate Lewis acid catalyst. The nitronium ion from concentrated nitric acid
reacted with benzene forming nitrobenzene. The synthesis was carried out by adding benzene
to a mixture of nitric and sulfuric acid and then the nitrobenzene was isolated and purified by
separation from the acid, a series of washing and finally, distillation. There was no final
product of nitrobenzene obtained in the synthesis due to failure in heating the sample in a hot
plate with a temperature of 210 C, thus the percent yield of nitrobenzene was not able to be
calculated.

III.

REFERNENCES
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Gerald Booth (2007). "Nitro Compounds, Aromatic". In: Ullmann's Encyclopedia of

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Mcmurry, S. (2008). Fundamentals of Organic Chemistry 6th Edition . Thompson

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