Experiment # 5:

Preparation of Nitro-
Benzene

Date: 23-11-10

Muhammad Usman

(2008-chem-02-B)
1. Benzene:

Carcinogenic:
Benzene exposure has serious health effects. The American Petroleum Institute
(API) stated in 1948 that "it is generally considered that the only absolutely
safe concentration for benzene is zero. The US Department of Health and
Human Services (DHHS) classifies benzene as a human carcinogen.

Highly flammable:
It has a flash point of -11 oC. It can readily catch fire. So care should be taken
while handling it.

Toxic:
The short term breathing of high levels of benzene can result in death.

Properties of Benzene:
IUPAC Name Benzene
Benzol
Other names
cyclohexa-1,3,5-triene

Appearance Colorless liquid

 Structure

Molecular formula C6H6

Molar mass 78.11 g mol-1
Density 0.8765 g cm-3
Melting point 5.5 oC
Boiling point 80.1 oC
Solubility in water 1.8 g/L at 15 oC
Flash point -11 oC

2. Nitric acid:

Toxic:
Fumes from concentrated nitric acid are very damaging if inhaled

Corrosive:
Concentrated and moderately concentrated solutions are very corrosive
and can cause serious skin damage

Oxidant:
Contact with the eyes can cause serious long-term damage.
Properties of Nitric acid:
IUPAC Name Nitric acid
Oxoazinic acid
Aqua fortis
Other names
Salpetre acid

Spirit of nitre

Appearance Colorless liquid

Structure

Molecular formula HNO3

Molar mass 63.012 g mol-1
Density 1.5129 g cm-3
Melting point -42 oC
Boiling point 83 oC
Solubility in water Miscible
Acidity (Pka) -1.4
Flash point Non-flammable

Sulphuric acid:

Corrosive:
It is a strongly corrosive compound as it readily oxidizes anything.
 Dangerous to Environment:
Although sulfuric acid is non-flammable, contact with metals in the event of a
spillage can lead to the liberation of hydrogen gas. The dispersal of acid aerosols
and gaseous sulfur dioxide is an additional hazard of fires involving sulfuric acid.

Very toxic:
Sulfuric acid is not considered toxic besides its obvious corrosive hazard, and the
main occupational risks are skin contact leading to burns and the inhalation of
aerosols. Exposure to aerosols at high concentrations leads to immediate and
severe irritation of the eyes, respiratory tract and mucous membranes.

Properties of sulfuric acid:

IUPAC name Sulfuric acid

Other names Oil of vitriol

Structure

Molecular formula H2SO4

Molar mass 98.06 g/gmol
 Appearance

Density 1.84 g/cm3 (liquid)

Melting point 10 oC
Boiling point 337 oC
Solubility in water Miscible
Acidity (Pka) -3
Viscosity 26.7 cP (20 oC)
Flash point Non- flammable

Water:
It is a non-hazardous compound.

Environmentally safe:
Water is an essential part of life. Life cannot be sustained without water.
Food & eatables contain some amount of water in them. It is a non-
hazardous compound.

Water
IUPAC name
Oxidane
Hydrogen oxide
Dihydrogen monoxide
Hydrogen monoxide
Hydroxylic acid
Other names
Hydrogen hydroxide
R-718
Oxygen dihydride
Oxygen hydride
 Oxane

Structure

Molecular formula H2O

Molar mass 18.0152833 gmol-1

Appearance

1000 kg m-3 (liquid)

Density 917 kg m-3 (solid)

Melting point 0 oC
Boiling point 99.98 oC
Acidity (Pka) 15.74
Basicity (Pkb) 15.74
Viscosity 0.001 Pa.S (20 oC)
 Preparation of Nitro-Benzene

Chemicals required:
1) Nitric acid 2) Benzene
3) Concentrated H2SO4 4) Cold Water

Chemical reaction:

Apparatus Required:
Bolt head flask Dropping funnel
Knee tube Water condenser
Adopter Conical flask beaker
Stirrer

Procedure:
1. Place 35 cm3 of concentrated nitric acid in a 500 cm3 round bottomed flask, and add slowly 40
cm3 of concentrated sulfuric acid, keeping the mixture cool during the addition by immersing the
flask in cold water.
2. 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 mixed after each addition.
The temperature of the mixture must not be allowed to rise above 50 oC, and should be kept under
control if necessary by immersing the flask in cold water.
3. 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 60 oC 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.
4. 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.
5. 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.
6. 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 207 oC
and 211oC.

Uses of Nitro-Benzene:
Aniline production:

Approximately 95% Nitro-benzene is used in aniline production.

Specialized applications:

1. As a precursor to Rubber chemicals, Pesticides, Dyes, Explosives, Pharmaceuticals

2. Shoe and floor polishes, leather dressings, paint solvents, and other materials to mask
unpleasant odors.
3. Used as an inexpensive perfume for soaps
Industrial preparation of Nitro-Benzene:
Industrially Nitro-Benzene is prepared from following procedure.

Feed tanks:

Raw materials are stored in feed tanks from where they can be supplied individually.

H2SO4 supply:

Hot Sulfuric acid at 90oC in run from the heat insulated storage tank (B).

A1-A4 units:
These are the battery of the nitrators. Here reactants are mixed together and nitration reaction takes place.

Nitric acid:
Under vigorous agitation, sufficient 63% HNO3 is added to the nitrators to produce a mixed acid
containing 4 % HNO3.
Benzene supply:
Sufficient benzene is then delivered from its storage scale tank to react with all the nitric acid in the
nitrators.

Time required for reaction......................................................................10 minutes

Upon Completion of reaction, agitation is stopped & charge permitted to settle. While the separation of
the nitrobenzene and spent acid proceed, another nitration is started, thus providing a continuity of
process.

Neutralizer:
The crude nitrobenzene is drawn off through the side outlet (C) on the nitrators & sent to the neutralizer.

Spent acid recovery:

Acid heater:
The spent acid has

HNO3 content.............................................0%

Nitrobenzene..............................................small quantities

From outlets D1-D4 spent acid is drawn off. Now it is directed towards the acid Heater (E). It is heated by
the low pressure steam to maintain the sensible heat of the spent acid (72% H2SO4).

Vapor separator:
The evaporator, operating under a vacuum of 29 in. , effectively removes the water of nitration by virtue
of sensible heat of the spent acid and returns the sulfuric acid to the system at its original 75% strength.
The small quantities of nitrobenzene present in water in the condenser is separated & added to the crude
charge.

References:
Unit processes in organic synthesis by P.H. GROGGINS

Fifth edition, page 112-113