Nitration

Introduction
Introduction of one or more nitro groups (-NO2)
into a reacting molecule.
Nitro aromatic or Nitro paraffinic compound:
When nitro group attached to carbon.
Nitrate ester:
When nitro group attached to oxygen.
Nitramine:
When nitro group attached to nitrogen.
We shall consider only those nitrations in
which nitro group replaces hydrogen atom,
since these reactions are technically
important

Applications of Nitration
products
As
Solvents
Dyestuffs
Pharmaceuticals
Explosives
They also serve as useful intermediates for
the preparation of other compounds,
particularly amines which are prepared by the
reduction of the corresponding nitro
compound.

Nitrating Agents
Fuming, concentrated, and aqueous nitric acid
Mixtures of nitric acid with sulfuric acid, acetic
acid, acetic anhydride, phosphoric acid, and
chloroform.
Nitrogen pentoxide , N2O5
Nitrogen tetroxide, N2O4

In order to make an intelligent

choice of nitrating system for
particular nitration, it is desirable
to know what species are present in
the various systems and to

The Nitryl ion NO

+
2

Mixed acid:
The system nitric acid-sulfuric acid is the most
important nitrating medium from a practical
standpoint.
Nitric acid exists in strong sulfuric acid as the
Nitryl ion, NO2+
The Vant Hoff i factor ( the number of particles
generated by one molecule of solute) of nitric acid
in sulfuric acid is found to be 4.

Aromatic Nitration
Nitryl ion is an electrophilic reactant.
Carbon atom of aromatic ring contains strong electron density.
Nitro group can attached to ortho, meta or para positions
depending upon the electron density.
The amount of these isomeric product will depend upon the
substituent.
Certain substituent cause the electron density to be greater at
ortho and para position than meta position, hence they yield
nitration products in which ortho and para isomers
predominate.
Other substituent cause the electron density to be greater at
meta position rather than ortho and meta, hence they are
called meta directing.

The isomer distribution arising from the

nitration of various monosubstituted
benzenes is shown as

Naphthalene Series
Two different mononitro derivatives, are generally
formed
The alpha and beta compounds, also known as 1nitronaphthalene and 2-nitronaphthalene.
Upon nitration , the first nitro group enters almost
into the alpha or 1 position;
a second nitro group enters into position 5 or 8.

Theory of Aromatic
Substitution
According to the theory , a substituent influences
the electron density in following two important
ways

1.Inductive effect (-I,+I)

2.Mesomeric effect (-M, +M)

Inductive effect
-I
Effect produces when substituent
attracts the electrons causing all the
position in the ring to be less
reactive than benzene.
The effect being greater on ortho
and para leaving meta more
reactive.

Making them meta directing group.

Groups which produce I effect in
order of decreasing strength are:
-NMe3, -NO2, - Halogen

+I
Effect produces when substituent repel
the electrons causing all the position in
the ring to be more reactive than in
substituted benzene.
The effect make ortho and para
positions more reactive than meta.
Making them ortho / para directing
group.
Groups which produce +I effect in
order of decreasing strength are: -O,
alkyl.

Effect of side chain reduces the effect of substituent

Mesomeric Effect
-M
Effect produces when substituent
is an electron with drawing group.
Substituent which shows a M
effect deactivate all the positions.
Meta position being less
deactivated then ortho and para
making them meta directing
compounds.
E.g. -NO2, Carbonyl group
(C=O), -CN, -COOH,
-SO3H etc.

+M

Effect produces when substituent is

from an electron donating group.
Substituent which shows a +M effect
activate all the positions.
Effect being more pronounced on
ortho and para positions making it
ortho / para directing compounds.

E.g. -OH, -OR, -SH, -SR,

-NH2, -NR2 etc.

Mesomeric effects are stronger than inductive effects

Mesomeric effect

INDUCTIVE EFFECT Vs RESONANCE

EFFECT

In most of the cases, resonance effect is stronger and

outweighs inductive effect.
For example, the -OH and -NH2 groups withdraw
electrons by inductive effect (-I). However they also
release electrons by delocalization of lone pairs (
+R effect). Since the resonance effect is more stronger
than inductive effect the net result is electron releasing
to rest of the molecule. This is clearly observed in
phenol and aniline, which are more reacting than
benzene towards electrophilic substitution reactions.
Whereas the inductive effect is stronger than the
resonance effect in case of halogen atoms. These are
electronegative and hence exhibit -I effect. However at
the same time they also release electrons by
delocalization (+R effect) of lone pair.
.

Kinetics of Aromatic Nitration

Kinetics of the nitration reactions depend upon the reacting
mixture.
Nitration in a mixed acid (mixture of nitric and sulfuric acid):
Compounds which are nitrated conveniently measurable rate in this
system are those which have strong I and M effects such as
nitrobenzene and ethyl benzoate.
Rate of these nitration is proportional to the concentration of the
added nitric acid and of organic substrate.

Nitration in organic solvents (Mixture of nitromethane or

acetic acid with nitric acid):
Kinetics of the process depend upon the aromatic compound being
nitrated.
Compound which posses strong deactivating group are nitrated at the
rate which is proportional to concentration of substrate.
Compound which are more reactive than benzene such as toluene
react at the rate which is independent of substrate.

Kinetics of Aromatic
Nitration
Nitration in aqueous nitric acid
highly reactive substrate shows zero order kinetics and less
reactive compound show first order kinetics

Effect of nitrous acid on nitration:

Causes inhabiting effect in the nitration of compound having no
activating group and thus the reaction should carried out in strong
acid or mixed acid.
Causes catalytic effect in the nitration of compound having
reactive group and thus can be nitrated in a weak nitric acid.

Oxynitration:
Reaction occur between benzene and 50 percent nitric acid
containing 0.2 molar mercuric nitrate.
Yield up to 85 percent dinitrophenol and picric acid.

Nitration of paraffinic compounds

Gas phase reaction
Unlike aromatic compounds the paraffinic compounds are quite inert to
nitrating agent.
Parrafins can be attacked by certain atoms and free radicals.
The nitration of these compounds is carried out commercially in vapour
phase at temperature of 350-450 degree centigrade.
It is a free radical reaction.
Nitric acid of 70 percent strength or less is generally used.
Variety of product are formed for example by the nitration of 2methylpentane which yields nitromethane, nitroethane, 2-nitropropane, 2nitrobutane, 1-nitroisobutane, 1-nitro-3-methylbutane, 2-nitro-3methylbutane.
The reaction is carried out by passing the reactant through the reaction
chamber in a flow system. Products are condensed and distilled.
There is optimum temperature at which highest yield is obtained.

 Oxygen increase the yield of nitromethane and nitroethane and decrease the
yield of nitrobutane. Addition of oxygen also lowers the optimum
temperature and improves conversion and yield.
Nitrogen dioxide also reacts with paraffins to yield nitroparaffins at 325 0C
Bromine has also a beneficial effect on yield and conversions.
Substitution is favorable when highly branched hydrocarbons are nitrated.

Liquid phase nitration

Less important because of low yield , low conversions and side reactions.
Replacement of hydrogen by nitro group.
No reaction possible involving replacement of alkyl group by nitro groups

Nitration of Acetylene
The reaction of acetylene with nitric acid yields tetranitromethane.
Tetranitromethane is useful compound that is used for increasing the
cetane number of diesel fuel and also used in military explosive.
The reaction occur in two steps.
In first step acetylene is allowed to react with highly concentrated
nitric acid at 500C contaning mercury nitrate in a reactor provided
with cooling coils and thermostat. Solution of
trinitromethane(nitroform) in 85% HNO3 containing NO2 results.
In second step sulfuric acid is added to the system and upon
heating nitroform is converted into tetranitromethane (TNM)

THERMODYNAMICS OF NITRATION
Nitration reaction is highly exothermic.
A study of the thermal properties of nitrating
acids is essential for an adequate understanding
of this unit process
The nitration reaction must be controlled by
systematic cooling designed to withdraw the
energy evolved
When all the energy set free by an exothermic
reaction is forced to appear as heat,
the
quantity of it lost to the cooling mechanism equal
the decrease in enthalpy
Q = -H

Engineering factors for nitration

1.
2.
3.
4.

TEMPERATURE
Temperature effect the following factors in
aromatic nitrations
Kinetic rate constant for various chemical
steps increase with temperature.
Solubilities in the acid phase of both nitrated
and unnitrated aromatics probably increase
with temperature
Viscosities
decrease
and
diffusivity
coefficients
increase
with
temperature.
interfacial area also changes with temperature.
Equilibrium constants changes with change in
temperature

continued
AGITATION
increase degree of agitation tend to promote
transfer of reactants in the two phase system,
as a result, increased agitation generally causes
increased rate of reaction.
COMPOSITION
Composition of the acid and organic phase effect
the concentration of reactants. in addition,
concentration effect,
to some extent, the
mutual Solubilities of two phases.
RATIO
Ratio of acid to organic phase is important
relative to the type of emulsion formed

Process Equipments For

Technical Nitration
Batch Nitration
Continuous Nitration

Batch Nitration
Nitration is usually done in closed cast iron
or steel vessels. Modern practice is to use
mild carbon steel.
Nitrator consists of a cylinderical vessel
containing some kind of cooling surface, a
means of agitation, feed inlets and product
outlet lines.
They are also equipped with a large
diameter quick dumping line for
emergency use if the reaction gets out of
control.
The contents of the nitrator are dumped
rapidly into a large volume of water

Batch Nitration
Cooling is generally accomplished by coils of tubes
through which either cold water or brine for
cooling may be circulated or hot water and steam
for heating.
For control of temperature in nitrations, a wall
jacket is usually not sufficient enough except in
the case of vessels of very small capacity.
Advantages of coils:
High coolant velocity is possible
More compact so can be installed anywhere in the tank.

Disadvantages of coils:
Fouling and scaling problem. Cleaning is no easy.

Batch Nitration
A common accessory for the nitrator is a suction
line in the vapour space above the liquid charge
to remove the acid fumes and oxides of nitrogen
which may be liberated.
Two factors which are of prime importance in the
design of nitrators are
Degree of agitations
Control of temperature

Continuous Nitration
The actual nitration reactions in a
continuous process are carried out in
the same type of vessel as used for
batch nitration, with the exception that
an overflow pipe or weir arrangement
is provided for the continuous
withdrawal of product and that
continuous feed of reactants is
provided.
Automization is there is continuous
processes.

Nitrators
Schmid Nitrator
Biazzi Nitrator

Schmid Nitrator
The material to be nitrated is fed into the top
of the nitrator and is immediately drawn
down through the sleeve and thoroughly
mixed with the spent acid and reacting
material.
In the bottom of the nitrator fresh mixed acid
is fed in and mixed with the other reactant by
means of agitator and baffles provided.
The reacting material then pass upwards with
high velocity through the tubes surrounded by
refrigerated brine. Product and spent acid are
withdrawn continuously from the nitrator
through the overflow line.

Biazzi Nitrator
In this apparatus the turbine type agitator
provides intensive agitation. A vortex is
formed in the center about the agitator shaft.
The reactants fed from the top are
immediately drawn into the vortex thoroughly
mixed and circulated down through the center
of the bank of cooling coils.
The high velocity imparted to the nitrator
contents makes for efficient mixing and heat
transfer. Due to throwing of cold body on hot
body flashing and evaporation takes place so
you have to provide suction line for vapours.

Mixed Acid Composition

From technical standpoint of using mixed
nitric and sulfuric acid, there are two
primary conditions that must be met.
these are
1. The
amount of 100%
nitric acid
present in nitration must be enough to
satisfy the stoichiometric requirements
of nitration reaction. it is usually
present in excess in order to maintain
reasonably fast overall reaction.
2. The amount of100% sulfuric acid with
its associate so3 must be sufficient to
promote reaction

Controlling quantities
D.V.S (dehydrating value of sulfuric acid)
D.V.S is the ratio of H2SO4 to H2O
present at the end of reaction.
Nitric ratio
nitric ratio is the ratio of the weights
of 100% nitric acid to weight of material
being nitrated.

D.V.S and stability of nitrator

charge
Increase in D.V.S favors high stability of
nitrator charge, while decrease in D.V.S
results in lowering stability.
Increasing D.V.S tends to derive the
nitration or esterification farther towards
completion, whereas too low D.V.S would
permit accumulation of
incompletely
nitrated materials, with increase dilution
and it would be favorable to oxidation.
D.V.S. ratio is always on the high, safer
side, kind of automatic safety factor.

Preparation of
nitro paraffin's

Preparation
Nitrobenzene

Preparation of nitro naphthalene