1.

Introduction
• Introduction of one or more nitro groups (-NO2)
into a reacting molecule.
Nitro aromatic or Nitro paraffinic compound:
When nitro group is attached to carbon then it is
nitro compound.
Nitrate ester: When nitro group attached to
oxygen for example nitro glycerin or nitro
cellolose.
Nitramine: When nitro group attached to
nitrogen.
We shall consider only those nitrations in which
nitro group replaces hydrogen atom, since these
reactions are of technically importance.
Applications of Nitration products
As
• Solvents eg. Nitro-paraffines, nitrobenzene
• Dyestuffs eg picric acid and intermediates eg. 2,4 dinitro
phenol
• Pharmaceuticals
• Explosives eg nitro glycerin, nitrocellulose, TNT
(Tri-nitro toluene)
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 compounds are present in the various
systems and to understand the mechanism of the
reaction under consideration.
The Nitronium ion NO2 +
Mixed acid: • The mixture nitric acid-sulfuric acid is
the most important nitrating medium from a
practical standpoint.
• Nitric acid exists in strong sulfuric acid as the
Nitronium ion, NO2 +
• The Van’t 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
• Nitronium ion NO2+ 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 in
the substituted benzene.
• The amount of these isomeric product will
depend upon the substituent.
• Certain substituent causes 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 substituents 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 group already
present that is mono-substituted benzene is
shown as (due to +I, -I, +M, -M effects)
Naphthalene Series
• Two different mono-nitro derivatives, are
generally formed • The alpha and beta
compounds, also known as 1- nitronaphthalene
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.

At lower temperture it is alpha and

at higher temperatyre it is beta product.
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), - C≡N, -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

Mesomericeffect
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 ofAromatic 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 2- methylpentane which yields
nitromethane, nitroethane, 2-nitropropane, 2-
nitrobutane, 1-nitroisobutane, 1-nitro-3-
methylbutane, 2-nitro-3- methylbutane. • 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 3250C • 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
• TEMPERATURE Temperature effect the
following factors in aromatic nitrations 1. Kinetic
rate constant for various chemical steps increase
with temperature. 2. Solubilities in the acid phase
of both nitrated and unnitrated aromatics probably
increase with temperature 3. Viscosities decrease
and diffusivity coefficients increase with
temperature. interfacial area also changes with
temperature. 4. Equilibrium constants changes
with change in temperature
• 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
Continuous Nitration Batch Nitration Process
Equipments For Technical 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 contained in a drowning tub.
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
[Link] of batch process 1) flexibility 2)
high rate of production 3) process variability
[Link] 1) labour intensive 2) high
capital cost
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
in continuous processes.
[Link] 1) less capital cost 2) less labour
requirement 3) better safety
[Link] 1) less flexibility 2) low rate of
production
Biazzi Nitrator Schmid Nitrator Nitrators
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.

6.
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
• 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. Controlling quantities
• 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. D.V.S
and stability of nitrator charge

Preparation of nitro paraffin's

7.
Preparation Nitrobenzene
8.

Preparation of α- nitro naphthalene