University of Engineering & Technology Lahore, KSK Campus
Unit Processes
Engr. Qazi M Omar
University of Engineering & Technology Lahore, KSK Campus
NITRATION
University of Engineering & Technology Lahore, KSK Campus
Topics to be covered
• Introduction
• Nitrating Agents
• Mechanism of Nitration
• Aromatic and Paraffinic Nitration
• Kinetics of Aromatic Nitration
• Thermodynamics of Nitration
• Equipment For Nitration Processes
• Industrial Applications
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INTRODUCTION
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Introduction
• The reaction between nitrating agent and another
reacting compound that results in one or more nitro
(--NO2) groups chemically bonded to an atom in this
compound.
• The nitro group (--NO2) may become chemically
attached to a carbon (nitroaromatic or
nitroparaffinic), oxygen (nitrate ester), or nitrogen
(nitramine) .
• A hydrogen atom is often replaced by the nitro group
and this is of great technical importance.
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Introduction (Contd.)
• Three general reactions summarize nitration
chemistry:
1. Carbon nitration:
2. Oxygen nitration:
3. Nitrogen nitration:
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NITRATING AGENTS
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Nitrating Agents
• A variety of reagents can be used for nitration.
• These include:
✓
Concentrated and aqueous nitric acid.
✓
Mixtures of nitric acid with sulfuric acid, acetic
anhydride, acetic acid, phosphoric acid and
chloroform.
✓
Nitrogen Pentoxide (N2O5) and nitrogen tetroxide (N2O4).
• For selecting suitable nitrating agent it is desirable
to know:
✓
Species present in the system for reaction.
✓
Mechanism of the reaction with the selected nitrating agent
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Nitryl Ion
• Mixture of nitric acid and sulfuric acid (mixed
acid) is the most important nitrating medium.
• Nitric acid exists in strong sulfuric acid as the
nitryl ion NO2+.
• In weaker solutions of sulfuric acid, ionization
of nitric acid is very slight but rapidly
increases as the sulfuric acid becomes more
concentrated.
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MECHANISM OF NITRATION
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Mechanism of Nitration
• The mechanism of nitration depends on
the reactants and the operating
conditions.
• The nitration reactions usually follow two
types of mechanism:
1. Ionic
2. Free-radical
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Mechanism of Nitration (Contd.)
• Ionic nitration is commonly used for
aromatics, heterocyclic compounds,
hydroxyl compounds and amines.
• Nitration of paraffins, cycloparaffins and
olefins frequently involves free-radical
mechanism.
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NITRATION OF AROMATICS
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Ionic Nitration of Aromatics
• Most ionic nitrations are performed at 0-120°C. For
nitrations of most aromatics, there are two liquid
phases: an organic and an acid phase.
• Sufficient pressure is provided to maintain the
liquid phases. A large interfacial area between the
two phases is needed to accelerate transfer of the
reactants to the interface and of the products from
the interface.
• The nitration agent is an electrophilic reactant,
therefore the substitution will be electrophilic
aromatic substitution.
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Electrophilic Aromatic Substitution
• The characteristic reaction of benzene is
electrophilic aromatic substitution, a hydrogen
atom replaced by an electrophile (E+).
• Benzene has six π electrons and these loosely
bound π electrons make the benzene ring electron
rich and so reacts with electrophiles.
• Unlike addition reactions, substitution of hydrogen
keeps the aromatic ring intact.
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Mechanism of Substitution Reaction
• Regardless of the electrophile used, all
electrophilic aromatic substitution
reactions occur by the same two-step
mechanism:
+
1. Addition of electrophile (E ) to form a
resonance-stabilized carbocation.
2. Deprotonation with base.
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Formation of Electrophile
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Electrophilic Aromatic Substitution
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Ionic Nitration of Aromatics
• NO2+ attacks an aromatic compound (ArH) as follows:
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Substitution of Substituted Benzenes
• Many substituted benzene rings undergo
electrophilic aromatic substitution.
• Already present substituent either increases
or decreases the electron density in the
benzene ring.
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Substitution of Substituted Benzenes
• A substituent affects two aspects of the
electrophilic aromatic substitution
reaction:
1. The rate of reaction: A substituted
benzene reacts faster or slower than
benzene itself.
2. The orientation: location of new group
with respect to the existing substituent.
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Questions for YOU!!!!
• How large interfacial area can be practically
provided between two phases during
nitration of aromatics????
• Which factors decide the position of
substitution (ortho, para or meta) in the
substituted benzene????
• What are the benefits of using sulfuric acid
with nitric acid during nitration reaction????
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KINETICS OF AROMATIC
NITRATION
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Kinetics of Aromatic Nitration
• The rate of nitration reaction can be written as:
• So, the kinetics of aromatic nitrations are functions
of temperature, which affects the kinetic rate
constant, and also of the concentration of both the
acid and hydrocarbon phases.
• In addition, a larger interfacial area between the
two phases increases the rate of nitration since the
main reactions occur at or near the interface.
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Kinetics of Aromatic Nitration
• The reaction rate also depends on sulfuric
acid concentration.
• Reaction rate rises sharply with increasing
sulfuric acid concentration and reaches a
maximum value at 90% H2SO4.
• This increase in reaction rate is due to the
increase in concentration of nitryl ion
(electrophile).
• But the rate start to decrease at
concentration higher than 90%.
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Question for YOU!!!!
• Why rate of reaction decreases with
sulfuric acid concentration higher than
90%?????
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Kinetics of Aromatic Nitration
• The viscosities and densities of the two
phases and the interfacial tension between
the phases are important physical
properties affecting the interfacial area.
• Such properties are, of course, dependent
on both temperature and the respective
compositions of the phases.
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Question for YOU!!!!
• How density, viscosity and interfacial
tension will effect the interfacial area???
How these parameters should be changed
to increase interfacial area?????
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