Unit Processes

5th Semester (Session 2020)

B.Sc. Chemical Engineering
Contents of Presentation
• Course Contents
• Recommended Books
• Nitration
 Course Contents & Recommended
Books
• Nitration • Shreve’s Chemical Process
Industries by G.T.
• Esterification
• A Textbook of Chemical Technology
• Animation by G.T. Pandey
• Halogenations • Chemical Process Technology by J.
• Sulphonation Moulijin, M. Makkee and A. Van
Diepen
• Oxidation
• Unit Process in Organic Synthesis
• Hydrogenation by P.H. Groggins
• Introduction to biochemical
engineering process
 Introduction
Chemical processes usually have three interrelated elementary
processes
 Transfer of reactants to the reaction zone
 Chemical reactions involving various unit processes
 Separation of the products from the reaction zone using various unit
operations
What is Unit Process

• Unit process involves principle chemical conversions

leading to synthesis of various useful product and provide

basic information regarding the reaction temperature and

pressure, extent of chemical conversions and yield of

product of reaction, nature of reaction whether

endothermic or exothermic, type of catalyst used.

Nitration
• Nitration involves the introduction of one or more nitro
groups into reacting molecules using various nitrating
agents like fuming, concentrated, aqueous nitric acid
mixture of nitric acid and sulphuric acid in batch or
continuous process.
• Nitration products find wide application in chemical
industry as solvent, dyestuff, pharmaceuticals, explosive,
chemical intermediates.
• Typical Products: TNT, Nitrobenzene, m-dinitrobenzene,
nitroacetanilide, alpha nitronaphthalene, nitroparaffins
Nitration
• Possible bond of nitryl group
– Bonded with carbon forms nitro paraffin and nitro
aromatic compounds
– Bonded with oxygen forms nitrate esters
– Bonded with nitrogen forms nitramine
Substitution Reaction
• Substitution reaction (also known as single
displacement reaction or single substitution
reaction) is a chemical reaction during which one
functional group in a chemical compound is replaced by
another functional group.
Nitrating Agents
1. Fuming, concentrated & aquaous Nitric acid
2. Mixtures of nitric acid with any one of (sulphuric acid,
acetic anhydride, acetic acid, phosphoric acid and
chloroformetc.)
3. Nitrogen Pentoxide N2O5
4. Nitrogen tetroxide N2O4
Applications of Nitration products
• 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.
Reaction Curves

In chemistry and physics, activation

energy is the energy which must be

available to a chemical or

nuclear system with potential reactants

to result in: a chemical

reaction, nuclear reaction, or various

other physical phenomena.

 Nitration of aromatic compounds
The Nitration of aromatic
compounds represented by
following simple reaction
Electron density is the measure of the
+O probability of an electron being present
at a specific location.
• 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.
 Theory of Aromatic Substitution
• According to the theory , a substituent influences the electron density
in following two important ways:
– Inductive effect (-I,+I)
– Mesomeric effect (-M, +M)
Kinetics of Nitration of aromatics
• The kinetics of the nitration of reaction depends upon:
– CONCENTRATION OF NITRIC ACID AND ORGANIC MOLECULE.
– CONCENTRATION OF SULPHURIC ACID.
– ORGANIC SOLVENTS.
Rate = k(HNO3)(ArH)
The generally accepted mechanism is compatible with the data and
my be represented by the following reactions:

HNO3 + 2 H2SO4 NO2 + H3O+ + 2HSO4- (Step – I)

ArH + NO2+ArHNO2+ (Step – II)
ArHNO2+ + HSO4  ArNO2 + H2SO4 (Step – III)
Kinetics of Nitration of aromatics
Nitration in a mixed acid (mixture of nitric and sulfuric acid):
• Compounds which are nitrated at a 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.
 Nitration of Paraffinic Hydrocarbons
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.
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
Process Equipment for Technical
Nitration
• Technical nitration can be discussed as
– Batch processes

• Nitration is usually done in closed cast iron or steel vessels. Modern practice is
to use mild carbon steel.
• Nitrator consists of a cylindrical 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.
• 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.
Process Equipment for Technical
Nitration
– Continuous process.

• 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.
Nitrators
• Schmid Nitrator • Biazzi Nitrator
• The material to be nitrated is fed into • In this apparatus the turbine type
the top of the nitrator and is agitator provides intensive agitation.
immediately drawn down through the A vortex is formed in the center about
sleeve and thoroughly mixed with the the agitator shaft.
spent acid and reacting material.
• The reactants fed from the top are
• In the bottom of the nitrator fresh immediately drawn into the vortex
mixed acid is fed in and mixed with thoroughly mixed and circulated
the other reactant by means of down through the center of the bank
agitator and baffles provided. of cooling coils.
• The reacting material then pass • The high velocity imparted to the
upwards with high velocity through nitrator contents makes for efficient
the tubes surrounded by refrigerated mixing and heat transfer. Due to
brine. Product and spent acid are throwing of cold body on hot body
withdrawn continuously from the flashing and evaporation takes place
nitrator through the overflow line. so you have to provide suction line for
vapours.
Nitrators
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 the nitration
must be enough to satisfy the stoichiometric requirements
of nitration reaction. It is usually present in access in
order to maintain reasonably fast overall reaction.
• 2. The amount of 100 % 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, 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 Nitrobenzene

Summary
•Overall transformation : Ar-H to Ar-NO2
•Reagent : for benzene, HNO3 in H2SO4 /
heat
•Electrophilic species : the nitronium ion
(i.e. NO2+) formed by the loss of water from
the nitric acid
Uses of Nitrobenzene
• Nitrobenzene is also used to mask unpleasant odors in
shoe and floor polishes, leather dressings, paint solvents,
and other materials. Redistilled, as oil of mirbane,
nitrobenzene had been used as an inexpensive perfume
for soaps. It has been replaced by less toxic chemicals for
this purpose.
• A significant merchant market for nitrobenzene is its use
in the production of the analgesic paracetamol (also
known as acetaminophen) (Mannsville 1991).
Preparation of Nitroparaffins
• Another reaction of commercial importance is the nitration of
alkanes to give nitroparaffins. Such reactions usually are carried
out in the vapor phase at elevated temperatures using nitric
acid (HNO3) or nitrogen tetroxide (N2O4) as the nitrating agent:

• Nitration of propane, the main products are:

– Nitro-methane
– Nitro-ethane
– Nitro-propane
– 2-nitropropane
There are five processes
involve in the preparation
of nitroparafins:
1. Nitration
2. Products Recovery
3. Products purification
4. Products Separation
5. Reactant Recovery
Uses of Nitroparaffins
• Production of the four commercial nitroparaffins is by vapor‐
phase nitration of propane with nitric acid. Some 41,000 ton
of mixed nitroparaffins can be produced annually.
• All the nitroparaffins are flammable liquids.
• Their principal hazard is by inhalation.
• Special attention is required for handling nitromethane
because it can be detonated under certain circumstances.
• The bulk of nitroparaffin production is used for synthesis of
other chemical products. Nitromethane is useful as a fuel in
drag racing and model airplanes, however, and nitroethane
and 1‐nitropropane see use as solvent in coatings.
Preparation of -nitro naphthalene