MODULE-3

INTRODUCTION TO UNIT PROCESSES & OPERATIONS

Introduction:

Unit process in organic synthesis deals with major chemical transformations which are of
importance to the chemical industry. In other words unit process deals with the chemical
changes. The unit process is a very useful concept for the technical chemical change and has
been described as the commercialization of a chemical reaction under such conditions as to be
economically profitable. This naturally includes machinery needed and the economics involved,
as well as the physical and chemical phases. The unit operation is physical change connected
with the industrial handling of chemicals or allied materials; it frequently is tied with the unit
processes as when heat flows into an endothermic chemical reaction or out of an exothermic
reaction. The unit operation may also be distinctly separated from the chemical change as when,
by flow of fluid, a liquid is move from one part of an industrial establishment to another.

Chemical engineering, if successfully practiced, requires that the respective unit

processes and operations be applied to the various manufacturing procedures. The study of the
unit operations on the one hand and of the unit processes on the other is characteristic of the
present stage of this branch of engineering. Indeed, the development of chemical manufacturing
procedure is largely coordinated sequence of unit processes and operations that fabricate the raw
materials into the finished product and by-products. In the actually technical application, both
unit processes and unit operations are carried on either simultaneously of independently in
suitable equipments under the guidance of skilled labor supervised by chemical engineers. It is
often called a Chemical Process.

Following is the some of the unit processes:

Combustion Oxidation
Neutralization Silicate formation
Causticization Electrolysis
Double decomposition Calcinations, dehydration
Nitration Esterification (Sulfonation)
Reduction Ammonolysis
Halogenation Sulfonation
Hydrolysis, Hydration Hydrogenation
Alkylation Condensation
Polymerization Diazotization & Coupling
Fermentation Pyrolysis
Aromatization Isomerization
Hydroformylation Ion Exchange
In this chapter we will study about Nitration, Amination, Hydrogenation, Halogenations,
Oxidation, Reduction, Sulphonation, Hydrolysis, Alkylation and Polymerization.
 NITRATION

The nitration reaction serves to introduce one or more nitro groups (-- NO 2) into reacting
molecule.

The nitro group may become attached to carbon to form a nitraromatic or nitroparaffinic
compounds.

It may become attached to nitrogen to form nitramine.

It may become attached to oxygen to form a nitrate ester.

In the nitration process the entering nitro group may replace a number of different monvalent
atoms or groups of atoms. In this topic well concentrate on the nitro group replacing hydrogen
atom, since these are the reactions of greatest importance.

Among the reactions in which nitro group replaces atoms or group other than hydrogen, the
following are shown by way of illustration. Certain alkyl halides can react with silver nitrate to
form the corresponding nitrate esters or with silver nitrite to form the corresponding nitro
compounds as per below:

RCl + AgNO3 RONO2 + AgCl

RCl + AgNO2 RNO2 + AgCl

In the aromatic series the sulfonic acid or acetyl group can, in certain instances, be replaced as
shown in the accompanying equations:
Nitration is one of the most important reactions in the industrial synthetic organic chemistry.
Because nitration products find wide applications as solvents, dyestuffs, pharmaceuticals,
explosives and also serves as s useful intermediates for the preparation of other compounds like
amines which are prepared by reduction of corresponding nitro compounds.

Variety of reagents is used to effect nitration reactions. Those are:

1. Fuming, Concentrated and aqueous nitric acid

 2. Mixtures of nitric acid with sulfuric acid
3. Acetic anhydride
4. Acetic acid
5. Phosphoric acid
6. Chloroform
7. Nitrogen pentoxide
8. Nitrogen tetroxide

Mechanism:

1. HNO3 + 2 H2SO4 NO2+ + H3O+ + 2 HSO4-

2. R H + NO2+ R HNO2+
3. R HNO2 + HSO4-1 R NO2 + H2SO4

Examples:

1.

TNT is used to prepare explosives.

2.

3.