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 (-- NO2) 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.

AMINATION

An introduction of an amino group (-NH2) in organic compound is called Amination.

Amination involves the synthesis of amines.

Amines may be defined as derivative of ammonia, where one or more of the hydrogen are
replaced by alkyl, aryl, hydroaryl, aralkyl, or heterolytic group.

Amines can be produced by reducing nitro, nitroso, hydroxylamino, azoxy, azo and hydroazo
compounds, as well as oximes, amides, nitriles, and azids. In each case carbon to nitrogen bond
already exists.

Amines may also be formed by reacting compounds containing certain liable groups with
ammonia.

Amines are divided into three classes- primary, secondary, and tertiary- depending upon the
number of replaced hydrogen in the parent substance ammonia. Primary amines contain two
remaining hydrogen atoms attached to the ammonia nitrogen, secondary amines contain one, and
tertiary amines have none remaining.
Amides, in contrast to amines, are derivatives of ammonia, where the hydrogen has been
replaced by an organic acid-derive groups, acyl, aroyl, heteroyl, sulfonyl, etc. An amide is one
which two hydrogen of the parent ammonia have been replaced. Amides generally prepared by
Ammonolysis reactions.
A great variety of reduction methods have been used for the preparation of amines. Among these
are:
1. Metal & acids
2. Catalytic
3. Sulfide
4. Electrolytic
5. Metal and alkali
6. Sodium hydrosulfite
7. Sulfite
8. Metal hydrides
9. Sodium and sodium alcoholate
10. Strong caustic oxidation reduction
11. Hydrogenated quinolines and naphthalene

HYDROGENATION

The unit process hydrogenation (as contrasted with the general term reduction) specifically refers
to the chemical reaction of a substance with molecular hydrogen in the presence of a catalyst.

The process includes reactions

In which hydrogen simply adds to a molecule (hydrogenation),

In which molecules are cleaved by hydrogen (hydrogenolysis or destructive
hydrogenation),
Reactions such as isomerization, cyclization, and the like which occur in the presence of
molecular hydrogen and catalysts.
Other reactions which involve molecular hydrogen and catalysts are reductive amination
(hydroammonolysis), hydroformylation (Oxo and Oxoyl reactions), and the synthesis of
ammonia.

Hydrogenation, in the exact usage of the designation, is synonymous with reduction, which is the
term usually applied to a reaction in which oxygen or some other element (most commonly
nitrogen, sulfur, carbon, or halogen) is withdrawn from or hydrogen is added to a molecule.
Examples of important methods of reduction other than catalytic hydrogenation are:

1. By metals in acid or basic solution,

2. By alkali metals in alcoholic solution,
3. By electrolysis,
4. By alkali metals and hydrazine,
5. By complex metal hydrides, and
6. By hydrogen transfer

Examples,

HALOGENATIONS

Halogenation may be defined as the process whereby one or more halogen atoms are introduced
into an organic compound.

The preparation of organic compounds containing fluorine, chlorine, bromine, and iodine can be
accomplished by a variety of methods. The conditions and procedures differ, not only for each
member of the halogen family but also with the type and structure of the compound undergoing
treatment.

As may be observed from the following examples, halogenations may involve reactions of (1)
addition, (2) substitution, i.e., of hydrogen, (3) replacement, i.e., of groups, for example, the
hydroxyl or sulfonic acid group.
From the preceding formulations, it becomes clear that each type of reaction may involve not
only a specific halogenating agent but also a suitable catalyst or activator.

Many of the catalysts are halogen carriers. Iron, antimony, and phosphorus, which are able to
exist in two valences as halogen compounds, are used as they are less stable at the higher valence
and give up part of their halogen during the process.

In the presence of free halogen, such compounds alternately add on and give up halogen to carry
on the reaction.

Iodine, bromine, and chlorine which are capable of forming mixed halogens are also frequently
employed as catalysts in halogenation processes.

Active carbon, clays, and other compounds also serve to catalyze halogenation processes. Where
the halogen is energized to an activated state by means of light, heat, nuclear energy, or free
radicals, it may then proceed to react by addition or by substitution without the need of a
catalyst.

Chlorination:

Chlorination may be defined as the process whereby one or more chlorine atoms are introduced
into an organic compound.

A number of methods are available for organizing the material relating to chlorination processes,
all of which are necessarily complex. The most important methods for preparing chlorine
compounds are the following:

1. Direct action of chlorine gas:

2. Hydrochloric acid as a chlorinating agent:

 3. Sodium hypochlorite as a chlorinating agent:

4. Chlorination with Phosgene (COCl2)

5. Chlorination with Thionylchloride (SOCl2)

6. Chlorination with Sulfuryl chloride

7. Chlorination with phosphorous chloride

Bromination:

Bromination may be defined as the process whereby one or more bromine atoms are introduced
into an organic compound.

In many instances, brominations may be carried out in a manner similar to that employed for the
preparation of chlorine derivatives. Thus, bromine, bromides, bromates, and alkaline
hypobromites may be employed instead of the corresponding chlorine compounds.

Bromine dissolved in water is frequently employed, particularly in the bromination of phenols.

Potassium bromide is generally added to aqueous bromine solutions to increase the concentration
of soluble molecular halogen.

Iodination:

Iodination may be defined as the process whereby one or more iodine atoms are introduced into
an organic compound.

The methods employed in iodination differ somewhat from those for chlorination or
bromination. The relatively weak C-I bond, which is indicated by the low heat of reaction and
which distinguishes iodine from other halogens, makes permanent, direct union of carbon to
iodine by the replacement of hydrogen possible only in exceptional cases.

Catalysts are only infrequently employed in iodination, phosphorus being the principal
accelerator.

Iodine monochloride, because of its activity under mild operating conditions, is a useful catalyst
for the iodination of amino compounds.

Fluorination:

Fluorination may be defined as the process whereby one or more fluorine atoms are introduced
into an organic compound.

Fluorine acts directly on hydrocarbons to produce fluorides, but the reaction is violent and
constitutes an explosion hazard.

Some reactions can be carried out by careful control of temperature and fluorine concentration,
but even then there may be a cleavage of carbon-carbon bonds.

The bonds holding the atoms in the fluorine molecule are stronger than in the other halogens; but
once the reaction is initiated and fluorine atoms are available, they combine more readily with
hydrogen and hydrocarbons than do the halogens of higher molecular weight.

Furthermore, the new bonds that are formed are so strong and the heat liberated is so great that
precautions must be taken to moderate the reaction so as to keep it under control.

OXIDATION

Oxidation reaction is referred to the reaction in which loss of electrons or an increase in

oxidation state by a molecule, atom or iron.

Oxidation reactions are commonly associated with the formation of oxides from oxygen
molecule, or addition of oxygen atom in the reaction.

In organic reaction, oxidation reaction includes dehydrogenation, molecular condensation,

Peroxidation.
When an organic compound is oxidized, the reagent that brings about the transformation is called
an oxidizing agent.

There are various oxidation agents are available i.e. chromate ion, permanganates, dichromate
ion, hydrochlorcus acid and its salts, sodium chlorite, chlorine oxide, chlorates, peroxides, ozone,
fuming sulfuric acid, copper salts etc.

SULPHONATION

Sulfonation may be defined as any chemical process by which the sulfonic acid group -S020H, or
the corresponding salt or sulfonyl halide group (e.g., -S02Cl), is introduced into an organic
compound.

These groups may be situated on either a carbon or a nitrogen atom.

Salfonates of the second type (e.g., RNHS020Na) are termed N-sulfonates or sulfamates.

Particular types of sulfonation include sulfochlorination (introduction of an -S02Cl group into an

alkane using sulfur dioxide and chlorine), halosulfonation (reaction of a halosulfonic acid-
ClS03H or FS03H with an aromatic or heterocyclic compound to introduce an -S02Cl or an -S02F
group), sulfoxidation (use of sulfur dioxide and oxygen to sulfonate an alkane), sulfoalkylation,
sulfoacylation, and sulfoarylation (introduction of sulfoalkyl, sulfoacyl, or sulfoaryl groups).

It is convenient to classify sulfonates into four main chemical types:

(1) Aliphatic and Alicyclic,

(2) Aromatic,
(3) Heterocyclic, and

(4) N-sulfonates or sulfamates.

There are four general procedures for preparing sulfonates:

(1) Treatment of an organic compound with S03 or a compound thereof;

(2) Treatment with a compound of S02;

(3) Condensation and polymerization methods;

(4) Oxidation of organic already containing sulfur in a lower state of oxidation, such as RSH.

Sulphonating agents:

These agents may be summarized as follows:

1. Sulfur trioxide and compounds thereof.

a. Sulfur trioxide, oleum, concentrated sulfuric acid (S03 plus water).

b. Chlorosulfonic acid (SO3 plus HCI).

c. Sulfur trioxide adducts with organic compounds.

d. Sulfamic acid.

2. The sulfur dioxide group.

a. Sulfurous acid, metallic sulfites.

b. Sulfur dioxide with chlorine.

c. Sulfur dioxide with oxygen.

3. Sulfoalkylating agents.

a. Sulfomethylating agents (hydroxy- and aminomethanesulfonates).

b. Sulfoethylating agents (hydroxy-, chloro-, and methylaminoethanesulfonates; ethylenesulfonic
acid).

c. Miscellaneous sulfoalkylating agents; sulfoacylation; sulfoarylation; sulfatoalkylation.

HYDROLYSIS

The term hydrolysis is applied to reactions of both organic and inorganic chemistry wherein
water affects a double decomposition with another compound, hydrogen going to one
component, and hydroxyl to the other. In other words water reacts, where in two compounds in
forms, in which hydrogen going to one component and hydroxyl ion going to 2nd compound.

XY + H2O HY + XOH

We may recognize, then, five types of hydrolysis:

1. Pure hydrolysis where water alone is used.

2. Hydrolysis with aqueous acid, dilute or concentrated.

3. Hydrolysis with aqueous alkali, dilute or concentrated.

 4. Alkali fusion, with little or no water but at high temperatures.

5. Hydrolysis with enzymes as catalysts.

They are classified into another two hydrolysis.

(1) Hydrolysis conducted at liquid phases and

(2) Those taking place in the vapor phase

Hydrolysis of any ester yield carboxylic acid and alcohol. This process is very slow. If
hydrolysis is conducted in diluted aqueous solution alkali or inorganic acid, it gives yield very
rapidly.

ALKYLATION

Alkylation may be defined as the introduction of an alkyl radical by substitution or addition into
an organic compound.

Alkylation is of six general types, depending on the linkage effected:

1. Substitution for hydrogen in carbon compounds. This is nuclear alkylation when aromatic
hydrogen is substituted. The carbon of the alkyl is bound to carbon of either aliphatic or
aromatic compounds. This is carbon-to-carbon alkylation and includes the alkylations
hereto classified under the Friedel-Crafts reaction, e.g.,

2. Substitution for hydrogen in the hydroxyl group of an alcohol or a phenol. Here the alkyl
is bound to oxygen, e.g.

3. Substitution for hydrogen attached to nitrogen. Here the alkyl is bound to trivalent
nitrogen, e.g.,
 4. Addition of an alkyl halide or an alkyl ester to a tertiary nitrogen compound. Here the
binding of the alkyl is to the nitrogen, and the trivalent nitrogen is often assumed to be
converted to a pentavalent linkage. In reality, the nitrogen possesses four ordinary
covalence and one electrostatic bond, e.g.,

5. Alkyl-metallic compounds. Here the alkyl is bound to the metal, e.g.,

6. Miscellaneous alkylations. In mercaptans, the alkyl group is bound to sulfur; in the alkyl
silanes, it is bound to silicon:

n-C 12H25-SH and C2H5-SiCl3

Alkylating Agents:

1. Olefins
2. Alcohols
3. Alkyl Halides
4. Alkyl Sulfates
5. Aralkyl Halides
6. Arylsulfonic Alkyl Esters
7. Alkyl Quaternary Ammonium Compounds
8. Metallic Alkyl Derivatives

POLYMERIZATION

Polymerization reactions are either condensation reactions or addition reactions.

The polymer formation in condensation polymerization proceeds stepwise, the various
intermediates, dimer, trimer, etc., existing as stable molecules until the next reaction step. Small
molecules, usually water, are split off at each step of the reaction.
Addition polymerization is characterized by the fact that the reaction from monomer to polymer
occurs without elimination of by-products. During the addition reaction, no stable compounds
are formed because the intermediates are comparatively short-lived radicals or ions.
The formation of the polymer chain is usually accomplished in a fraction of a second and in one
single sweep. Polymerization at the double bond is a typical addition reaction of this type.
Certain addition reactions, which proceed by first opening the ring of a cyclic compound, follow
a stepwise procedure. Thus they occupy a position in between the two reaction types, showing
certain similarities to each. A form of addition polymerization is that of copolymerization in
which two or more different monomers are linked together, either at random or alternating, to
form one single copolymer chain or network:

... AABABBBBABABBAAABBBAB . .. random

... ABABABABABABABAB . " alternating

Recently two special types of copolymerization have been investigated intensely and have shown
promise for use in large-scale industrial production. They are called block polymerization and
graft polymerization, respectively. In block polymerization, sequences of one type of monomer
are prepolymerized and then joined to the prepolymerized sequences of another monomer:

A typical example of graft polymerization is one in which sequences of monomer B are grafted
onto the main chain consisting of A units:

Finally a type of addition polymerization calling for the employment of stereo specific catalysts
has recently aroused much interest in the laboratory as well as in industry. With the aid of such
catalysts, an addition polymerization yields certain polymers in which the main chain as well as
the chemical substituent are situated in a highly ordered spatial pattern. Polymers of physical and
chemical characteristics are thus obtained which contrast markedly from those formed in normal
polymerizations.