INTRODUCTION
Chemical process is combination of unit processes and Unit
operation.
A process may require many unit operations to obtain the desired
product from the starting materials, or feedstocks.
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.
Unit operations involve the physical separation of the products
obtained during various unit processes. Various unit processes in
chemical industries are given in following Table
SULPHONATION
Overall transformation: Ar/R-H to Ar/R-SO3H
Reagents: Conc. H2SO4, chlorosulfonic acid, metallic sulfates,etc.
Electrophilic species: SO3 which can be formed by the loss of water from the sulphuric acid.
It is exothermic, but not highly corrosive.
Unlike the other electrophilic aromatic substitution reactions, sulphonation is reversible.
Reaction mechanism
Typical conditions involve heating the aromatic compound with sulfuric acid.
Sulfur trioxide or its protonated derivative is the actual electrophile in this electrophilic aromatic
substitution.
To drive the equilibrium, dehydrating agents such as thionylchloride can be added.
Applications:
In production of linear alkyl benzene sulphonates, toluene sulphonates, saccharin,etc.
REACTION MECHANISM
HALOGENATION
Overall transformation: Ar/R-H to Ar/R-X
Reagents: Chlorine, hypochloite ,hydrobromic acid,etc.
It is carried out in the presence of a catalyst which acts as a halogen carrier.
The main function of halogen carrier is to polarise the halgen-halogen bond and
generate the electrophile.
Halogenation of aromatic compounds differs from the halogenation of alkenes
,which do not require a lewis acid catalyst.
Halogenation by reaction type:-
1)Free radical halogenation
2)Addition of halogens to alkenes and alkynes
3) Halogenation of aromatic compounds
Applications:
In formation of halogen derivatives such as CCl4, CFCs, Alkyl halides,etc.
REACTION MECHANISM
NITRATION
• Overall transformation: Ar/R-H to Ar/R-NO2.
• Reagents: Fuming Conc. HNO3, mixture of HNO3 & H2SO4.
• It involves introduction of nitro group into a compound.
• Aromatic compounds are nitrated via EAS mechanism.
• The formation of a nitronium ion from HNO3 & H2SO4 and subsequent
reaction of the ion with the sample takes place.
• Nitration reactions are notably used for the production of
explosives, for example the conversion of guanidine to nitroguanidine
and the conversion of toluene to trinitrotoluene.
• Applications: The nitrated derivatives have applications in industry as
solvents, explosives, TNT, Nitro benzene, etc.
REACTION MECHANISM
Step 1: Nitric acid accepts a proton from sulphuric acid and then
dissociates to form nitronium ion.
Step 2: The nitronium ion acts as an electrophile in the process
which further reacts with benzene to form arenium ion.
Step 3: The arenium ion then loses its proton to Lewis base forming
nitrobenzene.
Examples:-
ESTERIFICATION
When alcohols or phenols reacts with carboxylic acid in presence of acidic
media formation of ester take place this process is know as Esterification
reaction.
Reversible reaction.
Known as (ficher-speier Esterification).
Uses of Esterification reaction
1.Polymer industry
Terylene,PMMA and cellulose ester.
2.Food industry
Synthetic oils,soap and artificial sweetening agent.
3.Pharmaceutical industry
Aspirin- in treatment of fever,as pain killer,to prevent heart attacks.
EXAMPLES OF ESTERIFICATION REACTION
MECHANISM OF REACTION
HYDROGENATION
• When unsaturated organic compound reacts with
Hydrogen gas in presence of a catalyst such as Ni,Pd,or
Pt.formation of less unsaturated organic compound take
place .these types of reaction is called Hydrogenation.
• Industrial application of Hydrogenation reaction
Food industry
Processing of vegetable oils.
Petro chemical industry
To convert alkenes and aromatics into saturated alkanes
and cycloalkanes.
Organic chemistry
EXAMPLES OF HYDROGENATION REACTION
MECHANISM OF REACTION AND EXAMPLE
OXIDATION
• In reference to organic molecules, carbon atom gain bond to
more electro negative elements, most commonly oxygen.
• some important oxidising agents.
KMnO4,K2Cr2O7, conc.H2So4,O2,O3, H2O2,Mno2, Oso4,pcc,m-cpba
etc.
• Important products of oxidation reaction and their application
1. ketone
• Acetone-nail paint remover and for acne treatment.
• Organic solvent.
2. Aldehyde
• Formaldehyde + 37% H2O=formalin.
• Germicide, fungicide and insecticide for plant and vegetables.
• For bakelite,u.f resin and melamine.
• Solvent
• Perfumes and flavouring agent.
3.Vanillin
• Flavouring agent of vanilla beans.
4.Benzoic acid
• It’s salts are used as food preservatives.
5.Acetic acid
• Solvent
• Food preservative.
• 3-9% acetic acid by volume is vinegar.
TABLE OF IMPORTANT OXIDATION REACTIONS
HYDROLYSIS
• Hydrolysis is a chemical reaction that occurs between water
and another compound.
• During the reaction, chemical bonds are broken in both
molecules, causing them to break apart. The water molecule
splits to form positively Charged hydrogen (H+) and
negatively charged hydroxide (OH-) ions, and the other
molecule splits into two simpler sections, also with positive
and negative charges. H+ and OH- ions attach to each of
these sections.
• Hydrolysis is used both in inorganic and organic
chemical industry. Typical application is in oil and
fats industry during soap manufacture where
hydrolysis of fats are carried out to obtain fatty acid
and glycerol followed by addition of sodium
hydroxide to form soap.
• Other application is in the manufacture of amyl
alcohols. Some of the major product using hydrogen
is methanol, propane, butane, production of alcohol.
• Various types of hydrolysis reaction may be pure hydrolysis,
hydrolysis with aqueous acid or alkali, dilute or concentrated,
alkali fusion, hydrolysis with enzyme and catalyst.
• Preparation of ethanol from ethylene:
catalyst
CH2 = CH2(g) + H2O(g) CH3CH2OH(g) + H
H = - 45 kJ mol -1
POLYMERIZATION
Polymerization is a chemical process by which polymer
molecule is formed the same or different types of monomers.
Polymerization maybe carried out either with single monomer
or with co monomer.
Polymerization reaction can be addition or condensation
reaction.
Various polymerization methods may be bulk, emulsion,
solution, suspension.
Application :
Manufacture of polymer, synthetic fiber, synthetic rubber,
polyurethane, paint and petroleum industry for high octane
gasoline.
Typical important products from polymerization are :
Polyethylene, PVC, poly styrene, nylon, polyester, poly
butadiene, poly styrene, phenyl, urea, melamine and alkyd
resins epoxy resin, silicon polymers, poly vinyl alcohol etc.
Example of polymerization reaction :
“WHAT IS BHOPAL GAS TRAGEDY ?”
• The Bhopal gas tragedy (commonly referred to as Bhopal disaster) was
a gas leak incident in India, considered one of the world's worst industrial
catastrophes.
• It occurred on the night of 2nd–3rd December 1984 at the Union Carbide
India Limited (UCIL) pesticide plant in Bhopal, Madhya Pradesh.
• A leak of methyl isocyanate (MIC) gas and other chemicals from the plant
resulted in the exposure of hundreds of thousands of people.
THE ACCIDENT
• During the night of 2–3 December 1984, water entered Tank
E610 containing 42 tons of MIC.
• The resulting exothermic reaction increased the temperature
inside the tank to over 200°C (392 °F) and raised the pressure.
• About 30 metric tons of methyl isocyanate (MIC) escaped
from the tank into the atmosphere of Bhopal in 45 to 60
minutes.
FACTORS LEADING TO THE GAS LEAK
• Storing MIC in large tanks and filling beyond recommended
levels,
• Poor maintenance,
• Failure of several safety systems,
• Safety systems being switched off to save money—including the
MIC tank refrigeration system which could have mitigated the
disaster severity,
• Plant location close to a densely populated area,
• Undersized safety devices,
• The dependence on manual operations,
THE DEVASTATION
The official immediate death toll was 2,259 and the government
of Madhya Pradesh has confirmed a total of 3,787 deaths
related to the gas release.
Others estimate 8,000 died within two weeks and another 8,000
or more have since died from gas-related diseases.
A government affidavit in 2006 stated the leak caused 5,58,125
injuries including 38,478 temporary partial and approximately
3,900 severely and permanently disabling injuries.
2,000 bloated animal carcasses had to be disposed.
HEALTH EFFECTS
• Short term health effects
– Apart from MIC, the dense gas cloud may have contained
• phosgene,
• hydrogen cyanide,
• carbon monoxide,
• hydrogen chloride,
• oxides of nitrogen,
• monomethyl amine (MMA) and
• carbon dioxide, either produced in the storage tank or in the
atmosphere.
– The initial effects of exposure were coughing, vomiting, severe eye
irritation and a feeling of suffocation.
– The acute symptoms were burning in the respiratory tract
and eyes, blepharospasm, breathlessness, stomach pains and
vomiting.
Bibliography
• http://www.hindustantimes.com/india/bhopal-gas-tragedy-burning-of-toxic-
waste-begins-secretly/story-6iqgPOBcpuQvF0aErdwYYJ.html
• http://timesofindia.indiatimes.com/city/bhopal/Sabotage-led-to-Bhopal-gas-
tragedy-Former-plant-manager-of-UCIL/articleshow/53303945.cms
• http://www.dnaindia.com/analysis/column-bhopal-gas-tragedy-will-the-
suffering-ever-end-2040370
• http://byjus.com/chemistry/benzene-reactions/
• http://nptel.ac.in/courses/103107082/module1/lecture3/lecture3.pdf
• https://en.wikipedia.org/wiki/Unit_operation
• BOOKS:- Organic Chemistry by Dr.O.P Tandon & R.T Morrison , Unit
Processes in Organic Synthesis. By P. H. Groggins.
•