CHANGING THE BAD OLD WAYS

STANLEY E. MANAHAN-453

GREEN CHEMISTRY

Instructor
Dr. Najbul Hoque

 Green Chemistry
Methodologies: Green Synthesis Of Adipic Acid
A feedstock is defined as any renewable, biological material that can be used directly as a fuel, or converted to another
form of fuel or energy product.

An ideal feedstock should be renewable and should not pose any potential hazards.

It should be converted into final products in a few steps with 100% atom economy and 100% yield.

Most feedstocks are derived from petroleum products which are a mixture of hydrocarbons.

The greener way is to use renewable feedstocks.

For example, solar energy and energy from biomass can be used as fuel.

 Green Chemistry
Methodologies: Green Synthesis Of Adipic Acid
Adipic acid used for the manufacture of nylon is conventionally prepared from the petroleum product, benzene (a
carcinogenic compound).

Benzene is oxidised to cyclohexanol and cyclohexanone which on further oxidation with nitric acid in the presence of Ni/
Al2O3 catalyst.

This is a feedstocks to prepare nylon.

This method not only uses benzene (a hazardous volatile compound), it also produces N2O that causes significant
environmental problems.

Conventional method of
synthesis of adipic acid

 Green Chemistry
Methodologies: Green Synthesis Of Adipic Acid
Adipic acid can be synthesised by using an alternative renewable feedstock, glucose.

Which on hydrogenation in the presence of genetically modified Escherichia coli bacteria yields cis, cis-muconic acid.

This acid converts to adipic acid when reduced with hydrogen at 3 atm pressure in the presence of platinum catalyst.

Green synthesis
of adipic acid

 Green Chemistry
Greener Approach Resulted
We successfully skipped use of carcinogenic benzene.

A bacteria performs the conversion of glucose to adipic acid.

Also involves less number of steps.

 Green Chemistry
Methodologies: Use Of Alternative Solvents
Solvents play a very important role in most chemical reactions.

Substances used as solvents are generally volatile and are used in large volumes.

These are carcinogenic and many hydrocarbon solvents have neuro toxicological effects.

In the light of the above hazards of solvents, green chemistry suggests the use of alternative solvents.

Some common alternate green solvents are

 Green Chemistry
Methodologies: Design Of Safer Chemicals
Green chemistry aims at designing chemicals that are eco-friendly and degrade safely after their use.

Analyse the parts of groups are responsible for toxic effect.

Possible ways to design safer chemicals.

I. Replacing the toxic functional group by a less toxic one.

II. Chemical modification of molecule that is toxic. If it is not possible to substitute the toxic functional group, then its
toxicity can be masked using a non-toxic group so that only the desired functional group is released.

III. For a clean environment, it is necessary to design chemicals that can degrade safely in the environment without
releasing toxic end products. This solves the problem of their disposal. Design of biodegradable plastic is an example of
the above type.

 Green Chemistry
Methodologies: Design Of Safer Chemicals
 Green Chemistry
Methodologies: Design Of Alternate Reaction Methodology

ALiquat 336 (Starks' Catalyst) Is A Quaternary Ammonium Salt Used As A Phase Transfer Catalyst And Metal Extraction Reagent.
 Green Chemistry
Methodologies: Use Of Green Reagents

The reaction occurs as follows

This problem is overcome by the use of ClO2 which although a very good disinfectant.

The reaction occurs as follows

 Green Chemistry
Methodologies: Use Of Green Reagents

The reaction use of carcinogenic methylating agents

 Green Chemistry
Methodologies: Use Of Green Reagents
 Green Chemistry
Methodologies: Use Of Ionic Liquids
Inorganic salts consisting of ions, such as NaCl composed of Na+ and Cl- ions, are normally hard, high-boiling solids.

When one or both of the ions are composed of large charged organic molecules, the salts can be liquids at room
temperature and are called ionic liquids.

 Green Chemistry
Methodologies: Use Of Ionic Liquids
The major advantage of using ionic liquids as solvents is, it has very low vapour pressure, which, coupled with the fact
that they can often act as both catalyst and solvent.

Tunability - by varying the cation/anion ratio, type and alkyl chain length properties such as acidity/basicity, melting
temperature and viscosity can be varied to meet particular demands.

Many ionic liquids are stable at temperatures over 300 "C, providing the opportunity to carry out high-temperature
reactions at low pressure.

Ionic liquids that are not miscible with organic solvents or water, easy to separate.

 Green Chemistry
Methodologies: Biocatalyst
Biocatalysis refers to the use of living (biological) systems or their parts to speed up (catalyze) chemical reactions. In
biocatalytic processes, natural catalysts, such as enzymes, perform chemical transformations on organic compounds.
 Green Chemistry
Methodologies: Advantages Of Biocatalyst
By using biocatalysts, biotransformation is carried out under neutral conditions and without the need for elevated
temperatures.

It is used in large scale formation of product. The largest scale industrial biotransformation is currently the conversion of
glucose to fructose by the enzyme glucose isomerase.

The chemical selectivity exhibited by biocatalysts under friendly conditions is the most attractive feature of using it.

Some biocatalysts (dioxygenase enzyme) replaces traditional synthesis (picolinic acids from 2-aminophenols) of some
chemicals.

 Green Chemistry
Methodologies: Use Of Microwave Heating
Traditional energy (heating plate) is non-specific and does not directly attack the bonds or chemicals undergoing the
reaction.

A large portion of the energy goes into heating the reactor, solvents or is dissipated into the environment.

Microwaves have long been used in domestic ovens.

These days microwave and ultrasonic radiation assisted chemical reactions are carried out.

It enables more energy-efficient heating as well as faster and cleaner chemical reactions.

With no direct contact between the chemical reactants and the energy source, it saves lots of energy.

 Green Chemistry
Methodologies: Use Of Microwave Heating
Microwave assisted synthesis requires less energy, generates less waste and avoids the use of solvent.

They are cleaner and eco-friendly with a high product yield and minimum waste.

 Green Chemistry
Methodologies: Use Of Microwave Heating
Microwave assisted synthesis requires less energy, generates less waste and avoids the use of solvent.

They are cleaner and eco-friendly with a high product yield and minimum waste.

 Green Chemistry
Methodologies: Use Of Ultrasound Radiation
Ultrasound radiations (20 kHz to 1 MHz) are very high energy radiations.

These waves propagate through the liquid medium and make the particles of the medium oscillate about their mean
position.

Bubbles are produced inside the liquid.

These bubbles collapse violently and generate very high temperature (5000 °C) and pressure (over 1000 atmosphere).

This effect is called cavitation and the chemical reaction is initiated because of this cavitation effect.