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Green Chemistry Lecture 1 & 2

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What is Green Chemistry?

• Green or Sustainable Chemistry is a term related to the creation of


chemical products and processes that reduce or eliminate the use and
production of. harmful substances.
• To be called "green," each reaction should have three green components:
1. solvent,

2. reagent / catalyst and energy

3. Consumption

• Green chemistry is not a separate scientific discipline, but a responsible


interdisciplinary approach to science, based on chemical, ecological and
social responsibility, which enables creativity and the advancement of
innovative research
Trends in Green Chemistry
• Research in the field of catalytic and biocatalytic reactions.
• Seeking new raw materials, harmless and renewable, such as biomass.
• Designing less toxic eco-compatible chemicals.
• Finding and testing new alternative, non-toxic and renewable reaction
media such as water, ionic liquids and supercritical fluids.
• Finding and testing new alternative reaction conditions, such as
microwave, ultrasound and light reacting.
• Exploration of alternative routes for the purification of poisoned air
and water to improve their quality, such as photocatalytic reactions.
12 Principles of Green Chemistry
• Developed by Paul Anastas and John Warner of EPA.
Principles of Green Chemistry
1.Prevention
• It is better to prevent waste than to treat or clean up waste after it has
been created.
• "Dirty reactions" during which toxic reactants and solvents are used, and
due to the harsh reaction conditions, a large number of toxic by-products
are formed.
• Halogenation, oxidation, alkylation, nitration and sulfonation.

• The paint and varnish industry already produces solvent-free paints and
lacquers. The detractors industry has already thrown out all phosphorus-
containing detergents. Asbestos is no longer used in practice.
Principles of Green Chemistry
1.Prevention Previously NaBH4

Sertralone
Principles of Green Chemistry
2. Atom Economy
• Synthetic methods should be designed to maximize the
incorporation of all materials used in the process into the final
product.
• Old synthesis of ibuprofen is low economic cost, because the
utilization of input raw materials is only about 40%.
• In the 1990s a new "green" method of ibuprofen synthesis was
developed, involving only three steps (yield up to 99%).
Principles of Green Chemistry
1-isobutylbenzene

1-(4-isobutylphenyl)ethanone

1-(4-isobutylphenyl)ethanol
Principles of Green Chemistry
3. Less Hazardous Chemical Syntheses
• Wherever practicable, synthetic methods should be designed to use and
generate substances that possess little or no toxicity to human health and
the environment.
• Most chemical synthesis reactions, which usually take place in multiple
stages, use toxic reagents which may contaminate product to certain extent.
• A new Asahi Kasei's polycarbamate synthesis (PC) process is conceptually
simple, based on the substitution of toxic carbonyl dichloride (COCl2) with
CO2.
• This process also results in the removal of dichloromethane (CH2Cl2) as a
solvent.
Principles of Green Chemistry
3. Less Hazardous Chemical Syntheses

1,3-dioxolan-2-one
dimethyl carbonate

diphenyl carbonate
Principles of Green Chemistry
4. Designing Safer Chemicals
• Chemical products should be designed to effect their desired function
while minimizing their toxicity.
• Minimizing toxicity, while maintaining function and efficiency, can be one
of the most challenging aspects of designing safer products and processes.
• This principle is used in the development of new insecticides and
pesticides that are specific to target organisms.
• Another example is the use of highly toxic organic tin-based organic
compounds (Sn), previously coated on the outside to prevent the capture
of seaweed and plankton. These organic compounds have been replaced by
a product called Sea-Nine which is completely degradable and non-toxic.
Principles of Green Chemistry
5. Safer Solvents and Auxiliaries
• The use of auxiliary substances (e.g., solvents, separation agents, etc.) should
be made unnecessary wherever possible.
• In Chromatographic Separation large quantities of solvents are used which
causes environmental disposal issues so use environment friendly solvents.
• The solvent should be chemically and physically stable, low volatility, easy to
use and easy to recycle.
• it is promising to replace the known organic solvents with recyclable solvents,
which are ionic liquids - salts at room temperature in the liquid state.
• Ionic liquids have low vapor pressure, do not vaporise and do so easily,
resulting in safer chemical processes
Principles of Green Chemistry
5. Safer Solvents and Auxiliaries
Principles of Green Chemistry
6. Design for Energy Efficiency
• Energy requirements of chemical processes should be recognized for
their environmental and economic impacts and should be
minimized. If possible, synthetic methods should be conducted at
ambient temperature and pressure.
• The oil crisis in 1973 has initiated the development of a number of
processes in which energy savings are taken into account, with the
aim of exploiting every kJ of energy in the production process.
Principles of Green Chemistry
6. Design for Energy Efficiency
Principles of Green Chemistry
7. Use of Renewable Feedstock
• A raw material or feedstock should be renewable rather than depleting
whenever technically and economically practicable.

• It is more convenient to use renewable raw materials than a variety of plastic


materials, and then to waste away the waste materials. Because of this, the
making of biodegradable plastic materials is a current trend.

• The principle also implies the use of renewable energy technologies that
include solar energy, wind power, hydropower, biomass energy and biofuels.

• In the case of bioplastics, the use of renewable raw materials in production


positively affects energy consumption and CO2 emissions i.e. Bottles made
from Poly Lactic Acid which is obtained from dextrose (corn starch).
Principles of Green Chemistry
8. Reduce Derivatives
• Unnecessary derivatization (use of blocking groups, protection/ deprotection,
temporary modification of physical/chemical processes) should be minimized or
avoided if possible, because such steps require additional reagents and can
generate waste.
• Typical example is the production of antibiotics based on penicillin or replacement
of classical chemical enzymatic processes whereby the 6-aminopenicillic acid is
obtained by reacting with the catalyzed immobilized enzyme penicillin amide.
• This resulted in several chemical steps being replaced by an enzymatic reaction,
and no longer required a low temperature (-60°C), organic solvents, and
completely unsuitable conditions that increased and complicated production in the
case of chemical synthesis.
Principles of Green Chemistry
9. Catalysis
• In order to protect the environment, the catalysis principle promotes the use of

biodegradable catalysts, which imply less energy use, avoiding the use of

organochlorine compounds and reducing the use of water or less waste water.

• Like all catalysts, enzymes function in a way that lowers the activation energy of

an individual reaction, and thus accelerates, up to several million times.

• The classic catechol synthesis is derived from benzene (non-renewable

feedstocks) in several reaction stages requiring severe reactions under which

undesirable byproducts are produced. It is replaced by a biocatalytic synthesis.


Principles of Green Chemistry
9. Catalysis

cumene

hydroquinone
Principles of Green Chemistry
10. Design for Degradation
• Chemical products should be designed so that at the
end of their function they break down into innocuous
degradation products and do not persist in the
environment.
• Fulfilment of this requirement is possible by
changing the technological parameters in the process
management and so-called classical methods.
Principles of Green Chemistry
11. Real-Time Analysis for Pollution Prevention
• Analytical methodologies need to be further developed to allow for real-
time, in-process monitoring and control prior to the formation of
hazardous substances.
• With the development of new methods and precision mobile
instruments, it is possible that the analyzes work with a small sample
size at the sampling site and with much less solvent.
• It is necessary to constantly monitor the production process at each
stage would prevent the occurrence of errors that could lead to the
emergence of dangerous substances, harmful to the environment and
human health.
Principles of Green Chemistry
12. Inherently Safer Chemistry for Accident
Prevention
• Substances and the form of a substance used in a chemical process
should be chosen to minimize the potential for chemical accidents,
including releases, explosions, and fires.
• The increasing use of supercritical CO2 that replaces organic solvents
and which, unlike organic solvents, is not toxic or explosive and is
environmentally acceptable.
• Safety can be defined as a control of known hazards by achieving an
acceptable level of risk and is achieved at several levels of the lowest use
of Personal Protective Equipment.
Principles of Green Chemistry
12. Inherently Safer Chemistry for Accident Prevention
• Then it follows the level of Administrative and Work Practice Controls) and
implies establishing effective procedures, rotating work tasks, adjusting
work schedules so that workers are not over-exposed to the impact of
dangerous chemicals, etc.
• The next higher level of security control is the expert Engineering Controls,
which implies the implementation of physical process change To reduce
contact with hazardous chemicals, isolate the process, use wet methods to
reduce dust formation, ventilation, digestion, etc. The highest level of safety
control is achieved by eliminating or replacing the procedure with safer
alternatives.
Principles of Green Chemistry
12. Inherently Safer Chemistry for Accident
Prevention
Principles of Green Chemistry
1. Prevention
2. Atom Economy
3. Less Hazardous Chemical Syntheses
4. Designing Safer Chemicals
5. Safer Solvents and Auxiliaries
6. Design for Energy Efficiency
7. Use of Renewable Feedstocks
8. Reduce Derivatives
9. Catalysis
10. Design for Degradation
11. Real-Time Analysis for Pollution Prevention
12. Inherently Safer Chemistry for Accident Prevention

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