Green Technology Notes

GREEN TECHNOLOGY 1
Mahima alekh
Notes on
GREEN TECHNOLOGY
Prepared by
PEDINA SIBAKRISHNA
ASSISTANT PROFESSOR
DEPARTMENT OF CHEMICAL ENGINEERING
GANDHI INSTITUTE OF ENGINEERING & TECHNOLOGY (AUTONOMOUS),
GUNUPUR-765022, DIST-RAYAGADA, ODISHA, INDIA
Prepared By Pedina Sibakrishna, Assistant Professor, Chemical engg. Deptt., GIET(Auto), Gunupur
GREEN TECHNOLOGY 2
GREEN TECHNOLOGY
Module I:
Principles of green technology and engineering, Principles of atom and mass economy, Efactor.
Module II:
Design of greener and safer chemicals, Solvent-free methods: Microwave, Ultraviolet, and Solar.
Green catalysts: ionic liquids, zeolites, photocatalyst, PEG, nanocatalyst, and biocatalyst. Green
solvents: Supercritical fluids, fluorous phase, and non-aqueous solvents.
Module III:
Scale-up effect, reactors, separators, Process intensification. Bio-conversion of renewables.
Reference Books:
1. Handbook of Green Chemistry, Vol. 1 to 9 by P T Anastas, Wiley VCH.
2. Green Chemistry and Engineering: A Practical Design Approach by C J González and D J C
Constable, Wiley.
3. Green Chemistry and Engineering: A Pathway to Sustainability by A E Marteel- Parrish and
M A Abraham, Wiley.
4. Green Chemistry for Environmental Sustainability by S K Sharma and AMudhoo, CRC Press.
5. Green Engineering: Environmentally Conscious Design of Chemical Processes by D T Allen
and D R Shonnard, PHI.
GREEN TECHNOLOGY 3
Module-I
{Principles of green technology and
engineering, Principles of atom and mass
economy, E-factor.}
GREEN TECHNOLOGY 4
AN OVERVIEW OF GREEN TECHNOLOGIES
Green technology is the application of the environmental science and technology for the
development and application of products, equipment and systems to conserve the natural
resources and environment, as well as to minimize or mitigate the negative impacts on the
environment from human activities. While ‘Green Technology’ is trendier terminology, it carries
meaning no other than ‘Clean Technology’ or the more traditionally used ‘Environmental
Technology’. The field of green technology encompasses a continuously evolving group of
environmental friendly methods and materials, from techniques for generating non-conventional
energy source such as solar power to management tools that help in auditing greenhouse gas
emissions. Green technology development must be sustainable, meaning “balancing the
fulfillment of human needs with the protection of the natural environment and resources so that
these needs can be met not only in the present, but in the indefinite future”. Scheme of
sustainable development can be fulfilled at the confluence of three key dimensions, viz.
environment-social-economic, thus satisfying ‘bearable’ environment and social impact,
‘equitable’ social and economic solutions, and ‘viable’ economic and environmental options.
Conventional green technologies have been applied in the fields of water and wastewater
treatment, air pollution control, environmental remediation, waste treatment and management,
and energy conservation. The following sections discuss some basic knowledge and applications
of green technologies in these fields.
WHAT IS TECHNOLOGY?
The word "technology" can also be used to refer to collection of techniques, skills,
methods and processes used in the production of goods or services or in the achieving of
objectives, such as scientific investigation. Technology can be the knowledge of how to combine
resources to produce desired products, to solve problems, fulfill needs, or satisfy wants; it
includes technical methods, skills, processes, techniques, tools and raw materials., etc. or it can
be embedded in machines, computers, devices and factories, which can be operated by
individuals without detailed knowledge of the workings of such things. In this context, it is the
current state of technology is the application of math, science, and the arts for the benefit of life
as it is known Technology.
WHAT IS GREEN TECHNOLOGY?
Green Technology is the development and application of products, equipment and

systems used to conserve the natural environment and resources, which minimize and reduces
the negative impact of human activities.
Green Technology refers to products, equipment or systems which satisfy the following criteria:
a) It minimizes the degradation of the environment;
b) It has zero or low greenhouse gas (GHG) emission is safe for use and promotes healthy
and improved environment for all forms of life;
c) It conserves the use of energy and natural resources;
GREEN TECHNOLOGY 5
d) It promotes the use of renewable resources.
BRIEF HISTORY OF GREEN TECHNOLOGY

Green technology seems to be a completely new concept that the majority do not know much
about. Green technology or renewable energy has been around for thousands of years. Wind was
used to carry ships over water as early as 7000 years ago by the Egyptians. The primary sources
of renewable energy in history were; human labor, animal power, water power, wind, and
firewood. In the 1800’s wind turbines powered irrigation systems for farming, and in 1830 a
book was written by John Etzler who talks about a city that is run by wind, tidal, and solar power.
In the 1860’s, when fossil fuels were beginning to be used, people feared about already running
out. Petroleum springs and coal mines are not inexhaustible but are rapidly diminishing in many
places. Will man, then, return to the power of water and wind? Or will he emigrate where the
most powerful source of heat sends its rays to all? History will show what will come.”
It is amazing how people back then already feared about running out of fossil fuels, so they
wanted to go back towards more renewable technology. Today we are so dependent on fossil
fuels it seems like it is an impossible task to switch over to alternative energies.
Wind power has been around since 5000 B.C. propelling boats in the nile river, and is still in
use today for mainly commercial use. The power produced by the wind turbine is only as good as
the wind it receives, so these units have to be strategically placed. Wind turbines are usually
placed together in groups, called “wind farms”.
Geothermal energy comes from thermal energy, stored in the earth. It is not certain how long
it has been around, but it only exists in certain regions. Some geothermal energy locations were
historically used as hot springs or for even heating homes, but now has been changed to create
energy.
Solar power was widely used in California homes, it was mostly used to power heaters back
in the 1940’s. Solar power was so commonly used, it almost became the main source of power
back in the 1970’s. Due to the increasing demand for solar power, the company creating the
heaters had to move to a bigger manufacturing space. Unfortunately this caused the price to go
up which led consumers to look elsewhere.
Gas heaters were created after discovering a plentiful amount of natural gas in southern
California, which is what people switched to save money. This is what killed the business of solar
heating.
Solar power technology is quite new, since it requires complex and expensive panels that can
store the sun's energy. Solar energy is widely used in homes, or even flat land that receives a lot
of sun, such as deserts. The power can be stored, or sold to whoever needs it.
Hydro-power uses the power of flowing water to generate electricity. In 2015 it generated
16.6% of the electricity in the world, as well as 70% of the total of renewable energy generated.
Hydro-power exists in many forms, such as dams, rivers, and other small installations. Hydro-
power is already being produced in over 150 countries, making it the most widely used form of
renewable energy.
Did you know that in the 1900s electric taxi cabs were widely used in Manhattan, or that in
California solar power was widely known about and was used to heat showers, or that windmills
were used to draw up water in the Midwest to help with drought? In fact the electric vehicle
GREEN TECHNOLOGY 6
company (EVC) was the first invention of an electric car (figure 1.1), called the electrobat.
Although the range was only fifty to one hundred miles, it was still impressive.
Figure :1.1:- Electrobat
IMPORTANCE OF GREEN TECHNOLOGY
Green technology, an environmentally friendly technology is developed and used in a way

that protects the environment and conserves natural resources. The intensive use of green
technology aims to slow down global warming. Thus, the green house effect will be significantly
reduced. The implementation of new technologies that preserve the natural resources will be
beneficial for the general health of our planet and for the well-being of people.
FOUR PILLARS OF GREEN TECHNOLOGY POLICY

1. Environment - Conserve and minimize the impact on the environment;
2. Social - Improve the quality of life for all
3. Economy - Enhance the national economic development through the use of technology;
and
4. Energy – Seek to attain energy independent and promote efficient utilization;
1. Environmental Pillar All human activities have an impact on the environment. Conversely,
the relative health of the environment will determine and will contribute to the nature and
scale of activities in the other pillar areas of this plan: economic, cultural and social. Earlier in
this plan, we noted some of the major global environmental challenges: climate change
exhausting nonrenewable resources, shrinking natural habitats, diminishing biodiversity,
ocean acidification; and increasing human population pressures. Clearly, all of these issues
have economic, social and cultural element
2. Social pillar The Social Equity Pillar will help social agencies and residents to raise
awareness about social needs and to engage both citizens and community partners to plan
and act in response to these needs. The end result will be to improve the well-being of the
GREEN TECHNOLOGY 7
whole community. Together, we will build social capital in the community between
individuals and groups in order to enable collaborative action on projects of common
interest. With this, we stress the importance of personal and group well-being and security,
including full access to effective health care, housing, food, and education services-these being
the essential components for full participation in cultural, environmental, and economic
activities.
3. Economic Pillar It is focused on the attraction of new businesses and people to India. This is
critical to the city’s growth and sustainability and assists us in building a strong and vibrant
local community. The recruitment of talented people in the public, private, and non‐profit
sectors in India are fundamental to achieving this. Present businesses and the jobs they create
are main components of a strong, sustainable economy. Together we can achieve and be the
difference that makes the difference.
4. Energy Harvesting An important pillar of green technology is energy harvesting, which seeks
new innovative ways to extract useful energy from otherwise useless waste by-products, as
well as to develop new technologies to maximize the harnessing of energy. Energy efficiency
has proven to be a cost-effective plan for building economies by minimizing the amount of
energy used.
OBJECTIVES
• To reduce the rate of growth of energy consumption while enhancing economic

development;
• To facilitate the growth of the Green Technology industry and enhance its contribution to
the national economy;
• To increase the capacity for innovation in Green Technology development and enhance
competitiveness in Green Technology in the field;
• To ensure sustainable development and preserve the environment for future generations,
and
• To increase public awareness and education on green technology and encourage its
widespread use Green Technology.
GOALS OF GREEN TECHNOLOGY
• Reduce
• Recycle
• Refuse
• Renew
• Responsibility
GREEN TECHNOLOGY 8
GREEN TECHNOLOGY 9
MAJOR SECTOR
• Energy Sector: Application of Green Technology in power generation and energy supply
management, including co-generation (co-generation) in the industrial and commercial
sectors, and Sector Energy Consumption Application of Green Technology in all sectors of
energy consumption and energy demand management programs.
• Building Sector: Adoption of Green Technology in the construction, management,
maintenance and destroying of buildings
• Water and Waste Management Sector: Adoption of Green Technology in the
management and use of water resources, wastewater treatment, solid waste landfill
• Transport Sector: Incorporation of Green Technology in the transportation
infrastructure and vehicles, in particular, biofuels and public road transport.
APPLICATIONS OF GREEN TECHNOLOGY IN OUR LIFE

 SOLAR ARRAY
One of the best known examples of green technology would be the solar cell. A solar cell
directly converts the energy in light into electrical energy through the process of photovoltaics.
Generating electricity from solar energy means less consumption of fossil fuels, reducing
pollution and greenhouse gas emissions.
 REUSABLE WATER BOTTLE
Another simple invention that can be considered green is the reusable water bottle. Drinking
lots of water is healthy. Reducing plastic waste is great for the environment. Hence, trendy
reusable water bottles that you can refill yourself are health-promoting, eco-friendly, and green.
 SOLAR WATER HEATER
Installing a solar water heater can be a great way to cut down on energy costs at a much
lower initial expense. The costs associated with the installation of a solar water heater are
actually recouped much faster than the costs associated with photovoltaic technology for power
generation. This is due to the increased efficiency of solar water heating systems, as well as their
reduced expense when compared to the large solar array required for powering a home.
 WIND GENERATOR
GREEN TECHNOLOGY 10
The costs of a home wind generator vary greatly. Some have built their own wind generators
with off-the-shelf parts from their local hardware stores. Others have purchased kits or paid for
professional installation to supplement the power purchased from their local electrical grid. The
power production capability of a home wind generator varies about as much as the initial
expense. Many kit based generators will produce only enough power to offset 10-15% of your
home energy costs.
 RAINWATER HARVESTING SYSTEM
Rain collector systems are extremely simple mechanical systems that connect to a gutter
system or other rooftop water collection network and store rain water in a barrel or cistern for
later non-potable use (like watering plants, flushing toilets, and irrigation). These systems are
extremely inexpensive.
 INSULATE OUR HOUSE
Based on EPA estimates, 10% of household energy usage a year is due to energy loss from
poor insulation. We will get an excellent return on investment from sealing our home to prevent
energy escape.
 BUILDING WITH GREEN TECHNOLOGY
Green buildings use a variety of environmentally friendly techniques to reduce their impact
on the environment. Reclaimed materials, passive solar design, natural ventilation and green
roofing technology can allow builders to produce a structure with a considerably smaller carbon
footprint than normal construction. These techniques not only benefit the environment, but they
can produce economically attractive buildings that are healthier for the occupants as well. The
chief benefit of building green is reducing a building’s impact on the environment. Using green
building techniques can also reduce the costs associated with construction and operation of a
building. Green ventilation techniques involve open spaces and natural airflow, reducing the
need for traditional air conditioning and preventing many of these problems.
 NATIONAL BENEFITS FOR ENERGY GENERATION
Power generation is another sector where green technology might create wonders.
Distributed generation technologies e.g. solar PV, biogas production, wind power etc. have
practically proven that they can provide more employment opportunities to people and can be
applied to provide energy solutions to communities in remote areas successfully. Live examples
exist in India where people have used alternative green power generation technologies and have
not only fulfilled their own energy needs but have also sold their energy to the grid thereby
making significant income. Same is in countries like Germany, where people sell the electricity
generated by their household Photovoltaic panels to the national grid and in rare cases may end
up charging money from the utility instead of paying! In this way a person not only helps him or
herself but also helps the nation by actually contributing to the national power generation and
thus proves to be an asset rather than a liability to the society.
 BENEFITS TO THE RURAL AREAS
Green technologies have had great impact on communities of the areas where they have been
implemented. Provision of bio-gas plants to rural households has empowered communities and
has increased their productivity. Same has been the case with distribution of solar lanterns
through certain programs. It is clear that people have benefited from it by not only using the
outputs personally but also by trading it. Initiatives such as the barefoot college in Rajasthan
empower villagers by teaching them how to use eco-friendly technologies like solar cookers, mud
GREEN TECHNOLOGY 11
refrigerators, and sustainable farming practices. Villagers have built their own water storage and
rainwater harvesting techniques and are not dependent on outside help. This has raised the
standard of living in the participating villages.
 BENEFIT TO THE URBAN AREAS
Cities which actively pursued their environmental concerns in the last ten years are showing
a marked improvement in their environment quality parameters. For example Delhi launched
CNG fuelled public transport in a phased manner. This was done as measures to improve air
quality of Delhi where the toxic gas levels were off the charts, sometimes exceeding 5-12 times
the normal values. Since then Delhi has shown steady improvement in the air quality.
 GREEN CHEMISTRY
Green chemistry, also called sustainable chemistry, is a philosophy of chemical research and
engineering that encourages the design of products and processes that minimize the use and
generation of hazardous substances. In 1990 the Pollution Prevention Act was passed in the
United States. This act helped create a model for dealing with pollution in an original and
innovative way. It aims to avoid problems before they happen. As a chemical philosophy, green
chemistry applies to organic chemistry, inorganic chemistry, biochemistry, analytical chemistry,
and even physical chemistry.
 GREEN NANOTECHNOLOGY
Nanotechnology involves the manipulation of materials at the scale of the nanometer, one
billionth of a meter. Some scientists believe that mastery of this subject is forthcoming that will
transform the way that everything in the world is manufactured. "Green nanotechnology" is the
application of green chemistry and green engineering principles to this field.
ADVANTAGES OF GREEN TECHNOLOGY
1. Does not emit anything harmful into the air

2. Can bring economic benefits to certain areas.
3. Requires less maintenance so you don’t have to shell out a lot of money to operate it
4. Renewable which means we will never run out?
5. Can slow the effects of global warming by reducing CO2 Emissions.
DISADVANTAGES TO ADOPTING GREEN TECHNOLOGIES
1. High implementing costs.

2. Lack of information.
3. No known alternative chemical or raw material inputs
4. No known alternative process technology
5. Uncertainty about performance impacts
6. Lack of human resources and skills.
GREEN TECHNOLOGY 12
GREEN ENGINEERING
Figure 1.2- Green Engineering is an added qualification. Green Engineers design and apply green principles in their
design of chemical processes and products to achieve sustainability and environmental protection .
INTRODUCTION
In the last decades scientists in developed and developing human societies became
aware that rapid economic growth and unrestrained use of natural resources caused substantial
environmental problems and disrupted the future sustainability of many regions of the world.
It has been recognized that pursuing high growth objectives without considerations of
environmental degradation and natural resources depletion threatens sustainability. The
environmental movements of the 1960s and 1970s protested for the trends in economic growth
and the inevitable environmental pollution on regional, national and global scale. Major
environmental problems, like the ozone hole in the stratosphere, the global warming and the
greenhouse effect, the spread of environmental pollution by polychlorinated compounds in
remote places of the planet, plastic pollution of the oceans, the depletion of natural resources of
fresh water, desertification, etc, are some of the problems causing international concern.
Green chemistry as a scientific movement of the 1990s for better design and innovations
in the chemical industry was extended to Green Engineering which covers technological
applications, engineering processes and products.
According to Environmental Protection Agency (EPA): Green Engineering
embraces the concept that decisions to protect human health and the environment can
have the greatest impact and cost effectiveness when applied early to the design and
development phase of an industrial process or product. The goal of the Green Engineering is to
incorporate risk related concepts into chemical processes and products designed by academia
and industry.
Green Engineering is aiming to four major sections of the scientific and technological
community : academia, university teachers (instructing students on new thinking in engineering
processes and applications, through academic lectures and workshops that disseminate green
engineering material), Software scientists (to provide engineers with integrated risk based tools
for assessing hazards in process design and other programmes), industrial chemical engineers
and other scientists (continuing education courses, providing new academic material,
methodologies and case studies which illustrate green engineering alternatives in chemical
process , new designs and technological innovations with green credentials for engineers),
GREEN TECHNOLOGY 13
Continuous dissemination of sources and green engineering materials to academia and industry
(continuous flow of information and ideas for new case studies and process design
methodologies of green engineering).
In fact ―Green Engineering is the process and design of products aiming to conserve
natural resources leading to sustainability goals. Also, green engineering aims to reduce the
impact of processes and products to the natural environment. The term ―green engineering is
applied to a variety of products, like houses, vehicles, consumer products (materials, electrical
and electronic equipment) and devices that requires engineering technologies in the construction
or making.
THE TWELVE PRINCIPLES OF GREEN ENGINEERING

Green Engineering (GE) focuses on how to achieve sustainability through science and
technology. Green Engineering are covered by 12 principles which were presented for the first
time by Paul T. Anastas and Julie B. Zimmerman (Environmental Science and Technology, March 1,
95A-, 2003). The 12 Principles of Green Engineering provide a framework for scientists and
engineers to engage in when designing new materials, products, processes, and systems that are
benign to human health and the environment. The Green Engineering principles must be
applicable, effective, and appropriate. Otherwise, these would not be principles but simply a list of
useful techniques. It is also useful to view the 12 principles as parameters in a complex and
integrated system. Just as every parameter in a system cannot be optimized at any one time,
especially when they are interdependent, the same is true of these principles. There are cases of
synergy in which the successful application of one principle advances one or more of the others. In
other cases, a balancing of principles will be required to optimize the overall system solution. In
the case of Green Engineering the twelve principles are similar aspects of basic aims and goals for
attaining sustainability through green engineering principles. The 12 Principles of Green
Engineering have been implemented by scientists of American Chemical Society (ACS).
Table 1.1. The Twelve Principles of Green Engineering
Principle No. 1. Materials and energy must be Inherently non-hazardous, Rather Than
Circumstantial
Designers need to strive to ensure that all materials and energy inputs and outputs are as
inherently nonhazardous as possible.
Principle No. 2. Prevention of Waste Instead of Treatment
It is better to prevent waste than to treat or clean up waste after it is formed.
Principle No. 3.Design for Separation and Purification Processes
Separation and purification operations should be designed to minimize energy consumption and
materials use.
Principle No. 4. Maximize Efficiency in products and processes
Products, processes, and systems should be designed to maximize mass, energy, space, and time
efficiency.
Principle No. 5. Output-Pulled Versus Input-Pushed
Products, processes, and systems should be "output pulled" rather than "input pushed" through
the use of energy and materials
GREEN TECHNOLOGY 14
Principle No. 6. Conserve Complexity

Embedded entropy and complexity must be viewed as an investment when making design
choices on recycle, reuse, or beneficial disposition.
Principle No. 7. Durability Rather than Immortality
Targeted durability, not immortality, should be a design goal for products.
After useful use of a product to disintegrate under natural conditions
Principle No. 8. Meet Need, Minimize Excess (Products)
Design for unnecessary capacity or capability (e.g., "one size fits all") solutions should be
considered a design flaw.
Principle No. 9. Minimize Material Diversity
Material diversity in multi component products should be minimized to promote disassembly and
value retention.
Principle No. 10. Integrate Material and Energy Flows
Design of products, processes, and systems must include integration and interconnectivity with
available energy and materials flows
Principle No. 11.Design for Commercial "Afterlife"
Products, processes, and systems should be designed for performance in a commercial "afterlife."
Principle No. 12. Renewable Rather Than Depleting
Material and energy inputs should be renewable rather than depleting
Principle No. 1. Inherent rather than circumstantial. There is a need for all materials and
energy inputs to be inherently non-hazardous as possible.
Many industrial starting materials are inherently hazardous from the beginning and their
products inevitably will be toxic and cause environmental problems. Although the trend now is to
minimize their negative aspects by investing in environmental mitigation processes, this is not an
environmentally sustainable approach. The initial design of the products must evaluate the
inherent nature of the selected material (toxicological and physicochemical properties) and
calculate the energy inputs required. The first step must aim for a sustainable product and process
with materials that are non-hazardous. Designers must developed methods and technological
innovations to create inherently non-hazardous materials, for humans and the environment. If
there is no alternative material, the design and the process must strive to remove the hazard in the
final steps of the process. These can be achieved during purification or the cleanup steps of the
product. The ideal case will be to use materials and inputs of energy and other reagents that are
less hazardous, thus reducing the risks for environmental impacts and the cost to monitor, control
and contain the environmental pollution caused by the rejection of the product as waste.
Principle No. 2. Prevention is best than treatment. Prevention of waste is better than to clean
up afterwards
The initial design of industrial processes and products contains the intention to produce
minimum waste (―zero-waste) but the notion is criticized from other scientists as ignoring the
laws of nature. These laws are the first and second thermodynamic axioms and rules of enthalpy
in systems.
Waste is assigned to material or energy that the present processes or systems are unable to
effectively exploit for beneficial use. It is natural when we use energy in the production of
products that this energy is absorbed and the e n t r o p y de cre a se s . With t h e u s e o f t h e
GREEN TECHNOLOGY 15
p r o d u c t s t he ― disturbance increases (entropy) , the products disintegrates and is transformed

into waste. The scientists of green chemistry indicate that the concept of waste is human. There
are no inherent properties in energy or products which inevitably will transform them into waste.
Waste generation can be avoided or prevented wherever possible.
Green chemistry scientists will like to redesign products and use of energy in industrial
processes in such a way so that waste is minimized.
There are new technologies that aim towards waste-free design at any scale and are based
on the same concept: inputs are designed to be part of the desired output. This concept at the
molecular scale (chemical reactions) has been described as ―atom economy and can be
extended across design scales as the ―material economy. There are now many options for
energy generation that do not produce waste, one of these systems are fusion energy which can
lead us to energy sustainability.
Principle No.3. Design strategy for separation and purification. Processes for products with
minimum energy consumption and material use
The traditional methods of manufacturing processes until now consume vast amounts of
energy for separation of the products and cleaning with toxic solvents. Heat and pressure is applied
in most conventional processes which increase the demand for energy. Green technologists would
like to change this trend and reduce the use of energy. This can be achieved by radical changes in
the design of the process. Green technologies will like to take design decisions at the earliest stage
of manufacturing process so that self- separation and purification will be included in the process.
Economic and technical limitations in separating materials and components are among the
greatest obstacles to recovery, recycle and reuse of materials and reagents. Green engineers
studied how these obstacles can be overcome. Avoiding permanent bonds between two different
materials is one solution. Fasteners that are designed for disassembly can be incorporated into the
design strategy. At the molecular level in the chemical industry and in the laboratory the
separation and purification is performed with distillations and column chromatography. Both
methods are energy intensive and consume large quantities of toxic solvents. Scientists should aim
to reduce the need for these wasteful processes. Design of self-separation and purification of
products from the reaction medium is s desired technology. Addition of polymers in the reaction
medium can be very useful in this process. Designed polymers can control the solubility of the
substrates, but also can be ligands and catalysts for separation and reuse.
Principle No. 4. Maximize mass, energy, space and time efficiency. By better designing in
chemical processes and systems
Efficiency is very important in every manufacturing process and makes economic sense.
Materials, energy, time and space are important variables that green engineers can take into
account when designing their alternative innovations in industrial processes. Large batch reactors
in chemical manufacturing are a typical example of how things were made in the conventional way.
These are considered now ―old technology. Micro reactors that operate continuously at very low
volume with efficient mixing, high productivity and digitalized information of the process are
considered more efficient. The reduction in scale of the production can be applied also to other
GREEN TECHNOLOGY 16
factors, such as eco-industrial plants in cities with easy access for the workers (less car
dependency, less suburban sprawl, less time consuming).
Figure 1.3. Green Engineering and its principles can maximize efficiency in manufacturing processes and minimize
waste and environmental pollution. Designing in the early stages and alternative innovations for the conventional
chemical processes can improve substantially their sustainability.
Principle No. 5. Output-pulled versus input-pushed. More energy or material (“input-pushed”)

can increase output, but the same output can be achieved by new designing where chemical
processes are “pulled” (e.g. removing products from reaction system) without additional
energy or material
Chemists and chemical engineers know from experience that a chemical reaction or
transformation under high temperature, pressure, and additional material, will push the balance
the reaction forward, i.e. produce higher output of a desired product. (Le Châtelier’s Principle, system
at equilibrium under stress). Chemical engineers in their desire to increase output of a
manufacturing reaction were adding more energy (heat, pressure) or starting material to shift the
equilibrium and get the desired output
An example at the molecular level which can describe the chemical transformation is
condensation reactions with the production of water. In order to increased the yield the water was
eliminated from the product stream and thus the reaction was pulled to completion without
additional energy or material. This is the new thinking in green engineering processes; the
transformations must be pushed without extra energy and material with planning in advance
manufacturing systems.
Another important aspect of manufacturing processes is the ―just-in- time manufacturing,
which means products can be produced to meet the demand of the end user (final purchaser of
the product) for the on exact for timeliness, quantity and quality. The good planning of
manufacturing systems for the final output of a product can overcome waste, which is associated
with overproduction, waiting time, processing, and inventory and resource inputs.
Principle No. 6. Conserve complexity. Products with high complexity should correspond to
reuse, products with minimal complexity are favoured for value-conserving recycling or
beneficial disposition.
GREEN TECHNOLOGY 17
This is another very important aspect of manufacturing products with in-build complexity.
The higher the complexity of a product the higher the expenditure on materials, energy and time.
A good example is the computer chips that have a significant level of complexity invested in
them. To recycle a silicon chip may not be efficient method for recovering the value of the starting
material. Whereas , for the paper bag the complexity is very low, but in this respect the value of the
product and its material do not warrant the energy for collection, recycling and remanufacturing of
the same product. Green engineers must think in the designing stage about the end-of-life of a
product. How important are the decisions to recycle, reuse or have a beneficial disposal, based on
the invested material and energy for the product and its complexity.
Principle No. 7. Durability rather than immortality. Design goal for products that will last
beyond their useful commercial life
It is desirable that products are well constructed and durable during their useful
commercial life, but not to be persistent and result in environmental problems. These two
properties, durability and persistence after use are two contrasting and must be balanced in the
designing stages by green engineers. The design must aim at products that are durable enough to
withstand operating conditions during their lifetime, and avoid premature disposal. Efficient
maintenance and repair of a product without added material is an advantage. Immortality or
persistence to environmental conditions after disposal are not desirable properties because
through bioaccumulation can be dangerous to living organisms.
The case of disposable plastic bags that everybody uses now for carrying consumer goods
has become an international environmental problem due to the persistence of plastic in the water.
Polymers made from biologically based materials are a new green chemistry initiative which
replaces the petroleum-based polyacrylic acid polymers. Polyactic acid or polylactide is a
thermoplastic aliphatic polyester derived from renewable resources, such as corn starch, tapioca
products (roots) or sugarcanes. Lactic acid is produced by bacterial fermentation of starch.
Polyactic acid is a product of green chemistry, can biodegrade under certain conditions, such as the
presence of oxygen, and is difficult to recycle.
Figure 1.4. Go green has become a slogan. Green Engineering is applied to many aspects of chemical
manufacturing and new electronic products. Green engineering concentrates on how to promote
sustainability through science and technology. Green engineers are engaged in designing new materials,
products, processes and systems.
GREEN TECHNOLOGY 18
Principle No 8. Green Engineering can meet needs and minimize excess.

The global economic competition of the last decades has changed dramatically the new
technological advances in great variety of consumer products. Although new technology covered
most of human consumer needs and social aspirations, it contributed also too many excesses,
waste and environmental degradation, New materials, natural resources, energy and technology
were wasted in many industrialized countries for overdesign and unusual capabilities of various
products. Many products after their commercial life cycle cause increasing environmental
problems as waste due to their complexity, extreme persistence and difficulty in recycling.
A good example is the disinfection of drinking water by chlorine. The technology is very
useful to protect human life. The centralized location of disinfection causes excess chlorination in
short distances and reduced disinfection in further distances. An alternative and sustainable policy
will be to install actuator and control system to regulate the dose of chlorination. Chemical industry
can apply a new strategy to limit material, energy and other reagents by introducing the use of
enzymes as catalysts that operate at mild condition.
Principle No. 9. Minimize material diversity. Reducing multiple components in products
increases the possibility of useful reuse or recyclability
Most of the consumer products of today (cars, electric and electronic equipments, food
packaging, etc) are made in such a way that include multiple components. Even plastic materials
contain a variety of other chemicals, such as plasticizers, dyes, stabilizers, flame retardants.
These are added chemicals and in general material diversity increases the properties and useful
function of products. But when these products come to the end of their life cycle they present a
series of problems when considering disassembly, reuse and recyclability. Some products can be
produced from one material than two or three. A good example is the new technology which is
applied in plastics for cars. Different forms of polymer can have diverse properties and used for the
construction of doors and instrument panels (metallocene and polyolefins have these properties
and can be engineered to the different design properties).
Principle No. 10. Integrate local material and energy flows. Products and processes must
integrate with available energy and materials flows, Industrial parks can take advantage of
the existing framework of energy.
Industrial products and processes must take advantage of local and existing energy and
material flows in the area where they operate, so that they can minimize the need for imports or
transport from fara way places of energy and raw materials. Also, at the local level they can
exchange heat from other industrial units if there are exothermic operations. Byproducts from one
industrial unit can become feed stocks for subsequent reaction processes in other industrial
operations. In industrial parks, ―waste materials and energy can be captured throughout the
production line and incorporated in other processes and other final products.35-38
Principle No. 11. Design for commercial “afterlife”. Products and processes and components
that remain functional can be recovered and reused.
Many commercial products, processes and systems after reaching their end of life become
obsolete and have to be thrown away as waste. Green engineers have to take into account when
designing these products. In order to reduce waste, some components or part of some processes as
GREEN TECHNOLOGY 19
long As they remain functional can be reused or recovered as materials for another useful
operation. Incorporating commercial afterlife properties into the initial design strategy of products
and processes can save lots of material and energy with reuse and recovery of various parts. Mobile
phones, computers, electrical equipment, printers, other commercial machines in offices or in the
house become outmoded premature and had to be replaced with modern items. Designing
products so that part of the components can be recovered would significantly reduce waste, and
energy and materials for future products. Commercial afterlife is part of the green engineering
design of new products.
There are many good examples of electrical machines and electronic products that have
―end-of-life design features so that can be disassembled into components, recycled, or reused with
maintenance and easy repair. Xerox printers are designed so that after their commercial use, can be
converted and be remanufactured. Various other big industrial companies have introduced green
engineering design features in their products for easy repairs, recyclability or reuse after
maintenance ((AT&T, General Electric, IBM, Procter & Gable, Whirlpool, etc).
In the last decade there is a major shift in the way industrial manufacturers have changed
the design of their products in order to reduce the end-of-life burdens to the environment. The
Product Life Cycle (PLC) analysis has become a standard method following the various stages of a
product’s life. From starting materials, manufacture and final disposition the life of a product is
analysed quantitatively from its environmental impact and natural resources use. It is represented
with a cycle: Design— Manufacturing—Distribution—Customer—End-of-Life. Many software
programmes have been developed recently dealing with PLC. The PLC is associated with
engineering tasks, materials and energy, but also can involve marketing activities and new product
development.
Figure 1.5. The Life Cycle of a product is considered a very valuable analysis of the manufacturing processes and the
environmental problems which might be caused by the circulation of a certain product.
Principle No. 12. Renewable rather than depleting. Materials and energy for
manufacturing must be renewable for sustainable development
The 20th century was characterized by a rapid economic growth that did not pay attention to
natural resources and energy sources. This was the main cause for the extended environmental
GREEN TECHNOLOGY 20
pollution and the depletion of valuable natural resources. Scientists and technologists agree that
human civilization cannot continue its path to material prosperity without renewable resources.
Sustainability is in danger and societies can collapse from lack of natural resources. Renewable
natural resources, that have the ability to be replaced through biological or other natural processes,
can be used in sustainable cycles without damaging effects, but even in this situation there are
limits. Renewable natural resources (material and energy) need to be managed carefully and to
avoid exceeding their capacity to replenish. Renewability of natural resources and appropriate use
is the key for sustainable development and protection of the environment.
Renewable natural resources are considered all biological materials, (biomass), solar
energy, winds, geothermal energy, tides and any natural elements that are replenished with time.
In the other end of the scale are depleting natural resources (which are cheaper and used
extensively now), such as coal, natural gas, petroleum(fossil fuels), minerals, agricultural land, the
seas, fresh water etc.
The framework of Green Engineering through its 12 principles covers some of the most
important industrial processes and technological issues developed in the last decades. The 12
principles of Green Engineering are not a list of goals, but a set of the important methodologies that
need changing in order o achieve these goals and promote sustainable development.
SYSTEMS APPROACH
To varying extents, all engineering disciplines engage in green engineering. This includes
sustainable design, life cycle analysis (LCA), pollution prevention, and design for the environment
(DfE), design for disassembly (DfD), and design for recycling (DfR). As such, green engineering is
a subset of sustainable engineering. Green engineering involves four basic approaches to improve
processes and products to make them more efficient from an environmental standpoint.
GREEN TECHNOLOGY 21
1. Waste reduction;
2. Materials management;
3. Pollution prevention; and,
4. Product enhancement.
Green engineering approaches design from a systematic perspective, which means that
numerous professional disciplines must be integrated. In addition to all engineering disciplines,
green engineering includes land use planning, architecture, landscape architecture, and other
design fields, as well as the social sciences e.g. to determine how various groups of people use
products and services. Designers have always been concerned with space. Architects consider the
sense of place. Engineers view the site map as a set of fluxes across the boundary. Planners
consider the combinations of these systems over larger regions, e.g. urban areas. The life cycle
analysis is an important green engineering tool, which provides a holistic view of the entirety of a
product, process or activity, encompassing raw materials, manufacturing, transportation,
distribution, use, maintenance, recycling, and final disposal. In other words, assessing its life cycle
should yield a complete picture of the product. The first step in a life cycle assessment is to gather
data on the flow of a material through an identifiable society. Once the quantities of various
components of such a flow are known, the important functions and impacts of each step in the
production, manufacture, use, and recovery/disposal are estimated. Thus, in sustainable design,
engineers must optimize for variables that give the best performance in temporal frames.
The systems approach employed in green engineering is similar to value engineering (VE).
Daniel A. Vallero considers green engineering to be a form of VE because both systems require
that all elements and linkages within the overall project be considered to enhance the value of the
project. Every component and step of the system must be challenged. Ascertaining overall value
is determined not only be a project's cost-effectiveness, but other values, including
environmental and public health factors. Thus, the broader sense of VE is compatible with and
can be identical to green engineering, since VE is aimed at effectiveness, not just efficiency, i.e. a
project is designed to achieve multiple objectives, without sacrificing any important values.
Efficiency is an engineering and thermodynamic term for the ratio of an input to an output of
energy and mass within a system. As the ratio approaches 100%, the system becomes more
efficient. Effectiveness requires that efficiencies be met for each component, but also that the
integration of components lead to an effective, multiple value-based design. Green engineering is
also a type of concurrent engineering, since tasks must be parallelized to achieve multiple design
objectives.
GREEN ENGINEERING APPLICATION
The potential for green engineering applications spans almost every industry. While there are
many ways to group these green applications, most fall into five categories:
 Environmental Monitoring
 Energy Storage Systems
 Power Quality Monitoring
GREEN TECHNOLOGY 22
 Solar Energy
 Wind Energy
ENVIRONMENTAL MONITORING
With the increased focus on the effects of climate change on the environment, there has
been a global effort to reduce the amount of greenhouse gases that cause them. There is a
growing need to measure and monitor the environment.
ENERGY STORAGE SYSTEMS
Energy storage systems (ESSs) and renewable energy sources are critical technologies
that combine to create power generation and transportation. ESSs also need to be renewable.
There are many types of ESSs including chemical, electrical, mechanical, and thermal. The focus in
this section is on electrochemical and electric ESSs including batteries, fuel cells, capacitors, and
super capacitors or ultra capacitors.
POWER QUALITY MONITORING
Power quality monitoring solutions combine rugged hardware for waveform
measurements with flexible software capable of performing any power monitoring, power
quality, or power metering analysis.
SOLAR ENERGY
The sun sustains life on Earth. For centuries humans have used solar heating to warm
houses and plant life has relied on sunlight for photosynthesis. Efficiently converting solar energy
into solar power or electricity is a recent challenge. Two common technologies for solar
electricity generation are photovoltaic (sunlight is converted directly to electricity) and solar
thermal (the sun heats water and creates steam that is then used to power steam engines).
WIND ENERGY
Wind power has become an important source of renewable energy around the world. In
the United States, wind power capacity increased by 45 percent in 2007, according to the
American Wind Energy Association (AWEA). Globally, wind power generation quadrupled
between 2000 and 2006, according to the World Wind Energy Association (WWEA). Engineers
across the wind power industry are using technologies to conduct research, from the design and
manufacturing of wind turbine blades to online machine condition monitoring for turbines
deployed at wind farms.
GREEN TECHNOLOGY 23
GREEN CHEMISTRY
Figure 1.6. Environmental Protection Agency (EPA) advanced the idea and applications of Green Chemistry
from the beginning of the 1990s.
INTRODUCTION
Green Chemistry and Green Engineering are an integral part of new thinking (we can called it
new philosophy) which is needed to advance the goals of sustainability. The chemical Industry and
synthetic chemical production is now the most important economic form in producing thousands of
chemical products, consumer goods and materials. So, the goal for changes in the design, production
and use of chemicals will contribute to sustainability. From the beginning the GC advances were
focusing in feed stocks, reagents, solvents and syntheses. Green chemistry wants to change how
things were working until now. Green Chemistry demands new standards for chemicals and chemical
processes. GC demands changes in the decisions made by chemists when are designing the industrial
production. GC provides new techniques to reduce or eliminate negative environmental impacts. The
use and production of these chemicals may involve reduced waste products, non-toxic components,
and improved efficiency. Green chemistry is a highly effective approach to pollution prevention
because it applies innovative scientific solutions to real-world environmental situation
Various Definitions of Green Chemistry are
• Green chemistry (which is also known as sustainable chemistry) is the design of

chemical products and processes that reduce or eliminate the use or generation of
hazardous substances. Green chemistry (GC) applies across the life cycle of a chemical
product, including its design, manufacture, and use.
• Green chemistry efficiently utilizes (preferably renewable) raw materials, eliminates
GREEN TECHNOLOGY 24
waste, and avoids the use of toxic and/or hazardous reagents and solvents in the
manufacture and application of chemical products.
• Green chemistry is the design, development, and implementation of chemical products
and processes to reduce or eliminate the use of substances hazardous to human health
and the environment.
• Green Chemistry has been defined as “the invention, design and application of
chemical products and processes to reduce or to eliminate the use and generation
of hazardous substances for workers and consumers”.
Green chemistry:
 Prevents pollution at the molecular level
 Is a philosophy that applies to all areas of chemistry, not a single discipline of chemistry
 Applies innovative scientific solutions to real-world environmental problems
 Results in source reduction because it prevents the generation of pollution
 Reduces the negative impacts of chemical products and processes on human health and
the environment
 Lessens and sometimes eliminates hazard from existing products and processes
 Designs chemical products and processes to reduce their intrinsic hazards
CHEMISTRY AND GREEN CHEMISTRY

Chemistry is the study of matter, the way matter (atoms and molecules and compounds)
interacts to give rise to a whole range of processes. It is also the study of the behavior of
individual atoms, molecules and compounds. Chemistry is also known as the “central science”
because the study of Chemistry is also important for Physics and Biology. Chemistry is, basically,
the study of all the different types of atoms, molecules, compounds and the processes and
phenomena that happen when they interact.
Green Chemistry is a specific field of Chemistry involving the study of atoms, molecules,
and compounds and determining whether the usage of such matter is safe for the environment.
DIFFERENCES:
1. Chemistry is a very broad science, meaning that it covers a large range of theories,
whereas, Green Chemistry is only a fraction of Chemistry.
2. Chemistry aims at developing chemicals for the welfare of the humans, whereas Green
Chemistry aims at developing chemicals for the welfare of the humans but in the same
time, not adversely affecting the environment.
ENVIRONMENTAL CHEMISTRY
Environmental chemistry is the scientific study of the chemical and biochemical
phenomena that occur in natural places. It should not be confused with green chemistry, which
seeks to reduce potential pollution at its source. It can be defined as the study of the sources,
reactions, transport, effects, and fates of chemical species in the air, soil, and water environments;
and the effect of human activity and biological activity on these. Environmental chemistry is an
interdisciplinary science that includes atmospheric, aquatic and soil chemistry, as well as heavily
relying on analytical chemistry and being related to environmental and other areas of science.
GREEN TECHNOLOGY 25
Environmental chemistry is the study of chemical processes occurring in the environment

which are impacted by humankind's activities. These impacts may be felt on a local scale, through
the presence of urban cities' air pollutants or toxic substances arising from a chemical waste site,
or on a global scale, through depletion of stratospheric ozone or global warming. The focus in our
courses and research activities is upon developing a fundamental understanding of the nature of
these chemical processes, so that humankind's activities can be accurately evaluated.
Environmental chemistry involves first understanding how the uncontaminated
environment works, which chemicals in what concentrations are present naturally, and with
what effects. Without this it would be impossible to accurately study the effects humans have on
the environment through the release of chemicals.
HISTORY OF GREEN CHEMISTRY
1960s
• Rachel Carson wrote the mainstream, scientific book, Silent Spring in 1962. It outlined the
devastation that certain chemicals had on local ecosystems. The book served as a wake-up
call for the public and scientists alike, and inspired the modern environmental movement.
• In 1969, Congress recognized the importance of the issue and passed the National
Environmental Policy Act (NEPA). The law's goal was to "create and maintain conditions
under which man and nature can exist in productive harmony," and called for a
Presidential Council on Environmental Quality.
• Growth of environmental awareness; early environmental legislation
1970s
• EPA established in 1970; significant environmental legislation passed; Love Canel disaster
leads up to "Superfund" act of 1980.
• In 1970, President Richard Nixon established the U.S. Environmental Protection Agency
(EPA), a federal regulatory agency devoted solely to protecting human health and the
environment. The EPA's first major decision was to ban the use of DDT and other chemical
pesticides.
• Congress passed a series of regulatory laws to stem the environmental impact of pollution,
such as the Safe Drinking Water Act in 1974.
• In the late 1970s, the discovery and publicity surrounding Love Canal in Niagara Falls, NY
scandalized the chemical industry. At this and other locations, thousands of barrels filled
with chemical waste - which had been buried by chemical companies over the previous
decades - rusted through, leaking toxic chemicals into the soil and contaminated
groundwater.
1980s
• Until the 1980s, the chemical industry and the EPA were focused mainly on pollution
clean-up and obvious toxins, but a major paradigm shift began to occur among chemists.
Scientists, who came of age during the decades of growing environmental awareness,
began to research avenues of preventing pollution in the first place. Leaders in the
industry and in government began international conversations addressing the problems
and looking for preventative solutions.
• The Organization for Economic Co-operation and Development (OECD), an international
GREEN TECHNOLOGY 26
body of over 30 industrialized countries, held meetings through the 1980s addressing
environmental concerns. They made a series of international recommendations which
focused on a co-operative change in existing chemical processes and pollution prevention.
• The Ofﬁce of Pollution Prevention and Toxics was established within the EPA in 1988 to
facilitate these environmental goals.
• Forward-looking chemists shift from pollution remediation to pollution prevention; EPA's
office of Pollution Prevention and Toxics established in 1988.
1990s
• Staff of the EPA Office of Pollution Prevention and Toxics, coined the phrase "Green
Chemistry"
• This decade marked accelerated acceptance of pollution prevention and the establishment
of green chemistry as a legitimate scientific field.
• The Pollution Prevention Act of 1990 marked a regulatory policy change from pollution
control to pollution prevention as the most effective strategy for these environmental
issues.
• The Chemistry Director at the National Science Foundation (NSF) at the time, Kenneth G.
Hancock, made a point to publicly advocate this approach as an economically viable
strategy. Chemists across the globe agreed that this could reverse the industrial tendency
toward environmental deterioration.
• In the early 1990s, the European Community's Chemistry Council published papers on the
subject, including the influential work, "Chemistry for a Clean World." The ﬁrst
symposium based on these ideas, "Benign by Design: Alternative Synthetic Design for
Pollution Prevention," was held in 1994 in Chicago and sponsored by the Division of
Environmental Chemistry of the American Chemical Society.
• In 1993 a consortium was established among Italian universities, the Interuniversity
Consortium Chemistry for the Environment (INCA). The purpose was to develop
cooperative themes among chemists of various universities for environmental,
technological and green chemistry issues.
• Staff of the EPA Office of Pollution Prevention and Toxins, coined the phrase "Green
Chemistry" and sowed the seeds of productive collaboration between government,
industry, and academia.
• In 1995, the US EPA received support from President Bill Clinton to establish an annual
awards program highlighting scientific innovations in academia and industry that
advanced Green Chemistry. This created the annual Presidential Green Chemistry
Challenge Awards.
• The University of Massachusetts at Boston established the field's first Green Chemistry
Ph.D. program in 1997.
• In that same year, in cooperation with the EPA, Dr. Joe Breen, a retired 20-year staff
member of the EPA and chemist, Dennis Hjeresen, co-founded the Green Chemistry
Institute (GCI) as an independent nonprofit with Mary Kirchoff as Assistant Director and a
staff devoted to working exclusively to advancing green chemistry.
• GCI established the Green Chemistry & Engineering Conference in 1997, which has
continued to convene annually.
GREEN TECHNOLOGY 27
• Another very active group of scientists on green chemistry and green engineering for
sustainable development developed in England. The Green Chemistry Network (GCN)
aims to promote awareness and facilitate education, training and practice of Green
Chemistry in industry, commerce, central, regional and local government, academia and
schools. The network was initially launched in 1998 with funding from the Royal Society of
Chemistry and is now funded on a project-by-project basis. The GCN is a not-for-profit
Company Limited by Guarantee. The centre of GCN is in the Chemistry Department of the
University of York.
• Paul Anastas and John C. Warner co-authored the groundbreaking book, Green Chemistry:
Theory and Practice in 1998. The 12 Principles of Green Chemistry outlined within this
work declared a philosophy that motivated academic and industrial scientists at the time
and continues to guide the green chemistry movement.
2000s
• In 2001, the Green Chemistry Institute became a part of the American Chemical Society,
the largest professional scientific society and membership organization for chemists in the
world.
• The Nobel Prize in Chemistry was won for research in areas of chemistry that were largely
seen as being green chemistry in both 2001 (Knowles, Noyori, Sharpless) and 2005
(Chauvin, Grubbs, Schrock). These Nobel Prizes helped solidify the importance of research
in green chemistry and helped create a higher awareness among scientists that the future
of chemistry should be greener.
• Green chemistry groups, journals, and conferences launched all over the world. Examples
include:
o The Mediterranean Countries Network on Green Chemistry (MEGREC)
o The Royal Society of Chemistry's (UK) journal Green Chemistry
o The Green and Sustainable Chemistry Network in Japan (co-organizers of the
Asian-Oceania Conference on Green and Sustainable Chemistry)
o The Centre of Green Chemistry of Monash University in Australia
o Journal of Clean Processes and Products (Springer-Verlag) ,
o Green Chemistry (Royal Society of Chemistry and the University of York).
o Green Chemistry for Sustainability (Open Access, Springer),
o The Green and Sustainable Chemistry is an international open access journal
dedicated to reporting on the latest advances in Green and Sustainable
Chemistry. Published by Scientific Research Publishing, Irvine, California, USA
o Journal of Green Engineering (River Publishers, October 2010, Aalborg,
Denmark)
o Environmental Science and Technology (USA) and in the Journal of Chemical
Education (USA).
 Links to more organizations, schools, and conferences are found throughout the current
ACS GCI website.
 Educational and research curriculums became available to many schools, kindergarten
through post-graduate.
 In 2005, the ACS GCI established an industrial roundtable for the Pharmaceutical industry,
GREEN TECHNOLOGY 28
to catalyze and enable green and engineering into chemical businesses. Since then, two
additional roundtables for a chemical manufacturing and a formulator’s roundtable have
been established.
 Many successful entrepreneurial companies, whose products are based on the application
of green chemistry and engineering, have been established, selling everything from 'green'
glue to sustainable water processing solutions.
Today and the Future

• After all of the research advancements in green chemistry and engineering, mainstream
chemical businesses have not yet fully embraced the technology. Today, more than 98% of
all organic chemicals are still derived from petroleum.
• Green chemists and engineers are working to take their research and innovations out of the
lab and into the board room through the creation of viable industrial products that can be
embraced by today’s industry leaders.
• The ACS Green Chemistry Institute® continues to be a clearing-house of information,
connection, and research sharing through The Nexus Newsletter and Blog, the annual GC&E
Conference, industrial roundtables, and a growing number of educational and research
programs.
SANDESTIN DECLARATION: 9 PRINCIPLES OF GREEN ENGINEERING

During the week of May 19, 2003, approximately 65 chemists and engineers from industry,
academia, and government met at the Sandestin Resort in Florida for a conference on “Green
Engineering: Defining the Principles.” Over four days, they presented research and discussed green
engineering principles. By the end of the conference, the scientists collectively agreed to a
compiled set of nine principles, now known as The Sandestin Declaration.
These principles represent a majority view of green engineering as determined during the
Sandestin Conference. The Environmental Protection Agency, National Science Foundation,
Department of Energy (Los Alamos National Laboratory), and the ACS Green Chemistry institute,
supported the meeting.
The Sandestin Declaration: 9 Principles of Green Engineering
1. Engineer processes and products holistically, use systems analysis, and integrate
environmental impact assessment tools.
2. Conserve and improve natural ecosystems while protecting human health and well-being.
3. Use life-cycle thinking in all engineering activities.
4. Ensure that all material and energy inputs and outputs are as inherently safe and benign as
possible.
5. Minimize depletion of natural resources.
6. Strive to prevent waste.
7. Develop and apply engineering solutions, while being cognizant of local geography,
aspirations, and cultures.
8. Create engineering solutions beyond current or dominant technologies; improve, innovate,
and invent (technologies) to achieve sustainability.
9. Actively engage communities and stakeholders in development of engineering solutions
GREEN TECHNOLOGY 29
BRIEF HISTORY OF GREEN CHEMISTRY
1991:- The phrase "Green Chemistry" invented by the chemist Paul Anastas of US
Environmental Protection Agency (EPA)
1992:- United Nations Conference on Environment and Development (UNCED) in Rio de
Janeiro. Agenda 21 was adopted.
1995:- On President Bill Clinton’s initiative, EPA started to give a yearly “the U.S.
Presidential Green Chemistry Challenge Award”
1997:- “The Green Chemistry Institute” is formed by Joe Breen in the United States
(became part of ACS operations since 2001)
1998:- Paul Anastas and John C. Warner published the book “Green Chemistry: Theory and
Practice” (the book includes “The Twelve Principles of Green Chemistry”
1999:- The Royal Society of Chemistry formed “The Green Chemistry Network” and started
the journal “Green Chemistry”
Dr. Paul Anastas Dr. John Warner
GLOBAL RECOGNITION OF GREEN CHEMISTRY

Australia: The Royal Australian Chemical Institute (RACI) presents Australia’s Green Chemistry
Challenge Awards;
Canada: The Canadian Green Chemistry Medal is an annual award given to any individual or group
for promotion and development of green chemistry;
Italy: Green Chemistry activities in Italy centre on interuniversity consortium known as INCA. In
1999, INCA has given three awards annually to industry for applications of green chemistry;
Japan: In Japan, The Green & Sustainable Chemistry Network (GSCN), formed in 1999, is an
organization consisting of representatives from chemical manufacturers and researcher;
UK: In the United Kingdom, the Crystal Faraday Partnership, a non-profit group founded in 2001,
awards businesses annually for incorporation of green chemistry;
USA: United States Environmental Protection Agency (EPA);
Nobel Prize: The Nobel Prize Committee recognized the importance of green chemistry in 2005 by
awarding Yves Chauvin, Robert H. Grubbs, and Richard R. Schrock the Nobel Prize for Chemistry
for "the development of the metathesis method in organic synthesis.”
INDIAN CHAPTER
The recently constituted Green Chemistry Chapter of India has already started working to
popularize green chemistry in India. As a part of environmental movement, a National Symposium
on Green Chemistry was organized by the Department of Chemistry, University of Delhi in January
1999 to bring together all who are practicing green chemistry in India for the first time. For green
chemistry education, a refresher course was organized for college teachers by the Centre for
GREEN TECHNOLOGY 30
Professional Development in Higher Education in University of Delhi. Inspired by the

overwhelming response of participants in these events, recently an IUPAC International
Symposium on Green Chemistry was organized by the Department of Chemistry, University of
Delhi, which proved to be an excellent event for scientists’ world over to interact on the one
common platform. The Green Chemistry Chapter of India was constituted recently to expand its
domain. Some future activities under the banner of the Green Chemistry Chapter of India have
been planned. Top on the priority list is to spread the awareness of green chemistry among
researchers and young students by means of workshops, conferences, scholarships, and awards.
Simultaneously, there is a need to encourage industries to collaborate with academia and
government for effective practice of green chemistry.
OBJECTIVES FOR GREEN CHEMISTRY: THE COSTS OF WASTE

Hundreds of tonnes of hazardous waste are released to the air, water, and land by industry
every hour of every day. The chemical industry is the biggest source of such waste. Ten years ago
less than 1% of commercial substances in use were classified as hazardous, but it is now clear that
a much higher proportion of chemicals present a danger to human health or to the environment.
The relatively small number of chemicals formally identified as being hazardous was due to very
limited testing regulations, which effectively allowed a large number of chemicals to be used in
everyday products without much knowledge of their toxicity and environmental impact. New
legislation will dramatically change that situation. In Europe, REACH (Registration, Evaluation,
Assessment of Chemicals) will come into force in the first decade of the twenty-first century and
whilst, at the time of writing, the final form of the legislation has yet to be decided, it is clear that it
will be the most important chemicals-related legislation in living memory and that it will have a
dramatic effect on chemical manufacturing and use. REACH will considerably extend the number of
chemicals covered by regulations, notably those that have been on market since 1981 (previously
exempt), will place the responsibility for chemicals testing with industry, and will require testing
whether the chemical is manufactured in Europe or imported for use there. Apart from the direct
costs to industry of testing, REACH is likely to result in some chemical substances becoming
restricted, prohibitively expensive, or unavailable. This will have dramatic effects on the supply
chain for many consumer goods that rely on multiple chemical inputs.
Increased knowledge about chemicals, and the classification of an increasing number of
chemical substances as being in some way “hazardous”, will have health and safety implications,
again making the use of those substances more costly and difficult. Furthermore, it will
undoubtedly cause local authorities and governments to restrict and increase the costs of disposal
of waste containing those substances (or indeed waste simply coming from processes involving
such substances). Thus, legislation will increasingly force industry and the users of chemicals to
change – both through substitution of hazardous substances in their processes or products and
through the reduction in the volume and hazards of their waste.
The costs of waste to a chemical manufacturing company are high and diverse (Fig. 1.7) and,
for the foreseeable future, they will get worse. These costs and other pressures are now evident
throughout the supply chain for a chemical product – from the increasing costs of raw materials, as
petroleum becomes more scarce and carbon taxes penalize their use, to a growing awareness
amongst end-users of the risks that chemicals are often associated with, and the need to
disassociate themselves from any chemical in their supply chain that is recognized as being
GREEN TECHNOLOGY 31
hazardous (e.g. phthalates, endocrine disrupters, polybrominated compounds, heavy metals, etc.;
Fig. 1.8)
Figure 1.7 The costs of waste.
Figure 1.8 Supply chain pressures
GREEN TECHNOLOGY 32
GREEN CHEMISTRY AND SUSTAINABLE DEVELOPMENT:

The UN defines sustainable development as ‘meeting the needs of present without
compromising the ability of future generation.’ Green chemistry focuses on how to achieve
sustainability through science and technology
To better understand and solve the issue of environmental pollution, many approaches and
models have been developed for environmental impact assessments.
Some of these approaches and models have been successful in predicting impacts for selected
chemicals in selected environmental settings.
These models have joined air and water quality aspects to point and nonpoint sources and
have been very useful for the development of emission control and compliance strategies.
However, some of the approaches and models were aimed primarily at evaluating the
quantity of pollutants that could be discharged into the environment with acceptable impact,
but failed to focus on pollution prevention.
The concept of end-of-pipe approaches to waste management decreased, and strategies
such as environmentally conscious manufacturing, eco efficient production or pollution prevention
gained recognition.
GREEN CHEMISTRY FROM THEORY TO PRACTICE
Environmental issues in the past were considered as part of the economic system and the
rapid exploitation of natural resources. It took many years to consider the established ways that
materials were used (feedstocks), the initial design of chemical processes, the hazardous properties
of products, the energy consumption and other parameters involved in the manufacture of products
(life cycle, recycling, etc).
The definition of Green Chemistry starts with the concept of invention and design. This
means we, scientists and technologists, must take into account from the start what we are looking
for, what kind of product, how we are going to design its manufacture and its use. The impact of
chemical products and chemical processes must be included as design criteria. Hazard
considerations for initial materials and final products must also be included in the performance
criteria.
Another aspect of the definition of Green Chemistry is in the phrase “use and generation of
hazardous substances”. We must think in advance if use of the product is going to be dangerous
(workers, consumers) or if it is going to generate environmental pollution through their use or after
their practical application (as waste). Rather than focusing only on those undesirable substances that
might be inadvertently produced in a process, Green Chemistry also includes all substances that are
part of the process. Also, Green Chemistry recognizes that there are significant consequences to the
use of hazardous substances, ranging from regulatory, handling and transport, production of waste
and liability issues.
Green Chemistry aims not only for safer products, less hazardous consequences to the
environment, saving energy and water, but includes broader issues which can promote in the end
Sustainable Development.
GREEN TECHNOLOGY 33
The rapid development of new chemical technologies and the vast number of new chemical
products in the last decades turned the attention of environmentalists to remedial actions for the
negative impacts (monitoring environmental pollution, reduction of pollutants, recycling, etc).But
the fact is that the most effective way to reduce the negative impacts is to design and innovation in
the manufacturing processes, taking into account energy, materials, atom economy, use and
generation of secondary materials which are dangerous and finally the life cycle of the products and
their practical recycling into new materials.
In the last decade’s 600-700 million tons of chemical materials are produced every year
(excluding fossil fuels, fertilizers and medicines) from the chemical industries of the world. More
than 120,000 chemicals are in circulation for various applications, of which, approximately, 2,500 are
high volume products. Some of these chemicals have been studied for their toxicological and
ecotoxicological effects, but these studies are expensive and most of the ecotoxicological studies are
lacking. Despite the stringent environmental laws and regulations in the developed countries, there
are numerous environmental problems and adverse effects in sensitive ecosystems and habitats.
Figure1.9. Green Chemistry is a new “philosophy” of how to make chemical products in the chemical industry and for
chemical research. Innovative design and changes in chemical processes can eliminate hazards and help scientists to
achieve the goals to sustainable development.
THE TWELVE PRINCIPLES OF GREEN CHEMISTRY
The twelve principles of Green Chemistry cover the fundamental aspects of chemistry,
chemical engineering and technology. The number twelve is highly significant and symbolic (like the
twelve months of the year) as a complete sum of the most important things that we have to do to
accomplish a multiple task. Green Chemistry has to cover a broad section of chemical and
technological aspects in order to offer its alternative vision for sustainable development. Green
chemistry had to include fundamental ways to reduce or to eliminate environmental pollution
through dedicated, sustainable prevention programs. Green Chemistry must focus on alternative,
environmentally friendly chemicals in synthetic routes but also to increase reaction rates and lower
reaction temperatures to save energy.
Paul T. Anastas, an organic chemist working in the Office of Pollution Prevention and Toxins
at the EPA, and John C. Warner developed the Twelve Principles of Green Chemistry in 1991. These
principles can be grouped into "Reducing Risk" and "Minimizing the Environmental Footprint." Risk
has been a legacy of some chemical industries in the past. Hazardous chemicals to humans and
GREEN TECHNOLOGY 34
environmental pollution risk were connected with new chemical products and that gave a “bad
name” to synthetic chemical materials. The environmental footprint is more to do with energy
consumption, the climate crisis and depleting natural resources.
The Twelve Principles of GC can be analyzed fully in the following set
Principle No. 1. Prevention: It is better to prevent than to clean or to treat afterwards (waste or
pollution). This is a fundamental principle. The preventative action can change dramatically many
attitudes among scientists developed in the last decades. Most of the chemical processes and
synthetic routes produce waste and toxic secondary substances. Green Chemistry can prevent waste
and toxic byproducts by designing the feedstocks and the chemical processes in advance and with
innovative changes.
“An ounce of prevention is worth a pound of cure”
EXAMPLE:-
E-factor =Weight of byproducts/weight of desired product
 Oil refining 0.1
 Bulk chemicals <15
 Fine chemicals 5-50
 Pharmaceuticals 25-100+
Aprepitant(Aprepitant is an antiemetic chemical compound that belongs to a class of drugs called
substance P antagonists.) Synthesis
 Doubles yield
 Eliminates 340,000 L waste/ton of product
GREEN TECHNOLOGY 35
Aprepitant Statistics
 85% reduction in raw materials usage
 80% reduction in water usage
 85% reduction in waste
 75% lower manufacturing costs
 E-factor
–Reduced from 477 to 66
Principle No. 2. Maximise synthetic methods, Atom Econοmy: All synthetic methods until now
were wasteful and their yields between 70-90%. Green Chemistry supports that synthetic methods
can be designed in advance to maximize the incorporation of all reagents used in the chemical
process into the final product, eliminating the need to recycling the byproducts. The concept of Atom
Economy was developed by Barry Trost of Stanford University (USA), for which he received the
Presidential Green Chemistry Challenge Award in 1998. It is a method of expressing how efficiently a
particular reaction makes use of the reactant atoms.
EXAMPLE:-
Ibuprofen (Ibuprofen is an medicine used to manage mild to moderate pain, fever, inflammation,
menstrual cramps, and types of arthritis.) Synthesis
Traditional synthesis of ibuprofen
 6 stoichiometric steps
 <40% atom utilization
GREEN TECHNOLOGY 36
Catalytic synthesis of ibuprofen

 3 catalytic steps
 80% atom utilization (99% with recovered acetic acid)
Principle No. 3. Less hazardous chemical syntheses: Green Chemistry must strive, wherever
practical, to design safer synthetic methods by using less toxic substances as well as the products of
the synthesis. Less toxic materials mean lower hazards to workers in industry and research
laboratories and less pollution to the environment.
EXAMPLE:-
RE-HEALING™ Foam
Firefighting foam that contains hydrocarbon surfactants, water, solvent, complex carbohydrates, a
preservative, and a corrosion inhibitor
 Effective for flame knockdown, fire control, extinguishment, and burn-back resistance
 Eliminates fluorinated surfactants (PBT)
Sodium iminodisuccinate 
 Biodegradable, environmentally friendly chelating agent
 Synthesized in a waste-free process
 Eliminates use of hydrogen cyanide
GREEN TECHNOLOGY 37
Principle No. 4. Designing safer chemicals: Designing must become a fundamental aim of Green
chemists to affect the desired function and properties of the chemical product while minimizing their
toxicity to human and the environment. At present, there are around 100000 chemical substances
and materials in the market. Most of these substances have been characterized as to their
physiochemical properties and toxicities, but there is lack of ecotoxicological data for most of them.
From the 1980s there is more stringent regulation and new chemicals are monitored more
effectively.
EXAMPLE:-
EVOQUE Polymer
 Binder technology that reduces TiO2 use in paints
–TiO2 most commonly used paint pigment due to its ability to scatter and reflect incident
light
–Most expensive and energy intensive component
 EVOQUE polymers provide improved coverage at lower TiO2 levels
–Reduced carbon emissions and water consumption
Principle No. 5. Safer solvents and auxiliary substances: Solvents, separation agents and auxiliary
chemicals used in synthetic chemistry must be replaced or reduced with less toxic chemicals. Green
Chemistry initiated big changes in chemical laboratories and in the last decade there are less toxic
solvents in chemical laboratories and alternative techniques.
EXAMPLE:-
Non-Traditional Solvents
 Supercritical CO2
 CO2-expanded liquids
 Ionic liquids
 Liquid polymers (PEG)
 Switchable solvents
 Water
Benign Solvents: H2O
 Carbon-carbon bond formation in water
–Diels-Alder, Barbier-Grignard
 Indium-mediated cyclopentanoid formation
Micellar Catalysis
 Amphiphilic surfactant (TPGS-750-M) enables metal-catalyzed organic reactions in water
–Surfactant composed of vitamin E, succinic acid, and MPEG-750
–Eliminates large volumes of organic solvents
GREEN TECHNOLOGY 38
Principle No. 6. Design for energy efficiency: Chemists must recognize that until now there was
very little thought to energy requirements in chemical synthetic chemical processes designing more
efficient methods is a necessity and if possible synthetic methods should be conducted at room
temperature and pressure to reduce energy requirements.
EXAMPLES:-
Renewable Fuel
 Biofene®
–Genetically engineered baker’s yeast converts sugarcane into β-farnesene
–Catalytic hydrogenation yields farnesane (Amyris Diesel), a drop-in replacement for
petroleum diesel
–Benefits relative to petroleum diesel: higher cetane number, lower SOx and particulate
emissions
Energy
 Conversion of industrial waste gases via a microbial process into ethanol and chemicals
–70% reduction in greenhouse gas emissions compared to fossil fuel gasoline
–Reduction in particulate and NOx emissions
–Three pre-commercial facilities (steel mills) operating in China
Energy Efficient Technologies
 MAX HT™ Bayer Sodalite Scale Inhibitor
–Bayer process converts bauxite ore to alumina
–Problem: aluminosilicate crystals build up in heat exchangers/pipes
o Decreases efficiency of heat exchange
o Requires cleaning with H2SO4
 MAX HT™ inhibits crystal formation
 Annual savings per plant: $2-20 M, 9.5-47.5 trillion BTU
Principle No. 7. Use of renewable raw materials and feed stocks: Starting raw material for
synthetic processes are mostly petrochemical substances and products of refining. Raw materials
must have very low toxicity and if possible to be renewable, rather than depleting. We know that
there are many practical problems in finding renewable raw materials. Green chemists must change
the manufacturing process by discovering renewable chemicals. Development with depleting natural
resources is a negative aspect of economic growth.
EXAMPLES:-
Green chemists look for alternative sources for making materials. Renewable feedstocks (corn,
potatoes, and biomass) can be used to make many products: fuels (ethanol and bio-diesel), plastics
and more.
Maximyze® Enzymes
 Cellulase enzymes produced by fermentation from renewable resources
 Improved paper strength
GREEN TECHNOLOGY 39
– Reduces wood pulp needed

– Increases use of recycled paper
– Decreases energy use
– Reduces use of chemicals added
Spinetoram
 Produced by fermentation of renewable feedstocks using Saccharopolyspora spinosa
(Saccharopolyspora spinosa is a species of bacteria first isolated from a sugar mill rum still.)
–Controls wider range of pests at lower use rates
Principle No. 8. Reduce intermediate derivatives: Chemists must aim for reducing unnecessary
derivatization (use of blocking groups, protection/deprotection techniques and temporary
modification of physical and chemical processes) in the synthetic routes. These derivatizations use
additional reagents, are wasteful and produce large amounts of by-products and waste. The principle
reminds chemists to change their old ways of producing chemicals with more chemical steps and
additional materials. Designing new chemical synthetic routes are desirable.
EXAMPLES:
PCR Reagents
 Deoxyribonucleotide triphosphates (dNTPs)
 One-pot synthesis eliminates need for protecting groups, improves yields, minimizes
hazardous reagent and solvent usage, and decreases waste production
 E-factor drops from 3200 to 400
Boric-Acid Mediated Amidation

 Direct amidation of carboxylic acids with amines
– Boric acid: nontoxic, safe, inexpensive
– Eliminates use of SOCl2, PCl3, phosgene
– Widely applicable
GREEN TECHNOLOGY 40
Principle No. 9. Catalysis, catalytic reagents: The use of catalysts is well known that can change
dramatically the efficiency of chemical reactions and the yield of products. Catalytic reagents with
great selectivity can be superior to stoichiometric reagents. New catalysts and more emphasis on
catalytic processes is the future of green chemistry techniques.
EXAMPLES:-
TAML Catalysts
 Activate H2O2 for chlorine-free wood pulp bleaching (1999 PGCC)
 New application: Degrade endocrine disruptors in wastewater
Sitagliptin
 Active ingredient in Januvia™
–Treatment for Type II diabetes
–Controls blood sugar without significant side effects
 Enzymatic transamination reaction

–Eliminates high pressure and heavy metals
–Generally applicable in converting ketones to chiral amines
 1st generation: 8 steps, 44% overall yield
 New route: 3 steps, 50% increase in overall yield
–22,000 kg less waste per 1,000 kg product
Principle No.10. Design products which degrade easily: Most chemical products and consumer
items do not degrade very easily, thus causing environmental problems. Green Chemistry aims at
designing products so that at the end of their useful life to break down into innocuous materials.
Persistence into the environment is a negative aspect of many consumer products (e.g. plastic
GREEN TECHNOLOGY 41
products) and this can be reversed by designing products which degrade in a short time.
EXAMPLES:-
Biodegradable Polymers
 CO and CO2 used as monomers
 Catalyst exhibits high activity and high turnover number
Principle No. 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 substance.
EXAMPLES:-
Protein Testing
 Automated protein tagging technique
–Tags amino acids commonly found in proteins
 Employs non-toxic solutions
 Generates no hazardous waste
 Does not bind to fillers and other sources of non-protein nitrogen
–Replaces hazardous materials and high temperatures in traditional methods
–Applications in the food and pet food sectors
Principle No. 12. Inherently safer chemistry for accident prevention. Raw materials and chemical
substances used in chemical process should be inherently safe, i.e. their properties and their
degradation products to be non- toxic and not dangerous (e.g. to explode, to be flammable, allergic to
humans, cause burns to skin, etc). Green Chemistry aims to stop the use of dangerous materials for
the health and safety of workers and the consumer.
EXAMPLES:-
Vegetable Oil Dielectric Insulating Liquid
Envirotemp FR3 fluid
–Made from vegetable oils, biodegradable, nontoxic, carbon neutral
–Used in high voltage transformers
o Lifetime of solid insulation system (paper, wood, paperboard) determines life of
transformer
o Fluid absorbs water as paper decomposes
GREEN TECHNOLOGY 42
–Replaces mineral oil (low flash point)

These principles are obviously very difficult to apply immediately for many chemical processes.
After twenty years of Green Chemistry initiatives and industrial applications it is amazing to see
many creative innovations at various scientific and industrial processes. The cooperation of
chemists, engineers, material scientists, bioscientists and technologists has achieved interesting
results. The interdisciplinary approach has expanded the fields of green chemistry and produced
some excellent non-toxic materials and feedstock savings in chemical industries.
BENEFITS OF GREEN CHEMISTRY

Human health:
 Cleaner air: Less release of hazardous chemicals to air leading to less damage to lungs
 Cleaner water: less release of hazardous chemical wastes to water leading to cleaner drinking
and recreational water
 Increased safety for workers in the chemical industry; less use of toxic materials; less
personal protective equipment required; less potential for accidents (e.g., fires or explosions)
 Safer consumer products of all types: new, safer products will become available for purchase;
some products (e.g., drugs) will be made with less waste; some products (i.e., pesticides,
cleaning products) will be replacements for less safe products
 Safer food: elimination of persistent toxic chemicals that can enter the food chain; safer
pesticides that are toxic only to specific pests and degrade rapidly after use
 Less exposure to such toxic chemicals as endocrine disruptors
Environment:
 Many chemicals end up in the environment by intentional release during use (e.g., pesticides),
by unintended releases (including emissions during manufacturing), or by disposal. Green
chemicals either degrade to innocuous products or are recovered for further use
 Plants and animals suffer less harm from toxic chemicals in the environment
 Lower potential for global warming, ozone depletion, and smog formation
 Less chemical disruption of ecosystems
GREEN TECHNOLOGY 43
 Less use of landfills, especially hazardous waste landfills

Economy and business:
 Higher yields for chemical reactions, consuming smaller amounts of feedstock to obtain the
same amount of product
 Fewer synthetic steps, often allowing faster manufacturing of products, increasing plant
capacity, and saving energy and water
 Reduced waste, eliminating costly remediation, hazardous waste disposal, and end-of-the-
pipe treatments
 Allow replacement of a purchased feedstock by a waste product
 Better performance so that less product is needed to achieve the same function
 Reduced use of petroleum products, slowing their depletion and avoiding their hazards and
price fluctuations
 Reduced manufacturing plant size or footprint through increased throughput
 Increased consumer sales by earning and displaying a safer-product label (e.g., Safer Choice
labeling)
 Improved competitiveness of chemical manufacturers and their customers
PRACTICAL APPLICATIONS OF GREEN CHEMISTRY
Already from the 1980s, chemical industries under the pressure of new environmental laws
and regulations for workers health and safety and environmental pollution, changed their processes
and introduced new technologies. The economic incentives and the avoidance of litigations from the
state, citizens and environmental organizations were major factors in changes towards more benign
technological applications. But in most areas of industrial production old methods prevailed, for
example the use of petroleum products for feed stocks, in organic synthetic routes and in the use of
organic chlorinated solvents for separation. But the first seeds of green chemistry ideas started to
have a more pronounced effects in the chemical industry.
From the beginning of the 1990s the ideas of Green Chemistry started to have a more
international outlook. In 1998 the OECD through programmes such as “Risk Management
Programme”, promoted new and innovative activities under the broader umbrella of “Sustainable
Chemistry”. The purpose was to initiate alternative practices in the chemical industry and processes
more benign to the environment. A committee of scientists and technological experts was convened
from many industrial countries (Japan, USA, Germany, Sweden, Canada, etc) to propose the basic
areas of research and development for Green Chemistry applications.
The areas proposed for special focus under the green chemistry principles were the
following. They were selected with emphasis on economic considerations and for their future
contribution to sustainable development.
1. Use of alternative feedstocks. There are already many new developments in this field, but
the emphasis on renewable raw materials and a shift from fossil fuels is very desirable for
sustainability. The starting materials for the chemical industry must be renewable and less
toxic for workers and the environment.
2. Use of less hazardous reagents. There are now enough data for the toxicological and for
the long term ecotoxicological properties of most of the high volume chemicals used for
industry. Chemists and technologists must divert their efforts to use less dangerous raw
materials and reagents for the synthetic routes of the production of chemical products. But
if there are major obstacles they must choose less toxic substances and change their
GREEN TECHNOLOGY 44
technologies accordingly, for example using catalysts and new synthetic techniques.
3. Use of natural processes, like biocatalytic techniques. New biosynthetic methods were
developed in the last decades which are more selective, use less energy, lower
temperatures, higher yields and demand raw materials which are less toxic. Green
Chemistry research in the last decades replaced many old methods and introduced some
innovative catalytic methods with high yields and less waste.
4. Use of alternative solvents. Many solvents, especially polychlorinated and aromatic
solvents were used for decades for extraction techniques in synthetic organic chemistry.
Some of these solvents (e.g. carbon tetrachloride) were banned and some others are
restricted. Chemists use now less toxic solvents and their waste can be recycled or
decomposed at high temperatures. The chemical industry invested, under the Green
chemistry principles, in new solvents which are less toxic to workers and can disintegrate
more easily under environmental conditions.
5. Design of safer chemicals and products. Many new developments in methodology and
toxicological tests improved our understanding of the toxicity and their mechanisms of new
chemicals and products. The methodology of Quantitative structure-activity
relationships, QSARs can be used to speed up the estimation of toxicity, carcinogenicity or
other toxicological property of a new substance. Thanks to Green Chemistry principles and
applications most new chemical products have very low toxicity and are more benign to the
environment.
Figure 1.10. Industrial chemists have changed to a great extend the synthetic routes used for the production of
chemical products. Renewable raw materials, lower temperature, energy savings, less waste, alternative
solvents.
6. Developing alternative reaction conditions. In recent years there are many more
alternative or “greener” reaction techniques improving substantially the product yield,
saving energy and minimize waste. Photochemical reactions, microwave and ultrasound
assisted organic synthetic techniques, reactions using water as solvent, catalytic reactions,
etc are some of the new techniques in synthesizing chemicals.
7. Minimizing e n e r g y c o n s u m p t i o n . This is a very important goal considering the
energy savings and the climatic change which has become a global environmental problem.
The chemical industry has invested enough resources to reduce energy demands with
GREEN TECHNOLOGY 45
innovations and changes in synthetic reactions (lower temperatures, reducing steps). Green
Chemistry is very interested to contribute through research to minimize energy
consumption in every step of the industrial process
This was a very brief description of the most important changes in future industrial
processes which are going to improve efficiency, save energy, minimize waste, and produce
safer products and with less environmental impacts.
Table 1.2: Green Engineering and Green Chemistry Principles
Principle Green Engineering Green Chemistry

1 Inherent rather than circumstantial Prevention
2 Prevention instead of treatment Atom economy
3 Design for separation Less hazardous chemical use
4 Maximize efficiency Design for safer chemicals
5 Output-pulled vs. input-pushed Safer solvents and auxiliaries
6 Conserve complexity Design for energy efficiency
7 Durability rather than immortality Use renewable feedstock
8 Meet need, minimize excess Reduce use of derivatives
9 Minimize material diversity Catalytic reagents rather than stoichiometric
reagents
10 Integrate material & energy flows Design for degradation
11 Design for commercial afterlife Use real-time analysis for pollution prevention
12 Renewable rather than depleting Use safer chemistry to prevent accidents
Table 1.3: Common Themes in Green Chemistry and Green Engineering Principles
Principles Chemistry & Mass and Energy Toxicity and Renewability of
Technology Efficiency Persistence Feedstocks
Innovation
Green Chemistry 2,4,5,8,9-12 1,2,5,6,8,9 3,4,10 7,10
Green Engineering 3,11 2-5,10 1,7 12
Table 1.4: Green Engineering and Chemistry Principles Related to Pollution Prevention
Green Engineering Green Chemistry
#1: Ensure designs are as efficient and non- #1: Preventing the production of waste is better than
hazardous as possible cleaning or treating the waste
#2: Preventing the production of waste is better #2: Maximize incorporation of raw materials in to
than cleaning or treating the waste product
#4: Any process should be designed to its #3: Use less hazardous chemicals
maximum efficiency in terms of mass, energy,
space, and time
#4: Design safer chemicals
#5 Use safer solvents and auxiliaries
GREEN TECHNOLOGY 46
GREEN CHEMISTRY METRICS

Green chemistry metrics are metrics that measure aspects of a chemical process relating to
the principles of green chemistry. These metrics serve to quantify the efficiency or environmental
performance of chemical processes, and allow changes in performance to be measured. The
motivation for using metrics is the expectation that quantifying technical and environmental
improvements can make the benefits of new technologies more tangible, perceptible, or
understandable. This, in turn, is likely to aid the communication of research and potentially facilitate
the wider adoption of green chemistry technologies in industry.
YIELD AND ATOM ECONOMY IN CHEMICAL REACTIONS
A fundamental concept basic to green chemistry that can be illustrated by chemical reactions
is the distinction between yield and atom economy.
YIELD
Most of the chemical industry is concerned with turning one material (the raw material) into
another one that is more useful and valuable (the product). This process may have several steps and
is called a ‘chemical synthesis.’ All the designers of chemical processes want to make the maximum
amount of product they can from a given raw material. It is possible to calculate how successful one
of these processes is by using the idea of yield. Yield was defined as a percentage of the degree to
which a chemical reaction or synthesis goes to completion.
Percentage yield is a way of comparing amount of product made (actual yield) to amount
expected (predicted yield). We want a high percentage yield so that no reactants are wasted.
- 100% Yield means that no product has been lost

- 0% Yield means that all of the product has been lost
Reasons for not getting expected mass:
- Loss when filtering
- Loss when transferring liquids
- Loss when evaporating
- Not all the reactant was made into a product
The percentage yield can be calculated by:
𝐴𝑐𝑡𝑢𝑎𝑙 𝑝𝑟𝑜𝑑𝑢𝑐𝑡,𝑚𝑜𝑙
% yield= × 100
𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑃𝑟𝑜𝑑𝑢𝑐𝑡,𝑚𝑜𝑙
SELECTIVITY
 The selectivity of a reaction is the ratio of the desired product formed (in moles) to the
undesired product formed (in moles).
 Selectivity (S) is referred to the ratio of one of the products (usually the desired one) arising
from the conversion of a certain reactant with respect to the other ones, or to the conversion
of the starting material.
GREEN TECHNOLOGY 47
ATOM ECONOMY or ATOM SELECTIVITY or ATOM UTILIZATION

The concept of atom economy (AE) was introduced in 1991 by Barry M. Trost at Stanford
University. In the past, the material efficiency of a chemical reaction was routinely quantified by
measurement of the product yield, with an ideal value of 100 %. Atom economy has since sparked a
“green” paradigm shift, as chemists began viewing reactions in terms of how much of the reactants
are converted into a desired product. With the goal of achieving “synthetic efficiency in transforming
readily available starting materials to the final target”, the primary motivation was to maximize the
incorporation of reactant atoms into final products. This goal has led many chemists to focus their
attention on adopting and developing processes that were inherently atom-efficient. The
development of theoretical aspects of atom economy has occurred both in isolation and from the
point of view of green metrics. Atom economy is an important concept of green chemistry
philosophy, and one of the most widely used metrics for measuring the "greenness" of a process or
synthesis.
Atom economy was defined as the fraction of reactants that go into final products. The percent
atom economy is calculated very simply by the relationship
Atom Economy (AE or atom utilization), has been first defined by Trost in 1991 [1] as “the
ability of a chemical process to incorporate as many as possible of the atoms” of the starting material
into the final products, and thus to the ratio of the molecular weights (MW).
How atom economy can benefit society

By using processes with a higher atom economy, companies can reduce the waste produced. The
type of reaction is a major factor in achieving a higher atom economy:
 Addition reactions have an atom economy of 100%.
 Reactions involving substitution or elimination have an atom economy of less than 100%.
To improve the atom economy, a use must be found for the by-products. In industry, this is
sometimes done by selling off by products.
GREEN TECHNOLOGY 48
Those two ideas are illustrated here for the preparation of HCl gas which, dissolved in water,
produces hydrochloric acid. There are several ways in which HCl can be prepared. One of these
commonly used in the laboratory is the reaction of concentrated sulfuric acid, H2SO4, with common
table salt, NaCl, accompanied by heating to drive off the volatile HCl vapor:
2NaCl(s) + H2SO4(l) →2HCl(g) + Na2SO4(s)
This reaction can be performed so that all of the NaCl and H2SO4 react, which gives a 100%
yield. But it produces Na2SO4 byproduct, so the atom economy is less than 100%.
In this case, the mass of the desired product is that of 2 HCl and the total mass of product is
that of 2HCl + Na2SO4. Given the atomic masses H 1.0, Cl 35.5, Na 23.0, and O 16.0 give the following:
This result shows that even with 100% yield, the reaction is only 34.0% atom economical and
if it were used as a means to prepare HCl large quantities of Na2SO4, a material with only limited
value, would be produced. In contrast, the direct reaction of hydrogen gas with chlorine gas to give
HCl gas,
can be carried out with 100% atom economy if all of the H2
reacts with Cl2. There is no waste byproduct.
Now we will consider the following example
If we split up the formulae, we can look at what happens to each atom in the reaction. The
atoms shown below in bold end up in the product we want, the rest do not:
From the original atoms, one C atom and two O atoms are wasted – they are not in the final, useful
product. Green chemists define atom economy as:
GREEN TECHNOLOGY 49
STEP-BY-STEP: HOW TO CALCULATE ATOM ECONOMY
Step 1. Write out the balanced equation.

Step 2. Calculate the relative molecular mass of each of the products.
Step 3. Calculate the total mass of all the products (remember to account for any numbers in front of
the symbols,
Step 4. Work out which of the products are wanted and calculate their mass (again, do not forget any
numbers in front of the symbols).
SOLVED NUMERICALS
Q1. Hydrogen can be manufactured by reacting methane with steam:
CH4(g) + H2O(g) → 3H2(g) + CO(g)
Calculate the atom economy for the reaction. (Ar of H = 1, Ar of C = 12, Ar of O = 16)
Solution
Mr of CH4 = 12 + (4 × 1) = 16
Mr of H2O = (2 × 1) + 16 = 18
Total Mr of reactants = 16 + 18 = 34
Ar of H2 = (2 × 1) = 2
Total Mr of desired product = 3 × 2 = 6 (there are three H2 in the balanced equation)
Atom economy = × 100
Atom economy =
Atom economy = 17.6% (to 3 significant figures)
Q2. Copper oxide reacts with sulfuric acid to make copper sulfate and water. In an experiment,
1.6 g of dry copper sulfate crystals is made. If the theoretical yield is 2.0 g, calculate the
percentage yield of copper sulfate.
Solution:-
Actual yield = 1.6 g
Percentage yield = × 100

Percentage yield = 80%
Q3. Ethanol may be synthesized by following two routes (in presence of catalyst):
I. C6H12O6(aq) → 2C2H5OH(aq) + 2CO2(g)
II. C2H4(g) + H2O(g) → C2H5OH(l)
a. What is the % atom economy of both the reactions?
b. Which route is to be considered greener for the production of Ethanol in your
opinion, give reasons of your answer?
GREEN TECHNOLOGY 50
Solution:-
The manufacture of ethanol, used as a fuel, provides a useful example for choosing reaction
pathways. Ethanol is manufactured in two ways.
1. Fermentation of plant sugars:
Glucose → ethanol + carbon dioxide
C6H12O6(aq) → 2C2H5OH(aq) + 2CO2(g)
2. Hydration of ethene, obtained from crude oil, using steam:
C2H4(g) + H2O(g) → C2H5OH(l)
The table summarizes some features of these two processes.
Process Yield Atom economy Reaction rate
Fermentation of sugars 15% 51.1% Low
Hydration of ethene 95% 100% High
Worked example
Use information in the table above to evaluate the two processes for producing ethanol.
Fermentation has a lower percentage yield and rate of reaction than the hydration of ethene. The
hydration of ethene has an atom economy of 100%, showing that all the atoms in the reactants form
the desired product. As it also has a higher rate of reaction, the hydration of ethene appears to be the
better way to make ethanol.
Equilibrium position
The hydration of ethene is a reversible reaction. The equilibrium position lies to the left, so
only about 5% of the ethene supplied is converted to ethanol. The overall yield of 95% is achieved by
recirculating unreacted ethene through the reactor.
Using by-products
Carbon dioxide is a by-product of the fermentation of plant sugars. It may be sold to fizzy
drinks manufacturers to provide the bubbles in lemonade and cola. This makes it a desirable product
as well, so the atom economy can be increased to 100%.
Q4. Consider the synthesis of maleic anhydride from benzene as shown below
Calculate the atom economy for this reaction.

Solution:-
GREEN TECHNOLOGY 51
Q5. Hydrogen is made by two complete processes. One involves reaction of steam and coal and
the other involves reaction between methane and steam
C(s) + 2H2O(g) → CO2(g) + 2H2(g)
CH4(g) + H2O (g)→ CO(g) + 3H2(g)
a) What is the atom economy for making hydrogen by reacting coal with steam
according to the equation above?
b) What is the atom economy for making hydrogen by reacting methane with steam
according to the equation above?
Solution:-
A low atom economy indicates that the reaction is inefficient
Q6. Consider the formation of ammonia via the Haber process.

Nitrogen is reacted with hydrogen to produce ammonia, according to the equation below.
N2(g) + 3H2(g) => 2NH3(g)
The hydrogen, however, comes from the reaction between methane and water according to the
equation below.
CH4(g) + H2O (g)→ CO(g) + 3H2(g)
a) Calculate the atom economy for the formation of ammonia.
b) What is the atom economy with respect to hydrogen gas production?
Solution:-
GREEN TECHNOLOGY 52
Q7. P-cresol (19.61 g, 0.22 mol), MTBE (24.31 g, 0.22 mol) and a silica/zirconia catalyst (3.5 %
in weight) are heated at 100oC for 3 hours. After cooling the products are identified by GC. The
main product is 2-t-butyl-p-cresol (13.0 g), 10.78 g of p-cresol remain unreacted.Calculate yield,
selectivity and atom economy.
Solution:-
GREEN TECHNOLOGY 53
Q8. Butyl ethanoate is an ester used as a flavouring. This ester can be synthesised from butan-1-
ol by two different processes.
Process 1 is a one-step process that involves a reversible reaction.
Calculate the %age yield and atom economy for process 1 and process 2.
Solution:-
REACTION MASS EFFICIENCY (RME)
The Curzons Definition

In 2001, researchers from GlaxoSmithKline (GSK) presented a list of green metrics used by
their company to promote sustainable development. Among these, reaction mass efficiency (RME)
was emphasized as a realistic metric for describing the greenness of a process. Calculated as product
mass divided by the sum of the masses of reactants appearing in the balanced chemical equation, it
was eventually recognized that RME accounts for yield, stoichiometry and atom economy. This
important connection can be drawn by considering a generic reaction (Fig. 1.11) where an excess
amount of reactant B is added to reactant A to form product C. Using this example, the Curzons
reaction mass efficiency is derived in Fig. 1.12.
GREEN TECHNOLOGY 54
Curzons et al. further justified their metric using cost comparison models for drug
manufactures at GSK . Using this data they showed that atom economy influences the manufacture
cost of pharmaceuticals much less than yield and stoichiometry. Developing a simple method to
account for all three variables thus proved valuable for GSK. In subsequent years, Curzon’s RME has
gained greater appreciation from chemists in research, commercial and educational settings.
Figure 1.11:-Generic addition reaction where it is assumed that reactant B is in excess (i.e. y>x)
Fig. 1.12:- Derivation of reaction mass efficiency as the product of yield, atom economy and the inverse of a stoichiometric factor
according to the Curzons definition
Figure 1.13:-Two calculations of the Curzons RME for the esterification of benzyl alcohol and p-toluenesulfonyl chloride
GREEN TECHNOLOGY 55
The Curzons RME is therefore equivalent to a mathematical product consisting of yield, atom
economy and the inverse of a stoichiometric factor, a term introduced by Andraos to measure
reactant excess. It is worthwhile to check this derivation via Curzons’ own example (Figure 1.13).
Here, it is given that 10.81 g of benzyl alcohol reacts with 21.9 g of p-toluenesulfonyl chloride to
form 23.6 g of the sulfonate ester. Applying the equation derived in Fig. 1.12 results in a matching
RME value of 0.72 for the reaction. Note that the values of yield, atom economy, stoichiometric factor
and RME are expressed in absolute form (i.e. as a value ranging between 0 and 1). This is done to
make the RME product meaningful. Percent values cannot achieve this, and are therefore omitted for
the remainder of the chapter. Understanding the Curzons RME as a product of distinct terms is
important as it allows for developing more rational optimization strategies when deciding how to
improve the greenness of a process.
GREEN CHEMISTRY METRICS:-THE ENVIRONMENTAL FACTOR E FOR WASTE IN CHEMICAL
REACTIONS
Green Chemistry introduced various general metrics to give quantitative meaning of chemical
processes. Considering the fact that the simplest solutions are the best, Sheldon has developed a
simple and fast metric for evaluation of environmental impact of industrial processes, referred to as
E-Factor (environmental factor). According to its definition, the E-Factor is calculated as a total
weight of all waste generated in technological or industrial process (in kilograms) per kilogram of a
product. The closer to zero the value of E-Factor (E-Factor ~0) is, the less waste generated and more
sustainable and greener the process will be. However, it should be realized that, depending on its
potential application, the E-Factor can be calculated including or excluding water used in the
process. This parameter can also be used for evaluation of environmental impact of a specific
industrial process, for example production of a certain electronic device. The E-factor calculation is
defined by the ratio of the mass of waste (kg) per unit of product in kilograms:
E-factor = total waste (kg) / product (kg)
The Green Chemistry metric is very simple to understand and to use. It highlights the waste
produced in the process as opposed to the reaction, thus helping those who try to fulfill one of the
twelve principles of green chemistry to avoid waste production. The environmental E-factors ignore
recyclable factors such as recycled solvents and re-used catalysts, which obviously increases the
accuracy but ignores the energy involved in the recovery.
Roger A. Sheldon took his publications one stage further and produced the following Table
for E-Factors across the chemical industry
Industry sector Annual production (t) E-factor Waste produced (t)
Oil refining 106-108 <0.1 105-107
Bulk chemicals 104-106 <1–5 104-5×106
Fine chemicals 102−104 5–50 5 × 102−5 × 105
Pharmaceuticals 10–103 25–100 2.5 × 102−105
GREEN TECHNOLOGY 56
Higher E-Factor values reported for pharmaceutical industry compared with these values for
other sectors of chemical industry result from a necessity to obtain a very high-purity product in
the multi-stage reactions during which many by-products (waste) are generated. Additionally,
production of pharmaceuticals requires the use of high-purity reagents. A major limitation of the E-
Factor as a metric of environmental impact of technologic process is that it neither considers the
hazards nor the environmental risk of the produced waste. The two examples of successful
application of the E-Factor to evaluation of the greenness of technologic process in pharmaceutical
industry are: synthesis of sildenafil citrate (Viagra™) and synthesis of antidepressant sertraline
hydrochloride (Zoloft®). In the case of sildenafil citrate synthesis, introduction of toluene and ethyl
acetate recovery as well as total elimination of highly volatile solvents (e.g., acetone, diethyl ether)
from the synthetic pathway, resulted in lowering of the E-Factor value from 105 (in the time of drug
discovery) to 7 in the production stage. The pharmaceutical company that produces Viagra™ has
established a future target of lowering the E-Factor value to 4, which would be possible to achieve
through elimination of titanium chloride, toluene and hexane. By re-designing the chemical process
the manufacturers of sertraline hydrochloride (Zoloft®) achieved the E-Factor value of 8.
In some cases, more than one green metric is used for evaluation of environmental impact of
an industrial process. E-Factor and the Product Mass Intensity (PMI) can be given as an example of
such multi-metrics approach. The PMI has found its widest application in pharmaceutical industry.
A relation between E-Factor and PMI can be described by the following formula: E-Factor = PMI −
1. It is easier to calculate the PMI than E-Factor because it only requires the knowledge about inputs
into a reaction. The E-Factor value is necessary for calculation of another popular green chemistry
metric, the Environmental Quotient (EQ). It is a product of E-Factor and a Q value. The Q value
is defined as Environmental Hazard Quotient. It is related to ecotoxicity of waste generated during
an industrial process or organic synthesis. For example, the Q value for sodium chloride is 1
whereas this value for heavy metals and their salts is in the range of 100–1000.
Recyclable materials such as solvents, reused reactants or catalysts are not considered as
waste and thus ignored, and the ideal value of E is 0. Different parts contribute to the value of the
total E-factor (Eglobal).E-factor (Eglobal) defined as the sum of different contributions deriving from
the core chemical equation (by-products, side-products, and unreacted starting materials, Ekernel),
from excess reagent (Eexcess), and from auxiliary materials used in the process, including work-up
and purification operations (Eaux).
GREEN TECHNOLOGY 57
SOLVED EXAMPLES
GREEN TECHNOLOGY 58
GREEN TECHNOLOGY 59
GREEN TECHNOLOGY 60
GREEN TECHNOLOGY 61
GREEN TECHNOLOGY 62
GREEN TECHNOLOGY 63
UNSOLVED EXAMPLES (Module-1)

1. Bromoethane may be synthesized by following two routes
(I) Bromoethane can be produced from the reactants ethene (ethylene) and hydrogen
bromide in an addition reaction.
C2H4 + HBr → C2H5Br
(II) Bromoethane can also be manufactured using the reactants ethane and bromine in a
substitution reaction
C2H6 + Br2 → C2H5Br + HBr
a. What is the % atom economy of both the reactions?
b. What advantages would be there if route (I) was offered as a green chemistry alternative
for the production of Bromoethane.
2. To make sulfur dioxide, sulfur is burnt in oxygen:
S + O2=SO2
a. If 8 g sulfur is used, what is the maximum mass of sulfur dioxide that could be
produced?
b. If 14 g sulfur dioxide is produced, what is the percentage yield?
3. Iron is extracted from its ore using carbon:
2 Fe2O3 + 3 C →4 Fe + 3 CO2
What is the atom economy of this reaction?
4. Titanium can be extracted from its ore by two different methods. One uses a more reactive
metal to displace the titanium:
TiO2 + 2 Mg →Ti + 2 MgO
The second method is electrolysis of the ore. The overall reaction for this method is:
TiO2 →Ti + O2
a. Calculate the atom economy for each reaction.
b. Which method is ‘greener’? What else might you want to know before making a final
decision?
c. Oxygen is a useful product and can be sold. What is the atom economy of the
electrolysis if the oxygen is collected and sold?
5. Alkanes can be cracked to form alkenes. Decane can be cracked to form two products:
C10H22 →C2H4 + C8H18
a. If only the alkene can be sold, what is the atom economy of this process?
b. If both products can be sold, what is the atom economy?
c. Explain why your answers to (a) and (b) are different.
6. The key reaction in the Haber process for making ammonia is:
N2 + 3H2 →2NH3
a. What is the atom economy of this reaction?
b. What does the symbol suggest about the likely yield of this reaction?
GREEN TECHNOLOGY 64
REVIEW QUESTIONS
Objective Questions
1. Green chemistry aims to?
a) Design chemical products and process that maximize profits
b) Design safer chemical products and processes that reduce or eliminate the use and
generation of hazardous substances
c) Design chemical products and processes that work most efficiently
d) Utilize non-renewable energy
Ans:-b
2. Business benefits of green chemistry include?
a) Reduced costs associated with waste treatment and disposal
b) Innovating 'greener' products to entice customers
c) Greater compliance with environmental legislation
d) All of the above
Ans:-d
3. Green chemistry can reduce all but which of the following?
a) Cost b) Risk & Hazard
c) Awareness d) Waste
Ans:-c
4. Biodiesel is an example of which of the 12 Principles of Green Chemistry?
a) #1 – Waste prevention b) #7 – Use of renewable feedstocks
c) #9 – Use of catalysis d) #5 – Safer solvents
Ans:- b
5. Soybean is used to replace traditional inks in printer cartridges, highlighting which of the
Green chemistry principles?
a) Atom economy b) Use of Renewable Feedstock's
c) Reduce derivatives d) Prevent waste
Ans:-b
6. An example of green chemistry is?
a) Recycled carpet b) A product made on Earth Day
c) A sublimation reaction d) Bio-plastics
Ans:-d
7. The use of solar power is covered within Green Chemistry Principle #6, which is?
a) Atom economy b) Design for energy efficiency
c) Design benign chemicals d) Less hazardous synthesis
Ans:-b
8. _________ was a co-founder of the worldwide green chemistry movement and the first director
of the Green Chemistry Institute, now part of ACS?
a) Joseph Breen b) Albert Einstein
c) John Warner d) Paul Anastas
Ans:-d
9. Bio-polymers exemplify Green Chemistry Principle # 10, which is?
a) Catalysis b) Prevent waste
GREEN TECHNOLOGY 65
c) Benign solvents & auxiliaries d) Design for degradation

Ans:-d
10. Green chemistry can provide green technology solutions for a sustainable future?
a) True b) False
Ans:-a
11. A chemical process with an E-Factor of 1 creates LESS waste than an E-Factor of 25?
a) True b) False
Ans:-a
12. This word is synonymous with green chemistry and also means harmless, or gentle and not
life threatening?
a) Sustainable b) Benign c) User friendly d) Greenness
Ans:-b
13. The first listed of the 12 Principles of Green Chemistry is?
a) Prevent waste b) Catalysis c) Atom economy d) Benign solvents
Ans:-a
14. What is the U.S. Presidential Green Chemistry Challenge Award?
a) An award related to recycling b) An award for industry only
c) The only chemistry award given by the President
d) Challenges companies to become fuel efficient
Ans:-c
15. Green chemistry is more expensive than traditional chemistry?
a) True b) False
Ans:-b
16. Which of the following are among the 12 Principles of Green Chemistry?
a) Design commercially viable products b) Use only new solvents
c) Use catalysts, not stoichiometric reagents d) Re-use waste
Ans:-c
Short questions
1. “Green Chemistry is sustainable chemistry”- Explain the statement.
2. Define Green Chemistry. Why it is called so?
3. What do you mean by Sustainable Development?
4. State the 6 R’s (Reductions) pointed out by Green Chemistry.
5. Explain atom economy.
6. What are auxiliaries?
7. What is the difference between Green Chemistry and Environmental Chemistry?
8. What is green engineering, and what does it encompass?
9. What are the four pillars of green technology?
Long questions
1. Explain benefits of ‘Green Chemistry’ to human health, environment and economy & business.
2. Write down the twelve basic principles of green engineering. Explain any five principles of
‘Green Engineering’.
3. Write short notes on (i)Atom Economy (ii)E-factor
4. Explain why using reactions with high atom economy is important for sustainable
development.
GREEN TECHNOLOGY 66
5. Write down the twelve basic principles of green chemistry. Explain any three principles of
‘Green Chemistry’ excluding atom economy, with examples.
6. Why does industry need Green Chemistry?
GREEN TECHNOLOGY 67
Module-II
{Design of greener and safer chemicals, Solvent-free
methods: Microwave, Ultraviolet, and Solar. Green
catalysts: ionic liquids, zeolites, photocatalyst, PEG,
nanocatalyst, and biocatalyst. Green solvents: Supercritical
fluids, fluorous phase, and non-aqueous solvents.}
GREEN TECHNOLOGY 68
DESIGN OF GREENER AND SAFER CHEMICALS

The 4th principle of green chemistry, Designing Safer Chemicals, might sound like a paradox to
many people. The very concept of safe chemicals is not exactly common. Usually, all chemicals are
depicted as toxic substances. However, the word chemicals are used misleadingly in our everyday
lives. Chemicals are literally everything around us – every substance that is made of matter is a
chemical. This makes consumer labels claiming to be “Chemical-Free” meaningless! If used
properly, chemical-free products would be completely empty. With this in mind, Principle #4 is a
reminder to chemists that it is our responsibility to design all chemicals to not only be efficient at
their given purpose, but to also reduce their toxicity by design. Reducing toxicity is a constant
priority in chemistry. The challenge comes in knowing what makes a molecule toxic. When it comes
to molecules that have never been made before, toxicity becomes an even bigger concern. The field
of toxicology allows us to either predict or test for a molecule’s toxicity, making partnerships
between chemists and toxicologists incredibly important. Many green chemistry educators are also
pushing towards including a working knowledge of basic toxicology into undergraduate
chemistry degrees, to train all future chemists to consider toxicity from the very beginnings of
molecular design.
An auxiliary substance is one that helps in manufacture of a substance, but does not become
an integral part of the chemical. Such substances are used in the manufacture, processing at every
step. Major problem with many solvents is their volatility that may damage human health and the
environment. Even processes like recrystalisation require energy and substances to change the
solubility. The problem of solvents has been overcome by using such solvents which do not pollute
the environment. Such solvents are known as green solvents. Examples include liquid carbon
dioxide (supercritical CO2), ionic liquid water. Even reactions have been conducted in solid state.
For example the condensation reaction of ortho esters with o-phenylenediamines in presence of
KSF clay under solvent free conditions using microwave.
Many solvents used in traditional organic synthesis are highly toxic. The Green Chemistry
approach to the selection of solvents has resulted in several strategies. One method that has been
developed is to use supercritical carbon dioxide as a solvent. Supercritical carbon dioxide is formed
under conditions of high pressure in which the gas and the liquid phases of carbon dioxide combine
to a single –phase compressible fluid that becomes an environmentally benign solvent (temperature
31oC, 7280 kPa, or 72 atmospheres). Supercritical CO2 has remarkable properties. It behaves as a
material whose properties are intermediate between those of a solid and those of a liquid. The
properties can be controlled by manipulating temperature and pressure. Supercritical CO2 is
environmentally benign because of its low toxicity and easy recyclability. Carbon dioxide is not
added to the atmosphere; rather, it is removed from the atmosphere for use in chemical processes.
It is used as a medium to carry out a large number of reactions that would otherwise have many
negative environmental consequences. It is even possible to perform stereo selective synthesis in
supercritical CO2.
Some reactions can be carried out in ordinary water, the greenest solvent possible. Recently,
there has been much success in using near-critical water at higher temperatures where water
behaves more like an organic solvent. Eckert and Liotta were able to run Friedel-Crafts reactions in
near –critical water without the need for the acid catalyst AlCl3, which is normally used in large
amounts in these reactions. In the past 5 years, many new ionic liquids have been developed with a
GREEN TECHNOLOGY 69
broad range of properties. By selecting the appropriate ionic liquid, it is now possible to carry out
many types of organic reactions in these solvents. In some reactions, a well –designed ionic solvent
can lead to better yields under milder conditions than is possible with traditional solvents.
Another approach to making organic chemistry greener involves the way in which a reaction
is carried out ,rather than in the selection of starting material, reagents, or solvents. Microwave
technology can be used in some reactions to provide the heat energy required to make the
transformation go to completion .With microwave technology ,reactions can take place with less
toxic reagents and in a shorter time, with fewer side reactions, all goals of Green Chemistry.
Microwave technology has also been used to create supercritical water that behaves more like an
organic solvent and could replace more toxic solvents in carrying out organic reactions.
Another Green Chemistry approach is the use of a catalyst which facilitates transformations
without the catalyst being consumed in the reaction and without being incorporated in the final
product. Therefore, use of catalyst should be preferred whenever possible.
An example of a green compound is sodium stearate, common hand soap. This common
substance is prepared by reacting byproduct animal fat with sodium hydroxide, which is prepared
by passing an electrical current through saltwater. Flushed down the drain, sodium stearate reacts
with calcium in water to form a solid, calcium stearate, the white solid that composes “bathtub
ring,” and is removed from the water. The nontoxic calcium stearate readily undergoes
biodegradation so that it does not persist in the environment.
There are several characteristics of compounds that meet the criteria of being green. These
are the following:
• Preparation from renewable or readily available resources by environmentally friendly
processes
• Low tendency to undergo sudden, violent, unpredictable reactions such as explosions that
may cause damage, injure personnel, or cause release of chemicals and byproducts to the
environment.
• Nonflammable or poorly flammable
• Low toxicity
• Absence of toxic or environmentally dangerous constituents, particularly heavy metals facile
degradability, especially biodegradability, in the environment.
• Low tendency to undergo bioaccumulation in food chains in the environment
SOLVENT-FREE METHODS
Green Chemistry is concerned with the amounts of toxic organic solvents used in synthetic
routes and overall chemical processes. One principle of green chemistry is to reduce the use of
solvent as much as possible, or if possible to replace with a less toxic or to use alternative
techniques in which solvents are not needed. Solvents in the chemical industry are one of the major
problems concerning workers health and safety and environmental pollution because of waste.
Synthesis, separation of product, cleaning, drying, analysis and recycling, etc. are some of the
processes where solvents are used. Changing solvents and technological processes is not an easy
task. There are many alternatives but can be more expensive, time consuming or difficult to
implement under the established order of chemical methodologies. Although environmental
pollution from solvents can be a serious problem for many chemical industries, the solutions are not
always there to replace solvents or to reduce their use.
GREEN TECHNOLOGY 70
The earlier belief that no reaction is possible without the use of a solvent is no more valid. It
has been found that a large number of reactions occur in solid state without the solvent. In fact in a
number of cases, such reactions occur more efficiently and with more selectivity compared to
reactions carried out in solvents. Such reactions are simple to handle, reduce pollution,
comparatively cheaper to operate and are especially important in industry. It is believed that
solvent free organic synthesis and transformations are industrially useful and largely green. Green
chemistry, also called sustainable chemistry, is a chemical philosophy encouraging the design of
products and processes that reduce or eliminate the use and generation of hazardous substances. It
covers such concepts as:
 The design of process to maximize the amount of raw material that ends up in the
product
 The use of safe, environment benign substances, including solvents, whenever
possible
 The design of energy efficient processes
 The best form of waste disposal: do not create it in the first place.
Solid state reaction follows the fifth principle of green chemistry which avoid using solvents
and chemical reactions mostly occurring at room temperature which lead to energy efficiency. A dry
media reaction or solid-state reaction or solvent less reaction is a chemical reaction system in the
absence of a solvent. The drive for the development of dry media reactions in chemistry is:
 Economics (save money on solvent)
 Not required to remove a solvent after reaction completion ultimetly purification step
not required
 Reaction rate is high due more avaibility of reactants
 Environmentaly friendly because solvent is not required
Some of the drawbacks are:
 Homogenous reactants should mix to a system
 Viscosity high in reaction sysyem
 Unsuitable for solvent assisted chemical reactions
It has been found that many reactions proceed efficiently in the solid state. The occurrence of
efficient solid-state reactions shows that the molecules reacting are able to move freely in the solid
state. In fact, host-guest inclusion complexation can occur by simply mixing and grinding both
crystals in the solid state. These solid-state reactions can be easily monitored by measurement of IR
and UV spectra in the solid state. Though it is a common practice to run the organic reactions in
solvent media, the chemists concern to minimize the environmental pollution caused by solvents
and also their academic interest in solid-solid reactions have led them in recent times to develop
methodologies for solvent-free reactions with considerable success.
Solvent-free synthesis is gaining importance as a tool for the synthesis of a wide variety of useful
and important compounds, with the number of reactions conducted under these conditions
increasing. Initially, conventional methods have been utilized for solvent-free synthesis, but lately
there has been a shift in utilizing nonconventional energy sources, such as microwaves, ultrasound
and mechano-chemical mixing to increase the efficiency of the reactions. This chapter highlights
activity using microwave- and ultrasound-assisted solvent-free synthesis, discusses their
advantages and limitations, and plausible mechanisms involved. The importance of solvent-free
synthesis using nonconventional methods is shown by selected examples.
GREEN TECHNOLOGY 71
Organic reactions under solvent-free conditions are advantageous because of enhanced

selectivity and efficiency, easy of manipulation, and more importantly, because toxic and often
volatile solvents are avoided. Solvent-free approaches involve mechanochemical mixing (grinding),
microwave (MW) irradiation of neat reactants (undiluted), or catalysis by the surfaces of
inexpensive and recyclable mineral supports, such as alumina, silica, clay, or ‘doped’ surfaces.
ADVANTAGES OF SOLVENT-FREE REACTIONS

A solvent-free or solid state reaction may be carried out using the reactants alone or
incorporating them in clays, zeolites, silica, alumina or other matrices. Thermal process or
irradiation with UV, microwave or ultrasound can be employed to bring about the reaction
Solvent-free reactions obviously reduce pollution and bring down handling costs due to
simplification of experimental procedure, work up technique and saving in labour. These
would be especially important during industrial production
Often, the products of solid state reactions turn out to be different from those obtained in
solution phase reactions. This is because of specific spatial orientation or packing of the
reacting molecules in the crystalline state. The orientational requirements of the substrate
molecules in the crystalline state have provided excellent opportunities to achieve high
degree of stereoselectivity in the products. This has made it possible to synthesize chiral
molecules from prochiral ones either by complexation with chiral hosts or formation of
intermediates with chiral partners.
If two or more substrates are involved in the reaction, they are thoroughly ground together
in a glass mortar or cocrystallized and allowed to stay at room temperature or transferred to
a suitable apparatus and heated carefully in an oil bath or exposed to appropriate radiation
until the reaction is complete. More sophisticated reaction procedures are also adopted, if
necessary. The progress of the reaction can be monitored by TLC. In some cases, a small
quantity of water or a catalyst may be added. If it is a single-compound reaction, it is
subjected to heat or radiation directly. Care is to be taken to collect the volatile products, if
they are produced.
MICROWAVE TECHNIQUES FOR ORGANIC SYNTHESIS

INTRODUCTION
Synthesis of new chemical entities is major bottleneck in drug discovery. Conventional
methods for various chemical syntheses is very well documented and practiced. The methods for
synthesis (Heating process) of organic compounds has continuously modified from the decade. In
1855, Robert Bunsen invented the burner which acts as energy source for heating a reaction vessel,
this was later superseded by isomental, oil bath or hot plate, but the drawback of heating, though
method remain the same. Microwave Assisted Organic Synthesis (MAOS), which has developed in
recent years, has been considered superior to traditional heating.
Microwave assisted organic synthesis (MAOS) has emerged as a new “lead” in organic
synthesis. The technique offers simple, clean, fast, efficient, and economic for the synthesis of a large
number of organic molecules. In the recent year microwave assisted organic reaction has emerged
as new tool in organic synthesis. Important advantage of this technology include highly accelerated
rate of the reaction, Reduction in reaction time with an improvement in the yield and quality of the
product. Now day’s technique is considered as an important approach toward green chemistry,
because this technique is more environmentally friendly. This technology is still under-used in the
GREEN TECHNOLOGY 72
laboratory and has the potential to have a large impact on the fields of screening, combinatorial
chemistry, medicinal chemistry and drug development. Conventional method of organic synthesis
usually need longer heating time, tedious apparatus setup, which result in higher cost of process
and the excessive use of solvents/ reagents lead to environmental pollution. This growth of green
chemistry holds significant potential for a reduction of the by product, a reduction in waste
production and a lowering of the energy costs. Due to its ability to couple directly with the reaction
molecule and by passing thermal conductivity leading to a rapid rise in the temperature, microwave
irradiation has been used to improve many organic syntheses.
MW irradiation, an unconventional energy source, has been used for a variety of organic
transformations wherein chemical reactions are accelerated because of selective absorption of MW
energy by polar molecules; non-polar molecules are inert to the MW dielectric loss. The MW
application under solvent fewer conditions enables rapid synthetic transformations at ambient
pressure, thus providing unique chemical processes with special attributes such as ease of
manipulation, enhanced reaction rates, and higher yields.
Figure 2.1. New equipment appeared in the market for microwave irradiation reactions with special reflux condensers
and digital indicators.
MICROWAVES – Out of Kitchen into the Chemical Laboratory

Although the use of microwaves in the preparation of food dates back to around forty years, it is
only since past two decades that they have found their way into the chemical laboratory.
“History of microwaves ovens”- An accidental discovery
In 1946, the real potential of microwaves came to lime light when Percy le Baron Spencer, an
American Engineer working with radar equipments while testing a new type of vacuum tube – the
magnetron, at Raytheon noticed that some candy he had in his pocket, melted when he accidentally
leant against an open wave guide( a rectangular hollow tube of metal used to conduct microwaves).
Spencer began conducting more experiments with uncooked kernels and raw eggs. He watched
popcorn bounce around the room and raw egg placed near the magnetron, explode from the pressure
built up inside. The potential of Spencer‟s discovery was soon realized at Raytheon who began to
produce the first microwave ovens called the “Radaranges”. It was first sold in 1946. Raytheon later
licensed its patents for a home-use microwave oven that was first introduced by Tappan in 1955, but
these units were still too large and expensive for general home use. Sharp Corporation introduced the
first microwave oven with a turntable between 1964 and 1966. The countertop microwave oven was
GREEN TECHNOLOGY 73
first introduced in 1967 by the Amana Corporation. After Sharp introduced low-cost microwave ovens
affordable for residential use in the late 1970s, their use spread into commercial and residential
kitchens around the world.
Since then, upto the middle of 1980‟s, microwave ovens were used only for cooking and
defrosting frozen food. The first application of microwaves irradiation in chemical synthesis was
published in 1986. However, in 1986, due to the independent work of Richard Gedye and co-
workers at Laurentain University, Canada and Majetich and Giguere at the University of Georgia,
USA, microwaves successfully made the transition from kitchen to the chemical laboratory as they
could do much more than mere cooking. The researchers reported increase in the rates of a number
of organic reactions using a commercially available microwave oven. These reports formed the
basis of an ever increasing range of research publications over the next twenty years. Later
considerations for the safety and the need to achieve controllable, reproducible and focused
homogenous heating led to the development of specially designed microwave equipments. The new
microwave ovens were fitted with temperature and pressure detection devices making it possible
to monitor a reaction while it is being irradiated under the oven.
MICROWAVE
Microwave heating refers the use of electromagnetic waves ranges from 0.01m to 1m wave
length of certain frequency to generate heat in the material. These microwaves lie in the region of
the electromagnetic spectrum between millimeter wave and radio wave i.e. between I.R and radio
wave. They are defined as those waves with wavelengths between 0.01metre to 1meter,
corresponding frequency of 30GHz to 0.3GHz.
microwave
PRINCIPLE OF MICROWAVE HEATING
Microwaves provide the only method of heating that does not involve thermal conduction.
While as infra red or heat radiations get absorbed on the surface of a material, microwaves
penetrate several centimeters deep into it carrying the electromagnetic energy to the core of the
GREEN TECHNOLOGY 74
material. The heat generated in a sample on microwave exposure has mainly been attributed to the
electric component of microwaves usually by two mechanisms - Dipolar polarization and ionic
conduction or charge space transfer.
1. Dipolar mechanism
Microwave heating of a solid or a liquid is related to the existence of an electric dipole in the
molecule of the material. In water, for example, the dipole arises due to the different affinities of
oxygen and hydrogen atoms for the available electron density and the angular shape of water
molecule. As the electron density is concentrated more on the electronegative oxygen atom, the
result is a net dipole moment for the water molecule.
Fig. 2.2. Dipolar molecules try to align with oscillating electric field of microwaves.
The heating effect generated in microwave-assisted organic transformations is mainly due to
the dielectric polarization i.e. orientation of a dipole with that of the applied field (figure 2.2). If the
field is alternating, the dipole tends to align and realign itself with the applied field leading to
thermal agitation which in turn produces heat. This effect can be explained as follows:-
The polar molecules, in the absence of an electric field, will have a random arrangement. This
chaotic order with greater entropy will be the natural, lowest energy configuration for the assembly
of molecules (figure 2.3). When placed in a strong electric field for some time, these polar molecules
will tend to align themselves parallel to this field (figure 2.4). This new arrangement of molecules
will therefore be higher in energy because of decrease in entropy and can be thought of as storing
potential energy due to the application of electric field. If the direction of the applied field is
changed slowly, the polar molecules will also rotate and try to keep themselves aligned with the
field (figure 2.5). If the direction of electric field is changed more quickly, some of the molecules may
not be able to remain in alignment with the direction of applied field. The molecules may try hard to
remain in parallel with the field but keep colliding with other molecules. The potential energy
stored in the changing molecular alignment no longer matches the applied field. This excess energy
is transformed into kinetic energy on collision between the molecules and this effect gives rise to
microwave heating.
Fig 2.3. Dipoles in absence of an electric field
GREEN TECHNOLOGY 75
Fig.2.4. Dipoles in presence of an electric field
Fig. 2.5. Dipoles rotating in case of changing electric field

A variable power output is achieved by switching the magnetron on and off according to a
duty cycle. The exposure of a molecule to this alternating current inverses the electric field at each
alternation, with a subsequent tendency for dipoles to move together to follow the field. Such a
characteristic changing field induces stirring and friction of molecules which appears as internal
homogeneous heat. In fact, the heating or cooking of food in microwave ovens is because of the
dipolar polarization of water molecules present in the food. Other biological molecules in food are
far too large to be able to rotate.
The ability of a material to convert electromagnetic energy into heat at a given frequency and
temperature is expressed by the following equation
tan δ = ε / έ
Where δ = dissipation factor of the sample
ε = dielectric loss, which measures the efficiency with which heat is generated from
the electromagnetic radiation
έ = dielectric constant which gives the ability of a molecule to be polarized by an
electric field.
The high value of dissipation factor δ indicates large susceptibility to microwave energy. In
addition to this, factors like interfacial polarization and Maxwell-Wagner effect may also contribute
to the heating effect when the conducting particles are in contact with a non-conducting medium,
for example, in heterogeneous reactions. Quantitatively, the larger the dielectric constants, the
greater the interaction with microwaves. Since the ability of a molecule to couple with the
microwave radiation is a function of its molecular polarisability (i.e. a function of its dipole
moment), only polar molecules interact with microwave energy. As a guide, compounds with high
dielectric constants such as water, ethanol, acetonitrile, N,N-dimethyl formamide (DMF), acetic acid,
GREEN TECHNOLOGY 76
chloroform. dichloromethane, acetone, ethylene glycol etc., tend to heat rapidly under microwave
irradiation, while less polar substances, such as aromatic and aliphatic hydrocarbons or compounds
with no net dipole moment, such as carbon dioxide, carbon tetrachloride, diethyl ether etc. as well
as highly ordered crystalline substances, are poorly absorbing hence microwave inactive. Thus,
polar molecules in a non-polar solvent would absorb energy, but not the solvent or the reaction
vessel, if it is made of teflon (μ = 2.1 at 22 °C) or ceramic or even pyrex (μ= 4.5–6.0). Sometimes it is
possible to use mixtures comprising microwave active reactants and microwave inactive solvents. It
has also been suggested that if microwave energy is absorbed by the solvent and not by the
substrate, only modest rate increase will result relative to those observed with conventional energy.
If, on the other hand, the microwave energy is absorbed selectively by a reactant, by a complex or
by an intermediate during the rate determining step, then large rate increase will result.
The mechanism by which the rotating molecule can grab the energy from microwaves and
thereby increase its rotational energy can be understood from the wave nature of the
electromagnetic radiation. The radiation is an oscillating electric field which effect tends to move
the charged particles one way or the other. If the rotating molecule possesses an electric dipole, the
positive and negative ends will change their orientation periodically due to the interaction with
electric field of microwaves.
Fig.2.6. The interaction of the electric field of radiation with the dipole of molecule
When the molecule is in position 1, the electric field is such that it pushes the negative end
up and therefore the positive end down making the molecule to rotate. When the molecule has
GREEN TECHNOLOGY 77
rotated to position 5, the radiation has also moved along to its next cycle, but the interacting force
will still make the molecule to rotate faster (figure 6). If the frequency of microwaves and that of the
molecular rotation are equal, the electric field can interact with the molecular dipole and keep the
molecule pushing to a higher rotational energy. It is this excess energy of the polar molecules that
appears as heat. It is noteworthy that if the electric field changes direction very rapidly, the polar
molecules will not have the time to react to the changing field and will remain randomly oriented
and consequently at these microwave frequencies, they will be unable to interact with the applied
field and no heat will get generated.
2. Ionic conduction mechanism
In a solution containing ions or even an isolated ion, ions will move in a solution under the
influence of an electric field resulting in expenditure of energy due to an increased collision rate
converting the kinetic energy to heat, for example, if two samples containing distilled water and tap
water are heated in a single mode microwave cavity at the same time and power level, the final
temperature will be higher in the tap water sample. It has been found that the conductivity
mechanism is much stronger than the dipolar mechanism with regard to the heat generation
capacity.
CONVENTIONAL VS MICROWAVE HEATING

It is worth stressing that microwaves, in contrast to conventional heating methods, are means
of volumetric heating of materials (Fig 2.7), which causes more extensive heating inside the material
in comparison with outer layers of the material, which in turn makes hard proper measurements of
the reaction temperature. Temperature measurement under microwaves conditions, particularly for
the reactions in dense and solvent fewer medium, is difficult. Therefore, it source of inappropriate
interpretation of experimental results and divergence in descriptions of the same experiments.
Figure:2.7 Different heating mechanisms for conventional and microwave heating.
GREEN TECHNOLOGY 78
INTERACTION OF MICROWAVES WITH DIFFERENT MATERIALS

Currently, in order not to cause interference with telecommunication devices, household and
industrial microwave ovens are operated at either 12.2 cm (2.45 GHz) or 32.7 cm (915MHz).
However, some other frequencies are also available for heating. Most common domestic microwave
ovens utilize the frequency of 2.45 GHz, and this may be a reason that all commercially available
microwave reactors for chemical use operate at the same frequency.
Heating in microwave cavities is based upon the ability of some liquid and solids to absorb and
transform electromagnetic energy into heat. In general, during the interaction of microwaves with
materials three different behaviors of a material can be observed depending whether the material is
counted among.
Figure:2.8. Interaction of microwaves with different materials (a) electrical conductor, b) insulator, (c) Lossy dielectric.
GREEN TECHNOLOGY 79
(1) Electrical conductors (e.g. metals, graphite- fig 2.8 a)

(2) Insulators, which are considered as materials with good dielectric properties ex-tremly
poor conductors) (e.g. quartz glass, porcelain, ceramics, Teflon-fig 2.8 b)
(3) Lossy dielectrics, which are materials that exhibit so called dielectric losses, which in turn
results in heat generation in an oscillating electromagnetic field (e.g. water fig 2.8 c ).
When a strongly conducting material (e.g. a metal) is exposed to microwave irradiation,
Microwaves are largely reflected from its surface (fig.2.8 a). However, the material is not effectively
heated by microwaves, in response to the electric field of microwave radiation, electrons move freely
on the surface of the material, and the flow of electrons can heat the material through a resistive
heating mechanism. In opposite, in the case of insulators ( e.g. porcelain), microwaves can penetrate
through the material without any absorption, losses or heat generation. They are transparent to
microwave (fig.2.8 b). Passage of microwave radiation which is electromagnetic in nature can give
rise to absorption of microwave energy and heat generation due to the so called dielectric heating
mechanism (fig.2.8 c).
MERITS AND DEMERITS OF MICROWAVE HEATING

MERITS/ADVANTAGES
 Microwave assisted synthesis reduces the time of reaction substantially. Microwave
enhancement may take several forms like reaction rates get accelerated, yields get improved
than the conventional counterparts and virtually no decomposition takes place during the
drying of samples.
 Microwaves form an essential aspect of green chemistry because of the solvent-free technique.
Reactants can be adsorbed on solid supports like clay, montmorillonite, silica gel, alumina, etc
and then exposed to microwaves. This eco-friendly procedure minimized the use of solvents
leading to cleaner reactions and improved yields in addition to being safer. Ability to control
the desired chemo, regio or stereo selectivity is possible using microwave assisted synthesis.
 Microwave heating can be used with less operator intervention, improved safety and greater
control over the reaction conditions as well as minimum sample contamination and loss.
 Use of continuous flow microwave systems allows the samples to be digested or extracted in
an online system for direct analysis.
 Microwave reactions are ecofriendly and can be achieved under solvent-free conditions.
 The advantages of microwaves are applicable to different disciplines of chemical research like
drying of samples, melting of solid samples and a variety of organic and inorganic synthetic
reactions.
DEMERITS/LIMITATIONS/DISADVANTAGES
 Reaction requiring the use of dry nitrogen atmosphere, fuming, lachrymatory substances or
substances which may corrode the interior of the oven cannot be conducted inside a
microwave oven.
 There is a possibility that the higher temperatures/superheating of the solvent in sealed
vessels may encourage the decomposition of the desired products or may lead to the
formation of thermodynamically stable product in preference to the kinetically favoured
product.
 Metals are reflective to microwaves and the radiation tends to bounce off them like the light
from a mirror. Due to this, metal particles or metals have to be avoided inside the microwave
oven because there is always a possibility of an electric spark in the oven.
 No closed vessels should be used except the ones specially designed for withstanding high
pressures like teflon tubes.
 One of the draw backs of domestic microwave ovens is the power levels which significantly
GREEN TECHNOLOGY 80
change from unit to unit.
MICROWAVE REACTOR
COMPONENTS AND FEATURES
A schematic diagram of a microwave reactor is shown in figure 2.9.
Fig.2.9. Cavity-type microwave reactor

The microwave oven consists of the following components:
 Magnetron/Klystron It is a thermionic diode possessing an anode and a directly heated
cathode. It emits the radiation over a narrow frequency range.
 Wave guide It is a hollow tube of metal of rectangular cross- section with reflective walls to
allow the transmission of microwaves from the magnetron to the microwave cavity.
 Microwave cavity It is the internal space of the oven where the samples are placed for
irradation and usually contains a turn table to ensure that each sample experiences the same
average heating. The cavity has reflective walls to prevent the leakage of microwaves as well
as to increase the efficiency of the oven.
 Mode Stirrer A reflective fan shaped paddle to ensure that the microwaves are evenly
distributed throughout the cavity.
 Door interlocks These are safety devices in the door of the oven to prevent the door from
being opened during microwave irradiation.
 Exhaust fan This isolates and ventilates the oven to prevent acid fumes from attacking the
electronics of the unit.
 Time control This allows the time to be set for which the sample is to be irradiated
 Power control This allows the power level to be set before microwave irradiation of a sample
is to be done.
GREEN TECHNOLOGY 81
TYPES OF MICROWAVE REACTOR

Two types of microwave reactors can be used in the Laboratory. Multimode Microwave Reactors and
Monomode Microwave Reactors.
1. MULTIMODE MICROWAVE REACTORS
Figure:2.10 Multimode Microwave Reactor

Multimode reactors have larger cavities in which the microwave field is distributed in a
chaotic manner. In common multimode reactors the waves are reflected from the cavity walls and
multiple modes of the electromagnetic waves interact with the cavity load (Figure 2.10). The
distribution of electric field is not homogeneous creating temperature gradients in different zones
called as “hot spots”. In addition, the multimode oven doesn‟t have any provision for accurate
temperature measurement Because of their larger size, these instruments can host different rotor
types. These are basically used for parallel reactions in a scale range from a 300 µL scale up to
multigram synthesis in 100 mL reaction vessels.
The use of multimode reactors has however, following limitations:
a) The distribution of electric field inside the cavity results from multiple reflections off the
walls and reaction vessel and is consequently heterogeneous;
b) The temperature cannot be simply and accurately measured;
c) The power is not tunable.
2. MONOMODE MICROWAVE REACTORS
Figure :2.11 Monomode Microwave Reactor
GREEN TECHNOLOGY 82
Monomode reactors have small compact cavities, in which microwave irradiation is directly
focused on one single vessel containing the reaction mixture (Figure 2.11). Consequently, a high
microwave field density is provided, resulting in exceedingly fast heating rates. The maximum
applicable reaction volume in monomode reactors is 20 mL, which makes them an ideal tool for
optimizing chemical reactions on a small scale. They are optionally equipped with a camera for
visually following the reaction process, with autosampler units allowing for automated overnight
processing as well as straightforward workflows in a multi-user environment.
3. MULTIMODE MICROWAVE REACTORS FOR SINGLE-BATCH SCALE-UP
Figure :2.12 Multimode Microwave Reactor for single Batch Scale-up

This special kind of multimode reactor features a circular waveguide in which various modes
of the electromagnetic waves interact with the vessel content at different spots for efficient heating of
larger volumes (Figure 2.12). A single 1 L vessel is positioned in a compact cavity, which provides a
relatively high field density (compared to common multimode microwave ovens as shown in Figure
2.10). This results in optimized heating rates for large scales. This kind of multimode reactor is used
for single-batch scale-up if amounts of up to 1 kilogram of reaction product per day are required.
The microwave oven used for cooking purposes is a multimode reactor. Moreover, for the
reaction vessel to withstand high pressures, teflon (polytetrafluoroethyene PTFE) has been employed
in the manufacture of reaction vessels and tubes that can withstand pressures upto 1500 psi unlike
glass vessels which cannot withstand such high pressures and lead to accidents. In spite of
reproducible results obtained using monomode ovens, the use of multimode ovens by chemists in
research laboratories continues because of convenience and economical benefit.
MICROWAVE IN ORGANIC SYNTHESIS

Microwaves have been used to speed up chemical reactions in the laboratories which led
scientists to investigate the mechanism of microwave dielectric heating and to identify the
advantages of the technique for chemical synthesis. During recent years, microwaves have been
extensively used for carrying out chemical reactions and have become a useful non-conventional
energy source for performing organic synthesis. The first recorded application of microwave energy
in organic synthesis is the aqueous emulsion polymerization of butyl acrylate, acrylic acid and
methacrylic acid using pulsed electromagnet radiation. The start of the rapid growth of microwave
assisted procedures in organic synthesis was ignited in 1986. Even microwave-assisted reactions
GREEN TECHNOLOGY 83
under solvent-free conditions promoted the synthesis of Zincke’s salt and its conversion to chiral
pyridinium salts in water and microwave- assisted organic transformations using benign reaction
media have also been reported.
VARIOUS TYPES OF MICROWAVE ASSISTED ORGANIC REACTIONS

The microwave-assisted organic reactions have been broadly classified into two categories:
I. Microwave-assisted reactions using solvents.
II. Microwave-assisted reactions using solvent-free conditions.
1. MICROWAVE ASSISTED REACTIONS USING SOLVENTS

In the case of the microwave-assisted reactions using (organic) solvents, the reactants are
usually dissolved in the solvent, which often couples effectively with microwaves and thus acts as the
energy transfer medium. The use of aqueous media for organic reactions is also under active
investigation and temperatures of up to 100 °C and above have been employed for the syntheses
often intended to exploit the hydrophobic effect. Water has a dielectric constant 78 at 25 °C which
decreases to 20 at 300 °C; the latter value being comparable with that of the solvents, such as acetone,
at ambient temperature. Thus, water at elevated temperature can behave as a pseudo-organic solvent
and is a possible environmentally benign replacement for organic solvents. In addition to the
environmental advantages of using water instead of the organic solvents, isolation of the products is
often facilitated by the decrease of the solubility of the organic material upon post-reaction cooling.
An alternative method for performing microwave assisted organic reactions, termed enhanced
microwave synthesis (EMS), has also been examined. By externally cooling the reaction vessel with
compressed air, while simultaneously administering microwave irradiation, more energy can be
directly applied to the reaction mixture. In the conventional microwave synthesis (CMS), the initial
microwave power is high, increasing the bulk temperature (TB) to the desired value very quickly.
However, upon reaching this temperature, microwave power decreases or shuts off completely in
order to maintain the desired bulk temperature without exceeding it. When microwave irradiation is
off, classical thermal chemistry takes over, losing the full advantage of microwave irradiation, which
is used to reach TB faster. Microwave enhancement of chemical reactions will only take place during
the application of the microwave energy. This source of energy will directly activate the molecules in
a chemical reaction, and therefore it is not desirable to suppress its application. EMS ensures that a
high, constant level of microwave energy is applied, resulting in the significantly greater yields and
cleaner chemistries.
Recently, the combination of two prominent green chemistry principles, namely microwaves
and water has become very popular and received substantial interest.
A plethora of very recent synthetic applications describes a variety of new chemistries that can
be performed with microwave irradiation but a wide range of microwave- assisted applications is still
waiting. Many organic transformations proceed via radical chemistry. As chemists wonder if
microwave irradiation can promote radical transformations, microwave-assisted free radical
chemistry is increasingly being explored. Microwave irradiation is applicable not only to the solvent
phase chemistry, but also to the solid-phase organic synthesis. Following are the example of
microwave assisted reaction using solvents.
(1) Hydrolysis
Hydrolysis of benzyl chloride with water in microwave oven gives 97 % yield of benzyl alcohol in 3
min. The usual hydrolysis in normal way takes about 35 min.
GREEN TECHNOLOGY 84
The usual hydrolysis of benzamide takes 1 hr. However, under microwave conditions, the hydrolysis
is completed in 7 min giving 99 % yield of benzoic acid.
(2) Oxidation
Oxidation of toluene with KMnO4 under normal conditions of refluxing takes 10-12 hr compared to
reaction in microwave conditions, which takes only 5 min and the yield is 40 %.
A Number of primary alcohols can be oxidized to the corresponding carboxylic acid using sodium
tungstate as catalyst in 30 % aqueous hydrogen peroxide.
(3) Esterification
A mixture of benzoic acid and n- propanol on heating in a microwave oven for 6 min in presence of
catalytic amount of conc. Sulfuric acid gives propylbenzoate.
(4) Decarboxylation
Conventional decarboxylation of carboxylic acids involves refluxing in quinoline in presence of
copper chromate and the yields are low. However, in the presence of microwaves decarboxylation
takes place in much shorter time.
(5) Cycloaddition
1,3-Dipolar cycloadditions are important reactions in organic synthesis. Cycloaducts were prepared
by carrying out the reaction between an azide and a substituted amide in toluene. This reaction was
carried out under microwave irradiation at 120 W at 75 °C for 1 h. The product was isolated in 70–80
% yield.
GREEN TECHNOLOGY 85
(6) N-Acylations
N-Acylations were carried out using secondary amines and isocyanate in dichloromethane under
microwave irradiation (8–10 min), yielding the product in 94% yield.
2. MICROWAVE ASSISTED REACTIONS UNDER SOLVENT-FREE CONDITIONS

Due to the environmental concerns, there has currently been an increasing demand for
efficient synthetic processes and solvent-free reactions. Some old and new methodologies are being
used to diminish and prevent pollution caused by chemical activities. In this context, the microwaves
have become an important source of energy in many laboratory procedures.
Furthermore, microwave-assisted solvent-free organic synthesis (MASFOS) has been
developed as an environmentally friendly process as it combines the selectivity associated with most
reactions carried out under microwaves with solvent and waste-free procedures in which organic
solvents are avoided throughout all stages. Environmental hazards and the subsequent degradations
are instrumental for the rapid evolution of green chemistry concept involving benign reagents and
conditions. The MASFOS reactions are of three types:
 Reactions using neat reactants;
 Reactions using solid-liquid phase transfer catalysis (PTC);
 Reactions using solid mineral supports.
REACTIONS USING NEAT REACTANTS

For carrying out reactions with neat reactants i.e without the use of a solvent or a support
(heterogeneous reactions), at least one of the reactants at the reaction temperature should normally
be liquid. In such a set-up, either the solid is partially soluble in the liquid phase or the liquid is
adsorbed onto the surface of solid with the reaction occurring at the interface. There is also another
possibility, namely that both the reactants are solid. Usually, they melt during the reaction course and
then undergo reaction as described above.
Following are the Examples of Microwaves assisted Reactions with neat reactants.
(1) Aromatic Nucleophilic Substitutions
Formation of Substituted Triazines Aromatic nucleophilic substitutions are carried out using sodium
phenoxide and 1,3,5-trichlorotriazine under microwave irradiation (6 min). The products, 1,3,5-
triarlyoxytriazines are obtained in 85–90% yields.
GREEN TECHNOLOGY 86
(2) Deacetylation
Aldehydes, phenol and alcohols are protected by acetylation. After the reaction, the deacetylation of
the product is carried out usually under acidic or basic conditions the process takes long time and the
yields are low. Use of microwave irradiation reduces the time of deacetylation and the yields are
good.
MICROWAVE ASSISTED REACTIONS USING SOLID LIQUID PHASE

Solid liquid phase transfer catalysis (PTC) has been described as an effective method in
organic synthesis and is under active investigation. This method is specific for anionic reactions as it
involves anionic activation. A catalytic amount of a tetralkylammonium salt or a cat ion complexing
agent is added to the mixture (in equimolar amounts) of both pure reactants. Reactions occur in the
liquid organic phase, which consists here only of the electrophilic R-X. The presence of an additional
liquid component is disadvantageous as it induces a dilution of reactants and consequently a decrease
in reactivity. The electrophile R-X is therefore both the reactant and the organic phase for the
reaction.
Following are the Example of Microwave assisted Reaction using Solid Liquid Phase
(1) O-Alkylation
Preparations of ethers were carried out from β-naphthol using benzyl bromide and 1-butyl-3-
methyl-imidazolium tetrafluoroborate under microwave irradiation (6-12 min) the products were
isolated in 75-90% yields.
(2) N-Alkylations
N-Alkylations under microwave irradiation using phase transfer catalysts occupy a unique place in
organic chemistry. Bogdal and co-workers reported the synthesis of N-alkyl phthalimides sing
phthalimide, alkyl halides, potassium carbonate and TBAB; giving products in 45–98% yields.
GREEN TECHNOLOGY 87
(3) Oxidations
Chakraborty reported the oxidation of secondary alcohol and benzyl alcohols using phase transfer
catalysts. Oxidation of secondary alcohols to acetone derivatives was carried out using PCC,
tetrabutylammonium bromide and dichloromethane under microwave irradiation (6–8min),
products were isolated in 70–99% yields. Oxidation of benzyl alcohols was conducted using BIFC
under microwave irradiation (1–8 min) yielding benzaldehyde derivatives in 70–92% yields.
(4) Knoevenagel Condensation

Knoevenagel condensation is a well known organic reaction, other applied in the synthesis of
unsaturated acids, which are used as precursors for perfumes, flavonoids and as building blocks of
many heterocycles. Gupta and Wakhloo studied knoevenagel condensation between carbonyl
compounds and active methylene compounds, such as malonic acid, using tetrabutylammonium
bromide, potassium carbonate in water forming unsaturated acids in excellent yield and purity under
microwave irradiation.
MICROWAVE ASSISTED REACTIONS ON MINERAL SUPPORTS IN DRY MEDIA

Solid supports are often very poor conductor of heat but behave as very efficient microwave
absorbents. This, in turn results in very rapid and homogeneous heating. Consequently, they display
very strong specific microwave effect with significant important in temperature homogeneity and
heating rates enabling faster reactions and less degradation of final products as compared to the
classical heating.
Following are the Example of the Microwave Activation with Supported Reagents
(1) N-Alkylation
N-Alkylation were carried out between piperidines and chloroalkanes in the presence of silica as the
solid support under microwave irradiation (6-10 min). N- Alkyl products were isolated in 79-99%
yields.
GREEN TECHNOLOGY 88
(2) S Alkylation
S-Alkylation was studied and accomplished by carrying out the reaction between mercaptobenzene
and alkyl halides using potassium carbonate and alumina under microwave irradiation (4-10 min).
Products were isolated in 70-89 % yields.
APPLICATION OF MICROWAVE
(1) Application of Microwave in material Chemistry
The use of microwave for synthesis of inorganic solid is very efficient and useful technique in
material chemistry. Microwave has been used in preparation of ceramics. wWhen Si and C (Charcoal)
in their powder form is taken in silica crucible and is exposed to microwave for 4 to 10 min in
domestic microwave oven operating at 2.45 GHz, SiC is obtained. SiC is a large volume ceramic and is
extensively used for industrial application such as for grinding wheels and in manufacture of abrasion
tools.
(2) Preparation of catalyst under microwave irradiation
Synthesis of a high permeance NaA zeolite YBa2Cu3O7-X membrance was prepared from an
aluminate and silicate sodium with molar ratio of 5 SiO2 : Al2O3: 50Na2O:1000H2O in a modified
domestic microwave oven operating at 2450 MHz in 15 min. It was observed that the permeance of
the zeolite membrane synthesized by the microwave heating is 4 times higher than that of the zeolite
membrane synthesized by conventional heating.
(3) Application of Microwave Technology for Nanotechnology
Today nanotechnology is being applied in the fields of synthesis of single-site catalyst,
antimicrobial nanocomposites, fire retardant materials, novel electro-optical devices, sensors, ultra
soft magnets and also in the area of drug delivery systems.
(4) Application of Microwave in polymer synthesis
The synthesis of polyacrylamide(PAM) was studied under microwave irradiation. PAM is used
as a flocculating agent in waste water treatment. Effects of microwave radiation power on acrylamide
molecular transformation ratio, with respect to PAM molecular weight, initiation and dissolve time
were discussed.
(5) Analytical Chemistry
The application of microwave irradiation is immense in the field of analytical chemistry.
Microwave irradiations are routinely used for sample digestion and solvent extraction techniques.
They have also been put to use for gravimetric, moisture determination and to find out enthalpy of
vaporization of solvents.
(6) Digestion
Development of high pressure Asher focused microwave(HPAFM) a novel approach to
microwave digestion is described by H. Matusiewics. The system uses focused MW operating at 2.45
GHz at 650 W power. The pressure vessels are made up of quartz discover pressure and temperature
GREEN TECHNOLOGY 89
can be conducted up to 130 bar and 3200C respectively. Using this apparatus the methodology was
developed for digestion of biological reference material such as bovine liver.
(7) Microwave irradiation in waste management
Microwave heating is playing an important role in treatment of domestic and hazardous
industrial and nuclear waste. Microwave heating can be advantageously used for waste management
in areas where human exposure can cause health problems. The MW and high frequency technology
needed for handling such type of hazardous waste is ready to use. A process for carbonization of
organic waste for manufacturing of activated carbon using MW heating has been patented. Activated
carbon can be manufactured form organic wastes such as used paper, wood, waste plastic etc. in high
carbonization efficiency using MW heating. In this process waste such as automobile shedder waste,
medical wastes, ores, sludge etc are treated by MW energy in anaerobic atmosphere.
SONOCHEMISTRY:-
Sonochemistry: A branch of chemical research dealing with the chemical effects and applications
of ultrasonic waves, that is, sound with frequencies above 20 kHz that lie beyond the upper limit of
human hearing.
• Sonochemistry is the application of ultrasound to chemical reactions and processes. The
mechanism causing sonochemical effects in liquids is the phenomenon of acoustic cavitation.
• Enhances reaction rates up to a million times
• Believed to be due to small cavities (100 microns) which implode, creating tremendous heat
and pressure, shock waves, and particle accelerations. This process is called “cavitation”
• Started gaining attention for organic chemists when someone noticed that organic solvents
formed cavities.
• sonochemistry--has huge potential for innovation in eco-friendly and eco-efficient chemistry,
which is precisely what we need in today's world.
• Jean-Louis Luche, one of the fathers of the modern sonochemistry, said that "success in
sonochemistry relies both on the quality of the equipment and expertise with its use to benefit
from the full potential offered by ultrasound in the field of chemistry".
• Sonochemistry is hypothesised to originate from acoustic cavitation and bubble collapse as a
result of the mechanical effects of sounds on liquids
• Sonochemistry is also considered a methodology of organic reactions without solvents.
The term “sonochemistry” is used to describe the chemical and physical processes occurring in
solution through the energy brought by power ultrasound. The effects of ultrasound are the
consequence of the cavitation phenomenon, which is the formation, the growth and the collapse of
gaseous microbubbles in liquid phase (Figure 2.13). Ultrasound is propagated through a series of
compression and rarefaction waves in the liquid medium. When the acoustic power is sufficiently
high, the rarefaction cycle exceeds the attractive forces of the molecules of the liquid and cavitation
bubbles of a few micrometers in diameter are formed. Small amounts of vapor or gas from the
medium enter in the bubble during its expansion phase and is not fully expelled during compression
phase. The bubbles grow over the period of a few cycles to an equilibrium size for the particular
frequency applied. The intense local effects (mechanical, thermal and chemical) due to the
sudden collapse of those bubbles are at the origin of all the applications of sonochemistry.
In water, at an ultrasonic frequency ( f ) of 20 kHz, each cavitation bubble collapse represents a
localized hot-spot, generating temperatures of about 5,000 K and pressures superior to 1,000 bars
GREEN TECHNOLOGY 90
(Figure 2.13). Many factors can affect the cavitation and the results of a sonochemical reaction: the
acoustic power, the frequency, the hydrostatic pressure, the nature and the temperature of the
solvent, the used gas and even the geometry of the reactor. The potential of sonochemistry is often
directly connected to the choice of the sonochemical parameters or experimental conditions.
Figure 2.13: Schematic representation of the acoustic cavitation phenomenon.

For example, the frequency is an essential parameter (Figure 2.14). Indeed, even if the whole
mechanism is not elucidated yet, it is usually accepted that, in water, low frequencies (20–80 kHz)
lead preferentially to physical effects (shockwaves, microjets, microconvection, etc.). On the contrary,
high ultrasonic frequencies (150–2,000 kHz) favor the production of hydroxyl radicals (HO•)
through the local hotspots produced by cavitation, mainly leading to chemical effects. In a broad
outline, it is possible to identify two great families of power ultrasound applications in chemistry
based either on sonophysical effects or sonochemical effects. Conditions obtained in a medium
submitted to ultrasound are accountable for a large number of physicochemical effects as increase in
kinetics of chemicals reactions, changes in reaction mechanisms, emulsification effects, erosion,
crystallization, precipitation, etc.
Figure 2.14: Predominant effects in water as a function of the frequency range.
THE BRIEF HISTORY OF SONOCHEMISTRY

The history of sonochemistry is relatively recent and to better understand, we have to date
back to the discovery of ultrasound. Indeed, this story starts with the Italian biologist Lazzaro
Spallanzani (1729–1799) who discovered in 1794 by binding bat eyes that their movements were
directed thanks to ultrasound: in fact, their eyes were their ears! However, ultrasound was really
discovered in 1883 by the English physiologist Sir Francis Galton (1822–1911) who invented the
silent whistle or “Galton’s whistle”, emitting sound in a range that only dogs heard, but not humans:
this range of sound was ultrasonic range! The discovery of the piezoelectricity by French physicists
Jacques Curie (1855–1941) and Pierre Curie (1859–1906) allowed the generation of ultrasound in
GREEN TECHNOLOGY 91
water from piezoelectric materials and some powerful electronic devices. After the Titanic tragedy of
1912, Paul Langevin (1872–1946) suggested the use of ultrasound for the detection of icebergs. In
1917, he developed a sonar system, called hydrophone, using the ultrasonic vibrations to detect
submarines by echolocation. This represents the first industrial application of ultrasound during the
World War. As a fundamental point of view, the cavitation phenomenon was first observed by Sir
John Isaac Thornycroft (1843–1928) and Sydney Walker Barnaby (1855–1925) with the propeller of
their submarine becoming pitted and eroded over a relatively short operation period. They reported
“unusual vibrations of their propeller due to large bubbles generated by the movement of the blades”
and “the implosion of these bubbles under the water pressure.” Lord Rayleigh (1842–1919) explained
the erosion of the propellers of boats by the formation and growth of vapor bubbles in the presence
of a depression caused by Bernoulli effect, followed by a violent collapse. He determined the first
mathematical model describing a cavitation event in an incompressible fluid.
The story of sonochemistry really started in 1927 when Alfred Lee Loomis (1887–1975),
Robert William Wood (1868–1955) and Theodore William Richards (1868–1928) reported for the
first time chemical and biological effects of ultrasound, showing that cavitation could be a useful tool
in chemistry. One of the first applications was the use of ultrasound inducing cavitation to degrade a
biological polymer. The use of ultrasound was industrially developed in the 1950s for cleaning
applications in heavy industry, medical instruments, clothing and textiles and food industry.
However, it took until the 1980s and the onset of reliable and marketed ultrasonic generators for the
researchers to demonstrate that the ultrasonic waves offer undeniable opportunities in chemistry. In
1980, Ernest Arthur Neppiras introduced the term “sonochemistry” in a review about acoustic
cavitation. From that moment, progress in the field of sonochemistry increased exponentially.
Timothy J. Mason particularly promoted the use of ultrasound in various areas of chemistry, through
fundamental aspects as well as innovative applications, and by co- founding in 1991 the European
Society of Sonochemistry and a new Elsevier® journal dedicated to sonochemistry works (Ultrasonics
Sonochemistry). In 1998, Jean-Louis Luche, also considered as a pioneer of modern sonochemistry,
described the true and false effects of sonochemistry. The major part of this handbook is dedicated to
understand why sonochemistry can be considered as a beneficial tool for green chemistry.
Figure 2.15: Development of ultrasound in organic synthesis
GREEN TECHNOLOGY 92
ULTRASOUND
Ultrasound is the part of sonic spectrum (20-10 MHz), can be divided into 3 regions.
1. Low frequency, High power Ultrasound (20-100 kHz)
2. High Frequency, High power Ultrasound (100 kHz-1 MHz)
3. High frequency, low power Ultrasound (1 MHz- 10 MHz)
The range from 20KHz to 1 MHz is generally used.
Best known uses of ultrasound

• Target detection using SONAR (Sound Navigation and Ranging)
• Medical applications:
– Medicalsonography (ultrasonography)
– Acoustic targeted drug delivery
– Cleaning teeth in dental hygiene
• Industrial Applications:
– Ultrasonic testing (non‐destructive)
– Ultrasonic cleaning
Ultrasound instruments for organic chemistry Ultrasound reactors in process chemistry
GREEN TECHNOLOGY 93
THE USE OF ULTRASOUND FOR ORGANIC SYNTHESIS

Ultrasound-assisted organic synthesis is another “green” methodology which is applied in
many organic synthetic routes with great advantages for high efficiency, low waste, low energy
requirements. Sonochemistry (in the region of 20 kHz to 1 MHz) has many applications due to its
high energy and the ability to disperse reagent in small particles and accelerate reactions.
Chemical reactions can start and enhanced by sonic waves. Sonochemical reactions by
ultrasound are very advanced “green” techniques with exceptional high yields. There are three classes
of sonochemical reactions: homogeneous sonochemistry of liquids, heterogeneous sonochemistry of
liquid-liquid or solid–liquid systems, and, overlapping with the previous techniques, sonocatalysis.
The chemical enhancement of reactions by ultrasound has been explored and has beneficial
applications in mixed phase synthesis, materials chemistry, and biomedical uses.
Other techniques advanced in the last decade in organic synthesis, with emphasis on toxic
solvent minimization, are soluble polymers as catalysts, thermoregulated systems, and enzymes. All
these techniques have been advanced with green chemistry principles in mind, since industrial
production of chemical substances is the fundamental technology producing environmental problems,
waste and toxic by-products.
Also, Sonochemical engineering is a new field involving the application of sonic and ultrasonic
waves to chemical processing. Sonochemistry enhances or promotes chemical reactions and mass
transfer. It offers the potential for shorter reaction cycles, cheaper reagents, and less extreme physical
conditions. Existing literature on sonochemical reacting systems is chemistry-intensive, and
applications of this novel means of reaction in environmental remediation and pollution prevention
seem almost unlimited and are rapidly growing area.
SONOCHEMICHAL REACTIONS
• Switching reactions
– Kornblum‐Russell reaction
• Homogeneous reactions
– Hetero Michael reaction
• Heterogeneous reactions
– Metal activation reactions
 Grignard reagent preparation
– Palladium catalyzed coupling reactions
 Suzuki coupling
Ultrasound‐assisted Kornblum‐Russell Reaction
GREEN TECHNOLOGY 94
Kornblum‐Russell reaction mechanism
Ultrasound‐assisted Hetero‐Michael Reaction
Ultrasound‐assisted Grignard Reagent preparation

• Traditional:
– Oxide free Magnesium
– Periodic crushing of metal
• Ultrasonication:
– Any grade of Magnesium
– Crushing not required
GREEN TECHNOLOGY 95
Ultrasound‐assisted Suzuki coupling
BENEFITS OF SONOCHEMISTRY
1. Decrease of reaction time and/or increase of yield.
2. Possible switching of reaction pathway.
3. Use of less or avoidance of phase transfer catalyst.
4. Activation of metals and solids.
CATALYSIS
Catalysis is the process of increasing the rate of a chemical reaction by adding a substance known as
a catalyst, which is not consumed in the catalyzed reaction and can continue to act repeatedly. Because of
this, only very small amounts of catalyst are required to alter the reaction rate in principle.
CATALYST
A catalyst is an agent or compound that is added to a process to make a chemical reaction
happen more quickly. The catalyst can increase the reaction rate of the steam and can participate in
the secondary reactions. The packing can also act as a catalyst to enhance desired chemical
transformations.
TYPES OF CATALYST
Catalysis is generally divided into two types, homogeneous and heterogeneous.
Heterogeneous catalysis is where the catalyst and the reactants are in the different physical phases,
while homogeneous is where both are in the same phase.
1.Homogeneous Catalysis
The field of homogeneous catalysis can be characterized as a source of easily arranged,
selective catalysts with high activity. In homogeneous catalysis, the catalyst is in the same phase as
the reactants and products. In general, homogeneous catalysts exhibit excellent catalytic activities
with high selectivities in particular. But, it is difficult for the homogeneous catalyst to be separated
from reaction media.
2 Heterogeneous Catalysis
Heterogeneous catalysts also offer many advantages, some of which are not displayed by their
homogeneous counterparts, including recyclability, ease of separation from the reaction mixture and
use in continuous flow processes. It is highly desirable to develop new systems that blend the many
advantages of heterogeneous catalysis with the versatility of homogeneous catalysts. Heterogeneous
catalysts have several advantages compared to other catalytic processes:
• they avoid formation of inorganic salts
• they are regenerable
• easy to handle, safe to store and has long life time
• easy and inexpensive of recovery and recycling
• The selectivity and activity of homogeneous catalysts under mild reaction conditions is
unbeaten by their heterogeneous counter parts.
GREEN TECHNOLOGY 96
GREEN CATALYSTS
Recently, growing attention is being directed towards the development of innovative catalytic
systems with high performance from the point of environmentally greener processes, economical
efficiency and minimum consumption of resources. The application of catalysis to reduce toxicity and
renewable energy systems, and efficiency makes it a central focus area for green chemistry research.
Green Catalysis is a subtitle of green chemistry but the most important one and one of the urgently
needed challenges facing engineers now is the design and use of environmentally benign catalysts.
Green and sustainable catalyst should possess higher activity, higher selectivity, efficient recovery
from reaction medium, durability or recyclability, cost effectiveness.
In recent years the development of catalysts for processes to replace conventional ones has
made a significant contribution to the reduction of environmental pollutants. Thus, there is an
increasing interest on the topic of green catalysis recently. It not only includes developing new
catalysts which can offer stable, highly effective catalytic performances, but considers the application
of environmentally friendly catalyst preparations.
The use of “green catalysts” will improve substantially the efficiency of many industrial
processes. The use of catalysts is one of the principles of Green Chemistry. Catalysis is considered a
cornerstone for innovative changes in chemical processes. Catalysts will affect energy use and
reaction time, will increase yield, reduce use of solvents, and lower production of by-products and
waste.
ZEOLITES AND ZEOTYPES: SYNTHESIS AND STRUCTURE
ZEOLITES
Zeolites are microporous, aluminosilicate minerals commonly used as commercial adsorbents
and catalysts. The term zeolite was originally coined in 1756 by Swedish mineralogist Axel Fredrik
Cronstedt, who observed that rapidly heating the material, believed to have been stilbite, produced
large amounts of steam from water that had been adsorbed by the material. Based on this, he called
the material zeolite, from the Greek zéō, meaning "to boil" and líthos, meaning "stone".Zeolites are
also called as “Boiling stone” as Many zeolites fuse readily with marked intumescence (a swelling up
which results when water is expelled during heating). Zeolites are crystalline alumino silicates
comprising corner-sharing SiO4 and AlO4– terahedra and consisting of a regular system of pores
(channels) and cavities (cages) with diameters of molecular dimensions (0.3 to 1.4 nm). A large
number of zeolites are known, some of which are naturally occurring, but most of which have been
synthesized. The general formula for a zeolite is Mx/n[(AlO2)x(SiO2)y].mH2O. M is the metal or
hydrogen cation of valency ‘n’ occupying the exchangeable cationic sites on zeolite framework. AlO2
and SiO2 are fundamental units sharing oxygen ions to form tetrahedral AlO4 and SiO4 building blocks
for zeolite unit cell. Since silicon ion has +4 and Aluminium has +3 charges there is an overall negative
charge on the aluminosilicate framework. The cationic charge of the metal or hydrogen ion balances
the negative charge on the alumino silicate framework.
ZEOTYPES
Any of a family of artificial materials based on the structure of zeolites. Analogous structures
containing TO4 tetrahedra composed of Si, Al or P as well as other main group and transition
elements, e.g. B, Ga, Fe, Ge, Ti, V, Cr, Mn and Co, have also been synthesized and are generically
referred to as zeotypes. They include, for example, AlPOs, SAPOs and MeAPOs.
GREEN TECHNOLOGY 97
SYNTHESIS
Zeolites are prepared by so-called hydrothermal synthesis a simplified scheme of which is
shown in Fig. 2.17. The basic ingredients – SiO2, Na2SiO3 or Si(OR)4 and Al2O3, NaAlO2 or Al(OR)3-
together with a structure directing agent (template), usually an amine or tetraalkylammonium salt,
are added to aqueous alkali (pH 8–12). This results in the formation of a sol–gel comprising
monomeric and oligomeric silicate species. Gradual heating of this mixture up to ca. 2000C results in
dissolution of the gel to form clusters of SiO4/AlO4– units which constitute the building blocks for the
zeolite structure. In the presence of the template these building blocks undergo polymerization to
form the zeolite which crystallizes slowly from the reaction mixture. At this point the zeolite still
contains the occluded organic template. This is subsequently removed by calcination, i.e. heating in
air at 400–6000C to burn out the template and evaporate water.
Fig. 2.16 Simplified zeolite synthesis scheme.
Similarly, zeotype molecular sieves are synthesized by mixing the basic ingredients with the
organic template, e.g. aluminophosphates are prepared from alumina and phosphoric acid. Other
main group or transition elements can be incorporated into the framework by adding them to the
initial sol–gel. Alternatively, different elements can be introduced by post-synthesis modification, e.g.
by dealumination followed by insertion of the new elements into the framework position.
STRUCTURE
Aluminosilicates are formed by polymerization of SiO4 and AlO 4 tetrahedra to form sheet like
polyhedral. The polyhedra forms cubes, hexagonal prisms and truncated octahedral. These 3D
tertiary building blocks in turn are arranged regularly to form a superstructure inside which pores
and super cage exists. Each supercage is characterized by a window size aperture which can block
entry of sufficiently large molecules. This is known as sieve effect. The zeolite structures have pores
oriented in one, two or three directions leading to 1D, 2D, 3D structures.
The most important feature of zeolites (and zeotypes), in the context of catalysis, is not their
range of acid–base properties, since that is also available with amorphous alumino-silicates. It is the
GREEN TECHNOLOGY 98
presence of a regular structure containing molecular sized cavities and channels that make them
unique as shape selective catalysts for a wide variety of organic transformations.
Fig. 2.17 Basic units in zeolites.
Representation of zeolite structures is different to that used by organic chemists. The

intersection of lines represents either a SiO4 or an AlO4– tetrahedron and the line itself represents an
O atom joining the two tetrahedral. In Fig. 2.17 eight TO4 octahedral are joined together in a ring,
commonly referred to as the 8-ring structure as there are eight oxygen atoms in the ring. These basic
ring structures are combined to form three dimensional arrangements which constitute the building
blocks for the zeolite. For example, one of these building units is the sodalite cage, a truncated
octahedron with four-membered rings made during truncation and six-membered rings as part of the
original octahedron.
Fig. 2.18 Structures of zeolite A and faujasite.

In zeolites derived from the sodalite unit these cages are joined together through extensions of
either the 4-ring or the 6-ring. Zeolite A (see Fig. 2.18) is an example of the former. The center of the
structure comprises a supercage, with a diameter of 1.14 nm, surrounded by eight sodalite cages.
Access to these cages is via the six mutually perpendicular 8-ring openings having a diameter of 0.42
nm, enabling linear hydrocarbons to enter. The Si/Al ratio is 1–1.2 making zeolite A among the least
acidic of all zeolites.
Faujasites are naturally occurring zeolites composed of sodalite cages joined through
extensions of their 6-ring faces. An internal supercage of ca. 1.3 nm diameters is accessed by four 12
ring openings with a diameter of 0.74 nm. The latter provide access for relatively large aliphatic and
aromatic molecules, e.g. naphthalene.
GREEN TECHNOLOGY 99
The synthetic zeolites X and Y have the same crystal structure as faujasite but differ in their
Si/Al ratios. In zeolites X and Y the Si/Al ratio is 1–1.5 and 1.5–3, respectively, while faujasite has
Si/Al ratio of ca. 2.2.
Fig. 2.19 Structures of mordenite and ZSM-5. Fig. 2.20 The pentasil unit.
Mordenite is a naturally occurring zeolite with a Si/Al ratio of ca. 10 and a structure composed
of 12-ring and 8-ring tunnels with diameters of 0.39 nm and ca. 0.7 nm, respectively, extending
through the entire framework (Fig. 2.19). Every framework atom forms a part of the walls of these
tunnels and is accessible to substrate molecules diffusing through them.
The synthetic zeolite, ZSM-5, is a highly siliceous material with a Si/Al ratio from 25 up to
2000 [32]. As shown in Fig. 2.19, it consists of a three-dimensional network of two intersecting 10-
ring tunnel systems of 0.55–0.6 nm diameter. One of these resembles the 12-ring tunnels passing
through mordenite (see above) while the other follows a sinusoidal path perpendicular to, and
intersecting with, the first. The basic structural unit of this zeolite is the pentasil unit composed of
fused 5-rings (Fig. 2.20).
GREEN TECHNOLOGY 100
Figure 2.21 Zeolite crystals
CLASSIFICATION OF ZEOLITES
Zeolites are conveniently divided into groups on the basis of their pore sizes – small, medium,
large and ultra large – which are determined by the ring size of the pore openings. Among
aluminosilicate zeolites 3A, 4A, 5A and erionite containing 8 number of rings have pore diameters in
the range of 3-5 Å. ZSM 5 and mordenite with 10 and 8 rings respectively have pore diameters in
range of 3 -5 Å. On the other hand, faujasite X and Y have 12 rings with larger pore diameter of 7 - 8 Å.
Aluminophosphates (ALPOs) have significantly extended range of pore sizes. ALPOs containing 12
rings have pore diameter of 10 Å while 18 ring ALPOs have pore diameter of 10- 15 Å.
Examples of commonly used zeolites and zeotypes are collected in Table 2.1.
Table 2.1 Pore dimensions of molecular sieves.
PROPERTIES OF ZEOLITES
a. High surface area and ordered pore structure
High surface area and ordered pore structure of zeolites result in their unique adsorption
properties. Zeolites are characterized by large surface area because of its highly porous nature. The
surface area of zeolites is in the range of 600-800 m2/g. As a result of high surface area zeolites can
adsorb large quantities of adsorbate depending on adsorbate size, aperture size, temperature and
surface acidity of zeolites.
Zeolites have aperture or pore diameter of the order of molecular dimension therefore
molecules having diameter of the same order or larger than pore diameter or aperture are excluded
from entering the pores or super cages. Since larger molecules are excluded, preferential adsorption
and reaction can be done using zeolites. For examples separation of O2 and N2 in air can be done using
and 13 X-NaX zeolites.
b. Acidity :
The OH bridging a framework of silicon to a framework of aluminum acts as the Bronsted acid
site. Coordinately unsaturated Al sites give rise to Lewis acidity. Acidity in zeolites increases with
decreasing Si: Al ratios because acid sites are associated with Al ions. Bronsted and Lewis acid sites
play important roles in various catalytic reactions involving hydrocarbons. Zeolites are used in
catalytic cracking reaction in petroleum industry.
c. Thermal stability :
Most of the zeolites are stable upto 4000C. Stability increases with increasing silica content.
Introduction of rare earth cations in zeolites result in stability upto 8000C
d. Shape selectivity
Unique pore structure of zeolites results in its high shape selective properties. Shape selectivity
results due to:
– Geometric restrictions on the access of reactants to the zeolite framework
– Geometric restrictions on diffusion of reactants in or diffusion of products out from catalysts
i. Reactant selectivity: Selective admission of reactants to zeolite pores due to pore size restrictions
is known as reactant selectivity. For example in case of cracking reactions, n-heptane undergoes
preferential cracking (relative rate 1) over dimethylhexane (relative rate 0.09). The dimethylhexane,
due to presence of branched carbons, is unable to enter the zeolite pores.
ii. Product selectivity: When there is possibility of formation of multiple products , selective
formation of product can occur due to restriction on size or diffusion rates of the larger molecule. For
examples when alkylation of methylbenzene is carried out over pentasil zeolites all isomers p-xylne,
m-xylene, and o-xylene are probable products. However, due to pore diameter restrictions in pentasil
zeolites there is preferential production of p-xylene over ortho and meta forms as shown in the figure
below.
iii. Molecular traffic control : This concept involves preferential diffusion of reactants through one
channel and diffusion of products out of another interconnecting channel of a zeolite. Counter
diffusion is minimized and product selectivity is maximized by this process.
APPLICATIONS OF ZEOLITES
The principal applications of zeolites are discussed below.
i. Catalysts and catalyst supports

Acidity and shape –selective properties of zeolites play major roles in their use as catalysts to
produce premium quality fuels and chemicals. Zeolites because of their acidity find applications in
catalytic cracking, isomerization, alkylation and aromatization reactions. Fluidized catalytic cracking
is the largest and oldest application of zeolite catalysts. Medium pore zeolites are being widely used
in conversion of light hydrocarbons to monocyclic aromatics, because of their ability to selectively
perform these reactions, while minimizing coke formation. For same reactions, when small pore
zeolites are used, no aromatics are produced and severe operating conditions are required, whereas
large pore zeolites produce heavy aromatics and deactivate rapidly. The major advantage of large
pore molecular sieves, developed recently, is their ability to crack larger molecules, such as present in
heavy petroleum residue, more efficiently. Major commercial catalytic processes using zeolites are
summarized in Table 1.
Table 2.2. Commercial catalytic processes using zeolite catalysts
In addition to the well established commercial processes some other new applications of
zeolites are being developed. Conversion of n-hexane and n-heptane to benzene and toluene is
carried out on a PtBa/Zeolite L catalyst while, isomerization of C5/C6 is done with Pt/mordenite
/alumina catalyst. For ZSM-5 catalysts various applications are developed. For example, alkylation of
benzene and toluene to form high octane alkyl aromatics, methanol to gasoline, methanol to alkene,
toluene disproportionation to p-xylene, or selective catalytic reduction of NO has been reported with
ZSM-5 or modified ZSM- 5 catalysts.
ii. Selective adsorbents and drying agents
Zeolites have unique ability to adsorb water while rejecting larger molecules. For many
applications they are the best available drying agents. Used in drying air, natural gas, organic solvents
and refrigerants.
iii. Separation and purification of gasses and liquids
Zeolites are used in purification of gases and hydrocarbon liquids. The 5A (CaA) and 13X(NaX)
zeolites have been the most commonly used sorbents for air separation. The typical commercial 5A
used for air separation is made by exchanging ~70% of the Na+ in NaA by Ca2+ ions. The nitrogen is
preferentially adsorbed on the zeolite.
iv. Various types of zeolites such as Zeolites A,X, ZSM-5, mordenite etc. are used for removing H2O,
NH3, NO,NO2,SO2, CO2 and other impurities from gas stream. In gas cleaning, zeolites are normally
used for the removal of H2O, SO2 and CO2 from sour natural gas stream. Zeolite 4A are used for
removal of CO2 from submarines and spacecraft. The CaA (Ca ion exchanged zeolites A) is used to
adsorb H2S from sour gas. They are also used for selective removal of NH3 produced during
gasification of coal and for removal of NH3, SO2, NOx and CO2 from air. Separation of close boiling
point mixtures of alkylphenols, such as mixture of p-cresol (201.8)/2,6-xylenol (203 0C) or m-cresol
(202.8 0C)/2,6-xylenol has been attempted using Na-X zeolites[3]. Effect of the cation on the
selectivity has also been investigated. The Na-X zeolite adsorbs p-cresol and m-cresol selectively from
their mixtures with 2,6-xylenol, while Ca-X and Ba-X zeolites preferentially adsorb 2,6-xylenol. The
selectivity seems to be decided by the diffusion in the zeolite framework.
v. Water and waste water treatment:
In water and waste water treatment zeolites are used for various purposes, mainly for water
softening, ammonia removal and heavy metal removal. Zeolite is used for exchange of hard ions
[Ca+2] with soft ions [Na+, H+] for softening water in a broad range of pH values. It is one of the
oldest applications. This is particularly important in detergent industry. Zeolites can also remove
dyes from the washing liquor by hetero-coagulation and adsorption. Another application of zeolites is
separation of ammonia from drinking or wastewater. Ammonia in the environment originates from
metabolic, agricultural and industrial processes and from water disinfection with chloramine. The
zeolites are very effective for ammonia removal, due to their high selectivity for ammonium ion in the
presence of competing cations, such as K+, Ca2+ or Mg2+. Metals having density higher than 5 g/cm3
are generally considered as heavy metals. Among the heavy metals Cd, Cr, Cu, Ni, Zn, Pb and Hg are
well known with their toxicity and considered as environmentally hazardous. Zeolites have been
widely explored for removal of heavy metals from natural or industrial wastewater. The removal
efficiency of zeolites depends upon the type and amount of zeolite, contact time, pH, temperature,
initial metal concentration as well as on presence of competitive ions.
PHOTOCATALYSIS
photocatalysis is the acceleration of a photoreaction in the presence of a catalyst. In catalysed
photolysis, light is absorbed by an adsorbed substrate. In photogenerated catalysis, the photocatalytic
activity (PCA) depends on the ability of the catalyst to create electron–hole pairs, which generate free
radicals (e.g. hydroxyl radicals: •OH) able to undergo secondary reactions. Its practical application
was made possible by the discovery of water electrolysis by means of titanium dioxide.
MECHANISM
When photocatalyst titanium dioxide (TiO2) absorbs Ultraviolet (UV) radiation from sunlight
or illuminated light source (fluorescent lamps), it will produce pairs of electrons and holes.
The electron of the valence band of titanium dioxide becomes excited when illuminated by
light. The excess energy of this excited electron promoted the electron to the conduction band of
titanium dioxide therefore creating the negative-electron (e-) and positive-hole (h+) pair. This stage
is referred as the semiconductor's ' photo-excitation ' state. The energy difference between the
valence band and the conduction band is known as the ' Band Gap '. Wavelength of the light
necessary for photo-excitation is:
1240 (Planck's constant, h) / 3.2 ev (band gap energy) = 388 nm
Fig 2.22 The overall mechanism of photocatalytic reaction of titanium dioxide.

The positive-hole of titanium dioxide breaks apart the water molecule to form hydrogen gas
and hydroxyl radical. The negative-electron reacts with oxygen molecule to form super oxide anion.
This cycle continues when light is available.
TYPES OF PHOTOCATALYSIS
HOMOGENEOUS PHOTOCATALYSIS
In homogeneous photocatalysis, the reactants and the photocatalysts exist in the same phase.
The most commonly used homogeneous photocatalysts include ozone and photo-Fenton systems (Fe+
and Fe+/H2O2). The reactive species is the •OH which is used for different purposes. The mechanism
of hydroxyl radical production by ozone can follow two paths.
O3 + hν → O2 + O(1D)
O(1D) + H2O → •OH + •OH
O(1D) + H2O → H2O2
H2O2 + hν → •OH + •OH
Similarly, the Fenton system produces hydroxyl radicals by the following mechanism
Fe2+ + H2O2→ HO• + Fe3+ + OH−
Fe3+ + H2O2→ Fe2+ + HO•2 + H+
Fe2+ + HO• → Fe3+ + OH−
In photo-Fenton type processes, additional sources of OH radicals should be considered: through
photolysis of H2O2, and through reduction of Fe3+ ions under UV light:
H2O2 + hν → HO• + HO•
Fe3+ + H2O + hν → Fe2+ + HO• + H+
The efficiency of Fenton type processes is influenced by several operating parameters like
concentration of hydrogen peroxide, pH and intensity of UV. The main advantage of this process is the
ability of using sunlight with light sensitivity up to 450 nm, thus avoiding the high costs of UV lamps
and electrical energy. These reactions have been proven more efficient than the other photocatalysis
but the disadvantages of the process are the low pH values which are required, since iron precipitates
at higher pH values and the fact that iron has to be removed after treatment.
HETEROGENEOUS PHOTOCATALYSIS
Heterogeneous catalysis has the catalyst in a different phase from the reactants.
Heterogeneous photocatalysis is a discipline which includes a large variety of reactions: mild or total
oxidations, dehydrogenation, hydrogen transfer, 18O2–16O2 and deuterium-alkane isotopic exchange,
metal deposition, water detoxification, gaseous pollutant removal, etc.
Most common heterogeneous photocatalysts are transition metal oxides and semiconductors,
which have unique characteristics. Unlike the metals which have a continuum of electronic states,
semiconductors possess a void energy region where no energy levels are available to promote
recombination of an electron and hole produced by photoactivation in the solid. The void region,
which extends from the top of the filled valence band to the bottom of the vacant conduction band, is
called the band gap. When a photon with energy equal to or greater than the materials band gap is
absorbed by the semiconductor, an electron is excited from the valence band to the conduction band,
generating a positive hole in the valence band. Such a photogenerated electron-hole pair is termed an
exciton. The excited electron and hole can recombine and release the energy gained from the
excitation of the electron as heat. Exciton recombination is undesirable and higher levels lead to an
inefficient photocatalyst. For this reason efforts to develop functional photocatalysts often emphasize
extending exciton lifetime, improving electron-hole separation using diverse approaches that often
rely on structural features such as phase hetero-junctions (e.g. anatase-rutile interfaces), noble-metal
nanoparticles, silicon nanowires and substitutional cation doping. The ultimate goal of photocatalyst
design is to facilitate reactions between the excited electrons with oxidants to produce reduced
products, and/or reactions between the generated holes with reductants to produce oxidized
products. Due to the generation of positive holes and electrons, oxidation-reduction reactions take
place at the surface of semiconductors. In the oxidative reaction, the positive holes react with the
moisture present on the surface and produce a hydroxyl radical.
Here MO stands for metal oxide:
UV + MO → MO (h + e−)
Oxidative reactions due to photocatalytic effect:
h+ + H2O → H+ + •OH
2 h+ + 2 H2O → 2 H+ + H2O2
H2O2→ 2 •OH
Reductive reactions due to photocatalytic effect:
e− + O2 → •O2−
•O2− + HO•2 + H+ → H2O2 + O2
HOOH → HO• + •OH
Ultimately, the hydroxyl radicals are generated in both the reactions. These hydroxyl radicals are
very oxidative in nature and non selective with redox potential of (E0 = +3.06 V)
MAJOR ADVANTAGES OF PHOTOCATALYSIS

(i) Photocatalysis offers a good replacement for the energy-intensive conventional treatment
methods (adsorption on activated carbon, ultrafiltration, reverse osmosis, coagulation by
chemical agents, ion exchange on synthetic adsorbent resins) with the capacity for using
renewable and pollution-free solar energy.
(ii) Photocatalysis leads to the formation of harmless products, unlike conventional treatment
measures which transfer pollutants from one phase to another.
(iii) The photocatalytic process can be used in the destruction of a variety of hazardous
compounds in different wastewater streams.

(iv) The reaction conditions for photocatalysis are mild, the reaction time is modest and a lesser
chemical input is required.
(v) Minimal of secondary waste generation and
(vi) It can be applied to hydrogen generation, gaseous phase, and aqueous treatments as well for
solid (soil) phase treatments to some extent.
LIMITATIONS OF PHOTOCATALYSIS
• interfacial charge transfer
• improve the charge separation and
• inhibition of charge carrier recombination.
APPLICATIONS
 Conversion of water to hydrogen gas by photocatalytic water splitting.[5] An efficient
photocatalyst in the UV range is based on a sodium tantalite (NaTaO3) doped with La and
loaded with a cocatalyst nickel oxide. The surface of the sodium tantalite crystals is grooved
with so called nanosteps that is a result of doping with lanthanum (3–15 nm range, see
nanotechnology). The NiO particles which facilitate hydrogen gas evolution are present on the
edges, with the oxygen gas evolving from the grooves.
 Use of titanium dioxide in self-cleaning glass. Free radicals generated from TiO2 oxidize
organic matter.
 Disinfection of water by supported titanium dioxide photocatalysts, a form of solar water
disinfection (SODIS).
 Use of titanium dioxide in self-sterilizing photocatalytic coatings (for application to food
contact surfaces and in other environments where microbial pathogens spread by indirect
contact).
 Oxidation of organic contaminants using magnetic particles that are coated with titanium
dioxide nanoparticles and agitated using a magnetic field while being exposed to UV light.
 Conversion of carbon dioxide into gaseous hydrocarbons using titanium dioxide in the
presence of water. As an efficient absorber in the UV range, titanium dioxide nanoparticles in
the anatase and rutile phases are able to generate excitons by promoting electrons across the
band gap. The electrons and holes react with the surrounding water vapor to produce
hydroxyl radicals and protons. At present, proposed reaction mechanisms usually suggest the
creation of a highly reactive carbon radical from carbon monoxide and carbon dioxide which
then reacts with the photogenerated protons to ultimately form methane. Although the
efficiencies of present titanium dioxide based photocatalysts are low, the incorporation of
carbon based nanostructures such as carbon nanotubes[15] and metallic nanoparticles[16] have
been shown to enhance the efficiency of these photocatalysts.
 Sterilization of surgical instruments and removal of unwanted fingerprints from sensitive
electrical and optical components.
 A less-toxic alternative to tin and copper-based antifouling marine paints, ePaint, generates
hydrogen peroxide by photocatalysis.
 Decomposition of crude oil with TiO2 nanoparticles: by using titanium dioxide photocatalysts
and UV-A radiation from the sun, the hydrocarbons found in crude oil can be turned into H 2O
and CO2. Higher amounts of oxygen and UV radiation increased the degradation of the model
organics. These particles can be placed on floating substrates, making it easier to recover and
catalyze the reaction. This is relevant since oil slicks float on top of the ocean and photons
from the sun target the surface more than the inner depth of the ocean. By covering floating
substrates like woodchips with epoxy adhesives, water logging can be prevented and TiO2
particles can stick to the substrates. With more research, this method should be applicable to
other organics.
 Decontamination of water with photocatalysis and adsorption: the removal and destruction of
organic contaminants in groundwater can be addressed through the impregnation of
adsorbents with photoactive catalysts. These adsorbents attract contaminating organic
atoms/molecules like tetrachloroethylene to them. The photoactive catalysts impregnated
inside speed up the degradation of the organics. Adsorbents are placed in packed beds for 18
hours, which would attract and degrade the organic compounds. The spent adsorbents would
then be placed in regeneration fluid, essentially taking away all organics still attached by
passing hot water counter-current to the flow of water during the adsorption process to speed
up the reaction. The regeneration fluid then gets passed through the fixed beds of silica gel
photocatalysts to remove and decompose the rest of the organics left. Through the use of fixed
bed reactors, the regeneration of adsorbents can help increase the efficiency.
 Decomposition of polyaromatic hydrocarbons (PAHs). Triethylamine (TEA) was utilized to
solvate and extract the polyaromatic hydrocarbons (PAHs) found in crude oil. By solvating
these PAHs, TEA can attract the PAHs to itself. Once removed, TiO2 slurries and UV light can
photocatalytically degrade the PAHs. The figure shows the high success rate of this
experiment. With high yielding of recoveries of 93–99% of these contaminants, this process
has become an innovative idea that can be finalized for actual environmental usage. This
procedure demonstrates the ability to develop photocatalysts that would be performed at
ambient pressure, ambient temperature, and at a cheaper cost.
PEG (POLYETHYLENE GLYCOL)

Polyethylene glycol (PEG) is a polyether compound with many applications from industrial
manufacturing to medicine. It has also been known as polyethylene oxide (PEO) or polyoxyethylene
(POE), depending on its molecular weight. PEG is a neutral, hydrophilic polyether and less expensive.
It avoids the use of acid or base catalysts and reagent can be recovered and reused. Thus, it offers a
convenient, inexpensive, nonionic, nontoxic, and recyclable reaction medium for the replacement of
volatile organic solvents (see Scheme 1).
Scheme 1: Structure of polyethylene glycol (PEG).

Polyethylene glycol (PEG) is a condensation polymer of ethylene oxide and water with the
general formula H−(O−CH2−CH2)n−OH , where n the average number of repeating oxyethylene is
groups typically from 4 to about 180. The low molecular weight members from n=2 to to 4 are
diethylene glycol, triethylene glycol, and tetra ethylene glycol, respectively, which are produced as
pure compounds. The wide range of chain lengths provides identical physical and chemical properties
for the proper application selections directly or indirectly in the field of chemical and biological
sciences. In recent past polyethylene glycols (PEGs) have been used as catalysts and catalyst supports
and also have been found to be an inexpensive, non-toxic, environmentally friendly reaction medium,
which avoid the use of acid or base catalysts.
PRODUCTION OF PEG
The production of polyethylene glycol was first reported in 1859. Both A. V. Laurence and
Charles Adolphe Wurtz independently isolated products that were polyethylene glycols.
Polyethylene glycol is produced by the interaction of ethylene oxide with water, ethylene glycol, or
ethylene glycol oligomers. The reaction is catalyzed by acidic or basic catalysts. Ethylene glycol and
its oligomers are preferable as a starting material instead of water, because they allow the creation of
polymers with a low polydispersity (narrow molecular weight distribution). Polymer chain length
depends on the ratio of reactants.
HOCH2CH2OH + n(CH2CH2O) → HO(CH2CH2O)n+1H
Depending on the catalyst type, the mechanism of polymerization can be cationic or anionic.
The anionic mechanism is preferable because it allows one to obtain PEG with a low polydispersity.
Polymerization of ethylene oxide is an exothermic process. Overheating or contaminating ethylene
oxide with catalysts such as alkalis or metal oxides can lead to runaway polymerization, which can
end in an explosion after a few hours.
Polyethylene oxide, or high-molecular weight polyethylene glycol, is synthesized by
suspension polymerization. It is necessary to hold the growing polymer chain in solution in the
course of the polycondensation process. The reaction is catalyzed by magnesium-, aluminium-, or
calcium-organoelement compounds. To prevent coagulation of polymer chains from solution,
chelating additives such as dimethylglyoxime are used.
Alkaline catalysts such as sodium hydroxide (NaOH), potassium hydroxide (KOH), or sodium
carbonate (Na2CO3) are used to prepare low-molecular-weight polyethylene glycol.
USES of PEG
MEDICAL USES
 PEG is the basis of a number of laxatives. Whole bowel irrigation with polyethylene glycol and
added electrolytes is used for bowel preparation before surgery or colonoscopy.
 PEG is also used as an excipient in many pharmaceutical products.
 When attached to various protein medications, polyethylene glycol allows a slowed clearance
of the carried protein from the blood.
 The possibility that PEG could be used to fuse nerve cells is being explored by researchers
studying spinal cord injury.
Chemical uses
 Because PEG is hydrophilic molecule, it has been used to passivate microscope glass slides for
avoiding non-specific sticking of proteins in single-molecule fluorescence studies.
 Polyethylene glycol has a low toxicity and is used in a variety of products. The polymer is used
as a lubricating coating for various surfaces in aqueous and non-aqueous environments.
 Since PEG is a flexible, water-soluble polymer, it can be used to create very high osmotic
pressures (on the order of tens of atmospheres). It also is unlikely to have specific interactions
with biological chemicals. These properties make PEG one of the most useful molecules for
applying osmotic pressure in biochemistry and biomembranes experiments, in particular
when using the osmotic stress technique.
 Polyethylene glycol is also commonly used as a polar stationary phase for gas
chromatography, as well as a heat transfer fluid in electronic testers.
 PEG has also been used to preserve objects that have been salvaged from underwater, as was
the case with the warship Vasa in Stockholm, and similar cases. It replaces water in wooden
objects, making the wood dimensionally stable and preventing warping or shrinking of the
wood when it dries. In addition, PEG is used when working with green wood as a stabilizer,
and to prevent shrinkage.
 PEG has been used to preserve the painted colors on Terra-Cotta Warriors unearthed at a
UNESCO World Heritage site in China. These painted artifacts were created during the Qin Shi
Huang Di dynasty (first emperor of China). Within 15 seconds of the terra-cotta pieces being
unearthed during excavations, the lacquer beneath the paint begins to curl after being exposed
to the dry Xian air. The paint would subsequently flake off in about four minutes. The German
Bavarian State Conservation Office developed a PEG preservative that when immediately
applied to unearthed artifacts has aided in preserving the colors painted on the pieces of clay
soldiers.
 PEG is often used (as an internal calibration compound) in mass spectrometry experiments,
with its characteristic fragmentation pattern allowing accurate and reproducible tuning.
 PEG derivatives, such as narrow range ethoxylates, are used as surfactants.
 PEG is a polyol and can be reacted with an isocyanate to make polyurethane.
 PEG has been used as the hydrophilic block of amphiphilic block copolymers used to create
some polymersomes.
BIOLOGICAL USES
 PEG is commonly used as a crowding agent in in vitro assays to mimic highly crowded cellular
conditions.
 PEG is commonly used as a precipitant for plasmid DNA isolation and protein crystallization.
X-ray diffraction of protein crystals can reveal the atomic structure of the proteins.
 PEG is used to fuse two different types of cells, most often B-cells and myelomas in order to
create hybridomas. César Milstein and Georges J. F. Köhler originated this technique, which
they used for antibody production, winning a Nobel Prize in Physiology or Medicine in 1984.
 Polymer segments derived from PEG polyols impart flexibility to polyurethanes for
applications such as elastomeric fibers (spandex) and foam cushions.
 In microbiology, PEG precipitation is used to concentrate viruses. PEG is also used to induce
complete fusion (mixing of both inner and outer leaflets) in liposomes reconstituted in vitro.
 Gene therapy vectors (such as viruses) can be PEG-coated to shield them from inactivation by
the immune system and to de-target them from organs where they may build up and have a
toxic effect. The size of the PEG polymer has been shown to be important, with larger
polymers achieving the best immune protection.
 PEG is a component of stable nucleic acid lipid particles (SNALPs) used to package siRNA for
use in vivo.
 In blood banking, PEG is used as a potentiator to enhance detection of antigens and antibodies.
 When working with phenol in a laboratory situation, PEG 300 can be used on phenol skin
burns to deactivate any residual phenol.
 In biophysics, polyethylene glycols are the molecules of choice for the functioning ion channels
diameter studies, because in aqueous solutions they have a spherical shape and can block ion
channel conductance.
COMMERCIAL USES
 PEG is the basis of many skin creams (as cetomacrogol) and personal lubricants (frequently
combined with glycerin).
 PEG is used in a number of toothpastes as a dispersant. In this application, it binds water and
helps keep xanthan gum uniformly distributed throughout the toothpaste.
 PEG is also under investigation for use in body armor, and in tattoos to monitor diabetes.
 In low-molecular-weight formulations (i.e. PEG 400), it is used in Hewlett-Packard designjet
printers as an ink solvent and lubricant for the print heads.
 PEG is also one of the main ingredients in paintball fills, because of its thickness and flexibility.
However, as early as 2006, some paintball manufacturers began substituting cheaper oil-based
alternatives for PEG.
 PEG is also used as an anti-foaming agent in food– its INS number is 1521 or E1521 in the EU.
INDUSTRIAL USES
 A nitrate ester-plasticized polyethylene glycol (NEPE-75) is used in Trident II submarine-
launched ballistic missile solid rocket fuel.
 Dimethyl ethers of PEG are the key ingredient of Selexol, a solvent used by coal-burning,
integrated gasification combined cycle (IGCC) power plants to remove carbon dioxide and
hydrogen sulfide from the gas waste stream.
 PEG has been used as the gate insulator in an electric double-layer transistor to induce
superconductivity in an insulator.
 PEG is also used as a polymer host for solid polymer electrolytes. Although not yet in
commercial production, many groups around the globe are engaged in research on solid
polymer electrolytes involving PEG, with the aim of improving their properties, and in
permitting their use in batteries, electro-chromic display systems, and other products in the
future.
 PEG is injected into industrial processes to reduce foaming in separation equipment.
 PEG is used as a binder in the preparation of technical ceramics.
NANOCATALYST:-
Nanocatalysis is a rapidly growing field which involves the use of nanomaterials as catalysts
for a variety of homogeneous and heterogeneous catalysis applications. Since nanoparticles have a
large surface-to-volume ratio compared to bulk materials, they are attractive candidates for use as
catalysts. Heterogeneous catalysis represents one of the oldest commercial practices of nanoscience;
nanoparticles of metals, semiconductors, oxides, and other compounds have been widely used for
important chemical reactions.
A key objective of nanocatalysis research is to produce catalysts with 100% selectivity,
extremely high activity, low energy consumption, and long lifetime. This can be achieved only by
precisely controlling the size, shape, spatial distribution, surface composition and electronic
structure, and thermal and chemical stability of the individual nanocomponents.
HOMOGENEOUS AND HETEROGENEOUS CATALYSIS
In homogeneous catalysis, transition metal nanoparticles in colloidal solutions are used as
catalysts. In this type of catalysis, the colloidal transition metal nanoparticles are finely dispersed in
an organic or aqueous solution, or a solvent mixture.
The colloidal nanoparticle solutions must be stabilized in order to prevent aggregation of the
nanoparticles and also to be good potential recyclable catalysts. Metal colloids are very efficient
catalysts because a large number of atoms are present on the surface of the nanoparticles. The
method that is used in synthesizing transition metal nanoparticles in colloidal solutions is very
important for catalytic applications. The reduction method employed controls the size and the shape
of the transition metal nanoparticles that are formed, which are very important in catalytic
applications.
The different reduction methods that have been used to synthesize colloidal transition metal
nanoparticles for homogeneous catalysis are summarized below. Chemical reduction of the
precursor transition metal salt is the most widely used method of synthesizing transition metal
nanocatalysts in colloidal solution. There are four other synthetic methods to prepare colloidal
transition metal nanocatalysts that are not as commonly used. These synthetic methods include
1. thermal, photochemical, or sonochemical reduction of the precursor transition metal salts
2. ligand reduction and displacement from organometallic precursors
3. metal vapor synthesis and
4. electrochemical reduction of transition metal precursor salts.
Stabilization of nanoparticles in the solution is necessary in order to prevent agglomeration and
aggregation. For catalytic applications, the choice of stabilizers plays an important role in
determining the reactivity of nanoparticles.
A good stabilizer is one that protects the nanoparticles during the catalytic process, but does not
neutralize the surface of nanoparticles resulting in loss of catalytic activity. The choice of a stabilizer
to be used for capping the nanoparticles is usually a balancing act between passivation of the
nanoparticle surface and the fraction of available sites for catalysis, and also affects the size and
shape of the nanoparticles formed.
Heterogeneous metal nanocatalysts are prepared by adsorption of nanoparticles on to supports,
which involves functionalization of supports to adsorb nanoparticles on to them and, fabrication of
nanostructures on the supports by lithographic techniques.
Nanomaterial-based catalysts are usually heterogeneous catalysts broken up into metal
nanoparticles in order to speed up the catalytic process. Metal nanoparticles have a higher surface
area so there is increased catalytic activity because more catalytic reactions can occur at the same
time. Nanoparticle catalysts can also be easily separated and recycled with more retention of catalytic
activity than their bulk counterparts. These catalysts can play two different roles in catalytic
processes: they can be the site of catalysis or they can act as a support for catalytic processes. They
are typically used under mild conditions to prevent decomposition of the nanoparticles at extreme
conditions.
FUNCTIONALIZED NANOPARTICLES
Functionalized metal nanoparticles are more stable in solution compared to non-
functionalized metal nanoparticles. In liquid solutions, the metal nanoparticles are close enough
together to be affected by van der Waals force. If there isn’t anything to oppose these forces, then the
nanoparticles will aggregate, which will lead to a decrease in catalytic activity by lowering the surface
area. For organometallic functionalized nanoparticles, ligands are coordinated to the metal center to
prevent aggregation. Using different ligands alters the properties and sizes of the nanoparticle
catalysts. Nanoparticles can also be functionalized with polymers or oligomers to sterically stabilize
the nanoparticles by providing a protective layer that prevents the nanoparticles from interacting
with each other. Alloys of two metals, called bimetallic nanoparticles, are used to create synergistic
effects on catalysis between the two metals.[5]
Benefits of nanocatalysts in the chemical industry
fig 2.23 Benefits of nanocatalysts

 Increased selectivity and activity of catalysts by controlling pore size and particle
characteristics
 Replacement of precious metal catalysts by catalysts tailored at the nanoscale and use of base
metals, thus improving chemical reactivity and reducing process costs
 Catalytic membranes by design that can remove unwanted molecules from gases or liquids by
controlling the pore size and membrane characteristics
APPLICATIONS OF NANOCATALYSIS
Sector: Biomass
1. Application: Biomass gasification to produce high syn gas and biomass pyrolysis for production
of bio-oil
Process Improvements: • Novel Al2O3 supported NiO catalyst reduces tar yield significantly
and increases tar removal efficiency to 99% • Significant increase in gas yield • Lighter
fractions of H2 & CO are increased in the syn gas composition while heavier fractions of CH4 &
CO are reduced, thus improving syn gas quality
Catalyst: Nano NiO catalyst supported on γ- Al2O3 microspheres of 3 mm size
2. Application: Production of biodiesel from waste cooking oil
Process Improvements: • Esterification of fatty acids (FFAs) and transesterification of
triglycerides to biodiesel in one pot • Solid acid nanocatalysis of Al0.9H0.3PW12O40

nanotubes with double acid sites yield 96% of biodiesel from waste cooking oil as compared to
42.6% with conventional H3PW12O40 catalyst
Catalyst: Aluminium dodeca-tungsto-phosphate (Al0.9H0.3PW12O40) nanotubes as solid
catalysts with surface area of 278 m2/g
3. Application: Green diesel production using Fischer-Tropsch Synthesis (FTS)
Process Improvements: • Improving the FTS technology for production of high molecular
weight waxes, followed by their hydrocracking to generate liquid fuels • Improved efficiency
of slurry and fixed-bed reactors, used in FTS from biosyngas • Produce long, linear-chain
paraffin waxes in fixed bed & slurry FTS reactors
Catalyst: • Nano Fe and Co powders (10-50 nm) are used as FTS catalysts in slurry reactors,
promoted by other metals like Mn, Cu & alkalis • Produced by thermal plasma chemical vapor
deposition (TPCVD) and cluster spray techniques • Minimize liquid-solid diffusion resistance •
Multi-walled carbon nanofilaments (MWCNF), produced by CO2 sequestration via dry
reforming for gas-to-liquid FTS, with the iron carbide content rendering catalytic activity
Sector: Oil, Gas & Fossil Fuels
• Paraffin Dehydrogenation • Naphtha Reforming • Selective Hydrogenation • Hydrodesufurization
1. Application: Improved economic catalytic combustion of JP-10 aviation fuel using hydrocarbon
fuel soluble nano catalyst
Process Improvements: • 50 ppm addition of catalyst in JP-10 reduces the ignition
temperature required to initiate combustion by about 240°C
Catalyst: Hexanethiol monolayer protected Palladium clusters < 1.5 nm
2. Application: Hydrogen production by steam reforming of ethanol over nanostructured indium
oxide catalysts
Process Improvements: • At 623K, 99% conversion with mesoporous In2O3/KIT-6 catalyst
exhibit high production rates from ethyl alcohol at low-temperatures and yield low
concentration of CO impurity in comparison with other reported catalysts
Catalyst: Mesoporous In2O3 prepared using Mobil Composition of Matter No. 41 (MCM-41)
silica catalyst as templates with particle size of 2-3 nm and surface area of 107 m2/g to 173
m2/g
3. Application: Adsorptive desulfurization and bio desulfurization of fossil oils
Process Improvements: In situ coupling desulfurization using assembly of nano adsorbents
(nano γ- Al2O3) onto surfaces of Pseudomonas de lafieldii
Catalyst: Nano γ- Al2O3 (10 nm in width and 100-200 nm in length) with specific surface area
of 339 m2/g
4. Application: Hydrodesulfurization of diesel
Process Improvements: Hydrodesulfurization of dibenzothiophene increased by 20% using
SDM NiMo/Al-HMS nanocatalyst at 330°C as compared to commercial catalysts.
Catalyst: Synthesis of new NiMo/Al hexagonal, mesoporous structured nanocomposite catalyst
by supercritical deposition method
Dehalogenation and hydrogenation
Nanoparticle catalysts can be used in the hydrogenolysis of C-Cl bonds such as polychlorinated
biphenyls. Hydrogenation of halogenated aromatic amines is also important for the synthesis of
herbicides and pesticides as well as diesel fuel. In organic chemistry, hydrogenation of a C-Cl bond
with deuterium is used to selectively label the aromatic ring for use in experiments dealing with the
kinetic isotope effect. Buil et al. created rhodium complexes that generated rhodium nanoparticles.
These nanoparticles catalyzed the dehalogenation of aromatic compounds as well as the
hydrogenation of benzene to cyclohexane. Polymer-stabilized nanoparticles can also be used for the
hydrogenation of cinnamaldehyde and citronellal.
Hydrosilylation reactions
Hydrosilylation reaction
The Reduction of gold, cobalt, nickel, palladium, or platinum organometallic complexes with
silanes creates a catalytically active metal nanoparticle that catalyzes the hydrosilylation reaction,
which is important for the synthesis of optically active alcohols. BINAP functionalized palladium
nanoparticles and gold nanoparticles have been used for the hydrosilylaytion of styrene under mild
conditions; they were found to be more catalytically active and more stable than non-nanoparticle
Pd-BINAP complexes. The reaction may also be catalyzed by a nanoparticle that consists of two
metals.
Organic redox reactions
Oxidation reaction of cyclohexane to synthesize adiapic acid

An oxidation reaction to form adipic acid is shown in figure 3 and it can be catalyzed by cobalt
nanoparticles. This is used in an industrial scale to produce the nylon 6,6 polymer. Other examples of
oxidation reactions that are catalyzed by metallic nanoparticles include the oxidation of cyclooctane,
the oxidation of ethene, and glucose oxidation.
C-C coupling reactions
Heck coupling reaction

Metallic nanoparticles can catalyze C–C coupling reactions such as the hydroformylation of
olefins, the synthesis of vitamin E and the Heck coupling and Suzuki coupling reactions.
Palladium nanoparticles were found to efficiently catalyze heck coupling reactions. It was
found that increased electronegativity of the ligands on the palladium nanoparticles increased their
catalytic activity.
The compound Pd2(dba)3 is a source of Pd(0), which is the catalytically active source of
palladium used for many reactions, including cross coupling reactions.[3] Pd2(dba)3 was thought to
be a homogeneous catalytic precursor, but recent articles suggest that palladium nanoparticles are
formed, making it a heterogeneous catalytic precursor.
Alternative fuels
Iron oxide and cobalt nanoparticles can be loaded onto various surface active materials like
alumina to convert gases such as carbon monoxide and hydrogen into liquid hydrocarbon fuels using
the Fischer-Tropsch process.
Much research on nanomaterial-based catalysts has to do with maximizing the effectiveness of

the catalyst coating in fuel cells. Platinum is currently the most common catalyst for this application,
however, it is expensive and rare, so a lot of research has been going into maximizing the catalytic
properties of other metals by shrinking them to nanoparticles in the hope that someday they will be
an efficient and economic alternative to platinum. Gold nanoparticles also exhibit catalytic properties,
despite the fact that bulk gold is unreactive.
Fuel cells take advantage of the reaction between hydrogen and oxygen but catalysts are
needed to facilitate this reaction. Nanomaterial catalysts can be used to improve energy production.
In one experiment, yttrium stabilized zirconium nanoparticles were found to increase the efficiency
and reliability of a solid oxide fuel cell. Nanomaterial ruthenium/platinum catalysts could potentially
be used to catalyze the purification of hydrogen for hydrogen storage. Palladium nanoparticles can be
functionalized with organometallic ligands to catalyze the oxidation of CO and NO to control air
pollution in the environment. Carbon nanotube supported catalysts can be used as a cathode catalytic
support for fuel cells and metal nanoparticles have been used to catalyze the growth of carbon
nanotubes. Platinum-cobalt bimetallic nanoparticles combined with carbon nanotubes are promising
candidates for direct methanol fuel cells since they produce a higher stable current electrode.
Nanozymes
Besides conventional catalysis, nanomaterials have been explored for mimicking natural
enzymes. The nanomaterials with enzyme mimicking activities are termed as nanozymes. Lots of
nanomaterials have been used to mimic varieties of natural enzymes, such as oxidase, peroxidase,
catalase, SOD, nuclease, etc. The nanozymes have found wide applications in many areas, from
biosensing and bioimaging to therapeutics and water treatment.
BIOCATALYST
Biocatalysis has many attractive features in the context of green chemistry: mild reaction
conditions (physiological pH and temperature), an environmentally compatible catalyst (an enzyme)
and solvent (often water) combined with high activities and chemo-, regio- and stereoselectivities in
multifunctional molecules. Furthermore, the use of enzymes generally circumvents the need for
functional group activation and avoids protection and deprotection steps required in traditional
organic syntheses. This affords processes which are shorter, generate less waste and are, therefore,
both environmentally and economically more attractive than conventional routes.
Biocatalysis requires using enzymes to promote chemical reactions. Although enzymes have
numerous green chemistry advantages including biodegradability, safety and high selectivity, it has
been estimated that only about 130 routes have been commercialized as of 2002. This figure has
steadily raised due to advances in recombinant DNA technology, protein engineering and
immobilization methods that make the production, manipulation and optimization of enzymes
economically feasible.
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. Both enzymes that have been more or less isolated and
enzymes still residing inside living cells are employed for this task. The modern usage of
biotechnologically produced and possibly modified enzymes for organic synthesis is termed
chemoenzymatic synthesis; the reactions performed are chemoenzymatic reactions.
HISTORY
Biocatalysis underpins some of the oldest chemical transformations known to humans, for
brewing predates recorded history. The oldest records of brewing are about 6000 years old and refer
to the Sumerians.
The employment of enzymes and whole cells have been important for many industries for
centuries. The most obvious uses have been in the food and drink businesses where the production of
wine, beer, cheese etc. is dependent on the effects of the microorganisms.
More than one hundred years ago, biocatalysis was employed to do chemical transformations
on non-natural man-made organic compounds, with the last 30 years seeing a substantial increase in
the application of biocatalysis to produce fine chemicals, especially for the pharmaceutical industry.
Since biocatalysis deals with enzymes and microorganisms, it is historically classified
separately from "homogeneous catalysis" and "heterogeneous catalysis". However, mechanistically
speaking, biocatalysis is simply a special case of heterogeneous catalysis.
ADVANTAGES OF CHEMOENZYMATIC SYNTHESIS

Enzymes display three major types of selectivities:
 Chemoselectivity: Since the purpose of an enzyme is to act on a single type of functional group,
other sensitive functionalities, which would normally react to a certain extent under chemical
catalysis, survive. As a result, biocatalytic reactions tend to be "cleaner" and laborious
purification of product(s) from impurities emerging through side-reactions can largely be
omitted.
 Regioselectivity and diastereoselectivity: Due to their complex three-dimensional structure,
enzymes may distinguish between functional groups which are chemically situated in different
regions of the substrate molecule.
 Enantioselectivity: Since almost all enzymes are made from L-amino acids, enzymes are chiral
catalysts. As a consequence, any type of chirality present in the substrate molecule is
"recognized" upon the formation of the enzyme-substrate complex. Thus a prochiral substrate
may be transformed into an optically active product and both enantiomers of a racemic
substrate may react at different rates.
These reasons, and especially the latter, are the major reasons why synthetic chemists have
become interested in biocatalysis. This interest in turn is mainly due to the need to synthesise
enantiopure compounds as chiral building blocks for Pharmaceutical drugs and agrochemicals.
Additionally, modified enzymes may have a broader substrate range than natural occurring ones,
or have a better reaction rate, or may be easier to produce using current biotechnology.
ASYMMETRIC BIOCATALYSIS
The use of biocatalysis to obtain enantiopure compounds can be divided into two different methods:
1. Kinetic resolution of a racemic mixture
2. Biocatalysed asymmetric synthesis
In kinetic resolution of a racemic mixture, the presence of a chiral object (the enzyme) converts
one of the stereoisomers of the reactant into its product at a greater reaction rate than for the other
reactant stereoisomer.
The stereochemical mixture has now been transformed into a mixture of two different
compounds, making them separable by normal methodology. The maximum yield in such kinetic
resolutions is 50%, since a yield of more than 50% means that some of wrong isomer also has
reacted, giving a lower enantiomeric excess. Such reactions must therefore be terminated before
equilibrium is reached. If it is possible to perform such resolutions under conditions where the two
substrate- enantiomers are racemizing continuously, all substrate may in theory be converted into
enantiopure product. This is called dynamic resolution.
In biocatalysed asymmetric synthesis, a non-chiral unit becomes chiral in such a way that
the different possible stereoisomers are formed in different quantities. The chirality is introduced
into the substrate by influence of enzyme, which is chiral. Yeast is a biocatalyst for the
enantioselective reduction of ketones.
The Baeyer–Villiger oxidation is another example of a biocatalytic reaction. In one study a

specially designed mutant of Candida antarctica was found to be an effective catalyst for the Michael
addition of acrolein with acetylacetone at 20 °C in absence of additional solvent.
Another study demonstrates how racemic nicotine (mixture of S and R-enantiomers 1 in
scheme 3) can be deracemized in a one-pot procedure involving a monoamine oxidase isolated from
Aspergillus niger which is able to oxidize only the amine S-enantiomer to the imine 2 and involving
an ammonia–borane reducing couple which can reduce the imine 2 back to the amine 1.[10] In this
way the S-enantiomer will continuously be consumed by the enzyme while the R-enantiomer
accumulates. It is even possible to stereoinvert pure S to pure R.
GREEN SOLVENTS
INTRODUCTION
Solvents define a major part of the environmental performance of processes in chemical
industry and also impact on cost, safety and health issues. The idea of “green” solvents expresses the
goal to minimize the environmental impact resulting from the use of solvents in chemical production.
The use of hazardous and toxic solvents in chemical laboratories and the chemical industry is
considered a very important problem for the health and safety of workers and environmental
pollution. Green Chemistry aims to change the use of toxic solvents with greener alternatives, with
replacement and synthetic techniques, separation and purification which do not need the use of
solvents.
Organic solvents are very important as liquid medium for reactions to take place, and after
the synthesis of a chemical product for extraction, separation, purification and drying. Solvents are
also very important in chemical analytical methodologies, spectrometry and measurements of
physicochemical properties. The majority of solvents are organic chemicals with hazardous and toxic
properties, costly (part of the petrochemical industry) and part of the large waste by-products of the
chemical industry causing environmental problems. Although most of their toxic potential is known
and there are safety rules for their use, prolonged and high concentration exposures can cause
occupational diseases.
Aromatic solvents (benzene, toluene, etc), chlorinated and polychlorinated solvents (carbon
tetrachloride, chloroform, dichloromethane, etc) and other organic solvents (DMSO, DMF, petroleum
ether, diethyl ether, acetone, etc) are used in great quantities in many laboratory and analytical
techniques. The persistent solvents (non-biodegradable) are difficult to recycle and their disposition
is very expensive.
One of principles of Green Chemistry is to promote the idea of “greener” solvents (non-toxic,
benign to environment), replacement in cases that can be substituted with safer alternatives, or
changes in the methodologies of organic synthesis, when solvents are not needed.
Green Chemistry (GC) has placed the solvent issue of synthetic organic chemistry and
practices in their use at the same level with alternative synthetic routes in chemical industry. “Green”
solvents, replacement with other methods or recycling and reuse is at the core of GC goals.
Organic solvents are a major part of chemical processes and research activities in chemical
laboratories. The Green Chemistry is aiming to promote the use of “greener” solvents, solvent-free
reactions or alternatives that can be benign to environment and human health.
Green solvents are environmentally friendly solvents or biosolvents, which are derived from the
processing of agricultural crops. The use of petrochemical solvents are the key to the majority of
chemical processes but not without severe implications on the environment. The Montreal Protocol
identified the need to re-evaluate chemical processes with regard to their use of volatile organic
compounds of VOCs and the impact theses VOCs has on the environment. Green solvents were
developed as a more environmentally friendly alternative to petrochemical solvents.
Why Reactions Are Performed Using Solvents?

• To dissolve reactants.
• To slow or increase the rate of reactions.
• To act as a heat sink or heat transfer agent.
• To prevent hot spots and run-away reactions.
Issues with Organic Solvents
• Organic solvents are of concern to the chemical industry because of the sheer volume used in
synthesis, processing, and separation.
• Organic solvents are expensive
• Organic solvents are highly regulated.
• Many organic solvents are volatile, flammable, toxic, and carcinogenic.
Solvent alternatives
A. Use of solvent less reactions
B. Use of “non-organic” solvents
C. Processing technology
Use of non-organic solvents
• Ionic liquids
• Liquid and supercritical CO2
• Fluorous Phase Chemistry
• Water
IONIC LIQUIDS
An ionic liquid (IL) is a salt in the liquid state. In some contexts, the term has been restricted to
salts whose melting point is below some arbitrary temperature, such as 100 °C (212 °F). While
ordinary liquids such as water and gasoline are predominantly made of electrically neutral
molecules, ionic liquids are largely made of ions and short-lived ion pairs. These substances are
variously called liquid electrolytes, ionic melts, ionic fluids, fused salts, liquid salts, or ionic glasses.
They are known as "solvents of the future" as well as "designer solvents".
Ionic liquids are used extensively in recent years as alternative solvents in organic synthesis.
Ionic liquids have many applications, as powerful solvents and electrically conducting fluids
(electrolytes). Salts that are liquid at near-ambient temperature are important for electric battery
applications. Ionic liquids are mixtures of anions and cations, fused salts with melting point less
than 100 oC, which can be used as alternative solvents in organic synthesis. Although ionic liquids
do not fit to the principles of green chemistry, they are considered as good candidates for future
improvements that can give “green” credentials to their use and applications.
In recent years ionic liquids (ILs) have attracted considerable attention owing to their potential
use in a diversified range of applications. It is believed that ILs can successfully replace volatile
organic media in a wide range of chemical processes. They have been studied and applied in
organometallic catalysis, organocatalysis and biocatalysis, where they provide unique reaction
media offering better selectivity, faster rates and greater catalyst or enzyme stability in comparison
to conventional solvents. Due to their remarkable properties, such as outstanding solvating
potential, thermal stability and their tunable propertiesby suitable choices of cations and anions,
they are considered favourable medium candidates for chemical syntheses.
ILs are characterized by properties such as negligible vapour pressure and non-flammability
under ambient conditions, high thermal conductivity, a wide electrochemical window and high
polarity. They also have the ability to dissolve a wide diversity of materials, including salts, fats,
proteins, amino acids, surfactants, sugars, polysaccharides and organic solvents. However, the most
important attribute of ILs is the possibility of designing their properties to order.
CLASSIFICATION OF IONIC LIQUIDS

ILs are usually categorized into four types based on their cation segment:
1) alkylammonium-ILs,
2) dialkylimidazolium-ILs,
3) phosphonium- ILs
4) N-alkylpyridinium based ILs
Figure 2.24 Alkylammonium, phosphonium, dialkylimidazolium and N-alkylpyridinium cations.
1) alkylammonium-ILs
Ammonium-based ILs have been used widely as electrolytes in high-energy electrochemical
devices owing to their good electrochemical cathodic stabilities, low melting points and low
viscosities.
2) dialkylimidazolium-ILs,
Popular imidazolium-based ILs are among the most studied ILs. Selection of the imidazolium
ring as a cation is often due to its stability within oxidative and reductive conditions, low viscosity of
imidazolium ILs and their ease of synthesis. There are also several reports regarding the application
of imidazolium- based ILs as catalysts for the improvement of reaction time, yield and
chemoselectivity of many organic reactions.
3) phosphonium- ILs
Phosphonium- based ILs are used as the catalyst and solvent for hydroformylation,
palladium-catalyzed Heck rEactions and palladium-mediated Suzuki cross- coupling reactions. In
addition, they are also powerful phase-transfer catalysts for the Halex reaction. Recently,
phosphonium-based ILs have been used for CO2 capture. Along with their application in the
synthesis of a novel polystyrene-based material [38], the styrenic derivatives of phosphonium-based
ILs are used as monomers in the synthesis of phosphonium-containing random copolymers. The
cyclohexadieneylradical in trihexyl (tetradecyl) phosphonium chloride (IL101) has been studied,

and the effects of temperature and solvent on the reaction have been investigated using muon
techniques at the TRIUMF National Laboratory of Canada. Although phosphonium-based ILs showed
good stability in the presence of bases (even in reactions involving strong bases such as Grignard
reagents), they are still susceptible to reaction with small bases. Unlike ammonium-based ILs, which
undergo Hoffman or -elimination in the presence of a base at high temperature, phosphonium-based
ILs tend to decompose to tertiary phosphine oxides and alkanes under alkaline conditions.
4) N-alkylpyridinium based ILs
Pyridinium-based ILs are more novel in comparison with their imidazolium-based
counterparts, and research on their stability, reactivity and catalytic role in organic synthesis is still
in progress Although they show poor regioselectivity in palladium-catalyzed telomerization of
butadiene with methanol, and they have a negative effect on the rate of some Diels-Alder reactions,
applications of this type of ILs are quite successful in reactions such as Friedel-Crafts and Grignard.
The catalytic role of pyridinium-based ILs has been shown to be remarkable in the synthesis of some
pharmaceutical agents such as 1,4-dihydropyridine, dihydropyrimidinones and 3,5-
bis(dodecyloxycarbonyl)- 1,4-dihydropyridine derivatives. Phosphonium-based ILs are more novel
than the imidazolium- and pyridinium-based ILs. They are more thermally stable (in some cases up
to nearly 400˚C!) in comparison with ammonium and imidazolium salts, and this remarkable
property makes them suitable for reactions that are carried out at greater than 100˚C.
Properties of Ionic Liquids

o Good solvents for a wide range of both organic and inorganic materials.
o Have potential to be highly polar yet noncoordinating.
o By varying cations and anions, ionic liquids can be tailored for specific applications.
o Possibility for reaction rate enhancement, higher selectivity and higher yields.
o High thermal stability
o Often immiscible with organic solvents and/or water
o No measurable vapor pressure
o Non-flammable
o Can be recycled
o Are they safer than solvents?
Ionic liquids have been used as solvents in a variety of reactions
o Heck Reaction1
o Friedel-Crafts reactions2
o Diels-Alder reactions3
o Hydrogenation reactons4
POTENTIAL APPLICATIONS
GAS HANDLING
ILs have been considered for a variety of industrial applications. Their properties of low
vapor pressure, thermal stability, and solvation for a wide variety of compounds and gases make
them attractive in gas storage and handling applications. Air Products uses ILs instead of pressurized
cylinders as a transport medium for reactive gases such as trifluoroborane, phosphine and arsine.
The gases are dissolved in the liquids at or below atmospheric pressure and are easily withdrawn
from the containers by applying a vacuum. Gas manufacturer Linde exploits the low solubility of
hydrogen in ILs to compress the gas up to 450 bar in filling stations by using an ionic liquid piston
compressor. The IL 1-butyl-3-methylimidazolium chloride has been investigated for separating
hydrogen from ammonia borane. ILs and amines have been investigated for capturing carbon
dioxide CO2 and purifying natural gas.
COAL PROCESSING
ILs, especially imidazolium-based ILs have been found effective in pretreatment of coal before
use in applications such as pyrolysis and gasification. Pretreatment with ionic liquids causes
'swelling' of the coal structure, allowing better gasification.
PHARMACEUTICALS
Recognizing that approximately 50% of commercial pharmaceuticals are organic salts, ionic
liquid forms of a number of pharmaceuticals have been investigated. Combining a pharmaceutically
active cation with a pharmaceutically active anion leads to a Dual Active ionic liquid in which the
actions of two drugs are combined. ILs can extract specific compounds from plants for
pharmaceutical, nutritional and cosmetic applications, such as the antimalarial drug artemisinin
from the plant Artemisia annua.
CELLULOSE PROCESSING
The dissolution of cellulose by ILs has attracted interest. A patent application from 1930
showed that 1-alkylpyridinium chlorides dissolve cellulose. Following in the footsteps of the lyocell
process, which uses hydrated N-Methylmorpholine N-oxide, as a non-aqueous solvent for the
dissolution of the pulp and paper? The dissolution of cellulose–based materials like tissue paper
waste, generated in chemical industries and at research laboratories, in room temperature IL 1-
butyl-3-methylimidazolium chloride, bmimCl and the recovery of valuable compounds by
electrodeposition from this cellulose matrix was studied. The "valorization" of cellulose, i.e. its
conversion to more valuable chemicals, has been achieved by the use of ionic liquids. Representative
products are glucose esters, sorbitol, and alkylgycosides.[41] IL 1-butyl-3-methylimidazolium chloride
dissolves freeze dried banana pulp and with an additional 15% DMSO, lends itself to Carbon-13 NMR
analysis. In this way the entire complex of starch, sucrose, glucose, and fructose can be monitored as
a function of banana ripening. ILs are effective for extracting chemicals potentially relevant to
biodiesel, ethanol, and other biofuels from algae.
NUCLEAR FUEL REPROCESSING
The IL 1-butyl-3-methylimidazolium chloride has been investigated as a non-aqueous
electrolyte media for the recovery of uranium and other metals from spent nuclear fuel and other
sources. Protonated betaine bis(trifluoromethanesulfonyl) imide has been investigated as a solvent
for uranium oxides. Ionic liquids, N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide
and N-methyl-N-propylpiperidinium bis(trifluoromethylsulfonyl)imide, have been investigated for
the electrodeposition of europium and uranium metals respectively.
SOLAR THERMAL ENERGY
ILs are potential heat transfer and storage media in solar thermal energy systems.
Concentrating solar thermal facilities such as parabolic troughs and solar power towers focus the
sun's energy onto a receiver which can generate temperatures of around 600 °C (1,112 °F). This heat
can then generate electricity in a steam or other cycle. For buffering during cloudy periods or to
enable generation overnight, energy can be stored by heating an intermediate fluid. Although nitrate
salts have been the medium of choice since the early 1980s, they freeze at 220 °C (428 °F) and thus
require heating to prevent solidification. Ionic liquids such as Cmim4[BF4] have more favorable liquid-
phase temperature ranges (-75 to 459 °C) and could therefore be excellent liquid thermal storage
media and heat transfer fluids.
WASTE RECYCLING
ILs can aid the recycling of synthetic goods, plastics, and metals. They offer the specificity
required to separate similar compounds from each other, such as separating polymers in plastic
waste streams. This has been achieved using lower temperature extraction processes than current
approaches and could help avoid incinerating plastics or dumping them in landfill.
BATTERIES
ILs can replace water as the electrolyte in metal-air batteries. ILs are attractive because of
their low vapor pressure, increasing battery life by drying slower. Furthermore, ILs have an
electrochemical window of up to six volts (versus 1.23 for water) supporting more energy-dense
metals. Energy densities from 900-1600 watt-hours per kilogram appear possible.[53]
DISPERSING AGENT
ILs can act as dispersing agents in paints to enhance finish, appearance and drying properties.
ILs are used for dispersing nanomaterials at IOLITEC.
CARBON CAPTURE
Main article: Ionic liquids in carbon capture Ionic liquids have been proposed as an absorbent in
carbon capture. They have various advantages over traditional absorbents, such as the currently
dominant amine-based technologies. 1-Butyl-3-methylimidazolium hexafluorophosphate is one
example of a proposed CO2 absorbent.
TRIBOLOGY
Some ionic liquids have been shown to reduce friction and wear in basic tribological testing,
and their polar nature makes them candidate lubricants for tribotronic applications. While the
comparatively high cost of ionic liquids currently prevents their use as neat lubricants, adding ionic
liquids in concentrations as low as 0.5 wt% may significantly alter the lubricating performance of
conventional base oils. Thus, the current focus of research is on using ionic liquids as additives to
lubricating oils, often with the motivation to replace widely used, ecologically harmful lubricant
additives. However, the claimed ecological advantage of ionic liquids has been questioned repeatedly
and is yet to be demonstrated from a lifecycle perspective.
SAFETY
Ionic liquids' low volatility effectively eliminates a major pathway for environmental release
and contamination. However, this property is distinct from toxicity. Ionic liquids' aquatic toxicity is
as severe as or more so than many current solvents. Mortality isn't necessarily the most important
metric for measuring impacts in aquatic environments, as sub-lethal concentrations change
organisms' life histories in meaningful ways. Balancing VOC reductions against waterway spills (via
waste ponds/streams, etc.) requires further research. Ionic liquids' substituent diversity simplifies
the process of identifying compounds that meet safety requirements.
Ultrasound can degrade solutions of imidazolium-based ionic liquids with hydrogen peroxide and
acetic acid to relatively innocuous compounds.
Despite low vapor pressure many ionic liquids are combustible and therefore require careful
handling. Brief exposure (5 to 7 seconds) to a flame torch can ignite some Ionic liquids. Complete
combustion is possible for some Ionic liquids.
Limitations of Ionic liquids
o Very expensive compared to organic solvents (100 to 1000 x).
o Have to be made, often using solvent.
o Products have to be extracted from ionic liquid using solvent.
o May have to wash with water prior to reuse.
GREEN SOLVENTS AND ALTERNATIVE METHODS
Green solvents have been characterised for their low toxicity, higher low solubility in water
(low miscibility), easily biodegradable under environmental conditions, high boiling point (not very
volatile, low odour, health problems to workers) and easy to recycle after use.
The topics are mainly based on the development and application of alternative solvents such
as aqueous media, ionic liquids, supercritical phases, green organic solvents, soluble polymers,
including phase-separable reagents or related separation strategies. There are increasing efforts
from both academia and industry to develop cleaner and more sustainable processes and
technologies.
In this brief presentation we provide a short description of some of the important changes in
the synthesis of chemicals under green chemistry principles and alternative methods.
1. ORGANIC SYNTHESIS IN WATER

Although water is considered a problem for organic synthesis and the purification processes
and drying in final products is very cumbersome, in recent years water is considered a good
solvent for organic reactions. A good example is the synthetic routes of the Diels-Alder
reactions in which the hydrophobic properties of some reagents makes water an ideal
solvent. Water as a solvent accelerates some reactions because some reagent is not soluble
and provides selectivity. The low solubility of Oxygen is also an advantage for some reactions
where metal catalysts are used.
Why Water?
o Cost - water is the world’s cheapest solvent.
o Safety – doesn’t get any safer than water.
o Some reactions work better in water.
Limitations of Water as a Solvent
o Some reactions will never work in water.
o Poor solubility of most organic compounds.
o Solubility may be increased by use of organic co-solvents, pH control, surfactants, and
hydrophilic auxiliaries.
Green Concerns of Water
o The product may need to be extracted into an organic solvent to purify it.
o This generates aqueous effluent containing solvent, which must be properly disposed.
Example Aqueous Reactions
o Diels-Alder reactions1
o Claisen-rearrangement2
o Aldol reactions3
o Allylation reactions4
o Oxidations5
o Hydrogenations6
2. ORGANIC SYNTHESIS IN POLYFLUORINATED PHASES

In these techniques chemists are using polyfluorinated two phase systems of solvents
which dissolve catalysts with a long hyperfluorinated alcylo- or aliphatic chain. These
catalysts can be very effective and provide high yields in some types of reactions where the
catalysts play an important part. Another advantage is that after the reaction the catalyst can
be separated and recycled. Reagents are dissolved in an organic solvent which is insoluble in
the hyperfluorinated phase. Warming up the mixture accelerates the reaction with excellent
yield of products.
Physical Properties of Perfluorinated Organic Compounds

o High affinity for other fluorinated compounds.
o High solubility in scCO2.
o Immiscible in water and most common organic solvents at room temperature.
o Forms homogenous solutions at elevated temperatures with many of these solvents.
o Chemically inert.
– Is this good or bad?
Uses for Fluorous Chemistry

o For the recovery and recycling of fluorous catalysts and fluorous reagents.
o Fluorous biphasic organic synthesis.
Principle of Fluorous Biphase Catalysis
Advantages
o Facile recovery of expensive catalysts.
o Complementary to other biphase chemistries.
o More facile separation.
o Design of novel catalysts and reagents.
o Alternative to the solid phase in combinatorial chemistry.
o Non-toxic?
Limitations
o Fluorous solvents and reagents are very expensive.
o 60% fluorine is usually considered the lower cutoff point for efficient fluorous
extraction.
o Still requires use of a second solvent for biphase.
3. SUPERCRITICAL CARBON DIOXIDE AND SUPERCRITICAL WATER
Supercritical fluid is called any liquid substance at a temperature and pressure
above its critical point, where distinct liquid and gas phases do not exist. It can effuse
through solids like a gas, and dissolve materials like a liquid. In addition, close to the
critical point, small changes in pressure or temperature result in large changes in density,
allowing many properties of a supercritical fluid to be "fine-tuned". Supercritical fluids are
suitable as a substitute for organic solvents in a range of industrial and laboratory processes.
Carbon dioxide and water are the most commonly used supercritical fluids. They are use
for supercritical fluid extraction (SFE). These supercritical properties can be applied as
“green chemistry” credentials in chemistry with high yields and minimum waste.
Supercritical CO2
What does it mean to be supercritical?
Supercritical CO2 is a viable alternative but its use has been restricted by its limited solvent
power. Beyond a specific temperature and pressure CO2 becomes a supercritical fluid, a
state that is neither a gas nor a liquid, but has properties of both, known as critical point. The
specific properties of ScCO2 make it an interesting “green” replacement for organic solvents,
which are often less than ideal owing to their acute toxicity, ecological hazards or difficulty
with disposal and recycling. Sc-CO2 has applications in diverse areas as the dyeing and
cleaning of fibres and textiles, Polymerization and polymer processing, purification and
crystallization of pharmaceuticals, and last but not the least as a reaction medium for
chemical synthesis.
Properties of scCO2
• Combination of properties from both the liquid and gas state.

• At liquid-like densities, scCO2 exhibits low viscosity and high diffusion rates.
• High compressibility of the supercritical phase allows for solvent properties to be varied
by small changes in temperature and pressure.
• Can be handled in standard high-pressure equipment on lab or industrial scale.
• Non-toxic, non-flammable, and inexpensive.
• Non-protic and generally unreactive.
• Product isolation to total dryness is achieved by simple decompression.
• CO2 can be recovered and reused.
Examples of scCO2 as Solvent in Synthetic Organic Chemistry
• Hydrogenation
• Hydroformylation
• Photochemical and radical reactions
• Dies-Alder cycloadditions
• Oxidations
• Palladium mediated couplings
• Biotransformations
Limitations of scCO2
• Poor solubility of many substrates in scCO2.
• Modifiers (organic solvents) can be added to regulate solubility, but this move the
process away from being green.
• CO2-philic surfactants are being developed.
– Are expensive and have to be separated from products.
Supercritical CO2 as A Solvent Media
A large number of industrial chemical reactions occur in organic solvents which

include chlorofluorocarbons, benzene, and carbon tetrachloride-all of which have such
environmental downside such as toxicity or damage to the stratosphere ozone layer. Many
of these solvents are among the ten most released chemicals to the environment.
Supercritical carbon dioxide (SC-CO2) has been identified as a promising environmentally
benign solvent. It is an energy conserving, selective and waste reducing alternative to
organic solvents. Fast and sensitive organic synthesis can be achieved with high levels of
functionality, controllability and energy efficiency. Product separation and fractionation may
accompany the reaction, reducing the number of process steps.
4. ORGANIC SYNTHESIS WITH CARBONIC ESTERS

Carbonic esters, such as DMC, dimethyl carbonate (CH3OCOOCH3) are considered a new class
of “green” solvents in many organic reaction processes. They can replace methychlorides and
dimethyl sulphate esters which are toxic and hazardous.
DMC can be used in methylation reactions of phenols, anilines and carboxylic acids.
DBU is an alternative solvent that can be used for methylation reactions of phenols, indoles
and benzimidazoles.
5. REPLACEMENT OF TOXIC SOLVENTS WITH LESS TOXIC ONES

The replacement of toxic or hazardous organic solvents in industrial processes and
systems has been initiated long time ago. Examples, like replacement of benzene with
toluene, cyclohexane instead of carbon tetrachloride, dichloromethane instead of
chloroform etc. The scientific literature contains many examples and practices with
replacement of the most toxic and hazardous solvents.
6. “GREEN SOLVENTS” FROM PLANTS
Plants are considered renewable sources of energy but also a resource for various
materials. Plant oils or vegetable oils derive from plant sources. Unlike petroleum which is
the main source of chemicals in the petrochemical industry they are renewable sources.
There are three primary types of plant oil, differing both by the means of extraction and by
the nature of the resulting oil:
Vegetable oils can replace petroleum derived organic solvents, with better properties
and more eco-friendly conditions as waste. Chemists have advanced recently techniques so
that some vegetable oils to become solvents and replace hazardous organic solvents.
As an example of plant-based oils we selected the research project by Spear et al. on
soybean oils and their esters , [Spear SK, Griffin ST, Granger KS, et al. “Renewable plant-
based soybean oil methyl esters as alternatives to organic solvents”. Green Chemistry
9:1008-1015, 2007.
Figure 5.8. Vegetable oils can become a starting material for the production of eco-friendly
solvents which are less toxic than the petrochemical industry’s organic solvents
In the last decade, scientists are researching the use of “green” solvents in
polymerization methods, since the polymer and plastics industries are using vast amounts
of solvents. There have been some successful uses of alternative solvents in polymerization
under the principles of Green Chemistry.
Figure 5. 9. Polymers can be prepared under industrial scale production with the use of
eco-friendly solvents.
PROCESSING TECHNOLOGY
• The use of environmentally sound processing techniques in industrial chemical applications.
Loss of Greenness
• Anytime water is used in an organic reaction, an additional waste stream is created.
• Solvent
• Aqueous quench / workup
• Aqueous wash
Green Process
• A purely organic solvent-based process (with solvent-based workup), with solvent
recovery, would generate little waste.
• The use of technology and good environmental practices to reduce VOCs.
Benefits of Organic Solvents
• Cheap relative to ionic liquids and fluorous solvents.
• Volatile – it takes less energy to remove solvents by evaporation.
• Solvents can be recycled by distillation, creating little waste.
• Regulated – Most countries already have industrial requirements limiting the release of
VOCs.
• Chemistry is known.
GREEN CHEMISTRY AND REGUCTION OF SOLVENT TOXICITY:-ALTERNATIVE SOLVENTS OR

REPLACEMENT
Green Chemistry is concerned with the amounts of toxic organic solvents used in synthetic
routes and overall chemical processes. One principle of green chemistry is to reduce the use of
solvent as much as possible, or if possible to replace with a less toxic or to use alternative
techniques in which solvents are not needed. Solvents in the chemical industry are one of the major
problems concerning workers health and safety and environmental pollution because of waste.
Synthesis, separation of product, cleaning, drying, analysis and recycling, etc. are some of the
processes where solvents are used. Changing solvents and technological processes is not an easy
task. There are many alternatives but can be more expensive, time consuming or difficult to
implement under the established order of chemical methodologies. Although environmental
pollution from solvents can be a serious problem for many chemical industries, the solutions are
not always there to replace solvents or to reduce their use.
In recent years, under the influence of green chemistry principles, some solvents have been
replaced and methodologies changed to more benign techniques. Some of these changes are listed
briefly below.
a) Oxidations under Green Chemistry principles to reduce solvents
Many oxidation techniques in chemical processes have changed under green
chemistry principles. Many oxidations now are performed in water, in supercritical CO 2 or
with less toxic solvents and under room temperatures. The hydrogen peroxide (H 2O2) is
considered as a very good oxidative reagent that performs at normal temperatures. There
are numerous research efforts to apply oxidations with high selectivity and as by-
production only water. Homogeneous and heterogeneous reactions in combination with
catalysts are used in many oxidations. Oxidations are very important in the pharmaceutical
industry and in many petrochemical processes. Oxygen and nitrogen oxides (NOx) are
oxidative agents with green chemistry credentials which are used in the oxidation of
benzene, cyclopentanone and propylene.
In recent years for oxidations chemists use catalytic methods with metallic
complexes. Some of these are: metal-peroxo systems, polyoxometallates (POM), metal oxide
clusters, especially metal Volfram (or Tungsten, W), and heteroanions. Heterogeneous
catalysis for oxidations with zeolitic materials is some other techniques used in recent
years.
b) Catalytic selectivity in synthesis to reduce solvents
Catalytic selectivity can be another research effort for the reduction in the use of
solvents and with higher yields and lower amounts of waste. Many industrial processes are
based in new catalysts, such as inorganic polyacids and heteropolyacids which act as green
catalysts in oxidations, in the hydration of butane mixtures and in the polymerization of
tetrahydrofuran (THF). The heterogeneous catalytic method showed cleaner products,
minimum waste and easy separation of the products. Various porous materials with small
pore diameter can be used as catalytic surfaces for the regulation of the dissipating
reactants (mesoporous solid acids). Selectivity and higher yields are achieved in this type of
reactions.
Polymer chemistry and production of plastics have achieved recently green
credentials with new methodologies. Renewable starting materials, higher yields with
biocatalytic methods, minimum use of solvents and less waste are some of the
achievements in the production of well known commercial polymers.
MODULE-3
PROCESS INTENSIFICATION
INTRODUCTION
Fig. 2.1 Role of process intensification within sustainable process design
The objective of process synthesis is the selection of the best (optimal) process flowsheet
from among numerous alternatives for converting specified raw materials into specific desired
products, subject to predefined performance criteria. Sustainable design is defined as the design of
process flowsheets that correspond to lower values of a set of targeted performance criteria based
on economical, operational, and environmental factors. As shown in Fig. 2.1, the sustainable design
is obtained through improvements with reference to the early stage design (also called reference
design or base-case design). The role of process synthesis in finding the early stage design and/or
the more sustainable design is to generate the feasible process alternatives. The generation of
alternatives can be done in various ways, for example, trial and error, rule-based heuristics,
process integration (mass and energy), process optimization, process intensification, and many
more. In this chapter, process intensification, which also includes process integration, is presented.
Through the improvements as shown in the middle layer of Fig. 2.1, the following improvements
related to the physical system can be obtained through process intensification:
• Catalysts—the screening and selection of novel catalysts for reactive systems

• Solvents—the generation, screening, and selection of environmentally friendly solvents
for separation processes
• Materials—the design of new materials for the design of novel, innovative unit
operations that combine reaction, separation, or reaction–separation systems
• Energy—the use of process integration concepts to generate more sustainable process
alternatives with respect to reduced waste and environmental impact
Process intensification has been receiving increased attention and importance because of
its potential to obtain innovative and more sustainable process design alternatives. But what is
process intensification? Many definitions have been proposed for process intensification and a few
are highlighted here.
o Stankiewicz and Moulijn defined process intensification as the development of novel and
sustainable equipment that compared to the existing state-of-the-art, produces dramatic
process improvements related to equipment sizes, waste production, and other factors.
o Reay et al. defined process intensification as process development that involves reduction
in equipment (unit operation) sizes that lead to improvements in reaction kinetics, better
energy efficiency, reduction in capital cost, and improvement in process safety.
o Ponce-Ortega et al. defined process intensification as an activity characterized by five
principles—reduced size of equipment, increased throughput of process, reduced
equipment holdup or inventory, reduced usage of utilities and raw materials, and, increase
efficiency of process equipment.
The above definitions provide insights into the different scales at which process intensification
can be employed.
With the exception of process integration, there are, however, not many published methods to
determine the intensified solutions for processes, even though successful intensified solutions
have been reported by many. Examples of process intensification methods have been proposed at
unit operation scale by Bessling et al. [7], at task scale by Agreda et al. and at
phenomena/molecular scale by Freund and Sundmacher [9]. These methods however, mainly
focus on the design of new/novel unit operations that enhances/integrates a particular set of tasks
and/or phenomena within the process, but does not consider the interaction of the rest of the unit
operations that constitute the final (total) process design. They are also specific to the
characteristic of the unit operations studied.
Fig. 2.2 Multiscale method for process intensification

With a systematic and generic method for find process intensification solutions, Lutze et al.
[10] recently proposed a definition for process intensification that covers all three scales and
consider the overall process. According to Lutze et al. [10], process intensification is defined as the
targeted improvement of a process at the unit operations scale, the task scale, and/or the
phenomena scale. With overall improvement as the objective, at the unit operations scale the
individual equipment that constitute the final process design of any chemical or biochemical
process is identified and/or designed; at the task scale, the functions (tasks) performed by each
unit operation are identified and analyzed; and, at the phenomena scale, the phenomena that
satisfies the tasks to be performed are identified and analyzed. In this way, links between the
scales are established and allows the search in various scales to find the design of new, innovative,
and sustainable processes. This method can be applied to the design of new processes as well as,
the retrofitting of existing processes, in order to make them more sustainable. This concept of
scales is illustrated through Fig. 2.2 where at the lower scales, a small set of tasks and phenomena
are employed to represent various process flowsheet alternatives. Moving from the higher to the
lower scale increases the possibility for process innovation because of the following reasons:
 New alternatives that match the functions of unit operations can be generated through the
combination of tasks, leading to new flowsheet alternatives.
 New ways to perform tasks can be generated by combining different phenomena, leading to
the generation of novel and (more sustainable) flowsheet alternatives.
Therefore, if processes are designed at scales lower than the unit operation scale,there is an
increased chance of finding a more sustainable overall process design. This is highlighted by the
process intensification solutions reported by Agreda et al. [8] and Siirola [11] for the production of
methyl-acetate from the reaction of methanol and acetic acid. Papalexandri and Pistikopoulos [12]
proposed the idea of combination of phenomena to generate new unit operations. Peschel et al.
[13], Lutze et al. [10, 14] and Babi et al. [2] illustrate the use of phenomena-based approaches to
achieve process intensification.
Process integration can be considered as a special case of process intensification and is
commonly defined as the design and analysis of the best (optimal) network for mass and energy
utilization applied to the design (or retrofitting) and operation of new as well as existing processes
[15]. Consequently, process integration is concerned with two integration concepts within a
chemical (and biochemical) process—mass and/or energy integration [16, 17]. Mass integration is
the efficient utilization of mass within the process (for example, minimization of fresh water use in
a process) through the analysis and optimization of mass flows within the process. Analogously,
energy integration is the efficient utilization of energy within the process (for example heat
integration) through the analysis and optimization of energy needs within the process. As the use
of water and energy are related to the performance criteria for more sustainable designs and are
achieved through the integration of two or more operations, they are therefore also regarded as
special cases of process intensification. Methods for performing process integration focus on the
selection and combination of existing as well as novel process technologies in the best (optimal)
manner for the efficient use and utilization of mass and/or energy. Therefore, in this chapter,
unless otherwise indicated, PI includes process intensification as well as process integration.
The objective of this chapter is to present and discuss the fundamentals of process
intensification. First, the concept of PI is introduced, followed by a discussion on when and how to
employ PI? This includes a discussion on the role of process intensification in sustainable process
design as well as the connection between process integration and process intensification. Also,
examples of successful application of process intensification are given. Next, the methods and tools
needed to determine process intensification solutions are presented in terms of a general
mathematical problem formulation, a brief overview of the different solution techniques, the need
for a systematic computer-aided framework, and the associated methods and tools. The
application of this framework is highlighted through a case study involving the production of
methyl-acetate by reaction of methanol with acetic acid. The chapter ends with a discussion of
perspectives, conclusions, and future work on the role of process intensification in relation to the
design of more sustainable and innovative processes as well as pointing out some of the recent
achievements. Note that even though process integration is regarded as aspecial case of process
intensification, it is only briefly covered in this chapter. Also, recent developments on process
integration can be found in the review of the state-of-the-art by Klemes et al. [18].
Process Intensification (PI) targets dramatic improvements in manufacturing and processing

by rethinking existing operation schemes into ones that are both more precise and efficient than
existing operations. PI frequently involves combining separate unit operations such as reaction
and separation into a single piece of equipment resulting in a more efficient, cleaner, and
economical manufacturing process. At the molecular level, PI technologies significantly enhance
mixing, which improves mass and heat transfer, reaction kinetics, yields, and specificity. These
improvements translate into reductions in equipment numbers, facility footprint, and process
complexity, and, thereby, minimize cost and risk in chemical manufacturing facilities.
At the core of PI is the optimization of process performance by focusing on molecular level
kinetics, 26 thermodynamics, and heat and mass transfer. Gerven and Stankiewicz (2009) provide
four guiding principles for PI1:
 Maximize effectiveness of intramolecular and intermolecular events (example: dynamically
changing conditions to attain kinetic regimes with higher conversion and selectivity)
 Provide all molecules the same process experience (example: plug flow reactor with
uniform, gradient-less heating)
 Optimize driving forces at all scales and maximize the specific surface areas to which they
apply (example: increase transfer surface area through microchannel designs)
 Maximize synergistic effects from partial processes (example: affecting reaction equilibrium
by removing products where and when they are formed)
PI designs that achieve all or some of these molecular-level optimal conditions are likely to be
transformative. Reactors that enable precise control of the reactor environment could dramatically
increase yields, conversions, and selectivity, which in turn would reduce material, energy, and
carbon intensities, minimize purification needs, and reduce waste disposal burdens. Additionally,
PI technologies could enable the manufacture of products that otherwise could not be safely or
successfully made.
WHEN AND HOW TO APPLY PI?
In the chemical and biochemical process industry, improvements in economic as well as

environmental factors are required for new as well as existing processes [3, 19]. PI plays a major
role in achieving the desired improvements in processing options through the design of processes
that constitute more sustainable alternatives, that is, hybrid/intensified unit operations
(equipment). A hybrid/intensified unit operation, is an operation that enhances the function of one
or more unit operations for performing a task or a set of tasks through a new design of the unit
operation or the combination of more than one unit operations. For example, reactive distillation is
a combination of reaction and separation (see Fig. 2.3a) and a membrane reactor is a combination
of reaction and in situ removal of a reactant or product (see Fig. 2.3b).
Process Integration can be applied in the following forms for achieving process
improvement:
• Heat integration (heat exchanger networks) where energy efficiency is increased
through energy consumption minimization. This was the first type of process
integration, first developed by Linnhoff et al. [20] and further extended and solved using
a mixed integer non-linear programming (MINLP) approach by Papoulias and
Grossmann [21].
• Mass integration (mass exchanger networks) where the flow route of mass within the
process is optimized, for example, through the use of concentration differences [16, 18].
• Supply-chain management where the total supply-chain cost (related to suppliers,
storage, retailers, customers etc.), is minimized based on the concepts applied for heat
and mass integration [18, 22].
Examples of hybrid/intensified unit operations: (a) reactive distillation (b) membrane reactor
The impact of process integration on cost reduction and environmental factors have been reported
by numerous authors, see for example, Papoulias and Grossmann [21], Singhvi et al. [22] and
Kazantzi and El-Halwagi [23] for overall capital cost and/or operating cost reduction through
increased process integration. As the cost reduction due to more efficient use of energy and water
resources is achieved, it also reduces the waste and has a positive impact on the environment,
making the process thereby more sustainable. Babi et al. [24] proposed a 3-stage sustainable
process synthesis–design method (see Fig. 2.4) including the use of PI. According to this method, in
the first stage, the optimal processing paths are synthesized to convert a set of raw materials into a
desired set of products. In the second, the optimal processing path (flowsheet) is selected for
further study that includes identification of the process bottlenecks or hot-spots. These hot-spots
help to define targets for improvement, which when matched would lead to more sustainable and
innovative solutions. In the thirdstage, methods with or without considering PI are applied to
generate process alternatives that match the desired targets for process improvements. Here,
applications of different PI methods are possible.
Fig. 2.4 Three-stage sustainable process design method that incorporates PI

From Fig. 2.4, it can be noted that for existing processes with already identified hot-spots,
entry to the 3-stage method is at stage 3. Alternatively, if the process exists but the hot-spots have
not been identified, then the entry to the 3-stage method is at stage 2, while for a totally new
process synthesis problem, the entry is at stage 1. Therefore, opportunities to apply PI exist
whenever deficiencies (bottlenecks or hot-spots) in design and/or operation of a process are
identified. A classic example is the flowsheet (see Fig. 2.5) for the production of methyl-acetate by
reaction of methanol with acetic acid. Can the number of unit operations be decreased? Can the
product yield and purity be increased? Can the process be made more sustainable? As Fig. 2.3b
indicate, the answer is yes. Another classic example in the case of heat integration is the
combination of a heat exchanger that needs to reduce the temperature of a stream with another
that needs to increase the temperature of a stream. Integration in this case saves energy as well as
cooling medium and thereby makes the process after integration more sustainable.
As the definition of PI implies, to apply PI, a combination of operations, tasks, and/or
phenomena need to occur simultaneously subject to the specified objectives and constraints of the
process. That is, which combination of operations, tasks, and/or phenomena would lead to an
alternative that is better than the base-case design according to a set of performance criteria and
subject to the principal requirements of PI? Siirola [11] proposed a combination of tasks that lead
to the well known intensified solution of a reactive distillation column for the production of
methyl-acetate (see Fig. 2.5). Babi et al. [24] proposed a phenomena-based approach where
combinations of a set of phenomena lead to a set of tasks, whose combinations lead to a set of new
or existing unit operations that when combined give a final set of PI solutions.
Babi et al. [24] also illustrated their method to the methyl-acetate production and reported
same reactive distillation solution as well as other feasible PI solution Through the use of
intensification design concepts, novel hybrid/intensified unit operations (see Table 2.1) that
exploit mechanisms (phenomena) related to, for example, heat and mass transfer are determined.
Heat-transfer mechanisms are enhanced through the use of passive and active techniques, for
example, rough surfaces (passive) and electrostatic fields (active). Mass transfer mechanisms are
enhanced through the use and enhancement of three external physical characteristics, rotation (for
example, use of a rotor), vibration (for example, high frequency ultrasound), and mixing (for
example, inline mixers) [5]. In a reactive distillation, on the other hand, the phenomena of reaction
and separation (for example, vapor liquid equilibrium) take place simultaneously on every stage or
transfer unit.
Fig. 2.5 When to apply PI—process flowsheet for the production of methyl-acetate
Table 2.1 List of reported hybrid/intensified unit operations
Another similar example is a membrane reactor, which provides the opportunity for in situ
product/by-product removal thereby simplifying the downstream processing steps [29, 34]. Table
2.1 lists various hybrid/intensified unit operations and their reported area of application.
The synthesis of heat exchanger networks using a pinch-based temperature interval method was
first introduced by Linhoff and Flower [35] for energy (heat) integration. The method utilizes
concepts based on thermodynamic and physical insights. The minimum utility requirements
(heating and cooling) are identified first, followed by the design and analysis of an (heat)
exchanger network. However, this method does not guarantee the best (optimal) solution to the
energy integration problem, that is, the use of the minimum number of heat exchangers for the
design of the integrated heat exchanger network. Therefore, the synthesis of heat exchanger
networks was further developed using mathematical programming, see for example, Papoulias and
Grossmann [21]. Here, the heat integration problem is defined as a MINLP problem that can be
reduced to a mixed integer linear programming (MILP) problem for design and analysis of the
optimal integrated heat exchanger network.
Similar concepts as proposed by Linhoff and Flower [35] have been extended to the design
and analysis of mass exchanger networks; see for example, El-Halwagi and Manousiouthakis [36].
The minimum mass requirements, that is, the amount (mass) of a targeted species p that can be
transferred into a lean process stream (above the mass pinch point) and the minimum amount
(mass) of an external mass separating agent required for removal of the targeted species p (below
the mass pinch point) are first identified followed by the design of the best (optimal) mass
exchanger network.
Fig. 2.6 The utilization of process integration in process intensification. Examples of process
intensification that employ mass and energy integration are shown. MEN mass exchanger network, HEN heat
exchanger networks, REAMEN reactive mass exchanger network
Process intensification also utilizes the concepts from process integration in order to design
hybrid/intensified unit operations that integrate mass and/or energy within a single-unit
operation and/or reduce the number of unit operations, compared to a conventional process. This
is shown in Fig. 2.6. As an example, consider a divided-wall column (single-unit operation) that
integrates the separation of a ternary zeotropic mixture (mass) having a lower utility consumption
(energy) compared to the conventional approach that uses a two-column sequence [24].
At whichever scale, process intensification is performed, the output is expected to be a
better, more sustainable process compared to a selected reference (basecase) design. Stankiewicz
and Moulijn [37] proposed that process intensification can be decomposed into two main
classifications [9], intensified unit operations (hybrid/intensified equipment) and intensified
methods. This is shown in Fig. 2.7. In each classification different subclassifications can be made
with respect to intensified unit operations and available methods.
Fig. 2.7 Classification of PI operations

Since according to Fig. 2.7, multiple intensified unit operations exist, therefore, there is a
need for the development of intensified methods that incorporate within their search space these
unit operations for the design of (sustainable) chemical and biochemical processes. However, to go
beyond the current search of these hybrid/ intensified unit operations and to find truly predictive
methods that also provide the opportunity to generate and design novel, innovative unit
operations, these methods must operate at lower scales, for example, the phenomena/molecular
scale [10, 38]. Table 2.2 provides examples of process intensification at the unit operations scale,
task scale, and phenomena scale.
Table 2.2 List of PI solutions at different scales: unit operations, tasks, and phenomena
Figure 1 Taxonomy of PI technologies
Figure 1 displays a taxonomy of PI technologies as formulated by Stankiewicz and Moulijn

(2000)2. PI equipment is characterized by designs that optimize mass, heat, and momentum
transfer (e.g., microreactors, spinning disk reactors, static mixers, monolithic catalysts). PI
methods involve integration of multiple processing steps (e.g., reactive distillation, membrane
reactors, hybrid separations, multicomponent distillation, fuel cells) and application of alternative
energy sources (e.g., microwaves, magnetic forces, ultrasound, centrifugal fields).
BIOMASS AND BIOFUELS. HOW GREEN ARE THEY?

Green Chemistry gave in the last decades numerous examples of research efforts for biofuels
and their applications in viable energy production. Biofuels can be one form of renewable energy
resources and in many cases can replace fossil fuels, since they can be come from biomass and are
considered to be less polluting and they can reduce global warming by absorbing CO2 during the
growing of plants. In the last decade because of the increasing oil prices and energy crisis in the
Middle East, biofuels are gaining increased public and scientific attention. There is a need for
increased energy security, renewable energy sources and minimize greenhouse gas emissions.
In the first few years of biofuel production there were some excesses and the use of useful
stable plants (sugar, wheat and corn) resulted in the sudden increase of food prices worldwide.
Inevitably, there were various social, economic, environmental and technical issues with biofuel
production and use. The most important was: the effect of moderating oil prices, the "food vs fuel"
debate. The other most important issue was the ―sustainable‖ biofuel production, deforestation and
soil erosion, loss of biodiversity and impact on water resources because of vast areas were
cultivated for producing biofuels.
The issue of biofuels and their status as ―green‖ fuels was the subject of an international
study ―Towards Sustainable Production and Use of Resources. Assessment of Biofuels” (UNEP.
International Resource Panel, United Nations Environment Programme, New York, 2009). The
study emphasized the many positives impacts on climate, energy security and biodiversity, but also
some negatives, such as environmental and social effects. The first generation of biofuels was
replaced very soon by the second generation which use more of non-food plants and animal fat
waste. Second generation biofuels are biofuels produced from sustainable feedstock. Many second
generation biofuels are under development such as cellulosic ethanol, algae fuel, biohydrogen,
biomethanol, DMF, BioDME, Fischer-Tropsch diesel, biohydrogen diesel, mixed alcohols and wood
diesel.
In 2010 worldwide biofuel production reached 105 billion liters (L), up 17% from 2009, and
biofuels provided 2.7% of the world's fuels for road transport, a contribution largely made up of
ethanol and biodiesel.
The international and European strategy for the increased production of biofuels was
dictated firstly from the effort to reduce the CO2 emissions and secondly for energy security
purposes and reduction of the monopoly of petroleum as basic energy source. Based on the
broader European energy strategy, the EU through the Directive 2003/30/EC supported the
biofuels with the intension to increase by 2010 their use to 5.7% in the transport sector. The main
biofuels replacing petroleum products were bioethanol and biodiesel.
In Greece, there is substantial progress in the production and use of biofuels fo transport.
Statistical data in 2008 showed that consumption in Greece reached 2.750.000 million tons (MT)
for diesel and 4.031.000 MT gasoline. In the same period there were 17 companies producing
diesel (13 are Greek producers and 4 are importing biodiesel from Europe). For the production of
biodiesel in Greece the raw material are oilseeds (sunflower, soya, cotton, rapeseed), vegetable oils
(corn, sugar beets, small grain cereals). The Biofuels Directive 2003/30/EC has been adopted by
the Greek government as Law3423/05].
TYPES OF BIOFUELS AND “GREEN” PROSPECTS FOR RENEWABLE FUELS

Biofuels are liquids and gas fuels which are produced from different types of biomass. The
term biomass according to scientists is every biological material from living organisms. Biomass
can be used as an energy source directly (combustion) or be converted in to another biofuel.
Examples of biomass can be forest residues (branches, tree stumps), wood chips, municipal solid
waste, agricultural waste (cereal straw, hay) and other cellulogic material. Also, plant and animal
matter that can be converted into fibers or other industrial chemicals by fermentation or
distillation (biodiesel, bioethanol). Biomass can be grown from various plants and trees (cereal
straw, switchgrass, hemp, corn, poplar, willow, palm trees, sugarcane etc).
The most important commercial types of biofuels are:18
a) Bioethanol. (CH3CH2OH).. Ethanol is produced by fermentation. This ethanol is mostly
from carbohydrates, such as sugar or starch crops (corn or sugarcane). Cellulosic biomass,
derived from non-food sources such as trees and grasses, also being developed as a feedstock
for ethanol production. Ethanol can be used as a fuel for vehicles in its pure form, but it is usually
used as a gasoline additive to increase octane and improve vehicle emissions. Bioethanol is widely
used in the USA and in Brazil.
b) Biodiesel. This is diesel fuel of biological origin and not from the usual petroleum
refining. .Biodiesel is made from vegetable oils and animal fats and can be used as a fuel for
vehicles in its pure form, but it is usually used as a diesel additive to reduce levels of
particulates, carbon monoxide, and hydrocarbons from diesel-powered vehicles. Biodiesel
is produced from oils or fats using transesterification and is the most common biofuel in
Europe
c) Biogas. This gas is mainly Methane (CH4) that is produced from biomass or as a
biodegradation of organic matter, such as industrial and municipal waste in the absence of
oxygen. The biogas can be cleaned sufficiently to become a good quality natural gas (~98%
methane).. Biogas is produced by the anaerobic digestion or fermentation of biodegradable
materials.
d) Biomethanol (CH3OH). Is pure Methanol that is produced from various types of
biomass by fermentation or special chemical process and can be used as a biofuel.
Biomethanol is the simplest (and cheapest) of the alcohols. It is a versatile chemical that can
produce a range of polymers and fuels. Its most immediate fuel use is to produce bio-
methyl tertiary butyl ether (MTBE) to increase octane levels in petrol to prevent 'knocking'.
e) Biodimethylether . Dimethylether (CH3-O-CH3) is another type of biofuel that can be
produced from biomass.
f) Synthetic biofuels (or synfuel). These fuels: are hydrocarbons or mixtures of synthetic
hydrocarbons that can be produced from biomass. Common use of the term "synthetic fuel"
is to describe fuels manufactured via Fischer- Tropsch conversion, methanol to gasoline
conversion, or direct coal liquefaction. In 2009 on global scale the production of synthetic
fuels were over 240.000 barrels per day.
g) Biohydrogen This biofuel is hydrogen gas that is produced from biomass or by
biodegradable fraction of industrial and municipal solid waste.
h) Clean Vegetable Oils. Vegetable oils that are produced from plants by extraction of
crashed and pressurized vegetables or extracted from plants by dissolving parts of plants in
water or another solvent. The mixture may also be separated by distilling the oil away from
the plant material. These vegetables can be converted into biofuels.
i) Bio−ΕΤΒΕ:Ethyl tert-butyl ether, ΕΤΒΕ) can be produced from bioethanol and can be
used as biofuel.
λ) Βιο−ΜΤΒΕ: [C5H12O, (CH3)3-C-O-CH3)] that is produced from biomethanol..
Figure 9.4. Biofuels can become important renewable sources of energy. Already, 9% of
the fuels used in transport worldwide are from renewable biofuels (2005). Green
Chemistry played an important part for the technological developments of biofuel
production and the use of renewable raw materials.
The future of biomass as a renewable source of energy is very important in combination

with other renewable sources (solar, wind, geothermal and wave energy). The planet Earth has
vast amounts of biological material that are formed daily through the photosynthetic action of
plants. This natural biomass can increase substantially with commercial plants cultivated in areas
but with no interference with food crops and crucial dietary materials. Also, biomass can be
produced from plant and animal natural waste and industrial and municipal solid waste. There are
many types of biological and agricultural waste which can be converted by biochemical processes
(enzymes and micro-organisms anaerobic ingestion, fermentation and composting) into gas or
liquid biofuels Other chemical processes for converting waste and vegetable oils into biodiesel is
transesterification or breaking down carbohydrates and simple sugars to make alcohols (ethanol,
methanol). Research scientists are Scientists are still researching the effects of converting biomass.
ADVANTAGES AND DISADVANTAGES OF BIOMASS AND VARIOUS BIOFUELS
Petroleum and its products from the 1960s were fundamental raw materials for many
industrial products and fuel for transport at a global scale. The 1973 oil crisis caused a big blow to
energy supplies and a major crisis. It started in October (and lasted until March 1974) when
members of the OAPEC (Organization of Arab Petroleum Exporting Countries, consisting of OPEC
plus Egypt, Syria and Tunisia) proclaiming an oil embargo and causing high oil prices. The
proclamation disrupted supply and caused strong recession in many developed countries. This
embargo was in response to the U.S. decision to re-supply the army of Israel during the Yom
Kippur was with other Arab countries.
This oil crisis started a big discussion among scientists and economic analysts on the fate of
future supplies of energy and forced many countries to look for alternatives. Biomass and the
derived biofuels were available sources for alternative energy supplies that for a long period were
neglected because petroleum was very cheap and easily available to be use as fuel and starting
material for the chemical industry. Biofuels had another important advantage in the decrease of
gases of greenhouse effect (especially CO2).
The main advantages of biofuels are:

i) Cost: Once the technology is widely available, biofuels can be significantly less
expensive than gasoline and other fossil fuels, particularly as worldwide demand for oil
increases. Energy security keeps cost of fuels very low.
ii) Source Material: Petroleum oil is a limited resource (depleting in the long term) that
comes from specific materials, biofuels can be manufactured from a wide range of
materials including crop waste, manure, and other byproducts, making it a efficient step
in recycling.
iii) Renewability: Fossil fuels are depleting and at some stage will be very few sources left.
In contrast, biofuels are much more easily renewable as new crops are grown and waste
materials are collected every year.
iv) Energy Security: Dependency on foreign fuel sources is a very insecure prospect.
Industrial developed countries can protect the integrity of their energy resources and
make them safe from outside influences.
v) Economic factors, employment: Biofuels that are produced locally, and biofuel
manufacturing plants can employ hundreds or thousands of workers, creating new jobs
in rural areas. Biofuel production will also increase the demand for suitable biofuel
crops, providing economic stimulation to the agriculture industry.
vi) Environment. Biomaterials and biodegradability: Biofuels are easily biodegradable
and far safer to handle than traditional fuels, making spills less hazardous and much
easier and less expensive to clean up. Environmental protection is more important.
vii) Lower Carbon Emissions: Burning biofuels produce significantly less carbon dioxide
(CO2) output and fewer pollutants making them a safer alternative to preserve
atmospheric quality and lower air pollution. Growing plants absorb CO2.
Despite the many positive characteristics of biofuels, there are also many disadvantages to these
energy sources.
i) Energy Output: Biofuels have a lower energy output than traditional petroleum fuels,
requiring greater quantities to be consumed in order to produce the same energy level.
ii) Carbon Emissions: Several studies analyzed the carbon footprint of biofuels, and while
they may be cleaner to burn, there are strong indications that the process to produce the
fuel (machinery necessary to cultivate the crops and the plants to produce the fuel)
produces a large amount of carbon emissions.
iii) .High Production Cost of Biofuel: To refine biofuels to more efficient energy outputs
and to build the necessary manufacturing plants to increase biofuel quantities will
require a high initial investment.
iv) High Food Prices: Some important food crops, such as corn and soybeans are grown for
biofuel production. This will affect future prices of staple food crops.
v) Crops Need Water: Massive quantities of water are required for proper irrigation of
biofuel crops as well as for the manufacture of the fuel, which could strain local and
regional water resources.
vi) Availability: Biofuels are not widely available for consumer purchase and most vehicles
are not equipped to run on biofuel products. Limited availability reduces the desirability
of biofuels as alternative energy sources.
vii) Biofuel Smell: Production of various biofuels produces heavy smells depending on the
type of materials used, and those smells are generally undesirable near large
communities..
If we balance advantages and disadvantages of biofuels there are more advantages for the
future of biofuels. Biofuels are a reliable alternative energy resource but more development and
research (Green Chemistry will play an important role in the future) is necessary to overcome the
disadvantages of biofuels and make them suitable for widespread consumer use. Transport
technology is already available for biofuels, but it needs more innovations and better strategies to
increase consumer demands.
In the first phase of the biodiesel production and other biofuels the increasing subsidies in
various countries caused a diversion of some staple crops towards biofuel production and
inevitable food prices increased. Particularly in some Asia countries food prices peaked causing
problems in some areas and social problems. Also, in some countries, vast areas of farmland were
planted with energy plants than staple crops causing increased food prices.
Green Chemistry and Green Engineering are striving to promote the alternative biofuels.
Despite the disadvantages Green Chemistry is promoting the 3rd and 4th generation biofuels with
decreases in cost, better energy efficiency and chemical processes that will transform biomass into
biofuels.
There are mixed experiences in the last decade with biofuel use in industrial countries. The
advantages were very obvious considering the energy security and the environmental problems.
The disadvantages are also numerous and can be reduced with more technical innovations. Many
scientists believe that there is scope for many improvements in the quality and the properties of
biofuels. Environmental advantages can be multiplied substantially if industrial, agricultural and
municipal waste will be converted in large amounts in biofuels.
GREEN CHEMISTRY AND ENERGY CONVERSION OF BIOMASS

Biomass was used for a long period of time by human civilization as a source of energy.
Biomass burning and other low technology conversions were very low efficiency methods. In
recent years the biofuel sector that is attracting many research projects and a great variety of
innovative applications is transport and engines of internal combustion. The main question facing
biofuels is not whether they can work, but how they might be developed further. There are many
unresolved issues to proceed to large scale developments. OECD and its sister organization
International Energy Agency (IEA) have defined several areas requiring extended research. All the
indications are that biofuels represent a serious alternative to conventional fuels, although for the
time being can complement the existing transport fuels. The production potential, cost and the
environmental impacts of producing ethanol, biodiesel and other liquid and gaseous fuels are still
uncertain.
The research strategy used until now in developed countries combines the principles of
Green Chemistry and Green Engineering for the conversion of various biomass materials into
hydrocarbons with higher efficiency. The main goals in the chemical processes are to decrease the
content in oxygen of the raw materials in order to achieve high density of energy, and to achieve
formation of C—C bonds among the biomass and the intermediate products in order to increase
the molecular weight of the final hydrocarbons.
Bioethanol and biodiesel are the two most important biofuels which are produced until now
from starchy products and triglycerides raw materials (vegetable and animal lipids). These starting
materials are connected with stable food (corn, sorghum, sugarcane, wheat, barley, straw). This is a
great disadvantage because food prices increase substantially any time there are major disasters,
floods or droughts and food production drops to low levels.
Scientists are trying to improve in the last decade the conversion efficiency of lignocellulogic
starting materials into biofuels. Green Chemistry TECHNIQUES AND INNovations improved
substantially the conversion with thermochemical processes (Vapourization, pyrolysis and
liquefaction)of biomass. Researcher believe that many new advances in the conversion of biomass
to Biofuels can be achieved with the use of catalytic methodologies and preliminary processes such
as hydrolysis of aqueous solutions of carbohydrates. Another great improvement in the process can
be achieved with adol condensation of ketones and oligomerization of alkenes to produce high
quality bio-gasoline and biodiesel.
Green Chemistry can play a vital role in the transformation of biomass through various
chemical processes into useful and effective biofuels which will be at the same time
environmentally benign. Also, Green Chemistry can be in the forefront of scientific research and
applications for new biomaterials from biomass. The practical experience of technological
development of the last 100 years was based on the petrochemical industry (crude oil, natural gas).
The majority of starting chemical materials for synthetic routes is products petroleum refining. The
most important petrochemical classes, produced by fluid catalytic cracking of petroleum fractions,
were olefins (ethylene and propylene). Also, chemical plants produce olefins (ethane, propane) by
steam cracking of natural gas. Aromatics (benzene, toluene and xylene) are produced by catalytic
reforming of naphtha. Olefins and aromatics are the building-blocks for a wide range of materials
such as solvents, detergents, and adhesives. Olefins are the basis for polymers and oligomers used
in plastics, resins, fibers, elastomers, lubricants, etc..
Figure 9.6. Green Chemistry and Biorefineries. A schematic diagram of Biomass in a network of production
of fuels, chemicals, materials, sugars and valuable secondary molecules by Green Chemistry principles and
benign chemical processes. (extraction, fermentation, pyrolysis, etc).
Green Chemistry aims to replace the petrochemical industry with biorefineries. Green
scientists envisaged various raw biomass materials and industrial or municipal solid waste playing
a fundamental role. Biomass platform molecules to give fuels and chemicals. Biomass producing
valuable secondary materials, sugars (by fermentation), mixed organics and others in a unified
network biotransformations.
The scientific literature in the last decade is full of new research, innovative ideas and
environmentally friendly methods for applying the principles of Green Chemistry in biorefineries.
These new processes presented alternative biomass material. A typical example is bana grass
(Pennisetum purpureum), a very high tree-like grass and the oil from seeds of Jatropha curcas (non
edible plant which produces vegetable oil, the plant is planted in India and Indonesia). These two
plants from plantations can become raw materials for the production of biofuels. There are many
advantages in the use of these plants because can be planted in poor quality soil, absorb CO2, grow
very fast and are not edible.
There is extensive research for new types of biomass. Scientists are very careful about the
type of plants which are going to grow for biofuels. The use of corn, sugar cane, soy and cereals
(based on subsidies) for the production of biodiesel caused extensive increase of food prices. Also,
scientists are researching methodically the chemical processes needed for their transformation
(hydrogenation, condensation, gasification, extraction, etc) into biofuels. These processes have to
be environmentally friendly (less toxic solvents, minimum energy use, atom economy synthesis,
etc).
Figure 9.7. The plant Bana grass, which looks like sugar cane and is used for elephants’ food (India, Indonesis) is ideal
for biomass material. Jatropha curcas (family Euphorbiaceae), is a species of flowering plant native of American
tropics (Mexico). Produces flowers, its seeds are toxic and can reach a height of 6 m. It is poisonous semi-evergreen
shrub. The seeds contain~30% oil that can be processed to produce a high quality biodiesel
Scientists devote extensive research efforts for the 3rd and 4th generation of biofuels. They
are interested for the all types of waste (industrial, agricultural, animal waste, municipal, etc).They
consider that conversion of waste into biofuels will be a very desirable and has great prospects to
reduce the environmental burden of waste and at the same time increase their usefulness.
Biofuels are now a new and advancing technological and commercial enterprise which has
to be regulated. New rules and restrictions have to apply for quality, properties and prices. The
European Union recently 7 different certification schemes of biofuels (19/7/2011, MEMO 11/522).
The EU decided that biofuels must not use for their production trees of forests not plantations but
mainly plant debris and microalgae. The biofuels must produce at least 35% less CO2 compared to
conventional fuels and other gases that contriburte to global warming. In 2007 the EU countries
were importing 26% of biodisel and 31% of bioethanol from USA and Brazil.84
RENEWABLE RAW MATERIALS AND WHITE BIOTECHNOLOGY

Another important goal of green chemistry is the utilisation of renewable raw materials, i.e.
derived from biomass, rather than crude oil. Here again, the processes used for the conversion of
renewable feedstocks – mainly carbohydrates but also triglycerides and terpenes – should produce
minimal waste, i.e. they should preferably be catalytic. In the processes described in the preceding
section a biocatalyst – whole microbial cells or an isolated enzyme – is used to catalyse a
transformation (usually one step) of a particular substrate. When growing microbial cells are used
this is referred to as a precursor fermentation. Alternatively, one can employ denovo fermentation
to produce chemicals directly from biomass. This has become known as white biotechnology, as
opposed to red biotechnology (biopharmaceuticals) and green biotechnology (genetically modified
crops). White biotechnology is currently the focus of considerable attention and is perceived as the
keymto developing a sustainable chemical industry.
Metabolic pathway engineering is used to optimise the production of the required product
based on the amount of substrate (usually biomass-derived) consumed. A so-called biobased
economy is envisaged in which commodity chemicals (including biofuels), specialty chemicals such
as vitamins, flavorsand fragrances and industrial monomers will be produced in biorefineries. De
novo fermentation has long been the method of choice for the manufacture of many natural L-amino
acids, such as glutamic acid and lysine, and hydroxyl acids such as lactic and citric acids. More
recently, de novo fermentation is displacing existing multistep chemical syntheses, for example in
the manufacture of vitamin B2 (riboflavin) and vitamin C. Other recent successes of white
biotechnology include the biodegradable plastic, polylactate, produced by Cargill-Dow and 1,3-
propanediol, a raw material for the new polyester fibre, Sorona (poly-trimethylene terephthalate)
developed by DuPont/Genencor. The latter process has become a benchmark in metabolic pathway
engineering. Both of these processes employ corn-derived glucose as the feedstock.
Fig. 1.43 Synthesis of a bioemulsifier from renewable raw materials.

Finally, an elegant example of a product derived from renewable raw materials is the
bioemulsifier, marketed by Mitsubishi, which consists of a mixture of sucrose fatty acid esters. The
product is prepared from two renewable raw materials – sucrose and a fatty acid – and is
biodegradable. In the current process the reaction is catalysed by a mineral acid, which leads to a
rather complex mixture of mono- and di-esters. Hence, a more selective enzymatic esterification
(Fig. 1.43) would haveobvious benefits. Lipase-catalysed acylation is possible [126] but reaction
rates are very low. This is mainly owing to the fact that the reaction, for thermodynamic reasons,
cannot be performed in water. On the other hand, sucrose is sparingly soluble in most organic
solvents, thus necessitating a slurry process.
SUSTAINABILITY AND RENEWABLE ENERGY SOURCES IN THE 21ST CENTURY

In the last 20 years developed countries faced major challenges in their economic and social
development. The energy crises and rising oil prices forced critical thinking about the future. At the
same time climatic changes and global warming continue to get worse due to increasing emissions
of carbon dioxide (CO2) and other gases of the green house effect.
The Earth's total endowment of fossil oil, before humans started using it, was roughly 2
trillion barrels of recoverable oil. Rising consumption has used already 50% of oil deposits.
Consumption is currently at 31 billion barrels each year. And increasing because of China, India
and other developing countries. There is no other solution than renewable energy sources and
sustainable use of existing energy resources. Solar, wind, geothermal, and other environmentally
friendly sources must replace the conventional fossil fuels and reduce emissions.
The global fresh water crisis is another serious problem in many developing countries and
its sustainability threatens major areas of the planet. Green Chemistry and Green Engineering
aiming to tackle these two problems by improving alternative and renewable energy sources,
cutting emissions and use in a sustainable matter water resources.
RENEWABLE ENERGY SOURCES
The most renewable sources of energy on the planet are.
1) Wind power: it can be used for the production of electricity and in many countries it
can produce up to 5-10% of the electricity needs.
2) Solar energy: Solar panels were used initially for heating water in house roofs. The
improved technology of photovoltaic panels is considered the future of electricity
production in many countries. At the end of 2010, cumulative global photovoltaic (PV)
installations production has been increasing by an average of more than 20% each
year since 2002, making it a fast-growing energy technology. In 2010, cumulative
global photovoltaic (PV) installations surpassed 40 GW.. Many solar photovoltaic
power stations have been built, mainly in Europe
3) Hydroelectricity. There are many for decades large hydroelectric power dams. In the
last decade small hydro stations proved to be more beneficial to the environment and
use water power in a sustainable way.
4) Geothermal energy. It is produced in the interior of the Earth from physical
radioactive decay of minerals and can be brought to the surface easily for electricity
use and house heating.
5) Tidal energy. is a form of hydropower that converts the energy of tides into useful
forms of power, mainly electricity. Although not yet widely used, tidal power has
potential for substantial electricity generation. Tides are more predictable than wind
energy and solar power. Tidal power has traditionally suffered from relatively high
cost and limited availability of sites with sufficiently high tidal ranges or flow
velocities,
6) Wave energy. Waves are caused by the wind blowing over the surface of the ocean.
In many areas the wind blows with enough consistency and force to provide continuous
waves. There is tremendous energy in the ocean waves. Wave power devices extract energy
directly from the surface motion of ocean waves or from pressure fluctuations below the
surface. Wave-power rich areas include the western coasts of Scotland, northern Canada,
southern Africa, Australia, USA, etc.
7) Oceanic energy. Systems to harvest utility-scale electrical power from ocean waves
have recently been gaining momentum as a viable technology. The potential for this
technology is considered promising, especially on west-facing coasts.
8) Biomass. Not only for heating but also from plant, industrial and municipal waste.
Production of bioethanol, biodiesel and biogas.
Figure 10.1. Solar Thermal Power , PS20, Sanlúcar la Mayor,

Sevilla, 20MWp, Open Apr 2009.
In 2010 about 16% of global final energy consumption comes from renewable energy
sources. On a global scale, 10% of energy is coming from traditional biomass (heating), 3.5% from
hydroelectricity and another 3% from solar,wind, geothermal, small hydro and biofuels. The share
of renewable energy sources in electricity generation is around 19%. Wind power is growing at
the rate of 30% annually, with a worldwide installed capacity of 198 gigawatts (GW) in 2010. Great
Britain produced in 2011 almost 12% of its electricity by wind energy sources. These are major
improvements in the production of energy by renewable energy sources.
Figure 10.2. Wind power turbines and photovoltaic panels are the.fastest- growing energy technologies in the last
decade
A recent report of the United Nations (2011) on renewable energy sources found that at a
global scale the investment flowing climbed from $80 billion (2005) to a record $100 billion in
2006. The trend continues in 2007 with another extra investment of $85 billion. In 2010 the
investment on renewable energy increased by 32% and reached the level of $211 billion.
Investments in renewable energy sources are fast growing in developed and developing
countries and new more efficient methods appear on the horizon at a fast pace. China for example
invested in renewable energy in 2010 $49 billion (28% increase compared to 2008). The same
happened in the countries of Latin America, $13 billion in 2010 (39% increase compared to 2009).
In Middle East $5 billion in 2010 (increase 104% compared to 2009) and in India $3.6 billion
(increase 25%).
In Europe the latest trend for investment in renewable energy sources was growing very
fast. Although there was a decrease of 22% compared to the previous year in wind parks (wind
turbine installations) the investment was $35 billion. Photovoltaic parks were the most fast
growing sector for investment. In Germany $34 billion (increase 132$ compared to 2009), Italy
$5.5 billion (59%), France $2.7 billion (increase 150%), etc. 5 Renewable energy sources now
compete head-on with coal and gas in terms of new installed generating capacity and the % of
world energy produced from renewable sources is sure to rise substantially as the tens of billions
of new investment dollars bear fruit.
In the USA there is increasing investment trends for renewable energy sources but not to
the same extend as in Europe. In 2009 renewable energy sources produced 8% of the total
electricity in the USA. Solar and wind power constitute now 10% of various renewable energy
producing sources.6
Figure 10.3. In 2009 the distribution of energy sources in U.S. Renewable energy sources cover 8% of the energy
produced. Renewable energy sources are: biomass 50%, hydroelectric 35%, wind power 9%, geothermal 5%, solar
(photovoltaic panels) ~1%.
Renewable energy sources in the countries of European Union (27 countries) in 2008
contributed to 10.3% of the total production of energy compared to 8.8% in 2006 and 9.7% in
2007. The EU in 2009 projected a new Directive on renewable energy sources and investments
aiming to increase their use at a level 20% by 2020. These goals were the results of studies and
statistical data of the conditions in various countries, the economic environment and investments
in the last decade.
RENEWABLE ENERGY SOURCES: ADVANTAGES AND DISADVANTAGES

Conventional fossil sources of energy were for decades very cheap and effective in the
production of electricity, in transport as fuels and for other uses. Renewable energy sources have
the main advantage that they are sustainable, at least in our lifetimes. Also, renewable sources do
not pollute the environment and can be extended without problems to the Earth ecosystems.
Renewable sources of energy will reduce global warming and keep the atmosphere clean. Non-
renewable resources such as fossil fuels are finite and their burning produces increasing amounts
of pollutants.
Advantages of Renewable Energy Resources
 Renewable energy sources are sustainable. Renewable energy sources are friendly to the
environment (zero emissions). They do not produce waste (solid or liquid). Green
Chemistry and Green Engineering aim to improve renewable methods of energy by
providing low cost materials, better technological improvements and “greener” processes in
their construction (such as and better materials and less toxic for photovoltaic panels).
 Renewable energy sources are not finite like fossil fuels.
 Renewable energy sources can help small countries for their energy security and provide
alternative sources liberating their economies for petroleum and fossil fuel dependence. At
the same time renewable energy offers economic independence from imports and materials
 Renewable energy sources offer flexible applications in the production of electricity for
the needs of small areas, away from urban areas. Also, renewable energy can be produced at
local level without need for transport of fuels in remote p-laces.
 Technological installations and equipment for renewable energy sources are very simple to
install and maintain and they have long life compared to conventional energy sources,
especially for electricity.
 Renewable energy sources are subsidised by state institutions and international energy
programmes because in the long term will offer energy security and provide local
population with employment and technical expertise. In this respect Green Chemistry and
Green Engineering can offer innovative ideas and methodologies.
Disadvantages of Renewable Energy Sources
Renewable energy sources have also many disadvantages compared to conventional energy
resources. Especially when compared to fossil fuels.
 In 2011, despite the rapid progress in the last decade, renewable energy sources cover only
10% of energy needs in most countries. High cost, technological problems and cheap fossil
fuels hampered their applications or postponed research and development. Renewable
sources need better networks and systematic management to become widespread.
 Renewable energy sources have very low efficiency (only 30%) compared to conventional
energy sources.
 Efficiency of energy production by solar, hydroelectric and wind power is restricted by
climate, seasons, temperature, lack of rain, cloudy atmosphere or lack of winds blowing in
the area. These limitations need to be overcome with better planning, networks and
connections to a larger energy system that uses also conventional means of energy
production at times of high demand.
 Wind turbines are expensive. Wind doesn't blow all the time, so they have to be part of a
larger plan. Wind turbines are causing problems with flying birds, they are noisy, and cause
esthetic problems in some mountain areas of natural beauty. Wind turbines need more
design and management in the areas of installation. Some offshore wind turbines have
become very effective in the production of electricity but are very expensive and have
maintenance problems. There is no 100% eco- environmentally “clean” technological
solution, even with renewable energy sources..
 River Dams are expensive to build and disrupt the environment. They have also caused
earthquakes. Smaller turbines are cheaper and easier to install
 Energy for sea waves -- different technologies are being tried around the world. They are
very expensive.
 Energy by tides -- barrages (dams) across river mouths are expensive to build and disrupt
shipping.
 Some hydroelectric dams cause the production of methane from the decomposition of
plants below the water. There is need for better “greener” technological solutions.
 Solar energy, photovoltaic panels. Some materials are still very toxic. Solar panels are
expensive. Not all climates are suitable for solar panels.
 biofuel -- Often uses crop lands and crops (like corn) to produce the bio- alcohol. This
means that more land has to be cleared to grow crops, or there is not enough food, or that
food becomes more expensive.
Figure 10.4. Renewable energy resources are sustainable sources and can be replace without harm to the
environment. Also, renewable energy sources are eco-friendly.

Green Technology Notes

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Green Technology Notes

Uploaded by

Copyright:

Available Formats

GREEN TECHNOLOGY 1

AN OVERVIEW OF GREEN TECHNOLOGIES

WHAT IS GREEN TECHNOLOGY?

Green Technology is the development and application of products, equipment and

d) It promotes the use of renewable resources.

BRIEF HISTORY OF GREEN TECHNOLOGY

Figure :1.1:- Electrobat

IMPORTANCE OF GREEN TECHNOLOGY

Green technology, an environmentally friendly technology is developed and used in a way

FOUR PILLARS OF GREEN TECHNOLOGY POLICY

• To reduce the rate of growth of energy consumption while enhancing economic

GOALS OF GREEN TECHNOLOGY

APPLICATIONS OF GREEN TECHNOLOGY IN OUR LIFE

ADVANTAGES OF GREEN TECHNOLOGY

1. Does not emit anything harmful into the air

1. High implementing costs.

THE TWELVE PRINCIPLES OF GREEN ENGINEERING

Table 1.1. The Twelve Principles of Green Engineering

Principle No. 6. Conserve Complexity

p r o d u c t s t he ― disturbance increases (entropy) , the products disintegrates and is transformed

Principle No. 5. Output-pulled versus input-pushed. More energy or material (“input-pushed”)

Principle No 8. Green Engineering can meet needs and minimize excess.

GREEN ENGINEERING APPLICATION

Various Definitions of Green Chemistry are

• Green chemistry (which is also known as sustainable chemistry) is the design of

CHEMISTRY AND GREEN CHEMISTRY

Environmental chemistry is the study of chemical processes occurring in the environment

Today and the Future

SANDESTIN DECLARATION: 9 PRINCIPLES OF GREEN ENGINEERING

BRIEF HISTORY OF GREEN CHEMISTRY

Dr. Paul Anastas Dr. John Warner

GLOBAL RECOGNITION OF GREEN CHEMISTRY

Professional Development in Higher Education in University of Delhi. Inspired by the

OBJECTIVES FOR GREEN CHEMISTRY: THE COSTS OF WASTE

Figure 1.7 The costs of waste.

Figure 1.8 Supply chain pressures

GREEN CHEMISTRY AND SUSTAINABLE DEVELOPMENT:

GREEN CHEMISTRY FROM THEORY TO PRACTICE

THE TWELVE PRINCIPLES OF GREEN CHEMISTRY

The Twelve Principles of GC can be analyzed fully in the following set

Catalytic synthesis of ibuprofen

– Reduces wood pulp needed

Boric-Acid Mediated Amidation

 Enzymatic transamination reaction

–Replaces mineral oil (low flash point)

BENEFITS OF GREEN CHEMISTRY

 Less use of landfills, especially hazardous waste landfills

Principle Green Engineering Green Chemistry

GREEN CHEMISTRY METRICS

- 100% Yield means that no product has been lost

ATOM ECONOMY or ATOM SELECTIVITY or ATOM UTILIZATION

How atom economy can benefit society

STEP-BY-STEP: HOW TO CALCULATE ATOM ECONOMY

Step 1. Write out the balanced equation.

Atom economy = × 100

Percentage yield = × 100

Calculate the atom economy for this reaction.

A low atom economy indicates that the reaction is inefficient

Q6. Consider the formation of ammonia via the Haber process.

REACTION MASS EFFICIENCY (RME)

The Curzons Definition

Industry sector Annual production (t) E-factor Waste produced (t)

Oil refining 106-108 <0.1 105-107

Bulk chemicals 104-106 <1–5 104-5×106