GREEN CHEMISTRY – UNIT (IV):

Green chemistry can be defined as the practice of chemical science and manufacturing in a manner that
is sustainable, safe, and non-polluting and that consumes minimum amounts of materials and energy
while producing little or no waste material. The practice of green chemistry begins with recognition that
the production, processing, use, and eventual disposal of chemical products may cause harm when
performed incorrectly. In accomplishing its objectives, green chemistry and green chemical engineering
may modify or totally redesign chemical products and processes with the objective of minimizing wastes
and the use or generation of particularly dangerous materials. Green chemistry is about increasing
profits and promoting innovation while protecting human health and the environment. Thus, the
practice of chemistry in a manner that maximizes its benefits while eliminating or at least greatly
reducing its adverse impacts has come to be known as green chemistry.

Green chemistry applies across the life cycle of a chemical product, including it’s:

Design,

Manufacture,

Use,

And

Ultimate disposal.

Basically, green chemistry harnesses a vast body of chemical knowledge and applies it to the production,
use, and ultimate disposal of chemicals in a way that minimizes consumption of materials, exposure of
living organisms, including humans, to toxic substances, and damage to the environment. And it does so
in a manner that is economically feasible and cost effective. In one sense, green chemistry is the most
efficient possible practice of chemistry and the least costly when all of the costs of the practice of
chemistry, including hazards and potential environmental damage are taken into account.

The idea of green chemistry was initially developed as a response to the Pollution Prevention Act of
1990, which declared that U.S national policy should eliminate pollution by improved design instead of
treatment and disposal.

Significance of Green Chemistry:

Small increases in environmental protection now require relatively large investments in money and
effort. Is there a better way? There is, indeed. The better way is through the practice of green chemistry.
What makes Green Chemistry Sustainable?

Green chemistry is sustainable chemistry. There are several important respects in which green chemistry
is sustainable:

• Economic: At a high level of sophistication green chemistry normally costs less in strictly economic
terms (to say nothing of environmental costs) than chemistry as it is normally practiced.

• Materials: By efficiently using materials, maximum recycling, and minimum use of virgin raw materials,
green chemistry is sustainable with respect to materials.

• Waste: By reducing it so far as possible or even totally eliminating their production, green chemistry is
sustainable with respect to wastes.

Difference b/w green chemistry and environmental chemistry:

Whereas environmental chemistry focuses on the effects of polluting chemicals on nature, green
chemistry focuses on technological approaches to preventing pollution and reducing consumption of
nonrenewable resources.

How green chemistry differs from cleaning up pollution

 Green chemistry reduces pollution at its source by minimizing or eliminating the hazards of
chemical feedstocks, reagents, solvents, and products.

 This is unlike cleaning up pollution (also called remediation), which involves treating waste
streams (end-of-the-pipe treatment) or cleanup of environmental spills and other releases.

 Remediation may include separating hazardous chemicals from other materials, then treating
them so they are no longer hazardous or concentrating them for safe disposal.

 Remediation removes hazardous materials from the environment; on the other hand, green
chemistry keeps the hazardous materials out of the environment in the first place.

12 principles of Green Chemistry:

Twelve principles of green chemistry have been developed by Paul Anastas and John Warner of EPA, and
in their Green Chemistry Theory and Practice book, 1998, they explained their meaning in practice.

1) Prevention:
The first principle of green chemistry is the principle of prevention, i.e. the prevention of waste
generation, which is more favorable for humans and the environment, and ultimately cheaper
than treating waste and destroying it after it has emerged.
 Any return of material goods to a circular stream of production - consumption represents a pure
economic gain but rather than devising a way in which the amount of waste produced in
production can be utilized in the best possible way, so it becomes useful, it is possible to prevent
the generation of waste. This approach to the problem has brought positive results: the paint
and varnish industry already produces solvent-free paints and lacquers. The detractors industry
has already thrown out all phosphorus-containing detergents. Asbestos is no longer used in
practice. Since nearly 80% of waste in the pharmaceutical industry is associated with solvents,
and that about 60% of their energy is consumed, the solution is to reduce the use of solvents. A
good example is the new "green" production process of sertraline (Figure1) by which the
introduction of ethanol as the sole solvent eliminates the need for the use, distillation and
recovery of four solvents (methylene chloride, tetrahydrofuran, toluene and hexanes) resulting
in a reduction in solvent consumption of 250 to 25 liters per kg of sertraline.

2. Maximize Atom Economy (Preventing Waste at the Atomic Scale):

The principle of increasing atomic usability was defined in 1991 by Barry Trost of Stanford University.
Synthetic methods should be designed to maximize the incorporation of all materials used in the process
into the final product. The principle of Atom Economy is logically linked to the principle of waste
prevention, since it requires all raw materials used in production to maximize utilization or inclusion in
the final product to ultimately reduce the amount of waste. This means that the chemical synthesis
should be designed in such a way that the final product maximizes the input of raw materials or designs
such synthetic products that will use the entire material used for synthesis in the final product.

Atom economy is defined as the ratio of relative molecular masses of the desired product and all
reactants expressed in percentages.
% of atomic efficiency = (Mr of the desired product/Mr of all reactants) x 100

For Example:

There is a known progress in the synthesis of ibuprofen. The main problem of old synthesis (boots
process) is low economic cost, because the utilization of input raw materials is only about 40%. In the
1990s a new "green" method of ibuprofen synthesis was developed, involving only three steps. The
Boots synthesis consists of six synthetic steps and yields 40%, while the Hoechst process of obtaining
ibuprofen consists of only three steps and yields a reaction of 77%, namely 99% if the fact that the acetic
acid is formed in the first the synthesis step is extracted and reused in production. That is why Hoechst is
a more economical and greener way to get ibuprofen.

E-factor:
The E-factor is used to compare the process of comparing the proportions of waste materials and the
desired product. The calculation of the E-factor is determined by the ratio of mass of waste (kg) per unit
of product in kilograms.

E-factor = kg of waste / kg of product

Sheldon points out that the use of E-factors varies greatly between the chemical industries and states
that the "good" E factor usually spends around 0.1, meaning that 10 kg of the desired product is only 1
kg of waste and by-products. The actual amount of waste also depends on the quantities of the product.
Even with a much lower E-factor, the oil industry produces higher amounts of waste than
pharmaceutical production where the E-factor is high but is significantly lower in production.

3. Design less Hazardous Chemical Synthesis:

Less Hazardous Chemical Synthesis advocates, wherever possible, the creation of synthetic methods for
the use and creation of substances that are little or no toxic to human health and the environment.
Replacing harmful chemicals with biological enzymes makes many industrial processes cleaner and
cheaper.

A Particular product can be prepared in Multiple Ways, so the method which is most secure should be
incorporated.

First step is to Identify RISK associated with the Multiple Chemical Processes (which are there)

The goal is to use less hazardous reagents whenever possible and design processes that do not produce
hazardous by-products.

Often a range of reagent choices exist for a particular transformation. This principle focuses on
choosing reagents that pose the least risk and generate only benign by-products.

For example:

CHLORALKALI processes used to produce Chlorine in the descending order of their toxicity are:

1) Mercury cell: produces mercuric waste.

2) Diaphragm cell: uses asbestos based diaphragms.
3) Membrane cell: uses cellulose based diaphragms.

4) Design Safer Chemicals and Products (Towards the Environment) :

Designing Safer Chemicals advocates the design of chemical products in a way that reduces their
toxicity and maintains their effectiveness. The goal of producing safe chemicals (non-
[carcinogenic, mutagenic, neurotoxic] ) is the balance between optimal performance and
 chemical product function, ensuring that toxicity and risk are reduced to the lowest possible
level. In other words, the use of toxic chemicals should be avoided and replaced inhospitable
wherever possible, but should take account of their efficacy.
This principle is used in the development of new insecticides and pesticides that are specific to
target organisms, i.e. they are toxic only to target organisms and decompose into
environmentally harmless substances.
Another Example (Fire Fighting Films):
1) Earlier FLUOROSURFACTANTS were used; those were TOXIC, PERSISTENT, BIOACCUMILATIVE
2) NON FLUORINATED SURFACTANTS: are non toxic, non persistent, and do not accumulate.

5) Safer Solvents and Auxiliaries:

Safer Solvents and Auxiliaries recommends that the process of synthesis be maximally reduced
and, whenever possible, avoid the use of auxiliary chemical substances (e.g. solvents, separating
agents, etc.) When used they should be harmless. According to the principles of green chemistry,
the choice of suitable substitutions for organic solvents is based on: worker safety, process
safety, environmental safety and sustainability of the process. The solvent should be chemically
and physically stable, low volatility, easy to use and easy to recycle.
For now, it is promising to replace the known organic solvents with recyclable solvents, which
are ionic liquids - salts at room temperature in the liquid state. Unlike volatile organic
compounds, ionic liquids have low vapor pressure, do not vaporize easily, resulting in safer
chemical processes.

6) Design for Energy Efficiency:

Energy requirements of chemical processes should be recognized for their environmental and
economic impacts and should be minimized. If possible, synthetic methods should be conducted at
ambient temperature and pressure. Principle of Energy Efficiency, as a fundamental requirement,
minimizes the use of energy.

For example:

Tomatoes that grow in a greenhouse that is heated by the use of waste steam from a nearby
chemical plant for the production of ammonia. Since CO2 concentrations in greenhouses fall below
50%, plant growth can be achieved, and by extrusion from greenhouse gas, carbon dioxide is used as
a tomato seed growth bi-activator.

7) Use of Renewable Feedstocks:

The seventh principle of green chemistry advocates Use of Renewable Feedstocks wherever it is
technically and economically acceptable. For example, it is more convenient to use renewable raw
materials than a variety of plastic materials, and then to waste away the waste materials. The
principle also implies the use of renewable energy technologies that include solar energy, wind
power, hydropower, biomass energy and biofuels.

For example, Brazil with its sugar cane production and bioethanol production ensures energy
independence and employment while Europe's biodiesel is produced from rapeseed oil.

In the case of bioplastics, the use of renewable raw materials in production positively affects energy
consumption and CO2 emissions. Coca-Cola, a world-widescale company for the time being,
manufactures bottles made of 30% polyethylene (PE) blends, while American company Nature
Works uses bottles made from lactic acid polymers (PLA) made from lactic acid, obtained by
fermentation of dextrose obtained from starch, most commonly corn. About 1 kg of PLA requires
about 2.5 kg of corn.

8) Reduce Derivatives:

One of the key principles of green chemistry in the synthesis of target molecules is to avoid the use
of chemical derivatives (Reduce Derivatives). The principle advocates, wherever possible, the
avoidance of physical-chemical processes in which blocking and unblocking of appropriate groups
during the synthesis are used, that is, whenever possible, the biological processes in the synthesis
should be used to avoid synthesis of the products for which they are not. There are enzymes to
degrade them. If possible, it is necessary to reduce or avoid unnecessary derivatization (group
blocking, protection / elimination protection, temporary physicochemical modification) because
such steps require additional reagents and can generate waste.

Typical example is the production of antibiotics (Figure 4) based on penicillin or replacement of

classical chemical enzymatic processes whereby the 6-aminopenicillic acid is obtained by reacting
with the catalyzed immobilized enzyme penicillin amide. This resulted in several chemical steps
being replaced by an enzymatic reaction, and no longer required a low temperature (-60°C), organic
solvents, and completely unsuitable conditions that increased and complicated production in the
case of chemical synthesis.

9) Catalysis:

Catalytic reagents (as selective as possible) are superior to stoichiometric reagents. In order to
protect the environment, the catalysis principle promotes the use of biodegradable catalysts, which
imply less energy use, avoiding the use of organochlorine compounds and reducing the use of water
or less waste water.

Like all catalysts, enzymes function in a way that lowers the activation energy of an individual
reaction, and thus accelerates, up to several million times. In doing so, the enzyme remains
unchanged throughout the duration of the reaction to which it affects, and this allows it to become
completely unchanged when the reaction comes to an end. Also, enzymes do not affect the relative
energy between the reactants and the products, nor to the related reactions. However, what makes
enzymes stand out among all other catalysts is their specificity in terms of stereochemistry, chemical
selectivity and specificity. Compared with non-biological catalysts, biocatalysts have a great
advantage given the rate of reaction, catalytic specificity, lower cost, etc., but lack of heat sensitivity
and poor stability.

The classic catechol synthesis is derived from benzene (non-renewable feedstocks) in several
reaction stages requiring severe reactions under which undesirable byproducts are produced. It is
replaced by a biocatalytic synthesis of D-glucose (renewable raw materials) in the presence of
genetically modified Escherichia coli and is performed in one reaction stage, no byproducts and
production is economically viable.

10) Design for Degradation:

The principle of creating degradable chemicals and products or design for degradation demands the
creation of chemical products that, upon termination of their activity, must be able to convert into
products that are harmless to the environment. Fulfillment of this requirement is possible by
changing the technological parameters in the process management and the change of so-called
auxiliary substances added at certain stages in the production process. The aim is to prevent the
formation of harmful substances and to return to production as much waste as possible, which is
achieved by recycling.

11) Real-Time Analysis for Pollution Prevention:

The principle of Real-Time Analysis for Pollution Prevention requires further development of
analytical methodology to enable real-time monitoring of the chemical production process with the
aim of preventing the formation of dangerous substances, i.e. it is necessary to constantly monitor
the production process at each stage that would prevent the occurrence of errors that could lead to
the emergence of dangerous substances, harmful to the environment and human health. Analytical
methodologies need to be further developed to allow for real-time, in-process monitoring and
control prior to the formation of hazardous substances.

12) Inherently Safer Chemistry for Accident Prevention:

The Twelfth Principle of Green Chemistry is the principle of Inherently Safer Chemistry for Accident
Prevention. The basic requirement is to reduce the use of substances in chemical processes that can
cause adverse effects (explosion, fire and harmful vapor). An example is today the increasing use of
supercritical CO2 that replaces organic solvents and which, unlike organic solvents, is not toxic or
explosive and is environmentally acceptable.

Safety can be defined as a control of known hazards by achieving an acceptable level of risk and is
achieved at several levels of the lowest use of Personal Protective Equipment. Then it follows the
level of Administrative and Work Practice Controls and implies establishing effective procedures,
rotating work tasks, adjusting work schedules so that workers are not over-exposed to the impact of
dangerous chemicals, etc. The next higher level of security control is the expert Engineering Controls,
which implies the implementation of physical process change to reduce contact with hazardous
chemicals, isolate the process, use wet methods to reduce dust formation, ventilation, digestion, etc.
The highest level of safety control is achieved by eliminating or replacing the procedure with safer
alternatives (Figure 6).

ADVANTAGES AND DISADVANTAGES OF GREEN CHEMISTRY:

Advantages:
1) 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.

2) 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.
• Less use of landfills, especially hazardous waste landfills.

3) 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.
• Increased consumer sales by earning and displaying a safer-product label (e.g., safer Choice
labeling.)
• Improved competitiveness of chemical manufacturers and their customers.

Disadvantages of Green Chemistry:

 Switching from an old, conventional product or process to a new "green" product or process
requires a lot of time, design or redesign of a new product and process is often difficult and
quite expensive, and there is also a lack of unity on what is considered safe.
 There is no known alternative to used chemical raw materials or alternative technologies for
green processes. There is also a lack of human resources and skills.
 The risks of switching to green products and processes are not divided within the supply chain,
and there is a lack of resources for further research.

R4M4 model:
R4 stands reduce, reuse, recycle, redesign and M4 stands for multipurpose, multidimensional, multi-
faceting and multi-tracking.
The principle of the theory is to work with materials and method with precise and accurate
experimental results along 100% inhibition of any polluting discharges in experiment.
The principle of R4M4 of materials and methods saves up to 90% of resources, time and can enhance
the accuracy and precision associated with the measurements.
R4 is concerned about material and M4 is concerned with method. One of the examples is Survismeter.
The Survismeter reduces multistep process to few fundamental steps as compared to separate
measurements. This instrument is completely jacketed, thereby reducing the chances of air
contamination and slippage of volatile organic compounds to the environment. Its specially designed
polyacrylic chamber that helps to carry out study of the physicochemical properties over a wide
temperature range from 0 – 80 degree.
Survismeter finds its major application in the thrust areas of research: dyes, surfactants, emulsions,
nanoparticles, polymers and biological molecules like proteins, DNA, polysaccharides, lipids, amino acids
and nucleic acids.

Life Cycle Analysis:

Life-cycle analysis (LCA), also known as life-cycle assessment, is a primary tool used to
support decision-making for sustainable development. LCA is a comprehensive method for
assessing all direct and indirect environmental impacts across the full life cycle of a product
system, from materials acquisition, to manufacturing, to use, and to final disposition (disposal
or reuse).

The LCA process is a systematic, phased approach and consists of four components: goal definition
and scoping, inventory analysis, impact assessment, and interpretation.
1) Goal definition and scoping − Define and describe the product, process or activity.
Establish the context in which the assessment is to be made and identify the boundaries
and environmental effects to be reviewed for the assessment.
2) Inventory analysis − Identify and quantify energy, water and materials usage and
environmental releases (e.g., air emissions, solid waste disposal, waste water discharges).
 3) Impact assessment − Assess the potential human and ecological effects of energy, water,
and material usage and the environmental releases identified in the inventory analysis.
4) Interpretation − Evaluate the results of the inventory analysis and impact assessment to
select the preferred product, process or service with a clear understanding of the
uncertainty and the assumptions used to generate the results.
By performing an LCA, decision-makers can for example:
 Develop a systematic evaluation of the environmental consequences associated with a given
product.
 Analyze the environmental trade-offs associated with one or more specific products/processes to
help gain stakeholder (state, community, etc.) acceptance for a planned action.
 Quantify environmental releases to air, water, and land in relation to each life cycle stage and/or
major contributing process.
 Assess the human and ecological effects of material consumption and environmental releases to
the local community, region, and world.
 Compare the health and ecological impacts between two or more rival products/processes or
identify the impacts of a specific product or process.

Assessing Green Chemistry and Engineering Technologies Using LCA:

An essential aspect of green chemistry and engineering is that it can facilitate environmental
improvements at every stage of the life cycle, which typically includes the stages of materials
extraction and acquisition; materials transformation, processing, and manufacturing; packaging,
transportation, and distribution; consumer use; and end-of-life management. A second essential
aspect is that effective implementation of a green chemistry technology can offer
environmental benefits that propagate throughout the life cycle.
Within the LCA framework, the first step in assessing technologies is to define the boundaries of
the study.
Several types of quantitative data throughout the life cycle of a product or process are desirable
to form an inventory analysis. Metrics can be tailored to a particular study to compare the
environmental impacts of a process or product. For example, we might want to know the
electricity use required by a traditional chemical process as compared to a process.
Here is an example of the life-cycle issues associated with green chemistry and engineering
technologies to have a flavor of the goals and benefits of life-cycle assessment:
Example: Alternatives to Chlorine Bleaching in the Pulp and Paper Industry:
The widespread generation and dissipation of organochlorines is a recognized hazard to the
health of people and wildlife. Chlorine bleaching has been used widely in the pulp and paper
industry. Much research is being done to find safer alternatives, and one alternative is using
elemental-chlorine-free (ECF) technologies. Even more environmentally friendly is the
replacement of chlorine-based bleaching with totally chlorine-free (TCF) methods.
One example of TCF methods is the use of the so called TAML (a trademark owned by Carnegie
Mellon University) catalysts as alternative reagents for paper bleaching. To assess this green
chemistry technology, we would like to be able to compare the resource use and environmental
impacts of the manufacture of alternative whitening agents in the pulp and paper industry to
those of traditional chlorine or ECF methods. Ideally, we would be able to collect and assess
quantitative data on the processes, as illustrated in Figure 3.