Green chemistry, also called sustainable chemistry, is an area of chemistry and chemical

engineering focused on the designing of products and processes that minimize or eliminate the
use and generation of hazardous substances. [1] While environmental chemistry focuses on the
effects of polluting chemicals on nature, green chemistry focuses on the environmental
impact of chemistry, including technological approaches to preventing pollution and reducing
consumption of nonrenewable resources.[2][3][4][5][6][7]
The overarching goals of green chemistry—namely, more resource-efficient and inherently
safer design of molecules, materials, products, and processes—can be pursued in a wide range
of contexts.

History[edit]

Green chemistry emerged from a variety of existing ideas and research efforts (such as atom
economy and catalysis) in the period leading up to the 1990s, in the context of increasing
attention to problems of chemical pollution and resource depletion. The development of green
chemistry in Europe and the United States was linked to a shift in environmental problem-
solving strategies: a movement from command and control regulation and mandated reduction
of industrial emissions at the "end of the pipe," toward the active prevention of pollution
through the innovative design of production technologies themselves. The set of concepts now
recognized as green chemistry coalesced in the mid- to late-1990s, along with broader
adoption of the term (which prevailed over competing terms such as "clean" and "sustainable"
chemistry).[10][11]

In the United States, the Environmental Protection Agency played a significant early role in
fostering green chemistry through its pollution prevention programs, funding, and professional
coordination. At the same time in the United Kingdom, researchers at the University of
York contributed to the establishment of the Green Chemistry Network within the Royal
Society of Chemistry, and the launch of the journal Green Chemistry.[11]

Principles[edit]

In 1998, Paul Anastas (who then directed the Green Chemistry Program at the US EPA)
and John C. Warner (then of Polaroid Corporation) published a set of principles to guide the
practice of green chemistry.[12] The twelve principles address a range of ways to reduce the
environmental and health impacts of chemical production, and also indicate research priorities
for the development of green chemistry technologies.

The principles cover such concepts as:

 the design of processes to maximize the amount of raw material that ends up in the
product;
 the use of renewable material feedstocks and energy sources;
 the use of safe, environmentally benign substances, including solvents, whenever possible;
 the design of energy efficient processes;
 avoiding the production of waste, which is viewed as the ideal form of waste management.
The twelve principles of green chemistry are:[13]

1. Prevention. Preventing waste is better than treating or cleaning up waste after it is

created.
2. Atom economy. Synthetic methods should try to maximize the incorporation of all
materials used in the process into the final product.This means that less waste will be
generated as a result.
3. Less hazardous chemical syntheses. Synthetic methods should avoid using or generating
substances toxic to humans and/or the environment.
4. Designing safer chemicals. Chemical products should be designed to achieve their
desired function while being as non-toxic as possible.
5. Safer solvents and auxiliaries. Auxiliary substances should be avoided wherever
possible, and as non-hazardous as possible when they must be used.
6. Design for energy efficiency. Energy requirements should be minimized, and processes
should be conducted at ambient temperature and pressure whenever possible.
7. Use of renewable feedstocks. Whenever it is practical to do so, renewable feedstocks
or raw materials are preferable to non-renewable ones.
8. Reduce derivatives. Unnecessary generation of derivatives—such as the use
of protecting groups—should be minimized or avoided if possible; such steps require
additional reagents and may generate additional waste.
9. Catalysis. Catalytic reagents that can be used in small quantities to repeat a reaction
are superior to stoichiometric reagents (ones that are consumed in a reaction).
10. Design for degradation. Chemical products should be designed so that they do not
pollute the environment; when their function is complete, they should break down into
non-harmful products.
11. Real-time analysis for pollution prevention. Analytical methodologies need to be
further developed to permit real-time, in-process monitoring and
control before hazardous substances form.
12. Inherently safer chemistry for accident prevention. Whenever possible, the substances
in a process, and the forms of those substances, should be chosen to minimize risks
such as explosions, fires, and accidental releases.

Trends[edit]

Attempts are being made not only to quantify the greenness of a chemical process but also to
factor in other variables such as chemical yield, the price of reaction components, safety in
handling chemicals, hardware demands, energy profile and ease of product workup and
purification. In one quantitative study,[14] the reduction of nitrobenzene to anilinereceives 64
points out of 100 marking it as an acceptable synthesis overall whereas a synthesis of
an amide using HMDS is only described as adequate with a combined 32 points.
Green chemistry is increasingly seen as a powerful tool that researchers must use to evaluate
the environmental impact of nanotechnology. [15] As nanomaterials are developed, the
environmental and human health impacts of both the products themselves and the processes to
make them must be considered to ensure their long-term economic viability.[citation needed]
Examples[edit]
Green solvents[edit]

Solvents are consumed in large quantities in many chemical syntheses as well as for cleaning
and degreasing. Traditional solvents are often toxic or are chlorinated. Green solvents, on the
other hand, are generally derived from renewable resources and biodegrade to innocuous,
often a naturally occurring product.[16][17]

Synthetic techniques[edit]

Novel or enhanced synthetic techniques can often provide improved environmental performance
or enable better adherence to the principles of green chemistry. For example, the 2005 Nobel
Prize for Chemistry was awarded, to Yves Chauvin, Robert H. Grubbs and Richard R. Schrock,
for the development of the metathesis method in organic synthesis, with explicit reference to
its contribution to green chemistry and "smarter production." [18] A 2005 review identified
three key developments in green chemistry in the field of organic synthesis: use
of supercritical carbon dioxide as green solvent, aqueous hydrogen peroxide for
clean oxidations and the use of hydrogen in asymmetric synthesis.[19] Some further examples
of applied green chemistry are supercritical water oxidation, on water reactions, and dry
media reactions.[citation needed]

Bioengineering is also seen as a promising technique for achieving green chemistry goals. A
number of important process chemicals can be synthesized in engineered organisms, such
as shikimate, a Tamiflu precursor which is fermented by Roche in bacteria. Click chemistry is
often cited[citation needed] as a style of chemical synthesis that is consistent with the goals of
green chemistry. The concept of 'green pharmacy' has recently been articulated based on
similar principles.[20]

Carbon dioxide as blowing agent[edit]

In 1996, Dow Chemical won the 1996 Greener Reaction Conditions award for their
100% carbon dioxide blowing agent for polystyrene foam production. Polystyrene foam is a
common material used in packing and food transportation. Seven hundred million pounds are
produced each year in the United States alone. Traditionally, CFC and other ozone-depleting
chemicals were used in the production process of the foam sheets, presenting a
serious environmental hazard. Flammable, explosive, and, in some cases toxic hydrocarbons
have also been used as CFC replacements, but they present their own problems. Dow Chemical
discovered that supercritical carbon dioxide works equally as well as a blowing agent, without
the need for hazardous substances, allowing the polystyrene to be more easily recycled. The
CO2 used in the process is reused from other industries, so the net carbon released from the
process is zero.
Hydrazine[edit]

Addressing principle #2 is the Peroxide Process for producing hydrazine without cogenerating
salt. Hydrazine is traditionally produced by the Olin Raschig process from sodium
hypochlorite (the active ingredient in many bleaches) and ammonia. The net reaction produces
one equivalent of sodium chloride for every equivalent of the targeted product hydrazine:[21]
NaOCl + 2 NH3 → H2N-NH2 + NaCl + H2O
In the greener Peroxide process hydrogen peroxide is employed as the oxidant and the
side product is water. The net conversion follows:
2 NH3 + H2O2 → H2N-NH2 + 2 H2O

Addressing principle #4, this process does not require auxiliary extracting
solvents. Methyl ethyl ketone is used as a carrier for the hydrazine, the intermediate
ketazine phase separates from the reaction mixture, facilitating workup without the
need of an extracting solvent.

1,3-Propanediol[edit]

Addressing principle #7 is a green route to 1,3-propanediol, which is traditionally

generated from petrochemical precursors. It can be produced from renewable
precursors via the bioseparation of 1,3-propanediol using a genetically
modified strain of E. coli.[22] This diol is used to make new polyesters for the
manufacture of carpets.

Lactide[edit]

Lactide

In 2002, Cargill Dow (now NatureWorks) won the Greener Reaction Conditions Award
for their improved method for polymerization of polylactic acid . Unfortunately,
lactide-base polymers do not perform well and the project was discontinued by Dow
soon after the award. Lactic acid is produced by fermenting corn and converted
to lactide, the cyclic dimer ester of lactic acid using an efficient, tin-catalyzed
cyclization. The L,L-lactide enantiomer is isolated by distillation and polymerized in
the melt to make a crystallizable polymer, which has some applications
including textiles and apparel, cutlery, and food packaging. Wal-Mart has announced
that it is using/will use PLA for its produce packaging. The NatureWorks PLA process
substitutes renewable materials for petroleum feedstocks, doesn't require the use of
hazardous organic solvents typical in other PLA processes, and results in a high-quality
polymer that is recyclable and compostable.
Carpet tile backings[edit]

In 2003 Shaw Industries selected a combination of polyolefin resins as the base

polymer of choice for EcoWorx due to the low toxicity of its feedstocks, superior
adhesion properties, dimensional stability, and its ability to be recycled. The EcoWorx
compound also had to be designed to be compatible with nylon carpet fiber. Although
EcoWorx may be recovered from any fiber type, nylon-6 provides a significant
advantage. Polyolefins are compatible with known nylon-6 depolymerization methods.
PVC interferes with those processes. Nylon-6 chemistry is well-known and not
addressed in first-generation production. From its inception, EcoWorx met all of the
design criteria necessary to satisfy the needs of the marketplace from a performance,
health, and environmental standpoint. Research indicated that separation of the fiber
and backing through elutriation, grinding, and air separation proved to be the best way
to recover the face and backing components, but an infrastructure for returning
postconsumer EcoWorx to the elutriation process was necessary. Research also
indicated that the postconsumer carpet tile had a positive economic value at the end
of its useful life. EcoWorx is recognized by MBDC as a certified cradle-to-cradle
design.

Trans and cis fatty acids

Transesterification of fats[edit]

In 2005, Archer Daniels Midland (ADM) and Novozymes won the Greener Synthetic
Pathways Award for their enzyme interesterification process. In response to the U.S.
Food and Drug Administration (FDA) mandated labeling of trans-fats on nutritional
information by January 1, 2006, Novozymes and ADM worked together to develop a
clean, enzymatic process for the interesterification of oils and fats by interchanging
saturated and unsaturated fatty acids. The result is commercially viable products
without trans-fats. In addition to the human health benefits of eliminating trans-
fats, the process has reduced the use of toxic chemicals and water, prevents vast
amounts of byproducts, and reduces the amount of fats and oils wasted.

Bio-succinic acid[edit]

In 2011, the Outstanding Green Chemistry Accomplishments by a Small Business

Award went to BioAmber Inc. for integrated production and downstream applications
of bio-based succinic acid. Succinic acid is a platform chemical that is an important
starting material in the formulations of everyday products. Traditionally, succinic acid
is produced from petroleum-based feedstocks. BioAmber has developed process and
technology that produces succinic acid from the fermentation of renewable feedstocks
at a lower cost and lower energy expenditure than the petroleum equivalent while
sequestering CO2 rather than emitting it.[23]
Laboratory chemicals[edit]

Several laboratory chemicals are controversial from the perspective of Green

chemistry. The Massachusetts Institute of Technology created a "Green" Alternatives
 Wizard [2] to help identify alternatives. Ethidium bromide, xylene, mercury,
and formaldehyde have been identified as "worst offenders" which have
alternatives.[24] Solvents in particular make a large contribution to the environmental
impact of chemical manufacturing and there is a growing focus on introducing Greener
solvents into the earliest stage of development of these processes: laboratory-scale
reaction and purification methods.[25] In the Pharmaceutical Industry, both GSK[26] and
Pfizer[27] have published Solvent Selection Guides for their Drug Discovery chemists
https://en.wikipedia.org/https://www.britannica.com/science/green-
chemistrywiki/Green_chemistry#Education