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Green chemistry
From Wikipedia, the free encyclopediaThis article is about the concept of the environmentally friendly design of
chemical products and processes. For the journal, see Green Chemistry (journal.
Green chemistry, also called sustainable chemistry, is an area of chemistry and
chemical engineering focused on the design of products and processes that
minimi!e the use and generation of ha!ardous substances."#$ 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 nonrene%able resources."&$"'$"$")$"*$"+$
Green chemistry overlaps %ith all subdisciplines of chemistry but %ith a particular focus on chemical synthesis, process chemistry, and chemical
engineering, in industrial applications. To a lesser etent, the principles of green
chemistry also affect laboratory practices. The overarching goals of green
chemistry-namely, more resourceefficient and inherently safer design of
molecules, materials, products, and processes-can be pursued in a %ide range of
contets.
Contents
• # /istory
• & 0rinciples
• ' Trends
• 1amples
o .# Green solvents
o .& 2ynthetic techni3ues
.&.# Carbon dioide as blo%ing agent
o .' /ydra!ine
o . #,'0ropanediol
o .) 4actide
o
.* Carpet tile backings
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o .+ Transesterification of fats
o .5 6iosuccinic acid
o .7 4aboratory chemicals
• ) 4egislation
o ).# 1urope
o ).& 8nited 2tates
• * Green Chemistry 1ducation
• + 2cientific journals speciali!ed in green chemistry
• 5 Contested definition
• 7 Green Chemistry 9%ards
• #: 2ee also
• ## ;eferences
History
Green chemistry emerged from a variety of eisting ideas and research efforts
(such as atom economy and catalysis in the period leading up to the #77:s, in the
contet of increasing attention to problems of chemical pollution and resource
depletion. The development of green chemistry in 1urope and the 8nited 2tates
%as linked to a shift in environmental problemsolving strategies< a movement
from commandandcontrol regulation and mandated reduction of industrial
emissions at the =end of the pipe,= to%ard the active prevention of pollution
through the innovative design of production technologies themselves. The set of
concepts no% recogni!ed as green chemistry coalesced in the mid to late#77:s,along %ith broader adoption of the term (%hich prevailed over competing terms
such as =clean= and =sustainable= chemistry."5$"7$
>n the 8nited 2tates, the 1nvironmental 0rotection 9gency played a significant
early role in fostering green chemistry through its pollution prevention programs,
funding, and professional coordination. 9t the same time in the 8nited ?ingdom,
researchers at the 8niversity of @ork contributed to the establishment of the Green
Chemistry Aet%ork %ithin the ;oyal 2ociety of Chemistry, and the launch of the
journal Green Chemistry."7$
Principles
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>n #775, 0aul 9nastas (%ho then directed the Green Chemistry 0rogram at the 82
109 and Bohn C. Warner (then of 0olaroid Corporation published a set of
principles to guide the practice of green chemistry."#:$ The t%elve principles
address a range of %ays to reduce the environmental and health impacts of
chemical production, and also indicate research priorities for the development ofgreen chemistry technologies.
The principles cover such concepts as<
• the design of processes to maimi!e the amount of ra% material that ends
up in the product
• the use of rene%able material feedstocks and energy sources
•
the use of safe, environmentally benign substances, including solvents,%henever possible
• the design of energy efficient processes
• avoiding the production of %aste, %hich is vie%ed as the ideal form of
%aste management.
The twelve principles of green chemistry are<
#. >t is better to prevent %aste than to treat or clean up %aste after it is
formed.
&. 2ynthetic methods should be designed to maimi!e the incorporation of all
materials used in the process into the final product.
'. Wherever practicable, synthetic methodologies should be designed to use
and generate substances that possess little or no toicity to human health
and the environment.
. Chemical products should be designed to preserve efficacy of function
%hile reducing toicity.
). The use of auiliary substances (e.g. solvents, separation agents, etc.
should be made unnecessary %herever possible and innocuous %hen used.
*. 1nergy re3uirements should be recogni!ed for their environmental and
economic impacts and should be minimi!ed. 2ynthetic methods should be
conducted at ambient temperature and pressure.
+. 9 ra% material or feedstock should be rene%able rather than depleting
%herever technically and economically practicable.
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5. ;educe derivatives D 8nnecessary derivati!ation (blocking group,
protectionEdeprotection, temporary modification should be avoided
%henever possible.
7. Catalytic reagents (as selective as possible are superior to stoichiometricreagents.
#:. Chemical products should be designed so that at the end of their function
they do not persist in the environment and break do%n into innocuous
degradation products.
##. 9nalytical methodologies need to be further developed to allo% for real
time, inprocess monitoring and control prior to the formation of
ha!ardous substances.
#&. 2ubstances and the form of a substance used in a chemical process should be chosen to minimi!e potential for chemical accidents, including releases,
eplosions, and fires.
Trends
9ttempts are being made not only to 3uantify 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, hard%are demands, energy profile and
ease of product %orkup and purification. >n one 3uantitative study,"##$ the reduction
of nitroben!ene to aniline receives * points out of #:: marking it as anacceptable synthesis overall %hereas a synthesis of an amide using /2 is only
described as ade3uate %ith a combined '& points.
Green chemistry is increasingly seen as a po%erful tool that researchers must use
to evaluate the environmental impact of nanotechnology."#&$ 9s 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
longterm economic viability."citation needed $
ExamplesGreen solvents
2olvents are consumed in large 3uantities in many chemical syntheses as %ell as
for cleaning and degreasing. Traditional solvents are often toic or are chlorinated.
Green solvents, on the other hand, are generally derived from rene%able resources
and biodegrade to innocuous, often naturally occurring product."#'$"#$
Synthetic techniques
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Aovel or enhanced synthetic techni3ues can often provide improved
environmental performance or enable better adherence to the principles of green
chemistry. For eample, the &::) Aobel 0ri!e for Chemistry %as a%arded for the
development of the metathesis method in organic synthesis, %ith eplicit
reference to its contribution to green chemistry and =smarter production.="#)$
9&::) revie% identified three key developments in green chemistry in the field of
organic synthesis< use of supercritical carbon dioide as green solvent, a3ueous
hydrogen peroide for clean oidations and the use of hydrogen in asymmetric
synthesis."#*$ 2ome further eamples of applied green chemistry are supercritical
%ater oidation, on %ater reactions, and dry media reactions."citation needed $
6ioengineering is also seen as a promising techni3ue for achieving green
chemistry goals. 9 number of important process chemicals can be synthesi!ed in
engineered organisms, such as shikimate, a Tamiflu precursor %hich is fermented
by ;oche in bacteria. Click chemistry is often cited"citation needed $ as a style of
chemical synthesis that is consistent %ith the goals of green chemistry. Theconcept of Hgreen pharmacyH has recently been articulated based on similar
principles."#+$
Carbon dioxide as blowing agent
>n #77*, o% Chemical %on the #77* Greener ;eaction Conditions a%ard for
their #::I carbon dioide blo%ing agent for polystyrene foam production.
0olystyrene foam is a common material used in packing and food transportation.
2even hundred million pounds are produced each year in the 8nited 2tates alone.
Traditionally, CFC and other o!onedepleting chemicals %ere used in the
production process of the foam sheets, presenting a serious environmental ha!ard.
Flammable, eplosive, and, in some cases toic hydrocarbons have also been used
as CFC replacements, but they present their o%n problems. o% Chemical
discovered that supercritical carbon dioide %orks e3ually as %ell as a blo%ing
agent, %ithout the need for ha!ardous substances, allo%ing the polystyrene to be
more easily recycled. The CJ& used in the process is reused from other industries,
so the net carbon released from the process is !ero.
Hydraine
9ddressing principle K& is the 0eroide 0rocess for producing hydra!ine %ithoutcogenerating salt. /ydra!ine is traditionally produced by the Jlin ;aschig process
from sodium hypochlorite (the active ingredient in many bleaches and ammonia.
The net reaction produces one e3uivalent of sodium chloride for every e3uivalent
of the targeted product hydra!ine<"#5$
AaJCl L & A/' M /& AA/& L AaCl L /&J
>n the greener 0eroide process hydrogen peroide is employed as the oidant, the
side product being %ater. The net conversion follo%s<
& A/' L /&J& M /& AA/& L & /&J
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9ddressing principle K, this process does not re3uire auiliary etracting
solvents. ethyl ethyl ketone is used as a carrier for the hydra!ine, the
intermediate keta!ide phase separates from the reaction miture, facilitating
%orkup %ithout the need of an etracting solvent.
!"#$Propanediol
9ddressing principle K+ is a green route to #,'propanediol, %hich is traditionally
generated from petrochemical precursors. >t can be produced from rene%able
precursors via the bioseparation of #,'propanediol using a genetically modified
strain of E. coli."#7$ This diol is used to make ne% polyesters for the manufacture
of carpets.
%actide
4actide
>n &::&, Cargill o% (no% AatureWorks %on the Greener ;eaction Conditions
9%ard for their improved method for polymeri!ation of polylactic acid .
8nfortunately, lactidebase polymers do not perform %ell and the project %as
discontinued by o% soon after the a%ard. 4actic acid is produced by fermentingcorn and converted to lactide, the cyclic dimer ester of lactic acid using an
efficient, tincataly!ed cycli!ation. The 4,4lactide enantiomer is isolated by
distillation and polymeri!ed in the melt to make a crystalli!able polymer , %hich
has some applications including tetiles and apparel, cutlery, and food packaging.
Walart has announced that it is usingE%ill use 049 for its produce packaging.
The AatureWorks 049 process substitutes rene%able materials for petroleum
feedstocks, doesnHt re3uire the use of ha!ardous organic solvents typical in other
049 processes, and results in a high3uality polymer that is recyclable and
compostable.
Carpet tile bac&ings
>n &::' 2ha% >ndustries selected a combination of polyolefin resins as the base
polymer of choice for 1coWor due to the lo% toicity of its feedstocks, superior
adhesion properties, dimensional stability, and its ability to be recycled. The
1coWor compound also had to be designed to be compatible %ith nylon carpet
fiber. 9lthough 1coWor may be recovered from any fiber type, nylon* provides
a significant advantage. 0olyolefins are compatible %ith kno%n nylon*
depolymeri!ation methods. 0NC interferes %ith those processes. Aylon*
chemistry is %ellkno%n and not addressed in firstgeneration production. From
its inception, 1coWor met all of the design criteria necessary to satisfy the needs
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of the marketplace from a performance, health, and environmental standpoint.
;esearch indicated that separation of the fiber and backing through elutriation,
grinding, and air separation proved to be the best %ay to recover the face and
backing components, but an infrastructure for returning postconsumer 1coWor to
the elutriation process %as necessary. ;esearch also indicated that the postconsumer carpet tile had a positive economic value at the end of its useful life.
1coWor is recogni!ed by 6C as a certified cradletocradle design.
Trans and cis fatty acids
Transesterification of fats
>n &::), 9rcher aniels idland (9 and Aovo!ymes %on the Greener
2ynthetic 0ath%ays 9%ard for their en!yme interesterification process. >n
response to the 8.2. Food and rug 9dministration (F9 mandated labeling of
transfats on nutritional information by Banuary #, &::*, Aovo!ymes and 9
%orked together to develop a clean, en!ymatic process for the interesterification of oils and fats by interchanging saturated and unsaturated fatty acids. The result
is commercially viable products %ithout transfats. >n addition to the human
health benefits of eliminating transfats, the process has reduced the use of toic
chemicals and %ater, prevents vast amounts of byproducts, and reduces the
amount of fats and oils %asted.
'io$succinic acid
>n &:##, the Jutstanding Green Chemistry 9ccomplishments by a 2mall 6usiness
9%ard %ent to 6io9mber >nc. for integrated production and do%nstreamapplications of biobased succinic acid. 2uccinic acid is a platform chemical that
is an important starting material in the formulations of everyday products.
Traditionally, succinic acid is produced from petroleumbased feedstocks.
6io9mber has developed process and technology that produces succinic acid from
the fermentation of rene%able feedstocks at a lo%er cost and lo%er energy
ependiture than the petroleum e3uivalent %hile se3uestering CJ& rather than
emitting it."&:$
%aboratory chemicals
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2everal laboratory chemicals are controversial from the perspective of Green
chemistry. The assachusetts >nstitute of Technology has created the "&$ to help
identify alternatives. 1thidium bromide, ylene, mercury, and formaldehyde have
been identified as =%orst offenders= %hich have alternatives."&#$ 2olvents in
particular make a large contribution to the environmental impact of chemicalmanufacturing and there is a gro%ing focus on introducing Greener solvents into
the earliest stage of development of these processes< laboratoryscale reaction and
purification methods."&&$ >n the 0harmaceutical >ndustry, both G2? "&'$ and 0fi!er "&$
have published 2olvent 2election Guides for their rug iscovery chemists.
%egislation
Europe
>n &::+, 1urope put into place the ;egistration, 1valuation, 9uthorisation, and;estriction of Chemicals (;19C/ program, %hich re3uires companies to
provide data sho%ing that their products are safe. This regulation (#7:+E&::*
ensures not only the assessment of the chemicalsH ha!ards as %ell as risks during
their uses but also includes measures for banning or restrictingEauthorising uses of
specific substances. 1C/9, the 18 Chemicals 9gency in /elsinki, is
implementing the regulation %hereas the enforcement lies %ith the 18 member
states.
(nited States
The 8.2. la% that governs the majority of industrial chemicals (ecluding pesticides, foods, and pharmaceuticals is the Toic 2ubstances Control 9ct
(T2C9 of #7+*. 1amining the role regulatory programs in shaping the
development of green chemistry in the 8nited 2tates, analysts have revealed
structural fla%s and longstanding %eaknesses in T2C9 for eample, a &::*
report to the California 4egislature concludes that T2C9 has produced a domestic
chemicals market that discounts the ha!ardous properties of chemicals relative to
their function, price, and performance."&)$ 2cholars have argued that such market
conditions represent a key barrier to the scientific, technical, and commercial
success of green chemistry in the 8.2., and fundamental policy changes are
needed to correct these %eaknesses."&*$
0assed in #77:, the 0ollution 0revention 9ct helped foster ne% approaches for
dealing %ith pollution by preventing environmental problems before they happen.
>n &::5, the 2tate of California approved t%o la%s aiming to encourage green
chemistry, launching the California Green Chemistry >nitiative. Jne of these
statutes re3uired CaliforniaHs epartment of Toic 2ubstances Control (T2C to
develop ne% regulations to prioriti!e =chemicals of concern= and promote the
substitution of ha!ardous chemicals %ith safer alternatives. The resulting
regulations took effect in &:#', initiating T2CHs Safer Consumer Products
Program."&+$
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Green Chemistry Education
any institutions offer courses"&5$ and degrees on Green Chemistry. 1amples
from across the globe are enmarkHs Technical 8niversity,"&7$ and several in the
82, e.g. at the 8niversities of assachusetts6oston, "':$ ichigan,"'#$ and Jregon."'&$ 9 masters level course in Green Technology, has been introduced by the
>nstitute of Chemical Technology, >ndia. >n the 8? at the 8niversity of @ork "''$
8niversity of 4eicester, epartment of Chemistry and ;es in Green Chemistry
at >mperial College 4ondon. >n 2pain different universities like the 8niversidad de
Baume >"'$ or the 8niversidad de Aavarra,"')$ offer Green Chemistry master
courses. There are also %ebsites focusing on green chemistry, such as the
ichigan Green Chemistry Clearinghouse at %%%.migreenchemistry.org.
9part from its Green Chemistry aster courses the Ourich 8niversity of 9pplied
2ciences O/9W presents an eposition and %eb page =aking chemistry green=
for a broader public, illustrating the #& principles."'*$
Scientific )ournals specialied in green chemistry
• Green Chemistry (;2C
• Chem2usChem (Wiley
• 9C2 2ustainable Chemistry P 1ngineering (9C2
Contested definition
There are ambiguities in the definition of green chemistry, and in ho% it is
understood among broader science, policy, and business communities. 1ven
%ithin chemistry, researchers have used the term =green chemistry= to describe a
range of %ork independently of the frame%ork put for%ard by 9nastas and
Warner (i.e., the #& principles."7$ While not all uses of the term are legitimate (see
green%ashing, many are, and the authoritative status of any single definition is
uncertain. ore broadly, the idea of green chemistry can easily be linked (or
confused %ith related concepts like green engineering, environmental design, or
sustainability in general. The compleity and multifaceted nature of greenchemistry makes it difficult to devise clear and simple metrics. 9s a result, =%hat
is green= is often open to debate."'+$
Green Chemistry *wards
2everal scientific societies have created a%ards to encourage research in green
chemistry.
• 9ustraliaQs Green Chemistry Challenge 9%ards overseen by The ;oyal
9ustralian Chemical >nstitute (;9C>.
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• The Canadian Green Chemistry edal."'5$
• >n >taly, Green Chemistry activities center around an interuniversity
consortium kno%n as >AC9."'7$
• >n Bapan, The Green P 2ustainable Chemistry Aet%ork oversees the G2C
a%ards program.":$
• >n the 8nited ?ingdom, the Green Chemical Technology 9%ards are given
by Crystal Faraday."#$
• >n the 82, the 0residential Green Chemistry Challenge 9%ards recogni!e
individuals and businesses."&$"'$
See also
Chemistry portal
Sustainable development portal
• Green Chemistry (journal D published by the ;oyal 2ociety of Chemistry
• Green chemistry metrics
•2ustainable engineering
• Green engineering
• 1nvironmental engineering science
• Green computing D a similar initiative in the area of computing
• 6ioremediation D a techni3ue that generally falls outside the scope of
green chemistry
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