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The green chemistry revolution is providing an enormous number of challenges to those who practice
chemistry in industry, education and research. With these challenges however, there are an equal number
of opportunities to discover and apply new chemistry, to improve the economics of chemical
manufacturing and to enhance the much-tarnished image of chemistry.
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Green chemistry initiatives are driven by government legislation, societal pressure, and economic
benefits.
What is the difference between Environmental Science and Green Chemistry?
Both areas of study seek to make the world a better place. The two are
complimentary to each other. Environmental Science identifies sources, elucidates mechanisms and
quantifies problems in the earths environment. Green Chemistry seeks to solve these problems by
creating alternative, safe technologies. Green Chemistry is not Environmental Chemistry. Green
Chemistry targets pollution prevention at the source, during the design stage of a chemical product or
process,
and thus prevents pollution before it begins.
Is Green Chemistry more expensive that traditional Chemistry?
No. A simplified analysis of the cost structure associated with any chemical
process takes into account the cost of materials, equipment and the human resources necessary.
But, in reality, disposal, treatment and regulatory costs associated with the buying, using and
generating hazardous materials involves numerous hidden costs. When you buy and use a
hazardous material you are paying for it twice, once when you use it and once when you get rid
of it. It makes sense that if you use materials that are non-hazardous and thus have minimal
regulatory or disposal costs associated with them, the benefit to the economic bottom line is
obvious. The Presidential Green Chemistry Challenge Award has provided illustrations of several
examples where industry has not only accomplished goals of pollution prevention, but has
achieved significant economic benefits simultaneously.
Chemical developments also bring new environmental problems and harmful unexpected side
effects, which result in the need for greener chemical products.
Green chemistry looks at pollution prevention on the molecular scale and is an extremely
important area of Chemistry due to the importance of Chemistry in our world today and the
implications it can show on our environment.
The Green Chemistry program supports the invention of more environmentally friendly
chemical processes which reduce or even eliminate the generation of hazardous substances.
This program works very closely with the twelve principles of Green Chemistry.
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It is better to prevent waste than to treat or clean up waste after it has been created.
2. Atom Economy
Synthetic methods should be designed to maximize the incorporation of all materials used in the
process into the final product.
3. Less Hazardous Chemical Syntheses
Wherever practicable, synthetic methods should be designed to use and generate substances that
possess little or no toxicity to human health and the environment.
4. Designing Safer Chemicals
Chemical products should be designed to effect their desired function while minimizing their
toxicity.
5. Safer Solvents and Auxiliaries
The use of auxiliary substances (e.g., solvents, separation agents, etc.) should be made
unnecessary wherever possible and innocuous when used.
The long-term availability of the energy source that guarantees to meet any present or
future consumption needs.
The amount of energy consumed to exploit the available resources should not exceed the
amount of energy these resources produce (ie, the energy efficiency of the source).
hydrocarbons is limited for all practical purposes. When we have extracted the last barrel from
the ground or tar sands its finished for these millennia.
Adopting a geological sense of time (billions of years), we can say that all energy
sources are renewable. If we could wait long enough, more oil would be created. The geological
sense of time doesnt help us to make good, sustainable energy decisions since our rate of
consumption far exceeds the rate of replenishment.
Keeping a human sense of time (generations), our most renewable sources of energy
are: solar, wind, hydroelectric, hydrokinetic, geothermal, and hydrogen fuel cells. Carbon-based
renewables include: biomass, biodiesel, waste to energy, anaerobic digestion and landfill
gas. These eleven energy sources are listed by most U.S. states in their Renewables Portfolio
Standards (RPS).
Sustainable vs Renewable Energy Are They the Same?
Many use the terms sustainable and renewable energy without any distinction.
Contrary to the common belief, there is a difference between them. Although renewable energy
sources share all the sustainable energy characteristics described above, they are clean sources
that do not pollute the environment during consumption and have minimum impact on human
health and the ecosystems. Therefore, the term "sustainable" is wider and includes all types of
renewable energy.
quantities of urine would have to be produced, which is almost impossible. Anyway, any kind of
urine could be used to produce hydrogen, which is a better fuel.
machines to convert one form of energy into another and the resources for those devices come
from the Earths crust. Those devices have a finite life span and depend on yet further
infrastructure (transport, cities, factories, universities, police, etc.) to maintain and operate them,
which in turn has a finite life span. Continued mining, refining and manufacturing is required.
The amount of energy captured from the sun by such devices can never be enough to restore the
Earth to its original condition. This is determined by the second law of thermodynamics. So the
process of mining, building and manufacturing, to convert and use energy, inexorably depletes
and degrades the Earths mineral resources. It is irreversible and unsustainable. It makes no
difference whether we consider solar, wind, hydro, coal, bio, nuclear or geothermal energy. They
are all unsustainable according to the laws of physics.
The second law of thermodynamics also tells us that we cannot completely recycle resources that
have been extracted from the Earth and refined for use (such as metals, helium or phosphate
fertiliser). The greater the percentage we try to recycle, so the energy cost increases
disproportionately. So whether the resources that we want to use are still in the ground or are in
circulation above ground, human industry will inevitably dissipate and lose those resources.
The more people we have on the planet, and the more energy we use, the faster and more
extensive is the degradation of Earths resources. Humanity is like a huge organic machine, using
energy to mine and deplete minerals. The more energy that is put into the system, the faster the
degradation occurs. Nuclear fusion energy, if it comes to be, might be particularly efficient at
degrading our resources and environment (one effect of such technology may be to convert our
lithium reserves into helium which will escape the Earths atmosphere and be lost forever).
Energy for human use is as unsustainable and non-renewable as mining. So to talk about
renewable energy or sustainable energy is an oxymoron, as is sustainable mining or
sustainable development. The more energy we use, the less sustainable is humanity. The
sooner that people realise this, the sooner we can embark on the process of reducing energy
consumption, rather than clutching at the straws of alternative energy sources to perpetuate the
unsustainable.
Quantifying Environmental Impact: Efficiency, E-factors, and Atom Economy
Everyone agrees that green chemistry and green manufacture are good things. The
websites and pamphlets of all the major chemical companies emphasize their concern for the
environment. They all say that their processes and products are efficient, green, and
environmentally friendly. But how should we compare these processes? How should we judge
such claims?
First, let us define some key terms. One method for quantifying a reactions
efficiency is by examining the reactant conversion, the product selectivity, and the
product yield over time. The reactant conversion is the fraction of reactant molecules
that have transformed to product molecules (regardless of which product it is). The
selectivity to product P is the fraction (or percentage) of the converted reactant
that has turned into this specific product P. The yield of P is simply conversion
selectivity. High conversions in short time spans mean smaller and safer reactors.
Similarly, high selectivity means less waste, and simpler and cheaper separation
units. Thus, conversion, selectivity, and yield are all measures of the reaction
efficiency.
In addition, there are specific rulers for measuring the greenness or eco friendliness
of processes and products. One such measure is the E-factor, introduced by Roger Sheldon in
1994. A reactions E-factor is the quotient kgwaste/kgproduct (here waste is everything formed in
the reaction except the desired product). The waste can be gases such as CO2 or NOx, water,
common
inorganic salts (e.g., NaCl, Na2SO4, or (NH4)2SO4), heavy metal salts, and/or
organic compounds. This is surprising, as we are used to thinking of such chemicals as
pollutants. In fact, E-factors increase substantially when going from bulk chemicals to fine
chemicals and specialties. This is partly because finechemicals production often involves
multistep syntheses, and partly because stoichiometric reagents are more often used for
producing
fine
chemicals
and
pharmaceuticals.
Atom economy
Generations of chemists, especially organic chemists, have been educated to devise
synthetic reactions to maximize yield and purity. Although these are worthy goals, reactions may
proceed in 100% yield to give a product of 100% purity and still produce more waste than
product. In simplistic terms, Equation 2.1:
A+BC+D+E
In which A and B react to give product C in high yield and high purity, also leads to
the formation of by-products (or waste) D and E in stoichiometric quantities. For many years
phenol was manufactured via the reaction of sodium benzene sulfonate (from benzene
sulfonation) with sodium hydroxide; the products of this reaction are sodium phenolate
(which is hydrolysed subsequently to phenol), sodium sulfite and water. Even if the reaction
proceeds in quantitative yield, it is evident from looking at the molecular weights of the product
(sodium phenolate) and unwanted by-products (sodium sulfite and water) that, in terms of
weight, the reaction produces more waste than product. Historically,however, the chemist would
not consider the production of this aqueous salt waste to be of any importance when designing
the process.
The atom economy concept proposed by Trost is one of the most useful tools
available for design of reactions with minimum waste. The concept is that for economic and
environmental reasons reactions should be designed to be atom efficient, i.e. as many of the
reacting atoms as possible should end up in useful products. In the example shown above all
the carbon atoms present in the starting material are incorporated into the product, giving a
carbon atom efficiency of 100%, but none of the sulfur ends up as useful product and hence the
atom efficiency for sulfur is 0%. Overall, the atom efficiency of the reaction is defined as the
ratio of the molecular weights of desired product to the sum of the molecular weights of all
materials produced in the process. In the above example the atom efficiency would be 116/260 or
44.6%.
Examining the E-factor for this reaction, we see that for every three moles
of benzophenone we produce one mole of chromium sulfate and six moles of water. The
molecular weight of benzophenone is 182.2 g mol1, so every kilogram of benzophenone contains
5.48 moles of benzophenone. This means that for every kilogram of benzophenone we generate
5.48/3 = 1.83 moles (or 0.717 kg) of
chromium sulfate and 10.98 moles (or 0.197 kg) of water. The overall Efactor is therefore given by Eq.
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Nearly a whole kilogram of waste for every kilogram of product! Remember, this is for
the ideal case of 100% yield and 100% selectivity. In real life, the E-factor is usually
much higher, because product yields are less than 100% and the reagents are often used in
excess. Furthermore, in many cases one needs to neutralize acid or base side products, so the
overall waste amounts are even higher.
The E-factor and atom economy can be used for comparing reaction alternatives,
but we should remember that there are different types of waste. The reaction example above has
two by-products: chromium sulfate and water. Obviously, water is GOOD WASTE, while
chromium sulfate is BAD WASTE, so evaluating a synthetic protocol on the basis of only the
amount of waste produced is insufficient. To solve this problem, Sheldon put forward the concept
of the environmental quotient. By multiplying the E-factor by Q, an arbitrarily assigned hazard
quotient, this measure takes both the amount and the nature of the waste into account.
Assigning absolute Q-values to waste streams is difficult, because cases differ
according to location and type of waste. Nevertheless, the EQ gives a better measure of the
environmental impact of a process than the E-factor or the atom economy alone.
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Green Metholodies
Propene oxide is an important bulk chemical, used for making propylene
glycol(propane-1,2-diol), polyethers, glycerol (propane-1,2,3-triol), and other products.
Currently there is no catalytic process for oxidizing propene directly to propene oxide using
molecular oxygen. The classic manufacturing route goes via chlorohydrin
The HCl by-product is neutralized with caustic soda or lime. Although this process
is wasteful and polluting, it still accounts for 40% of the global manufacture of propene oxide.
There are several alternatives to the polluting chlorohydrin route. One is the
styrene monomer propene oxide (SMPO) process, used by Shell and Lyondell.
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It is less polluting, but couples the epoxide production to that of styrene, a hugevolume product. Thus, this route depends heavily on the styrene market price. Another
alternative, the ARCO/Oxirane process, uses a molybdenum.
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Solvents
solvents are very useful. They can be used to
1. Place reagents into a common phase where they can
react
2. Dissolve solids so that they can be pumped from place to
place
3. Lower viscosity and facilitate mixing
4. Regulate temperatures of reactions by heating at reflux
5. Moderate the vigor of exothermic reactions
6. Allow recovery of solids by filtration or centrifugation
7. Extract compounds from mixtures
8. Purify compounds by recrystallization
9. Convert pyrophoric materials to nonpyrophoric solutions
(as for aluminum alkyls)
10. Remove azeotrope compounds from reactions
11. Clean equipment and clothing
12. Place a thin film of material on to a substrate
The disadvantages of solvents include the following:
1. Loss of 1015 million tons of solvents (with a fuel value
of 2 billion dollars) each year3
2. Reaction of lost solvents in air with nitrogen oxides in
sunlight to produce ground level ozone
3. Destruction of upper atmosphere ozone by chlorofluorocarbons
4. Toxicity of chlorinated and other solvents to workers
5. Miscarriages caused by ethers of ethylene glycol
6. Birth defects from exposure to solvents4
7. Fires and explosions that may result from use
8. Monetary cost
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.
There are many smaller commercial sources of solvent emissions, including
dry-cleaning shops, printing establishments, metal-cutting fluids in machine shops, auto body
repair shops, and many others. The consumers also emit solvents from their homes when they
use paint remover, oil-based paints, adhesives, spot remover, charcoal lighter fluid, aerosol
cans of personal care products, hair spray, nail polish, and gasoline-powered tools, among many.
The use of chlorinated solvents minimizes the risk of fire, but causes toxicity problems, such as
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liver damage and cancer. If other volatile solvents are used, all equipment in the plant must be
explosion-proof, which includes placing every electrical switch in a heavy metal container. The
limits being set on these volatile organic compound (VOC) emissions from various products
are the subject of some controversy in the United States.
A tiered approach to this problem from the least change
to the most change might be the following:
1. Place something on the plant outlet to destroy or recover the solvent.
2. Enclose the operation so that the solvent is not lost.
3. Substitute a less harmful solvent.
4. Use supercritical carbon dioxide (also written as sc carbon dioxide) as a solvent.
5. Use water.
6. Use no solvent.
7. Switch to another process that eliminates the need for
the solvent.
8. Can we do just as well without the product made with the
solvent?
For laboratory use and, perhaps, for small-volume production, another first stage can
be added. Microreactors, which require much less solvent, are being studied for fluorination,
DNA chips, and other uses.
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 Solvents and Alternative Methods
Green solvents have been characterized 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.
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Common or other otherwise valuable ionic liquid cations (a) and anions (b). R, alkyl group.
In the scientific literature there are a large number of research papers for the use
of ionic liquids in synthetic routes and various applications.
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Having said this, the low solubility of substrates in water is not always an unsurpassable
restriction, with several on-water reactions reported in the literature.
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.
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Biosolvents
An alternative approach to solvent substitution is to produce solvents from biomass. Not
only does this alleviate demand for depleting resources, but depending on the biomass used the
source can be replenished fairly rapidly and with little net pollution caused. Volatile bio-derived
solvents still retain the VOC hazards presented by many petroleum chemicals, and so this
solution is not comprehensive. The diversity of the potential feedstocks available but their
dissimilarity to petroleum means that a traditional organic solvent may not be feasibly supplanted
by an exact bio-derived version. However, the desirable physical properties characteristic of that
solvent will undoubtedly present themselves in the form of an easily accessible related
biosolvent.
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Of all the alternative reaction media, water has perhaps been used most extensively as
modifications to reagents are rarely required, and often the organic substrates do not even need to
be soluble in the aqueous phase for the reaction to proceed smoothly. Water has proven itself as a
very useful solvent for many types of reactions, including DielsAlder, aldol, other
carboncarbon
bond-forming
reactions
including
CH
activation
processes,
epoxidation reactions and alcohol oxidations. More recently, the hydrophobic effect has been
used in its most extreme form, where the organic substrates are hydrophobic and insoluble; such
reactions are said to proceed on water.
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bond network breaks down. In this temperature range, water can be called
high temperature, superheated or near critical (NCW). It has a lower polarity density, viscosity,
and surface tension than water at room temperature. However, (hydrogen bond acceptor
ability)
remains constant with changing temperature, and diffusivity and specific heat
capacity increase.