CHM 231 : Green Chemistry

Content:
- Concepts and principles for green chemistry. An introduction of the historical background
of Green Chemistry. Case-studies in Green and Environmental Chemistry (sustainable
development).
- Identification of issues that Green Chemistry could solve.
- Inorganic health- and environmental pollutants. Organic health- and environmental
pollutants.
What is Green Chemistry?
Green chemistry (sometimes referred to as sustainable chemistry) is the branch of chemistry that
deals with the design and optimization of processes and products in order to lower, or remove
altogether, the production and use of toxic substances. Green chemistry is not the same as
environmental chemistry.
The former focuses on the environmental impact of chemistry and the development of sustainable
practices that are environment-friendly (such as a reduction in the consumption of non-renewable
resources and strategies to control environmental pollution. The latter focuses on the effects that
certain toxic or hazardous chemicals have on the environment.
Green chemistry is not a new branch of chemistry, merely a different way of approaching the
design and development of products and processes
Historical background of Green Chemistry
During the twentieth century chemistry changed the way we live forever. Perhaps the greatest
perceived benefits, to the general public, have come from the pharmaceuticals industry with
developments of painkillers, antibiotics, heart drugs and targeted cancer drugs. However, it is
difficult to think of an important facet of modern life that has not been transformed by products of
the chemical and related industries, for example.
 Transportation – production of gasoline and diesel from petroleum and more recently
crops, fuel additives for greater efficiency and reduced emissions, catalytic converters,
plastics to reduce vehicle weight and improve energy efficiency.
 Clothing – man-made fibres such as rayon and nylon, dyes, waterproofing and other surface
finishing chemicals.
 Sport – advanced composite materials for tennis and squash rackets, all-weather surfaces,
textiles that let the body breathe and reduce wind resistance.
 Safety – lightweight polycarbonate cycle helmets, fire-retardant furniture, air bags.
 Food – refrigerants, packaging, containers and wraps, food processing aids and
preservatives.
  Health – chlorine for clean water supplies, blood bags, internal stitches that dissolve,
anaesthetics, disinfectants, vaccines, dental fillings, artificial joints, contact lenses,
contraceptives.
 Office – photocopying toner, inks, printed circuit boards, liquid crystal displays.
 Home – material and dyes for carpets, plastics for TVs, and mobile phones, CDs, paints,
detergents and self-cleaning windows.
 Farming – fertilisers, pesticides.
The value of the chemical industry is over 3000 billion Euro (Figure 1.1) with Asian production
and China in particular accounting for most of this. In Europe, 1.3 million people are directly
employed by the industry, and around 4 million including the supply chain and service sector.
Figure 1.1

Value of the global chemical industry.

In many countries, however, the chemical industry is often viewed, by the general public, as
causing more harm than good. There are several reasons for this including general ignorance of
the end use and value of the industry’s products, since the chemical industry rarely sells to the end
consumer. However, a major reason is that the industry is perceived as being polluting and causing
significant environmental damage. Although a very safe industry in general, well-publicised
disasters, such as Bhopal and Deepwater Horizon in the oil sector, causing both environmental
damage and loss of life have led to this generic view. As well as specific disasters, general pollution
that came to the public’s attention in the 1960s and 1970s through eutrophication, foaming rivers,
the discovery of persistent organic pollutants, and the famous ‘burning’ Cuyahoga river, have all
played a part in formulating this view of the chemical industry.
Chemists and engineers engaged in development of chemical products and processes have never
set out to cause damage to the environment or human health. Undoubtedly, risk taking and the
pressures to meet production targets and reduce cost have played their part but many early
incidents occurred largely through a lack of knowledge. In particular, the longer-term effects of
products entering the environment were not widely recognised until relatively recently. The
challenge for the chemical industry in the twenty-first century is to continue to provide the benefits
we have come to rely on, in an economically viable manner, but without the adverse environmental
side effects. This can be achieved through development of more environmentally benign products
using less hazardous processes and raw materials. With global warming being accepted as the
biggest environmental challenge we face, the chemical industry must also develop more energy-
efficient processes and reduce its reliance on fossil fuels. Nevertheless, the chemical industry is
also a solution provider for climate change with 3 tonnes of CO 2 being saved in downstream use
for every tonne of CO2 used in manufacture. In particular, products such as fuel additives and
insulation play a huge role in helping move towards a lower-carbon society.

Sustainable Development and Green Chemistry

Current thinking on sustainable development came out of a United Nations Commission on
Environment and Development in 1987 (Bruntland Commission), which defined sustainable
development as:
“…meeting the needs of the present without compromising the ability of future generations to meet
their own needs.”
Although the ideals on which sustainable development is based are not new, indeed Thomas
Jefferson made similar comments in 1789, the Bruntland commission did catalyse the
sustainability debate. Since 1987 governments, NGOs, society in general and industry sectors have
considered what sustainable development really means and how best to start to achieve it from
their own standpoint. Issues that will have a significant impact on how the move towards
sustainability is approached, include time scale, likely future technology developments, and
population forecasts. Two of the key aspects of sustainable development from a chemicals and
energy perspective are: how fast should we use up fossil fuels and how much ‘waste’ or pollution
can we safely release to the environment? There are no agreed answers to these questions but there
is general agreement to develop more renewable forms of energy and to reduce pollution.
The Natural Step, an international movement, started in Sweden, dedicated to helping society
reduce its impact on the environment, has developed four system conditions for sustainability:
a. Materials from the earth’s crust (e.g. heavy metals) must not systematically increase in
nature.
b. Persistent substances produced by society (e.g. DDT, CFCs) must not systematically
increase.
 c. The physical basis for the earth’s productive natural cycles must not be systematically
deteriorated.
d. There must be fair and efficient use of resources with respect to meeting human needs.
This approach recognises that the earth does have a natural capacity for dealing with much of the
waste and pollution that society generates, it is only when that capacity is exceeded that we become
unsustainable.
During the early 1990s the US Environmental Protection Agency (EPA) coined the phrase Green
Chemistry ‘To promote innovative chemical technologies that reduce or eliminate the use or
generation of hazardous substances in the design, manufacture and use of chemical products.’
Over the last 20 years Green Chemistry has gradually become recognised as both a culture and a
methodology for achieving sustainability. Green Chemistry is not a new branch of chemistry but
an approach to carrying out chemistry and engineering in a sustainable manner.

The 12 Key Principles of Green Chemistry

The twelve principles put forward by the American chemists Paul Anastas and John Warner in the
year 1998 to lay the foundation for green chemistry are listed below.
 Prevention of waste: Preventing the formation of waste products is always preferable to
the clean-up of the waste once it is generated.
 Atom economy: The synthetic processes and methods that are devices through green
chemistry must always try to maximise the consumption and incorporation of all the raw
materials into the final product. This must strictly be followed in order to minimise the
waste generated by any process.
 Avoiding the generation of hazardous chemicals: Reactions and processes that involve
the synthesis of certain toxic substances that pose hazards to human health must be
optimised in order to prevent the generation of such substances.
 The design of safe chemicals: During the design of chemical products that accomplish a
specific function, care must be taken to make the chemical as non-toxic to humans and the
environment as possible.
 Design of safe auxiliaries and solvents: The use of auxiliaries in processes must be
avoided to the largest possible extent. Even in the circumstances where they absolutely
need to be employed, they must be optimized to be as non-hazardous as possible.
 Energy efficiency: The amount of energy consumed by the process must be minimized to
the maximum possible extent.
 Incorporation of renewable feedstock: The use of renewable feedstock and renewable
raw materials must be preferred over the use of non-renewable ones.
  Reduction in the generation of derivatives: The unnecessary use of derivatives must be
minimalized since they tend to require the use of additional reagents and chemicals,
resulting in the generation of excess waste.
 Incorporation of Catalysis: In order to reduce the energy requirements of the chemical
reactions in the process, the use of chemical catalysts and catalytic reagents must be
advocated.
 Designing the chemicals for degradation: When designing a chemical product in order
to serve a specific function, care must be taken during the design process to make sure that
the chemical is not an environmental pollutant. This can be done by making sure that the
chemical breaks down into non-toxic substances.
 Incorporating real-time analysis: Processes and analytical methodologies must be
developed to the point that they can offer real-time data for their monitoring. This can
enable the involved parties to stop or control the process before toxic/dangerous substances
are formed.
 Incorporation of safe chemistry for the prevention of accidents: While designing
chemical processes, it is important to make sure that the substances that are used in the
processes are safe to use. This can help prevent certain workplace accidents, such as
explosions and fires. Furthermore, this can help develop a safer environment for the process
to take place in.
Examples of the Impact of Green Chemistry
Use of Green Solvents
Many chemical synthesis reactions that are carried out on an industrial scale require large amounts
of chemical solvents. Furthermore, these solvents are also used industrially for degreasing and
cleaning purposes. However, many traditional solvents that have been used for such purposes in
the past are known to be toxic to human beings. Some such solvents are also known to be
chlorinated.
Examples of green solvents.
Common examples of solvents include water, ethanol, methanol and acetone. The term ‘solvent’
can be defined as a substance that has the ability to dissolve a given solute to form a solution with
it. Although solvents are mostly used in the liquid state, it is possible for solvents to exist in the
solid and gaseous phases as well. Some common examples of solvents are listed below.
 Water
 Ethanol
 Methanol
 Acetone
 Toluene
  Methyl acetate
 Ethyl acetate
 Hexane
 Benzene
Water
Water is a polar, protic solvent with the chemical formula H 2O. Water has the ability to dissolve a
large variety of substances. This is the reason why it is regarded as a good solvent. Furthermore,
water is often referred to as the “universal solvent” because it is known to dissolve more substances
than all other liquid solvents. Water is crucial to every living organism on the planet Earth. As
water travels across the water cycle, through the ground and through the bodies of living
organisms, it transports several valuable minerals and nutrients with it.
Ethanol
Ethanol is considered by many to be a very versatile solvent. This organic compound forms
miscible mixtures with water and several other organic solvents such as benzene, acetone, ethylene
glycol, chloroform, toluene, glycerol, nitromethane, carbon tetrachloride, pyridine and diethyl
ether. This compound is also miscible with many light aliphatic hydrocarbons. Some examples
include pentane and hexane. Aliphatic chlorides such as tetrachloroethylene are also miscible with
ethanol.
Methanol
Methanol is an organic compound with the chemical formula CH 3-OH. This compound is also
referred to as methyl alcohol. Methanol is mainly used as an industrial solvent to help in the
manufacture of resins, inks, colours and adhesives. This compound is also used in the processing
of essential pharmaceutical ingredients and products such as cholesterol, vitamins, streptomycin
and hormones as a solvent.
Acetone
Due to its ability to dissolve both polar and nonpolar compounds, acetone is considered by many
to be a very good solvent (most other solvents can only dissolve either polar or non-polar
compounds). Furthermore, acetone is a strong solvent because it is a miscible material. This means
that it has the potential to mix in certain amounts with water. Acetone is used in a number of
important organic reactions (such as nucleophilic substitution reactions) as a polar, aprotic solvent.
The use of acetone solvent is also vital in the Jones oxidation reaction (an important named reaction
for the conversion of secondary alcohols into ketones). It is important to note that this compound
does not form an azeotrope with water

The advancement of green chemistry has brought many alternatives to these toxic solvents. The
green solvents that are coming up as alternatives are known to be derived from renewable sources
and are also known to be biodegradable. Thus, green chemistry has great potential to lower the
toxicity of certain industrial environments by developing safer alternatives.

Development of Specialized Synthetic Techniques

The development of specialized synthetic techniques can optimize processes in order to make them
more environmentally friendly by making them adhere to the principles of green chemistry. An
important example of such an enhanced synthetic technique is the development of the olefin
metathesis reaction in the field of organic chemistry. This reaction, developed by Robert Grubbs,
Richard Schrock, and Yves Chauvin, won the Nobel Prize for Chemistry in the year 2005.
Other notable developments brought forward by advancements in green chemistry include:
 The employment of supercritical carbon dioxide as a green solvent (as an alternative to
other toxic solvents).
 Incorporating the use of hydrogen in enantioselective synthesis reactions (also known as
asymmetric synthesis).
 Incorporating aqueous solutions of hydrogen peroxide (a chemical compound with the
formula H2O2) to drive relatively clean oxidation reactions.
Other notable applications of green chemistry include supercritical water oxidation (often
abbreviated to SCWO), dry media reactions (also known as solid-state reactions and solvent fewer
reactions), and on water reactions.
Production of Hydrazine
Initially, the most popular method for the production of hydrazine (an inorganic chemical
compound with the chemical formula N2H4) was the Olin Raschig process, which involved the use
of ammonia and sodium hypochlorite. However, with the development of green chemistry, a more
environment-friendly alternative to this process was discovered.
In the peroxide process for the production of hydrazine, ammonia is reacted with hydrogen
peroxide. In this alternate method, water is produced as the only side product. It can also be noted
that the peroxide process does not require any auxiliary extracting solvents.

Organic and Inorganic health- and environmental pollutants.

Chemical Pollutants
Chemical pollution from agriculture, industry, cities, and mining threatens global water quality.
Air pollutants from these activities can also enter bodies of water (and become water pollutants)
through dry deposition, precipitation, and runoff. Some chemical pollutants have serious and well-
known health effects, whereas many others have poorly known long-term health effects.
Any natural water contains dissolved chemicals, some of which are important human nutrients
while others can be harmful to human health. The concentration of a water pollutant is commonly
given in very small units such as parts per million (ppm) or even parts per billion (ppb). An arsenic
concentration of 1 ppm means 1 part of arsenic per million parts of water. This is equivalent to one
drop of arsenic in 50 liters of water. To give you a different perspective on appreciating small
concentration units, converting 1 ppm to length units is 1 cm (0.4 in) in 10 km (6 miles) and
converting 1 ppm to time units is 30 seconds in a year. Total dissolved solids (TDS) represent the
total amount of dissolved material in water. Average TDS values for rainwater, river water, and
seawater are about 4 ppm, 120 ppm, and 35,000 ppm, respectively.
Organic Pollutants
Organic pollutants include herbicides and pesticides, pharmaceuticals, fuel (such as oil spills),
industrial solvents and cleansers, and synthetic hormones associated with pharmaceuticals. These
synthetic hormones can act as endocrine disruptors. Many are persistent organic
pollutants (POPs), which are long-lived in the environment, biomagnify through the food chain,
and can be toxic. As previously mentioned, DDT (pesticide), dioxin (herbicide by-product), and
PCBs (polychlorinated biphenyls, which were used as a liquid insulator in electric transformers),
are all POPs.
An example of organic chemical contamination is the Love Canal, in Niagara Falls, New York
From 1942 to 1952, the Hooker Chemical Company disposed of over 21,000 tons of chemical
waste, including chlorinated hydrocarbons, into a canal and covered it with a thin layer of clay.
Chlorinated hydrocarbons are a large group of organic chemicals that have chlorine functional
groups, most of which are toxic and carcinogenic to humans (DDT and PCBs are an example.) The
company sold the land to the New York School Board, who developed it into a neighborhood.
After residents began to suffer from serious health ailments and pools of oily fluid started rising
into residents’ basements, the neighborhood had to be evacuated. This site became a U.S.
Environmental Protection Agency Superfund Site, a site with federal funding and oversight to
ensure its cleanup.
 Classes of Persistent Organic pollutant

Inorganic Pollutants
Inorganic pollutants include nutrients like nitrate (NO3-) and phosphate (PO43-), heavy metals,
chloride (Cl-), and radioactive isotopes released from mining or nuclear accidents (such as cesium,
iodine, uranium, and radon gas). Nutrients can be from geologic material, like phosphorus-rich
rock, but are most often sourced from fertilizer and animal and human waste.
Untreated sewage and agricultural runoff concentrate nitrogen and phosphorus which are essential
for the growth of microorganisms. Nutrients like nitrate and phosphate in surface water can
promote the growth of microbes, like blue-green algae (cyanobacteria), which in turn deplete
dissolved oxygen (O2) and produce toxins. This process is known as eutrophication .
Typically, inorganic pollutants are the compounds of inorganic by-products arising due to
radiant energy and noise, heat, or light. Generally, inorganic pollutants include arsenic,
cadmium, lead, mercury, chromium, aluminum, nitrates, nitrites, and fluorides.
Examples Inorganic compounds
Heath Effect of organic and inorganic pollutant

Oxygen-demanding waste is an extremely important pollutant to ecosystems. Most surface water

in contact with the atmosphere has a small amount of dissolved oxygen, which is needed by aquatic
organisms for cellular respiration. Decomposers, such as bacteria and fungi, also conduct cellular
respiration and consume oxygen as they break down dead organic matter.
Too much decaying organic matter in water is a pollutant because it removes oxygen from water,
which can kill fish, shellfish, and aquatic insects. The amount of oxygen used by aerobic (in the
presence of oxygen) decomposition of organic matter is called biochemical oxygen
demand (BOD). The major source of dead organic matter in many natural waters is sewage; grass
and leaves are smaller sources.

Green Solution to Chemical Pollutants