GREEN CHEMISTRY

SUBMITTED BY:MONIKA SHARMA COMPUTER SCIENCE AND ENGINEERING

INDEX

1. 2. 3. 4.

Introduction Milestones Why do we need green chemistry? Principles of green chemistry 5. Atom Economy - Synthesis of Ibuprofen and Producing Carbaryl 6. Ionic Liquids Green Solvents 7. Examples of green chemistry
1) 2) 3) 4) 5) 6) 7) 8) Extraction of D-Limonene Manufacture of Sodium-hypochlorite ( bleach) Production of allyl alcohol Production of polycarbonate (polymer) Production of styrene Reducing lead Pollution Putting out fires Safer dry cleaning

8. Uses of green chemistry 9. Benefits of green chemistry 10.Green Chemistry Projects 11. Bibliography

GREEN CHEMISTRY INTRODUCTION

Green chemistry is also known as environmentally benign chemistry, or sustainable chemistry. Perhaps the most widely accepted definition of green chemistry is the one offered by chemists Paul Anastas and John Warner, who defined green chemistry as the design of chemical products and processes that reduce or eliminate the use and generation of hazardous substances. As a chemical philosophy , green chemistry applies to organic chemistry,inorganic chemistry,biochemistry,analytical chemistry , and even physical chemistry.While green chemistry seems to focus on industrial applications,it does apply to any chemistry choice.Click chemistry is often cited as a style of chemical synthesis that is consistent with the goals of green chemistry.The focus is on minimizing the hazard and maximizing the efficiency of any chemical choice.It is distinct from environmental chemistry which focuses on chemical phenomena in the environment. In 2005 Ryoji Noyori identified three key developments in green chemistry: use of supercritical carbon dioxide as green solvent, aqueous hydrogen peroxide for clean oxidations and the use of hydrogen in asymmetric synthesis. Examples of applied green chemistry are supercritical water oxidation, on water reactions, and dry media reactions. 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. There is some debate as to whether green chemistry includes a consideration of economics, but by definition, if green chemistry is not applied, it cannot accomplish the reduction in the "use or generation of hazardous substances." Green chemistry is applicable to all aspects of the product life cycle as well. Finally, the definition of green chemistry includes the term hazardous. It is important to note that green chemistry is a way of dealing with risk reduction and pollution prevention by addressing the intrinsic hazards of the substances rather than those circumstances and conditions of their use that might increase their risk. Why is it important for green chemistry to adopt a hazard-based approach? To understand this, we have to revisit the concept of risk. Risk, in its most fundamental terms, is the product of hazard and exposure: Risk = Hazard X Exposure A substance manifesting some quantifiable hazard, together with a quantifiable exposure to that hazard, will allow us to calculate the risk associated with that substance. Virtually all common approaches to risk reduction focus on reducing exposure to hazardous substances. Regulations often require increases in control technologies and treatment technology, and in personal protective equipment such as respirators, gloves, etc., in order to reduce risk by restricting exposure. By achieving risk reduction through hazard reduction, green chemistry addresses concerns about the cost and potential for failure of exposure controls. Regardless of the type of

exposure control, ranging from engineering controls through personal protective gear, there is always going to be an upfront capital cost; to what degree this cost can be recouped will be situation-specific, but it will always be there. In contrast, there is no additional upfront capital cost necessarily associated with green chemistry. While some green chemistry options may require capital investment, others may actually lower total cost of operations from the outset. This result is frequently the case in some of the easiest ways of implementing green chemistry technologies. Exposure controls, because they rely on either equipment or human activity to accomplish their goals, are capable of failing. Respirators can rupture, air scrubbers can break down, and so forth. When failure occurs, risk is maximized because the resultant exposure is to a constant hazard. Green chemistry, in contrast, does not rely on equipment, human activity, or circumstances of use but, instead, changes the intrinsic hazard properties of the chemical products and transformations. Consequently, green chemistry is not as vulnerable to failure, as are the traditional approaches to hazard control. The definition of green chemistry also illustrates another important point about the use of the term hazard. This term is not restricted to physical hazards such as explosiveness, flammability, and corrosibility, but certainly also includes acute and chronic toxicity, carcinogenicity, and ecological toxicity. Furthermore, for the purposes of this definition, hazards must include global threats such as global warming, stratospheric ozone depletion, resource depletion and bioaccumulation, and persistent chemicals. To include this broad perspective is both philosophically and pragmatically consistent. It would certainly be unreasonable to address only some subset of hazards while ignoring or not addressing others. But more importantly, intrinsically hazardous properties constitute those issues that can be addressed through the proper design or redesign of chemistry and chemicals.

MILESTONES
The Pollution Prevention Act of 1990 set the stage for green chemistry: Its focus is the prevention of pollution at the source rather than the treatment of pollutants after they are formed. This goal became a formal objective of the Environmental Protection Agency (EPA) in 1991. Anastas coined the term "green chemistry" the same year. Two of the most prominent and early advocates of green chemistry were Kenneth Hancock of the National Science Foundation (NSF) and Joe Breen, who after twenty years of service at the EPA then became the first director of the Green Chemistry Institute (GCI) during the late 1990s. Anastas and Warner formulated the twelve principles of green chemistry in 1998. These serve as guidelines for chemists seeking to lower the ecological footprint of the chemicals they produce and the processes by which such chemicals are made.

Starting in 1996, outstanding examples of green chemistry have been recognized in the United States each year by the Presidential Green Chemistry Challenge (PGCC) awards. These are the only awards in chemistry that are bestowed at the presidential level. The EPA and the American Chemical Society (ACS) have played a major role in promoting research and development, as well as education, in green chemistry. In 2000 the GCI became a partner of the ACS. Chemical societies around the globe have recognized the importance of green chemistry and promote it through journals, conferences, educational activities, and the formation of GCI chapters. There are GCI chapter affiliates all over the world.

Why do we need Green Chemistry ?

1.Chemistry is undeniably a very prominent part of life. 2.Chemical developments also bring environmental problems and harmful side effects,which result in the need of greener chemical products.A famous example is the pesticide DDT. 3.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. 4.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. 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.

THE TWELVE PRINCIPLES OF GREEN CHEMISTRY

Paul Anastas and John C.Warner developed 12 principles of green chemistry ,which help to explain what the definitions mean in practice. 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 safe, environment-benign substances, including solvents, whenever possible; the design of energy efficient processes; the best form of waste disposal: not to create it in the first place.

Principles are the following :Prevention It is better to prevent waste than to treat or clean up waste after it has been created.

Atom economy Synthetic methods should be designed to maximize the incorporation of all materials used in the process into the final product.

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.

Designing safer chemicals Chemical products should be designed to effect their desired function while minimizing their toxicity.

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.

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.

Use of renewable resources A raw material or feedstock should be renewable rather than depleting wherever technically and economically practicable.

Reduce derivatives. Unnecessary derivatization (blocking group, protection/ deprotection, temporary

modification) should be avoided whenever possible.

Catalysis Catalytic reagents (as selective as possible) are superior to stoichiometric reagents.

Biodegradability Chemical products should be designed so that at the end of their function they do not persist in the environment and break down into innocuous degradation products.

Real-time -analysis for pollution prevention Analytical methodologies need to be further developed to allow for real-time, in-process monitoring and control prior to the formation of hazardous substances.

Inherently safer chemistry for accident prevention Substances and the form of a substance used in a chemical process should be chosen to minimize potential for chemical accidents, including releases, explosions, and fires

ATOM ECONOMY

Atom economy (atom efficiency) describes the conversion efficiency of a chemical process in terms of all atoms involved. In an ideal chemical process, the amount of starting materials or reactants equals the amount of all products generated (see stoichiometry) and no atom is wasted. Recent developments like high raw material (such as petrochemicals) costs and increased sensitivity to environmental concerns have made atom economical approaches more popular. Atom economy is an important concept of green chemistry philosophy. Atom economy can be written as: % atom economy =

Note that atom economy can be poor even when chemical yield is near 100%, see for instance the Cannizzaro reaction. A Diels-Alder reaction is an example of a potentially very atom efficient reaction. On the other hand if the desired product has an enantiomer the reaction needs to be sufficiently stereoselective even when atom economy is 100%. The Gabriel synthesis of amines is an example of extremely low atom economy, as stochiometric quantities of phthalic acid derivatives are formed. In most cases, the atom economy of the Gabriel synthesis is <<50%. Atom economy can also be adjusted if a pendant group is recoverable, for example Evans auxiliary groups. However, if this can be avoided it is more desirable, as recovery processes will never be 100%. Atom economy can be improved upon by careful selection of starting materials and a catalyst system. Atom economy is just one way to evaluate a chemical process. Other criteria can include energy consumption, pollutants released and price.

ATOM ECONOMY INVOLVED IN SYNTHESIS OF IBUPROFEN

Original synthesis of Ibuprofen 40 % Atom Economy

Improved Synthesis of Ibuprofen

77 % Atom Economy

ATOM ECONOMY INVOLVED IN PRODUCING CARBARYL

Conventional Method :The method used by Union Carbyde for producing carbaryl (in
India) is methyl isocyanate + -naphtol carbaryl Economics: Methyl isocyanate (57 grams/mole) purchased at $2.50/kg -naphtol (144 grams/mole) purchased at $3.99/kg Carbaryl (201 grams/mole) sold at $5.81/kg Profit per kg of carbaryl = $5.81 - $2.50 x 0.057 x 4.98 - $3.99 x 0.144 x 4.98 = $5.81 - $0.71 - $2.86 = $2.24

Green Method : The optimum from an environmental perspective, and one that does not
use methyl-isocyanate, is methyl formamide + -naphtol carbaryl + hydrogen Economics: Methyl formamide (59 grams/mole) purchased at $1.54/kg -naphtol (144 grams/mole) purchased at $3.99/kg Hydrogen (2 grams/mole) sold at $0.10/kg Carbaryl (201 grams/mole) sold at $5.81/kg Profit per kg of carbaryl = $5.81 + ($0.10 x 0.002 - $1.54 x 0.059 - $3.99 x 0.144) x 4.98 = $5.81 + $0.001 - $0.45 - $2.86 = $2.50

IONIC LIQUIDS -GREEN SOLVENTS

A solidified ionic liquid

An ionic liquid is a salt in which the ions are poorly coordinated, which results in these solvents being liquid below 100C, or even at room temperature (room temperature ionic liquids, RTIL's). At least one ion has a delocalized charge and one component is organic, which prevents the formation of a stable crystal lattice. The methylimidazolium and pyridinium ions have proven to be good starting points for the development of ionic liquids:

Properties, such as melting point, viscosity, and solubility of starting materials and other solvents, are determined by the substituents on the organic component and by the counterion.

Many ionic liquids have even been developed for specific synthetic problems. For this reason, ionic liquids have been termed "designer solvents". One of the first RTILs was a mixture of [emim]Cl with AlCl3 forming a series of equilibria between [emim][AlCl4], [emim][Al2Cl7], and [emim][Al3Cl10]. This RTIL is not water stable. The discovery of water-insoluble RTILs such as [bmim][PF6] allowed the development of new work-up methods, including the separation of water-soluble byproducts by simple extraction. Some transition metal catalysts that are soluble in ionic liquids may be recycled together with the ionic liquid, after extraction with water and the non-polar organic solvent used for product separation. The catalyst and ionic liquid may be recycled several times. In addition, the following RTIL, derived from fructose (a renewable feedstock), is a promising solvent for implementing fully "green" chemistry methods:

This ionic liquid was proven to be suitable for Heck Reactions:

The absence of volatility is one of the most important benefits of ionic liquids, offering a much lower toxicity as compared to low-boiling-point solvents. Ionic liquids can also make for safer microwave synthesis methods, because sudden pressure surges are not possible. The dipole characteristics of ionic liquids translate into rapid excitation by microwaves, and consequently faster reactions. CONCLUSIONS The range of reactions in ionic liquids gives a flavour of what can be achieved in these neoteric solvents.Because the properties and behavior of the ionic liquid can be adjusted to suit an individual reaction type, they can truly be described as designer solvents. We have shown that, by choosing the correct ionic liquid, high product yields can be obtained, and a reduced amount of waste can be produced in a given reaction. Often the ionic liquid can be recycled, and this leads to a reduction of the costs of the processes. It must be emphasized that reactions in ionic liquids are not difficult to perform and usually require no special

apparatus or methodologies. The reactions are often quicker and easier to carry out than in conventional organic solvents.

EXAMPLES

Example 1 : Extraction 0f D-Limonene Super critical CO2 is a very good solvent to extract various natural materials. Since especially designed equipment for supercritical CO2 generation is very expensive and intricate an effective yet affordable alternative in chemistry labs of schools and colleges is liquid CO2. It is useful as a green solvent because it provides environmental and safety advantages. It is nonflammable, relatively non-toxic readily available and environmentally benign. Processing with liquid CO2 also results in minimal liability in the event of unintentional release or residual solvent in the product. Due to solubility properties, less toxicity and ease of removal of CO2 have lead to extraction of various food products, essential oils, decaffeination of coffee etc. Essential oils are organic compounds that are extracted from natural sources and used in many products such as flavoring, fragrance and cleaning products etc. Many o these oils are classified as terpenes and terpenoids(oxygenated derivatives of terpenes). Conventional method of preparation: In many organic teaching laboratories, D-Limonene is extracted through a solvent extraction process with pentane or methylene chloride or by steam distillation. Green method of preparation: In this experiment the optically active enantiomer D-Limonene is extracted from peel of oranges and other citrus fruits (lemon) using CO2. D-Limonene is the major component of orange oil, which is found in the outer, colored portion of peels of oranges. The greenness of the liquid carbon dioxide extraction can be compared with different extraction procedures through the evaluation of waste, purity, energy used, yield and safety.

Example 2 : Manufacture of sodium hypochlorite (bleach)

The conventional way, known as the Berthollet method, is by reacting chlorine gas (Cl2) with caustic soda (NaOH). The reaction is Cl2 + 2 NaOH NaOCl + NaCl + H2O This method is somewhat dangerous because, on an industrial scale, it requires the storage of large quantities of chlorine gas, which is poisonous and has been used a chemical weapon. The safer way is to create a concentrated brine solution by dissolving salt (NaCl) in softened water (H2O) and passing electricity through this solution. Sodium hypochlorite (NaOCl) then forms in the water. A by-product is hydrogen gas (H2), which is highly flammable and explosive

Example 3 : Production of allyl alcohol CH2=CHCH2OH

Traditional route: Alkaline hydrolysis of allyl chloride, which generates the product and hydrochloric acid as a by-product CH2=CHCH2Cl + H2O CH2=CHCH2OH + HCl problem product Greener route: to avoid chlorine: Two-step using propylene (CH2=CHCH3),acetic acid (CH3COOH) and oxygen (O2) CH2=CHCH3 + CH3COOH + O2 CH2=CHCH2OCOCH3 + H2O CH2=CHCH2OCOCH3 + H2O CH2=CHCH2OH + CH3COOH Added benefit: The acetic acid produced in the 2nd reaction can be recovered and used again for the 1st reaction, leaving no unwanted by-product.

Example 4 : Production of polycarbonate (polymers)

Traditional route: Start with phosgene (COCl2), which is extremely toxic, and end with methyl chloride (CH2Cl), which is harmful, as a by-product. COCl2 + Biphenol A + NaOH Polycarbonate + H2O + CH2Cl

Greener route : to avoid phosgene: Biphenol A + Diphenylcarbonate Polycarbonate

Example 5 : Production of styrene (= benzene ring with CH=CH2 tail)

Traditional route: Two-step method starting with benzene, which is carcinogenic and ethylene to form ethylbenzene, followed by dehydrogenation to obtain styrene.

Greener route: To avoid benzene, start with xylenes (cheapest source of aromatics and environmentally safer than benzene). Another option: still under development, is to start with toluene (benzene ring with CH3 tail).

Example 6. Reducing Lead Pollution

Lead Pollution has been decreased by Replacing lead in paint with safe alternative. Replacing tetra-ethyl lead with less toxic additives such as lead-free gasoline.

Example 7.Putting out fires the green way

Conventional method : Chemical foams to fight fires: Millions of tons of chemical fire-fighting foams used worldwide have discharged toxic substances into the environment, contaminating water supplies and depleting the ozone layer.

Green method : A new foam called Pyrocool FEF has now been invented to put out fires effectively without producing the toxic substances found in other fire-fighting materials.

Example 8 : Safer Dry Cleaning

Conventional method: Chemicals for Dry cleaning Perchloroethylene (perc) is the solvent most widely used in dry cleaning clothing. Perc is suspected of causing cancer and its disposal can contaminate ground water. Green method : Liquid CO2 can be used as a safer solvent if a wetting agent is used with it to dissolve grease. This method is now being used commercially by some dry cleaners.

MAJOR USES OF GREEN CHEMISTRY

ENERGY
The vast majority of the energy generated in the world today is from non-renewable sources that damage the environment. Carbon dioxide Depletion of Ozone layer Effects of mining, drilling, etc Toxics

Green Chemistry will be essential in the alternatives for energy generation (photovoltaics, hydrogen, fuel cells, biobased fuels, etc.) as well as continue the path toward energy efficiency with catalysis and product design at the developing forefront.

GLOBAL CHANGE
Concerns for climate change, oceanic temperature, stratospheric chemistry and global distillation can be addressed through the development and implementation of green chemistry technologies.

RESOURCE DEPLETION
Due to the over utilization of non-renewable resources, natural resources are being depleted at an unsustainable rate. Fossil fuels are a central issue. Renewable resources can be made increasingly viable technologically and economically through green chemistry. Biomass Nanoscience & technology Solar Carbon dioxide Chitin Waste utilization

FOOD SUPPLY

While current food levels are sufficient, distribution is inadequate Agricultural methods are unsustainable Future food production intensity is needed. Green chemistry can address many food supply issues. Green chemistry is developing: Pesticides which only affect target organisms and degrade to innocuous by-products. Fertilizers and fertilizer adjuvants that are designed to minimize usage while maximizing effectiveness. Methods of using agricultural wastes for beneficial and profitable uses.

TOXICS IN THE ENVIRONMENT

Substances that are toxic to humans, the biosphere and all that sustains it, are currently still being released at a cost of life, health and sustainability. One of green chemistrys greatest strengths is the ability to design for reduced hazard.

BENEFITS OF GREEN CHEMISTRY

Businesses producing and using chemicals face increasingly stringent environmental legislation and a growing list of restricted substances and materials. Applying the principles of green chemistry can help your business to comply with existing and future legal requirements. This can enable you to gain a competitive advantage over your competitors by being the first to market. There is increasing pressure from your business' stakeholders to supply products that have less impact on human health and the environment. Your stakeholders can include customers, the local community, your supply chain, investors, insurers and regulatory authorities. Marketing your improved environmental performance can help you to raise your business' profile and increase sales. Other business benefits of green chemistry include:

improved resource efficiency and lower raw material and utility bills reduced waste treatment and disposal costs ability to capitalise on the environmental technology marketplace by designing new, 'greener' products improved health and safety for staff and customers

Environmental benefits include:

fewer raw materials and natural resources used lower levels of chemicals released to the environment cleaner production technologies reduced emissions and product impacts smaller quantities of hazardous waste to be treated and disposed of

GREEN CHEMISTRY PROJECTS

2006 -- Assessment of Environmentally Benign Photopolymers as an Alternative to the Use of Formaldehyde Based Textile Finishing Agents - Prof. John Warner, UMass Lowell Department of Plastics Engineering. 2003 -- Solvent-Free Synthesis of Phthalocyanines - Prof. Daniel Sandman, UMass Lowell, Chemistry Department, 2001 --Synthesis of Conjugated Polymers and Molecules Using Sugar Reagents and Solventless Reactions - Prof. Daniel J. Sandman, UMass Lowell, Department of Chemistry. 2000 -- Environmentally Benign Control of Polymer Solubility: Photoresist Materials Using DNA Mimics - Prof. John C. Warner, UMass Boston, Department of Chemistry. 1999 -- Enzymatic Synthesis of Non-Formaldehyde Phenolic Polymers: Control of Hydrogen Peroxide Concentration - Prof. Kenneth Marx, UMass Lowell, Department of Chemistry. 1999 -- Green Chemistry: Solubility Characterization of Molecular Self Assemblies Prof. John Warner, UMass Boston, Department of Chemistry. 1998 -- Green Chemistry: Computational Evaluation of Hydroquinone Non-Covalent Derivatives - Prof. John Warner, UMass Boston, Department of Chemistry Replace chromium in corrosion protection requires development of new redox chemistry Recycle rubber more effectively requires new ways of reversing cross-linking and vulcanization Replace traditional acid and base catalysts in bulk processes perhaps using new zeolites Develop new water-based synthesis and processing methods to minimize use of volatile organic solvents (VOCs) Develop new catalytic processes, based on light or catalytic antibodies Devise better chelates to separate and recycle heavy metals catalysts

BIBLIOGRAPHY

1. 2. 3. 4. 5. 6. 7.

Green Chemistry - by Roger Arthur Sheldon Green Chemistry : Theory and Practice - by Paul Anastas and John C Warner http://lem.ch.unito.it www.globalspec.com www.organic-chemistry.com www.docstoc.com www.cleanproduction.com