Pollution Prevention: A Paradigm Addressed Through GREEN CHEMISTRY

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Pollution Prevention A Paradigm Addressed
Through GREEN CHEMISTRY

• Michael Cann, Chemistry Department
• http//academic.scranton.edu/faculty/CANNM1/
• greenchemistry.html

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Better Things for Better Living Through
Chemistry DuPont

• Ibuprophen
• Lipitor
• Celebrex
• Vioxx
• Rogaine
• Prozac
• Viagra
• Prilosec

• Nylon
• Dacron
• PET
• Polystyrene
• Acrylics
• Teflon
• Rayon
• Polyaniline

• DNA
• Recombinant
• Technology
• PCR

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ENVIRONMENTAL DISASTERS

• DDT
• CFCs
• Cuyahoga River
• Love Canal

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ENVIRONMENTAL DISASTERS

• Became rallying points for environmental laws
• Cuyahoga River- 1972 Clean Water Act
• Love Canal- 1980 Comprehensive Environmental
  Response, Compensation Liability Act, better
  known as Superfund. Emergency Planning
  Community Right-to-Know Act, requires that
  industries
• report toxic releases.

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Toxic Release Inventory

• In 2000 7.1 billion pounds of hazardous chemicals
  were released to the air water and soil.
• Only includes 650 of the 75,000 chemicals in use
  in US commerce today
• Thresholds of 25,000 pounds (manufacture) and
  10,000 pounds (use)

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Risk Due to a Hazardous Substance
Riskf(Hazard, Exposure) environmental laws
attempt to control exposure

• Controlling Exposure end of the
• pipe solution
• Command and control laws

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Command and Control Cost to Industry

• Industries in the US spend over 100 billion/year
  on waste treatment, control, and disposal.
• 1996 Dupont spent 1 billion for environmental
  compliance (research budget 1 billion chemical
  sales of 18 billion)

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THE POLLUTION PREVENTION ACT OF 1990

• Riskf(HAZARD, Exposure)
• Eliminate the hazard, no need to worry about the
  exposure!

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Chemists Must Place a Major Focus on the
Environmental Consequences of Chemical Products
and the Processes by which these Products are
Made. We must consider our chemical
ecological footprint.
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GREEN CHEMISTRY

• Green Chemistry or environmentally benign
  chemistry is the design of chemical products and
  processes that reduce of eliminate the use and
  generation of hazardous substances
• Minimize
• waste
• energy use
• resource use (maximize efficiency)
• utilize renewable resources

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The Twelve Principles of GREEN CHEMISTRY
(Anastas and Warner 1998)

• 1. It is better to prevent waste than to treat or
  clean up waste after it is formed.
•  
• 2. Synthetic methods should be designed to
  maximize the incorporation of all materials used
  in the process into the final product.
•  
• 3. Wherever practicable, synthetic methodologies
  should be designed to use and generate substances
  that possess little or no toxicity to human
  health and the environment.
•  
• 4. Chemical products should be designed to
  preserve efficacy of function while reducing
  toxicity.
•  
• 5. The use of auxiliary substances (e.g.
  solvents, separation agents, etc.) should be made
  unnecessary whenever possible and, innocuous when
  used.
•  
• 6. Energy requirements should recognized for
  their environmental and economic impacts and
  should be minimized. Synthetic methods should be
  conducted at ambient temperature and pressure.
•  

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The Twelve Principles of GREEN CHEMISTRY (Anastas
and Warner 1998)

• 7.A raw material feedstock should be renewable
  rather than depleting whenever technically and
  economically practical.
•  
• 8. Unnecessary derivatization (blocking group,
  protection/deprotection, temporary modification
  of physical/chemical processes) should be avoided
  whenever possible.
•  
• 9. Catalytic reagents (as selective as possible)
  are superior to stoichiometric reagents.
•  
• 10. 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.
•  
• 11. Analytical methodologies need to be further
  developed to allow for real-time in-process
  monitoring and control prior to the formation of
  hazardous substances.
•  
• 12. Substances and the form of a substance used
  in a chemical process should chosen so as to
  minimize the potential for chemical accidents,
  including releases, explosions, and fires.
•     

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GREEN CHEMISTRY

• Pollution Prevention Act 1990
• GC Began in 1991 at EPA, Paul Anastas
• 1996 Presidential Green Chemistry Challenge
  Awards
• 1997 Green Chemistry and Engineering Conference
• 1999 Journal Green Chemistry
• Chemical Engineering News
• 2001 Journal of Chemical Education

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Examples of Green Chemistry
Presidential Green Chemistry Challenge Award
Winners For more informational on Presidential
Green Chemistry Challenge Award Winners
http//www.epa.gov/greenchemistry/presgcc.html

• New syntheses of Ibuprofen and Zoloft.
• Integrated circuit production.
• Removing Arsenic and Chromate from pressure
  treated wood.
• Many new pesticides.
• New oxidants for bleaching paper and disinfecting
  water.
• Getting the lead out of automobile paints.
• Recyclable carpeting.
• Replacing VOCs and chlorinated solvents.
• Biodegradable polymers from renewable resources.

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ATOM ECONOMYBarry Trost, Stanford
UniversityBecause an Atom is a Terrible Thing
to Waste

• How many of the atoms of the reactant are
  incorporated into the final product and how many
  are wasted? Infusing green chemistry into
  organic.

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ATOM ECONOMY

• Atom Economy Table
• Atom Economy (FW of atoms utilized/FW of all
  reactants) X 100 (137/275) X 100 50

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GREEN CHEMISTRYThe BHC Company

• The Synthesis of Ibuprofen (analgesic,
  anti-inflammatory)
• Advil, Motrin, Medipren
• 28-35 million pounds of ibuprofen are produced
  each year (37-46 million pounds of waste)

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Environmental Advantages of BHC Synthesis of
Ibuprofen

• Less waste
• greater atom economy
• catalytic versus stoichiometric reagents
• recycling, reuse, recovery of byproducts and
  reagents (acetic acid gt99 HF gt99.9)
• greater throughput (three steps versus five
  steps) and overall yield (virtually quantitative)
• Fewer auxiliary substances (solvents separation
  agents)

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Economic Advantages of BHC Synthesis of Ibuprofen

• Greater throughput and overall yield
• (three steps versus five steps)
• Greater atom economy (uses less feedstocks)
• Fewer auxiliary substances (solvents separation
  agents)
• Less waste (lower disposal costs)

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Other improved syntheses

• that are winners of Presidential Green Chemistry
  Awards include the pesticide Roundup (Rohm
  Haas), the antiviral agent Cytovene (Roche
  Colorado), and the active ingredient in the
  antidepressant Zoloft (Pfizer).

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Confirm, Mach 2 and Intrepid Selective Insect
Control

• Rohm and Haas Company

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DDT
Neurotransmitter and receptor ion channel
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ORGANOPHOSPHOROUS AND CARBAMATE INSECTICIDES
ACETYLCHOLINESTERASE INHIBITORS

• Less persistent than organochlorine insecticides
  no bioconcentration
• More toxic to mammals

Carbamate
X S, O R CH3, CH2CH3 Organophosphate
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Organophosphates
Hydrolysis of Acetylcholine
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GREEN CHEMISTRY Confirm, Mach 2 and Intrepid

• Selective toxicity achieved by targeting the
  unique physiology of insect growth
• The growth of certain insects is accompanied by
  the periodic shedding of their outer cuticle
  layers, a process called molting
• Molting is initiated by an increase in the levels
  of the steroid hormone 20-hydroxyecdysone (20E)
• A decline of 20E concentrations
• to basal levels ends molting
• Confirm, Mach 2 and Intrepid
• mimic 20E

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GREEN CHEMISTRY Confirm, Mach 2 and Intrepid

• Confirm, Mach 2 and Intrepid mimic 20E but the
  concentration of active ingredient does not
  decline insect never sheds its cuticle and thus
  never resume feeding
• Tebufenozide kills caterpillars while
• halofenozide kills beetle larvae,
• cutworms, and webworms
• No harm to beneficial insects
• Acute toxicity to
• higher organisms
• is very low

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GREEN CHEMISTRY

• Dry Cleaning
• Initially gasoline and kerosene were used.
• Chlorinated solvents are now used, such as perc.
• Infusing green chemistry into general chemistry
• Supercritical/liquid carbon dioxide (CO2)
• (also used for cleaning metal surfaces,
  integrated circuits,
• micro-electromechanical devices, flat panel
  displays)

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• Solubility of Substances in CO2
• Carbon dioxide a non polar molecule since the
  dipoles of the two bonds cancel one another.
• Carbon dioxide will dissolve smaller non polar
  molecules
• hydrocarbons having less than 20 carbon atoms
• other organic molecules such as aldehydes,
  esters, and ketones
• But it will not dissolve larger molecules such as
  oils, waxes, grease, polymers, and proteins, or
  polar molecules.

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Surfactants for H2O(soaps and detergents)
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CO2 Surfactant Joe DeSimone, UNC, NCSU, NSF
Science and Technology Center for
Environmentally Responsible Solvents and
Processes, PGCC Award 1997
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CO2 Surfactant
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• http//www.hangersdrycleaners.com/

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Environmental/Economic Advantages of Liquid CO2

• Using CO2 eliminates hazardous waste generation
  of perc.
• CO2 does not pose the environmental and human
  health risks associated with perc (used by 34,000
  dry cleaners in US).
• Using CO2 reduces environmental regulatory
  burdens for Hangers operators.
• Uses waste CO2 from other processes.

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Triple Bottom Line

• GREEN CHEMISTRYOffers the potential for
  Environmental, Economic and Social benefits
• John Tucker, of Pfizer Inc., said the green in
  green chemistry is also the color of money
  during a discussion of Pfizers new greener
  synthesis of sertraline.

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Green Chemistry Endeavors at Scranton

• Real-World Cases in Green Chemistry.
• Web based Green Chemistry Teaching Modules
  (Spanish, Portuguese).
• Greening existing chemistry textbooks.
• Environmental Chemistry, Colin Baird, W.H.
  Freeman
• Chemistry Foundations and Applications,
  Macmillan
• The business side of green chemistry.
• Survey of PGCC applicant
• Infusion into business courses
• Bringing green chemistry to the high school and
  secondary school level.
• Integrating sustainability throughout our
• campus.

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Acknowledgements

• Marc Connelly
• The Green Machine Trudy Dickneider, Tim Foley,
  David Marx, Donna Narsavage-Heald, Joan
  Wasilewski
• Camille and Henry Dreyfus Foundation
• American Chemical Society Sylvia Ware, Janet
  Boese, Mary Ann Ryan
• Environmental Protection Agency Tracy Williamson
• White House Office of Science and Technology
  Policy Paul Anastas
• Green Chemistry Institute Mary Kirchhoff
• Universidad de Las Palmas de Gran Canaria,
• Maria de la Concepcion, Sebastian Perez

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