Michael Cann, Chemistry Department

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GREENING THE CHEMISTRY CURRICULUM

• Michael Cann, Chemistry Department
• http//academic.scranton.edu/faculty/CANNM1/greenc
  hemistry.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)

• 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)
• Control 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 sustainable/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 and Engineering News
• 2000 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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GREEN CHEMISTRY

• "Green chemistry represents the pillars that hold
  up our sustainable future. It is imperative to
  teach the value of green chemistry to tomorrow's
  chemists."
• Daryle Busch, President ACS, June 26,
  2000, Color Me Green
• Chem. Eng. News 2000, 78 (28) 49-55.

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ENVIRONMENTAL CHEMISTRY

• Poster/Oral Presentation on one of the PGCC Award
  Winning Proposals 1996
• Cann, Michael C., J. Chem. Ed. 1999, 76 (12),
  1639-1641.

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REAL-WORLD CASES IN GREEN CHEMISTRY

• ACS/EPA Green Chemistry Educational Materials
  Development Project, 1998
• Compilation of materials on real-world green
  chemistry (based on PGCC) in a format that can be
  used for educational purposes
• Each case acts as an informational
  resource for instructors to use in
  greening their courses
• Marc Connelly
• http//www.acs.org/portal/Chemistry?PIDacsdisplay
  .html
• DOCeducation\greenchem\cases.html

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MAINSTREAMING GREEN CHEMISTRY

• Insertion of green chemistry into mainstream
  chemistry courses
• Need faculty who teach these courses to develop
  modules on green chemistry related to topics
  already covered in their course
• Make it easy (lower Eact) for other
• faculty to do the same
• place materials on the web

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WEB BASED GREEN CHEMISTRY MODULES FOR SPECIFIC
CHEMISTRY COURSES

• Major support-The Camille and Henry Dreyfus
  Foundation
• Additional support-ACS/EPA, University of
  Scranton
• T. Dickneider, T. Foley, D. Marx, D.
  Narsavage-Heald, J. Wasilewski
• (The Green Machine)

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GREEN CHEMISTRY MODULES FOR SPECIFIC CHEMISTRY
COURSES

• General -Surfactants for CO2
• Organic -Atom economy
• Inorganic Activators of hydrogen peroxide for
  green oxidation
• Biochemistry Confirm, Mach 2 and Intrepid
  pesticides
• Advanced Organic Elimination of Chlorine in NAS

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GREEN CHEMISTRY MODULES FOR SPECIFIC CHEMISTRY
COURSES

• Polymer Polyaspartic acid
• Industrial Petretec polyester regeneration
• Environmental Sea-nine antifoulant
• Toxicology Confirm,
• Mach 2, and Intrepid

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GREEN CHEMISTRY MODULES FOR SPECIFIC CHEMISTRY
COURSES

• Introduction to Green Chemistry
• Module text, questions and bibliography
• Notes to instructors
• Power Point presentation
• http//academic.scranton.edu/faculty/CANNM1/
• dreyfusmodules.html

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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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ATOM ECONOMY IN THE WITTIG REACTION
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GREEN CHEMISTRY

• The Synthesis of Ibuprofen
• 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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GREEN CHEMISTRY

• Major Focus Replacement of organic solvents
  -VOCs, halogenated, almost 15 billion kilograms
  produced wordwide each year
• Solvent free
• Solvent alternatives
• Ionic liquids
• Fluorous
• Carbon dioxide

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GREEN CHEMISTRY

• Dry Cleaning
• Initially gasoline and kerosene were used
• Chlorinated solvents are now used, such as perc
• Supercritical/liquid carbon
• dioxide (CO2) infusing green
• chemistry into general chemistry

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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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Surfactant
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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 the Hangers CO2 process lowers energy
  consumption.
• Using CO2 reduces environmental regulatory
  burdens for Hangers operators.
• Uses waste CO2 from other processes.

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GREEN CHEMISTRY

• Antifoulants (algae and seaweed
• barnacles and diatoms)
• Pesticides, infusing green
• chemistry into environmental chemistry

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Antifoulants

• TBTO
• Half-life of TBTO in seawater is gt 6 months
• Bioconcentration, 104
• Chronic Toxicity
• Thickness of oyster shells
• Sex changes in whelks
• Imposex in snails
• Immune system in dolphins and others?

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Antifoulants

• DCOI (PGCC award Rohm and Haas)
• Acutely toxic to a wide range of marine organisms
  (effective anitfoulant)
• Rapid biodegradation to nontoxic products
• (½ life lt 1 hour)
• Low Bioconcnetration
• (bioconcentration 13)
• Environmental Conc. lt Acute Toxicity level
• No Chronic Toxicity
• Rapid partitioning to the sediment
• (low bioavailability)
• 
  4,5-dichloro-2-n-octyl-4-isothiazolin
  -3-one

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Other Green Chemistry Education Efforts

• ACS
• Greener Approaches to Undergraduate Chemistry
  Experiments (Spanish)
• Introduction to Green Chemistry
• Innovations for a
• Cleaner World (video)

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Other Green Chemistry Education Efforts

• University of Oregon NSF Workshop
  http//www.uoregon.edu/hutchlab/greenchem/
• U Mass Boston
• Hendrix College
• University of Delaware
• Monash University

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Green Chemistry Endeavors at Scranton

• Greening existing chemistry textbooks.
• Environmental Chemistry, Colin Baird, W.H.
  Freeman
• Chemistry Foundations and Applications,
  Macmillan
• Translation of our web-based Green Chemistry
  Modules into Spanish Portuguese.
• 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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