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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Sustainability

• "Meeting the needs of the present without
  compromising the ability of future generations to
  meet their needs."
• (The U.N. Brundtland Commission 1987)
• JUSTICE?

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Sustainability?
Nature

• Are we exceeding the carrying capacity of the
  earth? Are we using resources and creating waste
  faster that the earth can take our wastes and
  convert them back into resources?

Resources
Consumption
Waste
Humans
Resources
Consumption
Waste
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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 GCI integrated into ACS
• 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
• 17,000 hits 500 different universities
• Module text, questions and bibliography
• Notes to instructors
• Power Point presentation
• http//academic.scranton.edu/faculty/CANNM1/dreyfu
  smodules.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 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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Green Chemistry Environmental Chemistry

• Ozone hole and troposheric air pollution carbon
  dioxide as a replacement for CFCs and hydrocarbon
  blowing agents surfactants for carbon dioxide so
  that carbon dioxide can be used to replace VOCs.
• Pesticides readily biodegradable marine
  antifoulant as replacement for tributyltin oxide
  selective pesticides as replacements for broad
  spectrum pesticides.
• Toxic organic chemicals (e.g. dioxins)
  activators of hydrogen peroxide to replace
  chlorine bleaching agents.
• Polluted water and sewage treatment
  biodegradable scale inhibitors and dispersing
  agents as a replacement for polyacrylate polymer.
  
• Solid waste, landfills and closed loop recycling
  Petretec process for conversion of PET back into
  its monomers and reformation into virgin PET.

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Environmental ChemistryBaird Cann

• Introduction to Green Chemistry Atom economy
  synthesis of ibuprofen.
• Ozone CO2 as a blowing agent Harpin as a
  replacement for methyl bromide fumigant.
• Tropospheric pollutants CO2 surfactants.
• Greenhouse gases scCO2 in photolithography.
• Energy/petroleum biodegradable polymers from
  renewable resources.
• Pesticides selective pesticides termite
  control/ reduced risk pesticides.

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Environmental ChemistryBaird Cann

• Toxic organics non-chlorine bleaching agents,
  H2O2 activators
• Water pollution/purification enzymatic
  preparation of cotton textiles biodegradable
  chelating agents
• Heavy metals removal of lead from automobile
  paint removal of arsenic and cadmium from
  pressure treated wood
• Solid waste biodegradable antiscalant recylable
  carpeting

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Green Chemistry Endeavors at Scranton

• Greening existing chemistry textbooks.
• Organic Chemistry, Solomons Fryhle, Wiley
• Chemistry Foundations and Applications,
  Macmillan
• Translation of our web-based Green Chemistry
  Modules into Spanish Portuguese.
• The business side of green chemistry.
• Infusion into business courses
• Bringing green chemistry to the high school and
  secondary school level.
• Integrating sustainability throughout our
• campus http//matrix.scranton.edu/sustainability/
  default.shtml

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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, Mary
  Kirchhoff, Janet Boese, Mary Ann Ryan
• Environmental Protection Agency Tracy Williamson
• Green Chemistry Institute Paul Anastas
• Universidad de Las Palmas de Gran Canaria,
• Maria de la Concepcion, Sebastian Perez
• Universidade Federal de Pelotas (UFPel)Eder J.
  Lenardãoa Colleagues

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