Michael Cann, Chemistry Department

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GREENING THE CHEMISTRY CURRICULUM
Syracuse ACS Section 9/24/ 2007

• 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

• Lipitor 8.4
• Zocor 4.4
• Nexium 4.4
• Prevacid 3.8
• Plavix 3.5
• Zoloft 3.1
• Procrit 3.1
• Rogaine
• Viagra
• Ibuprophen

• 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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Chemical Ecological Footprint How much land and
water area the production, use and disposal of
chemicals requires under prevailing technology.
(environmental consequences of chemical products
and the processes by which these products are
made)
We must lower our chemical ecological Footprint
by improving the prevailing technology
GREEN CHEMISTRY
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The Chemistry Enterprise in 2015A Report of the
ACS 2005

• By 2015, the chemistry enterprise will be judged
  under a new paradigm of sustainability.
  Sustainable operations will become both
  economically and ethically essential.

http//chemistry.org/chemistryenterprise2015.html
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Sustainability -"Meeting the needs of the present
generation without compromising the ability of
future generations to meet their needs."

• How can chemistry contribute?
• Enhanced global warming
• Renewable resources
• Food
• Water
• Housing
• Prevention of waste

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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 CHEMISTRYSome Milestones

• 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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'Green chemistry' work wins Nobel CNN 10/5/05

• France's Yves Chauvin and Americans Robert H.
  Grubbs and Richard R. Schrock won the award for
  their development of the metathesis method in
  organic synthesis.
• This represents a great step forward for 'green
  chemistry,' reducing potentially hazardous waste
  through smarter production. Metathesis is an
  example of how important basic science has been
  applied for the benefit of man, society and the
  environment,"

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Examples of Green Chemistry
Presidential Green Chemistry Challenge Award
Winners

• New syntheses of drugs such as Ibuprofen, taxol
  and Zoloft.
• SC CO2 -Integrated circuit production.
• Removing Arsenic and Chromium 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.
• Lowering of trans fats in oils.
• Using ionic liquids to dissolve cellulose.

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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-Present 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
• Volume 2, 2008
• 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 worldwide 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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Green Chemistry in Mainstream Textbooks Survey
Results
33/141 (23) at least some mention of green
chemistry

• Non science majors 7
• General chemistry 10
• Organic 7
• Organic lab 5
• Inorganic 1
• Environmental 3

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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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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
• Green Organic Chemistry Strategies, Tools and
  Laboratory Experiments
• Green Education Materials for Chemists
• U Mass Lowell
• 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 (23,000 hits).
• 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, 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

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