Green Chemistry: Chemistry for the Long Haul Sustainable

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Green Chemistry Chemistry for the Long
HaulSustainable Chemistry

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

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Mission

• To advance the broader chemistry enterprise and
  its practitioners for the benefit of Earth and
  its people.

https//portal.acs.org/portal/acs/corg/memberapp?_
nfpbtrue_ pageLabelPP_ARTICLEMAINnode
id1392use_secfalse
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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 without
  compromising the ability of future generations to
  meet their needs."
• (The U.N. Brundtland Commission 1987)

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Sustainability?Consumption Waste
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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By Nation

• There exists about 4.5 acres/person of
  biologically productive space on the earth

http//www.earthday.net/footprint/index_reset.asp?
pid2066614043005642
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"I Want to be like Mike"
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I Want to Be Like Mike!

• China's gross domestic product (GDP) surged by
  10.7 in 2006 .. fourth straight annual
  double-digit growth rate
• India 8.5
• World 5.1
• US 3.3

China Bureau National Statistics
http//english.gov.cn/2007-01/25/content_507608.ht
m
CIA World Fact Book https//cia.gov/library/publi
cations/the-world-factbook/rankorder/2003rank.html
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Population of the Earth

• Exponential population growth ranks high on the
  list of environmental threats
• 1 billion in 1804   
•  2 billion in 1927 (123 years later)  
•  3 billion in 1960 (33 years later)  
•  4 billion in 1974 (14 years later)  
•  5 billion in 1987 (13 years later)  
•  6 billion in 1999 (12 years later) 
• 2050 projections range from 7.5-11 billion
• At 1 growth rate the US will double in
• population in 70 years

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Sustainability -"Meeting the needs of the present
generation without compromising the ability of
future generations to meet their needs."

• Enhanced global warming
• Depletion of resources
• Food shortages
• Shortages of potable water
• Housing
• Waste
• How can chemistry contribute?

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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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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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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 Principals 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 Principals 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
• Roger Garret and Paul Anastas began the
  Alternative Synthetic Reactions Program in 1991
• Joe Breen coined "Green Chemistry" in 1993
• 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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'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 Ibuprofen and Zoloft.
• Integrated circuit production.
• Removing Arsenic and Chromate from pressure
  treated wood.
• Many new pesticides Harpin
• New oxidants for bleaching paper and disinfecting
  water.
• Getting the lead out of automobile paints.
• Recyclable carpeting.
• Replacing VOCs and chlorinated solvents.
• Lowering of trans fats in oils.
• Biodegradable polymers from renewable resources.
  
• Replacing petroleum based polymers with cellulose
  (ionic liquids)

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ATOM ECONOMY 1998 Barry 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?

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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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The Synthesis of Ibuprofen 1997BHC Company

• Advil, Motrin, Medipren
• 28-35 million pounds of ibuprofen are produced
  each year (37-46 million pounds of waste)

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77(99) vs. 40 atom economy
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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)

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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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Ionic Liquids Microwave Heating to
Dissolve/Process Cellulose 2005Robin Rogers,
Alabama
30 billion tons of cellulose is produced
naturally by terrestrial plants
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NatureWorks PLA 2002polymers from
cornNatureWorks LLC
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Environmental Advantages of Nature Works PLA

• Made from annually renewable resources (corn,
  sugar beets, eventually waste biomass)
• Consumes 20-50 less fossil fuel resources than
  petroleum based polymers
• Uses natural fermentation to produce lactic acid
• PLA converted back to monomer via hydrolysis,
  then repolymerized to produce virgin polymer)
  i.e. closed lop recycling
• PLA can be composted (biodegradable), complete
  degradation occurs in a few weeks under normal
  composting conditions

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Products Made From PLA

• Fibers for clothing, pillows, diapers
• Cups
• Bags for refuse
• Furnishings for home and office (carpet tile,
  upholstery, awnings, industrial
• wall panels)
• Rigid food containers, food
• wrappers/bags -October 2005
• Wal-Mart

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Trans Fatty Acids
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Hydrogenation of Oils and Fats
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Enzymatic Interesterification 2005 Novozymes,
Archer Daniels Midland Company
Higher melting triglceride
Lower melting triglceride
Mixture of intermediate melting triglycerides
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Preservation of Wood

• 4 billion dollar industry
• Industry annually pressure treats greater than 7
  billion board feet wood (about 1/5 of all
  softwood lumber sold)
• Untreated wood rots in 3-12 years, treated wood
  20-50
• Without treatment 15 billion dollar increase in
  lumber production (transportation, construction
  and utility industries)
• Estimates indicate about 6.5 billion board feet
  of wood conserved each year in the US (435,000
  new houses, or 226,000,000 trees)

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Production of Pressure Treated Wood (PTW)

• gt 95 PTW was treated with CCA, 2001 7 billion
  board feet of PTW produced (about 1/5 of all
  softwood lumber sold)
• 150 million pounds of CCA
• 40 million pounds of arsenic
• 64 million pounds of hexavalent chromium
• Wood is placed in a vacuum (depletes
• wood cells of air and water) CCA solution
• is applied under pressure infiltrating
• the wood

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Production of PTW

• Typical CCA solution 35.3 CrO3 19.6 CuO
  45.1 As2O3
• Cu, Cr and As levels in the wood 1000-5000mg/kg
• 8x10 deck, 4 lb
• metals (1.9 lb Cr,
• 1.36 As, 0.74 lb Cu)

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Potential Risks Associated with PTW

• Arsenic leaching from PTW
• Ingestion from contact with PTW
• Risk to workers in the production of PTW
• Waste generated from PTW production
• Disposal of PTW (burned, mulched)
• Hazards associated with
• transportation, production, use
• and disposal of CCA
• components
• http//www.cnn.com/2001/HEALTH/parenting/05/23/ars
  enic.playgrounds/index.html

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Removing the Arsenic and Chromium from PTW
2002Chemical Specialties Inc

• ACQ (Alkaline Copper Quarternary Ammonium
  Compound) Preserve, Chemical Specialties Inc
  (CSI)
• Similar copper formulations are used in
  controlling algae in various water systems
  Quaternary ammonium salts are routinely used in
  disinfectants and cleaners
• Low mammalian toxicity to the copper and ammonium
  salts (LD50730 800 mg/kg about the same as
  salt and ethanol) in ACQ
• Disposal of ACQ treated wood may be disposed of
  in general landfills

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Green Chemistry Endeavors at Scranton

• Greening existing chemistry textbooks.
• Environmental Chemistry. Baird Cann, 4th
  edition
• Other Freeman texts
• Chemistry for Changing Times, Hill Kolb,
  Prentice Hall
• Organic Chemistry, Solomons Fryhle, Wiley
• Chemistry Foundations and Applications,
  Macmillan
• Real-World Cases in Green Chemistry, Volume I
  II
• Web-based Green Chemistry Modules into Spanish
  Portuguese.
• Additional web based modules??????
• 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, Tom Umile
• 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, Rich Engler
• Green Chemistry Institute Kathryn Parent
• Center for Green Chemistry and Engineering at
  Yale 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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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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