UNHM Brown Bag Lecture Series
4/16/08
Assistant Professor of Chemistry
University of New Hampshire -
Manchester sarah.kenick@unh.edu

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An early chemist exploring the class of compounds known as isocyanides, moved his research outdoors when the overpowering disgusting odor of the compounds drove him there, then ceased work with them entirely when the complaints of the neighbors became too loud
(W.Lietke, Justus Liebigs Annalen de Chemie 1859, 112,316
(quoted in J.A. Green, II & P.T. Hoffman. “Isonitrile Chemistry,” I.Ugi, Ed,;Academic Press:
New York, 1971, p.1.))
The discoverer of mustard gas, a potent blistering agent used as a warfare agent in World War I, reported the terrible effects of his newly prepared compound on the nasal membranes when sniffed. In keeping with sound organic chemical practice of the times, he then tasted his compound! (if you are curious about the outcome, it caused a violent headache, dutifully reported in the manuscript reporting the isolation and analysis of mustard gas
(F.Guthrie, J.Chemical Society 1860, 12,109 (quoted in E.E.Reid, “Organic Chemistry of
Bivalent Sulfur,” Vol. 2; Chemical Publishing Co., New York, 1960, pp.238ff))

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Release of methyl isocyanate in Bhopal,
India killed 3800 people and permanently disabled another 2700

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Blue caused by copper contamination nothing lives - image is a collection basin used as part of remediation (water shunted to treatment plant)

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Love Canal - Niagara
Falls, NY
Burial site for 21,000 tons chemical waste
(1920’s-1950’s)
Heavy rains 1970’s leaching

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1936 - spark ignited floating debris and oil

Annual emissions of dioxins reduced 77% from 1987 - 1995
Sept 19-22,1999 lobsters died in large numbers - due to mosquito pesticides?
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Green chemistry is the utilization of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products
The emphasis is on eliminating hazard rather than just preventing exposure
Hazard is acknowledged as another important property of matter
Green chemistry must be the best chemistry practical and economically-driven

Anastas and Warner Green Chemistry Theory and Practice ･
Doxsee and Hutchison Green Organic Chemistry: Strategies,
Tools and Laboratory Experiments
Warner, Cannon and Dye- Green Chemistry, Environ. Impact
Assessment Review 2004 , 24 , 775-799.
Presidential Green Chemistry Challenge Awards -Winners and nominations: http://www.epa.gov/greenchemistry/
Real-World Cases in Green Chemistry by Michael C. Cann and
Marc E. Connelly....and .ppt presentations
( http://academic.scranton.edu/faculty/CANNM1/greenchemistry.
html )

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( Green Chemistry: Theory and Practice , Anastas and Warner, 1998)
#1: Prevent, rather than treat, waste
#2: Maximize use of materials - atom economy
#3: Avoid hazardous materials (reagents, starting materials and solvents) and products or by-products
#4: Design safer products -design in efficacy, design out hazards
#5: Minimize the use of solvents and auxiliary substances
#6: Recognize energy costs and minimize them
#7: Use renewable feedstocks
#8: Omit needless steps -protection/deprotection, e.g.
#9: Use catalysis!
#10: Design products for end of life -products should not persist in the environment, should degrade into innocuous substances
#11: Employ in-line, real-time monitoring/control to avoid generation of hazardous substances in transformations
#12: Whenever possible choose substances that minimize physical danger
(explosions, fires, etc.)

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Production of 2 bottles of ibuprofen generated 3 bottles of waste!

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3 bottles of ibuprofen generate less than
1 bottle of waste!

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#4: Design safer products -design in efficacy, design out hazards
#10: Design products for end of life products should not persistent in the environment, should degrade into innocuous substances

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Rohm and Haas Website

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(Film developing chemical)

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Which synthesis do you think is better - top or bottom?

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What can we do?
What are we doing?
industry academia

Green Chemistry in Industry - Driving forces
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Public Relations
Societal Concern
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University of Oregon
UMass Lowell
Others
University of Oregon - Organic
Laboratories first to be greened
Here!

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Organic Chemistry (traditional)
Green Organic Chemistry course FALL 2007
(active/inquiry/project based)
Hazardous/toxic chemicals as solvents
Little/no hazardous chemicals used
Large amount of hazardous waste
Very low (less than a 500 ml bottle for the class for the semester) hazardous waste
Little instruction on alternatives or purpose for use of solvents/chemicals
Little instruction on real life
(outside of generating chemicals/pharmaceuticals) applications
Direct in class and lab instruction and activities on the purpose of solvents and alternatives for toxic solvents
Student generated projects on real life applications of content knowledge Little hands on activity in the classroom (lecture) portion of the course
Guest speaker, student presentations throughout the semester, and interactive discussion on green and organic chemistry

Each in class exam had a take home essay component around some green chemistry related topic
Exam 1 - alternative solvents
Students given a list of solvents, and asked to devise their own system for ranking relative hazard to human health and the environment
Students also had to provide alternatives to their top two most hazardous substances on their list
MTBE (Methyl tert-butyl ether), Dichloromethane, Benzene,
Hexane, Pentane, Methanol, Acetic Acid, Water
Exam 2 - atom economy calculation
Exam 3 - Is It In Us reflective essay

The Princess Scale of Hazardous Chemicals
1. MTBE (Methyl tert-butyl ether)
2. Dichloromethane
3. Benzene
4. Hexane
5. Pentane
6. Methanol
7. Acetic Acid
8. Water
A number of subjective factors were factored when developing the schema for
The Princess Scale of Hazardous Chemicals. Categories were rated on a scale of 0-5, with 5 being the most severe rating and 0 being no effect. In the category of Health Effects, long term health effects (chronic exposure) were rated as less severe than a spontaneous effect. Whether a chemical was a known or suspected carcinogen was treated as a separate category. Other categories included Stability of the Chemical, Decomposition Product(s),
Flammability, Flash Fire, Effect of Accidental Release, Bioaccumulation
(degradation) effect in air, soil, and water
— with each earning 0-5 points for a total of 15 in this category, Transportation Hazard Class, and Handling
Challenges. Material Safety Data Sheet information was used to rate each category for each chemical from 0-5, the results tallied, and compiled in the chart found in the accompanying file.

5-10 minute presentations on a green chemistry topic of choice
Students presented throughout the semester scheduled relative to Organic Chemistry course topics
Students also produced a poster that was displayed at a Science Symposium at the end of the semester on the same topic

2
Supercritical CO
2 polymers
plasticizes
Poly Lactic Acid (PLA)
Poly Lactic Glycolic Acid
(PLGA)
Poly-DL-Lactic Acid
(P
DL
LA)
Drugs are mixed in to liquefied polymers
Creates homogenous mixture
Photo credit: bio-log.co.il

Mixture is sprayed in to collection chamber
Produces fibers or particles
Particles containing the polymer/drug mixture are injected under the skin
Gradual release of drug as polymer biodegrades
Photo credit: bio-log.co.il

2
Rapid Method
Very efficient
Inexpensive material
Widely available
Low operating costs
Moderate Temperatures
Minimal loss of proteins and growth factors.
Moderate temperature and pressure create safer production environments for workers.

2
Benign Solvent
Non-toxic to humans.
Reduced environmental hazard.
Non-flammable.
Minimal drug degradation.
Increased dose effectiveness
Decreased doses
Increased patient compliance.
More controlled release of the drug.
Reduced side effects.

Primary Carrier
Resins/Binders
Pigments
Additives
Application
Performance
Odor
Dry Time
Drying/Curing
Mechanism
Clean-up
Flashpoint
Traditional Paint
Oil or solvent based
Alkyds
Solvents added in tints
(heavy metals)
Biocides
May be difficult
Varies
Harsh odor
Longer
Evaporation, oxidation, polymerization
Mineral Spirits or solvents
Combustible
Low VOC paint
Water or latex based
100 % Acrylics, Polyvinyl
Acetates (PVA)
Less toxic solvents (if tinted)
Low Biocides
Easy
High overall performance
Low or No odor
Shorter
Evaporation, self coalescing
(stable)
Warm water and soap
None

Low VOC paint products (Green Seal Certified)
Benjamin Moore
Eco Spec  latex semi-gloss, flat, eggshell enamel, primer
Cloverdale Paint
Horizon Interior Line  flat, eggshell, semi-gloss, primer
Sherwin Williams
Harmony Interior Line  flat, eggshell, semi-gloss, primer
YOLO Colorhouse
Environmentally friendly company (all products zero VOC)
Variety of colors offered
Flat, eggshell, semi-gloss

Pros and Cons of Low VOC paints
Benefits
 ground level ozone pollution
Uses less toxic solvents
 long/short term health effects
 negative impact on indoor air quality
Equal or better performance
Easy clean-up (no solvents required)
Require less ventilation
Hospitals, nursing homes, schools, hotels utilize low-VOC paints
Downsides
Limited colors
Availability
Cost (of certain products)
100 % acrylics more expensive but best quality

July 2008 - NH Educator Green Chemistry Workshop
(flyer)
3 days
For NH High School Science Educators
Participants will work with student teams this fall
Supported by NH Dept. of Ed. LESCN Center Grant
Organic Chemistry Course Fall 08
Service learning project (extension of pilot)
Student teams will work with area high school educator to green a high school chemistry lab activity
Supported by UNHM Outreach Planning Grant
Green Chemistry INQ444 Course - Fall 09
Under Development
To be first offered (upon approval) fall 09
Will involve similar service learning/outreach projects
Supported by Inquiry course development funds

Establish a Green Chemistry Educator
Network in the state of New Hampshire and beyond
Provide training for NH (and Mass.) secondary school teachers in both green chemistry and in practice of greening their own labs extend to middle and elementary teachers once activities are established for these levels
Have my students serving as liaisons with schools and other interested groups to disseminate their work and help others to get “greened”!

Interested in sustainability issues in general
Got ideas on things we can do here at
UNHM to go “green”?
Contact - Pat Perkins ( dbz6052@yahoo.com
)

Organic Chemistry Students Fall 2007
Green Chemistry Colleagues
Ken Doxsee (University of Oregon)
Jim Hutchison (University of Oregon)
Rich Gurney (Simmons College)
NH Department of Education
LESCN Center
UNH

Doxsee and Hutchison Green Organic Chemistry: Strategies, Tools and Laboratory Experiments, Brooks Cole , 2003.
( lab manual used for some course materials - copy here)
GEMs database (Greener Educational Materials) for Chemists http://greenchem.uoregon.edu/gems.html
ACS- Green Chemistry site
Search “Green Chemistry Institute”
EPA - Green Chemistry Presidential Awards http://www.epa.gov/greenchemistry/index.html
My wiki http://sarahkenick.wikispaces.com/
Up to date information on ongoing projects, both here and collaborations with other institutions
Today’s presentation
Information on summer educator workshop
Links to other resources