Green Chemistry in Action! UNHM Brown Bag Lecture Series 4/16/08 Sarah Kenick Assistant Professor of Chemistry University of New Hampshire - Manchester

Green Chemistry in Action!UNHM Brown Bag Lecture Series

4/16/08

Sarah KenickAssistant Professor of Chemistry

University of New Hampshire - Manchester

[email protected]

mailto:[email protected]

Green Chemistry in Action

Why do we care?

What is Green Chemistry

12 Principles with examples

What can we do?

What are we doing here at UNHM?

QuickTime™ and aTIFF (LZW) decompressor

are needed to see this picture.

Why do we care?

Two stories - Chemists at workAn 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))



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



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



Love Canal - Niagara Falls, NY

Burial site for 21,000 tons chemical waste (1920’s-1950’s)

Heavy rains 1970’s - leaching



1936 - spark ignited floating debris and oil

http://www.epa.gov/glnpo/aoc/cuyahoga.html



Annual emissions of dioxins reduced 77% from 1987 - 1995

Sept 19-22,1999

lobsters died in large numbers - due to mosquito pesticides?









What is Green Chemistry?

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

Resources for the 12 Principles

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 )

http://www.epa.gov/greenchemistry/

http://academic.scranton.edu/faculty/CANNM1/greenchemistry.html

http://academic.scranton.edu/faculty/CANNM1/greenchemistry.html



12 Principles(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.)

#2: Maximize use of materials - atom economy



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



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

#3: Avoid hazardous materials (reagents, starting materials and solvents) and products or by-products



http://www.bt.cdc.gov/agent/phosgene/basics/facts.asp



#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





Rohm and Haas Website

http://www.rohmhaas.com/wcm/products/product_detail.page?product=1010157&application=1120196

#5: Minimize the use of solvents and auxiliary substances





#7: Use renewable feedstocks



(Film developing chemical)







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



What can we do?

What are we doing?

industry

academia







Green Chemistry in Industry - Driving forces

Public Relations

Societal Concern



Academic Green Chemistry Programs

Some PhD programs in Green Chemistry

University of OregonUMass LowellOthers

Undergraduate Programs/CoursesUniversity of Oregon - Organic Laboratories first to be greenedHere!



Green Chemistry in Action here

Organic Chemistry (traditional)Hazardous/toxic chemicals as solventsLarge amount of hazardous wasteLittle instruction on alternatives or purpose for use of solvents/chemicalsLittle instruction on real life (outside of generating chemicals/pharmaceuticals) applicationsLittle hands on activity in the classroom (lecture) portion of the course

Green Organic Chemistry course FALL 2007 (active/inquiry/project based)

Little/no hazardous chemicals usedVery low (less than a 500 ml bottle for the class for the semester) hazardous waste Direct in class and lab instruction and activities on the purpose of solvents and alternatives for toxic solventsStudent generated projects on real life applications of content knowledgeGuest speaker, student presentations throughout the semester, and interactive discussion on green and organic chemistry

Examples of Student Work - Exam Essays

Each in class exam had a take home essay component around some green chemistry related topic

Exam 1 - alternative solventsStudents given a list of solvents, and asked to devise their own system for ranking relative hazard to human health and the environmentStudents also had to provide alternatives to their top two most hazardous substances on their listMTBE (Methyl tert-butyl ether), Dichloromethane, Benzene, Hexane, Pentane, Methanol, Acetic Acid, Water

Exam 2 - atom economy calculationExam 3 - Is It In Us reflective essay

The Princess Scale of Hazardous Chemicals1. MTBE (Methyl tert-butyl ether)2. Dichloromethane 3. Benzene4. Hexane5. Pentane6. Methanol7. Acetic Acid8. 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.

Examples of student work -PPT presentations

5-10 minute presentations on a green chemistry topic of choice

Students presented throughout the semester - scheduled relative to Organic Chemistry course topicsStudents also produced a poster that was displayed at a Science Symposium at the end of the semester on the same topic

Drug coating using Supercritical CO2

MethodSupercritical CO2 plasticizes polymers

Poly Lactic Acid (PLA)Poly Lactic Glycolic Acid (PLGA)Poly-DL-Lactic Acid (PDLLA)

Drugs are mixed in to liquefied polymers

Creates homogenous mixture

Photo credit: bio-log.co.il

Drug coating using Supercritical CO2Method

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

Benefits to using Supercritical CO2

Drug delivery & coating biopharmaceuticals

Rapid MethodVery efficient

Inexpensive materialWidely availableLow operating costs

Moderate TemperaturesMinimal loss of proteins and growth factors.Moderate temperature and pressure create safer production environments for workers.

Benefits to using Supercritical CO2

Drug delivery & coating biopharmaceuticalsBenign Solvent

Non-toxic to humans.Reduced environmental hazard.Non-flammable.Minimal drug degradation.

Increased dose effectivenessDecreased doses

Increased patient compliance.

More controlled release of the drug.

Reduced side effects.

What’s the difference?? Traditional Paint Low VOC paint

Primary Carrier Oil or solvent based Water or latex based

Resins/Binders Alkyds100 % Acrylics, Polyvinyl

Acetates (PVA)

PigmentsSolvents added in tints

(heavy metals)Less toxic solvents (if

tinted)

Additives Biocides Low Biocides

Application May be difficult Easy

Performance Varies High overall performance

Odor Harsh odor Low or No odor

Dry Time Longer Shorter

Drying/Curing Mechanism

Evaporation, oxidation, polymerization

Evaporation, self coalescing (stable)

Clean-up Mineral Spirits or solvents Warm water and soap

Flashpoint Combustible None

What’s on the market you ask??

Low VOC paint products (Green Seal Certified)Benjamin Moore

Eco Spec latex semi-gloss, flat, eggshell enamel, primerCloverdale Paint

Horizon Interior Line flat, eggshell, semi-gloss, primerSherwin Williams

Harmony Interior Line flat, eggshell, semi-gloss, primerYOLO Colorhouse

Environmentally friendly company (all products zero VOC)Variety of colors offeredFlat, eggshell, semi-gloss

Pros and Cons of Low VOC paints

Benefits ground level ozone pollutionUses less toxic solvents long/short term health effects negative impact on indoor air qualityEqual or better performanceEasy clean-up (no solvents required)Require less ventilation

Hospitals, nursing homes, schools, hotels utilize low-VOC paints

DownsidesLimited colorsAvailabilityCost (of certain products)

100 % acrylics more expensive but best quality

Samples of Student Work - Posters at Symposium

Projects in progress

July 2008 - NH Educator Green Chemistry Workshop (flyer)3 daysFor NH High School Science EducatorsParticipants will work with student teams this fallSupported by NH Dept. of Ed. LESCN Center Grant

Organic Chemistry Course Fall 08Service learning project (extension of pilot)

Student teams will work with area high school educator to green a high school chemistry lab activitySupported by UNHM Outreach Planning Grant

Green Chemistry INQ444 Course - Fall 09Under DevelopmentTo be first offered (upon approval) fall 09Will involve similar service learning/outreach projectsSupported by Inquiry course development funds

My Grand Green Goal

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”!

The Green Team

UNHM Student Group Interested in sustainability issues in general

Got ideas on things we can do here at UNHM to go “green”?

Contact - Pat Perkins ([email protected] )

mailto:[email protected]

AcknowledgementsOrganic Chemistry Students Fall 2007

Green Chemistry ColleaguesKen Doxsee (University of Oregon)

Jim Hutchison (University of Oregon)

Rich Gurney (Simmons College)

NH Department of EducationLESCN Center

UNH

Useful Links/ResourcesDoxsee 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 Chemistshttp://greenchem.uoregon.edu/gems.html

ACS- Green Chemistry siteSearch “Green Chemistry Institute”

EPA - Green Chemistry Presidential Awardshttp://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 institutionsToday’s presentationInformation on summer educator workshopLinks to other resources

http://greenchem.uoregon.edu/gems.html

http://www.epa.gov/greenchemistry/index.html

http://sarahkenick.wikispaces.com/

Documents

Green Chemistry in Action! UNHM Brown Bag Lecture Series 4/16/08 Sarah Kenick Assistant Professor of Chemistry University of New Hampshire - Manchester