Green Chemistry in Undergraduate Science Education: A Case Study at St. Olaf College

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Green Chemistry in Undergraduate Science
Education A Case Study at St. Olaf College
Paul T. Jackson, Ph.D. Minnesota Air, Water, and
Waste Environmental Conference Chemistry
Department Environmental Studies Department 28
February 2007
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Green Chemistry
St. Olaf Green Chemistry Leadership Team Gary
Spessard, Robert Hanson Paul Jackson Post-doc
Marc Klingshirn (U Illinois Springfield) Resear
ch Team Tim Barker, Julia Brown, Allison
Christensen, Tyler Drake, David Harris, Eric
Scholten, David Vock
Top image courtesy of RSC
Top image courtesy of RSC
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Green Chemistry

• GOAL To design chemical products and processes
  that reduce or eliminate the use or generation of
  hazardous substances.
• Ecological-chemical footprint
• RISK (Hazard, Exposure)
• AVOID / MINIMIZE resource intensity
• Waste generation, disposal
• Energy transformation
• Materials choices, use and design
• Twelve Principles

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12 Principles of Green Chemistry

• Prevent waste
• Maximize atom economy
• Design safer chemicals and products
• Design less hazardous chemical syntheses
• Use renewable feedstocks
• Use catalysts, not stoichiometric reagents

• Avoid chemical derivatives
• Use safer solvents and reaction conditions
• Increase energy efficiency
• Design chemicals and products to degrade after
  use
• Analyze in real time to prevent pollution
• Minimize the potential for accidents

Anastas, P.T. Warner, J. C. Green Chemistry
Theory Practice, Oxford University Press New
York, 1998.
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What does GC mean to St. Olaf College?

• Prepare the next generation of chemical explorers
• who are sensitive to the impact the chemical
  profession has on the local and global
  environments
• who apply creative problem solving skills to
  issues related to building a sustainable, just,
  global society
• who ask questions, seek answers, engage others
• who create resources for chemical education
  (K-16)
• Supports college-wide initiatives

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Major Initiatives
Science Facility Planning
Natural Lands
Composting
Renewable Energy
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• provides an education committed to the liberal
  arts, rooted in the Christian Gospel, and
  incorporating a global perspective. it
  challenges them to be responsible and
  knowledgeable citizens of the world. (St. Olaf
  Mission Statement)
• Sustainable Development meeting the needs of the
  present without compromising the ability of
  future generations to meet their own needs (1987,
  UN Commission on Environment and Development)

• Principles for Thoughtful Action
• Culture of permanence
• Environmental literacy
• Energy flows
• Food that nourishes
• Build for the future
• Waste and wasting it
• Restoration
• Money Values
• Planning Accountability
• Performance
• Possibilities

http//www.stolaf.edu/green/
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The Green Chemistry Case at St. Olaf

• Alter the chemistry curriculum
• 1st year, 2nd year, 3rd year
• Design a science facility that reflects this
  effort
• LEED Gold Building www.stolaf.edu/sciencecompl
  ex/

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Web App Green Chemistry Assistant
http//fusion.stolaf.edu/gca
A collaborative project between St. Olaf College
and US EPA - an extension of the EPA Green
Chemistry Expert System SMART module
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GCA Graphical Output
Wittig Reaction Atom Economy 30.3 E-Factor
58.5 1
Desired Product
Coproduct
Other materials
Solvents
Catalysts
Ring Closing Metathesis of Diethyl
Diallylmalonate Atom Economy 88.3 E-Factor
25.5 1
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2nd Year Sonogashira Coupling Reaction
20 experiments evaluated and 7 changed
Palladium (5) and copper (8) catalyzed coupling
of terminal alkynes with aryl halides Uses
product made in 1st lab of second semester, PEG
200 solvent Microwave 1 minute at 240
Watts Moderate success recycling catalysts and
PEG solvent
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1st Year Periodic Trends Solubility

• Lab Manual includes Green Connections and new
  pre-/post-lab questions
• Replace heptane with ethyl acetate
• Volatile but with lesser hazards
• Option as a renewable resources
• Potentially less harmful degradation products
• Observed color differences
• Chlorine colorless, Bromine orange, and Iodine
  yellow
• Replace chromate anion with thiosulfate anion and
  eliminate barium cation

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1st Year Experimental Changes

• Ethanol oxidation kinetics study
• Eliminate the chromate oxidation process.
• Uses household bleach (6 sodium hypochlorite
  solution)
• Eliminates concentrated hydrochloric acid

• Mystery Product Reactions
• Replace permanganate with iodine redox system
• Eliminates phosphoric and hydrochloric acids
• 70 waste reduction (30 L annually)

7 experiments revised changes implemented
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3rd Year Goals Objectives

• Infuse Analytical Physical labs with green
  chemistry principles
• Develop appropriate metrics
• Test metrics and apply to current lab experiments
  (benchmarking)
• Determine labs with the least green
  characteristics
• NFPA ? 3
• High material/solvent use
• High energy use
• Nonrenewable feedstocks
• Stoichiometric reactions

• Reduce waste stream
• Develop new or modified experiments
• Change chemistry or chemical system
• Reducing material/solvent use in currents labs
• Make volumetric reductions
• Analysis of citrus fruit essential oils by GC,
  GC/MS, Raman and/or IR-ATR.

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Analytical Lab Benchmarks
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3rd Year Solvent Reduction - HPLC
Discovery HS C18 75 x 3 mm (3.5 mm dp), 20 mL
inj, 254 nm detection 68301.50.5
WaterMeOHformic acidtriethylamine 0.50
mL/min. Analytes a) procainamide,
b) qunidine, c) lidocaine, d) diisopyramide.
75 solvent reduction, 50 time reduction
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New Science Facility Dec 1, 2006
Groundbreaking

• Interdisciplinary
• Investigative
• Interactive
• Innovative
• Interconnected
• Inviting
• Integrity
• Green Team, Builder (Boldt), Architect (Holabird
  Root)
• LEED Gold target
• Building as Teacher
• Life-cycle costs
• Chemical Fume Hood Reductions (energy,
  operations, first costs)

• 120,000 NASF, 26 teaching labs
• Informal gathering spaces designed to extend
  learning beyond the classroom and laboratory.
• Green roof terrace
• Adjacent landscape
• Water management basins

65 decrease for intro/2nd year chemistry (2.5
linear ft/student std) 40 decrease across
facility compared to initial design
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Future/On-going Work

• Continue development and implementation in first
  two years of curriculum
• Ramp up development and implementation in third
  year of curriculum
• Piloting upper level p-chem lab (aqueous SEC
  w/proteins dextrans to calculate virial
  coefficients)
• LEED-NC Innovation Credit Green Chemistry
  Hood Reduction
• Presentations 2007 PittCon, 2008 ACS CHAS

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Green Chemistry Around the World
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More 2nd Year Experimental Pursuits

• Ring Closing Metathesis
• Catalytic ring closure with production of
  ethylene
• Microwave for heating proceeded to 98.3
  conversion

• Polyethylene glycol solvent
• potential to recycle the catalyst
• low toxicity, biodegradability, and low vapor
  pressure
• modest catalyst recycling success

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Analytical Metrics
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3rd Year Volumetric Reduction - Downsizing

• Iron determination via bipyridine complexation
• Automation (robotic) vs. human (volumetric)
  method.
• Challenge maintain sig figs and solution
  handling.

AAE 79.87 79.87 AME 1.67x10-5 3.34x10-5 MME
4.77x10-6 9.53x10-6
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3rd Year New Citrus Oil Analysis
Why is lemon oil used for some consumer products
and orange oil for others? How chemically
similar are citrus oil extracts? How would you
determine this when starting with a piece of
fruit (grapefruit, lemon, lime, or orange) and
doing as little sample preparation as possible? .

• SAMPLING STRATEGIES
• Solid Phase Microextraction
• Peel / zest into vial
• PMDS-DVB fiber
• Supercritical CO2 extraction
• Peel / zest into centrifuge tube
• Dry ice water bath

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Physical Properties of CO2
CO2 (l) Good solvent for small, nonpolar
molecules hydrocarbons lt 20 carbon atoms
some aldehydes, esters, and ketones
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Headspace Samples of Citrus Zest
Orange
Lime
Lemon
Grapefruit
GC Conditions VF-5 capillary column (30 m x
0.25 mm x 0.23 mm film), splitless inj 250 C
column oven hold 50 C 1 min, 10 C/min, hold 240
C for 10 min helium carrier gas 30 cm/s. MS
Conditions EI, Full scan 40-350 m/z. SPME
PDMS-DVB fiber, 65 mm, 30 s retracted headspace
exposure.
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Listen to Nature, Learn from Nature
Being less bad is no good.
The world will not evolve past its current state
of crisis by using the same thinking that created
the situation. -Albert Einstein