GREENING ACROSS THE CHEMISTRY CURRICULUM USING WEB-BASED TEACHING MODULES

Michael Cann, Chemistry Department University of Scranton http://academic.scranton.edu/faculty/CANNM1 /greenchemistry.html

Better Things for Better Living Through Chemistry

DuPont

Ibuprophen Lipitor Celebrex Vioxx Rogaine Prozac Viagra Prilosec

Nylon Dacron PET Polystyrene Acrylics Teflon Rayon Composites

DNA Recombinant Technology PCR

ENVIRONMENTAL DISASTERS
DDT CFCs Cuyahoga River Love Canal

Growth in Environmental Regul ation

EPACT FFCA CERFA CRAA AMFA ARPAA AJA ASBCAA ESAA-AECA FFRAA FEAPRA IRA NWPAA CODRA/NMSPAA FCRPA MMPAA APA SWDA CERCLA CZMIA COWLDA FWLCA MPRSAA CAAA CWA SMCRA SWRCA SDWAA RCRAA WLDI PPA PPVA IEREA ANTPA GLCPA ABA CZARA WRDA EDP OPA RECA CAAA GCRA GLFWRA HMTUSA NEEA SDWAA SARA MPRSAA BLRA ERDDAA EAWA NOPPA PTSA UMTRCA ESAA QGA NCPA TSCA FLPMA RCRA NFMA CZMAA NEPA EQIA CAA EPA EEA OSHA FAWRAA NPAA

120 110 100 90 80 70 Number of 60 Laws 50 40 30 20 10

YA WA NBRA IA AA NPS TA FWCA BPA MBCA AEPA

AQ A

NAWCA

WQA NWPA

ARPA

BLBA HMTA FWPCA MPRSA ESA CZMA NCA TAPA FEPCA PWSA MMPA AQA FOIA WRPA AFCA FHSA NFMUA FIFRA PAA

FRRRPA SOWA DPA

FCMHSA

NHPA

WSRA EA RCFHSA

RHA

FAWRA NLRA WPA

WLDA FWCAA FWA AEA

0 1870 1880 1890

1900

1910 1920

1930

1940

1950

1960

1970

1980

1990

2000

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)

Risk Due to a Hazardous Substance Risk=f(Hazard, Exposure)

Controlling Exposure = end of the pipe solution Command and control laws

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)

THE POLLUTION PREVENTION ACT OF 1990

Risk=f(HAZARD, Exposure) Control the hazard, no need to worry about the exposure!

It is Essential that Chemists Place a Major Focus on the Environmental Consequences of Chemical Products and the Processes by which these Products are Made

GREEN CHEMISTRY
Green Chemistry or 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 and resource use (maximize efficiency; utilize renewable resources).

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.

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.

GREEN CHEMISTRY
Pollution Prevention Act 1990 GC Began in 1991 at EPA, Paul Anastas 1996 Presidential Green Chemistry Challenge Awards 1996 Green Chemistry and Engineering Conference 1999 Journal Green Chemistry Chemical and Engineering News 2000 Journal of Chemical Education

Examples of Green Chemistry

New syntheses of Ibuprofen and Zoloft. Water based polyurethanes. Removing Arsenic and Chromate from pressure treated wood. Many new pesticides. New oxidants for bleaching paper and disinfecting water. Getting the lead out of automobile paints. Replacing VOCs and chlorinated solvents.

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.

ENVIRONMENTAL CHEMISTRY
Poster/Oral Presentation on one of the PGCC Award Winning Proposals 1996
Cann, Michael C., J. Chem. Ed. 1999, 76 (12), 1639-1641.

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 Marc Connelly
http://www.acs.org/portal/Chemistry?PID=acsdisplay.html &DOC=education\greenchem\cases.html

Real-World Cases in Green Chemistry

Michael C. Cann and Marc E. Connelly University of Scranton The Concept of Atom Economy How Many Reactant Atoms are Incorporated into the Desired Product and How Many are Wasted? Design and Application of Surfactants for Carbon Dioxide Replacing Smog-Producing and Ozone-Depleting Solvents with CO2 for Precision Cleaning in Manufacturing and Service Industries The BHC Company Synthesis of Ibuprofen A Greener Synthesis of Ibuprofen which Creates Less Waste and Fewer Byproducts DuPont Petretec Polyester Regeneration Technology Converting Scrap Polyethylene Terephthalate (PET) Back Into Its Monomers Bis(2hydroxyethyl)terephthalate and Ethylene Glycol and Conversion of These Monomers Back Into First Quality PET Use of Microbes as Environmentally-Benign Synthetic Catalysts The use of Genetically Altered Escherichia coli to Synthesize Adipic Acid, Catechol and DHS from Renewable Feedstocks Suggested courses are indicated as follows: general chemistry , organic , inorganic , physical b e p t in biochemistry , environmental , polymer , toxicology and industrial .
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Real-World Cases in Green Chemistry

Michael C. Cann and Marc E. Connelly University of Scranton Designing an Environmentally Safe Marine Antifoulant Reducing the Build up of Barnacles, Algae, and Plants on Boat Hulls by Employing a More Environmentally Benign Antifoulant The Invention and Commercialization of a New Chemical Family of Insecticides Exemplified by CONFIRM Selective Caterpillar Control Agent and the Related Selective o,b.e,t Insect Control Agent MACH 2 The Use of Molting Accelerators to Replace More Toxic and Environmentally Harmful Insecticides The Development and Commercial Implementation of 100% Carbon Dioxide as an Environmentally Friendly Blowing Agent for the Polystyrene Foam Sheet Packing o,e,p,in Market Replacing Volatile Organic Compounds and Ozone-Depleting Blowing Agents with CO 2 in the Manufacture of Foam Polystyrene TAML Oxidant Activators: General Activation of Hydrogen Peroxide for Green Oxidation g,o,i,b,e,in Processes Using a Catalyst to Improve the Delignifying (Bleaching) Activity of Hydrogen Peroxide Allowing for a Potential Replacement of Chlorine Based Delignification Processes Production and Use of Thermal Polyaspartate Polymers A Biodegradable Alternative to Current Scale Inhibitors and Dispersing Agents Suggested courses are indicated as follows: general chemistry , organic , inorganic , physical b e p t in biochemistry , environmental , polymer , toxicology and industrial .
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o,i,b,e,p,in g,b,e,t

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

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)

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

GREEN CHEMISTRY MODULES FOR SPECIFIC CHEMISTRY COURSES

Polymer Polyaspartic acid Industrial Petretec polyester regeneration Environmental Sea-nine antifoulant Toxicology Confirm, Mach 2, and Intrepid

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

ATOM ECONOMY Because 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.
H3C CH2 CH2 CH2 OH

Br -

H+

H3C CH2 CH2 CH2

Br

+ H2O

H3C CH2 CH2 CH2

OH

+ Na

Br

+ H2 SO 4

H3C CH2 CH2 CH2

Br

+ NaHSO 4 + H2 O

ATOM ECONOMY
Atom Economy Table

% Atom Economy = (FW of atoms utilized/FW of all reactants) X 100 = (137/275) X 100 = 50%

ATOM ECONOMY IN THE WITTIG REACTION

1 5
REAGENT MF 1 CH3Br 2 C 18H 15P 4 C 6H5Li 6 C 6H10O TOTAL C 31H 33BrLiOP MW 95 262 84 98 539 C 6H10 C 7H12
*

UTILIZED MF CH2

MW 14 0 0 82 96

UNUTILIZED MF HBr C 18H 15P C 6H5Li O C 24H 21BrLiOP

MW 81 262

MW of atoms utilized
% Atom Economy = MW of all the reactants used in the reaction
X100 (96/539) 18%

5)

P ( r

5)

Li

5)

7
*

84 16 443

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)

BHC
H 3C CH
3

BOOTS
H 3C CH
3

H
O

H
O O CH3

A l C l3
O O O CH3

H 3C

HF

H 3C

H 3C CH
3

CH O

H 3C CH
3

CH O

H 3C CH CH
3 3

H2 R a n e y N ic k e l
H 3C CH
3

CH

CH OH

CH

CH

CO Pd

H 3C CH
3

CH

H 3C CH
3

H 3C COOH CH CH
3

COOH CH

Ib u p ro fe n

Ib u p ro fe n

77

At

Ec

nomy

43

A to m E c o n o m y

H3C

H 3C

aO C2H 5

CH Cl COOEt

COOEt O

H 3O

CH

H 2O H
OH

Table 1 ATOM ECONOMY IN THE BROWN SYNTHESIS OF IBUPROFEN

REAGENT UTILIZED IN IBUPROFEN UNUTILIZED IN IBUPROFEN

MF 1 C10H14 2 C 4 H6 O3 4 C4H7ClO2 5 C2H5ONa 7 H3O 9 NH3O 12 H4O2

TOTAL

MW 134 102 122.5 68 19 33 36

MF C10H13 C2H3 CH

MW 133 27 13

MF H C2H3O3 C3H6ClO2

MW 1 75 109.5

0
HO2
IBUPROFEN

C2H5ONa
H3 O NH3O H3

68
19 33 3

0 0 33

WASTE PRODUCTS

C20H42N010ClNa 514.5 C13H18O2 206

C7H24NO8ClNa 308.5

ATOM ECONOMY=(MW Ibuprofen/MW all reactants)x100 =(206/514.5) x100=40

T a b le 2
R E A G E N T M F

A T O M E C O N O M Y IN T H E G R E E N S Y N T H E S IS O F IB U P R O F E N
U T IL IZ E D IN IB U P R O F E N M F M W U N U T IL IZ E D IB U P R O F E N M F M W IN

M W

1 2 4 6 T C

C 10H 14 C 4H 6O 3 H 2 C O O T A L 1 5 H 2 2 O 4

1 3 4 1 0 2 2 2 8 2 6 6

C 10H 13 C 2H 3O H 2 C O C
1 3

1 3 3 4 3 2 2 8
2

H C

1 5 9 0 0 6 0

1 8

2 0 6

A T O M

E C O N O M Y = (M W

Ib u p ro fe n /M W o f a ll re a c ta n ts )x 1 0 0 = ( 2 0 6 /2 6 6 ) X 1 0 0 = 7 7 %

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 >99%; HF >99.9%) greater throughput (three steps versus five steps) and overall yield (virtually quantitative) Fewer auxiliary substances (solvents separation agents)

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)

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

Surfactant

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.

CO2 Surfactant

 http://www.hangersdrycleaners.com/

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 the Hangers CO2 process lowers energy consumption. Using CO2 reduces environmental regulatory burdens for Hangers operators. Uses waste CO2 from other processes.

GREEN CHEMISTRY
Antifoulants (algae and seaweed;

barnacles and diatoms)

Pesticides, infusing green chemistry into environmental chemistry

Antifoulants TBTO
Half-life of TBTO in seawater is > 6 months Bioconcentration, 104 Chronic Toxicity
 Thickness of oyster shells  Sex changes in whelks  Imposex in snails  Immune system in dolphins and others?

Antifoulants
DCOI (PGCC award; Rohm and Haas)
Acutely toxic to a wide range of marine organisms (effective anitfoulant) Rapid biodegradation to nontoxic products ( life < 1 hour) Low Bioconcnetration (bioconcentration =13) Cl O Environmental Conc. < Acute Toxicity level No Chronic Toxicity C8H17 Rapid partitioning to the sediment N (low bioavailability) Cl

4,5-dichloro-2-n-octyl-4-isothiazolin-3-one

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, Janet Boese, Mary Ann Ryan Environmental Protection Agency: Tracy Williamson White House Office of Science and Technology Policy: Paul Anastas Green Chemistry Institute: Mary Kirchhoff