4. Drew University Summer College 2016 SIT IN TEAMS OF 4 “What Color is the Future? An Introduction to Green(er) Chemistry” Alan Mark Rosan, Chemistry Department, Drew University “The future is going to be largely what we design it to be” Paul Anastas, Environmental Science & Technology, 2003, 423A

5. ? BE$T PRACTICE$ ?

6. What “Color” Will The Future Be ?

7. 17 Billion Earths !?

10. US - EVERYBODY - EVERYTHING - EARTH

12. Who Has/Uses/Wants (all) This Stuff ?

13. Who Makes (all) This Stuff ?

14. Three Questions 1) What do chemists do? 2) How do they do what they do? 3) How do they measure success? In your teams talk and write down some ideas. We will share our responses.

15. What do chemists do? How do they do what they do? How do they measure success?

16. What do chemists do? SYNTHESIS & ANALYSIS How do they do what they do? REACTIONS & PROCESSES How do they measure success? METRICS

17. The Source of the Problem The Source of the Solution

20. EPA founded 12-2-1970 TSCA reform June 22, 2016 !

21. Frank R. Lautenberg Chemical Safety for the 21st Century Act Newly reformed law to allow for 66,000 unregulated chemicals to be tested by EPA (20/year)

22. “The world will not evolve past its current state of crisis by using the same thinking that created the situation” Albert Einstein

23. Mission “To advance the broader chemistry enterprise and its practitioners for the benefit of Earth and its people.” The Chemistry Enterprise in 2015 (A 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.” https://portal.acs.org/portal/acs/corg/memberapp?_nfpb=true&_ pageLabel=PP_ARTICLEMAIN&node id=1392&use_sec=false

24. Sustainability 1) What do you think it is ? 2) How can it be achieved ? In your teams talk and write down some ideas.

25. Sustainability "Meeting the needs of the present without compromising the ability of future generations to meet their needs.“ The U.N. Brundtland Commission, 1987 “Sustainability is about stabilizing the currently disruptive relationship between earth’s two most complex systems – human culture – and the living world.” Paul Harkin Blessed Unrest: How the Largest Movement in the World Came into Being and Why No One Saw It Coming (New York: Viking, 2007), 172. How can chemistry contribute in addressing: 1) Population 2) Global climate breakdown - change and chaos to come 3) Depletion of resources (‘fossil’ fuels, metals, land) 4) Food shortages 5) Decline of clean, potable water 6) Housing 7) Waste & Pollution TEACH/LEARN TOXICOLOGY

26. Sustainability? Are we exceeding the carrying capacity of the earth? Are we using resources and creating waste faster than the earth can take our wastes and convert them back into resources? Waste Resources Consumption Nature Humans

27. Sustainability Two Models - what factors impact sustainability ? Threats - what threats impact sustainability ?

28. What Questions Do We Ask About What We Make and What We Use ?

29. What Questions Do We Ask About What We Make and What We Use ? Each team - take an item Complete Activity 1 We will share our ideas. Then we’ll make a list of questions.

30. What Questions Do We Ask About What We Make and Use ? Performance Criteria What is its purpose ? - what does it do ? What is its structure ? How is it made ? What % yield ? What properties does it have ? How does it perform ? What does it cost to make ? How soon can it get to market ? What profit ($$) can be realized ?

31. What Questions Ought We To Ask About What We Make and What We Use ? Performance Criteria

32. What Questions Ought We To Ask About What We Make and Use ? Performance Criteria What is its structure ? Are any parts toxic ? How is it made ? What feedstocks, reagents, solvents, energy etc. ? What is the atom economy ? What is the “E factor” ? What properties ? Does it persist, bioaccumulate or degrade ? Is it (or any precursors) an irritant, mutagen, terratogen, carcinogen, neurotoxin, reproductive/developmental agent, endocrine disrupter ? How well does it perform ? For how long ? Can we design degradation as a function ? What does it cost to make, to use, to recycle, to dispose of ? How soon can it get to market ? What profit ($$) can be realized ?

33. “Why Aren’t We Asking the Right Questions” ? (Paul Anastas) What Questions Ought We to Ask ? 1)What are the properties and bioproperties of the structure and substructure? 2) What properties are important in evaluating bioactivity? 3) What is the behavior of the structure under different environmental conditions? 4) How does the bioactivity change over the life cycle of product and organism?

34. Molecular Design Pyramid - Questions 1. Is the substance fat or water soluble ? Is it persistent or bioaccumlative ? 2. Is it volatile, explosive, flammable ? What is the potential for atmospheric transport or deep lung penetration ? 3. What is the Molecular Weight ? 4. Can it become a gas ? 5. What is the charge ? How does this affect physical & biochemical behavior ? 6. How will the shape, structure and composition influence bioavailability and mechanism of action ? 7. Can it across the blood brain barrier ? Can it penetrate lungs, skin, GI tract ? Can it be taken up by cells ? 8. What is the potential for genetic receptor binding ? 9. What is the behavior of the structure under different environmental conditions ? 10. How does the bioactivity change over the life cycle of product and organism ? 11. What are the properties and bioproperties of the structure and substructure ? 12. What properties are important in evaluating bioactivity ?

35. How many chemicals are there ?

36. How many chemicals are there ? www.cas.org 1957 < 1 million 1990 10 million 1/1/09 40 million 9/8/09 50 millionth Today (2015) 100 million + ~ 75,000 chemicals in commercial use Of these only 650 are covered by the Toxic Release Inventory (TRI) / Emergency Planning and Community Right-to-Know Act for companies that process 25,000 lbs or use 10,000 lbs/yr

37. Chemicals The Good The Bad The Ugly

38. “Better Things for Better Living Through Chemistry” (DuPont) Aspirin Ibuprophen Lipitor Zoloft Prozac Rogaine Viagra Prilosec Tamiflu Nylon Dacron PET Polystyrene Acrylics Teflon Rayon Polyaniline Saran wrap DNA Recombinant Technology PCR Agriculture Electronics Optics Nanotechnology More to be Discovered

39. “Better Things for Better Living Through Chemistry” DuPont, 1939

40. “Better Things for Better Living” Re-source >93 % of production materials do NOT become product Reuse 80 % of all products including tote bags are single use then discard objects Recycle in the US only 33 % of trash gets recycled or composted only 25 % of PET bottles (=25 billion bottles) Remanufacture 1/3 of all plastic is used for packing = 300 lbs/person/yr Reduce to attain a global standard of living equivalent to that in the developed (1 st ) world requires the resources of 3 earths Goal: Acquisition and application of the knowledge that leads from opportunity to solutions CO 2 -> Fuel

41. Let’s Look at Trash C&EN 3/23/15 page 24

42. Let’s Talk Trash Chem & Eng News 3/23/15 page 24

43. GREEN CHEMISTRY What is it ? Nature, 469, 18-20, 2011 Katherine Sanderson In your teams talk about and write down 3 main points of this article. We will share our responses.

44. GREEN CHEMISTRY What is it ? Nature, 469, 18-20, 2011 Environmental Disasters – Bhopal, Love Canal Redesign Life Cycle E factor The 12 Principles Actionable definition Katherine Sanderson

45. GREEN CHEMISTRY What is it ? Nature, 469, 18-20, 2011

46. GREEN CHEMISTRY Sustainable/environmentally benign chemistry is ‘the design of chemical products and processes that reduce or eliminate the use and generation of hazardous substances’ Minimize: 1) waste type and generation 2) energy use 3) resource use (maximize efficiency) Maximize: 1) utility of renewable resources Five key areas : 1) feedstocks 2) reagents 3) reaction types 4) reaction conditions 5) target products

47. For what can Green Chemistry be used ? What makes it green ?

48. Michael C. Cann, University of Scranton Examples of Green Chemistry New syntheses of *Ibuprofen, *Januvia, *Lipitor 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 organic solvents. Lowering of trans fats in oils. Biodegradable polymers and plastics from renewable resources. Replacing petroleum based polymers with cellulose (ionic liquids). To Be Discovered ! Presidential Green Chemistry Challenge Award Winners (1996-present)

49. GREEN CHEMISTRY http://www.youtube.com/watch?v=JV8w6ZagTrE http://www.youtube.com/watch?v=JV8w6ZagTrE “Green chemistry come at the challenge of sustainabiity with the recognition that everything we see, touch and feel is a chemical, and as we look at the products and the processes that are the basis of our society and our economy, if we care about sustainability (and) environmental protection - that ranges from energy to the materials that we use - green chemistry shows us how to design things fundamentally so that they're sustainable and environmentally benign.” “The wonderful thing about green chemistry, and people think I’m joking when they ask me how did I come up with this term – green chemistry – I tell them that green is the color of the environment but it also happens to be in the U.S. the color of money. So what we‘re talking about is being able to meet our environmental and economic goals simultaneously.” Dr. Paul Anastas, EPA, Yale University

51. What is Risk ? Risk = f (Hazard x Exposure) What types of hazard ? Flammable, poison, toxicity, explosive, reproductive/developmental toxicity Toxicity: severity (how much), potency (target organ), reversibility (can you recover) Accidents happen 1,800/yr = 5/day Top 3: BP, Dow, DuPont

52. The Drivers of Green Chemistry The STEEP model: S ocial T echnological E conomic E nvironmental P olitical S ocial T echnological E conomic E nvironmental P olitical Social factors relate to the society and the social systems we live in. It includes demographics, lifestyle aspirations, choices, patterns of work and leisure, mobility and migration, and requirements for security, shelter and food. The elements of Maslow’s Hierarchy of Needs. Technological factors relate to the way that broad technological development changes the industrial environment. It includes changes in the way we can manipulate materials, delivery systems, packaging, transportation, communication, information systems and new business models. Economic factors relate to the impact of local and global financial systems on local, global, national, corporate and personal levels. Access to finance, management of risk, and exploitation of differing cost structures across the globe. Environmental factors relate to the physical environment in which we live. It includes resource consumption, waste generation and disposal, end of life disposal, environmental and health impacts and risks. Political factors relate to the systems that govern us at the global, national and local levels. It includes policy, regulation, laws, legislation, and the political processes that drive them.

53. E - F A C T O R A C T I V I T Y Green Chemistry Education and Outreach for a Sustainable Future Green Chemistry is the science of inventing sustainable products and processes to create safe, non-toxic materials for a sustainable society. The focus of green chemistry is innovation and creativity through chemistry. Throughout Green Chemistry, there are a number of ways to determine if one method of making a product is better than another. One such metric is called the E-Factor or the Environmental Impact Factor. The E-Factor is the measure of the amount of a waste generated while making a product. The simple ratio of units of waste divided by units of product tells us that the lower the E-factor, the less waste is produced. The E-factor is a measure of the quantity of waste produced in making something compared to the amount of useful material obtained in the process (the product). In principle this quantity is easy to compute. E-Factor is defined as: E-Factor = mass of waste ÷ mass of product In practice, it might be difficult to measure the amount of waste generated in a direct way. We could instead measure the quantity of material put into the system and subtract the mass of material output from the system. In the simplest case, the only output from the system would be the final product. If materials (e.g. solvents or catalysts) are recycled, however, then the output of the system would also include those materials. E-Factor = (mass of inputs - mass of outputs) ÷ mass of product The principles of green chemistry direct us to reduce waste rather than dealing with it afterwards. Clearly, the best scenario is one in which no waste is produced. All of the materials that go into the system are used in the final product or they are recycled. In this case, the E-factor is zero, leading to the challenge: "The Goal Is Zero". In this demonstration, imagine that a certain person only chose to eat green M&M's and disposed of the others. In that case, you might consider the input to the system to be a normal bag of M&M's and the output to be just the green ones. Use a bag of M&M’s to calculate the E-factor assuming that your product is the green M&M’s. What do you think the real E-Factor will be in a normal bag of M&M‘s when you try this exercise? # of Green M&M’s in the bag: __________ # of non-Green M&M’s in the bag: _________ E-Factor: _____________________________________________________________________ What suggestions do you have to improve your E-Factor and reduce the waste in your bag of M&M’s?

54. Atom Economy and E F M & M Activity Orange

55. Atom Economy and E F M & M Activity Orange + Red

56. Atom Economy and E F M & M Activity Orange + Red = Green

57. Atom Economy and E F M & M Activity Orange + Red = Green + Road

58. Atom Economy and E F M & M Activity Orange + Red = Green + Road Atom Economy (AE)is # letters in green = of M&M’s # total letters used Environmental FACTOR = waste/product =

59. Atom Economy and E F M & M Activity Orange + Red = Green + Road Atom Economy (AE)is # letters in green = 5/9 =.55 of M&M’s # total letters used (55 %) Environmental FACTOR = waste/product = 4/5 = 0.8

60. “And the best E FACTOR goes to …

62. “E” Factor R.A. Sheldon Chemistry & Industry (London) 1992, 903-906 Green Chemistry, 2007, 9(12), 1261-1384 E factor = mass waste / mass product = (mass in – mass all outputs) / total mass product Total Waste (ton) 10 6 10 5 10 4 10 3

63. Green Chemistry - Principles “As to methods, there may be a million and then some, but principles are few. The man who grasps principles can successfully select his own methods. The man who tries methods, ignoring principles, is sure to have trouble.” Ralph Waldo Emerson

65. The Twelve Principles of GREEN CHEMISTRY (Paul Anastas and John 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. Called Atom Economy. % Atom Economy = (MW of product/MW of all reactants) x 100 % 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.

66. The Twelve Principles of GREEN CHEMISTRY (Paul Anastas and John 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 be chosen so as to minimize the potential for chemical accidents, including releases, explosions, and fires.

69. Can It be Made Better ? An Example of Greener Chemistry

71. Imagine … a world in which – instead of toxic solvents and chemicals – industrial manufacturing used sugar, starch and sunlight as inputs. Imagine products that biodegrade into utterly benign substances. Imagine pure, clean water leaving factories and polluted sources brought back to life. What if industrial chemicals were bio-based and generated by farmers practicing sustainable agriculture? Imagine a workplace free of “hazmat” gear, factories without scrubbers, and a world where CO 2 is used as a valuable industrial input rather than emitted as a green house gas. Green Chemists are making this vision a reality. See: http://advancinggreenchemistry.org/#sthash.c6Jh2CXR.dpufhttp://advancinggreenchemistry.org/#sthash.c6Jh2CXR.dpuf

72. Green chemistry is: A reaction that utilizes a green liquid. The design of chemical products and processes that reduce or eliminate the use or generation of hazardous substances. Anything, including treatment or recycling, that reduces pollution. Any reaction performed by Kermit the Frog or his relatives. Question #1

73. Green chemistry is also be described as: Sustainable chemistry. Chemistry that is benign by design. Pollution prevention at the molecular level. All of the above. Question #2

74. The Future – It is up to us 50 % of the products & processes that will be needed in the next 10-25 years have not been invented yet … “Never doubt that a small group of thoughtful, committed people can change the world. Indeed, it is the only thing that ever has.“ Margaret Mead “There are those who look at things the way they are, and ask why.. I dream of things that never were, and ask why not?” Robert Kennedy “Unless someone like YOU cares a whole awful lot, nothing is going to get better. It's not.” The Lorax (Dr. Seuss) QUESTIONS ?

75. Think Green, Act Green, Be Green

76. Thank you and thanks to $upporters The Teagle Foundation Harlem Educational Activities Fund The Prudential Foundation Provident Bank Bank of America Independent College Fund of New Jersey And Partners Union Settlement Association (East Harlem) RU Ready for Work Programs at West Side High School (Newark, NJ) Marion Bolden Student Center in Newark Drew University “Building Bridges to (and from) the Liberal Arts” Project Leaders: Wendy Kolmar and Maya Sanyal (Drew University) and Steven Portericker (Union Settlement Association)

78. GREEN CHEMISTRY Major Focus: Replacement of volatile organic solvents called “VOC’s” and halogenated solvents. Almost 15 billion kilograms are produced worldwide each year. – Solvent free processes – Solvent alternatives: Ionic liquids Fluorous solvents Carbon dioxide (CO 2, O=C=O)

79. Solubility of Substances in CO 2 Carbon dioxide is a non polar molecule since the dipoles of the two bonds cancel one another. Thus dipole moment μ = 0 Carbon dioxide will dissolve small non polar molecules – hydrocarbons having less than 20 carbon atoms – other organic molecules such as aldehydes, esters, ketones But it will not dissolve larger molecules such as oils, waxes, grease, polymers, proteins or polar molecules

80. GREEN CHEMISTRY Dry Cleaning – Initially gasoline and kerosene were used – Chlorinated solvents are now used, such as “perc” – Supercritical/liquid carbon dioxide (CO 2 )

81. Surfactant surface active agent

82. CO 2 Surfactant a Green Solution ! Joe DeSimone, Univ. North Carolina and NCSU, NSF Science and Technology Center for Environmentally Responsible Solvents and Processes, Presidential Green Chemistry Award, 1997 http://www.hangersdry cleaners.com/

83. Environmental/Economic Advantages of Liquid CO 2 1) Using CO 2 eliminates hazardous associated with generation and disposal of PERC 2) CO 2 does not pose the environmental and human health risks associated with PERC (used by 34,000 dry cleaners in US) 3) Using CO 2 reduces environmental regulatory burdens for Hangers operators 4) Uses waste CO 2 from other processes

85. Think Green, Act Green, Be Green

87. Population of the Earth Population growth is # 1 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) * 7 billion in 2011 (12 years later) 2050 projections range from 7.5 - 11 billion At a 1% growth rate the US will double in population in 70 years. Current net increase is 2.5 new souls/second ≈ 10,000/hour ≈ 200,000/day ! all with increased life expectancy 1900, 47 years; 1990, 75 years

88. There exists about 4.5 acres/person of biologically productive space on the earth Of Some Nations http://www.earthday.net/footprint/index_reset.asp?pid=2066614043005642

89. In 2008 we required ͂ 6 acres per person, 33% more than the natural biological capacity of ͂ 4-5 acres

90. Michael C. Cann, University of Scranton Sustainability? Climate Change/Rising Temperatures 1900s 0.7-1.5 o F rise in temp; projected of 4.5 o F by 2100 Eight of the 10 warmest years since 1860 have occurred within the last –top 5: 2005, 1998, 2002, 2003, 2004 http://www.nasa.gov/vision/earth/environment/2005_warmest.html http://www.nasa.gov/vision/earth/environment/2005_warmest.html Tree rings and underwater sediments indicate the 20 th century is warmest in the last 1000 years

92. ENVIRONMENTAL DISASTERS DDT CFC’s (Cl-F-C) Cuyahoga River Love Canal, NY Bhopal, India [

93. “Better Things for Better Living” Re-source >93 % of production materials do NOT become product Reuse 80 % of all products are single use then discard objects Recycle in the US 33 % of trash gets recycled or composted Remanufacture Reduce to attain a global standard of living equivalent to that in the developed (1 st ) world requires the resources of 3 earths Goal: Acquisition of the knowledge that leads to solutions

94. “Better Things for Better Living Through Chemistry” DuPont, 1939

95. “Better Things for Better Living Through Chemistry” (DuPont) Aspirin Ibuprophen Lipitor Zoloft Prozac Rogaine Viagra Prilosec Tamiflu Nylon Dacron PET Polystyrene Acrylics Teflon Rayon Polyaniline Saran wrap DNA Recombinant Technology PCR Agriculture Electronics Optics Nanotechnology

96. GREEN CHEMISTRY History 1962 Rachel Carson “Silent Spring” 1970 US Environmental Protection Agency 1970 1 st Earth Day April 22 1970 Resource Recovery Act 1976 US Toxic Substances Control Act (TSCA) S.847 TSCA Reform Bill 1980 US Comprehensive Environmental Response Compensation and Liability Act (“Superfund”) 1990 US Pollution Prevention Act 1993 Joe Breen coined the term "Green Chemistry“ 1996 Presidential Green Chemistry Challenge Awards http://www.epa.gov/greenchemistry/pubs/pgcc 1997 1 st Green Chemistry and Engineering Conference 1998 “Green Chemistry-Theory & Practice” P. Anastas and J. Warner 1999 Journal “Green Chemistry” 2000 Green Chemistry Institute (GCI) integrated into ACS 2007 Europe Registration, Evaluation, Authorization and Restriction (REACH) 2008 California Green Chemistry Initiative

98. Presidential Green Chemistry Challenge Awards 1996 – present www.epa.gov

99. Major US Environmental Laws 1970 Clean Air Act. Regulates air emissions. 1972 National Environmental Policy Act. Requires in part that EPA review environmental impact statements of proposed major federal projects (e.g. highways, buildings, airports, parks and military complexes). 1972 Clean Water Act. Establishes the sewage treatment construction grants program and a regulatory and enforcement program for discharges of pollutants into U.S. waters. 1972 Federal Insecticide, Fungicide & Rodenticide Act. Governs distribution, sale and use of pesticide products. All pesticides must be registered (licensed) by EPA. 1972 Ocean Dumping Act. Regulates the intentional disposal of materials into ocean waters. 1974 Safe Drinking Water Act. Establishes primary drinking water standards. 1976 Toxic Substances Control Act. Requires the testing, regulating, and screening of all chemical produced or imported in the U.S. 1976 Resource Conservation & Recovery Act. Regulates solid and hazardous waste form “cradle to grave.” 1976 Environmental Research & Development Demonstration Act. Authorizes all EPA research programs. 1980 Comprehensive Environmental Response, Compensation & Liability Act, (Superfund). Provides for a federal “superfund” to clean up abandoned hazardous waste sites, accidental spills and other emergency releases of pollutants in the environment. Emergency Planning & Community Right-to-Know Act. Requires that industries report toxic releases and encourages planning by local communities to respond to chemical emergencies. 1990 Pollution Prevention Act*. Seeks to prevent pollution by encouraging companies to reduce the generation of pollutants through cost-effective changes in production, operation, and raw material use.

101. For what can Green Chemistry be used ? What makes it green ?

102. Michael C. Cann, University of Scranton Examples of Green Chemistry New syntheses of *Ibuprofen, *Januvia, *Lipitor 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). To Be Discovered ! Presidential Green Chemistry Challenge Award Winners (1996-present)

103. Principles of Green Engineering I Inherently non-hazardous and safe M Minimize material diversity P Prevention instead of treatment R Renewable material and energy inputs O Output-led design V Very simple E Efficient use of mass, energy, space & time M Meet the need E Easy to separate by design N Networks for exchange of local mass & energy T Test the life-cycle of the design S Sustainability throughout the product lifecycle

104. GREEN CHEMISTRY Major Focus: Replacement of organic solvents called “VOC’s” and halogenated solvents. Almost 15 billion kilograms are produced worldwide each year. – Solvent free processes – Solvent alternatives: Ionic liquids Fluorous solvents Carbon dioxide (CO 2, O=C=O)

105. Solubility of Substances in CO 2 Carbon dioxide is a non polar molecule since the dipoles of the two bonds cancel one another. Thus dipole moment μ = 0 Carbon dioxide will dissolve small non polar molecules – hydrocarbons having less than 20 carbon atoms – other organic molecules such as aldehydes, esters, ketones But it will not dissolve larger molecules such as oils, waxes, grease, polymers, proteins or polar molecules

106. GREEN CHEMISTRY Dry Cleaning – Initially gasoline and kerosene were used – Chlorinated solvents are now used, such as “perc” – Supercritical/liquid carbon dioxide (CO 2 )

107. Surfactant surface active agent

108. CO 2 Surfactant Joe DeSimone, Univ. North Carolina and NCSU, NSF Science and Technology Center for Environmentally Responsible Solvents and Processes, Presidential Green Chemistry Award, 1997

109. Michael C. Cann, University of Scranton CO 2 Surfactant - a Greener Solution !

110. http://www.hangersdrycleaners.com/

111. Environmental/Economic Advantages of Liquid CO 2 Using CO 2 eliminates hazardous associated with generation and disposal of PERC CO 2 does not pose the environmental and human health risks associated with PERC (used by 34,000 dry cleaners in US) Using CO 2 reduces environmental regulatory burdens for Hangers operators Uses waste CO 2 from other processes

112. Michael C. Cann, University of Scranton Preservation of Wood A $ 4 billion dollar industry Industry annually pressure treats more 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 yrs Without treatment $15 billion dollar increase in lumber production (transportation, construction, utilities) 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)

113. Production of Pressure Treated Wood (PTW) 95% PTW was treated with “CCA”. What is “CCA” ? In 2001 7 billion board feet of PTW produced (about 1/5 of all softwood lumber sold) 150 million pounds of “CCA” involved 40 million pounds of arsenic (As) 64 million pounds of hexavalent chromium (Cr) Wood is placed in a vacuum (depletes wood cells of air and water); “CCA” solution is applied under pressure infiltrating the wood

114. Michael C. Cann, University of Scranton Production of PTW Typical CCA solution: 35.3% CrO 3 ; 19.6% CuO; 45.1% As 2 O 3 Cu, Cr and As levels in the wood 1000-5000 mg/kg So … 8x10 deck => 4 lb of metals (1.9 lb Cr, 1.36 lb As, 0.74 lb Cu)

115. 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/arsenic.playgrounds/index.html

117. Removing the Arsenic and Chromium from PTW 2002 Chemical Specialties, Inc., ACQ (Alkaline Copper Quaternary Ammonium Compound) Preserve, Chemical Specialties, Inc., (CSI) 2002 Pres. Award GC 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 (LD 50 =730 – 800 mg/kg; about the same as salt and ethanol) in ACQ Disposal of ACQ treated wood: may be disposed of in general landfills

118. u Crystal Simple Green ® n Water based industrial cleaner n Non-toxic, biodegradable surfactants n Replaces traditional organic solvents n Eliminates hazardous waste sludge production and VOC pollution Sunshine Makers, Inc. Industrial Cleaning

119.  Isomet  Mixture of isoparaffinic hydrocarbon, propylene glycol monomethyl ether, and isopropyl alcohol  Replaces Typewash (mixture of methylene chloride, toluene, and acetone)  Excellent performance in postage stamp and overprinting presses  Acceptable properties (cleaning ability, solvent evaporation rate, odor, environmental compliance, and cost) U.S.Bureau of Engraving and Printing Industrial Cleaning