CHAPTER 1 CHEMISTRY GREEN CHEMISTRY AND ENVIRONMENTAL CHEMISTRY

CHAPTER 1 CHEMISTRY, GREEN CHEMISTRY, AND ENVIRONMENTAL CHEMISTRY From Green Chemistry and the Ten Commandments of Sustainability, Stanley E. Manahan, Chem. Char Research, Inc. , 2006 manahans@missouri. edu

1. 1. Chemistry is Good • All matter is chemical; we are chemical • The human body is a complex chemical factory • Green Chemistry seeks to present a body of chemical knowledge from the most fundamental level within a framework of the relationship of chemical science to human beings, their surroundings, and their environment. • Green chemistry is the practice of chemistry in a manner that maximizes its benefits while eliminating or at least greatly reducing its adverse impacts

Good Things from Chemistry • Pharmaceuticals that have improved health and extended life • Fertilizers that have greatly increased food productivity • Semiconductors that have made possible computers and other modern electronic devices The Downside of Chemistry • Pollutants • Toxic substances • Nonbiodegradable plastic containers These have resulted in harm to the environment

Major Categories of Chemistry • Inorganic chemistry deals with materials composed of most elements other than carbon (and includes a few carbon compounds) • Organic chemistry deals with carbon-containing materials, most having carbon-carbon bonds • Physical chemistry involves the underlying theory and physical phenomena that explain chemical processes • Biochemistry is the chemistry of living processes • Analytical chemistry is the identification and quantification of chemical species, often at very low levels

The Old Attitude: “By sensible definition any by-product of a chemical operation for which there is no profitable use is a waste. The most convenient, least expensive way of disposing of said waste—up the chimney or down the river—is best. ” From American Chemical Industry— A History, W. Haynes Van Nostrand Publishers, 1954

Chemists and Chemistry are Part of the Solution • Chemistry is required to deal with environmental problems and challenges to sustainability • Of all professionals, chemists are the best qualified to understand environmental problems from the misuse of chemistry • The practice of environmentally beneficial chemistry is not a burden, but rather an opportunity that challenges human imagination and ingenuity

1. 2. THE ENVIRONMENT AND THE FIVE ENVIRONMENTAL SPHERES

The Atmosphere • Very thin, most within several kilometers of Earth’s surface • Provides oxygen for animals and other organisms, carbon dioxide and nitrogen for plants • Vital protective function • Stratospheric ozone protects against harmful ultraviolet • Stabilizes Earth’s temperature by re-absorbing outgoing heat as infrared radiation • Conduit for fresh water by way of the hydrologic cycle

The Hydrosphere • More than 97% in oceans • Most of the remaining fresh water is ice and snow in polar ice caps and glaciers • Small fraction of water in atmospheric water vapor • Fresh water on the surface in lakes, reservoirs, and streams and as groundwater in underground aquifers

The Geosphere • Includes all rocks and minerals Soil, where present Crust, several km or less Lithosphere, 50 -100 km Molten rock • The crust is the part of the geosphere that is available to interact with the other environmental spheres and that is accessible to humans

The Biosphere • All living organisms • Most found in a very thin layer at the interface of the geosphere and atmosphere and in the hydrosphere • Involved with the geosphere, hydrosphere, atmosphere and even anthrosphere through biogeochemical cycles • Biogeochemical cycles involve important life elements including carbon, nitrogen, and phosphorus

The Anthrosphere • Strong interactions with other environmental spheres • Cultivation of land modifies the geosphere • Diversion and use of water affects the hydrosphere • Emission of particles, acid gases, organics, greenhouse warming carbon dioxide • Perturbation of biogeochemical cycles • Entering anthropocene era

Environmental Chemistry Environmental chemistry is the study of the sources, reactions, transport, and fates of chemical species involving all environmental spheres

Aquatic Chemistry Gas exchange with the atmosphere

Atmospheric Chemistry

Chemistry of the Geosphere and Soil

Chemistry of the Biosphere and Toxicological Chemistry

Chemistry of the Anthrosphere within a Framework of Industrial Ecology

1. 4. Environmental Pollution Awareness from • Silent Spring, Rachel Carson, 1962 • Approximately 10, 000 deformed children from thalidomide • Visible air pollution • “Dead” bodies of water • Love Canal around 1970

Command Control Approach Emphasizing End-of-Pipe Treatment Measures

1. 5. What is Green Chemistry? Green chemistry is the sustainable practice of chemical science and manufacturing within a framework of industrial ecology in a manner that is sustainable, safe, and non-polluting, consuming minimum amounts of energy and material resources while producing virtually no wastes.

Green Chemistry is Sustainable • Economic: At a high level of sophistication, green chemistry normally costs less in conventional economic terms (as well as environmental costs) than chemistry as it is traditionally practiced • Materials: By efficiently using materials, maximum recycling, and minimum use of virgin raw materials, green chemistry is sustainable with respect to materials • Waste: By reducing insofar as possible, or even totally eliminating their production, green chemistry is sustainable with respect to wastes

1. 6. Green Chemistry and Synthetic Chemistry Synthetic chemistry involves finding ways to make new chemicals and new ways to make known chemicals • Use existing feedstocks, but make them by more environmentally benign processes • Use other feedstocks made by environmental benign processes

Yield and Atom Economy (1) Typical reaction with less than 100% yield and with byproducts

Yield and Atom Economy (2)

1. 7. Reduction of Risk: Hazard and Exposure Risk = F{hazard exposure} • Reduced exposure: The hazard remains, but exposure to it is reduced, such as by wearing safety goggles around an eye hazard (a command control approach) • Reduced hazard: The hazard is diminished or eliminated at its source; measures still may be taken to reduce exposure to remaining hazard • Hazard exposure is less costly because costs of protective measures may be reduced

1. 8. The Risks of No Risks • Refusal to take any risks can cause scientific and economic progress to stagnate • Example: Refusal to take the risks of thermally treating wastes (hazardous waste incineration) can lead to waste accumulation, or important industrial processes making the waste may be ceased • Example: Unwillingness to take risks involved with nuclear energy can lead to greenhouse warming from using fossil fuels or to economic stagnation from energy shortages

1. 9. Waste Prevention • Costs of engineering controls, regulatory compliance, personnel protection, wastewater treatment, and safe disposal of hazardous solid wastes have become high costs of doing business • Waste prevention applying the principles of green chemistry and industrial ecology is a much better approach

1. 10. Twelve Principles of Green Chemistry (1) 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. Synthetic processes should avoid use and generation of toxic and environmentally damaging substances 4. Chemical products should be as effective as possible but with minimum toxicity 5. Auxiliary substances, such as solvents and separation agents should be avoided or should be as innocuous as possible 6. Energy requirements should be low; extreme temperatures and pressures should be avoided

Twelve Principles of Green Chemistry (2) 7. Raw materials should be from renewable sources 8. Derivatization for blocking groups protection and property modification should be avoided 9. Catalytic reagents should be used when possible because of their specificity and minimum amounts required 10. Chemical products should be designed so that at the end of their lifetime they readily break down to harmless products 11. The best analytical and monitoring capabilities should be employed to allow real-time, in-process monitoring that prevents formation of hazardous substances 12. Substances and forms of them used should be chosen to avoid potentially harmful releases, fires, and explosions

1. 11. Some Things to Know About Chemistry Before You Even Start • Fewer than 100 naturally occurring elements, about 30 made by humans • All elements composed of chemically identical atoms • Each atom of a particular element has the same number of positively charged protons in its nucleus equal to the atomic number of the element. • Electrons are in motion around the nucleus; a neutral atom has equal numbers of electrons and protons • Each element has a chemical symbol (nitrogen, N, sodium, Na, for Latin name natrium • The average mass of all atoms of an element is its atomic mass

1. 12. Combining Atoms to Make Molecules and Compounds • Two or more uncharged atoms bonded together by chemical bonds compose a molecule • A covalent chemical bond is composed of two or more shared electrons The H atoms in elemental hydrogen are held together by chemical bonds in molecules That have the chemical formula H 2

CHEMICAL COMPOUNDS • A chemical compound is a substance consisting of atoms of two or more elements joined together by chemical bonds Hydrogen atoms and To form molecules in oxygen atoms bond which 2 H atoms are together attached to 1 O atom The chemical formula of the resulting compound, water is H 2 O

Ionic Bonds • Ions are electrically charged atoms or groups of atoms • Cations are positively charged ions and anions are negatively charged ions • An ionic compound consists of cations and anions held together by their opposite charges—ionic bonds—in a crystalline lattice. The transfer of a negatively charged electron from a neutral sodium atom to a neutral chlorine atom produces positively charged Na+ cations and negatively charged Cl- ions held together by ionic bonds in the ionic compound sodium chloride

1. 13. Chemical Reactions • A chemical reaction occurs when chemical bonds are broken and formed and atoms are exchanged to produce chemically different species. CH 4 + 2 O 2 Reactants 2 H 2 O + CO 2 Products Yields Above is a chemical equation for the reaction of methane with oxygen. It is balanced because it has the same number of each kind of atom (1 C, 4 H, 4 O) among both the reactants and products.

1. 14. The Nature of Matter and States of Matter • Most matter consists of mixtures composed of two or more chemically distinct substances • A homogeneous mixture, such as air, consists of substances mixed at the molecular level that cannot be separated by mechanical means. • A heterogeneous mixture is composed of two or more substances that are visibly distinct and can be separated by mechanical means. • Mixtures are important in green chemistry; the separation of components of wastes and byproducts is often a significant expense in recycling

States of Matter A solid has a definite shape and volume regardless of the container into which it is placed. A quantity of liquid has a definite volume, but takes on the shape of its container. A quantity of gas has the shape and volume of the container it occupies.