Preface

This book is intended for chemists, chemical engineers, and others who want to see a better world through chemistry and a transition from its present unsustainable course1 to a sustainable future.2 (A sustainable future is one that allows future generations as many options as we have today.) It is meant to serve as an introduction to the emerging field of green chemistry of pollution prevention. It is based on a one-semester three-credit course3 given at the seniorgraduate level interface at the University of Delaware each year from 1995 to 1998. Books and courses in environmental chemistry usually deal with contaminants that enter air, water, and soil as a result of human activities: how to analyze for them and what to add to the smokestack or tailpipe to eliminate them. They are also concerned with how to get the contaminants out of the soil once they are there. Because texts such as those by Andrews et al.,4 Baird,5 Crosby,6 Gupta,7 Macalady,8 Manahan,9 and Spiro and Stigliani10 cover this area adequately, such material need not be repeated here. Green chemistry11 avoids pollution by utilizing processes that are benign by design. (The industrial ecology12 being studied by engineers and green chemistry are both parts of one approach to a sustainable future.) Ideally, these processes use nontoxic chemicals13 and produce no waste, while saving energy and helping our society achieve a transition to a sustainable economy. It had its origins in programs such as 3Ms Pollution Prevention Pays. It was formalized in the United States by the Pollution Prevention Act of 1990. Since then, the U.S. Environmental Protection Agency and the National Science Foundation have been making small grants for research in the area. Some of the results have been summarized in symposia organized by these agencies.14 This book cuts across traditional disciplinary lines in an effort to achieve a holistic view. The material is drawn from inorganic chemistry, biochemistry, organic chemistry, chemical engineering, materials science, polymer chemistry, conservation, etc. While the book is concerned primarily with chemistry, it is necessary to indicate how this fits into the larger societal problems. For example, in the discussion of the chemistry of low-emissivity windows and photovoltaic cells, it is also pointed out that enormous energy savings would result from incorporating passive solar heating and cooling in building design. Living close enough to walk or bike to work or to use public transportation instead of driving alone will save much more energy than would better windows. (Two common criticisms of scientists is that their training is too narrow and that they do not consider the social impacts of their work.) This book begins with a chapter on the need for green chemistry, including the toxicity of chemicals and the need for minimization of waste. The next three chapters deal with the methods that are being studied to replace some especially noxious materials. Chapters 58 cover various ways to improve separations and to reduce waste. Chapter 9 continues this theme and switches to combinations of biology and chemistry. Chapter 10 discusses many optical resolutions done by enzymes or whole cells. Chapter 11, on agrochemicals, continues the biological theme. Chapters 12 through 15 cover various aspects of sustainability, such as where energy and materials will come from if not from petroleum, natural gas, or coal; how to promote sustainability by making things last longer; and the role of recycling in reducing demands on the natural resource base. The last three chapters try to answer the question that arises at nearly every meeting on green chemistry: Why is it taking so long for society to implement new knowledge of how to be green? The topics within these chapters are not confined to specific areas. For example, cyclodextrins are discussed not only under supported reagents, but also under separations by inclusion compounds or under chemistry in water. Surfactants have
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Preface

been placed under doing chemistry in water. They are also mentioned as alternatives for cleaning with organic solvents and in the discussion on materials from renewable sources. An effort has been made to cross-reference such items. But for the reader who has any doubt about where to find an item, a comprehensive index is included. The industrial chemistry on which much green chemistry is based may be foreign to many in academia, but many good references are available.15 There is much more emphasis in industrial chemistry on catalysis and the organometallic mechanisms that often go with them. Improved catalysts are often the key to improved productivity, using less energy and generating less waste.16 Again, many good sources of information are available.17 In addition, there are two books on the chemistry and biology of water, air, and soil.18 Each chapter in Introduction to Green Chemistry lists recommended reading, consisting primarily of review papers and portions of books and encyclopedias. This allows detailed study of a subject. The introductions to current journal articles often contain valuable references on the status of a field and trends in research. However, the traditional grain of salt should be applied to some news items from trade journals, which may be little more than camouflaged advertisements. The examples in the book are drawn from throughout the world. In the student exercises that accompany each chapter, readers are often asked to obtain data on their specific location. In the United States, one need look no further than the local newspaper for the results of the toxic substances release inventory. This data can also be found on websites of the U.S. Environmental Protection Agency (http://www.epa.gov/opptintr/tri) and state environmental agencies,19 as well as on comparable websites of other countries (e.g., http:// www.unweltbundesamt.de for the German environmental agency). Nongovernmental organizations also post some of this data (e.g., the Environmental Defense Chemical Scorecard, www.scorecard.org, and the Committee for the National Institute for the Environment, www.cnie.org). The data available on the Internet is growing rapidly.20 The environmental compliance records of more than 600 U.S. companies can be found at http://es.epa.gov/oeca/sfi/index.html. A catalog of U.S. Environmental Protection Agency documents can be found at http://www.epa.gov/ ncepihom/catalog.html. Data on the toxic properties of chemicals can be found at toxnet.nlm.nih.gov and http:// www.chemquik.com. Some of the exercises sample student attitudes. Others call for student projects in the lab or in the community. Some of the questions are open-ended in the sense that society has yet to find a good answer for them, but they leave room for discussion. Those using this volume as a textbook will find field trips helpful. These might include visits to a solar house, a farm using sustainable agriculture, a tannery, a plant manufacturing solar cells, etc. Although the course at the University of Delaware had no laboratory, one would be useful to familiarize students with techniques of green chemistry that they might not encounter in the regular courses. These might include the synthesis, characterization, and evaluation of a zeolite, running a reaction in an extruder, using a catalytic membrane reactor, adding ultrasound or microwaves to a reaction, making a chemical by plant cell culture, doing biocatalysis, making a compound by organic electrosynthesis, running a reaction in supercritical carbon dioxide, and use of a heterogeneous catalyst in a hot tube. Ideally, students would run a known reaction first, then an unknown one of their own choice (with appropriate safety precautions). Such a lab would require the collaboration of several university departments. There is a myth that green chemistry will cost more. This might be true if something was to be added at the smokestack or outlet pipe. However, if the whole process is examined and rethought, being green can save money. For example, if a process uses solvent that escapes into the air, there may be an air pollution problem. If the solvent is captured and recycled to the process, the savings from not having to buy fresh solvent may be greater than the cost of the equipment that recycles it. If the process is converted to a water-based one, there may be additional savings. It is hoped that many schools will want to add green chemistry to their curricula. Sections of this book can be used in other courses or can be used by companies for in-house training. The large number of references makes the book a guide to the literature for anyone interested in a sustainable future.
Albert S. Matlack

REFERENCES
1. 2. 3. 4. J. Lubchenko, Science, 1998, 279, 491. (a) R. Goodland and H. Daly. Ecol. Appl., 1996, 6, 1002. (b) A. Merkel, Science, 1998, 281: 336. A.S. Matlack, Green Chem, 1999, 1(1): G17. J.E. Andrews, P. Brimblecombe, T.D. Jickells, P.S. Liss, eds. Introduction to Environmental Chemistry. Blackwell Science, Cambridge, MA 1995.