Introduction to Green Chemistry

564 Pages·2001·5.385 MB·English

by  Matlack A.S.

ISBN: 0-8247-0411-8
This book is printed on acid-free paper.
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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 course1to a sustainable future.2(A sustainable future is one that allows future gen-
erations 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 course3given at the senior–graduate 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.,4Baird,5Crosby,6Gupta,7Macalady,8Manahan,9and Spiro and Stigliani10cover 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 chemicals13and produce no waste, while saving energy and helping our society achieve a transition to a sustain-
able economy. It had its origins in programs such as 3M’s “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 in-
organic chemistry, biochemistry, organic chemistry, chemical engineering, materials science, polymer chemistry, conserva-
tion, etc. While the book is concerned primarily with chemistry, it is necessary to indicate how this fits into the larger soci-
etal 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 de-
sign. 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 min-
imization of waste. The next three chapters deal with the methods that are being studied to replace some especially noxious
materials. Chapters 5–8 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 pro-
mote 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 un-
der supported reagents, but also under separations by inclusion compounds or under chemistry in water. Surfactants have
iii
iv 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.15There is much more emphasis in industrial chemistry on catalysis and the organometallic mech-
anisms that often go with them. Improved catalysts are often the key to improved productivity, using less energy and gener-
ating less waste.16Again, many good sources of information are available.17In addition, there are two books on the chem-
istry and biology of water, air, and soil.18
Each chapter in Introduction to Green Chemistrylists 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. En-
vironmental Protection Agency (http://www.epa.gov/opptintr/tri) and state environmental agencies,19as well as on compa-
rable websites of other countries (e.g., http://www.unweltbundesamt.de for the German environmental agency). Non-
governmental 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.20The 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 dis-
cussion.
Those using this volume as a textbook will find field trips helpful. These might include visits to a solar house, a farm us-
ing 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 chem-
ical by plant cell culture, doing biocatalysis, making a compound by organic electrosynthesis, running a reaction in super-
critical 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 pro-
cess 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 lit-
erature for anyone interested in a sustainable future.
Albert S. Matlack
REFERENCES
1. J. Lubchenko, Science, 1998, 279, 491.
2. (a) R. Goodland and H. Daly. Ecol. Appl., 1996,6, 1002. (b) A. Merkel, Science, 1998, 281: 336.
3. A.S. Matlack, Green Chem, 1999, 1(1): G17.
4. J.E. Andrews, P. Brimblecombe, T.D. Jickells, P.S. Liss, eds. Introduction to Environmental Chemistry. Blackwell Science, Cam-
bridge, MA 1995.
Preface v
5. C.L. Baird, Environmental Chemistry, W.H. Freeman, New York, 1995.
6. D.G. Crosby, Environmental Toxicology and Chemistry, Oxford University Press, New York, 1998.
7. R.S. Gupta, Environmental Engineering and Science: An Introduction, Government Institutes, Rockville, MD, 1997.
8. D.L. Macalady, Perspectives in Environmental Chemistry, Oxford University Press, Oxford, England, 1997.
9. S.E. Manahan, Environmental Chemistry, 6th ed., Lewis Publishers, Boca Raton, FL, 1994; Fundamentals of Environmental Chem-
istry, Lewis Publishers, Boca Raton, FL, 1993.
10. T.C. Spiro, W.M. Stigliani, Chemistry of the Environment, Prentice Hall, Upper Saddle River, NJ, 1996.
11. J. Clark, Chem Br, 1998, 34(10): 43.
12. (a) B. Hileman, Chem Eng News, July 20, 1998, 41; (b) J. Darmstadter, Chem Eng News, August 10, 1998, 6; (c) N.E. Gallopou-
los, Chem Eng News, August 10, 1988, 7; (d) T.E. Graedel, B.R. Allenby, Industrial Ecology, 1995; Design for Environment, 1996;
Industrial Ecology and the Automobile, 1996, all from Prentice Hall, Paramus, NJ. (e) B.R. Allenby, Industrial Ecology: Policy
Framework and Implementation, Prentice Hall, Paramus, NJ, 1998.
13. A.W. Gessner, Chem. Eng. Prog., 1998, 94(12), 59.
14. (a) Anon., Preprints ACS Div. Environ Chem, 1994, 34(2), pp. 175–431. (b) P.T. Anastas, C.A. Farris, eds. Benign by Design: Al-
ternative Synthetic Design for Pollution Prevention, ACS Symp. 577, Washington, D.C., 1994; (c) P.T. Anastas, T.C. Williamson,
eds. Green Chemistry: Designing Chemistry for the Environment, ACS Symp 626, Washington, D.C., 1996; (d) S.C. DeVito, R.L.
Garrett, eds. Designing Safer Chemicals: Green Chemistry for Pollution Prevention, ACS Symp. 640, Washington, D.C., 1996;
Chemtech, 1996, 26(11):34. (e) J.J. Breen, M.J. Dellarco, eds. Pollution Prevention in Industrial Processes: The Role of Process An-
alytical Chemistry, ACS Symp. 508, Washington, D.C., 1994. (f) P.T. Anastas, T.C. Williamson, eds. Green Chemistry: Frontiers
in Benign Chemical Syntheses and Processes, Oxford University Press, Oxford, England, 1998.
15. (a) W. Buchner, R. Schliebs, G. Winter, K.H. Buchel, Industrial Inorganic Chemisty, VCH, Weinheim, 1989; (b) K. Weissermel,
H.-J. Arpe, Industrial Organic Chemistry, 3rd ed., VCH, Weinheim, 1997. (c) P.J. Chenier, Survey of Industrial Chemistry, 2nd ed.,
VCH, Weinheim, 1992; (d) H. Wittcoff, B. Reuben, Industrial Organic Chemicals, 2nd ed., John Wiley, New York, 1996; (e) J.I.
Kroschwitz, ed. Kirk-Othmer Encyclo Chem Technol, 4th ed., John Wiley, 1991; (f) J.I. Kroschwitz, ed. Encyclo Polymer Sci and
Eng, 2nd ed., John Wiley, New York, 1985–1989; (g) W. Gerhartz, ed., Ullmann’s Encyclo Ind Chem, 5th ed., VCH, Weinheim,
1985.
16. J. Haber, Pure Appl Chem, 1994, 66: 1597
17. (a) J.N. Armor, Environmental Catalysis, A.C.S. Symp. 552, Washington, D.C., 1993; (b) G.W. Parshall, S.D. Ittel, Homogeneous
Catalysis, 2nd ed. John Wiley, New York, 1992; (c) B.C. Gates, Kirk-Othmer Encyclo Chem Technol, 4th ed., 1993, 5, 320; (d) W.R.
Moser, D.W. Slocum, eds., Homogeneous Transition Metal-Catalyzed Reactions, Adv Chem 230, American Chemical Society,
Washington, D.C., 1992; (e) J. P. Collman, L. S. Hegedus, Principles and Applications of Organotransition Chemistry, University
Science Books, Mill Valley, CA, 1980; (f) C. Elschenbroich, A. Salzer, Organometallics—A Concise Introduction, VCH, Weinheim,
1992; (g) G. Braca, Oxygenates by Homologation or COHydrogenation with Metal Complexes, Kluwer Academic Publishers, Dor-
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18. (a) J. Tolgyessy, ed., Chemistry and Biology of Water, Air, Soil—Environmental Aspects, Elsevier, Amsterdam, 1993; (b) B. Evan-
gelou, Environmental Soil and Water Chemistry, Wiley, NY, 1998.
19. A. Kumar, R. Desai, R. Kumar, Environ. Prog., 1998, 17(2), S11. (gives a directory of World Wide Web sites)
20. (a) S.M. Bachrach, ed., The Internet: A Guide for Chemists, American Chemical Society, Washington, D.C., 1996; (b) T. Murphy,
C. Briggs-Erickson, Environmental Guide to the Internet, Government Institutes, Rockville, MD, 1998; (c) K. O’Donnell, L.
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949; (e) B.J. Thomas,The World Wide Web for Scientists and Engineers, SAE International, Warrendale, PA, 1998; (f) S. Lawrence,
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cators and Students, Wiley, NY, 1998.

Contents
Preface iii
1. INTRODUCTION 1
I. General Background 1
II. Toxicity of Chemicals in the Environment 2
III. Accidents with Chemicals 6
IV. Waste and Minimization 13
V. Conclusions 18
VI. Summary of Some Important Points 19
References 20
Recommended Reading 25
Exercises 25
2. DOING WITHOUT PHOSGENE 27
I. Introduction 27
II. Preparation of Isocyanates 28
III. Polycarbonates 39
IV. Summary and Conclusions 39
References 42
Recommended Reading 45
Exercises 45
3. THE CHLORINE CONTROVERSY 47
I. The Problem 47
II. Toxicity of Chlorine Compounds 50
III. Estrogen Mimics 51
IV. Bleaching Paper 52
V. Disinfecting Water 53
VI. Chlorofluorocarbons and Ozone Depletion 54
VII. Chlorinated Solvents 57
VIII. Syntheses Where the Chlorine Is Not in the Final Product 58
vii
viii Contents
IX. Summary and Conclusions 60
References 61
Recommended Reading 66
Exercises 66
4. TOXIC HEAVY METAL IONS 67
I. The Problem 67
II. End-of-the-Pipe Treatments 70
III. Biocides 72
IV. Catalysts for Reactions Other than Oxidation 74
V. Dyes and Pigments 75
VI. Electrical Uses 76
VII. Leather 77
VIII. Metal Finishing 77
IX. Oxidation 78
X. Miscellaneous 94
References 94
Recommended Reading 101
Exercises 101
5. SOLID CATALYST AND REAGENTS FOR EASE OF WORKUP 101
I. Introduction 103
II. The Use of Inorganic Supports 105
III. Ion-Exchange Resins 114
IV. Combinatorial Chemistry 118
V. Other Uses of Supported Reagents 120
VI. Cyclodextrins 126
References 128
Recommended Reading 135
Exercises 135
6. SOLID ACIDS AND BASES 137
I. Introduction 137
II. Polymeric Sulfonic Acids 138
III. Polymer-Supported Lewis Acids 139
IV. Sulfated Zirconia 140
V. Supported Metal Oxides 141
VI. Rare Earth Triflates 141
VII. Solid Bases 144
VIII. Zeolites and Related Materials 145
IX. Clays 155
X. Heteropolyacids 159
References 163
Recommended Reading 173
Exercises 173
7. CHEMICALSEPARATIONS 175
I. The General Picture 175
II. Inclusion Compounds 178
Contents ix
III. Separation of Ions 182
IV. Membrane Separations 185
References 192
Recommended Reading 200
Exercises 200
8. WORKING WITHOUT ORGANIC SOLVENTS 201
I. Advantages and Disadvantages of Solvents 201
II. Working Without Solvents 203
III. Reactions in Extruders 207
IV. Carbon Dioxide as a Solvent 210
V. Water as a Reaction Medium 214
VI. Surfactants and Cleaning 220
VII. Coatings 223
References 228
Recommended Reading 229
Exercises 229
9. BIOCATALYSIS AND BIODIVERSITY 241
I. Biocatalysis 241
II. Biodiversity 267
References 275
Recommended Reading 288
Exercises 288
10. STEREOCHEMISTRY 291
I. The Importance of Optical Isomers 291
II. The Chiral Pool 292
III. Resolution of Racemic Mixtures 295
IV. Asymmetric Synthesis 301
References 314
Recommended Reading 318
Exercises 318
11. AGROCHEMICALS 319
I. The Nature and Use of Agrochemicals 319
II. Problems with Agrochemicals 322
III. Alternative Agriculture 326
IV. Lawns 345
V. Genetic Engineering 346
VI. Integrated Pest Management 347
References 348
Recommended Reading 358
Exercises 358