Front matter

GREEN
CHEMISTRY

AN INCLUSIVE APPROACH
Edited by

BÉLA TÖRÖK
TIMOTHY DRANSFIELD
University of Massachusetts Boston, Boston, MA, United States


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Notices
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Practitioners and researchers must always rely on their own experience and knowledge in evaluating
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List of Contributors
Steven Ackerman University of Massachusetts
Boston, Boston, MA, United States

Daniel P. Dowling University of Massachusetts
Boston, Boston, MA, United States

Karelle Aiken Georgia Southern University,
Statesboro, GA, United States

Timothy Dransfield University of Massachusetts Boston, Boston, MA, United States

Nicholas D. Anastas United State Environmental
Protection Agency, Cincinnati, OH, United States

Clifford J. Ellstrom University of Massachusetts
Boston, Boston, MA, United States

Paul T. Anastas Yale University, New Haven,
CT, United States

Natalia Escobar-Pemberthy University of Massachusetts Boston, Boston, MA, United States

Gopalakrishnan Aridoss
Daejeon, South Korea

LG Life Sciences Ltd,

Daniel M. Genest University of Massachusetts
Boston, Boston, MA, United States

Johannes Bader Beuth University of Applied
Sciences, Berlin, Germany

Debanjana Ghosh Georgia Southern University,
Statesboro, GA, United States

Nadine
Borduas
Switzerland

Zurich,

Gerald E. Gilligan University of Massachusetts
Boston, Boston, MA, United States

Christopher Brigham University of Massachusetts Dartmouth, North Dartmouth, MA,
United States

Alain Goeppert University of Southern California,
Los Angeles, CA, United States

ETH

Zurich,

Gerald Gourdin Georgia Institute of Technology,
Atlanta, GA, United States

Gabriela Bueno University of Massachusetts
Boston, Boston, MA, United States

Robyn E. Hannigan University of Massachusetts Boston, Boston, MA, United States

Timothy P. Canty University of Maryland,
College Park, MD, United States

Julie A. Himmelberger DeSales University,
Center Valley, PA, United States

Philip Coish Yale University, New Haven, CT,

United States

William Horton University of Massachusetts
Boston, Boston, MA, United States

Kathryn
E.
Cole Christopher
Newport
University, Newport News, VA, United States

Patricia Hughes Center for Coastal Studies,
Provincetown, MA, United States

John Collins IBM Thomas J Watson Research
Center, Yorktown Heights, NY, United States
Studies,

Maria Ivanova University of Massachusetts
Boston, Boston, MA, United States

Levente Cseri The University of Manchester,
Manchester, United Kingdom

Stefan D. Kalev Gulf Coast Research and
Education Center, University of Florida,
Wimauma, FL, United States

Rupali Datta Michigan Technological University,
Houghton, MI, United States

Daniel Kirk-Davidoff University of Maryland,
College Park, MD, United States

Neil M. Donahue Carnegie Mellon University,
Pittsburgh, PA, United States

Anne Kokel University of Massachusetts Boston,
Boston, MA, United States

Amy Costa Center for Coastal
Provincetown, MA, United States

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xii

LIST OF CONTRIBUTORS

Kenneth K. Laali University of North Florida,
Jacksonville, FL, United States

Jonathan Rochford University of Massachusetts
Boston, Boston, MA, United States

Shainaz Landge Georgia Southern University,
Statesboro, GA, United States

Abhishek RoyChowdhury Stevens Institute of
Technology, Hoboken, NJ, United States

Nicholas A. Lee University of Massachusetts
Boston, Boston, MA, United States

Heather A. Rypkema Heritage Strategies, INTL,
Washington, DC, United States

Alexandra Maertens Johns Hopkins Bloomberg
School of Public Health, Baltimore, MD, United
States

Ross J. Salawitch University of Maryland,
College Park, MD, United States

Enda McGovern Sacred Heart
Fairfield, CT, United States

University,

Meaghan McKinnon University of Massachusetts Boston, Boston, MA, United States
Manisha Mishra University of Massachusetts
Boston, Boston, MA, United States
Ken T. Ngo University of Massachusetts
Boston, Boston, MA, United States
James Noblet California State University San
Bernardino, San Bernardino, CA, United States
George A. Olah University of Southern
California, Los Angeles, CA, United States

István Pálinkó
Hungary

University of Szeged, Szeged,

Peter Pogany Gedeon Richter Plc., Budapest,
Hungary
Helen C. Poynton University of Massachusetts
Boston, Boston, MA, United States
Deyang Qu University of Wisconsin Milwaukee,
Milwaukee, WI, United States
Mayamin Razali The University of Manchester,
Manchester, United Kingdom
William E. Robinson University of Massachusetts Boston, Boston, MA, United States

Dibyendu Sarkar Stevens Institute of Technology,
Hoboken, NJ, United States
Christian Schäfer University of Massachusetts
Boston, Boston, MA, United States
Laurel Schaider Silent Spring Institute, Newton,
MA, United States
Linda Schweitzer Oakland University, Rochester,
MI, United States
Abid Shaikh Georgia Southern
Statesboro, GA, United States

University,

G.K. Surya Prakash University of Southern
California, Los Angeles, CA, United States

Gyorgy Szekely The University of Manchester,
Manchester, United Kingdom
Gurpal S. Toor University of Maryland, College
Park, MD, United States
Béla Török University of Massachusetts Boston,
Boston, MA, United States
Marianna Török University of Massachusetts
Boston, Boston, MA, United States
David M. Wilmouth Harvard
Cambridge, MA, United States

University,

Julie B. Zimmerman Yale University, New
Haven, CT, United States

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Preface
The concept of this book was born in 2005
when we (along with Deyang Qu, who
wrote Chapter 3.23) taught Introduction to
Green Chemistry at UMass Boston. We teamtaught the course because none of us individually had expertise in everything we
wanted to cover. We were lucky to have
faculty whose specialties included air pollution, novel battery technologies, and green
synthesis, but even with our combined
backgrounds, we felt unprepared to show
the true breadth of the field of Green
Chemistry. We searched for a textbook to

help us fill in the gaps, but we could not find
one. We successfully ran the course using an
environmental chemistry textbook and a lot
of primary literature, but from the outset, we
realized that the course deserved a textbook
designed around it.
This, then, is the textbook we wish had
been available to us. It is intended for a
broad audience, including industry and
academia. It is aimed to be a contemporary
and inclusive Green Chemistry text that can
be used in undergraduate and graduate education and as a resource for researchers.
The main goal of the work was to be as
broad as possible, including many aspects of
Green Chemistry. The book includes three
main parts. The first two parts are intended
for those who teach Green Chemistry: it
covers the basic definitions, environmental
chemistry, renewable energy, sustainable
synthesis, fundamental chemical toxicology,
and the effect of environmental factors on
our genetic information. These chapters

follow a textbook style, providing examples,
recommended reading, and problem sets.
The third part of the work is designed for
researchers, as it contains in-depth reviews
on selected topics. Our intention is that educators, after covering the fundamentals laid
down in the first part, may select some of the
specialized research chapters as case studies

to further illustrate the state-of-the-art practice of Green Chemistry. Although the book
includes more topics than could be covered
in a typical undergraduate or even graduate
class, the variety of topics will provide opportunity for the faculty instructors to select
topics they are comfortable covering and can
fit into their schedules.
The centerpiece of the third part of the
book is Green Chemistry in practice. The
topics included in this part focus on special
areas of the field. Every chapter in this
part provides an up-to-date reference section, together comprising thousands of
original papers and review articles. We
believe that by including experts in many of
the fields discussed, the book provides the
readers with “insider information”: the aspects or challenges of a given field that the
specialists consider the most important and
urgent. This way, we hope that the book
will serve as a primary resource for those
who are new to Green Chemistry or those
who intend to branch out and discover
other topics that are related to their own
research fields.
We would like to thank our distinguished
colleagues and authors, experts in their fields,

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xiv

PREFACE

for contributing to this unique endeavor.
We also thank Kathryn Morrissey and Laura
Kelleher, who helped us through the proposal
phase of the book, and Anitha Sivaraj,
who handled the galley proofs. We are
indebted to Emily Thomson, our Editorial

Project Manager, for her enormous help and
continuous encouragements throughout the
process.

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Béla Török and Timothy Dransfield
Boston, May 1, 2017


C H A P T E R

1.1

Green Chemistry: Historical
Perspectives and Basic Concepts
Béla Török, Timothy Dransfield
University of Massachusetts Boston, Boston, MA, United States

Chemists and chemistry, in general, have made an enormous contribution to the history of

humankind. Beginning with the early alchemists, these contributions include several developments that changed the course of history for the better or, in some cases, for the worse.
Many of them may seem to be simple by today’s standards, but at the time, they were
groundbreaking discoveries and inventions. The fabrication of simple soaps made the formation of large cities possible by improving the personal hygiene. The production of dyes and
paints contributed significantly to fashion and art over the centuries. As the usefulness of
chemistry became clear, more people decided to pursue such endeavors, which brought
exponential growth in this field. As Dalton, Avogadro, and Lavoisier made their famous discoveries, chemistry became viewed more and more as science than as black magic. With significant developments in chemical theory came the increased pace of new applications that
inspired yet further progress. However, not every step along the way was problem free.
Several inventions that were made with the best intentions backfired and caused health or
environmental issues. The use of freons as inflammable carrier gases in all sorts of sprays
in the 1960se70s seemed to be perfect, until Rowland and Molina published their findings
on the terrible effect of these chemicals on the ozone layer that protects the earth from harmful ultraviolet radiation. Antibiotics were hot commodities after World War II, until it was
found that bacteria can develop resistance toward these compounds making them more difficult to fight against. Plastics seemed like a blessing until it was found that their degradation
takes over a thousand years. Dichlorodiphenyltrichloroethane (DDT) appeared to be an effective agent to fight malaria-spreading mosquitos, until it was found in fish around Antarctica,
proving that it lingers for a long time. Contemporary pesticides can leach into natural waters
and cause gender change in frogs. Many drugs have unintended harmful side effects. The list
is long. What is common in all these cases is that a product was developed for a certain purpose without a careful analysis of its broader impact on the ecosystem. All these disasters
initiated a different chemical thinking that now we call green chemistry.

Green Chemistry
/>
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1.1 GREEN CHEMISTRY: HISTORICAL PERSPECTIVES AND BASIC CONCEPTS

1.1.1 EMERGENCE OF GREEN CHEMISTRY
Early in the evolution of the chemical industry, scientists were already, although unconsciously, applying some of the much later formulated principles of green chemistry. For instance,
the development of heterogeneous catalytic petrochemical processes dates back to the 1930s. The
more conscious development of such thinking began after several major environmental disasters
and industrial accidents occurred. The aforementioned problems are just a few examples to
demonstrate the potentially harmful nature of chemicals if applied and introduced to the
biosphere without sufficiently careful forward thinking. Rachel Carson’s book, Silent Spring
(1962), which described the destruction of local ecosystems by toxic chemicals, likely was a
wake-up call for the society to address the issues or face grave consequences. As the first important step to address these issues the US Congress passed the National Environmental Policy Act in
1969. The US Environmental Protection Agency (US EPA) was established by President Nixon in
1970. Since the 1970s several environmental legislations have been implemented, such as the
Clean Air Act of 1970 and the Safe Drinking Water Act of 1974, that signaled the government’s
intention to solve the problems via regulations. The US Toxic Substances Control Act was passed
in 1976, and now it has over 80,000 chemicals in its listings. Later the more comprehensive Clean
Air Act and the Pollution Prevention Act were enacted, both in 1990. The term Green Chemistry was
coined by the EPA Office of Pollution Prevention and Toxins in the early 1990s. In 1995, the US
EPA established an annual awards program called the Presidential Green Chemistry Awards to
recognize the leaders of innovation from both industry and academia. In 1997, the first PhD
in Green Chemistry program was established at the University of Massachusetts Boston. In the
same year the Green Chemistry Institute was founded, which later became the American Chemical Society Green Chemistry Institute. Starting with the 1990s, several scientific journals devoted
to green chemistry research began publishing original research and review articles in the field.
Today, all major publishers have at least one journal devoted to green or sustainable chemistry
research with several books and textbooks published to aid research and education.

1.1.2 SUSTAINABLE PRODUCTION OF COMMODITIES:
PRINCIPLES AND BASIC CONCEPTS
Several tools and methods that are now considered as part of sustainable synthesis (e.g.,
catalysis) were developed much earlier than the formal green chemistry movement began.
It took concerted and conscious efforts to envision and design a framework that included
the earlier developments and initiated further progress in this field. The basic principle,

benign by design, emphasized that both the product and the process used to produce it should
conform to the basic rules of sustainability. In their seminal book in 1998, Anastas and
Warner established the major principles of green chemistry. Although since then several
“new principles” have been added to the list, the original list is still applicable.

1.1.2.1 Principles of Green Chemistry
1. Prevention: It is better to prevent waste than to treat or clean up waste after it has been
created.
2. Atom economy: Synthetic methods should be designed to maximize the incorporation of
all materials used in the process into the final product.
1. INTRODUCTION

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1.1.2 SUSTAINABLE PRODUCTION OF COMMODITIES: PRINCIPLES AND BASIC CONCEPTS

5

3. Less hazardous chemical syntheses: Wherever practicable, synthetic methods should be
designed to use and generate substances that possess little or no toxicity to human
health and the environment.
4. Designing safer chemicals: Chemical products should be designed to affect their desired
function while minimizing their toxicity.
5. Safer solvents and auxiliaries: The use of auxiliary substances (e.g., solvents, separation
agents, etc.) should be made unnecessary wherever possible and innocuous when
used.
6. Design for energy efficiency: Energy requirements of chemical processes should be recognized for their environmental and economic impacts and should be minimized. If
possible, synthetic methods should be conducted at ambient temperature and pressure.
7. Use of renewable feedstocks: A raw material or feedstock should be renewable rather

than depleting whenever technically and economically practicable.
8. Reduce derivatives: Unnecessary derivatization (use of blocking groups, protection/
deprotection, temporary modification of physical/chemical processes) should be minimized or avoided if possible, because such steps require additional reagents and can
generate waste.
9. Catalysis: Catalytic reagents (as selective as possible) are superior to stoichiometric
reagents
10. Design for degradation: Chemical products should be designed so that at the end of their
function they break down into innocuous degradation products and do not persist in
the environment.
11. Real-time analysis for pollution prevention: 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. Inherently safer chemistry for accident prevention: Substances and the form of a substance
used in a chemical process should be chosen to minimize the potential for chemical
accidents, including releases, explosions, and fires.
Since products that involve any chemistry during their preparation are all manufactured
by industry, the aforementioned list had to be amended to include specific issues that
chemical engineers face while transitioning a laboratory process to the industrial setting.
Hence, Anastas and Zimmerman developed a similar set of principles for engineering.

1.1.2.2 Principles of Green Engineering
1. Inherent rather than circumstantial: Designers need to strive to ensure that all materials
and energy inputs and outputs are as inherently nonhazardous as possible.
2. Prevention instead of treatment: It is better to prevent waste than to treat or clean up
waste after it is formed.
3. Design for separation: Separation and purification operations should be designed to
minimize energy consumption and materials use.
4. Maximize efficiency: Products, processes, and systems should be designed to maximize
mass, energy, space, and time efficiency.
5. Output pulled versus input pushed: Products, processes, and systems should be “output
pulled” rather than “input pushed” through the use of energy and materials.

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1.1 GREEN CHEMISTRY: HISTORICAL PERSPECTIVES AND BASIC CONCEPTS

6. Conserve complexity: Embedded entropy and complexity must be viewed as an investment when making design choices on recycle, reuse, or beneficial disposition.
7. Durability rather than immortality: Targeted durability, not immortality, should be a
design goal.
8. Meet need, minimize excess: Design for unnecessary capacity or capability (e.g., “one size
fits all”) solutions should be considered a design flaw.
9. Minimize material diversity: Material diversity in multicomponent products should be
minimized to promote disassembly and value retention.
10. Integrate material and energy flows: Design of products, processes, and systems must
include integration and interconnectivity with available energy and materials flows.
11. Design for commercial “afterlife”: Products, processes, and systems should be designed
for performance in a commercial “afterlife.”
12. Renewable rather than depleting: Material and energy inputs should be renewable rather
than depleting.
Several other sets of principles have been developed by different groups, for example,
Poliakoff’s mnemonic PRODUCTIVELY, that similarly summarizes the basic concepts
(Prevent waste, Renewable materials, Omit derivatization, Degradable products, Use of safe methods,
Catalysis, Temperature, pressure ambient, In-process monitoring, Very few auxiliaries, E-factor, Low
toxicity, Yes, it is safe). Certainly, the aforementioned principles were not developed overnight.
Several research groups have contributed to the development of the major concepts that
guided the growth of green chemistry. Here, we list these basic concepts and definitions

that will be used in the later chapters of this book.
E-factor: The E (environmental)-factor, developed by Roger Sheldon, is one of the most
practical descriptors of the efficiency; it is the mass ratio of waste to the target product.
For instance, E ¼ 20 means that 20 kg waste is produced to every kilogram of product.
Obviously, the smaller the number, the better; in the best possible circumstances (0 kg
waste is generated with the product), E ¼ 0. The E-factor is a commonly accepted and
applied measure to describe the efficiency of processes in the chemical and pharmaceutical industry for the assessment of the overall environmental impact.
Atom economy (AE): Atom economy (atom efficiency is also used), first described in 1991
by Trost, is defined by the ratio of the molecular weight of the product and the sum
of the molecular weights of all substances consumed in the stoichiometric equation
of a reaction. Commonly it is expressed as a percentage. It is important to highlight
that AE is based on the theoretical reaction (i.e., no unexpected by-products are
factored in) and 100% theoretical yield. Therefore the AE is the best possible scenario
and can be used to assess a reaction at the theoretical level. For example, if a reaction
scheme does not involve the formation of any expected by-product, the AE is 100%
(Scheme 1.1.1).
However, it is worth noting that it cannot be used exclusively to describe the environmental impact of a reaction: it may be that a reaction with 100% AE yields unexpected
by-products (e.g., stereo- or regioisomers) that would decrease the actual AE. Thus a highly
selective reaction with 80% theoretical AE and no unexpected by-products may have less

1. INTRODUCTION

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1.1.2 SUSTAINABLE PRODUCTION OF COMMODITIES: PRINCIPLES AND BASIC CONCEPTS

SCHEME 1.1.1

7

Hydration of cyclohexene to cyclohexanol; a 100% atom economic process.

environmental impact than a 100% AE reaction that is accompanied by extensive unexpected
by-product formation.
Although these are the two most important measures to describe the efficiency of a chemical process, several alternative metrics have been proposed, such as the reaction mass efficiency
(RME) defined as the mass ratio of the obtained product to the total mass of the reactants,
thus incorporating the actual percent yield into traditional AE calculations. Carbon efficiency
is similar to RME, but only considers carbon as a part of the product or starting materials
and reagents. Mass efficiency (total mass of the materials used divided by the mass of product
obtained given as a percentage) and effective mass yield (the ratio of the mass of the desired
product and the total mass of nonbenign reactants) are other available ways to describe
the environmental impact of processes. There is a general agreement in the literature that
the AE and E-factor are the most applicable and widely used measures in many industries.
Although the aforementioned metrics are able to estimate the impact of a process, there are
other considerations to discuss, such as the chemical characteristics of the waste. Obviously,
the ultimate process occurs with 100% AE and 0 E-factor; however, practical processes are
different and mostly produce either expected or unexpected by-products that are considered
waste. The nature of that waste is highly important. It is easy to realize that if the waste is
water (e.g., dehydration reactions) or sodium chloride (nucleophilic substitutions) that are
considered harmless, the process is quite different from, to choose one example from
many, the Jones oxidation of alcohols to ketones that generates a significant amount of chromium salt waste (Scheme 1.1.2).
To consider this highly important aspect, Sheldon introduced the environmental quotient
(EQ), which is calculated by multiplying the E-factor by an arbitrarily assigned environmental
unfriendliness quotient, Q. As an example, one can assign 1 to benign chemicals (such as water
or NaCl) and a large number (e.g., 100 or 1000) to chromium sulfate. Although as of yet a
clear definition or individual assignment of Q values to chemicals is not available, theoretically it is possible to quantify the environmental impact of chemical waste based on its
amount and toxicity. It is, however, a difficult task as compounds exhibit all sorts of harmful
biological activities, and although it is possible to rank them in terms of one effect (e.g., carcinogenicity or mutagenicity), the ranking (and the Q value) could be significantly different if
another type of toxicity is considered. In addition, when a process is generating a compound

that is not yet known, its biological effect only can be estimated, e.g., by quantitative structure-activity relationship models.
An even more extended approach that embraces the holistic evaluation of a process or
product is the life cycle assessment (LCA). The LCA considers a broad range of issues that

1. INTRODUCTION

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1.1 GREEN CHEMISTRY: HISTORICAL PERSPECTIVES AND BASIC CONCEPTS

SCHEME 1.1.2

Examples of chemical reactions producing toxic (red) and non-toxic (green) waste.

can be quantified by environmental friendliness metrics. These indicators include energy consumption, carbon footprint and emission of other greenhouse gases, potential contributions
to ozone depletion or smog formation, amount of waste generation, and toxicity of the waste
generated. The application of EQ or LCA, however, requires extended analysis before a process can be implemented, and this often contributes to the cost of a product. Nonetheless, as
highlighted by the original 12 principles, it is always better (and likely less expensive) to prevent problems by a thorough analysis than to clean up after an environmental disaster.

1.1.3 GREEN CHEMISTRY AND THE ENVIRONMENT
It is not within the scope of this text to provide a comprehensive examination of environmental chemistry. Indeed, many fine textbooks exist on that subject, and our goal is not to
reduplicate such works. Rather, the goal of the various environmental chemistry chapters in
this text is to put into context the impact of human society on the natural world. While the
precise placement of the dividing line between green chemistry and environmental chemistry can be debated, it is clear that the entire purpose of green chemistry is to minimize
that impact. This is most evident in principles 1 and 10: waste prevention and the design
of chemicals such that they degrade harmlessly in the environment. Obviously, then, the
practice of green chemistry requires an understanding of those degradation pathways

and an understanding of what happens to the waste and by-products when they are
emitted. Although various textbooks exist that provide greener pathways for industrial
synthesis, for example, there is an alarming shortage of texts that train green chemists to
think about the chemistry of their products in the wild. With this work, we hope to begin
to bridge that gap.

1. INTRODUCTION

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1.1.3 GREEN CHEMISTRY AND THE ENVIRONMENT

9

It may come as a surprise to some readers that society has long been aware of the impacts
of science and industry on the environment. The Mishnah laws of first- and second-century
Israel specified that threshing floors, leather tanneries, and lime kilns be removed 50 cubits
from the city to reduce exposure to airborne pollutants, and that flax stems be soaked at least
4e5 m from any vegetable fields to prevent water pollution from affecting the neighbor’s
food crops. The impetus for the construction of the Roman aqueducts was to transport clean
drinking water, as the Tiber had become so fouled with human waste. English laws attempted to curb pollution from the burning of coal as early as 1273, but the wave of the Industrial
Revolution overwhelmed those early efforts.
Even if we as a species were unaware of our effect on the environment, there has been
pollution as long as there has been civilization. There is evidence in ice core data that the
expansion of agriculture by the Romans and the cultivation of rice by the Han dynasty in
China, both in 1st century BCE, led to measurable increases in global methane concentrations.
Looking even further into the past, there is clear evidence of heavy metal pollution of soil and
water arising from metallurgy as long ago as 1500 BCE and continuing for nearly 2000 years.
Indeed, significant levels of these pollutants measured in modern lakes may in fact be

sourced to ancient industry rather than to more modern endeavors.
Ancient impacts aside, it is clear that since the Industrial Revolution the scale and the character of the pollution has fundamentally changed. Perhaps we can date this to 17th century
England, when John Evelyn wrote of the damage caused by London’s coal smoke in his
pamphlet, Fumifugium, although even this document refers to the history of England’s problems with coal dating back to the middle ages. Perhaps it dates to the cholera outbreaks
around the world in the 19th century, caused by contaminated drinking water in the growing
cities; or perhaps the burning of the Cuyahoga River, most notably in 1952, a result of the
accumulation of oil slicks on its surface; or the smog incidents of the mid-20th century in London, and Pennsylvania and Belgium, in which thousands of people died; or the widespread
use of DDT after World War II, now found in animal tissue samples from the most remote
locations on Earth; or the tragedy of Love Canal, where people living in houses built on a
landfill were exposed to toxic waste as the containers leeched into the soil; or the 1984 Union
Carbide disaster in Bhopal, India, where 4000 people died from exposure to methyl isocyanate; or the photochemical smog in Los Angeles during the 1980s, or that of Mexico City,
Delhi, and Beijing today; or Three Mile Island, Chernobyl, and Fukushima, reminding us
that the wonders of the nuclear age bring with them new dangers. It is true that human science and technology have combined to produce a society that is awe inspiring. However, it is
also true that this society has wreaked havoc on our natural environment.
According to most geology textbooks, the most recent geological epoch began nearly
12,000 years ago with the dawn of the Holocene. However, the conversation in recent years
has recognized the shift in mankind’s ability to harm our planet on a global scale. In 2000,
Nobel laureate Paul Crutzen argued for the use of the term Anthropocene, referencing that
our current period is defined by our species more than by any other characteristic. Crutzen
did not coin the phrasedit had been used by Soviet scientists as early as the 1960s, and
perhaps even predates them. However, the dawn of the 21st century was also the dawn of
widespread acceptance of the harsh realities of global warming and its associated climate

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1.1 GREEN CHEMISTRY: HISTORICAL PERSPECTIVES AND BASIC CONCEPTS

changes. Already the pH of the oceans is dropping, leading to the distinct possibility of mass
extinction of life in the sea. The ongoing “Holocene extinction” is removing up to 140,000 species from our planet each year, a rate that rivals that of the extinction that took the dinosaurs.
Left unchecked, the modern tail of the Industrial Revolution threatens all life on the planet.
Often doomsayers will claim that we are on the verge of destroying the planet itself. This is
presumably hyperboledthe planet has seen mass extinction before, and will again. However,
the same cannot be said of the human race.
To be clear, the authors do not believe that we are witnessing the end of human civilization. Because one way or another, our destruction of the environment will be checked. At
some point, the financial arguments against change will fall by the wayside as the need for
change becomes more urgent. Whether driven by government intervention or an industrial
recognition of the bottom line, at some point the solutions to these problems will become
financially competitive with the cost of doing nothing. It falls to practitioners of green chemistry to provide the solutions at a cost that obtains that result as soon as possible.

1.1.4 REGULATORY AGENCIES
Environmental regulatory agencies are part of life in most countries. They provide guidance for new developments and oversight for existing industrial technologies as well as common aspects of life, from the disposal of restaurant waste to application of cosmetics. Since
the detailed discussion of environmental law and regulatory agencies is far beyond the scope
of this introductory chapter, here we describe several of most visible regulatory agencies that
are charged with managing the environmental issues in the largest economies.

1.1.4.1 International: The United Nations
The United Nations (UN) took a leadership role in facilitating discussions, organizing international conferences where the member nations could develop strategies to combat environmental issues. Per the suggestion of Sweden, the UN organized the United Nations
Conference on Human Environment in Stockholm in 1972. The assembly agreed upon the Stockholm Declaration, which put forth 26 principles to guide environmental protection and development. The World Commission for Environment and Development, first chaired by Gro Harlem
Brundtland (former Prime Minister of Norway), was established in 1983. It was tasked with
generating a report on the environment and with making recommendations for a worldwide
sustainable and environmentally benign economic development to 2000 and beyond. The
assessment and recommendations of the commission were published in a book entitled
Our Common Future (Oxford University Press) in 1987. Since then, the UN has spearheaded
efforts on various environmental issues.
One enormously successful early agreement was the Montreal Protocol (1987) to combat the

depletion of ozone over the poles in spring, commonly referred to as the “ozone hole.” The
global ban on chlorofluorocarbons and related compounds succeeded in stopping the deterioration, and the atmosphere continues to recover slowly but surely. The success of the Montreal
Protocol was remarkable; former UN Secretary-General Kofi Annan hailed it as “perhaps the

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single most successful international agreement to date.” This is in marked contrast to the international community’s much slower and more contested response to global warming. The most
important and well-known treaties to combat climate change are the Kyoto Protocol (1997) and
the Paris Agreement (2015). The Kyoto Protocol described the commitment of the participating
countries to reduce the emission of greenhouse gases. The Paris Agreement, the result of the UN
Framework Convention on Climate Change, while aiming for a similar goal, made recommendations on how much to limit the annual temperature increase of the planet. As of today, 131
(out of 197) parties have ratified the Paris Agreement.
This leads us to mention the weaknesses of some of the UN-facilitated agreements. Given
the nature of the UN, these treaties are negotiated by the governments of the participating
countries. However, once the agreement is signed, the law-making bodies of the nations
have to ratify it; thus the countries essentially commit themselves by their own laws to uphold the agreement. That has been so far the Achilles’ heel of many such agreements: several
countries ratified it, whereas many others did not. The reasons for not ratifying vary from
country to country and depend on economic development, energy/fuel production and
use, and many other socioeconomic factors. Unfortunately, many of these agreements are
purely political and do not include the development of actual technologies as a response
to global warming.

1.1.4.2 International: International Organization for Standardization

The International Organization for Standardization (ISO) is a nongovernmental international organization with 161 members that are commonly the similar standards bodies of
the member countries. In 1946, 25 countries decided to establish the ISO to provide unified
industrial standards. It is a forum to share knowledge and develop consensus-based international standards that help innovation and offer solutions to global problems. Although
the ISO is not specifically an environmental organization, many of its approximately
21,000 international standards are related to environmental and safety issues. The most
relevant of these are ISO1400-Environmental Management, ISO45001-Occupational Health
and Safety, ISO50001-Energy Management, ISO22000-Food Safety Management, and
ISO31000-Risk Management. However, it is important to note that similar to the above
UN recommendations the ISO standards are applied voluntarily by the individual organizations (e.g., corporations) of the member countries.

1.1.4.3 United States
We have already introduced the US EPA earlier in this chapter, which takes the lead on
many issues from toxic waste cleanup to mitigation of global warming. The EPA fulfills the
roles of a regulatory agency and recommends changes and additions to current environmental laws that Congress considers. The EPA, however, is not just an agency that
regulates and enforces regulations. It has a broad network of research facilities, institutes
in which far-reaching scientific research is conducted in several areas of environmentrelated sciences, from sustainable synthesis to atmospheric chemistry. In addition,
all US states have their own EPA-like agencies, sometimes just one umbrellalike

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agency; however, in many states, there are separate entities to deal with separate issues
(water, agriculture, etc.).
The National Oceanic and Atmospheric Administration (NOAA) (part of the Department of

Commerce) also concerns itself with environmental issues. It grew out of some of the oldest
government branches dedicated to the environment, including the United States Coast and
Geodetic Survey, which was first established in 1807 by Thomas Jefferson. In 1970, President
Nixon created NOAA from several other agencies, including the Weather Bureau (1870) and
the Bureau of Commercial Fisheries (1871). Its current substructure includes the National
Weather Service, the National Ocean Service, and the Environmental Satellite, Data and Information Service, among others. Through these divisions it contributes by observing and
communicating data related to global warming and atmospheric and water pollution. Similar
to the EPA, the NOAA has facilities that conduct active research on the environment.

1.1.4.4 Canada
The Environment and Climate Change Canada is the major government agency that regulates and enforces environmental protection in Canada. It was established in 1971 by the
Department of Environment Act to assess, monitor, and protect the environment, including
providing basic weather and meteorological services to the citizens of Canada. The agency’s
responsibilities are those of a typical environmental agency: making environmental decisions/regulations based on available evidence, especially with regard to pollution prevention
and the like. In addition to its support to policy making, the agency is a supporter of a broad
variety of environment-related research through many funding initiatives. Just as in the
United States, the Canadian Provinces have their own environmental agencies.

1.1.4.5 European Union
The European Union established its main environmental agency, the European Environment Agency (EEA), in 1990, which became operational in 1994. The agency has 33 member
states (28 EU members and Norway, Iceland, Lichtenstein, Switzerland, and Turkey). Six
additional countries from the Balkans work with the Agency as cooperating countries. Given
the nature of the European Union, most member countries had established their own environmental agencies long before the EEA, such as the Federal Environmental Agency (and
others) in Germany (1974), the Environment Agency in the United Kingdom (1995), the Ministry of Ecology, Sustainable Development and Energy in France (since 1974 under various
names), just to name a few. Thus the EEA’s role is mainly to provide independent information on the environment. They are the major EU information source for policy makers as well
as the general public, integrating the principals of sustainability into political and economic
decisions.

1.1.4.6 Russia
The Ministry of Natural Resources and the Environment (MNRE) is the main policy-making

and enforcing body in Russia. Russia has had some sort of natural resources governmental

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unit since the 18th century. The MNRE was created in 2008 by merging the former Ministry of
Environment and Ministry of Natural Resources (both founded in 1996, after the collapse of
the Soviet Union). It has several agencies such as the Federal Service for the Supervision
of Natural Resources, the Service for Hydrometeorology and Environmental Monitoring,
and separate agencies for subsoil, water, and forestry management.

1.1.4.7 China
Immediately after the Stockholm Declaration, China created its Environmental Protection
Leadership Group (1974) and environmental protection became a state policy in 1983 with the
Environmental Protection Commission. After several upgrades and name changes, the current Ministry of Environmental Protection (MEP) was established in 2008. China, the most
populous country in the world, has seen an unprecedented industrial growth and urbanization since the 1980s, which has brought with it significant environmental problems, including
water and air pollution. The major mandates of the MEP include the design, organization,
and implementation of national policies, programs, and plans for environmental protection,
policy making, and regulations and leading the response to major environmental problems.
In addition, it carries out environmental protection science and technological activities
including the organization of projects on engineering, and facilitates the development of environmental technology management systems as well as conducts and organizes environmental education.

1.1.4.8 India
India, as the second most populous country in the world, with rapidly growing industrial

activity has its fair share of environmental problems. In addition to industrial accidents, water shortages, soil problems (e.g., exhaustion, erosion), deforestation, and, especially in the
major metropolitan areas, air and water pollution affect many areas in the country. To
address these problems, the Central Pollution Control Board (founded in 1974) created the
National Air Quality Monitoring Program. Due to the inspirational power of the Stockholm
Declaration, in 1972, the National Council for Environmental Policy and Planning within the
Department of Science and Technology was established to protect the environment. This
council later became the Ministry of Environment and Forest, which is India’s most important
governmental agency for environmental protection. The Environment Protection Act of 1986
is one of the major early milestones in its actions. The current legislative framework includes
climate change, deforestation management, coastal regulations zones, and pollution control,
among many other tasks.

1.1.4.9 Japan
Many countries started seriously considering environmental protection only after the
Stockholm Declaration (1972), whereas Japan was among the first countries to enact environmental regulations after four major pollution outbreaks occurred in the country in the
1950se60s. In 1958, a water quality conservation law was passed, which was followed in

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1962 by a smoke and soot emission control law. In 1971, the first Environmental Agency
was established in Japan. Currently, the Ministry of the Environment is the branch of the
Government of Japan that is responsible for activities related to the environment. This agency
has broad responsibilities, as it is involved in policy making concerning waste management

and recycling, pollution control, nature conservation, wildlife protection, air quality and
transportation, as well as health and chemicals, and is also charged with the care of Japan’s
national parks.

1.1.4.10 Australia
The Department of Environment and Energy (DEE) is the major government agency in
Australia in charge of environmental protection. It designs and implements government policies and programs to protect and conserve the environment, water, and heritage, and promotes climate action. DEE deals with a broad array of activities, such as far-reaching
environmental protection of Australian air, land, and water; managing the national parks;
conducting research on environmental problems; as well as acting as a funding agency for
environmental research. Similar to the United States and Canada, the Australian states also
have their own individual environmental agencies.

1.1.5 CLOSING THOUGHTS
The nature and scope of the field of chemistry has changed dramatically since the days of
the alchemists. Chemistry impacts nearly every aspect of modern life. The progression has
not always been smooth, and there have been significant missteps along the way. However,
the harnessing of chemistry in the interest of society has brought us to a modern age unimaginable by our ancestors. Toward the end of the 20th century, the field of green chemistry was
born from a recognition of those missteps and a desire to minimize the impact of human society, and especially of human industry, on our natural environment. The core philosophy
can be expressed in various ways, with lists of principles and metrics. The goal is always
the same: benign by design.
Societal impact on the environment presents us with multiple pressing problems, which
can be addressed by various means. All things considered, it would be preferable if chemical
solutions could be found before political solutions are required. This could entail, for
example, a reimagining of an existing technology (e.g., the electric car, biodegradable plastics), a means to reduce the environmental impact (e.g., solvent-free synthesis, exhaust plume
scrubbers), or a technology to remove existing pollutants (e.g., CO2 sequestration, bioreactor
landfills). By finding a way for companies to profit from the mitigation of pollution, green
chemists can encourage society to adopt these changes much more quickly and completely
than would a reluctant culture enforced by governmental policies. This is not to minimize
the importance of effective policies to control pollution; as we have seen, these efforts are critical to solving national- and global-scale problems. However, one of the goals of green chemistry must be to better facilitate widespread adoption of these new technologies and new
methodologies by making them acceptable for everyone.

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PROBLEMS

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PROBLEMS
1. Calculate the atom economy and E-factor of the following processes:

2. Reactions A and B are two different methods producing the same product P. Reaction
A has a theoretical atom economy of 100% with an actual yield of 65% for the product.
Reaction B only possesses 85% atom economy, with 95% actual yield for the product.
Which reaction is greener, that is, generates less waste considering 100% conversion of
A and B?
3. Research the similarities and differences between environmental quotient and life cycle
assessment.
4. Select any chemical product and design a green pathway for it considering the complete process (all details from finding/manufacturing starting materials, other components, minimizing environmental impact, etc.). Show your work in a flowchart from
the beginning of the manufacturing phase to the likely fate of the product/postproduct
in the environment.

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1.1 GREEN CHEMISTRY: HISTORICAL PERSPECTIVES AND BASIC CONCEPTS

5. Solar panels are a popular product marketed widely to offer consumers the opportunity to harness the energy of the sun. Research the manufacturing process of solar
panels and prepare an in-depth analysis on the cost and environmental impact of their
production. Compare the environmental impact of generating energy using solar
panels through the complete lifetime of these panels with that of the same amount energy generated by a coal-based power plant.
6. Several times in this chapter, the smoke from coal burning was mentioned as being
especially damaging to the environment and to human health. Research what compounds in coal smoke are primarily responsible for these effects.
7. John Evelyn’s Fumifugium detailed the health impacts of coal burning in 17th century
London and was written to request intervention by the Parliament and the King.
Investigate the alarming health statistics that led to his appeal.
8. How does an increase in pastoral agriculture result in an increase in methane emissions? What about rice cultivation?
9. The history of environmental pollution is often the history of unanticipated
consequences. Two excellent examples of this are the stories of DDT and CFCs.
a. In 1948, the Nobel Prize in medicine was awarded for the invention of DDT to
combat disease in the aftermath of World War II. Why was DDT so effective in this
role? What is it about DDT that made its widespread use so problematic?
b. CFCs were one of the “miracle” inventions of the 20th century, replacing toxic and/
or flammable gases in a variety of applications. What were some of these applications and what were the gases that they replaced?
10. A staggering variety of organic pollutants were found in the soil, water, and air
samples taken from Love Canal in 1977. One of the highest concentrations was of
benzene. Research the toxicity of benzene, including its mode of action and its
mandated concentration limits in the environment.
11. Analyze the 1997 Kyoto Protocol and 2015 Paris Agreement and describe the major
points in both. By comparing the two, summarize the development that occurred
during the nearly 20 years that passed between the two agreements.

Recommended Reading
1.

2.
3.
4.
5.
6.
7.
8.

Anastas PT, Warner JC. Green chemistry: theory and practice. New York: Oxford University Press; 1998.
Lancaster M. Green chemistry e an introductory text. 3rd ed. Cambridge: RSC; 2016.
Matlack AS. Introduction to green chemistry. 2nd ed. New York: CRC Press, Taylor & Francis; 2010.
Kovacs L, Csupor D, Lente G, Gunda T. 100 chemical myths: misconceptions, misunderstandings, explanations. Heidelberg,
New York, Dordrecht, London: Springer Cham; 2014.
Li C-J, Anastas PT. Green chemistry: present and future. Chem Soc Rev 2012;41(4):1413e4.
vanLoon GW, Duffy SJ. Environmental chemistry: a global perspective. 3rd ed. Oxford: Oxford University Press; 2010.
Spiro TG, Purvis-Roberts KL, Stigliani WM. Chemistry of the environment. 3rd ed. California: University Science
Books; 2012.
Baird C, Cann M. Environmental chemistry. 5th ed. New York: WH Freeman; 2012.

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C H A P T E R

2.1

Environmental Chemistry,
Renewable Energy, and Global

Policy
Heather A. Rypkema
Heritage Strategies, INTL, Washington, DC, United States

2.1.1 INTRODUCTION
The future welfare of our planet depends on a thorough understanding of our current technology and its effects on the environment. Earlier manifestations of mankind, in which the
height of environmental impact consisted of the occasional slaughtering of a large mammal,
had little or no impact on the world that surrounded it. Today, however, almost every aspect
of our lifestyle has a profound effect on the macrocosm of Earth’s ecosystems. Most daily activities contribute to this impact in varied, and often unexpected, ways.
Most people realize that the mundane act of driving a car contributes to one’s carbon footprint, thereby pouring carbon dioxide into the atmosphere, which contributes to global
warming, more currently enveloped into the phenomenon of climate change. But what
impact does this really have? What is the implicit environmental effect of trading in a traditional vehicle for a hybridddoes the increased fuel economy and reduced carbon footprint
counterbalance the addition of an otherwise usable vehicle to the exploding mass of metalcontaminated landfill? And, more generally, what is the difference between global warming
and climate change?
There are national movements to reduce the consumption of bottled water, but why? Most
obviously, there is the economic element of paying $1 or more for a bottle of water, when the
equivalent amount of tap water costs 0.1 cents. Additionally, there is the environmental waste
impact of the plastic container. What are the long-term environmental impacts of the plastic
bottle? In 2015, 11.7 billion gallons of bottled water were consumed in the United States, a
volume that equates to more than 75 billion individual 20-oz bottles, more than 60% of which
ultimately end up in landfills. Furthermore, how much energy is expended just to produce
this packaging? The annual energy cost of producing plastic bottles to contain commercial

Green Chemistry
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2.1 ENVIRONMENTAL CHEMISTRY, RENEWABLE ENERGY, AND GLOBAL POLICY

water is enough to fuel 1.3 million cars for a year. It is easy to muster outrage at a cartoon
image of a glowing, gelatinous goop being dumped into a pristine river full of happy, jumping fish, but too few people realize that even the most innocent and cleanest of man-made
products can carry a hidden environmental threat.
The ambiguous phrase, “pollution,” has been used for decades to excoriate emissions from
industry and other sources, but it is rarely explained in detail through mainstream media
coverage because to truly understand the threat of pollution, one must first understand the
chemistry of the pollutants being expelled. Yes, pollutants are bad, but what precisely are
the climatological, ecological, and economic impacts of their presence? How and why are
they so detrimental to ecosystems and human life? Without understanding these concepts,
one is poorly armed to argue against them. And without well-researched dissent, there can
be no change to the status quo of environmental pollution.
Today’s technology offers myriad pathways for improving the life of any human being
with access to it, but these advancements come with a cost. Almost any piece of technology
you use on a daily basis has a hidden price of environmental degradation. Cars, as previously
mentioned, contribute to your carbon footprint and add dangerous radicals to the atmosphere. Smartphones are now ubiquitous in the developed world and beyond, but the
disposal of faulty or unwanted phones provides a new challenge toward chemical remediation in landfills. Nearly every industry associated with natural resources, mining, agriculture,
drilling, etc., has a deleterious environmental impact that must ultimately be eliminated if we
are to cooperatively maintain the health of our planet.
The fundamental purposes of green chemistry are to:
1.
2.
3.
4.
5.

Identify environmental threats.
Understand the chemical processes leading to environmental threats.
Analyze how and why these threats are occurring.
Devise a way to alter current technology to avoid these problems.
Determine how to remediate damage already inflicted.

Each of these points is equally important, and the solution to any one of them will require a
wide variety of chemical and other scientific expertise. Nevertheless, a thorough understanding
of green chemistry can allow a scientist to initiate the process of resolution for any given step.

2.1.2 ENVIRONMENTAL CHALLENGES
2.1.2.1 Challenges by Air
Air pollution is one of the most immediate and visible forms of environmental harm
enacted by human technological advances and the source of many of the early environmental
disasters in human history. While far from being the earliest incident, the London killer fog is
one of the most notorious. In the winter of 1952, an unexpected cold snap hit London, causing
a rise in the level of coal burning, which infused the city’s air with sulfurous gas. An inversion
layer, in which higher altitude air is warmer than that nearer the ground, trapped the pollutants at ground level, resulting in a toxic miasma throughout the city. Exposure to sulfurous
compounds such as sulfuric acid (H2SO4) and sulfur trioxide (SO3) resulted in damage to the

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eyes, lungs, and gastrointestinal tracts of thousands of people. This convergence of human

pollution and meteorological happenstance is estimated to have caused the death of more
than 12,000 people, with young children and the elderly being particularly susceptible targets. This disaster led to the Clean Air Act of 1956, which was passed by the parliament to
impose restrictions on urban coal burning, and encouraged homeowners to upgrade to
more modern technologies for climate control (Fig. 2.1.1).
Although the killer fog is an exceptional example, it highlights the dangers of anthropogenic chemical emissions, which have increased exponentially in the half century since the
event itself. Furthermore, direct toxicity represents only a small portion of the environmental
threats caused by human production. Environmental scientists must also consider more subtle effects, such as the ultimate fate of a chemical in the atmospheredhow it will react and
what by-products it will producedas well as its interaction with the bombardment of
radiationdinfrared radiation (IR) from the earth and visible and ultraviolet (UV) from the
sundthat form a ceaseless flux of energy through our atmosphere.
Another significant example is the Bhopal, India, disaster of 1984, in which a leak from a
pesticide plant resulted in the death of at least 4000 people and injury to more than 500,000. In
this incident, at least 30 tons of methyl isocyanate (CH3NCO) was released from the plant to
the surrounding area. Additional toxins are believed to have included phosgene (COCl2),
chloroform (CHCl3), hydrogen chloride (HCl), and further organic pollutants, which were
either included in the tanks or were formed subsequently in the atmosphere. Children
were blinded and thousands of animals were killed, and Union Carbide, the company that
operated the plant, resumed operations without cleaning up the site (Fig. 2.1.2).
The challenges of environmental scientists in the atmospheric arena are multifold. They
must identify potentially toxic emissions, predict the fate of these emissions after exposure
to the chemical context of the atmosphere, develop alternative technologies to supplant

FIGURE 2.1.1 Westminster, London, 1952. A toxic fog has enveloped London due to increased coal burning in an
unexpected cold snap. Thousands of people died as a result of this deadly miasma. Image credit: George Tsiagalakis.

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2.1 ENVIRONMENTAL CHEMISTRY, RENEWABLE ENERGY, AND GLOBAL POLICY

FIGURE 2.1.2 Remains of the Bhopal chemical plant, following the 1984 disaster in which more than 4000 people
died as a result of substandard safety precautions. Image credit: Julian Nitzsche.

harmful substances, and advocate for policy changes, both local and international, that might
help prevent further environmental disasters from taking place.

2.1.2.2 Challenges by Sea
The oceans and natural waterways of our planet are particularly vulnerable to the damage
posed by environmental contaminants. Exposure to pollutants can occur through runoff from
common industries such as mining, direct dumping from industrial plants, pesticides transported through rainwater, or multitudinous other mechanisms (Fig. 2.1.3).
This waste poses a threat to both humans and wildlife, poisoning the species it encounters
as well as the humans who harvest them or drink the polluted water. The environmental
impact of water pollutants can affect humans and animals directly, or indirectly through
the transformations that occur via the chemical or biological environment. Microbes can
transform neutral species into toxic ones, and the acidity or basicity of waterways can alter
the reactivity of the otherwise harmless chemical compounds.
Although nearly every human industry contributes to water pollution, the most infamous
ecological disasters have come from the petrochemical industry. In 1989, the Exxon Valdez oil
tanker struck a reef off the coast of Alaska, spilling almost 11 million gallons of oil into open
waters (Fig. 2.1.4).

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FIGURE 2.1.3

Waste being dumped into a natural waterway. Chemical waste deposited directly into natural
waters is an efficient way to spread ecological harm. Image Credit: Frank J. Aleksandrowicz.

FIGURE 2.1.4 The Exxon Valdez oil tanker ran aground in 1989. At the time, this was one of the worst ecological
disasters on record, resulting in the death of between 100,000 and 250,000 animals, including sea birds, seals, orcas,
and otters. Photo courtesy of the Office of Response and Restoration, National Ocean Service, National Oceanic and Atmospheric Administration.

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